JP3753482B2 - Transparent laminate and display filter using the same - Google Patents

Description

電磁波遮蔽は電磁波の電磁波シールド体における▲１▼反射、▲２▼吸収の効果によってなされる。プラズマディスプレイの強度の電磁波を遮蔽するには、電磁波シールド体（透明積層体）に合成面抵抗４Ω／□以下、好ましくは３Ω／□以下の低抵抗な導電性が要求される。吸収には電磁波シールド体に導電性が必要で、ディスプレイから発生する電磁波をすべて吸収するには、導電層にはある値以上の厚みが必要であるが、導電層、つまり、金属薄膜層を厚くすると高屈折率透明薄膜層を用いても可視光線透過率の低いものとなってしまう。したがって、多層積層により反射界面を増やし、電磁波の反射を増やすことも重要である。
【００１８】
電磁波シールド能を表すシールド効果は、電磁波エネルギーをどの程度減衰させるかを表し、その大きさはデシベル（ｄＢ）で表される。シールド効果（ＳＥ）は、下記に示す式（２）で表される相対評価であり、この数値が大きいほどシールド効果があるといえる。Ｅｉは入射電界強度、Ｅｔは伝送電界強度、つまりシールド体を透過した電磁波の電界強度を示し、いずれも単位はＶ／ｍである。
ＳＥ＝２０Ｌｏｇ（Ｅｉ／Ｅｔ） （２）
ＶＣＣＩの規制値は、絶対値である放射電界強度で示され、その単位はｄＢμＶ／ｍである。工業用途の規制値を示すClass Ｉでは５０ｄＢμＶ／ｍであり、家庭用途の規制値を示すClass IIでは４０ｄＢμＶ／ｍである。プラズマディスプレイの放射電界強度は２０〜９０ＭＨｚ帯域内で４０ｄＢμＶ／ｍを越えているため、このままでは家庭用途には使用できない。実用的には放射電界強度が４０ｄＢμＶ／ｍ以下、好ましくは３５ｄＢμＶ／ｍ以下、より好ましくは３０ｄＢμＶ／ｍ以下にする必要がある。プラズマディスプレイの放射電界強度が５０ｄＢμＶ／ｍである場合は、１０ｄＢ以上、好ましくは１５ｄＢ以上、より好ましくは２０ｄＢ以上のシールド効果を有する電磁波シールドを必要とする。このためには、電磁波シールド体が面抵抗４Ω／□以下、好ましくは３Ω／□以下の高い導電性を有していれば良く、また多層積層により多くの反射界面を有していることも重要なのである。
【００１９】
また、プラズマディスプレイは、強度の近赤外線を発するため、近赤外領域である８００〜１０００nmの波長領域の光をカットすることが好ましく、８２０ｎｍより長波長の領域での光線透過率を１０％以下にすることが好ましい。部材数低減の要求や色素を用いた近赤外線吸収の限界から、電磁波シールド体自体が近赤外線抑止性を持つことが望ましい。近赤外線吸収色素を併用する場合は、電磁波シールド体に要求される近赤外線抑止性は上記要求性能より低いものになるが、電磁波シールド体の近赤外線抑止性があまり低いと近赤外線吸収色素の必要量が多くなり、可視光線透過率の減少を招く恐れがある。そのため、近赤外線吸収色素を併用する場合の電磁波シールド体は、例えば８２０nmより長波長の領域の光線透過率が、最低でも２０％以下であることが望ましい。
【００２０】
近赤外線カットには、金属の自由電子による反射を用いることができるが、金属薄膜層を厚くすると前述したように可視光線透過率も低くなり、薄くすると近赤外線の反射が弱くなる。そこで、ある厚さの金属薄膜層を高屈折率透明薄膜層で挟み込んだ積層構造を１回以上重ねることにより、可視光線透過率を高くし、かつ全体的な金属薄膜層の厚さを増やすことができ、また、それぞれの層の厚さを制御することにより可視光線透過率、近赤外線の透過率、色目をある範囲で変化させることができる。可視光線透過率が低いと、ディスプレイ設置時に画像の鮮明さが低下するため、フィルターの可視光線透過率は高い程良く、少なくとも４０％以上、好ましくは５０％以上である。さらに電磁波シールド体の色目は、ディスプレイのコントラスト等に大きく影響し、プラズマディスプレイ用電磁波シールド体には、赤紫不透過による緑色は不適であり、ニュートラルグレー、または、赤黄不透過によるブルーであることが要求される。このための色目や、可視光線透過率、近赤外線の透過率の制御は、一般に多層積層である方が光学的に設計しやすい。
【００２１】
また、酸化インジウムや酸化スズ、酸化亜鉛等の酸化物半導体や酸化インジウムと酸化スズの混合物（ＩＴＯ）をはじめとする２元系酸化物半導体等は、透明性に優れており、ＩＴＯといった比較的高い導電性を持つ酸化物半導体薄膜を数千Å〜数μｍと厚く形成することによって低抵抗な導電膜を形成することができる。酸化物半導体を形成した透明導電膜は、導電性を示すキャリア電子によりある程度近赤外線を反射するが、プラズマディスプレイ用フィルターに要求される近赤外線透過率を満たすことはできないため、近赤外線吸収色素を併用することが望ましい。
【００２２】
金属薄膜層を高屈折率透明薄膜層で挟み込んだ積層構造を多段重ねることは、使用できる生産装置が制限され、また、一度に多層の各膜厚等の制御をする必要もあるため、所望の光学特性、面抵抗を安定して得ることが困難であり、例えば１バッチで３段以上重ねることは、生産装置が高価なものに限られる上に７層以上の各膜厚を安定して制御しなければならない。また、酸化物半導体を厚く形成する透明導電膜の場合も、ラインスピードや成膜の安定性の問題から、上記要求の低抵抗を満たす程、一度に厚く成膜する事は難しい。また、一度成膜したものに、もう一度成膜する場合、歩留まりが低下する問題が生じる。
【００２３】
しかしながら、金属薄膜層を高屈折率透明薄膜層で挟み込んだ積層構造を１回以上重ねた透明導電層、または、酸化物半導体を厚く形成した透明導電層を透明基体の一方の主面上に形成した透明導電性積層体を、２枚以上重ねることによって、所望の合成面抵抗、またさらには、所望の近赤外線透過率を有する透明積層体が得られ、上記の効果が得られるのである。また、２枚以上重ねることによって電磁波の反射界面を増やすこともできる。重ねる透明導電性積層体は、同じものでも、異なったものでも良い。金属薄膜層を高屈折率透明薄膜層で挟み込んだ積層構造を１回以上重ねた透明導電層を形成した透明導電性積層体と、酸化物半導体を厚く形成した透明導電層を透明基体に形成した透明導電性積層体を重ねても良い。重ね方としては、透明導電性積層体同士を粘着材または接着剤を介して貼り合わせる。透明導電性積層体間に任意の機能を有する介在物があっても良いが、ディスプレイからの光線透過部分に介在する場合は、介在物が可視光線に対して充分透明であることが必要である。
【００２４】
金属薄膜層を高屈折率透明薄膜層で挟み込んだ積層構造を１回以上重ねた透明導電層を形成する場合、透明基体の一方の主面上に高屈折率透明薄膜層（Ｂ−１）、金属薄膜層（Ｂ−２）の順で、（Ｂ−１）／（Ｂ−２）を繰り返し単位として１回以上繰り返し積層し、さらにその上に少なくとも高屈折率透明薄膜層を積層する。繰り返し積層数は、１回〜３回が好ましい。つまり、透明基体／高屈折率透明薄膜層／金属薄膜層／高屈折率透明薄膜層、透明基体／高屈折率透明薄膜層／金属薄膜層／高屈折率透明薄膜層／金属薄膜層／高屈折率透明薄膜層、または、透明基体／高屈折率透明薄膜層／金属薄膜層／高屈折率透明薄膜層／金属薄膜層／高屈折率透明薄膜層／金属薄膜層／高屈折率透明薄膜層である。繰り返し回数が４回以上だと生産装置の制限、生産性の問題が大きくなる。
【００２５】
高屈折率透明薄膜層および金属薄膜層の多層積層で、可視光線透過率、近赤外線光の透過率、色目を制御し、所望の透明導電性積層体を得るには、透明基体および薄膜材料の屈折率、消衰係数を用いたベクトル法、アドミッタンス図を用いる方法等を使った光学設計を行い、各層の薄膜材料及び、層数、膜厚等を決定する。また、光学特性を観察しながら、層数、膜厚等を制御して成膜を行うこともできる。
【００２６】
金属薄膜層の厚さは導電性、光学特性等から光学設計的かつ実験的に求められ、得られる透明導電性積層体を重ねた透明積層体が要求特性を持てば特に限定されるものではないが、導電性等から薄膜が島状構造ではなく連続状態であることが必要なので４nm以上であることが望ましく、金属薄膜層が厚すぎると透明性が問題になるので３０nm以下が望ましい。
【００２７】
金属薄膜の具体的な材料としては、銀、金、白金、パラジウム、ニッケル、クロム、亜鉛、ジルコニウム、チタン、タングステン、スズ等、あるいはこれらの材料の２種類以上からなる合金があげられる。なかでも銀は、導電性、赤外線反射性および多層積層したときの可視光線透過性に優れるため好適に使用できる。しかし、銀は化学的、物理的安定性に欠け、環境中の汚染物質、熱、光等によって劣化するため、銀に金、白金、パラジウム、インジウム、スズ等の環境に安定な金属を一種以上含んだ合金が好適に使用される。ここで、銀を含む合金の銀の含有率は、特に限定されるものではないが銀薄膜の導電性、光学特性が大きく変わらないことが望ましく、５０重量％以上１００重量％未満程度である。しかしながら、銀に他の金属を添加すると、その優れた導電性を阻害するので、可能であれば少なくとも１つの層は銀を合金にしないで用いることが望ましい。また、隣接する高屈折率透明薄膜層が酸化物であると、該金属薄膜層の金属の一部は、実際には金属酸化物となっていることがあるが、非常に薄い領域であるため光学設計及び成膜上、特に問題はない。また、金属薄膜第１層、第２層、・・・、第ｎ層（ｎ≧２）は、同じ厚さとは限らず、同じ金属あるいは合金でなくともよい。金属薄膜層の形成には、スパッタリング、イオンプレーティング、真空蒸着、メッキ等、従来公知の方法のいずれでも採用できる。
【００２８】
高屈折率透明薄膜層としては、可視域において透明性を有し、金属薄膜層における可視域における光線反射を防止する効果を有するものであれば特に限定されるものではないが、可視光線に対する屈折率が１．６以上、好ましくは１．７以上の屈折率の高い材料が用いられる。このような高屈折率透明薄膜層を形成する具体的な材料としては、インジウム、チタン、ジルコニウム、ビスマス、スズ、亜鉛、アンチモン、タンタル、セリウム、ネオジウム、ランタン、トリウム、マグネシウム、ガリウム等の酸化物、または、これら酸化物の混合物や、硫化亜鉛などが挙げられる。これら酸化物あるいは硫化物は、金属と酸素あるいは硫黄と化学量論的な組成にズレがあっても、光学特性を大きく変えない範囲であるならば差し支えない。なかでも、酸化インジウムや酸化インジウムと酸化スズの混合物（ＩＴＯ）は、透明性、屈折率に加えて、成膜速度が速く金属薄膜層との密着性等が良好であることから好適に使用できる。また、ＩＴＯといった比較的高い導電性を持つ酸化物半導体薄膜を用いることによって、電磁波の吸収量を増やし、また電磁波シールド体の導電性を上げることができる。高屈折率透明薄膜層の厚さは、透明基体の光学特性、金属薄膜層の厚さ、光学特性、および、透明薄膜層の屈折率等から光学設計的かつ実験的に求められ、特に限定されるものではないが、５nm以上２００nm以下であることが好ましく、より好ましくは１０nm以上１００nm以下である。また、高屈折率透明薄膜第１層、第２層、・・・第ｎ層（ｎ≧２）は、同じ厚さとは限らず、同じ透明薄膜材料でなくともよい。高屈折率透明薄膜層の形成には、スパッタリング、イオンプレーティング、イオンビームアシスト、真空蒸着、湿式塗工等、従来公知の方法のいずれでも採用できる。
【００２９】
スパッタリングは、膜厚制御、多層積層には好適で、金属薄膜層と高屈折率透明薄膜層を容易に繰り返し連続的に成膜できる。具体例として実施例において後述するが、主として酸化インジウムで構成される高屈折率透明薄膜層と銀または銀を含む合金からなる金属薄膜層をスパッタリング法により連続成膜する。主として酸化インジウムで構成される高屈折率透明薄膜層の形成には、インジウムを主成分とする金属ターゲットまたは酸化インジウムを主成分とする焼結体ターゲットを用いた反応性スパッタリングを行う。反応性スパッタリング法においては、スパッタガスにはアルゴン等の不活性ガス、反応性ガスには酸素を用い、通常圧力０．１〜２０ｍＴｏｒｒ、直流（ＤＣ）あるいは高周波（ＲＦ）マグネトロンスパッタリング法等が利用できる。酸素ガス流量は得られる成膜速度等から実験的に求められ、所望の透明性を持つ薄膜が得られるように制御する。銀または銀を含む合金からなる金属薄膜層の形成には、銀または銀を含む合金をターゲットとしたスパッタリングを行う。スパッタガスにはアルゴン等の不活性ガスを用い、通常圧力０．１〜２０ｍＴｏｒｒ、直流（ＤＣ）あるいは高周波（ＲＦ）マグネトロンスパッタリング法等が利用できる。
【００３０】
また、酸化物半導体を成膜した透明導電層を用いて得られる本発明の透明積層体において、酸化物半導体は、可視域において透明性を有し、導電性を有していれば特に限定されるものではない。具体例としては、酸化インジウム、酸化スズ、酸化亜鉛等やＩＴＯをはじめとするこれら酸化物の混合物（二元系酸化物）、またはこれら酸化物あるいは二元系酸化物にアンチモンやフッ素、ケイ素、ホウ素、アルミニウム、ガリウム、マグネシウム等を微量添加したものが挙げられる。これら酸化物は、金属と酸素との化学量論的な組成にズレがあっても、光学特性、導電性を大きく変えない範囲であるならば差し支えない。なかでも、ＩＴＯは、高い透明性、導電性に加えて、成膜速度が速いことから好適に使用できる。透明導電膜の厚さは、導電性、光学特性等から実験的に求められ、得られる透明導電性積層体を重ねた透明積層体が要求特性を持てば特に限定されるものではないが、透明導電性積層体には低抵抗が要求されるため０．１μｍ以上１０μｍ以下であることが好ましく、より好ましくは０．５μｍ以上５μｍ以下である。
【００３１】
酸化物半導体の成膜には、スパッタリング、イオンプレーティング、イオンビームアシスト、真空蒸着、湿式塗工等、従来公知の方法のいずれでも採用でき、なかでもスパッタリングは、導電性、膜厚制御には好適である。例えばＩＴＯの形成には、インジウムとスズを主成分とする金属ターゲットまたは酸化インジウムを酸化スズを主成分とする焼結体ターゲットを用いた反応性スパッタリングを行う。反応性スパッタリング法においては、スパッタガスにはアルゴン等の不活性ガス、反応性ガスには酸素を用い、通常圧力０．１〜２０ｍＴｏｒｒ、直流（ＤＣ）あるいは高周波（ＲＦ）マグネトロンスパッタリング法等が利用できる。酸素ガス流量は得られる成膜速度等から実験的に求められ、所望の透明性、導電性を持つ薄膜が得られるように制御する。
【００３２】
本発明の透明導電性積層体においては、その機械的強度や耐環境性を向上させるために、透明基体（Ａ）の透明導電層（Ｂ）（以下、導電層とする）のない面に、透明性を有するハードコート層を設けたり、導電層の最外表面に、導電性、光学特性を損なわない程度に任意の保護層を設けてもよい。また、金属薄膜層の耐環境性や金属薄膜層と高屈折率透明薄膜層との密着性等を向上させるため、金属薄膜層と高屈折率透明薄膜層の間に、導電性、光学特性を損なわない程度に任意の無機物層を形成してもよい。具体的な材料としては銅、ニッケル、クロム、金、銀、白金、亜鉛、ジルコニウム、チタン、タングステン、スズ、パラジウム等、あるいはこれらの材料の２種類以上からなる合金があげられ、その厚さは、好ましくは０．０２nm〜２nm程度で、厚さが薄すぎると密着力向上の十分な効果が得られない。高屈折率透明薄膜層が酸化物であると、該無機物層の金属の一部または全部は、実際には金属酸化物となっているがその効果に問題はない。さらには、透明導電性積層体の主面に単層又は多層の任意の反射防止層を設けることによって、さらに透過率の高い透明積層体を得ることもできる。
【００３３】
上記の方法により形成した、酸化物導電膜または、高屈折率透明薄膜層および金属薄膜層の原子組成は、オージェ電子分光法（ＡＥＳ）、誘導結合プラズマ法（ＩＣＰ）、ラザフォード後方散乱法（ＲＢＳ）等により測定できる。また、これらの層構成および膜厚は、オージェ電子分光の深さ方向観察、透過型電子顕微鏡による断面観察等により測定できる。また膜厚は、成膜条件と成膜速度の関係をあらかじめ明らかにした上で成膜を行うことや水晶振動子等を用いた成膜中の膜厚モニタリングにより、制御される。
【００３４】
上記のようにして得られた透明導電性積層体を２枚以上重ねることによって本発明の透明積層体を得ることができる。透明導電性積層体の積層枚数は、可視光線透過率が４０％以上得られる範囲ならば良く、４枚以下が好ましい。積層構成の一例を〔図１〕に示す。透明導電性積層体１５の透明基体１１ともう一つの透明導電性積層体１５の透明導電層１２を向かい合わせて重ね、透明積層体１０としている。積層構成としては、後述するように電極を形成できれば良く、透明導電層同士、透明基体同士を向かい合わせて重ねても良い。
【００３５】
本発明のディスプレー用フィルターは、本発明の透明積層体に、金属電極、保護層、透明成形体（Ｄ）等の他の機能を有する部材を組み合わせて得られるものをいう。
【００３６】
本発明のディスプレー用フィルターのうち、電磁波シールド性を付与したディスプレイ用フィルターは、薄膜形成面すなわち導電層に金属電極を形成することによって得られる。電磁波は導電層において吸収されたのち電荷を誘起するため、アースをとる事によって電荷を逃がさないと、再び該導電層（電磁波シールド体）がアンテナとなって電磁波を発振してしまう。そのため、電磁波シールド体に電極を形成し、ディスプレイ本体のアース用電極に確実に接触させることが重要である。電極形状は特に限定しないが、透明積層体の導電層すなわち薄膜形成面の、ディスプレイからの光線透過部である中心部分を除く、周辺部分に、例えば枠状に、平面な金属電極を形成する。透明積層体の構成、すなわち透明導電性積層体の重ね方と電極形状の一例を〔図１〕及び〔図２〕に示すが、これらに限定されるものではない。
【００３７】
電極に用いる材料は、導電性、耐触性および導電面との密着性等の点から、銀、金、銅、白金、ニッケル、アルミニウム、クロム、鉄、亜鉛、等の単体もしくは２種以上からなる合金や、合成樹脂と銀または銀を含む合金の混合物、もしくは、ホウケイ酸ガラスと銀または銀を含む合金の混合物からなる銀ペーストを使用できる。電極形成にはメッキ法、真空蒸着法、スパッタ法など、銀ペーストといったものは印刷、塗工する方法など従来公知の方法を採用できる。金属電極の厚さは、これもまた特に限定されるものではないが、数μｍ〜数ｍｍ程度である。
【００３８】
また、透明積層体の薄膜形成面すなわち導電層には、耐擦傷性を付与するため、及び、ディスプレイから発せられる熱や使用環境中の熱、酸素、水蒸気等のガスによる薄膜の劣化を防ぐために、保護樹脂層を設けることも好ましい。特に金属薄膜層を高屈折率透明薄膜層で挟み込んだ積層構造を１回以上重ねた透明導電層を形成した透明導電性積層体を重ねて得られる透明積層体の場合、金属薄膜層に銀等の安定性に欠ける材料を用いるときは、保護樹脂層を設けることが好ましい。保護樹脂層としては、特に限定されるものではないが、アクリル系樹脂、シリコン系樹脂、メラミン系樹脂、ウレタン系樹脂、フッ素系樹脂等が挙げられる。保護樹脂層の形成には、用いる樹脂によって、印刷、塗工する方法など従来公知の方法を選定して用いることができ、その厚さは、これもまた特に限定されるものではないが、1 μｍ〜１００μｍ程度である。保護樹脂層は、単層であっても複数の樹脂層からなるものでも良い。この際肝要なことは、ディスプレイ用フィルターから電磁波シールドを目的として電気的接触を得る場合、保護樹脂層が金属電極とディスプレイ本体との接触を妨げないようにすることである。また、保護樹脂層中に金属薄膜の劣化を抑制する化合物を添加しても良く、金属薄膜の劣化を抑制する化合物を任意の溶剤に溶かし込み、透明積層体またはディスプレイ用フィルターの薄膜形成面の表面または端面に塗布しても良い。
【００３９】
上記のようにして得られた透明積層体やディスプレイ用フィルターは、透明基体に高分子フィルムを用いた場合、強度やディスプレイとの貼り合わせ時の平面性、設置方法の問題から、主面の平滑な板状の透明成形体（Ｄ）と貼り合わせて用いることが望ましい。透明成形体としては、機械的強度や、軽さ、割れにくさから、可視域において透明なプラスチック板が望ましいが、熱による変形等の少ない熱的安定性からガラス板も好適に使用できる。プラスチック板の具体例を挙げると、ポリメタクリル酸メチル（ＰＭＭＡ）をはじめとするアクリル樹脂、ポリカーボネート樹脂、透明ＡＢＳ樹脂等が使用できるが、これらの樹脂に限定されるものではない。特にＰＭＭＡはその広い波長領域での高透明性と機械的強度の高さから好適に使用できる。プラスチック板の厚みは十分な機械的強度と、たわまずに平面性を維持する剛性が得られればよく、特に限定されるものではないが、通常１ｍｍ〜１０ｍｍ程度である。ガラス板を透明成形体として使用する場合は、機械的強度を付加するために化学強化加工または風冷強化加工を行った半強化ガラス板または強化ガラス板を用いることが望ましい。ディスプレイ用フィルターと透明成形体の貼り合わせ方の一例を〔図３〕に示すが、これに限定されるものではない。
【００４０】
本発明においての貼り合わせには、任意の粘着材または接着剤を使用できる。この際肝要なことはディスプレイからの光線透過部である中心部分に用いられる粘着材または接着剤は可視光線に対して充分透明である必要がある。粘着材または接着剤は、実用上の接着強度があればシート上のものでも液状のものでもよく、粘着シート貼り付け後または接着剤塗布後に各部材をラミネートすることによって貼り合わせを行う。液状のものは塗布、貼り合わせ後に室温放置または加熱により硬化する接着剤であり、塗布方法としては、バーコート法、リバースコート法、グラビアコート法、ダイコート法、ロールコート法等が挙げられるが、接着剤の種類、粘度、塗布量等から考慮、選定される。粘着材もしくは接着剤層の厚みは、特に限定されるものではないが、０．５μｍ〜５０μｍ、好ましくは１μｍ〜３０μｍである。粘着材または接着剤を用いて貼り合わせた後は、貼り合わせ時に部材間に入り込んだ空気を、脱泡または、粘着材または接着剤に固溶させ、部材間の密着力を向上させる為に、加圧、加温の条件で養生を行うことが肝要である。このとき、加圧条件としては数気圧〜２０気圧以下程度、加温条件としては各部材の耐熱性に依るが、室温以上８０℃以下程度であるが、これらに特に制限を受けない。
【００４１】
上記のようにして得られた本発明の透明積層体及びディスプレイ用フィルターは、積層体やフィルターの主面とディスプレイ表面を密着させて使用する場合、ディスプレイ表面との密着度が場所によって異なるために、それによって生じる間隙を原因とするニュートンリングが発生してしまう。そのため、ディスプレイ表面と密着するそれぞれの主面上には、アンチニュートンリング層を形成することが好ましい。この際肝要なことは、ディスプレイ用フィルターから電磁波シールドを目的として電気的接触を得る場合、アンチニュートンリング層が金属電極とディスプレイ本体との接触を妨げることがあってはならない。
【００４２】
また、ディスプレイへの照明器具等の映り込みによって表示画面が見づらくなってしまうため、ディスプレイ用フィルターの人側すなわちディスプレイ本体と反対側の面に、反射防止層を形成することにより外光反射を抑制するか、ノングレア層を形成することによって防眩性を持たせることが好ましい。また、反射防止層の形成により、ディスプレイ用フィルターの反射を減じることによって、光線透過率を向上させることができる。
【００４３】
なお、前記の保護樹脂層がアンチニュートンリング性またはノングレア性を、あるいはアンチニュートンリング層またはノングレア層が保護樹脂層の役割を有していてもよい。この場合は、保護樹脂層上にさらにアンチニュートンリング層またはノングレア層を形成する必要が無く、構成部材数または構成層数が減ることにより工程、コストを減じることができ、より好適である。
【００４４】
本発明のアンチニュートンリング層、ノングレア層、保護樹脂層、反射防止層における層とは、各機能を有する膜、または、各機能を有する膜が形成されている高分子フィルム等を示しているのであって、各機能を有する膜を、塗布または印刷または従来公知の各種成膜法により形成しても、各機能を有する膜を形成した高分子フィルムを任意の接着剤または粘着材を介して貼り付けても良い。これらの作製方法は特に制限を受けない。高分子フィルムの種類、厚さも特に制限を受けない。
【００４５】
反射防止層は、反射防止膜を形成する基体の光学特性を考慮し、前述したような光学設計によって構成要素及び各構成要素の膜厚を決定する。具体的には、可視域において屈折率の低いフッ素系透明高分子樹脂やフッ化マグネシウムの薄膜等を単層形成したもの、屈折率の異なる、金属酸化物、フッ化物、ケイ化物、ホウ化物、炭化物、窒化物、硫化物等の無機化合物またはアクリル樹脂やフッ素系樹脂等の有機化合物の薄膜を２層以上多層積層したものがある。単層形成したものは、製造が容易であるが、反射防止性が多層積層に比べ劣る。多層積層したものは、広い波長領域にわたって反射防止能を有し、光学特性による光学設計の制限が少ない。これらの無機化合物薄膜は、スパッタリング、イオンプレーティング、イオンビームアシスト、真空蒸着、湿式塗工等、従来公知の方法のいずれでも採用できる。有機化合物薄膜は、湿式塗工等、従来公知の方法を採用できる。
【００４６】
本発明でいうところのアンチニュートンリング層とノングレア層は、用途が異なるだけで、０．１μｍ〜１０μｍ程度の微少な凹凸の表面状態を有する可視光線に対して透明な層を指している。具体的には、アクリル系樹脂、シリコン系樹脂、メラミン系樹脂、ウレタン系樹脂、アルキド系樹脂、フッ素系樹脂等の熱硬化型又は光硬化型樹脂に、シリカ、メラミン、アクリル等の無機化合物または有機化合物の粒子を分散させインキ化したものを、バーコート法、リバースコート法、グラビアコート法、ダイコート法、ロールコート法等によって、その層をなす基体上に塗布、硬化させて得られる。粒子の平均粒径は、１〜４０μｍ程度である。または、アクリル系樹脂、シリコン系樹脂、メラミン系樹脂、ウレタン系樹脂、アルキド系樹脂、フッ素系樹脂等の熱硬化型又は光硬化型樹脂を基体に塗布し、所望のヘイズまたは表面状態を有する型を押しつけ硬化することによってもアンチニュートンリング層またはノングレア層を得ることができる。さらには、例えばガラス板をフッ酸等でエッチングするように、基体を薬剤処理することによってもノングレア層を得ることができる。この場合は、処理時間、薬剤のエッチング性により、ノングレア層のヘイズを調節することができる。要は適当な凹凸を有することが重要であり、必ずしも上記方法に限定されるものではない。
【００４７】
ノングレア層またはアンチニュートンリング層のヘイズは0.5 ％以上20％以下であり、好ましくは１％以上10％以下である。ヘイズが小さすぎるとノングレア能またはアンチニュートンリング能が不十分であり、ヘイズが大きすぎると平行光線透過率が低くなり、ディスプレイの視認性が悪くなる。前述の保護樹脂層中に上記のような無機化合物または有機化合物の粒子を分散させた場合、保護樹脂層がアンチニュートンリング性またはノングレア性を有し、既に述べたように、より好適である。
【００４８】
フィルターがディスプレイ本体に密着せずに離れて設置される場合等、フィルター最外表面のノングレア層がディスプレイ表面から比較的距離があると、画像の拡散によるボケが生じる場合がある。この為このような設置方法の場合は、ノングレア層は防眩性を維持し、且つ、ディスプレイから適当な距離はなしても画像のボケのないヘイズのものを選択することが好ましい。
【００４９】
また、ディスプレイ用フィルターに静電防止能を付与するために、ディスプレイ用フィルターの人側となる面に、導電膜を設けても良い。ディスプレイ表面には静電気帯電により、ホコリが付着し易く、また人体が接触したときに放電して電気ショックを受けることがあるため、静電防止処理を行うことは好適である。導電膜は、可視域で透明な透明導電膜であればよい。静電防止能を有するディスプレイ用フィルターは、透明導電膜が以下のように形成されていればよい。すなわち、▲１▼透明積層体／透明成形体（Ｄ）／透明導電膜／反射防止層またはノングレア層、または、▲２▼透明積層体／透明成形体（Ｄ）／ノングレア層／透明導電膜であり、▲３▼反射防止層またはノングレア層が透明導電性を有するものでも良い。
【００５０】
▲１▼または▲２▼では、すでに述べたＩＴＯをはじめとする公知の透明導電膜を前述したような方法で成膜するか、ＩＴＯを成膜した高分子フィルムを貼り合わせることによって、透明導電膜を形成する。▲１▼では、ディスプレイ用フィルター最外表面の導電性が低い、または無いため、静電防止能が弱い。▲２▼で肝要なことは、透明導電膜を形成しても防眩性または反射防止性をあまり損なわないことである。ノングレア層上に透明導電層を形成する場合は、静電防止能の要求する導電性は比較的低くて良いため、防眩性を損なわない程度の薄い膜で十分効果がある。▲３▼では、ノングレア層中にＩＴＯ超微粒子や酸化スズ超微粒子をはじめとする導電性超微粒子を分散させたものである。▲１▼〜▲３▼のいずれの場合も反射防止層は、透明導電膜及び透明成形体との兼ね合いで、前述したような光学設計がなされ構成が決まる。▲３▼の場合は、構成要素として透明導電膜を含め、光学設計を行えばよく、反射防止層またはノングレア層の具体例を挙げれば、基体／ＩＴＯ／含ケイ素化合物／ＩＴＯ／含ケイ素化合物、基体／ＩＴＯ／含フッ素化合物等が挙げられる。
【００５１】
さらには、ディスプレイ用フィルターに耐擦傷性を付加させるために、フィルターの人側最外表面に、光学特性をはじめとするディスプレイ用フィルターの特性を損なわない程度に透明性を有するハードコート層を形成しても良い。ノングレア層がハードコート性を有していても良いし、反射防止層がハードコート層の構成要素として形成されていても良い。ハードコートの具体例としては、メラミン系樹脂、シリコン系樹脂、フッ素系樹脂等が挙げられる。
【００５２】
本発明の透明積層体は、特に金属薄膜層を高屈折率透明薄膜層で挟み込んだ積層構造を１回以上重ねた透明導電層を形成した透明導電性積層体を用いている場合、電磁波シールド能に加え、近赤外線抑止性を有するが、プラズマディスプレイは、強度の近赤外線を発するため、より近赤外線抑止性を持たせるために、近赤外線吸収色素を併用しても良い。ＩＴＯ等の酸化物半導体を成膜した透明導電性積層体を用いている場合は、近赤外線抑止性が低く、近赤外線吸収色素を用いることが肝要である。
【００５３】
すなわち、すでに述べてきた透明積層体の透明基体に近赤外線吸収色素を含有した透明積層体およびそれを用いたディスプレイ用フィルター、または、透明積層体の透明基体を貼り合わせる透明成形体、反射防止層、ノングレア層、アンチニュートンリング層、保護樹脂層のいずれか一つ以上が近赤外線吸収色素を含有しているディスプレイ用フィルター、または、ディスプレイ用フィルターの構成要素として近赤外線吸収色素を含有する透明成形物（Ｅ）を加えたディスプレイ用フィルターは、より高い近赤外線抑止能を有するのである。色素を含有する透明成形物を用いる場合は、ディスプレイ用フィルターを構成する各部材のいずれかの間に前述した任意の粘着材または接着剤を介して貼り合わせディスプレイ用フィルターの構成要素とする。
【００５４】
本発明で用いる近赤外線吸収色素は、透明積層体の近赤外線抑止能を補填し、プラズマディスプレイの発する強度の近赤外線を充分実用的になる程度に吸収するものであれば、有機、無機を問わず特に限定されるものではなく、濃度も限定されるものではない。しかしながら、以下の式（１）〔化１〕または式（２）〔化２〕で表されるジチオール錯体化合物、またはそれらの少なくとも１種以上の混合物である場合、本発明の透明積層体またはディスプレイ用フィルターは、より優れた近赤外線抑止能を有することができる。下記式（１）、（２）の化合物は市販されているので、入手可能である。
【００５５】
【化１】

［式中、Ａ¹ 〜Ａ⁸ は各々独立に、水素原子、ハロゲン原子、ニトロ基、シアノ基、チオシアナート基、シアナート基、アシル基、カルバモイル基、アルキルアミノカルボニル基、アルコキシカルボニル基、アリールオキシカルボニル基、置換又は未置換のアルキル基、置換又は未置換のアリール基、置換又は未置換のアルコキシ基、置換又は未置換のアリールオキシ基、置換又は未置換のアルキルチオ基、置換又は未置換のアリールチオ基、置換又は未置換のアルキルアミノ基、あるいは置換又は未置換のアリールアミノ基を表し、かつ、隣合う２個の置換基が連結基を介してつながっていてもよく、Ｒ¹ 〜Ｒ⁴ は各々独立に置換又は未置換のアルキル基、置換又は未置換のアリール基を表し、Ｍはニッケル、白金、パラジウムまたは銅を表し、Ｘは窒素原子又はリン原子を表す。］
【００５６】
【化２】

［式中、Ｂ¹ 〜Ｂ⁴ は各々独立に、水素原子、シアノ基、アシル基、カルバモイル基、アルキルアミノカルボニル基、アルコキシカルボニル基、アリールオキシカルボニル基、置換又は未置換のアルキル基、置換又は未置換のアリール基を表し、かつ、隣合う２個の置換基が連結基を介してつながっていてもよく、Ｍはニッケル、白金、パラジウムまたは銅を表す。］
本発明でいう含有とは、基材の内部に含有されることは勿論、基材の表面に塗布した状態、基材と基材の間に挟まれた状態等を意味する。ここでいう基材とは前述した透明積層体の透明基体、保護樹脂層、透明積層体を貼り合わせる透明成形体、反射防止層、ノングレア層、アンチニュートンリング層のいずれか、または、ディスプレイ用フィルターに形成される、色素を含有させる透明成形物である。反射防止層、ノングレア層、アンチニュートンリング層は各機能を有する膜中に色素を含有していても、各機能を有する膜が色素を含有する透明成形物上に形成されていても良い。色素を含有する透明成形物としては、透明プラスチック板、透明高分子フィルム、透明ガラス等が挙げられる。色素の含有量は、透明積層体の有する近赤外線抑止性とディスプレイ用フィルターに必要とする可視光線透過率と近赤外線抑止性等に依る。
【００５７】
本発明において、色素を用いて、色素を含有する透明成形物を作製する方法としては、特に限定されるものではないが、例えば、以下の３つの方法が利用できる。
（１）樹脂に色素を混練し、加熱成形してプラスチック板或いは高分子フィルムを作製する方法、
（２）色素を含有する塗料を作製し、透明プラスチック板、透明高分子フィルム、或いは透明ガラス板上にコーティングする方法、
（３）色素を接着剤に含有させて、合わせプラスチック板、合わせ高分子フィルム、合わせガラス等を作製する方法、等である。
【００５８】
まず、樹脂に色素を混練し、加熱成形する（１）の方法において、樹脂材料としては、プラスチック板または高分子フィルムにした場合にできるだけ透明性の高いものが好ましく、具体例として、ポリエチレン、ポリスチレン、ポリアクリル酸、ポリアクリル酸エステル、ポリ酢酸ビニル、ポリアクリロニトリル、ポリ塩化ビニル、ポリフッ化ビニル等のビニル化合物、及びそれらのビニル化合物の付加重合体、ポリメタクリル酸、ポリメタクリル酸エステル、ポリ塩化ビニリデン、ポリフッ化ビニリデン、ポリシアン化ビニリデン、フッ化ビニリデン／トリフルオロエチレン共重合体、フッ化ビニリデン／テトラフルオロエチレン共重合体、シアン化ビニリデン／酢酸ビニル共重合体等のビニル化合物又はフッ素系化合物の共重合体、ポリトリフルオロエチレン、ポリテトラフルオロエチレン、ポリヘキサフルオロプロピレン等のフッ素を含む化合物、ナイロン６、ナイロン６６等のポリアミド、ポリイミド、ポリウレタン、ポリペプチド、ポリエチレンテレフタレート等のポリエステル、ポリカーボネート、ポリオキシメチレン、ポリエチレンオキシド、ポリプロピレンオキシド等のポリエーテル、エポキシ樹脂、ポリビニルアルコール、ポリビニルブチラール等を挙げることが出来るが、これらの樹脂に限定されるものではない。
【００５９】
作製方法としては、用いる色素、ベース高分子成形体によって、加工温度、フィルム化条件等が多少異なるが、通常(i) 色素を、ベース高分子成形体の粉体或いはペレットに添加し、１５０〜３５０℃に加熱、溶解させた後、成形して樹脂板を作製する方法、(ii)押し出し機によりフィルム化する方法、(iii) 押し出し機により原反を作製し、３０〜１２０℃で２〜５倍に、１軸乃至は２軸に延伸して１０〜２００μｍ厚のフィルムにする方法、等が挙げられる。なお、混練する際に、紫外線吸収剤、可塑剤等の通常の樹脂成型に用いる添加剤を加えてもよい。色素の添加量は、色素の吸収係数、作製する高分子成形体の厚み、目的の吸収強度、目的の可視光透過率等によって異なるが、通常、１ｐｐｍ〜２０％である。
【００６０】
塗料化してコーティングする（２）の方法としては、色素をバインダー樹脂及び有機系溶媒に溶解させて塗料化する方法、ジチオール錯体化合物を数μｍ以下に微粒化してアクリルエマルジョン中に分散して水系塗料とする方法、等がある。前者の方法では、通常、脂肪族エステル系樹脂、アクリル系樹脂、メラミン樹脂、ウレタン樹脂、芳香族エステル系樹脂、ポリカーボネート樹脂、脂肪族ポリオレフィン樹脂、芳香族ポリオレフィン樹脂、ポリビニル系樹脂、ポリビニルアルコール樹脂、ポリビニル系変成樹脂（ＰＶＢ、ＥＶＡ等）或いはそれらの共重合樹脂をバインダー樹脂として用いる。
【００６１】
溶媒としては、ハロゲン系、アルコール系、ケトン系、エステル系、脂肪族炭化水素系、芳香族炭化水素系、エーテル系溶媒、あるいはそれらの混合物系等を用いる。
【００６２】
色素の濃度は、色素の吸収係数、コーティングの厚み、目的の吸収強度、目的の可視光透過率等によって異なるが、バインダー樹脂の重量に対して、通常、０．１〜３０％である。また、バインダー樹脂濃度は、塗料全体に対して、通常、１〜５０％である。アクリルエマルジョン系水系塗料の場合も同様に、未着色のアクリルエマルジョン塗料にジチオール錯体化合物を微粉砕（５０〜５００ｎｍ）したものを分散させて得られる。塗料中には、紫外線吸収剤、酸化防止剤等の通常塗料に用いるような添加物を加えてもよい。
【００６３】
上記の方法で作製した塗料は、透明高分子フィルム、透明樹脂、透明ガラス等の上にバーコーダー、ブレードコーター、スピンコーター、リバースコーター、ダイコーター、或いはスプレー等でコーティングして、色素を含有する基材を作製する。
【００６４】
コーティング面を保護するために保護層を設けたり、透明樹脂板、透明高分子フィルム等をコーティング面に貼り合わせることもできる。また、キャストフィルムも本方法に含まれる。
【００６５】
色素を接着剤に含有させて、合わせ樹脂板、合わせ樹脂フィルム、合わせガラス等を作製する（３）の方法においては、接着剤として、一般的なシリコン系、ウレタン系、アクリル系等の樹脂用、或いは合わせガラス用のポリビニルブチラール接着剤（ＰＶＢ）、エチレン−酢酸ビニル系接着剤（ＥＶＡ）等の合わせガラス用の公知の透明接着剤が使用できる。
【００６６】
色素を０．１〜３０％添加した接着剤を用いて透明な樹脂板同士、樹脂板と高分子フィルム、樹脂板とガラス、高分子フィルム同士、高分子フィルムとガラス、ガラス同士を接着してを作製する。
【００６７】
上記の色素を含有する接着剤は、透明積層体、透明成形体、反射防止層、ノングレア層、アンチニュートンリング層、色素を含有する透明成形物等の各部材の貼り合わせに用いても良い。
【００６８】
また、プラズマディスプレイ用フィルターは、８００〜１０００nmの波長領域で強度の近赤外線をカットする必要があり、このために必要であれば、上記の式（１）及び／または（２）で表されるジチオール錯体化合物を２種類以上組み合わせることもできる。
【００６９】
色素含有フィルターの耐光性を上げるためにＵＶ吸収剤を含有した透明フィルム（ＵＶカットフィルム）を色素含有部よりも外側（人側）にはりつけることもできる。
また、フィルターの色調を変えるためのに、市販の可視領域に吸収を持つ他の色素を加えることもできる。
【００７０】
本発明のディスプレー用フィルターの構成は、必要に応じて変えることができ、本発明の透明積層体に金属電極、保護樹脂層、透明成形体および反射防止層またはアンチニュートンリング層またはノングレア層からなる群から選択される、少なくとも２つを同時に備えていることが好ましい。
【００７１】
本発明の透明積層体およびディスプレイ用フィルターは、近赤外線抑止能に優れ、また、本発明の色素を併用しない透明積層体およびディスプレイ用フィルターは、通常一般の有機色素を用いたディスプレイ用近赤外線カットフィルターに比較して、湿度、熱、光といった環境による劣化が少ない。また先述した式（１）または式（２）で表されるジチオール錯体化合物、またはそれらの少なくとも１種以上の混合物は、耐環境性に優れるため、これらを色素として併用した場合も劣化が少ないディスプレイ用フィルターが得られる。従って、本発明のディスプレイ用フィルターは、近赤外線カットフィルターとしても好適に使用できる。
【００７２】
本発明のディスプレイ用フィルターの使用、装着方法としては大きく分けて、以下のものが挙げられるが、これらに特に制限されるものではない。▲１▼電磁波シールド能および近赤外線抑止能を有するディスプレイ用フィルターでフィルター主面をディスプレイ画面に密着させて装着して使用する。▲２▼電磁波シールド能および近赤外線抑止能を有するディスプレイ用フィルターでフィルター主面をディスプレイ画面から離して使用する。▲３▼近赤外線抑止能を有するディスプレイ用フィルターでディスプレイ画面に密着させて装着し使用する▲４▼近赤外線抑止能を有するディスプレイ用フィルターでフィルター主面をディスプレイ画面から離して使用する。
【００７３】
▲１▼は〔図４〕をもって説明するに、通常、ディスプレイ側から、アンチニュートンリング層５０及び／または保護樹脂層４０及び金属電極２０／透明積層体１０／透明成形体３０／反射防止層またはノングレア層６０の順で構成される。▲２▼は〔図５〕をもって説明するに、通常、ディスプレイ側から、保護樹脂層６０及び金属電極２０／透明積層体１０／透明成形体３０／反射防止層またはノングレア層６０の順で構成される。▲３▼は〔図６〕をもって説明するに、通常、ディスプレイ側から、アンチニュートンリング層５０／保護樹脂層４０／透明積層体１０／透明成形体３０／反射防止層またはノングレア層６０の順で構成される。▲４▼は〔図７〕をもって説明するに、通常、ディスプレイ側から、保護樹脂層４０／透明積層体１０／透明成形体３０／反射防止層またはノングレア層６０の順で構成される。近赤外線吸収色素を用いる場合は、色素が上記の各構成要素のいずれか１つ以上に含有されるか、色素を含有する透明成形物が上記の各構成要素の間のいずれかに挟み込まれる。
【００７４】
上記▲３▼の場合、通常アンチニュートンリング層はノングレア性を有しており、さらにディスプレイ用フィルターの人側面のノングレア層がアンチニュートンリング性を有していれば、フィルターのどちら面をディスプレイ画面に密着させて用いることができる。
【００７５】
本発明のディスプレイ用フィルターは、ディスプレイに装着したとき、装着用冶具、電極部分等が視認者から見えないようにするために、任意の額縁印刷を施して良い。印刷形状、印刷面、印刷色、印刷方法は特に特定されるものではない。また、ディスプレイに装着するための穴加工等の加工を施しても良い。
【００７６】
さらに偏光フィルムや位相差フィルム等をつけて円偏光フィルターの性能を付加することで、ディスプレー側からの反射光を抑えることができ、さらに優れたフィルターとなる。
【００７７】
本発明のディスプレー用フィルターは可視光線透過率が高いためディスプレーの鮮明度が損なわれず、ディスプレイから発生する健康に害をなすといわれている電磁波を遮断する電磁波シールド性に優れ、さらに、ディスプレーからでる８００〜１０００ｎｍ付近の近赤外線光を効率よくカットするため、周辺電子機器のリモコン、伝送系光通信等が使用する波長に悪影響を与えず、それらの誤動作を防ぐことができる。
【００７８】
【実施例】
つぎに、本発明を実施例により具体的に説明する。本発明はこれによりなんら制限されるものではない。以下の実施例および比較例で示す薄膜の厚さは、成膜条件から求めた値であり、実際に測定した膜厚ではない。
［実施例１］
ポリエチレンテレフタレートフィルム（厚さ：５０μｍ）の一方の主面に、ターゲットにインジウムを、スパッタガスにアルゴン・酸素混合ガス（全圧２６６mPa ：酸素分圧８０mPa ）を用いて、酸化インジウム薄膜を、ターゲットに銀を、スパッタガスにアルゴンガス（全圧２６６mPa ）を用いて銀薄膜を、マグネトロンＤＣスパッタリング法により、酸化インジウム薄膜４０nm、銀薄膜１０nm、酸化インジウム薄膜７０nm、銀薄膜１０nm、酸化インジウム薄膜４０nmの順に積層し、透明導電性積層体を作製し、粘着材を用いて２枚を〔図１〕の如く重ねて本発明の透明積層体を作製した。
【００７９】
［比較例１］
ポリエチレンテレフタレートフィルム（厚さ：５０μｍ）の一方の主面に、実施例１と同様に酸化インジウム薄膜４０nm、銀薄膜１０nm、酸化インジウム薄膜７０nm、銀薄膜１０nm、酸化インジウム薄膜４０nmの順に積層し、透明導電性積層体を作製した。
【００８０】
［実施例２］
ポリエチレンテレフタレートフィルム（厚さ：５０μｍ）の一方の主面に、ターゲットにインジウムとスズの合金（Ｉｎ：Ｓｎ= ９５：５）を、スパッタガスにアルゴン・酸素混合ガス（全圧２６６mPa ：酸素分圧８０mPa ）を用いて、ＩＴＯ薄膜１μｍをマグネトロンＤＣスパッタリング法により積層し、透明導電性積層体を作製し、粘着材を用いて２枚を〔図１〕の如く重ねて透明積層体を作製した。
【００８１】
［実施例３］
ポリエチレンテレフタレートペレット１２０３（ユニチカ（株）製）に下記式（３）〔化３〕で示されるジチオール錯体を０．３ｗｔ％混合し、260 〜280 ℃で溶融させ、押し出し機により厚み１００μｍのフィルムを作製した。その後、このフィルムを２軸延伸して、厚み５０μｍのフィルムとし、実施例１の透明積層体に粘着材を用いて貼り合わせ、本発明のディスプレイ用フィルターを作製した。
【００８２】
【化３】

【００８３】
［実施例４］
実施例３と同様に下記式（３）〔化３〕で示されるジチオール錯体０．６ｗｔ％、下記式（４）〔化４〕で示されるジチオール錯体を０．８ｗｔ％の厚み５０μｍのフィルムを作製し、実施例２の透明積層体に粘着材を用いて貼り合わせ、本発明のディスプレイ用フィルターを作製した。
【００８４】
【化４】

【００８５】
以上のようにして作製した実施例１、２の透明積層体、実施例３、４のディスプレイ用フィルター、及び比較例１の透明導電性積層体の可視光線透過率、合成面抵抗、近赤外線抑止能を以下の方法で評価した。
１）可視光線透過率（Ｔvis ）及び近赤外線透過率
測定対象物を小片に切り出し、（株）日立製作所製分光光度計（U-3400）により３００〜１０００nmの平行光線透過率を測定した。ここで求めた透過率からＴvis を計算した。近赤外線透過率は８２０nm、８５０nm、１０００nmで評価を行った。
２）合成面抵抗
四端子法（プローブ間隔１ｍｍ）により比較例１、実施例２の透明導電性積層体の面抵抗を測定し、実施例１と実施例２の透明積層体の合成面抵抗は、それぞれ比較例１、実施例２の透明導電性積層体の面抵抗から計算して求めた。
３）リモコン試験
プラズマディスプレイの画面に各積層体やフィルターを設置して、リモコンを使用する電子機器を0.2m〜3mディスプレイから離してその誤動作を確認した。誤動作がある場合は、その限界距離を求めた。限界距離が短いほど誤動作が少ないといえる。
以上の結果を〔表１〕に掲げる。
【００８６】
【表１】

【００８７】
表１から明らかなように、実施例１の透明積層体は、比較例１の透明導電性積層体を２枚貼りあわせたものであり、大きな近赤外線抑止能を有しており、誤動作限界距離は充分実用的である。また、実施例１の透明積層体に、近赤外線吸収色素を含有するフィルムを貼り合わせた実施例３では、可視光線透過率は減少したものの、近赤外線抑止性はさらに向上した。比較例１の透明導電性積層体単体では、誤動作限界距離が大きく、近赤外線カットフィルターとして使用できない。実施例２のＩＴＯを使用した透明積層体は、近赤外線抑止能が小さいが、この透明積層体に近赤外線吸収色素を含有するフィルムを貼り合わせた実施例４では、可視光線透過率は減少したものの、近赤外線抑止性は向上し、実用的になった。
【００８８】
［実施例５］
実施例１の透明積層体（４７２mm×３５０mm）の薄膜形成面すなわち導電面に〔図１〕及び〔図２〕に示すように銀ペースト（三井東圧化学（株）製）をスクリーン印刷し、乾燥させ厚さ２０μｍ、幅１０mmの金属電極を形成して、本発明のディスプレイ用フィルターを作製した。
【００８９】
［比較例２］
比較例１の透明積層体（４７２mm×３５０mm）に実施例５と同様に金属電極を形成して、本発明のディスプレイ用フィルターを作製した。
【００９０】
［実施例６］
実施例２の透明積層体（４７２mm×３５０mm）に実施例５と同様に金属電極を形成して、本発明のディスプレイ用フィルターを作製した。
【００９１】
以上のようにして作製した実施例５、６のディスプレイ用フィルター、及び比較例２のディスプレイ用フィルターの電磁波シールド能を以下のように評価した。
１）電磁波シールド能
ディスプレイ用フィルターをプラズマディスプレイの画面に設置して、ダイポールアンテナを画面中心位置から面の垂線方向３ｍの位置に設置し、アドバンテスト製スペクトラム・アナライザ（TP4172）で２０〜９０ＭＨｚ帯域における放射電界強度を測定した。この際、ディスプレイ用フィルターの金属電極部全体とディスプレイ本体のアース用電極全体を接触させ、アースをとった。33、62、70、80MHz での放射電界強度で評価を行った。
ディスプレイ用フィルターがないときの放射電界強度の測定結果と併せて、上記の評価結果を以下の〔表２〕に掲げる。
【００９２】
【表２】

【００９３】
〔表２〕から明らかなように、比較例２では帯域によってシールド効果がない。実施例５、６で示すように、合成面抵抗が４Ω／□以下では全帯域にわたって十分な効果があるが、合成面抵抗が３Ω／□以下である実施例４は、より実用的である。
【００９４】
［実施例７］
ポリエチレンテレフタレートフィルム（厚さ：５０μｍ）の一方の主面に、大日本インキ化学工業（株）製熱硬化ニス（SF-C-335）3gをトルエン／メチルケトン(10:1)の混合溶媒100gに溶解して、塗布、自然乾燥後、１５０℃で２０秒間硬化させて１μｍ厚のアンチニュートンリング層を形成し、アンチニュートンリングフィルムを作製した。実施例５のディスプレイ用フィルターの金属電極が形成されていない、貼り付けたときにディスプレイ本体の表示部と密着する方の面に、保護樹脂層としてアクリル系樹脂をスクリーン印刷、硬化処理にて１０μｍ形成し、該保護樹脂層上に該アンチニュートンリングフィルムをアンチニュートンリング層がディスプレイ側になるように粘着材を用いて貼り合わせた。さらに該ディスプレイ用フィルターの反対面と、片面にノングレア層を有する厚さ2mm のＰＭＭＡ板（三菱レイヨン（株）製アクリルフィルターMR-NG ）のノングレア層の形成されていない面を貼り合わせ、本発明のディスプレイ用フィルターを作製した。
【００９５】
該ディスプレイ用フィルターの可視光線透過率は６５％、合成面抵抗は２．９Ω／□、近赤外線透過率は、８２０ｎｍにおいて９．３％、８５０ｎｍにおいて２．７％、１０００ｎｍにおいて１．２％であった。該ディスプレイ用フィルターをプラズマディスプレイの画面に設置したところ、周辺の電子機器の誤動作は起こらなかった。また、ニュートンリングも発生せず、画像は鮮明であり、また映り込みが少なく視認性が良かった。
【００９６】
【発明の効果】
以上のごとく、本発明によれば、透明基体（Ａ）の一方の主面上に透明導電層（Ｂ）を積層した透明導電性積層体（Ｃ）が２枚以上重ねられてなる、合成面抵抗４Ω／□以下かつ可視光線透過率４０％以上の透明積層体が、電極を形成し接地することによってプラズマディスプレイの発する強度の電磁波を遮蔽でき、また、ディスプレイの鮮明性を損なわない可視域での高透明性と、周辺電子機器の誤動作を誘発する８２０nmより長波長の近赤外線光の抑止性を有する透明積層体を提供でき、さらにこの透明積層体を用いることによって電磁波シールド性、高透明性、近赤外線抑止性、防眩性または反射防止能、アンチニュートンリング性、または静電防止性に優れるディスプレイ用フィルターを提供できる。またさらに、近赤外線吸収色素を用いると、さらに近赤外線抑止能に優れるディスプレイ用フィルターを提供できる。
【図面の簡単な説明】
【図１】本発明のディスプレイ用フィルターの一例を示す断面図
【図２】本発明のディスプレイ用フィルターの一例を示すディスプレイ側から見た平面図
【図３】本発明のディスプレイ用フィルターの一例を示す断面図
【図４】本発明のディスプレイ用フィルターの一例を示す断面図
【図５】本発明のディスプレイ用フィルターの一例を示す断面図
【図６】本発明のディスプレイ用フィルターの一例を示す断面図
【図７】本発明のディスプレイ用フィルターの一例を示す断面図
【符号の説明】
１０ 透明積層体
１１ 透明基体（Ａ）
１２ 透明導電層（Ｂ）
１５ 透明導電性積層体（Ｃ）
２０ 金属電極
３０ 透明成形体（Ｄ）
４０ 保護樹脂層
５０ アンチニュートンリング層
６０ 反射防止層またはノングレア層[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a transparent laminate and a filter for a display using the same, and more specifically, electromagnetic shielding that blocks electromagnetic waves generated from a plasma display, which are said to be harmful to health, and leads to erroneous operation of peripheral electronic devices. Transparent laminated body with excellent near-infrared deterrence that blocks near-infrared rays, and electromagnetic shielding, near-infrared deterrence, high transparency, anti-reflection or anti-glare properties, anti-Newton ring property, anti-static using the same The present invention relates to a filter for a display having both functions.
[0002]
[Prior art]
As society becomes highly information-oriented, optoelectronic components and equipment are remarkably advanced and popularized. Among them, displays are remarkably widespread for televisions, personal computers, and the like, and their thickness and size have been reduced. In recent years, plasma displays have been attracting attention for large thin TVs, thin display applications, and the like, and have already begun to appear on the market. However, since the plasma display generates a strong leakage electromagnetic field due to its structural principle, the influence of the leakage electromagnetic field on the human body and other devices has recently been taken into account. It is necessary to clear.
Further, dust is likely to adhere to the display surface due to electrostatic charging, and when the human body comes into contact, it may be discharged and receive an electric shock, so it is necessary to perform antistatic treatment.
[0003]
In addition, the plasma display emits near infrared light and acts on peripheral electronic devices such as a cordless phone to cause a malfunction. Wavelengths that are particularly problematic include 820 nm, 880 nm, and 980 nm that are used for remote control and transmission optical communication. Therefore, it is necessary to cut light in a wavelength region of 800 to 1000 nm that is a near infrared region.
[0004]
Regarding the near-infrared deterring ability, it has been conventionally known to produce a near-infrared absorption filter using a near-infrared absorbing dye, but there are various problems. For example, cyanines are not practical due to their poor light stability, and anthraquinones and naphthoquinones are problematic because they absorb in the visible region and lower the visible light transmittance of the filter. On the other hand, phthalocyanine dyes have high light resistance and absorb near-infrared light in the 700-800 nm region well, but there are some that cannot absorb wavelengths of 800 nm or more where malfunction is a problem, and naphthalocyanine dyes are relatively Expensive.
[0005]
Since the plasma display emits intense near-infrared light, it is necessary to use a near-infrared absorption filter with a large absorption rate in the near-infrared region. In some cases, it is necessary to increase the amount of the dye to be contained, and in that case, a reduction in the visible light transmittance associated therewith becomes a problem.
[0006]
Moreover, the required performance to be satisfied as a filter for plasma display is not only near-infrared deterrence but also electromagnetic wave shielding ability, etc. Therefore, it is necessary to increase the number of members as the required performance increases, and of course the problem of cost This leads to problems such as a decrease in visible light transmittance caused by the bonding of the members and an increase in reflection due to the bonding interface. The plasma display filter is installed in front of the display in order to cut near-infrared light and electromagnetic waves emitted from the display. Therefore, if the transmittance of visible light is low, the sharpness of the image is lowered. In general, the higher the visible light transmittance of the filter, the better. At least 40% or more, preferably 50% or more is required.
[0007]
The antistatic ability can be solved by directly forming a conductive film on the display surface or attaching a member having a conductive film to the display surface and grounding the conductive film. In this case, the conductive film has a surface resistance of 10⁸It should be about Ω / □ or less, and it should not impair the transparency and resolution of the display screen. On the other hand, in order to shield the leakage electromagnetic field (electromagnetic wave), it is necessary to cover the display surface with a conductive material having higher conductivity. Generally, a metal mesh that is grounded or a metal mesh coated with a synthetic resin or metal fiber is used. However, these methods produce parts that do not transmit light emitted from the display, cause moire, and increase costs due to poor yield. Is a problem. Therefore, a transparent conductive film typified by ITO (Indium Tin Oxide) is used for the electromagnetic wave shielding layer.^FiveΩ / □ or less, preferably 10^ThreeΩ / □ or less. The transparent conductive film includes metal thin films such as gold, silver, copper, platinum, and palladium, oxide semiconductor thin films such as indium oxide, stannic oxide, and zinc oxide, and multilayer thin films in which metal thin films and high refractive index transparent thin films are laminated. There is. Among them, the metal thin film can obtain conductivity, but a metal thin film having high visible light transmittance cannot be obtained due to reflection and absorption over a wide wavelength region. In addition, an oxide semiconductor thin film is more transparent than a metal thin film, but is inferior in conductivity, and has no near infrared reflectivity. On the other hand, multilayer thin films composed of a metal thin film and a high refractive index transparent thin film have the conductivity and optical properties of metals such as silver and the prevention of reflection by metal in a certain wavelength region of the high refractive index transparent thin film. In addition, it has preferable characteristics in any of conductivity, near infrared ray deterrence ability, and visible light transmittance.
[0008]
However, in the electromagnetic wave shield body using ITO as a transparent conductive layer, there is no shield for the electromagnetic wave emitted by the plasma display, and it has high electromagnetic transparency that has the electromagnetic wave shielding ability of the plasma display and does not impair the transparency of the display. Neither the electromagnetic wave shield nor the electromagnetic wave shield having the ability to suppress near infrared rays has been obtained.
[0009]
From the viewpoint of productivity, profitability, and prevention of scattering when the glass of the display is broken, it is preferable to use a transparent plastic film as the base material for the electromagnetic wave shield, but the strength of the film alone is insufficient. Therefore, it is used as a display filter by being bonded to a transparent glass plate or plastic plate. However, when such a display filter is mounted in close contact with the display surface, the degree of adhesion between the display surface and the filter varies depending on the location, and Newton rings are generated due to gaps formed thereby. Also, if the reflection of the electromagnetic wave shield or other members is large, or if a display filter having electromagnetic wave shielding ability is made with a large number of members, the reflective interface increases, so that the reflection of the entire display incorporating the filter Since the rate increases, it is difficult to see the display screen due to the reflection of illumination or the like, it becomes difficult to read the image, and obstacles such as visual fatigue occur.
[0010]
[Problems to be solved by the invention]
An object of the present invention is to provide an electromagnetic shielding ability that blocks electromagnetic waves that are said to be harmful to health generated from a plasma display in view of the above-described prior art, and a near-infrared deterrent that blocks near-infrared rays that cause erroneous operation of peripheral electronic devices. Provides transparent laminates that are superior to the above, and display filters that combine electromagnetic shielding, high transparency, near-infrared deterrence, anti-reflection or anti-glare properties, anti-Newton ring properties, or anti-static properties using the same It is to be.
[0011]
[Means for Solving the Problems]
As a result of intensive investigations to solve the above problems, the present inventors have made it possible to shield a very strong, particularly problematic 20 to 90 MHz band electromagnetic wave generated from a plasma display by using a transparent substrate ( Two or more transparent conductive laminates (C) each having a transparent conductive layer (B) laminated on one main surface of A) are combined, and the combined surface resistance is 4Ω / □ or less, preferably 3Ω / □ or less, and visible. A transparent laminate having a light transmittance of 40% or more is preferable. Further, in order to suppress near-infrared light emitted by a plasma display to such an extent that malfunction of peripheral equipment does not occur, the light transmittance in a region longer than 820 nm is 10%. It was found that the content was preferably not more than%, and the present invention was completed.
[0012]
That is, the present invention provides (1) a transparent conductive laminate (C) in which a transparent conductive layer (B) is formed on at least one main surface of a transparent substrate (A).The transparent substrate (A) of one transparent conductive laminate (C) and the transparent conductive layer (B) of the other transparent conductive laminate (C) are opposed to each other with at least two sheets having different sizes. The transparent laminate has a visible light transmittance of 40% or more, a combined surface resistance of 4Ω / □ or less, and a metal electrode is formed on at least two transparent conductive layers (B). Filter for plasma display(2) The light transmittance in a region having a wavelength longer than 820 nm is 10% or less.plasmaThe filter for display, (3) The transparent conductive layer (B) is mainly composed of indium oxide and tin oxide, as described in (1) or (2)plasmaFilter for display, (4) transparent conductive layer (B), high refractive index transparent thin film layer (B-1), metal thin film layer (B-2) in this order (B-1) / (B-2) (1) or (2), characterized in that a high refractive index transparent thin film layer (B-1) is further laminated thereon at least once as a repeating unit.plasmaThe filter for display, (5) The high refractive index transparent thin film layer (B-1) is mainly composed of indium oxide, as described in (4)plasmaThe filter for display, (6) The metal thin film layer (B-2) is composed of silver or an alloy containing silver, (4) or (5)plasma(7) The filter for display, (7) The transparent substrate (A) is a transparent polymer molded product,plasmaThe filter for display, (8) The transparent substrate (A) contains a dye, (1) to (7),plasmaA filter for display, (9) According to any one of (1) to (8)plasmaA protective resin layer is formed on the surface of the transparent conductive layer (B) of the display filter.plasmaA filter for display, according to any one of (10) (1) to (9)plasmaOne surface of the transparent molded body (D) is bonded to the display filter.plasmaA filter for display according to any one of (11) (1) to (10)plasmaAn antireflection layer, an anti-Newton ring layer or a non-glare layer is formed on at least one surface of a display filterplasmaFilter for display, (12) Antireflection layer or non-glare layer, or anti-Newton ring layer / transparent molded article (D) / (1) to (8) display filter / protective resin layer and anti-Newton ring A filter for plasma display, wherein the filter for display according to any one of (13), (1) to (8) is provided with a protective resin layer and a transparent layer. It comprises at least two selected from the group consisting of a molded body and an antireflection layer, an anti-Newton ring layer or a non-glare layer at the same time.plasmaFilter for display, (14) Transparent substrate (A) and / or protective resin layer and / or transparent molded body (D) and / or anti-Newton ring layer and / or non-glare layer are characterized by containing pigment (1) to (13)plasmaA filter for display according to any one of (15) (1) to (14)plasmaA transparent molded product (E) containing a pigment is formed in a display filter.plasmaDisplay filterIt is.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The transparent laminate of the present invention is obtained by stacking at least two transparent conductive laminates (C) in which the transparent conductive layer (B) is laminated on at least one main surface of the transparent substrate (A). The laminate has a visible light transmittance of 40% or more and a combined surface resistance of 4Ω / □ or less, and preferably has a light transmittance of 10% or less in a wavelength region longer than 820 nm.
[0014]
Examples of the transparent substrate (A) in the present invention include glass, quartz and other inorganic compound moldings and transparent organic polymer moldings, but the polymer moldings can be used more suitably because they are light and difficult to break. The polymer molding may be transparent in the visible wavelength region, and specific examples thereof include polyethylene terephthalate, polyethersulfone, polystyrene, polyethylene naphthalate, polyarylate, polyetheretherketone, polycarbonate, polypropylene. , Polyimide, triacetyl cellulose and the like, but are not limited thereto. These transparent polymer molded products may be plate-shaped or film-shaped as long as the main surface is smooth. When a plate-shaped polymer molded product is used as a substrate, the substrate is excellent in dimensional stability and mechanical strength, so that a transparent laminate having excellent dimensional stability and mechanical strength can be obtained. It can be preferably used when required. In addition, the transparent polymer film has flexibility, and since the transparent conductive layer can be continuously formed by a roll-to-roll method, when this is used, the transparent laminate can be efficiently formed. This can also be suitably used because it can be produced and the film-like transparent laminate is affixed to the glass of the display to prevent scattering when the glass is broken. In this case, the thickness of the film is usually 10 to 250 μm. If the thickness of the film is less than 10 μm, the mechanical strength as a substrate is insufficient, and if it exceeds 250 μm, the flexibility is insufficient, so that the film is not suitable for being wound with a roll.
[0015]
The surface of these substrates is subjected to etching treatment such as sputtering treatment, corona treatment, flame treatment, ultraviolet ray irradiation, electron beam irradiation and undercoat treatment on the surface in advance to improve the adhesion of the film layer formed on the substrate to the substrate. You may perform the process to make. For example, in order to enhance the adhesion between the transparent substrate and the thin film layer, an arbitrary inorganic layer may be formed therebetween. Specific examples of the material include copper, nickel, chromium, gold, silver, platinum, zinc, zirconium, titanium, tungsten, tin, palladium and the like, or an alloy made of two or more of these materials. It is not limited to. The thickness may be a thickness that does not impair the transparency, and is preferably about 0.02 nm to 10 nm. If the thickness is thin, a sufficient effect of improving the adhesion cannot be obtained. On the other hand, if it is too thick, the transparency is impaired. When the thin film layer to be formed is an oxide, part or all of the metal of the inorganic layer is actually a metal oxide, but there is no problem in its effect. In addition, before forming the thin film layer, a dust-proof treatment such as solvent cleaning or ultrasonic cleaning may be performed as necessary.
[0016]
In the present invention, as the transparent conductive layer (B), the high refractive index transparent thin film layer (B-1) and the metal thin film layer (B-2) are repeated in this order (B-1) / (B-2). Examples of the unit that are repeatedly laminated at least once as a unit and that at least the high refractive index transparent thin film layer (B-1) is further laminated thereon, or that are composed of an oxide semiconductor, are included.
[0017]
The transparent conductive laminate (C) in the present invention is obtained by laminating a transparent conductive layer (B) on a transparent substrate (A).
In the present invention, the composite surface resistance means that when the transparent laminate has a plurality of conductive layers, the composite surface resistance Rs is expressed by the following formula (1) using the surface resistances R1, R2,. 1).

The electromagnetic wave shielding is performed by the effects of (1) reflection and (2) absorption by the electromagnetic wave shield body. In order to shield the electromagnetic wave having the intensity of the plasma display, the electromagnetic shielding body (transparent laminate) is required to have low resistance conductivity with a combined surface resistance of 4Ω / □ or less, preferably 3Ω / □ or less. For absorption, the electromagnetic shielding body needs to have conductivity, and in order to absorb all the electromagnetic waves generated from the display, the conductive layer needs to be thicker than a certain value, but the conductive layer, that is, the metal thin film layer is thickened. Then, even if a high refractive index transparent thin film layer is used, the visible light transmittance is low. Therefore, it is also important to increase the reflection interface by multilayer lamination and increase the reflection of electromagnetic waves.
[0018]
The shielding effect representing the electromagnetic wave shielding ability represents how much electromagnetic wave energy is attenuated, and its magnitude is expressed in decibels (dB). The shield effect (SE) is a relative evaluation represented by the following formula (2), and it can be said that the larger this value, the more effective the shield is. Ei represents the incident electric field intensity, Et represents the transmission electric field intensity, that is, the electric field intensity of the electromagnetic wave transmitted through the shield, and the unit is V / m.
SE = 20 Log (Ei / Et) (2)
The regulation value of VCCI is indicated by a radiation field intensity that is an absolute value, and its unit is dB μV / m. In Class I indicating the regulation value for industrial use, it is 50 dBμV / m, and in Class II indicating the regulation value for household use, it is 40 dBμV / m. Since the radiation electric field intensity of the plasma display exceeds 40 dBμV / m in the 20 to 90 MHz band, it cannot be used as it is for home use. Practically, the radiation electric field intensity needs to be 40 dBμV / m or less, preferably 35 dBμV / m or less, more preferably 30 dBμV / m or less. When the radiation field intensity of the plasma display is 50 dBμV / m, an electromagnetic wave shield having a shielding effect of 10 dB or more, preferably 15 dB or more, more preferably 20 dB or more is required. For this purpose, it is only necessary that the electromagnetic wave shield has a high conductivity of a surface resistance of 4Ω / □ or less, preferably 3Ω / □ or less, and it is also important to have a large number of reflective interfaces due to multilayer lamination. That's it.
[0019]
In addition, since the plasma display emits intense near-infrared light, it is preferable to cut light in the wavelength region of 800 to 1000 nm, which is the near-infrared region, and the light transmittance in the region of wavelengths longer than 820 nm is 10% or less. It is preferable to make it. From the demand for reducing the number of members and the limit of near-infrared absorption using dyes, it is desirable that the electromagnetic wave shield itself has near-infrared deterrence. When using near-infrared absorbing dyes, the near-infrared deterrence required for the electromagnetic wave shield is lower than the required performance, but if the near-infrared deterrence of the electromagnetic wave shield is too low, the near-infrared absorbing dye is necessary. The amount increases, and there is a risk of reducing the visible light transmittance. Therefore, it is desirable that the electromagnetic wave shield in the case of using the near-infrared absorbing dye has a light transmittance of 20% or less in a region having a wavelength longer than 820 nm, for example.
[0020]
In the near-infrared cut, reflection by free electrons of metal can be used. However, when the metal thin film layer is thickened, the visible light transmittance is lowered as described above, and when the metal thin film is thinned, the reflection of near-infrared light is weakened. Therefore, the visible light transmittance is increased and the overall thickness of the metal thin film layer is increased by stacking a laminated structure in which a metal thin film layer of a certain thickness is sandwiched between high refractive index transparent thin film layers at least once. In addition, by controlling the thickness of each layer, the visible light transmittance, the near infrared transmittance, and the color can be changed within a certain range. If the visible light transmittance is low, the sharpness of the image is lowered when the display is installed. Therefore, the higher the visible light transmittance of the filter, the better, and at least 40% or more, preferably 50% or more. Furthermore, the color of the electromagnetic shielding body greatly affects the contrast of the display, etc. For the electromagnetic shielding body for plasma display, the green color due to impervious reddish purple is unsuitable, and it is neutral gray or blue due to impervious red yellow. Is required. For this purpose, control of the color, visible light transmittance, and near-infrared transmittance is generally easier to optically design with a multilayer stack.
[0021]
In addition, oxide semiconductors such as indium oxide, tin oxide, and zinc oxide, and binary oxide semiconductors such as a mixture of indium oxide and tin oxide (ITO) are excellent in transparency. A low-resistance conductive film can be formed by forming a highly conductive oxide semiconductor thin film as thick as several thousand to several μm. A transparent conductive film formed with an oxide semiconductor reflects near infrared rays to some extent by carrier electrons exhibiting conductivity, but cannot satisfy the near infrared transmittance required for a filter for plasma display. It is desirable to use together.
[0022]
Multi-layer stacking with a metal thin film layer sandwiched between high refractive index transparent thin film layers limits the production equipment that can be used, and it is also necessary to control the thickness of each multilayer, etc. It is difficult to stably obtain optical characteristics and surface resistance. For example, stacking 3 or more stages in one batch is not limited to expensive production equipment, and each film thickness of 7 or more layers can be controlled stably. Must. In the case of a transparent conductive film in which an oxide semiconductor is formed thick, it is difficult to form a thick film at a time so as to satisfy the above-mentioned low resistance because of problems of line speed and film formation stability. Further, when the film is formed once again, there is a problem that the yield is lowered.
[0023]
However, a transparent conductive layer in which a laminated structure in which a metal thin film layer is sandwiched between high refractive index transparent thin film layers is stacked one or more times or a transparent conductive layer in which an oxide semiconductor is formed thick is formed on one main surface of a transparent substrate. By stacking two or more transparent conductive laminates, a transparent laminate having a desired composite surface resistance and further a desired near-infrared transmittance can be obtained, and the above-described effects can be obtained. Moreover, the reflection interface of electromagnetic waves can be increased by stacking two or more sheets. The transparent conductive laminate to be stacked may be the same or different. A transparent conductive laminate formed with a transparent conductive layer in which a laminated structure in which a metal thin film layer is sandwiched between high refractive index transparent thin film layers is stacked at least once, and a transparent conductive layer in which an oxide semiconductor is formed thickly are formed on a transparent substrate. Transparent conductive laminates may be stacked. As a stacking method, the transparent conductive laminates are bonded to each other via an adhesive or an adhesive. Inclusions having an arbitrary function may be present between the transparent conductive laminates. However, in the case where the inclusions are present in the light transmission part from the display, the inclusions must be sufficiently transparent to visible light. .
[0024]
When forming a transparent conductive layer in which a laminated structure in which a metal thin film layer is sandwiched between high refractive index transparent thin film layers is formed one or more times, a high refractive index transparent thin film layer (B-1) on one main surface of the transparent substrate, In the order of the metal thin film layer (B-2), (B-1) / (B-2) is repeatedly laminated one or more times, and at least a high refractive index transparent thin film layer is laminated thereon. The number of repeated lamination is preferably 1 to 3 times. That is, transparent substrate / high refractive index transparent thin film layer / metal thin film layer / high refractive index transparent thin film layer, transparent substrate / high refractive index transparent thin film layer / metal thin film layer / high refractive index transparent thin film layer / metal thin film layer / high refraction Or transparent substrate / high refractive index transparent thin film layer / metal thin film layer / high refractive index transparent thin film layer / metal thin film layer / high refractive index transparent thin film layer / metal thin film layer / high refractive index transparent thin film layer is there. If the number of repetitions is 4 times or more, the problem of production equipment limitations and productivity increases.
[0025]
In order to obtain a desired transparent conductive laminate by controlling the visible light transmittance, the transmittance of near-infrared light, and the color by multilayer lamination of a high refractive index transparent thin film layer and a metal thin film layer, a transparent substrate and a thin film material Optical design using a vector method using a refractive index and an extinction coefficient, a method using an admittance diagram, and the like are performed, and a thin film material, the number of layers, a film thickness, and the like of each layer are determined. In addition, film formation can be performed while controlling the number of layers, film thickness, and the like while observing optical characteristics.
[0026]
The thickness of the metal thin film layer is optically designed and experimentally determined from conductivity, optical characteristics, etc., and is not particularly limited as long as the transparent laminate obtained by laminating the obtained transparent conductive laminate has the required characteristics. However, since it is necessary for the thin film to have a continuous state rather than an island structure because of conductivity or the like, the thickness is preferably 4 nm or more. If the metal thin film layer is too thick, transparency is a problem, and 30 nm or less is desirable.
[0027]
Specific examples of the metal thin film include silver, gold, platinum, palladium, nickel, chromium, zinc, zirconium, titanium, tungsten, tin, and the like, or an alloy made of two or more of these materials. Among these, silver is preferably used because it is excellent in conductivity, infrared reflectivity, and visible light transmittance when multilayered. However, since silver lacks chemical and physical stability and degrades due to environmental pollutants, heat, light, etc., silver is one or more of environmentally stable metals such as gold, platinum, palladium, indium and tin. The contained alloy is preferably used. Here, the silver content of the alloy containing silver is not particularly limited, but it is desirable that the conductivity and optical characteristics of the silver thin film are not significantly changed, and is about 50 wt% or more and less than 100 wt%. However, the addition of other metals to silver hinders its excellent conductivity, so it is desirable to use at least one layer without alloying silver if possible. If the adjacent high refractive index transparent thin film layer is an oxide, a part of the metal of the metal thin film layer may actually be a metal oxide, but it is a very thin region. There is no particular problem in optical design and film formation. Further, the metal thin film first layer, second layer,..., N-th layer (n ≧ 2) are not necessarily the same thickness, and need not be the same metal or alloy. For the formation of the metal thin film layer, any conventionally known method such as sputtering, ion plating, vacuum deposition, or plating can be employed.
[0028]
The high refractive index transparent thin film layer is not particularly limited as long as it has transparency in the visible range and has an effect of preventing light reflection in the visible range in the metal thin film layer. A material having a high refractive index of 1.6 or more, preferably 1.7 or more is used. Specific materials for forming such a high refractive index transparent thin film layer include oxides such as indium, titanium, zirconium, bismuth, tin, zinc, antimony, tantalum, cerium, neodymium, lanthanum, thorium, magnesium, and gallium. Or a mixture of these oxides or zinc sulfide. These oxides or sulfides can be used as long as they do not significantly change the optical characteristics even if the stoichiometric composition of metal and oxygen or sulfur is different. Among them, indium oxide or a mixture of indium oxide and tin oxide (ITO) can be suitably used because of its high film forming speed and good adhesion to a metal thin film layer in addition to transparency and refractive index. . In addition, by using an oxide semiconductor thin film having a relatively high conductivity such as ITO, the amount of electromagnetic waves absorbed can be increased and the conductivity of the electromagnetic wave shield can be increased. The thickness of the high refractive index transparent thin film layer is determined by optical design and experiment from the optical characteristics of the transparent substrate, the thickness of the metal thin film layer, the optical characteristics, and the refractive index of the transparent thin film layer, and is particularly limited. Although it is not a thing, it is preferable that they are 5 nm or more and 200 nm or less, More preferably, they are 10 nm or more and 100 nm or less. Further, the high refractive index transparent thin film first layer, the second layer,..., The nth layer (n ≧ 2) are not necessarily the same thickness, and may not be the same transparent thin film material. For the formation of the high refractive index transparent thin film layer, any of conventionally known methods such as sputtering, ion plating, ion beam assist, vacuum deposition, and wet coating can be employed.
[0029]
Sputtering is suitable for film thickness control and multilayer lamination, and a metal thin film layer and a high refractive index transparent thin film layer can be formed easily and continuously. As a specific example, a high refractive index transparent thin film layer mainly composed of indium oxide and a metal thin film layer made of silver or an alloy containing silver are continuously formed by a sputtering method. The high refractive index transparent thin film layer mainly composed of indium oxide is formed by reactive sputtering using a metal target containing indium as a main component or a sintered body target containing indium oxide as a main component. In the reactive sputtering method, an inert gas such as argon is used as a sputtering gas, oxygen is used as a reactive gas, and a normal pressure of 0.1 to 20 mTorr, direct current (DC) or radio frequency (RF) magnetron sputtering is used. it can. The oxygen gas flow rate is experimentally determined from the obtained film forming speed and is controlled so as to obtain a thin film having a desired transparency. For forming a metal thin film layer made of silver or an alloy containing silver, sputtering using silver or an alloy containing silver as a target is performed. An inert gas such as argon is used as the sputtering gas, and a normal pressure of 0.1 to 20 mTorr, a direct current (DC) or a radio frequency (RF) magnetron sputtering method or the like can be used.
[0030]
In the transparent laminate of the present invention obtained using a transparent conductive layer formed with an oxide semiconductor, the oxide semiconductor is particularly limited as long as it has transparency in the visible range and has conductivity. It is not something. Specific examples include indium oxide, tin oxide, zinc oxide and the like, a mixture of these oxides including ITO (binary oxide), or these oxides or binary oxides such as antimony, fluorine, silicon, Examples thereof include boron, aluminum, gallium, magnesium and the like added in a small amount. These oxides can be used as long as the optical properties and conductivity are not significantly changed even if the stoichiometric composition of the metal and oxygen is different. Among these, ITO can be suitably used because of its high film forming speed in addition to high transparency and conductivity. The thickness of the transparent conductive film is experimentally determined from conductivity, optical characteristics, etc., and is not particularly limited as long as the transparent laminate obtained by laminating the obtained transparent conductive laminate has the required characteristics. Since the conductive laminate is required to have low resistance, it is preferably 0.1 μm or more and 10 μm or less, and more preferably 0.5 μm or more and 5 μm or less.
[0031]
The oxide semiconductor film can be formed by any of the conventionally known methods such as sputtering, ion plating, ion beam assist, vacuum deposition, wet coating, etc. Is preferred. For example, the ITO is formed by reactive sputtering using a metal target mainly composed of indium and tin or a sintered body target composed mainly of indium oxide and tin oxide. In the reactive sputtering method, an inert gas such as argon is used as a sputtering gas, oxygen is used as a reactive gas, and a normal pressure of 0.1 to 20 mTorr, direct current (DC) or radio frequency (RF) magnetron sputtering is used. it can. The oxygen gas flow rate is experimentally determined from the film forming speed obtained, and is controlled so as to obtain a thin film having desired transparency and conductivity.
[0032]
In the transparent conductive laminate of the present invention, in order to improve the mechanical strength and environmental resistance, on the surface of the transparent substrate (A) without the transparent conductive layer (B) (hereinafter referred to as a conductive layer), A transparent hard coat layer may be provided, or an optional protective layer may be provided on the outermost surface of the conductive layer to such an extent that the conductivity and optical properties are not impaired. In addition, in order to improve the environmental resistance of the metal thin film layer and the adhesion between the metal thin film layer and the high refractive index transparent thin film layer, electrical conductivity and optical characteristics are improved between the metal thin film layer and the high refractive index transparent thin film layer. You may form arbitrary inorganic substance layers to such an extent that it does not impair. Specific materials include copper, nickel, chromium, gold, silver, platinum, zinc, zirconium, titanium, tungsten, tin, palladium, etc., or an alloy composed of two or more of these materials, and the thickness is Preferably, it is about 0.02 nm to 2 nm, and if the thickness is too thin, a sufficient effect of improving the adhesion cannot be obtained. When the high refractive index transparent thin film layer is an oxide, part or all of the metal of the inorganic layer is actually a metal oxide, but there is no problem in its effect. Furthermore, by providing a single-layer or multilayer arbitrary antireflection layer on the main surface of the transparent conductive laminate, a transparent laminate having a higher transmittance can be obtained.
[0033]
The atomic composition of the oxide conductive film or the high-refractive-index transparent thin film layer and the metal thin film layer formed by the method described above is determined by Auger electron spectroscopy (AES), inductively coupled plasma method (ICP), Rutherford backscattering method (RBS). ) Etc. Moreover, these layer structures and film thicknesses can be measured by observation in the depth direction of Auger electron spectroscopy, cross-sectional observation using a transmission electron microscope, or the like. The film thickness is controlled by performing film formation after clarifying the relationship between the film formation conditions and the film formation speed in advance, or by film thickness monitoring during film formation using a crystal resonator or the like.
[0034]
The transparent laminate of the present invention can be obtained by stacking two or more transparent conductive laminates obtained as described above. The number of transparent conductive laminates may be in a range where the visible light transmittance is 40% or more, and is preferably 4 or less. An example of the laminated structure is shown in FIG. The transparent substrate 11 of the transparent conductive laminate 15 and the transparent conductive layer 12 of the other transparent conductive laminate 15 are stacked facing each other to form a transparent laminate 10. As a laminated structure, as long as an electrode can be formed as will be described later, the transparent conductive layers and the transparent substrates may be stacked face to face.
[0035]
The display filter of the present invention refers to a filter obtained by combining the transparent laminate of the present invention with members having other functions such as a metal electrode, a protective layer, and a transparent molded body (D).
[0036]
Among the display filters of the present invention, a display filter having an electromagnetic wave shielding property can be obtained by forming a metal electrode on a thin film forming surface, that is, a conductive layer. Since the electromagnetic wave is absorbed in the conductive layer and induces a charge, if the charge is not released by grounding, the conductive layer (electromagnetic wave shield) again becomes an antenna and oscillates the electromagnetic wave. Therefore, it is important to form an electrode on the electromagnetic wave shield body and to make sure that the electrode is in contact with the ground electrode of the display body. The shape of the electrode is not particularly limited, but a flat metal electrode is formed, for example, in a frame shape on the periphery of the conductive layer of the transparent laminate, that is, the thin film forming surface, excluding the central portion that is a light transmitting portion from the display. Examples of the structure of the transparent laminate, that is, how to overlap the transparent conductive laminate and the electrode shape are shown in [FIG. 1] and [FIG. 2], but are not limited thereto.
[0037]
The material used for the electrode is composed of a single substance or two or more kinds of silver, gold, copper, platinum, nickel, aluminum, chromium, iron, zinc, etc. in terms of conductivity, contact resistance and adhesion to the conductive surface. And a silver paste made of a mixture of a synthetic resin and an alloy containing silver or silver, or a mixture of a borosilicate glass and an alloy containing silver or silver. For the electrode formation, a conventionally known method such as a plating method, a vacuum deposition method, a sputtering method, or a silver paste printing or coating method can be employed. The thickness of the metal electrode is not particularly limited, but is about several μm to several mm.
[0038]
In addition, in order to impart scratch resistance to the thin film forming surface of the transparent laminate, that is, the conductive layer, and to prevent deterioration of the thin film due to heat emitted from the display, heat in the use environment, oxygen, water vapor, and other gases. It is also preferable to provide a protective resin layer. In particular, in the case of a transparent laminate obtained by laminating a transparent conductive laminate formed by laminating a laminated structure in which a metal thin film layer is sandwiched between high refractive index transparent thin film layers at least once, silver or the like is added to the metal thin film layer. When a material lacking in stability is used, it is preferable to provide a protective resin layer. The protective resin layer is not particularly limited, and examples thereof include acrylic resins, silicon resins, melamine resins, urethane resins, and fluorine resins. For the formation of the protective resin layer, a conventionally known method such as a printing or coating method can be selected and used depending on the resin to be used, and the thickness thereof is not particularly limited. It is about μm to 100 μm. The protective resin layer may be a single layer or a plurality of resin layers. In this case, it is important that the protective resin layer does not hinder the contact between the metal electrode and the display body when electrical contact is obtained from the display filter for the purpose of shielding electromagnetic waves. In addition, a compound that suppresses the deterioration of the metal thin film may be added to the protective resin layer, and the compound that suppresses the deterioration of the metal thin film is dissolved in an arbitrary solvent so that the thin film forming surface of the transparent laminate or the filter for display You may apply | coat to the surface or an end surface.
[0039]
The transparent laminate and display filter obtained as described above have a smooth main surface due to problems of strength, flatness when bonded to the display, and installation method when a polymer film is used for the transparent substrate. It is desirable to use by sticking together with a plate-like transparent molded body (D). The transparent molded body is preferably a plastic plate that is transparent in the visible range because of its mechanical strength, lightness, and resistance to cracking. However, a glass plate can also be suitably used from the viewpoint of thermal stability with little deformation due to heat. Specific examples of the plastic plate include acrylic resin such as polymethyl methacrylate (PMMA), polycarbonate resin, transparent ABS resin and the like, but are not limited to these resins. In particular, PMMA can be suitably used because of its high transparency in a wide wavelength region and high mechanical strength. The thickness of the plastic plate is not particularly limited as long as sufficient mechanical strength and rigidity to maintain flatness without bending are obtained, but it is usually about 1 mm to 10 mm. When a glass plate is used as a transparent molded body, it is desirable to use a semi-tempered glass plate or a tempered glass plate that has been subjected to chemical strengthening or air-cooling strengthening to add mechanical strength. An example of how the display filter and the transparent molded body are bonded together is shown in FIG. 3, but is not limited thereto.
[0040]
For the bonding in the present invention, any pressure-sensitive adhesive material or adhesive can be used. In this case, it is important that the pressure-sensitive adhesive or adhesive used in the central portion which is a light transmission portion from the display needs to be sufficiently transparent to visible light. The pressure-sensitive adhesive material or adhesive may be on the sheet or in liquid form as long as it has practical adhesive strength, and is bonded by laminating each member after the pressure-sensitive adhesive sheet is applied or after the adhesive is applied. Liquid is an adhesive that is cured by standing or heating at room temperature after coating and laminating, and examples of the coating method include bar coating, reverse coating, gravure coating, die coating, and roll coating. It is selected in consideration of the type of adhesive, viscosity, and coating amount. Although the thickness of an adhesive material or an adhesive bond layer is not specifically limited, It is 0.5 micrometer-50 micrometers, Preferably it is 1 micrometer-30 micrometers. After bonding using an adhesive or adhesive, in order to improve the adhesion between the members by defoaming or solidifying the air that has entered between the members during bonding, in the adhesive or adhesive, It is important to cure under pressure and warming conditions. At this time, the pressurizing condition is about several atmospheres to 20 atmospheres or less, and the heating condition depends on the heat resistance of each member, but is about room temperature to about 80 ° C., but is not particularly limited thereto.
[0041]
The transparent laminate and display filter of the present invention obtained as described above are used when the main surface of the laminate or the filter and the display surface are used in close contact with each other because the degree of adhesion with the display surface varies depending on the location. Newton rings are generated due to the gaps generated thereby. Therefore, it is preferable to form an anti-Newton ring layer on each main surface that is in close contact with the display surface. In this case, it is important that the anti-Newton ring layer should not interfere with the contact between the metal electrode and the display body when obtaining electrical contact from the display filter for the purpose of shielding electromagnetic waves.
[0042]
In addition, since the display screen is difficult to see due to the reflection of lighting fixtures on the display, reflection of external light is suppressed by forming an antireflection layer on the surface of the display filter on the human side, that is, on the side opposite to the display body. Alternatively, it is preferable to provide an antiglare property by forming a non-glare layer. Further, by forming the antireflection layer, the light transmittance can be improved by reducing the reflection of the display filter.
[0043]
The protective resin layer may serve as an anti-Newton ring property or non-glare property, or the anti-Newton ring layer or non-glare layer may serve as a protective resin layer. In this case, it is not necessary to further form an anti-Newton ring layer or a non-glare layer on the protective resin layer, and the number of constituent members or the number of constituent layers can be reduced, whereby the process and cost can be reduced.
[0044]
The layers in the anti-Newton ring layer, non-glare layer, protective resin layer, and antireflection layer of the present invention indicate a film having each function or a polymer film on which a film having each function is formed. Even if a film having each function is formed by coating or printing or various conventionally known film forming methods, a polymer film on which the film having each function is formed is bonded via an arbitrary adhesive or adhesive. May be attached. These production methods are not particularly limited. The type and thickness of the polymer film are not particularly limited.
[0045]
The antireflection layer considers the optical characteristics of the substrate on which the antireflection film is formed, and determines the constituent elements and the film thickness of each constituent element by the optical design as described above. Specifically, a fluorine-based transparent polymer resin having a low refractive index in the visible range or a thin film of magnesium fluoride formed in a single layer, a metal oxide, fluoride, silicide, boride having a different refractive index, There are multilayered thin films of inorganic compounds such as carbides, nitrides and sulfides, or organic compounds such as acrylic resins and fluorine resins. A single layer formed is easy to manufacture, but the antireflection property is inferior to that of a multilayer stack. Multi-layered ones have antireflection ability over a wide wavelength range, and there are few restrictions on optical design due to optical characteristics. These inorganic compound thin films can be employed by any of the conventionally known methods such as sputtering, ion plating, ion beam assist, vacuum deposition, and wet coating. A conventionally well-known method, such as wet coating, can be employ | adopted for an organic compound thin film.
[0046]
The anti-Newton ring layer and the non-glare layer referred to in the present invention refer to layers that are transparent to visible light having a minute uneven surface state of about 0.1 μm to 10 μm, only for different uses. Specifically, an inorganic compound such as silica, melamine, or acrylic, or a thermosetting or photocurable resin such as an acrylic resin, a silicon resin, a melamine resin, a urethane resin, an alkyd resin, or a fluorine resin, or An ink obtained by dispersing particles of an organic compound is obtained by coating and curing on a substrate forming the layer by a bar coating method, a reverse coating method, a gravure coating method, a die coating method, a roll coating method or the like. The average particle diameter of the particles is about 1 to 40 μm. Alternatively, a mold having a desired haze or surface state by applying a thermosetting or photocurable resin such as an acrylic resin, a silicon resin, a melamine resin, a urethane resin, an alkyd resin, or a fluorine resin to a substrate. An anti-Newton ring layer or a non-glare layer can also be obtained by pressing and curing. Furthermore, a non-glare layer can also be obtained by treating the substrate with chemicals such as etching a glass plate with hydrofluoric acid or the like. In this case, the haze of the non-glare layer can be adjusted by the processing time and the etchability of the chemical. In short, it is important to have appropriate irregularities and is not necessarily limited to the above method.
[0047]
The haze of the non-glare layer or the anti-Newton ring layer is 0.5% or more and 20% or less, preferably 1% or more and 10% or less. If the haze is too small, the non-glare ability or the anti-Newton ring ability is insufficient, and if the haze is too large, the parallel light transmittance is lowered and the visibility of the display is deteriorated. When the inorganic compound or organic compound particles as described above are dispersed in the protective resin layer, the protective resin layer has anti-Newton ring property or non-glare property, and is more preferable as described above.
[0048]
If the non-glare layer on the outermost surface of the filter is relatively far from the display surface, such as when the filter is placed away from the display main body, blur due to image diffusion may occur. For this reason, in the case of such an installation method, it is preferable to select a non-glare layer that has anti-glare properties and has a haze that does not blur the image even if it is at an appropriate distance from the display.
[0049]
Further, in order to impart antistatic ability to the display filter, a conductive film may be provided on the surface on the human side of the display filter. It is preferable to perform an antistatic treatment because dust tends to adhere to the display surface due to electrostatic charging, and when the human body comes into contact, it can be discharged and receive an electric shock. The conductive film may be a transparent conductive film that is transparent in the visible range. The display filter having antistatic ability may be formed of a transparent conductive film as follows. That is, (1) transparent laminated body / transparent molded body (D) / transparent conductive film / antireflection layer or non-glare layer, or (2) transparent laminated body / transparent molded body (D) / non-glare layer / transparent conductive film. Yes, (3) The antireflection layer or the non-glare layer may have a transparent conductivity.
[0050]
In {circle over (1)} or {circle around (2)}, a known transparent conductive film such as ITO described above is formed by the method described above, or a polymer film on which ITO is formed is bonded to form a transparent conductive film. A film is formed. In (1), since the conductivity of the outermost surface of the display filter is low or absent, the antistatic ability is weak. What is important in (2) is that even if a transparent conductive film is formed, the antiglare property or antireflective property is not significantly impaired. When the transparent conductive layer is formed on the non-glare layer, the conductivity required for the antistatic ability may be relatively low, so that a thin film that does not impair the antiglare property is sufficiently effective. In (3), conductive ultrafine particles such as ITO ultrafine particles and tin oxide ultrafine particles are dispersed in the non-glare layer. In any of the cases (1) to (3), the antireflection layer is determined by the optical design as described above in consideration of the transparent conductive film and the transparent molded body. In the case of (3), the optical design may be made by including a transparent conductive film as a constituent element. Specific examples of the antireflection layer or non-glare layer include: substrate / ITO / silicon-containing compound / ITO / silicon-containing compound, Examples include substrate / ITO / fluorine-containing compound.
[0051]
Furthermore, in order to add scratch resistance to the display filter, a hard coat layer with transparency is formed on the outermost surface of the filter so that it does not impair the characteristics of the display filter, including optical characteristics. You may do it. The non-glare layer may have a hard coat property, and the antireflection layer may be formed as a component of the hard coat layer. Specific examples of the hard coat include melamine resin, silicon resin, fluorine resin, and the like.
[0052]
When the transparent laminate of the present invention uses a transparent conductive laminate formed of a transparent conductive layer in which a laminated structure in which a metal thin film layer is sandwiched between high refractive index transparent thin film layers is used one or more times, In addition, the plasma display emits a strong near infrared ray, but the plasma display may be used in combination with a near infrared absorbing dye in order to give the near infrared ray inhibiting property. When a transparent conductive laminate in which an oxide semiconductor such as ITO is formed is used, it is important to use a near-infrared absorbing dye because the near-infrared deterrence is low.
[0053]
That is, a transparent laminate containing a near-infrared absorbing dye on a transparent substrate of the transparent laminate already described, and a display filter using the same, or a transparent molded body in which the transparent substrate of the transparent laminate is bonded, an antireflection layer , A non-glare layer, an anti-Newton ring layer, or a protective resin layer containing a near infrared absorbing dye, or a transparent molding containing a near infrared absorbing dye as a constituent of a display filter The display filter to which the product (E) is added has a higher near-infrared ray deterrence ability. When using the transparent molding containing a pigment | dye, it is set as the component of a display filter by bonding through the arbitrary adhesive materials or adhesives mentioned above between each of the members which comprise a display filter.
[0054]
The near-infrared absorbing dye used in the present invention may be organic or inorganic as long as it compensates the near-infrared deterring ability of the transparent laminate and absorbs near-infrared light emitted by the plasma display to a sufficiently practical level. There is no particular limitation, and the concentration is not limited. However, in the case of a dithiol complex compound represented by the following formula (1) [Chemical Formula 1] or Formula (2) [Chemical Formula 2], or a mixture of at least one of them, the transparent laminate or display of the present invention The filter for use can have a better near-infrared ray inhibiting ability. Since the compounds of the following formulas (1) and (2) are commercially available, they are available.
[0055]
[Chemical 1]

[Where A¹~ A⁸Are each independently a hydrogen atom, halogen atom, nitro group, cyano group, thiocyanate group, cyanate group, acyl group, carbamoyl group, alkylaminocarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, substituted or unsubstituted alkyl group Substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted alkylamino group Or a substituted or unsubstituted arylamino group, and two adjacent substituents may be connected via a linking group, R¹~ R^FourEach independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, M represents nickel, platinum, palladium or copper, and X represents a nitrogen atom or a phosphorus atom. ]
[0056]
[Chemical formula 2]

[Wherein B¹~ B^FourEach independently represents a hydrogen atom, a cyano group, an acyl group, a carbamoyl group, an alkylaminocarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and Two adjacent substituents may be connected via a linking group, and M represents nickel, platinum, palladium or copper. ]
The term “inclusion” as used in the present invention means, of course, a state of being applied to the surface of the substrate, a state of being sandwiched between the substrate and the like, and the like. The substrate here is any of the transparent substrate of the transparent laminate described above, a protective resin layer, a transparent molded body on which the transparent laminate is bonded, an antireflection layer, a non-glare layer, an anti-Newton ring layer, or a display filter. It is a transparent molded product that contains a pigment. The antireflection layer, non-glare layer, and anti-Newton ring layer may contain a dye in the film having each function, or the film having each function may be formed on a transparent molded product containing the dye. Examples of the transparent molded product containing a pigment include a transparent plastic plate, a transparent polymer film, and transparent glass. The content of the pigment depends on the near-infrared deterrence of the transparent laminate, the visible light transmittance required for the display filter, the near-infrared deterrence, and the like.
[0057]
In the present invention, the method for producing a transparent molded product containing a pigment using the pigment is not particularly limited, but for example, the following three methods can be used.
(1) A method of preparing a plastic plate or a polymer film by kneading a pigment in a resin and thermoforming it,
(2) A method for producing a coating material containing a pigment and coating it on a transparent plastic plate, a transparent polymer film, or a transparent glass plate,
(3) A method of producing a laminated plastic plate, a laminated polymer film, laminated glass and the like by incorporating a dye into an adhesive.
[0058]
First, in the method of (1) in which a pigment is kneaded into a resin and heat-molded, the resin material is preferably as transparent as possible when it is made into a plastic plate or a polymer film. Specific examples include polyethylene and polystyrene. , Polyacrylic acid, polyacrylic acid ester, polyvinyl acetate, polyacrylonitrile, polyvinyl chloride, polyvinyl fluoride, and other vinyl compounds, and addition polymers of these vinyl compounds, polymethacrylic acid, polymethacrylic acid ester, polychlorinated Vinyl compounds such as vinylidene, polyvinylidene fluoride, vinylidene polycyanide, vinylidene fluoride / trifluoroethylene copolymer, vinylidene fluoride / tetrafluoroethylene copolymer, vinylidene cyanide / vinyl acetate copolymer, etc. Copolymer, poly Fluorine-containing compounds such as trifluoroethylene, polytetrafluoroethylene, polyhexafluoropropylene, polyamides such as nylon 6 and nylon 66, polyimides such as polyimide, polyurethane, polypeptide, polyethylene terephthalate, polycarbonate, polyoxymethylene, polyethylene oxide Polyether such as polypropylene oxide, epoxy resin, polyvinyl alcohol, polyvinyl butyral and the like can be mentioned, but are not limited to these resins.
[0059]
As a production method, the processing temperature, filming conditions and the like are somewhat different depending on the dye used and the base polymer molded body, but usually (i) the dye is added to the powder or pellet of the base polymer molded body, and 150 to A method of forming a resin plate by heating and dissolving at 350 ° C. and then molding, (ii) a method of forming a film with an extruder, (iii) preparing an original fabric with an extruder, and 2 at 30 to 120 ° C. For example, the film may be stretched uniaxially or biaxially to obtain a film having a thickness of 10 to 200 μm. In addition, when kneading, additives used for ordinary resin molding such as an ultraviolet absorber and a plasticizer may be added. The addition amount of the dye varies depending on the absorption coefficient of the dye, the thickness of the polymer molded article to be produced, the target absorption strength, the target visible light transmittance, and the like, but is usually 1 ppm to 20%.
[0060]
The method of coating and coating (2) includes a method in which a pigment is dissolved in a binder resin and an organic solvent to form a coating, and a dithiol complex compound is atomized to several μm or less and dispersed in an acrylic emulsion to form a water-based coating. There is a method and so on. In the former method, usually, an aliphatic ester resin, an acrylic resin, a melamine resin, a urethane resin, an aromatic ester resin, a polycarbonate resin, an aliphatic polyolefin resin, an aromatic polyolefin resin, a polyvinyl resin, a polyvinyl alcohol resin, Polyvinyl modified resins (PVB, EVA, etc.) or copolymer resins thereof are used as the binder resin.
[0061]
As the solvent, a halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, ether-based solvent, or a mixture thereof is used.
[0062]
The concentration of the dye varies depending on the absorption coefficient of the dye, the thickness of the coating, the target absorption intensity, the target visible light transmittance, and the like, but is usually 0.1 to 30% with respect to the weight of the binder resin. Moreover, binder resin density | concentration is 1-50% normally with respect to the whole coating material. Similarly, in the case of an acrylic emulsion water-based paint, it can be obtained by dispersing a finely pulverized (50 to 500 nm) dithiol complex compound in an uncolored acrylic emulsion paint. In the coating material, additives such as ultraviolet absorbers, antioxidants and the like used in normal coating materials may be added.
[0063]
The paint prepared by the above method is coated with a bar coder, blade coater, spin coater, reverse coater, die coater, or spray on a transparent polymer film, transparent resin, transparent glass, etc., and contains a pigment. A substrate is prepared.
[0064]
A protective layer may be provided to protect the coating surface, or a transparent resin plate, a transparent polymer film, or the like may be bonded to the coating surface. A cast film is also included in the method.
[0065]
In the method (3) for producing a laminated resin plate, laminated resin film, laminated glass, etc. by incorporating a dye into the adhesive, as an adhesive, for general silicon-based, urethane-based, acrylic-based resins, etc. Alternatively, known transparent adhesives for laminated glass such as polyvinyl butyral adhesive (PVB) for laminated glass and ethylene-vinyl acetate adhesive (EVA) can be used.
[0066]
Bonding transparent resin plates, resin plates and polymer films, resin plates and glass, polymer films, polymer films and glass, and glass using an adhesive with 0.1 to 30% added pigment Is made.
[0067]
You may use the adhesive agent containing said pigment | dye for bonding each member, such as a transparent laminated body, a transparent molded object, an antireflection layer, a non-glare layer, an anti-Newton ring layer, and a transparent molded product containing a pigment | dye.
[0068]
In addition, the plasma display filter needs to cut near infrared rays having a high intensity in the wavelength region of 800 to 1000 nm. If necessary, the filter is represented by the above formula (1) and / or (2). Two or more dithiol complex compounds can be combined.
[0069]
In order to increase the light resistance of the dye-containing filter, a transparent film (UV cut film) containing a UV absorber can be attached to the outside (human side) of the dye-containing part.
Moreover, in order to change the color tone of a filter, the other pigment | dye which has absorption in a commercially available visible region can also be added.
[0070]
The configuration of the display filter of the present invention can be changed as necessary, and the transparent laminate of the present invention comprises a metal electrode, a protective resin layer, a transparent molded body, an antireflection layer, an anti-Newton ring layer, or a non-glare layer. Preferably, at least two selected from the group are provided at the same time.
[0071]
The transparent laminate and display filter of the present invention are excellent in near-infrared deterring ability, and the transparent laminate and display filter not using the dye of the present invention are generally near-infrared cuts for displays using general organic dyes. Compared to filters, there is less degradation due to the environment such as humidity, heat, and light. Further, the dithiol complex compound represented by the above formula (1) or formula (2), or a mixture of at least one of them is excellent in environmental resistance. Filter is obtained. Therefore, the display filter of the present invention can be suitably used as a near infrared cut filter.
[0072]
The use and mounting method of the display filter of the present invention can be broadly classified as follows, but are not particularly limited thereto. (1) A filter for display having electromagnetic wave shielding ability and near-infrared ray inhibiting ability is used by attaching the main surface of the filter to the display screen. {Circle around (2)} A display filter having electromagnetic wave shielding ability and near infrared ray inhibiting ability is used by separating the filter main surface from the display screen. (3) A display filter having a near-infrared deterring ability is attached and used in close contact with the display screen. (4) A display filter having a near-infrared deterring ability is used by separating the main surface of the filter from the display screen.
[0073]
(1) will be described with reference to FIG. 4. Usually, from the display side, the anti-Newton ring layer 50 and / or the protective resin layer 40 and the metal electrode 20 / transparent laminate 10 / transparent molded body 30 / antireflection layer or The non-glare layer 60 is configured in this order. (2) will be described with reference to [FIG. 5]. Usually, from the display side, the protective resin layer 60 and the metal electrode 20 / transparent laminate 10 / transparent molded body 30 / antireflection layer or non-glare layer 60 are arranged in this order. The (3) will be described with reference to [FIG. 6]. Normally, from the display side, the anti-Newton ring layer 50 / protective resin layer 40 / transparent laminate 10 / transparent molded body 30 / antireflection layer or non-glare layer 60 are arranged in this order. Composed. (4) will be described with reference to [FIG. 7]. Normally, the protective resin layer 40 / transparent laminate 10 / transparent molded body 30 / antireflection layer or non-glare layer 60 are arranged in this order from the display side. In the case of using a near-infrared absorbing dye, the dye is contained in any one or more of the above-described constituent elements, or a transparent molded product containing the dye is sandwiched between any of the above-described constituent elements.
[0074]
In the case of (3) above, the anti-Newton ring layer usually has non-glare properties, and if the non-glare layer on the human side of the display filter has anti-Newton ring properties, either side of the filter is displayed on the display screen. It can be used in close contact with.
[0075]
The display filter of the present invention may be subjected to arbitrary frame printing so that the mounting jig, the electrode portion and the like are not visible to the viewer when mounted on the display. The printing shape, printing surface, printing color, and printing method are not particularly specified. Further, processing such as hole processing for mounting on a display may be performed.
[0076]
Furthermore, by adding the performance of a circular polarizing filter by attaching a polarizing film, a retardation film, etc., the reflected light from the display side can be suppressed, resulting in a more excellent filter.
[0077]
The display filter of the present invention has a high visible light transmittance, so the display clarity is not impaired, the electromagnetic wave shielding property that is said to be harmful to the health generated from the display is excellent, and further, the display filter comes out of the display. Since near-infrared light in the vicinity of 800 to 1000 nm is efficiently cut, it does not adversely affect the wavelengths used by the remote control of peripheral electronic devices, transmission optical communication, and the like, and malfunctions thereof can be prevented.
[0078]
【Example】
Next, the present invention will be specifically described with reference to examples. The present invention is not limited thereby. The thicknesses of the thin films shown in the following examples and comparative examples are values obtained from the film forming conditions, and are not actually measured film thicknesses.
[Example 1]
On one main surface of a polyethylene terephthalate film (thickness: 50 μm), an indium oxide thin film is used as a target by using indium as a target and an argon / oxygen mixed gas (total pressure 266 mPa: oxygen partial pressure 80 mPa) as a sputtering gas. Silver, argon gas (total pressure: 266 mPa) as a sputtering gas, and silver thin film by magnetron DC sputtering, indium oxide thin film 40 nm, silver thin film 10 nm, indium oxide thin film 70 nm, silver thin film 10 nm, indium oxide thin film 40 nm in this order. A transparent conductive laminate was produced by laminating, and two sheets were laminated using an adhesive material as shown in FIG. 1 to produce a transparent laminate of the present invention.
[0079]
[Comparative Example 1]
As in Example 1, an indium oxide thin film 40 nm, a silver thin film 10 nm, an indium oxide thin film 70 nm, a silver thin film 10 nm, and an indium oxide thin film 40 nm are laminated in this order on one main surface of a polyethylene terephthalate film (thickness: 50 μm) and transparent. A conductive laminate was produced.
[0080]
[Example 2]
On one main surface of a polyethylene terephthalate film (thickness: 50 μm), an alloy of indium and tin (In: Sn = 95: 5) is used as a target, and an argon / oxygen mixed gas (total pressure 266 mPa: oxygen partial pressure) is used as a sputtering gas. 80 mPa), an ITO thin film having a thickness of 1 μm was laminated by a magnetron DC sputtering method to produce a transparent conductive laminate, and two sheets were laminated using an adhesive material as shown in FIG. 1 to produce a transparent laminate.
[0081]
[Example 3]
Polyethylene terephthalate pellet 1203 (manufactured by Unitika Ltd.) is mixed with 0.3 wt% of a dithiol complex represented by the following formula (3) [Chemical Formula 3], melted at 260 to 280 ° C., and a film having a thickness of 100 μm is formed by an extruder. Produced. Thereafter, this film was biaxially stretched to give a film having a thickness of 50 μm, and was bonded to the transparent laminate of Example 1 using an adhesive material to produce the display filter of the present invention.
[0082]
[Chemical Formula 3]

[0083]
[Example 4]
Similarly to Example 3, a dithiol complex represented by the following formula (3) [Chemical Formula 3] 0.6 wt%, a dithiol complex represented by the following formula (4) [Chemical Formula 4] was 0.8 wt% and a film having a thickness of 50 μm. It produced and bonded together to the transparent laminated body of Example 2 using the adhesive material, and the filter for displays of this invention was produced.
[0084]
[Formula 4]

[0085]
Visible light transmittance, synthetic surface resistance, near-infrared suppression of the transparent laminates of Examples 1 and 2, the display filters of Examples 3 and 4 and the transparent conductive laminate of Comparative Example 1 produced as described above. The ability was evaluated by the following method.
1) Visible light transmittance (Tvis) and near infrared transmittance
The object to be measured was cut into small pieces, and the parallel light transmittance at 300 to 1000 nm was measured with a spectrophotometer (U-3400) manufactured by Hitachi, Ltd. Tvis was calculated from the transmittance obtained here. The near-infrared transmittance was evaluated at 820 nm, 850 nm, and 1000 nm.
2) Composite surface resistance
The sheet resistances of the transparent conductive laminates of Comparative Examples 1 and 2 were measured by the four-terminal method (probe interval 1 mm), and the combined sheet resistances of the transparent laminates of Examples 1 and 2 were respectively Comparative Example 1. It was calculated from the sheet resistance of the transparent conductive laminate of Example 2.
3) Remote control test
Each laminate and filter were installed on the screen of the plasma display, and the malfunction was confirmed by moving the electronic device that uses the remote control away from the 0.2m to 3m display. When there was a malfunction, the limit distance was calculated. It can be said that the shorter the limit distance, the fewer malfunctions.
The above results are listed in [Table 1].
[0086]
[Table 1]

[0087]
As is clear from Table 1, the transparent laminate of Example 1 is a laminate of two transparent conductive laminates of Comparative Example 1 and has a large near-infrared deterring ability, and a malfunction limit distance. Is practical enough. In Example 3 in which a film containing a near-infrared absorbing dye was bonded to the transparent laminate of Example 1, the near-infrared deterrence was further improved although the visible light transmittance was reduced. The transparent conductive laminate alone of Comparative Example 1 has a large malfunction limit distance and cannot be used as a near infrared cut filter. The transparent laminate using the ITO of Example 2 has a small near-infrared deterrent ability, but in Example 4 in which a film containing a near-infrared absorbing dye was bonded to this transparent laminate, the visible light transmittance was reduced. However, the near-infrared deterrence improved and became practical.
[0088]
[Example 5]
Silver paste (manufactured by Mitsui Toatsu Chemical Co., Ltd.) was screen-printed on the thin film forming surface of the transparent laminate (472 mm × 350 mm) of Example 1, that is, the conductive surface, as shown in FIG. 1 and FIG. A metal electrode having a thickness of 20 μm and a width of 10 mm was formed by drying to produce a display filter of the present invention.
[0089]
[Comparative Example 2]
A metal electrode was formed on the transparent laminate (472 mm × 350 mm) of Comparative Example 1 in the same manner as in Example 5 to produce a display filter of the present invention.
[0090]
[Example 6]
A metal electrode was formed on the transparent laminate (472 mm × 350 mm) of Example 2 in the same manner as in Example 5 to produce a display filter of the present invention.
[0091]
The electromagnetic wave shielding ability of the display filters of Examples 5 and 6 and the display filter of Comparative Example 2 produced as described above was evaluated as follows.
1) Electromagnetic shielding ability
A display filter is installed on the screen of the plasma display, a dipole antenna is installed at a position 3 m from the center of the screen in the direction perpendicular to the surface, and the radiated electric field strength in the 20 to 90 MHz band is measured with Advantest's spectrum analyzer (TP4172). did. At this time, the entire metal electrode portion of the display filter and the entire ground electrode of the display body were brought into contact with each other to obtain ground. The evaluation was performed using the radiation field intensity at 33, 62, 70, and 80 MHz.
The above evaluation results are listed in the following [Table 2] together with the measurement results of the radiated electric field intensity when there is no display filter.
[0092]
[Table 2]

[0093]
As apparent from [Table 2], Comparative Example 2 has no shielding effect depending on the band. As shown in Examples 5 and 6, when the combined surface resistance is 4 Ω / □ or less, there is a sufficient effect over the entire band, but Example 4 where the combined surface resistance is 3 Ω / □ or less is more practical.
[0094]
[Example 7]
On one main surface of a polyethylene terephthalate film (thickness: 50 μm), 3 g of thermosetting varnish (SF-C-335) manufactured by Dainippon Ink & Chemicals, Ltd. was added to 100 g of toluene / methyl ketone (10: 1) mixed solvent. After dissolution, coating, and natural drying, it was cured at 150 ° C. for 20 seconds to form an anti-Newton ring layer having a thickness of 1 μm, and an anti-Newton ring film was produced. The metal electrode of the display filter of Example 5 is not formed, and an acrylic resin as a protective resin layer is screen-printed and cured on the surface that is in close contact with the display portion of the display body when pasted and cured by 10 μm. Then, the anti-Newton ring film was bonded onto the protective resin layer using an adhesive so that the anti-Newton ring layer was on the display side. Furthermore, the opposite surface of the display filter and the surface of the PMMA plate having a non-glare layer on one side (2 mm thick, acrylic filter MR-NG manufactured by Mitsubishi Rayon Co., Ltd.) where the non-glare layer is not formed are bonded together. A display filter was prepared.
[0095]
The display filter has a visible light transmittance of 65%, a combined surface resistance of 2.9Ω / □, a near-infrared transmittance of 9.3% at 820 nm, 2.7% at 850 nm, and 1.2% at 1000 nm. there were. When the display filter was installed on the screen of the plasma display, no malfunction of peripheral electronic devices occurred. In addition, Newton's ring did not occur, the image was clear, and there was little reflection and visibility was good.
[0096]
【The invention's effect】
As described above, according to the present invention, a composite surface comprising two or more transparent conductive laminates (C) in which a transparent conductive layer (B) is laminated on one main surface of a transparent substrate (A). A transparent laminate with a resistance of 4Ω / □ or less and a visible light transmittance of 40% or more can shield the electromagnetic wave generated by the plasma display by forming an electrode and grounding it, and in the visible range that does not impair the clearness of the display. Can be provided, and a transparent laminate having a deterrence of near-infrared light having a wavelength longer than 820 nm that induces malfunction of peripheral electronic devices can be provided. Further, by using this transparent laminate, electromagnetic shielding properties and high transparency can be provided. In addition, it is possible to provide a display filter having excellent near-infrared deterrence, antiglare property or antireflection property, anti-Newton ring property or antistatic property. Furthermore, when a near-infrared absorbing dye is used, it is possible to provide a display filter that is further excellent in near-infrared deterring ability.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing an example of a display filter of the present invention.
FIG. 2 is a plan view seen from the display side, showing an example of the display filter of the present invention.
FIG. 3 is a cross-sectional view showing an example of the display filter of the present invention.
FIG. 4 is a cross-sectional view showing an example of the display filter of the present invention.
FIG. 5 is a cross-sectional view showing an example of the display filter of the present invention.
FIG. 6 is a sectional view showing an example of the display filter of the present invention.
FIG. 7 is a cross-sectional view showing an example of the display filter of the present invention.
[Explanation of symbols]
10 Transparent laminate
11 Transparent substrate (A)
12 Transparent conductive layer (B)
15 Transparent conductive laminate (C)
20 Metal electrodes
30 Transparent molded body (D)
40 Protective resin layer
50 Anti-Newton ring layer
60 Anti-reflective layer or non-glare layer

Claims (15)

The transparent conductive laminate (C) having a transparent conductive layer (B) formed on at least one main surface of the transparent substrate (A) is divided into at least two sheets having different sizes and the smaller transparent conductive laminate. A transparent laminate in which the transparent substrate (A) of the body (C) and the transparent conductive layer (B) of the larger transparent conductive laminate (C) are opposed to each other. A filter for plasma display, having a light transmittance of 40% or more, a combined surface resistance of 4Ω / □ or less, and a metal electrode formed on at least two transparent conductive layers (B). The filter for a plasma display according to claim 1, wherein the light transmittance in a region having a wavelength longer than 820 nm is 10% or less. 3. The plasma display filter according to claim 1, wherein the transparent conductive layer (B) is mainly composed of indium oxide and tin oxide. The transparent conductive layer (B) is a high refractive index transparent thin film layer (B-1) and a metal thin film layer (B-2) in this order, at least once with (B-1) / (B-2) as a repeating unit. The filter for plasma display according to claim 1 or 2, wherein the filter is repeatedly laminated, and at least a high refractive index transparent thin film layer (B-1) is laminated thereon. 5. The plasma display filter according to claim 4, wherein the high refractive index transparent thin film layer (B-1) is mainly composed of indium oxide. 6. The plasma display filter according to claim 4, wherein the metal thin film layer (B-2) is made of silver or an alloy containing silver. The filter for plasma display according to any one of claims 1 to 6, wherein the transparent substrate (A) is a transparent polymer molded product. The filter for plasma display according to any one of claims 1 to 7, wherein the transparent substrate (A) contains a pigment. Plasma display filter, wherein the surface protective resin layer of the transparent conductive layer of a filter for a plasma display according to any one of claims 1 to 8 (B) is formed. Plasma display filter, wherein the plasma display filter according to claim 1, bonded to one surface of the transparent molded article (D). Plasma display filter, wherein at least one surface an antireflection layer or anti-Newton ring layer or a non-glare layer of the filter for a plasma display is formed of any one of claims 1 to 10. Antireflection layer, non-glare layer, anti-Newton ring layer / transparent molded body (D) / filter for plasma display according to any one of claims 1-8 / protective resin layer and / or anti-Newton ring layer A plasma display filter comprising layers in order. The filter for plasma display according to any one of claims 1 to 8, comprising at least two simultaneously selected from the group consisting of a protective resin layer, a transparent molded body and an antireflection layer, an anti-Newton ring layer or a non-glare layer. Filter for plasma display. 14. The transparent substrate (A) and / or the protective resin layer and / or the transparent molded body (D) and / or the anti-Newton ring layer and / or the non-glare layer contains a pigment. The filter for plasma displays in any one. Plasma display filter, wherein the transparent molded material containing the dye (E) is formed on the plasma display filter according to any one of claims 1 to 14.

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