JP2004002508A - Method of manufacturing hard coat-covered triacetylcellulose resin article and hard coat-covered triacetylcellulose resin article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To form a hard coat layer excellent in adhesive property, optical property and scratch resistance on the surface of triacetylcellulose (TAC) resin without alkali treatment of the TAC resin surface and without deteriorating the surface of the TAC substrate. <P>SOLUTION: The hard coat layer is formed by curing after coating, on the surface of the triacetylcellulose resin substrate, an active energy beam-curable hard coat liquid comprising (A) a multifunctional acrylate, (B) aminosilane and (C) colloidal silica. Antidazzle property and antifouling property are further imparted by adding to the hard coat liquid a fine particle having an average particle diameter of 0.05-10 μm and a fluoroalkylsilane. <P>COPYRIGHT: (C)2004,JPO

Description

【００５６】
ハードコート液１（活性エネルギーシリコーンハードコート）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、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、膜に可撓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））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。
【００５７】
ハードコート液２（防眩性付与ハードコート）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）、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。
【００５８】
ハードコート液３（撥水性付与ハードコート）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。
【００５９】
ハードコート液４（撥水性および防眩性付与ハードコート）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。
【００６０】
ハードコート液５（比較例）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、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（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、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添加し、撹拌し均質に分散させる。これにより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。
【００６１】
ハードコート液６（防眩・撥水性付与ハードコート）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％、日産化学工業製）を１４０ｇ、微粒子（Ｄ）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、フルオロアルキルシラン（Ｅ）としてパーフルオロオクチルエチルトリエトキシシランを１０ｇ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６を得た。
【００６２】
ハードコート液７（活性エネルギー線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：４０ｗｔ％　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７を得た。
【００６３】
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径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。
【００６４】
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。
【００６５】
低屈折率用コート液８（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８を得た。
【００６６】
低屈折率用コート液９（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９を得た。
【００６７】
塗布法および紫外線硬化法
上記ハードコート液１〜４、６、７はバーコート法により、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　ウシオ電機株式会社製）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。低屈折率用コート液８および９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。
【００６８】
評価方法
以下に示す各実施例で得られたＴＡＣフィルム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）後の被膜の密着性（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　５１〜１００−「剥離大」
（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。
【００６９】
実施例１
ＴＡＣフィルムにアルカリ処理をしないで前記ハードコート液１を塗布および紫外線照射による硬化を行い、３μｍの厚みのハードコート被膜を形成した。
次いで、被膜の付着性を評価した。初期及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。
上記の付着性を評価したサンプルとは別のサンプルを複数作製して、前記キズ付き性、汚れ性、光学特性、表面水滴接触角度をそれぞれ評価したところ、キズはなく、汚れがなく、可視光線透過率が９３％、曇価が０．１％であり、表面水滴接触角は８５度であった。なお、被膜を形成する前のＴＡＣフィルムについてのキズ付き性は３であった。
【００７０】
実施例２〜４
実施例１のハードコート液１の代わりにそれぞれハードコート液２（実施例２）、ハードコート液３（実施例３）、ハードコート液４（実施例４）を使用したこと以外は実施例１と同じＴＡＣフィルム上に被膜を形成した。
得られた被膜の付着性を評価した。実施例２〜４のいずれも初期及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。また実施例１と同様に前記キズ付き性、汚れ性、光学特性および表面水滴接触角度をそれぞれ評価したところ、表１に示す通りであり、いずれもキズはなく、汚れは「汚れ残りなし」または「少し汚れ残りあり」であった。また可視光線透過率、曇価および表面水滴接触角は表１に示す通りであった。実施例２、４の曇価は１３〜１４％であって実施例１、３や比較例の曇価に比して非常に高く、実施例２、４が高い防眩性を示すことがわかる。
【００７１】
比較例１
ＴＡＣフィルムにアルカリ処理をしないで前記ハードコート液５を塗布し、その後、実施例１と同じ条件で硬化してハードコート被膜を形成した。
次いで、被膜の前記付着性を評価した。初期にはごく一部で剥離があり、耐湿試験後には被膜が剥離した。実施例１と同様に前記キズ付き性、光学特性、表面水滴接触角度をそれぞれ評価したところ、わずかにキズがあり、可視光線透過率が９１％、曇価が０．１％であり、表面水滴接触角は８６度であった。
【００７２】
比較例２
アルカリ処理を行ったＴＡＣフィルムに前記ハードコート液５を塗布し、比較例１と同じ条件で硬化してハードコート被膜を形成した。
次いで、被膜の前記付着性を評価した。初期に被膜の剥離はなかったが、耐湿試験後には被膜が剥離した。
実施例１と同様に前記キズ付き性、光学特性、表面水滴接触角度をそれぞれ評価したところ、キズが多数あり、可視光線透過率が９１％、曇価が０．４％であり、表面水滴接触角は８７度であった。
【００７３】
実施例５〜１１
ＴＡＣフィルムにアルカリ処理をしないで前記ハードコート液１を塗布し、その後、実施例１と同じ条件で硬化してハードコート被膜を形成した。
次いで、このハードコート被膜の上にそれぞれ実施例５〜１１に応じて真空蒸着によるＴｉＯ_２／ＳｉＯ_２積層無機膜層（実施例５）、プラズマＣＶＤによるＳｉＯ_ｘの無機膜層（実施例６）、プラズマＣＶＤでＴｉＯ_２とＳｉＯ_２の積層無機膜層（実施例７）、プラズマＣＶＤでＳｉＯ_ｘＮ_ｙの無機膜層（実施例８）、スパッタリングによるＳｉＮ_ｘの無機膜層（実施例９）、スパッタリングによるＴｉＯ_２／ＳｉＯ_２の積層無機膜層（実施例１０）およびスパッタリングによるＩＴＯの無機膜層（実施例１１）を形成させた。得られた被膜の付着性を評価した。いずれの実施例についても、初期及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。キズ付き性についてはキズはなく、光学特性について、可視光線透過率および曇価は表２に示す通りであった。なお、実施例５、７、１０はいずれも５％の可視光反射率を示し、実施例１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。実施例６、８および９はいずれも優れた耐透湿性を示し、また実施例１１は優れた透明導電性を示した。
【００７４】
上記の付着性を評価したサンプルとは別のサンプルを複数作製して、前記キズ付き性、光学特性をそれぞれ評価したところ、いずれの実施例についても、キズはなく、可視光線透過率が９０〜９３％、曇価が０．１％であった。
【００７５】
比較例３〜７
ＴＡＣフィルムにアルカリ処理をして前記ハードコート液５を塗布し、その後、実施例１と同じ条件で硬化してハードコート被膜を形成した。
次いで、このハードコート被膜の上に、比較例３〜７に応じて、それぞれ真空蒸着によるＴｉＯ_２とＳｉＯ_２の無機膜層（比較例３）、プラズマＣＶＤによるＴｉＯ_２とＳｉＯ_２の無機膜層（比較例４）、プラズマＣＶＤによるＳｉＯ_ｘの無機膜層（比較例５）、スパッタリングによるＴｉＯ_２とＳｉＯ_２の無機膜層（比較例６）およびスパッタリングによるＩＴＯの無機膜層（比較例７）を形成させた。得られた積層被膜の付着性を評価した。いずれの比較例についても初期には被膜の部分的な剥離があり、耐湿試験後には被膜が大きく剥離した。これらの剥離はいずれも無機膜層とハードコート層との間で生じた。上記の付着性を評価したサンプルとは別のサンプルを複数作製して、前記キズ付き性、光学特性をそれぞれ評価したところ、表２に示すようにいずれの比較例についても多数のキズがあり、可視光線透過率が９１〜９４％、曇価はいずれも０．２％であった。
【００７６】
実施例１２
ＴＡＣフィルム（屈折率１．４８７）にアルカリ処理をしないで前記ハードコート液１を塗布し、その後、実施例１と同じ条件で硬化して膜厚３μｍのハードコート被膜（屈折率１．５３）を形成した。次いで、前記ハードコート被膜の上に前記屈折率調整用液１を塗布し、その後、実施例１と同じ条件で硬化して、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８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。得られた積層被膜の付着性を評価した。初期及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、表３に示すように、キズはなく、可視光線透過率が９４％、曇価が０．１％であった。そして可視光反射率を測定したところ５％であり、実施例１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。
【００７７】
実施例１３
実施例１２で使用した低屈折率用コート液８の代わりに低屈折率用コート液９（撥水性付与熱硬化型ハードコート液、硬化後の屈折率１．４１）を使用したこと以外は実施例１２と同様にしてＴＡＣフィルム上にハードコート被膜および屈折率調整層および低屈折率層被膜を形成した。
【００７８】
実施例１４
実施例１２で使用したハードコート液１の代わりにハードコート液２（防眩性付与ハードコート液）を使用したこと以外は実施例１２と同様にしてＴＡＣフィルム上にハードコート被膜および屈折率調整層および低屈折率層被膜を形成した。
【００７９】
実施例１３および１４で得られた被膜の付着性、キズ付き性および光学特性について実施例１２と同様に評価した。実施例１３および１４はともに５％の可視光反射率を有し優れた反射防止性能を示した。その他の結果は表３に示す通りであった。また実施例１３について汚れ性試験および表面水滴接触角を測定したところそれぞれ「汚れ残しなし」および１０３度であり、優れた防汚性を示した。また実施例１４は優れた防眩性を示した。
【００８０】
比較例８
実施例１２のハードコート液１の代わりにハードコート液５を使用したこと以外は実施例１４と同じＴＡＣフィルム上にハードコート被膜および屈折率調整層および低屈折率層被膜を形成した。
得られた被膜の付着性を評価した。初期には被膜の剥離がなく、耐湿試験後には極一部で剥離（屈折率調整層と低屈折率層との間の剥離）があった。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、少しキズがあり、可視光線透過率が９４％、曇価が０．１％であった。
【００８１】
実施例１５
実施例１２において低屈折率用コート液８を使用して低屈折率層を形成する代わりに真空蒸着によるＳｉＯ_２の低屈折率無機層を形成した他は実施例１２と同じＴＡＣフィルム上にハードコート被膜および屈折率調整層および低屈折率層被膜を形成した。初期及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。キズ付き性についてはキズはなく、光学特性について、可視光線透過率および曇価は表３に示す通りであった。また５％の可視光反射率を示した。
【００８２】
比較例９
実施例１２のハードコート液１の代わりにハードコート液５を使用したこと以外は実施例１５と同じＴＡＣフィルム上にハードコート被膜および屈折率調整層および低屈折率層被膜を形成した。初期には被膜は部分的に剥離し、耐湿試験後には大きく剥離した。剥離は低屈折率層と屈折調整層との間で生じた。キズ付き性については少しキズがあり、光学特性は表３に示す通りであった。
【００８３】
実施例１６
実施例１３において形成した屈折率調整層を形成せずにハードコート被膜の上に直接低屈折率用コート液９を塗布し加熱硬化させる他は実施例１３と同じＴＡＣフィルム上にハードコート被膜および低屈折率層被膜を形成した。初期及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。また６％の可視光反射率を有し優れた反射防止性能を示した。また表面水滴接触角は１０３度であった。キズ付き性についてはキズはなく、光学特性について、可視光線透過率および曇価は表３に示す通りであった。
【００８４】
実施例１７
ＴＡＣフィルムにアルカリ処理をしないで下地ハードコート層として前記ハードコート液７を塗布し、その後、実施例１と同じ条件で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た。その下地ハードコート層の上にハードコート液６をスピナー法で塗布し、その後、同様に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。得られた製品の性能を表１に示す。使用した微粒子（Ｄ）の粒径が実施例２、４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。
【００８５】
実施例１８
実施例１７で形成したハードコート層の上にさらにＴｉＯ_２とＳｉＯ_２の無機膜層を形成させた他は実施例１７と同様にしてＴＡＣフィルム上に下地ハードコート層、ハードコート層、および２層反射防止被膜を形成した。得られた製品の性能は表３に示す通りであり優れた防眩性を示した。また可視光反射率は５％であり、優れた反射防止性能を示した。
【００８６】
以上の実施例と比較例をそれぞれ表１〜表３にまとめて示す。表の結果を見れば明らかなように、本発明の実施例では、ＴＡＣフィルムに対して非常に付着性（密着性）が良好で、かつキズ付き性（耐擦傷性）が良好で透明性が良好なハードコート被膜が形成できている。
【００８７】
また、ＴＡＣフィルムの表面処理をすることなく高付着耐久性のあるハードコート被覆ＴＡＣフィルムが得られる。その理由は、ハードコート層がアミノ有機官能性シランを構成材料として含むことによりアミノ基とＴＡＣ中の官能基が相互作用するためと考えられる。
【００８８】
また、金属または無機化合物からなる微粒子添加による表面凹凸付与、フルオロアルキルシラン導入による塗膜表面の自由エネルギー低下、単層または多層の無機膜または有機膜の被覆により、防眩性、撥水性、汚れにくい、汚れ落ち易い、高い耐透湿性、反射防止性能、透明導電性といった種々の特性をＴＡＣフィルムの表面に付与できる。
【００８９】
【表１】

【００９０】
【表２】

【００９１】
【表３】

【００９２】
【発明の効果】
本発明によればＴＡＣ樹脂に対して基板表面に非常に密着性が良好で、かつ耐擦傷性の良好なハードコート被膜が形成できるので、例えば屋外など傷が付きやすい環境で使用される用途にも利用可能性が高まる。さらに、防眩性、防汚性の高いハードコート被膜が得られた。
【００９３】
また、本発明の被膜層は可視光線の吸収がないため、ＴＡＣ表面が被膜で影響を受けず、可視光線透過性が高い。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a coated triacetylcellulose resin article, and more particularly to a method for producing a hardcoat-coated triacetylcellulose resin article having excellent scratch resistance, transparency and adhesion.
[0002]
[Prior art]
Televisions, personal computers, word processors, and various other displays display images by passing light through a transparent substrate whose surface is made of glass, plastic, or surface-treated. Above all, a liquid crystal display uses a film-like polarizing element for controlling light transmission. As the film material containing the polarizing element, generally, uniaxially stretched polyvinyl alcohol is used. However, this has drawbacks such as easy tearing in the stretching axis direction and poor water resistance. Usually, in order to compensate for these drawbacks, the polarizing element-containing film is used as a polarizing plate by sandwiching both surfaces of a polarizing element-containing film with a transparent film. As a material of the transparent film, triacetyl cellulose (hereinafter, sometimes referred to as TAC) is applied in terms of transparency, adhesion, and moisture impermeability.
[0003]
However, the TAC film has poor scratch resistance, and has been improved in scratch resistance by performing various surface treatments. Some TAC films that have been subjected to various surface treatments (hard coats) have been able to satisfy the performance of the final product. However, in recent years, higher performance and higher durability have been required, and over a long period of time. There is a problem that the surface treatment layer is partially dropped or peeled off during use. In particular, when used in a high-temperature and high-humidity environment, the surface treatment layer is apt to fall off or peel off, and the adhesion to the TAC substrate is significantly reduced.
[0004]
As a method for improving the adhesion of the surface treatment layer (hard coat layer) to a TAC substrate, an alkali treatment is generally performed. Besides the alkali treatment, a corona treatment or a low-temperature plasma treatment is also conceivable. Japanese Patent Application Laid-Open No. 2001-279017 discloses a method of adjusting the amount of a plasticizer in TAC itself in order to improve the adhesion of a surface treatment layer to the surface of a TAC substrate. Furthermore, there is a method in which an easy-adhesion layer (primer layer) is provided between a hard coat layer of an ionizing radiation-curable resin such as polyester acrylate and polyurethane acrylate and a saponified TAC substrate to improve adhesion. (JP-A-7-151914). There is also a method (JP-A-11-209717) in which the solvent of the coating solution is changed to methyl isobutyl ketone (MIBK) to minimize the solvent attack on the TAC surface and improve the adhesion of the coating film.
[0005]
[Problems to be solved by the invention]
However, in the alkali treatment, although the adhesion of the hard coat layer is considerably improved, there is still a problem that the moisture resistance is still insufficient, and the number of treatment steps is increased and the treatment cost is high. Also, the corona treatment or the low-temperature plasma treatment has a problem that the treatment in a vacuum bleeds the plasticizer on the surface of the TAC substrate, and the treatment at normal pressure deteriorates the surface of the substrate. In addition, the method of adjusting the amount of the plasticizer of the TAC itself has a problem of lack of versatility. Further, in the method of providing the easy-adhesion layer (primer layer), the number of steps is increased, so that there is a problem in terms of an increase in defect occurrence rate and cost. In addition, in the case of using MIBK as the solvent, the optical characteristics deteriorate.
[0006]
It is an object of the present invention to provide adhesion, optical properties and resistance to triacetylcellulose (TAC) resin surfaces without the need for pretreatment such as alkali treatment and without degrading the TAC substrate surface. An object of the present invention is to form a hard coat layer having excellent scratch resistance.
[0007]
Another object of the present invention is to further impart antiglare properties, water repellency, antifouling properties and other functions to the above-mentioned hard coat layer having excellent adhesion, optical properties and scratch resistance.
[0008]
[Means for Solving the Problems]
That is, in the present invention, a hard coat liquid containing (A) a polyfunctional acrylate, (B) aminosilane and (C) colloidal silica is applied to the surface of a triacetyl cellulose resin substrate, and then cured to form a hard coat layer. This is a method for producing a hard coat-coated acetylcellulose resin article to be formed.
[0009]
The hard coat liquid in the present invention contains (A) a polyfunctional acrylate, (B) aminosilane, and (C) colloidal silica. Hereinafter, each component 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. 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. 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.
[0010]
One or more polyfunctional acrylates are used together.
The aminosilane as the component (B) is an alkoxysilane having an amino group or a substituted amino group. Preferably, the following formula (1)
X_aSi (R¹(NHR²)_bNR³H)_4-a(1)
Here, X is an alkoxyl group having 1 to 6 carbon atoms;¹, R²Are the same or different divalent hydrocarbon groups,³Is a hydrogen atom or a monovalent hydrocarbon group, a is an integer of 1 to 3, and b is 0 or an integer of 1 to 6,
Amino organofunctional silane. In the formula (1), a is preferably 2 or 3, and b is preferably 0 or 1.
Examples of the aminosilane represented by the formula (1) include, for example, n- (2-aminoethyl-3-aminopropyl) trimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, γ- (2 -Aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropylmethyl Examples include dimethoxysilane hydrochloride and γ-anilinopropyltrimethoxysilane.
[0011]
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).
[0012]
The surface of the composite oxide may be 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 with the organic silane compound used for the treatment having a hydrolyzable group or after the hydrolysis.
[0013]
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.
[0014]
The hard coat liquid used in the present invention preferably contains a polymerization initiator for polymerizing a polyfunctional acrylate. It is preferable to contain a photopolymerization initiator for photopolymerization, and it is preferable to contain a thermal polymerization initiator for heat polymerization. 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, and tetrakis (pentafluorodiphenyl) borate. .
[0015]
Examples of the thermal polymerization initiator include peroxyketals such as 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, hydroperoxides such as t-hexyl hydroperoxide, and lauroylperoxide. Peroxyesters such as diacyl peroxides such as oxides, peroxydicarbonates such as diisopropylperoxydicarbonate, and peroxyesters such as (aa-bis-neodecanoylperoxy) diisopropylbenzene can be used.
[0016]
The amount of the thermal polymerization initiator or the photopolymerization initiator is preferably 0.1 to 30 parts by weight, more preferably 1 to 15 parts by weight, based on 100 parts by weight of the polyfunctional acrylate of the hard coat composition.
[0017]
The hard coat liquid used in the present invention preferably contains a hydrolysis catalyst for hydrolysis and polycondensation of 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. Among them, 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).
[0018]
The hard coat liquid used in the present invention is preferably from 1.5 to 50 parts by weight, preferably from 8 to 25 parts by weight, based on 100 parts by weight of the polyfunctional acrylate (A), colloidal. Silica (C) (solid content) contains 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”.
[0019]
In order to impart antiglare properties to the hard coat-coated acetylcellulose resin article obtained in the present invention, the basic hard coat liquid contains fine particles having an average particle diameter of 0.05 μm (50 nm) to 10 μm as the component (D). be able to.
[0020]
As the fine particles (D) having an average particle diameter of 0.05 μm to 10 μm, fine particles (D) made of a metal or an inorganic compound are preferably used. The more preferable average particle diameter of the fine particles (D) is 2 to 10 μm, and the more preferable average particle diameter is 4 to 8 μm. Especially for display applications, the addition of the fine particles (D) can reduce the reflection of ambient light and sharpen the image display.
Examples of the material of the fine particles (D) 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.
[0021]
These fine particles (D) 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 above for modifying the surface of colloidal silica, particularly monofunctional silane, are preferably used.
[0022]
A product in which fine particles having an average particle size of 0.05 μm (50 nm) to 10 μm are dispersed in a dispersion medium at a ratio of 15 to 60% by weight can be obtained as a commercial product 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.).
[0023]
These fine particles (D) are preferably spherical or nearly spherical, and may be solid particles or porous particles. The refractive index is preferably equal to or smaller than the refractive index of the photocured product of the remaining hard coat liquid excluding the fine particles (D). This makes it easier to reduce interference unevenness due to uneven film thickness.
The above-mentioned colloidal silica (C) is a component for increasing the hardness of the hard coat layer. The fine particles (D) 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 size, for example, colloidal silica having an average particle size of 50 nm to 200 nm functions as fine particles (D). Therefore, if the hard coat liquid used in the present invention contains colloidal silica (C) having an average particle size of 50 nm to 200 nm, antiglare properties can be obtained without containing fine particles (D).
[0024]
In order to provide anti-glare properties, it is preferable to add the fine particles (D) to the basic hard coat liquid in an amount of 1.0 to 150 parts by weight, preferably 3 to 100 parts by weight, based on 100 parts by weight of the polyfunctional acrylate (A). . The more preferable content of the fine particles (D) depends on the average particle size of the fine particles (D). When the average particle size of the fine particles (D) is relatively large, for example, more than 2 μm and 10 μm or less, the content of the fine particles (D) is preferably 1.0 to 40 parts by weight, and more preferably 3 to 20 parts by weight. More preferred. When the average particle diameter of the fine particles (D) is relatively small, for example, 0.05 μm (50 nm) to 2 μm, the content of the fine particles (D) is preferably 20 to 150 parts by weight, and 50 to 100 parts by weight. Is more preferred. When only the colloidal silica (D) also serving as the fine particles (D) is contained, the content of the colloidal silica (C) (solid content) is 40 to 185 parts by weight, preferably 60 to 130 parts by weight.
[0025]
In order to impart water repellency to the hard coat-coated acetylcellulose resin article obtained in the present invention, the hard coat liquid may contain a fluoroalkylsilane as the component (E).
As the fluoroalkylsilane (E), the following formula (2)
R⁴ _cR⁵ _dSi (OR⁶)_4-cd (2)
Where R⁴Is a fluorine alkyl group having 1 to 12 carbon atoms;⁵Is an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkenyl group, a halogenated alkyl group or a halogenated aryl group;⁶Is a hydrogen atom or an alkyl group or an 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.
[0026]
Examples of the compound represented by the formula (2) 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.
[0027]
In order to impart water repellency, it is preferable to add 1.0 to 20 parts by weight, preferably 3 to 15 parts by weight, of the fluoroalkylsilane (E) to 100 parts by weight of the polyfunctional acrylate (A) to the basic hard coat liquid. Is more preferable.
[0028]
By adding each of the fine particles (D) and the fluoroalkylsilane (E) to the basic hard coat liquid in the above amounts, the hard coat-coated acetylcellulose resin article obtained in the present invention can be provided with anti-glare properties and water repellency. it can. 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. This physical property modifier can be added to the basic hard coat liquid 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).
[0029]
The hard coat liquid used in the present invention may 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.
[0030]
The inorganic oxide fine particles for refractive index adjustment 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 above for modifying the surface of colloidal silica, particularly monofunctional silane, are preferably used.
[0031]
The refractive index adjusting fine particles can be added to the basic hard coat liquid 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). The refractive index of the resulting hard coat layer can be increased by 0.01 to 0.50. When the colloidal silica (C) in the hard coat liquid or the fine particles (D) to be added to the hard coat liquid as needed corresponds to the refractive index adjusting fine particles, the refractive index adjusting fine particles are added separately. Even without this, the refractive index of the hard coat layer may be able to be increased to a predetermined value.
[0032]
The hard coat composition of the present invention is preferably prepared as a dispersion in a liquid medium containing a predetermined amount of the above-mentioned active ingredient.
The polyfunctional acrylate (A) and the aminoorganofunctional silane (B) react during the preparation of the hard coat composition or during aging after the preparation. In the reaction between the polyfunctional acrylate and the aminoorganofunctional silane, the primary or secondary amino functional group of the aminoorganofunctional silane is one or more of the (meth) acrylate double bonds of the polyfunctional acrylate monomer. To Michael.
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.
[0033]
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; alcohols such as methanol, ethanol, 1-propanol and 2-propanol.
[0034]
Further, the hard coat liquid may contain a leveling agent and a lubricity imparting agent for a cured film as optional components. As such an agent, 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 an agent is preferably used in an amount of 0.001 to 10% by weight based on the total amount of the solution. 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.
[0035]
The hard coat liquid is applied to the surface of a triacetyl cellulose resin base material, for example, one surface or both surfaces of a triacetyl cellulose 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 10 μm. If it is smaller than 1.0 μm, the hardness of the film is not sufficient, while if it is larger than 10 μm, the flexibility is reduced.
[0036]
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.
[0037]
After the application, the hard coat layer is formed by heating the coating film or irradiating it with an active energy ray such as an ultraviolet ray or an electron beam. 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) of ultraviolet light having a total ultraviolet irradiation energy of 300 to 3000 (mJ / cm).²) For several seconds to 30 minutes.
After application of the hardcoat liquid, the liquid medium is removed by drying or by evaporation during irradiation. By this irradiation, the (meth) acryloyl groups of the polyfunctional acrylate (A) are photopolymerized. The hydrolyzable groups such as the alkoxyl group of the aminosilane (B) (and the fluoroalkylsilane (E)) are hydrolyzed during the preparation of the hard coat composition, during aging, before irradiation after application or during irradiation after application. Polycondensate.
[0038]
The acetylcellulose resin article coated with the hard coat layer as described above has excellent surface hardness, and thus has improved scratch resistance. When the fine particles (D) are added to the hard coat liquid, anti-glare properties are imparted in addition to scratch resistance. The fine particles (D) 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 a water repellent function is imparted to the hard coat layer, the surface of the fine particles (D) protruding from the hard coat layer is preferably covered with a thin layer of the hard coat, whereby the above function is effectively exhibited. Is done. By embedding the fine particles (D) at a height of half or more, it is possible to advantageously prevent the fine particles (D) from falling off from the hard coat layer. Further, the fine particles (D) are preferably adjacent to 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 the 10-point average roughness (Rz) is 6 μm or less. However, if the entire fine particles (D) are buried in the hard coat layer, the anti-glare property cannot be exhibited. 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 (D) in the hard coat layer, the thickness of the hard coat layer, and the like.
[0039]
A base hard coat layer can be further provided between the resin base material and the hard coat layer containing fine particles (D). As the base hard coat layer, a hard coat layer obtained from a basic hard coat solution can be used. A fine particle (D) -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.
[0040]
The hard coat composition for the hard coat layer used in combination with the underlying hard coat layer contains fine particles (D) having a relatively small average particle size, for example, those having an average particle size of 0.05 μm (50 nm) to 2 μm. Is preferred. As a result, fine particles (D) having a small average particle diameter can be embedded in the hard coat layer, and a part of the fine particles can be made to protrude from the surface of the hard coat layer, so that uniform anti-glare properties can be easily provided. More preferably, the ratio of the thickness (μm) of the hard coat layer to the average particle size (μm) of the fine particles (D) is 50 to 95%. In this case, the fine particles (D) easily disperse as a single particle layer while making a part of the surface protrude from the surface of the hard coat layer in the hard coat layer and burying at a height of half or more of the surface. Uniform anti-glare properties are obtained.
[0041]
When a fluoroalkylsilane (E) 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.
[0042]
By adding both the fine particles (D) and the fluoroalkylsilane (E) to the basic hard coat liquid, the antiglare property is improved, and the adhesion of dirt to the fine uneven surface accompanying the antiglare property and the dirt removal property are improved. Can be improved.
[0043]
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 in the present invention. Examples of the material of the inorganic film layer include at least one metal selected from the group consisting of Ti, Sn, In, Si, Al, W, Mo, Ag, Zn, Zr, Mg, Cr, and Ni, and an oxide of the metal. And at least one inorganic compound selected from nitrides of the metal. 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.
[0044]
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.
[0045]
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)
[0046]
In order to impart an antireflection property to the hard coat-coated acetylcellulose resin article of the present invention, a single layer or a multilayer of the above 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, it is preferable to adjust the thickness of the underlayer of the single-layer or multilayer antireflection inorganic film layer to a range of 80 to 250 nm. Therefore, between the hard coat layer having a thickness of 1.0 to 10 μm (containing no fine particles for adjusting the refractive index) and the monolayer or multilayer antireflection inorganic film layer
(F) a polyfunctional acrylate,
(G) The following formula (3)
R⁹ _nSiZ_4-n(3)
Where R⁹Is an organic functional group having a functional group selected from a methacryloxy group, an acryloxy group, a vinyl group, an allyl group and an amino group, and Z is one or more hydrolyzable groups selected from an alkoxyl group, an acetoxyl group and chlorine. And n is 1, 2 or 3.
A silane compound represented by
(H) Fine particles for adjusting refractive index
It is preferable to provide a refractive index adjusting layer having a thickness of preferably 80 to 250 nm formed by applying a liquid containing and curing the liquid.
[0047]
Examples of the silane compound (G) 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 these, 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane are particularly preferably used.
[0048]
As the polyfunctional acrylate (F) and the refractive index adjusting fine particles (H), 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 refractive index adjustment is based on 100 parts by weight of the polyfunctional acrylate (F) in the above liquid so that the refractive index adjusting layer has a refractive index required as a base layer of the antireflection inorganic film layer. It is adjusted within the range of 1 to 900 parts by weight.
[0049]
Since the refractive index adjusting 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 (D), and a single or multilayer anti-reflection film layer is further provided on the refractive index adjusting layer, so that the reflection is maintained while maintaining the film strength. An anti-glare property and an anti-glare property can be provided. Further, the refractive index adjusting layer using a silane compound (G) 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 (D). If the requirements for the fine particles for adjusting the refractive index and the fine particles (D) are the same, 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 adjusting the refractive index (D).
[0050]
On the hard coat layer in the present invention, a single or multilayer antireflection organic layer 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 (4)
R¹ _aR² _bSi (OR³)_4-ab(4)
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, and an aromatic compound. 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, acyl, or alkylacyl group having 1 to 4 carbon atoms
A = 1,2,3, b = 0,1,2,
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.
[0051]
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 (4). 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 (4). Parts by weight, more preferably 250 to 500 parts by weight.
[0052]
Examples of the structure of the acetylcellulose resin article coated with the hard coat obtained according to the present invention include the following. The surface of the TAC substrate does not require a pretreatment such as an alkali treatment, but may be pretreated.
As a single layer
(1) TAC / hard coat layer
(2) TAC / anti-glare hard coat layer
(3) TAC / water-repellent hard coat layer
(4) TAC / water-repellent / anti-glare hard coat layer
With inorganic film
(5) TAC / hard coat layer / transparent conductive inorganic film
(6) TAC / hard coat layer / moisture permeable inorganic membrane
(7) TAC / hard coat layer / single-layer / multi-layer anti-reflective inorganic film
(8) TAC / hard coat layer (containing fine particles for adjusting refractive index) / single-layer / multi-layer anti-reflection inorganic film
(9) TAC / anti-glare hard coat (containing anti-glare fine particles) / single-layer / multi-layer anti-reflective inorganic film
With two hard coat layers
(10) TAC / underlying hard coat layer (thick film) / anti-glare hard coat containing small particle size fine particles (thin film)
(11) TAC / underlying hard coat layer (thick film) / water-repellent / anti-glare hard coat layer containing small particle size fine particles (thin film)
(12) TAC / underlying hard coat layer (thick film) / anti-glare hard coat layer containing small particle size fine particles (thin film) / single-layer / multi-layer anti-reflection film
With refractive index adjustment layer and single-layer / multi-layer anti-reflective inorganic or organic film
(13) TAC / hard coat layer / refractive index adjusting layer / single layer anti-reflective organic film
(14) TAC / hard coat layer / refractive index adjusting layer / water-repellent single layer anti-reflective organic film
(15) TAC / hard coat layer / refractive index adjustment layer / single-layer / multi-layer anti-reflection inorganic film
(16) TAC / antiglare hard coat layer / refractive index adjusting layer / single-layer antireflection organic film
(17) TAC / anti-glare hard coat layer / refractive index adjusting layer / single-layer / multi-layer anti-reflection inorganic film
(18) TAC / hard coat layer / water-repellent single layer anti-reflective organic film
[0053]
Although the application to the triacetylcellulose resin substrate itself has been described above, the invention is not limited thereto, and may be applied to the surface of a triacetylcellulose resin processed article of an acetylcellulose resin such as a polarizing film and a display panel.
[0054]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the present invention will be specifically described with reference to examples.
The base materials, treatment methods, inorganic film layer forming methods, hard coat liquid preparation methods, coating methods, ultraviolet curing methods, evaluation methods, and the like used in Examples and Comparative Examples are as follows.
Base material
A triacetyl cellulose (TAC) film (thickness: 80 μm, visible light transmittance: 92%, manufactured by Fuji Photo Film Co., Ltd., model number: FT-UV-80) was used.
Alkali treatment
It was immersed in a heated 3 mol / l NaOH aqueous solution at 60 ° C. for 1 minute, washed with water, further immersed in a 1 mol / l hydrochloric acid aqueous solution at room temperature for 1 minute, and then washed with water. The alkali treatment is a kind of saponification treatment, and hydrolyzes an acetyl group portion of TAC to introduce a hydroxyl group, thereby improving the reactivity of the TAC surface.
[0055]

[0056]
Preparation of hard coat liquid 1 (active energy silicone 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" (dispersed silica fine particles having an average particle size of 20 nm in n-propyl cellosolve in Nissan Chemical Industries, Ltd .; silica content of 30% by weight) as colloidal silica to impart flexibility to the film; 5.0 g of "Epoxy Ester 3002M" (Kyoeisha Chemical Co., Ltd.) and 14.5 g of butyl acetate are added as epoxy acrylate for 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.
[0057]
Preparation of hard coat liquid 2 (hard coat with anti-glare properties)
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, 45.0 g of colloidal silica “IPA-ST-ZL” (manufactured by Nissan Chemical Industries, silica fine particles having an average particle diameter of 80 to 100 nm dispersed in isopropanol; silica content 30% by weight), and 1.0 g of "UA-306H" (Kyoeisha Chemical Co., Ltd., urethane prepolymer of pentaerythritol triacrylate and hexamethylene diisocyanate) as urethane acrylate for increasing the hardness of the film and curing the film with low energy; Add flow control agent to 0. g 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 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 properties and scratch resistance was obtained.
[0058]
Preparation of hard coat liquid 3 (hard coat with water repellency)
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 a colloidal silica (manufactured by Nissan Chemical Industries, silica fine particles having an average particle diameter of 10 to 20 nm are dispersed in isopropanol; silica content: 30% by weight) Are added, and 9.0 g of perfluorooctylethyltriethoxysilane are added and reacted. Then, 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. As a result, a hard coat liquid 3 for imparting water repellency and scratch resistance was obtained.
[0059]
Preparation of hard coat liquid 4 (hard coat imparting water repellency and antiglare property)
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 to cause a reaction, 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.
[0060]
Preparation of Hard Coat Solution 5 (Comparative Example)
12.4 g of 1,6-hexanediol diacrylate as a polyfunctional acrylate, 6.3 g of 2-methoxypropanol, 4.0 g of acetic acid, 0.8 g of benzophenone as a photopolymerization initiator, and "NPC-ST-30" as colloidal silica 26.0 g of silica particles having an average particle size of 20 nm dispersed in n-propyl cellosolve (manufactured by Nissan Chemical Co., Ltd .; silica content: 30% by weight) and 14.5 g of butyl acetate are added. Next, 0.1 g of a flow control agent is added. Thereafter, 100 g of 2-methoxypropanol is added, and the mixture is stirred and uniformly dispersed. As a result, a hard coat liquid 5 for imparting scratch resistance was obtained.
[0061]
Preparation of hard coat liquid 6 (hard coat with anti-glare and water repellency)
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, average particle 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 (D) (particle size: 0.50 to 0.50) 0.56 μm, active ingredient: 15 parts by weight, 500 g of Nippon Shokubai Co., Ltd.) and 10 g of perfluorooctylethyltriethoxysilane as fluoroalkylsilane (E) were added and stirred, and then benzophenone was used as a photoinitiator. 5 g and a flow control agent 0.1 g were added, and the hard coat liquid 6 was added. Obtained.
[0062]
Preparation of hard coat liquid 7 (active energy ray-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 wt% @ Nissan Chemical Industries, Ltd.), 5.0 g of “Epoxyester 3002M” (Kyoeisha Chemical Co., Ltd.) as epoxy acrylate, acetic acid 14.5 g of butyl 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 7.
[0063]
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, "NPC-ST-30" as colloidal silica (manufactured by Nissan Chemical Industries, Ltd., silica fine particles having an average particle diameter of 20 nm dispersed in n-propyl cellosolve) (Silica content 30% by weight). Next, 0.1 g of a flow control agent is added.
[0064]
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.
[0065]
Preparation of low refractive index coating liquid 8 (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 are reacted. Further, 0.1 g of "Paint Additive 19" (manufactured by Dow Corning) was added as a flow control agent, followed by stirring to obtain a coating liquid 8 for low refractive index.
[0066]
Preparation of Coating Liquid 9 for Low Refractive Index (Heat-curing Hard Coating Liquid with Water Repellency)
600 g of "IPA-ST-ZL" (manufactured by Nissan Chemical Industries, 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 are reacted. After that, 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 and stirred to obtain a coating solution 9 for a low refractive index.
[0067]
Coating method and UV curing method
The hard coat liquids 1 to 4, 6, and 7 are applied by a bar coat method, and the hard coat liquid 5 is applied by a spinner method. Thereafter, the total ultraviolet irradiation energy is 1000 (mJ / cm) by an ultraviolet lamp having an output of 120 W / cm.²1) 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 refractive index adjusting layer liquid 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 coating liquids for low refractive index 8 and 9 were applied by a spin method, and the applied film was cured by heating at 80 ° C. for 30 minutes.
[0068]
Evaluation method
The evaluation method of the coating film coated with the TAC film 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. Before the moisture resistance test (initial) and the moisture resistance test (in a 50 ° C., 95% RH tank for 10 days) ) The adhesion (easy adhesion) and the moisture permeability of the coating film were evaluated, and the number of peeled squares out of the 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 # 51-100-"large peeling"
(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.
[0069]
Example 1
The hard coat liquid 1 was applied to the TAC film without alkali treatment and cured by irradiation with ultraviolet rays to form a hard coat film having a thickness of 3 μm.
Next, the adhesion of the coating was evaluated. There was no peeling of the coating even at the initial stage and after the moisture resistance test, and there was no problem in adhesion.
When a plurality of samples different from the sample for which the above-mentioned adhesion was evaluated were prepared, and the scratching property, dirtiness, optical properties, and surface water droplet contact angle were evaluated, there were no scratches, no stains, and no visible light. The transmittance was 93%, the haze was 0.1%, and the contact angle of water droplets on the surface was 85 degrees. The scratch resistance of the TAC film before forming the coating was 3.
[0070]
Examples 2 to 4
Example 1 except that the hard coat liquid 2 (Example 2), the hard coat liquid 3 (Example 3), and the hard coat liquid 4 (Example 4) were used instead of the hard coat liquid 1 of Example 1. A film was formed on the same TAC film as in Example 1.
The adhesion of the obtained coating was evaluated. In all of Examples 2 to 4, 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 adhesiveness. In addition, when the scratching property, stain property, optical property, and surface water droplet contact angle were respectively evaluated in the same manner as in Example 1, the results are as shown in Table 1, none of which was scratched, and the stain was "no stain remaining" or "There is a little dirt left." Further, the visible light transmittance, the haze value and the contact angle of the surface water droplet were as shown in Table 1. The haze value of Examples 2 and 4 is 13 to 14%, which is very high as compared with the haze values of Examples 1 and 3 and Comparative Example. It can be seen that Examples 2 and 4 show high antiglare properties. .
[0071]
Comparative Example 1
The hard coat liquid 5 was applied to the TAC film without alkali treatment, and then cured under the same conditions as in Example 1 to form a hard coat film.
Next, the adhesion of the coating was evaluated. Initially, only a small portion was peeled off, and the film was peeled off after the moisture resistance test. When the scratching property, the optical characteristics, and the contact angle of the surface water droplet were evaluated in the same manner as in Example 1, there were slight scratches, the visible light transmittance was 91%, the haze value was 0.1%, and the surface water droplet was found. The contact angle was 86 degrees.
[0072]
Comparative Example 2
The hard coat liquid 5 was applied to the TAC film subjected to the alkali treatment, and cured under the same conditions as in Comparative Example 1 to form a hard coat film.
Next, the adhesion of the coating was evaluated. Although there was no peeling of the film at the initial stage, the film peeled after the moisture resistance test.
The scratching property, optical properties, and contact angle of the surface water droplet were evaluated in the same manner as in Example 1. As a result, there were many scratches, the visible light transmittance was 91%, the haze value was 0.4%, and the surface water droplet contact was observed. The angle was 87 degrees.
[0073]
Examples 5 to 11
The hard coat liquid 1 was applied to the TAC film without alkali treatment, and then cured under the same conditions as in Example 1 to form a hard coat film.
Then, TiO was formed on the hard coat film by vacuum evaporation according to Examples 5 to 11, respectively.₂/ SiO₂Laminated inorganic film layer (Example 5), SiO by plasma CVD_xInorganic film layer (Example 6), TiO₂And SiO₂Layered inorganic film layer (Example 7), SiO 2_xN_yInorganic film layer (Example 8), SiN by sputtering_xInorganic film layer (Example 9), TiO by sputtering₂/ SiO₂To form a laminated inorganic film layer (Example 10) and an inorganic film layer of ITO (Example 11) by sputtering. The adhesion of the obtained coating was evaluated. In any of the examples, there was no peeling of the coating film even after the initial stage and after the moisture resistance test, and there was no problem in the adhesiveness. As for the scratching property, there were no scratches, and the visible light transmittance and haze of the optical properties were as shown in Table 2. In addition, Examples 5, 7, and 10 all show a visible light reflectance of 5%, which is smaller than the visible light reflectance of 9% similarly measured for the sample of Example 1, indicating excellent antireflection performance. Is shown. Examples 6, 8 and 9 all exhibited excellent moisture permeation resistance, and Example 11 exhibited excellent transparent conductivity.
[0074]
A plurality of samples different from the sample for which the above-mentioned adhesiveness was evaluated were prepared, and the scratching property and the optical characteristics were evaluated. For each of the examples, there was no scratch and the visible light transmittance was 90 to 90%. The haze was 93% and the haze was 0.1%.
[0075]
Comparative Examples 3 to 7
The TAC film was subjected to an alkali treatment to apply the hard coat liquid 5, and then cured under the same conditions as in Example 1 to form a hard coat film.
Next, on this hard coat film, according to Comparative Examples 3 to 7, TiO by vacuum deposition was used.₂And SiO₂Inorganic film layer (Comparative Example 3), TiO by plasma CVD₂And SiO₂Inorganic film layer (Comparative Example 4), SiO by plasma CVD_xInorganic film layer (Comparative Example 5), TiO by sputtering₂And SiO₂(Comparative Example 6) and an ITO inorganic film layer (Comparative Example 7) by sputtering. The adhesion of the obtained laminated film was evaluated. In all of the comparative examples, the coating was partially peeled at the initial stage, and the coating was largely peeled after the moisture resistance test. All of these peelings occurred between the inorganic film layer and the hard coat layer. A plurality of samples different from the sample for which the above-described adhesion was evaluated were prepared, and the scratching property and the optical characteristics were evaluated. As shown in Table 2, there were many scratches for any of the comparative examples. The visible light transmittance was 91 to 94%, and the haze was 0.2% in all cases.
[0076]
Example 12
The TAC film (refractive index: 1.487) is coated with the hard coat liquid 1 without alkali treatment, and then cured under the same conditions as in Example 1 to form a 3 μm-thick hard coat film (refractive index: 1.53) Was formed. Next, the refractive index adjusting liquid 1 is applied on the hard coat film, and then cured under the same conditions as in Example 1 to form a refractive index adjusting layer having a thickness of 110 nm and a refractive index of 1.72. Formed. The low-refractive-index coating liquid 8 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. The adhesion of the obtained laminated film was evaluated. There was no peeling of the coating even at 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, as shown in Table 3, no scratch was found, the visible light transmittance was 94%, and the haze value was 0.1%. When the visible light reflectance was measured, it was 5%, which was smaller than the visible light reflectance of 9% similarly measured for the sample of Example 1, indicating excellent antireflection performance.
[0077]
Example 13
Except that the coating liquid for low refractive index 9 (water-repellent thermosetting hard coating liquid, refractive index after curing 1.41) was used instead of the coating liquid for low refractive index 8 used in Example 12, A hard coat film, a refractive index adjusting layer and a low refractive index layer film were formed on the TAC film in the same manner as in Example 12.
[0078]
Example 14
A hard coat film and a refractive index adjustment were performed on a TAC film in the same manner as in Example 12 except that the hard coat liquid 2 (hard coat liquid having antiglare properties) was used instead of the hard coat liquid 1 used in Example 12. A layer and a low refractive index layer coating were formed.
[0079]
The coatings obtained in Examples 13 and 14 were evaluated in the same manner as in Example 12 for the adhesion, scratching property and optical properties. Examples 13 and 14 both had a visible light reflectance of 5% and exhibited excellent antireflection performance. Other results were as shown in Table 3. Further, the stain resistance test and the surface water droplet contact angle of Example 13 were measured and found to be "no stain remaining" and 103 degrees, respectively, indicating excellent stain resistance. Example 14 also showed excellent antiglare properties.
[0080]
Comparative Example 8
A hard coat film, a refractive index adjusting layer and a low refractive index layer film were formed on the same TAC film as in Example 14 except that the hard coat liquid 5 was used instead of the hard coat liquid 1 of Example 12.
The adhesion of the obtained coating was evaluated. Initially, there was no peeling of the coating, and there was peeling at a very small portion (peeling between the refractive index adjusting layer and the low refractive index layer) after the moisture resistance test. The scratching property and the optical properties were evaluated in the same manner as in Example 1. As a result, a slight scratch was found, the visible light transmittance was 94%, and the haze value was 0.1%.
[0081]
Example 15
Instead of forming the low-refractive-index layer using the low-refractive-index coating liquid 8 in Example 12, SiO₂A hard coat film, a refractive index adjusting layer and a low refractive index layer film were formed on the same TAC film as in Example 12 except that the low refractive index inorganic layer was formed. There was no peeling of the coating even at the initial stage and after the moisture resistance test, and there was no problem in the adhesion. There were no scratches on the scratching property, and the visible light transmittance and haze of the optical properties were as shown in Table 3. In addition, the visible light reflectance was 5%.
[0082]
Comparative Example 9
A hard coat film, a refractive index adjusting layer and a low refractive index layer film were formed on the same TAC film as in Example 15 except that the hard coat liquid 5 was used instead of the hard coat liquid 1 of Example 12. Initially, the coating was partially peeled, and largely peeled after the moisture resistance test. Peeling occurred between the low refractive index layer and the refraction adjusting layer. The scratching property was slightly scratched, and the optical characteristics were as shown in Table 3.
[0083]
Example 16
Except that the refractive index adjusting layer formed in Example 13 was not formed, the coating liquid 9 for low refractive index was directly applied on the hard coat film and cured by heating. A low refractive index layer coating was formed. There was no peeling of the coating even at the initial stage and after the moisture resistance test, and there was no problem in the adhesion. Also, it had a visible light reflectance of 6% and exhibited excellent antireflection performance. The surface water contact angle was 103 degrees. There were no scratches on the scratching property, and the visible light transmittance and haze of the optical properties were as shown in Table 3.
[0084]
Example 17
The TAC film was coated with the hard coat liquid 7 as an underlying hard coat layer without alkali treatment, and then cured under the same conditions as in Example 1 to form a 4 μm thick underlying hard coat layer. A hard coat layer 6 having a thickness of 0.15 μm was formed by applying a hard coat liquid 6 on the base hard coat layer by a spinner method, and thereafter similarly performing photo-curing. Table 1 shows the performance of the obtained products. Since the particle size of the fine particles (D) used was smaller than those of Examples 2 and 4, it was observed that the light diffusion state was uniform and uniform anti-glare properties were obtained.
[0085]
Example 18
TiO was further added on the hard coat layer formed in Example 17.₂And SiO₂A base hard coat layer, a hard coat layer, and a two-layer antireflection coating were formed on the TAC film in the same manner as in Example 17 except that the inorganic film layer was formed. The performance of the obtained product was as shown in Table 3, and showed excellent antiglare properties. The visible light reflectance was 5%, indicating excellent antireflection performance.
[0086]
The above Examples and Comparative Examples are summarized in Tables 1 to 3, respectively. As is clear from the results in the table, in the examples of the present invention, the adhesion to the TAC film (adhesion) was very good, the scratch resistance (scratch resistance) was good, and the transparency was high. A good hard coat film was formed.
[0087]
In addition, a hard coat-coated TAC film having high adhesion durability can be obtained without performing surface treatment of the TAC film. It is considered that the reason is that the amino group interacts with the functional group in the TAC when the hard coat layer contains an aminoorganofunctional silane as a constituent material.
[0088]
In addition, anti-glare properties, water repellency, and stains can be obtained by adding surface irregularities by adding fine particles made of a metal or an inorganic compound, reducing the free energy of the coating film surface by introducing a fluoroalkylsilane, and coating a single-layer or multilayer inorganic or organic film. Various properties, such as difficulty, easy dirt removal, high moisture permeability, antireflection performance, and transparent conductivity, can be imparted to the surface of the TAC film.
[0089]
[Table 1]

[0090]
[Table 2]

[0091]
[Table 3]

[0092]
【The invention's effect】
According to the present invention, a hard coat film having very good adhesion to a TAC resin and excellent scratch resistance can be formed on a substrate surface, and thus can be used in, for example, an environment where the surface is easily damaged, such as outdoors. Also increase the availability. Further, a hard coat film having high antiglare property and antifouling property was obtained.
[0093]
Further, since the coating layer of the present invention does not absorb visible light, the TAC surface is not affected by the coating, and the visible light transmittance is high.

Claims (12)

A hard coat solution containing (A) a polyfunctional acrylate, (B) aminosilane and (C) colloidal silica is applied to the surface of a triacetyl cellulose resin substrate, and then cured to form a hard coat layer. A method for producing a hard coat-coated acetylcellulose resin article. The aminosilane (B) is represented by the following formula (1)
X _a Si (R ¹ (NHR ² ) _b NR ³ H) _4-a (1)
Here, X is an alkoxyl group having 1 to 6 carbon atoms, R ¹ and R ² are the same or different divalent hydrocarbon groups, and R ³ 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 according to claim 1, wherein: The method according to claim 1, wherein the hard coat liquid further contains fine particles having an average particle diameter of 0.05 to 10 μm and / or fluoroalkylsilane. The fluoroalkylsilane is represented by the following formula (2)
^{_{R 4 c R 5 d Si (}} OR 6) 4-c-d (2)
Here, R ⁴ is a fluorine alkyl group having 1 to 12 carbon atoms, R ⁵ 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 ⁶ is a hydrogen atom or an alkyl group or an 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.
4. The method according to claim 3, wherein The method according to any one of claims 1 to 4, wherein the hard coat liquid further contains at least one of a polymerization initiator, a hydrolysis catalyst, and a physical property modifier. The production method according to claim 5, wherein the physical property modifier comprises one or more of epoxy (meth) acrylate, urethane (meth) acrylate, and polyester (meth) acrylate. The method according to any one of claims 1 to 6, 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 is 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 an oxide of the metal. The manufacturing method according to claim 7, wherein at least one inorganic compound selected from a metal nitride is formed by a vacuum deposition method, a plasma CVD method, a sputtering method, or an ion plating method. The method according to claim 7, wherein the inorganic film layer is a single-layer or multilayer anti-reflection layer. The method according to any one of claims 1 to 6, wherein a single layer or a multilayer antireflection organic layer is formed on the hard coat layer. Between the hard coat layer and the antireflection layer,
(J) polyfunctional acrylate,
(K) The following equation (3)
R ⁹ _n SiZ _4-n (3)
Here, R ⁹ is an organic functional group having a functional group selected from a methacryloxy group, an acryloxy group, a vinyl group, an allyl group, and an amino group, and Z is one or more of an alkoxyl group, an acetoxyl group, and chlorine. A hydrolysable group, n is 1, 2 or 3;
The production method according to claim 9, wherein a liquid containing the silane compound represented by the formula (1) and (L) fine particles for adjusting a refractive index is applied, and then a refractive index adjusting layer formed by curing is provided. A hard coat-coated acetylcellulose resin article manufactured by the manufacturing method according to claim 1.