TW202423682A - Anti-reflection film, method for manufacturing same, and image display device - Google Patents
Anti-reflection film, method for manufacturing same, and image display device Download PDFInfo
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- TW202423682A TW202423682A TW112136595A TW112136595A TW202423682A TW 202423682 A TW202423682 A TW 202423682A TW 112136595 A TW112136595 A TW 112136595A TW 112136595 A TW112136595 A TW 112136595A TW 202423682 A TW202423682 A TW 202423682A
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- Prior art keywords
- layer
- film
- reflection
- coating layer
- reflection film
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- 238000000034 method Methods 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 239000010408 film Substances 0.000 claims abstract description 173
- 239000000758 substrate Substances 0.000 claims abstract description 34
- 238000001514 detection method Methods 0.000 claims abstract description 23
- 239000010409 thin film Substances 0.000 claims abstract description 23
- 238000001228 spectrum Methods 0.000 claims abstract description 13
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical group [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 168
- 239000011247 coating layer Substances 0.000 claims description 77
- 229920005989 resin Polymers 0.000 claims description 44
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- 239000011859 microparticle Substances 0.000 claims description 23
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 22
- 229910001887 tin oxide Inorganic materials 0.000 claims description 22
- 238000004544 sputter deposition Methods 0.000 claims description 20
- 229910003437 indium oxide Inorganic materials 0.000 claims description 12
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 25
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- -1 ITO Chemical class 0.000 description 1
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
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- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
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- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
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- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
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- 239000010955 niobium Substances 0.000 description 1
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- 239000011368 organic material Substances 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
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- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
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- 150000004756 silanes Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
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- 238000009751 slip forming Methods 0.000 description 1
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- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- YRGLXIVYESZPLQ-UHFFFAOYSA-I tantalum pentafluoride Chemical compound F[Ta](F)(F)(F)F YRGLXIVYESZPLQ-UHFFFAOYSA-I 0.000 description 1
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- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/90—Other aspects of coatings
- C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
- C03C2217/948—Layers comprising indium tin oxide [ITO]
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Theoretical Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Human Computer Interaction (AREA)
- Inorganic Chemistry (AREA)
- Optics & Photonics (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Laminated Bodies (AREA)
- Optical Elements Other Than Lenses (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Position Input By Displaying (AREA)
Abstract
Description
本發明係關於一種抗反射膜及其製造方法。進而，本發明係關於一種具備抗反射膜之圖像顯示裝置。The present invention relates to an anti-reflection film and a manufacturing method thereof. Furthermore, the present invention relates to an image display device having the anti-reflection film.
為了提高顯示圖像之視認性，有時於液晶顯示器或有機EL(Electroluminescence，電致發光)顯示器等圖像顯示裝置之表面設置抗反射膜。抗反射膜於膜基材上具備包含折射率不同之複數個薄膜之抗反射層。使用無機氧化物等無機薄膜作為構成抗反射層之薄膜的抗反射膜由於折射率或膜厚之調整較容易，因此可實現較高之抗反射特性。In order to improve the visibility of displayed images, an anti-reflection film is sometimes provided on the surface of an image display device such as a liquid crystal display or an organic EL (Electroluminescence) display. The anti-reflection film has an anti-reflection layer including a plurality of thin films with different refractive indices on a film substrate. An anti-reflection film using an inorganic thin film such as an inorganic oxide as a thin film constituting the anti-reflection layer can achieve higher anti-reflection properties because the refractive index or film thickness can be adjusted more easily.
抗反射膜於樹脂膜上、或設置於樹脂膜之表面之硬塗層上具備包含無機薄膜之抗反射層，但樹脂膜或硬塗層等有機材料與無機薄膜之層間密接力較小。因此，提出於膜基材之表面設置無機氧化物底塗層，且於該無機氧化物底塗層上形成抗反射層，以提高抗反射層於膜基材上之密接性。The anti-reflection film has an anti-reflection layer including an inorganic thin film on a resin film or a hard coating layer disposed on the surface of the resin film, but the interlayer adhesion between organic materials such as the resin film or the hard coating layer and the inorganic thin film is relatively weak. Therefore, it is proposed to dispose an inorganic oxide undercoat layer on the surface of the film substrate and to form an anti-reflection layer on the inorganic oxide undercoat layer to improve the adhesion of the anti-reflection layer on the film substrate.
例如，專利文獻1中揭示有一種抗反射膜，其於硬塗層上設置氧化銦錫(ITO)等氧化銦系底塗層，且於該氧化銦系底塗層上形成包含複數個薄膜之抗反射層。 [先前技術文獻] [專利文獻] For example, Patent Document 1 discloses an anti-reflection film in which an indium oxide-based base coating layer such as indium tin oxide (ITO) is provided on a hard coating layer, and an anti-reflection layer including a plurality of thin films is formed on the indium oxide-based base coating layer. [Prior Art Document] [Patent Document]
[專利文獻1]國際公開第2021/106788號[Patent Document 1] International Publication No. 2021/106788
[發明所欲解決之問題][The problem the invention is trying to solve]
由於ITO具有導電性，因此具備ITO底塗層之抗反射膜具有抗靜電性，可抑制由靜電引起之觸控感測器之誤動作。但是，關於在具備觸控感測器之圖像顯示面板之視認側表面配置有抗反射膜之圖像顯示裝置，於抗反射膜之底塗層為ITO等導電性材料之情形時，於室外使用時，觸控感測器之檢測可能會發生異常，而難以進行或無法進行觸控操作。Since ITO is conductive, the anti-reflection film with an ITO base coat has anti-static properties, which can suppress malfunction of the touch sensor caused by static electricity. However, in the case of an image display device with an anti-reflection film on the viewing side of the image display panel with a touch sensor, if the base coat of the anti-reflection film is a conductive material such as ITO, the touch sensor detection may be abnormal when used outdoors, making it difficult or impossible to perform touch operations.
鑒於上述情況，本發明之目的在於提供一種抗反射膜，該抗反射膜於應用於具備觸控感測器之圖像顯示裝置之情形時，不易發生觸控檢測之異常。 [解決問題之技術手段] In view of the above situation, the purpose of the present invention is to provide an anti-reflection film, which is less likely to cause abnormal touch detection when applied to an image display device equipped with a touch sensor. [Technical means to solve the problem]
本發明人等對在室外使用圖像顯示裝置時發生觸控感測器之檢測異常之原因進行了研究，結果判明抗反射膜之底塗層之電阻由於紫外線照射而暫時變化，推測其係觸控檢測異常之一個原因。基於該推測進行了進一步研究，結果發現藉由抗反射膜具備特定之底塗層，可抑制紫外線下之觸控感測器之檢測異常。The inventors of the present invention studied the cause of abnormal detection of the touch sensor when the image display device is used outdoors, and found that the resistance of the bottom coating layer of the anti-reflection film temporarily changes due to ultraviolet irradiation, and speculated that this is one of the causes of the abnormal touch detection. Based on this speculation, further research was conducted, and it was found that by having a specific bottom coating layer of the anti-reflection film, the abnormal detection of the touch sensor under ultraviolet light can be suppressed.
本發明之一實施方式係關於一種抗反射膜，該抗反射膜於透明膜基材之一主面上具備底塗層、及抗反射層。抗反射層係折射率不同之複數個薄膜之積層體。抗反射膜亦可於抗反射層上具備防眩層。One embodiment of the present invention is an anti-reflection film, which has a base coat layer and an anti-reflection layer on a main surface of a transparent film substrate. The anti-reflection layer is a laminate of multiple thin films with different refractive indices. The anti-reflection film may also have an anti-glare layer on the anti-reflection layer.
底塗層係氧化銦錫(ITO)層。底塗層之厚度較佳為0.5～10 nm。於ITO底塗層中，相對於氧化銦與氧化錫之合計，氧化錫之量較佳為5～60重量%。ITO底塗層較佳為X射線電子分光光譜之532 eV之峰強度為530 eV之峰強度之0.93倍以下。The base coating layer is an indium tin oxide (ITO) layer. The thickness of the base coating layer is preferably 0.5 to 10 nm. In the ITO base coating layer, the amount of tin oxide is preferably 5 to 60% by weight relative to the total amount of indium oxide and tin oxide. The peak intensity of the ITO base coating layer at 532 eV in the X-ray electron spectroscopy is preferably less than 0.93 times the peak intensity at 530 eV.
底塗層之表面電阻R 0較佳為1×10 8～5×10 11Ω/sq。以1.6 W/m 2之輻射強度照射1分鐘紫外線後之底塗層之表面電阻R 1與照射紫外線前之底塗層之表面電阻R 0之比R 0/R 1較佳為100以下。 The surface resistance R 0 of the base coating is preferably 1×10 8 to 5×10 11 Ω/sq. The ratio R 0 /R 1 of the surface resistance R 1 of the base coating after irradiation with ultraviolet rays at a radiation intensity of 1.6 W/m 2 for 1 minute to the surface resistance R 0 of the base coating before irradiation is preferably 100 or less.
抗反射膜之透明膜基材可為於透明樹脂膜之一主面上具備硬塗層之硬塗膜。硬塗層包含硬化性樹脂之硬化物。硬塗層亦可進而包含微粒子。於透明膜基材為硬塗膜之情形時，較佳為底塗層與硬塗層相接而設置。The transparent film substrate of the anti-reflection film may be a hard coating film having a hard coating layer on one main surface of a transparent resin film. The hard coating layer includes a hardened material of a curable resin. The hard coating layer may further include microparticles. When the transparent film substrate is a hard coating film, it is preferred that the base coating layer and the hard coating layer are provided in contact with each other.
底塗層例如使用氧化物靶，藉由濺鍍法而成膜。抗反射層例如藉由濺鍍法而形成。抗反射層亦可藉由反應性濺鍍而成膜。The undercoat layer is formed by sputtering using, for example, an oxide target. The antireflection layer is formed by, for example, sputtering. The antireflection layer may also be formed by reactive sputtering.
抗反射膜適宜用作圖像顯示裝置之構成構件，例如配置於具備觸控感測器之圖像顯示裝置之視認側表面。 [發明之效果] The anti-reflection film is suitable for use as a component of an image display device, for example, arranged on the viewing side surface of an image display device with a touch sensor. [Effect of the invention]
本發明之抗反射膜由於在透明膜基材與抗反射層之間具備ITO底塗層，因此抗反射層之密接性優異，並且由於被賦予抗靜電性，因此可抑制由靜電引起之觸控感測器之誤動作。又，於室外使用圖像顯示裝置時等，即便於照射了紫外線之情形時，亦不易發生觸控感測器之誤動作。The anti-reflection film of the present invention has an ITO base coat between the transparent film substrate and the anti-reflection layer, so the anti-reflection layer has excellent adhesion, and because it is given anti-static properties, it can suppress malfunction of the touch sensor caused by static electricity. In addition, when the image display device is used outdoors, even when it is irradiated with ultraviolet rays, malfunction of the touch sensor is not likely to occur.
圖1係表示抗反射膜之積層構成例之剖視圖。抗反射膜101於透明膜基材1上具備底塗層3，於底塗層3上具備抗反射層5。抗反射層5係折射率不同之2層以上之無機薄膜之積層體。於圖1所示之抗反射膜101中，抗反射層5具有交替地積層高折射率層51、53及低折射率層52、54而成之構成。亦可於抗反射層5上設有防污層7。FIG. 1 is a cross-sectional view showing an example of a laminated structure of an antireflection film. The antireflection film 101 has a base coat 3 on a transparent film substrate 1, and an antireflection layer 5 on the base coat 3. The antireflection layer 5 is a laminate of two or more inorganic thin films having different refractive indices. In the antireflection film 101 shown in FIG. 1 , the antireflection layer 5 has a structure in which high refractive index layers 51, 53 and low refractive index layers 52, 54 are alternately laminated. An antifouling layer 7 may also be provided on the antireflection layer 5.
圖2係模式性地表示於圖像顯示面板8之視認側表面具備抗反射膜101之圖像顯示裝置之構成之剖視圖。於圖像顯示裝置201中，抗反射膜101經由適宜之黏著劑層2而貼合於圖像顯示面板8之視認側表面。圖像顯示面板8具有觸控感測器功能，於圖像顯示部81之視認側表面具備用於位置檢測之觸控感測器部85。FIG2 is a cross-sectional view schematically showing the structure of an image display device having an anti-reflection film 101 on the visual side surface of the image display panel 8. In the image display device 201, the anti-reflection film 101 is attached to the visual side surface of the image display panel 8 via an appropriate adhesive layer 2. The image display panel 8 has a touch sensor function, and has a touch sensor portion 85 for position detection on the visual side surface of the image display portion 81.
觸控感測器部85具備用於位置檢測之電極(未圖示)。當手指或觸控筆觸摸到圖像顯示裝置201之視認側表面(抗反射膜101之防污層7)時，電極之靜電電容發生變化。藉由檢測該靜電電容之變化，而檢測觸摸位置。The touch sensor unit 85 has an electrode (not shown) for position detection. When a finger or a stylus touches the visual side surface (the antifouling layer 7 of the antireflection film 101) of the image display device 201, the electrostatic capacitance of the electrode changes. By detecting the change in electrostatic capacitance, the touch position is detected.
[抗反射膜] ＜透明膜基材＞ 作為透明膜基材1，使用透明樹脂膜。透明膜基材1亦可為於透明樹脂膜10之一面具備硬塗層11者。透明膜基材1之全光線透過率較佳為80%以上，更佳為90%以上。透明膜基材1之厚度並無特別限定，基於強度或操作性等作業性、薄層性等之觀點考慮，較佳為5～300 μm左右，更佳為10～250 μm，進而較佳為20～200 μm。 [Anti-reflective film] <Transparent film substrate> As the transparent film substrate 1, a transparent resin film is used. The transparent film substrate 1 may also be a transparent resin film 10 having a hard coating layer 11 provided on one surface thereof. The total light transmittance of the transparent film substrate 1 is preferably 80% or more, more preferably 90% or more. The thickness of the transparent film substrate 1 is not particularly limited, but is preferably about 5 to 300 μm, more preferably 10 to 250 μm, and further preferably 20 to 200 μm, from the perspective of workability such as strength or operability, and thinness.
(透明樹脂膜) 作為構成透明樹脂膜10之樹脂材料，較佳為透明性、機械強度、及熱穩定性優異之樹脂材料。作為樹脂材料之具體例，可例舉：三乙醯纖維素等纖維素系樹脂、聚酯系樹脂、聚醚碸系樹脂、聚碸系樹脂、聚碳酸酯系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、聚烯烴系樹脂、(甲基)丙烯酸系樹脂、環狀聚烯烴系樹脂(降𦯉烯系樹脂)、聚芳酯系樹脂、聚苯乙烯系樹脂、聚乙烯醇系樹脂、及其等之混合物。 (Transparent resin film) As the resin material constituting the transparent resin film 10, it is preferred to use a resin material having excellent transparency, mechanical strength, and thermal stability. Specific examples of the resin material include: cellulose resins such as triacetyl cellulose, polyester resins, polyether sulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth)acrylic resins, cyclic polyolefin resins (northene resins), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, and mixtures thereof.
(硬塗層) 藉由在透明樹脂膜10之抗反射層形成面設置硬塗層11，可提高抗反射膜之表面硬度或耐擦傷性等機械特性。亦可於透明樹脂膜10之背面側亦設有硬塗層(未圖示)。 (Hard coating layer) By providing a hard coating layer 11 on the anti-reflection layer forming surface of the transparent resin film 10, the mechanical properties such as the surface hardness or scratch resistance of the anti-reflection film can be improved. A hard coating layer can also be provided on the back side of the transparent resin film 10 (not shown).
作為構成硬塗層11之硬化性樹脂，可例舉：熱硬化型樹脂、光硬化型樹脂、電子束硬化型樹脂等。作為硬化性樹脂之種類，可例舉：聚酯系、丙烯酸系、胺基甲酸酯系、丙烯酸胺基甲酸酯系、醯胺系、矽酮系、矽酸鹽系、環氧系、三聚氰胺系、氧雜環丁烷系、丙烯酸胺基甲酸酯系等。該等之中，就硬度較高、能夠進行光硬化而言，較佳為丙烯酸系樹脂、丙烯酸胺基甲酸酯系樹脂、及環氧系樹脂，其中較佳為丙烯酸胺基甲酸酯系樹脂。Examples of the curable resin constituting the hard coating layer 11 include thermosetting resins, light curing resins, electron beam curing resins, etc. Examples of the types of curable resins include polyester resins, acrylic resins, urethane resins, acrylic urethane resins, amide resins, silicone resins, silicate resins, epoxy resins, melamine resins, cyclohexane resins, acrylic urethane resins, etc. Among these, acrylic resins, acrylic urethane resins, and epoxy resins are preferred in terms of their high hardness and ability to be light cured, and acrylic urethane resins are preferred.
光硬化性樹脂組合物包含具有兩個以上光聚合性(較佳為紫外線聚合性)官能基之多官能化合物。多官能化合物可為單體或低聚物。作為光聚合性之多官能化合物，可較佳地使用在1分子中包含兩個以上(甲基)丙烯醯基之化合物(多官能(甲基)丙烯酸酯)。The photocurable resin composition includes a multifunctional compound having two or more photopolymerizable (preferably UV-polymerizable) functional groups. The multifunctional compound may be a monomer or an oligomer. As the photopolymerizable multifunctional compound, a compound having two or more (meth)acrylic groups in one molecule (multifunctional (meth)acrylate) may be preferably used.
硬塗層11可包含微粒子。藉由硬塗層包含微粒子，可調整表面形狀，可使硬塗層具有賦予防眩性等光學特性或提高抗反射層之密接性等作用。The hard coating layer 11 may contain fine particles. By containing fine particles in the hard coating layer, the surface shape can be adjusted, and the hard coating layer can have the effects of imparting optical properties such as anti-glare or improving the adhesion of the anti-reflection layer.
作為微粒子，可無特別限制地使用氧化矽、氧化鋁、氧化鈦、氧化鋯、氧化鈣、氧化錫、氧化銦、氧化鎘、氧化銻等無機氧化物微粒子、玻璃微粒子、包含聚甲基丙烯酸甲酯、聚苯乙烯、聚胺基甲酸酯、丙烯酸-苯乙烯共聚物、苯并胍胺、三聚氰胺、聚碳酸酯等透明聚合物之交聯或未交聯之有機系微粒子、矽酮系微粒子等。As the microparticles, inorganic oxide microparticles such as silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, calcium oxide, tin oxide, indium oxide, cadmium oxide, and antimony oxide, glass microparticles, cross-linked or non-cross-linked organic microparticles containing transparent polymers such as polymethyl methacrylate, polystyrene, polyurethane, acrylic-styrene copolymer, benzoguanamine, melamine, and polycarbonate, silicone microparticles, etc. can be used without particular limitation.
微粒子之平均粒徑(平均一次粒徑)較佳為10 nm～10 μm左右。微粒子根據粒徑，可大致區分成具有0.5 μm～10 μm左右之次微米或微米級之平均粒徑之微粒子(以下有時會記載為「微米粒子」)、具有10 nm～100 nm左右之平均粒徑之微粒子(以下有時會記載為「奈米粒子」)、及具有微米粒子與奈米粒子之中間之粒徑之微粒子。The average particle size (average primary particle size) of microparticles is preferably about 10 nm to 10 μm. Based on the particle size, microparticles can be roughly divided into microparticles with an average particle size of about 0.5 μm to 10 μm or micron level (hereinafter sometimes referred to as "microparticles"), microparticles with an average particle size of about 10 nm to 100 nm (hereinafter sometimes referred to as "nanoparticles"), and microparticles with a particle size between microparticles and nanoparticles.
藉由硬塗層11包含奈米粒子，從而於表面形成微細之凹凸，有硬塗層11與底塗層3及抗反射層5之密接性提高之傾向。作為奈米粒子，較佳為無機微粒子，其中較佳為無機氧化物微粒子。其中，就折射率較低、可減少與黏合劑樹脂之折射率差而言，較佳為氧化矽粒子。By including nanoparticles in the hard coating layer 11, fine concavities and convexities are formed on the surface, and the adhesion between the hard coating layer 11 and the base coating layer 3 and the anti-reflection layer 5 tends to be improved. As nanoparticles, inorganic microparticles are preferred, and inorganic oxide microparticles are preferred. Among them, silicon oxide particles are preferred because they have a low refractive index and can reduce the refractive index difference with the binder resin.
基於在硬塗層11之表面形成與底塗層3等無機薄膜之密接性優異之凹凸形狀之觀點考慮，奈米粒子之平均一次粒徑較佳為20～80 nm，更佳為25～70 nm，進而較佳為30～60 nm。又，基於抑制硬塗層表面處之反射光之色差之觀點考慮，奈米粒子之平均一次粒徑較佳為55 nm以下，更佳為50 nm以下，進而較佳為45 nm以下。平均一次粒徑係藉由庫爾特計數法測定之重量平均粒徑。From the viewpoint of forming a concavo-convex shape with excellent adhesion to the inorganic thin film such as the base coating layer 3 on the surface of the hard coating layer 11, the average primary particle size of the nanoparticles is preferably 20 to 80 nm, more preferably 25 to 70 nm, and further preferably 30 to 60 nm. In addition, from the viewpoint of suppressing the chromatic aberration of reflected light at the surface of the hard coating layer, the average primary particle size of the nanoparticles is preferably 55 nm or less, more preferably 50 nm or less, and further preferably 45 nm or less. The average primary particle size is a weight average particle size measured by the Coulter counter method.
硬塗層11之奈米粒子之量相對於黏合劑樹脂100重量份，可為1～150重量份左右。基於在硬塗層11之表面形成與無機薄膜之密接性優異之表面形狀之觀點考慮，硬塗層11中奈米粒子之含量相對於黏合劑樹脂100重量份，較佳為20～100重量份，更佳為25～90重量份，進而較佳為30～80重量份。The amount of nanoparticles in the hard coating layer 11 may be about 1 to 150 parts by weight relative to 100 parts by weight of the binder resin. From the viewpoint of forming a surface shape with excellent adhesion to the inorganic thin film on the surface of the hard coating layer 11, the content of nanoparticles in the hard coating layer 11 is preferably 20 to 100 parts by weight, more preferably 25 to 90 parts by weight, and further preferably 30 to 80 parts by weight relative to 100 parts by weight of the binder resin.
藉由硬塗層11包含微米粒子，從而於硬塗層11之表面及其上形成之薄膜之表面形成直徑為次微米或微米級之突起，而賦予防眩性。微米粒子較佳為與硬塗層之黏合劑樹脂之折射率差較小，較佳為氧化矽等低折射率無機氧化物粒子、或聚合物微粒子。The hard coating layer 11 includes micron particles, thereby forming protrusions with a diameter of submicron or micron on the surface of the hard coating layer 11 and the surface of the film formed thereon, thereby imparting anti-glare properties. The micron particles preferably have a small refractive index difference with the binder resin of the hard coating layer, and are preferably low-refractive-index inorganic oxide particles such as silicon oxide, or polymer microparticles.
基於形成適合賦予防眩性之表面形狀之觀點考慮，微米粒子之平均一次粒徑較佳為1～8 μm，更佳為2～5 μm。於粒徑較小之情形時，有防眩性不足之傾向，於粒徑較大之情形時，有圖像之清晰度下降之傾向。硬塗層11中之微米粒子之含量並無特別限制，相對於黏合劑樹脂100重量份較佳為1～15重量份，更佳為2～10重量份，進而較佳為3～8重量份。From the viewpoint of forming a surface shape suitable for imparting anti-glare properties, the average primary particle size of the micron particles is preferably 1 to 8 μm, more preferably 2 to 5 μm. When the particle size is smaller, the anti-glare properties tend to be insufficient, and when the particle size is larger, the image clarity tends to decrease. The content of the micron particles in the hard coating layer 11 is not particularly limited, and is preferably 1 to 15 parts by weight, more preferably 2 to 10 parts by weight, and further preferably 3 to 8 parts by weight relative to 100 parts by weight of the binder resin.
硬塗層11可包含奈米粒子及微米粒子中之任一者，亦可包含兩者。又，亦可包含具有奈米粒子與微粒子之中間之粒徑之微米粒子。The hard coating layer 11 may include either nanoparticles or microparticles, or both. Furthermore, it may include microparticles having a particle size between nanoparticles and microparticles.
硬塗層形成用組合物包含硬化性樹脂，視需要亦可包含能夠溶解硬化性樹脂之溶劑。如上所述，硬塗層形成用組合物可包含微粒子。於硬化性樹脂為光硬化型樹脂之情形時，較佳為於組合物中包含光聚合起始劑。硬塗層形成用組合物亦可除上述以外，還包含調平劑、觸變劑、抗靜電劑、抗黏連劑、分散劑、分散穩定劑、抗氧化劑、紫外線吸收劑、消泡劑、增黏劑、界面活性劑、潤滑劑等添加劑。The composition for forming a hard coating layer includes a hardening resin and may include a solvent capable of dissolving the hardening resin as required. As described above, the composition for forming a hard coating layer may include microparticles. When the hardening resin is a photocuring resin, it is preferred that a photopolymerization initiator is included in the composition. In addition to the above, the composition for forming a hard coating layer may also include additives such as a leveling agent, a contact modifier, an antistatic agent, an anti-adhesive agent, a dispersant, a dispersion stabilizer, an antioxidant, an ultraviolet absorber, a defoaming agent, a thickening agent, a surfactant, and a lubricant.
藉由在膜基材上塗佈硬塗層形成用組合物，視需要進行溶劑之去除及樹脂之硬化，而形成硬塗層。作為硬塗層形成用組合物之塗佈方法，可採用棒式塗佈法、輥塗法、凹版塗佈法、桿式塗佈法、孔縫式塗佈法、淋幕式塗佈法、噴注式塗佈法、缺角輪塗佈法等任意適宜之方法。塗佈後之加熱溫度可根據硬塗層形成用組合物之組成等設定為適宜之溫度，例如50℃～150℃左右。於黏合劑樹脂成分為光硬化性樹脂之情形時，藉由照射紫外線等活性能量線進行光硬化。照射光之累計光量較佳為100～500 mJ/cm 2左右。 The hard coating layer is formed by coating the hard coating layer forming composition on the film substrate, removing the solvent and curing the resin as needed. As the coating method of the hard coating layer forming composition, any appropriate method such as rod coating, roller coating, gravure coating, rod coating, hole coating, curtain coating, spray coating, notch wheel coating, etc. can be adopted. The heating temperature after coating can be set to an appropriate temperature according to the composition of the hard coating layer forming composition, for example, about 50°C to 150°C. When the adhesive resin component is a photocurable resin, it is photocured by irradiating active energy rays such as ultraviolet rays. The cumulative light intensity of the irradiated light is preferably about 100 to 500 mJ/ cm2 .
硬塗層11之厚度並無特別限定，基於在實現較高之硬度之同時，適宜地控制表面形狀之觀點考慮，較佳為1～30 μm左右，亦可為2～20 μm或3～10 μm。The thickness of the hard coating layer 11 is not particularly limited. From the perspective of achieving a higher hardness and appropriately controlling the surface shape, the thickness is preferably about 1 to 30 μm, and may also be 2 to 20 μm or 3 to 10 μm.
＜底塗層＞ 於透明膜基材1上(硬塗層11上)形成底塗層3，於該底塗層3上形成抗反射層5。藉由以相接於硬塗層11上之方式設置底塗層3，以相接於底塗層3上之方式設置抗反射層5，從而獲得層間之密接性提高、不易產生抗反射層之剝離之抗反射膜。 <Undercoat> An undercoat 3 is formed on a transparent film substrate 1 (on a hard coat 11), and an antireflection layer 5 is formed on the undercoat 3. By providing the undercoat 3 in contact with the hard coat 11 and the antireflection layer 5 in contact with the undercoat 3, an antireflection film is obtained in which the adhesion between the layers is improved and the antireflection layer is not easily peeled off.
底塗層3係氧化銦錫(ITO)層。ITO透明性高，密接性優異。又，由於ITO導電性較高，因此藉由設置ITO底塗層，從而對抗反射膜賦予抗靜電性。ITO中之氧化銦之量較佳為40～95重量%，氧化錫之量較佳為5～60重量%。The base coating 3 is an indium tin oxide (ITO) layer. ITO has high transparency and excellent adhesion. In addition, since ITO has high conductivity, the anti-static property is imparted to the anti-reflective film by providing an ITO base coating. The amount of indium oxide in ITO is preferably 40 to 95% by weight, and the amount of tin oxide is preferably 5 to 60% by weight.
基於在使抗反射膜具有適度之抗靜電性之同時，適當地進行圖像顯示裝置之觸控感測器之檢測之觀點考慮，底塗層3之表面電阻R 0較佳為1×10 8～5×10 11Ω/sq，更佳為1×10 9～1×10 11Ω/sq，進而較佳為5×10 9～8×10 10Ω/sq。 From the viewpoint of making the anti-reflection film have appropriate antistatic properties and appropriately testing the touch sensor of the image display device, the surface resistance R 0 of the base coating layer 3 is preferably 1×10 8 to 5×10 11 Ω/sq, more preferably 1×10 9 to 1×10 11 Ω/sq, and further preferably 5×10 9 to 8×10 10 Ω/sq.
底塗層3之厚度例如為0.5～10 nm左右，較佳為1～8 nm。底塗層之厚度亦可為6 nm以下、5 nm以下、或4 nm以下。若底塗層之厚度為上述範圍，則可提高透明膜基材1與抗反射層5之密接性，同時可將表面電阻控制於適宜之範圍內。The thickness of the undercoat layer 3 is, for example, about 0.5 to 10 nm, preferably 1 to 8 nm. The thickness of the undercoat layer may also be less than 6 nm, less than 5 nm, or less than 4 nm. If the thickness of the undercoat layer is within the above range, the adhesion between the transparent film substrate 1 and the anti-reflection layer 5 can be improved, and the surface resistance can be controlled within an appropriate range.
底塗層3較佳為C1s光譜之532 eV之峰強度I 532為530 eV之峰強度I 530之0.93倍以下。I 532/I 530更佳為0.92以下，進而較佳為0.91以下，亦可為0.90以下。 The base coating layer 3 preferably has a peak intensity I532 at 532 eV of the C1s spectrum that is 0.93 times or less of the peak intensity I530 at 530 eV. I532 / I530 is more preferably 0.92 or less, further preferably 0.91 or less, and may be 0.90 or less.
關於ITO等氧化銦系金屬氧化物，於XPS之C1s光譜中，在530 eV附近出現正常之完全氧化物(In 2O 3及SnO 2)之峰頂。再者，此處之鍵結能係以C1s光譜之源自C-C鍵之峰頂之位置成為285 eV之方式進行移動而修正所得之值。 For indium oxide-based metal oxides such as ITO, the peak of normal complete oxides (In 2 O 3 and SnO 2 ) appears around 530 eV in the C1s spectrum of XPS. The bonding energy here is a corrected value obtained by shifting the position of the peak originating from the CC bond in the C1s spectrum to 285 eV.
於正常之完全氧化物之情況下，C1s光譜之532 eV之峰強度I 532處於530 eV(峰頂)之峰強度I 530之0.80～0.90倍之範圍內。當ITO中包含過量之氧時，於531～533 eV附近出現肩峰，532 eV之峰強度I 532相對於530 eV之峰強度I 530之比I 532/I 530增大。 In the case of a normal fully oxidized material, the peak intensity I532 at 532 eV of the C1s spectrum is in the range of 0.80 to 0.90 times the peak intensity I530 at 530 eV (peak top). When ITO contains excessive oxygen, a shoulder peak appears near 531 to 533 eV, and the ratio of the peak intensity I532 at 532 eV to the peak intensity I530 at 530 eV, I532 / I530 , increases.
底塗層3較佳為由紫外線照射引起之電阻變化較小。若對ITO等導電性之底塗層照射紫外線，則電阻可能會降低(導電性增高)。若抗反射膜之底塗層之電阻降低，則可能會發生觸控感測器部之檢測異常。有I 532/I 530越小、即過量之氧越少，則由紫外線照射引起之電阻變化越小之傾向，從而具備抗反射膜之圖像顯示裝置中之觸控感測器部之檢測異常越受到抑制。 The base coat 3 preferably has a smaller resistance change caused by ultraviolet irradiation. If a conductive base coat such as ITO is irradiated with ultraviolet rays, the resistance may decrease (conductivity increases). If the resistance of the base coat of the anti-reflection film decreases, detection abnormality of the touch sensor portion may occur. The smaller I532 / I530 is, that is, the less excess oxygen is, the smaller the resistance change caused by ultraviolet irradiation tends to be, so that the detection abnormality of the touch sensor portion in the image display device with the anti-reflection film is suppressed.
自抗反射層5形成面側以1.6 W/m 2之輻射強度向抗反射膜照射1分鐘紫外線後之底塗層3之表面電阻R 1較佳為照射紫外線之前之底塗層3之表面電阻R 0之0.01倍以上。換而言之，R 0/R 1較佳為100以下。 The surface resistance R1 of the base coating 3 after irradiating the antireflection film with ultraviolet rays at a radiation intensity of 1.6 W/ m2 for 1 minute is preferably 0.01 times or more the surface resistance R0 of the base coating 3 before irradiation with ultraviolet rays. In other words, R0 / R1 is preferably 100 or less.
R 0/R 1較佳為50以下，亦可為30以下、10以下、7以下、或5以下。於R 0/R 1較小，接近1之情形時，外光下(太陽光等紫外線下)之觸控感測器之檢測異常得到抑制。R 0/R 1之下限並無特別限定，一般為0.1以上，亦可為0.5以上、1以上、1.5以上、或2以上。 R 0 /R 1 is preferably less than 50, and may be less than 30, less than 10, less than 7, or less than 5. When R 0 /R 1 is small and close to 1, the detection abnormality of the touch sensor under external light (sunlight or other ultraviolet light) is suppressed. The lower limit of R 0 /R 1 is not particularly limited, and is generally greater than 0.1, and may be greater than 0.5, greater than 1, greater than 1.5, or greater than 2.
自抗反射層5形成面側以1.6 W/m 2之輻射強度向抗反射膜照射1分鐘紫外線後之底塗層3之表面電阻R 1較佳為7×10 7Ω/sq以上，更佳為1×10 8Ω/sq以上，亦可為5×10 8Ω/sq以上或1×10 9Ω/sq以上。R 1較佳為5×10 11Ω/sq以下，更佳為1×10 11Ω/sq以下，進而較佳為8×10 10Ω/sq以下，亦可為5×10 10Ω/sq以下或1×10 10Ω/sq以下。 The surface resistance R1 of the base coating layer 3 after irradiating the antireflection film with ultraviolet rays at a radiation intensity of 1.6 W/ m2 for 1 minute from the antireflection layer 5 formation side is preferably 7×10 7 Ω/sq or more, more preferably 1×10 8 Ω/sq or more, and may be 5×10 8 Ω/sq or more or 1×10 9 Ω/sq or more. R1 is preferably 5×10 11 Ω/sq or less, more preferably 1×10 11 Ω/sq or less, further preferably 8×10 10 Ω/sq or less, and may be 5×10 10 Ω/sq or less or 1×10 10 Ω/sq or less.
如上所述，有底塗層3之C1s光譜之峰強度比I 532/I 530越小，則紫外線照射時之電阻變化率R 0/R 1越小，觸控感測器部之檢測異常越受到抑制之傾向。有於ITO底塗層中，氧化錫之比率越高，成膜時之氧氣導入量越少，則I 532/I 530越小之傾向。 As described above, the smaller the peak intensity ratio I 532 /I 530 of the C1s spectrum of the base coating 3 is, the smaller the resistance change rate R 0 /R 1 is when irradiated with ultraviolet light, and the more the detection abnormality of the touch sensor part is suppressed. In the ITO base coating, the higher the ratio of tin oxide is, the less the amount of oxygen introduced during film formation is, and the smaller the I 532 /I 530 is.
基於減小I 532/I 530之觀點考慮，相對於氧化銦與氧化錫之合計，氧化錫之量更佳為5重量%以上，進而較佳為10重量%以上，亦可為15重量%以上或20重量%以上。另一方面，基於在使底塗層具有適度之導電性之同時確保透明性之觀點考慮，相對於氧化銦與氧化錫之合計，氧化錫之量較佳為60重量%以下，更佳為50重量%以下，亦可為40重量%以下或30重量%以下。 From the viewpoint of reducing I532 / I530 , the amount of tin oxide is preferably 5% by weight or more, more preferably 10% by weight or more, and may be 15% by weight or more or 20% by weight or more relative to the total of indium oxide and tin oxide. On the other hand, from the viewpoint of ensuring transparency while providing the base coating with appropriate conductivity, the amount of tin oxide is preferably 60% by weight or less, more preferably 50% by weight or less, and may be 40% by weight or less or 30% by weight or less relative to the total of indium oxide and tin oxide.
＜抗反射層＞ 抗反射層5係折射率不同之複數個薄膜之積層體。一般而言，抗反射層係以入射光與反射光之相反之相位彼此抵消之方式調整薄膜之光學膜厚(折射率與厚度之乘積)。藉由折射率不同之複數個薄膜之多層積層體，可於可見光之寬波段之波長範圍內減小反射率。作為構成抗反射層5之薄膜，較佳為無機材料，較佳為包含金屬或半金屬之氧化物、氮化物、氟化物等之陶瓷材料，其中較佳為金屬或半金屬之氧化物(無機氧化物)。 <Anti-reflection layer> The anti-reflection layer 5 is a laminate of multiple thin films with different refractive indices. Generally speaking, the anti-reflection layer adjusts the optical film thickness (the product of the refractive index and the thickness) of the thin film in such a way that the opposite phases of the incident light and the reflected light cancel each other out. By using a multi-layer laminate of multiple thin films with different refractive indices, the reflectivity can be reduced within a wide wavelength range of visible light. The thin film constituting the anti-reflection layer 5 is preferably an inorganic material, preferably a ceramic material including metal or semi-metal oxides, nitrides, fluorides, etc., among which metal or semi-metal oxides (inorganic oxides) are preferred.
抗反射層5較佳為高折射率層與低折射率層之交替積層體。為了減少空氣界面處之反射，作為抗反射層5之最外層(距離透明膜基材1最遠之層)而設置之薄膜54較佳為低折射率層。The anti-reflection layer 5 is preferably an alternating laminate of high refractive index layers and low refractive index layers. In order to reduce reflection at the air interface, the thin film 54 provided as the outermost layer of the anti-reflection layer 5 (the layer farthest from the transparent film substrate 1) is preferably a low refractive index layer.
高折射率層51、53之折射率例如為1.9以上，較佳為2.0以上。作為高折射率材料，可例舉：氧化鈦、氧化鈮、氧化鋯、氧化鉭、氧化鋅、氧化銦、氧化銦錫(ITO)、摻銻氧化錫(ATO)等。其中，較佳為氧化鈦或氧化鈮。低折射率層52、54之折射率例如為1.6以下，較佳為1.5以下。作為低折射率材料，可例舉：氧化矽、氮化鈦、氟化鎂、氟化鋇、氟化鈣、氟化鉿、氟化鑭等。其中，較佳為氧化矽。尤其是，較佳為交替地積層作為高折射率層之氧化鈮(Nb 2O 5)薄膜51、53、及作為低折射率層之氧化矽(SiO 2)薄膜52、54。亦可除了低折射率層及高折射率層以外，還設置折射率1.6～1.9左右之中折射率層。 The refractive index of the high refractive index layers 51 and 53 is, for example, 1.9 or more, preferably 2.0 or more. Examples of high refractive index materials include titanium oxide, niobium oxide, zirconium oxide, tantalum oxide, zinc oxide, indium oxide, indium tin oxide (ITO), antimony-doped tin oxide (ATO), etc. Among them, titanium oxide or niobium oxide is preferred. The refractive index of the low refractive index layers 52 and 54 is, for example, 1.6 or less, preferably 1.5 or less. Examples of low refractive index materials include silicon oxide, titanium nitride, magnesium fluoride, barium fluoride, calcium fluoride, tantalum fluoride, etc. Among them, silicon oxide is preferred. In particular, it is preferred to alternately laminate niobium oxide ( Nb2O5 ) thin films 51 and 53 as high refractive index layers and silicon oxide ( SiO2 ) thin films 52 and 54 as low refractive index layers. In addition to the low refractive index layer and the high refractive index layer, a medium refractive index layer having a refractive index of about 1.6 to 1.9 may be provided.
高折射率層及低折射率層之厚度分別為5～200 nm左右，較佳為15～150 nm左右。根據折射率或積層構成等，以可見光之反射率減小之方式設計各層之厚度即可。例如，作為高折射率層及低折射率層之積層構成，可例舉如下之四層構成，即，自透明膜基材1側起為光學膜厚25～55 nm左右之高折射率層51、光學膜厚35～55 nm左右之低折射率層52、光學膜厚80～240 nm左右之高折射率層53、及光學膜厚120～150 nm左右之低折射率層54。抗反射層並不限定於四層構成，亦可為兩層構成、三層構成、五層構成、或六層以上之積層構成。The thickness of the high refractive index layer and the low refractive index layer is about 5 to 200 nm, preferably about 15 to 150 nm. The thickness of each layer can be designed in a manner that reduces the reflectivity of visible light according to the refractive index or layered structure. For example, as a layered structure of the high refractive index layer and the low refractive index layer, the following four-layer structure can be cited, that is, from the transparent film substrate 1 side, a high refractive index layer 51 with an optical film thickness of about 25 to 55 nm, a low refractive index layer 52 with an optical film thickness of about 35 to 55 nm, a high refractive index layer 53 with an optical film thickness of about 80 to 240 nm, and a low refractive index layer 54 with an optical film thickness of about 120 to 150 nm. The anti-reflection layer is not limited to a four-layer structure, and may also be a two-layer structure, a three-layer structure, a five-layer structure, or a six-layer or more layer structure.
＜底塗層及抗反射層之成膜＞ 藉由在透明膜基材1上形成底塗層3及抗反射層5，從而形成抗反射膜。於透明膜基材1係於透明樹脂膜10之表面具備硬塗層11之硬塗膜之情形時，於硬塗層11上依序形成底塗層3及抗反射層5。 <Film formation of base coat layer and anti-reflection layer> An anti-reflection film is formed by forming a base coat layer 3 and an anti-reflection layer 5 on a transparent film substrate 1. When the transparent film substrate 1 is a hard coat film having a hard coat layer 11 on the surface of a transparent resin film 10, the base coat layer 3 and the anti-reflection layer 5 are sequentially formed on the hard coat layer 11.
亦可於形成底塗層及抗反射層之前，對膜基材1進行表面處理。作為表面處理，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、鹼處理、酸處理、利用偶合劑之處理等表面改質處理。亦可進行真空電漿處理作為表面處理。藉由表面處理，亦可調整硬塗層之表面粗糙度。例如，於包含微粒子之硬塗層11上形成底塗層3時，若以高放電功率對硬塗層11之表面進行電漿處理，則樹脂成分被蝕刻，使得微粒子露出於表面，因此，有硬塗層表面之表面凹凸增大，與薄膜之密接性提高之傾向。Before forming the primer layer and the anti-reflection layer, the film substrate 1 may be subjected to surface treatment. Examples of surface treatment include: corona treatment, plasma treatment, flame treatment, ozone treatment, primer treatment, radiant treatment, alkaline treatment, acid treatment, treatment using a coupling agent, and other surface modification treatments. Vacuum plasma treatment may also be performed as the surface treatment. The surface roughness of the hard coating layer may also be adjusted by surface treatment. For example, when forming the base coat 3 on the hard coat 11 containing microparticles, if the surface of the hard coat 11 is subjected to plasma treatment with high discharge power, the resin component is etched, so that the microparticles are exposed on the surface. Therefore, the surface roughness of the hard coat surface increases, and the adhesion with the film tends to be improved.
構成底塗層3及抗反射層5之薄膜之成膜方法並無特別限定，可為濕式塗佈法、乾式塗佈法之任一者。就能夠形成膜厚均勻之薄膜而言，較佳為真空蒸鍍、CVD(Chemical Vapor Deposition，化學氣相沉積)、濺鍍、電子束蒸鍍等乾式塗佈法。其中，就膜厚之均勻性優異，且容易形成緻密之膜而言，較佳為濺鍍法。The film forming method of the thin film constituting the base coating layer 3 and the anti-reflection layer 5 is not particularly limited, and may be any of a wet coating method and a dry coating method. In terms of being able to form a thin film with uniform film thickness, a dry coating method such as vacuum evaporation, CVD (Chemical Vapor Deposition), sputtering, and electron beam evaporation is preferred. Among them, sputtering is preferred in terms of excellent uniformity of film thickness and easy formation of a dense film.
於濺鍍法中，可藉由卷對卷方式，一面沿一個方向(長邊方向)搬送膜基材，一面連續使薄膜成膜。因此，可提高於透明膜基材1上具備底塗層3及包含複數個薄膜之抗反射層5之抗反射膜之生產性。In the sputtering method, a film can be continuously formed on the film substrate by a roll-to-roll method while the film substrate is transported in one direction (longitudinal direction). Therefore, the productivity of the anti-reflection film having the base coating layer 3 and the anti-reflection layer 5 including a plurality of thin films on the transparent film substrate 1 can be improved.
於濺鍍法中，一面向腔室內導入氬氣等惰性氣體、及視需要而定之氧氣等反應性氣體，一面進行成膜。關於藉由濺鍍法進行之氧化物層之成膜，可藉由使用氧化物靶之方法、及使用(半)金屬靶之反應性濺鍍之任一者來實施。In the sputtering method, film formation is performed while introducing an inert gas such as argon and, if necessary, a reactive gas such as oxygen into a chamber. The film formation of an oxide layer by sputtering can be performed by either a method using an oxide target or reactive sputtering using a (semi)metal target.
就能夠以高速率使無機氧化物成膜而言，構成抗反射層5之薄膜較佳為藉由使用金屬或半金屬靶之反應性濺鍍而成膜。用於反應性濺鍍之濺鍍電源較佳為DC(Direct Current，直流)或MF-AC(Multi-Frequency Alternating Current，多頻交流)。In order to form an inorganic oxide film at a high rate, the thin film constituting the anti-reflection layer 5 is preferably formed by reactive sputtering using a metal or semi-metal target. The sputtering power source used for reactive sputtering is preferably DC (Direct Current) or MF-AC (Multi-Frequency Alternating Current).
於反應性濺鍍中，一面向腔室內導入氬氣等惰性氣體及氧氣等反應性氣體，一面進行成膜。於反應性濺鍍中，較佳為以成為金屬區域與氧化物區域之中間之過渡區域之方式調整氧量。藉由以濺鍍成膜成為過渡區域之方式調整氧量，從而可以高速率使氧化物膜成膜。In reactive sputtering, an inert gas such as argon and a reactive gas such as oxygen are introduced into a chamber while film formation is performed. In reactive sputtering, it is preferred to adjust the amount of oxygen so as to form a transition region between a metal region and an oxide region. By adjusting the amount of oxygen so as to form a transition region by sputtering, an oxide film can be formed at a high rate.
底塗層之成膜較佳為使用氧化物靶。雖然使用金屬靶之反應性濺鍍具有成膜速度較快之優點，但膜之質量有時因成膜條件(成膜環境)之微小變化而顯著改變。另一方面，藉由使用氧化物靶，底塗層之膜之質量變得穩定。ITO底塗層3之成膜較佳為使用包含氧化銦及氧化錫之混合氧化物靶。The base coating is preferably formed using an oxide target. Although reactive sputtering using a metal target has the advantage of faster film formation, the quality of the film sometimes changes significantly due to slight changes in the film formation conditions (film formation environment). On the other hand, by using an oxide target, the quality of the base coating becomes stable. The ITO base coating 3 is preferably formed using a mixed oxide target containing indium oxide and tin oxide.
使底塗層濺鍍成膜時之基板溫度為-30℃～150℃左右，只要處於透明膜基材具有耐久性之範圍內則並無特別限定。使底塗層濺鍍成膜時之壓力或功率密度可根據靶之種類、或底塗層之厚度而適當設定。The substrate temperature during sputtering of the base coating is about -30°C to 150°C, and is not particularly limited as long as it is within the range of durability of the transparent film substrate. The pressure or power density during sputtering of the base coating can be appropriately set according to the type of target or the thickness of the base coating.
於藉由使用氧化物靶之濺鍍而使底塗層成膜之情形時，亦可除了氬氣等惰性氣體以外，還導入氧氣等氧化性氣體。由於藉由導入氧氣，濺鍍時自靶脫離之氧得到補充，因此有容易形成化學計量組成之ITO，透明性提高之傾向。When forming a base coat by sputtering using an oxide target, an oxidizing gas such as oxygen may be introduced in addition to an inert gas such as argon. By introducing oxygen, the oxygen released from the target during sputtering is replenished, so that ITO with a stoichiometric composition is easily formed, and the transparency tends to be improved.
另一方面，於濺鍍成膜時之氧氣導入量較大之情形時，有過量之氧增多，532 eV之峰強度I 532相對於530 eV之峰強度I 530之比I 532/I 530增加之傾向。濺鍍成膜時之氧氣導入量相對於惰性氣體100體積份，較佳為5體積份以下，更佳為3體積份以下，更佳為2體積份以下，進而較佳為1體積份以下，亦可為0.5體積份以下、0.3體積份以下、或0.1體積份以下。亦可於不導入氧氣而僅導入惰性氣體之同時，使底塗層成膜。若使用氧化物靶，則即便於完全不導入氧氣之情形時，氧缺陷亦極少，可避免透明性之顯著降低。 On the other hand, when the amount of oxygen introduced during sputtering film formation is large, there is an excess of oxygen, and the ratio of the peak intensity I 532 at 532 eV to the peak intensity I 530 at 530 eV (I 532 /I 530) tends to increase. The amount of oxygen introduced during sputtering film formation is preferably 5 volume parts or less, more preferably 3 volume parts or less, more preferably 2 volume parts or less, and further preferably 1 volume part or less, and may also be 0.5 volume parts or less, 0.3 volume parts or less, or 0.1 volume parts or less. It is also possible to form a base coating film while introducing only an inert gas without introducing oxygen. When an oxide target is used, even when no oxygen is introduced, oxygen defects are extremely small, and a significant decrease in transparency can be avoided.
如上所述，有ITO底塗層3中之氧化錫之比率越高，則峰強度比I 532/I 530越小之傾向。即，有ITO層之成膜中使用之靶之氧化錫之比率越高，成膜時之氧氣導入量越少，則ITO底塗層之I 532/I 530越小，紫外線照射時之電阻率變化越小之傾向。 As described above, the higher the ratio of tin oxide in the ITO base coating 3, the smaller the peak intensity ratio I 532 /I 530 tends to be. That is, the higher the ratio of tin oxide in the target used in forming the ITO layer, the less the amount of oxygen introduced during film formation, the smaller the I 532 /I 530 of the ITO base coating, and the smaller the resistivity change during ultraviolet irradiation.
＜防污層＞ 抗反射膜亦可於抗反射層5上具備附加之功能層。於抗反射膜配置於具備觸控感測器之圖像顯示裝置之最表面之情形時，為了易於防止因觸控操作導致之指紋或手垢等污染物質之附著、或去除所附著之污染物質等，較佳為於抗反射層5上設置防污層7。 <Anti-fouling layer> The anti-reflection film may also have an additional functional layer on the anti-reflection layer 5. When the anti-reflection film is arranged on the outermost surface of an image display device having a touch sensor, it is preferable to provide an anti-fouling layer 7 on the anti-reflection layer 5 in order to prevent the adhesion of contaminants such as fingerprints or hand dirt caused by touch operation, or to remove the attached contaminants.
於在抗反射膜之表面設置防污層7之情形時，基於降低界面處之反射之觀點考慮，較佳為抗反射層5之最表面之低折射率層54與防污層7之折射率差較小。防污層之折射率較佳為1.6以下，更佳為1.55以下。作為防污層之材料，較佳為含氟基之矽烷系化合物、或含氟基之有機化合物等。防污層可藉由反向塗佈法、模嘴塗佈法、凹版塗佈法等濕式法、或真空蒸鍍法、CVD法等乾式法來形成。防污層之厚度通常為1～100 nm左右，較佳為2～50 nm，更佳為3～30 nm。When the antifouling layer 7 is provided on the surface of the antireflection film, it is preferred that the refractive index difference between the low refractive index layer 54 on the outermost surface of the antireflection layer 5 and the antifouling layer 7 is small from the viewpoint of reducing the reflection at the interface. The refractive index of the antifouling layer is preferably 1.6 or less, and more preferably 1.55 or less. As the material of the antifouling layer, fluorine-containing silane compounds or fluorine-containing organic compounds are preferred. The antifouling layer can be formed by a wet method such as reverse coating, die-mouth coating, gravure coating, or a dry method such as vacuum evaporation or CVD. The thickness of the antifouling layer is generally about 1 to 100 nm, preferably 2 to 50 nm, and more preferably 3 to 30 nm.
[圖像顯示裝置] 抗反射膜配置於圖像顯示裝置之表面而使用。藉由在包含圖像顯示介質(圖像顯示部)之圖像顯示面板之視認側表面配置抗反射膜，從而可減少外光之反射，提高圖像顯示裝置之視認性。 [Image display device] An anti-reflection film is arranged on the surface of an image display device for use. By arranging an anti-reflection film on the visual side surface of an image display panel including an image display medium (image display unit), the reflection of external light can be reduced, thereby improving the visibility of the image display device.
於圖2所示之圖像顯示裝置201中，於在圖像顯示部81上具備觸控感測器部85之圖像顯示面板8之視認側表面，經由黏著劑層2而貼合有抗反射膜101。In the image display device 201 shown in FIG. 2 , an anti-reflection film 101 is attached to the viewing side surface of the image display panel 8 having the touch sensor portion 85 on the image display portion 81 via an adhesive layer 2 .
黏著劑層2例如由丙烯酸系黏著劑、橡膠系黏著劑、矽酮系黏著劑等構成。黏著劑層2之厚度並無特別限定，例如為1～100 μm左右。圖像顯示面板8與抗反射膜101亦可經由硬化型接著劑而貼合。抗反射膜101並非必須與圖像顯示面板8貼合，抗反射膜亦可以與圖像顯示面板隔開空間之方式配置於圖像顯示面板上。The adhesive layer 2 is composed of, for example, an acrylic adhesive, a rubber adhesive, a silicone adhesive, etc. The thickness of the adhesive layer 2 is not particularly limited, and is, for example, about 1 to 100 μm. The image display panel 8 and the anti-reflection film 101 can also be bonded via a curing adhesive. The anti-reflection film 101 does not have to be bonded to the image display panel 8, and the anti-reflection film can also be arranged on the image display panel in a manner that is separated from the image display panel by a space.
圖像顯示部8係液晶單元、有機EL單元等圖像顯示單元。圖像顯示部8亦可於圖像顯示單元之表面具備偏光板等光學膜。The image display unit 8 is an image display unit such as a liquid crystal unit, an organic EL unit, etc. The image display unit 8 may also have an optical film such as a polarizing plate on the surface of the image display unit.
觸控感測器部85例如係靜電電容方式之觸控面板，具備用於位置檢測之電極。靜電電容方式觸控面板藉由檢測手指或觸控筆觸摸觸控面(圖像顯示裝置201之視認側表面)時之電極之靜電電容之變化，而檢測觸摸位置。The touch sensor unit 85 is, for example, an electrostatic capacitive touch panel having electrodes for position detection. The electrostatic capacitive touch panel detects the touch position by detecting the change in electrostatic capacitance of the electrodes when a finger or a stylus touches the touch surface (the viewing side surface of the image display device 201).
圖2中示出於圖像顯示部81之視認側表面配置有觸控感測器部85之表嵌型觸控面板，觸控面板亦可為於圖像顯示單元之內部設有觸控感測器之內嵌型觸控面板。又，觸控面板亦可以與圖像顯示單元隔開之方式配置。FIG2 shows a surface-embedded touch panel with a touch sensor portion 85 disposed on the visual side surface of the image display portion 81. The touch panel may also be an embedded touch panel with a touch sensor disposed inside the image display unit. In addition, the touch panel may also be disposed in a manner separated from the image display unit.
圖像顯示裝置201由於配置於觸控感測器部85之視認側表面之抗反射膜101具備ITO底塗層3，因此具有抗靜電性，可防止由靜電引起之觸控感測器之誤動作。又，由於底塗層3之紫外線照射時之電阻變化率R 0/R 1較小，因此即便於室外使用圖像顯示裝置時，底塗層之電阻變化亦較小，不易發生檢測異常。 The image display device 201 has an anti-reflection film 101 disposed on the viewing side surface of the touch sensor portion 85 and has an ITO base coat 3, so it has anti-static properties and can prevent malfunction of the touch sensor caused by static electricity. In addition, since the resistance change rate R 0 /R 1 of the base coat 3 when irradiated with ultraviolet light is small, the resistance change of the base coat is small even when the image display device is used outdoors, and detection abnormalities are not likely to occur.
抗反射膜101由於使用透明樹脂膜作為用以形成底塗層3及抗反射層5之基板材料，因此具有可撓性，可彎曲。因此，抗反射膜亦可用作具備曲面顯示器、或可摺疊顯示器(foldable display)之圖像顯示裝置之表面板(覆蓋窗)。 [實施例] Since the anti-reflection film 101 uses a transparent resin film as a substrate material for forming the base coating layer 3 and the anti-reflection layer 5, it is flexible and can be bent. Therefore, the anti-reflection film can also be used as a surface plate (cover window) of an image display device with a curved display or a foldable display. [Example]
以下，列舉實施例對本發明進行進一步詳細說明，但本發明並不限定於以下具體例。The present invention is further described in detail below with reference to the following embodiments, but the present invention is not limited to the following specific examples.
[比較例1] (硬塗膜之製作) 將以固形物成分換算為100重量份之含有平均粒徑為50 nm以下之氧化矽粒子之紫外線硬化型丙烯酸系硬塗劑(Aica Kogyo製造之「Aicaaitron Z-850-50H-D」，固形物成分濃度44重量%)、光聚合起始劑(BASF製造之「OMNIRAD 2959」)4重量份、及調平劑(共榮社化學製造之「LE-303」)0.05重量份加以混合，用甲基異丁基酮進行稀釋，從而製備固形物成分濃度40重量%之硬塗組合物。將上述硬塗組合物以乾燥後之厚度成為5 μm之方式塗佈於厚度50 μm之PET膜(東麗製造之「Lumirror U48」)之單面，於80℃下加熱1分鐘而使其乾燥。其後，使用高壓水銀燈，以波長365 nm下之累計光量成為300 mJ/cm 2之方式照射紫外線而使組合物硬化，從而製作於PET膜上具備硬塗層之硬塗膜。 [Comparative Example 1] (Preparation of hard coating film) A UV-curable acrylic hard coating agent containing silicon oxide particles having an average particle size of 50 nm or less ("Aicaaitron Z-850-50H-D" manufactured by Aica Kogyo, solid content concentration 44% by weight), 4 parts by weight of a photopolymerization initiator ("OMNIRAD 2959" manufactured by BASF), and 0.05 parts by weight of a leveling agent ("LE-303" manufactured by Kyoeisha Chemical) were mixed and diluted with methyl isobutyl ketone to prepare a hard coating composition having a solid content concentration of 40% by weight. The hard coating composition was applied to one side of a 50 μm thick PET film ("Lumirror U48" manufactured by Toray) in a manner to have a thickness of 5 μm after drying, and dried by heating at 80°C for 1 minute. Thereafter, the composition was cured by irradiating ultraviolet rays using a high-pressure mercury lamp in a manner to have a cumulative light amount of 300 mJ/ cm2 at a wavelength of 365 nm, thereby preparing a hard coating film having a hard coating layer on the PET film.
(電漿處理) 一面於卷對卷式方式之電漿處理裝置內搬送硬塗膜，一面於1.0 Pa之真空氛圍下以150 W之放電功率對硬塗層之表面進行氬電漿處理。 (Plasma treatment) While the hard coating film is transported in a roll-to-roll plasma treatment device, the surface of the hard coating layer is treated with argon plasma at a discharge power of 150 W in a vacuum atmosphere of 1.0 Pa.
(底塗層及抗反射層之形成) 將電漿處理後之硬塗膜導入至卷對卷式方式之濺鍍成膜裝置，將槽內減壓至1×10 -4Pa之後，一面使膜移行，一面以-8℃之基板溫度依序於硬塗層形成面成膜出1.5 nm之ITO底塗層、12 nm之Nb 2O 5層(第一高折射率層)、28 nm之SiO 2層(第一低折射率層)、100 nm之Nb 2O 5層(第二高折射率層)、及85 nm之SiO 2層(第二低折射率層)。 (Formation of base coat and anti-reflection layer) The hard coat film after plasma treatment is introduced into a roll-to-roll sputtering film forming device. After the pressure in the tank is reduced to 1×10 -4 Pa, the film is moved while a 1.5 nm ITO base coat layer, a 12 nm Nb 2 O 5 layer (first high refractive index layer), a 28 nm SiO 2 layer (first low refractive index layer), a 100 nm Nb 2 O 5 layer (second high refractive index layer), and an 85 nm SiO 2 layer (second low refractive index layer) are sequentially formed on the hard coat layer formation surface at a substrate temperature of -8°C.
ITO底塗層之形成係使用以96.7：3.3之重量比包含氧化銦及氧化錫之氧化物靶，一面相對於氬氣100體積份導入0.4體積份之氧氣，一面於壓力0.2 Pa、放電電壓400 V之條件下進行MF-AC濺鍍成膜。The ITO base coating was formed by MF-AC sputtering at a pressure of 0.2 Pa and a discharge voltage of 400 V while introducing 0.4 volume parts of oxygen to 100 volume parts of argon using an oxide target containing indium oxide and tin oxide in a weight ratio of 96.7:3.3.
Nb 2O 5層(高折射率層)之形成係使用Nb靶，SiO 2層(低折射率層)之形成係使用Si靶，於0.7 Pa之壓力下進行MF-AC濺鍍成膜。於第一高折射率層之成膜中，相對於氬氣100體積份導入5體積份之氧氣，將放電電壓設為415 V。於第一低折射率層之成膜中，相對於氬氣100體積份導入30體積份之氧氣，將放電電壓設為350 V。於第二高折射率層之成膜中，相對於氬氣100體積份導入13體積份之氧氣，將放電電壓設為460 V。於第二低折射率層之成膜中，相對於氬氣100體積份導入30體積份之氧氣，將放電電壓設為340 V。 The Nb 2 O 5 layer (high refractive index layer) was formed using an Nb target, and the SiO 2 layer (low refractive index layer) was formed using an Si target, and the MF-AC sputtering deposition was performed at a pressure of 0.7 Pa. In the deposition of the first high refractive index layer, 5 volume parts of oxygen were introduced relative to 100 volume parts of argon, and the discharge voltage was set to 415 V. In the deposition of the first low refractive index layer, 30 volume parts of oxygen were introduced relative to 100 volume parts of argon, and the discharge voltage was set to 350 V. In the deposition of the second high refractive index layer, 13 volume parts of oxygen were introduced relative to 100 volume parts of argon, and the discharge voltage was set to 460 V. During the deposition of the second low refractive index layer, 30 volume parts of oxygen gas was introduced with respect to 100 volume parts of argon gas, and the discharge voltage was set to 340 V.
(防污層之形成) 將使氟系防污塗佈劑(信越化學工業製造之「KY1903-1」)乾燥而固化者作為蒸鍍源，藉由真空蒸鍍法，於抗反射層上形成厚度12 nm之防污層。 (Formation of antifouling layer) The dried and solidified fluorine-based antifouling coating agent ("KY1903-1" manufactured by Shin-Etsu Chemical Co., Ltd.) was used as an evaporation source to form an antifouling layer with a thickness of 12 nm on the antireflection layer by vacuum evaporation.
根據上述，獲得於硬塗膜之硬塗層上依序具備厚度1.5 nm之ITO底塗層、共計包含四層之抗反射層、及厚度12 nm之防污層之抗反射膜。According to the above, an anti-reflection film having an ITO base coating layer with a thickness of 1.5 nm, an anti-reflection layer including four layers in total, and an anti-fouling layer with a thickness of 12 nm in sequence on the hard coating layer of the hard coating film is obtained.
[參考例1] 於比較例1中，進行直至形成ITO底塗層為止之步驟，從而於不形成抗反射層及防污層之情況下，製作於硬塗膜之硬塗層上具備厚度1.5 nm之ITO底塗層之膜。 [Reference Example 1] In Comparative Example 1, the steps are performed until the ITO base coating layer is formed, thereby producing a film having an ITO base coating layer with a thickness of 1.5 nm on the hard coating layer of the hard coating film without forming an anti-reflection layer and an anti-fouling layer.
[實施例1及實施例2] 變更比較例1中之ITO底塗層之形成所用之靶，於實施例1中使用氧化錫含量為10重量%之靶，於實施例2中使用氧化錫含量為30重量%之靶。除此以外，以與比較例1相同之方式，製作於硬塗膜之硬塗層上依序具備厚度1.5 nm之ITO底塗層、包含共計四層之抗反射層、及厚度12 nm之防污層之抗反射膜。 [Example 1 and Example 2] The target used for forming the ITO base coating layer in Comparative Example 1 was changed. A target with a tin oxide content of 10 wt% was used in Example 1, and a target with a tin oxide content of 30 wt% was used in Example 2. In addition, an anti-reflection film having an ITO base coating layer with a thickness of 1.5 nm, an anti-reflection layer including a total of four layers, and an anti-fouling layer with a thickness of 12 nm was prepared in the same manner as in Comparative Example 1.
[參考例2～5] 於參考例1中之ITO底塗層之形成中，將靶之組成(氧化錫含量)、及濺鍍成膜時之氧氣導入量變更為如表1所示。除此以外，以與參考例1相同之方式，製作於硬塗膜之硬塗層上具備厚度1.5 nm之ITO層之膜。 [Reference Examples 2 to 5] In the formation of the ITO base coating layer in Reference Example 1, the target composition (tin oxide content) and the amount of oxygen introduced during sputtering were changed as shown in Table 1. In addition, a film having an ITO layer with a thickness of 1.5 nm on the hard coating layer of the hard coating film was prepared in the same manner as in Reference Example 1.
[評價] ＜ITO底塗層之XPS分析＞ 將參考例1～5之試樣切成1 cm×1 cm之尺寸，固定於掃描式X射線光電子光譜(XPS)裝置(ULVAC-PHI製造之「Quantera SXM」)之試樣台。藉由Ar氣體團簇離子(Ar n +)，以加速電壓10 kV進行蝕刻(蝕刻區域：2 mm×2 mm)，對表面進行清潔。其後，於下述條件下，實施ITO底塗層之XPS測定(窄掃描)。 X射線源：單色AlKα X射線束直徑：100 μm X射線輸出：25 W(15 kV) 光電子掠出角度：相對於試樣面為5° 中和條件：中和槍與Ar離子槍(中和模式)之併用 [Evaluation] <XPS analysis of ITO base coating> The samples of Reference Examples 1 to 5 were cut into a size of 1 cm × 1 cm and fixed on the sample stage of a scanning X-ray photoelectron spectroscopy (XPS) device ("Quantera SXM" manufactured by ULVAC-PHI). The surface was cleaned by etching with Ar gas cluster ions (Ar n + ) at an accelerating voltage of 10 kV (etching area: 2 mm × 2 mm). Subsequently, XPS measurement of the ITO base coating was performed under the following conditions (narrow scan). X-ray source: Monochromatic AlKα X-ray beam diameter: 100 μm X-ray output: 25 W (15 kV) Photoelectron take-off angle: 5° relative to the sample surface Neutralization conditions: Neutralization gun and Ar ion gun (neutralization mode)
於窄掃描之C1s光譜中，讀取530 eV之光譜強度I 530及532 eV之光譜強度I 532，算出兩者之強度比I 532/I 530。再者，鍵結能係以C1s光譜之源自C-C鍵之峰頂之位置成為285 eV之方式進行移動而修正所得之值。 In the narrow scan C1s spectrum, the spectral intensity I 530 at 530 eV and the spectral intensity I 532 at 532 eV were read, and the intensity ratio I 532 /I 530 was calculated. In addition, the bonding energy was corrected by shifting the position of the peak originating from the CC bond in the C1s spectrum to 285 eV.
＜表面電阻＞ 使用電阻率計(TREK製造之「152-1」)，測定實施例1、2及比較例1之抗反射膜之防污層之表面、及參考例1～4之膜之ITO層之表面之表面電阻R 0。其後，利用氙氣耐候試驗機(ATLAS製造之「Ci4000」)，於溫度25℃、相對濕度25%之環境下，以1.6 W/m 2之輻射強度照射1分鐘紫外線。於紫外線照射後30秒以內，再次測定表面電阻，作為紫外線照射後之表面電阻R 1。 <Surface resistance> The surface resistance R 0 of the antifouling layer of the antireflection film of Examples 1, 2 and Comparative Example 1, and the surface resistance R 0 of the ITO layer of the film of Reference Examples 1 to 4 were measured using a resistivity meter ("152-1" manufactured by TREK). Subsequently, the film was irradiated with ultraviolet light at a radiation intensity of 1.6 W/m 2 for 1 minute at a temperature of 25°C and a relative humidity of 25% using a xenon weathering tester ("Ci4000" manufactured by ATLAS). Within 30 seconds after the ultraviolet light irradiation, the surface resistance was measured again and taken as the surface resistance R 1 after the ultraviolet light irradiation.
＜紫外線照射後之觸控操作性＞ 將實施例、比較例之抗反射膜、及參考例之附ITO膜之PET膜側之面經由黏著劑層貼合於Apple製造之「iPad Air」之畫面上。使用手持型黑光燈(Alonefire製造之「SV003」，輻射強度10 W，波長365 nm)，對該試樣照射紫外線1分鐘之後，觸摸膜之表面，按照下述基準對觸控操作性進行評價。 ○：與紫外線照射前同樣，能夠順利地進行觸控操作 ×：未檢測出觸控操作，無法進行操作 <Touch operability after UV irradiation> The anti-reflection film of the embodiment, the comparative example, and the PET film side with ITO film of the reference example were attached to the screen of the "iPad Air" manufactured by Apple through an adhesive layer. After irradiating the sample with UV rays for 1 minute using a handheld black light ("SV003" manufactured by Alonefire, radiation intensity 10 W, wavelength 365 nm), the surface of the touch film was touched and the touch operability was evaluated according to the following criteria. ○: The touch operation can be performed smoothly as before UV irradiation ×: The touch operation was not detected and the operation could not be performed
將實施例、比較例、及參考例之底塗層之成膜條件(靶之錫含量、相對於氬氣100體積份之氧氣流量)、及評價結果示於表1。再者，比較例1、實施例1、及實施例2之表面電阻Ro、R1係於底塗層上具備抗反射層及防污層之抗反射膜之表面電阻，由於其並非係直接測定底塗層之表面電阻所得者，因此記載為參考值。The film forming conditions (tin content of the target, oxygen flow rate relative to 100 parts by volume of argon) and evaluation results of the base coating of the embodiment, comparative example, and reference example are shown in Table 1. In addition, the surface resistance Ro and R1 of comparative example 1, embodiment 1, and embodiment 2 are the surface resistances of the anti-reflection film having an anti-reflection layer and an anti-fouling layer on the base coating, and are not obtained by directly measuring the surface resistance of the base coating, so they are recorded as reference values.
[表1]
關於ITO底塗層之C1s光譜中之峰強度比I 532/I 530為0.963之參考例1之膜，R 0/R 1為1000，表面電阻因紫外線照射而減少至1/1000。於將參考例1之膜配置於觸控面板之表面之狀態下照射紫外線之後，發生檢測異常，無法進行觸控操作。I 532/I 530為0.963之參考例2亦與參考例1同樣，於照射紫外線後發生觸控感測器之檢測異常。 Regarding the film of Reference Example 1, the peak intensity ratio I 532 /I 530 in the C1s spectrum of the ITO base coating is 0.963, R 0 /R 1 is 1000, and the surface resistance is reduced to 1/1000 due to ultraviolet irradiation. After the film of Reference Example 1 is placed on the surface of the touch panel and irradiated with ultraviolet rays, detection abnormality occurs and touch operation cannot be performed. Reference Example 2, with I 532 /I 530 of 0.963, also has detection abnormality of the touch sensor after irradiation with ultraviolet rays, similar to Reference Example 1.
關於在參考例1之膜之ITO底塗層上設有抗反射層及防污層的比較例1之抗反射膜，與參考例1同樣，於照射紫外線後發生觸控感測器之檢測異常。Regarding the anti-reflection film of Comparative Example 1 in which an anti-reflection layer and an anti-fouling layer are provided on the ITO base coating layer of the film of Reference Example 1, similarly to Reference Example 1, detection abnormality of the touch sensor occurred after irradiation with ultraviolet rays.
關於ITO底塗層之I 532/I 530為0.906之參考例3之膜，R 0/R 1為50，即便於配置於觸控面板之表面之狀態下照射紫外線之後，亦能夠正常地進行觸控操作。關於在參考例3之膜之ITO底塗層上設有抗反射層及防污層的實施例1之抗反射膜，與參考例3同樣，即便於照射紫外線之後，亦能夠正常地進行觸控操作。 Regarding the film of Reference Example 3, in which I532 / I530 of the ITO base coating is 0.906, R0 / R1 is 50, and even after being irradiated with ultraviolet rays in the state of being arranged on the surface of the touch panel, touch operation can be performed normally. Regarding the anti-reflection film of Example 1 in which an anti-reflection layer and an anti-fouling layer are provided on the ITO base coating of the film of Reference Example 3, touch operation can be performed normally even after being irradiated with ultraviolet rays, as in Reference Example 3.
關於ITO底塗層之I 532/I 530為0.898之參考例5之膜、以及於ITO層上設有抗反射層及防污層之實施例3之抗反射膜，與參考例3及實施例1同樣，即便於照射紫外線後，亦能夠正常地進行觸控操作。 The film of Reference Example 5 in which I532 / I530 of the ITO base coating layer is 0.898 and the anti-reflection film of Example 3 in which an anti-reflection layer and an anti-fouling layer are provided on the ITO layer, like Reference Example 3 and Example 1, can perform touch operation normally even after irradiation with ultraviolet rays.
關於R 0/R 1較小(由紫外線照射引起之表面電阻之變化率較小)之參考例4，與參考例3、5同樣，即便於照射紫外線後，亦能夠正常地進行觸控操作。 Regarding Reference Example 4 in which R 0 /R 1 is small (the rate of change of surface resistance caused by ultraviolet irradiation is small), similar to Reference Examples 3 and 5, normal touch operation can be performed even after ultraviolet irradiation.
根據該等結果可知，無論有無抗反射層(及防污層)，由紫外線照射導致之ITO底塗層之電阻之降低均引起觸控感測器之檢測異常，並且，於ITO底塗層之C1s光譜中之峰強度比I 532/I 530較小之情形時，由紫外線照射導致之ITO底塗層之電阻變化較小，不會發生觸控感測器之檢測異常。 According to these results, regardless of the presence or absence of an anti-reflection layer (and anti-fouling layer), the reduction in the resistance of the ITO undercoat caused by ultraviolet irradiation will cause detection abnormalities of the touch sensor. Moreover, when the peak intensity in the C1s spectrum of the ITO undercoat is smaller than I 532 /I 530 , the resistance change of the ITO undercoat caused by ultraviolet irradiation is smaller and no detection abnormalities of the touch sensor will occur.
根據參考例1、3、5之對比可知，有ITO底塗層之氧化錫含量(用於成膜之靶之氧化錫含量)越大，則I 532/I 530越小，R 0/R 1越小之傾向。又，根據參考例2～4之對比可知，有ITO底塗層成膜時之氧氣導入量越小，則I 532/I 530越小，R 0/R 1越小之傾向。 According to the comparison of reference examples 1, 3, and 5, it can be seen that the greater the tin oxide content of the ITO base coating (tin oxide content of the target used for film formation), the smaller I 532 /I 530 and R 0 /R 1 tend to be. In addition, according to the comparison of reference examples 2 to 4, it can be seen that the smaller the amount of oxygen introduced during the ITO base coating film formation, the smaller I 532 /I 530 and R 0 /R 1 tend to be.
根據以上結果可知，藉由提高ITO底塗層之氧化錫含量、及/或增加ITO底塗層成膜時之氧氣導入量，有XPS之C1s光譜中之峰強度比I 532/I 530減小之傾向，於I 532/I 530較小之情形時，由紫外線照射引起之底塗層之電阻變化率較小，可防止觸控感測器之檢測異常。 Based on the above results, it can be seen that by increasing the tin oxide content of the ITO undercoat and/or increasing the amount of oxygen introduced during the formation of the ITO undercoat, the peak intensity in the XPS C1s spectrum tends to decrease compared to I 532 /I 530. When I 532 /I 530 is smaller, the resistance change rate of the undercoat caused by ultraviolet irradiation is smaller, which can prevent abnormal detection of the touch sensor.
再者，於比較例1、及參考例1、2中，於紫外線照射之後立即發生觸控感測器之檢測異常，但當自紫外線照射起經過1小時後實施觸控操作時，可正常地進行觸控操作。認為由紫外線照射引起之電阻變化、及由此導致之觸控感測器之檢測異常於紫外線照射後立即暫時發生。Furthermore, in Comparative Example 1 and Reference Examples 1 and 2, the detection abnormality of the touch sensor occurred immediately after the ultraviolet irradiation, but when the touch operation was performed 1 hour after the ultraviolet irradiation, the touch operation could be performed normally. It is believed that the resistance change caused by the ultraviolet irradiation and the detection abnormality of the touch sensor caused by it occurred temporarily immediately after the ultraviolet irradiation.
1:透明膜基材(硬塗膜) 2:黏著劑層 3:底塗層 5:抗反射層 7:防污層 8:圖像顯示面板 10:透明樹脂膜 11:硬塗層 51:高折射率層 52:低折射率層 53:高折射率層 54:低折射率層 81:圖像顯示部 85:觸控感測器部 101:抗反射膜 201:圖像顯示裝置 1: Transparent film substrate (hard coating film) 2: Adhesive layer 3: Primer layer 5: Anti-reflection layer 7: Anti-fouling layer 8: Image display panel 10: Transparent resin film 11: Hard coating layer 51: High refractive index layer 52: Low refractive index layer 53: High refractive index layer 54: Low refractive index layer 81: Image display unit 85: Touch sensor unit 101: Anti-reflection film 201: Image display device
圖1係一實施方式之抗反射膜之剖視圖。 圖2係一實施方式之圖像顯示裝置之剖視圖。 FIG1 is a cross-sectional view of an anti-reflection film according to an embodiment. FIG2 is a cross-sectional view of an image display device according to an embodiment.
1:透明膜基材(硬塗膜) 1: Transparent film substrate (hard coating film)
3:底塗層 3: Base coating
5:抗反射層 5: Anti-reflective layer
7:防污層 7: Antifouling layer
10:透明樹脂膜 10: Transparent resin film
11:硬塗層 11: Hard coating
51:高折射率層 51: High refractive index layer
52:低折射率層 52: Low refractive index layer
53:高折射率層 53: High refractive index layer
54:低折射率層 54: Low refractive index layer
101:抗反射膜 101: Anti-reflective film
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