JP4589810B2 - Conductive fine particles and anisotropic conductive materials - Google Patents
Conductive fine particles and anisotropic conductive materials Download PDFInfo
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Description
本発明は、導通不良防止とともに抵抗値の低減化が可能な導電性微粒子及び異方性導電材料に関する。 The present invention relates to a conductive fine particle and an anisotropic conductive material capable of preventing conduction failure and reducing a resistance value.
導電性微粒子は、バインダー樹脂や粘接着剤等と混合、混練することにより、例えば、異方性導電ペースト、異方性導電インク、異方性導電粘接着剤、異方性導電フィルム、異方性導電シート等の異方性導電材料として広く用いられている。 The conductive fine particles are mixed and kneaded with a binder resin or an adhesive, for example, an anisotropic conductive paste, an anisotropic conductive ink, an anisotropic conductive adhesive, an anisotropic conductive film, Widely used as anisotropic conductive materials such as anisotropic conductive sheets.
これらの異方性導電材料は、例えば、液晶ディスプレイ、パーソナルコンピュータ、携帯電話等の電子機器において、回路基板同士を電気的に接続したり、半導体素子等の小型部品を回路基板に電気的に接続したりするために、相対向する回路基板や電極端子の間に挟み込んで使用されている。 These anisotropic conductive materials are used to electrically connect circuit boards to each other, for example, in electronic devices such as liquid crystal displays, personal computers, and mobile phones, and to electrically connect small components such as semiconductor elements to the circuit board. For this reason, it is used by being sandwiched between circuit boards and electrode terminals facing each other.
このような異方性導電材料に用いられる導電性微粒子としては、従来、粒子径が均一で、適度な強度を有する樹脂粒子等の非導電性微粒子の表面に、導電層として金属メッキ層を形成させた導電性微粒子が用いられている。しかしながら、このような異方性導電材料を用いて回路基板同士を電気的に接続すると、導電性微粒子表面の導電層と回路基板等との間にバインダー樹脂等がはさまり、導電性微粒子と回路基板等との間の接続抵抗が高くなることがあった。特に近年の電子機器の急激な進歩や発展に伴って、導電性微粒子と回路基板等との間の接続抵抗の更なる低減が求められてきている。 As the conductive fine particles used for such anisotropic conductive materials, conventionally, a metal plating layer is formed as a conductive layer on the surface of non-conductive fine particles such as resin particles having a uniform particle size and appropriate strength. Conductive fine particles are used. However, when the circuit boards are electrically connected using such an anisotropic conductive material, a binder resin or the like is sandwiched between the conductive layer on the surface of the conductive fine particles and the circuit board. In some cases, the connection resistance between them and the like increases. In particular, with the rapid progress and development of electronic devices in recent years, there has been a demand for further reduction in connection resistance between conductive fine particles and circuit boards.
接続抵抗を低減する目的で、表面に突起を有する導電性微粒子が開示されている（例えば、特許文献１参照）。この導電性微粒子は、導電性微粒子表面の導電層と回路基板等との間に存在するバインダー樹脂等を突起が突き破ることで（樹脂排除性）、突起と回路基板等とを確実に接続させることで、導電性微粒子と回路基板等との間の接続抵抗の低減化を図っている。 For the purpose of reducing connection resistance, conductive fine particles having protrusions on the surface are disclosed (for example, see Patent Document 1). This conductive fine particle ensures that the protrusion and the circuit board are connected by the protrusion breaking through the binder resin or the like existing between the conductive layer on the surface of the conductive fine particle and the circuit board. Therefore, the connection resistance between the conductive fine particles and the circuit board is reduced.
しかしながら、このような表面に突起を有する導電性微粒子を用いても、突起の大きさによっては突起と突起との間に樹脂噛みが生じたり、バインダー樹脂等を突起が突き破ることができないことがあったりするため、導電性微粒子と回路基板等との間の接続抵抗の低減化が充分に図られているとは言えなかった。
本発明は、上記現状に鑑み、導通不良防止とともに抵抗値の低減化が可能な導電性微粒子及び異方性導電材料を提供することを目的とする。 An object of the present invention is to provide conductive fine particles and an anisotropic conductive material capable of preventing conduction failure and reducing the resistance value in view of the above-described present situation.
本発明は、基材微粒子と、前記基材微粒子の表面に形成された導電層とからなる導電性微粒子であって、前記導電層は、表面に高さが２００〜４００ｎｍの突起Ａと５０〜１００ｎｍの突起Ｂとを有し、突起Ａの数をａ、突起Ｂの数をｂとするとき、３＜ａ／ｂ＜１０を満たす導電性微粒子である。
以下に本発明を詳述する。
The present invention is a conductive fine particle comprising a substrate fine particle and a conductive layer formed on the surface of the substrate fine particle, wherein the conductive layer has a protrusion A having a height of 200 to 400 nm on the surface and 50 to 50- The conductive fine particles satisfying 3 <a / b <10 when the number of protrusions A is a and the number of protrusions B is b.
The present invention is described in detail below.
本発明者らは、鋭意検討の結果、回路基板等の電気的接続に用いる導電性微粒子として、大小異なる突起を有する導電性微粒子を用いることで、突起間の樹脂噛みを防ぐことができるのに加え、樹脂排除して確実に導電性微粒子と回路基板等とを接触させることができることにより、回路基板と導電性微粒子とを確実に導電接続させることができ、接続抵抗を低減することができるということを見出し、本発明を完成させるに至った。 As a result of intensive studies, the present inventors have been able to prevent resin biting between protrusions by using conductive fine particles having protrusions of different sizes as conductive fine particles used for electrical connection of a circuit board or the like. In addition, since the conductive fine particles can be reliably brought into contact with the circuit board by eliminating the resin, the circuit board and the conductive fine particles can be reliably conductively connected, and the connection resistance can be reduced. As a result, the present invention has been completed.
本発明の導電性微粒子は、基材微粒子と、上記基材微粒子の表面に形成された導電層とからなる導電性微粒子である。 The conductive fine particles of the present invention are conductive fine particles composed of substrate fine particles and a conductive layer formed on the surface of the substrate fine particles.
上記基材微粒子としては特に限定されず、適度な弾性率、弾性変形性及び復元性を有するものであれば無機材料を用いてなるものでも有機材料を用いてなるものでもよいが、弾性変形性及び復元性に優れていることから、樹脂を用いてなる樹脂粒子であることが好ましい。 The substrate fine particles are not particularly limited, and may be made of an inorganic material or an organic material as long as it has an appropriate elastic modulus, elastic deformability, and resilience. And since it is excellent in the restoring property, it is preferable that it is a resin particle using resin.
上記樹脂粒子を構成する樹脂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、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリテトラフルオロエチレン、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；アクリレートとジビニルベンゼンとの共重合樹脂、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、メラニンホルムアルデヒド樹脂、ベンゾグアナミンホルムアルデヒド樹脂、尿素ホルムアルデヒド樹脂等が挙げられる。これらの樹脂は、単独で用いられてもよいし、２種以上が併用されてもよい。 The resin constituting the resin particles is not particularly limited. For example, polyolefin such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene, polyisobutylene, polybutadiene; polymethyl methacrylate, polymethyl acrylate Acrylic resin such as acrylate and divinylbenzene, polyalkylene terephthalate, polysulfone, polycarbonate, polyamide, phenol formaldehyde resin, melanin formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin and the like. These resins may be used alone or in combination of two or more.
上記基材微粒子の平均粒子径としては特に限定されないが、好ましい下限は１μｍ、好ましい上限は２０μｍである。１μｍ未満であると、例えば、無電解メッキをする際に凝集しやすく、単粒子としにくくなることがあり、２０μｍを超えると、異方性導電材料として回路基板等に用いられる範囲を超えることがある。
なお、上記基材微粒子の平均粒子径は、無作為に選んだ５０個の基材微粒子について粒子径を測定し、これらを算術平均したものとする。
Although it does not specifically limit as an average particle diameter of the said base material fine particle, A preferable minimum is 1 micrometer and a preferable upper limit is 20 micrometers. If it is less than 1 μm, for example, it is likely to aggregate when electroless plating is performed, and it may be difficult to form single particles. If it exceeds 20 μm, it may exceed the range used for circuit boards and the like as anisotropic conductive materials. is there.
In addition, the average particle diameter of the said base material fine particle shall measure the particle diameter about 50 base material microparticles | fine-particles selected at random, and shall mean these arithmetically.
上記導電層は、表面に高さが２００〜４００ｎｍの突起Ａと５０〜１００ｎｍの突起Ｂとを有する。
本発明の導電性微粒子においては、突起Ａにより回路基板等と本発明の導電性微粒子との間に存在する異方性導電材料中のバインダー樹脂等を突き破るとともに（樹脂排除性）、突起Ｂにより突起Ａ同士の間の存在する異方性導電材料中のバインダー樹脂（樹脂噛み）を排除することが可能となり、導通不良防止とともに、抵抗値の低減化が可能となる。
突起Ａの高さが２００ｎｍ未満であると、充分な樹脂排除性が得られず、４００ｎｍを超えると、突起が回路基板等に深くめり込み、回路基板等を破損するおそれがある。
また、突起Ｂの高さが５０ｎｍ未満であると、充分に樹脂噛みを排除することができず、１００ｎｍを超えると、本発明の導電性微粒子を回路基板等の間に挟んで用いた場合に突起がつぶれにくくなる。
The conductive layer has a protrusion A having a height of 200 to 400 nm and a protrusion B having a height of 50 to 100 nm on the surface.
In the conductive fine particle of the present invention, the protrusion A breaks through the binder resin or the like in the anisotropic conductive material existing between the circuit board or the like and the conductive fine particle of the present invention (resin eliminability). It is possible to eliminate the binder resin (resin bite) in the anisotropic conductive material existing between the protrusions A, and it is possible to prevent conduction failure and reduce the resistance value.
If the height of the protrusion A is less than 200 nm, sufficient resin eliminability cannot be obtained, and if it exceeds 400 nm, the protrusion may dig deep into the circuit board and the like, possibly damaging the circuit board.
Further, if the height of the protrusion B is less than 50 nm, the resin biting cannot be sufficiently eliminated, and if it exceeds 100 nm, the conductive fine particles of the present invention are sandwiched between circuit boards and the like. Protrusions are less likely to collapse.
上記導電層としては特に限定されないが、メッキがしやすく低抵抗であることからニッケルを含有することが好ましい。 The conductive layer is not particularly limited, but preferably contains nickel because it is easy to plate and has low resistance.
上記導電層の厚さとしては特に限定されないが、好ましい下限は１０ｎｍ、好ましい上限は５００ｎｍである。１０ｎｍ未満であると、所望の導電性が得られないことがあり、５００ｎｍを超えると、基材微粒子と導電層との熱膨張率の差から、上記導電層が剥離しやすくなることがある。
なお、上記導電層の厚さは、無作為に選んだ１０個の粒子について測定し、これらを算術平均した厚さである。
Although it does not specifically limit as thickness of the said conductive layer, A preferable minimum is 10 nm and a preferable upper limit is 500 nm. If the thickness is less than 10 nm, desired conductivity may not be obtained. If the thickness exceeds 500 nm, the conductive layer may be easily peeled off due to the difference in thermal expansion coefficient between the substrate fine particles and the conductive layer.
Note that the thickness of the conductive layer is a thickness obtained by measuring ten randomly selected particles and arithmetically averaging them.
上記突起のうち、突起Ａの数をａ、突起Ｂの数をｂとするとき、３＜ａ／ｂ＜１０である。ａ／ｂが３未満であると、充分な樹脂排除性が得られず、１０を超えると、突起間に樹脂噛みが発生しやすくなる。 Of the protrusions, 3 <a / b <10, where a is the number of protrusions A and b is the number of protrusions B. If a / b is less than 3, sufficient resin exclusion properties cannot be obtained, and if it exceeds 10, resin biting tends to occur between the protrusions.
突起Ａは、芯材を有することが好ましい。芯材を有していることにより、突起の高さを所望の範囲にすることが可能となり、上述したような接続抵抗の低減化等の効果を得ることができる。 The protrusion A preferably has a core material. By having a core material, it becomes possible to make the height of a protrusion into a desired range, and effects, such as a reduction in connection resistance as described above, can be obtained.
上記芯材を構成する物質としては特に限定されず、例えば、金属（合金を含む）、金属の酸化物、黒鉛等の導電性非金属、樹脂等が挙げられる。なかでも、本発明の導電性微粒子を回路基板等の間に挟んで導電接続する際に回路基板等の面で突起Ａがつぶれやすくなり、本発明の導電性微粒子と回路基板等との接続抵抗値を低減することが可能となることから、樹脂が好適に用いられる。 The substance constituting the core material is not particularly limited, and examples thereof include metals (including alloys), metal oxides, conductive nonmetals such as graphite, and resins. In particular, when the conductive fine particles of the present invention are sandwiched between the circuit boards and the like for conductive connection, the protrusions A are easily crushed on the surface of the circuit boards and the like, and the connection resistance between the conductive fine particles of the present invention and the circuit boards and the like Since the value can be reduced, a resin is preferably used.
上記樹脂としては回路基板等の面で突起Ａがつぶれる程度の軟らかさを有するものであれば特に限定されず、例えば、ポリアセチレン、ポリエチレン、ポリプロピレン、ポリメチルメタクリレート、ポリアミド、ポリスチレン、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリスルフォン、ポリフェニレンオキサイド、ポリアセタール、エポキシ樹脂、フェノール樹脂、メラミン樹脂、不飽和ポリエステル樹脂、ジビニルベンゼン重合体、ジビニルベンゼン−スチレン共重合体、ジビニルベンゼン−アクリル酸エステル共重合体、ジアリルフタレート重合体、トリアリルイソシアネート重合体、ベンゾグアナミン重合体等が挙げられる。 The resin is not particularly limited as long as it has such a softness that the protrusion A is crushed on the surface of a circuit board or the like. For example, polyacetylene, polyethylene, polypropylene, polymethyl methacrylate, polyamide, polystyrene, polyethylene terephthalate, polybutylene Terephthalate, polysulfone, polyphenylene oxide, polyacetal, epoxy resin, phenol resin, melamine resin, unsaturated polyester resin, divinylbenzene polymer, divinylbenzene-styrene copolymer, divinylbenzene-acrylic acid ester copolymer, diallylphthalate heavy Examples thereof include coalescence, triallyl isocyanate polymer, and benzoguanamine polymer.
上記金属としては特に限定されず、例えば、金、銀、銅、白金、亜鉛、鉄、鉛、錫、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；錫−鉛合金、錫−銅合金、錫−銀合金、錫−鉛−銀合金等の２種類以上の金属で構成される合金等が挙げられる。なかでも、ニッケル、銅、銀、金等が好ましい。上記芯材を構成する金属は、上記導電層を構成する金属と同じであってもよく、異なっていてもよいが、同じ金属により構成する場合には、芯材と導電層との添加剤成分等の含有割合を異ならせることが好ましい。 The metal is not particularly limited. For example, a metal such as gold, silver, copper, platinum, zinc, iron, lead, tin, aluminum, cobalt, indium, nickel, chromium, titanium, antimony, bismuth, germanium, cadmium; Examples of the alloy include two or more kinds of metals such as a tin-lead alloy, a tin-copper alloy, a tin-silver alloy, and a tin-lead-silver alloy. Of these, nickel, copper, silver, gold and the like are preferable. The metal constituting the core material may be the same as or different from the metal constituting the conductive layer, but in the case of being composed of the same metal, the additive component of the core material and the conductive layer It is preferable to vary the content ratio of the like.
上記突起Ａ、上記突起Ｂ、及び、本発明の導電性微粒子を製造する方法としては特に限定されないが、例えば、次のような方法が挙げられる。
まず、基材微粒子の表面に触媒付与を行い、ヘテロ凝集により該基材微粒子の表面に芯材となる樹脂を付着させるか、又は、該基材微粒子を脱イオン水に分散させ、金属粒子スラリーを添加し、該基材微粒子の表面に芯材となる金属を付着させる。
次いで、メッキ安定剤を含有する水溶液に上記基材微粒子を分散させ、この水溶液にメッキ安定剤、次亜リン酸ナトリウムを含有するニッケルメッキ液を添加することで芯材がニッケルにより被覆されてなる突起Ａを有する導電性微粒子を製造することができる。更に、この導電性微粒子に対して錯化剤及び結晶調整剤の濃度が低い金メッキ浴を用いて還元金メッキ法を行うことにより、金の異常析出による突起Ｂをも有する本発明の導電性微粒子を製造することができる。
ここで、上記触媒付与を行う方法としては、例えば、アルカリ溶液でエッチングされた基材粒子に酸中和、及び、二塩化スズ（ＳｎＣｌ２）溶液におけるセンシタイジングを行い、二塩化パラジウム（ＰｄＣｌ２）溶液におけるアクチベイジングを行う無電解メッキ前処理工程を行う方法等が挙げられる。
なお、センシタイジングとは、絶縁物質の表面にＳｎ２＋イオンを吸着させる工程であり、アクチベイチングとは、絶縁性物質表面にＳｎ２＋＋Ｐｄ２＋→Ｓｎ４＋＋Ｐｄ０で示される反応を起こしてパラジウムを無電解メッキの触媒核とする工程である。
Although it does not specifically limit as a method of manufacturing the said processus | protrusion A, the said processus | protrusion B, and the electroconductive fine particles of this invention, For example, the following methods are mentioned.
First, a catalyst is applied to the surface of the base particle, and a resin as a core material is attached to the surface of the base particle by heteroaggregation, or the base particle is dispersed in deionized water, and a metal particle slurry Is added, and a metal as a core material is adhered to the surface of the substrate fine particles.
Next, the base material fine particles are dispersed in an aqueous solution containing a plating stabilizer, and a nickel plating solution containing a plating stabilizer and sodium hypophosphite is added to the aqueous solution to coat the core material with nickel. Conductive fine particles having protrusions A can be produced. Furthermore, the conductive fine particles of the present invention having protrusions B due to abnormal precipitation of gold can be obtained by performing a reduced gold plating method on the conductive fine particles using a gold plating bath having a low concentration of the complexing agent and the crystal modifier. Can be manufactured.
Here, as a method for applying the catalyst, for example, acid neutralization and sensitizing in a tin dichloride (SnCl 2 ) solution are performed on the substrate particles etched with an alkaline solution, and palladium dichloride (PdCl 2 ) A method of performing an electroless plating pretreatment step for activating in solution.
Sensitizing is a process in which Sn 2+ ions are adsorbed on the surface of an insulating material, and activating is a reaction represented by Sn 2+ + Pd 2+ → Sn 4+ + Pd 0 on the surface of an insulating material. In this process, palladium is used as a catalyst core for electroless plating.
また、上記方法において、金の異常析出による凝集体からなる突起Ｂのかわりに、上記触媒となるパラジウム等の量を多くしたり、メッキ安定剤の量を少なくしてニッケルメッキ反応時のニッケルメッキ液を不安定化させたりすることにより、ニッケルの異常析出による突起Ｂとする方法も挙げられる。この場合には、このニッケルメッキ工程の後、従来公知の置換金メッキ法等により金メッキ工程を行えばよい。 Further, in the above method, instead of the protrusions B formed of aggregates due to abnormal precipitation of gold, the amount of palladium or the like as the catalyst is increased, or the amount of the plating stabilizer is decreased to reduce the nickel plating during the nickel plating reaction. A method of forming the protrusion B by abnormal precipitation of nickel by destabilizing the liquid is also mentioned. In this case, after the nickel plating step, a gold plating step may be performed by a conventionally known displacement gold plating method or the like.
本発明の導電性微粒子をバインダー樹脂に分散させることにより異方性導電材料を製造することができる。このような異方性導電材料もまた、本発明の１つである。 An anisotropic conductive material can be produced by dispersing the conductive fine particles of the present invention in a binder resin. Such an anisotropic conductive material is also one aspect of the present invention.
本発明の異方性導電材料の具体的な例としては、例えば、異方性導電ペースト、異方性導電インク、異方性導電粘着剤層、異方性導電フィルム、異方性導電シート等が挙げられる。 Specific examples of the anisotropic conductive material of the present invention include, for example, anisotropic conductive paste, anisotropic conductive ink, anisotropic conductive adhesive layer, anisotropic conductive film, anisotropic conductive sheet and the like. Is mentioned.
上記樹脂バインダーとしては特に限定されないが、絶縁性の樹脂が用いられ、例えば、酢酸ビニル系樹脂、塩化ビニル系樹脂、アクリル系樹脂、スチレン系樹脂等のビニル系樹脂；ポリオレフィン系樹脂、エチレン−酢酸ビニル共重合体、ポリアミド系樹脂等の熱可塑性樹脂；エポキシ系樹脂、ウレタン系樹脂、ポリイミド系樹脂、不飽和ポリエステル系樹脂及びこれらの硬化剤からなる硬化性樹脂；スチレン−ブタジエン−スチレンブロック共重合体、スチレン−イソプレン−スチレンブロック共重合体、これらの水素添加物等の熱可塑性ブロック共重合体；スチレン−ブタジエン共重合ゴム、クロロプレンゴム、アクリロニトリル−スチレンブロック共重合ゴム等のエラストマー類（ゴム類）等が挙げられる。これらの樹脂は、単独で用いられてもよいし、２種以上が併用されてもよい。
また、上記硬化性樹脂は、常温硬化型、熱硬化型、光硬化型、湿気硬化型のいずれの硬化型であってもよい。
The resin binder is not particularly limited, and an insulating resin is used. For example, vinyl resins such as vinyl acetate resins, vinyl chloride resins, acrylic resins, styrene resins; polyolefin resins, ethylene-acetic acid Thermoplastic resins such as vinyl copolymers and polyamide resins; Epoxy resins, urethane resins, polyimide resins, unsaturated polyester resins, and curable resins composed of these curing agents; styrene-butadiene-styrene block copolymer Polymers, thermoplastic block copolymers such as styrene-isoprene-styrene block copolymers and hydrogenated products thereof; elastomers such as styrene-butadiene copolymer rubber, chloroprene rubber, acrylonitrile-styrene block copolymer rubber (rubbers) ) And the like. These resins may be used alone or in combination of two or more.
Further, the curable resin may be any curable type of room temperature curable type, heat curable type, photo curable type, and moisture curable type.
本発明の異方性導電材料には、本発明の導電性微粒子、及び、上記樹脂バインダーの他に、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、増量剤、軟化剤（可塑剤）、粘接着性向上剤、酸化防止剤（老化防止剤）、熱安定剤、光安定剤、紫外線吸収剤、着色剤、難燃剤、有機溶媒等の各種添加剤を添加してもよい。 In addition to the conductive fine particles of the present invention and the resin binder described above, the anisotropic conductive material of the present invention includes, for example, a bulking agent and a softening agent (if necessary) within a range not impairing the achievement of the problems of the present invention. Additives such as plasticizers), adhesive improvers, antioxidants (anti-aging agents), heat stabilizers, light stabilizers, UV absorbers, colorants, flame retardants, organic solvents, etc. Good.
本発明の異方性導電材料の製造方法としては特に限定されず、例えば、絶縁性の樹脂バインダー中に本発明の導電性微粒子を添加し、均一に混合して分散させ、例えば、異方性導電ペースト、異方性導電インク、異方性導電粘接着剤等とする方法や、絶縁性の樹脂バインダー中に本発明の導電性微粒子を添加し、均一に溶解（分散）させるか、又は、加熱溶解させて、離型紙や離型フィルム等の離型材の離型処理面に所定のフィルム厚さとなる用に塗工し、必要に応じて乾燥や冷却等を行って、例えば、異方性導電フィルム、異方性導電シート等とする方法等が挙げられ、製造しようとする異方性導電材料の種類に対応して、適宜の製造方法をとればよい。
また、絶縁性の樹脂バインダーと、本発明の導電性微粒子とを混合することなく、別々に用いて異方性導電材料としてもよい。
The method for producing the anisotropic conductive material of the present invention is not particularly limited. For example, the conductive fine particles of the present invention are added to an insulating resin binder, and are mixed and dispersed uniformly. A method of using a conductive paste, anisotropic conductive ink, anisotropic conductive adhesive, etc., adding the conductive fine particles of the present invention in an insulating resin binder and uniformly dissolving (dispersing), or , Heat-dissolve, and apply to the release treatment surface of the release material such as release paper and release film to have a predetermined film thickness, and perform drying and cooling as necessary, for example, anisotropic For example, an appropriate manufacturing method may be employed in accordance with the type of anisotropic conductive material to be manufactured.
Moreover, it is good also as an anisotropic conductive material by using separately, without mixing an insulating resin binder and the electroconductive fine particles of this invention.
本発明によれば、導通不良防止とともに抵抗値の低減化が可能な導電性微粒子及び異方性導電材料を提供することができる。 According to the present invention, it is possible to provide conductive fine particles and anisotropic conductive material capable of preventing conduction failure and reducing the resistance value.
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.
（実施例１）
（無電解メッキ前処理工程）
平均粒子径３μｍのテトラメチロールメタンテトラアクリレートとジビニルベンゼンとの共重合樹脂を用いて構成された基材微粒子１０ｇに、５重量％水酸化ナトリウム水溶液によるアルカリ脱脂、酸中和、及び、二塩化スズ溶液におけるセンシタイジングを行った。その後、二塩化パラジウム溶液におけるアクチベイチングを行う無電解メッキ前処理を施し、濾過洗浄後、粒子表面にパラジウムを付着させた基材微粒子を得た。
Example 1
(Electroless plating pretreatment process)
Alkali degreasing, acid neutralization with 5% by weight aqueous sodium hydroxide, acid neutralization, and tin dichloride on 10 g of substrate fine particles composed of a copolymer resin of tetramethylolmethane tetraacrylate and divinylbenzene having an average particle diameter of 3 μm Sensitizing in solution was performed. Then, the electroless-plating pre-processing which performs activation in a palladium dichloride solution was performed, the base-material microparticles | fine-particles which made palladium adhere to the particle | grain surface after filtration washing | cleaning were obtained.
（芯物質複合化工程）
得られた基材微粒子を脱イオン水３００ｍＬ中で３分間攪拌し、分散させた。しかる後、その水溶液に金属ニッケル粒子スラリー（三井金属社製「２０２０ＳＵＳ」、平均粒子径２００ｎｍ）１ｇを３分間かけて添加し、芯物質を付着させた基材微粒子を得た。
(Core material compounding process)
The obtained base material fine particles were stirred and dispersed in 300 mL of deionized water for 3 minutes. Thereafter, 1 g of metallic nickel particle slurry (“2020SUS” manufactured by Mitsui Kinzoku Co., Ltd., average particle size 200 nm) was added to the aqueous solution over 3 minutes to obtain substrate fine particles to which a core substance was adhered.
（無電解ニッケルメッキ工程）
得られた基材微粒子を更に水１２００ｍＬで希釈し、メッキ安定剤４ｍＬを添加した。しかる後、この水溶液に、硫酸ニッケル４５０ｇ／Ｌ、次亜リン酸ナトリウム１５０ｇ／Ｌ、クエン酸ナトリウム１１６ｇ／Ｌ、及び、メッキ安定剤６ｍＬの混合溶液１２０ｍＬを、８１ｍＬ／分の添加速度で定量ポンプを通して添加した。その後、ｐＨが安定するまで攪拌し、水素の発泡が停止するのを確認し、無電解メッキ前期工程を行なった。
次いで、更に硫酸ニッケル４５０ｇ／Ｌ、次亜リン酸ナトリウム１５０ｇ／Ｌ、クエン酸ナトリウム１１６ｇ／Ｌ、及び、メッキ安定剤３５ｍＬの混合溶液６５０ｍＬを、２７ｍＬ／分の添加速度で定量ポンプを通して添加した。その後、ｐＨが安定するまで攪拌し、水素の発泡が停止するのを確認し、無電解メッキ後期工程を行なった。
次いで、メッキ液を濾過し、濾過物を水で洗浄した後、８０℃の真空乾燥機で乾燥して、ニッケルメッキされた（芯材がニッケルに被覆されてなる突起Ａを有する）導電性微粒子を得た。
(Electroless nickel plating process)
The obtained substrate fine particles were further diluted with 1200 mL of water, and 4 mL of a plating stabilizer was added. Thereafter, 120 mL of a mixed solution of 450 g / L of nickel sulfate, 150 g / L of sodium hypophosphite, 116 g / L of sodium citrate, and 6 mL of a plating stabilizer is added to this aqueous solution at an addition rate of 81 mL / min. Added through. Then, it stirred until pH became stable, it confirmed that the foaming of hydrogen stopped, and the electroless-plating pre-process was performed.
Subsequently, 650 mL of a mixed solution of 450 g / L of nickel sulfate, 150 g / L of sodium hypophosphite, 116 g / L of sodium citrate, and 35 mL of a plating stabilizer was added through a metering pump at an addition rate of 27 mL / min. Then, it stirred until pH was stabilized, it confirmed that hydrogen foaming stopped, and the electroless-plating late process was performed.
Next, the plating solution is filtered, and the filtrate is washed with water, and then dried with a vacuum dryer at 80 ° C. and is nickel-plated (having protrusions A in which the core material is covered with nickel). Got.
（金メッキ工程）
塩化金酸ナトリウム１０ｇとイオン交換水１０００ｍＬとを含む溶液を調製し、得られた無電解ニッケルメッキ粒子１２ｇを混合して水性懸濁液を調製した。得られた水性懸濁液に、チオ硫酸アンモニウム１５ｇ、亜硫酸アンモニウム８０ｇ、及び、リン酸水素アンモニウム４０ｇを投入しメッキ液を調製した。得られたメッキ液にヒドロキシルアミン４ｇを投入後、アンモニアを用いｐＨを９に合わせ、浴温を６０℃にし、１５〜２０分程度反応させることにより金メッキ被膜が形成された（芯材がニッケルに被覆されてなる突起Ａ及び金の異常析出による突起Ｂを有する）導電性微粒子を得た。
(Gold plating process)
A solution containing 10 g of sodium chloroaurate and 1000 mL of ion exchange water was prepared, and 12 g of the obtained electroless nickel plating particles were mixed to prepare an aqueous suspension. A plating solution was prepared by adding 15 g of ammonium thiosulfate, 80 g of ammonium sulfite, and 40 g of ammonium hydrogen phosphate to the obtained aqueous suspension. After 4 g of hydroxylamine was added to the obtained plating solution, the pH was adjusted to 9 using ammonia, the bath temperature was set to 60 ° C., and the reaction was performed for 15 to 20 minutes to form a gold plating film (the core material was nickel). Conductive fine particles (having coated protrusion A and protrusion B due to abnormal deposition of gold) were obtained.
（実施例２）
（無電解メッキ前処理工程）
平均粒子径３μｍのテトラメチロールメタンテトラアクリレートとジビニルベンゼンとの共重合樹脂を用いて構成された基材微粒子１０ｇに、８重量％水酸化ナトリウム水溶液によるアルカリ脱脂、酸中和、及び、二塩化スズ溶液におけるセンシタイジングを行った。その後、二塩化パラジウム溶液におけるアクチベイチングを行う無電解メッキ前処理を施し、濾過洗浄後、粒子表面にパラジウムを付着させた基材微粒子を得た。
(Example 2)
(Electroless plating pretreatment process)
10 g of substrate fine particles composed of a copolymer resin of tetramethylolmethane tetraacrylate having an average particle diameter of 3 μm and divinylbenzene, alkali degreasing with 8 wt% sodium hydroxide aqueous solution, acid neutralization, and tin dichloride Sensitizing in solution was performed. Then, the electroless-plating pre-processing which performs activation in a palladium dichloride solution was performed, the base-material microparticles | fine-particles which made palladium adhere to the particle | grain surface after filtration washing | cleaning were obtained.
（芯物質複合化工程）
得られた基材微粒子を脱イオン水３００ｍＬ中で３分間攪拌し、分散させた。しかる後、その水溶液に金属ニッケル粒子スラリー（三井金属社製「２０２０ＳＵＳ」、平均粒子径２００ｎｍ）１ｇを３分間かけて添加し、芯物質を付着させた基材微粒子を得た。
(Core material compounding process)
The obtained base material fine particles were stirred and dispersed in 300 mL of deionized water for 3 minutes. Thereafter, 1 g of metallic nickel particle slurry (“2020SUS” manufactured by Mitsui Kinzoku Co., Ltd., average particle diameter of 200 nm) was added to the aqueous solution over 3 minutes to obtain substrate fine particles to which a core substance was adhered.
（無電解ニッケルメッキ工程）
得られた基材微粒子を更に水１２００ｍＬで希釈し、メッキ安定剤１ｍＬを添加した。しかる後、この水溶液に、硫酸ニッケル４５０ｇ／Ｌ、次亜リン酸ナトリウム１５０ｇ／Ｌ、クエン酸ナトリウム１１６ｇ／Ｌ、及び、メッキ安定剤２ｍＬの混合溶液１２０ｍＬを、８１ｍＬ／分の添加速度で定量ポンプを通して添加した。その後、ｐＨが安定するまで攪拌し、水素の発泡が停止するのを確認し、無電解メッキ前期工程を行った。
次いで、更に硫酸ニッケル４５０ｇ／Ｌ、次亜リン酸ナトリウム１５０ｇ／Ｌ、クエン酸ナトリウム１１６ｇ／Ｌ、及び、メッキ安定剤３５ｍＬの混合溶液６５０ｍＬを、２７ｍＬ／分の添加速度で定量ポンプを通して添加した。その後、ｐＨが安定するまで攪拌し、水素の発泡が停止するのを確認し、無電解メッキ後期工程を行った。
次いで、メッキ液を濾過し、濾過物を水で洗浄した後、８０℃の真空乾燥機で乾燥して、ニッケルメッキされた（芯材がニッケルに被覆されてなる突起Ａ及びニッケルの異常析出による突起Ｂを有する）導電性微粒子を得た。
(Electroless nickel plating process)
The obtained substrate fine particles were further diluted with 1200 mL of water, and 1 mL of a plating stabilizer was added. Thereafter, 120 mL of a mixed solution of nickel sulfate 450 g / L, sodium hypophosphite 150 g / L, sodium citrate 116 g / L, and plating stabilizer 2 mL is metered into this aqueous solution at an addition rate of 81 mL / min. Added through. Then, it stirred until pH became stable, it confirmed that hydrogen foaming stopped, and the electroless-plating pre-process was performed.
Subsequently, 650 mL of a mixed solution of 450 g / L of nickel sulfate, 150 g / L of sodium hypophosphite, 116 g / L of sodium citrate, and 35 mL of a plating stabilizer was added through a metering pump at an addition rate of 27 mL / min. Then, it stirred until pH became stable, it confirmed that hydrogen foaming stopped, and the electroless-plating late process was performed.
Next, the plating solution is filtered, and the filtrate is washed with water, and then dried with a vacuum dryer at 80 ° C., and then nickel-plated (by the protrusion A formed by covering the core with nickel and abnormal precipitation of nickel). Conductive fine particles (with protrusions B) were obtained.
（金メッキ工程）
置換メッキ法により表面に金メッキを施すことで、金メッキ被膜が形成された導電性微粒子（芯材がニッケルに被覆されてなる突起Ａ及びニッケルの異常析出による突起Ｂを有する）を得た。
(Gold plating process)
By conducting gold plating on the surface by a displacement plating method, conductive fine particles (having protrusions A in which the core material is coated with nickel and protrusions B due to abnormal precipitation of nickel) were obtained.
（比較例１）
実施例１と同様にしてニッケルメッキされた導電性微粒子を得た後、置換メッキ法により表面に金メッキを施すことで、金メッキ被膜が形成された（芯材がニッケルに被覆されてなる突起Ａを有する）導電性微粒子を得た。
(Comparative Example 1)
After obtaining nickel-plated conductive fine particles in the same manner as in Example 1, the surface was plated with gold by a displacement plating method to form a gold-plated film (the protrusion A formed by covering the core with nickel). Conductive fine particles were obtained.
（比較例２）
実施例１と同様にしてニッケルメッキされた導電性微粒子を得た後、塩化金酸ナトリウム１０ｇとイオン交換水１０００ｍＬとを含む溶液を調製し、ニッケルメッキされた導電性微粒子１２ｇを混合して水性懸濁液を調製した。得られた水性懸濁液に、チオ硫酸アンモニウム３０ｇ、亜硫酸アンモニウム８０ｇ、及び、リン酸水素アンモニウム４０ｇを投入しメッキ液を調製した。得られたメッキ液にヒドロキシルアミン１０ｇを投入後、アンモニアを用いｐＨを１０に合わせ、浴温を６０℃にし、１５〜２０分程度反応させることにより金メッキ被膜が形成された（芯材がニッケルに被覆されてなる突起Ａを有する）導電性微粒子を得た。
(Comparative Example 2)
After obtaining nickel-plated conductive fine particles in the same manner as in Example 1, a solution containing 10 g of sodium chloroaurate and 1000 mL of ion-exchanged water was prepared, and 12 g of nickel-plated conductive fine particles were mixed to be aqueous. A suspension was prepared. To the obtained aqueous suspension, 30 g of ammonium thiosulfate, 80 g of ammonium sulfite, and 40 g of ammonium hydrogen phosphate were added to prepare a plating solution. After adding 10 g of hydroxylamine to the resulting plating solution, the pH was adjusted to 10 using ammonia, the bath temperature was set to 60 ° C., and the reaction was carried out for about 15 to 20 minutes, whereby a gold plating film was formed (the core material was nickel). Conductive fine particles (having coated projections A) were obtained.
＜評価＞
実施例１〜２及び比較例１〜２で得られた導電性微粒子について以下の評価を行った。結果を表１に示した。
<Evaluation>
The following evaluation was performed about the electroconductive fine particles obtained in Examples 1-2 and Comparative Examples 1-2. The results are shown in Table 1.
（１）接続抵抗値の測定
得られた導電性微粒子を用いて以下の方法により異方性導電材料を作製し、電極間の接続抵抗値の測定を行った。
樹脂バインダーの樹脂としてエポキシ樹脂（油化シェルエポキシ社製、「エピコート８２８」）１００重量部、トリスジメチルアミノエチルフェノール２重量部、及び、トルエン１００重量部を、遊星式攪拌機を用いて充分に混合した後、離型フィルム上に乾燥後の厚さが１０μｍとなるように塗布し、トルエンを蒸発させて接着性フィルムを得た。
次いで、樹脂バインダーの樹脂としてエポキシ樹脂（油化シェルエポキシ社製、「エピコート８２８」）１００重量部、トリスジメチルアミノエチルフェノール２重量部、及び、トルエン１００重量部に、得られたそれぞれの導電性微粒子を添加し、遊星式攪拌機を用いて充分に混合した後、離型フィルム上に乾燥後の厚さが７μｍとなるように塗布し、トルエンを蒸発させて導電性微粒子を含有する接着性フィルムを得た。なお、導電性微粒子の配合量は、フィルム中の含有量が５万個／ｃｍ２となるようにした。
得られた接着性フィルムと導電性微粒子を含有する接着性フィルムとを常温でラミネートすることにより、２層構造を有する厚さ１７μｍの異方性導電フィルムを得た。
得られた異方性導電フィルムを５×５ｍｍの大きさに切断した。これを、一方に抵抗測定用の引き回し線を有した幅２００μｍ、長さ１ｍｍ、高さ０．２μｍ、Ｌ／Ｓ２０μｍのアルミニウム電極のほぼ中央に貼り付けた後、ＩＴＯ電極を有するガラス基板を、電極同士が重なるように位置あわせをしてから貼り合わせた。
このガラス基板の接合部を、１０Ｎ、１００℃の圧着条件で熱圧着した後、電極間の接続抵抗値を測定した。
また、作製した試験片に対して信頼性試験（８０℃、９５％ＲＨの高温高湿環境下で１０００時間保持）を行った後、電極間の接続抵抗値を測定した。
(1) Measurement of connection resistance value An anisotropic conductive material was produced by the following method using the obtained conductive fine particles, and the connection resistance value between the electrodes was measured.
100 parts by weight of an epoxy resin (“Epicoat 828” manufactured by Yuka Shell Epoxy Co., Ltd.), 2 parts by weight of trisdimethylaminoethylphenol, and 100 parts by weight of toluene as a resin binder resin are sufficiently mixed using a planetary stirrer. Then, it was applied on the release film so that the thickness after drying was 10 μm, and toluene was evaporated to obtain an adhesive film.
Next, 100 parts by weight of an epoxy resin (“Epicoat 828” manufactured by Yuka Shell Epoxy Co., Ltd.), 2 parts by weight of trisdimethylaminoethylphenol, and 100 parts by weight of toluene as a resin binder resin were obtained. After adding fine particles and mixing well using a planetary stirrer, it is coated on a release film so that the thickness after drying is 7 μm, and toluene is evaporated to form an adhesive film containing conductive fine particles Got. In addition, the compounding quantity of electroconductive fine particles was made for the content in a film to be 50,000 pieces / cm < 2 >.
By laminating the obtained adhesive film and an adhesive film containing conductive fine particles at room temperature, an anisotropic conductive film having a two-layer structure and a thickness of 17 μm was obtained.
The obtained anisotropic conductive film was cut into a size of 5 × 5 mm. After affixing this to approximately the center of an aluminum electrode having a width of 200 μm, a length of 1 mm, a height of 0.2 μm, and an L / S of 20 μm having a lead wire for measuring resistance, a glass substrate having an ITO electrode is obtained. The electrodes were bonded together after being aligned so that the electrodes overlap each other.
The bonded portion of the glass substrate was thermocompression bonded under pressure bonding conditions of 10N and 100 ° C., and then the connection resistance value between the electrodes was measured.
Moreover, after performing the reliability test (80 degreeC, hold | maintained for 1000 hours in a high-temperature, high-humidity environment of 95% RH) with respect to the produced test piece, the connection resistance value between electrodes was measured.
（２）突起の平均高さ
得られた導電性微粒子について、日立ハイテクノロジーズ社製走査電子顕微鏡（ＳＥＭ）により、倍率１００００倍で粒子観察を行い、突起Ａ及び突起Ｂの高さを調べた。
突起Ａ及び突起Ｂの平均高さは、それぞれ確認された２０個の突起について高さを測定し、それを算術平均して突起の平均高さとした。
(2) Average height of protrusions The obtained conductive fine particles were observed with a scanning electron microscope (SEM) manufactured by Hitachi High-Technologies Corporation at a magnification of 10,000 times, and the heights of the protrusions A and B were examined.
The average heights of the protrusions A and B were measured for 20 protrusions that were confirmed, and the average height was calculated as the average height of the protrusions.
（３）突起の数
得られた導電性微粒子について、日立ハイテクノロジーズ社製走査電子顕微鏡（ＳＥＭ）により、倍率１００００倍で粒子観察を行い、突起Ａ及び突起Ｂの数を計測し、ａ／ｂ値を求めた。
(3) Number of protrusions The obtained conductive fine particles are observed with a scanning electron microscope (SEM) manufactured by Hitachi High-Technologies Corporation at a magnification of 10,000 times, and the number of protrusions A and protrusions B is measured. The value was determined.
本発明によれば、導通不良防止とともに抵抗値の低減化が可能な導電性微粒子及び異方性導電材料を提供することができる。 According to the present invention, it is possible to provide conductive fine particles and anisotropic conductive material capable of preventing conduction failure and reducing the resistance value.
Claims (2)
ことを特徴とする導電性微粒子。 Conductive fine particles comprising substrate fine particles and a conductive layer formed on the surface of the substrate fine particles, wherein the conductive layer has protrusions A having a height of 200 to 400 nm and protrusions B having a height of 50 to 100 nm on the surface. And the projection A has a core, and the conductive fine particles satisfying 3 <a / b <10, where a is the number of projections A and b is the number of projections B .
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| JP2000243132A (en) * | 1999-02-22 | 2000-09-08 | Nippon Chem Ind Co Ltd | Conductive electroless plating powder, manufacture thereof, and conductive material made thereof |
| JP2003234020A (en) * | 2002-02-06 | 2003-08-22 | Sekisui Chem Co Ltd | Conductive minute particle |
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