JP4341005B2 - Metal nanowires containing composition and electromagnetic shielding filter - Google Patents

Metal nanowires containing composition and electromagnetic shielding filter Download PDF

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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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metal nanowires
resin
film
metal
transparent
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JP2004196923A (en )
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聖人 室内
寛樹 平田
成圭 李
大剛 溝口
眞興 石原
佳明 高田
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三菱マテリアル株式会社
大日本塗料株式会社
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【0001】 [0001]
【発明の属する技術分野】 BACKGROUND OF THE INVENTION
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。 The present invention is a composition having an electromagnetic wave shielding function using the metallic nanowires, about electromagnetic wave shielding filter has high transmittance in the visible light region formed by this composition.
【0002】 [0002]
【従来の技術】 BACKGROUND OF THE INVENTION
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. As the light-transmitting shield having both translucency of shielding the visible light range of the electromagnetic waves, by interposing a conductive mesh made of plated fibers subjected to metal plating on the metal fibers and organic fibers "two transparent substrates those integrated by the adhesive resin "(JP 2000-174488) or that form a geometric figure by chemical etching and" transparent plastic film and a conductive material to a conductive material bonded with an adhesive "(lifting Hei 10-041682) and the like are used. 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。 However, these light-transmitting shield, the step of forming a geometric figure by a process or chemical etching for forming the metal fibers and plating the fibers in a mesh shape is complex, costly.
【0003】 [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。 Further, an In-Sn oxide (ITO) and electromagnetic shielding member using only transparent conducting oxide such as, but are also known translucent shield formed by laminating an oxide transparent conductor and a metal thin film (Japanese Patent No. 10-217380), the former has a low electromagnetic shielding ability, the latter requires a large apparatus such as a sputtering apparatus for forming a film, which is costly.
【0004】 [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)。 Further, for the purpose of forming a metal wiring pattern, the inorganic fine particles to plasmon absorption was supported on a solid surface to be used in the fine rod grown diameter of less than 100nm and an aspect ratio of 1 or more known ( JP 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。 However, this method is fine rod to grow in a state of being supported on a solid surface, it is impossible to paint various solvents, it can not be dispersed in a binder. 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。 Further, plasmon absorption of metal fine particles is used only to grow purposes in the synthesis process are not intended to be utilized for selective absorption of specific wavelengths of visible light and near-infrared light due to the long axis of the metal nanorods.
【0005】 [0005]
【発明が解決しようとする課題】 [Problems that the Invention is to Solve
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。 The present invention has solved the above problems of the conventional transparent conductive film, by using the metallic nanowires, the composition and its electromagnetic wave shielding filter having excellent filter electromagnetic wave shielding effect can be easily formed, and there is provided the coating or film.
【0006】 [0006]
【課題を解決する手段】 [It means for solving the problems]
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。 That is, the metal nanowire-containing composition comprising the following structure according to the present invention and its application are provided.
〔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。 [1] major axis 450Nm~1500nm, minor axis 1Nm~45nm, and an aspect ratio of 20 or more wire-like metal (not have been produced by electrolysis. Hereinafter referred to as metal nanowires) resin composition containing a is the surface of the metal nanowires is protected by an amino group-containing polymer-based dispersing agent, when forming a film with a thickness of 2 [mu] m, 70% or more visible light transmittance and 1.0 [Omega] / □ metal nanowires containing composition characterized by having the following surface resistance.
〔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。 [2] [1] electromagnetic wave shielding filter formed by the compositions of the electromagnetic wave shielding film or electromagnetic wave shielding film forming coating composition.
【0007】 [0007]
【発明の実施の形態】 DETAILED DESCRIPTION OF THE INVENTION
以下、本発明を実施形態に基づいて具体的に説明する。 It will be specifically described based on an embodiment of the present invention.
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。 The compositions of the present invention, the long axis 450Nm~1500nm, minor axis 1Nm~45nm, and an aspect ratio of 20 or more wire-like metal (not produced by electrolysis. Referred to as metal nanowires) resin containing a composition, the surface of the metal nanowires is protected by an amino group-containing polymer-based dispersant, at the time of forming the film thickness 2μm coating, over 70% of the visible light transmittance and 1.0Ω / □ is a metal nanowires-containing composition characterized by having the following surface resistance. 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。 As metal species of the metal nanowires can be used gold, silver, copper, and alloys thereof. 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。 Those major axis is greater than 50nm minor axis less than 400 nm, and those aspect ratio is less than 20, not a state where entangled while maintaining moderate intervals ones of the elongated fibers. 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。 Therefore, after that it can not be surface resistance obtain a high electromagnetic shielding effect does not become 1.0 [Omega] / □ or less, the transmittance of visible light is also reduced. 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。 Specific metal species and axial length may be determined as appropriate depending on the aspect ratio or the like intended use.
【0008】 [0008]
金属ナノワイヤーは、例えば、NRJana, L.Gearheart and CJMurphy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。 Metal nanowires, for example, NRJana, the method according L.Gearheart and CJMurphy (Chm.Commun., 2001, p617-p618) or, C.Ducamp-Sanguesa, R.Herrera-Urbina, and M.Figlarz such methods ( J. Solid State Chem., 100. 1992, can be prepared by p272~p280).
【0009】 [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。 Metal nanowires-containing composition of the present invention is a mixture of the metal nanowires such as the dispersion and resin. 分散液や樹脂の種類は限定されない。 Type of dispersion and the resin is not limited. また金属ナノワイヤーの量も限定されない。 Also not limited the amount of metal nanowires.
【0010】 [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。 Compositions of the metal nanowires are dispersed in the resin, are dispersed in a resin kneaded metal nanowires resin, those metal nanowires were mixed in the resin component, and coating material, or metal nanowires the etc. are dispersed by coating the resin surface. 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。 These metal nanowires can be obtained a resin film or a coating composition having an electromagnetic shielding function by composition dispersed in the resin. 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。 For example, the resin film may be molded into a film by kneading the metal nanowires resin. 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。 The coating composition of the metal nanowires are mixed in the paint component, obtained by adding various additives as necessary.
【0011】 [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。 In the resin film or coating composition, the kind of resin or solvent for dispersing the metal nanowires can be appropriately determined. 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。 Resin may be a normally used resin in the electromagnetic wave shielding film, also the paint component may be a resin component and water or various organic solvents which are usually used in the paint. 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。 Use of a dispersion amount and other binders and additives of the metal nanowires can be appropriately determined depending on the conditions. なお、塗料組成物の使用方法等も制限されない。 Even not limited like the use of the coating composition. 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。 Brushing, spraying, can be used by various methods such as roll coating or spin coating.
【0012】 [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。 The metal nanowires can be obtained a transparent electromagnetic wave shielding filter by composition dispersed in the resin. 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。 For example, the metal nanowires transparent resin film dispersed in the resin can be used as a transparent electromagnetic wave shielding filter. 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。 Further, it is possible to form a transparent electromagnetic wave shielding filter by coating a coating composition containing the metal nanowires on a substrate surface, such as a transparent resin film or transparent glass plate to form a film. 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。 These metal nanowires resin film or a coating film formed body in which is dispersed may be laminated with each laminated or other transparent material. 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。 Transparent electromagnetic wave shielding filter of the present invention include those of the laminated manner.
【0013】 [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。 In general, those transmittance in the visible light region is 70% or more surface resistance value of the filter surface is not more 2.5 Ohms / □ or less can be used as an electromagnetic wave shielding filter for a plasma display panel (PDP), transparent electromagnetic wave shielding filter of the present invention, since the surface resistance of the filter surface there is transmittance of visible light region of 70% or more is 1.0 [Omega] / □ or less, it is suitable as an electromagnetic wave shielding filter for PDP. 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。 Moreover, since those metal nanowires elongated fibrous present invention are dispersed in a state of intertwined, relatively few excellent conductivity even dispersion amount and the electromagnetic wave shielding effect is obtained. 従って、PDP画像の鮮明性が保たれる。 Therefore, sharpness of the PDP image can be maintained. 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。 The transparent electromagnetic wave shielding filter of the present invention has a light-transmitting property and a low surface resistance of the visible region can also be used as a transparent conductive film.
【0014】 [0014]
【実施例】 【Example】
本発明を実施例によって具体的に示す。 The present invention examples specifically shown.
【0015】 [0015]
〔実施例1〕 Example 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。 Amino group-containing polymer-based dispersant (Solsperse 24000SC) to protect the surface with a silver nanowire (longer axis average length 1 [mu] m, the minor axis average length 10 nm) and toluene dispersion 2g of (silver nanowires 1.0g containing) epoxy resin solution was mixed with (solid content 40 wt%) 0.625 g was paint. 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。 The paint was applied on a transparent substrate (PET sheet) (thickness: 2 [mu] m), and dried to form a film. 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。 The film was irradiated with visible light of 400 nm to 800 nm, a spectrophotometer (JASCO Corporation Product: V-570) was measured for transmittance by transmittance over the entire wavelength range was 80%. 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。 Also, the surface resistance on the basis of 4 Tanhari method resistivity meter of coating surface (Mitsubishi Chemical Co. Product: Loresta GP) was 1.9Ω / □ a was measured using a. この結果を表1に示した。 The results are shown in Table 1.
【0016】 [0016]
〔実施例2〜6〕 Example 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。 Metal species of the metal nanowires dispersion amount, aspect ratio, to form a film except that the like deposition conditions were adjusted as shown in Table 1 in the same manner as in Example 1. 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。 This film in the same manner as in Example 1 were measured the surface resistance of the transmittance and the film surface of the visible light region. この結果を表1に示した。 The results are shown in Table 1. 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。 Also, by forming a metal nanowire shown in Table 1 into a thin film kneaded into the resin (thickness 2 [mu] m). 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。 This the resin film in the same manner as in Example 1 were measured the surface resistance of the transmittance and the film surface of the visible light region. この結果を表1に示した。 The results are shown in Table 1.
【0017】 [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。 As shown in Table 1, any coatings and resin film metal nanowires according to the present invention is dispersed is also excellent in the transmittance is high transparency in the visible light region, yet the surface resistivity of the surface 1.0 [Omega] / □ or less , and the was confirmed to have an excellent electromagnetic wave shielding function.
【0018】 [0018]
【表1】 [Table 1]
【0019】 [0019]
【発明の効果】 【Effect of the invention】
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。 Compositions containing metal nanowires of the present invention, when forming the resin film or coating film, low surface resistance of the surface which has a high transparency in the visible light region, obtain a filter having an excellent electromagnetic shielding effect be able to. 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。 Therefore, this filter can be used as an electromagnetic wave shielding filter for PDP. 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。 Moreover, it can be widely used in the other transparent electromagnetic shielding applications.

Claims (2)

  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。 Major axis 450Nm~1500nm, minor axis 1Nm~45nm, and an aspect ratio of 20 or more wire-like metal (not have been produced by electrolysis. Hereinafter referred to as metal nanowires) a resin composition containing , the surface of the metal nanowires is protected by an amino group-containing polymer-based dispersing agent, when forming a film with a thickness of 2 [mu] m, 70% or more visible light transmittance and 1.0 [Omega] / □ or less of the surface metal nanowires containing composition characterized in that it comprises a resistor.
  2. 請求項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。 Electromagnetic wave shielding filter formed by composition of claim 1, the electromagnetic wave shielding film or electromagnetic wave shielding film forming coating composition.
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