200528267 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，形成硬塗 層之際，因硬塗層的硬化收縮而所引起的薄膜曲捲較小， 且經抑制過溼度依存性的硬塗層薄膜，詳言之，為關於適 用於如電視接收器或個人電腦螢幕顯示之類之電子資訊顯 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、電子 看板等各種顯示體或玻璃，為能保護其表面，便使用以熱 可塑性樹脂薄膜為支撐體，並在其上設置硬塗層的硬塗層 薄膜。特別係以液晶顯示器為代表的平面面板，就從光穿 透性較高、缺點較少、無偏光性等觀點而言，支撐體的熱 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上塗 敷紫外線硬化型樹脂或放射線硬化型樹脂，而形成硬塗 層。紫外線硬化型樹脂或放射線硬化型樹脂係由單體、寡 聚物、光起始劑構成，利用3次元交聯引起樹脂硬化而顯 現出硬性。隨此樹脂硬化所產生的硬化收縮而發生薄膜曲 捲。熱可塑性樹脂薄膜中，三乙醯纖維素薄膜雖因上述特 性而被廣泛的使用，但是因為薄膜剛性較低，明顯發生薄 膜曲捲，因而造成處理性變差、生產性降低的問題。今後， 在對顯示器的薄型、輕量化需求高漲之聲浪中，使用為支 撐體的薄膜將越薄且剛性較低，在薄膜曲捲的改善方面將 5 326\專利說明書(補件)\94-01\93129550 200528267 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（甲基）丙烯醯基及羥基的放射線硬 化型多官能基（甲基）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 6 4 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 0 1 - 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)具有效果，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\專利說明書(補件)\94-01\93129550 200528267 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 乙醯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 3 5 m N / 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以上之側的面上設置硬塗層。 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30〜90//m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3 0〜6 0 // m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 200528267 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 3 5 m N / 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： 326\專利說明書(補件)\94-01\93129550 8 200528267 磷酸三苯酯、磷酸聯苯二苯酯、磷酸二曱基乙酯、乙醇酸 乙基苯二曱醯乙酯等，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3 5 m N / m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3 0〜6 0 // m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3 5 m N / 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。 326\專利說明書(補件)\94-01\93129550 9 200528267 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3 0〜9 0 // m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，為以三乙醯纖維素薄 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硬塗層薄膜。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；甲基溶纖劑、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、胺基曱 10 326\專利說明書(補件)\94-01\93129550 200528267 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（曱基）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（曱基）丙烯酸三羥曱基丙酯、四（曱基） 丙烯酸二（三羥曱基）丙酯、季戊四醇四（曱基）丙烯酸酯、 季戊四醇三（曱基）丙烯酸酯、二季戊四醇六（曱基）丙烯酸 酯等聚醇聚丙婦酸S旨；雙紛A二縮水甘油謎之二丙稀酸 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（曱基）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，而所獲得胺基曱 酸酯（甲基）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 326\專利說明書(補件)\94-01\93129550 11 200528267 樹脂固形份，最好為1 0重量％以下的2 _羥基（曱基）丙 酯、2 -羥丙基（甲基）丙烯酸酯、（曱基）丙烯酸縮水甘 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 聚合性寡聚物。此種寡聚物可舉例如：末端（曱基）丙 酯聚（曱基）丙烯酸曱酯、末端苯乙烯基聚（甲基）丙烯 酯、末端（甲基）丙烯酸酯聚苯乙烯、末端（曱基）丙烯 聚乙二醇、末端（曱基）丙烯酸酯-丙烯腈-苯乙烯共聚 末端（甲基）丙烯酸酯-苯乙烯-甲基丙烯酸甲酯共聚物 型單體，其含有量係相對於硬塗層用塗料中的樹脂固 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 之硬化而形成。周知的塗佈裝置可使用如：微凹版塗科 凹版塗佈機、邁耶棒塗佈機（Mayer bar coater)、金 塗佈機等塗佈裝置。塗佈時的塗料組成物黏度、濃度 所使用的塗佈裝置，調整為適當值。經硬化後的硬塗 厚，通常為1〜20//m，最好為2〜10//m。若膜厚未滿: 的話，硬性將降低，反之，厚於2 0 // m的話，曲捲將變 [實施例] 以下，在實施例中詳細說明本發明，惟本發明並不 於此。另外，實施例中的「份」與「％」在無特別明示 提下，分別係指「重量份」與「重量！ϋ」。 對在實施例與比較例中所調製的硬塗層薄膜，針對 326\專利說明書(補件)\94-01\93129550 12 烯酸 油S旨 用的 烯酸 酸 酸酯 物、 等巨 形 線使 機、 屬型 可依 層膜 ;β m 大。 僅限 的前 下述 200528267 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 )錯筆硬度 使用HEID0N 14，根據JIS K 5 4 0 0實施。 5 )薄膜曲捲 將硬塗層薄膜細切為A 4尺寸（2 9 · 7 X 2 1 · 0 c m )，在一般環 境下（23°C、5 0%RH)及多濕環境下（30°C、90%RH)，進行24 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Omm〜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 μ 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/m之側的面上，利 13200528267 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a film curl caused by the hardening and shrinkage of a hard coating layer when a hard coating layer is formed on one side of a triethyl cellulose film. A small, hard-coated film with reduced dependence on over-humidity. Specifically, it is a hard-coating film that is suitable for protecting the surface of electronic information displays such as television receivers or personal computer screens. Coating film. [Previous technology] Various display bodies or glass such as liquid crystal displays, CRTs, plasma displays, outdoor display panels, electronic sign boards, etc., to protect the surface, use a thermoplastic resin film as a support, and provide a hard coating on it Layer of hard coating film. In particular, a flat panel typified by a liquid crystal display is a triethylfluorene cellulose film that can be used as a thermoplastic resin film for a support from the viewpoints of high light permeability, few defects, and no polarization. A general hard coating method is to form a hard coating layer by coating a surface of a thermoplastic resin film with an ultraviolet curing resin or a radiation curing resin. The ultraviolet-curable resin or the radiation-curable resin is composed of a monomer, an oligomer, and a photoinitiator, and the resin is hardened by three-dimensional cross-linking to show rigidity. Film curling occurs with the shrinkage of the hardening caused by the hardening of this resin. Among the thermoplastic resin films, triethyl cellulose film has been widely used due to the above characteristics, but because the film rigidity is low, the film curling obviously occurs, resulting in the problem of poor handling and lower productivity. In the future, in the growing demand for thinner and lighter displays, the thinner the film used as a support will be, the thinner and lower the rigidity will be. In terms of improving the film curl, 5 326 \ Patent Specification (Supplement) \ 94- 01 \ 93129550 200528267 became a big issue. In addition, since the film subjected to the hard coating treatment on the triethylammonium cellulose film is used as a constituent member of the polarizing plate, it is convenient to perform the test treatment in order to obtain the adhesion with the polarizing film. In this case, since the steps of laboratory treatment, cleaning, and drying are carried out in a humid environment, if there is a humidity dependency of the film curl, the handleability will be reduced. To improve such film curls, the following techniques are known. For example, a film containing a cured film layer of a radiation-curable resin composition contains a radiation-curable polyfunctional (meth) acrylate having at least two (meth) acryl groups and hydroxyl groups in the molecule, and Polyisocyanate polyfunctional urethane acrylate (Japanese Patent Laid-Open No. 2 0 1-1 1 3 6 4 8), or it is disclosed that a polymer containing a crosslinkable polymer and the same molecule has 2 Two or more ethylenically unsaturated compounds, a hardened composition that hardens by polymerizing both a ring-opening polymerizable group and an ethylenically unsaturated group in a crosslinkable polymer, and a hard coating using the same Process technology (Japanese Patent Laid-Open No. 2003-1477-1017). However, in the above-mentioned well-known technology, it is understood that each of the following problems. Although the technology disclosed in Japanese Patent Application Laid-Open No. 2000-1-1 1 3 6 4 8 is confirmed to have an effect on a thick and rigid polyester film (thickness 1 8 8 // m), However, in the case of a triethyl cellulose cellulose film having a relatively low substrate rigidity, the film curl cannot be suppressed to be small. In addition, in the technology disclosed in Japanese Patent Laid-Open No. 2000-314747017, when a hard coating process is performed on a triethyl cellulose film, the film cannot be sufficiently used because of its humidity dependence. Film curl is suppressed, and good handleability cannot be obtained. 6 326 \ Patent Specification (Supplement) \ 94-01 \ 93129550 200528267 Therefore, the problem of the present invention is to provide a triethyl cellulose cellulose film as a support body, which suppresses film curling and improves when a hard coating layer is formed. Film-coated hard-coated film with excellent humidity dependence and excellent transparency or surface hardness. [Summary of the Invention] In order to solve the above-mentioned problems, the present invention has in-depth research results to reduce the curing shrinkage of ultraviolet or radiation curable resins. It is still insufficient to investigate the structure of triethyl cellulose cellulose film (especially focusing on plasticizer distribution) The distribution of the plasticizer is inferred from the surface energy. As a result, it was found that the surface energy measured by the Japanese Industrial Standard (JIS) K 6768 based on the triethyl cellulose cellulose film as a support was hardened on the side of 3 5 m N / m or more. Coating can solve the problem. In other words, the hard coat film of the first invention is one in which a hard coat layer containing a UV-curable resin or a radiation-curable resin is provided on a support, and the support system is a triethyl cellulose film, and A hard coat layer is provided on the side of the support having a surface energy of 3 5 m N / m or more as measured in accordance with Japanese Industrial Standards (JIS) K 6 7 6 8. The hard coat film of the second invention is the first invention, and the support system uses a triethylammonium cellulose film having a thickness of 30 to 90 // m. The hard coating film according to the third invention is the first invention, and the supporting system uses a triethylammonium cellulose film having a thickness of 30 to 6 0 // m. The method for producing a hard coat film according to the fourth invention is a method in which a hard coat layer containing an ultraviolet curable resin or a radiation curable resin is provided on a support, and the support system is a triethyl cellulose film, and The surface energy measured at 7 326 \ Patent Specification (Supplement) \ 94-01 \ 93129550 200528267 of the support according to Japanese Industrial Standards (JIS) K 6 7 6 8 is 3 5 m N / m or more. A hard coat is provided on the surface. [Embodiment] Hereinafter, the present invention will be described in detail. Triethyl cellulose cellulose film is made by dissolving and dispersing triethyl cellulose, plasticizer, UV absorber, and slip agent in a solvent to prepare a transparent and viscous dopant, and then casting it thinly on a rotating metal. Film formation was performed on a plate. Then, it was dried by hot air, and after peeling from the metal plate, a transparent triethylammonium cellulose film was obtained. In this drying step, in the process of solvent volatilization from the surface in contact with air, it was confirmed that the plasticizer having a higher polarity tends to remain more than the solvent on the metal plate side. In addition, in the drying step after casting, although the triethylammonium cellulose film is intended to undergo volume shrinkage while evaporating the solvent, the film surface in contact with the metal plate is supported by the metal plate, so it cannot shrink. On the other hand, the film was formed and dried while the shrinkage stress was maintained. When the triethylcellulose film that maintains the shrinkage stress is used in a process or environment where the film is to be expanded, the shrinkage stress of the film itself will be released, and the contact with the metal plate will occur. The face (that is, the side where the plasticizer is distributed) produces a curl toward the inside. If 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 that comes into contact with the metal plate will curl to the inside. In addition, when the hard-coated film is exposed to a humid environment, the shrinkage stress retained by the film itself will be released, and the surface inwardly contacting the metal plate will also curl. Examples of plasticizers used in the manufacture of triethylammonium cellulose film include: 326 \ Patent Specification (Supplement) \ 94-01 \ 93129550 8 200528267 Triphenyl phosphate, diphenyl phosphate, difluorenyl phosphate Ethyl acetate, ethylbenzoic acid ethyl glycolate, etc., which are more polar than triethyl cellulose. In addition, the distribution of the plasticizer is related to the surface energy of the triethylammonium cellulose film. The more plasticizer with a higher polarity, the lower the surface energy. In other words, the plasticizer will be poorly distributed on the surface with the lower surface energy. During the production of triethyl cellulose film, the surface (band face) that touches the metal plate will be poorly distributed with more plasticity. Dose to make surface energy lower. The amount of poor plasticizer distribution can vary with the drying step of the film, the type of solvent used during the preparation of the dopant, and the type of plasticizer. The surface where the plasticizer is distributed more than a certain standard, that is, the surface whose surface energy is below 3 5 m N / m measured according to JISK 6 7 6 8 is usually the surface that contacts the metal plate. The plasticizer will be extremely poorly distributed. . It is conventionally known that if a hard coating layer is provided on the belt surface side, the adhesion between the hard coating layer and the triethyl cellulose film is better. Therefore, a hard coating layer is usually provided on the belt surface, that is, the surface with the lower surface energy. The present inventors have discovered that by providing a hard coat layer on one of the surfaces having a surface energy of 35 m N / m or more on the surface of the triethyl cellulose film, it is possible to suppress the film curl and improve the humidity dependence of the film curl Then, the present invention is completed. Especially in the triethyl cellulose cellulose film with a film thickness as thin as 30 to 6 0 // m, it is best to be provided on one of the sides with a surface energy of 37 mN / m or more (especially 40 mN / m or more). With a hard coating, film curl can be suppressed. In addition, when the surface energy of both sides is above 35 m N / m, a hard coat layer may be provided on either side. In a common triethylammonium cellulose film, the upper surface energy value is 50 mN / m. In addition, if the difference between the inner and outer surface energy is less than 2mN / m, the acetamidine cellulose film can significantly suppress the film curling. 326 \ Patent Specification (Supplement) \ 94-01 \ 93129550 9 200528267 Triethyl cellulose cellulose film can be produced by casting on a rotating metal plate and forming a film as described above, and metal plates generally use metal tape Or metal tube. In order to improve the surface energy of the triethyl cellulose cellulose film, it is an effective way to make the plasticizer uniform in the thickness direction of the film, and because the method made by the roller method will make the plasticizer more uniformly exist, the present invention is the most It is good to use the triethyl cellulose cellulose film prepared by the roller method. The triethyl cellulose cellulose film used as a hard coating film support body of the present invention may vary in size depending on the thickness of the film, but when the film thickness is in the range of 30 to 9 0 // m If the present invention is used, the curl suppression effect will be found. The curl suppression effect will be particularly significant for films with a film thickness as thin as 30 to 60 m. As described above, the hard coat film of the present invention is a hard coat film comprising a triethyl cellulose film as a support, and a hard coat containing a UV-curable resin or a radiation-curable resin is provided on the support. . The UV-curable resin or the radiation-curable resin is mixed with a solvent (dissolved or dispersed) and used as required. The solvents used can be aromatics such as: toluene; alcohols such as methanol, ethanol, isopropanol; methyl cellosolve, ethyl cellosolve, butyl cellosolve, etc. Mix well-known organic solvents and use. Triethylacetin cellulose film has low solvent resistance. To prevent whitening, it is best to use a solvent containing toluene as the main component. In addition, in order to improve performance, as long as the effect of the present invention is not affected, an antifoaming agent, a leveling agent, an antistatic agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a polymerization terminator, and the like may be contained. In addition, in order to impart anti-glare properties to the coating layer, silicon oxide particles or acrylic resins, silicone resins, amino fluorene 10 326 \ Patent Specification (Supplement) \ 94- 01 \ 93129550 200528267 Fine particles such as resin beads such as ester resin, organic or inorganic. The ultraviolet-curable resin or radiation-curable resin used in the present invention is only a transparent resin that can be cured by irradiating electron beams or ultraviolet rays, etc., and the rest is not particularly limited. Ester-based resins, polyester acrylate-based resins, and acrylic epoxy-based resins are appropriately selected. The more preferable one is composed of an ultraviolet-curable polyfunctional acrylate having two or more (fluorenyl) acrylic fluorenyl groups in the molecule. UV-curable polyfunctional acrylates with two or more (fluorenyl) acrylic fluorenyl groups in the molecule. Specific examples include neopentyl glycol di (meth) acrylate and 1,6 hexanediol di (fluorenyl group). ) Acrylate, tris (fluorenyl) trihydroxypropyl acrylate, tetra (fluorenyl) di (trihydroxymethyl) propyl acrylate, pentaerythritol tetra (fluorenyl) acrylate, pentaerythritol tri (fluorenyl) acrylate , Dipentaerythritol hexa (fluorenyl) acrylate, and other polyalcoholic acid; bisphenol A diglycidyl mystery diacrylate, neopentyl glycol diglycidyl ether diacrylate, 1, 6 hexane Glycol diglycidyl ether di (fluorenyl) acrylate and other (fluorenyl) acrylic epoxy esters; polyesters obtained by esterification of polyhydric alcohols and polycarboxylic acids and / or anhydrous substances with acrylic acid (曱Based) acrylic acid esters; by reacting polyols, polyisocyanates, and hydroxyl-containing (fluorenyl) acrylic esters, the amino phosphonate (meth) acrylates, polysiloxane poly (fluorenyl) acrylic acids Ester and so on. The above-mentioned ultraviolet-curable polyfunctional acrylate may be used singly or in combination of two or more kinds. The content is preferably 50 to 95% by weight based on the resin solid content of the coating material for a hard coat layer. In addition, in addition to the above-mentioned polyfunctional (fluorenyl) acrylate, 326 \ Patent Specification (Supplement) \ 94-01 \ 93129550 11 200528267 resin solid content relative to the coating for hard coatings is preferably, preferably Monofunctional acrylates such as 2-hydroxy (fluorenyl) propyl, 2-hydroxypropyl (meth) acrylate, (fluorenyl) glycidyl, and the like in an amount of 10% by weight or less. Furthermore, a polymerizable oligomer may be added to the hard coat layer for the purpose of adjusting the hardness. Examples of such oligomers include: terminal (fluorenyl) propyl poly (fluorenyl) fluorenyl acrylate, terminal styryl poly (meth) acrylate, terminal (meth) acrylate polystyrene, and terminal ( Fluorenyl) propylene polyethylene glycol, terminal (fluorenyl) acrylate-acrylonitrile-styrene copolymerized terminal (meth) acrylate-styrene-methyl methacrylate copolymer type monomer, the content is relative The solid content of the resin in the coating for a hard coat layer is preferably 5 to 50% by weight. The hard coat layer of the present invention is formed by applying a coating composition to a transparent support using a well-known coating device, and then hardening it by irradiating with ionizing radiation. Well-known coating apparatuses can use coating apparatuses such as a micro gravure coater, a gravure coater, a Mayer bar coater, and a gold coater. The viscosity and concentration of the coating composition at the time of coating are adjusted to appropriate values using a coating device used. The thickness of the hard coating after hardening is usually 1 to 20 // m, and preferably 2 to 10 // m. If the film thickness is less than:, the rigidity will be reduced. On the contrary, if it is thicker than 20 // m, the curl will change. [Example] Hereinafter, the present invention will be described in detail in the examples, but the present invention is not limited thereto. In addition, the "parts" and "%" in the examples refer to "parts by weight" and "weight!", Respectively, unless specifically mentioned. For the hard coat films prepared in the examples and comparative examples, 326 \ Patent Specification (Supplements) \ 94-01 \ 93129550 12 enoic acid esters for isoene oil S, etc. The machine and the type can be layer-by-layer; β m is large. Only the first and following 200528267 projects were evaluated. 1) Surface energy The surface energy of the support is measured according to J I S K 6 7 6 8. Table 4 shows the surface energy of the film used as a support in the examples and comparative examples. 2) Transparency of the coating layer The turbidity of the hard coating film was measured using a turbidimeter (manufactured by Murakami Color Research Co., Ltd.) in accordance with JIS K-7105. 3) Adhesiveness The substrate hole test (gap interval 1 mm) was evaluated according to J I S K 5400. The coating layer was not peeled off completely from the base film as "0", the peeling was less than 90% of the entire coating layer was marked as "△", and the coating layer was peeled as 90% or more as "△". "X". 4) Wrong pen hardness It is implemented in accordance with JIS K 5400 using HEID0N 14. 5) Thin film curling cuts the hard-coated film into A 4 size (2 9 · 7 X 2 1 · 0 cm), under normal environment (23 ° C, 50% RH) and in humid environment (30 ° C, 90% RH), and the humidity was measured for 24 hours after humidity conditioning for 24 hours. The average of the 4 corner heights was calculated. Average height Omm ~ 15mm: very good; 15mm ~ 30mm: good; 30mm ~ 50mm: bad; tube shape over 50mm: obviously bad. [Example 1] Using a triethyl cellulose cellulose film (Fuji Photo Soft (Strand Form A) Model A) with a thickness of 80 μm as a support, the surface with a surface energy of 37 mN / m was used.
326\專利說明書(補件)\94-01\93129550 200528267 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UV光，便獲得硬塗 層薄膜。此時的硬塗層厚度為5 // m。針對所獲得硬塗層薄 膜，就塗佈層的透明性、密接性、船筆硬度、薄膜曲捲進 行評估，結果如表5所示。326 \ Patent Specification (Supplement) \ 94-01 \ 93129550 200528267 The coating composition A in Table 1 below was applied with a bar coater, and the diluted solvent was evaporated with a 80 ° C blower, and then irradiated with UV light Then, a hard coat film is obtained. The thickness of the hard coating at this time is 5 // m. For the obtained hard coat film, the transparency, adhesion, boat hardness, and film curl of the coating layer were evaluated. 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 - 1 7 0 0 B、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 . 0 5重量份 [實施例2 ] 除以厚度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，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8 0 // m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41 mN/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 200528267 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4 ] 除以厚度8 0 // m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40mN/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5 ] 除以厚度80//m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37mN/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6 ] 除以厚度4 0 // m的三乙醯纖維素薄膜（富士照片軟膠（股） 製型D)為支撐體，並在其表面能量40mN/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7 ] 除塗佈著表2所示塗料組成物B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。 15 326\專利說明書(補件)\94·01\93129550 200528267Table 1: Coating composition A UV-curable resin (trade name ·· UV-17 0 0 B, manufactured by Yumoto Synthetic Chemical Co., Ltd.) 9 5.0 parts by weight of an initiator (trade name: Yier Jiaqiu 1 8 4. Manufactured by Ciba-Geigy) 5. 0 parts by weight of toluene 2 0 0 0 parts by weight of isopropanol 5 0 0 parts by weight of a fluorine-based surfactant (trade name: Megawak F-1 7 7 、 Da Yueben Ink (made by stock)) 0.5 parts by weight of the liquid [Example 2] divided by a thickness of 8 0 // m of triethylammonium cellulose film (Fuji Photo Soft Rubber (stock) Form A) It is a support, and the surface of the surface with a surface energy of 39 mN / m is coated with the coating composition A, and the rest are made in the same manner as in Example 1. A hard coating film is prepared for the transparency and adhesion of the coating layer. , Pencil hardness, and film curl. The results are shown in Table 5. [Example 3] A triethylcellulose cellulose film (Fuji Photo Soft Rubber (Strand Form B) Model B) with a thickness of 80 / m is used as a support, and the surface energy is 41 mN / m. Except that the coating composition A is coated, the rest are the same as in Example 1. 14 326 \ Patent Specification (Supplement) \ 94-01 \ 93129550 200528267 layer film is prepared. For the transparency, adhesion, The pencil hardness and film curl were evaluated. The results are shown in Table 5. [Example 4] Divided by a thickness of 8 0 // m of triethylammonium cellulose film (Fuji photograph soft rubber (strand) type B) as a support, and on the side with a surface energy of 40 mN / m, Except that the coating composition A was coated, the rest were made as in Example 1 to produce a hard coat film. The transparency, adhesion, pencil hardness, and film curl of the coating layer were evaluated. The results are shown in Table 5. [Example 5] A triethylammonium cellulose film (Konica (C) type C) having a thickness of 80 // m was divided as a support, and the surface having a surface energy of 37 mN / m was applied. Except for coating composition A, the rest was produced in the same manner as in Example 1. A coating layer was evaluated for transparency, adhesion, pencil hardness, and film curl. The results are shown in Table 5. [Example 6] Divided by a triethyl cellulose cellulose film (Fuji photograph soft rubber (strand) model D) with a thickness of 40 / m, as a support, and on the side with a surface energy of 40 mN / m, Except that the coating composition A was coated, the rest were made as in Example 1 to produce a hard coat film. The transparency, adhesion, pencil hardness, and film curl of the coating layer were evaluated. The results are shown in Table 5. [Example 7] Except that the coating composition B shown in Table 2 was applied, a hard coat film was produced in the same manner as in Example 1. The transparency, adhesion, pencil hardness, and film curl of the coating layer were measured. The results are shown in Table 5. 15 326 \ Patent Specification (Supplement) \ 94 · 01 \ 93129550 200528267
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 B、曰本 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 曱苯 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：BYK- 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//m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//m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)\94-01\93129550 200528267 除以厚度8 0 // m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 使用硬化收縮較小樹脂的下述表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, UV-curable resin (trade name: UV-1 700 0 B, manufactured by Yumoto Synthetic Chemical Co., Ltd.) 9 2. 5 parts by weight of Celestia 4 3 0 (Fuji Silesia The company has an average particle diameter of 4.0 // m 2.5 parts by weight of the starter (trade name: Yier Jiaqi 1 8 4. Made by Ciba Jiaji) 5. 0 parts by weight of toluene 0 parts by weight of isopropanol 5 0. 0 parts by weight of a siloxane-based surfactant (trade name: BYK- 3 2 5; manufactured by BYK Chemical Co.) 0.5 0 parts by weight of the liquid [Comparative Example 1] divided by 80 // m triethyl cellulose cellulose film (Konica Co., Ltd. type C) is a support, and the surface energy of 34 mN / m is coated with a coating composition other than The rest are made in the same manner as in Example 1. The coating layer was evaluated for transparency, adhesion, pencil hardness, and film curl. 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 // m was divided as a support, and a surface having a surface energy of 48 mN / m was coated on the surface. Except for the coating composition A, the rest were made as in Example 1 to evaluate the transparency, adhesion, pencil hardness, and film curl of the coating layer. The results are shown in Table 5. [Comparative Example 3] 16 326 \ Patent Specification (Supplement) \ 94-01 \ 93129550 200528267 Divided by a thickness of 8 0 // m of triethylammonium cellulose film (Konica (stock) type C) as a support , And the surface energy of 34 mN / m is coated with the coating composition C of the following Table 3 using a resin with a smaller hardening shrinkage, and the rest are made as in Example 1 to produce a hard coating film. The transparency, adhesion, pencil hardness, and film curl of the coating layer 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 甲苯 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 A4300(雙面易黏著處理） 48 48 一 17 326\專利說明書(補件)\94-01\93129550 200528267 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3 4 m N / 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\專利說明書(補件)\94-01\93129550 200528267 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，可提供當以三乙酿 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 an initiator (trade name ·· Irjiaqiu 184, Ciba Jiaji) (Manufactured by the company) 5. 0 parts by weight of toluene 200. 0 parts by weight of isopropanol 50. 0 parts by weight of a fluorine-based surfactant (trade name: Mika Wake F-177, made by Daiichi Ink (stock) Co., Ltd.) 0.05 Table 4 parts by weight Surface energy (mN / m) Surface energy (mN / m) Metal plate type during film making Fuji Photo Soft (strand) molding A 39 37 Metal band Fuji Photo soft (strand) molding B 41 40 Metal tube Konica (stock) molding C 37 34 Metal belt Fuji Photo soft rubber (stock) molding D 40 39 Metal belt A4300 (double-sided easy-adhesion treatment) 48 48 one 17 326 \ Patent specification (Supplement Pieces) \ 94-01 \ 93129550 200528267 Table 5 Turbidity (%) Adhesive Surface Hardness Film Curly 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 implementation Example 3 0.2 〇2H Very good Very good Example 4 0.2 〇2H Very good Good Very Good Example 5 0 · 1 〇2H Very Good Very Good Very 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 Bad Obviously Bad Comparative Example 2 0.5 〇2H Good Good Comparative Example 3 0.2 〇Η Very good Obviously bad As shown in Table 5, the hard coating layer was provided on the side of the triacetam cellulose film as a support at a surface energy of 3 5 m N / m or more. The hard-coated films of Examples 1 to 7 on the surface significantly suppress the curling of the film, and there is no problem in adhesion and surface hardness. Although Example 7 was formulated with silica as a pigment to impart anti-glare properties to the hard coat film, there were no problems with adhesion and surface hardness as in Examples 1 to 6. On the other hand, the hard coat film of Comparative Example 1 in which the hard coat layer was provided on a side with a surface energy of less than 35 m N / m was unable to sufficiently suppress film curling. In addition, in Comparative Example 3 in which a hard coating layer was provided on the surface with a surface energy of 34 m N / m and a resin with a smaller hardening shrinkage was used, it was confirmed that the surface hardness was lowered, and a film curl was confirmed in a general environment. Suppression effect, but film humidification suppression effect cannot be obtained in a humid environment. In addition, the hard-coated film of Comparative Example 2 using a polyester film as a support was found in a triethyl cellulose film, and the humidity of the film-free curl was 18 326 \ Patent Specification (Supplement) \ 94 -01 \ 93129550 200528267 It does not matter about adhesion and surface hardness (inventive effect) According to the present invention, it is possible to provide a moisture-dependent suppression of film curvature when a hard coating is formed with triethyl alcohol. 19, and excellent transparency or surface hardness. Cellulose films are hard-coated films that support rolls and improve film curl. 326 \ Patent Specification (Supplement) \ 94-01 \ 93129550