JP4391836B2 - Coated conductive particles, anisotropic conductive material, and conductive connection structure - Google Patents
Coated conductive particles, anisotropic conductive material, and conductive connection structure Download PDFInfo
- Publication number
- JP4391836B2 JP4391836B2 JP2004010754A JP2004010754A JP4391836B2 JP 4391836 B2 JP4391836 B2 JP 4391836B2 JP 2004010754 A JP2004010754 A JP 2004010754A JP 2004010754 A JP2004010754 A JP 2004010754A JP 4391836 B2 JP4391836 B2 JP 4391836B2
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- Prior art keywords
- particles
- particle
- coated
- hollow
- conductive
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- MSYLJRIXVZCQHW-UHFFFAOYSA-N formaldehyde;6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound O=C.NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 MSYLJRIXVZCQHW-UHFFFAOYSA-N 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- VMPHSYLJUKZBJJ-UHFFFAOYSA-N lauric acid triglyceride Natural products CCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCC)COC(=O)CCCCCCCCCCC VMPHSYLJUKZBJJ-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical group O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
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- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
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- 125000000542 sulfonic acid group Chemical group 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000002463 transducing effect Effects 0.000 description 1
- JRSJRHKJPOJTMS-UHFFFAOYSA-N trimethoxy(2-phenylethenyl)silane Chemical compound CO[Si](OC)(OC)C=CC1=CC=CC=C1 JRSJRHKJPOJTMS-UHFFFAOYSA-N 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
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- 238000007740 vapor deposition Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
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Description
本発明は、基板間の導電接続を確実に行うことができるとともに、隣接する粒子間でのリ
ークを防止することができる被覆導電粒子、該被覆導電粒子を用いてなる異方性導電材料
及び導電接続構造体に関する。
The present invention provides a coated conductive particle capable of reliably performing conductive connection between substrates and preventing leakage between adjacent particles, an anisotropic conductive material using the coated conductive particle, and a conductive film. It relates to a connection structure.
基材粒子の表面の一部を樹脂により被覆した粒子（以下、被覆粒子ともいう）は、基材粒
子に耐熱性、耐磨耗性、絶縁性、導電性、撥水性、接着性、分散性、光沢、着色等の性能
が付与可能であり、種々の充填剤、改質剤としてフィルム、粘着剤、接着剤、塗料等に用
いられている。なかでも、金属表面を有した導電性粒子の表面を絶縁性の樹脂で被覆した
被覆導電粒子を接着剤に分散した異方導電フィルムや異方導電接着剤は、被覆した絶縁樹
脂により隣接する導電粒子間の導通を防ぐことが可能となり、接続信頼性の向上が期待さ
れている。
Particles in which a part of the surface of the base particle is coated with a resin (hereinafter also referred to as coated particle) are heat resistance, wear resistance, insulation, conductivity, water repellency, adhesiveness, dispersibility on the base particle. Further, it is possible to impart performance such as gloss and coloring, and it is used as various fillers and modifiers for films, pressure-sensitive adhesives, adhesives, paints and the like. In particular, anisotropic conductive films and anisotropic conductive adhesives in which coated conductive particles whose surfaces are coated with an insulating resin are coated with an insulating resin are bonded to the adjacent insulating resin by the coated insulating resin. It is possible to prevent conduction between particles, and improvement in connection reliability is expected.
このような被覆導電粒子としては、例えば、特許文献１には、ハイブリダイゼーションに
より導電粒子の表面に絶縁層を形成させた被覆導電粒子が開示されており、また、例えば
、特許文献２には、導電粒子の表面に導電粒子より粒径が小さくかつ導電粒子と電荷の符
号が異なる子粒子を用いて被覆した被覆導電粒子が開示されている。
As such coated conductive particles, for example, Patent Document 1 discloses coated conductive particles in which an insulating layer is formed on the surface of the conductive particles by hybridization, and for example, Patent Document 2 A coated conductive particle is disclosed in which the surface of a conductive particle is coated with a child particle having a particle size smaller than that of the conductive particle and having a charge sign different from that of the conductive particle.
しかしながら、絶縁層や子粒子のガラス転移温度（Ｔｇ）又は軟化点温度が低いと、貯蔵
安定性が低く、被覆導電粒子同士が合着や凝集を起こしやすくなり、また、異方導電ペー
ストや異方導電フィルムとして電極間で熱圧着を行う際に、隣接粒子間でのリークが起こ
りやすくなるといった問題があり、絶縁層や子粒子のＴｇ又は軟化点温度が高いと、電極
間で熱圧着する際の条件が厳しくなり、基板や液晶セルガラスに大きな負担がかかるとい
った問題があった。
However, if the glass transition temperature (Tg) or softening point temperature of the insulating layer or the child particles is low, the storage stability is low, and the coated conductive particles tend to coalesce or agglomerate with each other. When performing thermocompression bonding between electrodes as a conductive film, there is a problem that leakage between adjacent particles is likely to occur. When the Tg or softening point temperature of the insulating layer or the child particles is high, thermocompression bonding is performed between the electrodes. The conditions at the time became severe, and there was a problem that a large burden was placed on the substrate and the liquid crystal cell glass.
本発明は、上記に鑑み、基板間の導電接続を確実に行うことができるとともに、隣接する
粒子間でのリークを防止することができる被覆導電粒子、該被覆導電粒子を用いてなる異
方性導電材料及び導電接続構造体を提供することを目的する。
In view of the above, the present invention can reliably perform conductive connection between substrates and can prevent leakage between adjacent particles, and an anisotropic film formed using the coated conductive particles. An object is to provide a conductive material and a conductive connection structure.
本発明は、表面が導電性を有する金属からなる基材粒子と前記基材粒子を被覆する絶縁性
の中空粒子とからなる被覆導電粒子である。
以下に本発明を詳述する。
The present invention is a coated conductive particle comprising substrate particles made of a metal having a conductive surface and insulating hollow particles covering the substrate particles.
The present invention is described in detail below.
本発明の被覆粒子は、基材粒子と該基材粒子を被覆する中空粒子とからなる。
上記基材粒子は、その表面が導電性を有する金属からなる。このような被覆導電粒子は、
半導体素子等の小型電機部品を基板に電気的に接続したり、基板同士を電気的に接続した
りするためのいわゆる異方性導電材料として用いることができる。
この場合、上記基材粒子は、後述する無機化合物や有機化合物からなる球状芯材粒子の表
面に上記導電性を有する金属の層が形成されていてもよく、上記導電性を有する金属のみ
からなる金属粒子であってもよい。なかでも、有機化合物からなる球状芯材粒子の表面に
導電性の金属層が形成されたものは、基板間を導電接続する際の圧着時に変形して接合面
積を増やすことができることから、接続安定性の点で好ましい。
The coated particles of the present invention comprise base particles and hollow particles that coat the base particles.
The base particles are made of a metal whose surface has conductivity. Such coated conductive particles are
It can be used as a so-called anisotropic conductive material for electrically connecting small electrical parts such as semiconductor elements to substrates or electrically connecting substrates.
In this case, the base material particle may be formed with the conductive metal layer on the surface of the spherical core particle made of an inorganic compound or an organic compound, which will be described later, and is made of only the conductive metal. Metal particles may also be used. Among them, those in which a conductive metal layer is formed on the surface of spherical core particles made of an organic compound can be deformed at the time of pressure bonding when conductively connecting between substrates, so that the joining area can be increased. From the viewpoint of sex.
上記導電性を有する金属としては特に限定されず、例えば、金、銀、銅、白金、亜鉛、鉄
、錫、鉛、アルミニウム、コバルト、インジウム、ニッケル、クロム、チタン、アンチモ
ン、ビスマス、ゲルマニウム、カドミウム等の金属や、ＩＴＯ、ハンダ等の金属化合物か
らなるもの等が挙げられる。
The conductive metal is not particularly limited. For example, gold, silver, copper, platinum, zinc, iron, tin, lead, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium, cadmium And those made of metal compounds such as ITO and solder.
上記導電性を有する金属からなる金属層が有機化合物からなる球状芯材粒子の表面に形成
されている場合、上記金属層は、単層構造であってもよく、複数の層からなる積層構造で
あってもよい。積層構造からなる場合には、最外層は金からなることが好ましい。最外層
を金からなるものにすることにより、耐食性が高く接触抵抗も小さいので、得られる被覆
粒子は更に優れたものとなる。
When the metal layer made of the conductive metal is formed on the surface of the spherical core particles made of an organic compound, the metal layer may have a single layer structure or a laminated structure made up of a plurality of layers. There may be. In the case of a laminated structure, the outermost layer is preferably made of gold. By making the outermost layer of gold, since the corrosion resistance is high and the contact resistance is small, the obtained coated particles are further improved.
上記有機化合物からなる球状芯材粒子の表面に導電性の金属層を形成する方法としては特
に限定されず、例えば、物理的な金属蒸着法、化学的な無電解メッキ法等の公知の方法が
挙げられるが、工程の簡便さから無電解メッキ法が好適である。無電解メッキ法で形成で
きる金属層としては、例えば、金、銀、銅、プラチナ、パラジウム、ニッケル、ロジウム
、ルテニウム、コバルト、錫及びこれらの合金等が挙げられるが、本発明の被覆導電粒子
においては、均一な被覆を高密度で形成できることから金属層の一部又は全部が無電解ニ
ッケルメッキによって形成されたものであることが好ましい。
The method for forming the conductive metal layer on the surface of the spherical core particles made of the organic compound is not particularly limited. For example, a known method such as physical metal vapor deposition or chemical electroless plating may be used. The electroless plating method is preferable because of the simplicity of the process. Examples of the metal layer that can be formed by the electroless plating method include gold, silver, copper, platinum, palladium, nickel, rhodium, ruthenium, cobalt, tin, and alloys thereof. In the coated conductive particles of the present invention, Since a uniform coating can be formed at a high density, it is preferable that a part or all of the metal layer is formed by electroless nickel plating.
上記金属層の最外層に金層を形成する方法としては特に限定されず、例えば、無電解メッ
キ、置換メッキ、電気メッキ、スパッタリング等の既知の方法等が挙げられる。
The method for forming the gold layer on the outermost layer of the metal layer is not particularly limited, and examples thereof include known methods such as electroless plating, displacement plating, electroplating, and sputtering.
上記金属層の厚みとしては特に限定されないが、好ましい下限は０．００５μｍ、好まし
い上限は２μｍである。０．００５μｍ未満であると、導電層としての充分な効果が得ら
れないことがあり、２μｍを超えると、得られる被覆導電粒子の比重が高くなりすぎたり
、有機化合物からなる母粒子の硬さがもはや充分変形できる硬度ではなくなったりするこ
とがある。より好ましい下限は０．０１μｍ、より好ましい上限は１μｍである。
Although it does not specifically limit as thickness of the said metal layer, A preferable minimum is 0.005 micrometer and a preferable upper limit is 2 micrometers. When the thickness is less than 0.005 μm, a sufficient effect as the conductive layer may not be obtained. When the thickness exceeds 2 μm, the specific gravity of the obtained coated conductive particles becomes too high, or the hardness of the mother particles made of an organic compound May no longer be hard enough to deform. A more preferable lower limit is 0.01 μm, and a more preferable upper limit is 1 μm.
また、上記金属層の最外層を金層とする場合には、金層の厚みの好ましい下限は０．００
１μｍ、好ましい上限は０．５μｍである。０．００１μｍ未満であると、均一に金属層
を被覆することが困難になり耐食性や接触抵抗値の向上効果が期待できないことがあり、
０．５μｍを超えると、その効果の割には高価である。より好ましい下限は０．０１μｍ
、より好ましい上限は０．３μｍである。
When the outermost layer of the metal layer is a gold layer, the preferred lower limit of the gold layer thickness is 0.00
1 μm and a preferable upper limit is 0.5 μm. If it is less than 0.001 μm, it may be difficult to uniformly coat the metal layer, and the improvement effect of corrosion resistance and contact resistance value may not be expected.
If it exceeds 0.5 μm, it is expensive for its effect. A more preferable lower limit is 0.01 μm.
A more preferable upper limit is 0.3 μm.
上記基材粒子が球状芯材粒子の表面に上記導電性を有する金属の層が形成されている場合
、上記球状芯材粒子としては特に限定されず、例えば、均一な組成からなる粒子や、複数
の原料が層状に構成された多層構造の粒子等が挙げられる。なかでも、基材粒子に機械的
特性や電気的特性等の種々の特性を付与したい場合には、多層構造の粒子が好適である。
When the base metal particles are formed with the conductive metal layer on the surface of the spherical core particles, the spherical core particles are not particularly limited. For example, particles having a uniform composition, And particles having a multilayer structure in which the raw materials are formed in layers. In particular, when it is desired to impart various properties such as mechanical properties and electrical properties to the base particles, particles having a multilayer structure are preferable.
上記球状芯材粒子を構成する材料としては特に限定されず、公知のシリカ等の無機材料や
有機材料等が挙げられる。なかでも、本発明の被覆導電粒子が異方性導電材料に用いられ
る場合に、基板間を導電接続する際の圧着時に変形して基材粒子表面と電極との接合面積
を増やすことができ、接続安定性に優れることから、有機材料が好ましい。
It does not specifically limit as a material which comprises the said spherical core material particle, Well-known inorganic materials, such as a silica, an organic material, etc. are mentioned. Among them, when the coated conductive particles of the present invention are used for an anisotropic conductive material, it can be deformed at the time of pressure bonding when conductively connecting between the substrates, and the bonding area between the surface of the base particle and the electrode can be increased. An organic material is preferable because of excellent connection stability.
上記有機材料としては特に限定されず、例えば、ポリエチレン、ポリプロピレン、ポリス
チレン、ポリプロピレン、ポリイソブチレン、ポリブタジエン等のポリオレフィン、ポリ
メチルメタクリレート、ポリメチルアクリレート等のアクリル樹脂、ポリアルキレンテレ
フタレート、ポリスルホン、ポリカーボネート、ポリアミド、フェノールホルムアルデヒ
ド樹脂等のフェノール樹脂、メラミンホルムアルデヒド樹脂等のメラミン樹脂、ベンゾグ
アナミンホルムアルデヒド樹脂等のベンゾグアナミン樹脂、尿素ホルムアルデヒド樹脂、
エポキシ樹脂、（不）飽和ポリエステル樹脂、ポリエチレンテレフタレート、ポリスルホ
ン、ポリフェニレンオキサイド、ポリアセタール、ポリイミド、ポリアミドイミド、ポリ
エーテルエーテルケトン、ポリエーテルスルホン等からなるものが挙げられる。なかでも
、エチレン性不飽和基を有する種々の重合性単量体を１種又は２種以上重合させてなる樹
脂を用いてなるものは、好適な硬さを得やすいことから好ましい。
The organic material is not particularly limited. For example, polyolefins such as polyethylene, polypropylene, polystyrene, polypropylene, polyisobutylene, and polybutadiene, acrylic resins such as polymethyl methacrylate and polymethyl acrylate, polyalkylene terephthalate, polysulfone, polycarbonate, polyamide, Phenol resin such as phenol formaldehyde resin, melamine resin such as melamine formaldehyde resin, benzoguanamine resin such as benzoguanamine formaldehyde resin, urea formaldehyde resin,
Examples thereof include epoxy resin, (un) saturated polyester resin, polyethylene terephthalate, polysulfone, polyphenylene oxide, polyacetal, polyimide, polyamideimide, polyetheretherketone, polyethersulfone and the like. Especially, what uses the resin formed by superposing | polymerizing 1 type, or 2 or more types of various polymerizable monomers which have an ethylenically unsaturated group is preferable from being easy to obtain suitable hardness.
上記エチレン性不飽和基を有する重合性単量体は、非架橋性の単量体でも架橋性の単量体
でもよい。
上記非架橋性の単量体としては、例えば、スチレン、α−メチルスチレン、ｐ−メチルス
チレン、ｐ−クロロスチレン、クロロメチルスチレン等のスチレン系単量体；（メタ）ア
クリル酸、マレイン酸、無水マレイン酸等のカルボキシル基含有単量体；メチル（メタ）
アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（
メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アク
リレート、セチル（メタ）アクリレート、ステアリル（メタ）アクリレート、シクロヘキ
シル（メタ）アクリレート、イソボルニル（メタ）アクリレート、エチレングリコール（
メタ）アクリレート、トリフルオロエチル（メタ）アクリレート、ペンタフルオロプロピ
ル（メタ）アクリレート等のアルキル（メタ）アクリレート類；２−ヒドロキシエチル（
メタ）アクリレート、グリセロール（メタ）アクリレート、ポリオキシエチレン（メタ）
アクリレート、グリシジル（メタ）アクリレート等の酸素原子含有（メタ）アクリレート
類；（メタ）アクリロニトリル等のニトリル含有単量体；メチルビニルエーテル、エチル
ビニルエーテル、プロピルビニルエーテル等のビニルエーテル類；酢酸ビニル、酪酸ビニ
ル、ラウリン酸ビニル、ステアリン酸ビニル、フッ化ビニル、塩化ビニル、プロピオン酸
ビニル等の酸ビニルエステル類；エチレン、プロピレン、ブチレン、メチルペンテン、イ
ソプレン、ブタジエン等の不飽和炭化水素等が挙げられる。
The polymerizable monomer having an ethylenically unsaturated group may be a non-crosslinkable monomer or a crosslinkable monomer.
Examples of the non-crosslinkable monomer include styrene monomers such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, chloromethylstyrene; (meth) acrylic acid, maleic acid, Carboxyl group-containing monomers such as maleic anhydride; methyl (meth)
Acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (
(Meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, ethylene glycol (
Alkyl (meth) acrylates such as meth) acrylate, trifluoroethyl (meth) acrylate and pentafluoropropyl (meth) acrylate; 2-hydroxyethyl (
(Meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth)
Oxygen atom-containing (meth) acrylates such as acrylate and glycidyl (meth) acrylate; Nitrile-containing monomers such as (meth) acrylonitrile; Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and propyl vinyl ether; Vinyl acetate, vinyl butyrate and laurin Acid vinyl esters such as vinyl acid vinyl, vinyl stearate, vinyl fluoride, vinyl chloride and vinyl propionate; and unsaturated hydrocarbons such as ethylene, propylene, butylene, methylpentene, isoprene and butadiene.
上記架橋性の単量体としては、例えば、テトラメチロールメタンテトラ（メタ）アクリレ
ート、テトラメチロールメタントリ（メタ）アクリレート、テトラメチロールメタンジ（
メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジペンタエリ
スリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリ
レート、グリセロールトリ（メタ）アクリレート；グリセロールジ（メタ）アクリレート
、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ
）アクリレート等の多官能（メタ）アクリレート類；トリアリル（イソ）シアヌレート、
トリアリルトリメリテート、ジビニルベンゼン、ジアリルフタレート、ジアリルアクリル
アミド、ジアリルエーテル等；γ―（メタ）アクリロキシプロピルトリメトキシシラン、
トリメトキシシリルスチレン、ビニルトリメトキシシラン等のシラン含有単量体；フタル
酸等のジカルボン酸類；ジアミン類；ジアリルフタレート、ベンゾグアナミン、トリアリ
ルイソシアネート等が挙げられる。
Examples of the crosslinkable monomer include tetramethylolmethane tetra (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (
(Meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate; glycerol di (meth) acrylate, polyethylene glycol di (meth) ) Polyfunctional (meth) acrylates such as acrylate and polypropylene glycol di (meth) acrylate; triallyl (iso) cyanurate,
Triallyl trimellitate, divinylbenzene, diallyl phthalate, diallyl acrylamide, diallyl ether, etc .; γ- (meth) acryloxypropyltrimethoxysilane,
Silane-containing monomers such as trimethoxysilylstyrene and vinyltrimethoxysilane; dicarboxylic acids such as phthalic acid; diamines; diallyl phthalate, benzoguanamine, triallyl isocyanate and the like.
上記基材粒子の平均粒子径の好ましい下限は０．５μｍ、好ましい上限は１０００μｍで
ある。０．５μｍ未満であると、球状芯材粒子の表面に金属層を形成する場合、球状芯材
粒子の凝集が生じやすく、このような凝集を起こした球状芯材粒子を用いて製造される被
覆導電粒子が、異方性導電材料に用いられると隣接電極間のショートを引き起こすことが
ある。１０００μｍを超えると、電極当たりの被覆導電粒子の個数が少なくなりすぎ接続
信頼性が低下し、基板間の導電接続が不良となることがある。なお、上記球状芯材粒子の
平均粒子径は光学顕微鏡、電子顕微鏡、粒度分布計等を用いて計測した粒子径を統計的に
処理して求めることができる。
The preferable lower limit of the average particle diameter of the substrate particles is 0.5 μm, and the preferable upper limit is 1000 μm. When the metal layer is formed on the surface of the spherical core particles when the thickness is less than 0.5 μm, the spherical core particles are likely to be aggregated, and the coating produced using the spherical core particles that have caused such aggregation When the conductive particles are used as an anisotropic conductive material, a short circuit between adjacent electrodes may be caused. If it exceeds 1000 μm, the number of coated conductive particles per electrode becomes too small, and the connection reliability may be lowered, resulting in poor conductive connection between the substrates. The average particle size of the spherical core particles can be obtained by statistically processing the particle size measured using an optical microscope, an electron microscope, a particle size distribution meter or the like.
上記球状芯材粒子の平均粒子径の変動係数は１０％以下であることが好ましい。１０％を
超えると、得られる被覆導電粒子が異方性導電材料に用いられると、相対向する電極間隔
を任意に制御することが困難になる。なお、上記変動係数とは、粒子径分布から得られる
標準偏差を平均粒子径で除して得られる数値である。
上記球状芯材粒子の１０％Ｋ値の好ましい下限は１０００ＭＰａ、好ましい上限は１５０
００ＭＰａである。１０００ＭＰａ未満であると、得られる被覆導電粒子の強度が不充分
であるため、本発明の被覆導電粒子が異方性導電材料に用いられると、圧縮変形させたと
きに粒子の破壊が生じ導電材料としての機能を果たさなくなることがあり、１５０００Ｍ
Ｐａを超えると、本発明の被覆導電粒子が異方性導電材料に用いられると、電極を傷つけ
ることがある。より好ましい下限は２０００ＭＰａ、より好ましい上限は１００００ＭＰ
ａである。なお、上記１０％Ｋ値は、微小圧縮試験器（例えば、島津製作所製ＰＣＴ−２
００等）を用い、粒子を直径５０μｍのダイアモンド製円柱からなる平滑圧子端面で、圧
縮速度２．６ｍＮ／秒、最大試験荷重１０ｇの条件下で圧縮した場合の圧縮変位（ｍｍ）
を測定し、下記式により求めることができる。
Ｋ値（Ｎ／ｍｍ２）＝（３／√２）・Ｆ・Ｓ−３／２・Ｒ−１／２
Ｆ：粒子の１０％圧縮変形における荷重値（Ｎ）
Ｓ：粒子の１０％圧縮変形における圧縮変位（ｍｍ）
Ｒ：粒子の半径（ｍｍ）
The variation coefficient of the average particle diameter of the spherical core particles is preferably 10% or less. If it exceeds 10%, when the coated conductive particles obtained are used as an anisotropic conductive material, it becomes difficult to arbitrarily control the distance between the opposing electrodes. The coefficient of variation is a numerical value obtained by dividing the standard deviation obtained from the particle size distribution by the average particle size.
The preferable lower limit of the 10% K value of the spherical core particles is 1000 MPa, and the preferable upper limit is 150.
00 MPa. If it is less than 1000 MPa, the strength of the coated conductive particles obtained is insufficient. Therefore, when the coated conductive particles of the present invention are used as an anisotropic conductive material, the particles are destroyed when compressed and deformed. 15000M may not function as
If it exceeds Pa, the electrode may be damaged when the coated conductive particles of the present invention are used as an anisotropic conductive material. A more preferable lower limit is 2000 MPa, and a more preferable upper limit is 10,000 MP.
a. In addition, the 10% K value is a micro compression tester (for example, PCT-2 manufactured by Shimadzu Corporation).
, Etc.), and the compression displacement (mm) when the particles are compressed on a smooth indenter end face made of a diamond cylinder having a diameter of 50 μm under a compression speed of 2.6 mN / sec and a maximum test load of 10 g.
Can be obtained by the following formula.
K value (N / mm 2) = ( 3 / √2) · F · S -3/2 · R -1/2
F: Load value at 10% compression deformation of particles (N)
S: Compression displacement (mm) in 10% compression deformation of particles
R: radius of particle (mm)
なお、１０％Ｋ値が上記条件を満たす基材粒子を得るためには、球状芯材粒子は、上述の
エチレン性不飽和基を有する重合性単量体を重合させてなる樹脂からなることが好ましく
、この場合、構成成分として架橋性単量体を少なくとも２０重量％以上含有することがよ
り好ましい。
In order to obtain base particles having a 10% K value satisfying the above conditions, the spherical core particles may be made of a resin obtained by polymerizing the above polymerizable monomer having an ethylenically unsaturated group. In this case, it is more preferable to contain at least 20% by weight of a crosslinkable monomer as a constituent component.
上記球状芯材粒子は、回復率が２０％以上であることが好ましい。２０％未満であると、
得られる被覆導電粒子を圧縮した場合に変形しても元に戻らないため接続不良を起こすこ
とがある。より好ましくは４０％以上である。なお、上記回復率とは、粒子に９．８ｍＮ
の荷重を負荷した後の回復率をいう。
The spherical core particles preferably have a recovery rate of 20% or more. If it is less than 20%,
If the resulting coated conductive particles are compressed, they will not return to their original shape even if they are deformed, which may cause poor connection. More preferably, it is 40% or more. The recovery rate is 9.8 mN per particle.
It means the recovery rate after applying the load.
このような球状芯材粒子の製造方法としては、従来公知の方法を用いることができ特に限
定されないが、例えば、エマルジョン重合法、転相乳化重合、懸濁重合法、分散重合法、
シード重合法、ソープフリー析出重合法等が挙げられる。なかでも粒径の制御性に優れる
シード重合法が好適である。
また、上記球状芯材粒子として市販されているものを用いることもできる。
As a method for producing such spherical core particles, conventionally known methods can be used and are not particularly limited. For example, emulsion polymerization, phase inversion emulsion polymerization, suspension polymerization, dispersion polymerization,
Examples thereof include a seed polymerization method and a soap-free precipitation polymerization method. Among these, a seed polymerization method that is excellent in controllability of particle diameter is preferable.
Moreover, what is marketed as said spherical core material particle can also be used.
本発明の被覆導電粒子において、上記基材粒子には絶縁性の中空粒子が被覆されている。
上記中空粒子は、その内部に大きな空隙が１つ形成された構造であってもよく、また、複
数個の空隙が形成されていてもよく、更にその内部に複数の小さな空隙が形成されスポン
ジ状となった構造であってもよい。また、上記中空粒子の内部がスポンジ状である場合、
各空隙は、互いに連通していてもよく、独立していてもよく、これらが混在していてもよ
い。更に、上記中空粒子は、その内部に形成された空隙が表面に開孔していてもよい。
In the coated conductive particles of the present invention, the base particles are coated with insulating hollow particles.
The hollow particles may have a structure in which one large void is formed therein, or a plurality of voids may be formed, and a plurality of small voids may be further formed therein to form a sponge. The resulting structure may be used. Further, when the inside of the hollow particles is sponge-like,
Each space | gap may be mutually connected, may be independent, and these may be mixed. Further, the hollow particles may have voids formed in the inside thereof on the surface.
上記中空粒子の空隙率は１０％以上であることが好ましい。１０％未満であると、基材粒
子を中空粒子で被覆する効果が余り得られず、本発明の被覆導電粒子を用いて圧着により
基板等の接続を行う際に、高い圧力をかけないと基材粒子と基板との間から中空粒子を排
除しきれないことがある。
なお、上記空隙率とは、上記中空粒子の空隙部分を含んだ全体の体積に占める空隙部分の
割合のことをいい、この中空粒子の空隙率は、例えば、透過型電子顕微鏡（ＴＥＭ）によ
る粒子断面の観察や粒子の比重を測定することによって得られる。
The porosity of the hollow particles is preferably 10% or more. If it is less than 10%, the effect of coating the base particles with the hollow particles is not so much obtained, and when connecting the substrate or the like by pressure bonding using the coated conductive particles of the present invention, a high pressure is not applied. The hollow particles may not be completely excluded from between the material particles and the substrate.
In addition, the said porosity means the ratio of the space | gap part which occupies for the whole volume including the space | gap part of the said hollow particle, The porosity of this hollow particle is particle | grains by a transmission electron microscope (TEM), for example It is obtained by observing the cross section or measuring the specific gravity of the particles.
また、上記中空粒子は、基材粒子が２％変形する程度の加熱及び加圧により、変形及び／
又は破壊されることが好ましい。上記条件で変形及び／又は破壊されないほど堅いと、導
電接続させる際に厳しい熱圧着条件を必要とし、ドライバーＩＣや基板等を損傷するおそ
れがある。
このような中空粒子が基材粒子に被覆された本発明の被覆導電粒子を用いて圧着により基
板等を導電接続する場合、圧着条件が低温、低圧であっても上記基材粒子と基板との間に
被覆された中空粒子が変形又は破壊されやすく、また、この変形又は破壊された中空粒子
が上記基材粒子と基板との間に残留する量も少ないため、基材粒子表面の導電性を有する
金属と基板の電極とを直接接続することができる。
The hollow particles are deformed and / or deformed by heating and pressurizing such that the base particles are deformed by 2%.
Or it is preferable to be destroyed. If it is hard enough not to be deformed and / or destroyed under the above conditions, severe thermocompression bonding conditions are required when conducting conductive connection, and there is a risk of damage to the driver IC, the substrate, or the like.
When conducting conductive connection of a substrate or the like by pressure bonding using the coated conductive particles of the present invention in which the base particles are coated with such hollow particles, the substrate particles and the substrate are bonded even when the pressure bonding conditions are low temperature and low pressure. The hollow particles coated in between are easily deformed or broken, and the amount of the deformed or broken hollow particles remaining between the substrate particles and the substrate is small, so that the conductivity of the surface of the substrate particles is reduced. The metal and the electrode of the substrate can be directly connected.
上記中空粒子を構成する材料としては、絶縁性を有するものであれば特に限定されないが
、基板等を圧着により接続する際に変形や破壊されやすいことから有機化合物からなるこ
とが好ましい。
絶縁性を有する上記有機化合物としては特に限定されず、例えば、上述の基材粒子に用い
られる有機化合物等が挙げられる。
なお、上記中空粒子を構成する材料としては上記有機化合物に限定されることはなく、例
えば、シリカ等の無機化合物からなるものであってもよい。
The material constituting the hollow particles is not particularly limited as long as it has insulating properties, but is preferably made of an organic compound because it is easily deformed or broken when a substrate or the like is connected by pressure bonding.
It does not specifically limit as said organic compound which has insulation, For example, the organic compound etc. which are used for the above-mentioned base material particle are mentioned.
In addition, as a material which comprises the said hollow particle, it is not limited to the said organic compound, For example, you may consist of inorganic compounds, such as a silica.
上記有機化合物の中では、本発明の被覆導電粒子が異方性導電材料として用いられる場合
には、加熱圧着の際に、上記被覆導電粒子と基板間の有機材料粒子が溶融又は軟化し、良
好な基板間の導電接続が得られるため、熱可塑性の樹脂が好適に用いられる。
Among the organic compounds, when the coated conductive particles of the present invention are used as an anisotropic conductive material, the organic material particles between the coated conductive particles and the substrate are melted or softened during thermocompression bonding. Since a conductive connection between the substrates can be obtained, a thermoplastic resin is preferably used.
なお、本発明の被覆導電粒子において、上記中空粒子を製造する方法としては特に限定さ
れず、公知の方法により製造することができる。例えば、ミニエマルジョン重合法、エマ
ルジョン重合法、転相乳化重合、マイクロサスペンジョン重合法、懸濁重合法、分散重合
法、シード重合法、ソープフリー析出重合法等が挙げられる。これらの中でも中空率の制
御性に優れるミニエマルジョン重合法又はシード重合法が好適に用いられる。また、中空
粒子として市販されているものを用いることもできる。
In addition, in the covering electroconductive particle of this invention, it does not specifically limit as a method to manufacture the said hollow particle, It can manufacture by a well-known method. Examples thereof include a mini-emulsion polymerization method, an emulsion polymerization method, a phase inversion emulsion polymerization, a micro suspension polymerization method, a suspension polymerization method, a dispersion polymerization method, a seed polymerization method, and a soap-free precipitation polymerization method. Among these, a mini-emulsion polymerization method or a seed polymerization method that is excellent in controllability of the hollow ratio is preferably used. Moreover, what is marketed as a hollow particle can also be used.
上記中空粒子の粒子径は、基材粒子の粒子径及び本発明の被覆粒子の用途によっても異な
るが、基材粒子の粒子径の１／１０以下であることが好ましい。１／１０を超えると、基
材粒子の物性が中空粒子の物性によって支配されることがあり、基材粒子を用いる効果が
得られにくくなる。更に好ましくは、中空粒子の粒子径の下限は１０ｎｍ、好ましい上限
は２０００ｎｍである。また、本発明の被覆導電粒子を異方性導電材料として用いる場合
は、上記中空粒子の粒子径の好ましい下限は５ｎｍ、上限は１０００ｎｍであり、より好
ましい下限は１０ｎｍ、上限は５００ｎｍである。５ｎｍ未満であると、隣接する被覆導
電粒子間の距離が電子のホッピング距離より小さくなり、リークが起こりやすくなり、１
０００ｎｍを超えると、圧着する際に必要な圧力や熱が大きくなりすぎることがある。
また、上記中空粒子の粒子径が上記基材粒子の粒子径の１／１０以下である場合、後述す
るヘテロ凝集法により本発明の被覆導電粒子を製造する際に、効率よく基材粒子上に中空
粒子を吸着させることができる。
なお、大きな中空粒子により被覆された隙間に小さな中空粒子が入り込み、被覆密度を向
上できるため、粒子径の異なる２種以上の中空粒子を併用してもよい。この際、小さな中
空粒子の粒子径は大きな中空粒子の粒子径の１／２以下であることが好ましく、また、小
さな中空粒子の数は大きな中空粒子の数の１／４以下であることが好ましい。
The particle diameter of the hollow particles varies depending on the particle diameter of the base particle and the application of the coated particle of the present invention, but is preferably 1/10 or less of the particle diameter of the base particle. If it exceeds 1/10, the physical properties of the base particles may be governed by the physical properties of the hollow particles, and the effect of using the base particles will be difficult to obtain. More preferably, the lower limit of the particle diameter of the hollow particles is 10 nm, and the preferable upper limit is 2000 nm. When the coated conductive particles of the present invention are used as an anisotropic conductive material, the preferable lower limit of the particle diameter of the hollow particles is 5 nm, the upper limit is 1000 nm, the more preferable lower limit is 10 nm, and the upper limit is 500 nm. If it is less than 5 nm, the distance between adjacent coated conductive particles becomes smaller than the electron hopping distance, and leakage tends to occur.
If it exceeds 000 nm, the pressure and heat required for pressure bonding may become too large.
Moreover, when the particle diameter of the hollow particles is 1/10 or less of the particle diameter of the substrate particles, when the coated conductive particles of the present invention are produced by the heteroaggregation method described later, the substrate particles are efficiently formed on the substrate particles. Hollow particles can be adsorbed.
In addition, since small hollow particles enter a gap covered with large hollow particles and the coating density can be improved, two or more kinds of hollow particles having different particle diameters may be used in combination. At this time, the particle diameter of the small hollow particles is preferably ½ or less of the particle diameter of the large hollow particles, and the number of small hollow particles is preferably ¼ or less of the number of large hollow particles. .
上記中空粒子は、粒子径のＣＶ値が２０％以下であることことが好ましい。２０％を超え
ると、得られる被覆粒子の被覆層の厚さが不均一となり、本発明の被覆粒子が異方性導電
材料に用いられる場合、電極間で圧着する際に均一に圧力がかけにくくなり、導通不良を
起こすことがある。なお、上記粒子径のＣＶ値は、下記式により算出することができる。
粒子径のＣＶ値（％）＝粒子径の標準偏差／平均粒子径×１００
上記粒子径分布の測定方法としては、基材粒子を被覆する前は粒度分布計等で測定できる
が、被覆した後はＳＥＭ写真の画像解析等で測定することができる。
The hollow particles preferably have a particle diameter CV value of 20% or less. If it exceeds 20%, the thickness of the coating layer of the resulting coated particles becomes non-uniform, and when the coated particles of the present invention are used for anisotropic conductive materials, it is difficult to apply pressure uniformly when crimping between electrodes. May cause poor conduction. The CV value of the particle diameter can be calculated by the following formula.
CV value of particle diameter (%) = standard deviation of particle diameter / average particle diameter × 100
As a method for measuring the particle size distribution, it can be measured with a particle size distribution meter or the like before coating the substrate particles, but after coating, it can be measured by image analysis of an SEM photograph or the like.
本発明の被覆導電粒子は、このような中空粒子が基材粒子の表面に被覆されているのであ
るが、上記中空粒子は、その表面積の２０％以下が上記基材表面粒子の表面と接触してい
ることが好ましい。２０％を超えると、上記中空粒子の変形が大きく、得られる被覆導電
粒子の被覆層の厚さが不均一となったり、また、中空粒子と基材粒子の結合力が強くなり
すぎて、本発明の被覆導電粒子が異方導電材料に用いられる場合に、電極間で圧着しても
基材粒子と電極との間から中空粒子が排除できずに、導通不良を起こしたりすることがあ
る。なお、下限については特に限定されず、中空粒子と基材粒子とが、例えば鎖長の長い
ポリマー等により結ばれている場合には、実質的に０％であってもよい。
In the coated conductive particles of the present invention, such hollow particles are coated on the surface of the substrate particles, but the hollow particles have a surface area of 20% or less in contact with the surface of the substrate surface particles. It is preferable. If it exceeds 20%, the deformation of the hollow particles is large, the thickness of the coating layer of the coated conductive particles obtained becomes non-uniform, and the bonding force between the hollow particles and the base particles becomes too strong. When the coated conductive particles of the invention are used as an anisotropic conductive material, the hollow particles cannot be excluded from between the base material particles and the electrodes even if they are pressure-bonded between the electrodes, which may cause poor conduction. The lower limit is not particularly limited, and may be substantially 0% when the hollow particles and the base particles are bound by, for example, a polymer having a long chain length.
本発明の被覆導電粒子は、上記基材粒子の表面の５％以上が上記中空粒子により被覆され
ていることが好ましい。５％未満であると、被覆導電粒子の絶縁性を確保できないことが
ある。また、本発明の被覆導電粒子が異方性導電材料に用いられる場合、中空粒子の被覆
密度の好ましい下限は５％、好ましい上限は６０％であることが好ましい。５％未満であ
ると、隣接粒子間で基材粒子の金属表面が接触して横方向のリークが起こりやすくなり、
６０％を超えると、充分な導通性を確保することができなくなるおそれがある。
なお、上記基材粒子表面の中空粒子による被覆率は、中空粒子の添加量（濃度）、基材粒
子表面に導入する官能基の量（密度）、反応溶媒の種類等によって制御可能である。
In the coated conductive particles of the present invention, it is preferable that 5% or more of the surface of the substrate particles is coated with the hollow particles. If it is less than 5%, the insulating properties of the coated conductive particles may not be ensured. When the coated conductive particles of the present invention are used as an anisotropic conductive material, the preferable lower limit of the coating density of the hollow particles is preferably 5%, and the preferable upper limit is preferably 60%. If it is less than 5%, the metal surface of the base material particle is in contact between adjacent particles, and lateral leakage is likely to occur.
If it exceeds 60%, sufficient conductivity may not be ensured.
In addition, the coverage with the hollow particles on the surface of the substrate particles can be controlled by the addition amount (concentration) of the hollow particles, the amount (density) of functional groups introduced to the surface of the substrate particles, the type of reaction solvent, and the like.
本発明の被覆粒子において、上記中空粒子と基材粒子との結合方法としては特に限定され
ないが、物理的な吸着や化学的な吸着いずれを用いてもよい。物理的な吸着方法としては
、例えば、高速攪拌機やハイブリタイザー等の乾式方法等が挙げられる。しかしながら、
上記高速攪拌機やハイブリダイザー等を用いた乾式方法により基材粒子表面に中空粒子を
導入すると、必要以上の圧力や摩擦熱等の負荷がかかりやすくなる。この際、中空粒子が
基材粒子との衝撃や摩擦熱により変形又は破壊し、被覆粒子の膜厚が不均一になったり、
中空粒子が積層付着し、被覆厚の制御が困難になったりすることがあるため、上記中空粒
子と基材粒子とは、化学結合していることが好ましく、共有結合していることが更に好ま
しい。上記中空粒子と上記基材粒子とが化学結合していると、ファンデルワールス力や静
電気力のみによる結合に比べて結合力が強く、中空粒子が基材粒子から剥がれ落ちるのを
防ぐことができる。また、この化学結合は基材粒子と中空粒子との間にのみ形成され、中
空粒子同士が結合することはないので、中空粒子による被覆層は単層となる。このことか
ら、基材粒子及び中空粒子として粒子径の揃ったものを用いれば、容易に本発明の被覆粒
子の粒子径を均一なものとすることができる。
In the coated particles of the present invention, the method for bonding the hollow particles and the base particles is not particularly limited, and either physical adsorption or chemical adsorption may be used. Examples of the physical adsorption method include dry methods such as a high-speed stirrer and a hybridizer. However,
When hollow particles are introduced onto the surface of the substrate particles by a dry method using the high-speed stirrer, a hybridizer, or the like, a load such as an excessive pressure or frictional heat is easily applied. At this time, the hollow particles are deformed or destroyed by impact and frictional heat with the base particles, and the coating particle thickness becomes non-uniform,
The hollow particles and the base particles may be chemically bonded, and more preferably covalently bonded, because the hollow particles may be laminated and the control of the coating thickness may be difficult. . When the hollow particles and the base particles are chemically bonded, the binding force is stronger than that by only van der Waals force or electrostatic force, and the hollow particles can be prevented from peeling off from the base particles. . Moreover, since this chemical bond is formed only between the base particles and the hollow particles, and the hollow particles are not bonded to each other, the coating layer of the hollow particles is a single layer. From this, if the thing with a uniform particle diameter is used as a base particle and a hollow particle, the particle diameter of the covering particle | grains of this invention can be made uniform easily.
本発明の被覆導電粒子において、上記中空粒子は、基材粒子に対して結合性を有する官能
基（Ａ）を介して上記基材粒子の表面を部分的に被覆していることが好ましい。この場合
、上記中空粒子は、上記基材粒子に化学結合されることとなり、ファンデルワールス力や
静電気力のみによる結合に比べて結合力が強く、本発明の被覆導電粒子が異方性導電材料
に用いられる場合、バインダー樹脂等に混練する際に中空粒子が剥がれ落ちたり、隣接す
る被覆導電粒子との接触により中空粒子が剥がれ落ちてリークが起こったりするのを防ぐ
ことができる。また、この化学結合は基材粒子と中空粒子との間にのみ形成され、中空粒
子同士が結合することはないので、中空粒子は単層で被覆されることとなる。このことか
ら、基材粒子及び中空粒子として粒子径の揃ったものを用いれば、容易に本発明の被覆導
電粒子の粒子径を均一なものとすることができる。
In the coated conductive particle of the present invention, it is preferable that the hollow particle partially covers the surface of the base particle through a functional group (A) having a binding property to the base particle. In this case, the hollow particles are chemically bonded to the base particles, and the bonding force is stronger than the bonding by van der Waals force or electrostatic force alone, and the coated conductive particles of the present invention are anisotropic conductive materials. In the case of being used, it is possible to prevent the hollow particles from peeling off when kneaded into the binder resin or the like, or the hollow particles from peeling off due to contact with the adjacent coated conductive particles to cause leakage. Moreover, since this chemical bond is formed only between the base particles and the hollow particles, and the hollow particles are not bonded to each other, the hollow particles are covered with a single layer. From this, if the base particles and hollow particles having the same particle diameter are used, the particle diameter of the coated conductive particles of the present invention can be easily made uniform.
上記官能基（Ａ）としては、金属とイオン結合、共有結合、配位結合が可能な基であれば
特に限定されず、例えば、シラン基、シラノール基、カルボキシル基、アミノ基、アンモ
ニウム基、ニトロ基、水酸基、カルボニル基、チオール基、スルホン酸基、スルホニウム
基、ホウ酸基、オキサゾリン基、ピロリドン基、燐酸基、ニトリル基等が挙げられる。基
材粒子が金属からなる表面を有する本発明の被覆導電粒子では、金属との結合は配位結合
が好適に用いられるため、Ｓ、Ｎ、Ｐ原子を有する官能基が好適に用いられる。例えば、
上記金属が金の場合には、金に対して配位結合を形成するＳ原子を有する官能基、特にチ
オール基、スルフィド基であることが好ましい。
The functional group (A) is not particularly limited as long as it is a group capable of ionic bond, covalent bond, and coordinate bond with a metal. For example, silane group, silanol group, carboxyl group, amino group, ammonium group, nitro group Group, hydroxyl group, carbonyl group, thiol group, sulfonic acid group, sulfonium group, boric acid group, oxazoline group, pyrrolidone group, phosphoric acid group, nitrile group and the like. In the coated conductive particles of the present invention in which the base particles have a surface made of a metal, a coordinate bond is preferably used for the bond with the metal, and therefore a functional group having S, N, and P atoms is preferably used. For example,
When the metal is gold, it is preferably a functional group having an S atom that forms a coordinate bond with gold, particularly a thiol group or a sulfide group.
このような官能基（Ａ）を用いて基材粒子と中空粒子とを化学結合させる方法としては特
に限定されないが、例えば、１）官能基（Ａ）を表面に有する中空粒子を基材粒子の表面
に導入する方法、２）官能基（Ａ）と反応性官能基（Ｂ）とを有する化合物を基材粒子表
面に導入し、その後一段階又は多段階の反応により反応性官能基（Ｂ）と中空粒子とを反
応させて結合する方法等が挙げられる。
The method of chemically bonding the base particles and the hollow particles using such a functional group (A) is not particularly limited. For example, 1) hollow particles having a functional group (A) on the surface are used as the base particles. 2) Introduction of a compound having a functional group (A) and a reactive functional group (B) onto the surface of the substrate particle, and then a reactive functional group (B) by a one-step or multi-step reaction. And a method in which the hollow particles are reacted and bonded.
上記１）の方法において、官能基（Ａ）を表面に有する中空粒子を作製する方法としては
特に限定されず、例えば、官能基（Ａ）を有するモノマーを中空粒子の製造時に混入させ
る方法；中空粒子の表面に化学結合により官能基（Ａ）を導入する方法；中空粒子の表面
を化学処理し官能基（Ａ）に改質する方法；中空粒子の表面をプラズマ等で官能基（Ａ）
に改質する方法等が挙げられる。
In the method 1), the method for producing the hollow particles having the functional group (A) on the surface is not particularly limited. For example, a method in which a monomer having the functional group (A) is mixed during the production of the hollow particles; A method of introducing a functional group (A) into the surface of the particle by chemical bonding; a method of chemically treating the surface of the hollow particle to modify the functional group (A); a surface of the hollow particle with a functional group (A) by plasma or the like
And the like.
上記２）の方法としては、例えば、同一分子内に官能基（Ａ）とヒドロキシル基、カルボ
キシル基、アミノ基、エポキシ基、シリル基、シラノール基、イソシアネート基等の反応
性官能基（Ｂ）とを有する化合物を基材粒子と反応させ、次いで、反応性官能基（Ｂ）に
共有結合可能な官能基を表面に有する有機化合物粒子を反応させる方法等が挙げられる。
このような同一分子内に官能基（Ａ）と反応性官能基（Ｂ）とを有する化合物としては、
例えば、２−アミノエタンチオール、ｐ−アミノチオフェノール等が挙げられる。２−ア
ミノエタンチオールを用いれば、基材粒子の表面にＳＨ基を介して２−アミノエタンチオ
ールを結合させ、一方のアミノ基に対して例えば表面にエポキシ基やカルボキシル基等を
有する中空粒子を反応させることにより、基材粒子と中空粒子とを結合することができる
。
Examples of the method 2) include a functional group (A) and a reactive functional group (B) such as hydroxyl group, carboxyl group, amino group, epoxy group, silyl group, silanol group, and isocyanate group in the same molecule. And a method of reacting organic compound particles having functional groups that can be covalently bonded to the reactive functional group (B) on the surface.
As such a compound having a functional group (A) and a reactive functional group (B) in the same molecule,
Examples thereof include 2-aminoethanethiol and p-aminothiophenol. If 2-aminoethanethiol is used, 2-aminoethanethiol is bonded to the surface of the base particle via an SH group, and hollow particles having, for example, an epoxy group or a carboxyl group on the surface with respect to one amino group. By making it react, a base particle and a hollow particle can be couple | bonded.
本発明の被覆粒子を製造する方法としては特に限定されず、例えば、静電相互作用、ドラ
イブレンド法、融解分散冷却法、溶解分散乾燥法、ヘテロ凝集法、スプレードライ法、界
面重合法等で基材粒子の表面に中空粒子を導入する方法が挙げられる。単層の中空粒子で
被覆する場合、中空粒子の導入の際にはヘテロ凝集法が好適に用いられる。
The method for producing the coated particles of the present invention is not particularly limited. For example, electrostatic interaction, dry blending method, melt dispersion cooling method, solution dispersion drying method, heteroaggregation method, spray drying method, interfacial polymerization method, etc. The method of introduce | transducing a hollow particle into the surface of a base particle is mentioned. In the case of coating with a single layer of hollow particles, a heteroaggregation method is suitably used when introducing the hollow particles.
上記ヘテロ凝集法は、水及び／又は有機溶剤中で中空粒子を基材粒子表面に凝集させこと
により導電性を有する金属からなる基材粒子表面に均一に中空粒子を被覆することができ
る。また、水及び／又は有機溶剤が介在することにより、溶媒効果により基材粒子表面又
は基材粒子表面に導入された官能基と中空粒子の官能基との化学反応が迅速に起こるため
、必要以上の圧力を必要とせず、また、系全体の温度の制御も容易であるため、基材粒子
への負荷が小さくなる。また、中空粒子が過剰の熱や圧力により変形や破壊するといった
問題が起こりにくくなり、被覆の精度が極めて高くなる。
上記有機溶剤としては、中空粒子を溶解しないのもであれば特に限定されない。
In the heteroaggregation method, the hollow particles can be uniformly coated on the surface of the base particles made of a conductive metal by aggregating the hollow particles on the surface of the base particles in water and / or an organic solvent. In addition, the presence of water and / or organic solvent causes a rapid chemical reaction between the functional group introduced to the surface of the base particle or the surface of the base particle due to the solvent effect and the functional group of the hollow particle. Is not required, and the temperature of the entire system is easily controlled, so the load on the base particles is reduced. In addition, the problem that the hollow particles are deformed or broken by excessive heat or pressure is less likely to occur, and the accuracy of the coating becomes extremely high.
The organic solvent is not particularly limited as long as it does not dissolve the hollow particles.
本発明の被覆導電粒子は、中空粒子によって基材粒子表面が単層で被覆されていることが
好ましい。単層であると、中空粒子の粒子径を制御することで、容易に本発明の被覆導電
粒子の粒子径を制御することができ、本発明の被覆導電粒子を用いて圧着により基板等の
接続を行う際、被覆導電粒子に加わる圧力を均一なものとすることができ、確実な導電接
続を実現することができるからである。なお、中空粒子によって基材粒子表面を単層で被
覆する方法としては、上述したヘテロ凝集法が好ましい。
In the coated conductive particles of the present invention, the surface of the base particle is preferably coated with a single layer by hollow particles. When it is a single layer, the particle diameter of the coated conductive particles of the present invention can be easily controlled by controlling the particle diameter of the hollow particles, and the substrate or the like can be connected by pressure bonding using the coated conductive particles of the present invention. This is because the pressure applied to the coated conductive particles can be made uniform when performing the above, and a reliable conductive connection can be realized. In addition, as a method of coating the surface of the base material particle with a single layer with the hollow particles, the heteroaggregation method described above is preferable.
本発明の被覆導電粒子は、被覆導電粒子１ｇと１０ｍＬの超純水とを石英管に封入し、１
２０℃、２４時間抽出したときに、上記超純水中に抽出されるイオンの濃度が１０ｐｐｍ
以下であることが好ましい。１０ｐｐｍを超えると、本発明の被覆導電粒子を液晶表示素
子用上下導通材料として用いた場合、被覆導電粒子に起因するイオンマイグレーションが
発生し、短絡等の原因となったり、液晶を汚染したりすることがある。
このような抽出されるイオンの濃度を達成する方法としては特に限定されないが、上記被
覆粒子を構成する基材粒子又は被覆する中空粒子を以下の方法により作製する方法が挙げ
られる。
The coated conductive particles of the present invention include 1 g of coated conductive particles and 10 mL of ultrapure water enclosed in a quartz tube.
When extracted at 20 ° C. for 24 hours, the concentration of ions extracted into the ultrapure water is 10 ppm.
The following is preferable. If it exceeds 10 ppm, when the coated conductive particles of the present invention are used as a vertical conduction material for a liquid crystal display element, ion migration caused by the coated conductive particles occurs, which may cause a short circuit or contaminate the liquid crystal. Sometimes.
A method for achieving the concentration of ions to be extracted is not particularly limited, and examples thereof include a method for producing the base particles constituting the coated particles or the hollow particles to be coated by the following method.
即ち、イオン性官能基を有する重合性単量体を含む重合性単量体混合物と、ノニオン性重
合開始剤とを含有する重合性組成物を水中に均一に分散した状態で重合して表面にイオン
性官能基を有する基材樹脂又は中空粒子となる樹脂微粒子を得る。更に、得られた樹脂微
粒子のイオン性官能基を非イオン性官能基に変換する方法により基材粒子又は被覆する中
空粒子を作製したり、基材粒子を中空粒子で被覆した後、中空粒子表面のイオン性官能基
を非イオン性官能基に変換したりすることによって作製する。
That is, a polymerizable composition containing a polymerizable monomer containing a polymerizable monomer having an ionic functional group and a polymerizable composition containing a nonionic polymerization initiator are polymerized in a state of being uniformly dispersed in water, and are then applied to the surface. Resin fine particles to be a base resin or hollow particles having an ionic functional group are obtained. Further, the surface of the hollow particle is prepared after the base particle or the hollow particle to be coated is prepared by the method of converting the ionic functional group of the obtained resin fine particle to the nonionic functional group, or the base particle is coated with the hollow particle. The ionic functional group is converted into a nonionic functional group.
本発明の被覆導電粒子は、異方性導電材料、熱線反射材料、電磁波シールド材料等の用途
に用いることができる。なかでも、絶縁性のバインダー樹脂中に分散させることにより異
方性導電材料として好適に用いることができる。
本発明の被覆導電性粒子が絶縁性のバインダー樹脂中に分散されている異方性導電材料も
また、本発明の１つである。
なお、本明細書において、異方性導電材料には、異方性導電膜、異方性導電ペースト、異
方性導電接着剤、異方性導電インク等が含まれる。
The coated conductive particles of the present invention can be used for applications such as anisotropic conductive materials, heat ray reflective materials, and electromagnetic shielding materials. Especially, it can use suitably as an anisotropic conductive material by disperse | distributing in insulating binder resin.
An anisotropic conductive material in which the coated conductive particles of the present invention are dispersed in an insulating binder resin is also one aspect of the present invention.
Note that in this specification, the anisotropic conductive material includes an anisotropic conductive film, an anisotropic conductive paste, an anisotropic conductive adhesive, an anisotropic conductive ink, and the like.
上記絶縁性のバインダー樹脂としては、絶縁性であれば特に限定されないが、例えば、ア
クリル酸エステル、エチレン−酢酸ビニル樹脂、スチレン−ブタジエンブロック共重合体
及びその水添物、スチレン−イソプレンブロック共重合体及びその水添物等の熱可塑性樹
脂；エポキシ樹脂、アクリル酸エステル樹脂、メラミン樹脂、尿素樹脂、フェノール樹脂
等の熱硬化性樹脂；多価アルコールのアクリル酸エステル、ポリエステルアクリレート、
多価カルボン酸の不飽和エステル等の紫外線、電子線等により硬化する樹脂等が挙げられ
る。なかでも、熱及び／又は光により硬化する粘接着剤が好適である。
The insulating binder resin is not particularly limited as long as it is insulative. For example, acrylic ester, ethylene-vinyl acetate resin, styrene-butadiene block copolymer and its hydrogenated product, styrene-isoprene block copolymer Thermoplastic resins such as coalesced and hydrogenated products; thermosetting resins such as epoxy resins, acrylate resins, melamine resins, urea resins, phenol resins; acrylic acid esters of polyhydric alcohols, polyester acrylates,
Examples include resins that are cured by ultraviolet rays, electron beams, and the like, such as unsaturated esters of polyvalent carboxylic acids. Especially, the adhesive agent hardened | cured with a heat | fever and / or light is suitable.
また、本発明の異方性導電材料を用いて液晶表示素子の液晶基板を導電接続する場合、上
記バインダー樹脂は、液晶の汚染を防止するために光及び／又は熱による硬化後の体積抵
抗値が１×１０１３Ω・ｃｍ以上、１００ｋＨｚにおける誘電率（比誘電率）が３以上で
あることが好ましい。
In addition, when the liquid crystal substrate of the liquid crystal display element is conductively connected using the anisotropic conductive material of the present invention, the binder resin has a volume resistance value after curing by light and / or heat in order to prevent contamination of the liquid crystal. Is 1 × 10 13 Ω · cm or more, and the dielectric constant (relative dielectric constant) at 100 kHz is preferably 3 or more.
本発明の異方性導電材料においては、含有される本発明の被覆導電粒子の中空粒子に含ま
れる官能基と、バインダー樹脂中の官能基とが化学結合することが好ましい。上記中空粒
子とバインダー樹脂とが化学結合することにより、バインダー樹脂中に分散された本発明
の被覆導電粒子の安定性に優れるとともに、熱溶融した中空粒子がブリードアウトして基
板や液晶を汚染することがなく、かつ、長期的な接続の安定性や信頼性に優れる異方性導
電材料となる。
In the anisotropic conductive material of the present invention, it is preferable that the functional group contained in the hollow particles of the coated conductive particle of the present invention contained is chemically bonded to the functional group in the binder resin. When the hollow particles and the binder resin are chemically bonded, the coated conductive particles of the present invention dispersed in the binder resin have excellent stability, and the hot-melt hollow particles bleed out to contaminate the substrate and the liquid crystal. And an anisotropic conductive material having excellent long-term connection stability and reliability.
このような中空粒子とバインダー樹脂との組み合わせとしては、例えば、中空粒子はカル
ボキシル基、エポキシ基、イソシアネート基、アミノ基、水酸基、スルホン酸、シラン基
、シラノール基等の官能基を有することが好ましく、なかでもエポキシ基を有することが
より好ましい。これに対して、バインダー樹脂は、常温下、加熱下又は光照射下でこれら
の官能基と反応性の官能基を有する（共）重合体や、上記反応性の官能基を有し、重合反
応や重縮合反応により（共）重合体や重縮合体を形成することができる単量体等を用いる
ことが好ましい。これらのバインダー樹脂は、単独で用いられても良いし、２種類以上が
併用されてもよい。
As a combination of such hollow particles and a binder resin, for example, the hollow particles preferably have a functional group such as a carboxyl group, an epoxy group, an isocyanate group, an amino group, a hydroxyl group, a sulfonic acid, a silane group, and a silanol group. Of these, it is more preferable to have an epoxy group. On the other hand, the binder resin has a (co) polymer having a functional group reactive with these functional groups at room temperature, under heating or under light irradiation, and has a reactive functional group as described above. It is preferable to use a monomer or the like that can form a (co) polymer or a polycondensate by a polycondensation reaction. These binder resins may be used alone or in combination of two or more.
本発明の異方性導電材料には、必須成分であるバインダー樹脂及び本発明の被覆導電粒子
以外に、本発明の課題達成を阻害しない範囲で必要に応じて、例えば、充填剤、増量剤、
軟化剤、可塑剤、重合触媒、硬化触媒、着色剤、酸化防止剤、熱安定剤、光安定剤、紫外
線吸収剤、滑剤、帯電防止剤、難燃剤等の各種添加剤の１種類又は２種類以上が添加され
てもよい。
In the anisotropic conductive material of the present invention, in addition to the binder resin which is an essential component and the coated conductive particles of the present invention, for example, a filler, an extender,
One or two kinds of various additives such as softener, plasticizer, polymerization catalyst, curing catalyst, colorant, antioxidant, heat stabilizer, light stabilizer, ultraviolet absorber, lubricant, antistatic agent, flame retardant, etc. The above may be added.
上記バインダー樹脂中に本発明の被覆導電性粒子を分散させる方法としては特に限定され
ず、従来公知の分散方法を用いることができ、例えば、バインダー樹脂中に被覆導電性粒
子を添加した後、プラネタリーミキサー等で混練して分散させる方法；被覆導電性粒子を
水や有機溶剤中にホモジナイザー等を用いて均一に分散させた後、バインダー樹脂中へ添
加し、プラネタリーミキサー等で混練して分散させる方法；バインダー樹脂を水や有機溶
剤等で希釈した後、被覆導電性粒子を添加し、プラネタリーミキサー等で混練して分散さ
せる方法等の機械的剪断力を付与する分散方法等が挙げられる。これらの分散方法は、単
独で用いられてもよいし、２種類以上が併用されてもよい。
The method for dispersing the coated conductive particles of the present invention in the binder resin is not particularly limited, and a conventionally known dispersion method can be used. For example, after adding the coated conductive particles to the binder resin, A method of kneading and dispersing with a Lee mixer or the like; after uniformly dispersing the coated conductive particles in water or an organic solvent using a homogenizer or the like, adding it to a binder resin and kneading and dispersing with a planetary mixer or the like A method of dispersing the binder resin with water, an organic solvent, or the like, and then adding a coated conductive particle, and a dispersion method of applying mechanical shearing force such as a method of kneading and dispersing with a planetary mixer or the like. . These dispersion methods may be used alone or in combination of two or more.
上記機械的剪断力を付与する方法としては特に限定されず、例えば、遊星式攪拌機、万能
攪拌機、プラネタリーミキサー、ロール、プロペラ撹拌機、ディスパー等の各種混合攪拌
機やこれらを用いる各種混合撹拌方法等が挙げられる。なお、上記機械的剪断力の付与に
際しては、バインダー樹脂中に分散させる本発明の被覆導電粒子の構造を破壊するほどの
機械的剪断力を加えないような方法や条件を適宜選択して行うことが好ましい。
The method for applying the mechanical shearing force is not particularly limited. For example, planetary stirrers, universal stirrers, planetary mixers, rolls, propeller stirrers, dispersers and the like, various mixing stirrers using these, and the like. Is mentioned. In addition, when applying the mechanical shearing force, a method and conditions that do not apply a mechanical shearing force that destroys the structure of the coated conductive particles of the present invention dispersed in the binder resin are appropriately selected. Is preferred.
本発明の異方性導電材料の形態としては特に限定されず、例えば、バインダー樹脂として
絶縁性の液状又は固形の粘接着剤を用い、この粘接着剤中に本発明の被覆導電粒子を分散
させてなる不定形の異方性導電接着剤であってもよいし、定形の異方性導電膜であっても
よい。
The form of the anisotropic conductive material of the present invention is not particularly limited. For example, an insulating liquid or solid adhesive is used as the binder resin, and the coated conductive particles of the present invention are used in the adhesive. An amorphous anisotropic conductive adhesive that is dispersed may be used, or a fixed anisotropic conductive film may be used.
本発明の異方性導電材料を用いて電極間の接合を行う場合、熱及び圧力を加えて圧着する
ことにより基材粒子の金属表面を露出させて導電接続を行う。ここで金属表面が露出する
とは、基材粒子の金属表面が中空粒子に妨げられずに直接基板の電極等と接することがで
きる状態になることをいう。なお、上記圧着の条件としては、異方性導電材料中の被覆粒
子の密度や接続する電子部品の種類等により必ずしも限定されないが、通常は１２０〜２
２０℃の温度で、９．８×１０４〜４．９×１０６Ｐａの圧力により行う。
When joining between electrodes using the anisotropic conductive material of the present invention, conductive connection is made by exposing the metal surface of the base particle by applying heat and pressure and pressing. Here, the exposure of the metal surface means that the metal surface of the base particle can be in direct contact with the electrode of the substrate without being obstructed by the hollow particles. The pressure bonding conditions are not necessarily limited depending on the density of the coated particles in the anisotropic conductive material, the type of electronic component to be connected, and the like.
It is performed at a temperature of 20 ° C. and a pressure of 9.8 × 10 4 to 4.9 × 10 6 Pa.
本発明の被覆導電粒子は、表面が導電性を有する金属からなる基材粒子の表面に絶縁性の
中空粒子が被覆されたものであるため、圧着により基板等の電極同士を電気的に接続する
際に、圧着条件が低圧であっても、上記基材粒子と基板との間の中空粒子が変形又は破壊
されやすく、また、この変形又は破壊された中空粒子が上記基材粒子と基板との間に残留
する量も少なく、基材粒子の金属表面が露出して確実に導電接続させることができ、隣接
する被覆導電粒子間の絶縁性は確保することができる。
The coated conductive particles of the present invention are such that the surface of base particles made of a metal having conductivity is coated with insulating hollow particles, so that electrodes such as substrates are electrically connected by pressure bonding. At this time, even if the pressure-bonding condition is low pressure, the hollow particles between the base particles and the substrate are easily deformed or broken, and the deformed or broken hollow particles are formed between the base particles and the substrate. The amount remaining in between is small, the metal surface of the base particle is exposed, and the conductive connection can be surely made, and the insulation between the adjacent coated conductive particles can be ensured.
また、本発明の被覆導電粒子の中空粒子が基材粒子に対して結合性を有する官能基（Ａ）
を介して基材粒子表面に被覆されている場合、隣接粒子間にかかる圧力や、バインダー樹
脂中に分散させる際の衝撃等によって絶縁性を有する中空粒子が基材粒子の表面から剥が
れることはなく、確実な絶縁性を得ることができる。
Moreover, the functional group (A) in which the hollow particles of the coated conductive particles of the present invention have a binding property to the base particles.
In the case where the surface of the base particle is coated via, the insulating hollow particles are not peeled off from the surface of the base particle due to the pressure applied between the adjacent particles or the impact when dispersed in the binder resin. And reliable insulation can be obtained.
このような本発明の被覆導電粒子が絶縁性のバインダー樹脂中に分散されている本発明の
異方性導電材料は、圧着により基板等の電極同士を電気的に接続する際に、基板と基材粒
子との間の中空粒子のみが変形又は破壊されることで排除され、基材粒子の金属表面が露
出して確実な導通が得られる。
The anisotropic conductive material of the present invention in which the coated conductive particles of the present invention are dispersed in an insulating binder resin is used to electrically connect the substrate and other electrodes to each other by pressure bonding. Only the hollow particles between the material particles are eliminated by being deformed or destroyed, and the metal surface of the substrate particles is exposed, and reliable conduction is obtained.
本発明の被覆導電粒子又は本発明の異方性導電材料により接続される対象物としては、例
えば、表面に電極若しくは導電パターンが形成された基板、又は、フィルム、半導体パッ
ケージ、半導体チップ等の微細な電子部品や、スイッチ、コネクタ等を含む電子部品等が
挙げられる。これらの電子部品が導電接続されてなる導電接続構造体もまた、本発明の１
つである。
Examples of the object to be connected by the coated conductive particle of the present invention or the anisotropic conductive material of the present invention include, for example, a substrate having an electrode or conductive pattern formed on the surface, or a fine film, semiconductor package, semiconductor chip or the like Electronic components including electronic components including switches and connectors. A conductive connection structure in which these electronic components are conductively connected is also a 1 of the present invention.
One.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定
されるものではない。
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
（合成例１）
ドデシルメルカプタン１０重量部、スチレン９５重量部、ジメチルアミノプロピルアクリ
ルアミド５重量部、イオン交換水１０００重量部に、ＡＩＢＡ１重量部、ドデシルトリメ
チルアンモニウムクロライド１重量部を添加し、７０℃で８時間重合させ、平均粒径８０
ｎｍ（ＣＶ値１０％）のラテックス分散液を得た。このラテックスを種粒子として用い、
このラテックスを固形分で１０重量部、ドデシルトリメチルアンモニウムクロライド２重
量部、及び、ＡＩＢＡ１重量部をイオン交換水９００重量部に分散させた。これに、メチ
ルメタクリレート４０重量部、グリシジルメタクリレート２０重量部、スチレン３０重量
部、及び、ジビニルベンゼン１０重量部の混合物を加えて、室温で４８時間攪拌したとこ
ろ、上記物質のほとんどが種粒子に吸収された。引き続き、これを６０℃で６時間重合し
たところ、平均粒径１８０ｎｍ（ＣＶ値１０％）の中空粒子（１）の分散液が得られた。
この粒子分散液を乾燥させ、透過型電子顕微鏡で観察したところ、粒子の中央部が透けて
おり、内径は９０ｎｍであった（中空率１２．５％）。また、この粒子のガラス転移温度
（Ｔｇ）は１０７℃であった。この中空粒子（１）の分散液を遠心分離によりアセトンに
置換し、中空粒子（１）のアセトン分散液（１）を得た。
(Synthesis Example 1)
To 10 parts by weight of dodecyl mercaptan, 95 parts by weight of styrene, 5 parts by weight of dimethylaminopropylacrylamide, 1000 parts by weight of ion-exchanged water, 1 part by weight of AIBA and 1 part by weight of dodecyltrimethylammonium chloride are added and polymerized at 70 ° C. for 8 hours. Average particle size 80
A latex dispersion having a nm (CV value of 10%) was obtained. Using this latex as seed particles,
10 parts by weight of this latex in solid content, 2 parts by weight of dodecyltrimethylammonium chloride, and 1 part by weight of AIBA were dispersed in 900 parts by weight of ion-exchanged water. When a mixture of 40 parts by weight of methyl methacrylate, 20 parts by weight of glycidyl methacrylate, 30 parts by weight of styrene and 10 parts by weight of divinylbenzene was added and stirred for 48 hours at room temperature, most of the above substances were absorbed by the seed particles. It was done. Subsequently, when this was polymerized at 60 ° C. for 6 hours, a dispersion of hollow particles (1) having an average particle diameter of 180 nm (CV value 10%) was obtained.
When this particle dispersion was dried and observed with a transmission electron microscope, the central portion of the particles was transparent and the inner diameter was 90 nm (hollow rate 12.5%). Moreover, the glass transition temperature (Tg) of this particle | grain was 107 degreeC. The hollow particle (1) dispersion was replaced with acetone by centrifugation to obtain an acetone dispersion (1) of the hollow particles (1).
（合成例２）
合成例１と同様にして得られたラテックスを種粒子に用い、このラテックスを固形分で１
０重量部及びドデシルトリメチルアンモニウムクロライド２重量部をイオン交換水９００
重量部に分散させた。これに、メチルメタクリレート４０重量部、グリシジルメタクリレ
ート２０重量部、スチレン３０重量部、過酸化ベンゾイル１重量部、ジビニルベンゼン１
０重量部、及び、エタノール４０重量部の混合物を加えて、室温で４８時間攪拌したとこ
ろ、上記物質のほとんどが種粒子に吸収された。引き続き、これを６０℃で６時間重合し
たところ、平均粒径１６０ｎｍ（ＣＶ値１０％）の中実粒子（１）の分散液が得られた。
この粒子分散液を乾燥させ、透過型電子顕微鏡で観察したところ、この粒子には空隙は認
められなかった。また、この粒子のガラス転移温度（Ｔｇ）は１０７℃であった。この中
実粒子（１）の分散液を遠心分離によりアセトンに置換し、中実粒子（１）のアセトン分
散液（１）を得た。
(Synthesis Example 2)
Latex obtained in the same manner as in Synthesis Example 1 was used as seed particles, and this latex was solid content of 1
0 parts by weight and 2 parts by weight of dodecyltrimethylammonium chloride were added to ion-exchanged water 900.
Dispersed in parts by weight. To this, 40 parts by weight of methyl methacrylate, 20 parts by weight of glycidyl methacrylate, 30 parts by weight of styrene, 1 part by weight of benzoyl peroxide, 1 divinylbenzene
When a mixture of 0 part by weight and 40 parts by weight of ethanol was added and stirred at room temperature for 48 hours, most of the substance was absorbed by the seed particles. Subsequently, when this was polymerized at 60 ° C. for 6 hours, a dispersion of solid particles (1) having an average particle size of 160 nm (CV value of 10%) was obtained.
When this particle dispersion was dried and observed with a transmission electron microscope, no voids were observed in the particles. Moreover, the glass transition temperature (Tg) of this particle | grain was 107 degreeC. The solid particle (1) dispersion was replaced with acetone by centrifugation to obtain an acetone dispersion (1) of solid particles (1).
（実施例１）
平均粒子径５μｍの金表面粒子（ミクロパールＡＵ−２０５：積水化学社製）１０重量部
をアセトンに分散させ、合成例１で得られた中空粒子（１）のアセトン分散液（１）を固
形分で１０重量部添加し、室温で３時間攪拌した。濾過後、更にアセトンで洗浄し、乾燥
させて被覆導電粒子（１）を得た。
Example 1
10 parts by weight of gold surface particles (Micropearl AU-205: manufactured by Sekisui Chemical Co., Ltd.) having an average particle size of 5 μm are dispersed in acetone, and the acetone dispersion liquid (1) of the hollow particles (1) obtained in Synthesis Example 1 is solid. 10 parts by weight per minute was added and stirred at room temperature for 3 hours. After filtration, it was further washed with acetone and dried to obtain coated conductive particles (1).
得られた被覆導電粒子（１）を２０重量部、エポキシ樹脂（エピコート８２８：油化シェ
ルエポキシ社製）１０重量部、トリスジメチルアミノエチルフェノール５重量部、及び、
トルエン１００重量部を遊星式攪拌機で充分に分散、混合させた後、離型フィルム上に一
定の厚みで塗布し、トルエンを蒸発させ、異方性導電膜（１）を得た。得られた異方性導
電膜（１）の厚みは１５μｍであり、被覆導電粒子の含有量は１００万個／ｍｍ３であっ
た。また、膜中には剥がれ落ちた中空粒子（１）は認められなかった。
20 parts by weight of the obtained coated conductive particles (1), 10 parts by weight of an epoxy resin (Epicoat 828: manufactured by Yuka Shell Epoxy Co., Ltd.), 5 parts by weight of trisdimethylaminoethylphenol, and
After 100 parts by weight of toluene was sufficiently dispersed and mixed with a planetary stirrer, it was applied on the release film with a certain thickness, and toluene was evaporated to obtain an anisotropic conductive film (1). The thickness of the obtained anisotropic conductive film (1) was 15 μm, and the content of the coated conductive particles was 1 million particles / mm 3 . Moreover, the hollow particle (1) which peeled off in the film | membrane was not recognized.
（比較例１）
合成例１で得られた中空粒子（１）を合成例２で得られた中実粒子（１）に変更した以外
は、実施例１と同様の操作により、被覆導電粒子（２）及び異方性導電膜（２）を得た。
得られた異方性導電膜（２）の厚みは１５μｍであり、被覆導電粒子の含有量は１００万
個／ｍ３であった。また、膜中に剥がれ落ちた中実粒子（１）は認められなかった。
(Comparative Example 1)
The coated conductive particles (2) and the anisotropic particles were obtained in the same manner as in Example 1, except that the hollow particles (1) obtained in Synthesis Example 1 were changed to the solid particles (1) obtained in Synthesis Example 2. Conductive film (2) was obtained.
The thickness of the obtained anisotropic conductive film (2) was 15 μm, and the content of the coated conductive particles was 1 million particles / m 3 . Moreover, the solid particle (1) which peeled off in the film | membrane was not recognized.
（比較例２）
被覆処理を行っていない金表面粒子を用い、実施例１と同様の操作で、異方性導電膜（３
）を得た。得られた異方性導電膜（３）の厚みは１５μｍであり、被覆導電粒子の含有量
は１００万個／ｍ３であった。
(Comparative Example 2)
Using the gold surface particles not subjected to the coating treatment, an anisotropic conductive film (3
) The thickness of the obtained anisotropic conductive film (3) was 15 μm, and the content of the coated conductive particles was 1 million particles / m 3 .
（被覆状態の観察）
実施例１及び比較例１で得られた被覆導電粒子（１）及び（２）を走査電子顕微鏡（ＳＥ
Ｍ）により表面観察したところ、実施例１で得られた被覆導電粒子（１）の中空粒子（１
）、及び、比較例１で得られた被覆導電粒子（２）の中実粒子（１）は、いずれも基材粒
子の表面に単層で被覆されていたことが確認された。
(Observation of coating state)
The coated conductive particles (1) and (2) obtained in Example 1 and Comparative Example 1 were scanned with a scanning electron microscope (SE
When the surface was observed by M), hollow particles (1) of the coated conductive particles (1) obtained in Example 1 were obtained.
) And the solid particles (1) of the coated conductive particles (2) obtained in Comparative Example 1 were confirmed to be coated with a single layer on the surface of the substrate particles.
（絶縁性の評価）
ライン／スペースが１００／５０μｍ、ライン高さが２０μｍの櫛形電極の中央部に５×
５ｍｍに切断した異方性導電膜（１）〜（３）を貼り付け、１０×１０ｍｍのガラス板で
挟み、ガラス板の接合部を１０Ｎ、１２０℃の圧着条件で６０秒間圧着を行った後、隣接
電極間の絶縁性を評価した。
その結果、異方性導電膜（１）、（２）とも隣接電極間でのリークは認められず、中空粒
子（１）で被覆した被覆導電粒子（１）の絶縁性は、中実粒子（１）で被覆した被覆導電
粒子（２）の絶縁性と同等であった。また、異方性導電膜（３）では隣接電極間でのリー
クが発生した。
(Insulation evaluation)
5 × at the center of the comb electrode with a line / space of 100/50 μm and a line height of 20 μm
After pasting anisotropic conductive films (1) to (3) cut to 5 mm and sandwiching them with a 10 × 10 mm glass plate, the bonded portion of the glass plate was subjected to pressure bonding for 60 seconds under pressure bonding conditions of 10 N and 120 ° C. The insulation between adjacent electrodes was evaluated.
As a result, in the anisotropic conductive films (1) and (2), no leakage between adjacent electrodes was observed, and the insulating properties of the coated conductive particles (1) coated with the hollow particles (1) were solid particles ( It was equivalent to the insulating property of the coated conductive particles (2) coated in 1). In the anisotropic conductive film (3), a leak occurred between adjacent electrodes.
（導電性の評価）
ＩＴＯ電極（幅１００μｍ、高さ０．２μｍ、長さ２ｃｍ）を有したガラス基板（幅１ｃ
ｍ、長さ２．５ｃｍ）のほぼ中央部に、５×５ｍｍに切断した異方性導電膜（１）〜（３
）を貼り付けた後、同じＩＴＯ電極を有したガラス基板を互いの電極が９０度に重なるよ
うに位置合わせを行って貼り付けた。ガラス基板の接合部を１０Ｎ、１２０℃の圧着条件
で６０秒間圧着を行った後、電極間の抵抗値を測定した。
その結果、実施例１で得られた異方性導電膜（１）は、１０組の試験の平均値が５．４Ω
であったのに対し、比較例１で得られた異方性導電膜（２）は、１０組の試験の平均値が
１２．３Ωと高かった。また、比較例２で得られた異方性導電膜（３）は、１０組の試験
の平均値が２．８Ωであった。
ほぼ同じ樹脂組成であっても、中空粒子（１）と中実粒子（１）とでは、熱圧着時に排除
必要な樹脂量が異なるため、同じ圧着条件では、中空粒子の方が熱変形性が高く、これに
伴い、導電粒子と電極間での樹脂排除性が高いため、低抵抗値が実現可能である。
(Evaluation of conductivity)
A glass substrate (width 1c) having an ITO electrode (width 100 μm, height 0.2 μm, length 2 cm)
m, length 2.5 cm) of the anisotropic conductive films (1)-(3
Then, the glass substrates having the same ITO electrodes were aligned and pasted so that the electrodes overlap each other at 90 degrees. After bonding the bonded portion of the glass substrate for 60 seconds under a pressure bonding condition of 10 N and 120 ° C., the resistance value between the electrodes was measured.
As a result, the anisotropic conductive film (1) obtained in Example 1 has an average value of 5.4Ω in 10 sets of tests.
On the other hand, the anisotropic conductive film (2) obtained in Comparative Example 1 had a high average value of 12.3Ω in 10 sets of tests. In addition, the anisotropic conductive film (3) obtained in Comparative Example 2 had an average value of 10 sets of tests of 2.8Ω.
Even if the resin composition is almost the same, the hollow particles (1) and the solid particles (1) differ in the amount of resin that needs to be excluded during thermocompression bonding. Along with this, the resin resistance between the conductive particles and the electrodes is high, and thus a low resistance value can be realized.
本発明は、上記の構成よりなるので、基板間の導電接続を確実に行うことができるととも
に、隣接する粒子間でのリークを防止することができる被覆導電粒子、該被覆導電粒子を
用いてなる異方性導電材料及び導電接続構造体を提供することができる。
Since the present invention has the above-described configuration, the conductive conductive particle can be reliably connected between the substrates, and leakage between adjacent particles can be prevented. The coated conductive particle is used. An anisotropic conductive material and a conductive connection structure can be provided.
Claims (8)
とからなることを特徴とする被覆導電粒子。 Coated conductive particles, characterized in that the surface is composed of base particles made of a metal having conductivity and insulating hollow particles covering the base particles.
求項１記載の被覆導電粒子。 The coated conductive particles according to claim 1, wherein the hollow particles are deformed and / or broken when the base particles are deformed by 2%.
子。 3. The coated conductive particle according to claim 1, wherein the hollow particle has a porosity of 10% or more.
面を部分的に被覆していることを特徴とする請求項１、２又は３記載の被覆導電粒子。 4. The hollow particle partially covers the surface of the base particle through a functional group (A) having a binding property to the base particle. Coated conductive particles.
３又は４記載の被覆導電粒子。 The surface of the base particle is covered with a single layer by hollow particles, 1, 2,
3. The coated conductive particle according to 3 or 4.
ときに、前記超純水中に抽出されるイオンの濃度が１０ｐｐｍ以下であることを特徴とす
る請求項１、２、３、４又は５記載の被覆導電粒子。 1 g of coated conductive particles and 10 mL of ultrapure water are enclosed in a quartz tube and extracted at 120 ° C. for 24 hours, and the concentration of ions extracted into the ultrapure water is 10 ppm or less. Coated conductive particles according to claim 1, 2, 3, 4 or 5.
されていることを特徴とする異方性導電材料。 An anisotropic conductive material, wherein the coated conductive particles according to claim 1, 2, 3, 4, 5, or 6 are dispersed in an insulating binder resin.
により導電接続されていることを特徴とする導電接続構造体。 A conductive connection structure, wherein the conductive connection structure is conductively connected by the coated conductive particles according to claim 1, or the anisotropic conductive material according to claim 7.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030728A (en) * | 2011-09-06 | 2013-04-10 | 日立化成工业株式会社 | Particle for insulation coating, insulating coated conductive particle, anisotropic conductive material, and connecting structure |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4967482B2 (en) * | 2006-02-27 | 2012-07-04 | 日立化成工業株式会社 | Conductive particles, adhesive composition and circuit connecting material |
| US20100065311A1 (en) * | 2006-07-03 | 2010-03-18 | Hitachi Chemical Company, Ltd. | Conductive particle, adhesive composition, circuit-connecting material, circuit-connecting structure, and method for connection of circuit member |
| WO2009034940A1 (en) * | 2007-09-11 | 2009-03-19 | Nippon Steel Chemical Co., Ltd. | Method for formation of conductive layer, method for production of circuit board, method for production of conductive microparticle, and composition for formation of conductive layer |
| EP2211354B1 (en) | 2007-10-22 | 2020-12-16 | Nippon Chemical Industrial Co., Ltd. | Coated conductive powder and conductive adhesive using the same |
| EP2502239A4 (en) * | 2009-11-20 | 2015-01-28 | 3M Innovative Properties Co | Compositions comprising conductive particles with surface-modified nanoparticles covalently attached thereto, and methods of making |
| JP5670133B2 (en) * | 2010-09-17 | 2015-02-18 | 株式会社日本触媒 | Resin particles, insulated conductive particles and anisotropic conductive materials using the same |
| JP5653737B2 (en) * | 2010-12-08 | 2015-01-14 | 株式会社日本触媒 | Resin particles, insulated conductive particles and anisotropic conductive materials using the same |
| WO2020175691A1 (en) * | 2019-02-28 | 2020-09-03 | 積水化学工業株式会社 | Conductive particles, conductive material, and connection structure |
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Cited By (1)
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| CN103030728A (en) * | 2011-09-06 | 2013-04-10 | 日立化成工业株式会社 | Particle for insulation coating, insulating coated conductive particle, anisotropic conductive material, and connecting structure |
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