TWI625214B - Conductive polymer self-standing film, method of forming the same, and conductive laminate - Google Patents
Conductive polymer self-standing film, method of forming the same, and conductive laminate Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/12—Spreading-out the material on a substrate, e.g. on the surface of a liquid
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
Abstract
本發明係一種導電性聚合物自立膜之形成方法，其特徵在於包含：於支持體上，依序形成阻劑層、導電性聚合物層之步驟；及去除上述阻劑層的同時，剝離上述導電性聚合物層，形成導電性聚合物自立膜之步驟；導電性聚合物自立膜、及導電性層積體。根據本發明，可提供可簡便且容易地在通常難以形成導電性聚合物之不織布、網目等的多孔質基材；或表面粗糙度大的材料；具有曲面的基材等之上，形成導電性聚合物層之奈米~次微米級之膜厚極薄之導電性聚合物自立膜，其形成方法，及導電性層積體。 The present invention relates to a method for forming a conductive polymer self-standing film, comprising: a step of sequentially forming a resist layer and a conductive polymer layer on a support; and removing the above-mentioned resist layer while peeling off the above a conductive polymer layer forming a conductive polymer self-standing film; a conductive polymer self-standing film; and a conductive laminate. According to the present invention, it is possible to provide a porous substrate which can be easily and easily formed into a nonwoven fabric or a mesh which is generally difficult to form a conductive polymer, or a material having a large surface roughness, a substrate having a curved surface, or the like, and forming conductivity. A conductive polymer self-standing film having a very thin film thickness of nanometer to submicron of a polymer layer, a method for forming the same, and a conductive laminate.
Description
本發明，係關於用於帶電防止膜或透明導電膜等的導電性聚合物自立膜、其形成方法及上述導電性聚合物自立膜之導電性層積體。 The present invention relates to a conductive polymer self-standing film for use in a charging prevention film, a transparent conductive film, or the like, a method for forming the same, and a conductive laminate of the above-described conductive polymer self-standing film.
近年，以聚(3,4-亞乙基二氧噻吩)：聚苯乙烯磺酸酯(PEDOT：PSS)，或聚苯胺：樟腦磺酸(PANI：CSA)等所代表的導電性聚合物，用於作為有機電子裝置用的緩衝層材料受到矚目。最近，由其優良的柔軟性，經濟性等的觀點，亦有研究作為代替以ITO(氧化銦錫)所代表的透明氧化物導電體所組成之透明電極之材料，利用導電性聚合物。 In recent years, a conductive polymer represented by poly(3,4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT: PSS) or polyaniline: camphorsulfonic acid (PANI: CSA), A buffer layer material for use as an organic electronic device has attracted attention. Recently, from the viewpoint of excellent flexibility, economy, and the like, a material which is a transparent electrode composed of a transparent oxide conductor represented by ITO (indium tin oxide) has been studied, and a conductive polymer is used.
先前，具有導電性聚合物之膜之成形體之製造方法，已知如下者。 Heretofore, a method of producing a molded body of a film having a conductive polymer is known as follows.
於專利文獻1，揭示有導電性成形體之製造方法，其係於形成在基材上之含有奈米碳管與含有導電性聚合物之導電性塗膜上形成成形體，之後，將上述基材剝離。 Patent Document 1 discloses a method for producing a conductive molded body in which a molded body is formed on a conductive coating film containing a carbon nanotube formed on a substrate and a conductive polymer, and then the base is formed. Material stripping.
於專利文獻2，揭示有在基板上，形成包含奈米碳管之導電性聚合物層，將此接著轉印於其他的基材，之後，將上述基板剝離之技術。 Patent Document 2 discloses a technique in which a conductive polymer layer containing a carbon nanotube is formed on a substrate, and then transferred to another substrate, and then the substrate is peeled off.
如該等文獻所記載，導電性聚合物層(膜)，通常， 係將導電性聚合物之水分散液或溶液，薄薄地塗佈在基板上，乾燥所形成。 As described in these documents, a conductive polymer layer (film), usually, An aqueous dispersion or solution of a conductive polymer is applied thinly on a substrate and dried.
但是，基板為紙類、不織布、網布等的多孔質基材或表面粗糙度大的基材時，即使將導電性聚合物的水分散液或溶液塗佈，該等溶液被基板表面的孔或凹凸吸收，有難以形成平滑而均勻的薄膜之情形。此外，使用具有曲面之基板時，有滴液等，技術上難以均勻地塗佈。 However, when the substrate is a porous substrate such as paper, non-woven fabric, or mesh, or a substrate having a large surface roughness, even if an aqueous dispersion or solution of the conductive polymer is applied, the solutions are holes in the surface of the substrate. Or bump absorption, it is difficult to form a smooth and uniform film. Further, when a substrate having a curved surface is used, there is a dropping liquid or the like, and it is technically difficult to apply uniformly.
因此，有將導電性聚合物之膜，另外製作成以其本身自立的狀態之膜(自立膜)，將該自立膜，層積在如上所述之難以直接形成均勻的膜的基板上之方法。 Therefore, there is a method in which a film of a conductive polymer is separately formed into a film (self-standing film) in a state of being self-standing, and the self-standing film is laminated on a substrate which is difficult to directly form a uniform film as described above. .
例如，於非專利文獻1，記載有將聚(3,4-亞乙基二氧噻吩)：聚苯乙烯磺酸酯(PEDOT：PSS)之聚苯乙烯磺酸酯(PSS)成分，以聚(β-羥基醚)之硫酸鹽(S-PHE)，或具有三氟甲基之聚(β-羥基醚)之硫酸鹽(S-PHEF)等的造膜性高的合成聚合物取代，可得導電性聚合物自立膜。 For example, Non-Patent Document 1 discloses a polystyrene sulfonate (PSS) component of poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS). (S-PHE) (S-PHE) or a synthetic polymer having a high film-forming property such as a trifluoromethyl group (β-hydroxy ether) sulfate (S-PHEF) A conductive polymer is self-standing film.
但是，於該方法，由於使用造膜性高的合成聚合物，所得導電性聚合物之自立膜之膜厚變大，而難以製造膜厚由奈米等級至微米等級之厚度較薄之導電性聚合物自立膜。 However, in this method, since a synthetic polymer having a high film forming property is used, the film thickness of the self-supporting film of the obtained conductive polymer becomes large, and it is difficult to produce a conductive polymerization having a thin film thickness from a nanometer to a micron. Self-standing film.
另一方面，於專利文獻3，揭示有將包含具有溶劑可溶性之聚合物醯亞胺分子之溶液，於基板成膜，成膜後，將基板烘烤使聚合物醯亞胺膜中的溶劑脫離，浸漬於剝離溶液，利用表面張力與膜的浮力，使聚醯亞胺膜由基板剝離之聚醯亞胺薄膜之製作方法。 On the other hand, Patent Document 3 discloses that a solution containing a solvent-soluble polymer quinone imine molecule is formed on a substrate, and after the film formation, the substrate is baked to desorb the solvent in the polymer quinone imide film. A method for producing a polyimide film which is immersed in a peeling solution and which is obtained by peeling a polyimide film from a substrate by surface tension and buoyancy of the film.
[先前技術文獻] [Previous Technical Literature]
[專利文獻] [Patent Literature]
[專利文獻1]日本特開2006-45383號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-45383
[專利文獻2]日本特表2008-536710號公報(WO2007/094757號小冊) [Patent Document 2] Japanese Patent Publication No. 2008-536710 (WO2007/094757 booklet)
[專利文獻3]日本特開2010-155919號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2010-155919
[非專利文獻] [Non-patent literature]
[非專利文獻1]Synthetic Metals, 83 (1996) 125-130 [Non-Patent Document 1] Synthetic Metals, 83 (1996) 125-130
本發明，係有鑑於該先前技術之實情而完成者，以提供可與紙類、不織布、網布等的多孔質基材，或表面粗糙度大的基材、具有曲面之基材等，簡便地形成層積體之導電性聚合物自立膜，其形成方法及具有上述導電性聚合物層之導電性層積體為目標 The present invention has been made in view of the facts of the prior art, and provides a porous substrate which can be used with paper, nonwoven fabric, mesh, or the like, or a substrate having a large surface roughness, a substrate having a curved surface, and the like. Conductive polymer self-standing film in which a laminate is formed, a method for forming the same, and a conductive laminate having the above-mentioned conductive polymer layer
本發明者們，為解決上述課題專心研究的結果，發現於支持體上，依序形成阻劑層、導電性聚合物層，藉由將上述阻劑層去除的同時，剝離上述導電性聚合物層，可簡便且容易地形成具有平滑而均勻的膜質之導電性聚合物自立膜，達至完成本發明。 As a result of intensive studies to solve the above problems, the present inventors have found that a resist layer and a conductive polymer layer are sequentially formed on a support, and the above-mentioned conductive polymer is removed while removing the above-mentioned resist layer. The layer can easily and easily form a conductive polymer self-standing film having a smooth and uniform film quality, and the present invention can be completed.
根據本發明，可提供下述(1)~(5)之導電性聚合物自立膜之形成方法、(6)導電性聚合物自立膜及(7)導電性層積 體。 According to the present invention, a method for forming a conductive polymer self-standing film of the following (1) to (5), (6) a conductive polymer self-standing film, and (7) conductive layering can be provided. body.
(1)一種導電性聚合物自立膜之形成方法，其特徵在於包含：於支持體上，依序形成阻劑層、導電性聚合物層之步驟；及去除上述阻劑層的同時，剝離上述導電性聚合物層，形成導電性聚合物自立膜之步驟。 (1) A method for forming a conductive polymer self-standing film, comprising: a step of sequentially forming a resist layer and a conductive polymer layer on a support; and removing the resist layer while peeling off The conductive polymer layer forms a step of forming a conductive polymer from the standing film.
(2)根據(1)之導電性聚合物自立膜之形成方法，其中上述阻劑層，係正片型阻劑層。 (2) The method for forming a conductive polymer self-standing film according to (1), wherein the resist layer is a positive-type resist layer.
(3)根據(2)之導電性聚合物自立膜之形成方法，其中包含將上述阻劑層曝光的步驟。 (3) A method of forming a conductive polymer self-standing film according to (2), which comprises the step of exposing the above-mentioned resist layer.
(4)根據(1)之導電性聚合物自立膜之形成方法，其中進一步包含將剝離之導電性聚合物層，離子交換處理之步驟。 (4) The method for forming a conductive polymer self-standing film according to (1), which further comprises the step of ion-exchange treatment of the peeled conductive polymer layer.
(5)根據(4)之導電性聚合物自立膜之形成方法步驟，其中上述離子交換處理，係藉由將剝離之導電性聚合物層，浸漬於離子交換溶液中而進行者。 (5) The method for forming a conductive polymer self-standing film according to (4), wherein the ion exchange treatment is performed by immersing the peeled conductive polymer layer in an ion exchange solution.
(6)根據(1)~(5)之任何一項之導電性聚合物自立膜的形成方法，其中形成之導電性聚合物自立膜之膜厚為10~5000nm。 (6) The method for forming a conductive polymer self-supporting film according to any one of (1) to (5), wherein the conductive polymer-free standing film has a film thickness of 10 to 5000 nm.
(7)一種導電性聚合物自立膜，其係以上述(1)~(6)之任何一項之形成方法所得。 (7) A conductive polymer self-standing film obtained by the method for forming any one of the above (1) to (6).
(8)一種導電性層積體，其係於基材上，層積(1)~(6)之任何一項之形成方法所得之導電性聚合物自立膜而成。 (8) A conductive laminate obtained by laminating a conductive polymer obtained by a method for forming any one of (1) to (6) on a substrate.
根據本發明之形成方法，可以較大面積，簡便且容易得到具有平滑而均勻的膜質之奈米級至次微米級之極薄膜厚之導電性聚合物自立膜。 According to the formation method of the present invention, it is possible to easily and easily obtain a conductive polymer self-supporting film having a smooth and uniform film quality from a nanometer to a submicron-thick film thickness with a large area.
使用本發明之導電性聚合物自立膜，可簡便且容易地在通常難以形成導電性聚合物之不織布、網目等的多孔質基材；或表面粗糙度大的材料；具有曲面的基材等之上，製造層積導電膜之導電性層積體。 By using the conductive polymer self-supporting film of the present invention, it is possible to easily and easily form a porous substrate such as a nonwoven fabric or a mesh which is generally difficult to form a conductive polymer; or a material having a large surface roughness; a substrate having a curved surface; In the above, a conductive laminate in which a conductive film is laminated is produced.
1‧‧‧支持體 1‧‧‧Support
2‧‧‧阻劑層 2‧‧‧Resist layer
3‧‧‧導電性聚合物層 3‧‧‧ Conductive polymer layer
3'‧‧‧導電性聚合物自立膜 3'‧‧‧ Conductive polymer self-standing film
4‧‧‧基材 4‧‧‧Substrate
5‧‧‧導電性層積體 5‧‧‧ Conductive laminate
第1圖係本發明之導電性聚合物自立膜之形成方法之步驟剖面圖。 Fig. 1 is a cross-sectional view showing the steps of a method for forming a conductive polymer self-standing film of the present invention.
第2圖係本發明之導電性層積體之形成方法之步驟剖面圖。 Fig. 2 is a cross-sectional view showing the steps of a method of forming a conductive laminate of the present invention.
以下，將本發明分項為1)導電性聚合物自立膜之形成方法、2)導電性聚合物自立膜、3)導電性層積體，詳細地說明。 Hereinafter, the present invention will be described in detail as 1) a method for forming a conductive polymer self-standing film, 2) a conductive polymer self-standing film, and 3) a conductive laminate.
1)導電性聚合物自立膜之形成方法 1) Method for forming conductive polymer self-standing film
本發明之導電性聚合物自立膜之形成方法，其特徵在於包含：於支持體上，依序形成阻劑層、導電性聚合物層之步驟(步驟1)；可按照必要，將上述阻劑層曝光的步驟(步驟2)；及去除上述阻劑層的同時，由上述支持體剝離導電性聚合物層，形成導電性聚合物自立膜之步驟(步驟3)。 A method for forming a conductive polymer self-supporting film according to the present invention, comprising the steps of: sequentially forming a resist layer and a conductive polymer layer on a support (step 1); and if necessary, the above-mentioned resist a step of layer exposure (step 2); and a step of removing the conductive layer from the support while removing the resist layer to form a conductive polymer self-standing film (step 3).
在此，所謂「自立膜」，係指即使沒有其他支持體的存在，亦可保持作為膜的形狀的膜 Here, the "self-standing film" means a film that retains the shape of the film even if no other support is present.
以下，將本發明之導電性聚合物自立膜之形成方法，參照圖面說明。 Hereinafter, a method of forming the conductive polymer self-standing film of the present invention will be described with reference to the drawings.
〔步驟1〕 〔step 1〕
首先，如圖1(a)所示，於支持體1上，形成阻劑層2。 First, as shown in FIG. 1(a), a resist layer 2 is formed on the support 1.
使用之支持體1，只要是可擔持阻劑層者，並無特別限定。其中，在於後述之曝光步驟，可使全曝光光的80%以上穿透者為佳。可使用例如，玻璃基板或透明的塑膠基板等。 The support 1 to be used is not particularly limited as long as it can support the resist layer. Among them, in the exposure step described later, it is preferable that 80% or more of the total exposure light is penetrated. For example, a glass substrate or a transparent plastic substrate or the like can be used.
構成塑膠基板的塑膠，可舉聚醯亞胺、聚醯胺、聚醯胺醯亞胺、聚苯醚、聚醚酮、聚醚醚酮、聚烯烴、聚酯、聚碳酸酯、聚碸、聚醚碸、對苯硫醚、聚芳酯、丙烯酸系樹脂、環烯烴系聚合物、芳香族系聚合物等。該等塑膠，可以一種單獨或組合二種以上使用。 The plastics constituting the plastic substrate may be polyimine, polyamine, polyamidamine, polyphenylene ether, polyether ketone, polyetheretherketone, polyolefin, polyester, polycarbonate, polyfluorene, Polyether oxime, p-phenylene sulfide, polyarylate, acrylic resin, cycloolefin polymer, aromatic polymer, and the like. These plastics may be used alone or in combination of two or more.
該等之中，由具有泛用性，以聚酯、聚醯胺或環烯烴系聚合物為佳，以聚酯更佳。 Among these, it is preferably versatile, and polyester, polyamine or a cycloolefin polymer is preferred, and polyester is more preferred.
聚酯，可舉聚對苯二甲酸乙二醇酯、聚對苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯、聚芳酯化合物等。 The polyester may, for example, be polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate or a polyarylate compound.
支持體1之厚度，並無特別限定，以玻璃基板之情形，通常為10~50000μm，以塑膠基板之情形，通常為10~1000μm，以10~100μm為佳 The thickness of the support 1 is not particularly limited. In the case of a glass substrate, it is usually 10 to 50,000 μm, and in the case of a plastic substrate, it is usually 10 to 1000 μm, preferably 10 to 100 μm.
形成之阻劑層2，可為正片型阻劑層，亦可為負片型阻劑層，以顯影液，導電性聚合物層之收縮或膨脹等的不良影響少，容易得到平滑而具有均勻的膜質之導電性聚合物自立膜之點以正片型阻劑層為佳。 The formed resist layer 2 may be a positive-type resist layer or a negative-type resist layer, which has less adverse effects such as shrinkage or expansion of the developing solution and the conductive polymer layer, and is easily and smoothly obtained. The film-forming conductive polymer is preferably a positive-type resist layer at the point of the self-standing film.
阻劑層2，可藉由先前習知的方法形成。可藉由例如，將光阻組成物溶解於溶劑之溶液(光阻材料)，以旋轉塗佈機或吹付等塗佈於支持體上之後，加熱(預烘烤)形成。 The resist layer 2 can be formed by a conventional method. For example, a solution (photoresist material) in which a photoresist composition is dissolved in a solvent is applied to a support by a spin coater or a blower, and then heated (prebaked) to form.
光阻組成物，並無特別限制，可由通常者之中任意選擇，可良好地使用可藉由鹼水溶液顯影者。如此之光阻組成物，可舉(i)含有二疊氮基萘醌化合物與酚醛樹脂之正片型光阻、(ii)含有可藉由曝光產生酸之化合物、藉由酸的分解對鹼水溶液之溶解性增大之化合物、及鹼可溶性樹脂之正片型光阻、(iii)含有藉由曝光產生酸的化合物、具有藉由酸分解增大對鹼性水溶液之溶解性之基之鹼可溶性樹脂之正片型光阻及(iv)含有藉由光產生酸之化合物、架橋劑及鹼可溶性樹脂之負片型光阻等。 The photoresist composition is not particularly limited and may be selected arbitrarily from the usual one, and can be favorably used for development by an aqueous alkali solution. Such a photoresist composition may, for example, be (i) a positive-type resist containing a diazide naphthoquinone compound and a phenol resin, (ii) a compound containing an acid which can be exposed by exposure, and an aqueous alkali solution by decomposition of an acid. a compound having an increased solubility and a positive-type resist of an alkali-soluble resin, (iii) a compound containing an acid generated by exposure, and an alkali-soluble resin having a base which increases solubility in an aqueous alkaline solution by acid decomposition The positive-type photoresist and (iv) a negative-type photoresist containing a compound which generates an acid by light, a bridging agent, and an alkali-soluble resin.
此外，正片型的光阻材料，亦可使用商品名：OFPR-800LB(東京應化工業公司製)等之市售品。 In addition, as a positive-type photoresist material, a commercial item such as OFPR-800LB (manufactured by Tokyo Ohka Kogyo Co., Ltd.) may be used.
形成之阻劑層2之厚度，只要可去除阻劑層，於支持體與導電性聚合物層之間形成空間，可使導電性聚合物層游離的程度的厚度，並無特別限制，通常為0.1~10μm，以0.5~2μm為佳。 The thickness of the resist layer 2 to be formed is not particularly limited as long as the resist layer can be removed, and a thickness is formed between the support and the conductive polymer layer, and the conductive polymer layer can be freed. 0.1~10μm, preferably 0.5~2μm.
其次，如第1圖(b)所示，於所得阻劑層2上形成導電性聚合物層3。 Next, as shown in Fig. 1(b), a conductive polymer layer 3 is formed on the obtained resist layer 2.
導電性聚合物層3，係於阻劑層2上，塗佈包含導電性材料之導電性聚合物層形成用組成物，藉由將所得塗膜乾燥，而形成。 The conductive polymer layer 3 is formed on the resist layer 2, and a composition for forming a conductive polymer layer containing a conductive material is applied, and the obtained coating film is dried.
使用之導電性材料，可舉藉由π電子共軛具有導電性之π電子共軛系導電性聚合物、奈米碳管等。π電子共軛系導電性聚合物，具體可舉，聚乙炔、聚苯硫醚、聚(1,6-庚二烯)、聚聯苯撐(聚對苯撐)、聚對苯硫醚、聚苯乙炔、聚(2,5- 噻吩)、聚噻吩類、聚苯胺類及聚吡咯類等。 The conductive material to be used may be a π-electron conjugated conductive polymer or a carbon nanotube which is electrically conductive by π electron conjugation. The π-electron conjugated conductive polymer may, specifically, be polyacetylene, polyphenylene sulfide, poly(1,6-heptadiene), polybiphenylene (polyphenylene), polyparaphenylene sulfide, or the like. Polyphenylacetylene, poly(2,5- Thiophene), polythiophenes, polyanilines, and polypyrroles.
聚噻吩類，可舉聚3-甲基噻吩、聚3-乙基噻吩、聚3-甲氧基噻吩、聚3-乙氧基噻吩、聚(3,4-亞乙基二氧噻吩)(PEDOT)等。 Polythiophenes, which may be poly-3-methylthiophene, poly-3-ethylthiophene, poly-3-methoxythiophene, poly-3-ethoxythiophene, poly(3,4-ethylenedioxythiophene) ( PEDOT) and so on.
聚苯胺類，可舉聚2-甲基苯胺、聚3-甲基苯胺、聚2-乙基苯胺、聚3-乙基苯胺、聚2-甲氧基苯胺、聚3-甲氧基苯胺、聚2-乙氧基苯胺、聚3-乙氧基苯胺、聚N-甲基苯胺、聚N-丙基苯胺、聚N-苯基-1-萘基苯胺、聚8-苯胺基-1-萘磺酸、聚2-胺基苯磺酸、聚7-苯胺基-4-羥基-2-萘磺酸等。 Polyaniline, which may be poly-2-methylaniline, poly-3-methylaniline, poly-2-ethylaniline, poly-3-ethylaniline, poly-2-methoxyaniline, poly-3-methoxyaniline, Poly 2-ethoxyaniline, poly-3-ethoxyaniline, poly-N-methylaniline, poly-N-propylaniline, poly-N-phenyl-1-naphthylaniline, poly(8-anilino-1- Naphthalenesulfonic acid, poly-2-aminobenzenesulfonic acid, poly 7-anilino-4-hydroxy-2-naphthalenesulfonic acid, and the like.
聚吡咯類，可舉聚1-甲基吡咯、聚3-甲基吡咯、聚1-乙基吡咯、聚3-乙基吡咯、聚1-甲氧基吡咯、3-甲氧基吡咯、聚1-乙氧基吡咯、聚3-乙氧基吡咯等。 Polypyrroles, which may be 1-methylpyrrole, poly-3-methylpyrrole, poly-1-ethylpyrrole, poly-3-ethylpyrrole, poly-1-methoxypyrrole, 3-methoxypyrrole, poly 1-ethoxypyrrole, poly-3-ethoxypyrrole, and the like.
π電子共軛系導電性聚合物，為使導電性更高，及/或，提高導電性聚合物之可溶性，亦可作為取代基，導入烷基、羧酸基、磺酸基、烷氧基、羥基、氰基等的官能基。 The π-electron conjugated conductive polymer may have a higher conductivity and/or improve the solubility of the conductive polymer, or may be introduced as an alkyl group, a carboxylic acid group, a sulfonic acid group or an alkoxy group. a functional group such as a hydroxyl group or a cyano group.
烷基，可舉甲基、乙基、丙基、異丙基、第三丁基、正丁基、異丁基、第二丁基、戊基、己基、辛基、癸基等的碳數1~10之烷基。烷氧基，可舉甲氧基、乙氧基、丙氧基、第三丁氧基、戊氧基等的碳數1~10之烷氧基。 The alkyl group may have a carbon number such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a n-butyl group, an isobutyl group, a second butyl group, a pentyl group, a hexyl group, an octyl group or a decyl group. 1 to 10 alkyl groups. The alkoxy group may, for example, be an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, a third butoxy group or a pentyloxy group.
該等導電性聚合物，可以一種單獨，或組合二種以上使用。 These conductive polymers may be used alone or in combination of two or more.
導電性聚合物，可使用藉由習知的方法，實施以酸之摻雜處理，添加外部摻雜物者。藉由添加摻雜物，可得充分的導電性。 As the conductive polymer, those doped with an acid and added with an external dopant can be used by a conventional method. By adding a dopant, sufficient conductivity can be obtained.
摻雜物，並無特別限定，可使用磺酸化合物等的 先前習知之摻雜物。具體，可舉苯醌磺酸、蒽磺酸、蒽醌磺酸、1,5-萘二磺酸、1,6-萘二磺酸、1-萘磺酸、2-萘磺酸、2,6-萘二磺酸、2,7-萘二磺酸、2-甲基-5-異丙基苯磺酸、4-辛基苯磺酸、4-硝基甲苯-2-磺酸、間硝基苯磺酸、鄰硝基苯磺酸、對乙基苯磺酸、對氯苯磺酸、對癸基苯磺酸、對十二基苯磺酸、對甲苯磺酸、對硝基苯磺酸、對戊基苯磺酸、二壬基萘苯磺酸、三氯苯磺酸、羥基苯磺酸、丁基萘苯磺酸、苯磺酸等的芳香族磺酸；甲磺酸、乙磺酸、正丁磺酸、正己磺酸、正辛磺酸、十二基磺酸、三氟甲磺酸、樟腦磺酸等的脂肪族磺酸；乙醯磺酸；聚乙烯基磺酸、聚苯乙烯磺酸(PSS)、聚(2-丙烯醯胺-2-甲基丙烷磺酸)等的聚合物磺酸；及該等鹽等。該等摻雜物，可以一種單獨，或組合二種以上使用。 The dopant is not particularly limited, and a sulfonic acid compound or the like can be used. Previously known dopants. Specific examples thereof include benzoquinonesulfonic acid, sulfonic acid, sulfonic acid, 1,5-naphthalenedisulfonic acid, 1,6-naphthalenedisulfonic acid, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, and 2, 6-naphthalene disulfonic acid, 2,7-naphthalene disulfonic acid, 2-methyl-5-isopropylbenzenesulfonic acid, 4-octylbenzenesulfonic acid, 4-nitrotoluene-2-sulfonic acid, Nitrobenzenesulfonic acid, o-nitrobenzenesulfonic acid, p-ethylbenzenesulfonic acid, p-chlorobenzenesulfonic acid, p-nonylbenzenesulfonic acid, p-dodecylbenzenesulfonic acid, p-toluenesulfonic acid, p-nitrobenzene An aromatic sulfonic acid such as sulfonic acid, p-pentylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, trichlorobenzenesulfonic acid, hydroxybenzenesulfonic acid, butylnaphthalenesulfonic acid or benzenesulfonic acid; methanesulfonic acid, An aliphatic sulfonic acid such as ethanesulfonic acid, n-butanesulfonic acid, n-hexylsulfonic acid, n-octanesulfonic acid, dodecylsulfonic acid, trifluoromethanesulfonic acid or camphorsulfonic acid; acetophenone sulfonic acid; polyvinylsulfonic acid a polymer sulfonic acid such as polystyrenesulfonic acid (PSS) or poly(2-propenylamine-2-methylpropanesulfonic acid); and the like. These dopants may be used alone or in combination of two or more.
鹽，可舉鋰鹽、鉀鹽、鈉鹽、銅鹽、鐵鹽、鋁鹽、鈰鹽、鎢鹽、鉻鹽、錳鹽、錫鹽等的金屬鹽、甲基銨鹽、二甲基銨鹽、三甲基銨鹽、四甲基銨鹽、乙基銨鹽、二乙基銨鹽、三乙基銨鹽、四乙基銨鹽、乙基甲基銨鹽、二乙基甲基銨鹽、二甲基乙基銨鹽、三乙基甲基銨鹽、三甲基乙基銨鹽、二乙基二甲基銨鹽、丙基銨鹽、二丙基銨鹽、異丙基銨鹽、二異丙基銨鹽、丁基銨鹽、二丁基銨鹽、甲基丙基銨鹽、乙基丙基銨鹽、甲基異丙基銨鹽、乙基異丙基銨鹽、甲基丁基銨鹽、乙基丁基銨鹽、四羥甲基銨鹽、四正丁基銨鹽、四第二丁基銨鹽、四第三丁基銨鹽等的烷基銨鹽、哌啶鹽、吡咯鹽、嗎啉鹽、哌嗪鹽、吡啶鹽、α-甲基吡啶鹽、β-甲基吡啶鹽、γ-甲基吡啶鹽、喹啉鹽、異喹啉鹽、吡咯啉鹽等的含氮雜環化合物之鹽；銨鹽等。 The salt may be a metal salt, a methyl ammonium salt or a dimethyl ammonium salt of a lithium salt, a potassium salt, a sodium salt, a copper salt, an iron salt, an aluminum salt, a barium salt, a tungsten salt, a chromium salt, a manganese salt or a tin salt. Salt, trimethylammonium salt, tetramethylammonium salt, ethylammonium salt, diethylammonium salt, triethylammonium salt, tetraethylammonium salt, ethylmethylammonium salt, diethylmethylammonium salt Salt, dimethylethylammonium salt, triethylmethylammonium salt, trimethylethylammonium salt, diethyldimethylammonium salt, propylammonium salt, dipropylammonium salt, isopropylammonium Salt, diisopropylammonium salt, butylammonium salt, dibutylammonium salt, methylpropylammonium salt, ethylpropylammonium salt, methylisopropylammonium salt, ethylisopropylammonium salt, An alkylammonium salt such as methyl butyl ammonium salt, ethyl butyl ammonium salt, tetramethylol ammonium salt, tetra-n-butyl ammonium salt, tetra-second butyl ammonium salt or tetra-tert-butyl ammonium salt, Piperidine salt, pyrrole salt, morpholine salt, piperazine salt, pyridinium salt, α-methylpyridine salt, β-methylpyridine salt, γ-methylpyridine salt, quinoline salt, isoquinoline salt, pyrroline a salt of a nitrogen-containing heterocyclic compound such as a salt; an ammonium salt or the like.
摻雜物的添加量，通常對導電性聚合物100質量部為100~300質量部，以100~250質量部為佳。 The amount of the dopant to be added is usually 100 to 300 parts by mass for the conductive polymer 100, and preferably 100 to 250 parts by mass.
該等之中，作為導電性聚合物，由可得很高的導電性的觀點，使用聚噻吩類、聚苯胺類或聚吡咯類為佳，使用對等聚合物添加摻雜物之混合物(摻雜處理之導電性聚合物)更佳。由透明性及成膜性優良之點，進一步使用對聚噻吩類添加摻雜物之混合物更佳，使用對聚(3,4-乙烯氧化吩)(PEDOT)，添加聚苯乙烯硫酸離子(PSS)作為摻雜物之混合物特別佳。 Among these, as the conductive polymer, a polythiophene, a polyaniline or a polypyrrole is preferably used from the viewpoint of obtaining high conductivity, and a mixture of dopants is added using a peer polymer. A miscellaneous conductive polymer) is preferred. From the point of excellent transparency and film formability, it is more preferable to use a mixture of polythiophene-added dopants, and to use poly(3,4-ethylene oxide phenoxide) (PEDOT) to add polystyrene sulfate ions (PSS). As a mixture of dopants, it is particularly preferred.
導電性聚合物層形成用組成物，係將上述導電性聚合物、或根據期望摻雜處理之導電性聚合物、奈米碳管等的導電性材料，按照必要添加膠合劑等的其他成分，溶解或分散於溶劑而調製。 The conductive polymer layer-forming composition is a conductive material such as a conductive polymer or a conductive material such as a carbon nanotube which is desirably doped, and other components such as a binder are added as necessary. It is prepared by dissolving or dispersing in a solvent.
使用之溶劑，以導電性聚合物的溶解度高者為佳。例如，水；丙酮、丁酮等的酮類；N-甲基吡咯烷酮等的胺類等。 The solvent to be used preferably has a high solubility of the conductive polymer. For example, water; ketones such as acetone and methyl ethyl ketone; and amines such as N-methylpyrrolidone.
導電性聚合物層形成用組成物之固體分濃度，通常為1~30質量% The solid concentration of the composition for forming a conductive polymer layer, usually 1 to 30% by mass
此外在於本發明，作為導電性聚合物層形成用組成物，亦可直接使用商品名：S305(日本AGFA Materials公司製)等的市售品。 Further, in the present invention, as a composition for forming a conductive polymer layer, a commercially available product such as S305 (manufactured by Japan AGFA Materials Co., Ltd.) may be used as it is.
將導電性聚合物層形成用組成物塗佈於阻劑層2上之方法，可舉網版印刷法、苯胺印刷法、凹版印刷法、旋轉塗佈法、浸漬法、模具塗佈法、噴霧塗佈法、棒塗佈法、刮刀法等的習知的塗層方法。 A method of applying a composition for forming a conductive polymer layer on the resist layer 2 may be a screen printing method, a flexographic printing method, a gravure printing method, a spin coating method, a dipping method, a die coating method, or a spray. A conventional coating method such as a coating method, a bar coating method, or a doctor blade method.
乾燥方法，可採用熱風乾燥、熱輥輪乾燥、紅外 線照射等，先前習知之乾燥方法。 Drying method, hot air drying, hot roller drying, infrared Line irradiation, etc., previously known drying methods.
加熱溫度，通常為80~150℃，加熱時間，根據加熱方法而異，但通常係由數10秒至數10分鐘。 The heating temperature is usually 80 to 150 ° C, and the heating time varies depending on the heating method, but it usually ranges from 10 seconds to 10 minutes.
所得導電性聚合物層3之厚度，只要是可作為自立膜操作之範圍，並無特別限定，通常為10~5000nm，以50~1000nm為佳，以50~500nm更佳，以50~200nm的厚度特別佳，未滿10nm則作為自立膜之操作性顯著變差，此外，超過5000nm，則透明性下降而不佳。 The thickness of the obtained conductive polymer layer 3 is not particularly limited as long as it can be operated as a self-standing film, and is usually 10 to 5000 nm, preferably 50 to 1000 nm, more preferably 50 to 500 nm, and 50 to 200 nm. The thickness is particularly good. When the thickness is less than 10 nm, the workability as a self-supporting film is remarkably deteriorated. Further, when it exceeds 5000 nm, the transparency is not preferable.
〔步驟2〕 [Step 2]
接著，按照必要，照射曝光光，使阻劑層2曝光為佳。如第1圖(c)所示，曝光，可將阻劑層全部曝光，亦可使用適當的掩模，僅曝光阻劑層之特定區域，由有效地得到導電性聚合物之自立膜之觀點，至少將包括阻劑層之端部的區域曝光為佳。 Next, the exposure light is irradiated as necessary to expose the resist layer 2 preferably. As shown in Fig. 1(c), the entire resist layer can be exposed by exposure, or a specific mask can be used to expose only a specific region of the resist layer, and the viewpoint of efficiently obtaining a self-supporting film of the conductive polymer can be obtained. It is preferable to expose at least the region including the end portion of the resist layer.
曝光光，由防止導電性聚合物層吸收曝光光而降低導電性能之點，由透明的支持體1側照射為佳。 The exposure light is preferably irradiated on the side of the transparent support 1 by preventing the conductive polymer layer from absorbing the exposure light and reducing the conductivity.
用於曝光之光(曝光光)，可舉紫外線、可見光線、雷射光等。曝光光的照射源，可使用由先前使用於光照射光硬化性光阻者。可舉例如，氙燈、可見光雷射、紫外線雷射、超高壓水銀燈、高壓水銀燈、氬雷射、準分子雷射等。 The light used for exposure (exposure light) may be ultraviolet light, visible light, or laser light. As the irradiation source of the exposure light, those which have been used for the light-curing photoresist previously used for light irradiation can be used. For example, xenon lamps, visible light lasers, ultraviolet lasers, ultra high pressure mercury lamps, high pressure mercury lamps, argon lasers, excimer lasers, and the like.
光的照射量，通常為0.5~2000mJ/cm2，以1~1000mJ/cm2的範圍為佳。 The amount of light to be irradiated is usually 0.5 to 2000 mJ/cm 2 , preferably in the range of 1 to 1000 mJ/cm 2 .
〔步驟3〕 [Step 3]
其次，將上述阻劑層2去除的同時，將導電性聚合物層剝離，形成導電性聚合物自立膜。阻劑層2為正片型阻劑層時， 如第1圖(d)所示，藉由顯影去除阻劑層2，則去除之阻劑層2上之導電性聚合物層3呈由支持體漂浮的狀態，結果，導電性聚合物層3全體被剝離而游離在顯影液中。即，可簡便而不會破損地，以游離在顯影液中的形式得到導電性聚合物自立膜3'。 Next, the resist layer 2 is removed, and the conductive polymer layer is peeled off to form a conductive polymer self-standing film. When the resist layer 2 is a positive-type resist layer, As shown in Fig. 1(d), when the resist layer 2 is removed by development, the conductive polymer layer 3 on the resist layer 2 removed is in a state of being floated by the support, and as a result, the conductive polymer layer 3 is removed. The whole was peeled off and released in the developer. That is, the conductive polymer self-standing film 3' can be obtained in a form free from the developer in a simple and non-destructive manner.
阻劑層2為正片型阻劑層時，曝光部藉由分解、離子形成等變得容易溶解於顯影液，曝光部藉由顯影去除。即，藉由將曝光部顯影去除，使導電性聚合物層3呈由支持體1漂浮的狀態，無須施加物理性的力量即可容易地剝離。結果，如第1圖(d)所示，可將極薄的導電性聚合物自立膜3'，簡便而不會破損地，以游離在顯影液中的形式得到。 When the resist layer 2 is a positive-type resist layer, the exposed portion is easily dissolved in the developer by decomposition, ion formation, or the like, and the exposed portion is removed by development. In other words, by developing and removing the exposed portion, the conductive polymer layer 3 is floated by the support 1, and can be easily peeled off without applying physical strength. As a result, as shown in Fig. 1(d), the extremely thin conductive polymer self-supporting film 3' can be obtained in a form which is free from the developer without being easily damaged.
另一方面，阻劑層2為負片型阻劑層時，未曝光部藉由顯影去除，而該未曝光部成為起點，使導電性聚合物層3被剝離，遊離在顯影液中。 On the other hand, when the resist layer 2 is a negative-type resist layer, the unexposed portion is removed by development, and the unexposed portion serves as a starting point, and the conductive polymer layer 3 is peeled off and released in the developing solution.
因此，阻劑層2為負片型阻劑層時，可省略上述步驟2。 Therefore, when the resist layer 2 is a negative-type resist layer, the above step 2 can be omitted.
顯影，係選擇使用對應所使用之光阻組成物之顯影液，以浸漬法、噴霧法、划槳法等進行。 The development is carried out by using a developing solution corresponding to the photoresist composition to be used, by a dipping method, a spraying method, a paddle method, or the like.
在於本發明，由操作性的觀點，以浸漬法為佳，浸漬法的顯影，係藉由將形成阻劑層等之支持體，浸漬於顯影液中所進行。 In the present invention, the dipping method is preferred from the viewpoint of workability, and the development by the dipping method is carried out by immersing a support such as a resist layer in a developing solution.
顯影液，只要選擇使用對應所使用之光阻組成物之顯影液即可。例如，光阻樹脂係含有鹼可溶性樹脂之正片型光阻時，顯影液，以包含：不含金屬離子之有機鹼；及非離子性界面活性劑為主成分之顯影液等。 For the developer, it is only necessary to use a developer corresponding to the photoresist composition used. For example, when the photoresist resin contains a positive-type resist of an alkali-soluble resin, the developer includes a developer containing no metal ions; and a developer containing a nonionic surfactant as a main component.
不含金屬離子之有機鹼，可直接使用作為鹼可溶性光阻組成物之顯影液所慣用者。具體可舉(i)於取代基包含直鏈狀、分枝狀或環狀一級、二級或三級胺之芳基胺、亞烷基胺及烷基胺；(ii)於環骨架具有3~5個碳原子及1~2個選自由氮、氧及硫之中之雜原子之雜環鹼等；(iii)低級烷基(碳數1~10之烷基)四級銨鹼等。 An organic base containing no metal ions can be directly used as a developer for an alkali-soluble photoresist composition. Specifically, (i) an arylamine, an alkyleneamine, and an alkylamine having a linear, branched or cyclic primary, secondary or tertiary amine; (ii) having a ring skeleton of 3 ~5 carbon atoms and 1 to 2 heterocyclic bases selected from heteroatoms among nitrogen, oxygen and sulfur; (iii) lower alkyl (alkyl 1 to 10 alkyl) quaternary ammonium bases.
(i)之具體例，可舉4,4'-二胺基二苯胺、1,3-二胺基丙烷、N,N'-二胺基二烷基胺等。(ii)之具體例，可舉吡咯、吡咯烷、吡咯烷酮、吡啶、嗎啉、哌嗪、哌啶、噁唑、噻唑等。(iii)之具體例，可舉四甲基氫氧化銨(=TMAH)、四乙基氫氧化銨、四丙基氫氧化銨、三甲基乙基氫氧化銨，(2-羥基乙基)三甲基氫氧化銨(=松脂)、(2-羥基乙基)三乙基氫氧化銨，(2-羥基乙基)三丙基氫氧化銨，(1-羥基丙基)三甲基氫氧化銨等。 Specific examples of (i) include 4,4'-diaminodiphenylamine, 1,3-diaminopropane, and N,N'-diaminodialkylamine. Specific examples of (ii) include pyrrole, pyrrolidine, pyrrolidone, pyridine, morpholine, piperazine, piperidine, oxazole, and thiazole. Specific examples of (iii) include tetramethylammonium hydroxide (=TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, trimethylethylammonium hydroxide, (2-hydroxyethyl). Trimethylammonium hydroxide (= rosin), (2-hydroxyethyl)triethylammonium hydroxide, (2-hydroxyethyl)tripropylammonium hydroxide, (1-hydroxypropyl)trimethylhydrogen Ammonium oxide, etc.
該等之中，由可簡便且容易地去除阻劑層2，以(iii)低級烷基(碳數1~10之烷基)四級銨鹼為佳，以四甲基氫氧化銨(TMAH)、(2-羥基乙基)三甲基氫氧化銨(=膽鹼)特別佳。 Among these, the resist layer 2 can be easily and easily removed, and (iii) a lower alkyl group (alkyl group having 1 to 10 carbon atoms) quaternary ammonium base is preferred, and tetramethylammonium hydroxide (TMAH) is used. (2-hydroxyethyl)trimethylammonium hydroxide (=choline) is particularly preferred.
顯影溫度，並無特別限定，通常為15~40℃。 The development temperature is not particularly limited and is usually 15 to 40 °C.
顯影時間，並無特別限定，以15秒至5分鐘的範圍為佳 The development time is not particularly limited, and it is preferably in the range of 15 seconds to 5 minutes.
〔步驟4〕 [Step 4]
在於本發明之形成方法，步驟3之後，進一步包含對剝離之導電性聚合物層，進行離子交換處理之步驟4為佳。 In the method for forming the present invention, after step 3, the step 4 of performing ion exchange treatment on the peeled conductive polymer layer is further preferred.
在於上述步驟3，藉由導電性聚合物層3浸漬於顯影液中，導電性聚合物的摻雜離子之全部或一部分以羥基離子交換。導電性聚合物的摻雜離子以羥基離子取代，則會發生導電 性聚合物膜的導電性顯著地下降的不適。因此，步驟4，係將該羥基離子，再交換成摻雜離子而進行者。 In the above step 3, the conductive polymer layer 3 is immersed in the developer, and all or a part of the dopant ions of the conductive polymer are exchanged with hydroxyl groups. When the doping ions of the conductive polymer are replaced by hydroxyl ions, conduction occurs. The conductivity of the polymer film is remarkably lowered. Therefore, in step 4, the hydroxyl ions are exchanged for doping ions.
離子交換處理，係藉由使導電性聚合物自立膜與離子交換溶液接觸而進行。離子交換處理的方法，具體而言，可舉對導電性聚合物自立膜噴霧離子交換溶液之方法、將導電性聚合物自立膜浸漬於離子交換溶液中的方法等，後者的方法較簡便而佳。更具體而言，將游離之導電性聚合物層(自立膜)由顯影液移到離子交換溶液之中之後，根據所期望進一步添加離子交換溶液，藉由以常溫靜置數秒至數分鐘而進行。 The ion exchange treatment is carried out by bringing the conductive polymer from the standing film into contact with the ion exchange solution. The method of ion exchange treatment specifically includes a method of spraying an ion exchange solution on a conductive polymer from a standing film, a method of immersing a conductive polymer in a separation membrane in an ion exchange solution, and the like, and the latter method is simple and preferable. . More specifically, after the free conductive polymer layer (self-standing film) is transferred from the developer to the ion exchange solution, the ion exchange solution is further added as desired, and is allowed to stand at room temperature for several seconds to several minutes. .
使用之離子交換溶液，只要按照所使用之導電性聚合物之種類選擇即可，使用作為上述摻雜物例示之離子之溶液為佳。具體而言，可舉甲苯磺酸鈉水溶液、聚苯乙烯磺酸鈉水溶液、樟腦磺酸鈉水溶液等。該等之中，由可良好地進行離子交換，可得導電性更優良的導電性聚合物自立膜之觀點，以聚苯乙烯磺酸鈉水溶液、樟腦磺酸鈉水溶液為佳。 The ion exchange solution to be used may be selected according to the type of the conductive polymer to be used, and a solution of the ions exemplified as the above dopant is preferably used. Specifically, an aqueous solution of sodium toluenesulfonate, an aqueous solution of sodium polystyrene sulfonate, an aqueous solution of sodium camphorsulfonate or the like can be given. Among these, it is preferable to use an aqueous solution of sodium polystyrene sulfonate or an aqueous solution of sodium camphorsulfonate from the viewpoint of obtaining a conductive polymer which is excellent in conductivity by ion exchange.
離子交換溶液之濃度，只要對離子交換充分的量的離子濃度，並無特別限定，通常為1~5質量% The concentration of the ion exchange solution is not particularly limited as long as the ion concentration is sufficient for ion exchange, and is usually 1 to 5% by mass.
根據本發明之形成方法，可將導電性聚合物自立膜，以遊離在溶液中的狀態得到，將此由溶液中撈起，以導電性聚合物自立膜使用於各種目的。 According to the formation method of the present invention, the conductive polymer can be obtained from the standing film in a state of being free from the solution, and this can be picked up from the solution to be used for various purposes with the conductive polymer-free film.
所得導電性聚合物自立膜之厚度，與上述導電性聚合物層的厚度大致相同，通常為10~5000nm，以50~1000nm為佳，以50~500nm更佳，以50~200nm的厚度特別佳，未滿10nm則作為自立膜之操作性顯著地變差，此外，超過5000nm， 則透明性下降而不佳。 The thickness of the obtained conductive polymer self-standing film is substantially the same as the thickness of the conductive polymer layer, and is usually 10 to 5000 nm, preferably 50 to 1000 nm, more preferably 50 to 500 nm, and particularly preferably 50 to 200 nm. When the thickness is less than 10 nm, the workability as a self-supporting film is remarkably deteriorated, and more than 5000 nm, Then the transparency is not good.
根據本發明之形成方法，即使不使用造膜性高的導電性聚合物，亦可以較大面積簡便地得到，具有平滑且均一，厚度由奈米級至次微米級的極薄導電性聚合物自立膜。 According to the formation method of the present invention, even if a conductive polymer having high film formability is not used, it can be easily obtained in a large area, and has a smooth and uniform thickness, and a very thin conductive polymer having a thickness ranging from nanometer to submicron is self-supporting. membrane.
2)導電性聚合物自立膜 2) Conductive polymer self-standing film
本發明之導電性聚合物自立膜3'，係藉由上述本發明之導電性聚合物自立膜之形成方法所得者。因此，本發明之導電性聚合物自立膜3'，係平滑且均勻而厚度為奈米級至次微米級之薄膜。 The conductive polymer self-standing film 3' of the present invention is obtained by the above-described method for forming a conductive polymer self-standing film of the present invention. Therefore, the conductive polymer self-standing film 3' of the present invention is a film which is smooth and uniform and has a thickness of from nanometer to submicron.
本發明之導電性聚合物自立膜3'，可於各種基材上，無須使用接著劑，即可層積。特別是，使用本發明之導電性聚合物自立膜，則通常難以形成導電性聚合物之紙類、不織布、網布等的多孔質基材；或表面粗糙度大的基材；具有曲面的基材等上，簡便地層積導電膜。 The conductive polymer self-standing film 3' of the present invention can be laminated on various substrates without using an adhesive. In particular, when the conductive polymer self-supporting film of the present invention is used, it is generally difficult to form a porous substrate such as a paper, a nonwoven fabric, or a mesh of a conductive polymer; or a substrate having a large surface roughness; A conductive film is simply laminated on a material or the like.
本發明之導電性聚合物自立膜3'之表面電阻值，通常為500~10000Ω/sq，可充份發揮作為導電膜之功能 The surface resistivity of the conductive polymer self-standing film 3' of the present invention is usually 500 to 10000 Ω/sq, and can fully function as a conductive film.
3)導電性層積體 3) Conductive laminate
本發明之導電性層積體，係將藉由上述本發明之導電性聚合物自立膜之形成方法所得之導電性聚合物自立膜3'，層積於基材上。 The conductive laminate of the present invention is obtained by laminating a conductive polymer self-standing film 3' obtained by the above-described method for forming a conductive polymer self-standing film of the present invention on a substrate.
藉由使用本發明之形成方法所得之導電性聚合物自立膜3'，僅於基材上層積乾燥，無須使用接著劑，即可簡便地得到導電性層積體 By using the conductive polymer self-standing film 3' obtained by the formation method of the present invention, it is only dried on the substrate, and the conductive laminate can be easily obtained without using an adhesive.
具體而言，如第2圖(a)所示，藉由上述本發明之 形成方法，將以游離在溶液中的狀態所得之導電性聚合物自立膜3'，由溶液中撈取層積於基材4。接著，藉由使附著於表面上的溶劑(水份)揮發，可得如第2圖(b)所示，導電性聚合物自立膜3'層積於基材4上之導電性層積體5。 Specifically, as shown in FIG. 2(a), by the above invention In the formation method, the conductive polymer self-standing film 3' obtained in a state of being freed from the solution is taken up from the solution and laminated on the substrate 4. Then, by volatilizing the solvent (moisture) adhering to the surface, the conductive laminate in which the conductive polymer self-standing film 3' is laminated on the substrate 4 can be obtained as shown in Fig. 2(b). 5.
此外，根據期望，為將游離的離子完全去除，可將導電性聚合物自立膜3'層積於基材4之後，以離子交換溶液沖洗導電性聚合物自立膜3'。 Further, as desired, in order to completely remove the free ions, the conductive polymer self-standing film 3' may be laminated on the substrate 4, and the conductive polymer-free film 3' may be washed with an ion exchange solution.
基材4，並無特別限制，可使用玻璃、紙類、纖維、合成樹脂等的各種材質者。此外，其表面，可為平滑者，亦可為粗糙者。此外，亦可為網目狀者。 The base material 4 is not particularly limited, and various materials such as glass, paper, fiber, and synthetic resin can be used. In addition, the surface may be smooth or rough. In addition, it can also be a mesh.
再者，基材之形狀，亦無特別限制，可為平坦的片狀，亦可為具有曲面者。 Further, the shape of the substrate is not particularly limited, and may be a flat sheet shape or a curved surface.
在於本發明，基材4，即使是紙類、不織布、網布等的多孔質基材；表面粗糙度大的基材；具有曲面的基材等的表面不平滑，而難以直接在基材上形成導電性聚合物層之基材之情形，亦可得到具有優良的導電性之導電性層積體。 In the present invention, the substrate 4 is a porous substrate such as paper, non-woven fabric, or mesh; a substrate having a large surface roughness; a surface of a substrate having a curved surface or the like is not smooth, and is difficult to directly on the substrate. In the case of forming a substrate of a conductive polymer layer, a conductive laminate having excellent conductivity can also be obtained.
本發明之導電性層積體之表面電阻值，通常為500~10000Ω/sq，可充分發揮作為導電膜之功能。 The surface resistivity of the conductive laminate of the present invention is usually 500 to 10000 Ω/sq, and the function as a conductive film can be sufficiently exhibited.
此外，本發明之導電性層積體5，由於具有本發明之導電性聚合物自立膜作為導電膜，故基材4即使是紙類、不織布、網布等的多孔質基材；表面粗糙度大的基材；具有曲面的基材等，難以直接在基材上形成導電性聚合物層之基材，亦可於其表面上，簡便且容易地形成具有奈米等級至次微米等級的膜厚非常薄，均勻的膜質之導電膜。所得導電性層積體，具 有優良的功能。 Further, since the conductive laminate 5 of the present invention has the conductive polymer self-standing film of the present invention as a conductive film, the substrate 4 is a porous substrate such as a paper, a nonwoven fabric or a mesh; A large substrate; a substrate having a curved surface; etc., it is difficult to form a substrate of a conductive polymer layer directly on a substrate, and a film having a nanometer to submicron order can be easily and easily formed on the surface thereof. A very thin, uniform film-like conductive film. The resulting conductive laminate, Has excellent features.
[實施例] [Examples]
以下將本發明，以實施例更詳細地說明，惟本發明不應有任何限定於實施例者。 The invention is described in more detail below by way of examples, but the invention should not be limited to the examples.
(表面電阻的測定) (Measurement of surface resistance)
將導電性聚合物自立膜，以四線式電阻率計(三菱化學ANALYTIC公司製，Loresta MCP-T360)測定 The conductive polymer was measured by a four-wire resistivity meter (manufactured by Mitsubishi Chemical Corporation, Loresta MCP-T360).
(實施例1) (Example 1)
於玻璃基板(支持體)上，將正片型光阻材料(東京應化工業公司製，OFPR-800LB)，塗佈使乾燥後的厚度為1μm，將所得塗膜以130℃加熱3分鐘加熱乾燥，形成阻劑層。 On a glass substrate (support), a positive-working photoresist (OFPR-800LB, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied to a thickness of 1 μm after drying, and the obtained coating film was heated and dried at 130 ° C for 3 minutes. Forming a resist layer.
於所得阻劑層上，作為導電性聚合物層形成用組成物，將聚(3,4)-亞乙基噻吩/聚苯乙烯磺酸酯(PEDOT：PSS)水分散液(日本AGFA Materials公司製，S305)塗佈，使乾燥後的厚度為100nm，將所得塗膜以130℃乾燥10分鐘，形成導電性聚合物層。 On the obtained resist layer, as a composition for forming a conductive polymer layer, a poly(3,4)-ethylene thiophene/polystyrene sulfonate (PEDOT:PSS) aqueous dispersion (Japan AGFA Materials Co., Ltd.) The coating was applied to S305) to a thickness of 100 nm after drying, and the obtained coating film was dried at 130 ° C for 10 minutes to form a conductive polymer layer.
之後，於光源使用氙燈，由支持體側對阻劑層進行光照射。接著，將阻劑層浸漬於顯影液〔東京應化工業公司製，NMD-3(四甲基氫氧化銨)〕使阻劑層溶解。藉此去除該阻劑層，使紅紫色的導電性聚合物層由支持體剝離，游離在顯影液中。 Thereafter, a xenon lamp was used for the light source, and the resist layer was irradiated with light by the support side. Next, the resist layer was immersed in a developing solution (manufactured by Tokyo Ohka Kogyo Co., Ltd., NMD-3 (tetramethylammonium hydroxide)) to dissolve the resist layer. Thereby, the resist layer is removed, and the red-violet conductive polymer layer is peeled off from the support and released in the developer.
將游離在顯影液中的導電性聚合物層，浸漬在作為離子交換溶液之對甲苯磺酸鈉水溶液(東京化成工業公司製，5質量%)10ml中，進行離子交換處理。藉此，得到厚度100nm之藍色透明的導電性聚合物自立膜。 The conductive polymer layer which was released in the developing solution was immersed in 10 ml of a sodium p-toluenesulfonic acid aqueous solution (manufactured by Tokyo Chemical Industry Co., Ltd., 5 mass%) as an ion exchange solution, and subjected to ion exchange treatment. Thereby, a blue transparent conductive polymer self-standing film having a thickness of 100 nm was obtained.
接著，將游離在離子交換溶液中的狀態的導電性聚合物自立膜，由離子交換溶液撈取，層積於作為基材之玻璃板上。接著，使表面的水分揮發，得到導電性層積體。 Next, the conductive polymer in a state of being freed in the ion exchange solution was taken up from the ion exchange solution and laminated on a glass plate as a substrate. Next, the water on the surface is volatilized to obtain a conductive laminate.
所得導電性聚合物自立膜之表面電阻值為6300Ω/sq，確認可充分作用作為導電膜。 The surface resistivity of the obtained conductive polymer self-standing film was 6300 Ω/sq, and it was confirmed that it can fully function as a conductive film.
(實施例2) (Example 2)
在於實施例1，作為離子交換溶液，將對甲苯磺酸鈉水溶液，以聚苯乙烯磺酸鈉水溶液(Sigma-Aldrich公司製)取代以外，以與實施例1同樣地，得到厚度100nm的藍色透明的導電性聚合物自立膜。接著，以與實施例1同樣地，製作導電性層積體。所得導電性聚合物自立膜之表面電阻值為1200Ω/sq，確認可充分作用作為導電膜。 In the same manner as in Example 1, except that the sodium p-toluenesulfonic acid aqueous solution was replaced with a sodium polystyrenesulfonate aqueous solution (manufactured by Sigma-Aldrich Co., Ltd.) as an ion exchange solution, a blue color of 100 nm was obtained. Transparent conductive polymer self-standing film. Next, a conductive laminate was produced in the same manner as in Example 1. The surface resistivity of the obtained conductive polymer self-standing film was 1200 Ω/sq, and it was confirmed that it can fully function as a conductive film.
(實施例3) (Example 3)
在於實施例1，作為離子交換溶液，將對甲苯磺酸鈉水溶液，以樟腦磺酸鈉水溶液(東京化成工業公司製)取代以外，以與實施例1同樣地，得到厚度100nm的藍色透明的導電性聚合物自立膜。接著，以與實施例1同樣地，製作導電性層積體。所得導電性聚合物自立膜之表面電阻值為1400Ω/sq，確認可充分作用作為導電膜。 In the same manner as in Example 1, except that the sodium p-toluenesulfonic acid aqueous solution was replaced with an aqueous solution of sodium camphorsulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) as an ion exchange solution, a blue transparent layer having a thickness of 100 nm was obtained. Conductive polymer self-standing film. Next, a conductive laminate was produced in the same manner as in Example 1. The surface resistivity of the obtained conductive polymer self-standing film was 1400 Ω/sq, and it was confirmed that it can fully function as a conductive film.
(實施例4) (Example 4)
在於實施例1，作為導電性聚合物層形成用的材料，取代PEDOT：PSS，使用聚苯胺鹽水分散液(日產化學工業公司製，D1033W)以外，以與實施例1同樣地，得到厚度100nm的綠色透明的導電性聚合物自立膜。接著，以與實施例1同樣地，製 作導電性層積體。所得導電性聚合物自立膜之表面電阻值為970Ω/sq，確認可充分作用作為導電膜。 In the same manner as in Example 1, except that PEDOT:PSS was used as the material for forming a conductive polymer layer, a polyaniline salt dispersion (D1033W, manufactured by Nissan Chemical Industries, Ltd.) was used. Green transparent conductive polymer self-standing film. Next, in the same manner as in the first embodiment, It is used as a conductive laminate. The surface resistivity of the obtained conductive polymer self-standing film was 970 Ω/sq, and it was confirmed that it can fully function as a conductive film.
(實施例5) (Example 5)
在於實施例1，作為導電性聚合物層形成用的材料，取代PEDOT：PSS，使用聚苯胺鹽水分散液(日產化學工業公司製，D1033W)，作為離子交換溶液，將對甲苯磺酸鈉水溶液以聚苯乙烯磺酸鈉水溶液(Sigma-Aldrich公司製)取代以外，以與實施例1同樣地，得到厚度100nm的綠色透明的導電性聚合物自立膜。接著，以與實施例1同樣地，製作導電性層積體。所得導電性聚合物自立膜之表面電阻值為650Ω/sq，確認可充分作用作為導電膜。 In the first embodiment, as a material for forming a conductive polymer layer, in place of PEDOT:PSS, a polyaniline salt dispersion (D1033W, manufactured by Nissan Chemical Industries, Ltd.) was used, and an aqueous solution of sodium p-toluenesulfonate was used as an ion exchange solution. A green transparent conductive polymer self-supporting film having a thickness of 100 nm was obtained in the same manner as in Example 1 except that a sodium polystyrenesulfonate aqueous solution (manufactured by Sigma-Aldrich Co., Ltd.) was used. Next, a conductive laminate was produced in the same manner as in Example 1. The surface resistivity of the obtained conductive polymer self-standing film was 650 Ω/sq, and it was confirmed that it can fully function as a conductive film.
(實施例6) (Example 6)
在於實施例1，作為導電性聚合物層形成用的材料，取代PEDOT：PSS使用聚苯胺鹽水分散液(日產化學工業公司製，D1033W)，作為離子交換溶液，將對甲苯磺酸鈉水溶液以樟腦磺酸鈉水溶液(東京化成工業公司製)取代外，以與實施例1同樣地，得到厚度100nm的綠色透明的導電性聚合物自立膜。接著，以與實施例1同樣地，製作導電性層積體。所得導電性聚合物自立膜之表面電阻值為700Ω/sq，確認可充分作用作為導電膜。 In the first embodiment, as a material for forming a conductive polymer layer, a polyaniline salt dispersion (D1033W, manufactured by Nissan Chemical Industries, Ltd.) was used instead of PEDOT:PSS, and an aqueous solution of sodium p-toluenesulfonate was used as a camphor solution. A green transparent conductive polymer self-supporting film having a thickness of 100 nm was obtained in the same manner as in Example 1 except that the sodium sulfonate aqueous solution (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced. Next, a conductive laminate was produced in the same manner as in Example 1. The surface resistivity of the obtained conductive polymer self-standing film was 700 Ω/sq, and it was confirmed that it can fully function as a conductive film.
(比較例1) (Comparative Example 1)
以與實施例1同樣地，於阻劑層上形成導電性聚合物層。接著，不以氙燈進行光照射，浸漬於顯影液(東京應化工業公司製，NMD-3)。導電性聚合物層無法在顯影液中由阻劑層剝 離，無法得到導電性聚合物自立膜。 In the same manner as in Example 1, a conductive polymer layer was formed on the resist layer. Then, the light was not irradiated with a xenon lamp, and it was immersed in a developing solution (NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.). The conductive polymer layer cannot be stripped by the resist layer in the developer The conductive polymer self-standing film could not be obtained.
(比較例2) (Comparative Example 2)
在於實施例1，不形成阻劑層，而直接將導電性聚合物層形成於支持體上。接著，以與實施例1同樣地浸漬於顯影液(東京應化工業公司製，NMD-3)。導電性聚合物層無法在顯影液中由阻劑層剝離，無法得到導電性聚合物自立膜。 In Example 1, the resist polymer layer was not formed, and the conductive polymer layer was directly formed on the support. Then, it was immersed in a developing solution (NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) in the same manner as in Example 1. The conductive polymer layer could not be peeled off from the resist layer in the developer, and the conductive polymer self-standing film could not be obtained.
(實施例7) (Example 7)
將實施例5所得之遊離在離子交換溶液之狀態之導電性聚合物自立膜，由離子交換溶液撈取，層積於作為基材之聚四氟乙烯網目(間距127μm)上。接著，使表面的水分揮發，得到導電性層積體。所得導電性層積體之導電性聚合物自立膜之表面電阻值為890Ω/sq，確認可充分作用作為導電膜。 The conductive polymer self-standing film obtained in the state of the ion exchange solution obtained in Example 5 was taken up from the ion exchange solution and laminated on a polytetrafluoroethylene mesh (pitch of 127 μm) as a substrate. Next, the water on the surface is volatilized to obtain a conductive laminate. The surface resistivity of the conductive polymer-free laminated film of the obtained conductive laminate was 890 Ω/sq, and it was confirmed that it can sufficiently function as a conductive film.
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| JPS6470537A (en) * | 1987-05-22 | 1989-03-16 | Mitsui Mining & Smelting Co | Highly electrically conductive high polymer film and production thereof |
| JPH11312627A (en) * | 1998-04-28 | 1999-11-09 | Matsushita Electric Ind Co Ltd | Capacitor and its manufacture |
| JP2003342307A (en) * | 2003-04-10 | 2003-12-03 | Japan Polyolefins Co Ltd | Protective film and its manufacturing process |
| WO2007122884A1 (en) * | 2006-04-21 | 2007-11-01 | Riken | Method for production of polymer thin film, and polymer thin film |
| JP2008285617A (en) * | 2007-05-21 | 2008-11-27 | Institute Of Physical & Chemical Research | Preparation of polymer thin film and polymer thin film |
| JP2009011103A (en) * | 2007-06-28 | 2009-01-15 | Nissan Motor Co Ltd | Movable conductive polymer resin material and manufacturing method thereof |
| JP2009029695A (en) * | 2007-06-29 | 2009-02-12 | Toray Ind Inc | Aggregate of carbon nanotubes, dispersion thereof and conductive film |
| WO2012070016A1 (en) * | 2010-11-24 | 2012-05-31 | Scuola Superiore Di Studi Universitari E Di Perfezionamento Sant'anna | Process for the preparation of biocompatible, free-standing nanofilms of conductive polymers |
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| JPS6470537A (en) * | 1987-05-22 | 1989-03-16 | Mitsui Mining & Smelting Co | Highly electrically conductive high polymer film and production thereof |
| JPH11312627A (en) * | 1998-04-28 | 1999-11-09 | Matsushita Electric Ind Co Ltd | Capacitor and its manufacture |
| JP2003342307A (en) * | 2003-04-10 | 2003-12-03 | Japan Polyolefins Co Ltd | Protective film and its manufacturing process |
| WO2007122884A1 (en) * | 2006-04-21 | 2007-11-01 | Riken | Method for production of polymer thin film, and polymer thin film |
| JP2008285617A (en) * | 2007-05-21 | 2008-11-27 | Institute Of Physical & Chemical Research | Preparation of polymer thin film and polymer thin film |
| JP2009011103A (en) * | 2007-06-28 | 2009-01-15 | Nissan Motor Co Ltd | Movable conductive polymer resin material and manufacturing method thereof |
| JP2009029695A (en) * | 2007-06-29 | 2009-02-12 | Toray Ind Inc | Aggregate of carbon nanotubes, dispersion thereof and conductive film |
| WO2012070016A1 (en) * | 2010-11-24 | 2012-05-31 | Scuola Superiore Di Studi Universitari E Di Perfezionamento Sant'anna | Process for the preparation of biocompatible, free-standing nanofilms of conductive polymers |
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