JP2004043689A - Amorphous polyolefin resin article covered with modified surface layer and production method used for the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an amorphous polyolefin resin article having enhanced adhesiveness of a surface of a base material thereby firmly covering the base material of an amorphous polyolefin resin with a functional thin film, and also provide a production method of the amorphous polyolefin resin article covered with the functional thin film imparting wear-resistance, antireflective function, antiglare property, water repellency, hydrophilicity, stain resistance or the like. <P>SOLUTION: The surface of the base material of the amorphous polyolefin resin is subjected to hydrophilization treatment, and then liquid for surface modification is applied onto the hydrophilized surface and cured, thus the amorphous polyolefin resin article covered with a modified surface layer is formed. Further, hard coat liquid containing colloidal silica and an organo-silicon compound can be applied onto the modified surface and cured to from a hard coat layer. <P>COPYRIGHT: (C)2004,JPO

Description

【００８０】
表面改質層用処理液の調製
表面改質用液１の調製
溶剤可溶型のアクリル樹脂「パラロイドＡ−１０Ｓ」（ローム・アンド・ハース・ジャパン（株））を５０ｇ、プロピレングリコールモノメチルエーテル５０ｇをそれぞれ秤量、混合し、均質な液とし、界面活性剤を少々加え、表面改質用液１とする。
表面改質用液２の調製
パラロイドＡ−１０Ｓ（ローム・アンド・ハース・ジャパン（株））を５０ｇ、プロピレングリコールモノメチルエーテル５０ｇをそれぞれ秤量、混合し、均質な液を調合し、γ−メタクリロキシプロピルトリメトキシシランを２ｇ添加し、撹拌し均質な液とし、界面活性剤を少々加え、表面改質用液２とする。
表面改質用液３の調製　
パラロイドＡ−１０Ｓ（ローム・アンド・ハース・ジャパン（株））を５０ｇ、プロピレングリコールモノメチルエーテル５０ｇをそれぞれ秤量、混合し、均質な液を調合し、γ−メタクリロキシプロピルトリメトキシシランを２ｇ添加し、２，４−ジヒドロキシベンゾフェノン４．５ｇを添加、撹拌し均質な液とし、界面活性剤を少々加え、表面改質用液３とする。
表面改質用液４の調製
エチルセロソルブ４００ｇ、メタアクリル酸エチル１９０ｇ、γ−メタクリロキシプロピルトリメトキシシランを１０ｇの混合物を、窒素雰囲気下で７５℃に保ちつつ、ベンゾイルパーオキサイド１．０ｇを、エチルセロソルブ２００ｇに溶かした溶液を２時間かかって加え、さらに６時間、７５℃に保つ。その後エチルセロソルブ１４００ｇ、過塩素酸アンモニウムの１０％水溶液を２ｇ、２，４−ジヒドロキシベンゾフェノン３０ｇを加え、表面改質用液４とする。
表面改質用液５の調製
エチルセロソルブ４００ｇ、メタアクリル酸エチル１９０ｇ、γ−メタクリロキシプロピルトリメトキシシラン１０ｇの混合物を、窒素雰囲気下で７５℃に保ちつつ、ベンゾイルパーオキサイド１．０ｇを、エチルセロソルブ２００ｇに溶かした溶液を２時間かかって加え、さらに６時間、７５℃に保つ。その後エチルセロソルブ１４００ｇ、γ−メタクリロキシプロピルトリメトキシシランを３．５ｇ、過塩素酸アンモニウムの１０％水溶液を２ｇ、２，４−ジヒドロキシベンゾフェノン３０ｇを加え、表面改質用液５とする。
【００８１】
表面改質用液６の調製
ブチルセロソルブ３００部を窒素雰囲気下で１００℃に保ちつつ、メタアクリル酸１６０部、γ−メタクリロキシプロピルトリメトキシシラン４０部、ベンゾイルパーオキサイド２．０部の混合物を３時間かかって加え、さらに３時間同温度に保った。その後ブチルセロソルブ１１５５部、エチレングリコールジアセテート３６３部、過塩素酸アンモニウムの１０％水溶液を３部、２−ヒドロキシ−４−メトキシベンゾフェノン１００部、およびフローコントロール剤少々を加え、表面改質用液６とした。
表面改質用液７の調製
メチルイソブチルケトンン３８４部、メチルエチルケトン２１６部の混合物を、窒素雰囲気下９０℃に保ちつつ、メタアクリル酸メチル１８０部、γ−メタクリロキシプロピルメチルジメトキシシラン２０部、アゾビスイソブチロニトリル１．０部の混合物を２時間かかって加え、さらに５時間同温度に保った。その後メチルイソブチルケトン６２４部、イソプロピルアルコール５７６部、過塩素酸アンモニウムの１０％水溶液１０部及び２−エチルヘキシル−２−シアノ−３，３−ジフェニルアクリレート４０部を加え、表面改質用液７とした。
表面改質用液８の調製
エチルセロソルブ４００部、メタアクリル酸エチル１４０部、γ−メタクリロキシプロピルトリメトキシシラン６０部の混合物を、窒素雰囲気下７５℃に保ちつつ、ベンゾイルパーオキサイド１．０部をエチルセロソルブ２００部に溶かした溶液を２時間かかって加え、更に８時間同温度に保った。その後エチルセロソルブ１４００部、過塩素酸アンモニウムの１０％水溶液１４部、２−（２′−ヒドロキシ−５′−オクチルフェニル）ベンゾトリアゾール３０部を加え、表面改質用液８とした。
表面改質用液９の調製
エチルセロソルブ４００部、メタアクリル酸エチル１９０部、γ−メタクリロキシプロピルトリメトキシシラン１０部の混合物を、窒素雰囲気下で７５℃に保ちつつ、ベンゾイルパーオキサイド１．０部をエチルセロソルブ２００部に溶かした溶液を２時間かかって加え、さらに６時間同温度に保った。その後、エチルセロソルブ１４８６部、過塩素酸アンモニウムの１０％水溶液２部、ヘキサ（メトキシメチル）メラミン２．６部、２，４−ジヒドロキシベンゾフェノン２０部を加え、表面改質用液９とした。
【００８２】
表面改質用液１０の調製
ブチルセロソルブ３００部を窒素雰囲気下１００℃に保ちつつ、メタアクリル酸メチル１６０部、γ−メタクリロキシプロピルトリメトキシシラン４０部、ベンゾイルパーオキサイド２．０部の混合物を３時間かかって加え、さらに３時間同温度に保った後、エチレングリコールジアセテート３６０部を加えた。こうして得られた共重合体２１５部に、過塩素酸アンモニウムの１０％水溶液１．０部、ヘキサ（メトキシメチル）メラミン０．８部、２，４−ジヒドロキシベンゾフェノン５０部、およびブチルセロソルブ２８５部を加えて、表面改質用液１０とした。
表面改質用液１１の調製
表面改質用液１０の調製に用いた共重合体２１５部に、過塩素酸アンモニウムの１０％水溶液０．５部、ヘキサ（メトキシメチル）メラミン０．３部、２，２′−ヒドロキシ−４−メトキシベンゾフェノン１０部、およびブチルセロソルブ２８５部を加えて、表面改質用液１１とした。
表面改質用液１２の調製
酢酸ｎ−ブチル３２０部を窒素雰囲気下９０℃に保ちつつ、メタアクリル酸メチル９０部、γ−メタクリロキシプロピルメチルジメトキシシラン１０部、アゾビスイソブチロニトリル０．８部の混合物を２時間かかって加え、さらに同温度に５時間保った。その後ブチルセロソルブ７６０部、過塩素酸アンモニウムの１０％水溶液５部、ヘキサ（メトキシメチル）メラミン１．８部、２−（２′−ヒドロキシ−５′−ｔ−ブチルフェニル）ベンゾトリアゾール２０部を加えて、表面改質用液１２とした。
表面改質用液１３の調製
エチルセロソルブ４００部、メタアクリル酸エチル１４０部、γ−メタクリロキシプロピルトリメトキシシラン６０部の混合物を窒素雰囲気下８０℃に保ちつつ、ベンゾイルパーオキサイド１．０部をエチルセロソルブ２００部に溶かした溶液を２時間かかって加え、さらに８時間同温度に保った。その後エチルセロソルブ１４００部、過塩素酸アンモニウムの１０％水溶液を６部、ヘキサ（メトキシメチル）メラミン４．７部、２−エチルヘキシル−２−シアノ−３，３ジフェニルアクリレート４０部を加えて、表面改質用液１３とした。
【００８３】
ハードコート液１（光硬化型ハードコート）の調製
多官能アクリレートとして１，６−ヘキサンジオールジアクリレート１２．４ｇ、γ−アミノプロピルトリメトキシシラン１．６ｇ、２−メトキシプロパノール６．３ｇ、酢酸４．０ｇ、光重合開始剤としてベンゾフェノンを０．８ｇ、コロイダルシリカとして「ＮＰＣ−ＳＴ−３０」（日産化学工業（株）製、ｎ−プロピルセロソルブ中に平均粒２０ｎｍのシリカ微粒子を分散。シリカ含有量３０重量％）を２６．０ｇ、膜に可とう性を与え、かつ膜の硬度を高めるためのエポキシアクリレートとして「エポキシエステル３００２Ｍ」（共栄社化学（株）製）を５．０ｇ、酢酸ブチル１４．５ｇを添加する。次に、フローコントロール剤（「ペインタッド１９」、ダウコーニングアジア（株）製）を０．１ｇ添加する。その後、２−メトキシプロパノールを１００ｇ添加し、撹拌し均質に分散させて、耐擦傷性を付与するためのハードコート液１が得られた。
【００８４】
ハードコート液２（防眩性付与光硬化型ハードコート）の調製
多官能アクリレートとしてポリエチレングリコールジアクリレート１６．０ｇ、γ−（２−アミノエチル）アミノプロピルトリメトキシシラン１．０ｇ、２−メトキシプロパノール６．３ｇ、酢酸４．０ｇ、光重合開始剤としてイソプロピルベンゾインエーテルを０．８ｇ、コロイダルシリカとして「ＩＰＡ−ＳＴ−ＺＬ」（日産化学工業（株）製、イソプロパノール中に平均粒径８０〜１００ｎｍのシリカ微粒子を分散。シリカ含有量３０重量％）を４５．０ｇ、次に、膜の硬度を高め、かつ、低エネルギーで膜を硬化させるためのウレタンアクリレートとして「ＵＡ−３０６Ｈ」（共栄社化学（株）製、ペンタエリスリトールトリアクリレートとヘキサメチレンジイソシアネートのウレタンプレポリマー）を１．０ｇ、フローコントロール剤を０．１ｇ添加する。その後、２−メトキシプロパノールを１００ｇ添加する。その後、前記溶液に平均粒径が６μｍの結晶質シリカ微粒子を０．８ｇ（ハードコート有効成分の２重量％）添加し、撹拌し均質に分散させる。これにより、防眩性および耐擦傷性を付与するためのハードコート液２が得られた。
【００８５】
ハードコート液３（撥水性付与光硬化型ハードコート）の調製
多官能アクリレートとして１，４−ブタンジオールジアクリレート１７ｇ、γ−アミノプロピルトリメトキシシラン８．０ｇ、２−メトキシプロパノール６．３ｇ、酢酸４．０ｇ、光重合開始剤として２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オンを０．８ｇ、コロイダルシリカとして「ＩＰＡ−ＳＴ」（日産化学工業（株）製、イソプロパノール中に平均粒径１０〜２０ｎｍのシリカ微粒子を分散。シリカ含有量３０重量％）を２０．０ｇ、パーフルオロオクチルエチルトリエトキシシランを９．０ｇ添加し反応させた後で、酢酸ブチル１４．５ｇを添加する。次に、フローコントロール剤を０．１ｇ添加する。その後、２−メトキシプロパノールを１００ｇ添加する。これにより、撥水性および耐擦傷性を付与するためのハードコート液３が得られた。
【００８６】
ハードコート液４（撥水性および防眩性付与光硬化型ハードコート）の調製
多官能アクリレートとしてトリメチロールプロパントリアクリレート１２．４ｇ、γ−アミノプロピルトリメトキシシラン２．６ｇ、２−メトキシプロパノール６．３ｇ、酢酸４．０ｇ、光重合開始剤としてベンゾフェノンを０．８ｇ、コロイダルシリカとして「ＩＰＡ−ＳＴ−ＺＬ」（日産化学工業（株）製）を２６．０ｇ、パーフルオロオクチルエチルトリエトキシシランを９．０ｇ添加し反応させた後で、酢酸ブチル１４．５ｇを添加する。次に、フローコントロール剤を０．１ｇ添加する。その後、２−メトキシプロパノールを１００ｇ添加する。その後、前記溶液に平均粒径が６μｍのシリカ微粒子を０．８ｇ（ハードコート有効成分の２重量％）添加し、撹拌し均質に分散させる。これにより防眩性、撥水性および耐擦傷性を付与するためのハードコート液４が得られた。
【００８７】
ハードコート液５（熱硬化型ハードコート）の調製
コロイダルシリカ「スノーテックス　Ｏ−４０」（日産化学（株）製：平均粒径２０ｎｍ、不揮発分４０％）１５０ｇ、メチルトリメトキシシラン１８３ｇを反応させた後、イソプロピルアルコール５０８ｇ、ノルマルブタノール１４０ｇ、酢酸１８ｇ、酢酸ナトリウム１ｇおよびＤｏｗ　Ｃｏｒｎｉｎｇペイントアディティブ１９を０．１ｇ加えて、耐擦傷性を付与するためのハードコート液５が得られた。
ハードコート液６（防眩付与熱硬化型ハードコート）の調製
前記コロイダルシリカ「スノーテックス　Ｏ−４０」５８ｇ、メチルトリメトキシシラン８６ｇを反応させた後、イソプロピルアルコール５０５ｇ、ノルマルブタノール１４０ｇ、酢酸１８ｇ、酢酸ナトリウム２ｇおよびＤｏｗ　Ｃｏｒｎｉｎｇペイントアディティブ１９を０．１ｇ加えた溶液に、平均粒径が６μｍのシリカ微粒子を２．４ｇ（ハードコート有効成分の２重量％）添加し、撹拌し均質に分散させた。これにより、防眩性および耐擦傷性を付与するためのハードコート液６が得られた。
【００８８】
ハードコート液７（撥水性付与熱硬化型ハードコート）の調製
前記コロイダルシリカ「スノーテックス　Ｏ−４０」５８ｇ、メチルトリメトキシシラン８６ｇ、およびパーフルオロオクチルエチルトリメトキシシラン４．３ｇを反応させた後、イソプロピルアルコール５０５ｇ、ノルマルブタノール１４０ｇ、酢酸１８ｇ、酢酸ナトリウム２ｇおよびＤｏｗ　Ｃｏｒｎｉｎｇペイントアディティブ１９を０．１ｇ加え、撹拌し均質に分散させた。これにより、撥水性および耐擦傷性を付与するためのハードコート液７が得られた。
ハードコート液８（防眩・撥水性付与熱硬化型ハードコート）の調製
前記コロイダルシリカ「スノーテックス　Ｏ−４０」５８ｇ、メチルトリメトキシシラン８６ｇ、およびパーフルオロオクチルエチルトリメトキシシラン４．３ｇを反応させた後、イソプロピルアルコール５０５ｇ、ノルマルブタノール１４０ｇ、酢酸１８ｇ、酢酸ナトリウム２ｇおよびＤｏｗ　Ｃｏｒｎｉｎｇペイントアディティブ１９を０．１ｇ加えた溶液に、平均粒径が６μｍのシリカ微粒子を２．４ｇ（ハードコート有効成分の２重量％）添加し、撹拌し均質に分散させたた。これにより防眩性、撥水防汚性および耐擦傷性を付与するためのハードコート液８が得られた。
【００８９】
ハードコート液９（防眩性付与光硬化型ハードコート）の調製
多官能アクリレート（Ａ）として１，６−ヘキサンジオールジアクリレート１００ｇに対し、アミノシラン（Ｂ）としてγ―アミノプロピルトリメトキシシラン１０ｇ、２−メトキシプロパノール５０ｇ、酢酸５ｇ、コロイダルシリカ（Ｃ）として平均粒子径１０〜２０ｎｍの「ＩＰＡ−ＳＴ」（有効成分：３０重量％、日産化学工業（株）製）を１４０ｇ、微粒子（Ｊ）としてアモルファスシリカ微粒子の分散液「ＫＥ−Ｗ５０」（粒径：０．５０〜０．５６μｍ、有効成分：１５重量部、（株）日本触媒製）を５００ｇ添加し、撹拌し、その後、光開始剤としてベンゾフェノンを５ｇ、フローコントロール剤を０．１ｇ添加してハードコート液９を得た。
【００９０】
ハードコート液１０（光硬化型下地ハードコート）の調製
多官能アクリレートとして１，６−ヘキサンジオールジアクリレート１２．４ｇ、γ−アミノプロピルトリメトキシシラン２．６ｇ、２−メトキシプロパノール６．３ｇ、酢酸０．４ｇ、コロイダルシリカとして（平均粒子径２０〜３０ｎｍ）の「ＭＡ−ＳＴ−Ｍ」（有効成分：４０重量％　日産化学工業（株）製）を２０．０ｇ、エポキシアクリレートとして「エポキシエステル３００２Ｍ」（共栄社化学（株）製）を５．０ｇ、酢酸ブチル１４．５ｇを添加する。次に、光重合開始剤としてベンゾフェノンを０．８ｇ、フローコントロール剤を０．１ｇ添加する。その後、２−メトキシプロパノールを１００ｇ添加し、撹拌し均質に分散させてハードコート液１０を得た。
【００９１】
屈折率調整層用液１の調製
多官能アクリレートとして１，４−ブタンジオールジアクリレート１２．４ｇ、３−アクロキシプロピルトリメトキシシラン１．０ｇ、２−メトキシプロパノール６．３ｇ、酢酸４．０ｇ、光重合開始剤として２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オンを０．８ｇ、コロイダルシリカとして「ＮＰＣ−ＳＴ−３０」（日産化学（株）製、ｎ−プロピルセロソルブ中に平均粒２０ｎｍのシリカ微粒子を分散。シリカ含有量３０重量％）を２０．０ｇを添加する。次に、フローコントロール剤を０．１ｇ添加する。
【００９２】
その後、２−メトキシプロパノールを１００ｇ添加し、撹拌し均質に分散させる。その液に「オプトレイク１１３０Ｆ２Ａ８」（ＴｉＯ_２およびＳｉＯ_２からなる複合酸化物微粒子（平均粒径約１０ｎｍ）をメタノール中に分散させたもの、触媒化成製、ＴｉＯ_２とＳｉＯ_２のモル比は８０：２０。複合酸化物含有量３０重量％）を３０ｇ添加した。このようにして、成膜後の屈折率がハードコート層のそれよりも高い層を形成するための屈折率調整層用液１を得た。
【００９３】
低屈折率用コート液１１（熱硬化型ハードコート）の調製
平均粒子径２０ｎｍのコリダルシリカとして「スノーテックス　Ｏ−４０」（日産化学（株）製：不揮発分４０％）１５０ｇ、メチルトリメトキシシラン１８３ｇを反応させた後、イソプロピルアルコール６４８ｇ、酢酸１８ｇ、酢酸ナトリウム１ｇ、およびフローコントロール剤として「ペイントアディティブ１９」（ダウコーニング社製）を０．１ｇ加え、撹拌して低屈折率用コート液１１を得た。
【００９４】
低屈折率用コート液１２（撥水性付与熱硬化型ハードコート液）の調製
平均粒子径８０〜１００ｎｍのコロイダルシリカとして「ＩＰＡ−ＳＴ−ＺＬ」（日産化学（株）製：不揮発分３０％）６００ｇ、メチルトリメトキシシラン８６ｇ、およびパーフルオロオクチルエチルトリメトキシシラン４．３ｇを反応させた後、イソプロピルアルコール６４５ｇ、酢酸１８ｇ、酢酸ナトリウム２ｇ、およびフローコントロール剤として「ペイントアディティブ１９」（ダウコーニング社製）を０．１ｇ加え、撹拌して低屈折率用コート液１２を得た。
【００９５】
塗布法および硬化法
表面改質層用液は、親水化処理を実施した樹脂（実施例）又は親水化処理をしていない基材（比較例）に対して、フローコート法で塗布し、８０℃で３０分間の熱硬化させて、厚み１０ｎｍの表面改質層を形成した。
上記ハードコート液１〜４、９、１０はフローコート法により、ハードコート液５はスピナー法によりそれぞれ塗布し、その後に、出力１２０Ｗ／ｃｍの紫外線ランプにより、総紫外線照射エネルギーが１０００（ｍＪ／ｃｍ^２）になるように、１秒〜３０秒間照射して、塗布膜を硬化した。なお、この総紫外線照射エネルギー値は、積算光量計（型式：ＵＩＴ−１０２　ウシオ電機（株）製）で測定した。また、屈折率調整層用液１はフレキソ印刷法により塗布し、上記と同様に塗布膜を紫外線硬化させた。ハードコート液６〜８については、フローコート法により塗布し、８０℃―１２０分間加熱して硬化させた。低屈折率用コート液１１および１２はスピン法で塗布し、塗布膜を８０℃で３０分間加熱して硬化させた。
【００９６】
評価方法
以下に示す各実施例で得られた非晶質ポリオレフィン樹脂基材を被覆した被膜の評価方法は、次の通りである。
（ａ）付着性試験：碁盤目試験ＪＩＳ　Ｋ５４００に準拠して行った。すなわち、ニチバン（株）製のセロハンテープをハードコート被膜上に貼り付けた後に、勢い良く引き剥がす方法で、耐湿試験前（初期）と耐湿試験（５０℃、９５％ＲＨの槽内に１０日間）後の被膜の付着性（易接着性）および耐透湿性を評価し、ハードコート被膜の１００個のます目のうち剥がれたます目の数によって次の基準で判定した。
剥がれたます目の数　０−−−−−−「剥離なし」
剥がれたます目の数　１〜５−−−−「極一部で剥離」
剥がれたます目の数　６〜５０−−−「部分的に剥離」
剥がれたます目の数　５１〜９９−−「剥離大」
剥がれたます目の数　１００−−−−「全面剥離」
（ｂ）耐湿試験：雰囲気温度５０℃、相対湿度９５％ＲＨの槽内に１０日間放置して行った。
（ｃ）キズ付き性（耐擦傷性）：市販のスチールウール（＃００００）で１０回表面を擦り、キズ付きかたを目視で判定した。判定基準は以下の４段階で行った。
１…キズなし、２…わずかにキズあり、３…キズ多数、４…膜が剥れるほどキズつく。
（ｄ）汚れ性試験：市販のワックスを付けた後で、綿製の無塵布で拭き取り、ワックスの拭き跡が汚れとして残る程度を目視で確認して防汚性を評価した。
（ｅ）接触角測定：０．１ｃｃの純水滴との接触角を測定した。接触角が大きいほど防汚性が高いことを表している。
（ｆ）光学特性測定：ＪＩＳ　Ｒ３２１２に準拠して可視光線透過率（％）および曇価（％）を測定した。曇価が高いほど防眩性が高いことを表している。
【００９７】
実施例１
前記非晶質ポリレフィン基材Ｂ１に前記コロナ放電処理を毎秒５ｍｍの速度で実施し、非晶質ポリオレフィン基材表面の水の接触角が４０度となるようにした。次いで、前記表面改質用液４を塗布して熱風乾燥炉で８０℃、３０分間加熱乾燥して厚み１０ｎｍの表面改質層を被覆した。
得られた表面改質層の成膜直後（初期）の付着性テストでは剥離がなかった。上記の付着性を評価したサンプルとは別のサンプルを作製して、キズ付き性を評価した。キズ付き性試験では多数のキズが見られた。また、光学特性は可視光透過率が９１％、３５０ｎｍの透過率は０％であった。
【００９８】
実施例２〜７
実施例１におけるコロナ放電処理５ｍｍ／ｓに代えて、それぞれ、
実施例２では前記プラズマ処理を実施して樹脂基材表面の水の接触角が２０度となるようにし、
実施例３では前記オゾン水洗浄処理を行って基材表面の水の接触角が５０度となるようにし、
実施例４では前記ＵＶオゾン照射時間を３０分間行って基材表面の水の接触角が５度となるようにし、
実施例５では前記ＵＶオゾン照射時間を１５分間行って基材表面の水の接触角が約１５度となるようにし、
実施例６では前記ＵＶオゾン照射時間を５分間行って基材表面の水の接触角が約４５度となるようにし、
実施例７では前記ＵＶオゾン照射時間を２分間行って基材表面の水の接触角が約６０度となるようにし、
それ以外は、実施例１と同じ基材Ｂ１、表面改質処理液４および硬化条件を使用し、実施例１と同様の方法で表面改質層を形成した。
さらに実施例１と同様の方法で被膜の付着性とキズ付き性を評価したところ、実施例２〜７のいずれも初期の付着性はいずれも「剥離なし」であり、いずれの実施例もキズ付き性試験では多数のキズが見られ、いずれの実施例も可視光透過率が９１％、３５０ｎｍの透過率は０％であった。
実施例１〜７の結果を表１にまとめて示す。
【００９９】
比較例１
実施例１で使用した非晶質ポリレフィン基材Ｂ１に親水化処理をしないで（ポリオレフィン基板表面の水の接触角が９０度）、表面改質用液４を塗布して熱風乾燥炉で８０℃、３０分間加熱乾燥して、厚み１０ｎｍの表面改質層を形成した。
得られた膜の成膜直後（初期）の付着性をテストしたが「剥離大」であった。キズ付き性試験では多数のキズが見られた。また、光学特性は可視光透過率が９１％、３５０ｎｍの透過率は０％であった。
比較例２
比較例１で得られた表面改質層付き非晶質ポリレフィン基材Ｂ１の表面に真空蒸着によって厚み１００ｎｍ／１００ｎｍのＴｉＯ_２／ＳｉＯ_２積層無機膜層（反射防止層）を形成させた。
比較例３
比較例１で得られた表面改質層付き非晶質ポリレフィン基材Ｂ１の表面にハードコート液１を塗布し、硬化させて膜厚３μｍのハードコート層を被覆した。
比較例２および３で得られた膜の成膜直後（初期）の付着性をテストしたが「剥離大」であった。キズ付き性試験ではいずれの比較例も多数のキズが見られた。また、比較例２、３のいずれについても光学特性は可視光透過率が９１％、３５０ｎｍの透過率は０％であった。
比較例１〜３の結果を表３にまとめて示す。
【０１００】
実施例８〜１９
実施例１において使用した表面改質処理液４に代えて、それぞれ、
実施例８では表面改質処理液１を使用し、
実施例９では表面改質処理液２を使用し、
実施例１０では表面改質処理液３を使用し、
実施例１１では表面改質処理液５を使用し、
実施例１２では表面改質処理液６を使用し、
実施例１３では表面改質処理液７を使用し、
実施例１４では表面改質処理液８を使用し、
実施例１５では表面改質処理液９を使用し、
実施例１６では表面改質処理液１０を使用し、
実施例１７では表面改質処理液１１を使用し、
実施例１８では表面改質処理液１２を使用し、
実施例１９では表面改質処理液１３を使用し、
それ以外は、実施例１と同じ基材Ｂ１、コロナ放電処理５ｍｍ／ｓ、および硬化条件で、実施例１と同様の方法で表面改質層を形成した。
さらに実施例１と同様の方法で被膜の付着性とキズ付き性を評価したところ、実施例８〜１９のいずれも初期の付着性はいずれも「剥離なし」であり、いずれの実施例もキズ付き性試験では多数のキズが見られ、いずれの実施例も可視光透過率が９１％であり、３５０ｎｍの透過率については実施例８および９では８８％であり実施例１０〜１９ではいずれも０％であった。
実施例８〜１９の結果を表１にまとめて示す。
【０１０１】
実施例２０〜２６
実施例１において使用した基材Ｂ１に代えて、それぞれ、
実施例２０では基材Ａ２を使用して親水化処理後の水滴接触角が４５度になるようにし、
実施例２１では基材Ａ１を使用して親水化処理後の水滴接触角が４０度になるようにし、
実施例２２では基材Ｃ１を使用して親水化処理後の水滴接触角が３５度になるようにし、
実施例２３では基材Ｃ２を使用して親水化処理後の水滴接触角が３５度になるようにし、
実施例２４では基材Ｅ１を使用して親水化処理後の水滴接触角が４０度になるようにし、
実施例２５では基材Ｄ１を使用して親水化処理後の水滴接触角が３５度になるようにし、
実施例２６では基材Ｄ２を使用して親水化処理後の水滴接触角が３５度になるようにし、
それ以外は、実施例１と同じコロナ放電処理５ｍｍ／ｓ、表面改質用液４および硬化条件で、実施例１と同様の方法で表面改質層を形成した。
さらに実施例１と同様の方法で被膜の付着性とキズ付き性を評価したところ、実施例２０〜２６のいずれも初期の付着性はいずれも「剥離なし」であり、いずれの実施例もキズ付き性試験では多数のキズが見られ、いずれの実施例も可視光透過率が９１〜９２％であり、３５０ｎｍの透過率についてはいずれの実施例も０％であった。
実施例２０〜２６の結果を表２にまとめて示す。
【０１０２】
実施例２７
実施例８と同じ方法で得た表面改質層被覆基材の上にハードコート液１を塗布し、硬化させて膜厚３μｍのハードコート層を被覆した。
得られた被膜の成膜直後（初期）と耐湿試験後の被膜の付着性を評価した。耐湿試験後に極一部で剥離が見られただけで初期の付着性では「剥離なし」であった。キズ付き性試験ではキズが見られなかった。また、光学特性は可視光透過率が９１％、３５０ｎｍの透過率は８８％であった。
実施例２８〜３１
実施例２７において使用した表面改質層用液１に代えて、それぞれ、
実施例２８では表面改質層用液２を使用し、
実施例２９では表面改質層用液３を使用し、
実施例３０では表面改質層用液４を使用し、
実施例３１では表面改質層用液５を使用し、
それ以外は、実施例２７と同じコロナ放電処理５ｍｍ／ｓ、ハードコート液１および硬化条件で、実施例２７と同様の方法でハードコート層を形成した。
さらに実施例１と同様の方法で被膜の付着性とキズ付き性を評価したところ、実施例２８〜３１のいずれも初期の付着性はいずれも「剥離なし」、耐湿試験後の付着性はいずれも「剥離なし」であり、いずれの実施例もキズ付き性試験ではキズがなく、いずれの実施例も可視光透過率が９１％であり、３５０ｎｍの透過率については実施例２８では８８％であり実施例２９〜３１のいずれも０％であった。
【０１０３】
実施例３２
実施例８と同じ方法で得た表面改質層被覆基材の上にハードコート液５を塗布し、硬化させて膜厚３μｍのハードコート層を被覆した。
得られた被膜の成膜直後（初期）と耐湿試験後の被膜の付着性を評価した。耐湿試験後に極一部で剥離が見られただけで初期の付着性は「剥離なし」であった。キズ付き性試験ではキズが見られなかった。また、光学特性は可視光透過率が９１％、３５０ｎｍの透過率は８８％であった。
実施例３３〜３６
実施例３２において使用した表面改質層用液１に代えて、それぞれ、
実施例３３では表面改質層用液２を使用し、
実施例３４では表面改質層用液３を使用し、
実施例３５では表面改質層用液４を使用し、
実施例３６では表面改質層用液５を使用し、
それ以外は、実施例３２と同じコロナ放電処理５ｍｍ／ｓ、ハードコート液５および硬化条件で、実施例３２と同様の方法でハードコート層を形成した。
さらに実施例１と同様の方法で被膜の付着性とキズ付き性を評価したところ、実施例３３〜３６のいずれも初期の付着性はいずれも「剥離なし」、耐湿試験後の付着性はいずれも「剥離なし」であり、いずれの実施例もキズ付き性試験ではキズがなく、いずれの実施例も可視光透過率が９１％であり、３５０ｎｍの透過率については実施例３３では８８％であり実施例３４〜３６のいずれも０％であった。
実施例２７〜３６の結果を表４にまとめて示す。
【０１０４】
実施例３７〜４２
実施例３０において使用したハードコート液１に代えて、それぞれ、
実施例３７ではハードコート液２を使用し、
実施例３８ではハードコート液３を使用し、
実施例３９ではハードコート液４を使用し、
実施例４０ではハードコート液６を使用し、
実施例４１ではハードコート液７を使用し、
実施例４２ではハードコート液８を使用し、
それ以外は、実施例３０と同じコロナ放電処理５ｍｍ／ｓ、表面改質用液４および硬化条件で、実施例３０と同様の方法でハードコート層を形成した。
さらに実施例１と同様の方法で被膜の付着性とキズ付き性を評価したところ、実施例３７〜４２のいずれも初期の付着性はいずれも「剥離なし」、耐湿試験後の付着性はいずれも「剥離なし」であり、いずれの実施例もキズ付き性試験ではキズがなく、いずれの実施例も可視光透過率が９１％であり、３５０ｎｍの透過率についてはいずれの実施例も０％であった。そして実施例３７および４０については曇価が１０〜１１％であり、防眩性が優れていた。実施例３８および４１について汚れ性試験による「汚れなし」であって撥水防汚性が優れていた。また実施例３９および４２については、曇価が１０〜１１％であり、汚れ性試験による「汚れなし」であり、防眩性および撥水防汚性が優れていた。
実施例３７〜４２の結果を表５にまとめて示す。
【０１０５】
実施例４３
実施例３０で得られたハードコート層付き基板の上に真空蒸着によって厚み１００ｎｍ／１００ｎｍのＴｉＯ_２／ＳｉＯ_２積層無機膜層（反射防止層）を形成させた。
実施例４４
実施例３５で得られたハードコート層付き基板の上に真空蒸着によるＳｉＯ_２無機膜層（反射防止層）を形成させた。
さらに実施例１と同様の方法で被膜の付着性とキズ付き性を評価したところ、実施例４３および４４のいずれも初期の付着性はいずれも「剥離なし」、耐湿試験後の付着性はいずれも「剥離なし」であり、実施例４３および４４のキズ付き性試験ではキズがなく、実施例４５〜５１のキズ付き性試験では多数のキズがあり、いずれの実施例も可視光透過率が９３％であり、３５０ｎｍの透過率についてはいずれの実施例も０％であった。また実施例４３および４４はいずれも５％の可視光反射率を示し、実施例２７の試料について同様に測定した可視光反射率９％よりも小さな値であり、優れた反射防止性能を示している。
【０１０６】
実施例４５〜５１
実施例１１で得られた表面改質層付き基板の上に、それぞれ実施例４５〜５１に応じて、スパタリングによるＴｉＯ_２／ＳｉＯ_２積層無機膜層（実施例４５）、真空蒸着によるＳｉＯ_２の無機膜層（実施例４６）、プラズマＣＶＤでＴｉＯ_２とＳｉＯ_２の積層無機膜層（実施例４７）、プラズマＣＶＤによるＳｉＯ_ｘの無機膜層（実施例４８）、スパッタリングによるＳｉＯ_ｘＮ_ｙの無機膜層（実施例４９）、スパッタリングによるＳｉＮ_ｘの無機膜層（実施例５０）およびスパッタリングによるＩＴＯの無機膜層（実施例５１）を形成させた。
さらに実施例１と同様の方法で被膜の付着性とキズ付き性を評価したところ、実施例４５〜５１のいずれも初期の付着性はいずれも「剥離なし」、耐湿試験後の付着性はいずれも「剥離なし」であり、実施例４３および４４のキズ付き性試験ではキズがないが実施例４５〜５１では多数のキズがあり、いずれの実施例も可視光透過率が８９〜９３％であり、３５０ｎｍの透過率についてはいずれの実施例も０％であった。実施例４５〜４７のいずれも５％の可視光反射率を示し、実施例２７の試料について同様に測定した可視光反射率９％よりも小さな値であり、優れた反射防止性能を示している。また実施例４８〜５０はいずれも優れた耐透湿性を示し、また実施例５１は優れた透明導電性を示した。
実施例４３〜５１の結果を表６にまとめて示す。
【０１０７】
比較例４
実施例３２で使用した表面改質処理液１に代えて表面改質処理液を全く使用しない他は実施例３２と同様にして厚み３μｍのハードコート層を形成した。
比較例５
実施例４４で使用した表面改質処理液４に代えて表面改質処理液を全く使用しない他は実施例４４と同様にしてスパッタリングによって厚み１００ｎｍ／１００ｎｍのＴｉＯ_２／ＳｉＯ_２積層膜反射防止層を形成した。
比較例６
比較例５で行った親水化処理表面を行わず、処理後の水滴接触角が９０度になるようにすること以外は比較例５と同様にしてスパッタリングによって厚み１００ｎｍ／１００ｎｍのＴｉＯ_２／ＳｉＯ_２積層膜反射防止層を形成した。
比較例４〜６で得られた膜の成膜直後（初期）の付着性をテストしたがいずれもすべて剥離した。キズ付き性試験では比較例４はキズがなかったが、比較例５および６のいずれも膜が剥がれるほどキズがついていた。また、比較例４〜６のいずれについても光学特性は可視光透過率が９１〜９２％であり、３５０ｎｍの透過率は８８〜８９％であった。
比較例４〜６の結果を表６にまとめて示す。
【０１０８】
実施例５２
実施例３０で得られたハードコート層付き基板の上に前記屈折率調整用液１を塗布、硬化して、膜厚が１１０ｎｍで屈折率が１．７２の屈折率調整層を形成した。その上に低屈折率用コート液１１を塗布し、８０℃で１時間加熱し、硬化させ、膜厚が１００ｎｍで屈折率が１．４１の低屈折率層を形成した。
実施例５３
実施例５２で用いた低屈折率用コート液１１に代えて低屈折率用コート液１２を使用した他は実施例５２と同様にしてハードコート層、屈折率調整層および低屈折率層を形成した。
実施例５４
実施例５２で用いたハードコート層付き基板（実施例３０で製造）に代えて実施例３７で製造したハードコート層付き基板を使用した他は実施例５２と同様にして屈折率調整層および低屈折率層を形成した。
実施例５２〜５４について得られた積層被膜の付着性を評価した。いずれの実施例も初期および耐湿試験後にも被膜の剥離がなく付着性に問題はなかった。実施例１と同様に前記キズ付き性、光学特性をそれぞれ評価したところ、いずれもキズはなく、可視光線透過率はいずれも９３％であった。また曇価については実施例５２および５３は０．１％であったが、実施例５４の曇価は１０％であり、実施例５４は優れた防眩性を示した。可視光反射率を測定したところいずれも６％であり、優れた反射防止性能を示している。汚れ性試験および表面の水滴接触角については、実施例５２および５４は「少し汚れ残りあり」でそれぞれ８５度、８６度であったが、実施例５３はそれぞれ「汚れ残しなし」および１０２度であり、優れた撥水、防汚性を示した。
【０１０９】
実施例５５
実施例５２で用いた低屈折率コート液１１の塗布、硬化に代えて、真空蒸着による低屈折率のＳｉＯ_２膜（膜厚１００ｎｍ）被覆を行った他は実施例５２と同様にしてハードコート層、屈折率調整層および低屈折率層を形成した。
実施例５６
実施例５５で用いたハードコート液１の塗布、硬化に代えて、ハードコート液５の塗布、硬化を行った他は実施例５５と同様にしてハードコート層、屈折率調整層および低屈折率層を形成した。
実施例５７
実施例１で得られた表面改質層付き基板の上に下地ハードコート液１０を塗布し、硬化することにより、４μｍの厚みの下地ハードコート層を形成し、その下地ハードコート層の上にハードコート液９をスピナー法で塗布し、光硬化させることにより、０．１５μｍの厚みのハードコート層を形成した。その上に真空蒸着によって厚み１００ｎｍ／１００ｎｍのＴｉＯ_２／ＳｉＯ_２積層無機膜層を形成させた。
実施例５８
実施例５７における真空蒸着によるＴｉＯ_２／ＳｉＯ_２積層無機膜層の形成を行わなかった他は実施例５７と同様にして表面改質層、下地ハードコート層、ハードコート層を形成した。
実施例５５〜５８について得られた被膜の付着性を評価した。いずれの実施例も初期および耐湿試験後にも被膜の剥離がなく付着性に問題はなかった。実施例１と同様に前記キズ付き性、光学特性をそれぞれ評価したところ、いずれもキズはなく、可視光線透過率はいずれも９０〜９２％であった。可視光反射率を測定したところ実施例５５〜５７はいずれも５％であり、優れた反射防止性能を示している。また曇価については実施例５５および５６は０．１％であったが、実施例５７および５８の曇価は１０％であった。実施例５７および５８で使用したハードコート液９中の微粒子（Ｊ）の粒径が実施例３７のそれよりも小さいので、光の拡散状態が均一であり均一な防眩性が得られることが観察された。汚れ性試験については、いずれも「少し汚れ残りあり」であり、表面の水滴接触角についてはそれぞれ８５度、８４度、８６度、８６度であった。
実施例５２〜５６の結果を表７にまとめて示す。
なお、各表中にはそれぞれの上記実施例及び比較例で述べていないデータも入れている場合がある。
【０１１０】
【表１】

【０１１１】
【表２】

【０１１２】
【表３】

【０１１３】
【表４】

【０１１４】
【表５】

【０１１５】
【表６】

【０１１６】
【表７】

[0001]
[Industrial applications]
The present invention relates to an amorphous polyolefin resin article coated with a surface modified layer, a method for producing an amorphous polyolefin resin article coated with a hard coat coating and a functional hard coat coating on the surface modified layer, and the resin article. About.
[0002]
[Prior art]
Amorphous polyolefin resins are used for various applications because of their excellent properties. For example, the polyolefin resin comprising a cyclopentene polymer described in JP-A-6-168625 has excellent electrical insulation properties and low water absorption, and thus has excellent dimensional stability even in a high humidity environment. Further, an amorphous polyolefin resin comprising a norbornene-based ring-opening polymer described in JP-A-10-152549 has excellent optical characteristics such as transparency, water resistance, and birefringence, and high optical characteristics are required. It is applied to products that are used. Specifically, amorphous polyolefin resins are widely used for optical parts, electronic parts, transparent automobile parts and the like used for display panels and the like.
[0003]
[Problems to be solved by the invention]
On the other hand, amorphous polyolefin resins have no functional groups in the structure, so it is difficult to coat functional materials or adhere to other materials, and it is difficult to provide a coating layer on the surface of the base material. was there. In addition, since the amorphous polyolefin resin has a small surface energy, it is difficult to apply the liquid easily when wet coating, and it is difficult to apply the liquid uniformly. Therefore, when producing various products using the amorphous polyolefin resin, there is a problem that the superiority of the base material cannot be sufficiently exhibited.
[0004]
In addition, since the amorphous polyolefin resin has a small surface hardness, it is easily damaged by external stress, and as a result, its application range is limited.
[0005]
An object of the present invention is to provide an amorphous polyolefin resin article having a surface with improved adhesion so that a functional thin film can be firmly coated. Another object of the present invention is to provide an amorphous polyolefin resin article with a thin film to impart abrasion resistance, an antireflection function, an antiglare property, a water repellency, a hydrophilic property, an antifouling property, etc. An object of the present invention is to provide a resin-coated article utilizing the characteristics of a polyolefin resin substrate and a method for producing the same.
[0006]
[Means for Solving the Problems]
That is, in the present invention, after a surface of an amorphous polyolefin resin substrate is subjected to a hydrophilic treatment, a surface modifying liquid containing a polymer of alkyl (meth) acrylate is applied to the surface of the hydrophilic treatment and cured. A method for producing a surface-modified layer-coated amorphous polyolefin resin article, characterized by forming a surface-modified layer.
[0007]
In the present invention, the surface of the amorphous polyolefin resin substrate is subjected to a hydrophilic treatment. As the hydrophilic treatment, for example, corona discharge treatment, plasma treatment, UV ozone treatment, ozone water cleaning, and organic peroxide treatment are used. By performing this step, the surface of the amorphous polyolefin resin base material is oxidized, and the adhesion of the coating film coated thereon is improved. Further, organic stains on the surface of the substrate can be removed. Before the treatment, the surface of the resin substrate having a water droplet contact angle of about 90 degrees preferably has a water droplet contact angle of 60 degrees or less by the hydrophilic treatment. When the elemental composition of the substrate surface after the hydrophilic treatment is measured by X-ray photoelectron spectroscopy (XPS), the amount of oxygen is larger than that before the hydrophilic treatment, and the oxygen is in the form of hydroxyl, carbonyl, and carboxyl groups in the resin. It is introduced only near the surface. When these functional groups serve as bonding sites with the coating, a coating having good adhesion can be formed. At this time, if the ratio of the number of oxygen atoms to the number of carbon atoms (O / C) on the resin surface is 0.05 or more, a film with even better adhesion can be formed.
[0008]
In order to enhance the adhesion of the inorganic film layer and the hard coat layer to the resin substrate, a surface modification layer is provided on the surface of the resin substrate that has been subjected to the hydrophilic treatment.
This surface-modified layer is obtained by applying a surface-modifying liquid containing a polymer of alkyl (meth) acrylate and then curing the liquid.
As a surface-modifying liquid containing an alkyl (meth) acrylic polymer,
(A) a surface modifying liquid containing a homopolymer of an alkyl (meth) acrylate dissolved in a solvent, or
(B) Surface-modifying liquid containing a copolymer (copolymer) of an alkyl (meth) acrylate and a (meth) acrylic monomer having an alkoxysilyl group
Is preferably used.
In this specification, an acryloyl group or a methacryloyl group is referred to as a (meth) acryloyl group, acrylate or methacrylate is referred to as a (meth) acrylate, and acrylic acid or methacrylic acid is referred to as a (meth) acrylic acid.
The surface modification liquid (A) was obtained by dissolving a homopolymer of a linear alkyl (meth) acrylate such as polymethyl methacrylate, polyethyl methacrylate, polymethyl acrylate, or polyethyl acrylate in a solvent. Contains in a state. These homopolymers preferably have a molecular weight of from 10,000 to 300,000. The linear alkyl (meth) acrylate homopolymer is commercially available, for example, as a solvent-soluble (meth) acrylic resin composition. For example, a methyl methacrylate polymer solution (“paraloid A-10” having a molecular weight of 100,000, 30%, solvent: propylene glycol monomethyl ether acetate, manufactured by Rohm and Haas Japan K.K. and methyl methacrylate polymer ("paraloid A-11" molecular weight: 125,000, solid content: 100%, ROHM & Haas Japan Co., Ltd.).
[0009]
The surface modification liquid (A) may further contain an organic silicon compound. By containing this, the adhesion between the surface-modified layer and the substrate or / and the adhesion between the surface-modified layer and the coating layer thereon can be further increased.
As the organosilicon compound, the following formula (1)
R¹nSi (R²)_4-n(1)
Where R¹Is an organic functional group having a functional group selected from a methacryloxy group, an acryloxy group, an epoxy group, a vinyl group, an allyl group and an amino group;²Is one or more hydrolyzable groups selected from an alkoxyl group, an acetoxyl group and chlorine, and n is an integer of 1 to 3,
Is preferably used.
R in the above formula (1)¹Preferred are methacryloxy, acryloxy and amino groups. In particular, R¹Is a methacryloxy group, and R²Is more preferably used, because alkoxysilane having a (meth) acryl group, which is a silicon compound of an alkoxyl group, further enhances adhesion. The addition amount of the organosilicon compound of the formula (1) is preferably 1 to 70 parts by weight, more preferably 2 to 40 parts by weight, based on 100 parts by weight of the alkyl (meth) acrylate homopolymer. Examples of the alkoxysilane having a (meth) acryl group include γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (Meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropyldimethylmethoxysilane, and γ- (meth) acryloxypropyldimethylethoxysilane.
[0010]
The surface modification liquid (B) includes a copolymer (copolymer) of an acrylic and / or methacrylic (hereinafter referred to as (meth) acrylic) monomer having an alkoxysilyl group and an alkyl (meth) acrylate monomer. ) Is contained.
The (meth) acrylic monomer having an alkoxysilyl group is usually represented by the following formula (6)
CH₂= C (R¹⁴) COOC₂H₆SiR^Fifteen ₄(OR¹⁶)_3-d(6)
Where R¹⁴Is hydrogen or a methyl group;^FifteenIs a hydrocarbon group having 1 to 6 carbon atoms;¹⁶Is independently a hydrocarbon group having 1 to 5 carbon atoms, an alkoxyalkyl group, or an acyl group having 1 to 4 carbon atoms, and d is 0, 1 or 2,
Is represented by
[0011]
In the (meth) acrylic monomer having an alkoxysilyl group represented by the formula (6), R in the formula^FifteenAs an alkyl group such as methyl, ethyl, propyl and butyl; an aryl group such as phenyl: an alkenyl group such as vinyl and allyl;¹⁶Examples of the alkyl group include an alkyl group such as methyl, ethyl, propyl, and butyl: an alkoxyalkyl group such as methoxyethoxy, ethoxyethoxy, and butoxyethoxy; an acyl group such as acetyl.¹⁴, R^Fifteen, R¹⁶Various compounds are used in the present invention depending on the type of and the number of d. Specific examples include the following.
[0012]
γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ -(Meth) acryloxypropyldimethylmethoxysilane, γ- (meth) acryloxypropyldimethylethoxysilane and the like.
Examples of the alkyl (meth) acrylate monomer copolymerized with the (meth) acrylic monomer having an alkoxysilyl group include the following. Examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
[0013]
The copolymer is obtained by addition polymerization of the monomer and an alkyl (meth) acrylate monomer. Note that R¹⁶Is a mixture of different groups, a monomer having a different group may be polymerized to obtain a copolymer, or a monomer having the same group may be polymerized to obtain a copolymer. Can be obtained by transesterification in the presence of an alcohol.
[0014]
The copolymer has a general formula in its molecule.
-(-CH₂-C (R¹⁴) -COOC₂H₆SiR^Fifteen ₄(OR¹⁶)_3-d)-
Where R¹⁴, R^Fifteen, R¹⁶And d are the same as defined in the above formula (6),
Is a copolymer having a structure represented by
The weight average molecular weight of the copolymer is preferably from 10,000 to 300,000, more preferably from 20,000 to 200,000. If it is smaller than 10,000, the adhesion to the polyolefin-based resin substrate is reduced. If it is larger than 300,000, the appearance of the surface-modified layer is undesirably deteriorated.
[0015]
The monomer represented by the formula (6) is contained in the copolymer in an amount of 1 to 70% by weight, preferably 2 to 40% by weight, more preferably 2 to 30% by weight. When the amount is less than 1% by weight, the adhesion between the surface-modified layer and the film coated thereon is reduced. When the amount is more than 70% by weight, the adhesion of the surface-modified layer to the polyolefin-based resin substrate is reduced. At the same time, the stability of the surface modifying liquid decreases.
[0016]
A curing catalyst can be added to the surface modification liquid (B). The curing catalyst is used for polycondensation of the alkoxysilyl group, and by the polycondensation of the alkoxysilyl group, the solvent in the coating solution for coating on the surface modification layer makes it difficult for the surface modification layer to be eluted. Become. Acids, alkalis, organic acid metal salts and the like can be used as the curing catalyst, and among them, ammonium perchlorate is preferably used. The amount of the curing catalyst added is about 0.005 to 5% by weight, more preferably about 0.01 to 1% by weight, based on the total amount of the copolymer and melamine described below. If the amount is less than about 0.005% by weight, the effect of the addition is small. If the amount exceeds 5% by weight, the surface-modified layer tends to become cloudy. Adhesion decreases.
[0017]
A crosslinking agent can be added to the surface modification liquid (B). The cross-linking agent causes a cross-linking reaction between the alkoxyl groups of the (meth) acrylic monomer by a hydroxyl group or an -OR group in the structure. Thereby, the adhesion durability between the surface modified layer and the film thereon is improved. As the cross-linking agent, methylol melamine partially or wholly alkylated is preferably used. Methylol melamine partially or wholly etherified is hexa (alkoxy) melamine, for example, hexa (methoxymethyl) melamine, hexa (ethoxymethyl) melamine, hexa (propoxymethyl) melamine, hexa (butoxymethyl) melamine, Hexa (cyclohexyloxymethyl) melamine and the like. Of these, hexa (methoxymethyl) melamine is most preferred. The addition amount of the methylol melamine partially or wholly alkylated is such that the reactive group of the crosslinking agent is 0.01 to 1.0 equivalent, more preferably 0 equivalent, relative to 1 equivalent of the alkoxysilyl group contained in the copolymer. It is more preferable to determine the amount to be added so as to be 0.03 to 0.3 equivalent.
[0018]
An ultraviolet absorber can be added to the surface modification liquids ((A) and (B)). By this addition, the surface-modified layer is provided with a function of blocking ultraviolet rays, and the weather resistance of the adhesive force between the surface-modified layer and the coating layer thereon can be increased. At the same time, an ultraviolet blocking function is imparted to the surface modified layer-coated amorphous polyolefin resin article. Examples of the ultraviolet absorber include benzophenones such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,4-dihydroxybenzophenone, and 2,2'-dihydroxy-4-methoxybenzophenone; (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-octylphenyl) benzotriazole Benzotriazoles such as 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole and 2- (2'-hydroxy-di-t-butylphenyl) -5-chlorobenzotriazole And ethyl-2-cyano-3,3-diphenylacrylate, 2 Cyanoacrylates such as ethylhexyl-2-cyano-3,3-diphenylacrylate. Among them, benzophenone or cyanoacrylate are preferred.
[0019]
The amount of the ultraviolet absorber to be added is 1 to 200 parts by weight, more preferably 10 to 100 parts by weight, based on 100 parts by weight of the alkyl (meth) acrylate polymer in the surface modifying liquid. If the amount is less than 1 part by weight, the adhesion durability between the surface-modified layer and the coating layer thereon, particularly the top coat containing the colloidal silica-containing organopolysiloxane, is insufficient. Of the surface-modified layer becomes poor, resulting in poor adhesion due to cohesive failure of the surface-modified layer.
[0020]
A surfactant can be added to the surface modification liquids ((A) and (B)). Since the surfactant acts as a leveling agent and a lubricity imparting agent, the smoothness of the surface-modified layer and the efficiency of the coating operation can be improved. As the surfactant, a copolymer of polyoxyalkylene and polydimethylsiloxane and a copolymer of polyoxyalkylene and fluorocarbon are preferably used. These are used in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the total liquid.
[0021]
In the surface modification liquid, a solvent is further added to the above components.
Examples of the solvent include alcohols such as methanol, ethanol, isopropanol, butanol and diacetone alcohol; ethers such as ethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, and dioxane; cellosolves such as methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, and butyl cellosolve; Esters such as ethyl acetate, butyl acetate, ethylene glycol diacetate and ethyl cellosolve acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and diisopropyl ketone; carboxylic acids such as formic acid, acetic acid and propionic acid; n-pentane, n Aliphatic hydrocarbons such as hexane and n-heptane; aromatic hydrocarbons such as benzene, toluene and xylene; dichloromethane; Halogenated hydrocarbons such as chloroethane, trichloroethane, trichloroethylene, 1,1,2-trichloro-1,2,2-trifluoroethane; nitro compounds such as nitromethane, nitroethane, and nitropropane; acetonitrile, propionitrile, butyronitrile And amides such as formamide, acetamide and N, N-dimethylformamide, and these may be used in combination. The amount of the solvent varies depending on the preferred thickness of the finally obtained modified layer and the coating method, but is adjusted so that the solid content of the surface modifying liquid is generally 1 to 20% by weight.
[0022]
The surface modification liquid is applied to the surface of the amorphous polyolefin resin substrate which has been subjected to the hydrophilic treatment in a suitable thickness. The coating method may be any of dipping, spraying, flow coating, roll coating, spin coating, gravure coating, flexographic printing, screen printing, brushing, and the like.
After applying the surface modification liquid, the surface modification layer is formed by holding at room temperature to the deformation temperature of the base material or lower, usually 70 to 130 ° C. for several seconds to several tens of minutes, and curing to cure. The thickness of the surface modified layer is preferably 0.005 to 20 μm from the viewpoint of the effect on the properties of the functional film coated thereon and the adhesion to the substrate and the functional film. More preferably, it is 0.01 to 5.0 μm (10 to 5,000 nm), and further preferably, it is 0.01 to 0.1 μm (10 to 100 nm).
[0023]
A hard coat liquid containing colloidal silica and an organosilicon compound is further applied to the surface of the amorphous polyolefin resin substrate on which the surface modified layer has been formed, and then cured to form a hard coat layer.
The first embodiment of the hard coat liquid in the present invention is:
(A) a polyfunctional acrylate,
(B) Formula (2) below
X_aSi (R³(NHR⁴)_bNR⁵H)_4-a(2)
Here, X is an alkoxyl group having 1 to 6 carbon atoms, and R³, R⁴Are the same or different divalent hydrocarbon groups,⁵Is a hydrogen atom or a monovalent hydrocarbon group, a is an integer of 1 to 3, b is 0 or an integer of 1 to 6,
An aminosilane represented by, and
(C) Colloidal silica
It contains.
[0024]
Hereinafter, each component of the first embodiment of the hard coat liquid (hereinafter, referred to as hard coat liquid (1)) will be described.
The polyfunctional acrylate as the component (A) is a (meth) acrylate having at least two hydroxyl groups and at least two (meth) acryloyl groups in a molecule. Examples of the polyfunctional acrylate include 1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, and neopentyl glycol diacrylate. 1,4-butanediol dimethacrylate, poly (butanediol) diacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, triethylene glycol diacrylate, triisopropylene glycol diacrylate, polyethylene glycol diacrylate And diacrylates such as bisphenol A dimethacrylate; trimethylolpropane triacrylate Triacrylates such as trimethylolpropane trimethacrylate, pentaerythritol monohydroxytriacrylate and trimethylolpropane triethoxytriacrylate; tetraacrylates such as pentaerythritol tetraacrylate and di-trimethylolpropane tetraacrylate; Pentaacrylates such as erythritol (monohydroxy) pentaacrylate may be mentioned. One or more polyfunctional acrylates are used together.
[0025]
The aminosilane as the component (B) is an alkoxysilane having an amino group or a substituted amino group represented by the formula (2). In the formula (2), a is preferably 2 or 3, and b is preferably 0 or 1.
Examples of the aminosilane represented by the formula (2) include, for example, n- (2-aminoethyl-3-aminopropyl) trimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, γ- (2-amino Ethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropylmethyldimethoxysilane Hydrochloride and γ-anilinopropyltrimethoxysilane can be mentioned.
[0026]
The colloidal silica as the component (C) is, for example, 10 to 50% by weight of SiO.₂(Colloidal silica sol having a particle size of 1 to 200 nm, preferably 1 to 100 nm) or SiO having a particle size of 1 to 200 nm, more preferably 1 to 100 nm.₂Can be derived from the composite oxide fine particles containing. This composite oxide is SiO 2₂And a metal oxide, wherein the metal oxide is one selected from the group consisting of Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, Pd, In and Ti. Two or more metal oxides can be mentioned. Specific example is Al₂O₃, SnO₂, Sb₂O₅, CeO₂, Ta₂O₅, La₂O₃, Fe₂O₃, ZnO, WO₃, ZrO₂, PdO₂, In₂O₃And TiO₂There is. SiO₂The composite oxide fine particles containing titanium and silicon (TiO 2)₂・ SiO₂), Composite oxide fine particles of titanium, cerium and silicon (TiO₂・ CeO₂・ SiO₂), Composite oxide fine particles of titanium, iron and silicon (TiO₂・ Fe₂O₃・ SiO₂), Composite oxide fine particles of titanium, zirconium and silicon (TiO₂・ ZrO₂・ SiO₂), Composite oxide fine particles of titanium, aluminum and silicon (TiO₂・ Al₂O₃・ SiO₂). In these composite oxide fine particles, SiO₂5 mol% or more of components (molar ratio ： metal: SiO₂= 9.5: 0.5 ° or more).
[0027]
The composite oxide may be surface-modified with an organic silane compound in order to enhance dispersibility in a solvent. The amount of the organic silane compound used is preferably 20% by weight or less based on the weight of the composite oxide fine particles. The surface treatment may be performed while the organic silane compound used for the treatment retains a hydrolyzable group, or after the hydrolysis.
[0028]
Such organic silane compounds include, for example, trimethylmethoxysilane, phenyldimethylmethoxysilane, vinyldimethylmethoxysilane, γ-acryloxypropyldimethylmethoxysilane, γ-mercaptopropyldimethylmethoxysilane, N-β (aminoethyl) γ-aminopropyl Monofunctional silanes such as dimethylmethoxysilane, β- (3.4-epoxycyclohexyl) ethyldimethylmethoxysilane; dimethyldimethoxysilane, phenylmethyldimethoxysilane, vinylmethyldimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ -Mercaptopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethoxydiethoxysilane and β- (3.4-epoxy Bifunctional silanes such as cyclohexyl) ethylmethyldimethoxysilane; methyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercapto Trifunctional silanes such as propyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β- (3.4-epoxycyclohexyl) ethyltrimethoxysilane; tetraethylorthosilicate and Mention may be made of tetrafunctional silanes such as tetramethylorthosilicate. When the complex oxide is treated with such a silane compound, it is preferably carried out in, for example, water, alcohol or another organic medium.
[0029]
The hard coat liquid (1) used in the present invention preferably contains a photopolymerization initiator for polymerizing a polyfunctional acrylate. As the photopolymerization initiator, a radical photopolymerization initiator, a cationic photopolymerization initiator, or the like can be used. Examples of the radical photopolymerization initiator include benzophenone, [2-hydroxy-2-methyl-1-phenylpropan-1-one] and [1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-. On], [4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl ketone)], [2,2-dimethoxy-1,2-diphenylethan-1-one], [1-hydroxy-cyclohexyl] -Phenyl-ketone], [2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one], [bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl -Pentylphosphine oxide] and [2-benzyl-2-dimethylamino-1--1- (4-morpholinophenyl) -butanone-1]. Examples of the cationic photopolymerization initiator include phenyl- [m- (2-hydroxytetradecyclo) phenyl] iodonium hexafluoroantimonate, dialkyliodonium, tetrakis (pentafluorodiphenyl) borate and the like. .
[0030]
The amount of the photopolymerization initiator is preferably from 0.1 to 30 parts by weight, more preferably from 1 to 15 parts by weight, based on 100 parts by weight of the polyfunctional acrylate of the hard coat composition.
[0031]
The hard coat liquid (1) used in the present invention preferably contains a hydrolysis catalyst for hydrolysis and polycondensation of the aminosilane (B). Examples of the hydrolysis catalyst include acid catalysts such as formic acid, acetic acid, propionic acid, butanoic acid, oxalic acid, acrylic acid, methacrylic acid, hydrochloric acid, nitric acid, and sulfuric acid, and basic catalysts such as ammonia, sodium hydroxide, and potassium hydroxide aqueous solution. A catalyst is used. Of these, an acid catalyst in the form of an aqueous solution, for example, acetic acid or (meth) acrylic acid is preferably used. The amount of the acid catalyst to be added is preferably 5 to 30 parts by weight based on 100 parts by weight of the aminosilane (B).
[0032]
The hard coat liquid (1) used in the present invention is preferably 1.5 to 50 parts by weight, and more preferably 8 to 25 parts by weight, based on 100 parts by weight of the polyfunctional acrylate (A). Parts, colloidal silica (C) (solid content) 10 to 150 parts by weight, preferably 40 to 85 parts by weight. The hard coat liquid containing the components (A) to (C) may be hereinafter referred to as “basic hard coat liquid 1”.
[0033]
The second embodiment of the hard coat liquid in the present invention is:
(D) The following formula (3)
R⁷ _aR⁸ _bSi (OR⁹)_4-ab(3)
Where R⁷Is an alkyl group having 1 to 4 carbon atoms, an allyl group or a halogenated alkyl group having 6 to 12 carbon atoms, a methacryloxyalkyl group having 5 to 8 carbon atoms, a ureidoalkylene group having 2 to 10 carbon atoms, A ureidoalkylene group, an aromatic alkylene group or a mercaptoalkylene group;⁸Is an alkyl group having 1 to 6 carbon atoms, an allyl group, an alkenyl group, a halogenated alkyl group or a halogenated allyl group;⁹Is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an acyl group or an alkylacyl group, a = 1, 2 or 3, and b = 0, 1 or 2.
An organosilicon compound represented by
(E) Colloidal silica
It contains.
[0034]
Hereinafter, each component of the second embodiment of the hard coat liquid (hereinafter, referred to as hard coat liquid (2)) will be described.
Among the organosilicon compounds (D), alkyl trialkoxysilanes such as methyltrimethoxysilane are particularly preferably used. As the colloidal silica (E), those described for the colloidal silica (C) in the hard coat liquid (1) can be used. The mixing ratio of each component is preferably from 40 to 85 parts by weight, more preferably from 50 to 75 parts by weight, based on 100 parts by weight of the compound (D) represented by the formula (3). The hard coat liquid containing the components (D) to (E) may be hereinafter referred to as “basic hard coat liquid 2”.
[0035]
In order to impart an antiglare property to the hard coat-coated amorphous polyolefin resin article obtained in the present invention, 0.05 μm (50 nm) to 10 μm of (J) component is added to the basic hard coat liquid (1) or (2). Fine particles having an average particle size can be contained.
[0036]
As the fine particles (J) having an average particle diameter of 0.05 μm to 10 μm, fine particles (J) made of a metal or an inorganic compound are preferably used. The more preferable average particle size of the fine particles (J) is 2 to 10 μm, and the more preferable average particle size is 4 to 8 μm. Especially for display applications, the addition of the fine particles (J) can reduce the reflection of ambient light and sharpen the image display.
[0037]
Examples of the material of the fine particles (J) made of a metal or an inorganic compound include Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, In, Ti, Mg, oxides thereof, and composite oxides thereof. Object or CaCO₃, BaSO₄And the like. These can be used alone or in combination of two or more. Of these, SiO₂Is most preferred.
[0038]
These fine particles (J) can be used after surface modification with an organic silane compound or an organic compound to enhance dispersibility in a solvent. As the organic silane compound, the organic silane compounds exemplified for modifying the surface of colloidal silica, particularly monofunctional silane, are preferably used.
[0039]
Products dispersed as fine particles (J) having an average particle size of 0.05 μm (50 nm) to 10 μm in a dispersion medium at a ratio of 15 to 60% by weight can be obtained as commercial products as described below. Examples of the silica fine particles include “Syloid C803” (average particle size: 3.6 μm, manufactured by WR Grace Japan), “Sylysia 350” (average particle size: 3.9 μm, manufactured by Fuji Silysia Chemical Ltd.), “Silo” "Sphere C-1504" (average particle size 4 m, same as above), "Sylosphere C-1510" (average particle size 10 m, same as above), "JA-450" (average particle size 4-8 m, Jujo Chemical Co., Ltd.) ), “MP-3040” (average particle size: 0.30 μm, manufactured by Nissan Chemical Industry Co., Ltd.), “MP-4540” (average particle size: 0.45 μm, manufactured by Nissan Chemical Industry Co., Ltd.), “ “KE-W50” (average particle size: 0.50 to 0.56 μm, manufactured by Nippon Shokubai Co., Ltd.), “KE-E150” (average particle size: 1.40 to 1.60 μm, manufactured by Nippon Shokubai Co., Ltd.) And the like. Other than the silica fine particles, titanium oxide fine particles “palladium characteristic matting agent N” (average particle size 2 to 5 μm, manufactured by Ohara Palladium Co., Ltd.), and calcium stearate fine particles “palladium # 1000” (average particle size 2 to 5 μm, Ohara palladium ( Co., Ltd.).
[0040]
These fine particles (J) are preferably spherical or nearly spherical, and may be solid particles or porous particles. The refractive index is preferably the same as or smaller than the refractive index of the photocured product of the remaining hard coat liquid excluding the fine particles (J). This makes it easier to reduce interference unevenness due to uneven film thickness.
The above-mentioned colloidal silicas (C) and (E) are components that increase the hardness of the hard coat layer. The fine particles (J) are components that form predetermined irregularities on the surface of the hard coat layer to impart antiglare properties. Colloidal silica having a large average particle diameter, for example, colloidal silica having an average particle diameter of 50 nm to 200 nm, functions as fine particles (J). Therefore, if the hard coat liquid used in the present invention contains colloidal silicas (C) and (E) having an average particle size of 50 nm to 200 nm, the anti-glare property can be obtained without containing the fine particles (J). Is obtained.
[0041]
In order to provide anti-glare properties, the fine particles (J) are added to the basic hard coat liquid 1 or 2 in an amount of 1.0 to 150 parts by weight, preferably 100 to 100 parts by weight of the polyfunctional acrylate (A) or the organosilicon compound (D). Is preferably added in an amount of 3 to 100 parts by weight. The more preferable content of the fine particles (J) depends on the average particle size of the fine particles (J). When the average particle diameter of the fine particles (J) is relatively large, for example, more than 2 μm and 10 μm or less, the content of the fine particles (J) is preferably 1.0 to 40 parts by weight, and more preferably 3 to 20 parts by weight. Is more preferred. When the average particle size of the fine particles (J) is relatively small, for example, 0.05 μm (50 nm) to 2 μm, the content of the fine particles (J) is preferably 20 to 150 parts by weight, and 50 to 100 parts by weight. Parts are more preferred. The content of the colloidal silica (C) and (E) (solid content) when containing only the colloidal silica (C) and (E) also serving as the fine particles (J) is 40 to 185 parts by weight, preferably 60 to 130 parts by weight. Parts by weight.
[0042]
In order to impart water repellency to the hard coat-coated amorphous polyolefin resin article obtained in the present invention, the hard coat liquid 1 or 2 may contain a fluoroalkylsilane as the component (K).
The following formula (4) is used as the fluoroalkylsilane (K).
R¹⁰ _cR¹¹ _dSi (OR¹²)_4-cd(4)
Where R¹⁰Is a fluorine alkyl group having 1 to 12 carbon atoms;¹¹Is an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkenyl group, a halogenated alkyl group or a halogenated aryl group;¹²Is a hydrogen atom or an alkyl or acyl group having 1 to 4 carbon atoms, c is 1, 2 or 3, and d is 0, 1 or 2. However, c + d is 1, 2 or 3.
Is preferably used.
[0043]
Examples of the compound represented by the formula (4) include 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, and heptadecafluoro Fluoroalkyl trialkoxysilanes such as decyltriethoxysilane; and fluoroalkylalkyldialkoxysilanes such as heptadecafluorodecylmethyldimethoxysilane and heptadecafluorodecylmethyldiethoxysilane. These can be used alone or in combination of two or more.
[0044]
In order to impart water repellency, 1.0 to 20 parts by weight of fluoroalkylsilane (K) is added to 100 parts by weight of the polyfunctional acrylate (A) or the organosilicon compound (D) to the basic hard coat liquid 1 or 2. And more preferably 3 to 15 parts by weight.
[0045]
By adding the above-mentioned fine particles (J) and the above-mentioned fluoroalkylsilane (K) to the basic hard coat liquid 1 or 2, respectively, the hard coat-coated amorphous polyolefin resin article obtained in the present invention has an antiglare property and Water repellency can be imparted.
[0046]
The hard coat liquid used in the present invention may contain one or more of epoxy (meth) acrylate, urethane (meth) acrylate, and polyester (meth) acrylate as physical property modifiers. Epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate can be applied to impart flexibility to the film, increase the hardness of the film, or cure with low energy. The physical property modifier is added to the basic hard coat liquid 1 or 2 in an amount of 10 to 200 parts by weight, preferably 50 to 150 parts by weight, based on 100 parts by weight of the polyfunctional acrylate (A) or the organosilicon compound (D). be able to.
[0047]
Further, the hard coat liquid used in the present invention can contain fine particles for adjusting the refractive index. The refractive index adjusting fine particles are preferably made of inorganic oxide fine particles having an average particle diameter of 1 to 100 nm. For example, aluminum oxide, tin oxide, antimony oxide, tantalum oxide, cerium oxide, lanthanum oxide, iron oxide, zinc oxide, tungsten oxide, zirconium oxide, indium oxide, titanium oxide, titanium oxide / zirconium oxide composite oxide, titanium oxide / oxide Fine particles such as zirconium / silicon oxide composite oxide can be used. The composite oxide preferably contains at least 50% by weight of titanium oxide.
[0048]
The inorganic oxide fine particles for adjusting the refractive index can be used after surface modification with an organic silane compound or an organic compound in order to enhance dispersibility in a solvent. As the organic silane compound, the organic silane compounds exemplified for modifying the surface of colloidal silica, particularly monofunctional silane, are preferably used.
[0049]
The refractive index adjusting fine particles are added to the basic hard coat liquid 1 or 2 in an amount of 1 to 900 parts by weight, preferably 100 to 400 parts by weight, based on 100 parts by weight of the polyfunctional acrylate (A) or the organosilicon compound (D). The refractive index of the hard coat layer obtained by the basic hard coat liquid 1 or 2 can be increased by 0.01 to 0.50. When the colloidal silica (C) or (E) in the hard coat liquid or the fine particles (J) to be added to the hard coat liquid as needed corresponds to the fine particles for adjusting the refractive index, the refractive index is separately determined. In some cases, the refractive index of the hard coat layer can be increased to a predetermined value without adding fine particles for adjustment.
[0050]
The hard coat liquid (1) of the present invention is preferably prepared as a dispersion in a liquid medium containing the above-mentioned active ingredient in a predetermined amount.
During the preparation of the hard coat liquid (1) or during the aging after the preparation, the polyfunctional acrylate (A) reacts with the aminoorganofunctional silane (B). In the reaction of the polyfunctional acrylate with the aminoorganofunctional silane, the primary or secondary amino functional group of the aminoorganofunctional silane is replaced by one or two of the (meth) acrylate double bonds of the polyfunctional acrylate monomer. Michael is added to the above.
This reaction can be carried out at a temperature from room temperature to 100 ° C. In the reaction, the polyfunctional acrylate and the aminoorganofunctional silane can be used alone or in combination of two or more.
[0051]
Examples of the liquid medium include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl. Ether acetate, propylene glycol monobutyl ether acetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Glycols such as propyl ether, diethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol monobutyl ether; cyclohexanone, o-methylcyclohexanone, m-methylcyclohexanone, p- Aliphatic cyclic ketones such as methylcyclohexanone; acetic esters such as ethyl acetate, n-propyl acetate and n-butyl acetate; and alcohols such as methanol, ethanol, 1-propanol and 2-propanol.
[0052]
Further, the hard coat liquid (1) or (2) may contain a leveling agent for a cured film and a lubricity imparting agent as optional components. As such an additive, for example, a copolymer of polyoxyalkylene and polydimethylsiloxane (Paint Additive 19 from Dow Corning) and a copolymer of polyoxyalkylene and fluorocarbon are preferably used. Such additives are preferably used in an amount of 0.001 to 10% by weight based on the total amount of the liquid. In addition, an antioxidant, a weather resistance imparting agent, an antistatic agent, a bluing agent and the like can be contained as other optional components.
The hard coat liquid is preferably used after the solid content concentration is adjusted to, for example, 2 to 50% by weight.
[0053]
The hard coat liquid is applied to the surface of the amorphous polyolefin resin substrate, for example, to one surface or both surfaces of the amorphous polyolefin resin film having a thickness of 30 to 500 μm. The coating can be performed by, for example, spin coating, flow coating, dip coating, spray coating, roll coating, bar coating, gravure coating, flexographic printing, screen printing, or brushing. The coating is preferably performed with a thickness such that the film thickness after curing is 1.0 to 30 μm. If it is smaller than 1.0 μm, the hardness of the film is not sufficient, and if it is larger than 30 μm, the flexibility is reduced. A more preferred thickness is from 1.0 to 10 μm.
[0054]
However, when the underlying hard coat layer is provided below the hard coat layer as described later, the thickness of the hard coat layer after curing can be 0.05 to 1.5 μm. Since the surface of the hard coat layer has minute irregularities, the thickness of the hard coat layer is defined as an average thickness including the surface irregularities.
[0055]
After the application, the hard coat layer is formed by heating the coating film in the case of the hard coat liquid (2) or by irradiating the hard coat liquid (1) with an active energy ray such as an ultraviolet ray or an electron beam. Is done. Heating is performed at 50 to 130 ° C. for several seconds to 5 hours. Various ultraviolet lamps such as a high-pressure mercury lamp and a carbon arc lamp, and laser light can be used for the ultraviolet irradiation. The irradiation conditions of the ultraviolet light are, for example, a wavelength of about 200 to 400 nm and an illuminance of several tens to 100 mW / cm.²(Wavelength 365 nm), the total ultraviolet irradiation energy is 300 to 3000 (mJ / cm).²) For several seconds to 30 minutes.
[0056]
After application of the hard coat liquid, the liquid medium is removed by drying or by vaporization during irradiation. When the hard coat liquid (1) is used, the irradiation causes the (meth) acryloyl groups of the polyfunctional acrylate (A) to be photopolymerized. The hydrolyzable group such as the alkoxyl group of the aminosilane (B) (and the fluoroalkylsilane (K)) is used during preparation of the hard coat composition, during aging, before irradiation after application, or during irradiation after application. Hydrolysis and polycondensation.
[0057]
As described above, the amorphous polyolefin resin article coated with the hard coat layer has excellent surface hardness, and thus has improved scratch resistance. When fine particles (J) are added to the hard coat liquid, antiglare properties are imparted in addition to scratch resistance. The fine particles (J) are preferably buried in the hard coat layer at a depth of at least half the height (diameter in the case of a true sphere) of the fine particles. When the water repellent function is imparted to the hard coat layer, the surface of the fine particles (J) protruding from the hard coat layer is preferably covered with a thin layer of the hard coat, whereby the above function is effectively performed. It is exhibited in. When the fine particles (J) are buried at a height of half or more, it is possible to advantageously prevent the fine particles (J) from falling off from the hard coat layer. Further, the fine particles (J) are preferably adjacent to each other on the outer surface of the hard coat layer and distributed as single particles (single particle layer) without overlapping in the layer thickness direction. The surface roughness of the outer surface of the hard coat layer is preferably such that a 10-point average roughness (Rz) is 6 μm or less. However, if the entire fine particles (J) are buried in the hard coat layer, the anti-glare property cannot be exerted. Therefore, the surface roughness may be 0.05 μm or more expressed as a 10-point average roughness (Rz). preferable. This preferable distribution or surface roughness can be achieved by appropriately adjusting the ratio of the fine particles (J) in the hard coat layer, the thickness of the hard coat layer, and the like.
[0058]
A base hard coat layer can be further provided between the resin base material and the hard coat layer containing fine particles (J). As the base hard coat layer, a hard coat layer obtained from the basic hard coat liquid 1 or 2 can be used. Then, a fine particle (J) -containing hard coat layer is provided on the underlying hard coat layer. The thickness of the hard coat layer is preferably 0.05 to 1.5 μm, and the thickness of the underlying hard coat layer is such that the sum of the thickness of this layer and the thickness of the hard coat layer is preferably 1.0 to 10 μm. Adjusted as follows.
[0059]
The hard coat composition for the fine particle (J) -containing hard coat layer used in combination with the underlying hard coat layer includes fine particles (J) having a relatively small average particle size, for example, an average particle size of 0.05 μm (50 nm) to 2 μm. It is preferable to include those having a diameter. As a result, fine particles (J) having a small average particle diameter can be embedded in the hard coat layer, and a part of the fine particles can be projected to the surface of the hard coat layer, so that uniform anti-glare property can be easily provided. . The ratio of the thickness (μm) of the hard coat layer to the average particle size (μm) of the fine particles (J) is more preferably 50 to 95%. In this case, the fine particles (J) protrude a part of the surface from the surface of the hard coat layer into the hard coat layer, and are more easily distributed as a single particle layer while being buried at a height of half or more thereof. Strong and uniform anti-glare properties can be obtained.
[0060]
Further, when a fluoroalkylsilane (K) is added to the basic hard coat liquid, water repellency is imparted in addition to scratch resistance. This makes it less susceptible to the effects of water adhesion and dew condensation, improves the adhesion of dirt and removes dirt, and can be applied as a member of a terminal display or an optical device.
[0061]
By adding both the fine particles (J) and the fluoroalkylsilane (K) to the basic hard coat liquid 1 or 2, the anti-glare property is improved, and the adhesion of dirt to the fine uneven surface accompanying the anti-glare property, The stain removal property can be improved.
[0062]
At least one inorganic film layer having a thickness of 20 nm to 50 μm (total thickness in the case of two or more layers) can be formed on the hard coat layer or the surface modification layer in the present invention. . As a material of the inorganic film layer, at least one kind of metal selected from the group consisting of Ti, Sn, In, Si, Al, W, Mo, Ag, Zn, Zr, Mg, Cr, and Ni; At least one inorganic compound selected from an oxide and a nitride of the metal is used. In particular, oxides, nitrides, and compounds having good adhesion include TiO.₂, SiO_x, SiN_x, ITO (indium tin oxide), MgF, SiO_xN_yIn addition, SnO₂, TiN₂, ZrO₂, ZnS, Al₂O₃Is mentioned.
[0063]
Examples of the method for coating the inorganic film include a chemical vapor deposition method (CVD method) and a physical vapor deposition method (PVD method). The CVD method includes a plasma CVD method, and the PVD method includes a vacuum deposition method, a sputtering method, and an ion plating method. By providing an inorganic film, anti-reflection properties, transparent conductivity, moisture resistance, and the like can be imparted.
[0064]
Specific examples of the configuration of the inorganic film layer include the following.
TiO by vacuum evaporation method₂/ SiO₂Of a multilayer film (TiO2)₂SiO on the layer₂Stack layers. Two-layer anti-reflection properties)
SiO by plasma CVD_xFilm formation (giving moisture resistance)
TiO by plasma CVD₂/ SiO₂Of a multilayer film (TiO2)₂SiO on the layer₂Stack layers. Adds anti-reflective properties)
SiO by plasma CVD_xFilm formation (single-layer anti-reflection properties)
SiO by sputtering method_xN_yFilm formation (giving moisture resistance)
TiO by sputtering method₂/ SiO₂Of a multilayer film (TiO2)₂SiO on the layer₂Stack layers. Adds anti-reflective properties)
ITO film formation by sputtering (giving transparent conductivity)
[0065]
In order to impart antireflection properties to the hard coat-coated amorphous polyolefin resin article of the present invention, a single-layer or multilayer inorganic film layer can be formed on the hard coat layer. In this case, the hard coat layer can be formed by a hard coat solution containing the above-described fine particles for adjusting refractive index. However, in order to apply optical interference in the visible light region, the thickness of the underlayer of the single-layer or multilayer antireflection inorganic film layer is preferably adjusted to a range of 80 to 250 nm. Therefore, a refractive index adjusting layer having a thickness of 80 to 250 nm is provided between the hard coat layer having a thickness of 1.0 to 10 μm (containing no fine particles for adjusting refractive index) and the single or multilayer antireflection inorganic film layer. It is preferable to provide them.
[0066]
When providing a hard coat layer using a hard coat liquid, the refractive index adjustment layer,
(L) a polyfunctional acrylate,
(M) The following formula (5)
R⁹ _nSiZ_4-n(5)
Where R⁹Is an organic functional group having a functional group selected from a methacryloxy group, an acryloxy group, an epoxy group, a vinyl group, an allyl group, and an amino group; A decomposable group, and n is 1, 2 or 3.
A silane compound represented by
(N) Fine particles for adjusting refractive index
Is applied and then cured to form a liquid.
[0067]
Examples of the silane compound (M) include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, and N- (2-aminoethyl) 3-aminopropyltrimethoxysilane , 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, N- [2- (vinylbenzylamino) ethyl] -3- Aminopropyltrimethoxysilane and the like can be mentioned. Among them, 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane are particularly preferably used.
[0068]
As the polyfunctional acrylate (L) and the refractive index adjusting fine particles (N), those described in the description of the polyfunctional acrylate (A) and the refractive index adjusting fine particles, respectively, can be similarly used. The content of the fine particles for adjusting the refractive index is determined based on 100 parts by weight of the polyfunctional acrylate (L) in the liquid so that the refractive index adjusting layer has a refractive index required as a base layer of the antireflection inorganic film layer. In the range of 1 to 900 parts by weight.
[0069]
Since the refractive index adjustment layer is three-dimensionally (vertically, horizontally, and obliquely) bonded to the hard coat layer, the adhesion to the hard coat layer is good. By providing this refractive index adjusting layer, both high antireflection performance and film strength can be achieved. The refractive index adjusting layer is provided on the hard coat layer containing the fine particles (J), and a single-layer or multilayer antireflection film layer is further provided on the refractive index adjusting layer to maintain the film strength. In addition, antireflection performance and antiglare property can be imparted. Further, the refractive index adjusting layer using a silane compound (M) having an amino group can also serve as a hard coat layer used in combination with the above-described base hard coat layer. In this case, the refractive index adjusting layer and the hard coat layer contain fine particles for adjusting the refractive index, colloidal silica (C) and fine particles (J). If the requirements for the fine particles for refractive index adjustment and the fine particles (J) match, for example, titanium oxide fine particles having an average particle diameter of 100 nm can be used as the fine particles and fine particles for refractive index adjustment (J). .
[0070]
On the hard coat layer in the present invention, a single-layer or multilayer anti-reflection organic layer, for example, a single-layer anti-reflection organic layer having a refractive index of 1.30 to 1.45 can be formed. Further, the above-described refractive index adjusting layer may be provided on the hard coat layer, and a single-layer antireflection organic layer may be further provided thereon. As the single antireflection organic layer, the following formula (7)
R¹ _aR² _bSi (OR³)_4-ab(7)
Where R¹Is an alkyl group having 1 to 4 carbon atoms, an allyl group or a halogenated alkyl group having 6 to 12 carbon atoms, a methacryloxyalkyl group having 5 to 8 carbon atoms, a ureidoalkylene group having 2 to 10 carbon atoms, Ureidoalkylene group, aromatic alkylene group, mercaptoalkylene group;²Is an alkyl group having 1 to 6 carbon atoms, an allyl group, an alkenyl group, a halogenated alkyl group or a halogenated allyl group;³Is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, an acyl group or an alkylacyl group, a is 1, 2 or 3, and b is 0, 1 or 2.
A compound represented by
And a coating solution containing the above-mentioned colloidal silica is applied and cured by heating at 50 to 130 ° C. for several seconds to 5 hours. In order to impart water repellency to this organic layer, the above-mentioned fluoroalkylsilane may be added to the above-mentioned coating solution.
[0071]
The mixing ratio of each component is preferably 40 to 900 parts by weight, more preferably 250 to 500 parts by weight, based on 100 parts by weight of the compound represented by the formula (7). It is prepared as a dispersion in a liquid medium containing a predetermined amount of the active ingredient. When imparting water repellency, 1 to 20 parts by weight, preferably 3 to 15 parts by weight, more preferably 3 to 15 parts by weight, and more preferably 40 to 900 parts by weight of colloidal silica, relative to 100 parts by weight of the compound represented by the above formula (7) Parts by weight, more preferably 250 to 500 parts by weight.
[0072]
Examples of the structure of the surface-modified layer or the hard coat-coated amorphous polyolefin resin article obtained by the present invention include the following.
Single layer, two layers
(1) Hydrophilized polyolefin resin substrate / surface modified layer
(2) Hydrophilized polyolefin resin substrate / surface modified layer / transparent conductive inorganic film
(3) Hydrophilized polyolefin resin base material / surface modified layer / moisture permeable inorganic film
(4) Hydrophilic polyolefin resin base material / Surface modified layer / Single-layer / multi-layer anti-reflective inorganic film
(5) Hydrophilized polyolefin resin substrate / surface modified layer / hard coat layer
(6) Hydrophilic polyolefin resin base material / surface modified layer / antiglare hard coat layer
(7) Hydrophilized polyolefin resin substrate / surface modified layer / water-repellent hard coat layer
(8) Hydrophilic polyolefin resin base material / Surface modification layer / Water-repellent / anti-glare hard coat layer
With hard coat layer and inorganic (or organic) film
(9) Hydrophilized polyolefin resin substrate / surface modified layer / hard coat layer / transparent conductive inorganic film
(10) Hydrophilized polyolefin resin substrate / surface modified layer / hard coat layer / moisture permeable inorganic membrane
(11) Hydrophilic polyolefin resin base material / Surface modification layer / Hard coat layer / Single-layer / multi-layer anti-reflection inorganic film
(12) Hydrophilic polyolefin resin base material / Surface modified layer / Hard coat layer / Single layer anti-reflective organic film
(13) Hydrophilic polyolefin resin base material / surface modified layer / hard coat layer (containing fine particles for adjusting refractive index) / single-layer / multi-layer anti-reflective inorganic film
(14) Hydrophilized polyolefin resin base material / surface modified layer / anti-glare hard coat (containing anti-glare fine particles) / single-layer / multi-layer anti-reflective inorganic film
(15) Hydrophilized polyolefin resin substrate / surface modified layer / antiglare hard coat (containing antiglare fine particles) / single-layer antireflective organic film
With two hard coat layers
(16) Hydrophilic polyolefin resin base material / surface modified layer / underlying hard coat (thick film) / anti-glare hard coat containing small particle size fine particles (thin film)
(17) Hydrophilic polyolefin resin substrate / underlying hard coat layer (thick film) / water-repellent / anti-glare hard coat layer containing small particle size fine particles (thin film)
(18) Hydrophilic polyolefin resin base material / surface modified layer / underlying hard coat layer (thick film) / water-repellent / anti-glare hard coat layer containing small particle size fine particles (thin film)
(19) Hydrophilized polyolefin resin base material / surface modified layer / underlying hard coat layer (thick film) / anti-glare hard coat layer containing small particle size fine particles (thin film) / single-layer / multi-layer anti-reflective inorganic film
(20) hydrophilic polyolefin resin base material / surface modified layer / underlying hard coat layer (thick film) / anti-glare hard coat layer containing small particle size fine particles (thin film) / single-layer antireflection organic film refractive index adjusting layer and Single or multi-layer with anti-reflective inorganic or organic film
(21) Hydrophilic polyolefin resin base material / surface modified layer / hard coat layer / refractive index adjusting layer / single layer anti-reflective organic film
(22) Hydrophilic polyolefin resin base material / surface modified layer / hard coat layer / refractive index adjusting layer / water-repellent single layer anti-reflective organic film
(23) Hydrophilized polyolefin resin substrate / surface modified layer / hard coat layer / refractive index adjusting layer / single-layer / multi-layer anti-reflective inorganic film
(24) Hydrophilic polyolefin resin base material / Surface modification layer / Anti-glare hard coat layer / Refractive index adjusting layer / Single layer anti-reflective organic film
(25) Hydrophilized polyolefin resin base material / surface modified layer / anti-glare hard coat layer / refractive index adjusting layer / single-layer / multi-layer anti-reflective inorganic film
(26) Hydrophilic polyolefin resin base material / surface modified layer / hard coat layer / water-repellent single layer anti-reflective organic film
[0073]
In the present invention, as the amorphous polyolefin resin substrate, a sterically bulky functional group is introduced into the polymer main chain to control crystallization (6-methyl-1,4,5,8-dimethano-1). , 4,4a, 5,6,7,8,8a-Hydrogenated product of ring-opening polymer of octahydronaphthalene) or "Zeonex" or "Zeonoa" (trade name of Zeon Corporation) , Norbornene resin-based "ARTON" (trade name of a product group manufactured by JSR Corporation), and "APEL" (ethylene-norbornene addition copolymer or ethylene-tetracyclododecene addition polymer) (Mitsui Petrochemical Industries, Ltd. ) Manufactured by Zeon Corporation (trade names “ZEONEX” (grades: 480 and 490K), “ZEONOR” (grades: 1020R, 1060R, 1420R, and 1). 00R), JSR Corporation: Trade name “ARTON” (grade: G, F, FX, D), Mitsui Petrochemical Industries, Ltd .: Trade name “APO”, “Apel” (grade: APS8009, APS5014, APS6518) )).
[0074]
Although the above description has been made on the application to the amorphous polyolefin resin substrate itself, the present invention is not limited to this, and is applied to the amorphous polyolefin resin surface of an amorphous polyolefin resin processed product such as a polarizing film and a display panel. May be.
[0075]
The present invention requires a light diffusion treatment film for a light guide plate of a mobile phone, a display (top surface treatment of a notebook computer, a monitor, a PDP, a PDA), a top surface treatment film of a touch panel monitor, a cell phone window, and high optical characteristics. It is used for parts, transparent parts for automobiles, and cover base materials made of materials that are sensitive to ultraviolet rays.
[0076]
【The invention's effect】
According to the present invention, the hydrophilic treatment of the surface of the amorphous polyolefin resin substrate, the reactivity of the substrate surface is increased by coating the surface modified layer, and the functional film is firmly attached to the substrate surface. be able to. In particular, the functional hard coat layer has good adhesion, and the surface of the polyolefin resin substrate is coated with a hard coat layer having excellent adhesion and moisture resistance, so that the scratch resistance of the coated amorphous polyolefin resin article is improved. Is improved. Then, by adding anti-glare fine particles and fluoroalkylsilane to the hard coat layer, an anti-glare property, water repellency and stain resistance can be imparted to the amorphous polyolefin resin article. Further, a film of a metal, a metal oxide, a metal nitride, or the like can be coated with a strong adhesive property on the hard coat layer or the surface modification layer, so that the anti-reflection property, the moisture permeability resistance, and the transparent conductive property can be achieved. Properties can be imparted. Further, by adding an ultraviolet absorber to the surface-modified layer, it is possible to achieve both the ultraviolet blocking property and the high visible light transmittance, and it has an ultraviolet blocking effect, so that it can be applied as an ultraviolet blocking cover.
[0077]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the present invention will be specifically described with reference to examples.
The substrates, hydrophilic treatment methods, inorganic film layer forming methods, various coating liquid preparation methods, coating methods, ultraviolet curing methods, evaluation methods, and the like used in Examples and Comparative Examples are as follows.
Amorphous polyolefin resin base material
The following cycloolefin polymer was used as the amorphous polyolefin resin.
(A1, A2) Norbornene-based monomer manufactured by ZEON CORPORATION was used as a raw material, and grades 490K and 480 of trade name “ZEONEX” (ZEONEX) were used. These were injection molded to obtain a base material A1 (grade 490K) and a base material A2 (grade 480) having a size of 100 mm × 150 mm and a thickness of 2 mm.
(B1) A ring-opening polymerization hydrogenated polymer of dicyclopentadiene manufactured by ZEON CORPORATION. Grade 1600R of trade name "ZEONOR" (Zeonor) was used. These were injection molded to obtain a base material B1 (grade 1600R) having a size of 100 mm × 150 mm and a thickness of 2 mm.
(C1, C2) Norbornene-based monomer manufactured by JSR Corporation was used as a raw material, and grade F and FX of trade name “ARTON” (ARTON) were used. These were injection-molded to obtain a base material C1 (grade F) and a base material C2 (grade FX) having a size of 100 mm × 150 mm and a thickness of 2 mm.
(D1, D2) A copolymer of cyclic olefin and ethylene (ethylene / tetracyclodecene copolymer) manufactured by Mitsui Chemicals, Inc., using grade APS5014 and grade APS6518 of trade name “Apel” (Apel) . These were injection molded to obtain a base material D1 (gray APS5014) and a base material D2 (grade APS6518) having a size of 100 mm × 150 mm and a thickness of 2 mm.
(E1) @Mitsui Petrochemical Co., Ltd. (trade name "APO") was used. This was injection molded to obtain a base material E1 having a size of 100 mm × 150 mm and a thickness of 2 mm.
[0078]
Hydrophilic treatment
<Corona treatment>
Using a corona discharge surface reformer “Corona Master” PS-1M type manufactured by Shinko Denshi Keiso Co., Ltd. on the amorphous polyolefin resin base material, a variable voltage of up to about 14,000 volts and an output of about 15 kHz The corona discharge treatment at a frequency was performed at a speed of 5 mm per second so that the contact angle of water on the surface of the amorphous polyolefin resin base material was 35 to 40 degrees.
<Plasma treatment>
Using a plasma reactor model PR-501A manufactured by Yamato Scientific Co., Ltd. for the base material, high-frequency 13.56 MHz (output: 100 to 200 W), and plasma used for 2 minutes under the condition of oxygen (flow rate 100 ml / min) This was performed so that the contact angle of water on the surface of the resin substrate was 20 degrees.
<Ozone water cleaning treatment>
The substrate was treated using an ozone water generator OM-2 manufactured by Sasakura Co., Ltd. under the condition that the substrate was immersed in ozone water at room temperature for 4 minutes, and the contact angle of water on the surface of the resin substrate was 50. Degree.
<UV ozone irradiation treatment>
Using a UV lamp (product number: SGL-18W18S-SA1) manufactured by Samco International Laboratories Co., Ltd. for the substrate, the UV illuminance immediately below the lamp was 20 mW / cm.²When UV irradiation is performed on the base material, ozone is generated on the base material to decompose dirt such as oil on the base material surface. The UV ozone irradiation treatment was performed for 2 minutes, 5 minutes, 15 minutes, or 30 minutes so that the contact angle of water on the surface of the resin substrate was 5 to 60 degrees.
[0079]

[0080]
Preparation of treatment liquid for surface modified layer
Preparation of surface modification liquid 1
50 g of solvent-soluble acrylic resin "Paraloid A-10S" (Rohm & Haas Japan K.K.) and 50 g of propylene glycol monomethyl ether are weighed and mixed to form a homogeneous liquid, and a small amount of surfactant is used. In addition, the surface modification liquid 1 is used.
Preparation of surface modification liquid 2
50 g of Paraloid A-10S (Rohm and Haas Japan K.K.) and 50 g of propylene glycol monomethyl ether were weighed and mixed, and a homogeneous liquid was prepared, and 2 g of γ-methacryloxypropyltrimethoxysilane was added. Then, the mixture is stirred to make a homogeneous liquid, and a small amount of a surfactant is added thereto to prepare a liquid 2 for surface modification.
Preparation of surface modification liquid 3
50 g of Paraloid A-10S (Rohm and Haas Japan K.K.) and 50 g of propylene glycol monomethyl ether were weighed and mixed, and a homogeneous liquid was prepared, and 2 g of γ-methacryloxypropyltrimethoxysilane was added. , 4.5 g of 2,4-dihydroxybenzophenone were added and stirred to obtain a homogeneous liquid, and a small amount of a surfactant was added to obtain a liquid 3 for surface modification.
Preparation of surface modification liquid 4
A solution prepared by dissolving 1.0 g of benzoyl peroxide in 200 g of ethyl cellosolve while maintaining a mixture of 400 g of ethyl cellosolve, 190 g of ethyl methacrylate, and 10 g of γ-methacryloxypropyltrimethoxysilane at 75 ° C. under a nitrogen atmosphere. Add over 2 hours and hold at 75 ° C. for an additional 6 hours. Thereafter, 1400 g of ethyl cellosolve, 2 g of a 10% aqueous solution of ammonium perchlorate, and 30 g of 2,4-dihydroxybenzophenone were added to prepare a surface modification liquid 4.
Preparation of surface modification liquid 5
A solution prepared by dissolving 1.0 g of benzoyl peroxide in 200 g of ethyl cellosolve while maintaining a mixture of 400 g of ethyl cellosolve, 190 g of ethyl methacrylate, and 10 g of γ-methacryloxypropyltrimethoxysilane at 75 ° C. under a nitrogen atmosphere was used. Add over time and hold at 75 ° C. for an additional 6 hours. Thereafter, 1400 g of ethyl cellosolve, 3.5 g of γ-methacryloxypropyltrimethoxysilane, 2 g of a 10% aqueous solution of ammonium perchlorate, and 30 g of 2,4-dihydroxybenzophenone were added to prepare a surface modification liquid 5.
[0081]
Preparation of surface modification liquid 6
While maintaining 300 parts of butyl cellosolve at 100 ° C. under a nitrogen atmosphere, a mixture of 160 parts of methacrylic acid, 40 parts of γ-methacryloxypropyltrimethoxysilane, and 2.0 parts of benzoyl peroxide was added over 3 hours, and further 3 hours. It was kept at the same temperature. Thereafter, 1155 parts of butyl cellosolve, 363 parts of ethylene glycol diacetate, 3 parts of a 10% aqueous solution of ammonium perchlorate, 100 parts of 2-hydroxy-4-methoxybenzophenone, and a small amount of a flow control agent were added. did.
Preparation of surface modification liquid 7
While maintaining a mixture of 384 parts of methyl isobutyl ketone and 216 parts of methyl ethyl ketone at 90 ° C. in a nitrogen atmosphere, 180 parts of methyl methacrylate, 20 parts of γ-methacryloxypropylmethyldimethoxysilane, and azobisisobutyronitrile 1.0 part The mixture was added over 2 hours and kept at the same temperature for a further 5 hours. Thereafter, 624 parts of methyl isobutyl ketone, 576 parts of isopropyl alcohol, 10 parts of a 10% aqueous solution of ammonium perchlorate, and 40 parts of 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate were added to prepare a liquid 7 for surface modification. .
Preparation of surface modification liquid 8
A mixture of 400 parts of ethyl cellosolve, 140 parts of ethyl methacrylate, and 60 parts of γ-methacryloxypropyltrimethoxysilane was dissolved in 200 parts of ethyl cellosolve while maintaining 1.0 part of benzoyl peroxide in a nitrogen atmosphere at 75 ° C. The solution was added over 2 hours and kept at the same temperature for another 8 hours. Thereafter, 1400 parts of ethyl cellosolve, 14 parts of a 10% aqueous solution of ammonium perchlorate, and 30 parts of 2- (2'-hydroxy-5'-octylphenyl) benzotriazole were added to prepare a liquid 8 for surface modification.
Preparation of surface modification liquid 9
While maintaining a mixture of 400 parts of ethyl cellosolve, 190 parts of ethyl methacrylate, and 10 parts of γ-methacryloxypropyltrimethoxysilane at 75 ° C. in a nitrogen atmosphere, 1.0 part of benzoyl peroxide was dissolved in 200 parts of ethyl cellosolve. The solution was added over 2 hours and kept at the same temperature for another 6 hours. Thereafter, 1486 parts of ethyl cellosolve, 2 parts of a 10% aqueous solution of ammonium perchlorate, 2.6 parts of hexa (methoxymethyl) melamine, and 20 parts of 2,4-dihydroxybenzophenone were added to prepare a surface modification liquid 9.
[0082]
Preparation of surface modification liquid 10
While maintaining 300 parts of butyl cellosolve at 100 ° C. under a nitrogen atmosphere, a mixture of 160 parts of methyl methacrylate, 40 parts of γ-methacryloxypropyltrimethoxysilane, and 2.0 parts of benzoyl peroxide was added over 3 hours, and further 3 hours. After maintaining the same temperature, 360 parts of ethylene glycol diacetate was added. To 215 parts of the copolymer thus obtained, 1.0 part of a 10% aqueous solution of ammonium perchlorate, 0.8 part of hexa (methoxymethyl) melamine, 50 parts of 2,4-dihydroxybenzophenone, and 285 parts of butyl cellosolve were added. Thus, a surface modification liquid 10 was obtained.
Preparation of surface modification liquid 11
To 215 parts of the copolymer used for preparing the surface modification liquid 10, 0.5 part of a 10% aqueous solution of ammonium perchlorate, 0.3 part of hexa (methoxymethyl) melamine, and 2,2'-hydroxy-4 -Methoxybenzophenone (10 parts) and butyl cellosolve (285 parts) were added to prepare Surface Modification Liquid 11.
Preparation of surface modification liquid 12
A mixture of 90 parts of methyl methacrylate, 10 parts of γ-methacryloxypropylmethyldimethoxysilane, and 0.8 part of azobisisobutyronitrile was taken for 2 hours while keeping 320 parts of n-butyl acetate at 90 ° C. under a nitrogen atmosphere. And kept at the same temperature for another 5 hours. Thereafter, 760 parts of butyl cellosolve, 5 parts of a 10% aqueous solution of ammonium perchlorate, 1.8 parts of hexa (methoxymethyl) melamine, and 20 parts of 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole were added. And a liquid 12 for surface modification.
Preparation of surface modification liquid 13
A solution prepared by dissolving 1.0 part of benzoyl peroxide in 200 parts of ethyl cellosolve while maintaining a mixture of 400 parts of ethyl cellosolve, 140 parts of ethyl methacrylate, and 60 parts of γ-methacryloxypropyltrimethoxysilane at 80 ° C. under a nitrogen atmosphere. Was added over 2 hours and kept at the same temperature for another 8 hours. Thereafter, 1400 parts of ethyl cellosolve, 6 parts of a 10% aqueous solution of ammonium perchlorate, 4.7 parts of hexa (methoxymethyl) melamine, and 40 parts of 2-ethylhexyl-2-cyano-3,3 diphenyl acrylate were added to modify the surface. This was used as a liquid for quality control 13.
[0083]
Preparation of hard coat liquid 1 (light-curable hard coat)
12.4 g of 1,6-hexanediol diacrylate as a polyfunctional acrylate, 1.6 g of γ-aminopropyltrimethoxysilane, 6.3 g of 2-methoxypropanol, 4.0 g of acetic acid, 0.8 g of benzophenone as a photopolymerization initiator 26.0 g of “NPC-ST-30” (a fine particle of silica having an average particle size of 20 nm dispersed in n-propyl cellosolve, manufactured by Nissan Chemical Industries, Ltd .; silica content of 30% by weight) as a colloidal silica was applied to the film. 5.0 g of "Epoxy Ester 3002M" (manufactured by Kyoeisha Chemical Co., Ltd.) and 14.5 g of butyl acetate are added as epoxy acrylate for imparting flexibility and increasing the hardness of the film. Next, 0.1 g of a flow control agent ("Paintad 19", manufactured by Dow Corning Asia Ltd.) is added. Thereafter, 100 g of 2-methoxypropanol was added, and the mixture was stirred and uniformly dispersed to obtain a hard coat liquid 1 for imparting scratch resistance.
[0084]
Preparation of hard coat liquid 2 (photocurable hard coat with antiglare property)
16.0 g of polyethylene glycol diacrylate as a polyfunctional acrylate, 1.0 g of γ- (2-aminoethyl) aminopropyltrimethoxysilane, 6.3 g of 2-methoxypropanol, 4.0 g of acetic acid, and isopropylbenzoin ether as a photopolymerization initiator 0.8 g, and 45.0 g of colloidal silica "IPA-ST-ZL" (manufactured by Nissan Chemical Industries, Ltd., silica fine particles having an average particle size of 80 to 100 nm dispersed in isopropanol; silica content 30% by weight). Next, "UA-306H" (a urethane prepolymer of pentaerythritol triacrylate and hexamethylene diisocyanate, manufactured by Kyoeisha Chemical Co., Ltd.) as a urethane acrylate for increasing the hardness of the film and curing the film with low energy. 1.0g, flow control Agent is added 0.1g. Thereafter, 100 g of 2-methoxypropanol is added. Thereafter, 0.8 g (2% by weight of the active ingredient of the hard coat) of crystalline silica fine particles having an average particle diameter of 6 μm is added to the solution, and the mixture is stirred and uniformly dispersed. As a result, a hard coat liquid 2 for imparting antiglare property and scratch resistance was obtained.
[0085]
Preparation of Hard Coating Liquid 3 (Water-Repellent Photocurable Hard Coat)
17 g of 1,4-butanediol diacrylate as a polyfunctional acrylate, 8.0 g of γ-aminopropyltrimethoxysilane, 6.3 g of 2-methoxypropanol, 4.0 g of acetic acid, 2-hydroxy-2-methyl as a photopolymerization initiator 0.8 g of -1-phenylpropan-1-one and "IPA-ST" as colloidal silica (manufactured by Nissan Chemical Industries, Ltd., silica fine particles having an average particle diameter of 10 to 20 nm are dispersed in isopropanol. Silica content 30) 20.0 g) and 9.0 g of perfluorooctylethyltriethoxysilane were added and reacted, and then 14.5 g of butyl acetate was added. Next, 0.1 g of a flow control agent is added. Thereafter, 100 g of 2-methoxypropanol is added. As a result, a hard coat liquid 3 for imparting water repellency and scratch resistance was obtained.
[0086]
Preparation of hard coat liquid 4 (light-curable hard coat imparting water repellency and anti-glare properties)
12.4 g of trimethylolpropane triacrylate as a polyfunctional acrylate, 2.6 g of γ-aminopropyltrimethoxysilane, 6.3 g of 2-methoxypropanol, 4.0 g of acetic acid, 0.8 g of benzophenone as a photopolymerization initiator, colloidal silica After adding 26.0 g of "IPA-ST-ZL" (manufactured by Nissan Chemical Industries, Ltd.) and 9.0 g of perfluorooctylethyltriethoxysilane and reacting, 14.5 g of butyl acetate is added. Next, 0.1 g of a flow control agent is added. Thereafter, 100 g of 2-methoxypropanol is added. Thereafter, 0.8 g (2% by weight of the active ingredient of the hard coat) of silica fine particles having an average particle diameter of 6 μm is added to the solution, and the mixture is stirred and uniformly dispersed. As a result, a hard coat liquid 4 for imparting antiglare properties, water repellency and scratch resistance was obtained.
[0087]
Preparation of hard coat liquid 5 (thermosetting hard coat)
After reacting 150 g of colloidal silica “Snowtex O-40” (manufactured by Nissan Chemical Co., Ltd .: average particle diameter 20 nm, nonvolatile content 40%) and 183 g of methyltrimethoxysilane, 508 g of isopropyl alcohol, 140 g of normal butanol, 18 g of acetic acid , 1 g of sodium acetate and 0.1 g of Dow Corning Paint Additive 19 were added to obtain a hard coat liquid 5 for imparting scratch resistance.
Preparation of Hard Coat Liquid 6 (Anti-glare-Providing Thermosetting Hard Coat)
After reacting 58 g of the above-mentioned colloidal silica "Snowtex @ O-40" and 86 g of methyltrimethoxysilane, a solution obtained by adding 505 g of isopropyl alcohol, 140 g of normal butanol, 18 g of acetic acid, 2 g of sodium acetate and 0.1 g of Dow Corning paint additive 19 was added. Then, 2.4 g (2% by weight of the active ingredient of the hard coat) of silica fine particles having an average particle diameter of 6 μm was added thereto, and the mixture was stirred and uniformly dispersed. As a result, a hard coat liquid 6 for imparting antiglare properties and scratch resistance was obtained.
[0088]
Preparation of hard coat liquid 7 (thermosetting hard coat with water repellency)
After reacting 58 g of the colloidal silica “Snowtex @ O-40”, 86 g of methyltrimethoxysilane, and 4.3 g of perfluorooctylethyltrimethoxysilane, 505 g of isopropyl alcohol, 140 g of normal butanol, 18 g of acetic acid, 2 g of sodium acetate and 0.1 g of Dow Corning Paint Additive 19 was added, and the mixture was stirred and uniformly dispersed. As a result, a hard coat liquid 7 for imparting water repellency and scratch resistance was obtained.
Preparation of hard coat liquid 8 (thermosetting hard coat with anti-glare and water repellency)
After reacting 58 g of the colloidal silica “Snowtex @ O-40”, 86 g of methyltrimethoxysilane, and 4.3 g of perfluorooctylethyltrimethoxysilane, 505 g of isopropyl alcohol, 140 g of normal butanol, 18 g of acetic acid, 2 g of sodium acetate and To a solution containing 0.1 g of Dow Corning Paint Additive 19, 2.4 g of silica fine particles having an average particle diameter of 6 μm (2% by weight of the hard coat active ingredient) was added, and the mixture was stirred and uniformly dispersed. As a result, a hard coat liquid 8 for imparting antiglare properties, water repellency and stain resistance, and scratch resistance was obtained.
[0089]
Preparation of hard coat liquid 9 (photocurable hard coat with antiglare property)
100 g of 1,6-hexanediol diacrylate as polyfunctional acrylate (A), 10 g of γ-aminopropyltrimethoxysilane as aminosilane (B), 50 g of 2-methoxypropanol, 5 g of acetic acid, and average particles as colloidal silica (C) 140 g of “IPA-ST” (active ingredient: 30% by weight, manufactured by Nissan Chemical Industries, Ltd.) having a diameter of 10 to 20 nm, and dispersion “KE-W50” of amorphous silica fine particles as fine particles (J) (particle size: 0) .50 to 0.56 μm, active ingredient: 15 parts by weight, 500 g of Nippon Shokubai Co., Ltd.) was added and stirred, and then 5 g of benzophenone as a photoinitiator and 0.1 g of a flow control agent were added. Coating liquid 9 was obtained.
[0090]
Preparation of hard coat liquid 10 (photo-curable base hard coat)
As a polyfunctional acrylate, 12.4 g of 1,6-hexanediol diacrylate, 2.6 g of γ-aminopropyltrimethoxysilane, 6.3 g of 2-methoxypropanol, 0.4 g of acetic acid, and as colloidal silica (average particle diameter of 20 to 30 nm) 2) g of “MA-ST-M” (active ingredient: 40% by weight @ Nissan Chemical Industries, Ltd.), 5.0 g of “Epoxy Ester 3002M” (Kyoeisha Chemical Co., Ltd.) as epoxy acrylate, 14.5 g of butyl acetate are added. Next, 0.8 g of benzophenone and 0.1 g of a flow control agent are added as a photopolymerization initiator. Thereafter, 100 g of 2-methoxypropanol was added, and the mixture was stirred and uniformly dispersed to obtain a hard coat liquid 10.
[0091]
Preparation of Liquid 1 for Refractive Index Adjusting Layer
12.4 g of 1,4-butanediol diacrylate as a polyfunctional acrylate, 1.0 g of 3-acryloxypropyltrimethoxysilane, 6.3 g of 2-methoxypropanol, 4.0 g of acetic acid, 2-hydroxy- as a photopolymerization initiator 0.8 g of 2-methyl-1-phenylpropan-1-one and "NPC-ST-30" as a colloidal silica (manufactured by Nissan Chemical Co., Ltd., silica fine particles having an average particle size of 20 nm are dispersed in n-propyl cellosolve). 20.0 g of silica content (30% by weight) are added. Next, 0.1 g of a flow control agent is added.
[0092]
Thereafter, 100 g of 2-methoxypropanol is added, and the mixture is stirred and uniformly dispersed. Add “OPTLAKE 1130F2A8” (TiO 2₂And SiO₂Of composite oxide fine particles (average particle size of about 10 nm) composed of₂And SiO₂Is 80:20. (Composite oxide content: 30% by weight). Thus, a liquid 1 for a refractive index adjusting layer for forming a layer having a higher refractive index after film formation than that of the hard coat layer was obtained.
[0093]
Preparation of coating liquid 11 for low refractive index (thermosetting hard coat)
After reacting 150 g of "Snowtex O-40" (manufactured by Nissan Chemical Co., Ltd., nonvolatile content: 40%) and 183 g of methyltrimethoxysilane as colloidal silica having an average particle diameter of 20 nm, 648 g of isopropyl alcohol, 18 g of acetic acid, and 1 g of sodium acetate And 0.1 g of "Paint Additive 19" (manufactured by Dow Corning) as a flow control agent, and the mixture was stirred to obtain a coating liquid 11 for low refractive index.
[0094]
Preparation of Coating Liquid 12 for Low Refractive Index (Heat Curing Type Hard Coating Liquid with Water Repellency)
600 g of “IPA-ST-ZL” (manufactured by Nissan Chemical Co., Ltd., nonvolatile content: 30%) as colloidal silica having an average particle diameter of 80 to 100 nm, 86 g of methyltrimethoxysilane, and 4.3 g of perfluorooctylethyltrimethoxysilane After the reaction, 645 g of isopropyl alcohol, 18 g of acetic acid, 2 g of sodium acetate, and 0.1 g of “Paint Additive 19” (manufactured by Dow Corning) as a flow control agent were added, followed by stirring to obtain a coating liquid 12 for a low refractive index. Was.
[0095]
Coating and curing methods
The liquid for the surface modification layer was applied to the resin subjected to the hydrophilization treatment (Example) or the base material not subjected to the hydrophilization treatment (Comparative Example) by a flow coating method, and was applied at 80 ° C. for 30 minutes. By heat curing, a surface-modified layer having a thickness of 10 nm was formed.
The hard coat liquids 1 to 4, 9, and 10 were applied by a flow coat method, and the hard coat liquid 5 was applied by a spinner method. Thereafter, the total ultraviolet irradiation energy was 1000 (mJ / m) by an ultraviolet lamp having an output of 120 W / cm. cm²1) to 30 seconds so as to cure the coating film. The total ultraviolet irradiation energy value was measured by an integrating light meter (model: UIT-102 @ manufactured by Ushio Inc.). The liquid for refractive index adjusting layer 1 was applied by a flexographic printing method, and the applied film was cured by ultraviolet rays in the same manner as described above. The hard coat liquids 6 to 8 were applied by a flow coat method, and were cured by heating at 80 ° C. for 120 minutes. The coating liquids 11 and 12 for low refractive index were applied by a spin method, and the applied films were cured by heating at 80 ° C. for 30 minutes.
[0096]
Evaluation method
The evaluation method of the coating film coated with the amorphous polyolefin resin substrate obtained in each of the following examples is as follows.
(A) Adhesion test: Cross-cut test was conducted in accordance with JIS K5400. That is, a cellophane tape manufactured by Nichiban Co., Ltd. is stuck on the hard coat film, and then vigorously peeled off. ) The adhesion (easy adhesion) and moisture permeability of the film after the evaluation were evaluated, and the number of peeled squares out of 100 squares of the hard coat film was evaluated according to the following criteria.
Number of peeled squares 0 --------- "No peeling"
Number of peeled squares 1-5 ---- "peeling at a very small part"
Number of peeled squares $ 6 to 50 --- "Partially peeled"
Number of peeled squares 51-99-"large peeling"
The number of peeled squares $ 100
(B) Moisture resistance test: The test was performed by standing in a tank at an atmospheric temperature of 50 ° C. and a relative humidity of 95% RH for 10 days.
(C) Scratch resistance (scratch resistance): The surface was rubbed ten times with commercially available steel wool (# 0000), and the scratch was visually determined. The criteria were determined in the following four stages.
1 ... no scratches 2 ... slight scratches 3 ... many scratches 4 ... scratches as the film comes off.
(D) Stain test: After attaching a commercially available wax, the sample was wiped off with a cotton dust-free cloth, and the extent to which the wiping marks of the wax remained as stains was visually checked to evaluate the stain resistance.
(E) Contact angle measurement: The contact angle with a 0.1 cc pure water droplet was measured. The larger the contact angle, the higher the antifouling property.
(F) Measurement of optical properties: Visible light transmittance (%) and haze value (%) were measured according to JIS R3212. The higher the haze value, the higher the antiglare property.
[0097]
Example 1
The corona discharge treatment was performed on the amorphous polyolefin substrate B1 at a speed of 5 mm / sec so that the contact angle of water on the surface of the amorphous polyolefin substrate was 40 degrees. Next, the surface modification liquid 4 was applied and dried by heating at 80 ° C. for 30 minutes in a hot-air drying oven to cover a surface modification layer having a thickness of 10 nm.
In the adhesion test immediately after the formation of the obtained surface-modified layer (initial stage), there was no peeling. A sample different from the sample for which the above adhesiveness was evaluated was prepared, and the scratching property was evaluated. A number of scratches were found in the scratching test. As for the optical characteristics, the visible light transmittance was 91%, and the transmittance at 350 nm was 0%.
[0098]
Examples 2 to 7
Instead of the corona discharge treatment of 5 mm / s in Example 1,
In Example 2, the plasma treatment was performed so that the contact angle of water on the surface of the resin base material became 20 degrees,
In the third embodiment, the ozone water cleaning treatment is performed so that the contact angle of water on the surface of the base material becomes 50 degrees,
In Example 4, the UV ozone irradiation time was performed for 30 minutes so that the contact angle of water on the substrate surface was 5 degrees,
In Example 5, the UV ozone irradiation time was performed for 15 minutes so that the contact angle of water on the substrate surface was about 15 degrees,
In the sixth embodiment, the UV ozone irradiation time is performed for 5 minutes so that the contact angle of water on the substrate surface becomes about 45 degrees,
In Example 7, the UV ozone irradiation time was performed for 2 minutes so that the contact angle of water on the substrate surface was about 60 degrees,
Otherwise, the same base material B1, surface modification treatment liquid 4, and curing conditions as in Example 1 were used, and a surface modified layer was formed in the same manner as in Example 1.
Furthermore, when the adhesion and the scratching property of the coating film were evaluated in the same manner as in Example 1, the initial adhesion in each of Examples 2 to 7 was "no peeling", and all of the examples were flawed. In the sticking test, a number of scratches were observed, and in all the examples, the visible light transmittance was 91%, and the transmittance at 350 nm was 0%.
Table 1 summarizes the results of Examples 1 to 7.
[0099]
Comparative Example 1
Without subjecting the amorphous polyolefin substrate B1 used in Example 1 to a hydrophilization treatment (contact angle of water on the surface of the polyolefin substrate is 90 degrees), the surface modification liquid 4 is applied and heated at 80 ° C. in a hot air drying furnace. And dried by heating for 30 minutes to form a surface-modified layer having a thickness of 10 nm.
The adhesion of the obtained film immediately after the film formation (initial stage) was tested, and the result was "large peeling". A number of scratches were found in the scratching test. As for the optical characteristics, the visible light transmittance was 91%, and the transmittance at 350 nm was 0%.
Comparative Example 2
100 nm / 100 nm-thick TiO2 by vacuum evaporation on the surface of the amorphous polyolefin substrate B1 with a surface-modified layer obtained in Comparative Example 1.₂/ SiO₂A laminated inorganic film layer (antireflection layer) was formed.
Comparative Example 3
A hard coat liquid 1 was applied to the surface of the amorphous polyolefin substrate B1 with a surface modified layer obtained in Comparative Example 1 and cured to coat a hard coat layer having a thickness of 3 μm.
The adhesion of the films obtained in Comparative Examples 2 and 3 immediately after the film formation (initial stage) was tested. In the scratching test, a number of scratches were observed in all the comparative examples. The optical characteristics of each of Comparative Examples 2 and 3 were such that the visible light transmittance was 91% and the transmittance at 350 nm was 0%.
Table 3 summarizes the results of Comparative Examples 1 to 3.
[0100]
Examples 8 to 19
Instead of the surface modification treatment liquid 4 used in Example 1,
In Example 8, the surface modification treatment liquid 1 was used,
In Example 9, the surface modification treatment liquid 2 was used,
In Example 10, the surface modification treatment liquid 3 was used,
In Example 11, the surface modification treatment liquid 5 was used,
In Example 12, the surface modification treatment liquid 6 was used,
In Example 13, the surface modification treatment liquid 7 was used,
In Example 14, the surface modification treatment liquid 8 was used,
In Example 15, the surface modification treatment liquid 9 was used,
In Example 16, the surface modification treatment liquid 10 was used,
In Example 17, the surface modification treatment liquid 11 was used,
In Example 18, the surface modification treatment liquid 12 was used,
In Example 19, the surface modification treatment liquid 13 was used,
Except for this, the surface modified layer was formed in the same manner as in Example 1 under the same conditions as in Example 1 under the same base material B1, corona discharge treatment at 5 mm / s, and curing conditions.
Furthermore, when the adhesion and scratching property of the coating film were evaluated in the same manner as in Example 1, the initial adhesion properties of all of Examples 8 to 19 were "no peeling", and all of the examples were flawed. A number of scratches were observed in the sticking test. The visible light transmittance of each example was 91%, the transmittance at 350 nm was 88% in Examples 8 and 9, and the transmittance was 350% in Examples 10 to 19. It was 0%.
Table 1 summarizes the results of Examples 8 to 19.
[0101]
Examples 20 to 26
Instead of the base material B1 used in Example 1,
In Example 20, the substrate A2 was used so that the water droplet contact angle after the hydrophilization treatment was 45 degrees,
In Example 21, the substrate A1 was used so that the water droplet contact angle after the hydrophilization treatment was 40 degrees,
In Example 22, the substrate C1 was used to make the water droplet contact angle after the hydrophilization treatment 35 degrees,
In Example 23, the contact angle of water droplets after the hydrophilization treatment was set to 35 degrees using the base material C2,
In Example 24, the contact angle of the water droplet after the hydrophilization treatment was set to 40 degrees using the base material E1,
In Example 25, the contact angle of the water droplet after the hydrophilization treatment was set to 35 degrees using the base material D1,
In Example 26, the water droplet contact angle after the hydrophilization treatment was set to 35 degrees using the base material D2,
Other than that, a surface modified layer was formed in the same manner as in Example 1 under the same corona discharge treatment of 5 mm / s, the surface modifying liquid 4 and the curing conditions as in Example 1.
Furthermore, when the adhesion and scratching property of the coating film were evaluated in the same manner as in Example 1, the initial adhesion properties of all of Examples 20 to 26 were "no peeling", and all the examples showed no flaws. Many flaws were observed in the sticking test, and the visible light transmittance of each example was 91 to 92%, and the transmittance of 350 nm was 0% in all examples.
Table 2 summarizes the results of Examples 20 to 26.
[0102]
Example 27
The hard coat liquid 1 was applied onto the surface-modified layer-coated substrate obtained in the same manner as in Example 8, and cured to coat a hard coat layer having a thickness of 3 μm.
The adhesion of the obtained film was evaluated immediately after film formation (initial stage) and after the moisture resistance test. After the moisture resistance test, peeling was observed only on a very small portion, and the initial adhesion was "no peeling". No scratch was observed in the scratching test. The optical characteristics were as follows: visible light transmittance was 91%, and transmittance at 350 nm was 88%.
Examples 28 to 31
Instead of the surface-modified layer liquid 1 used in Example 27,
In Example 28, the liquid 2 for a surface-modified layer was used,
In Example 29, the liquid 3 for surface modification layer was used,
In Example 30, the liquid 4 for surface modification layer was used,
In Example 31, the liquid 5 for surface modification layer was used,
Other than that, a hard coat layer was formed in the same manner as in Example 27 under the same corona discharge treatment of 5 mm / s, hard coat liquid 1 and curing conditions as in Example 27.
Furthermore, when the adhesion and the scratching property of the coating film were evaluated in the same manner as in Example 1, the initial adhesion in each of Examples 28 to 31 was "no peeling", and the adhesion after the moisture resistance test was none. Was “no peeling”, no scratch was found in any of the examples in the scratching test, the visible light transmittance was 91% in each example, and the transmittance at 350 nm was 88% in Example 28. Yes 0% in all of Examples 29 to 31.
[0103]
Example 32
The hard coat liquid 5 was applied on the surface-modified layer-coated substrate obtained in the same manner as in Example 8, and cured to coat a hard coat layer having a thickness of 3 μm.
The adhesion of the obtained film was evaluated immediately after film formation (initial stage) and after the moisture resistance test. After the moisture resistance test, peeling was seen only on a very small portion, and the initial adhesion was "no peeling". No scratch was observed in the scratching test. The optical characteristics were as follows: visible light transmittance was 91%, and transmittance at 350 nm was 88%.
Examples 33 to 36
Instead of the surface-modified layer liquid 1 used in Example 32,
In Example 33, the surface-modified layer liquid 2 was used,
In Example 34, the surface modified layer liquid 3 was used,
In Example 35, the liquid 4 for surface modification layer was used,
In Example 36, the liquid 5 for surface modification layer was used,
Other than that, a hard coat layer was formed in the same manner as in Example 32 under the same corona discharge treatment 5 mm / s, hard coat liquid 5 and curing conditions as in Example 32.
Furthermore, when the adhesion and the scratching property of the film were evaluated in the same manner as in Example 1, the initial adhesion was "no peeling" in any of Examples 33 to 36, and the adhesion after the moisture resistance test was all. Was also "no peeling", no scratch was found in any of the examples in the scratching test, the visible light transmittance was 91% in each example, and the transmittance at 350 nm was 88% in Example 33. Yes, all of Examples 34 to 36 were 0%.
Table 4 summarizes the results of Examples 27 to 36.
[0104]
Examples 37 to 42
Instead of the hard coat liquid 1 used in Example 30,
In Example 37, the hard coat liquid 2 was used.
In Example 38, the hard coat liquid 3 was used.
In Example 39, the hard coat liquid 4 was used,
In Example 40, the hard coat liquid 6 was used,
In Example 41, the hard coat liquid 7 was used,
In Example 42, the hard coat liquid 8 was used.
Other than that, a hard coat layer was formed in the same manner as in Example 30 under the same corona discharge treatment of 5 mm / s, the surface modifying liquid 4 and the curing conditions as in Example 30.
Furthermore, when the adhesion and the scratching property of the coating film were evaluated in the same manner as in Example 1, the initial adhesion in each of Examples 37 to 42 was “no peeling”, and the adhesion after the moisture resistance test was all. Was “no peeling”, no scratch was found in any of the examples in the scratching test, the visible light transmittance was 91% in each example, and the transmittance was 350% in all the examples at 0%. Met. In Examples 37 and 40, the haze value was 10 to 11%, and the antiglare property was excellent. Examples 38 and 41 were "no stain" in the stain test, and were excellent in water repellency and stain resistance. In Examples 39 and 42, the haze value was 10 to 11%, "no stain" was obtained by a stain test, and the anti-glare property and the water and stain resistance were excellent.
Table 5 summarizes the results of Examples 37 to 42.
[0105]
Example 43
TiO having a thickness of 100 nm / 100 nm was deposited on the substrate with a hard coat layer obtained in Example 30 by vacuum evaporation.₂/ SiO₂A laminated inorganic film layer (antireflection layer) was formed.
Example 44
SiO on the substrate with a hard coat layer obtained in Example 35 by vacuum evaporation₂An inorganic film layer (antireflection layer) was formed.
Further, the adhesion and scratching of the coating film were evaluated in the same manner as in Example 1. As a result, the initial adhesion of each of Examples 43 and 44 was "no peeling", and the adhesion after the moisture resistance test was all. Is also "no peeling", there is no scratch in the scratch test of Examples 43 and 44, and there are many scratches in the scratch test of Examples 45 to 51. The transmittance at 350 nm was 0% in all the examples. Further, Examples 43 and 44 each showed a visible light reflectance of 5%, which was smaller than the visible light reflectance of 9% similarly measured for the sample of Example 27, showing excellent antireflection performance. I have.
[0106]
Examples 45 to 51
On the substrate with a surface-modified layer obtained in Example 11, TiO by sputtering was used in accordance with Examples 45 to 51, respectively.₂/ SiO₂Laminated inorganic film layer (Example 45), SiO by vacuum evaporation₂Inorganic film layer (Example 46), TiO₂And SiO₂Laminated inorganic film layer (Example 47), SiO 2 by plasma CVD_xInorganic film layer (Example 48), SiO by sputtering_xN_yInorganic film layer (Example 49), SiN by sputtering_xAnd an inorganic film layer of ITO (Example 51) by sputtering.
Furthermore, when the adhesion and the scratching property of the coating film were evaluated in the same manner as in Example 1, the initial adhesion in each of Examples 45 to 51 was “no peeling”, and the adhesion after the moisture resistance test was all. Is "no peeling", and there is no scratch in the scratching test of Examples 43 and 44. However, there are many scratches in Examples 45 to 51, and in all Examples, the visible light transmittance is 89 to 93%. In each case, the transmittance at 350 nm was 0%. Each of Examples 45 to 47 exhibited a visible light reflectance of 5%, which was smaller than the visible light reflectance of 9% similarly measured for the sample of Example 27, indicating excellent antireflection performance. . Examples 48 to 50 all showed excellent moisture permeability, and Example 51 showed excellent transparent conductivity.
Table 6 summarizes the results of Examples 43 to 51.
[0107]
Comparative Example 4
A hard coat layer having a thickness of 3 μm was formed in the same manner as in Example 32 except that no surface modification treatment liquid was used in place of the surface modification treatment liquid 1 used in Example 32.
Comparative Example 5
TiO of 100 nm / 100 nm thickness by sputtering in the same manner as in Example 44 except that no surface modification treatment liquid was used in place of the surface modification treatment liquid 4 used in Example 44.₂/ SiO₂A laminated film antireflection layer was formed.
Comparative Example 6
A TiO having a thickness of 100 nm / 100 nm was formed by sputtering in the same manner as in Comparative Example 5 except that the surface of the hydrophilic treatment performed in Comparative Example 5 was not performed, and the contact angle of the water droplet after the treatment was 90 degrees.₂/ SiO₂A laminated film antireflection layer was formed.
The adhesion of the films obtained in Comparative Examples 4 to 6 was tested immediately after the film formation (initial stage), but all were peeled off. In the scratching property test, Comparative Example 4 had no scratches, but both Comparative Examples 5 and 6 were so scratched that the film was peeled off. In all of Comparative Examples 4 to 6, the optical characteristics were as follows: visible light transmittance was 91 to 92%, and transmittance at 350 nm was 88 to 89%.
Table 6 summarizes the results of Comparative Examples 4 to 6.
[0108]
Example 52
On the substrate with a hard coat layer obtained in Example 30, the refractive index adjusting liquid 1 was applied and cured to form a refractive index adjusting layer having a thickness of 110 nm and a refractive index of 1.72. The low refractive index coating liquid 11 was applied thereon, heated at 80 ° C. for 1 hour, and cured to form a low refractive index layer having a thickness of 100 nm and a refractive index of 1.41.
Example 53
A hard coat layer, a refractive index adjusting layer, and a low refractive index layer were formed in the same manner as in Example 52 except that the low refractive index coating liquid 12 used in Example 52 was replaced with the low refractive index coating liquid 12. did.
Example 54
A refractive index adjustment layer and a low refractive index layer were prepared in the same manner as in Example 52 except that the substrate with a hard coat layer manufactured in Example 37 was used instead of the substrate with a hard coat layer used in Example 52 (manufactured in Example 30). A refractive index layer was formed.
The adhesion of the laminated coating films obtained for Examples 52 to 54 was evaluated. In each of the examples, there was no peeling of the film even after the initial stage and after the moisture resistance test, and there was no problem in the adhesion. When the scratching property and the optical properties were evaluated in the same manner as in Example 1, no scratch was found and the visible light transmittance was 93% in each case. The haze value of Examples 52 and 53 was 0.1%, but the haze value of Example 54 was 10%, and Example 54 showed excellent antiglare properties. The measured visible light reflectance was 6% in all cases, indicating excellent antireflection performance. Regarding the stain test and the contact angle of water droplets on the surface, Examples 52 and 54 were 85 ° and 86 ° with “slight stain remaining”, respectively, whereas Example 53 was “No stain” and 102 ° respectively. Yes, showing excellent water repellency and antifouling properties.
[0109]
Example 55
Instead of applying and curing the low refractive index coating solution 11 used in Example 52, a low refractive index SiO₂A hard coat layer, a refractive index adjusting layer and a low refractive index layer were formed in the same manner as in Example 52 except that the film (film thickness: 100 nm) was coated.
Example 56
A hard coat layer, a refractive index adjusting layer and a low refractive index were obtained in the same manner as in Example 55 except that the hard coat liquid 5 was applied and cured instead of the application and curing of the hard coat liquid 1 used in Example 55. A layer was formed.
Example 57
The base hard coat liquid 10 was applied on the substrate with the surface modified layer obtained in Example 1 and cured to form a base hard coat layer having a thickness of 4 μm. A hard coat layer 9 having a thickness of 0.15 μm was formed by applying the hard coat liquid 9 by a spinner method and photo-curing. TiO of 100 nm / 100 nm thickness is formed thereon by vacuum evaporation.₂/ SiO₂A laminated inorganic film layer was formed.
Example 58
TiO by vacuum evaporation in Example 57₂/ SiO₂A surface modified layer, a base hard coat layer, and a hard coat layer were formed in the same manner as in Example 57 except that the laminated inorganic film layer was not formed.
The adhesion of the coatings obtained for Examples 55 to 58 was evaluated. In each of the examples, there was no peeling of the film even after the initial stage and after the moisture resistance test, and there was no problem in the adhesion. When the scratching property and the optical characteristics were evaluated in the same manner as in Example 1, no scratches were found and the visible light transmittance was 90 to 92%. When the visible light reflectance was measured, Examples 55 to 57 were all 5%, indicating excellent antireflection performance. The haze value of Examples 55 and 56 was 0.1%, whereas the haze value of Examples 57 and 58 was 10%. Since the particle diameter of the fine particles (J) in the hard coat liquid 9 used in Examples 57 and 58 is smaller than that of Example 37, the light diffusion state is uniform and uniform antiglare property can be obtained. Was observed. In the stain test, all were "slight stain remaining", and the contact angles of water droplets on the surface were 85 degrees, 84 degrees, 86 degrees, and 86 degrees, respectively.
Table 7 summarizes the results of Examples 52 to 56.
Note that data not described in the above Examples and Comparative Examples may be included in each table.
[0110]
[Table 1]

[0111]
[Table 2]

[0112]
[Table 3]

[0113]
[Table 4]

[0114]
[Table 5]

[0115]
[Table 6]

[0116]
[Table 7]

Claims (25)

After hydrophilizing the surface of the amorphous polyolefin resin substrate, a surface-modifying liquid containing a polymer of alkyl (meth) acrylate is applied to the hydrophilized surface, and cured to cure the surface. A method for producing an amorphous polyolefin resin article coated with a surface-modified layer, comprising forming a layer. The method for producing an amorphous polyolefin resin article coated with a surface-modified layer according to claim 1, wherein the polymer of alkyl (meth) acrylate is a homopolymer of alkyl (meth) acrylate. The method for producing a surface-modified layer-coated amorphous polyolefin resin article according to claim 2, wherein the surface-modifying liquid further contains an organosilicon compound. The organosilicon compound has the following formula (1)
R ¹ nSi (R ² ) _4-n (1)
Wherein, R ¹ is a methacryloxy group, an acryloxy group, an epoxy group, a vinyl group, an allyl group, an organic functional group having a functional group selected from amino group, 1 R ² is selected from alkoxy groups, acetoxyl groups and chlorine Species or a plurality of hydrolyzing groups, and n is an integer of 1 to 3,
The method for producing an amorphous polyolefin resin article coated with a surface-modified layer according to claim 3, which is an organosilicon compound represented by the formula: The method according to claim 3, wherein the organosilicon compound is an alkoxysilane having a (meth) acryl group. The amorphous polyolefin resin coated with a surface-modified layer according to claim 1, wherein the polymer of the alkyl (meth) acrylate is a copolymer of a (meth) acrylic monomer having an alkoxysilyl group and an alkyl (meth) acrylate. Article manufacturing method. The method for producing an amorphous polyolefin resin article coated with a surface-modified layer according to claim 6, wherein the surface-modifying liquid further contains a curing catalyst. The method for producing an amorphous polyolefin resin article coated with a surface-modified layer according to claim 7, wherein the curing catalyst is ammonium perchlorate. The method for producing a surface-modified layer-coated amorphous polyolefin resin article according to any one of claims 6 to 8, wherein the surface-modifying liquid further contains methylol melamine partially or wholly alkylated. . The method for producing an amorphous polyolefin resin article coated with a surface-modified layer according to any one of claims 1 to 6, wherein the surface-modifying liquid further contains at least one of an ultraviolet absorber and a surfactant. A hard coat liquid containing colloidal silica and an organosilicon compound is applied on the surface-modified layer according to any one of claims 1 to 10, and cured to form a hard coat layer. A method for producing a hard coat-coated amorphous polyolefin resin article. The hard coat liquid,
(A) a polyfunctional acrylate,
(B) Formula (2) below
X _a Si (R ³ (NHR ⁴ ) _b NR ⁵ H) _4-a (2)
Here, X is an alkoxyl group having 1 to 6 carbon atoms, R ³ and R ⁴ are the same or different divalent hydrocarbon groups, and R ⁵ is a hydrogen atom or a monovalent hydrocarbon group; a is an integer of 1 to 3, b is 0 or an integer of 1 to 6,
The method for producing an amorphous polyolefin resin article coated with a hard coat according to claim 11, which comprises an aminosilane represented by the formula: and (C) colloidal silica. The hard coat liquid,
(D) The following formula (3)
_{^{R 7 a R 8 b Si (}} OR 9) 4-a-b (3)
Here, R ⁷ is an alkyl group having 1 to 4 carbon atoms, an allyl group or a halogenated alkyl group having 6 to 12 carbon atoms, a methacryloxyalkyl group having 5 to 8 carbon atoms, and a 2 to 10 carbon atoms. A ureidoalkylene group, an aromatic ureidoalkylene group, an aromatic alkylene group or a mercaptoalkylene group, and R ⁸ is an alkyl group having 1 to 6 carbon atoms, an allyl group, an alkenyl group, a halogenated alkyl group or a halogenated allyl group. R ⁹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an acyl group or an alkylacyl group, a = 1, 2, or 3, and b = 0, 1, or 2,
The method for producing a hard coat-coated amorphous polyolefin resin article according to claim 11, comprising an organosilicon compound represented by the formula: and (E) colloidal silica. The hard coat-coated amorphous polyolefin resin article according to any one of claims 11 to 13, wherein the hard coat liquid further contains fine particles having an average particle diameter of 0.05 to 10 µm and / or fluoroalkylsilane. Manufacturing method. The fluoroalkylsilane is represented by the following formula (4)
R ¹⁰ _c R ¹¹ _d Si (OR ¹² ) _4-cd (4)
Here, R ¹⁰ is a fluorine alkyl group having 1 to 12 carbon atoms, R ¹¹ is an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkenyl group, a halogenated alkyl group or a halogenated aryl group, R ¹² is a hydrogen atom or an alkyl group or an acyl group having 1 to 4 carbon atoms, c is 1, 2 or 3, d is 0, 1 or 2, provided that c + d is 1, 2 or 3 is there,
The method for producing a hard coat-coated amorphous polyolefin resin article according to claim 14, represented by: The method for producing an amorphous polyolefin resin article coated with a hard coat according to any one of claims 11 to 15, wherein the hard coat liquid further contains at least one of a polymerization initiator, a hydrolysis catalyst and a physical property modifier. The method for producing an amorphous polyolefin resin article coated with a hard coat according to claim 16, wherein the physical property modifier comprises one or more of epoxy (meth) acrylate, urethane (meth) acrylate and polyester (meth) acrylate. The method for producing a hard coat-coated amorphous polyolefin resin article according to any one of claims 11 to 17, wherein an inorganic film layer made of a metal or an inorganic compound thereof is formed on the hard coat layer. The inorganic film layer includes at least one metal selected from the group consisting of Ti, Sn, In, Si, Al, W, Mo, Ag, Zn, Zr, Mg, Cr and Ni, an oxide of the metal, and 19. The hard coat-coated amorphous polyolefin resin article according to claim 18, wherein at least one inorganic compound selected from the metal nitrides is formed by vacuum deposition, plasma CVD, sputtering, or ion plating. Production method. The method for producing an amorphous polyolefin resin article coated with a hard coat according to claim 18 or 19, wherein the inorganic film layer is a single-layer or multilayer anti-reflection layer. The method for producing an amorphous polyolefin resin article coated with a hard coat according to any one of claims 11 to 17, wherein a single-layer or multilayer organic anti-reflection layer is formed on the hard coat layer. Between the hard coat layer and the antireflection layer,
(F) a polyfunctional acrylate,
(G) The following equation (5)
R ¹³ _n SiZ _4-n (5)
Here, R ¹³ is an organic functional group having a functional group selected from a methacryloxy group, an acryloxy group, an epoxy group, a vinyl group, an allyl group and an amino group, and Z is one or a group selected from an alkoxyl group, an acetoxyl group and chlorine. A plurality of hydrolyzable groups, n is 1, 2 or 3;
22. The hard coat-coated amorphous material according to claim 20, wherein a liquid containing the silane compound represented by the formula (1) and (H) refractive index adjusting fine particles is applied and then cured to form a refractive index adjusting layer. A method for producing a polyolefin resin article. The method for producing an amorphous polyolefin resin article coated with an inorganic film layer according to any one of claims 1 to 10, wherein an inorganic film layer made of a metal or an inorganic compound thereof is formed on the surface modified layer. An amorphous polyolefin resin article coated with a surface-modified layer produced by the production method according to claim 1. A hard coat-coated amorphous polyolefin resin article produced by the production method according to claim 11.