JP3761273B2 - Anti-reflection coating - Google Patents

Description

Ｒ；パーフルオロアルキレン基
ｐ；ゼロまたは１の数
ｑ；ゼロまたは１の数
の反復単位、下記式（３）
【００３４】
【化２】

Ｒ；パーフルオロアルキレン基
の反復単位、及び／または下記式（４）
【００３５】
【化３】

Ｒ；パーフルオロアルキレン基
の反復単位の少なくとも１種を含有するパーフルオロフッ素樹脂が挙げられる。
【００３６】
このパーフルオロフッ素樹脂は、反復単位の全てが上記環状の反復単位から成っていても、或いは反復単位の一部が上記環状の反復単位から反復単位の残りの一部が線状のパーフルオロ単量体単位から成っていてもよい。
【００３７】
上記パーフルオロ非晶質フッ素樹脂は、それ自体公知の方法で得ることができ、例えば両末端二重結合のパーフルオロエーテル単量体の環化重合や、環状パーフルオロ単量体のラジカル重合により得ることができる。これらの重合に際して他のパーフルオロ単量体を共存させることにより、共重合体を得ることができる。
【００３８】
両末端二重結合のパーフルオロエーテル単量体としては、下記式（５）
ＣＦ₂ ＝ＣＦ−（−ＣＦ₂ −）_n −Ｏ−（−ＣＦ₂ −）_m −ＣＦ＝ＣＦ₂ ‥（５）
（ｎ＝１〜５、ｍ＝１〜５、ｎ＋ｍ＝１〜６）
で表されるパーフルオロエーテルを挙げることができ、その例として、パーフルオロアリルビニルエーテル、パーフルオロジアリルエーテル、パーフルオロブテニルビニルエーテル、パーフルオロブテニルアリルビニルエーテル、パーフルオロジブテニルエーテルなどが例示される。
【００３９】
両末端二重結合のパーフルオロエーテル単量体の他のタイプとしては、下記式（６）
ＣＦ₂ ＝ＣＦＯ−Ｒ−Ｏ−ＣＦ＝ＣＦ₂ ‥（６）
Ｒ；パーフルオロアルキレン基
で表されるパーフルオロアルキレングリコールジビニルエーテルを挙げることができ、その例として、パーフルオロエチレングリコールジビニルエーテル、パーフルオロテトラメチレングリコールジビニルエーテルなどが例示される。
【００４０】
一方、環状パーフルオロ単量体としては、例えば、下記式（７）
【００４１】
【化４】

Ｒ；パーフルオロアルキレン基
で表される単量体、特にパーフルオロ−２，２−ジメチル−１，３−ジオキソールを挙げることができる。
【００４２】
共重合に使用する他の単量体としては、テトラフルオロエチレン、ヘキサフルオロプロピレン、パーフルオロビニルプロピルエーテル、パーフルオロアリルブチルエーテル、パーフルオロジビニルエチルエーテル、パーフルオロビニルアリルエーテルなどが例示される。
【００４３】
非晶質フッ素樹脂の適当な例は、これに制限されないが、環状エーテルとパーフルオロ−２，２−ジメチル−１，３−ジオキソールとの共重合体、テトラフルオロエチレンと環状パーフルオロエーテルの共重合体、パーフルオロビニルアリルエーテルとの環化共重合体等である。
【００４４】
具体的に入手可能なものとして、三井デュポンフロロケミカル（株）製「テフロンＡＦ」、旭硝子（株）製「サイトップ」、住友スリーエム（株）製「フロラードＦＣ−７２２」、デュポン社の「テフロンＡＦ１６００」等が挙げられる。
【００４５】
溶剤としては、パーフロオロオクタン、パーフルオロハイドロフラン等が揮発スピードのバランス的に良好であり、上記樹脂を１〜５％濃度で溶解し、コート液を作成することが出来る。
【００４６】
本発明で、オーバーコート層として使用され、耐磨耗性、耐擦傷性を付与する有機ポリシロキサン系材料としては、シラノール基、アルコキシ基、アセチル基、フェニル基、ポリエーテル基、パーフルオロアルキル基等を側鎖に持つメチルポリシロキサン又はジメチルポリシロキサンが挙げられる。
【００４７】
ポリシロキサン中のシラノール基、アルコキシ基（メトキシ基やエトキシ基等）、アセチル基等の官能基は、ポリシロキサンに架橋反応性を付与するものであり、一方フェニル基はポリシロキサンに耐熱性や耐久性等を付与するために有効であり、またポリエーテル基は界面活性作用を付与するものであり、パーフルオロアルキル基は耐化学薬品性や耐水性を付与するものである。用いるポリシロキサンは、好ましくは架橋反応性を有するものがよい。
【００４８】
具体的に、入手可能なものとして、有機シロキサンとしては、東レ・ダウコーニング（株）製シリコーンオイルＢＹ１６−８１７（シラノール基）、ＳＨ５１０（フェニル基）、ＳＦ８４２１（ポリエーテル基）、ＦＳ１２６５（フルオロアルキル基）等が挙げられるが、本発明は勿論この例に限定されない。
【００４９】
また、有機シロキサン系材料の表面張力や界面張力を下げ、非晶質フッ素樹脂上に塗布させるための添加剤として、界面活性能力を有するフッ素系材料の任意のものが使用されるが、好適なものとして、パーフルオロ基と親水基を側鎖に持つフッ素化アルキルエステルやパーフルオロ基と親油基とを側鎖に持つフッ素化脂肪族高分子エステル等が挙げられる。
【００５０】
具体的に入手可能なものとして、フッ素化アルキルエステルとしては、住友スリーエム（株）製「フロラードＦＣ４３０」、「フロラードＦＣ４３１」、フッ素化脂肪族高分子エステルとしては、住友スリーエム（株）製「フロラードＦＣ７４０」が挙げられる。但し、本発明はこの材料のみに限定するものではない。
【００５１】
界面活性能力を有するフッ素系材料の使用料は、非晶質フッ素樹脂膜上に十分な濡れが確保されるような量であれば良く、特に限定されないが、一般に有機シロキサン系材料を基準として、０．５〜１０．０重量％、好ましくは１．０〜３．０重量％で用いればよい。
【００５２】
有機シロキサン系材料及び界面活性能力を有するフッ素系材料は、有機溶媒に溶解して溶液の形でコーティングに用いるのがよい。有機溶媒としては非晶質フッ素樹脂を溶解、軟化しないようなものが好ましく、アルコール系、エステル系、或いはこれらの混合系などの易揮発性の溶剤が使用される。溶液中の固形分濃度は、０．０５〜３．０重量％程度であるのが望ましい。
【００５３】
この場合、有機シロキサン系材料の硬化を促進するために、ジブチルスズラウレート、スズオクトエート等の触媒を触媒量で用いることもできる。
【００５４】
高屈折率を有する樹脂として、ポリスチレン系樹脂、ポリカーボネート系樹脂、芳香族ポリエステル系樹脂、ポリサルホン系樹脂、ポリアリレート系樹脂、フェノキシ系樹脂、エポキシ系樹脂及びそれらの塩化物や臭素化物等があげられる。これらの樹脂のうち、フェノキシ系樹脂やエポキシ系樹脂はプラスチック基板への接着性に優れ、金属酸化物の分散用バインダーとしても好ましい。
【００５５】
エポキシ系樹脂とは、エピクロールヒドリンと多価フェノール或いは多価アルコールとから誘導されるエポキシ樹脂を基本とする樹脂類であり、これにはエポキシ樹脂そのものの他に、カルボキシル基末端、水酸基末端、アミド基末端、イソシアネート基末端の重合でこれを変成して成るエポキシエステル、エポキシビニル、エポキシアミド、エポキシウレタン等の変性エポキシ樹脂も使用される。また、フェノキシ系樹脂とは、エピクロールヒドリンと多価フェノール（ビスフェノール）とから誘導される点では、エポキシ樹脂と共通しているが、はるかに高分子量であり、熱可塑性である点でエポキシ樹脂と相違するものである。
【００５６】
具体的に入手可能な塗料用エポキシ樹脂としては、大日本インキ工業（株）製「エピクロン８５０」、東レ・ダウコーニング（株）製、シリコーンレジン「ＳＲ２４１０」、「ＳＲ２４１１」、「ＳＲ２１１５」、鐘淵化学工業（株）製「カネカゼムラックＹＣ３３１５」、「ＹＣ３８３５」などがあげられる。
もちろん、本発明はこの例に限定されない。
【００５７】
本発明において、高屈折率層の膜厚は５０〜４００ｎｍ、非晶質フッ素樹脂の反射防止層の膜厚が５０〜２００ｎｍ、有機ポリシロキサンを主成分とするコート層の膜厚が２００ｎｍ以下、好ましくは１００ｎｍ以下であることが好ましい。また、高屈折率層を複層に設ける場合には、第１層目の高屈折層の膜厚が５０〜６００ｎｍ、第２層目の高屈折層の膜厚が１００〜４００ｎｍであることが好ましい。
【００５８】
また、各層の屈折率及び厚みを制御することにより、反射防止性能を最大限に向上させることができる。プラスチック基板の屈折率をｎ_S 、第一の高屈折率層の屈折率をｎ₃ 、その厚みをｄ₃ （単位はｎｍ）、第二の高屈折率層の屈折率をｎ₂ 、その厚みをｄ₂ 、反射防止層の屈折率をｎ₁ 、その厚みをｄ₁ としたとき、次の層構成とすることが好ましい。
【００５９】
図１の反射防止膜の場合、下記式（８）及び（９）
ｎ₃ ・ｎ_S ² ＝ ｎ₁ ² ‥（８）
及び
ｎ₁ ・ｄ₁ ＝ｎ₃ ・ｄ₃ ＝λ／４ ‥（９）
を実質的に満足するように、高屈折率層及び反射防止層を設けるのがよい。
【００６０】
次ぎに、図２の反射防止膜の場合、下記式（１０）及び（１１）
ｎ₁ ・ｎ₃ ＝ｎ₂ ・（ｎ₀ ・ｎ_S ）^1/2 ‥（１０）
式中、ｎ₀ は空気の屈折率である、
及び
ｎ₁ ・ｄ₁ ＝ｎ₂ ・ｄ₂ ＝ｎ₃ ・ｄ₃ ＝λ／４ ‥（１１）
を実質的に満足するように、高屈折率層及び反射防止層を設けるのがよい。
【００６１】
また、図２の反射防止膜の場合、下記式（１２）及び（１３）
ｎ₃ ²・ｎ_S ＝ ｎ₀ ・ｎ₁ ² ・・（１２）
及び
ｎ₁ ・ｄ₁ ＝ｎ₂ ・ｄ₂ ／２＝ｎ₃ ・ｄ₃ ＝λ／４ ・・（１３）
を実質的に満足するように、高屈折率層及び反射防止層を設けることもできる。
【００６２】
また、図２の反射防止膜の場合、下記式（１４）及び（１５）
ｎ₃ ²・ｎ_S ＝ ｎ₀ ・ｎ₁ ² ‥（１４）
及び
ｎ₁ ・ｄ₁／３ ＝ｎ₂ ・ｄ₂ ／２＝ｎ₃ ・ｄ₃ ＝λ／４ ‥（１５）
を実質的に満足するように、高屈折率層及び反射防止層を設けることもできる。
【００６３】
【実施例】
本発明を次の例で説明する。
【００６４】
非晶質フッ素樹脂コート液（コート液１）の調製
テフロンＡＦ−１６００（三井デュポンフロロケミカル（株）製）を濃度２％となるよう、沸点１０２℃のパーフルオロオクタン、パーフルオロハイドロフランの混合溶剤であるフロリナートＦＣ−７５（住友スリーエム（株）製）に溶解しコート液を作成した（コート液１）。
【００６５】
第１層目の高屈折率層用コート液（コート液２）の調製
アルミゾル１０（川研ファインケミカル（株）製）が１．８重量％、チタンテトラブトキシドモノマー（和光純薬工業（株）製）が４．２重量％、アセト酢酸エチルが３重量％、エチルセロソルブが１０重量％になるように、メタノールを用いて調製する（コート液２）。
【００６６】
第２層目の高屈折率層用コート液（コート液３）の調製
アルミゾル１０（川研ファインケミカル（株）製）が０．７重量％、チタンテトラブトキシドモノマー（和光純薬工業（株）製）が６．３重量％、アセト酢酸エチルが３重量％、エチルセロソルブが１０重量％になるように、メタノールを用いて調製する（コート液３）。
【００６７】
第１層目の高屈折率層用コート液（コート液４）の調製
チタンテトラブトキシドモノマー（和光純薬工業（株）製）が６．０重量％、エピクロン８５０（大日本インキ化学工業（株）製）が２．０重量％、アセト酢酸エチルが２．５重量％、エピクロンＢ−５７０（大日本インキ化学工業（株）製）が０．２重量％になるように酢酸イソブチルを用いて調製する（コート液４）。
【００６８】
第２層目の高屈折率層用コート液（コート液５）の調製
三塩化アンチモン（III ）を１．５重量％になるようにエタノールに溶解させ、０．０５規定塩酸を用いて、加水分解させ、アンチモンゾルを作成する（調製液１）。
チタンテトラブトキシドモノマー（和光純薬工業（株）製）が３．０重量％、アセト酢酸エチルが３．０重量％になるようにイソプロピルアルコールを用いて調製する（調製液２）。
調製液１と調製液２を等重量づつ混合する（コート液５）。
【００６９】
オーバーコート液（コート液６）の調製
両端末にシラノール基を有するジメチルシリコーンオイル「ＢＹ１６−８１７」（東レ・ダウンコーニング（株）製）が０．２重量％になるよう、イソプロピルアルコールと酢酸イソブチルの重量比が２対３からなる混合溶媒を用いて希釈し、ポリシロキサンの３重量％のフッ素化アルキルエステル「フロラードＦＣ４３０」（住友スリーエム（株）製）を添加する（コート液６）。
【００７０】
実施例１
あらかじめシランカップリング剤にてプライマー処理を施した、肉厚２ｍｍのポリメチルメタクリレートキャスト基板に、コート液２を引き上げ速度２００ｍｍ／ｍｉｎで製膜した。
次に、コート液１を引き上げ速度２００ｍｍ／ｍｉｎで反射防止膜を製膜した。
更に、コート液６を１００ｍｍ／ｍｉｎでオーバーコートした。
この基板を１００℃、１時間の熱処理を行ない、反射防止性能を有する基板を得た。
表面反射率は０．１％Ｔ（測定波長５５０ｎｍ）であり、鉛筆硬度は３Ｈで爪で強く擦っても全く傷は付かなかった。また、この表面固有抵抗値は２×１０¹¹Ω・ｃｍであり、帯電防止効果を有していた。各層の屈折率及び厚みは前記式（８）及び（９）を実質上満足するものであった。
【００７１】
実施例２
あらかじめシランカップリング剤にてプライマー処理を施した、肉厚２ｍｍのポリメチルメタクリレートキャスト基板に、コート液２を引き上げ速度２００ｍｍ／ｍｉｎで製膜した。
次に、コート液３を引き上げ速度１２０ｍｍ／ｍｉｎで製膜した。
次に、コート液１を引き上げ速度２００ｍｍ／ｍｉｎで反射防止膜を製膜した。
更に、実施例１と同様にコート液６を１００ｍｍ／ｍｉｎでオーバーコートした。
この基板を１００℃、１時間の熱処理を行ない、反射防止機能を有する基板を得た。
表面反射率は０．１％Ｔ（５５０ｎｍ）であり、４００〜７００ｎｍでの平均表面反射率は１．０％Ｔであり、全可視領域で優れた反射防止性能を示した。鉛筆硬度は３Ｈで、爪で強く擦っても全く傷は付かなかった。また、この表面固有抵抗値は５×１０¹¹Ωであり、帯電防止効果を有していた。各層の屈折率及び厚みは前記式（１０）及び（１１）を実質上満足するものであった。
【００７２】
実施例３
あらかじめシランカップリング剤にてプライマー処理を施した、肉厚２ｍｍのポリメチルメタクリレートキャスト基板に、コート液２を引き上げ速度２００ｍｍ／ｍｉｎで製膜した。
次に、コート液３を引き上げ速度２００ｍｍ／ｍｉｎで２回コートした。
次に、コート液１を引き上げ速度２００ｍｍ／ｍｉｎで反射防止膜を製膜した。
更に、実施例１と同様にコート液６を１００ｍｍ／ｍｉｎでオーバーコートした。
この基板を１００℃、１時間の熱処理を行ない、反射防止性能を有する基板を得た。
表面反射率は０．２％Ｔ（測定波長５００ｎｍ）であり、４００〜７００ｎｍでの平均表面反射率は０．７％Ｔであり、全可視領域で優れた反射防止性能を示した。鉛筆硬度は３Ｈで、爪で強く擦っても全く傷はつかなかった。
また、この表面固有抵抗値は５×１０¹⁰Ωであり、帯電防止効果を有していた。各層の屈折率及び厚みは前記式（１２）及び（１３）を実質上満足するものであった。
【００７３】
実施例４
あらかじめシランカップリング剤にてプライマー処理を施した、肉厚２ｍｍのポリメチルメタクリレートキャスト基板に、コート液２を引き上げ速度２００ｍｍ／ｍｉｎで３回コートした。
次に、コート液３を引き上げ速度２００ｍｍ／ｍｉｎで２回コートした。
次に、コート液１を引き上げ速度２００ｍｍ／ｍｉｎで反射防止膜を製膜した。
更に、実施例１と同様に、コート液６を１００ｍｍ／ｍｉｎでオーバーコートした。
この基板を１００℃、１時間の熱処理を行ない、反射防止性能を有する基板を得た。
表面反射率は０．２％Ｔ（測定波長５５０ｎｍ）であり、４００〜７００ｎｍでの平均表面反射率は０．７％Ｔであり、全可視領域で優れた反射防止性能を示した。鉛筆硬度は３Ｈで、爪で強く擦っても全く傷は付かなかった。また、この表面固有抵抗値は５×１０¹⁰Ω・ｃｍであり、優れた帯電防止効果を有していた。各層の屈折率及び厚みは前記式（１４）及び（１５）を実質上満足するものであった。
【００７４】
実施例５
あらかじめシランカップリング剤にてプライマー処理を施した、肉厚２ｍｍのポリメチルメタクリレートキャスト基板に、コート液４を引き上げ速度２００ｍｍ／ｍｉｎで製膜した。
次に、コート液１を引き上げ速度２００ｍｍ／ｍｉｎで反射防止膜を製膜した。
更に、コート液６を１００ｍｍ／ｍｉｎでオーバーコートした。
この基板を１００℃、１時間の熱処理を行い、反射防止性能を有する基板を得た。
表面反射率は０．１％Ｔ（測定波長５５０ｎｍ）であり、鉛筆硬度は４Ｈで、爪で強く擦っても全く傷は付かなかった。また、この表面固有抵抗値は５×１０¹²Ω・ｃｍであり、やや帯電防止効果を有していた。各層の屈折率及び厚みは前記式（８）及び（９）を実質上満足するものであった。
【００７５】
実施例６
あらかじめシランカップリング剤にてプライマー処理を施した、肉厚２ｍｍのポリメチルメタクリレートキャスト基板に、コート液４を引き上げ速度２００ｍｍ／ｍｉｎで製膜した。
次に、コート液５を引き上げ速度１２０ｍｍ／ｍｉｎで製膜した。
次に、コート液１を引き上げ速度２００ｍｍ／ｍｉｎで反射防止膜を製膜した。
更に、実施例１と同様にコート液６を１００ｍｍ／ｍｉｎでオーバーコートした。
この基板を１００℃、１時間の熱処理を行ない、反射防止機能を有する基板を得た。
表面反射率は０．１％Ｔ（測定波長５５０ｎｍ）であり、４００〜７００ｎｍでの平均表面反射率は１．０％Ｔであり、全可視領域で優れた反射防止性能を示した。鉛筆硬度は３Ｈで、爪で強く擦っても全く傷は付かなかった。また、この表面固有抵抗値は５×１０¹¹Ωであり、帯電防止効果を有していた。各層の屈折率及び厚みは前記式（１０）及び（１１）を実質上満足するものであった。
【００７６】
実施例７
あらかじめシランカップリング剤にてプライマー処理を施した、肉厚２ｍｍのポリメチルメタクリレートキャスト基板に、コート液４を引き上げ速度２００ｍｍ／ｍｉｎで製膜した。
次に、コート液５を引き上げ速度２００ｍｍ／ｍｉｎで２回コートした。
次に、コート液１を引き上げ速度２００ｍｍ／ｍｉｎで反射防止膜を製膜した。
更に、実施例１と同様にコート液６を１００ｍｍ／ｍｉｎでオーバーコートした。
この基板を１００℃、１時間の熱処理を行ない、反射防止性能を有する基板を得た。
表面反射率は０．２％Ｔ（測定波長５００ｎｍ）であり、４００〜７００ｎｍでの平均表面反射率は０．７％Ｔであり、全可視領域で優れた反射防止性能を示した。鉛筆硬度は３Ｈで、爪で強く擦っても全く傷はつかなかった。
また、この表面固有抵抗値は５×１０¹¹Ωであり、帯電防止効果を有していた。各層の屈折率及び厚みは前記式（１２）及び（１３）を実質上満足するものであった。
【００７７】
実施例８
あらかじめシランカップリング剤にてプライマー処理を施した、肉厚２ｍｍのポリメチルメタクリレートキャスト基板に、コート液４を引き上げ速度２００ｍｍ／ｍｉｎで３回コートした。
次に、コート液５を引き上げ速度２００ｍｍ／ｍｉｎで２回コートした。
次に、コート液１を引き上げ速度２００ｍｍ／ｍｉｎで反射防止膜を製膜した。
更に、実施例１と同様に、コート液６を１００ｍｍ／ｍｉｎでオーバーコートした。
この基板を１００℃、１時間の熱処理を行ない、反射防止性能を有する基板を得た。
表面反射率は０．２％Ｔ（測定波長５５０ｎｍ）であり、４００〜７００ｎｍでの平均表面反射率は０．７％Ｔであり、全可視領域で優れた反射防止性能を示した。鉛筆硬度は３Ｈで、爪で強く擦っても全く傷は付かなかった。また、この表面固有抵抗値は５×１０¹⁰Ω・ｃｍであり、優れた帯電防止効果を有していた。各層の屈折率及び厚みは前記式（１４）及び（１５）を実質上満足するものであった。
【００７８】
比較例１
あらかじめシランカップリング剤にてプライマー処理を施した、肉厚２ｍｍのポリメチルメタクリレートキャスト基板に、コート液１を引き上げ速度２００ｍｍ／ｍｉｎで単層反射防止膜を製膜した。
次に、コート液６を１００ｍｍ／ｍｉｎでオーバーコートした。
この基板を１００℃、１時間の熱処理を行い、反射防止性能を有する基板を得た。
表面反射率は１．２％Ｔ（５５０ｎｍ）であり、鉛筆硬度は４Ｈで爪で強く擦っても全く傷は付かなかった。この表面固有抵抗値は１０¹⁵Ω・ｃｍ以上であり、全く帯電防止効果はなかった。
【００７９】
【発明の効果】
本発明によれば、非晶質フッ素樹脂を用いた反射防止膜のアンダー層に、コロイド状金属酸化物を用いた高屈折率層を１〜２層もうけることにより、全可視領域（４００〜７００ｎｍ）で一定して優れた反射防止性能を有し、かつ優れた帯電防止性能を有する反射防止膜を提供することができる。更に、反射防止性能を全く影響を与えない厚さのオーバーコート層を設けることで、膜強度の弱さ、即ち耐磨耗性、耐擦傷性を大幅に改善し、無機蒸着反射防止膜に引けを取らないＣＲＴディスプレー全面パネル等の使用に十分耐えうる反射防止膜を提供することができる。
【図面の簡単な説明】
【図１】本発明の反射防止膜の一例を示す断面図である。
【図２】本発明の反射防止膜の他の例を示す断面図である。
【記号の説明】
１ 透光性プラスチック基板
２、２ａ，２ｂ 高屈折率層
３ 反射防止層
４ コート層[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an antireflection film for producing a plastic material having excellent translucency.
[0002]
[Prior art and its problems]
Translucent plastic materials are also used in optical filters and optical lenses, but since the refractive index is in the range of 1.45 to 1.60, even though it is completely transparent, it is about 7 to 10%. Causes optical reflection.
[0003]
This light reflection causes a decrease in light transmittance, a ghost phenomenon due to reflection, and a difficulty in seeing an object through the light.
[0004]
As a method of removing or reducing this reflection, a combination of a λ / 4 film such as magnesium fluoride or silica having a low refractive index by vacuum deposition or a λ / 4 film such as titanium oxide or zirconium oxide having a high refractive index is used. Multilayer coats from have been used.
[0005]
For coating on small objects such as optical lenses, the film quality and productivity are good, but for large plates such as CRT display full-scale panels, the number of one-time injections into the evaporation pot is extremely high. However, there is a problem that the cost becomes high.
[0006]
On the other hand, another method is known in which a solvent-soluble amorphous fluororesin is dissolved in an appropriate solvent, and a film is formed by a dipping method to obtain an antireflection film. Although this method is relatively easy to coat on a large plate, the resin itself is poor in hardness, and a λ / 4 wavelength film, that is, a film having a thickness of 100 to 200 nm is easily peeled off. It is impossible to use it in the state. Moreover, due to the strong water repellency, strong oil repellency, and electrical insulation, which are the characteristics of fluororesin, there is also a problem that it is easily charged with static electricity and adsorbs dust. However, the biggest problem is that the antireflection performance is slightly inferior to the vacuum deposition method.
[0007]
[Problems to be solved by the invention]
The present invention provides a weakness of the film, that is, wear resistance, by providing an overcoat layer having a thickness that does not affect the antireflection performance on the antireflection film formed of an amorphous fluororesin. Provided is an antireflection film capable of greatly improving the scratch resistance and sufficiently withstanding the use of a CRT display full-surface panel or the like.
[0008]
In addition, as an underlayer of an antireflection film formed of an amorphous fluororesin, a combination of a metal alkoxide and a colloidal metal oxide and / or an inorganic precursor thereof is used. By providing one or two refractive index layers, an antireflection film having an antistatic effect is provided without deteriorating the strong water repellency and strong oil repellency characteristic of a fluororesin, and at least two layers of multilayer interference By the action of the film, it becomes possible to reduce the reflection in the entire visible region (400 to 700 nm), and for the purpose of providing an antireflection film similar to vacuum deposition by a film forming method by dipping using a sol-gel method. Yes.
[0009]
[Means for Solving the Problems]
According to the present invention, a plastic substrate having a light-transmitting property, a metal alkoxide coated on the substrate, a colloidal metal oxide and / or a metal halide, and, if necessary, an antistatic performance mainly comprising an epoxy resin. A high refractive index layer, an amorphous fluororesin antireflective layer having a refractive index (nd) of 1.36 or less coated on the high refractive index layer, and an organic polysiloxane coated on the antireflective film An antireflection film excellent in wear resistance, scratch resistance, adhesion, and translucency is provided, comprising a coating layer containing a fluorine-based material having a surface active ability as a main component. .
[0010]
DETAILED DESCRIPTION OF THE INVENTION
In FIG. 1 showing an example of the antireflection film of the present invention, the antireflection film includes a translucent plastic substrate 1, a high refractive index layer 2 provided on the substrate, and a reflection provided on the high refractive index layer. It consists of the coating layer 4 provided on the prevention layer 3 and the antireflection layer.
[0011]
In FIG. 2 showing another example of the antireflection film of the present invention, the antireflection film comprises a translucent plastic substrate 1, a first high refractive index layer 2a provided on the substrate, and a first high refraction. It comprises a second high refractive index layer 2b provided on the refractive index layer, an antireflection layer 3 provided on the second high refractive index layer, and a coating layer 4 provided on the antireflection layer.
[0012]
In the present invention, the high refractive index layers 2, 2a, 2b, etc. provided on the plastic substrate are composed mainly of a metal alkoxide, a colloidal metal oxide and / or a metal halide, and, if necessary, an epoxy resin. The high refractive index layer has antistatic performance.
[0013]
As the antireflection layer 3, an amorphous fluororesin having a refractive index (nd) of 1.36 or less is used, and as the coating layer 4, a fluorine-based material having organic polysiloxane as a main component and having a surface activity ability A composition containing is used.
[0014]
According to the present invention, under the antireflection layer made of the amorphous fluororesin, a metal alkoxide, a colloidal metal oxide and / or a metal halide, and if necessary, an epoxy resin as a main component. By providing a refractive index layer, dust that has been a drawback of amorphous fluororesins is imparted antistatic performance without impairing the water repellency, oil repellency, stain resistance, etc. inherent to amorphous fluororesins. It is possible to prevent such an adsorption tendency.
[0015]
In addition, since the high refractive index layer is provided under the low refractive index antireflection layer, the light reflectance can be further reduced, and it is exceptionally excellent as an antireflection film by the sol-gel coating method. Anti-reflection performance is obtained.
[0016]
Furthermore, by combining colloidal metal oxides and / or metal halides and metal alkoxides, it is possible not only to form a strong film, but also to adhere to various plastic substrates by combining epoxy resins as necessary. As a result, the high refractive index of the lower layer can be freely adjusted, so that it is possible to produce a multilayer antireflection film corresponding to various transparent plastic substrates.
[0017]
The low refractive index of the amorphous fluororesin effective as an antireflective coating is due to the large amount of fluorine atoms contained in the molecule. However, the presence of this fluorine atom makes the film surface highly water- and oil-repellent, and even if a hard coating agent or similar paint is formed on it, it is repelled and becomes polka dots. Can not be formed. In addition, the water repellency is very high, so that it is easy to be charged with static electricity and easily adsorbs dust and dirt in the air.
[0018]
However, a material having a hydrophilic and fluorophilic surface active ability, such as a low molecular weight copolymer of (meth) acrylate having a perfluoroalkyl group and ethylene glycol (meth) acrylate, is a fluororesin surface. It showed complete wettability, and by adding these, it became possible to coat the organic polysiloxane material on the surface of the fluororesin.
[0019]
In addition, due to the characteristics of organic polysiloxane materials, the slipperiness of the surface is greatly improved, scratch resistance and abrasion resistance are obtained, and the weakness of the film, which is the first difficulty of amorphous fluororesin, is reduced. It was possible to improve. Furthermore, it was also found that water resistance and alcohol resistance can be obtained by using a polysiloxane having a perfluoroalkyl group.
[0020]
The plastic substrate 1 is not particularly limited, but from the viewpoint of optical properties, polymethyl methacrylate, polycarbonate, polyallyl diglycol carbonate, polystyrene, etc. can be used, and those colored with a transparent or oil-soluble dye are used. The In order to increase the familiarity and adhesion between the fluororesin and the substrate, a primer-coated one can be used in the present invention.
[0021]
In the present invention, the colloidal metal oxide used as a component of the high refractive index layer 2 and imparting an antistatic effect to the antireflection film due to its hydrophilic property includes silica sol, titania sol, alumina sol, zirconium oxide sol, antimony oxide sol. In consideration of refractive index adjustment, dispersibility in organic solvents, coating solution stability, and wettability and adhesion to plastic substrates and amorphous fluororesin, silica sol, alumina sol Antimony oxide sol is preferred. Further, these colloidal metal oxides can be easily produced by performing hydrolysis of metal chloride in an organic solvent.
[0022]
In the present invention, a metal halide or metal bromide is used as a metal halide used as a component of the high refractive index layer 2 for the purpose of increasing the refractive index. More specifically, antimony trichloride is used. , Zirconium tetrachloride, bismuth trichloride, titanium tetrabromide, antimony tribromide, etc., but considering the point of increasing the refractive index, dispersibility in organic solvents, and stability of the coating solution, antimony trichloride Bismuth trichloride and antimony tribromide are preferred.
[0023]
Moreover, the metal alkoxide used as a binder for bonding these colloidal metal oxides to a plastic substrate and an amorphous fluororesin is represented by the following formula (1).
M (OR)_m                   (1)
Where M represents a metal,
R represents a hydrocarbon group having 1 to 5 carbon atoms,
m represents the valence (3 or 4) of the metal M,
It is represented by
[0024]
As the metal M, aluminum, titanium, zirconium, tin or the like is suitable.
Specific examples of the metal alkoxide include aluminum ethoxide, aluminum isopropoxide, aluminum butoxide, aluminum t-butoxide, tin t-butoxide, titanium methoxide, titanium ethoxide, titanium n-propoxide, titanium isopropoxide, and titanium n. -Butoxide, titanium isobutoxide, zirconium ethoxide, zirconium n-propoxide, zirconium isopropoxide, zirconium n-butoxide and the like.
[0025]
These metal alkoxides are very unstable substances that are characterized by reacting rapidly with moisture to form precipitates. These can be used as a stable coating composition by reacting with a β-diketone to form a chelate compound.
[0026]
Here, specific examples of β-diketone include methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, i-propyl acetoacetate, and acetylacetone, and most preferably ethyl acetoacetate.
The β-diketone is used in a molar ratio of 0.5 to 2.0 mol with respect to the metal alkoxide, more preferably 0.8 to 1.2 mol.
[0027]
Further, a compound obtained by chelating a metal alkoxide may be hydrolyzed and used.
As the hydrolyzing agent, a mineral acid such as hydrochloric acid, nitric acid or sulfuric acid, or an organic acid such as acetic acid or succinic acid may be used as the aqueous solution.
[0028]
In the hydrolysis, the acidic aqueous solution used is preferably 0.5 mol to 2.0 mol, more preferably 0.5 mol to 1.0 mol, relative to 1 mol of the metal alkoxide chelate compound. At this time, if the amount of water is large, the stability of the coating solution is deteriorated.
[0029]
A high refractive index layer formed only of a metal alkoxide chelate compound has a slightly difficult surface to use as an optical thin film by itself because the film strength is weak. Further, it is difficult to increase the film thickness only with a metal alkoxide chelate compound, and a colloidal metal oxide is added in order to compensate for its drawbacks and to impart an antistatic effect due to its hydrophilicity. Further, the refractive index can be further increased by adding a metal halide. Furthermore, by adding an epoxy resin, it is possible to prevent cracks due to thickening and to adhere to a plastic substrate.
[0030]
In the coating composition for a high refractive index layer in the present invention, an organic solvent can be used as a solvent. The organic solvent may be compatible with metal alkoxide or colloidal metal oxide, and is not particularly limited. Examples of the solvent include alcohols, ketones, esters, aromatic hydrocarbons and the like. Specific examples include methanol, isopropanol, methyl ethyl ketone, isobutyl acetate, toluene and the like.
Using these solvents, the concentration is adjusted so that the total solid concentration is 1 to 30% by weight of the total weight.
[0031]
As a coating method, a dipping method that can easily form a thin film can be preferably used. In general, the coated thin film is preferably heat-treated at a temperature of about 70 to 140 ° C.
[0032]
Refractive index n_ThreeThe perfluoro amorphous fluororesin having an A of 1.36 or less may be any perfluoro amorphous fluororesin having a ring structure in the main chain, but a suitable example of this perfluoro amorphous fluororesin In the main chain, the following formula (2)
[0033]
[Chemical 1]

R: perfluoroalkylene group
p: number of zero or one
q: Number of zero or one
Repeating unit of the following formula (3)
[0034]
[Chemical 2]

R: perfluoroalkylene group
And / or the following formula (4)
[0035]
[Chemical Formula 3]

R: perfluoroalkylene group
And a perfluoro fluororesin containing at least one of the above repeating units.
[0036]
This perfluoro fluororesin is a perfluoro single resin in which all of the repeating units are composed of the cyclic repeating unit, or a part of the repeating unit is formed from the cyclic repeating unit and the remaining part of the repeating unit is linear. It may consist of a monomer unit.
[0037]
The perfluoro amorphous fluororesin can be obtained by a method known per se, for example, by cyclopolymerization of a perfluoroether monomer having double bonds at both ends or radical polymerization of a cyclic perfluoromonomer. Obtainable. A copolymer can be obtained by allowing other perfluoromonomer to coexist in the polymerization.
[0038]
As the perfluoroether monomer having double bonds at both ends, the following formula (5)
CF₂= CF-(-CF₂−)_n-O-(-CF₂−)_m-CF = CF₂(5)
(N = 1-5, m = 1-5, n + m = 1-6)
And examples thereof include perfluoroallyl vinyl ether, perfluorodiallyl ether, perfluorobutenyl vinyl ether, perfluorobutenyl allyl vinyl ether, perfluorodibutenyl ether, and the like. .
[0039]
As another type of the perfluoroether monomer having double bonds at both ends, the following formula (6)
CF₂= CFO-R-O-CF = CF₂          (6)
R: perfluoroalkylene group
Perfluoroalkylene glycol divinyl ether represented by the formula: Examples thereof include perfluoroethylene glycol divinyl ether and perfluorotetramethylene glycol divinyl ether.
[0040]
On the other hand, as the cyclic perfluoromonomer, for example, the following formula (7)
[0041]
[Formula 4]

R: perfluoroalkylene group
And, in particular, perfluoro-2,2-dimethyl-1,3-dioxole.
[0042]
Examples of other monomers used for copolymerization include tetrafluoroethylene, hexafluoropropylene, perfluorovinyl propyl ether, perfluoroallyl butyl ether, perfluorodivinyl ethyl ether, and perfluorovinyl allyl ether.
[0043]
Suitable examples of the amorphous fluororesin include, but are not limited to, a copolymer of cyclic ether and perfluoro-2,2-dimethyl-1,3-dioxole, a copolymer of tetrafluoroethylene and cyclic perfluoroether. Polymers, cyclized copolymers with perfluorovinyl allyl ether, and the like.
[0044]
Specifically, “Teflon AF” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Cytop” manufactured by Asahi Glass Co., Ltd., “Florard FC-722” manufactured by Sumitomo 3M Co., Ltd., “Teflon manufactured by DuPont” AF1600 "etc. are mentioned.
[0045]
As the solvent, perfluorooctane, perfluorohydrofuran and the like are good in balance of volatilization speed, and the above resin can be dissolved at a concentration of 1 to 5% to prepare a coating solution.
[0046]
In the present invention, the organic polysiloxane material used as an overcoat layer and imparting abrasion resistance and scratch resistance includes silanol groups, alkoxy groups, acetyl groups, phenyl groups, polyether groups, perfluoroalkyl groups. Etc. in the side chain.
[0047]
Functional groups such as silanol groups, alkoxy groups (such as methoxy groups and ethoxy groups), and acetyl groups in polysiloxanes impart cross-linking reactivity to polysiloxanes, while phenyl groups provide heat resistance and durability to polysiloxanes. The polyether group imparts a surface active action, and the perfluoroalkyl group imparts chemical resistance and water resistance. The polysiloxane used preferably has cross-linking reactivity.
[0048]
Specifically, as the organic siloxane, available are silicone oil BY16-817 (silanol group), SH510 (phenyl group), SF8421 (polyether group), FS1265 (fluoroalkyl) manufactured by Toray Dow Corning Co., Ltd. Group) and the like, but the present invention is of course not limited to this example.
[0049]
Further, as an additive for lowering the surface tension or interfacial tension of the organic siloxane-based material and applying it on the amorphous fluororesin, any of fluorine-based materials having surface active ability is used. Examples thereof include a fluorinated alkyl ester having a perfluoro group and a hydrophilic group in the side chain, and a fluorinated aliphatic polymer ester having a perfluoro group and a lipophilic group in the side chain.
[0050]
Specifically, as the fluorinated alkyl ester, “Florard FC430” and “Florard FC431” manufactured by Sumitomo 3M Co., Ltd., and as the fluorinated aliphatic polymer ester, “Florard” manufactured by Sumitomo 3M Co., Ltd. are available. FC740 ". However, the present invention is not limited to this material.
[0051]
The usage fee of the fluorine-based material having the surface activity ability is not particularly limited as long as it is sufficient to ensure sufficient wetting on the amorphous fluororesin film, but generally, based on the organosiloxane material, The content may be 0.5 to 10.0% by weight, preferably 1.0 to 3.0% by weight.
[0052]
The organic siloxane-based material and the fluorine-based material having surface active ability are preferably dissolved in an organic solvent and used for coating in the form of a solution. As the organic solvent, those which do not dissolve or soften the amorphous fluororesin are preferable, and easily volatile solvents such as alcohols, esters, or mixtures thereof are used. The solid content concentration in the solution is preferably about 0.05 to 3.0% by weight.
[0053]
In this case, a catalyst such as dibutyltin laurate or tin octoate can be used in a catalytic amount in order to promote curing of the organosiloxane material.
[0054]
Examples of resins having a high refractive index include polystyrene resins, polycarbonate resins, aromatic polyester resins, polysulfone resins, polyarylate resins, phenoxy resins, epoxy resins, and chlorides and bromides thereof. . Among these resins, phenoxy resins and epoxy resins are excellent in adhesion to plastic substrates and are preferable as a binder for dispersing metal oxides.
[0055]
Epoxy resins are resins based on epoxy resins derived from epichlorohydrin and polyhydric phenols or polyhydric alcohols. In addition to the epoxy resin itself, there are also carboxyl group terminals, hydroxyl terminal groups. Further, modified epoxy resins such as epoxy esters, epoxy vinyls, epoxy amides, epoxy urethanes, etc., which are modified by polymerization of amide group terminals and isocyanate group terminals are also used. Phenoxy resins are common to epoxy resins in that they are derived from epichlorhydrin and polyphenols (bisphenols), but epoxy resins are much higher in molecular weight and thermoplastic. It is different from resin.
[0056]
Specifically available epoxy resins for paint include “Epicron 850” manufactured by Dainippon Ink Industries, Ltd., silicone resin “SR2410”, “SR2411”, “SR2115” manufactured by Toray Dow Corning Co., Ltd., bell Examples include “Kanekazemlac YC3315” and “YC3835” manufactured by Sakai Chemical Industry Co., Ltd.
Of course, the present invention is not limited to this example.
[0057]
In the present invention, the high refractive index layer has a thickness of 50 to 400 nm, the amorphous fluororesin antireflection layer has a thickness of 50 to 200 nm, the organic polysiloxane-based coating layer has a thickness of 200 nm or less, Preferably it is 100 nm or less. When the high refractive index layer is provided in multiple layers, the thickness of the first high refractive layer is 50 to 600 nm, and the thickness of the second high refractive layer is 100 to 400 nm. preferable.
[0058]
Moreover, the antireflection performance can be improved to the maximum by controlling the refractive index and thickness of each layer. The refractive index of the plastic substrate is n_S, The refractive index of the first high refractive index layer is n_Three, The thickness is d_Three(Unit: nm), the refractive index of the second high refractive index layer is n₂, The thickness is d₂, The refractive index of the antireflection layer is n₁, The thickness is d₁It is preferable to use the following layer structure.
[0059]
In the case of the antireflection film of FIG.
n_Three・ N_S ² = N₁ ²                    (8)
as well as
n₁・ D₁= N_Three・ D_Three= Λ / 4 (9)
Is preferably provided with a high refractive index layer and an antireflection layer.
[0060]
Next, in the case of the antireflection film of FIG. 2, the following equations (10) and (11)
n₁・ N_Three= N₂・ (N₀・ N_S)^1/2          (10)
Where n₀Is the refractive index of air,
as well as
n₁・ D₁= N₂・ D₂= N_Three・ D_Three= Λ / 4 (11)
Is preferably provided with a high refractive index layer and an antireflection layer.
[0061]
In the case of the antireflection film of FIG. 2, the following formulas (12) and (13)
n_Three ²・ N_S = N₀・ N₁ ²                        (12)
as well as
n₁・ D₁= N₂・ D₂/ 2 = n_Three・ D_Three= Λ / 4 (13)
Can be provided with a high refractive index layer and an antireflection layer.
[0062]
In the case of the antireflection film of FIG. 2, the following formulas (14) and (15)
n_Three ²・ N_S = N₀・ N₁ ²                      (14)
as well as
n₁・ D₁/ 3 = N₂・ D₂/ 2 = n_Three・ D_Three= Λ / 4 (15)
Can be provided with a high refractive index layer and an antireflection layer.
[0063]
【Example】
The invention is illustrated by the following examples.
[0064]
Preparation of amorphous fluororesin coating solution (Coating solution 1)
Fluorinert FC-75 (manufactured by Sumitomo 3M Limited) is a mixed solvent of perfluorooctane and perfluorohydrofuran having a boiling point of 102 ° C. so that the concentration of Teflon AF-1600 (manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) is 2%. ) To prepare a coating solution (Coating Solution 1).
[0065]
Preparation of coating liquid for first refractive index layer (Coating liquid 2)
Aluminum sol 10 (manufactured by Kawaken Fine Chemical Co., Ltd.) is 1.8% by weight, titanium tetrabutoxide monomer (manufactured by Wako Pure Chemical Industries, Ltd.) is 4.2% by weight, ethyl acetoacetate is 3% by weight, and ethyl cellosolve is It is prepared using methanol so as to be 10% by weight (Coating liquid 2).
[0066]
Preparation of coating liquid for second refractive index layer (Coating liquid 3)
Aluminum sol 10 (manufactured by Kawaken Fine Chemical Co., Ltd.) is 0.7% by weight, titanium tetrabutoxide monomer (manufactured by Wako Pure Chemical Industries, Ltd.) is 6.3% by weight, ethyl acetoacetate is 3% by weight, and ethyl cellosolve is It is prepared using methanol so as to be 10% by weight (Coating liquid 3).
[0067]
Preparation of coating liquid for first refractive index layer (coating liquid 4)
Titanium tetrabutoxide monomer (manufactured by Wako Pure Chemical Industries, Ltd.) is 6.0% by weight, Epicron 850 (manufactured by Dainippon Ink and Chemicals) is 2.0% by weight, and ethyl acetoacetate is 2.5% by weight. , Epicron B-570 (manufactured by Dainippon Ink & Chemicals, Inc.) is prepared using isobutyl acetate so as to be 0.2% by weight (coating liquid 4).
[0068]
Preparation of second layer high refractive index coating liquid (Coating liquid 5)
Antimony trichloride (III) is dissolved in ethanol so as to be 1.5% by weight and hydrolyzed with 0.05 N hydrochloric acid to prepare an antimony sol (Preparation Solution 1).
A titanium tetrabutoxide monomer (manufactured by Wako Pure Chemical Industries, Ltd.) is prepared using isopropyl alcohol so that 3.0% by weight and ethyl acetoacetate are 3.0% by weight (Preparation Solution 2).
Preparation liquid 1 and preparation liquid 2 are mixed in equal weights (coating liquid 5).
[0069]
Preparation of overcoat solution (coat solution 6)
A mixture of isopropyl alcohol and isobutyl acetate in a weight ratio of 2 to 3 so that dimethyl silicone oil “BY16-817” (manufactured by Toray Downcorning Co., Ltd.) having silanol groups at both ends is 0.2% by weight. The solution is diluted with a solvent, and 3% by weight of a fluorinated alkyl ester “Florard FC430” (manufactured by Sumitomo 3M Limited) of polysiloxane is added (coat liquid 6).
[0070]
Example 1
The coating liquid 2 was pulled up and formed into a film at a speed of 200 mm / min on a polymethyl methacrylate cast substrate having a thickness of 2 mm that had been previously primed with a silane coupling agent.
Next, the coating liquid 1 was pulled up to form an antireflection film at a speed of 200 mm / min.
Furthermore, the coating liquid 6 was overcoated at 100 mm / min.
This substrate was heat-treated at 100 ° C. for 1 hour to obtain a substrate having antireflection performance.
The surface reflectance was 0.1% T (measurement wavelength: 550 nm), the pencil hardness was 3H, and no flaws were observed even when rubbed strongly with a nail. The surface resistivity is 2 × 10¹¹It was Ω · cm and had an antistatic effect. The refractive index and thickness of each layer substantially satisfied the above formulas (8) and (9).
[0071]
Example 2
The coating liquid 2 was pulled up and formed into a film at a speed of 200 mm / min on a polymethyl methacrylate cast substrate having a thickness of 2 mm that had been previously primed with a silane coupling agent.
Next, the coating liquid 3 was formed at a pulling rate of 120 mm / min.
Next, the coating liquid 1 was pulled up to form an antireflection film at a speed of 200 mm / min.
Further, as in Example 1, the coating liquid 6 was overcoated at 100 mm / min.
This substrate was heat-treated at 100 ° C. for 1 hour to obtain a substrate having an antireflection function.
The surface reflectance was 0.1% T (550 nm), the average surface reflectance at 400 to 700 nm was 1.0% T, and excellent antireflection performance was exhibited in the entire visible region. The pencil hardness was 3H, and it was not scratched at all even when rubbed strongly with a nail. The surface resistivity is 5 × 10¹¹It was Ω and had an antistatic effect. The refractive index and thickness of each layer substantially satisfied the expressions (10) and (11).
[0072]
Example 3
The coating liquid 2 was pulled up and formed into a film at a speed of 200 mm / min on a polymethyl methacrylate cast substrate having a thickness of 2 mm that had been previously primed with a silane coupling agent.
Next, the coating liquid 3 was coated twice at a pulling rate of 200 mm / min.
Next, the coating liquid 1 was pulled up to form an antireflection film at a speed of 200 mm / min.
Further, as in Example 1, the coating liquid 6 was overcoated at 100 mm / min.
This substrate was heat-treated at 100 ° C. for 1 hour to obtain a substrate having antireflection performance.
The surface reflectance was 0.2% T (measurement wavelength: 500 nm), the average surface reflectance at 400 to 700 nm was 0.7% T, and excellent antireflection performance was exhibited in the entire visible region. The pencil hardness was 3H, and even when rubbed strongly with a nail, there was no scratch.
The surface resistivity is 5 × 10^TenIt was Ω and had an antistatic effect. The refractive index and thickness of each layer substantially satisfied the above formulas (12) and (13).
[0073]
Example 4
A coating solution 2 was pulled three times at a pulling rate of 200 mm / min on a polymethylmethacrylate cast substrate having a thickness of 2 mm which had been previously primed with a silane coupling agent.
Next, the coating liquid 3 was coated twice at a pulling rate of 200 mm / min.
Next, the coating liquid 1 was pulled up to form an antireflection film at a speed of 200 mm / min.
Furthermore, as in Example 1, the coating liquid 6 was overcoated at 100 mm / min.
This substrate was heat-treated at 100 ° C. for 1 hour to obtain a substrate having antireflection performance.
The surface reflectance was 0.2% T (measurement wavelength 550 nm), the average surface reflectance at 400 to 700 nm was 0.7% T, and excellent antireflection performance was exhibited in the entire visible region. The pencil hardness was 3H, and it was not scratched at all even when rubbed strongly with a nail. The surface resistivity is 5 × 10^TenIt was Ω · cm and had an excellent antistatic effect. The refractive index and thickness of each layer substantially satisfied the expressions (14) and (15).
[0074]
Example 5
The coating liquid 4 was pulled up and formed into a film at a speed of 200 mm / min on a polymethyl methacrylate cast substrate having a thickness of 2 mm that had been previously primed with a silane coupling agent.
Next, the coating liquid 1 was pulled up to form an antireflection film at a speed of 200 mm / min.
Furthermore, the coating liquid 6 was overcoated at 100 mm / min.
This substrate was heat-treated at 100 ° C. for 1 hour to obtain a substrate having antireflection performance.
The surface reflectance was 0.1% T (measurement wavelength: 550 nm), the pencil hardness was 4H, and no scratches were found even when rubbed strongly with a nail. The surface resistivity is 5 × 10¹²It was Ω · cm and had a slight antistatic effect. The refractive index and thickness of each layer substantially satisfied the above formulas (8) and (9).
[0075]
Example 6
The coating liquid 4 was pulled up and formed into a film at a speed of 200 mm / min on a polymethyl methacrylate cast substrate having a thickness of 2 mm that had been previously primed with a silane coupling agent.
Next, the coating solution 5 was formed at a pulling rate of 120 mm / min.
Next, the coating liquid 1 was pulled up to form an antireflection film at a speed of 200 mm / min.
Further, as in Example 1, the coating liquid 6 was overcoated at 100 mm / min.
This substrate was heat-treated at 100 ° C. for 1 hour to obtain a substrate having an antireflection function.
The surface reflectance was 0.1% T (measurement wavelength 550 nm), the average surface reflectance at 400 to 700 nm was 1.0% T, and excellent antireflection performance was exhibited in the entire visible region. The pencil hardness was 3H, and it was not scratched at all even when rubbed strongly with a nail. The surface resistivity is 5 × 10¹¹It was Ω and had an antistatic effect. The refractive index and thickness of each layer substantially satisfied the expressions (10) and (11).
[0076]
Example 7
The coating liquid 4 was pulled up and formed into a film at a speed of 200 mm / min on a polymethyl methacrylate cast substrate having a thickness of 2 mm that had been previously primed with a silane coupling agent.
Next, the coating liquid 5 was coated twice at a pulling rate of 200 mm / min.
Next, the coating liquid 1 was pulled up to form an antireflection film at a speed of 200 mm / min.
Further, as in Example 1, the coating liquid 6 was overcoated at 100 mm / min.
This substrate was heat-treated at 100 ° C. for 1 hour to obtain a substrate having antireflection performance.
The surface reflectance was 0.2% T (measurement wavelength: 500 nm), the average surface reflectance at 400 to 700 nm was 0.7% T, and excellent antireflection performance was exhibited in the entire visible region. The pencil hardness was 3H, and even when rubbed strongly with a nail, there was no scratch.
The surface resistivity is 5 × 10¹¹It was Ω and had an antistatic effect. The refractive index and thickness of each layer substantially satisfied the above formulas (12) and (13).
[0077]
Example 8
A coating solution 4 was pulled three times at a pulling rate of 200 mm / min on a polymethyl methacrylate cast substrate having a thickness of 2 mm that had been previously primed with a silane coupling agent.
Next, the coating liquid 5 was coated twice at a pulling rate of 200 mm / min.
Next, the coating liquid 1 was pulled up to form an antireflection film at a speed of 200 mm / min.
Furthermore, as in Example 1, the coating liquid 6 was overcoated at 100 mm / min.
This substrate was heat-treated at 100 ° C. for 1 hour to obtain a substrate having antireflection performance.
The surface reflectance was 0.2% T (measurement wavelength: 550 nm), the average surface reflectance at 400 to 700 nm was 0.7% T, and excellent antireflection performance was exhibited in the entire visible region. The pencil hardness was 3H, and it was not scratched at all even when rubbed strongly with a nail. The surface resistivity is 5 × 10^TenIt was Ω · cm and had an excellent antistatic effect. The refractive index and thickness of each layer substantially satisfied the expressions (14) and (15).
[0078]
Comparative Example 1
A single-layer antireflection film was formed at a rate of 200 mm / min by pulling up the coating liquid 1 on a polymethylmethacrylate cast substrate having a thickness of 2 mm that had been previously primed with a silane coupling agent.
Next, the coating liquid 6 was overcoated at 100 mm / min.
This substrate was heat-treated at 100 ° C. for 1 hour to obtain a substrate having antireflection performance.
The surface reflectance was 1.2% T (550 nm), the pencil hardness was 4H, and no scratches were observed even when rubbed strongly with a nail. This surface resistivity is 10¹⁵It was Ω · cm or more, and there was no antistatic effect.
[0079]
【The invention's effect】
According to the present invention, by providing one or two high refractive index layers using a colloidal metal oxide in the underlayer of an antireflection film using an amorphous fluororesin, the entire visible region (400 to 700 nm) is obtained. ) Can provide an antireflection film having constant and excellent antireflection performance and excellent antistatic performance. Furthermore, by providing an overcoat layer with a thickness that does not affect the antireflection performance at all, the weakness of the film, that is, abrasion resistance and scratch resistance, is greatly improved. Therefore, it is possible to provide an antireflection film that can sufficiently withstand the use of a CRT display full surface panel or the like that does not take off.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing an example of an antireflection film of the present invention.
FIG. 2 is a cross-sectional view showing another example of the antireflection film of the present invention.
[Explanation of symbols]
1 Translucent plastic substrate
2, 2a, 2b High refractive index layer
3 Antireflection layer
4 Coat layer

Claims (10)

  Translucent plastic substrate, high refractive index layer having antistatic performance mainly composed of metal alkoxide and colloidal metal oxide and / or metal halide coated on the substrate, and on high refractive index layer An amorphous fluororesin antireflection layer coated with a refractive index (nd) of 1.36 or less, and a fluorine-based material mainly composed of an organic polysiloxane coated on the antireflection film and having a surface activity An antireflective film excellent in wear resistance, scratch resistance, adhesion and translucency, comprising a coating layer containing   Amorphous fluororesin is a copolymer of cyclic ether and perfluoro-2,2-dimethyl-1,3-dioxole, a copolymer of tetrafluoroethylene and cyclic perfluoroether, or a ring of perfluorovinyl allyl ether The antireflection film according to claim 1, which is a fluorinated copolymer.   A metal alkoxide having a high refractive index layer having a high refractive index such as silane alkoxide, aluminum alkoxide, titanium alkoxide, zirconium alkoxide, and colloidal metal oxide and / or metal chloride such as silica sol, alumina sol, titania sol, zirconia sol, The antireflection film according to claim 1 or 2, which is a high refractive index layer whose refractive index (nd) can be freely adjusted between 1.5 and 2.0 by a combination with a metal halide such as metal bromide.   4. The antireflection film according to claim 1, wherein the high refractive index layer contains an epoxy resin having a high refractive index and good adhesion to the plastic substrate.   The fluorine-based material having the surface-active ability of the coat layer is a fluorinated alkyl ester having a perfluoro group and a hydrophilic group in the side chain or a fluorinated aliphatic polymer ester having a perfluoro group and a lipophilic group in the side chain. The antireflection film according to claim 1, wherein the coating layer has a thickness of 200 nm or less, preferably 100 nm or less.   The organic polysiloxane of the coating layer is methylpolysiloxane or dimethylpolysiloxane having a silanol group, an alkoxy group, an acetyl group, a phenyl group, a polyether group, a perfluoroalkyl group or the like in the side chain. The antireflection film according to any one of the above. When the refractive index of the plastic substrate is n _S , the refractive index of the high refractive index layer is n ₁ , the thickness is d ₁ (unit is nm), the refractive index of the antireflection layer is n ₃ , and the thickness is d ₃ , Following formula (8) and (9)
n ₃ · n _S ² = n ₁ ² ·· (8)
And n ₁ · d ₁ = n ₃ · d ₃ = λ / 4 (9)
The antireflection film according to any one of claims 1 to 6, which is a three-layer designed as described above . Two high refractive index layers are provided, the refractive index n _S of the plastic substrate, the refractive index of the first high refractive index layer n ₁ , its thickness d ₁ (unit: nm), and the second high refractive index layer When the refractive index is n ₂ , the thickness is d ₂ , the refractive index of the antireflection layer is n ₃ , the thickness is d ₃ , and the refractive index of air is n ₀ , the following formulas (10) and (11)
n ₁ · n ₃ = n ₂ · (n ₀ · n _S ) ^1/2 ·· (10)
And n ₁ · d ₁ = n ₂ · d ₂ = n ₃ · d ₃ = λ / 4 (11)
The antireflection film according to any one of claims 1 to 6, wherein a high refractive index layer and an antireflection layer are provided so that is substantially satisfied. Two high refractive index layers are provided, the refractive index n _S of the plastic substrate, the refractive index of the first high refractive index layer n ₁ , its thickness d ₁ (unit: nm), and the second high refractive index layer When the refractive index is n ₂ , the thickness is d ₂ , the refractive index of the antireflection layer is n ₃ , the thickness is d ₃ , and the refractive index of air is n ₀ , the following formulas (12) and (13)
n ₃ ² · n _S = n ₀ · n ₁ ² ·· (12)
And _{n 1 · d 1 = n 2} · d 2/2 = n 3 · d 3 = λ / 4 ·· (13)
The antireflection film according to any one of claims 1 to 6, wherein the first and second high-refractive-index layers and the antireflection layer are provided so that is substantially satisfied. Two high refractive index layers are provided, the refractive index n _S of the plastic substrate, the refractive index of the first high refractive index layer n ₁ , its thickness d ₁ (unit: nm), and the second high refractive index layer When the refractive index is n ₂ , the thickness is d ₂ , the refractive index of the antireflection layer is n ₃ , the thickness is d ₃ , and the refractive index of air is n ₀ , the following formulas (14) and (15)
n ₃ ² · n _S = n ₀ · n ₁ ² ·· (14)
And _{n 1 · d 1/3 =} n 2 · d 2/2 = n 3 · d 3 = λ / 4 ·· (15)
The antireflection film according to any one of claims 1 to 6, wherein the first and second high-refractive-index layers and the antireflection layer are provided so that is substantially satisfied.

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