本發明關於在透明塑膠薄膜基材上積層有結晶性銦-錫複合氧化物的透明導電膜之透明導電性薄膜，尤其關於用於電阻膜式觸控面板時的筆滑動耐久性、筆重加壓耐久性、高精細性優異之透明導電性薄膜。The present invention relates to a transparent conductive film having a crystalline indium-tin composite oxide layered on a transparent plastic film substrate, and more particularly to a transparent conductive film having excellent pen sliding durability, pen weight pressure durability, and high precision when used in a resistive film touch panel.
在透明塑膠基材上積層有透明且電阻小的薄膜之透明導電性薄膜，係被廣泛使用於利用其導電性的用途，例如如液晶顯示器或電致發光(EL)顯示器等之平板顯示器，或作為觸控面板的透明電極等，被使用於電氣・電子領域之用途。Transparent conductive films, which are thin films with low electrical resistance layered on transparent plastic substrates, are widely used for applications that utilize their electrical conductivity, such as flat panel displays such as liquid crystal displays and electroluminescent (EL) displays, or as transparent electrodes for touch panels, and are used in the electrical and electronic fields.
電阻膜式觸控面板係使在玻璃或塑膠的基板上塗布有透明導電性薄膜之固定電極與在塑膠薄膜上塗布有透明導電性薄膜之可動電極(=薄膜電極)組合者，以疊合於顯示體的上側之方式來使用。以手指或筆按壓薄膜電極，而使固定電極與薄膜電極的透明導性薄膜彼此接觸，即成為觸控面板的位置辨識用之輸入。與手指比較之下，筆施加於觸控面板的力大多較強。若以筆持續輸入觸控面板，則會在薄膜電極側的透明導電性薄膜發生裂痕、剝離、磨耗等之破壞。又，若以筆激烈地敲擊觸控面板、或以非常強的力量進行筆輸入等，而於觸控面板施加超出通常使用所設想的強力，則會在透明導電性薄膜發生裂痕、剝離等之破壞。為了解決該等問題，期待一種兼顧優異的筆滑動耐久性與優異的筆重加壓耐久性之透明導電性薄膜。再者，關於觸控面板之映像，亦要求為高精細。The resistive film touch panel is a combination of a fixed electrode coated with a transparent conductive film on a glass or plastic substrate and a movable electrode (= thin film electrode) coated with a transparent conductive film on a plastic film, and is used in a manner of overlapping on the upper side of a display. Pressing the thin film electrode with a finger or a pen causes the fixed electrode and the transparent conductive film of the thin film electrode to contact each other, which becomes the input for position recognition of the touch panel. Compared with fingers, the force applied to the touch panel by a pen is usually stronger. If the touch panel is continuously input with a pen, the transparent conductive film on the thin film electrode side will be damaged by cracks, peeling, abrasion, etc. Furthermore, if a pen is struck violently on the touch panel or a pen input is performed with a very strong force, a force greater than that normally expected is applied to the touch panel, and the transparent conductive film may be damaged by cracks or peeling. To solve these problems, a transparent conductive film having both excellent pen sliding durability and excellent pen weight pressure durability is desired. Furthermore, the image of the touch panel is also required to be highly precise.
作為提高筆滑動耐久性之手段，有使薄膜電極側的透明導電性薄膜成為結晶性之方法(例如參照專利文獻1)。然而，以往的透明導電性薄膜係藉由控制銦-錫複合氧化物的結晶性而實現筆滑動耐久性優異的透明導電性薄膜。但是，以往的透明導電性薄膜係在實施後述的筆重加壓耐久性試驗時不充分。 [先前技術文獻] [專利文獻]As a means of improving the pen sliding durability, there is a method of making the transparent conductive film on the thin film electrode side crystalline (for example, refer to Patent Document 1). However, the conventional transparent conductive film is a transparent conductive film with excellent pen sliding durability achieved by controlling the crystallinity of indium-tin composite oxide. However, the conventional transparent conductive film is insufficient when performing the pen heavy pressure durability test described later.[Prior Technical Document][Patent Document]
[專利文獻1]日本特開2004-071171號公報[Patent Document 1] Japanese Patent Application Publication No. 2004-071171
[發明欲解決之課題][Problems to be solved by the invention]
本發明之目的係鑒於上述習知的問題點，提供一種透明導電性薄膜，其係用於觸控面板時的筆滑動耐久性優異，同時筆重加壓耐久性亦優異，再者能提供高精細的映像。 [用以解決課題之手段]The purpose of the present invention is to provide a transparent conductive film in view of the above-mentioned known problems, which has excellent pen sliding durability when used for a touch panel, and also has excellent pen weight pressure durability, and can provide high-precision images.[Means for solving the problem]
本發明係鑒於如上述的狀況而完成者，能解決上述課題的本發明之透明導電性薄膜包含以下之構成。 1.一種透明導電性薄膜，其係在透明塑膠薄膜基材上的一面上積層有銦-錫複合氧化物的透明導電膜之透明導電性薄膜，利用以下之筆滑動耐久性試驗的透明導電薄膜之透明導電膜的ON電阻為10kΩ以下，利用以下之筆重加壓試驗的透明導電薄膜之透明導電膜的表面電阻值之增加率為1.5以下，再者梳寬0.125mm、0.25mm、0.5mm、1.0mm、2.0mm下之透明導電性薄膜的透過影像清晰度之總和為250%以上且小於500%； (筆滑動耐久性試驗方法) 使用本發明之透明導電性薄膜作為一面板，使用在玻璃基板上含有以濺鍍法形成厚度為20nm的銦-錫複合氧化物薄膜(氧化錫含量：10質量%)之透明導電性薄膜作為另一面板；以透明導電性薄膜呈對向之方式，隔著直徑30μm的環氧樹脂珠配置前述2片面板，以厚度為170μm的雙面膠帶貼附薄膜側的面板與玻璃側的面板，製作觸控面板；接著對於聚縮醛製的筆(前端的形狀：0.8mmR)施加2.5N的荷重，對於觸控面板進行18萬往返的直線滑動試驗；於此試驗中，對於本發明之透明導電性薄膜面施加筆的荷重； 此時的滑動距離係設為30mm，滑動速度係設為180mm/秒；於此滑動耐久性試驗後，測定以筆荷重0.8N按壓滑動部時的ON電阻(可動電極(薄膜電極)與固定電極接觸時的電阻值)； (筆重加壓試驗方法) 使用經切成50mm×50mm的本發明之透明導電性薄膜作為一面板，使用在玻璃基板上含有以濺鍍法形成厚度為20nm的銦-錫複合氧化物薄膜(氧化錫含量：10質量%)之透明導電性薄膜作為另一面板；以透明導電性薄膜呈對向之方式，隔著直徑30μm的環氧樹脂珠配置該2片面板，以厚度經調整成120μm的雙面膠帶貼附薄膜側的面板與玻璃側的面板，製作觸控面板；以聚縮醛製的筆(前端的形狀0.8mmR)將35N的荷重施加於距雙面膠帶的邊端2.0mm的位置，與雙面膠帶平行地實施10次(往返5次)的直線滑動；於此試驗中，對於本發明之透明導電性薄膜面施加筆的荷重。此時的滑動距離係設為30mm，滑動速度係設為20mm/秒；在無環氧樹脂珠的位置進行滑動；滑動後，卸除透明導電性薄膜，測定滑動部之任意5處的表面電阻(4端子法)，求出平均值；測定表面電阻時，在與滑動部垂直的方向上排列4端子，以使滑動部來到第2端子與第3端子之間的方式設定；將滑動部的表面電阻值之平均值除以未滑動部的表面電阻值(以4端子法測定)，算出表面電阻值之增加率。 2.如上述第1記載之透明導電性薄膜，其中銦-錫複合氧化物之透明導電膜的結晶粒徑為10～100nm，銦-錫複合氧化物之透明導電膜的結晶化度為20～80%，銦-錫複合氧化物之透明導電膜包含0.5～10質量%的氧化錫，銦-錫複合氧化物之透明導電膜的厚度為10～30nm，將銦-錫複合氧化物之透明導電膜的三次元表面粗糙度SRa當作X時，X為1～100nm，再者將透明塑膠薄膜基材上之與透明導電膜側相反面的三次元表面粗糙度SRa當作Y時，(X3+Y3)1/3為140nm以下。 3.如上述第1或第2記載之透明導電性薄膜，其中即使於透明導電膜之表面實施附著性試驗(JIS K5600-5-6：1999)，透明導電膜也不剝離，且於透明導電性薄膜的銦-錫複合氧化物之透明導電膜側進行耐彎曲性試驗(JIS K5600-5-1：1999)，以10倍的放大鏡觀察彎曲部時，發生破裂或剝落的心軸直徑小於20mm。 4.如上述第1至第3中任一項記載之透明導電性薄膜，其中透明導電性薄膜的厚度為100～250μm。 5.如上述第1至第4中任一項記載之透明導電性薄膜，其中在銦-錫複合氧化物的透明導電膜與透明塑膠薄膜基材之間具有硬化型樹脂層。 [發明之效果]The present invention is completed in view of the above-mentioned situation, and the transparent conductive film of the present invention that can solve the above-mentioned problem includes the following structure. 1. A transparent conductive film, which is a transparent conductive film having an indium-tin composite oxide layered on one side of a transparent plastic film substrate, wherein the ON resistance of the transparent conductive film in the following pen sliding durability test is less than 10kΩ, and the increase rate of the surface resistance value of the transparent conductive film in the following pen weight pressure test is less than 1.5, and the sum of the through image clarity of the transparent conductive film at comb widths of 0.125mm, 0.25mm, 0.5mm, 1.0mm, and 2.0mm is greater than 250% and less than 500%; (Pen sliding durability test method) The transparent conductive film of the present invention is used as one panel, and a transparent conductive film containing an indium-tin composite oxide film (tin oxide content: 10 mass %) formed by sputtering with a thickness of 20 nm on a glass substrate is used as the other panel; the two panels are arranged in a manner that the transparent conductive films are opposite to each other, and epoxy resin beads with a diameter of 30 μm are sandwiched therebetween, and the panel on the film side and the panel on the glass side are attached with a double-sided tape with a thickness of 170 μm to prepare a touch panel; then a load of 2.5 N is applied to a pen made of polyacetal (shape of the front end: 0.8 mmR), and a linear sliding test of 180,000 reciprocating strokes is performed on the touch panel; in this test, the load of the pen is applied to the transparent conductive film surface of the present invention; The sliding distance at this time is set to 30mm, and the sliding speed is set to 180mm/sec. After this sliding durability test, the ON resistance (resistance value when the movable electrode (thin film electrode) contacts the fixed electrode) is measured when the sliding part is pressed with a pen load of 0.8N. (Pen weight pressure test method) A transparent conductive film of the present invention cut into 50mm×50mm is used as one panel, and a transparent conductive film containing an indium-tin composite oxide film (tin oxide content: 10 mass %) with a thickness of 20nm formed by sputtering on a glass substrate is used as the other panel; the two panels are arranged in a manner that the transparent conductive films are opposite to each other, and epoxy resin beads with a diameter of 30μm are separated, and the thickness is A touch panel was made by attaching a film-side panel and a glass-side panel with a double-sided tape adjusted to 120 μm. A load of 35 N was applied with a polyacetal pen (the shape of the front end was 0.8 mmR) at a position 2.0 mm away from the edge of the double-sided tape, and a straight line slide was performed 10 times (5 times back and forth) parallel to the double-sided tape. In this test, the load of the pen was applied to the transparent conductive film surface of the present invention. The sliding distance at this time was set to 30 mm, and the sliding speed was set to 20 mm/sec. The sliding was performed at a position without epoxy resin beads. After sliding, the transparent conductive film was removed, and the surface resistance of any five locations of the sliding part was measured (4-terminal method), and the average value was calculated. When measuring the surface resistance, the four terminals were arranged in a direction perpendicular to the sliding part so that the sliding part came between the second terminal and the third terminal. The average value of the surface resistance value of the sliding part was divided by the surface resistance value of the non-sliding part (measured by the 4-terminal method), and the increase rate of the surface resistance value was calculated. 2. The transparent conductive film as described in item 1 above, wherein the crystal grain size of the transparent conductive film of indium-tin composite oxide is 10 to 100 nm, the degree of crystallization of the transparent conductive film of indium-tin composite oxide is 20 to 80%, the transparent conductive film of indium-tin composite oxide contains 0.5 to 10 mass % of tin oxide, the thickness of the transparent conductive film of indium-tin composite oxide is 10 to 30 nm, when the three-dimensional surface roughness SRa of the transparent conductive film of indium-tin composite oxide is taken as X, X is 1 to 100 nm, and when the three-dimensional surface roughness SRa of the surface opposite to the transparent conductive film side on the transparent plastic film substrate is taken as Y, (X3 +Y3 )1/3 is less than 140 nm. 3. The transparent conductive film as described in item 1 or 2 above, wherein the transparent conductive film does not peel off even when the adhesion test (JIS K5600-5-6: 1999) is performed on the surface of the transparent conductive film, and when the bending resistance test (JIS K5600-5-1: 1999) is performed on the transparent conductive film side of the indium-tin composite oxide of the transparent conductive film, the diameter of the mandrel where cracking or peeling occurs is less than 20 mm when the bending portion is observed with a 10-fold magnifying glass. 4. The transparent conductive film as described in any one of items 1 to 3 above, wherein the thickness of the transparent conductive film is 100 to 250 μm. 5. The transparent conductive film as described in any one of items 1 to 4 above, wherein a hardened resin layer is provided between the transparent conductive film of the indium-tin composite oxide and the transparent plastic film substrate. [Effect of the Invention]
根據本發明，可提供一種兼具優異的筆滑動耐久性及優異的筆重加壓耐久性，進而能提供高精細的映像之透明導電性薄膜。所得之透明導電性薄膜係極有用於電阻膜式觸控面板等之用途。According to the present invention, a transparent conductive film having both excellent pen sliding durability and excellent pen weight pressure durability can be provided, thereby providing high-precision images. The obtained transparent conductive film is very useful for applications such as resistive film touch panels.
[用以實施發明的形態][Form used to implement the invention]
本發明之透明導電性薄膜係在透明塑膠薄膜基材上的一面上積層有銦-錫複合氧化物的透明導電膜之透明導電性薄膜，較佳為：利用以下之筆滑動耐久性試驗的透明導電薄膜之透明導電膜的ON電阻為10kΩ以下，再者利用以下之筆重加壓試驗的透明導電薄膜之透明導電膜的表面電阻值之增加率為1.5以下，再者梳寬0.125mm、0.25mm、0.5mm、1.0mm、2.0mm下之透明導電性薄膜的透過影像清晰度之總和為250%以上且小於500%。 (筆滑動耐久性試驗) 使用本發明之透明導電性薄膜作為一面板，使用在玻璃基板上含有以濺鍍法形成厚度為20nm的銦-錫複合氧化物薄膜(氧化錫含量：10質量%)之透明導電性薄膜作為另一面板；以透明導電性薄膜呈對向之方式，隔著直徑30μm的環氧樹脂珠配置該2片面板，以厚度為170μm的雙面膠帶貼附薄膜側的面板與玻璃側的面板，製作觸控面板；接著對於聚縮醛製的筆(前端的形狀：0.8mmR)施加2.5N的荷重，對於觸控面板進行18萬往返的直線滑動試驗；於此試驗中，對於本發明之透明導電性薄膜面施加筆的荷重；此時的滑動距離係設為30mm，滑動速度係設為180mm/秒；於此滑動耐久性試驗後，測定以筆荷重0.8N按壓滑動部時的ON電阻(可動電極(薄膜電極)與固定電極接觸時的電阻值)。 (筆重加壓試驗) 使用經切成50mm×50mm的本發明之透明導電性薄膜作為一面板，使用在玻璃基板上含有以濺鍍法形成厚度為20nm的銦-錫複合氧化物薄膜(氧化錫含量：10質量%)之透明導電性薄膜作為另一面板；以透明導電性薄膜呈對向之方式，隔著直徑30μm的環氧樹脂珠配置該2片面板，以厚度經調整成120μm的雙面膠帶貼附薄膜側的面板與玻璃側的面板，製作觸控面板；以聚縮醛製的筆(前端的形狀0.8mmR)將35N的荷重施加於距雙面膠帶的邊端2.0mm的位置，與雙面膠帶平行地實施10次(往返5次)的直線滑動；於此試驗中，對於本發明之透明導電性薄膜面施加筆的荷重；此時的滑動距離係設為30mm，滑動速度係設為20mm/秒；惟，在無環氧樹脂珠的位置進行滑動；滑動後，卸除透明導電性薄膜，測定滑動部之任意5處的表面電阻(4端子法)，求出平均值；測定表面電阻時，在與滑動部垂直的方向上排列4端子，以使滑動部來到第2端子與第3端子之間的方式設定；將滑動部的表面電阻值之平均值除以未滑動部的表面電阻值(以4端子法測定)，算出表面電阻值之增加率。The transparent conductive film of the present invention is a transparent conductive film having an indium-tin composite oxide layered on one side of a transparent plastic film substrate. Preferably, the ON resistance of the transparent conductive film in the following pen sliding durability test is less than 10 kΩ, and the increase rate of the surface resistance value of the transparent conductive film in the following pen weight pressure test is less than 1.5, and the total of the through-image clarity of the transparent conductive film at comb widths of 0.125 mm, 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm is greater than 250% and less than 500%.(Pen sliding durability test)The transparent conductive film of the present invention is used as one panel, and a transparent conductive film containing an indium-tin composite oxide film (tin oxide content: 10 mass %) formed by sputtering with a thickness of 20 nm on a glass substrate is used as the other panel; the two panels are arranged in such a way that the transparent conductive films are opposite to each other, and epoxy resin beads with a diameter of 30 μm are interposed therebetween, and the panel on the film side and the panel on the glass side are attached with a double-sided tape with a thickness of 170 μm to produce a touch panel; then, polyacetal is used to form a touch panel. A pen (shape of the front end: 0.8mmR) was used to apply a load of 2.5N to perform a linear sliding test on the touch panel for 180,000 reciprocating strokes. In this test, the pen load was applied to the transparent conductive film surface of the present invention. The sliding distance at this time was set to 30mm, and the sliding speed was set to 180mm/second. After this sliding durability test, the ON resistance (resistance value when the movable electrode (thin film electrode) and the fixed electrode are in contact) when the sliding part is pressed with a pen load of 0.8N was measured.(Pen weight pressure test)A transparent conductive film of the present invention cut into 50 mm×50 mm is used as one panel, and a transparent conductive film containing an indium-tin composite oxide film (tin oxide content: 10 mass %) formed by sputtering with a thickness of 20 nm on a glass substrate is used as the other panel; the two panels are arranged in a manner that the transparent conductive films are opposite to each other, and epoxy resin beads with a diameter of 30 μm are interposed therebetween, and the panel on the film side and the panel on the glass side are attached with a double-sided tape with a thickness adjusted to 120 μm to prepare a touch panel; a load of 35 N is applied to a position 2.0 mm away from the edge of the double-sided tape with a polyacetal pen (the shape of the front end is 0.8 mmR), and the double-sided tape is parallel to the double-sided tape to achieve the desired effect. Apply 10 times (5 round trips) of linear sliding; in this test, apply a pen load to the transparent conductive film surface of the present invention; the sliding distance at this time is set to 30mm, and the sliding speed is set to 20mm/second; however, slide at a position without epoxy resin beads; after sliding, remove the transparent conductive film, measure the surface resistance of any 5 points of the sliding part (4-terminal method), and find the average value; when measuring the surface resistance, arrange 4 terminals in a direction perpendicular to the sliding part so that the sliding part comes between the second terminal and the third terminal; divide the average value of the surface resistance value of the sliding part by the surface resistance value of the non-sliding part (measured by the 4-terminal method), and calculate the increase rate of the surface resistance value.
本發明之透明導電性薄膜係筆滑動耐久性與筆重加壓耐久性優異。筆滑動耐久性與筆重加壓耐久性為相反的性質。首先，說明筆滑動耐久性。筆滑動耐久性優異的銦-錫複合氧化物之透明導電性薄膜係透明導電膜的結晶化度高，結晶粒徑大。針對結晶化度與結晶粒徑進行說明。將穿透型電子顯微鏡下觀察之具有圓形或多角形狀的區域之部分定義為透明導電膜的結晶(=結晶粒)，將其以外的部分定義為非晶。所謂結晶化度高，就是表示結晶的比例高。所謂結晶粒徑大，就是表示穿透型電子顯微鏡下觀察之圓形或多角形狀的區域大。結晶化度高的透明導電膜，由於硬結晶的比例高、結晶粒徑大者在結晶粒之周圍的應變會變大等，故透明導電膜會變硬，筆滑動耐久性優異。其次，說明筆重加壓耐久性。筆重加壓耐久性優異的銦-錫複合氧化物之透明導電性薄膜必須係透明導電膜的結晶化度低，結晶粒徑小，再者透明導電膜的三次元表面粗糙度小。三次元表面粗糙度係容後說明，但首先，結晶化度低的透明導電膜，由於柔軟的非晶之比例高、結晶粒徑小者在結晶粒之周圍的應變會變小等，故變成即使對透明導電膜施加荷重也不易有裂痕等，筆重加壓耐久性優異。如前述，可知筆滑動耐久性與筆重加壓耐久性為相反的性質。檢討之結果，發明出：藉由控制透明導電膜的結晶化度與結晶粒徑，而可兼顧筆滑動耐久性與筆重加壓耐久性。針對具有兼顧筆滑動耐久性與筆重加壓耐久性之透明導電膜的透明導電性薄膜，進行說明。The transparent conductive film of the present invention is excellent in pen sliding durability and pen weight pressure durability. Pen sliding durability and pen weight pressure durability are opposite properties. First, the pen sliding durability is explained. The transparent conductive film of indium-tin composite oxide with excellent pen sliding durability has a high degree of crystallization and a large crystal grain size. The degree of crystallization and the crystal grain size are explained. The part with a circular or polygonal area observed under a transmission electron microscope is defined as the crystal (= crystal grain) of the transparent conductive film, and the other part is defined as amorphous. The so-called high degree of crystallization means that the proportion of crystals is high. The so-called large crystal grain size means that the circular or polygonal area observed under a transmission electron microscope is large. A transparent conductive film with a high degree of crystallization has a high proportion of hard crystals and a large crystal grain size, so the strain around the crystal grains becomes larger. Therefore, the transparent conductive film becomes hard and has excellent pen sliding durability. Next, the durability against pen weight pressure is explained. A transparent conductive film of indium-tin composite oxide with excellent durability against pen weight pressure must have a low degree of crystallization, a small crystal grain size, and a small three-dimensional surface roughness. The three-dimensional surface roughness will be explained later, but first of all, a transparent conductive film with a low degree of crystallization has a high proportion of soft amorphous and a small crystal grain size, so the strain around the crystal grains becomes smaller. Therefore, even if a load is applied to the transparent conductive film, it is not easy to crack, and has excellent durability against pen weight pressure. As mentioned above, it is known that the pen sliding durability and the pen weight pressure durability are opposite properties. As a result of the review, it was found that the pen sliding durability and the pen weight pressure durability can be taken into account by controlling the crystallization degree and crystal grain size of the transparent conductive film. A transparent conductive film having a transparent conductive film that takes into account the pen sliding durability and the pen weight pressure durability is described.
若本發明中筆滑動耐久性試驗的透明導電薄膜之透明導電膜的ON電阻為10kΩ以下，則即使以筆連續輸入觸控面板，也對於透明導電膜抑制裂痕、剝離、磨耗等而較宜。於一態樣中ON電阻可為9.5kΩ以下，較佳為5kΩ以下。例如，ON電阻為3kΩ以下，可為1.5kΩ以下，較佳為1kΩ以下。若ON電阻為0kΩ，則筆滑動耐久性非常優異，只要是本發明，則ON電阻亦可為0kΩ。ON電阻例如可為3kΩ以上，也可為5kΩ以上。 由於ON電阻為如此的範圍內，故即使以筆連續輸入觸控面板，也對於透明導電膜抑制裂痕、剝離、磨耗等。 於一態樣中，可適宜組合該等上限及下限。If the ON resistance of the transparent conductive film of the transparent conductive film in the pen sliding durability test of the present invention is 10kΩ or less, it is preferable to suppress cracks, peeling, wear, etc. of the transparent conductive film even if the touch panel is continuously input with a pen. In one embodiment, the ON resistance can be 9.5kΩ or less, preferably 5kΩ or less. For example, the ON resistance is 3kΩ or less, can be 1.5kΩ or less, and preferably 1kΩ or less. If the ON resistance is 0kΩ, the pen sliding durability is very excellent, and as long as it is the present invention, the ON resistance can also be 0kΩ. The ON resistance can be, for example, 3kΩ or more, or 5kΩ or more.Since the ON resistance is within such a range, cracks, peeling, wear, etc. of the transparent conductive film can be suppressed even if the touch panel is continuously input with a pen.In one embodiment, such upper and lower limits may be appropriately combined.
本發明中筆重加壓試驗的透明導電薄膜之透明導電膜的表面電阻值之增加率宜為1.5以下。由於具有如此的特性，例如即使施加超出通常使用設想的強力，也能對於透明導電膜抑制裂痕、剝離等。表面電阻值之增加率更佳為1.2以下，特佳為1.0(無增大)。 此處，本發明之透明導電膜的表面電阻值之增加率較佳為1.0以上。The rate of increase of the surface resistance value of the transparent conductive film of the transparent conductive film in the pen weight pressure test of the present invention is preferably 1.5 or less. Due to such characteristics, even if a strong force exceeding the normal use assumption is applied, cracks and peeling of the transparent conductive film can be suppressed. The rate of increase of the surface resistance value is more preferably 1.2 or less, and particularly preferably 1.0 (no increase).Here, the rate of increase of the surface resistance value of the transparent conductive film of the present invention is preferably 1.0 or more.
於一態樣中，筆滑動耐久性試驗的透明導電薄膜之透明導電膜的ON電阻為0.05kΩ以上9.5kΩ以下，且筆重加壓(耐久性)試驗的透明導電薄膜之透明導電膜的表面電阻值之增加率為1.0以上1.5以下。 如上述，通常筆滑動耐久性與筆重加壓耐久性為相反的性質。本發明中，於如此的範圍內，可平衡良好地具有此等2個耐久性。又，即使以筆連續輸入觸控面板，對於透明導電膜也能抑制裂痕、剝離、磨耗等，而且對於筆滑動、筆重加壓所造成的負荷也能顯示優異的耐久性。尚且，數值範圍，可選擇本說明書中記載之範圍、值。In one embodiment, the ON resistance of the transparent conductive film of the transparent conductive film in the pen sliding durability test is 0.05kΩ or more and 9.5kΩ or less, and the rate of increase of the surface resistance value of the transparent conductive film of the transparent conductive film in the pen weight pressure (durability) test is 1.0 or more and 1.5 or less.As mentioned above, the pen sliding durability and the pen weight pressure durability are usually opposite properties. In the present invention, within such a range, these two durability can be well balanced. In addition, even if the touch panel is continuously input with a pen, cracks, peeling, wear, etc. can be suppressed for the transparent conductive film, and excellent durability can be shown for the load caused by pen sliding and pen weight pressure. Moreover, the numerical range can be selected from the range and value described in this manual.
本發明中，只要梳寬0.125mm、0.25mm、0.5mm、1.0mm、2.0mm下之透明導電性薄膜的透過影像清晰度之總和為250%以上且小於500%，則能提供高精細的映像故而較理想。透過影像清晰度之總和愈大，影像的清晰性愈高，亦即高精細性優異。透明導電性薄膜的透過影像清晰度之總和更佳為300%以上。透明導電性薄膜的透過影像清晰度之總和尤佳為400%以上。 尚且，本說明書中所謂「梳寬」，就是意指依據JIS-K7105的光學梳寬。In the present invention, as long as the sum of the clarity of the transmitted image of the transparent conductive film under the comb width of 0.125mm, 0.25mm, 0.5mm, 1.0mm, and 2.0mm is 250% or more and less than 500%, it can provide a high-precision image and is therefore more ideal. The larger the sum of the clarity of the transmitted image, the higher the clarity of the image, that is, the superior high-precision. The sum of the clarity of the transmitted image of the transparent conductive film is preferably 300% or more. The sum of the clarity of the transmitted image of the transparent conductive film is particularly preferably 400% or more.Moreover, the so-called "comb width" in this manual means the optical comb width according to JIS-K7105.
本發明中的透明導電性薄膜係銦-錫複合氧化物之透明導電膜的結晶粒徑較佳為10～100nm，銦-錫複合氧化物之透明導電膜的結晶化度較佳為20～80%。若銦-錫複合氧化物之透明導電膜的結晶粒徑為10nm以上，則因透明導電膜的結晶粒之周圍的應變，使透明導電膜適度地變硬，故筆滑動耐久性優異，而因此較宜。銦-錫複合氧化物之透明導電膜的結晶粒徑更佳為30nm以上。 另一方面，若銦-錫複合氧化物之透明導電膜的結晶粒徑為100nm以下，則透明導電膜不會因透明導電膜的結晶粒之周圍的應變而過硬，故筆重加壓耐久性優異，而因此較宜。銦-錫複合氧化物之透明導電膜的結晶粒徑更佳為90nm以下。 於一態樣中，銦-錫複合氧化物之透明導電膜的結晶粒徑為30nm以上95nm以下，例如為40nm以上90nm以下。 若銦-錫複合氧化物之透明導電膜的結晶化度為20%以上，則因透明導電膜中所佔的硬結晶而適度地變硬，筆滑動耐久性優異，而因此較宜。銦-錫複合氧化物之透明導電膜的結晶化度更佳為25%以上。另一方面，若銦-錫複合氧化物之透明導電膜的結晶化度為80%以下，則硬結晶所被含有的量多，但透明導電膜不會過硬，故筆重加壓耐久性優異，而因此較宜。 於一態樣中，銦-錫複合氧化物之透明導電膜的結晶化度為25%以上78%以下，例如為25%以上76%以下。The transparent conductive film of the present invention is an indium-tin composite oxide transparent conductive film, and the crystal grain size is preferably 10 to 100 nm, and the crystallization degree of the indium-tin composite oxide transparent conductive film is preferably 20 to 80%. If the crystal grain size of the transparent conductive film of the indium-tin composite oxide is greater than 10 nm, the transparent conductive film is moderately hardened due to the strain around the crystal grains of the transparent conductive film, so the pen sliding durability is excellent, and therefore it is more suitable. The crystal grain size of the transparent conductive film of the indium-tin composite oxide is more preferably greater than 30 nm.On the other hand, if the crystal grain size of the transparent conductive film of the indium-tin composite oxide is less than 100nm, the transparent conductive film will not be too hard due to the strain around the crystal grains of the transparent conductive film, so the pen weight pressure durability is excellent, and therefore it is more suitable. The crystal grain size of the transparent conductive film of the indium-tin composite oxide is more preferably less than 90nm.In one embodiment, the crystal grain size of the transparent conductive film of the indium-tin composite oxide is greater than 30nm and less than 95nm, for example, greater than 40nm and less than 90nm.If the crystallization degree of the transparent conductive film of the indium-tin composite oxide is greater than 20%, it becomes moderately hard due to the hard crystals occupying the transparent conductive film, and the pen sliding durability is excellent, and therefore it is more suitable. The crystallization degree of the transparent conductive film of the indium-tin composite oxide is preferably 25% or more. On the other hand, if the crystallization degree of the transparent conductive film of the indium-tin composite oxide is 80% or less, the amount of hard crystals contained is large, but the transparent conductive film will not be too hard, so the pen weight pressure durability is excellent, and therefore it is more suitable.In one embodiment, the crystallization degree of the transparent conductive film of the indium-tin composite oxide is 25% or more and 78% or less, for example, 25% or more and 76% or less.
本發明中的透明導電性薄膜係將透明導電膜的三次元表面粗糙度SRa當作X時，X較佳為1～100nm。若X為1～100nm，則透明導電膜之表面突起小，因此進行筆重加壓試驗時表面突起的變形量變小，而可抑制透明導電膜的裂痕發生，再者在透明導電膜會有一些表面突起，故亦能保持薄膜捲取性，而因此較宜。X更佳為1～80nm。X尤佳為1～65nm。The transparent conductive film of the present invention is preferably 1 to 100 nm when the three-dimensional surface roughness SRa of the transparent conductive film is taken as X. If X is 1 to 100 nm, the surface protrusions of the transparent conductive film are small, so the deformation amount of the surface protrusions during the pen weight pressure test becomes small, and the occurrence of cracks in the transparent conductive film can be suppressed. In addition, there are some surface protrusions in the transparent conductive film, so the film rollability can also be maintained, which is preferred. X is more preferably 1 to 80 nm. X is particularly preferably 1 to 65 nm.
本發明中的透明導電膜係由銦-錫複合氧化物所構成，較佳為包含0.5質量%以上10質量%以下的氧化錫。銦-錫複合氧化物中的氧化錫相當於對於氧化銦來說係雜質。藉由含有氧化錫的雜質，銦-錫複合氧化物的熔點會增大。亦即，含有氧化錫的雜質者，會朝向阻礙結晶化的方向進行作用，故其為與結晶粒徑或結晶化度等結晶性之相關性強的重要因子。若含有0.5質量%以上的氧化錫，則透明導電性薄膜之表面電阻會成為實用的水準而較宜。氧化錫之含有率更佳為1質量%以上，特佳為2質量%以上。若氧化錫之含有率為10質量%以下，則調節成後述的半結晶狀態後的結晶化變得容易發生，筆滑動耐久性變良好，而較宜。氧化錫之含有率更佳為8質量%以下，尤佳為6質量%以下，特佳為4質量%以下。尚且，本發明之透明導電性薄膜之表面電阻較佳為50～900Ω/□，更佳為50～600Ω/□。The transparent conductive film in the present invention is composed of indium-tin composite oxide, and preferably contains 0.5 mass% or more and 10 mass% or less tin oxide. Tin oxide in the indium-tin composite oxide is equivalent to an impurity for indium oxide. By containing impurities such as tin oxide, the melting point of the indium-tin composite oxide increases. That is, impurities containing tin oxide act in a direction that inhibits crystallization, and are therefore important factors that are strongly correlated with crystallinity such as crystal grain size and degree of crystallization. When 0.5% by mass or more of tin oxide is contained, the surface resistance of the transparent conductive film becomes a practical level, which is preferable. The content rate of tin oxide is more preferably 1 mass% or more, and particularly preferably 2 mass% or more. If the content of tin oxide is 10% by mass or less, crystallization after adjustment to the semi-crystalline state described below becomes easy to occur, and the pen sliding durability becomes good, which is preferred. The content of tin oxide is more preferably 8% by mass or less, more preferably 6% by mass or less, and particularly preferably 4% by mass or less. Moreover, the surface resistance of the transparent conductive film of the present invention is preferably 50 to 900Ω/□, more preferably 50 to 600Ω/□.
本發明中透明導電膜的厚度較佳為10nm以上30nm以下。透明導電膜的厚度，其係與結晶粒徑或結晶化度等結晶性之相關性強的重要因子。若透明導電膜的厚度為10nm以上，則在透明導電膜中非晶不會過多，容易給予成為後述的半結晶狀態之適度的結晶粒徑與結晶化度，結果保持筆滑動耐久性而較宜。透明導電膜的厚度更佳為13nm以上，尤佳為16nm以上。又，若透明導電膜的厚度為30nm以下，則透明導電膜的結晶粒徑不會過大、結晶化度不會過高，容易保持半結晶狀態，可保持筆重加壓耐久性而較宜。更佳為28nm以下，尤佳為25nm以下。In the present invention, the thickness of the transparent conductive film is preferably not less than 10nm and not more than 30nm. The thickness of the transparent conductive film is an important factor that is strongly correlated with crystallinity such as crystal grain size or degree of crystallization. If the thickness of the transparent conductive film is more than 10nm, there will not be too much amorphous in the transparent conductive film, and it is easy to give the appropriate crystal grain size and degree of crystallization to become the semi-crystalline state described later, and as a result, it is better to maintain the pen sliding durability. The thickness of the transparent conductive film is more preferably not less than 13nm, and particularly preferably not less than 16nm. Furthermore, if the thickness of the transparent conductive film is less than 30nm, the crystal grain size of the transparent conductive film will not be too large, the degree of crystallization will not be too high, and it is easy to maintain the semi-crystalline state, and it is better to maintain the pen weight pressure durability. It is more preferably less than 28nm, and particularly preferably less than 25nm.
本發明中的透明導電性薄膜係將透明塑膠薄膜基材上之與透明導電膜側相反面的三次元表面粗糙度SRa當作Y時，若(X3+Y3)1/3為140nm以下，則梳寬0.125mm、0.25mm、0.5mm、1.0mm、2.0mm下之透明導電性薄膜的透過影像清晰度之總和成為250%以上且小於500%，因此能提供高精細的映像而較理想。((X3+Y3)1/3之值愈小，透明導電性薄膜之兩面的凹凸愈小，因此確認並利用：對透明導電性薄膜的入射光之直進性提升用之透過影像清晰度有變高的傾向。(X3+Y3)1/3更佳為120nm以下。(X3+Y3)1/3尤佳為70nm以下。若(X3+Y3)1/3為1nm以上，則在透明導電性薄膜會有一些表面突起，因此能保持薄膜捲取性，而因此較宜。The transparent conductive film of the present invention is a film having a three-dimensional surface roughness SRa of the surface opposite to the transparent conductive film side on the transparent plastic film substrate as Y. If (X3 +Y3 )1/3 is less than 140 nm, the sum of the transparent image clarity of the transparent conductive film at comb widths of 0.125 mm, 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm becomes greater than 250% and less than 500%, thereby being able to provide high-precision images and being more ideal. The smaller the value of ((X3 +Y3 )1/3 is, the smaller the unevenness on both sides of the transparent conductive film is. Therefore, it is confirmed and utilized that the straightness of the incident light on the transparent conductive film tends to increase the clarity of the transmitted image. (X3 +Y3 )1/3 is more preferably 120nm or less. (X3 +Y3 )1/3 is even more preferably 70nm or less. If (X3 +Y3 )1/3 is more than 1nm, there will be some surface protrusions on the transparent conductive film, so the film rollability can be maintained, which is more suitable.
本發明中的透明導電性薄膜較佳為即使於透明導電膜面實施附著性試驗(JIS K5600-5-6：1999)，透明導電膜也不剝離。附著性試驗中透明導電膜不剝落的透明導電性薄膜，由於透明導電膜密接於透明塑膠基材或硬化型樹脂層等接觸透明導電膜之層，故即使以筆連續輸入觸控面板，對於透明導電膜也可抑制裂痕、剝離、磨耗等，再者即使施加超出通常使用所設想的強力，對於透明導電膜也可抑制裂痕、剝離等，而因此較宜。The transparent conductive film of the present invention is preferably such that the transparent conductive film does not peel off even when an adhesion test (JIS K5600-5-6: 1999) is performed on the transparent conductive film surface. The transparent conductive film that does not peel off in the adhesion test is preferably such that the transparent conductive film is closely attached to the transparent plastic substrate or the layer in contact with the transparent conductive film, such as the hardened resin layer, and therefore cracks, peeling, and abrasion of the transparent conductive film can be suppressed even when the touch panel is continuously input with a pen. Furthermore, cracks, peeling, and the like can be suppressed even when a strong force exceeding that expected for normal use is applied.
本發明中的透明導電性薄膜較佳為於透明導電性薄膜之透明導電膜側，進行耐彎曲性試驗(JIS K5600-5-1：1999)，以10倍的放大鏡觀察彎曲部時，發生破裂或剝落的心軸直徑小於20mm。若心軸直徑小於20mm，則在進行筆重加壓試驗時，接觸透明導電膜之層不會破裂，在透明導電膜中不會有裂痕，而因此較宜。更佳為18mm以下。 於一態樣中，耐彎曲性試驗之值可為1mm以上，例如可為8mm以上、10mm以上。又，於一態樣中，耐彎曲性試驗之值為13mm以上，可為15mm以上。 藉由如此的範圍內，在進行筆重加壓試驗時，接觸透明導電膜的層不破裂，在透明導電膜中不會有裂痕，而因此較宜。 又，可提供能兼具優異的筆滑動耐久性及優異的筆重加壓耐久性之透明導電性薄膜。The transparent conductive film of the present invention is preferably a transparent conductive film side of the transparent conductive film, and the bending resistance test (JIS K5600-5-1: 1999) is carried out. When the bending part is observed with a 10-fold magnifying glass, the mandrel diameter where cracking or peeling occurs is less than 20mm. If the mandrel diameter is less than 20mm, the layer in contact with the transparent conductive film will not be broken during the pen weight pressure test, and there will be no cracks in the transparent conductive film, so it is more suitable. It is more preferably less than 18mm.In one embodiment, the value of the bending resistance test can be more than 1mm, for example, more than 8mm, more than 10mm. In another embodiment, the value of the bending resistance test is more than 13mm, and can be more than 15mm.By keeping the thickness within such a range, the layer in contact with the transparent conductive film does not break during the pen weight pressure test, and there is no crack in the transparent conductive film, which is more suitable.In addition, a transparent conductive film having both excellent pen sliding durability and excellent pen weight pressure durability can be provided.
本發明中的透明導電性薄膜係透明塑膠薄膜基材的厚度較佳為100～250μm之範圍，更佳為130～220μm。若塑膠薄膜的厚度為100μm以上，則可保持機械的強度，尤其對於用於觸控面板時的筆輸入之變形小，筆滑動耐久性與筆重加壓耐久性優異，而因此較宜。另一方面，若厚度為250μm以下，則在用於觸控面板時，不必特別地增大用以使其位於筆輸入的位置之荷重而較宜。The transparent conductive film of the present invention is a transparent plastic film substrate with a thickness preferably in the range of 100 to 250 μm, more preferably 130 to 220 μm. If the thickness of the plastic film is 100 μm or more, the mechanical strength can be maintained, especially the deformation of the pen input when used in a touch panel is small, and the pen sliding durability and pen weight pressure durability are excellent, so it is more suitable. On the other hand, if the thickness is 250 μm or less, when used in a touch panel, it is not necessary to increase the load for the pen input position, so it is more suitable.
本發明中的透明導電性薄膜較佳為在透明導電膜與塑膠薄膜基材之間具有硬化型樹脂層。由於具有硬化型樹脂層，而可透明導電膜的密接力增加或分散施加於透明導電膜的力，因此於筆滑動試驗中對於透明導電膜可抑制裂痕、剝離、磨耗等，再者於筆重加壓試驗中對於透明導電膜可抑制裂痕、剝離等，故而較宜。The transparent conductive film of the present invention preferably has a hardened resin layer between the transparent conductive film and the plastic film substrate. The hardened resin layer can increase the adhesion of the transparent conductive film or disperse the force applied to the transparent conductive film, so that cracks, peeling, and wear of the transparent conductive film can be suppressed in the pen sliding test, and cracks, peeling, and the like can be suppressed in the pen weight pressure test, so it is more suitable.
本發明中的透明導電膜之結晶性為不過高、不過低之狀態(如此的結晶性，決定稱為半結晶性或半結晶質)。使透明導電膜安定地成為半結晶性者係非常困難的。其係因為從非晶性到結晶性的急劇相變化之途中停止的狀態為半結晶性。因此，敏感於與結晶性有關的參數，亦即成膜環境中的水量，尤其非常敏感於含氫原子的氣體，成膜環境中之含氫原子的氣體或水量即使只少一點點，也會變成幾乎完全的結晶性(高結晶性)，相反地，成膜環境中之含氫原子的氣體或水量即使只多一點點，也會變成非晶性(低結晶性)。The crystallinity of the transparent conductive film in the present invention is in a state of neither too high nor too low (such crystallinity is called semi-crystalline or semi-crystalline). It is very difficult to stably make the transparent conductive film semi-crystalline. This is because the state in which the film stops during the rapid phase change from amorphous to crystalline is semi-crystalline. Therefore, it is sensitive to parameters related to crystallinity, that is, the amount of water in the film-forming environment, and is particularly sensitive to hydrogen-containing gas. If the amount of hydrogen-containing gas or water in the film-forming environment is even slightly less, the film will become almost completely crystalline (high crystallinity). On the contrary, if the amount of hydrogen-containing gas or water in the film-forming environment is even slightly more, the film will become amorphous (low crystallinity).
用於得到本發明之透明導電性薄膜之製造方法係沒有特別的限定，但例如可較佳地例示如以下的製造方法。 作為在透明塑膠薄膜基材上之至少一面上形成結晶性銦-錫複合氧化物之透明導電膜之方法，較宜使用濺鍍法。為了以高生產性製造透明導電性薄膜，較佳為使用：供給薄膜捲筒，於成膜後，捲成薄膜捲筒的形狀之所謂輥式濺鍍裝置。可較宜採用：於成膜環境中以質流控制器導入下述記載的量之含氫原子的氣體(氫、氨、氫+氬混合氣體等，只要是含有氫原子的氣體，則沒有特別的限定；但水除外)，再將濺鍍時的薄膜溫度設為0℃以下，使用含有0.5～10質量%的氧化錫之銦-錫複合氧化物的燒結靶，以銦-錫複合氧化物之透明導電膜的厚度成為10～30nm之方式調整，在銦-錫複合氧化物之透明導電膜的三次元表面粗糙度SRa為1～100nm之透明塑膠薄膜上形成透明導電膜。於濺鍍時的成膜環境中，含氫原子的氣體係具有阻礙透明導電膜的結晶化之效果。於成膜環境中流動氫氣時，(氫氣流量)÷(惰性氣體流量+氫氣流量)×100之值(有時僅記載為氫濃度)為0.01～3.00%較理想。氫濃度例如為0.01%以上2.00%，也可為0.01%以上1.00%以下。 由於氫濃度為如此的範圍內，因此例如於筆滑動耐久性試驗ON電阻值、筆重加壓耐久性試驗之任一者中，皆可有助於引導至良好的結果。 又，作為惰性氣體，可舉出氦、氖、氬、氪、氙等。使用氫氣以外之含氫原子的氣體時，只要從含氫原子的氣體中含有的氫原子量來換算成氫氣(=氫分子)量進行計算即可。於成膜環境中以質流控制器精密地流動含氫原子的氣體時，對於與薄膜捲筒的長度方向呈垂直的方向，以能均勻地噴吹含氫原子的氣體之方式配置氣體吹出口，藉此不易成為如結晶性高的部分或低的部分混合存在的透明導電膜，而容易得到均勻的半結晶性之透明導電膜，故可適宜得到能兼具優異的筆滑動耐久性及筆重加壓耐久性之透明導電性薄膜。已知成膜環境中的水多時，透明導電膜的結晶性降低，因此成膜環境中的水量亦為重要的因子。使用含氫原子的氣體時，向薄膜捲筒進行濺鍍時之成膜環境的水分壓相對於惰性氣體之比的中心值(最大值與最小值的中間之值)係控制在1.0×10-4～2.0×10-3，再者關於濺鍍時之成膜環境的水分壓相對於惰性氣體之比，若從成膜開始時到成膜結束時的最大值與最小值之差為1.0×10-3以下，則在薄膜之全長上皆可保持透明導電膜的結晶性之均勻性，因此除了作為濺鍍機的排氣裝置較宜使用的旋轉泵、渦輪分子泵、低溫泵之外，還有下述之轟擊步驟、下述之薄膜捲筒端面的凹凸之高低差的限定等，若以將透明導電膜成膜時從薄膜所放出的水量減少、放出在薄膜全長上皆均勻的水量之方式來設定，則將變得不需要水量的精密控制而較宜。惟，水分壓相對於惰性氣體之比的中心值亦多少依賴於銦-錫複合氧化物之透明導電膜中的氧化錫之含有率或透明導電膜的厚度。銦-錫複合氧化物之透明導電膜中的氧化錫之添加量多時或透明導電膜薄時，宜將水分壓相對於惰性氣體之比的中心值設定在前述範圍中之低值。相反地，銦-錫複合氧化物之透明導電膜中的氧化錫之含有率少時或透明導電膜厚時，宜將水分壓相對於惰性氣體之比的中心值設定在前述範圍中之高值。較佳為將濺鍍時的薄膜溫度設為0℃以下，在透明塑膠薄膜上形成透明導電膜。成膜中的薄膜溫度，係以行進薄膜所接觸的中央輥之溫度調節用的調溫機之設定溫度來代用。此處，圖5中顯示本發明中所適宜使用的濺鍍裝置之一例的示意圖，行進薄膜1係部分地接觸中央輥2之表面而行進。通過煙囪3設置銦-錫的濺鍍靶4，於使中央輥2上行進的薄膜1之表面上沉積銦-錫複合氧化物之薄膜並積層。中央輥2係藉由未圖示的調溫機進行溫度控制。若薄膜溫度為0℃以下，則可抑制使透明導電膜的結晶性變動的來自薄膜之水、有機氣體等之雜質氣體的放出，從成膜開始時到成膜結束時的透明導電膜之結晶性容易均勻化而較宜。使用含氫原子的氣體時，濺鍍時之成膜環境的水分壓相對於惰性氣體之比的中心值(最大值與最小值的中間之值)宜為1.0×10-4～2.0×10-3。若濺鍍時之成膜環境的水分壓相對於惰性氣體之比為前述範圍，則含氫原子的氣體對於透明導電膜的結晶性之阻礙係有效地作用而較宜。又，為了使透明導電性薄膜之表面電阻及全光線透過率成為實用的水準，在濺鍍時宜添加氧氣。此製造方法係盡量排除使透明導電膜的結晶性變動之要因的水所造成的結晶性之影響，主要著眼於藉由含氫的氣體來控制結晶性。The manufacturing method for obtaining the transparent conductive film of the present invention is not particularly limited, but for example, the following manufacturing method can be preferably exemplified. As a method for forming a transparent conductive film of a crystalline indium-tin composite oxide on at least one side of a transparent plastic film substrate, a sputtering method is preferably used. In order to manufacture a transparent conductive film with high productivity, it is preferably used: a film roll is supplied, and after film formation, the film is rolled into the shape of a film roll. It is preferable to introduce the following amount of hydrogen atom-containing gas (hydrogen, ammonia, hydrogen + hydrogen mixed gas, etc., as long as it is a gas containing hydrogen atoms, there is no special limitation; but water is excluded) into the film forming environment by means of a mass flow controller, and then set the film temperature during sputtering to below 0°C, use a sintered target of an indium-tin composite oxide containing 0.5 to 10 mass % of tin oxide, and adjust the thickness of the transparent conductive film of the indium-tin composite oxide to 10 to 30 nm, and form a transparent conductive film on a transparent plastic film having a three-dimensional surface roughness SRa of 1 to 100 nm of the transparent conductive film of the indium-tin composite oxide. In the film-forming environment during sputtering, the gas containing hydrogen atoms has the effect of hindering the crystallization of the transparent conductive film. When hydrogen gas flows in the film-forming environment, the value of (hydrogen flow rate) ÷ (inert gas flow rate + hydrogen flow rate) × 100 (sometimes only recorded as hydrogen concentration) is preferably 0.01 to 3.00%. The hydrogen concentration is, for example, above 0.01% and 2.00%, or above 0.01% and below 1.00%. Since the hydrogen concentration is within such a range, it can help to lead to good results in any of the ON resistance value of the pen sliding durability test and the pen weight pressure durability test. In addition, as an inert gas, helium, neon, argon, krypton, xenon, etc. can be cited. When using a gas containing hydrogen atoms other than hydrogen gas, it is sufficient to convert the amount of hydrogen atoms contained in the gas containing hydrogen atoms into the amount of hydrogen gas (= hydrogen molecules) for calculation. When the gas containing hydrogen atoms is precisely flowed by a mass flow controller in the film forming environment, the gas blowing outlet is arranged in a direction perpendicular to the length direction of the film roll so that the gas containing hydrogen atoms can be uniformly sprayed. This makes it difficult for a transparent conductive film to be a mixture of high-crystalline parts and low-crystalline parts, and it is easy to obtain a uniform semi-crystalline transparent conductive film. Therefore, a transparent conductive film with excellent pen sliding durability and pen weight pressure durability can be appropriately obtained. It is known that when there is a lot of water in the film forming environment, the crystallinity of the transparent conductive film decreases, so the amount of water in the film forming environment is also an important factor. When using a gas containing hydrogen atoms, the central value (the middle value between the maximum and minimum values) of the ratio of the water pressure in the film-forming environment to the inert gas during sputtering onto the film roll is controlled to be 1.0×10-4 to 2.0×10-3 . Furthermore, regarding the ratio of the water pressure in the film-forming environment to the inert gas during sputtering, if the difference between the maximum and minimum values from the start of film formation to the end of film formation is 1.0×10-3 or less, the uniformity of crystallinity of the transparent conductive film can be maintained over the entire length of the film. Therefore, in addition to the rotary pump, turbomolecular pump, and cryogenic pump preferably used as the exhaust device of the sputtering machine, the following bombardment step and the following limitation of the height difference of the concave and convex end surface of the film roll can be set in such a way that the amount of water released from the film during the formation of the transparent conductive film is reduced and the amount of water released is uniform over the entire length of the film. This makes it unnecessary to precisely control the amount of water. However, the central value of the ratio of the water pressure to the inert gas also depends on the content of tin oxide in the transparent conductive film of the indium-tin composite oxide or the thickness of the transparent conductive film. When the amount of tin oxide added in the transparent conductive film of indium-tin composite oxide is large or the transparent conductive film is thin, the central value of the ratio of water pressure relative to inert gas is preferably set to a low value in the aforementioned range. On the contrary, when the content of tin oxide in the transparent conductive film of indium-tin composite oxide is low or the transparent conductive film is thick, the central value of the ratio of water pressure relative to inert gas is preferably set to a high value in the aforementioned range. It is preferred to set the film temperature during sputtering to below 0°C to form a transparent conductive film on a transparent plastic film. The film temperature during film formation is replaced by the set temperature of a temperature controller used to adjust the temperature of the center roller that the traveling film contacts. Here, FIG5 is a schematic diagram showing an example of a sputtering device suitable for use in the present invention, in which the traveling film 1 is traveling while partially contacting the surface of the central roller 2. An indium-tin sputtering target 4 is set through a chimney 3, and a thin film of an indium-tin composite oxide is deposited and layered on the surface of the film 1 traveling on the central roller 2. The central roller 2 is temperature-controlled by a temperature control machine not shown. If the film temperature is below 0°C, the emission of impurity gases such as water and organic gas from the film that change the crystallinity of the transparent conductive film can be suppressed, and the crystallinity of the transparent conductive film from the beginning of film formation to the end of film formation is easy to be uniform and preferred. When using a gas containing hydrogen atoms, the central value (the middle value between the maximum and minimum values) of the ratio of the water pressure in the film-forming environment during sputtering to the inert gas is preferably 1.0×10-4 to 2.0×10-3 . If the ratio of the water pressure in the film-forming environment during sputtering to the inert gas is within the aforementioned range, the gas containing hydrogen atoms is more effective in hindering the crystallinity of the transparent conductive film. Furthermore, in order to bring the surface resistance and total light transmittance of the transparent conductive film to a practical level, oxygen is preferably added during sputtering. This manufacturing method aims to eliminate the influence of water, which is the factor that causes the crystallinity of the transparent conductive film to change, as much as possible, and mainly focuses on controlling the crystallinity by using a gas containing hydrogen.
於塑膠薄膜上將銦-錫複合氧化物成膜時的水量之控制中，觀測實際成膜時的水量係基於以下的2個理由而優於觀測極限真空度(ultimate vacuum)。In controlling the amount of water when forming an indium-tin composite oxide film on a plastic film, observing the actual amount of water during film formation is better than observing the ultimate vacuum for the following two reasons.
就其理由之第1點而言，若以濺鍍來成膜為塑膠薄膜，則薄膜被加熱，從薄膜放出水分，因此成膜環境中的水量增加，比測定極限真空度時的水量較增加，故相較於以極限真空度表現，以成膜時的水量表現較正確。As for the first reason, if a plastic film is formed by sputtering, the film is heated and water is released from the film, so the amount of water in the film-forming environment increases, which is greater than the amount of water when the ultimate vacuum is measured. Therefore, it is more accurate to express it in terms of the amount of water when the film is formed than in terms of the ultimate vacuum.
其理由之第2點係大量地投入透明塑膠薄膜的裝置之情況。於如此的裝置中，將薄膜以薄膜捲筒之形態投入。若使薄膜成為捲筒而投入至真空槽，則捲筒的外層部分的水容易跑掉，但捲筒的內層部分的水難以跑掉。測定極限真空度時，薄膜捲筒會停止，但在成膜時薄膜捲筒會行進，因此多含水的薄膜捲筒之內層部分會被捲出，故成膜環境中的水量會增加，比起測定極限真空度時的水量還要增加。本發明中，於控制成膜環境中的水量時，藉由觀測濺鍍時之成膜環境的水分壓相對於惰性氣體之比，可較佳地對應。The second reason is the situation of a device that throws in a large amount of transparent plastic film. In such a device, the film is thrown in in the form of a film roll. If the film is rolled up and thrown into a vacuum tank, the water on the outer layer of the roll will easily escape, but the water on the inner layer of the roll will be difficult to escape. When measuring the ultimate vacuum degree, the film roll will stop, but when the film is formed, the film roll will move, so the inner layer of the film roll containing more water will be rolled out, so the amount of water in the film forming environment will increase, and it will increase more than the amount of water when the ultimate vacuum degree is measured. In the present invention, when controlling the amount of water in the film forming environment, it can be better corresponded by observing the ratio of the water pressure of the film forming environment during sputtering relative to the inert gas.
於將透明導電膜成膜前，宜使薄膜通過轟擊步驟。所謂轟擊步驟，就是於將僅氬氣等之惰性氣體，或氧等之反應性氣體與惰性氣體的混合氣體流動之狀態下，施加電壓而進行放電，使其產生電漿。具體而言，宜以SUS靶等，藉由RF濺鍍，轟擊薄膜。由於薄膜因轟擊步驟而暴露於電漿中，故會從薄膜放出水或有機成分，將透明導電膜成膜時從薄膜放出的水或有機成分會減少，因此從成膜開始時到成膜結束時的透明導電膜之結晶性容易均勻化，故而較宜。又，由於透明導電膜所接觸的層因轟擊步驟而活性化，故透明導電膜的密接性提升，因此筆滑動耐久性或筆重加壓耐久性提升，故而較宜。Before forming a transparent conductive film, it is preferable to make the film pass through a bombardment step. The so-called bombardment step is to apply voltage to discharge while flowing an inert gas such as argon alone, or a mixed gas of a reactive gas such as oxygen and an inert gas, so as to generate plasma. Specifically, it is preferable to bombard the film with a SUS target or the like by RF sputtering. Since the film is exposed to plasma due to the bombardment step, water or organic components are released from the film. When the transparent conductive film is formed, the water or organic components released from the film are reduced. Therefore, the crystallinity of the transparent conductive film is easy to be uniform from the beginning to the end of film formation, which is preferable. Furthermore, since the layer to which the transparent conductive film contacts is activated by the impact step, the adhesion of the transparent conductive film is improved, and thus the pen sliding durability or the pen weight pressure durability is improved, which is preferable.
用於將透明導電膜成膜的薄膜捲筒，係在捲筒端面中，最凸處與最凹處之高低差較佳為10mm以下。若為10mm以下，則將薄膜捲筒投入濺鍍裝置時，來自薄膜端面的水或有機成分之放出方式的不均變小，故從成膜開始時到成膜結束時的透明導電膜之結晶性容易均勻化而較宜。The film roll used for forming the transparent conductive film preferably has a height difference of 10 mm or less between the most convex part and the most concave part in the end surface of the roll. If it is 10 mm or less, when the film roll is put into the sputtering device, the unevenness of the release pattern of water or organic components from the end surface of the film becomes small, so the crystallinity of the transparent conductive film is easy to be uniform from the beginning of film formation to the end of film formation.
於透明塑膠薄膜基材上的至少一面上形成結晶性銦-錫複合氧化物之透明導電膜之方法中，宜在濺鍍時導入氧氣。若在濺鍍時導入氧氣，則銦-錫複合氧化物的透明導電膜之因氧欠缺所造成的不良狀況消失，透明導電性薄膜之表面電阻低，全光線透過率變高，而較宜。因此，為了使透明導電性薄膜之表面電阻及全光線透過率成為實用的水準，宜在濺鍍時導入氧氣。尚且，本發明之透明導電性薄膜的全光線透過率較佳為70～95%。In a method for forming a transparent conductive film of a crystalline indium-tin composite oxide on at least one side of a transparent plastic film substrate, oxygen is preferably introduced during sputtering. If oxygen is introduced during sputtering, the adverse condition of the transparent conductive film of the indium-tin composite oxide caused by oxygen deficiency disappears, the surface resistance of the transparent conductive film is low, and the total light transmittance becomes high, which is more preferable. Therefore, in order to make the surface resistance and total light transmittance of the transparent conductive film reach a practical level, oxygen is preferably introduced during sputtering. Moreover, the total light transmittance of the transparent conductive film of the present invention is preferably 70 to 95%.
本發明之透明導電性薄膜係在透明塑膠薄膜基材上成膜積層銦-錫複合氧化物之透明導電膜後，宜於含氧的環境下，施予80～200℃、0.1～12小時加熱處理。若為80℃以上，則為了成為半結晶狀態而稍微提高結晶性的處置係容易，筆滑動耐久性提升而較宜。若為200℃以下，則確保透明塑膠薄膜的平面性而較宜。The transparent conductive film of the present invention is formed by laminating a transparent conductive film of an indium-tin composite oxide on a transparent plastic film substrate, and then subjected to a heat treatment at 80 to 200°C for 0.1 to 12 hours in an oxygen-containing environment. If the temperature is above 80°C, it is easy to slightly increase the crystallinity in order to achieve a semi-crystalline state, and the pen sliding durability is improved. If the temperature is below 200°C, it is preferred to ensure the planarity of the transparent plastic film.
＜透明塑膠薄膜基材＞ 本發明所用的透明塑膠薄膜基材，係將有機高分子熔融擠出或溶液擠出成薄膜狀，視需要在長度方向及/或寬度方向上施予延伸、冷卻、熱定型後之薄膜，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、聚對苯二甲酸丙二酯、聚對苯二甲酸丁二酯、尼龍6、尼龍4、尼龍66、尼龍12、聚醯亞胺、聚醯胺醯亞胺、聚醚碸、聚醚醚酮、聚碳酸酯、聚芳酯、纖維素丙酸酯、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、對排聚苯乙烯、降莰烯系聚合物等。<Transparent plastic film substrate>The transparent plastic film substrate used in the present invention is a film formed by melt extrusion or solution extrusion of an organic polymer, and then stretched, cooled, and heat-set in the length direction and/or width direction as needed. Examples of the organic polymer include polyethylene, polypropylene, polyethylene terephthalate, polyethylene 2,6-naphthalate, polytrimethylene terephthalate, polybutylene terephthalate, nylon 6, nylon 4, nylon 66, nylon 12, polyimide, polyamide imide, polyether sulfide, polyether ether ketone, polycarbonate, polyarylate, cellulose propionate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyether imide, polyphenylene sulfide, polyphenylene ether, polystyrene, para-polystyrene, norbornene polymers, etc.
於此等有機高分子之中，宜為聚對苯二甲酸乙二酯、聚對苯二甲酸丙二酯、聚對苯二甲酸丁二酯、聚2,6-萘二甲酸乙二酯、對排聚苯乙烯、降莰烯系聚合物、聚碳酸酯、聚芳酯等。又，此等有機高分子亦可少量共聚合其它有機聚合物之單體，或摻合其它有機高分子。Among these organic polymers, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene 2,6-naphthalate, para-polystyrene, norbornene polymers, polycarbonate, polyarylate, etc. In addition, these organic polymers may be copolymerized with a small amount of monomers of other organic polymers, or may be blended with other organic polymers.
本發明所用的透明塑膠薄膜基材，係在不損害本發明目的之範圍內，可對於前述薄膜施予電暈放電處理、輝光放電處理、火焰處理、紫外線照射處理、電子線照射處理、臭氧處理等之表面活化處理。The transparent plastic film substrate used in the present invention may be subjected to surface activation treatments such as corona discharge treatment, fluorescence discharge treatment, flame treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, ozone treatment, etc. within the scope that does not impair the purpose of the present invention.
若將硬化型樹脂層塗布於透明塑膠薄膜基材，則透明導電膜可與硬化型樹脂層強地密接或可分散施加於透明導電膜之力，因此於筆滑動試驗中對於透明導電膜抑制裂痕、剝離、磨耗等，再者於筆重加壓試驗中對於透明導電膜抑制裂痕、剝離等而較宜。又，若使硬化型樹脂層之表面成為凹凸後將透明導電膜成膜，則在筆滑動試驗時透明導電薄膜與玻璃接觸時的真正接觸面積減少，因此玻璃面與透明導電膜之滑動性變良好，筆滑動耐久性提升，或者可期待薄膜捲筒之捲取性的提升或抗牛頓環性，但若凹凸過大，則在進行筆重加壓試驗時的表面突起之變形量變大，在透明導電膜中發生裂痕而不宜。因此作為表面凹凸，將透明導電膜的三次元表面粗糙度SRa當作X時，X較佳成為1～100nm。又，硬化型樹脂層亦可塗布於透明塑膠薄膜基材之兩面。將與形成透明導電膜之面相反面的硬化型樹脂層之三次元表面粗糙度SRa當作Y時，Y較佳成為1～139nm。以下記載硬化型樹脂層之詳細。If the hardening resin layer is coated on the transparent plastic film substrate, the transparent conductive film can be closely attached to the hardening resin layer or the force applied to the transparent conductive film can be dispersed, thereby suppressing cracks, peeling, abrasion, etc. of the transparent conductive film in the pen sliding test, and suppressing cracks, peeling, etc. of the transparent conductive film in the pen weight pressure test. Furthermore, if the transparent conductive film is formed after the surface of the hardening resin layer is made uneven, the actual contact area between the transparent conductive film and the glass during the pen sliding test is reduced, so the sliding property between the glass surface and the transparent conductive film becomes good, the pen sliding durability is improved, or the film roll can be expected to be rolled up or the anti-Newton ring property is improved. However, if the unevenness is too large, the deformation amount of the surface protrusions during the pen weight pressure test becomes large, and cracks occur in the transparent conductive film, which is not desirable. Therefore, as the surface unevenness, when the three-dimensional surface roughness SRa of the transparent conductive film is regarded as X, X is preferably 1 to 100 nm. In addition, the hardening resin layer can also be applied to both sides of the transparent plastic film substrate. When the three-dimensional surface roughness SRa of the hardening resin layer on the opposite side to the side on which the transparent conductive film is formed is represented by Y, Y is preferably 1 to 139 nm. The details of the hardening resin layer are described below.
又，作為本發明所較宜使用的前述硬化型樹脂，只要是因加熱、紫外線照射、電子線照射等之能量施加而硬化的樹脂，則沒有特別的限制，可舉出聚矽氧樹脂、丙烯酸樹脂、甲基丙烯酸樹脂、環氧樹脂、三聚氰胺樹脂、聚酯樹脂、胺基甲酸酯樹脂等。從生產性之觀點來看，較佳為以紫外線硬化型樹脂作為主成分。The curable resin preferably used in the present invention is not particularly limited as long as it is a resin that is cured by energy application such as heating, ultraviolet irradiation, electron beam irradiation, etc. Examples thereof include silicone resins, acrylic resins, methacrylic resins, epoxy resins, melamine resins, polyester resins, urethane resins, etc. From the viewpoint of productivity, it is preferred to use an ultraviolet curable resin as the main component.
作為如此的紫外線硬化型樹脂，例如可舉出如多元醇的丙烯酸或甲基丙烯酸酯之多官能性丙烯酸酯樹脂，如由二異氰酸酯、多元醇及丙烯酸或甲基丙烯酸的羥基烷酯等所合成之多官能性的胺基甲酸酯丙烯酸酯樹脂等。視需要，可於此等多官能性樹脂中添加單官能性單體，例如乙烯基吡咯啶酮、甲基丙烯酸甲酯、苯乙烯等，使其共聚合。As such UV-curable resins, for example, there can be cited multifunctional acrylate resins such as acrylic acid or methacrylic acid esters of polyols, and multifunctional urethane acrylate resins synthesized from diisocyanate, polyols, and hydroxyalkyl esters of acrylic acid or methacrylic acid. If necessary, monofunctional monomers such as vinyl pyrrolidone, methyl methacrylate, styrene, etc. can be added to these multifunctional resins to make them copolymerized.
又，為了提高透明導電性薄膜與硬化型樹脂層之附著力，用以下記載之手法處理硬化型樹脂層之表面者為有效。作為具體的手法，可舉出為了增加羰基、羧基、羥基而照射輝光或電暈放電之放電處理法，為了增加胺基、羥基、羰基等極性基而以酸或鹼處理之化學藥品處理法等。Furthermore, in order to improve the adhesion between the transparent conductive film and the curing resin layer, it is effective to treat the surface of the curing resin layer by the following methods. Specific methods include discharge treatment by irradiation with light or corona discharge to increase carbonyl, carboxyl, and hydroxyl groups, and chemical treatment by acid or alkali to increase polar groups such as amine, hydroxyl, and carbonyl groups.
紫外線硬化型樹脂通常係添加光聚合起始劑而使用。作為光聚合起始劑，可無特別限制地使用能吸收紫外線而產生自由基的眾所周知之化合物，作為如此的光聚合起始劑，例如可舉出各種苯偶姻類、苯基酮類、二苯基酮類等。光聚合起始劑之添加量係紫外線硬化型樹脂每100質量份通常為1～5質量份。UV-curable resins are usually used by adding a photopolymerization initiator. As the photopolymerization initiator, a well-known compound that can absorb ultraviolet light and generate free radicals can be used without particular limitation. Examples of such photopolymerization initiators include various benzoins, phenyl ketones, and diphenyl ketones. The amount of the photopolymerization initiator added is usually 1 to 5 parts by mass per 100 parts by mass of the UV-curable resin.
又，於本發明中的硬化型樹脂層中，除了主要構成成分的硬化型樹脂之外，較佳為還併用無機粒子或有機粒子。藉由使無機粒子或有機粒子分散於硬化型樹脂中，可在硬化型樹脂表面上形成凹凸，可提高廣域的表面粗糙度。In addition, in the hardening resin layer of the present invention, in addition to the hardening resin as the main component, inorganic particles or organic particles are preferably used in combination. By dispersing the inorganic particles or organic particles in the hardening resin, it is possible to form irregularities on the surface of the hardening resin, thereby improving the surface roughness over a wide area.
作為前述無機粒子，例示二氧化矽等。作為前述有機粒子，例示聚酯樹脂、聚烯烴樹脂、聚苯乙烯樹脂、聚醯胺樹脂等。Examples of the inorganic particles include silicon dioxide, and examples of the organic particles include polyester resins, polyolefin resins, polystyrene resins, and polyamide resins.
於無機粒子或有機粒子以外，亦較佳為除了主要構成成分的硬化型樹脂之外還併用不相溶於硬化型樹脂的樹脂。藉由少量併用不相溶於基質的硬化型樹脂之樹脂，可在硬化型樹脂中發生相分離，使不相溶樹脂分散成粒子狀。藉由此不相溶樹脂的分散粒子，可在硬化型樹脂表面上形成凹凸，提高廣域的表面粗糙度。In addition to the inorganic particles or organic particles, it is also preferred to use a resin that is incompatible with the hardening resin in addition to the hardening resin as the main component. By using a small amount of a resin that is incompatible with the hardening resin in the matrix, phase separation can occur in the hardening resin, and the incompatible resin can be dispersed in the form of particles. The dispersed particles of the incompatible resin can form irregularities on the surface of the hardening resin, thereby improving the surface roughness over a wide area.
作為不相溶樹脂，例示聚酯樹脂、聚烯烴樹脂、聚苯乙烯樹脂、聚醯胺樹脂等。Examples of the immiscible resin include polyester resin, polyolefin resin, polystyrene resin, polyamide resin and the like.
此處作為一例，顯示於透明導電膜的正下方之硬化型樹脂層中使用無機粒子時之摻合比例。紫外線硬化型樹脂每100質量份，較佳為無機粒子0.1～20質量份，更佳為0.1～15質量份，特佳為0.1～12質量份。 前述無機粒子之摻合量若紫外線硬化型樹脂每100質量份為0.1～20質量份，則在硬化型樹脂層表面所形成的凸部不過小，可有效果地賦予三次元表面粗糙度，於進行筆重加壓試驗時表面突起的變形量變小而抑制透明導電膜的裂痕發生，可提供高精細的映像，再者由於在透明導電膜中會有一些表面突起，故亦保持薄膜捲取性而較宜。Here, as an example, the mixing ratio when using inorganic particles in the curable resin layer directly below the transparent conductive film is shown. For every 100 parts by mass of the UV curable resin, the inorganic particles are preferably 0.1 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and particularly preferably 0.1 to 12 parts by mass.If the amount of the inorganic particles mixed is 0.1 to 20 parts by mass per 100 parts by mass of the UV-curable resin, the convex parts formed on the surface of the curable resin layer will not be too small, and the three-dimensional surface roughness can be effectively given. When the pen weight pressure test is performed, the deformation of the surface protrusions is reduced, thereby suppressing the occurrence of cracks in the transparent conductive film, and providing a high-precision image. In addition, since there will be some surface protrusions in the transparent conductive film, it is also preferable to maintain the film's rollability.
此處作為一例，顯示於與形成透明導電膜之面相反面的硬化型樹脂層中使用無機粒子時之摻合比例。紫外線硬化型樹脂每100質量，較佳為無機粒子0.1～25質量份，更佳為0.1～15質量份，特佳為0.1～12質量份。 前述無機粒子之摻合量若紫外線硬化型樹脂每100質量份為0.1～25質量份，則在硬化型樹脂層表面所形成的凸部不過小，可有效果地賦予三次元表面粗糙度，可提供高精細的映像，再者由於在透明導電膜中會有一些表面突起，故亦可保持薄膜捲取性而較宜。Here, as an example, the blending ratio when using inorganic particles in the curing resin layer on the opposite side to the side where the transparent conductive film is formed is shown. For every 100 mass parts of the UV curing resin, the inorganic particles are preferably 0.1 to 25 mass parts, more preferably 0.1 to 15 mass parts, and particularly preferably 0.1 to 12 mass parts.If the blending amount of the aforementioned inorganic particles is 0.1 to 25 mass parts per 100 mass parts of the UV curing resin, the convex parts formed on the surface of the curing resin layer are not too small, and the three-dimensional surface roughness can be effectively given, which can provide a high-precision image. In addition, since there will be some surface protrusions in the transparent conductive film, it is also preferable to maintain the film rollability.
前述紫外線硬化型樹脂、光聚合起始劑及無機粒子或有機粒子或不相溶於紫外線硬化型樹脂的樹脂，係各自溶解於共通的溶劑中而調製塗布液。所使用的溶劑係沒有特別的限制，例如可單獨或混合使用如乙醇、異丙醇等之醇系溶劑，如乙酸乙酯、乙酸丁酯等之酯系溶劑，如二丁基醚、乙二醇單乙基醚等之醚系溶劑，如甲基異丁基酮、環己酮等之酮系溶劑，如甲苯、二甲苯、溶劑油等之芳香族烴系溶劑等。The aforementioned UV curable resin, photopolymerization initiator, and inorganic particles or organic particles or resin insoluble in the UV curable resin are dissolved in a common solvent to prepare a coating liquid. The solvent used is not particularly limited, and for example, alcohol solvents such as ethanol and isopropanol, ester solvents such as ethyl acetate and butyl acetate, ether solvents such as dibutyl ether and ethylene glycol monoethyl ether, ketone solvents such as methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbon solvents such as toluene, xylene, and solvent oil can be used alone or in combination.
塗布液中的樹脂成分之濃度，可考慮對應於塗布法的黏度等而適當地選擇。例如，塗布液中紫外線硬化型樹脂、光聚合起始劑及高分子量的聚酯樹脂之合計量佔有的比例通常為20～80質量%。又，此於塗布液中，視需要可添加其它眾所周知的添加劑，例如聚矽氧系調平劑等。The concentration of the resin component in the coating liquid can be appropriately selected in consideration of the viscosity corresponding to the coating method. For example, the total amount of the UV curable resin, the photopolymerization initiator and the high molecular weight polyester resin in the coating liquid is usually 20 to 80% by mass. In addition, other well-known additives such as silicone leveling agents can be added to the coating liquid as needed.
本發明中，所調製的塗布液係塗布於透明塑膠薄膜基材上。塗布法係沒有特別的限制，可使用棒塗法、凹版塗布法、反向塗布法等習知的方法。In the present invention, the prepared coating liquid is coated on a transparent plastic film substrate. The coating method is not particularly limited, and known methods such as rod coating, gravure coating, and reverse coating can be used.
經塗布的塗布液係在下一乾燥步驟中蒸發去除溶劑。於此步驟中，塗布液中均勻溶解的高分子量聚酯樹脂係變成粒子，析出至紫外線硬化型樹脂中。於將塗膜乾燥後，藉由將紫外線照射至塑膠薄膜，而紫外線硬化型樹脂進行交聯・硬化，形成硬化型樹脂層。於此硬化步驟中，高分子量聚酯樹脂的粒子係在硬塗層中被固定，同時在硬化型樹脂層之表面形成突起，提高廣域的表面粗糙度。The applied coating liquid is evaporated in the next drying step to remove the solvent. In this step, the high molecular weight polyester resin uniformly dissolved in the coating liquid is transformed into particles and precipitated into the UV curing resin. After the coating film is dried, the UV curing resin is crosslinked and cured by irradiating the plastic film with ultraviolet light to form a hardening resin layer. In this hardening step, the particles of the high molecular weight polyester resin are fixed in the hard coating layer, and protrusions are formed on the surface of the hardening resin layer, thereby increasing the surface roughness over a wide area.
又，硬化型樹脂層的厚度較佳為0.1～15μm之範圍，更佳為0.5～10μm之範圍，特佳為1～8μm之範圍。硬化型樹脂層的厚度為0.1μm以上時，形成充分的突起而較宜。另一方面，若為15μm以下，則生產性良好而較宜。 [實施例]Furthermore, the thickness of the hardening resin layer is preferably in the range of 0.1 to 15 μm, more preferably in the range of 0.5 to 10 μm, and particularly preferably in the range of 1 to 8 μm. When the thickness of the hardening resin layer is 0.1 μm or more, sufficient protrusions are preferably formed. On the other hand, if it is 15 μm or less, productivity is good and it is preferred.[Example]
以下藉由實施例更詳細地說明本發明，惟本發明完全不受此等實施例所限定。尚且，實施例中的各種測定評價係藉由下述方法進行。 (1)全光線透過率 依照JIS-K7136-1：1997，使用日本電色工業(股)製NDH-2000，測定全光線透過率。The present invention is described in more detail below by way of examples, but the present invention is not limited to these examples. Moreover, various measurements and evaluations in the examples are performed by the following methods.(1) Total light transmittanceThe total light transmittance was measured using NDH-2000 manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS-K7136-1:1997.
(2)表面電阻值 依據JIS-K7194：1994，以4端子法測定。測定機係使用三菱化學分析科技(股)製Lotesta AX MCP-T370。(2) Surface resistance valueMeasured by the 4-terminal method in accordance with JIS-K7194:1994. The measuring machine used was Lotesta AX MCP-T370 manufactured by Mitsubishi Chemical Analytical Technology Co., Ltd.
(3)三次元中心面平均表面粗糙度SRa 三次元中心面平均表面粗糙度SRa係ISO 25178中規定者，使用3次元表面形狀測定裝置VertScan(菱化系統公司製，R5500H-M100(測定條件：wave模式、測定波長560nm、物鏡10倍))，求出三次元中心面平均表面粗糙度SRa。將測定數設為5，求出彼等之平均值。此處，將nm單位的小數點第一位四捨五入。此處，將透明導電膜的三次元表面粗糙度SRa當作X，將透明塑膠薄膜基材上之與透明導電膜側相反面的三次元表面粗糙度SRa當作Y。(3) Three-dimensional center plane average surface roughness SRaThe three-dimensional center plane average surface roughness SRa is specified in ISO 25178. The three-dimensional center plane average surface roughness SRa is calculated using the three-dimensional surface shape measuring device VertScan (R5500H-M100 manufactured by Ryoka Systems Co., Ltd. (measurement conditions: wave mode, measurement wavelength 560nm, objective 10x)). The number of measurements is set to 5, and the average value is calculated. Here, the first decimal point of the nm unit is rounded off. Here, the three-dimensional surface roughness SRa of the transparent conductive film is taken as X, and the three-dimensional surface roughness SRa of the transparent plastic film substrate on the opposite side of the transparent conductive film is taken as Y.
(4)結晶粒徑 從積層有透明導電性薄膜層的薄膜試料片切出1mm×10mm的大小，使導電性薄膜面向外，貼附於適當的樹脂塊之上面。修整它後，藉由一般的超薄切片機之技法，製作大致平行於薄膜表面的超薄切片。 以穿透型電子顯微鏡(JEOL公司製，JEM-2010)觀察該切片，選擇無顯著損傷的導電性薄膜表面部分，以加速電壓200kV、直接倍率40000倍進行照相攝影。 於穿透型電子顯微鏡下觀察的結晶粒中，測定全部結晶粒的最長部，將彼等測定值之平均值當作結晶粒徑。此處，圖1～4中顯示與結晶粒的最長部之測定時最長部的認定方法有關之例。亦即，藉由能最大地測定各結晶粒之粒徑的直線之長度，認定最長部。(4) Crystalline grain sizeA 1 mm × 10 mm piece was cut from a thin film sample sheet on which a transparent conductive film layer was laminated, and the conductive film was placed on a suitable resin block with the conductive film facing outward. After trimming, ultrathin slices roughly parallel to the film surface were made using a general ultrathin slicer technique.The slices were observed using a transmission electron microscope (JEM-2010, manufactured by JEOL Corporation), and the surface portion of the conductive film without significant damage was selected and photographed at an accelerating voltage of 200 kV and a direct magnification of 40,000 times.Among the crystal grains observed under the transmission electron microscope, the longest part of all the crystal grains was measured, and the average value of these measured values was taken as the crystal grain size. Here, Figures 1 to 4 show an example of a method for identifying the longest part when measuring the longest part of a crystal grain. That is, the longest part is identified by the length of the straight line that can measure the grain size of each crystal grain to the maximum.
(5)透明導電膜的厚度(膜厚) 從積層有透明導電性薄膜層的薄膜試料片切出1mm×10mm之大小，包埋於電子顯微鏡用環氧樹脂中。將此固定在超薄切片機的試料保持器，製作平行於經包埋的試料片之短邊的剖面薄切片。接著，於此切片之薄膜的無顯著損傷之部位，使用穿透型電子顯微鏡(JEOL公司製，JEM-2010)，以加速電壓200kV、明視野、觀察倍率1萬倍進行照相攝影，從所得之照片求出膜厚。(5) Thickness of transparent conductive film (film thickness)A 1 mm × 10 mm piece was cut from a thin film sample sheet laminated with a transparent conductive thin film layer and embedded in an epoxy resin for electron microscope. This was fixed to the sample holder of an ultra-thin slicer and a cross-sectional thin section parallel to the short side of the embedded sample sheet was made. Then, a transmission electron microscope (JEM-2010, manufactured by JEOL) was used to photograph a portion of the thin film without significant damage at an accelerating voltage of 200 kV, bright field, and an observation magnification of 10,000 times, and the film thickness was determined from the obtained photograph.
(6)筆滑動耐久性試驗 使用本發明之透明導電性薄膜作為一面板，使用在玻璃基板上含有以濺鍍法形成厚度為20nm的銦-錫複合氧化物薄膜(氧化錫含量：10質量%)之透明導電性薄膜作為另一面板。以透明導電性薄膜呈對向之方式，隔著直徑30μm的環氧樹脂珠配置該2片面板，製作觸控面板。接著對於聚縮醛製的筆(前端的形狀：0.8mmR)施加5.0N的荷重，對於觸控面板進行18萬往返的直線滑動試驗。於此試驗中，對於本發明之透明導電性薄膜面施加筆的荷重。此時的滑動距離係設為30mm，滑動速度係設為180mm/秒。於此滑動耐久性試驗後，測定以筆荷重0.8N按壓滑動部時的ON電阻(可動電極(薄膜電極)與固定電極接觸時的電阻值)。ON電阻宜為10kΩ以下。 尚且，於比較例中，代替本發明之透明導電性薄膜，使用各比較例中的薄膜。(6) Pen sliding durability testThe transparent conductive film of the present invention was used as one panel, and a transparent conductive film containing an indium-tin composite oxide film (tin oxide content: 10 mass %) formed by sputtering with a thickness of 20 nm on a glass substrate was used as the other panel. The two panels were arranged in a manner such that the transparent conductive films were facing each other, and epoxy resin beads with a diameter of 30 μm were placed between them to produce a touch panel. Then, a load of 5.0 N was applied to a polyacetal pen (shape of the front end: 0.8 mmR), and a straight line sliding test of 180,000 reciprocating strokes was performed on the touch panel. In this test, the load of the pen was applied to the transparent conductive film surface of the present invention. At this time, the sliding distance was set to 30 mm, and the sliding speed was set to 180 mm/sec. After this sliding durability test, the ON resistance (resistance value when the movable electrode (thin film electrode) contacts the fixed electrode) when the sliding part is pressed with a pen load of 0.8N is measured. The ON resistance is preferably 10kΩ or less.Moreover, in the comparative examples, the thin film in each comparative example is used instead of the transparent conductive film of the present invention.
(7)筆重加壓試驗 使用經切成50mm×50mm的本發明之透明導電性薄膜作為一面板，使用在玻璃基板上含有以濺鍍法形成厚度為20nm的銦-錫複合氧化物薄膜(氧化錫含量：10質量%)之透明導電性薄膜作為另一面板。以透明導電性薄膜呈對向之方式，隔著直徑30μm的環氧樹脂珠配置該2片面板，以厚度經調整成120μm的雙面膠帶貼附薄膜側的面板與玻璃側的面板，製作觸控面板。以聚縮醛製的筆(前端的形狀0.8mmR)將35N的荷重施加於距雙面膠帶的邊端2.0mm的位置，與雙面膠帶平行地實施10次(往返5次)的直線滑動。於此試驗中，對於本發明之透明導電性薄膜面施加筆的荷重。此時的滑動距離係設為30mm，滑動速度係設為20mm/秒。惟，在無環氧樹脂珠的位置進行滑動。滑動後，卸除透明導電性薄膜，測定滑動部之任意5處的表面電阻(4端子法)，求出平均值。測定表面電阻時，在與滑動部垂直的方向上排列4端子，以使滑動部來到第2端子與第3端子之間的方式設定。將滑動部的表面電阻值之平均值除以未滑動部的表面電阻值(以4端子法測定)，算出表面電阻值之增加率。 尚且，於比較例中，代替本發明之透明導電性薄膜，使用各比較例中的薄膜。(7) Pen weight pressure testA transparent conductive film of the present invention cut into 50 mm × 50 mm was used as one panel, and a transparent conductive film containing an indium-tin composite oxide film (tin oxide content: 10 mass %) formed by sputtering with a thickness of 20 nm on a glass substrate was used as the other panel. The two panels were arranged with the transparent conductive films facing each other with epoxy beads of 30 μm in diameter interposed therebetween, and the film-side panel and the glass-side panel were attached with double-sided tape adjusted to a thickness of 120 μm to produce a touch panel. A load of 35N is applied to a position 2.0mm away from the edge of the double-sided tape using a polyacetal pen (the shape of the front end is 0.8mmR), and a straight line slide is performed 10 times (5 times back and forth) parallel to the double-sided tape. In this test, the load of the pen is applied to the transparent conductive film surface of the present invention. The sliding distance at this time is set to 30mm, and the sliding speed is set to 20mm/second. However, the sliding is performed at a position without epoxy resin beads. After sliding, the transparent conductive film is removed, and the surface resistance of any 5 points of the sliding part is measured (4-terminal method), and the average value is calculated. When measuring the surface resistance, 4 terminals are arranged in a direction perpendicular to the sliding part, and are set in a manner so that the sliding part comes between the second terminal and the third terminal. The average value of the surface resistance of the sliding part is divided by the surface resistance of the non-sliding part (measured by the 4-terminal method), and the increase rate of the surface resistance is calculated.Moreover, in the comparative examples, the thin film in each comparative example is used instead of the transparent conductive film of the present invention.
(8)透明導電膜中含有的氧化錫之含有率之測定 切取試料(約15cm2)，置入石英製三角燒瓶內，添加6mol/l鹽酸20ml，進行薄膜密封而使酸不揮發。於室溫下邊時常搖動邊放置9日，而使透明導電膜溶解。取出殘留的薄膜，將溶解有透明導電膜的鹽酸當作測定液，溶解液中的In、Sn係使用ICP發光分析裝置(廠商名；RIGAKU，裝置型式；CIROS-120 EOP)，藉由校正曲線法求出。各元素之測定波長係選擇不干渉的感度高之波長。又，標準溶液係稀釋市售的In、Sn之標準溶液而使用。(8) Determination of the content of tin oxide in the transparent conductive film. Cut a sample (about 15cm2 ) and place it in a quartz Erlenmeyer flask. Add 20 ml of 6 mol/l hydrochloric acid and seal the film to prevent the acid from volatile. Leave it at room temperature for 9 days with constant shaking to dissolve the transparent conductive film. Take out the remaining film and use the hydrochloric acid in which the transparent conductive film is dissolved as the measuring solution. The In and Sn in the dissolved solution are determined by the calibration curve method using an ICP luminescence analyzer (manufacturer name: RIGAKU, device type: CIROS-120 EOP). The measurement wavelength of each element is a wavelength with high sensitivity that does not interfere. In addition, the standard solution is a commercially available In and Sn standard solution diluted and used.
(9)附著性試驗 依據JIS K5600-5-6：1999實施。(9) Adhesion testImplemented in accordance with JIS K5600-5-6:1999.
(10)耐彎曲性試驗 依據JIS K5600-5-1：1999實施。惟，心軸直徑到13mm為止不發生破裂或剝落時，其以上的耐彎曲試驗不進行，皆記載為13mm。(10) Bending resistance testThis test is carried out in accordance with JIS K5600-5-1:1999. However, if the mandrel diameter does not crack or peel off up to 13mm, the bending resistance test above this is not performed and 13mm is recorded in all cases.
(11)透過影像清晰度試驗 依據JIS-K7105，測定梳寬0.125mm、0.25mm、0.5mm、1.0mm、2.0mm下之透明導電性薄膜的透過影像清晰度，求出各梳寬的透過影像清晰度之總和。測定機係使用SUGA試驗機(股)製影像清晰度測定器ICM-1T。(11) Through-image clarity testAccording to JIS-K7105, the through-image clarity of the transparent conductive film at comb widths of 0.125mm, 0.25mm, 0.5mm, 1.0mm, and 2.0mm was measured, and the sum of the through-image clarity of each comb width was calculated. The measuring machine used was the image clarity measuring instrument ICM-1T manufactured by SUGA Testing Instruments Co., Ltd.
實施例、比較例中使用的透明塑膠薄膜基材係在兩面具有易接著層的雙軸配向透明PET薄膜(東洋紡公司製A4340，厚度記載於表1中)。作為硬化型樹脂層，在含有光聚合起始劑的丙烯酸系樹脂(大日精化工業公司製，Seikabeam(註冊商標)EXF-01J)100質量份中，摻合表1記載之量的二氧化矽粒子(日產化學公司製，Snowtex ZL)，將作為溶劑的甲苯/MEK(8/2：質量比)之混合溶劑以固體成分濃度成為50質量%之方式添加，攪拌而均勻地溶解，調製塗布液(將此塗布液在以下稱為塗布液A)。以塗膜的厚度成為5μm之方式，將所調製的塗布液，使用馬亞棒進行塗布。在80℃下進行1分鐘乾燥後，使用紫外線照射裝置(EYEGRAPHICS公司製，UB042-5AM-W型)照射紫外線(光量：300mJ/cm2)，而使塗膜硬化。又，硬化型樹脂層係設於透明塑膠基材之兩面。The transparent plastic film substrate used in the examples and comparative examples is a biaxially oriented transparent PET film (A4340 manufactured by Toyobo Co., Ltd., thickness is shown in Table 1) having an easy-adhesion layer on both sides. As a curable resin layer, 100 parts by weight of an acrylic resin containing a photopolymerization initiator (Seikabeam (registered trademark) EXF-01J manufactured by Dainichi Seika Co., Ltd.) was mixed with silica particles (Snowtex ZL manufactured by Nissan Chemical Co., Ltd.) in an amount shown in Table 1, and a mixed solvent of toluene/MEK (8/2: mass ratio) was added as a solvent so that the solid content concentration became 50% by weight, and the mixture was stirred and uniformly dissolved to prepare a coating liquid (hereinafter referred to as coating liquid A). The prepared coating solution was applied using a Maya rod so that the coating thickness was 5 μm. After drying at 80°C for 1 minute, the coating was cured by irradiating with ultraviolet rays (light intensity: 300 mJ/cm2 ) using an ultraviolet irradiation device (manufactured by EYEGRAPHICS, UB042-5AM-W model). The curable resin layer was provided on both sides of the transparent plastic substrate.
(實施例1～8) 各實施例水準係基於表1中所示的條件，如以下地實施。 於真空槽中投入薄膜，抽真空到1.5×10-4Pa為止。接著，於氧導入後，導入表1中記載之濃度的作為惰性氣體之氬、作為含氫的氣體之氫氣，使總壓成為0.6Pa。 對於銦-錫複合氧化物的燒結靶或不含氧化錫的氧化銦燒結靶，以3W/cm2之電力密度投入電力，藉由DC磁控濺鍍法，將透明導電膜成膜。膜厚係改變薄膜通過靶上時的速度而控制。又，關於濺鍍時之成膜環境的水分壓相對於惰性氣體之比，使用氣體分析裝置(INFICON公司製，Transpector XPR3)進行測定。於各實施例水準中，為了調節濺鍍時之成膜環境的水分壓相對於惰性氣體之比，如表1中記載，調節轟擊步驟之有無、薄膜捲筒端面之凹凸高低差、控制薄膜接觸行進的中央輥之溫度的調溫機之溫媒的溫度。將正好在從向薄膜捲筒的成膜開始時到成膜結束時的溫度之最大值與最小值的正中央之溫度當作中心值，記載於表1。 成膜積層有透明導電膜的薄膜，係在進行表1中記載的熱處理後，實施測定。表1中顯示測定結果。(Examples 1 to 8) Each example level is based on the conditions shown in Table 1 and is implemented as follows. A thin film is placed in a vacuum chamber and the vacuum is evacuated to 1.5×10-4 Pa. Then, after the introduction of oxygen, argon as an inert gas and hydrogen as a hydrogen-containing gas are introduced at the concentrations shown in Table 1 to make the total pressure 0.6 Pa. For a sintered target of indium-tin composite oxide or a sintered target of indium oxide without tin oxide, electric power is applied at an electric power density of 3 W/cm2 to form a transparent conductive film by DC magnetron sputtering. The film thickness is controlled by changing the speed at which the thin film passes over the target. In addition, the ratio of the water pressure in the film-forming environment during sputtering to the inert gas was measured using a gas analyzer (Inficon Transpector XPR3). In order to adjust the ratio of the water pressure in the film-forming environment during sputtering to the inert gas, the presence or absence of the impact step, the height difference of the film roll end surface, and the temperature of the temperature medium of the temperature controller that controls the temperature of the center roll on which the film is in contact were adjusted as shown in Table 1. The temperature at the exact center of the maximum and minimum values from the start of film formation to the end of film formation on the film roll was taken as the center value and recorded in Table 1. The thin film having the transparent conductive film laminated thereon was subjected to the heat treatment listed in Table 1 and then subjected to the measurement. Table 1 shows the measurement results.
(比較例1～9) 於表1中記載之條件下與實施例1同樣地製作透明導電性薄膜，進行評價。惟，比較例7不設置硬化型樹脂層。但，比較例8係將硬化型樹脂層的塗膜之厚度調整成20μm。表2中顯示結果。(Comparative Examples 1 to 9)Under the conditions listed in Table 1, a transparent conductive film was prepared in the same manner as in Example 1 and evaluated. However, in Comparative Example 7, no curable resin layer was provided. However, in Comparative Example 8, the thickness of the coating of the curable resin layer was adjusted to 20 μm. The results are shown in Table 2.
[表1A]
[表1B]
[表2A]
[表2B]
如表1A、1B中記載，實施例1～8記載之透明導電性薄膜係筆滑動耐久性、筆重加壓耐久性、高精細性優異，兼備全部的特性。然而，如表2中記載，比較例1～9無法全部滿足筆滑動耐久性、筆重加壓耐久性、高精細性。 [產業上利用之可能性]As shown in Tables 1A and 1B, the transparent conductive films described in Examples 1 to 8 are excellent in pen sliding durability, pen weight pressure durability, and high precision, and have all the characteristics. However, as shown in Table 2, Comparative Examples 1 to 9 cannot fully satisfy pen sliding durability, pen weight pressure durability, and high precision.[Possibility of industrial use]
如上述，根據本發明，可製作筆滑動耐久性、筆重加壓耐久性、高精細性優異之透明導電性薄膜，此係極有用於電阻膜式觸控面板等之用途。As described above, according to the present invention, a transparent conductive film having excellent pen sliding durability, pen weight pressure durability, and high precision can be produced, which is extremely useful for applications such as resistive film touch panels.
1:薄膜 2:中央輥 3:煙囪 4:銦-錫複合氧化物的靶1: Thin film2: Central roller3: Chimney4: Indium-tin composite oxide target
圖1係顯示本發明中的結晶粒之最長部的一例(其1)之示意圖。 圖2係顯示本發明中的結晶粒之最長部的其它一例(其2)之示意圖。 圖3係顯示本發明中的結晶粒之最長部的其它一例(其3)之示意圖。 圖4係顯示本發明中的結晶粒之最長部的其它一例(其4)之示意圖。 圖5係用於說明本發明中所適合使用的濺鍍裝置的一例之中央輥的位置之示意圖。FIG. 1 is a schematic diagram showing an example (part 1) of the longest part of the crystal grain in the present invention.FIG. 2 is a schematic diagram showing another example (part 2) of the longest part of the crystal grain in the present invention.FIG. 3 is a schematic diagram showing another example (part 3) of the longest part of the crystal grain in the present invention.FIG. 4 is a schematic diagram showing another example (part 4) of the longest part of the crystal grain in the present invention.FIG. 5 is a schematic diagram for explaining the position of the central roller of an example of a sputtering device suitable for use in the present invention.
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| TW110135760ATWI886342B (en) | 2020-09-29 | 2021-09-27 | Transparent conductive film |
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| TW202033628A (en)* | 2018-09-28 | 2020-09-16 | 日商住友化學股份有限公司 | Optical film |
| Publication number | Publication date |
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| TW202219989A (en) | 2022-05-16 |
| JP2024180466A (en) | 2024-12-26 |
| JP7732564B2 (en) | 2025-09-02 |
| WO2022070609A1 (en) | 2022-04-07 |
| CN115769315A (en) | 2023-03-07 |
| JP7582198B2 (en) | 2024-11-13 |
| JPWO2022070609A1 (en) | 2022-04-07 |
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