201249652 六、發明說明： 【發明所屬之技術領域】 本發明的一種方式涉及做為圖像顯示裝置等的保|蔓膜 使用的光學用硬塗層膜（hard coat film )。 【先前技術】 要求液晶顯示器、有機電致發光顯示器等圖像顯示梦 置的圖像顯示面具有耐損傷性’使得在使用時圖像顯示面 不會被損傷。因此，有時在圖像顯示面上黏貼表面具有硬 塗層的基膜（硬塗層膜）。由此，可以提高圖像顯示裝置的 圖像顯示面的耐損傷性。 I叹芍隹签朕的衣囱上形成硬 法。例如 一 工，曰；谷種方 ……種方法是在基膜表面上塗布含有熱固性樹脂 或紫外線固化性樹脂等光聚合性樹脂的塗布劑，並使塗布 劑固化。由此形成由包含更硬樹脂的塗膜構成的硬塗層。 例，，在專利文獻】公開的方法中，在基膜表面上^ 此後，通過使塗布的聚魏_統，形成做為 f塗層的魏_。在翻讀2公_方法中，在基膜 ==咖化性樹脂等樹脂，該紫外線固化性樹 膠體二氧切等錄。由此形成更硬 tZll 關於專利文獻！ 公開公報特開·2 —67238號 成的硬塗層的本身有足“化的氧化石夕膜構 題是：如果上述硬塗 二-疋，該方法存在的問 關於上述的問題^了㈣的錯筆硬度。 舄了鈇问釓筆硬度，可以考慮簡單 201249652 地使上述硬塗層變厚。如果硬塗層變厚，則確實可以提高 錯筆硬度。但是在該情況下’存在硬塗層易產生裂紋或硬 塗層本身易剝離的問題。 如果使硬塗層變厚，則也會損害積層膜整體的柔性 (flexible)。此外也存在當積層膜彎曲時，硬塗層產生裂紋 或產生層間剝離的問題。 如上所述，專利文獻2公開的方法是通過使用含有做 為填充劑的賴二氧化料微粒_脂，形成更硬的硬塗 層的方法。可是，在該方法中，由於含有填充劑，所以硬 塗層的透明性下降。其結果，產生如下的問題，即：在把 上述的硬塗層做為光學用途的硬塗層膜黏貼在圖像顯示裝 置的顯示面上的情沉下，會損害顯示面的透明性。 " 【發明内容】 、馨於上述問題’本發明一個方式的目的是提供一種硬 塗層膜’該硬塗層膜具有姆硬度爲5H以上的高硬度的表 面’具有優㈣耐損傷性和耐磨損性，並具有優良的柔性 和透明性，此外特別適合用作光學用膜。 爲了實現上述目的’本發明的方式i提供一種硬塗 :括做為基體材料的塑膠膜以及硬塗層，該硬塗層 j邊在上述轉膜的—個面上，上述塑膠膜是丙烯酸: ’械上述硬塗層㈣脂含有有機-無機雜化樹脂 该有機-無機雜化樹脂含有IU化合物的添加劑。 ^發明的方式2的硬塗層膜是方式丨的硬塗層膜，j =丙烯酸系樹脂膜是由以聚甲基丙烯酸甲g旨爲主要万 刀的樹脂製成的。 本發明的方式3的硬塗層膜是上述方式1或上述方式2 4/16 201249652 膜’並且形成上述硬塗層的樹 上5重量如下的上述氟系化合物。 有 $明的方式4的硬塗層膜是上述方式】至上述方式3 二曰。，—種硬塗輕’並且形成上述硬塗層的樹脂含有20 重以上8〇重量％町的二氧化石夕。 ^ f㈣的方式5的硬塗層膜是上述方式1至上述方式4 種硬塗層膜，並且上述硬塗層的厚度爲_以上 i為5ϋμηι以下。 為其雕好^方式！的硬塗層膜’使用丙烯酸系樹脂膜做 : = 塑膠膜。此外’形成硬塗層的樹脂含有有機_ 热機雜化樹脂。因此，由於其 '基胰和硬塗層的黏附性良好， 續以在一的介面產生剝 膜具有優良的柔性。此外，卜、十上述硬塗層 性、述更主層膜具有優良的透明 優㈣耐損傷性和優良的耐磨損性。 樹脂中含有氟“合物的添加劑。=機雜化 f曲時，在硬塗層中也難以產生裂紋。即 =良的柔性。此外’利簡系化合物提高硬 光滑性。由於硬塗層的表面變得滑溜，所以難以 t其結果，上述硬塗層膜具有優良的耐損傷性和_損 【實施方式】 [具體實施方式] 對本實施方式的硬塗層膜（本硬 本硬塗層膜包括做綱材料的塑；膜和=兒明。 塗層層疊在塑膠膜的單面或雙面上。胺更士層。硬 土縢軔是丙烯酸系樹 5/16 201249652 月曰膜。硬塗層含有有機·無機雜脂， 脂含有㈣化合_添加劑。 錢錢雜化Μ 材料本硬塗層膜使用丙稀酸系樹脂膜做為基體 °丙稀酸系樹脂膜是表面硬度優良並兼具透 =膜:=柔軟性的基膜。因此，較佳係使用丙嶋 為本硬塗層膜的基體材料。由此，可以很好地把 本更么層犋例如做為光學用膜使用。 以下，里較，塑膠膜的厚度爲5一以上且爲25_ 身㈣二ΐ膠？的厚度小於5〇μΠ1，則得到的硬塗層膜本 、、\有可能出現問題。如果上述厚度大於25〇哗， 則硬塗層膜本身㈣性、透明性有可能出現問題。 做為丙稀酸系樹脂膜，例如可以使用聚甲基丙稀酸甲 1^1嫩）膜。此外，也可以使用僅由聚丙_垸基醋 树月曰匕衣成的触及由以聚f基丙烯酸絲§旨爲基本成分的 =製成的膜。該由以聚甲基丙烯酸絲_爲基本成分的 ^月:衣成的膜可以是在由聚曱基丙稀酸烧編旨製成的硬質 树月曰中含有由共聚物橡膠成分、共輛二烯系聚合物橡膠、 烧製成的軟質樹脂而S成賴。通過含有軟質樹脂 可j k问膜的木权性和韋刃性。此外，也可以使用由通過把 不έ橡膠成刀的I丙烯酸垸基醋樹脂和其他高分子樹脂合 金化形成的樹脂製成的膜。 在，硬塗層膜中，使用以ΡΜΜΑ樹脂爲主要成分的聚 曱，丙稀酸甲g旨臈做為轉膜。其原因是：pMMA樹脂具 有局的透明度’並且輕而強物；以及pMMA樹脂是無色透 明的’具有比麵更好的透光率，並具有優㈣耐候性、 而才水性和耐衝擊性。 6/16 201249652 下面對本硬塗層膜中的硬塗層進行說明。 本硬塗層膜的硬塗層是含有氟系化合物的有機-無機雜 化樹脂。 a 較佳係上述有機-無機雜化樹脂例如是紫外線固化性樹 脂，在該紫外線固化性樹脂中分散有在表面導入了光聚1 反應性官能團的二氧化矽（silica)超細顆粒。較佳係1述 超細顆粒實際上均勻分散在紫外線固化性樹脂中。 a 做為光聚合反應性官能團，可以使用以（甲基）丙烯 醯氧基爲代表的聚合性不飽和基團等。做為紫 料 樹脂例如可以使用紫外線固化型丙烯酸系樹脂、紫外線固 化型丙烯酸聚氨賴樹脂、紫外線固化型聚㈣烯酸酉旨系 樹脂、紫外線1U化型環氧丙稀gu旨系樹脂、紫外線固化型 多元醇丙馳料樹脂或紫外線固化型環氧樹脂等。紫外 線固化性樹脂靴於上述賴脂，可㈣當選擇使用合適 的樹脂。在此，關於紫外_化讀脂省略了除上述二 以外的更多的描述。 分散在紫外線固化性樹脂中的二氧化石夕超細顆粒的平 均粒徑較佳為_〗〜()>。通過使用具有上述範圍的平 均粒徑的超細難’可以得到透明料光學特性和硬塗層 性能優良的硬塗層。此外，射更容易獲得上述效果，^ 佳係使用具有〇·_〜__的平触㈣超細顆粒。 同樣，爲了提高透明性等光學特性和硬塗層性能，較 超細雜相對於形成硬㈣的樹脂整體的 二二;^ %以上且爲⑽重量％以下。該範圍為較佳的 原因在於.在二氧切超細難的含量小於20重量％的情 況下’不能使表面的強度足夠高，如果二氧切超細顆粒 7/16 201249652 的含量大於8G重量％，則塗縣面不翻且不光滑。 明。在有機1 無機雜化樹脂中的氟系化合物進行說 二、:° ’上述㈣化合侧如是具有碳-碳雙鍵的 含全氟聚驗的化合物。 可 Μ通ΐΐί述氟系化合物添加到前述的有機無機雜化樹 月曰中’1成用於形成硬朗的樹脂。通過使用該樹脂，一 以使射相表面具有防污性，_是具有優㈣防止指 紋附者馳能。此外，硬塗層的表面成爲具核水拒油性 性 的低摩擦表©。而且層具有更高的錄性和優良的柔 乱系化合物的加入量相對於有機·無機雜化樹脂和氟系 化的總重量’在用去除溶劑後的有效成分比率表示的 ^兄Υ 丁乂仏為重以上且爲5.G重量％以下。該範 圍為知佳的原因在於：在氟系化合物的加人量小於W重量 /6的；^得到硬塗層膜的勃性，如果㈣化合物 的力入里大$、5.G重，則不能得到具有足夠高硬度的塗 本?塗層膜的硬塗層按以下方式形成。即，把前述的 添加了 H合物的有機_域雜化樹脂，塗布在做為基體 材^的__表面上。接著，通舰射紫外線等使上述 樹脂層固化。由此形成硬塗層。此時，在硬塗層中，通過 照射紫外線使紫外_化性樹脂成分與二氧㈣超細顆粒 的光聚合反躲官能團發生聚合反應。減，二氧化石夕超 細顆板通過化學__勻分散在有祕體巾的網狀的交 聯即’在硬塗層表面上形成與交麵牢固結合的氣系 化合物的膜。 8/16 201249652 在硬塗層的膜厚小於ιμ1Ώ的情況下，不能使表面的硬 度足夠高。另一方面，在硬塗層的膜厚大於50μιη的情況 下，硬塗層的柔性降低。因此，硬塗層的平均膜厚較佳為 1 μηι以上且爲5〇pm以下。爲了得到該範圍的膜厚，妥當的 是使在塑膠膜上塗布後的樹脂的骐厚（濕膜厚）大約爲2 〜ΙΟΟμηι。 做為在塑膠膜（基膜）的表面上層疊樹脂的方法（即 塗布樹脂的方法）’例如可以使用凹印塗布法、棒塗布法、 刀塗布法、輥塗布法、刮板塗布法 '模具塗布法等。在本 硬塗層膜的製造中，只要適當選擇使用合適的方法即可。 一此外，做為用於使紫外線固化性樹脂光聚合的紫外線 的光源，例如可以使用低壓水銀燈、中壓水銀燈、高壓水 銀燈、— 超高壓水銀燈、碳弧燈、金屬化物燈、氣氣燈等。 但本硬塗層膜 下麵對本硬塗層膜的實施例進行說明 不限於上述的實施例。 〈貫施例1〉 百先’準備了在形成實施例1的硬塗層膜的硬塗 所使用的實施例〗的樹脂（塗料）。該實施例1的塗料丄有 下面的配比組成。 在該實施例1的塗料中配入有：1〇〇重 機雜化型的硬塗層组合物（腿股份有限公⑽，、丁 ^ =的=:罐的固體成分的溶液)，該有機-無機 雜化i的射輕合物是通聽導人了絲合反應性 團的二氧切超细獅配人丙烯酸㈣ ^ 為添加劑物重量份的氣系化合物(大金工業=二 9/16 201249652 司製’ OPTOOL DAC-HP ’含有20重量％的氟系化合物 成分的溶液）’·以及做為稀釋溶劑的6.4重量份的甲乙綱 實施例1的硬塗層膜的塑料膜是厚度為125μιη的聚甲 基丙細酸曱酉旨膜（住友化学股份有限公司製，丁沈匕加此 S001G)。通過棒塗布法在該塑膠膜的一個面上塗布了實= 例1的塗料’使得固化後的膜厚爲15μπι。溶劑乾燥後 氣吹掃下利用尚壓水銀燈照射440mJ/cm2的紫外線，使淹 膜固化。這樣製作了實施例1的硬塗層膜。 〈實施例2〉 接著’準備了在形成實施例2的硬塗層膜的硬塗層中 使用的實施例2的樹脂（塗料）。該實施例2的塗料具有如 下的配比組成。 在該實施例2的塗料中配入有：1〇.〇重量份的機無-機 雜化型的硬塗層组合物（Momentive Performance Materials Japan共同會社製造’UVHC7000，含有32重量％的固體成 分的溶液h該有機-無機雜化型的硬塗層组合物是通過將導 入了光聚合反應性官能團的二氧化矽超细顆粒配入丙稀酸 系樹脂中而制成的；做為添加劑的0.3重量份的氟^系化合物 (DIC股份有限公司製造，Megaface RS —75，含有4〇重 量％的氟系化合物成分的溶液）；以及做為稀釋溶劑的0.7 重量份的甲乙嗣。 實施例2的硬塗層膜的塑料膜是與實施例1相同的厚 度為125μηι的聚曱基丙烯酸甲酯膜（住友化学股份有限公 司製，Technolloy S001G)。通過棒塗布法在該膜的一個面 上塗布了實施例2的塗料，使得固化後的膜厚爲15jLim。溶 劑乾燥後，在氮氣吹掃下利用高壓水銀燈照射440mJ/cm2 10/16 201249652 的紫外線，使塗膜固化。這樣製作了實施例2的硬塗層膜。 〈比較例1〉 爲了進行比較’製作了比較例1的硬塗層膜。在比較 例1的硬塗層膜和實施例1的硬塗層膜中，做為基體材料 使用的塑膠膜不同。在比較例1的硬塗層膜中，做為基體 材料的塑膠膜使用厚度爲125μιη的雙軸拉伸聚對苯二曱酸 • 乙二酯膜。 與實施例1相同，在製作比較例1的硬塗層膜過程中， 把實施例1的塗料塗布在厚度爲125μηι的雙軸拉伸聚對笨 二曱酸乙二酯膜的一個面上。溶劑乾燥後，使塗膜固化。 這樣製作了比較例1的硬塗層膜。 〈比較例2 > 此外，爲了進行比較，製作了比較例2的硬塗層膜。 在比較例2的硬塗層膜和實施例1的硬塗層膜中，用於形 成硬塗層的塗料不同。與實施例1的塗料不同，在比較例2 的塗料中沒有添加It系化合物。 即，比較例2的塗料具有如下的配比组成。在比较例2 的塗料中配入有：10.0重量份的有機-無機雜化型的硬塗層 组合物（JSR股份有限公司製造，OPSTER KZ6445，含有 50重量％的固體成分的溶液），該有機-無機雜化型的硬塗 層组合物是通過將導入了光聚合反應性官能團的二氧化石夕 超细顆粒配入丙稀酸系樹脂中而制成的；以及6.7重量份的 做為稀釋溶劑的曱乙酮。 與實施例1相同，比较例2的硬塗層膜的塑料膜是厚 度為125μπι的聚曱基丙烯酸曱酯膜（住友化学股份有限公 司製，Technolloy S001G)。在與上述實施例1相同的條件 Π / 16 201249652 下’把比較例2的塗料塗布在上述塑膠膜的一個面上後， 使塗料乾燥和固化，從而製作成比較例2的硬塗層膜。 對上述實施例1、實施例2、比較例1和比較例2四種 硬塗層膜㈣筆硬度和$性輯了職。其評價結果與硬 塗層膜的試樣内容—起表示在表1中。此外，按如下上述 的内容實施了上述的評價。 按JIS K5600- 5 ~~4標準進行了錯筆硬度的評價。進行 了所謂的劃痕試驗，即：把硬度不同的多根辟以45。的角 硬塗層膜的試樣表面上，此後對鉛筆施加負荷來劃 、面然後把不使表面產生傷痕的最硬的錯筆的硬度 做為該試樣的鉛筆硬度。 =IS K5_ — 5〜丨標準，使用圓筒形芯棒（_制） 生^價。使用的芯棒的直徑爲32mm。把各硬塗 。上曲後’觀察了試樣上有無裂紋或剝離。在硬 紋或剝離的評價爲χ。 ，、座生衣201249652 VI. Description of the Invention: [Technical Field of the Invention] One aspect of the present invention relates to an optical hard coat film used as an optical film for an image display device or the like. [Prior Art] An image display surface of an image display dream such as a liquid crystal display or an organic electroluminescence display is required to have damage resistance so that the image display surface is not damaged during use. Therefore, a base film (hard coat film) having a hard coat layer on the surface is sometimes adhered to the image display surface. Thereby, the damage resistance of the image display surface of the image display device can be improved. I sighed and formed a hard method on the chimney of the sign. For example, a coating method of a photopolymerizable resin such as a thermosetting resin or an ultraviolet curable resin is applied to the surface of the base film, and the coating agent is cured. Thus, a hard coat layer composed of a coating film containing a harder resin is formed. For example, in the method disclosed in the patent document, on the surface of the base film, by applying the coated poly-wei, it is formed as a coating of f. In the method of reading 2 _ in the method, a resin such as a base film == a curable resin, the ultraviolet curable resin colloidal dioxotomy or the like is recorded. This creates a harder tZll about the patent literature! The hard coat layer of the Japanese Laid-Open Patent Publication No. 2-67238 has a sufficient "oxidized oxidized stone structure": if the above-mentioned hard-coated di-ruthenium, the method exists, the above-mentioned problem is solved (4). Wrong pen hardness. 舄 鈇 鈇 釓 硬度 硬度 硬度 硬度 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 It is easy to cause cracks or the problem that the hard coat layer itself is easily peeled off. If the hard coat layer is thickened, the overall flexibility of the laminated film is also impaired. In addition, when the laminated film is bent, the hard coat layer is cracked or generated. The problem of the peeling between the layers. As described above, the method disclosed in Patent Document 2 is a method of forming a harder hard coat layer by using the ruthenium oxide fine particles as a filler. However, in this method, Since the filler is contained, the transparency of the hard coat layer is lowered. As a result, there is a problem that the hard coat film which is used for the optical coating described above is adhered to the display surface of the image display device. When it sinks, the transparency of the display surface is impaired. < SUMMARY OF THE INVENTION The object of one aspect of the present invention is to provide a hard coat film having a high hardness of 5H or more. The surface of the hardness has excellent (four) scratch resistance and abrasion resistance, and has excellent flexibility and transparency, and is particularly suitable for use as a film for optics. To achieve the above object, the method of the present invention provides a hard coat: a plastic film as a base material and a hard coat layer on the side of the transfer film, the plastic film is acrylic: 'The above hard coat layer (4) grease contains an organic-inorganic hybrid resin. The organic-inorganic hybrid resin contains an additive of the IU compound. The hard coat film of the second aspect of the invention is a hard coat film of the form, and the j=acrylic resin film is mainly composed of polymethyl methacrylate The hard coat film of the third aspect of the present invention is the film of the above-mentioned aspect 1 or the above-mentioned form 2 4/16 201249652 and the fluorine-based compound having the following weight of 5 on the tree forming the hard coat layer. $明的方式The hard coat film of 4 is in the above manner to the above-mentioned mode 3, the hard coat is light and the resin forming the hard coat layer contains 20 or more 8% by weight of the oxidized stone of the town. ^ f (d) The hard coat film of the fifth embodiment is the hard coat film of the above aspect 1 to the above-described form, and the thickness of the hard coat layer is _ or more i is 5 ϋ μηι or less. The acrylic resin film is made of: = plastic film. In addition, the resin that forms the hard coat layer contains organic _ heat machine hybrid resin. Therefore, due to its good adhesion of the base pancreas and hard coat layer, it continues to be produced in one interface. The film peeling film has excellent flexibility. In addition, the above-mentioned hard coat layer and the above-mentioned main layer film have excellent transparency and excellent scratch resistance and excellent wear resistance. The resin contains an additive of a fluorine compound. When the machine is hybridized, it is difficult to generate cracks in the hard coat layer. That is, it is good in flexibility. In addition, the 'simplified compound improves hardness and smoothness. The surface becomes slippery, so that it is difficult to achieve the above, and the hard coat film has excellent damage resistance and damage. [Embodiment] The hard coat film of the present embodiment (the present hard coat film) Included as the material of the material; film and = ming. The coating is laminated on one or both sides of the plastic film. Amines layer. Hard soil is acrylic tree 5/16 201249652 曰 film. Hard coating The layer contains organic and inorganic impurities, and the fat contains (4) compound_additive. Qian Qian hybrid Μ material The hard coat film uses acrylic resin film as the base. The acrylic resin film is excellent in surface hardness and has both Translucent film: = a flexible base film. Therefore, it is preferable to use B-based as the base material of the hard coat film, whereby the layer can be preferably used as an optical film. In the following, the thickness of the plastic film is 5 or more and 25_ body (four) two If the thickness is less than 5 〇μΠ1, the obtained hard coat film may be defective. If the thickness is more than 25 Å, the hard coat film itself may have problems in transparency and transparency. As the acrylic resin film, for example, a polymethyl methacrylate film can be used. Further, it is also possible to use a polyf-based acrylic acid. § § _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The sapling contains a copolymer rubber component, a total of a diene-based polymer rubber, and a soft resin obtained by baking, and the resin is made of S. The softness of the film can be used to determine the wood weight and the edge of the film. It is also possible to use a film made of a resin formed by alloying a non-rubber rubber-forming yttrium ruthenium vinegar resin with another polymer resin. In the hard coat film, a ruthenium-based polymer is used as a main component.曱, acrylic acid a g 臈 臈 as a transfer film. The reason is: pMMA tree Has a bureaucratic transparency 'and is light and strong; and pMMA resin is colorless and transparent' with better light transmittance than the surface, and has excellent (four) weather resistance, water and impact resistance. 6/16 201249652 The hard coat layer in the hard coat film is described. The hard coat layer of the hard coat film is an organic-inorganic hybrid resin containing a fluorine compound. a. Preferably, the above organic-inorganic hybrid resin is, for example, ultraviolet curable. In the resin, in the ultraviolet curable resin, silica ultrafine particles having a photopolymerizable functional group introduced on the surface thereof are dispersed. Preferably, the ultrafine particles are actually uniformly dispersed in the ultraviolet curable resin. a. As the photopolymerizable functional group, a polymerizable unsaturated group represented by a (meth) propylene decyloxy group or the like can be used. For the violet resin, for example, an ultraviolet curable acrylic resin, an ultraviolet curable acrylic polyurethane resin, an ultraviolet curable poly(tetra)enoic acid resin, an ultraviolet ray-based epoxy acryl resin, and an ultraviolet ray can be used. Curable polyol propylene resin or UV curable epoxy resin. UV curable resin boots are used in the above-mentioned lyophilized fat, and (4) when a suitable resin is selected. Here, more descriptions than the above two are omitted regarding the ultraviolet-chemical read grease. The average particle diameter of the ultrafine silica particles dispersed in the ultraviolet curable resin is preferably _ _ ~ () >. A hard coat layer excellent in optical properties of the transparent material and excellent in hard coat properties can be obtained by using an ultrafine particle having an average particle diameter in the above range. In addition, it is easier to obtain the above effects by shooting, and it is preferable to use a flat touch (four) ultrafine particles having 〇·_~__. Similarly, in order to improve the optical properties such as transparency and the performance of the hard coat layer, it is more than 2% by weight and more than (10) by weight or less with respect to the entire resin forming the hard (tetra). The reason why the range is preferable is that the surface strength cannot be made sufficiently high in the case where the content of the ultra-fine dioxo is less than 20% by weight, if the content of the dioxy-cut ultrafine particles 7/16 201249652 is more than 8 G weight. %, the county is not turned over and is not smooth. Bright. The fluorine-based compound in the organic-inorganic hybrid resin is described as follows: °' The above-mentioned (iv) compound side is a perfluoro-containing compound having a carbon-carbon double bond. It is possible to add a fluorine-based compound to the above-mentioned organic-inorganic hybrid tree, which is used to form a tough resin. By using the resin, the surface of the phase is made to have antifouling properties, and _ is excellent (4) to prevent the fingerprint from being attached. In addition, the surface of the hard coat layer becomes a low friction watch with nuclear water repellency. Moreover, the layer has higher visibility and the addition amount of the excellent flexible compound relative to the total weight of the organic-inorganic hybrid resin and the fluorine-based compound is expressed by the ratio of the active ingredient after removing the solvent.仏 is more than the weight and is 5. G weight% or less. The reason why the range is well known is that the addition amount of the fluorine-based compound is less than W weight/6; and the boring property of the hard coating film is obtained. If the force of the (4) compound is as large as $, 5.G, it cannot be A hard coat layer having a coating film having a sufficiently high hardness is obtained in the following manner. Namely, the above-mentioned organic-domain hybrid resin to which the H compound is added is applied onto the surface of the __ as a base material. Next, the resin layer is cured by ultraviolet rays or the like. A hard coat layer is thus formed. At this time, in the hard coat layer, the ultraviolet-polymerizable resin component is polymerized with the photopolymerization anti-doping functional group of the dioxane (tetra) ultrafine particles by irradiation of ultraviolet rays. The film of the gas-based compound which is firmly bonded to the interface on the surface of the hard coat layer is formed by chemically __ uniformly dispersed in a network of the secret tissue. 8/16 201249652 In the case where the film thickness of the hard coat layer is less than ιμ1Ώ, the hardness of the surface cannot be made sufficiently high. On the other hand, in the case where the film thickness of the hard coat layer is more than 50 μm, the flexibility of the hard coat layer is lowered. Therefore, the average film thickness of the hard coat layer is preferably 1 μη or more and 5 μm or less. In order to obtain a film thickness in this range, it is appropriate that the thickness (wet film thickness) of the resin coated on the plastic film is about 2 to ΙΟΟμηι. As a method of laminating a resin on the surface of a plastic film (base film) (that is, a method of coating a resin) 'for example, a gravure coating method, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a mold can be used. Coating method, etc. In the production of the hard coat film, a suitable method can be appropriately selected. In addition, as a light source for ultraviolet light for photopolymerizing an ultraviolet curable resin, for example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metallized lamp, a gas lamp, or the like can be used. However, the present embodiment of the present hard coat film is not limited to the above embodiment. <Example 1> The resin (coating material) of the Example used in the hard coating of the hard coat film of Example 1 was prepared. The coating material of this Example 1 had the following composition. In the coating material of the first embodiment, a 1 〇〇 heavy machine hybrid type hard coat composition (a leg stock limited (10), a butyl ^ = =: a solid solution of a can) is incorporated. The inorganic light-emitting i-light-emitting compound is a gas-based compound which is a component of the additive weight fraction of the dioxate ultrafine lion with human silky reactive group (4) ^Dajin Industry=2 9/16 201249652 "OPTOOL DAC-HP" solution containing 20% by weight of a fluorine-based compound component) and a plastic film of 6.4 parts by weight of the hard coat film of Example 1 as a diluent solvent, having a thickness of 125 μm Polymethyl propyl phthalate film (manufactured by Sumitomo Chemical Co., Ltd., Ding Shen 匕 plus this S001G). The coating material of Example 1 was applied to one surface of the plastic film by a bar coating method so that the film thickness after curing was 15 μm. After the solvent was dried, ultraviolet rays of 440 mJ/cm2 were irradiated with a mercury lamp under a gas purge to cure the flooded film. Thus, the hard coat film of Example 1 was produced. <Example 2> Next, the resin (coating material) of Example 2 used in forming the hard coat layer of the hard coat film of Example 2 was prepared. The coating of this Example 2 had the following composition. In the coating material of the second embodiment, a machine-free-machine hybrid type hard coat composition (manufactured by Momentive Performance Materials Japan, 'UVHC7000, containing 32% by weight of solid content) was blended. Solution h The organic-inorganic hybrid hard coat composition is prepared by incorporating cerium oxide ultrafine particles into which a photopolymerizable reactive functional group has been introduced into an acrylic resin; as an additive 0.3 parts by weight of a fluorine-based compound (manufactured by DIC Co., Ltd., Megaface RS-75, a solution containing 4% by weight of a fluorine-based compound component); and 0.7 parts by weight of methyl ethyl hydrazine as a diluent solvent. The plastic film of the hard coat film was a polymethyl methacrylate film (Technolloy S001G, manufactured by Sumitomo Chemical Co., Ltd.) having the same thickness as 125 μm as in Example 1. It was coated on one side of the film by a bar coating method. The coating of Example 2 was used so that the film thickness after curing was 15 jLim. After the solvent was dried, ultraviolet rays of 440 mJ/cm 2 10/16 201249652 were irradiated with a high pressure mercury lamp under a nitrogen purge to cure the coating film. The hard coat film of Example 2 was produced in this manner. <Comparative Example 1> The hard coat film of Comparative Example 1 was produced for comparison. The hard coat film of Comparative Example 1 and the hard coat film of Example 1 were produced. The plastic film used as the base material is different. In the hard coat film of Comparative Example 1, the plastic film used as the base material is a biaxially stretched polyethylene terephthalate/ethylene diester film having a thickness of 125 μm. In the same manner as in Example 1, in the process of producing the hard coat film of Comparative Example 1, the coating material of Example 1 was coated on one side of a biaxially oriented polyethylene tert-butyl phthalate film having a thickness of 125 μm. After the solvent was dried, the coating film was cured. Thus, the hard coat film of Comparative Example 1 was produced. <Comparative Example 2 > Further, for comparison, a hard coat film of Comparative Example 2 was produced. The hard coat film and the hard coat film of Example 1 were different in the coating for forming the hard coat layer. Unlike the paint of Example 1, the It-based compound was not added to the paint of Comparative Example 2. That is, the comparative example The coating of 2 has the following composition. The composition of the coating of Comparative Example 2 is blended. : 10.0 parts by weight of an organic-inorganic hybrid hard coat composition (manufactured by JSR Co., Ltd., OPSTER KZ6445, a solution containing 50% by weight of a solid component), the organic-inorganic hybrid type hard coat combination The product is prepared by blending a silica-based ultrafine particle into which a photopolymerizable reactive functional group has been introduced into an acrylic resin; and 6.7 parts by weight of an ethyl ketone as a diluent solvent. Similarly, the plastic film of the hard coat film of Comparative Example 2 was a polydecyl acrylate film (manufactured by Sumitomo Chemical Co., Ltd., Technolloy S001G) having a thickness of 125 μm. The same conditions as in the above Example 1 Π / 16 201249652 The coating of Comparative Example 2 was applied to one surface of the above-mentioned plastic film, and then the coating was dried and solidified to prepare a hard coat film of Comparative Example 2. For the above-mentioned Example 1, Example 2, Comparative Example 1, and Comparative Example 2, four hard coat films (4) were prepared for the pen hardness and the properties. The evaluation results are shown in Table 1 together with the contents of the sample of the hard coat film. Further, the above evaluation was carried out as described above. The wrong pen hardness was evaluated in accordance with JIS K5600-5~4. A so-called scratch test was carried out, that is, a plurality of different hardnesses were set at 45. The angle of the hard coating film on the surface of the sample, after which a pencil is applied to draw the surface, and then the hardness of the hardest stylus which does not cause scratches on the surface is taken as the pencil hardness of the sample. =IS K5_ — 5~丨 Standard, using a cylindrical mandrel (_ system) to produce a price. The mandrel used has a diameter of 32 mm. Put each hard coating. After the upper curve, the sample was observed for cracks or peeling. The evaluation of hard lines or peeling is χ. , clothes
12/16 201249652 如表1的評價結果所示，實施例〗和實施例2的硬塗 層膜的热筆硬度都爲非常硬的5H。即，上述的硬塗層膜具 有優良的耐損傷性和财磨損性。此外，關於上述的硬塗層 膜’即使把膜彎曲時’在硬塗層上也不產生裂紋或剝離。 即’上述的硬塗層膜具有優良的柔性。因此，可以確認： 上述的硬塗層膜做為用作圖像顯示裝置等的保護膜的光學 用的硬塗層膜，具有很好的實用性。 另一方面，比較例1的硬塗層膜把聚對苯二曱酸乙二 酯膜做為基膜。在該硬塗層膜中，做為有機_無機雜化型的 復蓋膜的硬塗層與基膜的黏附性惡化。因此，在把膜彎曲 3守’在硬塗層和基膜的介面上產生了剝離或裂紋。即，該 硬塗層膜具有不好的柔性。 此外，比較例2的硬塗層膜具有由未添加氟系化合物 的塗料形成的硬塗層。該硬塗層膜的硬塗層與實施例！和 實施例2的硬塗層相比，具有低的柔軟性。因此，對於比 較例2的硬塗層膜，用直徑32mm的芯棒使膜彎曲時，在 硬塗層上產生了裂紋。即，比較例2的硬塗層膜具有不好 的柔性。 此外，比較例1和比較例2的硬塗層膜的鉛筆硬度都 爲4H，比實施例1和實施例2的硬塗層膜的軟。即，在對 比較例1和比較例2的硬塗層膜的評價中，沒有得到做為 光學用的硬塗層膜所希望的鉛筆硬度（足夠的鉛筆硬度）。 、如上所述，關於本硬塗層膜，使用丙烯酸系樹脂膜做 為基體材料的塑膠膜。此外，做為硬塗層的材料使用了有 機-無機雜化樹脂。ϋ此，在本硬塗層膜中，由於基膜和硬 塗層的黏’好’所以在它們的介面上難以產生剝離或裂 13/16 201249652 紋。即，本硬塗層膜具有優良的柔性。此外，本硬塗層膜 具有優良的透明性、高的表面硬度、優良的耐損傷性和優 良的耐磨損性。 此外，關於本硬塗層膜的硬塗層，在有機-無機雜化樹 脂中含有氟系化合物的添加劑。由此，在把膜彎曲時也難 以在硬塗層中產生裂紋。即，本硬塗層膜具有優良的柔性。 此外，利用氟系化合物提高了硬塗層表面的光滑性。因此， 由於硬塗層表面變得滑溜，所以難以損傷該表面。因此， 本硬塗層膜還具有更優良的耐損傷性和耐磨損性。 產業上的可利用性 本發明一種方式的硬塗層膜具有優良的透明性，並且 具有優良的柔性和足夠的鉛筆硬度。即，該硬塗層膜具有 優良的耐損傷性和耐磨損性。因此，該硬塗層膜做為光學 用膜非常有用，該光學用膜做為以往用作圖像顯示裝置等 的保護膜的光學用玻璃的替代品使用。 【圖式簡單說明】 益〇 【主要元件符號說明】 益。 14/1612/16 201249652 As shown in the evaluation results of Table 1, the hot pen hardness of the hard coat film of Example and Example 2 was very hard 5H. Namely, the above hard coat film has excellent scratch resistance and wear resistance. Further, regarding the above-mentioned hard coat film 'when the film is bent', no crack or peeling occurs on the hard coat layer. Namely, the above hard coat film has excellent flexibility. Therefore, it has been confirmed that the above-mentioned hard coat film is an optical hard coat film used as a protective film for an image display device or the like, and has excellent practicability. On the other hand, the hard coat film of Comparative Example 1 used a polyethylene terephthalate film as a base film. In the hard coat film, the adhesion of the hard coat layer as the organic-inorganic hybrid type cover film to the base film is deteriorated. Therefore, peeling or cracking occurs at the interface between the hard coat layer and the base film by bending the film. That is, the hard coat film has poor flexibility. Further, the hard coat film of Comparative Example 2 had a hard coat layer formed of a coating material to which no fluorine-based compound was added. Hard coating of the hard coat film with the embodiment! Compared with the hard coat layer of Example 2, it has low flexibility. Therefore, with respect to the hard coat film of Comparative Example 2, when the film was bent by a core rod having a diameter of 32 mm, cracks were generated on the hard coat layer. Namely, the hard coat film of Comparative Example 2 had poor flexibility. Further, the hard coat films of Comparative Example 1 and Comparative Example 2 each had a pencil hardness of 4H, which was softer than those of the hard coat films of Examples 1 and 2. That is, in the evaluation of the hard coat film of Comparative Example 1 and Comparative Example 2, the pencil hardness (sufficient pencil hardness) desired as the hard coat film for optics was not obtained. As described above, regarding the hard coat film, a plastic film using an acrylic resin film as a base material is used. Further, an organic-inorganic hybrid resin is used as a material for the hard coat layer. Accordingly, in the present hard coat film, peeling or cracking is hard to occur on the interface of the base film and the hard coat layer due to the good adhesion of the base film and the hard coat layer 13/16 201249652. That is, the present hard coat film has excellent flexibility. Further, the hard coat film has excellent transparency, high surface hardness, excellent damage resistance, and excellent wear resistance. Further, regarding the hard coat layer of the present hard coat film, an additive of a fluorine-based compound is contained in the organic-inorganic hybrid resin. Therefore, it is difficult to cause cracks in the hard coat layer when the film is bent. That is, the present hard coat film has excellent flexibility. Further, the use of the fluorine-based compound improves the smoothness of the surface of the hard coat layer. Therefore, since the surface of the hard coat layer becomes slippery, it is difficult to damage the surface. Therefore, the present hard coat film also has more excellent damage resistance and wear resistance. Industrial Applicability The hard coat film of one embodiment of the present invention has excellent transparency, and has excellent flexibility and sufficient pencil hardness. Namely, the hard coat film has excellent scratch resistance and abrasion resistance. Therefore, the hard coat film is very useful as an optical film, and the film for optics is used as a substitute for optical glass which has been conventionally used as a protective film for an image display device or the like. [Simple description of the diagram] Benefits [Main component symbol description] Benefit. 14/16