TW201324546A - Substrate with transparent electrically conducting layer and method of producing the same - Google Patents

Abstract

The present invention relates to a substrate with transparent electrically conductive layer and a method of producing substrate with transparent electrically conductive layer. The substrate with transparent electrically conductive layer is including a colored transparent layer having the absorbance at wavelength of 450nm, 550nm, and 650nm in the range of 0.001 to 0.1 independently and value of Hayes in the range of 0.1 to 2%, and a transparent electrically conductive layer containing metal nanowire on a transparent layer substrate in turn. The method of producing substrate with transparent electrically conductive layer is to form above colored transparent layer and above transparent electrically conductive layer by coating on the transparent layer substrate, to peel off after bonding with support medium which is having a adhesion region layer has been negative patterned, and to transfer a part of above transparent electrically conductive layer contacting with above adhesion region to the above adhesion region to form the pattern of transparent electrically conductive layer on the transparent layer substrate, and then, to immobilise transparent electrically conductive layer on a substrate by applying a coating for protective layer.

Description

附透明導電層之基體及其製造方法 Substrate with transparent conductive layer and manufacturing method thereof

本發明係關於一種具有含金屬奈米線之透明導電層的附透明導電層之基體及其製造方法。 The present invention relates to a substrate having a transparent conductive layer having a metal nanowire-containing transparent conductive layer and a method of manufacturing the same.

於透明基體上形成有透明導電層之附透明導電層的基體，係在利用發光、受光功能之顯示元件等中，有許多被使用作為重要的功能性構件。尤其是藉由將透明導電層圖案化，於片狀之透明基體上配置排列許多導電性區域且具有電極或開關等之功能之透明導電性片，係成為用於上述顯示元件之薄型化、小型化、高功能化之必須之構件。 A substrate having a transparent conductive layer and a transparent conductive layer formed on a transparent substrate is used as an important functional member in display elements using light-emitting and light-receiving functions. In particular, by patterning a transparent conductive layer, a transparent conductive sheet having a plurality of conductive regions and having functions such as electrodes or switches is disposed on a sheet-like transparent substrate, and is used for thinning and small-sized display elements. The necessary components for the transformation and high functionality.

通常透明導電層之圖案係採用，於透明基體上藉由蒸鍍或濺鍍等形成ITO層或氧化鋅層，其後，併用電漿等之乾式蝕刻，或正型/負型光阻來圖案化的方法。然而，有蒸鍍或濺鍍法需要相當大的裝置或能量，或為了賦予高功能化之一的可撓性而使用塑膠薄膜作為透明基體時，蒸鍍或濺鍍時之熱所引起之塑膠薄膜翹曲等問題發生。因此，要求有不太需要熱能，且製造裝置簡便、生產性高之透明導電性片。 Generally, a pattern of a transparent conductive layer is used, and an ITO layer or a zinc oxide layer is formed on a transparent substrate by evaporation or sputtering, and thereafter, dry etching by plasma or the like, or positive/negative photoresist is used for patterning. Method. However, there are a large amount of equipment or energy required for vapor deposition or sputtering, or a plastic caused by heat during evaporation or sputtering when a plastic film is used as a transparent substrate in order to impart flexibility to one of high functionality. Problems such as film warpage occur. Therefore, there is a demand for a transparent conductive sheet which is less in need of heat energy and which is simple in manufacturing apparatus and high in productivity.

作為不太需要熱能且製造裝置簡便的方法，有研究將金屬或碳等之導電性奈米線之塗布液塗布於基體而獲得透明導電層之方法。尤其是金屬奈米線係作為電阻率小、可能形成更低表面電阻值之透明電極的材料而受到注目(例如：參照專利文獻1)。 As a method which does not require thermal energy and the manufacturing apparatus is simple, a method of applying a coating liquid of a conductive nanowire such as metal or carbon to a substrate to obtain a transparent conductive layer has been studied. In particular, the metal nanowire system is attracting attention as a material having a small resistivity and a transparent electrode which may have a lower surface resistance value (for example, refer to Patent Document 1).

而由於金屬奈米線係具有縱橫比之金屬，故入射並通過透明導電層之光不僅是金屬反射，係成為金屬奈米線獨特的亂反射、而有被辨識為帶黃色之顏色之事。其不適用於顯示元件等要求有正確的顏色再現性之電極，而用途受到限定。 Since the metal nanowire has a metal having an aspect ratio, the light incident on the transparent conductive layer is not only a metal reflection, but also a unique disordered reflection of the metal nanowire, and is recognized as a yellowish color. It is not suitable for an electrode such as a display element that requires correct color reproducibility, and its use is limited.

作為抑制上述金屬奈米線之亂反射的方法，已知有例如：於透明底漆上形成包含導電性粒子與經著色之樹脂黏合劑的透明導電構件之方法(例如參照專利文獻2)，或是使用了表面經黑化處理之金屬奈米線的透明導電構件(例如參照專利文獻3)。 As a method of suppressing the disordered reflection of the above-mentioned metal nanowires, for example, a method of forming a transparent conductive member containing conductive particles and a colored resin binder on a transparent primer (for example, refer to Patent Document 2), or It is a transparent conductive member using a metal nanowire whose surface is blackened (for example, refer to Patent Document 3).

然而，記載於專利文獻2之方法，由於經著色之樹脂黏合劑會阻礙金屬奈米線之接觸，因此有所得之導電層的電阻值上升之虞，或信賴性下降之虞。又專利文獻3之方法亦為處理金屬奈米線本身，也同樣有導電層之電阻值上升之虞，或信賴性下降之虞。 However, in the method described in Patent Document 2, since the colored resin binder hinders the contact of the metal nanowires, the resistance value of the obtained conductive layer may increase or the reliability may decrease. Further, in the method of Patent Document 3, the metal nanowire itself is treated, and the resistance value of the conductive layer is also increased, or the reliability is lowered.

另一方面，亦有提案以校正觸控面板之ITO透明電極的顏色為目的之色校正用片(例如參照專利文獻4)。此係設置一種利用濺鍍而獲得均勻之金屬膜的具有相對於ITO之色調為互補色之片的方法。然而，並無記載金屬奈米線之金屬亂反射的見解，又，亦無記載關於係為互補色之色材的見解。 On the other hand, there is a proposal for a color correction sheet for correcting the color of the ITO transparent electrode of the touch panel (see, for example, Patent Document 4). This is a method of providing a sheet having a complementary color to the ITO with a uniform metal film by sputtering. However, there is no description of the disordered reflection of the metal of the metal nanowire, and there is no description of the color material which is a complementary color.

先前技術文獻 Prior technical literature 專利文獻 Patent literature

專利文獻1 日本特表2009-505358號公報 Patent Document 1 Japanese Special Table 2009-505358

專利文獻2 日本特開2011-34889號公報 Patent Document 2 Japanese Patent Laid-Open Publication No. 2011-34889

專利文獻3 日本特開2011-70820號公報 Patent Document 3 Japanese Patent Laid-Open Publication No. 2011-70820

專利文獻4 日本特開2010-20682號公報 Patent Document 4 Japanese Patent Laid-Open Publication No. 2010-20682

本發明係提供一種顯示良好電阻值、且為透明而色再現性優異的附透明導電層之基體。 The present invention provides a substrate with a transparent conductive layer which exhibits a good electrical resistance value and is excellent in transparency and color reproducibility.

本發明人等，係於透明基體與含有金屬奈米線的透明導電層之間，設置波長450nm、波長550nm及波長650nm之吸光度分別獨立為在0.001~0.1之範圍，且霧度值為在0.1~2%之範圍的有色之透明層作為底塗(anchor coat)層，以解決前述課題。 The inventors of the present invention set the absorbance at a wavelength of 450 nm, a wavelength of 550 nm, and a wavelength of 650 nm between a transparent substrate and a transparent conductive layer containing a metal nanowire, respectively, in the range of 0.001 to 0.1, and a haze value of 0.1. The colored transparent layer in the range of ~2% is used as an anchor coat layer to solve the aforementioned problems.

藉由以設置有色之透明層，吸收一部份在金屬奈米線被亂反射之光，而使亂反射光不容易被辨識。作為有色之透明層，具體而言，含有π共軛系化合物之層，係可一面維持良好導電性，一面改善辨認性而較佳。 By arranging a colored transparent layer to absorb a portion of the light that is randomly reflected on the metal nanowire, the scattered reflected light is not easily recognized. As the colored transparent layer, specifically, the layer containing the π-conjugated compound is preferable because it can maintain good conductivity while improving the visibility.

即，本發明提供，一種附透明導電層之基體，其係於透明基體上，依序具有波長450nm、波長550nm及波長650nm之吸光度分別獨立為在0.001~0.1之範圍，且霧度值為在0.1~2%之範圍的有色之透明層(1)，與含有金屬奈米線之透明導電層(2)。 That is, the present invention provides a substrate with a transparent conductive layer which is attached to a transparent substrate, and has an absorbance of 450 nm, a wavelength of 550 nm, and a wavelength of 650 nm, respectively, independently ranging from 0.001 to 0.1, and the haze value is A colored transparent layer (1) in the range of 0.1 to 2%, and a transparent conductive layer (2) containing a metal nanowire.

又，本發明提供一種附透明導電層之基體之製造方法，其係具有下列步驟之上述附透明導電層之基體的製造方法： 於基體上，藉由塗布而形成波長450nm、波長550nm及波長650nm之吸光度分別獨立為在0.001~0.1之範圍，且霧度值為在0.1~2%之範圍的有色之透明層(1)的步驟1；與於上述透明層(1)上，藉由塗布而形成含有金屬奈米線之可剝離透明導電層(2)的步驟2；與於支撐體上，形成具有經負型圖案化的接著區域之層的步驟3；與將上述基體與上述支撐體貼合、使上述透明導電層(2)與具有上述接著區域之層的該接著區域相互密合的步驟4；與將上述支撐體自上述基體剝離，並藉由使與具有上述接著區域之層的該接著區域密合之部分的該透明導電層(2)，轉移至具有接著區域之層的該接著區域上，而於基體上形成透明導電層(2)之圖案之步驟5；與於形成有上述透明導電層(2)之圖案的基體整面，塗布保護層用途料，並將透明導電層(2)於基體上固定化的步驟6。 Moreover, the present invention provides a method of manufacturing a substrate with a transparent conductive layer, which is a method for manufacturing a substrate having the above transparent conductive layer having the following steps: Forming a colored transparent layer (1) having a wavelength of 450 nm, a wavelength of 550 nm, and a wavelength of 650 nm by coating, respectively, in a range of 0.001 to 0.1 and a haze value of 0.1 to 2% by coating. Step 1; and step 2 of forming a peelable transparent conductive layer (2) containing a metal nanowire by coating on the transparent layer (1); forming a negative pattern on the support Step 3 of the layer of the region; step 4 of bonding the substrate to the support to make the transparent conductive layer (2) and the bonding region having the layer of the bonding region adhere to each other; and the supporting body The substrate is peeled off, and the transparent conductive layer (2) adhered to the bonding region having the layer of the bonding region is transferred to the bonding region of the layer having the bonding region to form on the substrate Step 5 of patterning the transparent conductive layer (2); coating the protective layer with the entire surface of the substrate on which the pattern of the transparent conductive layer (2) is formed, and fixing the transparent conductive layer (2) on the substrate Step 6.

根據本發明，可以提供一種顯示良好電阻值、且抑制黃色性之係透明性而色再現性優異的附透明導電層之基體。 According to the present invention, it is possible to provide a substrate with a transparent conductive layer which exhibits a good electrical resistance value and which suppresses yellowness and is excellent in color reproducibility.

又，本發明之附透明導電層之基體的製造方法，係可全部以塗布步驟形成，且可不需對該透明導電層進行蝕刻等之濕式處理而圖案化，更進一步可良好地固定化如此而形成之透明導電層，而不需燒結或燒成處理。 Further, the method for producing a substrate with a transparent conductive layer of the present invention can be formed by a coating step, and can be patterned without performing a wet treatment such as etching on the transparent conductive layer, and can be further fixed. The transparent conductive layer is formed without sintering or firing treatment.

[實施發明之形態] [Formation of the Invention]

(有色之透明層(1)) (Colored transparent layer (1))

作為在本發明使用的有色之透明層(1)，只要是波長450nm、波長550nm及波長650nm之吸光度係分別獨立為在0.001~0.1之範圍，且霧度值為在0.1~2%之範圍，則無特別限定。 As the colored transparent layer (1) used in the present invention, the absorbance systems having a wavelength of 450 nm, a wavelength of 550 nm, and a wavelength of 650 nm are each independently in the range of 0.001 to 0.1, and the haze value is in the range of 0.1 to 2%. There is no particular limitation.

(吸光度) (absorbance)

本發明中之吸光度，係指於基於JIS K-0115之方法中所測定者，具體而言係顯示以以下之方法測定之值。 The absorbance in the present invention means a value measured in the method based on JIS K-0115, specifically, a value measured by the following method.

(吸光度測定方法) (absorbance measurement method)

使用分光光度計(日本分光公司製V-650)，測定波長380nm~780nm之吸光度，並測定波長450nm、波長550nm、波長650nm之吸光度α₄₅₀、α₅₅₀、α₆₅₀。 The absorbance at a wavelength of 380 nm to 780 nm was measured using a spectrophotometer (V-650, manufactured by JASCO Corporation), and the absorbances α ₄₅₀ , α ₅₅₀ , and α ₆₅₀ having a wavelength of 450 nm, a wavelength of 550 nm, and a wavelength of 650 nm were measured.

就謀求透射率與辨識性兩立之點，在本發明使用的有色之透明層(1)的吸光度，較佳為在上述波長450nm、波長550nm、波長650nm之範圍中，係為在0.001~0.1之範圍，更佳為在0.001~0.02之範圍，再更佳為在0.001~0.01之範圍。各波長之吸光度可相同亦可不同。若吸光度未滿0.001，係無法獲得充分之光吸收效果，而金屬奈米線之亂反射光會有容易被辨識之傾向。另一方面，若吸光度超過0.1，則光吸收效果變得過高，有總透光率降低之虞。 In order to achieve both transmittance and visibility, the absorbance of the colored transparent layer (1) used in the present invention is preferably in the range of 450 nm, 550 nm, and 650 nm, which is 0.001 to 0.1. The range is more preferably in the range of 0.001 to 0.02, and even more preferably in the range of 0.001 to 0.01. The absorbance at each wavelength may be the same or different. If the absorbance is less than 0.001, sufficient light absorption cannot be obtained, and the scattered light of the metal nanowire tends to be easily recognized. On the other hand, when the absorbance exceeds 0.1, the light absorbing effect becomes too high, and the total light transmittance is lowered.

例如作為觸控面板用之透明電極層而使用之情形時，由於係要求更高之透明度，吸光度較佳為在0.001 ~0.1之範圍。另一方面，作為太陽電池用之透明電極層而使用之情形時，由於不要求達到觸控面板用之透明度，只要吸光度為0.001~0.2之範圍左右即可。 For example, when used as a transparent electrode layer for a touch panel, since a higher transparency is required, the absorbance is preferably 0.001. The range of ~0.1. On the other hand, in the case of being used as a transparent electrode layer for a solar cell, since it is not required to achieve transparency for a touch panel, the absorbance may be in the range of about 0.001 to 0.2.

(霧度值、總透光率) (haze value, total light transmittance)

又，在本發明中，霧度值係指在基於JIS K-7136之方法中所測定者。又，總透光率，係指在基於JIS K-7361之方法中所測定者，具體而言係顯示以以下之方法測定之值。 Further, in the present invention, the haze value refers to one measured in the method based on JIS K-7136. In addition, the total light transmittance is measured by the method based on JIS K-7361, and specifically shows the value measured by the following method.

(霧度值、總透光率之測定方法) (Haze value, total light transmittance measurement method)

使用積分球式總透光率測定機(日本電色工業公司製NDH-2000)，測定霧度(霧度．Hz){根據JIS K-7136、NDH-2000測定方法3}，與總透光率(Tt){根據JIS K-7361、NDH-2000測定方法1}。 Using an integrating sphere type total light transmittance measuring machine (NDH-2000, manufactured by Nippon Denshoku Industries Co., Ltd.), measuring haze (haze. Hz) {according to JIS K-7136, NDH-2000 measuring method 3}, and total light transmission Rate (Tt) {Measurement method 1 according to JIS K-7361, NDH-2000.

於本發明使用的有色之透明層(1)之霧度值的範圍，係較佳為0.1~2%，更佳為0.1~1%，若為0.1~0.5%則再更佳。霧度值未滿0.1%之情形，意味著該透明層之厚度過薄，由於光吸收效果過低，會有金屬奈米線之亂反射容易辨識的情形。另一方面，霧度值超過2%之情形，意味著該透明層之厚度過厚，會有光吸收效果變得過高，總透光率降低之情形。 The range of the haze value of the colored transparent layer (1) used in the present invention is preferably 0.1 to 2%, more preferably 0.1 to 1%, and even more preferably 0.1 to 0.5%. When the haze value is less than 0.1%, it means that the thickness of the transparent layer is too thin, and since the light absorbing effect is too low, there is a case where the disordered reflection of the metal nanowire is easily recognized. On the other hand, when the haze value exceeds 2%, it means that the thickness of the transparent layer is too thick, and the light absorbing effect becomes too high, and the total light transmittance is lowered.

例如作為觸控面板用之透明電極層而使用之情形時，由於要求更高之透明度，所獲得之附透明導電層之基體的霧度值，係較佳為於0.1~2%之範圍，若為0.1~0.5%則又更佳。以使透明層之霧度值成為上述範圍，而使附透明導電層之基體的霧度值變得容易調整於 該範圍。另一方面，作為太陽電池用之透明電極層而使用之情形時，由於不要求達到觸控面板用所使用之透明導電層的透明度，霧度值係只要為0.1~10%之範圍左右即可。 For example, when used as a transparent electrode layer for a touch panel, since a higher transparency is required, the haze value of the obtained substrate with a transparent conductive layer is preferably in the range of 0.1 to 2%. It is better if it is 0.1~0.5%. In order to make the haze value of the transparent layer into the above range, the haze value of the substrate with the transparent conductive layer can be easily adjusted. The range. On the other hand, when it is used as a transparent electrode layer for a solar cell, since it is not required to achieve the transparency of the transparent conductive layer used for the touch panel, the haze value is only about 0.1 to 10%. .

在本發明使用的有色之透明層(1)，只要是具有上述吸光值及霧度的透明層，則無特別限制，但是若為包含含有著色材之透明樹脂被膜的有色之透明層(1)，則由於容易形成而較佳。含有該著色材之透明樹脂被膜，係以塗布至少含有著色劑與黏合劑樹脂之塗布組成物，並乾燥及/或硬化，而可容易地形成。 The colored transparent layer (1) used in the present invention is not particularly limited as long as it has the above-mentioned light absorption value and haze, but is a colored transparent layer containing a transparent resin film containing a coloring material (1) It is preferred because it is easy to form. The transparent resin film containing the coloring material can be easily formed by applying a coating composition containing at least a coloring agent and a binder resin, and drying and/or curing.

作為使用於上述有色之透明層(1)的著色材，由於容易將吸光度及霧度值調整於適當的範圍，係較佳使用π共軛系化合物。作為在本發明使用之π共軛系化合物，只要是具有芳香族烴環或芳香族雜環者，則任何構造亦可，可舉出例如：「Organic Field-Effect Transistors」(2007年刊、CRC Press)159-228頁記載之物，或其他習知的有機半導體分子。較佳為具有苯環、吡啶環、吡環、嘧啶環、三環、吡咯環、吡唑環、咪唑環、***環、唑環、噻唑環、呋喃環、噻吩環等芳香族烴環或芳香族雜環之構造，更佳為該等之芳香族烴環或芳香族雜環係2個以上被縮環，及/或被以共價鍵連結，該等之芳香族烴環或芳香族雜環較佳為分別所具有之π電子係寬廣的非定域化構造。被縮環及/或被以共價鍵連結之芳香族烴環或芳香族雜環之數量，較佳為1~20個，更佳為2~12個。 As a coloring material used for the above-mentioned colored transparent layer (1), it is preferable to use a π-conjugated compound because it is easy to adjust the absorbance and the haze value to an appropriate range. The π-conjugated compound to be used in the present invention may be any structure as long as it has an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and examples thereof include "Organic Field-Effect Transistors" (2007, CRC Press) ) 159-228, or other conventional organic semiconductor molecules. Preferably, it has a benzene ring, a pyridine ring, and a pyridyl group. Ring, pyrimidine ring, three Ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, a structure of an aromatic hydrocarbon ring or an aromatic heterocyclic ring such as an azole ring, a thiazole ring, a furan ring or a thiophene ring, more preferably two or more of these aromatic hydrocarbon rings or aromatic heterocyclic rings are condensed, and/or The aromatic hydrocarbon ring or the aromatic heterocyclic ring is preferably a non-localized structure having a wide π-electron system. The number of the aromatic hydrocarbon ring or the aromatic heterocyclic ring which is condensed and/or covalently bonded is preferably from 1 to 20, more preferably from 2 to 12.

作為上述π共軛系化合物之具體例，可舉出：酞青素類、卟啉類、蔥(anthracene)、稠四苯(tetracene)、稠五苯(pentacene)、伸三苯、六苯并蔻(hexabenzo coronene)、富勒烯(fullerene)、聚吡咯類、聚噻吩類、聚乙炔類、聚苯類、聚對苯乙烯(polyphenylene vinylene)類、聚苯胺類、聚并苯類、聚噻吩乙烯(polypyrrole vinylene)類，及此等之共聚物等。 Specific examples of the π-conjugated compound include anthracyclines, porphyrins, anthracene, tetracene, pentacene, triphenylene, and hexabenzopyrene. (hexabenzo coronene), fullerene, polypyrrole, polythiophene, polyacetylene, polyphenylene, polyphenylene vinylene, polyaniline, polyacene, polythiophene (polypyrrole vinylene), and copolymers thereof.

其中，被作為色素使用之酞青素類，或被作為抗靜電劑使用之聚吡咯類、聚噻吩類、聚乙炔類、聚苯類、聚對苯乙烯類、聚苯胺類、聚并苯類、聚噻吩乙烯類等之導電性高分子，由於透明性優異，可容易塗膜化而較佳。尤其是導電性高分子係作為抗靜電膜而作用之故，可防止靜電放電所引起之銀奈米線塗膜的靜電破壞等。 Among them, anthocyanins used as pigments, or polypyrroles, polythiophenes, polyacetylenes, polyphenyls, polyparaphenylenes, polyanilines, polyacenes used as antistatic agents A conductive polymer such as polythiophene ethylene is preferred because it is excellent in transparency and can be easily coated. In particular, since the conductive polymer acts as an antistatic film, it is possible to prevent electrostatic breakdown or the like of the silver nanowire coating film caused by electrostatic discharge.

又，呈現青色之色素，由於特別容易減低所獲得的附透明導電層之基體的黃色度而較佳。特佳使用聚噻吩系著色材，可使用PEDOT(SIGMA-ALDRICH公司製)，或含有聚噻吩系著色材之ARACOAT AS601(荒川化學工業公司製)等之市售品。 Further, a cyan coloring matter is preferable because it is particularly easy to reduce the yellowness of the obtained substrate with a transparent conductive layer. A commercially available product such as PEDOT (manufactured by SIGMA-ALDRICH Co., Ltd.) or ARACOAT AS601 (manufactured by Arakawa Chemical Industries Co., Ltd.) containing a polythiophene-based coloring material can be used as the polythiophene-based coloring material.

使用上述共軛系化合物作為上述有色之透明層(1)之情形時，由操作性及對基體之密合性之觀點，較佳係混合成為黏合劑之樹脂或各種溶劑等作為塗布溶液使用。作為混合之樹脂可舉出：聚酯系樹脂、聚胺甲酸酯樹脂、聚酯胺甲酸酯樹脂、丙烯酸系樹脂、三聚氰胺樹脂、氯乙烯系樹脂、苯乙烯系樹脂、聚碳酸酯系樹脂、環烯烴系樹脂(cycloolefin)等。其中，聚酯系樹脂、丙烯 酸系樹脂在透明性高之點係較佳。又於不損及本發明之效果的範圍內，使用各種添加劑亦無妨。又，即便是使用導電性高分子作為上述有色之透明層(1)的情形，為了提升與透明基體之密合性，亦可混合上述聚酯系樹脂等之樹脂。透明基體為塑膠等之樹脂片之情形時，以選擇具有與該透明基體之樹脂構造類似之構造的樹脂，而可更提高密合性。上述共軛系化合物之塗布溶液的濃度，視使用之共軛系化合物，只要可適當調整為如維持上述吸光度與霧度，則無特別地限定。 When the conjugated compound is used as the colored transparent layer (1), it is preferred to use a resin or a solvent which is a binder, as a coating solution, from the viewpoint of workability and adhesion to a substrate. Examples of the resin to be mixed include a polyester resin, a polyurethane resin, a polyester urethane resin, an acrylic resin, a melamine resin, a vinyl chloride resin, a styrene resin, and a polycarbonate resin. A cycloolefin or the like. Among them, polyester resin, propylene The acid resin is preferred in that the transparency is high. Further, it is also possible to use various additives within the range which does not impair the effects of the present invention. In addition, even when a conductive polymer is used as the colored transparent layer (1), a resin such as the above-mentioned polyester resin may be mixed in order to improve the adhesion to the transparent substrate. When the transparent substrate is a resin sheet such as plastic, the resin having a structure similar to that of the transparent substrate can be selected to improve the adhesion. The concentration of the coating solution of the above-mentioned conjugated compound is not particularly limited as long as it can be appropriately adjusted so as to maintain the above absorbance and haze, depending on the conjugated compound to be used.

作為上述有色之透明層(1)之厚度，只要是可維持吸光度與霧度之範圍，則無特別限定，例如：當以後述之剝離法製作本發明的附透明導電層之基體時，較佳為不與透明導電層被一同剝離之程度的膜厚。具體而言，較佳為在0.1μm~1.0μm之範圍。 The thickness of the colored transparent layer (1) is not particularly limited as long as it can maintain the range of absorbance and haze. For example, when the base material with a transparent conductive layer of the present invention is produced by a peeling method described later, it is preferred. It is a film thickness to the extent that it is not peeled off together with the transparent conductive layer. Specifically, it is preferably in the range of 0.1 μm to 1.0 μm.

作為設置上述有色之透明層(1)的方法，較佳為塗布法。作為塗布法係可使用噴霧塗布、棒塗布、輥塗布、模塗布、噴墨塗布、網版塗布、浸漬塗布等習知之塗布方法。又，可藉由在薄膜製造步驟設置塗布層之線上塗布(in-line coat)方式、在薄膜製造後設置塗布層之離線塗布(off-line coat)方式來設置。 As a method of providing the above colored transparent layer (1), a coating method is preferred. As the coating method, a conventional coating method such as spray coating, bar coating, roll coating, die coating, inkjet coating, screen coating, or dip coating can be used. Further, it can be provided by an in-line coating method in which a coating layer is provided in a film production step, and an off-line coating method in which a coating layer is provided after film production.

(透明基體) (transparent substrate)

作為使用作為本發明的附透明導電層之基體的支撐體之透明基體，只要是具有作為支撐體之充分的物理強度與透光性者，則無特別限定，但是片狀之透明基體係由於操作性良好而較佳。由表面之平滑性或機械強度之 觀點，具體而言，較佳為聚對苯二甲酸乙二酯(PET)、聚萘二甲酸乙二酯(PEN)、丙烯酸、聚丙烯、聚碳酸酯、環烯烴等透明或半透明樹脂之片或薄膜。此等係可為單層亦可為多層，亦可以提高密合性之目的而以電漿等習知的方法表面處理，或以獲得表面硬度之目的而以表面塗布材塗布。其中，由機械強度之方面，特佳為PET薄膜或PEN薄膜。 The transparent substrate to be used as the support of the substrate with the transparent conductive layer of the present invention is not particularly limited as long as it has sufficient physical strength and light transmittance as a support, but the sheet-like transparent base system is operated. Good and better. Smooth by surface or mechanical strength In view of the above, it is preferably a transparent or translucent resin such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), acrylic acid, polypropylene, polycarbonate, or cycloolefin. Tablet or film. These may be a single layer or a plurality of layers, or may be surface-treated by a conventional method such as plasma for the purpose of improving adhesion, or coated with a surface coating material for the purpose of obtaining surface hardness. Among them, from the aspect of mechanical strength, it is particularly preferred to be a PET film or a PEN film.

上述透明基體的厚度，若過薄則操作性困難；另一方面過厚時，則有可見光之透射率降低之虞。因此，5μm~300μm之範圍，係操作性良好且透射率優異而較佳。更佳為10μm~250μm之範圍，再更佳為25μm~200μm。 When the thickness of the transparent substrate is too thin, the handleability is difficult. On the other hand, when the thickness is too thick, the transmittance of visible light is lowered. Therefore, the range of 5 μm to 300 μm is excellent in workability and excellent in transmittance. More preferably, it is in the range of 10 μm to 250 μm, and more preferably in the range of 25 μm to 200 μm.

透明基體的總透光率，係較佳為90%以上，特佳為95%以上。又，透明基體係較佳為無著色之透明基體。藉由使用該透明基體，易於獲得透明性高的附透明導電層之基體。 The total light transmittance of the transparent substrate is preferably 90% or more, and particularly preferably 95% or more. Further, the transparent base system is preferably a transparent substrate having no coloration. By using the transparent substrate, it is easy to obtain a substrate having a transparent transparent conductive layer with high transparency.

(含有金屬奈米線之透明導電層(2)) (Transparent conductive layer containing metal nanowires (2))

在本發明使用之含有金屬奈米線的透明導電層(2)中，金屬奈米線，係表示形狀為直線或曲線之細棒狀、材質為金屬、粗度為奈米大小之細微的導電性物質。若細微之導電性物質為纖維狀，較佳為線狀，則藉由該等相互地交錯而成為網眼(mesh)狀，即使係少量之導電性物質亦可形成良好之電傳導通道，可使導電性層之電阻值更降低而較佳。進一步形成如此之網眼狀之情形，由於網眼之間隙部分的開口大，即便是纖維狀的導電性物質其本身係非透明，亦可達成作為塗膜之良好的透明性。 In the transparent conductive layer (2) containing the metal nanowire used in the present invention, the metal nanowire is a thin rod having a shape of a straight line or a curved line, a material of a metal, and a fineness of a nanometer size. Sexual substance. When the fine conductive material is fibrous, preferably linear, it is mutually meshed to form a mesh shape, and even a small amount of conductive material can form a good electrical conduction path. It is preferred to lower the resistance value of the conductive layer. Further, in the case of such a mesh shape, since the opening of the gap portion of the mesh is large, even if the fibrous conductive material itself is opaque, good transparency as a coating film can be achieved.

作為金屬奈米線之金屬，具體而言可舉出：鐵、鈷、鎳、銅、鋅、釕、銠、鈀、銀、鎘、鋨、銥、鉑、金，由導電性之觀點，較佳為銅、銀、鉑、金。金屬奈米線的至少一剖面尺寸，係較佳為剖面之最大直徑未滿500nm。更佳為未滿200nm，再更佳為未滿100nm。作為金屬奈米線，較佳為作為縱橫比係超過10。更佳為作為縱橫比超過50，再更佳為具有超過100之縱橫比。金屬奈米線之形狀或大小，可以掃描式電子顯微鏡或穿透式電子顯微鏡來確認。 Specific examples of the metal of the metal nanowire include iron, cobalt, nickel, copper, zinc, lanthanum, cerium, palladium, silver, cadmium, lanthanum, cerium, platinum, and gold, and from the viewpoint of electrical conductivity, Good for copper, silver, platinum, gold. At least one cross-sectional dimension of the metal nanowire is preferably such that the largest diameter of the cross-section is less than 500 nm. More preferably, it is less than 200 nm, and even more preferably less than 100 nm. The metal nanowire is preferably more than 10 as an aspect ratio. More preferably, it has an aspect ratio of more than 50, and more preferably has an aspect ratio of more than 100. The shape or size of the metal nanowire can be confirmed by a scanning electron microscope or a transmission electron microscope.

金屬奈米線，係可以在該技術領域之已知的方法製作、製備。可舉出例如：於溶液中還原硝酸銀之方法，或於前體表面由探針的尖端部使輸入電壓或電流作用，於探針尖端部拉出金屬奈米線，而連續地形成該金屬奈米線之方法等(日本特開2004-223693公報)。作為於溶液中還原硝酸銀之方法，更具體而言，銀奈米線，係能夠在乙醇等之多元醇，及聚乙烯吡咯啶酮之存在下，藉由硝酸銀等之銀鹽的液相還原而合成。均勻尺寸之銀奈米線之大量生產，係可根據例如於Xia,Y.etal.,Chem.Mater.(2002)、14、4736-4745及Xia,Y.etal.,Nano letters(2003)3(7)、955-960所記載之方法而製備，但不限定於此等所記載之方法。 Metal nanowires can be made and prepared by methods known in the art. For example, a method of reducing silver nitrate in a solution, or applying an input voltage or current to the tip end portion of the probe on the surface of the precursor, and pulling out the metal nanowire at the tip end portion of the probe, and continuously forming the metal naphthalene Method of rice noodle, etc. (JP-A-2004-223693). As a method of reducing silver nitrate in a solution, more specifically, a silver nanowire can be reduced by liquid phase of a silver salt such as silver nitrate in the presence of a polyol such as ethanol or polyvinylpyrrolidone. synthesis. The mass production of uniform size silver nanowires can be based, for example, on Xia, Y. et al., Chem. Mater. (2002), 14, 4736-4745 and Xia, Y. et al., Nano letters (2003) 3 (7), prepared by the method described in 955-960, but is not limited to the methods described herein.

具有如此之導電性的金屬奈米線，係於透明基體上以具有一面保持適當地間隔，一面相互交錯之狀態形成導電網，而能夠在實質上為透明導電網。具體的金屬種類或軸長、縱橫比等，只要視使用目的等適當決定即可。 The metal nanowire having such conductivity is formed on the transparent substrate so as to form a conductive mesh in a state of being staggered while being appropriately spaced apart from each other, and can be substantially a transparent conductive mesh. The specific metal type, the axial length, the aspect ratio, and the like may be appropriately determined depending on the purpose of use and the like.

含有金屬奈米線之透明導電層(2)，只要是金屬奈米線係於透明基體上以相互交錯之狀態形成導電網之透明導電層，則形成方法並無特別限制，但是藉由塗布使金屬奈米線分散於分散媒之分散液，並乾燥及/或硬化而可易於形成。 The transparent conductive layer (2) containing the metal nanowires is not particularly limited as long as the metal nanowires are formed on the transparent substrate to form a transparent conductive layer of the conductive mesh in a state of being interlaced with each other, but by coating The metal nanowires are dispersed in a dispersion of a dispersion medium and dried and/or hardened to be easily formed.

作為用於獲得上述金屬奈米線之分散液的分散媒之液體，並無特別限定，可使用已知之各種分散媒。可舉出例如：己烷等飽和烴類，甲苯、二甲苯等芳香族烴類，甲醇、乙醇、丙醇、丁醇等醇類，丙酮、甲基乙基酮(MEK)甲基異丁基酮、二異丁基酮等酮類，乙酸乙酯、乙酸丁酯等酯類，四氫呋喃、二烷、二***等醚類，N,N-二甲基甲醯胺、N-甲基吡咯啶酮(NMP)、N,N-二甲基乙醯胺等醯胺類，氯化乙烯、氯苯等鹵化烴等。又，亦可根據分散媒之種類，使用分散劑。在此等分散媒之中，較佳為具有極性之分散媒，特佳為如甲醇、乙醇等醇類，NMP等醯胺類之與水有親和性者，係不使用分散劑亦分散性良好而適宜。此等液體，可單獨亦可混合兩種以上而使用。 The liquid for dispersing the dispersion liquid of the above metal nanowire is not particularly limited, and various known dispersion media can be used. Examples thereof include saturated hydrocarbons such as hexane, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, ethanol, propanol and butanol, and acetone and methyl ethyl ketone (MEK) methyl isobutyl. Ketones such as ketone and diisobutyl ketone, esters such as ethyl acetate and butyl acetate, tetrahydrofuran, and Ethers such as alkane and diethyl ether, amides such as N,N-dimethylformamide, N-methylpyrrolidone (NMP) and N,N-dimethylacetamide, ethylene chloride and chlorine Halogenated hydrocarbons such as benzene. Further, a dispersing agent may be used depending on the type of the dispersing medium. Among these dispersing media, a dispersing medium having a polarity is preferable, and an alcohol such as methanol or ethanol is preferable, and those having affinity with water such as NMP such as NMP are also excellent in dispersibility without using a dispersing agent. And appropriate. These liquids may be used alone or in combination of two or more.

又，亦可使用水作為分散媒，但水之情形，係在上述有色之透明層(1)為疏水性時，水容易撥開而難以獲得均勻之膜。於此情形時，係可將醇混合於水中，或是選定並添加如改善對疏水性透明基體之濕潤性的界面活性劑，以獲得均勻之膜。 Further, water may be used as the dispersing medium. However, in the case of water, when the colored transparent layer (1) is hydrophobic, water is easily removed and it is difficult to obtain a uniform film. In this case, the alcohol may be mixed in water, or a surfactant such as an improved wettability to the hydrophobic transparent substrate may be selected and added to obtain a uniform film.

作為所使用之分散媒的液體量，並無特別限制，只要使上述金屬奈米線之分散液具有如適於塗布之黏度即 可。例如：相對於上述金屬奈米線100重量份，可設定為液體100~100,000重量份左右之廣泛範圍，可視上述金屬奈米線與分散媒之種類、所使用之攪拌、分散裝置而適當選擇。 The amount of the liquid to be used as the dispersion medium is not particularly limited as long as the dispersion of the above metal nanowire has a viscosity suitable for coating, that is, can. For example, it can be set to a wide range of about 100 to 100,000 parts by weight based on 100 parts by weight of the above-mentioned metal nanowire, and can be appropriately selected depending on the type of the metal nanowire and the dispersion medium, and the stirring and dispersing device to be used.

對上述金屬奈米線之對分散媒中的分散，係可視需要而對金屬奈米線與分散媒之液體的混合物，藉由適宜使用習知之分散方法來進行。但是，為了形成具有良好透明性與導電性之透明導電層，金屬奈米線之特性於分散處理前後無太大便化、混合物不失去透明性係為重要。尤其是由於金屬奈米線會因折疊而引起導電性的降低或透明性的降低，選擇不破壞金屬奈米線形狀的分散方法係為重要。 The dispersion of the metal nanowires in the dispersion medium may be carried out by a conventional dispersion method using a conventional mixture of the metal nanowire and the dispersion medium as needed. However, in order to form a transparent conductive layer having good transparency and conductivity, the characteristics of the metal nanowire are not so large before and after the dispersion treatment, and it is important that the mixture does not lose transparency. In particular, since the metal nanowire may cause a decrease in conductivity or a decrease in transparency due to folding, it is important to select a dispersion method that does not destroy the shape of the metal nanowire.

上述金屬奈米線之分散液，就提升導電性能之點，較佳為不含黏合劑樹脂。在導電性層中，若不使用黏合劑樹脂則不會阻礙金屬奈米線彼此之接觸。因此，可確保金屬奈米線相互間之導電性，更低地抑制所得之導電層之電阻值。 The dispersion of the above metal nanowires preferably improves the conductivity, and preferably does not contain a binder resin. In the conductive layer, if the binder resin is not used, the contact of the metal nanowires with each other is not hindered. Therefore, the electrical conductivity of the metal nanowires can be ensured, and the resistance value of the obtained conductive layer can be suppressed lower.

又，以後述之離線法製作本發明之附透明導電層之基體時，藉由金屬奈米線之分散液不含黏合劑樹脂，而在基體上形成透明導電性塗膜時，就透明導電性塗膜於下一步驟中可容易自該透明基體剝離之點亦較佳。進而，其後經圖案化之透明導電層的藉由保護層用塗料進行對基體上的固定化之時，由於藉由使導電層含浸保護層用塗料到達基體來進行，就透明導電性物質之分散液不含黏合劑樹脂，係意味著透明導電層包含更多間隙，不阻礙藉由保護層用塗料之含浸的固定化之點，係較佳。 Further, when the base material with a transparent conductive layer of the present invention is produced by an off-line method described later, the dispersion of the metal nanowire does not contain a binder resin, and when a transparent conductive coating film is formed on the substrate, the transparent conductivity is obtained. The point at which the coating film can be easily peeled off from the transparent substrate in the next step is also preferable. Further, when the patterned transparent conductive layer is fixed to the substrate by the protective layer coating, the conductive layer is impregnated with the protective layer to reach the substrate, and the transparent conductive material is used. The fact that the dispersion does not contain a binder resin means that the transparent conductive layer contains more gaps and does not hinder the point of immobilization by impregnation of the coating for the protective layer.

但是，若為不降低基體上之塗膜的導電性，或自基體之塗膜剝離性，不損及藉由保護層用塗料中之樹脂的導電性層之固定化步驟的程度之量，亦可包含樹脂。其種類與量，能夠在可獲得上述特性之範圍適當選擇。藉由少量調配如此適量之樹脂，會有基體上之導電層塗膜係良好地被固定，於圖案形成步驟時不發生脫落之效果。 However, if the conductivity of the coating film on the substrate is not lowered, or the peeling property of the coating film from the substrate is not impaired, the amount of the fixing step of the conductive layer of the resin in the coating material for the protective layer is not impaired. A resin may be included. The type and amount thereof can be appropriately selected within the range in which the above characteristics can be obtained. By disposing such an appropriate amount of the resin in a small amount, the conductive layer coating film on the substrate is well fixed, and the effect of falling off does not occur at the pattern forming step.

於上述之添加量範圍中金屬奈米線之分散液，為了控制黏度調整、抗腐蝕、提升對基體之接著性，及導電性物質之分散，亦可含有上述樹脂及其他之添加劑。作為適切的添加劑及結合劑之例，可舉出：羧甲基纖維素(CMC)、2-羥乙基纖維素(HEC)、羥丙基甲基纖維素(HPMC)、甲基纖維素(MC)、聚乙烯醇(PVA)、三丙二醇(TPG)；及三仙膠(XG)，及乙氧基化物、烷基化物、環氧乙烷及環氧丙烷等界面活性劑，及該等之共聚物、磺酸鹽、硫酸鹽、二磺酸鹽、磺琥珀酸鹽、磷酸酯，及鹵素系界面活性劑，但不限定於此。又，在金屬奈米線於水系製造之情形，係可使用聚乙烯醇系樹脂、乙烯吡咯啶酮系聚合物、纖維素衍生物等各種水溶性樹脂。 The dispersion of the metal nanowire in the above-mentioned addition amount range may contain the above-mentioned resin and other additives in order to control the viscosity adjustment, the corrosion resistance, the adhesion to the substrate, and the dispersion of the conductive material. Examples of suitable additives and binders include carboxymethyl cellulose (CMC), 2-hydroxyethyl cellulose (HEC), hydroxypropyl methyl cellulose (HPMC), and methyl cellulose ( MC), polyvinyl alcohol (PVA), tripropylene glycol (TPG); and Sanxian gum (XG), and surfactants such as ethoxylates, alkylates, ethylene oxide and propylene oxide, and the like The copolymer, the sulfonate, the sulfate, the disulfonate, the sulfosuccinate, the phosphate, and the halogen-based surfactant are not limited thereto. Further, in the case where the metal nanowire is produced in a water system, various water-soluble resins such as a polyvinyl alcohol resin, a vinyl pyrrolidone polymer, and a cellulose derivative can be used.

更者，亦可使用2-烷氧乙醇、β-二酮、乙酸烷基酯等非聚合物系有機化合物作為膜形成劑。 Further, a non-polymer organic compound such as 2-alkoxyethanol, β-diketone or alkyl acetate may be used as the film forming agent.

上述透明導電層(2)，視用途而所欲之物性質不同。例如作為觸控面板之透明電極層使用之情形，較佳為表面電阻率係0.01Ω/□~1000Ω/□，較佳為於可見光域具有高透明性。 The above transparent conductive layer (2) has different properties depending on the application. For example, when it is used as a transparent electrode layer of a touch panel, it is preferable that the surface resistivity is 0.01 Ω/□ to 1000 Ω/□, and it is preferable to have high transparency in the visible light region.

作為將上述透明導電層(2)，設置於有色之透明層(1)上之方法，較佳為塗布法。具體而言，係將上述金屬奈米線之分散液塗布於上述有色之透明層(1)上後，使其乾燥。 As a method of providing the transparent conductive layer (2) on the colored transparent layer (1), a coating method is preferred. Specifically, the dispersion of the above metal nanowire is applied onto the colored transparent layer (1), followed by drying.

作為塗布方法，可使用噴霧塗布、棒塗布、輥塗布、模塗布、噴墨塗布、網版塗布、浸漬塗布等習知之塗布方法。又，可藉由在薄膜的製造步驟設置塗布層之線上塗布方式、在薄膜製造後設置塗布層之離線塗布方式來設置。 As the coating method, a conventional coating method such as spray coating, bar coating, roll coating, die coating, inkjet coating, screen coating, or dip coating can be used. Further, it can be provided by an on-line coating method in which a coating layer is provided in a film production step, and an off-line coating method in which a coating layer is provided after film production.

上述透明導電層(2)之膜厚，可視用途適當調整，但越薄則導電性有降低之傾向；另一方面，若過厚，則霧度值上升、總透光率下降等而透明性有降低之傾向。由此等而言，例如作為觸控面板用之透明電極層使用的情形，多於10nm~10μm之間進行適當調整。尤其是由於金屬奈米線本身非透明，隨著膜厚之增加透明性係降低傾向強，因此多為形成較薄之膜厚的導電層。此情形係為極多開口部之導電層，但以接觸式之膜厚計測定時，作為平均膜厚較佳為10nm~500nm之膜厚範圍，更佳為30nm~300nm。最佳為50nm~150nm。 The film thickness of the transparent conductive layer (2) may be appropriately adjusted depending on the application, but the thinner the conductivity is, the lower the conductivity is. On the other hand, if the thickness is too thick, the haze value is increased, the total light transmittance is lowered, and the transparency is improved. There is a tendency to decrease. In this case, for example, when used as a transparent electrode layer for a touch panel, it is appropriately adjusted between more than 10 nm and 10 μm. In particular, since the metal nanowire itself is non-transparent, the transparency tends to decrease as the film thickness increases, so that a conductive layer having a thin film thickness is often formed. In this case, the conductive layer is extremely large, but when measured by a contact type film thickness meter, the average film thickness is preferably in the range of 10 nm to 500 nm, more preferably 30 nm to 300 nm. The optimum is 50 nm to 150 nm.

上述透明導電層(2)含有金屬奈米線、或金屬奈米線與樹脂及已述之其他添加劑。使用樹脂時之添加量係考慮導電性塗膜之導電性、剝離性、保護層用塗料之浸漬的容易度等來決定，但是較佳為僅止於添加為了透明導電層中之金屬奈米線相對於基體被良好地固定，而在之後的步驟中不易脫落之必要的最小限度之量。於此情 形，基體上形成透明導電層後，樹脂係容易集中於透明導電層之基體側，有金屬奈米線可容易固定於基體之傾向，但於較遠於基體側金屬奈米線係不被樹脂被覆而露出，容易成為導電性物質間有空隙之狀態。 The transparent conductive layer (2) contains a metal nanowire, a metal nanowire and a resin, and other additives as described above. The amount of addition when the resin is used is determined in consideration of the conductivity and the releasability of the conductive coating film, the ease of immersion of the coating material for the protective layer, and the like. However, it is preferable to merely add the metal nanowire in the transparent conductive layer. The minimum amount necessary to be well fixed with respect to the substrate and not easily detached in the subsequent steps. Here After the transparent conductive layer is formed on the substrate, the resin is easily concentrated on the base side of the transparent conductive layer, and the metal nanowire can be easily fixed to the substrate, but the metal nanowire is far away from the substrate. When it is covered and exposed, it is easy to become a state in which there is a gap between conductive materials.

再者，上述透明導電層(2)，更以提高導電性之目的，而在使塗布形成後之透明導電層(2)中的金屬奈米線彼此間交錯部分的接觸點增加之同時，可增加接觸面積，進行為了使其確實地接觸可進行加壓步驟。 Furthermore, the transparent conductive layer (2) further increases the conductivity, and increases the contact point of the interdigitated portions of the metal nanowires in the transparent conductive layer (2) after the coating is formed. The contact area is increased, and a pressurizing step can be performed in order to make it surely contact.

加壓導電性物質之交錯部分的步驟，具體而言係指加壓透明導電層面之步驟，係對網眼狀分散有金屬奈米線之透明導電層由正上方施加壓力，壓縮透明導電層，而增加內部之金屬奈米線的接觸點之步驟。藉由此步驟而金屬奈米線間之接觸電阻會下降。 The step of pressing the interlaced portion of the conductive material specifically refers to the step of pressing the transparent conductive layer, and applying a pressure to the transparent conductive layer in which the metal nanowire is dispersed in the mesh shape, compressing the transparent conductive layer, The step of increasing the contact point of the inner metal nanowire. By this step, the contact resistance between the metal nanowires is lowered.

本步驟只要是通常加壓塗膜面之習知的方法，則無特別限制，但將藉由塗布而獲得之層，可舉出例如，於可加壓之2片平板間配置透明導電層，而以一定時間加壓之平板壓機法，或在可加壓之2支輥間挾入透明導電層而線加壓，而藉由使輥旋轉來加壓面整體之壓延法等。 This step is not particularly limited as long as it is a conventional method of pressurizing the surface of the coating film. However, a layer obtained by coating may be, for example, a transparent conductive layer disposed between two sheets that can be pressurized. Further, a flat press method which pressurizes for a certain period of time, or a line in which a transparent conductive layer is interposed between two rolls which can be pressurized, and which is line-pressed, and the entire surface of the pressurizing surface is rolled by rotating the roll.

於利用輥之壓延法中，加壓上述透明導電層(2)之輥線壓為1kN/m~500 kN/m，較佳為5 kN/m~300 kN/m，更佳為10 kN/m~100 kN/m。 In the calendering method using a roll, the line pressure of the transparent conductive layer (2) is 1 kN/m to 500 kN/m, preferably 5 kN/m to 300 kN/m, more preferably 10 kN/. m~100 kN/m.

(附透明導電層之基體) (with a base of transparent conductive layer)

本發明之附透明導電層之基體，其係於上述透明基體上，依序具有有色之透明層(1)與透明導電層(2)之附透明導電層之基體。本發明之附透明導電層之基體，係藉 由此構成，因即使不進行金屬奈米線之被覆等亦可減輕由金屬奈米線之亂反射引起之黃色度，而具有良好的電阻值，且為透明並再現性優異， The substrate with a transparent conductive layer of the present invention is attached to the transparent substrate, and sequentially has a colored transparent layer (1) and a transparent conductive layer (2) with a transparent conductive layer. The substrate with the transparent conductive layer of the invention is borrowed According to this configuration, even if the coating of the metal nanowire is not performed, the yellowness caused by the disordered reflection of the metal nanowire can be reduced, and the electrical resistance value is good, and the transparency is excellent and the reproducibility is excellent.

本發明之附透明導電層之基體，較佳為其霧度值5%以下，更佳為3%以下，再更佳為2%以下，特佳為1%以下。尤其是作為觸控面板用之透明電極層使用的情形，較佳為0.1~2%之範圍，更佳為成為0.1~0.5%之範圍。又，總透光率係較佳為80%以上，更佳為85%以上，再更佳為88%以上。藉由成為上述範圍，可合適地使用於作為薄型且謀求高密度封裝之行動電子機器所使用之透明電極，尤其是作為觸控面板用之透明電極。 The substrate with a transparent conductive layer of the present invention preferably has a haze value of 5% or less, more preferably 3% or less, still more preferably 2% or less, and particularly preferably 1% or less. In particular, when it is used as a transparent electrode layer for a touch panel, it is preferably in the range of 0.1 to 2%, more preferably in the range of 0.1 to 0.5%. Further, the total light transmittance is preferably 80% or more, more preferably 85% or more, still more preferably 88% or more. By being in the above range, it can be suitably used for a transparent electrode used in a mobile electronic device which is a thin and high-density package, and is particularly used as a transparent electrode for a touch panel.

附透明導電層之基體之表面電阻值，係較佳為0.01~1000Ω/□，更佳為1Ω/□~500Ω/□，再更佳為10Ω/□~300Ω/□。藉由為上述範圍，可合適地使用於作為行動電子機器所使用之透明電極，尤其是作為觸控面板用之透明電極。 The surface resistance value of the substrate with the transparent conductive layer is preferably 0.01 to 1000 Ω/□, more preferably 1 Ω/□ to 500 Ω/□, and still more preferably 10 Ω/□ to 300 Ω/□. By being in the above range, it can be suitably used as a transparent electrode used as a mobile electronic device, particularly as a transparent electrode for a touch panel.

(透明導電層(2)之圖案化方法) (patterning method of transparent conductive layer (2))

將上述透明導電層(2)圖案化之時，可選用習知之圖案化方法。例如有： When the above transparent conductive layer (2) is patterned, a conventional patterning method can be selected. For example:

(A)使用網版印刷等之各種印刷法等，使用黏合劑樹脂等將銀奈米線固定化為圖案狀，其後，將非固定化區域以適當的溶劑洗淨或刷洗，或是藉由以具有黏著性之滾輪去除，而形成透明導電性圖案之方法。 (A) The silver nanowire is fixed to a pattern using a binder resin or the like using various printing methods such as screen printing, and thereafter, the non-immobilized region is washed or brushed with an appropriate solvent, or borrowed. A method of forming a transparent conductive pattern by removing it with an adhesive roller.

(B)於基體上形成銀奈米線之透明導電層後，對該導電層整面塗布可藉由光或熱而硬化之抗蝕塗料，僅對欲 殘留作為圖案之部分供給光或熱而硬化後，使用與上述(A)相同之方法」，去除不要部分來形成透明導電性圖案之方法。 (B) after forming a transparent conductive layer of a silver nanowire on the substrate, coating the entire surface of the conductive layer with a resist coating which can be hardened by light or heat, only for the desire The method of removing the unnecessary portion to form a transparent conductive pattern by using the same method as the above (A) after leaving a portion of the pattern to be light or heat and hardening is used.

(C)於基體上形成銀奈米線之透明導電層後，將另外準備之具有經負型圖案化的接著領域之層之片，貼附於上述透明電極層後剝離，而於基體上形成透明導電層之圖案的方法。 (C) after forming a transparent conductive layer of a silver nanowire on the substrate, separately preparing a sheet having a negatively patterned layer of the subsequent field, attaching to the transparent electrode layer, peeling off, and forming on the substrate A method of patterning a transparent conductive layer.

(D)於基體上形成銀奈米線之透明導電層後，將含有銀奈米線去除劑之液，圖案印刷在形成圖案電極時不要的部份後，使用與上述(A)相同之方法」去除不要部分來形成透明導電性圖案之方法。 (D) After the transparent conductive layer of the silver nanowire is formed on the substrate, the liquid containing the silver nanowire remover is printed on the unnecessary portion of the patterned electrode, and the same method as (A) above is used. A method of removing unnecessary portions to form a transparent conductive pattern.

等之方法。於本發明中(B)或(C)之方法，係可容易地且低成本地形成高精細圖案化之無斷線、短路之透明導電層圖案而較佳。 The method of waiting. In the method of (B) or (C) of the present invention, it is preferable to form a high-definition patterned non-broken, short-circuited transparent conductive layer pattern easily and at low cost.

作為上述(B)之方法中所使用之可藉由光或熱而硬化之抗蝕塗料，係通常可使用為了蝕刻氧化銦、氧化鋅、氧化錫等之透明導電層所使用之抗蝕塗料，但是因可藉由曝光使圖案形成，較佳為使用光蝕刻(photolithography)用之抗蝕塗料。將圖案曝光時之曝光條件，亦較佳為以適合上述抗蝕塗料之曝光條件來進行。又，於顯影所使用之顯影液係可使用硝酸、過硫酸銨，及其之同等物、或過錳酸鉀等氧化劑。 As the resist paint which can be cured by light or heat as used in the method of the above (B), a resist paint for etching a transparent conductive layer of indium oxide, zinc oxide, tin oxide or the like can be usually used. However, since the pattern can be formed by exposure, it is preferable to use a resist paint for photolithography. The exposure conditions at the time of exposing the pattern are also preferably carried out in an exposure condition suitable for the above-mentioned resist paint. Further, as the developing solution used for development, an oxidizing agent such as nitric acid, ammonium persulfate, an equivalent thereof, or potassium permanganate may be used.

又，上述(C)之方法，具體地以以下步驟1~步驟6進行說明。 Further, the method of the above (C) will be specifically described in the following steps 1 to 6.

步驟1：於基體上，藉由塗布而形成波長450nm、波長550nm及波長650nm之吸光度分別獨立在為0.001~0.1之範圍，且霧度值在為0.1~2%之範圍的有色之透明層(1)。 Step 1: On the substrate, a colored transparent layer having a wavelength of 450 nm, a wavelength of 550 nm, and a wavelength of 650 nm, which are independently in the range of 0.001 to 0.1 and having a haze value of 0.1 to 2%, is formed by coating ( 1).

步驟2：於上述透明層(1)上藉由塗布而形成含有金屬奈米線之可剝離的透明導電層(2)。 Step 2: Forming a peelable transparent conductive layer (2) containing a metal nanowire on the transparent layer (1) by coating.

步驟3：於支撐體上，形成具有經負型圖案化之接著區域之層。 Step 3: On the support, a layer having a negatively patterned subsequent region is formed.

步驟4：將上述基體與上述支撐體貼合、使上述透明導電層(2)與具有上述接著區域之層的該接著區域係如相互密合。 Step 4: bonding the substrate to the support, such that the transparent conductive layer (2) and the bonding region having the layer of the bonding region are in close contact with each other.

步驟5：將上述支撐體自上述基體剝離，並使與具有上述接著區域之層的該接著區域密合之部分的上述透明導電層(2)，轉移至具有接著區域之層的該接著區域上，藉此於基體上形成透明導電層(2)之圖案。 Step 5: peeling the support from the substrate, and transferring the portion of the transparent conductive layer (2) that is in close contact with the bonding region of the layer having the bonding region to the bonding region having a layer of the bonding region Thereby, a pattern of the transparent conductive layer (2) is formed on the substrate.

步驟6：對形成上述透明導電層(2)之圖案的基體整面，塗布保護層用塗料，將透明導電層(2)固定化於基體上。 Step 6: Applying a coating material for a protective layer to the entire surface of the substrate on which the pattern of the transparent conductive layer (2) is formed, and fixing the transparent conductive layer (2) to the substrate.

再者，於本發明中之負型圖案，係為表示與於基體上應形成之透明導電層之圖案(正型圖案)，成為負與正之相反之同比例尺的圖案者。 Further, the negative pattern in the present invention is a pattern indicating a transparent conductive layer to be formed on the substrate (positive pattern), and is a pattern of the same scale as the negative and positive.

步驟1、步驟2如上述。 Steps 1 and 2 are as described above.

在步驟3即於支撐體上，形成具有經負型圖案化之接著區域之層的步驟中，「於支撐體上具有形成經負型圖案化之接著區域之層」，即，為了將上述有色之透明層(1) 上所形成之透明導電層部分地剝離之剝離材。(之後「於支撐體上具有預先經負型圖案化之感熱接著劑層的剝離材」簡稱為「剝離材」)。 In step 3, in the step of forming a layer having a negative patterning succeeding region on the support, "having a layer on the support having a negative patterning succeeding region", that is, in order to color the above Transparent layer (1) The peeling material partially peeled off by the transparent conductive layer formed thereon. (Subsequently, "a release material having a heat-sensitive adhesive layer previously patterned negatively on the support" is simply referred to as a "release material").

作為剝離材，其係只要是於片狀之支撐體上形成有具有為了部分地剝離透明導電層之經負型圖案化的接著區域之層者，即可廣泛使用。作為此類之剝離材之製作方法，係可於支撐體上具有接著功能，或是使可表現之機能性塗膜均勻地形成後，以光等部分地圖案化而使其表現或失去接著功能而進行。或者亦可自一開始就使用接著劑將負型圖案直接印刷於支撐體上來製作剝離材。 As the release material, a layer having a negative-patterned adhesion region for partially peeling off the transparent conductive layer can be used as long as it is formed on a sheet-like support. As a method for producing such a release material, it is possible to have a function of the support on the support or to form a functional film which can be expressed uniformly, and then partially patterned by light or the like to cause or lose the subsequent function. And proceed. Alternatively, the negative pattern may be directly printed on the support using an adhesive from the beginning to prepare a release material.

為了將接著劑負型圖案化而印刷於支持體上，係必須製作對應負型圖案之印刷版。因此，就各種圖案可容易轉換之點，較佳為使用將光硬化組成物等之均勻的機能性塗膜，以部分性地光照射等使其接著功能部分地表現或失去之方法。 In order to pattern the adhesive negative pattern and print it on the support, it is necessary to produce a printing plate corresponding to the negative pattern. Therefore, in order to easily convert the various patterns, it is preferable to use a uniform functional coating film such as a photohardening composition to partially express or lose the function by partial light irradiation or the like.

製作如此之剝離材，係可例如，以於支撐體上塗布具有接著性之光硬化性組成物而形成均勻的塗膜，並於進行負型圖案狀的光罩狀態下光照射，使負型圖案以外之塗膜部分硬化，使該部分失去接著性來製作負型圖案狀之接著區域，而進行。 In order to produce such a release material, for example, a photocurable composition having an adhesiveness is applied to a support to form a uniform coating film, and light irradiation is performed in a state of a negative pattern, so that a negative type is formed. The coating film portion other than the pattern is hardened, and the portion is lost in adhesion to form a negative pattern-like succeeding region.

作為可使用於剝離材之製作之具有接著性的光硬化性組成物，可使用例如，對於在丙烯酸烷基酯系或甲基丙烯酸烷基酯系等聚合物內導入有光聚合性之不飽和鍵結的聚合性聚合物，添加例如，四羥甲基甲烷四丙烯酸酯(tetramethylolmethane tetraacrylate)、新戊四醇三丙烯 酸酯(pentaerythritol triacrylate)等之光聚合性的多官能寡聚物，而利用藉由光照射的硬化收縮或彈性率之下降低者。 As a photocurable composition which can be used for the production of a release material, for example, it is possible to introduce photopolymerizable unsaturated into a polymer such as an alkyl acrylate or an alkyl methacrylate. Bonded polymerizable polymer, for example, tetramethylolmethane tetraacrylate, neopentyl alcohol tripropylene A photopolymerizable polyfunctional oligomer such as a pentaerythritol triacrylate, which utilizes a hardening shrinkage by light irradiation or a decrease in an elastic modulus.

使用如此之剝離材來進行實際之剝離步驟之時，可對該基材之具有接著功能之層預先進行光照射，而使特定之圖案表現接著性或失去接著性，來進行透明導電層之部分剝離。或者亦可將光未照射之剝離材貼合於透明導電層後，透過光罩對貼合面進行光照射，而使部分地表現接著性或失去接著性，來進行透明導電層之部分剝離。 When such a peeling material is used for the actual peeling step, the layer having the function of the substrate may be previously irradiated with light to cause the specific pattern to exhibit adhesion or lose the adhesion, thereby performing a part of the transparent conductive layer. Stripped. Alternatively, the peeling material that has not been irradiated with light may be bonded to the transparent conductive layer, and then the bonding surface may be light-irradiated through the photomask to partially exhibit adhesion or lose adhesion, thereby performing partial peeling of the transparent conductive layer.

大量製作單一圖案之剝離材時，就製造效率之點，較佳為使用不需要於均勻塗膜上製作部分的接著區域之如光照射的步驟，而直接印刷於支撐體上。尤其是若使用感熱接著劑作為接著劑，由於一方面係在常溫為無接著性之通常的印刷薄膜，藉著剝離步驟中所施加之加熱程序，表現暫時性的接著功能，且於溫度下降後快速地失去功能，而剝離步驟前後之剝離材的操作性良好。 When the release material of a single pattern is produced in a large amount, it is preferable to directly print on the support by using a step of light irradiation which does not require a subsequent region of the portion on which the uniform coating film is formed. In particular, when a heat-sensitive adhesive is used as an adhesive, a normal printed film having no adhesion at normal temperature is used, and a temporary heating function is exhibited by a heating program applied in the peeling step, and after the temperature is lowered, The function is quickly lost, and the workability of the release material before and after the peeling step is good.

作為剝離材使用於支撐體上直接印刷經負型圖案化之感熱接著劑層之方法時，於本發明使用之剝離材，係於支撐體上，具有經負型圖案化之感熱接著劑層。剝離材，係可於支撐體上，藉由將含有感熱接著劑與溶劑之感熱接著劑層用塗料，形成並塗布為相對於基體上應形成之所欲的導電性圖案之相反的負型圖案，而形成。 When the negative-patterned heat-sensitive adhesive layer is directly printed on the support as the release material, the release material used in the present invention is attached to the support and has a negative-patterned heat-sensitive adhesive layer. The release material can be formed on the support by using a coating of the sensible thermal adhesive layer containing the sensible heat-sensitive adhesive and the solvent as a negative pattern opposite to the desired conductive pattern to be formed on the substrate. And formed.

感熱接著劑係於常溫完全不顯示黏著性，但是藉由加熱而表現黏著性。作為於支撐體上形成感熱接著劑層 的感熱接著劑，係對於上述透明基體上所形成之透明導電層(2)，與支撐體雙方有親和性，只要是可強力地接著兩者之感熱接著劑，可無特別限定的使用習知之各種感熱接著劑。作為表現黏著性之溫度，較佳係透明基體為熱可塑性塑膠時，以不會大幅超過該熱可塑性塑膠之玻璃轉移溫度的溫度來表現黏著性。又，較佳係加熱為該溫度時滲透於透明導電層(2)之金屬奈米線之間隙且良好地密合。更在加熱後，較佳為在常溫左右剝離支撐體時，對金屬奈米線與支撐體的兩者顯示強接著力。 The sensible heat adhesive does not exhibit adhesiveness at normal temperature, but exhibits adhesion by heating. Forming a thermal adhesive layer on the support The heat-sensitive adhesive is a transparent conductive layer (2) formed on the transparent substrate, and has affinity with both supports. As long as it is a heat-sensitive adhesive capable of strongly adhering both, it can be used without any particular limitation. A variety of thermal adhesives. As the temperature at which the adhesiveness is exhibited, it is preferred that when the transparent substrate is a thermoplastic plastic, the adhesiveness is expressed at a temperature which does not greatly exceed the glass transition temperature of the thermoplastic plastic. Further, it is preferable to infiltrate into the gap of the metal nanowire of the transparent conductive layer (2) when heated to a good temperature and to adhere well. Further, after heating, it is preferred to exhibit a strong adhesion force to both the metal nanowire and the support when the support is peeled off at a normal temperature.

作為如此之感熱接著劑，係可舉出例如：聚胺甲酸酯系接著劑、聚酯系接著劑、酸鹽雙(氯乙烯/醋酸乙烯共聚物)系接著劑、丙烯酸系接著劑等。其中，又以具常溫以上之玻璃轉移溫度Tg，含有羧酸基、磺酸基等之酸基，以非晶性聚酯樹脂、聚酯系聚胺甲酸酯樹脂為主劑之感熱接著劑為較佳，作為玻璃轉移溫度，較佳為20~100℃之範圍。又，以操作感熱溫度之目的，亦可適當調配與上述主劑有相溶性，玻璃轉移溫度Tg不同之樹脂。 Examples of such a heat-sensitive adhesive include a polyurethane-based adhesive, a polyester-based adhesive, an acid salt bis(vinyl chloride/vinyl acetate copolymer) adhesive, and an acrylic adhesive. Among them, a glass transition temperature Tg having a temperature above normal temperature, an acid group containing a carboxylic acid group or a sulfonic acid group, and a heat-sensitive adhesive agent mainly comprising an amorphous polyester resin or a polyester-based polyurethane resin. Preferably, as the glass transition temperature, it is preferably in the range of 20 to 100 °C. Further, for the purpose of operating the sensible heat temperature, a resin having compatibility with the above-mentioned main component and having a different glass transition temperature Tg may be appropriately prepared.

於感熱接著劑，可係視需要添加作為抗結塊劑之聚烯烴系樹脂粒子。其中，又以添加聚乙烯樹脂粒子或聚丙烯樹脂粒子為較佳，更具體而言，較佳為添加高密度聚乙烯樹脂粒子、低密度聚乙烯樹脂粒子、改質型聚乙烯樹脂粒子、分解型低密度聚乙烯樹脂粒子、分解型聚丙烯樹脂粒子。又，此等聚乙烯樹脂粒子、分解型聚乙烯樹脂粒子、聚丙烯樹脂粒子及分解型聚丙烯樹脂粒子 之重量平均粒徑為0.1~25μm，但是粒子為扁平狀、鱗片狀時，長軸長較佳為3~25μm之範圍，並分別較佳係分子量為在1,000~29,000之範圍，熔點為在100~150℃之範圍。 For the heat-sensitive adhesive, polyolefin-based resin particles as an anti-caking agent may be added as needed. Further, it is preferable to add polyethylene resin particles or polypropylene resin particles, and more specifically, it is preferable to add high-density polyethylene resin particles, low-density polyethylene resin particles, modified polyethylene resin particles, and decomposition. Type low density polyethylene resin particles and decomposed polypropylene resin particles. Further, these polyethylene resin particles, decomposed polyethylene resin particles, polypropylene resin particles, and decomposed polypropylene resin particles The weight average particle diameter is 0.1 to 25 μm, but when the particles are flat and scaly, the major axis length is preferably in the range of 3 to 25 μm, and preferably the molecular weight is in the range of 1,000 to 29,000, and the melting point is 100. ~150 ° C range.

用於感熱接著劑層用塗料之溶劑，只要將使用於感熱接著劑之黏合劑樹脂良好地溶解或分散，可無特別限定的使用任何非腐蝕性溶劑。作為更適切之溶劑的例子，可舉出有：水、醇類、酮類之外，還有四氫呋喃等環狀醚化合物類；環己烷等烴；或苯、甲苯、二甲苯等芳香族系溶劑。更者，溶劑係揮發性、並較佳為具有200℃以下之沸點，更佳為150℃以下、再更佳為具有100℃以下之沸點。 The solvent for the coating for the heat-sensitive adhesive layer can be any non-corrosive solvent to be used without particular limitation as long as the binder resin used for the heat-sensitive adhesive is well dissolved or dispersed. Examples of the more suitable solvent include water, alcohols, and ketones, and a cyclic ether compound such as tetrahydrofuran; a hydrocarbon such as cyclohexane; or an aromatic system such as benzene, toluene or xylene. Solvent. Further, the solvent is volatile, and preferably has a boiling point of 200 ° C or less, more preferably 150 ° C or less, still more preferably a boiling point of 100 ° C or less.

作為於上述剝離材所使用之支撐體，可使用包含主要為聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯等之聚酯類；聚乙烯、聚丙烯、聚苯乙烯、EVA等之聚烯烴類；聚氯乙烯、聚偏氯乙烯等之乙烯系樹脂；聚碸、聚醚碸、聚碳酸酯、聚醯胺、聚醯亞胺、丙烯酸樹脂等塑膠之片。其中，又以在使透明導電層與感熱接著劑層相互密合而加熱貼合之步驟中，不易引起熱變形者為較佳。 As the support used for the above-mentioned release material, a polyester containing mainly polyethylene terephthalate or polyethylene naphthalate; polyethylene, polypropylene, polystyrene, EVA, etc. can be used. Polyolefins; vinyl resins such as polyvinyl chloride and polyvinylidene chloride; plastic sheets such as polyfluorene, polyether oxime, polycarbonate, polyamide, polyimine, and acrylic resin. Further, in the step of heat-bonding the transparent conductive layer and the heat-sensitive adhesive layer to each other, it is preferable that the heat-deformation is less likely to occur.

上述支撐體係於不妨礙本發明之目的之程度亦可著色，進而能夠以單層使用，亦可作為組合兩層以上之多層薄膜而使用。其中，就透明性、耐熱性、操作容易性、價格點，最適合為聚對苯二甲酸乙二酯薄膜。 The support system may be colored to the extent that the object of the present invention is not impaired, and may be used in a single layer or as a multilayer film in which two or more layers are combined. Among them, polyethylene terephthalate film is most suitable in terms of transparency, heat resistance, ease of handling, and price point.

由於上述支撐體之厚度，若薄，則缺乏耐熱性；若厚，則熱容量變大，於表現感熱接著劑由加熱所引起黏 著性，需要長加熱時間，較佳為5μm~100μm，更佳為10μm~50μm，更較佳為15μm~30μm之膜厚。 Due to the thickness of the support, if it is thin, the heat resistance is lacking; if it is thick, the heat capacity is increased, and the heat-sensitive adhesive is caused by the heat. The property requires a long heating time, preferably 5 μm to 100 μm, more preferably 10 μm to 50 μm, still more preferably 15 μm to 30 μm.

上述支撐體上之感熱接著劑層，係將於基體上想獲得之所欲的透明導電性圖案反轉，形成所謂之負型圖案狀。 The heat-sensitive adhesive layer on the support is reversed in a desired transparent conductive pattern to be obtained on the substrate to form a so-called negative pattern.

作為接著劑之負型圖案形成方法，係可使用習知之印刷方法，藉由加熱表現黏著性之感熱接著劑層，只要可於下一步驟中，於基體上之透明導電層形成用於良好地接著之充分的感熱接著劑之厚度，可無特別限制的使用習知之方法。例如：可使用凹版印刷法、平版印刷法、凹版平版印刷法、網版印刷法、噴墨印刷法等。又，感熱接著劑層之厚度，較佳為0.05μm~5.0μm，更佳為0.1μm~2.0μm，再更佳為0.2μm~1.0 μm。 As a negative pattern forming method of an adhesive, a heat-sensitive adhesive layer exhibiting adhesiveness can be heated by a conventional printing method as long as the transparent conductive layer on the substrate can be formed in a good manner in the next step. Next, the thickness of the sufficient heat-sensitive adhesive can be used without any particular limitation. For example, a gravure printing method, a lithography method, a gravure lithography method, a screen printing method, an inkjet printing method, or the like can be used. Further, the thickness of the heat-sensitive adhesive layer is preferably from 0.05 μm to 5.0 μm, more preferably from 0.1 μm to 2.0 μm, still more preferably from 0.2 μm to 1.0 μm.

若使用如此之上述剝離材，則不需要用於圖案化之光照射處理，或藉由濕式處理去除要剝離部分之等處理。上述剝離材係可藉由於輥狀之支撐體塗布或印刷感熱接著劑層用塗料而連續地形成，可將此直接用於下一步驟之剝離步驟。 If such a release material as described above is used, the light irradiation treatment for patterning or the treatment of removing the portion to be peeled off by the wet treatment is not required. The above-mentioned release material can be continuously formed by coating or printing a coating for a heat-sensitive adhesive layer by a roll-shaped support, and this can be directly used for the peeling step of the next step.

(透明導電層(2)之圖案化步驟) (patterning step of transparent conductive layer (2))

透明導電層(2)之圖案化步驟，係由步驟4即將上述基體與上述支撐體貼合、使上述透明導電層(2)與感受接著劑層相互密合之步驟，以及步驟5即將上述支撐體自上述基體剝離，並藉由使與上述感熱接著劑層密合之部分的上述透明導電層(2)，轉移至感熱接著劑層上，而於基體上殘留所欲之透明導電層(2)來形成圖案之步驟所構成。 The step of patterning the transparent conductive layer (2) is a step of bonding the substrate to the support, bonding the transparent conductive layer (2) and the adhesive layer to each other in step 4, and step 5 is to support the support Stripping from the substrate, and transferring the transparent conductive layer (2) adhering to the heat-sensitive adhesive layer to the heat-sensitive adhesive layer to leave a desired transparent conductive layer on the substrate (2) The steps of forming a pattern are formed.

在進行貼合之步驟中，將設置有上述透明導電層(2)之基體，與上述剝離材，以使透明導電層(2)與感熱接著劑層係如相互密合而貼合並加熱及加壓。尤其是透明導電層(2)係不含黏合劑樹脂，或是雖即便含有但亦為含量少時，藉由感熱接著劑層之加熱、加壓，感熱接著劑軟化而滲透至透明導電層(2)之奈米金屬線之間隙，或是纖維狀導電性物質之網眼內，而接著感熱接著劑與透明導電層(2)內之金屬奈米線。 In the step of bonding, the substrate provided with the transparent conductive layer (2) and the release material are such that the transparent conductive layer (2) and the thermal adhesive layer are adhered to each other and heated and added. Pressure. In particular, the transparent conductive layer (2) does not contain a binder resin, or if it is contained in a small amount, the heat-sensitive adhesive layer is softened and penetrates into the transparent conductive layer by heating and pressurization of the heat-sensitive adhesive layer ( 2) The gap between the nanowires, or the mesh of the fibrous conductive material, followed by the thermal adhesive and the metal nanowires in the transparent conductive layer (2).

其後，將貼合部分之感熱接著劑層冷卻至常溫程度後，將上述剝離材自上述基體剝離，並藉由將與上述感熱接著劑層接著部分之透明導電層(2)，剝離、轉移至支撐體上經負型圖案化之感熱接著劑層上，而於基體上殘留透明導電層(2)之正型圖案，於基體上完成所欲之透明導電層(2)之圖案。 Thereafter, after the heat-sensitive adhesive layer of the bonded portion is cooled to a normal temperature, the release material is peeled off from the substrate, and the transparent conductive layer (2) adhering to the heat-sensitive adhesive layer is peeled off and transferred. To the negatively patterned thermal adhesive layer on the support, a positive pattern of the transparent conductive layer (2) remains on the substrate, and the desired pattern of the transparent conductive layer (2) is completed on the substrate.

作為本發明之製造方法中的貼合方法，只要是藉由貼合時之加熱、加壓而不產生基體之熱變形的方法，則無特別限定。可舉出例如：於可加熱、加壓之兩片平板間，配置具有上述透明導電層(2)之基體與上述剝離材之支撐體上的感熱接著劑層，一定時間加熱加壓之平板層合法，或於任一側或兩側為可加熱之兩支輥對的夾(nip)之間，搬送且挾入具有上述透明導電層(2)之基體與上述剝離材，藉由加熱、線加壓，使輥迴轉，而加壓面整體之輥層合法等。 The bonding method in the production method of the present invention is not particularly limited as long as it is a method of heating and pressurizing at the time of bonding without causing thermal deformation of the substrate. For example, a base layer having the transparent conductive layer (2) and a heat-sensitive adhesive layer on the support of the release material may be disposed between the two sheets that can be heated and pressurized, and the flat layer is heated and pressurized for a certain period of time. Between the nips of the two pairs of heated rolls on either side or both sides, the substrate having the transparent conductive layer (2) and the above-mentioned release material are conveyed and inserted, by heating, line Pressurization, the roller is rotated, and the roll layer of the entire pressing surface is legalized.

尤其是，後者之輥層合法，其係能夠以輥對輥(roll-to-roll)的連續處理，具有優異之生產效率。輥層合 方式之輥，如上述，只要任一側或兩側為可加熱輥即可。又，輥之材質，只要是所使用之透明基體或是支撐體不會產生熱變形，並可良好地熱接著透明導電層(2)與感熱接著材層，則無定別限定。具體而言，較佳為金屬輥為主體之剛體輥，與耐熱橡膠製為主體之彈性輥的組合，可使用金屬/金屬、金屬/彈性、彈性/彈性之所有組合。其中，又為了在輥對的夾之間使感熱接著劑之黏著性表現，較佳為夾寬廣、可加長加熱時間之彈性/彈性、彈性/金屬的輥對。 In particular, the latter roll layer is legal, which is capable of continuous roll-to-roll processing and has excellent production efficiency. Roll lamination The roller of the mode, as described above, may be any one of the sides or both sides of the heatable roller. Further, the material of the roller is not limited as long as it is a transparent substrate or a support which is not thermally deformed, and can be thermally adhered to the transparent conductive layer (2) and the heat-sensitive adhesive layer. Specifically, a combination of a metal roll as a main body rigid roll and a heat resistant rubber main body elastic roll can be used, and all combinations of metal/metal, metal/elasticity, and elasticity/elasticity can be used. Further, in order to express the adhesiveness of the heat-sensitive adhesive between the clips of the pair of rolls, it is preferable to form a pair of elastic/elastic, elastic/metal which has a wide width and can lengthen the heating time.

又，作為貼合時之處理條件，透明基體為熱可塑性塑膠之情形，只要不使透明基體之熱變形發生，而適當選擇表現感熱接著劑相對於透明導電層之黏著性的溫度、壓力條件即可。例如，處理溫度係較佳為70℃~150℃，更佳為80℃~130℃，再更佳為90℃~120℃。壓力係只要選擇以輥線壓於10kN/m~60kN/m之範圍可獲得良好之轉移狀態的最小線壓即可。又，亦可視需要，於貼合前預先加熱感熱接著劑層部分。 Further, in the case of the processing conditions at the time of bonding, the transparent substrate is a thermoplastic plastic, and the temperature and pressure conditions for expressing the adhesion of the heat-sensitive adhesive to the transparent conductive layer are appropriately selected as long as the thermal deformation of the transparent substrate is not caused. can. For example, the treatment temperature is preferably from 70 ° C to 150 ° C, more preferably from 80 ° C to 130 ° C, still more preferably from 90 ° C to 120 ° C. As long as the pressure system is selected to have a roll line pressure of 10 kN/m to 60 kN/m, a minimum line pressure of a good transfer state can be obtained. Further, the heat-sensitive adhesive layer portion may be previously heated before the bonding as needed.

於上述剝離材自基體剝離之步驟中，將經貼合的附透明導電層(2)之基體，與上述剝離材冷卻至室溫左右，將上述剝離材自基體剝離。對應於上述剝離材之支撐體上所所形成之感熱接著劑層的負型圖案，在剝離步驟與感熱接著劑層所接著之透明導電層(2)，係與感熱接著劑層一同自基體被剝離，未對應於感熱接著劑層所形成之部分的透明導電層(2)，係作為透明導電層(2)之正型圖案殘留於基體上，而於基體上完成透明導電層(2)之圖案。 再者，採取於剝離前吹付冷卻用空氣等之冷卻方法，於良好地進行剝離而防止產生未剝離部分之圖案缺陷之目的係為有效。 In the step of peeling the release material from the substrate, the bonded base material of the transparent conductive layer (2) is cooled to about room temperature with the release material, and the release material is peeled off from the substrate. Corresponding to the negative pattern of the heat-sensitive adhesive layer formed on the support of the above-mentioned release material, the transparent conductive layer (2) followed by the heat-sensitive adhesive layer in the peeling step and the heat-sensitive adhesive layer are The transparent conductive layer (2) which is not peeled off corresponding to the portion formed by the heat-sensitive adhesive layer remains as a positive pattern of the transparent conductive layer (2) on the substrate, and the transparent conductive layer (2) is completed on the substrate. pattern. In addition, it is effective to prevent the occurrence of pattern defects in the unpeeled portion by performing a cooling method in which cooling air or the like is blown before the peeling.

於本發明之經圖案化之透明導電層(2)的形成方法中，係於剝離材以感熱接著劑形成負型圖案，自均勻地形成於基體上設置之有色的透明層上之透明導電層(2)剝離不要部分。藉由剝離材之透明導電層(2)的圖案化，係僅以塗布於剝離材之支撐體上感熱接著劑之有無來決定，於對應透明導電層(2)之未剝離部分的剝離材之部份係未塗布感熱接著劑。因此，可將透明導電層(2)確實地殘留在有色之透明層(1)上，又沒有在透明導電層(2)上殘留不要之感熱接著劑而使透明導電層(2)之透光率下降之虞。 In the method for forming the patterned transparent conductive layer (2) of the present invention, the release material is formed into a negative pattern by a heat-sensitive adhesive, and is formed from a transparent conductive layer uniformly formed on the colored transparent layer provided on the substrate. (2) Do not peel off part. The patterning of the transparent conductive layer (2) of the release material is determined only by the presence or absence of the heat-sensitive adhesive applied to the support of the release material, and the release material corresponding to the unpeeled portion of the transparent conductive layer (2) Some were uncoated with a heat sensitive adhesive. Therefore, the transparent conductive layer (2) can be surely left on the colored transparent layer (1) without leaving a heat-sensitive adhesive on the transparent conductive layer (2) to make the transparent conductive layer (2) transparent. The rate of decline.

如此，若為使用藉由剝離材而自基體剝離、去除基體上之透明導電層(2)之不要部分而形成所欲之導電性圖案的方法，則利用藉由塗布而形成透明導電層(2)之步驟所形成之基體上之透明導電層(2)，係部分地以原樣殘留。因此，如利用正型圖案而使用剝離步驟中之剝離部分時，不會有緊鄰透明導電層(2)而形成感熱接著劑層。又，使用正型圖案之情形時，由於使用自基體剝離之圖案，連接導電層之基體之部分係成為圖案形成後之最上層。在導電層之形成使用樹脂時，係成為樹脂集中於此部分，而表面固有電阻亦高，又，樹脂干擾而於後步驟使保護層用塗料浸漬於導電層係為困難。 Thus, if a desired conductive pattern is formed by peeling off the substrate from the substrate by the release material and removing the unnecessary portion of the transparent conductive layer (2) on the substrate, the transparent conductive layer is formed by coating. The transparent conductive layer (2) on the substrate formed by the step is partially left as it is. Therefore, when the peeling portion in the peeling step is used by using the positive pattern, there is no adjacent heat conductive layer (2) to form the heat sensitive adhesive layer. Further, in the case of using a positive pattern, since the pattern peeled off from the substrate is used, the portion of the substrate to which the conductive layer is bonded is the uppermost layer after pattern formation. When a resin is used for the formation of the conductive layer, the resin is concentrated in this portion, and the surface specific resistance is also high. Further, the resin interferes, and it is difficult to immerse the protective layer coating material in the conductive layer in the subsequent step.

相對於此，使用負型圖案於剝離步驟進行導電層之剝離時，殘留之透明導電層係與形成時同樣地，少量樹脂成分集中於近基體側，固定金屬奈米線與基體而基體之遠離側為金屬奈米線自樹脂露出之狀態。因此下一步驟中之保護層用塗料良好地浸漬於導電層中，而將導電層中之金屬奈米線良好地固定於基體。保護層用塗料之塗布前，因基本上導電層表面露出金屬奈米線，成為表面固有電阻低導電性良好之狀態，可由此上方使保護層用塗料浸漬於導電層，而成為符合於使用目的之表面固有電阻。 On the other hand, when the conductive layer is peeled off in the peeling step using the negative pattern, the remaining transparent conductive layer is concentrated on the near substrate side in the same manner as in the formation, and the metal nanowire is fixed to the substrate while the substrate is away from the substrate. The side is the state in which the metal nanowire is exposed from the resin. Therefore, the protective layer coating layer in the next step is well immersed in the conductive layer, and the metal nanowire in the conductive layer is well fixed to the substrate. Before the coating of the protective layer, the metal nanowire is exposed on the surface of the conductive layer, and the surface has a low specific resistance and a good electrical conductivity. The coating for the protective layer is immersed in the conductive layer, thereby achieving the purpose of use. The inherent resistance of the surface.

更藉由於塗布保護層用塗料而固定化透明導電層前形成圖案，從與透明導電層之感熱接著劑連接之部分，該接著劑容易浸漬於導電層內之金屬奈米線內，可將導電層良好地自基體剝離。 Further, by forming a pattern before the transparent conductive layer is fixed by coating the protective layer coating, the adhesive is easily immersed in the metal nanowire in the conductive layer in a portion connected to the heat conductive adhesive of the transparent conductive layer, and the conductive material can be electrically conductive. The layer is well peeled off from the substrate.

(保護層) (The protective layer)

本發明之附透明導電層之基體，較佳為以保護上述透明導電層(2)之目的設置保護層。保護層，在以上述步驟(C)之方法將透明電極層圖案化之情形，係於形成所欲之圖案後，藉由於基體上及基體上所形成之透明導電層之整面進行保護層用塗料之塗布而得。 In the substrate with a transparent conductive layer of the present invention, it is preferred to provide a protective layer for the purpose of protecting the transparent conductive layer (2). In the case of patterning the transparent electrode layer by the method of the above step (C), after the formation of the desired pattern, the protective layer is used for the protective layer by the entire surface of the transparent conductive layer formed on the substrate and the substrate. Coating the coating.

保護層用塗料之塗布步驟，係利用上述之貼合步驟及剝離步驟，藉由將在一部分被所形成之透明導電層圖案所被覆之有色之透明層的整面，塗布保護層用塗料，使溶劑成分乾燥，視需要硬化所含有之樹脂成分而形成保護層來進行。藉由本步驟使透明導電層之表面被被 覆、保護之同時，保護層用塗料係一面填充透明導電層中之導電性微粒子之間隙、或纖維狀，較佳為線狀之導電性物質所形成之網眼的間隙，而到達基體，於硬化時將透明導電層整體牢固地固定化於基體上，形成附透明導電層之基體。 The coating step of the protective layer coating is carried out by applying the coating material for the protective layer to the entire surface of the colored transparent layer covered by the formed transparent conductive layer pattern by the above-mentioned bonding step and peeling step. The solvent component is dried, and if necessary, the resin component contained is hardened to form a protective layer. By this step, the surface of the transparent conductive layer is At the same time of covering and protecting, the protective layer coating material fills the gap of the conductive fine particles in the transparent conductive layer, or the fiber shape, preferably the gap of the mesh formed by the linear conductive material, and reaches the substrate. When curing, the transparent conductive layer is firmly fixed to the substrate as a whole to form a substrate with a transparent conductive layer.

上述保護層用塗料，並無限定為可經由聚合、交聯製程而硬化形成者，但是由塗膜之耐久性、耐摩擦性之方面，較佳為經過藉由可見光或紫外線、電子束、加熱等之單體的聚合，或是藉由交聯劑之高分子化合物之交聯而固定化者。具體而言，可舉出：包含黏合劑樹脂與反應性單體或是反應性寡聚物之塗料，或是包含反應性單體或是反應性寡聚物之塗料等。 The coating material for a protective layer is not limited to being formed by curing by a polymerization or crosslinking process, but it is preferably subjected to visible light or ultraviolet rays, electron beams, and heating in terms of durability and abrasion resistance of the coating film. The polymerization of the monomer or the like, or the crosslinking by the crosslinking of the polymer compound of the crosslinking agent. Specific examples thereof include a coating material containing a binder resin and a reactive monomer or a reactive oligomer, or a coating material containing a reactive monomer or a reactive oligomer.

作為黏合劑樹脂用於固體高分子基質之形成的有機聚合物，較佳為具有鍵結於碳骨架之極性官能基者。作為極性官能基，係可例示：羧基、酯基、酮基、腈基、胺基、磷酸基、硫醯基(sulfuryl)、磺酸基、聚烷二醇基及醇性羥基等。作為黏合劑之有用的聚合物之例有：丙烯酸樹脂、醇酸樹脂、聚胺甲酸酯、丙烯酸胺甲酸乙酯、聚碳酸酯、聚酯、聚苯乙烯、聚縮醛、聚醯胺、聚乙烯醇、聚乙烯乙酯(polyvinyl acetate)及纖維素等。又，無機聚合物之例有：藉由四烷氧基矽烷之水解．縮合而生成之矽氧烷系聚合物。 The organic polymer used as the binder resin for the formation of the solid polymer matrix is preferably one having a polar functional group bonded to the carbon skeleton. The polar functional group may, for example, be a carboxyl group, an ester group, a ketone group, a nitrile group, an amine group, a phosphoric acid group, a sulfuryl group, a sulfonic acid group, a polyalkylene glycol group or an alcoholic hydroxyl group. Examples of useful polymers as binders include acrylic resins, alkyd resins, polyurethanes, urethane acrylates, polycarbonates, polyesters, polystyrenes, polyacetals, polyamines, Polyvinyl alcohol, polyvinyl acetate, cellulose, and the like. Further, examples of inorganic polymers are: hydrolysis by tetraalkoxy decane. A siloxane-based polymer formed by condensation.

藉由聚合而形成包含有機聚合物之固體高分子基質的情形，作為單體之聚合性的有機單體或寡聚物之例有：丙烯酸甲酯、甲基丙烯酸甲酯、甲氧基聚乙二醇甲 基丙烯酸酯、縮水甘油丙烯酸酯、環氧乙烷改質磷酸丙烯酸酯、胺甲酸乙酯丙烯酸酯、聚乙二醇甲基丙烯酸酯、聚丁二烯丙烯酸酯、聚酯丙烯酸酯等所代表之丙烯酸酯及甲基丙烯酸酯型單體及寡聚物；單(2-甲基丙烯醯氧乙基)酸磷酸酯(rmono(2-methacryloyloxyethyl)acid phosphate)、丙烯酸、甲基丙烯酸、伊康酸、丙烯腈、甲基丙烯腈、苯乙烯、乙烯甲苯等之其他乙烯單體；雙酚A二縮水甘油醚等之環氧化合物等。 In the case of forming a solid polymer matrix containing an organic polymer by polymerization, examples of the polymerizable organic monomer or oligomer as a monomer include methyl acrylate, methyl methacrylate, and methoxy polyethylene. Glycol Base acrylate, glycidyl acrylate, ethylene oxide modified phosphoric acid acrylate, urethane acrylate, polyethylene glycol methacrylate, polybutadiene acrylate, polyester acrylate, etc. Acrylate and methacrylate type monomers and oligomers; mono (2-methacryloyloxyethyl) acid phosphate, acrylic acid, methacrylic acid, itaconic acid Other ethylene monomers such as acrylonitrile, methacrylonitrile, styrene, and vinyl toluene; and epoxy compounds such as bisphenol A diglycidyl ether.

藉由聚合而形成包含無機聚合物之固體高分子基質的情形，單體之聚合性的無機單體之例有：Si、Ti、Zr、Al、Sn、Fe、Co、Ni、Cu、Zn、Pb、Ag、In、Sb、Pt、Au等之金屬的無機酸鹽、有機酸鹽、烷氧化物，及錯體(螯合物)。因為此等係經由水解或熱分解而聚合，最後成為無機物(金屬氧化物、氧化物、碳化物、金屬等)，而於本發明作為無機單體來處理。此等之無機單體，亦可以其部分水解之狀態來使用。接著，例示各金屬化合物之具體例，但並非限定為此等者。 In the case where a solid polymer matrix containing an inorganic polymer is formed by polymerization, examples of the polymerizable inorganic monomer of the monomer include Si, Ti, Zr, Al, Sn, Fe, Co, Ni, Cu, Zn, A mineral acid salt, an organic acid salt, an alkoxide, and a complex (chelate) of a metal such as Pb, Ag, In, Sb, Pt, or Au. Since these are polymerized by hydrolysis or thermal decomposition, and finally become inorganic substances (metal oxides, oxides, carbides, metals, etc.), they are treated as inorganic monomers in the present invention. These inorganic monomers can also be used in a partially hydrolyzed state. Next, specific examples of the respective metal compounds are exemplified, but are not limited thereto.

上述之聚合物系黏合劑(有機聚合物、無機聚合物)樹脂，或形成聚合物系黏合劑之有機或無機之單體或寡聚物的一種或兩種以上，視需要以有機溶劑溶解或稀釋，而調製黏度為25cps以下，更佳為10cps以下之液體，使用於第1步驟所形成之塗膜的含浸。若該液體之黏度高於25cps，則於塗膜含浸時，液體無法使其如到達基體般而充分地滲透在塗膜內部，無法獲得作為目的之密合性及膜強度之提升效果。又，若液體為高黏度，則 由於過量之液體堆積於第1步驟所形成之透明導電層上，形成不含導電性微粉末之絕緣性之層，而導電性顯著地降低。 One or more of the above-mentioned polymer-based binder (organic polymer, inorganic polymer) resin or organic or inorganic monomer or oligomer forming a polymer-based binder, if necessary, dissolved in an organic solvent or The solution is diluted and prepared to have a viscosity of 25 cps or less, more preferably 10 cps or less, and is used for impregnation of the coating film formed in the first step. When the viscosity of the liquid is higher than 25 cps, when the coating film is impregnated, the liquid cannot sufficiently penetrate into the inside of the coating film as it reaches the substrate, and the effect of improving the adhesion and the film strength cannot be obtained. Also, if the liquid is highly viscous, then Since an excessive amount of liquid is deposited on the transparent conductive layer formed in the first step, an insulating layer containing no conductive fine powder is formed, and the electrical conductivity is remarkably lowered.

用於溶解或稀釋之有機溶劑並無特別限制，只要是可溶解上述黏合劑或形成黏合劑之單體，則亦可使用液狀有機化合物，及水作為溶劑。 The organic solvent to be dissolved or diluted is not particularly limited, and as long as it is a monomer which can dissolve the above-mentioned binder or form a binder, a liquid organic compound and water can also be used as a solvent.

作為此含浸用液體於所使用之保護層用塗料，可視需要添加：硬化觸媒(熱硬化之情形)、光聚合起始劑(紫外線硬化之情形)、交聯劑、水解觸媒(例：酸)、聚合起始劑、安定劑(例如：抗氧化劑及用於產品壽命長期化之紫外線安定劑，及用於保存期限改善之聚合防止劑)界面活性劑、pH調整劑等。進而亦可進一步包含防止金屬奈米線腐蝕之抗腐蝕劑。 The coating material for the impregnation liquid to be used may be added as needed: a curing catalyst (in the case of thermal curing), a photopolymerization initiator (in the case of ultraviolet curing), a crosslinking agent, and a hydrolysis catalyst (example: An acid), a polymerization initiator, a stabilizer (for example, an antioxidant, an ultraviolet stabilizer for long-term product life, and a polymerization inhibitor for improving the shelf life), a surfactant, a pH adjuster, and the like. Further, an anticorrosive agent for preventing corrosion of the metal nanowire may be further included.

作為適切之溶劑之例，可舉出：水、醇類、酮類、環狀醚化合物類(四氫呋喃等)、烴(例如：環己烷)，或芳香族系溶劑(苯、甲苯、二甲苯等)。更佳為溶劑係揮發性，具有200℃以下、150℃以下、或100℃以下之沸點。 Examples of the solvent to be used include water, alcohols, ketones, cyclic ether compounds (such as tetrahydrofuran), hydrocarbons (for example, cyclohexane), or aromatic solvents (benzene, toluene, and xylene). Wait). More preferably, the solvent is volatile, and has a boiling point of 200 ° C or less, 150 ° C or less, or 100 ° C or less.

作為形成保護層之方法只要是習知之濕式塗布法則無特別限制。具體而言，可舉出：噴霧塗布、棒塗布、輥塗布、模塗布、噴墨塗布、網版塗布、浸漬塗布等。 The method of forming the protective layer is not particularly limited as long as it is a conventional wet coating method. Specific examples thereof include spray coating, bar coating, roll coating, die coating, inkjet coating, screen coating, and dip coating.

利用保護層用塗料一面含浸透明導電層而形成保護層時，塗布、乾燥後之保護層之膜厚，相對於保護層用塗料塗布前之透明導電層，若過薄，則耐摩擦性、耐磨損性、耐候性等之作為保護層的功能降低，若過厚，則作為導體之接觸電阻增加。 When the protective layer is formed by impregnating the transparent conductive layer with the protective layer coating layer, the thickness of the protective layer after application and drying is thicker than the transparent conductive layer before the coating for the protective layer coating, and if it is too thin, the abrasion resistance and the resistance are resistant. The function as a protective layer such as abrasion resistance and weather resistance is lowered, and if it is too thick, the contact resistance as a conductor increases.

保護層用塗料之塗布係透明導電層之膜厚以50~150nm之範圍而形成時，塗布、乾燥後之膜厚較佳為30~150nm，可考慮透明導電層之膜厚而使表面電阻率、霧度等可實現所定之值來調整。較佳為40~175nm，最佳為50~150nm。保護層用塗料之乾燥後之膜厚，雖亦依據透明導電層之膜厚，但是若為30nm以上之膜厚，則金屬保護層不會過度露出於保護層表面，有藉由保護層之保護功能較良好地作用之傾向；若為150nm以下之膜厚，則於透明導電性物質之表面不會形成過厚之被膜，係有可確保較良好之導電性能之傾向。 When the film thickness of the coating-based transparent conductive layer of the protective layer coating is in the range of 50 to 150 nm, the film thickness after application and drying is preferably 30 to 150 nm, and the surface resistivity may be considered in consideration of the film thickness of the transparent conductive layer. , haze, etc. can be adjusted to achieve the desired value. It is preferably 40 to 175 nm, and most preferably 50 to 150 nm. The film thickness after drying of the coating for a protective layer depends on the film thickness of the transparent conductive layer. However, if the film thickness is 30 nm or more, the metal protective layer is not excessively exposed on the surface of the protective layer, and is protected by a protective layer. When the film thickness is 150 nm or less, an excessively thick film is not formed on the surface of the transparent conductive material, and a tendency to ensure good electrical conductivity is obtained.

藉由將保護層用塗料，整面塗布於利用經圖案化之透明導電層而其一部份被被覆之基體上，而於透明導電層部分係成為一面浸漬保護層用塗料而覆蓋基體的整面。藉由於最後進行保護層用塗料之塗布，相較於將導電層以保護層用塗料固定化後形成導電性圖案之情形，可使圖案化透明導電性薄膜之表面更平滑，且藉由保護層用塗料利用浸漬亦侵入導電層內，而可形成光學上均質之圖案化透明導電性薄膜。 By coating the protective layer with the entire surface of the substrate coated with a patterned transparent conductive layer, the transparent conductive layer portion is covered with a coating for impregnating the protective layer and covering the substrate. surface. By coating the protective layer coating at the end, the surface of the patterned transparent conductive film can be made smoother and the protective layer can be made smoother than when the conductive layer is fixed by the protective layer coating to form a conductive pattern. The coating is also impregnated into the conductive layer by impregnation to form an optically homogeneous patterned transparent conductive film.

[實施例] [Examples]

以下，進一步具體地說明本發明，但本發明並不限定於該等實施例。 Hereinafter, the present invention will be specifically described, but the present invention is not limited to the examples.

依以下之調整例所記載之調配量，調整用於形成有色之透明層的有色透明層用塗料。 The coating material for a colored transparent layer for forming a colored transparent layer was adjusted in accordance with the blending amount described in the following adjustment examples.

《有色之透明層(1-1)用塗料的調整例》 "Adjustment Example of Paint for Colored Transparent Layer (1-1)"

《有色之透明層(1-2)用塗料的調整例》 "Adjustment Example of Paint for Colored Transparent Layer (1-2)"

《有色之透明層(1-3)用塗料的調整例》 "Adjustment Example of Paint for Colored Transparent Layer (1-3)"

《有色之透明層(1-4)用塗料的調整例》 "Adjustment example of paint for colored transparent layer (1-4)"

《有色之透明層(1-5)用塗料的調整例》 "Adjustment Example of Paint for Colored Transparent Layer (1-5)"

《有色之透明層(1-6)用塗料的調整例》 "Adjustment example of paint for colored transparent layer (1-6)"

《有色之透明層(1-7)用塗料的調整例》 "Adjustment Example of Paint for Colored Transparent Layer (1-7)"

《有色之透明層(1-8)用塗料的調整例》 "Adjustment example of paint for colored transparent layer (1-8)"

[固體成分30%、固體成分之羥基值6、東洋紡績公司製] [30% solid content, hydroxyl value of solid content 6, manufactured by Toyobo Co., Ltd.]

《有色之透明層(1-9)用塗料的調整例》 "Adjustment Example of Paint for Colored Transparent Layer (1-9)"

《有色之透明層(1-10)用塗料的調整例》 "Adjustment example of paint for colored transparent layer (1-10)"

《比較用有色之透明層(1-H)用塗料的調整例》 "Adjustment of Coatings for Colored Transparent Layer (1-H)"

《樹脂透明層(1-I)用塗料的調整例》 "Adjustment Example of Coating for Transparent Layer of Resin (1-I)"

(有色之透明層(1)的製作) (production of colored transparent layer (1))

使用棒塗機，於厚度125μm之高透明PET薄膜(Teijin DuPont Films公司製HF1C22-125)的基體上，將上述有色之透明層(1-1)~(1-10)、(1-H)、(1-I)用塗料，塗布、乾燥使濕厚度如成為20μm。此處所使用的PET薄膜之利用後述的方法測定之霧度值為0.28，波長450nm之吸光度為0.0458、波長550nm之吸光度為0.0420、波長650nm之吸光度為0.0380。各別之霧度值與吸光度如下。再者，表中之霧度值、吸光度，均為自於PET上塗布有色之透明層之薄膜的霧度值、吸光度、扣除PET薄膜本身的霧度值、吸光度之值。 The colored transparent layers (1-1) to (1-10), (1-) were applied to a substrate of a transparent PET film (HF1C22-125 manufactured by Teijin DuPont Films Co., Ltd.) having a thickness of 125 μm using a bar coater. H), (1-I) coating, coating, drying to make the wet thickness as 20 μ m. The PET film used herein had a haze value of 0.28 as measured by a method described later, an absorbance at a wavelength of 450 nm of 0.0458, an absorbance at a wavelength of 550 nm of 0.0420, and an absorbance at a wavelength of 650 nm of 0.0380. The respective haze values and absorbances are as follows. Further, the haze value and the absorbance in the table are the values of the haze value, the absorbance, the haze value of the PET film itself, and the absorbance from the film on which the colored transparent layer is applied on the PET.

(銀奈米線之合成) (Synthesis of silver nanowires)

銀奈米線係於Y.Sun,B.Gates,B.Mayers & Y.Xia,”Crystalline silver nanowires by soft solution processing”,Nano letters,(2002),2(2)165~168所記載之使用多元醇之方法後，在聚乙烯吡咯啶酮(PVP)之存在下，將硫酸銀溶解於乙二醇，藉由將此還原而合成之奈米線。即，於本發明中，係使用利用於Cambrios Technologies Corporation美國暫時申請案60/815,627號所記載之經修正的多元醇方法，所合成之奈米線。 The silver nanowire is used in Y. Sun, B. Gates, B. Mayers & Y. Xia, "Crystalline silver nanowires by soft solution processing", Nano letters, (2002), 2(2) 165-168. After the method of the polyol, the silver sulfate is dissolved in ethylene glycol in the presence of polyvinylpyrrolidone (PVP), and the nanowire is synthesized by reduction. That is, in the present invention, the synthesized nanowires are used in the modified polyol method described in U.S. Patent Application Serial No. 60/815,627, the entire disclosure of which is incorporated herein.

(透明導電層(2)之製作) (Production of transparent conductive layer (2))

作為形成透明導電層(2)之金屬奈米線，將於水性溶劑含有0.1%w/v之以上述方法所合成的短軸徑約70nm~80nm、縱橫比100以上之銀奈米線之水分散體(Cambrios Technologies Corporation公司製ClearOhmTM,Ink-A AQ)，使用2支逆轉輥塗布機，於上述有色之透明層(1)上塗布、乾燥成濕厚度為20μm，作為輥狀之塗布物，獲得形成有透明導電層之基體。將此稱為附透明導電層之基體(PN)。 The metal nanowire which forms the transparent conductive layer (2) contains 0.1% w/v of water of a silver nanowire having a short axis diameter of about 70 nm to 80 nm and an aspect ratio of 100 or more synthesized by the above method in an aqueous solvent. The dispersion (ClearOhmTM, Ink-A AQ, manufactured by Cambrios Technologies Corporation) was coated on the above-mentioned colored transparent layer (1) using two reverse roll coaters to form a wet thickness of 20 μm as a roll coating. A substrate having a transparent conductive layer formed thereon is obtained. This is referred to as a substrate (PN) with a transparent conductive layer.

(包含具有經負型圖案化之感熱接著劑層之支撐體的剝離用基材之製作) (Production of a substrate for peeling comprising a support having a negatively patterned heat-sensitive adhesive layer)

將CRISVON NT-810-45(DIC公司製聚胺甲酸酯樹脂，45%溶液)100重量份，溶解於甲基乙基酮62.5重量份、甲苯62.5重量份來作為感熱接著劑。此聚胺甲酸酯樹脂之代表物性值，由以黏彈性測定(升溫速度3℃/分)所得之tan δ之峰值獲得的玻璃轉移溫度為42℃，以拉 伸速度300mm/分所得之拉伸斷裂強度為277×10E5Pa、拉伸斷裂伸度為665%、以高壓式流動測試機(flow tester)(鑄模：1 ψ×1L、加壓：98N)之測定所獲得的流動起始溫度為90℃。將厚度23μm之PET薄膜(Teijin DuPont Films公司製Tejintetron薄膜G2)作為支撐體，將上述之感熱接著劑用液於其上進行圖案印刷。此處作為於基體所形成之導電層圖案，係成為靜電容量方式投影型用觸控面板用之鑽石圖案。鑽石圖案係，將一邊之長度為4mm且內角為90度之鑽石形狀之靜電元件之圖案，與線寬度為600μm之細線圖案相互連續之直線狀圖案(Y圖案)，以及一邊之長度為4mm且內角為90度之鑽石形狀之靜電元件之圖案，與線寬度為400μm之細線圖案相互連續之直線狀圖案(X圖案)，以原料(後加工前之薄膜)之流動方向與細線方向如平行及垂直而配置的圖案。因此，於上述支撐體上，相對於根據透明導電層應形成之圖案(參照圖1)，將其之負型圖案即圖2之圖案利用凹版印刷進行印刷。乾燥印刷塗膜後，以感熱接著劑層之厚度成為如0.5μm~1.0μm而進行塗布，獲得如圖2之負型影像狀地圖案印刷感熱接著劑之剝離用基材。 100 parts by weight of CRISVON NT-810-45 (a PCT company's polyurethane resin, 45% solution) was dissolved in 62.5 parts by weight of methyl ethyl ketone and 62.5 parts by weight of toluene to obtain a heat-sensitive adhesive. The representative physical property value of the polyurethane resin is a glass transition temperature of 42 ° C obtained from a peak of tan δ obtained by a viscoelasticity measurement (temperature rising rate of 3 ° C /min), and a tensile strength of 300 mm / min. The tensile breaking strength was 277×10E5 Pa, the tensile elongation at break was 665,5%, and the flow initiation temperature obtained by the measurement of a high-pressure flow tester (molding mold: 1 ψ×1 L, pressure: 98 N) was 90 ° C. PET film of thickness 23 μ m (Teijin DuPont Films Corporation Tejintetron film G2) as a support, the above-described heat-sensitive adhesive solution on the printing pattern thereon. Here, the conductive layer pattern formed on the substrate is a diamond pattern for a touch panel for a capacitance type projection type. The diamond pattern is a linear pattern (Y pattern) in which a diamond-shaped electrostatic element having a length of 4 mm and an internal angle of 90 degrees is continuous with a fine line pattern having a line width of 600 μm , and the length of one side. A pattern of a diamond-shaped electrostatic element having a diameter of 4 mm and an internal angle of 90 degrees, and a linear pattern (X pattern) in which a thin line pattern having a line width of 400 μm is continuous with each other, and a flow direction of the raw material (film before post-processing) A pattern arranged in parallel and perpendicular to the direction of the thin line. Therefore, on the support, the negative pattern, that is, the pattern of FIG. 2, is printed by gravure printing with respect to the pattern to be formed according to the transparent conductive layer (see FIG. 1). After the printed film is dried, the thickness of the heat-sensitive adhesive layer is applied to a thickness of, for example, 0.5 μm to 1.0 μm to obtain a base material for peeling off the pattern-sensitive heat-sensitive adhesive as shown in FIG.

(透明導電層(2)之圖案化步驟) (patterning step of transparent conductive layer (2))

一面移動作為上述輥狀之塗布物而製成之形成了透明導電層的基體，與具有經負型圖案化之感熱接著劑層的剝離用基材，而將透明導電層與感熱接著劑層如相互相向地重疊，使用具有藉由金屬製加熱輥與耐熱矽輥之 加熱、加壓夾的疊合機，在加熱輥溫度115℃、輥夾持壓(線壓)30kN/m、速度3m/分之條件下，進行連續地貼合。一面移動經貼合之材料，而在貼合部分之溫度下降至室溫左右之時點，自基體連續地剝離支撐體，而獲得輥狀的薄膜基體。該輥狀的薄膜基體，係具有於基體上透明導電層(2)殘留為所欲之圖案的經圖案化之透明導電層(2)。將此稱為附圖案之附透明導電層之基體(P)。 a substrate formed with the transparent conductive layer formed by moving the coating material as the above-mentioned roll, and a substrate for peeling having a negatively patterned heat-sensitive adhesive layer, and a transparent conductive layer and a thermal adhesive layer such as Overlapping each other, using a metal heated roll and a heat resistant roll The laminating machine for heating and pressurizing was continuously bonded under the conditions of a heating roll temperature of 115 ° C, a roll nip pressure (linear pressure) of 30 kN/m, and a speed of 3 m/min. The material to be bonded is moved while the temperature of the bonded portion is lowered to about room temperature, and the support is continuously peeled off from the substrate to obtain a roll-shaped film substrate. The roll-shaped film substrate has a patterned transparent conductive layer (2) having a transparent conductive layer (2) remaining on the substrate in a desired pattern. This is referred to as a patterned base (P) with a transparent conductive layer.

(藉由保護層用塗料之塗布之保護層的形成) (Formation of a protective layer coated by a coating for a protective layer)

作為保護層用塗料，係將紫外線硬化樹脂(Cambrios Technologies Corporation公司製，不揮發成份40%)100份，充分溶解於Solmix AP-1(日本ALCOHOL販賣公司製)1950份、異丙醇975份、二丙酮醇975份之混合溶劑而作為保護層用塗料。 As a coating material for a protective layer, 100 parts of an ultraviolet curable resin (40% nonvolatile matter, manufactured by Cambrios Technologies Corporation) was sufficiently dissolved in 1950 parts of Solmix AP-1 (manufactured by ALCOHOL, Japan), and 975 parts of isopropyl alcohol. A mixed solvent of 975 parts of diacetone alcohol was used as a coating material for a protective layer.

保護層用塗料，係於附透明導電層之基體(PN)或附圖案之附透明導電層之基體(P)的透明導電層(2)之整面，使用2支逆轉輥塗布機，一面以該保護層用塗料填充透明導電層(2)中之網眼狀奈米線之間隙，而塗布、乾燥成濕厚度為10μm，其後照射紫外線而形成乾燥厚度約為0.2μm之保護層塗膜。 The coating for the protective layer is applied to the entire surface of the transparent conductive layer (2) of the substrate (P) with the transparent conductive layer or the patterned transparent conductive layer (P), using two reverse roll coaters, one side The protective layer fills the gap of the mesh-like nanowires in the transparent conductive layer (2) with a coating, and is coated and dried to a wet thickness of 10 μm , and then irradiated with ultraviolet rays to form a protective layer having a dry thickness of about 0.2 μm. Coating film.

(實施例1) (Example 1)

附透明導電層之基體(PN-1)及附圖案之附透明導電層之基體(P-1)之製作。 Fabrication of a substrate (PN-1) with a transparent conductive layer and a substrate (P-1) with a transparent conductive layer attached thereto.

使用有色之透明層(1-1)用塗料而形成厚度0.1μm之有色之透明層(1-1)，於其上製作透明導電層(2)。於此設置保護層，作為附透明導電層之基體(PN-1)。 A colored transparent layer (1-1) having a thickness of 0.1 μm was formed using a colored transparent layer (1-1) with a coating material, and a transparent conductive layer (2) was formed thereon. A protective layer is provided here as a substrate (PN-1) with a transparent conductive layer.

又，於其上製成透明導電層(2)後，進行圖案化，於此設置保護層，獲得附圖案之附透明導電層之基體(P-1)。 Further, after the transparent conductive layer (2) was formed thereon, patterning was performed, and a protective layer was provided thereon to obtain a patterned base (P-1) with a transparent conductive layer.

(實施例2) (Example 2)

除使用有色之透明層(1-2)代替有色之透明層(1-1)以外，與實施例1相同，獲得附透明導電層之基體(PN-1)，及附圖案之附透明導電層之基體(P-1)。 A substrate (PN-1) with a transparent conductive layer and a transparent conductive layer with a pattern are obtained, except that a colored transparent layer (1-2) is used instead of the colored transparent layer (1-1). The base (P-1).

(實施例3) (Example 3)

除使用有色之透明層(1-3)代替有色之透明層(1-1)以外，與實施例1相同地，獲得附透明導電層之基體(PN-1)，及附圖案之附透明導電層之基體(P-1)。 A substrate (PN-1) with a transparent conductive layer and a transparent conductive film with a pattern were obtained in the same manner as in Example 1 except that the colored transparent layer (1-3) was used instead of the colored transparent layer (1-1). The base of the layer (P-1).

(實施例4) (Example 4)

除使用有色之透明層(1-4)代替有色之透明層(1-1)以外，與實施例1相同地，獲得附透明導電層之基體(PN-1)，及附圖案之附透明導電層之基體(P-1)。 A substrate (PN-1) with a transparent conductive layer and a transparent conductive film attached thereto were obtained in the same manner as in Example 1 except that the colored transparent layer (1-4) was used instead of the colored transparent layer (1-1). The base of the layer (P-1).

(實施例5) (Example 5)

除使用有色之透明層(1-5)代替有色之透明層(1-1)以外，與實施例1相同地，獲得附透明導電層之基體(PN-1)，及附圖案之附透明導電層之基體(P-1)。 A substrate (PN-1) with a transparent conductive layer and a transparent conductive film with a pattern were obtained in the same manner as in Example 1 except that the colored transparent layer (1-5) was used instead of the colored transparent layer (1-1). The base of the layer (P-1).

(實施例6) (Example 6)

除使用有色之透明層(1-6)代替有色之透明層(1-1)以外，與實施例1相同地，獲得附透明導電層之基體(PN-1)，及附圖案之附透明導電層之基體(P-1)。 A substrate (PN-1) with a transparent conductive layer and a transparent conductive film with a pattern were obtained in the same manner as in Example 1 except that the colored transparent layer (1-6) was used instead of the colored transparent layer (1-1). The base of the layer (P-1).

(實施例7) (Example 7)

除使用有色之透明層(1-7)代替有色之透明層(1-1)以外，與實施例1相同地，獲得附透明導電層之基體(PN-1)，及附圖案之附透明導電層之基體(P-1)。 A substrate (PN-1) with a transparent conductive layer and a transparent conductive film with a pattern were obtained in the same manner as in Example 1 except that the colored transparent layer (1-7) was used instead of the colored transparent layer (1-1). The base of the layer (P-1).

(實施例8) (Example 8)

除使用有色之透明層(1-8)代替有色之透明層(1-1)以外，與實施例1相同地，獲得附透明導電層之基體(PN-1)，及附圖案之附透明導電層之基體(P-1)。 A substrate (PN-1) with a transparent conductive layer and a transparent conductive film with a pattern were obtained in the same manner as in Example 1 except that the colored transparent layer (1-8) was used instead of the colored transparent layer (1-1). The base of the layer (P-1).

(實施例9) (Example 9)

除使用有色之透明層(1-9)代替有色之透明層(1-1)以外，與實施例1相同地，獲得附透明導電層之基體(PN-1)，及附圖案之附透明導電層之基體(P-1)。 A substrate (PN-1) with a transparent conductive layer and a transparent conductive film with a pattern were obtained in the same manner as in Example 1 except that the colored transparent layer (1-9) was used instead of the colored transparent layer (1-1). The base of the layer (P-1).

(實施例10) (Embodiment 10)

除使用有色之透明層(1-10)代替有色之透明層(1-1)以外，與實施例1相同地，獲得附透明導電層之基體(PN-1)，及附圖案之附透明導電層之基體(P-1)。 A substrate (PN-1) with a transparent conductive layer and a transparent conductive film with a pattern were obtained in the same manner as in Example 1 except that the colored transparent layer (1-10) was used instead of the colored transparent layer (1-1). The base of the layer (P-1).

(比較例1) (Comparative Example 1)

除不形成有色之透明層以外，與實施例1相同地，獲得具有鑽石圖案之透明導電層(2)之附透明導電層之基體。 A substrate having a transparent conductive layer (2) having a diamond pattern and a transparent conductive layer was obtained in the same manner as in Example 1 except that a colored transparent layer was not formed.

(比較例2) (Comparative Example 2)

除使用有色之透明層(1-H)代替有色之透明層(1-1)以外，與實施例1相同地，獲得附透明導電層之基體(PN-1)，及附圖案之附透明導電層之基體(P-1)。 A substrate (PN-1) with a transparent conductive layer and a transparent conductive film with a pattern were obtained in the same manner as in Example 1 except that a colored transparent layer (1-H) was used instead of the colored transparent layer (1-1). The base of the layer (P-1).

(比較例3) (Comparative Example 3)

除使用有色之透明層(1-I)代替有色之透明層(1-1)以外，與實施例1相同地，獲得附透明導電層之基體(PN-1)，及附圖案之附透明導電層之基體(P-1)。 A substrate (PN-1) with a transparent conductive layer and a transparent conductive film with a pattern were obtained in the same manner as in Example 1 except that a colored transparent layer (1-I) was used instead of the colored transparent layer (1-1). The base of the layer (P-1).

以下，為了確認附透明導電層之基體之特性，進行評價項目與其測定方法表示如下。 Hereinafter, in order to confirm the characteristics of the base body with the transparent conductive layer, the evaluation items and the measurement methods thereof are shown below.

[表面電阻率之測定] [Measurement of surface resistivity]

將附透明導電層之基體(PN-1)由不同位置分別選定5個部位，使用4探針法電阻率計(三菱Analytech公司製Loresta EP)，將4探針按壓於試樣中央部來測定表面電阻率(Ω/□)，且取5個部位之平均。 The substrate (PN-1) with a transparent conductive layer was selected from five locations at different positions, and a 4-probe resistivity meter (Loresta EP, manufactured by Mitsubishi Analytech Co., Ltd.) was used to measure 4 probes at the center of the sample. Surface resistivity (Ω/□) and averaged over 5 locations.

[霧度值、總透光率之測定] [Measurement of haze value and total light transmittance]

將附透明導電層之基體(PN-1)由不同位置分別選定5個部位，測定中央部且取平均。測定係使用積分球式總透光率測定機(日本電色工業公司製NDH-2000)來測定總透光率(Tt){依據JIS K-7361、NDH-2000測定方法1}與霧度(霧度)(Hz){依據JIS K-7136、NDH-2000測定方法3}。 The base body (PN-1) with the transparent conductive layer was selected from five positions at different positions, and the center portion was measured and averaged. The measurement was carried out by using an integrating sphere type total light transmittance measuring machine (NDH-2000, manufactured by Nippon Denshoku Industries Co., Ltd.) to measure the total light transmittance (Tt) {measured according to JIS K-7361, NDH-2000 method 1} and haze ( Haze) (Hz) {Measurement Method 3 according to JIS K-7136, NDH-2000.

[黃色度*b之測定] [Measurement of yellowness *b]

將附透明導電層之基體(PN-1)使用測色色差計(日本電色工業公司製ZE-2000)，測定黃色度*b(依據JIS K-7105)。 The base (PN-1) with a transparent conductive layer was measured for yellowness *b (according to JIS K-7105) using a colorimetric color difference meter (ZE-2000, manufactured by Nippon Denshoku Industries Co., Ltd.).

[吸光度α之測定] [Measurement of absorbance α ]

將附透明導電層之基體(PN-1)使用分光光度計(日本分光公司製V-650)，測定波長380nm~780nm之吸光度 (依據JIS K-0115)，比較波長450nm、550nm、650nm之吸光度α ₄₅₀、α ₅₅₀、α ₆₅₀。 The base (PN-1) with a transparent conductive layer was measured for absorbance at a wavelength of 380 nm to 780 nm (according to JIS K-0115) using a spectrophotometer (V-650, manufactured by JASCO Corporation), and the absorbances at wavelengths of 450 nm, 550 nm, and 650 nm were compared. α ₄₅₀ , α ₅₅₀ , α ₆₅₀ .

[圖案辨識性之評價] [Evaluation of pattern identification]

於形成保護層塗膜之附圖案之附透明導電層之基體(P-1)中，自原料裁切Y電極之試樣、X電極之試樣後，相對於Y電極之細線方向X電極之細線方向係如直交而配置，使透明導電層(2)面向同一方向(例如：向上)，其中一透明導電層(2)形成部分係與另一導電層剝離部分如重疊般，相互不同地介由OCA(DIC公司製光學黏著片，ZB7032W、厚度50μm)重疊貼合，製作圖案辨識性評價用試樣(參照圖3)。 In the substrate (P-1) with the transparent conductive layer attached to the pattern of the protective layer coating film, after the Y electrode sample and the X electrode sample are cut from the material, the X electrode is thinned with respect to the Y electrode. The thin line direction is arranged such that the transparent conductive layer (2) faces in the same direction (for example, upward), wherein a transparent conductive layer (2) forming portion is overlapped with another conductive layer peeling portion, and is different from each other. An OCA (Optical Adhesive Sheet made of DIC Corporation, ZB7032W, thickness: 50 μm ) was laminated and laminated to prepare a sample for pattern identification evaluation (see FIG. 3).

辨識性評價時，係將試樣設置於黑台紙上，於螢光燈下，以目視比較X電極‧Y電極間之透明導電層(2)之不存在間隙部分之反射光強度，與透明導電膜之反射光強度。 For the identification evaluation, the sample was placed on a black table paper, and the reflected light intensity of the transparent conductive layer (2) between the X electrodes and the Y electrodes was visually compared under the fluorescent lamp, and the transparent conductive layer was transparently conductive. The intensity of the reflected light of the film.

○…幾乎無反射光強度差之情形 ○...there is almost no difference in reflected light intensity

×…反射光強度差大之情形 ×...The difference in reflected light intensity is large

將○判斷為合格程度 Judging ○ as acceptable

[透明性之評價] [Evaluation of transparency]

○…總透光率為88%以上 ○...the total light transmittance is 88% or more

△…總透光率為80%以上未滿88% △...The total light transmittance is 80% or more and less than 88%.

×…總透光率未滿80% ×...The total light transmittance is less than 80%

將△以上判斷為合格程度 Judging △ or above as acceptable

[總合評價] [Total evaluation]

○…圖案辨識性之評價為○，並且透明性之評價為△以上 ○...The evaluation of pattern recognition was ○, and the evaluation of transparency was Δ or more.

×…圖案辨識性之評價為×，或透明性之評價為× ×...The evaluation of pattern recognition is ×, or the evaluation of transparency is ×

將○判斷為合格程度 Judging ○ as acceptable

由表可知，形成有色之透明層的實施例1~10，係顯示良好的表面電阻值，又，總透光率、圖案辨識性及透明性良好。另一方面，未形成有色之透明層的比較例1、於有色之透明層未添加著色顏料，僅形成黏合劑樹脂之比較例3，係由於透明導電層之反射光強度大，圖案辨識性之評價為×。又比較例2，係有色之透明層中之顏料成分過多，霧度變高之同時透射率變低，透明性之評價為×。 As can be seen from the table, Examples 1 to 10 which form a colored transparent layer exhibited good surface resistance values, and also had good total light transmittance, pattern visibility, and transparency. On the other hand, Comparative Example 1 in which a colored transparent layer was not formed, Comparative Example 3 in which a colored pigment was not added to a colored transparent layer, and only a binder resin was formed, because the reflected light intensity of the transparent conductive layer was large, pattern recognition was The evaluation is ×. Further, in Comparative Example 2, the pigment component in the colored transparent layer was excessive, the transmittance was lowered while the haze was high, and the transparency was evaluated as ×.

1‧‧‧基體 1‧‧‧ base

2‧‧‧有色之透明層(1) 2‧‧‧Colored transparent layer (1)

3‧‧‧於X方向形成之鑽石圖案之透明導電層(2) 3‧‧‧Transparent conductive layer of diamond pattern formed in the X direction (2)

4‧‧‧於Y方向形成之鑽石圖案之透明導電層(2) 4‧‧‧Transparent conductive layer of diamond pattern formed in the Y direction (2)

5‧‧‧OCA(光學黏著片) 5‧‧‧OCA (Optical Adhesive Sheet)

圖1，係藉由本發明之方法而形成的觸控面板用透明導電層之鑽石圖案的平面圖。 Figure 1 is a plan view of a diamond pattern of a transparent conductive layer for a touch panel formed by the method of the present invention.

圖2，係在本發明中用於形成在支撐體上的感熱接著劑層之鑽石狀經負型圖案的平面圖。 Figure 2 is a plan view of a diamond-like negative pattern for forming a thermal adhesive layer on a support in the present invention.

圖3，係本發明中之圖案辨認性評價用試樣的剖面圖。 Fig. 3 is a cross-sectional view showing a sample for pattern recognition evaluation in the present invention.

1‧‧‧基體 1‧‧‧ base

2‧‧‧有色之透明層(1) 2‧‧‧Colored transparent layer (1)

3‧‧‧於X方向形成之鑽石圖案之透明導電層(2) 3‧‧‧Transparent conductive layer of diamond pattern formed in the X direction (2)

4‧‧‧於Y方向形成之鑽石圖案之透明導電層(2) 4‧‧‧Transparent conductive layer of diamond pattern formed in the Y direction (2)

5‧‧‧OCA(光學黏著片) 5‧‧‧OCA (Optical Adhesive Sheet)

Claims (5)

一種附透明導電層之基體，其特徵為於透明基體上，依序具有波長450nm、波長550nm及波長650nm之吸光度係分別獨立為在0.001~0.1之範圍，且霧度值為在0.1~2%之範圍的有色之透明層(1)，與含有金屬奈米線之透明導電層(2)。 A substrate with a transparent conductive layer, characterized in that the absorbance systems having a wavelength of 450 nm, a wavelength of 550 nm and a wavelength of 650 nm are respectively in the range of 0.001 to 0.1 and a haze value of 0.1 to 2% on the transparent substrate. A range of colored transparent layers (1), and a transparent conductive layer (2) containing metal nanowires. 如申請專利範圍第1項之附透明導電層之基體，其中，該有色之透明層(1)係含有π共軛系化合物。 A substrate comprising a transparent conductive layer according to claim 1, wherein the colored transparent layer (1) contains a π-conjugated compound. 如申請專利範圍第1或2項之附透明導電層之基體，其中，該透明基體為片狀。 A substrate comprising a transparent conductive layer according to claim 1 or 2, wherein the transparent substrate is in the form of a sheet. 如申請專利範圍第1至3項中任一項之附透明導電層之基體，其中，係圖案化該透明導電層(2)。 The substrate of the transparent conductive layer according to any one of claims 1 to 3, wherein the transparent conductive layer (2) is patterned. 一種附透明導電層之基體的製造方法，其係如申請專利範圍第4項之附透明導電層之基體的製造方法，其特徵為具有：於基體上，藉由塗布而形成波長450nm、波長550nm及波長650nm之吸光度係分別獨立為在0.001~0.1之範圍，且霧度值為在0.1~2%之範圍的有色之透明層(1)的步驟1；與於該透明層(1)上，藉由塗布而形成含有金屬奈米線之可剝離透明導電層(2)的步驟2；與於支撐體上，形成具有經負型圖案化的接著區域之層的步驟3；與將該基體與該支撐體貼合、使該透明導電層(2)與具有該接著區域之層的該接著區域相互密合的步驟4；與 將該支撐體自該基體剝離，並藉由使與具有該接著區域之層的該接著區域密合之部分的該透明導電層(2)，轉移至具有接著區域之層之該接著區域上，而於基體上形成透明導電層(2)之圖案之步驟5；與於形成有該透明導電層(2)之圖案之基體整面，塗布保護層用塗料，並將透明導電層(2)於基體上固定化的步驟6。 A method for manufacturing a substrate with a transparent conductive layer, which is a method for manufacturing a substrate with a transparent conductive layer according to claim 4, characterized in that it has a wavelength of 450 nm and a wavelength of 550 nm by coating on a substrate. And the absorbance at a wavelength of 650 nm is independently a step 1 of a colored transparent layer (1) having a haze value in the range of 0.001 to 0.1 and a haze value of 0.1 to 2%; and on the transparent layer (1), Step 2 of forming a strippable transparent conductive layer (2) containing a metal nanowire by coating; and forming a layer having a layer of a negatively patterned succeeding region on the support; and the substrate Step 4 of bonding the support body to make the transparent conductive layer (2) and the adhesion region of the layer having the adhesion region adhere to each other; Stripping the support from the substrate, and transferring the transparent conductive layer (2) to a portion of the layer having the succeeding region by the portion of the transparent conductive layer (2) that is in close contact with the succeeding region of the layer having the region Step 5 of forming a pattern of the transparent conductive layer (2) on the substrate; coating the protective layer with the entire surface of the substrate on which the transparent conductive layer (2) is formed, and applying the transparent conductive layer (2) to Step 6 of immobilization on the substrate.