TW202216426A - Optical film with antifouling layer - Google Patents

Optical film with antifouling layer Download PDF

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TW202216426A
TW202216426A TW110125727A TW110125727A TW202216426A TW 202216426 A TW202216426 A TW 202216426A TW 110125727 A TW110125727 A TW 110125727A TW 110125727 A TW110125727 A TW 110125727A TW 202216426 A TW202216426 A TW 202216426A
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layer
antifouling layer
antifouling
film
optical film
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TWI811735B (en
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宮本幸大
梨木智剛
角田豊
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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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • 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
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/083—Oxides of refractory metals or yttrium
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/10—Glass or silica
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/12—Organic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
    • C23C14/562—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks for coating elongated substrates
    • 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
    • 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

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Abstract

An optical film (F) with an antifouling layer according to the present invention comprises a transparent substrate (10) and an antifouling layer (30) in order in the thickness direction (T). The ratio of F to Si detected by elemental analysis according to X-ray photoelectron spectroscopy on the side of a surface (31) of the antifouling layer (30) opposite to the transparent substrate (10) is 20 or more at an analysis depth of 1 nm.

Description

附防污層之光學膜Optical film with antifouling layer

本發明係關於一種附防污層之光學膜。The present invention relates to an optical film with an antifouling layer.

為了實現防污性，於觸控面板顯示器等顯示器之圖像顯示側之外表面，例如貼合有附防污層之光學膜。附防污層之光學膜具備透明基材、及配置於該透明基材之一面側之最外表面之防污層。藉由防污層，抑制手部油脂等污染物質附著於顯示器表面，又，使附著之污染物質容易被去除。例如下述專利文獻1中記載有與此種附防污層之光學膜相關之技術。 [先前技術文獻] [專利文獻] In order to achieve antifouling properties, for example, an optical film with an antifouling layer is attached to the outer surface on the image display side of a display such as a touch panel display. The optical film with an antifouling layer includes a transparent substrate and an antifouling layer disposed on the outermost surface of one surface side of the transparent substrate. The antifouling layer prevents contaminants such as hand grease from adhering to the display surface, and makes it easy to remove the adhering contaminants. For example, Patent Document 1 below discloses a technique related to such an antifouling layer-attached optical film. [Prior Art Literature] [Patent Literature]

[專利文獻1]日本專利特開2020-52221號公報[Patent Document 1] Japanese Patent Laid-Open No. 2020-52221

[發明所欲解決之問題][Problems to be Solved by Invention]

使用附防污層之光學膜時，例如藉由擦拭作業去除附著於防污層之污染物質。然而，對防污層反覆進行擦拭作業會導致防污層之防污性下降。為了維持附防污層之光學膜之防污功能，不希望出現防污層之防污性下降。When an optical film with an antifouling layer is used, the contaminants attached to the antifouling layer are removed, for example, by wiping. However, the repeated wiping operation of the antifouling layer causes the antifouling property of the antifouling layer to decrease. In order to maintain the antifouling function of the antifouling layer-attached optical film, it is not desirable to reduce the antifouling property of the antifouling layer.

本發明提供一種適於抑制防污層之防污性下降的附防污層之光學膜。 [解決問題之技術手段] The present invention provides an antifouling layer-attached optical film suitable for suppressing the deterioration of the antifouling property of the antifouling layer. [Technical means to solve problems]

本發明[1]包含一種附防污層之光學膜，其於厚度方向上依序具備透明基材及防污層，藉由利用X射線光電子分光法進行之元素分析，檢測上述防污層之與上述透明基材相反之表面側的F相對於Si之比率，於分析深度為1 nm時該比率為20以上。The present invention [1] includes an antifouling layer-attached optical film, which includes a transparent substrate and an antifouling layer in this order in the thickness direction, and detects the presence of the antifouling layer by elemental analysis using X-ray photoelectron spectroscopy. The ratio of F to Si on the surface side opposite to the above-mentioned transparent substrate is 20 or more when the analysis depth is 1 nm.

本發明[2]包含如上述[1]所記載之附防污層之光學膜，其中上述防污層之上述比率自分析深度1 nm至分析深度5 nm單調遞減。The present invention [2] includes the antifouling layer-attached optical film according to the above [1], wherein the ratio of the antifouling layer monotonically decreases from an analysis depth of 1 nm to an analysis depth of 5 nm.

本發明[3]包含如上述[1]或[2]所記載之附防污層之光學膜，其中上述防污層含有具有全氟聚醚基之烷氧基矽烷化合物。The present invention [3] includes the antifouling layer-attached optical film according to the above [1] or [2], wherein the antifouling layer contains an alkoxysilane compound having a perfluoropolyether group.

本發明[4]包含如上述[1]至[3]中任一項所記載之附防污層之光學膜，其中上述防污層為乾式塗佈膜。The present invention [4] includes the optical film with an antifouling layer according to any one of the above [1] to [3], wherein the antifouling layer is a dry coating film.

本發明[5]包含如上述[1]至[4]中任一項所記載之附防污層之光學膜，其於上述透明基材與上述防污層之間具備無機氧化物基底層，於該無機氧化物基底層上配置有上述防污層。The present invention [5] includes the optical film with an antifouling layer according to any one of the above [1] to [4], which comprises an inorganic oxide base layer between the transparent substrate and the antifouling layer, The said antifouling layer is arrange|positioned on this inorganic oxide base layer.

本發明[6]包含如上述[5]所記載之附防污層之光學膜，其中上述無機氧化物基底層包含二氧化矽。The present invention [6] includes the antifouling layer-attached optical film according to the above [5], wherein the inorganic oxide base layer contains silicon dioxide.

本發明[7]包含如上述[5]或[6]所記載之附防污層之光學膜，其上述無機氧化物基底層之上述防污層側之表面具有0.5 nm以上10 nm以下之表面粗糙度Ra。 [發明之效果] The present invention [7] includes the antifouling layer-attached optical film according to the above [5] or [6], wherein the surface of the inorganic oxide base layer on the antifouling layer side has a surface of 0.5 nm to 10 nm. Roughness Ra. [Effect of invention]

如上所述，對於本發明之附防污層之光學膜，藉由利用X射線光電子分光法進行之元素分析，檢測防污層之與透明基材相反之表面側的F相對於Si之比率，於分析深度為1 nm時該比率為20以上。因此，本附防污層之光學膜適於抑制防污層之防污性下降。As described above, in the optical film with the antifouling layer of the present invention, the ratio of F to Si on the surface side of the antifouling layer opposite to the transparent substrate is detected by elemental analysis by X-ray photoelectron spectroscopy, This ratio is 20 or more at an analysis depth of 1 nm. Therefore, the optical film with the antifouling layer of the present invention is suitable for suppressing the deterioration of the antifouling property of the antifouling layer.

如圖1所示，光學膜F作為本發明之附防污層之光學膜之一實施方式，朝向厚度方向T之一側依序具備透明基材10、光學功能層20及防污層30。於本實施方式中，光學膜F朝向厚度方向T之一側依序具備透明基材10、密接層41、光學功能層20及防污層30。又，光學膜F具有於與厚度方向T正交之方向(面方向)上擴展之形狀。As shown in FIG. 1 , as an embodiment of the optical film with an antifouling layer of the present invention, the optical film F includes a transparent substrate 10 , an optical functional layer 20 and an antifouling layer 30 in this order toward one side in the thickness direction T. As shown in FIG. In this embodiment, the optical film F is provided with the transparent base material 10, the adhesive layer 41, the optical function layer 20, and the antifouling layer 30 in this order toward one side of the thickness direction T. As shown in FIG. Moreover, the optical film F has the shape which spreads in the direction (plane direction) orthogonal to the thickness direction T.

於本實施方式中，透明基材10朝向厚度方向T之一側依序具備樹脂膜11及硬塗層12。In this embodiment, the transparent base material 10 is provided with the resin film 11 and the hard-coat layer 12 in this order toward one side of the thickness direction T. As shown in FIG.

樹脂膜11係具有可撓性之透明樹脂膜。作為樹脂膜11之材料，例如可例舉聚酯樹脂、聚烯烴樹脂、聚苯乙烯樹脂、丙烯酸樹脂、聚碳酸酯樹脂、聚醚碸樹脂、聚碸樹脂、聚醯胺樹脂、聚醯亞胺樹脂、纖維素樹脂、降莰烯樹脂、聚芳酯樹脂及聚乙烯醇樹脂。作為聚酯樹脂，例如可例舉聚對苯二甲酸乙二酯(PET)、聚對苯二甲酸丁二酯、及聚萘二甲酸乙二酯。作為聚烯烴樹脂，例如可例舉聚乙烯、聚丙烯及環烯烴聚合物(COP)。作為纖維素樹脂，例如可例舉三乙醯纖維素(TAC)。該等材料可單獨使用，亦可併用兩種以上。作為樹脂膜11之材料，就透明性及強度之觀點而言，可使用選自由聚酯樹脂、聚烯烴樹脂、及纖維素樹脂所組成之群中之一種，更佳為使用選自由PET、COP、及TAC所組成之群中之一種。The resin film 11 is a flexible transparent resin film. As the material of the resin film 11, for example, polyester resin, polyolefin resin, polystyrene resin, acrylic resin, polycarbonate resin, polyether resin, polyamide resin, polyamide resin, polyimide can be mentioned. Resin, cellulose resin, norbornene resin, polyarylate resin and polyvinyl alcohol resin. As polyester resin, polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate are mentioned, for example. As a polyolefin resin, polyethylene, a polypropylene, and a cycloolefin polymer (COP) are mentioned, for example. As a cellulose resin, triacetyl cellulose (TAC) is mentioned, for example. These materials may be used alone or in combination of two or more. As the material of the resin film 11, from the viewpoint of transparency and strength, one selected from the group consisting of polyester resin, polyolefin resin, and cellulose resin can be used, and it is more preferable to use one selected from PET, COP , and one of the groups formed by TAC.

亦可對樹脂膜11之硬塗層12側之表面進行表面改質處理。作為表面改質處理，例如可例舉電暈處理、電漿處理、臭氧處理、底塗處理、輝光處理、及偶合劑處理。Surface modification treatment may also be performed on the surface of the resin film 11 on the hard coat layer 12 side. As the surface modification treatment, for example, corona treatment, plasma treatment, ozone treatment, primer treatment, glow treatment, and coupling agent treatment may be mentioned.

就強度之觀點而言，樹脂膜11之厚度較佳為5 μm以上，更佳為10 μm以上，進而較佳為20 μm以上。就操作性之觀點而言，樹脂膜11之厚度較佳為300 μm以下，更佳為200 μm以下。From the viewpoint of strength, the thickness of the resin film 11 is preferably 5 μm or more, more preferably 10 μm or more, and still more preferably 20 μm or more. From the viewpoint of workability, the thickness of the resin film 11 is preferably 300 μm or less, more preferably 200 μm or less.

樹脂膜11之全光線透過率(JIS K 7375-2008)較佳為80%以上，更佳為90%以上，進而較佳為95%以上。於觸控面板顯示器等之顯示器之表面具備光學膜F情形時，此種構成適於確保對該光學膜F要求之透明性。樹脂膜11之全光線透過率例如為100%以下。The total light transmittance (JIS K 7375-2008) of the resin film 11 is preferably 80% or more, more preferably 90% or more, and still more preferably 95% or more. When the optical film F is provided on the surface of a display such as a touch panel display, such a configuration is suitable for ensuring the transparency required for the optical film F. The total light transmittance of the resin film 11 is, for example, 100% or less.

硬塗層12配置於樹脂膜11之厚度方向T之一面上。硬塗層12係用以使光學膜F之露出表面(圖1中為上表面)不易形成擦傷之層。The hard coat layer 12 is arranged on one surface in the thickness direction T of the resin film 11 . The hard coat layer 12 is used to make the exposed surface (the upper surface in FIG. 1 ) of the optical film F difficult to form scratches.

硬塗層12係硬化性樹脂組合物之硬化物。作為硬化性樹脂組合物所含有之硬化性樹脂，例如可例舉聚酯樹脂、丙烯酸樹脂、胺基甲酸酯樹脂、胺基甲酸酯丙烯酸酯樹脂、醯胺樹脂、聚矽氧樹脂、環氧樹脂、及三聚氰胺樹脂。該等硬化性樹脂可單獨使用，亦可併用兩種以上。就確保硬塗層12之高硬度之觀點而言，作為硬化性樹脂，較佳為使用胺基甲酸酯丙烯酸酯樹脂。The hard coat layer 12 is a cured product of the curable resin composition. Examples of the curable resin contained in the curable resin composition include polyester resins, acrylic resins, urethane resins, urethane acrylate resins, amide resins, polysiloxane resins, cyclic resins Oxygen resin, and melamine resin. These curable resins may be used alone or in combination of two or more. From the viewpoint of securing high hardness of the hard coat layer 12, it is preferable to use a urethane acrylate resin as the curable resin.

又，作為硬化性樹脂組合物，例如可例舉紫外線硬化型樹脂組合物、及熱硬化型樹脂組合物。作為硬化性樹脂組合物，較佳為使用紫外線硬化型樹脂組合物，因其無須進行高溫加熱便可硬化，故而有助於提昇光學膜F之製造效率。紫外線硬化型樹脂組合物包括選自由紫外線硬化型單體、紫外線硬化型低聚物、及紫外線硬化型聚合物所組成之群中之至少一種。作為紫外線硬化型樹脂組合物之具體例，可例舉日本專利特開2016-179686號公報所記載之硬塗層形成用組合物。Moreover, as a curable resin composition, an ultraviolet curable resin composition and a thermosetting resin composition are mentioned, for example. As a curable resin composition, it is preferable to use an ultraviolet curable resin composition, and since it can harden|cure without high temperature heating, it contributes to the improvement of the manufacturing efficiency of the optical film F. The UV-curable resin composition includes at least one selected from the group consisting of UV-curable monomers, UV-curable oligomers, and UV-curable polymers. As a specific example of an ultraviolet curable resin composition, the composition for hard-coat layer formation described in Unexamined-Japanese-Patent No. 2016-179686 is mentioned.

硬化性樹脂組合物亦可含有微粒子。於硬化性樹脂組合物中調配微粒子，有助於調整硬塗層12之硬度、表面粗糙度、折射率，以及對硬塗層12賦予防眩性。作為微粒子，例如可例舉金屬氧化物粒子、玻璃粒子及有機粒子。作為金屬氧化物粒子之材料，例如可例舉氧化矽、氧化鋁、氧化鈦、氧化鋯、氧化鈣、氧化錫、氧化銦、氧化鎘、及氧化銻。作為有機粒子之材料，例如可例舉聚甲基丙烯酸甲酯、聚苯乙烯、聚胺基甲酸酯、丙烯酸系樹脂-苯乙烯共聚物、苯并胍胺、三聚氰胺、及聚碳酸酯。The curable resin composition may contain fine particles. The preparation of fine particles in the curable resin composition helps to adjust the hardness, surface roughness, and refractive index of the hard coat layer 12 , and to impart anti-glare properties to the hard coat layer 12 . As the fine particles, for example, metal oxide particles, glass particles, and organic particles may be mentioned. As the material of the metal oxide particles, for example, silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, calcium oxide, tin oxide, indium oxide, cadmium oxide, and antimony oxide can be mentioned. As a material of an organic particle, polymethyl methacrylate, polystyrene, polyurethane, acrylic resin-styrene copolymer, benzoguanamine, melamine, and polycarbonate are mentioned, for example.

為了確保硬塗層12之硬度從而以此確保防污層30表面之硬度，硬塗層12之厚度較佳為1 μm以上，更佳為3 μm以上，進而較佳為5 μm以上。就光學膜F之柔軟性確保之觀點而言，硬塗層12之厚度較佳為50 μm以下，更佳為40 μm以下，進而較佳為35 μm以下，尤其較佳為30 μm以下。In order to ensure the hardness of the hard coat layer 12 and thus the hardness of the surface of the antifouling layer 30, the thickness of the hard coat layer 12 is preferably 1 μm or more, more preferably 3 μm or more, and more preferably 5 μm or more. From the viewpoint of securing the flexibility of the optical film F, the thickness of the hard coat layer 12 is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 35 μm or less, and particularly preferably 30 μm or less.

亦可對硬塗層12之密接層41側之表面進行表面改質處理。作為表面改質處理，例如可例舉電漿處理、電暈處理、臭氧處理、底塗處理、輝光處理及偶合劑處理。要確保硬塗層12與密接層41之間之高密接力，較佳為對硬塗層12之密接層41側表面進行電漿處理。Surface modification treatment may also be performed on the surface on the side of the adhesive layer 41 of the hard coat layer 12 . As the surface modification treatment, for example, plasma treatment, corona treatment, ozone treatment, primer treatment, glow treatment, and coupling agent treatment may be mentioned. To ensure high adhesion between the hard coat layer 12 and the adhesive layer 41 , it is preferable to perform plasma treatment on the side surface of the adhesive layer 41 of the hard coat layer 12 .

就強度之觀點而言，透明基材10之厚度較佳為5 μm以上，更佳為10 μm以上，進而較佳為20 μm以上。就操作性之觀點而言，透明基材10之厚度較佳為300 μm以下，更佳為200 μm以下。From the viewpoint of strength, the thickness of the transparent substrate 10 is preferably 5 μm or more, more preferably 10 μm or more, and still more preferably 20 μm or more. From the viewpoint of workability, the thickness of the transparent substrate 10 is preferably 300 μm or less, and more preferably 200 μm or less.

透明基材10之全光線透過率(JIS K 7375-2008)較佳為80%以上，更佳為90%以上，進而較佳為95%以上。於觸控面板顯示器等顯示器之表面具備光學膜F之情形時，此種構成適於確保對該光學膜F所要求之透明性。透明基材10之全光線透過率例如為100%以下。The total light transmittance (JIS K 7375-2008) of the transparent substrate 10 is preferably 80% or more, more preferably 90% or more, and still more preferably 95% or more. When the optical film F is provided on the surface of a display such as a touch panel display, such a configuration is suitable for ensuring the transparency required for the optical film F. The total light transmittance of the transparent substrate 10 is, for example, 100% or less.

密接層41係用以確保無機氧化物層(於本實施方式中為後述第1高折射率層21)相對於透明基材10(於本實施方式中為硬塗層12)之密接力之層。密接層41配置於硬塗層12之厚度方向T之一面上。作為密接層41之材料，例如可例舉矽、銦、鎳、鉻、鋁、錫、金、銀、鉑、鋅、鈦、鎢、鋯、鈀等金屬、該等金屬之2種以上之合金及該等金屬之氧化物。為了兼具對於有機層(具體而言為硬塗層12)及無機氧化物層(於本實施方式中為具體而言第1高折射率層21)雙方之密接性、以及密接層41之透明性，作為密接層41之材料，較佳為使用銦錫氧化物(ITO)或氧化矽(SiOx)。於使用氧化矽作為密接層41之材料之情形時，較佳為使用氧量少於化學計量組成之SiOx，更佳為使用x為1.2以上1.9以下之SiOx。The adhesion layer 41 is a layer for ensuring the adhesion of the inorganic oxide layer (in this embodiment, the first high refractive index layer 21 described later) to the transparent substrate 10 (in this embodiment, the hard coat layer 12 ). . The adhesion layer 41 is arranged on one surface in the thickness direction T of the hard coat layer 12 . Examples of the material of the adhesion layer 41 include metals such as silicon, indium, nickel, chromium, aluminum, tin, gold, silver, platinum, zinc, titanium, tungsten, zirconium, and palladium, and alloys of two or more of these metals. and oxides of these metals. In order to have both adhesiveness with respect to both the organic layer (specifically, the hard coat layer 12 ) and the inorganic oxide layer (specifically, the first high refractive index layer 21 in this embodiment), and the transparency of the adhesive layer 41 As the material of the adhesion layer 41, indium tin oxide (ITO) or silicon oxide (SiOx) is preferably used. When silicon oxide is used as the material of the adhesion layer 41, it is preferable to use SiOx whose oxygen content is less than the stoichiometric composition, and it is more preferable to use SiOx whose x is 1.2 or more and 1.9 or less.

為了確保硬塗層12與無機氧化物層(於本實施方式中為第1高折射率層21)之間之密接力，同時實現密接層41之透明性，密接層41之厚度較佳為1 nm以上，又，較佳為10 nm以下。In order to ensure the adhesion between the hard coat layer 12 and the inorganic oxide layer (the first high refractive index layer 21 in this embodiment), and to achieve the transparency of the adhesion layer 41, the thickness of the adhesion layer 41 is preferably 1 nm or more, and preferably 10 nm or less.

光學功能層20配置於密接層41之厚度方向T之一面上。於本實施方式中，光學功能層20係用以抑制外界光之反射強度之抗反射層。即，光學膜F於本實施方式中為抗反射膜。The optical functional layer 20 is disposed on one surface in the thickness direction T of the adhesive layer 41 . In this embodiment, the optical functional layer 20 is an anti-reflection layer for suppressing the reflection intensity of external light. That is, the optical film F is an antireflection film in this embodiment.

光學功能層20(抗反射層)於厚度方向上交替具有折射率相對較大之高折射率層、及折射率相對較小之低折射率層。於抗反射層，藉由複數個薄層(高折射率層、低折射率層)之複數個界面產生之反射光間之干涉作用，使淨反射光強度衰減。又，於抗反射層，藉由調整各薄層之光學膜厚(折射率與厚度之積)，可表現出使反射光強度衰減之干涉作用。具體而言，作為此種抗反射層之光學功能層20朝向厚度方向T之一側依序具有第1高折射率層21、第1低折射率層22、第2高折射率層23及第2低折射率層24。The optical function layer 20 (anti-reflection layer) alternately has a high refractive index layer with a relatively large refractive index and a low refractive index layer with a relatively small refractive index in the thickness direction. In the anti-reflection layer, the net reflected light intensity is attenuated by the interference between the reflected light generated by the multiple interfaces of the multiple thin layers (high refractive index layer, low refractive index layer). In addition, in the antireflection layer, by adjusting the optical film thickness (the product of the refractive index and the thickness) of each thin layer, the interference effect of attenuating the reflected light intensity can be exhibited. Specifically, the optical functional layer 20 as such an anti-reflection layer has a first high refractive index layer 21 , a first low refractive index layer 22 , a second high refractive index layer 23 and a 2 low refractive index layer 24.

第1高折射率層21及第2高折射率層23分別包含波長550 nm下之折射率較佳為1.9以上之高折射率材料。要兼具高折射率與可見光之低吸收性，作為高折射率材料，例如可例舉氧化鈮(Nb 2O 5)、氧化鈦、氧化鋯、摻錫氧化銦(ITO)、及摻銻氧化錫(ATO)，較佳為使用氧化鈮。 The first high-refractive index layer 21 and the second high-refractive index layer 23 each contain a high-refractive-index material whose refractive index at a wavelength of 550 nm is preferably 1.9 or more. In order to have both high refractive index and low absorption of visible light, examples of high refractive index materials include niobium oxide (Nb 2 O 5 ), titanium oxide, zirconium oxide, tin-doped indium oxide (ITO), and antimony-doped oxide. Tin (ATO), preferably niobium oxide is used.

第1高折射率層21之光學膜厚(折射率與厚度之積)例如為20 nm以上，且例如為55 nm以下。第2高折射率層23之光學膜厚例如為60 nm以上，且例如為330 nm以下。The optical film thickness (the product of the refractive index and the thickness) of the first high refractive index layer 21 is, for example, 20 nm or more and, for example, 55 nm or less. The optical film thickness of the second high refractive index layer 23 is, for example, 60 nm or more and, for example, 330 nm or less.

第1低折射率層22及第2低折射率層24分別包含波長550 nm下之折射率較佳為1.6以下之低折射率材料。要兼具低折射率與可見光之低吸收性，作為低折射率材料，例如可例舉二氧化矽(SiO 2)及氟化鎂，較佳為使用二氧化矽。 The first low-refractive index layer 22 and the second low-refractive index layer 24 each contain a low-refractive-index material whose refractive index at a wavelength of 550 nm is preferably 1.6 or less. In order to have both low refractive index and low absorption of visible light, as the low refractive index material, for example, silicon dioxide (SiO 2 ) and magnesium fluoride can be exemplified, and silicon dioxide is preferably used.

第1低折射率層22之光學膜厚例如為15 nm以上，且例如為70 nm以下。第2低折射率層24之光學膜厚例如為100 nm以上，且例如為160 nm以下。The optical film thickness of the first low refractive index layer 22 is, for example, 15 nm or more and, for example, 70 nm or less. The optical film thickness of the second low refractive index layer 24 is, for example, 100 nm or more and, for example, 160 nm or less.

又，光學功能層20中，第1高折射率層21之厚度例如為1 nm以上，較佳為5 nm以上，且例如為30 nm以下，較佳為20 nm以下。第1低折射率層22之厚度例如為10 nm以上，較佳為20 nm以上，且例如為50 nm以下，較佳為30 nm以下。第2高折射率層23之厚度例如為50 nm以上，較佳為80 nm以上，且例如為200 nm以下，較佳為150 nm以下。第2低折射率層24之厚度例如為50 nm以上，較佳為60 nm以上，且例如為150 nm以下，較佳為100 nm以下。In the optical functional layer 20, the thickness of the first high refractive index layer 21 is, for example, 1 nm or more, preferably 5 nm or more, and, for example, 30 nm or less, preferably 20 nm or less. The thickness of the first low refractive index layer 22 is, for example, 10 nm or more, preferably 20 nm or more, and, for example, 50 nm or less, or preferably 30 nm or less. The thickness of the second high refractive index layer 23 is, for example, 50 nm or more, preferably 80 nm or more, and, for example, 200 nm or less, or preferably 150 nm or less. The thickness of the second low refractive index layer 24 is, for example, 50 nm or more, preferably 60 nm or more, and, for example, 150 nm or less, or preferably 100 nm or less.

於本實施方式中，第2低折射率層24兼作為確保防污層30之耐剝離性之無機氧化物基底層(無機氧化物基底層42)。作為此種第2低折射率層24之材料，就確保與防污層30之密接性之觀點而言，同樣例如可例舉二氧化矽及氟化鎂，較佳為使用二氧化矽。就確保防污層30之耐剝離性之觀點而言，第2低折射率層24之厚度較佳為50 nm以上，更佳為65 nm以上，進而較佳為80 nm以上，尤其較佳為90 nm以上。該厚度例如為150 nm以下。In the present embodiment, the second low-refractive index layer 24 also serves as an inorganic oxide base layer (inorganic oxide base layer 42 ) for ensuring peel resistance of the antifouling layer 30 . As such a material of the second low-refractive index layer 24, from the viewpoint of securing the adhesion with the antifouling layer 30, for example, silicon dioxide and magnesium fluoride can also be mentioned, and silicon dioxide is preferably used. From the viewpoint of ensuring the peeling resistance of the antifouling layer 30, the thickness of the second low refractive index layer 24 is preferably 50 nm or more, more preferably 65 nm or more, further preferably 80 nm or more, particularly preferably Above 90 nm. The thickness is, for example, 150 nm or less.

亦可對無機氧化物基底層42之防污層30側之表面進行表面改質處理。作為表面改質處理，例如可例舉電暈處理、電漿處理、臭氧處理、底塗處理、輝光處理、及偶合劑處理。Surface modification treatment may also be performed on the surface of the inorganic oxide base layer 42 on the antifouling layer 30 side. As the surface modification treatment, for example, corona treatment, plasma treatment, ozone treatment, primer treatment, glow treatment, and coupling agent treatment may be mentioned.

無機氧化物基底層42之防污層30側之表面之表面粗糙度Ra(算術平均表面粗糙度)較佳為0.5 nm以上，更佳為0.8 nm以上。該表面粗糙度Ra較佳為10 nm以下，更佳為8 nm以下。例如根據藉由AFM(原子力顯微鏡)所得之1 μm見方之觀察像求出表面粗糙度Ra。The surface roughness Ra (arithmetic mean surface roughness) of the surface on the antifouling layer 30 side of the inorganic oxide base layer 42 is preferably 0.5 nm or more, more preferably 0.8 nm or more. The surface roughness Ra is preferably 10 nm or less, more preferably 8 nm or less. Surface roughness Ra is calculated|required from the observation image of 1 micrometer square obtained by AFM (atomic force microscope), for example.

防污層30係具有防污功能之層。防污層30配置於無機氧化物基底層42之厚度方向T之一面上。防污層30於厚度方向T之一側具有表面31(外表面)。防污層30之防污功能包括抑制使用光學膜F時手部油脂等污染物質附著於膜露出面之功能、以及使附著之污染物質容易被去除之功能。The antifouling layer 30 is a layer having an antifouling function. The antifouling layer 30 is disposed on one surface in the thickness direction T of the inorganic oxide base layer 42 . The antifouling layer 30 has a surface 31 (outer surface) on one side in the thickness direction T. As shown in FIG. The antifouling function of the antifouling layer 30 includes a function of preventing contaminants such as hand grease from adhering to the exposed surface of the film when the optical film F is used, and a function of allowing the adhered contaminants to be easily removed.

作為防污層30之材料，例如可例舉有機氟化合物。作為有機氟化合物，較佳為可使用具有全氟聚醚基之烷氧基矽烷化合物。作為具有全氟聚醚基之烷氧基矽烷化合物，例如可例舉下述通式(1)所示之化合物。As a material of the antifouling layer 30, an organic fluorine compound is mentioned, for example. As the organic fluorine compound, an alkoxysilane compound having a perfluoropolyether group can be preferably used. As an alkoxysilane compound which has a perfluoropolyether group, the compound represented by following general formula (1) is mentioned, for example.

R 1-R 2-X-(CH 2) m-Si(OR 3) 3(1) R 1 -R 2 -X-(CH 2 ) m -Si(OR 3 ) 3 (1)

通式(1)中，R 1表示烷基中之一個以上之氫原子被氟原子取代之直鏈狀或支鏈狀之氟化烷基(碳數為例如1以上20以下)，較佳為表示烷基之所有氫原子被氟原子取代之全氟烷基。 In the general formula (1), R 1 represents a linear or branched fluorinated alkyl group in which one or more hydrogen atoms in the alkyl group are substituted with a fluorine atom (the number of carbon atoms is, for example, 1 to 20), preferably Represents a perfluoroalkyl group in which all hydrogen atoms of an alkyl group are replaced by fluorine atoms.

R 2表示至少包含一個全氟聚醚(PFPE)基之重複結構的結構，較佳為表示包含兩個PFPE基之重複結構的結構。作為PFPE基之重複結構，例如可例舉直鏈狀PFPE基之重複結構及支鏈狀PFPE基之重複結構。作為直鏈狀PFPE基之重複結構，例如可例舉-(OC nF 2n) p-所示之結構(n表示1以上20以下之整數，p表示1以上50以下之整數。下同)。作為支鏈狀PFPE基之重複結構，例如可例舉-(OC(CF 3) 2) p-所示之結構及-(OCF 2CF(CF 3)CF 2) p-所示之結構。作為PFPE基之重複結構，較佳為可例舉直鏈狀PFPE基之重複結構，更佳為可例舉-(OCF 2) p-及-(OC 2F 4) p-。 R 2 represents a structure containing at least one repeating structure of a perfluoropolyether (PFPE) group, preferably a structure containing a repeating structure containing two PFPE groups. As a repeating structure of a PFPE group, the repeating structure of a linear PFPE group and the repeating structure of a branched PFPE group are mentioned, for example. The repeating structure of the linear PFPE group may, for example, be the structure represented by -(OC n F 2n ) p - (n represents an integer of 1 or more and 20 or less, and p represents an integer of 1 or more and 50 or less. The same applies hereinafter). Examples of the repeating structure of the branched PFPE group include a structure represented by -(OC(CF 3 ) 2 ) p - and a structure represented by -(OCF 2 CF(CF 3 )CF 2 ) p -. As the repeating structure of the PFPE group, the repeating structure of the linear PFPE group is preferably exemplified, and -(OCF 2 ) p - and -(OC 2 F 4 ) p - are more preferred.

R 3表示碳數1以上4以下烷基，較佳為表示甲基。 R 3 represents an alkyl group having 1 to 4 carbon atoms, preferably a methyl group.

X表示醚基、羰基、胺基或醯胺基，較佳為表示醚基。X represents an ether group, a carbonyl group, an amino group or an amide group, preferably an ether group.

m表示1以上之整數。又，m表示較佳為20以下、更佳為10以下、進而較佳為5以下之整數。m represents an integer of 1 or more. Moreover, m represents an integer which is preferably 20 or less, more preferably 10 or less, and still more preferably 5 or less.

此種具有全氟聚醚基之烷氧基矽烷化合物中，較佳為使用下述通式(2)所示之化合物。Among the alkoxysilane compounds having such a perfluoropolyether group, those represented by the following general formula (2) are preferably used.

CF 3-(OCF 2) q-(OC 2F 4) r-O-(CH 2) 3-Si(OCH 3) 3(2) CF 3 -(OCF 2 ) q -(OC 2 F 4 ) r -O-(CH 2 ) 3 -Si(OCH 3 ) 3 (2)

通式(2)中，q表示1以上50以下之整數，r表示1以上50以下之整數。In the general formula (2), q represents an integer of 1 or more and 50 or less, and r represents an integer of 1 or more and 50 or less.

又，具有全氟聚醚基之烷氧基矽烷化合物可單獨使用，亦可併用兩種以上。Moreover, the alkoxysilane compound which has a perfluoropolyether group may be used individually, and may use 2 or more types together.

藉由利用X射線光電子分光法進行之元素分析，檢測防污層30之表面31(防污層30之與透明基材10為相反側之表面)F相對於Si之比率(F/Si，原子數比率)，於分析深度為1 nm時，該比率為20以上，較佳為22以上，更佳為24以上，進而較佳為26以上。防污層30之表面31存在之氟原子越多，則上述比率越高。於防污層30含有具有全氟聚醚基之烷氧基矽烷化合物之情形時，採取如下配向之該化合物之該配向性越高，則上述比率越高，又，採取此種配向之該化合物越多，則上述比率越高。上述配向係指如下配向：該化合物之長鏈結構之一端之氟化烷基(較佳為全氟烷基)位於表面31側，另一端之烷氧基矽烷結構部位於光學功能層20側，較佳為上述長鏈結構沿厚度方向T延伸。The ratio of F to Si (F/Si, atomic) on the surface 31 of the antifouling layer 30 (the surface on the opposite side to the transparent substrate 10 of the antifouling layer 30) was detected by elemental analysis using X-ray photoelectron spectroscopy When the analysis depth is 1 nm, the ratio is 20 or more, preferably 22 or more, more preferably 24 or more, and still more preferably 26 or more. The more fluorine atoms present on the surface 31 of the antifouling layer 30, the higher the above ratio. In the case where the antifouling layer 30 contains an alkoxysilane compound having a perfluoropolyether group, the higher the orientation of the compound in the following alignment, the higher the above ratio, and the compound in this alignment is The more, the higher the above ratio. The above-mentioned alignment refers to the following alignment: the fluorinated alkyl group (preferably perfluoroalkyl group) at one end of the long-chain structure of the compound is located on the side of the surface 31, and the alkoxysilane structure at the other end is located on the side of the optical functional layer 20, Preferably, the above-mentioned long-chain structure extends along the thickness direction T.

藉由利用X射線光電子分光法進行之元素分析，對防污層30之表面31，檢測F相對於Si之比率(F/Si)，較佳為於分析深度1 nm至分析深度5 nm，該比率單調遞減。於防污層30含有具有全氟聚醚基之烷氧基矽烷化合物之情形時，採取上述配向之該化合物之該配向性越高，則上述單調遞減之變化程度越大，又，採取上述配向之該化合物越多，則上述單調遞減之變化程度越大。The ratio of F to Si (F/Si) is detected on the surface 31 of the antifouling layer 30 by elemental analysis using X-ray photoelectron spectroscopy, preferably at an analysis depth of 1 nm to an analysis depth of 5 nm, the The ratio is monotonically decreasing. In the case where the antifouling layer 30 contains an alkoxysilane compound having a perfluoropolyether group, the higher the orientation of the compound in the above-mentioned alignment, the greater the degree of the above-mentioned monotonically decreasing change, and the above-mentioned alignment is adopted. The more of this compound, the greater the degree of the above monotonically decreasing change.

具體而言，對於實施例，藉由X射線光電子分光法進行之防污層30之元素分析係以後述方式實施。又，作為上述比率(F/Si)之調整方法，例如可例舉選擇上述有機氟化合物之種類、調整防污層30中有機氟化合物之含有比率、選擇防污層30之形成方法、選擇防污層30之基底層(於本實施方式中為第2低折射率層24)之材料、以及調整該基底層之防污層30側表面之表面粗糙度。作為上述比率(F/Si)之調整方法，亦可例舉是否選擇以輥對輥方式藉由連續之生產線(即，於兩步驟之間不捲取工作膜)來實施形成對防污層30而言之基底層(於本實施方式中為第2低折射率層24)之步驟與於基底層上形成防污層30之步驟。Specifically, in the examples, the elemental analysis of the antifouling layer 30 by X-ray photoelectron spectroscopy was carried out as described later. Further, as a method for adjusting the ratio (F/Si), for example, selection of the type of the organic fluorine compound described above, adjustment of the content ratio of the organic fluorine compound in the antifouling layer 30, selection of a method for forming the antifouling layer 30, selection of antifouling The material of the base layer of the contamination layer 30 (the second low refractive index layer 24 in this embodiment) and the surface roughness of the antifouling layer 30 side surface of the base layer are adjusted. As a method for adjusting the above ratio (F/Si), it can also be exemplified whether to choose to form the antifouling layer 30 by a continuous production line in a roll-to-roll manner (ie, without winding the working film between two steps). For example, the step of the base layer (the second low refractive index layer 24 in this embodiment) and the step of forming the antifouling layer 30 on the base layer.

於本實施方式中，防污層30係藉由乾式塗佈法形成之膜(乾式塗佈膜)。作為乾式塗佈法，可例舉濺鍍法、真空蒸鍍法及CVD。防污層30較佳為乾式塗佈膜，更佳為真空蒸鍍膜。In this embodiment, the antifouling layer 30 is a film (dry coating film) formed by a dry coating method. As a dry coating method, a sputtering method, a vacuum vapor deposition method, and CVD are mentioned. The antifouling layer 30 is preferably a dry coating film, more preferably a vacuum evaporation film.

防污層30之材料含有具有全氟聚醚基之烷氧基矽烷化合物，且防污層30為乾式塗佈膜(較佳為真空蒸鍍膜)，此種構成適於確保防污層30對光學功能層20之高接合力，因此，適於確保防污層30之耐剝離性。防污層30之耐剝離性較高，有助於維持防污層30之防污功能。The material of the antifouling layer 30 contains an alkoxysilane compound having a perfluoropolyether group, and the antifouling layer 30 is a dry coating film (preferably a vacuum evaporation film). The high bonding force of the optical functional layer 20 is therefore suitable for ensuring the peeling resistance of the antifouling layer 30 . The antifouling layer 30 has high peeling resistance, which helps to maintain the antifouling function of the antifouling layer 30 .

防污層30之外表面31之水接觸角(純水接觸角)為110°以上，較佳為111°以上，更佳為112°以上，進而較佳為113°以上，尤其較佳為114°以上。外表面31之水接觸角如此高之構成適於實現防污層30之高防污性。該水接觸角例如為130°以下。於防污層30之外表面31(露出表面)形成直徑2 mm以下之水滴(純水之液滴)，測定該水滴相對於防污層30表面之接觸角，藉此求出水接觸角。例如藉由調整防污層30之組成、外表面31之粗糙度、硬塗層12之組成、及硬塗層12之光學功能層20側之表面之粗糙度，可調整外表面31之水接觸角。The water contact angle (pure water contact angle) of the outer surface 31 of the antifouling layer 30 is 110° or more, preferably 111° or more, more preferably 112° or more, further preferably 113° or more, especially preferably 114° or more ° above. The constitution that the water contact angle of the outer surface 31 is so high is suitable for realizing the high antifouling property of the antifouling layer 30 . The water contact angle is, for example, 130° or less. Water droplets (droplets of pure water) with a diameter of 2 mm or less are formed on the outer surface 31 (exposed surface) of the antifouling layer 30, and the contact angle of the water droplets with respect to the surface of the antifouling layer 30 is measured to obtain the water contact angle. For example, by adjusting the composition of the antifouling layer 30, the roughness of the outer surface 31, the composition of the hard coat layer 12, and the roughness of the surface of the hard coat layer 12 on the optical function layer 20 side, the water contact of the outer surface 31 can be adjusted horn.

防污層30之厚度較佳為1 nm以上，更佳為3 nm以上，進而較佳為5 nm以上，尤其較佳為7 nm以上。此種構成適於確保防污層30之耐剝離性。防污層30之厚度較佳為25 nm以下，更佳為20 nm以下，進而較佳為18 nm以下。此種構成適於實現防污層30之上述水接觸角。The thickness of the antifouling layer 30 is preferably 1 nm or more, more preferably 3 nm or more, further preferably 5 nm or more, particularly preferably 7 nm or more. Such a configuration is suitable for securing the peeling resistance of the antifouling layer 30 . The thickness of the antifouling layer 30 is preferably 25 nm or less, more preferably 20 nm or less, and still more preferably 18 nm or less. Such a configuration is suitable for realizing the above-mentioned water contact angle of the antifouling layer 30 .

準備長條之透明基材10後，例如以輥對輥方式於透明基材10上依序積層密接層41、光學功能層20及防污層30，藉此可製作光學膜F。藉由於密接層41上依序積層第1高折射率層21、第1低折射率層22、第2高折射率層23及第2低折射率層24，可形成光學功能層20。After preparing the long transparent substrate 10 , the adhesive layer 41 , the optical functional layer 20 , and the antifouling layer 30 are sequentially laminated on the transparent substrate 10 by, for example, a roll-to-roll method, whereby the optical film F can be produced. The optical functional layer 20 can be formed by laminating the first high refractive index layer 21 , the first low refractive index layer 22 , the second high refractive index layer 23 , and the second low refractive index layer 24 in this order on the adhesion layer 41 .

藉由於樹脂膜11上形成硬塗層12，可製作透明基材10。例如於樹脂膜11上塗佈含有硬化性樹脂及視需要而定之微粒子之硬化性樹脂組合物而形成塗膜後，使該塗膜硬化，藉此可形成硬塗層12。於硬化性樹脂組合物含有紫外線化型樹脂之情形時，藉由照射紫外線使上述塗膜硬化。於硬化性樹脂組合物含有熱硬化型樹脂之情形時，藉由加熱使上述塗膜硬化。The transparent substrate 10 can be produced by forming the hard coat layer 12 on the resin film 11 . For example, after coating a curable resin composition containing a curable resin and optionally fine particles on the resin film 11 to form a coating film, the hard coat layer 12 can be formed by curing the coating film. When the curable resin composition contains an ultraviolet ray resin, the above-mentioned coating film is cured by irradiating ultraviolet rays. When the curable resin composition contains a thermosetting resin, the coating film is cured by heating.

視需要對形成於透明基材10上之硬塗層12之露出表面進行表面改質處理(硬塗層前處理步驟)。於進行電漿處理作為表面改質處理之情形時，作為處理氣體，例如可例舉氬氣及氧氣。又，電漿處理時之放電功率例如為10 W以上，且例如為10000 W以下。The exposed surface of the hard coat layer 12 formed on the transparent substrate 10 is subjected to surface modification treatment (hard coat pretreatment step) as necessary. In the case of performing plasma treatment as a surface modification treatment, examples of the treatment gas include argon gas and oxygen gas. In addition, the discharge power at the time of plasma treatment is, for example, 10 W or more, and, for example, 10,000 W or less.

藉由分別以乾式塗佈法依序成膜材料，可形成密接層41、第1高折射率層21、第1低折射率層22、第2高折射率層23、及第2低折射率層24(乾式成膜步驟)。作為乾式塗佈法，可例舉濺鍍法、真空蒸鍍法及CVD，較佳為使用濺鍍法。The adhesive layer 41 , the first high refractive index layer 21 , the first low refractive index layer 22 , the second high refractive index layer 23 , and the second low refractive index layer can be formed by sequentially forming film materials by the dry coating method. Layer 24 (dry film forming step). As a dry coating method, a sputtering method, a vacuum vapor deposition method, and CVD are mentioned, Preferably, a sputtering method is used.

濺鍍法係於濺鍍室內在真空條件下一面導入氣體，一面對配置於陰極上之靶施加負電壓。藉此，產生輝光放電，使氣體原子離子化，使該氣體離子高速碰撞靶表面，使靶材料自靶表面彈出，使彈出之靶材料沈積於規定面上。就成膜速度之觀點而言，作為濺鍍法，較佳為反應性濺鍍。反應性濺鍍係使用金屬靶作為靶，使用氬氣等惰性氣體與氧氣(反應性氣體)之混合氣體作為上述氣體。藉由調整惰性氣體與氧氣之流量比(sccm)，可調整成膜之無機氧化物所含之氧之比率。In the sputtering method, a gas is introduced into a sputtering chamber under vacuum conditions, and a negative voltage is applied to a target arranged on a cathode. Thereby, a glow discharge is generated, gas atoms are ionized, the gas ions collide with the target surface at a high speed, the target material is ejected from the target surface, and the ejected target material is deposited on a predetermined surface. From the viewpoint of the film-forming speed, reactive sputtering is preferable as the sputtering method. In reactive sputtering, a metal target is used as a target, and a mixed gas of an inert gas such as argon and oxygen (reactive gas) is used as the gas. By adjusting the flow ratio (sccm) of the inert gas and the oxygen gas, the ratio of the oxygen contained in the inorganic oxide of the film can be adjusted.

作為用以實施濺鍍法之電源，例如可例舉DC(Direct Current，直流)電源、AC(Alternating Current，交流)電源、RF(Radio Frequency，射頻)電源、及MFAC(Medium Frequency Alternating Current，中波交流)電源(頻帶為數kHz～數MHz之AC電源)。濺鍍法之放電電壓例如為200 V以上，且例如為1000 V以下。又，實施濺鍍法之濺鍍室內之成膜氣壓例如為0.01 Pa以上，且例如為2 Pa以下。As a power source for implementing the sputtering method, for example, a DC (Direct Current) power source, an AC (Alternating Current, alternating current) power source, an RF (Radio Frequency, radio frequency) power source, and an MFAC (Medium Frequency Alternating Current) power source can be exemplified. Wave AC) power supply (AC power supply with a frequency band of several kHz to several MHz). The discharge voltage of the sputtering method is, for example, 200 V or more and, for example, 1000 V or less. Moreover, the film-forming gas pressure in the sputtering chamber in which the sputtering method is performed is, for example, 0.01 Pa or more, and, for example, 2 Pa or less.

視需要對抗反射層之露出表面進行表面改質處理(基底層前處理步驟)。於進行電漿處理作為表面改質處理之情形時，作為處理氣體，例如可例舉氧氣及氬氣，較佳為使用氧氣。又，電漿處理時之放電功率例如為10 W以上，較佳為50 W以上，更佳為70 W以上。該放電功率例如為10000 W以下，較佳為8000 W以下，更佳為5000 W以下，進而較佳為4000 W以下，尤其較佳為3000 W以下。If necessary, the exposed surface of the anti-reflection layer is subjected to surface modification treatment (base layer pretreatment step). In the case of performing the plasma treatment as the surface modification treatment, as the treatment gas, for example, oxygen gas and argon gas can be mentioned, and oxygen gas is preferably used. Moreover, the discharge power at the time of plasma processing is 10 W or more, for example, Preferably it is 50 W or more, More preferably, it is 70 W or more. The discharge power is, for example, 10,000 W or less, preferably 8,000 W or less, more preferably 5,000 W or less, still more preferably 4,000 W or less, and particularly preferably 3,000 W or less.

藉由於光學功能層20上成膜上述有機氟化合物可形成防污層30(防污層形成步驟)。作為防污層30之形成方法，可例舉乾式塗佈法。作為乾式塗佈法，例如可例舉真空蒸鍍法、濺鍍法及CVD，較佳為使用真空蒸鍍法。The antifouling layer 30 can be formed by forming a film of the above-mentioned organic fluorine compound on the optical function layer 20 (the antifouling layer forming step). As a formation method of the antifouling layer 30, a dry coating method can be mentioned. As a dry coating method, a vacuum vapor deposition method, a sputtering method, and CVD are mentioned, for example, Preferably, a vacuum vapor deposition method is used.

較佳為，藉由輥對輥方式於使工作膜移行之狀態下，用一條連續生產線實施乾式成膜步驟至防污層形成步驟之一連串程序。更佳為，藉由輥對輥方式，於使工作膜移行之狀態下藉由一條連續生產線實施硬塗層前處理步驟至防污層形成步驟之一連串程序。於藉由一條連續生產線實施之程序中，工作膜始終不暴露於大氣中，較佳為不捲繞為卷狀。Preferably, a series of procedures from the dry film forming step to the antifouling layer forming step is carried out with a continuous production line in a state where the working film is moved by a roll-to-roll method. More preferably, a series of procedures from the hard coating pretreatment step to the antifouling layer forming step are carried out by a continuous production line in a state where the working film is moved by a roll-to-roll method. In a procedure carried out by a continuous production line, the working film is never exposed to the atmosphere, preferably not wound into a roll.

例如可以如上方式製造光學膜F。例如經由黏著劑將透明基材10側貼合於被黏著體來使用光學膜F。作為被黏著體，例如可例舉觸控面板顯示器等顯示器之圖像顯示側配置的透明罩。For example, the optical film F can be manufactured as described above. For example, the optical film F is used by bonding the transparent base material 10 side to the adherend via an adhesive. As a to-be-adhered body, the transparent cover arrange|positioned at the image display side of displays, such as a touch panel display, is mentioned, for example.

光學膜F中，如上所述，藉由利用X射線光電子分光法進行之元素分析，對防污層30之表面31，檢測F相對於Si之比率(F/Si、原子數比率)，於分析深度為1 nm時該比率為20以上，較佳為22以上，更佳為24以上，進而較佳為26以上。又，較佳為於分析深度1 nm至分析深度5 nm，上述比率單調遞減。該等構成適於使表面31同時表現出由有機氟化合物之末端氟化烷基獲得之高疏水性與高疏油性，因此表現出優異之防污性。另外，與比率(F/Si)相關之上述構成適於確保表面31為高配向性地緻密配置末端氟化烷基之狀態。於表面31，越是高配向性地緻密配置末端氟化烷基，越是能抑制表面31之劣化，因此，抑制防污層30之防污性下降。In the optical film F, the ratio of F to Si (F/Si, atomic ratio) is detected on the surface 31 of the antifouling layer 30 by elemental analysis by X-ray photoelectron spectroscopy as described above, and the analysis is performed. When the depth is 1 nm, the ratio is 20 or more, preferably 22 or more, more preferably 24 or more, and still more preferably 26 or more. Furthermore, it is preferable that the above-mentioned ratio decreases monotonically from an analysis depth of 1 nm to an analysis depth of 5 nm. These constitutions are suitable for the surface 31 to simultaneously exhibit high hydrophobicity and high oleophobicity obtained by the terminal fluorinated alkyl group of the organic fluorine compound, thus exhibiting excellent antifouling properties. In addition, the above-mentioned configuration related to the ratio (F/Si) is suitable for securing the state in which the terminal fluorinated alkyl groups are densely arranged on the surface 31 with high orientation. On the surface 31 , the more densely arranged terminal fluorinated alkyl groups with high orientation, the more the deterioration of the surface 31 can be suppressed, and thus the deterioration of the antifouling property of the antifouling layer 30 is suppressed.

光學膜F亦可為抗反射膜以外之其他光學膜。作為光學膜，例如可例舉透明導電性膜及電磁波屏蔽膜。The optical film F may also be other optical films other than the antireflection film. As an optical film, a transparent conductive film and an electromagnetic wave shielding film are mentioned, for example.

於光學膜F為透明導電性膜之情形時，該光學膜F之光學功能層20例如朝向厚度方向T之一側依序具備第1介電薄膜、ITO膜等透明電極膜、及第2介電膜。具有此種積層構成之光學功能層20兼具可見光透過性與導電性。When the optical film F is a transparent conductive film, the optical functional layer 20 of the optical film F includes, for example, a first dielectric film, a transparent electrode film such as an ITO film, and a second dielectric film in this order toward the side in the thickness direction T. Electric film. The optical functional layer 20 having such a laminated structure has both visible light transmittance and conductivity.

於光學膜F為電磁波屏蔽膜之情形時，該光學膜F之光學功能層20例如於厚度方向T上交替具備具有電磁波反射能之金屬薄膜及金屬氧化物膜。具有此種積層構成之光學功能層20兼具對於特定波長電磁波之屏蔽性與可見光透過性。When the optical film F is an electromagnetic wave shielding film, the optical function layer 20 of the optical film F alternately includes a metal thin film and a metal oxide film having electromagnetic wave reflection energy in the thickness direction T, for example. The optical functional layer 20 having such a laminated structure has both shielding properties against electromagnetic waves of a specific wavelength and visible light transmittance.

如圖2所示，又，光學膜F亦可具備光學功能層20。圖2所示之光學膜F朝向厚度方向T之一側依序具備透明基材10(樹脂膜11、硬塗層12)、密接層41、無機氧化物基底層42、及防污層30。於本變化例中，無機氧化物基底層42配置於密接層41上。 [實施例] As shown in FIG. 2 , the optical film F may also include the optical functional layer 20 . The optical film F shown in FIG. 2 includes a transparent substrate 10 (resin film 11 , hard coat layer 12 ), an adhesive layer 41 , an inorganic oxide base layer 42 , and an antifouling layer 30 in this order toward one side in the thickness direction T. As shown in FIG. In this modification, the inorganic oxide base layer 42 is disposed on the adhesion layer 41 . [Example]

以下示出實施例對本發明進行具體說明。本發明並不限定於實施例。又，以下記載之調配量(含量)、物性值、參數等具體數值可替換為上述「實施方式」中記載之與其對應之調配量(含量)、物性值、參數等相當記載之上限(定義為「以下」或「未達」之數值)或下限(定義為「以上」或「超過」之數值)。The present invention will be specifically described below with reference to Examples. The present invention is not limited to the Examples. In addition, the specific numerical values such as the compounding amount (content), physical property value, parameter, etc. described below can be replaced by the corresponding compounding amount (content), physical property value, parameter, etc. described in the above-mentioned "Embodiment". "under" or "under" value) or lower limit (defined as "above" or "over" value).

[實施例1] 首先，於作為透明樹脂膜之長條之三乙醯纖維素(TAC)膜(厚度80 μm)之單面形成硬塗層(硬塗層形成步驟)。於本步驟中，首先，將以下成分混合，製備固形物成分濃度55質量%之組合物(清漆)：紫外線硬化型丙烯酸單體(商品名「GRANDIC PC-1070」，DIC公司製造)100質量份、含有奈米氧化矽粒子之有機氧化矽凝膠(商品名「MEK-ST-L」，奈米氧化矽粒子之平均一次粒徑為50 nm，固形物成分濃度30質量%，日產化學公司製造)25質量份(奈米氧化矽粒子換算量)、觸變性賦予劑(商品名「Lucentite SAN」，作為有機黏土之合成膨潤石，CO-OP. CHEMICAL公司製造)1.5質量份、光聚合起始劑(商品名「OMNIRAD907」，BASF公司製造)3質量份、調平劑(商品名「LE303」，共榮社化學公司製造)0.15質量份。混合時使用超音波分散機。其次，於上述TAC膜之單面塗佈組合物，形成塗膜。其次，藉由照射紫外線使該塗膜硬化後，藉由加熱使其乾燥。照射紫外線時，使用高壓水銀燈作為光源，使用波長365 nm之紫外線，累計照射光量設為200 mJ/cm 2。又，加熱時間設為80，加熱溫度設為3分鐘。藉此，於TAC膜上形成厚度6 μm之硬塗(HC)層。 [Example 1] First, a hard coat layer (hard coat layer forming step) was formed on one side of a long strip of triacetyl cellulose (TAC) film (thickness 80 μm) as a transparent resin film. In this step, first, the following components were mixed to prepare a composition (varnish) with a solid content concentration of 55% by mass: 100 parts by mass of an ultraviolet curable acrylic monomer (trade name "GRANDIC PC-1070", manufactured by DIC Corporation) , Organosilica gel containing nano-silica particles (trade name "MEK-ST-L", the average primary particle size of the nano-silica particles is 50 nm, and the solid content concentration is 30% by mass, manufactured by Nissan Chemical Co., Ltd. ) 25 parts by mass (in terms of nano-silicon oxide particles), 1.5 parts by mass of a thixotropy imparting agent (trade name "Lucentite SAN", synthetic bentonite as organoclay, manufactured by CO-OP. CHEMICAL Co., Ltd.), photopolymerization initiation 3 parts by mass of an agent (trade name "OMNIRAD907", manufactured by BASF Corporation), and 0.15 parts by mass of a leveling agent (trade name "LE303", manufactured by Kyoeisha Chemical Co., Ltd.). Use an ultrasonic disperser when mixing. Next, the composition is applied to one side of the above-mentioned TAC film to form a coating film. Next, after hardening this coating film by irradiating an ultraviolet-ray, it is made to dry by heating. When irradiating ultraviolet rays, a high-pressure mercury lamp was used as a light source, and ultraviolet rays with a wavelength of 365 nm were used, and the cumulative irradiation light amount was set to 200 mJ/cm 2 . In addition, the heating time was set to 80, and the heating temperature was set to 3 minutes. Thereby, a hard coat (HC) layer with a thickness of 6 μm was formed on the TAC film.

其次，以輥對輥方式使作為工作膜之附HC層之TAC膜行走，同時藉由電漿處理裝置於1.0 Pa之真空環境下對該膜之HC層表面進行電漿處理(HC層前處理步驟)。該電漿處理使用氬氣作為處理氣體，放電功率(放電出力)設為150 W。Next, the TAC film with the HC layer attached to the working film was moved in a roll-to-roll manner, and at the same time, the surface of the HC layer of the film was plasma treated by a plasma treatment device in a vacuum environment of 1.0 Pa (HC layer pretreatment). step). In this plasma treatment, argon gas was used as the treatment gas, and the discharge power (discharge output) was set to 150 W.

其次，於電漿處理後之附HC層之TAC膜之HC層上依序形成密接層與抗反射層(濺鍍成膜步驟)。具體而言，藉由輥對輥方式之濺鍍成膜裝置，於附HC層之TAC膜之HC層上，依序形成作為密接層之厚度1.5 nm之銦錫氧化物(ITO)層、作為第1高折射率層之厚度12 nm之Nb 2O 5層、作為第1低折射率層之厚度28 nm之SiO 2層、作為第2高折射率層之厚度100 nm之Nb 2O 5層、作為第2低折射率層之厚度85 nm之SiO 2層。形成密接層時，使用ITO靶，使用氬氣作為惰性氣體，使用相對於氬氣100體積份為10體積份之氧氣作為反應性氣體，將放電電壓設為400 V，將成膜室內之氣壓(成膜氣壓)設為0.2 Pa，藉由MFAC濺鍍成膜ITO層。形成第1高折射率層時，使用Nb靶，使用100體積份之氬氣及5體積份之氧氣，將放電電壓設為415 V，將成膜氣壓設為0.42 Pa，藉由MFAC濺鍍成膜Nb 2O 5層。形成第1低折射率層時，使用Si靶，使用100體積份之氬氣及30體積份之氧氣，將放電電壓設為350 V，將成膜氣壓設為0.3 Pa，藉由MFAC濺鍍成膜SiO 2層。形成第2高折射率層時，使用Nb靶，使用100體積份之氬氣及13體積份之氧氣，將放電電壓設為460 V，將成膜氣壓設為0.5 Pa，藉由MFAC濺鍍成膜Nb 2O 5層。形成第2低折射率層時，使用Si靶，使用100體積份之氬氣及30體積份之氧氣，將放電電壓設為340 V，將成膜氣壓設為0.25 Pa，藉由MFAC濺鍍成膜SiO 2層。以如上方式，於附HC層之TAC膜之HC層上經由密接層積層形成抗反射層(第1高折射率層、第1低折射率層、第2高折射率層、第2低折射率層)。 Next, an adhesion layer and an anti-reflection layer are sequentially formed on the HC layer of the TAC film attached with the HC layer after the plasma treatment (sputtering film forming step). Specifically, an indium tin oxide (ITO) layer with a thickness of 1.5 nm as an adhesive layer was sequentially formed on the HC layer of the TAC film with the HC layer by means of a roll-to-roll sputtering film forming apparatus, Nb 2 O 5 layer with a thickness of 12 nm as the first high refractive index layer, SiO 2 layer with a thickness of 28 nm as the first low refractive index layer, and Nb 2 O 5 layer with a thickness of 100 nm as the second high refractive index layer , SiO 2 layer with a thickness of 85 nm as the second low refractive index layer. When forming the adhesion layer, an ITO target was used, argon gas was used as an inert gas, 10 parts by volume of oxygen gas was used as a reactive gas relative to 100 parts by volume of argon gas, the discharge voltage was set to 400 V, and the pressure in the film-forming chamber ( The film forming pressure) was set to 0.2 Pa, and the ITO layer was formed by MFAC sputtering. When forming the first high refractive index layer, a Nb target was used, 100 parts by volume of argon gas and 5 parts by volume of oxygen gas were used, the discharge voltage was set to 415 V, and the film-forming gas pressure was set to 0.42 Pa, and sputtered by MFAC. Membrane Nb2O5 layer. When forming the first low refractive index layer, a Si target was used, 100 parts by volume of argon gas and 30 parts by volume of oxygen gas were used, the discharge voltage was set to 350 V, and the film-forming pressure was set to 0.3 Pa, and sputtered by MFAC. film SiO 2 layer. When forming the second high refractive index layer, a Nb target was used, 100 parts by volume of argon gas and 13 parts by volume of oxygen gas were used, the discharge voltage was set to 460 V, and the film-forming gas pressure was set to 0.5 Pa, and sputtered by MFAC. Membrane Nb2O5 layer. When forming the second low-refractive index layer, a Si target was used, 100 parts by volume of argon gas and 30 parts by volume of oxygen gas were used, the discharge voltage was set to 340 V, and the film formation pressure was set to 0.25 Pa, and sputtered by MFAC. film SiO 2 layer. In the above manner, an anti-reflection layer (the first high refractive index layer, the first low refractive index layer, the second high refractive index layer, the second low refractive index layer) is formed on the HC layer of the TAC film with the HC layer through a close-contact layered layer. layer).

其次，藉由電漿處理裝置，於1.0 Pa之真空環境下對形成之抗反射層之表面進行電漿處理(基底層前處理步驟)。該電漿處理使用氧氣作為處理氣體，將放電功率設為100 W。Next, plasma treatment is performed on the surface of the formed anti-reflection layer in a vacuum environment of 1.0 Pa by a plasma treatment device (a base layer pretreatment step). In this plasma treatment, oxygen gas was used as the treatment gas, and the discharge power was set to 100 W.

其次，於抗反射層上形成防污層(防污層形成步驟)。具體而言，藉由使用含全氟聚醚基之烷氧基矽烷化合物作為蒸鍍源之真空蒸鍍法，於抗反射層上形成厚度8 nm之防污層。蒸鍍源係將大金工業公司製造之「OPTOOL UD509」(上述通式(2)所示之含全氟聚醚基之烷氧基矽烷化合物，固形物成分濃度20質量%)乾燥所得之固形物成分。又，真空蒸鍍法之蒸鍍源之加熱溫度設為260℃。Next, an antifouling layer is formed on the antireflection layer (antifouling layer forming step). Specifically, an antifouling layer with a thickness of 8 nm was formed on the antireflection layer by a vacuum evaporation method using a perfluoropolyether group-containing alkoxysilane compound as an evaporation source. The vapor deposition source is a solid obtained by drying "OPTOOL UD509" (a perfluoropolyether group-containing alkoxysilane compound represented by the above general formula (2), solid content concentration 20 mass %) manufactured by Daikin Industries, Ltd. material composition. In addition, the heating temperature of the vapor deposition source of the vacuum vapor deposition method was made into 260 degreeC.

於以輥對輥方式使工作膜移行之狀態下藉由一條連續生產線實施上述HC層前處理步驟至防污層形成步驟之一連串程序。該程序中，工作膜始終不暴露於大氣中。A series of procedures from the above-mentioned HC layer pretreatment step to the antifouling layer forming step is carried out through a continuous production line in a state where the working film is moved in a roll-to-roll manner. During this procedure, the working membrane is never exposed to the atmosphere.

以如上方式製作實施例1之光學膜。實施例1之光學膜朝向厚度方向一側依序具備透明基材(樹脂膜、硬塗層)、密接層、抗反射層、防污層。The optical film of Example 1 was produced in the above manner. The optical film of Example 1 includes a transparent substrate (resin film, hard coat layer), an adhesive layer, an antireflection layer, and an antifouling layer in this order toward one side in the thickness direction.

[實施例2] 除以下幾點以外，以與實施例1之光學膜同樣之方式製作實施例2之光學膜。未實施基底層前處理步驟(即，作為基底層前處理之電漿處理之放電功率設為0 W)。防污層形成步驟(真空蒸鍍)中，使用將信越化學公司製造之「KY1903-1」(含全氟聚醚基之烷氧基矽烷化合物)乾燥所得之固形物成分作為蒸鍍源。 [Example 2] Except for the following points, the optical film of Example 2 was produced in the same manner as the optical film of Example 1. The base layer pretreatment step was not performed (ie, the discharge power of the plasma treatment as the base layer pretreatment was set to 0 W). In the antifouling layer formation step (vacuum deposition), a solid content obtained by drying "KY1903-1" (perfluoropolyether group-containing alkoxysilane compound) manufactured by Shin-Etsu Chemical Co., Ltd. was used as a deposition source.

[比較例1] 於基底層前處理步驟後且防污層形成步驟前，將工作膜暫時捲取為卷狀，除此以外，以與實施例1之光學膜同樣之方式製作比較例1之光學膜。 [Comparative Example 1] The optical film of Comparative Example 1 was produced in the same manner as the optical film of Example 1, except that the working film was temporarily wound into a roll after the base layer pretreatment step and before the antifouling layer forming step.

[比較例2] 除防污層形成步驟以外，以與實施例1之光學膜同樣之方式製作比較例2之光學膜。本比較例之防污層形成步驟中，藉由濕式塗佈法形成防污層。具體而言，首先，用稀釋溶劑(商品名「Fluorinert」，3M公司製造)將作為塗佈劑之「OPTOOL UD509」(大金工業公司製造)稀釋，製備固形物成分濃度0.1質量%之塗佈液。其次，藉由凹版塗佈，將塗佈液塗佈於藉由濺鍍成膜步驟所形成之抗反射層之上形成塗膜。其次，藉由於60℃下加熱2分鐘，使該塗膜乾燥。藉此，於抗反射層上形成厚度7 nm之防污層。 [Comparative Example 2] Except for the antifouling layer forming step, the optical film of Comparative Example 2 was produced in the same manner as the optical film of Example 1. In the antifouling layer forming step of this comparative example, the antifouling layer was formed by a wet coating method. Specifically, first, "OPTOOL UD509" (manufactured by Daikin Industries, Ltd.) as a coating agent was diluted with a diluting solvent (trade name "Fluorinert", manufactured by 3M Corporation) to prepare a coating having a solid content concentration of 0.1% by mass. liquid. Next, by gravure coating, the coating liquid is coated on the anti-reflection layer formed by the sputtering film-forming step to form a coating film. Next, the coating film was dried by heating at 60°C for 2 minutes. Thereby, an antifouling layer with a thickness of 7 nm was formed on the antireflection layer.

＜藉由X射線光電子分光法進行之防污層之分析＞ 藉由X射線光電子分光法(ESCA)對實施例1、2及比較例1、2之各光學膜之防污層表面進行分析。自光學膜切出約10 mm×10 mm之尺寸，準備分析用試樣。分析使用X射線光電子分光裝置(商品名「Quantum 2000」，ULVAC-PHI公司製造)。本分析係於下述條件下進行X射線光電子分光測定。 <Analysis of antifouling layer by X-ray photoelectron spectroscopy> The surface of the antifouling layer of each of the optical films of Examples 1 and 2 and Comparative Examples 1 and 2 was analyzed by X-ray photoelectron spectroscopy (ESCA). A sample of about 10 mm × 10 mm was cut out from the optical film to prepare a sample for analysis. For the analysis, an X-ray photoelectron spectrometer (trade name "Quantum 2000", manufactured by ULVAC-PHI Corporation) was used. In this analysis, X-ray photoelectron spectroscopy was carried out under the following conditions.

激發X射線源：單色 AI Kα X-ray Setting：200 μm

Figure 02_image001
(15 kV、30 W) 光電子掠出角：相對於試樣表面為5度、15度、30度、45度 Excitation X-ray source: Monochromatic AI Kα X-ray Setting: 200 μm
Figure 02_image001
(15 kV, 30 W) Photoelectron grazing angle: 5 degrees, 15 degrees, 30 degrees, 45 degrees relative to the sample surface

本分析中，藉由調整光電子掠出角來調整分析深度。具體而言，藉由將光電子掠出角設為5度而將分析深度設為1 nm，藉由將光電子掠出角設為15度而將分析深度設為2 nm，藉由將光電子掠出角設為30度而將分析深度設為3 nm，藉由將光電子掠出角設為45度而將分析深度設為5 nm。將元素分析結果示於表1中。亦將所檢測之F相對於Si之比率示於表1中。In this analysis, the analysis depth is adjusted by adjusting the photoelectron grazing angle. Specifically, the analysis depth was set to 1 nm by setting the photoelectron grazing angle to 5 degrees, the analysis depth was 2 nm by setting the photoelectron grazing angle to 15 degrees, and the analysis depth was set to 2 nm by setting the photoelectron grazing angle to 15 degrees. The angle was set to 30 degrees and the analysis depth was set to 3 nm, and the analysis depth was set to 5 nm by setting the photoelectron grazing angle to 45 degrees. The results of elemental analysis are shown in Table 1. The detected ratios of F to Si are also shown in Table 1.

＜水接觸角＞ 實施例1、2及比較例1、2之各光學膜，調查防污層表面之水接觸角。首先，藉由對光學膜之防污層表面滴加約1 μL之純水而形成水滴。其次，測定防污層表面上之水滴之表面與防污層表面所成之角度。測定時使用接觸角計(商品名「DMo-501」，協和界面科學公司製造)。將其測定結果作為初始水接觸角θ 0表示於表1中。 <Water Contact Angle> For each of the optical films of Examples 1 and 2 and Comparative Examples 1 and 2, the water contact angle on the surface of the antifouling layer was investigated. First, water droplets were formed by dropping about 1 μL of pure water on the surface of the antifouling layer of the optical film. Next, the angle formed by the surface of the water droplet on the surface of the antifouling layer and the surface of the antifouling layer was measured. A contact angle meter (trade name "DMo-501", manufactured by Kyowa Interface Science Co., Ltd.) was used for the measurement. The measurement results are shown in Table 1 as the initial water contact angle θ 0 .

＜橡皮擦劃擦試驗＞ 對於實施例1、2及比較例1、2之各光學膜，調查經過橡皮擦劃擦試驗後防污層表面之防污性下降之程度。具體而言，首先，橡皮擦於光學膜之防污層表面往返移動進行劃擦，實施劃擦試驗。該試驗使用Minoan公司製造之橡皮擦(Φ6 mm)，將橡皮擦對防污層表面之負荷設為1 kg/6 mmΦ，將橡皮擦於防污層表面上之劃擦距離(往返移動之單程)設為20 mm，將橡皮擦之劃擦速度設為40 rpm，將橡皮擦在防污層表面往返移動之次數設為3000次往返。其次，以與初始水接觸角θ 0之測定方法相同之方法測定光學膜之防污層表面橡皮擦劃擦部位之水接觸角。將其測定結果作為橡皮擦劃擦試驗後之水接觸角θ 1示於表1中。 <Eraser scratch test> With respect to each of the optical films of Examples 1 and 2 and Comparative Examples 1 and 2, the degree to which the antifouling properties of the antifouling layer surface decreased after the eraser scratch test was investigated. Specifically, first, an eraser was moved back and forth on the surface of the antifouling layer of the optical film to scratch, and a scratch test was performed. In this test, an eraser (Φ6 mm) manufactured by Minoan Company was used, the load of the eraser on the surface of the antifouling layer was set to 1 kg/6 mmΦ, and the scratching distance of the eraser on the surface of the antifouling layer (one-way reciprocating movement) ) was set to 20 mm, the scratching speed of the eraser was set to 40 rpm, and the number of times the eraser moved back and forth on the surface of the antifouling layer was set to 3000 times. Next, the water contact angle at the portion scratched by the eraser on the surface of the antifouling layer of the optical film was measured by the same method as the measurement method of the initial water contact angle θ 0 . The measurement results are shown in Table 1 as the water contact angle θ1 after the eraser scratch test.

＜評估＞ 實施例1、2之光學膜與比較例1、2之各光學膜相比，經過橡皮擦劃擦試驗後防污層表面之水接觸角下降之程度明顯更小，因此，防污性之下降明顯更少(防污層表面，水接觸角下降越少，則防污性下降越少)。 ＜Assessment＞ Compared with the optical films of Comparative Examples 1 and 2, the optical films of Examples 1 and 2 show that the degree of decrease in the water contact angle of the antifouling layer surface after the eraser scratch test is significantly smaller. Therefore, the decline of the antifouling property is significantly smaller. Significantly less (the surface of the antifouling layer, the less the drop in water contact angle, the less the drop in antifouling).

[表1]    防污層 形成前之 捲取 防污層 水接觸角θ 0(°) 水接觸角θ 1(°) 藉由X射線光電子分光法進行之元素分析 形成方法 厚度(nm) 分析深度 (nm) C (%) O (%) F (%) Si (%) F/Si 實施例1 無 真空蒸鍍 8 116 93 1 26.4 18.9 52.8 1.9 27.8 2 26.6 19.4 51.2 2.9 17.6 3 26.8 19.8 49.5 3.9 12.7 5 25.4 22.3 45.8 6.5 7.1 實施例2 無 真空蒸鍍 8 117 100 1 26.7 19.0 52.9 1.4 37.8 2 25.7 19.8 52.5 2.2 24.4 3 24.6 20.5 52.0 2.9 17.9 5 24.3 21.6 49.3 4.7 10.5 比較例1 有 真空蒸鍍 8 115 75 1 15.3 47.1 21.1 16.5 1.3 2 14.7 47.8 19.6 18.0 1.1 3 14.1 48.4 18.0 19.5 0.9 5 12.4 51.4 15.8 20.4 0.8 比較例2 無 濕式塗佈 7 110 70 1 28.2 18.6 50.5 2.7 18.7 2 26.0 18.3 53.2 2.5 21.3 3 27.5 18.8 50.5 3.2 15.8 5 23.7 24.3 44.6 7.4 6.0 [Table 1] Coil before formation of antifouling layer Antifouling layer Water contact angle θ 0 (°) Water contact angle θ 1 (°) Elemental Analysis by X-ray Photoelectron Spectroscopy Formation method Thickness (nm) Analysis depth (nm) C (%) O (%) F (%) Si (%) F/Si Example 1 none Vacuum evaporation 8 116 93 1 26.4 18.9 52.8 1.9 27.8 2 26.6 19.4 51.2 2.9 17.6 3 26.8 19.8 49.5 3.9 12.7 5 25.4 22.3 45.8 6.5 7.1 Example 2 none Vacuum evaporation 8 117 100 1 26.7 19.0 52.9 1.4 37.8 2 25.7 19.8 52.5 2.2 24.4 3 24.6 20.5 52.0 2.9 17.9 5 24.3 21.6 49.3 4.7 10.5 Comparative Example 1 Have Vacuum evaporation 8 115 75 1 15.3 47.1 21.1 16.5 1.3 2 14.7 47.8 19.6 18.0 1.1 3 14.1 48.4 18.0 19.5 0.9 5 12.4 51.4 15.8 20.4 0.8 Comparative Example 2 none wet coating 7 110 70 1 28.2 18.6 50.5 2.7 18.7 2 26.0 18.3 53.2 2.5 21.3 3 27.5 18.8 50.5 3.2 15.8 5 23.7 24.3 44.6 7.4 6.0

10:透明基材 11:樹脂膜 12:硬塗層 20:光學功能層 21:第1高折射率層 22:第1低折射率層 23:第2高折射率層 24:第2低折射率層 30:防污層 31:表面 41:密接層 42:無機氧化物基底層 F:光學膜(附防污層之光學膜) T:厚度方向 10: Transparent substrate 11: Resin film 12: Hard coating 20: Optical functional layer 21: 1st high refractive index layer 22: 1st low refractive index layer 23: Second high refractive index layer 24: Second low refractive index layer 30: Antifouling layer 31: Surface 41: Adhesion layer 42: Inorganic oxide base layer F: Optical film (optical film with antifouling layer) T: thickness direction

圖1係本發明之光學膜之一實施方式之剖視模式圖。 圖2係本發明之光學膜之變化例之剖視模式圖(本變化例不具備光學功能層)。 FIG. 1 is a schematic cross-sectional view of one embodiment of the optical film of the present invention. 2 is a schematic cross-sectional view of a modification of the optical film of the present invention (this modification does not have an optical functional layer).

10:透明基材 10: Transparent substrate

11:樹脂膜 11: Resin film

12:硬塗層 12: Hard coating

20:光學功能層 20: Optical functional layer

21:第1高折射率層 21: 1st high refractive index layer

22:第1低折射率層 22: 1st low refractive index layer

23:第2高折射率層 23: Second high refractive index layer

24:第2低折射率層 24: Second low refractive index layer

30:防污層 30: Antifouling layer

31:表面 31: Surface

41:密接層 41: Adhesion layer

42:無機氧化物基底層 42: Inorganic oxide base layer

F:光學膜(附防污層之光學膜) F: Optical film (optical film with antifouling layer)

T:厚度方向 T: thickness direction

Claims (7)

一種附防污層之光學膜，其於厚度方向上依序具備透明基材及防污層， 藉由利用X射線光電子分光法進行之元素分析，檢測上述防污層之與上述透明基材相反之表面側的F相對於Si之比率，於分析深度為1 nm時該比率為20以上。 An optical film with an antifouling layer, comprising a transparent substrate and an antifouling layer in order in the thickness direction, The ratio of F to Si on the surface side of the antifouling layer opposite to the transparent substrate was detected by elemental analysis by X-ray photoelectron spectroscopy, and the ratio was 20 or more at an analysis depth of 1 nm. 如請求項1之附防污層之光學膜，其中上述防污層之上述比率自分析深度1 nm至分析深度5 nm單調遞減。The optical film with an antifouling layer according to claim 1, wherein the above ratio of the antifouling layer monotonically decreases from an analysis depth of 1 nm to an analysis depth of 5 nm. 如請求項1或2之附防污層之光學膜，其中上述防污層含有具有全氟聚醚基之烷氧基矽烷化合物。The optical film with an antifouling layer according to claim 1 or 2, wherein the antifouling layer contains an alkoxysilane compound having a perfluoropolyether group. 如請求項1或2之附防污層之光學膜，其中上述防污層為乾式塗佈膜。The optical film with an antifouling layer according to claim 1 or 2, wherein the antifouling layer is a dry coating film. 如請求項1或2之附防污層之光學膜，其於上述透明基材與上述防污層之間具備無機氧化物基底層，於該無機氧化物基底層上配置有上述防污層。The optical film with an antifouling layer according to claim 1 or 2, comprising an inorganic oxide base layer between the transparent substrate and the antifouling layer, and the antifouling layer is disposed on the inorganic oxide base layer. 如請求項5之附防污層之光學膜，其中上述無機氧化物基底層包含二氧化矽。The optical film with an antifouling layer according to claim 5, wherein the inorganic oxide base layer comprises silicon dioxide. 如請求項5之附防污層之光學膜，其中上述無機氧化物基底層之上述防污層側之表面具有0.5 nm以上10 nm以下之表面粗糙度Ra。The optical film with an antifouling layer according to claim 5, wherein the surface on the antifouling layer side of the inorganic oxide base layer has a surface roughness Ra of 0.5 nm to 10 nm.
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