TWI628456B - Antireflective film - Google Patents
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- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/111—Anti-reflection coatings using layers comprising organic materials
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Abstract
茲提供一種抗反射薄膜，係在抗反射薄膜中，不使來自正面的外來光之反射光帶有色澤，且對於由各種角度入射的外來光之反射光均可降低其色澤。具體而言係提供一種抗反射薄膜，其特徵為對於屬CIE標準光源之C光源之波長380nm至780nm之區域中的入射角為5°至50°之範圍的任一入射光，在入射角與反射角相等之反射條件下的反射光之色相在CIE1976L* a* b*色空間中均滿足-3≦a*≦3、-5≦b*≦5。 An anti-reflection film is provided in the anti-reflection film, so that the reflected light of external light from the front side is not colored, and the reflected light of external light incident from various angles can be reduced in color. Specifically, an anti-reflection film is provided, which is characterized in that for any incident light having an incident angle in a range of 5 ° to 50 ° in a region of a wavelength of 380 nm to 780 nm of a C light source that is a CIE standard light source, In the CIE1976L * a * b * color space, the hue of the reflected light under the same reflection angle conditions satisfy -3 ≦ a * ≦ 3, -5 ≦ b * ≦ 5.
Description
本說明書中所揭示之內容係有關於一種以防止外來光在顯示裝置等的顯示螢幕反射為目的而設置之抗反射薄膜、具備該抗反射薄膜之顯示裝置、具備該抗反射薄膜之偏光板及觸控面板。此種抗反射面板係適合設置於顯示裝置的顯示螢幕而使用。 The contents disclosed in this specification relate to an antireflection film provided for the purpose of preventing reflection of external light on a display screen of a display device or the like, a display device including the antireflection film, a polarizing plate provided with the antireflection film, and Touch panel. Such an anti-reflection panel is suitable for use in a display screen of a display device.
一般而言，顯示器不論在室內或室外使用，均係於外來光等入射的環境下使用。此外來光等之入射光在顯示器表面等經正反射，由此產生的反射影像與顯示影像混合而導致螢幕顯示品質降低。因此，對顯示器表面等賦予抗反射功能實屬必要，並要求抗反射功能的高性能化。 In general, whether the display is used indoors or outdoors, it is used under the environment where external light is incident. In addition, incident light such as incoming light is regularly reflected on the surface of the display, etc., and the resulting reflected image is mixed with the display image, resulting in a reduction in screen display quality. Therefore, it is necessary to provide an anti-reflection function to the display surface and the like, and to increase the performance of the anti-reflection function.
一般上，抗反射功能可藉由在透明支持體上形成包含金屬氧化物等透明材料之高折射率層與低折射率層的重複構造所衍生的多層構造之抗反射層來獲得。包含此等多層構造之抗反射層可採用化學沉積(CVD)法、或物 理沉積(PVD)法等乾式成膜法來形成。若採用乾式成膜法來形成抗反射層時，雖有可精密控制低折射率層、高折射率層之膜厚的優點，但另一方面由於在真空中進行成膜，而存有生產性低、不適合大量生產的問題。另外，作為抗反射層之形成方法，備受矚目的是採用可達大面積化、連續生產、低成本化之使用塗液的濕式成膜法之抗反射膜的生產。 Generally, the anti-reflection function can be obtained by forming an anti-reflection layer of a multilayer structure derived from a repeating structure of a high refractive index layer and a low refractive index layer containing a transparent material such as a metal oxide on a transparent support. The anti-reflection layer including these multilayer structures may be formed by a chemical deposition (CVD) method, or It is formed by a dry film formation method such as physical deposition (PVD) method. When the anti-reflection layer is formed by a dry film formation method, although the film thickness of the low-refractive index layer and the high-refractive index layer can be precisely controlled, on the other hand, it is productive because the film is formed in a vacuum. Low, not suitable for mass production. In addition, as a method for forming an anti-reflection layer, attention has been focused on the production of an anti-reflection film using a wet film formation method using a coating liquid that can achieve large area, continuous production, and low cost.
專利文獻1 特開2007-256346號公報 Patent Document 1 JP 2007-256346
近年隨著可移動終端的普及，在手上操作影像顯示裝置本體的場合日益增加。此外，在白晝的屋外比起在屋內使用的情況係暴露於較強的外來光下，因此，便要求一種在屋外亦無損視覺辨識性之低反射率的抗反射薄膜。 With the popularity of mobile terminals in recent years, the number of occasions when the main body of the image display device is operated on the hand has been increasing. In addition, the outside of the house is exposed to stronger external light than when it is used indoors. Therefore, an anti-reflection film with a low reflectance that does not impair the visibility of the house is required.
再者，對定置型影像顯示裝置應用抗反射薄膜時，其大部分係以減少來自固定光源的反射光為前提；此意指「外來光之入射角不改變」。與此相對，若為可移動終端時，由於係在屋外使用或在手上操作，外來光的入射會由各種角度入射，甚至觀看者亦經常以各種角度觀看 顯示器。因此，如欲對可移動終端應用抗反射薄膜時，則必需就對於各種入射角之光源的反射光，尤為反射光之色澤而非僅為來自正面的反射光進行探討。實際上，抗反射薄膜大部分係對應定置型影像顯示裝置來設計，其課題在於薄膜設計未假設外來光之入射角與反射角可能改變。 Furthermore, when an anti-reflection film is applied to a fixed-type image display device, most of it is based on the premise of reducing reflected light from a fixed light source; this means "the incident angle of external light does not change". In contrast, if it is a mobile terminal, because it is used outdoors or operated on the hand, the incidence of external light will be incident from various angles, and even viewers often watch from various angles monitor. Therefore, if an anti-reflection film is to be applied to a mobile terminal, it is necessary to discuss the reflected light of the light source at various incident angles, especially the color of the reflected light, not just the reflected light from the front. In fact, most anti-reflection films are designed for fixed-type image display devices. The problem is that the film design does not assume that the incident angle and reflection angle of external light may change.
本說明書中所揭示內容的目的之一在於提供一種可降低來自正面的反射光之色相，同時對於由各種角度入射的外來光的反射光均可降低其色相之抗反射薄膜、具備該抗反射薄膜之顯示裝置、具備該抗反射薄膜之偏光板及觸控面板。 One of the objects disclosed in this specification is to provide an anti-reflection film capable of reducing the hue of reflected light from the front side and reducing the hue of reflected light from external light incident from various angles, and the anti-reflection film provided with the same. A display device, a polarizing plate provided with the antireflection film, and a touch panel.
此目的係藉由提供一種如後述之抗反射薄膜、具備該抗反射薄膜之影像顯示裝置或液晶顯示裝置、具備該抗反射薄膜之偏光板來達成。 This object is achieved by providing an anti-reflection film, an image display device or a liquid crystal display device provided with the anti-reflection film, and a polarizing plate provided with the anti-reflection film as described later.
亦即，在一形態中，此抗反射薄膜之特徵為對於屬CIE標準光源之C光源之波長380nm至780nm之區域中的入射角為5°至50°之範圍的任一入射光，在入射角與反射角相等之反射條件下的反射光之色相在CIE1976L* a* b*色空間中均滿足-3≦a*≦3、-5≦b*≦5。 That is, in one form, the anti-reflection film is characterized in that any incident light having an incident angle in a range of 5 ° to 50 ° in a region of a wavelength of 380nm to 780nm of a C light source that is a CIE standard light source is incident. In the CIE1976L * a * b * color space, the hue of the reflected light under the same reflection conditions as the reflection angle is equal to -3 ≦ a * ≦ 3, -5 ≦ b * ≦ 5.
在一實施形態中，茲提供一種抗反射薄膜，其特徵為於上述抗反射薄膜表面之視覺平均反射率係為0.05%以上1.0%以下之範圍內。 In one embodiment, an anti-reflection film is provided, characterized in that the average visual reflectance of the surface of the anti-reflection film is within a range of 0.05% to 1.0%.
在另一形態中，還可提供一種具備上述抗反射薄膜之顯示裝置。 In another aspect, a display device including the anti-reflection film can be provided.
於本說明書中使用時，所謂「顯示裝置」之用語，係指用以對其使用者視覺地輸出之終端裝置，該顯示裝置係例如於其顯示螢幕(display screen)映射出影像。作為此類顯示裝置，尤其可列舉液晶顯示器(LCD)、CRT顯示器、有機電致發光顯示器(ELD)、電漿顯示器(PDP)、表面電場顯示器(SED)、場發射顯示器(FED)等，惟不限定於此等。 As used in this specification, the term "display device" refers to a terminal device for visually outputting to a user thereof, and the display device maps, for example, an image on a display screen thereof. Examples of such a display device include a liquid crystal display (LCD), a CRT display, an organic electroluminescence display (ELD), a plasma display (PDP), a surface electric field display (SED), and a field emission display (FED). It is not limited to these.
在又一形態中，亦可提供一種具備上述抗反射薄膜之偏光板。 In still another aspect, a polarizing plate including the antireflection film may be provided.
且在又一形態中，還可提供一種具備上述抗反射薄膜之觸控面板。 In still another aspect, a touch panel including the anti-reflection film is provided.
藉由將如上述之抗反射薄膜設置於影像顯示裝置或液晶顯示裝置，可使於抗反射薄膜表面之視覺平均反射率為0.05%以上1.0%以下之範圍內，使來自正面的反射光帶有色澤的情況得以減少，同時使由各種角度入射的外來光之反射光帶有色澤的情況得以減少。又，藉由將使用該抗反射薄膜之偏光板設置於液晶顯示裝置的表面，又藉由將該抗反射薄膜使用於觸控面板，皆可獲得同樣之效果。 By arranging the anti-reflection film as described above on an image display device or a liquid crystal display device, the average visual reflectance on the surface of the anti-reflection film can be in a range of 0.05% to 1.0%, so that the reflected light from the front side is provided with The condition of the color is reduced, and the condition of the reflected light of the external light incident from various angles is reduced. In addition, the same effect can be obtained by providing a polarizing plate using the antireflection film on the surface of a liquid crystal display device and using the antireflection film on a touch panel.
10‧‧‧抗反射薄膜 10‧‧‧Anti-reflective film
11‧‧‧透明支持體 11‧‧‧ transparent support
12‧‧‧硬塗層 12‧‧‧hard coating
13‧‧‧高折射率層 13‧‧‧High refractive index layer
14‧‧‧低折射率層 14‧‧‧ Low refractive index layer
21‧‧‧屬不使抗反射薄膜之反射光帶有色澤之中和色的色相範圍 21‧‧‧ is a hue range that does not make the reflected light of the anti-reflection film have a neutral color
第1圖為一實施形態之抗反射薄膜的示意剖面圖。 FIG. 1 is a schematic cross-sectional view of an anti-reflection film according to an embodiment.
第2圖為表示實施例及比較例中所製作之抗反射薄膜的反射光之色相的角度相關性的圖。 FIG. 2 is a graph showing the angular dependence of the hue of the reflected light of the antireflection films produced in the examples and comparative examples.
以下，就本說明書中所揭示之例示性抗反射薄膜詳細加以說明。 Hereinafter, exemplary antireflection films disclosed in this specification will be described in detail.
本說明書中所揭示之抗反射薄膜對於屬CIE標準光源之C光源之波長380nm至780nm之區域中的入射角為5°至50°之範圍的任一入射光，在入射角與反射角相等之反射條件下的反射光之色相在CIE1976L* a* b*色空間中均滿足-3≦a*≦3、-5≦b*≦5。因此，即使外來光之入射角度改變，抗反射薄膜的反射光之色相仍為中和色。 The anti-reflection film disclosed in this specification has an incident angle equal to the reflection angle for any incident light in the range of 5 ° to 50 ° in the wavelength range of 380nm to 780nm of the C light source that is a CIE standard light source. The hue of the reflected light under the reflection condition satisfies -3 ≦ a * ≦ 3, -5 ≦ b * ≦ 5 in the CIE1976L * a * b * color space. Therefore, even if the incident angle of the external light is changed, the hue of the reflected light of the antireflection film is a neutral color.
更者，對於入射角為5°之入射光，在反射角為-5°至-80°之範圍的反射光之色相在CIE1976L* a* b*色空間中均滿足-3≦a*≦3、-5≦b*≦5，藉此使僅改變對於抗反射薄膜的觀看角度時的反射光之色相為中和色，宜滿足此條件為佳。 Furthermore, for the incident light with an incident angle of 5 °, the hue of the reflected light in the range of -5 ° to -80 ° with the reflection angle satisfies -3 ≦ a * ≦ 3 in the CIE1976L * a * b * color space. , -5 ≦ b * ≦ 5, so that the hue of the reflected light when changing the viewing angle of the antireflection film is neutralized, and it is better to satisfy this condition.
若對於屬CIE標準光源之C光源之波長380nm至780nm之區域中的入射角為5°至50°之範圍的任一入射 光，在入射角與反射角相等之反射條件下的反射光之色相在CIE1976L* a* b*色空間中均滿足△a*≦3、△b*≦3(其中，△a*=a*max-a*min，△b*=b*max-b*min，a*max及a* min分別表示a*值之最大值及最小值，且b*max及b* min分別表示b*值之最大值及最小值)，入射角或反射角之角度改變時的色相變化減小，故宜滿足此條件為佳。色相變化的幅度愈小愈佳，因此，若△a*≦1、△b*≦1則更佳。 If the incident angle in the range of 380nm to 780nm of the C light source that is a CIE standard light source is in the range of 5 ° to 50 ° Light, the hue of the reflected light under the reflection conditions where the incident angle and the reflection angle are equal in the CIE1976L * a * b * color space all satisfy △ a * ≦ 3, △ b * ≦ 3 (where △ a * = a * max-a * min, △ b * = b * max-b * min, a * max and a * min respectively represent the maximum and minimum values of a * value, and b * max and b * min respectively represent b * value The maximum and minimum values), the hue change when the angle of the incident angle or the reflection angle is changed is reduced, it is better to meet this condition. The smaller the change in hue, the better, so it is better if Δa * ≦ 1 and Δb * ≦ 1.
在一實施形態中，抗反射薄膜之視覺平均反射率較佳為0.05%以上1.0%以下之範圍內。 In one embodiment, the visual average reflectance of the anti-reflection film is preferably within a range of 0.05% to 1.0%.
一面參照第1圖一面就抗反射薄膜之層構造詳細加以說明。本例之抗反射薄膜係以採用在透明支持體上塗布硬塗層，於其上依序積層高折射率層與低折射率層之多層構造的方式提供。此時，高折射率層與低折射率層的層數不拘。惟，當考量成本及良品生產率等時，若如第1圖所示，本例之抗反射薄膜(10)在透明支持體(11)上塗布硬塗層(12)，進而於其上塗布高折射率層(13)，再於其上積層低折射率層(14)，則可適用於作為抗反射薄膜。 The layer structure of the antireflection film will be described in detail with reference to FIG. 1. The anti-reflection film of this example is provided by applying a hard coat layer on a transparent support, and sequentially stacking a multilayer structure of a high refractive index layer and a low refractive index layer thereon. In this case, the number of layers of the high refractive index layer and the low refractive index layer is not limited. However, when considering cost and good product productivity, as shown in Fig. 1, the anti-reflection film (10) of this example is coated with a hard coat layer (12) on a transparent support (11), and then coated with a high The refractive index layer (13), and the low refractive index layer (14) laminated thereon, can be used as an anti-reflection film.
此時，透過持續調整各層之膜厚及折射率，可使作為反射光之色相參數的a*值、b*值符合目標值。例如， 較佳為可使硬塗層之膜厚為3.0μm以上10μm以下之範圍、使硬塗層之折射率為1.48以上1.53以下之範圍、使高折射率層之膜厚為230nm以上260nm以下之範圍、使高折射率層之折射率為1.58以上1.64以下之範圍、使低折射率層之膜厚為115nm以上135nm以下之範圍、使低折射率層之折射率中視覺平均反射率為0.05%以上1.0%以下之範圍內的折射率(例如折射率1.30)。 At this time, by continuously adjusting the film thickness and refractive index of each layer, the a * value and b * value, which are the hue parameters of the reflected light, can meet the target values. E.g, The thickness of the hard coat layer is preferably in the range of 3.0 μm to 10 μm, the refractive index of the hard coat layer is in the range of 1.48 to 1.53, and the thickness of the high refractive index layer is in the range of 230 nm to 260 nm. , The refractive index of the high refractive index layer should be in the range of 1.58 or more and 1.64 or less, the film thickness of the low refractive index layer should be in the range of 115 nm or more and 135 nm or less, and the average visual reflectance of the refractive index of the low refractive index layer should be 0.05% or more. A refractive index within a range of 1.0% or less (for example, a refractive index of 1.30).
作為如上述之硬塗層、高折射率層及低折射率層之塗布方法，可列舉噴射法、網版印刷法、刮刀成膜法、凹版印刷法、模具塗布法、噴墨法等既有之塗布方法，但不特別限定。 Examples of the coating method of the hard coat layer, the high refractive index layer, and the low refractive index layer described above include conventional methods such as a spray method, a screen printing method, a doctor blade film forming method, a gravure printing method, a mold coating method, and an inkjet method. The coating method is not particularly limited.
本例之抗反射薄膜中的透明支持體係考量透明性或光的折射率等光學特性、甚而耐衝撃性、耐熱性、耐久性等各物性，由各種有機高分子來調製。作為該有機高分子，可列舉以下者，惟不限定於此：聚乙烯、聚丙烯等聚烯烴系、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯等聚酯系、三乙醯基纖維素、二乙醯基纖維素、賽洛凡等纖維素系、6-尼龍、6,6-尼龍等聚醯胺系、聚甲基丙烯酸甲酯等丙烯酸系、聚苯乙烯、聚氯乙烯、聚醯亞胺、聚乙烯醇、聚碳酸酯、乙烯乙烯醇等。較佳的是，該有機高分子為聚對苯二甲酸乙二酯、三乙醯基纖維素、聚碳酸酯、聚甲基丙烯酸甲酯。更佳的是，該有機高分子為三乙醯基纖維素，其因複折射率小、透明性良好，對於各種顯示器可適用之。 The transparent support system in the anti-reflection film of this example is prepared by various organic polymers in consideration of optical properties such as transparency and light refractive index, and even physical properties such as impact resistance, heat resistance, and durability. Examples of the organic polymer include, but are not limited to, polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polyethylene naphthalate, and triethylene Cellulose based on fluorenyl cellulose, diethyl cellulose, xylofan, polyamine based on 6-nylon, 6,6-nylon, acrylic based on polymethyl methacrylate, polystyrene, poly Vinyl chloride, polyimide, polyvinyl alcohol, polycarbonate, ethylene vinyl alcohol, etc. Preferably, the organic polymer is polyethylene terephthalate, triethyl cellulose, polycarbonate, or polymethyl methacrylate. More preferably, the organic polymer is triethylfluorenyl cellulose, which is suitable for various displays due to its small complex refractive index and good transparency.
再者，藉由對此等有機高分子添加周知之添加劑，例如紫外線吸收劑、紅外線吸收劑、塑化劑、滑劑、著色劑、抗氧化劑、難燃劑等，可對透明支持體附加各種功能。又，透明支持體可由選自上述有機高分子的1種或2種以上之混合物、或者聚合物來調製，亦可為積層複數層而成者。 Furthermore, by adding well-known additives to these organic polymers, such as ultraviolet absorbers, infrared absorbers, plasticizers, lubricants, colorants, antioxidants, and flame retardants, various kinds of additives can be added to the transparent support. Features. The transparent support may be prepared from a mixture of one or two or more kinds of polymers selected from the above-mentioned organic polymers, or a polymer, or may be formed by laminating a plurality of layers.
另外，透明支持體之厚度較佳為20μm以上200μm以下之範圍內，更佳為20μm以上80μm以下之範圍內。 The thickness of the transparent support is preferably within a range of 20 μm to 200 μm, and more preferably within a range of 20 μm to 80 μm.
在一實施形態中，以抗反射薄膜中的硬塗層而言，可採用丙烯酸系材料。作為該丙烯酸系材料，可使用多元醇之丙烯酸或甲基丙烯酸酯之類的單官能、二官能或三官能以上之(甲基)丙烯酸酯化合物、合成自二異氰酸酯與多元醇及丙烯酸或甲基丙烯酸之羥基酯等之類的多官能胺基甲酸酯(甲基)丙烯酸酯化合物。又，除此之外，作為游離輻射線型材料，還可使用具有丙烯酸酯系官能基之聚醚樹脂、聚酯樹脂、環氧樹脂、醇酸樹脂、螺縮醛樹脂、聚丁二烯樹脂、多硫醇多烯樹脂等。 In one embodiment, the hard coat layer in the antireflection film may be an acrylic material. As the acrylic material, monofunctional, difunctional, or trifunctional or higher (meth) acrylate compounds such as acrylic acid or methacrylate of a polyhydric alcohol can be used, synthesized from a diisocyanate and a polyol, and acrylic or methyl. Polyfunctional urethane (meth) acrylate compounds such as hydroxy esters of acrylic acid and the like. In addition, as the radiation-free material, polyether resins having polyester functional groups, polyester resins, epoxy resins, alkyd resins, spiral resins, polybutadiene resins, Polythiol polyene resin and the like.
而且，於本說明書中使用時，所謂「(甲基)丙烯酸酯」之用語，係表示「丙烯酸酯」與「甲基丙烯酸酯」兩者。例如「胺基甲酸酯(甲基)丙烯酸酯」係表示「胺基甲酸酯丙烯酸酯」與「胺基甲酸酯甲基丙烯酸酯」兩者。 As used herein, the term "(meth) acrylate" means both "acrylate" and "methacrylate". For example, "urethane (meth) acrylate" means both "urethane acrylate" and "urethane methacrylate".
作為單官能之(甲基)丙烯酸酯化合物，可列舉例如(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸2-羥丁酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸縮水甘油酯、丙烯醯啉、N-乙烯吡咯烷酮、四氫呋喃丙烯酸酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十三酯、(甲基)丙烯酸十六酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸2-乙氧乙酯、(甲基)丙烯酸3-甲氧丁酯、乙基卡必醇(甲基)丙烯酸酯、(甲基)丙烯酸磷酸酯、環氧乙烷改質(甲基)丙烯酸磷酸酯、(甲基)丙烯酸苯氧酯、環氧乙烷改質(甲基)丙烯酸苯氧酯、環氧丙烷改質(甲基)丙烯酸苯氧酯、壬基酚(甲基)丙烯酸酯、環氧乙烷改質壬基酚(甲基)丙烯酸酯、環氧丙烷改質壬基酚(甲基)丙烯酸酯、甲氧基二乙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、甲氧基丙二醇(甲基)丙烯酸酯、鄰苯二甲酸2-(甲基)丙烯醯氧乙基-2-羥丙酯、(甲基)丙烯酸2-羥基-3-苯氧丙酯、氫鄰苯二甲酸2-(甲基)丙烯醯氧乙酯、氫鄰苯二甲酸2-(甲基)丙烯醯氧丙酯、六氫鄰苯二甲酸2-(甲基)丙烯醯氧丙酯、四氫鄰苯二甲酸2-(甲基)丙烯醯氧丙酯、(甲基)丙烯酸二甲胺基乙酯、(甲基)丙烯酸三氟乙酯、(甲基)丙烯酸四氟丙酯、(甲基)丙烯酸六氟丙酯、(甲基)丙烯酸八氟丙酯、(甲基)丙烯酸八氟丙酯、衍生自2-金剛烷及金剛烷 二醇之具有一價之單(甲基)丙烯酸酯的丙烯酸金剛烷酯等金剛烷衍生物單(甲基)丙烯酸酯等，惟不限定於此。 Examples of the monofunctional (meth) acrylate compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and (methyl) Base) n-butyl acrylate, isobutyl (meth) acrylate, third butyl (meth) acrylate, glycidyl (meth) acrylate, acrylic acid Phthaloline, N-vinylpyrrolidone, tetrahydrofuran acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isoamyl (meth) acrylate, isodecyl (meth) acrylate, Lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, 2-methacrylate Ethoxyethyl, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, (meth) acrylate phosphate, ethylene oxide modified (meth) acrylate phosphate Phenoxy (meth) acrylate, phenoxy acrylate (meth) acrylate, phenoxy (meth) acrylate propylene oxide, nonylphenol (meth) acrylate, cyclic Oxyethylene modified nonylphenol (meth) acrylate, propylene oxide modified nonylphenol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol Alcohol (meth) acrylate, methoxypropanediol (meth) acrylate, 2- (meth) acryloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy- (meth) acrylate- 3-phenoxypropyl ester, hydrogen phthalate 2- (meth) acrylic acid ethoxylate, 2- (meth) acrylic acid oxypropyl phthalate, 2- (meth) acrylic acid oxypropyl hexahydrophthalate, tetrahydro 2- (meth) acrylic acid oxypropyl phthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, (formyl) Hexafluoropropyl acrylate, octafluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, monovalent (meth) acrylic acid derived from 2-adamantane and adamantanediol However, the adamantane derivative mono (meth) acrylate and the like such as adamantane acrylate are not limited thereto.
作為前述二官能之(甲基)丙烯酸酯化合物，可列舉例如乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、己二醇二(甲基)丙烯酸酯、壬二醇二(甲基)丙烯酸酯、乙氧基化己二醇二(甲基)丙烯酸酯、丙氧基化己二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、乙氧基化新戊二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、羥基三甲基乙酸新戊二醇二(甲基)丙烯酸酯等二(甲基)丙烯酸酯等，惟不限定於此。 Examples of the difunctional (meth) acrylate compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, Hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, ethoxylated hexanediol di (meth) acrylate, propoxylated hexanediol di (meth) acrylate Ester, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol Di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, hydroxytrimethyl acetate neopentyl glycol di (meth) acrylate But not limited to di (meth) acrylate and the like.
作為前述三官能以上之(甲基)丙烯酸酯化合物，可列舉例如三羥甲基丙烷三(甲基)丙烯酸酯、乙氧基化三羥甲基丙烷三(甲基)丙烯酸酯、丙氧基化三羥甲基丙烷三(甲基)丙烯酸酯、三異三聚氰酸2-羥乙酯三(甲基)丙烯酸酯、三(甲基)丙烯酸甘油酯等三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、二新戊四醇三(甲基)丙烯酸酯、二三羥甲基丙烷三(甲基)丙烯酸酯等三官能之(甲基)丙烯酸酯化合物、或新戊四醇四(甲基)丙烯酸酯、二三羥甲基丙烷四(甲基)丙烯酸酯、二新戊四醇四(甲基)丙烯酸 酯、二新戊四醇五(甲基)丙烯酸酯、二三羥甲基丙烷五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、二三羥甲基丙烷六(甲基)丙烯酸酯等三官能以上之多官能(甲基)丙烯酸酯化合物、或此等(甲基)丙烯酸酯一部分經烷基或ε-己內酯取代之多官能(甲基)丙烯酸酯化合物等，惟不限定於此。 Examples of the trifunctional or higher (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, and propoxy Tri (meth) acrylate such as trimethylolpropane tri (meth) acrylate, 2-hydroxyethyl triisocyanurate tri (meth) acrylate, glyceryl tri (meth) acrylate, etc. Trifunctional (meth) acrylate compounds such as neopentyl tetraol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, Or neopentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dinepentaerythritol tetra (meth) acrylic acid Esters, dinepentaerythritol penta (meth) acrylate, ditrimethylolpropane penta (meth) acrylate, dinepentaerythritol hexa (meth) acrylate, ditrimethylolpropane hexa ( Trifunctional or higher polyfunctional (meth) acrylate compounds such as meth) acrylates, or polyfunctional (meth) acrylate compounds in which part of these (meth) acrylates are substituted with alkyl or ε-caprolactone Etc., but not limited to this.
丙烯酸系材料當中，基於可對所要之分子量、分子結構進行設計，並能容易取得形成之硬塗層之物性的平衡等理由，可適用多官能胺基甲酸酯丙烯酸酯。胺基甲酸酯丙烯酸酯可使多元醇、多元異氰酸酯及含羥基丙烯酸酯反應來獲得。具體可列舉共榮社化學公司製UA-306H、UA-306T、UA-3061等、日本合成化學公司製UV-1700B、UV-6300B、UV-7600B、UV-7605B、UV-7640B、UV-7650B等、新中村化學公司製U-4HA、U-6HA、UA-100H、U-6LPA、U-15HA、UA-32P、U-324A等、DAICEL-UCB公司製Ebecryl-1290、Ebecryl-1290K、Ebecryl-5129等、根上工業公司製UN-3220HA、UN-3220HB、UN-3220HC、UN-3220HS等，惟不在此限。 Among the acrylic materials, polyfunctional urethane acrylate is applicable for reasons such that the desired molecular weight and molecular structure can be designed, and the physical properties of the hard coat layer can be easily balanced. Urethane acrylates can be obtained by reacting polyols, polyisocyanates, and hydroxyl-containing acrylates. Specific examples include UA-306H, UA-306T, UA-3061, etc. manufactured by Kyoeisha Chemical Co., Ltd., UV-1700B, UV-6300B, UV-7600B, UV-7605B, UV-7640B, UV-7650B manufactured by Japan Synthetic Chemical Co., Ltd. U-4HA, U-6HA, UA-100H, U-6LPA, U-15HA, UA-32P, U-324A, etc., manufactured by Shin Nakamura Chemical Co., Ltd., Ebecryl-1290, Ebecryl-1290K, Ebecryl, manufactured by DAICEL-UCB -5129, etc., Gen-3 Industrial Co., Ltd. UN-3220HA, UN-3220HB, UN-3220HC, UN-3220HS, etc., but not limited to this.
另除此之外，作為游離輻射線型材料，可使用具有丙烯酸酯系官能基之聚醚樹脂、聚酯樹脂、環氧樹脂、醇酸樹脂、螺縮醛樹脂、聚丁二烯樹脂、多硫醇多烯樹脂等，不特別限定其材料。 In addition, as the free radiation type material, polyether resins having polyester functional groups, polyester resins, epoxy resins, alkyd resins, spiral resins, polybutadiene resins, and polysulfide can be used. The material of the alcohol polyene resin and the like is not particularly limited.
再者，由於游離輻射線硬化型材料係藉由紫外線硬化，故而在硬塗層形成用塗液中添加光聚合起始劑。作為光聚合起始劑，只要是照射紫外線時可產生自由基者即可，可使用例如苯乙酮類、安息香類、二苯甲酮類、膦氧化物類、縮酮類、蒽醌類、噻噸酮類。另，相對於100重量份之游離輻射線硬化型材料，光聚合起始劑之添加量係為0.1重量份~10重量份，較佳為1重量份~7重量份，更佳為1重量份~5重量份。 Furthermore, since the radiation-hardening material is hardened by ultraviolet rays, a photopolymerization initiator is added to the coating liquid for forming a hard coat layer. The photopolymerization initiator may be any one capable of generating free radicals when irradiated with ultraviolet rays, and examples thereof include acetophenones, benzoin, benzophenones, phosphine oxides, ketals, anthraquinones, Thioxanthone. In addition, the photopolymerization initiator is added in an amount of 0.1 to 10 parts by weight, preferably 1 to 7 parts by weight, and more preferably 1 part by weight relative to 100 parts by weight of the free radiation hardening type material. ~ 5 parts by weight.
更者，硬塗層形成用塗液中可視需求添加溶劑或各種添加劑。作為溶劑，可由甲苯、二甲苯、環己烷、環己苯等芳香烴類、正己烷等烴類、二丁醚、二甲氧基甲烷、二甲氧基乙烷、二乙氧基乙烷、環氧丙烷、二烷、二氧戊環、三烷、四氫呋喃、苯甲醚及乙基苯基醚等醚類、甲基異丁基酮、甲基丁基酮、丙酮、甲基乙基酮、二乙基酮、二丙基酮、二異丁基酮、環戊酮、環己酮、甲基環己酮、及甲基環己酮等酮類、且甲酸乙酯、甲酸丙酯、甲酸正戊酯、乙酸甲酯、乙酸乙酯、丙酸甲酯、丙酸乙酯、乙酸正戊酯、及γ-丁內酯等酯類、甚而甲基賽路蘇、賽路蘇、丁基賽路蘇、賽路蘇乙酸酯等賽路蘇類、甲醇、乙醇、異丙醇、丁醇等醇類當中考量塗布適性等來適當選擇。又，在塗液中還可添加表面調整劑、折射率調整劑、密接性提升劑、硬化劑等作為添加劑。 Furthermore, a solvent or various additives may be added to the coating liquid for forming a hard coat layer as required. As the solvent, aromatic hydrocarbons such as toluene, xylene, cyclohexane, and cyclohexylbenzene, hydrocarbons such as n-hexane, dibutyl ether, dimethoxymethane, dimethoxyethane, and diethoxyethane can be used. , Propylene oxide, two Alkane, dioxolane, trioxane Ethers such as alkane, tetrahydrofuran, anisole and ethylphenyl ether, methyl isobutyl ketone, methyl butyl ketone, acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, diiso Ketones such as butyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, and methylcyclohexanone, and ethyl formate, propyl formate, n-pentyl formate, methyl acetate, ethyl acetate, Esters such as methyl propionate, ethyl propionate, n-pentyl acetate, and γ-butyrolactone, and even methyl cyrus, cyrus, butyl cyrus, cyrus acetate, etc. Among alcohols such as luteus, methanol, ethanol, isopropanol, and butanol, they are appropriately selected in consideration of coating suitability. Moreover, a surface adjuster, a refractive index adjuster, an adhesiveness improving agent, a hardener, etc. may be added to the coating liquid as additives.
再者，在硬塗層形成用塗液中又可添加其他添加劑。作為此種添加劑，可列舉例如泡消劑、調平劑、抗氧化劑、紫外線吸收劑、光安定劑、聚合抑制劑等。 Further, other additives may be added to the coating liquid for forming a hard coat layer. Examples of such additives include a defoaming agent, a leveling agent, an antioxidant, an ultraviolet absorber, a light stabilizer, and a polymerization inhibitor.
在一實施形態中，作為抗反射薄膜中的高折射率層，可使用包含金屬烷氧化物、矽烷偶合劑、有機樹脂當中的任一種或多種組合而成之黏合劑，進而在黏合劑中添加金屬微粒或有機微粒者。此等成分係依據所要求之有機系塗布層之折射率來適當選擇，根據材料的組合、混合比等來調整折射率。例如，作為高折射率材料，係使用Ti、Ta、Zr、In、Zn等的金屬烷氧化物、或氧化鈦、氧化鋯、氧化鋅、氧化銦等的金屬微粒。 In one embodiment, as the high-refractive index layer in the antireflection film, an adhesive containing any one or more of a metal alkoxide, a silane coupling agent, and an organic resin may be used, and further added to the adhesive. Metal particles or organic particles. These components are appropriately selected according to the refractive index of the required organic coating layer, and the refractive index is adjusted according to the combination of materials, mixing ratio, and the like. For example, as the high refractive index material, metal alkoxides such as Ti, Ta, Zr, In, and Zn, or metal particles such as titanium oxide, zirconia, zinc oxide, and indium oxide are used.
供用作稀釋溶劑者不特別限定。然，考量到組成物之穩定性、對硬塗層之浸潤性、揮發性等，作為所利用之稀釋溶劑，可列舉甲醇、乙醇、異丙醇、丁醇、2-甲氧基乙醇等醇類、丙酮、甲基乙基酮、甲基異丁基酮等酮類、乙酸甲酯、乙酸乙酯、乙酸丁酯等酯類、二異丙醚等醚類、乙二醇、丙二醇、2-甲-2,4-戊二醇等二醇類、乙基賽路蘇、丁基賽路蘇、乙基卡必醇、丁基卡必醇等二醇醚類、己烷、庚烷、辛烷等脂肪烴類、鹵化烴、苯、甲苯、二甲苯等芳香烴、N-甲基吡咯烷酮、二甲基甲醯胺等。此外，溶劑係非僅為一種，亦可作為兩種以上之混合物使用。 It is not particularly limited for use as a diluent solvent. However, considering the stability of the composition, the wettability to the hard coating layer, volatility, etc., as the diluting solvent to be used, alcohols such as methanol, ethanol, isopropanol, butanol, and 2-methoxyethanol can be mentioned. Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, esters such as methyl acetate, ethyl acetate, butyl acetate, ethers such as diisopropyl ether, ethylene glycol, propylene glycol, 2 -Diols such as methyl-2,4-pentanediol, ethyl cyrus, butyl cyrus, glycol ethers such as ethyl carbitol, butyl carbitol, hexane, heptane, Aliphatic hydrocarbons such as octane, halogenated hydrocarbons, aromatic hydrocarbons such as benzene, toluene, and xylene, N-methylpyrrolidone, and dimethylformamide. In addition, the solvent is not limited to one type, and may be used as a mixture of two or more types.
作為供形成高折射率層之黏合劑基質形成材料，係包含游離輻射線硬化型材料。作為游離輻射線硬化型材料，可採用例示為硬塗層形成用塗液所含之游離輻射線硬化型材料的丙烯酸系材料。作為丙烯酸系材料，可使用多元醇之丙烯酸或甲基丙烯酸酯之類的單官能或多官能(甲基)丙烯酸酯化合物、合成自二異氰酸酯與多元醇及丙烯酸或甲基丙烯酸之羥基酯等之類的多官能胺基甲酸酯(甲基)丙烯酸酯化合物。又，除此之外，作為游離輻射線型材料，還可使用具有丙烯酸酯系官能基之聚醚樹脂、聚酯樹脂、環氧樹脂、醇酸樹脂、螺縮醛樹脂、聚丁二烯樹脂、多硫醇多烯樹脂等。 As a binder matrix forming material for forming a high-refractive index layer, a material containing a free radiation hardening type is included. As the radiation-hardenable material, an acrylic material exemplified as the radiation-hardenable material contained in the coating liquid for forming a hard coat layer can be used. As the acrylic material, monofunctional or polyfunctional (meth) acrylate compounds such as acrylic acid or methacrylate of polyhydric alcohols, synthetic compounds derived from diisocyanate and polyols, and hydroxy esters of acrylic acid or methacrylic acid can be used. Class of multifunctional urethane (meth) acrylate compounds. In addition, as the radiation-free material, polyether resins having polyester functional groups, polyester resins, epoxy resins, alkyd resins, spiral resins, polybutadiene resins, Polythiol polyene resin and the like.
在一實施形態中，作為抗反射薄膜中的低折射率層，就低折射粒子而言可採用包含LiF、MgF、3NaF．AlF或AlF(折射率皆為1.4)、或者Na3AlF6(冰晶石、折射率1.33)等低折射材料的低折射率粒子。此外，還可適用粒子內部含有空隙的粒子。在粒子內部含有空隙的粒子中，由於可使空隙部分成為空氣之折射率(≒1)，得以作成具極低折射率之低折射率粒子。具體可使用內部含有空隙之低折射率二氧化矽粒子。 In one embodiment, as the low-refractive index layer in the antireflection film, for low-refractive particles, LiF, MgF, and 3NaF may be used. Low-refractive index particles of low-refractive materials such as AlF or AlF (both refractive indices are 1.4), or Na 3 AlF 6 (cryolite, refractive index 1.33). In addition, particles having voids inside the particles can also be applied. Among particles containing voids inside the particles, the void portion can be made into the refractive index (空气 1) of air, so that low-refractive-index particles having extremely low refractive indices can be produced. Specifically, low-refractive-index silica particles containing voids can be used.
以低折射率層所使用之低折射率粒子而言，其粒徑較佳為1nm以上100nm以下。當粒徑大於100nm時，因瑞利散射使光明顯被反射，以致低折射率層發生白化而 有抗反射薄膜之透明性降低的傾向。另一方面粒徑小於1nm時，則發生粒子凝聚致使低折射率層中的粒子具不均勻性等問題。 For the low-refractive index particles used in the low-refractive index layer, the particle diameter is preferably 1 nm to 100 nm. When the particle diameter is greater than 100nm, light is significantly reflected due to Rayleigh scattering, so that the low refractive index layer is whitened and The transparency of the antireflection film tends to decrease. On the other hand, when the particle diameter is less than 1 nm, problems such as particle agglomeration and non-uniformity of particles in the low refractive index layer occur.
作為供形成低折射率層之黏合劑基質形成材料，係包含游離輻射線硬化型材料。作為游離輻射線硬化型材料，可採用例示為硬塗層形成用塗液所含之游離輻射線硬化型材料的丙烯酸系材料。作為丙烯酸系材料，可使用多元醇之丙烯酸或甲基丙烯酸酯之類的單官能或多官能(甲基)丙烯酸酯化合物、合成自二異氰酸酯與多元醇及丙烯酸或甲基丙烯酸之羥基酯等之類的多官能胺基甲酸酯(甲基)丙烯酸酯化合物。又，除此之外，作為游離輻射線型材料，還可使用具有丙烯酸酯系官能基之聚醚樹脂、聚酯樹脂、環氧樹脂、醇酸樹脂、螺縮醛樹脂、聚丁二烯樹脂、多硫醇多烯樹脂等。尚且，亦可適當使此等樹脂經氟化。 As a binder matrix forming material for forming a low-refractive-index layer, a material containing a radiation-hardening type is included. As the radiation-hardenable material, an acrylic material exemplified as the radiation-hardenable material contained in the coating liquid for forming a hard coat layer can be used. As the acrylic material, monofunctional or polyfunctional (meth) acrylate compounds such as acrylic acid or methacrylate of polyhydric alcohols, synthetic compounds derived from diisocyanate and polyols, and hydroxy esters of acrylic acid or methacrylic acid can be used. Class of multifunctional urethane (meth) acrylate compounds. In addition, as the radiation-free material, polyether resins having polyester functional groups, polyester resins, epoxy resins, alkyd resins, spiral resins, polybutadiene resins, Polythiol polyene resin and the like. Moreover, these resins may be appropriately fluorinated.
以下，就實施例及比較例進一步加以說明，惟該實施例係僅以例示目的而表示，本發明不限定於下述實施例。後述之調製例1至調製例3分別為實施例1中所使用之硬塗層形成用塗液、高折射率層形成用塗液、低折射率層形成用塗液的調製例。茲利用此等，並依循形成例1至3所示之程序來製作實施例1之抗反射薄膜。另外，透過改變後述製作條件來製作比較例1至比較例7之薄膜。 Hereinafter, examples and comparative examples will be further described, but the examples are shown for illustrative purposes only, and the present invention is not limited to the following examples. Preparation Examples 1 to 3 described later are preparation examples of the coating liquid for forming a hard coat layer, the coating liquid for forming a high refractive index layer, and the coating liquid for forming a low refractive index layer used in Example 1, respectively. Hereby, the anti-reflection film of Example 1 is manufactured by following the procedures shown in Formation Examples 1 to 3. In addition, the films of Comparative Examples 1 to 7 were produced by changing the production conditions described later.
使用25質量份之二新戊四醇三丙烯酸酯、25質量份之新戊四醇四丙烯酸酯、50質量份之胺基甲酸酯丙烯酸酯、5質量份之IRGACURE184(BASF公司製(光聚合起始劑))，將其溶於118質量份之甲基乙基酮來調製硬塗層形成塗液。 25 parts by mass of dipentaerythritol triacrylate, 25 parts by mass of neopentaerythritol tetraacrylate, 50 parts by mass of urethane acrylate, and 5 parts by mass of IRGACURE184 (manufactured by BASF (Photopolymerization) The initiator)) was dissolved in 118 parts by mass of methyl ethyl ketone to prepare a hard coating layer to form a coating solution.
使用3質量份之胺基甲酸酯丙烯酸酯、18質量份之氧化鋯微粒分散液(固體成分25%、溶劑：甲基異丁基酮)、0.1質量份之IRGACURE184(BASF公司製(光聚合起始劑))，以79重量份之甲基異丁基酮予以稀釋來調製高折射率層形成用塗液。 3 parts by mass of urethane acrylate, 18 parts by mass of zirconia fine particle dispersion (25% solids, solvent: methyl isobutyl ketone), and 0.1 part by mass of IRGACURE184 (manufactured by BASF (photopolymerization) The initiator)) was diluted with 79 parts by weight of methyl isobutyl ketone to prepare a coating solution for forming a high refractive index layer.
將18質量份之多孔質二氧化矽微粒分散液(固體成分20%、溶劑：甲基異丁基酮)、1.99質量份之EO改質二新戊四醇六丙烯酸酯(商品名：DPEA-12，日本化藥製)、0.07質量份之光聚合起始劑(BASF公司製，商品名：IRGACURE184)、0.20質量份之TSF4460(商品名， Momentive Performance Materials(股)製：烷基聚醚改質矽酮油)，以80重量份之作為溶劑的甲基異丁基酮予以稀釋來調製低折射率層形成用塗液。 18 parts by mass of a porous silica particle dispersion (20% solids, solvent: methyl isobutyl ketone) and 1.99 parts by mass of EO modified dipentaerythritol hexaacrylate (trade name: DPEA- 12, manufactured by Nippon Kayaku), 0.07 parts by mass of a photopolymerization initiator (manufactured by BASF, trade name: IRGACURE184), and 0.20 parts by mass of TSF4460 (trade name, Momentive Performance Materials (stock): Alkyl polyether modified silicone oil) was diluted with 80 parts by weight of methyl isobutyl ketone as a solvent to prepare a coating solution for forming a low refractive index layer.
在三乙醯基纖維素薄膜(FUJIFILM製：膜厚60μm)的單面塗布硬塗層形成用塗液，於80℃以烘箱乾燥60秒，乾燥後，利用紫外線照射裝置(Fusion UV Systems,Japan，光源H Bulb)以照射線量300mJ/m2進行紫外線照射，由此形成乾燥膜厚5μm的透明硬塗層。硬塗層之折射率為1.52。 A coating liquid for forming a hard coat layer was coated on one side of a triethylfluorinated cellulose film (manufactured by FUJIFILM: film thickness 60 μm), and dried in an oven at 80 ° C. for 60 seconds. After drying, an ultraviolet irradiation device (Fusion UV Systems, Japan) was used. The light source H Bulb) was irradiated with ultraviolet rays at an irradiation dose of 300 mJ / m 2 to form a transparent hard coat layer with a dry film thickness of 5 μm. The refractive index of the hard coating is 1.52.
在依上述方法形成的硬塗層上塗布高折射率層形成用塗液，使乾燥後之膜厚成為250nm。對其利用紫外線照射裝置(Fusion UV Systems,Japan，光源H Bulb)以照射線量192mJ/m2進行紫外線照射使其硬化而形成高折射率層。高折射率層之折射率為1.60。 A coating solution for forming a high refractive index layer was applied on the hard coat layer formed in the above-mentioned manner so that the film thickness after drying was 250 nm. This was irradiated with an ultraviolet ray of 192 mJ / m 2 using an ultraviolet irradiation device (Fusion UV Systems, Japan, light source H Bulb) to harden it to form a high refractive index layer. The refractive index of the high refractive index layer is 1.60.
在依上述方法形成的高折射率層上塗布低折射率層形成用塗液，使乾燥後之膜厚成為120nm。對其利用紫外線照射裝置(Fusion UV Systems,Japan，光源H Bulb)以照射線量192mJ/m2進行紫外線照射使其硬化而形成低折射率層，來製作抗反射薄膜。低折射率層之折射率為1.30。 A coating liquid for forming a low-refractive-index layer was applied on the high-refractive-index layer formed by the above method, so that the film thickness after drying was 120 nm. An ultraviolet ray irradiation device (Fusion UV Systems, Japan, light source H Bulb) was used to irradiate the ultraviolet rays at 192 mJ / m 2 and harden to form a low refractive index layer, thereby forming an antireflection film. The refractive index of the low refractive index layer is 1.30.
以調製例2之3質量份之胺基甲酸酯丙烯酸酯、18質量份之氧化鋯微粒分散液(固體成分20%、溶劑：甲基異丁基酮)、0.1質量份之IRGACURE184(BASF公司製(光聚合起始劑))、79重量份之甲基異丁基酮為基準，主要改變甲基異丁基酮的量來製作比較例2至比較例3之抗反射薄膜，又，主要改變胺基甲酸酯丙烯酸酯與氧化鋯微粒分散液的量來製作比較例4至比較例5之抗反射薄膜。 In Example 2, 3 parts by mass of urethane acrylate, 18 parts by mass of zirconia fine particle dispersion (solid content 20%, solvent: methyl isobutyl ketone), and 0.1 part by mass of IRGACURE184 (BASF Corporation) (Photopolymerization initiator)), 79 parts by weight of methyl isobutyl ketone as a reference, the amount of methyl isobutyl ketone was mainly changed to produce the antireflection films of Comparative Examples 2 to 3, and The antireflection films of Comparative Examples 4 to 5 were produced by changing the amounts of the urethane acrylate and the zirconia microparticle dispersion.
以調製例3之18質量份之多孔質二氧化矽微粒分散液(固體成分20%、溶劑：甲基異丁基酮)、1.99質量份之EO改質二新戊四醇六丙烯酸酯(商品名：DPEA-12，日本化藥製)、0.07質量份之聚合起始劑(BASF公司製，商品名：IRGACURE184)、0.20質量份之TSF4460(商品名，Momentive Performance Materials(股)製：烷基聚醚改質矽酮油)、80重量份之甲基異丁基酮為基準，主要改變甲基異丁基酮的量來製作比較例6至比較例7之抗反射薄膜。 In Example 3, 18 parts by mass of a porous silica particle dispersion (20% solids, solvent: methyl isobutyl ketone) and 1.99 parts by mass of EO modified dipentaerythritol hexaacrylate (commodity Name: DPEA-12, manufactured by Nippon Kayaku), 0.07 parts by mass of a polymerization initiator (manufactured by BASF, trade name: IRGACURE184), 0.20 parts by mass of TSF4460 (trade name, manufactured by Momentive Performance Materials (stock): alkyl Polyether modified silicone oil) and 80 parts by weight of methyl isobutyl ketone were used as the basis, and the amounts of methyl isobutyl ketone were mainly changed to produce antireflective films of Comparative Examples 6 to 7.
以下就比較例1至7之更具體的內容加以說明。 More specific contents of Comparative Examples 1 to 7 will be described below.
此為未將形成例2所示之高折射率層塗布於硬塗層上，取而代之將低折射率層塗布於硬塗層上之實例。 This is an example in which the high refractive index layer shown in Formation Example 2 is not coated on the hard coat layer, and the low refractive index layer is instead coated on the hard coat layer.
此為塗布成形成例2之高折射率層之乾燥後的膜厚成為290nm之實例。此處係取作為溶劑之甲基異丁基酮74重量份來調製高折射率層形成用塗液。 This is an example in which the thickness after drying of the high-refractive-index layer coated in Formation Example 2 was 290 nm. Here, 74 parts by weight of methyl isobutyl ketone as a solvent was used to prepare a coating solution for forming a high refractive index layer.
此為塗布成形成例2之高折射率層之乾燥後的膜厚成為190nm之實例。此處係取作為溶劑之甲基異丁基酮84重量份來調製高折射率層形成用塗液。 This is an example in which the thickness after drying of the high-refractive-index layer coated in Formation Example 2 was 190 nm. Here, 84 parts by weight of methyl isobutyl ketone as a solvent was used to prepare a coating liquid for forming a high refractive index layer.
此為取形成例2之高折射率層之胺基甲酸酯丙烯酸酯1.5重量份、氧化鋯微粒分散液24重量份，塗布成乾燥後之形成膜的折射率成為1.66之實例。 This is an example in which 1.5 parts by weight of urethane acrylate and 24 parts by weight of zirconia fine particle dispersion of the high refractive index layer of Formation Example 2 are applied, and the refractive index of the formed film after coating is 1.66.
此為取形成例2之高折射率層之胺基甲酸酯丙烯酸酯6重量份、氧化鋯微粒分散液6重量份，塗布成乾燥後之形成膜的折射率成為1.56之實例。 This is an example in which 6 parts by weight of urethane acrylate and 6 parts by weight of zirconia fine particle dispersion of the high refractive index layer of Formation Example 2 are applied, and the refractive index of the formed film after coating is 1.56.
此為塗布成形成例3之低折射率層之乾燥後的膜厚成為140nm之實例。此處係取作為溶劑之甲基異丁基酮75重量份來調製低折射率層形成用塗液。 This is an example in which the thickness after drying of the low-refractive-index layer coated in Formation Example 3 was 140 nm. Here, 75 parts by weight of methyl isobutyl ketone as a solvent was used to prepare a coating solution for forming a low refractive index layer.
此為塗布成形成例3之低折射率層之乾燥後的膜厚成為110nm之實例。此處係取作為溶劑之甲基異丁基酮85重量份來調製低折射率層形成用塗液。 This is an example in which the film thickness after drying of the low-refractive-index layer coated in Formation Example 3 was 110 nm. Here, 85 parts by weight of methyl isobutyl ketone as a solvent was used to prepare a coating solution for forming a low refractive index layer.
上述比較例之調製方法，就其未特別說明者，茲以實施例1中之操作為基準。 Regarding the modulation method of the above comparative example, the operation in the first embodiment is used as a reference, unless it is specifically described.
就實施例1、及比較例1至比較例7所得之抗反射薄膜，依以下方法進行評定。 The antireflection films obtained in Example 1 and Comparative Examples 1 to 7 were evaluated by the following methods.
對所得抗反射薄膜的低折射率層表面，利用自動分光光度計(日立製作所製U-4100)測定入射角5°之分光反射率。再者，由所得分光反射率曲線，基於JIS R3106求取視覺平均反射率。此外，於測定之際係在作為透明支持體之三乙醯基纖維素薄膜當中未形成低折射率層的面塗布消光黑色塗料，來施行抗反射處理。 The surface of the low-refractive-index layer of the obtained antireflection film was measured with an automatic spectrophotometer (U-4100, manufactured by Hitachi, Ltd.) for a spectral reflectance at an incident angle of 5 °. The visual average reflectance was calculated from the scored light reflectance curve based on JIS R3106. In addition, at the time of the measurement, an anti-reflective treatment was performed by applying a matte black paint to the surface of the triethylfluorene-based cellulose film that is a transparent support without forming a low refractive index layer.
對所得抗反射薄膜的低折射率層表面，利用自動分光光度計(日立製作所製U-4100)測定入射角5°之分光反射率，再由所得分光反射率曲線求取反射光之色相。此外，於測定之際係在作為透明支持體之三乙醯基纖維素薄膜當中未形成低折射率層的面塗布消光黑色塗料，來施行抗反射處理。 On the surface of the low refractive index layer of the obtained antireflection film, an automatic spectrophotometer (U-4100 manufactured by Hitachi, Ltd.) was used to measure the spectral reflectance at an incident angle of 5 °, and the hue of the reflected light was obtained from the scored light reflectance curve. In addition, at the time of the measurement, an anti-reflective treatment was performed by applying a matte black paint to the surface of the triethylfluorene-based cellulose film that is a transparent support without forming a low refractive index layer.
對所得抗反射薄膜的低折射率層表面，利用自動分光光度計(日立製作所製U-4100)，在入射角與反射角相同的條件下測定入射角5°至50°(5°、10°、20°、30°、40°及50°)之分光反射率，再由所得分光反射率曲線求取反射光之色相。此外，於測定之際係在作為透明支持體之三乙醯基纖維素薄膜當中未形成低折射率層的面塗布消光黑色塗料，來施行抗反射處理。 The surface of the low-refractive-index layer of the obtained antireflection film was measured with an automatic spectrophotometer (U-4100, manufactured by Hitachi, Ltd.) under the same conditions as the angle of incidence and the angle of reflection of 5 ° to 50 ° (5 °, 10 °). , 20 °, 30 °, 40 °, and 50 °), and then calculate the hue of the reflected light from the scored light reflectance curve. In addition, at the time of the measurement, an anti-reflective treatment was performed by applying a matte black paint to the surface of the triethylfluorene-based cellulose film that is a transparent support without forming a low refractive index layer.
評定結果係示於表1、第2圖。此外，第2圖中，箭號的端點為入射角5°至50°之範圍的端點所對應之色相的結果，亦即，箭號的起點為入射角5°的結果、箭號的終點為入射角50°的結果。 The evaluation results are shown in Tables 1 and 2. In addition, in Figure 2, the end point of the arrow is the result of the hue corresponding to the end point in the range of the incident angle of 5 ° to 50 °, that is, the start point of the arrow is the result of the 5 ° incident angle. The end point is the result of an angle of incidence of 50 °.
由表1之結果，實施例1顯示良好的性能。又就實施例1，由第2圖之結果，對於反射光之色相的角度相關性亦顯示良好的性能。另，第2圖中，以符號21表示之範圍係指屬不使抗反射薄膜之反射光帶有色澤之中和色的色相範圍。又，就比較例4而言，由於未形成均勻的膜，而無法測定。上述之實施例中，抗反射薄膜可使於抗反射薄膜表面之視覺平均反射率為0.05%以上1.0%以下之範圍內，可降低來自正面的反射光之色相，同時對於由各種角度入射的外來光之反射光亦可降低其色相。 From the results in Table 1, Example 1 showed good performance. Regarding Example 1, the results of FIG. 2 also show good performance with respect to the angle dependence of the hue of the reflected light. In FIG. 2, the range indicated by symbol 21 refers to a hue range in which the reflected light of the antireflection film does not have a neutral color. In Comparative Example 4, measurement was impossible because a uniform film was not formed. In the above-mentioned embodiment, the anti-reflection film can make the average visual reflectance of the surface of the anti-reflection film in a range of 0.05% to 1.0%, which can reduce the hue of the reflected light from the front side, and at the same time, the external light incident from various angles Reflected light can also reduce its hue.
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| JP6561519B2 (en) * | 2015-03-20 | 2019-08-21 | 大日本印刷株式会社 | Antireflection film, display device using the antireflection film, and method for selecting antireflection film |
| JP6561520B2 (en) * | 2015-03-20 | 2019-08-21 | 大日本印刷株式会社 | Antireflection film, display device using the antireflection film, and method for selecting antireflection film |
| KR101956830B1 (en) | 2015-08-18 | 2019-03-12 | 주식회사 엘지화학 | Low refractive layer and anti-reflective film comprising the same |
| KR101807208B1 (en) | 2015-08-18 | 2017-12-08 | 주식회사 엘지화학 | Low refractive layer and anti-reflective film comprising the same |
| JP2018072807A (en) * | 2016-10-20 | 2018-05-10 | 日油株式会社 | Glare and reflection preventing film and image display device having the same |
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| JP7100225B2 (en) * | 2017-08-02 | 2022-07-13 | 日東電工株式会社 | Anti-reflective film |
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| JP7515118B2 (en) * | 2019-04-23 | 2024-07-12 | パナソニックＩｐマネジメント株式会社 | Optical film laminate |
| JP7433779B2 (en) * | 2019-05-21 | 2024-02-20 | 日本ペイント・オートモーティブコーティングス株式会社 | Coated member and method for manufacturing coated member |
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