TWI744339B

TWI744339B - Anti-reflection film and manufacturing method thereof, and polarizing plate with anti-reflection layer

Info

Publication number: TWI744339B
Application number: TW106120134A
Authority: TW
Inventors: 宮本幸大; 金谷実; 梨木智剛
Original assignee: 日商日東電工股份有限公司
Priority date: 2016-06-17
Filing date: 2017-06-16
Publication date: 2021-11-01
Also published as: WO2017217526A1; TW201802504A

Abstract

本發明之抗反射膜100係於透明膜基材1之一個主表面具備包含折射率不同之複數個薄膜51、52、53、54之抗反射層5。抗反射膜係透濕度為15～1000 g/m² ・24 h。抗反射層5之表面之壓入彈性模數為20～100 GPa，算術平均粗糙度Ra為3 nm以下，較佳為1.5 nm以下。The anti-reflection film 100 of the present invention is provided with an anti-reflection layer 5 including a plurality of thin films 51, 52, 53, 54 having different refractive indexes on one main surface of the transparent film substrate 1. The moisture permeability of the anti-reflective film is 15～1000 g/m ² ·24 h. The indentation elastic modulus of the surface of the anti-reflection layer 5 is 20-100 GPa, and the arithmetic average roughness Ra is 3 nm or less, preferably 1.5 nm or less.

Description

Anti-reflection film and manufacturing method thereof, and polarizing plate with anti-reflection layer

本發明係關於一種於透明膜上具備包含複數個薄膜之抗反射層之抗反射膜、及其製造方法。The present invention relates to an anti-reflection film provided with an anti-reflection layer including a plurality of thin films on a transparent film, and a manufacturing method thereof.

於液晶顯示器或有機EL(Electroluminescence，電致發光)顯示器等圖像顯示裝置之視認側表面，為了防止由外光之反射或殘像所引起之畫質下降、提高對比度等，而使用抗反射膜。抗反射膜係於透明膜上具備抗反射層，該抗反射層包含折射率不同之複數個薄膜之積層體。作為抗反射膜之一形態，可列舉附有抗反射層之偏光板。附有抗反射層之偏光板係藉由如下方式形成：於偏光板之表面貼合抗反射膜，或於偏光元件之表面貼合抗反射膜作為保護膜。又，亦已知有藉由在偏光板上形成抗反射層而形成附有抗反射層之偏光板之方法。於專利文獻1中揭示：於透明塑膠基材上使用設有透濕度為10 g/m² ・24 h以下之兼作水蒸氣障壁層之抗反射層的抗反射膜，藉此抑制加熱及加濕環境下之偏光板之翹曲，從而可提高可靠性。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2002-189211號公報On the visible side surface of image display devices such as liquid crystal displays or organic EL (Electroluminescence) displays, in order to prevent deterioration of image quality caused by reflection of external light or residual images, and to improve contrast, anti-reflection films are used . The anti-reflection film is provided with an anti-reflection layer on the transparent film, and the anti-reflection layer includes a laminate of a plurality of thin films with different refractive indexes. As one form of the anti-reflection film, a polarizing plate with an anti-reflection layer can be cited. The polarizing plate with the anti-reflection layer is formed by attaching an anti-reflection film to the surface of the polarizing plate, or attaching an anti-reflection film to the surface of the polarizing element as a protective film. In addition, a method of forming a polarizing plate with an anti-reflection layer by forming an anti-reflection layer on a polarizing plate is also known. It is disclosed in Patent Document 1: The use of an anti-reflection film provided with an anti-reflection layer that doubles as a water vapor barrier layer ^{with a moisture permeability of 10 g/m 2·24 h or less on a transparent plastic substrate, thereby suppressing heating and humidification} The warpage of the polarizer under the environment can improve the reliability. [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open No. 2002-189211

[發明所欲解決之問題] 一般而言，與假設於室外使用之移動設備中所用之偏光板相比，於汽車用之圖像顯示裝置中所用之偏光板要求更高溫度(例如90℃以上)下之特性變化較小(高溫耐久性)。於使用專利文獻1等之抗反射膜之情形時，自外部之水分浸入等得到抑制，故而偏光板之耐濕性提高。另一方面已判明，具備專利文獻1之抗反射膜之偏光板若長時間暴露於高溫環境下，則偏光板容易產生不均，不滿足汽車用途中所要求之高溫下之可靠性。鑒於上述內容，本發明之目的在於提供一種於與偏光元件貼合之情形時，高溫下之耐久性優異之抗反射膜。 [解決問題之技術手段] 本發明之抗反射膜係於透明膜基材之一個主表面具備包含折射率不同之複數個薄膜之抗反射層，透濕度為15～1000 g/m² ・24 h。抗反射層表面之壓入彈性模數為20～100 GPa，算術平均粗糙度Ra為3 nm以下，較佳為1.5 nm以下。透明膜基材較佳為於抗反射層之形成面側具備硬塗層。硬塗層較佳為包含丙烯酸胺基甲酸酯系樹脂。硬塗層亦可為於樹脂基質中分散有微粒子之防眩性硬塗層。亦可於抗反射層之表面設有防污層。抗反射層較佳為高折射率層與低折射率層之交替積層體。作為高折射率層，較佳為氧化鈮薄膜，作為低折射率層，較佳為氧化矽薄膜。本發明之附有抗反射層之偏光板係於偏光元件之一個面具備上述抗反射膜。進而，本發明係關於本發明之上述抗反射膜之製造方法。構成抗反射層之薄膜較佳為藉由濺鍍法而成膜，特佳為反應性濺鍍。於反應性濺鍍中，一面向成膜室內導入惰性氣體及反應性氣體一面進行成膜。較佳為以藉由反應性濺鍍進行之成膜成為過渡區域之方式控制反應性氣體之導入量。例如可列舉：檢測放電之電漿發光強度，根據電漿發光強度而控制導入至成膜室內之反應性氣體之導入量的方法；檢測濺鍍時之放電電壓，以放電電壓成為固定之方式控制反應性氣體之導入量的方法等。濺鍍成膜時之壓力較佳為0.4 Pa以上。濺鍍成膜時之靶材表面之磁通密度較佳為20 mT以上。 [發明之效果] 本發明之抗反射膜由於抗反射層之透濕度較高，故而於製作附有抗反射層之偏光板之情形時，高溫下之耐久性優異。又，抗反射層之機械強度較高且表面平滑，故而耐擦傷性及指紋擦拭性亦優異。[Problem to be solved by the invention] Generally speaking, the polarizing plate used in the image display device of the automobile requires a higher temperature (for example, 90°C or higher) than the polarizing plate used in the mobile equipment that is supposed to be used outdoors. ) The characteristic changes under) are small (high temperature durability). In the case of using the anti-reflection film of Patent Document 1, etc., intrusion of moisture from the outside, etc., is suppressed, and therefore the moisture resistance of the polarizing plate is improved. On the other hand, it has been found that if the polarizing plate provided with the anti-reflection film of Patent Document 1 is exposed to a high temperature environment for a long time, the polarizing plate is prone to unevenness and does not meet the high temperature reliability required for automotive applications. In view of the foregoing, the object of the present invention is to provide an anti-reflection film with excellent durability at high temperatures when it is bonded to a polarizing element. [Technical Means to Solve the Problem] The anti-reflection film of the present invention is provided on one main surface of a transparent film substrate with an anti-reflection layer containing multiple films with different refractive indexes, and the moisture permeability is 15～1000 g/m ² ·24 h . The indentation elastic modulus of the surface of the anti-reflection layer is 20-100 GPa, and the arithmetic average roughness Ra is 3 nm or less, preferably 1.5 nm or less. The transparent film substrate preferably has a hard coat layer on the side where the anti-reflection layer is formed. The hard coat layer preferably contains acrylic urethane-based resin. The hard coat layer may also be an anti-glare hard coat layer in which fine particles are dispersed in a resin matrix. An anti-fouling layer can also be provided on the surface of the anti-reflective layer. The anti-reflection layer is preferably an alternate laminate of a high refractive index layer and a low refractive index layer. As the high refractive index layer, a niobium oxide film is preferred, and as the low refractive index layer, a silicon oxide film is preferred. The polarizing plate with an anti-reflection layer of the present invention is provided with the anti-reflection film on one surface of the polarizing element. Furthermore, this invention relates to the manufacturing method of the said antireflection film of this invention. The thin film constituting the anti-reflection layer is preferably formed by a sputtering method, and particularly preferably is reactive sputtering. In reactive sputtering, the film is formed while introducing inert gas and reactive gas into the film forming chamber. It is preferable to control the introduction amount of the reactive gas so that the film formation by reactive sputtering becomes a transition area. Examples include: detecting the plasma luminous intensity of discharge, and controlling the amount of reactive gas introduced into the film-forming chamber based on the plasma luminous intensity; detecting the discharge voltage during sputtering, and controlling the discharge voltage to be fixed How to introduce the amount of reactive gas, etc. The pressure during sputtering film formation is preferably 0.4 Pa or more. The magnetic flux density on the surface of the target during sputtering film formation is preferably 20 mT or more. [Effects of the Invention] The anti-reflection film of the present invention has a high moisture permeability of the anti-reflection layer, so when manufacturing a polarizing plate with an anti-reflection layer, it has excellent durability at high temperatures. In addition, the anti-reflection layer has high mechanical strength and a smooth surface, so it has excellent scratch resistance and fingerprint wiping properties.

[抗反射膜之構成] 圖1係模式性地表示一實施形態之抗反射膜之構成之剖視圖。圖2係模式性地表示具備抗反射層之偏光板之一形態之剖視圖，於偏光元件8之一個面貼合有抗反射膜。圖1之抗反射膜100係於透明膜基材1上介隔密接性提高層3而設有抗反射層5。抗反射層為2層以上之薄膜之積層體，於圖1中，圖示有包含4層薄膜51、52、53、54之積層體之抗反射層5。＜透明膜基材＞透明膜基材1包含可撓性之透明膜10。較佳為於透明膜10之形成抗反射層5之面側設有硬塗層11。 (透明膜) 透明膜10之可見光透過率較佳為80%以上，更佳為90%以上。透明膜10之厚度並無特別限定，就強度或處理性等作業性、薄層性等觀點而言，較佳為5～300 μm左右，更佳為10～300 μm，進而較佳為20～200 μm。作為構成透明膜10之樹脂材料，例如可列舉透明性、機械強度、及熱穩定性優異之熱塑性樹脂。作為此種熱塑性樹脂之具體例，可列舉：三乙醯纖維素等纖維素系樹脂、聚酯系樹脂、聚醚碸系樹脂、聚碸系樹脂、聚碳酸酯系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、聚烯烴系樹脂、(甲基)丙烯酸系樹脂、環狀聚烯烴系樹脂(降𦯉烯系樹脂)、聚芳酯系樹脂、聚苯乙烯系樹脂、聚乙烯醇系樹脂、及其等之混合物。如圖2所示，於將抗反射膜與偏光元件8積層之情形時，透明膜10具有作為用以形成抗反射層5之基材之功能、及作為偏光元件8之保護膜之功能。於將透明膜10與偏光元件8積層而使用之情形時，透明膜10之透濕度較佳為100 g/m² ・24 h以上，更佳為130 g/m² ・24 h以上，進而較佳為150 g/m² ・24 h以上。透濕度係以40℃、90%之相對濕度差以24小時透過面積為1 m² 之試樣的水蒸氣之重量，係依據JIS(Japanese Industrial Standards，日本工業標準)K7129：2008附錄B而測定。若透明膜10之透濕度較大，則於偏光板放置於加熱環境下時，偏光元件中之水分容易經由透明膜而釋出至外部，故而可抑制由水分引起之偏光元件之劣化。另一方面，若透明膜10之透濕度過高，則存在偏光板之加濕耐久性下降之情形。因此，透明膜10之透濕度較佳為2000 g/m² ・24 h以下，更佳為1500 g/m² ・24 h以下。為了將透濕度設為上述範圍，可較佳地使用纖維素系樹脂作為透明膜10之材料。作為纖維素系樹脂，例如可列舉纖維素與脂肪酸之酯。作為纖維素酯之具體例，可列舉：三乙酸纖維素酯、二乙酸纖維素酯等乙酸纖維素，三丙酸纖維素酯、二丙酸纖維素酯等。於該等中，特佳為三乙酸纖維素酯。亦可於透明膜中含有一種以上之任意之添加劑。作為添加劑，例如可列舉：紫外線吸收劑、抗氧化劑、潤滑劑、塑化劑、脫模劑、防著色劑、阻燃劑、成核劑、抗靜電劑、顏料、著色劑等。 (硬塗層) 較佳為於透明膜10之表面設有硬塗層11。藉由在透明膜基材1之形成抗反射層5之面側設置硬塗層11，可提高抗反射層之硬度或彈性模數等機械特性。硬塗層11較佳為表面之硬度較高，且耐擦傷性優異。硬塗層11例如可藉由在透明膜10上塗佈含有硬化性樹脂之溶液而形成。作為硬化性樹脂，可列舉熱硬化型樹脂、紫外線硬化型樹脂、電子束硬化型樹脂等。作為硬化性樹脂之種類，可列舉：聚酯系、丙烯酸系、胺基甲酸酯系、丙烯酸胺基甲酸酯系、醯胺系、聚矽氧系、矽酸鹽系、環氧系、三聚氰胺系、氧雜環丁烷系、丙烯酸胺基甲酸酯系等之各種樹脂。該等硬化性樹脂可適當地選擇一種或兩種以上而使用。於該等中，就硬度較高、可進行紫外線硬化且生產性優異之方面而言，較佳為丙烯酸系樹脂、丙烯酸胺基甲酸酯系樹脂、及環氧系樹脂，其中較佳為丙烯酸胺基甲酸酯系樹脂。紫外線硬化型樹脂中包括紫外線硬化型之單體、寡聚物、聚合物等。可較佳地使用之紫外線硬化型樹脂例如可列舉具有紫外線聚合性之官能基者，其中亦可列舉包含具有2個以上、特別是3～6個該官能基之丙烯酸系之單體或寡聚物作為成分者。為了使抗反射膜具有防眩性及防炫光性，設於透明膜之表面的硬塗層較佳為具有防眩性。作為防眩性硬塗層，例如可列舉使微粒子分散於上述硬化性樹脂基質中而成者。作為分散於樹脂基質中之微粒子，可無特別限制地使用：氧化矽、氧化鋁、氧化鈦、氧化鋯、氧化鈣、氧化錫、氧化銦、氧化鎘、氧化銻等各種金屬氧化物微粒子，玻璃微粒子，包含聚甲基丙烯酸甲酯、聚苯乙烯、聚胺基甲酸酯、丙烯酸-苯乙烯共聚物、苯胍胺、三聚氰胺、聚碳酸酯等各種透明聚合物之交聯或未交聯之有機系微粒子，聚矽氧系微粒子等具有透明性者。該等微粒子可適當地選擇1種或2種以上而使用。其中，較佳為折射率高於基質樹脂之微粒子，例如較佳為苯乙烯珠粒(折射率為1.59)等折射率為1.5以上之有機系微粒子。微粒子之平均粒徑較佳為1～10 μm，更佳為2～5 μm。微粒子之比率並無特別限制，較佳為相對於基質樹脂100重量份而為6～20重量份。硬塗層例如可藉由在透明膜10上塗佈含有硬化性樹脂之溶液而形成。較佳為於用以形成硬塗層之溶液中調配有紫外線聚合起始劑。為了形成包含微粒子之防眩性硬塗層，較佳為於透明膜上塗佈除了硬化性樹脂以外含有上述微粒子之溶液。於溶液中，亦可含有調平劑、搖變劑、抗靜電劑等添加劑。於形成防眩性硬塗層時，藉由在溶液中含有搖變劑(粒徑為0.1 μm以下之氧化矽、雲母等)，可於硬塗層之表面容易地形成由突出粒子所得之微細凹凸構造。硬塗層11之厚度並無特別限定，為了實現較高之硬度，較佳為0.5 μm以上，更佳為1 μm以上。若考慮利用塗佈之形成之容易性，則硬塗層之厚度較佳為15 μm以下，更佳為12 μm以下，進而較佳為10 μm以下。又，亦為了維持膜基材之透濕度較高以不阻礙水分自偏光元件向外部之釋出，硬塗層11之厚度較佳為上述範圍。透明膜基材1之形成抗反射層5之面側之表面的算術平均粗糙度Ra較佳為1.5 nm以下，更佳為1.0 nm以下。於在透明膜10上形成有硬塗層11之情形時，硬塗層11之算術平均粗糙度成為透明膜10之形成抗反射層5之面側的表面之算術平均粗糙度。算術平均粗糙度Ra係根據使用原子力顯微鏡(AFM)之1 μm見方之觀察像而求出。若如上所述般藉由塗佈而形成硬塗層11，則可減小透明膜基材1之表面之算術平均粗糙度。若透明膜基材1之表面平滑，則存在如下傾向：形成於該透明膜基材上之抗反射層5之表面之算術平均粗糙度亦變小，抗反射膜之耐擦傷性提高。 (表面處理) 對於透明膜基材1之表面，亦能以提高與抗反射層5之密接性等為目的而進行電暈處理、電漿處理、火焰處理、臭氧處理、底塗處理、輝光處理、皂化處理、利用偶合劑進行之處理等表面改質處理。例如，藉由在真空中實施電漿處理，而將基材之表面改質，並且於表面形成適當之凹凸，可提高透明膜基材1(硬塗層11)與抗反射層5之密接性。又，藉由在利用電漿處理而形成於表面之凹凸上將抗反射層成膜，而存在抗反射膜之透濕度變大之傾向。如下所述，為了提高透明膜基材1與抗反射層5之密接性，亦可於透明膜基材1上設置密接性提高層3。＜抗反射層＞於透明膜基材1上形成抗反射層5。抗反射層5包含2層以上之薄膜。一般而言，抗反射層係以入射光與反射光之反轉之相位彼此抵消之方式調整薄膜之光學膜厚(折射率與厚度之乘積)。藉由將抗反射層設為折射率不同之2層以上之薄膜之多層積層體，可於可見光之寬頻帶之波長範圍內減小反射率。作為構成抗反射層5之薄膜之材料，可列舉金屬之氧化物、氮化物、氟化物等。例如，作為波長550 nm下之折射率為1.6以下之低折射率材料，可列舉氧化矽、氟化鎂等。作為波長550 nm下之折射率為1.9以上之高折射材料，可列舉氧化鈦、氧化鈮、氧化鋯、摻錫氧化銦(ITO)、摻銻氧化錫(ATO)等。除低折射率層與高折射率層以外，例如亦可形成包含氧化鈦、或上述低折射率材料與高折射材料之混合物之薄膜作為折射率為1.50～1.85左右之中折射率層。構成抗反射層之薄膜較佳為可見光之光吸收較小，可較佳地使用波長550 nm下之消光係數為0.5以下之材料。作為抗反射層5之積層構成，自透明膜10側起可列舉：光學膜厚為240 nm～260 nm左右之高折射率層、與光學膜厚為120 nm～140 nm左右之低折射率層之2層構成；光學膜厚為170 nm～180 nm左右之中折射率層、光學膜厚為60 nm～70 nm左右之高折射率層、與光學膜厚為135 nm～145 nm左右之低折射率層之3層構成；光學膜厚為20 nm～55 nm左右之高折射率層、光學膜厚為15 nm～70 nm左右之低折射率層、光學膜厚為60 nm～330 nm左右之高折射率層、與光學膜厚為100 nm～160 nm左右之低折射率層之4層構成；光學膜厚為15 nm～30 nm左右之低折射率層、光學膜厚為20 nm～40 nm左右之高折射率層、光學膜厚為20 nm～40 nm左右之低折射率層、光學膜厚為240 nm～290 nm左右之高折射率層、與光學膜厚為100 nm～200 nm左右之低折射率層之5層構成。構成抗反射層之薄膜之折射率或膜厚之範圍並不限定於上述示例。又，抗反射層5亦可為6層以上之薄膜之積層體。抗反射層較佳為低折射率層與高折射率層之交替積層體。為了減少空氣界面之反射，作為抗反射層之最表面層(與透明膜基材1為相反側之面)而設置之薄膜54較佳為低折射率層。如上所述，作為低折射率層及高折射率層之材料，較佳為氧化物。其中，抗反射層5較佳為作為低折射率層之氧化矽(SiO₂ )薄膜52、54與作為高折射率層之氧化鈮(Nb₂ O₅ )薄膜51、53之交替積層體。抗反射層5之透濕度較佳為15 g/m² ・24 h以上，更佳為20 g/m² ・24 h以上，進而較佳為30 g/m² ・24 h以上。藉由提高抗反射層之透濕度，可抑制水分之滯留，使高溫下之耐久性提高。就使高溫下之耐久性進一步提高等觀點而言，抗反射層5之透濕度亦可為100 g/m² ・24 h以上或130 g/m² ・24 h以上。若抗反射層之透濕度過高，則存在高濕下之耐久性下降之傾向，故而抗反射層5之透濕度較佳為1000 g/m² ・24 h以下，更佳為500 g/m² ・24 h以下。抗反射層為薄膜，以單體之形式求出透濕度係較為困難。因此，只要於透明膜基材上形成抗反射層而測定透濕度即可。多數樹脂膜之透濕度充分大於無機氧化物層之透濕度，故而於透明膜基材1上設有抗反射層5之抗反射膜之透濕度被視為等於抗反射層5之透濕度。因此，本發明之抗反射膜之透濕度較佳為15～1000 g/m² ・24 h，更佳為20～500 g/m² ・24 h以上。若將於透明膜基材1上設有抗反射層5之抗反射膜或附有抗反射層之偏光板暴露於加熱環境下，則透明膜10或偏光元件8中之水分蒸散至膜外。於抗反射層之透濕度較小之情形時，水分難以擴散至系統外。若水分滯留於偏光板之內部，則存在如下傾向：透明膜10之三乙醯纖維素等容易被水解，偏光元件之保護性能下降。又，若乙醯纖維素被水解，則產生游離酸。於酸之存在下，容易發生構成偏光元件之聚乙烯醇之多烯化，導致偏光板之劣化。與此相對，認為於抗反射層5之透濕度較大之情形時，自偏光元件或透明膜蒸散之水分容易自抗反射層5之表面擴散至系統外，故而水分之滯留得到抑制，高溫下之偏光板之劣化得到抑制。抗反射層5之壓入彈性模數較佳為20 GPa以上，更佳為30 GPa以上。藉由增大抗反射層之彈性模數而耐擦傷性提高。另一方面，若彈性模數過大，則存在膜之搬送性等處理性下降之情形。因此，抗反射層5之壓入彈性模數較佳為100 GPa以下，更佳為70 GPa以下。就相同之原因而言，抗反射層之壓入硬度較佳為0.5～10 GPa，更佳為1～5 GPa。壓入彈性模數及壓入硬度係藉由奈米壓痕而測定。抗反射層5之表面之算術平均粗糙度Ra較佳為3 nm以下，更佳為1.8 nm以下，進而較佳為1.5 nm以下，特佳為1.3 nm以下。藉由減小算術平均粗糙度，而存在耐擦傷性提高之傾向。尤其若抗反射層5之表面之算術平均粗糙度為1.5 nm以下，則存在皮脂等污物附著時之擦拭性提高之傾向。另一方面，若抗反射層5之表面之算術平均粗糙度過小，則存在膜製造時等之輥搬送變困難之傾向，故而抗反射層5之表面之算術平均粗糙度較佳為0.3 nm以上，更佳為0.5 nm以上。構成抗反射層之薄膜之成膜方法並無特別限定，可為濕式塗佈法、乾式塗佈法之任一種。就可形成膜厚均勻且緻密之薄膜之方面而言，較佳為真空蒸鍍、CVD(Chemical Vapor Deposition，化學氣相沈積)、濺鍍、電子束蒸鍍等乾式塗佈法。其中，就容易形成具有上述彈性模數之機械強度較高之膜之方面而言，特佳為濺鍍法。藉由利用輥對輥方式一面向一個方向(長度方向)搬送長條之膜基材一面進行連續成膜，可提高抗反射膜之生產性。藉由濺鍍法進行之氧化矽或氧化鈮等氧化物層之成膜可藉由使用氧化物靶材之方法、及使用金屬靶材之反應性濺鍍之任一種而實施。為了使用氧化物靶材將氧化矽等絕緣性之氧化物成膜，需要RF(Radio Frequency，射頻)放電，故而成膜速率較小且生產性較低。因此，氧化物之濺鍍成膜較佳為使用金屬靶材之反應性濺鍍。於反應性濺鍍中，一面將氬氣等惰性氣體及氧氣等反應性氣體導入至腔室內一面進行成膜。反應性濺鍍中，較佳為以成為金屬區域與氧化物區域之中間之過渡區域之方式調整氧量。若以氧量不足之金屬區域進行成膜，則存在如下傾向：所獲得之膜之氧量遠遠小於化學計量組成，抗反射層帶有金屬光澤而透明性下降。又，氧量較大之氧化物區域存在成膜速率極度下降之傾向。藉由以濺鍍成膜成為過渡區域之方式調整氧量，能以高速率將氧化物膜成膜。又，藉由以過渡區域進行成膜，而存在所獲得之膜之透濕度上升，高溫下之耐久性提高的傾向。作為使用於反應性濺鍍之濺鍍電源，較佳為DC(Direct Current，直流)或MF(Medium Frequency，中頻)-AC(Alternating Current，交流)。於反應性雙磁控濺鍍法中，作為以成膜模式成為過渡區域之方式控制氧導入量之方法，可列舉檢測放電之電漿發光強度而控制向成膜室之氣體導入量的電漿發射監控方式(PEM方式)。PEM係藉由檢測電漿發光強度並反饋給氧導入量之方式進行控制。例如藉由將發光強度之控制值(設定點)設定為特定之範圍而進行PEM控制，調整氧導入量，可維持過渡區域內之成膜。又，亦可進行利用阻抗方式之控制，該阻抗方式係以電漿阻抗成為固定之方式、即以放電電壓成為固定之方式控制氧導入量。若藉由PEM方式或阻抗方式控制氧導入量，則可於長度方向上保持輥對輥方式下之薄膜之連續成膜中之成膜速率固定。因此，薄膜之膜厚變均勻，可獲得抗反射特性優異之抗反射膜。藉由在寬度方向上設置複數個氧導入配管，並個別地控制自各配管導入之氧流量，亦可提高寬度方向之品質之均勻性。於濺鍍成膜中，存在因微粒對靶材表面之附著等而產生放電異常之情形，於產生放電異常之部分，薄膜之膜質下降。此種放電異常亦可藉由電漿發光、或放電電壓而監控。於因放電異常等而電漿發光量偏離控制範圍之情形時，產生膜質或膜厚之異常之可能性較高，故而若將該部分判斷為「有缺陷」，並藉由設置於較濺鍍成膜部更靠下游側之標記裝置實施標記，則可自長條之抗反射膜中容易地去除不良部分。於濺鍍法中，藉由使高能量之濺鍍氣體(例如Ar)碰撞靶材而自靶材彈出材料，故而濺鍍粒子亦具有高能量。因此，與真空蒸鍍法或CVD法相比，濺鍍法容易形成緻密之膜。一般而言，藉由濺鍍法而形成之薄膜係透濕度較小，例如氧化矽膜之透濕度大多情況下為10 g/m² ・24 h以下。藉由調整濺鍍成膜條件，可形成透濕度為15 g/m² ・24 h以上之薄膜。例如，於濺鍍成膜時之放電電壓較小之情形時，濺鍍粒子之運動能量較小，於基板表面之擴散得到抑制。因此，膜容易成長為柱狀，膜質容易成為多孔。於放電電壓較高之情形時，膜容易形成為面狀，容易成為緻密之膜質。另一方面，若放電電壓過大，則存在如下傾向：反撞之Ar等中性粒子對膜表面造成損傷而產生缺陷，故而膜密度下降。關於磁控濺鍍，磁場較強(磁通密度較大)之情況下存在電漿之擴散得到抑制，電漿密度變高之傾向。伴隨於此，可減小放電電壓，故而如上所述般存在膜容易成長為柱狀而透濕度變大之傾向。又，由於伴隨放電電壓之下降的濺鍍粒子之運動能量下降，而可減少由反撞Ar粒子等引起之損傷。因此，膜表面容易變平滑，可獲得算術平均粗糙度Ra較小且耐擦傷性或指紋擦拭性優異之抗反射膜。濺鍍成膜時之靶材表面之磁通密度較佳為20 mT以上，更佳為35 mT以上，進而較佳為45 mT以上，特佳為55 mT以上。若成膜時之壓力較高，則濺鍍粒子之平均自由行程變小，濺鍍粒子之指向性下降而變得容易因Ar而擴散，故而膜質容易變為多孔。另一方面，若成膜壓力過高，則成膜速率下降。又，若成膜壓力較高，則存在電漿放電變得不穩定之傾向。為了形成透濕度較高且具有充分之機械強度之氧化物薄膜，成膜壓力較佳為0.4 Pa～1.5 Pa。有時除了該等濺鍍成膜條件以外，成為成膜基底之基板之表面形狀等亦對膜成長圖案造成影響。例如若如上所述般對透明膜基材之表面實施電漿處理，則存在因形成於表面之凹凸而濺鍍膜容易成長為柱狀，透濕度變大之傾向。 (密接性提高層) 大多情況下硬塗層11等有機材料與氧化物薄膜之密接性不充分。因此，較佳為於透明膜基材1與抗反射層5之間設置密接性提高層3。作為密接性提高層3之材料，可列舉：矽、鎳、鉻、鋁、錫、金、銀、鉑、鋅、鈦、鎢、鋯及鈀等金屬；包含2種以上之該等金屬之合金；該等金屬之氧化物、氮化物及氟化物等。就透光率較高且對有機層與氧化物層兩者之接著力較高之方面而言，作為密接性提高層3，特佳為氧量少於化學計量組成之氧化物。密接性提高層3之氧量較佳為化學計量組成之60～95%左右。例如於形成氧化矽(SiO_x )層作為密接性提高層3之情形時，x較佳為1.2～1.9。密接性提高層3之厚度只要為不損及透明膜基材1之透明性之程度即可，例如為1～10 nm以下左右。密接性提高層3可藉由濺鍍法、真空蒸鍍法、離子鍍覆法、CVD法等而形成。於藉由濺鍍法而形成抗反射層5之情形時，可一面搬送透明膜基材1，一面以1行程將密接性提高層3與抗反射層5連續成膜。因此，密接性提高層3較佳為藉由濺鍍法而成膜。於氧量少於化學計量組成之氧化物薄膜之濺鍍成膜中，亦可藉由PEM方式或阻抗方式而控制氧導入量。 (防污層) 抗反射膜係配置至液晶顯示裝置等顯示器之最表面而使用，故而容易受到來自外部環境之污染(指紋、手垢、灰塵等)之影響。尤其設置於抗反射層之最表面之SiO₂ 等低折射率層係潤濕性良好，指紋或手垢等污染物質容易附著。又，與一般之透明膜相比，包含氧化物之抗反射層係污染容易顯眼，污染物質容易附著，故而存在因表面反射率之變化、或附著物泛白浮現被看到而顯示變得不清晰之情形。為了使自外部環境之污染之防止、或所附著之污染物質之去除變容易，較佳為於抗反射層5之表面設置防污層7。為了提高防污性及污染物質之去除性，防污層7之純水接觸角較佳為100°以上，更佳為102°以上，進而較佳為105°以上。純水接觸角可藉由如下方式求出：於污染防止層之表面形成直徑為2 mm以下之水滴並對其接觸角進行測定。為了維持抗反射層5之抗反射特性，防污層7較佳為與抗反射層5之最表面之低折射率層54之折射率差較小。防污層7之折射率較佳為1.6以下，更佳為1.55以下。作為防污層7之材料，較佳為含有氟基之矽烷系化合物、或含有氟基之有機化合物等。防污層7可藉由反向塗佈法、模嘴塗佈法、凹版塗佈法等濕式法或CVD法等乾式法等而形成。防污層7之厚度通常為1～100 nm左右，較佳為2～50 nm，更佳為3～30 nm。為了維持抗反射層5所具有之耐擦傷性等機械強度，防污層7亦較佳為與抗反射層5同樣地表面之算術平均粗糙度Ra較小。防污層7之表面之算術平均粗糙度(即，抗反射膜表面之算術平均粗糙度)較佳為3 nm以下，更佳為2 nm以下，進而較佳為1.8 nm以下，特佳為1.5 nm以下，最佳為1.3 nm以下。若抗反射膜表面之算術平均粗糙度為1.5 nm以下，則存在指紋擦拭性提高之傾向。 [附有抗反射層之偏光板] 如圖2所示，本發明之抗反射膜可與偏光元件積層，作為附有抗反射層之偏光板而供於實際使用。圖2所示之附有抗反射層之偏光板110係於與透明膜基材1之與形成抗反射層之面為相反側的主面貼合偏光元件8之一個面。於偏光元件8之另一面貼合有透明膜9。作為偏光元件8，可列舉：使聚乙烯醇系膜、部分縮甲醛化聚乙烯醇系膜、乙烯-乙酸乙烯酯共聚物系部分皂化膜等親水性高分子膜吸附碘或二色性染料等二色性物質並進行單軸延伸所得者；聚乙烯醇之脫水處理物或聚氯乙烯之脫鹽酸處理物等之多烯系配向膜。其中，就具有較高之偏光度之方面而言，較佳為使聚乙烯醇或部分縮甲醛化聚乙烯醇等聚乙烯醇系膜吸附碘或二色性染料等二色性物質並於特定方向上配向而成之聚乙烯醇(PVA)系偏光元件。例如藉由對聚乙烯醇系膜實施碘染色及延伸而獲得PVA系偏光元件。作為PVA系偏光元件，亦可使用厚度為10 μm以下之薄型之偏光元件。作為薄型之偏光元件，例如可列舉日本專利特開昭51-069644號公報、日本專利特開2000-338329號公報、WO2010/100917號手冊、日本專利第4691205號說明書、日本專利第4751481號說明書等中記載之薄型偏光膜。此種薄型偏光元件係例如可藉由包括如下步驟之製造方法而獲得：將PVA系樹脂層與延伸用樹脂基材以積層體之狀態延伸之步驟；及進行碘染色之步驟。作為透明膜9，可較佳地使用與作為透明膜10之材料而於上文所述者相同之材料。再者，透明膜9之材料與透明膜10之材料可相同，亦可不同。於將偏光元件與透明膜貼合時，較佳為使用接著劑。作為接著劑，可適當地選擇以丙烯酸系聚合物、聚矽氧系聚合物、聚酯、聚胺基甲酸酯、聚醯胺、聚乙烯醇、聚乙烯醚、乙酸乙烯酯/氯乙烯共聚物、改性聚烯烴、環氧系聚合物、氟系聚合物、橡膠系聚合物等作為基礎聚合物者而使用。於接著PVA系偏光元件時，可較佳地使用聚乙烯醇系接著劑。本發明之抗反射膜及附有抗反射層之偏光板可用於液晶顯示裝置或有機EL顯示裝置等顯示器。尤其於用作顯示器之最表面層之情形時，有助於藉由抗反射而提高顯示器之視認性。本發明之抗反射膜及附有抗反射層之偏光板即便於長時間暴露於高溫環境下之情形時亦難以發生劣化，高溫可靠性優異，故而可特佳地用於汽車用顯示器等。 [實施例] 以下，列舉實施例對本發明更詳細地進行說明，但本發明並不限定於以下之實施例。 [附有防眩性硬塗層之膜之製作] 將紫外線硬化型丙烯酸胺基甲酸酯系單體(折射率為1.51)100重量份、平均粒徑為3.5 μm(粒子分佈範圍為3.0～4.1 μm)之聚苯乙烯珠粒(折射率為1.59)14重量份、二苯甲酮系光聚合起始劑5重量份、及甲苯171重量份混合，將混合所得之固形物成分濃度為40重量%之溶液塗佈於厚度為80 μm之三乙醯纖維素膜(折射率為1.49)上，於120℃乾燥5分鐘。此後，藉由紫外線照射進行硬化處理，形成於表面具有凹凸構造之厚度為約4 μm之防眩性硬塗層。該防眩性硬塗層之算術平均粗糙度Ra為0.43 nm。 [實施例1] 將形成有防眩性硬塗層之三乙醯纖維素膜導入至輥對輥方式之濺鍍成膜裝置中，一面使膜移行，一面對防眩性硬塗層形成面進行轟擊處理(利用Ar氣體之電漿處理)，然後將3.5 nm之SiO_x 層(x＜2)成膜作為密接性提高層，於該SiO_x 層上將12 nm之Nb₂ O₅ 層、28 nm之SiO₂ 層、100 nm之Nb₂ O₅ 層及85 nm之SiO₂ 層依序成膜。於抗反射層上，以厚度成為5 nm之方式形成氟系樹脂作為防污層，製作抗反射膜。 (轟擊處理) 轟擊處理係以壓力0.5 Pa、有效功率密度0.34 W・min/m・cm² 之條件實施。再者，轟擊處理後之防眩性硬塗層(未形成密接性提高層及抗反射層者)之表面之算術平均粗糙度Ra為0.51 nm，Ra與處理前相比變大。所謂有效功率密度，係將電漿輸出之功率密度(W/cm² )除以輥對輥方式之膜基材之搬送速度(m/min)所得的值。即便電漿功率相同，於搬送速度較大之情形時，有效之處理功率亦下降。 (濺鍍成膜) 作為密接性提高層之SiOx層係以壓力0.4 Pa對Si靶材施加3 W/cm² 之MF-AC電力40 kHz而成膜。於SiO₂ 層之成膜時使用Si靶材，於Nb₂ O₅ 層之成膜時使用Nb靶材，以表1所示之電壓、壓力進行成膜。於氧化物薄膜之成膜中，藉由調整氬氣之導入量及排氣量而保持壓力固定，藉由電漿發光監控(PEM)控制以成膜模式維持過渡區域之方式調整導入之氧量。 [實施例2～5及比較例1～4] 如表1所示般變更轟擊處理之有效功率密度、與成膜SiO₂ 層及Nb₂ O₅ 層時之放電電壓及壓力。實施例4、5及比較例1～4係變更磁體而以靶材表面之磁通密度為80 mT之條件進行成膜。實施例5及比較例3係藉由PEM控制以成膜模式維持氧化區域之方式調整氧導入量。 [比較例5] 以壓力0.15 Pa、有效功率密度0.10 W・min/m・cm² 之條件對形成有防眩性硬塗層之三乙醯纖維素膜之硬塗層表面實施轟擊處理。此後，藉由真空蒸鍍法而將12 nm之Nb₂ O₅ 層、28 nm之SiO₂ 層、100 nm之Nb₂ O₅ 層及85 nm之SiO₂ 層依序成膜，與實施例1同樣地於抗反射層上形成防污層，製作抗反射膜。 [比較例6] 藉由濕式塗佈而於形成有防眩性硬塗層之三乙醯纖維素膜之硬塗層表面形成100 nm之低折射率層，製作抗反射膜。作為低折射率層之材料，使用藉由聚矽氧烷與氟烷基矽烷之混合物之溶膠凝膠反應而生成之氟化合物聚合物。 [比較例7] 以壓力0.5 Pa、有效功率密度0.10 W・min/m・cm² 之條件對防眩性硬塗層之表面實施轟擊處理。此後，與比較例6同樣地製作抗反射膜。 [抗反射膜之評估] 藉由下述方法對實施例及比較例之抗反射膜進行評估。 (透濕度) 依據JIS K7129：2008附錄B於溫度40℃、濕度90%RH之環境中測定抗反射膜之透濕度。由於膜基材之透濕度充分大於抗反射層之透濕度，故而抗反射膜整體之透濕度被視為等於抗反射層之透濕度。 (算術平均粗糙度) 根據使用原子力顯微鏡(AFM)之1 μm見方之觀察像求出算術平均粗糙度。 (壓入彈性模數) 對於將抗反射膜之透明膜側之面貼附於載玻片之試樣，以抗反射層朝上而固定於奈米壓痕儀(Hysitron, Inc.製造，TI950 TriboIndenter)之平台上。測定係於23℃、50%RH之測定環境下，使用三角錐(berkovich)型之金剛石製壓頭(前端之曲率半徑：0.1 μm)緩緩施加負重，於達到最大負重後使負重緩緩恢復至0。藉由下述式而算出深度為10 nm左右之壓入彈性模數Er。 Er＝(S√π)/(2√A) S：卸載曲線之傾斜度 π：圓周率 A：壓頭與試樣之投影接觸面積再者，壓頭與試樣之投影接觸面積A係藉由日本專利特開2005-195357號公報中所記載之方法而求出。 (耐擦傷強度) 將鋼絲絨(日本鋼絲絨Bonstar #0000)固定於擦傷試驗機，施加2000 g之負重而進行往返10次之擦傷試驗，藉由目測而確認試驗後之抗反射膜之表面之外觀。將未確認到劃傷者設為〇，將確認到劃傷者設為×。 (指紋擦拭性) 使皮脂強制性地附著於抗反射膜之表面(於實施例1～5及比較例1～5中為防污層，於比較例6、7中為氟系抗反射層)。於滑動試驗機中安裝纖維素不織布刮擦器(旭化成，Bemcot M-1)，施加200 g之負重而於防污層之表面往返10次，藉由目測而確認皮脂是否被擦拭。將皮脂被擦拭者設為〇，將未完全被擦拭者設為×。 [附有抗反射層之偏光板之製作] 於偏光元件之一個面貼合實施例及比較例之抗反射膜，於偏光元件之另一面貼合包含具有內酯環結構之改性丙烯酸系聚合物的厚度為30 μm之透明膜(透濕度：125 g/m² ・24 h)，製作附有抗反射層之偏光板。作為偏光元件，使用將平均聚合度為2700、厚度為75 μm之聚乙烯醇膜一面進行碘染色一面延伸至6倍而成之PVA系偏光元件。於將PVA系偏光元件與透明膜接著時，使用包含以重量比3∶1含有具有乙醯乙醯基之聚乙烯醇樹脂(平均聚合度為1200，皂化度為98.5莫耳%，乙醯乙醯化度為5莫耳%)與羥甲基三聚氰胺之水溶液的接著劑，藉由輥貼合機進行貼合之後，於烘箱內進行加熱乾燥。 [偏光板之加熱可靠性評估] 將所獲得之附有抗反射層之偏光板投入至95℃之熱風烘箱內，於1000小時後取出。於背光上載置市售之偏光板，此後於其上以正交偏光而載置加熱試驗後之附有抗反射層之偏光板，藉由目測而確認有無外觀之變化。將於加熱試驗前後外觀未見變化者設為〇，將可見變化者設為×。將實施例及比較例之抗反射膜之製作條件、抗反射膜之評估結果、及偏光板之加熱可靠性評估結果示於表1。又，將實施例1～3及比較例1之偏光板之加熱試驗前後之外觀(正交偏光觀察)示於圖3。 [表1]

若觀察實施例1～3之抗反射層之濺鍍成膜條件、與抗反射層之特性之關聯，則可見如下傾向：濺鍍成膜時之壓力越低，則機械強度(壓入彈性模數)越高，抗反射層之透濕度越小，算術平均粗糙度Ra越變小。又，根據實施例4與比較例2之對比亦可知，存在伴隨濺鍍成膜時之壓力之下降而抗反射層之透濕度變小的傾向。根據該等結果可認為，若以低壓進行濺鍍成膜，則容易形成緻密之膜，伴隨成膜壓力之上升而容易形成更多孔之膜，故而透濕度上升。根據實施例3與實施例4之對比可知，藉由提高磁通密度而濺鍍成膜所需之放電電壓變小，抗反射層之透濕度上升，算術平均粗糙度Ra變小。根據實施例4與實施例5之對比可知，若以氧化區域將氧化物薄膜成膜，則抗反射層之透濕度減少，算術平均粗糙度Ra變小。根據比較例1與比較例2之對比、及實施例5與比較例3之對比可知，存在基材之轟擊處理時之壓力越大，則抗反射層之透濕度越高之傾向。如上所述，認為存在藉由轟擊處理而基材表面之算術平均粗糙度變大之傾向，由於藉由轟擊處理形成於表面之凹凸而濺鍍膜成長為柱狀，這有助於透濕度之上升。藉由減小濺鍍成膜壓力而形成有低透濕度之抗反射層之比較例1係如圖3所示，加熱試驗後之偏光板產生不均。另一方面，形成有高透濕之抗反射層之實施例1～5係與藉由真空蒸鍍法而形成有抗反射層之比較例5及藉由濕式塗佈而形成有抗反射層之比較例6、7相同，於加熱試驗前後外觀未見差異。根據該等結果可知，藉由增大抗反射層之透濕度，附有抗反射層之偏光板之加熱耐久性提高。藉由真空蒸鍍法而形成有抗反射層之比較例5係抗反射層之透濕度較高，偏光板之加熱耐久性良好，但膜之機械強度較小，耐擦傷性不充分。藉由濕式塗佈而形成有抗反射層之比較例6、7係抗反射層之機械強度較比較例5進一步下降。若將比較例6與比較例7進行對比，則藉由轟擊處理而增大基材之表面凹凸之比較例7係設於該基材上之抗反射層的算術平均粗糙度變大，指紋擦拭性下降。實施例1～5之抗反射膜均係表面之算術平均粗糙度Ra與比較例6等同或者小於比較例6，故而指紋擦拭性良好。根據以上之結果可知，藉由調整濺鍍成膜條件而形成透濕度較高且機械強度較高之抗反射層，獲得偏光板之高溫下之可靠性及機械強度優異之抗反射膜。又，於抗反射膜表面之算術平均粗糙度Ra較小之情形時，指紋擦拭性提高。根據上述實施例1～5與比較例1～4之對比，可謂作為兼具機械強度、由高透濕度所得之偏光板之加熱耐久性、及基於表面形狀之指紋擦拭性之抗反射膜之製造條件，較佳為藉由電漿處理(轟擊處理)等進行之基材表面形狀之調整、高磁場成膜、表面凹凸不變得過大之範圍內之高壓成膜、藉由調整氧流量而實現之過渡區域內之成膜等。[Configuration of Anti-Reflection Film] Fig. 1 is a cross-sectional view schematically showing the configuration of an anti-reflection film according to an embodiment. FIG. 2 is a cross-sectional view schematically showing a form of a polarizing plate provided with an anti-reflection layer, and an anti-reflection film is attached to one surface of the polarizing element 8. The anti-reflective film 100 of FIG. 1 is provided with an anti-reflective layer 5 on a transparent film substrate 1 with an adhesion improving layer 3 interposed therebetween. The anti-reflection layer is a laminate of two or more films. In FIG. 1, the anti-reflection layer 5 including a laminate of four

films

51, 52, 53, 54 is shown. <Transparent film base material> The transparent film base material 1 includes a flexible transparent film 10. It is preferable to provide a hard coat layer 11 on the side of the transparent film 10 where the anti-reflection layer 5 is formed. (Transparent film) The visible light transmittance of the transparent film 10 is preferably 80% or more, more preferably 90% or more. The thickness of the transparent film 10 is not particularly limited, but from the viewpoints of workability such as strength and handling properties, thin layer properties, etc., it is preferably about 5 to 300 μm, more preferably 10 to 300 μm, and still more preferably 20 to 200 μm. As the resin material constituting the transparent film 10, for example, a thermoplastic resin excellent in transparency, mechanical strength, and thermal stability can be cited. Specific examples of such thermoplastic resins include: cellulose resins such as triacetyl cellulose, polyester resins, polyether-based resins, poly-based resins, polycarbonate-based resins, and polyamide-based resins. , Polyimide resins, polyolefin resins, (meth)acrylic resins, cyclic polyolefin resins (butene resins), polyarylate resins, polystyrene resins, polyvinyl alcohol System resins, and their mixtures. As shown in FIG. 2, when the anti-reflection film and the polarizing element 8 are laminated, the transparent film 10 has a function as a base material for forming the anti-reflection layer 5 and a function as a protective film of the polarizing element 8. When the transparent film 10 and the polarizing element 8 are laminated and used, the moisture permeability of the transparent film 10 is preferably 100 g/m ² · 24 h or more, more preferably 130 g/m ² · 24 h or more, and more Preferably, it is 150 g/m ²・24 h or more. ^{The moisture permeability is the weight of water vapor passing through a sample with an area of 1 m 2} in 24 hours at 40°C and a relative humidity difference of 90%. It is measured in accordance with JIS (Japanese Industrial Standards) K7129:2008 Appendix B . If the moisture permeability of the transparent film 10 is large, when the polarizing plate is placed in a heated environment, the moisture in the polarizing element is easily released to the outside through the transparent film, so the deterioration of the polarizing element caused by moisture can be suppressed. On the other hand, if the moisture permeability of the transparent film 10 is too high, the humidification durability of the polarizing plate may decrease. Therefore, the moisture permeability of the transparent film 10 is preferably 2000 g/m ² ·24 h or less, and more preferably 1500 g/m ² ·24 h or less. In order to set the moisture permeability to the above-mentioned range, a cellulose resin can be preferably used as the material of the transparent film 10. Examples of cellulose resins include esters of cellulose and fatty acids. Specific examples of cellulose esters include cellulose acetate such as cellulose triacetate and cellulose diacetate, cellulose tripropionate, cellulose dipropionate, and the like. Among them, particularly preferred is cellulose triacetate. It is also possible to contain one or more arbitrary additives in the transparent film. Examples of additives include ultraviolet absorbers, antioxidants, lubricants, plasticizers, mold release agents, anti-coloring agents, flame retardants, nucleating agents, antistatic agents, pigments, colorants, and the like. (Hard coat layer) It is preferable to provide a hard coat layer 11 on the surface of the transparent film 10. By disposing the hard coat layer 11 on the surface of the transparent film substrate 1 where the anti-reflection layer 5 is formed, mechanical properties such as the hardness or elastic modulus of the anti-reflection layer can be improved. The hard coat layer 11 preferably has high surface hardness and excellent scratch resistance. The hard coat layer 11 can be formed by coating a solution containing a curable resin on the transparent film 10, for example. Examples of curable resins include thermosetting resins, ultraviolet curing resins, electron beam curing resins, and the like. The types of curable resins include polyester, acrylic, urethane, acrylic urethane, amide, silicone, silicate, epoxy, Various resins such as melamine series, oxetane series, and acrylic urethane series. One kind or two or more kinds of these curable resins can be appropriately selected and used. Among them, acrylic resins, acrylic urethane resins, and epoxy resins are preferred in terms of high hardness, UV curability, and excellent productivity. Among them, acrylic resins are preferred. Urethane resin. UV-curing resins include UV-curing monomers, oligomers, polymers, etc. UV-curable resins that can be preferably used include, for example, those having UV-polymerizable functional groups, and among them, acrylic monomers or oligomers containing two or more, especially 3-6 functional groups can also be cited. The thing as an ingredient. In order to make the anti-reflective film have anti-glare properties and anti-glare properties, the hard coat layer provided on the surface of the transparent film preferably has anti-glare properties. Examples of the anti-glare hard coat layer include those obtained by dispersing fine particles in the above-mentioned curable resin matrix. As the fine particles dispersed in the resin matrix, it can be used without particular limitation: various metal oxide fine particles such as silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, calcium oxide, tin oxide, indium oxide, cadmium oxide, and antimony oxide, glass Micro particles, including cross-linked or uncross-linked of various transparent polymers such as polymethyl methacrylate, polystyrene, polyurethane, acrylic-styrene copolymer, benzoguanamine, melamine, polycarbonate, etc. Organic type fine particles, silicone type fine particles, etc. have transparency. One kind or two or more kinds of these fine particles can be appropriately selected and used. Among them, fine particles having a refractive index higher than that of the matrix resin are preferred, and for example, organic fine particles having a refractive index of 1.5 or more such as styrene beads (with a refractive index of 1.59) are preferred. The average particle diameter of the fine particles is preferably 1-10 μm, more preferably 2-5 μm. The ratio of the fine particles is not particularly limited, but it is preferably 6 to 20 parts by weight relative to 100 parts by weight of the matrix resin. The hard coat layer can be formed, for example, by coating a solution containing a curable resin on the transparent film 10. It is preferable to prepare an ultraviolet polymerization initiator in the solution for forming the hard coat layer. In order to form the anti-glare hard coat layer containing fine particles, it is preferable to coat a solution containing the above fine particles in addition to the curable resin on the transparent film. The solution may also contain additives such as leveling agents, thixotropic agents, and antistatic agents. When forming an anti-glare hard coating layer, by containing a thixotropic agent (silica, mica, etc. with a particle size of 0.1 μm or less) in the solution, the fine particles obtained from the protruding particles can be easily formed on the surface of the hard coating layer. Concavo-convex structure. The thickness of the hard coat layer 11 is not particularly limited. In order to achieve a higher hardness, it is preferably 0.5 μm or more, and more preferably 1 μm or more. Considering the ease of formation by coating, the thickness of the hard coat layer is preferably 15 μm or less, more preferably 12 μm or less, and still more preferably 10 μm or less. In addition, in order to maintain a high moisture permeability of the film substrate so as not to hinder the release of moisture from the polarizing element to the outside, the thickness of the hard coat layer 11 is preferably within the above-mentioned range. The arithmetic average roughness Ra of the surface of the transparent film substrate 1 on the side where the anti-reflection layer 5 is formed is preferably 1.5 nm or less, more preferably 1.0 nm or less. When the hard coat layer 11 is formed on the transparent film 10, the arithmetic average roughness of the hard coat layer 11 becomes the arithmetic average roughness of the surface of the transparent film 10 on the side where the anti-reflection layer 5 is formed. The arithmetic average roughness Ra is obtained from an observation image of 1 μm square using an atomic force microscope (AFM). If the hard coat layer 11 is formed by coating as described above, the arithmetic average roughness of the surface of the transparent film substrate 1 can be reduced. If the surface of the transparent film substrate 1 is smooth, there is a tendency that the arithmetic average roughness of the surface of the anti-reflection layer 5 formed on the transparent film substrate also becomes smaller, and the scratch resistance of the anti-reflection film is improved. (Surface treatment) The surface of the transparent film substrate 1 can also be subjected to corona treatment, plasma treatment, flame treatment, ozone treatment, primer treatment, and glow treatment for the purpose of improving the adhesion with the anti-reflection layer 5, etc. , Saponification treatment, treatment with coupling agent and other surface modification treatments. For example, by performing plasma treatment in a vacuum to modify the surface of the substrate and form proper unevenness on the surface, the adhesion between the transparent film substrate 1 (hard coat layer 11) and the anti-reflective layer 5 can be improved . In addition, by forming an anti-reflection layer on the unevenness formed on the surface by plasma treatment, the moisture permeability of the anti-reflection film tends to increase. As described below, in order to improve the adhesiveness between the transparent film base material 1 and the anti-reflection layer 5, the adhesiveness improvement layer 3 may be provided on the transparent film base material 1. <Anti-reflection layer> The anti-reflection layer 5 is formed on the transparent film base material 1. The anti-reflection layer 5 includes two or more films. Generally speaking, the anti-reflection layer adjusts the optical thickness (the product of the refractive index and the thickness) of the film in such a way that the phases of the incident light and the reflected light cancel each other out. By setting the anti-reflection layer as a multilayer laminate of two or more thin films with different refractive indexes, the reflectance can be reduced in the wide-band wavelength range of visible light. As the material of the thin film constituting the anti-reflection layer 5, metal oxides, nitrides, fluorides, etc. can be cited. For example, as a low refractive index material having a refractive index of 1.6 or less at a wavelength of 550 nm, silicon oxide, magnesium fluoride, and the like can be cited. Examples of high refractive materials with a refractive index of 1.9 or more at a wavelength of 550 nm include titanium oxide, niobium oxide, zirconium oxide, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), and the like. In addition to the low-refractive index layer and the high-refractive index layer, for example, a thin film containing titanium oxide or a mixture of the aforementioned low-refractive index material and high-refractive material may be formed as the intermediate refractive index layer with a refractive index of about 1.50 to 1.85. The film constituting the anti-reflection layer preferably has a low light absorption of visible light, and a material with an extinction coefficient of 0.5 or less at a wavelength of 550 nm can be preferably used. As a laminated structure of the anti-reflection layer 5, from the side of the transparent film 10, a high refractive index layer with an optical film thickness of about 240 nm to 260 nm and a low refractive index layer with an optical film thickness of about 120 nm to 140 nm can be cited. The two-layer structure; the optical film thickness is about 170 nm to 180 nm, the middle refractive index layer, the optical film thickness is about 60 nm to 70 nm, and the optical film thickness is about 135 nm to 145 nm. Three layers of refractive index layer; high refractive index layer with an optical film thickness of about 20 nm to 55 nm, a low refractive index layer with an optical film thickness of about 15 nm to 70 nm, and an optical film thickness of about 60 nm to 330 nm The high refractive index layer and the low refractive index layer with an optical film thickness of about 100 nm to 160 nm are composed of 4 layers; the optical film thickness is about 15 nm to 30 nm, and the optical film thickness is about 20 nm to low refractive index layer. A high refractive index layer of about 40 nm, a low refractive index layer with an optical film thickness of about 20 nm to 40 nm, a high refractive index layer with an optical film thickness of about 240 nm to 290 nm, and an optical film thickness of 100 nm to 200 It is composed of 5 layers of low refractive index layer around nm. The range of the refractive index or the film thickness of the film constituting the anti-reflection layer is not limited to the above-mentioned examples. In addition, the anti-reflection layer 5 may be a laminate of 6 or more films. The anti-reflection layer is preferably an alternate laminate of a low refractive index layer and a high refractive index layer. In order to reduce the reflection at the air interface, the thin film 54 provided as the outermost layer of the anti-reflection layer (the surface opposite to the transparent film substrate 1) is preferably a low refractive index layer. As described above, as the material of the low refractive index layer and the high refractive index layer, oxides are preferred. Among them, the anti-reflection layer 5 is preferably an _{alternate laminate of silicon oxide (SiO 2} )

films

52 and 54 as a low refractive index layer and niobium oxide (Nb ₂ O ₅ )

films

51 and 53 as a high refractive index layer. The moisture permeability of the anti-reflection layer 5 is preferably 15 g/m ² · 24 h or more, more preferably 20 g/m ² · 24 h or more, and still more preferably 30 g/m ² · 24 h or more. By increasing the moisture permeability of the anti-reflective layer, the retention of moisture can be suppressed, and the durability under high temperature can be improved. From the viewpoint of further improving the durability at high temperature, the moisture permeability of the anti-reflection layer 5 may be 100 g/m ² ·24 h or more or 130 g/m ² ·24 h or more. If the moisture permeability of the anti-reflective layer is too high, the durability under high humidity tends to decrease. Therefore, the moisture permeability of the anti-reflective layer 5 is preferably 1000 g/m ² ·24 h or less, more preferably 500 g/m ²・24 hours or less. The anti-reflection layer is a thin film, and it is difficult to determine the moisture permeability in the form of a monomer. Therefore, what is necessary is just to form an anti-reflection layer on a transparent film base material, and to measure the moisture permeability. The moisture permeability of most resin films is sufficiently greater than the moisture permeability of the inorganic oxide layer. Therefore, the moisture permeability of the anti-reflective film provided with the anti-reflective layer 5 on the transparent film substrate 1 is regarded as equal to the moisture permeability of the anti-reflective layer 5. Therefore, the moisture permeability of the anti-reflection film of the present invention is preferably 15 to 1000 g/m ² · 24 h, more preferably 20 to 500 g/m ² · 24 h or more. If the anti-reflection film provided with the anti-reflection layer 5 or the polarizing plate with the anti-reflection layer on the transparent film substrate 1 is exposed to a heating environment, the moisture in the transparent film 10 or the polarizing element 8 will evaporate to the outside of the film. When the moisture permeability of the anti-reflective layer is small, it is difficult for moisture to diffuse outside the system. If moisture stays inside the polarizing plate, there is a tendency that the triacetyl cellulose of the transparent film 10 is easily hydrolyzed, and the protective performance of the polarizing element is reduced. In addition, when acetyl cellulose is hydrolyzed, free acid is generated. In the presence of acid, the polyvinyl alcohol that constitutes the polarizing element is prone to polyolefination, resulting in the deterioration of the polarizing plate. In contrast, when the moisture permeability of the anti-reflective layer 5 is large, the moisture evaporated from the polarizing element or the transparent film is likely to diffuse from the surface of the anti-reflective layer 5 to the outside of the system. Therefore, the retention of moisture is suppressed, and under high temperature The deterioration of the polarizing plate is suppressed. The compression modulus of elasticity of the anti-reflection layer 5 is preferably 20 GPa or more, more preferably 30 GPa or more. By increasing the elastic modulus of the anti-reflection layer, the scratch resistance is improved. On the other hand, if the modulus of elasticity is too large, handling properties such as transportability of the film may decrease. Therefore, the compression modulus of the anti-reflection layer 5 is preferably 100 GPa or less, more preferably 70 GPa or less. For the same reason, the indentation hardness of the anti-reflection layer is preferably 0.5-10 GPa, more preferably 1-5 GPa. The indentation elastic modulus and indentation hardness are measured by nanoindentation. The arithmetic average roughness Ra of the surface of the anti-reflection layer 5 is preferably 3 nm or less, more preferably 1.8 nm or less, still more preferably 1.5 nm or less, particularly preferably 1.3 nm or less. By reducing the arithmetic average roughness, there is a tendency to improve scratch resistance. In particular, if the arithmetic average roughness of the surface of the anti-reflection layer 5 is 1.5 nm or less, there is a tendency for the wiping property to improve when dirt such as sebum adheres. On the other hand, if the arithmetic average roughness of the surface of the anti-reflection layer 5 is too small, there is a tendency that roll conveyance during film production becomes difficult, so the arithmetic average roughness of the surface of the anti-reflection layer 5 is preferably 0.3 nm or more , More preferably 0.5 nm or more. The film forming method of the thin film constituting the anti-reflection layer is not particularly limited, and may be any of a wet coating method and a dry coating method. In terms of forming a uniform and dense thin film, dry coating methods such as vacuum evaporation, CVD (Chemical Vapor Deposition), sputtering, and electron beam evaporation are preferred. Among them, the sputtering method is particularly preferred in terms of easy formation of a film with high mechanical strength having the above-mentioned elastic modulus. By using a roll-to-roll method to continuously form a film while conveying a long film substrate in one direction (longitudinal direction), the productivity of the anti-reflective film can be improved. The film formation of an oxide layer such as silicon oxide or niobium oxide by a sputtering method can be performed by either a method using an oxide target material or reactive sputtering using a metal target material. In order to use an oxide target to form an insulating oxide such as silicon oxide into a film, RF (Radio Frequency) discharge is required, so the film formation rate is low and the productivity is low. Therefore, the sputtering of oxides is preferably reactive sputtering using a metal target. In reactive sputtering, an inert gas such as argon and a reactive gas such as oxygen are introduced into the chamber while forming a film. In reactive sputtering, it is preferable to adjust the amount of oxygen so as to become a transition region between the metal region and the oxide region. If the film is formed in a metal region with insufficient oxygen content, there is a tendency that the oxygen content of the obtained film is much less than the stoichiometric composition, and the anti-reflection layer has metallic luster and the transparency is reduced. In addition, the oxide region with a large amount of oxygen tends to extremely decrease the film formation rate. By adjusting the amount of oxygen such that the sputtering film becomes a transition area, the oxide film can be formed at a high rate. In addition, by forming the film in the transition region, the moisture permeability of the obtained film increases, and the durability at high temperatures tends to increase. As a sputtering power source used for reactive sputtering, DC (Direct Current) or MF (Medium Frequency)-AC (Alternating Current) is preferred. In the reactive dual magnetron sputtering method, as a method of controlling the amount of oxygen introduced in such a way that the film forming mode becomes a transition zone, a plasma that detects the plasma luminous intensity of the discharge and controls the amount of gas introduced into the film forming chamber can be cited Transmission monitoring mode (PEM mode). PEM is controlled by detecting the luminous intensity of the plasma and feeding back the amount of oxygen introduced. For example, PEM control can be performed by setting the control value (set point) of the luminous intensity to a specific range, and the amount of oxygen introduced can be adjusted to maintain the film formation in the transition region. In addition, it is also possible to perform control using an impedance method in which the plasma impedance is fixed, that is, the discharge voltage is fixed to control the amount of oxygen introduced. If the oxygen introduction amount is controlled by the PEM method or the impedance method, the film formation rate in the continuous film formation of the film under the roll-to-roll method can be kept constant in the length direction. Therefore, the film thickness of the film becomes uniform, and an anti-reflection film with excellent anti-reflection properties can be obtained. By arranging a plurality of oxygen introduction pipes in the width direction and individually controlling the oxygen flow rate introduced from each pipe, the uniformity of the quality in the width direction can also be improved. In sputtering film formation, abnormal discharge occurs due to the adhesion of particles to the surface of the target, etc., and the film quality of the thin film decreases in the part where the abnormal discharge occurs. Such abnormal discharge can also be monitored by plasma glow or discharge voltage. When the plasma luminescence amount deviates from the control range due to abnormal discharge, etc., the possibility of abnormal film quality or film thickness is higher. Therefore, if the part is judged as "defective", and by setting it in the more sputtering The film forming part is marked by the marking device on the downstream side, and the defective part can be easily removed from the long anti-reflective film. In the sputtering method, the material is ejected from the target by making high-energy sputtering gas (for example, Ar) collide with the target, so the sputtering particles also have high energy. Therefore, compared with the vacuum evaporation method or the CVD method, the sputtering method is easier to form a dense film. Generally speaking, a thin film formed by a sputtering method has a low moisture permeability. For example, the moisture permeability of a silicon oxide film is 10 g/m ² · 24 h or less in most cases. By adjusting the sputtering film forming conditions, a film with a moisture permeability of 15 g/m ² ·24 h or more can be formed. For example, when the discharge voltage during sputtering film formation is small, the movement energy of the sputtered particles is small, and the diffusion on the surface of the substrate is suppressed. Therefore, the membrane tends to grow into a columnar shape, and the membrane quality tends to become porous. When the discharge voltage is high, the film is easy to be formed into a surface shape, and it is easy to become a dense film. On the other hand, if the discharge voltage is too high, there is a tendency that neutral particles such as Ar colliding against the surface of the film damage the film surface and cause defects, so the film density decreases. Regarding magnetron sputtering, in the case of a strong magnetic field (higher magnetic flux density), there is a tendency for plasma diffusion to be suppressed and the plasma density to increase. Along with this, the discharge voltage can be reduced, so as described above, the film tends to grow into a columnar shape and the moisture permeability tends to increase. In addition, since the kinetic energy of the sputtered particles decreases with the decrease in the discharge voltage, the damage caused by the collision of the Ar particles and the like can be reduced. Therefore, the film surface is easily smoothed, and an anti-reflective film having a small arithmetic average roughness Ra and excellent scratch resistance or fingerprint wiping properties can be obtained. The magnetic flux density on the surface of the target during sputtering film formation is preferably 20 mT or more, more preferably 35 mT or more, still more preferably 45 mT or more, particularly preferably 55 mT or more. If the pressure at the time of film formation is high, the mean free path of the sputtered particles becomes smaller, the directivity of the sputtered particles decreases, and the sputtered particles are easily diffused by Ar, so the film quality is likely to become porous. On the other hand, if the film formation pressure is too high, the film formation rate decreases. In addition, if the film formation pressure is high, the plasma discharge tends to become unstable. In order to form an oxide film with high moisture permeability and sufficient mechanical strength, the film forming pressure is preferably 0.4 Pa to 1.5 Pa. Sometimes in addition to the sputtering film formation conditions, the surface shape of the substrate that becomes the film formation base also affects the film growth pattern. For example, if plasma treatment is performed on the surface of the transparent film substrate as described above, the sputtered film tends to grow into a columnar shape due to the unevenness formed on the surface, and the moisture permeability tends to increase. (Adhesion Improving Layer) In many cases, the adhesion between the organic material such as the hard coat layer 11 and the oxide thin film is insufficient. Therefore, it is preferable to provide the adhesion improving layer 3 between the transparent film base material 1 and the anti-reflection layer 5. Examples of the material for the adhesion-improving layer 3 include metals such as silicon, nickel, chromium, aluminum, tin, gold, silver, platinum, zinc, titanium, tungsten, zirconium, and palladium; alloys containing two or more of these metals ; Oxides, nitrides and fluorides of these metals. In terms of high light transmittance and high adhesion to both the organic layer and the oxide layer, as the adhesion enhancing layer 3, an oxide having an oxygen content less than a stoichiometric composition is particularly preferred. The oxygen content of the adhesion-improving layer 3 is preferably about 60 to 95% of the stoichiometric composition. For example, when a silicon _{oxide (SiO x} ) layer is formed as the adhesion improving layer 3, x is preferably 1.2 to 1.9. The thickness of the adhesion-improving layer 3 may be such as long as it does not impair the transparency of the transparent film substrate 1, and is, for example, about 1 to 10 nm or less. The adhesion-improving layer 3 can be formed by a sputtering method, a vacuum vapor deposition method, an ion plating method, a CVD method, or the like. In the case of forming the anti-reflection layer 5 by the sputtering method, the transparent film base material 1 can be transported while the adhesion-improving layer 3 and the anti-reflection layer 5 are continuously formed in one pass. Therefore, it is preferable that the adhesiveness improvement layer 3 is formed into a film by a sputtering method. In sputtering of oxide thin films with less than stoichiometric composition, the amount of oxygen introduced can also be controlled by the PEM method or the impedance method. (Anti-fouling layer) The anti-reflective film is used on the top surface of displays such as liquid crystal display devices, so it is susceptible to pollution from the external environment (fingerprints, hand dirt, dust, etc.). _{In particular, the low-refractive index layer such as SiO 2} provided on the outermost surface of the anti-reflection layer has good wettability, and contaminants such as fingerprints or hand dirt are easy to adhere. In addition, compared with general transparent films, the contamination of the anti-reflection layer containing oxides is more conspicuous, and contaminants are easy to adhere. Therefore, the display becomes invisible due to changes in surface reflectivity or whitening of adherents. A clear situation. In order to facilitate the prevention of pollution from the external environment or the removal of attached pollutants, it is preferable to provide an anti-fouling layer 7 on the surface of the anti-reflection layer 5. In order to improve the antifouling property and the removal of pollutants, the pure water contact angle of the antifouling layer 7 is preferably 100° or more, more preferably 102° or more, and still more preferably 105° or more. The pure water contact angle can be determined by the following method: forming water droplets with a diameter of 2 mm or less on the surface of the pollution prevention layer and measuring the contact angle. In order to maintain the anti-reflection characteristics of the anti-reflection layer 5, the anti-fouling layer 7 preferably has a smaller refractive index difference with the low-refractive-index layer 54 on the outermost surface of the anti-reflection layer 5. The refractive index of the antifouling layer 7 is preferably 1.6 or less, more preferably 1.55 or less. The material of the antifouling layer 7 is preferably a silane compound containing a fluorine group, or an organic compound containing a fluorine group, or the like. The antifouling layer 7 can be formed by a wet method such as a reverse coating method, a die nozzle coating method, a gravure coating method, or a dry method such as a CVD method. The thickness of the antifouling layer 7 is usually about 1-100 nm, preferably 2-50 nm, more preferably 3-30 nm. In order to maintain the mechanical strength such as scratch resistance of the anti-reflective layer 5, the anti-fouling layer 7 is also preferably the same as the anti-reflective layer 5, and the arithmetic average roughness Ra of the surface is small. The arithmetic average roughness of the surface of the antifouling layer 7 (ie, the arithmetic average roughness of the surface of the anti-reflection film) is preferably 3 nm or less, more preferably 2 nm or less, further preferably 1.8 nm or less, particularly preferably 1.5 Below nm, preferably below 1.3 nm. If the arithmetic average roughness of the surface of the anti-reflection film is 1.5 nm or less, there is a tendency for fingerprint wiping properties to improve. [Polarizing plate with anti-reflection layer] As shown in Fig. 2, the anti-reflection film of the present invention can be laminated with a polarizing element to be used as a polarizing plate with an anti-reflection layer for practical use. The polarizing plate 110 with an anti-reflection layer shown in FIG. 2 is attached to one surface of the polarizing element 8 on the main surface of the transparent film substrate 1 opposite to the surface on which the anti-reflection layer is formed. A transparent film 9 is attached to the other side of the polarizing element 8. Examples of the polarizing element 8 include: absorbing iodine or dichroic dyes on hydrophilic polymer films such as polyvinyl alcohol-based films, partially formalized polyvinyl alcohol-based films, ethylene-vinyl acetate copolymer-based partially saponified films, etc. Dichroic substances obtained by uniaxial stretching; polyene-based alignment films such as dehydrated polyvinyl alcohol or dehydrated polyvinyl chloride. Among them, in terms of having a high degree of polarization, it is preferable to make a polyvinyl alcohol film such as polyvinyl alcohol or partially formalized polyvinyl alcohol adsorb dichroic substances such as iodine or dichroic dyes, and to specify Polyvinyl alcohol (PVA)-based polarizing elements aligned in the direction. For example, a PVA-based polarizing element can be obtained by performing iodine dyeing and stretching on a polyvinyl alcohol-based film. As the PVA-based polarizing element, a thin polarizing element with a thickness of 10 μm or less can also be used. Examples of thin polarizing elements include Japanese Patent Laid-Open No. 51-069644, Japanese Patent Laid-Open No. 2000-338329, WO2010/100917 brochure, Japanese Patent No. 4693205, Japanese Patent No. 4751481, etc. The thin polarizing film described in. Such a thin polarizing element can be obtained, for example, by a manufacturing method including the following steps: a step of extending the PVA-based resin layer and a resin substrate for stretching in the state of a laminate; and a step of performing iodine dyeing. As the transparent film 9, the same material as that described above as the material of the transparent film 10 can be preferably used. Furthermore, the material of the transparent film 9 and the material of the transparent film 10 may be the same or different. When bonding the polarizing element and the transparent film, it is preferable to use an adhesive. As the adhesive, acrylic polymer, silicone polymer, polyester, polyurethane, polyamide, polyvinyl alcohol, polyvinyl ether, vinyl acetate/vinyl chloride copolymer can be appropriately selected. It is used as the base polymer, such as modified polyolefin, epoxy-based polymer, fluorine-based polymer, rubber-based polymer, etc. When bonding the PVA-based polarizing element, a polyvinyl alcohol-based adhesive can be preferably used. The anti-reflection film and the polarizing plate with the anti-reflection layer of the present invention can be used in displays such as liquid crystal display devices or organic EL display devices. Especially when used as the most surface layer of a display, it helps to improve the visibility of the display by anti-reflection. The anti-reflection film and the polarizing plate with the anti-reflection layer of the present invention are hard to be degraded even when exposed to a high-temperature environment for a long time, and have excellent high-temperature reliability, so they can be particularly preferably used in automotive displays and the like. [Examples] Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited to the following examples. [Production of film with anti-glare hard coat layer] 100 parts by weight of ultraviolet curable acrylic urethane monomer (refractive index: 1.51), average particle size of 3.5 μm (particle distribution range of 3.0～ 4.1 μm) polystyrene beads (refractive index of 1.59) 14 parts by weight, 5 parts by weight of benzophenone-based photopolymerization initiator, and 171 parts by weight of toluene were mixed, and the solid component concentration obtained by mixing was 40 The weight% solution was coated on a 80 μm-thick triacetyl cellulose film (refractive index: 1.49), and dried at 120° C. for 5 minutes. After that, it was cured by ultraviolet radiation to form an anti-glare hard coating with a thickness of about 4 μm with a concavo-convex structure on the surface. The arithmetic average roughness Ra of the anti-glare hard coating is 0.43 nm. [Example 1] A triacetyl cellulose film formed with an anti-glare hard coating was introduced into a roll-to-roll sputtering film forming device, and the film was moved while the anti-glare hard coating was formed. The surface is bombarded (plasma treatment with Ar gas), and then a 3.5 nm SiO _x layer (x<2) is formed as an adhesion-improving layer, and a 12 nm Nb ₂ O ₅ layer is formed _{on the SiO x layer} , 28 nm SiO ₂ layer, 100 nm Nb ₂ O ₅ layer and 85 nm SiO ₂ layer are formed sequentially. On the anti-reflective layer, a fluorine-based resin is formed as an anti-fouling layer so that the thickness becomes 5 nm to produce an anti-reflective film. (Bombardment treatment) The bombardment treatment is carried out under the conditions of a pressure of 0.5 Pa and an effective power density of 0.34 W·min/m·cm ² . Furthermore, the arithmetic average roughness Ra of the surface of the anti-glare hard coat layer (without the adhesion-improving layer and the anti-reflection layer) after the bombardment treatment is 0.51 nm, which is larger than that before the treatment. The so-called effective power density is ^{the value obtained by dividing the power density (W/cm 2} ) of the plasma output by the transport speed (m/min) of the film substrate in the roll-to-roll method. Even if the plasma power is the same, the effective processing power decreases when the conveying speed is high. (Sputtering film formation) The SiOx layer as the adhesion improving layer is formed by applying 3 W/cm ² MF-AC power 40 kHz to the Si target at a pressure of 0.4 Pa. The _{Si target was used for the formation of the SiO 2} layer, and the Nb target was used for the formation of the Nb ₂ O ₅ layer, and the film was formed at the voltage and pressure shown in Table 1. In the formation of oxide thin films, the pressure is kept constant by adjusting the amount of argon introduced and the amount of exhaust gas, and the amount of oxygen introduced is adjusted to maintain the transition zone in the film forming mode by the plasma luminescence monitoring (PEM) control . [Examples 2 to 5 and Comparative Examples 1 to 4] As shown in Table 1, the effective power density of the bombardment treatment, the discharge voltage and the pressure when the _{SiO 2} layer and the Nb ₂ O _{5 layer were formed were changed.} In Examples 4 and 5 and Comparative Examples 1 to 4, the magnet was changed and the film was formed under the condition that the magnetic flux density on the surface of the target material was 80 mT. In Example 5 and Comparative Example 3, the amount of oxygen introduced was adjusted by PEM control to maintain the oxidation region in the film formation mode. [Comparative Example 5] Under the conditions of a pressure of 0.15 Pa and an effective power density of 0.10 W·min/m·cm ² , the surface of the hard coat layer of the triacetyl cellulose film with the anti-glare hard coat layer was subjected to bombardment treatment. After that, a Nb ₂ O ₅ layer of 12 nm, a SiO ₂ layer of 28 nm, a Nb ₂ O ₅ layer of 100 nm, and a SiO ₂ layer of 85 nm were sequentially formed by vacuum evaporation, as in Example 1. Similarly, an anti-fouling layer is formed on the anti-reflection layer to produce an anti-reflection film. [Comparative Example 6] A low refractive index layer of 100 nm was formed on the hard coat surface of the triacetyl cellulose film formed with an anti-glare hard coat layer by wet coating to produce an anti-reflection film. As the material of the low refractive index layer, a fluorochemical polymer produced by a sol-gel reaction of a mixture of polysiloxane and fluoroalkyl silane is used. [Comparative Example 7] The surface of the anti-glare hard coating was bombarded under the conditions of a pressure of 0.5 Pa and an effective power density of 0.10 W·min/m·cm ^2. Thereafter, in the same manner as in Comparative Example 6, an anti-reflection film was produced. [Evaluation of Anti-Reflection Film] The anti-reflection films of the Examples and Comparative Examples were evaluated by the following methods. (Moisture permeability) According to JIS K7129:2008 Appendix B, the moisture permeability of the anti-reflective film is measured in an environment with a temperature of 40°C and a humidity of 90%RH. Since the moisture permeability of the film substrate is sufficiently greater than the moisture permeability of the anti-reflective layer, the moisture permeability of the entire anti-reflective film is regarded as equal to the moisture permeability of the anti-reflective layer. (Arithmetic average roughness) The arithmetic average roughness is calculated from the observation image of 1 μm square using an atomic force microscope (AFM). (Indentation modulus of elasticity) For the sample with the transparent film side of the anti-reflection film attached to the glass slide, fix it on a nanoindenter (manufactured by Hysitron, Inc., TI950) with the anti-reflection layer facing upwards TriboIndenter) on the platform. The measurement is performed under a measurement environment of 23°C and 50%RH, using a berkovich type diamond indenter (curvature radius of the tip: 0.1 μm) to slowly apply the load, and then slowly recover the load after reaching the maximum load. To 0. The indentation elastic modulus Er with a depth of about 10 nm is calculated by the following formula. Er=(S√π)/(2√A) S: the inclination of the unloading curve π: the circumference ratio A: the projected contact area between the indenter and the sample. Furthermore, the projected contact area A between the indenter and the sample is determined by It is determined by the method described in Japanese Patent Laid-Open No. 2005-195357. (Scratch resistance strength) Fix steel wool (Japanese steel wool Bonstar #0000) on the scratch tester, apply a load of 2000 g and carry out the scratch test 10 times back and forth. The surface of the anti-reflective film after the test is confirmed by visual inspection. Exterior. The person who has not been confirmed to be scratched is set to 0, and the person who is confirmed to be scratched is set to ×. (Fingerprint wipeability) Forcibly attaching sebum to the surface of the anti-reflection film (anti-fouling layer in Examples 1 to 5 and Comparative Examples 1 to 5, and fluorine-based anti-reflection layer in Comparative Examples 6 and 7) . Install a cellulose non-woven wiper (Asahi Kasei, Bemcot M-1) in the sliding tester, apply a load of 200 g and reciprocate 10 times on the surface of the antifouling layer, and confirm whether the sebum is wiped by visual inspection. The person whose sebum was wiped was set to 0, and the person who was not completely wiped was set to ×. [Production of polarizing plate with anti-reflective layer] The anti-reflective film of the embodiment and the comparative example was laminated on one side of the polarizing element, and the modified acrylic polymer containing the lactone ring structure was laminated on the other side of the polarizing element The thickness of the object is a transparent film with a thickness of 30 μm (humidity permeability: 125 g/m ² · 24 h), and a polarizing plate with an anti-reflection layer is produced. As the polarizing element, a PVA-based polarizing element obtained by extending a polyvinyl alcohol film with an average degree of polymerization of 2700 and a thickness of 75 μm to 6 times while dyeing with iodine was used. When bonding the PVA-based polarizing element and the transparent film, use a polyvinyl alcohol resin containing an acetyl acetyl group in a weight ratio of 3:1 (average degree of polymerization is 1200, degree of saponification is 98.5 mol%, acetyl acetate) The adhesive of 5 mol%) and an aqueous solution of methylol melamine is bonded by a roll laminator, and then heated and dried in an oven. [Evaluation of heating reliability of polarizing plate] Put the obtained polarizing plate with anti-reflection layer into a 95℃ hot air oven, and take it out after 1000 hours. A commercially available polarizing plate is placed on the backlight, and then the polarizing plate with anti-reflection layer after the heating test is placed on it with orthogonal polarization, and whether there is any change in appearance is confirmed by visual inspection. If there is no change in appearance before and after the heating test, it is set as 0, and the one with visible change is set as ×. Table 1 shows the production conditions of the anti-reflection film of the embodiment and the comparative example, the evaluation result of the anti-reflection film, and the heating reliability evaluation result of the polarizing plate. In addition, the appearance (observed by crossed polarization) of the polarizing plates of Examples 1 to 3 and Comparative Example 1 before and after the heating test is shown in FIG. 3. [Table 1]

Observing the correlation between the sputtering film forming conditions of the anti-reflection layer of Examples 1 to 3 and the characteristics of the anti-reflection layer, the following tendency can be seen: the lower the pressure during sputtering film formation, the mechanical strength (pressing into the elastic mold) The higher the number, the lower the moisture permeability of the anti-reflection layer, and the smaller the arithmetic average roughness Ra. In addition, it can be seen from the comparison between Example 4 and Comparative Example 2 that the moisture permeability of the anti-reflection layer tends to decrease as the pressure during sputtering film formation decreases. From these results, it can be considered that if the sputtering film is formed at a low pressure, a dense film is easily formed, and a more porous film is easily formed with an increase in the film forming pressure, so the moisture permeability increases. According to the comparison between Example 3 and Example 4, by increasing the magnetic flux density, the discharge voltage required for sputtering film formation becomes smaller, the moisture permeability of the anti-reflection layer increases, and the arithmetic average roughness Ra becomes smaller. According to the comparison between Example 4 and Example 5, it can be seen that if an oxide thin film is formed in an oxidized area, the moisture permeability of the anti-reflection layer will decrease, and the arithmetic average roughness Ra will decrease. According to the comparison between Comparative Example 1 and Comparative Example 2, and the comparison between Example 5 and Comparative Example 3, it can be seen that the greater the pressure during the bombardment treatment of the substrate, the higher the moisture permeability of the anti-reflection layer. As described above, it is considered that the arithmetic average roughness of the substrate surface tends to increase by the bombardment treatment, and the sputtering film grows into a columnar shape due to the unevenness formed on the surface by the bombardment treatment, which contributes to the increase in moisture permeability. . The comparative example 1 in which the anti-reflection layer with low moisture permeability was formed by reducing the pressure of sputtering film formation is shown in FIG. On the other hand, Examples 1 to 5 in which an anti-reflective layer with high moisture permeability was formed, and Comparative Example 5 in which an anti-reflective layer was formed by a vacuum evaporation method, and an anti-reflective layer was formed by wet coating The comparative examples 6 and 7 are the same, and there is no difference in appearance before and after the heating test. According to these results, by increasing the moisture permeability of the anti-reflection layer, the heating durability of the polarizing plate with the anti-reflection layer is improved. In Comparative Example 5 with an anti-reflection layer formed by a vacuum evaporation method, the anti-reflection layer has a higher moisture permeability, and the heating durability of the polarizing plate is good, but the mechanical strength of the film is low, and the scratch resistance is insufficient. The mechanical strength of the anti-reflection layer of Comparative Examples 6 and 7 in which the anti-reflection layer was formed by wet coating was further lower than that of Comparative Example 5. If Comparative Example 6 is compared with Comparative Example 7, the comparative example 7 in which the surface unevenness of the substrate is increased by the bombardment treatment is that the arithmetic average roughness of the anti-reflection layer on the substrate becomes larger, and the fingerprint wipes Sexual decline. The arithmetic average roughness Ra of the surface of the anti-reflection films of Examples 1 to 5 is equal to or less than that of Comparative Example 6, so the fingerprint wiping property is good. Based on the above results, it can be seen that by adjusting the sputtering film forming conditions to form an anti-reflection layer with high moisture permeability and high mechanical strength, an anti-reflection film with excellent reliability and mechanical strength at high temperatures of the polarizing plate can be obtained. In addition, when the arithmetic average roughness Ra of the surface of the anti-reflection film is small, the fingerprint wiping property is improved. According to the comparison between the above-mentioned Examples 1 to 5 and Comparative Examples 1 to 4, it can be described as the manufacture of an anti-reflective film that has both mechanical strength, heating durability of polarizing plates obtained from high moisture permeability, and fingerprint wiping properties based on the surface shape The conditions are preferably adjustment of the substrate surface shape by plasma treatment (bombardment treatment), high magnetic field film formation, high-pressure film formation within a range where the surface unevenness does not become too large, and it is achieved by adjusting the oxygen flow rate. Film formation in the transition zone, etc.

1‧‧‧透明膜基材 3‧‧‧密接性提高層 5‧‧‧抗反射層 7‧‧‧防污層 8‧‧‧偏光元件 9‧‧‧透明膜 10‧‧‧透明膜 11‧‧‧硬塗層 51、52、53、54‧‧‧薄膜 100‧‧‧抗反射膜 110‧‧‧附有抗反射層之偏光板 1‧‧‧Transparent film substrate 3‧‧‧Adhesion improvement layer 5‧‧‧Anti-reflective layer 7‧‧‧Antifouling layer 8‧‧‧Polarization element 9‧‧‧Transparent film 10‧‧‧Transparent film 11‧‧‧Hard coating 51, 52, 53, 54‧‧‧Film 100‧‧‧Anti-reflective film 110‧‧‧Polarizer with anti-reflection layer

圖1係模式性地表示抗反射膜之一形態之剖視圖。圖2係模式性地表示附有抗反射層之偏光板之一形態之剖視圖。圖3係實施例及比較例之偏光板之加熱試驗(95℃、1000小時)前後之外觀照片。Fig. 1 is a cross-sectional view schematically showing one form of the anti-reflection film. Fig. 2 is a cross-sectional view schematically showing one form of a polarizing plate with an anti-reflection layer. Fig. 3 is the appearance photos before and after the heating test (95°C, 1000 hours) of the polarizing plates of the Examples and Comparative Examples.

1‧‧‧透明膜基材 1‧‧‧Transparent film substrate

3‧‧‧密接性提高層 3‧‧‧Adhesion improvement layer

5‧‧‧抗反射層 5‧‧‧Anti-reflective layer

7‧‧‧防污層 7‧‧‧Antifouling layer

10‧‧‧透明膜 10‧‧‧Transparent film

11‧‧‧硬塗層 11‧‧‧Hard coating

51、52、53、54‧‧‧薄膜 51, 52, 53, 54‧‧‧Film

100‧‧‧抗反射膜 100‧‧‧Anti-reflective film

Claims

An anti-reflective film, which is provided on a main surface of a transparent film substrate with an anti-reflective layer containing a plurality of films with different refractive indexes, and has a moisture permeability of 15~1000g/m ² ‧24h. The pressure on the surface of the anti-reflective layer The input elastic modulus is 20~100GPa, and the arithmetic average roughness Ra is 1.5nm or less.

The anti-reflection film according to claim 1, wherein the transparent film substrate has a hard coat layer on the side where the anti-reflection layer is formed.

The anti-reflective film according to claim 2, wherein the hard coat layer comprises an acrylic urethane resin.

The anti-reflection film of claim 2 or 3, wherein the hard coat layer is an anti-glare hard coat layer in which fine particles are dispersed in a resin matrix.

The anti-reflective film according to any one of claims 1 to 3, wherein an anti-fouling layer is provided on the anti-reflective layer.

The anti-reflection film according to any one of claims 1 to 3, wherein the anti-reflection layer is an alternating laminate of niobium oxide thin films and silicon oxide thin films.

A polarizing plate with an anti-reflection layer, wherein the anti-reflection film according to any one of claims 1 to 6 is provided on one surface of the polarizing element.

A manufacturing method of an anti-reflection film, which is a method of manufacturing the anti-reflection film as claimed in any one of claims 1 to 5, and the thin film constituting the anti-reflection layer is formed by sputtering.

The method for manufacturing an anti-reflection film of claim 8, wherein the pressure during sputtering of the thin film constituting the anti-reflection layer is 0.4 Pa or more.

The method for manufacturing an anti-reflection film of claim 8 or 9, wherein the thin film constituting the anti-reflection layer is formed by reactive sputtering while introducing inert gas and reactive gas into the film forming chamber.

The method for manufacturing an anti-reflection film according to claim 10, wherein the introduction amount of the reactive gas is controlled so that the film formation by reactive sputtering becomes a transition area.

The method for manufacturing an anti-reflection film of claim 10, wherein the plasma luminescence intensity of the discharge is detected, and the introduction amount of the reactive gas is controlled based on the plasma luminescence intensity.

The method for manufacturing an anti-reflection film of claim 10, wherein the discharge voltage is detected, and the introduction amount of the reactive gas is controlled based on the discharge voltage.

The method for manufacturing an anti-reflection film of claim 8 or 9, wherein the magnetic flux density on the target surface during sputtering of the thin film constituting the anti-reflection layer is 20 mT or more.