JP2021161281A - Anisotropic conductive resin composition and micro-led display device - Google Patents

Abstract

To provide an anisotropic conductive resin composition excellent in optical transparency.SOLUTION: An anisotropic conductive resin composition comprises (A) a silicone-modified epoxy resin, (B) a curative, and (C) conductive particles, where the (A) silicone-modified epoxy resin has a structure represented by the general formula (1) in the figure, where R1, R2, Y, a, b and n are as defined in the specification.SELECTED DRAWING: None

Description

The present invention relates to an anisotropic conductive resin composition and a micro LED display device.

In recent years, so-called micro LEDs using small LEDs (Light Emitting Diodes) have been attracting attention as display elements next to liquid crystal display elements and organic electroluminescence elements. Similar to the organic electroluminescence element, the micro LED is a light emitting element, and an active matrix type display device using the light emitting element is known (Patent Document 1 and Patent Document 2).
In addition, conventionally, as a method of mounting a drive circuit on a display element, a display is performed via an anisotropic conductive film (ACF) (hereinafter, may be referred to as an "alien conductive adhesive"). The extraction electrode portion of the element and the connection terminal on the drive circuit board are electrically connected (Patent Document 3).

WO2019 / 220267A Japanese Unexamined Patent Publication No. 2007-123861 Japanese Unexamined Patent Publication No. 2010-192802

However, when mounting small LED chips used for micro LEDs or repairing them, alignment marks for positioning may be collated. For example, when mounting a small LED chip on a mounting board via an anisotropic conductive adhesive, the positioning is formed on the mounting board in order to mount the small LED chip at a predetermined position on the mounting board with high accuracy. It is necessary to recognize the alignment mark by a camera or the like including an image pickup element. In such a case, in order to avoid recognition errors, an anisotropic conductive adhesive made of an anisotropic conductive resin composition having high optical transmittance and excellent discoloration resistance may be required.

The present invention has been made in view of such circumstances, and an object of the present invention is to provide an anisotropic conductive resin composition having excellent light transmission.

［式（１）中、Ｒ^１はそれぞれ独立に１価の有機基を示し、Ｒ^２はそれぞれ独立に炭素数１〜１０の鎖状の脂肪族炭化水素基、炭素数３〜１０の環状の脂肪族炭化水素基及びフェニル基から選ばれる基を示し、Ｙは環状エーテル基を含有する有機基を示す。Ｘはそれぞれ同一であっても異なってもよい。ａとｂは正の数であってａ＋ｂ＝１かつ０．３≦ａ＜１であり、ｎは１〜２５である。］
（２）前記（Ｃ）導電性粒子が、金属被覆樹脂粒子を含む、上記（１）に記載の異方導電性樹脂組成物。
（３）前記金属被覆樹脂粒子の平均粒径が０．５〜１０μｍである、上記（２）に記載の異方導電性樹脂組成物。
（４）前記金属被覆樹脂粒子が、前記異方導電性樹脂組成物１００質量部に対して、０．１〜５０質量部含有する、上記（２）又は（３）に記載の異方導電性樹脂組成物。
（５）さらに、（Ｄ）無機充填剤を含む、上記（１）〜（４）のいずれかに記載の異方導電性樹脂組成物。
（６）前記（Ｄ）無機充填剤の平均粒径が１〜５００ｎｍである、上記（５）に記載の異方導電性樹脂組成物。
（７）前記（Ｄ）無機充填剤が、前記異方導電性樹脂組成物１００質量部に対して、０．３〜２．５質量部含有する、上記（５）又は（６）に記載の異方導電性樹脂組成物。
（８）上記（１）〜（７）のいずれかに記載の異方導電性樹脂組成物を用いて、基板上にマイクロＬＥＤをアレイ状に並べて実装してなる、マイクロＬＥＤディスプレイ装置。 As a result of diligent studies to solve the above problems, the present inventors have found, for example, an anisotropic conductive resin composition containing a silicone-modified epoxy resin having a specific structure, a curing agent, and conductive particles, for example, a display element. A cured product suitable for an adhesive that easily and accurately connects the electrodes on the substrate and the connection terminals of the drive circuit board, and the electrical connection when mounting a small LED chip or the like. The present invention was completed by finding that
That is, the present invention provides the following (1) to (8).
An anisotropic conductive resin composition containing (1) (A) a silicone-modified epoxy resin, (B) a curing agent, and (C) conductive particles, wherein the (A) silicone-modified epoxy resin is An anisotropic conductive resin composition having a structure represented by the following general formula (1).

[In the formula (1), R ¹ independently represents a monovalent organic group, and R ² is a chain aliphatic hydrocarbon group having 1 to 10 carbon atoms and a cyclic cyclic group having 3 to 10 carbon atoms, respectively. It represents a group selected from an aliphatic hydrocarbon group and a phenyl group, and Y represents an organic group containing a cyclic ether group. X may be the same or different. a and b are positive numbers, a + b = 1 and 0.3 ≦ a <1, and n is 1 to 25. ]
(2) The anisotropic conductive resin composition according to (1) above, wherein the conductive particles (C) contain metal-coated resin particles.
(3) The anisotropic conductive resin composition according to (2) above, wherein the metal-coated resin particles have an average particle size of 0.5 to 10 μm.
(4) The anisotropic conductivity according to (2) or (3) above, wherein the metal-coated resin particles are contained in an amount of 0.1 to 50 parts by mass with respect to 100 parts by mass of the anisotropic conductive resin composition. Resin composition.
(5) The anisotropic conductive resin composition according to any one of (1) to (4) above, further comprising (D) an inorganic filler.
(6) The anisotropic conductive resin composition according to (5) above, wherein the average particle size of the inorganic filler (D) is 1 to 500 nm.
(7) The above-mentioned (5) or (6), wherein the inorganic filler (D) is contained in an amount of 0.3 to 2.5 parts by mass with respect to 100 parts by mass of the anisotropic conductive resin composition. An anisotropic conductive resin composition.
(8) A micro LED display device in which micro LEDs are arranged and mounted on a substrate in an array using the anisotropic conductive resin composition according to any one of (1) to (7) above.

According to the present invention, it is possible to provide an anisotropic conductive resin composition having excellent light transmission.

［式（１）中、Ｒ^１はそれぞれ独立に１価の有機基を示し、Ｒ^２はそれぞれ独立に炭素数１〜１０の鎖状の脂肪族炭化水素基、炭素数３〜１０の環状の脂肪族炭化水素基及びフェニル基から選ばれる基を示し、Ｙは環状エーテル基を含有する有機基を示す。Ｘはそれぞれ同一であっても異なってもよい。ａとｂは正の数であってａ＋ｂ＝１かつ０．３≦ａ＜１であり、ｎは１〜２５である。］ [Anteroconductive resin composition]
The anisotropic conductive resin composition of the present invention is an anisotropic conductive resin composition containing (A) a silicone-modified epoxy resin, (B) a curing agent, and (C) conductive particles. The silicone-modified epoxy resin (A) is characterized by having a structure represented by the following general formula (1).

[In the formula (1), R ¹ independently represents a monovalent organic group, and R ² is a chain aliphatic hydrocarbon group having 1 to 10 carbon atoms and a cyclic cyclic group having 3 to 10 carbon atoms, respectively. It represents a group selected from an aliphatic hydrocarbon group and a phenyl group, and Y represents an organic group containing a cyclic ether group. X may be the same or different. a and b are positive numbers, a + b = 1 and 0.3 ≦ a <1, and n is 1 to 25. ]

[(A) Silicone modified epoxy resin]
The anisotropic conductive resin composition of the present invention contains a silicone-modified epoxy resin having a structure represented by the following general formula (1) as an essential component.

In the formula (1), R ¹ independently represents a monovalent organic group, and R ² is a chain aliphatic hydrocarbon group having 1 to 10 carbon atoms and a cyclic fat having 3 to 10 carbon atoms, respectively. A group selected from a group hydrocarbon group and a phenyl group is shown, and Y represents an organic group containing a cyclic ether group. X may be the same or different. a and b are positive numbers, a + b = 1 and 0.3 ≦ a <1, and n is 1 to 25.
Examples ^{of the monovalent organic group of R 1} include a monovalent organic group having a hydroxy group, a linear or branched alkyl group, an alkoxy group, an aryl group and the like.
As the chain aliphatic hydrocarbon group having 1 to 10 carbon atoms R ^2, a methyl group, an ethyl group, a propyl group, n- butyl group, n- pentyl group, or n- hexyl group and the like to.
The cyclic aliphatic hydrocarbon group of carbon number 3 to 10 R ^2, cyclopropyl group, Shikuropuchiru group, a cyclopentyl group, a cyclohexyl group, or cyclooctyl group, and the like.
Examples of the organic group containing a cyclic ether group of Y include a cyclic ether group having a structure of a 3- to 6-membered ring, and a 3-membered or 4-membered ring cyclic ether group having a particularly large ring strain energy and high reactivity. Is preferable, and a 3-membered ring ether group is more preferable. A glycidoxyalkyl group in which an oxyglycidyl group is bonded to an alkyl group having 1 to 3 carbon atoms such as a β-glycidoxyethyl group, a γ-glycidoxypropyl group, and a β- (3,4-epoxycyclohexyl) ethyl group. , An alkyl group having 3 or less carbon atoms substituted with a cycloalkyl group having 5 to 8 carbon atoms having an oxylane group is preferable.

In the present embodiment, the silicone-modified epoxy resin is preferably 30 to 80 parts by mass, more preferably 40 to 70 parts by mass, and 45 parts by mass with respect to 100 parts by mass of the total mass of the anisotropic conductive resin composition. It is more preferably ~ 60 parts by mass.
When the mass portion of the silicone-modified epoxy resin is in this range, it becomes easy to have heat resistance, light resistance, and migration resistance.
The silicone-modified epoxy resin is described in, for example, Japanese Patent Application Laid-Open No. 2012-241136.

[(B) Hardener]
The anisotropic conductive resin composition of the present invention contains (B) a curing agent as an essential component.
As the curing agent (B), since the silicone-modified epoxy resin (A) has an epoxy group, for example, an amine-based curing agent and an acid anhydride curing agent that are generally used in thermosetting can be mentioned. Among these, it is preferable to use an acid anhydride curing agent from the viewpoint of light transmission, heat resistance and the like.
Examples of the acid anhydride curing agent include succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, and 4-methyl-. Hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, nadicic anhydride, methylnadic anhydride, norbornan-2,3-dicarboxylic acid anhydride, methylnorbornan-2,3-dicarboxylic acid anhydride and methyl Cyclohexendicarboxylic acid anhydride and the like can be mentioned. Among these, 4-methyl-hexahydrophthalic anhydride, tetrahydrophthalic anhydride, nadicic anhydride, or methylcyclohexene dicarboxylic acid anhydride are preferable from the viewpoint of light transmission.
These can be used alone or in combination of two or more.

In the present embodiment, the curing agent is preferably 4 to 70 parts by mass with respect to 100 parts by mass of the total mass of the anisotropic conductive resin composition from the viewpoint of obtaining good curability and cured product properties. , More preferably 10 to 50 parts by mass, and even more preferably 15 to 35 parts by mass.

Further, a curing accelerator and a curing catalyst effective for the reaction with the curing agent can be used in combination.
Examples of the curing accelerator include organic phosphorus compounds such as triphenylphosphine and tributylphosphine; ethyltriphenylphosphine bromide, diethyl methyltriphenylphosphonium phosphate, tetra-n-butylphosphonium-O, O'-diethyl. Tertiary phosphineium salts such as phosphorodithionates; 1,8-diazabicyclo (5,4,0) undecane-7-ene, 1,8-diazabicyclo (5,4,0) undecane-7-ene and octylic acid. Salts, quaternary ammonium salts such as zinc octylate, tetrabutylammonium bromide and the like. Of these, tetra-n-butylphosphonium-O, O'-diethylphosphologithionate, and 4-hydroxy2 (triphenylphosphonium) phenolato are preferable from the viewpoint of adhesion.
These can be used alone or in combination of two or more.

Examples of the curing catalyst include organic phosphine-based curing catalysts such as triphenylphosphine and diphenylphosphine; 1,8-diazabicyclo (5,4,0) undecene-7, triethanolamine, benzyldimethylamine and the like. Secondary amine-based curing catalysts; imidazoles such as 2-methylimidazole and 2-phenyl-4-methylimidazole can be mentioned.
These can be used alone or in combination of two or more.

Further, a thermocation curing catalyst or a photocationic curing catalyst can be added to perform thermosetting and photocuring.
Examples of the thermal cation curing catalyst include benzylsulfonium salt, thiophenium salt, thiolanium salt, benzylammonium, pyridinium salt, hydrazinium salt, carboxylic acid ester, sulfonic acid ester and amineimide.
These can be used alone or in combination of two or more.
Examples of the photocationic curing catalyst include a sulfonium salt type and an iodonium salt type. Examples of the sulfonium salt system include, for example, triphenylsulfonium hexafluorophosphate and triphenylsulfonium hexafluoroantimonate, and examples of the iodonium salt system include, for example, diphenyliodonium tetrakis (pentafluorophenyl) borate and diphenyliodonium. Hexafluorophosphate and the like can be mentioned.
These can be used alone or in combination of two or more.

[(C) Conductive particles]
The anisotropic conductive resin composition of the present invention contains (C) conductive particles as an essential component.
Examples of the conductive particles (C) include metals and carbon. Examples of the metal include transition metals such as nickel (Ni) and copper (Cu); precious metals such as gold (Au), silver (Ag) and platinum group metals; and alloys such as solder.
The conductive particles are preferably coated particles in which core particles are coated with the above metal or carbon.
The outermost layer of the conductive particles preferably contains a noble metal such as Au, Ag, or a platinum group metal, and more preferably Au, from the viewpoint that a sufficient pot life can be easily obtained.
The conductive particles may be, for example, those in which a transition metal such as Ni is used as a core and the surface thereof is coated with a noble metal such as Au. The conductive layer of the metal or the like may be formed by coating or the like. The conductive layer may be a single layer or a plurality of layers, but the outermost layer is preferably a noble metal layer.

Since the coated particles (for example, conductive particles having a plastic as a core) or the heat-melted metal particles can impart deformability due to heating and pressurization, it is possible to eliminate variations in the height of circuit electrodes and the like at the time of connection. It is easy to increase the contact area with the circuit electrodes and the like, which is considered to further improve the reliability.

When the outermost layer of the conductive particles is a noble metal layer, the thickness of the noble metal layer is usually 10 nm or more from the viewpoint of easily sufficiently reducing the resistance between the connected circuits. However, when the noble metal layer is provided on the transition metal such as Ni, for example, the transition metal such as Ni is an heterogeneous conductive resin composition due to the loss of the noble metal layer at the time of mixing and dispersing the conductive particles. Free radicals may be generated due to the oxidation-reduction action of the transition metal, which may reduce the storage stability of the heteroconductive resin composition. Therefore, the thickness of the noble metal layer is preferably 30 nm or more, more preferably 60 nm or more, and further preferably 100 nm or more.
The upper limit of the thickness of the noble metal layer is not particularly limited, but is usually 1 μm or less from the viewpoint of manufacturing cost.

The average particle size of the conductive particles is preferably 0.5 μm or more, more preferably 1 μm or more, from the viewpoint that it is easy to cope with variations in the height of the circuit electrodes and the conductivity between the circuit electrodes is unlikely to decrease. The average particle size of the conductive particles is preferably 10 μm or less, more preferably 5 μm or less, from the viewpoint that the insulation between adjacent circuit electrodes is unlikely to decrease. From these viewpoints, the average particle size of the conductive particles is preferably 0.5 to 10 μm, more preferably 1 to 5 μm, and even more preferably 1.5 to 4.5 μm.
The average particle size of the conductive particles can be measured by observing any 100 conductive particles with a microscope.

The content of the conductive particles is preferably 0.1 part by mass or more with respect to 100 parts by mass of the total mass of the anisotropic conductive resin composition from the viewpoint of excellent conductivity. The content of the conductive particles is preferably 50 parts by mass or less, more preferably 40 parts by mass, based on 100 parts by mass of the total mass of the anisotropic conductive resin composition from the viewpoint of easily suppressing a short circuit of an adjacent circuit. It is as follows. From these viewpoints, the content of the conductive particles is preferably 0.1 to 50 parts by mass, more preferably 0.1 to 40 parts by mass, based on 100 parts by mass of the total mass of the anisotropic conductive resin composition. It is by mass, more preferably 0.1 to 30 parts by mass.
The conductive particles are dispersed in the anisotropic conductive composition at a density capable of exerting a function as an anisotropic conductive adhesive after the anisotropic conductive resin composition is pressurized and heated. There is. Specifically, the conductive particles occupy preferably 15 to 60%, more preferably 25 to 60% per horizontal projected area. The number of particles per unit area largely depends on the average particle size, but from the viewpoint of conductivity, it is preferably 10,000 to 100,000 particles / mm ² , and more preferably 20,000 to 70,000. ^{The number is 2} mm / mm 2, and more preferably 30,000 to 60,000 pieces / mm ^2.

[(D) Inorganic filler]
The anisotropic conductive resin composition of the present invention preferably further contains (D) an inorganic filler.
Examples of the inorganic filler include metal carbides, metal oxides, silica particles, carbon particles, metal carbonate particles, metal nitride particles, metal hydroxide particles, metal sulfate particles, barium titanate particles, and the like. And so on. Among these, silica particles are preferable from the viewpoint of suppressing a decrease in light transmission and a decrease in a coefficient of thermal expansion. Examples of the silica particles include various types of silica used in the art such as amorphous silica, crystalline silica, molten silica, amorphous fused silica, pulverized silica, and nanosilica, and amorphous fused silica is preferable.
These can be used alone or in combination of two or more.

The average particle size of the inorganic filler (D) is preferably 1 to 500 nm, more preferably 5 to 300 nm, and even more preferably 10 to 200 nm from the viewpoint of not reducing the light transmittance.
The content of the inorganic filler (D) is preferably 0.3 to 2.5 parts by mass with respect to 100 parts by mass of the anisotropic conductive resin composition from the viewpoint of maintaining the shape of the anisotropic conductive resin composition. Yes, more preferably 0.5 to 2.0 parts by mass, and even more preferably 0.7 to 1.7 parts by mass.
Unless otherwise specified, the average particle size of the inorganic filler is a particle size corresponding to a cumulative frequency of 50% by volume from the smaller particle size side in the volume-based particle size distribution based on the laser diffraction / light scattering method (D50, Also called the median diameter).

(Other ingredients)
A coupling agent may be added to the anisotropic conductive resin composition of the present invention. The coupling agent is not particularly limited as long as it is a known coupling agent blended in this type of resin composition, and examples thereof include a silane coupling agent and a titanate-based coupling agent. Examples of the silane coupling agent usually include epoxysilane-based, aminosilane-based, cationicsilane-based, vinylsilane-based, acrylicsilane-based, mercaptosilane-based, and composite systems thereof, and can be used in any addition amount. .. Further, as the titanate-based coupling agent, usually, a titanate-based coupling agent having an alkylate group having at least 1 to 60 carbon atoms, a titanate-based coupling agent having an alkylphosphite group, and a titanate-based cup having an alkylphosphate group. Examples thereof include a ring agent or a titanate-based coupling agent having an alkylpyrophosphate group, and a composite coupling agent thereof, which can be used in any addition amount.
The blending amount of the coupling agent is typically 5% by mass or less with respect to 100% by mass of the anisotropic conductive resin composition.

Further, additives such as an antioxidant, a mold release agent, and an ion scavenger may be added to the anisotropic conductive resin composition of the present invention, if necessary.

[Manufacturing method of anisotropic conductive resin composition]
The anisotropic conductive resin composition of the present invention can be produced by applying a known method.
For example, a known kneader such as a pot mill, a ball mill, a bead mill, a roll mill, a homogenizer, a super mill, or a raikai machine is used to mix the components (A) to (C) and various components arbitrarily blended as needed. After kneading at room temperature or under heating, the solvent can be diluted if necessary to obtain an anisotropic conductive resin composition.

[Manufacturing method of micro LED array display device]
The method for manufacturing the micro LED array display device of the present invention is to apply the anisotropic conductive resin composition on a substrate by a known means such as a printing method or a dispensing method, and then mount the micro LEDs at predetermined intervals. It is obtained by arranging micro LEDs in an array and bonding them to a substrate by heat curing for 0.1 to 2 hours under the conditions of 150 to 200 ° C. and 1 to 10 MPa.
The array shape means, for example, arranging the micro LEDs in M rows and N columns, although not particularly limited. However, here, M and N are integers, and at least one of M and N is 2 or more.

Next, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these examples.

[Synthesis Example 1]
(A1) Synthesis of silicone-modified epoxy resin Hydrogen polydimethylsiloxane [trade name: DMS-H03, Gelest, Inc.] in a 500 ml 4-port separable flask equipped with a thermometer, a cooling tube, a nitrogen introduction tube, and a stirring blade. .. 85.0 parts by mass and 100 parts by mass of toluene were added, and the mixture was stirred at room temperature. Platinum divinyltetramethyldisiloxane complex xylene solution [trade name: SIP6831.2, Gelest, Inc. ] Was added in an amount of 0.075 parts by mass and heated to 60 ° C. using a mantle heater. 53.1 parts by mass of monoallyl glycidyl isocyanuric acid [trade name: MADGIC, manufactured by Shikoku Chemicals Corporation] was added thereto and dissolved. Then, the temperature was raised to 110 ° C., and the mixture was stirred as it was for 4 hours.
Next, 11.9 parts by mass of liquid polybutadiene [trade name: NISSO PB G-1000, manufactured by Nippon Soda Corporation] dissolved in 50 parts by mass of toluene was added dropwise to the reaction solution over 30 minutes, and further at 110 ° C. 4 Stirred for hours. The solvent of the obtained reaction mixture was distilled off under reduced pressure to obtain a silicone-modified epoxy resin.

[Synthesis Example 2]
(A2) Synthesis of Silicone Modified Epoxy Resin In a flask similar to that used in Synthesis Example 1, 123 parts by mass of epoxidized polybutadiene [epoxy equivalent 203 g / eq, double bond equivalent 83 g / eq, number average molecular weight 1000], 200 parts by mass of toluene was added to dissolve the epoxidized polybutadiene. Platinum divinyltetramethyldisiloxane complex xylene solution [trade name: SIP6831.2, Gelest, Inc. ] Was added in an amount of 0.033 parts by mass and heated to 60 ° C. using a mantle heater. Hydrogenpolydimethylsiloxane dissolved therein in 70 parts by mass of toluene [trade name: DMS-H03, Gelest, Inc. 6 parts by mass was added dropwise to the reaction solution over 30 minutes, and the mixture was further stirred at 110 ° C. for 4 hours. The solvent of the obtained reaction mixture was distilled off under reduced pressure to obtain a silicone-modified epoxy resin.

(Examples 1 and 2, Comparative Examples 1 to 4)
Each component was mixed at the compounding ratio shown in Table 1 to obtain an anisotropic conductive resin composition. The obtained anisotropic conductive resin composition was evaluated by the method described later. The results are also shown in Table 1. The materials used in Examples and Comparative Examples had the following characteristics.

(A1) Silicone-modified epoxy resin: Synthesis Example 1
(A2) Silicone-modified epoxy resin: Synthesis Example 2
Other resins / silicone resins (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KER-3000-M2)
-Epoxy resin with isocyanuric acid structure (manufactured by Nissan Chemical Industries, Ltd., trade name: TEPIC-FL)

(B) Hardener (B1) 4-Methyl-Hexahydrophthalic anhydride (manufactured by Shin Nihon Rika Co., Ltd., trade name: Ricacid MH)
・ (B2) Isocyanate-based curing agent (manufactured by Tosoh, trade name: Coronate HX)

-Curing accelerator: tetra-n-butylphosphonium-O, O'-diethylphosphologithionate (manufactured by Nippon Chemical Industrial Co., Ltd., trade name: PX-4ET)

(C) Conductive particles / gold-plated resin particles (manufactured by Sekisui Chemical Co., Ltd., trade name: Micropearl AU, average particle size: 5 μm)

(D) Inorganic filler / amorphous fused silica (manufactured by Nippon Aerosil Co., Ltd., trade name: R972, average particle size: 15 nm)
For the average particle size of the (D) inorganic filler, the median size was measured by a laser diffraction / scattering method using a laser diffraction / scattering type particle size distribution measuring device (manufactured by HORIBA, Ltd., product name: LA-920). Was taken as the average particle size.

Other ingredients ・ Silane coupling agent (manufactured by Shinetsu Silicone Co., Ltd., trade name: KBM-303)

<Evaluation method>
(1) Adhesiveness An anisotropic conductive resin composition is applied to a print evaluation substrate, an LED of 50 μm × 50 μm is further mounted, and after heating at 200 ° C. for 1 hour to join, an adhesive strength measuring device (Nishishin Shoji Co., Ltd.) The adhesive strength in the environment of 25 ° C. and 260 ° C. was measured using the product, model name: SS-30WD), and the rate of change (decrease rate) of the adhesive strength at 260 ° C. with respect to the adhesive strength at 25 ° C. was calculated. .. The evaluation criteria are as follows.
[Evaluation criteria]
◯: Less than 10% Δ: 10% or more and less than 20% ×: 20% or more

(2) Initial transmission rate A cell produced by sandwiching a 0.5 mm thick silicone rubber sheet as a spacer between two 1 mm thick glass plates (manufactured by Matsunami Glass Co., Ltd., product name: S1112) facing each other. The heteroconductive resin composition is poured into the glass, heated at 120 ° C. for 2 hours, then heated to 150 ° C., and then further heated for 5 hours to cure the resin composition to a thickness of 0.5 mm. A plate-shaped cured product was prepared.
Using an ultraviolet-visible spectrophotometer (manufactured by JASCO Corporation, product name: V-570), the light transmittance of the plate-shaped cured product after heat curing was measured at a wavelength of 460 nm. The evaluation criteria are as follows.
[Evaluation criteria]
◯: 90% or more Δ: 80% or more and less than 90% ×: less than 80%

(3) Heat resistance test (1)
The heat-cured plate-shaped cured product obtained in (2) above was heat-treated in an air oven at 150 ° C. for 24 hours. In addition, the light transmittance of the plate-shaped cured product after this heat treatment at 460 nm was measured, and the rate of change was calculated. The evaluation criteria are as follows.
[Evaluation criteria]
◯: 90% or more Δ: 80% or more and less than 90% ×: less than 80%

(4) Heat resistance test (2)
The heat-cured plate-shaped cured product obtained in (2) above was heat-treated in an air oven at 150 ° C. for 1000 hours. In addition, the light transmittance of the plate-shaped cured product after this heat treatment at 460 nm was measured, and the rate of change was calculated. The evaluation criteria are as follows.
[Evaluation criteria]
◯: 90% or more Δ: 80% or more and less than 90% ×: less than 80%

(5) Light resistance test (1)
For the plate-shaped cured product obtained in (2) above, a UV irradiation device (manufactured by ORC Manufacturing Co., Ltd., product name: UV-300, high-pressure mercury lamp, wavelength cut filter of 400 nm or less is used) for 24 hours. UV irradiation treatment was performed. In addition, the light transmittance of the plate-shaped cured product after this irradiation treatment at 460 nm was measured, and the rate of change was calculated. The evaluation criteria are as follows.
[Evaluation criteria]
◯: 90% or more Δ: 80% or more and less than 90% ×: less than 80%

(6) Light resistance test (2)
The plate-shaped cured product obtained in (2) above was subjected to a UV irradiation device (manufactured by ORC Manufacturing Co., Ltd., product name: UV-300, high-pressure mercury lamp, wavelength cut filter of 400 nm or less) for 1000 hours. UV irradiation treatment was performed. Next, the light transmittance of the plate-shaped cured product after the irradiation treatment at 460 nm was measured, and the rate of change was calculated. The evaluation criteria are as follows.
[Evaluation criteria]
◯: 90% or more Δ: 80% or more and less than 90% ×: less than 80%

(7) Migration resistance The anisotropic conductive resin composition obtained in the example was applied to a comb-shaped pattern substrate (board material: aluminum nitride, electrode material: Cu, 5 pieces at 0.1 mm intervals), and the temperature was 200 ° C. A migration test was performed on a sample (50 x 50 mm, thickness: 0.1 mm) thermoset at 1 MPa for 60 minutes by applying a voltage of 100 V to the electrodes for 1000 hours in an environment of 85 ° C. and 85% humidity RH. By doing so, the migration resistance was evaluated. The evaluation criteria are as follows.
[Evaluation criteria]
○: No migration occurred ×: Migration occurred

Examples 1 and 2 using a silicone modified epoxy resin as the main component resin are Comparative Examples 1 and 3 using a silicone resin (poor adhesion and migration resistance) and Comparative Example 2 using an epoxy resin. It can be seen that, as compared with 4 (poor light resistance), all of adhesion, light transmission, heat resistance, light resistance and migration resistance are satisfied at the same time.

Claims (8)

An anisotropic conductive resin composition containing (A) a silicone-modified epoxy resin, (B) a curing agent, and (C) conductive particles.
An anisotropic conductive resin composition in which the silicone-modified epoxy resin (A) has a structure represented by the following general formula (1).

[In the formula (1), R ¹ independently represents a monovalent organic group, and R ² is a chain aliphatic hydrocarbon group having 1 to 10 carbon atoms and a cyclic cyclic group having 3 to 10 carbon atoms, respectively. It represents a group selected from an aliphatic hydrocarbon group and a phenyl group, and Y represents an organic group containing a cyclic ether group. X may be the same or different. a and b are positive numbers, a + b = 1 and 0.3 ≦ a <1, and n is 1 to 25. ] The anisotropic conductive resin composition according to claim 1, wherein the conductive particles (C) include metal-coated resin particles. The anisotropic conductive resin composition according to claim 2, wherein the metal-coated resin particles have an average particle size of 0.5 to 10 μm. The anisotropic conductive resin composition according to claim 2 or 3, wherein the metal-coated resin particles are contained in an amount of 0.1 to 50 parts by mass with respect to 100 parts by mass of the anisotropic conductive resin composition. The anisotropic conductive resin composition according to any one of claims 1 to 4, further comprising (D) an inorganic filler. The anisotropic conductive resin composition according to claim 5, wherein the inorganic filler (D) has an average particle size of 1 to 500 nm. The anisotropic conductive resin composition according to claim 5 or 6, wherein the inorganic filler (D) is contained in an amount of 0.3 to 2.5 parts by mass with respect to 100 parts by mass of the anisotropic conductive resin composition. thing. A micro LED display device in which micro LEDs are arranged and mounted on a substrate in an array using the anisotropic conductive resin composition according to any one of claims 1 to 7.