TW202215074A - Optical film with anti-fouling layer - Google Patents

Optical film with anti-fouling layer Download PDF

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TW202215074A
TW202215074A TW110125740A TW110125740A TW202215074A TW 202215074 A TW202215074 A TW 202215074A TW 110125740 A TW110125740 A TW 110125740A TW 110125740 A TW110125740 A TW 110125740A TW 202215074 A TW202215074 A TW 202215074A
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layer
antifouling
refractive index
antifouling layer
optical film
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TWI817160B (en
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宮本幸大
梨木智剛
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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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1687—Use of special additives
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    • 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
    • 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
    • C23C14/08—Oxides
    • C23C14/083—Oxides of refractory metals or yttrium
    • 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
    • C23C14/10—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
    • C23C14/56—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 with an anti-fouling layer according to the present invention comprises a substrate layer, an optical function layer comprising an inorganic layer, and an anti-fouling layer arranged in this order towards one side of the film in the thickness direction. The surface roughness Ra of the anti-fouling layer is 2-15 nm inclusive.

Description

附防汙層之光學膜Optical film with antifouling layer

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

先前，就防止汙垢(手漬及指紋)附著之觀點而言，已知於膜基材之表面、及光學零件之表面形成防汙層。Heretofore, from the viewpoint of preventing the adhesion of dirt (hand stains and fingerprints), it is known to form an antifouling layer on the surface of a film substrate and the surface of an optical component.

具體而言，提出一種朝厚度方向之一側依次具備透明膜、抗反射層及防汙層之抗反射膜(例如，參照專利文獻1)。 [先前技術文獻] [專利文獻] Specifically, an antireflection film including a transparent film, an antireflection layer, and an antifouling layer in this order toward one side in the thickness direction is proposed (for example, refer to Patent Document 1). [Prior Art Literature] [Patent Literature]

[專利文獻1]日本專利特開2017-227898號公報[Patent Document 1] Japanese Patent Laid-Open No. 2017-227898

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

於汙垢附著於防汙層之情形時，則有擦拭該汙垢而去除該汙垢之情形。因此，對防汙層要求對擦拭(滑動)之耐久性。When the dirt adheres to the antifouling layer, there is a case where the dirt is removed by wiping the dirt. Therefore, durability against wiping (sliding) is required for the antifouling layer.

另一方面，若對防汙層照射紫外線，則有如下缺陷，即，防汙層對滑動之耐久性降低。On the other hand, when the antifouling layer is irradiated with ultraviolet rays, there is a disadvantage that the durability of the antifouling layer to sliding is lowered.

本發明提供一種附防汙層之光學膜，其即便對防汙層照射紫外線，亦可抑制防汙層對滑動之耐久性之降低。 [解決問題之技術手段] The present invention provides an optical film with an antifouling layer, which can suppress the decrease in the durability of the antifouling layer to sliding even if the antifouling layer is irradiated with ultraviolet rays. [Technical means to solve problems]

本發明[1]係一種附防汙層之光學膜，其朝厚度方向之一側依次具備基材層、包含無機層之光學功能層、及防汙層，且上述防汙層之表面粗糙度Ra為2 nm以上15 nm以下。The present invention [1] is an optical film with an antifouling layer, which includes a base material layer, an optical functional layer including an inorganic layer, and an antifouling layer in this order toward one side in the thickness direction, and the surface roughness of the antifouling layer is Ra is 2 nm or more and 15 nm or less.

本發明[2]包含如上述[1]所記載之附防汙層之光學膜，其中上述光學功能層為抗反射層。The present invention [2] includes the antifouling layer-attached optical film according to the above [1], wherein the optical functional layer is an antireflection layer.

本發明[3]包含如上述[2]所記載之附防汙層之光學膜，其中上述抗反射層交替地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。The present invention [3] includes the optical film with an antifouling layer as described in the above [2], wherein the antireflection layer alternately has a high refractive index layer with a relatively large refractive index and a low refractive index with a relatively small refractive index rate layer.

本發明[4]包含如上述[1]至[3]中任一項之附防汙層之光學膜，其中基材層朝厚度方向之一側依次具備基材及硬塗層。The present invention [4] includes the antifouling layer-attached optical film according to any one of the above [1] to [3], wherein the base material layer includes a base material and a hard coat layer in this order toward one side in the thickness direction.

本發明[5]包含如上述[4]所記載之附防汙層之光學膜，其中上述硬塗層包含金屬氧化物微粒子。The present invention [5] includes the antifouling layer-attached optical film according to the above [4], wherein the hard coat layer contains metal oxide fine particles.

本發明[6]包含如上述[5]所記載之附防汙層之光學膜，其中上述金屬氧化物微粒子為奈米二氧化矽粒子。The present invention [6] includes the optical film with an antifouling layer according to the above [5], wherein the metal oxide fine particles are nano-silica particles.

本發明[7]包含如上述[4]至[6]中任一項之附防汙層之光學膜，其中上述硬塗層之厚度方向上之一面之表面粗糙度Ra為0.5 nm以上20 nm以下。 [發明之效果] The present invention [7] includes the antifouling layer-attached optical film according to any one of the above [4] to [6], wherein the surface roughness Ra of one surface in the thickness direction of the hard coat layer is 0.5 nm or more and 20 nm the following. [Effect of invention]

於本發明之附防汙層之光學膜中，防汙層之表面粗糙度Ra為2 nm以上15 nm以下。因此，即便對防汙層照射紫外線，亦可抑制防汙層對滑動之耐久性之降低。In the optical film with an antifouling layer of the present invention, the surface roughness Ra of the antifouling layer is 2 nm or more and 15 nm or less. Therefore, even if an ultraviolet-ray is irradiated to an antifouling layer, the fall of the durability to sliding of an antifouling layer can be suppressed.

參照圖1，對本發明之附防汙層之光學膜之一實施方式進行說明。1, an embodiment of the optical film with an antifouling layer of the present invention will be described.

於圖1中，紙面上下方向為上下方向(厚度方向)。又，紙面上側為上側(厚度方向之一側)。又，紙面下側為下側(厚度方向之另一側)。又，紙面左右方向及深度方向為與上下方向正交之面方向。具體而言，依據各圖之方向箭頭。In FIG. 1 , the up-down direction on the paper is the up-down direction (thickness direction). In addition, the upper side of the paper is the upper side (one side in the thickness direction). In addition, the lower side of the paper surface is the lower side (the other side in the thickness direction). In addition, the left-right direction and the depth direction of the paper surface are surface directions orthogonal to the up-down direction. Specifically, according to the direction arrows in each figure.

＜附防汙層之光學膜＞ 附防汙層之光學膜1有具有特定厚度之膜形狀(包含片材形狀)。附防汙層之光學膜1於與厚度方向正交之面方向上延伸。附防汙層之光學膜1具有平坦之上表面及平坦之下表面。 ＜Optical film with antifouling layer＞ The optical film 1 with an antifouling layer has a film shape (including a sheet shape) having a specific thickness. The optical film 1 with the antifouling layer extends in the plane direction orthogonal to the thickness direction. The optical film 1 with the antifouling layer has a flat upper surface and a flat lower surface.

如圖1所示，附防汙層之光學膜1朝厚度方向之一側依次具備基材層2、密接層3、光學功能層4及防汙層5。更具體而言，附防汙層之光學膜1具備基材層2、直接配置於基材層2之上表面(厚度方向上之一面)之密接層3、直接配置於密接層3之上表面(厚度方向上之一面)之光學功能層4、及直接配置於光學功能層4之上表面(厚度方向上之一面)之防汙層5。As shown in FIG. 1 , the antifouling layer-attached optical film 1 includes a base material layer 2 , an adhesive layer 3 , an optical function layer 4 and an antifouling layer 5 in this order toward one side in the thickness direction. More specifically, the antifouling layer-attached optical film 1 includes a base material layer 2 , an adhesive layer 3 directly disposed on the upper surface (one side in the thickness direction) of the base material layer 2 , and directly disposed on the upper surface of the adhesive layer 3 . The optical functional layer 4 (one surface in the thickness direction), and the antifouling layer 5 directly disposed on the upper surface (one surface in the thickness direction) of the optical functional layer 4 .

附防汙層之光學膜1之厚度例如為300 μm以下，較佳為200 μm以下，又，例如為1 μm以上，較佳為5 μm以上。The thickness of the antifouling layer-attached optical film 1 is, for example, 300 μm or less, preferably 200 μm or less, and, for example, 1 μm or more, or preferably 5 μm or more.

＜基材層＞ 基材層2係藉由防汙層5而被賦予有防汙性之被處理體。 <Substrate layer> The base material layer 2 is a to-be-processed object provided with the antifouling property by the antifouling layer 5 .

基材層2之全光線透過率(JIS K 7375-2008)例如為80%以上，較佳為85%以上。The total light transmittance (JIS K 7375-2008) of the base material layer 2 is, for example, 80% or more, preferably 85% or more.

基材層2朝厚度方向之一側依次具備基材10及硬塗層11。The base material layer 2 includes a base material 10 and a hard coat layer 11 in this order toward one side in the thickness direction.

＜基材＞ 基材10具有膜形狀。基材10具有可撓性。基材10係以與硬塗層11之下表面接觸之方式配置於硬塗層11之整個下表面。 ＜Substrate＞ The substrate 10 has a film shape. The base material 10 has flexibility. The substrate 10 is disposed on the entire lower surface of the hard coat layer 11 so as to be in contact with the lower surface of the hard coat layer 11 .

作為基材10，例如可例舉：高分子膜。As the base material 10, a polymer film is mentioned, for example.

作為高分子膜之材料，例如可例舉：聚酯樹脂、(甲基)丙烯酸樹脂、烯烴樹脂、聚碳酸酯樹脂、聚醚碸樹脂、聚芳酯樹脂、三聚氰胺樹脂、聚醯胺樹脂、聚醯亞胺樹脂、纖維素樹脂、及聚苯乙烯樹脂。作為聚酯樹脂，例如可例舉：聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、及聚萘二甲酸乙二酯。作為(甲基)丙烯酸樹脂，例如可例舉：聚甲基丙烯酸甲酯。作為烯烴樹脂，例如可例舉：聚乙烯、聚丙烯、及環烯烴聚合物。作為纖維素樹脂，例如可例舉：三乙醯纖維素。Examples of materials for the polymer film include polyester resins, (meth)acrylic resins, olefin resins, polycarbonate resins, polyether resins, polyarylate resins, melamine resins, polyamide resins, polyamide resins, and polyamide resins. Imide resin, cellulose resin, and polystyrene resin. As polyester resin, polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate are mentioned, for example. As (meth)acrylic resin, polymethyl methacrylate is mentioned, for example. As an olefin resin, polyethylene, a polypropylene, and a cycloolefin polymer are mentioned, for example. As a cellulose resin, triacetyl cellulose is mentioned, for example.

作為高分子膜之材料，較佳可例舉纖維素樹脂，更佳可例舉三乙醯纖維素。As a material of a polymer film, a cellulose resin is preferably mentioned, and a triacetyl cellulose is more preferable.

基材10之厚度例如為1 μm以上，較佳為5 μm以上，更佳為10 μm以上，又，例如為200 μm以下，較佳為150 μm以下，更佳為100 μm以下。The thickness of the base material 10 is, for example, 1 μm or more, preferably 5 μm or more, more preferably 10 μm or more, and, for example, 200 μm or less, preferably 150 μm or less, and more preferably 100 μm or less.

基材10之厚度可使用針盤量規(PEACOCK公司製造，「DG-205」)進行測定。The thickness of the base material 10 can be measured using a dial gauge (manufactured by PEACOCK, "DG-205").

＜硬塗層＞ 硬塗層11係用於抑制基材10上產生損傷之保護層。又，硬塗層11係可根據目的及用途而對基材10賦予防眩性之層。 ＜Hard Coating＞ The hard coat layer 11 is a protective layer for suppressing damage on the substrate 10 . Moreover, the hard-coat layer 11 is a layer which can provide anti-glare property to the base material 10 according to the objective and use.

硬塗層11例如由硬塗組合物形成。The hard coat layer 11 is formed of, for example, a hard coat composition.

硬塗組合物包含樹脂及粒子。即，硬塗層11包含樹脂及粒子。The hard coat composition contains resin and particles. That is, the hard coat layer 11 contains resin and particles.

作為樹脂，例如可例舉：熱塑性樹脂、及硬化性樹脂。作為熱塑性樹脂，例如可例舉：聚烯烴樹脂。As resin, a thermoplastic resin and a curable resin are mentioned, for example. As a thermoplastic resin, a polyolefin resin is mentioned, for example.

作為硬化性樹脂，例如可例舉：藉由活性能量射線(例如，紫外線、及電子束)之照射而硬化之活性能量射線硬化性樹脂、及藉由加熱而硬化之熱硬化性樹脂。作為硬化性樹脂，較佳可例舉：活性能量射線硬化性樹脂。Examples of curable resins include active energy ray curable resins cured by irradiation with active energy rays (eg, ultraviolet rays and electron beams), and thermosetting resins cured by heating. Preferable examples of the curable resin include active energy ray curable resins.

作為活性能量射線硬化性樹脂，例如可例舉：(甲基)丙烯酸系紫外線硬化性樹脂、聚胺基甲酸酯樹脂、三聚氰胺樹脂、醇酸樹脂、矽氧烷系聚合物、及有機矽烷縮合物。作為活性能量射線硬化性樹脂，較佳可例舉：(甲基)丙烯酸系紫外線硬化性樹脂。Examples of active energy ray-curable resins include (meth)acrylic-based ultraviolet curable resins, polyurethane resins, melamine resins, alkyd resins, siloxane-based polymers, and organosilane condensation thing. Preferable examples of the active energy ray-curable resin include (meth)acrylic-based ultraviolet curable resins.

又，樹脂例如可包含日本專利特開2008-88309號公報所記載之反應性稀釋劑。具體而言，樹脂可包含多官能(甲基)丙烯酸酯。Moreover, the resin may contain the reactive diluent described in Unexamined-Japanese-Patent No. 2008-88309, for example. Specifically, the resin may contain a polyfunctional (meth)acrylate.

作為粒子，例如可例舉：金屬氧化物微粒子及有機系微粒子。作為金屬氧化物微粒子之材料，例如可例舉：二氧化矽、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。作為金屬氧化物微粒子之材料，較佳可例舉：二氧化矽。即，作為金屬氧化物微粒子，較佳可例舉二氧化矽粒子，就將下述防汙層5之表面粗糙度Ra調整至下述特定範圍之觀點而言，更佳可例舉：奈米二氧化矽粒子。作為有機系微粒子之材料，可例舉：聚甲基丙烯酸甲酯、矽酮、聚苯乙烯、聚胺基甲酸酯、丙烯酸-苯乙烯共聚物、苯并胍胺、三聚氰胺、及聚碳酸酯。作為有機系微粒子之材料，較佳可例舉：矽酮、及聚甲基丙烯酸甲酯。As particles, for example, metal oxide fine particles and organic fine particles may be mentioned. As a material of metal oxide fine particles, for example, silicon dioxide, aluminum oxide, titanium oxide, zirconium oxide, calcium oxide, tin oxide, indium oxide, cadmium oxide, and antimony oxide can be mentioned. As the material of the metal oxide fine particles, preferably, silicon dioxide can be exemplified. That is, as the metal oxide fine particles, silicon dioxide particles are preferably used, and from the viewpoint of adjusting the surface roughness Ra of the antifouling layer 5 described below to the following specific range, nanometer particles are more preferably used. Silica particles. As the material of the organic fine particles, polymethyl methacrylate, silicone, polystyrene, polyurethane, acrylic-styrene copolymer, benzoguanamine, melamine, and polycarbonate may, for example, be mentioned. . As the material of the organic fine particles, preferably, silicone and polymethyl methacrylate can be mentioned.

粒子可單獨使用或併用2種以上。Particles can be used alone or in combination of two or more.

並且，藉由將粒子之調配比率及/或粒子之平均粒徑調整至特定比率，可將下述防汙層5之表面粗糙度Ra調整至下述特定之範圍。Furthermore, by adjusting the mixing ratio of the particles and/or the average particle diameter of the particles to a specific ratio, the surface roughness Ra of the antifouling layer 5 described below can be adjusted to the following specific range.

具體而言，粒子之調配比率相對於樹脂100質量份，例如為1質量份以上，較佳為3質量份以上，又，例如為30質量份以上，又，例如為20質量份以下。Specifically, the mixing ratio of the particles is, for example, 1 part by mass or more, preferably 3 parts by mass or more, for example, 30 parts by mass or more, and, for example, 20 parts by mass or less, relative to 100 parts by mass of the resin.

只要粒子之調配比率為上述上限以下，則可將下述防汙層5之表面粗糙度Ra調整至下述特定之範圍。The surface roughness Ra of the antifouling layer 5 described below can be adjusted to the following specific range as long as the mixing ratio of the particles is below the above upper limit.

粒子之平均粒徑例如為10 μm以下，較佳為8 μm以下，又，例如為1 nm以上。於使用奈米粒子作為粒子之情形時，粒子之平均粒徑例如為100 nm以下，較佳為70 nm以下，又，例如為1 nm以上。關於粒子之平均粒徑，例如可基於藉由雷射散射中之粒度分佈測定法求出之粒度分佈，以D50值(累積50%中值粒徑)之形式而求出。The average particle diameter of the particles is, for example, 10 μm or less, preferably 8 μm or less, and, for example, 1 nm or more. When using nanoparticles as the particles, the average particle diameter of the particles is, for example, 100 nm or less, preferably 70 nm or less, and, for example, 1 nm or more. The average particle diameter of the particles can be obtained, for example, as a D50 value (cumulative 50% median diameter) based on the particle size distribution obtained by the particle size distribution measurement method in laser scattering.

只要粒子之平均粒徑為上述範圍內，則可將下述防汙層5之表面粗糙度Ra調整至下述特定之範圍。As long as the average particle diameter of the particles is within the above range, the surface roughness Ra of the antifouling layer 5 described below can be adjusted to the following specific range.

又，可於硬塗組合物中視需要以適當之比率調配觸變賦予劑、光聚合起始劑、填充劑(例如，有機黏土)、及調平劑。又，硬塗組合物可藉由公知之溶劑進行稀釋。In addition, a thixotropy imparting agent, a photopolymerization initiator, a filler (eg, organoclay), and a leveling agent can be blended in the hard coating composition at an appropriate ratio as necessary. In addition, the hard coating composition can be diluted with a well-known solvent.

又，為了形成硬塗層11，詳情如下所述，將硬塗組合物之稀釋液塗佈於基材10之厚度方向上之一面，使之乾燥。乾燥後，例如藉由活性能量射線照射而使硬塗組合物硬化。Moreover, in order to form the hard-coat layer 11, the diluent of the hard-coat composition is apply|coated to one side in the thickness direction of the base material 10, and it is made to dry as described below. After drying, the hard coating composition is hardened, for example, by irradiation with active energy rays.

藉此，形成硬塗層11。Thereby, the hard coat layer 11 is formed.

硬塗層11之表面粗糙度Ra(詳細而言，硬塗層11之厚度方向上之一面之表面粗糙度Ra)例如為0.5 nm以上，又，例如為20 nm以下。The surface roughness Ra of the hard coat layer 11 (specifically, the surface roughness Ra of one surface in the thickness direction of the hard coat layer 11 ) is, for example, 0.5 nm or more, and, for example, 20 nm or less.

只要硬塗層11之表面粗糙度Ra為上述範圍內，則可將下述防汙層5之表面粗糙度Ra調整至下述特定之範圍。As long as the surface roughness Ra of the hard coat layer 11 is within the above-mentioned range, the surface roughness Ra of the antifouling layer 5 described below can be adjusted to the following specific range.

再者，表面粗糙度Ra例如可根據利用AFM(原子力顯微鏡)所得之1 μm見方之觀察圖像而求出(以下相同)。In addition, the surface roughness Ra can be calculated|required from the observation image of 1 micrometer square obtained by AFM (atomic force microscope), for example (it is the same below).

就耐擦損傷性之觀點而言，硬塗層11之厚度例如為0.1 μm以上，較佳為0.5 μm以上，更佳為3 μm以上，又，例如為50 μm以。硬塗層11之厚度例如可使用穿透式電子顯微鏡，藉由截面觀察進行測定。From the viewpoint of scratch resistance, the thickness of the hard coat layer 11 is, for example, 0.1 μm or more, preferably 0.5 μm or more, more preferably 3 μm or more, and, for example, 50 μm or more. The thickness of the hard coat layer 11 can be measured by cross-sectional observation using, for example, a transmission electron microscope.

＜密接層＞ 密接層3係用於確保基材層2與光學功能層4之間之密接力之層。 <Adhesive layer> The adhesive layer 3 is a layer for securing the adhesive force between the base material layer 2 and the optical functional layer 4 .

密接層3具有膜形狀。密接層3係以與基材層2(硬塗層11)之上表面接觸之方式配置於基材層2(硬塗層11)之整個上表面。The adhesive layer 3 has a film shape. The adhesive layer 3 is arranged on the entire upper surface of the base material layer 2 (hard coat layer 11 ) so as to be in contact with the upper surface of the base material layer 2 (hard coat layer 11 ).

作為密接層3之材料，例如可例舉：金屬。作為金屬，例如可例舉：矽、銦、鎳、鉻、鋁、錫、金、銀、鉑、鋅、鈦、鎢、鋯、及鈀。又，作為密接層3之材料，亦可例舉：上述金屬之2種以上之合金、及上述金屬之氧化物。As a material of the adhesion layer 3, a metal is mentioned, for example. Examples of the metal include silicon, indium, nickel, chromium, aluminum, tin, gold, silver, platinum, zinc, titanium, tungsten, zirconium, and palladium. Moreover, as a material of the adhesive layer 3, the alloy of 2 or more types of the said metal, and the oxide of the said metal can also be mentioned.

作為密接層3之材料，就密接性及透明性之觀點而言，較佳可例舉：氧化矽(SiO x)、及銦錫氧化物(ITO)。於使用氧化矽作為密接層3之材料之情形時，較佳為使用氧量比化學計量組成更少之SiO x，更佳為使用x為1.2以上1.9以下之SiO x。 As a material of the adhesive layer 3, from a viewpoint of adhesiveness and transparency, silicon oxide ( SiOx ) and indium tin oxide (ITO) are mentioned preferably. When silicon oxide is used as the material of the adhesion layer 3, it is preferable to use SiO x whose oxygen content is less than the stoichiometric composition, and it is more preferable to use SiO x whose x is 1.2 or more and 1.9 or less.

就兼顧基材層2與光學功能層4之間之密接力之確保、及密接層3之透明性之觀點而言，密接層3之厚度例如為1 nm以上，又，例如為10 nm以下。The thickness of the adhesive layer 3 is, for example, 1 nm or more and, for example, 10 nm or less, from the viewpoint of both securing the adhesion between the base material layer 2 and the optical functional layer 4 and the transparency of the adhesion layer 3 .

＜光學功能層＞ 於一實施方式中，光學功能層4係用於抑制外界光之反射強度之抗反射層。即，附防汙層之光學膜1係附防汙層之抗反射膜。 <Optical functional layer> In one embodiment, the optical functional layer 4 is an anti-reflection layer for suppressing the reflection intensity of external light. That is, the optical film 1 with an antifouling layer is an antireflection film with an antifouling layer.

光學功能層4(抗反射層)包含無機層，於厚度方向上交替地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。於抗反射層中，藉由其所包含之複數個薄層(高折射率層、低折射率層)中之複數個界面之反射光間之干擾作用，而使淨反射光強度衰減。又，於抗反射層中，藉由各薄層之光學膜厚(折射率與厚度之積)之調整，可表現出使反射光強度衰減之干擾作用。作為此種抗反射層之光學功能層4於本實施方式中，具體而言，朝厚度方向之一側依次具備第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 functional layer 4 (anti-reflection layer) includes an inorganic layer, and 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 at the interfaces of the multiple thin layers (high refractive index layer, low refractive index layer) contained in the anti-reflection layer. In addition, in the anti-reflection 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. In the present embodiment, the optical functional layer 4 serving as such an antireflection layer specifically includes a first high refractive index layer 21 , a first low refractive index layer 22 and a second high refractive index layer in this order toward one side in the thickness direction. layer 23 and second 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。就兼顧高折射率與可見光之低吸收性之觀點而言，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)，較佳可例舉氧化鈮。即，較佳為第1低折射率層22之材料及第2低折射率層24之材料均為氧化鈮。 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 terms of 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 tin oxide (ATO), preferably niobium oxide. That is, it is preferable that the material of the first low refractive index layer 22 and the material of the second low refractive index layer 24 are both niobium oxide.

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，又，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，又，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。就兼顧低折射率與可見光之低吸收性之觀點而言，作為低折射率材料，例如可例舉：二氧化矽(SiO 2)、及氟化鎂，較佳為二氧化矽。即，較佳為第1低折射率層22之材料及第2低折射率層24之材料均為二氧化矽。 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. From the viewpoint of both low refractive index and low absorption of visible light, examples of the low refractive index material include silicon dioxide (SiO 2 ) and magnesium fluoride, and silicon dioxide is preferred. That is, it is preferable that the material of the first low refractive index layer 22 and the material of the second low refractive index layer 24 are both silicon dioxide.

尤其是，只要第2低折射率層24之材料為二氧化矽，則第2低折射率層24與防汙層5之間之密接性優異。In particular, as long as the material of the second low refractive index layer 24 is silicon dioxide, the adhesion between the second low refractive index layer 24 and the antifouling layer 5 is excellent.

第1低折射率層22之光學膜厚例如為15 nm以上，又，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，又，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，於光學功能層4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，又，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，又，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，又，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60 nm以上，較佳為80 nm以上，又，例如為150 nm以下，較佳為100 nm以下。In the optical functional layer 4, 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, or 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, 60 nm or more, preferably 80 nm or more, and, for example, 150 nm or less, or preferably 100 nm or less.

＜防汙層＞ 防汙層5係用於防止汙垢(例如，垢及指紋)附著於基材層2之厚度方向之一側之層。 ＜Anti-fouling layer＞ The antifouling layer 5 is a layer for preventing dirt (eg, dirt and fingerprints) from adhering to one side in the thickness direction of the base material layer 2 .

防汙層5具有膜形狀。防汙層5係以與光學功能層4之上表面接觸之方式配置於光學功能層4之整個上表面。The antifouling layer 5 has a film shape. The antifouling layer 5 is disposed on the entire upper surface of the optical functional layer 4 so as to be in contact with the upper surface of the optical functional layer 4 .

作為形成防汙層5之材料，可例舉：具有全氟聚醚基之烷氧基矽烷化合物。換言之，防汙層5包含具有全氟聚醚基之烷氧基矽烷化合物。防汙層5較佳為包含具有全氟聚醚基之烷氧基矽烷化合物。As a material for forming the antifouling layer 5, an alkoxysilane compound having a perfluoropolyether group may, for example, be mentioned. In other words, the antifouling layer 5 contains an alkoxysilane compound having a perfluoropolyether group. The antifouling layer 5 preferably contains an alkoxysilane compound having a perfluoropolyether group.

若防汙層5包含具有全氟聚醚基之烷氧基矽烷化合物，則使防汙層5之防汙性提高。When the antifouling layer 5 contains an alkoxysilane compound having a perfluoropolyether group, the antifouling property of the antifouling layer 5 is improved.

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。 R 1-R 2-X-(CH 2) l-Si(OR 3) 3(1) (於上述式(1)中，R 1表示1個以上之氫原子被氟原子取代之氟化烷基。R 2表示至少包含1個全氟聚醚基之重複結構之結構。R 3表示碳數1以上4以下之烷基。l表示1以上之整數) R 1表示1個以上之氫被氟原子取代之直鏈狀或支鏈狀之氟化烷基(碳數1以上20以下)。R 1較佳為表示烷基之氫原子全部被氟原子取代之全氟烷基。 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 ) l -Si(OR 3 ) 3 (1) (In the above formula (1), R 1 represents a fluorinated alkyl group in which one or more hydrogen atoms are substituted with fluorine atoms 。 R 2 represents a repeating structure containing at least one perfluoropolyether group. R 3 represents an alkyl group with a carbon number of 1 or more and 4 or less. 1 represents an integer of 1 or more) R 1 represents one or more hydrogen and fluorine atoms A substituted linear or branched fluorinated alkyl group (1 to 20 carbon atoms). R 1 is preferably a perfluoroalkyl group in which all hydrogen atoms of an alkyl group are substituted with fluorine atoms.

R 2表示至少包含1個全氟聚醚基之重複結構之結構。R 2較佳為表示包含2個全氟聚醚基之重複結構。 R 2 represents a structure of a repeating structure including at least one perfluoropolyether group. R 2 preferably represents a repeating structure comprising 2 perfluoropolyether groups.

作為全氟聚醚基之重複結構，例如可例舉：直鏈狀之全氟聚醚基之重複結構、及支鏈狀之全氟聚醚基之重複結構。作為直鏈狀之全氟聚醚基之重複結構，例如可例舉：-(OC nF 2n) m-(m表示1以上50以下之整數。n表示1以上20以下之整數。以下相同)。作為支鏈狀之全氟聚醚基之重複結構，例如可例舉：-(OC(CF 3) 2) m-、及-(OCF 2CF(CF 3)CF 2) m-。 As a repeating structure of a perfluoropolyether group, the repeating structure of a linear perfluoropolyether group, and the repeating structure of a branched perfluoropolyether group are mentioned, for example. As the repeating structure of the linear perfluoropolyether group, for example, -(OC n F 2n ) m -(m represents an integer of 1 or more and 50 or less. n represents an integer of 1 or more and 20 or less. The same applies hereinafter) . Examples of the repeating structure of the branched perfluoropolyether group include -(OC(CF 3 ) 2 ) m - and -(OCF 2 CF(CF 3 )CF 2 ) m -.

作為全氟聚醚基之重複結構，較佳可例舉：直鏈狀之全氟聚醚基之重複結構，更佳可例舉：-(OCF 2) m-、及-(OC 2F 4) m-。 As the repeating structure of the perfluoropolyether group, preferably, the repeating structure of the linear perfluoropolyether group may be mentioned, more preferably, -(OCF 2 ) m - and -(OC 2 F 4 ) ) m- .

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

l表示1以上且20以下之整數，較佳為10以下之整數，更佳為5以下之整數。l進而較佳為表示3。l represents an integer of 1 or more and 20 or less, preferably an integer of 10 or less, more preferably an integer of 5 or less. l is more preferably expressed as 3.

此種具有全氟聚醚基之烷氧基矽烷化合物之中，較佳為可例舉：下述通式(2)所示之化合物。 CF 3-(OCF 2) P-(OC 2F 4) Q-O-(CH 2) 3-Si(OCH 3) 3(2) (於上述式(2)中，P表示1以上50以下之整數。Q表示1以上50以下之整數) Among the alkoxysilane compounds having such a perfluoropolyether group, a compound represented by the following general formula (2) can be preferably exemplified. CF 3 -(OCF 2 ) P -(OC 2 F 4 ) Q -O-(CH 2 ) 3 -Si(OCH 3 ) 3 (2) (In the above formula (2), P represents 1 or more and 50 or less Integer. Q represents an integer of 1 or more and 50 or less)

具有全氟聚醚基之烷氧基矽烷化合物亦可使用市售品。作為市售品，具體而言，可例舉：KY-1901(含全氟聚醚基之烷氧基矽烷化合物，信越化學工業公司製造)、OPTOOL UD120(含全氟聚醚基之烷氧基矽烷化合物)。A commercial item can also be used for the alkoxysilane compound which has a perfluoropolyether group. Specific examples of commercial products include: KY-1901 (perfluoropolyether group-containing alkoxysilane compound, manufactured by Shin-Etsu Chemical Co., Ltd.), OPTOOL UD120 (perfluoropolyether group-containing alkoxysilane compound) silane compounds).

又，藉由對形成防汙層5之材料進行變更，可將下述防汙層5之表面粗糙度Ra調整至下述特定之範圍。Moreover, by changing the material which forms the antifouling layer 5, the surface roughness Ra of the following antifouling layer 5 can be adjusted to the following specific range.

具有全氟聚醚基之烷氧基矽烷化合物可單獨使用或併用2種以上。The alkoxysilane compound having a perfluoropolyether group may be used alone or in combination of two or more.

防汙層5可藉由下述方法而形成。The antifouling layer 5 can be formed by the following method.

防汙層5之厚度例如為1 nm以上，較佳為5 nm以上，又，例如為30 nm以下，較佳為20 nm以下，更佳為15 nm以下。The thickness of the antifouling layer 5 is, for example, 1 nm or more, preferably 5 nm or more, and, for example, 30 nm or less, preferably 20 nm or less, and more preferably 15 nm or less.

只要防汙層5之厚度為上述下限以上，則可提高防汙層5之防汙性。The antifouling property of the antifouling layer 5 can be improved as long as the thickness of the antifouling layer 5 is equal to or more than the above lower limit.

只要防汙層5之厚度為上述上限以下，則當製造防汙層5時，可抑制不均。結果，使防汙層5之設計性提高。As long as the thickness of the antifouling layer 5 is equal to or less than the above upper limit, unevenness can be suppressed when the antifouling layer 5 is produced. As a result, the designability of the antifouling layer 5 is improved.

再者，防汙層5之厚度可藉由螢光X射線(Rigaku製造之ZXS PrimusII)進行測定。In addition, the thickness of the antifouling layer 5 can be measured by fluorescent X-ray (ZXS Primus II by Rigaku).

又，防汙層5之水接觸角例如為100°以上，較佳為110°以上，更佳為114°以上，又，例如為130°以下。Moreover, the water contact angle of the antifouling layer 5 is, for example, 100° or more, preferably 110° or more, more preferably 114° or more, and, for example, 130° or less.

只要防汙層5之水接觸角為上述下限以上，則可提高防汙層5之防汙性。As long as the water contact angle of the antifouling layer 5 is at least the above lower limit, the antifouling property of the antifouling layer 5 can be improved.

再者，關於防汙層5之水接觸角之測定方法，可藉由下述實施例詳細地進行描述。In addition, the measuring method of the water contact angle of the antifouling layer 5 can be described in detail by the following Example.

並且，於此種防汙層5中，表面粗糙度Ra為特定之範圍。And in such an antifouling layer 5, the surface roughness Ra is a specific range.

具體而言，防汙層5之表面粗糙度Ra為2 nm以上，較佳為3nm以上，更佳為5 nm以上，又，為15 nm以下，較佳為10 nm以下，更佳為7 nm以下。Specifically, the surface roughness Ra of the antifouling layer 5 is 2 nm or more, preferably 3 nm or more, more preferably 5 nm or more, and 15 nm or less, preferably 10 nm or less, more preferably 7 nm the following.

只要防汙層5之表面粗糙度Ra為上述下限以上，則即便照射紫外線，亦可抑制防汙層5對滑動之耐久性之降低。As long as the surface roughness Ra of the antifouling layer 5 is at least the above-mentioned lower limit, even if it is irradiated with ultraviolet rays, it is possible to suppress a decrease in the durability of the antifouling layer 5 to sliding.

另一方面，只要防汙層5之表面粗糙度Ra未達上述下限，則投錨效應變得不充分，防汙層5自光學功能層4剝離，藉此，無法抑制防汙層5對滑動之耐久性之降低。On the other hand, as long as the surface roughness Ra of the antifouling layer 5 does not reach the above-mentioned lower limit, the anchoring effect becomes insufficient, and the antifouling layer 5 is peeled off from the optical functional layer 4, whereby the effect of the antifouling layer 5 on sliding cannot be suppressed. Decreased durability.

又，只要防汙層5之表面粗糙度Ra為上述上限以下，則即便照射紫外線，亦可抑制防汙層5對滑動之耐久性之降低。Moreover, as long as the surface roughness Ra of the antifouling layer 5 is equal to or less than the above-mentioned upper limit, even if it is irradiated with ultraviolet rays, the deterioration of the durability against sliding of the antifouling layer 5 can be suppressed.

另一方面，若防汙層5之表面粗糙度Ra超過上述上限，則紫外線對防汙層5之照射量增加，因此無法抑制防汙層5對滑動之耐久性之降低。On the other hand, if the surface roughness Ra of the antifouling layer 5 exceeds the upper limit, the irradiation amount of ultraviolet rays to the antifouling layer 5 increases, so that the durability against sliding of the antifouling layer 5 cannot be suppressed from decreasing.

將防汙層5之表面粗糙度Ra調整至上述特定之範圍，例如：將硬塗層11(硬塗組合物)中之粒子之種類及/或粒子之調配比率及/或粒子之平均粒徑調整至特定比率；及/或製備硬塗層11之表面粗糙度Ra；及/或將形成防汙層5之材料變更成特定材料；及/或將於光學功能層4配置防汙層5之方法變更成特定方法。Adjust the surface roughness Ra of the antifouling layer 5 to the above-mentioned specific range, for example: adjust the type of particles and/or the mixing ratio of the particles and/or the average particle size of the particles in the hard coat layer 11 (hard coating composition) and/or preparing the surface roughness Ra of the hard coat layer 11; and/or changing the material for forming the antifouling layer 5 to a specific material; and/or disposing the antifouling layer 5 on the optical functional layer 4 The method is changed to a specific method.

＜附防汙層之光學膜之製造方法＞ 參照圖2A～圖2D，對附防汙層之光學膜1之製造方法進行說明。 <Manufacturing method of optical film with antifouling layer> 2A-2D, the manufacturing method of the optical film 1 with an antifouling layer is demonstrated.

附防汙層之光學膜1之製造方法具備：第1步驟，其準備基材層2；第2步驟，其依次配置基材層2、密接層3及光學功能層4；及第3步驟，其於光學功能層4配置防汙層5。The manufacturing method of the optical film 1 with the antifouling layer comprises: a first step, which prepares a base material layer 2; a second step, which sequentially arranges the base material layer 2, the adhesive layer 3 and the optical function layer 4; and the third step, The antifouling layer 5 is arranged on the optical functional layer 4 .

(第1步驟) 於第1步驟中，準備基材層2。 (Step 1) In the first step, the base material layer 2 is prepared.

為了準備基材層2，首先，如圖2A所示，準備基材10。In order to prepare the base material layer 2, first, as shown in FIG. 2A, the base material 10 is prepared.

其次，如圖2B所示，於基材10配置硬塗層11。具體而言，於基材10之厚度方向上之一面配置硬塗層11。Next, as shown in FIG. 2B , the hard coat layer 11 is arranged on the base material 10 . Specifically, the hard coat layer 11 is arranged on one surface in the thickness direction of the base material 10 .

具體而言，於基材10之厚度方向上之一面塗佈硬塗組合物之稀釋液，使之乾燥。乾燥後，藉由紫外線照射使硬塗組合物硬化。藉此，於基材10之厚度方向上之一面形成硬塗層11。Specifically, a diluent of the hard coating composition is applied to one surface in the thickness direction of the substrate 10 and dried. After drying, the hard coat composition is hardened by ultraviolet irradiation. As a result, the hard coat layer 11 is formed on one surface in the thickness direction of the base material 10 .

(第2步驟) 於第2步驟中，如圖2C所示，於基材層2(硬塗層11)依次配置密接層3及光學功能層4。具體而言，於基材層2(硬塗層11)之厚度方向上之一面配置密接層3，其次，於密接層3之厚度方向上之一面配置光學功能層4。更具體而言，於基材層2(硬塗層11)之厚度方向上之一面配置密接層3，於密接層3之厚度方向上之一面配置第1高折射率層21，於第1高折射率層21之厚度方向上之一面配置第1低折射率層22，於第1低折射率層22之厚度方向上之一面配置第2高折射率層23，於第2高折射率層23之厚度方向上之一面配置第2低折射率層24。 (Step 2) In the second step, as shown in FIG. 2C , the adhesive layer 3 and the optical function layer 4 are sequentially arranged on the base material layer 2 (hard coat layer 11 ). Specifically, the adhesive layer 3 is arranged on one surface in the thickness direction of the base material layer 2 (hard coat layer 11 ), and then the optical functional layer 4 is arranged on one surface in the thickness direction of the adhesive layer 3 . More specifically, the adhesive layer 3 is arranged on one surface in the thickness direction of the base layer 2 (hard coat layer 11 ), the first high refractive index layer 21 is arranged on one surface in the thickness direction of the adhesive layer 3 , and the first high refractive index layer 21 is arranged on the surface of the adhesive layer 3 in the thickness direction. The first low-refractive index layer 22 is disposed on one surface of the refractive index layer 21 in the thickness direction, the second high-refractive index layer 23 is disposed on one surface of the first low-refractive index layer 22 in the thickness direction, and the second high-refractive index layer 23 The second low refractive index layer 24 is disposed on one surface in the thickness direction.

為了於基材層2依次配置密接層3及光學功能層4，就提高基材層2及密接層3之間之密接性之觀點而言，首先，對基材層2之表面實施表面處理。In order to arrange the adhesive layer 3 and the optical function layer 4 in this order on the base layer 2, from the viewpoint of improving the adhesiveness between the base layer 2 and the adhesive layer 3, first, the surface of the base layer 2 is subjected to surface treatment.

作為表面處理，例如可例舉：電暈處理、電漿處理、火焰處理、臭氧處理、底塗處理、輝光處理、及皂化處理。作為表面處理，較佳可例舉：電漿處理。As a surface treatment, a corona treatment, plasma treatment, flame treatment, ozone treatment, primer treatment, glow treatment, and saponification treatment are mentioned, for example. Preferable examples of the surface treatment include plasma treatment.

並且，作為於基材層2依次配置密接層3及光學功能層4之方法，例如可例舉：真空蒸鍍法、濺鍍法、層壓法、鍍覆法、及離子鍍覆法。作為依次配置各層之方法，較佳可例舉：濺鍍法。Moreover, as a method of arrange|positioning the adhesive layer 3 and the optical function layer 4 in this order on the base material layer 2, a vacuum vapor deposition method, a sputtering method, a lamination method, a plating method, and an ion plating method are mentioned, for example. As a method of arranging each layer in sequence, a sputtering method is preferably mentioned.

於濺鍍法中，於真空腔室內對向配置靶(各層(密接層3、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)之材料)及基材層2。其次，藉由供給氣體且自電源施加電壓，而使氣體離子加速並照射至靶，使靶材料自靶表面濺出。然後，使該靶材料形成之各層依次堆積於基材層2之表面。In the sputtering method, the target (each layer (the adhesion layer 3 , 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 22 ) is arranged to face each other in a vacuum chamber. rate layer 24)) and the base material layer 2. Next, by supplying gas and applying a voltage from a power source, gas ions are accelerated and irradiated to the target, so that the target material is sputtered from the target surface. Then, each layer formed of the target material is sequentially deposited on the surface of the base material layer 2 .

作為氣體，例如可例舉：惰性氣體。作為惰性氣體，例如可例舉：氬氣。又，例如，可視需要併用反應性氣體(例如氧氣)。於併用反應性氣體之情形時，反應性氣體之流量比(sccm)無特別限定。具體而言，相對於濺鍍氣體及反應性氣體之合計流量比，反應性氣體之流量比例如為0.1流量%以上100流量%以下。As a gas, an inert gas is mentioned, for example. As an inert gas, argon gas is mentioned, for example. Also, for example, a reactive gas (eg, oxygen) may be used in combination if necessary. When the reactive gas is used together, the flow ratio (sccm) of the reactive gas is not particularly limited. Specifically, the flow rate ratio of the reactive gas with respect to the total flow rate ratio of the sputtering gas and the reactive gas is, for example, 0.1 flow % or more and 100 flow % or less.

濺鍍時之氣壓例如為0.1 Pa以上，又，例如為1.0 Pa以下，較佳為0.7 Pa以下。The gas pressure at the time of sputtering is, for example, 0.1 Pa or more, and, for example, 1.0 Pa or less, or preferably 0.7 Pa or less.

電源例如可為DC(Direct Current，直流)電源、AC(Alternating Current，交流)電源、MF(Medium Frequency，中頻)電源、及RF(Radio Frequency，射頻)電源中之任一種。又，亦可為該等之組合。The power source may be, for example, any one of a DC (Direct Current, direct current) power source, an AC (Alternating Current, alternating current) power source, an MF (Medium Frequency, intermediate frequency) power source, and an RF (Radio Frequency, radio frequency) power source. Moreover, these combinations may be sufficient.

藉此，於基材層2之厚度方向上之一面依次配置密接層3及光學功能層4。Thereby, the adhesive layer 3 and the optical function layer 4 are arranged in this order on one surface in the thickness direction of the base material layer 2 .

(第3步驟) 於第3步驟中，如圖2D所示，於光學功能層4配置防汙層5。具體而言，於光學功能層4之厚度方向上之一面配置防汙層5。 (Step 3) In the third step, as shown in FIG. 2D , the antifouling layer 5 is arranged on the optical functional layer 4 . Specifically, the antifouling layer 5 is arranged on one surface in the thickness direction of the optical functional layer 4 .

作為於光學功能層4配置防汙層5之方法，例如可例舉：幹式塗佈法。作為幹式塗佈法，例如可例舉：真空蒸鍍法、濺鍍法及CVD(Chemical Vapor Deposition，化學氣相沈積)，就將防汙層5之表面粗糙度Ra調整至上述特定範圍之觀點而言，較佳可例舉：真空蒸鍍法。As a method of disposing the antifouling layer 5 on the optical functional layer 4, a dry coating method is mentioned, for example. Examples of dry coating methods include vacuum evaporation, sputtering, and CVD (Chemical Vapor Deposition). The surface roughness Ra of the antifouling layer 5 is adjusted to within the above-mentioned specific range. From a viewpoint, a vacuum deposition method is preferably mentioned.

藉此，於光學功能層4配置防汙層5。然後，可製造附防汙層之光學膜1，上述附防汙層之光學膜1朝厚度方向之一側依次具備基材層2、密接層3、光學功能層4及防汙層5。Thereby, the antifouling layer 5 is arranged on the optical functional layer 4 . Then, an antifouling layer-attached optical film 1 can be produced, which includes a substrate layer 2 , an adhesive layer 3 , an optical functional layer 4 , and an antifouling layer 5 in this order toward one side in the thickness direction.

並且，於該附防汙層之光學膜1中，防汙層5之表面粗糙度Ra為特定之範圍。因此，即便照射紫外線，亦可抑制防汙層5對滑動之耐久性之降低。In addition, in the optical film 1 with the antifouling layer, the surface roughness Ra of the antifouling layer 5 is in a specific range. Therefore, even if an ultraviolet-ray is irradiated, the fall of the durability to sliding of the antifouling layer 5 can be suppressed.

＜變化例＞ 於變化例中，對於與一實施方式相同之構件及步驟，標註相同之參照符號，省略其詳細之說明。又，變化例除特別記載以外，可發揮與第一實施方式相同之作用效果。進而，可適當地組合一實施方式及其變化例。 <Variation example> In the modified example, the same components and steps as in the first embodiment are marked with the same reference numerals, and detailed descriptions thereof are omitted. In addition, the modified example can exhibit the same functions and effects as those of the first embodiment unless otherwise specified. Furthermore, one embodiment and its modification examples can be appropriately combined.

於一實施方式中，基材層2朝厚度方向之一側依次具備基材10及硬塗層11。但，基材層2亦可包含基材10而不具備硬塗層11。In one embodiment, the base material layer 2 includes the base material 10 and the hard coat layer 11 in this order toward one side in the thickness direction. However, the base material layer 2 may include the base material 10 and not include the hard coat layer 11 .

於一實施方式中，附防汙層之光學膜1具備密接層3。但，附防汙層之光學膜1亦可不具備密接層3。於此種情形時，附防汙層之光學膜1朝厚度方向之一側依次具備基材層2、光學功能層4及防汙層5。In one embodiment, the optical film 1 with an antifouling layer includes an adhesive layer 3 . However, the optical film 1 with an antifouling layer may not include the adhesive layer 3 . In this case, the antifouling layer-attached optical film 1 includes the base material layer 2 , the optical function layer 4 and the antifouling layer 5 in this order toward one side in the thickness direction.

於一實施方式中，光學功能層4具備2層折射率相對較高之高折射率層，且具備2層折射率相對較低之低折射率層。但，高折射率層及低折射率層之數量無特別限定。In one embodiment, the optical functional layer 4 includes two high-refractive-index layers with relatively high refractive indices, and two low-refractive-index layers with relatively low refractive indices. However, the number of the high refractive index layer and the low refractive index layer is not particularly limited.

於一實施方式中，光學功能層4為抗反射層，但不限定於此。作為光學功能層4，例如可例舉：透明電極膜(ITO膜)、電磁波屏蔽層(具有電磁波反射能力之金屬薄膜)。 [實施例] In one embodiment, the optical functional layer 4 is an anti-reflection layer, but is not limited thereto. As the optical functional layer 4 , for example, a transparent electrode film (ITO film) and an electromagnetic wave shielding layer (a metal thin film having electromagnetic wave reflection ability) can be mentioned. [Example]

以下表示實施例及比較例，更具體地對本發明進行說明。再者，本發明不限定於任何實施例及比較例。又，以下之記載中所使用之調配比率(含有比率)、物性值、參數等具體數值可替換為上述「實施方式」中所記載之與其等對應之調配比率(含有比率)、物性值、參數等之相應記載之上限值(定義為「以下」、「未達」之數值)或下限值(定義為「以上」、「超過」之數值)。Hereinafter, an Example and a comparative example are shown, and this invention is demonstrated more concretely. In addition, this invention is not limited to any Example and a comparative example. In addition, specific numerical values such as the blending ratio (content ratio), physical property value, and parameter used in the following description can be replaced by the blending ratio (content ratio), physical property value, and parameter corresponding to the blending ratio (content ratio), physical property value, and parameter described in the above-mentioned "Embodiment". The upper limit value (defined as the value of "below" and "less than") or the lower limit value (defined as the value of "above" and "exceeding") of the corresponding records.

1.附防汙層之光學膜之製造 實施例1 (第1步驟) 於作為透明樹脂膜之三乙醯纖維素(TAC)膜(厚度80 μm)之單面形成硬塗層。於本步驟中，首先，將紫外線硬化型丙烯酸系單體(商品名「GRANDIC PC-1070」，DIC公司製造)100質量份、含有作為粒子之奈米二氧化矽粒子之有機矽溶膠(商品名「MEK-ST-L」，奈米二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(奈米二氧化矽粒子換算量)、觸變賦予劑(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「OMNIRAD 907」，BASF公司製造)3質量份、及調平劑(商品名「LE303」，共榮社化學公司製造)0.15質量份加以混合，製備固形物成分濃度55質量%之組合物(清漆)。使用超音波分散機進行混合。其次，於上述TAC膜之單面塗佈組合物，形成塗膜。其次，藉由紫外線照射使該塗膜硬化後，藉由加熱使之乾燥。於紫外線照射中，使用高壓水銀燈作為光源，使用波長365 nm之紫外線，將累計照射光量設為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之硬塗層(第2 HC層)。藉此，獲得基材層(附HC層之TAC膜)。 1. Manufacture of the optical film with an antifouling layer Example 1 (1st step) A hard coat layer was formed on one side of a triacetyl cellulose (TAC) film (thickness 80 μm) as a transparent resin film. In this step, first, 100 parts by mass of an ultraviolet-curable acrylic monomer (trade name "GRANDIC PC-1070", manufactured by DIC Corporation) and an organosilicon sol containing nano-silica particles as particles (trade name "MEK-ST-L", the average primary particle size of nano-silica particles is 50 nm, the solid content concentration is 30% by mass, manufactured by Nissan Chemical Co., Ltd.) 25 parts by mass (in terms of nano-silica particles), Thixotropy imparting agent (trade name "Lucentite SAN", synthetic bentonite as organoclay, manufactured by Co-op Chemical Corporation) 1.5 parts by mass, photopolymerization initiator (trade name "OMNIRAD 907", manufactured by BASF Corporation) 3 mass part and 0.15 parts by mass of a leveling agent (trade name "LE303", manufactured by Kyoeisha Chemical Co., Ltd.) to prepare a composition (varnish) having a solid content concentration of 55% by mass. Mix using an ultrasonic disperser. Next, the composition is applied to one side of the above-mentioned TAC film to form a coating film. Next, after curing the coating film by ultraviolet irradiation, it is dried by heating. In the ultraviolet irradiation, 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 . Moreover, the heating time was set to 80 degreeC, and the heating temperature was set to 3 minutes. Thereby, a hard coat layer (second HC layer) having a thickness of 6 μm was formed on the TAC film. Thereby, a base material layer (TAC film with HC layer) was obtained.

(第2步驟) 其次，藉由卷對卷方式之電漿處理裝置，於1.0 Pa之真空氛圍下對附HC層之TAC膜之HC層表面進行電漿處理。於該電漿處理中，使用氬氣作為惰性氣體，將放電功率設為150 W。 (Step 2) Next, plasma treatment was performed on the surface of the HC layer of the TAC film with the HC layer under a vacuum atmosphere of 1.0 Pa by means of a roll-to-roll plasma treatment device. In this plasma treatment, argon gas was used as an inert gas, and the discharge power was set to 150 W.

其次，於電漿處理後之附HC層之TAC膜之HC層上依次形成密接層及抗反射層。具體而言，藉由卷對卷方式之濺鍍成膜裝置，於電漿處理後之附HC層之TAC膜之HC層上依次形成：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、及作為第2低折射率層之厚度85 nm之SiO 2層。於密接層之形成中，使用ITO靶，使用作為惰性氣體之氬氣、及相對於氬氣100體積份為10體積份之作為反應性氣體之氧氣，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(Model Free Adaptive Control，無模型自適應控制)濺鍍而成膜ITO層。實施例2中之第1高折射率層、第1低折射率層、第2高折射率層、及第2低折射率層之形成條件與比較例1中之第1高折射率層、第1低折射率層、第2高折射率層、及第2低折射率層之上述形成條件相同。 Next, an adhesion layer and an anti-reflection layer are sequentially formed on the HC layer of the TAC film with the HC layer after the plasma treatment. Specifically, by means of a roll-to-roll sputtering film-forming device, on the HC layer of the TAC film with the HC layer attached after the plasma treatment, indium tin oxide (ITO) with a thickness of 1.5 nm as the adhesion layer is sequentially formed. ) layer, a Nb 2 O 5 layer with a thickness of 12 nm as the first high refractive index layer, a SiO 2 layer with a thickness of 28 nm as the first low refractive index layer, and a Nb 2 O layer with a thickness of 100 nm as the second high refractive index layer 2 O 5 layer, and SiO 2 layer with a thickness of 85 nm as the second low refractive index layer. In the formation of the adhesive layer, an ITO target was used, argon as an inert gas, and 10 parts by volume of oxygen as a reactive gas relative to 100 parts by volume of argon were used, and the discharge voltage was set to 400 V to form a film. The indoor air pressure (film forming air pressure) was set to 0.2 Pa, and an ITO layer was formed by sputtering by MFAC (Model Free Adaptive Control). The formation conditions of the first high refractive index layer, the first low refractive index layer, the second high refractive index layer, and the second low refractive index layer in Example 2 are the same as those of the first high refractive index layer, the first high refractive index layer and the second low refractive index layer in Comparative Example 1. The above-mentioned formation conditions of the 1st low-refractive-index layer, the 2nd high-refractive-index layer, and the 2nd low-refractive-index layer are the same.

(第3步驟) 其次，於所形成之抗反射層上形成防汙層。具體而言，與比較例1中之第3步驟相同(作為蒸鍍源，使用對大金工業公司製造之「OPTOOL UD120」(含全氟聚醚基之烷氧基矽烷化合物)進行乾燥所獲得之固形物成分)。藉此，製造附防汙層之光學膜。 (Step 3) Next, an antifouling layer is formed on the formed antireflection layer. Specifically, it was the same as that of the third step in Comparative Example 1 (as a vapor deposition source, "OPTOOL UD120" (perfluoropolyether group-containing alkoxysilane compound) manufactured by Daikin Industries, Ltd. was used and dried. solid content). Thereby, the optical film with an antifouling layer was manufactured.

實施例2 以與實施例1相同之方式製造附防汙層之光學膜。 Example 2 An antifouling layer-attached optical film was produced in the same manner as in Example 1.

其中，如下所示變更第3步驟。However, the third step is changed as follows.

作為蒸鍍源，使用對信越化學工業公司製造之「KY-1901」(含全氟聚醚基之烷氧基矽烷化合物)進行乾燥所獲得之固形物成分。As a vapor deposition source, the solid content obtained by drying "KY-1901" (perfluoropolyether group-containing alkoxysilane compound) manufactured by Shin-Etsu Chemical Co., Ltd. was used.

實施例3 以與實施例1相同之方式製造附防汙層之光學膜。 Example 3 An antifouling layer-attached optical film was produced in the same manner as in Example 1.

其中，如下所示變更第1步驟。However, the first step is changed as follows.

(第1步驟) 將含奈米二氧化矽粒子之丙烯酸系單體組合物(商品名「NC035」，奈米二氧化矽粒子之平均一次粒徑為40 nm，固形物成分濃度50%，固形物成分中之奈米二氧化矽粒子之比率為60質量%，荒川化學工業公司製造)67質量份、紫外線硬化型之多官能丙烯酸酯(商品名「黏合劑A」，固形物成分濃度100%，荒川化學工業公司製造)33質量份、作為粒子之聚甲基丙烯酸甲酯粒子(商品名「Techpolymer」，平均粒徑3 μm，折射率1.525，積水化成品工業公司製造)3質量份、作為粒子之矽酮粒子(商品名「Tospearl 130」，平均粒徑3 μm，折射率1.42，邁圖高新材料日本有限公司製造)1.5質量份、觸變賦予劑(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「OMNIRAD 907」，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、及甲苯加以混合，製備固形物成分濃度45質量%之組合物(清漆)。使用超音波分散機進行混合。其次，於上述TAC膜之單面塗佈組合物，形成塗膜。其次，藉由紫外線照射使該塗膜硬化後，藉由加熱使之乾燥。於紫外線照射中，使用高壓水銀燈作為光源，使用波長365 nm之紫外線，將累計照射光量設為200 mJ/cm 2。又，加熱時間設為60℃，加熱溫度設為60秒。藉此，於TAC膜上形成厚度7 μm之防眩性硬塗層(第3 HC層)。藉此，獲得基材層(附HC層之TAC膜)。 (Step 1) The acrylic monomer composition containing nano-silica particles (trade name "NC035", the average primary particle size of the nano-silica particles is 40 nm, the solid content concentration is 50%, the solid The ratio of nano-silica particles in the material component is 60% by mass, manufactured by Arakawa Chemical Industry Co., Ltd.) 67 parts by mass, UV-curable polyfunctional acrylate (trade name "Binder A", solid content concentration 100% , manufactured by Arakawa Chemical Industry Co., Ltd.) 33 parts by mass, polymethyl methacrylate particles (trade name "Techpolymer", average particle size 3 μm, refractive index 1.525, manufactured by Sekisui Chemical Industry Co., Ltd.) as particles 3 mass parts, as Silicone particles (trade name "Tospearl 130", average particle size 3 μm, refractive index 1.42, manufactured by Momentive Advanced Materials Japan Co., Ltd.) 1.5 parts by mass, thixotropy imparting agent (trade name "Lucentite SAN", as organic Clay synthetic bentonite, manufactured by Co-op Chemical Co.) 1.5 parts by mass, photopolymerization initiator (trade name "OMNIRAD 907", manufactured by BASF Corporation) 3 mass parts, leveling agent (trade name "LE303", Kyoei 0.15 mass part by the company chemical company) and toluene were mixed, and the composition (varnish) of 45 mass % of solid content concentration was prepared. Mix using an ultrasonic disperser. Next, the composition is applied to one side of the above-mentioned TAC film to form a coating film. Next, after curing the coating film by ultraviolet irradiation, it is dried by heating. In the ultraviolet irradiation, 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 made into 60 degreeC, and the heating temperature was made into 60 second. Thereby, an anti-glare hard coat layer (third HC layer) with a thickness of 7 μm was formed on the TAC film. Thereby, a base material layer (TAC film with HC layer) was obtained.

比較例1 (第1步驟) 於作為透明樹脂膜之三乙醯纖維素(TAC)膜(厚度80 μm)之單面形成防眩性硬塗層。於本步驟中，首先，將紫外線硬化型丙烯酸胺基甲酸酯(商品名「UV1700TL」，日本合成化學工業公司製造)50質量份、紫外線硬化型之多官能丙烯酸酯(商品名「Viscoat#300」，主成分為季戊四醇三丙烯酸酯，大阪有機化學工業公司製造)50質量份、作為粒子之聚甲基丙烯酸甲酯粒子(商品名「Techpolymer」，平均粒徑3 μm，折射率1.525，積水化成品工業公司製造)3質量份、作為粒子之矽酮粒子(商品名「Tospearl 130」，平均粒徑3 μm，折射率1.42，邁圖高新材料日本有限公司製造)1.5質量份、觸變賦予劑(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「OMNIRAD 907」，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、甲苯-乙酸乙酯-環戊酮混合溶劑(質量比35：41：24)加以混合，製備固形物成分濃度55質量%之組合物(清漆)。使用超音波分散機進行混合。 其次，於上述TAC膜之單面塗佈組合物，形成塗膜。其次，藉由紫外線照射使該塗膜硬化後，藉由加熱使之乾燥。於紫外線照射中，使用高壓水銀燈作為光源，使用波長365 nm之紫外線，將累計照射光量設為300 mJ/cm 2。又，加熱溫度設為80℃，加熱時間設為60秒。藉此，於TAC膜上形成厚度8 μm之防眩性硬塗層(第1 HC層)。藉此，獲得基材層(附HC層之TAC膜)。 Comparative Example 1 (1st step) An anti-glare hard coat layer was formed on one side of a triacetyl cellulose (TAC) film (thickness 80 μm) as a transparent resin film. In this step, first, 50 parts by mass of UV-curable urethane acrylate (trade name "UV1700TL", manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and UV-curable polyfunctional acrylate (trade name "Viscoat#300") were prepared. ”, the main component is pentaerythritol triacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 50 parts by mass, polymethyl methacrylate particles as particles (trade name “Techpolymer”, average particle size 3 μm, refractive index 1.525, hydrated 3 parts by mass of finished product industry company), 1.5 parts by mass of silicone particles (trade name "Tospearl 130", average particle size 3 μm, refractive index 1.42, Momentive High-tech Materials Japan Co., Ltd.), thixotropy imparting agent (trade name "Lucentite SAN", synthetic bentonite as organoclay, manufactured by Co-op Chemical Corporation) 1.5 parts by mass, photopolymerization initiator (trade name "OMNIRAD 907", manufactured by BASF Corporation) 3 mass parts, leveling 0.15 parts by mass of a solvent (trade name "LE303", manufactured by Kyōeisha Chemical Co., Ltd.) and a toluene-ethyl acetate-cyclopentanone mixed solvent (mass ratio 35:41:24) were mixed to prepare a solid content concentration of 55% by mass composition (varnish). Mix using an ultrasonic disperser. Next, the composition is applied to one side of the above-mentioned TAC film to form a coating film. Next, after curing the coating film by ultraviolet irradiation, it is dried by heating. In the ultraviolet irradiation, a high pressure mercury lamp was used as a light source, and ultraviolet rays having a wavelength of 365 nm were used, and the cumulative irradiation light amount was set to 300 mJ/cm 2 . In addition, the heating temperature was 80 degreeC, and the heating time was 60 second. Thereby, an anti-glare hard coat layer (1st HC layer) with a thickness of 8 μm was formed on the TAC film. Thereby, a base material layer (TAC film with HC layer) was obtained.

(第2步驟) 其次，藉由卷對卷方式之電漿處理裝置，於1.0 Pa之真空氛圍下對附HC層之TAC膜之HC層表面進行電漿處理。於該電漿處理中，使用氬氣作為惰性氣體，將放電功率設為2400 W。 (Step 2) Next, plasma treatment was performed on the surface of the HC layer of the TAC film with the HC layer under a vacuum atmosphere of 1.0 Pa by means of a roll-to-roll plasma treatment device. In this plasma treatment, argon gas was used as an inert gas, and the discharge power was set to 2400 W.

其次，於電漿處理後之附HC層之TAC膜之HC層上依次形成密接層及抗反射層。具體而言，藉由卷對卷方式之濺鍍成膜裝置，於電漿處理後之附HC層之TAC膜之HC層上依次形成：作為密接層之厚度3.5 nm之SiO x層(x＜2)、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、及作為第2低折射率層之厚度85 nm之SiO 2層。於密接層之形成中，使用Si靶，使用作為惰性氣體之氬氣、及相對於氬氣100體積份為3體積份之作為反應性氣體之氧氣，將放電電壓設為520 V，將成膜室內之氣壓(成膜氣壓)設為0.27 Pa，藉由MFAC濺鍍而成膜SiO x層(x＜2)。於第1高折射率層之形成中，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濺鍍而成膜Nb 2O 5層。於第1低折射率層之形成中，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濺鍍而成膜SiO 2層。於第2高折射率層之形成中，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濺鍍而成膜Nb 2O 5層。於第2低折射率層之形成中，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濺鍍而成膜SiO 2層。如上所示，於附HC層之TAC膜之HC層上經由密接層而積層並形成抗反射層(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 with the HC layer after the plasma treatment. Specifically, by means of a roll-to-roll sputtering film-forming device, on the HC layer of the TAC film with the HC layer attached after the plasma treatment, a layer of SiO x with a thickness of 3.5 nm as the adhesion layer (x< 2) 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 with a thickness of 100 nm as the second high refractive index layer 2 O 5 layer, and SiO 2 layer with a thickness of 85 nm as the second low refractive index layer. In the formation of the adhesive layer, a Si target was used, argon as an inert gas, and 3 parts by volume of oxygen as a reactive gas relative to 100 parts by volume of argon, and a discharge voltage of 520 V was used to form a film. The air pressure in the chamber (film formation air pressure) was set to 0.27 Pa, and a SiO x layer (x<2) was formed by MFAC sputtering. In the formation of 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 formation pressure was set to 0.42 Pa, and sputtered by MFAC. Plating to form a Nb 2 O 5 layer. In the formation of 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 formation pressure was set to 0.3 Pa, and sputtered by MFAC. Plating to form a SiO 2 layer. In the formation of 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 formation pressure was set to 0.5 Pa, and sputtered by MFAC. Plating to form a Nb 2 O 5 layer. In the formation of 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-forming pressure was set to 0.25 Pa, and sputtered by MFAC. Plating to form a SiO 2 layer. As described above, an antireflection layer (a first high refractive index layer, a first low refractive index layer, a second high refractive index layer, a second low refractive index layer, a first high refractive index layer, a first low refractive index layer, a second high refractive index layer, a second low refractive index layer).

(第3步驟) 其次，於所形成之抗反射層上形成防汙層。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，而於抗反射層上形成厚度7 nm之防汙層。蒸鍍源係對大金工業公司製造之「OPTOOL UD509」(上述通式(2)所表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%)進行乾燥所獲得之固形物成分。又，真空蒸鍍法中之蒸鍍源之加熱溫度設為260℃。 (Step 3) Next, an antifouling layer is formed on the formed antireflection layer. Specifically, an antifouling layer with a thickness of 7 nm was formed on the antireflection layer by a vacuum evaporation method using an alkoxysilane compound containing a perfluoropolyether group as an evaporation source. The vapor deposition source was obtained by drying "OPTOOL UD509" (a perfluoropolyether group-containing alkoxysilane compound represented by the general formula (2) above, solid content concentration 20 mass %) manufactured by Daikin Industries, Ltd. the solid content. In addition, the heating temperature of the vapor deposition source in the vacuum vapor deposition method was made into 260 degreeC.

藉此，製造附防汙層之光學膜。Thereby, the optical film with an antifouling layer was manufactured.

比較例2 以與實施例1相同之方式製造附防汙層之光學膜。 Comparative Example 2 An antifouling layer-attached optical film was produced in the same manner as in Example 1.

其中，如下所示變更第3步驟。 (第3步驟) 藉由稀釋溶劑(商品名「Fluorinert」，3M公司製造)稀釋作為塗佈劑之「OPTOOL UD509」(大金工業公司製造)，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第2步驟所形成之抗反射層之上，形成塗膜。其次，於60℃下藉由2分鐘之加熱使該塗膜乾燥。藉此，於抗反射層上形成厚度7 nm之防汙層。 However, the third step is changed as follows. (Step 3) "OPTOOL UD509" (manufactured by Daikin Industries, Ltd.) as a coating agent was diluted with a dilution solvent (trade name "Fluorinert", manufactured by 3M Corporation) to prepare a coating liquid with a solid content concentration of 0.1% by mass. Next, the coating liquid is coated on the antireflection layer formed in the second step by gravure coating 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.

2.評價 (表面粗糙度Ra) 對於各實施例及各比較例之附防汙層之光學膜之防汙層及硬塗層，研究防汙層之表面粗糙度Ra。具體而言，藉由原子力顯微鏡(商品名「SPI3800」，Seiko Instruments公司製造)觀察各附防汙層之光學膜之防汙層表面，於1 μm見方之觀察圖像中，求出表面粗糙度Ra(算術平均粗糙度)。將其結果示於表1。 2. Evaluation (Surface Roughness Ra) For the antifouling layer and the hard coat layer of the optical film with antifouling layer of each Example and each Comparative Example, the surface roughness Ra of the antifouling layer was investigated. Specifically, the surface of the antifouling layer of each antifouling layer-attached optical film was observed with an atomic force microscope (trade name "SPI3800", manufactured by Seiko Instruments Co., Ltd.), and the surface roughness was determined in the observed image of 1 μm square. Ra (arithmetic mean roughness). The results are shown in Table 1.

(水接觸角) 於各實施例及各比較例之附防汙層之光學膜中，對於防汙層，使用協和界面科學公司製造之DMo-501，基於以下條件，測定防汙層對純水之水接觸角(初始水接觸角)。將其結果示於表1。 (water contact angle) In the optical films with the antifouling layer of each example and each comparative example, for the antifouling layer, DMo-501 manufactured by Kyowa Interface Science Co., Ltd. was used, and the water contact angle of the antifouling layer to pure water was measured based on the following conditions ( initial water contact angle). The results are shown in Table 1.

＜測定條件＞ 液滴量：2 μl 溫度：25℃ 濕度：40% (耐久性試驗) [紫外線之照射] 將各實施例及各比較例之附防汙層之光學膜投入至岩崎電氣製造之Eye Super(SUV-W161)。然後，於下述條件下，自防汙層側實施紫外線照射。 <Measurement conditions> Droplet volume: 2 μl Temperature: 25℃ Humidity: 40% (durability test) [Ultraviolet radiation] The antifouling layer-attached optical films of each Example and each Comparative Example were put into Eye Super (SUV-W161) manufactured by Iwasaki Electric. Then, ultraviolet irradiation was performed from the antifouling layer side under the following conditions.

＜照射條件＞ BPT(Black Panel Thermometer，黑色面板溫度計)溫度：80℃ 濕度：45℃ 紫外線強度：150 mW/cm 2時間：32.5小時 <Irradiation conditions> BPT (Black Panel Thermometer) temperature: 80°C Humidity: 45°C UV intensity: 150 mW/cm 2 Time: 32.5 hours

[紫外線照射後之水接觸角之測定] 紫外線照射後，以與上述相同之方法，測定防汙層對純水之水接觸角(紫外線照射後之水接觸角)。將其結果示於表1。 [Measurement of water contact angle after ultraviolet irradiation] After ultraviolet irradiation, the water contact angle of the antifouling layer with respect to pure water (water contact angle after ultraviolet irradiation) was measured in the same manner as described above. The results are shown in Table 1.

[耐久性之觀察] 連續滴加異丙醇2 mL，使得紫外線照射後之試樣之表面不會乾燥，使固定於20 mm×20 mm之SUS製治具之聚酯擦拭布(Sanplatec製造之「Anticon Gold」)於柵格上滑動(負荷：1.5 kg，往返1000次)。其後，目測確認有無剝離。將其結果示於表1。 [Observation of Durability] 2 mL of isopropyl alcohol was continuously added dropwise so that the surface of the sample after ultraviolet irradiation would not dry, and a polyester wiping cloth (“Anticon Gold” manufactured by Sanplatec) fixed on a 20 mm × 20 mm SUS jig was placed on the surface. Sliding on the grid (load: 1.5 kg, 1000 round trips). Then, the presence or absence of peeling was confirmed visually. The results are shown in Table 1.

[表1] 表1 實施例、比較例No. 硬塗層 防汙層 Ra [nm] 初始水接觸角 (°) 紫外線照射後之水接觸角 (°) 初始水接觸角－紫外線照射後之水接觸角 (°) 耐久性 材料 防汙層形成方法 防汙層 HC層 實施例1 第2 HC層 UD120 真空蒸鍍法 5.01 5.0 114.2 111.1 3.1 無剝離 實施例2 第2 HC層 KY1901 真空蒸鍍法 5.64 5.0 114.6 111.9 2.7 無剝離 實施例3 第3 HC層 UD120 真空蒸鍍法 5.47 3.1 114.3 112.7 1.6 無剝離 比較例1 第1 HC層 UD509 真空蒸鍍法 17.7 1.2 120.1 106.2 13.9 有剝離 比較例2 第1 HC層 UD509 濕式塗佈 1.3 1.2 109.4 106 3 有剝離 [Table 1] Table 1 Example, Comparative Example No. hard coating Antifouling layer Ra [nm] Initial water contact angle (°) Water contact angle after UV irradiation (°) Initial water contact angle - water contact angle after UV irradiation (°) Durability Material Antifouling layer formation method Antifouling layer HC layer Example 1 Layer 2 HC UD120 Vacuum evaporation method 5.01 5.0 114.2 111.1 3.1 no peeling Example 2 Layer 2 HC KY1901 Vacuum evaporation method 5.64 5.0 114.6 111.9 2.7 no peeling Example 3 Layer 3 HC UD120 Vacuum evaporation method 5.47 3.1 114.3 112.7 1.6 no peeling Comparative Example 1 1st HC layer UD509 Vacuum evaporation method 17.7 1.2 120.1 106.2 13.9 have peeling Comparative Example 2 1st HC layer UD509 wet coating 1.3 1.2 109.4 106 3 have peeling

再者，上述發明係作為本發明之例示實施方式而提供，其等僅為例示，不應限定性地解釋。該技術領域之業者所知之本發明之變化例包含於下述申請專利範圍內。 [產業上之可利用性] In addition, the above-mentioned invention is provided as an exemplary embodiment of this invention, and it is only an illustration, and should not be interpreted restrictively. Variations of the present invention known to those skilled in the art are included within the scope of the following claims. [Industrial Availability]

本發明之附防汙層之光學膜例如適合用於附防汙層之抗反射膜、附防汙層之透明導電性膜、及附防汙層之電磁波屏蔽膜。The optical film with an antifouling layer of the present invention is suitable for, for example, an antireflection film with an antifouling layer, a transparent conductive film with an antifouling layer, and an electromagnetic wave shielding film with an antifouling layer.

1:附防汙層之光學膜 2:基材層 3:密接層 4:光學功能層 5:防汙層 10:基材 11:硬塗層 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 1: Optical film with antifouling layer 2: substrate layer 3: Adhesion layer 4: Optical functional layer 5: Antifouling layer 10: Substrate 11: Hard coating 21: 1st high refractive index layer 22: 1st low refractive index layer 23: Second high refractive index layer 24: Second low refractive index layer

圖1表示本發明之附防汙層之光學膜之一實施方式。 圖2A～圖2D表示本發明之附防汙層之光學膜之製造方法之一實施方式。圖2A表示第1步驟中準備基材之步驟。圖2B表示第1步驟中於基材配置硬塗層之第1步驟。圖2C表示於基材層依次配置密接層及光學功能層之第2步驟。圖2D表示於光學功能層配置防汙層之第3步驟。 FIG. 1 shows an embodiment of the optical film with an antifouling layer of the present invention. 2A to 2D show one embodiment of the method for manufacturing the optical film with an antifouling layer of the present invention. FIG. 2A shows the step of preparing the base material in the first step. FIG. 2B shows the first step of disposing the hard coat layer on the base material in the first step. FIG. 2C shows the second step of disposing the adhesive layer and the optical function layer in this order on the base material layer. FIG. 2D shows the third step of disposing the antifouling layer on the optical functional layer.

1:附防汙層之光學膜 1: Optical film with antifouling layer

2:基材層 2: substrate layer

3:密接層 3: Adhesion layer

4:光學功能層 4: Optical functional layer

5:防汙層 5: Antifouling layer

10:基材 10: Substrate

11:硬塗層 11: Hard coating

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

Claims (7)

一種附防汙層之光學膜，其朝厚度方向之一側依次具備基材層、包含無機層之光學功能層、及防汙層，且 上述防汙層之表面粗糙度Ra為2 nm以上15 nm以下。 An optical film with an antifouling layer, which is sequentially provided with a base material layer, an optical functional layer including an inorganic layer, and an antifouling layer toward one side in the thickness direction, and The surface roughness Ra of the antifouling layer is 2 nm or more and 15 nm or less. 如請求項1之附防汙層之光學膜，其中上述光學功能層為抗反射層。The optical film with an antifouling layer according to claim 1, wherein the above-mentioned optical functional layer is an antireflection layer. 如請求項2之附防汙層之光學膜，其中上述抗反射層交替地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。The optical film with an antifouling layer according to claim 2, wherein the antireflection 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. 如請求項1至3中任一項之附防汙層之光學膜，其中基材層朝厚度方向之一側依次具備基材及硬塗層。The optical film with an antifouling layer according to any one of claims 1 to 3, wherein the base material layer is provided with a base material and a hard coat layer in this order toward one side in the thickness direction. 如請求項4之附防汙層之光學膜，其中上述硬塗層包含金屬氧化物微粒子。The optical film with an antifouling layer according to claim 4, wherein the hard coat layer contains metal oxide fine particles. 如請求項5之附防汙層之光學膜，其中上述金屬氧化物微粒子為奈米二氧化矽粒子。The optical film with an antifouling layer according to claim 5, wherein the metal oxide fine particles are nano-silicon dioxide particles. 如請求項4之附防汙層之光學膜，其中上述硬塗層之厚度方向上之一面之表面粗糙度Ra為0.5 nm以上20 nm以下。The optical film with an antifouling layer according to claim 4, wherein the surface roughness Ra of one surface in the thickness direction of the hard coat layer is 0.5 nm or more and 20 nm or less.
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