JP2004196923A - Metal nanowire-containing composition and electromagnetic wave-shielding filter - Google Patents
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は金属ナノワイヤーを用いた電磁波遮蔽機能を有する組成物と、この組成物によって形成された可視光域での透過率が高い電磁波遮蔽フィルターに関する。
【０００２】
【従来の技術】
電磁波の遮蔽と可視光域の透光性を兼ね備えた透光性シールドとしては、「２枚の透明基板に金属繊維や有機繊維に金属めっきを施したメッキ繊維からなる導電性メッシュを介在させて接着樹脂で一体化したもの」（特開２０００−１７４４８８）や、「透明プラスチックフィルムと導電性材料とを接着剤を介して貼り合せた導電性材料にケミカルエッチングにより幾何学図形を形成させたもの」（持開平１０−０４１６８２）などが用いられている．しかし、これら透光性シールドは、金属繊維やメッキ繊維をメッシュ状に成形する工程やケミカルエッチングによって幾何学図形を形成させる工程が複雑であり、コスト高である。
【０００３】
また、Ｉｎ−Ｓｎ酸化物（ＩＴＯ）等の酸化物透明導電体のみを用いた電磁波シールド体や、金属薄膜と酸化物透明導電体を積層させた透光性シールドも知られているが（特開平１０−２１７３８０）、前者は電磁波遮蔽能が低く、後者では成膜を行うのにスパッタリング装置などの大がかりな装置が必要であり、コスト高である。
【０００４】
さらに、金属配線パターンを形成することを目的として、固体表面に担持させたプラズモン吸収する無機質微粒子を直径１００nm未満およびアスペクト比１以上に成長させた微細ロッドにして使用することが知られている（特開２００１−６４７９４）。しかし、この方法は、微細ロッドは固体表面に担持された状態で成長するため、各種溶媒、バインダーに分散させることができないので塗料化することができない。また、金属微粒子のプラズモン吸収は合成過程における成長目的にのみ利用されており、金属ナノロッドの長軸に起因する可視光・近赤外光の特定波長の選択的な吸収に利用したものではない。
【０００５】
【発明が解決しようとする課題】
本発明は、従来の透明導電膜における上記問題を解決したものであり、金属ナノワイヤーを用いることによって、電磁波遮蔽効果に優れたフィルターを容易に形成することができる組成物とその電磁波遮蔽フィルター、およびその塗料ないしフィルムを提供するものである。
【０００６】
【課題を解決する手段】
すなわち、本発明によれば以下の構成からなる金属ナノワイヤー含有組成物とその用途が提供される。
（１）長軸が４００nm以上であって短軸が５０nm以下であるワイヤー状の金属（金属ナノワイヤー）を含有する電磁波遮蔽機能を有することを特徴とする金属ナノワイヤー含有組成物。
（２）金属ナノワイヤーを樹脂に分散させた上記(1)の組成物。
（３）金属ナノワイヤーのアスペクト比が２０以上である上記(1)または(2)の組成物。
（４） 上記(1)、(2)または(3)の組成物によって形成された電磁波遮蔽フィルター。
（５）可視光域の透過率が７０％以上である上記(4)の電磁波遮蔽フィルター。
（６）フィルターの表面抵抗が１.０Ω/□以下である上記(4)または(5)の電磁波遮蔽フィルター。
（７）上記(2)または(3)の組成物によって形成された電磁波遮蔽フィルム。
（８）上記(2)または(3)の組成物からなる電磁波遮蔽膜形成用塗料組成物。
【０００７】
【発明の実施の形態】
以下、本発明を実施形態に基づいて具体的に説明する。
本発明の組成物は、長軸が４００nm以上、好ましくは４５０〜１５００nmであって、短軸が５０nm以下、好ましくは１〜４５nmであり、また、好ましくはアスペクト比が２０以上であるワイヤー状の金属（金属ナノワイヤー）を含有し、電磁波遮蔽機能を有することを特徴とする金属ナノワイヤー含有組成物である。金属ナノワイヤーの金属種としては金、銀、銅、およびそれらの合金などを用いることができる。長軸が４００nm未満であって短軸が５０nmより大きいもの、およびアスペクト比が２０より小さいものは、細長い繊維状のものが適度な間隔を保ちながら互いに絡み合った状態にはならない。従って、表面抵抗が１.０Ω/□以下にならず高い電磁波遮蔽効果を得ることができないうえ、可視光線の透過率も低下する。具体的な金属種や軸長さ、アスペクト比等は使用目的等に応じて適宜定めればよい。
【０００８】
金属ナノワイヤーは、例えば、N.R.Jana, L.Gearheart and C.J.Murphyによる方法（Chm.Commun.,2001, p617-p618）や、C.Ducamp-Sanguesa, R.Herrera-Urbina, and M.Figlarz等の方法（J. Solid State Chem.,100. 1992, p272〜p280）によって製造することができる。なお、金属ナノワイヤーの製造はこれらの方法に限らない。
【０００９】
本発明の金属ナノワイヤー含有組成物は上記金属ナノワイヤーを分散液や樹脂などに混合したものである。分散液や樹脂の種類は限定されない。また金属ナノワイヤーの量も限定されない。
【００１０】
上記金属ナノワイヤーを樹脂に分散させた組成物は、金属ナノワイヤーを樹脂に練り込んで樹脂中に分散させたもの、金属ナノワイヤーを樹脂成分に混合し、塗料化したもの、あるいは金属ナノワイヤーを樹脂表面にコーティングして分散させたものなどを含む。これらの金属ナノワイヤーを樹脂に分散させた組成物によって電磁波遮蔽機能を有する樹脂フィルムや塗料組成物を得ることができる。例えば、この樹脂フィルムは上記金属ナノワイヤーを樹脂に練り込んでフィルム状に成形すれば良い。また塗料組成物は上記金属ナノワイヤーを塗料成分に混合し、必要に応じて各種添加剤を加えて得られる。
【００１１】
上記樹脂フィルムや塗料組成物において、金属ナノワイヤーを分散させる樹脂や溶媒の種類は適宜定めることができる。樹脂は電磁波遮蔽フィルムに通常用いる樹脂であれば良く、また塗料成分は塗料に通常使用されている樹脂成分や水ないし各種有機溶剤であれば良い。金属ナノワイヤーの分散量やその他のバインダーや添加剤などの使用は条件に応じて適宜定めることができる。なお、塗料組成物の使用方法等も制限されない。刷毛塗り、吹き付け、ロールコーティングやスピンコーティングなどの各種の方法によって使用することができる。
【００１２】
上記金属ナノワイヤーを樹脂に分散させた組成物によって透明な電磁波遮蔽フィルターを得ることができる。例えば、上記金属ナノワイヤーを樹脂に分散させた透明な樹脂フィルムは透明電磁波遮蔽フィルターとして用いることができる。また、透明な樹脂フィルムや透明なガラス板などの基板表面に上記金属ナノワイヤーを含有する塗料組成物をコーティングして被膜を形成することによって透明な電磁波遮蔽フィルターを形成することができる。これらの金属ナノワイヤーを分散させた樹脂フィルムやコーティング被膜形成体は各々積層し、あるいは他の透明材料と積層して用いることができる。本発明の透明電磁波遮蔽フィルターはこれらの積層した態様を含む。
【００１３】
一般に、フィルター表面の表面抵抗値が２.５Ω/□以下であって可視光域の透過率が７０％以上であるものはプラズマディスプレーパネル(ＰＤＰ)用の電磁波遮蔽フィルターとして用いることができるが、本発明の透明電磁波遮蔽フィルターは可視光域の透過率が７０％以上であってフィルター表面の表面抵抗値が１.０Ω/□以下であるので、ＰＤＰ用の電磁波遮蔽フィルターとして好適である。また、本発明の金属ナノワイヤーは細長い繊維状のものが互いに絡み合った状態で分散されているので、比較的少ない分散量でも優れた導電性と電磁波遮蔽効果が得られる。従って、ＰＤＰ画像の鮮明性が保たれる。また、本発明の透明電磁波遮蔽フィルターは可視域の透光性と低い表面抵抗を有するため、透明導電膜としても使用することができる。
【００１４】
【実施例】
本発明を実施例によって具体的に示す。
【００１５】
〔実施例１〕
アミノ基含有高分子系分散剤（ソルスハ゜ース24000SC）で表面を保護した銀ナノワイヤー（長軸平均長さ１μm、短軸平均長さ１０nm）のトルエン分散液２ｇ（銀ナノワイヤー１.０ｇ含有）をエポキシ樹脂溶液（固形分４０質量％）０.６２５ｇと混合して塗料化した。この塗料を透明な基材(PETシート)に塗布し(厚さ２μm)、乾燥して被膜を形成した。この被膜に４００nm〜８００nmの可視光を照射し、分光光度計（日本分光社製品：V-570）によって透過率を測定したところ、この全波長域にわたって透過率は８０％であった。また、この被膜表面の表面抵抗を４端針法に基づき抵抗率計（三菱化学社製品：ロレスタGP）を用いて測定したところ１.９Ω/□であった。この結果を表１に示した。
【００１６】
〔実施例２〜６〕
金属ナノワイヤーの金属種、分散量、アスペクト比、成膜条件などを表１に示すように調整した以外は実施例１と同様にして被膜を形成した。この被膜について実施例１と同様にして可視光域の透過率と被膜表面の表面抵抗を測定した。この結果を表１に示した。また、表１に示す金属ナノワイヤーを樹脂に練り込んで薄いフィルム（厚さ２μm）に成形した。この樹脂フィルムについて実施例１と同様にして可視光域の透過率と被膜表面の表面抵抗を測定した。この結果を表１に示した。
【００１７】
表１に示すように、本発明に係る金属ナノワイヤーが分散した被膜および樹脂フィルムは何れも可視光域の透過率が高く透明性に優れ、しかも表面の表面抵抗値は１.０Ω/□以下であり、優れた電磁波遮蔽機能を有することが確認された。
【００１８】
【表１】
【発明の効果】
本発明の金属ナノワイヤーを含有する組成物は、樹脂フィルムやコーティング膜を形成した場合、可視光域において高い透明性を有すると共に表面の表面抵抗が小さく、優れた電磁波遮蔽効果を有するフィルターを得ることができる。従って、このフィルターはＰＤＰ用の電磁波遮蔽フィルターとして利用することができる。また、この他の透明な電磁波遮蔽の用途に広く用いることができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a composition having an electromagnetic wave shielding function using metal nanowires, and an electromagnetic wave shielding filter formed by the composition and having a high transmittance in a visible light region.
[0002]
[Prior art]
As a translucent shield that has both electromagnetic wave shielding and translucency in the visible light range, "A transparent mesh consisting of plated fibers made of metal fibers or organic fibers coated with metal is interposed between two transparent substrates. "Integrated with adhesive resin" (Japanese Patent Laid-Open No. 2000-174488) or "A transparent plastic film and a conductive material bonded together via an adhesive to form a geometric figure by chemical etching." (Kyohei Hei 10-041682). However, these translucent shields are complicated in the steps of forming metal fibers or plated fibers into a mesh and the steps of forming geometric figures by chemical etching, resulting in high costs.
[0003]
Further, an electromagnetic wave shield using only an oxide transparent conductor such as an In-Sn oxide (ITO) and a light-transmitting shield in which a metal thin film and an oxide transparent conductor are laminated are known. The former has low electromagnetic wave shielding ability, and the latter requires a large-scale apparatus such as a sputtering apparatus to form a film, and is expensive.
[0004]
Further, for the purpose of forming a metal wiring pattern, it is known that plasmon-absorbing inorganic fine particles supported on a solid surface are used as fine rods grown to a diameter of less than 100 nm and an aspect ratio of 1 or more ( JP-A-2001-64794). However, according to this method, since the fine rod grows while being supported on the solid surface, it cannot be dispersed in various solvents and binders, and thus cannot be formed into a paint. Further, plasmon absorption of metal fine particles is used only for the purpose of growth in the synthesis process, and is not used for selective absorption of a specific wavelength of visible light / near infrared light caused by the long axis of the metal nanorod.
[0005]
[Problems to be solved by the invention]
The present invention has solved the above-mentioned problem in the conventional transparent conductive film, and by using metal nanowires, a composition and an electromagnetic wave shielding filter that can easily form a filter having an excellent electromagnetic wave shielding effect, And a paint or film thereof.
[0006]
[Means to solve the problem]
That is, according to the present invention, a metal nanowire-containing composition having the following constitution and its use are provided.
(1) A metal nanowire-containing composition having an electromagnetic wave shielding function containing a wire-shaped metal (metal nanowire) having a major axis of 400 nm or more and a minor axis of 50 nm or less.
(2) The composition according to (1) above, wherein the metal nanowires are dispersed in a resin.
(3) The composition according to the above (1) or (2), wherein the aspect ratio of the metal nanowire is 20 or more.
(4) An electromagnetic wave shielding filter formed from the composition of (1), (2) or (3).
(5) The electromagnetic wave shielding filter according to the above (4), wherein the transmittance in the visible light region is 70% or more.
(6) The electromagnetic wave shielding filter according to (4) or (5), wherein the surface resistance of the filter is 1.0 Ω / □ or less.
(7) An electromagnetic wave shielding film formed from the composition of (2) or (3).
(8) A coating composition for forming an electromagnetic wave shielding film comprising the composition of (2) or (3).
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be specifically described based on embodiments.
The composition of the present invention has a long axis of 400 nm or more, preferably 450 to 1500 nm, and a short axis of 50 nm or less, preferably 1 to 45 nm, and preferably has a wire-like aspect ratio of 20 or more. A metal nanowire-containing composition containing a metal (metal nanowire) and having an electromagnetic wave shielding function. As the metal species of the metal nanowire, gold, silver, copper, and alloys thereof can be used. When the major axis is less than 400 nm and the minor axis is greater than 50 nm, and when the aspect ratio is less than 20, elongated fibrous materials are not entangled with each other while maintaining an appropriate interval. Accordingly, the surface resistance is not less than 1.0 Ω / □, a high electromagnetic wave shielding effect cannot be obtained, and the transmittance of visible light is also reduced. The specific metal type, shaft length, aspect ratio, etc. may be determined appropriately according to the purpose of use.
[0008]
Metal nanowires can be prepared by, for example, a method according to NRJana, L. Gearheart and CJMurphy (Chm. Commun., 2001, p617-p618), a method such as C. Ducamp-Sanguesa, R. Herrera-Urbina, and M. Figlarz ( J. Solid State Chem., 100. 1992, p272-p280). The production of metal nanowires is not limited to these methods.
[0009]
The metal nanowire-containing composition of the present invention is obtained by mixing the above metal nanowire with a dispersion, a resin, or the like. The types of the dispersion and the resin are not limited. Also, the amount of the metal nanowire is not limited.
[0010]
The composition in which the metal nanowires are dispersed in a resin is a composition in which the metal nanowires are kneaded into a resin and dispersed in the resin, a composition in which the metal nanowires are mixed with a resin component and formed into a coating, or a composition in which the metal nanowires are coated. On the resin surface and dispersed. A resin film or a coating composition having an electromagnetic wave shielding function can be obtained by a composition in which these metal nanowires are dispersed in a resin. For example, the resin film may be formed into a film by kneading the metal nanowires into a resin. The coating composition is obtained by mixing the above metal nanowires with a coating component and adding various additives as necessary.
[0011]
In the resin film and the coating composition, the type of the resin or the solvent in which the metal nanowires are dispersed can be appropriately determined. The resin may be any resin commonly used for electromagnetic wave shielding films, and the paint component may be a resin component or water or various organic solvents commonly used in paint. The amount of the metal nanowires dispersed and the use of other binders and additives can be appropriately determined according to the conditions. The method of using the coating composition is not limited. It can be used by various methods such as brushing, spraying, roll coating and spin coating.
[0012]
A transparent electromagnetic wave shielding filter can be obtained by a composition in which the metal nanowires are dispersed in a resin. For example, a transparent resin film in which the metal nanowires are dispersed in a resin can be used as a transparent electromagnetic wave shielding filter. In addition, a transparent electromagnetic wave shielding filter can be formed by coating the surface of a substrate such as a transparent resin film or a transparent glass plate with the coating composition containing the metal nanowires to form a coating. The resin film or the coating film forming body in which these metal nanowires are dispersed can be laminated or used with another transparent material. The transparent electromagnetic wave shielding filter of the present invention includes these laminated embodiments.
[0013]
Generally, a filter having a surface resistance of 2.5 Ω / □ or less and a transmittance in the visible light region of 70% or more can be used as an electromagnetic wave shielding filter for a plasma display panel (PDP). The transparent electromagnetic wave shielding filter of the present invention has a transmittance in the visible light region of 70% or more and a surface resistance value of the filter surface of 1.0Ω / □ or less, and thus is suitable as an electromagnetic wave shielding filter for PDP. In addition, since the metal nanowires of the present invention are dispersed in a state in which elongated fibrous materials are entangled with each other, excellent conductivity and electromagnetic wave shielding effect can be obtained even with a relatively small amount of dispersion. Therefore, the sharpness of the PDP image is maintained. In addition, since the transparent electromagnetic wave shielding filter of the present invention has translucency in the visible region and low surface resistance, it can be used as a transparent conductive film.
[0014]
【Example】
The present invention is specifically illustrated by examples.
[0015]
[Example 1]
2 g of toluene dispersion (containing 1.0 g of silver nanowires) of silver nanowires (long axis average length 1 μm, short axis average length 10 nm) whose surface is protected with an amino group-containing polymer dispersant (Solution 24000SC) It was mixed with 0.625 g of an epoxy resin solution (solid content: 40% by mass) to form a coating. This paint was applied to a transparent substrate (PET sheet) (thickness: 2 μm) and dried to form a coating. The coating was irradiated with visible light of 400 to 800 nm, and the transmittance was measured by a spectrophotometer (V-570, manufactured by JASCO Corporation). The transmittance was 80% over the entire wavelength range. The surface resistance of the surface of the film was measured using a resistivity meter (Loresta GP, manufactured by Mitsubishi Chemical Corporation) based on the four-point probe method and found to be 1.9 Ω / □. The results are shown in Table 1.
[0016]
[Examples 2 to 6]
A coating was formed in the same manner as in Example 1 except that the metal species, the amount of dispersion, the aspect ratio, the film forming conditions, and the like of the metal nanowires were adjusted as shown in Table 1. The transmittance of this coating film in the visible light range and the surface resistance of the coating film surface were measured in the same manner as in Example 1. The results are shown in Table 1. Further, the metal nanowires shown in Table 1 were kneaded into a resin and formed into a thin film (thickness: 2 μm). For this resin film, the transmittance in the visible light region and the surface resistance of the coating surface were measured in the same manner as in Example 1. The results are shown in Table 1.
[0017]
As shown in Table 1, both the coating and the resin film in which the metal nanowires according to the present invention are dispersed have high transmittance in the visible light region and excellent transparency, and the surface resistance of the surface is 1.0Ω / □ or less. It was confirmed to have an excellent electromagnetic wave shielding function.
[0018]
[Table 1]
【The invention's effect】
The composition containing the metal nanowires of the present invention, when a resin film or a coating film is formed, has a high transparency in the visible light region and a small surface resistance of the surface, thereby obtaining a filter having an excellent electromagnetic wave shielding effect. be able to. Therefore, this filter can be used as an electromagnetic wave shielding filter for PDP. Further, it can be widely used for other transparent electromagnetic wave shielding applications.
Claims (8)
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| JP2002365949A JP4341005B2 (en) | 2002-12-17 | 2002-12-17 | Metal nanowire-containing composition and electromagnetic wave shielding filter |
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| JP2002365949A JP4341005B2 (en) | 2002-12-17 | 2002-12-17 | Metal nanowire-containing composition and electromagnetic wave shielding filter |
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| JP2004196923A true JP2004196923A (en) | 2004-07-15 |
| JP4341005B2 JP4341005B2 (en) | 2009-10-07 |
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