1289414 玖、發明說明： - (~ )發明所屬之技術領域 ^ 本發明係有關一種具有所欲圖案之機能性薄膜的形成 ^ 方法、藉由該方法所得的具有機能性薄膜圖案之基材、以 及以具有該薄膜圖案之基材所成的電極。 (一）先前技術 在基板上形成圖案化的機能性薄膜（例如導電性薄膜） 且進行電子電路調製等，調製成在很多領域中具有機能性 薄膜圖案之基材。 φ 調製具有所定機能性薄膜圖案之基材時，爲形成機能 性薄膜之材料不具感放射線性（例如感光性）時，典型例使 用下述藉由鈾刻的方法以進行圖案化；在基板上形成機能 型薄膜之步驟；在該薄膜上藉由感放射線性樹脂組成物形 成與目的圖案相同圖案的步驟；使沒有形成該圖案部分之 機能性薄膜藉由蝕刻去除的步驟；以及去除該圖案的步驟 。然而，該方法不適於不易蝕刻的薄膜，會有步驟數繁多 的缺點。 ⑩ 不需鈾刻步驟之習知簡易圖案化方法例如日本特開昭 61- 24 5 5 3 3號公報記載。該方法包含使基板上目的機能性圖 案之相反圖案藉由感放射線性樹脂組成物形成的步驟；於 其上由金屬或金屬氧化物等所成機能性薄膜藉由蒸鍍形成 的步驟；以及由感放射線性樹脂組成物所形成圖案藉由可 溶解的剝離液處理以去除該圖案與圖案上之機能性薄膜， 使目的機能性薄膜之圖案殘留的步驟（參照該公報之第2圖） -7- 1289414 。於該方法中在以感放射線性樹脂組成物形成的圖案側面 上存在沒有形成機能性薄膜的部分，在該部分上與上述剝 ' 離液接觸以去除該圖案及該圖案上之薄膜。爲避免蒸鍍時 · 自側方附著薄膜成分時，於該公報中提案調製第1圖所示 特定截面形狀之圖案。以相同目的使該圖案之垂直方向截 面形狀形成倒錐形的方法係爲已知。 此等方法適用於在所形成的圖案側面上具有沒有附著 機能性薄膜時，僅利用主要使金屬、金屬氧化等之機能性 成分藉由蒸鍍形成。 Φ 於特表2 0 0 2 - 5 0 0 4 0 8號公報中記載使用含有導電性聚 合物之機能性成分的溶液或分散液之具有特定黏度的印刷 漿料，藉由篩網印刷法直接描繪圖案，去除漿料中之溶劑 或分散媒以形成目的機能性薄膜之圖案。然而，其解像度 不充分，使印刷漿料調整爲特定黏度之手續麻煩。 另外，於特開平1 0 - 1 5 3 967號公報中揭示藉由噴墨印 表機裝置使作爲機能性材料之發光材料圖案化的方法。該 方法係爲使液狀發光材料藉由印表機裝置供應給基板上， 鲁 且藉由加熱處理高分子化。然而，將液狀發光材料供應基 板時，必須預先形成防垂壁，以及調整液狀發光材料之黏 度及表面張力的手續麻煩。 (三）發明內容 本發明爲解決上述習知課題時，其目的係提供一種簡 單形成精度高的機能性薄膜圖案之方法。特別是提供一種 即使形成機能性薄膜的材料不具感放射線時、機能性薄膜 一 8- 1289414 之蝕刻不易時、或藉由蒸鍍形成該薄膜不易時，仍容易形 成圖案的方法。本發明之另一目的係提供一種藉由上述方 · 法所得具有具所定機能之機能性薄膜圖案的基材。本發明 - 之另一目的係提供一種藉由上述方法所得導電性與透明性 優異的透明電極。 本發明人等爲解決上述課題時再三深入硏究的結果， 開發使用含機能性成分之液狀組成物形成具有所欲圖案之 機能性薄膜的方法，遂而完成本發明。 本發明具有所欲圖案之機能性薄膜的方法，包含 鲁 (1)在基板上藉由感放射線性樹脂組成物形成與目的機能性 薄膜圖案相反圖案之步驟、 (2 )在該具有相反圖案之基板表面上使含機能性成分之液狀 組成物塗覆•乾燥，形成該圖案與被覆基板表面全體的 機能性薄膜之步驟、 (3 )藉由使形成該機能性薄膜之基板以剝離劑處理，使該相 反圖案與該圖案上之機能性薄膜同時去除，製得目的機 $ 能性薄膜之圖案步驟。 較佳的實施形態係上述機能性成分爲導電性聚合物。 較佳的實施形態係上述導電性聚合物具有以下述式（1 ) 所示重覆構造之聚（3, 4 -二烷氧基噻吩）與聚陰離子之複合 物，該複合物分散於水系溶劑中。 1289414 【化2】1289414 玖, invention description: - (~) Technical field to which the invention pertains. The present invention relates to a method for forming a functional film having a desired pattern, a substrate having a functional film pattern obtained by the method, and An electrode formed of a substrate having the film pattern. (1) Prior Art A patterned functional film (e.g., a conductive film) is formed on a substrate, and electronic circuit modulation or the like is performed to prepare a substrate having a functional film pattern in many fields. When φ is used to modulate a substrate having a predetermined functional film pattern, when the material for forming the functional film is not radiation-sensitive (for example, photosensitive), a typical example is used for patterning by uranium engraving; on the substrate; a step of forming a functional film; forming a pattern of the same pattern as the target pattern by the radiation-sensitive resin composition on the film; a step of removing the functional film without forming the pattern portion by etching; and removing the pattern step. However, this method is not suitable for a film which is not easily etched, and has a disadvantage of a large number of steps. 10 A conventional simple patterning method that does not require an uranium engraving step is described in, for example, Japanese Laid-Open Patent Publication No. 61-24 5 5 3 . The method comprises the steps of: forming a reverse pattern of a desired functional pattern on a substrate by a radiation-sensitive resin composition; forming a functional film formed of a metal or a metal oxide or the like by evaporation; The step of treating the pattern formed by the radiation-sensitive resin composition by removing the functional film on the pattern and the pattern by the soluble stripping solution, and leaving the pattern of the target functional film (refer to FIG. 2 of the publication) - 1289414. In this method, on the side of the pattern formed by the radiation-sensitive resin composition, there is a portion where no functional film is formed, and the portion is contacted with the above-mentioned peeling liquid to remove the pattern and the film on the pattern. In order to avoid vapor deposition, when the film component is adhered to the side, it is proposed in this publication to modulate the pattern of the specific cross-sectional shape shown in Fig. 1. A method of forming a cross-sectional shape in the vertical direction of the pattern for the same purpose is known. These methods are suitable for forming a functional film having no adhesion property on the side surface of the formed pattern, and forming only the functional component mainly oxidizing metal or metal by vapor deposition. Φ 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于 于The pattern is drawn to remove the solvent or dispersion medium in the slurry to form a pattern of the desired functional film. However, the resolution is insufficient, and the procedure for adjusting the printing paste to a specific viscosity is troublesome. Further, a method of patterning a light-emitting material as a functional material by an ink jet printer device is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. This method is such that the liquid luminescent material is supplied onto the substrate by the printer device, and is polymerized by heat treatment. However, when the liquid luminescent material is supplied to the substrate, it is necessary to form an anti-drop wall in advance, and it is troublesome to adjust the viscosity and surface tension of the liquid luminescent material. (III) SUMMARY OF THE INVENTION The present invention has been made in an effort to solve the above problems, and an object thereof is to provide a method for simply forming a functional thin film pattern having high precision. In particular, it is a method of easily forming a pattern even when the material forming the functional film is not radiation-sensitive, when the etching of the functional film 8- 889414 is not easy, or when the film is formed by vapor deposition. Another object of the present invention is to provide a substrate having a functional film pattern having a predetermined function obtained by the above method. Another object of the present invention is to provide a transparent electrode which is excellent in conductivity and transparency by the above method. In order to solve the above problems, the inventors of the present invention have further intensively studied and developed a method of forming a functional film having a desired pattern by using a liquid composition containing a functional component, and completed the present invention. The method of the present invention has a functional film of a desired pattern, comprising the steps of: (1) forming a reverse pattern with a target functional film pattern by a radiation sensitive resin composition on a substrate, and (2) having an opposite pattern a step of coating and drying a liquid composition containing a functional component on the surface of the substrate to form a functional film of the pattern and the entire surface of the coated substrate, and (3) treating the substrate forming the functional film with a release agent And the opposite pattern is simultaneously removed from the functional film on the pattern to obtain a pattern step of the objective film. In a preferred embodiment, the functional component is a conductive polymer. In a preferred embodiment, the conductive polymer has a complex of poly(3,4-disalkoxythiophene) and a polyanion having a repetitive structure represented by the following formula (1), and the complex is dispersed in an aqueous solvent. in. 1289414 【化2】
(其中，R1及R2互相獨立地爲氫或碳數1〜4之院基，或— 起形成碳數1〜4之伸院基，且該伸院基可以經任意取代> 較佳的實施形態係上述機能性薄膜爲透明導電膜。 本發明包含藉由上述方法形成的具有機能性薄膜圖案 φ 之基材。 本發明包含以上述所形成的具有機能性薄膜圖案之透 明電極。 1 (四）實施方式 於下述中詳細說明本發明之內容。 本說明書之「放射線」係爲可視光線、紫外線、遠紫 外線、X光線、電子線、分子線、r線、同步加速器放射線 、質子束等之總稱。 β 於本發明機能性薄膜之形成方法中，首先在基板上藉 由感放射線性樹脂組成物形成與目的機能性薄膜圖案之相 反圖案。 爲形成上述圖案時基板例如矽晶圓、玻璃板等以無機 材料所成的基板；以及聚酯、聚醯亞胺、聚碾、聚碳酸醋 、聚氯乙烯基、聚乙烯、聚丙烯、此等之混合物、含有構 成此等聚合物之單體單位的共聚物、苯酚樹脂、環氧樹脂 一 1 0 - 1289414 、ABS樹脂等所成的基板（塑膠薄膜、塑膠片等）。 上述感放射線性樹脂組成物可使用正型感放射線性樹 脂組成物及負型感放射線性樹脂組成物中任何一種。正型 感放射線性樹脂組成物，典型例如苯酚酚醛淸漆樹脂與萘 醌二疊氮之混合物（例如苯酚酚醛淸漆樹脂約80%與萘醌二 疊氮約20%之混合物）。負型感放射線性樹脂組成物爲環化 橡膠與芳香族雙疊氮之混合物、以及苯酚樹脂與芳香族疊 氮之混合物等。 於上述基板上形成相反圖案時，例如首先如第1 ( a )圖 所示、在基板1上塗覆含溶劑或分散媒之上述感放射線性 樹脂組成物後，使其加熱•乾燥，形成感放射線性樹脂組 成物2。塗覆方法例如旋轉塗覆、輥塗覆、浸漬塗覆、隙縫 塗覆、刮刀塗覆、噴霧塗覆等之方法。 如此形成的感放射線性樹脂組成物2之膜厚，沒有特 別的限制，以0 . 5〜5 0 μ m較佳、更佳者爲1〜1 〇 μ m。膜厚 過薄時機能性薄膜之圖案解像度降低，反之，即使膜厚較 必要以上爲厚時解像度不會提高。 其次，使所得感放射線性樹脂組成物2藉由下述圖案 化，形成與目的機能性薄膜圖案相反的圖案。使用正型感 放射線性樹脂組成物作爲感放射線性樹脂組成物時，首先 如第1 ( b )圖所示在基板上之感放射線性樹脂組成物層2表 面上載負具有目的機能性薄膜圖案之相反圖案（與所形成感 放射線性樹脂組成物薄膜之圖案相同的圖案）的遮光層之光 罩3，通過它照射放射線。經照射的部分21對所定溶劑具 - 1 1 - 1289414 有可溶性（第1 ( c )圖）。然後，藉由該溶劑使照射部分溶解 、去除，製得與目的機能性薄膜圖案相反之圖案20 (第1 ( d ) 圖）。 另外，爲負型感放射線性樹脂組成物時，首先與正型 時相同地，在基板1上準備具有感放射線性樹脂組成物層2 之積層體（第2(a)圖）。在該樹脂組成物層表面上載負具有 與目的機能性薄膜圖案相反之圖案（與所形成感放射線性樹 脂組成物薄膜之圖案相同的圖案）的遮光層之光罩4，通過 它照射放射線。經照射的部分21對所定溶劑具有可溶性（ 第2 ( b )圖）。然後，照射前感放射線性樹脂組成物薄膜之圖 案雖可溶解於所定溶劑，惟經照射的部分22硬化、不溶於 該溶劑中’故遮光部分2 3可藉由該溶劑溶解、去除，製得 與目的機能性薄膜圖案相反之圖案2〇 (第2 ( d )圖）。 才幾能性薄膜所含的機能性成分物爲具有目的機能之成 分’可溶解或分散於下述所定溶劑或分散媒者即可，沒有 特別的限制。例如目的機能爲導電性時爲導電性聚合物、 I S '金屬氧化物等導電材料，目的機能爲絕緣性時爲絕 緣彳生樹脂等之絕緣材料，目的機能爲有色時爲染料、顏料 '發光體等。特別是適於形成製得含有下述聚（3，4 _二烷氧 基IS吩）與聚陰離子之複合物的導電性聚合物作爲機能性成 分之薄膜。 於上述液狀組成物中除加入機能性成分外，通常含有 浴齊u ^分散媒。該溶劑或分散媒可溶解或分散機能性成分 且不會使上述基板及上述感放射線性樹脂組成物或該組 -12- 1289414 成物由來的硬化物腐蝕之液體即可，沒有特別的限μ。『見 使用的機能性成分而定，採用適當的溶劑或分散媒。例如 可使用水系溶劑，特別是水。除水外之水系溶劑例如甲醇 、乙醇、2 -丙醇、1 -丙醇等之醇；丙酮、乙烯腈等水溶性 溶劑與水之混合物。 本發明方法所使用的液狀組成物，另視其所需可含有 黏合劑、交聯劑、均平劑等。 上述黏合劑以機能性成分本身缺乏成膜性者爲宜。可 含有的黏合劑例如具有選自於聚酯、聚（甲基）丙烯酸酯、 聚胺甲酸酯、聚醋酸乙烯酯、聚氯化次乙烯基、聚醯胺、 聚醯亞fl女、乙烯系或丙嫌酸系共聚物（苯乙烯、氯化次乙燒 基、氯化乙烯基、及烷基（甲基）丙烯酸酯之共聚合成分單 位的共聚物）等之樹脂；以及3 -環氧丙基丙基三甲氧基矽烷 、3 -環氧丙基丙基甲基二甲氧基矽烷、2-(3,4 -環氧基環己 基）乙基三甲氧基矽烷等之烷氧基矽烷化合物。 交聯劑係以提高機能性薄膜之強度爲目的所使用。交 聯劑爲蜜胺系、聚羰基二醯亞胺系、聚噁唑啉系、聚環氧 系、及聚異氰酸酯系交聯劑。 均平劑可使用界面活性劑等，或以提高均平性及提高 乾燥性爲目的時使用醇等。 上述液狀組成物可以旋轉塗覆法、輥塗覆法、浸漬塗 覆法、隙縫塗覆法、刮刀塗覆法、噴霧塗覆法等方法塗覆 於具有相反圖案2 0之基板上，藉由加熱•乾燥，形成機能 丨生溥S旲5 (爹如、弟3 ( a )及（b )圖）。爲塗覆液狀組成物時’機 1289414 能性薄膜賦予基板1表面及相反圖案20之薄膜表面全體（ 含側面）。 機能性薄膜之膜厚沒有特別的限制’以〇 · 〇 1〜〇 · 8μπι ^ 較佳、更佳者爲0 . 0 4〜0 . 3 μ ιτι。膜厚過薄時薄膜無法具有 充分機能，反之，薄膜過厚時圖案之解像度降低。 其次，在上述基板上所形成的相反圖案20與該圖案上 之機能性薄膜5同時去除。此係例如使上述第3 ( b )圖所示 形成機能性薄膜之基板，藉由在使感放射線性樹脂組成物 或可溶化的感放射線性樹脂組成物所成薄膜溶解於所得剝 @ 離劑中浸漬處理予以達成。 上述剝離劑係視感放射線性樹脂組成物之種類而不同 ，例如爲正型感放射性樹脂之甲酚酚醛淸漆樹脂與萘醌二 疊氮的混合物時，含有胺等鹼作爲剝離劑之水溶液；爲負 型放射性樹脂之環化橡膠與芳香族雙疊氮之混合物時，例 用院基苯磺酸等作爲剝離劑；爲苯酣樹脂與芳香族二疊氮 之混合物時，利用含胺等鹼的水溶液等作爲剝離劑。剝離 劑係使機能性薄膜5之空孔部分通過，或在該機能性薄膜5 # 所含的黏合劑溶解、侵入，與該圖案2 0接觸且使其溶解。 藉此可得目的機能性薄膜之圖案5 0。 藉由本發明之方法，可在基板上形成含有上述所欲的 機此丨'生成分之機#性薄g吴圖案。該方法可製得各種型式的 機#性薄膜。特別是調製電子電路、透明電極等時，可形 成以導電性聚合物作爲機能性成分之薄膜。其中，利用於 使用上述聚（3，4 -二烷氧基噻吩）與聚陰離子之複合物作爲 -14- 1289414 導電性聚合物之機能性薄膜。 於下述中說明有關上述導電性成分之（3 , 4 -二烷氧基噻 吩）與聚陰離子之複合物。 該（3，4 -二烷氧基噻吩）與聚陰離子之複合物係爲具有 下述式（1 )所示重複構造之聚（3，4 -二烷基噻吩）與聚陰離子 之複合物。 【化3】(wherein R1 and R2 are each independently hydrogen or a carbon number of 1 to 4, or a base of carbon number 1 to 4, and the extension base may be optionally substituted> The functional film is a transparent conductive film. The present invention comprises a substrate having a functional thin film pattern φ formed by the above method. The present invention comprises a transparent electrode having a functional thin film pattern formed as described above. Embodiments The present invention will be described in detail below. The "radiation" of the present specification is visible light, ultraviolet light, far ultraviolet light, X-ray, electron beam, molecular line, r-line, synchrotron radiation, proton beam, etc. In the method for forming the functional film of the present invention, first, a reverse pattern of the target functional film pattern is formed on the substrate by the radiation-sensitive resin composition. In order to form the pattern, the substrate is, for example, a germanium wafer or a glass plate. a substrate made of an inorganic material; and a mixture of polyester, polyimine, poly-milling, polycarbonate, polyvinyl chloride, polyethylene, polypropylene, and the like, a substrate (plastic film, plastic sheet, etc.) formed of a copolymer of a monomer unit constituting the polymer, a phenol resin, an epoxy resin, a 10 0 1289414, an ABS resin, etc. The radiation sensitive resin composition may be used. A positive-type radiation-sensitive resin composition and a negative-type radiation-sensitive resin composition are used. A positive-type radiation-sensitive resin composition, typically, for example, a mixture of a phenol novolac resin and a naphthoquinone diazide (for example, a phenol novolac) a mixture of about 80% of enamel resin and about 20% of naphthoquinone diazide). The negative radiation sensitive resin composition is a mixture of a cyclized rubber and an aromatic diazide, and a mixture of a phenol resin and an aromatic azide. When the opposite pattern is formed on the substrate, for example, first, as shown in the first (a) diagram, the radiation sensitive resin composition containing a solvent or a dispersion medium is applied onto the substrate 1, and then heated and dried to form a film. Radiation-sensitive resin composition 2. A coating method such as a method of spin coating, roll coating, dip coating, slit coating, blade coating, spray coating, or the like. The film thickness of the radiation sensitive resin composition 2 is not particularly limited, and is preferably 0.5 to 500 μm, more preferably 1 to 1 μm. When the film thickness is too thin, the film is functional. The resolution of the pattern is lowered, and the resolution is not improved even when the film thickness is thicker than necessary. Next, the obtained radiation sensitive resin composition 2 is patterned by the following pattern to form a pattern opposite to the intended functional film pattern. When the positive-type radiation-sensitive resin composition is a radiation-sensitive resin composition, first, as shown in Fig. 1 (b), the opposite surface of the radiation-sensitive resin composition layer 2 on the substrate is loaded with a target functional film pattern. a mask 3 of a light-shielding layer of a pattern (the same pattern as the pattern of the film of the radiation-sensitive resin composition formed), through which radiation is irradiated. The irradiated portion 21 is soluble for the predetermined solvent - 1 1 - 1289414 (1st) (c) Figure). Then, the irradiated portion is dissolved and removed by the solvent to obtain a pattern 20 opposite to the intended functional film pattern (Fig. 1 (d)). Further, in the case of a negative-type radiation-sensitive resin composition, first, a laminate having the radiation-sensitive resin composition layer 2 is prepared on the substrate 1 in the same manner as in the case of the positive type (Fig. 2(a)). A mask 4 having a light-shielding layer having a pattern opposite to the intended functional film pattern (the same pattern as the pattern of the radiation-sensitive resin composition film formed) is carried on the surface of the resin composition layer, and the radiation is irradiated thereon. The irradiated portion 21 is soluble in a predetermined solvent (Fig. 2(b)). Then, the pattern of the radiation-sensitive linear resin composition film is dissolved in the predetermined solvent, but the irradiated portion 22 is hardened and insoluble in the solvent. Therefore, the light-shielding portion 23 can be dissolved and removed by the solvent. The pattern 2〇 opposite to the objective functional film pattern (Fig. 2(d)). The functional component contained in the functional film is not particularly limited as long as it is a component having a desired function and can be dissolved or dispersed in a solvent or a dispersion medium as described below. For example, when the target function is conductive, it is a conductive polymer such as a conductive polymer or IS 'metal oxide, and the target function is an insulating material such as an insulating resin when it is insulating. The objective function is a dye, a pigment 'illuminant when it is colored. Wait. In particular, it is suitable to form a film in which a conductive polymer containing a complex of the following poly(3,4-dialkyloxy IS phenoxide) and a polyanion is prepared as a functional component. In addition to the functional component, the liquid composition usually contains a bathing agent. The solvent or the dispersing medium can dissolve or disperse the functional component without causing the substrate and the radiation sensitive resin composition or the cured product of the group of 12-1249814 to be corroded, and there is no particular limitation. . 『Depending on the functional ingredients used, use a suitable solvent or dispersion medium. For example, an aqueous solvent, especially water, can be used. An aqueous solvent other than water, for example, an alcohol such as methanol, ethanol, 2-propanol or 1-propanol; a mixture of a water-soluble solvent such as acetone or vinyl nitrile and water. The liquid composition used in the method of the present invention may further contain a binder, a crosslinking agent, a leveling agent and the like as needed. The above binder is preferably one in which the functional component itself lacks film forming properties. The binder which may be contained, for example, has a pigment selected from the group consisting of polyester, poly(meth)acrylate, polyurethane, polyvinyl acetate, polychlorinated vinylidene, polydecylamine, polyfluorene, and ethylene. a resin such as a copolymer of a copolymer of acrylic acid (styrene, a chlorinated vinyl group, a vinyl chloride group, and a copolymerization unit of an alkyl (meth) acrylate); and a 3-ring Alkoxy groups such as oxypropylpropyltrimethoxydecane, 3-glycidylpropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane Decane compound. The crosslinking agent is used for the purpose of improving the strength of the functional film. The crosslinking agent is a melamine-based, polycarbonyldiamine-based, polyoxazoline-based, polyepoxy-based or polyisocyanate-based crosslinking agent. The leveling agent may be a surfactant or the like, or an alcohol or the like may be used for the purpose of improving the leveling property and improving the drying property. The liquid composition may be applied to a substrate having an opposite pattern 20 by a spin coating method, a roll coating method, a dip coating method, a slit coating method, a knife coating method, a spray coating method, or the like. It is heated and dried to form a function 丨S旲5 (爹如,弟3 (a) and (b)). In order to apply the liquid composition, the machine 1289414 energy film is provided to the entire surface of the substrate 1 and the film surface of the opposite pattern 20 (including the side surface). The film thickness of the functional film is not particularly limited. 〇 〇 1 〇 8 8 μπι ^ is preferably, more preferably 0. 0 4 to 0 . 3 μ ιτι. When the film thickness is too thin, the film cannot have sufficient function, and conversely, when the film is too thick, the resolution of the pattern is lowered. Next, the opposite pattern 20 formed on the above substrate is simultaneously removed from the functional film 5 on the pattern. For example, the substrate on which the functional film is formed as shown in the above FIG. 3(b) is obtained by dissolving a film formed by a radiation sensitive resin composition or a solubilized radiation sensitive resin composition on the obtained peeling agent. The middle immersion treatment is achieved. The release agent is different depending on the type of the radiation-sensitive linear resin composition, and is, for example, a mixture of a cresol novolac lacquer resin of a positive-type radiation-sensitive resin and naphthoquinone diazide, and an aqueous solution containing a base such as an amine as a release agent; When it is a mixture of a cyclized rubber of a negative-type radioactive resin and an aromatic diazide, a hospital-based benzenesulfonic acid or the like is used as a release agent; when it is a mixture of a benzoquinone resin and an aromatic diazide, an alkali such as an amine is used. An aqueous solution or the like is used as a release agent. The release agent passes through the pore portion of the functional film 5, or dissolves and invades the binder contained in the functional film 5#, and comes into contact with the pattern 20 to dissolve it. Thereby, the pattern 50 of the objective functional film can be obtained. According to the method of the present invention, it is possible to form a pattern containing the above-mentioned desired machine on the substrate. This method can produce various types of machine-like films. In particular, when an electronic circuit, a transparent electrode, or the like is modulated, a film having a conductive polymer as a functional component can be formed. Among them, a composite of the above poly(3,4-disalkoxythiophene) and a polyanion is used as a functional film of a conductive polymer of -14-1289414. A complex of (3,4-disalkoxythiophene) and a polyanion relating to the above conductive component will be described below. The complex of the (3,4-disalkoxythiophene) and the polyanion is a complex of poly(3,4-dialkylthiophene) having a repeating structure represented by the following formula (1) and a polyanion. [化3]
於上述聚（3, 4-二烷氧基噻吩）中，Ri及R2之碳數1〜4 之烷基例如甲基、乙基、正丙基等。Ri及R2 一起形成的碳 數1〜4之伸烷基例如丨，2 -伸烷基、1 , 3 -伸烷基等，較佳者 爲伸甲基、1，2 -伸乙基、1，3 -伸丙基等。其中，以1，2 -伸乙 基更佳。而且，碳數1〜4〜之伸烷基可經取代，取代基例 如碳數1〜1 2之烷基、苯基等。取代的碳數1〜4之伸烷基 Φ 例如1，2 -環伸己基、2，3 -伸丁基等。該伸烷基之典型例如 由R1及R2 —起形成的以碳數1〜1 2烷基取代之1，2 _伸院 基係自使乙條基、丙烯基、己烯基、辛嫌基、癸條基、十 一烯基、苯乙烯等之α -烯烴類溴化所得的1，2 _二溴鏈院類 衍生。 、聚乙 產生上述聚陰離子所得的化合物例如聚丙烯酸、聚甲 基丙烯酸、聚馬來酸等之聚羧酸類；聚苯乙烯磺酸 -15- 1289414 烯基磺酸等之聚磺酸類等。此等之中以聚苯乙烯磺酸更佳 · 。此等可與乙細基駿酸類或乙烯基擴酸類與其他可聚合的 二 單體類（例如丙烯酸酯類、苯乙烯等）之共聚物。該聚陰離 · 子之數里平均分子重以1，〇〇〇〜2，〇〇〇,〇〇〇較佳、更佳者爲 2,000〜500,〇〇〇、最佳者爲1〇,〇〇〇〜2〇〇,〇〇〇。 使用上述複合物作爲機能性成分時，分散媒爲水系分 散媒。上述聚（3，4 -二烷氧基噻吩）與聚陰離子之複合物的 製法例如專利第2 6 3 6 9 6 8號公報記載。該聚（3 , 4 _二院氧基 噻吩）係聚陰離子爲漿料狀時，本說明書中記載爲「聚（3，4 _ · 一丨兀氧基曝吩）與聚陰離子之複合物」、或簡稱爲「複合物 j ° 如此在基板上形成含有上述所欲機能性成分之機能性 薄膜圖案。特別是使用上述聚（3，4 _二烷氧基噻吩）與聚陰 離子之複合物作爲導電性聚合物時，可得具有透明性與導 電性優異的導電性薄膜圖案之基材。基板選擇透明材料所 成的基板時，可得透明性優異的電極，此係作爲液晶顯示 器之映像電極等、透明電極極爲有用。具有本發明所得的 g 機能性薄膜圖案之基材視其目的而定可利用於各種領域。 【實施例】 於下述中以實施例基準具體地說明本發明，惟本發曰月 不受此等實施例所限制。本實施例及比較例所使用的材料 及各種評估方法如下述說明。於下述實施例中「份」係赛 示「重量份」。 1 .使用材料 1289414 (1 · 1 )基板 使用玻璃板（直徑4吋（1 Ο . 1 6 c m )、厚度Ο · 7 m m圓盤狀 ;全光線透過率：91 . 4%)。 (1 . 2 )正型感放射線性樹脂組成物 使2 9 · 6重量份甲酚酚醛淸漆樹脂（間位及對位之混合 物）、與7 · 4重量份2，3，4，4 ’ -四羥基二甲苯酮-1，2 -萘焜二 疊氮基-5 -磺酸酯、與Ο · 1重量份氟系界面活性劑、6 3 . 0重 量份丙二醇單甲醚乙酸酯混合，使用所得的混合物。 (1 · 3 )顯像液 以2 . 3 8重量％四甲銨氫氧化物水溶液作爲顯像液。 (1 . 4 )含機能性成分之水分散體 在1，887份含有20.8份重量平均分子量75000之聚苯 乙烯磺酸之水溶液中加入4 9份1重量％硫酸鐵（I I I )水溶液 、8 · 8份3，4-伸乙基二氧化噻吩 '及1 1 7份1 0 · 9重量％過 氧化二硫酸水溶液，使所得混合物在1 8 °C下攪拌2 3小時， 製得聚（3, 4 -伸乙基二氧化噻吩）與聚苯乙烯磺酸之複合物 的水分散體。於其中加入1 5 4份陽離子交換樹脂及2 3 2份 陰離子交換樹脂予以攪拌2小時後，過濾分別離子交換樹 脂、予以脫鹽，製得含有1 · 4重量％聚（3 , 4 -伸乙基二氧化 噻吩）與聚苯乙烯磺酸之複合物的水分散體。 (1 . 5 )含機能性成分之液狀組成物 使70 · 0份以（1 · 4 )項所得的機能性成分之水分散體、 1 · 4份之25重量％聚酯樹脂水分散體（那卡西肯姆迪克斯（譯 首）股份有限公司製卡布西（譯音）ES-210)、與〇.7份之1〇 1289414 重量％氟系界面活性劑（互應化學工業股份有限公司製布拉 斯克頓（譯音）R γ - 2 )、與3 . 0份N -甲基甲醯胺、與0 . 7份之 10重量％銨水溶液、23 . 5份脫鹽水、〇 . 7份之40重量％甲基 化蜜胺樹脂水溶液混合，所得的混合物爲含機能性成分之 液狀組成物。 (1 · 6 )剝離劑 使用那卡西肯姆迪克斯（譯音）股份有限公司製剝離劑 N - 3 2 1 (胺水溶液）。 2 .評估方法 (2 · 1 )藉由正型感放射線性樹脂組成物所形成圖案之膜厚 使用 NANOMETERRICS 製 NanoSpec/AFT 領 ϋ 定 ° (2 . 2 )機能性薄膜之膜厚 使用 Sloan Technology 製 DEKTAK3 測定。 (2 . 3 )機能性薄膜圖案之解像度 使用描繪以50〜0 . 88μπι之36階段線寬平行的數線之光 罩，形成圖案化的機能性薄膜。藉由光學顯微鏡觀察進行 觀察，觀察通過光罩之圖案以何種線寬所得，作爲解像度 〇 (2 . 4 )機能性薄膜之表面電阻率、體積電阻率及全光線透過率 在基板上使機能性薄膜形成用液狀組成物使用旋轉塗覆 器、以700 rpm、8秒鐘之條件塗覆，在熱板上、115°C下加 熱•乾燥5分鐘。使其浸漬於剝離劑中1分鐘、洗淨、風 乾，製得全面形成機能性薄膜之基板。如下述評估表面電 阻率、體積電阻率、及全光線透過率。 -1 8 - 1289414 (2.4.1) 表面電阻率及體積電阻率以；[13 1$7194爲基準 ’使用三菱化學（股）製羅雷史塔（譯音）GP(MCP-T600 )測定 〇 (2.4.2) 全光線透過率以；ns K7150爲基準，使用史卡 5式驗機（股）製海陸（譯首）電腦H G Μ - 2 B測定。 (實施例1 ) 在基板上使上述正型感放射線性樹脂組成物使用旋轉塗 覆器、以25〇rpm、30秒鐘之條件塗覆，在熱板上、90°C下 加熱•乾燥2分鐘，形成5μπι膜厚之正型感放射線性樹脂 組成物層。 在該形成有正型感放射線性樹脂組成物層之基板上載負 光罩，使用肯農（譯音）股份有限公司製曝光機PLA-5 G1 AF， 以150m】/cm2之曝光量接觸曝光。然後，使其在23°C之顯 像液中浸漬1分鐘，使曝光部分溶解•去除，藉由水洗形 成正型感放射線性樹脂組成物之所定圖案。 然後，在該具有以正型感放射線性樹脂組成物形成的圖 案之基板表面上，使機能性薄膜形成用液狀組成物使用旋 轉塗覆器、以 7 0 0 1· p m、8秒鐘之條件塗覆，在熱板上、 1 1 5 °C下加熱•乾燥5分鐘，形成〇 . 1 3 μηι膜厚之機能性薄膜 〇 最後，使上述具有機能性薄膜之基板在2 3 °C之剝離劑中 浸漬1分鐘’使該圖案之感放射線性樹脂組成物彳谷解’使 其水洗。藉此可去除不需部分之機能性薄膜與上述圖案’ 製得機能性薄膜之圖案。 _1 9- 1289414 該機能性薄膜圖案之解像度爲3 μπι (具有直至3 μιτι線寬 之解像度）。機能性薄膜之表面電阻率爲3 . Οχ 1 03 Ω / □、 、 體積電阻率爲4 · 4χ 1 0 - 2 Ω · cm。含基板之機能性薄膜的全 · 光線透過率爲8 7 . 1 %。 該所得的具有機能性薄膜圖案之基材可使用作爲液晶顯 示器之映像電極’具有可使用的解像度、導電性、及透明 性。 【發明之效果】 藉此該具有所欲機能之機能性薄膜圖案，可容易且以 0 高解像度形成。以往，爲形成機能性薄膜時材料本身不具 感放射線性時，不易形成解像度佳且機能性薄膜圖案。藉 由本發明形成解像度高的機能性薄膜圖案。一般而言，爲 形成機能性薄膜時之材料爲水系塗覆液時，由於不易設計 成具有感放射線性，故本發明之方法特別有效。藉由本發 明不需使用濺射裝置等、可容易形成機能性薄膜，例如使 用由透明材料所成的基板，可容易形成機能性薄膜。本發 明所得的具有機能性薄膜之圖案可視其目的而定利用於各 ϋ 種領域中。 (五）圖式簡單說明 第1 ( a )〜（d )圖係爲使用正型感放射線性組成物，在 基板上形成與所欲機能性薄膜圖案相反的圖案之步驟簡略 圖。 第2 ( a )〜（d )圖係爲使用負型感放射線性組成物，在 基板上形成與所欲機能性薄膜圖案相反的圖案之步驟簡略 -20 - 1289414 該機能性薄膜圖案之解像度爲3 Km (具有直至3 _線寬 之解像度）。機能性薄膜之表面電阻率爲3 · Ο X 1 0 3 Ω /匚]、 體積電阻率爲4 . 4 X 1 〇 - 2 Ω · c m。含基板之機能性薄膜的全 光線透過率爲8 7 . 1 %。 該所得的具有機能性薄膜圖案之基材可使用作爲液晶顯 示器之映像電極，具有可使用的解像度、導電性、及透明 性。 【發明之效果】 藉此該具有所欲機能之機能性薄膜圖案，可容易且以 高解像度形成。以往，爲形成機能性薄膜時材料本身不具 感放射線性時，不易形成解像度佳且機能性薄膜圖案。藉 由本發明形成解像度高的機能性薄膜圖案。一般而言，爲 形成機能性薄膜時之材料爲水系塗覆液時，由於不易設計 成具有感放射線性，故本發明之方法特別有效。藉由本發 明不需使用濺射裝置等、可容易形成機能性薄膜，例如使 用由透明材料所成的基板，可容易形成機能性薄膜。本發 明所得的具有機能性薄膜之圖案可視其目的而定利用於各 種領域中。 (五）圖式簡單說明 第1 ( a )〜（d )圖係爲使用正型感放射線性組成物，在 基板上形成與所欲機能性薄膜圖案相反的圖案之步驟簡略 圖。 第2 ( a )〜（d )圖係爲使用負型感放射線性組成物，在 基板形成與所欲機能性薄膜圖案相反的圖案之步驟簡略 -2 0 - 1289414 圖。 第 3(a)〜（c)圖係爲藉由本發明之方法、在基板上形 成機能性薄膜圖案之步驟簡略圖。 【符號說明】 1 :基板 2 :感放射線性樹脂組成物層 5 :機能性薄膜 20 :相反圖案 50 :機能性薄膜之圖案 -21In the above poly(3,4-dialkoxythiophene), an alkyl group having 1 to 4 carbon atoms of Ri and R2 is, for example, a methyl group, an ethyl group, a n-propyl group or the like. The alkyl group having a carbon number of 1 to 4 formed by Ri and R2 together is, for example, an anthracene, a 2-alkylene group, a 1,3-alkylene group, etc., preferably a methyl group, a 1,2-ethyl group, and 1 , 3 - stretch propyl and so on. Among them, the 1,2-extension ethyl group is more preferable. Further, the alkylene group having 1 to 4 carbon atoms may be substituted, and the substituent may be, for example, an alkyl group having 1 to 12 carbon atoms, a phenyl group or the like. The substituted alkylene group Φ having a carbon number of 1 to 4 is, for example, 1,2-cyclohexylene, 2,3-butylene or the like. Typical examples of the alkylene group are, for example, R1 and R2, which are substituted by a carbon number of 1 to 12 alkyl groups, and the alkyl group, the propylene group, the hexenyl group, and the octyl group. 1,2 - dibromo chain derived from the bromination of α-olefins such as sulfonium, undecenyl and styrene. Polyethylene A compound obtained by producing the above polyanion, for example, a polycarboxylic acid such as polyacrylic acid, polymethacrylic acid or polymaleic acid; a polysulfonic acid such as polystyrenesulfonic acid -15-1248914 alkenylsulfonic acid or the like. Among these, polystyrene sulfonic acid is preferred. These may be copolymers with an ethylenic acid or a vinyl acid extended with other polymerizable dimonomers (e.g., acrylates, styrene, etc.). The average molecular weight in the number of the cations and the sub-numbers is 1, 〇〇〇~2, 〇〇〇, 〇〇〇 is better, and the better is 2,000~500, 〇〇〇, the best is 1〇, 〇〇〇~2〇〇, 〇〇〇. When the above composite is used as a functional component, the dispersion medium is a water-based dispersion medium. The method for producing a complex of the above poly(3,4-disalkoxythiophene) and a polyanion is described, for example, in Japanese Patent No. 2 6 3 6 9 8 . When the poly(3,4-di-enoxythiophene)-based polyanion is in the form of a slurry, the present specification describes "a complex of poly(3,4 _ ·monooxyl phenanthrene) and a polyanion" Or simply referred to as "composite j ° such that a functional thin film pattern containing the above-mentioned desired functional component is formed on the substrate. In particular, a composite of the above poly(3,4-dialkyloxythiophene) and a polyanion is used as In the case of a conductive polymer, a substrate having a conductive thin film pattern having excellent transparency and conductivity can be obtained. When a substrate made of a transparent material is selected as the substrate, an electrode having excellent transparency can be obtained, which is used as a image electrode of a liquid crystal display. The transparent electrode is extremely useful. The substrate having the g functional thin film pattern obtained by the present invention can be used in various fields depending on the purpose. [Examples] The present invention will be specifically described below on the basis of examples. The present invention is not limited by these examples. The materials and various evaluation methods used in the examples and comparative examples are as follows. In the following examples, "parts" are the "parts by weight". 1. Materials used 1289414 (1 · 1) Substrate A glass plate (4 吋 (1 Ο .16 cm) in diameter, Ο · 7 m m disk shape; total light transmittance: 91.4%) was used. (1.2) a positive-type radiation-sensitive resin composition such that 29.6 parts by weight of cresol novolac resin (mixture of meta and para), and 7.4 parts by weight of 2,3,4,4' - tetrahydroxy xylone-1,2-naphthoquinonediazide-5-sulfonate, mixed with Ο · 1 part by weight of a fluorine-based surfactant, 6.3 parts by weight of propylene glycol monomethyl ether acetate Use the resulting mixture. (1 · 3 ) Developing solution A 2.38 wt% aqueous solution of tetramethylammonium hydroxide was used as a developing solution. (1.4) An aqueous dispersion containing a functional component is added to 49 parts of an aqueous solution of 20.8 parts by weight of polystyrenesulfonic acid having a weight average molecular weight of 75,000, and 49 parts of a 1% by weight aqueous solution of iron (III) sulfate, 8 · 8 parts of 3,4-extended ethyl thiophene' and 1 1 7 parts of a 10% by weight aqueous solution of peroxodisulfate, and the resulting mixture was stirred at 18 ° C for 23 hours to obtain poly(3, An aqueous dispersion of a complex of 4-ethyl thiophene and polystyrene sulfonic acid. After adding 1 5 4 parts of cation exchange resin and 232 parts of anion exchange resin, the mixture was stirred for 2 hours, and then the respective ion exchange resins were filtered and desalted to obtain 1.4 wt% poly(3,4-ethylene). An aqueous dispersion of a complex of thiophene sulphide and polystyrene sulfonic acid. (1.5) A liquid composition containing a functional component, 70. 0 parts of an aqueous dispersion of a functional ingredient obtained in (1. 4), and 1 4 parts by weight of a 25% by weight aqueous dispersion of a polyester resin (Nakasikam Dix Co., Ltd., Kabusi (transliteration) ES-210), and 〇.7 parts of 1〇 1289414% by weight of fluorine-based surfactants (mutual chemical industry limited shares) Company made Brasston (transliteration) R γ - 2 ), with 3.0 parts of N-methylformamide, and 0.7 parts of 10% by weight aqueous ammonium solution, 23.5 parts of desalted water, 〇. 7 A 40% by weight aqueous solution of methylated melamine resin was mixed, and the resulting mixture was a liquid composition containing a functional ingredient. (1 · 6 ) Stripper A stripper N - 3 2 1 (aqueous amine solution) manufactured by Naksim Kendix Co., Ltd. was used. 2. Evaluation method (2 · 1) The film thickness of the pattern formed by the positive-type radiation-sensitive resin composition is NANOMETERRICS NanoSpec/AFT. The film thickness of the functional film is Sloan Technology. DEKTAK3 determination. (2.3) Resolution of Functional Film Pattern A patterned functional film was formed by using a mask of a number of lines parallel to the 36-step line width of 50 to 0.88 μm. Observing by optical microscopy, observing the line width obtained by the pattern of the reticle, the surface resistivity, volume resistivity and total light transmittance of the functional 〇 (2.4) functional film are functional on the substrate. The liquid composition for forming a thin film was coated at 700 rpm for 8 seconds using a spin coater, and heated and dried at 115 ° C for 5 minutes on a hot plate. This was immersed in a release agent for 1 minute, washed, and air-dried to obtain a substrate in which a functional film was formed in its entirety. The surface resistivity, volume resistivity, and total light transmittance were evaluated as follows. -1 8 - 1289414 (2.4.1) Surface resistivity and volume resistivity are determined by [13 1$7194] using Mitsubishi Chemical's (R) GP (MCP-T600) 〇 (2.4) .2) The total light transmittance is measured on the basis of ns K7150, using the Ska 5 type test machine (share) system sea and land (translation) computer HG Μ - 2 B measurement. (Example 1) The positive-type radiation sensitive resin composition was applied onto a substrate by a spin coater at 25 rpm for 30 seconds, and heated and dried on a hot plate at 90 ° C. In a minute, a positive-type radiation-sensitive resin composition layer having a film thickness of 5 μm was formed. A negative mask was placed on the substrate on which the positive-type radiation-sensitive resin composition layer was formed, and exposure was performed at an exposure amount of 150 m/cm 2 using an exposure machine PLA-5 G1 AF manufactured by Kennon Co., Ltd. Then, it was immersed in a developing solution at 23 ° C for 1 minute to dissolve and remove the exposed portion, and a predetermined pattern of the positive-acting radiation-sensitive resin composition was formed by water washing. Then, on the surface of the substrate having the pattern formed of the positive-type radiation-sensitive resin composition, the liquid composition for forming a functional film was applied at a speed of 70 Å pm for 8 seconds. Conditional coating, heating and drying on a hot plate at 1 15 ° C for 5 minutes to form a functional film of 3 1 3 μηι film thickness. Finally, the substrate with the functional film described above is at 23 ° C. The stripper was immersed for 1 minute to "make the pattern of the radiation-sensitive resin composition of the pattern" to be washed with water. Thereby, the pattern of the functional film which does not require a part of the functional film and the above pattern can be removed. _1 9- 1289414 The functional film pattern has a resolution of 3 μm (with a resolution of up to 3 μιτι line width). The surface resistivity of the functional film is 3. Οχ 1 03 Ω / □, and the volume resistivity is 4 · 4 χ 1 0 - 2 Ω · cm. The full light transmittance of the functional film containing the substrate is 87. 1%. The obtained substrate having a functional thin film pattern can be used as a photo electrode of a liquid crystal display, and has usable resolution, conductivity, and transparency. [Effect of the Invention] The functional film pattern having a desired function can be easily formed at a high resolution of 0. Conventionally, in order to form a functional film, the material itself is not sensitive to radiation, and it is difficult to form a functional film pattern with good resolution and functionality. By the present invention, a functional film pattern having a high resolution is formed. In general, when the material for forming a functional film is an aqueous coating liquid, the method of the present invention is particularly effective because it is not easily designed to have a sensitizing radiation. According to the present invention, a functional film can be easily formed without using a sputtering apparatus or the like. For example, a substrate made of a transparent material can be used, and a functional film can be easily formed. The pattern of the functional film obtained by the present invention can be utilized in various fields depending on the purpose. (5) Brief description of the drawings The first (a) to (d) diagrams are schematic diagrams showing the steps of forming a pattern opposite to the desired functional film pattern on the substrate using the positive-type radiation-radiating composition. The second (a) to (d) diagram is a step of forming a pattern opposite to the desired functional film pattern on the substrate using a negative-type radiation linear composition -20 - 1289414 The resolution of the functional thin film pattern is 3 Km (with resolution up to 3 _ line width). The surface resistivity of the functional film is 3 · Ο X 1 0 3 Ω / 匚], and the volume resistivity is 4. 4 X 1 〇 - 2 Ω · c m. The total light transmittance of the functional film containing the substrate was 87. 1%. The obtained substrate having a functional thin film pattern can be used as a image electrode of a liquid crystal display, and has usable resolution, conductivity, and transparency. [Effects of the Invention] The functional film pattern having a desired function can be easily formed with high resolution. Conventionally, in order to form a functional film, the material itself is not sensitive to radiation, and it is difficult to form a functional film pattern with good resolution and functionality. By the present invention, a functional film pattern having a high resolution is formed. In general, when the material for forming a functional film is an aqueous coating liquid, the method of the present invention is particularly effective because it is not easily designed to have a sensitizing radiation. According to the present invention, a functional film can be easily formed without using a sputtering apparatus or the like. For example, a substrate made of a transparent material can be used, and a functional film can be easily formed. The pattern of the functional film obtained by the present invention can be utilized in various fields depending on the purpose. (5) Brief description of the drawings The first (a) to (d) diagrams are schematic diagrams showing the steps of forming a pattern opposite to the desired functional film pattern on the substrate using the positive-type radiation-radiating composition. The second (a) to (d) diagram is a simple -2 0 - 1289414 diagram of the step of forming a pattern opposite to the desired functional thin film pattern on the substrate using the negative-type radiation linear composition. Figures 3(a) to (c) are schematic diagrams showing the steps of forming a functional thin film pattern on a substrate by the method of the present invention. [Description of Symbols] 1 : Substrate 2 : Radiation-sensitive resin composition layer 5 : Functional film 20 : Reverse pattern 50 : Pattern of functional film -21