JP2004126532A - Optical member - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は、耐久性に優れた撥水性薄膜を有する光学部材及び光学部材の製造方法に関する。
【０００２】
【従来の技術】
レンズ等の光学部材上に施された反射防止膜は、一般にＺｒＯ２，ＳｉＯ２などの無機酸化物により形成されている。そのため、汗、指紋などによる汚れが付着しやすく、かつ、これらの汚れを除去することが困難であった。こうした問題を解決するために、反射防止膜上に撥水膜を施すことはよく知られている。
かかる撥水膜において、近年、撥水性が時間とともに、できるだけ低下しない性能が求められている。その性能を得る方法として、例えば特許文献１には、真空下、有機ケイ素化合物を加熱蒸着させて反射防止膜上に撥水膜を形成する方法が開示されている。
ところで、撥水膜を反射防止膜上に施した光学部材が汚れた場合、布等で撥水膜上の汚れを取り去る。布等で汚れを取り去るとき、撥水膜上の摩擦係数の関係で、布が引っかかるように感じる場合があった。そのため、強く拭きすぎてレンズに傷が生じる可能性があった。
【特許文献１】特開平５−２１５９０５号公報
【０００３】
【発明が解決しようとする課題】
本発明は上記課題を解決するためになされたもので、その目的は、布等で撥水膜上の汚れを取り去るとき、スム−ズに撥水膜上を拭くことができる光学部材を提供することにある。また本発明の目的はこれらの要求される有利な効果を示す光学部材を製造する方法を提供することにある。
【０００４】
【課題を解決するための手段】
上述した課題は、以下の手段により解決された。その手段は、光学基板と、該光学基板上に施された多層反射防止膜と、該多層反射防止膜の最外層に施された撥水層とを有する光学部材であって、前記多層反射防止膜の最外層が二酸化ケイ素を主成分とする層であり、前記撥水層は、フッ素置換アルキル基含有有機ケイ素化合物と、ケイ素非含有のパ−フルオロポリエ−テルとの２成分を主成分とする原料より構成される第１層と、該第１層上に接して施され、ケイ素非含有のパ−フルオロポリエ−テルを主成分とする原料より構成される第２層からなる光学部材である。
また光学基板上に施された多層反射防止膜の二酸化ケイ素を主成分とする最外層にフッ素置換アルキル基含有有機ケイ素化合物とケイ素非含有のパ−フルオロポリエ−テルとの２成分を主成分とする原料より構成される第１層を設ける工程と、該第１層の表面にケイ素非含有のパ−フルオロポリエ−テルを主成分とする原料より構成される第２層を設ける工程を有する光学部材の製造方法である。
【０００５】
【発明の実施の形態】
本発明の構成上の特徴は、特定組成からなる２層構造の撥水膜を反射防止膜の最外層に施したことにある。第１層は、反射防止膜の最外層上に、フッ素置換アルキル基含有有機ケイ素化合物と、ケイ素非含有のパ−フルオロポリエ−テルとの２成分を主成分とする原料より構成される層である。第２層は第１層上に接して施されるケイ素非含有のパ−フルオロポリエ−テルを主成分とする層である。ここで主成分とは各層における各化合物の含有量が５０質量％以上であることを意味し、特に好ましい含有量は７０質量％以上である。
【０００６】
従来、一般的に反射防止膜の最外層は、二酸化ケイ素からなる層が用いられる。これに対し、フッ素置換アルキル基含有有機ケイ素化合物を原料とする層は、反射防止膜の最外層で一般的に用いられる二酸化ケイ素からなる層と良好な密着性を有し、良好な撥水性及び耐擦傷性を有する。またケイ素非含有のパ−フルオロポリエ−テルを主成分とする層は、撥水効果及び布で擦った場合における滑り性は極めて良好であるが、反射防止膜の最外層で一般的に用いられる二酸化ケイ素層及びフッ素置換アルキル基含有有機ケイ素化合物からなる層との密着性が不十分であり、布で拭くとケイ素非含有のパ−フルオロポリエ−テルを主成分とする層が容易に剥離する可能性がある。
【０００７】
本発明者らは、ケイ素非含有のパ−フルオロポリエ−テルを主成分とする層の利点である表面の摩擦を低減させる特性、即ち、滑り性を向上させて、撥水性を維持しつつ、さらに、反射防止膜との密着性及び耐擦傷性を向上させることを目的として鋭意検討を行った。
その結果、撥水膜を２層構造とし、反射防止膜の最外層に接する第１層を、フッ素置換アルキル基含有有機ケイ素化合物と、ケイ素非含有のパ−フルオロポリエ−テルとの２成分を主成分とする原料より構成される層として、撥水性及び反射防止膜との密着性を良好にする。そして、前記第１層で含有されているケイ素非含有のパ−フルオロポリエ−テルと、第２層で構成されるケイ素非含有のパ−フルオロポリエ−テルとにより撥水膜の第１層と第２層との密着性を良好にすることができることを見出した。
【０００８】
上記フッ素置換アルキル基含有有機ケイ素化合物としては、特に限定されず、その例として以下の一般式（Ｉ）で表せる化合物を挙げることができる。
【化２】
（式中、Ｒｆは炭素数１〜１６の直鎖状のパーフルオロアルキル基、Ｘは水素または炭素数１〜５の低級アルキル基、Ｒ１は加水分解可能な基、ｍは１〜５０の整数、ｎは０〜２の整数、ｐは１〜１０の整数）
上記Ｒ１で示される加水分解可能な基としてはアミノ基、アルコキシ基、特にアルキル部が炭素数１〜２であるアルコキシ基、塩素原子等が挙げられる。
【０００９】
また前記フッ素置換アルキル基含有有機ケイ素化合物の例として、下記単位式（ＩＩ）：
ＣｑＦ２ｑ＋１ＣＨ２ＣＨ２Ｓｉ２（ＮＨ）３ ・・・（ＩＩ）
（ただし、ｑは１以上の整数である）で表される化合物を挙げることができる。
具体的には、ｎ−ＣＦ３ＣＨ２ＣＨ２Ｓｉ（ＮＨ２）３；ｎ−トリフロロ（１，１，２，２−テトラヒドロ）プロピルシラザン、ｎ−Ｃ３Ｆ７ＣＨ２ＣＨ２Ｓｉ（ＮＨ２）３；ｎ−ヘプタフロロ（１，１，２，２−テトラヒドロ）ペンチルシラザン、ｎ−Ｃ４Ｆ９ＣＨ２ＣＨ２Ｓｉ（ＮＨ２）３；ｎ−ノナフロロ（１，１，２，２−テトラヒドロ）ヘキシルシラザン、ｎ−Ｃ６Ｆ１３ＣＨ２ＣＨ２Ｓｉ（ＮＨ２）３；ｎ−トリデオフロロ（１，１，２，２−テトラヒドロ）オクチルシラザン、ｎ−Ｃ８Ｆ１７ＣＨ２ＣＨ２Ｓｉ（ＮＨ２）３；ｎ−ヘプタデカフロロ（１，１，２，２−テトラヒドロ）デシルシラザン等を例示することができる。
【００１０】
さらに、特開昭５８−１６７４４８号公報、特開昭６０−２２１４７０号公報、特開昭６１−１００４３号公報に開示されているフッ素含有有機ケイ素は、本願のフッ素置換アルキル基含有有機ケイ素化合物に該当する。
尚、市販されている前記フッ素置換アルキル基含有有機ケイ素化合物としては、ＫＰ−８０１（商品名、信越化学工業（株）製）、オプツ−ルＤＳＸ（ダイキン工業（株）製）、フッ素系コ−ティング剤Ｘ−７１−１３０（商品名、信越化学工業（株）製）などを挙げることができる。
【００１１】
ケイ素非含有のパ−フルオロポリエ−テルは、ケイ素を含有しない以下の構造式（ＩＩＩ）
−（ＲＯ）− ・・・（ＩＩＩ）
（式中、Ｒは炭素数１〜３のパーフルオロアルキレン基である）
で表される単位からなるものが好ましく用いられ、平均分子量が１０００〜１００００、特に２０００〜１００００のものが好ましい。Ｒは炭素数１〜３のパーフルオロアルキレン基であり、具体的にはＣＦ２，ＣＦ２−ＣＦ２，ＣＦ２ＣＦ２ＣＦ２，ＣＦ（ＣＦ３）ＣＦ２等の基が挙げられる。これらのパ−フルオロポリエ−テル（以下「ＰＦＰＥ」ということがある）は常温で液状であり、いわゆるフッ素オイルと称されるものである。
本発明に使用可能なＰＦＰＥとしては、たとえばダイキン工業（株）製の商品名デムナムシリーズ、ＮＯＫクリューバー社製の商品名バリエルタシリーズ、旭硝子（株）製の商品名フォンブリンシリーズ、デュポン社製の商品名ＫＲＹＴＯＸシリーズ、ダウコ−ニング社の商品名モリコ−トＨＦ−３０オイルなどが挙げられる。
【００１２】
本発明では上記フッ素置換アルキル基含有有機ケイ素化合物とケイ素非含有のパ−フルオロポリエ−テルとの２成分を混合し、これを主成分とする原料を用いて撥水層の第１層を設けることを特徴とするが、その混合割合は重量換算にして、フッ素置換アルキル基含有有機ケイ素化合物１に対して、ケイ素非含有のパ−フルオロポリエ−テルが０．０１〜１００の範囲内であることが好ましい。
なお、フッ素置換アルキル基含有有機ケイ素化合物と、ケイ素非含有のパ−フルオロポリエ−テルとの混合物としては、前述したダイキン工業（株）製の商品名オプツ−ルＤＳＸが市販されている。
【００１３】
前記フッ素を含有した撥水層を形成する薄膜の膜厚は、基本的にフッ素置換アルキル基含有有機ケイ素化合物及びケイ素非含有のパ−フルオロポリエ−テル量に依存して変化する。従って、例えば、該薄膜をオングストロ−ムオ−ダ−で制御する際には、フッ素置換アルキル基含有有機ケイ素化合物及びケイ素非含有のパ−フルオロポリエ−テルを、溶媒で希釈した溶液を用いることが好ましい。かかる溶媒としては、ｍ−キシレンヘキサフロライド、パーフルオロヘキサン、ハイドロフロロエーテルなどのフッ素系溶媒が挙げられる。
また、溶液中のフッ素置換アルキル基含有有機ケイ素化合物の濃度は、所望の目的を果たせれば特に制限はなく、フッ素置換アルキル基含有有機ケイ素化合物の種類及び所望する薄膜の膜厚などを考慮して適宜決めることができる。撥水膜の第１層の形成方法は特に限定されず、例えば、蒸着加熱、漬浸塗布法により撥水層が形成される。
【００１４】
以下、蒸着加熱法で第１層を形成する場合について説明する。
上記フッ素置換アルキル基含有有機ケイ素化合物及びケイ素非含有のパ−フルオロポリエ−テル溶液はそのまま容器に入れて加熱しても良いが、均一な蒸着膜を多く得られるとの観点から、多孔性材料に含浸させることがより好ましく、多孔性材料としては、銅やステンレスなどの熱伝導性の高い金属粉末を焼結した焼結フィルターを用いることが好ましい。
又、多孔性材料は、適度な蒸着速度を得るという観点からそのメッシュを４０〜２００ミクロン、好ましくは、８０〜１２０ミクロンとすることが適当である。
【００１５】
フッ素置換アルキル基含有有機ケイ素化合物及びケイ素非含有のパ−フルオロポリエ−テルは、加熱蒸着によって基材上に蒸着される場合には、減圧下、加熱して蒸着することが好ましい。その場合の真空蒸着装置内の真空度としては、特に限定はないが、均質な撥水膜を得るとの観点から、好ましくは、８．０×１０−１Ｐａ〜１．０×１０−６Ｐａ、特に好ましくは、５．０×１０−１Ｐａ〜６．０×１０−４Ｐａである。
フッ素置換アルキル基含有有機ケイ素化合物及びケイ素非含有のパ−フルオロポリエ−テルを加熱する際の具体的温度は、有機ケイ素化合物の種類、蒸着する真空条件により異なるが、所望の真空度における該有機ケイ素化合物の蒸着開始温度から該有機ケイ素化合物の分解温度を超えない範囲で行うことが好ましい。
【００１６】
蒸着速度は、上記温度範囲に保つことを条件に、前記有機ケイ素化合物の加熱開始から蒸着を完結させるまでの時間を９０秒以内とすることが好ましく、さらには５０秒以内、４０秒以内、３０秒以内、２０秒以内、１０秒以内と短くするほど好ましく、特に、５秒以内とすることが好ましい。上記加熱温度範囲で、且つ短時間で蒸着を完結させること、即ち、前記有機ケイ素化合物に短時間で高エネルギ−を与えることにより、耐久性に優れた撥水膜を有する光学部材を提供することができる。
また、本発明における撥水膜の第１層のように、蒸着開始温度が多少異なる２成分の撥水剤を用いても、短時間で、撥水剤の分解温度を超えない高エネルギ−を与えて蒸着させることにより、ほぼ同時に蒸着でき、均一な膜を得ることができる。
【００１７】
前記蒸着速度を達成する方法としては、前記有機ケイ素化合物に電子ビ−ムを照射する方法が好ましく挙げられる。電子ビ−ムを発生する方法は、従来、蒸着装置で用いられている電子銃を用いることができる。電子銃を用いれば、前記有機ケイ素化合物全体に、均一のエネルギ−を照射することができ均一な撥水膜を施しやすくなる。
電子銃のパワーについては、使用物質、蒸着装置、真空度、照射面積によって異なるが、好ましい条件は、加速電圧が６ｋＶ前後で、印加電流５〜８０ｍＡ程度である。
かかる方法で光学部材を製造すると、耐久性に優れた撥水層を得ることができる。
【００１８】
次に、本発明では前記第１層上に接して、ケイ素非含有のパ−フルオロポリエ−テルを主成分とする原料より構成される第２層を有することを特徴とする。第２層の形成に使用されるＰＦＰＥとしては、第１層に使用されるものと同様のものを使用することができ、第１層と第２層で使用されるＰＦＰＥはそれぞれ同一でも異なってもよい。但し、第１層と第２層の接着性及び製造の簡便さを考慮すると、第１層に使用するＰＦＰＥと第２層に使用するＰＦＰＥとが同一の化合物であることがより好ましい。
第２層の形成方法は、特に限定されず、前記第１層と同様な方法で行うことができる。またＰＦＰＥを室温にてそのまま塗布することも可能である。このように、ＰＦＰＥを室温にてそのまま塗布して第２層を形成しても、第１層に含まれているケイ素非含有のパ−フルオロポリエ−テルとの関係で密着性が良好となり、ケイ素非含有のパ−フルオロポリエ−テルからなる層の特性である滑り性が良くなるため、耐久性のある撥水性能を得ることができる。
【００１９】
本発明に用いる光学基板としては、メチルメタクリレート単独重合体、メチルメタクリレートと１種以上の他のモノマーとをモノマー成分とする共重合体、ジエチレングリコールビスアリルカーボネート単独重合体、ジエチレングリコールビスアリルカーボネートと１種以上の他のモノマーとをモノマー成分とする共重合体、イオウ含有共重合体、ハロゲン含有共重合体、ポリカーボネート、ポリスチレン、ポリ塩化ビニル、不飽和ポリエステル、ポリエチレンテレフタレート、ポリウレタンなどのプラスチック製光学基板、あるいは無機ガラス製光学基板などが挙げられる。尚、上記基板は基板上にハードコート層を有するものであってもよい。ハードコート層としては、有機ケイ素化合物、アクリル化合物等を含んだ硬化膜を例示できる。
【００２０】
また、反射防止膜（蒸着膜）とは、例えばレンズ等の光学基板表面の反射を減少させるために設けられた ＺｒＯ２、ＳｉＯ２、ＴｉＯ２、Ｔａ２Ｏ５ 、Ｙ２Ｏ３、ＭｇＦ２、Ａｌ２Ｏ３などから形成される単層または多層膜（但し、最外層にＳｉＯ２膜を有する）、またＣｒＯ２などの着色膜（但し、最外層にＳｉＯ２膜を有する）をいう。本発明においては、反射防止膜の最外層に二酸化ケイ素を主成分とする層が用いられることを必須とする。
【００２１】
【実施例】
以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
１．反射防止膜付プラスチックレンズの作成
光学基板として、ジエチレングリコ−ルビスアリルカ−ボネ−ト重合体系レンズ（ＨＯＹＡ（株）製Ｈｉ−Ｌｕｘ（商品名）、屈折率１．４９９、度数０．００）を用い、かかるプラスチックレンズ基材上に、特開昭６３−１０６４０号公報に開示されている硬化膜を施した。具体的には、ＳｉＯ２濃度４０％のコロイダルシリカ（日産化学（株）製スノーテックス−４０（商品名）、水分散シリカ）２４０質量部に、０．５Ｎ塩酸２．０質量部、酢酸２０質量部を加えた溶液を、３５℃にて攪拌しながら、γ−グリシドキシプロピルトリメトキシシラン（３官能有機ケイ素化合物）９５質量部を滴下し、室温にて８時間攪拌し、室温にて１６時間放置した。この加水分解溶液に、メチルセロソルブ８０質量部、イソプロピルアルコール１２０質量部、ブチルアルコール４０質量部、アルミニウムアセチルアセトン１６質量部、シリコーン系界面活性剤（日本ユニカ（株）製ＮＵＣ ＳＩＬＷＥＴ Ｙ−７００６（商品名））０．２質量部、紫外線吸収剤（チバガイギー製Ｔｉｎｕｖｉｎ Ｐ（商品名））０．１質量部を加えて、８時間攪拌後、室温にて２４時間熟成させコーティング組成物を得た。該組成物を、引き上げ速度１５ｃｍ／ｍｉｎで浸漬法により塗布、室温にて１５分放置後、１２０℃で２時間加熱硬化することによって硬化膜を施した。
次に、前記硬化膜上に真空蒸着法（真空度２．６７×１０−３Ｐａ（２×１０−５Ｔｏｒｒ） ）により、二酸化ケイ素からなる下地層〔屈折率１．４６、光学膜厚０．５λ（λに関する設計波長を５５０ｎｍとした。）〕を形成し、該下地層の上に、酸素イオンビームを照射するイオンビームアシスト法によって二酸化チタンからなる層を（光学膜厚０．０６λ）、次いで真空蒸着法により二酸化ケイ素からなる層を（光学膜厚０．１２λ）、さらにイオンビームアシスト法により二酸化チタンからなる層（光学膜厚０．０６λ）を施し、３層等価膜である第１層〔屈折率１．７０、光学膜厚０．２４λ〕を形成した。この第１層の上に、イオンビームアシスト法により二酸化チタンからなる第２層（屈折率２．４０、光学膜厚０．５λ）を形成し、該第２層の上に、真空蒸着法（真空度２．６７×１０−３Ｐａ（２×１０−５ Ｔｏｒｒ））により二酸化ケイ素からなる第３層〔屈折率１．４６、光学膜厚０．２５λ〕を形成して、反射防止膜付きプラスチックレンズを得た。このレンズの視感反射率は０．４％であった。
【００２２】
２．使用撥水剤
（１）第１層で用いる撥水処理剤１
オプツ−ルＤＳＸ（製品名、ダイキン工業（株）、フッ素置換アルキル基含有有機ケイ素化合物と、ケイ素非含有のパ−フルオロポリエ−テルとを主成分とする混合物）を用いた。
（２）第２層で用いる撥水処理剤２
デムナムシリ−ズ４種（Ｓ−２０，Ｓ−６５，Ｓ−１００，Ｓ−２００）（製品名、ダイキン工業（株）、ケイ素非含有のパ−フルオロポリエ−テル）を用いた。
【００２３】
３．物性評価
本実施例で得られたプラスチックレンズは以下に示す評価方法により諸物性を評価した。
（１）外観
目視にて干渉色の色ムラ及び干渉色変化があるかどうかを調べ、眼鏡レンズとして使用できる外観かどうか評価した。
（２）耐久性
セーム皮を２５℃の水に５分間浸漬し、その後空気中に取出した。このセーム皮を空気中（２５℃、湿度５０〜６０％）で１分間放置した後、５００ｇの荷重をかけて撥水膜を有するプラスチックレンズ表面を５０００回及び１００００回擦り（空気中、２５℃、湿度５０〜６０％）、その後以下に示す水に対する静止接触角を測定した。５０００回擦るのに６５分、１００００回擦るのに１３０分を要した。なお、セ−ム皮は、米国連邦規格（Ｆｅｄｅｒａｌ Ｓｐｅｃｉｆｉｃａｔｉｏｎｓ ａｎｄ Ｓｔａｎｄａｒｄｓ）ＫＫ−Ｃ−３００Ｃのグレ−ドＢを用いた。またセーム皮は久保田鹿皮（株）製のものを用い、耐久性試験は図１に示す装置を用いて行った。
水に対する静止接触角；接触角計（協和界面科学（株）製品、ＣＡ−Ｄ型）を使用し、２５℃で直径２ｍｍの水滴を針先に作り、これをレンズの凸面の最上部に触れさせて、液滴を作った。この時に生ずる液滴と面との角度を測定し静止接触角とした。静止接触角θは液滴の底の部分の半径ｒ（すなわち液滴がレンズ表面と接触する部分の半径）と液滴の高さｈから次の式で計算される。
θ＝２×ｔａｎ−１（ｈ／ｒ）
尚、測定は水の蒸発による誤差を最小限にするため、液滴をレンズ上に作ったのち１０秒以内に行った。
（３）視感反射率（片面）
日立製作所製Ｕ−３４１０型自記分光高度型を用い、撥水膜形成前後の視感反射率を測定した。
（４）滑り性
新東科学（株）製の連続加重式表面性測定機ＴＹＰＥ：２２Ｈを使用して開始前及び終了後における摩擦係数、摩擦力（ｇｆ）を測定した。測定は、前記（２）に記載した耐久性テストを行う前、耐久性テストを５０００回行った後、耐久性テストを１００００回行った後にそれぞれ測定した。
【００２４】
実施例１
撥水処理剤１（オプツ−ルＤＳＸ：商品名（ダイキン工業（株）製））を０．１５ｍｌしみ込ませたステンレス製焼結フィルタ−（メッシュ８０〜１００ミクロン、１８φ×３ｍｍ）を真空蒸着装置内にセットし、以下の条件で電子銃を用いて該焼結フィルタ−全体を加熱して、上記レンズ枠形状に切削された反射防止膜付プラスチックレンズに撥水膜の第１層を形成した。
▲１▼真空度：３．１×１０−４〜８×１０−４Ｐａ（２．３×１０−６ 〜 ６．０×１０−６ Ｔｏｒｒ）
▲２▼電子銃の条件：加速電圧：６ｋＶ、印加電流：４０ｍＡ、照射面積：３．５×３．５ｃｍ平方、蒸着時間：１０秒
なお、蒸着時間は、加熱開始時間から蒸着完了時間を意味する。
その後、紙に適量しみ込ませたケイ素非含有のパ−フルオロポリエ−テルとして「デムナムＳ−２０」（ダイキン工業（株）製）を、前記撥水膜の第１層上に塗布した。評価結果を第１表に示す。滑り性、及び耐久性が良好で、さらに撥水性も良好なものであった。
【００２５】
実施例２〜４
実施例１で使用した撥水剤に代えて第１表に示す撥水剤を用いたこと以外は実施例１と同様にして撥水膜を形成した。評価結果を第１表に示す。実施例１同様、撥水性、滑り性及び耐久性が良好なものであった。
【００２６】
参考例
撥水膜の第２層を施さなかった以外は、すべて実施例１と同様に行った。その結果を第１表に示す。実施例１〜４に比べ、滑り性が劣るものであった。
【００２７】
【表１】
注）Ａ；オプツールＤＳＸ（商品名（ダイキン工業（株）製））
ａ；デムナムＳ−２０（ダイキン工業（株）製）（平均分子量２７００）
ｂ；デムナムＳ−６５（ダイキン工業（株）製）（平均分子量４５００）
ｃ；デムナムＳ−１００（ダイキン工業（株）製）（平均分子量５６００）
ｄ；デムナムＳ−２００（ダイキン工業（株）製）（平均分子量８４００）
【００２９】
【発明の効果】
本発明によって、滑り性、撥水性が良好で、布等で撥水膜上の汚れを取り去るとき、スム−ズに撥水膜上を拭くことができる光学部材を得ることができた。
【図面の簡単な説明】
【図１】本発明における耐久性試験を行う装置を示す概略図である。
【符号の説明】
１：レンズ
２：セーム皮
３：六面体板[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an optical member having a water-repellent thin film having excellent durability and a method for manufacturing the optical member.
[0002]
[Prior art]
The antireflection film provided on an optical member such as a lens is generally formed of an inorganic oxide such as ZrO 2 or SiO 2 . Therefore, dirt due to sweat, fingerprints, and the like easily adheres, and it is difficult to remove these dirt. It is well known that a water-repellent film is formed on an antireflection film in order to solve such a problem.
In recent years, such a water-repellent film has been required to have a performance in which the water repellency does not decrease as much as possible over time. As a method for obtaining the performance, for example,
By the way, when the optical member having the water-repellent film formed on the antireflection film becomes dirty, the dirt on the water-repellent film is removed with a cloth or the like. When removing dirt with a cloth or the like, there was a case where the cloth was felt to be caught due to the friction coefficient on the water-repellent film. For this reason, there is a possibility that the lens will be damaged due to excessive wiping.
[Patent Document 1] JP-A-5-215905
[Problems to be solved by the invention]
SUMMARY OF THE INVENTION The present invention has been made to solve the above-described problems, and an object of the present invention is to provide an optical member that can smoothly wipe the surface of a water-repellent film when removing dirt on the water-repellent film with a cloth or the like. It is in. Another object of the present invention is to provide a method for manufacturing an optical member exhibiting these required advantageous effects.
[0004]
[Means for Solving the Problems]
The above-mentioned problem has been solved by the following means. The means is an optical member having an optical substrate, a multilayer antireflection film provided on the optical substrate, and a water-repellent layer provided on the outermost layer of the multilayer antireflection film, wherein the multilayer antireflection film is provided. The outermost layer of the film is a layer containing silicon dioxide as a main component, and the water-repellent layer mainly contains two components of a fluorine-substituted alkyl group-containing organosilicon compound and silicon-free perfluoropolyether. An optical member comprising a first layer composed of a raw material to be formed and a second layer composed of a raw material containing a silicon-free perfluoropolyether as a main component and applied on the first layer. is there.
The outermost layer containing silicon dioxide as a main component of the multilayer antireflection film formed on the optical substrate contains two components of a fluorine-substituted alkyl group-containing organosilicon compound and a silicon-free perfluoropolyether as a main component. Providing a first layer composed of a raw material to be formed and providing a second layer composed of a raw material containing silicon-free perfluoropolyether as a main component on the surface of the first layer. It is a manufacturing method of a member.
[0005]
BEST MODE FOR CARRYING OUT THE INVENTION
A structural feature of the present invention resides in that a water-repellent film having a two-layer structure having a specific composition is applied to the outermost layer of the antireflection film. The first layer is a layer formed on the outermost layer of the antireflection film from a raw material mainly composed of two components of a fluorine-substituted alkyl group-containing organosilicon compound and a silicon-free perfluoropolyether. is there. The second layer is a layer containing silicon-free perfluoropolyether as a main component and applied on the first layer. Here, the main component means that the content of each compound in each layer is 50% by mass or more, and a particularly preferred content is 70% by mass or more.
[0006]
Conventionally, a layer made of silicon dioxide is generally used as the outermost layer of the antireflection film. In contrast, a layer made of a fluorine-substituted alkyl group-containing organosilicon compound has a good adhesion to a layer made of silicon dioxide generally used as the outermost layer of the antireflection film, and has good water repellency and Has scratch resistance. A layer containing silicon-free perfluoropolyether as a main component has a very good water-repellent effect and a good sliding property when rubbed with a cloth, but is generally used as the outermost layer of an antireflection film. Adhesion with the silicon dioxide layer and the layer comprising the fluorine-substituted alkyl group-containing organosilicon compound is insufficient, and the layer mainly containing silicon-free perfluoropolyether is easily peeled off when wiped with a cloth. there is a possibility.
[0007]
The present inventors have found that a layer containing silicon-free perfluoropolyether as a main component has the property of reducing surface friction, which is an advantage of a layer containing silicon-free perfluoropolyether. Further, intensive studies were conducted for the purpose of improving the adhesion to the antireflection film and the scratch resistance.
As a result, the water-repellent film has a two-layer structure, and the first layer in contact with the outermost layer of the anti-reflection film is formed of two components of a fluorine-substituted alkyl group-containing organosilicon compound and a silicon-free perfluoropolyether. As a layer composed of a raw material as a main component, water repellency and adhesion to an antireflection film are improved. Then, the first layer of the water-repellent film is formed by the silicon-free perfluoropolyether contained in the first layer and the silicon-free perfluoropolyether constituted by the second layer. It has been found that the adhesion to the second layer can be improved.
[0008]
The fluorine-substituted alkyl group-containing organosilicon compound is not particularly limited, and examples thereof include compounds represented by the following general formula (I).
Embedded image
(Wherein, Rf is a linear perfluoroalkyl group having 1 to 16 carbon atoms, X is hydrogen or a lower alkyl group having 1 to 5 carbon atoms, R1 is a hydrolyzable group, and m is an integer of 1 to 50. , N is an integer of 0 to 2, p is an integer of 1 to 10)
Examples of the hydrolyzable group represented by R1 include an amino group, an alkoxy group, particularly an alkoxy group having an alkyl portion having 1 to 2 carbon atoms, a chlorine atom and the like.
[0009]
Examples of the fluorine-substituted alkyl group-containing organosilicon compound include the following unit formula (II):
C q F 2q + 1 CH 2
(Where q is an integer of 1 or more).
Specifically, n-CF 3 CH 2 CH 2 Si (NH 2) 3; n- trifluoro (1,1,2,2-tetrahydro) propyl disilazane, n-C 3 F 7 CH 2 CH 2 Si (NH 2 ) 3 ; n-heptafluoro (1,1,2,2-tetrahydro) pentylsilazane, nC 4 F 9 CH 2 CH 2 Si (NH 2 ) 3 ; n-nonafluoro (1,1,2,2- tetrahydro)
[0010]
Further, the fluorine-containing organosilicon disclosed in JP-A-58-167448, JP-A-60-221470 and JP-A-61-10043 is different from the fluorine-substituted alkyl group-containing organosilicon compound of the present application. Applicable.
Examples of commercially available organosilicon compounds containing a fluorine-substituted alkyl group include KP-801 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), Optole DSX (manufactured by Daikin Industries, Ltd.), -Ting agent X-71-130 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.
[0011]
The silicon-free perfluoropolyether has the following structural formula (III) containing no silicon:
-(RO)-... (III)
(Wherein, R is a perfluoroalkylene group having 1 to 3 carbon atoms)
Those having the unit represented by are preferably used, and those having an average molecular weight of 1,000 to 10,000, particularly preferably 2,000 to 10,000, are preferred. R is a perfluoroalkylene group having 1 to 3 carbon atoms, and specific examples thereof include groups such as CF 2 , CF 2 —CF 2 , CF 2 CF 2 CF 2 , and CF (CF 3 ) CF 2 . These perfluoropolyethers (hereinafter sometimes referred to as “PFPE”) are liquid at ordinary temperature and are so-called fluorine oils.
Examples of the PFPE that can be used in the present invention include the Demnum series (trade name, manufactured by Daikin Industries, Ltd.), the Varierta series (trade name, manufactured by NOK Kluber), the Fomblin series (trade name, manufactured by Asahi Glass Co., Ltd.), and DuPont (Dupont). KRYTOX series manufactured by Dow Corning Co., Ltd., and Moricoat HF-30 oil manufactured by Dow Corning.
[0012]
In the present invention, the first component of the water-repellent layer is provided by mixing two components of the above-mentioned fluorine-substituted alkyl group-containing organosilicon compound and silicon-free perfluoropolyether, and using a raw material containing this as a main component. It is characterized in that, in terms of the mixing ratio, in terms of weight, the silicon-free perfluoropolyether is in the range of 0.01 to 100 with respect to the fluorine-substituted alkyl group-containing
As a mixture of a fluorine-substituted alkyl group-containing organosilicon compound and a silicon-free perfluoropolyether, the above-mentioned trade name Optole DSX manufactured by Daikin Industries, Ltd. is commercially available.
[0013]
The thickness of the thin film forming the fluorine-containing water-repellent layer basically changes depending on the amounts of the fluorine-substituted alkyl group-containing organosilicon compound and the silicon-free perfluoropolyether. Therefore, for example, when controlling the thin film by angstrom order, a solution obtained by diluting a fluorine-substituted alkyl group-containing organosilicon compound and a silicon-free perfluoropolyether with a solvent is used. preferable. Examples of such a solvent include fluorinated solvents such as m-xylene hexafluoride, perfluorohexane, and hydrofluoroether.
Further, the concentration of the fluorine-substituted alkyl group-containing organosilicon compound in the solution is not particularly limited as long as the desired purpose can be achieved, and the type of the fluorine-substituted alkyl group-containing organosilicon compound and the desired thin film thickness are taken into consideration. Can be determined appropriately. The method for forming the first layer of the water-repellent film is not particularly limited, and the water-repellent layer is formed by, for example, evaporation heating and immersion coating.
[0014]
Hereinafter, the case where the first layer is formed by the evaporation heating method will be described.
The above-mentioned fluorine-substituted alkyl group-containing organosilicon compound and the silicon-free perfluoropolyether solution may be directly placed in a container and heated, but from the viewpoint that a large number of uniform deposited films can be obtained, a porous material is used. It is more preferable to use a sintered filter obtained by sintering a metal powder having high thermal conductivity such as copper or stainless steel as the porous material.
The mesh of the porous material is suitably from 40 to 200 microns, preferably from 80 to 120 microns, from the viewpoint of obtaining an appropriate deposition rate.
[0015]
When the fluorine-substituted alkyl group-containing organosilicon compound and the silicon-free perfluoropolyether are deposited on a substrate by heating and vapor deposition, it is preferable to heat and deposit under reduced pressure. In this case, the degree of vacuum in the vacuum evaporation apparatus is not particularly limited, but is preferably 8.0 × 10 −1 Pa to 1.0 × 10 −6 from the viewpoint of obtaining a uniform water-repellent film. Pa, particularly preferably 5.0 × 10 −1 Pa to 6.0 × 10 −4 Pa.
The specific temperature for heating the fluorine-substituted alkyl group-containing organosilicon compound and the silicon-free perfluoropolyether varies depending on the type of the organosilicon compound and the vacuum conditions for vapor deposition. It is preferable to perform the step within a range from the temperature at which the silicon compound is vapor-deposited to the temperature at which the decomposition temperature of the organic silicon compound is not exceeded.
[0016]
The deposition rate is preferably 90 seconds or less from the start of the heating of the organosilicon compound to the completion of the deposition, provided that the temperature is maintained in the above temperature range, and more preferably 50 seconds or less, 40 seconds or less, and 30 seconds or less. It is more preferable to shorten the time to within 20 seconds, within 10 seconds, and particularly within 5 seconds. To provide an optical member having a water-repellent film excellent in durability by completing vapor deposition in the above heating temperature range and in a short time, that is, by applying high energy to the organosilicon compound in a short time. Can be.
Even when a two-component water repellent having slightly different deposition start temperatures is used as in the first layer of the water repellent film of the present invention, high energy that does not exceed the decomposition temperature of the water repellent can be obtained in a short time. By applying and vapor-depositing, vapor deposition can be performed almost simultaneously, and a uniform film can be obtained.
[0017]
As a method of achieving the deposition rate, a method of irradiating the organic silicon compound with an electron beam is preferable. As a method of generating an electron beam, an electron gun conventionally used in a vapor deposition apparatus can be used. When an electron gun is used, uniform energy can be applied to the entire organosilicon compound, and a uniform water-repellent film can be easily formed.
The power of the electron gun varies depending on the substance to be used, the vapor deposition device, the degree of vacuum, and the irradiation area, but preferable conditions are an acceleration voltage of about 6 kV and an applied current of about 5 to 80 mA.
When an optical member is manufactured by such a method, a water-repellent layer having excellent durability can be obtained.
[0018]
Next, the present invention is characterized in that a second layer composed of a raw material containing silicon-free perfluoropolyether as a main component is provided in contact with the first layer. As the PFPE used for forming the second layer, the same PFPE used for the first layer can be used, and the PFPE used for the first layer and the PFPE used for the second layer are different even if they are the same. Is also good. However, in consideration of the adhesion between the first layer and the second layer and the simplicity of production, it is more preferable that the PFPE used for the first layer and the PFPE used for the second layer are the same compound.
The method for forming the second layer is not particularly limited, and the second layer can be formed in the same manner as the first layer. It is also possible to apply PFPE at room temperature as it is. Thus, even if PFPE is applied as it is at room temperature to form the second layer, the adhesion becomes good in relation to the silicon-free perfluoropolyether contained in the first layer, Since the layer made of perfluoropolyether containing no silicon has improved sliding properties, it is possible to obtain durable water repellency.
[0019]
Examples of the optical substrate used in the present invention include methyl methacrylate homopolymer, a copolymer containing methyl methacrylate and one or more other monomers as monomer components, diethylene glycol bisallyl carbonate homopolymer, and diethylene glycol bisallyl carbonate. Copolymers containing the above other monomers as monomer components, sulfur-containing copolymers, halogen-containing copolymers, polycarbonate, polystyrene, polyvinyl chloride, unsaturated polyester, polyethylene terephthalate, plastic optical substrates such as polyurethane, Alternatively, an inorganic glass optical substrate may be used. The substrate may have a hard coat layer on the substrate. As the hard coat layer, a cured film containing an organosilicon compound, an acrylic compound or the like can be exemplified.
[0020]
The antireflection film (evaporated film) is, for example, ZrO 2 , SiO 2 , TiO 2 , Ta 2 O 5 , Y 2 O 3 , and MgF 2 provided to reduce reflection on the surface of an optical substrate such as a lens. , Al 2 O 3, etc. means a single-layer or multilayer film (provided that the outermost layer has a SiO 2 film), and a colored film such as CrO 2 (provided that the outermost layer has a SiO 2 film). In the present invention, it is essential that a layer containing silicon dioxide as a main component is used as the outermost layer of the antireflection film.
[0021]
【Example】
Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.
1. Preparation of a Plastic Lens with an Antireflection Film A diethylene glycol bisallyl carbonate-based polymer lens (Hi-Lux (trade name, manufactured by HOYA Co., Ltd., refractive index: 1.499, frequency: 0.00)) was used as an optical substrate. On such a plastic lens substrate, a cured film disclosed in JP-A-63-10640 was applied. Specifically, 2.0 parts by mass of 0.5 N hydrochloric acid and 20 parts by mass of acetic acid were added to 240 parts by mass of colloidal silica having a SiO 2 concentration of 40% (Snowtex-40 (trade name, manufactured by Nissan Chemical Industries, Ltd., water-dispersed silica)). 95 parts by mass of γ-glycidoxypropyltrimethoxysilane (trifunctional organosilicon compound) was added dropwise while stirring the solution to which the parts by mass had been added at 35 ° C., and the mixture was stirred at room temperature for 8 hours and then at room temperature. It was left for 16 hours. 80 parts by mass of methyl cellosolve, 120 parts by mass of isopropyl alcohol, 40 parts by mass of butyl alcohol, 16 parts by mass of aluminum acetylacetone, and a silicone-based surfactant (NUC SILWET Y-7006 manufactured by Nippon Unica Co., Ltd.) )) 0.2 parts by mass and 0.1 parts by mass of an ultraviolet absorber (Tinuvin P (trade name) manufactured by Ciba Geigy) were added, and the mixture was stirred for 8 hours and then aged at room temperature for 24 hours to obtain a coating composition. The composition was applied by a dipping method at a pulling rate of 15 cm / min, left at room temperature for 15 minutes, and then cured by heating at 120 ° C. for 2 hours to form a cured film.
Next, an underlayer made of silicon dioxide [refractive index 1.46, optical film thickness 0] is formed on the cured film by a vacuum deposition method (degree of vacuum 2.67 × 10 −3 Pa (2 × 10 −5 Torr)). .5λ (design wavelength for λ was 550 nm)], and a layer made of titanium dioxide was formed on the underlayer by an ion beam assist method of irradiating an oxygen ion beam (optical thickness: 0.06λ). Then, a layer made of silicon dioxide (optical thickness: 0.12λ) is applied by a vacuum deposition method, and a layer made of titanium dioxide (optical thickness: 0.06λ) is further applied by an ion beam assist method to obtain a three-layer equivalent film. One layer [refractive index 1.70, optical film thickness 0.24λ] was formed. A second layer (refractive index: 2.40, optical film thickness: 0.5λ) made of titanium dioxide is formed on the first layer by an ion beam assist method, and a vacuum evaporation method ( A third layer (refractive index: 1.46, optical thickness: 0.25λ) made of silicon dioxide is formed at a degree of vacuum of 2.67 × 10 −3 Pa (2 × 10 −5 Torr), and an antireflection film is provided. A plastic lens was obtained. The luminous reflectance of this lens was 0.4%.
[0022]
2. Water repellent used (1)
Optole DSX (product name, Daikin Industries, Ltd., a mixture containing a fluorine-substituted alkyl group-containing organosilicon compound and a silicon-free perfluoropolyether as main components) was used.
(2)
Four types of Demnum series (S-20, S-65, S-100, S-200) (product name, Daikin Industries, Ltd., silicon-free perfluoropolyether) were used.
[0023]
3. Evaluation of Physical Properties The plastic lens obtained in this example was evaluated for various physical properties by the following evaluation methods.
(1) The appearance was visually examined to determine whether or not there was color unevenness of the interference color and a change in the interference color.
(2) Durability Chamois skin was immersed in water at 25 ° C. for 5 minutes, and then taken out into the air. After leaving the chamois in the air (25 ° C., humidity 50 to 60%) for 1 minute, the surface of the plastic lens having a water-repellent film was rubbed 5000 times and 10000 times by applying a load of 500 g (in air, 25 ° C. , Humidity of 50 to 60%), and then the static contact angle to water shown below was measured. It took 65 minutes to rub 5000 times and 130 minutes to rub 10,000 times. In addition, grade B of United States federal standards (Federal Specifications and Standards) KK-C-300C was used for the same. The chamois was made by Kubota Kaseki Co., Ltd., and the durability test was performed using the apparatus shown in FIG.
Static contact angle with water; Using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., type CA-D), make a water drop of 2 mm in diameter at the needle point at 25 ° C, and touch this with the top of the convex surface of the lens. Then, a droplet was formed. The angle between the droplet and the surface generated at this time was measured and defined as the static contact angle. The static contact angle θ is calculated from the radius r of the bottom portion of the droplet (that is, the radius of the portion where the droplet contacts the lens surface) and the height h of the droplet by the following formula.
θ = 2 × tan −1 (h / r)
The measurement was performed within 10 seconds after the droplet was formed on the lens in order to minimize the error due to the evaporation of water.
(3) Luminous reflectance (one side)
The luminous reflectance before and after the formation of the water-repellent film was measured using a U-3410 self-recording spectral height type manufactured by Hitachi, Ltd.
(4) Slipperiness The coefficient of friction and the friction force (gf) before and after the start were measured using a continuous weighted surface property measuring device TYPE: 22H manufactured by Shinto Kagaku Co., Ltd. The measurement was performed before the durability test described in the above (2), after the durability test was performed 5,000 times, and after the durability test was performed 10,000 times, respectively.
[0024]
Example 1
A stainless steel sintered filter (mesh 80 to 100 microns, 18φ × 3 mm) impregnated with 0.15 ml of water-repellent agent 1 (Optole DSX: trade name (manufactured by Daikin Industries, Ltd.)) is vacuum-deposited. And the entire sintered filter was heated using an electron gun under the following conditions to form a first layer of a water-repellent film on the plastic lens with an antireflection film cut into the lens frame shape. .
(1) Vacuum degree: 3.1 × 10 −4 to 8 × 10 −4 Pa (2.3 × 10 −6 to 6.0 × 10 −6 Torr)
(2) Electron gun conditions: acceleration voltage: 6 kV, applied current: 40 mA, irradiation area: 3.5 × 3.5 cm square, vapor deposition time: 10 seconds. The vapor deposition time means the time from the start of heating to the completion of vapor deposition. I do.
Thereafter, "Demunum S-20" (manufactured by Daikin Industries, Ltd.) as a silicon-free perfluoropolyether impregnated into paper was applied on the first layer of the water-repellent film. Table 1 shows the evaluation results. Slipperiness and durability were good, and water repellency was also good.
[0025]
Examples 2 to 4
A water-repellent film was formed in the same manner as in Example 1 except that the water-repellent shown in Table 1 was used instead of the water-repellent used in Example 1. Table 1 shows the evaluation results. As in Example 1, water repellency, slipperiness and durability were good.
[0026]
Reference Example The same procedure was performed as in Example 1 except that the second layer of the water-repellent film was not applied. Table 1 shows the results. The slipperiness was inferior to Examples 1-4.
[0027]
[Table 1]
Note) A: Optool DSX (trade name (manufactured by Daikin Industries, Ltd.))
a: Demnum S-20 (manufactured by Daikin Industries, Ltd.) (average molecular weight 2700)
b; Demnum S-65 (manufactured by Daikin Industries, Ltd.) (average molecular weight 4500)
c; Demnum S-100 (manufactured by Daikin Industries, Ltd.) (average molecular weight 5600)
d; Demnum S-200 (manufactured by Daikin Industries, Ltd.) (average molecular weight 8400)
[0029]
【The invention's effect】
According to the present invention, it is possible to obtain an optical member that has good slipperiness and water repellency and can smoothly wipe the water repellent film when removing dirt on the water repellent film with a cloth or the like.
[Brief description of the drawings]
FIG. 1 is a schematic view showing an apparatus for performing a durability test in the present invention.
[Explanation of symbols]
1: lens 2: chamois skin 3: hexahedral plate
Claims (11)
（式中、Ｒｆは炭素数１〜１６の直鎖状のパーフルオロアルキル基、Ｘは水素または炭素数１〜５の低級アルキル基、Ｒ１は加水分解可能な基、ｍは１〜５０の整数、ｎは０〜２の整数、ｐは１〜１０の整数）
で表される請求項１記載の光学部材。The fluorine-substituted alkyl group-containing organosilicon compound has the following general formula (I)
(Wherein, Rf is a linear perfluoroalkyl group having 1 to 16 carbon atoms, X is hydrogen or a lower alkyl group having 1 to 5 carbon atoms, R1 is a hydrolyzable group, and m is an integer of 1 to 50. , N is an integer of 0 to 2, p is an integer of 1 to 10)
The optical member according to claim 1, wherein
ＣｑＦ２ｑ＋１ＣＨ２ＣＨ２Ｓｉ（ＮＨ２）３ ・・・（ＩＩ）
（ただし、ｑは１以上の整数である）で表される請求項１に記載の光学部材。The fluorine-substituted alkyl group-containing organosilicon compound has the following unit formula (II):
C q F 2q + 1 CH 2 CH 2 Si (NH 2) 3 ··· (II)
The optical member according to claim 1, wherein q is an integer of 1 or more.
−（ＲＯ）− ・・・（ＩＩＩ）
（式中、Ｒは炭素数１〜３のパーフルオロアルキレン基である）The optical member according to claim 1, wherein the silicon-free perfluoropolyether comprises a unit represented by the general formula (III).
-(RO)-... (III)
(Wherein, R is a perfluoroalkylene group having 1 to 3 carbon atoms)
条件１：前記有機ケイ素化合物の加熱温度が、該有機ケイ素化合物の蒸着開始温度から該有機ケイ素化合物の分解温度までの範囲であること。
条件２：有機ケイ素化合物の加熱開始から加熱蒸発の完結までの時間が９０秒以内であること。The optical member according to claim 7, which is deposited on a substrate under the following conditions.
Condition 1: the heating temperature of the organosilicon compound is in the range from the vapor deposition start temperature of the organosilicon compound to the decomposition temperature of the organosilicon compound.
Condition 2: The time from the start of the heating of the organosilicon compound to the completion of the heating evaporation is within 90 seconds.
条件１：前記有機ケイ素化合物の加熱温度が、該有機ケイ素化合物の蒸着開始温度から該有機ケイ素化合物の分解温度までの範囲であること。
条件２：有機ケイ素化合物の加熱開始から加熱蒸発の完結までの時間が９０秒以内であること。The method for manufacturing an optical member according to claim 10, wherein the method is performed by vapor deposition on a substrate under the following conditions.
Condition 1: the heating temperature of the organosilicon compound is in the range from the vapor deposition start temperature of the organosilicon compound to the decomposition temperature of the organosilicon compound.
Condition 2: The time from the start of the heating of the organosilicon compound to the completion of the heating evaporation is within 90 seconds.
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