KR102114802B1 - Anisotropic conductive film, connection method, and connected body - Google Patents

Abstract

An anisotropic conductive film for anisotropically connecting the terminals of the first electronic component and the terminals of the second electronic component, the conductive particle-containing layer containing the conductive particles, the filler and the cationic curing agent, and containing the cationic curing agent and not containing the filler An anisotropic conductive film having an insulating adhesive layer, wherein the conductive particles are at least one of metal particles and metal-coated resin particles, and the filler is at least one of metal hydroxides and metal oxides.

Description

Anisotropic conductive film, connection method and bonding body {ANISOTROPIC CONDUCTIVE FILM, CONNECTION METHOD, AND CONNECTED BODY}

The present invention relates to an anisotropic conductive film, a connection method and a joined body.

Conventionally, as a means for connecting electronic components, a tape-shaped connection material (for example, anisotropic conductive film (ACF)) in which a curable resin in which conductive particles are dispersed is applied to a release film is used.

This anisotropic conductive film includes various terminals, for example, when connecting a terminal of a flexible printed circuit board (FPC) or an IC chip and an ITO (Indium Tin Oxide) electrode formed on a glass substrate of an LCD panel. It is used in the case of electrically connecting together with bonding.

In recent years, in anisotropic conductive connection between electronic components using the anisotropic conductive film, low-temperature curing and low-temperature curing are necessary to cope with the increase in density of the bonded body obtained by the connection, cost reduction of the connection, suppression of warpage of the substrate due to the high-temperature connection, and the like. An anisotropic conductive film using a cationic curing agent capable of rapid curing is used.

However, in the anisotropic conductive film using a cationic curing agent, there is a problem that the wiring of the electronic component is corroded by the acid generated when the cationic curing agent is used. In addition, there is a problem that adhesion is not sufficient.

In order to prevent wiring corrosion, it is known that a metal hydroxide or a metal oxide can be used for the connection material (for example, see paragraph [0040] of Patent Document 1). However, corrosion of wiring cannot be prevented only by simply adding a metal hydroxide or a metal oxide to the anisotropic conductive film using a cationic curing agent. In addition, adhesion is not sufficient.

Therefore, it is possible to perform low-temperature curing and fast curing while satisfying short-circuit resistance, excellent particle trapping ratio and low connection resistance in electronic components in the resulting bonded body, which are required for anisotropic conductive films, and also prevent corrosion of wirings in electronic components. In addition, it is a phenomenon that an anisotropic conductive film using a cationic curing agent having excellent adhesiveness, a connection method using the anisotropic conductive film, and a bonded body obtained by the connection method are required.

Japanese Patent Application Publication No. 2011-111556

It is an object of the present invention to solve the above problems in the related art and achieve the following objects. That is, the present invention is capable of low-temperature curing and fast curing while satisfying short-circuit resistance, excellent particle trapping ratio and low connection resistance in electronic components in the resulting bonded body required for anisotropic conductive films, and also for wiring of electronic components. An object of the present invention is to provide an anisotropic conductive film using a cationic curing agent, which prevents corrosion, and has excellent adhesion, a connection method using the anisotropic conductive film, and a joined body obtained by the connection method.

The means for solving the above problems are as follows. In other words,

<1> It is an anisotropic conductive film which connects the terminal of the first electronic component and the terminal of the second electronic component anisotropically

A conductive particle-containing layer containing conductive particles, a filler, and a cationic curing agent,

Has an insulating adhesive layer containing a cationic curing agent and no filler,

The conductive particles are at least one of metal particles and metal-coated resin particles,

The filler is an anisotropic conductive film, characterized in that at least one of a metal hydroxide and a metal oxide.

<2> The anisotropic conductive film according to the above <1>, wherein at least one of the metal hydroxide and the metal oxide is at least one of aluminum hydroxide, magnesium hydroxide and aluminum oxide.

The <3> electroconductive particle containing layer is an anisotropic electrically conductive film in any one of said <1> to <2> which contains a film forming resin and curable resin.

<4> The anisotropic conductive film according to the above <3>, wherein the content of the filler in the conductive particle-containing layer is 0.20 parts by mass to 90 parts by mass relative to 100 parts by mass of the total amount of the film-forming resin, the curable resin, and the cationic curing agent.

<5> The filler is an anisotropic conductive film according to any one of <1> to <4>, wherein the filler has a particulate shape and an average particle diameter of the filler is 0.5 μm to 3.5 μm.

<6> The filler is an anisotropic conductive film according to any one of <1> to <5>, wherein the filler is non-spherical.

<7> An anisotropic conductive connection between the terminals of the first electronic component and the terminals of the second electronic component.

A first arrangement step of disposing the anisotropic conductive film according to any one of <1> to <6> above on a terminal of the second electronic component;

A second arrangement step of arranging the first electronic component on the anisotropic conductive film so that a terminal of the first electronic component contacts the anisotropic conductive film;

It is a connection method characterized by including the heating pressurization process of heating and pressurizing the said 1st electronic component by a heating pressurizing member.

<8> It is a joined body characterized by being obtained by the connection method described in <7> above.

According to the present invention, it is possible to solve the above-mentioned various problems in the prior art, achieve the above object, and prevent short circuits in electronic components in the obtained bonded body, required for anisotropic conductive films, excellent particle trapping rate and low connection resistance. An anisotropic conductive film using a cationic curing agent, a connection method using the anisotropic conductive film, and a connection method that is capable of low temperature curing and rapid curing while preventing satisfactory, and also prevents corrosion of wirings of electronic components and has excellent adhesion. The conjugate obtained by can be provided.

(Anisotropic conductive film)

The anisotropic conductive film of the present invention has at least a conductive particle-containing layer and an insulating adhesive layer, and has other layers as necessary.

The said anisotropic conductive film is an anisotropic conductive film which connects the terminal of a 1st electronic component and the terminal of a 2nd electronic component anisotropically.

The structure of the anisotropic conductive film is not particularly limited and may be appropriately selected according to the purpose, but a two-layer structure including the conductive particle-containing layer and the insulating adhesive layer is preferable.

<First electronic component and second electronic component>

As said 1st electronic component and said 2nd electronic component, if it is an electronic component which has a terminal which becomes the object of the anisotropic conductive connection using the said anisotropic conductive film, there is no restriction | limiting in particular, It can select suitably according to the objective, for example And glass substrates, flexible substrates, rigid substrates, IC (Integrated Circuit) chips, TAB (Tape Automated Bonding), and liquid crystal panels. As said glass substrate, an Al wiring formation glass substrate, an ITO wiring formation glass substrate, etc. are mentioned, for example. As said IC chip, the IC chip for liquid crystal screen control in a flat panel display (FPD), etc. are mentioned, for example.

<Conductive particle-containing layer>

The conductive particle-containing layer contains at least conductive particles, a filler, and a cationic curing agent, preferably contains a film-forming resin and a curable resin, and further contains other components as necessary.

-Conductive particle-

The conductive particles are not particularly limited as long as they are at least one of metal particles and metal-coated resin particles, and can be appropriately selected according to the purpose.

The metal particles are not particularly limited and can be appropriately selected according to the purpose, and examples thereof include nickel, cobalt, silver, copper, gold, and palladium. These may be used individually by 1 type and may use 2 or more types together.

Among these, nickel, silver, and copper are preferable. For the purpose of preventing surface oxidation of these metal particles, gold or palladium may be applied to the surface. Moreover, you may use what gave the surface an insulating coating with a metal protrusion or an organic substance.

The metal-coated resin particle is not particularly limited as long as it is a particle coated with a metal surface of the resin particle, and can be appropriately selected according to the purpose. For example, the surface of the resin particle is at least any of nickel, copper, gold, and palladium. And particles coated with a single metal. Moreover, you may use what gave the surface an insulating coating with a metal protrusion or an organic substance.

The method of coating the metal with the resin particles is not particularly limited, and can be appropriately selected according to the purpose, and examples thereof include an electroless plating method and sputtering method.

The material of the resin particles is not particularly limited and can be appropriately selected according to the purpose. For example, styrene-divinylbenzene copolymer, benzoguanamine resin, crosslinked polystyrene resin, acrylic resin, styrene-silica composite resin, etc. Can be lifted.

The said electroconductive particle should just have electroconductivity at the time of anisotropic conductive connection. For example, even if the particles are coated with an insulating film on the surface of the metal particles, they function as the conductive particles as long as the particles are deformed during the anisotropic conductive connection and the metal particles are exposed.

There is no restriction | limiting in particular as content of the said electroconductive particle in the said electroconductive particle containing layer, It can adjust suitably according to the wiring pitch of a circuit member, connection area, etc ..

-Filler-

The filler is not particularly limited as long as it is at least one of a metal hydroxide and a metal oxide, and can be appropriately selected according to the purpose.

The metal hydroxide and metal oxide are used to prevent corrosion of the wiring, improve adhesion, and improve insulation.

As said metal hydroxide, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, etc. are mentioned, for example.

Examples of the metal oxide include aluminum oxide, silicon oxide, magnesium oxide, antimony oxide, tin oxide, titanium oxide, manganese oxide, and zirconium oxide.

Among these, at least one of aluminum hydroxide, magnesium hydroxide and aluminum oxide is preferable, and at least one of aluminum hydroxide and magnesium hydroxide is more preferable from the viewpoint of corrosion resistance and adhesion.

In addition, preventing corrosion of metal hydroxides and metal oxides and improving adhesion are known as described in Japanese Patent Publication No. 2004-523661, Japanese Patent Publication No. 2011-111556, and the like.

It is preferable that the filler is particulate.

As said particulate filler, a spherical filler, a non-spherical filler, etc. are mentioned, for example. Among these, non-spherical fillers are preferable from the viewpoint of insulation, and amorphous fillers are more preferable.

The non-spherical shape is a shape other than the spherical shape.

The irregular shape means that the non-spherical shape is mixed with not only one type of shape but also various shapes. Examples of the various forms include irregularities, angles, and protrusions.

When the filler is in the form of particles, the average particle diameter of the filler is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.5 μm to 3.5 μm, and more preferably 0.5 μm to 2.0 μm. When the average particle diameter is within the above-mentioned preferred range, it is advantageous in that the insulating property, particle trapping rate and connection resistance are more excellent.

The average particle diameter is an arithmetic mean of particle diameters, optionally measured for 10 fillers.

When the filler is non-spherical, the maximum length of the particles is the particle diameter.

The particle diameter can be obtained, for example, by observation with a scanning electron microscope, measurement by a particle size distribution meter, or the like.

The ratio (A / B) of the average particle diameter (A) of the filler and the average particle (B) of the conductive particles when the filler is particulate is not particularly limited and may be appropriately selected according to the purpose. / 10 to 2/3 are preferred, and 1/10 to 1/2 are more preferred. When the ratio is within the above-described preferred range, it is advantageous in that the insulating property, particle trapping rate and connection resistance are more excellent.

In addition, the measuring method of the average particle diameter of the said electroconductive particle is the same as the measuring method of the average particle diameter of the said filler.

The content of the filler is not particularly limited and may be appropriately selected according to the purpose, but is preferably 0.20 parts by mass to 90 parts by mass with respect to 100 parts by mass of the total amount of the film-forming resin, the curable resin, and the cationic curing agent. It is more preferably from 4.0 parts by mass to 30 parts by mass. When the content is within the more preferable range, it is advantageous in that corrosion resistance, adhesion, and insulation are more excellent while maintaining low temperature curing and rapid curing.

-Cationic curing agent-

The cationic curing agent is not particularly limited as long as it is a curing agent that generates cationic species, and can be appropriately selected according to the purpose, and examples thereof include onium salts and the like.

As said onium salt, a sulfonium salt, an iodonium salt, etc. are mentioned, for example.

As said sulfonium salt, triaryl sulfonium salt etc. are mentioned, for example.

The O as a counter anion of the salt is not particularly limited, can be appropriately selected according to the purpose, for example, _{^{SbF 6 -, AsF 6 -,}} PF 6 -, BF 4 -, CH 3 SO 3 -, CF 3 SO ₃ ^- and the like.

The cationic curing agent may be a commercial product. As said commercial item, for example, Adeka Optomer SP-172 (made by Adeka, Inc.), Adeka Optomer SP-170 (made by Adeka, Inc.), Adeka Optomer SP-152 ( Adeka Co., Ltd., Adeka Optomer SP-150 (Adeka Co., Ltd.), Sun-Aid SI-60L (manufactured by Sanshin Chemical Co., Ltd.), Sun-Aid SI-80L (manufactured by Sanshin Chemical Co., Ltd. Kabukiki) Manufactured by Kaisha), Sun-Aid SI-100L (manufactured by Sanshin Chemical High School Co., Ltd.), Sun-aid SI-150L (manufactured by Sanshin Chemical High School Co., Ltd.), CPI-100P (manufactured by San-Afro Co., Ltd.), CPI- And 101A (manufactured by San-Afro Chemical Co., Ltd.), CPI-200K (manufactured by San-Afro Chemical Co., Ltd.), IRGACURE 250 (manufactured by BASF), and the like.

The content of the cationic curing agent in the conductive particle-containing layer is not particularly limited, and may be appropriately selected depending on the purpose, but is 10 parts by mass to 50 parts by mass based on 100 parts by mass of the total amount of the film-forming resin and the curable resin. Addition is preferable, and 20 to 40 parts by mass is more preferable.

-Film-forming resin-

The film-forming resin is not particularly limited and can be appropriately selected according to the purpose. For example, phenoxy resin, unsaturated polyester resin, saturated polyester resin, urethane resin, butadiene resin, polyimide resin, polyamide resin, And polyolefin resins. The said film forming resin may be used individually by 1 type, and may use 2 or more types together. Among these, a phenoxy resin is preferred from the viewpoints of film forming properties, workability, and connection reliability.

Examples of the phenoxy resin include resins synthesized from bisphenol A and epichlorohydrin.

As for the phenoxy resin, those synthesized as appropriate may be used, or commercial products may be used.

There is no restriction | limiting in particular as content of the said film forming resin in the said electroconductive particle containing layer, It can select suitably according to the objective.

-Curable resin-

The curable resin is not particularly limited as long as it is a resin cured by the action of a cationic curing agent, and can be appropriately selected depending on the purpose. Examples thereof include epoxy resins and the like.

There is no restriction | limiting in particular as said epoxy resin, It can select suitably according to the objective, For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, these modified epoxy resins, etc. are mentioned.

There is no restriction | limiting in particular as content of the said curable resin in the said electroconductive particle containing layer, It can select suitably according to the objective.

-Other ingredients-

There is no restriction | limiting in particular as said other component, It can select suitably according to the objective, For example, a silane coupling agent etc. are mentioned.

The silane coupling agent is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include an epoxy-based silane coupling agent, an acrylic-based silane coupling agent, a thiol-based silane coupling agent, and an amine-based silane coupling agent.

The content of the silane coupling agent in the conductive particle-containing layer is not particularly limited and can be appropriately selected according to the purpose.

The average thickness of the conductive particle-containing layer is not particularly limited and may be appropriately selected according to the purpose, but is preferably 3 μm to 30 μm, more preferably 4 μm to 20 μm, and particularly preferably 4 μm to 10 μm. .

There is no restriction | limiting in particular as a manufacturing method of the said electroconductive particle containing layer, It can select suitably according to the objective, For example, it contains the said electroconductive particle, the said filler, and the said cation-type hardening agent, Preferably it is the said film forming resin. And a method in which the blend containing the curable resin is mixed so as to be uniform, and then the blended blend is coated on a polyethylene terephthalate (PET) film subjected to peeling treatment.

<Insulating adhesive layer>

The insulating adhesive layer contains at least a cationic curing agent, no filler, and other components as necessary.

-Cationic curing agent-

The cationic curing agent is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include the cationic curing agent exemplified in the description of the conductive particle-containing layer. The preferred form is also the same.

The content of the cationic curing agent in the insulating adhesive layer is not particularly limited and can be appropriately selected depending on the purpose, but is 10 parts by mass to 50 parts by mass with respect to 100 parts by mass of the total amount of the film-forming resin and the curable resin. It is preferable, and 20 to 40 parts by mass is more preferable.

-Filler-

As said filler, if it is at least any one of a metal hydroxide and a metal oxide, there is no restriction | limiting in particular, It can select suitably according to the objective, For example, the filler etc. which were illustrated in the description of the said electroconductive particle containing layer are mentioned.

-Other ingredients-

There is no restriction | limiting in particular as said other component, It can select suitably according to the objective, For example, a film forming resin, curable resin, a silane coupling agent, etc. are mentioned.

The film-forming resin, the curable resin, and the silane coupling agent are not particularly limited and can be appropriately selected according to the purpose. For example, the film-forming resin, the curable resin, and the film-forming resin exemplified in the description of the conductive particle-containing layer and The said silane coupling agent is mentioned, respectively. The preferred form is also the same.

The average thickness of the insulating adhesive layer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 3 µm to 30 µm, more preferably 5 µm to 20 µm, and particularly preferably 7 µm to 15 µm.

There is no restriction | limiting in particular as a manufacturing method of the said insulating adhesive layer, It can select suitably according to the objective, For example, the formulation containing the said cation-type hardening agent, and if necessary, the said film forming resin and the said curable resin After mixing so as to become uniform, a method of coating the blended mixture on a polyethylene terephthalate (PET) film subjected to peeling may be mentioned.

The method for producing the anisotropic conductive film is not particularly limited, and can be appropriately selected according to the purpose. For example, the conductive particle-containing layer produced by the method for producing the conductive particle-containing layer described above, and the method for producing the insulating adhesive layer described above And a method of laminating the insulating adhesive layer produced by using a roll laminator or the like.

(Connection method and bonding body)

The connection method of the present invention includes at least a first batch process, a second batch process, and a heating and pressing process, and further includes other processes as necessary.

The connection method is a method of anisotropically conducting a connection between a terminal of the first electronic component and a terminal of the second electronic component.

The joined body of the present invention is obtained by the above-mentioned connection method of the present invention.

The first electronic component and the second electronic component are not particularly limited and can be appropriately selected according to the purpose. For example, the first electronic component and the second illustrated in the description of the anisotropic conductive film of the present invention. And electronic components, respectively.

<First batch process>

The first arrangement step is not particularly limited as long as it is a step of disposing the anisotropic conductive film of the present invention on the terminal of the second electronic component, and can be appropriately selected according to the purpose.

When the second electronic component is a substrate such as a glass substrate or a flexible substrate, and the first electronic component is an IC chip, TAB, etc., in the first arrangement step, for example, on the terminal of the second electronic component, An anisotropic conductive film is disposed so that the terminal and the conductive particle-containing layer of the anisotropic conductive film are in contact.

<Second batch process>

The second arrangement step is not particularly limited as long as the first electronic component is placed on the anisotropic conductive film so that the terminal of the first electronic component is in contact with the anisotropic conductive film. Can be.

<Heat pressurization process>

The heating and pressing step is not particularly limited as long as it is a step of heating and pressing the electronic component with a heating and pressing member, and can be appropriately selected according to the purpose.

As said heating pressurizing member, the pressurizing member etc. which have a heating mechanism are mentioned, for example. A heat tool etc. are mentioned as a pressurizing member which has the said heating mechanism, for example.

There is no restriction | limiting in particular as a temperature of the said heating, Although it can select suitably according to the objective, 120 degreeC-200 degreeC is preferable.

There is no restriction | limiting in particular as a pressure of the said pressurization, Although it can select suitably according to the objective, 0.1 kPa to 100 kPa is preferable.

The time for heating and pressurization is not particularly limited, and may be appropriately selected depending on the purpose, but is preferably 0.5 to 120 seconds.

Example

Hereinafter, examples of the present invention will be described, but the present invention is not limited to these examples at all.

(Production example)

<Preparation of filler>

Each aluminum hydroxide used in the following Examples and Comparative Examples was prepared by appropriate adjustment with reference to the production method of aluminum hydroxide described in paragraphs [0019] to [0023] of Japanese Patent Application Publication No. 2005-162606. .

In addition, about magnesium hydroxide, aluminum oxide, and magnesium oxide, it manufactured by the method similar to the manufacturing method of aluminum hydroxide.

(Example 1)

<Preparation of anisotropic conductive film>

-Production of conductive particle-containing layer-

Phenoxy resin (PKHH, manufactured by Tomoe High School Co., Ltd.) 25 parts by mass, epoxy resin (EP1001, manufactured by Mitsubishi Chemical Co., Ltd.) 10 parts by mass, cationic curing agent (SI-60L, Sanshin Chemical Co., Ltd., Sulfonium salt cationic curing agent) 10 parts by mass, silane coupling agent (A-187, Momentive Performance Materials, Inc.) 2 parts by mass, conductive particles (AUL704, Sekisui Chemicals Co., Ltd., acrylic resin particles, acrylic resin particles) Metal coating resin particles with an Ni / Au plating film formed on the surface, 30 parts by mass of an average particle diameter of 4.0 µm, and 0.1 parts by mass of aluminum hydroxide (amorphous, average particle diameter of 0.7 µm), a stirring device (rotating revolution mixer, Awatori Renta (Awatori Rentaro), manufactured by Shinki Co., Ltd.) and mixed to be uniform. The blended product after mixing was applied to the peeled PET film so that the average thickness after drying was 10 µm, thereby producing a conductive particle-containing layer.

-Production of insulating adhesive layer-

Phenoxy resin (PKHH, manufactured by Tomoe Kyohyo Co., Ltd.) 25 parts by mass, epoxy resin (EP1001, Mitsubishi Chemical Co., Ltd.) 10 parts by mass, cationic curing agent (SI-60L, Sanshin Chemical Co., Ltd., Sulfonium salt type cationic curing agent) 10 parts by mass and silane coupling agent (A-187, manufactured by Momentive Performance Materials) 2 parts by mass, stirring device (automatic revolution mixer, Awatori Rentaro, manufactured by Shinki) It was mixed so as to be uniform. The blended mixture was coated on a peeled PET film so that the average thickness after drying was 10 µm, to prepare an insulating adhesive layer.

The conductive particle-containing layer and the insulating adhesive layer obtained above were laminated at a roll temperature of 45 ° C using a roll laminator to obtain an anisotropic conductive film.

<Production of the conjugate and evaluation of the conjugate>

The joined body was manufactured by the following method, and evaluation shown below was performed. The results are shown in Table 2-1.

On the second electronic component, the anisotropic conductive film obtained above was disposed so that the conductive particle-containing layer was in contact with the second electronic component. Subsequently, the first electronic component was disposed on the insulating adhesive layer of the anisotropic conductive film. Subsequently, a Teflon (registered trademark) sheet having an average thickness of 50 µm was used as a buffer material, and the first electronic component was heated and pressurized under heating conditions of 170 ° C, 60 kPa, and 5 seconds.

<< Erosion resistance evaluation >>

-Test IC chip and glass substrate-

As the first electronic component, a test IC chip (size 1.8 mm × 20 mm, thickness 0.5 mm, size of gold plated bump 30 μm × 85 μm, bump height 15 μm) was used.

As the second electronic component, a glass substrate having a thickness of 0.7 mm on which an Al comb-shaped wiring was formed was used.

-evaluation-

DC 5 V was applied to the Al comb-shaped wiring of the obtained joined body for 12 hours. The 12 sets of Al comb-shaped wiring after application were observed with a metal microscope, and evaluated according to the following evaluation criteria.

〔Evaluation standard〕

○: No corrosion was observed.

Δ: Corrosion sites were observed in 1 to 4 locations.

X: Five or more corrosion sites were observed.

<< Adhesion evaluation >>

-Test IC chip and glass substrate-

As the first electronic component, a test IC chip (size 1.8 mm × 20 mm, thickness 0.5 mm, size of gold plated bump 30 μm × 85 μm, bump height 15 μm) was used.

As the second electronic component, a glass substrate having a thickness of 0.5 mm with an ITO film formed on the entire surface was used.

-evaluation-

The degree of excitation of the anisotropic conductive film on the glass substrate after the pressure cooker test (PCT) was visually observed and evaluated according to the following evaluation criteria. In addition, PCT was performed on conditions of 121 ° C, 2 atm, and 5 hours.

〔Evaluation standard〕

○: No excitation was observed.

Δ: Excitation of more than 0% and less than 10% was observed for the compressed area.

X: Excitation of 10% or more was observed with respect to the compressed area.

<< insulation evaluation >>

-Test IC chip and glass substrate-

As the first electronic component, a test IC chip (size 1.5 mm × 300 mm, thickness 0.5 mm, inter-bump space of gold-plated bumps of 10 μm, bump height of 15 μm) was used.

As the second electronic component, a glass substrate having a thickness of 0.5 mm with a comb-shaped ITO wiring pattern was used.

-evaluation-

By the two-terminal method, the number of shots between bumps at 16 points (total 160 points) was arbitrarily counted for each 10 sets of ITO comb-type wirings, and evaluated according to the following evaluation criteria. In addition, when the resistance value measured by the two-terminal method was 10 ⁸ Ω or less, it was judged to be short.

〔Evaluation standard〕

○: There was no short.

Δ: There were one or two shorts.

×: There were three or more shorts.

<< Evaluation of particle capture rate >>

-Test IC chip and glass substrate-

As the first electronic component, a test IC chip (size 1.8 mm × 20 mm, thickness 0.5 mm, size of gold plated bump 30 μm × 85 μm, bump height 15 μm) was used.

As the second electronic component, a glass substrate having a thickness of 0.7 mm on which ITO wiring was formed was used.

-evaluation-

The particle trapping rate was determined by the following method and evaluated.

Before the connection between the first electronic component and the second electronic component, the number of conductive particles (the number of particles before connection) on the bump (terminal) of the first electronic component was calculated by the following equation (1).

<Equation 1>

Number of particles before connection = particle (plane) density of conductive particles in the conductive particle-containing layer (pieces / mm 2) × area of terminals (mm 2)

In addition, the number of conductive particles on the terminal after connection (number of particles after connection) was measured by counting with a metal microscope. And the particle trapping rate of electroconductive particle was computed by following Formula (2). And it evaluated by the following evaluation criteria.

<Equation 2>

Particle capture rate (%) = (number of particles after connection / number of particles before connection) x 100

〔Evaluation standard〕

○: Particle capture rate is 20% or more

△: Particle capture rate of 17% or more and less than 20%

×: Particle capture rate is less than 17%

<< connection resistance evaluation >>

-Test IC chip and glass substrate-

As the first electronic component, a test IC chip (size 1.8 mm × 20 mm, thickness 0.5 mm, size of gold plated bump 30 μm × 85 μm, bump height 15 μm) was used.

As the second electronic component, a glass substrate having a thickness of 0.7 mm on which ITO wiring was formed was used.

-evaluation-

The initial resistance value of the obtained joined body was measured by the following method and evaluated.

Using a digital multimeter (Product No .: Digital Multimeter 7555, manufactured by Yokogawa Denki Co., Ltd.), the connection resistance when a current of 1 µA was passed through a 4-terminal method was measured. The obtained resistance value was evaluated by the following evaluation criteria.

〔Evaluation standard〕

○: Initial resistance value is less than 1 Ω

△: Initial resistance value is 1 Ω or more but less than 3 Ω

×: Initial resistance value is 3 Ω or more

(Examples 2 to 6)

In Example 1, an anisotropic conductive film and a bonded body were produced in the same manner as in Example 1, except that the compounding amount of aluminum hydroxide (filler) at the time of production of the conductive particle-containing layer was changed to the compounding amount shown in Table 1 below.

Evaluation similar to Example 1 was performed about the obtained joined body. The results are shown in Table 2-1.

<Table 1>

(Example 7)

In Example 4, an anisotropic conductive film and a bonded body were produced in the same manner as in Example 4, except that aluminum hydroxide was replaced with magnesium hydroxide (amorphous, average particle diameter of 0.7 µm).

Evaluation similar to Example 1 was performed about the obtained joined body. The results are shown in Table 2-1.

(Example 8)

In Example 4, an anisotropic conductive film and a bonded body were produced in the same manner as in Example 4, except that aluminum hydroxide was replaced with aluminum oxide (amorphous, average particle diameter of 0.7 µm).

Evaluation similar to Example 1 was performed about the obtained joined body. The results are shown in Table 2-2.

(Example 9)

In Example 4, an anisotropic conductive film and a bonded body were produced in the same manner as in Example 4, except that the amorphous aluminum hydroxide was replaced with a spherical aluminum hydroxide (average particle diameter of 0.7 µm).

Evaluation similar to Example 1 was performed about the obtained joined body. The results are shown in Table 2-2.

(Example 10)

In Example 4, an anisotropic conductive film and a bonded body were produced in the same manner as in Example 4, except that aluminum hydroxide having an average particle diameter of 0.7 µm was replaced with aluminum hydroxide having an average particle diameter of 0.5 µm (irregular shape).

Evaluation similar to Example 1 was performed about the obtained joined body. The results are shown in Table 2-2.

(Example 11)

In Example 4, an anisotropic conductive film and a bonded body were produced in the same manner as in Example 4, except that aluminum hydroxide having an average particle diameter of 0.7 µm was replaced with aluminum hydroxide having an average particle diameter of 2.0 µm (irregular shape).

Evaluation similar to Example 1 was performed about the obtained joined body. The results are shown in Table 2-2.

(Example 12)

In Example 4, an anisotropic conductive film and a bonded body were produced in the same manner as in Example 4, except that aluminum hydroxide having an average particle diameter of 0.7 µm was replaced with aluminum hydroxide having an average particle diameter of 3.5 µm (irregular shape).

Evaluation similar to Example 1 was performed about the obtained joined body. The results are shown in Table 2-2.

(Example 13)

In Example 4, an anisotropic conductive film and a bonded body were produced in the same manner as in Example 4, except that aluminum hydroxide was replaced with magnesium oxide (amorphous, average particle diameter of 0.7 µm).

Evaluation similar to Example 1 was performed about the obtained joined body. The results are shown in Table 2-2.

(Example 14)

Example 4, except that 10 parts by mass of aluminum hydroxide was replaced with 5 parts by mass of aluminum hydroxide (amorphous, average particle diameter of 0.7 µm) and 5 parts by mass of aluminum oxide (amorphous, average particle diameter of 0.7 µm), Example 4 In the same manner, an anisotropic conductive film and a joined body were produced.

Evaluation similar to Example 1 was performed about the obtained joined body. The results are shown in Table 2-2.

(Comparative Example 1)

In Example 4, an anisotropic conductive film and a bonded body were produced in the same manner as in Example 1, except that 10 parts by mass of aluminum hydroxide (irregular shape, average particle diameter of 0.7 µm) was blended at the time of production of the insulating adhesive layer.

Evaluation similar to Example 1 was performed about the obtained joined body. The results are shown in Table 2-3.

(Comparative Example 2)

In Example 1, the same procedure as in Example 1 was carried out, except that aluminum hydroxide was not contained in the conductive particle-containing layer, and 10 parts by mass of aluminum hydroxide (amorphous, average particle diameter of 0.7 µm) was added during the production of the insulating adhesive layer. Thus, an anisotropic conductive film and a joined body were produced.

Evaluation similar to Example 1 was performed about the obtained joined body. The results are shown in Table 2-3.

(Comparative Example 3)

In Example 1, an anisotropic conductive film and a bonded body were produced in the same manner as in Example 1, except that aluminum hydroxide was not contained in the conductive particle-containing layer.

Evaluation similar to Example 1 was performed about the obtained joined body. The results are shown in Table 2-3.

(Comparative Example 4)

Phenoxy resin (PKHH, manufactured by Tomoe Kyohyo Co., Ltd.) 25 parts by mass, epoxy resin (EP1001, Mitsubishi Chemical Co., Ltd.) 10 parts by mass, cationic curing agent (SI-60L, Sanshin Chemical Co., Ltd., Sulfonium salt type cationic curing agent) 10 parts by mass, silane coupling agent (A-187, Momentive Performance Materials, Inc.) 2 parts by mass, conductive particles (AUL704, manufactured by Sekisui Chemicals Co., Ltd.) 30 parts by mass, and 10 parts by mass of aluminum hydroxide (irregular shape, average particle diameter of 0.7 µm) were uniformly mixed using a stirrer (rotating revolution mixer, Awatori Renta, manufactured by Shinki Co., Ltd.). The blended mixture was coated on the peeled PET so that the average thickness after drying was 20 µm, to prepare an anisotropic conductive film.

A bonded body was produced in the same manner as in Example 1 using the obtained anisotropic conductive film.

Evaluation similar to Example 1 was performed about the obtained joined body. The results are shown in Table 2-3.

The results of the above Examples and Comparative Examples are summarized in Tables 2-1 to 2-3 below.

In addition, content of a filler is content of a filler with respect to 100 mass parts of total amount of phenoxy resin, epoxy resin, and cationic curing agent of each layer.

<Table 2-1>

<Table 2-2>

<Table 2-3>

In Examples 1 to 14, since only the conductive particle-containing layer contained a filler (at least one of a metal hydroxide and a metal oxide), corrosion of the wiring could be suppressed, and corrosion resistance was good. Moreover, the adhesiveness was also excellent, and the insulating property, particle capture rate, and connection resistance were also good.

Particularly, when the content of the filler in the conductive particle-containing layer is 4.0 parts by mass to 30 parts by mass with respect to 100 parts by mass of the total amount of the film-forming resin, the curable resin, and the cationic curing agent, corrosion resistance and adhesion are more excellent. (For example, Examples 3 and 4).

In addition, when the filler is aluminum hydroxide, which is a metal hydroxide, or magnesium hydroxide, corrosion resistance and adhesion are more excellent results (for example, Examples 4 and 7).

When the filler was in the amorphous form, it resulted in better insulating properties than the spherical case (for example, Examples 4 and 9).

When the average particle diameter of the filler was 0.5 µm to 2.0 µm, insulating properties, particle trapping rate, and connection resistance were more excellent results (for example, Examples 4, 10, and 11).

On the other hand, when the filler was contained not only in the conductive particle-containing layer but also in the insulating adhesive layer, the insulating properties and the particle trapping rate were insufficient (Comparative Example 1).

When the filler was contained only in the insulating adhesive layer, corrosion resistance and adhesion were lowered compared to Comparative Example 1 (Comparative Example 2).

When neither the conductive particle-containing layer nor the insulating adhesive layer contains a filler, corrosion resistance, adhesion, and insulation were insufficient (Comparative Example 3).

When the anisotropic conductive film had a single-layer structure of only the conductive particle-containing layer and a filler was contained in the conductive particle-containing layer, corrosion resistance, adhesion, insulation, and particle trapping rate were insufficient (Comparative Example 4).

Since the anisotropic conductive film of the present invention is excellent in corrosion resistance and adhesion, low-temperature curing using a cationic curing agent can also be suitably used in the manufacture of a joined body by fast curing connection.

Claims (8)

An anisotropic conductive film for anisotropically connecting the terminals of the first electronic component and the terminals of the second electronic component,
A conductive particle-containing layer containing conductive particles, a filler, and a cationic curing agent,
Has an insulating adhesive layer containing a cationic curing agent and no filler,
The conductive particles are at least one of metal particles and metal-coated resin particles,
The anisotropic conductive film, characterized in that the filler is at least one of a metal hydroxide and a metal oxide. The anisotropic conductive film according to claim 1, wherein at least one of the metal hydroxide and the metal oxide is at least one of aluminum hydroxide, magnesium hydroxide and aluminum oxide. The anisotropic conductive film according to claim 1, wherein the conductive particle-containing layer contains a film-forming resin and a curable resin. The anisotropic conductive film according to claim 3, wherein the content of the filler in the conductive particle-containing layer is 0.20 parts by mass to 90 parts by mass relative to 100 parts by mass of the total amount of the film-forming resin, the curable resin, and the cationic curing agent. The anisotropic conductive film according to claim 1, wherein the filler is particulate and the filler has an average particle diameter of 0.5 µm to 3.5 µm. The anisotropic conductive film according to claim 1, wherein the filler is non-spherical particulate. It is the connection method which connects the terminal of a 1st electronic component and the terminal of a 2nd electronic component anisotropically conductively,
A first arrangement step of disposing the anisotropic conductive film according to any one of claims 1 to 6 on a terminal of the second electronic component,
A second arrangement step of arranging the first electronic component on the anisotropic conductive film so that a terminal of the first electronic component contacts the anisotropic conductive film;
And a heating pressurizing step of heating and pressurizing the first electronic component with a heat pressurizing member. The bonding body in which the terminal of a 1st electronic component and the terminal of a 2nd electronic component are anisotropically conductive-connected through the hardened | cured material of the anisotropic conductive film in any one of Claims 1-6.