TWI785140B - Polarizing plate with anti-reflection layer and manufacturing method thereof - Google Patents

Polarizing plate with anti-reflection layer and manufacturing method thereof Download PDF

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TWI785140B
TWI785140B TW107139145A TW107139145A TWI785140B TW I785140 B TWI785140 B TW I785140B TW 107139145 A TW107139145 A TW 107139145A TW 107139145 A TW107139145 A TW 107139145A TW I785140 B TWI785140 B TW I785140B
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layer
polarizer
polarizing plate
laminate
antireflection
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TW201922483A (en
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望月政和
八重樫將寬
伊崎章典
北村吉紹
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日商日東電工股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • G02B1/115—Multilayers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

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  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Polarising Elements (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Laminated Bodies (AREA)

Abstract

本發明可提供一種即使在高溫高濕環境下尺寸變化仍小且抑制住翹曲的附抗反射層之偏光板。本發明之附抗反射層之偏光板具備：偏光板，其具有偏光件及設置在偏光件之一側的保護層；基材，其貼合在保護層上；及抗反射層，其係直接形成在基材上。在本發明實施形態中，偏光板之水分率為0.5重量%以上。在一實施形態中，保護層之透濕度為1.0g/m2 /24hr以下。The present invention can provide a polarizing plate with an anti-reflection layer that has a small dimensional change and suppresses warpage even under high-temperature and high-humidity environments. The polarizing plate with an antireflection layer of the present invention comprises: a polarizing plate having a polarizer and a protective layer arranged on one side of the polarizer; a base material attached to the protective layer; and an antireflection layer directly formed on the substrate. In an embodiment of the present invention, the moisture content of the polarizing plate is 0.5% by weight or more. In one embodiment, the moisture permeability of the protective layer is 1.0 g/m 2 /24hr or less.

Description

附抗反射層之偏光板及其製造方法Polarizing plate with anti-reflection layer and manufacturing method thereof

本發明涉及一種附抗反射層之偏光板及其製造方法。The invention relates to a polarizing plate with anti-reflection layer and its manufacturing method.

發明背景 在影像顯示裝置(譬如液晶顯示裝置、有機EL顯示裝置、量子點顯示裝置)，由於其影像形成方式，多數情況下係於顯示單元之至少一側配置有偏光板。在配置於影像顯示裝置之視辨側的偏光板上，為了防止於顯示畫面上倒映出外光，會在其視辨側設置抗反射層(施行抗反射處理)已廣為眾知。但，習知設有抗反射層之偏光板在高溫高濕環境下的尺寸變化很大，有翹曲(尤其在視辨側呈凸狀的翹曲)明顯之問題。其結果，有時偏光板所採用的顯示單元也會隨之翹曲，而對影像顯示裝置之顯示特性帶來不良影響。Background of the invention In image display devices (such as liquid crystal display devices, organic EL display devices, quantum dot display devices), due to the image forming method, in most cases, a polarizer is arranged on at least one side of the display unit. It is known that an anti-reflection layer (anti-reflection treatment) is provided on the viewing side of a polarizer arranged on the viewing side of an image display device in order to prevent external light from being reflected on the display screen. However, conventionally known polarizers provided with anti-reflection layers have large dimensional changes in high-temperature and high-humidity environments, resulting in significant warping (especially convex warping on the viewing side). As a result, sometimes the display unit used in the polarizing plate will warp accordingly, which will adversely affect the display characteristics of the image display device.

先前技術文獻 專利文獻 專利文獻1：日本專利特開第2012-27322號公報prior art literature patent documents Patent Document 1: Japanese Patent Laid-Open No. 2012-27322

發明概要 發明欲解決之課題 本發明係為了解決上述課題而成者，其主要目的在於提供一種即使在高溫高濕環境下尺寸變化仍小且抑制住翹曲的附抗反射層之偏光板。Summary of the invention The problem to be solved by the invention The present invention was made in order to solve the above-mentioned problems, and its main object is to provide a polarizing plate with an antireflection layer that has a small dimensional change even in a high-temperature and high-humidity environment and suppresses warpage.

用以解決課題之手段 本發明之附抗反射層之偏光板具備：偏光板，其具有偏光件及設置在該偏光件之一側的保護層；基材，其貼合在該保護層上；及抗反射層，其係直接形成在該基材上；且該偏光板之水分率為0.5重量%以上。 在一實施形態中，上述保護層之透濕度為1.0g/m2 /24hr以下。 在一實施形態中，上述保護層含有(甲基)丙烯酸系樹脂。 在一實施形態中，上述基材於抗反射層側之表面具有硬塗層。 在一實施形態中，上述附抗反射層之偏光板於上述偏光件之與上述保護層相反之側更具備第1相位差層，該第1相位差層具有nx＞ny＞nz之折射率特性。 在一實施形態中，上述附抗反射層之偏光板於上述第1相位差層之與上述偏光件相反之側更具備第2相位差層，該第2相位差層具有nz＞nx＞ny之折射率特性。 在一實施形態中，上述附抗反射層之偏光板在65℃及90%RH之條件下保持500小時後，上述偏光件之吸收軸方向的尺寸變化率低於0.10%。 在一實施形態中，上述附抗反射層之偏光板在65℃及90%RH之條件下保持500小時後可能產生的捲曲在與上述抗反射層相反之側呈凸狀。 根據本發明之另一面向，可提供一種上述附抗反射層之偏光板的製造方法。該製造方法包含：製作包含偏光件及保護層之偏光件積層體；於基材形成抗反射層，製作抗反射積層體；及將該抗反射積層體之基材貼合至該偏光件積層體之保護層表面。 在一實施形態中，上述抗反射層係利用濺鍍形成。Means for Solving the Problems The polarizing plate with an antireflection layer of the present invention includes: a polarizing plate having a polarizer and a protective layer provided on one side of the polarizer; a base material bonded to the protective layer; and an anti-reflection layer, which is directly formed on the substrate; and the moisture content of the polarizer is above 0.5% by weight. In one embodiment, the moisture permeability of the protective layer is 1.0 g/m 2 /24hr or less. In one embodiment, the protective layer contains a (meth)acrylic resin. In one embodiment, the base material has a hard coat layer on the antireflection layer side surface. In one embodiment, the polarizing plate with an antireflection layer further includes a first retardation layer on the side of the polarizer opposite to the protective layer, and the first retardation layer has a refractive index characteristic of nx>ny>nz . In one embodiment, the polarizing plate with an antireflection layer further includes a second retardation layer on the opposite side of the first retardation layer to the polarizer, and the second retardation layer has a condition of nz>nx>ny. Refractive index properties. In one embodiment, after the above-mentioned polarizing plate with anti-reflection layer is kept at 65° C. and 90% RH for 500 hours, the rate of dimensional change in the direction of the absorption axis of the above-mentioned polarizer is less than 0.10%. In one embodiment, the curl that may be generated after the polarizing plate with antireflection layer is kept at 65° C. and 90% RH for 500 hours is convex on the side opposite to the antireflection layer. According to another aspect of the present invention, a method for manufacturing the above-mentioned polarizing plate with an antireflection layer can be provided. The manufacturing method includes: manufacturing a polarizer laminate including a polarizer and a protective layer; forming an antireflection layer on a substrate to produce an antireflection laminate; and attaching the base material of the antireflection laminate to the polarizer laminate the surface of the protective layer. In one embodiment, the antireflection layer is formed by sputtering.

發明效果 根據本發明，藉由令附抗反射層之偏光板的偏光板之水分率在0.5重量%以上，可實現即使在高溫高濕環境下尺寸變化仍小且抑制住翹曲的附抗反射層之偏光板。Invention effect According to the present invention, by setting the moisture content of the polarizing plate with an antireflective layer at 0.5% by weight or more, it is possible to realize a polarizing plate with an antireflective layer that has a small dimensional change and suppresses warpage even in a high-temperature and high-humidity environment. polarizer.

以下說明本發明之實施形態，惟本發明不受該等實施形態限定。Embodiments of the present invention will be described below, but the present invention is not limited to these embodiments.

A.附抗反射層之偏光板的整體構成 圖1係本發明之一實施形態之附抗反射層之偏光板的概略截面圖。附抗反射層之偏光板100依序具備具有偏光件11及保護層12之偏光板10、基材20、抗反射層30。基材20代表上係透過任意適當之接著層(接著劑層、黏著劑層：未圖示)而貼合在偏光板20之保護層12上。接著層代表上為丙烯酸系黏著劑層。抗反射層30係直接形成在基材20上。在本說明書中，「直接」意指接著層未介入其間。在一實施形態中，基材20亦可於抗反射層30側之表面具有硬塗層及/或密著層(皆未圖示)。該構成亦包含在「抗反射層係直接形成在基材上」之形態內。抗反射層30之表面亦可視需求設置防污層(未圖示)。A. Overall composition of polarizing plate with anti-reflection layer Fig. 1 is a schematic cross-sectional view of a polarizing plate with an antireflection layer according to an embodiment of the present invention. The polarizing plate with antireflection layer 100 includes a polarizing plate 10 having a polarizer 11 and a protective layer 12 , a substrate 20 , and an antireflection layer 30 in sequence. The base material 20 is typically attached to the protective layer 12 of the polarizer 20 through any appropriate adhesive layer (adhesive layer, adhesive layer: not shown). The next layer represents an acrylic adhesive layer. The anti-reflection layer 30 is directly formed on the substrate 20 . In this specification, "directly" means that an adhesive layer is not interposed therebetween. In one embodiment, the substrate 20 may also have a hard coat layer and/or an adhesive layer (both not shown) on the surface on the side of the antireflection layer 30 . This configuration is also included in the form of "the antireflection layer is directly formed on the substrate". An anti-fouling layer (not shown) may also be provided on the surface of the anti-reflection layer 30 as required.

在本發明實施形態中，偏光板10之水分率為0.5重量%以上，宜為0.6重量%以上，較宜為0.8重量%以上，更宜為1.0重量%以上。偏光板之水分率上限譬如為1.5重量%。該水分率比一般的附抗反射層之偏光板中之偏光板的水分率更高。藉由偏光板含有這般高的水分率，可顯著抑制偏光板在高溫高濕環境下的吸濕膨脹。其結果，可顯著抑制偏光板在高溫高濕環境下的尺寸變化(尤其是偏光件於吸收軸方向的尺寸變化)。譬如，本發明實施形態之附抗反射層之偏光板在65℃及90%RH之條件下保持500小時後，其偏光件之吸收軸方向的尺寸變化率低於0.10%，宜為0.08%以下，較宜為0.06%以下。此外，藉由偏光板具有這般高的水分率，本發明實施形態之附抗反射層之偏光板在高溫高濕環境下，假設即使產生捲曲，該捲曲的方向通常為逆向。具體來說，本發明實施形態之附抗反射層之偏光板在65℃及90%RH之條件下保持500小時後可能產生的捲曲，係在與抗反射層相反之側(與視辨側相反之側)呈凸狀。另，在一般的附抗反射層之偏光板中，在多數情況下捲曲係在抗反射層側呈凸狀。其結果，就算假設本發明實施形態之附抗反射層之偏光板產生了捲曲，依舊可縮小對影像顯示裝置的不良影響。誠如以上，藉由偏光板具有高水分率而抑制尺寸變化與捲曲方向的相承效果，將本發明實施形態之附抗反射層之偏光板應用在影像顯示裝置時，可明顯抑制高溫高濕環境下的翹曲、剝離及/或顯示特性降低之情況。In the embodiment of the present invention, the moisture content of the polarizing plate 10 is 0.5% by weight or more, preferably 0.6% by weight or more, more preferably 0.8% by weight or more, and more preferably 1.0% by weight or more. The upper limit of the moisture content of the polarizing plate is, for example, 1.5% by weight. The moisture content is higher than that of the polarizing plate in the general polarizing plate with anti-reflection layer. Because the polarizer contains such a high moisture content, the hygroscopic expansion of the polarizer in a high-temperature and high-humidity environment can be significantly suppressed. As a result, the dimensional change of the polarizing plate (especially the dimensional change of the polarizer in the direction of the absorption axis) can be significantly suppressed in a high-temperature and high-humidity environment. For example, after the polarizing plate with anti-reflection layer according to the embodiment of the present invention is kept at 65°C and 90% RH for 500 hours, the dimensional change rate of the absorption axis of the polarizer is less than 0.10%, preferably less than 0.08%. , preferably below 0.06%. In addition, since the polarizer has such a high moisture content, the polarizer with an anti-reflection layer according to the embodiment of the present invention is assumed to be curled in a high-temperature and high-humidity environment, and the direction of the curl is usually reversed. Specifically, the curl that may occur after the polarizing plate with anti-reflection layer in the embodiment of the present invention is kept at 65°C and 90%RH for 500 hours is on the side opposite to the anti-reflection layer (opposite to the viewing side) side) is convex. In addition, in a general polarizing plate with an antireflection layer, the curl is often convex on the antireflection layer side. As a result, even if the polarizing plate with antireflection layer according to the embodiment of the present invention is assumed to be warped, the adverse effect on the image display device can still be reduced. As mentioned above, due to the high moisture content of the polarizing plate, the effect of suppressing the dimensional change and the curling direction is suppressed. When the polarizing plate with an anti-reflection layer according to the embodiment of the present invention is applied to an image display device, high temperature and high humidity can be significantly suppressed. Warpage, peeling and/or degradation of display characteristics under environmental conditions.

在圖示例中，僅於偏光件11之一側設有保護層12，惟亦可視目的，在和保護層12相反之側設置另一個保護層。此時，可在偏光件兩側設置保護層，亦可省略保護層12僅設置另一個保護層。僅設置另一個保護層時，基材30可作為視辨側保護層發揮功能。此外，亦可視目的設置任意且適當的功能層。功能層之代表例可舉相位差層、導電層。功能層的種類、數量、組合、配置位置、特性(譬如，折射率特性、面內相位差、厚度方向相位差、Nz係數等光學特性)可視目的適當設定。在一實施形態中，可於偏光件11之與保護層12相反之側設置具有nx＞ny＞nz之折射率特性的第1相位差層(未圖示)。此時，宜在第1相位差層之與偏光件相反之側進一步設置具有nz＞nx＞ny之折射率特性的第2相位差層。第1相位差層亦可兼作與偏光件之視辨側相反之側的保護層。設置相位差層時，相位差層之慢軸(在存在之情況下)和偏光件之吸收軸構成的角度，可因應目的、相位差層之面內相位差、厚度方向相位差、折射率特性等適當設定。此外，亦可在偏光件11之與保護層12相反之側設置導電層。藉由在所述位置設置導電層，附抗反射層之偏光板很適合用於內觸控面板型輸入顯示裝置。此時，相位差層可有可無。In the illustrated example, the protective layer 12 is only provided on one side of the polarizer 11 , but another protective layer may be provided on the opposite side to the protective layer 12 depending on the purpose. At this time, protective layers may be provided on both sides of the polarizer, or the protective layer 12 may be omitted and only another protective layer may be provided. When only another protective layer is provided, the base material 30 can function as a viewing side protective layer. In addition, an arbitrary and appropriate functional layer may be provided depending on the purpose. Typical examples of functional layers include retardation layers and conductive layers. The type, number, combination, arrangement position, and characteristics (for example, optical characteristics such as refractive index characteristics, in-plane retardation, thickness direction retardation, and Nz coefficient) of functional layers can be appropriately set depending on the purpose. In one embodiment, a first retardation layer (not shown) having a refractive index characteristic of nx>ny>nz may be provided on the side of the polarizer 11 opposite to the protective layer 12 . In this case, it is preferable to further provide a second retardation layer having a refractive index characteristic of nz>nx>ny on the side opposite to the polarizer of the first retardation layer. The first retardation layer may also serve as a protective layer on the side opposite to the viewing side of the polarizer. When installing a retardation layer, the angle formed by the slow axis of the retardation layer (if it exists) and the absorption axis of the polarizer can be adjusted according to the purpose, the in-plane retardation of the retardation layer, the retardation in the thickness direction, and the refractive index characteristics. and other appropriate settings. In addition, a conductive layer may also be disposed on the side of the polarizer 11 opposite to the protective layer 12 . By disposing the conductive layer at the said position, the polarizing plate with anti-reflection layer is suitable for the inner touch panel type input display device. In this case, the retardation layer is optional.

以下，說明附抗反射層之偏光板的構成要素。Hereinafter, the constituent elements of the polarizing plate with an antireflection layer will be described.

B.偏光板 B-1.偏光件 偏光件11代表上係以含有二色性物質之樹脂薄膜構成。B. Polarizer B-1. Polarizer The polarizer 11 is typically composed of a resin film containing a dichroic substance.

就樹脂薄膜而言，可採用能作為偏光件使用之任意且適當的樹脂薄膜。樹脂薄膜代表上為聚乙烯醇系樹脂(以下稱為「PVA系樹脂」)薄膜。As the resin film, any appropriate resin film that can be used as a polarizer can be used. The resin film is typically a polyvinyl alcohol-based resin (hereinafter referred to as "PVA-based resin") film.

形成上述PVA系樹脂薄膜之PVA系樹脂可使用任意且適當的樹脂。譬如可舉聚乙烯醇、乙烯-乙烯醇共聚物。聚乙烯醇可藉由將聚乙酸乙烯酯皂化而得。乙烯-乙烯醇共聚物可藉由將乙烯-乙酸乙烯酯共聚物皂化而得。PVA系樹脂之皂化度通常為85莫耳%~100莫耳%，宜為95.0莫耳%~99.95莫耳%，更宜為99.0莫耳%~99.93莫耳%。皂化度係依JIS K 6726-1994而求得。藉由使用所述皂化度的PVA系樹脂，可獲得耐久性優異的偏光件。皂化度太高時，會有膠化之虞。Arbitrary and appropriate resins can be used for the PVA-type resin which forms the said PVA-type resin film. Examples thereof include polyvinyl alcohol and ethylene-vinyl alcohol copolymers. Polyvinyl alcohol can be obtained by saponifying polyvinyl acetate. Ethylene-vinyl alcohol copolymer can be obtained by saponifying ethylene-vinyl acetate copolymer. The saponification degree of the PVA-based resin is usually 85 mol %-100 mol %, preferably 95.0 mol %-99.95 mol %, more preferably 99.0 mol %-99.93 mol %. The degree of saponification is obtained in accordance with JIS K 6726-1994. By using a PVA-based resin having such a degree of saponification, a polarizer excellent in durability can be obtained. When the degree of saponification is too high, gelation may occur.

PVA系樹脂的平均聚合度可按目的適當選擇。平均聚合度通常為1000~10000，宜為1200~4500，更宜為1500~4300。另，平均聚合度可按JIS K 6726-1994而求得。The average degree of polymerization of the PVA-based resin can be appropriately selected according to the purpose. The average degree of polymerization is usually 1000-10000, preferably 1200-4500, more preferably 1500-4300. In addition, the average degree of polymerization can be obtained according to JIS K 6726-1994.

樹脂薄膜中所含二色性物質譬如可舉碘、有機染料等。該等可單獨使用或可將二種以上組合使用。較佳可使用碘。譬如，利用化學處理進行脫色來形成非偏光部時，樹脂薄膜(偏光件)中所含碘錯合物會被適當還原，因此譬如使用在攝影機部位時，可形成具有適當特性的非偏光部。Examples of the dichroic substance contained in the resin film include iodine and organic dyes. These may be used alone or in combination of two or more. Preferably iodine can be used. For example, when the non-polarizing part is formed by decolorizing by chemical treatment, the iodine complex contained in the resin film (polarizer) will be appropriately reduced, so for example, when used in a camera part, a non-polarizing part with appropriate characteristics can be formed.

樹脂薄膜可為單層樹脂薄膜亦可為二層以上之積層體。The resin film may be a single-layer resin film or a laminate of two or more layers.

由單層樹脂薄膜構成之偏光件的具體例，可舉PVA系樹脂薄膜業已施行碘之染色處理及延伸處理(代表上為單軸延伸)者。上述利用碘之染色譬如可將PVA系薄膜浸漬於碘水溶液中來進行。上述單軸延伸之延伸倍率宜為3~7倍。延伸可在染色處理後進行，亦可在染色的同時進行。又，亦可延伸後再染色。可因應需求對PVA系樹脂薄膜施行膨潤處理、交聯處理、洗淨處理、乾燥處理等。譬如，在染色前將PVA系樹脂薄膜浸漬於水中進行水洗，不僅可洗淨PVA系薄膜表面的污垢或抗黏結劑，還可使PVA系樹脂薄膜膨潤，從而防止染色不均等情況。A specific example of a polarizer made of a single-layer resin film is a PVA-based resin film that has been dyed with iodine and stretched (typically uniaxially stretched). The above-mentioned dyeing with iodine can be carried out, for example, by immersing a PVA-based film in an iodine aqueous solution. The elongation ratio of the above-mentioned uniaxial stretching is preferably 3 to 7 times. The elongation may be performed after the dyeing treatment or simultaneously with the dyeing. In addition, dyeing after stretching is also possible. Swelling treatment, cross-linking treatment, cleaning treatment, drying treatment, etc. can be performed on PVA-based resin films according to needs. For example, immersing the PVA-based resin film in water for washing before dyeing can not only clean the dirt or anti-adhesive agent on the surface of the PVA-based film, but also make the PVA-based resin film swell, thereby preventing uneven dyeing.

使用積層體而獲得之偏光件的具體例，可舉出樹脂基材與積層在該樹脂基材之PVA系樹脂層(PVA系樹脂薄膜)的積層體，或者是使用樹脂基材與塗佈形成於該樹脂基材之PVA系樹脂層的積層體而獲得之偏光件。使用樹脂基材與塗佈形成於該樹脂基材之PVA系樹脂層的積層體而獲得之偏光件，舉例而言可透過下列程序製作：將PVA系樹脂溶液塗佈於樹脂基材，並使其乾燥而於樹脂基材上形成PVA系樹脂層，而獲得樹脂基材與PVA系樹脂層之積層體；將該積層體延伸並染色而將PVA系樹脂層製成偏光件。本實施形態中，延伸代表上包含使積層體浸漬於硼酸水溶液中並進行延伸。而且，視需要，延伸可更進一步地包含在硼酸水溶液中進行延伸前以高溫(例如95℃以上)將積層體進行空中延伸。可以直接使用所得樹脂基材/偏光件之積層體(即，可將樹脂基材作為偏光件之保護層)，亦可從樹脂基材/偏光件之積層體剝離樹脂基材並於該剝離面視目的積層任意且適當的保護層後來使用。所述偏光件之製造方法的詳細內容記載於例如日本特開2012-73580號公報。本說明書中援用該公報之其整體的記載作為參考。Specific examples of polarizers obtained by using a laminate include a laminate of a resin substrate and a PVA-based resin layer (PVA-based resin film) laminated on the resin substrate, or a laminate formed using a resin substrate and coating. A polarizer obtained from a laminate of PVA-based resin layers on the resin substrate. A polarizer obtained by using a laminate of a resin base material and a PVA-based resin layer coated on the resin base material can be produced, for example, by the following procedure: apply a PVA-based resin solution to the resin base material, and use It is dried to form a PVA-based resin layer on the resin substrate to obtain a laminate of the resin substrate and the PVA-based resin layer; the laminate is stretched and dyed to make the PVA-based resin layer into a polarizer. In this embodiment, stretching typically includes immersing the laminate in an aqueous solution of boric acid and stretching it. If necessary, the stretching may further include stretching the laminate in air at a high temperature (for example, 95° C. or higher) before stretching in an aqueous boric acid solution. The obtained resin substrate/polarizer laminate can be used directly (that is, the resin substrate can be used as a protective layer of the polarizer), or the resin substrate can be peeled off from the resin substrate/polarizer laminate and placed on the peeled surface Depending on the purpose, an arbitrary and appropriate protective layer is laminated for later use. The details of the manufacturing method of the polarizer are described in, for example, Japanese Patent Application Laid-Open No. 2012-73580. In this specification, the entire description of this publication is incorporated by reference.

偏光件厚度宜為15μm以下，較宜為1μm~12μm，更宜為3μm~10μm，尤宜為3μm~8μm。只要偏光件厚度在所述範圍內，即可良好地抑制加熱時之捲曲，並且可獲得良好的加熱時之外觀耐久性。此外，偏光件厚度若在所述範圍內，便有助於附抗反射層之偏光板(就結果論，即影像顯示裝置)的薄型化。The thickness of the polarizer is preferably less than 15 μm, preferably 1 μm to 12 μm, more preferably 3 μm to 10 μm, and especially preferably 3 μm to 8 μm. As long as the thickness of the polarizer is within the above range, curling during heating can be well suppressed, and good appearance durability during heating can be obtained. In addition, if the thickness of the polarizer is within the above range, it will help to reduce the thickness of the polarizer with anti-reflection layer (in terms of the result, that is, the image display device).

偏光件宜在波長380nm~780nm的任一波長下顯示吸收二色性。偏光件之單體透射率宜為43.0%~46.0%，較宜為44.5%~46.0%。偏光件的偏光度以97.0%以上為佳，99.0%以上較佳，99.9%以上更佳。The polarizer should exhibit absorption dichroism at any wavelength between 380nm and 780nm. The single transmittance of the polarizer is preferably 43.0%~46.0%, more preferably 44.5%~46.0%. The degree of polarization of the polarizer is preferably above 97.0%, more preferably above 99.0%, and more preferably above 99.9%.

B-2.保護層 保護層12可使用任意且適當的樹脂薄膜。樹脂薄膜之形成材料可舉如(甲基)丙烯酸系樹脂、二乙醯纖維素、三乙醯纖維素等纖維素系樹脂、降莰烯系樹脂等環烯烴系樹脂、聚丙烯等烯烴系樹脂、聚對苯二甲酸乙二酯系樹脂等酯系樹脂、聚醯胺系樹脂、聚碳酸酯系樹脂及該等之共聚物樹脂等。此外，「(甲基)丙烯酸系樹脂」是指丙烯酸系樹脂及/或甲基丙烯酸系樹脂。B-2. Protective layer Any appropriate resin film can be used for the protective layer 12 . Examples of materials for forming the resin film include (meth)acrylic resins, cellulose resins such as diacetyl cellulose and triacetyl cellulose, cycloolefin resins such as norbornene resins, and olefin resins such as polypropylene. , polyester resins such as polyethylene terephthalate resins, polyamide resins, polycarbonate resins and their copolymer resins, etc. In addition, "(meth)acrylic resin" means an acrylic resin and/or a methacrylic resin.

在一實施形態中，就上述(甲基)丙烯酸系樹脂，係使用戊二醯亞胺結構之(甲基)丙烯酸系樹脂。具有戊二醯亞胺結構之(甲基)丙烯酸系樹脂(以下亦稱戊二醯亞胺樹脂)譬如下列文獻所記載：日本特開2006-309033號公報、日本特開2006-317560號公報、日本特開2006-328329號公報、日本特開2006-328334號公報、日本特開2006-337491號公報、日本特開2006-337492號公報、日本特開2006-337493號公報、日本特開2006-337569號公報、日本特開2007-009182號公報、日本特開2009-161744號公報、日本特開2010-284840號公報。本說明書即援用該等記載作為參考。In one embodiment, a (meth)acrylic resin having a glutarimide structure is used as the (meth)acrylic resin. (Meth)acrylic resins having a glutarimide structure (hereinafter also referred to as glutarimide resins) are described in the following documents, for example: Japanese Patent Laid-Open No. 2006-309033, Japanese Patent Laid-Open No. 2006-317560, JP 2006-328329, JP 2006-328334, JP 2006-337491, JP 2006-337492, JP 2006-337493, JP 2006- 337569, JP-A-2007-009182, JP-A-2009-161744, and JP-A-2010-284840. These descriptions are used as a reference in this specification.

保護層12之透濕度宜為1.0g/m2 /24hr以下，較宜為0.8g/m2 /24hr以下，更宜為0.6g/m2 /24hr以下，尤宜為0.4g/m2 /24hr以下。保護層之透濕度若在所述範圍內，便更能抑制高溫高濕環境下的尺寸變化。The moisture permeability of the protective layer 12 is preferably less than 1.0g/m 2 /24hr, preferably less than 0.8g/m 2 /24hr, more preferably less than 0.6g/m 2 /24hr, especially preferably 0.4g/m 2 / Below 24 hours. If the moisture permeability of the protective layer is within the above-mentioned range, the dimensional change in a high-temperature and high-humidity environment can be more suppressed.

保護層厚度代表上為10μm~100μm，宜為20μm~40μm。保護層代表上係透過接著層(具體上為接著劑層、黏著劑層)積層在偏光件上。接著劑層代表上係以PVA系接著劑或活性化能量線硬化型接著劑形成。黏著劑層代表上係以丙烯酸系黏著劑形成。The thickness of the protective layer is typically 10 μm to 100 μm, preferably 20 μm to 40 μm. The protective layer means that the upper system is laminated on the polarizer through an adhesive layer (specifically, an adhesive layer, an adhesive layer). The adhesive layer represents that the upper part is formed with a PVA-based adhesive or an activated energy ray-curable adhesive. The adhesive layer represents that the top is formed with an acrylic adhesive.

C.基材 C-1.基材本體 基材20可用來形成抗反射層30。如後述，藉由在基材形成抗反射層，並將基材/抗反射層之積層體貼合至偏光板，便無須對偏光板進行抗反射層形成製程(代表上為濺鍍)。其結果，無須使偏光板曝露在高溫下，因此可將偏光板之水分率維持在上述期望範圍內。C. Substrate C-1. Substrate body The substrate 20 can be used to form the anti-reflection layer 30 . As will be described later, by forming an anti-reflection layer on a base material and bonding the base material/anti-reflection layer laminate to a polarizer, the process of forming an anti-reflection layer (typically, sputtering) on the polarizer is unnecessary. As a result, it is not necessary to expose the polarizing plate to high temperature, so the moisture content of the polarizing plate can be maintained within the above-mentioned desired range.

基材可使用任意且適當的樹脂薄膜。樹脂薄膜之形成材料可舉如聚對苯二甲酸乙二酯(PET)等聚酯系樹脂、降莰烯系樹脂等環烯烴系樹脂、利用環烯烴(譬如降莰烯)與α-烯烴(譬如乙烯)加成聚合而製得的樹脂(COC)、三乙酸纖維素(TAC)等纖維素系樹脂。Arbitrary and appropriate resin films can be used as the base material. The forming material of the resin film can be, for example, polyester-based resins such as polyethylene terephthalate (PET), cycloolefin-based resins such as norbornene-based resins, cycloolefins (such as norbornene) and α-olefins ( For example, cellulose-based resins such as resin (COC) obtained by addition polymerization of ethylene) and cellulose triacetate (TAC).

基材厚度可因應目的適當設定。基材厚度代表上為20μm~200μm，宜為25μm~100μm。The thickness of the substrate can be appropriately set according to the purpose. The thickness of the base material is typically 20 μm to 200 μm, preferably 25 μm to 100 μm.

C-2.硬塗層 如上述，於基材之抗反射層側的表面亦可形成有硬塗層。藉由形成硬塗層，具有可能提升基材與抗反射層之密著性的優點。此外，適度調整硬塗層與抗反射層之折射率差，可進一步降低反射率。C-2. Hard coating As described above, a hard coat layer may be formed on the surface of the substrate on the antireflection layer side. By forming a hard coat layer, there is an advantage that it is possible to improve the adhesion between the base material and the antireflection layer. In addition, moderately adjusting the refractive index difference between the hard coat layer and the antireflection layer can further reduce the reflectivity.

硬塗層宜具有充分的表面硬度、優異的機械強度及優異的透光性。硬塗層只要具有所述期望的特性，可由任意且適當的樹脂形成。樹脂之具體例可舉熱硬化型樹脂、熱可塑型樹脂、紫外線硬化型樹脂、電子線硬化型樹脂、二液混合型樹脂。且以紫外線硬化型樹脂為宜。因為能以簡便操作及高效率形成硬塗層。The hard coat layer preferably has sufficient surface hardness, excellent mechanical strength, and excellent light transmittance. The hard coat layer may be formed of any appropriate resin as long as it has the above-mentioned desired properties. Specific examples of the resin include thermosetting resins, thermoplastic resins, ultraviolet curable resins, electron beam curable resins, and two-component mixed resins. In addition, ultraviolet curable resin is suitable. Because the hard coat layer can be formed with simple operation and high efficiency.

紫外線硬化型樹脂之具體例可舉聚酯系、丙烯酸系、胺甲酸酯系、醯胺系、聚矽氧系、環氧系紫外線硬化型樹脂。紫外線硬化型樹脂包含紫外線硬化型之單體、寡聚物、聚合物。理想的紫外線硬化型樹脂，可舉含有宜具有2個以上且較宜為3~6個紫外線聚合性官能基之丙烯酸系單體成分或寡聚物成分的樹脂組成物。代表上，紫外線硬化型樹脂中可摻混有光聚合起始劑。Specific examples of ultraviolet curable resins include polyester-based, acrylic-based, urethane-based, amide-based, silicone-based, and epoxy-based ultraviolet-curable resins. UV-curable resins include UV-curable monomers, oligomers, and polymers. An ideal UV-curable resin includes a resin composition containing an acrylic monomer component or an oligomer component preferably having 2 or more, preferably 3-6 UV-polymerizable functional groups. Typically, a photopolymerization initiator may be blended in an ultraviolet curable resin.

硬塗層可利用任意且適當的方法形成。譬如，硬塗層可於基材上塗敷硬塗層形成用樹脂組成物後使其乾燥，再對已乾燥塗敷膜照射紫外線使其硬化來形成。The hard coat layer can be formed by any appropriate method. For example, a hard coat layer can be formed by applying a resin composition for forming a hard coat layer on a base material, drying it, and irradiating the dried coating film with ultraviolet rays to harden it.

硬塗層厚度譬如為0.5μm~20μm，宜為1μm~15μm。The thickness of the hard coat layer is, for example, 0.5 μm to 20 μm, preferably 1 μm to 15 μm.

關於硬塗層以及硬塗層與抗反射層之密著結構的詳細，譬如日本特開2016-224443號公報中所記載。本說明書中係援用該公報之記載作為參考。Details of the hard coat layer and the adhesion structure of the hard coat layer and the antireflection layer are described in, for example, Japanese Patent Laid-Open No. 2016-224443. In this specification, the description of this publication is cited as a reference.

D.抗反射層 抗反射層之構成可採用任意且適當的構成。抗反射層的代表性構成可舉：(1)光學膜厚為120nm~140nm且折射率1.35~1.55左右之低折射率層的單一層；(2)從基材側起依序具有中折射率層、高折射率層與低折射率層之積層體；(3)高折射率層與低折射率層的交錯多層積層體。D. Anti-reflection layer Arbitrary and appropriate configurations can be adopted for the configuration of the antireflection layer. Typical configurations of the antireflection layer include: (1) a single layer of a low refractive index layer with an optical thickness of 120nm to 140nm and a refractive index of about 1.35 to 1.55; layer, a laminate of high-refractive-index layers and low-refractive-index layers; (3) an alternate multilayer laminate of high-refractive-index layers and low-refractive-index layers.

可形成低折射率層之材料可舉如氧化矽(SiO2 )、氟化鎂(MgF2 )。低折射率層之折射率代表是1.35~1.55左右。可形成高折射率層之材料可舉如氧化鈦(TiO2 )、氧化鈮(Nb2 O3 或Nb2 O5 )、錫摻雜氧化銦(ITO)、銻摻雜氧化錫(ATO)、ZrO2 -TiO2 。高折射率層之折射率代表是1.60~2.20左右。可形成中折射率層之材料可舉如氧化鈦(TiO2 )、可形成低折射率層之材料與可形成高折射率層之材料的混合物(譬如氧化鈦與氧化矽之混合物)。中折射率層之折射率代表是1.50~1.85左右。低折射率層、中折射率層及高折射率層之厚度可因應抗反射層之層結構、期望之抗反射性能等能實現適當之光學膜厚的方式來做設定。Materials that can form the low refractive index layer include silicon oxide (SiO 2 ) and magnesium fluoride (MgF 2 ). The refractive index of the low refractive index layer is typically about 1.35~1.55. Materials that can form a high refractive index layer include titanium oxide (TiO 2 ), niobium oxide (Nb 2 O 3 or Nb 2 O 5 ), tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), ZrO 2 -TiO 2 . The typical refractive index of the high refractive index layer is about 1.60~2.20. Materials that can form the middle refractive index layer include titanium oxide (TiO 2 ), a mixture of materials that can form the low refractive index layer and materials that can form the high refractive index layer (such as a mixture of titanium oxide and silicon oxide). The representative refractive index of the middle refractive index layer is about 1.50~1.85. The thicknesses of the low-refractive-index layer, the medium-refractive-index layer, and the high-refractive-index layer can be set according to the layer structure of the antireflection layer, desired antireflection performance, etc., so as to achieve an appropriate optical film thickness.

抗反射層代表上可利用乾式製程形成。乾式製程之具體例可舉PVD(Physical Vapor Deposition，物理氣相沉積)法、CVD(Chemical Vapor Deposition，化學氣相沉積)法。PVD法可舉真空蒸鍍法、反應性蒸鍍法、離子束輔助法、濺鍍法、離子鍍法。CVD法可舉電漿CVD法。且宜為濺鍍法。因為可做到膜厚參差小、更為均勻的成膜。The anti-reflection layer can be formed on the representative surface by using a dry process. Specific examples of the dry process include PVD (Physical Vapor Deposition, physical vapor deposition) method and CVD (Chemical Vapor Deposition, chemical vapor deposition) method. Examples of the PVD method include a vacuum evaporation method, a reactive evaporation method, an ion beam-assisted method, a sputtering method, and an ion plating method. The CVD method includes plasma CVD method. And it is preferably a sputtering method. Because it can achieve less variation in film thickness and more uniform film formation.

抗反射層厚度譬如為20nm~300nm左右。The thickness of the anti-reflection layer is, for example, about 20 nm to 300 nm.

抗反射層在波長400nm~700nm之範圍內的最大反射率與最小反射率之差宜為2.0%以下，較宜為1.9%以下，更宜為1.8%以下。最大反射率與最小反射率之差只要在所述範圍內，便可良好地防止反射光的著色。The difference between the maximum reflectance and the minimum reflectance of the anti-reflection layer in the wavelength range of 400nm~700nm is preferably 2.0% or less, more preferably 1.9% or less, more preferably 1.8% or less. If the difference between the maximum reflectance and the minimum reflectance is within the above-mentioned range, coloring of reflected light can be prevented favorably.

可視需求於抗反射層表面設置防污層。防污層譬如含有含氟基之矽烷系化合物(譬如具有全氟聚醚基之烷氧矽烷化合物)或含氟基之有機化合物。防污層宜能展現水接觸角為110度以上之撥水性。An anti-fouling layer may be provided on the surface of the anti-reflection layer as required. The antifouling layer contains, for example, a fluorine-containing silane compound (such as an alkoxysilane compound having a perfluoropolyether group) or a fluorine-containing organic compound. The antifouling layer should be able to exhibit water repellency with a water contact angle of 110 degrees or more.

E.附抗反射層之偏光板的製造方法 本發明之一實施形態的附抗反射層之偏光板的製造方法包含：製作包含偏光件及保護層之偏光件積層體；於基材形成抗反射層，製作抗反射積層體；及將該抗反射積層體之基材貼合至該偏光件積層體之保護層表面。E. Manufacturing method of polarizing plate with anti-reflection layer A method of manufacturing a polarizing plate with an anti-reflection layer according to an embodiment of the present invention includes: manufacturing a polarizer laminate including a polarizer and a protective layer; forming an anti-reflection layer on a base material to manufacture an anti-reflection laminate; and The substrate of the reflective laminate is bonded to the surface of the protective layer of the polarizer laminate.

偏光件積層體可利用任意且適當的方法製作。在使用由單層樹脂薄膜構成之偏光件的情況下，將偏光件與構成保護層之樹脂薄膜隔著任意且適當的接著層(接著劑層或黏著劑層)貼合即可。在使用樹脂基材與積層在該樹脂基材上之PVA系樹脂層(PVA系樹脂薄膜)的積層體的情況下，亦可對該積層體進行染色及延伸處理，將PVA系樹脂層當作偏光件，並將該積層體直接當作偏光件積層體使用。或者，亦可於該積層體之偏光件表面貼合構成保護層之樹脂薄膜來使用。此時，樹脂基材可剝離亦可不剝離。在使用利用樹脂基材與經塗佈形成在該樹脂基材上之PVA系樹脂層的積層體而製得的偏光件的情況下，可以如上述B-1項中所記載(譬如以如日本特開2012-73580號公報中所記載)來製作樹脂基材/偏光件之積層體後，將該積層體直接當作偏光件積層體使用。或者，亦可於該積層體之偏光件表面貼合構成保護層之樹脂薄膜來使用。此時，樹脂基材可剝離亦可不剝離。The polarizer laminate can be produced by any appropriate method. In the case of using a polarizer composed of a single-layer resin film, the polarizer and the resin film constituting the protective layer may be bonded via an arbitrary and appropriate adhesive layer (adhesive layer or adhesive layer). In the case of using a laminate of a resin substrate and a PVA-based resin layer (PVA-based resin film) laminated on the resin substrate, the laminate may also be dyed and stretched to treat the PVA-based resin layer as polarizer, and use the laminate directly as a polarizer laminate. Alternatively, a resin film constituting a protective layer may be bonded to the surface of the polarizer of the laminate for use. At this time, the resin substrate may or may not be peeled off. In the case of using a polarizer made of a laminate of a resin base material and a PVA-based resin layer coated and formed on the resin base material, it can be as described in the above item B-1 (for example, in Japan 2012-73580 A) to produce a laminate of resin base material/polarizer, the laminate is directly used as a polarizer laminate. Alternatively, a resin film constituting a protective layer may be bonded to the surface of the polarizer of the laminate for use. At this time, the resin substrate may or may not be peeled off.

抗反射積層體可藉由在基材形成抗反射層來製作。形成抗反射層時，亦可視需求淤先對基材施行表面處理。表面處理可舉如低壓電漿處理、紫外線照射處理、電暈處理、火焰處理、酸或鹼處理。或者，亦可在基材表面形成譬如由SiOx所構成之密著層。抗反射層如上述，代表上可利用乾式製程(譬如濺鍍)形成。舉例而言，當抗反射層為高折射率層與低折射率層之交錯多層積層體時，可在基材表面利用濺鍍譬如依序製膜Nb2 O5 膜(高折射率層)、SiO2 膜(低折射率層)、Nb2 O5 膜(高折射率層)及SiO2 膜(低折射率層)，來形成抗反射層。An antireflection laminate can be produced by forming an antireflection layer on a substrate. When forming the anti-reflection layer, the base material may also be subjected to surface treatment as required. Examples of surface treatment include low-pressure plasma treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, acid or alkali treatment. Alternatively, an adhesive layer made of, for example, SiOx may also be formed on the surface of the substrate. As mentioned above, the anti-reflection layer can typically be formed by a dry process (such as sputtering). For example, when the anti-reflection layer is an interlaced multilayer laminate of high refractive index layers and low refractive index layers, sputtering can be used on the surface of the substrate, such as sequentially forming Nb 2 O 5 film (high refractive index layer), SiO 2 film (low refractive index layer), Nb 2 O 5 film (high refractive index layer) and SiO 2 film (low refractive index layer) to form an anti-reflection layer.

最後，於偏光件積層體之保護層表面隔著任意且適當的接著層(譬如接著劑層、黏著劑層)貼合抗反射積層體之基材，可製得附抗反射層之偏光板。如上述說明所明示，根據所述製造方法，不會在抗反射層之形成製程(乾式製程)中提供偏光板。因此，偏光板不會被曝露在高溫下，所以可將偏光板之水分率維持在上述期望範圍內。結果，所得附抗反射層之偏光板不僅可在高溫高濕環境下抑制尺寸變化，且假設就算產生了捲曲，該捲曲之方向也會在與視辨側相反之側呈凸狀。藉此，當將附抗反射層之偏光板應用在影像顯示裝置時，可明顯抑制高溫高濕環境下的翹曲、剝離及/或顯示特性降低之情況。Finally, a polarizing plate with an antireflection layer can be produced by laminating the base material of the antireflection laminate on the surface of the protective layer of the polarizer laminate via an arbitrary and appropriate adhesive layer (such as an adhesive layer, an adhesive layer). As apparent from the above description, according to the manufacturing method, no polarizing plate is provided in the antireflection layer forming process (dry process). Therefore, the polarizing plate will not be exposed to high temperature, so the moisture content of the polarizing plate can be maintained within the above-mentioned desired range. As a result, the obtained polarizing plate with an antireflection layer not only suppresses dimensional changes in a high-temperature, high-humidity environment, but even if curling occurs, the direction of the curling is convex on the side opposite to the viewing side. Thereby, when the polarizing plate with the anti-reflection layer is applied to an image display device, warpage, peeling and/or degradation of display characteristics in a high-temperature and high-humidity environment can be significantly suppressed.

F.影像顯示裝置 本發明實施形態之附抗反射層之偏光板可應用在影像顯示裝置。代表上，附抗反射層之偏光板可以抗反射層為視辨側的方式配置在影像顯示裝置之視辨側。影像顯示裝置之代表例可舉如液晶顯示裝置、有機電致發光(EL)顯示裝置、量子點顯示裝置。 實施例F. Image display device The polarizing plate with an antireflection layer according to the embodiment of the present invention can be applied to an image display device. Typically, the polarizing plate with an antireflection layer can be arranged on the viewing side of the image display device so that the antireflection layer is on the viewing side. Representative examples of image display devices include liquid crystal display devices, organic electroluminescence (EL) display devices, and quantum dot display devices. Example

以下，以實施例來具體說明本發明，惟本發明不受該等實施例限定。又，各特性之測定方法如以下所述。Hereinafter, the present invention will be specifically described with examples, but the present invention is not limited by these examples. In addition, the measurement method of each characteristic is as follows.

(1)透濕度 將實施例及比較例中使用之保護層(用以構成之樹脂薄膜)裁成10cmΦ之圓形，做成測定試料。針對該測定試料，使用日立製作所公司製造之「MOCON」，在40℃、90%RH之試驗條件下測定透濕度。 (2)偏光板之水分率 將實施例及比較例中使用之偏光板裁成100mm×100mm之大小並將之在23℃、55%RH之環境下保管72小時以上後之物當作測定試料，測定該測定試料之重量。如此所測得之重量即為初始重量。接著，將該測定試料在120℃下乾燥24小時後，測定乾燥重量，並按下述式決定水分率。另，下述式中，初始重量及乾燥重量係使用分別進行3次測定後之平均值。 水分率(重量%)=[(初始重量-乾燥重量)/初始重量]×100 (3)尺寸變化率 將實施例及比較例中所得附抗反射層之偏光板以偏光件之吸收軸方向為長邊切成112mm×65mm(5吋尺寸)，做成測定試料。將該測定試料在65℃及90%RH之環境下放置500小時後，使用Mitutoyo Co.製造之大型CNC影像測定機(商品名：QV ACCEL808)，測出測定試料之長邊方向的尺寸變化。相對於初始長度(100mm)之尺寸變化量視為尺寸變化率。另，尺寸膨脹(尺寸變長)之情況表記為「+」，尺寸收縮(尺寸變短)之情況表記為「-」。 (4)翹曲 將實施例及比較例中所得附抗反射層之偏光板以偏光件之吸收軸方向為長邊切成112mm×65mm(5吋尺寸)，做成測定試料。將該測定試料在65℃及90%RH之環境下放置500小時置後，以肉眼觀察翹曲(捲曲)。翹曲在與抗反射層相反之側呈凸狀時視為「良好」，在抗反射層側呈凸狀時則視為「不良」。(1) Moisture permeability The protective layer (resin film used for forming) used in the examples and comparative examples was cut into a circle of 10 cmΦ to prepare a measurement sample. With respect to the measurement sample, the moisture permeability was measured under the test conditions of 40° C. and 90% RH using “MOCON” manufactured by Hitachi, Ltd. (2) Moisture content of polarizer The polarizing plate used in the examples and comparative examples was cut into a size of 100mm×100mm and stored at 23°C and 55%RH for more than 72 hours as a measurement sample, and the weight of the measurement sample was measured. The weight thus measured is the initial weight. Next, after drying this measurement sample at 120 degreeC for 24 hours, the dry weight was measured, and the moisture content was determined according to the following formula. In addition, in the following formula, the average value of the initial weight and dry weight which measured each 3 times is used. Moisture rate (weight%)=[(initial weight-dry weight)/initial weight]×100 (3) Dimensional change rate The polarizing plates with anti-reflection layers obtained in Examples and Comparative Examples were cut into 112mm×65mm (5-inch size) with the absorption axis direction of the polarizer as the long side to make measurement samples. After the measurement sample was left in an environment of 65°C and 90%RH for 500 hours, the dimensional change in the longitudinal direction of the measurement sample was measured using a large CNC image measuring machine manufactured by Mitutoyo Co. (trade name: QV ACCEL808). The amount of dimensional change relative to the initial length (100mm) is regarded as the rate of dimensional change. In addition, the case of size expansion (lengthening) is indicated as "+", and the case of size contraction (dimension shortening) is indicated as "-". (4) warping The polarizing plates with anti-reflection layers obtained in Examples and Comparative Examples were cut into 112mm×65mm (5-inch size) with the absorption axis direction of the polarizer as the long side to make measurement samples. The measurement sample was left to stand for 500 hours in an environment of 65° C. and 90% RH, and the warpage (curl) was observed with the naked eye. When the warpage was convex on the side opposite to the antireflection layer, it was rated as "good", and when it was convex on the side of the antireflection layer, it was rated as "defective".

[實施例1] 1.製作偏光板(偏光件積層體) 樹脂基材係使用長條狀、吸水率0.75%、Tg75℃之非晶質異酞酸共聚聚對苯二甲酸乙二酯(IPA共聚PET)薄膜(厚度：100μm)。於基材單面施以電暈處理，於該電暈處理面上於25℃下塗佈以9：1之比含有聚乙烯醇(聚合度4200，皂化度99.2莫耳%)及乙醯乙醯基改質PVA(聚合度1200，乙醯乙醯基改質度4.6%，皂化度99.0莫耳%以上，日本合成化學工業公司製，商品名「GOHSEFIMER Z200」)之水溶液後使其乾燥，而形成厚度11μm之PVA系樹脂層，製出積層體。 在120℃之烘箱內，使所獲得之積層體在周速相異的輥間往縱方向(長邊方向)進行自由端單軸延伸2.0倍(空中輔助延伸)。 接著，將積層體浸漬於液溫30℃的不溶解浴(相對於水100重量份，摻混4重量份之硼酸而得的硼酸水溶液)中30秒(不溶解處理)。 接著，浸漬於液溫30℃的染色浴中並同時調整碘濃度、浸漬時間以使偏光板成預定之透射率。本實施例係將之浸漬於相對於100重量份的水摻混0.2重量份的碘、1.5重量份的碘化鉀所得之碘水溶液中60秒(染色處理)。 接著，使其於液溫30℃的交聯浴(相對於水100重量份，摻混3重量份的碘化鉀並摻混3重量份的硼酸而獲得之硼酸水溶液)中浸漬30秒(交聯處理)。 其後，一邊使積層體浸漬於液溫70℃之硼酸水溶液(相對於100重量份的水，摻混4重量份硼酸、5重量份碘化鉀所得之水溶液)，一邊於不同周速之輥件間往縱方向(長邊方向)進行單軸延伸以使總延伸倍率達5.5倍(水中延伸)。 之後，將積層體浸漬於液溫30℃的洗淨浴(相對於水100重量份摻混4重量份的碘化鉀而獲得之水溶液)中(洗淨處理)。 接著，於積層體之PVA系樹脂層(偏光件)表面以硬化後之接著劑層厚度為1.0μm的方式塗佈下述所示接著劑，並貼合構成保護層之甲基丙烯酸樹脂薄膜(厚度：40μm，透濕度：0.6g/m2 /24hr，具有戊二醯亞胺結構)後，從該甲基丙烯酸系樹脂薄膜側用IR加熱器加熱至50℃，並照射下述紫外線，使接著劑硬化。然後將基材從PVA系樹脂層剝離，而獲得偏光件積層體(具有偏光件/保護層之構成的偏光板)。另，偏光件厚度為5μm，單體透射率為42.3%。又，所製得之偏光板的水分率為1.0重量%。 (接著劑組成) 將N-羥乙基丙烯醯胺(HEAA)40重量份、丙烯醯基嗎福林(ACMO)60重量份與光引發劑「IRGACURE 819」(BASF公司製)3重量份摻混，而調製出硬化前之黏度為40mPa・S之接著劑。 (紫外線) 活性能量線係使用紫外線(鎵封入金屬鹵素燈，照射裝置：Fusion UV Systems，Inc公司製造之Light HAMMER10，燈泡：V燈泡，峰照度：1600mW/cm2 ，累積照射量1000/mJ/cm2 (波長380~440nm))。此外，紫外線之照度係使用Solatell公司製造之Sola-Check系統測得。[Example 1] 1. Production of a polarizing plate (polarizer laminate) The resin substrate is a long strip of amorphous isophthalic acid copolymerized polyethylene terephthalate (IPA) with a water absorption rate of 0.75% and a Tg of 75°C. copolymerized PET) film (thickness: 100 μm). Corona treatment is applied to one side of the substrate, and a 9:1 ratio of polyvinyl alcohol (polymerization degree 4200, saponification degree 99.2 mole%) and acetylene is coated on the corona treatment surface at 25 ° C. Acyl-modified PVA (polymerization degree 1200, acetyl acetyl-modification degree 4.6%, saponification degree 99.0 mol% or more, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "GOHSEFIMER Z200") and then dried. Then, a PVA-based resin layer having a thickness of 11 μm was formed to produce a laminate. In an oven at 120°C, the obtained laminate was uniaxially stretched 2.0 times in the longitudinal direction (longitudinal direction) between rolls having different circumferential speeds (assisted stretching in the air). Next, the laminated body was immersed in an insoluble bath (an aqueous solution of boric acid obtained by mixing 4 parts by weight of boric acid with respect to 100 parts by weight of water) at a liquid temperature of 30° C. for 30 seconds (insoluble treatment). Next, dip in a dyeing bath with a liquid temperature of 30° C. while adjusting the iodine concentration and dipping time so that the polarizing plate has a predetermined transmittance. In this example, it was immersed in an iodine aqueous solution obtained by mixing 0.2 parts by weight of iodine and 1.5 parts by weight of potassium iodide with respect to 100 parts by weight of water for 60 seconds (dyeing treatment). Then, it was immersed in a cross-linking bath (with respect to 100 parts by weight of water, 3 parts by weight of potassium iodide and 3 parts by weight of boric acid in an aqueous solution of boric acid) at a liquid temperature of 30° C. for 30 seconds (cross-linking treatment). ). Thereafter, while the laminate was immersed in an aqueous solution of boric acid at a liquid temperature of 70°C (an aqueous solution obtained by mixing 4 parts by weight of boric acid and 5 parts by weight of potassium iodide with respect to 100 parts by weight of water), it was placed between rollers with different peripheral speeds. Uniaxial stretching was performed in the longitudinal direction (longitudinal direction) so that the total stretching ratio became 5.5 times (stretching in water). Thereafter, the laminate was immersed in a cleaning bath (an aqueous solution obtained by mixing 4 parts by weight of potassium iodide with respect to 100 parts by weight of water) at a liquid temperature of 30° C. (washing treatment). Next, apply the adhesive shown below on the surface of the PVA-based resin layer (polarizer) of the laminate so that the thickness of the adhesive layer after hardening is 1.0 μm, and attach the methacrylic resin film constituting the protective layer ( Thickness: 40 μm, moisture permeability: 0.6 g/m 2 /24hr, having a glutarimide structure), after heating to 50° C. with an IR heater from the side of the methacrylic resin film, and irradiating the following ultraviolet rays, the The adhesive hardens. Then, the substrate was peeled off from the PVA-based resin layer to obtain a polarizer laminate (polarizing plate having a configuration of a polarizer/protective layer). In addition, the thickness of the polarizer is 5 μm, and the single transmittance is 42.3%. Moreover, the moisture content of the obtained polarizing plate was 1.0 weight%. (Adhesive composition) 40 parts by weight of N-hydroxyethylacrylamide (HEAA), 60 parts by weight of acryloylmorpholin (ACMO) and 3 parts by weight of photoinitiator "IRGACURE 819" (manufactured by BASF Corporation) were blended. Mix to prepare an adhesive with a viscosity of 40mPa·S before hardening. (Ultraviolet) The active energy line uses an ultraviolet (gallium-enclosed metal halide lamp, irradiation device: Light HAMMER10 manufactured by Fusion UV Systems, Inc., bulb: V bulb, peak illuminance: 1600mW/cm 2 , cumulative irradiation 1000/mJ/ cm 2 (wavelength 380~440nm)). In addition, the illuminance of ultraviolet rays was measured using a Sola-Check system manufactured by Solatell.

2.製作抗反射積層體 於FUJIFILM Co.製造之TAC薄膜(製品名：TD80-UL，厚度：80μm)單面，利用硬塗處理形成硬塗(HC)層(厚度：7μm)而獲得HC-TAC薄膜(厚度：87μm)。將該HC-TAC薄膜作為抗反射層形成用基材使用。於基材之HC層表面利用濺鍍形成由SiOx所構成之密著層(厚度：10nm)後，再於該密著層上依序製膜Nb2 O5 膜(高折射率層)、SiO2 膜(低折射率層)、Nb2 O5 膜(高折射率層)及SiO2 膜(低折射率層)而形成抗反射層(4層合計厚度：200nm)。接著於抗反射層上形成由具有全氟聚醚基之烷氧矽烷化合物所構成的防污層(厚度：10nm)，製出抗反射積層體。2. Manufacture of anti-reflection laminate on one side of TAC film (product name: TD80-UL, thickness: 80 μm) manufactured by FUJIFILM Co., and use hard coating to form a hard coating (HC) layer (thickness: 7 μm) to obtain HC- TAC film (thickness: 87 μm). This HC-TAC film was used as a substrate for forming an antireflection layer. After forming an adhesive layer (thickness: 10nm) made of SiOx by sputtering on the surface of the HC layer of the substrate, a Nb 2 O 5 film (high refractive index layer), SiO 2 film (low refractive index layer), Nb 2 O 5 film (high refractive index layer) and SiO 2 film (low refractive index layer) to form an antireflection layer (total thickness of 4 layers: 200nm). Next, an antifouling layer (thickness: 10 nm) composed of an alkoxysilane compound having a perfluoropolyether group was formed on the antireflection layer to produce an antireflection laminate.

3.製作附抗反射層之偏光板 於上述偏光件積層體之偏光件表面依序貼合作為第1相位差層之環狀烯烴系薄膜(折射率特性：nx＞ny＞nz，面內相位差：116nm)及作為第2相位差層之改質聚乙烯薄膜(折射率特性：nz＞nx＞ny，面內相位差：35nm)。貼合係使用與上述相同之紫外線硬化型接著劑。另，第1相位差層係以其慢軸相對於偏光件之吸收軸構成0°，且第2相位差層係以其慢軸相對於偏光件之吸收軸構成90°角的方式予以貼合。此外，於上述偏光件積層體之保護層(甲基丙烯酸系樹脂薄膜)表面，隔著丙烯酸系黏著劑(厚度：20μm)貼合抗反射積層體之HC-TAC薄膜而獲得附抗反射層之偏光板。將所製得之附抗反射層之偏光板供於上述(3)及(4)之評估。結果列於表1。3. Production of polarizing plate with anti-reflection layer On the surface of the polarizer of the above-mentioned polarizer laminate, a cyclic olefin film (refractive index characteristic: nx>ny>nz, in-plane retardation: 116nm) and a second retardation layer are bonded sequentially. Layer modified polyethylene film (refractive index characteristics: nz>nx>ny, in-plane retardation: 35nm). The bonding system uses the same UV-curable adhesive as above. In addition, the slow axis of the first retardation layer forms 0° with respect to the absorption axis of the polarizer, and the second retardation layer is bonded so that its slow axis forms an angle of 90° with respect to the absorption axis of the polarizer. . In addition, on the surface of the protective layer (methacrylic resin film) of the above-mentioned polarizer laminate, the HC-TAC film of the antireflection laminate was bonded through an acrylic adhesive (thickness: 20 μm) to obtain an antireflection layer. polarizer. The prepared polarizing plate with an antireflection layer was used for the evaluations in (3) and (4) above. The results are listed in Table 1.

[實施例2] 除了將偏光板之水分率設為0.6重量%以外，依與實施例1同樣方式製作出附抗反射層之偏光板。將所製得之偏光板供於進行與實施例1相同之評估。結果顯示於表1。[Example 2] A polarizing plate with an antireflective layer was produced in the same manner as in Example 1 except that the moisture content of the polarizing plate was set at 0.6% by weight. The obtained polarizing plate was subjected to the same evaluation as in Example 1. The results are shown in Table 1.

[實施例3] 除了將保護層之透濕度設為0.2g/m2 /24hr以外，依與實施例1同樣方式製作出附抗反射層之偏光板。將所製得之偏光板供於進行與實施例1相同之評估。結果顯示於表1。[Example 3] A polarizing plate with an antireflection layer was produced in the same manner as in Example 1 except that the moisture permeability of the protective layer was set at 0.2 g/m 2 /24hr. The obtained polarizing plate was subjected to the same evaluation as in Example 1. The results are shown in Table 1.

[實施例4] 除了將偏光板之水分率設為0.6重量%以外，依與實施例3同樣方式製作出附抗反射層之偏光板。將所製得之偏光板供於進行與實施例1相同之評估。結果顯示於表1。[Example 4] A polarizing plate with an antireflection layer was produced in the same manner as in Example 3 except that the moisture content of the polarizing plate was set at 0.6% by weight. The obtained polarizing plate was subjected to the same evaluation as in Example 1. The results are shown in Table 1.

[實施例5] 除了將偏光板之水分率設為2.0重量%以外，依與實施例1同樣方式製作出附抗反射層之偏光板。將所製得之偏光板供於進行與實施例1相同之評估。結果顯示於表1。[Example 5] A polarizing plate with an antireflective layer was produced in the same manner as in Example 1 except that the moisture content of the polarizing plate was set at 2.0% by weight. The obtained polarizing plate was subjected to the same evaluation as in Example 1. The results are shown in Table 1.

[比較例1] 於與實施例2相同之偏光件積層體之保護層表面，隔著丙烯酸系黏著劑(厚度：20μm)貼合實施例1中使用之HC-TAC薄膜。於所製得之積層體之HC-TAC薄膜表面，依與實施例1同樣方式形成抗反射層(含有密著層及防污層)。然後，於偏光件表面依與實施例1同樣方式貼合第1相位差層及第2相位差層。即，將含有偏光板之積層體用供於進行抗反射層形成製程之順序製作出附抗反射層之偏光板。將所製得之偏光板供於進行與實施例1相同之評估。結果顯示於表1。[Comparative example 1] The HC-TAC film used in Example 1 was bonded to the surface of the protective layer of the same polarizer laminate as in Example 2 via an acrylic adhesive (thickness: 20 μm). On the surface of the HC-TAC film of the obtained laminate, an antireflection layer (including an adhesion layer and an antifouling layer) was formed in the same manner as in Example 1. Then, the first retardation layer and the second retardation layer were bonded on the surface of the polarizer in the same manner as in Example 1. That is, a polarizing plate with an antireflection layer is produced by using a laminate including a polarizer in the order of performing the antireflection layer forming process. The obtained polarizing plate was subjected to the same evaluation as in Example 1. The results are shown in Table 1.

[表1]

Figure 02_image001
[Table 1]
Figure 02_image001

如表1所明示，可知藉由調整偏光板之水分率，可抑制附抗反射層之偏光板在高溫高濕環境下的尺寸變化，並可抑制翹曲。此外，從比較實施例1及3與實施例2及4的結果可知，藉由縮小偏光板之保護層的透濕度，可進一步抑制尺寸變化。As shown in Table 1, it can be seen that by adjusting the moisture content of the polarizing plate, the dimensional change of the polarizing plate with an anti-reflection layer in a high-temperature and high-humidity environment can be suppressed, and warpage can also be suppressed. In addition, comparing the results of Examples 1 and 3 with Examples 2 and 4, it can be seen that the dimensional change can be further suppressed by reducing the moisture permeability of the protective layer of the polarizing plate.

產業上之可利用性 本發明之附抗反射層之偏光板可適宜使用在液晶顯示裝置、有機EL顯示裝置、量子點顯示裝置等之影像顯示裝置。Industrial availability The polarizing plate with an antireflection layer of the present invention can be suitably used in image display devices such as liquid crystal display devices, organic EL display devices, and quantum dot display devices.

10‧‧‧偏光板 11‧‧‧偏光件 12‧‧‧保護層 20‧‧‧基材 30‧‧‧抗反射層 100‧‧‧附抗反射層之偏光板10‧‧‧polarizer 11‧‧‧Polarizer 12‧‧‧protective layer 20‧‧‧Substrate 30‧‧‧anti-reflection layer 100‧‧‧Polarizing plate with anti-reflection layer

圖1係本發明之一實施形態之附抗反射層之偏光板的概略截面圖。Fig. 1 is a schematic cross-sectional view of a polarizing plate with an antireflection layer according to an embodiment of the present invention.

10‧‧‧偏光板 10‧‧‧polarizer

11‧‧‧偏光件 11‧‧‧Polarizer

12‧‧‧保護層 12‧‧‧protective layer

20‧‧‧基材 20‧‧‧Substrate

30‧‧‧抗反射層 30‧‧‧anti-reflection layer

100‧‧‧附抗反射層之偏光板 100‧‧‧Polarizing plate with anti-reflection layer

Claims (8)

一種附抗反射層之偏光板，具備：偏光板，其具有偏光件及設置在該偏光件之一側的保護層；基材，其貼合在該保護層上；及抗反射層，其係直接形成在該基材上；並且其於該偏光件之與該保護層相反之側更具備第1相位差層，該第1相位差層具有nx>ny>nz之折射率特性；其於該第1相位差層之與該偏光件相反之側更具備第2相位差層，該第2相位差層具有nz>nx>ny之折射率特性；且該偏光板之水分率為0.5重量%以上且2.0重量%以下。 A polarizing plate with an anti-reflection layer, comprising: a polarizing plate having a polarizer and a protective layer arranged on one side of the polarizer; a base material attached to the protective layer; and an anti-reflection layer, which is It is directly formed on the substrate; and it has a first retardation layer on the opposite side of the polarizer to the protective layer, and the first retardation layer has a refractive index characteristic of nx>ny>nz; The side of the first retardation layer opposite to the polarizer is further equipped with a second retardation layer, the second retardation layer has a refractive index characteristic of nz>nx>ny; and the moisture content of the polarizer is 0.5% by weight or more And 2.0% by weight or less. 如請求項1之附抗反射層之偏光板，其中前述保護層之透濕度為1.0g/m2/24hr以下。 The polarizing plate with an anti-reflection layer according to claim 1, wherein the moisture permeability of the protective layer is 1.0 g/m 2 /24hr or less. 如請求項2之附抗反射層之偏光板，其中前述保護層含有(甲基)丙烯酸系樹脂。 The polarizing plate with an antireflection layer according to claim 2, wherein the protective layer contains (meth)acrylic resin. 如請求項1至3中任一項之附抗反射層之偏光板，其中前述基材在抗反射層側之表面具有硬塗層。 The polarizing plate with an antireflection layer according to any one of claims 1 to 3, wherein the surface of the substrate on the side of the antireflection layer has a hard coat layer. 如請求項1至3中任一項之附抗反射層之偏光板，其在65℃及90%RH之條件下保持500小時後，前述偏光件之吸收軸方向的尺寸變化率低於0.10%。 A polarizing plate with an anti-reflection layer according to any one of claims 1 to 3, after being kept at 65°C and 90% RH for 500 hours, the rate of dimensional change in the direction of the absorption axis of the polarizer is less than 0.10% . 如請求項5之附抗反射層之偏光板，其在65℃及90%RH之條件下保持500小時後可能產生的捲曲 在與前述抗反射層相反之側呈凸狀。 For example, the polarizing plate with anti-reflection layer as claimed in claim 5, the curl that may occur after it is kept at 65°C and 90%RH for 500 hours It is convex on the side opposite to the aforementioned antireflection layer. 一種如請求項1至6中任一項之附抗反射層之偏光板的製造方法，其包含下述步驟：製作包含偏光件及保護層之偏光件積層體；於基材形成抗反射層，製作抗反射積層體；及將該抗反射積層體之基材貼合至該偏光件積層體之保護層表面。 A method of manufacturing a polarizing plate with an antireflection layer according to any one of claims 1 to 6, comprising the following steps: making a polarizer laminate including a polarizer and a protective layer; forming an antireflection layer on a substrate, making an anti-reflection laminate; and attaching the base material of the anti-reflection laminate to the surface of the protective layer of the polarizer laminate. 如請求項7之製造方法，其中前述抗反射層係利用濺鍍形成。 The manufacturing method according to claim 7, wherein the antireflection layer is formed by sputtering.
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