TW201436001A - Film forming method, conductive film and insulating film - Google Patents

Film forming method, conductive film and insulating film Download PDF

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Publication number
TW201436001A
TW201436001A TW102147085A TW102147085A TW201436001A TW 201436001 A TW201436001 A TW 201436001A TW 102147085 A TW102147085 A TW 102147085A TW 102147085 A TW102147085 A TW 102147085A TW 201436001 A TW201436001 A TW 201436001A
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Taiwan
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layer
forming method
film
film forming
resin
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TW102147085A
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Chinese (zh)
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Hiroshi Matsugi
Motomi Matsushima
Tomiaki Otake
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Kuraray Co
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/027—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed by irradiation, e.g. by photons, alpha or beta particles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0242—Shape of an individual particle
    • H05K2201/026—Nanotubes or nanowires
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/032—Materials
    • H05K2201/0323—Carbon
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
    • H05K2203/1142—Conversion of conductive material into insulating material or into dissolvable compound
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces

Abstract

To provide a patterned film having high resolution. This film forming method comprises: a step wherein a conductive carbon layer is provided a step wherein an overcoating layer is provided on the conductive carbon layer a step wherein a resin layer of a predetermined pattern is provided on the overcoating layer and a step wherein portions of the conductive carbon layer, on said portions the resin layer being not provided, are irradiated with ultraviolet light in an atmosphere containing oxygen.

Description

膜形成方法、導電膜、及絕緣膜 Film forming method, conductive film, and insulating film

本發明係關於例如透明導電膜。 The present invention relates to, for example, a transparent conductive film.

周知有一種透明導電膜基板，其係使透明導電膜(例如包含銦錫氧化物(ITO)等的透明導電膜)設置於透明基板上。此種基板，例如被使用於顯示面板；例如被使用於液晶顯示器；被使用於電漿顯示器；被使用於有機EL顯示器。或被使用於觸控面板；或被使用於太陽能電池。其他亦在各種領域被使用。 There is known a transparent conductive film substrate in which a transparent conductive film (for example, a transparent conductive film containing indium tin oxide (ITO) or the like) is provided on a transparent substrate. Such a substrate is used, for example, for a display panel; for example, for a liquid crystal display; for a plasma display; for use in an organic EL display. Or used in touch panels; or used in solar cells. Others are also used in various fields.

透明導電膜被形成於所期望之圖案。作為此圖案形成方法，一般而言，係採用化學蝕刻方法(使用光阻或蝕刻液的光微影法手段)。 A transparent conductive film is formed in a desired pattern. As the pattern forming method, in general, a chemical etching method (photolithography using a photoresist or an etching liquid) is employed.

該化學蝕刻方法，需要多種步驟，如光阻膜成膜步驟(在基板之全面成膜的ITO膜上塗布光阻塗料)→光阻膜圖案化步驟(藉由曝光顯影而將光阻膜成形為預定圖案)→ITO膜蝕刻步驟(將預定圖案之光阻膜作為遮罩，蝕刻ITO膜)→光阻膜除去步驟。因此，該化學蝕刻之方法係繁雜。該化學蝕刻之方法有著起因於溶液中的光阻膜之膨潤，使得蝕刻精密度降低之問題。該化學蝕刻之方法具有蝕刻液之處理操作性或廢液處理問題。 The chemical etching method requires various steps such as a photoresist film forming step (coating a photoresist coating on the ITO film of the entire film formed by the substrate) → a photoresist film patterning step (forming the photoresist film by exposure and development) For the predetermined pattern) → ITO film etching step (the photoresist film of a predetermined pattern is used as a mask, the ITO film is etched) → the photoresist film removing step. Therefore, the method of chemical etching is complicated. This chemical etching method has a problem that the etching precision is lowered due to the swelling of the photoresist film in the solution. This chemical etching method has the problem of handling operability of the etching liquid or waste liquid treatment.

作為解決該課題之方法，有提案一種雷射剝 蝕法。此方法係藉由將雷射直接照射於導電膜而除去不需要部分的方法。此方法不需光阻，精密度高的圖案化係成為可能。 As a method for solving this problem, there is a proposal for a laser stripping Eclipse method. This method is a method of removing an unnecessary portion by directly irradiating a laser to a conductive film. This method does not require photoresist, and a highly precise patterning system is possible.

但是，該雷射剝蝕法可適用的基材受到限定。該雷射剝蝕法係製程成本高。該雷射剝蝕法係處理速度慢。因此，該雷射剝蝕法並非適合於量產製程的方法。 However, the substrate to which the laser ablation method is applicable is limited. The laser ablation method has a high process cost. The laser ablation method is slow in processing. Therefore, the laser ablation method is not a suitable method for mass production processes.

作為不需光微影法步驟的化學蝕刻技術，有提案「在用以蝕刻氯化鐵(III)(ferric chloride)或氯化鐵(III)六水合物之氧化物表面之組成物中，作為蝕刻成分之使用」、「在氯化鐵(III)或氯化鐵(III)六水合物之顯示器技術(TFT)中；太陽光發電、半導體技術、高性能電子、礦物學或玻璃工業中；在OLED照明、OLED顯示器之製造中；及於光電二極體之製造；及用於平板面板網版印刷用途(電漿顯示器)之ITO玻璃之建構用的糊形態之組成物中，作為蝕刻成分之使用」、「一種用於氧化物層之蝕刻的組成物，該組成物係包含：a)作為蝕刻成分之氯化鐵(III)或氯化鐵(III)六水合物、b)溶劑、c)任意地經均質的溶解之有機增黏劑、d)任意地至少一種的無機酸及/或有機酸、及任意地e)添加劑，例如消泡劑、觸變劑、流動控制劑、脫氣劑、黏結促進劑，且為糊形態，可印刷者」(日本特表2008-547232號公報)。 As a chemical etching technique that does not require a photolithography step, there is a proposal "in a composition for etching the surface of an oxide of ferric chloride or iron (III) hexahydrate, as Use of etching components, "in the display technology (TFT) of iron (III) chloride or iron (III) hexahydrate; in solar power generation, semiconductor technology, high performance electronics, mineralogy or glass industry; In the manufacture of OLED lighting, OLED display; and in the manufacture of photodiode; and in the composition of paste form for the construction of ITO glass for flat panel screen printing (plasma display), as an etching component "Use", "a composition for etching an oxide layer, the composition comprising: a) iron (III) chloride or iron (III) chloride hexahydrate as an etching component, b) a solvent, c) optionally homogenized dissolved organic tackifier, d) optionally at least one inorganic acid and / or organic acid, and optionally e) additives, such as defoamers, thixotropic agents, flow control agents, off Gas agent, adhesion promoter, and paste form, can be printed" (Japanese special Gazette No. 2008-547232).

有提案：「一種蝕刻介質，其係用於蝕刻氧化物之透明的導電層之蝕刻介質，其係包含蝕刻液，該蝕刻液係包含磷酸、或者其鹽或磷酸加成物或磷酸、與 磷酸鹽及/或磷酸加成物之混合物中之至少一種的蝕刻劑」、「一種方法，其係用於蝕刻氧化物之透明的導電層之方法，其特徵為適用於藉由印刷步驟而蝕刻該蝕刻介質之基板」(日本特表2009-503825號公報)。 There is a proposal: "An etching medium, which is an etching medium for etching a transparent conductive layer of an oxide, which comprises an etching solution containing phosphoric acid, or a salt thereof or a phosphate adduct or phosphoric acid, and An etchant for at least one of a mixture of phosphate and/or phosphoric acid adducts," a method for etching a transparent conductive layer of an oxide, characterized by being suitable for etching by a printing step The substrate of the etching medium" (Japanese Laid-Open Patent Publication No. 2009-503825).

但是，日本特表2008-547232號公報或日本特表2009-503825號公報之技術，蝕刻在面內難以均勻地進行。因此發生不勻。 However, in the technique of JP-A-2008-547232 or JP-A-2009-503825, etching is difficult to perform uniformly in the plane. Therefore, unevenness occurs.

然而，透明導電膜，除了ITO製之透明導電膜之外，周知也有碳奈米管製之透明導電膜。碳奈米管係直徑1μm以下之粗細的管狀材料。理想的碳奈米管，係使碳六角網眼的面成為平行於管之軸而形成管之結構。該管亦有成為多重。碳奈米管係藉由以碳製成的六角網眼之連接方法或管之粗細，而顯示金屬的或者半導體的性質。由此，碳奈米管被期待作為功能材料。但是，依據碳奈米管之構成或製造法，粗細及方向皆為隨機。因此，在利用時，亦有需在合成後予以回收且精製，以合乎利用形態的處理的情形。作為此種碳奈米管之圖案化之方法，有提案下述之方法(日本特表2006-513557號公報、日本特表2007-529884號公報(國際公開2005/086982號小冊))。例如在基板表面塗布碳奈米管分散液。藉此，形成碳奈米管被膜。將黏合劑溶液以預定圖案塗布此碳奈米管被膜。塗布後，使溶劑經乾燥除去。藉此，使黏合劑殘留於碳奈米管被膜中，使碳奈米管的網絡被強化。此後，以不溶解黏合劑的溶劑，使基板洗淨。藉此，僅黏合劑存在(經黏合劑塗布)之部分殘留而形 成圖案。亦可使用光阻材料以替代黏合劑。亦即，在碳奈米管被膜塗布含有光阻之塗料。藉此，光阻浸漬於碳奈米管的網絡內。此後，使用光微影法形成預定圖案。但是，形成碳奈米管被膜於基板表面全體之後進行圖案化之方法，係步驟繁雜。 However, the transparent conductive film is known to have a carbon nanotube-regulated transparent conductive film in addition to a transparent conductive film made of ITO. The carbon nanotube tube is a tubular material having a diameter of 1 μm or less. An ideal carbon nanotube is a structure in which the surface of the carbon hexagonal mesh is formed parallel to the axis of the tube. The tube has also become multiple. The carbon nanotube tube exhibits metallic or semiconducting properties by a connection method of a hexagonal mesh made of carbon or a thickness of a tube. Thus, the carbon nanotube is expected to be a functional material. However, depending on the composition or manufacturing method of the carbon nanotubes, the thickness and direction are random. Therefore, in the case of use, there is a case where it is necessary to recover and refine after synthesis to conform to the treatment of the form. As a method of patterning such a carbon nanotube, there are proposed methods (Japanese Patent Publication No. 2006-513557, Japanese Patent Publication No. 2007-529884 (International Publication No. 2005/086982)). For example, a carbon nanotube dispersion is applied to the surface of the substrate. Thereby, a carbon nanotube film is formed. The carbon nanotube coating is applied to the binder solution in a predetermined pattern. After coating, the solvent was removed by drying. Thereby, the binder remains in the carbon nanotube film, and the network of the carbon nanotubes is strengthened. Thereafter, the substrate is washed with a solvent that does not dissolve the binder. Thereby, only the part of the adhesive (coated by the adhesive) remains. Into a pattern. A photoresist material can also be used instead of the binder. That is, a coating containing a photoresist is applied to the carbon nanotube film. Thereby, the photoresist is immersed in the network of the carbon nanotubes. Thereafter, a predetermined pattern is formed using photolithography. However, the method of patterning the carbon nanotube film on the entire surface of the substrate is complicated.

可列舉一種方法，其藉由網版印刷、噴墨、凹版印刷等之塗布方法，使預先經圖案化的碳奈米管被膜，直接塗布、形成於基板上的方法。在將經圖案化的碳奈米管被膜以網版印刷等之塗布方法形成之情形，有需要將含碳奈米管之塗料的物性調整為合乎塗布方法的物性。碳奈米管分散液，一般而言係包含界面活性劑等之分散劑。碳奈米管分散液為比較地低黏度。為了使其為合乎塗布方法之油墨物性者，變得需要將用以調整黏度或表面張力的材料添加於碳奈米管分散液。在此情形，有碳奈米管之分散性惡化之虞。 A method of directly coating a previously formed carbon nanotube coating film on a substrate by a coating method such as screen printing, inkjet or gravure printing may be mentioned. In the case where the patterned carbon nanotube film is formed by a coating method such as screen printing, it is necessary to adjust the physical properties of the carbon nanotube-containing coating to conform to the physical properties of the coating method. The carbon nanotube dispersion is generally a dispersant containing a surfactant or the like. The carbon nanotube dispersion is relatively low viscosity. In order to make it suitable for the ink properties of the coating method, it has become necessary to add a material for adjusting the viscosity or surface tension to the carbon nanotube dispersion. In this case, there is a problem that the dispersibility of the carbon nanotubes deteriorates.

有下述技術之提案(國際公開2010/113744號小冊)，以替代在日本特表2006-513557號公報或日本特表2007-529884號公報所提案的技術。亦即，有提案一種導電膜除去劑，其包含：沸點為80℃以上之酸(例如硫酸或磺酸化合物)或沸點為80℃以上之鹼或由外部能量發生酸或鹼之化合物、溶劑、樹脂(例如，含於一級至四級胺基之任一種結構之一部分的陽離子性樹脂)及調平劑。有提案一種導電膜除去方法，其具備：在基材上具有包含晶鬚狀導電體、纖維狀導電體(例如碳奈米管)或粒狀導電體的導電膜之附有導電膜之基材的至少一部分上 ，塗布該導電膜除去劑之步驟；在80℃以上進行加熱處理之步驟及藉由使用液體之洗淨而除去導電膜之步驟。有提案一種導電膜除去方法，該導電膜除去方法係自在導電膜上具有外護層的附有導電膜之基材除去外護層與導電膜的方法。藉由在塗布該導電膜除去劑後，進行80至200℃加熱處理，而塗布有導電膜除去劑的部分之導電膜，被分解、溶解或可溶化，又，在具有外護層之情形，則強調外護層與導電膜被分解、溶解或可溶化。 There is a proposal of the following technique (International Publication No. 2010/113744), in place of the technique proposed in Japanese Laid-Open Patent Publication No. 2006-513557 or Japanese Patent Publication No. 2007-529884. That is, there is proposed a conductive film removing agent comprising: an acid having a boiling point of 80 ° C or higher (for example, a sulfuric acid or a sulfonic acid compound) or a base having a boiling point of 80 ° C or higher or a compound or a solvent which generates an acid or a base from an external energy; A resin (for example, a cationic resin containing a part of any one of the first to fourth amine groups) and a leveling agent. There is proposed a conductive film removing method comprising: a substrate with a conductive film having a conductive film including a whisker-like conductor, a fibrous conductor (for example, a carbon nanotube) or a particulate conductor on a substrate At least part of a step of applying the conductive film removing agent; a step of performing heat treatment at 80 ° C or higher; and a step of removing the conductive film by washing with a liquid. There has been proposed a method of removing a conductive film which is a method of removing an outer cover layer and a conductive film from a substrate with a conductive film having an outer cover layer on a conductive film. After the conductive film removing agent is applied, heat treatment at 80 to 200 ° C is performed, and a portion of the conductive film coated with the conductive film removing agent is decomposed, dissolved, or solubilized, and in the case of having an outer sheath, It is emphasized that the outer sheath and the conductive film are decomposed, dissolved or solubilized.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特表2008-547232號公報 [Patent Document 1] Japanese Patent Publication No. 2008-547232

[專利文獻2]日本特表2009-503825號公報 [Patent Document 2] Japanese Patent Publication No. 2009-503825

[專利文獻3]日本特表2006-513557號公報 [Patent Document 3] Japanese Patent Publication No. 2006-513557

[專利文獻4]日本特表2007-529884號公報(國際公開2005/086982號小冊) [Patent Document 4] Japanese Patent Publication No. 2007-529884 (International Publication No. 2005/086982)

[專利文獻5]國際公開2010/113744號小冊 [Patent Document 5] International Publication No. 2010/113744

專利文獻5之使用導電膜除去劑的方法所形成的圖案，在其側面(垂直壁面)，碳奈米管外露。這是因為即使在碳奈米管層上面設置有外護層，也會藉由導電膜除去劑而使碳奈米管層及外護層除去。亦即，存在不被外護層所覆蓋之碳奈米管面。因此認為耐久性降低(例如，碳奈米管之脫落、水分所致之物性變化等)。 In the pattern formed by the method using the conductive film removing agent of Patent Document 5, the carbon nanotube tube is exposed on the side surface (vertical wall surface). This is because even if the outer sheath is provided on the carbon nanotube layer, the carbon nanotube layer and the outer sheath are removed by the conductive film removing agent. That is, there is a carbon nanotube surface that is not covered by the outer sheath. Therefore, it is considered that the durability is lowered (for example, the carbon nanotubes are detached, the physical properties due to moisture, etc.).

進一步地，亦要考慮表面產生凹凸的問題。 Further, it is also necessary to consider the problem that the surface is uneven.

專利文獻5之技術，需要加熱步驟，其係將塗布於預定圖案的導電膜除去劑加熱至80℃以上。因此，作業性不良。再者，要求基板具有80℃以上的抗熱性。此係降低基板選擇的自由度。 The technique of Patent Document 5 requires a heating step of heating the conductive film removing agent applied in a predetermined pattern to 80 ° C or higher. Therefore, workability is poor. Further, the substrate is required to have heat resistance of 80 ° C or more. This reduces the degree of freedom in substrate selection.

本發明之目的在於解決上述問題。尤其是，本發明欲解決課題，係以簡便方法提供解析度高且耐久性優異之導電性(或絕緣性)的膜。 The object of the present invention is to solve the above problems. In particular, in order to solve the problem, the present invention provides a film having high conductivity and excellent electrical conductivity (or insulating property) by a simple method.

戮力推動進行了針對該問題的研討。 Philip promoted the discussion on this issue.

其結果，判明下列事實。在導電性膜(例如，藉由塗布導電性碳奈米管而構成的導電性膜)上設置外護層。在該外護層上設置屏蔽(遮光)紫外線的預定圖案的樹脂層。將該樹脂層作成遮罩，照射紫外線。尤其是，在有氧的環境中，照射紫外線。如此所形成的圖案，係圖案精密度高。導電膜(絕緣膜)之耐久性優異。而且，圖案形成係簡單。預定圖案之導電膜由相反立場觀察，則為預定圖案之絕緣膜。 As a result, the following facts were found. An outer sheath is provided on the conductive film (for example, a conductive film formed by applying a conductive carbon nanotube). A resin layer of a predetermined pattern of shielding (light-shielding) ultraviolet rays is provided on the outer sheath. The resin layer was made into a mask and irradiated with ultraviolet rays. In particular, in an aerobic environment, ultraviolet rays are irradiated. The pattern thus formed has a high pattern precision. The conductive film (insulating film) is excellent in durability. Moreover, the pattern formation is simple. The conductive film of the predetermined pattern is an insulating film of a predetermined pattern as viewed from the opposite position.

根據上述真知灼見而達成本發明。 The present invention has been achieved in light of the above-mentioned insights.

本發明係提案一種膜形成方法，其係使照射紫外線區域之導電性碳層改質為絕緣性，未照射紫外線區域之導電性碳層保持導電性的預定圖案之膜形成方法，其特徵為具備：設置導電性碳層的步驟；在該導電性碳層上設置外護層的步驟； 在該外護層上密接預定圖案之樹脂層而設置之步驟；在有氧之環境下，對應於無該樹脂層之處，使紫外線照射於該導電性碳層之步驟。 According to the present invention, there is provided a film forming method which is characterized in that a conductive carbon layer irradiated in an ultraviolet region is modified into an insulating property, and a film forming method of a predetermined pattern in which a conductive carbon layer which is not irradiated with an ultraviolet region maintains conductivity is provided. a step of providing a conductive carbon layer; a step of providing an outer sheath on the conductive carbon layer; a step of adhering a resin layer of a predetermined pattern to the outer sheath; and irradiating the conductive carbon layer with ultraviolet rays in an aerobic environment corresponding to the absence of the resin layer.

本發明係提案一種膜形成方法，其係使照射紫外線區域之導電性碳層改質為絕緣性，使未照射紫外線區域之導電性碳層保持導電性的預定圖案之膜形成方法，其特徵為具備：設置導電性碳層之步驟；在該導電性碳層上設置外護層的步驟；在該外護層上密接預定圖案之樹脂層而設置之步驟；在有氧之環境下，對應於無該樹脂層之處，使紫外線照射於該導電性碳層之步驟；在該紫外線照射後，除去該樹脂層之步驟。 The present invention proposes a film forming method which is a film forming method in which a conductive carbon layer irradiated in an ultraviolet region is modified into an insulating property, and a conductive pattern in which a conductive carbon layer not irradiated with an ultraviolet region is maintained in conductivity is characterized. a step of: providing a conductive carbon layer; a step of providing an outer sheath on the conductive carbon layer; a step of arranging a resin layer of a predetermined pattern on the outer sheath; and in an aerobic environment, corresponding to The step of irradiating the conductive carbon layer with ultraviolet rays without the resin layer; and the step of removing the resin layer after the ultraviolet irradiation.

本發明係提案一種膜形成方法，其係該膜形成方法，該外護層較佳為由含有選自水解性有機矽烷之水解物之群組中至少一個之組成物所構成。 The present invention proposes a film formation method which is a film formation method, and the outer sheath layer is preferably composed of a composition containing at least one selected from the group consisting of hydrolyzable hydrolyzable organic decane.

本發明係提案一種膜形成方法，其係該膜形成方法，該外護層係較佳為厚度為1nm至1μm。 The present invention proposes a film forming method which is a film forming method, and the outer sheath layer preferably has a thickness of from 1 nm to 1 μm.

本發明係提案一種膜形成方法，其係該膜形成方法，該預定圖案之樹脂層係較佳為使用不穿透紫外線的材料之樹脂，以印刷手段所設置者。 The present invention proposes a film forming method which is a film forming method, and the resin layer of the predetermined pattern is preferably a resin which is provided by a printing means using a resin which does not penetrate ultraviolet rays.

本發明係提案一種膜形成方法，其係該膜形成方法，該紫外線係較佳為具有10至400nm的範圍之波長的紫外線。 The present invention proposes a film forming method which is preferably a film forming method, and the ultraviolet light is preferably an ultraviolet light having a wavelength in the range of 10 to 400 nm.

本發明係提案一種膜形成方法，其係該膜形成方法，該紫外線係較佳為具有150至180nm的範圍之波長的紫外線。 The present invention proposes a film forming method which is preferably a film forming method, and the ultraviolet light is preferably ultraviolet light having a wavelength in the range of 150 to 180 nm.

本發明係提案一種膜形成方法，其係該膜形成方法，該紫外線的照射累計光量係較佳為50至500000mJ/cm2。 The present invention proposes a film forming method which is a film forming method, and the cumulative amount of the ultraviolet light irradiation is preferably from 50 to 500,000 mJ/cm 2 .

本發明係提案一種膜形成方法，其係該膜形成方法，該紫外線的照射累計光量係較佳為500至30000mJ/cm2。 The present invention proposes a film forming method which is a film forming method, and the cumulative amount of the ultraviolet light irradiation is preferably from 500 to 30,000 mJ/cm 2 .

本發明係提案一種膜形成方法，其係該膜形成方法，該有氧之環境，係氧壓較佳為101至21273Pa。 The present invention proposes a film forming method which is a film forming method in which the oxygen pressure is preferably 101 to 21273 Pa.

本發明係提案一種膜形成方法，其係該膜形成方法，該有氧之環境，係氧壓較佳為1013至10130Pa。 The present invention proposes a film forming method which is a film forming method in which the oxygen pressure is preferably from 1013 to 10130 Pa.

本發明係提案一種膜形成方法，其係該膜形成方法，該導電性碳層係較佳為由石墨烯所構成。 The present invention proposes a film forming method which is a film forming method, and the conductive carbon layer is preferably composed of graphene.

本發明係提案一種膜形成方法，其係該膜形成方法，該導電性碳層係較佳為以碳奈米管構成。 The present invention proposes a film forming method which is a film forming method, and the conductive carbon layer is preferably composed of a carbon nanotube.

本發明係提案一種膜形成方法，其係該膜形成方法，該導電性碳層係較佳為以接受酸處理的單層碳奈米管構成。 The present invention proposes a film forming method which is a film forming method, and the conductive carbon layer is preferably composed of a single-layer carbon nanotube which is subjected to acid treatment.

本發明係提案一種導電膜，其係藉由該膜形成方法所形成。 The present invention proposes a conductive film formed by the film forming method.

本發明係提案一種絕緣膜，其係藉由該膜形成方法所形成。 The present invention proposes an insulating film formed by the film forming method.

可簡單獲得解析度高的導電性(或絕緣性)的膜。 A film having high conductivity (or insulation) with high resolution can be easily obtained.

1‧‧‧透明導電性碳層(碳奈米管層) 1‧‧‧Transparent conductive carbon layer (carbon nanotube layer)

1a‧‧‧紫外線照射處(絕緣性改質處) 1a‧‧‧UV irradiation (insulation modification)

1b‧‧‧紫外線未照射處(透明導電性處) 1b‧‧‧Unilluminated areas of ultraviolet light (transparent conductivity)

2‧‧‧基板 2‧‧‧Substrate

3‧‧‧外護層(含有水解性有機矽烷之組成物層) 3‧‧‧ outer sheath (layer containing hydrolyzable organodecane)

4‧‧‧樹脂層(遮罩) 4‧‧‧Resin layer (mask)

5‧‧‧開口部(紫外線穿透部) 5‧‧‧ Opening (UV penetration)

41‧‧‧導電部 41‧‧‧Electrical Department

51‧‧‧絕緣部 51‧‧‧Insulation

6‧‧‧細線部 6‧‧‧ Thin line department

第1圖係表示照射紫外線前之層構成的概要剖面圖 Fig. 1 is a schematic cross-sectional view showing the structure of a layer before ultraviolet irradiation

第2圖係表示照射紫外線後之層構成的概要剖面圖 Fig. 2 is a schematic cross-sectional view showing the layer structure after ultraviolet irradiation

第3圖係樹脂層(遮罩)平面圖 Figure 3 is a plan view of the resin layer (mask)

第4圖係導電性評價圖案之平面圖 Figure 4 is a plan view of the conductivity evaluation pattern

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

第一本發明係膜形成方法。該方法係例如形成預定圖案之導電膜之方法。或，形成預定圖案之絕緣膜之方法。該方法係形成預定圖案之透明導電膜的方法。或，形成預定圖案之透明絕緣膜的方法。該方法係使照射紫外線區域之導電性碳層改質為絕緣性，使未照射紫外線區域之導電性碳層保持導電性的預定圖案之膜形成方法。若特別採用改質為絕緣性之處，則該方法為絕緣膜形成方法。若特別採用導電性之處，則該方法為導電膜形成方法。該方法係具備設置導電性碳層之步驟。在基板上，例如塗布含有(例如，分散)導電性碳(例如，導電性石墨烯(導電性碳奈米管))之塗料。藉此塗布而設置導電性碳層。亦可使用塗布方法以外之方法。例如，亦可使用CVD(化學氣相沉積方法)或PVD(物理氣相沉積方法)。但，較佳為採用塗布方法。該方法，係具備在該導電性碳層上設置外護層的步驟。例如，外護塗料係塗布於該導電性碳層上。藉由此塗布而構成外護層。該方法係具備使樹脂層(不穿透紫外線之材料的樹脂層)設置 於該外護層上之步驟。該外護層與該樹脂層為密接。密接係指對剝離需額外的力之意。亦即，[該外護層與該樹脂層之黏著強度(剝離強度)]>0之意。紫外線並無在該外護層與該樹脂層之邊界潛行(sneak)之意。係指氧(活性氧)不侵入該外護層與該樹脂層之邊界之意。就此意義並無需特別大的黏著強度(剝離強度)。該樹脂層具有預定之圖案。在對應該導電性碳層維持導電性之處(圖案)之處，設置該樹脂層。在對應該導電性碳層喪失導電性成為絕緣性之處(圖案)之處，不設置該樹脂層。亦即，該預定圖案之樹脂層，係發揮用於形成預定圖案之導電膜(絕緣膜)之遮罩的功能。以不穿透紫外線之樹脂而言，可列舉各種之物。可列舉例如光阻材料、光硬化性樹脂、熱硬化性樹脂、熱塑性樹脂等。當然，並不限於此。該預定圖案之樹脂層，例如可以網版印刷等之印刷手段形成。或，使用光微影技術而形成。當然，並不限於此。該方法係具備在設置該預定圖案之樹脂層後，在有氧之環境下，照射紫外線之步驟。在此照射步驟，存在該樹脂層之處的下方位置之導電性碳係無照射紫外線。無存在該樹脂層之處的下方位置之導電性碳係照射紫外線。在應為絕緣性之處，照射紫外線。未照射紫外線區域則為應確保導電性之區域。照射紫外線區域為應喪失導電性之區域。為了形成預定圖案導電性之膜(或絕緣性膜)，進行紫外線照射。藉由使用樹脂層(樹脂製遮罩)，提高外護層與遮罩之密接性。藉此，在紫外線被遮蔽之處或因紫外線照射所致之活性化氧被遮蔽之處，紫外線變 得難以到達。此結果，導電性膜(絕緣性膜)之圖案精密度變高。可獲得解析度高之圖案的膜。該外護層係較佳為由含有選自水解性有機矽烷水解物之群組中至少一個之組成物所構成。該紫外線係較佳為具有10至400nm的範圍之波長的紫外線。更佳為具有150至260nm的範圍之波長的紫外線。特佳為具有150至180nm的範圍之波的紫外線。該有氧之環境係較佳為氧壓(在混合氣體的情形為氧分壓)為101至21273Pa。更佳為氧壓為507至20260Pa。特佳為氧壓為1013至10130Pa。該導電性碳層係例如以石墨烯構成。該導電性碳層(石墨烯層)係例如以碳奈米管構成。該導電性碳層(碳奈米管層)係例如以單層碳奈米管構成。該導電性碳層(碳奈米管層)係例如以接受酸處理的單層碳奈米管構成。碳奈米管係較佳為G(出現於1590cm-1附近的石墨物質所共通的拉曼波峰之強度)/D(出現於1350cm-1附近的缺陷所起因之拉曼波峰之強度)≧10之碳奈米管。G/D之上限值係例如為150左右。 The first invention film forming method. This method is, for example, a method of forming a conductive film of a predetermined pattern. Or, a method of forming an insulating film of a predetermined pattern. This method is a method of forming a transparent conductive film of a predetermined pattern. Or, a method of forming a transparent insulating film of a predetermined pattern. This method is a film forming method in which a conductive carbon layer that irradiates an ultraviolet ray region is modified into an insulating property, and a conductive carbon layer that is not irradiated with an ultraviolet ray region maintains a predetermined pattern of conductivity. If it is specifically modified to be insulative, the method is an insulating film forming method. If conductivity is particularly used, the method is a method of forming a conductive film. This method has the step of providing a conductive carbon layer. On the substrate, for example, a coating containing (for example, dispersed) conductive carbon (for example, conductive graphene (conductive carbon nanotube)) is applied. A conductive carbon layer is provided by this coating. A method other than the coating method can also be used. For example, CVD (Chemical Vapor Deposition) or PVD (Physical Vapor Deposition) can also be used. However, it is preferred to employ a coating method. This method includes a step of providing an outer sheath on the conductive carbon layer. For example, an exterior coating is applied to the conductive carbon layer. The outer sheath is formed by coating. This method is a step of providing a resin layer (a resin layer of a material that does not penetrate ultraviolet rays) on the outer sheath. The outer sheath is in close contact with the resin layer. Adhesion refers to the additional force required for stripping. That is, [the adhesion strength (peeling strength) of the outer sheath and the resin layer] is >0. Ultraviolet light does not mean to sneak at the boundary between the outer sheath and the resin layer. It means that oxygen (active oxygen) does not intrude into the boundary between the outer sheath and the resin layer. In this sense, no particularly large adhesive strength (peel strength) is required. The resin layer has a predetermined pattern. The resin layer is provided where the conductive carbon layer is maintained in electrical conductivity (pattern). The resin layer is not provided where the conductive carbon layer loses conductivity and becomes insulative (pattern). That is, the resin layer of the predetermined pattern functions as a mask for forming a conductive film (insulating film) of a predetermined pattern. Examples of the resin that does not penetrate ultraviolet rays include various materials. For example, a photoresist material, a photocurable resin, a thermosetting resin, a thermoplastic resin, etc. are mentioned. Of course, it is not limited to this. The resin layer of the predetermined pattern can be formed, for example, by a printing means such as screen printing. Or, formed using photolithography. Of course, it is not limited to this. This method is a step of irradiating ultraviolet rays in an aerobic environment after the resin layer of the predetermined pattern is provided. In this irradiation step, the conductive carbon in the lower position where the resin layer exists is not irradiated with ultraviolet rays. The conductive carbon in the lower position where no such resin layer exists is irradiated with ultraviolet rays. Irradiation of ultraviolet light should be performed where insulation is required. The area where the ultraviolet ray is not irradiated is an area where electrical conductivity should be ensured. The area irradiated with ultraviolet rays is an area where conductivity should be lost. In order to form a film (or an insulating film) of a predetermined pattern conductivity, ultraviolet irradiation is performed. By using a resin layer (resin mask), the adhesion between the outer sheath and the mask is improved. Thereby, it is difficult to reach the ultraviolet ray where the ultraviolet ray is shielded or the activated oxygen due to the ultraviolet ray is blocked. As a result, the pattern precision of the conductive film (insulating film) becomes high. A film having a high resolution pattern can be obtained. The outer sheath layer is preferably composed of a composition containing at least one selected from the group consisting of hydrolyzable organodecane hydrolysates. The ultraviolet ray is preferably an ultraviolet ray having a wavelength in the range of 10 to 400 nm. More preferably, it is an ultraviolet ray having a wavelength in the range of 150 to 260 nm. Particularly preferred is ultraviolet rays having a wave in the range of 150 to 180 nm. The aerobic environment is preferably an oxygen pressure (oxygen partial pressure in the case of a mixed gas) of 101 to 21,273 Pa. More preferably, the oxygen pressure is 507 to 20260 Pa. Particularly preferred is an oxygen pressure of 1013 to 10130 Pa. The conductive carbon layer is made of, for example, graphene. The conductive carbon layer (graphene layer) is made of, for example, a carbon nanotube. The conductive carbon layer (carbon nanotube layer) is composed of, for example, a single-layer carbon nanotube. The conductive carbon layer (carbon nanotube layer) is composed of, for example, a single-layer carbon nanotube that is subjected to acid treatment. The carbon nanotube system is preferably G (the intensity of the Raman peak common to the graphite substance present in the vicinity of 1590 cm -1 ) / D (the intensity of the Raman peak which is caused by the defect occurring around 1350 cm -1 ) ≧ 10 Carbon nanotubes. The upper limit of G/D is, for example, about 150.

第二本發明係導電膜。該膜係藉由該膜形成方法所形成之導電膜。 The second invention is a conductive film. This film is a conductive film formed by the film formation method.

第三本發明為絕緣膜。該膜係藉由該膜形成方法所形成之絕緣膜。 The third invention is an insulating film. This film is an insulating film formed by the film formation method.

以下係進一步詳細說明。 The following is further detailed.

第1圖至第3圖係本發明之一實施形態的說明圖。第1圖係表示紫外線照射前之層構成的概要剖面圖；第2圖係表示紫外線照射後之層構成的概要剖面圖；第3圖係設置於外護層上的樹脂層(遮罩)之平面圖。 Fig. 1 to Fig. 3 are explanatory views of an embodiment of the present invention. 1 is a schematic cross-sectional view showing a layer structure before ultraviolet irradiation; FIG. 2 is a schematic cross-sectional view showing a layer structure after ultraviolet irradiation; and FIG. 3 is a resin layer (mask) provided on an outer sheath. Floor plan.

1為透明導電性碳層。 1 is a transparent conductive carbon layer.

該透明導電性碳層1，係例如以石墨烯構成。 The transparent conductive carbon layer 1 is made of, for example, graphene.

該透明導電性碳層1，係例如以碳奈米管構成。 The transparent conductive carbon layer 1 is made of, for example, a carbon nanotube.

該透明導電性碳層1，係例如以單層碳奈米管構成。 The transparent conductive carbon layer 1 is composed of, for example, a single-layer carbon nanotube.

該透明導電性碳層1，係例如以接受酸處理的單層碳奈米管構成。 The transparent conductive carbon layer 1 is made of, for example, a single-layer carbon nanotube that is subjected to acid treatment.

作為構成透明導電性碳層1的碳奈米管(CNT)，可列舉單層碳奈米管、二層碳奈米管、多層碳奈米管等。 Examples of the carbon nanotube (CNT) constituting the transparent conductive carbon layer 1 include a single-layer carbon nanotube, a two-layer carbon nanotube, and a multilayer carbon nanotube.

較佳為單層碳奈米管。特佳為G/D為10以上(例如，20至60)的單層碳奈米管。 A single layer carbon nanotube is preferred. A single layer carbon nanotube having a G/D of 10 or more (for example, 20 to 60) is particularly preferred.

較佳為直徑為0.3至100nm之CNT。特佳為直徑為0.3至2nm之CNT。 CNTs having a diameter of 0.3 to 100 nm are preferred. Particularly preferred are CNTs having a diameter of 0.3 to 2 nm.

較佳為長度為0.1至100μm之CNT。特佳為長度為0.1至5μm之CNT。 CNTs having a length of 0.1 to 100 μm are preferred. Particularly preferred are CNTs having a length of 0.1 to 5 μm.

透明導電性碳層1之CNT，例如為相互纏繞。 The CNTs of the transparent conductive carbon layer 1 are, for example, entangled with each other.

單層碳奈米管可為藉由任意製法所得之單層碳奈米管。例如，可使用電弧放電法、化學氣相法或雷射蒸發法等之製法所得之單層碳奈米管。 The single-layer carbon nanotube can be a single-layer carbon nanotube obtained by any method. For example, a single-layer carbon nanotube obtained by a method such as an arc discharge method, a chemical vapor method, or a laser evaporation method can be used.

由結晶性之觀點而言，較佳為以弧光放電法所得之單層碳奈米管。其取得亦為容易。 From the viewpoint of crystallinity, a single-layer carbon nanotube obtained by an arc discharge method is preferred. It is also easy to obtain.

單層碳奈米管係較佳為實施酸處理的單層碳奈米管。酸處理係藉由在酸性液體中浸漬單層碳奈米管而實施。亦可採用噴霧的方法以替代浸漬。在酸性液體有各種之物。例如，可使用無機酸或有機酸。但較佳為無機酸 。可列舉例如硝酸、鹽酸、硫酸、磷酸或該等之混合物。其中較佳為使用硝酸、或硝酸與硫酸之混合酸的酸處理。藉由此酸處理，在單層碳奈米管與碳微粒經由非晶形碳而物理性鍵結的情形，非晶形碳分解。兩者分離。在單層碳奈米管製作時所使用的金屬觸媒之微粒分解。藉由該酸處理，附著官能基。藉由該酸處理提高導電性。 The single layer carbon nanotube system is preferably a single layer carbon nanotube to which acid treatment is carried out. The acid treatment is carried out by impregnating a single layer of carbon nanotubes in an acidic liquid. A spray method can also be used instead of impregnation. There are various kinds of substances in acidic liquids. For example, a mineral acid or an organic acid can be used. But preferably inorganic acid . For example, nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid or a mixture of these may be mentioned. Among them, acid treatment using nitric acid or a mixed acid of nitric acid and sulfuric acid is preferred. By this acid treatment, the amorphous carbon is decomposed in the case where the single-layer carbon nanotubes and the carbon particles are physically bonded via the amorphous carbon. The two are separated. The particles of the metal catalyst used in the production of the single-layer carbon nanotubes are decomposed. The functional group is attached by the acid treatment. The conductivity is improved by the acid treatment.

單層碳奈米管較佳為藉由過濾除去雜質，而純度提高的單層碳奈米管。這是因為可防止因雜質所致之導電性的降低或透光率的降低。過濾可採用各種方法。例如，可使用吸引過濾、加壓過濾、掃流過濾(cross flow filtration)等。其中，由規模放大的觀點而言，較佳為採用使用中空纖維薄膜的掃流過濾。 The single-layer carbon nanotube is preferably a single-layer carbon nanotube having improved purity by filtration to remove impurities. This is because the decrease in conductivity or the decrease in light transmittance due to impurities can be prevented. Various methods can be used for filtration. For example, suction filtration, pressure filtration, cross flow filtration, or the like can be used. Among them, from the viewpoint of scale-up, it is preferred to use a sweep filtration using a hollow fiber membrane.

在導電層(碳奈米管層)1中，除了該CNT之外，較佳為含有富勒烯。 In the conductive layer (carbon nanotube layer) 1, in addition to the CNT, fullerene is preferably contained.

導電層1較佳為含有該特徵之CNT、及富勒烯。 The conductive layer 1 is preferably a CNT and a fullerene containing the feature.

在本說明書的情況下，「富勒烯」亦包含「富勒烯類似物」。 In the case of the present specification, "fullerene" also includes "fullerene analogs".

這是因為藉由含有富勒烯而可提高抗熱性。這也是因為導電性亦優異。 This is because heat resistance can be improved by containing fullerenes. This is also because the conductivity is also excellent.

富勒烯為任一種富勒烯均可。可列舉例如C60、C70、C76、C78、C82、C84、C90、C96等。當然，亦可為複數種之富勒烯的混合物。 Fullerenes are any of the fullerenes. For example, C60, C70, C76, C78, C82, C84, C90, C96, etc. are mentioned. Of course, it can also be a mixture of a plurality of fullerenes.

由分散性能之觀點而言，特佳為C60。再者，C60易於取得。不僅C60，C60與其他種類之富勒烯(例如，C70) 的混合物亦可。 From the viewpoint of dispersion performance, it is particularly preferred to be C60. Furthermore, C60 is easy to obtain. Not only C60, C60 and other types of fullerenes (eg, C70) The mixture can also be.

亦可在富勒烯內部內包有金屬原子之物。 It is also possible to encapsulate a metal atom in the interior of the fullerene.

作為富勒烯類似物，可列舉具有官能基(例如，OH基、環氧基、酯基、醯胺基、磺醯基、醚基等之官能基)之物。亦可列舉苯基-C61-丙酸烷酯、苯基-C61-丁酸烷酯。亦可列舉氫化富勒烯等。其中，較佳為具有OH基(羥基)的富勒烯(氫氧化富勒烯)。此係因為單層碳奈米管分散液塗布時之分散性變高。另外，若OH基數少時，則單層碳奈米管之分散性提高度降低。相反地，過多時則合成困難。因此，OH基數係較佳為富勒烯每1分子為5至30個。特佳為8至15個。富勒烯的添加量(含量)過多時，則導電性降低。相反地，過少時，則效果缺乏。因此，較佳為相對於100質量份之CNT，富勒烯量為10至1000質量份(尤其是20質量份以上。100質量份以下。)。 Examples of the fullerene analog include those having a functional group (for example, a functional group such as an OH group, an epoxy group, an ester group, a decylamino group, a sulfonyl group, or an ether group). Phenyl-C61-propionic acid alkyl ester and phenyl-C61-butyric acid alkyl ester can also be mentioned. Hydrogenated fullerenes and the like can also be mentioned. Among them, fullerene (fullerene) having an OH group (hydroxyl group) is preferred. This is because the dispersibility of the single-layer carbon nanotube dispersion is high. Further, when the number of OH groups is small, the degree of improvement in dispersibility of the single-layer carbon nanotubes is lowered. Conversely, when it is too much, it is difficult to synthesize. Therefore, the OH group number is preferably from 5 to 30 per molecule of fullerene. Very good for 8 to 15. When the amount (content) of fullerene added is too large, conductivity is lowered. Conversely, when there are too few, the effect is lacking. Therefore, the amount of fullerene is preferably 10 to 1000 parts by mass (particularly 20 parts by mass or more. 100 parts by mass or less) with respect to 100 parts by mass of the CNT.

透明導電性碳層(碳奈米管層)1亦可含有黏合劑樹脂。但從導電性觀點而言，較佳為不含黏合劑樹脂者。例如，當使用相互纏繞的CNT時，則即使無黏合劑樹脂也可完成。相互纏繞的CNT係CNT彼此間直接接觸。因無絕緣物介在其中故導電性良好。如果以掃描型電子顯微鏡觀察導電膜表面，則可確認、判定CNT是否為相互纏繞的結構。 The transparent conductive carbon layer (carbon nanotube layer) 1 may also contain a binder resin. However, from the viewpoint of conductivity, it is preferably one which does not contain a binder resin. For example, when intertwined CNTs are used, even a binder-free resin can be completed. The intertwined CNT-based CNTs are in direct contact with each other. Since there is no insulation in it, the conductivity is good. When the surface of the conductive film was observed with a scanning electron microscope, it was confirmed whether or not the CNTs were entangled with each other.

透明導電性碳層1係藉由使CNT分散液(使上述特徵之CNT及可依照需要添加的富勒烯分散的分散液)塗布於基板2上所構成。作為塗布方法，可列舉例如模具塗布、刮刀塗布、噴灑塗布、旋轉塗布、狹縫塗布、 微凹版印刷、柔版等。當然不限於此。碳奈米管分散液的塗布係在基板2之全面進行。為了均勻地進行紫外線照射時之絕緣化，較佳為透明導電性碳層(碳奈米管層)1均勻地成膜。 The transparent conductive carbon layer 1 is formed by applying a CNT dispersion (a CNT having the above characteristics and a dispersion of a fullerene which can be added as needed) to the substrate 2. Examples of the coating method include die coating, blade coating, spray coating, spin coating, and slit coating. Micro gravure printing, flexography, etc. Of course not limited to this. The coating of the carbon nanotube dispersion is performed on the entire substrate 2. In order to uniformly insulate the ultraviolet ray, it is preferable that the transparent conductive carbon layer (carbon nanotube layer) 1 is uniformly formed.

作為基板2的構成材料可適宜使用各種之物。可使用例如聚苯乙烯(PS)、聚甲基丙烯酸甲酯(PMMA)、苯乙烯-甲基丙烯酸甲酯共聚物(MS)、聚碳酸酯(PC)、環烯烴聚合物(COP)、環烯烴共聚物(COC)、聚對苯二甲酸乙二酯(PET)、聚萘二甲酸乙二酯(PEN)等之樹脂。在本發明，因圖案形成時不需過度的加熱，故抗熱性的要求度低。因此，即使在使用樹脂作為基板2構成材料之情形，樹脂選擇的自由度高。除了樹脂之外，亦可使用無機玻璃材料或陶瓷材料。 As the constituent material of the substrate 2, various materials can be suitably used. For example, polystyrene (PS), polymethyl methacrylate (PMMA), styrene-methyl methacrylate copolymer (MS), polycarbonate (PC), cycloolefin polymer (COP), ring can be used. A resin such as an olefin copolymer (COC), polyethylene terephthalate (PET) or polyethylene naphthalate (PEN). In the present invention, since the pattern is formed without excessive heating, the heat resistance is required to be low. Therefore, even in the case where a resin is used as the constituent material of the substrate 2, the degree of freedom in resin selection is high. In addition to the resin, an inorganic glass material or a ceramic material can also be used.

在本發明的情況下，係在透明導電性碳層1上設置外護層(保護層)3。 In the case of the present invention, an outer sheath (protective layer) 3 is provided on the transparent conductive carbon layer 1.

外護層3係包含有機系高分子材料、無機系高分子材料或有機-無機之混合樹脂等。 The outer sheath 3 includes an organic polymer material, an inorganic polymer material, or an organic-inorganic hybrid resin.

作為有機系高分子材料，可列舉熱塑性樹脂、熱硬化性樹脂、纖維素樹脂、光硬化性樹脂等。由可視光透過性、基板之抗熱性、玻璃轉移點及膜硬化度等觀點，適宜選擇。作為熱塑性樹脂，可列舉例如聚甲基丙烯酸甲酯、聚苯乙烯、聚對苯二甲酸乙二酯、聚碳酸酯、聚乳酸、ABS樹脂等。作為熱硬化性樹脂，可列舉例如酚樹脂、三聚氰胺樹脂、醇酸樹脂、聚醯亞胺、環氧樹脂、氟樹脂、胺基甲酸酯樹脂等。作為纖維素樹脂，可列 舉例如乙醯纖維素、三乙醯纖維素等。作為光硬化性樹脂，可列舉例如含有各種寡聚物、單體、光聚合起始劑之樹脂等。 Examples of the organic polymer material include a thermoplastic resin, a thermosetting resin, a cellulose resin, and a photocurable resin. It is suitably selected from the viewpoints of visible light transmittance, heat resistance of the substrate, glass transition point, and film hardening degree. Examples of the thermoplastic resin include polymethyl methacrylate, polystyrene, polyethylene terephthalate, polycarbonate, polylactic acid, and ABS resin. Examples of the thermosetting resin include a phenol resin, a melamine resin, an alkyd resin, a polyimide, an epoxy resin, a fluororesin, a urethane resin, and the like. As a cellulose resin, it can be listed Examples are acetaminophen, triethylcellulose, and the like. The photocurable resin may, for example, be a resin containing various oligomers, monomers, and photopolymerization initiators.

作為無機系材料，可列舉例如二氧化矽溶膠、鋁氧溶膠、氧化鋯溶膠、二氧化鈦溶膠等。亦可列舉在該無機系材料添加水或酸觸媒予以水解、脫水縮合的聚合物等。 Examples of the inorganic material include a cerium oxide sol, an aluminum oxysol, a zirconia sol, and a titania sol. A polymer obtained by adding water or an acid catalyst to the inorganic material to be hydrolyzed, dehydrated and condensed may be mentioned.

作為有機-無機之混合樹脂，可列舉例如將該無機材料的一部分以有機官能基修飾(例如，取代或加成)之樹脂、或將矽烷偶合劑等之各種偶合劑作為主成分之樹脂等。 The organic-inorganic hybrid resin may, for example, be a resin in which a part of the inorganic material is modified (for example, substituted or added) with an organic functional group, or a resin containing a coupling agent such as a decane coupling agent as a main component.

外護層3，其膜厚過厚時，則導電膜之接觸電阻變大。相反地，若外護層3膜厚過薄，則難以獲得作為保護膜之效果。因此，外護層3厚度係較佳為1nm至1μm。特佳為10nm以上。較佳為200nm以下。更佳為150nm以下。 When the film thickness of the outer sheath 3 is too thick, the contact resistance of the conductive film becomes large. On the contrary, if the film thickness of the outer sheath 3 is too thin, it is difficult to obtain an effect as a protective film. Therefore, the thickness of the outer sheath 3 is preferably from 1 nm to 1 μm. Particularly preferred is 10 nm or more. It is preferably 200 nm or less. More preferably, it is 150 nm or less.

設置於透明導電性碳層(碳奈米管層)1上的外護層3，特佳為例如包含一種組成物，其含有水解性有機矽烷的水解物。 The outer sheath 3 provided on the transparent conductive carbon layer (carbon nanotube layer) 1 preferably contains, for example, a composition containing a hydrolyzate of hydrolyzable organodecane.

較佳為包含一種組成物，其含有四官能水解性有機矽烷。 It preferably contains a composition containing a tetrafunctional hydrolyzable organodecane.

特佳為包含一種組成物，其含有：四官能水解性有機矽烷；與具有環氧基及烷氧基之水解性有機矽烷的水解物。 It is particularly preferable to contain a composition comprising: a tetrafunctional hydrolyzable organodecane; and a hydrolyzate of a hydrolyzable organodecane having an epoxy group and an alkoxy group.

其中，相對於樹脂的全固體成分，該具有環氧基及烷氧基之水解性有機矽烷的水解物含量較佳為1至10重 量%之物。 Wherein the hydrolyzate content of the hydrolyzable organodecane having an epoxy group and an alkoxy group is preferably from 1 to 10, based on the total solid content of the resin. Amount of money.

在含有具有環氧基及烷氧基之水解性有機矽烷的共水解物時，於塗布該組成物予以硬化之情形，共水解物之環氧基係與含於基板的羥基或羰基等的氧部位鍵結。因此，可提高外護層(保護膜)與透明導電性碳層(碳奈米管層)1之密接性。 In the case of containing a cohydrolyzate of a hydrolyzable organodecane having an epoxy group and an alkoxy group, when the composition is cured, the epoxy group of the cohydrolyzate and the hydroxyl group or the carbonyl group contained in the substrate are oxygenated. Site bonding. Therefore, the adhesion between the outer sheath (protective film) and the transparent conductive carbon layer (carbon nanotube layer) 1 can be improved.

包含一種組成物，其含有二氧化矽系金屬氧化物微粒。視情況包含一種組成物，其進一步含有具有氟取代烷基之水解性有機矽烷的水解物。 A composition comprising ceria-based metal oxide fine particles is included. A composition comprising, as the case may be, a hydrolyzate of a hydrolyzable organodecane having a fluorine-substituted alkyl group.

該水解性有機矽烷的水解物較佳為相對於含於該水解性有機矽烷之烷氧基的水比在1.0至3.0予以反應之物。 The hydrolyzate of the hydrolyzable organodecane is preferably a reaction which is reacted at 1.0 to 3.0 with respect to the water ratio of the alkoxy group contained in the hydrolyzable organodecane.

該水解性有機矽烷的水解物，較佳為聚苯乙烯換算重量平均分子量1000至2000之化合物之物。 The hydrolyzate of the hydrolyzable organodecane is preferably a compound having a weight average molecular weight of 1,000 to 2,000 in terms of polystyrene.

該四官能水解性有機矽烷，例如為以SiX4所示之化合物。該X為水解基。例如烷氧基、乙醯氧基、肟基、烯氧基(Enoxy)等。尤其是，以Si(OR1)4所示之四官能水解性有機烷氧基矽烷。該R1係較佳為一價烴基。例如，為碳數1至8之一價烴基。例如，為碳數1至8之烷基(甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基)。作為本實施形態所使用之四官能水解性有機矽烷，可列舉例如四甲氧基矽烷或四乙氧基矽烷等。具有環氧基及烷氧基之水解性有機矽烷，例如以R2Si(OR3)3、R2R4Si(OR3)2所示之化合物。R2係選自環氧基、環氧丙氧基及該等之取代物之基。R3與該R1相同，為一價烴基。例如，為甲基、乙基、丙基、丁基、戊基等。R4係選自 氫、烷基、氟烷基、芳基、烯基、甲基丙烯醯氧基(methacryloxy)、環氧基、環氧丙氧基、胺基及該等之取代物之基。 The tetrafunctional hydrolyzable organodecane is, for example, a compound represented by SiX 4 . This X is a hydrolyzable group. For example, an alkoxy group, an ethyloxy group, a decyl group, an enoxy group (Enoxy) or the like. In particular, a tetrafunctional hydrolyzable organoalkoxydecane represented by Si(OR 1 ) 4 . The R 1 is preferably a monovalent hydrocarbon group. For example, it is a one-valent hydrocarbon group having 1 to 8 carbon atoms. For example, it is an alkyl group having 1 to 8 carbon atoms (methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl). The tetrafunctional hydrolyzable organodecane used in the present embodiment may, for example, be tetramethoxydecane or tetraethoxydecane. The hydrolyzable organodecane having an epoxy group and an alkoxy group is, for example, a compound represented by R 2 Si(OR 3 ) 3 or R 2 R 4 Si(OR 3 ) 2 . R 2 is selected from the group consisting of epoxy groups, glycidoxy groups, and the substituents of such substituents. R 3 is the same as the R 1 and is a monovalent hydrocarbon group. For example, it is methyl, ethyl, propyl, butyl, pentyl or the like. R 4 is selected from the group consisting of hydrogen, alkyl, fluoroalkyl, aryl, alkenyl, methacryloxy, epoxy, propylene propoxy, amine, and the substituents thereof. .

作為本實施形態所使用之具有環氧基及烷氧基之水解性有機矽烷，可列舉例如γ-環氧丙氧丙基三甲氧基矽烷、γ-環氧丙氧丙基甲基二乙氧基矽烷、γ-環氧丙氧丙基三乙氧基矽烷、γ-環氧丙氧丙基二甲氧基甲基矽烷等。 Examples of the hydrolyzable organodecane having an epoxy group and an alkoxy group used in the present embodiment include γ-glycidoxypropyltrimethoxydecane and γ-glycidoxypropylmethyldiethoxylate. Base decane, γ-glycidoxypropyl triethoxy decane, γ-glycidoxypropyl dimethoxymethyl decane, and the like.

作為二氧化矽系金屬氧化物微粒，較佳為使用中空二氧化矽微粒。中空二氧化矽微粒係形成空洞於二氧化矽系金屬氧化物之外殼的內部之物。外殼係較佳為具有細孔之多孔質之物。亦可為使細孔閉塞，密封空洞之物。只要是有助於所形成之被膜的低折射率化者，則未必限於上述中空二氧化矽。 As the cerium oxide-based metal oxide fine particles, hollow cerium oxide fine particles are preferably used. The hollow ceria particles form a cavity which is hollow inside the outer shell of the ceria-based metal oxide. The outer casing is preferably a porous material having fine pores. It is also possible to seal the pores and seal the voids. As long as it contributes to the low refractive index of the formed film, it is not necessarily limited to the above hollow cerium oxide.

在如此組成之外護層的情形，光反射率降低，透光率提高。相對於摩擦等的物理性保護高。對於熱或濕度等之環境變化的保護也高。如此在設置外護層3時，則藉由短時間的紫外線照射，而可確認透明導電性碳層(碳奈米管層)1自導電性改質為絕緣性的現象。在本發明，如此之外護層在紫外線照射步驟前，係設置於透明導電性碳層(碳奈米管層)1上。 In the case where the outer sheath is composed as described above, the light reflectance is lowered and the light transmittance is improved. Physical protection against friction and the like is high. Protection against environmental changes such as heat or humidity is also high. When the outer sheath 3 is provided in this manner, it is confirmed that the transparent conductive carbon layer (carbon nanotube layer) 1 is modified from the conductivity to the insulating property by the ultraviolet irradiation for a short period of time. In the present invention, the outer cover layer is provided on the transparent conductive carbon layer (carbon nanotube layer) 1 before the ultraviolet irradiation step.

外護層3，係藉由塗布含有上述組成物的塗料而設置。作為塗布方法，可採用以上述CNT分散液的塗布所說明的方法。塗布係在導電層(碳奈米管層)上進行。而且，全面塗布。為了均勻進行照射紫外線時之絕緣化，較佳為外護層3亦可均勻地成膜。 The outer sheath 3 is provided by applying a coating material containing the above composition. As the coating method, a method described by coating the above CNT dispersion liquid can be employed. The coating is carried out on a conductive layer (carbon nanotube layer). Moreover, it is fully coated. In order to uniformly insulate the ultraviolet ray when irradiated, it is preferable that the outer sheath 3 is uniformly formed into a film.

使預定圖案之樹脂層4設置於外護層3上。存在樹脂層4之處的下方位置之透明導電性碳層(碳奈米管層)1，不照射紫外線。無存在樹脂層4之處的下方位置之透明導電性碳層(碳奈米管層)1，照射紫外線。樹脂層4可發揮作為遮罩之功能。構成樹脂層4之樹脂，係不穿透為了絕緣化所使用之波長的紫外線的樹脂。可列舉例如光阻材料(例如，酚醛清漆樹脂、三聚氰胺樹脂等)、光硬化性樹脂(例如，丙烯醯基改質樹脂等)、熱硬化性樹脂(例如，環氧樹脂等)、熱塑性樹脂(例如，丙烯酸樹脂、芳香族系樹脂等)。樹脂層4並非僅發揮屏蔽紫外線之功能。樹脂層4因與外護層3的高密接性，故可防止對欲保持導電性之部分的紫外線的漏出(潛行)、防止發生自氧產生的臭氧等之活性氧的漏出(進入)。藉此，可獲得精密度高的圖案化。樹脂層4之形成方法並無特別限定。例如，可使用網版印刷、套版印刷、噴墨印刷、凹版印刷等的印刷手段。若採用印刷手段，則可在預定之圖案對應處的外護層3上設置樹脂。 The resin layer 4 of a predetermined pattern is placed on the outer cover 3. The transparent conductive carbon layer (carbon nanotube layer) 1 at a position below the resin layer 4 is not irradiated with ultraviolet rays. The transparent conductive carbon layer (carbon nanotube layer) 1 at a position where there is no resin layer 4 is irradiated with ultraviolet rays. The resin layer 4 functions as a mask. The resin constituting the resin layer 4 is a resin that does not penetrate ultraviolet rays of a wavelength used for insulating. For example, a photoresist (for example, a novolak resin, a melamine resin, etc.), a photocurable resin (for example, an acryl-based modified resin, etc.), a thermosetting resin (for example, an epoxy resin, etc.), and a thermoplastic resin ( For example, an acrylic resin, an aromatic resin, etc.). The resin layer 4 does not function only to shield ultraviolet rays. Since the resin layer 4 has high adhesion to the outer sheath 3, it is possible to prevent leakage (intrusion) of ultraviolet rays in a portion where conductivity is to be maintained, and prevention of leakage (entry) of active oxygen such as ozone generated by oxygen. Thereby, high-precision patterning can be obtained. The method of forming the resin layer 4 is not particularly limited. For example, printing means such as screen printing, pattern printing, inkjet printing, gravure printing, or the like can be used. If a printing means is employed, a resin can be provided on the outer sheath 3 at a position corresponding to the predetermined pattern.

紫外線照射於透明導電性碳層(碳奈米管層)1。此紫外線係較佳為波長為10至400nm。更佳為波長為150至260nm。特佳為波長為150至180nm。最佳為波長為160至175nm。例如，在照射超過400nm之長波長的紫外線的情形，則難以產生由導電性碳奈米管至絕緣性碳奈米管的改質。因此，在通常的光微影法製程所使用之高壓汞燈的紫外線(波長：365nm)照射下，難以產生改質。為了將導電性碳奈米管改質為絕緣性碳奈米管，照射紫 外線較佳為波長為260nm以下之物。更佳為180nm以下的紫外線。例如，依照低壓汞燈的紫外線(波長：185nm、254nm)照射，在照射處，碳奈米管容易自導電性改質為絕緣性。但，基板2為樹脂製之情形，亦有可確認在基板2變色的現象之情形。由此可知，照射紫外線為180nm以下，進一步係特佳為175nm以下的波長。例如，以氙準分子燈所致之紫外線(波長：172nm)格外良好。上述特性之紫外線照射的時間，例如為10秒至1小時左右。較佳為1分鐘以上。較佳為40分鐘以下。紫外線的照射累計光量，例如為50至500,000mJ/cm2左右。較佳為100至100,000mJ/cm2。更佳為500至30,000mJ/cm2。較佳的累計光量係藉由碳奈米管層1之厚度，而稍微變動。因有無外護層而大幅變動。具有外護層時，則碳奈米管在短時間自導電性改質為絕緣性。亦因外護層種類或厚度而變動。若外護層係含有水解性有機矽烷水解物之組成物，則照射時間大幅縮短。外護層3的厚度係較佳為10至200nm。更佳為50至150nm。1a係紫外線照射之處。紫外線照射處1a改質為絕緣性。1b為紫外線未照射之處。紫外線未照射之處1b則保持導電性原樣。 Ultraviolet rays are irradiated on the transparent conductive carbon layer (carbon nanotube layer) 1. This ultraviolet ray is preferably at a wavelength of from 10 to 400 nm. More preferably, the wavelength is from 150 to 260 nm. Particularly preferred is a wavelength of from 150 to 180 nm. The optimum wavelength is 160 to 175 nm. For example, in the case of irradiating ultraviolet rays having a long wavelength of more than 400 nm, it is difficult to reform from a conductive carbon nanotube to an insulating carbon nanotube. Therefore, it is difficult to produce a modification under ultraviolet light (wavelength: 365 nm) of a high-pressure mercury lamp used in a usual photolithography process. In order to reform a conductive carbon nanotube into an insulating carbon nanotube, the ultraviolet ray is preferably a wavelength of 260 nm or less. More preferably, it is ultraviolet light of 180 nm or less. For example, according to the ultraviolet rays (wavelength: 185 nm, 254 nm) of a low-pressure mercury lamp, the carbon nanotubes are easily modified from the conductivity to the insulation at the irradiation. However, in the case where the substrate 2 is made of a resin, there is a case where it is confirmed that the substrate 2 is discolored. From this, it is understood that the irradiation ultraviolet ray is 180 nm or less, and further preferably a wavelength of 175 nm or less. For example, ultraviolet rays (wavelength: 172 nm) caused by a quinone excimer lamp are exceptionally good. The time of ultraviolet irradiation of the above characteristics is, for example, about 10 seconds to 1 hour. It is preferably 1 minute or more. It is preferably 40 minutes or less. The cumulative amount of ultraviolet light irradiation is, for example, about 50 to 500,000 mJ/cm 2 . It is preferably from 100 to 100,000 mJ/cm 2 . More preferably, it is 500 to 30,000 mJ/cm 2 . The preferred cumulative amount of light varies slightly by the thickness of the carbon nanotube layer 1. Greatly changed due to the presence or absence of the outer sheath. When the outer sheath is provided, the carbon nanotubes are modified from electrical conductivity to insulation in a short time. It also changes due to the type or thickness of the outer sheath. When the outer sheath contains a composition of a hydrolyzable organodecane hydrolyzate, the irradiation time is greatly shortened. The thickness of the outer sheath 3 is preferably from 10 to 200 nm. More preferably 50 to 150 nm. 1a is where the ultraviolet light is irradiated. The ultraviolet irradiation 1a is modified to be insulating. 1b is where the ultraviolet light is not irradiated. The portion 1b where the ultraviolet ray is not irradiated remains as it is.

在紫外線照射時，在環境中較佳為存在氧(或活性氧)。即使進行紫外線照射，在無氧狀態，則無法確認由透明導電性碳層(碳奈米管層)1之導電性至絕緣性的改質。該具有氧之環境，較佳為氧壓為101至21273Pa。更佳為氧壓為507至20260Pa。特佳為氧壓為1013至10130Pa。 In the case of ultraviolet irradiation, oxygen (or active oxygen) is preferably present in the environment. Even when ultraviolet irradiation was performed, the conductivity from the transparent conductive carbon layer (carbon nanotube layer) 1 to the insulating property could not be confirmed in the oxygen-free state. The oxygen-containing environment preferably has an oxygen pressure of 101 to 21,273 Pa. More preferably, the oxygen pressure is 507 to 20260 Pa. Particularly preferred is an oxygen pressure of 1013 to 10130 Pa.

透明導電性碳層(碳奈米管層)1，藉由紫外線照射，而成為預定圖案之導電性(或絕緣性)膜。此本發明與先前之圖案形成方法大為不同。亦即，外護層(被覆層)3係照樣殘留。導電層(絕緣層)係照樣被外護層3所覆蓋。並無外露。此結果，導電層(絕緣層)之保護效果高。亦即，耐久性高。例如，難以引起導電層(絕緣層)剝落(chipping)(脫落)。水份(濕氣)難以進入導電層(絕緣層)。為了獲得預定圖案之導電膜，無需除去(蝕刻除去)透明導電性碳層(碳奈米管層)1。因無需為了除去而使用藥劑，故對環境溫和。可以非常簡單的作業獲得導電膜(絕緣膜)。 The transparent conductive carbon layer (carbon nanotube layer) 1 is a conductive (or insulating) film having a predetermined pattern by ultraviolet irradiation. This invention is quite different from previous patterning methods. That is, the outer sheath (cover layer) 3 remains as it is. The conductive layer (insulating layer) is also covered by the outer sheath 3 as it is. No exposure. As a result, the conductive layer (insulating layer) has a high protective effect. That is, the durability is high. For example, it is difficult to cause the conductive layer (insulating layer) to chip off (fall off). It is difficult for moisture (moisture) to enter the conductive layer (insulating layer). In order to obtain a conductive film of a predetermined pattern, it is not necessary to remove (etch away) the transparent conductive carbon layer (carbon nanotube layer) 1. Since it is not necessary to use a chemical for removal, it is mild to the environment. A conductive film (insulating film) can be obtained in a very simple operation.

藉由紫外線照射而形成預定圖案之膜後，樹脂層4可依照需要予以除去。除去方法並無特別限定。例如，適宜地利用使用黏著片或輥予以剝離之方法，使用刷洗等擦掉(rub off)之方法、使用溶解或膨脹之藥液予以溶解(或剝離)之方法。 After the film of the predetermined pattern is formed by ultraviolet irradiation, the resin layer 4 can be removed as needed. The removal method is not particularly limited. For example, a method of peeling off using an adhesive sheet or a roll, a method of rubbing off by rubbing or the like, and a method of dissolving (or peeling off) using a dissolved or expanded chemical liquid are suitably employed.

以下，列舉具體實施例進行說明。但本發明並不限定於下述實施例。 Hereinafter, specific examples will be described. However, the invention is not limited to the following examples.

[實施例1] [Example 1]

對於藉由弧光放電所合成的單層壁碳奈米管(市售品)，進行酸處理、水洗淨、離心分離、過濾。界面活性劑(十二烷基苯磺酸鈉：SDBS)0.2wt%水溶液被添加於該精製碳奈米管。對此含碳奈米管之水溶液，藉由超音波裝置進行分散處理。接著，進行離心分離。如此可獲得碳奈米管分散液(CNT：3200ppm)。 The single-walled carbon nanotubes (commercially available) synthesized by arc discharge were subjected to acid treatment, water washing, centrifugation, and filtration. A surfactant (sodium dodecylbenzenesulfonate: SDBS) 0.2 wt% aqueous solution was added to the refined carbon nanotube. The aqueous solution containing the carbon nanotubes was subjected to dispersion treatment by an ultrasonic device. Next, centrifugation is carried out. Thus, a carbon nanotube dispersion (CNT: 3200 ppm) was obtained.

上述碳奈米管分散液係塗布於基板2上。基板2為PET薄膜(MKZ-T4A：東山film公司製)。塗布方法為模具塗布法。塗布厚度為0.05μm(乾燥後之厚度)。塗布後，進行離子交換水洗淨。藉此，除去塗膜(碳奈米管層)中所含之界面活性劑。此後，進行乾燥(1.5分鐘；120℃)。如此，碳奈米管層(透明導電性碳層)1係設置於PET薄膜2上。 The carbon nanotube dispersion is applied to the substrate 2. The substrate 2 is a PET film (MKZ-T4A: manufactured by Higashiyama Film Co., Ltd.). The coating method is a die coating method. The coating thickness was 0.05 μm (thickness after drying). After coating, it was washed with ion exchange water. Thereby, the surfactant contained in the coating film (carbon nanotube layer) is removed. Thereafter, drying was carried out (1.5 minutes; 120 ° C). Thus, the carbon nanotube layer (transparent conductive carbon layer) 1 is provided on the PET film 2.

外護層3係設置於碳奈米管層1上。在外護層3之構成，可使用1.8wt% Earosera(含有水解性有機矽烷之組成物：Panasonic公司製)。塗布方法為模具塗布法。塗布厚度為0.1μm(乾燥後之厚度)。 The outer sheath 3 is disposed on the carbon nanotube layer 1. In the configuration of the outer sheath 3, 1.8 wt% Earosera (a composition containing a hydrolyzable organic decane: manufactured by Panasonic) can be used. The coating method is a die coating method. The coating thickness was 0.1 μm (thickness after drying).

樹脂層(遮罩)4被設置於外護層3上。預定圖案之遮罩(樹脂層)4係藉由網版印刷而形成。亦即，在預定之處，印刷UV硬化性樹脂(JELCON GEC-10H：十條化學公司製)。塗布厚度為50μm。此後，照射紫外線(波長365nm)。累計光量為1,330mJ/cm2。藉由紫外線照射使樹脂硬化。在無設置樹脂層4之處則成為開口部5。自開口部5照射紫外線於碳奈米管層(透明導電性碳層)1。開口部5係線寬為100μm，一邊之長度為5mm之□形。 A resin layer (mask) 4 is provided on the outer sheath 3. A mask (resin layer) 4 of a predetermined pattern is formed by screen printing. That is, a UV curable resin (JELCON GEC-10H: manufactured by Shika Chemical Co., Ltd.) was printed at a predetermined place. The coating thickness was 50 μm. Thereafter, ultraviolet rays (wavelength 365 nm) were irradiated. The cumulative amount of light was 1,330 mJ/cm 2 . The resin is hardened by ultraviolet irradiation. The opening 5 is formed where the resin layer 4 is not provided. The ultraviolet light is applied to the carbon nanotube layer (transparent conductive carbon layer) 1 from the opening 5. The opening 5 has a line width of 100 μm and a side length of 5 mm.

此後，自預定圖案之樹脂層(遮罩)4上方，照射氙準分子燈所致之紫外線(波長：172nm)。紫外線照射時之環境為氮94%、氧6%。因混合氣體所致之壓力為1.013×105Pa。照射紫外線的累計光量為10,560mJ/cm2。照射後使用黏著片，使樹脂層4剝離、除去。 Thereafter, ultraviolet rays (wavelength: 172 nm) caused by the xenon excimer lamp were irradiated from the resin layer (mask) 4 of the predetermined pattern. The environment under ultraviolet irradiation is 94% nitrogen and 6% oxygen. The pressure due to the mixed gas was 1.013 × 10 5 Pa. The cumulative amount of light irradiated with ultraviolet rays was 10,560 mJ/cm 2 . After the irradiation, the adhesive sheet was used to peel off and remove the resin layer 4.

該□形狀之開口部的內側與外側間之通導係 以測試器(tester)調查。此結果可明白在兩者之間無通導(被絕緣)。 a guide between the inside and the outside of the opening of the □ shape Investigate with a tester. This result shows that there is no conduction between the two (insulated).

將遮罩4之開口部5之圖案形狀(□形狀)與碳奈米管導電層之圖案形狀(□形狀)加以比較。兩者的一致度極高。亦即，透明導電膜以高精密度形成。 The pattern shape (□ shape) of the opening portion 5 of the mask 4 is compared with the pattern shape (□ shape) of the carbon nanotube conductive layer. The consistency between the two is extremely high. That is, the transparent conductive film is formed with high precision.

為了評價導電性，第4圖所示導電性評價圖案與上述□形狀圖案同樣地形成。在此圖案，相當於樹脂層的部分係成為導電部41，相當於開口部的部分係成為絕緣部51。在導電性評價圖案中導電部41兩端的端子間電阻值係以測試器測定。此結果，端子間電阻值為約20kΩ。此時，相對於樹脂膜之細線部的寬為721μm，導電膜之細線部6的寬為729μm。 In order to evaluate the conductivity, the conductivity evaluation pattern shown in Fig. 4 is formed in the same manner as the above-described □ shape pattern. In this pattern, the portion corresponding to the resin layer serves as the conductive portion 41, and the portion corresponding to the opening portion serves as the insulating portion 51. The resistance value between the terminals at both ends of the conductive portion 41 in the conductivity evaluation pattern was measured by a tester. As a result, the resistance between the terminals was about 20 kΩ. At this time, the width of the thin line portion with respect to the resin film was 721 μm, and the width of the thin line portion 6 of the conductive film was 729 μm.

[實施例2] [Embodiment 2]

除了在實施例1，於樹脂層4使用熱硬化性樹脂(X-100 CL1：太陽油墨製造公司製)，並在烤爐中使用於100℃、30分鐘之硬化處理的方法以外，其他則同樣地進行。 In the same manner as in the first embodiment, a thermosetting resin (X-100 CL1: manufactured by Sun Ink Co., Ltd.) was used for the resin layer 4, and a method of hardening treatment at 100 ° C for 30 minutes in an oven was used. Conducted.

該□形狀開口部的內側與外側之間之通導係以測試器調查。此結果可明白在兩者之間並無通導(被絕緣)。 The conduction between the inner side and the outer side of the □-shaped opening portion was investigated by a tester. This result shows that there is no general conduction between the two (insulated).

比較遮罩之開口部的圖案形狀(□形狀)與碳奈米管導電層的圖案形狀(□形狀)。兩者的一致度極高。亦即，透明導電膜以高精密度所形成。 The pattern shape (□ shape) of the opening portion of the mask and the pattern shape (□ shape) of the carbon nanotube conductive layer were compared. The consistency between the two is extremely high. That is, the transparent conductive film is formed with high precision.

為了評價導電性，如第4圖所示，導電性評價圖案與上述□形狀圖案同樣地形成。導電性評價圖案之導電部41兩端的端子間電阻值係以測試器測定。此結果 可知端子間電阻值為約20kΩ。此時，相對於在樹脂膜之細線部的寬為699μm，導電膜之細線部6的寬為729μm。 In order to evaluate the conductivity, as shown in FIG. 4, the conductivity evaluation pattern was formed in the same manner as the above-described □ shape pattern. The inter-terminal resistance values at both ends of the conductive portion 41 of the conductivity evaluation pattern were measured by a tester. This result It can be seen that the resistance between the terminals is about 20 kΩ. At this time, the width of the thin line portion 6 of the conductive film was 729 μm with respect to the width of the thin line portion of the resin film of 699 μm.

[比較例1] [Comparative Example 1]

除了在實施例1，設為氮環境下(氧分壓0Pa：無氧)以外，其他同樣地進行。 The same procedure was carried out in the same manner as in Example 1 except that the nitrogen atmosphere (oxygen partial pressure 0 Pa: no oxygen) was used.

紫外線照射處，在比較例1並無自導電性改質為絕緣性。 In the ultraviolet irradiation, the comparative example 1 did not change from conductivity to insulation.

[比較例2] [Comparative Example 2]

除了在實施例1不設置外護層3以外，其他則同樣地進行。 Except that the outer sheath 3 was not provided in the first embodiment, the other was carried out in the same manner.

紫外線照射處，即使在比較例2亦無自導電性改質為絕緣性。 In the ultraviolet irradiation, even in Comparative Example 2, there was no self-conductivity modification to insulation.

[比較例3] [Comparative Example 3]

在實施例1，更換樹脂遮罩，改用金屬(Ni)製遮罩進行。金屬製遮罩僅配置於外護層上，並無密接。 In the first embodiment, the resin mask was replaced and changed to a mask made of metal (Ni). The metal mask is only placed on the outer sheath and is not in close contact.

□形狀之開口部的內側與外側之間的通導係以測試器調查。 The conduction between the inside and the outside of the opening portion of the shape is investigated by a tester.

此結果可知在兩者之間並無通導(被絕緣)。 This result shows that there is no conduction between the two (insulated).

比較遮罩開口部之圖案形狀(□形狀)與碳奈米管導電層之圖案形狀(□形狀)。此結果可知經絕緣的部分相較於該遮罩開口部為擴大。亦即，透明導電圖案之形成精密度變低。 The pattern shape (□ shape) of the mask opening portion and the pattern shape (□ shape) of the carbon nanotube conductive layer were compared. As a result, it is understood that the insulated portion is enlarged compared to the opening of the mask. That is, the formation precision of the transparent conductive pattern becomes low.

除了將金屬製遮罩之圖案設成如第4圖所示之導電性評價圖案之外，其他與上述□形狀圖案同樣地進行，在導電膜形成導電性評價圖案。該圖案之導電部 41兩端的端子間電阻值以測試器測定。此結果，端子間電阻值為356kΩ，電阻值相較於實施例變大。 The conductive evaluation pattern was formed on the conductive film in the same manner as the above-described □ shape pattern except that the pattern of the metal mask was set to the conductivity evaluation pattern as shown in FIG. 4 . Conductive part of the pattern The resistance between the terminals at both ends of 41 is measured by a tester. As a result, the resistance value between the terminals was 356 kΩ, and the resistance value was larger than that of the embodiment.

[參考例1] [Reference Example 1]

除了在實施例1使用光硬化性樹脂(JELCON RIP-2A：十條化學公司製)以外，其他則同樣地進行。 The photocurable resin (JELCON RIP-2A: manufactured by Shijo Chemical Co., Ltd.) was used in the same manner as in Example 1.

在參考例1，光硬化性樹脂的硬化收縮變大。因此，無法獲得如實施例1的結果。 In Reference Example 1, the curing shrinkage of the photocurable resin became large. Therefore, the result as in Example 1 could not be obtained.

[參考例2] [Reference Example 2]

除了在實施例2，使用熱硬化性樹脂(JELCON MS-03B：十條化學公司製)，在烤爐中使用以100℃、1分鐘之硬化處理的方法以外，其他則同樣地進行。 In the same manner as in the second embodiment, a thermosetting resin (JELCON MS-03B: manufactured by Shijo Chemical Co., Ltd.) was used, and in the oven, a method of curing at 100 ° C for 1 minute was used, and the others were carried out in the same manner.

在參考例2，熱硬化性樹脂自塗布面被拒斥。因此，無法獲得如實施例2的結果。 In Reference Example 2, the thermosetting resin was rejected from the coated surface. Therefore, the result as in Example 2 could not be obtained.

1‧‧‧透明導電性碳層(碳奈米管層) 1‧‧‧Transparent conductive carbon layer (carbon nanotube layer)

1a‧‧‧紫外線照射處(絕緣性改質處) 1a‧‧‧UV irradiation (insulation modification)

1b‧‧‧紫外線未照射處(透明導電性處) 1b‧‧‧Unilluminated areas of ultraviolet light (transparent conductivity)

2‧‧‧基板 2‧‧‧Substrate

3‧‧‧外護層(含有水解性有機矽烷之組成物層) 3‧‧‧ outer sheath (layer containing hydrolyzable organodecane)

4‧‧‧樹脂層(遮罩) 4‧‧‧Resin layer (mask)

Claims (16)

一種膜形成方法，其係使紫外線照射區域之導電性碳層改質為絕緣性，紫外線未照射區域之導電性碳層係保持導電性之預定圖案的膜形成方法，其特徵為具備：設置導電性碳層之步驟；在該導電性碳層上設置外護層的步驟；在該外護層上密接預定圖案之樹脂層而設置的步驟；在有氧之環境下，對應於無該樹脂層之處，照射紫外線於該導電性碳層的步驟。 A film forming method for reforming a conductive carbon layer in an ultraviolet irradiation region into an insulating property, and a conductive carbon layer in an ultraviolet non-irradiated region is a film forming method for maintaining a predetermined pattern of conductivity, and is characterized in that: a conductive layer is provided a step of providing a cover layer on the conductive carbon layer; a step of providing a resin layer of a predetermined pattern on the outer cover layer; and a corresponding layer of the resin layer in an aerobic environment Wherein, the step of irradiating ultraviolet rays on the conductive carbon layer. 如請求項1之膜形成方法，其中該外護層係以含有選自水解性有機矽烷之水解物之群組中至少一個之組成物構成。 The film forming method of claim 1, wherein the outer sheath is composed of a composition containing at least one selected from the group consisting of hydrolyzable hydrolyzable organic decane. 如請求項1或2之膜形成方法，其中該外護層係厚度為1nm至1μm。 The film forming method of claim 1 or 2, wherein the outer cover layer has a thickness of from 1 nm to 1 μm. 如請求項1至3中任一項之膜形成方法，其中該預定圖案之樹脂層係使用不穿透紫外線的材料之樹脂，以印刷手段設置。 The film forming method according to any one of claims 1 to 3, wherein the resin layer of the predetermined pattern is provided by a printing means using a resin which does not penetrate the ultraviolet ray material. 如請求項1至4中任一項之膜形成方法，其中該紫外線係具有10至400nm的範圍之波長的紫外線。 The film forming method according to any one of claims 1 to 4, wherein the ultraviolet ray has ultraviolet rays having a wavelength in the range of 10 to 400 nm. 如請求項1至4中任一項之膜形成方法，其中該紫外線係具有150至180nm的範圍之波長的紫外線。 The film forming method according to any one of claims 1 to 4, wherein the ultraviolet ray has ultraviolet rays having a wavelength in the range of 150 to 180 nm. 如請求項1至6中任一項之膜形成方法，其中該紫外線之照射累計光量為50至500000mJ/cm2。 The film formation method according to any one of claims 1 to 6, wherein the ultraviolet light irradiation cumulative light amount is from 50 to 500,000 mJ/cm 2 . 如請求項1至6中任一項之膜形成方法，其中該紫外線之照射累計光量為500至30000mJ/cm2。 The film forming method according to any one of claims 1 to 6, wherein the ultraviolet light irradiation cumulative light amount is 500 to 30,000 mJ/cm 2 . 如請求項1至8中任一項之膜形成方法，其進一步具備在該紫外線照射後，除去該樹脂層之步驟。 The film forming method according to any one of claims 1 to 8, further comprising the step of removing the resin layer after the ultraviolet irradiation. 如請求項1至9中任一項之膜形成方法，其中該有氧之環境係氧壓為101至21273Pa。 The film forming method according to any one of claims 1 to 9, wherein the aerobic environment has an oxygen pressure of 101 to 21273 Pa. 如請求項1至9中任一項之膜形成方法，其中該有氧之環境係氧壓為1013至10130Pa。 The film forming method according to any one of claims 1 to 9, wherein the aerobic environment has an oxygen pressure of 1013 to 10130 Pa. 如請求項1至11中任一項之膜形成方法，其中該導電性碳層係以石墨烯構成。 The film formation method according to any one of claims 1 to 11, wherein the conductive carbon layer is composed of graphene. 如請求項1至12中任一項之膜形成方法，其中該導電性碳層係以碳奈米管構成。 The film forming method according to any one of claims 1 to 12, wherein the conductive carbon layer is composed of a carbon nanotube. 如請求項1至13中任一項之膜形成方法，其中該導電性碳層係以接受酸處理的單層碳奈米管構成。 The film forming method according to any one of claims 1 to 13, wherein the conductive carbon layer is composed of a single-layer carbon nanotube which is subjected to acid treatment. 一種導電膜，其係藉由如請求項1至14中任一項之膜形成方法所形成。 A conductive film formed by the film forming method according to any one of claims 1 to 14. 一種絕緣膜，其係藉由如請求項1至14中任一項之膜形成方法所形成。 An insulating film formed by the film forming method according to any one of claims 1 to 14.
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