200916819 九、發明說明 【發明所屬之技術領域】 本發明係關於具備防反射層之防反射薄膜及使用其之 顯示器用前面板。 【先前技術】 近年來，液晶顯示器或電漿顯示器（plasma display panel，PDP )等所代表之高精細且大螢幕顯示器之開發急 速發展。對於顯示器之顯示面，爲提高該視認性，爲防止 螢光燈等之外來光線映照於螢幕，必須配置具有防反射機 能之防反射層於表面。 作爲防反射層之形成方法，已知於顯示器表面，蒸著 或濺鍍無機金屬之所謂的乾式塗佈法，及塗佈溶液或分散 液等液狀之低折射率材料等於基材，使乾燥，因應需要使 硬化’製造具有防反射機能之薄膜等之濕式塗佈法等。隨 著近年來顯示器之大型化，以連續運轉（roll-to-roll)價 廉且容易對應大型化之濕式塗佈法逐漸成爲主流。亦即， 使用液晶顯示器或電漿顯示器（PDP )等所代表之高精細 且大螢幕顯示器之電視機等之價格亦於國際上競爭激烈者 ，以無機金屬之蒸著或濺鍍，生產性亦差，並且成本高。 雖然價廉且容易對應大型化之濕式塗佈法逐漸成爲主流， 但以濕式塗佈製造之防反射薄膜，經常被要求更進一步降 低成本。因此，於濕式塗佈法中，製造使具備相同機能之 光學薄膜’例如防反射薄膜等時，可製造可減少製造步騾 -4- 200916819 之防反射薄膜，具體上，更少的形成層或加工步驟，而且 具備必要的機能、品質之防反射薄膜，有效地減低成本。 以濕式塗佈法所製作之防反射層係於透明基材薄膜上 ，以膜厚各約100nm左右的提高基材本身硬度用之硬塗佈 層、及於其上之單層或多層之折射率相異層所形成之防反 射薄膜（專利文獻1 )。 另外，作爲透明基材薄膜，經常使用聚酯樹脂薄膜， 尤其聚對苯二甲酸乙二醇酯（PET )之二軸延伸薄膜。二 軸延伸PET薄膜係具有透明性，因具有優異的機械性質、 耐熱性或耐藥品性等，所以作爲上述防反射薄膜之基材薄 膜，必要的延伸明顯。 但是，如此聚酯基材一般係難以良好地保持與防反射 層之密合性，例如使用二軸延伸PET薄膜作爲透明基材時 ，爲提高PET薄膜與防反射層之密合性，幾乎都是於PET 薄膜之表面，設置亦稱爲易黏著層之賦予易黏著性用之底 漆層（亦稱爲增黏塗（anchor coat )層。以下賦予易黏著 性用之底漆層，除非例外，簡稱爲「底漆層」）。亦即， 以濕式塗佈法於PET薄膜上形成防反射層時，於現實生產 係如後述專利文獻 2 之[0032]或專利文獻 3 之 [0077]〜[0079]、專利文獻4之[0024]、專利文獻5之 [0004]、專利文獻6之[0003]等所記載，現階段係於PET 薄膜之至少形成防反射層之主面側，形成作爲易黏著層之 底漆層，或使用其所形成之PET薄膜者。 然而，基材上所設置之各層的膜厚及折射率之關係係 -5- 200916819 非常重要的防反射層中，底漆層亦對防反射性能的影響大 ，必須考慮基材、底漆層、防反射層3種之折射率及膜厚 而設計（專利文獻2~專利文獻4 )。 但是，此光學設計困難，難以抑制干涉斑發生。另外 ，除了硬塗佈層、低折射率層以外，亦設置底漆層，增加 製造步驟，變得難以對應市場低成本的要求。 作爲設置底漆層以外之方法，雖亦提出於聚酯基材施 以電暈處理、電漿處理等之易黏著化表面前處理（所謂「 易黏著化表面前處理」，並非另外形成底漆層等之新層， 而係藉由將基材表面改質以改良黏著性之處理），僅電暈 處理、電漿處理係難以表現充份的密合性（專利文獻5 ) 〇 另一方面’揭示使用特定的樹脂於硬塗佈層，不設置 底漆層’提高與聚酯樹脂基材之密合性（專利文獻6 )。 然而’以此方法，基材與硬塗佈層之黏著性稱不上充份。 [專利文獻1]特開2002-200690號公報 [專利文獻2]特開2003-177209號公報 [專利文獻3]特開2004-345333號公報 [專利文獻4]特開2006_258897號公報 [專利文獻5]特開2006_235125號公報 [專利文獻6]特開2 005_ 1 96065號公報 【發明內容】 發明之揭示 -6- 200916819 發明所欲解決之課題 因此’本發明係提供即使使用不具有底漆層之聚酯基 材於形成防反射層之主面側上時，仍可確保聚酯基材與防 反射層之黏著性’而且防止干涉斑發生之具有優異的防反 射性能之防反射薄膜’以及使用上述防反射薄膜之顯示器 用前面板爲目的。 課題之解決手段 (1)爲解決上述課題之本發明之防反射薄膜係含有 聚酯基材、及於該聚酯基材之單方主面側，以濕式塗佈法 所配置之防反射層之防反射薄膜， 上述防反射層係由上述聚酯基材側含有硬塗佈層及比 該硬塗佈層更上側所配置之低折射率層， 上述硬塗佈層係直接設置於上述聚酯基材上， 上述硬塗佈層係含金屬氧化物，該金屬氧化物之比率 爲20體積％〜42體積％爲特徵。 (2 )上述（1 )項記載之防反射薄膜，其中配置上述 防反射層側之上述聚酯基材主面係以未進行易黏著化表面 前處理之聚酯基材爲宜。 (3 )上述（1 )或（2 )項記載之防反射薄膜，其中 上述防反射層係以基於JIS K5 600-5 -6進行棋盤狀方格剝 離試驗中，認爲不自上述聚酯基材剝離之防反射薄膜爲宜 (4 )上述（1 )〜（3 )項中任一項記載之防反射薄膜 200916819 ’其中上述防反射薄膜於38〇nm〜780nm之反射率振幅差 之最大値係以1 · 〇 %以下爲宜。 (5) 上述（〗）〜（4)項中任一項記載之防反射薄膜 ，其中以於上述聚酯基材之另一方之主面側，配置近紅外 線吸收層爲宜。 (6) 另外，本發明之顯示器用前面板係於基板上， 配置上述（1)〜（5)項中任一項記載之防反射薄膜爲特 徵。 發明之功效 (1 )依據本發明，可提供可確保聚酯基材及防反射 層之密合性，進而可防止干涉斑，防反射性性能優異之防 反射薄膜，而且，因爲上述硬塗佈層係直接設置於上述聚 酯基材上，不介由易黏著化用之底漆層，無須形成底漆層 ，所以可提供價廉之防反射薄膜。而且，即使無上述底漆 層，仍可確保聚酯基材及防反射層之密合性。 (2)另外，依據上述（1)項記載之防反射薄膜中， 配置上述防反射層側之上述聚酯基材主面係未進行易黏著 化表面前處理之聚酯基材之本發明之適合型態，因爲即使 未進行易黏著化表面前處理，仍可確保聚酯基材及防反射 層之密合性，所以可省略易黏著化表面前處理，因此可提 供價廉之防反射薄膜。（另外，有關申請專利範圍第1項 之本發明中，並不排除使用經施以易黏著化表面前處理之 聚酯基材。） -8- 200916819 (3 )另外，依據於上述（1 )或（2 )項記載之防反 射薄膜中，上述防反射層係基於JIS K5600-5-6進行棋盤 狀方格剝離試驗中，認爲不自上述聚酯基材剝離之本發明 之適合型態，可提供不發生防反射層之剝離，品質信賴性 優異之防反射薄膜。 (4 )另外，依據於上述（丨）〜（3 )項中任一項記載 之防反射薄膜中，上述防反射薄膜於3 80nm~78〇nin之反 射率振幅差之最大値爲1 .〇%以下之本發明之適合型態， 可提供干涉斑發生少之防反射薄膜。 (5 )另外，依據於上述（1 )〜（4 )項中任一項記載 之防反射薄膜中，上述聚酯基材之另一方之主面側，配置 近紅外線吸收層之本發明之適合型態，藉由將此配置近紅 外線吸收層之防反射薄膜，設置於作爲以大型電視機爲首 之各種電子機器顯示板所使用之電漿顯示器（PDP )之前 面，可提供可更加發揮於此等電子機器使用中，作爲遮蔽 自PDP前面發生不要的近紅外線之過濾器之機能，適合防 止因該近紅外線外洩而發生周圍電子機器，例如電視機或 冷氣機等之錯誤動作之問題，且具有防反射機能之防反射 薄膜。 (6)另外，因爲本發明之顯示器用前面板係於基板 上，配置上述（】）〜（5 )項中任一項記載之防反射薄膜 ，所以可提供成本更便宜之顯示器用前面板，而且，關於 防反射薄膜層，可提供發揮對應上述（1 )〜（5 )項各項 之機能之顯示器用前面板。 -9- 200916819 用以實施發明之最佳型態 本發明之防反射薄膜中使用之聚酯基材係以 圍之透光率爲8 0 %以上爲宜，以8 8 %以上尤佳。 度係以2.0%以下爲宜，以1.0%以下尤佳。作爲 ，作爲代表例，雖可舉例如聚對苯二甲酸乙二醇 烯-2,6-萘二羧酸酯等，尤其，就雖價廉，但具有 兼具優異的機械性質、耐熱性（難燃性質）以及 等上，以聚對苯二甲酸乙二醇酯（PET )之二軸 爲宜。上述基材的厚度通常爲1〇〜500μηι程度。 成上述聚酯基材之樹脂中，亦可添加抗氧化劑、 抗耐熱劑、紫外線吸收劑、易滑劑等之添加劑。 形成上述硬塗佈層用之塗料，可組合、調整 之電離放射線硬化型樹脂、導電性及/或非導電 化物微粒子、光開始劑、溶劑等，亦可使用已經 所調合之墨水化者。使用下述成份，調整硬塗佈 可依塗佈液之一般的調整方法分散處理。 硬塗佈層之折射率係必須考慮與基材之折射 而設計。例如聚酯基材之PET基材之折射率約赁 右。上方所設置之硬塗佈層之折射率對此之差異 爲干涉斑的發生原因。通常硬塗佈層與基材薄膜 差爲土0.03以上時發生干涉斑。因此，上述硬塗 射率係以1.60〜1.7〇爲宜。加入折射率大的金屬 硬塗佈層之折射率變得接近於基材薄膜。金屬氧 可見光範 另外，曇 聚酯基材 酯或聚乙 透明性， 耐藥品性 延伸薄膜 另外，構 難燃劑、 如下所舉 性金屬氧 混合此等 層塗料， 率的關係 ".66 左 大時，成 之折射率 佈層之折 氧化物， 化物係可 -10- 200916819 使用1種，亦可2種以上。 另外’本發明之防反射薄膜中，藉由上述防反射薄膜 於3 8 0nm〜780nm之反射率振幅差之最大値爲1.0%以下， 可提供干涉斑發生少之防反射薄膜。因此，如上所述，聚 酯基材之折射率與其上所配置之硬塗佈層之折射率的差小 於±0.03爲宜，因爲不能簡單地改變聚酯基材之折射率， 所以通常藉由選擇、組合構成硬塗佈層之材料，亦即電離 放射線硬化型樹脂、金屬氧化物微粒子，調整硬塗佈層之 材料，可使所得之防反射薄膜於3 80nm〜78 0nm之反射率 振幅差之最大値爲1.0 %以下。 使用導電性金屬氧化物於硬塗佈層使用之金屬氧化物 ’可同時給予防反射薄膜防靜電性能。僅以1種導電性金 屬氧化物形成規定的折射率，硬塗佈層中之金屬氧化物之 含量可能變多。因此，此時爲2種以上之金屬氧化物時， 可提高折射率而金屬氧化物之含量不會過多。 另外，硬塗佈層係使用含電離放射線硬化型樹脂之樹 脂所形成。藉由可合理的形成硬塗佈層。 作爲上述硬塗佈層所含之金屬氧化物，可使用例如銻 摻雜錫氧化物（ΑΤΟ )、銦摻雜錫氧化物（ΙΤΟ )、磷摻 雜錫氧化物（phosphorus-doped tin oxide，ΡΤΟ)、氧化 鋅（ZnO )、氧化錫（Sn〇2 )、氧化鉻（Zr02 )、銻酸鋅 C ZnSb2〇6 )等。此金屬氧化物係適合使用微粒子狀物， 該平均粒徑係以l〇〇nm以下爲宜，以50nm以下尤佳，以 20nm以下更好。因爲若於此範圍內時，提升電離放射線 -11 - 200916819 硬化型樹脂中之分散性，塗膜形成時之曇度變小。金屬氧 化物之平均粒徑之下限雖無特別限制，但就導電性表現或 高折射率表現之觀點，以2 . Onm以上爲宜。 另外，此等金屬氧化物粒子之平均粒徑之測定係將含 有金屬氧化物粒子之防反射薄膜，以切片機（microtome )切片，拍攝所切片之薄膜斷面片之20萬倍之TEM (穿 透式電子顯微鏡）照片，以300個粒子之平均値作爲平均 粒徑。所拍攝的粒子若非圓形而有長徑及短徑時，測定每 1個粒子之長徑及短徑，算出此等之平均。測定、算出 3 0 0個粒子之此平均値，作爲平均粒徑。 接著，本發明中重要的係金屬氧化物相對於硬塗佈層 之含有比率爲20體積％〜42體積％，以25〜35體積％爲宜 。藉由使硬塗佈層中金屬氧化物之含有比率於上述範圍， 於聚酯基材之設置硬塗佈層側之主面，不形成底漆層，可 使硬塗佈層對聚酯基材主面之黏著性爲可實用之堅固者， 可形成作爲塗膜之強度亦高者。若金屬氧化物相對於硬塗 佈層之比率過小時，推測此時之體積收縮大，容易自聚酯 基材剝離，另一方面，若金屬氧化物相對於硬塗佈層之比 率過大時，不僅作爲塗膜之強度降低，過多時甚至連形成 塗膜變得困難，所以藉由於上述範圍，可不形成底漆層， 使硬塗佈層對聚酯基材主面之黏著性爲可實用之堅固者， 另外，因爲不設置底漆層於聚酯基材之設置硬塗佈層側之 主面，所以可以防止干涉斑的發生，可提供防反射性性能 優異之防反射薄膜。 -12- 200916819 另外’所謂上述金屬氧化物之比率係指金屬氧化物之 體積相對於硬塗佈層所含之金屬氧化物與樹脂固形物之體 積總和。體積比係金屬氧化物與樹脂固形物之重量比、及 由各材料之比重文獻値計算所求出。 作爲形成上述硬塗佈層之電離放射線硬化型樹脂，可 使用具有乙烯基、（甲基）丙烯醯基、環氧基、氧雜環丁 基之單體'此等之預聚物、聚合物。此等係可單獨，亦可 組合2種以上使用。就同時符合生產性及硬度之觀點，以 使用多官能單體或寡聚物爲宜。作爲多官能單體或寡聚物 係適合使用具有2個以上的不飽和基之多官能丙稀基系單 體或其寡聚物。另外，若於單體或寡聚物分子中具有許多 如形成氨鍵之鍵結基或官能基時，提升與聚醋基材之密合 性。另外’藉由使用雙酚A變性（甲基）丙烯酸酯等之高 折射率之單體或寡聚物，可提高硬塗佈層之折射率。 作爲多官能丙烯基系單體或寡聚物，可舉例如乙二醇 一（甲基）丙嫌酸醋、一乙一醇二（甲基）丙嫌酸酯、三 乙二醇二（甲基）丙烯酸酯、1,4-環己烷二丙烯酸酯、季 戊四醇四（甲基）丙烯酸酯、季戊四醇三（甲基）丙稀酸 酯、三甲醇丙烷三（甲基）丙烯酸酯、三甲醇乙垸三（甲 基）丙烯酸酯、二季戊四醇四（甲基）丙烯酸酯、二季戊 四醇五（甲基）丙烯酸酯、二季戊四醇六（甲基）丙烯酸 酯、1，2,3-環己烷三甲基丙烯酸酯、聚胺基甲酸乙酯聚丙 烯酸酯、聚酯聚丙烯酸酯等之由多元醇及（甲基）丙嫌酸 所產生的酯類、：M-二乙烯基苯、4-乙烯基苯甲酸-2-丙嫌 -13- 200916819 醯基乙基酯、1，4 -二乙烯基己烷等之乙烯基苯及其 等。此等雖可單獨使用，但亦可組合2種以上使用 就可更提高耐擦傷性之觀點，以至少1種選自季戊 甲基丙烯酸酯及二季戊四醇六甲基丙烯酸酯爲宜。 膜強度之觀點，以季戊四醇四（甲基）丙烯酸酯、 醇三（甲基）丙烯酸酯、三甲醇丙烷三（甲基）丙 、三甲醇乙烷三（甲基）丙烯酸酯、二季戊四醇四 )丙烯酸酯、二季戊四醇五（甲基）丙烯酸酯、及 四醇六（甲基）丙烯酸酯爲宜。在此”…（甲基） 酯…”係指”…丙烯酸酯···”及/或”…甲基丙烯酸酯· 使上述硬塗佈層中所含之電離放射線硬化型樹 時，進行紫外線照射時，添加光聚合開始劑於硬塗 塗佈液。作爲光聚合開始劑，可使用乙醯苯類、二 類、縮酮類、蒽醌類、噻噸酮類、偶氮化合物、過 、2,3-二烷基二酮化合物類、二硫化物類、二烴胺 合物類、氟胺化合物等。此等係可單獨，亦可組合 上使用。光聚合物開始劑之使用量通常相對於電離 硬化型樹脂質量，以質量％程度爲宜。 亦可添加作爲上述硬塗佈層組成物之其他成份 合抑制劑、抗氧化劑、分散劑、界面活性劑、光安 塡平劑等之添加劑。另外，只要使濕式塗佈法成膜 ，可添加任意量之溶劑。 關於聚酯基材上形成硬塗佈層之方法，並無特 ，可塗佈含上述材料之塗佈液於聚酯基材上而形成 衍生物 。其中 四醇三 就提高 季戊四 烯酸酯 (甲基 二季戊 丙烯酸 脂硬化 佈層之 苯甲酮 氧化物 荒醯化 2種以 放射線 ，如聚 定劑及 後乾燥 別限制 。塗佈 -14- 200916819 方法亦無特別限制’例如可使用滾輪塗佈、塑模塗佈（ die coat)、風刀塗佈（air knife coat)、刮刀塗佈（ blade coat )、旋轉塗佈（spin coat )、反向塗佈（ reverse coat)、凹版塗佈（gravure coat)等之塗佈法、 或凹版印刷、網版印刷（screen printing )、平版印刷（ 〇 f f s e t p r i n t i n g )、噴墨印刷等之印刷法等。 上述硬塗佈層之表面硬度係依JIS K5600規定之鉛筆 硬度試驗評估，以Η以上爲宜，以2H以上尤佳。 另外，硬塗佈層之厚度係以 〇.3~3·Ομιη爲宜，以 0.3〜2.0μιη尤佳，以0.3〜1·5μιη更好。 硬塗佈層之厚度未滿〇.3μιη時，有難以維持硬度之趨 勢。另外，硬塗佈層之厚度若超過3.Ομιη時，有發生斷裂 、捲曲（薄膜反翹）、防反射薄膜之全透光率降低之趨勢 ，並且，電離放射線硬化型樹脂的體積收縮變大，有硬塗 佈層容易自聚酯基材剝離之趨勢。因此，硬塗佈層之厚度 係以於上述範圍爲宜。 上述硬塗佈層上所配置之低折射率層若設定接近於折 射率與膜厚之乘積之光學膜厚度爲λ/4 (λ:人類可見光的 波長。尤其多設定於人類眼睛視感度高之光波長5 50nm ) 時，反射率變得更低尤佳。另外，低折射率層之折射率與 硬塗佈層之折射率差愈大，防反射性升高。另外，使低折 射率層設置於本實施型態之抗反射薄膜之最表面時（亦即 ’低折射率層上未再設置其他機能性層），具有強度及防 污性爲宜，就此等觀點係以含有含全氟基或聚二甲基矽氧 -15- 200916819 烷部位之樹脂爲宜。 形成上述低折射率層用之塗料係可組合、調整如下所 舉之膠黏劑樹脂形成用材料、低折射率微粒子、光開始劑 、溶劑寺’亦可使用已經混合此等所調合之墨水化者。可 使用下述成份調整低折射塗料係可依據塗佈液一般調整方 法分散處理。 作爲形成上述低折射率層之材料，可使用一般所使用 之形成低折射率層之已知材料。例如可使用含具有空隙之 二氧化砂或氟化鎂等之低折射率無機微粒子與膠黏劑樹脂 形成用材料之塗佈液、或含氟系樹脂等之塗佈液。 作爲形成上述低折射率層之膠黏劑樹脂形成用材料， 可使用具有乙烯基、（甲基）丙烯醯基、環氧基、環丁基 之單體、此等之預聚物、聚合物之電離放射線硬化型樹脂 。在此”（甲基）丙烯醯基”係表示”丙烯醯基”及/或”甲 基丙烯醯基”。另外，使用熱硬化型膠黏劑時，亦可使用 無機膠黏劑。作爲無機膠黏劑，可舉例如二氧化矽溶膠等 。作爲二氧化矽溶膠’可舉例如矽醇鹽與酸觸媒或鹼觸媒 爲開始原料之二氧化矽溶膠。作爲矽醇鹽，可舉例如四甲 氧基矽烷或四乙氧基矽烷等。 使上述低折射率層所含之電離放射線硬化型樹脂硬化 時，進行紫外線照射時，添加光聚合開始劑於低折射率層 之塗佈液。作爲光聚合開始劑，可使用乙醯苯類、二苯甲 酮類、縮酮類、蒽醌類、噻噸酮類、偶氮化合物、過氧化 物、2,3-二烷基二酮化合物類、二硫化物類、二烴胺荒醯 -16- 200916819 化合物類、氟胺化合物等。此等係可單獨，亦可組合2種 以上使用。光聚合物開始劑之使用量通常相對於電離放射 線硬化型樹脂質量，以1〜1 5質量％程度爲宜。 亦可添加作爲上述低折射率層組成物之其他成份，如 聚合抑制劑、抗氧化劑、分散劑、界面活性劑、光安定劑 及塡平劑等之添加劑。另外，只要使濕式塗佈法成膜後乾 燥，可添加任意量之溶劑。 關於硬塗佈層上形成低折射率層之方法，並無特別限 制，可與上述硬塗佈層同樣地塗佈含上述材料之塗佈液於 硬塗佈層上而形成。 另外，本發明之防反射薄膜中，可於上述聚酯基材之 另一方之主面側，再配置近紅外線吸收層。藉此，若配置 本實施型態之防反射薄膜於PDP表面時，遮斷發生電漿放 電時所放出之不要的近紅外線，不對使用周邊的電子零件 的機器造成不良影響，尤其可解除使電視或冷氣機等之遙 控器之錯誤動作之問題。 上述近紅外線吸收層之材料係吸收近紅外線之具有透 光性之材料即可，並無特別的限制，通常係使用使吸收近 紅外線之化合物分散之樹脂。 上述吸收近紅外線之化合物係以於8 5 0~ 1 1 0 0 nm之波 長範圍具有最大吸收波長之化合物爲宜。近紅外線吸收層 右a上述化合物時’ ^、會大幅減低於波長400~850nm之可 見光的穿透率，可減低於波長850〜llOOnm之近紅外線穿 透率。藉此’可適合使用本實施型態之防反射薄膜作爲 -17- 200916819 PDP等之近紅外線吸收薄膜。 作爲於850~1100nm之波長範圍具有最大吸收波長之 化合物’可使用例如胺鎗系、偶氮系、fly曝系、意驅系、 旋藍系、螺嗓系、喹駄酮系、Squalium系、二苯乙嫌系、 二苯基甲垸系、萘醌系、diimonium系、酞菁系、花青苷 系、聚甲炔（polymethine)系等之有機色素。 作爲使吸收近紅外線之化合物分散之樹脂，可使用聚 酯樹脂、丙烯酸樹脂、聚胺基甲酸乙酯樹脂、聚氯化乙烯 樹脂、環氧樹脂、聚乙酸乙烯樹脂、聚苯乙烯樹脂、纖維 素樹脂、聚丁縮醛樹脂等，並且，亦可組合2種以上之此 等樹脂作爲聚合物共混物（Polymer blend)使用。 關於形成近紅外線吸收層於聚酯基材上之方法，並無 特別限制，可藉由與上述硬塗佈層時同樣地塗佈含上述材 料之塗佈液於基材而形成。近紅外線吸收層之厚度係以 1〜ΙΟμπι爲宜，以2〜7μιη尤佳。厚度未滿Ιμιη時，有難以 吸收近紅外線之趨勢，超過1〇μιη時，因有發生斷裂、發 生捲曲（薄膜反翹）之趨勢，所以近紅外線吸收層之厚度 係以於上述範圍爲宜。 於近紅外線吸收層，亦可適當添加遮斷PDP之氖明線 光譜（橘色）之化合物。藉此可使於PDP發色更鮮豔的紅 色。作爲遮斷氖明線光譜之化合物，可使用於5 8 0〜620 nm 之波長範圍具有最大吸收波長之有機色素’可使用例如花 青苷系、azulenium系、squalium系、一苯基甲院系、二 苯基甲烷系、噁嗪系、吖嗪系、thiopyrium系、紫蘿驗（ -18- 200916819[Technical Field] The present invention relates to an antireflection film having an antireflection layer and a front panel for display using the same. [Prior Art] In recent years, the development of high-definition and large-screen displays represented by liquid crystal displays or plasma display panels (PDPs) has been rapidly developed. In order to improve the visibility of the display surface of the display, in order to prevent the light from being reflected on the screen, such as a fluorescent lamp, an anti-reflection layer having an anti-reflection function must be disposed on the surface. As a method of forming the antireflection layer, a so-called dry coating method in which an inorganic metal is vaporized or sputtered on a surface of a display, and a liquid low refractive index material such as a coating solution or a dispersion are equal to a substrate to be dried. In the case of hardening, a wet coating method or the like for producing a film having an antireflection function or the like is required. With the recent increase in the size of displays, wet-coating methods that are inexpensive to roll-to-roll and are easy to cope with large-scale are becoming mainstream. That is, the price of a high-definition and large-screen display such as a liquid crystal display or a plasma display (PDP) is also highly competitive internationally, with steaming or sputtering of inorganic metals, and productivity. Poor and costly. Although the wet coating method which is inexpensive and easy to cope with large-scale is gradually becoming the mainstream, the anti-reflection film manufactured by wet coating is often required to further reduce the cost. Therefore, in the wet coating method, when an optical film having the same function, such as an antireflection film or the like, is produced, an antireflection film capable of reducing the manufacturing step -4-200916819 can be manufactured, and specifically, a smaller layer is formed. Or the processing steps, and the anti-reflection film with the necessary function and quality, effectively reducing the cost. The antireflection layer produced by the wet coating method is applied to a transparent substrate film, and has a hard coating layer for improving the hardness of the substrate itself, and a single layer or a plurality of layers thereon, each having a thickness of about 100 nm. An antireflection film formed of a refractive index dissimilar layer (Patent Document 1). Further, as the transparent base film, a polyester resin film, in particular, a biaxially stretched film of polyethylene terephthalate (PET) is often used. The biaxially stretched PET film has transparency, and since it has excellent mechanical properties, heat resistance, chemical resistance, and the like, it is necessary to extend the base film of the antireflection film as necessary. However, in such a polyester substrate, it is generally difficult to maintain good adhesion to the antireflection layer. For example, when a biaxially stretched PET film is used as a transparent substrate, almost all of the adhesion between the PET film and the antireflection layer is improved. On the surface of the PET film, a primer layer (also known as an anchor coat layer) which is also called an easy-adhesion layer for imparting adhesion is provided. The primer layer for adhesion is given below, unless exception , referred to as "primer layer"). In other words, when the antireflection layer is formed on the PET film by the wet coating method, the actual production system is [0032] of the following Patent Document 2 or [0077] to [0079] of Patent Document 3, and [Patent Document 4] 0024], [0004] of Patent Document 5, [0003] of Patent Document 6, etc., at the present stage, at least the main surface side of the PET film formed with the antireflection layer, forming a primer layer as an easy adhesion layer, or The PET film formed by it is used. However, the relationship between the film thickness and the refractive index of each layer provided on the substrate is a very important antireflection layer in the anti-reflection layer. The primer layer also has a great influence on the antireflection performance, and the substrate and the primer layer must be considered. The antireflection layer has three types of refractive index and film thickness (Patent Document 2 to Patent Document 4). However, this optical design is difficult and it is difficult to suppress the occurrence of interference spots. Further, in addition to the hard coat layer and the low refractive index layer, a primer layer is also provided, which increases the number of manufacturing steps and makes it difficult to meet the requirements of low cost in the market. As a method other than the provision of the primer layer, it is also proposed to apply an easy adhesion surface pretreatment to a polyester substrate by corona treatment, plasma treatment, etc. (so-called "adhesive surface pretreatment", and no primer is additionally formed. A new layer such as a layer is treated by modifying the surface of the substrate to improve adhesion. Only corona treatment or plasma treatment is difficult to express sufficient adhesion (Patent Document 5). 'Exposing the use of a specific resin in a hard coat layer without providing a primer layer' improves adhesion to a polyester resin substrate (Patent Document 6). However, in this way, the adhesion of the substrate to the hard coat layer is not sufficient. [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. No. Hei. JP-A-2006-235125 [Patent Document 6] JP-A-2002-13596 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION OBJECTS TO BE SOLVED BY THE INVENTION Therefore, the present invention provides that even if a primer layer is not used, When the polyester substrate is formed on the main surface side of the antireflection layer, the adhesion between the polyester substrate and the antireflection layer can be ensured, and the antireflection film having excellent antireflection properties that prevents interference spots from occurring and use The display of the above antireflection film is intended for the front panel. Solution to Problem (1) An antireflection film of the present invention which solves the above-described problems includes a polyester base material and an antireflection layer which is disposed on a single main surface side of the polyester base material by a wet coating method. In the antireflection film, the antireflection layer is provided with a hard coating layer on the side of the polyester substrate and a low refractive index layer disposed above the hard coating layer, and the hard coating layer is directly provided on the poly layer. In the ester substrate, the hard coat layer contains a metal oxide, and the ratio of the metal oxide is 20% by volume to 42% by volume. (2) The antireflection film according to the above aspect (1), wherein the polyester base material on the side of the antireflection layer is preferably a polyester substrate which is not subjected to an easy adhesion surface pretreatment. (3) The antireflection film according to the above (1) or (2), wherein the antireflection layer is not subjected to the polyester base in a checkerboard peeling test based on JIS K5 600-5 -6. The anti-reflection film of any one of the above (1) to (3), wherein the antireflection film of the above-mentioned antireflection film has a maximum amplitude difference of reflectance at 38 〇 nm to 780 nm. It is preferably 1 · 〇% or less. (5) The antireflection film according to any one of the above (1) to (4), wherein a near-infrared ray absorbing layer is preferably disposed on the other main surface side of the polyester substrate. (6) The front panel for a display of the present invention is characterized in that the antireflection film according to any one of the above items (1) to (5) is characterized in that the front panel is attached to the substrate. EFFECTS OF THE INVENTION (1) According to the present invention, it is possible to provide an antireflection film which can ensure adhesion between a polyester base material and an antireflection layer, and which can prevent interference spots and excellent antireflection performance, and also because of the above hard coating. The layer is directly disposed on the above-mentioned polyester substrate, and the primer layer for easy adhesion is not required, and it is not necessary to form a primer layer, so that an inexpensive antireflection film can be provided. Further, even without the above primer layer, the adhesion between the polyester substrate and the antireflection layer can be ensured. (2) The antireflection film according to the above (1), wherein the polyester substrate having the main surface of the polyester substrate disposed on the side of the antireflection layer is not subjected to an easy adhesion surface pretreatment It is suitable for the type, because the adhesion of the polyester substrate and the antireflection layer can be ensured even without the easy adhesion surface pretreatment, so that the easy adhesion surface pretreatment can be omitted, so that an inexpensive antireflection film can be provided. . (In addition, in the present invention relating to the first aspect of the patent application, the use of the polyester substrate subjected to the pre-treatment of the adhesion-prone surface is not excluded.) -8- 200916819 (3) In addition, according to the above (1) In the antireflection film according to (2), the antireflection layer is a suitable type of the present invention which is not peeled off from the polyester substrate in a checkerboard peel test based on JIS K5600-5-6. It is possible to provide an antireflection film which does not cause peeling of the antireflection layer and is excellent in quality reliability. (4) The antireflection film according to any one of the above (A) to (3), wherein the maximum 値 of the reflectance amplitude difference of the antireflection film at 380 nm to 78 〇 nin is 1. The suitable form of the present invention below % can provide an antireflection film with less interference spots. (5) The antireflection film according to any one of the items (1) to (4), wherein the other side of the polyester substrate is provided with a near-infrared absorbing layer. The anti-reflection film having the near-infrared absorbing layer is disposed in front of a plasma display (PDP) used for various electronic device display panels including large-sized televisions, and can be provided to be more useful. In the use of these electronic devices, as a function of shielding the near-infrared filter from the front of the PDP, it is suitable to prevent the malfunction of surrounding electronic devices such as televisions or air conditioners due to the leakage of the near-infrared rays. And an anti-reflection film with anti-reflection function. (6) In addition, since the front panel for a display of the present invention is attached to a substrate, the antireflection film according to any one of the above items (5) to (5) is disposed, so that a front panel for a display which is less expensive can be provided. Further, regarding the antireflection film layer, a front panel for a display which exhibits functions corresponding to the above items (1) to (5) can be provided. -9- 200916819 BEST MODE FOR CARRYING OUT THE INVENTION The polyester substrate used in the antireflection film of the present invention preferably has a light transmittance of 80% or more, more preferably 88% or more. The degree is preferably 2.0% or less, and preferably 1.0% or less. As a representative example, for example, polyethylene terephthalate-2,6-naphthalenedicarboxylate or the like is mentioned, and in particular, it is inexpensive, but has both excellent mechanical properties and heat resistance ( The flame retardant properties) and the like, preferably the two axes of polyethylene terephthalate (PET). The thickness of the above substrate is usually about 1 500 to 500 μη. An additive such as an antioxidant, a heat resistant agent, an ultraviolet absorber, or a slip agent may be added to the resin of the polyester substrate. The coating material for the hard coating layer may be used, and the ionizing radiation-curable resin, the conductive and/or non-conductive fine particles, the photoinitiator, the solvent, and the like may be combined and adjusted, and an ink which has been blended may be used. The hard coating can be adjusted by the following adjustment methods using the following ingredients. The refractive index of the hard coat layer must be designed in consideration of the refraction of the substrate. For example, the refractive index of a PET substrate of a polyester substrate is about right. The difference in the refractive index of the hard coating layer set above is the cause of the interference spots. Usually, interference spots occur when the difference between the hard coat layer and the base film is 0.03 or more. Therefore, the above hard coat rate is preferably 1.60 to 1.7 Torr. The refractive index of the metal hard coat layer to which the refractive index is large becomes close to that of the base film. Metal Oxygen Visible Light In addition, 昙 polyester base material ester or polyethylene transparent, chemical-resistant stretch film, in addition, a flame retardant, the following metal oxygen mixed with these layers of paint, the relationship of the rate ".66 left When it is large, it is a folded oxide of the refractive index of the layer, and the compound can be used in one or more than one or two or more. Further, in the antireflection film of the present invention, the maximum 値 of the reflectance amplitude difference of the antireflection film at 380 nm to 780 nm is 1.0% or less, and an antireflection film having less interference plaque can be provided. Therefore, as described above, the difference between the refractive index of the polyester substrate and the refractive index of the hard coating layer disposed thereon is preferably less than ±0.03, because the refractive index of the polyester substrate cannot be simply changed, so Selecting and combining the materials constituting the hard coating layer, that is, the ionizing radiation hardening resin and the metal oxide fine particles, and adjusting the material of the hard coating layer, the reflectance amplitude difference of the obtained antireflection film at 380 nm to 78 nm The maximum 値 is less than 1.0%. The metal oxide used in the hard coat layer using a conductive metal oxide can simultaneously impart antistatic properties to the antireflection film. The predetermined refractive index is formed only by one type of conductive metal oxide, and the content of the metal oxide in the hard coat layer may become large. Therefore, when two or more kinds of metal oxides are used at this time, the refractive index can be increased and the content of the metal oxide is not excessive. Further, the hard coat layer is formed using a resin containing an ionizing radiation curable resin. The hard coat layer can be formed by rationality. As the metal oxide contained in the hard coat layer, for example, antimony-doped tin oxide (ΑΤΟ), indium-doped tin oxide (ΙΤΟ), or phosphorous-doped tin oxide (ΡΤΟ) can be used. ), zinc oxide (ZnO), tin oxide (Sn〇2), chromium oxide (Zr02), zinc antimonate C ZnSb2〇6), and the like. The metal oxide is preferably a fine particle, and the average particle diameter is preferably 10 nm or less, more preferably 50 nm or less, and still more preferably 20 nm or less. When it is within this range, the dispersibility in the ionizing radiation -11 - 200916819 hardened resin is increased, and the degree of twist in the formation of the coating film becomes small. The lower limit of the average particle diameter of the metal oxide is not particularly limited, but is preferably 2. On or more from the viewpoint of conductivity or high refractive index. In addition, the average particle diameter of the metal oxide particles is measured by using an antireflection film containing metal oxide particles, and slicing with a microtome to take a 200,000-fold TEM of the sliced film cross section. A transmission electron microscope) photograph, with an average enthalpy of 300 particles as the average particle diameter. When the photographed particles have a long diameter and a short diameter without being circular, the long diameter and the short diameter of each particle are measured, and the average of these is calculated. The average enthalpy of 300 particles was measured and calculated as an average particle diameter. Next, the content ratio of the metal oxide which is important in the present invention to the hard coat layer is from 20% by volume to 42% by volume, preferably from 25 to 35% by volume. By setting the content ratio of the metal oxide in the hard coat layer to the above range, the hard coat layer can be made to the polyester base on the main surface of the polyester substrate provided with the hard coat layer side, without forming a primer layer. The adhesiveness of the main surface of the material is practical and strong, and the strength of the coating film is also high. When the ratio of the metal oxide to the hard coat layer is too small, it is presumed that the volume shrinkage at this time is large, and it is easy to peel off from the polyester substrate. On the other hand, if the ratio of the metal oxide to the hard coat layer is too large, Not only the strength of the coating film is lowered, but it is difficult to form a coating film even when it is too large. Therefore, the primer layer is not formed by the above range, and the adhesion of the hard coating layer to the main surface of the polyester substrate is practical. Further, since the primer layer is not provided on the main surface of the polyester substrate on the side of the hard coat layer, the occurrence of interference spots can be prevented, and an antireflection film excellent in antireflection performance can be provided. -12- 200916819 Further, the ratio of the above-mentioned metal oxide means the sum of the volume of the metal oxide relative to the volume of the metal oxide and the resin solid contained in the hard coat layer. The volume ratio is determined by the weight ratio of the metal oxide to the resin solid matter and the specific gravity of each material. As the ionizing radiation-curable resin for forming the hard coat layer, a monomer having a vinyl group, a (meth)acryl fluorenyl group, an epoxy group, or an oxetanyl group can be used. . These may be used singly or in combination of two or more. It is preferred to use a polyfunctional monomer or oligomer in view of compatibility with both productivity and hardness. As the polyfunctional monomer or oligomer, a polyfunctional acryl monomer having two or more unsaturated groups or an oligomer thereof is suitably used. Further, if there are many bonding groups or functional groups such as an amino bond in the monomer or oligomer molecule, the adhesion to the polyester substrate is improved. Further, by using a high refractive index monomer or oligomer such as bisphenol A denatured (meth) acrylate, the refractive index of the hard coat layer can be increased. Examples of the polyfunctional propylene-based monomer or oligomer include ethylene glycol mono(methyl)propyl citrate, monoethyl propylene di(methyl) propyl acrylate, and triethylene glycol bis (methyl). Acrylate, 1,4-cyclohexane diacrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tris(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylacetate Tris (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexane trimethyl Esters derived from polyols and (meth)acrylic acid, such as acrylate, polyurethane polyacrylate, polyester polyacrylate, etc., M-divinylbenzene, 4-vinylbenzene Formic acid-2-propanoid-13-200916819 decyl ethyl ester, vinylbenzene such as 1,4-divinylhexane and the like. These may be used alone or in combination of two or more kinds, and it is preferable to use at least one selected from the group consisting of pentaerythritol acrylate and dipentaerythritol hexamethacrylate. From the viewpoint of film strength, pentaerythritol tetra(meth)acrylate, alcohol tri(meth)acrylate, trimethylolpropane tri(methyl)propene, trimethylolethane tri(meth)acrylate, dipentaerythritol tetra) Acrylate, dipentaerythritol penta (meth) acrylate, and tetraol hexa(meth) acrylate are preferred. Here, "...(meth)ester"" means "...acrylate" and/or "...methacrylate". When the ionizing radiation-curable tree contained in the hard coating layer is used, ultraviolet rays are applied. At the time of irradiation, a photopolymerization initiator is added to the hard coating liquid. As the photopolymerization initiator, acetophenone, a second type, a ketal, an anthracene, a thioxanthone, an azo compound, or the like can be used. 2,3-dialkyldione compounds, disulfides, dihydrocarbon amine compounds, fluoroamine compounds, etc. These may be used singly or in combination. The amount of photopolymer initiator used is usually The amount of the ionization-curable resin is preferably about 3% by mass. Other component inhibitors, antioxidants, dispersants, surfactants, light-amplifiers, and the like may be added as the hard coat layer composition. Further, any amount of the solvent may be added as long as the wet coating method is formed. The method of forming the hard coat layer on the polyester substrate is not particularly limited, and the coating liquid containing the above material may be applied. a derivative formed on a polyester substrate. To increase the concentration of pentaerythritol esters (the benzophenone oxides in the hardened layer of methyl dipentaacrylate), the radiation is limited, such as the polymerization agent and the post-drying. Coating-14- 200916819 There is no particular limitation 'for example, roll coating, die coating, air knife coating, blade coat, spin coat, reverse coating can be used. (coating method such as reverse coat), gravure coat, or printing method such as gravure printing, screen printing, lithography (printing), inkjet printing, etc. The surface hardness of the layer is evaluated according to the pencil hardness test specified in JIS K5600, preferably Η or more, more preferably 2H or more. In addition, the thickness of the hard coating layer is preferably 〇.3~3·Ομιη, with 0.3~ 2.0μιη is particularly preferable, and it is more preferably 0.3 to 1.5 μm. When the thickness of the hard coating layer is less than 3 μm, it is difficult to maintain the hardness. Further, when the thickness of the hard coating layer exceeds 3. Ομιη, there is Breaking, curling (film The overall light transmittance of the anti-reflective film is reduced, and the volume shrinkage of the ionizing radiation-curable resin is increased, and the hard coating layer tends to be easily peeled off from the polyester substrate. Therefore, the hard coating layer is used. The thickness is preferably in the above range. The thickness of the optical film disposed on the hard coat layer is set to be close to the product of the refractive index and the film thickness, and the thickness of the optical film is λ/4 (λ: the wavelength of human visible light. When the wavelength of the light of the human eye is high (5 50 nm), the reflectance becomes lower, and the refractive index difference between the refractive index of the low refractive index layer and the hard coat layer is increased, and the antireflection property is increased. Further, when the low refractive index layer is provided on the outermost surface of the antireflection film of the present embodiment (that is, the other functional layer is not provided on the low refractive index layer), it is preferable to have strength and antifouling properties. The viewpoint is preferably a resin containing a perfluoro group or a polydimethyl oxime-15-200916819 alkane moiety. The coating material for forming the low refractive index layer can be combined and adjusted as follows: the adhesive resin forming material, the low refractive index fine particles, the photoinitiator, and the solvent temple can also be mixed with the ink which has been blended. By. The low refractive index coating can be adjusted using the following ingredients, which can be dispersed according to the general adjustment method of the coating liquid. As the material for forming the above-mentioned low refractive index layer, a known material which is generally used to form a low refractive index layer can be used. For example, a coating liquid containing a low refractive index inorganic fine particle such as silica sand or magnesium fluoride having a void, a material for forming an adhesive resin, or a coating liquid such as a fluorine-containing resin can be used. As the material for forming the adhesive resin forming the low refractive index layer, a monomer having a vinyl group, a (meth) acrylonitrile group, an epoxy group, a cyclobutyl group, a prepolymer or the like, and a polymer can be used. Ionizing radiation hardening resin. Here, "(meth)acrylonitrile" means "acryloyl" and/or "methacryloyl". Further, when a thermosetting adhesive is used, an inorganic adhesive can also be used. The inorganic binder may, for example, be a cerium oxide sol or the like. The cerium oxide sol can be, for example, a cerium oxide sol which is a starting material of a cerium alkoxide, an acid catalyst or an alkali catalyst. The decyl alkoxide may, for example, be tetramethoxy decane or tetraethoxy decane. When the ionizing radiation-curable resin contained in the low refractive index layer is cured, when a UV irradiation is performed, a coating liquid of a photopolymerization initiator in the low refractive index layer is added. As the photopolymerization initiator, acetophenones, benzophenones, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds can be used. Classes, disulfides, dihydrocarbylamines 醯-16- 200916819 Compounds, fluoroamines, etc. These may be used alone or in combination of two or more. The amount of the photopolymerization initiator to be used is usually from 1 to 15% by mass based on the mass of the ionizing radiation-curable resin. Other components such as a polymerization inhibitor, an antioxidant, a dispersing agent, a surfactant, a photostabilizer, and a leveling agent may be added as the other components of the above low refractive index layer composition. Further, any amount of the solvent may be added as long as it is dried by film formation by a wet coating method. The method of forming the low refractive index layer on the hard coat layer is not particularly limited, and a coating liquid containing the above material may be applied onto the hard coat layer in the same manner as the hard coat layer. Further, in the antireflection film of the present invention, the near infrared ray absorbing layer may be further disposed on the other main surface side of the polyester substrate. Therefore, when the antireflection film of the present embodiment is disposed on the surface of the PDP, the near-infrared rays emitted when the plasma discharge occurs are blocked, and the device using the peripheral electronic components is not adversely affected, and in particular, the television can be released. Or the problem of incorrect operation of the remote controller such as an air conditioner. The material of the near-infrared ray absorbing layer is a material which absorbs near-infrared rays and is transparent, and is not particularly limited. Usually, a resin which disperses a compound which absorbs near-infrared rays is used. The above-mentioned compound which absorbs near-infrared light is preferably a compound having a maximum absorption wavelength in the wavelength range of 850 to 1100 nm. Near-infrared absorbing layer When the above compound is right a, the transmittance of the visible light which is significantly lower than the wavelength of 400 to 850 nm can be reduced, and the near-infrared transmittance of the wavelength of 850 to 110 nm can be reduced. Therefore, the antireflection film of this embodiment can be suitably used as a near-infrared absorbing film of -17-200916819 PDP or the like. As the compound having a maximum absorption wavelength in the wavelength range of 850 to 1100 nm, for example, an amine gun system, an azo system, a fly exposure system, an Italian drive system, a spin blue system, a snail system, a quinophthalone system, a Squalium system, or the like can be used. An organic pigment such as a diphenylethylene, a diphenylcarbendene, a naphthoquinone, a diimonium, a phthalocyanine, an anthocyanine or a polymethine. As the resin for dispersing the near-infrared absorbing compound, a polyester resin, an acrylic resin, a polyurethane resin, a polyvinyl chloride resin, an epoxy resin, a polyvinyl acetate resin, a polystyrene resin, or a cellulose can be used. A resin, a polybutyral resin, or the like may be used, and two or more of these resins may be used in combination as a polymer blend. The method of forming the near-infrared ray absorbing layer on the polyester substrate is not particularly limited, and the coating liquid containing the above-mentioned material can be applied to the substrate in the same manner as in the case of the hard coat layer. The thickness of the near-infrared absorbing layer is preferably 1 to ΙΟμπι, and particularly preferably 2 to 7 μm. When the thickness is less than ιμιη, there is a tendency that it is difficult to absorb near-infrared rays. When the thickness exceeds 1 μm, the thickness of the near-infrared absorbing layer is preferably in the above range due to the tendency to break and curl (film anti-warping). In the near-infrared absorbing layer, a compound which blocks the spectrum of the bright line of the PDP (orange) may be added as appropriate. This allows the PDP to emit a more vivid red color. As a compound for blocking the spectrum of the bright line, an organic dye having a maximum absorption wavelength in the wavelength range of 580 to 620 nm can be used, for example, anthocyanin, azulenium, squalium, or phenyl group can be used. , diphenylmethane, oxazine, pyridazine, thiopyrium, zirconia ( -18- 200916819
Viologen)系、偶氮系、偶氮金屬錯鹽系、氮卟H林系、雙 偶氮系、蒽醌系、酞菁系等之有機色素。 可適當決定上述近紅外線吸收層之厚度、材料的種類 、含有率等，使於波長850~1100nm之全範圍，防反射薄 膜之分光穿透率爲20%以下。另外，近紅外線吸收層所設 置側之聚酯基材之主面上，設置易黏著化用之底漆層並無 妨，並且，通常以設置底漆層爲宜。另外，因應需要，近 紅外線吸收層所設置層側之聚酯基材之主面係可以電暈處 理、電漿處理等之易黏著化表面前處理。 以下係基於圖式說明本發明，但關於與上述實施型態 說明事項共通的事項，省略該說明。 圖1係表示本發明之防反射薄膜之一例的斷面圖。圖 1中，防反射薄膜1係聚酯基材1 〇、硬塗佈層1 1不介由 易黏接化用之底漆層等之中間層而直接設置於聚酯基材10 之一方主面10a上，另外，設置低折射率層12於硬塗佈 層1 1上。藉由硬塗佈層1 1及低折射率層1 2，形成防反射 層。 另外，圖2係表示本發明之防反射薄膜之其他一例的 斷面圖。除了圖2表示之防反射薄膜2係介由底漆層13 設置近紅外線吸收層1 4於聚酯基材1 0之另一方之主面 1 〇b以外，其他部份與圖1之防反射薄膜相同，所以與圖 1之防反射薄膜相同部份，標示相同符號，省略重複說明 〇 另外，本發明中，硬塗佈層雖必須不介由易黏接化用 -19- 200916819 之底漆層而直接設置於上述聚酯基材上，但上述聚酯基材 之設置硬塗佈層側相反側之主面側，亦可如圖2所示’因 應需要，設置易黏著化用之底漆層。本發明中所謂「直接 設置硬塗佈層於聚酯基材上」係指不僅未設置易黏著化用 之底漆層，亦不設置其他層於硬塗佈層與聚酯基材之間。 但是，硬塗佈層係直接設置於上述聚酯基材上以外， 因應要求，可將其他之抗靜電層、高折射率層、防污層等 之適合的機能性層，設置於硬塗佈層及低折射率層之間， 或設置於低折射率層上，只要不阻礙本發明之目的皆可。 上述聚酯基材之設置硬塗佈層側相反側之主面側上，只要 不阻礙本發明之目的，因應所需，設置如圖2所示之近紅 外線吸收層之其他黏著層或電磁波遮蔽層等之適當的機能 性層亦無妨。 如上述之本發明之防反射薄膜雖使用於例如設置於作 爲大型電視機爲首之各種電子機器之顯示器所使用之電漿 顯示器（PDP )或液晶顯示器等之前面，此時，與防反射 薄膜之防反射層相反側之主面成爲顯示側使用。 另外，本發明之顯不器用前面板係於基板上所配置如 上述之本發明之防反射薄膜者所形成。 作爲本發明之顯示器用前面板之基板，只要光；學上胃 明，具備保護顯示器用之充份強度者即可，雖非特別限定 者，但可使用例如玻璃基材、塑膠基材等。 基板的厚度亦依顯示器之種類或基板之材質而異，H 非特別限定者，通常可使用〇_2〜20mm，以0.2〜l5mm者爲 -20- 200916819 宜。 本發明之防反射薄膜黏膜對基板之黏著 以黏合劑或黏著劑等貼附於基板上。此時亦 ，本發明之防反射薄膜係貼附於基板上，使 相反側之主面成爲顯示器用前面板之基板側 本發明之顯示器用前面板係適用於液晶 顯示器（PDP )等之顯示器之顯示面前面側 之防反射薄膜之構成層之種類，可提供可發 、或防反射機能及作爲遮蔽近紅外線之過爐 示器用前面板。 【實施方式】 實施例 以下係基於實施例說明本發明，但本發 下述實施例者。另外，實施例、比較例中「 量份」。體積含有率係金屬氧化物與樹脂固 、及由各材料之比重文獻値計算所求出。 (實施例1 ) 如下所述製作與圖2所示之防反射薄膜 估用之防反射薄膜。 作爲聚酯基材，準備僅單面形成由含丙 形成之含有二氧化矽之底漆層之添加紫外線 爲ΙΟΟμιη之紫外線遮斷性聚對苯二甲酸乙二 係可以適當地 與上述同樣地 與該防反射層 〇 顯示器或電漿 ，因應所使用 揮防反射機能 器之機能之顯 明並非局限於 份」係指「重 形物之重量比 相同結構之評 稀基系樹脂所 吸收劑之厚度 .醇醋（Ρ Ε Τ ) 200916819 薄膜（全光線穿透率：92.0%，折射率1.66 )。接著，放 入 摻雜氧化錫微粒子（三菱Material製，平均粒徑爲20nm )5.5 份 氧化鉻微粒子（第一希元素製，平均粒徑爲10nm) 4.5 份An organic pigment such as a Viologen system, an azo system, an azo metal salt system, a nitrogen hydrazine H system, a bisazo system, an anthraquinone system, or a phthalocyanine system. The thickness of the near-infrared ray absorbing layer, the type of the material, the content ratio, and the like can be appropriately determined so that the spectral transmittance of the antireflection film is 20% or less over the entire range of the wavelength of 850 to 1100 nm. Further, it is not necessary to provide a primer layer for easy adhesion on the main surface of the polyester base material on the side on which the near infrared ray absorbing layer is provided, and it is usually preferable to provide a primer layer. Further, if necessary, the main surface of the polyester substrate provided on the layer side of the near-infrared absorbing layer can be pretreated by an easy adhesion surface such as corona treatment or plasma treatment. Hereinafter, the present invention will be described based on the drawings, but the description of the matters common to the above-described embodiments will be omitted. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an example of an antireflection film of the present invention. In Fig. 1, the antireflection film 1 is a polyester substrate 1 and the hard coat layer 11 is directly disposed on one of the polyester substrates 10 without interposing an intermediate layer such as a primer layer for easy adhesion. On the surface 10a, in addition, a low refractive index layer 12 is provided on the hard coat layer 11. An antireflection layer is formed by hard coating layer 11 and low refractive index layer 12. Further, Fig. 2 is a cross-sectional view showing another example of the antireflection film of the present invention. In addition to the anti-reflection film 2 shown in FIG. 2, the near-infrared absorbing layer 14 is disposed on the other main surface 1 〇b of the polyester substrate 10 via the primer layer 13, and the other portions are the anti-reflection of FIG. The same components as those of the antireflection film of FIG. 1 are denoted by the same reference numerals, and the repeated description is omitted. In addition, in the present invention, the hard coat layer must not pass through the primer for easy adhesion -19-200916819. The layer is directly provided on the polyester base material, but the main surface side of the polyester base material opposite to the side on which the hard coat layer side is provided may be provided with a bottom for easy adhesion as shown in FIG. 2 Paint layer. In the present invention, "directly providing a hard coat layer on a polyester substrate" means that not only a primer layer for easy adhesion is provided, but also no other layer is provided between the hard coat layer and the polyester substrate. However, the hard coat layer is directly provided on the polyester base material, and a suitable functional layer such as an antistatic layer, a high refractive index layer, or an antifouling layer may be provided on the hard coat layer if required. Between the layer and the low refractive index layer, or on the low refractive index layer, as long as the object of the present invention is not hindered. On the main surface side of the polyester substrate on the side opposite to the side on which the hard coat layer is disposed, as long as the object of the present invention is not hindered, other adhesive layers or electromagnetic wave shields of the near infrared ray absorbing layer as shown in FIG. 2 are provided as needed. It is also possible to have a suitable functional layer such as a layer. The antireflection film of the present invention is used for, for example, a plasma display (PDP) or a liquid crystal display used in a display of various electronic devices including a large-sized television, and in this case, an antireflection film. The main surface on the opposite side of the antireflection layer is used as the display side. Further, the front panel for a display of the present invention is formed by arranging the antireflection film of the present invention as described above on a substrate. The substrate of the front panel for a display of the present invention is not particularly limited as long as it has light and is suitable for protecting the display. However, for example, a glass substrate or a plastic substrate can be used. The thickness of the substrate varies depending on the type of the display or the material of the substrate. H is not particularly limited, and generally 〇 2 to 20 mm can be used, and 0.2 to 15 mm is preferably -20 to 200916819. The anti-reflection film of the present invention is adhered to the substrate by an adhesive or an adhesive or the like adhered to the substrate. In this case, the antireflection film of the present invention is attached to the substrate, and the main surface on the opposite side is the substrate side of the front panel for display. The front panel for a display of the present invention is applied to a display such as a liquid crystal display (PDP). The type of the constituent layer of the anti-reflection film on the front side of the display surface can provide a hair-emitting or anti-reflection function and a front panel for the over-infrared lamp for shielding near-infrared rays. [Embodiment] Hereinafter, the present invention will be described based on examples, but the following examples are given. In addition, in the examples and comparative examples, "volumes". The volume content ratio is determined by the calculation of the metal oxide and the resin, and the specific gravity of each material. (Example 1) An antireflection film for evaluation of the antireflection film shown in Fig. 2 was produced as follows. As the polyester base material, an ultraviolet ray-blocking polyethylene terephthalate system in which an ultraviolet ray having a ruthenium-containing primer layer formed of propylene is formed on one side, and the ultraviolet ray-blocking polyethylene terephthalate system is prepared in a manner similar to the above The anti-reflection layer 〇 display or plasma, in view of the function of the anti-reflection function used by the anti-reflection function is not limited to "the weight of the weight of the weight of the absorbent structure of the same structure of the absorbent resin. Alcohol vinegar (Ρ Ε Τ ) 200916819 Film (total light transmittance: 92.0%, refractive index 1.66). Next, doped tin oxide microparticles (Mitsubishi Material, average particle size 20nm) 5.5 parts of chromium oxide microparticles ( The first element is made of an average particle size of 10 nm) 4.5 parts
Disperbyk-180 ( BYK Chemie 社製分散劑）1.0 份 乙醯丙酮 5.0份 丙二醇單甲基醚 30份 及直徑爲0 · 3 mm之氧化鍩顆粒於容器，以塗料搖擺器（ Paint shaker )分散3小時後，除去氧化鍩顆粒，製作 AT0/Zr02之重量比爲5 5 : 45之分散液。 於此分散液，添加 季戊四醇三丙烯酸酯 2份 二季戊四醇六丙烯酸酯 2.7份 IRGCURE907 (CIBA Specialty Chemicals 製光聚合開始劑 )〇.3 份， 調製硬塗佈層形成用塗料（以下簡稱爲硬塗佈層用塗料） 〇 將此硬塗佈層用塗料，使用微凹版塗佈機（康井精機 社製）塗佈上述硬塗佈層用塗料於上述附底漆層之透光性 PET薄膜之未設置底漆層之面側後，使乾燥。接著，以 5 0 0m J/cm2之光線量之紫外線照射塗膜，使塗膜硬化’形 成厚度爲1·5μπι之硬塗佈層（塗膜中之金屬氧化物之比率 -22- 200916819 爲29vol%，塗膜之折射率爲164)。 之後’使用微凹版塗佈機塗佈中空二氧 散電離放射線硬化型低折射率塗料（觸媒 ’’ELCOM P-5013”）於上述硬塗佈層，使乾 800mJ/cm2之光線量之紫外線照射塗膜，使 成厚度爲l〇7nm之低折射率層。 <製作近紅外線吸收層用塗料> 混合' 攪拌下述材料，製作近紅外線吸, (1) 丙稀酸樹脂” DIANAL”（二菱Rayon社 (2) 芳香族”diimonium 色素 ’’CIR-1085 (日 ):6份 (3) 含有花青苷·二噻茂（dithiole )金屬 位之近紅外線吸收化合物”SD50-E04N”（住 最大吸收波長：877nm ) : 1份 (4) 含有花青苷·二噻茂（dithiole)金屬 位之近紅外線吸收化合物” S D 5 0 - E 0 5 N ”（住 最大吸收波長：83 3nm ) : 1份 (5 )甲基乙基酮·_ 1 2 5份 (6 )甲苯：4 6 0份 接著，於上述PET基材之底漆層上，使 版塗佈機塗佈上述近紅外線吸收層用塗料 4μιη之近紅外線吸收層，製作評估用之防反. 化矽微粒子分 化成（股）製 燥。接著，以 塗膜硬化，形 收層用塗料。 製）：1 0 0份 本Carlit社製 配位化合物部 友精化社製， 配位化合物部 友精化社製， 用上述之微凹 ’形成厚度成 时薄膜。 -23- 200916819 (實施例2 ) 放入 銻摻雜氧化錫微粒子（三菱Material製，平均粒徑爲 2 0 n m ) 6 份 氧化锆微粒子（第一希元素製，平均粒徑爲l〇nm) 4份 Disperbyk-180 ( BYK Chemie 社製分散劑）1.0 份 乙醯丙酮 5.0份 丙二醇單甲基醚30份 及直徑爲〇.3mm之氧化鉻顆粒於容器，以塗料搖擺器分散 3小時後，除去氧化鉻顆粒製作，使用 a T 0 / Z r 0 2之重量 比爲60: 40之分散液調整。 於此分散液，添加 季戊四醇三丙烯酸酯1.7份 二季戊四醇六丙烯酸酯 1.6份 IRGCURE907 ( CIBA Specialty Chemicals 製光聚合開始劑 )0.3 份， 調製硬塗佈層用塗料。 除了使用此硬塗佈層用塗料以外，與實施例1同樣地形成 防反射層及近紅外線吸收層，製作評估用之防反射薄膜（ 硬塗佈層中之金屬氧化物之比率爲36vol%，硬塗佈層之 折射率爲1 · 6 8 )。 (實施例3 ) 放入 -24- 200916819 銻摻雜氧化錫微粒子（三菱Material製，平均粒徑爲 20nm ) 4.5 份 氧化锆微粒子（第一希元素製，平均粒徑爲l〇nm) 5.5 份Disperbyk-180 (Dispersant made by BYK Chemie) 1.0 part acetonitrile acetone 5.0 parts propylene glycol monomethyl ether 30 parts and 0. 3 mm diameter cerium oxide particles in a container, dispersed by a paint shaker for 3 hours Thereafter, the cerium oxide particles were removed to prepare a dispersion of AT0/ZrO 2 in a weight ratio of 5 5 : 45. In this dispersion, pentaerythritol triacrylate, 2 parts of dipentaerythritol hexaacrylate, 2.7 parts of IRGCURE 907 (photopolymerization starter manufactured by CIBA Specialty Chemicals), and 3 parts were added, and a coating for forming a hard coat layer (hereinafter referred to as hard coating) was prepared.层层涂料) The coating material for the hard coating layer is coated with the coating material for the hard coating layer on the light-transmitting PET film of the primer layer by using a micro gravure coating machine (manufactured by Kangjing Seiki Co., Ltd.) After setting the side of the primer layer, it is allowed to dry. Next, the coating film is irradiated with ultraviolet rays of a light amount of 500 mJ/cm2 to harden the coating film to form a hard coating layer having a thickness of 1.5 μm (the ratio of the metal oxide in the coating film-22-200916819 is 29 vol %, the refractive index of the coating film is 164). Then, a hollow dioxodesed ionizing radiation-curable low-refractive-index paint (catalyst ''ELCOM P-5013') was applied to the hard coating layer using a micro gravure coater to dry ultraviolet rays of 800 mJ/cm 2 . The coating film is irradiated to a low refractive index layer having a thickness of 10 〇 7 nm. <Production of a coating for a near-infrared absorbing layer> Mixing 'Agitating the following materials to produce a near-infrared ray, (1) Acrylic resin DIANAL (Mitsubishi Rayon (2) Aromatic "diimonium pigment" 'CIR-1085 (Day): 6 parts (3) Near-infrared absorbing compound "SD50-E04N" containing anthocyanin and dithiole metal sites (Maximum absorption wavelength: 877 nm): 1 part (4) Near-infrared absorbing compound containing an anthocyanin/dithiole metal position "SD 5 0 - E 0 5 N " (maximum absorption wavelength: 83 3 nm) : 1 part (5) methyl ethyl ketone · _ 1 2 5 parts (6 ) toluene: 460 parts Next, on the primer layer of the above PET substrate, the plate coater is coated with the above-mentioned near infrared rays The absorption layer is coated with a near-infrared absorbing layer of 4 μm, and the anti-reflection for evaluation is made. Co., Ltd., which is made of a coating film and hardened, and a coating for forming a layer. System): 100 parts of the compound compound of Carlit Corporation, manufactured by Minyou Seika Co., Ltd. The aforementioned dimples 'form a thin film at a thickness. -23- 200916819 (Example 2) 锑-doped tin oxide fine particles (manufactured by Mitsubishi Material, average particle size 20 nm) 6 parts of zirconia fine particles (made of the first element, average particle diameter l〇nm) 4 Disperbyk-180 (Dispersant made by BYK Chemie) 1.0 part acetonitrile acetone 5.0 parts propylene glycol monomethyl ether 30 parts and chrome oxide particles of diameter 〇3mm in a container, dispersed by a paint shaker for 3 hours, remove oxidation The chrome particles were prepared using a dispersion of a T 0 / Z r 0 2 weight ratio of 60:40. To the dispersion, pentaerythritol triacrylate 1.7 parts of dipentaerythritol hexaacrylate 1.6 parts of IRGCURE 907 (light polymerization initiator of CIBA Specialty Chemicals) was added in an amount of 0.3 parts, and a coating for a hard coat layer was prepared. An antireflection layer and a near-infrared ray absorbing layer were formed in the same manner as in Example 1 except that the coating material for the hard coating layer was used, and an antireflection film for evaluation was prepared (the ratio of the metal oxide in the hard coating layer was 36 vol%, The refractive index of the hard coat layer is 1 · 6 8 ). (Example 3) Into -24-200916819 antimony-doped tin oxide fine particles (manufactured by Mitsubishi Material, average particle diameter: 20 nm) 4.5 parts of zirconia fine particles (manufactured by the first element, average particle diameter l〇nm) 5.5 parts
Disperbyk-180 ( BYK Chemie 社製分散劑）1.0 份 乙醯丙酮 5.0份 丙二醇單甲基醚30份 及直徑爲0.3mm之氧化銷顆粒於容器，以塗料搖擺器分散 3小時後，除去氧化銷顆粒製作，使用 AT0/Zr02之重量 比爲45 : 55之分散液調整。 於此分散液，添加 季戊四醇三丙烯酸酯3份 二季戊四醇六丙烯酸酯 3份 IRGCURE907 ( CIBA S p e c i a 11 y C h e mi c al s 製光聚合開始劑 )0.5 份， 調製硬塗佈層用塗料。 ' 除了使用此硬塗佈層用塗料以外，與實施例1同樣地形成 防反射層及近紅外線吸收層’製作評估用之防反射薄膜（ 硬塗佈層中之金屬氧化物之比率爲24vol%，硬塗佈層之 折射率爲1 · 6 3 )。 (實施例4 ) 放入 銻摻雜氧化錫微粒子（三菱 Material製，平均粒徑爲 -25- 200916819 2 0 n m ) 6 {分 氧化鍩微粒子（第一希元素製，平均粒徑爲1 Οηηι ) 4份Disperbyk-180 (Dispersant made by BYK Chemie) 1.0 part of acetonitrile acetone 5.0 parts of propylene glycol monomethyl ether 30 parts and 0.3mm diameter of oxidized pin particles in a container, dispersed by a paint shaker for 3 hours, removes the oxidized pin particles Manufactured using a dispersion of AT0/Zr02 with a weight ratio of 45:55. To the dispersion, 5 parts of pentaerythritol triacrylate, 3 parts of dipentaerythritol hexaacrylate, and 3 parts of IRGCURE 907 (CIBA S p e c i a 11 y C h e mi c al s photopolymerization initiator) were added, and a coating for a hard coating layer was prepared. In the same manner as in Example 1, except that the coating material for the hard coating layer was used, an antireflection film for forming an antireflection layer and a near infrared ray absorbing layer was prepared (the ratio of the metal oxide in the hard coating layer was 24 vol%). The hard coat layer has a refractive index of 1 · 6 3 ). (Example 4) 锑-doped tin oxide fine particles (manufactured by Mitsubishi Material, average particle size -25-200916819 2 0 nm) 6 {min. cerium oxide microparticles (manufactured by the first element, average particle size 1 Οηηι) 4 Share
Disperbyk-180 ( BYK Chemie 社製分散劑）1.0 份 乙醯丙酮 5 · 0份 丙二醇單甲基醚 3 0份 及直徑爲〇 . 3 mm之氧化锆顆粒於容器，以塗料搖擺器分散 3小時後，除去氧化鉻顆粒製作，使用 AT〇/Zr〇2之重量 比爲60 : 40之分散液調整。 於此分散液，添加 季戊四醇三丙烯酸酯 1.9份 二季戊四醇六丙烯酸酯1.9份 IRGCURE907 ( CIBA Specialty Chemicals 製光聚合開始劑 )〇·3 份， 調製硬塗佈層用塗料。 除了使用此硬塗佈層用塗料以外，與實施例1同樣地形成 防反射層及近紅外線吸收層，製作評估用之防反射薄膜（ 硬塗佈層中之金屬氧化物之比率爲3 1 vol%，硬塗佈層之 折射率爲1.66)。 (比較例1 ) 放入 銻摻雜氧化錫微粒子（三菱 Material製，平均粒徑爲 2 Onm ) 6.5 份 氧化鉻微粒子（第一希元素製，平均粒徑爲l〇nm ) 3.5 -26- 200916819 份Disperbyk-180 (Dispersant made by BYK Chemie) 1.0 part of acetamidine acetone 5 · 0 parts of propylene glycol monomethyl ether 30 parts and zirconia particles of diameter 〇 3 mm in a container, dispersed by a paint shaker for 3 hours The chromium oxide particles were removed and adjusted using a dispersion of AT 〇/Zr 〇 2 in a weight ratio of 60:40. To the dispersion, pentaerythritol triacrylate was added, 1.9 parts of dipentaerythritol hexaacrylate, 1.9 parts of IRGCURE 907 (photopolymerization initiator of CIBA Specialty Chemicals), and 3 parts, and a coating for a hard coat layer was prepared. An antireflection layer and a near-infrared ray absorbing layer were formed in the same manner as in Example 1 except that the coating material for the hard coating layer was used, and an antireflection film for evaluation was prepared (the ratio of the metal oxide in the hard coating layer was 3 1 vol). %, the refractive index of the hard coat layer is 1.66). (Comparative Example 1) 锑-doped tin oxide fine particles (manufactured by Mitsubishi Materials, average particle size: 2 Onm) 6.5 parts of chromium oxide fine particles (manufactured by the first element, average particle diameter l〇nm) 3.5 -26- 200916819 parts
Disperbyk-180 ( BYK Chemie 社製分散劑）ι·〇 份 乙醯丙酮 5.0份 丙二醇單甲基醚 30份 及直徑爲〇.3mm之氧化銷顆粒於容器，以塗料搖擺器分散 3小時後，除去氧化銷顆粒製作，使用AT〇/Zr〇2之重量 比爲6 5 : 3 5之分散液調整。 於此分散液，添加 季戊四醇三丙烯酸酯 5份 二季戊四醇六丙烯酸酯 5份 IRGCURE907 ( CIBA Specialty Chemicals 製光聚合開始劑 )0.7 份 丙二醇單甲基醚 13份， 調製硬塗佈層用塗料。 除了使用此硬塗佈層用塗料以外，與實施例1同樣地形成 防反射層及近紅外線吸收層，製作評估用之防反射薄膜（ 硬塗佈層中之金屬氧化物之比率爲1 6vol%，硬塗佈層之 折射率爲1 . 5 9 )。 (比較例2 ) 除了作爲基材係使用兩面上形成由含有二氧化矽之丙 烯基系樹脂所形成之底漆層（折射率爲1.58)，厚度爲 ΐΟΟμπι之紫外線遮蔽性聚對苯二甲酸乙二醇酯（PET )薄 膜（全光線穿透率：92.1% )以外，與實施例1同樣地形 -27- 200916819 成防反射層及近紅外線吸收層，製作評估用之防反射薄膜 (比較例3 ) 放入 銻摻雜氧化錫微粒子（三菱Material製，平均粒徑爲 2 0 n m ) 1 〇 份Disperbyk-180 (Dispersant made by BYK Chemie) ι·〇份乙醯acetone 5.0 parts of propylene glycol monomethyl ether 30 parts and oxidized pin particles of diameter 〇3mm in a container, dispersed by a paint shaker for 3 hours, removed The oxidized pin particles were prepared and adjusted using a dispersion of AT 〇 / Zr 〇 2 in a weight ratio of 6 5 : 3 5 . To the dispersion, pentaerythritol triacrylate was added, 5 parts of dipentaerythritol hexaacrylate, 5 parts of IRGCURE 907 (photopolymerization initiator of CIBA Specialty Chemicals), 0.7 parts of propylene glycol monomethyl ether, and a coating for a hard coat layer. An antireflection layer and a near-infrared ray absorbing layer were formed in the same manner as in Example 1 except that the coating material for the hard coating layer was used, and an antireflection film for evaluation was prepared (the ratio of the metal oxide in the hard coating layer was 16 vol%). The refractive index of the hard coating layer is 1.59). (Comparative Example 2) A UV-shielding polyethylene terephthalate having a thickness of ΐΟΟμπι was formed by using a primer layer (refractive index of 1.58) formed of a propylene-based resin containing cerium oxide on both sides as a substrate. An antireflection film and an near-infrared absorbing layer were prepared in the same manner as in Example 1 except that the diol ester (PET) film (total light transmittance: 92.1%) was used as the film of Comparative Example 3 (Comparative Example 3). ) 锑 doped tin oxide microparticles (Mitsubishi Material, average particle size 20 nm) 1 〇份
Disperbyk-180 ( BYK Chemie 社製分散劑）1.0 份 乙醯丙酮 5.0份 丙二醇單甲基醚 30份 及直徑爲〇.3mm之氧化锆顆粒於容器，以塗料搖擺器分散 3小時後’除去氧化锆顆粒製成，使用ΑΤΟ分散液調整。 於此分散液，添加 季戊四醇三丙烯酸酯 1 . 1份 二季戊四醇六丙烯酸酯 1 · 1份 IRGCURE907 ( CIBA Specialty Chemicals 製光聚合開始劑 )0_15 份， 調製硬塗佈層用塗料。除了使用此硬塗佈層用塗料以外， 與實施例1同樣地形成防反射層及近紅外線吸收層，製作 評估用之防反射薄膜（硬塗佈層中之金屬氧化物之比率爲 4 5 v ο 1 %，硬塗佈層之折射率爲丨.6 9 )。 上述實施例1〜4及比較例1〜1 3之抗反射薄膜之特性 係如下評估。 -28- 200916819 <折射率> 藉由折射率測定裝置”Film Tek3000”（ SCI社製）測 定各評估用之防反射薄膜之硬塗佈層之折射率。 <抗刮硬度（scratch hardness)(錯筆法）> 基於JIS K5600-5_4: 1 999測定各評估用之防反射薄 膜之硬塗佈層之抗刮硬度（鉛筆法）。 <附著性> 依據JIS Κ5600-5 -6 : 1 999，進行附著性（交叉切割 (Cross-Cut )法）試驗，評估PET基材與防反射層之黏 著性（但是，切割使以交叉切割產生的四角形圖形（棋盤 狀方格）成爲100個）。該結果如表1所示，表1中具體 上無自1 00個棋盤狀方格剝離處者爲〇，除此以外以X表 示。 <反射率•視感度反射率> 使用分光光度計”Ubest V-5 70”（日本分光社製），以 砂紙削去防反射層側及相反面側後，以黑色油性麥克筆塗 黑後，使用分光光度計”Ubest V-5 7 0”（日本分光社製）測 定防反射薄膜之視感度反射率。 <近紅外線穿透率> 使用上述分光光度計，對於設置近紅外線吸收層後之 -29- 200916819 防反射薄膜，以近紅外線吸收層側作爲入射光側，測定於 8 5 0〜1 1 0 0 n m之近紅外線波長範圍之穿透率的最大値。其 結果係實施例1〜4及比較例1〜3之評估用抗反射薄膜之近 紅外線穿透率皆爲1 2%以下。 <曇度> 使用日本電色工業股份有限公司製曇度測定器測定。 <表面電阻値> 表面高電阻率計“HirestaHT_2〇”（三菱油化社製）， 使用設置近紅外線吸收層後之各評估用防反射薄膜，測定 低折射率層側之表面電阻値。 近紅外線穿透率除外，上述測定結果如表1所示。 [表1] 實施例1 實施例2 實施例3 實施例4 比較例1 比較例2 比較例3 金屬氧化物（vol.%) 29 36 24 31 16 29 45 底漆層 紐 無 無 Μ yi W 输 有 Μ 曇度（％) 0.4 0.7 0.4 0.4 0.3 0.4 1.7 視感度反射率（％) 0.83 0.61 0.88 0.85 1.11 1.3 0.56 於380nm〜780nm之反射 0.19 0.14 0.31 0.08 1.05 1.64 0.25 率振幅差最大値（％) 黏著性 〇 〇 〇 〇 X 〇 X 鉛筆硬度 2H Η 2Η Η 2H 2H Β 表面電阻値（Ω/D) lxlO10 6χ109 8x10" lxlO10 2x10" 2x10'° 3χ108 如表1所示’可知實施例1〜4之防反射薄膜與不具備 -30- 200916819 申請專利範圍第1項之構成要件之比較例i〜 膜比較，硬度亦硬，密合性良好，於3 8 Onm 射率振幅差之最大値小。 本發明係於不超出該主旨之範圍，亦可J 態實施。本申請書所揭示之實施型態係一例 等。本發明之範圍係由上述說明書記載，優3 請專利範圍之記載，與申請範圍平等之範圍；； 包含於申請之範圍者。 產業上利用性 如上述說明之本發明係依據本發明，可援 ，防反射性能力優異，進而具備具有高耐傷但 之防反射薄膜。使用本發明之防反射薄膜或價 射薄膜之顯示器用前面板，可提供對各種顯 PDP適合的前面薄膜。 【圖式簡單說明】 [圖1]表示本發明之防反射薄膜之一例之_ [圖2]表示本發明之防反射薄膜之其他一 【主要元件符號說明】 1 :防反射薄膜 1 0 :聚醋基材 之防反射薄 7 8 0 n m之反 上述以外型 不局限於此 解釋所附申 全部改變亦 供無干涉斑 之防反射層 用上述防反 示器，尤其 :面圖。 例之斷面圖 -31 - 200916819 1 1 :硬塗佈層 1 2 ·_低折射率層 13 :底漆層 1 4 :近紅外線吸收層 -32-Disperbyk-180 (Dispersant made by BYK Chemie) 1.0 part acetonitrile acetone 5.0 parts propylene glycol monomethyl ether 30 parts and zirconia particles of diameter 〇3 mm in a container, dispersed by a paint shaker for 3 hours, 'removed zirconia Made of granules, adjusted with hydrazine dispersion. To the dispersion, pentaerythritol triacrylate was added. 1 part Dipentaerythritol hexaacrylate 1 · 1 part IRGCURE 907 (Photopolymerization starter of CIBA Specialty Chemicals) 0 to 15 parts, and a coating for a hard coating layer was prepared. An antireflection layer and a near-infrared ray absorbing layer were formed in the same manner as in Example 1 except that the coating material for the hard coating layer was used, and an antireflection film for evaluation was prepared (the ratio of the metal oxide in the hard coating layer was 4 5 v). ο 1 %, the refractive index of the hard coat layer is 丨.6 9 ). The characteristics of the antireflection films of the above Examples 1 to 4 and Comparative Examples 1 to 13 were evaluated as follows. -28-200916819 <Refractive Index> The refractive index of the hard coat layer of each of the antireflection films for evaluation was measured by a refractive index measuring apparatus "Film Tek 3000" (manufactured by SCI). <Scratch hardness (error method)> The scratch resistance (pencil method) of the hard coat layer of each of the antireflection films for evaluation was measured based on JIS K5600-5_4: 1 999. <Adhesion> According to JIS Κ5600-5 -6 : 1 999, an adhesion (Cross-Cut) test was performed to evaluate the adhesion of the PET substrate to the antireflection layer (however, the cut was made to cross The quadrilateral shape (checkerboard square) produced by the cut becomes 100). The results are shown in Table 1. Specifically, in Table 1, there is no 剥离 from the checkerboard of 100 checkerboards, and otherwise indicated by X. <Reflectance and sensibility reflectance> Using a spectrophotometer "Ubest V-5 70" (manufactured by JASCO Corporation), the anti-reflection layer side and the opposite side were scraped off with a sandpaper, and blackened with a black oily stylus Thereafter, the reflectance reflectance of the antireflection film was measured using a spectrophotometer "Ubest V-5 7 0" (manufactured by JASCO Corporation). <Near-infrared transmittance> Using the above spectrophotometer, the anti-reflection film of the -29-200916819 after the near-infrared absorbing layer was provided, and the side of the near-infrared absorbing layer was used as the incident light side, and it was measured at 8 5 0 to 1 1 0 The maximum 穿透 of the transmittance of the near-infrared wavelength range of 0 nm. As a result, the near-infrared transmittances of the evaluation antireflection films of Examples 1 to 4 and Comparative Examples 1 to 3 were all 12% or less. <昙度> Measured using a sputum measuring device manufactured by Nippon Denshoku Industries Co., Ltd. <Surface Resistance 値> The surface high resistivity meter "Hiresta HT_2" (manufactured by Mitsubishi Petrochemical Co., Ltd.) was used to measure the surface resistance 侧 on the side of the low refractive index layer using each of the antireflection films for evaluation after the near infrared ray absorbing layer was provided. Except for the near-infrared transmittance, the above measurement results are shown in Table 1. [Table 1] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Metal oxide (vol.%) 29 36 24 31 16 29 45 Primer layer no flaws yi W Μ 昙 ( (%) 0.4 0.7 0.4 0.4 0.3 0.4 1.7 Vision reflectance (%) 0.83 0.61 0.88 0.85 1.11 1.3 0.56 Reflection at 380nm~780nm 0.19 0.14 0.31 0.08 1.05 1.64 0.25 Rate amplitude difference maximum 値 (%) Adhesion Sex 〇〇〇〇X 〇X Pencil hardness 2H Η 2Η Η 2H 2H Β Surface resistance 値(Ω/D) lxlO10 6χ109 8x10" lxlO10 2x10" 2x10'° 3χ108 As shown in Table 1, 'Isolation of Examples 1 to 4 The reflective film is harder than the film of the comparative example i~ which does not have the constituent elements of the first application of the -30-200916819 patent application. The hardness is also good, and the adhesion is good, and the maximum difference in the amplitude difference of the 3 8 Onm is small. The present invention is not limited to the scope of the gist, and may be implemented in the J state. The embodiment disclosed in the present application is an example. The scope of the present invention is described in the above description, and the scope of the patent is as described in the scope of the patent, and the scope of the application is equal; Industrial Applicability The present invention described above is based on the present invention and is excellent in antireflection ability and further has an antireflection film having high scratch resistance. The front panel for a display using the antireflection film or the priced film of the present invention can provide a front film suitable for various display PDPs. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] shows an example of an antireflection film of the present invention. [Fig. 2] shows another one of the antireflection film of the present invention. [Main component symbol description] 1 : Antireflection film 10: Poly The anti-reflection thin of the vinegar base material is not limited to this explanation. The above-mentioned anti-reflection layer is also provided for the anti-reflection layer without interference spots, especially the surface view. Sectional view -31 - 200916819 1 1 : Hard coating layer 1 2 ·_Low refractive index layer 13 : Primer layer 1 4 : Near infrared absorption layer -32-