JP2011148946A - Adhesive for connecting circuit and anisotropic electroconductive film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive for connecting a circuit for forming an anisotropic electroconductive film improving the capturing rate of electroconductive particles, insulating properties and conduction properties. <P>SOLUTION: The adhesive for connecting the circuit includes: an adhesive 20; and inorganic oxide particles 9. Furthermore, the inorganic oxide particles 9 include: a first hydrophobic layer 32 covering the inorganic oxide particles 9; and a second hydrophobic layer 34 covering the inorganic oxide particles 9 or the first hydrophobic layer 32. The whole mass of the inorganic oxide particles 9 based on the total amount of the adhesive 20 is &gt;5 mass%. The first hydrophobic layer 32 or second hydrophobic layer 34 contains a silicone oligomer. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to an adhesive for circuit connection and an anisotropic conductive film.

  An anisotropic conductive adhesive in which conductive particles are dispersed in an adhesive is used for electrical connection between circuit boards, or electrical connection between an IC chip or an electronic component and a circuit board. Such a development of the connection form is remarkable in the liquid crystal field. The method of mounting a liquid crystal driving IC on a liquid crystal display glass panel can be broadly classified into two types, COG (Chip-on-Glass) mounting and COF (Chip-on-Flex). In COG mounting, an IC for liquid crystal is directly bonded onto a glass panel using an anisotropic conductive adhesive containing conductive particles. On the other hand, in COF mounting, a liquid crystal driving IC is bonded to a flexible tape having metal wiring, and these are bonded to a glass panel using an anisotropic conductive adhesive containing conductive particles. The anisotropy here means that the anisotropic conductive adhesive is conductive in the pressurizing direction at the time of pressure bonding, and the insulating property is maintained in the non-pressurizing direction. As the conductive particles, particles obtained by performing nickel plating or nickel / gold plating on the outside of the plastic particles are used. Nickel / gold plated particles have better insulation.

With the recent high definition of liquid crystal displays, gold bumps, which are circuit electrodes of liquid crystal driving ICs, are becoming narrower in pitch and area. Therefore, there is a problem that the conductive particles of the anisotropic conductive adhesive flow out between adjacent circuit electrodes and cause a short circuit. This tendency is particularly remarkable in COG mounting. If conductive particles flow out between adjacent circuit electrodes, the number of conductive particles in the anisotropic conductive adhesive trapped between the gold bump and the glass panel decreases, and the connection resistance between the opposing circuit electrodes increases. There was a problem of poor connection. Particularly in recent years, since 20,000 particles / mm ² or more of conductive particles are introduced per unit area by narrowing the pitch and area of gold bumps, the tendency is remarkable.

  Therefore, as a method for solving these problems, as exemplified in Patent Document 1 below, by forming an insulating adhesive on at least one surface of the anisotropic conductive adhesive, the bonding in COG mounting or COG mounting There are ways to prevent quality degradation. Further, as exemplified in Patent Document 2 below, there is a method of covering the entire surface of the conductive particles with an insulating film.

JP-A-8-279371 Japanese Patent No. 2779409 JP 2004-210875 A JP 2004-168559 A

However, in the method of forming an insulating adhesive on one side of the circuit connection member, when the bump area is less than 3000 μm ² and the conductive particles are increased in order to obtain a stable connection resistance, the insulation between adjacent electrodes There is still room for improvement in sex. Furthermore, the method of covering the entire surface of the conductive particles with an insulating coating has a problem that the conductivity tends to be low although the insulating property is high.

In addition, despite the increase in conductive particles, there is a problem that it is difficult for the conductive particles to ride on the bumps due to the resin flow during pressure bonding. Therefore, it is important to prevent the conductive particles from moving as much as possible at the time of crimping from the viewpoints of both conductivity and insulation. In other words, in order to improve both the electrical conductivity between the circuits facing each other in the pressurizing direction and the insulation between the adjacent electrodes in the non-pressurizing direction, trapping of the conductive particles defined by the following formula (B) It is important to increase the rate.
Capture rate (%) = (Average number of conductive particles on bump / Bump area / Number of conductive particles contained per unit area of anisotropic conductive film) × 100 (B)

  In the method of covering the surface of the conductive particles with the insulating child particles, the balance between the initial insulating property and the conductivity is good. However, this measure alone cannot sufficiently prevent insulation deterioration during a long-term reliability test due to migration of conductive particles.

  Therefore, the present inventors tried to improve the capture rate by adding inorganic oxide particles to the anisotropic conductive film and increasing the viscosity of the anisotropic conductive film. Examples of the inorganic oxide particles include inorganic oxide particles coated with hydrophobic molecules (see Patent Documents 3 and 4 above). Commercially available hydrophobic inorganic oxide particles include R202 (manufactured by Nippon Aerosil Co., Ltd.) coated with dimethylsiloxane and φ14 nm silica, R805 (manufactured by Nippon Aerosil Co., Ltd.) coated with octylsilane and φ12 nm silica. .

  However, when nanoscale inorganic oxide particles coated with hydrophobic molecules are added in a large amount to the adhesive for circuit connection, aggregation of the inorganic oxide particles causes a difference formed by applying the adhesive for circuit connection. The appearance of the directionally conductive film is deteriorated. Moreover, even if the inorganic oxide particles crushed in the organic solvent are added to the adhesive for circuit connection, the inorganic oxide particles are immediately re-agglomerated.

  The present invention has been made in view of the above-described problems of the prior art, and improves the trapping rate of conductive particles and simultaneously improves the insulation in the non-pressurization direction and the conductivity in the pressurization direction. It aims at providing the adhesive for circuit connection for forming a film, and an anisotropic conductive film.

  In order to achieve the above object, an adhesive for circuit connection according to the present invention comprises an adhesive and inorganic oxide particles, and the first oxide layer covers the inorganic oxide particles. A second hydrophobic layer covering the inorganic oxide particles or the first hydrophobic layer, and the total mass of the inorganic oxide particles relative to the total amount of the adhesive is greater than 5% by mass, and the first hydrophobic layer or the second hydrophobic layer The layer includes a silicone oligomer. The circuit connecting adhesive according to the present invention may include conductive particles.

  An anisotropic conductive film according to the present invention includes a conductive particle layer having the circuit connecting adhesive according to the present invention and conductive particles contained in the circuit connecting adhesive.

  In the said invention, the insulation of the adhesive agent for circuit connection improves significantly by addition of an inorganic oxide particle. In the present invention, addition of inorganic oxide particles improves the monodispersity of the conductive particles in the conductive particle layer and makes the conductive particles difficult to move. As a result, according to the present invention, it is possible to improve the capturing rate of the conductive particles and simultaneously improve the insulation in the non-pressurization direction and the conductivity in the pressurization direction. Furthermore, according to the present invention, since the capture rate is improved, the amount of conductive particles introduced into the anisotropic conductive film can be suppressed.

  In the present invention, the inorganic oxide particles preferably have a particle size of 5 to 30 nm. In the present invention, the inorganic oxide particles are preferably silica. Hydrophobic treatment of silica having the above particle diameter is easy to perform stably, and the size of the silica after the hydrophobization treatment is easy to stabilize. As a result, it is easy to increase the viscosity of the conductive particle layer and increase the capture rate of the conductive particles.

  In the said invention, it is preferable that the total mass of the said inorganic oxide particle with respect to the whole quantity of an adhesive agent is 10-40 mass%. As a result, it becomes easy to achieve both improvement in the capture rate and monodispersity of the conductive particles and improvement in adhesive strength.

In the said invention, it is preferable that the grafting rate represented by following formula A is 2 mass% or more.
Grafting rate = 100 × (total value of mass of first hydrophobic layer and second hydrophobic layer) / (mass of inorganic oxide particles) (A)

  When the grafting rate is 2% by mass or more, the monodispersity of the conductive particles in the conductive particle layer is easily improved.

  In the said invention, it is preferable that a 1st hydrophobic layer and a 1st hydrophobic layer contain a silicone oligomer. Thereby, the effect of the present invention becomes remarkable. The silicone oligomer contained in the first hydrophobic layer may be the same as or different from the silicone oligomer contained in the second hydrophobic layer.

  In the said invention, it is preferable that a 1st hydrophobic layer is formed by processing the surface of an inorganic oxide particle in the gaseous phase containing a silicone oligomer. In the said invention, it is preferable that a 2nd hydrophobic layer is formed by processing the surface of the inorganic oxide particle in which the 1st hydrophobic layer was formed in the liquid phase containing a silicone oligomer. Thereby, the hydrophobicity of the inorganic oxide particles is significantly improved.

  In the said invention, it is preferable that the weight average molecular weights of a silicone oligomer are 500-6000. Thereby, the surface of the inorganic oxide particles can be easily coated with the silicone oligomer with a desired thickness.

  In the present invention, the silicone oligomer is preferably three-dimensionally crosslinked. Thereby, the hydrophobicity of the inorganic oxide particles is significantly improved.

  In the present invention, the silicone oligomer preferably has at least one of a trifunctional siloxane unit and a tetrafunctional siloxane unit. In the said invention, it is preferable that a silicone oligomer has both a bifunctional siloxane unit and a trifunctional siloxane unit. In the said invention, it is preferable that a silicone oligomer has both a bifunctional siloxane unit and a tetrafunctional siloxane unit.

  When a silicone oligomer has said siloxane unit and those combination, a silicone oligomer becomes easy to carry out a three-dimensional bridge | crosslinking.

  In the present invention, it is preferable that a methyl group or a phenyl group is bonded to silicon having at least one of a bifunctional siloxane unit, a trifunctional siloxane unit, and a tetrafunctional siloxane unit. When a methyl group is bonded to silicon of a siloxane unit, it is easy to achieve both ease of hydrophobizing the surface of the inorganic oxide particles and insulation of the inorganic oxide particles. When a phenyl group is bonded to silicon of a siloxane unit, the heat resistance and insulating properties of the inorganic oxide particles are remarkably improved, and the characteristics of the adhesive for circuit connection are improved.

  In the said invention, it is preferable that a silicone oligomer has a functional group which reacts with an adhesive agent. Thereby, the interface between the inorganic oxide fine particles and the adhesive is reinforced, and it becomes easy to obtain the insulating property and the thickening of the adhesive for circuit connection.

  The adhesive for circuit connection of the present invention is formed by mixing a slurry containing inorganic oxide particles and an organic solvent and an adhesive, and the viscosity of the slurry is preferably less than 17 mPa · s. Thereby, the insulation in the non-pressurizing direction is remarkably improved.

  According to the present invention, an adhesive for circuit connection for forming an anisotropic conductive film that improves the trapping rate of conductive particles and simultaneously improves the insulation in the non-pressurization direction and the conductivity in the pressurization direction, And an anisotropic conductive film can be provided.

FIG. 1 is a schematic cross-sectional view of an anisotropic conductive film, IC chip, and glass substrate according to an embodiment of the present invention. FIG. 2 is a partially enlarged view of the conductive particle layer shown in FIG. FIG. 3 is a schematic cross-sectional view of inorganic oxide particles provided in the anisotropic conductive film according to an embodiment of the present invention. FIG. 4 is a schematic cross-sectional view of a connection structure formed using an anisotropic conductive film according to an embodiment of the present invention.

  Hereinafter, a preferred embodiment of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the following embodiments. In the description of the drawings, the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted. In addition, the dimensional ratio in each drawing does not necessarily match the actual dimensional ratio.

(Anisotropic conductive film)
An anisotropic conductive film 12 according to this embodiment shown in FIGS. 1 and 2 includes a conductive particle layer 5 and an adhesive layer 3. The adhesive layer 3 is laminated on one surface of the conductive particle layer 5. Further, the anisotropic conductive film 12 may include an adhesive layer 6 laminated on the other surface of the conductive particle layer 5.

  The conductive particle layer 5 contains conductive particles 10, inorganic oxide particles 9, and an adhesive 22. A part of the surface of the conductive particles 10 is covered with an insulator 11. The inorganic oxide particles 9 have a hydrophobic surface. The conductive particles 10 and the inorganic oxide particles 9 are each uniformly dispersed in the adhesive 22 of the conductive particle layer 5. The adhesive layer 3 and the adhesive layer 6 each contain an adhesive and do not contain the conductive particles 10. The conductive particle layer 5 is formed by adding the conductive particles 10 to an adhesive for circuit connection according to this embodiment, which will be described later, and then molding the adhesive for circuit connection into a film shape.

  By connecting the IC chip 1 and the glass substrate 8 through the anisotropic conductive film 12 by the following procedure, the connection structure 42 shown in FIG. 4 is formed.

  As shown in FIG. 1, the anisotropic conductive film 12 is disposed between the IC chip 1 and the glass substrate 8. Of the surface of the IC chip 1, the surface on which the metal bumps 2 are formed is opposed to the adhesive layer 3. The surface of the glass substrate 8 on which the electrode 7 is formed is opposed to the adhesive layer 6. The electrode 7 is made of ITO (Indium Tin Oxide) or IZO (Indium Zinc Oxide). The metal bump 2 included in the IC chip is opposed to the electrode 7 included in the glass substrate 8.

  With the anisotropic conductive film 12, the IC chip 1 and the glass substrate 8 arranged as described above, the IC chip 1 and the glass substrate 8 are pressed and laminated while being heated. Thereby, the connection structure 42 of FIG. 4 is completed. The metal bumps 2 of the IC chip 1 and the electrodes 7 of the glass substrate 8 are electrically connected through the conductive particles 10.

  In order to improve the adhesiveness between the IC chip 1 and the glass substrate 8, it is desirable that the fluidity at the time of pressure bonding of the adhesive layer 3 disposed on the metal bump 2 side is desirable. Moreover, in order to improve the adhesiveness between the IC chip 1 and the glass substrate 8, it is desirable that the fluidity at the time of pressure bonding of the adhesive layer 6 disposed on the glass substrate 8 side is good. Furthermore, in order to improve the capture rate of the conductive particles 10 and simultaneously improve the insulation in the non-pressurization direction and the conductivity in the pressurization direction, it is desirable that the viscosity of the conductive particle layer 5 at the time of pressure bonding is high. Moreover, it is desirable that the conductive particles 10 in the conductive particle layer 5 at the time of pressure bonding are not dispersed but monodispersed. The present embodiment has been found by the present inventors to achieve these requirements.

  In this embodiment, since the conductive particle layer 5 contains the inorganic compound particles 9, the viscosity of the conductive particle layer 5 at the time of heating is increased as compared with the adhesive layer 3 and the adhesive layer 6. This thickening effect makes it difficult for the conductive particles 10 to move when the IC chip 1 and the glass substrate 8 are pressure-bonded, thereby improving the capture rate. Moreover, the inorganic compound particle 9 exhibits the effect as a spacer by making the conductive particle layer 5 contain the inorganic compound particle 9. That is, in this embodiment, the monodispersity of the conductive particles 10 in the conductive particle layer 5 is dramatically improved as compared with the conventional anisotropic conductive film in which the inorganic compound particles are not added to the conductive particle layer.

  In the present embodiment, the flow of the conductive particles 10 in the heated conductive particle layer 5 is suppressed by the inorganic oxide particles 9 when the IC chip 1 and the glass substrate 8 are pressed. As a result, the conductive particles 10 are easily captured on the metal bumps 2, and the conductivity in the vertical direction (pressure direction) is increased. Since the ratio of the conductive particles 10 flowing out between the metal bumps 2 is reduced by improving the capture rate, the insulation in the lateral direction (non-pressurizing direction) is improved. Therefore, even when the coverage of the insulator 11 on the surface of the conductive particles 10 is low, it is easy to ensure the insulation in the lateral direction. Lowering the coverage further improves the longitudinal conductivity. The adhesive layer 3 or 6 having a lower content of inorganic oxide particles 9 than the conductive particle layer 5 is in contact with the metal bumps 2 and the electrodes 7. Therefore, embedding property and adhesiveness can be maintained.

The number of conductive particles 10 present per unit area of the conductive particle layer 5 is preferably 20,000 / mm ² or more. The unit area is a unit area on the surface of the conductive particle layer 5 facing the IC chip 1 or the glass substrate 8. When the conductive particle layer 5 contains a large amount of the conductive particles 10, the conductivity in the pressurizing direction is increased, and the number of conductive particles captured between the metal bumps 2 and the electrodes 7 is also stabilized. When the number of conductive particles per unit area of the conductive particle layer not containing inorganic compound particles is 20,000 / mm ² or more, migration tends to occur. However, in this embodiment, since a large amount of inorganic compound particles 9 are present in the conductive particle layer 5, migration is prevented, and insulation in the non-pressurizing direction is improved.

  When the anisotropic conductive film 12 does not include the adhesive layer 6 and is composed of two layers of the conductive particle layer 5 and the adhesive layer 3, the adhesive layer 3 is disposed on the IC chip 1 side, and the conductive particle layer 5 is disposed on the glass substrate. It is preferable to arrange on the 8 side. Thereby, the conductive particles 10 are captured on the metal bump 2 side with high efficiency. For this purpose, the conductive particle layer 5 is preferably as thin as possible. The adhesive layer 3 is preferably thicker than the conductive particle layer 5 and has higher fluidity.

  Since a large amount of inorganic oxide particles 9 are mixed in the conductive particle layer 5, the fluidity of the conductive particle layer 5 is lower than that of the adhesive layer 3, and the adhesiveness may be insufficient. Therefore, in order to reinforce the adhesiveness between the glass substrate 8 or the electrode 7 (ITO) and the anisotropic conductive film, as described above, the adhesive layer is formed on one surface of the conductive particle layer 5 opposite to the adhesive layer 3. 6 are preferably laminated. That is, it is preferable that the anisotropic conductive film 12 is composed of the conductive particle layer 5 and the three layers of the adhesive layer 3 and the adhesive layer 6 laminated on both surfaces thereof. The adhesive layer 6 is preferably disposed on the glass substrate 8 side in order to adhere to the glass substrate 8 and the electrode 7 (ITO). The fluidity of the adhesive layer 6 is preferably higher than that of the conductive particle layer 5.

  The total thickness of the anisotropic conductive film 12 is relatively determined in consideration of the particle size of the conductive particles 10 and the characteristics of the anisotropic conductive adhesive. The average thickness of the conductive particle layer 5 may be 3 μm or more and 15 μm or less. The average thickness of the adhesive layer 3 facing the IC chip 1 may be 7 μm or more and 20 μm or less. The average thickness of the adhesive layer 6 facing the glass substrate 8 may be 1 μm or more and 4 μm or less.

  The volume of the conductive particle layer 5 is preferably 50% by volume or less with respect to the entire anisotropic conductive film 12. Thereby, a capture rate, insulation, and electrical conductivity improve remarkably.

The content of the inorganic oxide particles 9 in the conductive particle layer 5 is defined by the following formula (C).
Content ratio of the inorganic oxide particles 9 in the conductive particle layer 5 = {(total mass of the inorganic oxide particles 9 included in the conductive particle layer 5) / (total mass of the adhesive 22 included in the conductive particle layer 5)} × 100 ·・ ・ (C)

  The content of the inorganic oxide particles 9 in the conductive particle layer 5 is greater than 5% by mass. The content of the inorganic oxide particles 9 in the conductive particle layer 5 is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, and 30% by mass or more. Most preferably. The content of the inorganic oxide particles 9 in the conductive particle layer 5 is preferably 40% by mass or less, and more preferably 30% by mass or less.

  The more the inorganic oxide particles 9 are added to the conductive particle layer 5, the better the capture rate of the conductive particles 10 and the monodispersity of the conductive particles 10 in the film. However, if the inorganic oxide particles 9 are added too much, the adhesive strength tends to decrease. That is, in order to improve the capture rate and monodispersity of the conductive particles 10, the more inorganic oxide particles 9 are better, and in order to improve the adhesive strength, the fewer inorganic oxide particles 9 are better. From the above viewpoint, the addition amount of the inorganic oxide particles 9 in the conductive particle layer 5 is preferably within the above numerical range.

The content (% by mass) of the inorganic oxide particles 9 in the adhesive layer 3 is defined by the following formula (D).
Content of inorganic oxide particles 9 in adhesive layer 3 = {(total mass of inorganic oxide particles 9 included in adhesive layer 3) / (total mass of adhesive included in adhesive layer 3)} × 100 (D )

  The content of the inorganic oxide particles 9 in the adhesive layer 3 is preferably less than 10% by mass, and more preferably less than 5% by mass. When the content rate of the inorganic oxide particles 9 in the adhesive layer 3 is too high, the fluidity of the adhesive layer 3 tends to decrease, and the capture rate of the conductive particles 10 tends to decrease. The fluidity of the adhesive layer 3 is high, and the higher the adhesiveness, the better. Therefore, the smaller the number of inorganic oxide particles 9 contained in the adhesive layer 3, the better. The adhesive layer 3 may not contain the inorganic oxide particles 9. The content of the inorganic oxide particles 9 in the adhesive layer 6 is the same as that of the adhesive layer 3.

(Adhesive for circuit connection)
<Adhesive>
As an adhesive used for the conductive particle layer 5, the adhesive layer 3, and the adhesive layer 6, for example, a mixture of a heat-reactive resin and a curing agent may be used. A preferable adhesive includes, for example, a mixture of an epoxy resin and a latent curing agent. Examples of latent curing agents include imidazole curing agents, hydrazide curing agents, boron trifluoride-amine complexes, sulfonium salts, amine imides, polyamine salts, dicyandiamide, and the like. In addition, an energy ray curable resin such as a mixture of a radical reactive resin and an organic peroxide or an ultraviolet curable resin may be used as the adhesive.

Epoxy resins include bisphenol type epoxy resins derived from epichlorohydrin and bisphenol A, F, AD, etc., epoxy novolac resins derived from epichlorohydrin and phenol novolac or cresol novolac, and naphthalene type epoxy resins having a skeleton containing a naphthalene ring. , Various epoxy compounds having two or more glycidyl groups in one molecule such as glycidylamine, glycidyl ether, biphenyl, and alicyclic can be used alone or in admixture of two or more. As these epoxy resins, it is preferable to use high-purity products in which the content of impurity ions (Na ⁺ , Cl ^−, etc.), hydrolyzable chlorine, etc. is reduced to 300 ppm or less. Thereby, electromigration is prevented.

  The adhesive may be mixed with butadiene rubber, acrylic rubber, styrene-butadiene rubber, silicone rubber, or the like. Thereby, the adhesiveness of an anisotropic conductive film improves, or the stress in the anisotropic conductive film after adhesion | attachment reduces. Further, as the adhesive, a paste or film is used. In order to form a film, it is effective to blend a thermoplastic resin such as a phenoxy resin, a polyester resin, or a polyamide resin. These film-forming polymers are also effective in stress relaxation when the reactive resin is cured. In particular, the film-forming polymer preferably has a functional group such as a hydroxyl group. In this case, the adhesiveness is improved.

  In the preparation of an adhesive for circuit connection, the adhesive composition comprising at least the above-mentioned epoxy resin, acrylic rubber, and latent curing agent is liquefied by dissolving or dispersing it in an organic solvent. And the adhesive for circuit connection which concerns on this embodiment is obtained by disperse | distributing an inorganic oxide particle in the liquefied adhesive composition. As the solvent used for liquefaction, an aromatic hydrocarbon-based and oxygen-containing mixed organic solvent is preferable. By using this mixed organic solvent, the solubility of the adhesive composition is improved. Specific examples of the mixed organic solvent include a mixed solvent of toluene and ethyl acetate or methyl ethyl ketone.

  The total mass of the inorganic oxide particles with respect to the total amount of the adhesive composition (solid content) contained in the circuit connecting adhesive is greater than 5% by mass. Thereby, the viscosity of the conductive particle layer formed from the adhesive for circuit connection containing the conductive particles is improved, and the capture rate of the conductive particles is improved.

  In the formation of the conductive particle layer 5, an adhesive for circuit connection in which conductive particles are dispersed is applied on a peelable substrate, and the solvent is removed at an activation temperature or lower of the curing agent. Thereby, a conductive particle layer is formed on the peelable substrate. In the formation of the adhesive layers 3 and 6, the above liquefied adhesive composition is applied on a peelable substrate, and the solvent is removed at a temperature lower than the activation temperature of the curing agent. Thereby, an adhesive layer is formed on the peelable substrate.

  An anisotropic conductive film 12 is obtained by laminating the adhesive layer 3, the conductive particle layer 5 and the adhesive layer 6 formed on the peelable substrate.

<Inorganic oxide particles>
As shown in FIG. 3, at least a part of the surface of the inorganic oxide particle 9 is covered with the first hydrophobic layer 32. At least a part of the surface of the first hydrophobic layer 32 facing away from the inorganic oxide particles 9 is covered with a second hydrophobic layer 34. These hydrophobic layers impart hydrophobicity to the surface of the inorganic oxide particles 9. That is, the surface of the inorganic oxide particles 9 is at least double-hydrophobized. A part of the surface of the inorganic oxide particle 9 may be directly covered with the second hydrophobic layer 34.

  Inorganic oxide particles are superior to other particles in terms of fineness of particle diameter, uniformity of particle diameter, and insulation. Examples of the inorganic oxide constituting the inorganic oxide particles include silica, alumina, zirconium oxide, antimony trioxide, antimony pentoxide, magnesium oxide, titanium oxide, and zinc oxide. Among these, silica is preferable from the viewpoints of particle diameter, uniformity of particle diameter, insulation, and ease of surface treatment. The average particle size of the inorganic oxide particles is preferably 5 to 30 nm. The smaller the particle size of the inorganic oxide particles, the greater the thickening effect of the conductive particle layer. This is because the surface area per unit weight of the inorganic oxide particles increases as the particle size of the inorganic oxide particles decreases. When the particle size is less than 5 nm, it is difficult to stably surface-treat the inorganic oxide particles with a hydrophobic substance, and the size of the inorganic oxide particles after the surface treatment tends to be unstable. Moreover, when a particle size is larger than 30 nm, the thickening effect of a conductive particle layer is small, and there exists a tendency for a capture rate to be hard to improve. The average particle size of the inorganic oxide particles is calculated by the BET specific surface area method.

  The surface of the inorganic oxide particles not covered with the hydrophobic layer is covered with a hydroxyl group and is hydrophilic. When such hydrophilic inorganic oxide particles are put into a varnish which is a raw material of the conductive particle layer, they are aggregated, so it is difficult to add a certain amount or more of the inorganic oxide particles to the conductive particle layer. . Therefore, it is necessary to make the surface of the inorganic oxide particles hydrophobic. In addition, the use of hydrophilic inorganic oxide particles becomes a factor in forming scratches on the conductive particle layer when the conductive particle layer is formed by coating.

  In order to form the first hydrophobic layer 32 and the second hydrophobic layer 34 on the surface of the inorganic oxide particle, a coating agent having both a functional group that easily reacts with a hydroxyl group on the surface of the inorganic oxide particle and a hydrophobic functional group, It is desirable to subject the inorganic oxide particles to a hydrophobic treatment. As such a coating agent, a silane coupling agent, an alkylsilazane, or silicone is preferable. That is, the hydrophobic substance constituting the first hydrophobic layer 32 or the second hydrophobic layer 34 is preferably a silane compound, a silazane compound, or a silicone oligomer. However, a silicone oligomer is contained in either the first hydrophobic layer 32 or the second hydrophobic layer 34.

  Specific methods for hydrophobizing inorganic oxide fine particles include vapor phase treatment and liquid phase treatment. It is not possible to disperse the inorganic oxide fine particles directly in the above-mentioned mixed organic solvent of aromatic hydrocarbon and oxygen containing. Furthermore, such nanoscale inorganic oxide particles are difficult to filter. Therefore, it is desirable to form the first hydrophobic layer by a hydrophobizing treatment in the gas phase.

  In the hydrophobization treatment in the gas phase, for example, the inorganic oxide particles are first put in a flask and stirred. Next, a coating agent such as a silane coupling agent, an alkylsilazane, or a silicone oligomer is dropped or sprayed onto the inorganic oxide particles and adsorbed on the surface of the inorganic oxide particles. Next, the entire flask is heated under a nitrogen atmosphere to promote adhesion between the silane coupling agent, alkylsilazane, silicone oligomer, and the like and the surface of the inorganic oxide particles. Thereby, the first hydrophobic layer is formed. Thereafter, the inorganic oxide particles are crushed to be once powdered.

The silane coupling agent is a compound represented by the following chemical formula (I).
X _m SiY _n (I)
In said formula (I), X is a functional group couple | bonded with the inorganic oxide particle surface, and is an alkoxy group, an acyloxy group, an oxime group, or a halogen. m is an integer of 1-3. Y is a hydrophobic functional group such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, phenyl group, glycidoxypropyl group, 3-aminopropyl group, vinyl group, etc. is there.

  Silica hydrophobized with a silane coupling agent is generally sold and readily available. You may form the inorganic oxide particle which has a 1st hydrophobic layer and a 2nd hydrophobic layer using this.

  As the alkylsilazane, hexamethyldisilazane, vinylsilazane, or the like can be used.

  However, since the molecular weight of the silane compound is low, it is difficult to uniformly form a film made of a hydrophobic silane compound on the inorganic oxide particles. Therefore, when a coating agent having a molecular weight larger than that of the silane compound is used, it becomes easy to form a uniform hydrophobic film on the inorganic oxide particles. The molecular weight of the silicone oligomer is larger than that of the silane compound. Accordingly, a silicone oligomer is preferable as the coating agent for forming the first hydrophobic layer. That is, the first hydrophobic layer is preferably made of a silicone oligomer. Although it is difficult to three-dimensionally attach the silane coupling agent to the inorganic oxide particles, it is easy to three-dimensionally bond the silicone oligomer to the surface of the inorganic oxide particles. When the coating amount is the same, the effect of the present invention is more remarkable when the silicone oligomer is used as the coating agent than the silane coupling agent.

As the silicone oligomer, those having a three-dimensional condensation reaction in advance and having both a functional group that reacts with an inorganic material such as silica and a hydrophobic functional group are preferable. The silicone oligomer preferably contains at least one kind selected from a bifunctional siloxane unit (R ₂ SiO _2/2 ), a trifunctional siloxane unit (RSiO _3/2 ), and a tetrafunctional siloxane unit (SiO _4/2 ). . In the above chemical formula, R is a functional group, for example, an alkyl group having 1 or 2 carbon atoms such as a methyl group, an ethyl group, or a glycidoxypropyl group, an aryl group having 6 to 12 carbon atoms such as a phenyl group, or Vinyl group and the like. The plurality of R groups contained in the silicone oligomer may be the same as or different from each other.

  When the functional group R is a phenyl group, the heat resistance and insulation of the inorganic oxide particles are remarkably improved, and the characteristics of the adhesive for circuit connection are improved. When the functional group R is a methyl group, it is easy to achieve both ease of hydrophobization treatment and insulation of the inorganic oxide particles. When the functional group R has a functional group that reacts with the adhesive, the interface between the inorganic oxide fine particles and the adhesive is reinforced, and it becomes easy to obtain the insulating property and the viscosity increase of the circuit connecting adhesive. When the resin constituting the adhesive is an epoxy resin or an acrylic resin, the functional group R may be a glycidyl group, a vinyl group, an amino group, an epoxy group, or the like. These functional groups react with an epoxy resin or an acrylic resin to form a chemical bond.

The bifunctional siloxane unit (R ₂ SiO _2/2 ) is represented by the following chemical structural formula (1). The trifunctional siloxane unit (RSiO _3/2 ) is represented by the following chemical structural formula (2). The tetrafunctional siloxane unit (SiO _4/2 ) is represented by the following chemical structural formula (3).

  The silicone oligomer preferably has at least one of a trifunctional siloxane unit and a tetrafunctional siloxane unit. Such a silicone oligomer is previously three-dimensionally crosslinked. Specific examples of the silicone oligomer include those composed only of trifunctional siloxane units, those composed only of tetrafunctional siloxane units, those composed of bifunctional siloxane units and trifunctional siloxane units, and bifunctional siloxane units and 4 Examples thereof include those composed of functional siloxane units, those composed of trifunctional siloxane units and tetrafunctional siloxane units, and those composed of bifunctional siloxane units, trifunctional siloxane units and tetrafunctional siloxane units. Moreover, it is preferable that the ratio of a tetrafunctional siloxane unit is 15 mol% or more in all the siloxane units which a silicone oligomer has, and it is more preferable that it is 20-60 mol%.

  The degree of polymerization of the silicone oligomer is preferably 3 to 90, and more preferably 5 to 80. The degree of polymerization is a converted value from the weight average molecular weight measured by gel permeation chromatography (GPC). When the degree of polymerization exceeds 80, when the inorganic oxide particles are surface-treated with a silicone oligomer, uneven treatment may occur and reliability may be lowered. Moreover, when the degree of polymerization is less than 5, the thickness of the hydrophobic layer made of the silicone oligomer cannot be obtained, and the effect relating to the silicone oligomer tends to be insufficient. For the same reason as in the case of the degree of polymerization, the weight average molecular weight of the silicone oligomer is preferably 500 to 10,000, and more preferably 500 to 6,000.

  In order to cover the surface of the inorganic oxide particles with a silicone oligomer having a sufficient three-dimensional crosslinked structure, the degree of polymerization of the silicone oligomer containing a trifunctional siloxane unit and / or a tetrafunctional siloxane unit is 6 to 70. Is preferable, and it is more preferable that it is 10-50. Such a silicone oligomer can be synthesized, for example, by condensing chlorosilane or alkoxysilane corresponding to a desired siloxane unit using an acid catalyst in the presence of water. The condensation reaction is performed to such an extent that it does not become a gel before the surface treatment. For this purpose, the reaction temperature, reaction time, oligomer composition ratio, and type and amount of the catalyst are adjusted. As the catalyst, acetic acid, hydrochloric acid, maleic acid, phosphoric acid and the like are preferably used.

  The silicone oligomer solution (treatment liquid) and treatment conditions used for the hydrophobic treatment of the inorganic oxide particles are not particularly limited. As an example of a simple hydrophobization treatment method, a method of dropping a treatment liquid having a silicone oligomer content of 5 to 100% by mass to inorganic oxide particles while stirring the inorganic oxide particles in a heated nitrogen atmosphere There is.

  Various solvents, silane coupling agents, coupling agents such as titanate coupling agents, and other additives may be blended in the treatment liquid. Examples of the silane coupling agent include epoxy silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, hydrochloride, and the like. And aminosilane coupling agents, cationic silane coupling agents, vinyl silane coupling agents, acrylic silane coupling agents, mercaptosilane coupling agents, and composite coupling agents thereof. Examples of titanate coupling agents include isopropyl tris (dioctylpyrophosphate) titanate. These coupling agents are used in an arbitrary amount. Further, the surface of the inorganic oxide particles before or after the treatment with the silicone oligomer may be further treated with a silane coupling agent or a titanate coupling agent.

  The inorganic oxide fine particles on which the first hydrophobic layer is formed by the gas phase treatment tend to aggregate. Therefore, it is better to crush the aggregated inorganic oxide fine particles with a collision type crusher or the like. However, a part of the hydroxyl groups on the surface of the inorganic oxide fine particles may be exposed again by this crushing step. As a result, the hydrophobicity and insulating properties of the inorganic oxide fine particles are impaired. In addition, the inorganic oxide fine particles having hydroxyl groups exposed to the surface again tend to aggregate again. On the other hand, when the crushing step is not performed, the inorganic oxide fine particles are easily maintained in a state of being aggregated in a solid state. In the preparation of an adhesive for circuit connection, it is difficult to disperse the aggregated inorganic oxide fine particles in the adhesive. When an anisotropic conductive film is formed by applying an adhesive for circuit connection containing agglomerated inorganic oxide fine particles, streaks occur in the film or other problems occur.

  In this embodiment, it is preferable that the inorganic oxide fine particles on which the first hydrophobic layer is formed are crushed in a liquid phase containing the above coating agent. That is, it is preferable to form the second hydrophobic layer by a hydrophobic treatment in the liquid phase. Thereby, the surface of the inorganic oxide fine particle in which the hydroxyl group is exposed by crushing is immediately covered with the second hydrophobic layer. The first hydrophobic layer is also covered with the second hydrophobic layer. As described above, the surface of the inorganic oxide particles is double-hydrophobized, so that the inorganic oxide particles hardly aggregate in the liquid phase and the dispersibility of the inorganic oxide particles in the liquid phase is improved. .

  As the liquid layer used for forming the second hydrophobic layer, the same solvent as that used for the adhesive for circuit connection may be used. That is, an aromatic hydrocarbon-based and oxygen-containing mixed organic solvent may be used as the liquid layer. Specific examples include a mixed solvent of toluene and ethyl acetate or methyl ethyl ketone. When the second hydrophobic layer is formed in the gas phase, the inorganic oxide particles need to be crushed again, making it difficult to obtain the above-described effect relating to the formation of the second hydrophobic layer.

  As the coating agent used for the hydrophobization treatment in the liquid phase, it is preferable to use the above silicone oligomer. That is, the second hydrophobic layer preferably contains a silicone oligomer. In the hydrophobization treatment in the liquid phase, the molecular weight of the silicone oligomer becomes particularly important. When a silicone oligomer having a weight average molecular weight of 6000 or more is used, inorganic oxide particles tend to aggregate and it is difficult to obtain original characteristics.

  In the hydrophobization treatment in the liquid phase using the silicone oligomer, the inorganic oxide particles on which the first hydrophobic layer is formed are dispersed in the above mixed organic solvent, and 2 to 100% by mass with respect to the inorganic oxide particles. Add silicone oligomer. Then, the inorganic oxide particles in the mixed organic solvent are crushed using a liquid layer collision type pulverizing and dispersing device. Thereby, the slurry containing the inorganic oxide particle which has a 1st hydrophobic layer and a 2nd hydrophobic layer is obtained. The hydroxyl groups on the surface of the inorganic oxide particles exposed by crushing are again treated with the silicone oligomer in the liquid phase. Therefore, according to the hydrophobizing treatment method in the liquid phase, the coverage of the hydrophobic layer on the surface of the inorganic oxide particles is higher than that of the conventional hydrophobic treatment method.

The grafting rate represented by the following formula A is preferably 2.0% by mass or more.
Grafting rate = 100 × (total value of mass of first hydrophobic layer and second hydrophobic layer) / (weight of inorganic oxide particles) (A)
When the grafting rate is less than 2% by mass, hydroxyl groups on the surface of the inorganic oxide particles tend to remain. As a result, it is easy to generate | occur | produce the deterioration of insulation, the fall of the capture rate of electroconductive particle, and the monodispersity of the electroconductive particle in a film. The grafting rate is desirably 20% by mass or less. When the grafting ratio exceeds 20% by mass, the particle size of the inorganic oxide particles after the double hydrophobization treatment is too large, and it is difficult to obtain the desired thickening of the conductive particle layer.

  As described above, it is preferable that both the first hydrophobic layer and the second hydrophobic layer are made of a silicone oligomer. Thereby, the hydrophobicity of the inorganic oxide particles is remarkably improved, and the effect of the present invention becomes remarkable.

  When the first hydrophobic layer and the second hydrophobic layer are made of a silicone oligomer, for example, the grafting rate is measured as follows. In the method for measuring the grafting rate, the inorganic oxide particles coated with the first hydrophobic layer and the second hydrophobic layer are heated at 1000 ° C. By this heating, the silicone oligomer constituting the first hydrophobic layer and the second hydrophobic layer is thermally decomposed. The amount of decrease in the weight of the inorganic oxide particles accompanying thermal decomposition corresponds to the mass of the first hydrophobic layer and the second hydrophobic layer.

  A slurry composed of double hydrophobized inorganic oxide particles and the above mixed organic solvent is mixed with a liquefied adhesive composition, and a large amount of inorganic oxide particles are dispersed in the adhesive composition. By doing so, an adhesive for circuit connection is obtained. The viscosity of the slurry during mixing with the adhesive composition is preferably less than 17 mPa · s. Thereby, the dispersibility of the inorganic oxide particles in the circuit connecting adhesive is easily improved, and the insulating property of the circuit connecting adhesive is easily improved.

<Conductive particles>
As shown in FIG. 2, a part of the surface of the conductive particle 10 is covered with an insulator 11 (insulating child particles).

The coverage of the insulator 11 in the conductive particles 10 is preferably 10 to 40%, and more preferably 10 to 30%. The coverage of the insulator 11 in the conductive particles 10 is defined by the following formula (E). Each area in the formula (E) may be obtained by analyzing the SEM image of the conductive particles 10.
Coverage of insulator 11 in conductive particle 10 = (surface area covered with insulator 11 / surface area of the entire conductive particle 10) × 100 (E)

The insulation and conductivity can be balanced by the coverage of the insulator 11. That is, according to the experience of the present inventors, when the number of conductive particles per unit area of the metal bump is 20,000 / mm ² or more in the conventional connection structure, It is necessary to set the coverage to 40% or more. However, in this embodiment, sufficient insulation is achieved even if the coverage of the insulator 11 is 10 to 30%. Thus, since the insulation coverage of the insulator 11 can be set lower than before, the continuity is improved accordingly.

  The particle diameter of the conductive particles 10 is preferably smaller than the minimum value of the distance between the metal bumps 2 and the distance between the electrodes 7. When the heights of the metal bumps 2 and the electrodes 7 vary, the particle diameter of the conductive particles 10 is preferably larger than the height variations. For these reasons, the particle size of the conductive particles 10 is preferably 1 to 10 μm, more preferably 2.5 to 5 μm, and most preferably 2.5 to 4 μm.

  As the conductive particles 10, particles made of only metal may be used. Further, as the conductive particles 10, those obtained by coating core particles such as organic compound particles or inorganic compound particles with metal plating may be used. In the present embodiment, as shown in FIG. 2, the conductive particles 10 are preferably those in which the core particles 24 made of an organic compound are coated with the metal plating 22.

  Although it does not specifically limit as a metal which comprises the metal plating 22, Gold, silver, copper, platinum, zinc, iron, palladium, nickel, tin, chromium, titanium, aluminum, cobalt, germanium, cadmium etc. are mentioned. From the viewpoint of corrosion resistance, nickel, palladium, and gold are preferable. Further, the core particles 24 may be covered with a conductive metal compound such as ITO or solder.

  The structure of the metal plating 22 may be a single layer structure or a laminated structure composed of a plurality of layers. In the case of a laminated structure, the outermost layer of the metal plating 22 is preferably composed of gold or palladium from the viewpoint of corrosion resistance and conductivity.

  Methods for forming the metal plating 22 include methods such as electroless plating, displacement plating, electroplating, and sputtering.

  The thickness of the metal plating 22 is not particularly limited, but is preferably 0.001 to 1.0 μm, and more preferably 0.005 to 0.3 μm. If the thickness of the metal plating 22 is less than 0.001 μm, poor conduction is likely to occur, and if it exceeds 1.0 μm, it is not preferable in terms of cost.

  The organic compound constituting the core particle 22 is not particularly limited, and examples thereof include acrylic resins such as polymethyl methacrylate and polymethyl acrylate, and polyolefin resins such as polyethylene, polypropylene, polyisobutylene, and polybutadiene.

  The insulating child particles 11 covering the conductive particles 10 are preferably fine particles made of an organic compound or fine particles made of an inorganic compound. The method for coating the conductive particles 10 with the child particles 11 is not limited.

  Below, the case where the electrically-conductive particle 10 is coat | covered with the insulating child particle 11 which consists of an inorganic compound as an example is demonstrated. Hereinafter, the insulating child particles made of an inorganic compound are referred to as “inorganic child particles”.

The inorganic compound constituting the inorganic particles is preferably an oxide containing each element of silicon, aluminum, zirconium, titanium, niobium, zinc, tin, cerium, and magnesium. These can be used alone or in admixture of two or more. Among these, the inorganic particles are most preferably water-dispersed colloidal silica (SiO ₂ ) having excellent insulating properties and controlled particle diameter. Since water-dispersed colloidal silica (SiO ₂ ) has a hydroxyl group on the surface, it has excellent bonding properties with conductive particles. Moreover, the water-dispersed colloidal silica is easy to make the particle diameter uniform. Furthermore, water-dispersed colloidal silica is inexpensive. Examples of such commercially available inorganic particles include Snowtex, Snowtex UP (manufactured by Nissan Chemical Industries), Quatron PL series (manufactured by Fuso Chemical Industries), and the like. As the inorganic particles, inorganic particles produced by metal alkoxide hydrolysis reaction, so-called sol-gel method, are suitable.

  The particle size of the inorganic particles is preferably 20 to 500 nm. When the particle diameter is smaller than 20 nm, the inorganic particles adsorbed on the conductive particles do not act as an insulating film and tend to cause a short circuit in a part of the connection structure. On the other hand, when the particle diameter is larger than 500 nm, it tends to be difficult to obtain conductivity in the pressurizing direction. The particle diameter of the inorganic particles is measured by the specific surface area conversion method by the BET method or the X-ray small angle scattering method.

  The hydroxyl group on the surface of the inorganic particles can be modified to an amino group, a carboxyl group, or an epoxy group with a silane coupling agent or the like. However, when the particle diameter of the inorganic particles is 500 nm or less, modification of the hydroxyl group is difficult. Accordingly, it is desirable to coat the conductive particles with inorganic particles without modifying the functional group.

  In general, a hydroxyl group is known to form a strong bond with a hydroxyl group, a carboxyl group, an alkoxyl group, or an alkoxycarbonyl group. Examples of the mode of bonding between the hydroxyl group and these functional groups include covalent bonding by dehydration condensation and hydrogen bonding. Therefore, these functional groups may be formed on the surface of the conductive particles. The inorganic particles having a hydroxyl group on the surface can be strongly adsorbed to the conductive particles having a functional group formed on the surface.

  When the outermost surface of the conductive particles (the surface of the metal plating 22) is a gold layer or a palladium layer, it is a compound having any of a mercapto group, a sulfide group, and a disulfide group that forms a coordinate bond with gold or palladium. A hydroxyl group, a carboxyl group, an alkoxyl group, or an alkoxycarbonyl group is preferably formed on the outermost surface of the conductive particle. Specifically, the outermost surface of the conductive particles may be treated with mercaptoacetic acid, 2-mercaptoethanol, methyl mercaptoacetate, mercaptosuccinic acid, thioglycerin, cysteine, or the like.

  A method for treating the outermost surface of the conductive particles with the above compound is not particularly limited, and a compound such as mercaptoacetic acid is dispersed in an organic solvent such as methanol or ethanol at a concentration of about 10 to 100 mmol / l. And a method of dispersing conductive particles having a surface made of gold or palladium.

  Below, the case where the outermost surface (surface of the metal plating 22) of the electrically-conductive particle 10 is a palladium layer is demonstrated. After the surface of the palladium layer on which the functional group is formed is treated with a polymer electrolyte, inorganic particles are chemically adsorbed on the surface of the palladium layer.

  The surface potential (zeta potential) of a palladium layer having a functional group such as a hydroxyl group, a carboxyl group, an alkoxyl group, or an alkoxycarbonyl group is usually negative if the pH is in a neutral region. On the other hand, since the surface of the inorganic particle to be adsorbed on the surface of the palladium layer in the subsequent step is composed of an inorganic oxide having a hydroxyl group, the surface potential of the inorganic particle is usually negative. As described above, inorganic particles having a negative surface potential tend not to be adsorbed around the palladium layer having a negative surface potential. Therefore, by treating the surface of the palladium layer with a polymer electrolyte, the surface of the palladium layer can be easily coated with inorganic particles.

As a method of adsorbing the inorganic particles on the surface of the palladium layer after the treatment with the polymer electrolyte, a method of alternately laminating the polymer electrolyte and the inorganic particles on the surface of the palladium layer is preferable. More specifically, the conductive particles in which a part of the surface is coated with an insulating coating film in which a polymer electrolyte and inorganic particles are laminated by sequentially performing the following steps (1) and (2). Can be manufactured.
Step (1): A step of dispersing conductive particles having a functional group on the surface of the palladium layer in a polymer electrolyte solution, adsorbing the polymer electrolyte on the surface of the palladium layer, and then rinsing the conductive particles.
Step (2): A step of rinsing the conductive particles after dispersing the rinsed conductive particles in a dispersion solution of inorganic particles and adsorbing the inorganic particles on the surface (palladium layer) of the conductive particles.

  That is, in the step (1), a polymer electrolyte thin film is formed on the surface of the conductive particles, and in the step (2), the inorganic particles are immobilized on the surface of the conductive particles through the polymer electrolyte thin film by chemical adsorption. By using this polymer electrolyte thin film, the surface of the conductive particles can be uniformly coated with inorganic particles without defects. When circuit electrodes are connected using an anisotropic conductive film using conductive particles obtained through such steps (1) and (2), insulation is ensured even when the circuit electrode interval is narrow, and electrical The connection resistance is low and good between the electrodes connected to.

  The method having the above steps (1) and (2) is referred to as an alternating lamination method (Layer-by-Layer assembly). The alternate lamination method is described in G.H. This is a method of forming an organic thin film published by Decher et al. In 1992 (see Thin Solid Films, 210/211, p831 (1992)).

  In this alternate lamination method, a polymer adsorbed on a substrate by electrostatic attraction by alternately immersing the substrate in an aqueous solution of a polymer electrolyte having a positive charge (polycation) and a polymer electrolyte having a negative charge (polyanion). A combination of a cation and a polyanion is laminated to obtain a composite film (alternate laminated film).

  In the alternating layering method, the film is grown by attracting the charge of the material formed on the substrate and the material having the opposite charge in the solution by electrostatic attraction, so that the adsorption proceeds and the charge is neutralized. When this occurs, no further adsorption occurs. Therefore, when reaching a certain saturation point, the film thickness does not increase any more.

  Lvov et al. Applied the alternate lamination method to fine particles and reported a method of laminating a polymer electrolyte having a charge opposite to the surface charge of the fine particles by using the fine particle dispersions of silica, titania and ceria. (See Langmuir, Vol. 13, (1997) p6195-6203).

  By using this method, by alternately laminating silica fine particles having a negative surface charge and polydiallyldimethylammonium chloride (PDDA) or polyethyleneimine (PEI) which are polycations having the opposite charge, It is possible to form a fine particle laminated thin film in which silica fine particles and polymer electrolyte are alternately laminated.

  In this embodiment, after immersing the conductive particles in the polymer electrolyte solution and before immersing in the dispersion of inorganic particles having opposite charges, the excess polymer electrolyte solution is washed away from the conductive particles by rinsing with only the solvent. Is preferred. Alternatively, in this embodiment, after immersing the conductive particles in the dispersion of inorganic particles, and before immersing the conductive particles in the polymer electrolyte solution having an opposite charge, the dispersion of excess inorganic particles by rinsing with a solvent alone Is preferably washed away from the conductive particles.

  Since the polymer electrolyte and inorganic particles adsorbed on the conductive particles are electrostatically adsorbed on the surface of the conductive particles, they are not separated from the surface of the conductive particles in this rinsing step. However, if excess polymer electrolyte or inorganic particles that are not adsorbed with conductive particles are brought into a solution having the opposite charge to them, cations and anions are mixed in the solution, causing aggregation of the polymer electrolyte and inorganic particles. And precipitation may occur. Such a malfunction can be prevented by rinsing.

  Solvents used for rinsing include water, alcohol, acetone and the like. Usually, an ion exchange having a specific resistance value of 18 MΩ · cm or more is easy in that excessive polymer electrolyte solution or inorganic particle dispersion can be easily removed. Water (so-called ultrapure water) is used.

  The polymer electrolyte solution is obtained by dissolving a polymer electrolyte in water or a mixed solvent of water and a water-soluble organic solvent. Examples of water-soluble organic solvents that can be used include methanol, ethanol, propanol, acetone, dimethylformamide, acetonitrile, and the like.

  As the polymer electrolyte, a polymer that is ionized in an aqueous solution and has a charged functional group in the main chain or side chain can be used. In this case, a polycation is preferably used.

  The polycation generally has a positively charged functional group such as polyamines such as polyethyleneimine (PEI), polyallylamine hydrochloride (PAH), polydiallyldimethylammonium chloride (PDDA). , Polyvinyl pyridine (PVP), polylysine, polyacrylamide, and a copolymer containing at least one of them can be used.

  Among polyelectrolytes, polyethyleneimine has a high charge density and a strong binding force. Among these polymer electrolytes, alkali metal (Li, Na, K, Rb, Cs) ions, alkaline earth metal (Ca, Sr, Ba, Ra) ions, halide ions are used to avoid electromigration and corrosion. Those not containing (fluorine ion, chloride ion, bromine ion, iodine ion) are preferred.

  These polymer electrolytes are either water-soluble or soluble in a mixture of water and an organic solvent, and the molecular weight of the polymer electrolyte is generally determined depending on the type of polymer electrolyte used. Although it cannot be determined, generally about 500 to 200,000 is preferable. In general, the concentration of the polymer electrolyte in the solution is preferably about 0.01 to 10% by mass. The pH of the polymer electrolyte solution is not particularly limited.

  By adjusting the type, molecular weight, or concentration of the polymer electrolyte thin film that coats the conductive particles, the coverage of the inorganic particles can be controlled within the above range.

  Specifically, when a polymer electrolyte thin film with a high charge density such as polyethyleneimine is used, the coverage of inorganic particles tends to be high, and a polymer electrolyte thin film with a low charge density such as polydiallyldimethylammonium chloride. When is used, the coverage of inorganic particles tends to be low.

  Further, when the molecular weight of the polymer electrolyte is large, the coverage of the inorganic particles tends to be high, and the inorganic particles can be firmly adsorbed to the palladium layer. On the other hand, when the molecular weight of the polymer electrolyte is small, the coverage of the inorganic particles tends to be low.

  Furthermore, when the polymer electrolyte is used at a high concentration, the coverage of the inorganic particles tends to be high, and when the polymer electrolyte is used at a low concentration, the coverage of the inorganic particles tends to be low. When the coverage of the inorganic particles is high, the insulation tends to be high and the conductivity tends to be poor, and when the coverage of the inorganic particles is low, the conductivity tends to be high and the insulation is poor.

  Only one layer of the inorganic particles is preferably coated with the conductive particles. Multi-layer stacking makes it difficult to control the stacking amount.

  The concentration of alkali metal ions and alkaline earth metal ions in the dispersion of inorganic particles is preferably 100 ppm or less. Thereby, it becomes easy to improve the insulation reliability between adjacent electrodes.

  By heating and drying the conductive particles coated with the inorganic particles, the bond between the inorganic particles and the conductive particles can be further strengthened. The reason why the binding force is increased is, for example, a chemical bond between a functional group such as a carboxyl group on the surface of the palladium layer and a hydroxyl group on the surface of the inorganic particle. From the viewpoint of preventing metal rust, heating in a vacuum is preferred.

  The drying temperature is preferably 60 to 200 ° C., and the heating time is preferably 10 to 180 minutes. When the temperature is less than 60 ° C. or when the heating time is less than 10 minutes, the inorganic particles are easily peeled off from the conductive particles, and when the temperature exceeds 200 ° C. or the heating time exceeds 180 minutes, the conductive particles Since it is easy to deform, it is not preferred.

  Since the conductive particles coated with inorganic particles have a hydroxyl group on the surface, the insulation reliability may be insufficient. Therefore, the surface of the conductive particles coated with the inorganic particles may be further treated with a hydrophobic silicone oligomer. Thereby, insulation reliability increases.

(Conductive particles 1)
A nickel layer having a thickness of 0.2 μm was formed by electroless plating on the surface of crosslinked polystyrene particles (core particles) having an average particle size of 2.8 μm. Furthermore, a palladium layer having a thickness of 0.04 μm was provided outside the nickel layer. Thereby, mother particle 1 provided with metal plating which consists of two layers of the nickel layer which coats a core particle, and the palladium layer which coats a nickel layer was produced.

  Next, 8 mmol of mercaptoacetic acid was dissolved in 200 ml of methanol to prepare a reaction solution. Next, 10 g of the mother particle 1 was added to the above reaction solution, and the mixture was stirred at room temperature for 2 hours with a three-one motor and a stirring blade having a diameter of 45 mm. After washing with methanol, 10 g of mother particles 1 having a carboxyl group on the surface were obtained by filtering the mother particles 1 with a membrane filter (manufactured by Millipore) having a diameter of 3 μm.

  Next, a 30% polyethyleneimine aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) having a molecular weight of 70,000 was diluted with ultrapure water to obtain a 0.3 mass% polyethyleneimine aqueous solution. The mother particle 1 (10 g) having a carboxyl group was added to a 0.3% by mass polyethyleneimine aqueous solution and stirred at room temperature for 15 minutes. Next, the mother particle 1 was filtered with a φ3 μm membrane filter (manufactured by Millipore), put in 200 g of ultrapure water, and stirred at room temperature for 5 minutes. Further, the mother particle 1 is filtered through a φ3 μm membrane filter (manufactured by Millipore), and the polyethyleneimine not adsorbed on the mother particle 1 is removed by washing twice with 200 g of ultrapure water on the membrane filter. did.

  Next, the mother particles 1 treated with polyethyleneimine were immersed in pure water, and a liquid obtained by diluting a colloidal silica dispersion with ultrapure water was added dropwise. As a result, mother particles 1 coated with silica as an insulator were obtained. The silica coverage was adjusted to 30%. The coverage was adjusted by the amount of the diluted colloidal silica dispersion added dropwise. As the colloidal silica dispersion, Quatron PL-13 manufactured by Fuso Chemical Industry Co., Ltd. was used. The concentration of colloidal silica in the colloidal silica dispersion was 20% by mass. The average particle size of colloidal silica was 130 nm.

  Next, the mother particle 1 was filtered with a φ3 μm membrane filter (manufactured by Millipore), put in 200 g of ultrapure water, and stirred at room temperature for 5 minutes. Further, the base particle 1 was filtered with a membrane filter (manufactured by Millipore) having a diameter of 3 μm, and the silica not adsorbed on the base particle 1 was removed by washing twice with 200 g of ultrapure water on the membrane filter. . Thereafter, the mother particles 1 were immersed in a silicone solution, and the surface of the silica covering the mother particles 1 was hydrophobized. Thereafter, drying was performed at 80 ° C. for 30 minutes, and further, heat drying was performed at 120 ° C. for 1 hour to obtain conductive particles 1.

(Silicone oligomer 1)
In a glass flask equipped with a stirrer, a condenser and a thermometer, 0.60 g of acetic acid and 17.8 g of distilled water were added to a solution prepared by mixing 20 g of dimethoxydimethylsilane, 25 g of tetramethoxysilane, and 105 g of methanol, and at 50 ° C. The mixture was stirred for a certain time to conduct hydrolysis and polycondensation reaction. Silicone oligomer 1 having a molecular weight of 2500 was synthesized. The molecular weight is a weight average molecular weight measured by GPC. The silicone oligomer 1 has a methoxy group and a silanol group as terminal functional groups that react with a hydroxyl group. Methanol was added to the silicone oligomer 1 solution to prepare a treatment liquid (coating agent) having a solid content of 10% by mass.

(Silicone oligomer 2)
A solution was prepared by blending 50 g of triethoxyphenylsilane with 10 g of methanol. While stirring this, a solution of 6 g of distilled water and 0.5 g of acetic acid was added, and the mixture was heated at 80 ° C. for a certain time to perform hydrolysis and polycondensation reaction. The solution after the polycondensation reaction is once cooled to 0 ° C., then 6 g of tetraethoxysilane is added dropwise and stirred at room temperature for 2 hours to contain a phenyl group in the siloxane skeleton and a trifunctional silicone polymer at the terminal. (Silicone oligomer 2) was obtained. The weight average molecular weight of the silicone oligomer 2 by GPC was 1100. Methanol was added to the silicone oligomer 2 solution to prepare a treatment liquid having a solid content of 10% by mass.

(Silicone oligomer 3)
In a glass flask equipped with a stirrer, a condenser and a thermometer, 3 g of activated clay and 6.3 g of distilled water were added to a solution containing 110 g of 3-glycidoxypropyloxysilane and 2 g of methanol, and constant at 75 ° C. The mixture was stirred for a time to synthesize silicone oligomer 3. The weight average molecular weight of the silicone oligomer 3 by GPC was 900. The silicone oligomer 3 has a glycidyl group and a silanol group as terminal functional groups that react with a hydroxyl group. Methanol was added to the obtained silicone oligomer 3 solution to prepare a treatment liquid having a solid content of 10% by mass.

(Silicone oligomer 4)
A treatment liquid containing the silicone oligomer 4 having a weight molecular weight of 600 was prepared in the same manner as the silicone oligomer 1 except that the temperature and time during the hydrolysis and polycondensation reaction were adjusted.

(Silicone oligomer 5)
Silicone oligomer 5 having a weight average molecular weight of 6000 was produced in the same manner as silicone oligomer 1 except that the temperature and time during the hydrolysis and polycondensation reactions were adjusted.

(Silica nanoparticles 1)
10 g of untreated silica nanoparticles having an average particle diameter of 12 nm (Aerosil 200, manufactured by Aerosil Co., Ltd.) were placed in a glass flask equipped with a stirrer, a condenser and a thermometer, and stirred in a nitrogen atmosphere. While stirring, 10 g of the treatment solution for the silicone oligomer 1 was gradually added, and after the addition, the particle size was 12 nm whose surface was covered with the first hydrophobic layer formed from the silicone oligomer 1 by stirring at 120 ° C. for 24 hours. The silica nanoparticles 1 were prepared.

  Silica nanoparticles 1 were heated to 1000 ° C. with a micro thermogravimetric apparatus, and the weight change was measured. The amount of weight change corresponds to the total weight of the resin (silicone) removed from the silica nanoparticles 1 by thermal decomposition. As a result, it was confirmed that the weight reduction amount of the silica nanoparticles 1 was 2.5% by weight.

(Silica nanoparticles 2)
Silica nanoparticles 2 having a first hydrophobic layer formed from silicone oligomer 2 were produced in the same manner as silica nanoparticles 1 except that silicone oligomer 2 was used instead of silicone oligomer 1. The weight reduction amount of the silica nanoparticles 2 measured by the same method as that for the silica nanoparticles 1 was 4.4% by weight.

(Silica nanoparticles 3)
Silica nanoparticles 3 having a first hydrophobic layer formed from silicone oligomer 3 were produced in the same manner as silica nanoparticles 1 except that silicone oligomer 3 was used instead of silicone oligomer 1. The amount of weight reduction of the silica nanoparticles 3 measured by the same method as that for the silica nanoparticles 1 was 4.4% by weight.

(Silica nanoparticles 4)
Silica nanoparticles 4 having a first hydrophobic layer formed from silicone oligomer 4 were produced in the same manner as silica nanoparticles 1 except that silicone oligomer 4 was used instead of silicone oligomer 1. The weight reduction amount of the silica nanoparticles 4 measured by the same method as that for the silica nanoparticles 1 was 2.2% by weight.

(Silica nanoparticles 5)
Silica nanoparticles 5 having a first hydrophobic layer formed from silicone oligomer 5 were produced in the same manner as silica nanoparticles 1 except that silicone oligomer 5 was used instead of silicone oligomer 1. The amount of weight reduction of the silica nanoparticles 4 measured by the same method as that for the silica nanoparticles 1 was 2.8% by weight.

(Silica nanoparticles 6)
Silica nanoparticles 6 having a first hydrophobic layer formed from silicone oligomer 1 in the same manner as silica nanoparticles 1 except that untreated silica nanoparticles AEROSIL300 having an average particle diameter of 7 nm were used instead of silica nanoparticles AEROSIL200. Was made. The weight reduction amount of the silica nanoparticles 4 measured by the same method as that for the silica nanoparticles 1 was 2.2% by weight.

(Silica nanoparticles 7)
Silica nanoparticles 7 having a first hydrophobic layer formed from silicone oligomer 1 are produced in the same manner as silica nanoparticles 1 except that untreated silica nanoparticles AEROSIL 50 having an average particle diameter of 30 nm are used instead of AEROSIL 200. did. The amount of weight reduction of the silica nanoparticles 7 measured by the same method as that for the silica nanoparticles 1 was 2.8% by weight.

(Silica nanoparticles 8)
In the production of the silica nanoparticles 8, the amount of the silicone oligomer 1 treatment solution dropped was adjusted to 5 g instead of 10 g. Except for this, silica nanoparticles 8 having a first hydrophobic layer formed from silicone oligomer 1 were produced in the same manner as silica nanoparticles 1. The weight reduction amount of the silica nanoparticles 8 measured by the same method as that for the silica nanoparticles 1 was 1.4% by weight.

(Silica slurry 1)
After adding the silica nanoparticle 1 and the silicone oligomer 3 to the ethyl acetate solvent and dispersing the silica nanoparticle 1 in the ethyl acetate solvent, the silica nanoparticle 1 in the ethyl acetate solvent was crushed with a wet crushing apparatus. Thereby, the silica slurry 1 was produced. Silica nanoparticles in silica slurry 1 were coated with a first hydrophobic layer formed from silicone oligomer 1 and a second hydrophobic layer formed from silicone oligomer 3. In the production of the silica slurry 1, the content of the silica nanoparticles 1 in the ethyl acetate solvent was adjusted to 20% by mass. In preparation of the silica slurry 1, the silicone oligomer 3 having the same mass as the silica nanoparticles 1 was added to the ethyl acetate solvent.

(Silica slurry 2)
A silica slurry 2 was prepared in the same manner as the silica slurry 1 except that the silica nanoparticles 2 were used instead of the silica nanoparticles 1. Silica nanoparticles in the silica slurry 2 were coated with a first hydrophobic layer formed from the silicone oligomer 2 and a second hydrophobic layer formed from the silicone oligomer 3.

(Silica slurry 3)
A silica slurry 3 was prepared in the same manner as the silica slurry 1 except that the silica nanoparticles 3 were used instead of the silica nanoparticles 1. Silica nanoparticles in the silica slurry 3 were coated with a first hydrophobic layer formed from the silicone oligomer 3 and a second hydrophobic layer formed from the silicone oligomer 3.

(Silica slurry 4)
A silica slurry 4 was produced in the same manner as the silica slurry 1 except that the silica nanoparticles 4 were used instead of the silica nanoparticles 1. Silica nanoparticles in the silica slurry 4 were coated with a first hydrophobic layer formed from the silicone oligomer 4 and a second hydrophobic layer formed from the silicone oligomer 3.

(Silica slurry 5)
A silica slurry 5 was produced in the same manner as the silica slurry 1 except that the silica nanoparticles 5 were used instead of the silica nanoparticles 1. Silica nanoparticles in the silica slurry 5 were coated with a first hydrophobic layer formed from the silicone oligomer 5 and a second hydrophobic layer formed from the silicone oligomer 3.

(Silica slurry 6)
A silica slurry 6 was produced in the same manner as the silica slurry 1 except that the silica nanoparticles 6 were used instead of the silica nanoparticles 1. Silica nanoparticles in the silica slurry 6 were coated with a first hydrophobic layer formed from the silicone oligomer 1 and a second hydrophobic layer formed from the silicone oligomer 3.

(Silica slurry 7)
A silica slurry 7 was produced in the same manner as the silica slurry 1 except that the silica nanoparticles 7 were used instead of the silica nanoparticles 1. Silica nanoparticles in the silica slurry 7 were coated with a first hydrophobic layer formed from the silicone oligomer 1 and a second hydrophobic layer formed from the silicone oligomer 3.

(Silica slurry 8)
After adding the silica nanoparticle 8 and the silicone oligomer 3 to the ethyl acetate solvent and dispersing the silica nanoparticle 8 in the ethyl acetate solvent, the silica nanoparticle 8 in the ethyl acetate solvent was crushed with a wet crushing apparatus. Thereby, the silica slurry 8 was produced. Silica nanoparticles in the silica slurry 8 were coated with a first hydrophobic layer formed from the silicone oligomer 1 and a second hydrophobic layer formed from the silicone oligomer 3. In the production of the silica slurry 8, the content of the silica nanoparticles 8 in the ethyl acetate solvent was adjusted to 20% by mass. In preparation of the silica slurry 8, 20 mass% of the silicone oligomer 3 with respect to the silica nanoparticles 8 was added to the ethyl acetate solvent.

(Silica slurry 9)
After adding only the silica nanoparticle 1 to the ethyl acetate solvent and dispersing the silica nanoparticle 1 in the ethyl acetate solvent, the silica nanoparticle 1 in the ethyl acetate solvent was pulverized with a wet pulverizer. Thereby, the silica slurry 9 was produced. In the preparation of the silica slurry 9, the coating agent for forming the second hydrophobic layer was not used. Therefore, the silica nanoparticles in the silica slurry 9 are covered only with the first hydrophobic layer formed from the silicone oligomer 1. In preparation of the silica slurry 8, the ratio of the silica nanoparticles 1 in the ethyl acetate solvent was adjusted to 20% by mass.

(Silica slurry 10)
A silica slurry 10 was prepared in the same manner as silica slurry 1 except that commercially available silica (trade name: R805, manufactured by Nippon Aerosil Co., Ltd.) surface-treated with octylsilane was used instead of silica nanoparticle 1. Silica nanoparticles in the silica slurry 10 were coated with a first hydrophobic layer formed from octylsilane and a second hydrophobic layer formed from silicone oligomer 3.

(Silica slurry 11)
Silica nanoparticles 1 and 3-glycidoxypropyltrimethoxysilane are added to an ethyl acetate solvent to disperse the silica nanoparticles 1 in the ethyl acetate solvent, and then the silica nanoparticles 1 in the ethyl acetate solvent are dissolved by a wet crushing apparatus. Crushed. Thereby, the silica slurry 11 was produced. Silica nanoparticles in the silica slurry 11 were coated with a first hydrophobic layer formed from the silicone oligomer 1 and a second hydrophobic layer formed from 3-glycidoxypropyltrimethoxysilane. In the production of the silica slurry 11, the content of the silica nanoparticles 1 in the ethyl acetate solvent was adjusted to 20% by mass. In preparation of the silica slurry 1, 20% by mass of 3-glycidoxypropyltrimethoxysilane with respect to the silica nanoparticles 1 was added to the ethyl acetate solvent.

(Evaluation example 1)
100 g of phenoxy resin (trade name, Union Carbide, PKHC) and 75 g of acrylic rubber were dissolved in 300 g of ethyl acetate to obtain a resin solution having a solid content of 30% by mass. The acrylic rubber was a copolymer formed from 40 parts by weight of butyl acrylate, 30 parts by weight of ethyl acrylate, 30 parts by weight of acrylonitrile, and 3 parts by weight of glycidyl methacrylate. The molecular weight of the acrylic rubber was 850000.

  An adhesive solution 1a was prepared by adding 300 g of liquid epoxy containing a microcapsule-type latent curing agent to the above resin solution and stirring. As the liquid epoxy, NovaCure HX-3941 manufactured by Asahi Kasei Epoxy Corporation was used. The epoxy equivalent of the liquid epoxy was 185. The adhesive 1b for circuit connection of Evaluation Example 1 was prepared by mixing the silica slurry 1 immediately after preparation with the adhesive solution 1a. In the preparation of the circuit connecting adhesive 1b, the silica slurry 1 and the adhesive solution 1a are mixed so that the compounding amount of the silica nanoparticles 1 with respect to the total mass of the adhesive solid content contained in the adhesive solution 1a is 30% by mass. Blended. The viscosity of the silica slurry 1 immediately after preparation used in Evaluation Example 1 was measured with a vibration viscometer. The measurement results are shown in Table 1 below.

  4 g of conductive particles 1 were ultrasonically dispersed in 10 g of ethyl acetate to prepare a dispersion of conductive particles 1. In ultrasonic dispersion, a sample immersed in a beaker was placed in an ultrasonic device (trade name: US107, manufactured by Fujimoto Kagaku Co., Ltd.) and stirred for 1 minute. The frequency of the ultrasonic wave was 38 kHz, and the output was 400 W. The capacity of the ultrasonic device was 20L.

A dispersion of conductive particles 1 was dispersed in an adhesive 1b for circuit connection to prepare an adhesive solution 1c. The solution of the adhesive solution 1c was applied to the separator with a roll coater, and dried at 90 ° C. for 10 minutes to prepare a film-like conductive particle layer (A layer). The thickness of the A layer was adjusted to 10 μm. The number of the conductive particles 1 per unit area of the A layer was controlled to 30,000 / mm ² by adjusting the blending ratio of the dispersion of the conductive particles 1 and the circuit connecting adhesive 1b. As the separator, a polyethylene terephthalate film whose surface was treated with silicone was used. The thickness of the separator was 40 μm.

  The adhesive solution 1a was applied to the separator with a roll coater and dried at 90 ° C. for 10 minutes to produce a film-like adhesive layer (B layer). The thickness of the B layer was adjusted to 3 μm.

  The adhesive solution 1a was applied to the above separator with a roll coater and dried at 90 ° C. for 10 minutes to produce a film-like adhesive layer (C layer). The thickness of the C layer was adjusted to 10 μm.

  After laminating the A layer on the B layer, the C layer was laminated on the A layer to prepare an anisotropic conductive film D consisting of three layers.

  Using the anisotropic conductive film D, the chip with gold bumps and the glass substrate with circuit were connected in the following procedure to obtain a connection structure of Evaluation Example 1. The area of the gold bump was 30 × 90 μm. The space of the gold bump was 8 μm. The height of the gold bump was 15 μm. The number of bumps included in the chip was 362. The area of the chip was 1.7 × 1.7 mm. The thickness of the chip was 0.5 μm. The thickness of the glass substrate with circuit was 0.7 mm.

The layer B included in the anisotropic conductive film D was attached to a glass substrate with a circuit at 0.98 MPa (10 kgf / cm ² ) while heating to 80 ° C. After separating the separator from the anisotropic conductive film D and aligning the gold bumps of the chip with the glass substrate with circuit, the chip was laminated on the C layer included in the anisotropic conductive film D. The chip was pressed at a pressure of 40 [g / bump area] for 10 seconds while being heated to 190 ° C., and the chip and the glass substrate were finally connected. Thereby, the connection structure of Evaluation Example 1 was obtained.

(Evaluation example 2)
In Evaluation Example 2, an adhesive 1b for circuit connection was prepared using silica slurry 2 immediately after preparation instead of silica slurry 1. Except for this, the connection structure of Evaluation Example 2 was produced in the same manner as in Evaluation Example 1. The viscosity of the silica slurry 2 immediately after preparation used in Evaluation Example 2 was measured with a vibration viscometer. The measurement results are shown in Table 1 below.

(Evaluation example 3)
In Evaluation Example 3, a circuit connecting adhesive 1 b was prepared using silica slurry 3 instead of silica slurry 1. Except for this, the connection structure of Evaluation Example 3 was produced in the same manner as in Evaluation Example 1. The viscosity of the silica slurry 3 immediately after preparation used in Evaluation Example 3 was measured with a vibration viscometer. The measurement results are shown in Table 1 below.

(Evaluation example 4)
In Evaluation Example 4, an adhesive 1b for circuit connection was prepared using silica slurry 4 instead of silica slurry 1. Except for this, the connection structure of Evaluation Example 4 was produced in the same manner as in Evaluation Example 1. The viscosity of the silica slurry 4 immediately after preparation used in Evaluation Example 4 was measured with a vibration viscometer. The measurement results are shown in Table 1 below.

(Evaluation example 5)
In Evaluation Example 5, an adhesive 1b for circuit connection was prepared using silica slurry 5 instead of silica slurry 1. Except for this, the connection structure of Evaluation Example 5 was produced in the same manner as in Evaluation Example 1. The viscosity of the silica slurry 5 immediately after preparation used in Evaluation Example 5 was measured with a vibration viscometer. The measurement results are shown in Table 1 below.

(Evaluation example 6)
In Evaluation Example 6, a circuit connecting adhesive 1b was prepared using silica slurry 6 instead of silica slurry 1. Except for this, the connection structure of Evaluation Example 6 was produced in the same manner as in Evaluation Example 1. The viscosity of the silica slurry 6 immediately after preparation used in Evaluation Example 6 was measured with a vibration viscometer. The measurement results are shown in Table 1 below.

(Evaluation example 7)
In Evaluation Example 7, an adhesive 1b for circuit connection was prepared using silica slurry 7 instead of silica slurry 1. Except for this, the connection structure of Evaluation Example 7 was produced in the same manner as in Evaluation Example 1. The viscosity of the silica slurry 7 immediately after preparation used in Evaluation Example 7 was measured with a vibration viscometer. The measurement results are shown in Table 1 below.

(Evaluation example 8)
In Evaluation Example 8, an adhesive 1b for circuit connection was prepared using silica slurry 8 instead of silica slurry 1. Except for this, the connection structure of Evaluation Example 8 was produced in the same manner as in Evaluation Example 1. The viscosity of the silica slurry 8 immediately after preparation used in Evaluation Example 8 was measured with a vibration viscometer. The measurement results are shown in Table 1 below.

(Evaluation example 9)
In Evaluation Example 9, an adhesive 1b for circuit connection was prepared using silica slurry 9 instead of silica slurry 1. Except for this, the connection structure of Evaluation Example 9 was produced in the same manner as in Evaluation Example 1. The viscosity of the silica slurry 9 immediately after preparation used in Evaluation Example 9 was measured with a vibration viscometer. The measurement results are shown in Table 1 below.

(Evaluation example 10)
In Evaluation Example 10, an adhesive 1b for circuit connection was prepared using silica slurry 10 instead of silica slurry 1. Except for this, the connection structure of Evaluation Example 10 was produced in the same manner as in Evaluation Example 1. The viscosity of the silica slurry 10 immediately after preparation used in Evaluation Example 10 was measured with a vibration viscometer. The measurement results are shown in Table 1 below.

(Evaluation example 11)
In Evaluation Example 11, a circuit connecting adhesive 1 b was prepared using silica slurry 11 instead of silica slurry 1. Except for this, the connection structure of Evaluation Example 11 was produced in the same manner as in Evaluation Example 1. The viscosity of the silica slurry 11 immediately after preparation used in Evaluation Example 11 was measured with a vibration viscometer. The measurement results are shown in Table 1 below.

(Evaluation example 12)
In the preparation of the adhesive 1b for circuit connection of the evaluation example 12, the silica slurry 1 and the adhesive are adjusted so that the blending amount of the silica nanoparticles 1 is 10% by mass with respect to the total mass of the adhesive solid content contained in the adhesive solution 1a. Solution 1a was blended. Except for this, the connection structure of Evaluation Example 12 was produced in the same manner as in Evaluation Example 1. The viscosity of the silica slurry 1 immediately after preparation used in Evaluation Example 12 was measured with a vibration viscometer. The measurement results are shown in Table 1 below.

(Evaluation example 13)
In the preparation of the circuit connection adhesive 1b of Evaluation Example 13, the silica slurry 1 and the adhesive were adjusted so that the compounding amount of the silica nanoparticles 1 with respect to the total mass of the adhesive solid content contained in the adhesive solution 1a was 40% by mass. Solution 1a was blended. Except for this, the connection structure of Evaluation Example 13 was produced in the same manner as in Evaluation Example 1. The viscosity of the silica slurry 1 immediately after preparation used in Evaluation Example 13 was measured with a vibration viscometer. The measurement results are shown in Table 1 below.

(Evaluation Example 14)
In the preparation of the adhesive 1b for circuit connection of the evaluation example 14, the silica slurry 1 and the adhesive so that the blending amount of the silica nanoparticles 1 with respect to the total mass of the adhesive solid content contained in the adhesive solution 1a is 5% by mass. Solution 1a was blended. Except for this, the connection structure of Evaluation Example 14 was produced in the same manner as in Evaluation Example 1. The viscosity of the silica slurry 1 immediately after preparation used in Evaluation Example 14 was measured with a vibration viscometer. The measurement results are shown in Table 1 below.

(Evaluation Example 15)
In Evaluation Example 15, an adhesive 1b for circuit connection was prepared using the silica slurry 1 which had been left for 10 days (240 hours) after the adjustment instead of the silica slurry 1 immediately after the adjustment. Except for this, the connection structure of Evaluation Example 15 was produced in the same manner as in Evaluation Example 1. The viscosity of the silica slurry 1 used in Evaluation Example 15 was measured with a vibration viscometer. The measurement results are shown in Table 1 below.

(Evaluation Example 16)
In Evaluation Example 16, an adhesive 1b for circuit connection was prepared using the silica slurry 2 which had been left for 10 days (240 hours) after the adjustment instead of the silica slurry 2 immediately after the adjustment. Except for this, the connection structure of Evaluation Example 16 was produced in the same manner as in Evaluation Example 2. The viscosity of the silica slurry 2 used in Evaluation Example 16 was measured with a vibration viscometer. The measurement results are shown in Table 1 below.

(Evaluation Example 17)
In Evaluation Example 17, an adhesive 1b for circuit connection was prepared using the silica slurry 3 that had been allowed to stand for 10 days (240 hours) after the adjustment instead of the silica slurry 3 immediately after the adjustment. Except for this, a connection structure of Evaluation Example 17 was produced in the same manner as in Evaluation Example 3. The viscosity of the silica slurry 3 used in Evaluation Example 17 was measured with a vibration viscometer. The measurement results are shown in Table 1 below.

(Evaluation Example 18)
In Evaluation Example 18, an adhesive 1b for circuit connection was prepared using the silica slurry 4 which had been left for 10 days (240 hours) after the adjustment instead of the silica slurry 4 immediately after the adjustment. Except for this, the connection structure of Evaluation Example 18 was produced in the same manner as in Evaluation Example 4. The viscosity of the silica slurry 4 used in Evaluation Example 18 was measured with a vibration viscometer. The measurement results are shown in Table 1 below.

(Evaluation Example 19)
In Evaluation Example 19, a circuit connecting adhesive 1b was prepared using the silica slurry 5 which had been left for 10 days (240 hours) after the adjustment instead of the silica slurry 5 immediately after the adjustment. Except for this, the connection structure of Evaluation Example 19 was produced in the same manner as in Evaluation Example 5. The viscosity of the silica slurry 5 used in Evaluation Example 19 was measured with a vibration viscometer. The measurement results are shown in Table 1 below.

(Evaluation Example 20)
In Evaluation Example 20, an adhesive 1b for circuit connection was prepared using the silica slurry 6 which had been left for 10 days (240 hours) after the adjustment instead of the silica slurry 6 immediately after the adjustment. Except for this, the connection structure of Evaluation Example 20 was produced in the same manner as in Evaluation Example 6. The viscosity of the silica slurry 6 used in Evaluation Example 20 was measured with a vibration viscometer. The measurement results are shown in Table 1 below.

(Evaluation Example 21)
In Evaluation Example 21, an adhesive 1b for circuit connection was prepared using the silica slurry 7 that had been allowed to stand for 10 days (240 hours) after the adjustment instead of the silica slurry 7 immediately after the adjustment. Except for this, the connection structure of Evaluation Example 21 was produced in the same manner as in Evaluation Example 7. The viscosity of the silica slurry 7 used in Evaluation Example 21 was measured with a vibration viscometer. The measurement results are shown in Table 1 below.

(Evaluation example 22)
In Evaluation Example 22, an adhesive 1b for circuit connection was prepared using the silica slurry 8 which had been left for 10 days (240 hours) after the adjustment instead of the silica slurry 8 immediately after the adjustment. Except for this, the connection structure of Evaluation Example 22 was produced in the same manner as in Evaluation Example 8. The viscosity of the silica slurry 8 used in Evaluation Example 22 was measured with a vibration viscometer. The measurement results are shown in Table 1 below.

(Evaluation Example 23)
In Evaluation Example 23, an adhesive 1b for circuit connection was prepared using the silica slurry 9 that had been left for 10 days (240 hours) after the adjustment instead of the silica slurry 9 immediately after the adjustment. Except for this, the connection structure of Evaluation Example 23 was produced in the same manner as in Evaluation Example 9. The viscosity of the silica slurry 9 used in Evaluation Example 23 was measured with a vibration viscometer. The measurement results are shown in Table 1 below.

(Evaluation Example 24)
In Evaluation Example 24, an adhesive 1b for circuit connection was prepared using the silica slurry 10 that had been allowed to stand for 10 days (240 hours) after the adjustment instead of the silica slurry 10 immediately after the adjustment. Except for this, the connection structure of Evaluation Example 24 was produced in the same manner as in Evaluation Example 10. The viscosity of the silica slurry 10 used in Evaluation Example 24 was measured with a vibration viscometer. The measurement results are shown in Table 1 below.

(Evaluation Example 25)
In Evaluation Example 25, an adhesive 1b for circuit connection was prepared using the silica slurry 11 that had been left for 10 days (240 hours) after the adjustment instead of the silica slurry 11 immediately after the adjustment. Except for this, the connection structure of Evaluation Example 25 was produced in the same manner as in Evaluation Example 11. The viscosity of the silica slurry 11 used in Evaluation Example 25 was measured with a vibration viscometer. The measurement results are shown in Table 1 below.

[Weight change of silica nanoparticles]
The grafting rate of the silica nanoparticles in each silica slurry used in Evaluation Examples 1 to 25 was measured. In the measurement of the grafting rate, the silica nanoparticles taken out from the silica slurry by centrifugation were washed several times. The silica nanoparticles after washing were dried. The dried silica nanoparticles were heated to 1000 ° C. with a micro thermogravimetric apparatus, and the weight change was measured. The amount of change in weight is the weight reduction rate of silica nanoparticles accompanying heating at 1000 ° C. The weight change amount corresponds to the total value of the masses of the resin (first hydrophobic layer and second hydrophobic layer) removed from the silica nanoparticles by thermal decomposition. As shown in the following formula (A1), the measured weight change amount is equal to the grafting rate.
Grafting rate = 100 × (total value of mass of first hydrophobic layer and second hydrophobic layer) / (mass of silica nanoparticles) (A1)

[Appearance inspection of conductive particle layer]
When the conductive particle layers of Evaluation Examples 1 to 25 were formed by coating, the appearance of the conductive particle layers was inspected. The inspection results are shown in Table 2 below. When a large amount of nanoparticles that are difficult to disperse in the conductive particle layer are introduced into the conductive particle layer, the nanoparticles become an aggregate of several microns, and streaks are generated in the conductive particle layer during coating. Since there are almost no conductive particles in the portion where the streaks are generated, the streaks cause poor conduction.

[Insulation resistance test]
The insulation resistance test of the connection structures of Evaluation Examples 1 to 25 was performed. In the insulation resistance test, the resistance value (insulation resistance) between the gold bumps of the chip was measured. The distance between the gold bumps was 8 μm. The higher the insulation resistance, the better.

In the insulation resistance test, 20 connection structures of each evaluation example were prepared. In the insulation resistance test, the insulation resistance (initial value) before the migration test of each connection structure and the insulation resistance after the migration test were measured. Table 2 below shows the minimum value of the insulation resistance shown in each evaluation example. In the insulation resistance test, the ratio (yield) of the number of connection structures showing an insulation resistance greater than 10 ⁹ (Ω) among the 20 connection structures of each evaluation example was calculated. The yield (%) of the connection structure of each evaluation example is shown in Table 2 below. In the migration test, the connection structure was left in an environment of 60 ° C. temperature and 90% humidity for 1000 hours while applying a voltage of 20 V between the gold bumps.

[Conduction resistance test]
The conduction resistance test of the connection structures of Evaluation Examples 1 to 25 was performed. In the conduction resistance test, the resistance value (conduction resistance) between the gold bump of the chip and the circuit of the glass substrate was measured. The lower the conduction resistance, the better.

  In the conduction resistance test, the average value of the conduction resistance of the 14 connection structures was measured. In the conduction resistance test, the conduction resistance (initial value) before the moisture absorption heat test of the connection structure and the conduction resistance after the moisture absorption heat test were measured. The average value of the conduction resistance of each evaluation example is shown in Table 2 below. In the moisture absorption heat resistance test, each connection structure was left for 1000 hours in an environment where the temperature was 85 ° C. and the humidity was 85%.

[Measurement of capture rate]
The capture rate (%) of the connection structures of Evaluation Examples 1 to 25 was measured. The capture rate of each evaluation example is shown in Table 2 below. The capture rate is a ratio of the density of the conductive particles on the gold bump to the density of the conductive particles in the anisotropic conductive film, and is calculated by the following formula (B). The capture rate is a desired characteristic, the higher the better. The average value of the number of conductive particles on the gold bump was calculated from the number of conductive particles on 100 gold bumps. The number of conductive particles on each gold bump was confirmed by SEM.
Capture rate (%) = (average number of particles on gold bump / gold bump area / number of conductive particles contained per unit area of anisotropic conductive film) × 100 (B)

  Table 1 shows the structures of the silica nanoparticles and silica slurry used in each evaluation example. Table 2 shows the results of visual inspection, insulation resistance test, conduction resistance test, and capture rate measurement of the conductive particle layer of each evaluation example.

  The “blending amount” shown in Table 1 is the ratio of the mass of the silica nanoparticles to the total mass of the adhesive solid content contained in the conductive particle layer (adhesive solution 1a). The functional groups shown in parentheses in Table 1 are functional groups possessed by the silicone oligomer that is a coating agent. The weight reduction amount of the silica nanoparticles shown in Table 1 corresponds to the grafting rate of the silica nanoparticles contained in the conductive particle layer (circuit connection adhesive 1b).

  In Table 2, it was evaluated as “B” that there were no noticeable streaks in the appearance of the coated conductive particle layer. It was evaluated as “C” that there were slight streaks in the appearance of the coated conductive particle layer. It was evaluated as “D” that the appearance of the coated conductive particle layer had many streaks.

In Table 2, an insulation resistance of 10 ¹⁰ (Ω) or more is evaluated as A. An insulation resistance of 10 ⁹ (Ω) or more and less than 10 ¹⁰ (Ω) is evaluated as B. An insulation resistance of 10 ⁸ (Ω) or more and less than 10 ⁹ (Ω) is evaluated as C. An insulation resistance of less than 10 ⁵ (Ω) is evaluated as D. An evaluation example evaluated as D is not practical.

  In the column of the conduction resistance after the test in Table 2, a conduction resistance of 10 (Ω) or less is evaluated as A. A conduction resistance greater than 10 (Ω) and less than or equal to 16 (Ω) is evaluated as B. An insulation resistance greater than 16 (Ω) and not greater than 20 (Ω) is evaluated as C. A conduction resistance greater than 20 (Ω) is evaluated as D.

  In Table 2, a capture rate of 50% or more is evaluated as A. A capture rate of 40% or more and less than 50% is evaluated as B. A capture rate of 30% or more and less than 40% is evaluated as C. A capture rate of less than 30% is rated as D.

  In Evaluation Examples 1 to 6, the capture rate is greatly improved by increasing the blending amount of silica nanoparticles. As Evaluation Examples 1 to 3 show, as the silicone oligomer constituting the first hydrophobic layer, a type having a methyl group, a type having a phenyl group, and a type having a γ-glycidoxypropyl group can be used. In particular, by using a silicone oligomer having a phenyl group as in Evaluation Example 2, the insulating characteristics (bias characteristics) are dramatically improved.

  Evaluation Examples 15 to 20 differ from Evaluation Examples 1 to 6 only in that a silica slurry that has been left for a long time is used. In Evaluation Examples 15 to 20, since the surface of the silica nanoparticles is completely covered with the first hydrophobic layer and the second hydrophobic layer, the characteristics are stable regardless of the standing time of the slurry.

  Evaluation Example 6 using silica nanoparticles having a particle size of 7 nm tends to be excellent in insulation and capture rate. This means that the use of small particles increases the surface area of the silica nanoparticles per unit weight, making it easier to obtain desired characteristics. Conversely, in evaluation example 7, silica nanoparticles having a large particle size were used. In this Evaluation Example 7, a practical evaluation result was obtained, but the insulation resistance and the capture rate were lower than in Evaluation Example 6. Moreover, since the silica nanoparticles of Evaluation Example 7 are larger than those of Evaluation Example 6, the silica nanoparticles of Evaluation Example 6 tend to inhibit conduction.

  In Evaluation Example 8, the weight loss (grafting rate) is less than 2% by weight. In this case, since the hydroxyl groups on the surface of the silica nanoparticles cannot be completely covered with each hydrophobic layer, the silica nanoparticles in the silica slurry are aggregated by hydrogen bonding, and the viscosity of the silica slurry is increased. Moreover, since the hydroxyl group exposed on the silica nanoparticle surface remains, there exists a tendency for insulation resistance to be low. From this, it was confirmed that a grafting rate of 2% by mass or more is preferable.

  In Evaluation Example 9, no double hydrophobization treatment was performed. Also in this case, the insulating property tends to decrease.

  In Evaluation Example 10, octylsilane was used instead of silicone as a coating agent for forming the first hydrophobic layer. Also in this case, the insulating property tends to decrease. In Evaluation Example 11, a silane coupling agent was used as a coating agent for forming the second hydrophobic layer. Also in this case, the insulating property tends to decrease.

  Evaluation Examples 22 to 25 differ from Evaluation Examples 8 to 11 only in that a silica slurry left for a long time is used. In Evaluation Examples 22 to 25, due to the hydroxyl groups on the surface of the silica nanoparticles that are not completely covered with each hydrophobic layer, the aggregation of the silica nanoparticles gradually proceeds while the slurry is left, and the viscosity of the silica slurry tends to increase. is there. As a result, in Evaluation Examples 22 to 25, a large number of streaks were formed on the conductive particles in the coating. Furthermore, in Evaluation Examples 22 to 25, the insulation and conductivity deteriorated and the capture rate decreased.

  In Evaluation Example 12, the compounding amount of silica nanoparticles was reduced to 10% by mass. In this case, although the capture rate was slightly lowered, a practical evaluation result was obtained. In Evaluation Example 13, the compounding amount of silica nanoparticles was increased to 40 wt%. In this case, the conduction resistance is increased, but a practical evaluation result was obtained. In Evaluation Example 14, the compounding amount of silica nanoparticles was further reduced to 5 wt%. In this case, the capture rate becomes as low as that of the conventional anisotropic conductive film. However, in Evaluation Example 14, since the blending amount of the silica nanoparticles was small, a good appearance of the conductive particle layer was obtained. In view of Evaluation Examples 12 to 14, the compounding amount of silica nanoparticles is preferably 10 to 40% by mass.

  DESCRIPTION OF SYMBOLS 1 ... IC chip, 2 ... Metal bump, 3, 6 ... Adhesion layer, 5 ... Conductive particle layer, 7 ... Electrode, 8 ... Glass substrate, 9 ... Inorganic oxidation 10 ... conductive particles, 11 ... insulator, 12 ... anisotropic conductive film, 20 ... adhesive, 22 ... metal plating, 24 ... core particles, 32 ... ..First hydrophobic layer, 34... Second hydrophobic layer, 42.

Claims (16)

An adhesive, and inorganic oxide particles,
The inorganic oxide particles have a first hydrophobic layer that covers the inorganic oxide particles, and a second hydrophobic layer that covers the inorganic oxide particles or the first hydrophobic layer,
The total mass of the inorganic oxide particles relative to the total amount of the adhesive is greater than 5% by mass;
The first hydrophobic layer or the second hydrophobic layer comprises a silicone oligomer;
Adhesive for circuit connection. The inorganic oxide particles have a particle size of 5 to 30 nm.
The adhesive for circuit connection according to claim 1. The total mass of the inorganic oxide particles with respect to the total amount of the adhesive is 10 to 40% by mass.
The adhesive for circuit connection according to claim 1 or 2. The inorganic oxide particles are silica;
The adhesive for circuit connection as described in any one of Claims 1-3. The grafting rate represented by the following formula A is 2% by mass or more,
The adhesive for circuit connection as described in any one of Claims 1-4.
Grafting rate = 100 × (total value of mass of first hydrophobic layer and second hydrophobic layer) / (mass of inorganic oxide particles) (A) The first hydrophobic layer and the second hydrophobic layer comprise a silicone oligomer;
The adhesive for circuit connection as described in any one of Claims 1-5. The first hydrophobic layer is formed by treating the surface of the inorganic oxide particles with a gas phase containing a silicone oligomer,
The second hydrophobic layer is formed by treating the surface of the inorganic oxide particles on which the first hydrophobic layer is formed in a liquid phase containing a silicone oligomer.
The adhesive for circuit connection as described in any one of Claims 1-6. The silicone oligomer has a weight average molecular weight of 500 to 6000,
The adhesive for circuit connection as described in any one of Claims 1-7. The silicone oligomer is three-dimensionally crosslinked,
The adhesive for circuit connection as described in any one of Claims 1-8. The silicone oligomer has at least one of a trifunctional siloxane unit and a tetrafunctional siloxane unit;
The adhesive for circuit connection according to claim 9. The silicone oligomer has both bifunctional and trifunctional siloxane units;
The adhesive for circuit connection according to claim 9. The silicone oligomer has both bifunctional and tetrafunctional siloxane units;
The adhesive for circuit connection according to claim 9. A methyl group or a phenyl group is bonded to silicon which at least one of the bifunctional siloxane unit, the trifunctional siloxane unit, and the tetrafunctional siloxane unit has,
The adhesive for circuit connection according to claim 11 or 12. The silicone oligomer has a functional group that reacts with the adhesive,
The adhesive for circuit connection as described in any one of Claims 1-13. Formed by mixing the slurry containing the inorganic oxide particles and the organic solvent, and the adhesive,
The slurry has a viscosity of less than 17 mPa · s,
The adhesive for circuit connection as described in any one of Claims 1-14. A conductive particle layer comprising the adhesive for circuit connection according to any one of claims 1 to 15 and conductive particles contained in the adhesive for circuit connection,
Anisotropic conductive film.