JP2019207889A - Conductive particles and use thereof - Google Patents
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本発明は、導電粒子に係り、より詳しくはタッチスクリーンパネル用導電粒子に関する。 The present invention relates to conductive particles, and more particularly to conductive particles for touch screen panels.
導電粒子は、硬化剤、接着剤、樹脂バインダーと混合して分散した形で使用されるもので、異方性導電材料、例えば異方性導電フィルム（Ａｎｉｓｏｔｒｏｐｉｃ Ｃｏｎｄｕｃｔｉｖｅ Ｆｉｌｍ）、異方性導電ペースト（Ａｎｉｓｏｔｒｏｐｉｃ Ｃｏｎｄｕｃｔｉｖｅ Ｐａｓｔｅ）、異方性導電インク（Ａｎｉｓｏｔｒｏｐｉｃ Ｃｏｎｄｕｃｔｉｖｅ Ｉｎｋ）、異方性導電シート（Ａｎｉｓｏｔｒｏｐｉｃ Ｃｏｎｄｕｃｔｉｖｅ Ｓｈｅｅｔ）などとして幅広く用いられている。 The conductive particles are used in a form dispersed and mixed with a curing agent, an adhesive, and a resin binder. An anisotropic conductive material, such as an anisotropic conductive film, an anisotropic conductive paste ( It is widely used as Anisotropic Conductive Paste, Anisotropic Conductive Ink, Anisotropic Conductive Sheet, and the like.
例えば、異方性導電材料は、ＬＣＤ（Ｌｉｑｕｉｄ Ｃｒｙｓｔａｌ Ｄｉｓｐｌａｙ）、ＡＭＯＬＥＤ（Ａｃｔｉｖｅ Ｍａｔｒｉｘ Ｏｒｇａｎｉｃ Ｌｉｇｈｔ Ｅｍｉｔｔｉｎｇ Ｄｉｏｄｅ）、ＰＤＰ（Ｐｌａｓｍａ Ｄｉｓｐｌａｙ Ｐａｎｅｌ）などの平板ディスプレイパネルの組立に際して、基板上のＴＦＴ（Ｔｈｉｎ Ｆｉｌｍ Ｔｒａｎｓｉｓｔｏｒ）とこれを駆動するためのドライバーＩＣ（Ｉｎｔｅｇｒａｔｅｄ Ｃｉｒｃｕｉｔ）との電気的接続や、ＴＳＰ（Ｔｏｕｃｈ Ｓｃｒｅｅｎ Ｐａｎｅｌ）の駆動モジュールと電極との接続などに用いられる。 For example, an anisotropic conductive material may be a TFT (Thin) on a substrate when a flat panel display panel such as an LCD (Liquid Crystal Display), an AMOLED (Active Matrix Organic Emitting Diode), or a PDP (Plasma Display Panel) is assembled. And a driver IC (Integrated Circuit) for driving it, and a connection between a TSP (Touch Screen Panel) drive module and an electrode.
このような異方性導電材料として用いられる導電粒子は、ニッケル、銅、銀、金などの金属系；カーボン粉末、カーボン繊維、カーボンフレーク（ｆｌａｋｅ）などのカーボン系；樹脂粒子に金属物質をコートまたはメッキして使用する複合系の粒子などが例示される。 Conductive particles used as such anisotropic conductive materials include nickel, copper, silver, gold, and other metal systems; carbon powder, carbon fiber, carbon flake, and other carbon systems; resin particles are coated with a metal substance Alternatively, composite particles used by plating are exemplified.
金属系粒子は、粒子全体が導電性を有し且つ粒度の分布が広いため、回路の微細ピッチや高精密を要求する分野よりは、回路のピッチが大きく高電流を要求するＰＤＰに主に用いられている。 Metal-based particles are mainly used for PDPs that require a large circuit pitch and a high current, rather than fields that require fine circuit pitch and high precision, because the entire particle is conductive and has a wide particle size distribution. It has been.
カーボン系粒子は、金属系粒子より電気伝導度が低いため、高い電気伝導度を要求する分野には使用が制限される。 Since carbon-based particles have a lower electrical conductivity than metal-based particles, their use is limited in fields requiring high electrical conductivity.
一方、複合系粒子は、電気伝導度が前記金属系粒子とカーボン系粒子との中間程度であって、微粒子の分布を非常に狭くすることができるため、現在最も多く使われている導電粒子である。 On the other hand, composite particles are the most commonly used conductive particles because the electrical conductivity is about the middle between the metal particles and the carbon particles and the distribution of fine particles can be made very narrow. is there.
複合系導電粒子は、球状の樹脂上に無電解メッキ方法でニッケル−リンまたはニッケル−ホウ素またはニッケル−リン−タングステンまたはニッケル−ホウ素−タングステンなどの合金メッキ層を形成してそのまま使用し、或いは腐食防止および電気伝導度向上の目的で金または銀などの貴金属を最外殻に構成して使用することもある。 Composite conductive particles can be used as they are by forming an alloy plating layer such as nickel-phosphorus, nickel-boron, nickel-phosphorus-tungsten, nickel-boron-tungsten or the like on a spherical resin by electroless plating. A precious metal such as gold or silver may be used in the outermost shell for the purpose of prevention and improvement of electrical conductivity.
最近、モバイル機器、特にスマートフォンの普及拡大により、導電粒子はＴＳＰ（Ｔｏｕｃｈ Ｓｃｒｅｅｎ Ｐａｎｅｌ）分野で使用量が急激に増加しつつある。ＴＳＰは、ディスプレイ（ｄｉｓｐｌａｙ）面には互いに接触しない直角の透明電極を被せ、ディスプレイの縁部にはＡｇ粉末またはＣｕ粉末などの金属粉末、バインダーおよび溶媒を混合して製造されたペースト（ｐａｓｔｅ）を用いて、駆動モジュールと連結することが可能な電極を形成する。 Recently, with the spread of mobile devices, particularly smartphones, the amount of conductive particles is rapidly increasing in the TSP (Touch Screen Panel) field. TSP is a paste made by mixing display electrodes with right-angled transparent electrodes that do not contact each other, and mixing the metal powder such as Ag powder or Cu powder, binder and solvent on the edge of the display. Is used to form an electrode that can be connected to the drive module.
形成された電極は、ディスプレイ（ｄｉｓｐｌａｙ）の特性上、高温で熱処理が不可能であるため、一般に揮発成分のみ無くす方法を使用する。よって、電極は非常に弱く形成されている。このため、ＴＳＰと駆動モジュールとを連結するための導電粒子は、非常に柔らかくて変形し易いことが求められた。なぜなら、一般な導電粒子は、ＴＳＰに接合ボンディングを行う場合、ペーストから形成された電極が簡単に破損して短絡となり、或いは抵抗が急激に増加するという問題点があるためである。 Since the formed electrode cannot be heat-treated at a high temperature due to the characteristics of the display, a method of removing only volatile components is generally used. Therefore, the electrode is formed very weakly. For this reason, the conductive particles for connecting the TSP and the drive module are required to be very soft and easily deformed. This is because, when general conductive particles are bonded to TSP, there is a problem that the electrode formed from the paste is easily broken and short-circuited, or the resistance is rapidly increased.
本発明は、前述した問題点を解決するために導出されたもので、その目的は、接続抵抗が低くかつ誤作動が少ない、タッチスクリーンパネル用導電粒子を提供することにある。本発明の他の目的は、前述した導電粒子を用いた異方性導電材料を提供することにある。 The present invention has been derived to solve the above-described problems, and an object thereof is to provide conductive particles for a touch screen panel having low connection resistance and few malfunctions. Another object of the present invention is to provide an anisotropic conductive material using the above-described conductive particles.
上記目的を達成するために、本発明のある観点によれば、樹脂微粒子、および前記樹脂微粒子の外面に形成される被覆層を有する導電粒子であって、下記式１によるＶ値が６≦Ｖ≦２５であり、変曲点発生力が１．０〜１５ｍＮである、タッチスクリーンパネル用導電粒子を提供する。 In order to achieve the above object, according to an aspect of the present invention, there is provided conductive particles having resin fine particles and a coating layer formed on an outer surface of the resin fine particles, wherein a V value according to the following formula 1 is 6 ≦ V Provided is a conductive particle for a touch screen panel in which ≦ 25 and the inflection point generation force is 1.0 to 15 mN.
（式１）
Ｖ（％）＝Ｓｖ／Ｄ＊１００
(Formula 1)
V (%) = Sv / D * 100
（式中、Ｓｖは導電粒子に外力（ｌｏａｄ）を増加させるときに導電粒子の変形増加率（＝△圧縮変形量／△外力）の増加が発生する時点の圧縮変形量を示し、Ｄは導電粒子の平均直径（μｍ）を示す。） (In the formula, Sv indicates the amount of compressive deformation at the time when an increase in the deformation rate of the conductive particles (= Δcompression deformation / Δexternal force) occurs when the external force (load) is increased on the conductive particles, and D indicates the conductivity. (The average diameter (μm) of the particles is shown.)
この際、前記導電粒子の平均直径は４〜１６μｍであることが好ましい。 At this time, the average diameter of the conductive particles is preferably 4 to 16 μm.
また、前記被覆層は３０〜４００ｎｍの厚さを有することが好ましい。 The covering layer preferably has a thickness of 30 to 400 nm.
また、前記被覆層は表面に高さ５０ｎｍ〜５００ｎｍの突起を備えることが好ましい。 The covering layer preferably has a protrusion having a height of 50 nm to 500 nm on the surface.
また、前記突起は前記被覆層と同一の物質からなることが好ましい。 The protrusions are preferably made of the same material as the coating layer.
この際、前記被覆層は、Ｎｉ、Ｓｎ、Ａｇ、Ｃｕ、Ｐｄ、Ｚｎ、Ｗ、Ｐ、ＢおよびＡｕよりなる群から選ばれる１種または２種以上の合金からなることが好ましい。 At this time, the coating layer is preferably made of one or more alloys selected from the group consisting of Ni, Sn, Ag, Cu, Pd, Zn, W, P, B, and Au.
また、前記被覆層の外面には、Ａｕ、Ｐｔ、ＡｇおよびＰｄよりなる群から選ばれる１種または２種以上の合金からなる追加の被覆層をさらに含むことができる。 The outer surface of the coating layer may further include an additional coating layer made of one or more alloys selected from the group consisting of Au, Pt, Ag, and Pd.
また、前記導電粒子はＴＳＰ（Ｔｏｕｃｈ Ｓｃｒｅｅｎｉｎｇ Ｐａｎｅｌ）用異方性導電フィルム（ＡＣＦ）に含まれ得る。 The conductive particles may be included in an anisotropic conductive film (ACF) for TSP (Touch Screening Panel).
本発明の他の観点によれば、前述した導電粒子を含む異方性導電材料を提供する。 According to another aspect of the present invention, an anisotropic conductive material including the above-described conductive particles is provided.
本発明の別の観点によれば、前述した導電粒子または異方性導電材料を含む電子装置を提供する。 According to another aspect of the present invention, an electronic device including the above-described conductive particles or anisotropic conductive material is provided.
本発明のある観点による導電粒子は、外力が加えられたときに圧縮変形が調節されるため、回路の接続不良または抵抗の急激な増加による回路の誤作動を起こさない。また、本発明の他の観点による異方性導電材料は、電気抵抗が低くかつ導電信頼性に優れる導電粒子を用いることにより、優れた電気抵抗及び導電信頼性を有する。 In the conductive particles according to an aspect of the present invention, the compression deformation is adjusted when an external force is applied, so that the circuit does not malfunction due to poor connection of the circuit or a sudden increase in resistance. In addition, the anisotropic conductive material according to another aspect of the present invention has excellent electrical resistance and conductive reliability by using conductive particles having low electrical resistance and excellent conductive reliability.
本発明をさらに具体的に説明する前に、本明細書に使用された用語は、特定の実施例を記述するためのものに過ぎず、特許請求の範囲によって定められる本発明の範囲を限定するものではないことを理解すべきである。本明細書に使用されるすべての技術用語および科学用語は、特に言及がない限りは、当該技術分野における通常の技術を有する者に一般に理解されることと同一の意味を有する。 Before further describing the present invention, the terminology used herein is for the purpose of describing particular embodiments only and limits the scope of the invention as defined by the claims. It should be understood that it is not a thing. All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art unless otherwise specified.
本明細書および請求の範囲の全般にわたって、特に言及がない限り、「含む（ｃｏｍｐｒｉｓｅ、ｃｏｍｐｒｉｓｅｓ、ｃｏｍｐｒｉｓｉｎｇ）」という用語は、言及された物、段階または一群の物、および段階を含むことを意味し、任意のある他の物、段階または一群の物または一群の段階を排除する意味で使用されたものではない。 Throughout this specification and the claims, unless otherwise stated, the term “comprise”, “comprises”, “comprising” is meant to include the stated thing, step or group of things, and steps. It is not intended to exclude any certain other thing, step or group of things or group of steps.
一方、本発明の様々な実施例は、明確な反対の指摘がない限り、いかなる他の実施例と組み合わせてもよい。特に、好適または有利であることを示すいかなる特徴も、好適または有利であることを示す他のいかなる特徴と組み合わせてもよい。 On the other hand, the various embodiments of the present invention may be combined with any other embodiment, unless expressly indicated to the contrary. In particular, any feature that indicates suitability or advantage may be combined with any other feature that indicates suitability or advantage.
本発明の一実施例に係る導電粒子は樹脂微粒子と被覆層を含む。樹脂微粒子は単量体の重合体からなる。その材料は、非制限的に、スチレン系、アクリル系、ジビニルベンゼン系などの単量体またはそれらの変形した単量体または前記単量体の混合された単量体を用いて、重合して得られる重合体を使用することが好ましい。例えば、エチルアクリレート、メチルアクリレート、ブチルアクリレート、グリシジルメタクリレート、エチレングリコールジメタクリレート、プロピレングリコールジアクリレート、イソオクチルアクリレート、メチルメタクリレート、ヘキサンジオールジアクリレート、スチレン、メチルスチレン、エチルスチレン、ジビニルベンゼンなどの単量体を単独で使用し或いは２種以上組み合わせて使用することができる。 The conductive particles according to an embodiment of the present invention include resin fine particles and a coating layer. The resin fine particles are made of a monomer polymer. The material can be polymerized using, without limitation, monomers such as styrene, acrylic, divinylbenzene, or modified monomers thereof or a mixture of the above monomers. It is preferred to use the resulting polymer. For example, ethyl acrylate, methyl acrylate, butyl acrylate, glycidyl methacrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate, isooctyl acrylate, methyl methacrylate, hexanediol diacrylate, styrene, methylstyrene, ethylstyrene, divinylbenzene, etc. The body can be used alone or in combination of two or more.
被覆層は、Ｎｉ、Ｓｎ、Ａｇ、Ｃｕ、Ｐｄ、Ｚｎ、Ｗ、Ｐ、ＢおよびＡｕよりなる群から選ばれる１種または２種以上の合金からなる。すなわち、被覆層は、金属、例えば金、銀、ニッケル、銅、錫、亜鉛、チタンなどの単一金属からなってもよく、錫−鉛、錫−銅、錫−亜鉛、ニッケル−リン、ニッケル−ホウ素、ニッケル−タングステンなどの合金からなってもよい。 The coating layer is made of one or more alloys selected from the group consisting of Ni, Sn, Ag, Cu, Pd, Zn, W, P, B, and Au. That is, the coating layer may be made of a metal, for example, a single metal such as gold, silver, nickel, copper, tin, zinc, titanium, tin-lead, tin-copper, tin-zinc, nickel-phosphorus, nickel. -You may consist of alloys, such as boron and nickel-tungsten.
被覆層の厚さは３０〜４００ｎｍ程度であることが好ましい。被覆層の厚さが３０ｎｍ未満の場合は、抵抗値が増加し、被覆層の厚さが４００ｎｍを超える場合は、被覆層の剥離が起こるため、製品の信頼性が低下する。特に好ましい厚さは１００〜２５０ｎｍである。 The thickness of the coating layer is preferably about 30 to 400 nm. When the thickness of the coating layer is less than 30 nm, the resistance value increases. When the thickness of the coating layer exceeds 400 nm, peeling of the coating layer occurs, so that the reliability of the product is lowered. A particularly preferred thickness is 100 to 250 nm.
被覆層の表面には突起が突設されてもよい。突起の高さは、特に限定されないが、好ましい突起の高さは５０ｎｍ〜５００ｎｍである。これは、突起の高さが前述の範囲を外れると、金属酸化層とバインダー樹脂を壊すことが可能な効果が弱くなるためである。一方、さらに好ましい突起の高さは１００〜３００ｎｍである。被覆層の厚さは、例えば以下のように測定される。すなわち、Ｐａｒｔｉｃｌｅ Ｓｉｚｅ Ａｎａｌｙｚｅｒ（ＢＥＣＫＭＡＮ ＭＵＬＴＩＳＩＺＥＲ ＴＭ３）を用いてメッキ前の微粒子の直径ｍｏｄｅ値とメッキ後の導電粒子の直径ｍｏｄｅ値とを測定し、これらの差の１／２を被覆層の厚さとする。なお、測定の対象となる粒子の数は例えば１５０，０００個である。以下の実施例及び比較例では、この方法により被覆層の厚さを測定した。実施例及び比較例では、測定対象となる粒子の数を１５０，０００個とした。 A protrusion may be provided on the surface of the coating layer. The height of the protrusion is not particularly limited, but the preferable height of the protrusion is 50 nm to 500 nm. This is because if the height of the protrusion is out of the above range, the effect of breaking the metal oxide layer and the binder resin is weakened. On the other hand, the height of the protrusion is more preferably 100 to 300 nm. The thickness of the coating layer is measured as follows, for example. That is, using a Particle Size Analyzer (BECKMAN MULTISIZER TM3), the diameter mode value of fine particles before plating and the diameter mode value of conductive particles after plating are measured, and ½ of these differences is taken as the thickness of the coating layer. . Note that the number of particles to be measured is 150,000, for example. In the following examples and comparative examples, the thickness of the coating layer was measured by this method. In the examples and comparative examples, the number of particles to be measured was 150,000.
突起の高さは、例えば以下の方法により測定される。すなわち、走査電子顕微鏡（ＳＥＭ：Ｓｃａｎｎｉｎｇ Ｅｌｅｃｔｒｏｎ Ｍｉｃｒｏｓｃｏｐｅ）を用いて導電粒子の球状の仮想地平線から１０個の突起の高さを測定し、その平均値（算術平均値）を突起の高さとする。実施例及び比較例では、この方法により突起の高さを測定した。 The height of the protrusion is measured by the following method, for example. That is, the height of 10 protrusions is measured from the spherical virtual horizon of the conductive particles using a scanning electron microscope (SEM), and the average value (arithmetic average value) is defined as the protrusion height. In Examples and Comparative Examples, the height of the protrusion was measured by this method.
突起の形状は、特に限定されないが、凸形状であることが好ましい。このような硬度を備える材料としては、被覆層と同一の物質が挙げられる。具体的には、Ｎｉ、Ｓｎ、Ａｇ、Ｃｕ、Ｐｄ、Ｚｎ、Ｗ、Ｐ、ＢおよびＡｕよりなる群から選ばれる１種または２種以上の合金が挙げられる。突起は被覆層と異なる材料で構成されていてもよい。すなわち、突起は、主に金属であって、例えば金、銀、銅、ニッケル、チタン、ビスマス、アンチモンなどの単一金属からなってもよく、または銅−亜鉛、銅−錫、ニッケル−リン、ニッケル−タングステン、ニッケル−ホウ素などの合金からなってもよい。好ましい金属はニッケル、金、銀、パラジウム、タングステンなどである。 The shape of the protrusion is not particularly limited, but is preferably a convex shape. Examples of the material having such hardness include the same substance as the coating layer. Specific examples include one or more alloys selected from the group consisting of Ni, Sn, Ag, Cu, Pd, Zn, W, P, B, and Au. The protrusion may be made of a material different from that of the coating layer. That is, the protrusion is mainly a metal and may be made of a single metal such as gold, silver, copper, nickel, titanium, bismuth, antimony, or copper-zinc, copper-tin, nickel-phosphorus, It may be made of an alloy such as nickel-tungsten or nickel-boron. Preferred metals are nickel, gold, silver, palladium, tungsten and the like.
前述した導電粒子の表層に、金、銀、白金、パラジウムなどの貴金属を含む追加の被覆層を備えてもよい。これは導電粒子の伝導度を高め、酸化防止の効果も得ることができるためである。前記層の形成方法は、特に限定されるものではなく、一般なスパッタリング、メッキ、蒸着の技術を使用することができる。 You may provide the additional coating layer containing noble metals, such as gold | metal | money, silver, platinum, palladium, on the surface layer of the electrically-conductive particle mentioned above. This is because the conductivity of the conductive particles can be increased and an antioxidant effect can be obtained. The method for forming the layer is not particularly limited, and general sputtering, plating, and vapor deposition techniques can be used.
本発明の実施例に係る導電粒子は、外力が加えられると、外力が益々強くなることにより、初期には外力が増加するにつれて変形増加率が一定に増加し、ある時点には小さい外力でも変形増加率が急激に増加する変曲点が発生する。この際、変曲点以前までは弾性変形が行われ、変曲点より後は塑性変形が主に行われる。 In the conductive particles according to the embodiment of the present invention, when an external force is applied, the external force becomes stronger and stronger, so that the rate of increase in deformation increases at an initial stage as the external force increases. An inflection point where the rate of increase rapidly increases occurs. At this time, elastic deformation is performed before the inflection point, and plastic deformation is mainly performed after the inflection point.
この際、本発明の実施例に係る導電粒子は、下記式１による変曲開始変形率（Ｖ）値が６≦Ｖ≦２５であることを満足する。Ｖが６未満の場合、外力によって持続的に変形が行われて第１電極と第２電極間の距離が非常に近くなるため、小さい外力が加わっても、第１電極が第２電極を破壊する問題点が発生し、導電粒子の耐久性が非常に脆弱であるため、異方性導電材料の製造過程または接合ボンディングの際に容易に溶解または変形が生ずる可能性がある。 At this time, the conductive particles according to the example of the present invention satisfy that the inflection start deformation rate (V) value according to the following formula 1 is 6 ≦ V ≦ 25. When V is less than 6, the external electrode is continuously deformed and the distance between the first electrode and the second electrode becomes very close, so even if a small external force is applied, the first electrode destroys the second electrode. And the durability of the conductive particles is very fragile. Therefore, the anisotropic conductive material may be easily dissolved or deformed during the manufacturing process or bonding bonding.
また、Ｖが２５を超過する場合は、導電粒子の変形に必要な力が大きいため、前述した電極の破壊が起こるため、抵抗が急激に増加し或いは短絡が起こるという問題点がある。また、弾性変形による回復力が強いため、ＡＣＦ接合ボンディングの際に外力が除去された後にも、電極を押し上げる効果が起こり、これは短絡或いは抵抗増加をもたらす。 In addition, when V exceeds 25, the force necessary for deformation of the conductive particles is large, so that the electrode is destroyed as described above, so that there is a problem that the resistance increases rapidly or a short circuit occurs. Further, since the recovery force due to elastic deformation is strong, the effect of pushing up the electrode occurs even after the external force is removed during ACF bonding, which causes a short circuit or an increase in resistance.
（式１）
Ｖ（％）＝Ｓｖ／Ｄ＊１００
(Formula 1)
V (%) = Sv / D * 100
ここで、Ｓｖは２５℃に加熱した導電粒子に加える外力を増加させるときに導電粒子の変形増加率（△圧縮変形量／△外力）の増加が発生する時点の圧縮変形量を示し、Ｄは導電粒子の平均直径（μｍ）を示す。導電粒子の加熱は例えばホットプレートによって行われる。 Here, Sv indicates the amount of compressive deformation at the time when an increase in the deformation increase rate of the conductive particles (Δcompression deformation / Δexternal force) occurs when the external force applied to the conductive particles heated to 25 ° C. is increased. The average diameter (μm) of the conductive particles is shown. The conductive particles are heated by, for example, a hot plate.
さらに、導電粒子の変曲点発生力は、１．０〜１５ｍＮである。ここで、変曲点発生力は、上記の変曲点が得られた際の外力を意味する。このように、本実施形態の導電粒子は、変曲点発生力が非常に小さい。したがって、本実施形態の導電粒子は、タッチパネル用の導電粒子として特に好適である。タッチパネルに与えられる外力は小さいことが多いからである。本実施形態の導電粒子をタッチパネル用の導電粒子に適用することで、タッチパネルの電極の破壊を防ぎつつ、電極同士の短絡を防止することができる。変曲開始変形率（Ｖ）値に必要なデータ及び変曲点発生力は微小圧縮試験機（ＭＣＴ、Ｍｉｃｒｏ Ｃｏｍｐｒｅｓｓ Ｔｅｓｔｅｒ）を用いて得ることができる。これを図１及び図２を参照して説明する。図１は微小圧縮試験機によって０．３３ｍＮ／ｓｅｃの速度で力を増加させて最大５０ｍＮまで加えたときの変形量を示すグラフであり、図２は図１の変形量を説明するための説明図である。この際、圧縮変形量（Ｓ）とは、力（Ｆ）を加えるときに力の印加方向に導電粒子の高さが減少した分のことをいう。 Furthermore, the inflection point generating force of the conductive particles is 1.0 to 15 mN. Here, the inflection point generating force means an external force when the above inflection point is obtained. Thus, the conductive particles of this embodiment have a very small inflection point generating force. Therefore, the conductive particles of the present embodiment are particularly suitable as conductive particles for touch panels. This is because the external force applied to the touch panel is often small. By applying the conductive particles of the present embodiment to the conductive particles for a touch panel, it is possible to prevent a short circuit between the electrodes while preventing the electrodes of the touch panel from being destroyed. Data necessary for the inflection starting deformation rate (V) value and the inflection point generating force can be obtained using a micro compression tester (MCT). This will be described with reference to FIGS. FIG. 1 is a graph showing a deformation amount when a force is increased at a speed of 0.33 mN / sec by a micro compression tester and applied up to a maximum of 50 mN, and FIG. 2 is an explanation for explaining the deformation amount of FIG. FIG. At this time, the amount of compressive deformation (S) means that the height of the conductive particles is reduced in the direction of application of force (F).
このことから、導電粒子に対して５０ｍＮの力で圧縮試験を行う場合、導電粒子は、初期に変形し始めて変形増加率が一定に維持され、ある時点には変形増加率（△圧縮変形量／△外力）の増加が発生するが、この時点の一定の力（Ｆ１）に該当する圧縮変形量（Ｓｖ）を求めることができる。 Therefore, when a compression test is performed on the conductive particles with a force of 50 mN, the conductive particles start to be deformed at an initial stage and the deformation increase rate is maintained constant. At a certain point in time, the deformation increase rate (Δcompression deformation amount / (External force) increases, but the amount of compression deformation (Sv) corresponding to the constant force (F1) at this time can be obtained.
例えば、平均直径（Ｄ）８μｍの導電粒子に対して最大５０ｍＮの荷重で圧縮試験を行うとき、導電粒子の変形増加率の増加が発生する時点である、グラフ上の変曲点が生ずる地点における圧縮変形量を求めることができる。さらに、この地点における外力、すなわち変曲点発生力を測定することができる。 For example, when a compression test is performed on a conductive particle having an average diameter (D) of 8 μm with a load of 50 mN at the maximum, at a point where an inflection point on the graph is generated, which is the point at which the increase rate of deformation of the conductive particle occurs The amount of compressive deformation can be determined. Furthermore, the external force at this point, that is, the inflection point generating force can be measured.
一方、導電粒子は、サイズは非制限的であるが、４〜１６μｍの平均直径を有するように製造されることが好ましい。導電粒子のサイズが４μｍ未満の場合は、ＴＳＰの電極材料として用いられる金属粉末のサイズと類似し或いはそれよりやや大きいため、ＴＳＰ用電極の破壊を起こして接続信頼性を低下させ、導電粒子のサイズが１６μｍを超える場合は、一定の電極面積に存在する導電粒子の数が少なくて抵抗が増加する現象を示すおそれがある。 On the other hand, the conductive particles are not limited in size, but are preferably manufactured to have an average diameter of 4 to 16 μm. When the size of the conductive particles is less than 4 μm, it is similar to or slightly larger than the size of the metal powder used as the electrode material of TSP, so that the TSP electrode is destroyed and connection reliability is lowered. When the size exceeds 16 μm, there is a possibility that the resistance increases due to the small number of conductive particles existing in a certain electrode area.
前述した導電粒子の平均直径は、例えば粒子サイズ分析器（Ｐａｒｔｉｃｌｅ Ｓｉｚｅ Ａｎａｌｙｚｅｒ）（ＢＥＣＫＭＡＮ ＭＵＬＴＩＳＩＺＥＲ ＴＭ３）を用いて測定されたモード値である。この際、測定された導電粒子の数は１５０，０００個が好ましい。 The above-mentioned average diameter of the conductive particles is a mode value measured using, for example, a particle size analyzer (BECKMAN MULTISIZER TM3). At this time, the number of measured conductive particles is preferably 150,000.
以下に図３〜図８を参照しながら、本発明に係る導電粒子が作用する段階別メカニズムについて説明する。各図面は第１電極と第２電極との間にＡＣＦが位置した状態を示す。第１電極はＦＰＣＢ（フレキシブルプリント基板）に位置し、第２電極はＴＳＰ基板上に位置する。ＴＳＰ基板の第２電極はペーストを用いて形成された電極であって、非常に小さい力でも電極が破壊される傾向がある。 The mechanism according to the stage at which the conductive particles according to the present invention act will be described below with reference to FIGS. Each drawing shows a state in which the ACF is located between the first electrode and the second electrode. The first electrode is located on the FPCB (flexible printed circuit board) and the second electrode is located on the TSP substrate. The second electrode of the TSP substrate is an electrode formed using a paste, and the electrode tends to be destroyed even with a very small force.
図３は電極の間における電極間の接合のための予備接合段階であって、この段階は作業の便利性と電極の正確な位置決めを図るためである。この際、第１電極と第２電極との間に力が加えられず、導電粒子と電極とは未だ接触していない。 FIG. 3 shows a pre-joining stage for joining the electrodes between the electrodes, and this stage is for convenience of operation and accurate positioning of the electrodes. At this time, no force is applied between the first electrode and the second electrode, and the conductive particles and the electrode are not yet in contact with each other.
図４は電極の間に力が加わり始める段階であって、第１電極に力を加えることにより、第１電極と第２電極との間にある導電粒子が各電極に接触する状態である。電極の間への力の印加は治具（Ｊｉｇ）などを介して行われる。 FIG. 4 is a stage in which a force starts to be applied between the electrodes, and is a state where the conductive particles between the first electrode and the second electrode come into contact with each electrode by applying a force to the first electrode. Application of force between the electrodes is performed through a jig (Jig) or the like.
図５は電極の間に力がさらに加わる段階であって、第１電極に力がさらに加わることにより導電粒子の変形が発生する段階である。この際、導電粒子が変形しなければ、図６に示すように、導電粒子が電極を入り込む現象が発生し、これにより第２電極に亀裂が発生して不良の原因となる。よって、本発明で提示した圧縮変形量（Ｓｖ）が重要な意味を持つ。 FIG. 5 is a stage where a force is further applied between the electrodes, and the conductive particles are deformed when a force is further applied to the first electrode. At this time, if the conductive particles are not deformed, a phenomenon that the conductive particles enter the electrode occurs as shown in FIG. Therefore, the amount of compression deformation (Sv) presented in the present invention is important.
図７は電極の間に加わる力が除去される段階であって、異方性導電フィルム用樹脂は硬化が進み、導電粒子は変形した状態をそのまま維持する。 FIG. 7 is a stage in which the force applied between the electrodes is removed. The anisotropic conductive film resin is cured and the conductive particles are maintained in a deformed state.
図８はＡＣＦ用樹脂が完全に硬化した段階であって、電極の間の導電粒子が第１電極と第２電極との間を電気的に安全に接続する。 FIG. 8 is a stage where the ACF resin is completely cured, and the conductive particles between the electrodes electrically connect the first electrode and the second electrode safely.
本実施形態の導電粒子は、ＴＳＰ用異方性導電フィルム（ＡＣＦ）に含まれてもよく、他の異方性導電材料に含めてもよい。また、導電粒子を含む異方性導電材料（ＡＣＦ含む）は、各種の電子装置（例えばタッチスクリーンパネル）等に適用出来る。ここで、導電粒子を異方性導電材料に含める方法、及び異方性導電材料を電子装置に適用する方法は特に制限されず、従来の方法が任意に適用される。 The conductive particles of the present embodiment may be included in an anisotropic conductive film (ACF) for TSP, or may be included in another anisotropic conductive material. An anisotropic conductive material (including ACF) containing conductive particles can be applied to various electronic devices (for example, touch screen panels). Here, the method of including the conductive particles in the anisotropic conductive material and the method of applying the anisotropic conductive material to the electronic device are not particularly limited, and a conventional method is arbitrarily applied.
（実施例１）
（前処理）
脱イオン水１６００ｇに分散安定剤「ＰＶＰ−３０Ｋ」１５ｇを溶かした。該溶液にポリスチレンモノマー８５ｇとメチルメタクリレートモノマー８５ｇを入れて攪拌しながら懸濁液を作った。該懸濁液に重合剤としての過酸化ベンゾイル（Ｂｅｎｚｏｙｌ ｐｅｒｏｘｉｄｅ）を１．５ｇ添加し、攪拌してよく混合させた。モノマー懸濁液を８５℃で加熱して重合反応を行い、反応が完結するまで１２時間を維持した。合成が完了した後、懸濁液中の微粒子に対して濾過、洗浄、分級、乾燥工程を行って平均直径７．７μｍのコア樹脂微粒子を得た。
Example 1
(Preprocessing)
15 g of a dispersion stabilizer “PVP-30K” was dissolved in 1600 g of deionized water. To this solution, 85 g of polystyrene monomer and 85 g of methyl methacrylate monomer were added and a suspension was prepared while stirring. 1.5 g of benzoyl peroxide as a polymerization agent was added to the suspension, and the mixture was stirred and mixed well. The monomer suspension was heated at 85 ° C. to conduct the polymerization reaction, and maintained for 12 hours until the reaction was completed. After the synthesis was completed, the fine particles in the suspension were filtered, washed, classified, and dried to obtain core resin fine particles having an average diameter of 7.7 μm.
（活性化核形成処理）
一方、樹脂粒子に突起があるように無電解メッキを施す場合は、メッキの際に還元された金属粒子がくっ付く活性化核を樹脂コアの表面に処理する追加の工程が必要である。例えば、アルカリ溶液または酸溶液でエッチングした樹脂コア粒子に対して、脱イオン水に塩酸（ＨＣｌ）と塩化錫（ＳｎＣｌ２）を溶かした溶液でセンシタイジング（ｓｅｎｓｉｔｉｚｉｎｇ）を行い、脱イオン水に塩酸と塩化パラジウム（ＰｄＣｌ２）を溶かした溶液でアクセレレイション（ａｃｃｅｌｅｒａｔｉｏｎ）を行う。前記センシタイジングは絶縁物質の表面にＳｎ２＋イオンを吸着させる工程であり、アクセレレイションはＳｎ２＋＋Ｐｄ２＋→Ｓｎ４＋＋Ｐｄ０で表示される反応によって無電解メッキの触媒核（活性化核）を形成するための触媒処理工程である。本実施例１では、この方法により活性化核を形成した。
(Activated nucleation treatment)
On the other hand, when electroless plating is performed so that the resin particles have protrusions, an additional step of treating the surface of the resin core with activated nuclei to which the reduced metal particles adhere during plating is necessary. For example, resin core particles etched with an alkali solution or an acid solution are sensitized with a solution of hydrochloric acid (HCl) and tin chloride (SnCl 2 ) in deionized water, Acceleration is performed with a solution of hydrochloric acid and palladium chloride (PdCl 2 ). The sensitizing is a step of adsorbing Sn 2+ ions on the surface of the insulating material, and the acceleration is a catalyst nucleus (activated nucleus) of electroless plating by a reaction represented by Sn 2+ + Pd 2+ → Sn 4+ + Pd 0. It is a catalyst processing process for forming. In Example 1, activated nuclei were formed by this method.
（メッキ処理）
次に、３Ｌの反応器に脱イオン水２２００ｍＬを投入し、Ｎｉ塩として硫酸ニッケル２４０ｇ、錯化剤として酢酸ナトリウム５ｇ、安定剤としてＰｂ−酢酸塩０．００２ｇ、および界面活性剤として３ｇのＰＥＧ−４００を順次脱イオン水に溶解させてメッキ液（ａ）を製造した。前述した活性化核形成処理を済ませた、平均直径７．７μｍのコア樹脂粒子５０ｇをメッキ液（ａ）に入れ、ホモジナイザー（ｈｏｍｏｇｅｎｉｚｅｒ）を用いて５分間分散処理を行った。分散処理の後、アンモニア水を用いてｐＨを６．５にした。
(Plating treatment)
Next, 2200 mL of deionized water was charged into a 3 L reactor, 240 g of nickel sulfate as the Ni salt, 5 g of sodium acetate as the complexing agent, 0.002 g of Pb-acetate as the stabilizer, and 3 g of PEG as the surfactant. -400 was sequentially dissolved in deionized water to produce a plating solution (a). 50 g of core resin particles having an average diameter of 7.7 μm, which had been subjected to the above-described activation nucleation treatment, were placed in the plating solution (a) and subjected to a dispersion treatment for 5 minutes using a homogenizer. After the dispersion treatment, the pH was adjusted to 6.5 using aqueous ammonia.
１Ｌのビーカーに脱イオン水３００ｍＬ、還元剤として次亜リン酸ナトリウム２６０ｇ、安定剤としてＰｂ−酢酸塩０．００１ｇを順次溶解させて溶液（ｂ）を得た。 In a 1 L beaker, 300 mL of deionized water, 260 g of sodium hypophosphite as a reducing agent, and 0.001 g of Pb-acetate as a stabilizer were sequentially dissolved to obtain a solution (b).
前記３Ｌの反応器の温度を６５℃に維持し、２５０ｒｐｍで攪拌しながら前記溶液（ｂ）を定量ポンプで初期５分間２０ｍＬ／ｍｉｎの速度で添加した後、残りは８ｍＬ／ｍｉｎで投入した。（ｂ）溶液が全て投入されると、２０分間反応を維持させて平均直径８．０１μｍ、Ｓｖ１．５１μｍ、Ｖ１８．９％の導電粒子を製造した。Ｎｉ被覆層の層厚は１５５ｎｍ、突起の高さは３５６ｎｍであった。 The temperature of the 3 L reactor was maintained at 65 ° C., and the solution (b) was added at a rate of 20 mL / min for 5 minutes with a metering pump while stirring at 250 rpm, and the rest was charged at 8 mL / min. (B) When all the solutions were added, the reaction was maintained for 20 minutes to produce conductive particles having an average diameter of 8.01 μm, Sv 1.51 μm, and V18.9%. The thickness of the Ni coating layer was 155 nm, and the height of the protrusion was 356 nm.
この際、コア樹脂微粒子及び導電粒子の平均直径は、Ｐａｒｔｉｃｌｅ Ｓｉｚｅ Ａｎａｌｙｚｅｒ（ＢＥＣＫＭＡＮ ＭＵＬＴＩＳＩＺＥＲ ＴＭ３）を用いて測定されたモード値を用いた。測定されたコア樹脂微粒子及び導電粒子の数は１５０，０００個であった。また、導電粒子の平均直径は、突起を除いた部分の平均直径である。 At this time, the average values of the core resin fine particles and the conductive particles used were mode values measured using a Particle Size Analyzer (BECKMAN MULTISIZER TM3). The number of measured core resin fine particles and conductive particles was 150,000. The average diameter of the conductive particles is the average diameter of the portion excluding the protrusions.
また、圧縮変形量は、１辺の長さが５０μｍの平面圧子（Ｉｎｄｅｎｔｅｒ）を用いて、微小圧縮試験機（ＦＩＳＨＥＲＳＣＯＰＥ ＨＭ２０００）で測定した。圧縮変形量は、５個の導電粒子を測定し、その平均値（算術平均値）とした。具体的に、２５℃でホットプレートを加熱し、その上に導電粒子をのせ、圧子（Ｉｎｄｅｎｔｅｒ）の下降速度を０．３３ｍＮ／ｓｅｃにしてＭＡＸ ５０ｍＮの力で測定し、導電粒子の変形した圧縮変形量を測定した。また、変曲点が発生した際の外力を変曲点発生力として測定した。変曲点発生力については表１に他の実施例及び比較例とまとめて示す。 The amount of compressive deformation was measured with a micro compression tester (FISHERSCOPE HM2000) using a flat indenter (Indenter) having a side length of 50 μm. The amount of compressive deformation was determined by measuring five conductive particles and averaging them (arithmetic average value). Specifically, a hot plate is heated at 25 ° C., conductive particles are placed thereon, the indenter descending speed is set to 0.33 mN / sec, and measured with a force of MAX 50 mN. The amount of deformation was measured. The external force when the inflection point was generated was measured as the inflection point generation force. The inflection point generation force is shown in Table 1 together with other examples and comparative examples.
（実施例２）
実施例１の前処理においてメチルメタクリレートモノマー１４０ｇとジビニルベンゼンモノマー１０ｇを用いた他は、実施例１の前処理と同様の処理を行うことで、平均直径７．６μｍのコア樹脂微粒子を作製した。その後、実施例１と同様の処理を行ったが、メッキ処理においては、溶液（ｂ）を５分間２０ｍＬ／ｍｉｎの速度で投入した後、残りは１０ｍＬ／ｍｉｎの速度で投入した。これにより、平均直径８．０５μｍ、Ｓｖ１．３２μｍ、Ｖ１６．４％、被覆層の層厚２２５ｎｍ、突起の高さ２７５ｎｍの導電粒子を製造した。
(Example 2)
Core resin fine particles having an average diameter of 7.6 μm were prepared by performing the same treatment as that of Example 1 except that 140 g of methyl methacrylate monomer and 10 g of divinylbenzene monomer were used in the pretreatment of Example 1. Thereafter, the same treatment as in Example 1 was performed. In the plating treatment, the solution (b) was charged at a rate of 20 mL / min for 5 minutes, and the rest was charged at a rate of 10 mL / min. As a result, conductive particles having an average diameter of 8.05 μm, Sv of 1.32 μm, V16.4%, a coating layer thickness of 225 nm, and a protrusion height of 275 nm were produced.
（実施例３）
実施例１の前処理においてヘキサンジオールジアクリレートモノマー８５ｇとジビニルベンゼンモノマー８５ｇを用いた他は実施例１の前処理と同様の処理を行うことで、平均直径１０μｍのコア樹脂微粒子を作製した。その後、実施例１と同様の処理を行ったが、メッキ処理においては、コア樹脂微粒子の使用量を３０ｇ、硫酸ニッケルの使用量を１２０ｇ、次亜リン酸ナトリウムの使用量を１４０ｇに変更した。また、溶液（ｂ）を５分間２０ｍＬ／ｍｉｎの速度で投入した後、残りは１２ｍＬ／ｍｉｎの速度で投入した。これにより、平均直径１０．３μｍ、Ｓｖ１．６１μｍ、Ｖ１５．６％、被覆層の層厚１５０ｎｍおよび突起の高さ７２ｎｍの導電粒子を製造した。
(Example 3)
Core resin fine particles having an average diameter of 10 μm were prepared by performing the same treatment as that of Example 1 except that 85 g of hexanediol diacrylate monomer and 85 g of divinylbenzene monomer were used in the pretreatment of Example 1. Thereafter, the same treatment as in Example 1 was performed, but in the plating treatment, the amount of core resin fine particles used was changed to 30 g, the amount of nickel sulfate used was 120 g, and the amount of sodium hypophosphite used was changed to 140 g. Moreover, after charging the solution (b) at a rate of 20 mL / min for 5 minutes, the rest was charged at a rate of 12 mL / min. As a result, conductive particles having an average diameter of 10.3 μm, Sv of 1.61 μm, V of 15.6%, a coating layer thickness of 150 nm and a protrusion height of 72 nm were produced.
（実施例４）
実施例１の前処理においてポリエチレングリコールジメタクリレート＃４００モノマー８５ｇとエチルアクリレートモノマー８５ｇとを用いた他は、実施例１の前処理と同様の処理を行うことで、平均直径９．６６μｍのコア樹脂微粒子を作製した。その後、実施例１と同様の処理を行ったが、メッキ処理においては、コア樹脂微粒子の使用量を３０ｇ、硫酸ニッケルの使用量を１２０ｇ、次亜リン酸ナトリウムの使用量を１４０ｇに変更した。また、溶液（ｂ）を５分間２０ｍＬ／ｍｉｎの速度で投入した後、残りは９ｍＬ／ｍｉｎの速度で投入した。これにより、平均直径１０．１μｍ、Ｓｖ０．６２μｍ、Ｖ６．１％、被覆層の層厚２２０ｎｍおよび突起の高さ１５７ｎｍの導電粒子を製造した。
Example 4
A core resin having an average diameter of 9.66 μm is obtained by performing the same treatment as that of Example 1 except that 85 g of polyethylene glycol dimethacrylate # 400 monomer and 85 g of ethyl acrylate monomer are used in the pretreatment of Example 1. Fine particles were prepared. Thereafter, the same treatment as in Example 1 was performed, but in the plating treatment, the amount of core resin fine particles used was changed to 30 g, the amount of nickel sulfate used was 120 g, and the amount of sodium hypophosphite used was changed to 140 g. Further, the solution (b) was charged at a rate of 20 mL / min for 5 minutes, and the rest was charged at a rate of 9 mL / min. As a result, conductive particles having an average diameter of 10.1 μm, Sv of 0.62 μm, V6.1%, a layer thickness of the coating layer of 220 nm, and a protrusion height of 157 nm were produced.
（実施例５）
実施例１の前処理においてスチレンモノマー１５０ｇとジビニルベンゼンモノマー１０ｇを用いた他は、実施例１の前処理と同様の処理を行うことで、平均直径１４．９μｍのコア樹脂微粒子を作製した。その後、実施例１と同様の処理を行ったが、メッキ処理においては、コア樹脂微粒子の使用量を３０ｇ、硫酸ニッケルの使用量を１２０ｇ、次亜リン酸ナトリウムの使用量を１４０ｇに変更した。また、溶液（ｂ）を５分間２０ｍＬ／ｍｉｎの速度で投入した後、残りは８ｍＬ／ｍｉｎの速度で投入した。これにより、平均直径１５．４μｍ、Ｓｖ３．４μｍ、Ｖ２２．１％、被覆層の層厚２５０ｎｍおよび突起の高さ１８４ｎｍの導電粒子を製造した。
(Example 5)
Core resin fine particles having an average diameter of 14.9 μm were prepared by carrying out the same treatment as that of Example 1 except that 150 g of styrene monomer and 10 g of divinylbenzene monomer were used in the pretreatment of Example 1. Thereafter, the same treatment as in Example 1 was performed, but in the plating treatment, the amount of core resin fine particles used was changed to 30 g, the amount of nickel sulfate used was 120 g, and the amount of sodium hypophosphite used was changed to 140 g. Further, the solution (b) was charged at a rate of 20 mL / min for 5 minutes, and the rest was charged at a rate of 8 mL / min. As a result, conductive particles having an average diameter of 15.4 μm, Sv of 3.4 μm, V22.1%, a coating layer thickness of 250 nm, and a protrusion height of 184 nm were produced.
（実施例６）
実施例１の前処理においてスチレンモノマー８０ｇとメチルメタクリレートモノマー８０ｇとを用いた他は実施例１と同様の処理を行うことで平均直径３．９０μｍのコア樹脂微粒子を作製した。その後、実施例１と同様の処理を行ったが、メッキ処理においては、コア樹脂微粒子の使用量を２５ｇ、硫酸ニッケルの使用量を１２０ｇ、次亜リン酸ナトリウムの使用量を１４０ｇに変更した。また、溶液（ｂ）を５分間２０ｍＬ／ｍｉｎの速度で投入した後、残りは１２ｍＬ／ｍｉｎの速度で投入した。これにより、平均直径４．０８μｍ、Ｓｖ０．７８μｍ、Ｖ１９．５％、被覆層の層厚９０ｎｍおよび突起の高さ１０１ｎｍの導電粒子を製造した。
(Example 6)
Core resin fine particles having an average diameter of 3.90 μm were prepared by carrying out the same treatment as in Example 1 except that 80 g of styrene monomer and 80 g of methyl methacrylate monomer were used in the pretreatment of Example 1. Thereafter, the same treatment as in Example 1 was performed, but in the plating treatment, the amount of core resin fine particles used was changed to 25 g, the amount of nickel sulfate used was 120 g, and the amount of sodium hypophosphite used was changed to 140 g. Moreover, after charging the solution (b) at a rate of 20 mL / min for 5 minutes, the rest was charged at a rate of 12 mL / min. Thus, conductive particles having an average diameter of 4.08 μm, Sv of 0.78 μm, V of 19.5%, a coating layer thickness of 90 nm, and a protrusion height of 101 nm were produced.
（実施例７）
実施例１で製造された導電粒子にＡｕメッキを施すことで、平均粒径８．０μｍ、Ｓｖ１．５μｍ、Ｖ１８．８％、Ｎｉ／Ａｕ被覆層の層厚１５０ｎｍおよび突起の高さ３４０ｎｍのＮｉ／Ａｕ導電粒子を製造した。なお、Ａｕメッキは、Ｎｉ金属との置換反応により行われた。このため、Ｎｉ／Ａｕ被覆層の厚さは、実施例１のＮｉ被覆層の厚さと略同一となる。
(Example 7)
By subjecting the conductive particles produced in Example 1 to Au plating, Ni having an average particle size of 8.0 μm, Sv of 1.5 μm, V18.8%, a Ni / Au coating layer thickness of 150 nm, and a protrusion height of 340 nm. / Au conductive particles were produced. In addition, Au plating was performed by substitution reaction with Ni metal. For this reason, the thickness of the Ni / Au coating layer is substantially the same as the thickness of the Ni coating layer of Example 1.
（実施例８）
活性化核形成処理を行わなかったこと、及びメッキ処理において溶液（ｂ）を定量ポンプで２０ｍＬ／ｍｉｎの速度で添加し、しかる後に、２０分間反応を維持させたこと以外は実施例１と同様の処理を行った。これにより、平均直径８．２μｍ、Ｓｖ１．５２μｍ、Ｖ１８．５％および被覆層の層厚２５０ｎｍを有する、突起のない導電粒子を製造した。
(Example 8)
The same as in Example 1 except that the activated nucleation treatment was not performed and the solution (b) was added at a rate of 20 mL / min with a metering pump in the plating treatment, and then the reaction was maintained for 20 minutes. Was processed. As a result, conductive particles without protrusions having an average diameter of 8.2 μm, Sv of 1.52 μm, V of 18.5% and a coating layer thickness of 250 nm were produced.
（実施例９）
実施例８で製造された導電粒子にＡｕメッキを施すことで、平均直径８．２μｍ、Ｓｖ１．５０μｍ、Ｖ１８．３％およびＮｉ／Ａｕ被覆層の層厚２５０ｎｍを有する、突起のないＮｉ／Ａｕ導電粒子を製造した。なお、Ａｕめっきは、Ｎｉ金属との置換反応により行われた。このため、Ｎｉ／Ａｕ被覆層の厚さは、実施例８のＮｉ被覆層の厚さと略同一になる。
Example 9
By applying Au plating to the conductive particles produced in Example 8, Ni / Au without protrusions having an average diameter of 8.2 μm, Sv of 1.50 μm, V18.3% and a Ni / Au coating layer thickness of 250 nm. Conductive particles were produced. In addition, Au plating was performed by substitution reaction with Ni metal. For this reason, the thickness of the Ni / Au coating layer is substantially the same as the thickness of the Ni coating layer of Example 8.
（実施例１０）
実施例１の前処理で製造されたコア樹脂微粒子にＣｕメッキを施した。ＣｕメッキはＣｕめっき液ＭＳ−ＫＡＰＡ（ＭＳＣ社製）製品を使用した。これにより、平均直径７．９μｍ、Ｓｖ１．３０μｍ、Ｖ１６．５％および被覆層の層厚１００ｎｍを有する、突起のない導電粒子を製造した。
(Example 10)
The core resin fine particles produced by the pretreatment of Example 1 were subjected to Cu plating. For Cu plating, a Cu plating solution MS-KAPA (manufactured by MSC) was used. As a result, conductive particles without protrusions having an average diameter of 7.9 μm, Sv 1.30 μm, V 16.5% and a coating layer thickness of 100 nm were produced.
（実施例１１）
２Ｌの反応器にＤＩＷ（脱イオン水）５００ｇおよびＥｔＯＨ５００ｇを仕込み、アクリルアミド２ｇと少量の界面活性剤を添加し、１２０ｍＬのＡｇ２ｇを溶液に添加した後、溶液を６５℃に２時間維持した。その後、実施例８で製造された導電粒子２０ｇを上記溶液に入れて２５０ｒｐｍで１２時間維持することで、平均直径８．２μｍ、Ｓｖ１．４３μｍ、Ｖ１７．４％、被覆層の層厚２５０ｎｍおよび突起の高さ１２０ｎｍのＮｉ／Ａｇ突起付き導電粒子を製造した。
(Example 11)
A 2 L reactor was charged with 500 g DIW (deionized water) and 500 g EtOH, 2 g acrylamide and a small amount of surfactant were added, 120 mL Ag 2 g was added to the solution, and then the solution was maintained at 65 ° C. for 2 hours. Thereafter, 20 g of the conductive particles produced in Example 8 were placed in the above solution and maintained at 250 rpm for 12 hours, whereby an average diameter of 8.2 μm, Sv of 1.43 μm, V of 17.4%, a coating layer thickness of 250 nm and protrusions The conductive particles with Ni / Ag protrusions having a height of 120 nm were produced.
（比較例１）
実施例１の前処理においてモノマーエチレングリコールジメタクリレート８５ｇとジビニルベンゼンモノマー８５ｇを用いた他は実施例１と同様の処理を行うことで平均直径８．８μｍのコア樹脂微粒子を作製した。その後、実施例１と同様の処理を行ったが、メッキ処理においては、コア樹脂微粒子５５ｇを用いた。これにより、平均直径９．１μｍ、Ｓｖ４．２５μｍおよびＶ４６．７％の導電粒子を製造した。Ｎｉ被覆層の層厚は１５０ｎｍ、突起の高さは１５４ｎｍであった。
(Comparative Example 1)
Core resin fine particles having an average diameter of 8.8 μm were prepared by performing the same treatment as in Example 1 except that 85 g of monomer ethylene glycol dimethacrylate and 85 g of divinylbenzene monomer were used in the pretreatment of Example 1. Thereafter, the same treatment as in Example 1 was performed, but 55 g of core resin fine particles were used in the plating treatment. As a result, conductive particles having an average diameter of 9.1 μm, Sv 4.25 μm, and V46.7% were manufactured. The thickness of the Ni coating layer was 150 nm, and the height of the protrusion was 154 nm.
（比較例２）
実施例１の前処理においてエチレングリコールジメタクリレートモノマー１００ｇとジビニルベンゼンモノマー６０ｇとを用いた他は、実施例１の前処理と同様の処理を行うことで、平均直径４．０μｍのコア樹脂微粒子を作製した。その後、実施例１と同様の処理を行ったが、メッキ処理においては、コア樹脂微粒子の使用量を３０ｇとした。これにより、平均直径４．２５μｍ、Ｓｖ２．５５μｍ、Ｖ４６．７％、被覆層の層厚１２５ｎｍおよび突起の高さ１３５ｎｍの導電粒子を製造した。
(Comparative Example 2)
The core resin fine particles having an average diameter of 4.0 μm were obtained by performing the same treatment as that of Example 1 except that 100 g of ethylene glycol dimethacrylate monomer and 60 g of divinylbenzene monomer were used in the pretreatment of Example 1. Produced. Thereafter, the same treatment as in Example 1 was performed, but the amount of the core resin fine particles used was 30 g in the plating treatment. Thus, conductive particles having an average diameter of 4.25 μm, Sv 2.55 μm, V46.7%, a coating layer thickness of 125 nm, and a protrusion height of 135 nm were manufactured.
（実験例）
（実験例１：接続抵抗の測定）
接続抵抗を測定するためにエポキシ樹脂と前記導電粒子を混合し、フィルム状に作って電極と接合させた後、初期抵抗を測定した。
(Experimental example)
(Experimental example 1: measurement of connection resistance)
In order to measure the connection resistance, the epoxy resin and the conductive particles were mixed, formed into a film, joined to the electrode, and then the initial resistance was measured.
これによれば、本発明の実施例に係る６≦Ｖ≦２５であり、かつ、変曲点発生力が１．０〜１５ｍＮであるものの抵抗が低いことが分かる。また、これらの条件が成立し、かつ、平均直径が４〜１６μｍ、被覆層の厚さが３０〜４００ｎｍ、または突起の高さが５０ｎｍ〜５００ｎｍとなる場合には、初期抵抗が特に低くなる。 According to this, it can be seen that the resistance is low although 6 ≦ V ≦ 25 according to the embodiment of the present invention and the inflection point generation force is 1.0 to 15 mN. In addition, when these conditions are satisfied and the average diameter is 4 to 16 μm, the thickness of the coating layer is 30 to 400 nm, or the height of the protrusion is 50 nm to 500 nm, the initial resistance is particularly low.
以上、本発明の実施例について説明したが、本発明は、上述した実施例に限定されず、本発明の属する分野における通常の知識を有する者であれば、本発明の概念を外れることなく変形を加えることが可能である。それらの変形は本発明の範囲に属する。 Although the embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments, and any person having ordinary knowledge in the field to which the present invention belongs can be modified without departing from the concept of the present invention. Can be added. These variations belong to the scope of the present invention.
前述した発明に対する権利範囲は、特許請求の範囲によって定められるものであって、明細書本文の記載にはなんら拘束されない。さらに、特許請求の範囲の均等範囲に属する変形や変更はすべて本発明の範囲内のものである。 The scope of the right to the invention described above is defined by the scope of the claims, and is not restricted by the description of the specification. Further, all modifications and changes belonging to the equivalent scope of the claims are within the scope of the present invention.
Claims (19)
当該導電粒子は、樹脂微粒子、および前記樹脂微粒子の外面に形成される被覆層を有し、
前記導電粒子を圧縮変形させる場合、前記導電粒子の変形増加率の増加が発生する時点よりも前では、前記導電粒子は弾性変形をし、当該時点よりも後では、前記導電粒子は、塑性変形（前記導電粒子全体が破壞される場合は除く）することを特徴とする導電粒子。 Conductive particles that electrically connect a plurality of electrodes to each other,
The conductive particles have resin fine particles and a coating layer formed on the outer surface of the resin fine particles,
When the conductive particles are compressively deformed, the conductive particles undergo elastic deformation before the time point at which the deformation increase rate of the conductive particles increases, and after the time point, the conductive particles are plastically deformed. Conductive particles (except when the entire conductive particles are broken).
（式１）
Ｖ（％）＝Ｓｖ／Ｄ＊１００
（式中、Ｖは変曲開始変形率を示し、Ｓｖは前記導電粒子を前記導電粒子に加える外力（ｌｏａｄ）を増加させたときに前記導電粒子の前記変形増加率（＝△圧縮変形量／△外力）の増加が発生する時点の圧縮変形量を示し、Ｄは前記導電粒子の平均直径（μｍ）を示し、前記変形増加率の増加が開始する時点における前記外力は、１.９〜１３.５ｍＮである。） 6. The inflection start deformation rate (V value) represented by the following formula 1 of the conductive particles has a V value of 6 ≦ V ≦ 25, according to claim 1, wherein: Conductive particles.
(Formula 1)
V (%) = Sv / D * 100
(Where V represents the inflection start deformation rate, and Sv represents the deformation increase rate of the conductive particles when the external force (load) applied to the conductive particles is increased (= Δ compression deformation amount / [Delta] indicates the amount of compressive deformation at the time when an increase in external force occurs, D indicates the average diameter ([mu] m) of the conductive particles, and the external force at the time when the increase in deformation increases starts is 1.9 to 13 .5mN.)
タッチスクリーンパネル用導電粒子として、樹脂微粒子、および前記樹脂微粒子の外面に形成される被覆層を有する導電粒子を用い、
当該導電粒子の平均直径は、４μｍ〜１６μｍであり、
前記被覆層の厚さは、１００ｎｍ〜２５０ｎｍであり、
下記式１による変曲開始変形率（Ｖ値）が６≦Ｖ≦２５であり、
前記導電粒子を圧縮変形させる場合、前記導電粒子の変形増加率の増加が発生する時点よりも前では、前記導電粒子は弾性変形をし、当該時点よりも後では、前記導電粒子は、塑性変形（前記導電粒子全体が破壞される場合は除く）することを特徴とする方法。
（式１）
Ｖ（％）＝Ｓｖ／Ｄ＊１００
（式中、Ｖは変曲開始変形率を示し、Ｓｖは前記導電粒子を前記導電粒子に加える外力（ｌｏａｄ）を増加させたときに前記導電粒子の前記変形増加率（＝△圧縮変形量／△外力）の増加が発生する時点の圧縮変形量を示し、Ｄは前記導電粒子の平均直径（μｍ）を示し、前記変形増加率の増加が開始する時点における前記外力は、１．９〜１３．５ｍＮである。） A method for preventing a short circuit between electrodes while preventing destruction of the electrodes of the touch panel,
As conductive particles for touch screen panel, using conductive particles having resin fine particles and a coating layer formed on the outer surface of the resin fine particles,
The average diameter of the conductive particles is 4 μm to 16 μm,
The coating layer has a thickness of 100 nm to 250 nm,
The inflection start deformation rate (V value) according to the following formula 1 is 6 ≦ V ≦ 25,
When the conductive particles are compressively deformed, the conductive particles undergo elastic deformation before the time point at which the deformation increase rate of the conductive particles increases, and after the time point, the conductive particles are plastically deformed. (Excluding the case where the entire conductive particle is broken).
(Formula 1)
V (%) = Sv / D * 100
(Where V represents the inflection start deformation rate, and Sv represents the deformation increase rate of the conductive particles when the external force (load) applied to the conductive particles is increased (= Δ compression deformation amount / Δ represents the amount of compressive deformation at the time when the increase in external force occurs, D represents the average diameter (μm) of the conductive particles, and the external force at the time when the increase in the deformation increase rate starts is 1.9 to 13 .5mN.)
The method according to claim 18, wherein the inflection point generation force of the conductive particles is 1.0 to 15 mN.
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