1364364 九、發明說明： 【發明所屬之技術領域】 本發明係關於當在三乙醯纖維素薄膜單面上，形成 層之際，因硬塗層的硬化收縮而所引起的薄膜曲捲較 且經抑制過溼度依存性的硬塗層薄膜，詳言之，為關 用於如電視接收器或個人電腦螢幕顯示之類之電子資 示體表面的保護，且處理性優越的硬塗層薄膜。 【先前技術】 液晶顯示器、CRT、電漿顯示器、室外顯示面板、ί 看板等各種顯示體或玻璃，為能保護其表面，便使用 可塑性樹脂薄膜為支撐體，並在其上設置硬塗層的硬 薄膜。特別係以液晶顯示器為代表的平面面板，就從 透性較高、缺點較少、無偏光性等觀點而言，支撐體 可塑性樹脂薄膜可使用三乙醯纖維素薄膜。 一般硬塗處理的方法，係在熱可塑性樹脂薄膜表面 敷紫外線硬化型樹脂或放射線硬化型樹脂，而形成硬 層。紫外線硬化型樹脂或放射線硬化型樹脂係由單體 聚物、光起始劑構成，利用3次元交聯引起樹脂硬化 現出硬性。隨此樹脂硬化所產生的硬化收縮而發生薄 捲。熱可塑性樹脂薄膜中，三乙醯纖維素薄膜雖因上 性而被廣泛的使用，但是因為薄膜剛性較低，明顯發 膜曲捲，因而造成處理性變差、生產性降低的問題。今 在對顯示器的薄型、輕量化需求高漲之聲浪中，使用 撐體的薄膜將越薄且剛性較低，在薄膜曲捲的改善方 3%傳利說明書(補件)\94-01\93丨2955〇 5 硬塗 小， 於適 訊顯 i子 以熱 塗層_ 光穿 的熱 上塗 塗 、寡 而顯 膜曲 述特 生薄 後， 為支 面將 1364364 成為大課題。 再者，對三乙醯纖維素薄膜施行硬塗處理過的薄膜，係 因為使用作為偏光板的構成構件，故為能獲得與偏光膜間 的黏著性，便利用驗施行驗化處理。此時，驗化處理、洗 淨、乾燥的步驟，因為在多濕環境中實施，因此若具有薄 膜曲捲之溼度依存性的話，將導致處理性降低。 為改善該等薄膜曲捲，已知有下述技術》例如，含有放 射線硬化型樹脂組成物之硬化皮膜層的薄膜，係含有使分 子中至少具有2個以上（曱基）丙烯醯基及羥基的放射線硬 化型多官能基（曱基）丙烯酸酯，與聚異氰酸酯進行反應的 多官能基胺基甲酸酯丙烯酸酯（日本專利特開 2 0 0 1 _ 1 1' 3 Μ 8號公報），或揭示關於含有交聯性聚合物與同 一分子内具2個以上乙烯性不飽和基之化合物二者，藉由 使交聯性聚合物中的開環聚合性基與乙烯性不飽和基二者 進行聚合而硬化的硬化組成物，及使用其之硬塗處理物的 技術（日本專利特開2 0 0 3 - 1 4 7 0 1 7號公報）。 但是，在上述周知技術中，得知分別有下述問題點。曰 本專利特開2 0 CM - 1 1 3 6 4 8號公報中所揭技術，雖確認對基 材較厚且剛性較高的聚酯薄膜（厚度1 8 8 // m)具有效杲，但 是，在基材剛性較低的三乙醯纖維素薄膜方面，並無法將 薄膜曲捲抑制為較小。此外，日本專利特開2 0 0 3 - 1 4 7 0 1 7 號公報所揭技術，當對三乙醯纖維素薄膜施行硬塗處理之 情況時，因為薄膜具溼度依存性，因而無法充分的抑制薄 膜曲捲，無法獲得良好的處理性。 6 326傳利說明書(補件)\94-01 \9312955〇 1364364 所以，本發明之課題便在於提供一種以三乙醯纖維素薄 膜為支撐體，當形成硬塗層時抑制薄膜曲捲，並改善薄膜 曲捲的溼度依存性，且透明性或表面硬度優越的硬塗層薄 膜。 【發明内容】 本發明為解決上述課題，經深入鑽研結果，減小紫外線 或放射線硬化型樹脂的硬化收縮尚嫌不足，且針對三乙醯 纖維素薄膜構造（特別著眼於可塑劑分布），探討從表面能 量推測可塑劑的分布。結果，發現藉由在作為支撐體的三 乙酿纖維素薄膜之依據日本工業規格（Japanese Industrial Standard: JIS) K 6768 所測得表面能量在 35mN/m以上之側的面上設置硬塗層，便可解決課題。 換句話說，第1發明的硬塗層薄膜，係在支撐體上設置 含有紫外線硬化型樹脂或放射線硬化型樹脂之硬塗層者， 其特徵為，該支撐體係三乙醯纖維素薄膜，且在該支撐體 之依據日本工業規格（J I S ) K 6 7 6 8所測得表面能量為 3 5 m N / m以上之側的面上言il置硬塗層。 第2發明的硬塗層薄膜，係在第1發明中，該支撐體係 使用厚度30〜9〇Adm的三乙醯纖維素薄膜。 第3發明的硬塗層薄膜，係在第1發明中，該支撐體係 使用厚度30〜60/zm的三乙醯纖維素薄膜。 第4發明的硬塗層薄膜之製造方法，係在支撐體上，設 置含有紫外線硬化型樹脂或放射線硬化型樹脂之硬塗層 者，其特徵為，該支撐體係三乙醯纖維素薄膜，且在該支 7 326\專利說明書(補件)\94-01\93129550 1364364 撐體之依據日本工業規格（J I S ) Κ 6 7 6 8所測得表面能量為 35mN/m以上之側的面上設置硬塗層。 【實施方式】 以下，對本發明進行詳細說明。 三乙醯纖維素薄膜係將三乙醯纖維素、可塑劑、UV吸收 劑、滑劑，溶解、分散於溶劑中，調製成透明黏稠的摻雜 劑之後，再薄薄的澆注於旋轉的金屬板上而進行製膜。然 後，利用熱風施行乾燥，經從金屬板上剝離之後，便獲得 透明的三乙醯纖維素薄膜。在此乾燥步驟中，於從接觸空 氣之面進行溶劑揮發的過程中，確認到極性較高的可塑劑 將有較溶劑殘存更多於金屬板側的傾向。 再者，三乙醯纖維素薄膜在澆注後的乾燥步驟中，雖欲 一邊進行溶劑揮發一邊進行體積收縮，但是，因為接觸到 金屬板的薄膜面被金屬板所支撐著，因而並無法收縮，而 在保持著收縮應力的狀態下進行製膜、乾燥。當將保持著 收縮應力的三乙醯纖維素薄膜，使用於如欲使薄膜‘膨脹的 處理或環境中之情況時，薄膜本身所具有的收縮應力將放 開，而發生以接觸到金屬板側的面（即，可塑劑分布較多的 面）朝内側產生曲捲。若以此種薄膜為支撐體，使用含有溶 劑等的塗料以形成硬塗層的話，便將使接觸到金屬板側朝 内側發生曲捲。此外，當將硬塗層薄膜曝曬於多濕環境下 的情況時，薄膜本身所保持的收縮應力將放開，同樣的將 發生接觸到金屬板側的面朝内側產生曲捲。 三乙醯纖維素薄膜製造時所使用的可塑劑，可舉例如： 8 326傳利說明書(補件)\94-01\93129550 1364364 磷酸三苯酯、磷酸聯苯二苯酯、磷酸二曱基乙酯、乙醇酸 乙基笨二曱醖乙酯等，該等相較於三乙醯纖維素之下，屬 於極性較高。此外，可塑劑的分布與三乙醯纖維素薄膜的 表面能量具有關聯，極性較高的可塑劑量越多，表面能量 越低。換言之，在表面能量較低側的面上可塑劑將有不良 分布，在三乙醯纖維素薄膜製造時，接觸到金屬板的面（帶 面（band face))將不良分布有較多的可塑劑量，使表面能 量較低。可塑劑不良分布的多寡，可隨薄膜的乾燥步驟、 摻雜劑製作時所使用的溶劑種類、可塑劑種類而改變。可 塑劑分布較某基準為多的面，即根據J I S K 6 7 6 8所測得表 面能量在35mN/ni以下之側的面，通常屬於接觸金屬板的 面，可塑劑將極端分布不良。習知因為在帶面側設置硬塗 層的話，硬塗層與三乙醯纖維素薄膜間的密接性較佳，故 通常在帶面，即表面能量較低側的面上設置硬塗層。 本發明者等，發現藉由在三乙醯纖維素薄膜表面能量 3 5 m N / m以上之一側的面上設置硬塗層，而可抑制薄膜曲捲 與改善薄膜曲捲的溼度依存性，遂完成本發明"特別係在 薄膜厚度薄至30~60 Am的三乙醯纖維素薄膜中，最好在表 面能量37mN/m以上（尤以40mN/m以上為佳）之一側的面上 設置硬塗層的話，便可抑制薄膜曲捲。另外，當雙面的表 面能量均在35mN/m以上的情況時，亦可在任一面上設置硬 塗層。在普通的三乙醯纖維素薄膜中，表面能量上限值為 50mN/m。此外，若使用内外表面能量差在2mN/m以内之三 乙醯纖維素薄膜的話，將可明顯的抑制薄膜曲捲。 9 326\專利說明書(補件)\94-01\93129550 1364364 三乙醯纖維素薄膜，係如前述藉由澆注於旋轉的金屬板 上並成膜便可製得，金屬板一般係使用金屬帶或金屬筒。 在為提昇三乙醯纖維素薄膜表面能量方面，使薄膜厚度方 向的可塑劑分布均勻化乃屬有效方式，而因為利用滾筒法 製造的方式將可使可塑劑更均勻的存在，因此本發明最好 使用依滾筒法所製得的三乙醯纖維素薄膜。 本發明之當作硬塗層薄膜支撐體使用的三乙醯纖維素 薄膜，雖隨薄膜厚度，薄膜曲捲大小將有所變化，但是當 薄膜厚度在30~90/zm的情況時，若使用本發明的話，將發 現到曲捲抑制效果，對薄膜厚度薄至3 0〜6 0 // m的薄膜，曲 捲抑制效果將特別顯著。 本發明的硬塗層薄膜係如上述般，為以三乙醢纖維素薄 膜為支撐體，並在該支撐體上設置含有紫外線硬化型樹脂 或放射線硬化型樹脂之硬塗層的嗔塗層薄膜。紫外線硬化 型樹脂或放射線硬化型樹脂係配合需要，與溶劑混合（溶解 或分散）使用。所使用的溶劑可使用如：曱苯等芳香族類； 曱醇、乙醇、異丙醇等醇類；曱基溶纖劑、乙基溶纖劑、 丁基溶纖劑等溶纖劑類等等，混合周知有機溶劑使用。三 乙醯纖維素薄膜的耐溶劑性較低，為防止白化，最好使用 以甲苯為主成分的溶劑。此外，為求性能改良，在不影響 本發明效果的範疇下，可含有消泡劑、均塗劑、抗靜電劑、 抗氧化劑、紫外線吸收劑、光安定劑、聚合終止劑等。另 外，為對塗佈層賦予防眩性，在不影響本發明效果的範疇 下，亦可添加氧化矽粒子或丙烯酸樹脂、矽樹脂、胺基甲 10 326\專利說明書(補件)\94-01 \931295 50 1364364 酸酯樹脂等樹脂珠等、有機或無機的微粒子。 本發明所使用的紫外線硬化型樹脂或放射線硬化型樹 脂，係僅要利用照射電子束或紫外線等便硬化之透明樹脂 的話便可，其餘並無特別限制，可從如：胺基曱酸酯丙烯 酸酯系樹脂、聚酯丙烯酸酯系樹脂及丙烯酸環氧酯系樹脂 等之中適當選擇。 較佳者有如由分子内具2個以上（曱基）丙烯醯基之可紫 外線硬化的多官能基丙烯酸酯所構成者。分子内具2個以 上（甲基）丙烯醯基之可紫外線硬化的多官能基丙烯酸酯， 具體例有如：新戊二醇二（甲基）丙烯酸酯、1，6己二醇二 (曱基）丙烯酸酯、三（甲基）丙烯酸三羥甲基丙酯、四（甲基） 丙烯酸二（三羥曱基）丙酯、季戊四醇四（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 酯等聚醇聚丙烯酸酯；雙酚A二縮水甘油醚之二丙烯酸 酯、新戊二醇二縮水甘油醚之二丙烯酸酯、1，6己二醇二 縮水甘油醚之二（曱基）丙烯酸酯等（曱基）丙烯酸環氧酯； 由多元醇與多元羧酸及/或無水物，與丙烯酸進行酯化而所 獲得之聚酯（甲基）丙烯酸酯；利用使多元醇、多元異氰酸 酯及含羥基之（曱基）丙烯酸酯進行反應，而所獲得胺基甲 酸酯（曱基）丙烯酸酯、聚矽氧烷聚（曱基）丙烯酸酯等等。 上述可紫外線硬化的多官能基丙烯酸酯，可單獨使用， 亦可混合2種以上使用。其含有量係相對於硬塗層用塗料 的樹脂固形份，最好為5 0 ~ 9 5重量％。另外，除上述多官能 基（曱基）丙烯酸酯之外，亦可添加相對於硬塗層用塗料的 11 3%傳利說明書(補件)\94-01\9312955〇 1364364 樹脂固形份，最好為1 0重量％以下的2 -羥基（曱基）丙烯酸 醋、2 -經丙基（曱基）丙稀酸酯、（曱基）丙稀酸縮水甘油酯 等單官能基丙稀酸酯。 再者，在硬塗層中亦可添加以調整硬度為目的而使用的 聚合性寡聚物。此種寡聚物可舉例如：末端（曱基）丙烯酸 酯聚（曱基）丙烯酸曱酯、末端苯乙烯基聚（曱基）丙烯酸 酯、末端（曱基）丙烯酸酯聚苯乙烯、末端（曱基）丙烯酸酯 聚乙二醇、末端（甲基）丙烯酸酯-丙烯腈-苯乙烯共聚物、 末端（曱基）丙烯酸酯-苯乙烯-曱基丙烯酸曱酯共聚物等巨 型單體，其含有量係相對於硬塗層用塗料中的樹脂固形 份，最好為5〜5 0重量％。 本發明的硬塗層係將塗料組成物採用周知的塗佈裝 置，塗佈於透明支撐體上之後，再藉由照射電離輻射線使 之硬化而形成。周知的塗佈裝置可使用如：微凹版塗佈機、 凹版塗佈機、邁耶棒塗佈機（Mayer bar coater)、金屬型 塗佈機等塗佈裝置。塗佈時的塗料組成物黏度、濃度可依 所使用的塗佈裝置，調整為適當值。經硬化後的硬塗層膜 厚，通常為l~20/zm，最好為2〜10;zme若膜厚未滿l/zrn 的話，硬性將降低，反之，厚於2 0 a m的話，曲捲將變大。 [實施例] 以下，在實施例中詳細說明本發明，惟本發明並不僅限 於此。另外，實施例中的「份」與「％ j在無特別明示的前 提下，分別係指「重量份」與[重量％」。 對在實施例與比較例中所調製的硬塗層薄膜，針對下述 12 326傳利說明書(補件)\94-01\93129550 1364364 項目進行評估。 1 )表面能量 支撐體的表面能量係根據J I S K 6 7 6 8進行測量。表4 中所示係在實施例與比較例中，當作支撐體使用的薄膜表 面能量。 2 )塗佈層透明性 使用濁度計（村上色彩研究所公司製），根據J I S K - 7 1 0 5，測量硬塗層薄膜的濁度。 3 )密接性 根據J I S K 5 4 0 0，評估基板孔測試（間隙間隔1 m m )。將 塗佈層完全未從基材薄膜上剝落者記為「〇」，剝落未滿整 體塗佈層之9 0 %者記為「△」，整體塗佈層有9 0 %以上剝落 者記為 「X」。 4 )鉛筆硬度 使用HEIDON 14，根據JIS K 5400實施。 5 )薄膜曲捲 將硬塗層薄膜細切為A4尺寸（29.7x21. 0cm)，在一般環 境下（2 3 °C、5 0 % R Η )及多濕環境下（3 0 °C、9 0 % R Η ) ’進行2 4 小時調濕之後，實施薄膜曲捲高度的測量。計算出4角高 度的平均值。平均高度0mm~15mm:非常良好；15mm~30mm: 良好；30mm~50mm:不良；超過50mm的筒狀：明顯不良。 [實施例1 ] 以厚度8 0 // m的三乙醯纖維素薄膜（富士照片軟膠（股） 製型A)為支撐體，在其表面能量37mN/ni之側的面上，利 13 326\專利說明書(補件)\94-01\93129550 1364364 用棒塗佈機將下述表1的塗料組成物A進行塗佈，並利用 8 0 °C吹風機使稀釋溶劑蒸發之後，照射U V光，便獲得硬塗 層薄膜。此時的硬塗層厚度為5#πι。針對所獲得硬塗層薄 膜，就塗佈層的透明性、密接性、鉛筆硬度、薄膜曲捲進 行評估，結果如表5所示。1364364 IX. Description of the Invention: [Technical Field] The present invention relates to a film curl caused by hardening shrinkage of a hard coat layer when a layer is formed on a single side of a triacetyl cellulose film. A hard coat film which suppresses the humidity dependency, in particular, is a hard coat film which is excellent in handleability for protection of an electronic indicator surface such as a television receiver or a personal computer screen display. [Prior Art] Various display bodies or glass such as a liquid crystal display, a CRT, a plasma display, an outdoor display panel, and an illuminating board, in order to protect the surface thereof, a plastic resin film is used as a support, and a hard coat layer is provided thereon. Hard film. In particular, a flat panel represented by a liquid crystal display can be made of a triacetyl cellulose film from the viewpoints of high permeability, few defects, and no polarization. In general, the hard coating treatment is performed by applying an ultraviolet curable resin or a radiation curable resin to the surface of a thermoplastic resin film to form a hard layer. The ultraviolet curable resin or the radiation curable resin is composed of a monomer polymer and a photoinitiator, and the resin is hardened by the three-dimensional cross-linking to be hard. The thin roll occurs with the hardening shrinkage caused by the hardening of the resin. Among the thermoplastic resin films, the triethylene fluorene cellulose film is widely used because of its superiority. However, since the film has low rigidity and is markedly curled, the handleability is deteriorated and the productivity is lowered. Nowadays, in the sound of the thin and lightweight demand for the display, the thinner the film and the lower the rigidity of the film using the support, the 3% of the improvement of the film curl (the patch)\94-01\93丨2955〇5 Hard coating is small, and it is a big problem for the support surface after the thermal coating is applied to the thermal coating _ light-through coating, and the film is smattered. Further, since the hard-coated film is applied to the triacetyl cellulose film, since the constituent member as the polarizing plate is used, the adhesion to the polarizing film can be obtained, and the test can be easily carried out. At this time, the steps of the chemical treatment, washing, and drying are carried out in a humid environment, and therefore, if the humidity dependency of the film curl is obtained, the handleability is lowered. In order to improve the film curls, for example, a film containing a hardened film layer of a radiation curable resin composition containing at least two or more (fluorenyl) acrylonitrile groups and a hydroxyl group in the molecule is known. a radiation-curable polyfunctional (mercapto) acrylate, a polyfunctional urethane acrylate which is reacted with a polyisocyanate (Japanese Patent Laid-Open Publication No. 2000), Or revealing both a crosslinkable polymer and a compound having two or more ethylenically unsaturated groups in the same molecule, by making both a ring-opening polymerizable group and an ethylenically unsaturated group in the crosslinkable polymer A hardened composition which is hardened by polymerization, and a technique of using a hard-coating material thereof (Japanese Patent Laid-Open Publication No. 2000-1477-1978). However, in the above-mentioned well-known technology, it is known that there are the following problems. The technique disclosed in the Japanese Patent Publication No. 20 CM - 1 1 3 6 4 8 confirms that the polyester film (thickness 1 8 8 // m) having a thick base material and high rigidity is effective. However, in the case of a triacetyl cellulose film having a low substrate rigidity, the film curl cannot be suppressed to be small. In addition, in the technique disclosed in Japanese Laid-Open Patent Publication No. 2000-1277-1, when the triethyl fluorene cellulose film is subjected to a hard coat treatment, since the film has humidity dependency, it is not sufficient. The film curl is suppressed, and good handleability cannot be obtained. 6 326 Chuanli Manual (Supplement)\94-01 \9312955〇 1364364 Therefore, the object of the present invention is to provide a support film of triacetyl cellulose film, which suppresses film curling when forming a hard coat layer, and A hard coat film that improves the moisture dependence of the film curl and is excellent in transparency or surface hardness. SUMMARY OF THE INVENTION In order to solve the above problems, the present invention has been insufficiently studied to reduce the hardening shrinkage of ultraviolet rays or radiation curable resins, and to investigate the structure of triacetyl cellulose film (particularly focusing on the distribution of plasticizers). The distribution of the plasticizer is estimated from the surface energy. As a result, it was found that a hard coat layer was provided on the surface of the triethylene cellulose film as a support according to the surface of the Japanese Industrial Standard (JIS) K 6768 having a surface energy of 35 mN/m or more. The problem can be solved. In other words, the hard coat film according to the first aspect of the invention is a hard coat layer containing an ultraviolet curable resin or a radiation curable resin on a support, characterized in that the support system is a triacetyl cellulose film, and A hard coat layer is formed on the side of the support which is measured on the side of the surface energy of 3 5 m N / m or more according to Japanese Industrial Standards (JIS) K 6 7 6 8 . The hard coat film according to the second aspect of the invention is the first invention, wherein the support system uses a triethylene fluorene cellulose film having a thickness of 30 to 9 Å Adm. The hard coat film according to the third aspect of the invention is the first invention, wherein the support system uses a triacetyl cellulose film having a thickness of 30 to 60/zm. The method for producing a hard coat film according to the fourth aspect of the present invention is characterized in that the support system is provided with a hard coat layer containing an ultraviolet curable resin or a radiation curable resin, and the support system is a triacetyl cellulose film, and In the section on the side of the side where the surface energy is 35 mN/m or more measured by the Japanese Industrial Standard (JIS) Κ 6 7 6 8 in the support of the 7 326\patent specification (supplement)\94-01\93129550 1364364 Hard coating. [Embodiment] Hereinafter, the present invention will be described in detail. The triethylene fluorene cellulose film is prepared by dissolving and dispersing triacetyl cellulose, a plasticizer, a UV absorber, and a slip agent in a solvent to prepare a transparent viscous dopant, and then pouring the thin metal onto the rotating metal. Film formation was performed on the plate. Then, drying was carried out by hot air, and after peeling off from the metal plate, a transparent film of triacetyl cellulose was obtained. In this drying step, it was confirmed that the solvent having a higher polarity had a tendency to remain more on the side of the metal plate than in the process of volatilization of the solvent from the surface in contact with the air. Further, in the drying step after casting, the triethylene fluorene cellulose film undergoes volume shrinkage while volatilizing the solvent, but since the film surface contacting the metal plate is supported by the metal plate, it cannot be shrunk. Film formation and drying are carried out while maintaining the contraction stress. When the triethylene fluorene cellulose film which will maintain the contraction stress is used in the process of "expanding the film or in the environment", the shrinkage stress of the film itself will be released, and it will occur to contact the side of the metal plate. The face (i.e., the face with a large distribution of plasticizer) produces a curl toward the inside. When such a film is used as a support, and a coating material containing a solvent or the like is used to form a hard coat layer, the side contacting the metal plate side is curled. Further, when the hard coat film is exposed to a wet environment, the shrinkage stress held by the film itself is released, and the curling of the side contacting the metal plate side is also caused to occur. The plasticizer used in the manufacture of the triacetyl cellulose film may, for example, be as follows: 8 326 Licensing Instructions (Supplement)\94-01\93129550 1364364 Triphenyl phosphate, biphenyl diphenyl phosphate, dinonyl phosphate Ethyl ester, ethyl glutamate ethyl glycolate, etc., which are higher in polarity than triethylene fluorene cellulose. In addition, the distribution of the plasticizer is related to the surface energy of the triacetyl cellulose film, and the higher the plastic dose of higher polarity, the lower the surface energy. In other words, the plasticizer will have a poor distribution on the surface with the lower surface energy. When the triethylenesulfide cellulose film is manufactured, the surface (the band face) that contacts the metal plate will have a poor distribution of more plasticity. The dose makes the surface energy lower. The amount of poor distribution of the plasticizer may vary depending on the drying step of the film, the type of solvent used in the preparation of the dopant, and the type of the plasticizer. The plasticizer has a larger surface than a certain reference, that is, the surface whose surface energy is less than 35 mN/ni as measured according to J I S K 6 7 6 8 , which usually belongs to the surface of the contact metal plate, and the plasticizer will have an extremely poor distribution. Conventionally, since a hard coat layer is provided on the belt side, the adhesion between the hard coat layer and the triacetyl cellulose film is preferable, and therefore a hard coat layer is usually provided on the surface of the belt surface, that is, the surface having the lower surface energy. The inventors of the present invention have found that by providing a hard coat layer on the surface of the surface of the triethylene fluorene cellulose film having a surface energy of 3 5 m N / m or more, it is possible to suppress the film curl and improve the humidity dependency of the film curl.遂 遂 本 本 本 遂 遂 遂 遂 遂 遂 遂 遂 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别 特别When a hard coat layer is provided on the surface, the film curl can be suppressed. Further, when the surface energy of both sides is 35 mN/m or more, a hard coat layer may be provided on either side. In the conventional triacetyl cellulose film, the upper limit of the surface energy is 50 mN/m. Further, if a triacetyl cellulose film having an inner and outer surface energy difference of 2 mN/m or less is used, the film curl can be remarkably suppressed. 9 326\Patent Specification (Repair)\94-01\93129550 1364364 Triethylene phthalate film can be obtained by casting on a rotating metal plate and forming a film as described above. Metal plates are generally made of metal tape. Or a metal tube. In order to improve the surface energy of the triacetyl cellulose film, it is an effective way to homogenize the distribution of the plasticizer in the thickness direction of the film, and since the method of manufacturing by the roller method can make the plasticizer more uniform, the present invention is the most It is preferable to use a triacetone cellulose film obtained by a roller method. The triacetyl cellulose film used as the hard coat film support of the present invention may vary in film roll size depending on the film thickness, but when the film thickness is 30 to 90/zm, if used In the case of the present invention, the effect of suppressing the curl is found, and the film suppressing effect is particularly remarkable for a film having a film thickness as thin as 30 to 60 // m. The hard coat film of the present invention is a ruthenium-coated film containing a hard coat layer of an ultraviolet curable resin or a radiation curable resin, which is supported by a triethylene fluorene cellulose film as described above. . The ultraviolet curable resin or the radiation curable resin is used in combination with a solvent (dissolved or dispersed). The solvent to be used may be, for example, an aromatic such as toluene; an alcohol such as decyl alcohol, ethanol or isopropanol; a cellosolve, a cellosolve, a cellosolve such as butyl cellosolve, etc. Mixing well-known organic solvents is used. The triacetyl cellulose film has low solvent resistance, and in order to prevent whitening, it is preferred to use a solvent containing toluene as a main component. Further, in order to improve the performance, an antifoaming agent, a leveling agent, an antistatic agent, an antioxidant, an ultraviolet absorber, a photostabilizer, a polymerization terminator or the like may be contained in the range which does not impair the effects of the present invention. Further, in order to impart anti-glare property to the coating layer, cerium oxide particles or acrylic resin, anthraquinone resin, and an amine group 10 326\patent specification (supplement)\94- may be added without affecting the effects of the present invention. 01 \931295 50 1364364 Organic or inorganic fine particles such as resin beads such as acid ester resins. The ultraviolet curable resin or the radiation curable resin used in the present invention may be a transparent resin which is cured by irradiation with an electron beam or ultraviolet rays, and is not particularly limited, and may be, for example, an amino phthalate acrylic acid. The ester resin, the polyester acrylate resin, and the epoxy acrylate resin are appropriately selected. Preferably, it is composed of a polyfunctional acrylate which is ultraviolet-curable by having two or more (fluorenyl) acrylonitrile groups in the molecule. The ultraviolet curable polyfunctional acrylate having two or more (meth) acrylonitrile groups in the molecule, and specific examples thereof include neopentyl glycol di(meth)acrylate and 1,6 hexanediol di(decyl) group Acrylate, trimethylolpropyl tri(meth)acrylate, bis(trihydroxymethyl)propyl tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate Polyalcoholic acid polyacrylate such as dipentaerythritol hexa(meth) acrylate; diacrylate of bisphenol A diglycidyl ether, diacrylate of neopentyl glycol diglycidyl ether, dihydrogenation of 1,6 hexanediol Ethylene (meth) acrylate such as glyceryl ether bis(indenyl) acrylate; polyester (meth) acrylate obtained by esterification of polyhydric alcohol with polycarboxylic acid and/or anhydrate and acrylic acid The urethane (mercapto) acrylate, the polydecyl oxyalkylene acrylate, and the like are obtained by reacting a polyol, a polyvalent isocyanate, and a hydroxyl group-containing (mercapto) acrylate. The ultraviolet curable polyfunctional acrylate may be used singly or in combination of two or more. The content thereof is preferably from 50 to 9.5 wt% based on the resin solid content of the coating for a hard coat layer. In addition, in addition to the above polyfunctional (fluorenyl) acrylate, it is also possible to add 11% of the transfer specification (supplement) \94-01\9312955〇1364364 resin solid content relative to the coating for hard coat layer, most Preferably, it is a monofunctional acrylate such as 2-hydroxy(indenyl)acrylic acid vinegar, 2-propyl (indenyl) acrylate, or (mercapto) acrylic acid glycidyl ester. . Further, a polymerizable oligomer used for the purpose of adjusting the hardness may be added to the hard coat layer. Such an oligomer may, for example, be a terminal (fluorenyl) acrylate poly(fluorenyl) decyl acrylate, a terminal styryl poly(fluorenyl) acrylate, a terminal (fluorenyl) acrylate polystyrene, a terminal ( a mega-monomer such as acrylate-based polyethylene glycol, terminal (meth) acrylate-acrylonitrile-styrene copolymer, terminal (fluorenyl) acrylate-styrene-mercapto methacrylate copolymer, The content is preferably from 5 to 50% by weight based on the solid content of the resin in the coating for a hard coat layer. The hard coat layer of the present invention is formed by applying a coating composition to a transparent support by a well-known coating device, followed by hardening by irradiation with ionizing radiation. A coating device such as a micro gravure coater, a gravure coater, a Mayer bar coater, or a metal coater can be used. The viscosity and concentration of the coating composition at the time of coating can be adjusted to an appropriate value depending on the coating device to be used. The hard coating film thickness after hardening is usually 1~20/zm, preferably 2~10; if the film thickness is less than l/zrn, the hardness will decrease, and if it is thicker than 20am, the curve will be The volume will grow larger. [Examples] Hereinafter, the present invention will be described in detail in the examples, but the present invention is not limited thereto. In addition, "parts" and "% j" in the examples mean "parts by weight" and "% by weight", respectively, unless otherwise specified. The hard coat film prepared in the examples and the comparative examples was evaluated for the following 12 326 patent specification (supplement)\94-01\93129550 1364364 item. 1) Surface energy The surface energy of the support is measured in accordance with J I S K 6 7 6 8 . The surface energy of the film used as a support in the examples and comparative examples is shown in Table 4. 2) Coating layer transparency The turbidity of the hard coat film was measured by a turbidity meter (manufactured by Murakami Color Research Co., Ltd.) in accordance with J I S K - 7 105. 3) Adhesion According to J I S K 5 400, the substrate hole test (gap interval 1 m m ) was evaluated. The coating layer was not peeled off from the base film as "〇", and the 90% of the entire coating layer was "△", and the entire coating layer was 90% or more. "X". 4) Pencil hardness Using HEIDON 14, it was carried out in accordance with JIS K 5400. 5) The film roll is finely cut into A4 size (29.7x21. 0cm), under normal conditions (23 °C, 50% R Η) and humid environment (30 °C, 9) 0 % R Η ) 'After 24 hours of humidity conditioning, measure the film curl height. Calculate the average of the four corner heights. Average height 0mm~15mm: very good; 15mm~30mm: good; 30mm~50mm: bad; more than 50mm tubular: obviously bad. [Example 1] A triacetonitrile cellulose film (Fuji Photo Soft Co., Ltd. type A) having a thickness of 80 μm was used as a support, and a surface having a surface energy of 37 mN/ni was used. 326\Patent specification (supplement)\94-01\93129550 1364364 The coating composition A of the following Table 1 was coated with a bar coater, and the diluted solvent was evaporated by a hair dryer at 80 ° C, and then irradiated with UV light. A hard coat film is obtained. The hard coat thickness at this time is 5#πι. The transparency, adhesion, pencil hardness, and film curl of the coating layer were evaluated for the obtained hard coat film, and the results are shown in Table 5.
表1 :塗料組成物A 紫外線硬化型樹脂（商品名： UV-1700B、曰本合成化學（股）製） 9 5 . 0重量份 起始劑（商品名：伊爾佳邱1 8 4、汽巴 嘉基公司製） 5 . 0重量份 甲苯 2 0 0 . 0重量份 異丙醇 5 0 . 0重量份 氟系界面活性劑（商品名：美嘉華克 F - 1 7 7、大曰本油墨（股）製） 對液0. 05重量份 [實施例2 ] 除以厚度80//m的三乙醯纖維素薄膜（富士照片軟膠（股） 製型A)為支撐體，並在其表面能量39mN/m之側的面上， 塗佈著塗料組成物A之外，其餘均如同實施例1製作硬塗 層薄膜，針對塗佈層的透明性、密接性、鉛筆硬度、薄膜 曲捲進行評估，結果如表5所示。 [實施例3 ] 除以厚度的三乙醯纖維素薄膜（富士照片軟膠（股） 製型B)為支撐體，並在其表面能量41mN/m之側的面上， 塗佈著塗料組成物A之外，其餘均如同實施例1製作硬塗 14 326\專利說明書(補件)\94-01 \93129550 1364364 層薄膜，針對塗佈層的透明性、密接性、鉛筆硬度 曲捲進行評估，結果如表5所示。 [實施例4 ] 除以厚度80〆m的三乙醯纖維素薄膜（富士照片4 製型B)為支撐體，並在其表面能量40mN/m之側的 塗佈著塗料組成物A之外，其餘均如同實施例1製 層薄膜，針對塗佈層的透明性、密接性、鉛筆硬度 曲捲進行評估，結果如表5所示。 [實施例5 ] 除以厚度80// m的三乙醯纖維素薄膜（科尼卡（股 C)為支撐體，並在其表面能量37mN/m之側的面上， 塗料組成物A之外，其餘均如同實施例1製作硬塗3 針對塗佈層的透明性、密接性、鉛筆硬度、薄膜曲 評估，結果如表5所示。 [實施例6 ] 除以厚度4 0 y m的三乙醯纖維素薄膜（富士照片孝 製型D)為支撐體，並在其表面能量40mN/m之側的 塗佈著塗料組成物A之外，其餘均如同實施例1.製 層薄膜，針對塗佈層的透明性、密接性、鉛筆硬度 曲捲進行評估，結果如表5所示。 [實施例7 ] 除塗佈著表2所示塗料組成物B之外，其餘均如 例1製作硬塗層薄膜，針對塗佈層的透明性、密接 筆硬度、薄膜曲捲進行評估，結果如表5所示。 326\專利說明書(補件)\94-01 \93129550 15 、薄膜 匕膠（股） 面上 ， 作硬塗 、薄膜 )製型 塗佈著 卜薄膜， 捲進行 t膠（股） 面上， 作硬塗 、薄膜 同實施 性、船 1364364Table 1: Coating composition A UV-curable resin (trade name: UV-1700B, manufactured by 曰本合成化学), 9 5 parts by weight of starting agent (trade name: Iljiaqiu 1 8 4, steam Bajiaji Company) 5.0 parts by weight of toluene 2 0 0. 0 parts by weight of isopropanol 5 0. 0 parts by weight of fluorine-based surfactant (trade name: Mega Wagke F - 1 7 7, Otsuka ink) (Stock) system 0. 05 parts by weight [Example 2] Divided by a thickness of 80 / / m of triacetyl cellulose film (Fuji Photosoft (stock) type A) as a support, and in The surface of the surface energy of 39 mN/m was coated with the coating composition A, and the other hard coating film was produced as in Example 1, and the transparency, adhesion, pencil hardness, and film curl of the coating layer were applied. The evaluation was carried out and the results are shown in Table 5. [Example 3] A triacetonitrile cellulose film (Fuji Photosoft Co., Ltd. type B) was used as a support, and a coating composition was applied on the surface having a surface energy of 41 mN/m. Except for the material A, the remaining hard coating 14 326\patent specification (supplement)\94-01 \93129550 1364364 film was prepared as in Example 1, and the transparency, adhesion, and pencil hardness of the coating layer were evaluated. The results are shown in Table 5. [Example 4] A triacetonitrile cellulose film (Fuji Photo 4 Model B) having a thickness of 80 μm was used as a support, and a coating composition A was coated on the side having a surface energy of 40 mN/m. The rest were evaluated as in the film of Example 1, and the transparency, adhesion, and pencil hardness of the coating layer were evaluated. The results are shown in Table 5. [Example 5] Divided by a triacetonitrile cellulose film having a thickness of 80 / / m (Konica (C) C as a support, and on the side of the surface energy of 37 mN / m side, the coating composition A Except that the hard coat 3 was evaluated for transparency, adhesion, pencil hardness, and film curvature of the coating layer as in Example 1, and the results are shown in Table 5. [Example 6] Divided by three thicknesses of 40 μm The acetaminophen film (Fuji Photo D) was a support, and the coating composition A was coated on the side of the surface energy of 40 mN/m, and the rest was as in Example 1. The transparency, adhesion, and pencil hardness of the coating layer were evaluated, and the results are shown in Table 5. [Example 7] Except that the coating composition B shown in Table 2 was applied, the same was carried out as in Example 1. The hard coat film was evaluated for the transparency of the coating layer, the hardness of the tacky pen, and the film curl. The results are shown in Table 5. 326\Patent Specification (Supplement)\94-01 \93129550 15 , Film Silicone ( On the surface, as a hard coat, film), coated with a film, and rolled onto a t-rubber surface to make a hard coat. Film of the same embodiment, boats 1364364
表2 :塗料組成物B 紫外線硬化型樹脂（商品名：U V - 1 7 0 0 Β、日本 合成化學（股）製） 9 2 . 5重量份 塞利希亞4 3 0 (富士希利西亞公司製）平均粒徑 4 . 0 // m 2. 5重量份 起始劑（商品名：伊爾佳邱1 8 4、汽巴嘉基公司 製） 5. 0重量份 甲苯 2 0 0 . 0重量份 異丙醇 5 0 . 0重量份 矽氧烷系界面活性劑（商品名：Β Y K - 3 2 5、畢克 化學公司製） 對液0 . 0 5重量 份 [比較例1 ] 除以厚度80/zm的三乙醯纖維素薄膜（科尼卡（股）製型 C)為支撐體，並在其表面能量34mN/m之側的面上，塗佈著 塗料組成物A之外，其餘均如同實施例1製作硬塗層薄膜， 針對塗佈層的透明性、密接性、鉛筆硬度、薄膜曲捲進行 評估，結果如表5所示。 [比較例2 ] 除以厚度38/zm的聚酯薄膜（商品名：A4300、東洋紡積 (股）製）為支撐體，並在其表面能量48mN/m之側的面上， 塗佈著塗料組成物A之外，其餘均如同實施例1製作硬塗 層薄膜，針對塗佈層的透明性、密接性、鉛筆硬度、薄膜 曲捲進行評估，結果如表5所示。 [比較例3 ] 16 326\專利說明書(補件)\9Φ01\93129550 1364364 除以厚度80/zm的三乙醯纖維素薄膜（科尼卡（股）製型 C)為支撐體，並在其表面能量34mN/m之側的面上，塗佈著 使用硬化收缩較小樹脂的下述表3之塗料組成物C之外， 其餘均如同實施例1製作硬塗層薄膜，針對塗佈層的透明 性、密接性、鉛筆硬度、薄膜曲捲進行評估，結果如表5 所示。Table 2: Coating composition B Ultraviolet curing resin (trade name: UV - 1 7 0 0 Β, manufactured by Nippon Synthetic Chemical Co., Ltd.) 9 2 . 5 parts by weight Celicia 4 3 0 (Fuji Hilicia Co., Ltd. Manufactured by an average particle size of 4. 0 // m 2. 5 parts by weight of starting agent (trade name: Iljiaqiu 1 8 4, manufactured by Cibajiaji Co., Ltd.) 5. 0 parts by weight of toluene 2 0 0 . 0 weight Part by weight of isopropanol 5 0. 0 parts by weight of a siloxane surfactant (trade name: Β YK - 3 2 5, manufactured by BYK Chemical Co., Ltd.) 0. 0 parts by weight [Comparative Example 1] Divided by thickness 80/zm of triethylene fluorene cellulose film (Konica) is a support, and is coated with a coating composition A on the surface having a surface energy of 34 mN/m. The hard coat film was produced as in Example 1, and the transparency, adhesion, pencil hardness, and film curl of the coating layer were evaluated. The results are shown in Table 5. [Comparative Example 2] A polyester film (trade name: A4300, manufactured by Toyobo Co., Ltd.) having a thickness of 38/zm was used as a support, and a coating was applied to the surface having a surface energy of 48 mN/m. Except for the composition A, a hard coat film was produced as in Example 1, and the transparency, adhesion, pencil hardness, and film curl of the coating layer were evaluated. The results are shown in Table 5. [Comparative Example 3] 16 326\Patent Specification (Replenishment)\9Φ01\93129550 1364364 Divided by a thickness of 80/zm of triacetyl cellulose film (Konica) (C), as a support, and The surface of the surface energy of 34 mN/m was coated with a coating composition C of the following Table 3 using a resin having a small hardening shrinkage, and the other was a hard coat film as in Example 1, for the coating layer. Transparency, adhesion, pencil hardness, and film curl were evaluated. The results are shown in Table 5.
表3:塗料組成物C 紫外線硬化型樹脂（商品名：UV-7640B、日本合成化 學（股）製） 95. 0重量份 起始劑（商品名：伊爾佳邱184、汽巴嘉基公司製） 5.0重量份 曱苯 200. 0重量份 異丙醇 50. 0重量份 氟系界面活性劑（商品名：美嘉華克F-177、大曰本油 墨（股）製） 對液0. 05重量份 表4 支撐體 表面能量 (mN/m) 表面能量 (mN/m) 製膜時的金屬板型式 富士照片軟膠（股）製型A 39 37 金屬帶 富士照片軟膠（股）製型B 41 40 金屬筒 科尼卡（股）製型C 37 34 金屬帶 富士照片軟膠（股）製型D 40 39 金屬帶 A4300C雙面易黏著處理） 48 48 一 326\專利說明書(補件)\94-01\93129550 17 1364364 表5 濁度 (%) 密接性 表面硬度 薄膜曲捲 一般環境下 多濕環境下 實施例1 0.2 〇 2H 非常良好 良好 實施例2 0.2 〇 2H 非常良好 非常良好 實施例3 0.2 〇 2H 非常良好 非常良好 實施例4 0. 2 〇 2H 非常良好 非常良好 實施例5 0. 1 〇 2H 非常良好 非常島好 實施例6 0‘ 1 〇 2H 非常良好 非常良好 實施例7 5.3 〇 2H 非常良好 非常良好 比較例1 0.2 〇 2H 不良 明顯不良 比較例2 0.5 〇 2H 良好 良好 比較例3 0.2 〇 Η 非常良好 明顯不良 如表5所示，將硬塗層設置於為支撐體的三乙醯纖維素 薄膜之表面能量3 5 m N / m以上之側的面上之實施例1〜7的硬 塗層薄膜，係明顯的抑制薄膜曲捲，密接性、表面硬度均 無問題。實施例7雖調配作為顏料的氧化矽，而對硬塗層 薄膜賦予防眩性，但是如同實施例1 ~ 6，密接性、表面硬 度亦均無問題。相對於此，將硬塗層設置於表面能量未滿 3 5 m N / m侧之面上的比較例1之硬塗層薄膜，係無法充分的 抑制薄膜曲捲。此外，將硬塗層設置於表面能量34mN/m 側之面，且使用硬化收縮較小樹脂的比較例3，係確認到 表面硬度降低，且在一般環境下雖確認到薄膜曲捲抑制效 果，但是在多濕環境下則無法獲得薄膜曲捲抑制效果。另 外，使用聚酯薄膜作為支撐體的比較例2之硬塗層薄膜， 係如三乙醯纖維素薄膜中所發現般，無薄膜曲捲的溼度依 18 326傳利說明書(補件)\94-01\93129550 1364364 存性，且關於密接性、表面硬度亦無問 (發明效果） 依照本發明的話，可提供當以三乙醯 體，形成硬塗層的情況時，抑制薄膜曲 的溼度依存性，且透明性或表面硬度優 19 題。 纖維素薄膜為支撐 捲並改善薄膜曲捲 越的硬塗層薄膜。 326\專利說明書(補件)\94-01\93129550Table 3: Coating composition C UV-curable resin (trade name: UV-7640B, manufactured by Nippon Synthetic Chemical Co., Ltd.) 95. 0 parts by weight of starting agent (trade name: Iljiaqiu 184, Cibajiaji Company) 0重量份为0. 05 parts by weight of isopropyl alcohol 50. 0 parts by weight of fluorochemical surfactant (trade name: Mika Wagke F-177, Otsuka ink (share) made) 0. 05 Parts by weight Table 4 Surface energy of support (mN/m) Surface energy (mN/m) Metal plate type Fujifilm photo soft film (sand) type A 39 37 Metal tape Fuji photo soft rubber (stock) type B 41 40 Metal tube Konica (stock) type C 37 34 Metal belt Fuji photo soft (stock) type D 40 39 Metal belt A4300C double-sided easy adhesion treatment 48 48 a 326\patent specification (supplement) \94-01\93129550 17 1364364 Table 5 Turbidity (%) Adhesive surface hardness Film curling Under normal environment, in a humid environment Example 1 0.2 〇 2H Very good Good Example 2 0.2 〇 2H Very good Very good example 3 0.2 〇2H Very good Very good Example 4 0. 2 〇2H Very good Very good example 5 0. 1 〇 2H Very good very good island Good example 6 0' 1 〇 2H Very good Very good Example 7 5.3 〇 2H Very good Very good Comparative example 1 0.2 〇 2H Poorly apparently poor Comparative example 2 0.5 〇2H Good and good Comparative Example 3 0.2 〇Η Very good and significant failure As shown in Table 5, the hard coat layer was placed on the side of the surface energy of the triethylene fluorene cellulose film as a support of 3 5 m N / m or more. The hard coat film of Examples 1 to 7 on the surface significantly suppressed the film curl, and had no problem in adhesion and surface hardness. In Example 7, although the ruthenium oxide as a pigment was blended to impart anti-glare properties to the hard coat film, as in Examples 1 to 6, there was no problem in adhesion and surface hardness. On the other hand, in the hard coat film of Comparative Example 1 in which the hard coat layer was provided on the surface having a surface energy of less than 3 5 m N / m side, the film curl could not be sufficiently suppressed. In addition, in Comparative Example 3 in which the hard coat layer was provided on the surface having a surface energy of 34 mN/m and the resin having a small shrinkage shrinkage was used, it was confirmed that the surface hardness was lowered, and the film curl suppressing effect was confirmed in a general environment. However, in a humid environment, the film curl suppression effect cannot be obtained. Further, the hard coat film of Comparative Example 2 using a polyester film as a support is as found in a film of triethylene fluorene cellulose, and the humidity of the film-free curl is in accordance with the specification (Supplement). -01\93129550 1364364 Dependence on the adhesion and surface hardness (invention effect) According to the present invention, it is possible to suppress the humidity dependence of the film curvature when a hard coat layer is formed by triethylene oxime Sexuality, and transparency or surface hardness is excellent. The cellulose film is a hard coat film which supports the roll and improves the film curl. 326\ patent specification (supplement)\94-01\93129550