JP2019067693A - Anisotropic conductive film and manufacturing method thereof - Google Patents

Abstract

To provide an anisotropic conductive film for connecting circuit electrodes each having a fine pattern.SOLUTION: A anisotropic conductive film 6 includes a base layer 2 including an insulating resin on a releasable substrate 1, and on the base layer 2, bumps 3 that are conductive nanoparticle aggregates are arranged at intervals of 1 μm to 100 μm, and a covering layer 4 including an insulating resin is formed on the base layer 2 so as to cover the bumps 3, and the releasable substrate 1 has releasability with respect to the base layer 2.SELECTED DRAWING: Figure 3

Description

  The present invention relates to an anisotropic conductive film and a method of manufacturing the same.

  In recent years, when connecting flat panel displays such as liquid crystal displays (LCD: Liquid Crystal Display) and electronic parts of precision instruments, an anisotropic conductive film (ACF: Anisotropic Conductive Film) is used instead of solder. There is. The anisotropic conductive film is mainly made of an insulating resin containing conductive particles, and can be disposed between the circuit electrodes and can be electrically connected between the circuits by pressure bonding and pressure bonding by heating.

  In Patent Document 1, an anisotropic conductive film is produced by applying a mixture of a polyvinyl butyral resin and an epoxy resin containing tin-lead solder particles having an average particle diameter of 10 μm and a maximum particle diameter of 15 μm. In patent document 2, the nickel particle of average particle diameter 2 micrometers is mixed with a phenoxy resin, and the anisotropic conductive film is produced using the coating apparatus. In patent document 3, an anisotropic conductive film is produced by mixing and apply | coating silver-plated resin particle with an average particle diameter of 20 micrometers to insulating resin. In Patent Document 4, a silver powder-containing epoxy resin having an average particle diameter of 5 to 10 μm is printed on an epoxy resin layer, an epoxy resin is coated thereon, and printing of the silver powder-containing epoxy resin and coating of the epoxy resin are performed. The anisotropic conductive film is produced by repeating.

  However, since all the films described in the above-mentioned patent documents are mixed with micro-particles and coated, aggregation of the particles occurs, and the insulation property of the film is maintained to 100 μm or less It is difficult to maintain the conductive area of On the other hand, when the particle concentration is lowered to prevent aggregation of particles, it is difficult to maintain the conductivity in the cross-sectional direction of the film. For this reason, circuit electrodes having fine patterns can not be electrically connected to each other.

  Patent Documents 5 and 6 report anisotropic conductive films in which conductive particles are arranged in a grid, and in at least one direction, the spacing between adjacent arrays is wide and narrow. In this method, one electrode is energized by a plurality of micro conductive particles, and the distance between the bumps is not constant, so it is not suitable to connect circuit electrodes having fine patterns.

  In Patent Document 7, a porous plate having a hole smaller than the particle diameter of the conductive particles is placed in a container containing the conductive particles, and the opposite side of the side on which the conductive particles exist separated by the porous plate is decompressed. The conductive particles are captured by the porous plate by setting the thickness to make an anisotropic conductive film. However, since it is necessary to prepare a porous plate having pores smaller than the particle diameter, the particles necessarily become large, and it is necessary to reduce the pressure on the side opposite to the side on which the conductive particles exist. The cost is extremely high because As described above, it was difficult to arrange conductive particles regularly at low cost.

JP-A-5-154857 JP, 2008-112713, A JP, 2015-147832, A JP 2003-151713 A JP, 2016-0885931, A International Publication WO2016 / 104463 JP 2005-209454 A

  This invention is made in view of the said problem, Comprising: It aims at providing the anisotropic conductive film for connecting the circuit electrodes which have a fine pattern.

  In order to achieve the above-mentioned subject, in the present invention, it is an anisotropic conductive film, and it has a base layer containing insulating resin on a exfoliation base material, and 1 micrometer-on the base layer. A bump, which is a conductive nanoparticle aggregate, is arranged at intervals of 100 μm, and a covering layer containing an insulating resin is formed on the base layer to cover the bump, and the peelable group An anisotropic conductive film is provided, wherein the material has releasability with respect to the base layer.

  With such an anisotropic conductive film, circuit electrodes having a fine pattern can be connected to each other.

  Moreover, it is preferable that the average diameter of the said bump is 1 micrometer-100 micrometers.

  With such an average diameter of the bumps, it is possible to more reliably connect circuit electrodes having a fine pattern.

  Moreover, it is preferable that the said electroconductive nanoparticle assembly is an assembly which consists of an electroconductive nanoparticle with a primary particle diameter of 1 nm-500 nm.

  With such a conductive nanoparticle assembly, bumps of a desired size can be easily formed.

  The thickness of the base layer is preferably 1% to 100% of the average diameter of the bumps.

  With such a thickness of the base layer, the bumps can be easily arranged without the peelable substrate repelling the conductive nanoparticles.

  The thickness of the covering layer is preferably 101% to 500% of the average diameter of the bumps.

  With such a thickness of the covering layer, since the conductive nanoparticle aggregate is not exposed to the surface, deterioration of the conductive nanoparticles can be avoided, and when the circuit electrode is pressed, the electrodes and bumps can be more reliably Can be electrically connected by contact.

In addition, at least one of the base layer and the covering layer contains a silicone resin as an insulating resin, and includes the following components (A), (B), and (C): Is preferred.
(A) Silicone resin represented by the following average formula (1) R ¹ _a R ² _b R ³ _c (OX) _d SiO _{(4-a-b-c-d) / 2} (1)
Wherein R ¹ is a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, R ² is a saturated hydrocarbon group having 1 to 6 carbon atoms, and R ³ is an alkenyl group having 2 to 6 carbon atoms X is a monovalent hydrocarbon group having 1 to 6 carbon atoms or a hydrogen atom, and a, b, c and d are aa0, b> 0, c> 0 and dd0, respectively. And a + b + c + d = 1 to 2, provided that at least two alkenyl groups are contained in one molecule.
(B) Silicone resin represented by the following average formula (2) R ¹ _e R ² _f H _g (OX) _h SiO _{(4-e-f-g-h) / 2} (2)
(Wherein, R ¹ , R ² and X are the same as the aforementioned R ¹ , R ² and X. e, f, g and h are respectively e ≧ 0, f> 0, g> 0 and h ≧ 0, and e + f + g + h = 1 to 2, provided that at least two hydrogen atoms bonded to silicon atoms are contained in one molecule.
(C) Hydrosilylation catalyst

  If it is such an anisotropic conductive film, it can be set as the anisotropic conductive film which was more excellent in heat resistance and light resistance.

  The silicone resin is preferably solid at 25 ° C.

  With such a silicone resin, it is possible to make an anisotropic conductive film more excellent in manufacturing workability.

Moreover, in the present invention, it is a method for producing an anisotropic conductive film,
(1) A step of coating a composition containing an insulating resin on a peelable substrate to form a base layer,
(2) A conductive nanoparticle aggregate is applied onto the base layer by applying a voltage to the conductive nanoparticle dispersion and applying the conductive nanoparticle dispersion to the base layer from a nozzle by electrostatic force Forming a coating layer on the base layer by arranging the bumps in the body at intervals of 1 μm to 100 μm, and (3) coating a composition containing an insulating resin to cover the surface of the bumps The process to
A method of producing an anisotropic conductive film comprising:

  If it is a manufacturing method of such an anisotropic conductive film, it has a base layer containing an insulating resin on the above-mentioned exfoliation base material, and it will conduct electricity at intervals of 1 micrometer-100 micrometers on the base layer. And the covering layer containing the insulating resin is formed on the base layer so as to cover the bumps, and the peelable substrate is the base layer. An anisotropic conductive film having a releasability can be easily produced.

  Further, (1) ′ step of curing the base layer between the step (1) and the step (2) may be carried out, and / or the covering layer may be formed after the step (3). It is preferable to carry out step (3) 'which is the step of curing.

  With such a method for producing an anisotropic conductive film, it is possible to easily produce an anisotropic conductive film having high heat resistance and light resistance.

  As described above, according to the anisotropic conductive film of the present invention, circuit electrodes having very fine patterns can be electrically joined with each other, thereby achieving downsizing, thinning, and weight reduction of electronic devices. be able to.

In Example 1, it is a schematic diagram of the cross section after forming a base layer in a peelable base material. In Example 1, it is a schematic diagram of the cross section after forming the bump which is an electroconductive nanoparticle assembly on a base layer. In Example 1, after forming a bump, it is a schematic diagram of the cross section after forming a coating layer. It is an example of the photograph of the external appearance after apply | coating a silver nanoparticle to a base layer in Example 1. FIG. It is an example of the photograph of the external appearance after apply | coating a silver nanoparticle to a base layer in Example 2. FIG. It is an example of the photograph of the external appearance after apply | coating a silver nanoparticle to a base layer in Example 3. FIG. It is an example of the photograph of the external appearance after apply | coating a silver nanoparticle to a base layer in Example 4. FIG. It is an example of the photograph of the external appearance after apply | coating a silver nanoparticle to a base layer in Example 5. FIG. In an Example and a comparative example, it is a schematic diagram of the cross section of the film after pressing a circuit electrode (micro LED) in the case of an electricity supply test.

  As mentioned above, development of the anisotropic conductive film for connecting the circuit electrodes which have a fine pattern was called for.

  The inventors of the present invention conducted intensive studies to achieve the above object, and as a result, it is an anisotropic conductive film, which has a base layer containing an insulating resin on a peelable base material, The bumps, which are conductive nanoparticle aggregates, are arranged at intervals of 1 μm to 100 μm, and a covering layer containing an insulating resin is formed on the base layer so as to cover the bumps, and It is found that circuit electrodes having fine patterns can be electrically connected to each other by using an anisotropic conductive film in which the releasable substrate has releasability from the base layer. The present invention has been achieved.

  That is, the present invention is an anisotropic conductive film, having a base layer containing an insulating resin on a peelable base material, and conductive on the base layer at intervals of 1 μm to 100 μm. A bump, which is an aggregate of nanoparticles, is arranged, and a covering layer containing an insulating resin is formed on the base layer so as to cover the bump, and the peelable substrate is the base layer It is an anisotropic conductive film which has releasability with respect to.

  Hereinafter, although the anisotropic conductive film of this invention is demonstrated in detail, this invention is not limited to these.

[Peelable substrate]
The releasable substrate used in the present invention is not particularly limited as long as it is a substrate which can be peeled off after curing or semi-curing the below-mentioned base layer and coating layer, and for example, a fluorine-based film, mold release Agent treated PET film and the like. There is no restriction | limiting in particular as a thickness of a peelable base material, Although it can select according to the objective, It is preferable that they are 10 micrometers-1,000 micrometers.

  Here, "semi-hardening" refers to being in the so-called "B-stage state", and in the case where the insulating resin contained in the base layer described later is a thermosetting resin, heating is performed from the uncured state. After being treated, the surface of the resin refers to an intermediate state which is not tacky but not completely cured.

[Base layer]
The base layer contains an insulating resin, and is used to align the bumps, which are the aggregate of conductive nanoparticles described later. Without the base layer, the peelable substrate repels the conductive nanoparticles and can not form a desired bump.

  The insulating resin contained in the base layer is not particularly limited as long as it can be peeled off from the peelable substrate, and acrylic resin, polyester resin, polyethylene resin, cellulose resin, styrene resin, polyamide resin, polyimide resin And thermoplastic resins such as melamine resin, silicone resins, epoxy resins, silicone epoxy resins, phenolic resins, thermosetting resins such as perfluoropolyether resins, etc., but in view of heat resistance and light resistance, silicone Resin and epoxy resin are preferable, and silicone resin is more preferable. Examples of silicone resins include UV-curable, thermosetting and moisture-curable silicone resins.

  The thickness of the base layer is preferably 1% to 100%, more preferably 5% to 80%, of the average diameter of the bumps, which are the aggregate of conductive nanoparticles described later. More preferably, it is 50%. With such a range of base layer thickness, the bumps can be easily aligned without the releasable substrate repelling the conductive nanoparticles.

[Conductive nanoparticles]
There is no restriction | limiting in particular as an electroconductive nanoparticle used for this invention, According to the objective, it can select suitably, For example, a metal particle, electroconductive polymer particle, metal coating particle etc. are mentioned.

  Examples of the metal particles include metals such as gold, silver, copper, palladium, aluminum, nickel, iron, titanium, manganese, zinc, tungsten, platinum, lead, and tin, or alloys such as solder, steel, and stainless steel. Be Each of these may be used alone or in combination of two or more. Examples of conductive polymer particles include carbon, polyacetylene nanoparticles, polypyrrole nanoparticles and the like. Examples of the metal-coated particles include those in which the surface of resin particles is coated with metal, and those in which the surface of inorganic substances such as glass and ceramic is covered with metal. There is no restriction | limiting in particular as a metal coating method of the surface, For example, the electroless-plating method, sputtering method, etc. are mentioned.

  The above-described conductive nanoparticles may be conductive as long as they are electrically connected to the circuit electrode. For example, even if it is the particle which gave the insulating film to the particle | grain surface, when it electrically connects, a particle | grain deform | transforms and if metal particle is exposed, it is an electroconductive nanoparticle.

  The average particle diameter of the conductive nanoparticles described above is not particularly limited, but is preferably 1 nm to 500 nm in order to form a bump which is an aggregate of conductive nanoparticles having an average diameter of 1 μm to 100 μm described later. More preferably, they are 5 nm-400 nm, More preferably, they are 10 nm-300 nm. Within this range, as described later, when the conductive nanoparticle dispersion liquid is applied, bumps having an average diameter of 1 μm to 100 μm can be easily formed. In addition, the average particle diameter of a nanoparticle can be made into the average value of the maximum diameter of 100 particle | grains observed by the transmission electron microscope, for example.

[Bump which is a conductive nanoparticle aggregate]
The average diameter of the bumps as the conductive nanoparticle assembly is preferably 1 μm to 100 μm, more preferably 2 μm to 50 μm, and still more preferably 3 μm to 20 μm. The bumps described above are arranged at an interval of 1 μm to 100 μm, more preferably 2 μm to 50 μm, and still more preferably 3 μm to 20 μm. In the present invention, the average diameter of the bumps described above can be, for example, the average value of the maximum diameters of 100 bumps observed by an optical microscope. Also, the distance between bumps can be, for example, an average value of 99 points of the distance between any two adjacent bumps observed by an optical microscope.

  The method for applying the conductive nanoparticles to the base layer is not particularly limited, but in order to arrange the above-mentioned bumps at an interval of 1 μm to 100 μm, it is preferable to apply the conductive nanoparticle dispersion by electrostatic force . By suctioning the conductive nanoparticle dispersion from the nozzle and applying a voltage to the conductive nanoparticle dispersion, a charge is applied to the conductive nanoparticle dispersion, and when applied, the conductive nanoparticle aggregates repel each other. Use what you do.

[Covering layer]
After the bumps are arranged on the base layer, a covering layer including an insulating resin is formed to cover the bumps. There is no restriction | limiting in particular as insulating resin contained in a coating layer, The same thing as what was mentioned by the above-mentioned base layer can be illustrated. Specifically, thermoplastic resins such as acrylic resin, polyester resin, polyethylene resin, cellulose resin, styrene resin, polyamide resin, polyimide resin, melamine resin, silicone resin, epoxy resin, silicone epoxy resin, phenol resin, perfluoro resin A thermosetting resin such as a polyether resin may, for example, be mentioned, but in consideration of heat resistance and light resistance, silicone resins and epoxy resins are preferable, and silicone resins are more preferable. Examples of silicone resins include UV-curable, thermosetting and moisture-curable silicone resins. In addition, the kind of insulating resin used for a coating layer may be the same as or different from the insulating resin contained in the above-mentioned base layer.

  The thickness of the covering layer is preferably 101% to 500%, and more preferably 101% to 300% of the average diameter of the above-mentioned bumps. Within this range, since the conductive nanoparticle aggregate is not exposed to the surface, deterioration of the conductive nanoparticles can be avoided, and when the circuit electrode is pressed, the electrode and the bump contact more reliably. Connection is possible.

  Moreover, after forming a coating layer, you may bond a peelable film on this coating layer. The peelable film may, for example, be a PET film coated with a fluorine resin, a PET film coated with a silicone resin, a fluorine resin film or the like.

  As mentioned above, if it is the anisotropic conductive film of this invention, the anisotropic conductive film for connecting the circuit electrodes which have a fine pattern can be provided.

Moreover, in the present invention, it is a method for producing an anisotropic conductive film,
(1) A step of coating a composition containing an insulating resin on a peelable substrate to form a base layer,
(2) A conductive nanoparticle aggregate is applied onto the base layer by applying a voltage to the conductive nanoparticle dispersion and applying the conductive nanoparticle dispersion to the base layer from a nozzle by electrostatic force Forming a coating layer on the base layer by arranging the bumps in the body at intervals of 1 μm to 100 μm, and (3) coating a composition containing an insulating resin to cover the surface of the bumps The process to
A method of producing an anisotropic conductive film comprising:

  Hereinafter, although the manufacturing method of the anisotropic conductive film of this invention is demonstrated in detail, this invention is not limited to these.

[Step (1)]
The step (1) is a step of coating a composition containing an insulating resin on a peelable substrate to form a base layer.

  In addition to the insulating resin contained in the above-mentioned base layer, arbitrary components can be mix | blended with the composition containing insulating resin, for example, a solvent etc. can be mix | blended.

  The base layer may be formed according to a conventionally known method, for example, a film coater, a heat press or the like can be used. As a film coater, for example, a direct gravure coater, a chamber doctor coater, an offset gravure coater, a roll kiss coater, a reverse kiss coater, a bar coater, a die coater, a reverse roll coater, a slot die, an air doctor coater, a positive rotation roll coater, a blade coater , Knife coater, impregnation coater, MB coater, and MB reverse coater. In addition, as described later, the same device as the device for applying the conductive nanoparticle dispersion may be used, and spray application may be performed from the nozzle.

[(1) 'process]
(1) The 'process is a process of curing the base layer. When using a thermoplastic resin for the base layer, it is not necessary to carry out the step (1) '. Although the method for curing is not particularly limited, for example, it can be cured by methods such as UV curing, heat curing, moisture curing and the like.

[Step (2)]
In step (2), a voltage is applied to the conductive nanoparticle dispersion, and the conductive nanoparticle dispersion is applied to the base layer from the nozzle by electrostatic force, whereby the conductive layer is conductive on the base layer. This is a step of arranging the bumps, which are nanoparticle aggregates, at an interval of 1 μm to 100 μm.

[Conductive nanoparticle dispersion]
The conductive nanoparticles as described above can be used for the conductive nanoparticle dispersion liquid. There is no restriction | limiting in particular as a dispersion medium of an electroconductive nanoparticle dispersion liquid, According to the wettability to the base layer containing volatility, polarity, or a curable silicone resin, etc., it can select suitably. For example, alcohols such as methanol, ethanol, 1-propanol, isopropyl alcohol, 1-butanol, terpineol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, propylene glycol-1-monomethyl ether-1-acetate, etc. Esters of N, N-dimethylformamide, amides such as N, N-dimethylacetamide, ethers such as diethyl ether, dibutyl ether and tetrahydrofuran, aromatic hydrocarbons such as benzene, toluene and xylene, hexane, heptane and the like Aliphatic hydrocarbons, halogenated hydrocarbons such as methylene chloride and chloroform, carboxylic acids such as formic acid and acetic acid, acetonitrile, dimethyl sulfoxide, and water, among which methanol and ethanol are particularly preferable. Terpineol, it is preferable to use water or the like. Each of these may be used alone or in combination of two or more. The concentration of the nanoparticles in the conductive nanoparticle dispersion is preferably 10% by mass to 80% by mass, more preferably 20% by mass to 70% by mass, and still more preferably 30% by mass to 60% by mass .

  The conductive nanoparticle dispersion may further contain a resin component as a binder, and the resin component may be, for example, polyester resin, polyethylene resin, cellulose resin, acrylic resin, styrene resin, polyamide resin, melamine resin, phenol resin, Epoxy resin, silicone resin and the like can be mentioned. Each of these may be used alone or in combination of two or more. When these resin components are contained as a binder, it is preferable to use the same resin as that of the base layer or the covering layer from the viewpoint of immobilization of nanoparticles, adhesion, and the like.

  In the case of the conductive nanoparticle dispersion containing a resin, the viscosity is not particularly limited, but is preferably 10,000 mPa · s or less, preferably 5,000 mPa · s or less for applying from a nozzle by electrostatic force. More preferably 1,000 mPa · s or less. In the present specification, the viscosity refers to a value measured at 25 ° C. using a rotational viscometer by the method described in JIS K 7117-1: 1999.

[Application]
The apparatus used to apply the conductive nanoparticle dispersion is to apply the conductive nanoparticle dispersion by electrostatic force. The conductive nanoparticle dispersion is sucked from the nozzle and applied by applying a voltage to the conductive nanoparticle dispersion. As an apparatus, what is mentioned, for example in Unexamined-Japanese-Patent No. 2009-016490 and 2014-120490 can be used.

  The shape of the nozzle is not particularly limited, but in order to uniformly apply a voltage to the conductive nanoparticle dispersion, it is preferably circular.

  The diameter of the nozzle is not particularly limited, but is preferably 1 μm to 300 μm, more preferably 3 μm to 200 μm, and still more preferably 5 μm to 100 μm in order to form a bump of 1 μm or more and less than 100 μm. Within this range, bumps of 1 μm to 100 μm can be easily applied.

  The voltage to be applied is not particularly limited, but is preferably 1,000 V to 10,000 V, more preferably 1,500 V to 8,000 V, and still more preferably 2,000 V to 5,000 V. The distance between the tip of the nozzle and the above-mentioned peelable substrate is, for example, 10 μm to 3,000 μm, preferably 20 μm to 2,000 μm.

[Step (3)]
The step (3) is a step of forming a covering layer on the base layer by coating a composition containing an insulating resin so as to cover the surface of the bump.

  In addition to the insulating resin contained in the above-mentioned coating layer, an arbitrary component can be mix | blended with the composition containing insulating resin, for example, a solvent etc. can be mix | blended.

  The method for forming the coating layer may be in accordance with a conventionally known method, and for example, a film coater, a heat press or the like can be used. As a film coater, for example, a direct gravure coater, a chamber doctor coater, an offset gravure coater, a roll kiss coater, a reverse kiss coater, a bar coater, a die coater, a reverse roll coater, a slot die, an air doctor coater, a positive rotation roll coater, a blade coater , Knife coater, impregnation coater, MB coater, and MB reverse coater. Also, as described above, the same device as the device for applying the conductive nanoparticle dispersion may be applied by spraying from the nozzle.

[(3) 'process]
(3) The 'process is a process of curing the coating layer. When using a thermoplastic resin for a coating layer, it is not necessary to perform (3) 'process. Although the method for curing is not particularly limited, for example, it can be cured by methods such as UV curing, heat curing, moisture curing and the like.

  Thus, according to the method for producing an anisotropic conductive film of the present invention, a base layer containing an insulating resin is provided on a peelable substrate, and 1 μm to 100 μm on the base layer. A bump, which is a conductive nanoparticle aggregate, is arranged at intervals, and a covering layer containing an insulating resin is formed on a base layer so as to cover the bump, and a peelable substrate is a base An anisotropic conductive film having releasability for a layer can be easily produced.

  Hereinafter, the present invention will be described in more detail by way of synthesis examples, examples and comparative examples, but the present invention is not limited to the following examples.

  In the following examples, the weight average molecular weight is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance under the following conditions. In the following synthesis examples, Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group.

[Measurement condition]
Developing solvent: THF (tetrahydrofuran)
Flow rate: 0.6 mL / min
Detector: Differential Refractive Index Detector (RI)
Column: TSK Guardcolomn SuperH-L
TSKgel SuperH4000 (6.0 mm ID × 15 cm × 1)
TSKgel Super H 3000 (6.0 mm ID × 15 cm × 1)
TSKgel Super H 2000 (6.0 mm ID × 15 cm × 2)
(All are made by Tosoh Corporation)
Column temperature: 40 ° C
Sample injection volume: 20 μL (THF solution with a concentration of 0.5% by weight)

Synthesis Example 1
Synthesis of alkenyl group-containing organopolysiloxane 1142.1 g (87.1 mol%) of phenyltrichlorosilane, 529 g (3.2 mol%) of ClMe ₂ SiO (Me ₂ SiO) ₃₃ SiMe ₂ Cl, and 72.4 g (9 of dimethylvinylchlorosilane .7 mol%) is dissolved in toluene solvent, dropped into water, cohydrolyzed, co-hydrolyzed, washed with water, neutralized with alkali washing, dewatered, stripped of solvent, and phenyl group-containing vinyl silicone solid at 25 ° C. Resin A1 was obtained. The weight average molecular weight was 63,000.

Synthesis Example 2
Synthesis of organohydrogenpolysiloxane 1142.1 g (87.1 mol%) of phenyltrichlorosilane, 529 g (3.2 mol%) of ClMe ₂ SiO (Me ₂ SiO) ₃₃ SiMe ₂ Cl, and 69 g (9.7 mol%) of methyldichlorosilane ) Is dissolved in toluene solvent, then added dropwise to water, cohydrolyzed, washed with water, neutralized with alkali washing and dewatered, stripped of solvent, and solid phenyl group-containing hydrogen silicone resin B1 at 25 ° C. I got The weight average molecular weight was 58,000.

Preparation of Conductive Nanoparticle Dispersion [Preparation Example 1]
Silver nano ink (Sigma-Aldrich, concentration: 30 wt%, median diameter: 70 nm) 10 g, vinyl silicone resin A1 synthesized in Synthesis Example 1 1 g, Hydrogen silicone resin B1 synthesized in Synthesis Example 2 1 g, platinum ( 0) A mixture of 2 mg of 1,3-divinyltetramethyldisiloxane complex (platinum concentration: 1% by mass), 6 mg of ethynylcyclohexanol and 1 g of toluene is obtained to obtain a silver nanoparticle dispersion (23 wt%, viscosity: 200 mPa · s) The

Preparation Example 2
Silver nanoparticle dispersion liquid NAG-25T (Daken Chemical Industry Co., Ltd., concentration: 50 wt%, median diameter: 30 nm) 10 g, vinyl silicone resin A1 synthesized in Synthesis Example 1 1 g, Hydrogen silicone synthesized in Synthesis Example 2 1 g of resin B1, 2 mg of platinum (0) -1,3-divinyl tetramethyldisiloxane complex (platinum concentration 1 mass%), 6 mg of ethynyl cyclohexanol were mixed, and a silver nanoparticle dispersion (42 wt%, viscosity: 600 mPa · s) got.

Preparation Example 3
10 g of a silver nanoparticle aqueous dispersion NAG-28 (Daken Chemical Industry Co., Ltd., concentration: 25 wt%, median diameter: 30 nm) is concentrated under reduced pressure, and a silver nanoparticle dispersion (80 wt%, viscosity: 2,000 mPa · s) I got

Adjustment Example 4
240 g of terpineol was added to 10 g of silver nanoparticle aqueous dispersion NAG-28 (Daken Chemical Industry Co., Ltd., concentration: 25 wt%, median diameter: 30 nm), and a silver nanoparticle dispersion (1 wt%, viscosity: 3 mPa · s) Obtained.

[Comparative Preparation Example 1]
10 g of the vinyl silicone resin A1 synthesized in Synthesis Example 1 and 10 g of the hydrogen silicone resin B1 synthesized in Synthesis Example 2 platinum (0) -1,3-divinyl tetramethyl disiloxane complex (platinum concentration: 1% by mass) 0 0.2 g of ethynyl cyclohexanol, 5 g of toluene, and 10 g of silver nanoparticles (made by As One Corp., median diameter: 30 nm) were mixed to obtain a silver nanoparticle paste (29 wt%).

[Comparative Preparation Example 2]
10 g of the vinyl silicone resin A1 synthesized in Synthesis Example 1 and 10 g of the hydrogen silicone resin B1 synthesized in Synthesis Example 2 platinum (0) -1,3-divinyl tetramethyl disiloxane complex (platinum concentration: 1% by mass) 0 .02 g, ethynyl cyclohexanol 0.06 g, and 50 g of silver nanoparticles (manufactured by As One Corp., median diameter: 30 nm) were mixed to obtain a silver nanoparticle paste (71 wt%).

Production of Anisotropic Conductive Film [Example 1]
100 g of the vinyl silicone resin A1 synthesized in Synthesis Example 1, 100 g of the hydrogen silicone resin B1 synthesized in Synthesis Example 2, platinum (0) -1,3-divinyl tetramethyl disiloxane complex (platinum concentration: 1% by mass) 0 .2 g, ethynyl cyclohexanol 0.6 g and toluene 50 g were mixed to prepare organopolysiloxane composition 1. As shown in FIG. 1, an organopolysiloxane composition 1 is applied onto an ETFE (ethylene-tetrafluoroethylene) film (peelable substrate 1) using an automatic coating apparatus PI-1210 (manufactured by Tester Sangyo Co., Ltd.). And formed into a film having a length of 150 mm × width 150 mm and a thickness of 15 μm. Then, the toluene was volatilized by heating at 100 ° C. for 30 minutes to form a base layer 2 having a glass transition point of 40 ° C. and a solid state at 25 ° C., 150 mm long × 150 mm wide and 10 μm thick. Next, the silver nanoparticle dispersion prepared in Preparation Example 1 was coated on the base layer 2 using an electrostatic spray / coating experimental machine (manufactured by Apic Yamada) (nozzle diameter: 25 μm, applied voltage: 2) , 000 V, distance to base layer: 20 μm) (see FIG. 2). The average diameter of the bump 3 which is a silver nanoparticle assembly was 20 μm, and the average interval was 40 μm (see FIG. 4). Next, as shown in FIG. 3, the same organopolysiloxane composition 1 as the base layer 2 is applied as the coating layer 4 of the bumps using the automatic coating apparatus PI-1210, and the toluene is volatilized by heating. The covering layer 4 of 150 mm long × 150 mm wide and 30 μm thick was formed, and an anisotropic conductive film 6 was obtained.

Example 2
A 5 μm thick base layer 2 is prepared in the same manner as in Example 1, and the silver nanoparticle dispersion prepared in Preparation Example 2 is coated on the base layer 2 using an electrostatic spray / coating test machine. (Nozzle diameter: 15 μm, applied voltage: 4,000 V, distance to base layer: 100 μm). The average diameter of the bumps 3 was 10 μm, and the average spacing was 30 μm (see FIG. 5). Then, in the same manner as in Example 1, a covering layer 4 150 mm long × 150 mm wide and 30 μm thick was formed, and an anisotropic conductive film 6 was obtained.

[Example 3]
A 25 μm thick base layer 2 was prepared in the same manner as in Example 1, and the silver nanoparticle dispersion prepared in Preparation Example 3 was coated on the base layer 2 using an electrostatic spray / coating test machine. (Nozzle diameter: 40 μm, applied voltage: 5,000 V, distance to base layer: 100 μm). The average diameter of the bumps 3 was 30 μm, and the average spacing was 30 μm (see FIG. 6). Then, in the same manner as in Example 1, a covering layer 4 150 mm long × 150 mm wide and 50 μm thick was formed, and an anisotropic conductive film 6 was obtained.

Example 4
A base layer 2 having a thickness of 20 μm and a glass transition temperature of 100 ° C. was produced in the same manner as in Example 1 except that the epoxy resin HB-EP100CL (made by HUCKLEBORN) was used as the base layer 2, and electrostatic spraying / coating was performed. The silver nanoparticle dispersion prepared in Preparation Example 3 was coated on the base layer 2 (nozzle diameter: 70 μm, applied voltage: 3,000 V, distance to the base layer: 200 μm) using an experimental machine. The average diameter of the bumps 3 was 100 μm, and the average interval was 90 μm (see FIG. 7). Then, a coating layer 4 150 mm long × 150 mm wide and 150 μm thick was formed in the same manner as in Example 1 except that the coating layer 4 was used as the HB-EP100CL, and an anisotropic conductive film 6 was obtained.

[Example 5]
A base layer 2 having a thickness of 3 μm and a glass transition temperature of 270 ° C. was produced in the same manner as in Example 1 except that polyimide resin UPIA-AT (manufactured by Ube Industries, Ltd.) was used as the base layer 2. The silver nanoparticle dispersion prepared in Preparation Example 4 was coated on the base layer 2 using a coating experiment machine (nozzle diameter: 10 μm, applied voltage: 5,000 V, distance to the base layer: 10 μm) . The average diameter of the bumps 3 was 4 μm, and the average interval was 3 μm (see FIG. 8). Then, a coating layer 4 150 mm long × 150 mm wide and 10 μm thick was formed in the same manner as in Example 1 except that UPIA-AT was used as the coating layer 4, to obtain an anisotropic conductive film 6.

Comparative Example 1
The silver nanopaste produced in Comparative Preparation Example 1 was applied onto an ETFE film using an automatic coating apparatus PI-1210, and formed into a film having a length of 150 mm × width 150 mm and a thickness of 30 μm. Then, toluene was volatilized by heating at 100 ° C. for 30 minutes to obtain an anisotropic conductive film having a length of 150 mm × width 150 mm and a thickness of 25 μm.

Comparative Example 2
A mold with a 50 μm thick grid-like array pattern with wide and narrow intervals between adjacent arrays is prepared, and pellets of a known transparent resin are melted and poured into the mold, and then cooled and solidified. The resin mold of the grid | lattice-like array pattern which has a concave part wide and narrow was formed. The silver nanopaste prepared in Comparative Preparation Example 2 is filled in the concave portion of this resin mold, an ETFE film is covered thereon, and it is formed into a film having 150 mm long × 150 mm wide and 50 μm thickness, and an anisotropic conductive film I got

Comparative Example 3
A 20 μm thick base layer was prepared in the same manner as in Example 1, and the silver nanoparticle dispersion prepared in Preparation Example 3 was applied onto the base layer using an electrostatic spray / coating experiment machine ( Nozzle diameter: 70 μm, applied voltage: 5,000 V, distance to base layer: 500 μm). The average diameter of the bumps was 100 μm, and the average spacing was 200 μm. Then, in the same manner as in Example 1, a covering layer 150 mm long × 150 mm wide and 150 μm thick was formed to obtain an anisotropic conductive film.

Comparative Example 4
A 500 nm thick base layer was prepared in the same manner as in Example 1, and the silver nanoparticle dispersion prepared in Preparation Example 4 was coated on the base layer using an electrostatic spray / coating experimental machine ( Nozzle diameter: 3 μm, applied voltage: 5,000 V, distance to base layer: 1 μm). The average diameter of the bumps was 1 μm, and the average spacing was 700 nm. Then, in the same manner as in Example 1, a covering layer 150 mm long × 150 mm wide and 1 μm thick was formed to obtain an anisotropic conductive film.

Measurement of Average Diameter of Bumps The average diameter of the bumps arranged on the base layer was measured with a semiconductor / FPD inspection microscope MX61 (manufactured by Olympus). The results are shown in Table 1.

Measurement of Average Spacing of Bumps The average spacing of the bumps arranged on the base layer was measured with a semiconductor / FPD inspection microscope MX61 (manufactured by Olympus). The results are shown in Table 1.

After peeling off the release substrate from the films obtained in the current tests of Examples 1 to 5 and Comparative Examples 1 to 4, 50 μm × 50 μm and 20 μm thick micro LEDs are pressed onto the film using pick and place. As shown in the schematic view of the cross section of the film of FIG. 9, the micro LED 5 was pressed against the film. After that, dicing was performed, the substrate was mounted and energized, and the number of lights was measured. The results are shown in Table 1.

  As shown in Table 1, unlike the conventional anisotropic conductive film, the anisotropic conductive film of the present invention ensures conduction without shorting even to a semiconductor device having a fine electrode such as a micro LED. can do.

  On the other hand, in the comparative example 1 and the comparative example 2 which are not the anisotropic conductive film of this invention, electricity supply was not securable. In Comparative Example 3, the average distance between the bumps was too wide, so that it was not possible to secure the energization. In Comparative Example 4, since the average distance between the bumps was too narrow, both the anode and the cathode of the micro LED were in contact and shorted.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has the substantially same constitution as the technical idea described in the claims of the present invention, and the same effects can be exhibited by any invention. It is included in the technical scope of

  DESCRIPTION OF SYMBOLS 1 ... Peelable base material 2 ... Base layer, 3 ... Bump, 4 ... Coating layer, 5 ... Circuit electrode (micro LED), 6 ... Anisotropic conductive film.

The voltage to be applied is not particularly limited, but is preferably 1,000 V to 10,000 V, more preferably 1,500 V to 8,000 V, and still more preferably 2,000 V to 5,000 V. The distance between the tip of the nozzle and the above-mentioned base layer is, for example, 10 μm to 3,000 μm, preferably 20 μm to 2,000 μm.

Claims (9)

An anisotropic conductive film,
A base layer containing an insulating resin is provided on a peelable substrate, and bumps, which are conductive nanoparticle aggregates, are arranged at intervals of 1 μm to 100 μm on the base layer to cover the bumps. As described above, a coating layer containing an insulating resin is formed on the base layer, and the peelable substrate has releasability from the base layer. Anisotropic conductive film.   The average diameter of the said bump is 1 micrometer-100 micrometers, The anisotropic conductive film of Claim 1 characterized by the above-mentioned.   The anisotropic conductive film according to claim 1 or 2, wherein the conductive nanoparticle aggregate is an aggregate consisting of conductive nanoparticles having a primary particle diameter of 1 nm to 500 nm.   The thickness of the said base layer is 1%-100% of the average diameter of the said bump, The anisotropic conductive film as described in any one of the Claims 1-3 characterized by the above-mentioned.   The thickness of the said coating layer is 101%-500% of the average diameter of the said bump, The anisotropic conductive film as described in any one of the Claims 1-4 characterized by the above-mentioned. At least one of the base layer and the covering layer contains a silicone resin as an insulating resin, and contains the following components (A), (B), and (C): The anisotropic conductive film according to any one of claims 1 to 5, wherein
(A) Silicone resin represented by the following average formula (1) R ¹ _a R ² _b R ³ _c (OX) _d SiO _{(4-a-b-c-d) / 2} (1)
Wherein R ¹ is a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, R ² is a saturated hydrocarbon group having 1 to 6 carbon atoms, and R ³ is an alkenyl group having 2 to 6 carbon atoms X is a monovalent hydrocarbon group having 1 to 6 carbon atoms or a hydrogen atom, and a, b, c and d are aa0, b> 0, c> 0 and dd0, respectively. And a + b + c + d = 1 to 2, provided that at least two alkenyl groups are contained in one molecule.
(B) Silicone resin represented by the following average formula (2) R ¹ _e R ² _f H _g (OX) _h SiO _{(4-e-f-g-h) / 2} (2)
(Wherein, R ¹ , R ² and X are the same as the aforementioned R ¹ , R ² and X. e, f, g and h are respectively e ≧ 0, f> 0, g> 0 and h ≧ 0, and e + f + g + h = 1 to 2, provided that at least two hydrogen atoms bonded to silicon atoms are contained in one molecule.
(C) Hydrosilylation catalyst   The anisotropic conductive film according to claim 6, wherein the silicone resin is solid at 25 ° C. It is a manufacturing method of anisotropic conductive film, and
(1) A step of coating a composition containing an insulating resin on a peelable substrate to form a base layer,
(2) A conductive nanoparticle aggregate is applied onto the base layer by applying a voltage to the conductive nanoparticle dispersion and applying the conductive nanoparticle dispersion to the base layer from a nozzle by electrostatic force Forming a coating layer on the base layer by arranging the bumps in the body at intervals of 1 μm to 100 μm, and (3) coating a composition containing an insulating resin to cover the surface of the bumps The process to
A method of producing an anisotropic conductive film, comprising:   Between the step (1) and the step (2), performing the step (1) 'which is a step of curing the base layer, and / or curing the covering layer after the step (3) The method of producing an anisotropic conductive film according to claim 8, wherein the step (3) 'is performed.