201000311 六、發明說明： 【發明所屬之技術領域】 本發明係有關一種接著性改質基材薄膜’特別是適合 於顯示器用構件中主要使用的硬塗膜之基材薄膜的接著性 改質基材薄膜、及其硬塗膜。更詳言之，係有關作爲具有 黏著劑層之硬塗膜的基材薄膜時，可抑制彩虹狀色彩，且 硬塗膜層與基材薄膜間之密接性優異的接著性改質基材薄 膜及其硬塗膜。 【先前技術】 一般而言，於液晶顯示器（LCD)、電漿顯示板（PDP)等 顯示器之構件中所使用的硬塗膜，係使熱塑性樹脂膜作爲 基材薄膜、且作爲具有硬塗膜層之積層薄膜所構成。 爲了表現光學的機能，前述之顯示器構件中係有設置 含有各種色素之機能層的情形。可舉例如PDP爲含有二亞 銨化合物或含氟酞菁系化合物等之近紅外線吸收劑的近紅 外線遮斷層；LCD爲含有碘色素之PVA層；電子紙爲含有彩 色油墨之色素層等。此等機能性色素一般會因太陽光線中 所含有的紫外線而分解，會有因耐候性不佳、因長期間使 用導致性能降低的問題。因此’也有藉由於基材薄膜中混 練紫外線吸收劑，而使用賦予有紫外線吸收性之基材薄膜 的情形。 成爲硬塗膜基材之熱塑性樹脂薄膜，係使用聚對酞酸 乙二酯（PET)、聚醯胺、丙烯酸、聚碳酸酯（PC)、三乙醯纖 維素（TAC)、環狀聚烯烴等所成的透明薄膜。特別是二軸配 向熱塑性聚酯薄膜，就優異的尺寸安定性、耐藥品性而言 -4- 201000311 ，被廣泛地使用作爲各種光學機能性薄膜之基材薄膜。 一般而言，爲二軸配向熱塑性樹脂薄膜時，由於薄膜 表面高度化結晶配向，會有與各種塗料、接著劑、油墨等 缺乏接著性的缺點。因此，自古以來提案在二軸配向熱塑 性樹脂薄膜表面上，以各種方法賦予易接著性之方法。 例如，使含有聚酯、丙烯酸、聚胺基甲酸酯、丙烯酸 接枝聚酯等樹脂之易接著層，藉由塗布法設置於熱塑性樹 脂薄膜表面上，以使熱塑性樹脂薄膜具有易接著性的方 法，係爲一般已知的方法。於該塗布法中，在結晶配向完 成前之熱塑性樹脂薄膜上直接或視其所需實施電暈放電處 理後，使含有上述樹脂之溶液或以分散媒分散樹脂的分散 體之水性塗布液塗布於基材薄膜上且予以乾燥後，至少朝 單軸方向進行延伸，接著實施熱處理，以完成熱塑性樹脂 薄膜之結晶配向的方法（即線上塗布（in-line coating)法）， 或於製造熱塑性樹脂薄膜後，在該薄膜上塗布水系或溶劑 系塗布液後’予以乾燥的方法（即離線塗布（off-line coating) 法），在工業上廣爲被實施。 然而，熱塑性樹脂薄膜爲二軸配向聚酯薄膜時，對折 射率（面方向）爲1.62〜1.65而言，例如以丙烯酸樹脂等所 形成的硬塗布層之折射率，通常爲以1 . 5 3爲中心之1 . 5 0〜 1.56。此外，一般而言位於中間之易接著層，係以丙烯酸 樹脂、聚胺基甲酸酯樹脂、聚酯樹脂等、或組合此等所成 的樹脂爲主成分予以形成。而且，該樹脂組成物層之折射 率’通常爲1.49〜1.54。 因此’藉由二軸配向聚酯薄膜與易接著層之折射率 201000311 差，在該界面上引起光反射’與硬塗布表面之反射光的干 涉而產生干涉斑（彩虹狀色彩）。因此，在硬塗膜上形成抗 反射層（AR層）或防污層後，會有經貼合的影像顯示裝置等 物品之視認性惡化情形或高級感受損的情形。 特別是在3波長螢光燈下，由於亮線光譜成分之比例 高，導致干涉斑顯著。近年來，3波長螢光燈之普及化在 一般家庭中急速成長，故該干涉斑問題變得極爲重要。因 此，干涉斑成爲問題之用途中，在二軸配向聚酯薄膜作爲 基材之機能性塑膠薄膜的使用上，係明顯受限了。要不然 就是直接使用具有干涉斑問題之機能性薄膜。實際上，在 使用二軸配向聚酯薄膜作爲基材之大型平面電視的領域 中，目前搭載的抗反射膜幾乎都觀察得到干涉斑。 另一方面，在硬塗布層表面上積層由高折射率層/低折 射率層、或高折射率層/中折射率層/低折射率層所構成的 抗反射層時，藉由使硬塗布層予以高折射率化，可自抗反 射層省略高折射率層。結果，於製造抗反射膜時，可大幅 地減低成本。該傾向係因近年來強烈要求低成本化時，愈 來愈被推廣。然而，使硬塗布層予以高折射率化時，由於 與易接著層之折射率差變得更大，上述干涉斑之問題更爲 顯著。 本發明人揭不一種積層聚酯薄膜，其係著重於薄膜之 局部厚度不均勻性對干涉斑的影響，且於製造具有以共聚 合聚醋與聚胺基甲酸酯爲主成分、固體成分的塗布厚度爲 0· 1 g/m2之易接著層的薄膜後’藉由在該薄膜上進行壓延處 理’使薄膜之局部厚度的不均勻性變小，以減低因基材薄 201000311 膜厚度之不均勻性所引起的干涉斑之積層聚酯薄膜（專利 文獻1 )。然而，在積層如上述般折射率較高（例如1 .60以 上）之硬塗布層時，雖具有優異的接著性，惟上述干涉斑情 形顯著。 專利文獻1 日本特開200卜71 439號公報 使硬塗膜之折射率與二軸配向聚酯薄膜同等時，就減 低干涉斑而言，沒有在二軸配向聚酯薄膜與硬塗布層之間 設置樹脂組成物層下，使硬塗布層與二軸配向聚酯薄膜予 以光學一體化，實質上沒有該兩層間之反射光，係爲理想 化。於專利文獻2中揭示以減低干涉斑爲目的，沒有經由 易接著被膜下、在經電暈放電處理或電漿處理的聚酯薄膜 表面上直接積層折射率爲1.55〜2.0之硬塗布層的硬塗 膜。然而，在二軸配向聚酯薄膜上直接設置硬塗布層時， 無法得到充分的接著力。 專利文獻2 日本特賻200 6-23 5 1 2 5號公報 此外，於專利文獻3^4中嘗試藉由使易接著層之塗布 厚度薄化，以保持接著性且抑制干涉斑。於專利文獻3中 例示具有由聚酯樹脂與曙唑啉系交聯劑所形成的塗布厚度 爲5〜30nm之不含粒子的塗布層之積層聚酯薄膜。於專利 文獻4中掲示’使由聚酯樹脂與蜜胺系交聯劑與平均粒徑 爲65 nm之粒子所形成的水性塗料於乾燥後之塗布量爲 0.005〜0.05 g/m2下進行塗布’形成具有經高度硬化的塗布 層之積層聚酯薄膜。 專利文獻3 日本特開2008-18543號公報 專利文獻4 日本特開2008-23718號公報 201000311 另外，爲積層、或貼合其他的光學機能層時，在與硬 塗布層的相反側上設置以丙烯酸系樹脂爲主成分之黏合劑 層。爲提高與該黏合劑層之密接性時，在基材薄膜上設置 塗布層，惟藉由另外設置的塗布層，在相反面上亦會產生 界面反射，成爲千涉斑之要因。 另一方面，其他減低干涉斑的方法，如專利文獻5揭 示，具有含2種以上具金屬元素之有機化合物的塗布層之 積層聚酯薄膜。 專利文獻5 日本特開2006-76292號公報 另外，在密接性改質基材薄膜之製造、加工中，有實 施加熱處理之情形。伴隨生產性之提高，會有在較短時間 、且高溫下實施處理的傾向，惟因加工處理時之熱經歷， 於加工製程中會有低聚物析出、且透明性降低。 於下述專利文獻中，亦揭示使用低聚物含量經減少的 對苯二甲酸乙二酯之薄膜作爲基材薄膜。惟此等所揭示的 薄膜，雖具有低聚物性，惟使用作爲硬塗膜之基材薄膜時 ，無法得到充分的干涉斑之降低效果。 專利文獻6 日本特開平9-99 5 3 0號公報 專利文獻7 日本特開2000-141570號公報 專利文獻8 日本特開2003-191413號公報 專利文獻9 日本特開2003-301057號公報 【發明内容】 發明所欲解決之課題 於較爲廣泛的視野角中使用的顯示器中’爲對應於更 爲高精細化時，考慮自所有角度觀看時皆必須具有充分的 201000311 干涉斑降低效果之硬塗膜。然而，上述專利文獻3、4中所 揭示的積層薄膜，即使於硬塗膜形成後，由於仍殘留有易 接著層之層構成，故無法得到充分的干涉斑減低效果。 因此，本發明人等所進行的先前發明1(日本特願 2 0 07-2 7 0 9 09號），係爲使充分的干涉斑減低效果與接著性 兩立。於先前發明1中，係提案藉由於形成硬塗膜時與硬塗 布劑成爲一體化下，塗布極薄的塗布液，而具有在基材薄 膜與硬塗布層之邊界範圍上分散有機-無機複合物之硬塗 膜、及由該基材所形成的接著性改質基材薄膜。先前發明1 藉由在基材薄膜與硬塗布層之邊界範圍上分散有機-無機 複合物，可謀求充分的干涉斑減低性與密接性兩立。 如先前發明1之接著性改質基材薄膜，塗布極薄的含無 機粒子之塗布液所形成的接著性改質層，由於層厚較薄， 會有藉由樹脂之粒子的保持力變小傾向。此處，製造基材 薄膜之生產速度、或硬塗膜之加工時的加工速度，係逐年 高速化的。因此，可知使先前發明1之接著性改質基材薄膜 提供給高速製膜或後加工處理時，會在接著性改質層中產 生粒子脫落（落粉）的情形，而會有導輥等之製程污染問題 。而且，因落粉情形導致接著性改質基材薄膜之表面凹凸 狀態產生變化時，無法得到安定的表面摩擦，產生加工特 性變動的問題。而且，實施較高溫之加工處理時，會有透 明性降低的問題。 本發明之課題係提供一種積層硬塗布層時，自所有角 度觀看時皆沒有顯著的千涉斑，具有優異的接著性、且接 著性改質層中所含的粒子之脫落情形少的接著性改質基材 201000311 薄膜。另外’本發明提供—種即使在硬塗布層之另一面上 具有黏合劑層時’仍可作爲積層體全體之干涉斑經抑制的 接著性改質基材薄膜。 換言之’本發明爲減低前述之干涉斑時，提供一種藉 由塗布極限薄度的特定樹脂、且塗布厚度小，可抑制粒子 之保持力降低情形，且可幾乎達到未來所需的高速加工化 ’可得安定的摩擦係數之接著性改質基材薄膜。此外，提 供一種即使設置有黏合劑層時，仍可作爲全體之干涉斑經 減低的硬塗膜用接著性改質基材薄膜。而且，亦提供一種 即使藉由加工實施熱經歷時，仍可得透明性之接著性改質 基材薄膜。 解決課題之手段 上述之課題’藉由下述解決方法可予以達成。 (1) 一種接著性改質基材薄膜，其係由在由熱塑性樹脂 薄膜所形成的基材薄膜之至少一面上積層有接著性改質層 (A)的接著性改質基材薄膜’其特徵爲前述接著性改質層 (A)係含有至少一種選自聚酯系樹脂、胺基甲酸酯系樹脂、 丙稀酸系樹脂之樹脂、及無機粒子，前述接著性改質層（A) 之塗布量爲3〜12mg/m2’且前述接著性改質層（A)表面之高 度爲lOOnm以上之表面突起的山麓部之最大直徑平均値爲 1 0 /z m以上。 (2) 前述之接著性改質基材薄膜，其中前述接著性改質 層（A)面間之靜摩擦係數（μ s)與動摩擦係數（μ d)之差（△ // )爲0 2 0以下。 (3) 則述之接著性改質基材薄膜，其中前述基材薄膜係 -10- 201000311 由實質上不含粒子之熱塑性樹脂薄膜所形成。 (4) 前述之接著性改質基材薄膜，其中前述基材薄膜係 由3層以上之積層聚酯薄膜所形成，前述基材薄膜中之低聚 物含量爲0.6質量％以上、0.90質量％以下。 (5) 前述之接著性改質基材薄膜，其中前述基材薄膜係 由3層以上之積層聚酯薄膜所形成，在中間層中含有紫外線 吸收劑。 (6) 前述之接著性改質基材薄膜，其中前述基材薄膜係 * 由在b層之至少一面上藉由共押出法積層有a層的積層聚酯 薄膜所形成，至少在前述a層面上積層有接著性改質層（A) ，前述a層含有0.05〜0.1質量％之平均粒徑爲1〜10/Z m的惰 性粒子。 (7) 前述之接著性改質基材薄膜，其中係爲在前述基材 薄膜之一面上積層接著性改質層（A)，在另一面上積層有塗 布層（B)之接著性改質基材薄膜，前述塗布層（B)含有聚酯 系樹脂與鈦化合物。 I (8)前述之接著性改質基材薄膜，其中前述塗布層（B)係 爲塗布、乾燥含有水性聚酯樹脂與乳酸鈦化合物與三乙醇 胺鈦化合物之塗布液（B)所形成者， 以前述塗布液（B)中所含的水性聚酯樹脂之質量爲（a)，以乳 酸鈦化合物之質量爲（b)，及以三乙醇胺鈦化合物之質量爲 (c)時，（a)/[(b) + (c)]爲 5 0/5 0 〜80/20，且（b)/(c)爲 3 5 /6 5 〜 65/35 ° (9)前述之接著性改質基材薄膜，其中前述接著性改質 層（A)含有共聚合聚酯、聚胺基甲酸酯與無機粒子。 -11 - 201000311 (10) —種硬塗膜，其係在前述之接著性改質基材薄膜的 前述接著性改質層（A)面上，藉由塗布未硬化的硬化型樹脂 積層硬塗布層時，前述硬塗布層直接積層於前述基材薄膜 上，且具有在前述基材薄膜與前述硬塗布層之邊界範圍上 分散之有機-無機複合物。 (11) 前述之硬塗膜，其中前述硬塗布層之折射率爲1.60 〜1 . 6 5 〇 發明之效果 本發明之接著性改質基材薄膜，爲硬塗膜時，可得作 爲全體之優異的干涉斑減低情形、且具有高接著性、可得 安定的表面摩擦性。因此，較佳的實施形態係積層爲形成 硬塗布層時之未硬化的硬化樹脂時，使未硬化的硬化樹脂 與接著性改質層中所含的樹脂混合，基本上在使基材薄膜 與硬塗布層直接積層下予以一體化。而且，較佳的實施形 態係即使於後加工處理之高速加工時，仍可製得製程污染 情形少，換言之即該脫落物之缺點少的硬塗布用接著性改 質基材薄膜。 較佳的實施形態，除上述效果外，於硬塗布處理加工 、及於其前後之加工處理中，即使實施加溫處理時，可製 得具有高透明性與優異的干涉斑減低情形、且高接著性之 硬塗膜。 較佳的實施形態，除上述效果外，使用作爲顯示器構 件使用時，可抑制近紅外線吸收劑、碘色素、彩色色素等 之光學機能性色素的惡化情形。 較佳的形態係除上述效果外，即使在硬塗布層之相反 -12- 201000311 側上設置黏合劑層時，亦可減低作爲積層體全體之干涉斑 〇 【實施方式】 實施發明之最佳形態 本發明之接著性改質基材薄膜，於塗布未硬化的硬化 樹脂時膨脹，與硬塗布層一體化下、具有極薄的接著性改 質層。因此，本發明之接著性改質基材薄膜，其特徵爲在 接著性改質層上積層硬塗布層時，在基材薄膜表面上直接 形成硬塗布層。換言之，使用透過型電子顯微鏡（TEM),自 倍率5萬倍至20萬倍進行攝影時，在基材薄膜與硬塗布層之 界面上沒有觀察到連續的樹脂組成物層。而且，可觀察到 在基材薄膜與硬塗布層之邊界範圍上獨立分散下述之有機 -無機複合物。藉由具有該構造，本發明之硬塗膜可減低 來自易接著層之界面反射的干渉斑。此外，藉由在基材薄 膜與硬塗布層之邊界範圍上分散的有機-無機複合物，可 得高密接性。 該有機-無機複合物，係在硬塗布層積層前之接著性 改質基材薄膜’可觀察到藉由無機粒子之突起高度爲 10 Onm以上的表面突起。然而，接著性改質層之塗布量爲 20mg/tn2以下（例如塗布層之比重爲1.2時，厚度約爲I7nm 以下）之極薄樹脂塗布層，由於無機粒子之保持力小，於 接著性改質基材薄膜以高速、連接於導輥時，不易防止粒 子脫落的情形。 本發明人等經過再三深入硏究有關表面突起形狀之微 細構造與粒子之脫落機構的關係，結果發現僅單純藉由樹 -13- 201000311 脂層之厚度與表面突起之高度，不能決定粒子容易脫落的 情形’形成山狀之表面突起的山麓變得寬廣，可影響無機 粒子容易脫落之新穎見解，遂而完成本發明。此處，樹脂 層之厚度變薄時，山狀之表面突起土台部變得貧弱，導致 尖銳突起之山麓寬度變得狹窄。可知該山麓之狹窄的表面 突起，無機粒子變得容易脫落。因此，本發明中藉由在表 面突起周圍積極地形成由塗布液中所含的樹脂成分所形成 之特定大小以上的山麓部，可解決該課題。而且，本發明 所指的藉由無機粒子、以高度爲l〇〇nm以上之突起爲中心的 周圍山麓部之最大直徑，係爲如第3圖所示以接著性改質層 中所含的無機粒子或其凝聚體爲核，在一個核之周圍上樹 脂成分爲山麓狀寬廣的形態時、山麓部之最大直徑。 藉由該構成，可減低因粒子之脫落導致的製程汚染情 形，且減低於積層硬塗布層（特別是高折射率之硬塗布層） 時，由所有角度所見的干涉斑，達成充分的密接性，係爲 本發明之新見解。 本發明之接著性改質基材薄膜中接著性改質層之粒子 脫落的容易性，係可由接著性改質層面之靜摩擦係數（V s )與動摩擦係數d )之差求取。塗布層係以儘可能 可使無機粒子堅固地固定的塗布量’幾乎完全沒有無機粒 子脫落的情形，薄膜之靜摩擦係數（^ s )與動摩擦係數 (V d )係幾乎相同或與動摩擦係數稍有關係。然而’無 機粒子容易脫落時，測定動摩擦時會有粒子脫落、且動摩 擦之値急速變大的情形。該薄膜會導致製造製程、或後加 工製程時加工設備在短時間受到顯著的污染’製品之品質 -14- 201000311 與生產性降低的問題。該現象在一般的塗布層（例如塗布 量爲50mg/m2以上、粒子之平均粒徑爲20〜150nm)幾乎完 全沒有問題，惟塗布量小至極限時，容易變得顯著。 本發明之接著性改質基材薄膜中接著性改質層間之靜 摩擦係數S )與動摩擦係數（/zd)的差= μ d 一 V s )，以0.20以下爲宜，較佳者爲0.19以下，更佳者爲 0.18以下。靜摩擦係數（/z S )與動摩擦係數（// d )的 差（Δ )爲0.2 0以下時，由於可控制落粉情形，且製程污 染亦變少，故較佳。藉此可減少因落粉情形所導致的光學 缺點。而且，由於可得安定的摩擦特性，就加工特性而言 較佳。而且，動摩擦係數及靜摩擦係數之値以〇 . 8以下較佳 ，更佳者爲0.6以下。大於0.8時，耐破裂性降低、且於加工 製程中變得容易受到傷害。 (1)基材薄膜 本發明使用的基材薄膜之厚度，沒有特別的限制，可 在20〜400 # m範圍內，視使用的用途規格而定任意決定。 基材薄膜之厚度上限値，以350//m較佳，以300；am更佳。 此外，薄膜之厚度下限値，以5 0 # m較佳，以7 5 # m更佳， 以1 0 0 // m最佳。薄膜厚度小於2 0 m時，剛性或機械強 度容易變得不充分。另外，薄膜厚度超過400#111時，由於 薄膜中存在的異物之絕對量增加，故形成光學缺點之頻率 增高。而且，使薄膜切斷成所定寬度時之隙縫性亦會惡化， 製造成本提高。此外，由於剛性變強，容易使長尺狀薄膜 變得不易捲取成輥狀。 構成基材薄膜之熱塑性樹脂以聚對酞酸乙二酯、聚對 駄酸丙二酯、聚對酞酸丁二酯、聚乙烯-2,6-萘酸酯、間規 -15- 201000311 聚苯乙烯、原菠烯系聚合物、聚碳酸酯、聚丙烯酸酯等爲 宜。而且’具有如聚酯或聚醯胺之極性官能基的樹脂，就 與接著性改質層之接著性而言較佳。 其中，以聚對酞酸乙二酯、聚乙烯-2,6-萘酸酯、聚對 酞酸丁二酯、聚對酞酸丙二酯或以此等樹脂之構成成分爲 主成分之共聚物較佳，換言之，以由聚對酞酸乙二酯所形 成的二軸配向薄膜更佳。 例如，形成基材薄膜之樹脂，使用以聚對酞酸乙二酯 爲基本架構之聚酯共聚物時，共聚合成分之比例小於2 0莫 耳％較佳。爲2 0莫耳％以上時，薄膜強度、透明性、耐熱 性不佳。可作爲共聚合成分使用的二羧酸成分，例如己二 酸、癸二酸等之脂肪族二羧酸、異酞酸、酞酸、及2,6-萘 二羧酸等之芳香族二羧酸、偏苯三酸及均苯四甲酸等之多 官能羧酸等。而且，可作爲共聚合成分使用的二醇，例如 二甘醇、1，4-丁二醇、丙二醇及新戊二醇等之脂肪酸二醇； p-二甲苯醇等之芳香族二醇；1，4-環己烷二甲醇等之脂肪族 二醇；平均分子量爲150〜20000之聚乙二醇等。 (低聚物之減低） 本發明之接著性改質基材薄膜的較佳形態’爲防止因 加熱加工處理所導致的透明性降低情形時’使在1 7 0 °C下進 行熱處理20分鐘時對薄膜之霧度變化量」Ηζ ( ΖΐΗζ =加熱 後霧度一加熱前霧度）小於1.5% ’以0.5 %較佳’以0.3 %更 佳。此時，基材薄膜之低聚物含量以0.9 0質量％以下較佳。 基材薄膜之低聚物含量爲〇.9〇質量％以下時’即使經由高溫 化處理時，低聚物之析出情形少’藉由加熱之霧度變化量 在上述範圍內，故爲企求。 -16- 201000311 然而，爲使低聚物含量變少時’進行下述處理時’產 生聚酯樹脂之氧化惡化’聚酯樹脂會有帶黃色的情形。顯 示器用構件所使用的薄膜之彩色値b値’爲4.0以下。因此 ，本發明之基材薄膜的低聚物含量爲0·60質量％以上、較佳 者爲0.70質量％以上、更佳者爲〇.8〇質量％以上。低聚物含 量爲0.60質量％以上時，不會有薄膜帶黄色的情形’適合使 用作爲液晶顯示器或電漿顯示器等之高品質的顯示器構件 〇 爲使加熱前後之薄膜霧度變化量在上述範圍內’且薄 膜之彩色度b値在上述範圍時，以具有3層以上使用表層上 低聚物含量少的聚酯樹脂之層構成的積層聚酯薄膜爲較佳 的實施形態。積層聚酯薄膜之層構成’由低聚物含量少的 聚酯樹脂所形成的b層、此等以外之聚酯樹脂爲a層、c層時 ，薄膜層構可爲 a/b、b/a/b、b/a/c/b、或 b/a/c / a/ b等。於任何一種中，使用積層聚酯薄膜作爲本發明 之基材薄膜時，以使用在構成最表層之A層中低聚物含量 少的聚酯樹脂較佳。 低聚物係包含以環狀三聚物爲主的環狀低聚物、線狀 二聚物及線狀三聚物爲主的線狀低聚物、對酞酸、對酞酸 單乙二醇酯等，惟本發明之低聚物係主要由環狀三聚物所 形成。形成該低聚物少的聚酯薄膜層之方法’沒有特別的 限制，如日本特開昭48-101462號公報、特開昭49-32973號 等所揭示，可使用藉由使經聚合的薄片再以固相予以聚合 ，以薄片狀態減少低聚物等的低分子量體，且使用此等原 料製膜的方法，或使用溶劑以除去薄片中低聚物等之低分 子量體、予以製膜的方法，或使用溶劑、自二軸延伸熱固 -17- 201000311 定的薄膜萃取除去低聚物等之低分子量物的方法等。特別 是附加前者之固相聚合操作的方法，在對薄膜之押出製程 中溫度高、時間長時，由於以熱平衡關係增加折角經減少 的低聚物等之低分子量體，故以儘可能的低溫下且在短時 間內押出較佳。 (紫外線吸收劑） 本發明之較佳實施形態，爲防止光學機能性色素惡化 時，以使用3層以上之積層聚酯薄膜作爲基材薄膜，在該中 間層中含有紫外線吸收劑較佳。此時，以具有紫外線吸收 劑之層爲a層、除此等以外之面爲b層、c層時，薄膜層構成 可爲 b / a/b、b / a/ c、b / a/c/b，或 b/a/ c/a/b 等 ° a〜c層之各層可各與聚酯樹脂之構成相同，或不相同。 於此等之中，以b/ a/ b構成（2種3層構成）較佳。於任何 一種之中，皆以設置含有紫外線吸收劑之層作爲中間層爲 較佳的形態。藉由在中間層中含有紫外線吸收劑，可防止 添加劑之外滲情形，且可抑制因添加劑之外滲情形所導致 的密接性降低現象。 於本發明中可使用習知的紫外線吸收劑。紫外線吸收 劑’例如有機系紫外線吸收劑與無機系紫外線吸收劑，就 透明性而言以有機系紫外線吸收劑較佳。有機系紫外線吸 收劑’例如苯并***系、二苯甲酮系、環狀亞胺酯系等、 及其組合，只要是在本發明規定的吸光度之範圍內即可， 沒有特別的限制。然而，就耐久性而言以苯并***系、環 狀亞胺酯系更佳。倂用2種以上之紫外線吸收劑時，由於可 同時吸收各種波長之紫外線，故可一倂改善紫外線吸收效 果。 -18- 201000311 使用含有紫外線吸收劑之基材薄膜時，本發明之接著 性改質基材薄膜在波長380nm之透過率，以20 %以下較佳。 特別是使用作爲PDP用過濾器或偏光板保護薄膜等之顯示 器構件的基材時’在380nm之透過率爲15%以下較佳，以5% 以下更佳。前述之透過率爲20%以下時，可抑制光學機能 層中所含的近紅外線吸收色素或碘色素等之光學機能性色 素因紫外線所導致的變質情形。爲使接著性改質基材薄膜 在波長380nm之透過率爲20 %以下時’可適當調整前述紫外 線吸收劑之濃度、及基材薄膜之厚度。而且，本發明之透 過率係爲對接著性改質基材薄膜光學積層薄膜之平面而言 ’以垂直方法所測定者’可使用分光光度計（例如日立 U-3 500型）予以測定。 (不含粒子之構成） 另外’本發明所使用的接著性改質基材薄膜，由於被 要求高度的透明性’故以實質上在基材薄膜中不含使透明 性降低的粒子較佳。 前述之「實質上不含粒子」’係指例如爲無機粒子時， 以砂光X射線分析定量無機元素時爲50ppm以下，較佳者 爲1 Op pm以下，更佳者爲檢測臨界値以下之含量。此係即 使沒有在基材薄膜中積極添加粒子時，由於來自外來異物 之污染成分、或原料樹脂或薄膜製造製程中附著於管線或 裝置之污垢剝離，混入薄膜中之故。 (表層粒子構成） 本發明之較佳實施形態，爲得更安定的表面摩擦特性 時’可使用僅在表層中含有惰性粒子之積層聚酯作爲基材 薄膜。該基材薄膜以使用具有在b層之至少一面上含有惰性 -19 - 201000311 粒子之a層藉由共押出法予以積層所形成的積層構成之聚 酯薄膜較佳。藉由使基材薄膜爲上述之構成，可維持高透 明性、且賦予安定的易滑性。 本發明之基材薄膜，可爲2層構成、亦可爲具有3層 以上之多層構造。實質上不含粒子之b層、含有惰性粒子 之a層、除此等以外之面爲c層時，薄膜厚度方向之層構 成可考慮爲 b / a、a/b / a、a/b / c、a/b/c/a、或 a /b / c/b / a等之構成。a〜c層之各層’亦可各與聚酯樹 脂之構成相同、或不相同，惟爲控制藉由兩種金屬構成時 所產生的翹曲情形時，以各層之聚酯樹脂爲相同構成、及 /或a/b/a構成（2種3層構成）較佳。爲任何一種時， 爲使在下述之a層表面上積層密接性改質層時，以含有惰 性粒子之a層構成至少基材薄膜之一面的表層較佳。 在a層中所含的惰性粒子，例如碳酸鈣、磷酸鈣、非晶 性二氧化矽、球狀二氧化矽、結晶性玻璃纖維、高嶺土、 滑石、二氧化鈦、氧化鋁、二氧化矽-氧化鋁複合氧化物粒 子、硫酸鋇、氟化鈣、氟化鋰、沸石、硫化鉬、雲母等之 無機粒子、或交聯聚苯乙烯粒子、交聯丙烯酸系樹脂粒子 、交聯甲基丙烯酸甲酯系粒子、苯并鳥糞胺•甲醛縮合物 粒子、蜜胺•甲醛縮合物粒子、聚四氟乙烯粒子等之耐熱 性高分子微粒子。特別是就透明性而言，以樹脂成分與折 射率較爲接近的二氧化矽粒子（特別是非晶性二氧化矽）爲 宜。 a層中所含的惰性粒子之平均粒徑’以1〜1 0 A m較佳、 更佳者爲1·5〜7//m之範圍，最佳者爲2〜5#m之範圍。惰 性粒子之平均粒徑爲1.0# m以上時，以可賦予a層表面具有 -20- 201000311 易滑性之適當的凹凸構造較佳。另外，惰性粒子之平均粒 徑爲ΙΟ/zm以下時，由於可維持高的透明性，故較佳。而且 ’ a層中惰性粒子之含量，以0.005〜0.1質量％爲宜，較佳 者爲0.008〜0.07%，更佳者爲〇.〇1〜〇.〇5%。惰性粒子之含 量爲0.005質量％以上時，a層表面具有易滑性、可賦予適當 的凹凸構造，故較佳。另外，惰性粒子之含量爲0.1質量％ 以下時，由於可維持高的透明性，故較佳。 含有惰性粒子之a層的厚度，在基材薄膜全層中之合計 厚度以3〜30/zm較佳，更佳者爲5〜20ym。a層之厚度爲3 以m以上時，上述惰性粒子容易保持於a層内，即使在高速 加工下仍可容易得到安定的易滑性。此外，B層之厚度爲 30/zm以下時，就透明性而言較佳。a層之厚度，於使用透 過型電子顯微鏡（TEM )觀察基材薄膜時，惰性粒子之含 有密度的差異可判斷邊界、且予以測定。而且，於製造薄 膜時，可藉由自押出機之積層比（吐出量比）計算薄膜全 體厚度予以求取。 前述惰性粒子之平均粒徑的測定，係藉由下述方法進 行。 使粒子以電子顯微鏡進行照相，1個最小粒子之大小爲 2〜5mm的倍率，測定300〜500個粒子之最大直徑，以其平 均値作爲平均一次粒徑或平均粒徑。而且，求取接著性改 質基材薄膜之接著性改質層中粒子的平均粒徑時，可使用 透過型電子顯微鏡（TEM )，以倍率12萬倍攝影接著性改質 基材薄膜之截面，求取複合物之粒子的最大粒徑。由凝集 體所形成的粒子之平均粒徑，係使接著性改質基材薄膜之 接著性改質層的截面，使用光學顯微鏡、以倍率200倍攝影 -21 - 201000311 20 0個以上，且測定其最大粒徑。 如上述藉由在Β層中添加特定大小的惰性粒子，ί 層側表面上形成適合賦予安定易滑性之表面凹凸。藉 述構成，以使密接性改質基材薄膜之Β層側表面的中心 均粗糙度（SRa)爲0.005〜0.05/zm爲宜，較佳者爲0 0.03/zm。而且，十個平均粗糙度（SRz)以0.5〜2.0/； 宜，較佳者爲0.8〜1·5/ζιη。藉由在至少薄膜表層之一 形成上述範圍之表面凹凸，即使在高速加工下、仍可 得到安定的易滑性與加工處理性。 密接性改質基材薄膜之霧度在上述範圍內時，a層1 可含有適當的惰性粒子。例如，使含有粒子之聚酯薄 以再生利用時，以在上述霧度之範圍內、調整混合比 。然而，就可得高的透明性爲目的時，以於a層中實質 含惰性粒子爲較佳的形態。 (基材薄膜之製造方法） 於本發明之熱塑性樹脂中，在不會妨礙本發明效 範圍內’除觸媒以外可含有各種添加劑。添加劑例如 粒子、耐熱性高分子粒子、鹼金屬化合物、驗土類金 合物、磷化合物、抗靜電劑、紫外線吸收劑、耐光劑 燃劑、熱安定劑、抗氧化劑、凝膠化防止劑、界面活 等。 本發明所使用的基材薄膜，以使熱塑性樹脂熔 出’或使熔融押出所得的未配向薄片視其所需朝長度 或寬度方向之單軸方向進行延伸，或朝二軸方向逐次 延伸或同時二軸延伸，且實施熱固定處理之二軸配向 性樹脂薄膜爲宜。 在B 由上 面平 .0 1〜 i in爲 面上 容易 中亦 膜予 爲宜 上不 果之 無機 屬化 、難 性劑 融押 方向 二軸 熱塑 -22- 201000311 以使用聚酯作爲基材薄膜之原料時作爲典型例 基材薄膜之製造方法，於下述中詳細地說明。 作爲薄膜原料所使用的聚酯料粒之固有黏度， 〜0.70dl/g之範圍較佳。固有黏度小於〇.45dl/g時 造薄膜時大多容易產生斷裂情形。另外，固有黏 0.70dl/g時，濾壓大爲上昇，不易進行高精度過濾 容易產生生產性降低的情形。而且，聚酯之固有黏 使聚酯溶解於苯酚（6質量份）、與1，1，2,2-四氯乙烷 份）之混合溶劑中溶解，在3 0 °C下進行測定。 另外，以除去造成光學缺點原因之原料聚酯中 異物較佳。爲除去聚酯中之異物時，在熔融押出時 脂保持於270〜29 5 °C之任意時段進行高精度過濾處 融樹脂於高精度過濾處理時所使用的濾材，沒有特 制，爲不銹鋼燒結體之濾材時，以Si、Ti、Sb、Ge 主成分之凝聚物及高熔點有機物之除去性能優異爲 熔融樹脂於高精度過濾處理時所使用的濾材之 子尺寸（初期過濾效率9 5 %)，以1 5 m以下較佳。 過濾粒子尺寸大於15μιη時，導致20/zm以上異物 效果變得不充分。 使聚酯料粒充分進行真空乾燥後，供應給押出 在270〜295°C下熔融押出成薄片狀，且予以冷卻硬 得未配向的流延薄膜。使所得的流延薄膜以在80〜 加熱的輥、朝長度方向予以延伸2.5〜5.0倍，製得澤 聚酯薄膜。 然後，在單軸配向聚酯薄膜之兩面上塗布下述 液。然後，使薄膜的兩端部以夾子固定，導入加熱 ，有關 以 0.45 ，於製 度大於 處理， 度係可 (4質量 所含的 熔融樹 理。熔 別的限 、Cu爲 宜。 過濾粒 濾材之 J之除去 機、且 化，製 120〇C 下 【軸配向 之塗布 成8 0〜 -23- 201000311 180 °C之熱風區，乾燥後朝寬度方向延伸2.5〜5.0倍。其次 ’導入加熱成22〇〜240°C之熱風區’進行熱處理以完成結 晶配向處理。在該熱處理製程中，視其所需亦可朝寬度方 向或長度方向實施1〜12%之鬆驰處理。 而且’基材薄膜在不會損害本發明目的之範圍內，亦 可在前述之基材薄膜上實施電暈放電處理、輝光放電處理 、火焰處理、紫外線照射處理、電子線照射處理、臭氧處 理等之表面活性化處理。 (2 )接著性改質層（a ) 本發明之接著性改質基材薄膜，係由至少在基材薄膜 之一面上積層接著性改質層（A )所形成。本發明之接著性 改質層（A)係含有至少一種選自聚酯系樹脂、胺基甲酸酯系 樹脂、丙烯酸系樹脂之樹脂、及無機粒子。構成本發明之 接著性改質層（A)的聚酯樹脂、丙烯酸樹脂、胺基甲酸酯 樹脂，係對基材薄膜及硬塗布層兩方而言具有接著性，且 在硬塗布劑中所含的有機溶劑中適當地膨脹。上述之樹脂 可單獨使用，亦可不同的2種樹脂（例如聚酯樹脂樹脂與胺 基甲酸酯樹脂、聚酯樹脂與丙烯酸樹脂、或胺基甲酸酯樹 脂與丙烯酸樹脂）組合使用。 其中，作爲基材之基材薄膜爲聚酯系基材薄膜時，就 與硬塗布層之接著性而言、及前述膨脹性而言，以含有共 聚合聚酯及聚胺基甲酸酯作爲構成複合物之主要樹脂成分 較佳。共聚合聚酯單獨時，與聚酯基材薄膜之接著性雖充 分，惟與硬塗布層之接著性不佳。而且，由於爲較脆的樹 脂，對切割時之衝擊而言容易產生凝聚破壞情形。 此外，聚胺基甲酸酯單獨時，與硬塗布層之接著性雖 -24- 201000311 較爲優異，惟與聚酯系薄膜之接著形不佳。另外，使接著 性改質基材薄膜捲取成輥狀時之耐黏連性不佳。因此，使用 具有由聚胺基甲酸酯單獨所形成的接著性改質層（A )之接 著性改質基材薄膜所製造的硬塗膜，會有品質不佳的情形。 爲避免該問題時，必須使於基材薄膜中含有多量的粒 子之複合物中含有粒徑大的粒子，或增加構成複合物之粒 子的含量。結果，由於薄膜之霧度上昇，特別是作爲透明 性要求強的硬塗膜之基材薄膜，不爲企求。 本發明之接著性改質層（A )，可經由使塗布液（A ) 連續塗布於行走的熱塑性樹脂薄膜之至少一面上的塗布製 程，乾燥塗布液之乾燥製程，然後，至少朝單軸方向進行 延伸的延伸製程、以及使經延伸的薄膜予以熱固定處理的 熱固定處理製程予以形成，製造設置有接著性改質層（A )之接著性改質基材薄膜。設置下述之塗布層（B)時，以 使塗布層（A)與塗布液（B)連續塗布於塗布另一面上爲 宜。而且，視其所需可在塗布液（A)中混合至少一種選自 環氧系交聯劑、蜜胺系交聯劑、噚唑啉系交聯劑，藉由熱 處理、形成適當的交聯構造。 (塗布液（A)之調合製程） 於本說明書中，分別以爲形成接著性改質層（A)時之 塗布液爲塗布液（A)，以在另一面上形成下述之塗布層（ B)的塗布液爲塗布液（B)(而且，實施例中之表記以另 外指示爲基準）。使用塗布法形成本發明之接著性改質層（ A)時，塗布液（A)中所使用的材料，係爲樹脂及分散媒 或溶劑。於本發明中，塗布液（A )以水性較佳。另外，本 發明中除樹脂成分以外，可倂用無機粒子。此外，以倂用 -25- 201000311 界面活性劑較佳，視其所需可使用界面活性劑、抗靜電劑 、紫外線吸收劑、有機潤滑劑、抗菌劑、光氧化觸媒等之 添加劑。 另外，於塗布液（A )中，爲促進樹脂之熱交聯反應時 ，亦可添加觸媒，例如可使用無機物質、鹽類、有機物質 、鹼性物質、酸性物質及含金屬有機化合物等之各種化學 物質。而且，爲調節水溶液之pH値時，亦可添加鹼性物質 或酸性物質。塗布液（A )係在分散媒或溶劑中、攪拌下， 使樹脂予以分散化或溶解，然後，除下述所調整的無機粒 子分散液外，可倂用界面活性劑、視其所需各種添加劑， 稀釋至企求的固體成份濃度爲止予以調整。 而且，爲使塗布液（A)之樹脂成分及粒子均勻地分散 時，另外除去粗大的粒子凝聚物及製程内塵埃等之異物時 ，以使塗布液（A )予以精密過濾較佳。 爲使塗布液（A)予以精密過濾時之濾材型式，只要是 具有前述性能即可，沒有特別的限制，例如單絲型、絨毛 型、篩網型。爲使塗布液（A)予以精密過濾時之濾材的材 質，只要是具有前述之性能且對塗布液（A)不會有不良影響 即可，沒有特別的限制，例如不銹鋼、聚乙烯、聚丙烯、 耐龍等。 爲使塗布液（A )予以精密過濾時之濾材，過濾粒子大 小尺寸（初期過過效率：9 5 % )以2 5 m以下之濾材較佳， 更佳者爲過濾性能1 〇 # m以下之濾材。最佳者係爲使用組合 過濾性能不同的過濾器之方法。使用過濾粒子大小大於2 5 Mm之濾材時，粗大凝聚物之除容易變得不充分。因此，無 法以過濾除去的粗大凝聚物，藉由以塗布乾燥後之單軸配 -26- 201000311 向或二軸配向製程之配向應力變得更爲寬廣，有100/zm以 上的凝聚物存在，容易變成光學缺點之原因。 (A )樹脂 於本發明中，使用聚酯系樹脂（特別是共聚合聚酯 (PEs))與聚胺基甲酸酯系樹脂（特別是聚胺基甲酸酯（PU)) 作爲構成複合物之樹脂時，就接著性而言較佳。此時，塗 布液（A)中之共聚合聚酯（PEs)與聚胺基甲酸酯（PU)之固形 成分基準的質量比，以（PEs)/(PU) = 70/30〜30/70較佳，以 60M0〜4〇/60更佳。而且，複合物之樹脂可倂用上述共聚 合聚酯與聚胺基甲酸酯外之第3樹脂。此外，亦可倂用交 聯劑。 (聚酯系樹脂） 例如’在複合物中使用共聚合聚酯作爲聚酯系樹脂 時，以芳香族二羧酸成分、與作爲二醇成分之乙二醇與分 枝狀二醇爲構成成分較佳。上述分枝狀二醇例如2,2-二甲 基-1,3-丙二醇、2-甲基-2-乙基-1,3-丙二醇、2-甲基-2-丁基 -1,3-丙二醇、2 -甲基-2-丙基-1，3-丙二醇、2 -甲基-2-異丙基 -1,3-丙二醇、2-甲基-2-正己基-13·丙二醇、2,2·二乙基 -1，3-丙二醇、2-乙基-2-正丁基-^―丙二醇、2_乙基_2·正己 基-1，3-丙二醇、2,2-二-正丁基-丨，3_丙二醇、2_正丁基_2_ 丙基-1，3-丙二醇、及2,2-二正己基-丨，3_丙二醇等。 分枝狀二醇成分之莫耳比，對全部二醇成分而言下限 値爲1 〇莫耳°/。較佳、更佳者爲2 〇莫耳％、最佳者爲3 〇莫 耳％。另外，上限値爲9 0莫耳％較佳、更佳者爲8 〇莫耳％。 另外’視其所需亦可倂用二甘醇、丙二醇、丁二醇、己二 醇或1，4_環己烷二甲醇等。 -27- 201000311 芳香族二羧酸成分以對酞酸或異酞酸最佳。對全部二 羧酸成分而言，亦可加入10莫耳％以下之範圍的其他芳香 族二羧酸、特別是二苯基羧酸及2,6-萘二羧酸等之芳香族 二羧酸予以共聚合。 使用聚酯系樹脂作爲水系塗液時，以使用水溶性或可 水分散性聚酯系樹脂較佳，爲進行該水溶性化或水分散化 時，以使含磺酸鹽基之化合物、含羧酸鹽基之化合物予以 共聚合較佳。因此’除前述之二羧酸成分外，爲使聚酯具 有水分散性時，以使用1〜1 0莫耳％之範圍的5 ·磺基異酞 酸的鹼金屬鹽較佳，例如磺基對酞酸、5-磺基異酞酸、4_ 磺基萘異酞酸-2,7-二羧酸及5-(4-磺基苯氧基）異舦酸或其 驗金屬鹽。 (聚胺基甲酸酯系樹脂） 作爲聚胺基甲酸酯系樹脂之含有複合物所得的聚胺基 甲酸酯、以熱反應型聚胺基甲酸酯樹脂較佳，例如使末端 異氰酸酯基以活性氫基封端（以下簡稱爲嵌段）之水溶性或 水分散性聚胺基甲酸酯等。 異氰酸酯基之嵌段化劑，例如重亞硫酸鹽類、苯酚類、 醇類、內醯胺類、肟類及丙二酸二甲酯等之酯類、乙醯基 醋酸甲酯等之二酮類、毓醇類、尿素類、咪唑類、琥珀酸 醯亞胺等之醯亞胺類、二苯胺等之胺類、亞胺類、2-噚唑 烷等之胺基甲酸酯系等。水溶性或水分散性聚胺基甲酸 酯’以在分子中具有親水性基較佳。因此，以使用在使用 的分子內至少具有1個以上之活性氫原子的化合物中具有 親水性基，或前述的嵌段化劑具有親水性之化合物較佳。 在使用的分子內至少具有1個以上之活性氫原子的化合物 -28- 201000311 中具有親水性基之例，如牛磺酸、二羥甲基丙酸、具有羧 酸基或磺酸基之聚酯多醇、聚氧化伸烷基多醇等。而且’ 嵌段化劑具有親水性之化合物’例如重亞硫酸鹽類、及含 有磺酸基之苯酚類等。藉由製造薄膜時之乾燥製程或熱固 定處理製程，使上述之樹脂具有熱能量時，爲使嵌段化劑 自異氰酸酯基脫離時，使上述樹脂混入自己交聯的架構之 水分散性共聚合聚酯予以固定化，且同時與上述之樹脂末 端基等進行反應。特別是水溶性或水分散性聚胺基甲酸 酯，以使用嵌段化劑具有親水性之化合物者較佳。此等之 聚胺基甲酸酯，由於塗布液調整中的樹脂爲親水性，故耐 水性不佳，惟進行塗布、乾燥、熱固定、完成熱反應時， 由於胺基甲酸酯樹脂之親水基、即嵌段化劑被脫離，故可 製得耐水性良好的塗膜。 作爲上述聚胺基甲酸酯系樹脂中所使用的胺基甲酸酯 預聚物的化學組成，使（1 )在分子內至少具有2個活性氫原 子之分子量爲200〜20,000的化合物，（2)在分子內具有2 個以上異氰酸酯基之有機聚異氰酸酯，及視其所需（3)在分 子內至少具有2個活性氫原子之鏈伸長劑進行反應所得的 具有末端異氰酸酯基之化合物。 上述（1)的在分子內至少具有2個活性氫原子之分子量 爲200〜20,000的化合物，一般已知者爲含有在末端或分 子中具有2個以上羥基、羧基、胺基或锍基者，更佳的化 合物例如聚醚多醇及聚酯多醇等。 聚酯多醇可藉由使琥珀酸、己二酸、酞酸及馬來酸酐 等之多元飽和或不飽和羧酸、或該羧酸酐等、與乙二醇、 二甘醇、1,4-丁二醇、新戊二醇、1,6-己二醇及三羥甲基丙 -29- 201000311 烷等之多元飽和及不飽和醇類、較低的分子量之聚乙二醇 及聚丙二醇等之聚伸烷基醚二醇類、或此等醇類之混合物 進行縮合、製得。 另外，聚酯多醇例如可使用由內酯及羥基酸所得的聚 酯類、或在預先製造的聚酯類中使環氧乙烷或環氧丙烷等 加成的聚醚酯多醇類。 上述（2)之有機聚異氰酸酯，例如甲代亞苯基二異氰酸 酯之異構物類、4，4_二苯基甲烷二異氰酸酯等之芳香族二 異氰酸酯類、苯二甲基二異氰酸酯等之芳香族脂肪族二異 氰酸酯類、異佛爾酮二異氰酸酯及4,4-二環己基甲烷二異 氰酸酯等之脂環式二異氰酸酯類、六亞甲基二異氰酸酯及 2,2,4 -三甲基六亞甲基二異氰酸酯等之脂肪族二異氰酸酯 類、或使1種以上此等之化合物加成於三羥甲基丙烷等所 得的聚異氰酸酯類。 上述（3)之在分子內至少具有2個活性氫原子之鏈伸長 劑，例如乙二醇、二甘醇、1，4 - 丁二醇、及1,6 -己二醇等之 二醇類、丙三醇、三羥甲基丙烷 '及季戊四醇等之多元醇 類、乙二胺、六甲二胺、及吡畊等之二胺類、單乙醇胺及 二乙醇胺等之胺醇類、硫代二甘醇等之硫代二甘醇類、或 水。 使胺基甲酸酯預聚物合成時，通常使用上述（1)與上述 (2)、及視其所需上述（3) ’藉由一段式或多段式異氰酸酯聚 加成方法，在150 °C以下、較佳者爲7〇〜120 °C之溫度下進 行反應5分鐘〜數小時。對上述（1)及上述（3)之活性氫原子 而言，上述（2)之異氰酸酯基之比只要爲1以上時可自由選 擇，惟所得的胺基甲酸酯聚合物中必須殘存有游離的異氰 -30- 201000311 酸酯基。此外’游離的異氰酸酯基之含量’對所得的胺基 甲酸酯預聚物之全部質量而言’只要是1〇質量％以下即 可，就考慮經嵌段化後之胺基甲酸酯聚合物之水溶液的安 定性時，以7質量％以下較佳。 所得的上述胺基甲酸酯預聚物’較佳者係使用重亞硫 酸鹽進行末端異氰酸酯基的嵌段化。使胺基甲酸酯預聚物 與重亞硫酸鹽水溶液混合，在約5分鐘〜1小時中均句攪 拌且進行反應。反應溫度以6 0 °C以下較佳。然後，以水稀 , 釋反應混合物成適當濃度，形成熱反應型水溶性胺基甲酸 酯組成物。使用該組成物時，調製成適當的濃度及黏度， 通常在約8 0〜2 0 0 °C下進行加熱時，爲使嵌段化劑之重亞硫 酸鹽進行解離，爲使活性異氰酸酯基再生時，藉由在預聚 物之分子內或分子間引起聚加成反應，生成聚胺基甲酸酯 聚合物，或具有引起加成於其他的官能基之性質。 (丙烯酸系樹脂） 在複合物中使用丙烯酸系樹脂時之水分散性或水溶性 ， 丙烯酸樹脂，例如具有丙烯酸酯及/或甲基丙烯酸酯、或此 等與苯乙烯等之不飽和雙鍵、可與丙烯酸樹脂共聚合的脂 肪族化合物或芳香族化合物之共聚物。以作爲對硬塗布層 而言接著性優異的接著性改質層（A)作爲親水性優異的丙 儲酸-苯乙烯共聚合樹脂，以藉由乳化聚合之水分散性丙烯 酸-苯乙稀無規共聚合樹脂最佳。 另外’本發明由於藉由使水分散性丙烯酸-苯乙烯共聚 合樹脂更堅固地接著於基材薄膜上，對該共聚合樹脂以外 而言’倂用10〜90質量％共聚合聚酯系樹脂時爲有效。較 佳者使含水分散性磺酸金屬鹼之聚酯共聚合樹脂混合於水 31 - 201000311 . · 分散性丙烯酸-苯乙烯共聚合樹脂塗布液（A)中，適合塗布 於基材薄膜上。 構成含水分散性磺酸金屬鹼之聚酯共聚合樹脂的聚酯 之較佳例’如聚對酞酸乙二酯、聚伸乙基-2，6_萘二甲酸酯、 聚-1，4-環己烷二亞甲基對酞酸酯。該聚酯視其所需爲3〇 莫耳％以下、較佳者爲1 5莫耳％以下之上述酸成分或二醇 成分進行共聚合者，或與以該莫耳比由上述酸成分及二醇 成分所得的聚酯混合者。 另外，藉由在水分散性丙烯酸-苯乙烯共聚合樹脂中混 合有含水分散性磺酸金屬鹼之聚酯共聚合樹脂的塗布液（A) 中’添加水分散性或水溶性胺基甲酸酯樹脂（較佳者爲水分 散性、具有3個以上官能基之嵌段異氰酸酯樹脂），藉由水 分散性丙烯酸-苯乙烯共聚合樹脂與含水分散性磺酸金屬 鹼之聚酯共聚合樹脂的交聯反應，不會使與硬塗布層之接 著性降低’且可提高塗膜表面之耐黏連性。 使用上述之各樹脂時，藉由使含有上述成分之塗布液 (A)塗布於至少基材薄膜之一面上予以乾燥進行。例如水分 散性丙嫌酸-苯乙烯共聚合樹脂、較佳者丙烯酸酯及/或甲 基丙烯酸酯樹脂與苯乙烯之無規共聚合樹脂，及作爲水分 散性聚酯共聚合樹脂之含水分散性磺酸金屬鹼的聚酯共聚 合樹脂’以固體成份換算3 : 2〜1 : 1之質量比例所配合的含 樹脂之塗布液（A)時，固體成份濃度爲4〜15質量％，黏度 爲4〜60cps(藉由b型黏度計、在25cps下測定）。此外， 本視其所須爲使丙烯酸樹脂進行交聯時，可使用異氰 酸酯、環氧樹脂、噚唑啉、蜜胺等之交聯劑。 (b)溶劑 -32- 201000311 於本發明中，溶劑係廣泛包含不僅是可使樹脂溶解 者，且可使樹脂分散成粒子狀時所使用的分散媒。爲實施 本發明時，可使用有機溶劑、水性溶劑等之各種溶劑。 塗布液（A )所使用的溶劑，以使水、與乙醇、異丙醇、 苯甲醇等之醇類以佔全部塗布液（A)之比例爲10〜50質量 %範圍混合的混合液較佳，以2 0〜4 0質量％更佳。另外， 小於1 〇質量％時，亦可在可使醇類外之有機溶劑溶解的範 圍內進行混合。惟於塗布液（A)中，醇類與其他有機溶劑之 . 合計量以小於5 0質量％較佳。 有機溶劑之添加量對全部溶劑而言小於5 0質量％時， 具有於塗布乾燥時可提高乾燥性，且與水單獨相比時可提 高塗布接著性改質層（A)之外觀的優點。有機溶劑之添加 量，對全部溶劑而言爲50質量％以上時，溶劑之蒸發速度 變快，容易引起塗布中塗布液（A)之濃度變化。結果，由於 塗布液（A)之黏度上昇，塗布性降低，引起塗布膜之外觀不 佳情形。另外，因有機溶劑揮發，亦使火災等之危險性增 高。 (d) 界面活性劑之倂用 使上述之水性塗布液（A)塗布於熱塑性樹脂薄膜（基材 薄膜）表面時，爲提高對該薄膜之濕潤性，且使塗布液（A) 均勻地塗布時，一般而言以使用界面活性劑較佳。 界面活性劑只要是可得良好的塗布性即可，沒有特別 限定種類。於界面活性劑中，爲以微量添加得到良好的塗 布性時，以氟系界面活性劑較佳。添加量對塗布液（A)而言 以配合0.001〜0.018質量％較佳。 (e) 無機粒子 -33- 201000311 使用硬塗膜或該薄膜作爲要求高度透明性之光學機能 性薄膜時，基材薄膜之霧度以1 · 5 %以下較佳。霧度大於 1.5 %時’使薄膜使用於顯示器構件等時，由.於畫面之鮮明 度降低，故不爲企求。 爲使基材薄膜之霧度爲1.5 %以下時，本發明係在基材 薄膜中實質上不含粒子。基材薄膜中不含粒子時，爲改善 耐擦傷性或捲取成輥狀時或捲出時之加工處理性（平滑 性、行走性、黏連性、捲取時伴隨空氣之除去空氣性等）時， 在接著性改質層（A)中含有無機粒子。藉此，本發明之接著 性改質基材薄膜，可保持高的透明性、且可賦予平滑性、 捲取性 '耐擦傷性。 接著性改質層（A)中所含的無機粒子，例如碳酸鈣、磷 酸鈣、非晶性二氧化矽、結晶性玻璃纖維、高嶺土、滑石、 二氧化鈦、氧化鋁、二氧化矽-氧化鋁複合氧化物粒子、硫 酸鋇、氟化鈣、氟化鋰、沸石、硫化鉬、雲母等之無機粒 子、交聯聚苯乙烯粒子、交聯丙烯酸系樹脂粒子、交聯甲 基丙烯酸甲酯系粒子、苯并鳥糞胺•甲醛縮合物粒子、蜜 胺•甲醛縮合物粒子、聚四氟乙烯粒子等之耐熱性高分子 粒子。 於此等之粒子中，由於與樹脂成分之折射率較近，就 容易製得高透明之薄膜而言以二氧化矽粒子爲宜。 而且，粒子之形狀沒有特別的限制，就賦予易滑性而 固’以接近球狀之粒子較佳。 接著劑改質層（A)全量中佔有的粒子之含量，以20質 量％以下較佳，以1 5質量％以下更佳，以1 〇質量％以下最 佳。複合物中之粒子含量大於2 0質量。/〇時，透明性容易惡 -34- 201000311 化且薄膜之密接性亦容易變得不充分。另外，粒子之含量 的下限値，對複合物層而言以0 . 1質量。/。較佳，以1質量％ 更佳，以3質量％更佳。 此外，複合物中亦可含有2種以上平均粒徑不同的粒 子。而且，亦可含有同種粒子、平均粒徑不同者。於塗布 前述之塗布液（A)時，爲除去塗布液（A)中粒子之粗大凝聚 物時，以配置塗布前塗布液經精密過濾處理的濾材較佳。 另外，粒子爲1種時、或爲2種以上時作爲主體之粒 子（A)的平均粒徑以20〜150nm較佳，以40〜60nm更佳。 平均粒徑小於2 Onm時，不易得到充分的耐黏連性外，會有 耐擦傷性惡化的傾向。此外，使用2種以上之粒子時，添 加補助性平均粒徑大的粒子B時，粒子B之平均粒徑以1 60 〜lOOOnm較佳，以200〜800nm更佳。粒子B之平均粒徑 小於1 60nm時，會有耐擦傷性、平滑性、捲取性惡化的情 形。另外，粒子B之平均粒徑大於lOOOnm時，不僅粒子 變得容易脫落，且會有霧度提高的傾向。此外，粒子B(平 均粒徑：160nm〜lOOOnm)可藉由乾式法二氧化矽，使一次平 均粒徑爲40〜60nm之凝聚物不易脫落，故爲企求。此係推 測於製膜製程中，於塗布接著性改質層（A)後，藉由延伸製 程、熱固定製程可形成平坦、安定的形狀。另外，使用凝 聚狀態之平均粒徑與一次粒子之平均粒徑的比爲4倍以上 之粒子，就耐擦傷性而言較佳。 上述粒子之平均一次粒徑及平均粒徑之測定，藉由下 述方法進行。 使粒子以電子顯微鏡攝影，以1個最小粒子之大小爲 2〜5mm之倍率，測定300〜500個粒子之最大粒徑，且其 -35- 201000311 平均値作爲平均一次粒徑或平均粒徑。而且，求取接著性 改質基材薄膜之接著性改質層（A)中粒子之平均粒徑時，使 用透過型電子顯微鏡（TEM) ’以倍率12萬倍攝影接著性改 質層基材薄膜之截面，求取複合物之粒.子的最大粒徑。由 凝聚體所形成的粒子之平均粒徑，係使接著性改質基材薄 膜之接著性改質層（A)的截面使用光學顯微鏡、以倍率200 倍攝影3 00〜5 00個，測定其最大粒徑。 本發明之接著性改質層（A)，含有上述適當粒徑之無機 粒子’且在接著性改質層（A)表面上具有藉由無機粒子之突 起高度爲1 〇〇nm以上的表面突起。爲賦予接著性改質基材 薄膜具有適當的易滑性時’以非接觸性表面粗糙度計測定 時’以高度1 〇〇nm以上之表面突起的密度爲10個/mm2以 上、1 00 0個/mm2以下較佳。爲達i 〇個/mm2時，摩擦係數 變大，且大多產生形成光學缺點之要因的表面擦傷情形。 另外’大於1000個/mm2時，霧度變高，粒子之脫落發生 量增多，故不爲企求。 本發明中藉由在接著性改質層（A)中藉由無機粒子形 成高度爲lOOnm以上之表面突起，不僅可賦予易滑性，且 可於形成硬塗膜時形成在基材薄膜與硬塗布層之邊界範圍 上分散下述之有機-無機複合物的構造。藉由具有該分散的 有機-無機複合物’可賦予基材薄膜與硬塗布層之密接性。 藉由該有機-無機複合物以提高密接性時，可考慮爲藉由賦 予複合物具有一種底層機能、增加邊界層面之面積的效果 等。 此外’本發明之有機-無機複合物，具有優異的干涉班 減低效果’可考慮爲來自上述表面突起之有機-無機複合物 -36- 201000311 藉由其形狀以達成光散射效果，具有干涉斑減低效果。此 處所指的藉由突起之光散射效果，係推測爲具有藉由具二 軸延伸薄膜之面內光學各向異性（視觀察的角度而定，折射 率不同的性質），補助干涉斑之不均勻性的效果。因此，本 發明之接著性改質基材薄膜，可達成自硬塗布積層時之所 有角度觀察時之實用的干涉斑減低效果。 本發明中爲得優異的干涉斑減低效果時，以使部分粒 子適當地凝聚的狀態下均勻地予以分散較佳。藉此，即使 在硬塗布層與基材薄膜之折射率差爲0.02以上之較大値 時、自得光散射效果時之所有角度觀察時，仍可得實用的 干涉斑減低效果。製得適當的凝聚體之具體方法，如下所 述。 本發明中在接著性改質層（A)表面上所形成的上述高 度爲lOOnm以上之表面突起的山麓部之最大直徑平均値必 須爲1 Ο μ m以上。如下所述，本發明之接著性改質基材薄 膜，於積層硬塗布層時，使基材薄膜與硬塗布層直接積層 下具有極薄的接著性改質層（A)。如此使樹脂層厚度薄時， 形成山狀的表面突起之山麓部容易變小，粒子變得容易脫 落。因此，藉由使高度爲lOOnm以上之表面突起的山麓部 之最大直徑平均値爲ΙΟμιη以上，較佳者爲ll#m以上， 更佳者爲15//m以上，可使粒子之保持力變高。高度爲 lOOnm以上之表面塗起的最大直徑平均値爲以上 時，可抑制落粉情形、減少製程污染，同時可得安定的表 面摩擦特性。 此處，表面突起之山麓部，係爲表面突起之土台部分， 具體而言，係指以非接觸式表面粗糙度形態測定時，1視 -37- 201000311 野（測定範圍）內之平均高度以上的凸狀堆起的部分。例 如’使測定三次元形狀所得的結果以測定範圍內之平均高 度爲Onm、所定顏色區分的等高線表示方式進行觀察時， 以表面突起爲中心 '在同心圓上所形成的等高線之平均高 度以上的色區分部分爲山麓部。 山麓部之最大直徑’係指於觀察一個表面突起之截面 圖像時，1視野（測定範圍）內之平均高度線與截面圖交叉的 2點間距離之最大値。例如’以上等高線表示形態測定時， 爲使表面突起之頂點內封的平均高度之圓狀色區分部分之 最大直徑。具體而言’由等高線表示方式表示截面圖方式 時，在截面移動畫面上使游標之兩端通過表面突起之最大 高度的位置下，朝平均高度之圓狀色區分部分的長度方向 移動。讀取所得的表面突起之截面圖曲線與測定視野內之 平均高度線相交的2個焦點間之距離，作爲山麓部之最大 直徑。山麓部之最大直徑的平均値，以任意選擇2 0點以上 之高度爲l〇〇nm以上的表面突起，求取測定上述山麓部之 最大直徑時的平均値爲宜。而且，非接觸式表面粗糙度計， 可使用麥古羅馬布（譯音）公司製非接觸三次元形狀測定裝 置、或使用雷射之非接觸粗糙度測定器等。 於本發明中，高度爲lOOnm以上之表面塗起的山麓部 之最大直徑平均値爲l〇#m以上時，以形成適當的無機粒 子之凝聚體、與藉由塗布液（A)之樹脂被覆無機粒子爲宜。 於本發明中，爲形成適當粒子之凝聚體、及減低粒子及該 粒子之凝聚體的脫落情形時，於塗布液（A)調合階段中添加 粒子時，預先進行以粒子與親和性高的樹脂被覆時之前處 理爲宜。粒子與親和性高的樹脂，沒有特別的限制，以與 -38- 201000311 部分在接著性改質層（A)中所含的樹脂之主成分相同的樹 脂被覆’就親和性而言較佳，此外，被覆的樹脂中具有的 極性基之極性與被被覆的無機粒子之極性相反時，由於與 無機粒子之親和性高，可容易地更爲堅固地被被覆，故較 佳。另外，柔軟性愈高的樹脂，無機粒子之保持力更高。 具體而言’玻璃轉移溫度爲60 °C以下之具有柔軟性的樹 脂’就保持無機粒子而言較佳。被覆的樹脂爲富含柔軟性 的聚胺基甲酸酯系樹脂，粒子爲二氧化矽粒子，係爲較佳 的實施形態之一例。其中’被覆的樹脂與無機粒子之關係， 爲電氣性陰陽相反的組合，係爲更佳的實施形態。藉由該 前處理，考慮係於使塗布液（A)進行塗布乾燥時，在上述之 無機粒子周圍上聚集多數的該樹脂成分，形成本發明規定 的表面突起之山麓部，可減低無機粒子之脫落情形。於下 述中’具體說明有關該粒子之前處理方法，只要是可在粒 子上被覆粒子與親和性高的樹脂之方法即可，沒有特別的 限制。 首先’使無機粒子以0.0 1質量％以上、小於5質量％ 之濃度之分散液預先添加於含有無機粒子與親和性高的樹 脂之水、或有機溶劑或此等之混合溶液中。小於〇. 〇丨質量 %時’會有無法製得以充分量被覆的無機粒子。爲5質量％ 以上時’容易產生很多的必要量以上之粗大凝聚體，故不 爲企求。 親和性高的樹脂濃度以〇· 1質量％以上、小於25質量 %較佳。小於0 · 1質量％時，無法得到充分的被覆效果。爲 2 5質量％以上時，容易產生很多的必要量以上之粗大凝聚 體’故不爲企求。 -39- 201000311 然後’使所得的分散液在2 0 °C以上、小於5 0。(^之條件 下進行攪拌’且在無機粒子或無機粒子之凝聚體上被覆無 機粒子與親和性筒的樹脂。小於2 0 t：時，於被覆時極爲耗 時，大於50 °C時’樹脂惡化（變色），故不爲企求。攪拌機 例如粉體溶解機（T.K.均混器Μ型），分散條件係以對10kg 分散液而言’回轉數爲5000rpm以上、較佳係i〇〇〇〇rpm以 上，攪拌時間爲1小時以上、較佳係小於3小時。小於1 小時的話，無法得到充分的被覆效果，此外，爲3小時以 上時，即使分散時效果仍然沒有很大的變化。 (f)交聯劑 如手機、PDA、手提型電腦之資訊終端機，在屋外使 用的機會增加。另外，衛星導航系統等所使用的觸控板， 在夏天高溫下之車內所使用的材料亦增加。而且，即使在 該高溫、高濕之嚴苛環境下品質變化少之硬塗膜、即耐濕 熱接著性優異的薄膜，在該用途中極爲企求。 該用途中使用本發明之硬塗膜時，爲提高耐濕熱性 時，可藉由在塗布液（A)中添加交聯劑，再進行熱處理，在 樹脂中具有交聯構造。交聯劑至少使用—種選自環氧系交 聯劑、蜜胺系交聯劑、噚唑啉系交聯劑、異氰酸酯系交聯 劑。交聯劑可考慮與塗布液（A)中使用的共聚合聚酯樹脂之 親和性、及耐濕熱接著性予以選擇。而且，由於過度的交 聯時會損害適當的膨脹性，故不爲企求。 使用上述交聯劑時，對複合物之共聚合聚酯樹脂與交 聯劑之合計量（1 0 0質量％)而言，較佳者爲5〜4 0質量％， 更佳者爲1 〇〜3 0質量％。交聯劑之含量大於4 0質量％時， 複合物變脆，且於形成由丙烯酸酯系樹脂所成的硬塗布層 -40- 201000311 或擴散層等之機能層後的加工製程中，無法得到充分的可 忍耐高速切斷之接著性。另外，交聯劑之含量小於5質量 %時，不易得到近年來所要求的耐久性。而且，於塗布液（A) 中，爲促進交聯時，視其所需亦可添加觸媒。 (3)塗布製程 塗布上述塗布液（A)之製程，以在該薄膜之製程中進行 塗布的線上塗布法較佳。更佳者爲塗布於結晶配向完成前 之基材薄膜上。塗布液（A)中之固形成分濃度以2質量％以 β 下較佳，更佳者爲1質量％以下。固形成分濃度之下限値 以〇 . 1質量％較佳，更佳者爲0.3質量％。塗布有該塗布液 (Α)之薄膜，爲進行配向及熱固定處理時導入拉幅器中，然 後進行加熱，藉由熱交聯反應形成安定的被膜，形成接著 性改質基材薄膜。 未乾燥時之塗布量（以下簡稱爲濕式塗布量），以2g/m2 以上、小於10 g/m2較佳。濕式塗布量小於2 g/m2時，得 到設計之乾式塗布量（接著性改質層（A)之塗布量）時，必須 使塗布液（A)之固形成分濃度提高。塗布液（A)之固形成分 i 濃度提高時，由於塗布液（A)之黏度變高，容易產生條狀塗 布斑。另外，濕式塗布量爲1 0 g/m2以上時，容易受到乾 燥爐內之乾燥風的影響，容易產生塗布斑。而且，爲防止 因塵埃附著之缺點時，以在清潔度爲等級5000以下之清潔 環境下進行塗布塗布液（A)較佳。 本發明之接著性改質層（A)之塗布量（乾燥後之最終塗 布量），必須爲3〜12 g/m2。塗布量過多時，積層塗布層時， 爲在折射率高的塗布層與基材薄膜之間形成折射率低、獨 立的接著性改質層（A)時，干涉斑容易變得顯著。塗布量過 -41 - 201000311 少時’不僅容易產生無機粒子脫落的情形，且無法得到實 用的接著性。 (3)塗布層（B) 本發明之較佳實施形態，係可在另一面上設置含有聚 酯系樹脂與鈦化合物之塗布層（B)。此時，積層構造係爲塗 布層（B)/基材薄膜/接著性改質層（A)之順序。 塗布層（B)以藉由在基材薄膜上塗布塗布液（B)，再予 以乾燥製得較佳。如上所述，爲製得該塗布層（B)時塗布的 塗布液定義爲「塗布液（B)」。於本發明中，爲形成塗布層 (B)時所使用的塗布液（B)，係爲由聚酯系樹脂、特別是水 性聚酯樹脂、與水溶性鈦化合物、與水系溶劑爲主所形成 的水系塗布液。塗布液（B)中所含的鈦化合物，可與水性聚 酯樹脂進行交聯反應，藉由該交聯反應生產更爲均勻的膜 較佳。該交聯反應藉由使基材薄膜延伸時，藉由熱予以促 進，結果會有上述鈦化合物因熱分解的情形，並不一定必 須以與塗布液中相同的狀態包含於所得的塗布層（B)中。 塗布層（B)之折射率，藉由鈦化合物之組成比變大，可 較水性聚酯樹脂單獨時更高。藉此，即使積層以下述丙烯 酸系樹脂爲主體之黏著劑層，仍可抑制干涉斑產生。爲提 高塗布層（B)之折射率時，亦可藉由含有金屬微粒子予以達 成，惟藉由含有金屬微粒子，會使塗布層之延伸性及硬塗 布層與基材薄膜間之密接性降低。 本發明使用的水性聚酯樹脂，亦可在其分子鏈中導入 羥或羧基等之活性部位，特別是即使沒有導入時，由於酯 鍵結部位引起可逆反應，且在任意位置引起交聯反應，結 果可製得緻密的膜。 -42- 201000311 本發明使用的鈦化合物’由於作爲水性塗布液使用， 以水溶性鈦化合物爲宜。該水溶性鈦化合物，可使用水溶 性欽螯合物化合物、水溶性醯化鈦化合物、水溶性之锆蝥 合物化合物、或水溶性醯化鉻化合物。 水溶性鈦螯合物化合物’例如二異丙氧基雙（乙醯基乙 酸）鈦、異丙氧基（2-乙基-1，3-己烷二油酸）鈦、二異丙氧 基雙（三乙醇胺）鈦、二-正丁氧基雙（三乙醇胺）鈦、羥 基雙（乳酸）鈦、羥基雙（乳酸）鈦之銨鹽、鈦過氧化檸 檬酸銨鹽等。 另外’水溶性之醯化鈦化合物例如有雙（乙二酸單銨） 羰基鈦等’而且，水溶性鉻化合物例如有四乙醯基乙酸锆 鹽、乙酸鉻鹽等。 於此等之中’就塗布液之pH値調整、塗布層之折射率 調整及密接性而言，以倂用乳酸鈦化合物及三乙醇胺鈦化 合物較佳。 塗布層（B)之水性聚酯樹脂，與基材薄膜之密接性有 關。因此，以塗布層中所含的水性聚酯樹脂之質量爲（a ) 、以鈦化合物之質量爲（d)時，（a) / (d)之値以50/50 以上較佳。前述値爲5 0/5 0以上時，可提高作爲光學用之必 要透明性，且於塗布層上所形成的黏合層之密接性良好。 而且，（a )/( d )之値以80/20以下較佳，此時，藉由前 述鈦化合物充分地交聯，可提高折射率，因此，可提高在 高溫高濕下之密接性（耐濕熱性）、且在螢光燈下之彩虹狀 色彩之抑制效果變得充分。 上述之鈦化合物，係爲乳酸鈦化合物及三乙醇胺鈦化 合物，爲本發明之較佳的一實施形態’以乳酸鈦化合物之 -43 - 201000311 質量爲（b)、及以三乙醇胺鈦化合物之質量爲（c)時，以 上述（d)與〔（b) + (c)〕相同者較佳。此時，上述（b) 及（C)之關係’以（b) / (C)之値爲35/65〜65/35較 佳。在前述範圍内時’塗布液（B )之p Η値大約變爲中性 (pH値爲ό〜8)，結果，在該塗布層上積層異氰酸酯硬化型 丙烯酸樹脂系黏合劑時’伴隨塗布層與黏合劑層間之密接 性提高時，可減低在黏合劑層側所產生的干涉斑。 在塗布層（Β )中含有乳酸鈦化合物及三乙醇胺鈦化合 物兩者在技術上的意義，如下所述。 僅前述鈦化合物1種時，會有塗布液（Β)之pH値大爲 偏向於酸性、或鹼性的傾向。由大爲偏向於鹼性之塗布液 (B)所得的塗布層（B)上積層異氰酸酯硬化型丙烯酸樹 脂系黏合劑時，在黏合劑層之厚度方向容易產生硬化斑， 結果，貼附於顯示器前面時，會降低貼附不佳時的再作業 性。再作業性（re work性）降低時，會產生於剝離時黏著 劑層自顯示器前面開始殘存量變多的問題。另外，由大爲 偏向於酸性之塗布液（B)所得的塗布層（B)上積層異氰 酸酯硬化型丙烯酸樹脂系接著劑時，容易引起黏合劑之硬 化阻害情形，相同地前述之再作業性降低。僅爲前述鈦化 合物1種時，塗布液（B)之pH値爲酸性、或鹼性。爲調整 塗布液之pH値時，爲酸性時可藉由添加胺、銨、氫氧化鈉 等之鹼性化合物，爲鹼性時可藉由添加羧酸、鹽酸、磺酸 等之酸性化合物，以調整pH値，此時，塗布層（B )中鈦 化合物與水性聚酯樹脂之相溶性降低，結果，塗膜變得不 均勻，與黏合層之彩虹狀色彩的抑制效果降低，且密接性 降低，故不適合於本發明之用途。 -44 - 201000311 於本說明書中，在經加熱的丁基溶纖劑中使聚酯樹脂 予以可塑化後，再加入溫水時，該聚酯樹脂達到分散狀態 時，該聚酯樹脂變成水性聚酯樹脂。使聚酯樹脂具有水性 時，使羥基、羧基、磺酸基、磷酸基、醚基等之親水性基 導入聚酯樹脂之分子鏈中，係爲重要。於前述之親水性基 中，就塗膜物性及密接性而言以磺酸基較佳。 在聚酯中導入磺酸基時，磺酸化合物於聚酯之全部酸 成分中、以1〜1 0莫耳％更佳。磺酸基量小於1莫耳％時，由 於聚酯樹脂變得不具水性，與水溶性之鈦化合物的相溶性 亦降低，不易得到均勻且透明的塗布層。而且，磺酸基量 大於1 0莫耳％時，高溫高濕下之密接性（耐濕熱性）容易 惡化。 此外，水性聚酯樹脂以玻璃轉移溫度爲40°c以上較佳 。因此，水性聚酯樹脂之酸成分以對酞酸、異酞酸、萘二 羧酸等之芳香族系爲主成分較佳。而且，二醇成分以乙二 醇、丙二醇、1,4-丁二醇、新戊二醇等之碳數較少的二醇 、或雙酚A之氧化乙烯加成物等芳香族系較佳。另外，聚 酯樹脂之原料亦可在不會降低薄膜物性之範圍內，使用聯 苯等之剛直成分、或具有溴、硫等折射率高的原子之二羧 酸成分或二醇成分。水性聚酯樹脂之玻璃轉移溫度爲40 °C 以上時，在高溫高濕下之密接性（耐濕熱性）充分。此外 ，爲使聚酯樹脂之折射率提高時，塗布層（B)之折射率亦 隨之提高。結果，可容易充分地抑制在螢光燈下之彩虹狀 色彩。 在塗布層（B)中亦包含乳酸鈦化合物與三乙醇胺鈦化 合物。水溶性乳酸鈦化合物之典型例，如雙（乳酸）氧化鈦 -45 - 201000311 。另外’水溶性三乙醇胺鈦化合物之典型例如二異丙氧基 雙（三乙醇胺）鈦。 塗布層（B)中，在不會影響本發明效果的範圍內，除上 述之主成分以外的樹脂、亦可倂用例如丙烯酸樹脂、聚胺 基甲酸酯樹脂、聚酯樹脂、醇酸樹脂、聚乙烯醇等之乙烯 樹脂。而且’在不會影響本發明效果之範圍內亦可倂用交 聯劑’沒有特別的限制。可使用的交聯劑例如尿素、蜜胺、 苯并鳥糞胺等與甲醒之加成物、此等加成物與碳數爲1〜6 之醇所形成的烷醚化合物等之胺基樹脂、多官能性環氧化 合物、多官能性異氰酸酯化合物、嵌段異氰酸酯化合物、 多官能性氮雜環丙烷化合物、噚唑啉化合物等。 於塗布層（B)中以含有二氧化矽粒子較佳。藉由二氧化 矽之存在，可提高耐嵌段性或加工處理性。二氧化矽粒子 可適當使用市售的膠體二氧化矽粒子等。塗布層（B)中所佔 的二氧化矽粒子之含量，以0 · 1〜2 0重量％較佳。 使上述水系塗布液（B)塗布於聚酯薄膜表面時，爲提高 對薄膜之濕潤性、均勻地塗布塗布液（B)時，以適量添加習 知的陰離子系界面活性劑或非離子系界面活性劑較佳。 此外，於水系塗布液（B)中，爲使薄膜具有加工處理 性、抗靜電性、抗菌性等其他的機能性時，可含有無機及/ 或耐熱性高分子粒子、抗靜電劑、紫外線吸收劑、有機潤 滑劑、抗菌劑、光氧化觸媒等之添加劑。 塗布液（B)中使用的溶劑，可在對全部塗布液（B)而言 以小於5 0質量％之範圍內混合水以外之乙醇、異丙醇、苯 甲醇等之醇類。另外’小於10質量％時，亦可在可溶解醇 類以外之有機溶劑的範圍內混合。惟塗布液（B)中之醇類與 -46 - 201000311 其他有機溶劑之合計量，以小於5 0質量％較佳。 於本發明中，最終所得的塗布層（Β)之塗布量，可視使 用的黏合劑層之折射率而定予以調整，具體而言以〇.〇2〜 0.5g/m2 較佳，以 0.05 〜0.3g/m2 較佳，以 〇.〇7 〜〇.2g/m2 較佳。塗布層（B)之塗布量爲0.02 g/m2以上時，對接著性 而言效果顯著，容易使螢光燈下彩虹狀色彩之抑制效果變 得充分。另外，塗布量爲0.5 g/m2以下時，螢光燈下之彩 虹狀色彩的抑制效果容易變得充分。 , (4)硬塗膜 (a)硬塗布層 構成硬塗布層之硬化型樹脂，以電離放射線硬化型樹 脂較佳。電離放射線硬化型樹脂例如下述之樹脂。 於電離放射線硬化型樹脂中，以具有丙烯酸系官能基 之樹脂較佳，更佳者爲聚酯丙烯酸酯、或胺基甲酸酯丙烯 酸酯。聚酯丙烯酸酯係由聚酯系多醇之低聚物的丙烯酸酯 或甲基丙烯酸酯（以下，丙烯酸酯及/或甲基丙烯酸酯記載 γ 爲（甲基）丙烯酸酯）、或其混合物所構成。另外，胺基甲酸 \ , 酯（甲基）丙烯酸酯係使由多醇化合物與二異氰酸酯化合物 所形成的低聚物予以（甲基）丙烯酸酯化者所構成。 構成（甲基）丙烯酸酯之單體，例如（甲基）丙烯酸甲酯、 (甲基）丙烯酸乙酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸2-乙基己基酯、（甲基）丙烯酸甲氧基乙基酯、（甲基）丙烯酸丁 氧基乙基酯、（甲基）丙烯酸苯基酯。 此外，必須提高硬塗布層之硬度時，以倂用多官能單 體較佳。多官能單體例如三羥甲基丙烷三（甲基）丙烯酸 酯、己二醇（甲基）丙烯酸酯、三丙二醇二（甲基）丙烯酸酯、 -47- 201000311 二甘醇二（甲基）丙烯酸酯、季戊四醇三（甲基）丙烯酸酯、二 季戊四醇六（甲基）丙烯酸酯、1，6 -己二醇二（甲基）丙烯酸 酯、新戊二醇二（甲基）丙烯酸酯。 聚酯系多醇之低聚物例如己二酸與二醇（乙二醇、聚乙 二醇、丙二醇、聚丙二醇、丁二醇、聚丁二醇等）或三醇（丙 三醇、三羥甲基丙烷等）、癸酸與二醇或三醇之縮合生成物 的聚己二酸酯多醇、或聚癸二酸酯多醇。而且，部分或全 部上述脂肪族二羧酸可以其他有機酸取代。例如，異酞酸、 對酞酸、或酞酸酐可使用作爲提高硬塗布層之硬度的成分。 在基材薄膜上形成硬塗布層時’爲提高水平性時，視 其所需可使用稀釋劑予以稀釋。稀釋劑例如苯、甲苯、二 甲苯等之芳香族烴、己烷、庚烷、辛烷、壬烷、癸烷等之 脂肪族烴、甲基乙酮、二乙酮、二異丙酮等之酮等。稀釋 劑之配合量在適當的黏度下予以適當選擇。 硬塗布層中所含的無機微粒子，例如非晶性二氧化 矽、結晶性玻璃塡充劑、二氧化矽、氧化锆、二氧化鈦、 氧化鋁、等之無機氧化物、二氧化矽-氧化鋁複合氧化物粒 子、碳酸鎂、氫氧化鋁、硫酸鋇、碳酸鈣、磷酸鈣、高嶺 土、滑石、硫酸鋇、氟化鈣、氟化鋰、沸石、硫化鉬、雲 母。 本發明之硬塗膜，以設置折射率爲1.60〜1.65之硬塗 布層爲宜。在硬塗布層表面上積層筒折射率層/低折射率 層、或高折射率層/中折射率層/低折射率層所構成的抗反 射層時，藉由使硬塗布層予以高折射率化，可自抗反射層 省略高折射率層。結果，可減低成本。爲提高硬塗布層之 折射率時，在硬塗布層中含有折射率高的無機微粒子係爲 -48 - 201000311 有效。折射率高的無機微粒子，例如氧化鉻、氧化鈦。 此外，無機微粒子之含量大於80質量％時，會有透明 性降低的傾向。而且，無機微粒子之平均粒徑，就易滑性、 透明性而言以5〜1 0 0 n m較佳。 該含有無機微粒子之高折射率硬塗布劑，可取自市售 品。例如 JSR股份有限公司製之紫外線硬化型樹脂 (Desolite); Z7400B、Z7410B)。而且，在丙烯酸系樹脂中 適量添加折射率高的無機微粒子，且使折射率調整爲1.60 〜1.65之範圍。 電離放射線硬化型樹脂，可藉由紫外線或電子線照射 予以硬化。照射紫外線時，係使用超高壓水銀燈、高壓水 銀燈、低壓水銀燈、碳弧、金屬鹵化物燈等，在1 0 〇〜 400 nm、較佳係 200〜400 nm之波長範圍、以 1〇〇〜 3 000m J/m2之能量照射紫外線。另外，照射電子線時，使 用掃描型或簾幕型電子線加速器，具有加速電壓100 OkeV 以下（較佳者爲1〇〇〜3 00keV)之能量，且照射ΙΟΟηιη以下 波長範圍之電子線。 硬塗布層之厚度，在0.1〜30#m之範圍，視其用途予 以決定。更佳者爲1〜15/zm。硬塗布層之厚度在上述範圍 內時，硬塗布層之表面硬度高，不易受到擦傷。另外，硬 塗布層不易變脆，於使硬塗膜彎曲時硬塗布層不易產生破 裂情形。 其次，本發明可在與本發明之硬塗膜的硬塗布層相反 面或其上，積層其他的光學機能層，有下述2種實施形態。 (A)在與硬塗布層相反面上至少積層一層選自硬塗布 層、光擴散層、菱形狀透鏡層、電磁波吸收層、近紅線遮 -49- 201000311 斷層，透明導電層之光學機能層的光學機能性薄膜。 (B)在硬塗布層上積層抗反射層或防污層之光學機能 性薄膜。 (b)有機-無機複合物 在本發明之接著性改質基材薄膜的接著性改質層（A) 表面上積層硬塗布層時，硬塗布層直接積層於基材薄膜 上，在基材薄膜與硬塗布層之邊界範圍上分散有機-無機複 合物（以下記載爲「複合物」）。有機-無機複合物具有在至 少含一種選自聚酯樹脂、胺基甲酸酯樹脂、丙烯酸樹脂中 包埋無機粒子之構造。 上述複合物例如作成本發明之硬塗膜的超薄切片，藉 由使用透過型電子顯微鏡（TEM)，以倍率5萬倍〜20萬倍 進行觀察’可確認獨立存在於基材薄膜與硬塗布層之邊界 範圍。上述複合物具有使無機粒子包埋於至少一種選自聚 酯樹脂、胺基甲酸酯樹脂、丙烯酸樹脂之樹脂組成物中的 構造。TEM觀察影像，視電子密度而定可觀察對比之濃淡 情形。無機粒子係對電子密度高、濃而言，選自聚酯樹脂、 胺基甲酸酯樹脂、丙烯酸樹脂之樹脂組成物，係電子密度 低、淡。因此，上述複合物係爲與基材薄膜同等、或較基 材薄膜更淡·的樹脂組成物包圍於較濃的無機粒子周圍之構 造。本發明中一個獨立的複合物，以含有一個無機粒子、 或一個無機粒子凝聚體所成者爲較佳的形態。 使有機-無機複合物中所含的至少1種選自聚酯樹脂、 胺基甲酸酯樹脂、丙烯酸樹脂之樹脂組成物，藉由透過型 電子顯微鏡（TEM)觀察時，以進行釕染色、餓染色、磷鎢酸 染色等之染色處理較佳。特別是釕染色可以聚酯樹脂、胺 -50- 201000311 基甲酸酯樹脂適合地染色。有機-無機複合物之各構成，可 藉由上述染色之染色像予以判斷。另外，亦可藉由局部元 素分析（SEM/EDX等），判斷有機-無機複合物之各構成。而 且，形成硬塗膜後，構成接著性改質層（A)之樹脂組成、即 構成有機-無機複合物之樹脂組成物，例如使接著性改質基 材薄膜之塗布表面、或硬塗布層/基材薄膜界面藉由紅外線 分光進行分析、予以特定。 上述複合物存在於基材薄膜與硬塗布層之邊界範圍。 ,, 邊界範圍係指基材薄膜與硬塗布層之界面附近。使本發明 之硬塗膜藉由TE Μ觀察時，在基材薄膜與硬塗布層相接的 邊界上可觀察到上述複合物。上述各複合物以連接基材薄 膜與硬塗布層等兩方、存在較佳。 上述複合物分散於基材薄膜與硬塗布層之邊界範圍。 複合物分散係指使本發明之硬塗膜藉由ΤΕΜ觀察時，數個 複合物沒有全部聯接一起，爲分散存在之意。換言之，無 機粒子包圍於樹脂組成物所成的複合物，係個別獨立存 在，在基材薄膜與硬塗布層之間數個無機粒子沒有藉由樹 脂組成物連續連接的構造。連續連接的構造係指基材薄膜 與硬塗布層之邊界上有作爲樹脂組成物之有機物的狀態。 本發明使用倍率5萬倍〜20萬倍之透過型電子顯微鏡（TEM) 觀察時，在硬塗膜之基材薄膜與硬塗布層之邊界上，沒有 觀察到由至少一種選自有機-無機複合物之構成成分的聚 酯樹脂、胺基甲酸酯樹脂、丙烯酸樹脂所成的樹脂之樹脂 組成物層，係爲重要。此處，沒有觀察到樹脂組成物層， 係指使用倍率5萬倍〜20萬倍之透過型電子顯微鏡（TEM) 觀察時，邊界範圍之樹脂層的厚度爲觀察之臨界値以下， -51 - 201000311 與沒有設置樹脂組成物層之基材薄膜同等的狀態。具體而 言，硬塗布層與基材層之邊界爲l〇nm以下，較佳者爲5nm 以以下。此係因藉由染色時之運作等，在硬塗布層與基材 層之邊界有染色劑沉澱之故。有關邊界範圍內鄰接的2個 複合物間之距離，沒有特別的限制，以具有1 0 0〜1 0 0 0 nm 之距離較佳。 該複合物之較佳製法，如下所述，例如在含有構成複 合物之樹脂與無機粒子的塗布液（A)，在基材薄膜上極薄地 塗布•乾燥，然後，使爲形成硬塗布層時之硬化型樹脂所 成的硬塗布劑進行塗布•乾燥的方法。藉由該製法，構成 複合物之樹脂至少部分藉由爲形成硬塗布層時之硬塗布劑 予以膨脹，然後，與硬塗布層之樹脂一體化。結果，在沒 有上述無機粒子存在的範圍內，藉由TEM觀察沒有塗布層 存在的程度下，與硬塗布層之樹脂一體化。換言之，使用 倍率5萬倍〜20萬倍之透過型電子顯微鏡（TEM)觀察時， 邊界範圍之樹脂組成物層的厚度爲觀察臨界値以下。 此外，藉由在上述無機粒子之周圍殘存構成複合物之 樹脂，結果，形成在基材薄膜與硬塗布層之間包埋複合物 的構造。習知技術對爲使基材薄膜與硬塗布層接著時所設 置的獨立「層」而言，本發明改變其全部的想法，藉由使 複合物分散，使基材薄膜與硬塗布層接著。藉此，可維持 充分的接著性，且可顯著減低干涉斑。 (c)黏合劑層 本發明之較佳實施形態，係爲在塗布層（B)表面上另外 積層有黏合劑層之硬塗膜。本發明所使用的黏合劑，就密 接性及減低干涉斑而言，以丙烯酸系聚合物爲主成分、且 -52- 201000311 添加異氰酸酯系硬化劑爲宜。藉由設置該黏合劑層，可適 合作爲與各種構件一體化的積層薄膜。另外，於黏合劑層 中，視其所需亦可添加近紅外線吸收劑等之色素。有關該 丙烯酸系黏合劑層中含有的丙烯酸系樹脂，例如以下述形 態較佳。 上述丙烯酸系樹脂係以（甲基）丙烯酸烷酯之均聚物、 或其共聚物較佳。作爲上述丙烯酸系樹脂之單體所使用的 丙烯酸酯，例如具有碳數1〜12之烷基者，具體而言，如（甲 基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸正丙酯、 (甲基）丙烯酸異丙酯、（甲基）丙烯酸正丁酯、（甲基）丙烯酸 異丁酯、（甲基）丙烯酸戊酯、（甲基）丙烯酸環己酯、（甲基） 丙烯酸2-乙基己酯、（甲基）丙烯酸正辛酯、（甲基）丙烯酸異 辛酯、（甲基）丙烯酸月桂酯等。此等可單獨或2種以上組 合使用。 除上述（甲基）丙烯酸酯外，亦可含有具有其他不飽和 雙鍵之單體，例如烯烴系、乙烯系（除丙烯酸系）等之單體（如 含有乙烯、醋酸乙烯酯、苯乙烯等）作爲共聚合成分。此等 、' 具有其他不飽和雙鍵之單體，可含有20重量％以下之範圍。 而且，以於（甲基）丙烯酸酯中使上述（甲基）丙烯酸酯與 具有官能基之單體共存較佳。藉此，可使上述（甲基）丙烯 酸酯與具有官能基之單體共聚合，製得具有官能基之（甲基） 丙烯酸系樹脂。藉由在（甲基）丙烯酸系樹脂中具有官能基 的單體，可使該官能基與下述之交聯劑進行反應，使（甲基） 丙烯酸系樹脂予以交聯。藉由該交聯可防止黏合劑層與基 材薄膜產生剝離情形，且提高黏合劑層之機械強度。上述 具有官能基之單體，例如（甲基）丙烯酸、馬來酸、衣康酸、 -53- 201000311 檸康酸等之含羧基的脂肪族不飽和羧酸。該脂肪族不飽和 羧酸，在（甲基）丙烯酸系樹脂中較佳者爲5重量％以下、更 佳爲3 . 5重量％以下之範圍。大於5重量％時’於剝離後容 易產生殘糊情形。具有其他官能基之單體’例如（甲基）丙 烯酸-2-羥基乙酯、（甲基）丙烯酸-2-羥基丙酯、2-羥基乙烯 醚等之具有羥基者、Ν,Ν-二甲基胺基乙基（甲基）丙烯酸 酯、胺基乙基（甲基）丙烯酸酯、二甲基胺基丙基（甲基）丙烯 酸酯等之具有胺基者、丙烯酸環氧丙酯、甲基丙烯酸環氧 丙酯等之具有環氧基者、以及丙烯腈及丙烯醯胺等，此等 可單獨或2種以上組合使用。具有官能基之單體的全含 量，在（甲基）丙烯酸系樹脂中以〇·1〜20重量％之範圍較 佳。其中，特別是使用丙烯醯胺等具有醯胺基之單體，可 防止黏合劑之剝離或發泡情形，故較佳。 含有上述具有官能基之（甲基）丙烯酸系樹脂作爲黏合 劑層之構成成分時’以在黏合劑層中含有交聯劑較佳。交 聯劑例如多官能異氰酸醋系交聯劑之甲代亞苯基二異氰酸 酯、六亞甲基二異氰酸酯、三羥甲基丙烷改性甲代亞苯基 二異氰酸醋等’多官能環氧基之乙二醇二環氧丙酸、丙二 醇環氧丙醚等、多官能氮雜環丙烷系交聯劑之Ν,Ν_六亞甲 基-1,6-雙（1-氮雜環丙烷羧基醯胺）、三羥甲基丙垸氮雜 環丙烷基丙酸酯等、金屬螯合物系交聯劑之鋁的乙醯基丙 酮錯合物、過氧化物之苯甲醯基過氧化物、蜜胺系交聯劑 等。此等可單獨或2種以上組合使用。其含量爲〇〇1〜5 重量％之範圍較佳。 於本發明中，（甲基）丙烯酸系樹脂之重量平均分子量 以20萬〜200萬者較佳、更佳者爲5〇萬〜200萬者、最佳 -54- 201000311 者爲70萬〜150萬者。而且，重量平均分子量係爲以凝膠 滲透色層分析法測定的結果。 而且’於上述之黏合劑層中，亦可含有可塑劑、矽烷 偶合劑等之黏合特性改質劑、顏料用等之著色劑、二氧化 矽、二氧化鈦、氧化鋁、金屬粉、金屬氧化物粉等之無機 塡充物、樹脂微粒子等，視各目的而定適量使用。所形成 的黏合劑層之膜厚，適當地設定於5〜50;zm之範圍。 【實施例】 其次’有關本發明之接著性改質基材薄膜及硬塗膜，使 用實施例與比較例說明，惟本發明當然不受此等之實施例 所限制。另外，實施例中記載的接著性改質基材薄膜、硬 塗膜之物性或特性，使用下述之方法予以評估。 (1)與硬塗布層之接著性 在貼附有兩面膠帶之厚度5min的玻璃板上，塗布有實 施例及比較例所得的硬塗布劑（A)之硬塗膜的硬塗布層爲 表側’貼附於相反面上。然後，貫通硬塗布層，到達基材 薄膜之1 〇〇個格子狀切傷，使用間隙間隔2mm之切斷導束 予以形成。然後，將膠帶（Nichiban公司製、405號；24mm 寬度）貼附於格子狀切傷面上。於貼附時以橡皮擦押除殘留 於界面的空氣，予以完全接著後，使膠帶垂直剝離，藉由 目視由下述式求取接著性。而且，在1個格子內部分被剝 離者亦包含於剝離的個數中。 接著性（％ ) = ( 1 一格子之剝離個數/ 1 〇 〇個）X 1 〇 〇 接著性（％)爲90〜100%: ◎201000311 VI. Description of the Invention: [Technical Field] The present invention relates to an adhesive modified base film, in particular, an adhesive modified base of a base film suitable for a hard coat film mainly used in a member for display. Film, and its hard coating. More specifically, in the case of a base film which is a hard coat film having an adhesive layer, it is possible to suppress a rainbow-like color and an adhesive modified base film excellent in adhesion between the hard coat layer and the base film. And its hard coating film. [Prior Art] Generally, a hard coat film used in a member such as a liquid crystal display (LCD) or a plasma display panel (PDP) has a thermoplastic resin film as a base film and has a hard coat film. The layer is formed by a laminated film. In order to express the optical function, the display member described above is provided with a functional layer containing various pigments. For example, the PDP is a near-infrared shielding layer containing a near-infrared absorbing agent such as a diimonium compound or a fluorine-containing phthalocyanine compound; the LCD is a PVA layer containing an iodine dye; and the electronic paper is a pigment layer containing a color ink. These functional pigments are generally decomposed by the ultraviolet rays contained in the sunlight, and there is a problem that the weather resistance is poor and the performance is lowered due to long-term use. Therefore, there is a case where a substrate film to which ultraviolet absorbing property is imparted is used by kneading a UV absorber in a base film. A thermoplastic resin film which becomes a hard coating film substrate using polyethylene terephthalate (PET), polyamide, acrylic acid, polycarbonate (PC), triacetyl cellulose (TAC), cyclic polyolefin The transparent film formed. In particular, the biaxially oriented thermoplastic polyester film is widely used as a base film of various optical functional films in terms of excellent dimensional stability and chemical resistance. In general, when the thermoplastic resin film is biaxially aligned, the surface of the film is highly crystallized, which has the disadvantage of lacking adhesion to various coating materials, adhesives, inks, and the like. Therefore, since the past, it has been proposed to impart an easy adhesion method in various ways on the surface of the biaxially oriented thermoplastic resin film. For example, an easy-adhesion layer containing a resin such as polyester, acrylic, polyurethane, acrylic graft polyester or the like is provided on the surface of the thermoplastic resin film by a coating method so that the thermoplastic resin film has an easy adhesion property. The method is a generally known method. In the coating method, after the corona discharge treatment is performed directly or after the completion of the crystal alignment, the aqueous coating liquid containing the solution of the above resin or the dispersion of the dispersion medium is applied to the aqueous coating liquid. After drying on the base film, at least in a uniaxial direction, followed by heat treatment to complete the crystal alignment of the thermoplastic resin film (ie, in-line coating method), or to manufacture a thermoplastic resin film Thereafter, a method of drying the aqueous or solvent-based coating liquid on the film (that is, an off-line coating method) is widely carried out industrially. However, when the thermoplastic resin film is a biaxially oriented polyester film, the refractive index (face direction) is 1. 62~1. In the case of 65, for example, the refractive index of the hard coat layer formed of an acrylic resin or the like is usually 1 degree. 5 3 is the center of 1 . 5 0~ 1. 56. Further, in general, an easy-to-adhere layer located in the middle is formed by using an acrylic resin, a polyurethane resin, a polyester resin, or the like as a main component. Further, the refractive index of the resin composition layer is usually 1. 49~1. 54. Therefore, the difference between the refractive index of the biaxially oriented polyester film and the easy-adhesion layer 201000311 causes interference between the light reflection at the interface and the reflected light of the hard coated surface to cause interference spots (rainbow color). Therefore, when an antireflection layer (AR layer) or an antifouling layer is formed on the hard coat film, the visibility of the article such as the bonded image display device may be deteriorated or the sense of high quality may be impaired. Especially under the 3-wavelength fluorescent lamp, the interference speckle is noticeable due to the high proportion of the spectral components of the bright line. In recent years, the popularity of three-wavelength fluorescent lamps has rapidly grown in the general household, and this interference spot problem has become extremely important. Therefore, in the use of the interference spot as a problem, the use of the functional plastic film as the substrate of the biaxially oriented polyester film is significantly limited. Otherwise, it is a direct use of a functional film with interference spot problems. In fact, in the field of large flat-panel televisions using a biaxially oriented polyester film as a substrate, interference patches are almost always observed in the antireflection film currently mounted. On the other hand, when an antireflection layer composed of a high refractive index layer/low refractive index layer or a high refractive index layer/medium refractive index layer/low refractive index layer is laminated on the surface of the hard coat layer, by hard coating The layer is made to have a high refractive index, and the high refractive index layer can be omitted from the antireflection layer. As a result, when the antireflection film is produced, the cost can be greatly reduced. This tendency has been increasingly promoted due to the strong demand for cost reduction in recent years. However, when the hard coat layer is made to have a high refractive index, the problem of the above interference spots is more remarkable because the difference in refractive index from the easy-adhesion layer becomes larger. The present inventors have devised a laminated polyester film which focuses on the influence of local thickness unevenness of the film on interference spots, and is manufactured by copolymerizing polyester and polyurethane as a main component and solid component. After coating a film having an easy adhesion layer of 0·1 g/m2, 'the calendering treatment on the film' reduces the local thickness unevenness of the film to reduce the film thickness of the substrate 201000311. A laminated polyester film of interference spots caused by unevenness (Patent Document 1). However, the refractive index is higher in the laminate as described above (for example, 1). When the hard coat layer of 60 or more has excellent adhesion, the above interference pattern is remarkable. When the refractive index of the hard coat film is equal to that of the biaxially oriented polyester film, there is no difference between the biaxially oriented polyester film and the hard coat layer when the refractive index of the hard coat film is equal to that of the biaxially oriented polyester film. Under the resin composition layer, the hard coating layer and the biaxial alignment polyester film are optically integrated, and substantially no reflected light between the two layers is ideal. It is disclosed in Patent Document 2 that for the purpose of reducing interference spots, the refractive index is not directly deposited on the surface of the polyester film which is easily subjected to the film under the corona discharge treatment or the plasma treatment. 55~2. A hard coat film of a hard coat layer of 0. However, when a hard coat layer is directly provided on the biaxially oriented polyester film, sufficient adhesion is not obtained. Japanese Patent Publication No. 200 6-23 5 1 2 5 In addition, in Patent Document 3^4, it is attempted to maintain adhesion and to suppress interference spots by thinning the coating thickness of the easy-adhesion layer. Patent Document 3 exemplifies a laminated polyester film having a coating layer containing no particles and having a coating thickness of 5 to 30 nm formed of a polyester resin and an oxazoline crosslinking agent. It is shown in Patent Document 4 that the coating amount of the aqueous coating formed by the polyester resin and the melamine-based crosslinking agent and the particles having an average particle diameter of 65 nm is 0. 005~0. Coating was carried out at 05 g/m 2 to form a laminated polyester film having a highly hardened coating layer. In the case of laminating or laminating another optical functional layer, acrylic acid is provided on the opposite side to the hard coating layer, in the case of laminating or laminating another optical functional layer, Patent Document 3: JP-A-2008-18, 543, pp. A layer of a binder mainly composed of a resin. In order to improve the adhesion to the adhesive layer, a coating layer is provided on the base film. However, by additionally providing a coating layer, interface reflection occurs on the opposite surface, which is a cause of thousands of spots. On the other hand, another method of reducing interference spots, as disclosed in Patent Document 5, is a laminated polyester film having a coating layer containing two or more organic compounds having a metal element. Further, in the production and processing of the adhesion-modified substrate film, heat treatment is actually applied. With the increase in productivity, there is a tendency to carry out the treatment in a short period of time and at a high temperature. However, due to the heat history during the processing, oligomers are precipitated during the processing and the transparency is lowered. It is also disclosed in the following patent documents that a film of ethylene terephthalate having a reduced oligomer content is used as a substrate film. However, the films disclosed herein have oligomeric properties, and when a substrate film as a hard coat film is used, a sufficient effect of reducing interference spots cannot be obtained. Japanese Patent Laid-Open Publication No. JP-A No. 2003-301570 (Patent Document No. JP-A-2003-301057). The problem to be solved by the invention is that in the display used in a wide range of viewing angles, in order to correspond to higher definition, it is necessary to have a sufficient hard coating film of 201000311 interference spot reduction effect when viewed from all angles. . However, in the laminated film disclosed in the above Patent Documents 3 and 4, even after the formation of the hard coat film, since the layer structure of the easy-to-layer layer remains, a sufficient interference spot reduction effect cannot be obtained. Therefore, the prior invention 1 (Japanese Patent Application No. 2 07 07-2 7 0 09 09) performed by the inventors of the present invention is to make a sufficient interference spot reduction effect and adhesion. In the first invention, it is proposed to disperse an organic-inorganic composite on the boundary of the base film and the hard coat layer by applying an extremely thin coating liquid by integrating the hard coat agent with the hard coat film. A hard coating film of the material and a film of the adhesion-modified substrate formed of the substrate. According to the first aspect of the invention, by dispersing the organic-inorganic composite in the boundary between the base film and the hard coat layer, sufficient interference spot reduction and adhesion can be achieved. According to the adhesive-modified substrate film of the first invention of the first aspect, the adhesion-modifying layer formed by coating the extremely thin coating liquid containing inorganic particles has a small holding thickness, and the holding force by the particles of the resin becomes small. tendency. Here, the production speed of the substrate film to be produced or the processing speed at the time of processing the hard coat film is increased year by year. Therefore, it is understood that when the adhesion-modified base film of the first invention is supplied to a high-speed film formation or post-treatment, particles fall off (falling powder) may occur in the adhesion-modifying layer, and there may be a guide roll or the like. Process pollution problems. Further, when the surface unevenness state of the adhesive-modified substrate film changes due to the powder falling, the stable surface friction cannot be obtained, and the processing characteristics fluctuate. Further, when the processing at a relatively high temperature is performed, there is a problem that the transparency is lowered. An object of the present invention is to provide a laminate in which a hard coating layer is laminated, which has no significant number of spots when viewed from all angles, has excellent adhesion, and has insufficient adhesion of particles contained in the adhesion-modifying layer. Modified substrate 201000311 film. Further, the present invention provides a subsequent modified base film which is capable of suppressing interference spots of the entire laminate even when the adhesive layer is provided on the other surface of the hard coat layer. In other words, in order to reduce the aforementioned interference spots, the present invention provides a specific resin which is coated with a minimum thickness, and has a small coating thickness, which can suppress the reduction of the holding power of the particles, and can almost achieve the high-speed processing required in the future. A film of a substrate having a stable coefficient of friction can be obtained. Further, there is provided an adhesive-modified substrate film for a hard coat film which can be reduced as a whole interference spot even when an adhesive layer is provided. Further, there is also provided an adhesive modified base film which is transparent even when a heat history is carried out by processing. Means for Solving the Problem The above-mentioned problem can be achieved by the following solutions. (1) An adhesive-modified substrate film which is an adhesive-modified substrate film in which an adhesive layer (A) is laminated on at least one surface of a base film formed of a thermoplastic resin film. The adhesive layer (A) is characterized in that it contains at least one resin selected from the group consisting of a polyester resin, a urethane resin, and an acrylic resin, and inorganic particles, and the adhesive layer (A) The maximum diameter 値 of the haw portion of the surface protrusion of the surface of the adhesion-modifying layer (A) having a surface height of 100 nm or more is 10 to 12 mg/m 2 '. (2) The above-mentioned adhesive modified base film, wherein a difference (Δ // ) between the static friction coefficient (μ s) and the dynamic friction coefficient (μ d ) between the surfaces of the adhesive layer (A) is 0 2 0 the following. (3) The adhesive modified base film described above, wherein the base film -10-201000311 is formed of a thermoplastic resin film substantially free of particles. (4) The above-mentioned adhesive modified base film, wherein the base film is formed of three or more layers of a polyester film, and the oligomer content of the base film is 0. 6 mass% or more, 0. 90% by mass or less. (5) The above-mentioned adhesive modified base film, wherein the base film is formed of three or more laminated polyester films, and an ultraviolet absorber is contained in the intermediate layer. (6) The above-mentioned adhesive modified base film, wherein the base film layer* is formed of a laminated polyester film laminated with at least one layer on at least one side of the b layer by a co-extrusion method, at least in the aforementioned a layer The upper layer has an adhesive layer (A), and the a layer contains 0. 05~0. 1% by mass of inert particles having an average particle diameter of 1 to 10/Z m . (7) The above-mentioned adhesive modified base film, wherein an adhesive layer (A) is laminated on one surface of the base film, and a coating layer (B) is laminated on the other surface. In the base film, the coating layer (B) contains a polyester resin and a titanium compound. I (8) The above-mentioned adhesive-modified substrate film, wherein the coating layer (B) is formed by coating and drying a coating liquid (B) containing an aqueous polyester resin, a titanium lactate compound, and a triethanolamine titanium compound. The mass of the aqueous polyester resin contained in the coating liquid (B) is (a), the mass of the titanium lactate compound is (b), and the mass of the titanium compound of triethanolamine is (c), (a) /[(b) + (c)] is 5 0/5 0 to 80/20, and (b)/(c) is 3 5 /6 5 to 65/35 ° (9) The above-mentioned adhesive modification base The material film, wherein the adhesion-modifying layer (A) contains a copolymerized polyester, a polyurethane, and an inorganic particle. -11 - 201000311 (10) A hard coat film which is hard-coated by coating an uncured hardened resin layer on the surface of the adhesive layer (A) of the above-mentioned adhesive modified base film. In the case of the layer, the hard coat layer is directly laminated on the base film, and has an organic-inorganic composite dispersed over the boundary between the base film and the hard coat layer. (11) The hard coat film described above, wherein the hard coat layer has a refractive index of 1. 60 ~ 1 . [Effects of the Invention] The adhesive modified base film of the present invention, when it is a hard coat film, is excellent in interference fringes as a whole, and has high adhesion and stable surface friction. Therefore, in a preferred embodiment, when the hard layer is a hardened resin when the hard coat layer is formed, the uncured hard resin is mixed with the resin contained in the adhesive layer, and the base film is substantially The hard coat layer is integrated under direct laminate. Further, in a preferred embodiment, even in the high-speed processing of the post-processing, it is possible to obtain a film for the hard coat adhesive-modified substrate which has less process contamination, in other words, has less disadvantages of the detachment. In addition to the above-described effects, in the hard coating treatment and the processing before and after the treatment, even when the heating treatment is performed, high transparency and excellent interference spot reduction can be obtained and high. A hard coating film is then applied. In addition to the above-described effects, when used as a display member, it is possible to suppress deterioration of an optical functional dye such as a near-infrared ray absorbing agent, an iodine dye, or a coloring matter. In a preferred embodiment, in addition to the above effects, even when an adhesive layer is provided on the opposite side of the hard coating layer from the -12 to 201000311 side, the interference fringes which are the entire laminated body can be reduced. [Embodiment] The best mode for carrying out the invention The adhesive modified base film of the present invention expands when the uncured hardened resin is applied, and has an extremely thin adhesive modified layer in combination with the hard coat layer. Therefore, the adhesive-modified substrate film of the present invention is characterized in that a hard coat layer is directly formed on the surface of the base film when a hard coat layer is laminated on the subsequent modified layer. In other words, when a photograph was taken by a transmission electron microscope (TEM) at a magnification of 50,000 times to 200,000 times, a continuous resin composition layer was not observed at the interface between the base film and the hard coat layer. Further, it was observed that the following organic-inorganic composite was independently dispersed over the boundary between the substrate film and the hard coat layer. By having this configuration, the hard coat film of the present invention can reduce dry freckles from the interface reflection of the easy-adhesion layer. Further, high adhesion can be obtained by the organic-inorganic composite dispersed over the boundary between the substrate film and the hard coat layer. In the organic-inorganic composite, a film protrusion having a protrusion height of 10 nm or more by the inorganic particles was observed in the adhesive-modified substrate film before the hard coat layer. However, the coating amount of the adhesion modifying layer is 20 mg/tn2 or less (for example, the specific gravity of the coating layer is 1. At 2 o'clock, the extremely thin resin coating layer having a thickness of about 1 nm or less has a small holding force of the inorganic particles, and when the subsequent modified base film is connected to the guide rolls at a high speed, it is difficult to prevent the particles from falling off. The inventors of the present invention have further studied the relationship between the fine structure of the surface protrusion shape and the falling mechanism of the particles, and as a result, it has been found that the thickness of the lipid layer and the height of the surface protrusion are simply determined by the height of the tree-13-201000311, and the particles are not easily separated. In the case where the mountain ridges which form a mountain-like surface are broadened and the inorganic particles are easily detached, the present invention can be completed. Here, when the thickness of the resin layer is reduced, the surface-protrusion soil portion of the mountain shape becomes weak, and the width of the mountain portion of the sharp protrusion becomes narrow. It is known that the narrow surface of the haw is protuberance, and the inorganic particles are easily peeled off. Therefore, in the present invention, this problem can be solved by actively forming a haw portion having a specific size or more formed by a resin component contained in the coating liquid around the surface projection. Further, the maximum diameter of the surrounding mantle portion centering on the inorganic particles and the protrusions having a height of l〇〇nm or more as referred to in the present invention is as shown in Fig. 3, which is included in the adhesive layer as shown in Fig. 3. The inorganic particles or aggregates thereof are nuclei, and the maximum diameter of the hawthorn portion when the resin component is in the form of a broad mountain shape around one core. According to this configuration, it is possible to reduce the process contamination caused by the falling off of the particles, and to reduce the interference layer of the hard coat layer (especially the hard coat layer having a high refractive index) at all angles to achieve sufficient adhesion. Is a new insight into the invention. The easiness of detachment of particles in the adhesion-modifying layer in the adhesive-modified substrate film of the present invention can be determined by the difference between the static friction coefficient (V s ) and the dynamic friction coefficient d ) of the adhesion-modifying layer. The coating layer is in such a manner that the coating amount of the inorganic particles can be firmly fixed as much as possible. The static friction coefficient (^ s ) and the dynamic friction coefficient (V d ) of the film are almost the same or slightly different from the dynamic friction coefficient. relationship. However, when the inorganic particles are easily detached, the particles may fall off when the dynamic friction is measured, and the kinetic friction may rapidly increase. The film can cause significant contamination of the processing equipment in a short period of time during the manufacturing process or after the manufacturing process, the quality of the product -14-201000311 and the problem of reduced productivity. This phenomenon is almost completely satisfactory in a general coating layer (e.g., a coating amount of 50 mg/m2 or more and an average particle diameter of the particles of 20 to 150 nm), but it is likely to become remarkable when the coating amount is as small as the limit. In the adhesive modified base film of the present invention, the difference between the static friction coefficient S) and the dynamic friction coefficient (/zd) of the adhesive modification layer (μd - V s ) is 0. 20 or less is preferred, preferably 0. Below 19, better is 0. 18 or less. The difference between the static friction coefficient (/z S ) and the dynamic friction coefficient (// d ) is Δ. When the temperature is below 20, it is preferable since the powder falling can be controlled and the process contamination is also reduced. Thereby, the optical disadvantage caused by the powder falling situation can be reduced. Moreover, since stable friction characteristics are obtained, processing characteristics are preferred. Moreover, the dynamic friction coefficient and the static friction coefficient are different. 8 is better, and better is 0. 6 or less. Greater than 0. At 8 o'clock, the crack resistance is lowered and it is easily damaged during the processing. (1) Base film The thickness of the base film used in the present invention is not particularly limited, and may be arbitrarily determined in the range of 20 to 400 #m depending on the intended use. The upper limit of the thickness of the substrate film is preferably 350//m, more preferably 300; am. Further, the lower limit of the thickness of the film is preferably 5 0 # m, more preferably 7 5 # m, and most preferably 1 0 0 // m. When the film thickness is less than 20 m, the rigidity or mechanical strength tends to be insufficient. Further, when the film thickness exceeds 400 #111, since the absolute amount of foreign matter present in the film increases, the frequency of forming optical defects increases. Further, the slit property when the film is cut into a predetermined width is also deteriorated, and the manufacturing cost is improved. Further, since the rigidity is increased, it is easy to make the long-length film difficult to be wound into a roll shape. The thermoplastic resin constituting the base film is polyethylene terephthalate, propylene terephthalate, polybutyl phthalate, polyethylene-2,6-naphthalate, syndiotactic -15-201000311 Styrene, raw spinylene-based polymer, polycarbonate, polyacrylate, and the like are preferred. Further, the resin having a polar functional group such as polyester or polyamine is preferable in terms of adhesion to the adhesion modifying layer. Among them, copolymerization of polyethylene terephthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate, propylene terephthalate or the constituents of such resins as a main component Preferably, in other words, a biaxial alignment film formed of polyethylene terephthalate is more preferred. For example, when a resin which forms a base film is a polyester copolymer having polyethylene terephthalate as a basic structure, the proportion of the copolymerization component is preferably less than 20 mol%. When it is 20% by mole or more, the film strength, transparency, and heat resistance are not good. A dicarboxylic acid component which can be used as a copolymerization component, for example, an aliphatic dicarboxylic acid such as adipic acid or sebacic acid, an isophthalic acid, a citric acid, or an aromatic dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid. A polyfunctional carboxylic acid such as acid, trimellitic acid or pyromellitic acid. Further, a diol which can be used as a copolymerization component, for example, a fatty acid diol such as diethylene glycol, 1,4-butanediol, propylene glycol or neopentyl glycol; an aromatic diol such as p-xylitol; An aliphatic diol such as 4-cyclohexanedimethanol; a polyethylene glycol having an average molecular weight of 150 to 20,000 or the like. (Reduction of oligomer) The preferred embodiment of the adhesive-modified substrate film of the present invention is such that when the transparency is lowered by the heat treatment process, the heat treatment is performed at 170 ° C for 20 minutes. The amount of haze change on the film "Ηζ (ΖΐΗζ = haze after heating - haze before heating) is less than 1. 5% ' to 0. 5 % is better' to 0. 3 % is better. At this time, the oligomer content of the substrate film is 0. It is preferably 90% by mass or less. The oligomer content of the substrate film is 〇. When the amount is less than or equal to 9% by mass, the amount of precipitation of the oligomer is small even when the temperature is increased by the high temperature treatment. The amount of change in haze by heating is within the above range. -16-201000311 However, in order to reduce the oligomer content, 'the oxidative deterioration of the polyester resin is produced when the following treatment is carried out." The polyester resin may be yellowish. The color 値b値' of the film used for the member for the display is 4. 0 or less. Therefore, the base film of the present invention has an oligomer content of 0. 60% by mass or more, preferably 0. 70% by mass or more, and even better. 8〇% by mass or more. The oligomer content is 0. When the amount is 60% by mass or more, the film does not have a yellow color. It is suitable for use as a high-quality display member such as a liquid crystal display or a plasma display, so that the film haze change amount before and after heating is within the above range' and the film is When the color degree b is in the above range, a laminated polyester film having three or more layers of a polyester resin having a small amount of oligomers on the surface layer is preferably a preferred embodiment. The layer of the laminated polyester film constitutes a layer b formed of a polyester resin having a small oligomer content, and when the polyester resin other than the layer is a layer or a layer c, the film layer structure may be a/b or b/. a/b, b/a/c/b, or b/a/c / a/b, etc. In any of the cases, when a laminated polyester film is used as the base film of the present invention, it is preferred to use a polyester resin having a small oligomer content in the layer A constituting the outermost layer. The oligomer includes a linear oligomer mainly composed of a cyclic trimer, a linear dimer and a linear trimer, and a phthalic acid or a phthalic acid monoethyl phthalate. An alcohol ester or the like, but the oligomer of the present invention is mainly formed of a cyclic trimer. The method of forming the polyester film layer having a small amount of the oligomer is not particularly limited, and as disclosed in JP-A-48-101462, JP-A-49-32973, etc., it is possible to use a polymerized sheet. Further, the polymer is polymerized in a solid phase, and a low molecular weight body such as an oligomer is reduced in a sheet state, and a film is formed by using such a raw material, or a solvent is used to remove a low molecular weight body such as an oligomer in a sheet. The method, or a method of removing a low molecular weight substance such as an oligomer by a film extraction from a biaxially stretched thermosetting -17 to 201000311, or the like. In particular, the method of solid phase polymerization operation in addition to the former, when the temperature is high and the time is long in the extrusion process of the film, the low molecular weight body such as the oligomer which is reduced in folding angle is increased in the heat balance relationship, so that the temperature is as low as possible. It is better to push out in a short time. (Ultraviolet absorber) In the preferred embodiment of the present invention, in order to prevent deterioration of the optical functional dye, it is preferable to use three or more layers of the polyester film as the base film, and it is preferable to contain the ultraviolet absorber in the intermediate layer. In this case, when the layer having the ultraviolet absorber is the a layer and the other surfaces are the b layer and the c layer, the film layer composition may be b / a / b, b / a / c, b / a / c /b, or b/a/c/a/b, etc. The layers of the layers a to c may each be the same as or different from the composition of the polyester resin. Among them, b/a/b (two types of three-layer structure) is preferable. In any of the above, it is preferred to provide a layer containing an ultraviolet absorber as an intermediate layer. By containing the ultraviolet absorber in the intermediate layer, the outflow of the additive can be prevented, and the decrease in the adhesion due to the extravasation of the additive can be suppressed. A conventional ultraviolet absorber can be used in the present invention. The ultraviolet absorber **, for example, an organic ultraviolet absorber and an inorganic ultraviolet absorber are preferably an organic ultraviolet absorber in terms of transparency. The organic ultraviolet ray absorbing agent, for example, a benzotriazole-based, benzophenone-based, cyclic urethane-based or the like, and a combination thereof are not particularly limited as long as they are within the range of the absorbance specified in the present invention. However, in terms of durability, a benzotriazole-based or cyclic imidate system is more preferable. When two or more types of ultraviolet absorbers are used, ultraviolet rays of various wavelengths can be absorbed at the same time, so that the ultraviolet absorption effect can be improved at the same time. -18-201000311 When a substrate film containing a UV absorber is used, the transmittance of the adhesion-modified base film of the present invention at a wavelength of 380 nm is preferably 20% or less. In particular, when a substrate of a display member such as a filter for a PDP or a protective film for a polarizing plate is used, the transmittance at 380 nm is preferably 15% or less, more preferably 5% or less. When the transmittance is 20% or less, it is possible to suppress the deterioration of the optical functional color such as the near-infrared absorbing dye or the iodine dye contained in the optical function layer due to ultraviolet rays. When the transmittance of the adhesive modified base film at a wavelength of 380 nm is 20% or less, the concentration of the ultraviolet absorber and the thickness of the base film can be appropriately adjusted. Further, the transmittance of the present invention is measured by a spectrophotometer (e.g., Hitachi U-3 500 type) for the plane of the optically laminated film of the adhesive-modified substrate film. (Structure without particles) The "adhesive modified base film used in the present invention is required to have a high degree of transparency", so that it is preferable that substantially no particles having a reduced transparency are contained in the base film. The term "substantially free of particles" as used herein means, for example, inorganic particles, which is 50 ppm or less, preferably 1 Op pm or less, more preferably 1 MPa or less, by sand X-ray analysis. content. In this case, even if particles are not actively added to the base film, the contaminated components from the foreign matter or the dirt adhering to the line or the device during the production process of the raw material resin or the film are peeled off and mixed into the film. (Structure of surface layer particles) In the preferred embodiment of the present invention, in order to obtain a more stable surface friction property, a laminate polyester containing only inert particles in the surface layer can be used as the substrate film. The base film is preferably a polyester film formed by laminating a layer having a layer of inert -19 - 201000311 containing at least one side of the b layer by a co-extrusion method. By making the base film into the above configuration, it is possible to maintain high transparency and impart stability and smoothness. The base film of the present invention may have a two-layer structure or a multilayer structure of three or more layers. When the b layer containing no particles, the a layer containing inert particles, or the other layer other than the c layer, the layer thickness in the film thickness direction can be considered as b / a, a / b / a, a / b / c, a / b / c / a, or a / b / c / b / a and so on. Each of the layers a to c may be the same or different from the composition of the polyester resin. However, when the warpage caused by the two metals is controlled, the polyester resin of each layer has the same composition. And / or a / b / a composition (two kinds of three-layer structure) is preferred. In any case, in order to laminate the adhesion-modifying layer on the surface of the layer a to be described later, it is preferred to form at least one surface layer of the substrate film with the layer a containing the inert particles. Inert particles contained in layer a, such as calcium carbonate, calcium phosphate, amorphous cerium oxide, spherical cerium oxide, crystalline glass fiber, kaolin, talc, titanium dioxide, aluminum oxide, cerium oxide-alumina Inorganic particles such as composite oxide particles, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, mica, or crosslinked polystyrene particles, crosslinked acrylic resin particles, and crosslinked methyl methacrylate Heat-resistant polymer fine particles such as particles, benzoguanamine, formaldehyde condensate particles, melamine-formaldehyde condensate particles, and polytetrafluoroethylene particles. In particular, in terms of transparency, cerium oxide particles (especially amorphous cerium oxide) having a resin component and a refractive index are preferably used. The average particle diameter ' of the inert particles contained in the a layer is preferably from 1 to 10 A m, more preferably from 1. 5 to 7 // m, and most preferably from 2 to 5 #m. The average particle size of the inert particles is 1. When it is 0 or more, it is preferable to have an appropriate uneven structure which can impart a smoothness of -20 to 201000311 to the surface of the layer a. Further, when the average particle diameter of the inert particles is ΙΟ/zm or less, it is preferable because high transparency can be maintained. Moreover, the content of inert particles in the layer a is 0. 005~0. 1% by mass is preferred, preferably 0. 008~0. 07%, the better is 〇. 〇1~〇. 〇5%. The content of inert particles is 0. When the amount of the layer of 5% is 005 mass% or more, the surface of the layer a has a slipperiness and can provide an appropriate uneven structure, which is preferable. In addition, the content of inert particles is 0. When it is 1% by mass or less, it is preferable because it can maintain high transparency. The thickness of the layer a containing inert particles is preferably from 3 to 30/zm in the total thickness of the base film, and more preferably from 5 to 20 μm. When the thickness of the a layer is 3 or more, the inert particles are easily retained in the layer a, and stable slipperiness can be easily obtained even under high speed processing. Further, when the thickness of the layer B is 30/zm or less, transparency is preferred. When the thickness of the layer a is observed by using a transmission electron microscope (TEM), the difference in density of the inert particles can be judged and determined. Further, in the case of producing a film, the film thickness can be calculated by calculating the film thickness ratio (discharge amount ratio) of the self-pressing machine. The measurement of the average particle diameter of the above inert particles was carried out by the following method. The particles were photographed by an electron microscope, and the size of one of the smallest particles was a magnification of 2 to 5 mm, and the maximum diameter of 300 to 500 particles was measured, and the average 値 was used as the average primary particle diameter or average particle diameter. Further, when the average particle diameter of the particles in the adhesion-modifying layer of the adhesive-modified substrate film is determined, a cross-section of the substrate film can be modified by a transmission electron microscope (TEM) at a magnification of 120,000 times. The maximum particle size of the particles of the composite is determined. The average particle diameter of the particles formed by the aggregates is a cross section of the adhesive modified layer of the adhesive-modified substrate film, and is photographed by an optical microscope at a magnification of 200 times - 21,001,001,011, and more. Its largest particle size. As described above, by adding inert particles of a specific size to the ruthenium layer, surface unevenness suitable for imparting stability and slipperiness is formed on the surface of the LY layer. The composition is such that the center roughness (SRa) of the side surface of the tantalum layer of the adhesion-modified substrate film is 0. 005~0. 05/zm is preferred, preferably 0 0. 03/zm. Moreover, ten average roughness (SRz) is 0. 5~2. 0/; Preferably, the preferred one is 0. 8~1·5/ζιη. By forming the surface unevenness in the above range at least one of the surface layers of the film, stable slipperiness and processability can be obtained even under high speed processing. When the haze of the adhesion-modified substrate film is within the above range, the a layer 1 may contain appropriate inert particles. For example, when the polyester containing particles is made thinner for recycling, the mixing ratio is adjusted within the range of the above haze. However, in the case where high transparency can be obtained, it is preferable that the a layer contains substantially inert particles. (Method for Producing Base Film) The thermoplastic resin of the present invention may contain various additives in addition to the catalyst, without impairing the effects of the present invention. Additives such as particles, heat-resistant polymer particles, alkali metal compounds, soil-based gold compounds, phosphorus compounds, antistatic agents, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, gelation inhibitors, The interface is alive. The base film used in the present invention is such that the thermoplastic resin is melted out or the unaligned sheet obtained by melt extrusion is extended in a uniaxial direction as long as necessary in the length or width direction, or sequentially extended in the two-axis direction or simultaneously. A biaxially oriented resin film which is biaxially stretched and which is subjected to heat setting treatment is preferred. In B is flat from the top. 0 1~ i in is a surface that is easy to be in the middle of the film. It is not suitable for the inorganic genus, and the difficult agent is in the direction of the two-axis thermoplastic -22-201000311. It is typical when using polyester as the raw material of the base film. The method for producing a base film will be described in detail below. The inherent viscosity of the polyester pellets used as the raw material of the film, ~0. A range of 70 dl/g is preferred. Intrinsic viscosity is less than 〇. At 45 dl/g, most of the film formation is prone to breakage. In addition, the inherent viscosity is 0. At 70 dl/g, the filtration pressure is greatly increased, and it is difficult to perform high-precision filtration, which tends to cause a decrease in productivity. Further, the inherent viscosity of the polyester was dissolved in a mixed solvent of phenol (6 parts by mass) and 1,1,2,2-tetrachloroethane), and the measurement was carried out at 30 °C. Further, it is preferred to remove foreign matter in the raw material polyester which causes optical defects. In order to remove foreign matter in the polyester, the filter material used for high-precision filtration at the time of high-precision filtration at a time when the fat is kept at 270 to 29 ° C during the melt extrusion is not specially made, and is a stainless steel sintered body. In the case of the filter material, the removal property of the aggregate of the Si, Ti, Sb, and Ge main components and the high-melting-point organic material is excellent as the sub-size (initial filtration efficiency: 95%) of the filter material used in the high-precision filtration treatment of the molten resin. It is preferably 1 5 m or less. When the filtered particle size is larger than 15 μm, the effect of foreign matter of 20/zm or more becomes insufficient. After the polyester pellets were sufficiently vacuum-dried, they were supplied to a cast film which was melted and extruded into a sheet at 270 to 295 ° C and cooled to obtain an unaligned film. The obtained cast film is extended in the longitudinal direction by a heated roll of 80~2. 5~5. 0 times, the polyester film is obtained. Then, the following liquid was applied to both sides of the uniaxially oriented polyester film. Then, the two ends of the film are fixed by clips, and the heating is introduced, and the correlation is 0. 45, in the system is greater than the treatment, the degree can be (4 quality of the melting of the tree. The limit of melting, Cu is appropriate. Filter filter material J of the removal machine, and the process, made at 120 ° C [axis alignment coating In the hot air zone of 180 °C, it will extend in the width direction after drying. 5~5. 0 times. Next, 'introduction into a hot air zone heated to 22 Torr to 240 ° C' is performed to heat-treat to complete the crystal alignment treatment. In the heat treatment process, a relaxation treatment of 1 to 12% may be carried out in the width direction or the length direction as needed. Further, the base film may be subjected to corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, ozone treatment, etc. on the base film described above without impairing the object of the present invention. Surface activation treatment. (2) Adhesive modified layer (a) The adhesive modified base film of the present invention is formed by laminating an adhesive modifying layer (A) on at least one side of a base film. The adhesive layer (A) of the present invention contains at least one selected from the group consisting of polyester resins, urethane resins, acrylic resins, and inorganic particles. The polyester resin, the acrylic resin, and the urethane resin constituting the adhesive modified layer (A) of the present invention have adhesiveness to both the base film and the hard coat layer, and are in a hard coater. The organic solvent contained is appropriately expanded. The above resins may be used singly or in combination of two different resins (e.g., a polyester resin resin and a urethane resin, a polyester resin and an acrylic resin, or a urethane resin and an acrylic resin). In the case where the base film of the substrate is a polyester base film, the adhesion to the hard coat layer and the expandability include the copolymerized polyester and the polyurethane. The main resin component constituting the composite is preferred. When the copolymerized polyester is used alone, the adhesion to the polyester base film is sufficient, but the adhesion to the hard coat layer is not good. Moreover, since it is a relatively brittle resin, it is easy to cause agglomeration damage to the impact at the time of cutting. Further, when the polyurethane is used alone, the adhesion to the hard coat layer is excellent in the range of -24 to 201000311, but the shape of the polyester film is not good. Further, when the adhesive modified base film is wound into a roll, the blocking resistance is poor. Therefore, the use of a hard coat film having a film of the adhesion-modified substrate having the adhesion-modifying layer (A) formed of a polyurethane alone may result in poor quality. In order to avoid this problem, it is necessary to include a particle having a large particle diameter in the composite containing a large amount of particles in the base film, or to increase the content of the particles constituting the composite. As a result, since the haze of the film rises, particularly as a base film of a hard coat film which is required to have high transparency, it is not desired. The adhesive modifying layer (A) of the present invention can be dried by applying a coating liquid (A) continuously to at least one side of the running thermoplastic resin film, and then drying the coating liquid at least in a uniaxial direction. A stretching process for stretching and a heat setting process for thermally fixing the stretched film are formed, and an adhesive modified base film provided with the adhesive modifying layer (A) is produced. When the coating layer (B) described below is provided, it is preferred that the coating layer (A) and the coating liquid (B) are continuously applied to the other surface. Further, at least one selected from the group consisting of an epoxy crosslinking agent, a melamine crosslinking agent, and an oxazoline crosslinking agent may be mixed in the coating liquid (A) as needed, and heat-treated to form an appropriate crosslinking. structure. (Coating Process of Coating Liquid (A)) In the present specification, the coating liquid when the adhesive layer (A) is formed is used as the coating liquid (A), and the coating layer (B) described below is formed on the other surface. The coating liquid is the coating liquid (B) (however, the expression in the examples is based on another indication). When the adhesion-modifying layer (A) of the present invention is formed by a coating method, the material used in the coating liquid (A) is a resin, a dispersion medium or a solvent. In the present invention, the coating liquid (A) is preferably water-based. Further, in the present invention, in addition to the resin component, inorganic particles may be used. Further, it is preferable to use a surfactant of -25 to 201000311, and an additive such as a surfactant, an antistatic agent, an ultraviolet absorber, an organic lubricant, an antibacterial agent, or a photocatalytic catalyst may be used as needed. Further, in the coating liquid (A), in order to promote the thermal crosslinking reaction of the resin, a catalyst may be added, and for example, an inorganic substance, a salt, an organic substance, a basic substance, an acidic substance, a metal-containing organic compound, or the like may be used. Various chemicals. Further, in order to adjust the pH of the aqueous solution, an alkaline substance or an acidic substance may be added. The coating liquid (A) is obtained by dispersing or dissolving the resin in a dispersion medium or a solvent under stirring, and then, in addition to the inorganic particle dispersion liquid adjusted as described below, a surfactant may be used, and various kinds of surfactants may be used. The additive is adjusted until it is diluted to the desired solid concentration. In addition, when the resin component and the particles of the coating liquid (A) are uniformly dispersed, and the foreign matter such as coarse particle agglomerates and dust in the process is removed, the coating liquid (A) is preferably finely filtered. The filter medium type in order to precisely filter the coating liquid (A) is not particularly limited as long as it has the above-described properties, and is, for example, a monofilament type, a fluff type, or a screen type. The material of the filter medium in order to precisely filter the coating liquid (A) is not particularly limited as long as it has the above-described properties and does not adversely affect the coating liquid (A), such as stainless steel, polyethylene, and polypropylene. , Nair and so on. In order to precisely filter the coating liquid (A), it is preferred to filter the particle size (initial over-efficiency: 9.5 %) to a filter material of 25 m or less, and more preferably a filter performance of 1 〇# m or less. Filter material. The best is to use a combination of filters that filter different properties. When a filter medium having a particle size larger than 25 Mm is used, the removal of coarse aggregates tends to be insufficient. Therefore, the coarse aggregate which cannot be removed by filtration is more broadly distributed by the uniaxial distribution of the -26-201000311 or the two-axis alignment process after coating and drying, and there is agglomerates of 100/zm or more. It is easy to become the cause of optical defects. (A) Resin In the present invention, a polyester resin (particularly, a copolymerized polyester (PEs)) and a polyurethane resin (particularly a polyurethane) are used as a composite. When the resin is used, it is preferable in terms of adhesion. At this time, the mass ratio of the solid content of the copolymerized polyester (PEs) to the polyurethane (PU) in the coating liquid (A) is (PEs) / (PU) = 70/30 to 30 / 70 is better, preferably 60M0~4〇/60. Further, the resin of the composite may be a third resin other than the above-mentioned copolymerized polyester and polyurethane. In addition, a crosslinking agent can also be used. (Polyester-based resin) For example, when a copolymerized polyester is used as the polyester-based resin in the composite, an aromatic dicarboxylic acid component and ethylene glycol as a diol component and a branched diol are constituent components. Preferably. The above branched diols such as 2,2-dimethyl-1,3-propanediol, 2-methyl-2-ethyl-1,3-propanediol, 2-methyl-2-butyl-1,3 -propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-methyl-2-isopropyl-1,3-propanediol, 2-methyl-2-n-hexyl-13-propanediol, 2,2·diethyl-1,3-propanediol, 2-ethyl-2-n-butyl-^-propanediol, 2-ethyl-2-n-hexyl-1,3-propanediol, 2,2-di - n-Butyl-indole, 3-propanediol, 2-n-butyl-2-propane-1,3-propanediol, and 2,2-di-n-hexyl-anthracene, 3-propanediol, and the like. The molar ratio of the branched diol component has a lower limit of 1 〇 mol/° for all diol components. Preferably, the better is 2 〇 mol%, and the best is 3 〇 mol%. Further, the upper limit 値 is preferably 90% by mole, and more preferably 8% by mole. Further, diethylene glycol, propylene glycol, butylene glycol, hexanediol or 1,4-cyclohexanedimethanol may be used as needed. -27- 201000311 The aromatic dicarboxylic acid component is best for citric acid or isophthalic acid. For all the dicarboxylic acid components, other aromatic dicarboxylic acids in the range of 10 mol% or less, particularly aromatic dicarboxylic acids such as diphenylcarboxylic acid and 2,6-naphthalenedicarboxylic acid may be added. Co-polymerization. When a polyester-based resin is used as the aqueous coating liquid, it is preferred to use a water-soluble or water-dispersible polyester-based resin, and when the water-soluble or water-dispersible is used, the sulfonate-containing compound may be contained. It is preferred that the carboxylate group compound be copolymerized. Therefore, in addition to the above-mentioned dicarboxylic acid component, in order to impart water dispersibility to the polyester, an alkali metal salt of 5 · sulfisoisodecanoic acid in a range of 1 to 10 mol% is preferably used, for example, a sulfo group. For citric acid, 5-sulfoisodecanoic acid, 4-sulfophthalic acid-2,7-dicarboxylic acid and 5-(4-sulfophenoxy)isodecanoic acid or a metal salt thereof. (Polyurethane-based resin) The polyurethane obtained from the composite containing the polyurethane resin is preferably a thermally reactive polyurethane resin, for example, a terminal isocyanate. A water-soluble or water-dispersible polyurethane which is blocked with an active hydrogen group (hereinafter simply referred to as a block). Blocking agents for isocyanate groups, such as esters of bisulfites, phenols, alcohols, indoleamines, anthraquinones and dimethyl malonate, and diketones such as methyl acetoxyacetate Examples include hydrazines such as hydrazines, steroids, ureas, imidazoles, and quinone iminoamines, amines such as diphenylamine, imines, and urethanes such as 2-oxazolidine. The water-soluble or water-dispersible polyurethane is preferably a hydrophilic group in the molecule. Therefore, it is preferred to use a compound having a hydrophilic group in a compound having at least one or more active hydrogen atoms in the molecule to be used, or a compound having hydrophilicity as described above. An example of a hydrophilic group in the compound -28-201000311 having at least one or more active hydrogen atoms in the molecule to be used, such as taurine, dimethylolpropionic acid, or a carboxylic acid group or a sulfonic acid group Ester polyol, polyoxyalkylene alkyl alcohol, and the like. Further, the 'blocking agent has a hydrophilic compound' such as a bisulfite, a phenol having a sulfonic acid group, and the like. When the above-mentioned resin has thermal energy by a drying process or a heat-fixing process for producing a film, the water-dispersible copolymerization of the above-mentioned resin into the self-crosslinking structure is carried out in order to separate the blocking agent from the isocyanate group. The polyester is immobilized and simultaneously reacted with the above-mentioned resin terminal group or the like. Particularly, a water-soluble or water-dispersible polyurethane is preferably a compound having a hydrophilicity using a blocking agent. Since the polyurethane in the coating liquid is hydrophilic, the water resistance is not good, but the coating, drying, heat setting, and completion of the thermal reaction are due to the hydrophilicity of the urethane resin. Since the base, that is, the blocking agent is detached, a coating film having good water resistance can be obtained. The chemical composition of the urethane prepolymer used in the above-mentioned polyurethane resin is such that (1) a compound having a molecular weight of at least two active hydrogen atoms in the molecule of 200 to 20,000 ( 2) A compound having a terminal isocyanate group obtained by reacting an organic polyisocyanate having two or more isocyanate groups in a molecule, and (3) a chain extender having at least two active hydrogen atoms in the molecule. The compound of the above (1) having a molecular weight of at least two active hydrogen atoms in the molecule of 200 to 20,000 is generally known to contain two or more hydroxyl groups, carboxyl groups, amine groups or sulfhydryl groups at the terminal or molecule. More preferred compounds are, for example, polyether polyols and polyester polyols. The polyester polyol can be obtained by using a polyvalent saturated or unsaturated carboxylic acid such as succinic acid, adipic acid, citric acid or maleic anhydride, or the like, and the like, and ethylene glycol, diethylene glycol, and 1,4-. Butanediol, neopentyl glycol, 1,6-hexanediol, trimethylolpropane-29-201000311, etc., multi-saturated and unsaturated alcohols, lower molecular weight polyethylene glycol, polypropylene glycol, etc. The polyalkyl ether glycols or a mixture of such alcohols are condensed and obtained. Further, as the polyester polyol, for example, a polyester obtained from a lactone or a hydroxy acid or a polyether ester polyol obtained by adding ethylene oxide or propylene oxide to a polyester produced in advance can be used. The organic polyisocyanate of the above (2), for example, an isomer of methylphenylene diisocyanate, an aromatic diisocyanate such as 4,4-diphenylmethane diisocyanate, or an aromatic benzene diisocyanate Aliphatic diisocyanates, isophorone diisocyanates, and alicyclic diisocyanates such as 4,4-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and 2,2,4-trimethyl-6 An aliphatic diisocyanate such as methylene diisocyanate or a polyisocyanate obtained by adding one or more of these compounds to trimethylolpropane or the like. The chain extender having at least two active hydrogen atoms in the molecule (3), for example, glycols such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol Polyols such as glycerol, trimethylolpropane and pentaerythritol, diamines such as ethylenediamine, hexamethyldiamine, and pyridinium, amines such as monoethanolamine and diethanolamine, and thiodi A thiodiglycol such as glycol or water. When synthesizing the urethane prepolymer, the above (1) and the above (2), and the above-mentioned (3) 'required by the one-stage or multi-stage isocyanate polyaddition method, at 150 °, are usually used. The reaction is carried out for 5 minutes to several hours at a temperature of 7 Torr to 120 ° C, preferably C or less. In the active hydrogen atom of the above (1) and (3), the ratio of the isocyanate group of the above (2) can be freely selected as long as it is 1 or more, and only the remaining urethane polymer must remain free. Isocyanide-30- 201000311 acid ester base. Further, the 'content of the free isocyanate group' may be as long as it is 1% by mass or less based on the total mass of the obtained urethane prepolymer, and the blocked urethane polymerization is considered. When the stability of the aqueous solution of the substance is 7% by mass or less, it is preferably 7.7% by mass or less. The above-mentioned urethane prepolymer of the above is preferably a blocker of a terminal isocyanate group using a heavy sulfite. The urethane prepolymer is mixed with the aqueous bisulfite solution, and the mixture is stirred and reacted for about 5 minutes to 1 hour. The reaction temperature is preferably 60 ° C or lower. Then, the reaction mixture is diluted to a suitable concentration with water to form a thermally reactive water-soluble urethane composition. When the composition is used, it is prepared to have an appropriate concentration and viscosity. Usually, when heated at about 80 to 200 ° C, the bisulfite salt of the blocking agent is dissociated to regenerate the active isocyanate group. At the time, a polyurethane polymer is formed by causing a polyaddition reaction in or between molecules of the prepolymer, or has a property of causing addition to other functional groups. (Acrylic resin) Water dispersibility or water solubility when an acrylic resin is used in the composite, and the acrylic resin has, for example, an acrylate and/or a methacrylate, or an unsaturated double bond such as styrene or the like. A copolymer of an aliphatic compound or an aromatic compound copolymerizable with an acrylic resin. The adhesive modified layer (A) which is excellent in adhesion to the hard coat layer is used as a highly acidic hydrophilic acid-styrene copolymerized resin, and is water-dispersible acrylic-styrene by emulsion polymerization. The copolymerized resin is the best. Further, in the present invention, since the water-dispersible acrylic-styrene copolymer resin is more firmly adhered to the base film, the copolymerized resin is used in an amount of 10 to 90% by mass of the copolymerized polyester resin. Time is valid. Preferably, the polyester dispersible sulfonic acid metal base polyester copolymer resin is mixed with water 31 - 201000311 . • The dispersible acrylic-styrene copolymer resin coating liquid (A) is suitably applied to a substrate film. Preferred examples of the polyester constituting the polyester-polymerized resin of the aqueous dispersible sulfonic acid metal base such as polyethylene terephthalate, polyethylene-2,6-naphthalate, poly-1, 4-cyclohexane dimethylene terephthalate. The polyester is copolymerized with the above-mentioned acid component or diol component, which is required to be 3 〇 mol% or less, preferably 15 mol% or less, or the above-mentioned acid component and the molar ratio The polyester blend obtained from the diol component. In addition, by adding a water-dispersible or water-soluble uric acid to a coating liquid (A) in which a water-dispersible acrylic-styrene copolymer resin is mixed with a polyester dispersing sulfonic acid metal base polyester copolymer resin Ester resin (preferably water-dispersible, block isocyanate resin having three or more functional groups), copolymerized resin of water-dispersible acrylic-styrene copolymerized resin and aqueous dispersible sulfonic acid metal base The crosslinking reaction does not lower the adhesion to the hard coat layer' and the adhesion resistance of the surface of the coating film can be improved. When each of the above resins is used, the coating liquid (A) containing the above components is applied to at least one surface of the base film to be dried. For example, a water-dispersible acrylic acid-styrene copolymer resin, preferably a random copolymerized resin of acrylate and/or methacrylate resin and styrene, and an aqueous dispersion as a water-dispersible polyester copolymer resin The polyester copolymerized resin of the sulfonic acid metal base is a solid content of 4 to 15% by mass, and the viscosity of the solid content is 4 to 15% by mass in terms of a solid content of 3:2 to 1 :1 by mass of the resin-containing coating liquid (A). It is 4 to 60 cps (measured by a b-type viscometer at 25 cps). Further, in the case where the acrylic resin is required to be crosslinked, a crosslinking agent such as an isocyanate, an epoxy resin, an oxazoline or a melamine may be used. (b) Solvent - 32 - 201000311 In the present invention, the solvent generally includes a dispersion medium which is used not only for dissolving the resin but also for dispersing the resin into particles. In order to carry out the invention, various solvents such as an organic solvent and an aqueous solvent can be used. The solvent used in the coating liquid (A) is preferably a mixture of water and an alcohol such as ethanol, isopropyl alcohol or benzyl alcohol in a ratio of 10 to 50% by mass based on the total coating liquid (A). , to 2 0 to 40% by mass is better. Further, when it is less than 1% by mass, it may be mixed in a range in which an organic solvent other than the alcohol is dissolved. Only in the coating liquid (A), alcohol and other organic solvents. The total amount is preferably less than 50% by mass. When the amount of the organic solvent added is less than 50% by mass based on the total amount of the solvent, the drying property can be improved when the coating is dried, and the appearance of the coating-adhesive modified layer (A) can be improved when compared with water alone. When the amount of the organic solvent is 50% by mass or more based on the total amount of the solvent, the evaporation rate of the solvent becomes high, and the concentration of the coating liquid (A) during coating tends to change. As a result, the viscosity of the coating liquid (A) rises, the coatability is lowered, and the appearance of the coating film is unfavorable. In addition, since the organic solvent is volatilized, the risk of fire or the like is also increased. (d) When the aqueous coating liquid (A) is applied to the surface of the thermoplastic resin film (base film), the wettability of the film is improved, and the coating liquid (A) is uniformly coated. In general, it is preferred to use a surfactant. The surfactant is not particularly limited as long as it has good coatability. Among the surfactants, when a good coating property is obtained in a small amount, a fluorine-based surfactant is preferred. The amount of addition to the coating liquid (A) to match 0. 001~0. 018% by mass is preferred. (e) Inorganic particles -33- 201000311 When a hard coat film or the film is used as an optical functional film which is required to have high transparency, the substrate film has a haze of preferably 5% or less. Haze is greater than 1. When 5% is used, when the film is used for a display member or the like, The sharpness of the picture is reduced, so it is not intended. In order to make the substrate film have a haze of 1. When it is 5 % or less, the present invention is substantially free of particles in the substrate film. When the base film does not contain particles, the processability (smoothness, running property, blocking property, and air removal air accompanying the air during winding) in order to improve the scratch resistance or the roll-to-roll shape or the roll-out property In the case of the adhesion-modifying layer (A), inorganic particles are contained. Thereby, the adhesive modified base film of the present invention can maintain high transparency and impart smoothness and take-up resistance to scratch resistance. Next, the inorganic particles contained in the modified layer (A), such as calcium carbonate, calcium phosphate, amorphous cerium oxide, crystalline glass fiber, kaolin, talc, titanium dioxide, aluminum oxide, cerium oxide-alumina composite Inorganic particles such as oxide particles, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, mica, crosslinked polystyrene particles, crosslinked acrylic resin particles, crosslinked methyl methacrylate particles, Heat-resistant polymer particles such as benzoguanamine-formaldehyde condensate particles, melamine-formaldehyde condensate particles, and polytetrafluoroethylene particles. Among these particles, since the refractive index of the resin component is relatively close, it is preferred to use a ruthenium dioxide particle in the case of a film which is highly transparent. Further, the shape of the particles is not particularly limited, and it is preferable to impart a smoothness to the particles which are close to a spherical shape. The content of the particles constituting the entire amount of the modifying layer (A) is preferably 20% by mass or less, more preferably 15% by mass or less, and most preferably 1% by mass or less. The particle content in the composite is greater than 20 mass. When it is 〇, transparency is easy to be evil -34-201000311 and the adhesion of the film is also likely to become insufficient. Further, the lower limit of the content of the particles is 0, and is 0 for the composite layer. 1 quality. /. Preferably, it is more preferably 1% by mass, more preferably 3% by mass. Further, the composite may contain two or more kinds of particles having different average particle diameters. Further, it may contain the same kind of particles and have different average particle diameters. When the coating liquid (A) is applied, in order to remove coarse aggregates of particles in the coating liquid (A), it is preferred to arrange a filter material which is subjected to precision filtration treatment before coating. Further, when the particles are one type or two or more types, the average particle diameter of the particles (A) as a main component is preferably 20 to 150 nm, more preferably 40 to 60 nm. When the average particle diameter is less than 2 Onm, it is difficult to obtain sufficient blocking resistance, and the scratch resistance tends to be deteriorated. Further, when two or more kinds of particles are used, when particles B having a large auxiliary particle diameter are added, the average particle diameter of the particles B is preferably from 1 60 to 100 nm, more preferably from 200 to 800 nm. When the average particle diameter of the particles B is less than 1 60 nm, the scratch resistance, the smoothness, and the windability are deteriorated. Further, when the average particle diameter of the particles B is more than 100 nm, not only the particles are liable to fall off, but also the haze tends to increase. Further, the particles B (average particle diameter: 160 nm to 100 nm) can be easily obtained by the dry method of cerium oxide, and the aggregate having a primary average particle diameter of 40 to 60 nm is not easily detached. This is inferred in the film forming process, and after the adhesion modifying layer (A) is applied, a flat, stable shape can be formed by the elongation process and the heat setting process. Further, the use of particles having a ratio of the average particle diameter in the aggregated state to the average particle diameter of the primary particles of 4 or more is preferable in terms of scratch resistance. The measurement of the average primary particle diameter and the average particle diameter of the above particles was carried out by the following method. The particles were photographed by an electron microscope, and the maximum particle diameter of 300 to 500 particles was measured with a minimum particle size of 2 to 5 mm, and the average 値 of -35 - 201000311 was taken as the average primary particle diameter or the average particle diameter. Further, when the average particle diameter of the particles in the adhesion-modifying layer (A) of the adhesive-modified substrate film is determined, a transmission electron microscope (TEM) is used to photograph the adhesion-modified layer substrate at a magnification of 120,000 times. The cross section of the film, the particles of the composite are obtained. The maximum particle size of the child. The average particle diameter of the particles formed by the aggregates is measured by using an optical microscope at a cross section of the adhesive modified layer (A) of the adhesive-modified substrate film at a magnification of 200 times 300 to 500. Maximum particle size. The adhesion-modifying layer (A) of the present invention contains the above-mentioned inorganic particles of an appropriate particle diameter and has surface protrusions having a protrusion height of 1 〇〇 nm or more by the inorganic particles on the surface of the adhesion-modifying layer (A). . In order to impart an appropriate smoothness to the adhesive-modified substrate film, the density of surface protrusions at a height of 1 〇〇 nm or more when measured by a non-contact surface roughness meter is 10/mm 2 or more and 100 00. /mm2 or less is preferred. In order to achieve i/mm2, the coefficient of friction becomes large, and most of the surface scratches which cause the optical defects are generated. Further, when the amount is more than 1000/mm2, the haze becomes high, and the amount of occurrence of falling off of the particles increases, so that it is not desired. In the present invention, by forming surface protrusions having a height of 100 nm or more by inorganic particles in the adhesion-modifying layer (A), not only smoothness but also a base film and a hard film can be formed when a hard coat film is formed. The structure of the organic-inorganic composite described below was dispersed over the boundary of the coating layer. The adhesion between the base film and the hard coat layer can be imparted by the organic-inorganic composite having the dispersion. When the organic-inorganic composite is used to improve the adhesion, it is considered that the composite has an underlayer function, an effect of increasing the area of the boundary layer, and the like. Further, the 'organic-inorganic composite of the present invention has an excellent interference reduction effect' can be considered as an organic-inorganic composite from the above surface protrusion-36-201000311, which has a shape to achieve a light scattering effect, and has an interference spot reduction effect. The light scattering effect by the protrusion referred to herein is presumed to have an in-plane optical anisotropy (a property different in refractive index depending on the angle of observation) of the biaxially stretched film, and the interference interference spot is not provided. The effect of uniformity. Therefore, the adhesive modified base film of the present invention can attain a practical interference spot reduction effect when viewed from the angle of the hard coat layer. In the present invention, in order to obtain an excellent effect of reducing the interference spot, it is preferable to uniformly disperse a part of the particles in a state of being appropriately agglomerated. Thereby, even if the refractive index difference between the hard coating layer and the substrate film is 0. When the angle of 02 or more is large, and the angle of light scattering is observed at all angles, a practical interference spot reduction effect can still be obtained. The specific method for producing an appropriate agglomerate is as follows. In the present invention, the maximum diameter 麓 of the haw portion of the above-mentioned surface protrusion having a height of 100 nm or more formed on the surface of the adhesion-modifying layer (A) must be 1 μm or more. As described below, in the adhesive-modified substrate film of the present invention, when the hard coat layer is laminated, the base film and the hard coat layer are directly laminated to have an extremely thin adhesion-modifying layer (A). When the thickness of the resin layer is made thin as described above, the haw portion which forms a mountain-like surface protrusion tends to be small, and the particles are easily detached. Therefore, the average diameter of the haw portion of the surface protrusion having a height of 100 nm or more is ΙΟμιη or more, preferably ll#m or more, more preferably 15/m or more, and the retention of the particles can be changed. high. When the maximum diameter of the surface coated with a height of lOOnm or more is more than the above, the powder falling condition can be suppressed, the process contamination can be reduced, and the stable surface friction characteristics can be obtained. Here, the mountain portion of the surface protrusion is a soil portion of the surface protrusion, and specifically, the average height in the field of 1 to 37-201000311 (measurement range) when measured in a non-contact surface roughness form. The convex piled up part. For example, when the result of measuring the three-dimensional shape is observed by the contour line indicating that the average height in the measurement range is Onm and the predetermined color is different, the average height of the contour line formed on the concentric circle is centered on the surface protrusion. The color distinguishing part is the hawthorn part. The maximum diameter of the mantle portion refers to the maximum distance between the two points at which the average height line in the one field of view (measurement range) intersects the cross-sectional view when observing the cross-sectional image of one surface protrusion. For example, the above-mentioned contour line indicates the maximum diameter of the circular color-division portion of the average height of the inner surface of the apex of the surface protrusion when the morphometry is performed. Specifically, when the cross-sectional view is expressed by the contour line, the two ends of the cursor are moved to the longitudinal direction of the circular height-division portion of the average height at the position where the both ends of the cursor pass the maximum height of the surface protrusion. The distance between the two focuss at which the cross-sectional curve of the surface protrusion obtained is read and the average height line in the measurement field of view is taken as the maximum diameter of the haw. The average 値 of the maximum diameter of the hawthorn portion is arbitrarily selected from the surface protrusions having a height of 20 or more and a height of l 〇〇 nm or more, and the average enthalpy when measuring the maximum diameter of the above-mentioned haw portion is determined. Further, as the non-contact surface roughness meter, a non-contact three-dimensional shape measuring device manufactured by Meco Roman Co., Ltd., or a non-contact roughness measuring device using a laser or the like can be used. In the present invention, when the maximum diameter of the haw portion of the surface coated with a height of 100 nm or more is l〇#m or more, the aggregate of the appropriate inorganic particles is formed and the resin coated with the coating liquid (A) is coated. Inorganic particles are preferred. In the present invention, in order to form agglomerates of suitable particles and to reduce the detachment of the particles and the aggregates of the particles, when particles are added in the coating liquid (A) mixing stage, the particles and the resin having high affinity are previously prepared. It is advisable to treat it before it is covered. The resin having a high affinity for the particles is not particularly limited, and is preferably coated with a resin having the same main component as the main component of the resin contained in the adhesive layer (A) of -38 to 201000311. Further, when the polarity of the polar group contained in the coated resin is opposite to the polarity of the inorganic particles to be coated, since it has high affinity with the inorganic particles, it can be easily and more strongly coated, which is preferable. Further, the higher the flexibility, the higher the retention of the inorganic particles. Specifically, the "flexible resin having a glass transition temperature of 60 ° C or less" is preferable in terms of retaining inorganic particles. The coated resin is a flexible polyurethane-based resin, and the particles are cerium oxide particles, which is an example of a preferred embodiment. The relationship between the resin to be coated and the inorganic particles is a combination of electrical yin and yang, which is a better embodiment. In the pretreatment, it is considered that when the coating liquid (A) is applied and dried, a large amount of the resin component is accumulated around the inorganic particles to form a haw portion of the surface protrusion defined by the present invention, which can reduce the inorganic particles. Shedding situation. In the following description, the method for treating the particles is not particularly limited as long as it is a method in which particles can be coated on the particles and a resin having high affinity. First, make the inorganic particles 0. The dispersion having a concentration of 0% by mass or more and less than 5% by mass is previously added to water containing an inorganic particle and a resin having high affinity, or an organic solvent or a mixed solution thereof. Less than 〇. When the mass is %, there are inorganic particles that cannot be sufficiently coated. When it is 5% by mass or more, it is easy to produce a large amount of coarse aggregates having a required amount or more, and therefore it is not desired. The resin having a high affinity is preferably 〇·1% by mass or more and less than 25% by mass. When it is less than 0 · 1 mass%, a sufficient coating effect cannot be obtained. When it is 25 mass% or more, it is easy to produce a large amount of coarse aggregates which are necessary or more. -39- 201000311 Then, the obtained dispersion was at 20 ° C or more and less than 50 °. (Stirring under the condition of ^) and coating the inorganic particles or the aggregate of the inorganic particles with the inorganic particles and the resin of the affinity cylinder. When less than 20 t:, it is extremely time consuming at the time of coating, and when it is more than 50 ° C, the resin Deterioration (discoloration), so it is not required. Mixer such as powder dissolving machine (T. K. The homomixer type) is such that the number of revolutions is 5,000 rpm or more, preferably 〇〇〇〇 rpm or more, and the stirring time is 1 hour or more, preferably less than 3 hours, for 10 kg of the dispersion. When it is less than 1 hour, a sufficient coating effect cannot be obtained, and when it is 3 hours or more, the effect does not largely change even when dispersed. (f) Crosslinking agents Information terminals such as mobile phones, PDAs, and hand-held computers have increased opportunities for use outside the home. In addition, the touch panels used in satellite navigation systems and the like have increased the materials used in the cars at high temperatures in summer. Further, even in a high-temperature, high-humidity environment, a hard coating film having a small change in quality, that is, a film excellent in wet heat resistance is extremely desirable for this application. When the hard coat film of the present invention is used for this application, in order to improve the moist heat resistance, a crosslinking agent may be added to the coating liquid (A), followed by heat treatment to have a crosslinked structure in the resin. The crosslinking agent is at least selected from the group consisting of an epoxy crosslinking agent, a melamine crosslinking agent, an oxazoline crosslinking agent, and an isocyanate crosslinking agent. The crosslinking agent can be selected in consideration of the affinity with the copolymerized polyester resin used in the coating liquid (A) and the wet heat resistance. Moreover, since excessive expansion may impair proper expandability, it is not desirable. When the above-mentioned crosslinking agent is used, the total amount of the copolymerized polyester resin and the crosslinking agent of the composite (100% by mass) is preferably 5 to 40% by mass, more preferably 1 〇. ~30% by mass. When the content of the crosslinking agent is more than 40% by mass, the composite becomes brittle and cannot be obtained in a processing process after forming a hard coating layer of the acrylate-based resin, such as a hard coating layer-40-201000311 or a diffusion layer. Adequate tolerability of high-speed cutting. Further, when the content of the crosslinking agent is less than 5% by mass, the durability required in recent years is not easily obtained. Further, in the coating liquid (A), in order to promote crosslinking, a catalyst may be added as needed. (3) Coating process An in-line coating method in which the above coating liquid (A) is applied to apply the coating in the film process is preferred. More preferably, it is applied to the substrate film before the completion of the crystal alignment. The solid content concentration in the coating liquid (A) is preferably 2% by mass or less, more preferably 1% by mass or less. The lower limit of the solid component concentration is 〇. 1% by mass is better, and more preferably 0. 3 mass%. The film coated with the coating liquid is introduced into a tenter during the alignment and heat setting treatment, and then heated to form a stable film by thermal crosslinking reaction to form a film of the adhesive modified base material. The coating amount in the case of not drying (hereinafter referred to as wet coating amount) is preferably 2 g/m 2 or more and less than 10 g/m 2 . When the amount of the wet coating is less than 2 g/m2, the dry coating amount of the design (the amount of the coating layer of the next modified layer (A)) is required, and the solid content concentration of the coating liquid (A) must be increased. When the solid content of the coating liquid (A) is increased, the viscosity of the coating liquid (A) is increased, and strip coating spots are likely to occur. Further, when the wet coating amount is 10 g/m2 or more, it is likely to be affected by the dry wind in the drying oven, and the coating spot is likely to occur. Further, in order to prevent the disadvantage of adhesion due to dust, it is preferred to apply the coating liquid (A) in a clean environment having a cleanliness level of 5000 or less. The coating amount (the final coating amount after drying) of the adhesion-modifying layer (A) of the present invention must be 3 to 12 g/m2. When the coating amount is too large, when the coating layer is laminated, when the refractive index is low and the independent adhesion-modifying layer (A) is formed between the coating layer having a high refractive index and the base film, the interference spots are likely to become conspicuous. When the amount of coating is -41 - 201000311, it is less likely to cause the inorganic particles to fall off, and the practical adhesion cannot be obtained. (3) Coating layer (B) In a preferred embodiment of the present invention, a coating layer (B) containing a polyester resin and a titanium compound may be provided on the other surface. At this time, the buildup structure is the order of the coating layer (B) / the base film / the adhesion modifying layer (A). The coating layer (B) is preferably obtained by applying a coating liquid (B) to a substrate film and drying it. As described above, the coating liquid applied when the coating layer (B) is obtained is defined as "coating liquid (B)". In the present invention, the coating liquid (B) used to form the coating layer (B) is formed mainly of a polyester resin, particularly an aqueous polyester resin, a water-soluble titanium compound, and an aqueous solvent. Water coating solution. The titanium compound contained in the coating liquid (B) can be crosslinked with an aqueous polyester resin, and a more uniform film is preferably produced by the crosslinking reaction. The crosslinking reaction is promoted by heat when the base film is stretched, and as a result, the titanium compound is thermally decomposed, and it is not necessarily required to be contained in the obtained coating layer in the same state as in the coating liquid ( B). The refractive index of the coating layer (B) is increased by the composition ratio of the titanium compound, which is higher than that of the aqueous polyester resin alone. Thereby, even if an adhesive layer mainly composed of the following acrylic resin is laminated, generation of interference spots can be suppressed. In order to increase the refractive index of the coating layer (B), it may be achieved by containing metal fine particles, but the adhesion of the coating layer and the adhesion between the hard coating layer and the base film are lowered by the inclusion of the metal fine particles. The aqueous polyester resin used in the present invention may also introduce an active site such as a hydroxyl group or a carboxyl group into the molecular chain thereof, in particular, even if it is not introduced, a reversible reaction is caused by the ester bond site, and a crosslinking reaction is caused at any position. As a result, a dense film can be obtained. -42-201000311 The titanium compound used in the present invention is preferably used as an aqueous coating liquid, and a water-soluble titanium compound is preferred. As the water-soluble titanium compound, a water-soluble chelate compound, a water-soluble titanium telluride compound, a water-soluble zirconium chelate compound, or a water-soluble chromium telluride compound can be used. A water-soluble titanium chelate compound such as titanium diisopropoxy bis(acetic acid), titanium isopropoxy (2-ethyl-1,3-hexanedioleate), diisopropoxy Bis(triethanolamine)titanium, di-n-butoxybis(triethanolamine)titanium, hydroxybis(lactic acid)titanium, hydroxybis(lactic acid)titanium ammonium salt, titanium peroxycitrate ammonium salt, and the like. Further, the water-soluble titanium telluride compound is, for example, bis(monoammonium methoxide) carbonyl titanium or the like. Further, the water-soluble chromium compound may, for example, be a tetrakisuccinic acid zirconium salt or a chromium acetate salt. Among them, in order to adjust the pH of the coating liquid, the refractive index adjustment of the coating layer, and the adhesion, it is preferable to use a titanium lactate compound and a triethanolamine titanium compound. The aqueous polyester resin of the coating layer (B) is related to the adhesion of the base film. Therefore, when the mass of the aqueous polyester resin contained in the coating layer is (a) and the mass of the titanium compound is (d), the ratio of (a) / (d) is preferably 50/50 or more. When the enthalpy is 5 0/5 0 or more, the transparency required for optical use can be improved, and the adhesion of the adhesive layer formed on the coating layer is good. Further, it is preferable that the enthalpy of (a)/(d) is 80/20 or less. In this case, since the titanium compound is sufficiently crosslinked, the refractive index can be increased, and therefore, the adhesion under high temperature and high humidity can be improved ( The effect of suppressing the heat and humidity of the rainbow and the rainbow color under the fluorescent lamp is sufficient. The titanium compound described above is a titanium lactate compound and a triethanolamine titanium compound, and is a preferred embodiment of the present invention. The quality of the titanium lactate compound is -43 - 201000311 (b), and the mass of the triethanolamine titanium compound. In the case of (c), the above (d) and [(b) + (c)] are preferred. In this case, the relationship (b) / (C) above is preferably 35/65 to 65/35 after (b) / (C). When it is within the above range, the p Η値 of the coating liquid (B) becomes approximately neutral (pH 値 ό 8), and as a result, the coating layer is accompanied by the isocyanate-curable acrylic resin-based adhesive on the coating layer. When the adhesion to the adhesive layer is improved, the interference spots generated on the side of the adhesive layer can be reduced. The technical significance of both the titanium lactate compound and the triethanolamine titanium compound in the coating layer (Β) is as follows. When only one type of the titanium compound is used, the pH of the coating liquid tends to be too acidic or alkaline. When an isocyanate-curable acrylic resin-based adhesive is laminated on the coating layer (B) obtained by the coating liquid (B) which is largely alkaline, the curing layer is likely to be formed in the thickness direction of the adhesive layer, and as a result, it is attached to the display. In the front, it will reduce the reworkability when the attachment is not good. When the reworkability is lowered, there arises a problem that the amount of the adhesive layer increases from the front of the display at the time of peeling. In addition, when the isocyanate-curable acrylic resin-based adhesive is applied to the coating layer (B) obtained by the coating liquid (B) which is highly acidic, the adhesive tends to be hardened and prevented, and the reworkability is lowered as described above. . When only one of the above titanium compounds is used, the pH of the coating liquid (B) is acidic or alkaline. In order to adjust the pH of the coating liquid, when it is acidic, an alkaline compound such as amine, ammonium or sodium hydroxide may be added, and when it is alkaline, an acidic compound such as a carboxylic acid, a hydrochloric acid or a sulfonic acid may be added. When the pH is adjusted, the compatibility between the titanium compound and the aqueous polyester resin in the coating layer (B) is lowered, and as a result, the coating film becomes uneven, and the effect of suppressing the rainbow color of the adhesive layer is lowered, and the adhesion is lowered. Therefore, it is not suitable for the use of the present invention. -44 - 201000311 In the present specification, after the polyester resin is plasticized in the heated butyl cellosolve, when the polyester resin reaches a dispersed state when warm water is added, the polyester resin becomes an aqueous polyester resin. . When the polyester resin is aqueous, it is important to introduce a hydrophilic group such as a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group or an ether group into a molecular chain of the polyester resin. Among the above hydrophilic groups, a sulfonic acid group is preferred in terms of physical properties of the coating film and adhesion. When a sulfonic acid group is introduced into the polyester, the sulfonic acid compound is more preferably 1 to 10 mol% based on the total acid component of the polyester. When the amount of the sulfonic acid group is less than 1 mol%, since the polyester resin is rendered non-aqueous, the compatibility with the water-soluble titanium compound is also lowered, and it is difficult to obtain a uniform and transparent coating layer. Further, when the amount of the sulfonic acid group is more than 10% by mole, the adhesion (heat and humidity resistance) under high temperature and high humidity is liable to deteriorate. Further, the aqueous polyester resin is preferably a glass transition temperature of 40 ° C or more. Therefore, the acid component of the aqueous polyester resin is preferably an aromatic component such as citric acid, isophthalic acid or naphthalene dicarboxylic acid. Further, the diol component is preferably an aromatic compound such as a glycol having a small carbon number such as ethylene glycol, propylene glycol, 1,4-butanediol or neopentyl glycol, or an ethylene oxide adduct of bisphenol A. . Further, the raw material of the polyester resin may be a rigid component such as biphenyl or a dicarboxylic acid component or a diol component having an atom having a high refractive index such as bromine or sulfur, insofar as the physical properties of the film are not lowered. When the glass transition temperature of the aqueous polyester resin is 40 ° C or more, the adhesion (heat and humidity resistance) under high temperature and high humidity is sufficient. Further, in order to increase the refractive index of the polyester resin, the refractive index of the coating layer (B) also increases. As a result, the rainbow-like color under the fluorescent lamp can be easily and sufficiently suppressed. A titanium lactate compound and a triethanolamine titanium compound are also contained in the coating layer (B). A typical example of a water-soluble titanium lactate compound, such as bis(lactic acid) titanium oxide -45 - 201000311. Further, typical of the water-soluble triethanolamine titanium compound is, for example, diisopropoxy bis(triethanolamine) titanium. In the coating layer (B), a resin other than the above-mentioned main component may be used, for example, an acrylic resin, a polyurethane resin, a polyester resin, or an alkyd resin, insofar as the effects of the present invention are not impaired. A vinyl resin such as polyvinyl alcohol. Further, 'the crosslinking agent' can be used in a range that does not affect the effects of the present invention, and is not particularly limited. A crosslinking agent which can be used, for example, an amine group such as urea, melamine, benzoguanamine or the like, and an alkyl ether compound formed from an adduct and an alcohol having 1 to 6 carbon atoms. A resin, a polyfunctional epoxy compound, a polyfunctional isocyanate compound, a blocked isocyanate compound, a polyfunctional aziridine compound, an oxazoline compound, or the like. It is preferred to contain the cerium oxide particles in the coating layer (B). The block resistance or processability can be improved by the presence of ruthenium dioxide. As the cerium oxide particles, commercially available colloidal cerium oxide particles or the like can be suitably used. The content of the cerium oxide particles in the coating layer (B) is preferably from 0.1 to 2% by weight. When the aqueous coating liquid (B) is applied to the surface of the polyester film, a conventional anionic surfactant or a nonionic interface is added in an appropriate amount in order to improve the wettability of the film and uniformly apply the coating liquid (B). The active agent is preferred. Further, in the aqueous coating liquid (B), in order to impart other functions such as processability, antistatic property, and antibacterial property to the film, inorganic or/or heat resistant polymer particles, an antistatic agent, and ultraviolet absorption may be contained. Additives such as agents, organic lubricants, antibacterial agents, photo-oxidation catalysts, and the like. The solvent to be used in the coating liquid (B) may be an alcohol such as ethanol, isopropyl alcohol or benzyl alcohol other than water in a range of less than 50% by mass based on the entire coating liquid (B). Further, when it is less than 10% by mass, it may be mixed in a range in which an organic solvent other than the alcohol is soluble. The total amount of the alcohol in the coating liquid (B) and the other organic solvent of -46 - 201000311 is preferably less than 50% by mass. In the present invention, the coating amount of the finally obtained coating layer can be adjusted depending on the refractive index of the adhesive layer used, specifically, 〇. 〇 2~ 0. 5g/m2 is better, with 0. 05 ~ 0. 3g/m2 is better, 〇. 〇7 ~〇. 2 g/m2 is preferred. The coating amount of the coating layer (B) is 0. When it is 02 g/m2 or more, the effect is remarkable for the adhesion property, and it is easy to make the suppression effect of the rainbow color under the fluorescent lamp sufficient. In addition, the coating amount is 0. When the color is 5 g/m2 or less, the suppression effect of the rainbow color under the fluorescent lamp is likely to be sufficient. (4) Hard coat film (a) Hard coat layer A hardened resin constituting a hard coat layer is preferably an ionizing radiation curable resin. The ionizing radiation curable resin is, for example, the following resin. Among the ionizing radiation curable resins, a resin having an acrylic functional group is preferred, and a polyester acrylate or a urethane acrylate is more preferred. The polyester acrylate is an acrylate or methacrylate of an oligomer of a polyester-based polyol (hereinafter, acrylate and/or methacrylate describes that γ is (meth) acrylate), or a mixture thereof Composition. Further, the carbamic acid carboxylic acid (meth) acrylate is composed of a (meth) acrylated oligomer composed of a polyol compound and a diisocyanate compound. a monomer constituting a (meth) acrylate such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (a) Base) methoxyethyl acrylate, butoxyethyl (meth) acrylate, phenyl (meth) acrylate. Further, when it is necessary to increase the hardness of the hard coat layer, it is preferred to use a polyfunctional monomer. Polyfunctional monomers such as trimethylolpropane tri(meth)acrylate, hexanediol (meth)acrylate, tripropylene glycol di(meth)acrylate, -47-201000311 diethylene glycol di(methyl) Acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate. Polyester-based polyol oligomers such as adipic acid and diol (ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, butanediol, polybutylene glycol, etc.) or triol (glycerol, three A polyadipate polyol or a polysebacate polyol in which a condensation product of citric acid and a diol or a triol is condensed. Further, some or all of the above aliphatic dicarboxylic acids may be substituted with other organic acids. For example, isophthalic acid, p-citric acid, or phthalic anhydride can be used as a component for increasing the hardness of the hard coat layer. When the hard coat layer is formed on the base film, in order to improve the level, it may be diluted with a diluent as needed. The diluent is an aromatic hydrocarbon such as benzene, toluene or xylene, an aliphatic hydrocarbon such as hexane, heptane, octane, decane or decane, or a ketone such as methyl ethyl ketone, diethyl ketone or diisopropanone. Wait. The amount of the diluent is appropriately selected at an appropriate viscosity. The inorganic fine particles contained in the hard coating layer, for example, amorphous cerium oxide, crystalline glass cerium, cerium oxide, zirconium oxide, titanium oxide, aluminum oxide, inorganic oxide, cerium oxide-alumina composite Oxide particles, magnesium carbonate, aluminum hydroxide, barium sulfate, calcium carbonate, calcium phosphate, kaolin, talc, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, mica. The hard coat film of the present invention has a refractive index of 1. 60~1. A hard coat layer of 65 is preferred. When the anti-reflective layer composed of the cylindrical refractive index layer/low refractive index layer or the high refractive index layer/medium refractive index layer/low refractive index layer is laminated on the surface of the hard coating layer, the hard coating layer is subjected to a high refractive index The high refractive index layer can be omitted from the antireflection layer. As a result, the cost can be reduced. In order to increase the refractive index of the hard coat layer, the inorganic fine particles having a high refractive index in the hard coat layer are effective from -48 to 201000311. Inorganic fine particles having a high refractive index such as chromium oxide or titanium oxide. Further, when the content of the inorganic fine particles is more than 80% by mass, the transparency tends to be lowered. Further, the average particle diameter of the inorganic fine particles is preferably from 5 to 100 nm in terms of slipperiness and transparency. The high refractive index hard coating agent containing inorganic fine particles can be obtained from a commercially available product. For example, UV-curable resin (Desolite) manufactured by JSR Co., Ltd.; Z7400B, Z7410B). Further, an appropriate amount of inorganic fine particles having a high refractive index is added to the acrylic resin, and the refractive index is adjusted to 1. 60 ~ 1. The scope of 65. The ionizing radiation-curable resin can be cured by ultraviolet light or electron beam irradiation. When irradiating ultraviolet rays, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide lamp, or the like is used, and a wavelength range of 10 〇 to 400 nm, preferably 200 to 400 nm, is 1 〇〇 3 The energy of 000m J/m2 is irradiated with ultraviolet light. Further, when irradiating an electron beam, a scanning type or a curtain type electron beam accelerator is used, and an energy having an acceleration voltage of 100 OkeV or less (preferably 1 〇〇 to 300 keV) is applied, and an electron beam having a wavelength range of not more than ηηη is irradiated. The thickness of the hard coating layer is at 0. The range of 1~30#m is determined by its use. More preferably, it is 1 to 15/zm. When the thickness of the hard coat layer is within the above range, the surface of the hard coat layer is high in hardness and is not easily scratched. Further, the hard coat layer is less likely to become brittle, and the hard coat layer is less likely to be broken when the hard coat film is bent. Further, in the present invention, another optical functional layer may be laminated on the surface opposite to or on the hard coat layer of the hard coat film of the present invention, and the following two embodiments may be employed. (A) at least one layer of an optical functional layer selected from the group consisting of a hard coating layer, a light diffusion layer, a diamond lens layer, an electromagnetic wave absorbing layer, a near red line mask-49-201000311, and a transparent conductive layer on the opposite surface of the hard coating layer Optical functional film. (B) An optical functional film in which an antireflection layer or an antifouling layer is laminated on a hard coat layer. (b) Organic-inorganic composite When a hard coating layer is laminated on the surface of the adhesive modifying layer (A) of the adhesive-modified substrate film of the present invention, the hard coating layer is directly laminated on the substrate film on the substrate. An organic-inorganic composite (hereinafter referred to as "composite") is dispersed over the boundary between the film and the hard coat layer. The organic-inorganic composite has a structure in which at least one type of inorganic particles are embedded in a polyester resin, a urethane resin, or an acrylic resin. The above-mentioned composite, for example, an ultrathin section of the hard coat film of the invention, can be observed by using a transmission electron microscope (TEM) at a magnification of 50,000 to 200,000 times. The boundary range of the layer. The above composite has a structure in which inorganic particles are embedded in at least one resin composition selected from the group consisting of a polyester resin, a urethane resin, and an acrylic resin. TEM observation of the image, depending on the electron density can be observed in contrast to the shade. The inorganic particles have a high electron density and a thick resin composition selected from the group consisting of polyester resins, urethane resins, and acrylic resins, and have low electron density. Therefore, the above composite is a structure in which a resin composition which is equivalent to the base film or which is lighter than the base film is surrounded by the rich inorganic particles. In the present invention, a separate composite is preferably in the form of an inorganic particle or an inorganic particle agglomerate. When at least one resin composition selected from the group consisting of a polyester resin, a urethane resin, and an acrylic resin contained in the organic-inorganic composite is observed by a transmission electron microscope (TEM), ruthenium dyeing is performed. Dyeing treatment such as hungry dyeing, phosphotungstic acid dyeing or the like is preferred. In particular, hydrazine dyeing can be suitably dyed with a polyester resin, an amine-50-201000311 urethane resin. The respective constitutions of the organic-inorganic composite can be judged by the dyed image of the above dyeing. Further, the respective constitutions of the organic-inorganic composites can be judged by local elemental analysis (SEM/EDX, etc.). Further, after forming the hard coat film, the resin composition constituting the adhesive layer (A), that is, the resin composition constituting the organic-inorganic composite, for example, the coated surface of the adhesive modified base film or the hard coat layer / The substrate film interface is analyzed and specified by infrared spectroscopy. The above composite exists in the boundary range between the base film and the hard coat layer. , the boundary range refers to the vicinity of the interface between the substrate film and the hard coat layer. When the hard coat film of the present invention was observed by TE Μ, the above composite was observed at the boundary where the base film and the hard coat layer were in contact. It is preferred that each of the above composites is bonded to both the base film and the hard coat layer. The above composite is dispersed in a boundary range between the base film and the hard coat layer. The composite dispersion means that when the hard coat film of the present invention is observed by hydrazine, a plurality of composites are not all joined together, and are dispersed. In other words, the composite formed by the inorganic particles surrounding the resin composition is independently present, and a plurality of inorganic particles are not continuously connected by the resin composition between the base film and the hard coat layer. The structure of continuous connection means a state in which an organic substance as a resin composition is present on the boundary between the base film and the hard coat layer. When the present invention is observed by a transmission electron microscope (TEM) at a magnification of 50,000 times to 200,000 times, at least one selected from the group consisting of organic-inorganic composites is not observed at the boundary between the base film of the hard coat film and the hard coat layer. A resin composition layer of a resin composed of a polyester resin, a urethane resin or an acrylic resin which is a constituent component of the composition is important. Here, the resin composition layer was not observed, and when it was observed by a transmission electron microscope (TEM) at a magnification of 50,000 times to 200,000 times, the thickness of the resin layer in the boundary range was below the critical value of observation. 201000311 is in a state equivalent to the base film in which the resin composition layer is not provided. Specifically, the boundary between the hard coat layer and the base material layer is 10 nm or less, preferably 5 nm or less. This is due to the precipitation of the dye at the boundary between the hard coat layer and the substrate layer by the operation during dyeing or the like. The distance between the adjacent two composites in the boundary range is not particularly limited, and it is preferable to have a distance of 1 0 0 to 1 0 0 nm. The preferred method for producing the composite is as follows. For example, when the coating liquid (A) containing the resin and the inorganic particles constituting the composite is applied to the base film, it is extremely thinly coated and dried, and then, when the hard coating layer is formed. A method of coating and drying a hard coating agent made of a curable resin. According to this production method, the resin constituting the composite is at least partially expanded by a hard coating agent for forming a hard coat layer, and then integrated with the resin of the hard coat layer. As a result, in the range where the above inorganic particles were not present, the resin of the hard coat layer was integrated to the extent that the coating layer was not observed by TEM. In other words, when observed by a transmission electron microscope (TEM) at a magnification of 50,000 to 200,000 times, the thickness of the resin composition layer in the boundary range is below the observation threshold. In addition, a resin constituting the composite remains around the inorganic particles, and as a result, a structure in which the composite is embedded between the base film and the hard coat layer is formed. The present invention changes the overall idea of the separate "layer" provided for the base film and the hard coat layer, and the base film and the hard coat layer are subsequently joined by dispersing the composite. Thereby, sufficient adhesion can be maintained, and the interference spots can be remarkably reduced. (c) Adhesive layer A preferred embodiment of the present invention is a hard coat film in which an adhesive layer is additionally laminated on the surface of the coating layer (B). The adhesive used in the present invention preferably contains an acrylic polymer as a main component and -52-201000311, an isocyanate-based curing agent, in terms of adhesion and reduction of interference spots. By providing the adhesive layer, it is possible to cope with a laminated film which is integrated with various members. Further, in the adhesive layer, a pigment such as a near-infrared ray absorbing agent may be added as needed. The acrylic resin contained in the acrylic adhesive layer is preferably, for example, in the following form. The acrylic resin is preferably a homopolymer of an alkyl (meth)acrylate or a copolymer thereof. The acrylate used as the monomer of the acrylic resin has, for example, an alkyl group having 1 to 12 carbon atoms, specifically, methyl (meth)acrylate, ethyl (meth)acrylate, or (methyl). N-propyl acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, amyl (meth) acrylate, cyclohexyl (meth) acrylate, (Methyl) 2-ethylhexyl acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, and the like. These may be used alone or in combination of two or more. In addition to the above (meth) acrylate, a monomer having another unsaturated double bond, such as an olefin-based or vinyl-based (except acrylic acid) monomer (for example, containing ethylene, vinyl acetate, styrene, etc.) may be contained. ) as a copolymerization component. Such a monomer having other unsaturated double bonds may contain a range of 20% by weight or less. Further, it is preferred that the (meth) acrylate is coexistent with the monomer having a functional group in the (meth) acrylate. Thereby, the above (meth) acrylate can be copolymerized with a monomer having a functional group to obtain a (meth)acrylic resin having a functional group. By the monomer having a functional group in the (meth)acrylic resin, the functional group can be reacted with a crosslinking agent to crosslink the (meth)acrylic resin. By this crosslinking, the peeling of the adhesive layer and the substrate film can be prevented, and the mechanical strength of the adhesive layer can be improved. The above-mentioned monomer having a functional group such as a carboxyl group-containing aliphatic unsaturated carboxylic acid such as (meth)acrylic acid, maleic acid, itaconic acid or -53-201000311 citraconic acid. The aliphatic unsaturated carboxylic acid is preferably 5% by weight or less, and more preferably 3, based on the (meth)acrylic resin. The range of 5% by weight or less. When it is more than 5% by weight, it is easy to cause a residual paste after peeling. A monomer having another functional group such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxyvinyl ether or the like having a hydroxyl group, hydrazine, hydrazine-dimethyl Amino group (ethyl) acrylate, aminoethyl (meth) acrylate, dimethylamino propyl (meth) acrylate, etc. having an amine group, glycidyl acrylate, A Examples of the epoxy group-containing acryl acrylate such as acrylonitrile, acrylonitrile, acrylamide, and the like may be used alone or in combination of two or more. The total content of the monomer having a functional group is preferably in the range of from 1 to 20% by weight based on the (meth)acrylic resin. Among them, in particular, a monomer having a guanamine group such as acrylamide can be used to prevent peeling or foaming of the binder, which is preferable. When the (meth)acrylic resin having the above functional group is contained as a constituent component of the binder layer, it is preferred to include a crosslinking agent in the binder layer. Crosslinking agent such as polyfunctional isocyanate-based cross-linking agent, phenylene diisocyanate, hexamethylene diisocyanate, trimethylolpropane modified methyl phenylene diisocyanate, etc. Functional epoxy group ethylene glycol diglycidyl acid, propylene glycol epoxidized ether, etc., polyfunctional aziridine-based crosslinking agent, Ν_hexamethylene-1,6-bis(1-nitrogen a heterocyclic propane carboxy decylamine, a trimethylol propyl aziridine propionate, a metal chelate-crosslinking agent, an aluminum acetoacetate complex, and a peroxide benzamidine A base peroxide, a melamine crosslinking agent, and the like. These may be used alone or in combination of two or more. The content is preferably in the range of 〜1 to 5% by weight. In the present invention, the weight average molecular weight of the (meth)acrylic resin is preferably from 200,000 to 2,000,000, more preferably from 50,000 to 2,000,000, and most preferably from -54 to 201000311, from 700,000 to 150. Ten thousand. Further, the weight average molecular weight is a result measured by gel permeation chromatography. Further, in the above adhesive layer, a binder such as a plasticizer or a decane coupling agent, a coloring agent such as a pigment, cerium oxide, titanium oxide, aluminum oxide, metal powder, and metal oxide powder may be contained. Inorganic sputum, resin granules, etc., etc., are used in an appropriate amount for each purpose. The film thickness of the formed adhesive layer is appropriately set in the range of 5 to 50; zm. [Examples] Next, the adhesive-modified substrate film and the hard coat film of the present invention will be described using examples and comparative examples, but the present invention is of course not limited by the examples. Further, the physical properties and properties of the adhesive modified base film and the hard coat film described in the examples were evaluated by the following methods. (1) Adhesion to Hard Coating Layer The hard coating layer on which the hard coating film of the hard coating agent (A) obtained in the examples and the comparative examples was applied was on the front side of the glass plate to which the thickness of the double-sided tape was applied for 5 minutes. Attached to the opposite side. Then, the hard coat layer was passed through to reach one of the lattice-shaped cuts of the base film, and formed by cutting the bundle with a gap of 2 mm. Then, a tape (manufactured by Nichiban Co., Ltd., No. 405; width of 24 mm) was attached to a lattice-shaped cut surface. At the time of attachment, the air remaining in the interface was removed by an eraser, and after completely adhering, the tape was peeled off vertically, and the adhesiveness was obtained by visual observation from the following formula. Further, the portion which is partially peeled off in one grid is also included in the number of peeling. Subsequent (%) = (1 the number of strips of one grid / 1 〇 〇) X 1 〇 〇 The following (%) is 90~100%: ◎
接著性（％)爲80〜89%:〇 接著性（％)爲〇〜7 9 % : X -55- 201000311 (2) 硬塗布層側之干涉斑的評估 使塗布有實施例及比較例所得的硬塗布劑（A)或（B)之 硬塗膜切成面積10cmx50cm，作成試料薄膜。在與所得的 試料薄膜之硬塗布層的相反面上，貼合黑色光澤膠帶。以 該試料薄膜之硬塗布面爲上面，以3波長白色螢光燈（國際 牌燈泡、F.L 15EX-N 15W)爲光源，自斜上方以目視觀察反 射光。以目視觀察的結果，以下述基準評估。而且，觀察 係以精通該評估的5名人員進行，以最多等級作爲評估等 級。假設2個等級爲相同數目時採用分爲3個等級之中心。 例如’各採用〇與△各爲2名、X爲1名時爲△;〇爲1名、 △與X爲2名時爲△;〇與X各爲2名、△爲1名時爲△。 〇：塗布劑（A)及（B)雙方自各種角度觀察時，皆沒有彩虹 狀色彩現象。 △ ··塗布劑（A)及（B)中任一方、或雙方視某角度而定稍微 有彩虹狀色彩現象。 X :塗布劑（A)及（B)中任何一方、或雙方皆有明顯的彩虹 狀色彩現象。 (3) 接著性改質層（A)及塗布層（B)之塗布量 自實施例及比較例所得的接著性改質基材薄膜切出 1 Ocmx 1 0cm之面積’做成10張之試料薄膜。使試料薄膜之 接者性改質層（A)面、或塗布層（b)面以滲染有甲基乙酮/甲 苯=1/1之混合有機溶劑之擦布擦拭，使於擦拭前後之重量 使用精密天砰（島津製作所公司製AUW120D)，使塵埃之影 響爲最小値、清潔度等級1 000之環境中進行測定。自所測 定的重量差以平方公尺換算求取塗布量（mg/m2)。 而且，有機溶劑只要是可除去接著性改質層（A)及塗布 -56- 201000311 層（B)者即可，沒有特別的限制。 另外’塗布量之測定亦可以預先做成的檢測線爲基 準，使用螢光X光裝置予以測定。 (4) 靜摩擦係數（//s)及動摩擦係數（^d)之差 自實施例及比較例所得的接著性改質基材薄膜切出 8 cmx 5 cm之面積，做成試料薄膜。使該物以接著性改質層 (A)面爲外側固定於具有大小爲6cmx5cm之底面的重量 4.4kg之金屬製四方體底面上。此時，組合試料薄膜之5cm 寬度方向與金屬四方體之5cm寬度方向’使試料薄膜之長 度方向的一邊折彎，在金屬四方體的側面上以膠帶固定。 接著，自相同的接著性改質基材薄膜切出爲2〇cmx l〇cm面積的試料’使接著性改質層（A)面爲上方以黏著膠 帶固定於平坦的金屬板上。使試料薄膜連接貼附有金屬製 四方體的測定面放置於其上，以拉伸速度爲200mm/分鐘、 2 3 °C、6 5 % R Η條件下測定靜摩擦係數（μ s)及動摩擦係數 (# d)。測定係使用東洋BALDWIN公司製RTM-1 00，靜摩 擦係數（ys)及動摩擦係數（yd)以；FIS K-7125爲基準計 算’求取其差（△ μ )。 (5) 突起之山麓大小的測定 使以實施例及比較例所得的接著性改質基材薄膜之接 箸性改質層（Α)表面使用麥谷羅馬布（譯音）公司製非接觸3 次元形狀測定裝置ΤΥΡΕ5 5 0，使8 3.2x 8 3.2 // m之視野（測 定範圍）的表面形狀以下述測定條件進行測定。 測定條件：w a v e型式 對物透鏡：5 0倍 其次’以等高線表示型式，藉由測定面藉由高度以表 -57- 201000311 示顏色不同的影像。此時，爲除去表面形狀之扭轉時，進 行面修正（4次係數修正）。等咼線表示型式，使測定範圍內 之平均筒度設定爲Onm，高度最高値設定爲1〇〇nm，高度 最低値lx定爲- lOOnm’局度l〇〇nm以上之突起部分以紅色 表示時’計算每1平方米之高度爲100nm以上的表面突起 數。 然後，以同一測定視野之截面圖表示型式予以表示。 使山麓兩端固定’使山麓兩端沿著高度l〇〇nm以上之表面 突起的長度方向’且山麓通過表面突起之最高高度位置下 移動。繪製畫面係在高度之標度以表面突起全體表示下予 以調整。使截面圖表示畫面以第3圖所示之高度（ + 40nm〜 -5nm)x寬度（Omm〜0.05mm)表示，讀取截面圖與測定範圍 內之平均高度線之高度爲0nm之線相交的2個交點間之距 離，測定山麓部之最大直徑。使上述測定重複進行有關突 起30點，求取其平均値。 在基材薄膜之表層上含有惰性粒子時，對於沒有來自 基材薄膜之大凹凸的範圍，藉由上述測定，測定1 〇〇nm以 上之表面突起的山麓大小，表面突起之山麓部的最大直徑 平均値爲l〇/zm以上時爲〇。 而且，具有同等以上之機能的測定機時，亦可爲使用 雷射之非接觸粗糙度的測定器。 (6) 硬塗布層之折射率測定 以JIS K 7 1 42爲基準，使用阿貝折射率計進行測定。 (7) 硬塗布層/基材薄膜界面之評估 使以實施例及比較例所得的塗布有硬塗布劑（A)之硬 塗膜之試料包埋於可見光硬化型樹脂（日本迪塔姆（譯音）公 -58- 201000311 司製、D-800)，在室溫下照射可見光予以硬化。自所得的 包埋區域使用裝設有鑽石刀之超薄切片機，製作厚度約70 〜100nm之超薄切片，且在四氧化鈮蒸氣中進行染色處理 30分鐘。使經染色的超薄切片使用透過型電子顯微鏡（日本 電子股份有限公司製、TEM2010)，觀察硬塗布層之截面， 是否有獨立的有機-無機複合物存在。而且，使照片之擴 大倍率適當地設定於10, 〇〇〇〜100, 〇〇〇倍之範圍內。此外， 於本發明之實施例1中，擴大倍率爲8 0,000倍（加速電壓 /爲 200kv)。 (8) 玻璃轉移溫度 以JIS-K7121爲基準，使用示差掃描熱量計（精工儀器 股份有限公司製、DSC6200)，在-100°C〜30(TC之溫度範 圍內、以l〇°C / mi η予以昇溫，由DSC曲線所得的玻璃轉移 開始溫度作爲玻璃轉移溫度。 (9) 霧度變化量（J Hz )評估 使接著性改質基材薄膜切出50mm寬之正方形，以JIS K 7105「塑膠之光學特性試驗方法」霧度（曇價）爲基準， 測定加熱前霧度。測定器係使用日本電色工業社製 NDH-3 00A型濁度計。於測定後，使薄膜固定於加熱成17〇 t之烤箱中，經過20分鐘後取出薄膜。使該加熱後薄膜以 與上述相同的方法測定霧度，得到加熱後之霧度。該加熱 前後霧度差爲d Hz。 ZHz =加熱後霧度一加熱前霧度 (1〇) 聚酯樹脂、接著性改質基材薄膜之低聚物含量 稱取〇.lg之聚酯樹脂、或接著性改質基材薄膜，溶解 於3ml之1，1，1，3,3,3-六氟-2-丙醇/氯仿（2/3(容量比））之混合 -59- 201000311 溶劑中。在所得的溶液中加入20ml氯仿，予以均勻地混合 。在所得的混合液中加入1 0ml甲醇，使線狀聚酯予以再沈 殿處理。然後，使該混合液過濾過，使沈殿物以30ml之氯 仿/甲醇（2/1 (容量比））之混合溶劑洗淨，再進行過濾。使 所得的濾液以旋轉蒸餾器予以濃縮乾固。在濃縮乾固物中 加入1 0ml之二甲基甲醯胺，形成環狀低聚物測定溶液。使 該測定溶液使用横河電機（股）公司製LC 100型之高速液體 色層分析法予以定量。 (Π)接著性改質基材薄膜之色度b*値 使接著性改質基材薄膜切出50mm寬之正方形，各以10 張重疊，做成5組試樣。測定器係使用日本電色工業公司製 Color Meter ZE2000，以JIS K 7105「塑膠之光學特性試驗 方法」色、色差爲基準，以反射型測定色度b *値。測定係 進行5次，以平均値作爲接著性改質基材薄膜之色度b*値。 (12) 在波長380nm之光線透過率 使用分光光度計（日立製作所製、U-3 500型），以空氣 層爲標準，測定波長3 00〜5 00nm範圍之光線透過率，求取 波長3 80nm之透過率。 (13) 聚酯樹脂之固有黏度 使〇.4之聚酯溶解於25§之苯酚/四氯乙醇（體積比3/2)之 混合溶液中，在3 0 °C中使用奧氏黏度計進行測定。 (1 4 )惰性粒子之平均粒徑 使基材薄膜所使用的惰性粒子以掃描型電子顯微鏡（曰 立製作所製、S-5 10型）觀察，視粒子之大小而定適當地變 化倍率，放大影印照片中所攝影者。然後，有關無規選取 的至少200個以上之粒子，追跡各粒子之外周，由以影像解 -60- 201000311 析裝置測定此等之追跡影像測定粒子之相當圓徑’以此等 之平均値作爲平均粒徑。 (15)霧度、全光線透過率 以JIS-K7105爲基準，使用濁度計（NHD2000、日本電色 工業製），測定基材薄膜之霧度、全光線透過率。 (16 ) a層側表面之三次元表面粗糙度（SRa、SRz ) 使在表層（a層）中含有惰性粒子之接著性改質基材薄 膜的a層側表面使用觸針式三次元粗糙度計（SE-3AK、小 阪硏究所股份有限公司製），針之半徑2/zm、荷重3 0mg之 條件下，朝薄膜之長度方向、以切斷値爲〇.25mm、通過測 定長度1 m m、針之移送速度0.1 m m /秒進行測定，以2 // m間 距分割成500點，使各點之高度裝設於三次元粗糙度解析裝 置（SPA-11)中。使與此相同的操作朝薄膜之寬度方向、 以2 # m間隔、連續進行150次，即經過0.3mm薄膜之寬度方 向進行，以解析裝置讀取數據。其次，使用解析裝置，求 取中心面平均粗糙度（SRa)、十點平均粗糙度（SRz)。 (1 7 )黏合劑層之剝離性 (黏合劑層之形成） 在醋酸乙酯中，使100份以單體基體爲35 %之丙烯酸2- 乙基己酯及3份之丙嫌酸予以共聚合，製得含有重量平均分 子量50萬（聚苯乙烯換算）之丙烯酸系聚合物的溶液。在 該溶液中、對1〇〇份之丙烯酸系聚合物（乾燥重量）而言， 配合4份之環氧系交聯劑（三菱瓦斯化學（股）製，迪頓拉 頓（譯音）C )及1份之異氰酸酯系交聯劑（日本聚胺基甲酸 酯工業（股）製，克羅尼頓（譯音）L ),然後，加入醋酸乙 酯，調製固體成份濃度調整爲20 %之黏合劑溶液。使該黏 -61 - 201000311 合劑溶液以乾燥膜厚爲2 5 v m、塗布於實施例、比較例所 得的接著性改質基材薄膜之塗布層（B)表面上，在140 °C 下進行乾燥處理2分鐘，形成黏合劑層。 (剝離性評価） 以JIS-Z- 02 3 7爲基準，在SUS板上貼合薄膜片’藉由手 動進行1 8 0 °剝離試驗，以目視觀察S U S板上之狀態，以下述 基準判斷。 ◎:自任何視野角、SUS板上皆沒有觀察到附著物及 痕跡。 〇：在SUS板上雖沒有附著物，惟以某些視野角有觀 察到痕跡。 △:以某些視野角、在SUS板上有觀察到附著物。 X :在SUS板上有觀察到附著物。 (1 8 )黏合劑層側之干渉斑評估 有關上述（3)之評估對象的具有黏合劑層之接著性改 質基材薄膜，藉由與上述（2)相同的方法，自黏合劑層側 觀察所看到的干渉斑。然後’除去黏合劑層後，再觀察干 渉斑。是否伴隨有黏合劑層’如下述評估所觀察的干渉斑 是否有變化。 藉由具有黏合劑層， ◎:自所有角度觀察，皆沒有彩虹狀色彩 〇·僅視某些角度而定觀察有彩虹狀色彩 △:稍有僅彩虹狀色彩 x:有顯著的彩虹狀色彩 (實施例1 ) (1 )塗布液（A-1 )之調合 -62- 201000311 藉由下述之方法調製爲製得接著性改質層（A)時之塗 布液（A -1 )。 (共聚合聚酯樹脂之合成） 在反應容器中加入對酞酸二甲酯（95質量份）、異酞酸 二甲酯（95質量份）、乙二醇（35質量份）、新戊二醇（145 質量份）、醋酸鋅（〇.1質量份）及三氧化銻（0.1質量份） ，在180°C下進行酯交換反應3小時。然後，添加5-鈉磺基 異酞酸（6.0質量份），在240 °C下進行酯化反應1小時後， 在250 °C、減壓下〜〇.2mmHg)進行聚縮合反應2小時 ，製得數量平均分子量爲19,500、玻璃轉移溫度爲62 °C之 共聚合聚酯樹脂（A)。 使3 00質量份所得的共聚合聚酯系樹脂與140質量份丁 基溶纖劑，在1 6 0°C下進行攪拌3小時，製得黏稠的熔融液 ，在該熔融液中慢慢地添加水，於1小時後製得均勻的淡白 色之固體成份濃度爲15%的水分散液。 (聚胺基甲酸酯系樹脂之合成） 使100質量份己二酸//1,6-己烷二醇/新戊二醇（莫耳比 :4//2/3)之組成所形成的聚酯二醇（〇HV:2000eq/t〇n)、41.4 質量份苯二甲基二異氰酸酯混合’在氮氣氣流、80〜90 °C 下進行反應1小時後，冷卻至6 〇 °C ’加入7 0質量份四氫呋喃 予以溶解，製得胺基甲酸酯預聚物溶液（NCO/OH比：2.2 、遊離異氰酸酯基：3.30質量％)。其次’使上述之胺基甲 酸酯預聚物溶液在40。(3下’再加入45·5質量份之20質量°/。的 重亞硫酸鈉水溶液，激烈地進行攪拌，在4 0〜5 0 °C下進行 反應3 0分鐘。確認遊離異氰酸酯基含量（固體成份換算） 消失後，以乳化水予以稀釋，以固體成份2〇質量％之重亞 -63- 201000311 硫酸鈉、製得含有嵌段的異氰酸酯基之自己交聯型聚胺基 甲酸醋系樹脂水溶液（B)°玻璃轉移溫度爲45 °C ° (粒子之前處理） 在1 6.3質量份水、1 1 · 6質量份異丙醇質量份之混合溶液 中，添加0.16質量份作爲粒子A之平均粒徑爲40nm之球狀二 氧化矽的20質量％水分散液、〇·〇37質量份之3_5質量份作爲 粒子B之平均粒徑爲200 nm(平均一次粒徑40 nm)的乾式法 二氧化砍之水分散液，再添加〇.8質量份之固體成份20質量 %的聚胺基甲酸酯樹脂（B )，然後’使該分散液在3 0 °C下 進行攪拌1小時，製得粒子分散液。此時’使用粉體溶解機 (T · K ·均混器Μ型）作爲攪拌機，分散條件係對1 〇kg分 散液而言回轉數爲lOOOOrpm。 (塗布液（A-1)之調製） 各使28.9質量份所得的粒子分散液、1.1質量份之共聚 合聚酯（A)爲15質量％之水分散液、40質量份水、30質量 份異丙醇、〇 . 0 2質量份氟系非離子型界面活性劑之1 0質量 %水溶液、0 · 0 3質量份觸媒（二丁基月桂酸錫）混合。然 後，以5質量％之碳酸氫鈉水溶液使塗布液之pH値調整爲 6.2，過濾粒子尺寸（初期過濾效率：9 5 % )爲1 0 /z m之毛 毯型聚丙烯製過濾器進行精密過濾處理，調製塗布液（A-1 )。 (2)接著性改質基材薄膜之製造 使作爲原料聚合物、不含粒子之固有黏度爲0.62 dl/g (以苯酚：^,2,2 —四氯乙烷=6: 4混合溶劑溶解，且 在3 〇 °C下進行測定）之聚對酞酸乙二酯（p E T )樹脂料粒 ，在1 3 5 °C下進行減壓乾燥6小時（1 T 〇 r r )。然後，使乾燥 -64 - 201000311 後之PET樹脂料粒供應給押出機’在約2 8 5 °C下熔融押出成 薄片狀，在表面溫度保持於20 °C之金屬輥上進行急冷硬化 處理，製得流延薄膜。此時’使用過濾粒子尺寸（初期過 濾、效率·· 95%)爲15"m之不銹鋼製燒結濾材作爲除去熔融 樹脂中之異物的濾材。 使所得的流延薄膜在經加熱的輥群及紅外線加熱器加 熱成95 °C，然後，以具有周速差之輥群、朝長度方向進行 延伸3.5倍延伸，製得單軸配向PET薄膜。其次，使上述之 塗布液（A - 1 )以過濾粒子尺寸（初期過濾效率：9 5 % ) 1 0 从m之毛毯型聚丙烯製濾材進行精密過濾處理，以輥塗布法 塗布於單軸配向PET薄膜之一面上。 然後，在乾燥爐中、丨3 5 °C下進行乾燥5秒鐘。 繼後，使薄膜端部以夾子固定，且導入溫度爲125 t之 熱風區，朝寬度方向進行延伸4.3倍。其次，保持朝寬度方 向延伸的寬度下，在溫度225 °C下進行處理30秒鐘，再朝寬 度方向進行3 %之緩和處理，製得接著性改質層（A)之塗 布量7mg/m2、薄膜厚度125νιη的接著性改質聚酯薄膜。 (硬塗膜之製作） 在所得的接著性改質聚酯薄膜之接著性改質層（A)面 上，以乾燥厚度爲3/zm塗布下述硬塗布劑（A)或（B)，在 8〇°C下乾燥3分鐘。然後，以高壓水銀燈、在1 OOOmJ/cm2 之條件下照射紫外線，且使樹脂硬化，形成硬塗布層。 (硬塗布劑（A)) 準備紫外線硬化型丙烯酸酯單體、氧化锆超微粒子、 甲基乙酮爲主成分之有機/無機混合系硬塗布劑（JSR股份 有限公司製、DeS〇lite2：7410B;固形成分濃度：50質量％)。 -65- 201000311 藉此所得的硬塗布層之折射率爲1.65。 (硬塗布劑（B)) 使二氧化鈦微粒子（石原產業（股）製、TTO-55B)、含羧 酸基之單體（東亞合成（股）製、Aronix M-5300)及環己酮， 藉由砂磨機予以分散，調製重量平均粒徑爲55nm之二氧化 鈦微粒子的分散液。 於上述二氧化鈦微粒子之分散液中，混合二季戊四醇 六丙烯酸酯（日本化藥（股）製、DPHA)、與光游離聚合起始 劑（Ciba-geigy公司製、irgacure丨84;單體之合計量（二季 戊四醇六丙烯酸酯與陰離子性單體之合計量）而言爲5質量 %)，硬塗布層之折射率調整爲1 . 6 0。 (實施例2) 於調製接著性改質層（A)時，除使用水分散性丙嫌酸-苯乙烯共聚合樹脂（日本觸媒化學（股）公司製之Acryl set 270E)之15質量％水分散液的塗布液（A_2)取代實施例1所 使用的共聚合聚酯（A)之1 5質量。/。之水分散液外，以與實施 例1相同的方法，製得接著性改質層（A)之塗布量7mg/m2、 薄膜厚度125/zm之接著性改質聚酯薄膜。 (實施例3) 除使接著性改質層（A)之塗布量改爲9mg/m2外，以與 實施例1相同的方法製得接著性改質聚酯薄膜。 (實施例4) 除使接著性改質層（A)之塗布量改爲3mg/m2外，以與 實施例1相同的方法製得接著性改質聚酯薄膜。 (實施例5) 除使接著性改質層（A)之塗布量改爲12mg/m2外，以與 -66 - 201000311 實施例1相同的方法製得接著性改質聚酯薄膜。 (實施例6) 於調製接著性改質層（A)之塗布液時，除使用平均粒徑 6 5 n m之球狀二氧化矽作爲粒子A，使用沒有添加粒子B之 塗布液（A- 3)外，以與實施例1相同的方法製得接著性改質 聚酯薄膜。 (實施例7) 於調製接著性改質層（A)之塗布液時，除使用使聚胺基 甲酸酯系樹脂（B)與粒子A，B之分散液的攪拌時間爲3小時 之塗布液（A - 4 )外，以與實施例1相同的方法製得接著性改 質聚酯薄膜。 (實施例8 ) 於調製接著性改質層（A)之塗布液時，除使用以〇4質 量份、玻璃轉移點35°C之聚胺基甲酸酯系樹脂（Takeraku w_511(三井Takeda化學公司製））取代〇·8質量份聚胺基甲 酸酯（B)所調整的塗布液（a-5)外，以與實施例1相同的方 法製得接著性改質聚酯薄膜。 (實施例9) 於調製接著性改質層（A)之塗布液時，除使用聚胺基甲 酸醋（B)與粒子A，B之分散液的攪拌時間爲〇·5小時之塗布 液（A-6)外，以與實施例丨相同的方法製得接著性改質聚酯 薄膜。 (比較例1 ) 於實施例1中，除沒有塗布塗布液（A_ i )、即沒有形成 接著性改質層（A)外，與實施例〗相同地製得接著性改質聚 酯薄膜。所得的薄膜之摩擦阻力變大，無法測定摩擦係數。 -67- 201000311 (比較例2) 除使接著性改質層（A)之塗布液改爲下述所示之塗布 液（A-7)’且使塗布量改爲l〇〇mg/m2外，以與實施例1相 同的方法製得接著性改質聚酯薄膜。 (接著性改質塗布液A-7之調合） 除實施例1所得的共聚合聚酯（A)之固體成份濃度改爲 3 0質量％外’與實施例1相同地使7.5質量份所得的共聚 合聚酯（A)之水分散液、11.3質量份;固體成份濃度爲20質 量％之聚胺基甲酸酯（B)的水溶液、0.02質量份作爲觸媒之 二丁基月桂酸錫、37.9質量份水及39.6質量份異丙醇混 合。另外，添加〇 · 3質量份氟系非離子型界面活性劑之1 〇 質量％水溶液、2,3質量份作爲粒子A之平均粒徑40nm之 膠體二氧化矽的20質量％水分散液、0.5質量份作爲粒子B 之平均粒徑爲200ηιη(平均一次粒徑40nm)的乾式法二氧化 矽之3 .5質量％水分散液。然後，以5質量％碳酸氫鈉水溶 液使塗布液之pH値調整爲6.2,且以過濾粒子尺寸（初期過 濾效率：95%)爲l〇Mm之毛毯型聚丙烯製過濾器進行精密 過據處理，調整塗布液（A-7)。 (比較例3) 除接著性改質層（A)之塗布液改爲下述所示之塗布液 (A-8)、即沒有進行粒子添加時之前處理外，以與實施例1 相同的方法製得塗布量爲7mg/m2之接著性改質聚酯薄膜。 (接著性改質塗布液（A-8)之調合） 使1.1質量份所得的共聚合聚酯（A)之15質量。/。的水分 散液、0.8質量份固體成份濃度爲20質量％之聚胺基甲酸 酯（B)、0.02質量份作爲觸媒之二丁基月桂酸錫、56.3質量 -68- 201000311 份水及41.6質量份異丙醇混合。另外，添加0.02質量份氟 系非離子型界面活性劑之1 0質量％水溶液、0. 1 6質量份作 爲粒子A之平均粒徑40nm之球狀二氧化矽的20質量％水 分散液、0.037質量份作爲粒子B之平均粒徑爲200nm(平 均一次粒徑40nm)的乾式法二氧化矽之3.5質量份的水分 散液。然後，以5質量％碳酸氫鈉水溶液使塗布液之pH値 調整爲6.2，且以過濾粒子尺寸（初期過濾效率：95%)爲 l〇Vm之毛毯型聚丙烯製過濾器進行精密過濾處理，調整 塗布液（A - 8 )。 (比較例4) 除接著性改質層（A)之塗布液改爲下述所示之塗布液 (A-9)外，以與實施例1相同的方法製得塗布量爲7mg/rn2 之接著性改質聚酯薄膜。 (接著性改質塗布液（A-9)之調合） 使22.9質量份實施例1所得的共聚合聚酯樹脂（A)之 30質量％水分散液、2.3質量份甲基化蜜胺系交聯劑（住友 化學公司製、SimimaruM-100)之固體成分20質量％之水分 k 散液、39.7質量份水及37.5質量份異丙醇混合。另外，添 加0.6質量份氟系非離子型界面活性劑之1 〇質量％水溶 液、2.3質量份作爲粒子A之平均粒徑40nm之膠體二氧化 矽的20質量％水分散液、〇·5質量份作爲粒子B之平均粒 徑爲200nm(平均一次粒徑4〇nm)的乾式法二氧化矽之3.5 質量份的水分散液。然後’以5質量％碳酸氫鈉水溶液使 塗布液之pH値調整爲6.2,且以過濾粒子尺寸（初期過濾效 率：95%)爲l〇gm之毛毯型聚丙烯製過濾器進行精密過濾 處理，調整塗布液（A-8)。 -69- 201000311 (比較例5 ) 除接者性改質層（A)之塗布液改爲下述所示之塗布液 (A-10)、即不含粒子之塗布液、以及沒有設置塗布層 外，以與實施例1相同的方法製得塗布量爲Umg/m2之接 著性改質聚醋薄膜。所得的薄膜之摩擦阻力變大，無法測 定摩擦係數。 (接著性改質塗布液（A - 1 0)之調合） 使22.9質量份實施例1所得的共聚合聚酯（A)之3〇質 量％水分散液、2 _ 3質量份甲基化蜜胺系交聯劑（住友化學公 司製、SimimaruM-l〇〇)之固體成份20質量％之水分散液、 42·〇質量份水及38.0質量份異丙醇混合。另外，添加〇·6 質量份氟系非離子型界面活性劑之10質量％水溶液。然 後’以5質量％碳酸氫鈉水溶液使塗布液之pH値調整爲 6.2，且以過濾粒子尺寸（初期過濾效率：95%)爲10 # m之 毛毯型聚丙烯製過濾器進行精密過濾處理，調整塗布液 (A-1〇 )。 -70- 201000311 【表1】 塗 布 液 塗布量 (g/m2) 無機粒 子之前 處理 高度100 上之表面 nm以 -突起 動摩 擦係 數與 靜摩 擦係 數之 差 有 ψ Arrr IMI /\\\ 機 複 的 有 干涉 斑 與硬塗布 層之密接 性 突起密 度(個 /mm2) 山麓 部之 最大 粒徑 平均 値 (#m) 實施例1 A-1 7 有 110 21 0.05 有 〇 ◎ 實施例2 A-2 7 有 100 17 0.09 有 〇 〇 實施例3 A-1 9 有 15 20 0.02 有 〇 〇 實施例4 A-1 3 有 50 27 0.18 有 〇 ◎ 實施例5 A-1 12 有 70 41 0.01 有 〇 ◎ 實施例6 A-3 7 有 490 31 0.10 有 〇 ◎ 實施例7 A-4 7 有 850 49 0.02 有 〇 ◎ 實施例8 A-5 7 有 124 29 0.01 有 〇 ◎ 實施例9 A-6 7 有 98 11 0.10 有 〇 ◎ 比較例1 - - - - - 〇 X 比較例2 A-7 100 Atrr. 1111: y»、、 220 85 -0.06 Απτ. ΤΤΤΤΤ X ◎ 比較例3 A-8 7 Arrt MM? 105 4 0.31 有 〇 ◎ 比較例4 A-9 7 137 8 0.24 無 Δ 〇 比較例5 A-10 15 - - - Μ Δ ◎ (實施例1 0) 使酯化反應罐昇溫，到達2 00 °c時，加入由86.4質量 份對酞酸及64.4質量份乙二醇所形成的漿料’進行攪拌且 添加作爲觸媒之0.017質量份三氧化銻及0.16質量份三乙 胺。然後，進行加壓昇溫，以臨界壓3.5kgf/cm2、240 °C之 條件進行加壓酯化反應。然後，使酯化反應罐内回復至常 -71 - 201000311 條件進行加壓酯化反應。然後，使酯化反應罐内回復至常 壓，添加0.071質量份醋酸鎂4水合物、再添加0.014質量 份磷酸三甲酯。此外，在15分鐘內昇溫爲260 °C，添加0.012 質量份磷酸三甲酯，再添加0.0036質量份醋酸鈉。於15 分鐘後，使所得的酯化反應生成物移送於聚縮合反應罐 中，在減壓下由260 T：慢慢地昇至280 °C ’在285 °C下進行 聚縮合反應。 於聚縮合反應完成後，以9 5 %切斷直徑爲5 μ m之納斯 龍（譯音）製之過濾器進行過濾處理自噴嘴押出成條狀’使 用預先進行過濾處理（孔徑：1 // m以下）之冷卻水進行冷 卻、固化，切斷成料粒狀。所得的PET樹脂(Ml)之固有黏 度爲0.62dl/g，低聚物含量爲0.97質量％，實質上不含惰性 粒子及內部析出粒子。 (2 ) PET樹脂（M2 )之製造 使用與PET樹脂（Ml)相同的方法，藉由改變聚縮合 反應時間，製得固有黏度爲〇.47dl/g之PET樹脂（M2)。 (3 ) PET樹脂（M3 )之製造 使P E T樹脂（Μ 2 )預先在1 6 0 °C下予以預備結晶化處理 後，在溫度220 °C之氮氣氣體環境下進行固相聚合，製得固 有黏度爲〇.63dl/g、低聚物含量爲0.26質量％之PET樹脂（ M3 )。 (4)接著性改質基材薄膜之製造 各使PET樹脂（Ml)、PET樹脂（M3)在135 °C下進 行減壓乾燥處理6小時（lTorr)後，以PET樹脂（Ml )作爲 -72- 201000311 A層之原料，且以PET樹脂（M3)作爲B層之原料，供應 給2台押出機，各在285 °C下予以熔融。以a層爲最外層、 b層爲中間層，以2種3層（a/ b/ a )合流區段予以積層， 藉由噴嘴押出成薄片狀，使用流延法捲取於表面溫度爲30 °C之鑄造桶上予以冷卻固化，製作未延伸薄膜。另外，使 最外層（a層）之厚度比例對全部厚度而言爲20%下，調整 各押出機之吐出量。除使用未延伸薄膜外，以與實施例1 相同的方法，製得接著性改質聚酯薄膜。 (實施例1 1 ) 於實施例1 0中，除使最外層（a層）厚度之比例對全部 厚度而言爲40%下，調整各押出機之吐出量外，以與實施 例1 〇相同的方法，製得接著性改質聚酯薄膜。 (實施例1 2 ) 於實施例1 0中，除a層之原料爲PET樹脂（Ml ),且形 成1種3層構成外，以與實施例1 0相同的方法，製得接著性 改質聚酯薄膜。 (實施例1 3 ) 於實施例10中，除a層之原料爲PET樹脂（M3)，且形 成1種3層構成外，以與實施例1 〇相同的方法，製得接著性 改質聚酯薄膜。 -73- 201000311 【表2】 塗布 液 鈽量 (g/m2) 纖 粒子 之前 離 高度100nm以 上之表面魏 動摩 mm 麟 靜摩 麟 差 有 ψ k 靈 杨 的 I 干涉 斑 層之密接 性 ZlHz 賴物 m. b*値 魏 密度 個 /mm2) ύΜ 部之 駄 雖 平均 値 ("m) (%) 質量(％) 實施例10 A-1 7 有 110 21 0.05 有 〇 ◎ 0.2 0.88 2.9 實施例11 A-1 7 有 110 21 0.05 有 〇 ◎ 0.1 0.74 3.6 實施例12 A-1 7 有 110 21 0.05 有 〇 ◎ 19.3 0.99 2.7 實施例13 A-1 7 有 110 21 0.05 有 〇 ◎ 0.1 0.26 5.9 (實施14 ) (1)接著性改質基材薄膜之製造 使10重量份經乾燥的紫外線吸收劑（2,2’-(1,4-伸苯基 )雙（4H-3,1-苯并噚二酮-4-酮）、90重量份之不含粒子的PET 樹脂料粒（固有黏度爲〇.62dl/g)混合，使用混練押出機， 製作含紫外線吸收劑之主浴（A)。此時，押出溫度爲2 8 5 °C 〇 使9 0重量份作爲基材薄膜中間層用原料之不含粒子的 固有黏度爲〇·62 dl/g之PET樹脂料粒與10重量份含紫外線 吸收劑之主浴（A)，在135°C下進行減壓乾燥6小時（ITorr) 後，在押出機2(中間層b層用）中各供應不含粒子之聚對苯 二甲酸乙二酯之料粒（固有黏度爲0·62 dl/g)給押出機1( 外層a層用）及3 (外層c層用），在285 °C下溶解。使該2種 聚合物各以不銹鋼燒結體之濾材（公稱過濾精度1 0 # m粒子 9 5 %切斷）過濾，積層3層合流區域，藉由噴嘴押出薄片狀後 -74- 201000311 ’使用施加靜電流延法，捲取於表面溫度30 °C之鑄造桶上 予以冷卻硬化，製作未延伸薄膜。此時，a層、b層、c層之 厚度比例爲5: 90: 5下，調整各押出機之吐出量。使用該 未延伸薄膜外，以與實施例1相同的方法，接著性改質聚酯 薄膜。 (實施例1 5 ) 除8 0重量份作爲基材薄膜之中間層用原料的不含粒子 之固有黏度爲0.62 dl/g的PET樹脂料粒，與20重量份紫外線 吸收劑之主浴（A)，使a層、b層、c層之厚度比例直至5 : 90 :5爲止，接著性改質聚酯薄膜之厚度爲lOO/zm外，以與實 施例14相同的方法製得接著性改質聚酯薄膜。 (實施例1 6 ) 除80重量份作爲基材薄膜之中間層用原料的不含粒子 之固有黏度爲〇.62dl/g的PET樹脂料粒，與14重量份紫外線 吸收劑之主浴（A) ’使a層、b層、c層之厚度比例直至5 : 9〇 :5爲止，接著性改質聚酯薄膜之厚度爲50//m外，以與實 施例1 4相同的方法製得接著性改質聚酯薄膜。 (實施例1 7 ) 除80重量份作爲基材薄膜之中間層用原料的不含f立子 之固有黏度爲〇·62 dl/g的PET樹脂料粒，與8重量份紫外線 吸收劑之主浴（A) ’使a層、b層、c層之厚度比例直至5 : ·_ 5爲止，接著性改質聚酯薄膜之厚度爲50从„1外，以與胃 施例1 4相同的方法製得接著性改質聚酯薄膜。 (實施例1 8 ) -75- 201000311 除80重量份作爲基材薄膜之中間層用原料的不含彳立^ 之固有黏度爲0.62 dl/g的PET樹脂料粒，與6重量份紫外線 吸收劑之主浴（A) ’使a層、b層、c層之厚度比例直至$ : 9〇 :5爲止，接著性改質聚酯薄膜之厚度爲50/z m外，以與實 施例1 4相同的方法製得接著性改質聚酯薄膜。 (實施例1 9 ) 除80重量份作爲基材薄膜之中間層用原料的不含|立子_ 之固有黏度爲〇_62 dl/g的PET樹脂料粒，與20重量份紫外線 吸收劑之主浴（A) ’使a層、b層、c層之厚度比例直至5 : 9〇 ·· 5爲止，接著性改質聚酯薄膜之厚度爲3 8 // m外，以與實 施例1 4相同的方法製得接著性改質聚酯薄膜。 (實施例2 0 ) 除8 3重量份作爲基材薄膜之中間層用原料的不含粒子 之固有黏度爲〇.62dl/g的PET樹脂料粒，與17重量份紫外線 吸收劑之主浴（A)，使a層、b層、c層之厚度比例直至5 : 90 :5爲止，接著性改質聚酯薄膜之厚度爲25/im外，以與實 施例1 4相同的方法製得接著性改質聚酯薄膜。 (實施例2 1 ) 使1 〇重量份經乾燥的紫外線吸收劑之2，2 ’ -亞甲基雙（ 4H-1，1，3,3-四甲基丁基）-6-(2H-苯并***-2-基）苯酚（旭 電化公司製、LA31)、90重量份之不含粒子的PET樹脂料粒 (固有黏度爲0.62 dl/g)混合，使用混練押出機，製作含 紫外線吸收劑之主浴（B )。此時，押出溫度爲2 8 5 °C。 使9 0重量份作爲基材薄膜中間層用原料之不含粒子的 -76- 201000311 固有黏度爲〇_62 dl/g之PET樹脂料粒與ι〇重量份含紫外線 吸收劑之主浴（B) ’在1 35 °C下進行減壓乾燥6小時（lT〇rr) 後，在押出機2(中間層b層用）中各供應不含粒子之聚對苯 二甲酸乙二酯之料粒（固有黏度爲0.62 dl/g )給押出機1 ( 外層a層用）及3(外層c層用），在285 °C下溶解。除使用該 2種聚合物外，以與實施例16相同的方法，製得厚度爲50 # m之接著性改質聚酯薄膜。 (實施例22) 使1 0重量份經乾燥的紫外線吸收劑之2-(5-氯（2H)-苯 并***-2-基）-4-甲基-6-(第3-丁基）苯酚（千葉特殊化學品 公司製TINUVIN 3 26)、與90重量份之不含粒子的PET樹脂 料粒（固有黏度爲0.62 dl/g )混合，使用混練押出機，製 作含紫外線吸收劑之主浴（C)。此時，押出溫度爲28 5 t。 使90重量份作爲基材薄膜中間層用原料之不含粒子的 固有黏度爲0.62 dl/g之PET樹脂料粒與10重量份含紫外線 吸收劑之主浴（C)，在1 3 5 °C下進行減壓乾燥6小時（1 Torr) k.y 後，在押出機2(中間層b層用）中各供應不含粒子之聚對苯 二甲酸乙二酯之料粒（固有黏度爲〇·62 dl/g)給押出機1( 外層a層用）及3 (外層c層用），在2 8 5 °C下溶解。除使用該 2種聚合物外，以與實施例1 6相同的方法，製得厚度爲5 0 // m之接著性改質聚酯薄膜。 -77- 201000311 【表3】 塗布 液 薄膜 之厚 度 塗布量 無機 粒子 之則 處理 高度100nm以 上之表面突起 動摩 擦係 數與 靜摩 擦係 數之 差 有 ψ Μ /»、、 機 複 合 杨 的 有 Μ /1 干涉 斑 與 硬 塗 布 層 之 密 接 性 380nm 之透過 率 突起 密度 (個 /mm2) 山麓 部之 最大 粒徑 平均 値 (jum) (/zm) (mg/m2) (%) 實施例14 A-1 125 7 有 111 21 0.05 有 〇 ◎ 0,8 實施例15 A-1 100 7 有 111 21 0.05 有 〇 ◎ 0.6 實施例16 A-l” 50 7 有 111 21 0.05 有 〇 ◎ 2.0 實施例17 A-1 50 7 有 111 21 0.05 有 〇 ◎ 10.5 實施例18 A-1 50 7 有 111 21 0.05 有 〇 ◎ 15.1 實施例19 A-1 38 7 有 109 20 0.05 有 〇 ◎ 5.5 實施例20 A-1 25 7 有 107 19 0.05 有 〇 ◎ 19.0 實施例21 A-1 50 7 有 111 21 0.05 有 〇 ◎ 6.8 實施例22 A-1 50 7 有 111 21 0.05 有 〇 ◎ 9.7 (實施例23 ) (1 )接著性改質基材薄膜之製造 使作爲b層用原料之不含惰性粒子的固有黏度爲0.62 dl/g之聚對苯二甲酸乙二酯（PET)樹脂料粒A，在U5°C 下進行減壓乾燥6小時（ITorr)。然後，使乾燥後之PET料粒 供應給A層用押出機（1)。使上述之樹脂料粒A、與含有 1 5 00ppm、平均粒徑2.3/zm之不定形塊狀二氧化矽粒子、 固有黏度爲0.62 dl/g之樹脂料粒B以80:20之比例混合後， 作爲B層用原料，在1 35°C下進行減壓乾燥6小時（lTorr)。然 後’使乾燥後之P E T料粒供應給B層用押出機（2)。使供應給 押出機之聚合物在2 8 5 °C下溶解後，各過濾粒子尺寸（初期 -78- 201000311 過濾效率95%)以15/zm之過濾材予以過濾，在以a層/ b層/ a 層積層下、積層比爲5: 90: 5下’調整各押出機之吐出量 後，在285 °C下自T塑模押出成層狀，密接於25 °C之回轉式 冷卻輥予以固化，製得未延伸PET薄膜。 使所得的未延伸PET薄膜在經加熱的輥群及紅外線加 熱器加熱成95 °C，然後，以具有周速差之輥群、朝長度方 向進行延伸3. 5倍延伸，製得單軸配向PET薄膜。其次，使 上述之塗布液（A-1 )以過濾粒子尺寸（初期過濾效率：95% )10 # m之毛毯型聚丙烯製濾材進行精密過濾處理，以輥塗 布法、乾燥後之塗布量爲7mg/m2塗布於單軸配向PET薄膜 之一面上。 繼後，使該單軸配向PET薄膜端部導入夾子方式之橫延 伸機’在130 °C下朝寬度方向延伸4.0倍，再於230 °C下進行 熱固定處理後，在200 °C下朝寬度方向進行3%緩和處理， 製得厚度100 V m的接著性改質基材薄膜。 (硬塗膜之製作） 在所得的接著性改質基材薄膜之接著性改質層面上， 以乾燥厚度爲3/zm塗布下述硬塗布劑，在80 ^下乾燥3 分鐘。然後，以高壓水銀燈、在1 OOOmJ/cm2之條件下照射 紫外線’且使樹脂硬化，形成硬塗布層。 (硬塗布劑） 以紫外線硬化型丙烯酸酯單體、氧化鍩超微粒子、甲 基乙酮爲主成分之有機/無機混合系硬塗布劑（JSR股份有 限公司製、DesoliteZ7410B;固形成分濃度：50質量％)。 -79- 201000311 藉此所得的硬塗布層之折射率爲1 · 6 5。 (實施例24) 於實施例23中，除使用含有1 5 00ppm、平 // m之不定形塊狀二氧化矽粒子、固有黏度爲C 脂料粒C取代樹脂料粒b外，以與實施例2 3相|1 得接著性基材薄膜。 (實施例25) 於實施例23中，除使用含有1 5 00ppm、平 V m之不定形塊狀二氧化矽粒子、固有黏度爲< 脂料粒D取代樹脂料粒B外，以與實施例23相[1 得接著性基材薄膜。 (實施例2 6 ) 於實施例2 3中，除樹脂料粒A與樹脂料） 9 〇 : 1 〇予以混合外，以與實施例2 3相同的方法 基材薄膜。 均粒徑爲3 . 5 .62 dl/g 之樹 丨的方法，製 均粒徑爲4 · 0 |.62 dl/g 之樹 Ϊ的方法，製 立B之比例爲 製得接著性 -80- 201000311 【表4】 塗 布 液 塗 布 量 山麓 部之 最大 粒徑 平均 値10 βτη 以上 基材 薄膜 層構 成 Β層之構成 霧 度 全光 線透 過率 有 機 1 热 機 複 合 物 的 有 無 干 涉 斑 與硬 塗布 層之 密接 性 粒子 之平 均粒 徑 粒子 之含 量 厚 度 SRa SRz (mg/m2) (_ (質量 %) (_ (㈣） ("m) (%) (%) 實施例23 A-1 7 〇 Β/Α/ Β 2.3 0.03 10 0.013 0.86 1.00 90.25 有 ◎ ◎ 實施例24 A-1 7 〇 Β/Α/ Β 3.5 0.03 10 0.019 1.30 1.40 89.88 有 ◎ ◎ 實施例25 A-1 7 〇 Β/Α/ Β 4.0 0.03 10 0.020 1.45 1.50 89.60 有 ◎ ◎ 寅施例26 A-1 7 〇 Α/Β 2.3 0.03 20 0.015 0.95 0.85 90.35 有 ◎ ◎ (實施例27) (1)塗布液（B-1)之調製 使13.74質量份共聚合聚酯之水分散液（Α)、2·51質量 份雙（乳酸）羰基鈦之4 4質量％溶液、1 · 3 8質量份二異丙氧 基雙（三乙醇胺）鈦之80質量％溶液、41.37質量份水及4〇·〇〇 質量份異丙醇混合。另外，添加0.50質量份氟系非離子型 界面活性劑之10質量％水溶液、0.50質量份膠體二氧化砂 粒子（平均粒徑80nm)水分散液，調製塗布液（Β-1)。使該塗 布液之pH値調整爲6.4。而且，於水性聚酯樹脂之質量 (a)、乳酸鈦化合物之質量（b)、及三乙醇胺鈦化合物之 質量（c )中，爲 (a) / 〔（ b) + ( 〇〕= 6 5.1 / 3 4.9 -81 - 201000311 (b ) / ( b ) = 50/50。 (2 )接著性改質基材薄膜之製造 於實施例1中，在單軸配向PET薄膜上，一面塗布上述 之塗布液（A-1 )、另一面塗布上述之塗布液（B-1 )外’以 與實施例1相同的方法，製得接著性改質聚酯薄膜。 (實施例2 8 ) 於調製塗布層（B)之塗布液時，除使用如下述之配合 比例所調製的塗布液（B-2)外，以與實施例27相同的方法’ 製得接著性改質聚酯薄膜。 (a) /〔（b) + (c)〕= 65.1/34.9 (b) / (c) = 60.2/39.8 (實施例2 9 ) 於調製塗布層（B)之塗布液時，除使用如下述之配合 比例所調製的塗布液（B - 3 )外，以與實施例2 7相同的方法’ 製得接著性改質聚酯薄膜。 (a) / [(b) + (c)〕= 6 5.1 / 3 4.9 (b) / (c) = 39.9/60.1 (實施例3 0 ) 於調製塗布層（B)之塗布液時，除使用如下述之配合 比例所調製的塗布液（B - 4 )外，以與實施例2 7相同的方法’ 製得接著性改質聚酯薄膜。 (a) / [(b) + ( c ) ] = 5 0.0/ 5 0.0 (b) / (c) = 50.1/49.9 (實施例3 1 ) -82- 201000311 除調製塗布層（B)之塗布液時，使用以下述配合比所 調製的塗布液（B-5)外，以與實施例27相同的方法，製得接 著性改質聚酯薄膜。 (a) / [(b) + (c)] = 80.0/ 20.0 (b) / (c) = 50.1/ 49.9 (實施例32) 除使用以實施例8所使用的塗布液（A-5)作爲製得塗布 層（B)時之塗布液，使塗布量爲1 00mg/m2外，以與實施例27 相同的方法，製得接著性改質聚酯薄膜。 【表5】 接著性改質層(A) 塗布層⑻ 塗布液 塗布量 無機粒子之前處理 塗布液 (a) / [(b) + (〇)] (b) / (c) (mg/m2) 實施例27 A-1 7 有 B-1 65.1/34.9 50.0/50.0 實施例28 A-1 7 有 B-2 65.1/34.9 60.2/39.8 實施例29 A-1 7 有 B-3 65.1/34.9 39.9/60.1 實施例3〇 A-1 7 有 B-4 50.0/50.0 50.1/49.9 實施例31 A_1 7 有 B-5 80.0/20.0 50.1/49/9 實施例32 A-1 7 有 A-5 - - 201000311 【表6】 接著性改質層(A)之評估 塗布層φ)之評估 高度lOOnm以上之表 面突起 動摩擦係 數與靜摩 擦係數之 差 有機-無 機複合物 的有無 硬塗布層 側之干涉 斑 與硬塗布 層之密接 性 黏著劑層 側之干涉 斑 與黏著劑 層之剝離 性 突起密度 山麓部之 最大直徑 平均値 (個/mm2) (jtzm) 實施例27 110 21 0.05 有 〇 ◎ ◎ ◎ 實施例28 105 20 0.06 有 〇 ◎ ◎ ◎ 實施例29 108 20 0.05 有 〇 ◎ 〇 ◎ 實施例30 109 19 0.06 有 〇 ◎ 〇 ◎ 實施例31 110 21 0.06 有 〇 ◎ 〇 ◎ 實施例32 109 20 0.05 有 〇 ◎ X ◎ 【產業上之利用價値】 本發明之接著性改質基材薄膜，由於沒有因落粉導致 製程污染的情形少，積層硬塗布層及黏著劑層時可維持實 用的密接性，特別是即使於長螢光燈下之干涉斑少，就提 高作爲液晶顯示器、電漿顯示器、ITO、有機EL顯示器等 之顯示器用途的構件之視認性而言極爲有用。 【圖式簡單說明】 第1圖係藉由非接觸三次元形狀測定裝置所得的1視野 之接著性改質層（A)表面的高度爲l〇〇nm以上之表面突起的 等局線表示模式。 第2圖係藉由非接觸三次元形狀測定裝置所得的接著 性改質層（A)表面的高度爲100nm以上之表面突起的截面圖 型（表面突起全體影像）。 -84- 201000311 第3圖係計算接著性改質層表面的高度爲100nm以上 之表面突起的山麓最大直徑時之截面圖與平均高度的關係 〇 【主要元件符號說明】 〇 -85-The following (%) is 80 to 89%: 〇 adhesion (%) is 〇~7 9 % : X -55- 201000311 (2) Evaluation of interference spots on the hard coat layer side is obtained by coating the examples and comparative examples The hard coating film of the hard coating agent (A) or (B) was cut into an area of 10 cm x 50 cm to prepare a sample film. A black glossy tape was attached to the opposite side of the hard coating layer of the obtained sample film. The hard coated surface of the sample film is topped with a 3-wavelength white fluorescent lamp (International brand bulb, F. L 15EX-N 15W) is the light source, and the reflected light is visually observed from obliquely above. The results of the visual observation were evaluated on the basis of the following criteria. Moreover, the observations were conducted with 5 individuals who were proficient in the assessment, with the most grades as the assessment level. Assuming that the two levels are the same number, a center divided into three levels is used. For example, 'each is 2 and △ each is 2, X is 1 △; 〇 is 1; △ and X are 2 △; 〇 and X are 2, △ is 1 △ . 〇: When the coating agents (A) and (B) are observed from various angles, there is no rainbow color phenomenon. △ · · One of the coating agents (A) and (B), or both, may have a rainbow-like color depending on the angle. X: Any one or both of the coating agents (A) and (B) have a distinct rainbow-like color phenomenon. (3) The coating amount of the next modified layer (A) and the coating layer (B) was cut out from the adhesive modified base film obtained in the examples and the comparative examples by an area of 1 Ocm x 10 cm. film. The surface of the sample modified film (A) or the surface of the coated layer (b) is wiped with a cloth impregnated with a mixed organic solvent of methyl ethyl ketone / toluene = 1 / 1, so as to be wiped before and after wiping. The weight was measured using a precision scorpion (AUW120D manufactured by Shimadzu Corporation) to minimize the influence of dust and the cleanliness level of 1,000. The coating amount (mg/m2) was obtained by converting the measured weight difference in square meters. Further, the organic solvent is not particularly limited as long as it can remove the adhesion-modifying layer (A) and the layer-56-201000311 layer (B). Further, the measurement of the coating amount can be measured using a fluorescent X-ray apparatus based on a detection line prepared in advance. (4) Difference between static friction coefficient (//s) and dynamic friction coefficient (^d) From the adhesive modified base film obtained in the examples and the comparative examples, an area of 8 cm x 5 cm was cut out to prepare a sample film. The object was fixed to the outside with a weight of 6 cm x 5 cm on the outer side of the adhesive layer (A). 4kg of metal on the bottom of the square. At this time, the 5 cm width direction of the combined sample film and the 5 cm width direction of the metal rectangular body were bent at one side in the longitudinal direction of the sample film, and the tape was fixed on the side surface of the metal rectangular body. Next, a sample having an area of 2 〇 cm x l 〇 cm was cut out from the same adhesive modified base film. The surface of the adhesive modified layer (A) was fixed to the flat metal plate with an adhesive tape. The measurement film was attached to the measurement surface to which the metal tetragonal body was attached, and the static friction coefficient (μs) and the dynamic friction coefficient were measured at a tensile speed of 200 mm/min, 23 ° C, and 65 % R Η. (# d). For the measurement, RTM-1 00 manufactured by Toyo BALDWIN Co., Ltd., static friction coefficient (ys) and dynamic friction coefficient (yd) were used; and FIS K-7125 was used as a reference to calculate the difference (Δ μ ). (5) Measurement of the size of the ridges of the protrusions The non-contact 3 epochs made by Maigu Romano Co., Ltd. were used for the surface of the adhesive modified layer (Α) of the adhesive modified base film obtained in the examples and the comparative examples. Shape measuring device ΤΥΡΕ 5 5 0, make 8 3. 2x 8 3. The surface shape of the field of view of 2 / m (measurement range) was measured under the following measurement conditions. Measurement conditions: w a v e type Object lens: 50 times Next, the pattern is expressed by a contour line, and the images of different colors are shown by the height of the surface by the measuring surface by -57-201000311. At this time, in order to remove the twist of the surface shape, the surface correction (fourth coefficient correction) is performed. The isobaric line indicates that the average tube size in the measurement range is set to Onm, the height is the highest 値 is set to 1 〇〇 nm, and the height is the lowest 値 lx is set to - lOOnm. The protrusion portion above the 〇〇nm is expressed in red. When 'calculating the number of surface protrusions per 100 square meters with a height of 100 nm or more. Then, it is represented by a cross-sectional representation of the same measurement field of view. The ends of the haw are fixed so that both ends of the haw are along the length direction of the surface protrusions above the height l〇〇nm and the haw moves downward through the highest height position of the surface protrusions. The drawing picture is adjusted to the height scale by the overall surface protrusion. Let the cross-sectional view show the height (+ 40nm~ -5nm) x width (Omm~0. 05 mm) indicates the distance between the two intersections at which the cross-sectional view intersects the line where the height of the average height line in the measurement range is 0 nm, and the maximum diameter of the haw portion is measured. The above measurement was repeated to raise 30 points, and the average enthalpy was obtained. When inert particles are contained on the surface layer of the base film, the size of the haw of the surface protrusion of 1 〇〇 nm or more and the maximum diameter of the haw of the surface protrusion are measured by the above measurement in the range where there is no large unevenness from the base film. When the average 値 is l〇/zm or more, it is 〇. Further, in the case of a measuring machine having an equivalent function or more, a measuring device using a non-contact roughness of a laser may be used. (6) Measurement of refractive index of hard coating layer The measurement was carried out using an Abbe refractometer based on JIS K 7 1 42. (7) Evaluation of Hard Coating Layer/Substrate Film Interface The samples of the hard coating film coated with the hard coating agent (A) obtained in the examples and the comparative examples were embedded in a visible light curing resin (Ditham, Japan) ) -58-201000311 Division, D-800), hardened by irradiation with visible light at room temperature. An ultrathin section having a thickness of about 70 to 100 nm was produced from the obtained embedding area using an ultramicrotome with a diamond knife, and dyeing was carried out in osmium tetroxide vapor for 30 minutes. The dyed ultrathin section was observed using a transmission electron microscope (manufactured by JEOL Ltd., TEM2010) to observe the cross section of the hard coat layer, and whether or not an independent organic-inorganic composite was present. Further, the magnification of the photograph is appropriately set within a range of 10, 〇〇〇 100, and 〇〇〇. Further, in the first embodiment of the present invention, the magnification ratio is 80,000 times (acceleration voltage / 200 kv). (8) The glass transition temperature is based on JIS-K7121, using a differential scanning calorimeter (manufactured by Seiko Instruments Inc., DSC6200) at -100 ° C to 30 (in the temperature range of TC, at 10 ° C / mi η is heated, and the glass transition starting temperature obtained from the DSC curve is taken as the glass transition temperature. (9) The haze change amount (J Hz ) is evaluated by cutting the adhesive-modified substrate film into a square of 50 mm width to JIS K 7105. The test method for the optical properties of plastics is based on the haze (deuterium price). The haze before heating is measured. The measuring instrument is a turbidity meter NDH-3 00A manufactured by Nippon Denshoku Industries Co., Ltd. After the measurement, the film is fixed to the heating. In a 17 〇t oven, the film was taken out after 20 minutes, and the heated film was measured for haze in the same manner as above to obtain a haze after heating. The difference in haze before and after heating was d Hz. ZHz = heating After haze - pre-heating haze (1 〇) polyester resin, adhesive modified substrate film oligomer content weigh. A lg polyester resin or a film of an adhesive modified substrate is dissolved in 3 ml of 1,1,1,3,3,3-hexafluoro-2-propanol/chloroform (2/3 (capacity ratio)) Mix -59- 201000311 in solvent. To the resulting solution, 20 ml of chloroform was added and uniformly mixed. To the resulting mixture, 10 ml of methanol was added to subject the linear polyester to a sinking treatment. Then, the mixture was filtered, and the precipitate was washed with 30 ml of a mixed solvent of chloroform/methanol (2/1 (capacity ratio)), followed by filtration. The resulting filtrate was concentrated to dryness in a rotary distiller. To the concentrated dry solid, 10 ml of dimethylformamide was added to form a cyclic oligomer assay solution. The measurement solution was quantified using a high-speed liquid chromatography method of LC 100 type manufactured by Yokogawa Electric Co., Ltd. (Π) The chromaticity b* of the adhesively modified base film The cut-off modified base film was cut into a square of 50 mm width, and each of 10 sheets was overlapped to form five sets of samples. The color meter ZE2000 manufactured by Nippon Denshoku Industries Co., Ltd. was used, and the chromaticity b*値 was measured by a reflection type based on the color and color difference of JIS K 7105 "Test method for optical properties of plastics". The measurement was carried out 5 times, and the average enthalpy was used as the chromaticity b* 接着 of the adhesive modified base film. (12) The light transmittance at a wavelength of 380 nm is measured by a spectrophotometer (U-3 Model, manufactured by Hitachi, Ltd.), and the light transmittance in the wavelength range of 300 to 500 nm is measured using an air layer as a standard to obtain a wavelength of 3 80 nm. Transmittance. (13) The inherent viscosity of polyester resin makes 〇. The polyester of 4 was dissolved in a mixed solution of 25 § phenol/tetrachloroethanol (3/2 by volume), and was measured at 30 ° C using an Oswald viscometer. (1 4 ) The average particle diameter of the inert particles is observed by a scanning electron microscope (S-5 10 type manufactured by Kyoritsu Seisakusho Co., Ltd.), and the magnification is appropriately changed depending on the size of the particles. Photographed in the photo. Then, at least 200 or more particles randomly selected are traced to the outer circumference of each particle, and the average circular diameter of the particles is determined by measuring the trace image of these trace images by the image resolution-60-201000311 analyzer. The average particle size. (15) Haze and total light transmittance The haze and total light transmittance of the base film were measured using a turbidimeter (NHD2000, manufactured by Nippon Denshoku Industries Co., Ltd.) based on JIS-K7105. (16) The ternary surface roughness (SRa, SRz) of the side surface of the a layer is such that the side surface of the a layer of the adhesive-modified substrate film containing the inert particles in the surface layer (layer a) is stylus-type three-dimensional roughness (SE-3AK, Kosaka Research Institute Co., Ltd.), with a needle radius of 2/zm and a load of 30 mg, the length of the film is cut off. 25mm, passing the measured length of 1 m m, the transfer speed of the needle is 0. The measurement was performed at 1 m m / sec, and divided into 500 points at a distance of 2 // m, so that the height of each point was installed in the three-dimensional roughness analysis device (SPA-11). The same operation was carried out 150 times in the width direction of the film at intervals of 2 #m, that is, after 0. The width of the 3 mm film was made to read the data by the analysis device. Next, using the analysis device, the center plane average roughness (SRa) and the ten point average roughness (SRz) were obtained. (1 7) Adhesion of the adhesive layer (formation of the adhesive layer) In ethyl acetate, 100 parts of 2-ethylhexyl acrylate having a monomer base of 35% and 3 parts of acrylic acid are collectively used. Polymerization was carried out to obtain a solution containing an acrylic polymer having a weight average molecular weight of 500,000 (in terms of polystyrene). In this solution, for one part of the acrylic polymer (dry weight), 4 parts of epoxy-based crosslinking agent (Mitsubishi Gas Chemical Co., Ltd., Diton Raton (trans)) And 1 part isocyanate cross-linking agent (manufactured by Japan Polyurethane Industry Co., Ltd., Clonington (trans) L), and then added ethyl acetate to prepare a solid concentration adjustment of 20%. Solution solution. The viscous-61 - 201000311 mixture solution was applied to the surface of the coating layer (B) of the adhesive modified base film obtained in the examples and the comparative examples at a dry film thickness of 25 vm, and dried at 140 ° C. The treatment was carried out for 2 minutes to form a binder layer. (Peelability evaluation) The film sheet was bonded to a SUS plate with reference to JIS-Z-02733, and the 180 ° peel test was performed by hand, and the state of the S U S plate was visually observed and judged on the following basis. ◎: No deposits or marks were observed from any viewing angle and SUS plate. 〇: Although there is no attachment on the SUS plate, traces are observed at some viewing angles. △: Attachments were observed on the SUS plate at some viewing angles. X: Attachment was observed on the SUS plate. (1) Evaluation of the dry plaque on the side of the adhesive layer. The adhesive-modified substrate film having the adhesive layer in the evaluation object of the above (3), by the same method as (2) above, the self-adhesive layer side Observe the dry ecchymoses seen. Then, after removing the adhesive layer, dry ecchymoses were observed. Whether or not the adhesive layer is accompanied by the change in dry ecchymoses observed as described below. By having a layer of adhesive, ◎: no rainbow color when viewed from all angles 〇 · Rainbow color is observed only for certain angles △: slightly rainbow-like color x: significant rainbow color ( Example 1) (1) Blending of coating liquid (A-1) - 62 - 201000311 The coating liquid (A -1 ) at the time of producing the adhesion modifying layer (A) was prepared by the following method. (Synthesis of copolymerized polyester resin) Dimethyl phthalate (95 parts by mass), dimethyl isononanoate (95 parts by mass), ethylene glycol (35 parts by mass), and neopentane were added to the reaction vessel. Alcohol (145 parts by mass), zinc acetate (〇. 1 part by mass) and antimony trioxide (0. 1 part by mass), the transesterification reaction was carried out at 180 ° C for 3 hours. Then, add 5-sodium sulfoisophthalic acid (6. 0 parts by mass), after esterification at 240 ° C for 1 hour, at 250 ° C, under reduced pressure ~ 〇. 2 mmHg) A polycondensation reaction was carried out for 2 hours to obtain a copolymerized polyester resin (A) having a number average molecular weight of 19,500 and a glass transition temperature of 62 °C. 300 parts by mass of the obtained copolymerized polyester resin and 140 parts by mass of butyl cellosolve were stirred at 160 ° C for 3 hours to obtain a viscous melt, and water was slowly added to the melt. After 1 hour, a uniform pale white solid dispersion having a solid concentration of 15% was obtained. (Synthesis of Polyurethane Resin) The composition of 100 parts by mass of adipic acid//1,6-hexanediol/neopentyl glycol (mole ratio: 4//2/3) is formed. Polyester diol (〇HV: 2000eq/t〇n), 41. 4 parts by mass of benzene dimethylene diisocyanate mixed 'reacted in a nitrogen gas stream at 80 to 90 ° C for 1 hour, then cooled to 6 〇 ° C ', and dissolved in 70 parts by mass of tetrahydrofuran to obtain a urethane. Prepolymer solution (NCO/OH ratio: 2. 2, free isocyanate group: 3. 30% by mass). Next, the above urethane prepolymer solution was brought to 40. (3) 'Addition of 45. 5 parts by mass of a 20% by mass aqueous solution of sodium sulfite, vigorously stir, and carry out a reaction at 40 to 50 ° C for 30 minutes. Confirm the free isocyanate group content (solid content After the disappearance, it is diluted with emulsified water, and the self-crosslinking type polyurethane acetal resin aqueous solution containing block isocyanate groups is obtained by using sodium sulfonate-63-201000311 sodium sulfate as a solid component (% by mass). B) ° glass transfer temperature is 45 ° C ° (particles before treatment) in 1 6. 3 parts by mass of water, 1 1 · 6 parts by mass of a mixture of isopropyl alcohol parts, 0. 16 parts by mass of a 20% by mass aqueous dispersion of spherical cerium oxide having an average particle diameter of 40 nm as particles A, and 3 to 5 parts by mass of 37 parts by mass of cerium lanthanum as an average particle diameter of particles B of 200 nm (average primary particle size) The dry method of oxidizing chopped water dispersion with a diameter of 40 nm), and adding 〇. 8 parts by mass of the solid component 20% by mass of the polyurethane resin (B), and then the dispersion was stirred at 30 ° C for 1 hour to obtain a particle dispersion. At this time, a powder dissolving machine (T · K · homomixer type) was used as a stirrer, and the dispersion condition was 100 rpm for 1 〇 kg of the dispersion. (Modulation of coating liquid (A-1)) 28. 9 parts by mass of the obtained particle dispersion, 1. 1 part by mass of the copolymerized polyester (A) is an aqueous dispersion of 15% by mass, 40 parts by mass of water, 30 parts by mass of isopropyl alcohol, hydrazine. 0 2 parts by mass of a fluorine-based nonionic surfactant, 10% by mass of an aqueous solution, and 0.03 parts by mass of a catalyst (dibutyltin laurate) are mixed. Then, the pH of the coating liquid was adjusted to 6. by a 5 mass% aqueous sodium hydrogencarbonate solution. 2. A filter-type polypropylene filter was prepared by subjecting a filter having a particle size (initial filtration efficiency: 9.5 %) to 1 0 /z m to a precision filtration treatment to prepare a coating liquid (A-1). (2) Manufacture of adhesively modified base film The intrinsic viscosity as a raw material polymer and no particles is 0. 62 dl / g (polyphenol terephthalate (p ET ) resin material dissolved in phenol: ^, 2, 2 - tetrachloroethane = 6: 4 mixed solvent and measured at 3 ° C) The pellet was dried under reduced pressure at 1 3 5 ° C for 6 hours (1 T 〇rr ). Then, the PET resin pellets after drying -64 - 201000311 are supplied to the extruder to be melted and extruded into a sheet at about 285 ° C, and subjected to rapid hardening treatment on a metal roll having a surface temperature of 20 ° C. A cast film was produced. At this time, a stainless steel sintered filter material having a filter particle size (initial filtration, efficiency: 95%) of 15 " m was used as a filter material for removing foreign matter in the molten resin. The obtained cast film was heated to 95 ° C in a heated roll group and an infrared heater, and then extended in the longitudinal direction by a roll group having a peripheral speed difference. A 5-fold extension produces a uniaxially oriented PET film. Next, the above-mentioned coating liquid (A - 1 ) is subjected to precision filtration treatment of a filter material having a filter particle size (initial filtration efficiency: 9 5 %) 10 from a blanket type polypropylene, and is applied by a roll coating method to a uniaxial alignment. One side of the PET film. Then, it was dried in a drying oven at 丨 3 5 ° C for 5 seconds. Subsequently, the end of the film was fixed by a clip and introduced into a hot air zone at a temperature of 125 t, extending in the width direction. 3 times. Next, while maintaining the width extending in the width direction, the treatment was carried out at a temperature of 225 ° C for 30 seconds, and then tempered by a 3% in the width direction to obtain a coating amount of the adhesion-modified layer (A) of 7 mg/m 2 . An adhesive modified polyester film having a film thickness of 125 νηη. (Production of Hard Coating Film) The following hard coating agent (A) or (B) was applied to the surface of the adhesive modified layer (A) of the obtained adhesive modified polyester film at a dry thickness of 3/zm. Dry at 8 ° C for 3 minutes. Then, ultraviolet rays were irradiated under a condition of 10,000 mJ/cm 2 with a high pressure mercury lamp, and the resin was cured to form a hard coat layer. (Hard coating agent (A)) An organic/inorganic hybrid hard coating agent containing an ultraviolet curable acrylate monomer, zirconia ultrafine particles, and methyl ethyl ketone as a main component (DeS〇lite 2: 7410B, manufactured by JSR Corporation) ; solid component concentration: 50% by mass). -65- 201000311 The refractive index of the hard coating layer thus obtained is 1. 65. (Hard coating agent (B)) Titanium dioxide fine particles (manufactured by Ishihara Sangyo Co., Ltd., TTO-55B), a monomer containing a carboxylic acid group (manufactured by Toagos Co., Ltd., Aronix M-5300), and cyclohexanone The dispersion was dispersed by a sand mill to prepare a dispersion of titanium dioxide fine particles having a weight average particle diameter of 55 nm. In the dispersion of the titanium dioxide fine particles, dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., DPHA) and a photo-free polymerization initiator (manufactured by Ciba-geigy Co., Ltd., irgacure 丨84; (5% by mass of the dipentaerythritol hexaacrylate and the anionic monomer), and the refractive index of the hard coat layer was adjusted to 1. 6 0. (Example 2) When the adhesive-modified layer (A) was prepared, 15% by mass of water-dispersible acrylic acid-styrene copolymer resin (Acryl set 270E manufactured by Nippon Shokubai Chemical Co., Ltd.) was used. The coating liquid (A_2) of the aqueous dispersion was substituted for 15 masses of the copolymerized polyester (A) used in Example 1. /. An adhesive modified polyester film having a coating amount of 7 mg/m 2 and a film thickness of 125 / zm of the adhesive modified layer (A) was obtained in the same manner as in Example 1 except for the aqueous dispersion. (Example 3) An adhesive modified polyester film was obtained in the same manner as in Example 1 except that the coating amount of the adhesive modifying layer (A) was changed to 9 mg/m2. (Example 4) An adhesive modified polyester film was obtained in the same manner as in Example 1 except that the coating amount of the adhesive layer (A) was changed to 3 mg/m2. (Example 5) An adhesive modified polyester film was obtained in the same manner as in Example 1 of -66 - 201000311 except that the coating amount of the adhesion-modifying layer (A) was changed to 12 mg/m2. (Example 6) When the coating liquid of the adhesive layer (A) was prepared, a spherical cerium oxide having an average particle diameter of 65 nm was used as the particle A, and a coating liquid (A-3) containing no particles B was used. Further, an adhesive modified polyester film was obtained in the same manner as in Example 1. (Example 7) When the coating liquid of the adhesive layer (A) was prepared, the stirring time of the dispersion of the polyurethane resin (B) and the particles A and B was used for 3 hours. An adhesive modified polyester film was obtained in the same manner as in Example 1 except for the liquid (A - 4 ). (Example 8) When preparing a coating liquid of the adhesive layer (A), a polyurethane resin (Takeraku w_511 (Mitsui Takeda Chemical Co., Ltd.) using 4 parts by mass of ruthenium and a glass transition point of 35 ° C was used. The company's product))) An adhesive modified polyester film was produced in the same manner as in Example 1 except that the coating liquid (a-5) adjusted with 8 parts by mass of the polyurethane (B) was used. (Example 9) When the coating liquid of the adhesive layer (A) was prepared, a coating liquid having a stirring time of 〇·5 hours was used in addition to the dispersion of the polyurethane (B) and the particles A and B ( In the same manner as in Example 外, an adhesive modified polyester film was obtained in the same manner as in A-6). (Comparative Example 1) An adhesive modified polyester film was produced in the same manner as in Example except that the coating liquid (A_ i ) was not applied, that is, the subsequent modified layer (A) was not formed. The frictional resistance of the obtained film became large, and the friction coefficient could not be measured. -67-201000311 (Comparative Example 2) The coating liquid of the adhesive layer (A) was changed to the coating liquid (A-7)' shown below and the coating amount was changed to l〇〇mg/m2. An adhesive modified polyester film was obtained in the same manner as in Example 1. (The blending of the adhesive-modified coating liquid A-7) The solid content of the copolymerized polyester (A) obtained in Example 1 was changed to 30% by mass, and the same as in Example 1. 5 parts by mass of the obtained aqueous dispersion of the copolymerized polyester (A), 11. 3 parts by mass; an aqueous solution of a polyurethane having a solid concentration of 20% by mass of the polyurethane (B), 0. 02 parts by mass of dibutyl laurate as a catalyst, 37. 9 parts by mass of water and 39. 6 parts by mass of isopropanol were mixed. Further, a 〇 mass% aqueous solution containing 2 parts by mass of a fluorine-based nonionic surfactant, and 2,3 parts by mass of a 20% by mass aqueous dispersion of colloidal cerium oxide having an average particle diameter of 40 nm as the particle A, 0 . 5 parts by mass of dry-process cerium oxide as the average particle diameter of the particles B of 200 ηηη (average primary particle diameter: 40 nm). 5 mass% aqueous dispersion. Then, the pH of the coating liquid was adjusted to 6. by a 5 mass% aqueous solution of sodium hydrogencarbonate. 2, and a blanket-type polypropylene filter having a filter particle size (initial filtration efficiency: 95%) of l〇Mm was subjected to precision treatment, and the coating liquid (A-7) was adjusted. (Comparative Example 3) The same procedure as in Example 1 was carried out except that the coating liquid of the adhesive modification layer (A) was changed to the coating liquid (A-8) shown below, that is, the treatment before the particle addition was performed. An adhesive modified polyester film having a coating amount of 7 mg/m 2 was obtained. (Adjustment of the subsequent modified coating liquid (A-8)) 15 parts by mass of the obtained copolymerized polyester (A). /. Moisture, 0. 8 parts by mass of a polyurethane having a solid content concentration of 20% by mass (B), 0. 02 parts by mass of dibutyl laurate as a catalyst, 56. 3 quality -68- 201000311 parts of water and 41. 6 parts by mass of isopropyl alcohol were mixed. In addition, add 0. 02 parts by mass of a fluorine-based nonionic surfactant, 10% by mass aqueous solution, 0. 16 parts by mass of 20% by mass aqueous dispersion of spherical cerium oxide having an average particle diameter of 40 nm as particle A, 0. 037 parts by mass of dry-process cerium oxide having an average particle diameter of particle B of 200 nm (average primary particle diameter of 40 nm). 5 parts by mass of water. Then, the pH of the coating liquid was adjusted to 6. by a 5 mass% aqueous sodium hydrogencarbonate solution. 2, and a filter-type polypropylene filter having a filter particle size (initial filtration efficiency: 95%) of l〇Vm was subjected to precision filtration treatment, and the coating liquid (A - 8 ) was adjusted. (Comparative Example 4) A coating amount of 7 mg/rn2 was obtained in the same manner as in Example 1 except that the coating liquid of the adhesive layer (A) was changed to the coating liquid (A-9) shown below. The polyester film is then modified. (Adjustment of the subsequent modified coating liquid (A-9)) 22. 9 parts by mass of the 30% by mass aqueous dispersion of the copolymerized polyester resin (A) obtained in Example 1, 2. 3 parts by mass of a methylated melamine-based crosslinking agent (manufactured by Sumitomo Chemical Co., Ltd., Simimaru M-100), 20% by mass of the solid component of the water k dispersion, 39. 7 parts by mass of water and 37. Mix 5 parts by weight of isopropyl alcohol. In addition, add 0. 6 parts by mass of a fluorine-based nonionic surfactant, 1% by mass of aqueous solution, 2. 3 parts by mass of a 20% by mass aqueous dispersion of colloidal cerium oxide having an average particle diameter of 40 nm as particles A, and 5 parts by mass of dry particles having an average particle diameter of particles B of 200 nm (average primary particle diameter: 4 〇 nm) Antimony dioxide 5 parts by mass of aqueous dispersion. Then, the pH of the coating liquid was adjusted to 6. by a 5 mass% aqueous sodium hydrogencarbonate solution. 2, and a filter made of a blanket type polypropylene having a filter particle size (initial filtration efficiency: 95%) of l〇gm was subjected to precision filtration treatment, and the coating liquid (A-8) was adjusted. -69-201000311 (Comparative Example 5) The coating liquid of the detacher-modified layer (A) was changed to the coating liquid (A-10) shown below, that is, the coating liquid containing no particles, and the coating layer was not provided. Further, an adhesive modified polyester film having a coating amount of Umg/m2 was obtained in the same manner as in Example 1. The frictional resistance of the obtained film became large, and the coefficient of friction could not be measured. (Adjustment of the subsequent modified coating liquid (A - 1 0)) 9 parts by mass of the 3 % by mass aqueous dispersion of the copolymerized polyester (A) obtained in Example 1, and 2 - 3 parts by mass of the methylated melamine-based crosslinking agent (manufactured by Sumitomo Chemical Co., Ltd., Simimaru M-l) The solid component is 20% by mass of an aqueous dispersion, 42% by mass of water and 38. 0 parts by mass of isopropyl alcohol was mixed. Further, a 10% by mass aqueous solution of 6% by mass of a fluorine-based nonionic surfactant was added. Then, the pH of the coating liquid was adjusted to 6. by a 5 mass% aqueous sodium hydrogencarbonate solution. 2, and a blanket type polypropylene filter having a filter particle size (initial filtration efficiency: 95%) of 10 #m was subjected to precision filtration treatment, and the coating liquid (A-1〇) was adjusted. -70- 201000311 [Table 1] Coating liquid coating amount (g/m2) The surface of the inorganic particles before the treatment height of 100 is the difference between the coefficient of friction and the static friction coefficient. Arrr IMI /\\\ Density of adhesion between spot and hard coating layer (number/mm2) Maximum particle size of hawthorn average 値(#m) Example 1 A-1 7 There are 110 21 0. 05 有 〇 ◎ Example 2 A-2 7 Yes 100 17 0. 09 有〇 实施 Example 3 A-1 9 Yes 15 20 0. 02 有〇 实施 Example 4 A-1 3 Yes 50 27 0. 18 有 〇 ◎ Example 5 A-1 12 Yes 70 41 0. 01 有〇 ◎ Example 6 A-3 7 Yes 490 31 0. 10 有 〇 ◎ Example 7 A-4 7 Yes 850 49 0. 02 有〇 ◎ Example 8 A-5 7 Yes 124 29 0. 01 有〇 ◎ Example 9 A-6 7 Yes 98 11 0. 10 Yes 〇 ◎ Comparative Example 1 - - - - - 〇 X Comparative Example 2 A-7 100 Atrr. 1111: y»,, 220 85 -0. 06 Απτ. ΤΤΤΤΤ X ◎ Comparative Example 3 A-8 7 Arrt MM? 105 4 0. 31 有 〇 ◎ Comparative Example 4 A-9 7 137 8 0. 24 Δ 〇 〇 Comparative Example 5 A-10 15 - - - Δ Δ ◎ (Example 1 0) The temperature of the esterification reactor was raised, and when it reached 200 ° C, it was added. 4 mass parts of citric acid and 64. 4 parts by mass of the slurry formed of ethylene glycol was stirred and added as a catalyst. 017 parts by mass of antimony trioxide and 0. 16 parts by mass of triethylamine. Then, the pressure is raised to a critical pressure of 3. The pressure esterification reaction was carried out under conditions of 5 kgf/cm2 and 240 °C. Then, the esterification reaction tank was returned to the normal -71 - 201000311 condition to carry out a pressure esterification reaction. Then, the internal pressure of the esterification reactor was returned to normal pressure, and 0 was added. 071 parts by mass of magnesium acetate tetrahydrate, and then added 0. 014 parts by weight of trimethyl phosphate. In addition, the temperature is raised to 260 ° C in 15 minutes, adding 0. 012 parts by mass of trimethyl phosphate, then add 0. 0036 parts by mass of sodium acetate. After 15 minutes, the obtained esterification reaction product was transferred to a polycondensation reaction tank, and a polycondensation reaction was carried out at 285 ° C under a reduced pressure from 260 T: slowly to 280 ° C. After the completion of the polycondensation reaction, the filter made by Nasron (transliteration) having a diameter of 5 μm was cut at 95%, and the filter was processed from the nozzle into a strip shape. [Pre-filtering was used (aperture: 1 // The cooling water of m or less is cooled, solidified, and cut into pellets. The inherent viscosity of the obtained PET resin (Ml) was 0. 62dl / g, the oligomer content is 0. 97% by mass, substantially free of inert particles and internally precipitated particles. (2) Manufacture of PET resin (M2) The intrinsic viscosity was obtained by changing the polycondensation reaction time in the same manner as the PET resin (Ml). 47 dl / g of PET resin (M2). (3) Production of PET resin (M3) The PET resin (Μ 2 ) was preliminarily crystallized at 160 ° C and then solid-phase polymerized in a nitrogen gas atmosphere at a temperature of 220 ° C to obtain an inherent Viscosity is 〇. 63dl / g, oligomer content is 0. 26% by mass of PET resin (M3). (4) Production of adhesive modified base film Each of PET resin (Ml) and PET resin (M3) was subjected to vacuum drying treatment at 135 ° C for 6 hours (1 Torr), and then PET resin (Ml) was used as - 72- 201000311 Raw material of layer A, and PET resin (M3) as raw material of layer B, supplied to two extruders, each melted at 285 °C. The a layer is the outermost layer and the b layer is the intermediate layer. The two layers of the three layers (a/b/a) are layered, and are extruded into a sheet shape by a nozzle, and are wound up at a surface temperature of 30. The casting barrel of °C was cooled and solidified to produce an unstretched film. Further, when the thickness ratio of the outermost layer (layer a) was 20% for the entire thickness, the discharge amount of each extruder was adjusted. An adhesive modified polyester film was obtained in the same manner as in Example 1 except that the unstretched film was used. (Example 1 1) In Example 10, except that the ratio of the thickness of the outermost layer (layer a) was 40% for the entire thickness, the discharge amount of each extruder was adjusted, and the same as in Example 1 The method of producing an adhesive modified polyester film. (Example 1 2) In the same manner as in Example 10 except that the raw material of the a layer was a PET resin (Ml) and one type of three layers was formed, the adhesive modification was carried out in the same manner as in Example 10 Polyester film. (Example 1 3) In the same manner as in Example 1 except that the raw material of the a layer was a PET resin (M3) and a three-layer structure was formed, the adhesive modification polymerization was carried out in the same manner as in Example 1 Ester film. -73- 201000311 [Table 2] The amount of coating liquid (g/m2) Before the fiber particles are separated from the height of 100nm or more, the surface of the surface is 动 动 mm mm mm M. b*値 Wei Density /mm2) ύΜ 之 Although average 値 ("m) (%) Quality (%) Example 10 A-1 7 Yes 110 21 0. 05 有 〇 ◎ 0. 2 0. 88 2. 9 Example 11 A-1 7 Yes 110 21 0. 05 有 〇 ◎ 0. 1 0. 74 3. 6 Example 12 A-1 7 Yes 110 21 0. 05 有 〇 ◎ 19. 3 0. 99 2. 7 Example 13 A-1 7 Yes 110 21 0. 05 有 〇 ◎ 0. 1 0. 26 5. 9 (Implementation 14) (1) Production of adhesive modified base film 10 parts by weight of dried ultraviolet absorber (2,2'-(1,4-phenylene) bis(4H-3,1- Benzoindolinone-4-one), 90 parts by weight of PET resin pellets without particles (inherent viscosity is 〇. 62 dl/g) was mixed, and a master bath (A) containing a UV absorber was prepared using a kneading extruder. At this time, the extrusion temperature is 2 8 5 ° C, and 90 parts by weight of the raw material for the base film intermediate layer is a particle-free internal viscosity of PET resin particles of 〇·62 dl/g and 10 parts by weight of ultraviolet rays. The main bath (A) of the absorbent is dried under reduced pressure at 135 ° C for 6 hours (ITorr), and then the polyethylene terephthalate containing no particles is supplied to each of the extruder 2 (for the intermediate layer b layer). The ester pellets (inherent viscosity: 0·62 dl/g) were applied to the extruder 1 (for the outer layer a) and 3 (for the outer layer c), and dissolved at 285 °C. Each of the two kinds of polymers was filtered with a filter material of a stainless steel sintered body (a nominal filtration accuracy of 10 #m particles, 95% cut), and a three-layered merged region was laminated, and the sheet was extruded by a nozzle. -74-201000311 The electrostatic casting method was carried out by coiling on a casting barrel having a surface temperature of 30 ° C to be cooled and hardened to produce an unstretched film. At this time, the thickness ratio of the a layer, the b layer, and the c layer is 5:90:5, and the discharge amount of each extruder is adjusted. Using this unstretched film, the polyester film was adhesively modified in the same manner as in Example 1. (Example 1 5) The intrinsic viscosity of the particle-free material of the raw material for the intermediate layer as a base film of 80 parts by weight was 0. 62 dl / g of PET resin pellets, and 20 parts by weight of the main bath (A) of the ultraviolet absorber, the thickness ratio of the a layer, the b layer, and the c layer is up to 5:90:5, followed by the modified polyester An adhesive modified polyester film was obtained in the same manner as in Example 14 except that the thickness of the film was 100/zm. (Example 1 6) The intrinsic viscosity of the particle-free material of the raw material for the intermediate layer of 80 parts by weight as the base film was 〇. 62 dl / g of PET resin pellets, with 14 parts by weight of UV absorber main bath (A) 'the thickness ratio of layer a, layer b, layer c up to 5: 9 〇: 5, followed by modified polyester An adhesive modified polyester film was obtained in the same manner as in Example 14 except that the thickness of the film was 50 / / m. (Example 1 7) The main bath of the PET resin pellet having an intrinsic viscosity of 〇·62 dl/g and the main absorbent of 8 parts by weight of the ultraviolet absorber in addition to 80 parts by weight of the raw material for the intermediate layer as the base film (A) 'The thickness ratio of the a layer, the b layer, and the c layer is up to 5: · 5, and the thickness of the adhesive modified polyester film is 50 from 1:1, in the same manner as in the stomach example 14 An adhesive modified polyester film was obtained. (Example 18) -75- 201000311 The intrinsic viscosity of the raw material for the intermediate layer as the base film was 80. 62 dl / g of PET resin pellets, and 6 parts by weight of the main bath of the UV absorber (A) 'The thickness ratio of the a layer, the b layer, and the c layer is up to $:9〇:5, followed by the modified polycondensation An adhesive modified polyester film was obtained in the same manner as in Example 14 except that the thickness of the ester film was 50/zm. (Example 1 9) In addition to 80 parts by weight of the raw material for the intermediate layer as the base film, the PET resin pellet having an intrinsic viscosity of 〇_62 dl/g, and 20 parts by weight of the ultraviolet absorbent Bath (A) 'The thickness ratio of the a layer, the b layer, and the c layer is up to 5:9 〇··5, and the thickness of the adhesive modified polyester film is 3 8 // m, in the same manner as in the example 14 The adhesive modified polyester film was obtained in the same manner. (Example 20) The intrinsic viscosity of the particle-free material of the raw material for the intermediate layer of 83 parts by weight is 〇. 62 dl / g of PET resin pellets, and 17 parts by weight of the main bath (A) of the ultraviolet absorber, the thickness ratio of the a layer, the b layer, and the c layer is up to 5:90:5, and the modified polyester film is further modified. An adhesive modified polyester film was obtained in the same manner as in Example 14 except that the thickness was 25/im. (Example 2 1 ) 2,2 '-methylenebis(4H-1,1,3,3-tetramethylbutyl)-6-(2H-) of 1 part by weight of a dried ultraviolet absorber Benzotriazol-2-yl)phenol (manufactured by Asahi Kasei Co., Ltd., LA31), 90 parts by weight of PET resin pellets containing no particles (inherent viscosity is 0. 62 dl/g) was mixed, and a master bath (B) containing a UV absorber was prepared using a kneading extruder. At this time, the extrusion temperature was 2 8 5 °C. 90 parts by weight of the raw material for the base film for the base film, the particle-free -76-201000311 PET resin pellet having an intrinsic viscosity of 〇_62 dl/g and the main bath containing the ultraviolet absorber in the ι by weight ' After drying under reduced pressure at 1 35 °C for 6 hours (lT〇rr), the particles of polyethylene terephthalate containing no particles are supplied to each of the extruder 2 (for the intermediate layer b layer). (Intrinsic viscosity is 0. 62 dl/g ) was applied to the extruder 1 (for the outer layer a) and 3 (for the outer layer c), and dissolved at 285 °C. An adhesive modified polyester film having a thickness of 50 #m was obtained in the same manner as in Example 16 except that the two polymers were used. (Example 22) 10 parts by weight of a dried ultraviolet absorber of 2-(5-chloro(2H)-benzotriazol-2-yl)-4-methyl-6-(3-butyl group) Phenol (TINUVIN 3 26 manufactured by Chiba Specialty Chemicals Co., Ltd.) and 90 parts by weight of PET resin pellets containing no particles (inherent viscosity is 0. Mixing 62 dl/g), using a mixing extruder, to make a main bath (C) containing UV absorbers. At this time, the extrusion temperature was 28 5 t. 90 parts by weight of the material-free intermediate material used as the base material for the base film is 0. 62 dl/g of PET resin pellets and 10 parts by weight of a main bath (C) containing an ultraviolet absorber were dried under reduced pressure at 1 35 ° C for 6 hours (1 Torr) k. After y, the pellets of the polyethylene terephthalate containing no particles (inherent viscosity: 〇·62 dl/g) are supplied to the extruder 2 (outer layer b layer) to the extruder 1 (outer layer a For layer) and 3 (for outer layer c layer), dissolve at 2 8 5 °C. An adhesive modified polyester film having a thickness of 50 // m was obtained in the same manner as in Example 16 except that the two polymers were used. -77- 201000311 [Table 3] Thickness of coating liquid film Coating amount of inorganic particles The difference between the dynamic friction coefficient and the static friction coefficient of surface protrusions with a height of 100 nm or more is ψ » /», and the composite yang has a Μ /1 interference spot Adhesion density to hard coating layer 380 nm transmittance protrusion density (pieces/mm2) Maximum particle size of haw portion (jum) (/zm) (mg/m2) (%) Example 14 A-1 125 7 111 21 0. 05 有 〇 ◎ 0,8 Example 15 A-1 100 7 Yes 111 21 0. 05 有 〇 ◎ 0. 6 Example 16 A-l" 50 7 Yes 111 21 0. 05 Yes 〇 ◎ 2. 0 Example 17 A-1 50 7 Yes 111 21 0. 05 有 〇 ◎ 10. 5 Example 18 A-1 50 7 Yes 111 21 0. 05 Yes 〇 ◎ 15. 1 Example 19 A-1 38 7 Yes 109 20 0. 05 Yes 〇 ◎ 5. 5 Example 20 A-1 25 7 Yes 107 19 0. 05 有 〇 ◎ 19. 0 Example 21 A-1 50 7 Yes 111 21 0. 05 Yes 〇 ◎ 6. 8 Example 22 A-1 50 7 Yes 111 21 0. 05 有 〇 ◎ 9. 7 (Example 23) (1) Production of adhesive modified base film The intrinsic viscosity of the raw material for the b layer containing no inert particles was 0. 62 dl/g of polyethylene terephthalate (PET) resin pellet A was dried under reduced pressure at U5 ° C for 6 hours (ITorr). Then, the dried PET pellets are supplied to the layer A extruder (1). The above resin pellet A is contained with 1 500 ppm and an average particle diameter of 2. 3/zm of amorphous block-shaped cerium oxide particles with an intrinsic viscosity of 0. 62 dl/g of the resin pellets B were mixed at a ratio of 80:20, and then dried under reduced pressure at 1,35 ° C for 6 hours (1 Torr) as a raw material for the layer B. Then, the dried P E T pellets are supplied to the B layer extruder (2). After dissolving the polymer supplied to the extruder at 2 8 5 ° C, each filter particle size (initial -78-201000311 filtration efficiency 95%) was filtered with 15/zm filter material in a layer / b layer / a Under the laminated layer, the lamination ratio is 5: 90: 5 times. After adjusting the discharge amount of each extruder, it is extruded from the T mold at 285 °C, and is attached to a rotary cooling roller at 25 °C. Curing, an unstretched PET film was produced. The obtained unstretched PET film was heated to 95 ° C in a heated roll group and an infrared heater, and then extended in a length direction by a roll group having a peripheral speed difference. A 5-fold extension produces a uniaxially oriented PET film. Next, the coating liquid (A-1) was subjected to precision filtration treatment using a blanket type polypropylene filter material having a filter particle size (initial filtration efficiency: 95%) of 10 # m, and the coating amount by the roll coating method and drying was 7 mg/m2 was coated on one side of the uniaxially oriented PET film. Subsequently, the uniaxially-oriented PET film was introduced into the clip-type cross-extension machine to extend in the width direction at 130 °C. After 0 times and further heat-fixing at 230 ° C, 3% relaxation treatment was carried out in the width direction at 200 ° C to obtain a film of the adhesion-modified substrate having a thickness of 100 V m. (Production of Hard Coating Film) On the adhesive modification layer of the obtained adhesive modified base film, the following hard coating agent was applied at a dry thickness of 3/zm, and dried at 80 ° for 3 minutes. Then, the resin was cured by irradiating ultraviolet rays under a condition of 10,000 mJ/cm 2 with a high pressure mercury lamp to form a hard coat layer. (Hard coating agent) An organic/inorganic hybrid hard coating agent containing ultraviolet curable acrylate monomer, cerium oxide ultrafine particles, and methyl ethyl ketone as a main component (Desolite Z7410B, manufactured by JSR Co., Ltd.; solid component concentration: 50 mass) %). -79- 201000311 The hard coating layer thus obtained has a refractive index of 165. (Example 24) In Example 23, except that the amorphous cerium oxide particles containing 1 500 00 ppm and 1/4 m were used, and the intrinsic viscosity was C resin granule C instead of the resin granule b, Example 2 3 phase|1 gave an adhesive substrate film. (Example 25) In Example 23, except that amorphous block-shaped cerium oxide particles containing 1 500 ppm and flat V m were used, the intrinsic viscosity was < The lipid granule D was substituted for the resin granule B, and the film was bonded to Example 23 [1 to obtain an adhesive base film. (Example 2 6) A substrate film was obtained in the same manner as in Example 23 except that the resin pellet A and the resin pellet were mixed with 9 〇 : 1 Torr in Example 23. A method for producing a tree raft having an average particle diameter of 3.55.62 dl/g, a method for producing a tree raft having an average particle diameter of 4 · 0 |.62 dl/g, and the ratio of the standing B is made to an adhesive-80 - 201000311 [Table 4] Coating liquid coating amount The maximum particle size of the hawthorn portion is 値10 βτη. The base film layer is composed of the base layer. The haze is the total light transmittance. The organic 1 composite has the interference speckle and the hard coating layer. Average Particle Size of the Adhesive Particles Thickness of the Particles SRa SRz (mg/m2) (_ (% by mass) (_ ((4)) ("m) (%) (%) Example 23 A-1 7 〇Β /Α/ Β 2.3 0.03 10 0.013 0.86 1.00 90.25 ◎ ◎ Example 24 A-1 7 〇Β / Α / Β 3.5 0.03 10 0.019 1.30 1.40 89.88 Yes ◎ ◎ Example 25 A-1 7 〇Β / Α / Β 4.0 0.03 10 0.020 1.45 1.50 89.60 ◎ ◎ 寅 Example 26 A-1 7 〇Α/Β 2.3 0.03 20 0.015 0.95 0.85 90.35 ◎ ◎ (Example 27) (1) Preparation of coating liquid (B-1) 13.74 parts by mass of an aqueous dispersion of a copolymerized polyester (Α), 2.51 parts by mass of a 4% by mass solution of bis(lactic acid) carbonyl titanium, and a mass of 1 · 38 An 80% by mass solution of diisopropoxy bis(triethanolamine) titanium, 41.37 parts by mass of water, and 4 parts by mass of isopropyl alcohol are mixed. Further, 0.50 parts by mass of a fluorine-based nonionic surfactant is added. 10% by mass aqueous solution, 0.50 parts by mass of colloidal silica sand particles (average particle diameter: 80 nm) aqueous dispersion, and a coating liquid (Β-1) was prepared. The pH of the coating liquid was adjusted to 6.4. Further, the aqueous polyester resin was used. The mass (a), the mass of the titanium lactate compound (b), and the mass of the triethanolamine titanium compound (c) are (a) / [( b) + ( 〇 ] = 6 5.1 / 3 4.9 -81 - 201000311 (b) / (b) = 50/50. (2) Production of adhesively modified base film In Example 1, the above-mentioned coating liquid (A-1) was applied to one side of the uniaxially oriented PET film. On the other hand, the above-mentioned coating liquid (B-1) was applied. In the same manner as in Example 1, an adhesive modified polyester film was obtained. (Example 28) When the coating liquid of the coating layer (B) was prepared In the same manner as in Example 27 except that the coating liquid (B-2) prepared by the mixing ratio described below was used, the adhesiveness was changed. Polyester film. (a) /[(b) + (c)] = 65.1/34.9 (b) / (c) = 60.2/39.8 (Example 2 9 ) When preparing the coating liquid of the coating layer (B), An adhesive modified polyester film was produced in the same manner as in Example 27 except that the coating liquid (B-3) prepared in the proportion was blended. (a) / [(b) + (c)] = 6 5.1 / 3 4.9 (b) / (c) = 39.9/60.1 (Example 3 0) When the coating liquid of the coating layer (B) is prepared, An adhesive modified polyester film was produced in the same manner as in Example 27 except that the coating liquid (B-4) prepared in the following mixing ratio was used. (a) / [(b) + ( c ) ] = 5 0.0 / 5 0.0 (b) / (c) = 50.1/49.9 (Example 3 1 ) -82- 201000311 In addition to the coating liquid of the coating layer (B) In the same manner as in Example 27, an adhesive modified polyester film was obtained in the same manner as in Example 27 except that the coating liquid (B-5) prepared in the following mixing ratio was used. (a) / [(b) + (c)] = 80.0 / 20.0 (b) / (c) = 50.1 / 49.9 (Example 32) Except that the coating liquid (A-5) used in Example 8 was used as The coating liquid in the case where the coating layer (B) was obtained was applied to a coating amount of 100 mg/m2, and an adhesive modified polyester film was obtained in the same manner as in Example 27. [Table 5] Subsequent modified layer (A) Coating layer (8) Coating liquid coating amount of inorganic particles before treatment coating liquid (a) / [(b) + (〇)] (b) / (c) (mg/m2) Example 27 A-1 7 B-1 65.1/34.9 50.0/50.0 Example 28 A-1 7 B-2 65.1/34.9 60.2/39.8 Example 29 A-1 7 B-3 65.1/34.9 39.9/ 60.1 Example 3〇A-1 7 Yes B-4 50.0/50.0 50.1/49.9 Example 31 A_1 7 Yes B-5 80.0/20.0 50.1/49/9 Example 32 A-1 7 Yes A-5 - - 201000311 [Table 6] Evaluation of the coating layer φ) of the next modified layer (A) The difference between the surface protrusion dynamic friction coefficient and the static friction coefficient of the above-described height of 100 nm or more The interference of the organic-inorganic composite on the hard coating layer side and the hard coating layer The interference plaque on the adhesive layer side of the layer and the peeling protrusion density of the adhesive layer The maximum diameter of the hawthorn portion 値(mm/mm2) (jtzm) Example 27 110 21 0.05 〇 ◎ ◎ ◎ Example 28 105 20 0.06 〇 ◎ ◎ ◎ Example 29 108 20 0.05 〇 ◎ 〇 ◎ Example 30 109 19 0.06 〇 ◎ 〇 ◎ Example 31 110 21 0.06 〇 ◎ 〇 ◎ Example 32 109 20 0.05 〇 ◎ X ◎ [Industrial use price 値] The adhesive-modified substrate film of the present invention has no coating contamination due to falling powder, and the hard coat layer and the adhesive are laminated. In the case of the layer, it is possible to maintain practical adhesion, and in particular, it is extremely effective in improving the visibility of components used for display applications such as liquid crystal displays, plasma displays, ITO, and organic EL displays, even when there are few interference spots under long fluorescent lamps. it works. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an isometric representation pattern of surface protrusions having a height of 1 〇〇 nm or more on the surface of the adhesion-correcting layer (A) of one field of view obtained by a non-contact three-dimensional shape measuring device. . Fig. 2 is a cross-sectional view of a surface protrusion having a height of 100 nm or more on the surface of the adhesive modified layer (A) obtained by a non-contact three-dimensional shape measuring device (a total surface projection). -84- 201000311 Fig. 3 is a graph showing the relationship between the cross-sectional view and the average height of the maximum diameter of the hawthorn with a surface protrusion of a height of 100 nm or more on the surface of the adhesive layer. 〇 [Description of main components] 〇 -85-