TW200838700A

TW200838700A - Method of manufacturing hard-coated film, hard-coated film, polarizing plate, and image display

Info

Publication number: TW200838700A
Application number: TW096147189A
Authority: TW
Inventors: Teppei Niinou; Hiroyuki Takao; Seiichi Kusumoto; Daisuke Hamamoto; Takayuki Shigematsu
Original assignee: Nitto Denko Corp
Priority date: 2006-12-18
Filing date: 2007-12-11
Publication date: 2008-10-01
Also published as: JP2008151998A; KR20080056642A; CN101204697A

Abstract

To provide a manufacturing method of a hard coat film with which occurrence of curl and snapping can be prevented by a simple method by using a simple manufacturing apparatus without increasing the number of steps, by which the hard coat film of flatness and high hardness can be manufactured and which is excellent in continuous productivity.; In manufacture of the hard coat film 3 which has a hard coat layer 2 at least on one face of a transparent plastic film base material 1, a hard coat layer forming material containing a hard coat resin and a solvent is prepared, the hard coat layer forming material is applied at least onto one face of the transparent plastic film base material 1 to form a coating film and then the coating film is cured to form the hard coat layer 2. A ratio of thickness (A) of the hard coat layer to thickness (B) of the transparent plastic film base material(A/B) is adjusted to be in a range of ≥ 1/2.6.

Description

200838700 九、發明說明：【發明所屬之技術領域】發明領域本發明係有關於硬塗薄膜之製造方法、硬塗薄膜、偏 5 光板及圖像顯示裝置。【先前技術3 發明背景伴隨近年來的技術進步，作為圖像顯示裝置，除了以往的CRT(Cathode Ray Tube)以外，液晶顯示裝置（LCD)、電 10襞顯示裝置(PDP)和電致發光顯示裝置(ELD)等一直被開發出來，並實用化。其中，伴隨有關高視角化、高精細化、高速響應性、色彩再現性等的技術革新，利用LCD的應用也正在從筆記型個人電腦和螢幕向電視變化。LCd的基本構造係在以達到一定間隔的間隙的方式隔著隔板相對配置 15分別具有透明電極的平板上的玻璃基板，且在上述玻璃基板之間注入液晶材料並密封而製成液晶單元，再在一對玻璃基板的外側面分別設置偏光板。以往，在液晶單元表面安裝由玻璃或塑膠形成的蓋板，以便防止對液晶單元表面貝占附的偏光板造成損傷。但是，如果安裝蓋板，在成本和 20重里方面不利’目前逐漸成為在偏光板表面進行硬塗處理。在上述硬塗處理中’ _般是在透明塑膠薄膜基材的單 Φ或兩面上使用形成有硬塗層的硬塗薄膜。上述硬塗層通 $使用熱硬化型樹脂或紫外線硬化型樹脂等來形成。由於LCD的應用轉移到家用電視，可輕易假定一般的 200838700 家用電視使用者即使是使用了 LCD的電視，也會和以往的利用玻璃製CRT的電視進行同樣的操作。因此，對在lcd 上使用的硬塗薄膜要求硬度提高。 , ㈣薄膜的硬度提高可透過使硬塗層的層厚增加而達 5成。但是，如果增大層厚，就有可能由於形成硬塗層時的硬化收縮而産生捲曲。另外，在輥狀透明塑膠薄膜基材上形成硬塗層時’在上述透明塑膠薄膜基材的寬度方向的硬 • 塗層形成材料的塗布區域和其他部分（即硬塗層形成材料的塗布部分和透明塑膠薄膜基材端部的未塗布部分）的邊 1〇界附近，有可能在硬塗薄膜上產生斷裂。如果上述硬塗薄膜産生斷裂，則會給硬塗薄膜的連續生産.步驟和硬塗薄膜向偏光板等貼附層疊作業帶來障礙。針對該問題，已有人提出了利用減少硬塗層的層厚，從而減小形成硬塗層時的硬化收縮力，防止硬塗薄膜發生 15捲曲和斷裂的方法。但是，在該方法中，如果減薄硬塗層 # 的層厚，就有硬塗薄膜硬度下降的問題。另外，有人提出了在透明塑膠薄膜基材的與形成硬塗層相反的一側的表面上形成用於防止捲曲的背塗層的硬塗薄膜之製造方法(參照專利文獻丨）。但是，形成上述背塗層 ^ 2〇的方法有製造裝置變得複雜的問題。另外，該方法也有步 • 驟數增加、生産性差的問題。又，到目前為止，該方法還不此解決上述硬塗薄膜斷裂的問題。專利文獻1:日本特開2004— 109771號公報【内^§1】 6 200838700 發明概要因此’本發明的目的在於提供連續生産性優異的硬塗 '、 °万法，其能夠在不增加步驟數的情況下使用簡 g的製造筆| 、夏、以簡便的方法防止硬塗薄膜發生捲曲和斷 5衣並月b约製造平坦且高硬度的硬塗薄膜。為了達到上述目的，本發明的硬塗薄膜之製造方法是在透明塑膠u 得膜基材的至少一面上具有硬塗層的硬塗薄膜之装&方去’其包含：準備含有硬塗樹脂和溶劑的硬塗層形成材料的準備步驟；在上述透明塑膠薄膜基材的至少一 10面上塗布上述硬塗層形成材料而形成塗膜的塗膜形成步驟；及藉由使上述塗膜硬化，形成上述硬塗層的硬塗層形成步驟’且該製造方法更包含調整上述硬塗層厚度(A)和上述透明塑膠薄膜基材厚度(B)之至少一者，使得上述硬塗層厚度(A)和上述透明塑膠薄膜基材厚度(B)之比(八/；8)為1/2·6 15 以上。本發明的硬塗薄膜是由上述本發明的硬塗薄膜之製造方法製成的硬塗薄膜。本發明的偏光板是具有偏光元件和硬塗薄膜的偏光板，且上述硬塗薄膜是上述本發明的硬塗薄膜。 2〇本發明的圖像顯示裝置是包含硬塗薄膜和偏光板之至少一者的圖像顯示裝置，且上述硬塗薄膜是上述本發明的硬塗薄膜，並且上述偏光板是上述本發明的偏光板。如上所述’在本發明的硬塗薄膜之製造方法中，調整上述硬塗層厚度(Α)和上述透明塑膠薄膜基材厚度(Β)之至 7 200838700 少一者，使得硬塗層厚度(A)和透明塑膠薄膜基材厚度(B) 之比(A/B)為1/2.6以上。透過這樣地調整，在上述塗膜硬化收縮時，上述透明塑膠薄膜基材也與上述塗膜一起沿寬度方向收縮’結果，整個硬塗薄膜沿寬度方向收縮。因此， 5本發明之製造方法防止了硬塗薄膜發生捲曲和斷裂。因此，根據本發明之製造方法，能夠在不增加步驟數的情況下製造平坦的硬塗薄膜。另外，在本發明之製造方法中，由於透過上述比值(A/B)的調整這樣極其簡便的方法實現防止硬塗薄膜發生捲曲和斷裂，所以能夠使用簡易的製造 10裝置(例如以往公知的製造裝置）。此外，在本發明之製造方法中’因為即使在例如輥狀透明塑膠薄膜基材上形成硬塗薄膜時，也能夠防止硬塗薄膜發生捲曲和斷裂，所以連續生産性優異。根據本發明之製造方法，只要調整上述比值 (A/B) ’即使加厚上述硬塗層的層厚，也能防止硬塗薄膜發 15生捲曲和斷裂。因此，根據本發明之製造方法，可以在硬塗層上得到具有充分厚度的高硬度的硬塗薄膜。圖式簡單說明第1圖是顯示本發明的硬塗薄膜的一個例子的結構的剖面示意圖。 20 第2圖是顯示本發明的硬塗薄膜的另一個例子的結構的剖面示意圖。第3圖是顯示本發明的硬塗薄膜的又一個例子的結構的剖面示意圖。第4圖是說明本發明的塗膜的寬度方向的硬化收縮力 8 200838700 的測定方法的圖。第4(A)圖是說明試驗片的製作方法的圖、第4(B)圖是說明硬化收縮力的測定方法的圖。第5圖是說明本發明的實施例的硬塗層的厚度和塗膜的寬度方向的硬化收縮力的關係的曲線圖。 5 第6圖是顯示在本發明的實施例中的塗膜的寬度方向的硬化收縮力和硬塗薄膜的寬度方向的收縮率的關係的曲線圖。【】實施發明之最佳形態 10 在本發明的硬塗薄膜之製造方法中，以調整上述硬塗層厚度(A)和上述透明塑膠薄膜基材厚度(B)之至少一者，使得上述硬塗層厚度(A)和上述透明塑膠薄膜基材厚度(B)之比（A/B)為1/2.5以上為佳，且以調整上述硬塗層上述透明塑膠薄膜基材厚度(B)之至少一者，使得上^硬塗 15層厚度(A)和上述透明塑膠薄膜基材厚度(B)之比（A/B)為 1/2.0以上更佳。在本發明的硬塗薄膜之製造方法中，以將上述硬塗層厚度(A)娜為15〜範圍，將上料_膠薄膜基材厚度(B)優選調整為15〜5G/zm的範圍為佳，且以將上述 20硬塗層厚度⑷調整為16〜3〇㈣的範圍較佳，以調整為Μ 〜25 _的耽圍更佳。另外’將上述透明歸薄膜基材厚度 (B)調整為2G〜5G/zm的範圍較佳，調整為35〜45#瓜的範圍更佳。在本發明的硬塗薄膜之製造方法中，在上述硬塗層形 9 200838700 成步驟中’以上述塗膜的寬度方向的硬化收縮力是9N/cm2 以上為佳。上述硬化收縮力是10N/cm2以上較佳，且以 13N/cm2以上更佳。上述硬化收縮力的上限雖沒有特別的限制，但可為例如34N/cm2。上述硬化收縮力是以9〜19N/cm2 5 的範圍較佳、且以10〜16N/cm2的範圍更佳。上述硬化收縮力可以利用例如在後述的實施例中記載的方法來測定。較佳地，在本發明的硬塗薄膜之製造方法中，上述硬蜜樹脂含有下述(A)成分、（B)成分和(C)成分。 (A) 成分：胺甲酸乙酯丙烯酸酯和胺甲酸乙酯甲基丙烯 10 酸酯之至少一者； (B) 成分：多元醇丙烯酸酯和多元醇甲基丙烯酸酯之至少一者； (C) 成分：由下述(C1)和(C2)之至少一者形成的聚合物或共聚物、或上述聚合物和共聚物的混合聚合物； 15 (C1):具有包括羥基和丙烯醯基之至少一個基團的烧基的丙烯酸烷基酯；和 (C2):具有包括經基和丙烯醯基之至少一個基團的烧基的甲基丙烯酸烷基酯。本發明的硬塗薄膜之製造方法宜更包含形成防反射層 20 的步驟。此時，上述防反射層宜含有中空之球形氧化石夕微粒。較佳地，在本發明的硬塗薄膜中，上述硬塗層的外侧表面結構是凹凸結構。接著，詳細說明本發明。但是，本發明不受下述的記 10 200838700 載限制。本發明的硬塗薄膜是藉由準備含有硬塗樹脂和溶劑的硬塗層形成材料，在透明塑膠薄膜基材的至少一面上塗布上述硬塗層形成材料而形成塗膜，並使上述塗膜硬化而形 5 成硬塗層來製造。乂上述透明塑膠薄膜基材沒有特別的限制。上述透明塑膠薄膜基材宜為可見光的光線透過率優異（光線透過率最好為90%以上）、透明性優異（霧度值最好為1%以下）的美材。上述透明塑膠薄膜基材的形成材料包括例如聚酯系^ 10合物、纖維素系聚合物、聚碳酸酯系聚合物、丙烯酸系聚合物等。上述聚酯系聚合物包括例如聚對苯二曱酸乙二酯、聚萘二甲酸乙二酯等。上述纖維素系聚合物包括例如二乙醯基纖維素、三乙醯基纖維素(TAC)等。上述丙烯酸系聚合物包括例如聚甲基丙烯酸甲酯等。上述透明塑膠薄膜 15基材的形成材料也包括例如苯乙烯系聚合物、烯烴系聚人物、氯乙烯系聚合物、醯胺系聚合物等。上述苯乙烯系聚合物包括例如聚苯乙晞、丙烯腈一苯乙烯共聚物等。上述姆炫糸t合物包括例如I乙稀、聚丙稀、含有環狀纟士構的聚烯烴、含有降冰片烯結構的聚烯烴、乙烯一丙烯共聚物 2〇等。上述醯胺系聚合物包括例如尼龍、芳香族聚醯胺等。上述透明塑膠薄膜基材的形成材料也包括例如醯亞胺系聚合物、颯糸聚合物、聚醚石風系聚合物、聚醚醚酮系聚合物、聚苯硫系聚合物、乙烯醇系聚合物、偏二氯乙烯系聚合物、乙体縮丁酸系聚合物、芳基化物系聚合物、聚甲酸系聚人 11 200838700 物、環氧系聚合物和上述聚合物的混合物等。在這些材料二 ==雙折射少的材料。本發明的硬塗薄膜也可使在偏光板中作為例如賴膜。此時，上述透明塑膠薄膜基材最好是由TAC、聚碳_旨、⑽_聚合物、[Technical Field] The present invention relates to a method for producing a hard coat film, a hard coat film, a partial light plate, and an image display device. [Prior Art 3] With the recent advancement of technology, as an image display device, in addition to a conventional CRT (Cathode Ray Tube), a liquid crystal display device (LCD), an electric display device (PDP), and an electroluminescence display Devices (ELD) and the like have been developed and put into practical use. Among them, with the technological innovations such as high viewing angle, high definition, high-speed responsiveness, and color reproducibility, applications using LCDs are changing from notebook PCs and screens to televisions. The basic structure of the LCd is a glass substrate on a flat plate having a transparent electrode disposed opposite to each other with a gap therebetween at a certain interval, and a liquid crystal material is injected between the glass substrates and sealed to form a liquid crystal cell. Further, polarizing plates are respectively disposed on the outer surfaces of the pair of glass substrates. Conventionally, a cover plate made of glass or plastic is attached to the surface of the liquid crystal cell to prevent damage to the polarizing plate which is attached to the surface of the liquid crystal cell. However, if the cover is installed, it is disadvantageous in terms of cost and 20 weights. At present, it is gradually becoming a hard coating treatment on the surface of the polarizing plate. In the above hard coat treatment, a hard coat film formed with a hard coat layer is used on a single Φ or both sides of a transparent plastic film substrate. The hard coat layer is formed by using a thermosetting resin or an ultraviolet curable resin. Since the application of the LCD is transferred to the home TV, it can be easily assumed that the general 200838700 home television user will perform the same operation as the conventional television using the glass CRT even if the television using the LCD. Therefore, the hard coat film used on the lcd is required to have an increased hardness. (4) The hardness of the film can be increased by 50% by increasing the layer thickness of the hard coat layer. However, if the layer thickness is increased, it is possible to cause curling due to hardening shrinkage when the hard coat layer is formed. Further, when a hard coat layer is formed on a roll-shaped transparent plastic film substrate, 'the coating region and other portions of the hard coating layer forming material in the width direction of the above transparent plastic film substrate (i.e., the coated portion of the hard coat forming material) Near the boundary of the side of the uncoated portion of the end portion of the transparent plastic film substrate, there is a possibility that cracks may occur on the hard coat film. If the hard coat film is broken, the continuous production of the hard coat film and the hard coat film may cause an obstacle to the lamination operation of the polarizing plate or the like. In response to this problem, there has been proposed a method of reducing the layer thickness of the hard coat layer, thereby reducing the hardening shrinkage force at the time of forming the hard coat layer, and preventing the hard coat film from being curled and broken. However, in this method, if the layer thickness of the hard coat layer is thinned, there is a problem that the hardness of the hard coat film is lowered. Further, a method of producing a hard coat film for forming a back coat layer for preventing curl on the surface of the transparent plastic film substrate opposite to the side on which the hard coat layer is formed has been proposed (see Patent Document). However, the method of forming the above-mentioned back coat ^ 2 有 has a problem that the manufacturing apparatus becomes complicated. In addition, this method also has the problem of increasing the number of steps and poor productivity. Moreover, up to now, this method has not solved the problem of the above-mentioned hard coat film fracture. Patent Document 1: Japanese Laid-Open Patent Publication No. 2004-109771 [Embodiment 1] 6 200838700 SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a hard coating having excellent continuous productivity and a method of not increasing the number of steps. In the case of the use of the simple pen manufacturing, | summer, in a simple way to prevent the hard coating film from curling and breaking, and to produce a flat and high hardness hard coating film. In order to achieve the above object, the method for producing a hard coat film of the present invention is a hard coat film having a hard coat layer on at least one side of a film substrate of a transparent plastic u, which comprises: preparing to contain a hard coat resin a step of preparing a material for forming a hard coat layer with a solvent; a step of forming a coating film by coating the hard coat layer forming material on at least one surface of the transparent plastic film substrate to form a coating film; and hardening the coating film a hard coat forming step of forming the hard coat layer', and the manufacturing method further comprises adjusting at least one of the hard coat layer thickness (A) and the transparent plastic film substrate thickness (B) to make the hard coat layer thickness The ratio (eight/8) of (A) to the thickness (B) of the transparent plastic film substrate is 1/2·6 15 or more. The hard coat film of the present invention is a hard coat film produced by the above-described method for producing a hard coat film of the present invention. The polarizing plate of the present invention is a polarizing plate having a polarizing element and a hard coat film, and the hard coat film is the above-described hard coat film of the present invention. 2. The image display device of the present invention is an image display device comprising at least one of a hard coat film and a polarizing plate, wherein the hard coat film is the hard coat film of the present invention described above, and the polarizing plate is the above-described present invention Polarizer. As described above, in the method for producing a hard coat film of the present invention, the thickness of the hard coat layer (Α) and the thickness of the transparent plastic film substrate (Β) are reduced to 7 200838700, so that the thickness of the hard coat layer is A) The ratio (A/B) of the thickness (B) of the transparent plastic film substrate is 1/2.6 or more. By the adjustment, when the coating film is cured and shrunk, the transparent plastic film substrate is also shrunk in the width direction together with the coating film, and the entire hard coating film is shrunk in the width direction. Therefore, the manufacturing method of the present invention prevents the hard coat film from being curled and broken. Therefore, according to the manufacturing method of the present invention, a flat hard coat film can be produced without increasing the number of steps. Further, in the production method of the present invention, it is possible to prevent the hard coat film from being curled and broken by the extremely simple method of adjusting the ratio (A/B). Therefore, it is possible to use a simple manufacturing apparatus 10 (for example, a conventionally known manufacturing method). Device). Further, in the production method of the present invention, since the hard coat film can be prevented from being curled and broken even when a hard coat film is formed on, for example, a roll-shaped transparent plastic film substrate, the continuous productivity is excellent. According to the production method of the present invention, it is possible to prevent the hard coat film from being curled and broken even if the ratio (A/B)' is adjusted to increase the layer thickness of the hard coat layer. Therefore, according to the production method of the present invention, a hard coat film having a high hardness and a sufficient thickness can be obtained on the hard coat layer. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing the structure of an example of a hard coat film of the present invention. Fig. 2 is a schematic cross-sectional view showing the structure of another example of the hard coat film of the present invention. Fig. 3 is a schematic cross-sectional view showing the structure of still another example of the hard coat film of the present invention. Fig. 4 is a view for explaining a method of measuring the curing shrinkage force 8 200838700 in the width direction of the coating film of the present invention. Fig. 4(A) is a view for explaining a method of producing a test piece, and Fig. 4(B) is a view for explaining a method of measuring a hardening contraction force. Fig. 5 is a graph for explaining the relationship between the thickness of the hard coat layer and the hardening shrinkage force in the width direction of the coating film of the embodiment of the present invention. [Fig. 6] Fig. 6 is a graph showing the relationship between the hardening shrinkage force in the width direction of the coating film and the shrinkage ratio in the width direction of the hard coat film in the examples of the present invention. [Best Mode for Carrying Out the Invention] In the method for producing a hard coat film of the present invention, at least one of the thickness of the hard coat layer (A) and the thickness (B) of the transparent plastic film substrate is adjusted to make the hard The ratio (A/B) of the coating thickness (A) to the thickness (B) of the transparent plastic film substrate is preferably 1/2.5 or more, and the thickness of the transparent plastic film substrate (B) of the hard coating layer is adjusted. In at least one, it is more preferable that the ratio (A/B) of the thickness (A) of the upper layer 15 layer and the thickness (B) of the transparent plastic film substrate is 1/2.0 or more. In the method for producing a hard coat film of the present invention, the thickness (B) of the coating material is preferably adjusted to a range of 15 to 5 G/zm by setting the thickness (A) of the hard coat layer to a range of 15 to 15 mm. Preferably, the range of adjusting the thickness (4) of the above 20 hard coat layers to 16 to 3 〇 (4) is preferable, and the pitch of Μ 〜 25 _ is preferably adjusted. Further, it is preferable to adjust the thickness of the transparent film substrate (B) to 2G to 5G/zm, and to adjust the range of 35 to 45# melon. In the method for producing a hard coat film of the present invention, it is preferable that the hardening shrinkage force in the width direction of the coating film is 9 N/cm 2 or more in the step of forming the hard coat layer 9 200838700. The hardening shrinkage force is preferably 10 N/cm2 or more, and more preferably 13 N/cm2 or more. The upper limit of the above-described hardening shrinkage force is not particularly limited, but may be, for example, 34 N/cm2. The hardening shrinkage force is preferably in the range of 9 to 19 N/cm 2 5 and more preferably in the range of 10 to 16 N/cm 2 . The hardening shrinkage force can be measured by, for example, the method described in the examples below. Preferably, in the method for producing a hard coat film of the present invention, the hard honey resin contains the following components (A), (B) and (C). (A) component: at least one of urethane acrylate and urethane methacrylate 10; (B) component: at least one of a polyol acrylate and a polyol methacrylate; Component: a polymer or copolymer formed of at least one of the following (C1) and (C2), or a mixed polymer of the above polymer and copolymer; 15 (C1): having a hydroxyl group and an acrylonitrile group An alkyl acrylate of at least one group; and (C2): an alkyl methacrylate having a alkyl group including at least one of a trans group and an acryl group. The method for producing a hard coat film of the present invention preferably further comprises the step of forming the antireflection layer 20. In this case, the antireflection layer preferably contains hollow spherical oxidized oxide particles. Preferably, in the hard coat film of the present invention, the outer surface structure of the hard coat layer is a textured structure. Next, the present invention will be described in detail. However, the present invention is not limited by the following description 10 200838700. The hard coat film of the present invention is formed by applying a hard coat layer forming material containing a hard coat resin and a solvent, coating the hard coat layer forming material on at least one surface of the transparent plastic film substrate to form a coating film, and forming the coating film. It is hardened and shaped into a hard coat to make it.乂 The above transparent plastic film substrate is not particularly limited. The transparent plastic film substrate is preferably a material having excellent light transmittance (light transmittance of 90% or more) and excellent transparency (having a haze value of preferably 1% or less). The material for forming the transparent plastic film substrate includes, for example, a polyester-based compound, a cellulose-based polymer, a polycarbonate-based polymer, an acrylic polymer, and the like. The above polyester-based polymer includes, for example, polyethylene terephthalate, polyethylene naphthalate, and the like. The above cellulose-based polymer includes, for example, diethyl cellulose, triethyl cellulose (TAC), and the like. The above acrylic polymer includes, for example, polymethyl methacrylate or the like. The material for forming the transparent plastic film 15 substrate also includes, for example, a styrene polymer, an olefin polymer, a vinyl chloride polymer, a guanamine polymer, or the like. The above styrene-based polymer includes, for example, polystyrene, acrylonitrile-styrene copolymer, and the like. The above compound includes, for example, ethylene, polypropylene, a polyolefin having a cyclical gentleman structure, a polyolefin containing a norbornene structure, an ethylene-propylene copolymer, and the like. The above amide-based polymer includes, for example, nylon, aromatic polyamine, and the like. The material for forming the transparent plastic film substrate also includes, for example, a quinone imine polymer, a fluorene polymer, a polyether stone polymer, a polyetheretherketone polymer, a polyphenylene sulfide polymer, or a vinyl alcohol system. A polymer, a vinylidene chloride-based polymer, a acetylated butyric acid-based polymer, an arylate-based polymer, a polycarboxylic acid-based polymer 11 200838700, a mixture of an epoxy-based polymer and the above polymer, and the like. In these materials two == less birefringent material. The hard coat film of the present invention can also be used as, for example, a film in a polarizing plate. In this case, the transparent plastic film substrate is preferably made of TAC, polycarbonate, (10) polymer,

10 在上述透明歸薄膜基材是偏光元件時，硬塗層就可發揮以往的保護層的作用。如果是這樣的結構，硬塗薄膜即可兼具安裝在液晶單元表面的蓋板的功能。包含％狀結構的聚烯煙、包含降冰片烯結構的聚埽煙等形成的膜在本I明中，上述透明塑膠薄膜基材也可以是偏光70件本纟如果疋适樣的結構，就不需要由TAC等形成的保護層，相將偏光_結姻單化。藉此，可使偏光板或圖像顯示裝㈣製造步雖減少，使生産效率提高。另外，如果是這樣的結構，還可以使偏光板進-步薄層化。10 When the transparent film substrate is a polarizing element, the hard coat layer functions as a conventional protective layer. In the case of such a structure, the hard coat film can function as a cover plate mounted on the surface of the liquid crystal cell. a film formed of a polyene smoke containing a % structure, a polymethane containing a norbornene structure, etc., in the present invention, the transparent plastic film substrate may be a polarized 70 piece, if a suitable structure, There is no need for a protective layer formed by TAC or the like, and the phase is monotonized. Thereby, the manufacturing steps of the polarizing plate or the image display device (4) can be reduced, and the production efficiency can be improved. Further, if it is such a structure, the polarizing plate can be further thinned.

在本發明中，上述透明塑膠薄膜基材厚度如上所述。 15另外’調整上述透明塑膠薄膜基材的厚度包括：根據本發明選擇適當厚度的透明塑膠薄膜基材以及通過拉伸、收縮等調整透明塑膠薄膜基材厚度之至少一者。上述透明塑膠薄膜基材的折射率沒有特別限制，可為例如i 3G〜i 8〇的範圍，且以1.40〜1.70的範圍為佳。如前所述，上述硬塗層形成材料包含硬塗樹脂和溶劑。上述硬塗樹脂可例如：熱硬化型樹脂、熱塑性樹脂、紫外線硬化型樹脂、電離放射線硬化型樹脂、雙成分混合型樹脂等。在這些樹脂中，特別以使用以藉紫外線照射硬化處理的簡單加工操作就可以高效率地形成硬塗層的紫外 12 200838700 線硬化型樹脂為佳。另外，在上述紫外線硬化型樹脂中可以混合紫外線聚合引發劑(光聚合引發劑）。上述紫外線硬化型樹脂可舉例如：聚酯系、丙烯酸系、胺甲酸乙酯系、聚矽氧系、環氧系等各種樹脂。該紫外線 5硬化型樹脂包括紫外線硬化型單體、低聚物、聚合物等。特別好使用的紫外線硬化型樹脂是具有紫外線聚合性的官能基的樹脂，尤其可舉包含具有2個以上、特別是具有3〜6 個上述官能基的丙烯酸系單體和低聚物的樹脂為例。這樣的紫外線硬化型樹脂的具體例子可舉例如：多元 10 醇的丙烯酸酯等丙烯酸酯樹脂、多元醇的甲基丙烯酸酯等甲基丙烯酸酯樹脂、由二異氰酸酯、多元醇和丙烯酸的輕烷基酯合成的多官能性胺甲酸乙酷丙烯酸酯樹脂、由多元醇和甲基丙烯酸的甲基丙烯酸經基酯等合成的多官能性胺甲酸乙酯甲基丙烯酸酯樹脂等。另外，還可以根據需要.、 15 適當使用具有丙烯酸自旨系官能基的聚醚樹脂、聚酯樹脂、環氧樹脂、酵酸樹脂、螺縮酸樹脂、聚丁二烯樹脂、聚琉醇聚烯樹脂等。另外’亦可使用二聚氰胺系樹脂、胺曱酸乙酉旨系樹脂、醇酸系樹脂、聚碎氧糸樹脂等。上述光聚合引發劑可舉例如：2,2 —二甲氧基一2—苯 20基苯乙酮、苯乙酮、二苯甲嗣、°山_、3 —甲基苯乙酮、4 —氣二苯甲酮、4,4’一二甲氧基二苯甲酮、苯偶姻丙基醚、节基二曱基縮酮、N，N，N，，N —四甲基一 4,4’ 一二胺基二本甲酮、1一（4一異丙基苯基）一2—經基―2—甲基丙烧―1一酮等，此外可以使用氧硫山嗟系化合物等。 13 200838700 上述硬塗樹脂可以單獨使用一種，也可以並用2種以上。另外，也可以使用市售的紫外線硬化型樹脂等作為上述硬塗樹脂。如前所述，上述硬塗樹脂宜含有下述(A)成分、成分 5 和(C)成分。 (A) 成分·胺甲酸乙_丙稀酸醋和胺曱酸乙g旨甲基丙烯酸酯之至少一者； (B) 成分：多元醇丙烯酸酯和多元醇甲基丙烯酸酯之至少一者； 10 (C)成分：由下述(C1)和（C2)之至少一者形成的聚合物或共聚物、或上述聚合物和共聚物的混合聚合物； (C1):具有包括羥基和丙烯醯基之至少一個基團的烷基的丙烯酸烷基酯；和 (C2) ·具有包括經基和丙稀酿基之至少一個基團的烧 15 基的甲基丙烯酸烷基酯。上述(A)成分，即上述胺甲酸乙酯丙烯酸酯和胺甲酸乙酉旨甲基丙稀酸醋’可以使用含有丙稀酸、甲基丙稀酸、丙烯酸酯、甲基丙烯酸酯、多元醇、二異氰酸酯作為構成成分的化合物。例如，使用丙烯酸、甲基丙烯酸、丙烯酸酯 20 和曱基丙烯酸酯之至少一種單體和多元醇，製作具有1個以上羥基的丙烯酸羥基酯和具有丨個以上羥基的甲基丙烯酸趣基酯之至少1者，再透過使其和二異氰酸酯反應，就可以製造胺甲酸乙酯丙稀酸酯和胺甲酸乙酯甲基丙烯酸酯之至少一者。在上述(A)成分中，胺甲酸乙酯丙烯酸酯和胺甲酸 14 200838700 乙酯甲基丙烯酸酯可以單獨使用1種，也可以並用2種以上。上述丙酸S曰包括例如丙稀酸烧^基g旨、丙稀酸烧基酯等。上述丙稀酸烧基酯包括例如丙稀酸甲酯、丙烯酸乙酯、丙烯酸異丙酯、丙烯酸丁酯等。上述丙烯酸環烷基酯 5 包括例如丙烯酸環己酯等。上述甲基丙烯酸酯包括例如甲基丙稀酸烷基酯、甲基丙烯酸環烷基酯等。上述甲基丙烯酸烧基酯包括例如甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸異丙酯、甲基丙稀酸丁酯等。上述甲基丙烯酸環烧基酯包括例如甲基丙烯酸環己酯等。 10 上述多元醇是具有至少2個經基的化合物。上述多元醇包括例如乙二醇、1，3 —丙二醇、1,2—丙二醇、二乙二醇、二丙二醇、新戊二醇、1，3—丁二醇、1，4一丁二醇、1，6 — 己二醇、1，9一壬二醇、1，10-癸二醇、2,2,4一三甲基一 U 一戊二醇、3 —甲基一 1，5—戊二醇、經基新戊酸新戊二醇 15 酯、環己烷二甲醇、1，4一環己二醇、螺環二醇、三環癸炫甲醇、加氫雙酚A、環氧乙烷加成雙酚A、環氧丙烷加成雙酚A、三羥甲基乙烷、三羥甲基丙烷、甘油、3—甲基戊炼一 1,3,5—三醇、季戊四醇、二季戊四醇、三季戊四醇、葡萄糖類等。 20 作為上述二異氰酸酯，例如可以使用芳香族、脂肪族或脂環族的各種二異氰酸酯類。上述二異氰酸酯包括例如四亞甲基二異氰酸酷、六亞甲基二異氰酸_、異佛酮二異氰酸酯、2,4—甲苯二異氰酸酯、4,4—二苯基二異氰酸_、 1，5—萘二異氰酸酯、3,3—二甲基一4,4一二苯基二異氰酸 15 200838700 5 ❿ 10 15 20 酯、一甲苯二異氰酸酯、三甲基，、亞甲基二異氰酸酯、4,4 --本基r二異驗料，以及它們K化物等。細上 =A)成分的齡比例沒有朗㈣制。透過使用上述⑷成二可以使所形成的上述硬塗層的柔軟性和對上述 ^明_賴基材的密著性提高。從這些方面和上述硬塗曰的硬度的賴等出發，相對於上述硬塗層整個樹脂成分，上述⑷成分的混合比例是例如15〜^= %的範圍，且以25〜45重量%的範圍為佳。所謂上述整個：脂成分，M(AM分、⑻成分和(eM分料計量在使用其他劃旨成分時，是指上述三種成分的合計量和述樹脂成分的合計量合起來的量，以下也是同樣的里上述(B)成分包括例如季戊四醇二丙稀酸酯、季戊四三丙烯酸酯、季戊四醇四丙烯酸酯、二李，子戍四醇六丙烯酸酉旨、1，6-己二醇丙烯酸_、季戊四醇二甲基⑽_ 戊四醇三甲基丙烯酸_、季戊四醇四甲基Μ酸酸、戊四醇六甲基丙烯酸S旨、1，6-己二醇甲基㊅烯㈣旨等。… 們可以單獨使用，也可以並用2種以上。例如，、匕上述多元醇丙烯酸酯最好為包含由季戊四醇三丙烯酸酷 /、字戊四醇四丙烯酸酯的聚合物形成的單體成分及季戊臀二丙烯酸@旨以及季戊四醇四丙烯酸酯的混合成分。上述(Β)成分的混合比例沒有特別的限制。例如於上述(Α)成分’上述(Β)成分的混合比例是以％〜“ο %的範圍為佳，且以100〜150重量％的範圍更佳。如果》上述 (Β)成分的混合比例是上述(Α)成分的70重量❶/〇以八上，就可以 16 200838700 使所形成的硬塗層的硬度進一步提高，能夠使耐擦傷性提南0 在上述(C)成分中，上述(C1)和(C2)的上述烷基是例如碳原子數為1〜10的烧基。上述烧基可以是直鏈狀的，也可以是支鏈狀的。上述(C)的成分可舉例如：含有下述通式（1) 的重覆單元的聚合物、共聚物、或者上述聚合物和上述共聚物的混合物。 r R1 CH2—c c=o ο—R2 _(1) 10 在上述式(1)中，Rl 是、R2 是 _cH2CH2〇x 或下述通式(2)表示的基®，上述X是·Η或由下述通式(3)表的丙烯醯基。 -CH2—ch^Ch2_〇一X 〇In the present invention, the thickness of the above transparent plastic film substrate is as described above. 15 additionally adjusting the thickness of the transparent plastic film substrate comprises: selecting a transparent plastic film substrate of a suitable thickness according to the present invention and adjusting at least one of the thicknesses of the transparent plastic film substrate by stretching, shrinking, or the like. The refractive index of the above transparent plastic film substrate is not particularly limited and may be, for example, a range of i 3G to i 8 ,, and preferably in the range of 1.40 to 1.70. As described above, the above hard coat forming material contains a hard coat resin and a solvent. The hard coat resin may be, for example, a thermosetting resin, a thermoplastic resin, an ultraviolet curable resin, an ionizing radiation curable resin, or a two-component mixed resin. Among these resins, it is preferable to use a UV 12 200838700 wire-curable resin which can form a hard coat layer efficiently by a simple processing operation by hardening treatment by ultraviolet rays. Further, an ultraviolet polymerization initiator (photopolymerization initiator) may be mixed in the ultraviolet curable resin. The ultraviolet curable resin may, for example, be a polyester, an acrylic, an urethane, a polyoxyn, or an epoxy. The ultraviolet ray-curable resin includes an ultraviolet curable monomer, an oligomer, a polymer, and the like. The ultraviolet curable resin which is particularly preferably used is a resin having an ultraviolet polymerizable functional group, and particularly includes a resin having two or more acrylic monomers and oligomers having 3 to 6 functional groups as described above. example. Specific examples of such an ultraviolet curable resin include, for example, an acrylate resin such as an acrylate of a polyhydric alcohol, a methacrylate resin such as a methacrylate of a polyhydric alcohol, and a light alkyl ester of a diisocyanate, a polyhydric alcohol, and an acrylic acid. A synthetic polyfunctional urethane acrylate resin, a polyfunctional urethane methacrylate resin synthesized from a polyol and a methacrylic acid methacrylic acid via a base ester or the like. In addition, a polyether resin having an acrylic acid functional group, a polyester resin, an epoxy resin, a yeast resin, a spirulina resin, a polybutadiene resin, and a polydecyl alcohol can be suitably used as needed. Alkene resin, etc. Further, a melamine-based resin, an amine phthalic acid-based resin, an alkyd-based resin, or a polyoxyanthracene resin may be used. The photopolymerization initiator may, for example, be 2,2-dimethoxy-2-phenyl-phenylacetophenone, acetophenone, benzophenone, ～山-3, 3-methylacetophenone, 4 — Gas benzophenone, 4,4'-dimethoxybenzophenone, benzoin propyl ether, stilbene dimethyl ketal, N, N, N, N-tetramethyl-4 4'-diamino-based di- ketone, 1-(4-isopropylphenyl)- 2-trans-yl-2-methylpropanone-1-one, etc., in addition to oxygenous sulphate compounds, etc. . 13 200838700 The hard coat resin may be used singly or in combination of two or more. Further, a commercially available ultraviolet curable resin or the like may be used as the above hard coat resin. As described above, the hard coat resin preferably contains the following components (A), 5 and (C). (A) at least one of a component, a urethane acetate, and an amide methacrylate; (B) a component: at least one of a polyol acrylate and a polyol methacrylate; 10 (C) component: a polymer or copolymer formed of at least one of the following (C1) and (C2), or a mixed polymer of the above polymers and copolymers; (C1): having a hydroxyl group and an acrylonitrile group An alkyl acrylate of an alkyl group having at least one group; and (C2) an alkyl methacrylate having a 15 group including at least one of a trans group and an acryl. The above component (A), that is, the above-mentioned ethyl urethane acrylate and urethane formic acid methyl acrylate vinegar may be used, including acrylic acid, methyl acrylate, acrylate, methacrylate, polyol, A compound of a diisocyanate as a constituent component. For example, at least one monomer of acrylic acid, methacrylic acid, acrylate 20, and mercapto acrylate and a polyhydric alcohol are used to prepare a hydroxy acrylate having one or more hydroxyl groups and a methacrylic acid ester having more than one hydroxy group. At least one of them can be at least one of ethyl urethane acrylate and urethane methacrylate by reacting it with a diisocyanate. In the above-mentioned component (A), the urethane acrylate and the uric acid 14 200838700 ethyl methacrylate may be used singly or in combination of two or more. The above-mentioned propionic acid S 曰 includes, for example, an acrylic acid group, an alkyl acrylate, and the like. The above-mentioned acrylonitrile ester includes, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate or the like. The above cycloalkyl acrylate 5 includes, for example, cyclohexyl acrylate or the like. The above methacrylates include, for example, alkyl methacrylate, cycloalkyl methacrylate and the like. The above methacrylic acid ester includes, for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, butyl methacrylate and the like. The above cycloalkyl methacrylate includes, for example, cyclohexyl methacrylate and the like. 10 The above polyol is a compound having at least 2 mercapto groups. The above polyols include, for example, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,6 — hexanediol, 1,9-nonanediol, 1,10-nonanediol, 2,2,4-trimethyl-U-pentanediol, 3-methyl-1,5-pentyl Glycol, pentaerythritol neopentyl glycol 15 ester, cyclohexane dimethanol, 1,4-cyclohexanediol, spiro diol, tricyclic hydrazine methanol, hydrogenated bisphenol A, ethylene oxide Addition of bisphenol A, propylene oxide addition bisphenol A, trimethylolethane, trimethylolpropane, glycerol, 3-methyl pentane-1,3,5-triol, pentaerythritol, dipentaerythritol , three pentaerythritol, glucose, and the like. 20 As the above diisocyanate, for example, various diisocyanates of an aromatic, aliphatic or alicyclic group can be used. The above diisocyanate includes, for example, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 2,4-toluene diisocyanate, 4,4-diphenyl diisocyanate. _, 1,5-naphthalene diisocyanate, 3,3-dimethyl- 4,4-diphenyl diisocyanate 15 200838700 5 ❿ 10 15 20 ester, mono-toluene diisocyanate, trimethyl, and methylene Diisocyanate, 4,4 -benyl r diisoassay, and their K compounds. The ratio of the age of the =A) component is not the same. By using the above (4), the flexibility of the formed hard coat layer and the adhesion to the above-mentioned substrate can be improved. In view of these aspects and the hardness of the hard coat layer, the mixing ratio of the component (4) is, for example, in the range of 15 to 2% by weight, and in the range of 25 to 45 wt%, based on the entire resin component of the hard coat layer. It is better. The above-mentioned whole: fat component, M (AM component, (8) component, and (eM component measurement, when other components are used, means the total amount of the above three components and the total amount of the resin components combined, and the following is also In the same manner, the above component (B) includes, for example, pentaerythritol diacrylate, pentaerythritol, pentaerythritol tetraacrylate, di-li, tetradecyl hexaacrylate, 1,6-hexanediol acrylate. Pentaerythritol dimethyl (10) pentylenetetraol trimethacrylate _, pentaerythritol tetramethyl phthalic acid, pentaerythritol hexamethyl acrylate, 1,6-hexanediol methyl hexene (IV), etc. These may be used singly or in combination of two or more kinds. For example, the above polyol acrylate is preferably a monomer component comprising a polymer of pentaerythritol triacrylate or a pentaerythritol tetraacrylate and a quaternary buttock. The mixing ratio of the above-mentioned (Β) component is not particularly limited. For example, in the above (Α) component, the mixing ratio of the above (Β) component is % to “ο %. Fan Preferably, it is more preferably in the range of 100 to 150% by weight. If the mixing ratio of the above (Β) component is 70% by weight of the above (Α) component, it can be formed by the hardening of 16 200838700. The hardness of the coating layer is further increased, and the scratch resistance can be improved. In the above component (C), the alkyl group of the above (C1) and (C2) is, for example, a burning group having 1 to 10 carbon atoms. The group may be linear or branched. The component (C) may, for example, be a polymer, a copolymer, or the above polymer containing a repeating unit of the following formula (1). a mixture of the above copolymers r R1 CH2—cc=o ο—R2 _(1) 10 In the above formula (1), R1 is, R2 is _cH2CH2〇x or a group represented by the following formula (2) The above X is Η or an acrylonitrile group represented by the following formula (3): -CH2—ch^Ch2_〇-X 〇

II

X (2)X (2)

CHOCHO

H2 CH 二 Η C (3) 17 200838700 在上述通式(2)中，上述叉是—丑或由上述通式(3)表示、丙烯醯基’上述X可以相同、也可以不同。 /' ' 上述(C)成分可舉例如··選自於由丙烯酸2____ ’ 一輕兩酯、丙烯酸2,3 —二丙烯醯氧基丙酯、丙烯酸2〜羥義〜3 丙烯醯氧基丙酯、丙烯酸2〜丙烯醯氧基一3〜叙 t内S旨、甲基丙烯酸2,3—二羥丙酯、甲基丙烯酸2,3一二丙埽醯氧美丙酯、甲基丙烯酸2—羥基—3—丙烯醯氧基丙土㈡甲基丙烯酸2—丙烯醯氧基一3—羥丙酯、丙烯酸2—_ Γ狀 tGS曰、丙烯酸 10 15 20 2—丙烯醯氧基乙酯、甲基丙烯酸2一羥乙酯和甲美丙烯妒2 —丙烯醯氧基酯組成的群中的至少一個單體形成的浐入物、共聚物、或者上述聚合物和上述共聚物的混八物上述(C)成分的混合比例沒有特別的限制。例如，相對於上述(A)成分、上述(c)成分的混合比例是以11〇重真 %的範圍為佳，且以45〜85重量％的範圍更佳。如果上述成分的混合比例相對於上述(A)成分是HQ會旦；、至里/〇以下，則硬塗層形成材料的塗布性優異。上述溶劑沒有特別的限定。上述溶劑包括例如：二丁醚、二甲氧基甲烷、二曱氧基乙烷、二乙氧，乳基乙烷、環氧丙烷、1，4~二噁烷、U一二氧雜戊環斤 ^ 三°惡烧、四氧吱喃、丙酮、甲乙酮、二乙基_、— … 一丙基、二显丁基酮、環戊酮、環己酮、甲基環己_、甲 " ^ ^ x , 6^曰、甲酸丙酯、甲酸正戍_、乙酸甲酯、乙酸乙酯、 rT丄、 T 09、丙酸乙酯、乙酉欠正戊酯、乙醯丙酮、雙丙鲷醇、乙醯乙乙酸乙酯、甲醇、乙醇、；1一丙醇、 9、乙如 2丙醇、丁醇、2 18 200838700 丁醇、戊醇、2—甲基—2—丁醇、環己醇、乙酸異丁醋、甲基異頂(MIBK)、2一辛_、2—戊_、2—己酮、2 庚綱3-庚酮、乙二醇單乙鱗乙酸醋、乙二醇單乙鱗、乙二醇單丁 it、乙二醇單甲鱗、丙二醇單㈣乙酸酯、丙 5二醇單甲鱗等。這些溶劑可以單獨使用、也可以並用2種以 j攸使上述透明塑膠薄膜基材和上述硬塗層的密著性提 I的觀點出發，上述溶劑以占整體的20重量％以上的比例 a有乙酸乙酯為佳’且以占整體的25重量％以上的比例含有乙&L乙g曰更佳，並以占整體的川〜％重量％的比例含有乙酉欠乙酯最佳。上述溶劑中的乙酸乙酯的比例如果是川重里竓以下，就可以使溶劑的揮發速度適當，能夠有效地防止塗布不均或者乾燥不均。和上述乙酸乙醋並用的溶劑種颏/又有特別的限制，例如，上述溶劑包括乙酸丁醋、甲乙酮乙一醇單丁鱗、丙二醇單甲醚等。在上述硬塗層形成材料中，可以添加各種調平劑。上述調平劑可舉舉就系或聚石夕氧系調平劑為例，且以聚石夕氧系調平劑為佳。上述聚矽氧系調平劑包括例如：反應性聚矽氧、聚二曱基矽氧烷、聚醚改質聚二甲基矽氧烷、聚甲基烷基矽氧烷等。在這些聚矽氧系調平劑中，以上述反應 2〇性石夕氧燒尤佳。透過添加上述反應性聚石夕氧，可對表面賦予潤滑性，使得在長時間期間内持續耐擦傷性。另外，如果使用具有羥基的反應性聚矽氧作為上述反應性聚矽氧，則在上述硬塗層上形成含有矽氧烷成分的防反射層作為防反射層（低折射率層）時，上述防反射層和上述硬塗層的密著 19 200838700 性提高。 2對於上述整個樹脂成分咖重量份，上賴平劑的混。里疋例如5重1份以下，且以〇〇1〜5重量份的範圍為佳。H2 CH Di Η C (3) 17 200838700 In the above formula (2), the above-mentioned cross is ugly or represented by the above formula (3), and the above-mentioned X may be the same or different. The above component (C) may, for example, be selected from the group consisting of 2?'-light diester of acrylic acid, 2,3-dipropenyl propyl acrylate, and 2~hydroxyl~3 propylene decyl acrylate. Ester, acrylic acid 2~ propylene oxime a 3~ S, S, methacrylic acid 2,3-dihydroxypropyl ester, methacrylic acid 2,3 dipropylene propoxy propyl methacrylate, methacrylic acid 2 —Hydroxy—3-propenyloxypropane (2) 2-propenyloxy 3-hydroxypropyl methacrylate, 2- Γ t tGS 丙烯酸, acrylic acid 10 15 20 2 — propylene methoxyethyl ester, An intrusion, a copolymer, or a mixture of the above polymer and the above copolymer, formed by at least one monomer in a group consisting of 2-hydroxyethyl methacrylate and methacryl oxime 2-propenyl methoxy ester The mixing ratio of the above component (C) is not particularly limited. For example, the mixing ratio of the component (A) and the component (c) is preferably in the range of 11% by weight, and more preferably in the range of 45 to 85% by weight. When the mixing ratio of the above-mentioned components is HQ with respect to the above-mentioned (A) component, the coating property of the hard coat layer forming material is excellent. The above solvent is not particularly limited. The above solvent includes, for example, dibutyl ether, dimethoxymethane, dimethoxyethane, diethoxy, lactylethane, propylene oxide, 1,4-dioxane, U-dioxolane斤^ Three-degree smoldering, tetraoxan, acetone, methyl ethyl ketone, diethyl _, - propyl, di- butyl ketone, cyclopentanone, cyclohexanone, methylcyclohexyl, a " ^ ^ x , 6^曰, propyl formate, formic acid, 戍, methyl acetate, ethyl acetate, rT丄, T 09, ethyl propionate, acetamidine, acetoacetate, dipropanol Ethyl acetate, methanol, ethanol, 1 -propanol, 9, b, such as 2 propanol, butanol, 2 18 200838700 butanol, pentanol, 2-methyl-2-butanol, cyclohexane Alcohol, isobutyl acetonate, methyl isotop (MIBK), 2-mono-, 2-penta-, 2-hexanone, 2-heptan-3-heptanone, ethylene glycol monoethyl acetate, ethylene glycol Single-ethyl scale, ethylene glycol monobutyl it, ethylene glycol monomethyl scale, propylene glycol mono (tetra) acetate, propane 5 glycol monomethyl scale, and the like. These solvents may be used singly or in combination of two kinds of materials to improve the adhesion of the transparent plastic film substrate and the hard coat layer. The solvent has a ratio of 20% by weight or more of the total. Ethyl acetate is preferred, and it is more preferable to contain B&L-g 曰 in a ratio of 25% by weight or more of the whole, and it is preferable to contain acetamoxime in a ratio of ～% by weight of the whole. When the ratio of ethyl acetate in the above solvent is less than or equal to the weight of lanthanum, the solvent volatilization rate can be appropriately adjusted, and coating unevenness or uneven drying can be effectively prevented. The solvent used in combination with the above-mentioned ethyl acetate is particularly limited. For example, the above solvent includes butyl acetate, methyl ethyl ketone monobutyl sulphate, propylene glycol monomethyl ether, and the like. In the above hard coat forming material, various leveling agents may be added. The above-mentioned leveling agent may be exemplified by a poly orthosilicate-based leveling agent, and a poly-stone oxide leveling agent is preferred. The above polyfluorinated leveling agent includes, for example, reactive polyfluorene oxide, polydidecyloxyne, polyether modified polydimethylsiloxane, polymethylalkyloxane, and the like. Among these polyoxane-based leveling agents, it is particularly preferable to use the above-mentioned reaction. By adding the above-mentioned reactive polychlorinated oxygen, the surface can be imparted with lubricity so that the scratch resistance is maintained for a long period of time. Further, when a reactive polyfluorene having a hydroxyl group is used as the reactive polyfluorene, when the antireflection layer containing a decane component is formed on the hard coat layer as an antireflection layer (low refractive index layer), The adhesion of the antireflection layer and the above hard coat layer is improved. 2 For the above-mentioned entire resin component, the weight of the coffee is mixed with the upper leveling agent. The ridge is, for example, 5 parts by weight or less, and preferably in a range of 1 to 5 parts by weight.

在上述硬塗層形成材料中，可以添加各種反應性稀釋 5劑。上述反應性稀釋劑沒有特別的限定。上述反應性稀釋劑包括例如：黏度比較低的心己二醇二丙烯酸§旨、Μ -己二醇二甲基丙稀酸醋、三丙二醇二丙烯酸醋、三丙二醇二甲基丙婦酸酿、二乙二醇二丙稀酸醋、二乙二醇二甲基丙烯酸龍、己二醇丙稀酸酉旨、己二醇甲基丙稀酸醋、季 W戊四醇三丙烯酸酷、季戊四醇三甲基丙稀酸醋、三經甲基丙烧三丙烯酸醋、三經甲基丙燒三甲基丙稀酸醋、二季戊四醇八丙烯酸醋、二季戊四醇六甲基丙烯酸醋、新戊二醇 -丙烯Μ曰、新戊二醇二甲基丙烯酸醋等2官能以上的單體 1 #低來物等。上述反應性稀釋劑也包括例如：作為單官能單體的Ν-乙稀基*各烧酮、丙烯酸乙自旨、丙烯酸丙醋等丙歸H頁、曱基丙烯酸乙醋、甲基丙稀酸丙酿、甲基丙稀酸異丙醋、甲基丙稀酸丁酿、甲基丙稀酸己醋、甲基丙稀酸八辛@日曱基丙婦酸2—經乙醋、甲基丙烯酸環己醋、甲基丙烯酸壬基苯酉曰等甲基丙稀酸醋類、甲基丙稀酸四氮口夫 20喃醋及其己内醋改質物等衍生物、苯乙稀、卜甲基苯乙烯、丙稀酸等以及它們的混合物等。根據需要，在不損害性能的範圍内，在上述硬塗層的 I成材料巾也可以添加顏料、填充劑、分散劑、增塑劑、紫外線吸收劑、表面活性劑、抗氧化劑、觸變劑等。上述 20 200838700 添加劑可以單獨使用1種，也可以並用2種以上。在上述透明塑膠薄膜基材上塗布上述硬塗層形成材料的方法可以使用，例如，喷射塗布法、擠壓式塗布（die coatin&)法疑轉塗布法、喷霧塗布法、凹版塗布法、輥塗 5布法、刮棒塗布法等塗布法。塗布上述硬塗層形成材料，在上述透明塑膠薄膜基材上形成塗膜。 • 接著，使上述塗膜硬化。在上述硬化前，最好使上述塗膜乾燥。例如，上述塗膜可以自然乾燥，也可以利用吹 10風來風乾，也可以加熱乾燥，也可以是組合這些的方法。上述塗膜的硬化手段沒有特別的限制，而上述硬化手段最好是紫外線硬化或電離放射線硬化。上述硬化手段中可以使用各種活性能量，且上述活性能量最好是紫外線。能量線源最好是，例如，高壓水銀燈、鹵素燈、氙燈、金 15屬函素燈、氮雷射、電子束加速裝置、放射性元素等線源。 ® 以备、外線波長為365nm的累積曝光量計，上述能量線源的照射量最好是50〜5000mJ/cm2。如果上述照射量是5〇mJ/cm2 以上，則硬化變得更充分，且所形成的上述硬塗層硬度也受件更充分。如果上述照射量是5〇〇〇mJ/cm2以下，則可以 20防止所形成的上述硬塗層著色，可以使透明性提高。在上述硬化中，上述塗膜的寬度方向的硬化收縮力如上所述。另外，上述塗膜的寬度方向的硬化收縮率是例如 0.2%以上的範圍，且以0.3%以上的範圍為佳，〇4%以上的範圍更佳。上述塗膜的寬度方向的硬化收縮力和硬化收縮 21 200838700 率會因上述硬塗層形成材料的組成(上述硬塗樹脂、溶劑、添加劑的種類和混合比等）不同而不同，而上述塗膜厚声越厚，則硬化收縮力和硬化收縮率越大。另外，上述塗膜的寬度方向的硬化收縮力和硬化收縮率可以通過例如調整上 5述硬塗層形成材料的組成、調整上述塗臈厚度(硬塗層的厚度）等來調節，對於發明所屬技術領域中具通常知識者來說，不需進行過度的嘗試錯誤，便可以容易地得到具有上 ❿ 述物性(硬化收縮力、硬化收縮率等）的塗膜。因此，在本發明的硬塗薄膜之製造方法中，如上所述，可調整上述硬塗 10層厚度(A)和上述透明塑膠薄膜基材厚度(B)之至少一者，使得上述硬塗層厚度(A)和上述透明塑膠薄膜基材厚度(B)之比(A/B)為1/2.6以上。在本發明中，上述硬塗層厚度的調整可以藉由調整上述塗膜的厚度來進行。即，藉由調整上述塗膜厚度，可以調整作為其硬化物的上述硬塗層厚度。即， 15對於發明所屬技術領域中具通常知識者來說，就可以輕易鲁握上述塗膜厚度和上述硬塗層厚度的關係，不需進行過度的嘗試錯誤，就可以實現本發明的硬塗層厚度。另外， T為硬塗層極薄，所以可以將上述塗膜厚度和上述硬塗層厚度視作為相同（塗膜厚度，塗層厚度）。藉由調整上述比 20 ’上述透明塑膠薄膜基材變成具有與上述塗膜的收 . ，起&見度方向收縮的厚度。結果，因為硬塗薄膜整體 /口見度方向上收縮，所以能夠防止硬塗薄膜發生捲曲和斷裂。 H乂上的操作’藉由在上述透明塑膠薄膜基材之至 22 200838700 少一個面上形成上述硬塗層，可以製造本發明的硬塗薄膜。本發明的硬塗薄膜的硬度沒有特別的限制，例如以錯 ♦ 筆硬度計可以是例如4H以上。第1圖是表示本發明的硬塗薄膜一個例子的剖面示意 5圖。如第1圖中所示，該例子的硬塗薄膜3包含透明塑膠薄膜基材1，在該透明塑膠薄膜基材1的單個表面上形成硬塗層2。本發明不限定於第1圖的結構，硬塗薄膜也可以包含 ^ 透明塑膠薄膜基材1，並在其兩面上形成硬塗層2。該例子的硬塗層2是單層的。但是，本發明不限定於此，上述硬塗 10層2也可以是層疊2層以上的多層結構。上述硬塗層為了使其表面結構為凹凸結構，也可以含有微粒。這是因為如果將上述硬塗層的表面結構製成凹凸結構，就可以賦予防眩性。上述微粒包括，例如，無機微粒和有機微粒。上述無機微粒沒有特別的限定。上述無機 15微粒包括例如：氧化石夕齡、氧化鈦微粒、氧化紹微粒、 _ t化鋅聽、氧化錫餘、碳目_微粒、硫酸鋇微粒、滑石粉微粒、高嶺土微粒、硫酸辦微粒等。上述有機微粒沒有特別的限定。上述有機微粒包括例如：聚甲基丙稀酸甲酯樹脂粉末(PMMA微粒）、聚石夕氧樹脂粉末、聚笨乙稀樹脂 • 20粉末、聚碳酸輯脂粉末、丙稀酸笨乙烯樹脂粉末、苯並 m胺樹脂粉末、三聚氰胺樹脂粉末1烯烴樹脂粉末、聚 _脂粉末、？長醯胺樹脂粉末、聚醯亞胺樹脂粉末、聚氣乙烯樹脂粉末等。這些無機微粒和有機微粒可以單獨使用i 種，也可以並用2種以上。 23 200838700 上述微_形狀沒有特職_。上述㈣的形狀例如可以是珠粒狀的大致球形。例如，上述微粒的形狀也可 . 从粉料蚊_雜。上额_重量平均粒徑是例如1〜的範圍，且以2〜2G㈣的範圍為佳，上述微粒 5宜為大致球形的微粒，且以展弦比紅5以下的大致球形的微粒更佳。上述微粒的混合比沒有特別的限制。上述微粒的混合 • &例可以適當地設定。相對於⑽重量份上述硬塗層形成材料’上述微粒的混合比例是例如2，重量份的範圍，且以 10 1〜50重量份的範圍為佳。從防止在上述微粒和上述硬塗層的介面産生光散射和干涉條紋等觀點出發，最好減小上述微粒和上述硬塗層的折射率差。上述干涉條紋是射入硬塗薄膜中的外光的反射光呈現出虹的顏色的色相的現象。最近，在辦公室等中，夕使用月冗性優異的二波長螢光燈。在上述三波長螢光 _ \下$上述干'歩條紋顯著地顯現。因為上述硬塗層的折射系疋在1.4〜1.6的範圍，所以最好具有接近該折射率範圍的折射率的微粒。上述微粒和上述硬塗層的折射率之差最好小於〇.〇5。 • 第2圖疋顯不具有被軾予了防眩性的硬塗層的本發明的硬塗薄膜的-個例子的剖面示意圖。在第2圖中，對和第 1圖相同的部分標註相同的符號。如第2圖中所示，本例的 =薄膜5的硬塗層2包含微粒4，上述硬塗層2的表面為凹凸、、.構。如果上述硬塗層2的表面是凹凸結構，可以發揮防 24 200838700 眩性（防眩光性）。本例子的硬塗薄膜除了上述硬塗層的表面是凹凸結構以外，其他和第1圖的硬塗薄膜相同。在本發明的硬塗薄膜中，在上述硬塗層上也可以形成防反射層（低折射率層）。第3圖是顯示具有上述防反射層的 5本發明的硬塗薄膜的一個例子的剖面示意圖。在第3圖中，對和第2圖相同的部分標註相同的符號。如第3圖中所示，本例子的硬塗薄膜7是在表面為凹凸結構的硬塗層2上形成防反射層(低折射率層）6的結構，其他結構與第2圖中所示的硬塗薄膜相同。當光照射到物體上時，在其介面上發生的 10反射、在内部發生的吸收、散射的現象反覆進行，從物體背面透過去。例如，在圖像顯示裝置中安裝有硬塗薄膜時，在空氣和硬塗層介面的光反射增加，成為使圖像的視覺辨認性下降的主要原因之一，而防反射層係使其表面反射下降者。另外，如在第3圖中所示的硬塗薄膜7中，防反射層6 15是單層。但是，本發明不限於此。上述防反射層6也可以是層疊2層以上的多層結構。在本發明中，上述防反射層是將嚴密控制了厚度和折射率的光學薄膜或上述光學薄膜層疊2層以上而得到者。上述防反射層利用光的干涉效應將入射光和反射光反轉的相 20 位互相抵消而顯現防反射功能。例如，使上述防反射功能顯現的可見光線的波長區域是380〜780nm，特別是可見度高的波長區域是450〜650nm的範圍。上述防反射層最好設計成使其中心波長，即550nm的反射率為最小。在基於光的干涉效應的上述防反射層的設計中，作為 25 200838700 使其干涉效果提南的手段包括，例如，增大上述防反射層和上述硬塗層的折射率差的方法。一般來說，在層疊2至5 層的光學薄層（嚴密控制了厚度和折射率的薄膜)而成的結構的多層防反射層中，僅以預定厚度將折射率不同的成分 5形成為多數層。因此，上述防反射層的光學設計自由度提高，可以使防反射效果進一步提高，分光反射特性在可見光區域也能夠變得均勻（平坦）。在上述光學薄膜中要求高的 Φ 厚度精度。因此，各層的形成一般是以乾式的真空蒸鍍、濺射、CVD等實施。 10 上述多層防反射層宜為在折射率高的氧化鈦層（折射率為約1·8)上層疊折射率低的氧化矽層（折射率為約145)而成的2層結構的防反射層。更佳的是在氧化鈦層上層疊氧化矽層、在氧化矽層上層疊另外的氧化鈦層、在另外的氧化鈦層上層疊另外的氧化矽層而成的四層結構防反射層。藉 15由形成這些二層防反射層或四層防反射層，能夠均勻地降鲁低可見光線的波長區域(例如380〜780nm的範圍）的反射。藉由在上述硬塗層上形成單層的光學薄膜（防反射層），也能狗顯現出防反射效果。一般來說，在單層防反射層的形成時採用例如濕式的噴射塗布（f〇untain c〇ating)、擠 20壓式塗布、旋轉塗布、喷霧塗布、凹版塗布、報塗布、刮棒塗布等塗布法。上述單層防反射層的形成材料包括例如：紫外線硬化型丙烯酸樹脂等樹脂類材料；使膠體二氧化矽等無機微粒分散在樹脂中而得到的混合系材料；使用四乙氧基矽烷、 26 200838700 四乙氧基鈦等燒氧基金屬鹽的溶膠一凝膠類材料等。為了賦予表面防污染性，最好在上述形成材料中含有氟基。基於耐擦傷性等理由，上述形成材料最好是無機成分含量多的形成材料，且更佳的是上述溶膠一凝膠類材料。上述溶 5膠一凝膠系材料可以部分縮合後使用。In the above hard coat forming material, various reactive dilutions of 5 agents may be added. The above reactive diluent is not particularly limited. The above reactive diluent includes, for example, a relatively low viscosity of hexamethylene glycol diacrylate, Μ-hexanediol dimethyl acrylate vinegar, tripropylene glycol diacrylate vinegar, tripropylene glycol dimethyl propylene glycol acid, Diethylene glycol diacrylic acid vinegar, diethylene glycol dimethacrylate dragon, hexanediol acrylic acid, hexanediol methyl acrylate vinegar, quaternary W pentaerythritol triacrylate cool, pentaerythritol three Methyl acrylate vinegar, trimethoprim triacetate vinegar, trimethyl methacrylate trimethyl acrylate vinegar, dipentaerythritol octa acrylate vinegar, dipentaerythritol hexamethacrylate vinegar, neopentyl glycol - A bifunctional or higher monomer such as propylene fluorene or neopentyl glycol dimethacrylate vinegar. The above reactive diluent also includes, for example, a fluorene-ethylene group as a monofunctional monomer, a ketone, an acrylic acid, a propyl acrylate, a propyl acrylate, a methacrylic acid, a methyl acrylate. Acrylic, isopropyl methacrylate, methacrylic acid butyl, methyl propylene hexanoic acid, methacrylic acid octacycline @ 曱曱 propyl ketone 2 - ethyl acetonate, methyl Methyl acrylate acrylate such as cyclohexyl acrylate or decyl phenyl methacrylate; tetramethyl sulfonate 20 vaginal acid and its internal vinegar modified product, styrene, methyl Styrene, acrylic acid, and the like, and mixtures thereof and the like. If necessary, pigments, fillers, dispersants, plasticizers, ultraviolet absorbers, surfactants, antioxidants, and thixotropic agents may be added to the I-formed material of the above-mentioned hard coat layer insofar as the performance is not impaired. Wait. The above-mentioned 20 200838700 additives may be used alone or in combination of two or more. A method of applying the hard coat layer forming material to the transparent plastic film substrate may be, for example, a spray coating method, a die coating method, a spray coating method, a gravure coating method, or the like. A coating method such as a roll coating method or a bar coating method. The hard coat layer forming material is applied to form a coating film on the transparent plastic film substrate. • Next, the coating film is cured. Preferably, the coating film is dried before the hardening. For example, the above-mentioned coating film may be naturally dried, or may be air-dried by blowing 10 winds, or may be dried by heating, or may be a combination of these. The hardening means of the above coating film is not particularly limited, and the hardening means is preferably ultraviolet curing or ionizing radiation hardening. Various kinds of active energy can be used in the above hardening means, and the above-mentioned active energy is preferably ultraviolet light. The source of the energy source is preferably, for example, a high-pressure mercury lamp, a halogen lamp, a xenon lamp, a gold-based lamp, a nitrogen laser, an electron beam acceleration device, a radioactive element, or the like. The cumulative amount of the above-mentioned energy source is preferably 50 to 5000 mJ/cm 2 in terms of a cumulative exposure meter having an external line wavelength of 365 nm. If the above irradiation amount is 5 〇 mJ/cm2 or more, the hardening becomes more sufficient, and the hardness of the hard coat layer formed is also more sufficient. When the irradiation amount is 5 〇〇〇 mJ/cm 2 or less, the formation of the hard coat layer can be prevented from being colored, and the transparency can be improved. In the above hardening, the curing shrinkage force in the width direction of the coating film is as described above. Further, the curing shrinkage ratio in the width direction of the coating film is, for example, in the range of 0.2% or more, preferably in the range of 0.3% or more, and more preferably in the range of 〇4% or more. The curing shrinkage force and the curing shrinkage 21 in the width direction of the coating film are different depending on the composition of the hard coat layer forming material (the type of the hard coating resin, the solvent, the type of the additive, the mixing ratio, etc.), and the coating film is different. The thicker the thicker, the greater the hardening shrinkage and hardening shrinkage. Further, the curing shrinkage force and the curing shrinkage ratio in the width direction of the coating film can be adjusted by, for example, adjusting the composition of the hard coat layer forming material described above, adjusting the thickness of the coating layer (thickness of the hard coat layer), and the like. A person having ordinary skill in the art can easily obtain a coating film having a physical property (hardening shrinkage force, hardening shrinkage ratio, etc.) without excessive trial error. Therefore, in the method for producing a hard coat film of the present invention, as described above, at least one of the hard coat 10 layer thickness (A) and the transparent plastic film substrate thickness (B) may be adjusted such that the hard coat layer is formed. The ratio (A/B) of the thickness (A) to the thickness (B) of the above transparent plastic film substrate is 1/2.6 or more. In the present invention, the adjustment of the thickness of the hard coat layer can be carried out by adjusting the thickness of the coating film. Namely, by adjusting the thickness of the coating film described above, the thickness of the hard coat layer as the cured product can be adjusted. That is, 15 for the person having ordinary knowledge in the technical field of the invention, the relationship between the thickness of the above coating film and the thickness of the hard coating layer can be easily grasped, and the hard coating of the present invention can be realized without excessive trial error. Layer thickness. Further, since T is extremely thin, the thickness of the above coating film and the thickness of the above-mentioned hard coat layer can be regarded as the same (coating film thickness, coating thickness). By adjusting the above ratio of 20', the transparent plastic film substrate becomes a thickness which shrinks in the direction of the coating film and the viewing direction. As a result, since the hard coat film is contracted in the overall/visibility direction, it is possible to prevent the hard coat film from being curled and broken. Operation on H乂 The hard coat film of the present invention can be produced by forming the above hard coat layer on one surface of the above transparent plastic film substrate to 22 200838700. The hardness of the hard coat film of the present invention is not particularly limited, and may be, for example, 4H or more in terms of a pen hardness. Fig. 1 is a schematic cross-sectional view showing an example of a hard coat film of the present invention. As shown in Fig. 1, the hard coat film 3 of this example comprises a transparent plastic film substrate 1 on which a hard coat layer 2 is formed on a single surface of the transparent plastic film substrate 1. The present invention is not limited to the structure of Fig. 1, and the hard coat film may also comprise a transparent plastic film substrate 1 and a hard coat layer 2 formed on both sides thereof. The hard coat layer 2 of this example is a single layer. However, the present invention is not limited thereto, and the hard coat layer 10 may have a multilayer structure in which two or more layers are laminated. The hard coat layer may contain fine particles in order to make the surface structure into a concave-convex structure. This is because if the surface structure of the above hard coat layer is made into a concave-convex structure, the anti-glare property can be imparted. The above microparticles include, for example, inorganic microparticles and organic microparticles. The above inorganic fine particles are not particularly limited. The inorganic 15 fine particles include, for example, an oxidized stone age, a titanium oxide fine particle, a oxidized fine particle, a zinc oxide, a tin oxide residue, a carbon mesh particle, a barium sulfate particle, a talc powder particle, a kaolin particle, a sulfuric acid particle, or the like. . The above organic fine particles are not particularly limited. The above organic fine particles include, for example, polymethyl methacrylate resin powder (PMMA microparticles), polyoxin resin powder, polystyrene resin, 20 powder, polycarbonate powder, acrylic acid stupid resin powder. , benzomamine resin powder, melamine resin powder 1 olefin resin powder, poly-lipid powder, ? Long amide resin powder, polyimide resin powder, polyethylene resin powder, and the like. These inorganic fine particles and organic fine particles may be used singly or in combination of two or more. 23 200838700 The above micro_shape has no special _. The shape of the above (4) may be, for example, a substantially spherical shape in the form of beads. For example, the shape of the above-mentioned fine particles is also possible. The upper weight-weight average particle diameter is, for example, in the range of 1 to 2, and preferably in the range of 2 to 2 G (d), and the fine particles 5 are preferably substantially spherical fine particles, and more preferably have substantially spherical fine particles having an aspect ratio of red or less. The mixing ratio of the above fine particles is not particularly limited. The mixing of the above particles can be appropriately set. The mixing ratio of the above fine particles with respect to (10) parts by weight of the above-mentioned hard coat layer forming material is, for example, in the range of 2 parts by weight, and preferably in the range of 10 1 to 50 parts by weight. From the viewpoint of preventing light scattering and interference fringes on the interface between the fine particles and the hard coat layer, it is preferable to reduce the difference in refractive index between the fine particles and the hard coat layer. The interference fringe described above is a phenomenon in which the reflected light of the external light incident into the hard coat film exhibits a hue of a rainbow color. Recently, in an office or the like, a two-wavelength fluorescent lamp having excellent monthly redundancy is used. In the above three-wavelength fluorescence _ \ the above-mentioned dry '歩 stripes appear remarkably. Since the refractive index of the above hard coat layer is in the range of 1.4 to 1.6, it is preferable to have fine particles having a refractive index close to the refractive index range. The difference in refractive index between the above fine particles and the above hard coat layer is preferably less than 〇.〇5. • Fig. 2 is a schematic cross-sectional view showing an example of the hard coat film of the present invention which does not have a hard coat layer which is antiglare. In Fig. 2, the same portions as those in Fig. 1 are denoted by the same reference numerals. As shown in Fig. 2, the hard coat layer 2 of the film 5 of this example contains the fine particles 4, and the surface of the hard coat layer 2 is concave and convex. If the surface of the hard coat layer 2 is a concave-convex structure, it can exhibit glare (anti-glare). The hard coat film of the present example is the same as the hard coat film of Fig. 1 except that the surface of the hard coat layer is a concave-convex structure. In the hard coat film of the present invention, an antireflection layer (low refractive index layer) may be formed on the hard coat layer. Fig. 3 is a schematic cross-sectional view showing an example of a hard coat film of the present invention having the above antireflection layer. In the third embodiment, the same portions as those in Fig. 2 are denoted by the same reference numerals. As shown in FIG. 3, the hard coat film 7 of the present example has a structure in which an antireflection layer (low refractive index layer) 6 is formed on the hard coat layer 2 having a textured structure on the surface, and other structures are as shown in FIG. The hard coat film is the same. When light is irradiated onto an object, the phenomenon of 10 reflection occurring on the interface, absorption and scattering occurring inside is repeated, and is transmitted from the back surface of the object. For example, when a hard coat film is mounted on an image display device, light reflection on the air and hard coat layer interface increases, which is one of the main causes of degrading the visibility of an image, and the antireflection layer is a surface thereof. The reflection is reduced. Further, as in the hard coat film 7 shown in Fig. 3, the antireflection layer 615 is a single layer. However, the invention is not limited thereto. The antireflection layer 6 may have a multilayer structure in which two or more layers are laminated. In the present invention, the antireflection layer is obtained by laminating two or more optical films or optical films having a thickness and a refractive index tightly controlled. The anti-reflection layer uses the interference effect of light to cancel the phase 20 of the incident light and the reflected light, thereby exhibiting an anti-reflection function. For example, the wavelength region of the visible ray that causes the anti-reflection function to appear is 380 to 780 nm, and particularly, the wavelength region where the visibility is high is in the range of 450 to 650 nm. The antireflection layer is preferably designed such that its central wavelength, i.e., the reflectance at 550 nm, is minimized. In the design of the above-described antireflection layer based on the interference effect of light, the means for making the interference effect of 25 200838700 include, for example, a method of increasing the refractive index difference between the antireflection layer and the hard coat layer. In general, in a multilayer antireflection layer having a structure in which two to five optical thin layers (thickness in which thickness and refractive index are tightly controlled) are laminated, a component 5 having a different refractive index is formed into a plurality of only a predetermined thickness. Floor. Therefore, the optical design freedom of the above-mentioned antireflection layer is improved, the antireflection effect can be further improved, and the spectral reflection characteristic can be made uniform (flat) in the visible light region. High Φ thickness accuracy is required in the above optical film. Therefore, the formation of each layer is generally carried out by dry vacuum deposition, sputtering, CVD, or the like. The above-mentioned multilayer antireflection layer is preferably a two-layer anti-reflection layer in which a ruthenium oxide layer having a low refractive index (refractive index of about 145) is laminated on a titanium oxide layer having a high refractive index (refractive index of about 1.8). Floor. More preferably, a four-layered antireflection layer is formed by laminating a ruthenium oxide layer on a titanium oxide layer, laminating another titanium oxide layer on the ruthenium oxide layer, and laminating another ruthenium oxide layer on the other titanium oxide layer. By forming these two antireflection layers or four antireflection layers, it is possible to uniformly reduce the reflection of the wavelength region of the visible light (for example, a range of 380 to 780 nm). By forming a single-layer optical film (anti-reflection layer) on the above hard coat layer, the dog can also exhibit an anti-reflection effect. In general, in the formation of a single-layer anti-reflective layer, for example, wet spray coating, extrusion coating, spin coating, spray coating, gravure coating, coating, and scraping Coating method such as coating. The material for forming the single-layer antireflection layer includes, for example, a resin material such as an ultraviolet curable acrylic resin; a mixed material obtained by dispersing inorganic fine particles such as colloidal ceria in a resin; and using tetraethoxydecane, 26 200838700 A sol-gel type material such as an alkoxy metal salt such as tetraethoxytitanium. In order to impart surface contamination resistance, it is preferred to contain a fluorine group in the above-mentioned forming material. The above-mentioned forming material is preferably a forming material having a large content of an inorganic component, and more preferably a sol-gel type material, for the purpose of scratch resistance or the like. The above gel-gel-gel material can be partially condensed and used.

上述防反射層（低折射率層）最好是由含有以乙二醇換算計的數平均分子量為·〜1G_㈣的⑦纽低聚物；和以聚苯乙烯換算計的數平均分子量為5_以上、具有氣烷基結構和聚石夕氧烧結構的氟化合物的材料（在特開編 10 1678275虎公報中記載的材料)形成的防反射層，藉此可以兼顧耐擦傷性和低反射等。在上述防反射層（低折射率層）中，為了提高膜強度，也可以含有無機溶膠，上述無機溶膠沒有特勿的限定。上述無機溶膠包括例如二氧化石夕、氧化銘、氟化鎂等。其中， Μ以二氧化石夕凝膠為佳。相對於刚重量份上述防反射層形成材料的全部固體成分，上述無機凝膠的混合比例是例如10 〜80重量份的範圍。上述無機凝膠中的無機微粒粒徑以2〜 5〇邮的範圍為佳，且以5〜3〇nm的範圍更佳。 20 *上述防反射層㈣成材财，最好含有中空且球狀、乳切超微粒子。上魏切超錄子的平均粒徑是$〜二且以1〇〜2°°啲的範圍更佳。上述氧切 ^粒子疋在具有細孔的外殼的内部形成有空洞的中空球體之=空Γ含t錢切超微粒子製備時的溶劑和氣體之至V-者。另外，用於形成上述氧切超微粒子的上 27 200838700 述空洞的前驅體物質最好殘留在上述空洞内。上述外私的厚度是卜知邮左右的範圍，並且最好是上述氧化石夕超ς粒 . ㈣料粒徑的1/50〜1/5左右的範圍。上述外殼最好是由多個覆盍層形成。在上述氧化石夕超微粒子中，最好上述七 .5㈣雜、且上述空減上述外殼縣。這是因為在上述防反射層中，維持上述氧化石夕超微粒子的多孔質或*同，可能會使以防反射層的折射率進—步降低。這樣的中空 • 纟球狀的氧切超微粒子之製造方法適合採用例如在特開 2000-23則號公報中揭示的二氧化㈣微粒之製造方 10 法。形成上述防反射層（低折射率層）時的乾燥和硬化的溫度沒有特別的限制。例如，上述乾燥和硬化的溫度是60〜 15〇°C的範圍、最好是70〜130°C的範圍，上述乾燥和硬化的時間是齡1〜3G分鐘的範®，在考慮生錄的情況下， 15最好是1〜1〇分鐘的範圍。另外，上述乾燥和硬化後，藉由 • ㊆一錢行加熱處理’可以得到具有防反射層的高硬i的硬塗薄膜。上述加熱處理的溫度沒有特別的限制。上述加減理的溫度是例如4〇〜13代的範圍，最好是％〜⑽。C 的範圍。上述加熱處理的時間沒有特別的限制。上述加熱 20處理的時間例如是1分鐘〜刚小時，從提高耐擦傷性的觀 .點㈣’以進行叫如上加減理更佳。上述加熱處理可以藉由使用電熱板、㈣t、帶式爐等的方法來實施。在圖像顯不衣置中安裝具有上述防反射層的硬塗薄膜時’上述防反射層成為最外層的頻率高。因此，上述防反 28 200838700 射層容易受到來自外部環境的污染。相較於單純的透明板等，上述防反射層的污染容易變得明顯。上述防反射層由於附著例如指紋、手垢、汗和整髮劑等污染物而發生表面反射率變化，有時附著物發白地浮現出來而使顯示内^變 5得不夠鮮明。為了提高防止上述污染物附著和除去附著的上述污染物的容易性，最好在上述防反射層上層疊由含氟基的矽烧系化合物或含氟基的有機化合物等形成的防污染層。在本發明的硬塗薄膜中，最好對上述透明塑膠薄膜基 10材和上述硬塗層之至少一者進行表面處理。如果對上述透明塑膠薄膜基材進行表面處理，就可以進一步提高與上述硬塗層、偏光元件或偏光板的密著性。另外，如果對上述硬塗層表面進行表面處理，就可以進一步提高與上述防反射層、偏光元件或偏光板的密著性。上述表面處理可舉例 15如：低壓電漿處理、紫外線照射處理、電暈處理、火焰處理、酸或鹼處理。作為上述透明塑膠薄膜基材，使用TAC 膜時的表面處理最好為驗處理。例如，該鹼處理可以在使 TAC膜表面接觸鹼溶液後，進行水洗並乾燥來實施。例如，上述驗溶液可以使用氫氧化鉀溶液、氫氧化鈉溶液。上述 20 鹼溶液的氫氧化物離子的規定濃度（摩爾濃度）以0.1〜 3.0N(mol/L)的範圍為佳、且以〇·5〜2.0N(mol/L)的範圍更佳。本發明的硬塗薄膜通常可以透過黏合劑和黏接劑將上述透明塑膠薄膜基材一側貼合在LCD和ELD中使用的光學 29 200838700 構件上。在該貼合時，對上述透明塑膠薄膜基材表面也可以進行上述的各種表面處理。The antireflection layer (low refractive index layer) is preferably a 7-Nu oligomer having a number average molecular weight of -1 G_(iv) in terms of ethylene glycol; and a number average molecular weight of 5 _ in terms of polystyrene The antireflection layer formed of the material of the fluorine compound having a gas-alkyl structure and a polyoxo-oxygen structure (the material described in JP-A No. 10 1678275), thereby achieving both scratch resistance and low reflection. . In the antireflection layer (low refractive index layer), an inorganic sol may be contained in order to increase the film strength, and the inorganic sol is not particularly limited. The above inorganic sol includes, for example, sulphur dioxide, oxidized, magnesium fluoride, and the like. Among them, strontium dioxide is preferred. The mixing ratio of the inorganic gel is, for example, in the range of 10 to 80 parts by weight, based on the total solid content of the material of the antireflection layer forming material. The inorganic fine particles in the inorganic gel preferably have a particle diameter of 2 to 5 Å, and more preferably 5 to 3 Å. 20 * The above anti-reflective layer (4) is a material, preferably containing hollow and spherical, milk-cut ultrafine particles. The average particle size of the upper Wei cut ultra-recorder is $~2 and the range of 1〇~2°°啲 is better. The above oxygen cleaved particle enthalpy is formed in a hollow sphere having a void inside the outer shell having pores = the space containing the solvent and the gas to the V- when the ultrafine particles are prepared. Further, it is preferable that the precursor material for forming the above-mentioned oxygen-cut ultrafine particles of the above-mentioned oxygen-cut ultrafine particles remains in the above-mentioned cavity. The thickness of the above-mentioned outer private is the range around the Buchi Post, and it is preferable that the above-mentioned oxidized stone is ultra-fine granules. (4) The range of the material particle diameter is about 1/50 to 1/5. Preferably, the outer casing is formed of a plurality of covering layers. In the above-mentioned oxidized stone ultrafine particles, it is preferable that the above-mentioned seven to five (four) impurities are mixed with the above-mentioned shell county. This is because, in the above-mentioned antireflection layer, maintaining the porosity or the like of the above-mentioned oxidized oxide ultrafine particles may cause the refractive index of the antireflection layer to be further lowered. The method for producing such hollow hollow spheroidal oxygen-cut ultrafine particles is suitably carried out, for example, in the method of producing the oxidized (tetra) fine particles disclosed in Japanese Laid-Open Patent Publication No. 2000-23. The temperature of drying and hardening when the above antireflection layer (low refractive index layer) is formed is not particularly limited. For example, the drying and hardening temperature is in the range of 60 to 15 ° C, preferably 70 to 130 ° C, and the drying and hardening time is a range of 1 to 3 G minutes, considering the birth record. In the case, 15 is preferably a range of 1 to 1 minute. Further, after the above drying and hardening, a hard coating film having a high hardness i having an antireflection layer can be obtained by heat treatment of ? The temperature of the above heat treatment is not particularly limited. The temperature of the above addition and subtraction is, for example, a range of 4 〇 to 13 generations, preferably % to (10). The scope of C. The time of the above heat treatment is not particularly limited. The time for the above-described heating treatment is, for example, 1 minute to just hour, and it is more preferable to perform the above-mentioned addition and subtraction from the viewpoint of improving the scratch resistance. The above heat treatment can be carried out by a method using a hot plate, a (d) t, a belt furnace or the like. When the hard coat film having the above antireflection layer is mounted in the image display device, the frequency at which the antireflection layer becomes the outermost layer is high. Therefore, the above-mentioned anti-reverse 28 200838700 shot layer is susceptible to contamination from the external environment. The contamination of the above-mentioned antireflection layer is likely to be conspicuous compared to a simple transparent plate or the like. The above-mentioned antireflection layer undergoes a change in surface reflectance due to adhesion of contaminants such as fingerprints, hand scale, sweat, and hair styling agents, and sometimes the deposits appear whitish and the display is not sufficiently sharp. In order to improve the easiness of preventing the above-mentioned contaminants from adhering and removing the adhered contaminants, it is preferable to laminate an anti-contamination layer formed of a fluorine-based antimony-based compound or a fluorine-containing organic compound or the like on the antireflection layer. In the hard coat film of the present invention, at least one of the above transparent plastic film base material and the hard coat layer is preferably subjected to surface treatment. When the transparent plastic film substrate is surface-treated, the adhesion to the hard coat layer, the polarizing element or the polarizing plate can be further improved. Further, if the surface of the hard coat layer is subjected to surface treatment, the adhesion to the above-mentioned antireflection layer, polarizing element or polarizing plate can be further improved. The above surface treatment can be exemplified by low pressure plasma treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, acid or alkali treatment. As the transparent plastic film substrate, the surface treatment when the TAC film is used is preferably an inspection treatment. For example, the alkali treatment can be carried out by bringing the surface of the TAC film into contact with an alkali solution, washing with water, and drying. For example, a potassium hydroxide solution or a sodium hydroxide solution can be used for the above test solution. The predetermined concentration (molar concentration) of the hydroxide ions of the above 20 alkali solution is preferably in the range of 0.1 to 3.0 N (mol/L), and more preferably in the range of 〇 5 to 2.0 N (mol/L). The hard coat film of the present invention can usually be attached to the optical 29 200838700 member used in the LCD and ELD by a side of the transparent plastic film substrate through an adhesive and an adhesive. At the time of the bonding, the above various surface treatments can be performed on the surface of the above transparent plastic film substrate.

上述光學構件可舉偏光元件或偏光板為例。偏光板包含偏光元件，一般使用在上述偏光元件的一側或兩側上形 5 成透明保護膜者。在上述偏光元件的兩面上設置透明保護膜時，正面和背面的保護膜可以是相同的材料、也可以是不同的材料。偏光板通常被配置在液晶單元的兩侧，且偏光板被配置成使2片偏光板的吸收轴相互大致垂直。接著，對層疊了本發明的硬塗薄膜的光學構件，以偏 1〇光板為例進行說明。使用黏合劑和黏接劑等，將本發明的硬塗薄膜和偏光元件或偏光板層疊，可以得到具有本發明功能的偏光板。上述偏光兀件沒有特別的限定。上述偏光元件可以舉例如：於聚乙烯醇系膜、部分甲縮駿化聚乙稀醇系膜、乙 15烯-乙酸乙烯酿共聚物系部分皂化膜等親水性高分子膜上吸附破和雙色性染料等雙色性物質後單軸拉伸而得者；聚乙烯醇的脫水處理物和聚氣乙烯的脫鹽酸處理物等的聚婦系取向膜#纟中，由聚乙烯醇系膜和峨等雙色性物質组成的偏光元件的偏振雙色比高，故較為理想。上述偏光元如件厚度沒有特別的限制，上述偏光元件厚度是例如$〜 m左六。龜例如-將*㈣醇㈣料染色錢行單軸拉伸而得中而^①件可"^由將聚乙騎系膜浸潰在㈣水溶液中而仏且拉伸到原始長度的3〜7倍來製作铺需要， 30 200838700 上述碘的水溶液也可以含有硼酸和硫酸鋅、氯化鋅等。又，也可以另外在含有硼酸和硫酸鋅、氯化鋅等的水溶液中， ^ 浸潰聚乙烯醇系膜。根據需要，在染色前，也可以將聚乙烯醇系膜輯在水巾，進行水洗。藉由水洗聚⑽醇系膜， 5可以洗滌聚乙烯醇系膜表面的汙物和防黏連劑，此外也具有透過使聚乙烯醇系膜膨潤，防止染色不均等不均勻的效果。拉伸可以在用碘染色後進行，也可以邊染色邊拉伸， Φ 還也可以在拉伸後用碘染色。也可以在硼酸和碘化鉀等的水溶液中或水浴中拉伸。 10 在上述偏光元件的單面或兩面設置的透明保護膜最好是透明性、機械強度、熱穩定性、水分遮蔽性、相位差值的穩定性等優異者。形成上述透明保護膜的材料例如可舉和上述透明塑膠薄膜基材同樣的材料為例。上述透明保護膜可舉在特開2〇〇1 一 343529號公報 15 (WO01/37⑼7)中記載的高分子膜為例。例如，在上述公報 # 中記載的高分子膜可以舉例如由含有（A)在側鏈上具有取The optical member may be exemplified by a polarizing element or a polarizing plate. The polarizing plate includes a polarizing element, and generally a transparent protective film is formed on one side or both sides of the above polarizing element. When a transparent protective film is provided on both surfaces of the above polarizing element, the front and back protective films may be the same material or different materials. The polarizing plates are usually disposed on both sides of the liquid crystal cell, and the polarizing plates are arranged such that the absorption axes of the two polarizing plates are substantially perpendicular to each other. Next, an optical member in which the hard coat film of the present invention is laminated will be described by taking a polarizing plate as an example. The hard coat film of the present invention and a polarizing element or a polarizing plate are laminated by using a binder, an adhesive or the like to obtain a polarizing plate having the function of the present invention. The above polarizing element is not particularly limited. The polarizing element may be, for example, adsorbed on a hydrophilic polymer film such as a polyvinyl alcohol-based film, a partially condensed polyethylene-based film, or a partially saponified film of an ethylene-vinylene-vinyl acetate-branched copolymer. A dichroic material such as a dye is uniaxially stretched; a polylactic acid-treated film such as a dehydrated material of polyvinyl alcohol or a dehydrochlorinated product of polyethene is used, and a polyvinyl alcohol film and a ruthenium are used. A polarizing element composed of a dichroic material preferably has a high polarization double color ratio. The thickness of the polarizer is not particularly limited, and the thickness of the polarizing element is, for example, $ to m left six. The turtle, for example, dyes the *(tetra) alcohol (four) material and uniaxially stretches it to obtain a medium and ^1 piece can be immersed in the (four) aqueous solution by the polytetracycline film and stretched to the original length of 3 ~7 times to make a shop, 30 200838700 The above aqueous solution of iodine may also contain boric acid, zinc sulfate, zinc chloride, and the like. Further, the polyvinyl alcohol-based film may be impregnated in an aqueous solution containing boric acid, zinc sulfate, zinc chloride or the like. If necessary, the polyvinyl alcohol-based film may be placed on a water towel and washed with water before dyeing. By washing the poly(10) alcohol-based film with water, 5 can wash the dirt and the anti-blocking agent on the surface of the polyvinyl alcohol-based film, and also has the effect of preventing the unevenness of the dyeing unevenness by swelling the polyvinyl alcohol-based film. The stretching may be carried out after dyeing with iodine, or may be carried out while dyeing, and Φ may also be dyed with iodine after stretching. It may also be stretched in an aqueous solution of boric acid or potassium iodide or in a water bath. The transparent protective film provided on one side or both sides of the above polarizing element is preferably excellent in transparency, mechanical strength, thermal stability, moisture shielding property, stability of phase difference, and the like. The material for forming the transparent protective film is exemplified by the same material as the above-mentioned transparent plastic film substrate. The polymer film described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. For example, the polymer film described in the above publication # can be obtained, for example, by containing (A) in the side chain.

代亞胺基和非取代醯亞胺基之至少一個醯亞胺基的熱塑性樹脂，和(B)在側鏈上具有取代苯基和非取代苯基之至少一個苯基以及硝基的熱塑性樹脂的樹脂組合物形成的高分 20子膜。由上述樹脂組合物形成的高分子膜可舉由異丁烯和N 一甲基馬來醯亞胺形成的交替共聚物和丙烯腈一苯乙烯共水物的樹脂組合物形成的高分子膜為例。上述高分子膜可以藉由將上述樹脂組合物押出成型為膜狀來製造。上述高分子膜因為相位差小、光彈性係數小，所以用作偏光板等 31 200838700 的保護膜時，可以消除由變形引起的不均勻等不利情況。上述岗分子膜因為透濕度小，所以加濕耐久性優異。從偏振特性和耐久性等觀點來看，上述透明保護膜以 TAC等纖維素系樹脂製造的膜和降冰片烯系樹脂製造的膜為佳。例如，上述透明保護膜的市售品可以舉例如：商品名Fujitac，，(富士膠片株式會社生産）、商品名”Ze〇n〇r，，（日本 Ze〇n公司生產）、商品名，，Arton，，(JSR社生産）等。上述透明保護膜厚度沒有特別的限制。從強度、操作性等作業性、薄層性等方面來看，上述透 10 15 20 例如1〜5叫m的範圍。如果是上述的範圍，射機械㈣保護偏光元件，且即使暴露在高溫高濕下，偏光元件也不收縮’可以保持穩定的光學特性。上述透明保護膜的厚度以5〜200/zm的範圍為佳，且以10〜H〇 — 的範圍更佳。層疊了硬塗薄膜的偏光板的結構沒有特別的限制。例如，上述偏光板可以是在硬塗薄膜上依序層疊透明㈣膜、偏光元件和透明保護膜的結構。例又上述偏先板也可以是在硬塗薄膜上依序層疊偏光元件 …旅透明保護膜而成的結構。本發明的硬塗薄膜和使用了該硬塗薄、/ 、的偏光板等各種光學元件可以在CRT、液晶顯示事晉口、、電漿顯示梦置(PDP)和電致發光顯示裝置(ELD)等各種β ^ ”、理想地使用。本發明的液晶顯示裝置& ·、示Γ使用本發明的硬塗薄膜以外，具有和以往的液晶顯示穿Wri ^ 丄又置同樣的結構。例如，可以藉由適當裝配液晶單元、低本& > 揭九板荨光學構件和根 32 200838700 據而要的照明糸統（背光等）等各結構構件，並仙& ^ 動雷路專來製造。上述液晶單元沒有特別的限制，可以如ΤΝ型、STN型、7Γ型等各種類型。用例在本發明中，液晶顯示裝置的結構沒有特別的例如，本發明的液晶顯示裝置包括在液晶單元、】側上配置了上述光學元件的液晶顯示裝置；和 ^ 々隹照明系絲中使用了背光或反射板的液晶顯示裝置等。在 A Α液晶_ 示裝置中，本發明的光學元件可以配置在液曰留 * &日日早元的—# 或兩侧上。在上述液晶單元的兩側配置上述光战- 10 15 20 予疋件時，它們可以相同，也可以不同。在上述液晶顯示# , 置中例如也可以配置擴散板、防眩光層、防反射層、保雜 :X板、後鐘陣列、透鏡陣列片、光擴散板、背光等各種光學、兄學零件。 & 實施例以下，將本發明的實施例和比較例一起進行*兒曰月是，本發明不受下述的實施例和比較例任何限定戈把，另外，在各實施例和各比較例中的各種特性和物和評價是透過下述方法實施。 ^ (硬塗層的厚度）使用Mitutoyo公司生産的微計量式厚度計剛定％ ^ 膜的整個厚度，從上述整個厚度減去透明塑膠薄膜式專度。由此算出硬塗層的厚度。厚 (硬化收縮力）如第4(A)圖所示，在透明塑膠薄膜基材1的單上塗布 33 200838700 硬塗層形成材料後，加熱乾燥而形成塗膜8。接著，從上述塗膜8切出40mmxll5mm的塗膜切片、將其作為試驗片9。接著，如第4(B)圖所示，固定上述試驗片9的一端（該圖中的左側端部），將上述試驗片9的另一端（該圖中的右側端部） 5 固定在張力測定器（數位測力計）10上，使紫外線照射面積為 40cm2。然後，藉由紫外線照射來硬化上述試驗片9，用上述張力測定器10來測定硬化收縮時的應力，從而求出硬化收縮力。 (收縮率） 10 用直尺測定塗布硬‘塗層形成材料前的透明塑膠薄膜基材寬度方向的長度(L1)。接著，在上述透明塑膠薄膜基材的單面上塗布硬塗層形成材料，再藉由紫外線照射來硬化，從而形成硬塗層。用直尺測定上述形成硬塗層後的透明塑膠薄膜基材的長度(L2)，由下式（I )求出收縮率(％)。 15 收縮率(％)= { 1 —(L2/L1) } xlOO (I) L1 :硬塗層形成前的透明塑膠薄膜的長度(mm) L2 :硬塗層形成後的透明塑膠薄膜的長度(mm) (捲曲值）從形成硬塗層後的透明塑膠薄膜基材（寬度為1330mm) 20 的一端切出在610〜710mm之間的100mm寬的硬塗薄膜切片，使用數位遊標尺測定捲曲後的上述硬塗薄膜切片的寬度(W)，由下式（π)求出捲曲值(mm)。捲曲值(mm)= 100 —W (Π) W :捲曲後的硬塗薄膜切片的寬度(mm) 34 200838700 (鉛筆硬度）將透明塑膠薄膜基材一側朝下，在玻璃板上載置硬塗薄膜。此後，按照JIS K5400記載的錯筆硬度試驗(其中荷重是500g)，對上述硬塗層表面测定鉛筆硬度。 5 (實施例1) 準備厚度為40μπι、覓度為133〇111111的丁八(：膜作為透明塑膠薄膜基材。另外，硬塗層形成材料係按照如下的方式準 φ 備··在由異三聚氰酸系丙烯酸酯、季戊四醇三丙烯酸酯、異佛酮二異氰酸醋聚胺基甲酸乙醋組成的紫外線硬化型樹 ίο脂（日本油墨化學工業社生産、商品名，，GRANDIC pCM〇7〇”) 中，以相對於每100重量份樹脂固體成分加入0·5重量份調平劑（曰本油墨化學工業社生産、商品名”grandic PC-4100 )’將由此所得的材料用乙酸乙酯稀釋成固體成分》辰度為50重1 %者。 15 在上述透明塑膠薄膜基材的單面上，從上述透明塑膠 _ ’薄膜基材的見度方向的兩側端部除去l〇mm的部分，用擠壓式塗布機塗布上述硬塗層形成材料而形成塗膜。此時，調整上述塗膜厚度使得硬塗層厚度⑷獅，。接著，藉由在100 C下加熱1分鐘，使上述塗膜乾燥。然後，用高壓水 • 20銀燈照射累肖光量為300mJ/cm2的紫外線來進行硬化處理，從而形成厚度為20的硬塗層。利用這樣的操作，製作本實％例的硬塗薄膜。在本實施例中的上述硬塗層厚度 (A)和上述透明塑膠薄膜基材厚度(b)之比(八瓜)是1/2。 (實施例2) 35 200838700 除了變更上述塗膜厚度、形成厚度為16gm的硬塗層以外，和實施例1同樣地操作，製作本實施例的硬塗薄膜。在 . 本實施例中的上述硬塗層厚度(A)和上述透明塑膠薄膜基材厚度(B)之比(A/B)是1/2.5。 5 (比較例1) 除了變更上述塗膜厚度、形成厚度為14//m的硬塗層以外，和實施例1同樣地操作，製作本比較例的硬塗薄膜。在 Φ 本比較例中的上述硬塗層厚度(A)和上述透明塑膠薄膜基材厚度(B)之比(A/B)是1/2.86。 10 (比較例2) 除了變更上述塗膜厚度、形成厚度為11 μ m的硬塗層以外，和實施例1同樣地操作，製作本比較例的硬塗薄膜。在本比較例中的上述硬塗層厚度(A)和上述透明塑膠薄膜基材厚度(B)之比(A/B)是1/3.64。 15 (比較例3) ® 除了使用厚度為80μιη、寬度為1330mm的TAC膜作為透明塑膠薄膜基材以外，和實施例i同樣地操作，製作本比較例的硬塗薄膜。在本比較例中的上述硬塗層厚度和上述透明塑膠薄膜基材厚度(B)之比(A/B)是1/4。 20 ，對由上述方式得到的實施例和比較例的各硬塗薄膜進行各種特性和物性的測定和評價，其結果顯示在下述表1 中。另外，在第5圖的曲線圖中顯示了在實施例1、2和比較例1、2中的硬塗層厚度和塗膜的寬度方向的硬化收縮力的關係。另外，在第6圖的曲線圖中顯示了在實施例1、2和比 36 200838700 較例1、2中的塗膜的寬度方向的硬化收縮力和硬塗薄膜的寬度方向的收縮率的關係。表1a thermoplastic resin of at least one quinone imine group of a substituted imido group and an unsubstituted quinone group, and (B) a thermoplastic resin having at least one phenyl group and a nitro group substituted with a phenyl group and an unsubstituted phenyl group in a side chain The resin composition formed a high score of 20 sub-films. The polymer film formed of the above resin composition is exemplified by a polymer film formed of a resin composition of an alternating copolymer of isobutylene and N-methylmaleimide and a resin composition of acrylonitrile-styrene. The above polymer film can be produced by extruding the above resin composition into a film shape. Since the above-mentioned polymer film has a small phase difference and a small photoelastic coefficient, it can be used as a protective film for a polarizing plate or the like 31 200838700, thereby eliminating disadvantages such as unevenness due to deformation. Since the above-mentioned gang film has a small moisture permeability, it is excellent in humidifying durability. The transparent protective film is preferably a film made of a cellulose resin such as TAC or a film made of a norbornene-based resin, from the viewpoints of polarization characteristics and durability. For example, the commercially available product of the above-mentioned transparent protective film may be, for example, a product name Fujitac, (produced by Fujifilm Co., Ltd.), a trade name of "Ze〇n〇r", (produced by Zezen Corporation, Japan), a trade name, Arton, (manufactured by JSR), etc. The thickness of the transparent protective film is not particularly limited. From the viewpoints of workability such as strength and workability, and thin layer properties, the above-mentioned range of 10 15 20, for example, 1 to 5 is called m. If it is the above range, the injection machine (4) protects the polarizing element, and the polarizing element does not shrink even when exposed to high temperature and high humidity, and can maintain stable optical characteristics. The thickness of the transparent protective film is in the range of 5 to 200/zm. Preferably, the range of 10 to H 〇 is more preferable. The structure of the polarizing plate on which the hard coat film is laminated is not particularly limited. For example, the polarizing plate may be a transparent (four) film laminated on the hard coat film, and polarized light. The structure of the element and the transparent protective film. The above-mentioned partial plate may be a structure in which a polarizing element, a transparent protective film, is sequentially laminated on the hard coat film. The hard coat film of the present invention is used. Various optical components such as hard-coated thin and/or polarizing plates can be ideally used in various types such as CRT, liquid crystal display, and plasma display (PDP) and electroluminescence display devices (ELD). . The liquid crystal display device of the present invention has the same structure as the conventional liquid crystal display Wri ^ 以外 except that the hard coat film of the present invention is used. For example, it is possible to assemble the liquid crystal cell, the low-end &> to uncover the nine-plate optical member, and to illuminate various structural components such as illumination systems (backlights, etc.) Dedicated to manufacturing. The liquid crystal cell is not particularly limited and may be of various types such as a ΤΝ type, an STN type, and a 7 Γ type. In the present invention, the liquid crystal display device has no particular structure. For example, the liquid crystal display device of the present invention includes a liquid crystal display device in which the optical element is disposed on the liquid crystal cell side, and is used in the illumination system. A liquid crystal display device or the like of a backlight or a reflector. In the A Α liquid crystal display device, the optical element of the present invention can be disposed on the -# or both sides of the liquid retention * & day and day. When the above-described light warfare 10 10 20 pre-bonding members are disposed on both sides of the liquid crystal cell, they may be the same or different. In the above liquid crystal display #, for example, various optical and sibling components such as a diffusion plate, an anti-glare layer, an anti-reflection layer, and a miscellaneous: X plate, a rear bell array, a lens array sheet, a light diffusing plate, and a backlight may be disposed. & EXAMPLES Hereinafter, the examples of the present invention and the comparative examples are carried out together, and the present invention is not limited by the following examples and comparative examples, and in each of the examples and comparative examples. Various characteristics and substances and evaluations were carried out by the following methods. ^ (Thickness of Hard Coating Layer) Using a micro-meter thickness gauge manufactured by Mitutoyo Co., Ltd., the entire thickness of the film was reduced, and the thickness of the transparent plastic film was subtracted from the entire thickness. From this, the thickness of the hard coat layer was calculated. Thickness (hardening shrinkage force) As shown in Fig. 4(A), a hard coat material is formed by coating 33 200838700 on a single sheet of the transparent plastic film substrate 1, and then dried by heating to form a coating film 8. Then, a coating film of 40 mm x 11 mm was cut out from the coating film 8 and used as the test piece 9. Next, as shown in Fig. 4(B), one end (the left end portion in the drawing) of the test piece 9 is fixed, and the other end (the right end portion in the drawing) 5 of the test piece 9 is fixed to the tension. The measuring device (digital dynamometer) 10 was provided with an ultraviolet irradiation area of 40 cm 2 . Then, the test piece 9 was cured by ultraviolet irradiation, and the stress at the time of curing shrinkage was measured by the above-described tension measuring device 10 to obtain a hardening contraction force. (Shrinkage ratio) 10 The length (L1) in the width direction of the transparent plastic film substrate before the application of the hard 'coating material was measured by a ruler. Then, a hard coat layer forming material is applied to one surface of the transparent plastic film substrate, and then hardened by ultraviolet irradiation to form a hard coat layer. The length (L2) of the transparent plastic film substrate on which the hard coat layer was formed was measured with a ruler, and the shrinkage ratio (%) was determined from the following formula (I). 15 Shrinkage ratio (%) = { 1 —(L2/L1) } xlOO (I) L1 : Length of the transparent plastic film before the formation of the hard coat layer (mm) L2 : Length of the transparent plastic film after the formation of the hard coat layer ( Mm) (curl value) A 100 mm wide hard-coated film slice between 610 and 710 mm was cut from one end of a transparent plastic film substrate (width: 1330 mm) 20 which was formed into a hard coat layer, and the curl was measured using a digital vernier scale. The width (W) of the hard coat film slice described above was determined by the following formula (π). Curl value (mm) = 100 —W (Π) W : width of the hard coated film slice after crimping (mm) 34 200838700 (pencil hardness) Place the transparent plastic film substrate side down and apply hard coating on the glass plate film. Thereafter, the pencil hardness was measured on the surface of the hard coat layer in accordance with the pen hardness test described in JIS K5400 (where the load was 500 g). 5 (Example 1) A Ding Ba having a thickness of 40 μm and a twist of 133 〇 111111 was prepared (the film was used as a transparent plastic film substrate. Further, the hard coat forming material was prepared in the following manner. UV-curable tree composed of cyanuric acid acrylate, pentaerythritol triacrylate, and isophorone diisocyanate urethane urethane (produced by Nippon Ink Chemical Industry Co., Ltd., trade name, GRANDIC pCM〇) In the case of 7 〇"), 0.5 parts by weight of a leveling agent (produced by Sakamoto Ink Chemical Co., Ltd., trade name "grandic PC-4100") is added per 100 parts by weight of the resin solid component. The ethyl ester is diluted to a solid content of 50% by weight. 15 On the single side of the transparent plastic film substrate, the side of the transparent plastic _ 'film substrate is removed from both sides of the visibility direction. In the portion of mm, the hard coat forming material is applied by a squeeze coater to form a coating film. At this time, the thickness of the coating film is adjusted so that the thickness of the hard coat layer is (4) lion, and then, by heating at 100 C for 1 minute. The above coating film is dried. Then, it was hardened by irradiating ultraviolet rays having a light amount of 300 mJ/cm 2 with a high-pressure water/20 silver lamp to form a hard coat layer having a thickness of 20. Using such an operation, a hard coat film of the present example was produced. The ratio of the thickness (A) of the hard coat layer (b) to the thickness (b) of the transparent plastic film substrate in the present embodiment is 1/2. (Example 2) 35 200838700 In addition to changing the thickness and formation of the above coating film A hard coat film of the present example was produced in the same manner as in Example 1 except for a hard coat layer having a thickness of 16 gm. The thickness of the hard coat layer (A) and the thickness of the above transparent plastic film substrate in the present embodiment ( The ratio (A/B) of B) is 1/2.5. (Comparative Example 1) The same procedure as in Example 1 was carried out except that the thickness of the coating film was changed to form a hard coat layer having a thickness of 14/m. The hard coat film of the comparative example. The ratio (A/B) of the thickness (A) of the hard coat layer (B) to the thickness (B) of the transparent plastic film substrate in the comparative example was 1/2.86. 10 (Comparative Example 2 The same procedure as in Example 1 was carried out except that the thickness of the coating film was changed to form a hard coat layer having a thickness of 11 μm. The hard coat film of the comparative example. The ratio (A/B) of the thickness (A) of the hard coat layer to the thickness (B) of the transparent plastic film substrate in the comparative example was 1/3.64. 15 (Comparative Example 3) ® A hard coat film of this comparative example was produced in the same manner as in Example i except that a TAC film having a thickness of 80 μm and a width of 1330 mm was used as the transparent plastic film substrate. The thickness of the hard coat layer in the comparative example was The ratio (A/B) of the thickness (B) of the transparent plastic film substrate was 1/4. 20 . The respective hard coat films of the examples and the comparative examples obtained as described above were subjected to measurement and evaluation of various properties and physical properties. The results are shown in Table 1 below. Further, in the graph of Fig. 5, the relationship between the thickness of the hard coat layer and the hardening shrinkage force in the width direction of the coating film in Examples 1 and 2 and Comparative Examples 1 and 2 is shown. Further, in the graph of Fig. 6, the relationship between the hardening shrinkage force in the width direction of the coating film and the shrinkage ratio in the width direction of the hard coat film in Comparative Examples 1 and 2 and Examples 36 and 200838 is shown. . Table 1

硬塗層厚度(A)(/zm) 基材厚度 (Β)( β m) A/B 硬化收縮力(N/cm2) 收縮率(％) 捲曲值 (mm) 鉛筆硬度實施例1 20 40 1/2 13.45 0.60 5.6 4H 實施例21 16 40 1/2.5 10.3 0.30 17.2 4H 比較例1 14 40 1/2.86 8.38 0.15 55.6 3H 比較例2 11 40 1/3.64 5.07 0.075 62.6 2H 比較例3 20 80 一 1/4 14.3 0.00 54.8 4H 5 -- 如第5圖所示’塗膜的寬度方向的硬化收縮力隨硬塗層厚度變得越厚而變得越大。另外，如第6圖所示，硬塗薄膜的寬度方向的收縮率隨塗膜的寬度方向的硬化收縮力變得越大而變得越大。從上述表1可知，在上述硬塗層厚度(A) 10和上述透明塑膠薄膜基材厚度(B)之比(A/B)是1/2.6以上的實施例1(Α/Β=1/2)和實施例2(Α/Β=1/2.5)中，在上述塗膜硬化收縮時，在上述塗膜進行收縮的同時，上述透明塑膠薄膜基材也沿寬度方向收縮，從而得到捲曲值小的平坦的硬塗薄膜。與此相對，在上述比（A/B)小於1/2.6的比較例 15 1(Α/Β=1/2·86)和比較例2(Α/Β=1/3·64)中，因為只有上述塗膜沿寬度方向硬化收縮，上述透明塑膠薄膜基材不收縮，所以捲曲值變大。另外，在上述透明塑膠薄膜基材較厚，且上述比值(八/8)小於1/2.6的比較例3(八/；6=1/4)，也只有上述塗膜沿寬度方向硬化收縮，上述透明塑膠薄膜基材 20 不收縮，所以捲曲值變大。根據本發明的硬塗薄膜之製造方法，就能夠製造平坦且高硬度的硬塗薄膜。因此，本發明的硬塗薄膜可適合使 37 200838700 用在例如偏光板等光學元件、CRT、LCD、PDP和ELD等各種圖像顯示裝置中，其用途不受限制，能夠應用於廣泛的領域。【圖式簡單說明】 5 第1圖是顯示本發明的硬塗薄膜的一個例子的結構的剖面示意圖。Hard coat thickness (A) (/zm) Substrate thickness (Β) (β m) A/B Hardening shrinkage force (N/cm2) Shrinkage (%) Curl value (mm) Pencil hardness Example 1 20 40 1 /2 13.45 0.60 5.6 4H Example 21 16 40 1/2.5 10.3 0.30 17.2 4H Comparative Example 1 14 40 1/2.86 8.38 0.15 55.6 3H Comparative Example 2 11 40 1/3.64 5.07 0.075 62.6 2H Comparative Example 3 20 80 1/ 4 14.3 0.00 54.8 4H 5 -- As shown in Fig. 5, the hardening shrinkage force in the width direction of the coating film becomes larger as the thickness of the hard coat layer becomes thicker. Further, as shown in Fig. 6, the shrinkage ratio in the width direction of the hard coat film becomes larger as the hardening shrinkage force in the width direction of the coating film becomes larger. As is apparent from the above Table 1, Example 1 (Α/Β=1/) in which the ratio (A/B) of the thickness (A) of the hard coat layer to the thickness (B) of the transparent plastic film substrate was 1/2.6 or more. 2) and in the second embodiment (Α/Β=1/2.5), when the coating film is cured and shrunk, the transparent plastic film substrate is also shrunk in the width direction while the coating film is shrunk, thereby obtaining a curl value. Small flat hard coated film. On the other hand, in the comparative example 15 1 (Α/Β = 1/2·86) and the comparative example 2 (Α/Β = 1/3·64) in which the above ratio (A/B) is less than 1/2.6, Only the above-mentioned coating film is hardened and contracted in the width direction, and the above-mentioned transparent plastic film substrate does not shrink, so the curl value becomes large. Further, in the comparative example 3 (eight/; 6 = 1/4) in which the above-mentioned transparent plastic film substrate is thick and the above ratio (eight/8) is less than 1/2.6, only the above-mentioned coating film is hardened and shrunk in the width direction. Since the transparent plastic film substrate 20 does not shrink, the curl value becomes large. According to the method for producing a hard coat film of the present invention, it is possible to produce a flat and high hardness hard coat film. Therefore, the hard coat film of the present invention can be suitably used in various image display devices such as optical elements such as a polarizing plate, CRT, LCD, PDP, and ELD, and its use is not limited, and can be applied to a wide range of fields. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing the structure of an example of a hard coat film of the present invention.

第2圖是顯示本發明的硬塗薄膜的另一個例子的結構的剖面示意圖。第3圖是顯示本發明的硬塗薄膜的又一個例子的結構 10 的剖面示意圖。第4圖是說明本發明的塗膜的寬度方向的硬化收縮力的測定方法的圖。第4(A)圖是說明試驗片的製作方法的圖、第4(B)圖是說明硬化收縮力的測定方法的圖。第5圖是說明本發明的實施例的硬塗層的厚度和塗膜 15 的寬度方向的硬化收縮力的關係的曲線圖。第6圖是顯示在本發明的實施例中的塗膜的寬度方向的硬化收縮力和硬塗薄膜的寬度方向的收縮率的關係的曲線圖。【主要元件符號說明】 1.··透明塑膠薄膜基材 2…硬塗層 3、5、7·.·硬塗薄膜 4· · .^^赤立 6…防反射層 8…塗膜 9…試驗片 10···張力測定器(數位測力計) 38Fig. 2 is a schematic cross-sectional view showing the structure of another example of the hard coat film of the present invention. Fig. 3 is a schematic cross-sectional view showing a structure 10 of still another example of the hard coat film of the present invention. Fig. 4 is a view for explaining a method of measuring the hardening shrinkage force in the width direction of the coating film of the present invention. Fig. 4(A) is a view for explaining a method of producing a test piece, and Fig. 4(B) is a view for explaining a method of measuring a hardening contraction force. Fig. 5 is a graph for explaining the relationship between the thickness of the hard coat layer and the hardening shrinkage force in the width direction of the coating film 15 of the embodiment of the present invention. Fig. 6 is a graph showing the relationship between the hardening shrinkage force in the width direction of the coating film and the shrinkage ratio in the width direction of the hard coat film in the examples of the present invention. [Description of main component symbols] 1.··Transparent plastic film substrate 2...hard coating 3,5,7·.·hard coating film 4···^^赤立6...antireflection layer 8...coating film 9... Test piece 10··· Tension measuring device (digital dynamometer) 38

Claims

200838700 X. Patent application garden: 1. A method for manufacturing a hard coated film having a hard coat layer on at least one side of a transparent plastic film substrate, and the method for manufacturing the hard coated film comprises: preparing to contain a hard coat a step of preparing a hard coat layer forming material of a resin and a solvent; a coating film forming step of applying the hard coat layer forming material on at least one surface of the transparent plastic film substrate to form a coating film; and Hardening, forming a hard coat forming step of the hard coat layer, the manufacturing method further comprising adjusting at least one of the hard coat layer thickness A and the transparent plastic film substrate thickness B such that the hard coat layer is 0 degree A and The ratio A/B of the thickness B of the transparent plastic film substrate is 1/2.6 or more. 2. The method for manufacturing a hard coat film according to claim 1, wherein at least one of the hard coat layer thickness A and the transparent plastic film substrate thickness b is adjusted such that the hard coat layer thickness A and the transparent plastic are The ratio A/B of the film base material 15 thickness B is 1/2.5 or more. #3. The method for manufacturing a hard coat film according to claim 1 is to adjust the thickness A of the hard coat layer to a range of 15 to 35/m, and to adjust the thickness B of the transparent plastic film substrate to 15 ~50#111 range. 4. The method for producing a hard coat film according to the first aspect of the invention, wherein in the hard coat layer forming step, the hardening shrinkage force in the width direction of the coating film is 9 N/cm 2 or more. 5. The method for producing a hard coat film according to the first aspect of the invention, wherein the hard coat resin comprises the following A component, B component and C component, and component A: urethane acrylate and urethane methyl ester丙39 200838700 At least one of the enoic acid S; at least one of a succinyl acrylate vinegar and a polyol methacrylic acid vinegar; and a polymerization of 77 formed by at least one of C1 and C 2 Or 5 before copolymerization: a mixed polymer of a polymer and a copolymer, C1 /, a acrylic acid acetal having an alkyl group including at least one group of a fluorenyl group and an acryl fluorenyl group; and _C2', including A radical alkyl methacrylate of at least one group of a benzyl group. 10 6. The method for manufacturing a hard coated film according to the range of the material of the towel, further comprising the step of forming an antireflection layer. A method of producing a hard coat film according to the sixth aspect of the invention, wherein the antireflection layer comprises hollow spherical oxygen cut particles. 8. The hard coating 4 film is made by the manufacturing method of the first item of the patent scope. 9. If the application is specifically applied to the slave, the outer surface structure of the aforementioned hard coat layer is (4) structure. The 10^ polarizing plate is a hard coat film having a polarizing element and a hard coat film, and the above-mentioned hard 20 and special film are in the eighth scope of the patent scope. U.:?c" is a hard coat film comprising a hard coat film, and the hard coat film of the above-mentioned patent application. 12. The application of the polarizer is the polarizer of the 10th item of the Shen-Patent Circumference. 40