JP4731743B2 - Abrasion resistant film and laminate - Google Patents

Description

（式中Ｒ^６およびＲ^７は炭素数１〜１０の一価の脂肪族炭化水素基、フェニル基または一価のハロゲン化炭化水素基を表し、ｑは１以上の正数である。）
【００３６】
【化２】

（式中Ｒ^８は水素原子またはメチル基を表し、Ｒ^９はメチル基、エチルまたはフェニル基を表し、２個のＲ^９は互いに同一もしくは異なっていてもよく、Ｚは塩素原子、メトキシ基またはエトキシ基を表す。）
【００３７】
前記式（III）で示されるシリコーンは市販品として入手でき、目的にあったものを使用することができる。前記式（III）におけるＲ^６およびＲ^７は炭素数１〜１０の一価の脂肪族炭化水素基、フェニル基または一価のハロゲン化炭化水素であり、炭素数１〜１０の一価の脂肪族炭化水素基としては、例えばメチル基、エチル基、アシル基等が挙げられ、一価のハロゲン化炭化水素としては、例えば３,３,３−トリフルオロプロピル基、４,４,４−トリフルオロ−３,３−ジフルオロブチル基、２−クロロエチル基等が挙げられる。Ｒ^８およびＲ^９として特に好ましいのはメチル基である。
【００３８】
前記式（III）でｑは１以上の正数であるが、一般にｑの数が１００以上という高分子量のシリコーンから誘導されるアクリル変性シリコーンとラジカル重合性単量体との共重合からはオイル状のものが得られやすい傾向にあり、ｑの数が１００以下という低分子量シリコーンから誘導されるアクリル変性シリコーンとラジカル重合性単量体との共重合からは用いるモノマーの種類によりオイル状、ゼリー状、固体状等各種のものを得ることができる。
【００３９】
次に前記式（IV）で示されるアクリルシラン化合物としては、例えばγ−メタクリルオキシプロピルジメチルクロロシラン、γ−メタクリルオキシプロピルジメチルエトキシシラン、γ−メタクリルオキシプロピルジフェニルクロロシラン、γ−アクリルオキシプロピルジメチルクロロシラン、γ−メタクリルオキシプロピルトリエトキシシラン、γ−メタクリルオキシプロピルトリクロロシラン等が挙げられる。これらのアクリルシラン化合物は、特公昭３３−９９６９号の方法等に従い、ケイ素化合物と脂肪族性多重結合を有する化合物とを塩化白金酸の存在下で反応させることにより容易に得られる。
【００４０】
また、アクリル変性シリコーンとラジカル重合性単量体とのラジカル共重合は、従来公知の方法を使用でき、放射線照射法、ラジカル重合開始剤を用いる方法を使用できる。さらに紫外線照射法により共重合させる場合は、ラジカル重合開始剤として公知の増感剤を使用し、電子線照射により共重合させる場合はラジカル重合開始剤を使用する必要はない。このようにして得られたシリコーン共重合体は、ラジカル重合性単量体を幹とし、シリコーンを枝とする櫛形グラフト共重合体である。
【００４１】
シリコーン共重合体の市販品としては、サイマックＵＳ−１５０、ＵＳ−２７０、ＵＳ−３５０、ＵＳ−４５０、レゼダＧＰ−７００（以上、東亞合成（株）製）等を挙げることができる。
【００４２】
本発明のハードコート層は、前述のようにシリカ微粒子を７０〜９０質量％の高濃度で含有している。好ましくは７５〜８５質量％である。
【００４３】
上記シリカ微粒子は、粉体状シリカまたはコロイダルシリカであり、一次粒径が一般に１〜２００ｎｍ（ｍμ）の範囲、好ましくは１〜１００ｎｍの範囲、さらに好ましくは２０〜５０ｎｍの範囲である。シリカ微粒子の形状は球状、中空状、多孔質状、棒状、板状、繊維状、もしくは不定形状であり、好ましくは球状である。シリカ微粒子の比表面積は０.１〜３０００ｍ^２／ｇであり、好ましくは１０〜１５００ｍ^２／ｇである。これらのシリカ微粒子の使用形態は乾燥状態の粉末、もしくは水もしくは有機溶剤で分散した状態で用いることができ、コロイダルシリカとして知られている微粒子状のシリカ微粒子の分散液を直接用いることができる。特に透明性を得るためにはコロイダルシリカの利用が好ましい。コロイダルシリカの分散溶媒が水の場合、その水素イオン濃度はｐＨ値として２〜１０の範囲であり、好ましくはｐＨ３〜７の酸性コロイダルシリカが用いられる。また、コロイダルシリカの分散溶媒が有機溶剤の場合、有機溶剤としてメタノ−ル、イソプロピルアルコ−ル、エチレングリコ−ル、ブタノ−ル、エチレングリコ−ルモノプロピルエ−テル、メチルエチルケトン、メチルイソブチルケトン、トルエン、キシレン、ジメチルホルムアミド等の溶剤もしくはこれらと相溶する有機溶剤もしくは水との混合物として用いても良い。好ましい分散溶剤はメタノ−ル、イソプロピルアルコ−ル、メチルエチルケトン、キシレンである。シリカ微粒子の市販品としては、例えば、コロイダルシリカとしては日産化学工業（株）製のメタノ−ルシリカゾル、ＩＰＡ−ＳＴ、ＭＥＫ−ＳＴ、ＮＢＡ−ＳＴ、ＸＢＡ−ＳＴ、ＤＭＡＣ−ＳＴおよびＳＴ−ＵＰ、ＳＴ−ＯＵＰ、ＳＴ−２０、ＳＴ−４０、ＳＴ−Ｃ、ＳＴ−Ｎ、ＳＴ−Ｏ、ＳＴ−５０、ＳＴ−ＯＬ等をあげることができる。また粉体状シリカとしては、日本アエロジル（株）製のアエロジル１３０、アエロジル３００、アエロジル３８０、アエロジルＴＴ６００及びアエロジルＯＸ５０、旭硝子（株）製のシルデックスＨ３１、Ｈ３２、Ｈ５１、Ｈ５２、Ｈ１２１、Ｈ１２２、日本シリカ工業（株）製のＥ２２０Ａ、Ｅ２２０ 富士シリシア（株）製のサイリシア４７０、日本板硝子（株）製のＳＧフレ−ク等を挙げることができる。
【００４４】
本発明のハードコート層形成用の硬化性樹脂に含まれるシリカ微粒子として、シリカ微粒子と重合性不飽和基（及び好ましくはウレタン結合）を有するアルコキシシラン化合物との反応により形成されるもの（以下「変性シリカ微粒子」と言う）が好ましく、これは下記の構成を有するものが好ましい。
【００４５】
本発明の上記変性シリカ微粒子は、重合性不飽和基とウレタン結合基、式（Ｉ）−Ｘ−Ｃ（＝Ｙ）−ＮＨ−で表される有機基とを有するアルコキシシラン化合物とシリカ微粒子を反応させて得られる反応生成物であることが好ましい（上記式（Ｉ）中、Ｘは−ＮＨ−、−Ｏ−または−Ｓ−であり、Ｙは酸素原子またはイオウ原子である、但しＸが−Ｏ−のときＹはイオウ原子である）。
【００４６】
上記変性シリカ微粒子は、アルコキシシラン化合物とシリカ微粒子とを少なくとも混合する操作を含む方法により製造される。シリカ微粒子に固定されたアルコキシシラン化合物残渣の含有量は０.０１質量％以上であり、好ましくは０.１質量％以上、特に好ましくは１質量％以上のものが用いられる。シリカ微粒子中に固定されたアルコキシシラン化合物残渣の含有量が０.０１質量％未満の場合、組成物中のシリカ微粒子或いはコロイダルシリカの分散性、透明性、耐磨耗性が十分でない場合がある。また製造時の原料組成物中におけるアルコキシシラン化合物の割合は好ましくは１０質量％以上であり、特に好ましくは３０質量％以上である。アルコキシシラン化合物の割合が１０質量％未満の場合、紫外線硬化性樹脂の成膜性が悪い場合がある。また、紫外線硬化性樹脂中のシリカ微粒子の割合は好ましくは５０質量％以下であり、特に好ましくは２０質量％以下である。紫外線硬化性樹脂中のシリカ微粒子の割合が５０質量％以上の場合、本発明組成物の分散性、透明性、耐磨耗性が十分でない場合がある。
【００４７】
アルコキシシラン化合物は分子中に重合性不飽和基、ウレタン結合基、前記式（Ｉ）で表される有機基およびアルコキシシリル基を構成成分として少なくともそれぞれ１個含んでいる。アルコキシシリル基は加水分解、縮合反応によりシリカ微粒子の表面に存在するシラノ−ル基と結合する成分であり、また、重合性不飽和基とは、活性ラジカル種により付加重合を経て分子間で化学架橋する成分である。また、前記式（Ｉ）で表される２価の有機基である−Ｘ（Ｃ＝Ｙ）ＮＨ−基およびウレタン結合基はこれらアルコキシシリル基を有する分子片と重合性不飽和基を有する分子片とを直接もしくは他の分子片を介して結合する構成単位であると同時に分子間において水素結合による適度の凝集力を発生させ、本発明ハードコート層に優れた力学的強度、基材との密着性、耐熱性等の性能を発生させると考えられる。−Ｘ（Ｃ＝Ｙ）ＮＨ−基としては、−Ｓ（Ｃ＝Ｏ）ＮＨ−基が好ましい。
【００４８】
アルコキシシラン化合物の構造としては例えば、一般式（II）；
【００４９】
【化３】

で表されるアルコキシシラン化合物をあげることができる。
【００５０】
上記一般式（II）において、Ｒ^１は水素原子、およびＣ_１〜Ｃ_８の１価の有機基であり、例えば、メチル、エチル、プロピル、ブチル、フェニル、オクチル基等である。Ｒ^２は水素原子、およびＣ_１〜Ｃ_３の１価のアルキル基である。ｍは１、２もしくは３であり、（Ｒ^１Ｏ）_ｍＲ^２Ｓｉ_３−ｍで示されるアルコキシシリル基としては例えば、トリメトキシシリル基、トリエトキシシリル基、トリフェノキシシリル基、メチルジメトキシシリル基、ジメチルメトキシシリル基等をあげることができ、好ましくは、トリメトキシシリル基およびトリエトキシシリル基である。
【００５１】
また、式中、−［（Ｃ＝Ｏ）ＮＨ−Ｒ^４−ＮＨ（Ｃ＝Ｏ）Ｏ−Ｘ−Ｏ］_ｐ−として示される構造単位は前記式（II）に示す構造において分子鎖を延長することを目的として導入される。Ｒ^３はＣ^１〜Ｃ^３の２価の有機基である。Ｒ^４は２価の有機基であり、Ｒ^３と同一でも異なっていてもよく、通常、分子量１４〜１万、好ましくは、分子量７８〜１０００の２価の有機基の中から選ばれ、例えば、メチレン、エチレン、プロピレン、ヘキサメチレン、オクタメチレン、ドデカメチレン等の鎖状ポリアルキレン基；シクロヘキシレン、ノルボルニレン等の脂環式または多環式の２価の有機基；ビニレン、フェニレン、ナフチレン、ビフェニレン、ポリフェニレン等の２価の芳香族基；等をあげることができ、また、これらのアルキル基置換体、アリ−ル基置換体も用いることができる。これら２価有機の構造中には炭素、水素原子以外の元素から構成される原子団を含んでいてもよい。式中、ｐは０もしくは１であり、Ｘは２価の有機基であり、さらにイソシアネ−ト基と付加反応できる活性水素原子を分子内に２個以上有する化合物から誘導される２価の有機基であり、例えば、ポリアルキレングリコ−ル類、ポリアルキレンチオグリコ−ル類、ポリエステル類、ポリアミド類、ポリカ−ボネ−ト類、ポリアルキレンジアミン類、ポリアルキレンジカルボン酸類、ポリアルキレンジオ−ル類、ポリアルキレンジメルカプタン類から活性水素原子を２個除くことで誘導される２価の有機基をあげることができる。また、Ｒ^５は（ｎ＋１）価の有機基である。このような有機基は、好ましくは鎖状、分岐状または環状の飽和炭化水素基、不飽和炭化水素基、脂環式基の中から選ばれる。また、ｎは好ましくは１〜２０の正の整数であり、より好ましくは１〜１０であり、さらに好ましくは３〜５である。前記式中Ｙは活性ラジカル種の存在下、分子間架橋反応をする重合性不飽和基を分子中に有する１価の有機基を表し、例えば、アクリロキシ基、メタクリロキシ基、ビニル基、プロペニル基、ブタジエニル基、スチリル基、エチニイル基、シンナモイル基、マレエ−ト基、アクリルアミド基等があげられる。これらの中でアクリロキシ基が好ましい。
【００５２】
アルコキシシラン化合物の分子構造の形成には、通常、メルカプト基を有するアルコキシシラン、すなわちメルカプトアルコキシシランと、ポリイソシアネ−ト化合物およびイソシアネ−ト基と付加反応を起こす活性水素を有する活性水素基含有重合性不飽和化合物との付加反応により行うことができる。
【００５３】
アルコキシシラン化合物の製造方法としては例えば、（Ａ）法；まずメルカプトアルコキシシランとポリイソシアネ−ト化合物との付加体を反応させることにより分子中にアルコキシシリル基、−Ｓ（Ｃ＝Ｏ）ＮＨ−結合基、及びイソシアネ−ト基を含む中間体を製造し、次に中間体中に残存するイソシアネ−トに対して活性水素基含有重合性不飽和化合物を反応させウレタン基を介して結合させる方法。
（Ｂ）法；まずポリイソシアネ−ト化合物と活性水素基含有重合性不飽和化合物との付加体を反応させることにより分子中に重合性不飽和基、ウレタン結合基、およびイソシアネ−ト基を含む中間体を形成し、これにメルカプトアルコキシシランを反応させ−Ｓ（Ｃ＝Ｏ）ＮＨ−基を介して結合させる方法等をあげることができる。さらに、前記（Ａ）または（Ｂ）法において、鎖延長単位としてさらに、イソシアネ−トと付加反応を起こす活性水素を分子内に２個以上有する鎖状、環状または分岐状の化合物をポリイソシアネ−ト化合物とのウレタン結合を介して延長することもできる。
【００５４】
前記式（II）に示した化合物を製造において、直接、ポリイソシアネ−ト化合物との反応により−Ｓ（Ｃ＝Ｏ）ＮＨ−結合を形成することができるアルコキシシランの例としては、反応生成物としてアルコキシシリル基とメルカプト基を分子中にそれぞれ１個以上有する化合物の中から選ぶことができる。例えば、メルカプトプロピルトリメトキシシラン、メルカプトプロピルトリエトキシシラン、メルカプトプロピルメチルジエトキシシラン、メルカプトプロピルジメトキシメチルシラン、メルカプイトプロピルメトキシジメチルシラン、メルカプトプロピルトリエトキシシラン、メルカプトプロピルトリフェノキシシラン、メルカプトプロピルトリブトキシシラン等のメルカプトアルコキシシランをあげることができ、好ましくはメルカプトプロピルトリメトキシシラン、メルカプトプロピルトリエトキシシランである。市販されているメルカプトアルコキシシランとしては、例えば東レ・ダウ・コ−ニング（株）製のＳＨ６０６２をあげることができる。これらメルカプトアルコキシシランは単独または２種以上を混合して用いてもよく、さらに、メルカプトアルコキシシランの例としては、アミノ置換アルコキシシランとエポキシ基置換メルカプタンとの付加生成物、エポキシシランとα、ω−ジメルカプト化合物との付加生成物を利用することができる。アルコキシシラン化合物を製造する際に利用する、ポリイソシアネ−ト化合物としては鎖状飽和炭化水素、環状飽和炭化水素、芳香族炭化水素で構成されるポリイソシアネ−ト化合物の中から選ぶことができ、単独もしくは２種以上混合して用いることができる。１分子中のイソシアネ−ト基の個数は、通常２以上、３０未満であり、好ましくは２以上１０未満である。３０を超えると生成物の粘度が高くなり作業性が低下する場合がある。
【００５５】
このようなポリイソシアネ−ト化合物の例としては、例えば、テトラメチレンジイソシアネ−ト、ヘキサメチレンジイソシアネ−ト、２,２,４−トリメチルヘキサメチレンジイソシアネ−ト等の鎖状炭化水素ポリイソシアネ−ト化合物；イソフォロンジイソシアネ−ト、ジシクロヘキシルメタンジイソシアネ−ト、メチレンビス（４−シクロヘキシルイソシアネア−ト）、水添ジフェニルメタンジイソシアネ−ト、水添キシレンジイソシアネ−ト、水添トルエンジイソシアネ−ト、１,３−ビス（イソシアナ−トメチル）シクロヘキサン等の環状飽和炭化水素ポリイソシアネ−ト化合物；２,４−トリレンジイソシアネ−ト、２,６−トリレンジイソシアネ−ト、１,３−キシリレンジイソシアネ−ト、１,４−キシリレンジイソシアネ−ト、パラフェニレンジイソシアネ−ト、３,３’−ジメチル−４,４’−ジフェニルメタンジイソシアネ−ト、ジフェニルメタン−４,４’−ジイソシアネ−ト、４,４’−ビフェニレンジイソシアネ−ト、６−イソプロピル−１,３−フェニルジイソシアネ−ト、４−ジフェニルプロパンジイソシアネ−ト、リジンジイソシアネ−ト、１,５−ナフタレンジイソシアネ−ト、ポリジフェニ−ルメタンのポリイソシアネ−ト等の芳香族炭化水素ポリイソシアネ−ト化合物を挙げることができる。
【００５６】
これらの中で好ましい例としては、環状飽和炭化水素ポリイソシアネ−ト化合物および芳香族炭化水素ポリイソシアネ−ト化合物であり、さらに好ましくは環状飽和炭化水素のポリイソシアネ−ト化合物をあげることができる。好ましい具体例としては、イソホロンジイソシアネ−ト、水添キシレンジイソシアネ−ト、水添トルエンジイソシアネ−トである。また市販されているポリイソシアネ−ト化合物を例示すると、三井日曹ウレタン（株）製のＴＤＩ−８０／２０、ＴＤＩ−１００、ＭＤＩ−ＣＲ１００、ＭＤＩ−ＣＲ３００、ＭＤＩ−ＰＨ、ＮＤＩや日本ポリウレタン工業（株）製のコロネ−トＴ、ミリオネ−トＭＴ、ミリオネ−トＭＲ、ＨＤＩ、武田薬品工業（株）製 のタケネ−ト６００をあげることができる。
【００５７】
これらポリイソシアネ−ト化合物の使用量は、前記（Ａ）法に示す製造法においては、メルカプトアルコキシシランのメルカプト基１当量に対してのイソシアネ−ト基当量としては、通常０.１〜１００の範囲内で、好ましくは０.５から１０の範囲で、さらに好ましくは０.９〜１.２の範囲で添加される。ポリイソシアネ−ト化合物基当量の添加量が０.１当量未満の場合、未反応メルカプトシランが０.９当量以上存在することになり、塗膜の磨耗性が十分でない場合がある。また、１００当量を超えたポリイソシアネ−ト化合物の使用は、未反応イソシアネ−ト基が過剰に存在することになり耐候性が低下する場合がある。
【００５８】
一方、前記（Ｂ）法に示す製造法においては、活性水素基含有重合性不飽和化合物中の活性水素基１当量に対し、ポリイソシアネート化合物はイソシアネート基当量として通常０.１〜１００の範囲であり、好ましくは０.５〜１０当量の範囲で、さらに好ましくは０.９〜１.２の範囲で添加される。
【００５９】
前記（Ａ）または（Ｂ）法いずれの方法においても、反応時間の短縮を目的として触媒を添加してもよい。このような触媒としては、塩基性触媒および酸性触媒のいずれかが用いられる。塩基性触媒の例としては、ピリジン、ピロ−ル、トリエチルアミン、ジエチルアミン、ジブチルアミン、アンモニアなどのアミン類；トリブチルフォスフィン、トリフェニルフォスフィン等のフォスフィン類を挙げることができる。これらの中でピリジン、トリエチルアミン等の第３級アミンが好ましい。また酸性触媒としては、ナフテン酸銅、ナフテン酸コバルト、ナフテン酸亜鉛、１,４−ジアザビシクロ［２.２.２］オクタン（ＤＡＢＣＯ）、メチルＤＡＢＣＯ、トリブトキシアルミニウム、トリチタニウムテトラブトキシド、ジルコニウムテトラブトキシド等の金属アルコキシド類；３フッ化硼素ジエチルエ−テラ−ト、塩化アルミニウムなどのルイス酸類；２−エチルヘキサン酸錫、オクチル錫トリラウレ−ト、ジブチル錫ジラウレ−ト、オクチル錫ジアセテ−ト等の錫化合物をあげる。これら触媒の中で好ましいものは酸性触媒であり、特に好ましくは錫化合物であり、さらに好ましくはオクチル錫トリラウレ−ト、ジブチル錫ジラウレ−ト、オクチル錫ジアセテ−ト等である。これら触媒の添加量はポリイソシアネ−ト化合物１００質量部に対して０.０１〜５質量部であり、好ましくは０.１〜１質量部である。０.０１質量部未満では触媒添加による反応時間の短縮効果はわずかであり、一方、５質量部を超えると生成物の保存安定性が低下する場合がある。
【００６０】
アルコキシシリル化合物の製造において、前記ポリイソシアネ−ト化合物と付加反応によりウレタン結合を介し結合できる重合性不飽和化合物の例としては、分子内にイソシアネ−ト基との付加反応によりウレタン結合を形成できる活性水素原子を分子中に１個以上有し、重合性不飽和基を分子中に１個以上含む化合物の中から単独もしくは２種以上の混合物として用いることができる。
【００６１】
そのような化合物としては、カルボン酸含有重合性不飽和化合物、水酸基含有重合性不飽和化合物がある。例えば、カルボン酸を含有する重合性不飽和化合物としては、（メタ）アクリル酸、イタコン酸、ケイヒ酸、マレイン酸、フマル酸、２−（メタ）アクリロキシプロピルヘキサヒドロゲンフタレ−ト、２−（メタ）アクリロキシエチルヘキサヒドロゲンフタレ−ト等の不飽和脂肪族カルボン酸類；２−（メタ）アクリロキシプロピルフタレ−ト、２−（メタ）アクリロキシプロピルエチルフタレ−ト等の不飽和芳香族カルボン酸類；をあげることができる。また、水酸基含有重合性不飽和化合物として、２−ヒドロキシエチル（メタ）アクリレ−ト、２−ヒドロキシプロピル（メタ）アクリレ−ト、２−ヒドロキシブチル（メタ）アクリレ−ト、２−ヒドロキシ−３−フェニルオキシプロピル（メタ）アクリレ−ト、１,４ブタンジオ−ルモノ（メタ）アクリレ−ト、２−ヒドロキシアルキル（メタ）アクリロイルフォスフェ−ト、４−ヒドロキシシクロヘキシル（メタ）アクリレ−ト、ネオペンチルグリコ−ルモノ（メタ）アクリレ−ト、ポリ（ペンタメチレンオキシカルボキシレ−ト）エトキシ（メタ）アクリレ−ト、ヒドロキシスチレン、ヒドロキシアルファメチルスチレン、ヒドロキシエチルスチレン、ヒドロキシ末端ポリエチレングリコ−ルスチリルエ−テル、ヒドロキシ末端ポリプロピレングリコ−ルスチリルエ−テル、ヒドロキシ末端ポリテトラメチレングリコ−ルスチリルエ−テル、末端ヒドロキシポリエチレングリコ−ル（メタ）アクリレ−ト、末端ヒドロキシポリプロピレングリコ−ル（メタ）アクリレ−ト、末端ヒドロキシポリテトラエチレングリコ−ル（メタ）アクリレ−ト、トリメチロ−ルプロパンジ（メタ）アクリレ−ト、トリメチロ−ルプロパンモノ（メタ）アクリレ−ト、ＥＯ変性トリメチロ−ルプロパントリ（メタ）アクリレ−ト、ＰＯ変性トリメチロ−ルプロパントリ（メタ）アクリレ−ト、ペンタエリスリト−ルトリ（メタ）アクリレ−ト、ペンタエリスリト−ルジ（メタ）アクリレ−ト、ペンタエリスリト−ルモノ（メタ）アクリレ−ト、ジペンタエリスルト−ルペンタ（メタ）アクリレ−ト、ジペンタエリスリト−ルテトラ（メタ）アクリレ−ト、ジペンタエリスリト−ルトリ（メタ）アクリレ−ト、ジペンタエリスリト−ルジ（メタ）アクリレ−ト、ジペンタエリスリト−ルモノ（メタ）アクリレ−ト、等の水酸基含有アクリレ−ト類、水酸基含有メタクリレ−ト類、水酸基含有スチレン類をあげることができる。
【００６２】
これらの中で好ましいのは、不飽和脂肪族カルボン酸類、水酸基含有アクリレ−ト化合物であり、さらに好ましくは、水酸基含有アクリレ−ト化合物であり、例えば、２−ヒドロキシルエチルアクリレ−ト、２−ヒドロキシプロピルアクリレ−ト、ペンタエリスリト−ルトリアクリレ−ト、ジペンタエリスルト−ルペンタアクリレ−トをあげることができる。
【００６３】
これら重合性不飽和化合物の使用量はその活性水素基の当量として、メルカプトアルコキシシランとポリイソシアネ−ト化合物との付加反応により得られる中間体中の残存イソシアネ−ト基１当量に対し、通常、１当量以上である。１当量未満ではアルコキシシリル化合物中に活性イソシアネ−ト基が残存する為、水分との反応による発泡、増粘、着色などの好ましくない性能が発現する場合がある。
【００６４】
アルコキシシリル化合物の製造においては、塗膜の柔軟性や基材に対する密着性向上を目的として、ポリイソシアネ−ト化合物との付加反応によりアルコキシシリル基と重合性不飽和基との間に２価の有機基を導入してもよく、そのような２価の有機化合物単位の前駆体としてはイソシアネ−ト基と付加反応を起こす活性水素を分子内に２個以上有する鎖状、環状、分岐状の有機化合物を利用できる。ここで活性水素を有する基の例としては、水酸基、カルボキシル基、メルカプト基、アミノ基、スルホン酸基、リン酸基、シラノ−ル基等をあげることができる。これらの有機化合物は、活性水素を２個以上、好ましくは２個以上１０個未満、さらに好ましくは２個を有する。そのような活性水素を有する化合物の分子量は通常、５０〜１０万であり、好ましくは１００〜５万、さらに好ましくは５００〜１万である。そのような２価の有機化合物としては、例えば、ポリアルキレングリコ−ル類、ポリアルキレンチオグリコ−ル類、ポリエステルジオ−ル類、ポリアミド類、ポリカ−ボネ−トジオ−ル類、ポリアルキレンジアミン類、ポリアルキレンジカルボン酸類、ポリアルキレンジオ−ル類、ポリアルキレンジメルカプタン類を挙げることができる。これらの中でポリアルキレングリコ−ルが好ましい。市販されているポリアルキレングリコ−ル類としては例えば、ポリエチレングリコ−ル、ポリプロピレングリコ−ル、ポリテトラエチレングリコ−ル、ポリヘキサメチレングリコ−ルや、これらの２種以上のポリアルキレングリコ−ルとの共重合体の中から選ぶことができ、日本油脂（株）製のユニセ−フＤＣ１１００、ユニセ−フＤＣ１８００、ユニセ−フＤＣＢ１１００、ユニセ−フＤＣＢ１８００、保土谷化学（株）製のＰＰＴＧ４０００,ＰＰＴＧ２０００、ＰＰＴＧ１０００、ＰＴＧ２０００、ＰＴＧ３０００、ＰＴＧ６５０、ＰＴＧＬ２０００、ＰＴＧＬ１０００、旭硝子（株）製のＥＸＥＮＯＬ１０２０、第一工業製薬（株）製のＰＢＧ３０００、ＰＢＧ２０００、ＰＢＧ１０００、Ｚ３００１等を挙げルコとができる。
【００６５】
上記の２価の有機基を構成成分として含む重合性不飽和基含有アルコキシシランを製造する場合を、ポリアルキレングリコ−ルを例にとって製造法（Ｃ）法および（Ｄ）法として示す。
【００６６】
製造法（Ｃ）法：末端に活性イソシアネ−ト基を有する、メルカプトアルコキシシランとポリシソシアネ−ト化合物との付加体に対し、ポリアルキレングリコ−ルを加え、片末端ヒドロキシのアルコキシシランとしたのち、これに対し別途合成した、末端に水酸基を有する重合性不飽和化合物とポリイソシアネ−ト化合物との付加体を反応させウレタン結合で両者をつなぐ方法。
【００６７】
製造法（Ｄ）法：末端に活性イソシアネ−ト基を有する、メルカプトアルコキシシランとポリイソシアネ−ト化合物との付加体に対し、別途合成した、末端に活性水酸基を有する、ポリアルキレングリコ−ルポリイソシアネ−ト化合物、水酸基含有重合性不飽和化合物との付加体を反応させウレタン結合で両者をつなぐ方法を挙げることができる。前記（Ｃ）法または（Ｄ）法におけるウレタン結合の形成条件は前記（Ａ）または（Ｂ）法と同様であり、結合に関与する、末端に活性イソシアネ−ト基を有する化合物に対する末端に水酸基を有する化合物の当量比は通常、１.０〜１.２の範囲である。１.０未満の場合は未反応のイソシアネ−ト基による着色、増粘が起こりやすい。
【００６８】
また、アルコキシシラン化合物の製造において重合性不飽和基修飾アルコキシシランの加水分解物として他の有機アルコキシシランとの加水分解生成物を用いてもよく、例えば、テトラメトキシシラン、テトラエトキシシラン、テトラブトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、ジメチルジメトキシシラン、フェニルトリメトキシシラン等のアルキルアルコキシシランとの縮合物を用いても良い。加水分解生成物を製造する場合、加水分解に用いる水の量は全アルコキシ基に対して通常０.５〜１.５当量であり、溶剤の存在下もしくは非存在下で、０℃から成分の沸点以下の温度で５分〜２４時間加熱攪拌することで加水分解、縮重合物を得ることができる。その際、反応時間の短縮を目的に酸性触媒もしくは塩基触媒を併用することもできる。
【００６９】
変性シリカ微粒子の製造において用いられるシリカ微粒子は前述のものを同様に使用することができる。
【００７０】
変性シリカ微粒子に固定されたアルコキシシラン化合物は通常、乾燥粉体を空気中で完全に燃焼させた場合の質量減少％の恒量値として、例えば、空気中で室温から通常８００℃までの熱質量分析により求めることが出来る。
【００７１】
変性シリカ微粒子の製造においてアルコキシシラン化合物の加水分解で消費される水の量は、１分子中のケイ素上のアルコキシ基の少なくとも１個が加水分解される量あればよい。好ましくは加水分解の際に添加、もしくは存在する水の量は、ケイ素上の全アルコキシ基のモル数に対し３分の１以上であり、さらに好ましくは全アルコキシ基のモル数の２分の１以上３倍未満である。完全に水分の存在しない条件下で前記式（II）に示すアルコキシシラン化合物とシリカ微粒子とを混合して得られる生成物は、シリカ微粒子表面にアルコキシシラン化合物が物理吸着した生成物であり、そのような成分から構成される組成物においては本発明の組成物の一つの目的である耐磨耗性の発現の効果は低い。
【００７２】
本発明の変性シリカ微粒子の製造においては前記式（II）に表されるアルコキシシラン化合物を別途加水分解操作を行った後、これと粉体シリカ微粒子もしくはコロイダルシリカを混合し、加熱、攪拌操作を行う方法；もしくは、前記式（II）で表されるアルコキシシラン化合物の加水分解をシリカ微粒子の存在下で行う方法；また、他の成分、例えば、多官能不飽和有機化合物、単価不飽和有機化合物、光重合開始剤等の存在下、シリカ微粒子の表面処理を行う方法等を選ぶことができるが、前記式（II）で表されるアルコキシシラン化合物の加水分解をシリカ微粒子の存在下で行う方法が好ましい。成分Ｂを製造する際、その製造時の温度は通常、２０℃〜１５０℃であり、また処理時間は５分〜２４時間の範囲である。
【００７３】
シリカ微粒子は、通常の保管状態として粒子表面に吸着水として水分を含むことが知られている。例えば、有機溶剤分散コロイダルシリカ中においても通常製品として０.５％相当の水分を含有する。したがって、変性シリカ微粒子の製造においては、アルコキシシラン化合物とシリカ微粒子とを混合し、加熱、攪拌処理することにより原料中に含まれる水分を利用して製造することも可能である。
【００７４】
本発明の変性シリカ微粒子の製造において、粉体状のシリカを用いる場合、アルコキシシラン化合物との反応を円滑にかつ、均一に行わせるこために、水と相溶する有機溶媒を添加してもよい。このような有機溶媒の好ましい種類は、アルコ−ル類、ケトン類、エ−テル類、アミド類であり、アルコ−ル類としてはメタノ−ル、エタノ−ル、イソプロピルアルコ−ル、ブタノ−ル、エチレングリコ−ルモノメチルエ−テル、エチレングリコ−ルモノブチルエ−テル等、ケトン類としては、アセトン、メチルエチルケトン、メチルイソブチルケトン、アミド類としてはジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン、ガンマブチロラクトン等をあげることができる。これらの溶剤の添加量は反応を円滑、均一に行わせる目的に合致する限り特に制限はない。
【００７５】
また、変性シリカ微粒子の製造において、反応を促進するため、触媒として酸もしくは塩基を添加してもよく、酸としては、塩酸、硝酸、硫酸、リン酸、等の無機酸、もしくはメタンスルフォン酸、トルエンスルフォン酸、フタル酸、マロン酸、蟻酸、酢酸、蓚酸等の有機酸や、メタクリル酸、アクリル酸、イタコン酸等の不飽和有機酸やテトラメチルアンモニウム塩酸塩、テトラブチルアンモニウム塩酸塩等のアンモニウム塩をあげることがでる。また、塩基としては、アンモニア水、ジエチルアミン、トリエチルアミン、ジブチルアミン、シクロヘキシルアミン等の第１級、２級または３級脂肪族アミン、ピリジン等の芳香族アミン、水酸化ナトリウム、水酸化カリウム、テトラメチルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド等の第４級アンモニウムヒドロキシド類を挙げることができる。これらの中で好ましい例を挙げると酸としては、有機酸、不飽和有機酸、塩基としては第３級アミンもしくは第４級アンモニウムヒドロキシドを挙げられる。これら、酸もしくは塩基の添加量は、アルコキシシラン化合物１００質量部に対して０.００１質量部〜１.０質量部、好ましくは０.０１質量部〜０.１質量部である。
【００７６】
本発明のシリカ微粒子含有ハードコート層は、さらにシリコーン系又はフッ素系化合物の撥水・撥油剤を含有し、８０度以上の水との接触角を有することが好ましい。上記撥水・撥油剤は、市販のシリコーン系又はフッ素系界面活性剤を適量添加することにより、８０度以上の水接触角となるように表面張力を調整することにより得られる。これにより防湿性に優れたハードコート層が得られる。
【００７７】
或いは、例えば前述のシリコン変性、フッ素変性したオリゴマー、モノマー或いは樹脂等を用いた紫外線硬化性樹脂を用いてハードコート層を形成することによっても得ることができる。低透湿性ハードコート層は、水蒸気を殆ど透過しない層であり、本発明では、通常、透湿度が０．５ｇ／ｍ^２・２４ｈ以下（ＪＩＳ−Ｚ−０２０８）の層を言う。この低透湿性ハードコート層は通常シリカ微粒子を含んでいないので、この層の上に本発明のシリカ微粒子含有ハードコート層を設ける必要がある。
【００７８】
本発明のハードコート層には、必要に応じて各種添加剤を添加することができるが、これらの添加剤としては、例えば酸化防止剤、紫外線吸収剤、光安定剤、シランカップリング剤、老化防止剤、熱重合禁止剤、着色剤、レベリング剤、界面活性剤、保存安定剤、可塑剤、滑剤、溶媒、無機系充填材、有機系充填材、フィラー、濡れ性改良剤、塗面改良剤等を挙げることができる。
【００７９】
本発明の耐摩耗性フィルムのハードコート層の表面には、反射防止層を設けることが好ましい。
【００８０】
反射防止層としては、例えば下記のものを使用することができる。
【００８１】
ａ） 高屈折率透明薄膜を１層のみ設けたもの（ｂ） 中屈折率透明薄膜／高屈折率透明薄膜の順で各１層ずつ、合計２層に積層したもの（ｃ） 中屈折率透明薄膜／低屈折率透明薄膜／高屈折率透明薄膜の順で各１層ずつ、合計３層に積層したもの（ｄ） 高屈折率透明薄膜／低屈折率透明薄膜／高屈折率透明薄膜／低屈折率透明薄膜の順で各１層ずつ、合計４層に積層したもの（ｅ） 高屈折率透明薄膜／低屈折率透明薄膜／高屈折率透明薄膜／低屈折率透明薄膜／高屈折率透明薄膜の順で各１層ずつ、合計５層に積層したものここで、高屈折ないし中屈折率透明薄膜としては、ＩＴＯ（スズインジウム酸化物）又はＺｎＯ、ＡｌをドープしたＺｎＯ、ＴｉＯ_２、ＳｎＯ_２、ＺｒＯ等の屈折率１．８以上の薄膜を採用することができる。
【００８２】
また、低屈折ないし中屈折率透明薄膜としては、ＳｉＯ_２、ＭｇＦ_２、Ａｌ_２Ｏ_３、アクリル樹脂、ウレタン樹脂、シリコーン樹脂、フッ素樹脂等の屈折率が１．６以下の薄膜を用いることができる。
【００８３】
これら高屈折率透明薄膜、中屈折率透明薄膜及び低屈折率透明薄膜の膜厚は、光の干渉で可視光領域での反射率を下げることができるように、膜構成、膜種、中心波長等により適宜決定される。
【００８４】
このような透明薄膜は、蒸着、スパッタリング、イオンプレーティング、ＣＶＤ、マイクログラビアコーティング、ダイレクトグラビアコーティング、スロットダイコーティング法等により形成することができる。
【００８５】
或いは、反射防止層が、ハードコート層上に形成された高屈折率導電層と該高屈折率導電層上に形成された低屈折率層とからなり、該高屈折率導電層は厚さが１００〜６００ÅのＩＴＯ膜（スズ・インジウム酸化物膜）であり、該低屈折率層は厚さが９００〜１５００ÅのＳｉＯ_２膜であることも好ましい。
【００８６】
このような反射防止層は、高屈折率導電層と低屈折率層の２層構造であるため、単層構造の反射防止層を設けたものに比べて反射防止性能が良好であり、しかも、多層構造の反射防止層を設けたものに比べて構成が簡易で低コストにて形成することができる。また、高屈折率導電層を有するため、反射防止性能に加えて帯電防止性能も兼備する。
【００８７】
上記のように、反射防止層として、厚さが１００〜６００ÅのＩＴＯ膜よりなる高屈折率導電層と、厚さが９００〜１５００ÅのＳｉＯ_２膜よりなる低屈折率層５との２層構造の反射防止層を形成する場合、ＩＴＯ膜の厚さが１００Å未満では十分な帯電防止機能が得られず、６００Åを超えると膜形成コストが高騰する。また、このＩＴＯ膜の厚さが１００〜６００Åの範囲外であると、厚さ９００〜１５００ÅのＳｉＯ_２との積層構造で良好な反射防止性能を得ることができなくなる。
【００８８】
また、ＳｉＯ_２膜の厚さが９００〜１５００Åの範囲外では、１００〜６００Åの厚さのＩＴＯ膜との積層構造で良好な反射防止性能を得ることができなくなる。
【００８９】
ＩＴＯ膜及びＳｉＯ_２膜は、蒸着、スパッタリング、イオンプレーティング、ＣＶＤ法等により形成することができる。
【００９０】
本発明のハードコート層上に反射防止層を設けられた場合、有機ポリマーフィルムとハードコート層と反射防止層の３層からなる積層体の３６５ｎｍにおける光線透過率が４０％以下であることが好ましい。
【００９１】
３６５ｎｍにおける光線透過率が４０％以下にすると、本発明の耐摩耗性フィルムは紫外線等の周囲環境に大きな影響を及ぼされることなく、耐候性、耐久性に優れるため、黄変や膜剥離の問題が防止される。
【００９２】
上記積層体は、例えば下記▲１▼、▲２▼又は▲３▼の構成とすることができる。
【００９３】
▲１▼有機ポリマーフィルムとハードコート層との間に紫外線カット層を設ける。
【００９４】
▲２▼ハードコート層を紫外線カット層とする。
【００９５】
▲３▼ 反射防止層を紫外線カット層とする。
【００９６】
上記積層体の３６５ｎｍにおける光線透過率は低い程好ましく、本発明において、３６５ｎｍにおける光線透過率は好ましくは３０％以下であり、３５０ｎｍの波長の光に対する光線透過率が２０％以下、特に１０％以下、とりわけ５％以下であることが望ましい。
【００９７】
上記▲２▼のように紫外線カット層を形成する場合、この紫外線カット層としては、アクリル樹脂、ウレタン樹脂、シリコーン樹脂、エポキシ樹脂等の適当なコーティング材に公知の紫外線吸収材を０．０５〜１０質量％程度配合してベースフィルム１上にコーティングすれば良い。このようにして形成される紫外線カット層７の厚さは０．５〜２０μｍ程度とするのが好ましい。
【００９８】
▲２▼のハードコート層自体を紫外線カット性とする場合、紫外線カットハードコート層は、このようなハードコート用の材料（紫外線硬化性樹脂）に公知の紫外線吸収材を０．０５〜５質量％の範囲で配合してコーティングすることにより形成することができる。
【００９９】
▲３▼反射防止層自体を紫外線カット性とするためには、高屈折率透明薄膜の材料として４００ｎｍ付近の光の通過性が高く、３５０ｎｍ付近及びそれ以下の光の吸収が多い材料を用いるのが好ましく、このような材料としては、ＩＴＯ、ＺｎＯ等が挙げられる。
【０１００】
こうして得られる耐摩耗性フィルムは、自動車、鉄道車両、ビル、ショーケース等に使用される耐擦傷性、耐衝撃性、耐貫通性等に優れたフィルム強化ガラス、太陽電池用セルの表面側保護部材又は裏面側保護部材等に有利に使用することができる。具体的には、自動車の嵌め込みガラス、サイドガラス及びリヤガラス、鉄道車両、例えば普通車両、急行車両、特急車両及び寝台車両等の乗客出入り用開閉ドアの扉ガラス、窓ガラス及び室内ドアガラス、ビル等の建物における窓ガラス及び室内ドアガラス等、室内展示用ショーケース及びショーウィンド等である。
【０１０１】
【実施例】
以下に実施例を示し、本発明についてさらに詳述する。
【０１０２】
［実施例１］
（１）ハードコート形成用紫外線硬化性樹脂塗布液の調製
ジペンタエリスリトールヘキサアクリレート（ＤＰＨＡ）１０．９２質量部、光重合開始剤として１−ヒドロキシシクロヘキシルフェニルケトン（ＨＣＨＰＫ）１．０８質量部及びコロイダルシリカ分散液（商品名：ＭＥＫ−ＳＴ、日産化学（株）社製、シリカの１次粒子径１０〜２０ｎｍ、シリカ含有量３０質量％、メチルエチルケトン分散液）１５０質量部を混合し、紫外線硬化性樹脂塗布液を得た。
（２）耐摩耗性フィルムの作製
ＰＥＴフィルム（１２５μｍ厚；商品名テトロンＨＳ、帝人デュポン社製）の表面に、上記紫外線硬化性樹脂塗布液を、ワイヤーバーコータＮｏ．１０により塗布し、６０℃で５分間溶剤を蒸発させた後、空気雰囲気下で高圧水銀灯で紫外線照射し（０．５Ｊ／ｃｍ^２）、層厚５μｍのハードコート層を形成した。
【０１０３】
こうして耐摩耗性フィルムを得た。
【０１０４】
［実施例２］
（１）ハードコート形成用紫外線硬化性樹脂塗布液の調製
実施例１において、さらにフッ素含有シランカップリング剤（パーフルオロアルキルシラン、ＦＡＳ）０．１６質量部を添加した以外同様に作製した。
（２）耐摩耗性フィルムの作製
上記の塗布液を用いて実施例１と同様に耐摩耗性フィルムを得た。
【０１０５】
［実施例３］
（１）ハードコート形成用紫外線硬化性樹脂塗布液の調製
実施例１において、さらにフッ素含有シランカップリング剤（パーフルオロアルキルシラン、ＦＡＳ）０．１６質量部を添加した以外同様に作製した。
（２）耐摩耗性フィルムの作製
上記の塗布液をワイヤーバーコータＮｏ．３０で塗布することにより、ハードコート層の層厚を１５μｍに変更した実施例１と同様に耐摩耗性フィルムを得た。
【０１０６】
［実施例４］
（１）ハードコート形成用熱硬化性組成物塗布液の調製
コロイダルシリカ分散液（商品名：０−４０、日産化学（株）社製、シリカの１次粒子径１０〜２０ｎｍ、シリカ含有量４０質量％、水分散液）２０７質量部、メチルトリメトキシシラン（ＭＴＳ）２０．７質量部及び酢酸０．７質量部を混合し、温度５０℃に保持し、２時間撹拌し、加水分解させた。得られた反応混合物にｎ−ブチルアルコール１．９５質量部、イソプロピルアルコール１．９５質量部、酢酸ナトリウム０．１２６質量部及び酢酸１．１質量部を添加し、熱硬化性組成物塗布液を得た。
（２）耐摩耗性フィルムの作製
ＰＥＴフィルム（１２５μｍ厚；商品名テトロンＨＳ、帝人デュポン社製）の表面に、上記熱硬化性組成物塗布液を、ワイヤーバーコータＮｏ．１０により塗布し、１００〜１２０℃で３０分間加熱硬化させ、層厚５μｍのハードコート層を形成した。
【０１０７】
こうして耐摩耗性フィルムを得た。
【０１０８】
［実施例５］
（１）ハードコート形成用熱硬化性組成物塗布液の調製
実施例４において、さらにフッ素含有シランカップリング剤（パーフルオロアルキルシラン、ＦＡＳ）０．２３質量部を添加した以外同様に作製した。
（２）耐摩耗性フィルムの作製
上記の塗布液を用いて実施例４と同様に耐摩耗性フィルムを得た。
【０１０９】
［実施例６］
（１）ハードコート形成用熱硬化性組成物塗布液の調製
実施例４において、さらにフッ素含有シランカップリング剤（パーフルオロアルキルシラン、ＦＡＳ）０．２３質量部を添加した以外同様に作製した。
（２）耐摩耗性フィルムの作製
上記の塗布液をワイヤーバーコータＮｏ．３０で塗布することにより、ハードコート層の層厚を１５μｍに変更した実施例４と同様に耐摩耗性フィルムを得た。
【０１１０】
［比較例１］
（１）ハードコート形成用紫外線硬化性樹脂塗布液の調製
実施例１において、コロイダルシリカ分散液の量を６０質量部に変更した以外同様に作製した。
（２）耐摩耗性フィルムの作製
上記の塗布液を用いて実施例１と同様に耐摩耗性フィルムを得た。
【０１１１】
［比較例２］
（１）ハードコート形成用紫外線硬化性樹脂塗布液の調製
実施例１において、コロイダルシリカ分散液を使用しなかった以外同様に作製した。
（２）耐摩耗性フィルムの作製
上記の塗布液を用いて実施例１と同様に耐摩耗性フィルムを得た。
【０１１２】
［比較例３］
（１）ハードコート形成用紫外線硬化性樹脂塗布液の調製
実施例４において、コロイダルシリカ分散液を使用しなかった以外同様に作製した。
（２）耐摩耗性フィルムの作製
上記の塗布液を用いて実施例４と同様に耐摩耗性フィルムを得た。
【０１１３】
＜耐摩耗性フィルムの評価＞
（１）耐摩耗性は、ＪＩＳ−Ｒ３２２１に従い、テーバー摩耗試験機を用いてハードコート層側の表面に対してテーバー試験（摩耗輪：ＣＳ−１０Ｆ；荷重：５００ｇ；１０００回の条件）を行い、試験後のヘイズを測定した。ヘイズ値５未満を◎、５〜１０を○、１０超過を×とした。
【０１１４】
（２）耐擦傷性は、ハードコート層の表面に、スチールウール＃００００を、スチールウールの上に２００ｇ／ｃｍ^２の荷重を載せて、１０往復させ、傷が付かないものを◎、傷が若干付くものを○、傷が目立って付くものを×とした。
【０１１５】
（３）密着性は、ＪＩＳ−Ｋ５４００に従い測定した。即ち、ハードコート層の表面に１ｍｍ間隔で１００個の碁盤目をつくり、市販のセロファンテープをその表面に密着させた後、急激に剥がした時に剥離せずに残存したマス目の数（Ｘ）をＸ／１００で表示した。
【０１１６】
（４）干渉縞の評価は、三波長型蛍光灯下にサンプルを置き、ハードコート層表面を目視で観察し、干渉縞が全くないものを◎、わずかにあるものを○、目立つものを×とした。
【０１１７】
（５）水に対する接触角は、温度２３℃、湿度５０％RHでハードコート層表面に蒸留水を一滴落とし（水滴直径２ｍｍ）、滴下後１分後に、層表面と蒸留水との接触角を、接触角計（ＣＡ−ＤＴ−Ａ型、協和界面化学（株）製）を用いて測定した。試料数３個で、左右２カ所の、計６回測定し、これらの平均値を求め接触角とした。
【０１１８】
各例の組成、測定結果を下記の表１に示す。

上記実施例で得られた耐擦傷性、耐摩耗性が優れ、実施例３、６ではさらに防湿性（水との接触角が大きい）も優れていることがわかる。
【０１１９】
［実施例７］
図２に示す構成を有する耐摩耗性フィルムを作製した。
（２）耐摩耗性フィルムの作製
ＰＥＴフィルム（１２５μｍ厚；商品名テトロンＨＳ、帝人デュポン社製）の表面に、比較例２で使用した紫外線硬化性樹脂塗布液を、ワイヤーバーコータＮｏ．１６により塗布し、６０℃で５分間溶剤を蒸発させた後、空気雰囲気下で高圧水銀灯で紫外線照射し（０．５Ｊ／ｃｍ^２）、層厚１０μｍのハードコート層を形成し、次いで実施例２で使用した紫外線硬化性樹脂塗布液を、ワイヤーバーコータＮｏ．１０により塗布し、６０℃で５分間溶剤を蒸発させた後、空気雰囲気下で高圧水銀灯で紫外線照射し（０．５Ｊ／ｃｍ^２）、層厚５μｍのハードコート層を形成した。こうして耐摩耗性フィルムを得た。
【０１２０】
上記実施例７で得られた耐摩耗性フィルムは、実施例３と同様に全ての評価が優れたものであり、さらに目視による透明性も優れていた。また、シリカ量を低く押さえることができたので経済的にも有利なものである。
【０１２１】
【発明の効果】
以上説明した本発明による耐摩耗性フィルムは、耐擦傷性、耐摩耗性に優れており、好適態様ではさらに防湿性も優れている。このため本発明の耐摩耗性フィルムは、自動車、鉄道車両、ビル、ショーケース等に使用される耐擦傷性、耐衝撃性、耐貫通性等に優れたフィルム強化ガラス、太陽電池用セルの表面側保護部材又は裏面側保護部材等に有利に使用することができる。具体的には、自動車の嵌め込みガラス、サイドガラス及びリヤガラス、鉄道車両、例えば普通車両、急行車両、特急車両及び寝台車両等の乗客出入り用開閉ドアの扉ガラス、窓ガラス及び室内ドアガラス、ビル等の建物における窓ガラス及び室内ドアガラス等、室内展示用ショーケース及びショーウィンド等である。
【０１２２】
【図面の簡単な説明】
【図１】本発明の耐摩耗性フィルムの基本構成を示す断面図である。
【図２】本発明の耐摩耗性フィルムの好ましい基本構成を示す断面図である。
【図３】本発明の積層体の基本構造を示す断面図である。
【符号の説明】
１１，２１，３１ 有機ポリマーフィルム
１２，２２ａ，２２ｂ，３２ ハードコート層
３３ 透明接着剤層[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an abrasion-resistant film having a hard coat layer on the surface and a laminate having a transparent adhesive layer. In particular, it is advantageous for glass having excellent scratch resistance, impact resistance, penetration resistance, etc. used for automobiles, railway vehicles, buildings, showcases, etc. The present invention relates to a wear-resistant film and a laminate that can be used in the manufacturing process.
[0002]
[Prior art]
Plastic is widely used as a three-dimensional molded body or as a film for various applications. However, depending on the application, the surface characteristics of these molded products may be insufficient, and various surface treatments are applied.
[0003]
For example, inorganic fillers such as silica, polyethylene powder, or organic fillers of polycarbonate have been added to improve the scratch resistance, slipperiness, and contamination resistance of plastic molded parts such as plastic optical parts, touch panels, and liquid crystal elements. And a method of adding an additive such as silicone. When the filler is added, the haze value is increased, and when silicone is added, the scratch resistance is insufficient.
[0004]
Further, in order to improve the scratch resistance and stain resistance of the surface of a plastic molded product, particularly a plastic film, a process of providing a hard coat layer of an ultraviolet curable resin on the surface is also performed. As a result, the scratch resistance and the like are improved.
[0005]
As a material for forming a hard coat layer formed on the film surface, a silicon alkoxide-based coating agent containing a vinyl group-containing silicon compound having excellent hardness, light resistance and wear resistance (Japanese Patent Laid-Open No. 6-73329), A liquid curable resin composition (JP-A-10-273595) containing a reaction product of an alkoxysilane compound and silica particles having improved scratch resistance, slipperiness, weather resistance, stain resistance, etc., and colloidal silica A radiation curable resin composition (Japanese Patent Laid-Open No. 2000-7944) containing 50% by mass or less is known.
[0006]
[Problems to be solved by the invention]
However, when the plastic film with a hard coat layer is used as a reinforcing material for a side glass of an automobile, a high degree of wear resistance is required. Therefore, the above-mentioned colloidal silica-containing hard coat with improved wear resistance is sufficient. I can't say that. Moreover, when the above-mentioned plastic film with a hard coat layer is used as a protective member for a solar battery cell, the effect of suppressing moisture permeability is not sufficient, and problems such as rust generation and peeling of the protective member may occur in the cell. is there.
[0007]
Accordingly, an object of the present invention made in view of such a point is to provide an abrasion resistant film having excellent scratch resistance and abrasion resistance.
[0008]
Another object of the present invention is to provide an abrasion-resistant film having excellent scratch resistance, abrasion resistance, and moisture resistance.
[0009]
In particular, glass (film tempered glass) excellent in scratch resistance, impact resistance, penetration resistance, etc. used in automobiles, etc., and can be advantageously used for the surface side protection member or the back side protection member of solar cell. The object is to provide an abradable film.
[0010]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors,
On one side of the organic polymer film, a hard coat layer made of a cured film of an ultraviolet curable resin that does not contain silica fine particles is provided. Has a primary particle size in the range of 1 to 200 nm A hard coat layer comprising a cured film of an ultraviolet curable resin containing silica fine particles, the content of the silica fine particles with respect to the cured film being 70 to 90% by mass, and
A transparent adhesive layer is provided on the surface of the organic polymer film where the hard coat layer is not provided, and
The layer thickness of the hard coat layer not containing silica fine particles is 10 to 15 μm, Has a primary particle size in the range of 1 to 200 nm It came to obtain the abrasion-resistant film characterized by the layer thickness of the hard-coat layer containing a silica fine particle being 2-5 micrometers.
[0011]
The above wear-resistant film smell In the hard coat layer containing silica fine particles, Primary particle size of Rica fine particles As above 1 to 200 nm range And In particular, it is preferably in the range of 20 to 50 nm (transparency is improved). The silica fine particles have a polymerizable unsaturated group, and those formed by a reaction between the silica fine particles and an alkoxysilane compound having a polymerizable unsaturated group (and preferably a urethane bond) are particularly preferable.
[0012]
The hard coat layer preferably further contains a silicone-based or fluorine-based compound water / oil repellent and preferably has a contact angle with water of 80 ° or more. The moisture-proof property is further improved, and the transparency is not lowered as in the case where a vapor-deposited film of an inorganic oxide is provided as the moisture-proof layer. It is preferable that an antireflection layer is further formed on the surface of the hard coat layer. This is advantageous for applications requiring anti-glare properties (for example, automobiles).
[0013]
The organic polymer of the film is preferably polyethylene terephthalate, polypropylene, poly (meth) acrylate or polyethersulfone.
[0015]
The silica fine particle-containing hard coat layer tends to decrease in transparency as the silica content increases, and the hardness tends to decrease as the hard coat layer thickness decreases. The above-mentioned invention eliminates this disadvantage, and the lower layer is a relatively thick hard coat layer not containing silica fine particles, and the upper layer is a hard coat layer containing silica fine particles that is relatively thin. Further, when the thickness of the hard coat layer is about 5 μm or less, interference fringes are generated. Therefore, in order to prevent this, when the layer thickness is about 15 μm, the price of the high silica content layer increases, but the above configuration is adopted. This can be solved.
[0016]
The layer thickness of the hard coat layer not containing silica fine particles is 2 to 20 μm (preferably 10 to 15 μm), and the layer thickness of the hard coat layer containing silica fine particles is 2 to 20 μm (preferably 2 to 5 μm). It is common. It is preferable that the hard coat layer not containing silica fine particles is a cured film of only a radiation curable resin or a thermosetting silicone composition. The curable composition containing silica fine particles is preferably a radiation curable resin or a thermosetting silicone composition. The preferred embodiment of the primary particle size of the silica fine particles is as described above. The preferred embodiment of the silica fine particles is also as described above. It is preferable that the silica fine particle-containing hard coat layer further contains a silicone-based or fluorine-based compound water / oil repellent and has a contact angle with water of 80 degrees or more. It is preferable that an antireflection layer is further formed on the surface of the silica fine particle-containing hard coat layer. Preferred embodiments of the organic polymer are as described above.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
The abrasion-resistant film of the present invention has a basic structure in which a hard coat layer containing a high amount of silica fine particles is provided on an organic polymer film.
[0019]
Hereinafter, with reference to FIG.1 and FIG.2, the abrasion-resistant film of this invention is explained in full detail.
[0020]
FIG. 1 shows the basic structure of the wear-resistant film of the present invention. In FIG. 1, a silica fine particle-containing hard coat layer 12 is provided on the surface of an organic polymer film 11. The hard coat layer 12 may also be provided on the opposite surface of the film 11. The hard coat layer 12 contains 70 to 90% by mass of silica fine particles with respect to the total amount of the cured coating. Since the hard coat layer of the wear resistant film of the present invention contains silica fine particles at a high concentration, the scratch resistance and the wear resistance are remarkably improved as compared with the conventional one.
[0021]
FIG. 2 shows the basic structure of a preferred embodiment of the wear-resistant film of the present invention. In FIG. 2, a silica fine particle-free hard coat layer 22b is provided on the surface of the organic polymer film 21, and a silica fine particle-containing hard coat layer 22a is further provided thereon. Two layers of the hard coat layers 22 a and 22 b or any one of these layers may be provided on the opposite surface of the film 21. The upper hard coat layer 22a contains 70 to 90% by mass of silica fine particles with respect to the total amount of the cured coating.
[0022]
The silica fine particle-containing hard coat layer tends to decrease in transparency as the silica content increases, and the hardness tends to decrease as the hard coat layer thickness decreases. The disadvantage shown in FIG. 2 is eliminated. That is, the lower layer is a relatively thick hard coat layer containing no silica fine particles, and the upper layer is a hard coat layer containing 70 to 90% by mass of silica fine particles and a relatively thin hard coat layer. Further, interference fringes generally occur when the thickness of the hard coat layer is about 5 μm or less. In order to prevent this, it is necessary to make the layer thickness about 15 μm. However, since the price is high in the high silica content layer, by using the configuration of FIG. Since the layer thickness of the high silica content layer can be reduced, the price can be suppressed.
[0023]
Since the wear-resistant film of the present invention is particularly excellent in wear resistance and scratch resistance as described above, it is of course used for ordinary applications, and particularly scratch resistance of automobile side glass, Films with excellent impact resistance, penetration resistance, etc. can be advantageously used for films of tempered glass, and are excellent in moisture resistance containing a water- or oil-repellent agent of a silicone or fluorine compound that is a preferred embodiment of the present invention. By setting it as a hard-coat layer, it can be used especially advantageously for the film of the surface side protection member or back surface side protection member of the cell for solar cells. When used for a side glass, the abrasion-resistant film of the present invention is adhered to the glass via a transparent adhesive layer made of an ethylene vinyl acetate copolymer, PVB (polyvinyl butyral) or the like. Moreover, when using for a solar cell, the abrasion-resistant film of this invention is arrange | positioned, for example on both sides of a cell, and it laminates | stacks on both sides of a cell so that it may seal with the said transparent adhesive layer.
[0024]
When a film is used for the side glass, the hard coat layer faces the indoor side, and comes into contact with the frame around the window by opening and closing the window, so that high wear resistance is required. In addition, when used for solar cells, if the surface is scratched, the amount of light received from the embodiment is reduced, and if moisture penetrates, it causes rusting of the cell. The abrasion-resistant film of the present invention is excellent in the above performance and can be suitably used for these.
[0025]
For the use as described above, the laminate of the present invention in which a transparent adhesive layer is provided on the surface on which the hard coat layer of the wear-resistant film of the present invention is not provided can be advantageously used. it can. By using such a laminate, adhesion with glass or the like can be appropriately performed, and a flexible production system can be adopted.
[0026]
In FIG. 3, the basic structure of the said laminated body of this invention is shown. In FIG. 3, a silica fine particle-containing hard coat layer 32 is provided on the surface of an organic polymer film 31, and a transparent adhesive layer 33 is provided on the opposite side. The hard coat layer 32 can have the two-layer configuration described above.
[0027]
Examples of the organic polymer used in the organic polymer films 11, 21, 31 of the present invention include polyester (eg, polyethylene terephthalate, polyethylene naphthalate, polyethylene butyrate), polycarbonate, poly (meth) acrylate (acrylic resin), polyamide ( Examples include nylon) and polyethersulfone. Polyethylene terephthalate (PET), polycarbonate, and poly (meth) acrylate polyethersulfone are preferable, and PET is particularly preferable. The thickness of the film is generally 6 to 250 μm.
[0028]
The curable material used for the hard coat layers 12 and 22a of the present invention provided on the organic polymer film is composed of a radiation curable resin (generally an ultraviolet curable resin) or a cured film of a thermosetting composition. A hard coat layer excellent in scratch resistance can be provided on the film very easily by using an ultraviolet curable resin.
[0029]
As the thermosetting composition, a thermosetting silicone composition (for example, methyltrimethoxysilane forming an organic polysiloxane) is preferable. The main component of the composition is generally R _x Si (OR ') _4-x [Wherein R and R ′ represent an organic group, preferably a methyl group or an ethyl group, and X is 0, 1, 2, or 3]. This composition is three-dimensionally cross-linked by dehydration condensation of silanol groups to obtain a high hardness coating. Generally, it can be cured by heating at 80 to 220 ° C. for 10 minutes to 1 hour. It is also possible to obtain a curable resin using an ultraviolet curable resin and a thermal polymerization initiator.
[0030]
As the ultraviolet curable resin, a known ultraviolet curable resin (including a polymerizable oligomer, a polyfunctional monomer, a monofunctional monomer, a photopolymerization initiator, an additive, and the like) can be used. When using an electron beam etc. as a radiation, it can use similarly, However, In the case of an electron beam, generally a photoinitiator is not required.
[0031]
Such ultraviolet curable resins include, for example, urethane oligomers having a plurality of ethylenic double bonds (preferably acryloyl groups or methacryloyl groups), oligomers such as polyester oligomers or epoxy oligomers, pentaerythritol tetraacrylate (PETA), pentaerythritol tetra It is preferably composed mainly of a polymerizable oligomer such as methacrylate and dipentaerythritol hexaacrylate (DPEHA) and / or a polyfunctional monomer. The functional polymerization monomer used for the production of the modified silica fine particles described later can also be used as appropriate.
[0032]
As described above, the resin is generally composed of an oligomer, and if necessary, a reactive diluent (polyfunctional monomer, monofunctional monomer) and a photopolymerization initiator. Examples of photopolymerization initiators include benzoin, benzophenone, benzoyl methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, dibenzyl, 5-nitroacenaphthene, hexachlorocyclopentadiene, p-nitrodiphenyl, p-nitroaniline. 2,4,6-trinitroaniline, 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9-benzanthrone;
Acetophenone, acetophenone benzyl ketal, anthraquinone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone compound, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4 ' -Dimethoxybenzophenone, 4,4'-diaminobenzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one Carbazole, xanthone, 1,1-dimethoxydeoxybenzoin, 3,3′-dimethyl-4-methoxybenzophenone, thioxanthone compounds, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothi Xanthone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, tri Phenylamine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bisacylphosphine oxide, benzyldimethyl ketal, 1- Hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, fluorenone, fluorene, benzaldehyde, Michler ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane -1-one, 3-methylacetate Enone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone (BTTB) and the like, and BTTB and dye sensitizers such as xanthene, thioxanthene, coumarin, ketocoumarin and the like. And the like. Of these, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one is preferred.
[0033]
These can be used alone or in combination of two or more. One kind of each of the oligomer, the reactive diluent and the initiator may be used, or two or more kinds thereof may be used in combination. The content of the photopolymerization initiator is preferably 5 parts by mass or less with respect to 100 parts by mass of the ultraviolet curable resin.
[0034]
The ultraviolet curable resin used in the present invention may further contain a silicone polymer. A graft copolymer having a silicone as a side chain is preferred, and an acrylic graft copolymer having a silicone as a side chain is more preferred. As the silicone-based graft copolymer obtained by radical polymerization of an acrylic-modified silicone polymer monomer and a radical polymerizable monomer, the acrylic-modified silicone is represented by the following formula (III) and the following formula (IV): A product obtained by condensing the acrylic compound shown can be mentioned.
[0035]
[Chemical 1]

(Where R ⁶ And R ⁷ Represents a monovalent aliphatic hydrocarbon group, phenyl group or monovalent halogenated hydrocarbon group having 1 to 10 carbon atoms, and q is a positive number of 1 or more. )
[0036]
[Chemical 2]

(Where R ⁸ Represents a hydrogen atom or a methyl group, R ⁹ Represents a methyl group, an ethyl group or a phenyl group, and two R ⁹ May be the same or different from each other, and Z represents a chlorine atom, a methoxy group or an ethoxy group. )
[0037]
The silicone represented by the formula (III) can be obtained as a commercial product, and those suitable for the purpose can be used. R in the formula (III) ⁶ And R ⁷ Is a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a phenyl group or a monovalent halogenated hydrocarbon. Examples of the monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms include a methyl group, Examples of the monovalent halogenated hydrocarbon include a 3,3,3-trifluoropropyl group, a 4,4,4-trifluoro-3,3-difluorobutyl group, and a monovalent halogenated hydrocarbon. -A chloroethyl group etc. are mentioned. R ⁸ And R ⁹ Particularly preferred is a methyl group.
[0038]
In the formula (III), q is a positive number of 1 or more, but generally an oil is obtained from copolymerization of an acrylic-modified silicone derived from a high molecular weight silicone having a q number of 100 or more and a radical polymerizable monomer. From the copolymerization of an acrylic-modified silicone derived from a low molecular weight silicone having a q number of 100 or less and a radical polymerizable monomer, an oily or jelly-like material tends to be obtained. Various types such as a solid and a solid can be obtained.
[0039]
Next, examples of the acrylsilane compound represented by the formula (IV) include γ-methacryloxypropyldimethylchlorosilane, γ-methacryloxypropyldimethylethoxysilane, γ-methacryloxypropyldiphenylchlorosilane, γ-acryloxypropyldimethylchlorosilane, Examples include γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltrichlorosilane, and the like. These acrylic silane compounds can be easily obtained by reacting a silicon compound and a compound having an aliphatic multiple bond in the presence of chloroplatinic acid according to the method of JP-B-33-9969.
[0040]
In addition, radical copolymerization of an acrylic-modified silicone and a radical polymerizable monomer can be performed by a conventionally known method, such as a radiation irradiation method or a method using a radical polymerization initiator. Furthermore, when copolymerizing by the ultraviolet irradiation method, a known sensitizer is used as a radical polymerization initiator, and when copolymerizing by electron beam irradiation, it is not necessary to use a radical polymerization initiator. The silicone copolymer thus obtained is a comb-shaped graft copolymer having a radical polymerizable monomer as a trunk and silicone as a branch.
[0041]
Examples of commercially available silicone copolymers include Cymac US-150, US-270, US-350, US-450, Reseda GP-700 (manufactured by Toagosei Co., Ltd.), and the like.
[0042]
As described above, the hard coat layer of the present invention contains silica fine particles at a high concentration of 70 to 90% by mass. Preferably it is 75-85 mass%.
[0043]
The silica fine particles are powdery silica or colloidal silica and generally have a primary particle size in the range of 1 to 200 nm (mμ), preferably in the range of 1 to 100 nm, and more preferably in the range of 20 to 50 nm. The shape of the silica fine particles is spherical, hollow, porous, rod-like, plate-like, fibrous, or indefinite, and preferably spherical. The specific surface area of silica fine particles is 0.1 to 3000 m. ² / G, preferably 10 to 1500 m ² / G. These silica fine particles can be used in a dry state or dispersed in water or an organic solvent, and a dispersion of fine silica particles known as colloidal silica can be used directly. In particular, it is preferable to use colloidal silica in order to obtain transparency. When the dispersion solvent of colloidal silica is water, the hydrogen ion concentration is in the range of 2 to 10 as a pH value, and acidic colloidal silica having a pH of 3 to 7 is preferably used. When the colloidal silica dispersion solvent is an organic solvent, methanol, isopropyl alcohol, ethylene glycol, butanol, ethylene glycol monopropyl ether, methyl ethyl ketone, methyl isobutyl ketone, toluene are used as the organic solvent. In addition, a solvent such as xylene and dimethylformamide, an organic solvent compatible with these solvents, or a mixture with water may be used. Preferred dispersing solvents are methanol, isopropyl alcohol, methyl ethyl ketone, and xylene. Examples of commercially available silica fine particles include, as colloidal silica, methanol silica sol, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST and ST-UP manufactured by Nissan Chemical Industries, Ltd. ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL and the like can be mentioned. Examples of the powdered silica include Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600 and Aerosil OX50 manufactured by Nippon Aerosil Co., Ltd., Sildex H31, H32, H51, H52, H121, H122, manufactured by Asahi Glass Co., Ltd. Examples include E220A manufactured by Nippon Silica Kogyo Co., Ltd., E220 Silicia 470 manufactured by Fuji Silysia Co., Ltd., SG flake manufactured by Nippon Sheet Glass Co., Ltd., and the like.
[0044]
Silica fine particles contained in the curable resin for forming a hard coat layer of the present invention are formed by reaction of silica fine particles with an alkoxysilane compound having a polymerizable unsaturated group (and preferably a urethane bond) (hereinafter referred to as “ "Modified silica fine particles") are preferred, and those having the following constitution are preferred.
[0045]
The modified silica fine particle of the present invention comprises an alkoxysilane compound and a silica fine particle having a polymerizable unsaturated group, a urethane bonding group, and an organic group represented by the formula (I) -X-C (= Y) -NH-. A reaction product obtained by reaction is preferable (in the above formula (I), X is —NH—, —O— or —S—, Y is an oxygen atom or a sulfur atom, provided that X is When -O-, Y is a sulfur atom).
[0046]
The modified silica fine particles are produced by a method including an operation of mixing at least an alkoxysilane compound and silica fine particles. The content of the alkoxysilane compound residue fixed to the silica fine particles is 0.01% by mass or more, preferably 0.1% by mass or more, particularly preferably 1% by mass or more. When the content of the alkoxysilane compound residue fixed in the silica fine particles is less than 0.01% by mass, the dispersibility, transparency and abrasion resistance of the silica fine particles or colloidal silica in the composition may not be sufficient. . Moreover, the ratio of the alkoxysilane compound in the raw material composition at the time of manufacture is preferably 10% by mass or more, particularly preferably 30% by mass or more. When the proportion of the alkoxysilane compound is less than 10% by mass, the film-forming property of the ultraviolet curable resin may be poor. The proportion of silica fine particles in the ultraviolet curable resin is preferably 50% by mass or less, and particularly preferably 20% by mass or less. When the ratio of the silica fine particles in the ultraviolet curable resin is 50% by mass or more, the dispersibility, transparency, and abrasion resistance of the composition of the present invention may not be sufficient.
[0047]
The alkoxysilane compound contains at least one polymerizable unsaturated group, urethane bond group, organic group represented by the formula (I) and alkoxysilyl group as constituent components in the molecule. The alkoxysilyl group is a component that is bonded to the silanol group present on the surface of the silica fine particles by hydrolysis and condensation reactions. The polymerizable unsaturated group is chemically intermolecularly subjected to addition polymerization by active radical species. It is a component that crosslinks. In addition, the —X (C═Y) NH— group and the urethane bonding group, which are divalent organic groups represented by the formula (I), are molecules having an alkoxysilyl group and molecules having a polymerizable unsaturated group. It is a structural unit that bonds pieces directly or via other molecular pieces, and at the same time generates moderate cohesive force due to hydrogen bonds between molecules, and has excellent mechanical strength in the hard coat layer of the present invention. It is considered that performance such as adhesion and heat resistance is generated. The —X (C═Y) NH— group is preferably a —S (C═O) NH— group.
[0048]
Examples of the structure of the alkoxysilane compound include the general formula (II);
[0049]
[Chemical 3]

The alkoxysilane compound represented by these can be mentioned.
[0050]
In the general formula (II), R ¹ Is a hydrogen atom, and C ₁ ~ C ₈ For example, methyl, ethyl, propyl, butyl, phenyl, octyl group, and the like. R ² Is a hydrogen atom, and C ₁ ~ C ₃ These are monovalent alkyl groups. m is 1, 2 or 3, and (R ¹ O) _m R ² Si _3-m Examples of the alkoxysilyl group represented by the formula include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, a dimethylmethoxysilyl group, and the like, preferably a trimethoxysilyl group and a trimethoxysilyl group. An ethoxysilyl group.
[0051]
In the formula,-[(C = O) NH-R ⁴ —NH (C═O) O—X—O] _p The structural unit represented by − is introduced for the purpose of extending the molecular chain in the structure represented by the formula (II). R ³ Is C ¹ ~ C ³ These are divalent organic groups. R ⁴ Is a divalent organic group, R ³ May be the same as or different from, and is usually selected from divalent organic groups having a molecular weight of 14 to 10,000, preferably 78 to 1000, such as methylene, ethylene, propylene, hexamethylene, octamethylene, A chain polyalkylene group such as dodecamethylene; an alicyclic or polycyclic divalent organic group such as cyclohexylene or norbornylene; a divalent aromatic group such as vinylene, phenylene, naphthylene, biphenylene or polyphenylene; These alkyl group-substituted products and aryl group-substituted products can also be used. These divalent organic structures may contain atomic groups composed of elements other than carbon and hydrogen atoms. In the formula, p is 0 or 1, X is a divalent organic group, and a divalent organic group derived from a compound having two or more active hydrogen atoms in the molecule capable of addition reaction with an isocyanate group. Groups such as polyalkylene glycols, polyalkylene thioglycols, polyesters, polyamides, polycarbonates, polyalkylene diamines, polyalkylene dicarboxylic acids, polyalkylene diols And a divalent organic group derived by removing two active hydrogen atoms from the polyalkylene dimercaptans. R ⁵ Is an (n + 1) -valent organic group. Such an organic group is preferably selected from a chain, branched or cyclic saturated hydrocarbon group, unsaturated hydrocarbon group, and alicyclic group. Moreover, n is preferably a positive integer of 1 to 20, more preferably 1 to 10, and further preferably 3 to 5. In the above formula, Y represents a monovalent organic group in the molecule having a polymerizable unsaturated group that undergoes an intermolecular crosslinking reaction in the presence of an active radical species. For example, acryloxy group, methacryloxy group, vinyl group, propenyl group, Examples thereof include a butadienyl group, a styryl group, an ethynyl group, a cinnamoyl group, a maleate group, and an acrylamide group. Of these, acryloxy groups are preferred.
[0052]
For the formation of the molecular structure of an alkoxysilane compound, usually an alkoxysilane having a mercapto group, that is, an active hydrogen group-containing polymerizable compound having an active hydrogen that causes an addition reaction with a mercaptoalkoxysilane, a polyisocyanate compound and an isocyanate group. It can be carried out by addition reaction with an unsaturated compound.
[0053]
As a method for producing an alkoxysilane compound, for example, the method (A); first, an adduct of a mercaptoalkoxysilane and a polyisocyanate compound is reacted to form an alkoxysilyl group, —S (C═O) NH—bond in the molecule. And an isocyanate group containing an isocyanate group is produced, and then the isocyanate remaining in the intermediate is reacted with an active hydrogen group-containing polymerizable unsaturated compound and bonded via a urethane group.
Method (B): First, an intermediate containing a polymerizable unsaturated group, a urethane bond group, and an isocyanate group in the molecule by reacting an adduct of a polyisocyanate compound and an active hydrogen group-containing polymerizable unsaturated compound. A method of forming a body and reacting it with mercaptoalkoxysilane through a —S (C═O) NH— group can be used. Further, in the above method (A) or (B), a chain, cyclic or branched compound having two or more active hydrogens in the molecule which cause an addition reaction with the isocyanate as a chain extension unit is added to the polyisocyanate. It can also be extended through a urethane bond with the compound.
[0054]
As an example of an alkoxysilane capable of forming a —S (C═O) NH— bond by directly reacting with a polyisocyanate compound in the production of the compound represented by the formula (II), as a reaction product A compound having at least one alkoxysilyl group and one mercapto group in the molecule can be selected. For example, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptopropylmethyldiethoxysilane, mercaptopropyldimethoxymethylsilane, mercaptopropylmethoxymethoxysilane, mercaptopropyltriethoxysilane, mercaptopropyltriphenoxysilane, mercaptopropyltri Mercaptoalkoxysilanes such as butoxysilane can be mentioned, and mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane are preferable. Examples of commercially available mercaptoalkoxysilanes include SH6062 manufactured by Toray Dow Corning Co., Ltd. These mercaptoalkoxysilanes may be used alone or in admixture of two or more. Further, examples of mercaptoalkoxysilanes include addition products of amino-substituted alkoxysilane and epoxy-group-substituted mercaptan, epoxysilane and α, ω Addition products with dimercapto compounds can be used. The polyisocyanate compound used when producing the alkoxysilane compound can be selected from polyisocyanate compounds composed of chain saturated hydrocarbons, cyclic saturated hydrocarbons, and aromatic hydrocarbons, alone or Two or more kinds can be mixed and used. The number of isocyanate groups in one molecule is usually 2 or more and less than 30, preferably 2 or more and less than 10. If it exceeds 30, the viscosity of the product becomes high and workability may be reduced.
[0055]
Examples of such polyisocyanate compounds include chain hydrocarbons such as tetramethylene diisocyanate, hexamethylene diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate. Polyisocyanate compounds; isophorone diisocyanate, dicyclohexylmethane diisocyanate, methylenebis (4-cyclohexylisocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, Cyclic saturated hydrocarbon polyisocyanate compounds such as hydrogenated toluene diisocyanate and 1,3-bis (isocyanatomethyl) cyclohexane; 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate -1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, paraffin Enylene diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, diphenylmethane-4,4′-diisocyanate, 4,4′-biphenylene diisocyanate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, 1,5-naphthalene diisocyanate, polyisocyanate of polydiphenylmethane And aromatic hydrocarbon polyisocyanate compounds such as
[0056]
Among these, preferable examples are a cyclic saturated hydrocarbon polyisocyanate compound and an aromatic hydrocarbon polyisocyanate compound, and a cyclic saturated hydrocarbon polyisocyanate compound is more preferable. Preferable specific examples are isophorone diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated toluene diisocyanate. Examples of commercially available polyisocyanate compounds include TDI-80 / 20, TDI-100, MDI-CR100, MDI-CR300, MDI-PH, NDI and Nippon Polyurethane Industry (manufactured by Mitsui Nisso Urethane Co., Ltd.). Examples thereof include Coronet T, Millionate MT, Millionate MR, HDI, and Takenate 600 manufactured by Takeda Pharmaceutical Company Limited.
[0057]
The amount of the polyisocyanate compound used is usually in the range of 0.1 to 100 as the isocyanate group equivalent to 1 equivalent of mercapto group of mercaptoalkoxysilane in the production method shown in the above-mentioned method (A). Of these, it is preferably added in the range of 0.5 to 10, more preferably in the range of 0.9 to 1.2. When the addition amount of the polyisocyanate compound group equivalent is less than 0.1 equivalent, the unreacted mercaptosilane is present in an amount of 0.9 equivalent or more, and the wear resistance of the coating film may not be sufficient. In addition, the use of a polyisocyanate compound exceeding 100 equivalents may cause an unreacted isocyanate group to be present in excess, resulting in a decrease in weather resistance.
[0058]
On the other hand, in the production method shown in the method (B), the polyisocyanate compound is usually in the range of 0.1 to 100 as the isocyanate group equivalent with respect to 1 equivalent of the active hydrogen group in the active hydrogen group-containing polymerizable unsaturated compound. Yes, preferably in the range of 0.5 to 10 equivalents, more preferably in the range of 0.9 to 1.2.
[0059]
In any of the methods (A) and (B), a catalyst may be added for the purpose of shortening the reaction time. As such a catalyst, either a basic catalyst or an acidic catalyst is used. Examples of the basic catalyst include amines such as pyridine, pyrrole, triethylamine, diethylamine, dibutylamine and ammonia; and phosphines such as tributylphosphine and triphenylphosphine. Of these, tertiary amines such as pyridine and triethylamine are preferred. Acid catalysts include copper naphthenate, cobalt naphthenate, zinc naphthenate, 1,4-diazabicyclo [2.2.2] octane (DABCO), methyl DABCO, tributoxyaluminum, trititanium tetrabutoxide, zirconium tetrabutoxide. Metal alkoxides; Lewis acids such as boron trifluoride diethyl etherate and aluminum chloride; tin such as tin 2-ethylhexanoate, octyltin trilaurate, dibutyltin dilaurate, octyltin diacetate List compounds. Among these catalysts, preferred are acidic catalysts, particularly preferred are tin compounds, and more preferred are octyltin trilaurate, dibutyltin dilaurate, and octyltin diacetate. The addition amount of these catalysts is 0.01-5 mass parts with respect to 100 mass parts of polyisocyanate compounds, Preferably it is 0.1-1 mass part. If the amount is less than 0.01 parts by mass, the effect of shortening the reaction time due to the addition of the catalyst is slight.
[0060]
In the production of alkoxysilyl compounds, examples of polymerizable unsaturated compounds that can be bonded to the polyisocyanate compound via a urethane bond by an addition reaction include an activity capable of forming a urethane bond by an addition reaction with an isocyanate group in the molecule. The compound having one or more hydrogen atoms in the molecule and one or more polymerizable unsaturated groups in the molecule can be used alone or as a mixture of two or more.
[0061]
Such compounds include carboxylic acid-containing polymerizable unsaturated compounds and hydroxyl group-containing polymerizable unsaturated compounds. For example, polymerizable unsaturated compounds containing carboxylic acid include (meth) acrylic acid, itaconic acid, cinnamic acid, maleic acid, fumaric acid, 2- (meth) acryloxypropyl hexahydrogen phthalate, 2 -Unsaturated aliphatic carboxylic acids such as (meth) acryloxyethyl hexahydrogen phthalate; 2- (meth) acryloxypropyl phthalate, 2- (meth) acryloxypropyl ethyl phthalate, etc. Of unsaturated aromatic carboxylic acids. Moreover, as a hydroxyl-containing polymerizable unsaturated compound, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3- Phenyloxypropyl (meth) acrylate, 1,4 butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, neopentylglycol -Rumono (meth) acrylate, poly (pentamethyleneoxycarboxylate) ethoxy (meth) acrylate, hydroxystyrene, hydroxyalphamethylstyrene, hydroxyethylstyrene, hydroxy-terminated polyethylene glycol styryl ether, hydroxy-terminated Polypropy Lenglycol styryl ether, hydroxy-terminated polytetramethylene glycol styryl ether, terminal hydroxypolyethylene glycol (meth) acrylate, terminal hydroxypolypropylene glycol (meth) acrylate, terminal hydroxypolytetraethyleneglycol Ru (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane mono (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylolpropane tri (meth) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol mono (meth) acrylate, dipentaerythritol penta (meth) acrylate -G Pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol mono (meth) acrylate And the like, hydroxyl group-containing acrylates, hydroxyl group-containing methacrylates, and hydroxyl group-containing styrenes.
[0062]
Among these, unsaturated aliphatic carboxylic acids and hydroxyl group-containing acrylate compounds are preferred, and hydroxyl group-containing acrylate compounds are more preferred. For example, 2-hydroxylethyl acrylate, 2-hydroxyl Examples thereof include hydroxypropyl acrylate, pentaerythritol triacrylate and dipentaerythritol pentaacrylate.
[0063]
The amount of these polymerizable unsaturated compounds used is usually 1 equivalent to 1 equivalent of the remaining isocyanate group in the intermediate obtained by the addition reaction of mercaptoalkoxysilane and polyisocyanate compound as the equivalent of active hydrogen group. More than equivalent. If the amount is less than 1 equivalent, the active isocyanate group remains in the alkoxysilyl compound, and therefore unfavorable performance such as foaming, thickening, and coloring due to reaction with moisture may be exhibited.
[0064]
In the production of alkoxysilyl compounds, for the purpose of improving the flexibility of the coating film and the adhesion to the substrate, a divalent organic compound is formed between the alkoxysilyl group and the polymerizable unsaturated group by an addition reaction with a polyisocyanate compound. As a precursor of such a divalent organic compound unit, a chain, cyclic or branched organic compound having at least two active hydrogens that cause an addition reaction with an isocyanate group in the molecule. Compounds can be used. Examples of the group having active hydrogen include a hydroxyl group, a carboxyl group, a mercapto group, an amino group, a sulfonic acid group, a phosphoric acid group, and a silanol group. These organic compounds have 2 or more active hydrogens, preferably 2 or more and less than 10, more preferably 2. The molecular weight of such a compound having active hydrogen is usually from 500,000 to 100,000, preferably from 100 to 50,000, more preferably from 500 to 10,000. Examples of such divalent organic compounds include polyalkylene glycols, polyalkylene thioglycols, polyester diols, polyamides, polycarbonate diols, and polyalkylene diamines. , Polyalkylene dicarboxylic acids, polyalkylene diols, and polyalkylene dimercaptans. Of these, polyalkylene glycol is preferred. Examples of commercially available polyalkylene glycols include polyethylene glycol, polypropylene glycol, polytetraethylene glycol, polyhexamethylene glycol, and two or more kinds of these polyalkylene glycols. And UNICEF DC1100, UNICEF DC1800, UNICEF DCB1100, UNICEF DCB1800 manufactured by NOF Corporation, PPTG4000 manufactured by Hodogaya Chemical Co., Ltd. Examples include PPTG2000, PPTG1000, PTG2000, PTG3000, PTG650, PTGL2000, PTGL1000, EXENOL1020 manufactured by Asahi Glass Co., Ltd., PBG3000, PBG2000, PBG1000, Z3001 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and the like.
[0065]
The production of the polymerizable unsaturated group-containing alkoxysilane containing the above divalent organic group as a constituent component will be described as production methods (C) and (D) taking polyalkylene glycol as an example.
[0066]
Production Method (C) Method: After adding a polyalkylene glycol to an adduct of a mercaptoalkoxysilane and a polyisocyanate compound having an active isocyanate group at the terminal, to obtain a one-terminal hydroxy alkoxysilane, On the other hand, a separately synthesized method of reacting an adduct of a polymerizable unsaturated compound having a hydroxyl group at the terminal and a polyisocyanate compound, and linking them together with a urethane bond.
[0067]
Production method (D): Polyalkylene glycol polyisocyanate having an active hydroxyl group at the terminal, separately synthesized for an adduct of mercaptoalkoxysilane and polyisocyanate compound having an active isocyanate group at the terminal Examples thereof include a method in which an adduct of a compound and a hydroxyl group-containing polymerizable unsaturated compound is reacted to connect them with a urethane bond. The urethane bond formation conditions in the method (C) or (D) are the same as those in the method (A) or (B), and the hydroxyl group at the terminal of the compound having an active isocyanate group at the terminal is involved in the bond. The equivalent ratio of the compound having is usually in the range of 1.0 to 1.2. When it is less than 1.0, coloring and thickening due to unreacted isocyanate groups are likely to occur.
[0068]
In the production of alkoxysilane compounds, hydrolysis products with other organic alkoxysilanes may be used as hydrolysates of polymerizable unsaturated group-modified alkoxysilanes, such as tetramethoxysilane, tetraethoxysilane, tetrabutoxy. Condensates with alkylalkoxysilanes such as silane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, and phenyltrimethoxysilane may also be used. When producing the hydrolysis product, the amount of water used for the hydrolysis is usually 0.5 to 1.5 equivalents based on the total alkoxy groups, and from 0 ° C. in the presence or absence of a solvent. Hydrolysis and polycondensation products can be obtained by heating and stirring at a temperature below the boiling point for 5 minutes to 24 hours. At that time, an acidic catalyst or a base catalyst may be used in combination for the purpose of shortening the reaction time.
[0069]
The silica fine particles used in the production of the modified silica fine particles can be the same as those described above.
[0070]
The alkoxysilane compound fixed to the modified silica fine particles is usually a constant value of mass reduction% when the dry powder is completely burned in air, for example, thermal mass spectrometry from room temperature to normal 800 ° C. in air. Can be obtained.
[0071]
The amount of water consumed by the hydrolysis of the alkoxysilane compound in the production of the modified silica fine particles may be an amount by which at least one alkoxy group on silicon in one molecule is hydrolyzed. Preferably, the amount of water added or present during hydrolysis is at least one third of the number of moles of all alkoxy groups on the silicon, more preferably one half of the number of moles of all alkoxy groups. It is less than 3 times. The product obtained by mixing the alkoxysilane compound represented by the formula (II) and the silica fine particles under the condition where water is completely absent is a product in which the alkoxysilane compound is physically adsorbed on the surface of the silica fine particles. In a composition composed of such components, the effect of the expression of wear resistance, which is one purpose of the composition of the present invention, is low.
[0072]
In the production of the modified silica fine particles of the present invention, the alkoxysilane compound represented by the above formula (II) is separately hydrolyzed, and then mixed with powdered silica fine particles or colloidal silica, followed by heating and stirring. Or a method of hydrolyzing the alkoxysilane compound represented by the formula (II) in the presence of silica fine particles; and other components such as a polyfunctional unsaturated organic compound and a monovalent unsaturated organic compound. A method for performing surface treatment of silica fine particles in the presence of a photopolymerization initiator or the like can be selected. A method for hydrolyzing an alkoxysilane compound represented by the above formula (II) in the presence of silica fine particles Is preferred. When component B is produced, the production temperature is usually 20 ° C. to 150 ° C., and the treatment time is in the range of 5 minutes to 24 hours.
[0073]
Silica fine particles are known to contain moisture as adsorbed water on the particle surface in a normal storage state. For example, an organic solvent-dispersed colloidal silica also contains 0.5% of water as a normal product. Therefore, in the production of modified silica fine particles, it is also possible to produce using the moisture contained in the raw material by mixing the alkoxysilane compound and the silica fine particles, and heating and stirring.
[0074]
In the production of the modified silica fine particles of the present invention, when powdered silica is used, an organic solvent compatible with water may be added in order to carry out the reaction with the alkoxysilane compound smoothly and uniformly. Good. Preferred types of such organic solvents are alcohols, ketones, ethers, and amides. Examples of alcohols include methanol, ethanol, isopropyl alcohol, and butanol. , Ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, etc., ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, amides include dimethylformamide, dimethylacetamide, N-methylpyrrolidone, gamma butyrolactone, etc. Can do. The amount of these solvents added is not particularly limited as long as it meets the purpose of carrying out the reaction smoothly and uniformly.
[0075]
In the production of modified silica fine particles, an acid or base may be added as a catalyst to promote the reaction. Examples of the acid include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid, or methanesulfonic acid, Organic acids such as toluenesulfonic acid, phthalic acid, malonic acid, formic acid, acetic acid, oxalic acid, unsaturated organic acids such as methacrylic acid, acrylic acid, itaconic acid, and ammonium such as tetramethylammonium hydrochloride and tetrabutylammonium hydrochloride You can give salt. Examples of the base include ammonia water, primary amines such as diethylamine, triethylamine, dibutylamine and cyclohexylamine, secondary or tertiary aliphatic amines, aromatic amines such as pyridine, sodium hydroxide, potassium hydroxide and tetramethyl. There may be mentioned quaternary ammonium hydroxides such as ammonium hydroxide and tetrabutylammonium hydroxide. Of these, preferred examples of the acid include organic acids and unsaturated organic acids, and examples of the base include tertiary amines and quaternary ammonium hydroxides. The addition amount of these acids or bases is 0.001 to 1.0 part by mass, preferably 0.01 to 0.1 part by mass, with respect to 100 parts by mass of the alkoxysilane compound.
[0076]
The silica fine particle-containing hard coat layer of the present invention further contains a silicone-based or fluorine-based compound water / oil repellent and preferably has a contact angle with water of 80 ° C. or more. The water / oil repellent can be obtained by adjusting the surface tension so that the water contact angle is 80 degrees or more by adding an appropriate amount of a commercially available silicone-based or fluorine-based surfactant. Thereby, a hard coat layer excellent in moisture resistance can be obtained.
[0077]
Alternatively, it can also be obtained by forming a hard coat layer using an ultraviolet curable resin using, for example, the aforementioned silicon-modified or fluorine-modified oligomer, monomer or resin. The low moisture permeability hard coat layer is a layer that hardly transmits water vapor. In the present invention, the moisture permeability is usually 0.5 g / m. ² -A layer of 24 hours or less (JIS-Z-0208). Since this low moisture-permeable hard coat layer usually does not contain silica fine particles, it is necessary to provide the silica fine particle-containing hard coat layer of the present invention on this layer.
[0078]
Various additives can be added to the hard coat layer of the present invention as necessary. Examples of these additives include antioxidants, ultraviolet absorbers, light stabilizers, silane coupling agents, and aging. Inhibitor, thermal polymerization inhibitor, colorant, leveling agent, surfactant, storage stabilizer, plasticizer, lubricant, solvent, inorganic filler, organic filler, filler, wettability improver, coating surface improver Etc.
[0079]
An antireflection layer is preferably provided on the surface of the hard coat layer of the wear-resistant film of the present invention.
[0080]
As the antireflection layer, for example, the following can be used.
[0081]
a) Only one high refractive index transparent thin film is provided (b) Medium refractive index transparent thin film / High refractive index transparent thin film, one layer each in that order, laminated in two layers in total (c) Medium refractive index transparent Thin film / low refractive index transparent thin film / high refractive index transparent thin film, one layer each in that order, 3 layers in total (d) high refractive index transparent thin film / low refractive index transparent thin film / high refractive index transparent thin film / low (E) High refractive index transparent thin film / low refractive index transparent thin film / high refractive index transparent thin film / low refractive index transparent thin film / high refractive index transparent Each of the layers in the order of the thin film is laminated in a total of 5 layers. Here, as the high refractive or medium refractive index transparent thin film, ITO (tin indium oxide) or ZnO, Al doped ZnO, TiO ₂ , SnO ₂ A thin film having a refractive index of 1.8 or more, such as ZrO, can be used.
[0082]
Moreover, as a low refractive index or a medium refractive index transparent thin film, SiO ₂ , MgF ₂ , Al ₂ O ₃ A thin film having a refractive index of 1.6 or less, such as acrylic resin, urethane resin, silicone resin, or fluororesin can be used.
[0083]
The film thickness of these high refractive index transparent thin film, medium refractive index transparent thin film, and low refractive index transparent thin film is such that the reflectance in the visible light region can be lowered by light interference, the film type, the film thickness, and the center wavelength. It is determined as appropriate.
[0084]
Such a transparent thin film can be formed by vapor deposition, sputtering, ion plating, CVD, micro gravure coating, direct gravure coating, slot die coating method and the like.
[0085]
Alternatively, the antireflective layer comprises a high refractive index conductive layer formed on the hard coat layer and a low refractive index layer formed on the high refractive index conductive layer, and the high refractive index conductive layer has a thickness of It is an ITO film (tin / indium oxide film) of 100 to 600 mm, and the low refractive index layer has a thickness of 900 to 1500 mm. ₂ A film is also preferred.
[0086]
Since such an antireflection layer has a two-layer structure of a high-refractive-index conductive layer and a low-refractive-index layer, the antireflection performance is better than that provided with a single-layer antireflection layer, The structure is simple and can be formed at a lower cost than those provided with a multilayer antireflection layer. Moreover, since it has a high refractive index conductive layer, it has antistatic performance in addition to antireflection performance.
[0087]
As described above, as the antireflection layer, a high refractive index conductive layer made of an ITO film having a thickness of 100 to 600 mm, and an SiO film having a thickness of 900 to 1500 mm. ₂ When forming an antireflection layer having a two-layer structure with a low refractive index layer 5 made of a film, if the thickness of the ITO film is less than 100 mm, a sufficient antistatic function cannot be obtained, and if it exceeds 600 mm, the film formation cost increases. To do. Further, when the thickness of the ITO film is out of the range of 100 to 600 mm, SiO having a thickness of 900 to 1500 mm is obtained. ₂ With such a laminated structure, good antireflection performance cannot be obtained.
[0088]
In addition, SiO ₂ When the thickness of the film is outside the range of 900 to 1500 mm, good antireflection performance cannot be obtained with a laminated structure with an ITO film having a thickness of 100 to 600 mm.
[0089]
ITO film and SiO ₂ The film can be formed by vapor deposition, sputtering, ion plating, CVD, or the like.
[0090]
When an antireflection layer is provided on the hard coat layer of the present invention, the light transmittance at 365 nm of a laminate composed of three layers of an organic polymer film, a hard coat layer and an antireflection layer is preferably 40% or less. .
[0091]
When the light transmittance at 365 nm is 40% or less, the abrasion-resistant film of the present invention is excellent in weather resistance and durability without greatly affecting the surrounding environment such as ultraviolet rays. Is prevented.
[0092]
The laminate can be configured, for example, as follows (1), (2), or (3).
[0093]
(1) An ultraviolet cut layer is provided between the organic polymer film and the hard coat layer.
[0094]
(2) The hard coat layer is an ultraviolet cut layer.
[0095]
(3) The antireflection layer is an ultraviolet cut layer.
[0096]
The light transmittance at 365 nm of the laminate is preferably as low as possible. In the present invention, the light transmittance at 365 nm is preferably 30% or less, and the light transmittance for light having a wavelength of 350 nm is 20% or less, particularly 10% or less. In particular, it is desirable to be 5% or less.
[0097]
In the case of forming an ultraviolet cut layer as in the above (2), as the ultraviolet cut layer, a known ultraviolet absorber is added to an appropriate coating material such as an acrylic resin, a urethane resin, a silicone resin, an epoxy resin, etc. What is necessary is just to mix about 10 mass% and coat on the base film 1. The thickness of the ultraviolet cut layer 7 thus formed is preferably about 0.5 to 20 μm.
[0098]
When the hard coat layer itself of (2) is made to be UV-cutting, the UV-cutting hard coat layer is 0.05 to 5 mass of a known UV absorbing material in such a hard coat material (UV curable resin). % Can be formed by coating in the range of%.
[0099]
(3) In order to make the antireflective layer itself UV-cutting, a material having a high light-transmitting property near 400 nm and a large amount of light absorption near 350 nm or less is used as the material for the high refractive index transparent thin film. And such materials include ITO, ZnO and the like.
[0100]
The wear-resistant film thus obtained is a film tempered glass excellent in scratch resistance, impact resistance, penetration resistance, etc. used for automobiles, railway vehicles, buildings, showcases, etc., and the surface side protection of solar cells. It can be advantageously used for a member or a back side protection member. Specifically, such as automobile fitting glass, side glass and rear glass, railway cars such as ordinary vehicles, express vehicles, express vehicles and sleeper vehicles, door windows for passenger access doors, window glasses and indoor door glasses, buildings, etc. It is a showcase and a show window for indoor display, such as window glass and indoor door glass in a building.
[0101]
【Example】
The following examples further illustrate the present invention.
[0102]
[Example 1]
(1) Preparation of UV curable resin coating solution for hard coat formation
Dipentaerythritol hexaacrylate (DPHA) 10.92 parts by mass, 1-hydroxycyclohexyl phenyl ketone (HCHPK) 1.08 parts by mass as a photopolymerization initiator, and colloidal silica dispersion (trade name: MEK-ST, Nissan Chemical Co., Ltd.) ) 150 parts by mass of a silica particle primary particle diameter of 10 to 20 nm, silica content of 30% by mass, methyl ethyl ketone dispersion) manufactured by the company was obtained to obtain an ultraviolet curable resin coating solution.
(2) Production of wear-resistant film
On the surface of a PET film (thickness: 125 μm; trade name: Tetron HS, manufactured by Teijin DuPont), the above UV curable resin coating solution was applied to a wire bar coater No. After evaporating the solvent at 60 ° C. for 5 minutes, it was irradiated with ultraviolet light with a high-pressure mercury lamp in an air atmosphere (0.5 J / cm ² ), A hard coat layer having a layer thickness of 5 μm was formed.
[0103]
Thus, an abrasion resistant film was obtained.
[0104]
[Example 2]
(1) Preparation of UV curable resin coating solution for hard coat formation
In Example 1, it produced similarly except having added 0.16 mass part of fluorine-containing silane coupling agents (perfluoroalkyl silane, FAS) further.
(2) Production of wear-resistant film
A wear-resistant film was obtained in the same manner as in Example 1 using the above coating solution.
[0105]
[Example 3]
(1) Preparation of UV curable resin coating solution for hard coat formation
In Example 1, it produced similarly except having added 0.16 mass part of fluorine-containing silane coupling agents (perfluoroalkyl silane, FAS) further.
(2) Production of wear-resistant film
The above coating solution was applied to a wire bar coater No. By applying at 30, an abrasion resistant film was obtained in the same manner as in Example 1 in which the thickness of the hard coat layer was changed to 15 μm.
[0106]
[Example 4]
(1) Preparation of thermosetting composition coating solution for hard coat formation
Colloidal silica dispersion (trade name: 0-40, manufactured by Nissan Chemical Co., Ltd., silica primary particle diameter 10-20 nm, silica content 40 mass%, aqueous dispersion) 207 parts by mass, methyltrimethoxysilane ( MTS) 20.7 parts by mass and 0.7 parts by mass of acetic acid were mixed, kept at a temperature of 50 ° C., stirred for 2 hours, and hydrolyzed. To the obtained reaction mixture, 1.95 parts by mass of n-butyl alcohol, 1.95 parts by mass of isopropyl alcohol, 0.126 parts by mass of sodium acetate and 1.1 parts by mass of acetic acid are added, and a thermosetting composition coating liquid is added. Obtained.
(2) Production of wear-resistant film
On the surface of a PET film (thickness 125 μm; trade name Tetron HS, manufactured by Teijin DuPont), the above thermosetting composition coating solution was applied to a wire bar coater No. And hardened at 100 to 120 ° C. for 30 minutes to form a hard coat layer having a layer thickness of 5 μm.
[0107]
Thus, an abrasion resistant film was obtained.
[0108]
[Example 5]
(1) Preparation of thermosetting composition coating solution for hard coat formation
In Example 4, it produced similarly except having added 0.23 mass part of fluorine-containing silane coupling agents (perfluoroalkyl silane, FAS).
(2) Production of wear-resistant film
A wear-resistant film was obtained in the same manner as in Example 4 using the above coating solution.
[0109]
[Example 6]
(1) Preparation of thermosetting composition coating solution for hard coat formation
In Example 4, it produced similarly except having added 0.23 mass part of fluorine-containing silane coupling agents (perfluoroalkyl silane, FAS).
(2) Production of wear-resistant film
The above coating solution was applied to a wire bar coater No. By coating at 30, an abrasion-resistant film was obtained in the same manner as in Example 4 in which the thickness of the hard coat layer was changed to 15 μm.
[0110]
[Comparative Example 1]
(1) Preparation of UV curable resin coating solution for hard coat formation
In Example 1, it produced similarly except having changed the quantity of the colloidal silica dispersion liquid to 60 mass parts.
(2) Production of wear-resistant film
A wear-resistant film was obtained in the same manner as in Example 1 using the above coating solution.
[0111]
[Comparative Example 2]
(1) Preparation of UV curable resin coating solution for hard coat formation
In Example 1, it produced similarly except not using colloidal silica dispersion liquid.
(2) Production of wear-resistant film
A wear-resistant film was obtained in the same manner as in Example 1 using the above coating solution.
[0112]
[Comparative Example 3]
(1) Preparation of UV curable resin coating solution for hard coat formation
In Example 4, it produced similarly except not using colloidal silica dispersion liquid.
(2) Production of wear-resistant film
A wear-resistant film was obtained in the same manner as in Example 4 using the above coating solution.
[0113]
<Evaluation of wear-resistant film>
(1) Wear resistance is tested in accordance with JIS-R3221 using a Taber abrasion tester on the hard coat layer side surface (wear wheel: CS-10F; load: 500 g; 1000 conditions). The haze after the test was measured. A haze value of less than 5 was evaluated as ◎, 5-10 as ◯, and 10 exceeding as x.
[0114]
(2) Scratch resistance is steel wool # 0000 on the surface of the hard coat layer and 200 g / cm on the steel wool. ² The load was applied 10 times and reciprocated 10 times. The case where the scratches did not occur was marked as ◎, the case where the scratches were slightly attached was marked as ◯, and the case where the scratches were conspicuous was marked as x.
[0115]
(3) Adhesion was measured according to JIS-K5400. That is, after forming 100 grids at 1 mm intervals on the surface of the hard coat layer and closely attaching a commercially available cellophane tape to the surface, the number of cells remaining without peeling (X) Was displayed in X / 100.
[0116]
(4) Interference fringes are evaluated by placing a sample under a three-wavelength fluorescent lamp and visually observing the surface of the hard coat layer. It was.
[0117]
(5) The contact angle for water is a drop of distilled water on the surface of the hard coat layer at a temperature of 23 ° C. and a humidity of 50% RH (water droplet diameter: 2 mm). One minute after the dropping, the contact angle between the layer surface and distilled water is , Measured using a contact angle meter (CA-DT-A type, manufactured by Kyowa Interface Chemical Co., Ltd.). A total of 6 measurements were taken with 3 samples and 2 left and right locations, and the average value of these was obtained as the contact angle.
[0118]
The composition and measurement results of each example are shown in Table 1 below.

It can be seen that the scratch resistance and wear resistance obtained in the above examples are excellent, and in Examples 3 and 6, the moisture resistance (the contact angle with water is large) is also excellent.
[0119]
[Example 7]
A wear-resistant film having the configuration shown in FIG. 2 was produced.
(2) Production of wear-resistant film
The UV curable resin coating solution used in Comparative Example 2 was applied to the surface of a PET film (thickness: 125 μm; trade name: Tetron HS, manufactured by Teijin DuPont) using a wire bar coater No. 16 and after evaporating the solvent at 60 ° C. for 5 minutes, it was irradiated with ultraviolet rays with a high-pressure mercury lamp in an air atmosphere (0.5 J / cm ² ), A hard coat layer having a layer thickness of 10 μm was formed, and the UV curable resin coating solution used in Example 2 was then added to the wire bar coater No. After evaporating the solvent at 60 ° C. for 5 minutes, it was irradiated with ultraviolet light with a high-pressure mercury lamp in an air atmosphere (0.5 J / cm ² ), A hard coat layer having a layer thickness of 5 μm was formed. Thus, an abrasion resistant film was obtained.
[0120]
The abrasion-resistant film obtained in Example 7 was excellent in all evaluations as in Example 3, and further had excellent visual transparency. Moreover, since the amount of silica can be kept low, it is economically advantageous.
[0121]
【The invention's effect】
The abrasion-resistant film according to the present invention described above is excellent in scratch resistance and abrasion resistance, and is further excellent in moisture resistance in a preferred embodiment. Therefore, the wear-resistant film of the present invention is a film tempered glass excellent in scratch resistance, impact resistance, penetration resistance, etc. used for automobiles, railway vehicles, buildings, showcases, etc. It can be advantageously used for a side protection member or a back side protection member. Specifically, such as automobile fitting glass, side glass and rear glass, railway cars such as ordinary vehicles, express vehicles, express vehicles and sleeper vehicles, door windows for passenger access doors, window glasses and indoor door glasses, buildings, etc. It is a showcase and a show window for indoor display, such as window glass and indoor door glass in a building.
[0122]
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing the basic configuration of an abrasion-resistant film of the present invention.
FIG. 2 is a cross-sectional view showing a preferred basic configuration of the wear-resistant film of the present invention.
FIG. 3 is a cross-sectional view showing the basic structure of the laminate of the present invention.
[Explanation of symbols]
11, 21, 31 Organic polymer film
12, 22a, 22b, 32 Hard coat layer
33 Transparent adhesive layer

Claims (7)

A UV coat containing silica fine particles having a primary particle size in the range of 1 to 200 nm on which a hard coat layer made of a cured film of an ultraviolet curable resin not containing silica fine particles is provided on one side of the organic polymer film. A hard coat layer having a content of 70 to 90% by mass with respect to the cured coating of silica fine particles, and a surface of the organic polymer film on which the hard coat layer is not provided And a hard coat layer containing silica fine particles having a primary particle size in the range of 1 to 200 nm, wherein the layer thickness of the hard coat layer not including the silica fine particles is 10 to 15 μm. A wear-resistant film having a thickness of 2 to 5 μm. The wear-resistant film according to claim 1 , wherein the primary particle diameter of silica fine particles having a primary particle diameter in the range of 1 to 200 nm is in the range of 20 to 50 nm. The abrasion-resistant film according to claim 1 or 2 , wherein the silica fine particles having a primary particle size in the range of 1 to 200 nm have a polymerizable unsaturated group. Silica fine particles having a primary particle size in the range of 1~200nm are resistant according to claim 1 in which are formed by reaction of the alkoxysilane compound having silica particles and a polymerizable unsaturated group Abrasive film. The wear-resistant film according to any one of claims 1 to 4 , wherein the hard coat layer further contains a water- or oil-repellent agent of a silicone or fluorine compound and has a contact angle with water of 80 degrees or more. The abrasion-resistant film according to any one of claims 1 to 5, wherein an antireflection layer is further formed on the surface of the hard coat layer. The abrasion-resistant film according to any one of claims 1 to 6 , wherein the organic polymer is polyethylene terephthalate, polypropylene, poly (meth) acrylate, or polyethersulfone.

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