JP4341005B2 - Metal nanowire-containing composition and electromagnetic wave shielding filter - Google Patents
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- JP4341005B2 JP4341005B2 JP2002365949A JP2002365949A JP4341005B2 JP 4341005 B2 JP4341005 B2 JP 4341005B2 JP 2002365949 A JP2002365949 A JP 2002365949A JP 2002365949 A JP2002365949 A JP 2002365949A JP 4341005 B2 JP4341005 B2 JP 4341005B2
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【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４５０nm〜１５００nm、短軸１nm〜４５nm、およびアスペクト比２０以上のワイヤー状の金属（電解法によって製造されたものではない。以下、金属ナノワイヤーと云う）を含有する樹脂組成物であって、上記金属ナノワイヤーの表面はアミノ基含有高分子系分散剤によって保護されており、膜厚２μmの被膜を形成したときに、７０％以上の可視光透過率および１.０Ω/□以下の表面抵抗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〕 上記[１]の組成物によって形成された電磁波遮蔽フィルター、電磁波遮蔽フィルム、または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４５０nm〜１５００nm、短軸１nm〜４５nm、およびアスペクト比２０以上のワイヤー状の金属（電解法によって製造されたものではない。金属ナノワイヤーと云う）を含有する樹脂組成物であって、上記金属ナノワイヤーの表面はアミノ基含有高分子系分散剤によって保護されており、膜厚２μmの被膜を形成したときに、７０％以上の可視光透過率および１.０Ω/□以下の表面抵抗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。
【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（ソルスパース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]
BACKGROUND 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 having a high transmittance in the visible light region formed by this composition.
[0002]
[Prior art]
As a translucent shield having both shielding of electromagnetic waves and translucency in the visible light region, “a conductive mesh composed of plated fibers obtained by metal plating of metal fibers or organic fibers on two transparent substrates is interposed. "Integrated with adhesive resin" (Japanese Patent Laid-Open No. 2000-174488) or "Conductive material in which a transparent plastic film and a conductive material are bonded via an adhesive, and a geometric figure is formed by chemical etching "(Kaikaihei 10-04682)" is used. However, these translucent shields are complicated in the process of forming metal fibers or plated fibers into a mesh shape and the process of forming geometric figures by chemical etching, and are expensive.
[0003]
In addition, an electromagnetic wave shield using only an oxide transparent conductor such as In-Sn oxide (ITO) and a translucent shield in which a metal thin film and an oxide transparent conductor are laminated are also known (special features). Kaihei 10-217380), the former has a low electromagnetic wave shielding ability, and the latter requires a large-scale apparatus such as a sputtering apparatus to form a film, which is expensive.
[0004]
Furthermore, for the purpose of forming a metal wiring pattern, it is known to use plasmon-absorbing inorganic fine particles carried on a solid surface as a fine rod grown to a diameter of less than 100 nm and an aspect ratio of 1 or more ( JP 2001-64794). However, in this method, since the fine rod grows in a state of being supported on the solid surface, it cannot be dispersed in various solvents and binders, so that it cannot be made into a paint. In addition, 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 specific wavelengths of visible light and near infrared light caused by the long axis of metal nanorods.
[0005]
[Problems to be solved by the invention]
The present invention solves the above-mentioned problems in the conventional transparent conductive film, and by using metal nanowires, a composition capable of easily forming a filter excellent in electromagnetic wave shielding effect and its electromagnetic wave shielding filter, And a paint or film thereof.
[0006]
[Means for solving the problems]
That is, according to this invention, the metal nanowire containing composition which consists of the following structures, and its use are provided.
[1] A resin composition containing a wire-shaped metal (not manufactured by an electrolysis method; hereinafter referred to as metal nanowire) having a major axis of 450 nm to 1500 nm, a minor axis of 1 nm to 45 nm, and an aspect ratio of 20 or more. The surface of the metal nanowire is protected by an amino group-containing polymer dispersant, and when a film having a thickness of 2 μm is formed, the visible light transmittance of 70% or more and 1.0Ω / □ Metal nanowire containing composition characterized by having the following surface resistance .
[2] An electromagnetic wave shielding filter, an electromagnetic wave shielding film, or a coating composition for forming an electromagnetic wave shielding film, formed of the composition according to [1] .
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be specifically described based on embodiments.
The composition of the present invention is a resin containing a wire-like metal (not produced by an electrolytic method, referred to as metal nanowire) having a major axis of 450 nm to 1500 nm, a minor axis of 1 nm to 45 nm, and an aspect ratio of 20 or more. The surface of the metal nanowire is protected with an amino group-containing polymer dispersant, and when a film having a film thickness of 2 μm is formed, the visible light transmittance of 70% or more and 1.0Ω A metal nanowire-containing composition having a surface resistance of / □ or less . Gold, silver, copper, and alloys thereof can be used as the metal species of the metal nanowire. When the major axis is less than 400 nm, the minor axis is greater than 50 nm, and the aspect ratio is less than 20, the elongated fibers are not intertwined with each other while maintaining an appropriate interval. Accordingly, the surface resistance is not less than 1.0Ω / □, and a high electromagnetic shielding effect cannot be obtained, and the visible light transmittance is also reduced. Specific metal types, shaft lengths, aspect ratios, and the like may be appropriately determined according to the purpose of use.
[0008]
Metal nanowires are, for example, methods by NRJana, L. Gearheart and CJMurphy (Chm. Commun., 2001, p617-p618) and methods by C. Ducamp-Sanguesa, R. Herrera-Urbina, and M. Figlarz ( J. Solid State Chem., 100. 1992, p272-p280).
[0009]
The metal nanowire-containing composition of the present invention is obtained by mixing the metal nanowire in a dispersion or a resin. The type of dispersion or resin is not limited. Further, the amount of the metal nanowire is not limited.
[0010]
The composition in which the metal nanowires are dispersed in the resin is one in which the metal nanowires are kneaded into the resin and dispersed in the resin, the metal nanowires are mixed into the resin component, and the paint is formed, or the metal nanowires Including those in which the resin surface is coated and dispersed. A resin film or 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 metal nanowires with a coating component and adding various additives as necessary.
[0011]
In the resin film or coating composition, the type of resin or solvent in which the metal nanowires are dispersed can be determined as appropriate. The resin may be a resin usually used for an electromagnetic wave shielding film, and the paint component may be a resin component usually used for a paint, water, or various organic solvents. The amount of dispersion of metal nanowires and the use of other binders and additives can be appropriately determined according to conditions. In addition, the usage method etc. of a coating composition are not restrict | 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 nanowire is 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. Moreover, a transparent electromagnetic wave shielding filter can be formed by coating a coating composition containing the metal nanowires on the surface of a substrate such as a transparent resin film or a transparent glass plate. A resin film or a 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]
In general, a filter having a surface resistance value of 2.5Ω / □ or less and a transmittance of 70% or more in the visible light region can be used as an electromagnetic wave shielding filter for a plasma display panel (PDP). Since the transparent electromagnetic wave shielding filter of the present invention has a visible light transmittance of 70% or more and a surface resistance value of the filter surface of 1.0 Ω / □ or less, it is suitable as an electromagnetic wave shielding filter for PDP. Moreover, since the metal nanowire of this invention is disperse | distributed in the state in which the elongate fibrous thing was mutually entangled, the outstanding electroconductivity and electromagnetic wave shielding effect are acquired even with a comparatively small dispersion amount. Therefore, the clearness of the PDP image is maintained. Moreover, since the transparent electromagnetic wave shielding filter of the present invention has a translucency in the visible range and a low surface resistance, it can also 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 (major axis average length 1 μm, minor axis average length 10 nm) whose surface was protected with an amino group-containing polymer dispersant (Solsperse 24000SC) The mixture was mixed with 0.625 g of an epoxy resin solution (solid content: 40% by mass) to form a paint. This paint was applied to a transparent substrate (PET sheet) (thickness 2 μm) and dried to form a film. When this film was irradiated with visible light of 400 nm to 800 nm and the transmittance was measured with a spectrophotometer (product of JASCO Corporation: V-570), the transmittance was 80% over the entire wavelength range. Further, the surface resistance of the coating surface was measured by using a resistivity meter (product of Mitsubishi Chemical Corporation: Loresta GP) based on the four-end needle method, and found to be 1.9Ω / □. The results are shown in Table 1.
[0016]
[Examples 2 to 6]
A film was formed in the same manner as in Example 1 except that the metal species, dispersion amount, aspect ratio, film formation conditions, and the like of the metal nanowire were adjusted as shown in Table 1. With respect to this film, the transmittance in the visible light region and the surface resistance of the film surface were measured in the same manner as in Example 1. The results are shown in Table 1. In addition, metal nanowires shown in Table 1 were kneaded into a resin to form a thin film (thickness 2 μm). With respect to 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 film 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 value of the surface is 1.0Ω / □ or less. It was confirmed that it has an excellent electromagnetic wave shielding function.
[0018]
[Table 1]
【The invention's effect】
When a resin film or a coating film is formed, the composition containing the metal nanowire of the present invention has a high transparency in the visible light region and a small surface resistance on the surface, and obtains 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. Moreover, it can use widely for the use of the other transparent electromagnetic wave shielding.
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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 JP2004196923A (en) | 2004-07-15 |
| JP4341005B2 true JP4341005B2 (en) | 2009-10-07 |
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