TWI397926B - Transparent electrically conductive film and touch panel using the same - Google Patents

Transparent electrically conductive film and touch panel using the same Download PDF

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TWI397926B
TWI397926B TW98135390A TW98135390A TWI397926B TW I397926 B TWI397926 B TW I397926B TW 98135390 A TW98135390 A TW 98135390A TW 98135390 A TW98135390 A TW 98135390A TW I397926 B TWI397926 B TW I397926B
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transparent conductive
film
refractive index
conductive film
layer
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TW98135390A
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TW201115594A (en
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Hideo Murakami
Toshiyuki Oya
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Toyo Boseki
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透明導電性薄膜及使用它之觸控面板Transparent conductive film and touch panel using the same

本發明係關於在透明塑膠薄膜所構成的基材上，將高折射率層、低折射率層及透明導電性薄膜層依此順序積層而成之透明導電性薄膜或透明導電性薄片(以下，亦簡稱透明導電性薄膜)及使用該等而成之觸控面板。特別是作為組入高精細之液晶顯示器等顯示體的觸控面板之電極用薄膜時，目視辨認性優異並且在觸控面板的框緣附近的筆滑動耐久性優異，因此可擴展顯示區域之透明導電性薄膜及使用它之觸控面板。The present invention relates to a transparent conductive film or a transparent conductive sheet in which a high refractive index layer, a low refractive index layer, and a transparent conductive thin film layer are laminated in this order on a substrate made of a transparent plastic film (hereinafter, Also referred to as a transparent conductive film) and a touch panel using the same. In particular, when a thin film for a touch panel of a display body such as a high-definition liquid crystal display is incorporated, the visibility is excellent and the pen sliding durability in the vicinity of the frame edge of the touch panel is excellent, so that the transparent display area can be expanded. Conductive film and touch panel using the same.

在透明塑膠薄膜所構成的基材上，積層有透明且電阻小的薄膜而成之透明導電性薄膜，係廣泛地被使用在利用其導電性之用途，例如液晶顯示器或電激發光(有時略記EL)顯示器等平面顯示器、或觸控面板之透明電極等電氣、電子領域之用途。A transparent conductive film in which a transparent and low-resistance film is laminated on a substrate made of a transparent plastic film is widely used for its use in conductivity, such as liquid crystal display or electroluminescence (sometimes A brief description of the use in the electrical and electronic fields, such as a flat panel display such as a display or a transparent electrode of a touch panel.

近年來，觸控面板作為輸入介面受到廣泛的認知，特別是行動資訊終端機或數位攝影機、數位相機等行動終端機，為了省略操作鍵而在顯示器增加了用於搭載觸控面板的殼體。另一方面，用於該等行動終端的液晶顯示器等顯示體之高精細化日益進步，強烈地期待不會使組入在這種顯示體的前面之觸控面板用電極薄膜之目視辨認性降低。In recent years, touch panels have been widely recognized as input interfaces, and particularly mobile terminal devices such as mobile information terminals, digital cameras, and digital cameras, and a housing for mounting a touch panel has been added to the display in order to omit the operation keys. On the other hand, the display quality of liquid crystal displays and the like for such mobile terminals has been increasing, and it is strongly expected that the visibility of the electrode film for touch panels incorporated in front of such a display body will not be lowered. .

亦即，電極薄膜的透過率低時，液晶顯示器等顯示體的亮度降低且顯示畫面變暗，因此顯變得不易觀看。而且電極薄膜有著色時，液晶顯示器等的顯示色(特別是白色)之色顯示改變，變得不易獲得鮮明之圖像。因此，期待電極薄膜之透過率高且著色少。In other words, when the transmittance of the electrode film is low, the brightness of the display body such as a liquid crystal display is lowered and the display screen is darkened, so that it becomes difficult to view. Further, when the electrode film is colored, the color of the display color (especially white) of the liquid crystal display or the like is changed, and it becomes difficult to obtain a clear image. Therefore, it is expected that the electrode film has a high transmittance and a small amount of coloration.

另一方面，期待液晶顯示器等顯示體為大畫面化。因此，包含顯示用顯示器之框體區域(框緣)變得更狹窄，作為觸控面板也期待框緣更窄化，進一步觸控面板的框緣附近不收納於框體內而形成存在於顯示區上之狀態。On the other hand, it is expected that a display body such as a liquid crystal display will be enlarged. Therefore, the frame area (frame edge) including the display for display is narrower, and the frame edge is also expected to be narrower as the touch panel, and the vicinity of the frame edge of the touch panel is not stored in the frame to form the display area. The state of the upper.

觸控面板係將具有透明導電層的一對透明導電性基板隔著間隔物配置成透明導電層相對向而構成。在觸控面板進行筆輸入時，固定電極側的透明導電性薄膜和可動電極(薄膜電極)側的透明導電性薄膜彼此接觸，但特別是在框緣附近，於可動電極側的透明導電性薄膜被施加筆負荷造成的較強的彎曲應力。因此，期望有即使被施加筆負荷造成的較強的彎曲應力，透明導電性薄膜也不會產生龜裂、剝離等破壞、在框緣附近的筆滑動耐久性優異之透明導電性薄膜。In the touch panel, a pair of transparent conductive substrates having a transparent conductive layer are disposed such that a transparent conductive layer faces each other with a spacer interposed therebetween. When the pen input is performed on the touch panel, the transparent conductive film on the fixed electrode side and the transparent conductive film on the movable electrode (thin film electrode) side are in contact with each other, but in particular, in the vicinity of the frame edge, the transparent conductive film on the movable electrode side Strong bending stress caused by the applied pen load. Therefore, it is desired that the transparent conductive film does not cause cracking, peeling, or the like, and the transparent conductive film having excellent pen sliding durability in the vicinity of the frame edge, even if a strong bending stress is applied by the pen load.

為了提高目視辨認性，提出有將防止反射加工等所用的折射率相異之層加以積層，利用光干涉之方案。亦即，提出有在透明導電膜和基材薄膜之間設置折射率相異之層、利用光學干涉之方案(專利文獻1~3)。In order to improve the visibility, it has been proposed to laminate a layer having a different refractive index for use in antireflection processing or the like, and to use optical interference. In other words, it has been proposed to provide a layer having a refractive index difference between the transparent conductive film and the base film, and to use optical interference (Patent Documents 1 to 3).

[專利文獻1]日本特開平11-286066號公報[Patent Document 1] Japanese Patent Laid-Open No. Hei 11-286066

[專利文獻2]日本特許第3626624號公報[Patent Document 2] Japanese Patent No. 3626624

[專利文獻3]日本特開2006-346878號公報[Patent Document 3] Japanese Patent Laid-Open Publication No. 2006-346878

但是，該等專利文獻1~3記載的透明導電性薄膜係可改善目視辨認性但環境穩定性或觸控面板框緣附近的筆滑動耐久性有問題。亦即，如專利文獻1之實施例1所記載，將真空槽排氣至高真空狀態之後形成的相對於銦之錫含有率低之膜，用於作為高折射率層時，在成膜中或觸控面板之製造工程中，因相關之熱處理使ITO膜容易引起結晶化。將具有將如此地經結晶化之ITO膜作為高折射層或透明導電層之透明導電性薄膜，用於作為電極薄膜之觸控面板，則在觸控面板框緣附近的筆滑動耐久性不佳。且，利用將專利文獻2記載的氧化鈦膜作為高折射層使用的透明導電性薄膜之觸控面板，會產生在屋外使用時產生輸入位置偏移之問題。且，將專利文獻3記載的含有氧化錫及氧化鈰之氧化銦膜用於作為高折射率層時，由於含有氧化鈰而變成硬又脆之膜，因此觸控面板的框緣附近之筆滑動耐久性不足，且成膜速度變慢故生產性降低。However, the transparent conductive film described in the above Patent Documents 1 to 3 can improve the visibility, but the environmental stability or the pen sliding durability in the vicinity of the frame edge of the touch panel is problematic. In other words, as described in the first embodiment of Patent Document 1, a film having a low tin content with respect to indium formed after evacuating the vacuum chamber to a high vacuum state is used as a high refractive index layer in film formation or In the manufacturing process of the touch panel, the ITO film is likely to cause crystallization due to the related heat treatment. A transparent conductive film having an ITO film thus crystallized as a high refractive layer or a transparent conductive layer is used as a touch panel as an electrode film, and the pen sliding durability near the frame edge of the touch panel is poor. . In addition, the touch panel using the transparent conductive film used as the high refractive layer of the titanium oxide film described in Patent Document 2 has a problem that the input position is shifted when it is used outdoors. In addition, when the indium oxide film containing tin oxide and yttrium oxide described in Patent Document 3 is used as a high refractive index layer, since it contains a ruthenium oxide and becomes a hard and brittle film, the pen slip near the frame edge of the touch panel. The durability is insufficient, and the film formation speed is slow, so that productivity is lowered.

即，本發明之目的係鑑於上述以往之問題點，提供一透明導電性薄膜及使用它之觸控面板，作為使用於高精細之液晶顯示器等顯示體的前面之觸控面板用之電極薄膜用時，目視辨認性優異，且生產性優異、且框緣附近的筆滑動耐久性(邊緣耐久性)優異。In other words, the present invention provides a transparent conductive film and a touch panel using the same as the electrode film for a touch panel used in front of a display body such as a high-definition liquid crystal display. In view of the above, the visibility is excellent, the productivity is excellent, and the pen sliding durability (edge durability) in the vicinity of the frame edge is excellent.

本發明係鑑於如上述之狀況而研發者，可解決上述課題之透明導電性薄膜、及觸控面板係由以下構成所成。The present invention has been made in view of the above circumstances, and a transparent conductive film and a touch panel which can solve the above problems are formed by the following constitution.

1.一種透明導電性薄膜，係於透明塑膠薄膜所構成的基材上，將高折射率層、低折射率層及透明導電性薄膜層依此順序積層而成之透明導電性薄膜，其特徵為高折射率層係由氧化錫之含有率為10~60質量%之非晶質銦-錫複合氧化物所構成的無機薄膜，低折射率層係由折射率1.30~1.60之無機薄膜所構成，透明導電性薄膜層係由折射率1.80~2.20之無機薄膜所構成，且透明導電性薄膜之分光透過率之峰值係存在於450~530nm，且全部光線透過率為90%以上，色彩b值為-2~2。A transparent conductive film which is a transparent conductive film formed by laminating a high refractive index layer, a low refractive index layer and a transparent conductive film layer on a substrate made of a transparent plastic film. The high refractive index layer is an inorganic thin film composed of an amorphous indium-tin composite oxide having a tin oxide content of 10 to 60% by mass, and the low refractive index layer is composed of an inorganic thin film having a refractive index of 1.30 to 1.60. The transparent conductive film layer is composed of an inorganic film having a refractive index of 1.80 to 2.20, and the peak of the spectral transmittance of the transparent conductive film is 450 to 530 nm, and the total light transmittance is 90% or more, and the color b value is It is -2~2.

2.如前述1.之透明導電性薄膜，其中前述高折射率層之氧化錫之含有率為20~60質量%。2. The transparent conductive film according to the above 1, wherein the high refractive index layer has a tin oxide content of 20 to 60% by mass.

3.如前述1.或2.之透明導電性薄膜，其中在由前述透明塑膠薄膜所構成的基材之積層有透明導電性薄膜層的面之相反面係經施行低反射處理。3. The transparent conductive film according to the above 1. or 2. wherein the opposite surface of the surface of the substrate made of the transparent plastic film which is laminated with the transparent conductive film layer is subjected to a low reflection treatment.

4.一種透明導電性薄片，其特徵為在如前述1至3中任一項之透明導電性薄膜之積層有透明導電性薄膜層的面之相反面，藉由黏合劑貼合著透明樹脂薄片。4. A transparent conductive sheet characterized in that the transparent conductive film of any one of the above-mentioned 1 to 3 is laminated on the opposite side of the surface of the transparent conductive film layer, and the transparent resin sheet is bonded by an adhesive. .

5.一種觸控面板，係將具有透明導電性薄膜層的一對面板，隔著間隔物配置成透明導電性薄膜層相對向而構成的觸控面板，其特徵為至少一方之面板係由如前述1至4中任一項之透明導電性薄膜或透明導電性薄片所構成。A touch panel comprising a pair of panels having a transparent conductive thin film layer and a transparent conductive thin film layer disposed opposite to each other via a spacer, wherein at least one of the panels is composed of The transparent conductive film or the transparent conductive sheet according to any one of the above 1 to 4.

本發明之透明導電性薄膜係於透明塑膠薄膜所構成的基材上，具有以高折射率層、低折射率層及透明導電性薄膜層之順序積層而成的構成，由於透過率之峰值係存在特定波長區域，因此即使配置於高精細之顯示體的前面，仍可抑制目視辨認性降低。且，前述高折射率層係使用氧化錫的含有率為所定值之非晶質銦-錫複合氧化物所構成的層，藉此可使生產性優異且提高對於彎曲之機械強度。因此，在觸控面板框緣附近進行筆滑動實驗時，透明導電性薄膜不易產生剝離及龜裂，具有可提高框緣附近的筆滑動耐久性之優點。The transparent conductive film of the present invention is formed by laminating a high refractive index layer, a low refractive index layer, and a transparent conductive thin film layer on a substrate made of a transparent plastic film, and the transmittance is a peak. Since there is a specific wavelength region, even if it is disposed in front of a high-definition display body, deterioration in visibility can be suppressed. Further, the high refractive index layer is a layer composed of an amorphous indium-tin composite oxide having a predetermined content of tin oxide, whereby the productivity is excellent and the mechanical strength against bending is improved. Therefore, when the pen sliding test is performed in the vicinity of the frame edge of the touch panel, the transparent conductive film is less likely to be peeled and cracked, and the pen sliding durability in the vicinity of the frame edge can be improved.

本發明之透明導電性薄膜係於透明塑膠薄膜所構成的基材上，將高折射率層、低折射率層及透明導電性薄膜層依此順序積層而成之透明導電性薄膜。以下，依各層別詳細地說明。The transparent conductive film of the present invention is a transparent conductive film in which a high refractive index layer, a low refractive index layer, and a transparent conductive thin film layer are laminated in this order on a substrate made of a transparent plastic film. Hereinafter, each layer will be described in detail.

(透明塑膠薄膜所構成的基材)(substrate composed of transparent plastic film)

本發明中使用的透明塑膠薄膜所構成的基材，係將有機高分子溶融壓出或溶液壓出後因應必要朝長度方向及/或寬方向施行延伸、冷卻、熱固定之薄膜。作為有機高分子，可舉出聚乙烯、聚丙烯、聚對苯二甲酸乙二酯、聚-2,6-萘二甲酸乙二酯、聚對苯二甲酸二丙酯、耐綸6、耐綸4、耐綸66、耐綸12、聚醯亞胺、聚醯胺醯亞胺、聚醚硫、聚醚醚酮、聚碳酸酯、聚芳酯、丙酸纖維素、聚氯乙烯、聚偏二氯乙烯、聚乙烯醇、聚醚醯亞胺、聚苯硫醚、聚苯醚、聚苯乙烯、間規聚苯乙烯、降冰片烯系聚合物等。The substrate made of the transparent plastic film used in the present invention is a film which is stretched, cooled, and thermally fixed in the longitudinal direction and/or the width direction after the organic polymer is melted and extruded or the solution is extruded. Examples of the organic polymer include polyethylene, polypropylene, polyethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, polypropylene terephthalate, nylon 6, and resistant. Polyester 4, nylon 66, nylon 12, polyimine, polyamidamine, polyether sulfur, polyetheretherketone, polycarbonate, polyarylate, cellulose propionate, polyvinyl chloride, poly Dichloroethylene, polyvinyl alcohol, polyether phthalimide, polyphenylene sulfide, polyphenylene ether, polystyrene, syndiotactic polystyrene, norbornene-based polymer, and the like.

該等有機高分子之中，聚對苯二甲酸乙二酯、聚對苯二甲酸二丙酯、聚-2,6-萘二甲酸乙二酯、間規聚苯乙烯、降冰片烯系聚合物、聚碳酸酯、聚芳酯等較適合。且，該等有機高分子可以和其他有機聚合體的單體少量共聚合，混合其他有機高分子亦可。Among these organic polymers, polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, syndiotactic polystyrene, norbornene polymerization Materials, polycarbonates, polyarylates, etc. are suitable. Further, the organic polymers may be copolymerized with a small amount of monomers of other organic polymers, and other organic polymers may be mixed.

本發明中使用的透明塑膠薄膜所構成的基材之厚度，在超過10μm、300μm以下之範圍為佳，上限值為260μm、下限值為70μm特佳。塑膠薄膜之厚度為10μm以下時機械強度不足，特別是用於觸控面板時有對於筆輸入之變形變大之傾向，容易變成耐久性不足。另一方面，若厚度超過300μm，則用於觸控面板時，為了使薄膜變形，必須加大筆負荷。因此，施加在透明導電性薄膜之負荷必然變大，就透明導電性薄膜之耐久性而言不佳。The thickness of the base material composed of the transparent plastic film used in the present invention is preferably in the range of more than 10 μm and 300 μm, and the upper limit is 260 μm, and the lower limit is preferably 70 μm. When the thickness of the plastic film is 10 μm or less, the mechanical strength is insufficient, and particularly when used for a touch panel, the deformation of the pen input tends to be large, and it tends to be insufficient in durability. On the other hand, when the thickness exceeds 300 μm, when used for a touch panel, in order to deform the film, it is necessary to increase the pen load. Therefore, the load applied to the transparent conductive film is inevitably increased, and the durability of the transparent conductive film is not good.

本發明中使用的透明塑膠薄膜所構成的基材只要在無損於本發明之目的之範圍內，對前述薄膜施行電暈放電處理、輝光放電處理、火燄處理、紫外線照射處理、電子束照射處理、臭氧處理等表面活性化處理亦可。The substrate made of the transparent plastic film used in the present invention is subjected to corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, and the like, as long as the object of the present invention is not impaired. Surface activation treatment such as ozone treatment is also possible.

且，本發明係以使基材和透明導電性薄膜層之密合性提高、筆輸入耐久性、賦予耐藥性、防止寡聚物等低分子量物析出為目的，在基材和透明導電性薄膜層之間，設置以硬化型樹脂為主要構成成分之硬化物層亦可。Further, in the present invention, the substrate and the transparent conductive property are improved in order to improve the adhesion between the substrate and the transparent conductive thin film layer, pen input durability, drug resistance, and prevention of precipitation of low molecular weight substances such as oligomers. A cured layer containing a curable resin as a main component may be provided between the film layers.

前述硬化型樹脂只要是藉由加熱、紫外線照射、電子束照射等能量施加而硬化之樹脂，則無特別限定，可舉出聚矽氧樹脂、丙烯酸樹脂、甲基丙烯酸酯樹脂、環氧樹脂、三聚氰胺樹脂、聚酯樹脂、胺基甲酸酯樹脂等。從生產性之觀點而言，以紫外線硬化型樹脂為主成分之硬化型樹脂為佳。The curable resin is not particularly limited as long as it is cured by energy application such as heating, ultraviolet irradiation, or electron beam irradiation, and examples thereof include polyfluorene oxide resin, acrylic resin, methacrylate resin, and epoxy resin. Melamine resin, polyester resin, urethane resin, and the like. From the viewpoint of productivity, a curable resin containing an ultraviolet curable resin as a main component is preferred.

作為這種紫外線硬化型樹脂，例如可舉出如多元醇之丙烯酸或甲基丙烯酸酯之多官能性丙烯酸酯樹脂、二異氰酸酯、多元醇及丙烯酸或甲基丙烯酸之羥基烷基酯等所合成之多官能性胺基甲酸酯丙烯酸酯樹脂等。因應必要，可在該等多官能性樹脂加入單官能性單體，例如乙烯吡咯啶酮、甲基丙烯酸甲酯、苯乙烯等使其共聚合。Examples of such an ultraviolet curable resin include a polyfunctional acrylate resin of acrylic acid or methacrylic acid ester of a polyhydric alcohol, a diisocyanate, a polyhydric alcohol, and a hydroxyalkyl ester of acrylic acid or methacrylic acid. A polyfunctional urethane acrylate resin or the like. If necessary, a monofunctional monomer such as vinylpyrrolidone, methyl methacrylate, styrene or the like may be added to the polyfunctional resin to be copolymerized.

且，為了提高透明導電性薄膜和硬化物層之附著力，將硬化物層予以表面處理為有效。作為具體方法，可舉出利用照射輝光或電暈放電之放電處理法、增加羰基、羧基、烴基之方法、利用酸或鹼處理之化學藥品處理法、增加胺基、羥基、羰基等極性基之方法等。Further, in order to improve the adhesion between the transparent conductive film and the cured layer, it is effective to surface-treat the cured layer. Specific examples of the method include a discharge treatment method using irradiation of glow or corona discharge, a method of increasing a carbonyl group, a carboxyl group, or a hydrocarbon group, a chemical treatment method using an acid or a base treatment, and a polar group such as an amine group, a hydroxyl group, or a carbonyl group. Method, etc.

紫外線硬化型樹脂通常被添加光聚合引發劑而使用。作為光聚合引發劑，可以不特別限定使用吸收紫外線產生自由基之眾知之化合物，作為這種光聚合引發劑，例如可舉出各種苯偶姻類、苯酮類、二苯甲酮類等。光聚合引發劑之添加量相對於紫外線硬化型樹脂100質量份而言，以1~5質量份為佳。The ultraviolet curable resin is usually used by adding a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and a known compound that absorbs ultraviolet rays to generate a radical is used. Examples of such a photopolymerization initiator include various benzoin, benzophenone, and benzophenone. The amount of the photopolymerization initiator to be added is preferably 1 to 5 parts by mass based on 100 parts by mass of the ultraviolet curable resin.

塗布液中之樹脂成分濃度可以考慮配合塗布法之黏度等而適當地選擇。例如，塗布液中紫外線硬化型樹脂、光聚合引發劑之合計量所佔的比例通常為20~80質量%。且，在該塗布液中，亦可配合必要添加其他眾知之添加劑，例如聚矽氧系界面活性劑、氟系界面活性劑等塗平劑等。The concentration of the resin component in the coating liquid can be appropriately selected in consideration of the viscosity of the coating method or the like. For example, the ratio of the total amount of the ultraviolet curable resin and the photopolymerization initiator in the coating liquid is usually 20 to 80% by mass. Further, in the coating liquid, other known additives such as a polyfluorene surfactant or a fluorine-based surfactant may be added as needed.

本發明中，經調製之塗布液被塗布於透明塑膠薄膜所構成之基材上。對於塗布法並無特別限定，可使用硬塗法、凹版印刷塗布法、逆向輥塗法等習知之方法。In the present invention, the prepared coating liquid is applied onto a substrate composed of a transparent plastic film. The coating method is not particularly limited, and a conventional method such as a hard coating method, a gravure coating method, or a reverse roll coating method can be used.

且，硬化物層之厚度為0.1~15μm之範圍為佳。硬化物層之厚度的下限值為0.5μm更佳，特佳為1μm。且，硬化物層之厚度的上限值為10μm更佳，特佳為8μm。硬化物層之厚度為未達0.1時，由於無法充份地形成經交聯之構造，因此筆輸入耐久性或耐藥品性容易降低，也容易引起寡聚物等的低分子量造成之密合性降低。另一方面，硬化物層之厚度為超過15μm時，有生產性降低之傾向。Further, the thickness of the cured layer is preferably in the range of 0.1 to 15 μm. The lower limit of the thickness of the cured layer is preferably 0.5 μm, more preferably 1 μm. Further, the upper limit of the thickness of the cured layer is more preferably 10 μm, particularly preferably 8 μm. When the thickness of the cured layer is less than 0.1, since the crosslinked structure cannot be formed sufficiently, the pen input durability or chemical resistance is liable to be lowered, and the adhesion due to the low molecular weight of the oligomer or the like is likely to occur. reduce. On the other hand, when the thickness of the cured layer is more than 15 μm, the productivity tends to be lowered.

(高折射率層)(high refractive index layer)

本發明中之高折射率層係由氧化錫之含有率為10~60質量%之非晶質銦-錫複合氧化物所構成的無機薄膜。更佳為氧化錫之含有率為20~50質量%，又更佳為30~45質量%。The high refractive index layer in the present invention is an inorganic thin film composed of an amorphous indium-tin composite oxide having a tin oxide content of 10 to 60% by mass. More preferably, the content of tin oxide is 20 to 50% by mass, and more preferably 30 to 45% by mass.

高折射率層係至少具有較低折射率層(折射率為1.30~1.60)高的折射率之層。藉由將具有較低折射率層高的折射率之層形成於透明塑膠薄膜基材，可獲得光之干涉效果。The high refractive index layer has at least a layer having a refractive index of a lower refractive index layer (refractive index of 1.30 to 1.60). By forming a layer having a refractive index of a lower refractive index layer on a transparent plastic film substrate, an interference effect of light can be obtained.

一般而言，作為高折射率層係使用TiO2 、Nb2 O5 、In2 O3 。但是例如藉由濺鍍法形成TiO2 、Nb2 O5 膜時，成膜速度慢、生產性降低。因此從生產性之觀點來看，作為高折射率層以銦氧化物為佳。In general, TiO 2 , Nb 2 O 5 , and In 2 O 3 are used as the high refractive index layer. However, when a TiO 2 or Nb 2 O 5 film is formed by a sputtering method, for example, the film formation rate is slow and the productivity is lowered. Therefore, from the viewpoint of productivity, indium oxide is preferable as the high refractive index layer.

但是，形成In2 O3 或氧化錫含有率低的銦-錫複合氧化膜時，雖然生產性優異但因為施行於濺鍍成膜中或觸控面板製造工程中之熱處理，而使高折射率層結晶化。使用高折射率層結晶化之透明導電性薄膜製作的觸控面板中，框緣附近的筆滑動耐久性差。因而，高折射率層中不存在結晶粒為佳。具體而言，實施例之欄記載的測量中未觀測到結晶粒者為佳。However, when an indium-tin composite oxide film having a low In 2 O 3 or tin oxide content is formed, although it is excellent in productivity, it has a high refractive index due to heat treatment performed in a sputtering film formation process or a touch panel manufacturing process. The layer is crystallized. In the touch panel manufactured using the transparent conductive film crystallized by the high refractive index layer, the pen sliding durability in the vicinity of the frame edge is poor. Therefore, it is preferred that no crystal grains are present in the high refractive index layer. Specifically, it is preferred that no crystal grains are observed in the measurement described in the column of the examples.

因此，在本發明中所用的高折射率層，就生產性之觀點而言為銦-錫複合氧化物所構成，氧化錫的含有率為10~60質量%。氧化錫的含有率為未達10質量%時，難以抑制關於成膜中或觸控面板製造工程中之熱處理所造成的結晶化。另一方面，氧化錫的含有率為超過60質量%時，難以使標靶密度提高，生產中容易產生異常放電，就生產性之觀點而言不佳。Therefore, the high refractive index layer used in the present invention is composed of an indium-tin composite oxide from the viewpoint of productivity, and the content of tin oxide is 10 to 60% by mass. When the content of tin oxide is less than 10% by mass, it is difficult to suppress crystallization caused by heat treatment in film formation or in a touch panel manufacturing process. On the other hand, when the content of tin oxide is more than 60% by mass, it is difficult to increase the target density, and abnormal discharge is likely to occur during production, which is not preferable from the viewpoint of productivity.

此外，即使氧化錫的含有率為10~60質量%之範圍，在氧化錫的含量低的區域仍有因製膜條件而結晶化的情形。特別是水分壓對惰性氣體之比低時，容易結晶化。在這種氧化錫的含量低的情形下(例如20質量%以下)，特別是藉由提高水分壓對惰性氣體之比，可抑制結晶化。較佳之水分壓對惰性氣體之比係根據氧化錫的含有率量而異，但例如錫含有率為10質量%時，3×10-3 以上為佳。為了提高水分壓對惰性氣體之比，藉由調整製膜前的真空暴露條件，可舉出提高薄膜之含水量的方法、製膜時使薄膜溫度較高的方法、蓄意地導入水蒸氣的方法等任意方法。其他，由於會受到使用的基材薄膜之水分含有率左右，因此必須考慮此點決定適當條件。且，藉由降低氧的分壓比也可抑制結晶化。In addition, even if the content of the tin oxide is in the range of 10 to 60% by mass, the region where the content of the tin oxide is low may be crystallized due to the film formation conditions. In particular, when the ratio of the water pressure to the inert gas is low, crystallization is easy. In the case where the content of the tin oxide is low (for example, 20% by mass or less), in particular, by increasing the ratio of the water pressure to the inert gas, crystallization can be suppressed. The ratio of the water pressure to the inert gas is preferably in accordance with the content of the tin oxide. However, for example, when the tin content is 10% by mass, 3 × 10 -3 or more is preferable. In order to increase the ratio of the water pressure to the inert gas, by adjusting the vacuum exposure conditions before film formation, a method of increasing the water content of the film, a method of making the film temperature high during film formation, and a method of intentionally introducing water vapor are mentioned. Any method. In addition, since the moisture content of the base film to be used is about to be affected, it is necessary to consider the appropriate conditions. Further, crystallization can be suppressed by lowering the partial pressure ratio of oxygen.

作為本發明中所用的高折射率層之膜厚，以35~50nm為佳，更佳為38~48nm。超過50nm時，高折射率層在成膜中或加熱處理後容易結晶化。且，未達35nm時，難以改善透明導電性薄膜之光學特性。此外，高折射率層之折射率為1.70~2.50為佳，更佳為1.90~2.30，特佳為1.90~2.10。The film thickness of the high refractive index layer used in the present invention is preferably 35 to 50 nm, more preferably 38 to 48 nm. When it exceeds 50 nm, the high refractive index layer is easily crystallized during film formation or after heat treatment. Further, when it is less than 35 nm, it is difficult to improve the optical characteristics of the transparent conductive film. Further, the refractive index of the high refractive index layer is preferably 1.70 to 2.50, more preferably 1.90 to 2.30, and particularly preferably 1.90 to 2.10.

作為本發明中的高折射率層之成膜方法，已知有真空蒸鍍法、濺鍍法、CVD法、離子電鍍法、噴霧法等，可配合需要之膜厚適當地使用前述方法，但是從降低膜厚不均的觀點而言，以濺鍍法為佳。As a film forming method of the high refractive index layer in the present invention, a vacuum vapor deposition method, a sputtering method, a CVD method, an ion plating method, a spray method, or the like is known, and the above method can be suitably used in accordance with the required film thickness, but From the viewpoint of reducing film thickness unevenness, a sputtering method is preferred.

濺鍍法中，一般有從金屬標靶導入反應性氣體製作金屬氧化物之反應性濺鍍法、和從氧化物標靶製作金屬氧化物之方法。為了抑制膜厚之不均，使用氧化物標靶為佳。In the sputtering method, there are generally a reactive sputtering method in which a reactive gas is introduced from a metal target to form a metal oxide, and a method of producing a metal oxide from an oxide target. In order to suppress the unevenness of the film thickness, it is preferred to use an oxide target.

為了抑制對隔著低折射率層積層之透明導電性薄膜之導電性的影響，本發明中所使用之高折射率層係以絕緣體為佳。具體而言為1×106 Ω/□以上。因此形成銦-錫複合氧化物層時，將反應性氣體設定為表面電阻值為最小值時之氣體流量的1.5~5倍流量為佳。未達1.5倍時，難以將表面電阻值設定為上述範圍。且，若流過超過5.0倍之氣體流量，則膜中被攙入化學計量比以上之氧、或容易形成因氧負離子過剩之生成所形成之損傷大的膜，由於形成不穩定的膜，降低環境實驗後透明導電性薄膜之穩定性。In order to suppress the influence on the conductivity of the transparent conductive film interposed between the low refractive index laminated layers, the high refractive index layer used in the present invention is preferably an insulator. Specifically, it is 1 × 10 6 Ω / □ or more. Therefore, when the indium-tin composite oxide layer is formed, it is preferable to set the reactive gas to a flow rate of 1.5 to 5 times the gas flow rate when the surface resistance value is the minimum value. When it is less than 1.5 times, it is difficult to set the surface resistance value to the above range. In addition, when a gas flow rate exceeding 5.0 times is passed, the film is filled with oxygen having a stoichiometric ratio or higher, or a film having a large damage due to generation of an excess of oxygen anion is likely to be formed, and an unstable film is formed to lower the film. Stability of transparent conductive film after environmental experiment.

因此為了獲得在高溫、高濕環境下(85℃、85% RH、1000小時)的穩定性，將氣體流量設定為表面電阻值成為最小值的氣體流量之1.5~3倍為佳，因此氧化錫的含有率為20~60質量%為佳。未達20質量%時，上述氣體流量難以使表面電阻值達到1×106 Ω/□以上。Therefore, in order to obtain stability in a high-temperature, high-humidity environment (85 ° C, 85% RH, 1000 hours), it is preferable to set the gas flow rate to 1.5 to 3 times the gas flow rate at which the surface resistance value becomes the minimum value. The content ratio is preferably 20 to 60% by mass. When the amount is less than 20% by mass, the gas flow rate is difficult to achieve a surface resistance value of 1 × 10 6 Ω/□ or more.

(低折射率層)(low refractive index layer)

本發明中的低折射率層之折射率為1.30~1.60為佳，更佳為1.40~1.50。具體可舉出SiO2 、Al2 O3 等透明金屬氧化物、或SiO2 -Al2 O3 等複合金屬氧化物所構成之層。折射率為未達1.30時，低折射率層變成多孔之膜，將阻礙其上方形成的透明導電性薄膜層之電氣特性。另一方面，折射率為超過1.60時，難以滿足前述光學特性。The refractive index of the low refractive index layer in the present invention is preferably from 1.30 to 1.60, more preferably from 1.40 to 1.50. Specific examples thereof include SiO 2, Al 2 O 3 and other transparent metal oxide, or SiO 2 -Al 2 O 3 and other layers constituting the composite metal oxide. When the refractive index is less than 1.30, the low refractive index layer becomes a porous film, and the electrical characteristics of the transparent conductive thin film layer formed thereon are inhibited. On the other hand, when the refractive index is more than 1.60, it is difficult to satisfy the aforementioned optical characteristics.

低折射率層之膜厚只要滿足本申請案之發明範圍的分光透過率、全光線透過率及色彩值，即可適當選擇。例如SiO2 薄膜的情形為45~60nm較佳，更佳為50~58nm。超過60nm時，透明導電性薄膜的光線透過率提高，但是產生著色而使分光透過率和色彩b值偏離目標。另一方面，未達45nm的情形下，難以獲得目標之全光線透過率。The film thickness of the low refractive index layer can be appropriately selected as long as it satisfies the spectral transmittance, the total light transmittance, and the color value within the scope of the invention of the present application. For example, in the case of a SiO 2 film, it is preferably 45 to 60 nm, more preferably 50 to 58 nm. When the thickness exceeds 60 nm, the light transmittance of the transparent conductive film is improved, but coloring occurs, and the spectral transmittance and the color b value are deviated from the target. On the other hand, in the case of less than 45 nm, it is difficult to obtain the total light transmittance of the target.

作為本發明中的低折射率層之成膜方法，已知有真空蒸鍍法、濺鍍法、CVD法、離子電鍍法、噴霧法等，可配合需要之膜厚適當地使用前述方法，從減少膜厚不均的觀點而言，以濺鍍法為佳。一般以濺鍍形成時係使用反應性DC或AC濺鍍法。為了提高成膜速度，使用控制反應性氣體流量之電阻控制以使DC或AC電源的電壓值保持為一定，或使用控制反應性氣體流量之電漿放射法以使特定元素之電漿中的發光強度保持為一定。As a film forming method of the low refractive index layer in the present invention, a vacuum vapor deposition method, a sputtering method, a CVD method, an ion plating method, a spray method, or the like is known, and the above method can be suitably used in accordance with the required film thickness. From the viewpoint of reducing film thickness unevenness, sputtering is preferred. Reactive DC or AC sputtering is generally used when forming by sputtering. In order to increase the film formation speed, resistance control for controlling the flow rate of the reactive gas is used to keep the voltage value of the DC or AC power source constant, or plasma irradiation method for controlling the flow rate of the reactive gas is used to cause luminescence in the plasma of a specific element. The strength is kept constant.

(透明導電性薄膜層)(transparent conductive film layer)

本發明中的透明導電性薄膜層係由折射率為1.80~2.20之無機薄膜所構成。較佳為1.90~2.10之無機薄膜，更佳為1.93~2.05之無機薄膜。透明導電性薄膜的折射率為未達1.80時，難以形成導電性良好之透明導電性薄膜層。另一方面，折射率為超過2.20時，亦難以形成導電性良好之透明導電性薄膜層，進一步，在空氣和透明導電性薄膜層之界面的反射變大，難以滿足前述光學特性。The transparent conductive thin film layer in the present invention is composed of an inorganic thin film having a refractive index of 1.80 to 2.20. Preferably, it is an inorganic film of 1.90 to 2.10, more preferably an inorganic film of 1.93 to 2.05. When the refractive index of the transparent conductive film is less than 1.80, it is difficult to form a transparent conductive thin film layer having good conductivity. On the other hand, when the refractive index is more than 2.20, it is difficult to form a transparent conductive thin film layer having good conductivity, and further, the reflection at the interface between the air and the transparent conductive thin film layer becomes large, and it is difficult to satisfy the optical characteristics described above.

具體而言，可舉出氧化銦、氧化錫、氧化鋅、銦-錫複合氧化物、錫-銻複合氧化物、鋅-鋁複合氧化物、銦-鋅複合氧化物等。且，為了調整折射率，亦可適當添加金屬氧化物。該等之中，從環境穩定性和電路加工性之觀點而言，以銦-錫複合氧化物較適合。Specifically, indium oxide, tin oxide, zinc oxide, an indium-tin composite oxide, a tin-bismuth composite oxide, a zinc-aluminum composite oxide, an indium-zinc composite oxide, or the like can be given. Further, in order to adjust the refractive index, a metal oxide may be added as appropriate. Among these, an indium-tin composite oxide is suitable from the viewpoint of environmental stability and circuit processability.

本發明中，積層透明導電性薄膜層，藉由將透明導電性薄膜的表面電阻值較佳設為50~5000Ω/□，更佳設為100~2000Ω/□的方式，可將透明導電性薄膜使用在觸控面板等。表面電阻值為未達100Ω/□時，觸控面板的位置辨識精確度變差，而超過2000Ω/□時，會有必須提高施加在觸控面板的電極間之電壓的情形，因而不佳。In the present invention, the transparent conductive film layer can be transparent conductive film by setting the surface resistivity of the transparent conductive film to 50 to 5000 Ω/□, more preferably 100 to 2000 Ω/□. Use on touch panels, etc. When the surface resistance value is less than 100 Ω/□, the position recognition accuracy of the touch panel is deteriorated, and when it exceeds 2000 Ω/□, there is a case where it is necessary to increase the voltage applied between the electrodes of the touch panel, which is not preferable.

且，從生產性之觀點而言，透明導電性薄膜和高折射率層為相同素材，例如銦-錫組成為佳。組成相異時，必須有高折射率用、透明導電性薄膜用之各自之標靶及陰極，設備方面也變成龐大的裝置。Further, from the viewpoint of productivity, the transparent conductive film and the high refractive index layer are the same material, and for example, an indium-tin composition is preferable. When the composition is different, it is necessary to have a target and a cathode for the high refractive index and the transparent conductive film, and the device is also a bulky device.

透明導電性薄膜之層構造為單層構造亦可，為2層以上之積層構造亦可。於具有2層以上之積層構造之透明導電性薄膜的情形下，構成各層之前述金屬氧化物為相同亦可，為相異亦可。The layer structure of the transparent conductive film may be a single layer structure, and may have a laminated structure of two or more layers. In the case of a transparent conductive film having a laminated structure of two or more layers, the metal oxides constituting each layer may be the same or different.

透明導電性薄膜之膜厚為4~25nm之範圍較佳，特佳為5~20nm，更佳為8~18nm。透明導電性薄膜之膜厚未達4nm時，難以形成連續之薄膜，因而難以獲得良好的導電性。另一方面，透明導電性薄膜之膜厚為較25nm更厚時，透明性容易降低，並且難以獲得具有可承受觸控面板的框緣附近之彎曲應力的機械強度之膜。The film thickness of the transparent conductive film is preferably in the range of 4 to 25 nm, more preferably 5 to 20 nm, still more preferably 8 to 18 nm. When the film thickness of the transparent conductive film is less than 4 nm, it is difficult to form a continuous film, and thus it is difficult to obtain good conductivity. On the other hand, when the film thickness of the transparent conductive film is thicker than 25 nm, the transparency is liable to be lowered, and it is difficult to obtain a film having mechanical strength capable of withstanding the bending stress near the frame edge of the touch panel.

作為本發明中的透明導電性薄膜之成膜方法，眾知有真空蒸鍍法、濺鍍法、CVD法、離子電鍍法、噴塗法等，配合必要之膜厚可適當使用前述方法。As a method of forming a transparent conductive film in the present invention, a vacuum deposition method, a sputtering method, a CVD method, an ion plating method, a spray method, or the like is known, and the above method can be suitably used in accordance with the film thickness required.

例如濺鍍法的情形，係利用使用氧化物標靶之通常的濺鍍法、或使用金屬標靶之反應性濺鍍法等。此時，作為反應性氣體，可導入氧、氮等、或倂用臭氧添加、電漿照射、離子輔助等手段。且，在無損本發明之目的的範圍，亦可於基板施加直流、交流、高頻等偏壓。For example, in the case of the sputtering method, a usual sputtering method using an oxide target or a reactive sputtering method using a metal target is used. In this case, as the reactive gas, oxygen, nitrogen, or the like may be introduced, or ozone, ozone, plasma, or ion assist may be used. Further, a bias voltage such as direct current, alternating current, or high frequency may be applied to the substrate insofar as the object of the present invention is not impaired.

(透明導電性薄膜之光學特性)(Optical characteristics of transparent conductive film)

本發明之透明導電性薄膜係於由上述透明塑膠薄膜所構成的基材上，依高折射率層、低折射率層及透明導電性薄膜層之順序積層而成之構成，由於在特定波長區域存在透過率之峰值，即使配置於高精細之顯示體的前面仍可抑制目視辨認性降低。The transparent conductive film of the present invention is formed by laminating a high refractive index layer, a low refractive index layer and a transparent conductive thin film layer on a substrate composed of the above transparent plastic film, in a specific wavelength region. There is a peak in transmittance, and even if it is disposed in front of a high-definition display body, the deterioration of visibility can be suppressed.

本發明之透明導電性薄膜的分光透過率之峰值係存在於450~530nm，因此著色極少且透過率優異，所以將本發明之透明導電性薄膜使用於觸控面板等構件時，目視辨認性優異。較佳之分光透過率之峰值為460~520nm，更佳之分光透過率之峰值為470~510nm。Since the transparent conductive film of the present invention has a spectral light transmittance of 450 to 530 nm, the coloring is extremely small and the transmittance is excellent. Therefore, when the transparent conductive film of the present invention is used for a member such as a touch panel, the visibility is excellent. . The peak light transmittance is preferably 460 to 520 nm, and the peak of the light transmittance is 470 to 510 nm.

且，本發明之透明導電性薄膜的全光線透過率為90%以上，因此將本發明之透明導電性薄膜使用於觸控面板等構件時，可抑制液晶顯示器等的亮度降低。Further, since the transparent conductive film of the present invention has a total light transmittance of 90% or more, when the transparent conductive film of the present invention is used for a member such as a touch panel, it is possible to suppress a decrease in luminance of a liquid crystal display or the like.

再者，由於本發明之透明導電性薄膜的色彩b值為-2~2，因此將本發明之透明導電性薄膜使用於觸控面板等構件時，可抑制損壞液晶顯示器等顯示體之顯示色。較佳之色彩b值為-1.0~1.5，更佳為0~1.5。In addition, since the color b value of the transparent conductive film of the present invention is -2 to 2, when the transparent conductive film of the present invention is used for a member such as a touch panel, it is possible to suppress damage to the display color of a display such as a liquid crystal display. . The preferred color b value is -1.0 to 1.5, more preferably 0 to 1.5.

(防止牛頓環產生)(Preventing the generation of Newton's rings)

且，當作觸控面板時，以防止牛頓環產生為目的，在透明塑膠薄膜之說明中記載的硬化物層，以中心線平均粗度(Ra)為0.1~0.5μm之範圍的方式含有粒子為佳。Ra為未達0.1時，難以防止牛頓環產生。另一方面，Ra為超過0.5μm時，透明導電性薄膜表面過粗，筆滑動耐久性有變差之傾向。In the case of the touch panel, the cured layer described in the description of the transparent plastic film contains the particles in such a manner that the center line average roughness (Ra) is in the range of 0.1 to 0.5 μm for the purpose of preventing the generation of the Newton's ring. It is better. When Ra is less than 0.1, it is difficult to prevent the generation of Newton's rings. On the other hand, when Ra is more than 0.5 μm, the surface of the transparent conductive film is too thick, and the pen sliding durability tends to be deteriorated.

作為含於硬化物層之粒子並無特別限定，但可例示無機粒子(例如二氧化矽、碳酸鈣等)、耐熱性有機粒子(例如聚矽氧粒子、PTFE粒子、聚醯亞胺粒子等)、交聯高分子粒子(交聯PS粒子、交聯丙烯酸系粒子等)。該等粒子之平均粒徑(根據電子顯微鏡法)為0.5~5μm為佳。且，含有於硬化物層中的粒子之含量為0.01~10質量%為佳。The particles to be contained in the cured layer are not particularly limited, and examples thereof include inorganic particles (for example, ceria, calcium carbonate, and the like) and heat-resistant organic particles (for example, polyfluorene oxide particles, PTFE particles, and polyimide particles). And crosslinked polymer particles (crosslinked PS particles, crosslinked acrylic particles, etc.). The average particle diameter of the particles (according to an electron microscope method) is preferably 0.5 to 5 μm. Further, the content of the particles contained in the cured layer is preferably 0.01 to 10% by mass.

(硬塗層)(hard coating)

且，為了進一步改善作為觸控面板時的最外層(筆輸入面)之耐擦傷性，在透明塑膠薄膜的形成有透明導電性薄膜之表面的相反面(作為觸控面板時的最外層之筆輸入面)，設有硬塗層為佳。前述硬塗層之硬度係鉛筆硬度2H以上為佳。未達2H之硬度時，作為透明導電性薄膜之硬塗層，於耐擦傷性之處不夠充分。Further, in order to further improve the scratch resistance of the outermost layer (pen input surface) when the touch panel is used, the opposite surface of the surface of the transparent plastic film on which the transparent conductive film is formed (the outermost layer of the pen as the touch panel) Input surface), preferably with a hard coat. The hardness of the hard coat layer is preferably 2H or more in pencil hardness. When the hardness is less than 2H, the hard coat layer as a transparent conductive film is insufficient in scratch resistance.

前述硬塗層之厚度為0.5~10μm為佳。厚度為未達0.5μm時，容易變成耐擦傷性不足，比10μm更厚時，從生產性之觀點而言不佳。The thickness of the hard coat layer is preferably 0.5 to 10 μm. When the thickness is less than 0.5 μm, the scratch resistance is likely to be insufficient, and when it is thicker than 10 μm, it is not preferable from the viewpoint of productivity.

使用於前述硬塗層之硬化型樹脂組成物係具有丙烯酸酯系官能基之樹脂為佳，例如可舉出較低分子量的聚酯樹脂、聚醚樹脂、丙烯酸樹脂、環氧樹脂、胺基甲酸酯樹脂、醇酸樹脂、螺縮醛(Spiroacetal)樹脂、聚丁二烯樹脂、多硫醇多烯樹脂、多元醇等多官能性化合物之(甲基)丙烯酸酯等寡聚物或預聚物等。The curable resin composition used for the hard coat layer is preferably a resin having an acrylate functional group, and examples thereof include a polyester resin having a lower molecular weight, a polyether resin, an acrylic resin, an epoxy resin, and an amine group. Oligomers or prepolymers such as (meth) acrylates of polyfunctional compounds such as acid ester resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, and polyhydric alcohols Things and so on.

且，作為反應性稀釋劑，係使用較多量地含有(甲基)丙烯酸乙酯、(甲基)丙烯酸乙基己酯、苯乙烯、甲基苯乙烯、N-乙烯吡咯啶酮等單官能單體以及多官能單體者，例如三羥甲基丙烷三(甲基)丙烯酸酯、己二醇(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、雙新戊四醇六(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯等。Further, as the reactive diluent, a monofunctional single substance such as ethyl (meth)acrylate, ethylhexyl (meth)acrylate, styrene, methylstyrene or N-vinylpyrrolidone is used in a large amount. And polyfunctional monomers such as trimethylolpropane tri(meth)acrylate, hexanediol (meth)acrylate, tripropylene glycol di(meth)acrylate, diethylene glycol di(methyl) Acrylate, neopentyl alcohol tri(meth) acrylate, dipentaerythritol hexa(meth) acrylate, 1,6-hexanediol di(meth) acrylate, neopentyl glycol di Methyl) acrylate or the like.

本發明中，作為寡聚物，混合氨酯丙烯酸酯、作為單體混合六(甲基)丙烯酸雙新戊四醇酯等為佳。In the present invention, as the oligomer, it is preferred to mix a urethane acrylate, and to mix, as a monomer, bis(pentaerythritol pentoxide).

且，作為使用於前述硬塗層之硬化型樹脂組成物，聚酯丙烯酸酯和聚胺基甲酸酯丙烯酸酯之混合物特別適合。聚酯丙烯酸酯係塗膜非常硬，適合作為硬塗層。但是，聚酯丙烯酸酯單獨之塗膜時，有耐衝撃性低且容易變脆之問題。因此，為了在塗膜賦予耐衝撃性及柔軟性，倂用聚胺基甲酸酯丙烯酸酯為佳。亦即，藉由在聚酯丙烯酸酯倂用聚胺基甲酸酯丙烯酸酯，可維持塗膜作為硬塗層之硬度，並具備耐衝撃性及柔軟性之機能。Further, as a hardening type resin composition used for the aforementioned hard coat layer, a mixture of a polyester acrylate and a polyurethane acrylate is particularly suitable. The polyester acrylate coating film is very hard and is suitable as a hard coat layer. However, when the polyester acrylate is coated alone, it has a problem that it is low in impact resistance and easily becomes brittle. Therefore, in order to impart impact resistance and flexibility to the coating film, it is preferred to use a polyurethane acrylate. That is, by using polyurethane acrylate in polyester acrylate, the hardness of the coating film as a hard coat layer can be maintained, and the function of punching resistance and flexibility can be maintained.

兩者之配合比例相對於聚酯丙烯酸酯樹脂100質量份而言，聚胺基甲酸酯丙烯酸酯樹脂為30質量份以下為佳。聚胺基甲酸酯丙烯酸酯樹脂之添加比例為超過30質量份時，塗膜過軟而有耐衝擊性不足之傾向。The blending ratio of the two is preferably 30 parts by mass or less based on 100 parts by mass of the polyester acrylate resin. When the addition ratio of the polyurethane acrylate resin is more than 30 parts by mass, the coating film is too soft and the impact resistance tends to be insufficient.

前述硬化型樹脂組成物之硬化方法可使用通常之硬化方法，亦即藉由加熱、電子束或紫外線照射而硬化之方法。例如電子束硬化之情形，係利用由考瓦(Cockcroft-Walton)型、范德格雷夫氏(Van de Graaff)型、共振變壓型、絕緣核芯變壓器型、直線型、地那米(Dynamitron)型、高頻型等各種電子束加速器所放出之具有50~1000keV、較佳為100~300keV能量之電子束等。且，於紫外線硬化之情形可利用由超高壓水銀燈、高壓水銀燈、低壓水銀燈、碳弧、氙弧、金屬鹵素燈等光線發出之紫外線等。The hardening method of the above-mentioned hardening type resin composition can be carried out by a usual hardening method, that is, a method of hardening by heating, electron beam or ultraviolet irradiation. For example, in the case of electron beam hardening, it is a Cockcroft-Walton type, a Van de Graaff type, a resonant transformer type, an insulated core transformer type, a linear type, and a Dynamitron. An electron beam having an energy of 50 to 1000 keV, preferably 100 to 300 keV, which is emitted by various electron beam accelerators such as a high frequency type. Further, in the case of ultraviolet curing, ultraviolet rays emitted from light such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, or a metal halide lamp can be used.

再者，於電離放射線硬化之情形，使前述硬化型樹脂組成物中含有光聚合引發劑或光增感劑為佳。作為光聚合引發劑可舉出苯乙酮類、二苯甲酮類、米氏苯甲酸苄酯(Michler-Benzoyl benzoate)、α-阿米羅基酯(α-Amyloxim ester)、一硫化四甲基秋蘭姆(Tetramethyithiuram monosulfide)、硫雜蒽酮類等。且，作為光增感劑係正-丁胺、三乙胺、三正丁膦等為佳。Further, in the case of ionizing radiation hardening, it is preferred that the curable resin composition contains a photopolymerization initiator or a photosensitizer. Examples of the photopolymerization initiator include acetophenones, benzophenones, Michler-Benzoyl benzoate, α-Amyloxim ester, and tetrasulfide tetrasulfide. Tetramethyithiuram monosulfide, thioxanthone, etc. Further, as the photosensitizer, n-butylamine, triethylamine, tri-n-butylphosphine or the like is preferred.

為了賦予硬塗層防眩性，將CaCO3 或SiO2 等無機粒子分散至硬化型樹脂之方法、或在硬塗層的表面形成凹凸狀之方法為有效。例如為了形成凹凸，在含有硬化型樹脂組成物之塗液塗敷後，將表面具有凸狀之賦形薄膜積層，從該賦形薄膜上照射紫外線使硬化型樹脂硬化後，藉由僅剝離賦形薄膜而獲得。In order to impart anti-glare property to the hard coat layer, a method of dispersing inorganic particles such as CaCO 3 or SiO 2 to the curable resin or a method of forming irregularities on the surface of the hard coat layer is effective. For example, in order to form irregularities, after coating with a coating liquid containing a curable resin composition, a film having a convex shape on the surface is laminated, and ultraviolet rays are irradiated from the shaped film to harden the hardening resin, and only the peeling is performed. Obtained as a film.

前述賦型薄膜可使用在具有脫模性之聚對苯二甲酸乙二酯(以下有時簡稱PET)等基材薄膜上設有所要的凸狀者、或者在PET等基材薄膜上形成有纖細之凸層者等。其凸層之形成，例如可藉由使用無機粒子和黏合劑樹脂所構成的樹脂組成物塗敷於基材薄膜上而獲得。The above-mentioned shaped film can be formed by providing a desired convex shape on a base film such as polyethylene terephthalate having a release property (hereinafter sometimes referred to as PET) or on a base film such as PET. Slim convex layer, etc. The formation of the convex layer can be obtained, for example, by applying a resin composition composed of inorganic particles and a binder resin to a base film.

作為前述黏合劑樹脂係例如使用經聚異氰酸酯交聯之丙烯酸多元醇，作為無機粒子可使用CaCO3 或SiO2 等。且，其他在製造PET時亦可使用混入有SiO2 等無機粒子之粗糙(mat)型PET。As the binder resin, for example, an acrylic polyol crosslinked with a polyisocyanate is used, and as the inorganic particles, CaCO 3 or SiO 2 or the like can be used. Further, other types of mat type PET in which inorganic particles such as SiO 2 are mixed may be used in the production of PET.

將該賦型薄膜積層於紫外線硬化型樹脂之塗膜後，照射紫外線使塗膜硬化時、賦型薄膜為將PET作為基材之薄膜時，紫外線之短波長側被吸收到該薄膜，而有紫外線硬化型樹脂之硬化不足的缺點。因而，必須使用積層於紫外線硬化型樹脂之塗膜的賦型薄膜之全光線透過率為20%以上者。When the coating film is laminated on the coating film of the ultraviolet curable resin, and the coating film is a film using PET as a substrate when the coating film is cured by ultraviolet rays, the short-wavelength side of the ultraviolet light is absorbed into the film. The shortcoming of insufficient curing of the ultraviolet curable resin. Therefore, it is necessary to use a coating film laminated on the coating film of the ultraviolet curable resin to have a total light transmittance of 20% or more.

且，使用於觸控面板時，由於可視光線之透過率進一步提高，因此在硬塗層上施行低反射處理亦可。該低反射處理係將具有與硬塗層之折射率相異的折射率之材料積層單層或2層以上為佳。Moreover, when used in a touch panel, since the transmittance of visible light is further improved, it is also possible to perform low reflection treatment on the hard coat layer. This low-reflection treatment is preferably a single-layer or two-layer material having a refractive index different from the refractive index of the hard coat layer.

單層構造時，使用比硬塗層具有更小的折射率之材料為佳。且，若是2層以上之多層構造時，鄰接硬塗層之層係使用比硬塗層具有更大的折射率之材料，在其上之層選用具有較其小的折射率之材料為佳。作為構成這種低反射處理之材料，不論有機材料或無機材料只要是滿足上述折射率關係則不受特別限定。例如使用CaF2 、MgF2 、NaAlF4 、SiO2 、ThF4 、ZrO2 、Nd2 O3 、SnO2 、TiO2 、CeO2 、ZnS、In2 O3 等介電質為佳。In the case of a single layer construction, it is preferred to use a material having a smaller refractive index than the hard coat layer. Further, in the case of a multilayer structure of two or more layers, a layer adjacent to the hard coat layer is made of a material having a larger refractive index than the hard coat layer, and a layer having a smaller refractive index is preferably used as the layer thereon. The material constituting such a low reflection treatment is not particularly limited as long as the organic material or the inorganic material satisfies the above refractive index relationship. For example, a dielectric such as CaF 2 , MgF 2 , NaAlF 4 , SiO 2 , ThF 4 , ZrO 2 , Nd 2 O 3 , SnO 2 , TiO 2 , CeO 2 , ZnS or In 2 O 3 is preferably used.

該低反射處理為真空蒸鍍法、濺鍍法、CVD法、離子電鍍法等乾式塗布法、或凹版印刷塗布方式、逆向輥塗方式、模塗方式等濕式塗布法。The low-reflection treatment is a dry coating method such as a vacuum deposition method, a sputtering method, a CVD method, or an ion plating method, or a wet coating method such as a gravure coating method, a reverse roll coating method, or a die coating method.

再者，該低反射處理層積層之前，作為前處理，亦可在硬塗層施行電暈放電處理、電漿處理、濺鍍蝕刻處理、電子束照射處理、紫外線照射處理、底層塗料處理(primer treatment)、易接合處理等眾知之表面處理。Further, before the low-reflection treatment layer is laminated, as a pre-treatment, corona discharge treatment, plasma treatment, sputtering etching treatment, electron beam irradiation treatment, ultraviolet irradiation treatment, primer treatment (primer) may be performed on the hard coat layer. Treatment), easy bonding treatment, and other known surface treatments.

(透明導電性薄片)(transparent conductive sheet)

本發明之透明導電性薄片，係於本發明之透明導電性薄膜之積層有透明導電性薄膜層之面的相反面，藉由黏合劑貼合透明樹脂薄片積層所得。本發明之透明導電性薄片可使用在觸控面板之固定電極。亦即，將觸控面板之固定電極之基板從玻璃變更為本發明之透明樹脂薄片，藉此可製作輕量且不易裂開的觸控面板。The transparent conductive sheet of the present invention is obtained by laminating a transparent resin sheet by a bonding agent on the opposite side of the surface of the transparent conductive film of the present invention in which the transparent conductive film layer is laminated. The transparent conductive sheet of the present invention can be used for a fixed electrode of a touch panel. That is, the substrate of the fixed electrode of the touch panel is changed from glass to the transparent resin sheet of the present invention, whereby a lightweight and non-cleavable touch panel can be produced.

前述黏合劑只要是具有透明性者則無特別限定，但例如丙烯酸系黏合劑、聚矽氧系黏合劑、橡膠系黏合劑等較合適。該黏合劑之厚度並無特別限定，但通常期望設定在1~100μm之範圍。黏合劑之厚度為未達1μm之厚度時，難以獲得實用上沒有問題之接著性，超過100μm之厚度時，從生產性之觀點而言不佳。The binder is not particularly limited as long as it has transparency. For example, an acrylic binder, a polyoxynene binder, a rubber binder, or the like is suitable. The thickness of the binder is not particularly limited, but it is usually desirably set in the range of 1 to 100 μm. When the thickness of the binder is less than 1 μm, it is difficult to obtain a practically non-problem adhesive property, and when it exceeds a thickness of 100 μm, it is not preferable from the viewpoint of productivity.

此藉由黏合劑貼合之透明樹脂薄片係為了賦予與玻璃同等的機械強度而使用者，厚度為0.05~5mm之範圍為佳。前述透明樹脂薄片之厚度為未達0.05mm時，機械強度較玻璃不足。另一方面，厚度為超過5mm時，過厚而不適於使用在觸控面板。且，該透明樹脂薄片之材質可使用與前述透明塑膠薄膜同樣者。The transparent resin sheet to be bonded by the adhesive is preferably used in a range of 0.05 to 5 mm in order to impart mechanical strength equivalent to that of glass. When the thickness of the transparent resin sheet is less than 0.05 mm, the mechanical strength is insufficient compared to glass. On the other hand, when the thickness is more than 5 mm, it is too thick and is not suitable for use in a touch panel. Further, the material of the transparent resin sheet can be the same as that of the transparent plastic film.

(觸控面板)(touch panel)

觸控面板係將具有透明導電性薄膜層的一對透明導電性基板(薄膜、玻璃、薄片任一種)，隔著間隔物配置成透明導電性薄膜層呈相對向。藉由筆輸入文字時，由於筆的推壓使呈相對向之透明導電性薄膜彼此接觸，電源成為ON狀態，而可檢測出觸控面板上之筆位置。藉由連續且正確地檢測出該筆位置之方式，可從筆的軌跡辨識文字。In the touch panel, a pair of transparent conductive substrates (any of a film, a glass, and a sheet) having a transparent conductive film layer are disposed so that the transparent conductive film layers face each other with a spacer interposed therebetween. When the characters are input by the pen, the opposing transparent conductive films are brought into contact with each other by the push of the pen, and the power source is turned on, and the position of the pen on the touch panel can be detected. The text can be recognized from the trajectory of the pen by continuously and correctly detecting the position of the pen.

本發明之觸控面板係至少在一方之透明導電性基板使用上述本發明之透明導電性薄膜者。此時，若筆接觸側的可動電極係使用本發明之透明導電性薄膜，則即使組入於高精細之液晶顯示器等顯示體，目視辨認性亦不會降低，且由於筆滑動耐久性優異而能夠成為長期穩定之觸控面板。於第1圖顯示使用本發明之透明導電性薄膜的觸控面板之例。In the touch panel of the present invention, the transparent conductive film of the present invention is used in at least one of the transparent conductive substrates. In this case, when the transparent conductive film of the present invention is used as the movable electrode of the present invention, the visibility is not lowered even if it is incorporated in a display such as a high-definition liquid crystal display, and the pen sliding durability is excellent. Can become a long-term stable touch panel. Fig. 1 shows an example of a touch panel using the transparent conductive film of the present invention.

且，於第2圖顯示使用本發明之透明導電性薄膜及透明導電性薄片所得之不使用玻璃基板的塑膠製觸控面板之剖視圖。由於該塑膠製觸控面板不使用玻璃，因此非常輕且不會因為衝擊而裂開。Further, in Fig. 2, a cross-sectional view of a touch panel made of plastic which does not use a glass substrate obtained by using the transparent conductive film of the present invention and a transparent conductive sheet is shown. Since the plastic touch panel does not use glass, it is very light and does not crack due to impact.

[實施例][Examples]

以下根據實施例進一步詳細地說明本發明，但本發明並非受該等實施例限定者。此外，透明導電性薄膜之性能及高折射率層、透明導電性薄膜之結晶性、觸控面板之筆滑動耐久性實驗係藉由下述方法測量。The invention is further illustrated by the following examples, but the invention is not limited by the examples. Further, the performance of the transparent conductive film, the crystallinity of the high refractive index layer, the transparent conductive film, and the pen sliding durability test of the touch panel were measured by the following methods.

(1)全光線透過率(1) Total light transmittance

根據JIS-K7136，利用日本電色工業(股)製NDH-1001DP測量光線透過率。According to JIS-K7136, the light transmittance was measured using a NDH-1001DP manufactured by Nippon Denshoku Industries Co., Ltd.

(2)表面電阻值(2) Surface resistance value

根據JIS-K7194，以4端子法測量。測量機係使用三菱油化(股)製Lotest AMCP-T400。It is measured by the 4-terminal method according to JIS-K7194. The measuring machine uses the Mitsubishi Oil Chemical Co., Ltd. Lotest AMCP-T400.

(3)色彩(a值、b值)(3) Color (a value, b value)

根據JIS-K7105，利用色差計(日本電色工業製、ZE-2000)，以標準光C/2測量色彩a值、b值。According to JIS-K7105, color a value and b value were measured with a standard light C/2 using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., ZE-2000).

(4)分光透過率之峰值波長(4) Peak wavelength of spectral transmittance

利用分光光度計(日立U-3500型)，於380~780nm之範圍在透明導電性薄膜側照射光，測量室內空氣作為透過率之參照來測定。根據測量結果以透過率為最大值之波長作為峰值波長。The spectrophotometer (Hitachi U-3500 type) was used to irradiate light on the side of the transparent conductive film in the range of 380 to 780 nm, and the measurement of indoor air as a reference of the transmittance was measured. According to the measurement result, the wavelength at which the transmittance is the maximum is taken as the peak wavelength.

(5)高折射率層、透明導電性薄膜之結晶性(5) Crystallinity of high refractive index layer and transparent conductive film

將積層有高折射率層、透明導電性薄膜之薄膜試料片切成300μm×300μm之正方形，於超薄切片機(Ultramicrotome)的試料保持具，將薄膜面固定於前方。接著，以能獲得具有1μm×1μm以上之目的觀察部位之切片的程度，將小刀對薄膜面設置成極銳角，以設定厚度70nm切削。A film sample sheet in which a high refractive index layer and a transparent conductive film were laminated was cut into a square of 300 μm × 300 μm, and placed on a sample holder of an ultramicrotome to fix the film surface to the front. Next, the knives were placed at an extremely acute angle with respect to the film surface to the extent that a slice having a target of 1 μm × 1 μm or more was obtained, and the thickness was cut at a thickness of 70 nm.

在該切片之導電性薄膜表面側且薄膜沒有顯著損傷之部位，確保1μm×1μm之觀察視野，利用透過型電子顯微鏡(JEOL公司製、JEM-2010)，以加速電壓200kV、明視野觀察倍率5萬倍進行照相攝影，評價結晶性。On the surface side of the conductive film of the slice and the portion where the film was not significantly damaged, an observation field of 1 μm × 1 μm was secured, and an acceleration electron beam (JEOL, JEM-2010) was used, and an acceleration voltage of 200 kV and a bright field observation magnification of 5 were observed. Photographic photography was performed 10,000 times to evaluate crystallinity.

(6)框緣附近之筆滑動耐久性實驗(6) Pen sliding durability test near the edge of the frame

從觸控面板的貼合部內側偏離1.5mm之位置以聚縮醛製之筆(前端形狀：0.8mm R)施加2.5N之負荷，在觸控面板進行1萬次(往復5000次)直線滑動實驗。此時之滑動距離為30mm、滑動速度為60mm/秒。再者，觸控面板的上下基板的間隙為150μm。此滑動耐久性實驗後，首先目視觀察滑動部是否白化。且，以顯微鏡觀察滑動部位附近，觀察有無龜裂產生。再者，測量以筆負荷1.0N推壓滑動部時之ON電阻(可動電極(薄膜電極)和固定電極接觸時之電阻值)。A load of 2.5 N was applied from a polyacetal pen (front end shape: 0.8 mm R) from a position of 1.5 mm inside the bonding portion of the touch panel, and 10,000 times (reciprocating 5000 times) linear sliding was performed on the touch panel. experiment. At this time, the sliding distance was 30 mm and the sliding speed was 60 mm/sec. Furthermore, the gap between the upper and lower substrates of the touch panel was 150 μm. After this sliding durability test, first, it was visually observed whether or not the sliding portion was whitened. Further, the vicinity of the sliding portion was observed with a microscope to observe the presence or absence of cracking. In addition, the ON resistance (resistance value when the movable electrode (thin film electrode) and the fixed electrode are in contact with each other) when the sliding portion is pressed by the pen load of 1.0 N is measured.

(7)筆滑動耐久性實驗(7) Pen sliding durability test

以聚縮醛製之筆(前端形狀：0.8mm R)施加2.5N之負荷，在觸控面板進行10萬次(往復5萬次)直線滑動實驗。此時之滑動距離為30mm、滑動速度為60mm/秒。此滑動耐久性實驗後，首先目視觀察滑動部是否白化。再者，以筆負荷0.5N施加在上述滑動部，將20mmΦ 之記號○印記做筆記，評價觸控面板是否能正確地讀取此紀錄。再者，測量以筆負荷0.5N推壓滑動部時之ON電阻(可動電極(薄膜電極)和固定電極接觸時之電阻值)。A load of 2.5 N was applied to a pen made of polyacetal (front end shape: 0.8 mm R), and a linear sliding test was performed on the touch panel 100,000 times (reciprocating 50,000 times). At this time, the sliding distance was 30 mm and the sliding speed was 60 mm/sec. After this sliding durability test, first, it was visually observed whether or not the sliding portion was whitened. Further, a pen load of 0.5 N was applied to the sliding portion, and a mark of 20 mm Φ was marked as a note to evaluate whether the touch panel can correctly read the record. Further, the ON resistance (resistance value when the movable electrode (thin film electrode) and the fixed electrode are in contact with each other) when the sliding portion is pressed by a pen load of 0.5 N is measured.

(8)高溫‧高濕下之環境實驗(8) Environmental experiment under high temperature and high humidity

利用NAGANO(股)科學機械製作所製之LH43-12P，在85℃、85% RH的環境下將透明導電性薄膜暴露1000小時。該處理後測量表面電阻值、光線透過率、色彩。The transparent conductive film was exposed to an environment of 85 ° C and 85% RH for 1000 hours using LH43-12P manufactured by NAGANO Scientific Machinery Co., Ltd. After the treatment, the surface resistance value, the light transmittance, and the color were measured.

(9)高折射率層、低折射率層、透明導電性薄膜層之膜厚(9) Film thickness of the high refractive index layer, the low refractive index layer, and the transparent conductive thin film layer

將積層有高折射率層、低折射率層、透明導電性薄膜層之薄膜試料片切成1mm×10mm之大小，包埋於電子顯微鏡用環氧樹脂。將其固定在超薄切片機(Ultramicrotome)的試料保持具，製作平行於經包埋的試料片之短邊的斷面薄切片。接著，在該切片之薄膜沒有顯著損傷的部位，利用透過型電子顯微鏡(JEOL公司製、JEM-2010)，以加速電壓200kV、明視野觀察倍率1萬倍進行照片攝影，從所獲得的照片求出膜厚。The film sample sheet in which the high refractive index layer, the low refractive index layer, and the transparent conductive thin film layer were laminated was cut into a size of 1 mm × 10 mm, and embedded in an epoxy resin for electron microscopy. This was fixed to a sample holder of an ultramicrotome, and a thin section of a section parallel to the short side of the embedded sample piece was produced. Then, a photograph was taken by a transmission electron microscope (JE-2010, manufactured by JEOL Co., Ltd.) at an acceleration voltage of 200 kV and a bright field observation magnification of 10,000 times in a portion where the film of the slice was not significantly damaged, and the photograph was obtained from the obtained photograph. The film is thick.

(10)高折射率層、低折射率層、透明導電性薄膜層之折射率(10) Refractive index of high refractive index layer, low refractive index layer, and transparent conductive thin film layer

針對在矽晶圓上將各層分別以相同的成膜條件製作而成的試料，利用分光光譜儀(Ellipsometer)(大塚電子股份有限公司製、FE-5000)，評價550nm之折射率。且，利用光學模擬軟體對設有各層之薄膜的分光透過率測量資料進行擬合(Fitting)，算出折射率。此時，各層之膜厚係使用前述膜厚評價方法所評價之值。進一步確認如此地算出之各層折射率和矽晶圓上各層折射率沒有太大的差異。The refractive index at 550 nm was evaluated by a spectrophotometer (Ellipsometer (manufactured by Otsuka Electronics Co., Ltd., FE-5000) for a sample prepared by the same film formation conditions on the enamel wafer. Further, the optical transmittance software was used to fit the spectral transmittance measurement data of the film provided with each layer, and the refractive index was calculated. At this time, the film thickness of each layer was the value evaluated by the said film thickness evaluation method. It was further confirmed that the refractive index of each layer thus calculated and the refractive index of each layer on the germanium wafer were not greatly different.

[實施例1][Example 1]

在含有光聚合引發劑之100質量份的丙烯酸系樹脂(大日精化工業公司製、Seikabeam EXF-01J)，加入作為溶劑的甲苯/MEK(80/20：質量比)之混合溶劑，至固體分濃度成為50質量%，攪拌且均等地溶解，調製成塗布液。100 parts by mass of an acrylic resin (Seikabeam EXF-01J, manufactured by Daisei Seiki Co., Ltd.) containing a photopolymerization initiator, and a mixed solvent of toluene/MEK (80/20: mass ratio) as a solvent was added to the solid fraction. The concentration was 50% by mass, and the mixture was stirred and uniformly dissolved to prepare a coating liquid.

在兩面具有易接合層之二軸配向透明PET薄膜(東洋紡績公司製、A4340、厚度188μm)，使用邁耶棒(Meyer Bar)塗布經調製之塗布液形成塗膜厚度形成5μm。以80℃進行1分鐘乾燥後，利用紫外線照射裝置(Eye Graphics公司製、UB042-5AM-W型)照射紫外線(光量：300mJ/cm2 )，使塗膜硬化。接著，針對反面也同樣地塗設塗膜後，以180℃施行1分鐘加熱處理，進行減少揮發成分。A biaxially oriented transparent PET film (manufactured by Toyobo Co., Ltd., A4340, thickness: 188 μm) having an easy-bonding layer on both sides was coated with a prepared coating liquid using a Meyer Bar to form a coating film thickness of 5 μm. After drying at 80 ° C for 1 minute, ultraviolet rays (light amount: 300 mJ/cm 2 ) were irradiated by an ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd., UB042-5AM-W type) to cure the coating film. Next, the coating film was applied similarly to the reverse side, and then heat-treated at 180 ° C for 1 minute to reduce the volatile component.

且，為了將積層有該硬化物層之二軸配向透明PET薄膜進行真空暴露，因此在真空處理室中進行反捲處理。此時的壓力為0.002Pa，暴露時間為20分鐘。且，中央輥的溫度為40℃。Further, in order to vacuum-expose the biaxially oriented transparent PET film in which the cured layer is laminated, the rewinding treatment is performed in the vacuum processing chamber. The pressure at this time was 0.002 Pa and the exposure time was 20 minutes. Moreover, the temperature of the center roll was 40 °C.

接著，在該硬化物層上將銦-錫複合氧化物所構成的高折射率層成膜。此時，將濺鍍前的壓力設定為0.0001Pa，利用含有36質量%氧化錫之氧化銦(住友金屬鑛山公司製、密度6.9g/cm3 )作為標靶，施加2W/cm2 之DC電力。且，將Ar氣體以130sccm、O2 氣體以表面電阻值為最小時之O2 流量的3倍流速流過，在0.4Pa之大氣下利用DC磁控濺鍍法成膜。但是，並非通常的DC，為了防止電弧放電，利用日本ENI製RPG-100，以50kHz周期施加5μs寬之脈衝。且，中央輥溫度為0℃，進行濺鍍。Next, a high refractive index layer composed of an indium-tin composite oxide is formed on the cured layer. In this case, the pressure before the sputtering was set to 0.0001 Pa, and a DC of 2 W/cm 2 was applied using indium oxide (manufactured by Sumitomo Metal Mining Co., Ltd., density: 6.9 g/cm 3 ) containing 36% by mass of tin oxide as a target. electric power. Further, Ar gas was flowed at a flow rate of three times the flow rate of O 2 at a surface resistance value of 130 sccm and O 2 gas, and a film was formed by DC magnetron sputtering at an atmosphere of 0.4 Pa. However, it is not a normal DC, and in order to prevent arc discharge, a pulse of 5 μs width is applied at a cycle of 50 kHz by using RPG-100 manufactured by ENI, Japan. Further, the center roll temperature was 0 ° C, and sputtering was performed.

且，以濺鍍製程監視器(LEYBOLD INFICON公司製、XPR2)長時觀測大氣之氧分壓，反饋到氧氣之流量計及DC電源，使銦-錫複合氧化物薄膜中的氧化度成為一定。如以上方式，堆積成厚度45nm之銦-錫複合氧化物所構成的高折射率層。如此地獲得之高折射率層之表面電阻值為1×106 Ω/□以上。In addition, the oxygen partial pressure of the atmosphere is observed for a long time by a sputtering process monitor (XPR2 manufactured by LEYBOLD INFICON Co., Ltd.), and is fed back to the oxygen flow meter and the DC power source to make the degree of oxidation in the indium-tin composite oxide film constant. As described above, a high refractive index layer composed of an indium-tin composite oxide having a thickness of 45 nm was deposited. The surface resistivity of the high refractive index layer thus obtained was 1 × 10 6 Ω/□ or more.

再者，為了在前述高折射層上形成SiO2 薄膜作為低折射率層，而用矽作為標靶，利用直流磁控濺鍍法、真空度為0.27Pa、作為氣體之Ar氣體為500sccm、O2 氣體為80sccm之流速流過。且，在基板的背面設有0℃之冷卻輥，將透明塑膠薄膜冷卻。對此時的標靶供給7.8W/cm2 之電力，動態率為23nm‧m/分。Further, in order to form a SiO 2 film as a low refractive index layer on the high refractive layer, and using ruthenium as a target, a DC magnetron sputtering method, a degree of vacuum of 0.27 Pa, and an Ar gas of a gas of 500 sccm, O are used. 2 The gas flows at a flow rate of 80 sccm. Further, a chill roll of 0 ° C was placed on the back surface of the substrate to cool the transparent plastic film. At this time, the target was supplied with electric power of 7.8 W/cm 2 and the dynamic rate was 23 nm ‧ m/min.

且，一面長時觀測成膜中的電壓值，一面反饋到氧氣之流量計，使電壓值成為一定。如以上方式，堆積成厚度55nm、折射率1.46之低折射率層。Further, while observing the voltage value in the film formation for a long period of time, the flow rate of the oxygen is fed back to make the voltage value constant. As described above, a low refractive index layer having a thickness of 55 nm and a refractive index of 1.46 was deposited.

接著，在該低折射率層上將銦-錫複合氧化物所構成的透明導電性薄膜成膜。此時，將濺鍍前的壓力設定為0.0001Pa，利用含有36質量%氧化錫之氧化銦(住友金屬鑛山公司製、密度6.9g/cm3 )作為標靶，施加2W/cm2 之DC電力。且，以Ar氣體為130sccm、O2 氣體以表面電阻值為最小時之流速流過、在0.4Pa之大氣下利用DC磁控濺鍍法成膜。但是，並非通常之DC，為了防止電弧放電，使用日本ENI製RPG-100，以50kHz周期施加5μs寬之脈衝。且，中央輥溫度為10℃，進行濺鍍。Next, a transparent conductive film made of an indium-tin composite oxide is formed on the low refractive index layer. In this case, the pressure before the sputtering was set to 0.0001 Pa, and a DC of 2 W/cm 2 was applied using indium oxide (manufactured by Sumitomo Metal Mining Co., Ltd., density: 6.9 g/cm 3 ) containing 36% by mass of tin oxide as a target. electric power. Further, a film was formed by a DC magnetron sputtering method in which an Ar gas was 130 sccm and an O 2 gas flowed at a flow rate at which the surface resistance value was the smallest. However, instead of the usual DC, in order to prevent arc discharge, a pulse of 5 μs width was applied at a cycle of 50 kHz using an RPG-100 manufactured by NEI Japan. Further, the center roll temperature was 10 ° C, and sputtering was performed.

且，利用濺鍍製程監視器(LEYBOLD INFICON公司製、XPR2)長時觀測大氣之氧分壓，並反饋到氧氣的流量計及DC電源，使銦-錫複合氧化物薄膜中的氧化度成為一定。如以上方式，堆積厚度15nm、折射率1.96之銦-錫複合氧化物所構成的透明導電性薄膜。In addition, the oxygen partial pressure of the atmosphere is observed for a long time by a sputtering process monitor (XPR2 manufactured by LEYBOLD INFICON Co., Ltd.), and the oxygen flow meter and the DC power source are fed back to make the oxidation degree in the indium-tin composite oxide film constant. . As described above, a transparent conductive film composed of an indium-tin composite oxide having a thickness of 15 nm and a refractive index of 1.96 was deposited.

<觸控面板之製作><Manufacture of touch panel>

將該透明導電性薄膜作為一方之面板使用，作為另一方之面板，係於玻璃基板上使用以電漿CVD法、厚度為20nm之銦-錫複合氧化物薄膜(氧化錫含量：10質量%)所構成的透明導電性薄膜(日本曹達公司製、S500)。使該2枚面板隔著直徑30μm之環氧化物珠配置成透明導電性薄膜為相對向，製作成觸控面板。The transparent conductive film was used as one of the panels, and the other panel was an indium-tin composite oxide film (tin oxide content: 10% by mass) having a thickness of 20 nm by a plasma CVD method on the glass substrate. A transparent conductive film (manufactured by Nippon Soda Co., Ltd., S500). The two panels were placed so as to face each other with a transparent conductive film interposed between the epoxide beads having a diameter of 30 μm to form a touch panel.

[實施例2][Embodiment 2]

實施例1中，作為製作高折射率層之標靶係含有10質量%氧化錫之氧化銦(住友金屬鑛山公司製、密度7.1g/cm3 )，O2 氣體流量係表面電阻值為最小時之流量的5倍以外，與實施例1同樣地製作成透明導電性薄膜。所獲得之高折射率層的表面電阻值為1×106 Ω/□以上。再者，使用該透明導電性薄膜，與實施例1同樣地製作成觸控面板。此外，水分壓對惰性氣體之比為5×10-3 。In the first embodiment, as a target for producing a high refractive index layer, indium oxide containing 10% by mass of tin oxide (manufactured by Sumitomo Metal Mining Co., Ltd., density: 7.1 g/cm 3 ) is used, and the surface resistance value of the O 2 gas flow rate is the highest. A transparent conductive film was produced in the same manner as in Example 1 except that the flow rate was 5 times. The surface resistivity of the obtained high refractive index layer was 1 × 10 6 Ω/□ or more. Further, a touch panel was produced in the same manner as in Example 1 using this transparent conductive film. Further, the ratio of the water pressure to the inert gas was 5 × 10 -3 .

[比較例1][Comparative Example 1]

實施例1中，作為製作高折射率層之標靶，除了是含有5質量%氧化錫之氧化銦(三井金屬鑛業公司製、密度7.1g/cm3 )以外，與實施例1同樣地製作成透明導電性薄膜。再者，使用該透明導電性薄膜，與實施例1同樣地製作成觸控面板。In the same manner as in Example 1, except that the indium oxide (manufactured by Mitsui Mining and Mining Co., Ltd., density: 7.1 g/cm 3 ) containing 5% by mass of tin oxide was used as the target for producing the high refractive index layer. Transparent conductive film. Further, a touch panel was produced in the same manner as in Example 1 using this transparent conductive film.

[比較例2][Comparative Example 2]

實施例1中，除了低折射率層之膜厚為70nm以外，與實施例1同樣地製作成透明導電性薄膜。再者，使用該透明導電性薄膜，與實施例1同樣地製作成觸控面板。In the same manner as in Example 1, except that the film thickness of the low refractive index layer was 70 nm, a transparent conductive film was produced. Further, a touch panel was produced in the same manner as in Example 1 using this transparent conductive film.

[比較例3][Comparative Example 3]

實施例1中，除了低折射率層之膜厚為40nm以外，與實施例1同樣地製作成透明導電性薄膜。再者，使用該透明導電性薄膜，與實施例1同樣地製作成觸控面板。In the same manner as in Example 1, except that the film thickness of the low refractive index layer was 40 nm, a transparent conductive film was produced. Further, a touch panel was produced in the same manner as in Example 1 using this transparent conductive film.

[實施例3][Example 3]

與實施例1同樣地製作由硬塗層/二軸配向透明PET薄膜所構成的基材/硬化物層/高折射率層/低折射率層/透明導電性薄膜層所構成的積層體，接著在該硬塗層上順序地積層TiO2 薄膜層(折射率：2.30、膜厚15nm)、SiO2 薄膜層(折射率：1.46、膜厚29nm)、TiO2 薄膜層(折射率：2.30、膜厚109nm)、SiO2 薄膜層(折射率：1.46、膜厚87nm)，藉此形成反射防止處理層。為了形成TiO2 薄膜層，用鈦作為標靶，利用直流磁控濺鍍法、真空度為0.27Pa、作為氣體之Ar氣體為500sccm、O2 氣體為80sccm之流速流過。且，在基板背面設有表面溫度為0℃之冷卻輥，冷卻了透明塑膠薄膜。對此時之標靶供給7.8W/cm2 之電力，動態率為23nm‧m/分。In the same manner as in Example 1, a laminate comprising a base material/cured layer/high refractive index layer/low refractive index layer/transparent conductive thin film layer composed of a hard coat layer/biaxially oriented transparent PET film was produced, and then on the hard coat layer are sequentially laminated layer TiO 2 thin film (refractive index: 2.30, thickness of 15nm), SiO 2 thin-film layer (refractive index: 1.46, thickness of 29nm), TiO 2 thin-film layer (refractive index: 2.30, film A film thickness of 109 nm) and a SiO 2 film layer (refractive index: 1.46, film thickness: 87 nm) were used to form an antireflection treatment layer. In order to form a TiO 2 film layer, titanium was used as a target, and a flow rate of a DC magnetron sputtering method, a vacuum degree of 0.27 Pa, a gas Ar gas of 500 sccm, and an O 2 gas of 80 sccm was flown. Further, a cooling roll having a surface temperature of 0 ° C was provided on the back surface of the substrate to cool the transparent plastic film. At this time, the target was supplied with electric power of 7.8 W/cm 2 and the dynamic rate was 23 nm ‧ m/min.

為了形成SiO2 薄膜，用矽作為標靶，利用直流磁控濺鍍法、以真空度為0.27Pa、作為氣體之Ar氣體為500sccm、O2 氣體為80sccm之流速流過。且，在基板背面設有0℃之冷卻輥，冷卻了透明塑膠薄膜。對此時之標靶供給7.8W/cm2 之電力，動態率為23nm‧m/分。再者，將該透明導電性薄膜作為一方之面板使用，與與實施例1同樣地製作成觸控面板。In order to form a SiO 2 film, ruthenium was used as a target, and a DC magnetron sputtering method was used to flow at a flow rate of 0.27 Pa, a gas of 500 Vcm as a gas, and an O 2 gas of 80 sccm. Further, a cooling roll of 0 ° C was placed on the back surface of the substrate to cool the transparent plastic film. At this time, the target was supplied with electric power of 7.8 W/cm 2 and the dynamic rate was 23 nm ‧ m/min. Further, this transparent conductive film was used as one of the panels, and a touch panel was produced in the same manner as in Example 1.

[實施例4][Example 4]

將與實施例1同樣地製作成的透明導電性薄膜，藉由丙烯酸系黏合劑，貼合於厚度為1.0mm之聚碳製薄片，製作成透明導電性積層薄片。將該透明導電性積層薄片作為固定電極使用，將實施例1之透明導電性薄膜用於可動電極，與實施例1同樣地製作成觸控面板。The transparent conductive film produced in the same manner as in Example 1 was bonded to a polycrystalline carbon sheet having a thickness of 1.0 mm by an acrylic adhesive to prepare a transparent conductive laminated sheet. The transparent conductive laminated sheet was used as a fixed electrode, and the transparent conductive film of Example 1 was used for a movable electrode, and a touch panel was produced in the same manner as in Example 1.

[實施例5][Example 5]

實施例1中，作為低折射率層，除了將氟化鎂(MgF2 )所構成的薄膜成膜以外，與實施例1同樣地形成了透明導電性薄膜。In the first embodiment, a transparent conductive film was formed in the same manner as in Example 1 except that a film made of magnesium fluoride (MgF 2 ) was formed as a low refractive index layer.

此時，將濺鍍前的壓力設定為0.0001Pa，作為標靶係使用氟化鎂(三井金屬製)，施加2W/cm2 之13.56MHz高頻電力，利用磁控濺鍍法、真空度為0.27Pa、作為氣體之Ar氣體係以500sccm之流速流過，進行成膜。且，長時觀測成膜中的電壓值，並反饋到氧氣的流量計使電壓值成為一定。如以上方式，堆積成厚度60nm、折射率1.36之低折射率層。In this case, the pressure before the sputtering was set to 0.0001 Pa, and magnesium fluoride (manufactured by Mitsui Metals Co., Ltd.) was used as the target system, and 13.56 MHz high-frequency power of 2 W/cm 2 was applied, and the magnetron sputtering method and the degree of vacuum were used. 0.27 Pa and an Ar gas system as a gas flowed at a flow rate of 500 sccm to form a film. Further, the flow rate value in the film formation is observed for a long period of time, and the flow rate fed back to the oxygen gas makes the voltage value constant. As described above, a low refractive index layer having a thickness of 60 nm and a refractive index of 1.36 was deposited.

再者，使用該透明導電性薄膜，與實施例1同樣地製作成觸控面板。Further, a touch panel was produced in the same manner as in Example 1 using this transparent conductive film.

[實施例6][Embodiment 6]

實施例1中，除了在硬化物層上將鋁-矽複合氧化物(Al2 O3 -SiO2 )所構成的薄膜予以成膜作為低折射率層以外，與實施例1同樣地形成了透明導電性薄膜。In the first embodiment, a film formed of an aluminum-bismuth composite oxide (Al 2 O 3 -SiO 2 ) was formed as a low refractive index layer on the cured layer, and a transparent film was formed in the same manner as in the first embodiment. Conductive film.

此時，將濺鍍前的壓力設定為0.0001Pa，用Al-Si(50：50wt%)(三井金屬製)作為標靶，施加2W/cm2 之DC電力，利用磁控濺鍍法、真空度為0.27Pa、作為氣體之Ar氣體係以500sccm、O2 氣體係以80sccm之流速流過，進行成膜。且，長時觀測成膜中的電壓值，並反饋到氧氣的流量計使電壓值成為一定。如以上方式，堆積成厚度50nm、折射率1.55之低折射率層。再者，使用該透明導電性薄膜，與實施例1同樣地製作成觸控面板。At this time, the pressure before sputtering was set to 0.0001 Pa, and Al-Si (50:50 wt%) (manufactured by Mitsui Metals Co., Ltd.) was used as a target, and DC power of 2 W/cm 2 was applied, using magnetron sputtering, vacuum. The film was formed into a film having a degree of 0.27 Pa, a gas system of Ar gas at 500 sccm, and an O 2 gas system at a flow rate of 80 sccm. Further, the flow rate value in the film formation is observed for a long period of time, and the flow rate fed back to the oxygen gas makes the voltage value constant. As described above, a low refractive index layer having a thickness of 50 nm and a refractive index of 1.55 was deposited. Further, a touch panel was produced in the same manner as in Example 1 using this transparent conductive film.

[實施例7][Embodiment 7]

實施例1中，作為製作高折射率層之標靶，係含有20質量%氧化錫之氧化銦(住友金屬鑛山公司製、密度7.0g/cm3 )，除了O2 氣體流量係表面電阻值為最小時的流量之4倍以外，與實施例1同樣地製作成透明導電性薄膜。獲得之高折射率層的表面電阻值為1×106 Ω/□以上。再者，使用該透明導電性薄膜，與實施例1同樣地製作成觸控面板。In the first embodiment, as a target for producing a high refractive index layer, indium oxide containing 20% by mass of tin oxide (manufactured by Sumitomo Metal Mining Co., Ltd., density: 7.0 g/cm 3 ) is used, except for the O 2 gas flow rate surface resistance value. A transparent conductive film was produced in the same manner as in Example 1 except that the flow rate at the minimum was four times. The surface resistivity of the obtained high refractive index layer was 1 × 10 6 Ω/□ or more. Further, a touch panel was produced in the same manner as in Example 1 using this transparent conductive film.

[實施例8][Embodiment 8]

實施例1中，除了將經摻雜鎵之氧化鋅薄膜用於作為透明導電性薄膜以外，與實施例1同樣地製作成透明導電性薄膜。作為標靶係使用含有5質量%氧化鎵之氧化鋅(東曹公司製)，施加有2W/cm2 之DC電力。且，Ar氣體為130sccm、O2 氣體係以表面電阻值成為最小時之流速流過，0.4Pa之雰圍下，利用DC磁控濺鍍法成膜，獲得厚度14nm、折射率2.05的透明導電性薄膜。再者，使用該透明導電性薄膜、與實施例1同樣地製作成觸控面板。In the first embodiment, a transparent conductive film was produced in the same manner as in Example 1 except that a gallium-doped zinc oxide film was used as the transparent conductive film. As the target system, zinc oxide containing 5% by mass of gallium oxide (manufactured by Tosoh Corporation) was used, and DC power of 2 W/cm 2 was applied. Further, the Ar gas was 130 sccm, and the O 2 gas system was flowed at a flow rate at which the surface resistance value became the smallest, and a film was formed by DC magnetron sputtering in an atmosphere of 0.4 Pa to obtain a transparent conductivity of 14 nm in thickness and a refractive index of 2.05. film. Further, a touch panel was produced in the same manner as in Example 1 using this transparent conductive film.

[實施例9][Embodiment 9]

除了高折射率層之厚度為40nm以外，與實施例1同樣地製作成透明導電性薄膜及觸控面板。A transparent conductive film and a touch panel were produced in the same manner as in Example 1 except that the thickness of the high refractive index layer was 40 nm.

[實施例10][Embodiment 10]

除了低折射率層之厚度為50nm以外，與實施例1同樣地製作成透明導電性薄膜及觸控面板。A transparent conductive film and a touch panel were produced in the same manner as in Example 1 except that the thickness of the low refractive index layer was 50 nm.

[實施例11][Example 11]

除了透明導電性薄膜之厚度為10nm以外，與與實施例1同樣地製作成透明導電性薄膜及觸控面板。A transparent conductive film and a touch panel were produced in the same manner as in Example 1 except that the thickness of the transparent conductive film was 10 nm.

[實施例12][Embodiment 12]

除了透明導電性薄膜之厚度為22nm以外，與實施例1同樣地製作成透明導電性薄膜及觸控面板。A transparent conductive film and a touch panel were produced in the same manner as in Example 1 except that the thickness of the transparent conductive film was 22 nm.

[實施例13][Example 13]

實施例1中，作為製作高折射率層之標靶，除了含有55質量%氧化錫之氧化銦(住友金屬鑛山公司製、密度6.7g/cm3 )、O2 氣體流量係表面電阻值為最小時之流量的2.5倍以外，與實施例1同樣地製作成透明導電性薄膜。獲得之高折射率層的表面電阻值為1×106 Ω/□以上。再者，使用該透明導電性薄膜，與實施例1同樣地製作成觸控面板。In the first embodiment, as a target for producing a high refractive index layer, indium oxide containing 55 mass% of tin oxide (manufactured by Sumitomo Metal Mining Co., Ltd., density: 6.7 g/cm 3 ), and O 2 gas flow rate surface resistance value A transparent conductive film was produced in the same manner as in Example 1 except that the flow rate was 2.5 times the minimum. The surface resistivity of the obtained high refractive index layer was 1 × 10 6 Ω/□ or more. Further, a touch panel was produced in the same manner as in Example 1 using this transparent conductive film.

[比較例4][Comparative Example 4]

實施例1中，除了將鋯氧化-矽複合氧化物(ZrO2 -SiO2 )所構成的薄膜予以成膜作為低折射率層以外，與實施例1同樣地形成了透明導電性薄膜。In the first embodiment, a transparent conductive film was formed in the same manner as in Example 1 except that a film made of a zirconium oxide-yttrium composite oxide (ZrO 2 -SiO 2 ) was formed as a low refractive index layer.

此時，將濺鍍前的壓力設定為0.0001Pa，使用ZrSi2 (三井金屬製)作為標靶，施加2W/cm2 之DC電力，利用直流磁控濺鍍法、真空度為0.27Pa、作為氣體之Ar氣體係以500sccm、O2 氣體係以80sccm之流速流過，進行成膜。且，長時觀測成膜中的電壓值，並反饋到氧氣的流量計使電壓值成為一定。如以上方式，堆積成厚度45nm、折射率1.75之低折射率層。In this case, the pressure before the sputtering was set to 0.0001 Pa, and ZWSi 2 (manufactured by Mitsui Metals Co., Ltd.) was used as a target, and DC power of 2 W/cm 2 was applied, and the DC magnetron sputtering method was used, and the degree of vacuum was 0.27 Pa. The gas Ar gas system was flowed at a flow rate of 80 sccm at 500 sccm and an O 2 gas system to form a film. Further, the flow rate value in the film formation is observed for a long period of time, and the flow rate fed back to the oxygen gas makes the voltage value constant. As described above, a low refractive index layer having a thickness of 45 nm and a refractive index of 1.75 was deposited.

[比較例5][Comparative Example 5]

實施例2中，除了使製膜前之重繞時的壓力進一步提高1位為0.0002Pa以外，與實施例2同樣地製作成透明導電性薄膜。此時的水分壓對惰性氣體之比為1×10-3 。再者，使用該透明導電性薄膜，與實施例1同樣地製作成觸控面板。In the second embodiment, a transparent conductive film was produced in the same manner as in Example 2 except that the pressure at the time of rewinding before film formation was further increased by one position to 0.0002 Pa. The ratio of the water pressure to the inert gas at this time was 1 × 10 -3 . Further, a touch panel was produced in the same manner as in Example 1 using this transparent conductive film.

[比較例6][Comparative Example 6]

實施例1中，作為製作高折射率層之標靶，係含有75質量%氧化錫之氧化銦(住友金屬鑛山公司製、密度5.8g/cm3 )，O2 氣體流量係表面電阻值為最小時之流量的2倍。但是，濺鍍中經常發生異常放電，無法將高折射率層成膜。In the first embodiment, as a target for producing a high refractive index layer, indium oxide containing 75 mass% of tin oxide (manufactured by Sumitomo Metal Mining Co., Ltd., density: 5.8 g/cm 3 ) is used, and the surface resistance value of the O 2 gas flow rate is 2 times the flow rate of the hour. However, abnormal discharge often occurs during sputtering, and the high refractive index layer cannot be formed into a film.

[比較例7][Comparative Example 7]

實施例1中，除了將摻雜有鈦及錫之氧化銦薄膜使用於透明導電性薄膜以外，與與實施例1同樣地製作成透明導電性薄膜。作為標靶係使用氧化銦：氧化錫：氧化鈦=60：10：30重量%(住友金屬鑛山公司製)，施加2W/cm2 之DC電力。且，Ar氣體係以130sccm、O2 氣體係以表面電阻值為最小時之流速流過，在0.4Pa之大氣下利用DC磁控濺鍍法成膜，獲得厚度15nm、折射率2.25之透明導電性薄膜。In the first embodiment, a transparent conductive film was produced in the same manner as in Example 1 except that an indium oxide film doped with titanium and tin was used for the transparent conductive film. Indium oxide: tin oxide: titanium oxide = 60:10:30% by weight (manufactured by Sumitomo Metal Mining Co., Ltd.) was used as a target system, and DC power of 2 W/cm 2 was applied. Further, the Ar gas system was flowed at a flow rate at a surface resistance value of 130 sccm and an O 2 gas system, and a film was formed by DC magnetron sputtering at an atmosphere of 0.4 Pa to obtain a transparent conductive layer having a thickness of 15 nm and a refractive index of 2.25. Film.

再者，使用該透明導電性薄膜，與實施例1同樣地製作成觸控面板。Further, a touch panel was produced in the same manner as in Example 1 using this transparent conductive film.

[比較例8][Comparative Example 8]

實施例1中，將摻雜有矽及錫之氧化銦薄膜使用於透明導電性薄膜以外，與實施例1同樣地製作成透明導電性薄膜。作為標靶係使用氧化銦：氧化錫：氧化矽=60：10：30重量%(住友金屬鑛山公司製)，施加2W/cm2 之DC電力。且，Ar氣體係以130sccm、O2 氣體係以表面電阻值為最小時之流速流過，在0.4Pa之雰圍下利用DC磁控濺鍍法成膜，獲得厚度18nm、折射率1.75之透明導電性薄膜。再者，使用該透明導電性薄膜，與實施例1同樣地製作成觸控面板。In the first embodiment, a transparent conductive film was produced in the same manner as in Example 1 except that the indium oxide film doped with antimony and tin was used for the transparent conductive film. Indium oxide: tin oxide: yttrium oxide = 60:10:30% by weight (manufactured by Sumitomo Metal Mining Co., Ltd.) was used as a target system, and DC power of 2 W/cm 2 was applied. Further, the Ar gas system was flowed at a flow rate of a surface resistance value of 130 sccm and an O 2 gas system, and a film was formed by DC magnetron sputtering in an atmosphere of 0.4 Pa to obtain a transparent conductive layer having a thickness of 18 nm and a refractive index of 1.75. Film. Further, a touch panel was produced in the same manner as in Example 1 using this transparent conductive film.

[比較例9][Comparative Example 9]

除了高折射率層之厚度為30nm以外，與實施例1同樣地製作成透明導電性薄膜及觸控面板。A transparent conductive film and a touch panel were produced in the same manner as in Example 1 except that the thickness of the high refractive index layer was 30 nm.

[比較例10][Comparative Example 10]

除了高折射率層之厚度為60nm以外，與與實施例1同樣地製作成透明導電性薄膜及觸控面板。A transparent conductive film and a touch panel were produced in the same manner as in Example 1 except that the thickness of the high refractive index layer was 60 nm.

[比較例11][Comparative Example 11]

除了透明導電性薄膜之厚度為30nm以外，與實施例1同樣地製作成透明導電性薄膜及觸控面板。A transparent conductive film and a touch panel were produced in the same manner as in Example 1 except that the thickness of the transparent conductive film was 30 nm.

根據表1、2之結果，滿足本申請案發明的範圍之使用實施例1~13記載的透明導電性薄膜或透明導電性薄片之觸控面板，係目視辨認性優異，且在框緣附近對聚縮醛製筆(前端形狀：0.8mm R)施加2.5N之負荷，進行1萬次滑動實驗後，仍不會產生剝離或龜裂，ON電阻亦無異常。According to the results of Tables 1 and 2, the touch panel using the transparent conductive film or the transparent conductive sheet described in Examples 1 to 13 which satisfies the scope of the invention of the present application is excellent in visual visibility and is adjacent to the frame edge. The polyacetal pen (front end shape: 0.8 mm R) was applied with a load of 2.5 N, and after 10,000 sliding tests, peeling or cracking did not occur, and the ON resistance was not abnormal.

另一方面，使用高折射率層為結晶質之比較例1記載的透明導電性薄膜或透明導電性薄片之觸控面板，係在框緣附近對聚縮醛製筆(前端形狀：0.8mm R)施加2.5N之負荷，進行1萬次滑動實驗後，ON電阻產生異常。再者，以顯微鏡評價筆滑動部分時，看見透明導電性薄膜剝離或龜裂。透明導電性薄膜為結晶質之比較例5也同樣。On the other hand, the touch panel of the transparent conductive film or the transparent conductive sheet described in Comparative Example 1 in which the high refractive index layer is crystalline is used to form a polyacetal pen near the frame edge (front end shape: 0.8 mm R After applying a load of 2.5 N and performing a sliding test of 10,000 times, the ON resistance was abnormal. Further, when the pen sliding portion was evaluated by a microscope, peeling or cracking of the transparent conductive film was observed. The same applies to Comparative Example 5 in which the transparent conductive film is crystalline.

且，低折射率層或高折射率層或透明導電性薄膜之膜厚厚[比較例2、10、11]係全光線透過率為本申請案發明之範圍外、透明性差，低折射率層或高折射率層之膜厚薄[比較例3、9]係色彩b值為本申請案發明之範圍外、色彩差，使用該等透明導電性薄膜之觸控面板係目視辨認性差者。比較例4、比較例7係因低折射率層或透明導電性薄膜之折射率高，因此色彩b值為本申請案發明之範圍外、色彩差。Further, the film thickness of the low refractive index layer or the high refractive index layer or the transparent conductive film is relatively thick [Comparative Examples 2, 10, and 11], and the total light transmittance is outside the range of the present invention, and the transparency is poor, and the low refractive index layer is low. Or the film thickness of the high refractive index layer is thin [Comparative Examples 3 and 9] The color b value is outside the range of the invention of the present application, and the color is poor, and the touch panel using the transparent conductive film is poor in visual recognition. In Comparative Example 4 and Comparative Example 7, since the refractive index of the low refractive index layer or the transparent conductive film was high, the color b value was outside the range of the invention of the present application, and the color was poor.

比較例7、8係表面電阻過高，不適於觸控面板用途。再者，比較例6係氧化錫對氧化銦的比例過多、異常放電多，濺鍍中的異常放電多，無法進行成膜。Comparative Examples 7 and 8 have excessive surface resistance and are not suitable for touch panel applications. Further, in Comparative Example 6, the ratio of tin oxide to indium oxide was too large, abnormal discharge was large, and abnormal discharge was excessive during sputtering, and film formation was impossible.

[產業上之可利用性][Industrial availability]

本發明之透明導電性薄膜或透明導電性薄片，當用於配置在高精細之液晶顯示器等顯示體的前面之觸控面板時，目視辨認性優異並且即使在觸控面板的框緣附近亦不會產生剝離、龜裂等，筆滑動耐久性優異，且位置檢測精確度和顯示品位亦優異，因此可對應觸控面板之窄框緣化，用於行動資訊終端、數位攝影機、數位相機等，強烈要求記錄媒體小型化和顯示器大畫面化之觸控面板特別合適。When the transparent conductive film or the transparent conductive sheet of the present invention is used for a touch panel disposed in front of a display body such as a high-definition liquid crystal display, the visibility is excellent and it is not near the frame edge of the touch panel. Peeling, cracking, etc., excellent pen sliding durability, excellent position detection accuracy and display quality, so it can be used for mobile information terminals, digital cameras, digital cameras, etc., in accordance with the narrow frame of the touch panel. A touch panel that strongly requires recording media miniaturization and a large display screen is particularly suitable.

10．．．透明導電性薄膜10. . . Transparent conductive film

11．．．透明塑膠薄膜(基材)11. . . Transparent plastic film (substrate)

12．．．硬化物層12. . . Hardened layer

13．．．高折射率層13. . . High refractive index layer

14．．．低折射率層14. . . Low refractive index layer

15．．．透明導電性薄膜層15. . . Transparent conductive film layer

16．．．硬塗層16. . . Hard coating

20．．．珠20. . . Bead

30．．．玻璃板30. . . glass plate

40．．．透明導電性薄片40. . . Transparent conductive sheet

41．．．黏合劑41. . . Adhesive

42．．．透明樹脂薄片42. . . Transparent resin sheet

第1圖係本發明之使用透明導電性薄膜之觸控面板的說明圖。Fig. 1 is an explanatory view of a touch panel using a transparent conductive film of the present invention.

第2圖係本發明之使用透明導電性薄膜之不使用玻璃基板的觸控面板之說明圖。Fig. 2 is an explanatory view of a touch panel which does not use a glass substrate using a transparent conductive film of the present invention.

Claims (5)

一種透明導電性薄膜，其係於由透明塑膠薄膜所構成的基材上，將高折射率層、低折射率層及透明導電性薄膜層依此順序積層而成之透明導電性薄膜，其特徵為高折射率層係由氧化錫之含有率為10~60質量%之非晶質銦-錫複合氧化物所構成的無機薄膜，低折射率層係由折射率1.30~1.60之無機薄膜所構成，透明導電性薄膜層係由折射率1.80~2.20之無機薄膜所構成，且透明導電性薄膜之分光透過率之峰值係存在於450~530nm，且全部光線透過率為90%以上，色彩b值為-2~2。 A transparent conductive film which is a transparent conductive film formed by laminating a high refractive index layer, a low refractive index layer and a transparent conductive thin film layer on a substrate made of a transparent plastic film. The high refractive index layer is an inorganic thin film composed of an amorphous indium-tin composite oxide having a tin oxide content of 10 to 60% by mass, and the low refractive index layer is composed of an inorganic thin film having a refractive index of 1.30 to 1.60. The transparent conductive film layer is composed of an inorganic film having a refractive index of 1.80 to 2.20, and the peak of the spectral transmittance of the transparent conductive film is 450 to 530 nm, and the total light transmittance is 90% or more, and the color b value is It is -2~2. 如申請專利範圍第1項之透明導電性薄膜，其中該高折射率層之氧化錫之含有率為20~60質量%。 The transparent conductive film of claim 1, wherein the high refractive index layer has a tin oxide content of 20 to 60% by mass. 如申請專利範圍第1或2項之透明導電性薄膜，其中在由該透明塑膠薄膜所構成的基材之積層有透明導電性薄膜層的面之相反面係經施行低反射處理。 The transparent conductive film according to claim 1 or 2, wherein the opposite surface of the surface of the substrate made of the transparent plastic film in which the transparent conductive film layer is laminated is subjected to a low reflection treatment. 一種透明導電性薄片，其特徵為在如申請專利範圍第1至3項中任一項之透明導電性薄膜之積層有透明導電性薄膜層的面之相反面，藉由黏合劑貼合著透明樹脂薄片。 A transparent conductive sheet characterized by being bonded to a transparent surface of a transparent conductive film according to any one of claims 1 to 3, wherein the surface of the transparent conductive film is laminated with a transparent adhesive film Resin sheet. 一種觸控面板，其係將具有透明導電性薄膜層的一對面板，隔著間隔物配置成透明導電性薄膜層相對向而構成的觸控面板，其特徵為至少一方之面板係由如申請專利範圍第1至4項中任一項之透明導電性薄膜或透明導電性薄片所構成。 A touch panel is a touch panel in which a pair of panels having a transparent conductive thin film layer are disposed such that a transparent conductive thin film layer is opposed to each other via a spacer, and at least one of the panels is applied by A transparent conductive film or a transparent conductive sheet according to any one of claims 1 to 4.
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JPH11286066A (en) * 1998-03-31 1999-10-19 Oike Ind Co Ltd Transparent conductive film
JP2004152727A (en) * 2002-11-01 2004-05-27 Toyo Metallizing Co Ltd Transparent conductive film
WO2006126604A1 (en) * 2005-05-26 2006-11-30 Gunze Limited Transparent planar body and transparent touch switch
WO2009054227A1 (en) * 2007-10-26 2009-04-30 Teijin Limited Transparent conductive laminate and touch panel

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JPH11286066A (en) * 1998-03-31 1999-10-19 Oike Ind Co Ltd Transparent conductive film
JP2004152727A (en) * 2002-11-01 2004-05-27 Toyo Metallizing Co Ltd Transparent conductive film
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WO2009054227A1 (en) * 2007-10-26 2009-04-30 Teijin Limited Transparent conductive laminate and touch panel

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