TWI786475B - Anti-reflection film and image display device - Google Patents
Anti-reflection film and image display device Download PDFInfo
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- TWI786475B TWI786475B TW109141310A TW109141310A TWI786475B TW I786475 B TWI786475 B TW I786475B TW 109141310 A TW109141310 A TW 109141310A TW 109141310 A TW109141310 A TW 109141310A TW I786475 B TWI786475 B TW I786475B
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- 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
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- 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
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- G—PHYSICS
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- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
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- G—PHYSICS
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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- G—PHYSICS
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- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
Abstract
本發明之抗反射膜(101)具備依序設置於硬塗膜(1)之硬塗層(11)上之抗反射層(5)及防污層(7)，上述硬塗膜(1)係於透明膜基材(10)之一主面上具備硬塗層(11)者。硬塗層包含黏合劑及1～8 μm粒徑之微粒子。抗反射層包含折射率不同之複數層薄膜之積層體。抗反射膜之霧度為1～18%，防污層表面之算術平均粗糙度Ra為0.05～0.25 μm，凹凸之平均間隔RSm為60～200 μm。The antireflection film (101) of the present invention has an antireflection layer (5) and an antifouling layer (7) sequentially arranged on the hard coat layer (11) of the hard coat film (1), and the above hard coat film (1) A hard coat layer (11) is provided on one main surface of a transparent film substrate (10). The hard coat layer contains binders and fine particles with a particle size of 1-8 μm. The antireflection layer includes a laminate of multiple thin films with different refractive indices. The haze of the anti-reflection film is 1-18%, the arithmetic average roughness Ra of the surface of the anti-fouling layer is 0.05-0.25 μm, and the average interval RSm of the unevenness is 60-200 μm.
Description
本發明係關於一種於透明膜基材上具備抗反射層及防污層之抗反射膜。進而，本發明係關於一種具備該抗反射膜之圖像顯示裝置。 The invention relates to an antireflection film with an antireflection layer and an antifouling layer on a transparent film substrate. Furthermore, the present invention relates to an image display device including the antireflection film.
為了防止外界光之反射引起之畫質降低、提昇對比度等，而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視認側表面使用有抗反射膜。抗反射膜於透明膜上具備抗反射層，該抗反射層包含折射率不同之複數層薄膜之積層體。抗反射膜配置於圖像顯示裝置之最表面，以可自外部接觸之狀態使用，故易受到指紋、手垢、灰塵等污染之影響。因此，為了防止來自外部環境之污染或容易去除附著之污染物質，而於抗反射層之表面設置有防污層(例如專利文獻1)。 In order to prevent the degradation of image quality caused by the reflection of external light, improve the contrast, etc., an anti-reflection film is used on the viewing side surface of image display devices such as liquid crystal displays or organic EL (Electroluminescence) displays. The antireflection film is provided with an antireflection layer on a transparent film, and the antireflection layer includes a laminated body of a plurality of thin films having different refractive indices. The anti-reflection film is arranged on the outermost surface of the image display device and used in a state that can be accessed from the outside, so it is easily affected by pollution such as fingerprints, hand dirt, and dust. Therefore, in order to prevent pollution from the external environment or to easily remove adhering pollutants, an antifouling layer is provided on the surface of the antireflection layer (for example, Patent Document 1).
有實施防眩(Anti-glare)處理以防止外界光映入引起對比度降低之方法。例如，專利文獻2中提出有一種於防眩性硬塗膜上設置有抗反射層之防眩性抗反射膜，上述防眩性硬塗膜係於透明膜上形成有包含微粒子之硬塗層者。 There is a method of implementing anti-glare (Anti-glare) treatment to prevent the reduction of contrast caused by external light. For example, Patent Document 2 proposes an antiglare antireflection film having an antireflection layer on an antiglare hard coat film in which a hard coat layer containing fine particles is formed on a transparent film. By.
[專利文獻1]日本專利特開2015-69008號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2015-69008
[專利文獻2]日本專利特開2008-90263號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2008-90263
防眩性塗層藉由利用表面凹凸使外界光散射反射而減少了外界光之映入。另一方面，防眩性塗層之表面凹凸具有使來自顯示面板之光(影像光)折射之透鏡作用，故有時會強調顯示裝置之局部性亮度不均，而使畫面出現眩光。尤其是，若為了提高圖像清晰度(通透感)而降低防眩性塗層之霧度，則有容易出現眩光之傾向。又，近年來，圖像顯示裝置不斷高清化，像素尺寸逐漸變小。進而，經由透明黏著片而於圖像顯示面板上配置有觸控面板或覆蓋窗之構成中，配置於圖像顯示裝置之表面之防眩性塗層與圖像顯示面板之間之間隙較大，有時超過1mm。 The anti-glare coating reduces the reflection of external light by using surface unevenness to scatter and reflect external light. On the other hand, the surface unevenness of the anti-glare coating acts as a lens to refract the light (image light) from the display panel, so it sometimes emphasizes the local uneven brightness of the display device, causing glare on the screen. In particular, if the haze of the anti-glare coating is reduced in order to improve image clarity (transparency), glare tends to easily occur. In addition, in recent years, image display devices have become increasingly high-definition, and pixel sizes have gradually decreased. Furthermore, in the structure in which the touch panel or the cover window is arranged on the image display panel through the transparent adhesive sheet, the gap between the anti-glare coating layer arranged on the surface of the image display device and the image display panel is relatively large. , sometimes exceeding 1mm.
隨著圖像顯示裝置之構成之改變，諸如高清化、寬間隙化等，有更容易出現由防眩性塗層之凹凸引起之眩光之傾向，先前之防眩性塗層不易獲得充分之視認性。又，表面具備防污層之抗反射膜存在如下問題：隨著使用，防污層磨耗，防污性降低。 With changes in the composition of image display devices, such as high-definition, wide-gap, etc., there is a tendency that glare caused by the unevenness of the anti-glare coating is more likely to occur, and it is difficult to obtain sufficient visual recognition with the previous anti-glare coating. sex. Also, the antireflection film provided with an antifouling layer on the surface has a problem that the antifouling layer wears away with use and the antifouling property decreases.
鑒於上述情況，本發明之目的在於提供一種抗反射膜，其發揮出高防眩性，並且於寬間隙構成之圖像顯示裝置中亦不易產生眩光不良，防污層之耐磨耗性優異。 In view of the above circumstances, an object of the present invention is to provide an anti-reflection film that exhibits high anti-glare properties and is less likely to cause glare defects in an image display device having a wide gap structure, and has excellent abrasion resistance of the anti-fouling layer.
本發明之抗反射膜具備依序設置於硬塗膜之硬塗層上之抗反射層及防污層，上述硬塗膜係於透明膜基材之一主面上具備硬塗層者。硬塗層包含黏合劑及1~8μm粒徑之微粒子。抗反射層包含折射率不同之複數層薄膜之積層體。構成抗反射層之薄膜較佳為無機氧化物。抗反射層可為藉由濺鍍形成之濺鍍膜。硬塗層與抗反射層之間亦可設置有包含氧化矽等無機氧化物之底塗層。 The antireflection film of the present invention comprises an antireflection layer and an antifouling layer sequentially provided on a hard coat layer of a hard coat film having a hard coat layer on one main surface of a transparent film substrate. The hard coat layer contains binder and fine particles with particle size of 1~8μm. The antireflection layer includes a laminate of multiple thin films with different refractive indices. The thin film constituting the antireflection layer is preferably an inorganic oxide. The antireflection layer may be a sputtered film formed by sputtering. An undercoat layer containing inorganic oxides such as silicon oxide may also be provided between the hard coat layer and the antireflection layer.
抗反射膜之霧度較佳為1~18%，亦可為4~18%。抗反射膜之表面(防污層之表面)之算術平均粗糙度Ra較佳為0.05~0.25μm，凹凸之平均間隔RSm較佳為60~200μm。 The haze of the anti-reflection film is preferably 1-18%, and can also be 4-18%. The arithmetic mean roughness Ra of the surface of the antireflection film (the surface of the antifouling layer) is preferably 0.05-0.25 μm, and the average interval RSm of the concavo-convex is preferably 60-200 μm.
硬塗層除1~8μm粒徑之微粒子以外，亦可包含平均一次粒徑為100nm以下之奈米粒子。相對於黏合劑100重量份，硬塗層中之1~8μm粒徑之微粒子(微粒子)之量較佳為3~10重量份。黏合劑之折射率與微粒子之折射率的差較佳為0.01~0.06。 In addition to fine particles with a particle size of 1-8 μm, the hard coat layer may also contain nanoparticles with an average primary particle size of 100 nm or less. The amount of fine particles (fine particles) with a particle size of 1 to 8 μm in the hard coat layer is preferably 3 to 10 parts by weight relative to 100 parts by weight of the binder. The difference between the refractive index of the binder and the refractive index of the microparticles is preferably 0.01-0.06.
於圖像顯示介質之視認側表面配置有本發明之抗反射膜的圖像顯示裝置表現出優異之防眩性，並且不易產生顯示圖像之眩光不良，視認性優異。又，本發明之抗反射膜於防污層之耐磨耗性方面優異，長期使用後仍表現出較高之防污性及去污性。 The image display device provided with the antireflection film of the present invention on the viewing side surface of the image display medium exhibits excellent anti-glare properties, is less likely to cause glare defects of displayed images, and has excellent visibility. In addition, the antireflection film of the present invention is excellent in abrasion resistance of the antifouling layer, and exhibits high antifouling and decontamination properties after long-term use.
1:硬塗膜 1: Hard coating film
3:底塗層 3: Base coat
5:抗反射層 5: Anti-reflection layer
7:防污層 7: Antifouling layer
8:覆蓋窗 8: Covering window
9:黏著片 9: Adhesive sheet
10:透明膜基材 10: Transparent film substrate
11:硬塗層 11: Hard coating
20:圖像顯示單元 20: Image display unit
51,53:高折射率層 51,53: high refractive index layer
52,54:低折射率層 52,54: low refractive index layer
101:抗反射膜 101: Anti-reflection film
201:圖像顯示裝置 201: Image display device
D:間隙 D: Gap
圖1係表示抗反射膜之積層構成例之剖視圖。 Fig. 1 is a cross-sectional view showing an example of a laminated structure of an antireflection film.
圖2係表示具備抗反射膜之圖像顯示裝置之構成例的剖視圖。 FIG. 2 is a cross-sectional view showing a configuration example of an image display device provided with an antireflection film.
圖1係表示本發明之一實施方式之抗反射膜之積層構成例的剖視圖。抗反射膜101於硬塗膜1之硬塗層11上具備抗反射層5，且於抗反射層5上具備防污層7。硬塗膜1於透明膜基材10之一主面上具備硬塗層11。抗反射層5為折射率不同之2層以上無機薄膜之積層體。硬塗層11與抗反射層5之間亦可設置有底塗層3。
FIG. 1 is a cross-sectional view showing an example of a laminated structure of an antireflection film according to an embodiment of the present invention. The
硬塗膜1於透明膜基材10之一主面上具備硬塗層11。藉由於抗反射層5形成面側設置硬塗層11，可提昇抗反射膜之表面硬度或耐擦傷性等機械特性。
The
透明膜基材10之可見光透過率較佳為80%以上，更佳為90%以上。作為構成透明膜基材10之樹脂材料，例如較佳為透明性、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，可列舉：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
透明膜基材之厚度並無特別限制，就強度或操作性等作業性、薄層性等之觀點而言，較佳為5~300μm左右，更佳為10~250μm，進而較佳為20~200μm。 The thickness of the transparent film substrate is not particularly limited, but it is preferably about 5 to 300 μm, more preferably 10 to 250 μm, and still more preferably 20 to 200 μm.
藉由於透明膜基材10之主面上設置硬塗層11而形成硬塗膜1。硬塗層11係包含黏合劑及微粒子之防眩性硬塗層，藉由利用微粒子形成之表面凹凸來發揮防眩性。
The
作為硬塗層11之黏合劑，較佳為使用熱固性樹脂、光硬化性樹脂、電子束硬化性樹脂等硬化性樹脂。作為硬化性樹脂之種類，可列舉：聚酯系、丙烯酸系、胺基甲酸酯系、聚胺基甲酸酯丙烯酸酯系、醯胺系、矽酮系、矽酸鹽系、環氧系、三聚氰胺系、氧雜環丁烷系、聚胺基甲酸酯丙烯酸酯系等。其中，就硬度高、可光硬化之方面而言，較佳為丙烯酸系樹脂、聚胺基甲酸酯丙烯酸酯系樹脂及環氧系樹脂，其中較佳為丙烯酸系樹脂及聚胺基甲酸酯丙烯酸酯系樹脂。如下文所述，黏合劑除樹脂成分(有機成分)以外，亦可包含無機奈米粒子等無機成分。
As the binder of the
黏合劑之折射率一般為1.4~1.6左右。如下文所詳述，就降低硬塗層 之霧度之觀點而言，較佳為黏合劑與微粒子之折射率差較小。 The refractive index of the adhesive is generally around 1.4~1.6. As detailed below, reducing the hardcoat From the viewpoint of haze, it is preferable that the refractive index difference between the binder and the fine particles is small.
光硬化性之黏合劑樹脂成分包含具有2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，亦可為低聚物。作為光聚合性之多官能化合物，較佳為使用1分子中包含2個以上(甲基)丙烯醯基之化合物。 The photocurable adhesive resin component contains a polyfunctional compound having two or more photopolymerizable (preferably ultraviolet polymerizable) functional groups. The polyfunctional compound may be a monomer or an oligomer. As the photopolymerizable polyfunctional compound, it is preferable to use a compound containing two or more (meth)acryloyl groups in one molecule.
作為1分子中具有2個以上(甲基)丙烯醯基之多官能化合物之具體例，可列舉：三環癸烷二甲醇二丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、三羥甲基丙烷三丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二羥甲基丙烷四丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、1,6-己二醇(甲基)丙烯酸酯、1,9-壬二醇二丙烯酸酯、1,10-癸二醇(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、二丙二醇二丙烯酸酯、異三聚氰酸三(甲基)丙烯酸酯、乙氧化甘油三丙烯酸酯、乙氧化季戊四醇四丙烯酸酯及該等之低聚物或預聚物等。再者，於本說明書中，「(甲基)丙烯酸」意為丙烯酸及/或甲基丙烯酸。 Specific examples of polyfunctional compounds having two or more (meth)acryloyl groups in one molecule include tricyclodecane dimethanol diacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(methyl) ) acrylate, trimethylolpropane triacrylate, pentaerythritol tetra(meth)acrylate, dimethylolpropane tetraacrylate, dipentaerythritol hexa(meth)acrylate, 1,6-hexanediol (meth)acrylate base) acrylate, 1,9-nonanediol diacrylate, 1,10-decanediol (meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate Dipropylene glycol diacrylate, isocyanuric acid tri(meth)acrylate, ethoxylated glycerin triacrylate, ethoxylated pentaerythritol tetraacrylate and their oligomers or prepolymers. In addition, in this specification, "(meth)acryl" means acryl and/or methacryl.
1分子中具有2個以上(甲基)丙烯醯基之多官能化合物亦可具有羥基。藉由使用含羥基之多官能化合物作為黏合劑樹脂成分，而有透明基材與硬塗層之密接性提昇之傾向。作為1分子中具有羥基及2個以上(甲基)丙烯醯基之化合物，可列舉季戊四醇三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯等。 A polyfunctional compound having two or more (meth)acryloyl groups in one molecule may also have a hydroxyl group. By using a hydroxyl-containing polyfunctional compound as a binder resin component, the adhesiveness of a transparent base material and a hard-coat layer tends to improve. Pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, etc. are mentioned as a compound which has a hydroxyl group and 2 or more (meth)acryloyl groups in 1 molecule.
聚胺基甲酸酯丙烯酸酯樹脂包含聚胺基甲酸酯(甲基)丙烯酸酯之單體或低聚物作為多官能化合物。聚胺基甲酸酯(甲基)丙烯酸酯所具有之(甲基)丙烯醯基之數量較佳為3以上，更佳為4~15，進而較佳為6~12。聚胺基甲酸酯(甲基)丙烯酸酯低聚物之分子量例如為3000以下，較佳為500~2500，更佳為800~2000。聚胺基甲酸酯(甲基)丙烯酸酯例如藉由使由(甲基)丙烯酸或(甲基)丙烯酸酯及多元醇所得之(甲基)丙烯酸羥基酯與二異氰酸酯發生反應而獲得。 The polyurethane acrylate resin contains a monomer or oligomer of polyurethane (meth)acrylate as a polyfunctional compound. The number of (meth)acryloyl groups that polyurethane (meth)acrylate has is preferably at least 3, more preferably 4-15, and still more preferably 6-12. The molecular weight of the polyurethane (meth)acrylate oligomer is, for example, 3000 or less, preferably 500-2500, more preferably 800-2000. Polyurethane (meth)acrylate is obtained, for example, by reacting hydroxy (meth)acrylate obtained from (meth)acrylic acid or (meth)acrylate, and a polyhydric alcohol with diisocyanate.
相對於黏合劑樹脂成分(藉由硬化而形成黏合劑樹脂之單體、低聚物及預聚物)之總計100重量份，硬塗組合物中之多官能化合物之含量較佳為50重量份以上，更佳為60重量份以上，進而較佳為70重量份以上。若多官能單體之含量為上述範圍，則有提高硬塗層之硬度之傾向。 The content of the polyfunctional compound in the hard coat composition is preferably 50 parts by weight relative to 100 parts by weight of the binder resin component (monomers, oligomers, and prepolymers that form the binder resin by curing) in total. The above, more preferably 60 parts by weight or more, further preferably 70 parts by weight or more. It exists in the tendency for the hardness of a hard-coat layer to improve that content of a polyfunctional monomer is the said range.
黏合劑樹脂成分亦可進而包含單官能單體。相對於黏合劑樹脂成分100重量份，單官能單體之含量較佳為50重量份以下，更佳為40重量份以下，進而較佳為30重量份以下。 The binder resin component may further include a monofunctional monomer. The content of the monofunctional monomer is preferably not more than 50 parts by weight, more preferably not more than 40 parts by weight, and still more preferably not more than 30 parts by weight relative to 100 parts by weight of the binder resin component.
藉由在硬塗層中包含1μm以上粒徑之微粒子(以下稱為「微粒子」)，而於硬塗層之表面形成凹凸，賦予硬塗層防眩性。又，微粒子亦有助於控制硬塗層之霧度。 By including fine particles with a particle size of 1 μm or more (hereinafter referred to as "fine particles") in the hard coat layer, irregularities are formed on the surface of the hard coat layer, thereby imparting anti-glare properties to the hard coat layer. In addition, fine particles also help to control the haze of the hard coat layer.
作為微粒子，並無特別限制，可使用：氧化矽、氧化鋁、氧化鈦、 氧化鋯、氧化鈣、氧化錫、氧化銦、氧化鎘、氧化銻等各種金屬氧化物微粒子；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、丙烯酸酯-苯乙烯共聚物、苯并胍胺、三聚氰胺、聚碳酸酯等各種透明聚合物的交聯或未交聯之有機系微粒子；矽酮系微粒子等具有透明性者。該等微粒子可適當選擇使用1種或2種以上。 There are no particular limitations on fine particles, and silicon oxide, aluminum oxide, titanium oxide, Zirconia, calcium oxide, tin oxide, indium oxide, cadmium oxide, antimony oxide and other metal oxide particles; glass particles; including polymethyl methacrylate, polystyrene, polyurethane, acrylate-benzene Cross-linked or uncross-linked organic microparticles of various transparent polymers such as ethylene copolymer, benzoguanamine, melamine, polycarbonate, etc.; silicone microparticles and other transparent ones. One or more of these fine particles can be appropriately selected and used.
較佳為微粒子與硬塗層之黏合劑樹脂之折射率差較小。藉由減小黏合劑與微粒子之折射率差，黏合劑與微粒子之界面處之光散射減少，霧度變小，因此可實現高通透感之顯示。另一方面，於硬塗層之霧度過小之情形時，防眩性有可能不充分。就使硬塗層具有適度之霧度並且減少眩光之觀點而言，黏合劑與微粒子之折射率差較佳為0.01~0.06左右，更佳為0.02~0.05。 It is preferable that the difference in refractive index between the fine particles and the binder resin of the hard coat layer is small. By reducing the refractive index difference between the binder and the microparticles, the light scattering at the interface between the binder and the microparticles is reduced, and the haze becomes smaller, so a display with high transparency can be realized. On the other hand, when the haze of a hard-coat layer is too small, antiglare property may be insufficient. From the viewpoint of making the hard coat layer have moderate haze and reducing glare, the refractive index difference between the binder and the microparticles is preferably about 0.01-0.06, more preferably 0.02-0.05.
微粒子之粒徑較佳為10μm以下。硬塗層中所含之微粒子(1μm以上粒徑之粒子)之平均粒徑較佳為1~8μm，更佳為2~5μm。於微粒子之粒徑較小之情形時，有防眩性不足之傾向。於微粒子之粒徑較大之情形時，有圖像清晰度降低之傾向，尤其於像素尺寸較小之高清顯示器中，該傾向較為顯著。於硬塗層中包含2種以上微粒子之情形時，較佳為微粒子整體之平均粒徑處於上述範圍內。平均粒徑係藉由庫爾特計數法測得之重量平均粒徑。 The particle size of the fine particles is preferably 10 μm or less. The average particle size of the microparticles (particles with a particle size of 1 μm or more) contained in the hard coat layer is preferably 1 to 8 μm, more preferably 2 to 5 μm. When the particle size of the fine particles is small, the antiglare property tends to be insufficient. When the particle size of the fine particles is large, there is a tendency to reduce the image definition, especially in a high-definition display with a small pixel size, this tendency is more significant. When two or more types of microparticles are contained in the hard coat layer, it is preferable that the average particle diameter of the whole microparticles|fine-particles exists in the said range. The average particle size is the weight average particle size measured by the Coulter counter method.
微粒子之形狀並無特別限制，就減少眩光之觀點而言，較佳為縱橫比為1.5以下之球狀粒子。球狀粒子之縱橫比較佳為1.3以下，更佳為1.1以 下。 The shape of the fine particles is not particularly limited, but spherical particles with an aspect ratio of 1.5 or less are preferred from the viewpoint of reducing glare. The aspect ratio of spherical particles is preferably 1.3 or less, more preferably 1.1 or less Down.
硬塗層中之微粒子之含量並無特別限制。就於硬塗層之表面均勻地形成凹凸之觀點而言，相對於黏合劑100重量份，微粒子之含量較佳為0.5重量份以上，更佳為0.8重量份以上，進而較佳為1.0重量份以上，亦可為1.5重量份以上、2.0重量份以上或2.5重量份以上。相對於黏合劑100重量份，微粒子之含量較佳為12重量份以下，亦可為11重量份以下。於微粒子之含量較少之情形時，硬塗層表面之凹凸之平均間隔(粗糙度曲線要素之平均長度)RSm較大，易產生眩光不良。另一方面，於微粒子之含量較多之情形時，有霧度上升、圖像清晰度下降之傾向。硬塗層中之微粒子之含量亦可為3~10重量份或3.5~8重量份。 The content of fine particles in the hard coat layer is not particularly limited. From the viewpoint of uniformly forming unevenness on the surface of the hard coat layer, the content of the fine particles is preferably at least 0.5 parts by weight, more preferably at least 0.8 parts by weight, and still more preferably 1.0 parts by weight relative to 100 parts by weight of the binder. The above may be 1.5 parts by weight or more, 2.0 parts by weight or more, or 2.5 parts by weight or more. The content of the microparticles is preferably 12 parts by weight or less, and may be 11 parts by weight or less with respect to 100 parts by weight of the binder. When the content of microparticles is small, the average interval of roughness (average length of roughness curve elements) RSm on the surface of the hard coat layer is large, and glare defects are likely to occur. On the other hand, when the content of fine particles is large, the haze increases and the image definition tends to decrease. The content of fine particles in the hard coat layer may also be 3-10 parts by weight or 3.5-8 parts by weight.
硬塗層除1μm以上粒徑之微粒子以外，亦可包含粒徑未達1μm之微粒子(以下有時稱為「奈米粒子」)。例如，藉由使硬塗層包含平均一次粒徑為10nm~100nm左右之奈米粒子，有於硬塗層6之表面上形成尺寸小於由微粒子形成之凹凸的微細凹凸，提昇硬塗層11與形成於其上之抗反射層5之密接性的傾向。又，藉由包含粒徑尺寸遠小於可見光之波長(例如100nm以下)之奈米粒子，可於不使硬塗層之透明性降低之情況下調整黏合劑之折射率。
The hard coat layer may contain fine particles with a particle size of less than 1 μm (hereinafter sometimes referred to as “nanoparticles”) in addition to fine particles with a particle size of 1 μm or more. For example, by making the hard coat layer include nanoparticles with an average primary particle size of about 10 nm to 100 nm, fine unevenness smaller than that formed by fine particles can be formed on the surface of the hard coat layer 6, thereby improving the relationship between the
就提高於黏合劑中之分散性之觀點而言，奈米粒子之平均一次粒徑較佳為15nm以上，更佳為20nm以上。就形成有助於提昇密接性之微細 凹凸形狀之觀點而言，奈米粒子之平均一次粒徑較佳為90nm以下，更佳為70nm以下，進而較佳為50nm以下。 From the viewpoint of improving the dispersibility in the binder, the average primary particle size of the nanoparticles is preferably 15 nm or more, more preferably 20 nm or more. to form fine particles that help to improve adhesion From the viewpoint of the concave-convex shape, the average primary particle diameter of the nanoparticles is preferably 90 nm or less, more preferably 70 nm or less, and still more preferably 50 nm or less.
作為奈米粒子之材料，較佳為無機氧化物。作為無機氧化物，可列舉：氧化矽、氧化鈦、氧化鋁、氧化鋯、氧化鈦、氧化鈮、氧化鋅、氧化錫、氧化鈰、氧化鎂等金屬或半金屬之氧化物。無機氧化物亦可為複數種(半)金屬之複合氧化物。例示之無機氧化物之中，就提昇密接性之效果較高之方面而言，較佳為氧化矽。為了提高與樹脂之密接性或親和性，亦可向無機氧化物粒子之表面導入丙烯醯基、環氧基等官能基。 As the material of the nanoparticles, inorganic oxides are preferred. Examples of inorganic oxides include metal or semimetal oxides such as silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, titanium oxide, niobium oxide, zinc oxide, tin oxide, cerium oxide, and magnesium oxide. Inorganic oxides may also be composite oxides of multiple (semi)metals. Among the exemplified inorganic oxides, silicon oxide is preferable in that the effect of improving adhesion is high. In order to improve the adhesion or affinity with the resin, functional groups such as acryl groups and epoxy groups can also be introduced into the surface of the inorganic oxide particles.
於為了提昇密接性而使用奈米粒子之情形時，相對於黏合劑成分之總量(黏合劑樹脂與奈米粒子之總計)100重量份，硬塗層中之奈米粒子之量較佳為5重量份以上，亦可為10重量份以上、20重量份以上或30重量份以上。有奈米粒子之量越多，則越能提昇硬塗層與形成於其上之薄膜之密接性的傾向。 In the case of using nanoparticles to improve adhesion, the amount of nanoparticles in the hard coat layer is preferably 5 parts by weight or more, may be 10 parts by weight or more, 20 parts by weight or more, or 30 parts by weight or more. There is a tendency that the adhesion between the hard coat layer and the thin film formed thereon can be improved as the amount of nanoparticles increases.
藉由於透明膜基材10上塗佈硬塗組合物，並視需要進行溶劑之去除及樹脂之硬化，而形成硬塗層11。硬塗組合物包含上述黏合劑成分及微粒子，視需要包含可使黏合劑成分溶解或分散之溶劑。於黏合劑樹脂成分為硬化性樹脂之情形時，較佳為於組合物中包含適當之聚合起始劑。例如，於黏合劑樹脂成分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。
The
硬塗組合物除上述成分以外，亦可包含調平劑、黏度調整劑(觸變劑、增黏劑等)、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、界面活性劑、潤滑劑等添加劑。 In addition to the above components, the hard coating composition may also contain leveling agents, viscosity modifiers (thixotropic agents, tackifiers, etc.), antistatic agents, antiblocking agents, dispersants, dispersion stabilizers, antioxidants, ultraviolet rays, etc. Absorbents, defoamers, surfactants, lubricants and other additives.
藉由使硬塗組合物包含觸變劑，而有容易抑制微粒子之沈降，於硬塗層之表面均勻地形成由微粒子形成之凹凸，形成適於減少眩光之表面形狀的傾向。作為觸變劑，可列舉：有機黏土、氧化聚烯烴、改性脲等。其中較佳為膨潤石等有機黏土。相對於黏合劑100重量份，較佳為調配0.3~5重量份左右之觸變劑。 When the hard coat composition contains a thixotropic agent, the sedimentation of the fine particles is easily suppressed, and unevenness made of the fine particles is uniformly formed on the surface of the hard coat layer, thereby tending to form a surface shape suitable for reducing glare. Examples of the thixotropic agent include organoclay, oxidized polyolefin, modified urea, and the like. Among them, organic clays such as bentonite are preferable. With respect to 100 parts by weight of the adhesive, it is preferable to prepare about 0.3 to 5 parts by weight of the thixotropic agent.
藉由使硬塗組合物包含調平劑，而有使硬塗層之表面形狀均勻之傾向。作為調平劑，例如可列舉氟系或矽酮系之調平劑，相對於黏合劑100重量份，調平劑之調配量較佳為0.01~3重量份左右。 When the hard-coat composition contains a leveling agent, it exists in the tendency which makes the surface shape of a hard-coat uniform. As the leveling agent, for example, a fluorine-based or silicone-based leveling agent can be mentioned, and the amount of the leveling agent is preferably about 0.01 to 3 parts by weight relative to 100 parts by weight of the adhesive.
作為硬塗組合物之塗佈方法，可採用棒式塗佈法、輥式塗佈法、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、逗號刀塗佈法等任意適當之方法。塗佈後之加熱溫度可根據硬塗組合物之組成等而設定為適當溫度，例如為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來進行光硬化。照射光之累計光量較佳為100~500mJ/cm2左右。 As the coating method of the hard coating composition, bar coating method, roll coating method, gravure coating method, rod coating method, slot coating method, curtain coating method, spray coating method, etc. Any appropriate method such as injection coating method and comma knife coating method. The heating temperature after coating can be set to an appropriate temperature according to the composition of the hard coat composition, etc., for example, it is about 50°C to 150°C. When the binder resin component is a photocurable resin, photocuring is performed by irradiating active energy rays such as ultraviolet rays. The cumulative light intensity of the irradiation light is preferably about 100 to 500 mJ/cm 2 .
硬塗層11之厚度並無特別限制，為了實現高硬度，較佳為2μm以上，更佳為4μm以上，進而較佳為5μm以上。另一方面，若硬塗層11之厚度過大，則有可能無法適當地形成硬塗層之表面凹凸或因凝聚破壞而使膜強度降低。因此，硬塗層11之厚度較佳為20μm以下，更佳為15μm以下，進而較佳為12μm以下。又，硬塗層11之厚度較佳為微粒子平均粒徑之1.2~4倍之範圍，更佳為1.5~3倍之範圍內。藉由使微粒子之粒徑與硬塗層之厚度的比為上述範圍，易使硬塗層表面上形成之凹凸形狀成為防眩性優異且適於眩光較少之顯示的形狀。
The thickness of the
硬塗膜之霧度為1%以上，較佳為1.5%以上，更佳為2%以上，進而較佳為3%以上。硬塗膜之霧度較佳為20%以下。硬塗膜之霧度較佳為4~20%，更佳為6~17%，進而較佳為7~15%。若硬塗膜之霧度為上述範圍，則可兼具防眩性及圖像清晰度。於霧度過小之情形時，防眩性有可能較差，於霧度過大之情形時，有圖像清晰度降低之傾向。如上所述，藉由調整硬塗層中所含之黏合劑與微粒子之折射率差及微粒子之含量，可將硬塗層(及硬塗膜)之霧度控制於適當範圍內。 The haze of the hard coat film is 1% or more, preferably 1.5% or more, more preferably 2% or more, still more preferably 3% or more. The haze of the hard coat film is preferably 20% or less. The haze of the hard coat film is preferably from 4 to 20%, more preferably from 6 to 17%, and still more preferably from 7 to 15%. If the haze of the hard coat film is within the above-mentioned range, both anti-glare properties and image clarity can be achieved. When the haze is too small, the anti-glare property may be poor, and when the haze is too large, the image definition tends to decrease. As mentioned above, the haze of the hard coat layer (and hard coat film) can be controlled within an appropriate range by adjusting the refractive index difference between the binder contained in the hard coat layer and the microparticles and the content of the microparticles.
硬塗層表面之算術平均粗糙度Ra較佳為0.05~0.25μm，更佳為0.06~0.2μm，進而較佳為0.07~0.18μm。硬塗層表面之凹凸之平均間隔RSm較佳為60~200μm，更佳為80~180μm，進而較佳為100~160μm。硬塗層之表面形狀參數及抗反射膜(防污層)之表面形狀參數可根據如下獲得之粗糙度曲線，依據JIS B0601：2001而算出，上述粗糙度曲線係使利用觸針式表面粗糙度測定器測得之長度4mm之剖面曲線通過截止值 0.8mm之廣域濾波器所得。 The arithmetic average roughness Ra of the hard coat surface is preferably 0.05-0.25 μm, more preferably 0.06-0.2 μm, and still more preferably 0.07-0.18 μm. The average interval RSm of the unevenness|corrugation on the surface of a hard-coat layer becomes like this. Preferably it is 60-200 micrometers, More preferably, it is 80-180 micrometers, More preferably, it is 100-160 micrometers. The surface shape parameters of the hard coat layer and the surface shape parameters of the anti-reflection film (anti-fouling layer) can be calculated according to the roughness curve obtained as follows according to JIS B0601:2001. The profile curve with a length of 4mm measured by the measuring device passes the cut-off value 0.8mm wide area filter obtained.
藉由調整微粒子之粒徑及含量，可調整算術平均粗糙度Ra及凹凸之平均間隔RSm。有微粒子之含量越多，則由微粒子形成之凸部之數量越多，因此RSm變小之傾向。又，有微粒子之平均粒徑越大，微粒子之含量越多，則Ra越大之傾向。 By adjusting the particle size and content of fine particles, the arithmetic mean roughness Ra and the average interval RSm between bumps and bumps can be adjusted. As the content of fine particles increases, the number of convex portions formed by fine particles increases, so RSm tends to decrease. Also, the larger the average particle diameter of the fine particles and the larger the content of the fine particles, the larger the Ra tends to be.
硬塗層表面之均方根粗糙度Rq較佳為0.06~0.3μm，更佳為0.08~0.25μm，進而較佳為0.09~0.2μm。硬塗層表面之最大剖面高度Rt較佳為0.3~2.5μm，更佳為0.5~2μm，進而較佳為0.7~1.7μm。硬塗層表面之最大高度Rz較佳為0.1~1.5μm，更佳為0.3~1μm，進而較佳為0.4~0.9μm。硬塗層表面之十點平均高度RzJIS較佳為0.05~1μm，更佳為0.1~0.8μm，進而較佳為0.2~0.6μm。 The root mean square roughness Rq of the hard coat surface is preferably 0.06-0.3 μm, more preferably 0.08-0.25 μm, further preferably 0.09-0.2 μm. The maximum sectional height Rt of the hard coat surface is preferably 0.3-2.5 μm, more preferably 0.5-2 μm, further preferably 0.7-1.7 μm. The maximum height Rz of the hard coat surface is preferably 0.1 to 1.5 μm, more preferably 0.3 to 1 μm, further preferably 0.4 to 0.9 μm. The ten-point average height Rz JIS of the hard coat surface is preferably from 0.05 to 1 μm, more preferably from 0.1 to 0.8 μm, and still more preferably from 0.2 to 0.6 μm.
硬塗層表面之平均傾斜角θa較佳為0.1°~1.1°，更佳為0.15~1.0°，進而較佳為0.2°~0.8°，尤佳為0.3°~0.6°。平均傾斜角θa係以如下方式算出，即，將基準長度L(=4mm)之粗糙度曲線中相鄰之山頂點與山谷最下點的差(高度h)之總計(h1+h2+h3……+hn)除以基準長度L，而獲得值△a，使用該值△a，根據下述式算出平均傾斜角θa。 The average inclination angle θa of the hard coat surface is preferably 0.1°-1.1°, more preferably 0.15-1.0°, further preferably 0.2°-0.8°, and especially preferably 0.3°-0.6°. The average inclination angle θa is calculated by taking the sum (h 1 +h 2 + h 3 ...+h n ) is divided by the reference length L to obtain a value Δa, and using this value Δa, the average inclination angle θa is calculated from the following formula.
θa=tan-1△a θa=tan -1 △a
於硬塗層11上形成抗反射層5之前，亦可對硬塗層11進行表面處理，
以進一步提昇硬塗層11與抗反射層5之密接性等。作為表面處理，可列舉：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、利用偶合劑進行之處理等表面改質處理。作為表面處理，亦可進行真空電漿處理。亦可藉由真空電漿處理來調整硬塗層之表面粗糙度。真空電漿處理(例如氬電漿處理)之放電電力為0.5~10kW左右，較佳為1~5kW左右。
Before forming the
於硬塗膜1之硬塗層11上，視需要經由底塗層3形成抗反射層5，並於抗反射層5上形成防污層7，藉此獲得抗反射膜。
On the
較佳為於硬塗膜1之硬塗層11與抗反射層5之間設置底塗層3。作為底塗層3之材料，可列舉：矽、鎳、鉻、錫、金、銀、鉑、鋅、鈦、銦、鎢、鋁、鋯、鈀等金屬；該等金屬之合金；該等金屬之氧化物、氟化物、硫化物或氮化物等。其中，底塗層之材料較佳為無機氧化物，尤佳為氧化矽或氧化銦。構成底塗層3之無機氧化物亦可為氧化銦錫(ITO)等複合氧化物。
Preferably, an
於底塗層3為氧化矽之情形時，就透光率高且對有機層(硬塗層)及無機層(抗反射層)兩者之接著力高之方面而言，尤佳為氧量少於化學計量組成者。非化學計量組成之底塗層3之氧量較佳為化學計量組成之60~99%左右。例如，於形成氧化矽(SiOx)層作為底塗層3之情形時，x較佳為1.20~
1.98。
In the case where the
底塗層3之厚度例如為1~20nm左右，較佳為3~15nm。若底塗層之厚度為上述範圍，則可兼具與硬塗層11之密接性及高透光性。
The thickness of the
抗反射層5包含折射率不同之2層以上薄膜。一般而言，抗反射層係以入射光與反射光之反轉相位互相抵消之方式調整薄膜之光學膜厚(折射率與厚度之積)。藉由使抗反射層為折射率不同之2層以上薄膜之多層積層體，可於可見光之寬頻帶波長範圍內減小反射率。
The
作為構成抗反射層5之薄膜之材料，可列舉金屬之氧化物、氮化物、氟化物等。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。為了減少與防污層之界面處之反射，設置為抗反射層5之最外層之薄膜54較佳為低折射率層。
Examples of the material of the thin film constituting the
高折射率層51、53例如折射率為1.9以上，較佳為2.0以上。作為高折射率材料，可列舉：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例如折射率為1.6以下，較佳為1.5以下。作為低折射率材料，可列舉：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。尤佳為使作為高折射率層之氧化鈮(Nb2O5)薄膜51、33與作為低折射率層之氧化矽(SiO2)薄膜52、54交替積
層。除低折射率層及高折射率層以外，亦可設置折射率為1.6~1.9左右之中等折射率層。
The high refractive index layers 51 and 53 have a refractive index of, for example, 1.9 or higher, preferably 2.0 or higher. 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), and the like. Among them, titanium oxide or niobium oxide is preferable. The low refractive index layers 52 and 54 have a refractive index of, 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, hafnium fluoride, and lanthanum fluoride. Among them, silicon oxide is preferred. More preferably, niobium oxide (Nb 2 O 5 )
高折射率層及低折射率層之膜厚分別為5~200nm左右，較佳為15~150nm左右。可根據折射率或積層構成等，以可見光之反射率變小之方式設計各層之膜厚。例如，作為高折射率層與低折射率層之積層構成，可列舉自硬塗膜側起為光學膜厚25nm~55nm左右之高折射率層51、光學膜厚35nm~55nm左右之低折射率層52、光學膜厚80nm~240nm左右之高折射率層53及光學膜厚120nm~150nm左右之低折射率層54的4層構成。
The film thicknesses of the high refractive index layer and the low refractive index layer are respectively about 5-200 nm, preferably about 15-150 nm. The film thickness of each layer can be designed so that the reflectance of visible light becomes small according to the refractive index or the composition of the laminated layers. For example, as a lamination structure of a high-refractive-index layer and a low-refractive-index layer, a high-refractive-
構成抗反射層5之薄膜之成膜方法並無特別限制，可為濕式塗佈法、乾式塗佈法之任一者。就可形成膜厚均勻的薄膜之方面而言，較佳為真空蒸鍍、CVD(Chemical vapor deposition，化學氣相沈積)、濺鍍、電子束蒸鍍等乾式塗佈法。其中，就易形成膜厚之均勻性優異、緻密且高強度之膜之方面而言，較佳為濺鍍法。藉由利用濺鍍法形成抗反射層，有設置於抗反射層5上之防污層7之耐磨耗性提昇之傾向。
The film-forming method of the thin film constituting the
於濺鍍法中，可藉由卷對卷式方式一面於一方向(長度方向)上搬送長條之硬塗膜，一面使薄膜連續成膜。於濺鍍法中，一面將氬等惰性氣體及視需要而存在之氧等反應性氣體導入至腔室內一面進行成膜。利用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金屬靶之反應性濺鍍之任一者來實施。為了以高速率使金屬氧化物成膜，較佳為使用金屬 靶之反應性濺鍍。 In the sputtering method, a long hard coating film can be continuously formed while transporting a long hard coating film in one direction (longitudinal direction) by a roll-to-roll method. In the sputtering method, a film is formed while introducing an inert gas such as argon and optionally a reactive gas such as oxygen into the chamber. Formation of the oxide layer by the sputtering method can be implemented by any of the method using an oxide target and reactive sputtering using a metal target. In order to form a metal oxide film at a high rate, it is preferable to use a metal Reactive sputtering of targets.
抗反射膜於抗反射層5上具備防污層7作為最表面層(面塗層)。藉由於最表面上設置防污層，可減少來自外部環境之污染(指紋、手垢、灰塵等)之影響，並且容易去除附著於表面之污染物質。
The antireflection film has an
為了維持抗反射層5之抗反射特性，較佳為防污層7與抗反射層5之最表面之低折射率層54的折射率差較小。防污層7之折射率較佳為1.6以下，更佳為1.55以下。
In order to maintain the anti-reflection properties of the
作為防污層7之材料，較佳為含氟之化合物。含氟之化合物可賦予防污性，並且可有助於低折射率化。其中，就撥水性優異，可發揮高防污性之方面而言，較佳為含有全氟聚醚骨架之氟系聚合物。就提高防污性之觀點而言，尤佳為具有可剛性並列之主鏈結構之全氟聚醚。作為全氟聚醚之主鏈骨架之結構單元，較佳為碳數1~4之可具有支鏈之全氟環氧烷，例如可列舉：全氟環氧甲烷(-CF2O-)、全氟環氧乙烷(-CF2CF2O-)、全氟環氧丙烷(-CF2CF2CF2O-)、全氟環氧異丙烷(-CF(CF3)CF2O-)等。
The material of the
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CVD法等乾式法等而形成。防污層之厚度通常為2~50nm左右。有防污層7之厚度越大，則防污性越高之傾向。又，有防污層7之厚度越大，則越能抑制因磨耗引起之防污特定之降低的傾向。防污層之厚度較佳為5nm
以上，更佳為7nm以上，進而較佳為8nm以上。另一方面，就於防污層表面形成反映硬塗層表面之凹凸形狀之表面形狀，提高防眩性之觀點而言，防污層之厚度較佳為30nm以下，更佳為20nm以下。
The antifouling layer can be formed by a wet method such as a reverse coating method, a die coating method, and a gravure coating method, or a dry method such as a CVD method. The thickness of the antifouling layer is usually about 2~50nm. The larger the thickness of the
為了提高防污染性及污染物質去除性，防污層7之水接觸角較佳為100°以上，更佳為102°以上，進而較佳為105°以上。有水接觸角越大，則撥水性越高，防止污染物質附著之效果或污染物質去除性越高之傾向。水接觸角一般而言為125°以下。
In order to improve the anti-pollution property and the removability of pollutants, the water contact angle of the
抗反射膜之霧度為1%以上，較佳為1.5%以上，更佳為2%以上，進而較佳為3%以上。抗反射膜之霧度較佳為20%以下。抗反射膜之霧度較佳為4~20%，更佳為6~17%，進而較佳為7~15%。於抗反射膜之霧度過小之情形時，防眩性有可能較差，於霧度過大之情形時，有圖像清晰度降低之傾向。抗反射層5及防污層7之厚度較小，幾乎不產生霧度，因此抗反射膜之霧度與硬塗膜之霧度大致相等。
The haze of the antireflection film is 1% or more, preferably 1.5% or more, more preferably 2% or more, still more preferably 3% or more. The haze of the antireflection film is preferably 20% or less. The haze of the antireflection film is preferably 4-20%, more preferably 6-17%, and still more preferably 7-15%. When the haze of the antireflection film is too small, the anti-glare property may be poor, and when the haze is too large, the image definition tends to decrease. The thickness of the
抗反射膜之表面、即防污層7之表面之算術平均粗糙度Ra較佳為0.05~0.25μm，更佳為0.06~0.2μm，進而較佳為0.07~0.18μm。防污層表面之凹凸之平均間隔RSm較佳為60~200μm，更佳為80~180μm，進而較佳為100~160μm。
The arithmetic average roughness Ra of the surface of the antireflection film, that is, the surface of the
由於硬塗層11上形成之抗反射層5及防污層7之厚度較小，故易於防
污層7之表面形成反映硬塗層11之表面形狀之凹凸形狀。因此，可藉由調整硬塗層11之微粒子之粒徑或調配量等，來調整硬塗層之表面形狀，而獲得具有上述Ra及RSm之抗反射膜。又，亦可藉由對硬塗層11實施真空電漿處理等表面處理來調整表面形狀。
Since the thickness of the
藉由於抗反射膜之表面形成凹凸，可減少外界光或影像之映入。藉由使抗反射膜之算術平均粗糙度Ra為0.05μm以上，而有提高防眩性之傾向。另一方面，於Ra過大之情形時，有可能產生眩光不良。又，藉由使利用微米級粒子形成之凸部均勻地分散於面內，而有凹凸之平均間隔RSm變小，於圖像顯示面板與抗反射膜之間之間隙較大之情形時，亦可抑制眩光不良的傾向。 By forming concavities and convexities on the surface of the anti-reflection film, reflection of external light or images can be reduced. When the arithmetic average roughness Ra of the antireflection film is 0.05 μm or more, the antiglare property tends to be improved. On the other hand, when Ra is too large, glare defects may occur. In addition, by uniformly dispersing the protrusions formed by micron-sized particles in the plane, the average interval RSm between the protrusions and recesses becomes smaller, and when the gap between the image display panel and the antireflection film is large, it is also Can suppress the tendency of glare defect.
表面之算術平均粗糙度Ra及凹凸之平均間隔RSm為上述範圍的抗反射膜由於能夠使外界光均勻地散射，故具有優異之防眩性，且有抑制眩光之傾向。又，Ra及RSm處於上述範圍內之抗反射膜藉由表面之凹凸而具有優異之滑動性，耐擦傷性優異，並且防污層之耐磨耗性亦優異。關於抗反射膜，較佳為於使用鋼絲絨施加2kg/cm2之負載之狀態下實施往返10次之滑動試驗時，表面未確認到擦傷。 The anti-reflection film whose arithmetic average surface roughness Ra and average spacing RSm of concavities and convexities fall within the above ranges has excellent anti-glare property and tends to suppress glare since it can uniformly scatter external light. In addition, the antireflection film having Ra and RSm within the above ranges has excellent sliding properties due to surface irregularities, is excellent in scratch resistance, and is also excellent in abrasion resistance of the antifouling layer. Regarding the anti-reflective film, it is preferable that no scratches are confirmed on the surface when a sliding test is performed 10 times in a state where a load of 2 kg/cm 2 is applied using steel wool.
抗反射膜表面之平均傾斜角θa較佳為0.1°~1.1°，更佳為0.15~1.0°，進而較佳為0.2°~0.8°，尤佳為0.3°~0.6°。於θa過小之情形時，有防眩性變得不充分之傾向，於θa過大之情形時，有眩光變強之傾向。 The average inclination angle θa of the surface of the antireflection film is preferably 0.1°-1.1°, more preferably 0.15-1.0°, still more preferably 0.2°-0.8°, especially preferably 0.3°-0.6°. When θa is too small, the anti-glare property tends to be insufficient, and when θa is too large, glare tends to become strong.
抗反射膜表面之均方根粗糙度Rq較佳為0.06~0.3μm，更佳為0.08~0.25μm，進而較佳為0.09~0.2μm。抗反射膜表面之最大剖面高度Rt較佳為0.3~2.5μm，更佳為0.5~2μm，進而較佳為0.7~1.7μm。抗反射膜表面之最大高度Rz較佳為0.1~1.5μm，更佳為0.3~1μm，進而較佳為0.4~0.9μm。抗反射膜表面之十點平均高度RzJIS較佳為0.05~1μm，更佳為0.1~0.8μm，進而較佳為0.2~0.6μm。於除Ra及RSm處於上述範圍內以外，Rq、Rt、Rz、RzJIS亦處於上述範圍內之情形時，有抗反射膜之防眩性優異，並且於圖像顯示面板與抗反射膜之間之間隙較大之情形時，亦可抑制眩光的傾向。 The root mean square roughness Rq of the surface of the antireflection film is preferably 0.06-0.3 μm, more preferably 0.08-0.25 μm, and still more preferably 0.09-0.2 μm. The maximum cross-sectional height Rt of the surface of the antireflection film is preferably 0.3-2.5 μm, more preferably 0.5-2 μm, and still more preferably 0.7-1.7 μm. The maximum height Rz of the antireflection film surface is preferably 0.1-1.5 μm, more preferably 0.3-1 μm, and still more preferably 0.4-0.9 μm. The ten-point average height Rz JIS of the surface of the antireflection film is preferably from 0.05 to 1 μm, more preferably from 0.1 to 0.8 μm, and still more preferably from 0.2 to 0.6 μm. When Rq, Rt, Rz, and Rz JIS are also within the above ranges in addition to Ra and RSm within the above ranges, the anti-reflection film has excellent anti-glare properties, and the anti-reflection film is between the image display panel and the anti-reflection film. In the case of a large gap, the tendency of glare can also be suppressed.
抗反射膜例如可配置於液晶顯示器或有機EL顯示器等圖像顯示裝置之表面而使用。例如，藉由於包含液晶單元或有機EL單元等圖像顯示介質之面板之視認側表面配置抗反射膜，可減少外界光之反射，可提昇圖像顯示裝置之視認性。 The antireflection film can be used, for example, by placing it on the surface of an image display device such as a liquid crystal display or an organic EL display. For example, by disposing an anti-reflection film on the viewing side surface of a panel including an image display medium such as a liquid crystal unit or an organic EL unit, the reflection of external light can be reduced, and the visibility of the image display device can be improved.
抗反射膜可直接貼合於圖像顯示裝置之表面而使用，亦可與其他膜積層。例如，藉由於透明膜基材10之不形成硬塗層之面上貼合偏光元件，可形成附帶抗反射層之偏光板。
The anti-reflection film can be directly attached to the surface of the image display device, and can also be laminated with other films. For example, a polarizing plate with an antireflection layer can be formed by attaching a polarizing element to the surface of the
抗反射膜亦可經由其他光學構件而配置於圖像顯示單元之視認側表面。例如，於圖2所示之圖像顯示裝置201中，於圖像顯示單元20之視認側表面上，經由透明黏著片9而配置有覆蓋窗8，於覆蓋窗8之視認側表
面上配置有抗反射膜101。覆蓋窗8與抗反射膜101之間亦可設置有適當之接著劑層或黏著劑層(未圖示)。圖像顯示單元20與覆蓋窗8之間亦可配置有偏光板等光學膜或觸控感測器等。
The anti-reflection film can also be arranged on the viewing side surface of the image display unit through other optical components. For example, in the
於圖像顯示單元20上配置有覆蓋窗等光學構件之情形時，圖像顯示單元20與抗反射膜101之間存在特定之間隙D。有該間隙D越大，則越易因硬塗層表面之凹凸而產生眩光之傾向，尤其是若間隙超過1mm，則該傾向越顯著。
When an optical member such as a cover window is disposed on the
如上所述，藉由使用具有特定之表面形狀之抗反射膜，即使於間隙D較大之情形時，亦可實現眩光受到抑制之良好顯示。圖像顯示單元20與抗反射膜101之間隙D可為1.2mm以上、1.5mm以上或1.8mm以上。間隙D可為5mm以下或4mm以下或3mm以下。
As described above, by using an antireflection film having a specific surface shape, good display with suppressed glare can be realized even when the gap D is large. The gap D between the
以下，列舉實施例更詳細地說明本發明，但本發明並不限定於以下實施例。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.
將作為黏合劑樹脂成分之季戊四醇聚丙烯酸酯(大阪有機化學公司製造之「Viscoat#300」)50重量份、聚胺基甲酸酯丙烯酸酯預聚物(日本合 成化學公司製造之「紫光UV-1700TL」)50重量份、苯乙烯與甲基丙烯酸甲酯(MMA)之共聚交聯粒子(積水化成品工業公司製造之「Techpolymer SSX-540TNR」，平均粒徑3.6μm，折射率1.56)4重量份、作為觸變劑之有機化膨潤石(國峰工業公司製造之「Sumecton SAN」)1.5重量份、光聚合起始劑(IGM Resins公司製造之「Omnirad 907」)3重量份以及矽酮系調平劑(共榮社化學公司製造之「Polyflow LE303」)0.15重量份加以混合，並利用甲苯/環戊酮混合溶劑(重量比70/30)進行稀釋，而製備固形物成分濃度50重量%之硬塗組合物。再者，上述調配量為固形物成分(不揮發分)之量，有機化膨潤石係以固形物成分成為6重量%之方式用甲苯進行稀釋後再使用(以下組合物亦相同)。黏合劑(不含微粒子，僅使黏合劑樹脂成分硬化而成)之折射率為1.51。 50 parts by weight of pentaerythritol polyacrylate (manufactured by Osaka Organic Chemical Co., Ltd. "Viscoat #300"), polyurethane acrylate prepolymer (Nippon Co., Ltd.) "Ultraviolet UV-1700TL" manufactured by Cheng Chemical Co., Ltd.) 50 parts by weight, copolymerized cross-linked particles of styrene and methyl methacrylate (MMA) ("Techpolymer SSX-540TNR" manufactured by Sekisui Chemical Industry Co., Ltd., average particle diameter 3.6 μm, refractive index 1.56) 4 parts by weight, 1.5 parts by weight of organic bentonite ("Sumecton SAN" manufactured by Guofeng Industrial Co., Ltd.) as a thixotropic agent, photopolymerization initiator ("Omnirad 907" manufactured by IGM Resins, ”) and 0.15 parts by weight of a silicone-based leveling agent ("Polyflow LE303" manufactured by Kyoeisha Chemical Co., Ltd.) were mixed and diluted with a toluene/cyclopentanone mixed solvent (weight ratio 70/30), A hard coating composition having a solid content concentration of 50% by weight was prepared. In addition, the above-mentioned compounding quantity is the quantity of solid content (non-volatile matter), and the organic bentonite was used after diluting with toluene so that the solid content may become 6 weight% (the following composition is also the same). The refractive index of the binder (does not contain microparticles, but only hardens the binder resin component) is 1.51.
使用缺角輪塗佈機(註冊商標)將上述硬塗組合物塗佈於厚度40μm之三乙醯纖維素膜(Konica Minolta Opto公司製造之「KC4UA」)上，並於80℃下加熱1分鐘。然後，利用高壓水銀燈照射累計光量300mJ/cm2之紫外線，使塗佈層硬化，而形成厚度8.0μm之防眩性硬塗層。 The above-mentioned hard coating composition was coated on a triacetyl cellulose film ("KC4UA" manufactured by Konica Minolta Opto Co., Ltd.) with a thickness of 40 μm using a notched wheel coater (registered trademark), and heated at 80° C. for 1 minute . Then, the coating layer was cured by irradiating ultraviolet rays with a cumulative light intensity of 300 mJ/cm 2 using a high-pressure mercury lamp, thereby forming an anti-glare hard coat layer with a thickness of 8.0 μm.
將形成有硬塗層之三乙醯纖維素膜導入至卷對卷式方式之濺鍍成膜裝置中，一面使膜移行，一面對防眩性硬塗層形成面進行轟擊處理(利用氬氣進行之電漿處理)，然後使3.5nm之SiOx層(x<2)成膜作為底塗層，並於其上依序使10.1nm之Nb2O5層、27.5nm之SiO2層、105.0nm之 Nb2O5層及83.5nm之SiO2層成膜。底塗層及SiO2層成膜時使用Si靶，Nb2O5層成膜時使用Nb靶。於SiO2層成膜及Nb2O5層成膜時，藉由電漿發光監測(PEM)控制，使成膜模式以維持過渡區域之方式調整導入之氧量。 The triacetyl cellulose film formed with the hard coat layer was introduced into a roll-to-roll type sputtering film forming device, and while the film was moving, bombardment treatment was performed on the surface where the antiglare hard coat layer was formed (using argon Plasma treatment by gas), and then make a 3.5nm SiO x layer (x<2) as an undercoat layer, and sequentially make a 10.1nm Nb 2 O 5 layer and a 27.5nm SiO 2 layer on it , 105.0nm Nb 2 O 5 layer and 83.5nm SiO 2 layer. A Si target was used for forming an undercoat layer and an SiO 2 layer, and a Nb target was used for forming a Nb 2 O 5 layer. During the formation of the SiO 2 layer and the Nb 2 O 5 layer, the amount of oxygen introduced is adjusted to maintain the transition region in the film formation mode by controlling the plasma luminescence monitoring (PEM).
以乾燥後厚度成為10nm之方式，將含有主鏈骨架上包含-(O-CF(CF3)-CF2)-之全氟醚的氟系樹脂溶液塗佈於抗反射層之表面SiO2層上，而形成作為面塗層之防污層。 Apply a fluororesin solution containing perfluoroether containing -(O-CF(CF 3 )-CF 2 )- on the main chain skeleton to the SiO 2 layer on the surface of the antireflection layer so that the thickness after drying becomes 10nm To form an anti-fouling layer as a top coat.
於製備硬塗組合物時，將粒子之調配量變更為如表1所示，除此以外，以與實施例1相同之方式進行防眩性硬塗膜之製作、底塗層及抗反射層之形成以及防污層之形成。 When preparing the hard coating composition, the formulation amount of the particles was changed as shown in Table 1. Except that, the production of the antiglare hard coating film, the primer layer and the antireflection layer were carried out in the same manner as in Example 1. Formation and antifouling layer formation.
將奈米氧化矽粒子與硬化性丙烯酸樹脂之複合物之溶液(奈米氧化矽粒子之平均一次粒徑：40nm；固形物成分中之奈米氧化矽粒子之比率：60重量%；固形物成分：50重量%)67重量份、及多官能丙烯酸酯33重量份加以混合。向該溶液之固形物成分100重量份中混合2.0重量份之交聯聚甲基丙烯酸甲酯(PMMA)粒子(積水化成品工業公司製造之「Tech Polymer SSX-103」，平均粒徑3.0μm，折射率1.50)、1.5重量份之作為觸變劑之有機化膨潤石(國峰工業公司製造之「Sumecton SAN」)、3重量份之光聚合起始劑(IGM Resins公司製造之「OMNIRAD 907」)以及0.15重 量份之矽酮系調平劑(共榮社化學公司製造之「Polyflow LE303」)，並利用甲苯/環戊酮混合溶劑(重量比70/30)進行稀釋，而製備固形物成分濃度45重量%之硬塗組合物。黏合劑(不包含PMMA粒子，使丙烯酸樹脂與奈米氧化矽粒子之混合材料硬化而成)之折射率為1.48。 Solution of composite of nano-silicon oxide particles and curable acrylic resin (average primary particle size of nano-silicon oxide particles: 40nm; ratio of nano-silicon oxide particles in solid content: 60% by weight; solid content : 50% by weight) 67 parts by weight and 33 parts by weight of multifunctional acrylate were mixed. 2.0 parts by weight of cross-linked polymethyl methacrylate (PMMA) particles ("Tech Polymer SSX-103" manufactured by Sekisui Chemical Industry Co., Ltd., with an average particle diameter of 3.0 μm) were mixed with 100 parts by weight of the solid content of the solution. Refractive index 1.50), 1.5 parts by weight of organic bentonite as a thixotropic agent ("Sumecton SAN" manufactured by Guofeng Industrial Co., Ltd.), 3 parts by weight of photopolymerization initiator ("OMNIRAD 907" manufactured by IGM Resins Co., Ltd. ) and 0.15 weight A quantity of silicone-based leveling agent ("Polyflow LE303" manufactured by Kyoeisha Chemical Co., Ltd.) was diluted with a mixed solvent of toluene/cyclopentanone (weight ratio 70/30) to prepare a solid content concentration of 45 wt. % of the hard coating composition. The refractive index of the binder (which does not contain PMMA particles and is made by hardening a mixture of acrylic resin and nano-silicon oxide particles) is 1.48.
除了使用上述硬塗組合物以外，以與實施例1相同之方式進行防眩性硬塗膜之製作、底塗層及抗反射層之形成以及防污層之形成。 Production of an antiglare hard coat film, formation of an undercoat layer and an antireflection layer, and formation of an antifouling layer were performed in the same manner as in Example 1 except for using the above-mentioned hard coat composition.
於製備硬塗組合物時，將PMMA粒子之調配量變更為1.0重量份，除此以外，以與實施例6相同之方式進行防眩性硬塗膜之製作、底塗層及抗反射層之形成以及防污層之形成。 When preparing the hard coating composition, the compounding amount of the PMMA particles was changed to 1.0 parts by weight, except that, in the same manner as in Example 6, the preparation of the antiglare hard coating film, the primer layer and the antireflection layer were carried out. Formation and formation of antifouling layer.
於製備硬塗組合物時，將PMMA粒子之調配量變更為8.0重量份，且除PMMA粒子以外，還調配1.4重量份之矽酮粒子(邁圖高新材料日本有限公司製造之「Tospearl 130」，平均粒徑3μm，折射率1.43)。除此以外，以與實施例6相同之方式進行防眩性硬塗膜之製作、底塗層及抗反射層之形成以及防污層之形成。 When preparing the hard coating composition, the blending amount of PMMA particles was changed to 8.0 parts by weight, and in addition to PMMA particles, 1.4 parts by weight of silicone particles ("Tospearl 130" manufactured by Momentive High-Tech Materials Japan Co., Ltd., Average particle size 3μm, refractive index 1.43). Except for this, preparation of an antiglare hard coat film, formation of a primer layer and an antireflection layer, and formation of an antifouling layer were performed in the same manner as in Example 6.
將50重量份之作為黏合劑樹脂之季戊四醇三丙烯酸酯(大阪有機化學公司製造之「Viscoat#300」)、50重量份之聚胺基甲酸酯丙烯酸酯預聚物
(新中村化學工業公司製造之「UA-53H-80BK」)、3.5重量份之矽酮粒子(邁圖高新材料日本有限公司製造之「Tospearl 130」，平均粒徑3μm，折射率1.43)、2重量份之有機化膨潤石(國峰工業公司製造之「Sumecton SAN」)、3重量份之光聚合起始劑(IGM Resins公司製造之「OMNIRAD 907」)以及0.2重量份之矽酮系調平劑(DIC公司製造之「Grandic PC4100」)加以混合，並利用甲苯/環戊酮混合溶劑(重量比70/30)進行稀釋，而製備固形物成分濃度33重量%之硬塗組合物。黏合劑之折射率為1.52。
50 parts by weight of pentaerythritol triacrylate (manufactured by Osaka Organic Chemicals Co., Ltd. "Viscoat #300") as a binder resin, 50 parts by weight of polyurethane acrylate prepolymer
("UA-53H-80BK" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 3.5 parts by weight of silicone particles ("Tospearl 130" manufactured by Momentive High-Tech Materials Japan Co., Ltd.,
除了使用上述硬塗組合物，並將硬塗層之厚度變更為6.3μm以外，以與實施例1相同之方式製作防眩性硬塗膜，並於硬塗層上形成抗反射層及防眩層。 Except using the above-mentioned hard coat composition and changing the thickness of the hard coat layer to 6.3 μm, an antiglare hard coat film was prepared in the same manner as in Example 1, and an antireflection layer and an antiglare layer were formed on the hard coat layer. Floor.
將100重量份之作為黏合劑樹脂之以聚胺基甲酸酯丙烯酸酯為主成分之紫外線硬化型樹脂組合物(DIC公司製造之「UNIDIC 17-806」)、14重量份之交聯苯乙烯粒子(綜研化學公司製造之「SX-350H」，平均粒徑3.5μm，折射率1.59)、2.5重量份之作為觸變劑之有機化膨潤石(國峰工業公司製造之「Sumecton SAN」)、5重量份之光聚合起始劑(IGM Resins公司製造之「OMNIRAD 907」)及1重量份之氟系調平劑(DIC公司製造之「MEGAFAC F40N」)加以混合，並利用甲苯/環戊酮混合溶劑(重量比70/30)進行稀釋，而製備固形物成分濃度40重量%之硬塗組合物。黏合劑之折射率為1.51。 100 parts by weight of an ultraviolet curable resin composition ("UNIDIC 17-806" manufactured by DIC Corporation) mainly composed of polyurethane acrylate as a binder resin, 14 parts by weight of cross-linked styrene Particles ("SX-350H" manufactured by Soken Chemical Co., Ltd., average particle diameter 3.5 μm, refractive index 1.59), 2.5 parts by weight of organic bentonite as a thixotropic agent ("Sumecton SAN" manufactured by Guofeng Industrial Co., Ltd.), 5 parts by weight of a photopolymerization initiator ("OMNIRAD 907" manufactured by IGM Resins) and 1 part by weight of a fluorine-based leveling agent ("MEGAFAC F40N" manufactured by DIC Corporation) were mixed and mixed with toluene/cyclopentanone The mixed solvent (weight ratio 70/30) was diluted to prepare a hard coating composition with a solid content concentration of 40% by weight. The refractive index of the adhesive is 1.51.
除了使用上述硬塗組合物，於120℃下進行5分鐘加熱處理，並將硬塗層之厚度變更為7.0μm以外，以與實施例1相同之方式製作防眩性硬塗膜，並於硬塗層上形成抗反射層及防眩層。 Except using the above-mentioned hard coating composition, heat treatment was carried out at 120° C. for 5 minutes, and the thickness of the hard coating was changed to 7.0 μm, an antiglare hard coating film was prepared in the same manner as in Example 1, and the An antireflective layer and an antiglare layer are formed on the coating.
將100重量份之作為黏合劑樹脂之以聚胺基甲酸酯丙烯酸酯為主成分之紫外線硬化型樹脂組合物(DIC公司製造之「UNIDIC 17-806」)、5重量份之光聚合起始劑(IGM Resins公司製造之「OMNIRAD 907」)及0.01重量份之矽酮系調平劑(DIC公司製造之「GRANDIC PC4100」)加以混合，並利用丙二醇單甲醚/環戊酮混合溶劑(重量比55/45)進行稀釋，而製備固形物成分濃度36重量%之硬塗組合物。 100 parts by weight of an ultraviolet curable resin composition ("UNIDIC 17-806" manufactured by DIC Corporation) mainly composed of polyurethane acrylate as a binder resin, 5 parts by weight of a photopolymerization initiator ("OMNIRAD 907" manufactured by IGM Resins Company) and 0.01 parts by weight of a silicone-based leveling agent ("GRANDIC PC4100" manufactured by DIC Company) were mixed, and a mixed solvent of propylene glycol monomethyl ether/cyclopentanone (weight Ratio 55/45) was diluted to prepare a hard coating composition with a solid content concentration of 36% by weight.
除了使用上述硬塗組合物，於90℃下進行1分鐘加熱處理，並將硬塗層之厚度變更為7.8μm以外，以與實施例1相同之方式製作硬塗膜，並於硬塗層上形成抗反射層及防眩層。 Except using the above-mentioned hard coating composition, performing heat treatment at 90° C. for 1 minute, and changing the thickness of the hard coating to 7.8 μm, a hard coating film was prepared in the same manner as in Example 1, and coated on the hard coating Form anti-reflective layer and anti-glare layer.
藉由霧度計(村上色彩技術研究所公司製造之「HM-150」)，自防污層形成面側照射光，依據JIS K7136測定反射膜之霧度。 With a haze meter ("HM-150" manufactured by Murakami Color Technology Research Institute Co., Ltd.), light is irradiated from the side where the antifouling layer is formed, and the haze of the reflective film is measured in accordance with JIS K7136.
於抗反射膜之三乙醯纖維素膜側之面(不形成抗反射層之面)上，介以厚度20μm之丙烯酸系黏著劑而貼合厚度1.3mm之載玻片(MATSUNAMI公司製造之「MICRO SLIDE GLASS」，45×50mm)，而製作測定用試樣。使用具有測定針(頭端部(金剛石)之曲率半徑R=2μm)之觸針式表面粗糙度測定器(小阪研究所公司製造之高精度微細形狀測定器「Surfcorder ET4000」)，於掃描速度0.1mm/秒、測定長度4mm之條件下，於固定方向上測定上述試樣之防眩層之表面形狀，並藉由測定裝置附帶之程式，依據JIS B0601：2001，根據通過截止值0.8mm之廣域濾波器而獲得之粗糙度曲線，求出算術平均粗糙度Ra、粗糙度曲線要素之平均長度RSm、最大剖面高度Rt、十點平均高度RzJIS、均方根粗糙度Rq、最大高度Rz及平均傾斜角θa。 On the surface of the triacetyl cellulose film side of the antireflection film (the surface on which the antireflection layer is not formed), a glass slide with a thickness of 1.3 mm (manufactured by MATSUNAMI Co., Ltd. MICRO SLIDE GLASS", 45×50mm), and make a sample for measurement. Using a stylus-type surface roughness measuring instrument (a high-precision micro-shape measuring instrument "Surfcorder ET4000" manufactured by Kosaka Laboratory Co., Ltd.) with a measuring needle (the radius of curvature of the tip (diamond) R = 2 μm), at a scanning speed of 0.1 Under the conditions of mm/sec and measuring length 4mm, measure the surface shape of the anti-glare layer of the above sample in a fixed direction, and use the program attached to the measuring device, according to JIS B0601:2001, according to the width of the cut-off value of 0.8mm The roughness curve obtained by the domain filter is used to calculate the arithmetic mean roughness Ra, the average length RSm of roughness curve elements, the maximum profile height Rt, the ten-point average height Rz JIS , the root mean square roughness Rq, the maximum height Rz and Average inclination angle θa.
於抗反射膜之三乙醯纖維素膜側之面上，介以厚度20μm之丙烯酸系黏著劑而貼合厚度1.5mm之無鹼玻璃，並以抗反射層形成面成為上側之方式載置於Apple公司製造之iPhone7(於畫面尺寸4.7英吋、326ppi之液晶面板上，介以厚度約200μm之透明黏著片而貼合有厚度約1mm之覆蓋玻璃)上。畫面(液晶面板)與抗反射膜之間之間隙為2.7mm。將亮度設為最大，使其顯示綠色畫面，自距離試樣30cm之正上方視認畫面。將視認到畫面眩光者設為×，將未見到眩光者設為○。 On the surface of the triacetyl cellulose film side of the anti-reflection film, a non-alkali glass with a thickness of 1.5 mm was bonded through an acrylic adhesive with a thickness of 20 μm, and placed on the surface with the anti-reflection layer forming surface on the upper side. iPhone7 manufactured by Apple (on a liquid crystal panel with a screen size of 4.7 inches and 326ppi, a cover glass with a thickness of about 1mm is pasted through a transparent adhesive sheet with a thickness of about 200μm). The gap between the screen (liquid crystal panel) and the antireflection film is 2.7 mm. Set the brightness to the maximum to make it display a green screen, and recognize the screen from directly above the sample at a distance of 30cm. Those who visually recognized glare on the screen were rated as x, and those who did not see glare were rated as ○.
向防污層表面滴加約5.0μL之水。自滴加起2秒鐘後，使用接觸角測 定裝置(協和界面化學公司製造之「DMo-701」)，測定防污層表面與液滴端部之切線之角度(水接觸角之初始值)。拭去水滴之後，使用加工毛氈(Kaifelt工業公司製造、Φ10×L10、密度0.52g/cm3)，以負載200g、5m/分鐘之速度滑動3000次之後，測定水接觸角(滑動後之水接觸角)。 Add about 5.0 μL of water dropwise to the surface of the antifouling layer. After 2 seconds from the drop, measure the angle of the tangent between the surface of the antifouling layer and the end of the drop (initial value of the water contact angle) using a contact angle measuring device (“DMo-701” manufactured by Kyowa Interface Chemical Co., Ltd.) . After wiping off the water droplets, use a processing felt (manufactured by Kaifelt Industries, Φ10×L10, density 0.52g/cm 3 ), slide 3000 times with a load of 200g and a speed of 5m/min, and measure the water contact angle (water contact angle after sliding) horn).
於擦傷試驗機之直徑11mm之圓柱之平面上安裝鋼絲絨(NIHON STEEL WOOL製造之「Bonstar # 0000)，於負載1.0kg、2.0kg及3.0kg之條件下，於上述樣品表面上以100mm/秒之速度往返10次之後，目視觀察樣品表面上之擦傷，並藉由以下指標進行判定。 Install steel wool ("Bonstar # 0000" manufactured by NIHON STEEL WOOL) on the flat surface of a cylinder with a diameter of 11mm in the scratch tester, and under the conditions of loads of 1.0kg, 2.0kg and 3.0kg, the speed of 100mm/second on the surface of the above sample After reciprocating 10 times at the speed, visually observe the scratches on the surface of the sample, and judge by the following indicators.
○：於負載3kg之試驗中未見到擦傷 ○: No scratches were seen in the test with a load of 3kg
△：於負載3kg之試驗中見到擦傷，但於負載2kg之試驗中未見到擦傷 △: Scratches were seen in the test with a load of 3kg, but no scratches were seen in the test with a load of 2kg
×：於負載2kg之試驗中見到擦傷 ×: Scratches were seen in the test with a load of 2kg
將上述實施例及比較例中之抗反射膜之構成(硬塗層之黏合劑及微粒子之組成)及抗反射膜之評價結果示於表1。 Table 1 shows the composition of the antireflection film (composition of the binder of the hard coat layer and the composition of fine particles) and the evaluation results of the antireflection film in the above-mentioned examples and comparative examples.
於不含微粒子之硬塗層上設置有底塗層、抗反射層及防污層之比較例3中，抗反射膜之耐擦傷性差。又，滑動試驗後水接觸角大幅降低。認為其原因在於：防污層之耐磨耗性低，滑動試驗後防污層有磨耗。 In Comparative Example 3 in which a primer layer, an antireflection layer, and an antifouling layer were provided on a hard coat layer not containing fine particles, the antireflection film had poor scratch resistance. Also, the water contact angle decreased significantly after the sliding test. The reason for this is considered to be that the abrasion resistance of the antifouling layer was low, and the antifouling layer was abraded after the sliding test.
形成有含苯乙烯微粒子之硬塗層之比較例2中，黏合劑與微粒子之折射率差大，故霧度高，圖像通透感差。比較例1與比較例2相比霧度降低，但視認到圖像眩光，視認性差。再者，以畫面與抗反射膜之間之間隙成為0.5mm之方式配置比較例1之抗反射膜，對眩光進行評價後，未見到眩光，視認性良好。 In Comparative Example 2 in which the hard coat layer containing styrene microparticles was formed, the difference in refractive index between the binder and the microparticles was large, so the haze was high, and the transparency of the image was poor. In Comparative Example 1, the haze was lower than that of Comparative Example 2, but image glare was seen and the visibility was poor. Furthermore, the antireflection film of Comparative Example 1 was placed so that the gap between the screen and the antireflection film was 0.5 mm, and the glare was evaluated. No glare was observed, and the visibility was good.
認為：凹凸之間隔RSm較大之比較例1之抗反射膜於接近圖像顯示單元而配置之情形時，不易產生眩光，但於與圖像顯示單元之間隙較大之情形時，易強調形成有由粒子產生之凹凸之區域與未形成凹凸之區域的亮度差，而產生眩光。又，比較例1中，初始水接觸角為112°，於滑動試驗後降低至104°，耐磨耗性不充分。 It is considered that the anti-reflection film of Comparative Example 1, which has a relatively large interval RSm between concavities and convexities, is less likely to generate glare when it is arranged close to the image display unit, but it is easy to emphasize the formation when the gap with the image display unit is large. Glare is caused by the difference in brightness between the area with the unevenness produced by the particles and the area without the unevenness. Also, in Comparative Example 1, the initial water contact angle was 112°, which decreased to 104° after the sliding test, and the abrasion resistance was insufficient.
實施例1~8之抗反射膜均無眩光，表現出良好的視認性，且於滑動試驗後亦表現出高水接觸角度。根據以上結果可知，藉由調整硬塗層中所含之微粒子之種類及含量，將霧度及表面形狀參數設為特定範圍，可獲得低霧度、且於以較大間隙配置於圖像顯示單元之情形時亦不易產生眩光不良、防污層之耐磨耗性優異的抗反射膜。 The anti-reflective films of Examples 1-8 have no glare, show good visibility, and also show high water contact angle after sliding test. According to the above results, it can be known that by adjusting the type and content of fine particles contained in the hard coat layer, setting the haze and surface shape parameters in a specific range, low haze can be obtained, and it can be displayed in an image with a larger gap. In the case of the unit, the anti-reflection film is less likely to cause glare defects and has excellent abrasion resistance of the antifouling layer.
1:硬塗膜 1: Hard coating film
3:底塗層 3: Base coat
5:抗反射層 5: Anti-reflection layer
7:防污層 7: Antifouling layer
10:透明膜基材 10: Transparent film substrate
11:硬塗層 11: Hard coating
51,53:高折射率層 51,53: high refractive index layer
52,54:低折射率層 52,54: low refractive index layer
101:抗反射膜 101: Anti-reflection film
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