TWI673308B - Conductive polymer material and substrate - Google Patents

Conductive polymer material and substrate Download PDF

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TWI673308B
TWI673308B TW104129666A TW104129666A TWI673308B TW I673308 B TWI673308 B TW I673308B TW 104129666 A TW104129666 A TW 104129666A TW 104129666 A TW104129666 A TW 104129666A TW I673308 B TWI673308 B TW I673308B
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畠山潤
長澤賢幸
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日商信越化學工業股份有限公司
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    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
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Abstract

本發明係提供一種酸性度低，可抑制經過時間之粒子之凝聚，且在溶液中之安定性良好的導電性聚合物材料。本發明之導電性聚合物材料，其係含有(A)π共軛系聚合物、及(B)具有磺基之重複單位，且重量平均分子量為1,000~500,000之範圍者的摻雜劑聚合物、(C)下述一般式(1-1)、(1-2)表示之鋶鹽化合物之任一方或兩方者。 The present invention provides a conductive polymer material with low acidity, which can suppress the aggregation of particles that have passed over time, and has good stability in solution. The conductive polymer material of the present invention is a dopant polymer containing (A) a π-conjugated polymer and (B) a repeating unit having a sulfo group and having a weight average molecular weight in the range of 1,000 to 500,000. (C) Either or both of the phosphonium salt compounds represented by the following general formulae (1-1) and (1-2).

Description

導電性聚合物材料及基板 Conductive polymer materials and substrates

本發明係有關導電性聚合物材料及藉由該導電性聚合物材料形成導電膜的基板。 The present invention relates to a conductive polymer material and a substrate on which a conductive film is formed from the conductive polymer material.

具有共軛雙鍵之聚合物(π共軛系聚合物)，此聚合物本身不具有導電性，但藉由摻雜適當的陰離子分子而展現導電性，成為導電性高分子材料(導電性聚合物組成物)。π共軛系聚合物可使用聚乙炔(Polyacetylene)、聚噻吩、聚硒吩、聚碲吩、聚吡咯、聚苯胺等之(雜)芳香族聚合物及此等之混合物等，而陰離子分子(摻雜劑)最常使用磺酸系之陰離子。此乃是因為強酸的磺酸與上述π共軛系聚合物以效率良好相互作用的緣故。 A polymer with a conjugated double bond (π-conjugated polymer). This polymer does not have conductivity by itself, but it exhibits conductivity by doping an appropriate anionic molecule and becomes a conductive polymer material (conductive polymer物 组合 物)). As the π-conjugated polymer, (hetero) aromatic polymers such as polyacetylene, polythiophene, polyselenophene, polytellurene, polypyrrole, polyaniline, and mixtures thereof can be used, and the anionic molecules ( Dopants) most commonly use sulfonic acid based anions. This is because the strong acid sulfonic acid and the π-conjugated polymer interact with each other with good efficiency.

磺酸系之陰離子摻雜劑(dopant)，例如聚乙烯基磺酸或聚苯乙烯磺酸(PSS)等之磺酸聚合物被廣泛使用(專利文獻1)。又，磺酸聚合物也有註冊商標NAFION所代表之乙烯基全氟烷基醚磺酸，其被使用於燃 料電池用途。 A sulfonic acid-based anionic dopant such as a sulfonic acid polymer such as polyvinyl sulfonic acid or polystyrene sulfonic acid (PSS) is widely used (Patent Document 1). In addition, the sulfonic acid polymer also has a vinyl perfluoroalkyl ether sulfonic acid represented by the registered trademark NAFION, which is used for combustion Battery use.

磺酸均聚合物之聚苯乙烯磺酸(PSS)係對於聚合物主鏈，磺酸以單體單位連續存在，因此相對於π共軛系聚合物之摻雜為高效率，又可提升摻雜後之π共軛系聚合物對於水的分散性。此乃是因為藉由過剩存在於PSS之磺基之存在，而保持親水性，故可飛躍式提升對於水之分散性的緣故。 Polystyrene sulfonic acid (PSS) of homopolymer of sulfonic acid is a kind of polymer main chain, the sulfonic acid continuously exists in monomer units, so it is more efficient than the doping of π-conjugated polymers, and can improve the doping. Dispersibility of the hybrid π-conjugated polymer in water. This is because the presence of sulfo groups in the PSS is excessive and the hydrophilicity is maintained, so the dispersibility with respect to water can be greatly improved.

以PSS作為摻雜劑之聚噻吩因高導電性且可作為水分散液處理，故被期待作為取代ITO(銦-錫氧化物)之塗佈型導電膜材料。但是如上述，PSS為水溶性樹脂，且幾乎不溶解於有機溶劑。因此，以PSS作為摻雜劑之聚噻吩，其親水性變高，但對於有機溶劑或有機基板之親和性低，故分散於有機溶劑，於有機基板上成膜困難。 Polythiophene using PSS as a dopant is expected to be used as a coating-type conductive film material that replaces ITO (indium-tin oxide) because it has high conductivity and can be treated as an aqueous dispersion. However, as described above, PSS is a water-soluble resin and is hardly soluble in organic solvents. Therefore, polythiophene using PSS as a dopant has higher hydrophilicity, but has lower affinity for organic solvents or organic substrates, so it is difficult to disperse in organic solvents and form films on organic substrates.

又，將以PSS作為摻雜劑之聚噻吩，例如使用於有機EL照明用之導電膜的情形，如上述，以PSS作為摻雜劑之聚噻吩之親水性非常高，故導電膜中容易殘存大量水份，又形成之導電膜易由外部環境吸取水份。結果有機EL之發光體產生化學變化而降低發光能力，隨著時間經過，水份凝聚成為缺陷，故有縮短有機EL裝置整體壽命的問題。又，以PSS為摻雜劑之聚噻吩有在水分散液中之粒子大，膜形成後之膜表面之凹凸大，或使用於有機EL照明時，產生被稱為暗點(dark spot)之未發光部分的問題。 In addition, polythiophene using PSS as a dopant, for example, is used in a conductive film for organic EL lighting. As described above, polythiophene using PSS as a dopant is very hydrophilic, so it is easy to remain in the conductive film. A large amount of water, and the conductive film formed can easily absorb water from the external environment. As a result, the luminous body of the organic EL is chemically changed to reduce the luminous ability. As time passes, water condensation becomes a defect, so there is a problem of shortening the overall life of the organic EL device. In addition, polythiophene using PSS as a dopant has large particles in an aqueous dispersion, and has a large unevenness on the surface of the film after the film is formed, or when used in organic EL lighting, it produces a dark spot. Problems with non-lighting parts.

又，將PSS作為摻雜劑的聚噻吩係因在波長 500nm附近的藍色區域具有吸收，故將該材料塗佈於透明電極等之透明的基板上來使用的情形，為了使裝置產生功能所需要的導電率，以固體成份濃度或膜厚來補足時，會有影響對於作為構件之透過率的問題。 In addition, the polythiophene system using PSS as a dopant has a wavelength The blue area near 500nm has absorption, so when this material is applied to a transparent substrate such as a transparent electrode and used, in order to make the device have the required conductivity, the solid content concentration or film thickness is used to make up There is a problem that affects the transmittance as a component.

此外，將PSS作為摻雜劑的聚噻吩中，π共軛系聚合物與摻雜劑聚合物之量關係係PSS之磺基的莫耳數相對於噻吩之莫耳數為過剩。如此，因高親水性之磺基過剩存在，而使導電性複合體分散於水中。因此，導電性聚合物水分散液為強酸性。但是強酸性的水溶液對金屬之腐蝕性高，使用上要注意。 In addition, in the polythiophene using PSS as a dopant, the relationship between the amount of the π-conjugated polymer and the dopant polymer is that the mole number of the sulfo group of the PSS is excessive relative to the mole number of the thiophene. In this manner, the sulfo group with high hydrophilicity is excessively present, and the conductive composite is dispersed in water. Therefore, the conductive polymer aqueous dispersion is strongly acidic. However, the strongly acidic aqueous solution is highly corrosive to metals and should be used with caution.

為了中和強酸性的水溶液，而提案添加作為導電性材料組成物之鹼性化合物的方法(專利文獻2、專利文獻3)。在此，例示添加具有胺基之鹼性化合物。 In order to neutralize a strongly acidic aqueous solution, a method of adding a basic compound as a conductive material composition is proposed (Patent Document 2, Patent Document 3). Here, the addition of a basic compound having an amine group is exemplified.

專利文獻4提案一種藉由下述導電性高分子所形成之導電性聚合物組成物，其中前述導電性高分子包含：藉由選自噻吩、硒吩、碲吩、吡咯、苯胺、多環式芳香族化合物之重複單位所形成之π共軛系聚合物；與可以有機溶劑潤濕，且50%以上被陽離子中和的氟化酸聚合物。在此，陽離子例如有鋰或鈉等之鹼金屬、胺化合物。 Patent Document 4 proposes a conductive polymer composition formed by the following conductive polymer, wherein the conductive polymer includes: selected from the group consisting of thiophene, selenophene, tellurene, pyrrole, aniline, and polycyclic A π-conjugated polymer formed by repeating units of aromatic compounds; and a fluorinated acid polymer that can be wetted with an organic solvent and more than 50% neutralized by cations. Examples of the cation include alkali metals such as lithium and sodium, and amine compounds.

但是以前述陽離子或胺化合物進行中和的情形，水溶液可為中性化，但是產生導電性降低的問題。因此，期望開發導電性不會降低，且為中性之溶液的導電性材料。 However, in the case of neutralization with the aforementioned cation or amine compound, the aqueous solution may be neutralized, but there is a problem that the conductivity is lowered. Therefore, it is desired to develop a conductive material that does not decrease in conductivity and is a neutral solution.

又，將PSS作為摻雜劑之聚噻吩的水分散液 成為粒子的集合體。將PSS作為摻雜劑之聚噻吩的複合體在聚合後，必須藉由分散機將粒子微細粉碎，但是經過時間，粒子會變大。此可能是因PSS-聚噻吩複合體之粒子間之離子鍵，使集合體成長的緣故。粒子變大時，旋轉塗佈等塗佈導電性溶液時，產生條紋，變得無法形成平坦的膜，將此使用於有機EL照明時，成為暗點的原因。因此，需要開發一種經過時間，不會產生凝聚的導電性溶液材料。 An aqueous dispersion of polythiophene using PSS as a dopant Become an aggregate of particles. After polymerization of a polythiophene composite using PSS as a dopant, the particles must be finely pulverized by a disperser, but the particles become larger over time. This may be due to the ionic bond between the particles of the PSS-polythiophene complex, which makes the aggregate grow. When the particles become larger, streaks occur when a conductive solution is applied, such as spin coating, and a flat film cannot be formed. When this is used for organic EL lighting, it becomes a cause of dark spots. Therefore, it is necessary to develop a conductive solution material that does not cause aggregation over time.

又，將PSS作為摻雜劑的聚噻吩，亦可作為電洞注入層使用。此時，於ITO等之透明電極與發光層之中間設置電洞注入層。因為藉由下部的透明電極確保導電性，故電洞注入層不需要高的導電性。而電洞注入層需要不發生暗點及高的電洞輸送能力。 In addition, polythiophene using PSS as a dopant can also be used as a hole injection layer. At this time, a hole injection layer is provided between a transparent electrode such as ITO and the light emitting layer. Since the conductivity is ensured by the lower transparent electrode, the hole injection layer does not need high conductivity. The hole injection layer needs no dark spots and high hole transport capacity.

[先前技術文獻] [Prior technical literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特開2008-146913號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2008-146913

[專利文獻2]日本特開2006-321840號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2006-321840

[專利文獻3]日本特開2014-15550號公報 [Patent Document 3] Japanese Patent Laid-Open No. 2014-15550

[專利文獻4]日本專利第5264723號 [Patent Document 4] Japanese Patent No. 5264723

[發明之概要] [Summary of Invention]

如上述，將具有磺基之摻雜劑聚合物與π共軛系聚合物進行複合化，而分散於水中的導電性聚合物溶液為強酸性，有經過時間，粒子產生凝聚的問題。 As described above, the dopant polymer having a sulfo group is compounded with the π-conjugated polymer, and the conductive polymer solution dispersed in water is strongly acidic, and there is a problem that particles agglomerate over time.

本發明有鑑於上述情形而完成者，本發明之目的係提供酸性度低，可抑制經過時間之粒子之凝聚，在溶液中之安定性良好的導電性聚合物材料。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a conductive polymer material having low acidity, which can suppress the aggregation of particles that have passed over time, and has good stability in a solution.

為了解決上述課題，本發明係提供一種導電性聚合物材料，其係含有(A)π共軛系聚合物、及(B)具有磺基之重複單位，且重量平均分子量為1,000~500,000之範圍者的摻雜劑聚合物、(C)-下述一般式(1-1)、(1-2)表示之鋶鹽化合物之任一方或兩方者。 In order to solve the above problems, the present invention provides a conductive polymer material which contains (A) a π-conjugated polymer and (B) a repeating unit having a sulfo group, and has a weight average molecular weight in a range of 1,000 to 500,000. Or dopant polymer, (C)-either or both of the phosphonium salt compounds represented by the following general formulae (1-1) and (1-2).

(式中，R1、R2、及R3各自表示鹵素原子、或具有碳數1~4之烷基的胺基、碳數1~12之直鏈狀、分枝狀或環狀之烷基、烯基、氧烷基或氧烯基、碳數6~20之芳基、或 碳數7~12之芳烷基或芳基氧烷基，也可具有烷氧基、羥基、羧基、硝基、氰基、胺基、鹵素原子、酯基、醚基、硫醚基。又，R1與R2可形成環，形成環的情形，R1與R2表示碳數1~6之伸烷基，R4、R5、及R6各自為碳數1~4之烷基。K-表示氫氧離子、氯離子、溴離子、碳酸根離子、碳酸氫根離子、硝酸根離子、羧酸根離子、磺酸根離子、亞磺酸根離子之任一者，K-為羧酸根離子的情形，可成為R1、R2、及R3之任一的取代基，形成分子內鹽)。 (Wherein R 1 , R 2 , and R 3 each represent a halogen atom or an amine group having an alkyl group having 1 to 4 carbon atoms, or a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms. Group, alkenyl, oxyalkyl or oxyalkenyl, aryl having 6 to 20 carbons, or aralkyl or aryloxyalkyl having 7 to 12 carbons, and may have alkoxy, hydroxyl, carboxyl, Nitro, cyano, amine, halogen, ester, ether, and thioether. Also, when R 1 and R 2 can form a ring to form a ring, R 1 and R 2 represent a carbon number of 1 to 6. Alkyl, R 4 , R 5 , and R 6 are each an alkyl group having a carbon number of 1 to 4. K - represents hydroxide ion, chloride ion, bromide ion, carbonate ion, bicarbonate ion, nitrate ion, In the case of any of a carboxylate ion, a sulfonate ion, and a sulfinate ion, when K − is a carboxylate ion, it may be a substituent of any of R 1 , R 2 , and R 3 to form an intramolecular salt).

若為這種導電性聚合物材料，則為酸性度低，可抑制經過時間之粒子之凝聚，在溶液中之安定性良好的導電性聚合物材料。 If it is such a conductive polymer material, it is a conductive polymer material with low acidity, which can suppress the aggregation of particles over time, and has good stability in a solution.

此時，前述(B)成分為具有α位經氟化的磺基及鍵結於經氟化之芳香族基之磺基之任一或兩方者為佳。 In this case, the component (B) is preferably any one or both of a sulfonic group having a fluorinated α-position and a sulfonic group bonded to a fluorinated aromatic group.

如此，(B)成分較佳為如上述者，藉由將此與(A)成分之π共軛系聚合物進行複合化，可提高過濾性或旋轉塗佈之成膜性，可提高膜形成時之平坦性、及可見光區域之透明性。 As described above, the component (B) is preferably as described above. By compounding this with the π-conjugated polymer of the component (A), the filterability or the film-forming property of spin coating can be improved, and the film formation can be improved. Flatness at the time, and transparency in the visible light region.

此時，前述(B)成分為含有選自下述一般式(2)表示之重複單位a1~a4之1種以上者為佳。 In this case, it is preferable that the component (B) contains one or more kinds of repeating units a1 to a4 selected from the following general formula (2).

(式中，R7、R9、R12、及R14為氫原子或甲基，R8、R10、R13為單鍵、酯基、或可具有醚基、酯基之任一或此等之兩方之碳數1~12之直鏈狀、分枝狀、環狀之烴基之任一，R11為碳數1~4之直鏈狀、分枝狀之伸烷基，R11中之氫原子之中，1個或2個可被氟原子取代。R15為氟原子或三氟甲基。Z1、Z2為伸苯基、伸萘基、酯基之任一，Z3為單鍵、伸苯基、伸萘基、醚基、酯基之任一，Z4為單鍵或酯基。Z2為伸苯基的情形，R10不含醚基。p為1~4之整數，a1、a2、a3、及a4為0≦a1≦1.0、0≦a2≦1.0、0≦a3≦1.0、0≦a4≦1.0、0<a1+a2+a3+a4≦1.0)。 (Wherein R 7 , R 9 , R 12 , and R 14 are a hydrogen atom or a methyl group, and R 8 , R 10 , and R 13 are a single bond, an ester group, or any of an ether group and an ester group or Any of these two straight-chain, branched, or cyclic hydrocarbon groups having 1 to 12 carbons, and R 11 is a linear or branched alkylene group having 1 to 4 carbons, R Among the hydrogen atoms in 11 , one or two may be substituted by a fluorine atom. R 15 is a fluorine atom or a trifluoromethyl group. Z 1 and Z 2 are any of phenylene, naphthyl, and ester groups, Z 3 is any of a single bond, phenylene, naphthyl, ether group, and ester group, and Z 4 is a single bond or ester group. When Z 2 is a phenylene group, R 10 does not contain an ether group. P is Integers 1 to 4, a1, a2, a3, and a4 are 0 ≦ a1 ≦ 1.0, 0 ≦ a2 ≦ 1.0, 0 ≦ a3 ≦ 1.0, 0 ≦ a4 ≦ 1.0, 0 <a1 + a2 + a3 + a4 ≦ 1.0 ).

如此，(B)成分較佳為如上述者，可提高材料之過濾性及成膜性，對有機溶劑、基板之親和性，提高成膜後的透過率。 As described above, the component (B) is preferably as described above, which can improve the filterability and film-forming properties of the material, its affinity for organic solvents and substrates, and its transmittance after film formation.

此時，前述(B)成分為含有下述一般式(3)表示之重複單位b者為佳。 In this case, the component (B) preferably includes a repeating unit b represented by the following general formula (3).

(式中，b為0<b≦1.0)。 (In the formula, b is 0 <b ≦ 1.0).

藉由含有這種重複單位b，可進一步提高導電性。 By including such a repeating unit b, the conductivity can be further improved.

此時，前述(B)成分為嵌段共聚物為佳。 In this case, the component (B) is preferably a block copolymer.

(B)成分為嵌段共聚物時，可進一步提高導電性。 When the component (B) is a block copolymer, the conductivity can be further improved.

此時，前述(A)成分為選自由吡咯、噻吩、硒吩、碲吩、苯胺、多環式芳香族化合物、及此等之衍生物所成群之1種以上的前驅物單體進行聚合者為佳。 In this case, the component (A) is polymerized from one or more precursor monomers selected from the group consisting of pyrrole, thiophene, selenophene, tellurene, aniline, polycyclic aromatic compounds, and derivatives thereof. Those are better.

若為這種單體，則聚合容易，又在空氣中之安定性良好，故可容易合成(A)成分。 If it is such a monomer, since polymerization is easy and stability in the air is good, the component (A) can be easily synthesized.

此時，前述導電性聚合物材料係對於水或有機溶劑具有分散性者為佳。 In this case, the conductive polymer material is preferably one having dispersibility with respect to water or an organic solvent.

又，本發明係提供藉由前述導電性聚合物材料形成導電膜的基板。 The present invention also provides a substrate in which a conductive film is formed from the conductive polymer material.

如此，本發明之導電性聚合物材料，藉由塗佈、成膜於基板等，可作為導電膜。 Thus, the conductive polymer material of the present invention can be used as a conductive film by coating, forming a film on a substrate, or the like.

又，本發明係將前述導電性聚合物材料塗佈、成膜於基板等後，藉由照射波長140~400nm之光、或電子線，可提高導電性。 In addition, the present invention is to increase the conductivity by applying the above-mentioned conductive polymer material, forming a film on a substrate, or the like, and then irradiating light with a wavelength of 140 to 400 nm or an electron beam.

又，如此形成的導電膜係因導電性、透明性優異，故可作為透明電極層的功能者。 Moreover, since the conductive film formed in this way is excellent in electrical conductivity and transparency, it can function as a transparent electrode layer.

如以上，若為本發明之導電性聚合物材料， 則含有強酸之磺基的(B)成分之摻雜劑聚合物，與(A)成分之π共軛系聚合物形成複合體，藉由在此添加(C)成分之鋶鹽化合物，使溶液之酸性度降低，經過時間之粒子之凝聚被抑制，低腐蝕性且低黏性，且在溶液中之安定性及過濾性良好，旋轉塗佈之成膜性佳，又形成膜時，可形成透明性、平坦性、平滑性、耐久性、及導電性之良好的導電膜。又，若為這種導電性聚合物材料，則對於有機基板、無機基板之任一，均成為成膜性良好者。 As mentioned above, if it is the conductive polymer material of the present invention, The dopant polymer containing the strong acid sulfo (B) component and the π-conjugated polymer of the (A) component form a complex, and the sulfonium salt compound of the (C) component is added here to make the solution The acidity is reduced, the agglomeration of particles over time is suppressed, low corrosion and low viscosity, and the stability and filtration in the solution are good, the film forming property of spin coating is good, and it can form when forming a film A conductive film having good transparency, flatness, smoothness, durability, and conductivity. Moreover, if it is such a conductive polymer material, it will become a film-forming thing with respect to either an organic substrate or an inorganic substrate.

又，藉由這種導電性聚合物材料所形成之導電膜，因導電性、透明性等優異，故可成為作為透明電極層產生功能者。 In addition, a conductive film formed using such a conductive polymer material is excellent in conductivity, transparency, and the like, and thus can be used as a transparent electrode layer.

[實施發明之形態] [Form of Implementing Invention]

如上述，可開發一種酸性度低，可抑制經過時間之粒子之凝聚，在溶液中之安定性良好的導電膜形成用材料。 As described above, it is possible to develop a material for forming a conductive film that has a low acidity, can suppress the aggregation of particles with time, and has good stability in a solution.

本發明人等精心檢討上述課題的結果，作為導電性高分子材料之摻雜劑被廣泛使用之聚苯乙烯磺酸(PSS)或含有具有α位經氟化的磺基或鍵結於經氟化之芳香族基之磺基之重複單位者作為摻雜劑聚合物使用，強酸之摻雜劑聚合物與π共軛系聚合物強力相互作用，展現導電性之導電性材料中，藉由添加鋶鹽化合物，因磺基之強酸性被中和，腐蝕性降低，或導電性聚合物複合體之凝聚性降低，即使經過時間，製膜後之膜之平滑性優異，藉 由形成膜後之光照射使鋶鹽化合物分解，提高導電性，而完成本發明。 As a result of careful review of the above problems by the present inventors, polystyrene sulfonic acid (PSS), which is widely used as a dopant for conductive polymer materials, contains a fluorinated sulfo group having an α-position or is bonded to fluorine. The repeating unit of the sulfo group of the converted aromatic group is used as a dopant polymer. A strong acid dopant polymer and a π-conjugated polymer strongly interact with each other to add conductivity to a conductive material. The sulfonium salt compound is neutralized due to the strong acidity of the sulfo group, which reduces the corrosiveness, or the cohesiveness of the conductive polymer composite is reduced. Even after time passes, the smoothness of the film after film formation is excellent. The present invention is completed by decomposing the sulfonium salt compound by irradiation with light after the film is formed and improving the conductivity.

以下詳細說明本發明，但是本發明不限定於此。 Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[(A)π共軛系聚合物] [(A) π conjugated polymer]

本發明之導電性聚合物材料係包含作為(A)成分之π共軛系聚合物。此(A)成分只要是形成π共軛系鏈(單鍵與雙鍵交替地連續的結構)之前驅物單體(有機單體分子)經聚合而成者即可。 The conductive polymer material of the present invention contains a π-conjugated polymer as a component (A). This (A) component may be formed by polymerizing a precursor monomer (organic monomer molecule) that forms a π-conjugated tether (a structure in which single and double bonds are alternately continuous).

這種前驅物單體，可舉例如吡咯類、噻吩類、噻吩伸乙烯基(thiophene vinylene)類、硒吩類、碲吩類、伸苯基類、伸苯基伸乙烯基類、苯胺類等之單環式芳香族類；并苯(acene)類等之多環式芳香族類；乙炔類等，此等之單體的均聚物或共聚物可作為(A)成分使用。 Such precursor monomers include, for example, pyrrole, thiophene, thiophene vinylene, selenophene, tellurene, phenylene, phenylene, and aniline. Monocyclic aromatics; polycyclic aromatics such as acene; acetylenes; homopolymers or copolymers of these monomers can be used as the component (A).

上述單體之中，從聚合之容易度、在空氣中之穩定性的觀點，較佳為吡咯、噻吩、硒吩、碲吩、苯胺、多環式芳香族化合物、及此等之衍生物，特佳為吡咯、噻吩、苯胺、及此等之衍生物，但並非限定於此等。 Among the above monomers, from the viewpoints of ease of polymerization and stability in air, pyrrole, thiophene, selenophene, tellurene, aniline, polycyclic aromatic compounds, and derivatives thereof are preferred, Particularly preferred are pyrrole, thiophene, aniline, and derivatives thereof, but are not limited thereto.

本發明之導電性聚合物材料含有作為(A)成分特別是聚噻吩的情形，因具有高導電性與於可見光下之高透明性的特性，故認為可用於對於觸控面板或有機EL顯示器、有機EL照明等之用途。另一方面，本發明之導電性聚合物材料含有作為(A)成分之聚苯胺的情形，相 較於包含聚噻吩的情形，因於可見光下的吸收較大且導電性較低，故在顯示器相關之應用較困難，但因低黏度且旋轉塗佈容易，故認為可用於電容器之用途或在EB微影中以防止電子之帶電用之阻劑(resist)上層膜的面塗層(top coat)的用途。 When the conductive polymer material of the present invention contains (A) component, especially polythiophene, it has high conductivity and high transparency under visible light. Therefore, it is considered that it can be used for touch panels or organic EL displays, Applications for organic EL lighting. On the other hand, when the conductive polymer material of the present invention contains polyaniline as the component (A), Compared with the case of containing polythiophene, it is more difficult to be used in display-related applications due to greater absorption under visible light and lower conductivity, but because of its low viscosity and easy spin coating, it is considered to be used for capacitors or in In EB lithography, it is used as a top coat of a resist upper layer film for preventing the charging of electrons.

又，構成π共軛系聚合物之單體，即使無取代狀態，(A)成分仍可得到充份的導電性，但為了更提高導電性，亦可使用以烷基、羧基、磺基、烷氧基、羥基、氰基、鹵原子等所取代的單體。 In addition, the monomer constituting the π-conjugated polymer can obtain sufficient conductivity in the (A) component even in an unsubstituted state. However, in order to further improve the conductivity, an alkyl group, a carboxyl group, a sulfo group, A monomer substituted with an alkoxy group, a hydroxyl group, a cyano group, a halogen atom, or the like.

吡咯類、噻吩類、苯胺類之單體之具體例，可舉例吡咯、N-甲基吡咯、3-甲基吡咯、3-乙基吡咯、3-n-丙基吡咯、3-丁基吡咯、3-辛基吡咯、3-癸基吡咯、3-十二烷基吡咯、3,4-二甲基吡咯、3,4-二丁基吡咯、3-羧基吡咯、3-甲基-4-羧基吡咯、3-甲基-4-羧基乙基吡咯、3-甲基-4-羧基丁基吡咯、3-羥基吡咯、3-甲氧基吡咯、3-乙氧基吡咯、3-丁氧基吡咯、3-己氧基吡咯、3-甲基-4-己氧基吡咯；噻吩、3-甲基噻吩、3-乙基噻吩、3-丙基噻吩、3-丁基噻吩、3-己基噻吩、3-庚基噻吩、3-辛基噻吩、3-癸基噻吩、3-十二烷基噻吩、3-十八烷基噻吩、3-溴噻吩、3-氯噻吩、3-碘噻吩、3-氰基噻吩、3-苯基噻吩、3,4-二甲基噻吩、3,4-二丁基噻吩、3-羥基噻吩、3-甲氧基噻吩、3-乙氧基噻吩、3-丁氧基噻吩、3-己氧基噻吩、3-庚氧基噻吩、3-辛氧基噻吩、3-癸氧基噻吩、3-十二烷氧基噻吩、3-十八烷氧基噻吩、3,4-二羥基噻吩、3,4-二甲氧 基噻吩、3,4-二乙氧基噻吩、3,4-二丙氧基噻吩、3,4-二丁氧基噻吩、3,4-二己氧基噻吩、3,4-二庚氧基噻吩、3,4-二辛氧基噻吩、3,4-二癸氧基噻吩、3,4-二(十二烷氧基)噻吩、3,4-乙烯二氧噻吩(ethylenedioxythiophene)、3,4-乙烯二硫代噻吩、3,4-丙烯二氧噻吩、3,4-丁烯二氧噻吩、3-甲基-4-甲氧基噻吩、3-甲基-4-乙氧基噻吩、3-羧基噻吩、3-甲基-4-羧基噻吩、3-甲基-4-羧基甲基噻吩、3-甲基-4-羧基乙基噻吩、3-甲基-4-羧基丁基噻吩、3,4-(2,2-二甲基丙烯二氧基(Propylenedioxy))噻吩、3,4-(2,2-二乙基丙烯二氧基)噻吩、(2,3-二氫噻吩并[3,4-b][1,4]戴奧辛(dioxin)-2-基)甲醇；苯胺、2-甲基苯胺、3-甲基苯胺、2-乙基苯胺、3-乙基苯胺、2-丙基苯胺、3-丙基苯胺、2-丁基苯胺、3-丁基苯胺、2-異丁基苯胺、3-異丁基苯胺、2-甲氧基苯胺、2-乙氧基苯胺、2-苯胺磺酸、3-苯胺磺酸等。 Specific examples of the monomers of pyrrole, thiophene, and aniline include pyrrole, N-methylpyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, and 3-butylpyrrole. , 3-octylpyrrole, 3-decylpyrrole, 3-dodecylpyrrole, 3,4-dimethylpyrrole, 3,4-dibutylpyrrole, 3-carboxypyrrole, 3-methyl-4 -Carboxypyrrole, 3-methyl-4-carboxyethylpyrrole, 3-methyl-4-carboxybutylpyrrole, 3-hydroxypyrrole, 3-methoxypyrrole, 3-ethoxypyrrole, 3-butyl Oxypyrrole, 3-hexyloxypyrrole, 3-methyl-4-hexyloxypyrrole; thiophene, 3-methylthiophene, 3-ethylthiophene, 3-propylthiophene, 3-butylthiophene, 3 -Hexylthiophene, 3-heptylthiophene, 3-octylthiophene, 3-decylthiophene, 3-dodecylthiophene, 3-octadecylthiophene, 3-bromothiophene, 3-chlorothiophene, 3- Iodothiophene, 3-cyanothiophene, 3-phenylthiophene, 3,4-dimethylthiophene, 3,4-dibutylthiophene, 3-hydroxythiophene, 3-methoxythiophene, 3-ethoxy Thiophene, 3-butoxythiophene, 3-hexyloxythiophene, 3-heptyloxythiophene, 3-octyloxythiophene, 3-decoxythiophene, 3-dodecyloxythiophene, 3-octadecyl Thiophene, 3,4-dihydroxy thiophene, 3,4- Thiophene, 3,4-diethoxythiophene, 3,4-dipropoxythiophene, 3,4-dibutoxythiophene, 3,4-dihexyloxythiophene, 3,4-diheptyloxy Thiophene, 3,4-dioctyloxythiophene, 3,4-didecyloxythiophene, 3,4-bis (dodecyloxy) thiophene, 3,4-ethylenedioxythiophene, 3 1,4-ethylenedithiothiophene, 3,4-propylene dioxythiophene, 3,4-butene dioxythiophene, 3-methyl-4-methoxythiophene, 3-methyl-4-ethoxy Thiophene, 3-carboxythiophene, 3-methyl-4-carboxythiophene, 3-methyl-4-carboxymethylthiophene, 3-methyl-4-carboxyethylthiophene, 3-methyl-4-carboxybutyl Thiothiophene, 3,4- (2,2-Dimethylpropylenedioxy) thiophene, 3,4- (2,2-Diethylpropylenedioxy) thiophene, (2,3-Di Hydrothieno [3,4-b] [1,4] dioxin-2-yl) methanol; aniline, 2-methylaniline, 3-methylaniline, 2-ethylaniline, 3-ethyl Aniline, 2-propylaniline, 3-propylaniline, 2-butylaniline, 3-butylaniline, 2-isobutylaniline, 3-isobutylaniline, 2-methoxyaniline, 2-ethyl Oxyaniline, 2-anilinesulfonic acid, 3-anilinesulfonic acid, etc.

其中，就電阻值、反應性的觀點適合使用以選自由吡咯、噻吩、N-甲基吡咯、3-甲基噻吩、3-甲氧基噻吩、3,4-乙烯二氧噻吩之1種或2種所成之(共)聚合物。此外，以吡咯、3,4-乙烯二氧噻吩而成的均聚物為導電性高，故更佳。 Among them, from the viewpoint of resistance value and reactivity, one selected from the group consisting of pyrrole, thiophene, N-methylpyrrole, 3-methylthiophene, 3-methoxythiophene, and 3,4-ethylenedioxythiophene is suitably used. 2 types of (co) polymers. In addition, a homopolymer made of pyrrole and 3,4-ethylenedioxythiophene is more conductive because of its high conductivity.

又，由實用上的理由，(A)成分中之此等重複單位(前驅物單體)之重複數，較佳為2~20範圍內，更佳為6~15範圍內。 In addition, for practical reasons, the repeating number of such repeating units (precursor monomers) in the component (A) is preferably in the range of 2 to 20, and more preferably in the range of 6 to 15.

又，(A)成分之分子量，較佳為130~5,000左右。 The molecular weight of the component (A) is preferably about 130 to 5,000.

[(B)摻雜劑聚合物] [(B) Dopant polymer]

本發明之導電性聚合物材料含有作為(B)成分之摻雜劑聚合物。此(B)成分之摻雜劑聚合物係包含具有磺基之重複單位，較佳為具有α位經氟化的磺基及鍵結於經氟化之芳香族基之磺基之任一或兩方者，特佳為為含有選自下述一般式(2)表示之重複單位a1~a4之1種以上的超強酸性聚合物。 The conductive polymer material of the present invention contains a dopant polymer as a component (B). The dopant polymer of the component (B) contains a repeating unit having a sulfo group, preferably any one having a fluorinated sulfo group at the α position and a sulfo group bonded to a fluorinated aromatic group. In both cases, it is particularly preferred that the polymer is a super acidic polymer containing one or more kinds of repeating units a1 to a4 selected from the following general formula (2).

(式中，R7、R9、R12、及R14為氫原子或甲基，R8、R10、R13為單鍵、酯基、或可具有醚基、酯基之任一或此等之兩方之碳數1~12之直鏈狀、分枝狀、環狀之烴基之任一，R11為碳數1~4之直鏈狀、分枝狀之伸烷基，R11中之氫原子之中，1個或2個可被氟原子取代，R15為氟原子或三氟甲基。Z1、Z2為伸苯基、伸萘基、酯基之任一，Z3為單鍵、伸苯基、伸萘基、醚基、酯基之任一，Z4為單鍵或酯基。Z2為伸苯基的情形，R10不含醚基。p為1~4之整數，a1、a2、a3、及a4為0≦a1≦1.0、0≦a2≦1.0、0≦a3≦1.0、0≦a4≦1.0、0<a1+a2+a3+a4≦1.0)。 (Wherein R 7 , R 9 , R 12 , and R 14 are a hydrogen atom or a methyl group, and R 8 , R 10 , and R 13 are a single bond, an ester group, or any of an ether group and an ester group or Any of these two straight-chain, branched, or cyclic hydrocarbon groups having 1 to 12 carbons, and R 11 is a linear or branched alkylene group having 1 to 4 carbons, R Among the hydrogen atoms in 11 , one or two may be substituted by a fluorine atom, R 15 is a fluorine atom or a trifluoromethyl group. Z 1 and Z 2 are any of a phenylene group, a naphthyl group, and an ester group, Z 3 is any of a single bond, phenylene, naphthyl, ether group, and ester group, and Z 4 is a single bond or ester group. When Z 2 is a phenylene group, R 10 does not contain an ether group. P is Integers 1 to 4, a1, a2, a3, and a4 are 0 ≦ a1 ≦ 1.0, 0 ≦ a2 ≦ 1.0, 0 ≦ a3 ≦ 1.0, 0 ≦ a4 ≦ 1.0, 0 <a1 + a2 + a3 + a4 ≦ 1.0 ).

為了得到重複單位a1用之單體，具體而言， 例如下述例示。 In order to obtain a monomer for the repeating unit a1, specifically, For example, the following examples.

(式中，R7係與前述同樣，X為氫原子、鋰原子、鈉原子、鉀原子、胺化合物、或鋶化合物。) (In the formula, R 7 is the same as described above, and X is a hydrogen atom, a lithium atom, a sodium atom, a potassium atom, an amine compound, or a sulfonium compound.)

為了得到重複單位a2用之單體，具體而言，例如下述例示。 To obtain a monomer for the repeating unit a2, specifically, for example, the following examples are given.

(式中，R9係與前述同樣，X為氫原子、鋰原子、鈉原子、鉀原子、胺化合物、或鋶化合物。) (In the formula, R 9 is the same as described above, and X is a hydrogen atom, a lithium atom, a sodium atom, a potassium atom, an amine compound, or a sulfonium compound.)

為了得到重複單位a3用之單體，具體而言，例如下述例示。 To obtain a monomer for the repeating unit a3, specifically, for example, the following examples are given.

(式中，R12係與前述同樣，X為氫原子、鋰原子、鈉原子、鉀原子、胺化合物、或鋶化合物。) (In the formula, R 12 is the same as described above, and X is a hydrogen atom, a lithium atom, a sodium atom, a potassium atom, an amine compound, or a sulfonium compound.)

為了得到重複單位a4用之單體，具體而言，例如下述例示。 To obtain a monomer for the repeating unit a4, specifically, for example, the following examples are given.

(式中，R14係與前述同樣，X為氫原子、鋰原子、鈉原子、鉀原子、胺化合物、或鋶化合物。) (In the formula, R 14 is the same as described above, and X is a hydrogen atom, a lithium atom, a sodium atom, a potassium atom, an amine compound, or a sulfonium compound.)

(B)成分較佳為含有以下述一般式(3)表示之重複單位b者。藉由含有這種重複單位b，可更提高導電性。 The component (B) preferably contains a repeating unit b represented by the following general formula (3). By including such a repeating unit b, the conductivity can be further improved.

(式中，b為0<b≦1.0。) (In the formula, b is 0 <b ≦ 1.0.)

提供重複單位b之單體，具體而言，例如有下述者。 The monomer which provides the repeating unit b is specifically, for example, the following.

(式中，X2為氫原子、鋰原子、鈉原子、鉀原子、胺化合物、或鋶化合物。) (In the formula, X 2 is a hydrogen atom, a lithium atom, a sodium atom, a potassium atom, an amine compound, or a sulfonium compound.)

前述X、X2為胺化合物的情形，可列舉例如日本特開2013-228447號公報之段落[0048]所記載的(P1a-3)。 When X and X 2 are amine compounds, for example, (P1a-3) described in paragraph [0048] of Japanese Patent Application Laid-Open No. 2013-228447 may be mentioned.

在此，如上述，a1、a2、a3、及a4為0≦a1≦1.0、0≦a2≦1.0、0≦a3≦1.0、0≦a4≦1.0、0<a1+a2+a3+a4≦1.0較佳，更佳為0.2≦a1≦1.0、0.2≦a2≦1.0、0.2≦a3≦1.0、0.2≦a4≦1.0，0.2≦a1+a2+a3+a4≦1.0。又，含有重複單位b的情形，由提高導電性的觀點，較佳為0.2≦b≦1.0，更佳為0.3≦b≦1.0。 Here, as described above, a1, a2, a3, and a4 are 0 ≦ a1 ≦ 1.0, 0 ≦ a2 ≦ 1.0, 0 ≦ a3 ≦ 1.0, 0 ≦ a4 ≦ 1.0, and 0 <a1 + a2 + a3 + a4 ≦ 1.0 Preferably, more preferably 0.2 ≦ a1 ≦ 1.0, 0.2 ≦ a2 ≦ 1.0, 0.2 ≦ a3 ≦ 1.0, 0.2 ≦ a4 ≦ 1.0, and 0.2 ≦ a1 + a2 + a3 + a4 ≦ 1.0. In the case where the repeating unit b is included, from the viewpoint of improving the conductivity, it is preferably 0.2 ≦ b ≦ 1.0, and more preferably 0.3 ≦ b ≦ 1.0.

又，(B)成分之摻雜劑聚合物可具有重複單位a1~a4、重複單位b以外之重複單位c，此重複單位c可列舉例如苯乙烯系、乙烯基萘系、乙烯基矽烷系、苊烯、茚、乙烯基咔唑等。 The dopant polymer of the component (B) may have repeating units c other than repeating units a1 to a4 and repeating unit b. Examples of the repeating unit c include styrene-based, vinylnaphthalene-based, vinylsilane-based, Pinene, indene, vinylcarbazole, etc.

提供重複單位c之單體，具體而言，例如有下述者。 The monomer which provides the repeating unit c is specifically, for example, the following.

合成(B)成分之摻雜劑聚合物的方法，可舉例如藉由將提供上述重複單位a1~a4、b、c之單體中所期望的單體，在有機溶劑中，添加自由基聚合起始劑來進行加熱聚合，而得到(共)聚合物之摻雜劑聚合物的方法。 The method of synthesizing the dopant polymer of the component (B) may be, for example, by adding a desired monomer among the monomers that provide the above-mentioned repeating units a1 to a4, b, and c, in an organic solvent, by radical polymerization A method of polymerizing a dopant polymer by heating polymerization with an initiator to obtain a (co) polymer.

於聚合時所使用的有機溶劑，可例示如甲苯、苯、四氫呋喃、二乙基醚、二噁烷、環己烷、環戊烷、甲基乙基酮、γ-丁內酯等。 Examples of the organic solvent used in the polymerization include toluene, benzene, tetrahydrofuran, diethyl ether, dioxane, cyclohexane, cyclopentane, methyl ethyl ketone, and γ-butyrolactone.

自由基聚合起始劑，可例示如2,2’-偶氮雙異丁腈(AIBN)、2,2’-偶氮雙(2,4-二甲基戊腈)、二甲基2,2’-偶氮雙(2-甲基丙酸酯)、過氧化苯甲醯、過氧化月桂醯等。 Examples of the radical polymerization initiator include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis (2,4-dimethylvaleronitrile), and dimethyl 2, 2'-azobis (2-methylpropionate), benzamidine peroxide, lauryl peroxide, and the like.

反應溫度較佳為50~80℃，反應時間較佳為2~100小時，更佳為5~20小時。 The reaction temperature is preferably 50 to 80 ° C, and the reaction time is preferably 2 to 100 hours, and more preferably 5 to 20 hours.

(B)成分的摻雜劑聚合物中，提供重複單位a1~a4、b、c之單體可為1種類亦可為2種類以上，但為了提高聚合性時，以組合甲基丙烯酸型與苯乙稀型之單體為佳。 In the dopant polymer of the component (B), the monomers providing repeating units a1 to a4, b, and c may be one type or two or more types. However, in order to improve the polymerizability, a combination of methacrylic type and Styrene-based monomers are preferred.

又，提供重複單位a1~a4、b、c之單體使用2種類以上的情形，各自的單體也可以無規共聚合、亦可以嵌段共聚合。若作為嵌段共聚合聚合物(嵌段共聚物)的情形，可期待藉由2種類以上的重複單位a1~a4、b、c所構成之重複部分彼此凝集後形成海島構造，而在摻雜劑聚合物周邊產生特異的構造，提高導電率的優點。 In addition, when two or more types of monomers providing repeating units a1 to a4, b, and c are used, the respective monomers may be randomly copolymerized or block copolymerized. In the case of a block copolymer polymer (block copolymer), it is expected that the repetitive portions composed of two or more kinds of repeating units a1 to a4, b, and c are aggregated with each other to form an island structure, and doped with The specific polymer structure around the polymer has the advantage of improving conductivity.

又，提供重複單位a1~a4、b、c之單體也可 以無規共聚合、或各自也可以嵌段共聚合。此時，與上述重複單位a1~a4、b、c的情形同樣，可期待藉由形成嵌段共聚物來提高導電率的優點。 It is also possible to provide the monomers of repeating units a1 to a4, b, and c. It may be random copolymerization, or each may be block copolymerization. At this time, as in the case of the above-mentioned repeating units a1 to a4, b, and c, the advantage of improving the conductivity by forming a block copolymer can be expected.

以自由基聚合進行無規共聚合的情形，一般為將進行共聚合之單體或自由基聚合起始劑混合後，藉由加熱進行聚合的方法。若於第1單體與自由基聚合起始劑存在下開始進行聚合，然後添加第2單體的情形，聚合物分子之一側成為第一單體進行聚合的構造，另一側則為第2單體進行聚合的構造。然而，此時於中間部分混合有第1單體與第2單體之重複單位，與嵌段共聚物的形態不同。以自由基聚合來形成嵌段共聚物時，較佳為使用活性自由基聚合。 In the case of random copolymerization by radical polymerization, a method in which a monomer to be copolymerized or a radical polymerization initiator is mixed and then polymerized by heating is generally used. When the polymerization is started in the presence of the first monomer and the radical polymerization initiator, and then the second monomer is added, one side of the polymer molecule becomes the structure in which the first monomer is polymerized, and the other side is the first polymer. A structure in which two monomers are polymerized. However, at this time, the repeating units of the first monomer and the second monomer are mixed in the middle portion, which is different from the morphology of the block copolymer. When the block copolymer is formed by radical polymerization, it is preferable to use living radical polymerization.

被稱為RAFT聚合(Reversible Addition Fragmentation chain Transfer polymerization)之活性自由基的聚合方法係因聚合物末端之自由基經常保持活性狀態，故藉由以第1單體開始聚合，在此單體被消耗的階段添加第2單體，可形成以第1單體之重複單位的嵌段與第2單體之重複單位的嵌段形成的二嵌段共聚物。又，以第1單體開始聚合，並在此單體被消耗的階段添加第2單體，接著添加第3單體的情形，亦可形成三嵌段共聚物。 The active radical polymerization method called RAFT polymerization (Reversible Addition Fragmentation chain Transfer polymerization) is because the free radicals at the ends of the polymer often remain active, so by starting the polymerization with the first monomer, the monomer is consumed here When the second monomer is added at the stage of the process, a diblock copolymer formed by a block of a repeating unit of the first monomer and a block of a repeating unit of the second monomer can be formed. In addition, when the polymerization is started with the first monomer, and the second monomer is added at the stage where the monomer is consumed, and then the third monomer is added, a triblock copolymer may be formed.

進行RAFT聚合的情形，具有可形成分子量分布(分散度)狹窄之窄分散聚合物的特徵，特別是一次性添加單體後進行RAFT聚合的情形，可形成分子量分布更狹窄的聚合物。 When RAFT polymerization is performed, it has the characteristics of forming a narrowly dispersed polymer with a narrow molecular weight distribution (dispersion). In particular, when RAFT polymerization is performed after monomers are added all at once, a polymer with a narrower molecular weight distribution can be formed.

又，(B)成分的摻雜劑聚合物中，分子量分布(Mw/Mn)較佳為1.0~2.0，特佳為1.0~1.5的窄分散。只要是窄分散時，可防止藉由使用此摻雜劑聚合物之導電性聚合物材料所形成的導電膜之透過率降低。 In the dopant polymer of the component (B), the narrow molecular weight distribution (Mw / Mn) is preferably 1.0 to 2.0, and particularly preferably a narrow dispersion of 1.0 to 1.5. As long as the dispersion is narrow, the transmittance of the conductive film formed by using the conductive polymer material using the dopant polymer can be prevented from decreasing.

進行RAFT聚合時，需要鏈轉移劑，具體而言，可列舉例如2-氰基-2-丙基苯并二硫酸酯(2-cyano-2-propyl benzodithioate)、4-氰基-4-苯基羰基硫代硫代戊酸(4-cyano-4-phenylcarbonothioylthiopentanoic acid)、2-氰基-2-丙基十二烷基三硫代碳酸酯、4-氰基-4-[(十二烷基磺醯基硫代羰基)磺醯基]戊酸、2-(十二烷基三硫代碳酸酯基(thiocarbonothioylthio)-2-甲基丙酸、氰基甲基十二烷基硫代碳酸酯、氰基甲基甲基(苯基)硫代胺基甲酸酯(carbamothioate)、雙(硫代苯甲醯基)二硫醚、雙(十二烷基磺醯基硫代羰基)二硫醚。此等之中，特佳為2-氰基-2-丙基苯并二硫酸酯。 When RAFT polymerization is performed, a chain transfer agent is required, and specific examples include 2-cyano-2-propyl benzodithioate and 4-cyano-4-benzene. 4-cyano-4-phenylcarbonothioylthiopentanoic acid, 2-cyano-2-propyldodecyltrithiocarbonate, 4-cyano-4-[(dodecane Sulfofluorenylthiocarbonyl) sulfofluorenyl] pentanoic acid, 2- (dodecyltrithiocarbonate-2-methylpropanoic acid, cyanomethyldodecylthiocarbonate Ester, cyanomethylmethyl (phenyl) thiocarbamate (carbamothioate), bis (thiobenzyl) disulfide, bis (dodecylsulfonyl thiocarbonyl) di Sulfide. Among these, 2-cyano-2-propylbenzodisulfate is particularly preferred.

(B)成分之摻雜劑聚合物若包含上述重複單位c的情形，重複單位a1~a4、b、c的比例，較佳為0≦a1+a2+a3+a4≦1.0、0≦b<1.0、0<c<1.0，更佳為0.1≦a1+a2+a3+a4≦0.9、0.1≦b≦0.9、0<c≦0.8，又更佳為0.2≦a1+a2+a3+a4≦0.8、0.2≦b≦0.8、0<c≦0.5。 When the dopant polymer of the component (B) contains the above-mentioned repeating unit c, the ratio of the repeating units a1 to a4, b, and c is preferably 0 ≦ a1 + a2 + a3 + a4 ≦ 1.0, 0 ≦ b < 1.0, 0 <c <1.0, more preferably 0.1 ≦ a1 + a2 + a3 + a4 ≦ 0.9, 0.1 ≦ b ≦ 0.9, 0 <c ≦ 0.8, and more preferably 0.2 ≦ a1 + a2 + a3 + a4 ≦ 0.8 , 0.2 ≦ b ≦ 0.8, and 0 <c ≦ 0.5.

又，a1+a2+a3+a4+b+c=1較佳。 Also, it is preferable that a1 + a2 + a3 + a4 + b + c = 1.

(B)成分的摻雜劑聚合物之重量平均分子量為1,000~500,000，較佳為2,000~200,000之範圍者。重量平均分子量未達1,000時，成為耐熱性差者，又與(A) 成分之複合體溶液之均勻性會變差。另一方面，重量平均分子量超過500,000時，除了導電性惡化外，黏度上昇，作業性變差，對水或有機溶劑之分散性會降低。 The weight average molecular weight of the component (B) dopant polymer is 1,000 to 500,000, and preferably a range of 2,000 to 200,000. When the weight-average molecular weight is less than 1,000, it becomes a person with poor heat resistance. The homogeneity of the complex solution of the components is deteriorated. On the other hand, when the weight average molecular weight exceeds 500,000, in addition to deterioration of conductivity, viscosity increases, workability deteriorates, and dispersibility to water or an organic solvent decreases.

又，重量平均分子量(Mw)係藉由使用作為溶劑之水、二甲基甲醯胺(DMF)、四氫呋喃(THF)之凝膠滲透層析法(GPC)而得到的聚環氧乙烷、聚乙二醇、或聚苯乙烯換算測定值。 The weight average molecular weight (Mw) is polyethylene oxide obtained by gel permeation chromatography (GPC) using water as a solvent, dimethylformamide (DMF), and tetrahydrofuran (THF), Measured in terms of polyethylene glycol or polystyrene.

又，構成(B)成分之摻雜劑聚合物的單體，亦可使用具有磺基之單體，也可將磺酸基的鋰鹽、鈉鹽、鉀鹽、銨鹽、鋶鹽作為單體使用，進行聚合反應，於聚合後，使用離子交換樹脂變換成磺基。 In addition, as the monomer constituting the dopant polymer of the component (B), a monomer having a sulfo group may be used, and lithium salts, sodium salts, potassium salts, ammonium salts, and sulfonium salts of the sulfonic acid group may be used as the monomers. The polymer is used for polymerization, and after polymerization, it is converted into a sulfo group using an ion exchange resin.

[(C)鋶鹽化合物] [(C) phosphonium salt compound]

本發明之導電性聚合物材料包含作為(C)成分之鋶鹽化合物。上述一般式(1-1)、(1-2)表示之鋶鹽化合物，具體而言，可列舉例如下述例示者。 The conductive polymer material of the present invention contains a sulfonium salt compound as a component (C). Specific examples of the sulfonium salt compounds represented by the general formulae (1-1) and (1-2) include the following examples.

(式中，K-表示氫氧離子、氯離子、溴離子、碳酸根離子、碳酸氫根離子、硝酸根離子、羧酸根離子、磺酸根離子、亞磺酸根離子之任一者)。 (In the formula, K - represents any one of hydroxide ion, chloride ion, bromide ion, carbonate ion, hydrogen carbonate ion, nitrate ion, carboxylate ion, sulfonate ion, and sulfinate ion).

與氫氧離子、氯離子、溴離子、碳酸根離子、碳酸氫根離子、硝酸根離子、羧酸根離子、磺酸根離離子、亞磺酸離子之鋶鹽化合物，添加於π共軛系聚合物與具有磺基之摻雜劑聚合物之複合體溶液時，過剩存在之摻雜劑聚合物之磺基，因變成SO3 -之硫酸酯基(sulfonate)，而形成鋶鹽，釋放出水、鹽酸、溴酸、碳酸、硝酸、羧酸、磺酸、亞磺酸。強酸之磺基藉由形成鋶鹽而被中和，取而代之，藉此釋放出酸強度低的酸，使酸性度降低。 Compounds with hydroxide, chloride, bromide, carbonate, bicarbonate, nitrate, carboxylate, sulfonate, and sulfinate, added to π-conjugated polymers In the case of a complex solution with a dopant polymer having a sulfo group, the sulfo group of the excessively present dopant polymer becomes a SO 3 - sulfonate to form a sulfonium salt, releasing water and hydrochloric acid. , Bromic acid, carbonic acid, nitric acid, carboxylic acid, sulfonic acid, sulfinic acid. The sulfo group of a strong acid is neutralized by forming a sulfonium salt, thereby replacing it, thereby releasing an acid having a low acid strength and reducing the acidity.

磺酸不僅酸性度高，且磺基彼此有強的氫鍵。藉此，π共軛系聚合物與具有磺基之摻雜劑聚合物之複合體粒子(以下也稱為導電性聚合物複合體)進行凝聚。但是藉由添加鋶鹽化合物，因磺基變成鹽，故氫鍵性降低。而且，形成鹽的部分存在著正與負之兩方之電荷，故因粒子間產生拉力與排斥力兩方，而抑制粒子間之凝聚。 Not only are sulfonic acids highly acidic, but the sulfo groups have strong hydrogen bonds to each other. Thereby, the composite particles (hereinafter also referred to as a conductive polymer composite) of the π-conjugated polymer and the dopant polymer having a sulfo group are aggregated. However, by adding a sulfonium salt compound, since the sulfo group becomes a salt, the hydrogen bonding property decreases. In addition, the salt-forming portion has both positive and negative charges, and therefore, both the pulling force and the repulsive force between the particles are generated, thereby suppressing the aggregation between the particles.

[導電性聚合物材料] [Conductive polymer material]

本發明之導電性聚合物材料係包含上述(A)成分之π共軛系聚合物與(B)成分之摻雜劑聚合物及(C)成分的鋶鹽化合物者。(B)成分的摻雜劑聚合物係藉由配位於(A)成分的π共軛系聚合物來形成複合體。 The conductive polymer material of the present invention includes the π-conjugated polymer of the component (A), the dopant polymer of the component (B), and the sulfonium salt compound of the component (C). The dopant polymer of the component (B) is a π-conjugated polymer coordinated with the component (A) to form a composite.

本發明之導電性聚合物材料，較佳為對於水或有機溶劑具有分散性者，對於無機或有機基板(於基板表面上形成無機膜或有機膜的基板)，可使旋轉塗佈成膜性或膜之平坦性良好。 The conductive polymer material of the present invention is preferably one having dispersibility with respect to water or an organic solvent. For inorganic or organic substrates (substrates having an inorganic film or an organic film formed on the substrate surface), spin-coating film forming properties can be achieved. Or the flatness of the film is good.

(導電性聚合物材料之製造方法) (Manufacturing method of conductive polymer material)

本發明之導電性聚合物材料(溶液)之製造方法，無特別限定，例如可在包含上述之(A)成分的π共軛系聚合物與(B)成分之摻雜劑聚合物的複合體溶液中，添加(C)成分的鋶鹽化合物來製造。 The method for producing the conductive polymer material (solution) of the present invention is not particularly limited. For example, the conductive polymer material (solution) may be a composite of a π-conjugated polymer containing the component (A) and a dopant polymer containing the component (B). The solution is produced by adding a sulfonium salt compound of the component (C).

(A)成分與(B)成分之複合體係例如在(B)成分的水溶液或(B)成分的水．有機溶劑混合溶液中，添加成為(A)成分之原料的單體(較佳為吡咯、噻吩、苯胺、或此等之衍生物單體)，可藉由添加氧化劑及視情形添加氧化觸媒來進行氧化聚合而得。 The composite system of the component (A) and the component (B) is, for example, an aqueous solution of the component (B) or water of the component (B). In the organic solvent mixed solution, a monomer (preferably pyrrole, thiophene, aniline, or a derivative monomer thereof) serving as a raw material of the component (A) is added, and an oxidizing agent and an oxidation catalyst may be added as appropriate. Obtained by oxidative polymerization.

氧化劑及氧化觸媒，可使用過氧二硫酸銨(過硫酸銨)、過氧二硫酸鈉(過硫酸鈉)、過氧二硫酸鉀(過硫酸鉀)等之過氧二硫酸鹽(過硫酸鹽)、氯化鐵、硫酸亞鐵、氯化銅等之過渡金屬化合物、氧化銀、氧化銫等之金屬氧化物、過氧化氫、臭氧等之過氧化物、過氧化苯甲醯等之有機過氧化物、氧等。 As the oxidant and oxidation catalyst, peroxodisulfate (persulfate) such as ammonium peroxodisulfate (ammonium persulfate), sodium peroxodisulfate (sodium persulfate), potassium peroxodisulfate (potassium persulfate) and the like can be used. Salt), transition metal compounds such as ferric chloride, ferrous sulfate, copper chloride, metal oxides such as silver oxide, cesium oxide, peroxides such as hydrogen peroxide, ozone, and organics such as benzamidine peroxide Peroxide, oxygen, etc.

進行氧化聚合時所使用之反應溶劑，可使用水或水與溶劑之混合溶劑。於此所使用之溶劑可與水混合，且以可溶解或分散(A)成分及(B)成分的溶劑為佳。可列舉例如N-甲基-2-吡咯烷酮、N,N’-二甲基甲醯胺、N,N’-二甲基乙醯胺、二甲基亞碸、六甲基磷三胺等之極性溶劑、甲醇、乙醇、丙醇、丁醇等之醇類、乙二醇、丙二醇、二丙二醇、1,3-丁二醇、1,4-丁二醇、D-葡 萄糖、D-葡萄糖醇、異戊二醇、丁二醇、1,5-戊二醇、1,6-己二醇、1,9-壬二醇、新戊二醇等之多元脂肪族醇類、碳酸伸乙酯、碳酸伸丙酯等之碳酸酯化合物、二噁烷、四氫呋喃等之環狀醚化合物、二烷基醚、乙二醇單烷基醚、乙二醇二烷基醚、丙二醇單烷基醚、丙二醇二烷基醚、聚乙二醇二烷基醚、聚丙二醇二烷基醚等之鏈狀醚類、3-甲基-2-噁唑烷酮等之雜環化合物、乙腈、戊二腈、甲氧基乙腈、丙腈、苯甲腈等之腈化合物等。此等溶劑可以單獨來使用，亦可以2種類以上之混合物來使用。此等可與水混和的溶劑之調合量係以反應溶劑整體的50質量%以下為較佳。 As the reaction solvent used in the oxidative polymerization, water or a mixed solvent of water and a solvent can be used. The solvent used here can be mixed with water, and a solvent which can dissolve or disperse the component (A) and the component (B) is preferred. Examples thereof include N-methyl-2-pyrrolidone, N, N'-dimethylformamide, N, N'-dimethylacetamide, dimethylsulfine, and hexamethylphosphotriamine. Polar solvents, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, D-glucose Multi-component aliphatics such as glucose, D-glucosyl alcohol, isoamyl glycol, butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, etc. Alcohols, carbonate compounds such as ethyl carbonate and propylene carbonate, cyclic ether compounds such as dioxane and tetrahydrofuran, dialkyl ethers, ethylene glycol monoalkyl ethers, and ethylene glycol dialkyl ethers , Chain ethers such as propylene glycol monoalkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, and heterocyclic rings such as 3-methyl-2-oxazolidinone Compounds, nitrile compounds such as acetonitrile, glutaronitrile, methoxyacetonitrile, propionitrile, benzonitrile, and the like. These solvents may be used alone or as a mixture of two or more kinds. The blending amount of these water-miscible solvents is preferably 50% by mass or less of the entire reaction solvent.

又，除了(B)成分的摻雜劑聚合物以外，亦可併用可摻雜於(A)成分之π共軛系聚合物的陰離子。這種陰離子從調整自π共軛系聚合物之脫摻雜特性、導電性聚合物材料之分散性、耐熱性、及耐環境特性的觀點而言，較佳為有機酸。有機酸可列舉例如有機羧酸、酚類、有機磺酸等。 In addition to the dopant polymer of the component (B), an anion which can be doped to the π-conjugated polymer of the component (A) may be used in combination. This anion is preferably an organic acid from the viewpoint of adjusting the dedoping characteristics of the π-conjugated polymer, the dispersibility of the conductive polymer material, heat resistance, and environmental resistance characteristics. Examples of the organic acid include organic carboxylic acids, phenols, and organic sulfonic acids.

有機羧酸可使用在脂肪族、芳香族、環狀脂肪族等中包含一個或二個以上的羧基者。可舉例如甲酸、乙酸、草酸、苯甲酸、鄰苯二甲酸、馬來酸、富馬酸、丙二酸、酒石酸、檸檬酸、乳酸、琥珀酸、單氯乙酸、二氯乙酸、三氯乙酸、三氟乙酸、硝基乙酸、三苯基乙酸等。 As the organic carboxylic acid, one containing two or more carboxyl groups in an aliphatic, aromatic, cyclic aliphatic, or the like can be used. Examples include formic acid, acetic acid, oxalic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, malonic acid, tartaric acid, citric acid, lactic acid, succinic acid, monochloroacetic acid, dichloroacetic acid, and trichloroacetic acid. , Trifluoroacetic acid, nitroacetic acid, triphenylacetic acid, etc.

酚類可舉例甲酚、酚、二甲酚等之酚類。 Examples of the phenols include phenols such as cresol, phenol, and xylenol.

有機磺酸可使用在脂肪族、芳香族、環狀脂 肪族等中包含一個或二個以上的磺酸基者。包含一個磺酸基者，可例示如甲烷磺酸、乙烷磺酸、1-丙烷磺酸、1-丁烷磺酸、1-己烷磺酸、1-庚烷磺酸、1-辛烷磺酸、1-壬烷磺酸、1-癸烷磺酸、1-十二烷磺酸、1-十四烷磺酸、1-十五烷磺酸、2-溴乙烷磺酸、3-氯-2-羥基丙烷磺酸、三氟甲烷磺酸、多黏桿菌素甲烷磺酸、2-丙烯醯胺-2-甲基丙烷磺酸、胺基甲烷磺酸、1-胺基-2-萘酚-4-磺酸、2-胺基-5-萘酚-7-磺酸、3-胺基丙烷磺酸、N-環己基-3-胺基丙烷磺酸、苯磺酸、p-甲苯磺酸、二甲苯磺酸、乙基苯磺酸、丙基苯磺酸、丁基苯磺酸、戊基苯磺酸、己基苯磺酸、庚基苯磺酸、辛基苯磺酸、壬基苯磺酸、癸基苯磺酸、十一烷基苯磺酸、十二烷基苯磺酸、十五烷基苯磺酸、十六烷基苯磺酸、2,4-二甲基苯磺酸、二丙基苯磺酸、4-胺基苯磺酸、o-胺基苯磺酸、m-胺基苯磺酸、4-胺基-2-氯甲苯-5-磺酸、4-胺基-3-甲基苯-1-磺酸、4-胺基-5-甲氧基-2-甲基苯磺酸、2-胺基-5-甲基苯-1-磺酸、4-胺基-2-甲基苯-1-磺酸、5-胺基-2-甲基苯-1-磺酸、4-乙醯胺-3-氯苯磺酸、4-氯-3-硝基苯磺酸、p-氯苯磺酸、萘磺酸、甲基萘磺酸、丙基萘磺酸、丁基萘磺酸、戊基萘磺酸、二甲基萘磺酸、4-胺基-1-萘磺酸、8-氯基萘-1-磺酸、萘磺酸福馬林縮聚物、三聚氰胺磺酸福馬林縮聚物等含有磺酸基的磺酸化合物等。 Organic sulfonic acid can be used in aliphatic, aromatic, cyclic aliphatic Fatty groups include one or more sulfonic acid groups. Those containing one sulfonic acid group can be exemplified by methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, 1-butanesulfonic acid, 1-hexanesulfonic acid, 1-heptanesulfonic acid, 1-octane Sulfonic acid, 1-nonanesulfonic acid, 1-decanesulfonic acid, 1-dodecanesulfonic acid, 1-tetradecanesulfonic acid, 1-pentadecansulfonic acid, 2-bromoethanesulfonic acid, 3 -Chloro-2-hydroxypropanesulfonic acid, trifluoromethanesulfonic acid, polymyxin methanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, aminomethanesulfonic acid, 1-amino-2 -Naphthol-4-sulfonic acid, 2-amino-5-naphthol-7-sulfonic acid, 3-aminopropanesulfonic acid, N-cyclohexyl-3-aminopropanesulfonic acid, benzenesulfonic acid, p -Toluenesulfonic acid, xylenesulfonic acid, ethylbenzenesulfonic acid, propylbenzenesulfonic acid, butylbenzenesulfonic acid, pentylbenzenesulfonic acid, hexylbenzenesulfonic acid, heptylbenzenesulfonic acid, octylbenzenesulfonic acid , Nonylbenzenesulfonic acid, decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid, cetylbenzenesulfonic acid, 2,4-di Methylbenzenesulfonic acid, dipropylbenzenesulfonic acid, 4-aminobenzenesulfonic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, 4-amino-2-chlorotoluene-5-sulfonic acid Acid, 4-amino-3-methylbenzene-1-sulfonic acid, 4- Amino-5-methoxy-2-methylbenzenesulfonic acid, 2-amino-5-methylbenzene-1-sulfonic acid, 4-amino-2-methylbenzene-1-sulfonic acid, 5 -Amino-2-methylbenzene-1-sulfonic acid, 4-acetamidin-3-chlorobenzenesulfonic acid, 4-chloro-3-nitrobenzenesulfonic acid, p-chlorobenzenesulfonic acid, naphthalenesulfonic acid , Methylnaphthalenesulfonic acid, propylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, pentylnaphthalenesulfonic acid, dimethylnaphthalenesulfonic acid, 4-amino-1-naphthalenesulfonic acid, 8-chloronaphthalene-1 -Sulfonic acid groups containing sulfonic acid groups, such as sulfonic acid, naphthalenesulfonic acid formalin polycondensate, and melamine sulfonic acid formalin polycondensate.

包含二個以上的磺酸基者，可列舉例如乙烷二磺酸、丁烷二磺酸、戊烷二磺酸、癸烷二磺酸、m-苯二 磺酸、o-苯二磺酸、p-苯二磺酸、甲苯二磺酸、二甲苯二磺酸、氯苯二磺酸、氟苯二磺酸、苯胺-2,4-二磺酸、苯胺-2,5-二磺酸、二乙基苯二磺酸、二丁基苯二磺酸、萘二磺酸、甲基萘二磺酸、乙基萘二磺酸、十二烷基萘二磺酸、十五烷基萘二磺酸、丁基萘二磺酸、2-胺基-1,4-苯二磺酸、1-胺基-3,8-萘二磺酸、3-胺基-1,5-萘二磺酸、8-胺基-1-萘酚-3,6-二磺酸、蒽二磺酸、丁基蒽二磺酸、4-乙醯胺-4’-異硫氰基二苯乙烯-2,2’-二磺酸、4-乙醯胺-4’-異硫氰基二苯乙烯-2,2’-二磺酸、4-乙醯胺-4’-馬來醯亞胺基二苯乙烯-2,2’-二磺酸、1-乙醯氧基芘-3,6,8-三磺酸、7-胺基-1,3,6-萘三磺酸、8-胺基萘-1,3,6-三磺酸、3-胺基-1,5,7-萘三磺酸等。 Examples of those containing two or more sulfonic acid groups include ethanedisulfonic acid, butanedisulfonic acid, pentanedisulfonic acid, decanedisulfonic acid, and m-benzenedisulfonic acid. Sulfonic acid, o-benzenedisulfonic acid, p-benzenedisulfonic acid, toluene disulfonic acid, xylene disulfonic acid, chlorobenzene disulfonic acid, fluorobenzene disulfonic acid, aniline-2,4-disulfonic acid, Aniline-2,5-disulfonic acid, diethylbenzenedisulfonic acid, dibutylbenzenedisulfonic acid, naphthalenedisulfonic acid, methylnaphthalenedisulfonic acid, ethylnaphthalenedisulfonic acid, dodecylnaphthalene Disulfonic acid, pentadecylnaphthalenedisulfonic acid, butylnaphthalenedisulfonic acid, 2-amino-1,4-benzenedisulfonic acid, 1-amino-3,8-naphthalenedisulfonic acid, 3- Amino-1,5-naphthalenedisulfonic acid, 8-amino-1-naphthol-3,6-disulfonic acid, anthracene disulfonic acid, butyl anthracene disulfonic acid, 4-acetamidin-4 ' -Isothiocyanatostilbene-2,2'-disulfonic acid, 4-acetamido-4'-isothiocyanatostilbene-2,2'-disulfonic acid, 4-acetamidoamine- 4'-maleimidoiminostilbene-2,2'-disulfonic acid, 1-ethoxyfluorenyl-3,6,8-trisulfonic acid, 7-amino-1,3,6 -Naphthalenetrisulfonic acid, 8-aminonaphthalene-1,3,6-trisulfonic acid, 3-amino-1,5,7-naphthalenetrisulfonic acid, and the like.

此等(B)成分以外的陰離子可於(A)成分之聚合前，添加於含有(A)成分的原料單體、(B)成分、氧化劑及/或氧化聚合觸媒的溶液中，又亦可添加於聚合後之含有(A)成分與(B)成分之導電性聚合物複合體(溶液)中。 The anions other than the component (B) may be added to the solution containing the raw material monomer of the component (A), the component (B), the oxidizing agent and / or the oxidative polymerization catalyst before the polymerization of the component (A). It can be added to the conductive polymer composite (solution) containing (A) component and (B) component after polymerization.

如此所得之(A)成分與(B)成分之複合體，必要時可以均質機或球磨機等進行細粒化來使用。 The composite of the component (A) and the component (B) obtained in this manner can be finely granulated using a homogenizer, a ball mill, or the like, if necessary.

對於細粒化較佳為使用可賦予高剪切力之混合分散機。混合分散機可列舉例如均質機、高壓均質機、珠磨機等，其中較佳為高壓均質機。 For fine granulation, a mixing and dispersing machine capable of imparting high shearing force is preferably used. Examples of the mixing and dispersing machine include a homogenizer, a high-pressure homogenizer, and a bead mill. Among them, a high-pressure homogenizer is preferred.

高壓均質機之具體例，可舉例吉田機械興業公司製的NanoVater、Powrex公司製的微射流、SUGINO MACHINE公司製的Ultimizer等。 Specific examples of high-pressure homogenizers include NanoVater manufactured by Yoshida Machinery Industrial Co., Ltd., microjet, manufactured by Powrex Corporation, and SUGINO. Ultimizer manufactured by MACHINE Corporation.

使用高壓均質機之分散處理，可舉例如以高壓使實施分散處理前之複合體溶液進行對向衝撞處理、以高壓來通過注孔或狹縫的處理等。 For the dispersion treatment using a high-pressure homogenizer, for example, the composite solution before the dispersion treatment is subjected to a high-pressure collision treatment, and the injection hole or the slit is subjected to a high-pressure treatment.

於細粒化之前或後，藉由過濾、超過濾、透析等之手法來除去雜質，亦可以陽離子交換樹脂、陰離子交換樹脂、螯合物樹脂等來進行純化。 Before or after fine granulation, impurities are removed by filtration, ultrafiltration, dialysis, or the like, and purification can also be performed by cation exchange resin, anion exchange resin, chelate resin, and the like.

又，導電性聚合物材料溶液中之(A)成分與(B)成分及添加劑之(C)成分之合計含量，較佳為0.05~10.0質量%。若(A)成分與(B)成分及添加劑之(C)成分之合計含量為0.05質量%以上時，可得到充份的導電性，若為10.0質量%以下時，可容易得到均勻的導電性塗膜。 The total content of the component (A), the component (B) and the component (C) in the conductive polymer material solution is preferably from 0.05 to 10.0% by mass. When the total content of the component (A), the component (B) and the component (C) of the additive is 0.05% by mass or more, sufficient conductivity can be obtained, and if it is 10.0% by mass or less, uniform conductivity can be easily obtained Coating film.

(B)成分之含量係相對於(A)成分1莫耳時，(B)成分中之磺基成為0.1~10莫耳範圍內的量為佳，成為1~7莫耳範圍內的量更佳。(B)成分中的磺酸基為0.1莫耳以上時，對(A)成分之摻雜效果高，且可確保充份的導電性。又，(B)成分中的磺酸基為10莫耳以下時，(A)成分的含量成為適當者，且可得到充份的導電性。 The content of the component (B) is more than the amount of the sulfo group in the component (B) in the range of 0.1 to 10 mol when the content of the component (A) is 1 mol, and the amount in the range of 1 to 7 mol is more preferable. good. When the sulfonic acid group in the component (B) is 0.1 mol or more, the doping effect on the component (A) is high, and sufficient conductivity can be secured. When the sulfonic acid group in the component (B) is 10 mol or less, the content of the component (A) becomes appropriate, and sufficient conductivity can be obtained.

導電性聚合物材料溶液中之(C)成分係相對於(A)成分1莫耳，成為0.01~50莫耳之範圍的量為佳，成為0.1~20莫耳之範圍的量更佳。(C)成分為0.01莫耳以上時，可發揮抑制導電性聚合物複合體之凝聚的效 果。又，(C)成分為20莫耳以下時，可充分抑制導電性聚合物材料溶液因強酸性所導致之腐蝕性。 The component (C) in the conductive polymer material solution is preferably an amount in the range of 0.01 to 50 mol, and more preferably an amount in the range of 0.1 to 20 mol relative to 1 mol of the (A) component. (C) When the component is 0.01 mol or more, the effect of suppressing the aggregation of the conductive polymer composite is exhibited fruit. When the component (C) is 20 mol or less, the corrosiveness of the conductive polymer material solution due to strong acidity can be sufficiently suppressed.

可添加於聚合反應水溶液中、或可稀釋單體之有機溶劑，可列舉例如甲醇、乙醇、丙醇、丁醇等之醇類、乙二醇、丙二醇、1,3-丙二醇、二丙二醇、1,3-丁二醇、1,4-丁二醇、D-葡萄糖、D-葡萄糖醇、異戊二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、1,2-戊二醇、1,5-戊二醇、1,2-己二醇、1,6-己二醇、1,9-壬二醇、新戊二醇等之多元脂肪族醇類、二烷基醚、乙二醇單烷基醚、乙二醇二烷基醚、丙二醇單烷基醚、丙二醇二烷基醚、聚乙二醇二烷基醚、聚丙二醇二烷基醚等之鏈狀醚類、二噁烷、四氫呋喃等之環狀醚化合物、環己酮、甲基戊基酮、乙酸乙酯、丁二醇單甲基醚、丙二醇單甲基醚、乙二醇單甲基醚、丁二醇單乙基醚、丙二醇單乙基醚、乙二醇單乙基醚、丙二醇二甲基醚、二乙二醇二甲基醚、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、丙酮酸乙酯、乙酸丁酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙酸tert-丁酯、丙酸t-丁酯、丙二醇單t-丁基醚乙酸酯、γ-丁內酯、N-甲基-2-吡咯烷酮、N,N’-二甲基甲醯胺、N,N’-二甲基乙醯胺、二甲基亞碸、六亞甲基磷醯三醯胺等之極性溶劑、碳酸伸乙酯、碳酸伸丙酯等之碳酸酯化合物、3-甲基-2-噁唑烷酮等之雜環化合物、乙腈、戊二腈、甲氧基乙腈、丙腈、苯甲腈等之腈化合物及此等之混合物等。 Organic solvents that can be added to the polymerization reaction aqueous solution or dilutable monomers, for example, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, 1,3-propanediol, dipropylene glycol, 1 1,3-butanediol, 1,4-butanediol, D-glucose, D-glucosanol, isoamyl glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol Glycol, 2,3-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,9-nonanediol Polyhydric aliphatic alcohols, neopentyl glycol, etc., dialkyl ethers, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, polyethylene glycols Chain ethers such as dialkyl ethers, polypropylene glycol dialkyl ethers, cyclic ether compounds such as dioxane, tetrahydrofuran, cyclohexanone, methylpentyl ketone, ethyl acetate, butanediol monomethyl Ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether Ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Ethyl ketoacetate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, t-butyl propionate, propylene glycol mono t-butyl ether ethyl Acid ester, γ-butyrolactone, N-methyl-2-pyrrolidone, N, N'-dimethylformamide, N, N'-dimethylacetamide, dimethylmethane, hexamethylene Polar solvents such as methylphosphonium trioxamine, carbonate compounds such as ethyl carbonate and propyl carbonate, heterocyclic compounds such as 3-methyl-2-oxazolidinone, acetonitrile, glutaronitrile, Nitrile compounds such as methoxyacetonitrile, propionitrile, benzonitrile, and mixtures thereof.

又，有機溶劑之使用量係相對於單體1莫耳，較佳為0~1,000mL，特佳為0~500mL。有機溶劑之使用量為1,000mL以下時，由於反應容器無變得過大的情形，故符合經濟效益。 The amount of the organic solvent used is 1 mole to the monomer, preferably 0 to 1,000 mL, and particularly preferably 0 to 500 mL. When the amount of the organic solvent is 1,000 mL or less, the reaction vessel does not become too large, so it is economical.

[其他之成分] [Other ingredients] (界面活性劑) (Surfactant)

本發明中，為了提高對基板等之被加工體的潤濕性，故亦可添加界面活性劑。這種界面活性劑可列舉例如非離子系、陽離子系、陰離子系之各種界面活性劑。具體而言，可舉例如聚氧乙烯烷基醚、聚氧乙烯烷基苯基醚、聚氧乙烯羧酸酯、山梨糖醇酐酯(Sorbitan)、聚氧乙烯山梨糖醇酐酯等之非離子系界面活性劑、烷基三甲基氯化銨、烷基苄基氯化銨等之陽離子系界面活性劑、烷基或烷基烯丙基硫酸鹽、烷基或烷基烯丙基磺酸鹽、二烷基磺基琥珀酸鹽等之陰離子系界面活性劑、胺基酸型、甜菜鹼型等之兩性離子型界面活性劑、炔醇系界面活性劑、羥基經聚環氧乙烷或聚環氧丙烷化而成的炔醇系界面活性劑等。 In the present invention, in order to improve the wettability of a substrate such as a substrate, a surfactant may be added. Examples of such a surfactant include nonionic, cationic, and anionic surfactants. Specific examples include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene carboxylic acid esters, sorbitan esters, polyoxyethylene sorbitan esters, and the like. Ionic surfactants, cationic surfactants such as alkyl trimethyl ammonium chloride, alkyl benzyl ammonium chloride, alkyl or alkyl allyl sulfate, alkyl or alkyl allyl sulfonate Salt, dialkyl sulfosuccinate and other anionic surfactants, amino acid type, betaine type and other zwitterionic surfactants, alkynol surfactants, hydroxyl via polyethylene oxide Or alkynol-based surfactants obtained by alkylating polypropylene oxide.

(高導電化劑) (Highly conductive agent)

於本發明中，以提高導電性聚合物材料之導電率為目的，與主劑不同，亦可添加有機溶劑。這種添加溶劑可列舉極性溶劑，具體而言，可列舉例如乙二醇、二乙二醇、聚乙二醇、二甲基亞碸(DMSO)、二甲基甲醯胺 (DMF)、N-甲基-2-吡咯烷酮(NMP)、環丁碸及此等之混合物。添加量較佳為1.0~30.0質量%，特佳為3.0~10.0質量%。 In the present invention, in order to improve the conductivity of the conductive polymer material, an organic solvent may be added, unlike the main agent. Examples of such an addition solvent include polar solvents, and specific examples thereof include ethylene glycol, diethylene glycol, polyethylene glycol, dimethylsulfinium (DMSO), and dimethylformamide. (DMF), N-methyl-2-pyrrolidone (NMP), cyclobutane, and mixtures thereof. The addition amount is preferably 1.0 to 30.0% by mass, and particularly preferably 3.0 to 10.0% by mass.

(中和劑) (Neutralizing agent)

本發明中，為了中和導電性聚合物材料之水溶液中之pH的酸性而添加(C)成分為特徵，此外，也可添加其他中和劑，亦可添加日本特開2006-96975公報中的段落[0033]~[0045]記載之含氮之芳香族性環式化合物、日本專利5264723記載之段落[0127]記載的陽離子，也可將pH控制為中性。藉由使溶液的pH趨近於中性，可防止使用於印刷機時生鏽。 In the present invention, the component (C) is added to neutralize the acidity of the pH in the aqueous solution of the conductive polymer material. In addition, other neutralizing agents may be added. The nitrogen-containing aromatic cyclic compound described in paragraphs [0033] to [0045] and the cation described in paragraph [0127] of Japanese Patent 5264723 may be controlled to have a neutral pH. By making the pH of the solution near neutral, it is possible to prevent rust when used in a printing machine.

如以上說明之本發明之導電性聚合物材料時，由於酸性度低，可抑制經過時間之粒子之凝聚，而成為在溶液中之安定性良好者。 As described above, when the conductive polymer material of the present invention has a low acidity, it can suppress the aggregation of particles that have passed over time, and it has a good stability in a solution.

[導電膜] [Conductive film]

如上述所得之導電性聚合物材料(溶液)，藉由塗佈於基板等之被加工體而可形成導電膜。導電性聚合物材料(溶液)之塗佈方法，可列舉例如經由旋轉塗佈機等之塗佈、棒式塗佈、浸漬、雙輥筒(comma)塗佈、噴塗、輥塗佈、網板印刷、凸版印刷、凹版印刷、噴墨印刷等。塗佈後，進行經由熱風循環爐、加熱板等之加熱處理、IR、UV照射等後可形成導電膜。 The conductive polymer material (solution) obtained as described above can be formed into a conductive film by being applied to a processing object such as a substrate. The method for applying the conductive polymer material (solution) includes, for example, coating by a spin coater, rod coating, dipping, double-roller (comma) coating, spray coating, roll coating, and stencil. Printing, letterpress printing, gravure printing, inkjet printing, etc. After coating, a conductive film can be formed by performing heat treatment through a hot-air circulation furnace, a heating plate, and the like, IR, and UV irradiation.

如上述，本發明之導電性聚合物材料藉由塗佈．成膜於基板等，可形成導電膜。又，如此形成的導電膜，由於導電性、透明性優異，故可作為透明電極層及電洞注入層產生功能者。 As mentioned above, the conductive polymer material of the present invention is coated. The film is formed on a substrate or the like to form a conductive film. In addition, the conductive film thus formed is excellent in conductivity and transparency, and thus can function as a transparent electrode layer and a hole injection layer.

將本發明之導電性聚合物材料塗佈於基板等成膜後，藉由照射波長140~400nm之光或電子線，可分解(C)成分之鋶鹽化合物。藉此，僅(A)成分與(B)成分所成之導電性聚合物複合體殘留於膜中，因此提高導電性。光照射之後，為了使分解物蒸發為目的，也可在50~200℃之範圍內進行烘烤。 After the conductive polymer material of the present invention is coated on a substrate or the like and formed into a film, the phosphonium salt compound of the component (C) can be decomposed by irradiating light or electron rays with a wavelength of 140 to 400 nm. Thereby, only the conductive polymer composite formed by the (A) component and the (B) component remains in the film, and thus the conductivity is improved. After light irradiation, in order to evaporate the decomposed matter, baking may be performed in a range of 50 to 200 ° C.

[基板] [Substrate]

又，本發明係提供一種藉由上述本發明之導電性聚合物材料而形成導電膜的基板。 The present invention also provides a substrate on which a conductive film is formed from the conductive polymer material of the present invention.

基板可列舉例如玻璃基板、石英基板、光罩基板、樹脂基板、矽晶圓、砷化鎵晶圓、磷化銦晶圓等之化合物半導體晶圓、軟性基板等。又，塗佈於光阻膜上，亦可作為防靜電面塗層使用。 Examples of the substrate include compound semiconductor wafers such as glass substrates, quartz substrates, photomask substrates, resin substrates, silicon wafers, gallium arsenide wafers, indium phosphide wafers, and flexible substrates. Moreover, it can also be used as an antistatic top coat by coating on a photoresist film.

如上述，本發明之導電性聚合物材料時，藉由含有強酸的磺基之(B)成分的摻雜劑聚合物與(A)成分之π共軛系聚合物形成複合體，其中添加(C)成分之鋶鹽化合物，由於溶液之酸性度降低，經過時間之粒子之凝聚被抑制，低腐蝕性且低黏性，在溶液中之安定性及過濾性良好，旋轉塗佈之成膜性佳，又，形成膜時，可形 成透明性、平坦性、平滑性、耐久性、及導電性良好的導電膜。又，這種導電性聚合物材料時，對有機溶劑及有機基板之親和性良好，又對於有機基板、無機基板之任一，也為成膜性良好者。 As described above, in the conductive polymer material of the present invention, a complex is formed by a dopant polymer containing a strong acid sulfo group (B) component and a (A) component π conjugated polymer, wherein ( C) The osmium salt compound of the component, because the acidity of the solution is reduced, the aggregation of particles over time is suppressed, low corrosion and low viscosity, good stability and filterability in solution, and film formation of spin coating Good, also, formable It forms a conductive film with good transparency, flatness, smoothness, durability, and conductivity. In addition, when such a conductive polymer material has good affinity for an organic solvent and an organic substrate, it also has good film-forming properties for any of an organic substrate and an inorganic substrate.

又，藉由這種導電性聚合物材料所形成之導電膜，因導電性、透明性等優異，故可作為透明電極層產生功能者。 In addition, a conductive film formed using such a conductive polymer material can be used as a transparent electrode layer because it has excellent conductivity and transparency.

[實施例] [Example]

以下使用合成例、調製例、比較調製例、實施例、及比較例具體說明本發明，但本發明不限定於此等者。 Hereinafter, the present invention will be specifically described using synthesis examples, modulation examples, comparative modulation examples, examples, and comparative examples, but the present invention is not limited to these.

[摻雜劑聚合物之合成] [Synthesis of Dopant Polymer] (合成例1~15) (Synthesis examples 1 to 15)

於氮環境下，將2,2’-偶氮雙(異丁酸)二甲酯溶解於甲醇之溶液，以4小時滴入於在甲醇中以64℃進行攪拌之溶解有單體之溶液中，攪拌4小時。冷卻至室溫後，一邊劇烈地攪拌一邊滴入於乙酸乙酯中。將產生的固形物過濾，於50℃下真空乾燥15小時，將所得之白色聚合物溶解於甲醇中，使用離子交換樹脂，將單體之陽離子交換成氫原子，變換成磺基。 Under a nitrogen environment, a solution of 2,2'-azobis (isobutyric acid) dimethyl ester in methanol was dripped into the monomer-dissolved solution stirred at 64 ° C in methanol for 4 hours. And stir for 4 hours. After cooling to room temperature, it was dropped into ethyl acetate with vigorous stirring. The resulting solid was filtered and vacuum dried at 50 ° C for 15 hours. The obtained white polymer was dissolved in methanol, and the ion exchange resin was used to exchange the cations of the monomers into hydrogen atoms and convert them into sulfo groups.

以這種方法得到以下所示摻雜劑聚合物1~15。 In this way, dopant polymers 1 to 15 shown below were obtained.

摻雜劑聚合物1 Dopant polymer 1

重量平均分子量(Mw)=46,000 Weight average molecular weight (Mw) = 46,000

分子量分布(Mw/Mn)=1.55 Molecular weight distribution (Mw / Mn) = 1.55

摻雜劑聚合物2 Dopant polymer 2

重量平均分子量(Mw)=41,000 Weight average molecular weight (Mw) = 41,000

分子量分布(Mw/Mn)=1.66 Molecular weight distribution (Mw / Mn) = 1.66

摻雜劑聚合物3 Dopant polymer 3

重量平均分子量(Mw)=57,000 Weight average molecular weight (Mw) = 57,000

分子量分布(Mw/Mn)=1.84 Molecular weight distribution (Mw / Mn) = 1.84

摻雜劑聚合物4 Dopant polymer 4

重量平均分子量(Mw)=47,000 Weight average molecular weight (Mw) = 47,000

分子量分布(Mw/Mn)=1.87 Molecular weight distribution (Mw / Mn) = 1.87

摻雜劑聚合物5 Dopant polymer 5

重量平均分子量(Mw)=53,000 Weight average molecular weight (Mw) = 53,000

分子量分布(Mw/Mn)=1.81 Molecular weight distribution (Mw / Mn) = 1.81

摻雜劑聚合物6 Dopant polymer 6

重量平均分子量(Mw)=51,000 Weight average molecular weight (Mw) = 51,000

分子量分布(Mw/Mn)=1.79 Molecular weight distribution (Mw / Mn) = 1.79

摻雜劑聚合物7 Dopant polymer 7

重量平均分子量(Mw)=39,300 Weight average molecular weight (Mw) = 39,300

分子量分布(Mw/Mn)=1.91 Molecular weight distribution (Mw / Mn) = 1.91

摻雜劑聚合物8 Dopant polymer 8

重量平均分子量(Mw)=41,100 Weight average molecular weight (Mw) = 41,100

分子量分布(Mw/Mn)=1.98 Molecular weight distribution (Mw / Mn) = 1.98

摻雜劑聚合物9 Dopant polymer 9

重量平均分子量(Mw)=51,000 Weight average molecular weight (Mw) = 51,000

分子量分布(Mw/Mn)=1.75 Molecular weight distribution (Mw / Mn) = 1.75

摻雜劑聚合物10 Dopant polymer 10

重量平均分子量(Mw)=51,000 Weight average molecular weight (Mw) = 51,000

分子量分布(Mw/Mn)=1.79 Molecular weight distribution (Mw / Mn) = 1.79

摻雜劑聚合物11 Dopant polymer 11

重量平均分子量(Mw)=33,100 Weight average molecular weight (Mw) = 33,100

分子量分布(Mw/Mn)=1.66 Molecular weight distribution (Mw / Mn) = 1.66

摻雜劑聚合物12 Dopant polymer 12

重量平均分子量(Mw)=42,100 Weight average molecular weight (Mw) = 42,100

分子量分布(Mw/Mn)=1.86 Molecular weight distribution (Mw / Mn) = 1.86

摻雜劑聚合物13 Dopant polymer 13

重量平均分子量(Mw)=42,000 Weight average molecular weight (Mw) = 42,000

分子量分布(Mw/Mn)=1.79 Molecular weight distribution (Mw / Mn) = 1.79

摻雜劑聚合物14 Dopant polymer 14

重量平均分子量(Mw)=21,000 Weight average molecular weight (Mw) = 21,000

分子量分布(Mw/Mn)=1.50 Molecular weight distribution (Mw / Mn) = 1.50

摻雜劑聚合物15 Dopant polymer 15

重量平均分子量(Mw)=44,000 Weight average molecular weight (Mw) = 44,000

分子量分布(Mw/Mn)=1.69 Molecular weight distribution (Mw / Mn) = 1.69

[含有作為π共軛系聚合物之聚噻吩之導電性聚合物複合體分散液之調製] [Preparation of a conductive polymer composite dispersion containing polythiophene as a π-conjugated polymer] (調製例1) (Modulation example 1)

將3.82g之3,4-乙烯二氧噻吩、與在1,000mL之超純水中溶解有12.5g之摻雜劑聚合物1的溶液，於30℃下進行混合。 3.82 g of 3,4-ethylenedioxythiophene and a solution in which 12.5 g of dopant polymer 1 was dissolved in 1,000 mL of ultrapure water were mixed at 30 ° C.

將藉此所得之混合溶液保持在30℃，一邊攪拌一邊緩慢地添加溶於100mL之超純水中之8.40g的過硫酸鈉與2.3g之硫酸亞鐵的氧化觸媒溶液，並攪拌4小時使其反應。 The mixed solution thus obtained was kept at 30 ° C, and an oxidation catalyst solution of 8.40 g of sodium persulfate and 2.3 g of ferrous sulfate dissolved in 100 mL of ultrapure water was slowly added while stirring, and stirred for 4 hours. Make it react.

於所得之反應液中添加1,000mL的超純水，使用超過濾法來除去約1,000mL的溶液。此操作重覆3次。 1,000 mL of ultrapure water was added to the obtained reaction solution, and about 1,000 mL of the solution was removed using an ultrafiltration method. This operation is repeated 3 times.

又，於進行上述過濾處理後之處理液中，添加200mL之稀釋成10質量%的硫酸與2,000mL的離子交換水，使用超過濾法來除去約2,000mL的處理液，並於此者中加入2,000mL的離子交換水，使用超過濾法來除去約2,000mL的液體。此操作重覆3次。 In addition, to the treatment solution after the above-mentioned filtration treatment, 200 mL of sulfuric acid diluted to 10% by mass and 2,000 mL of ion-exchanged water were added, and about 2,000 mL of the treatment solution was removed using an ultrafiltration method, and then added to 2,000 mL of ion-exchanged water was removed by ultrafiltration using about 2,000 mL of liquid. This operation is repeated 3 times.

此外，於所得之處理液中加入2,000mL的離子交換水，使用超過濾法來除去約2,000mL的處理液。此操作重覆5次，得到1.3質量%的藍色導電性聚合物複合體分散液1。 In addition, 2,000 mL of ion-exchanged water was added to the obtained treatment solution, and about 2,000 mL of the treatment solution was removed using an ultrafiltration method. This operation was repeated 5 times to obtain 1.3% by mass of the blue conductive polymer composite dispersion liquid 1.

超過濾條件係設定如下述。 The ultrafiltration conditions are set as follows.

超過濾膜之劃分(fraction)分子量：30K Fraction molecular weight of ultrafiltration membrane: 30K

交叉流式 Cross-flow

供給液流量：3,000mL/分鐘 Supply liquid flow: 3,000mL / min

膜分壓：0.12Pa Membrane partial pressure: 0.12Pa

又，其他的調製例亦以相同的條件進行超過濾。 Moreover, other modulation examples are also subjected to ultrafiltration under the same conditions.

(調製例2) (Modulation example 2)

除了將12.5g的摻雜劑聚合物1變更為10.0g的摻雜劑聚合物2，將3.82g之3,4-乙烯二氧噻吩之調合量變更成2.41g、過硫酸鈉之調合量變更為5.31g、硫酸亞鐵之調合量變更為1.50g外，以與調製例1相同之方法來進行調製，得到導電性聚合物複合體分散液2。 In addition to changing 12.5 g of dopant polymer 1 to 10.0 g of dopant polymer 2, changing the blending amount of 3.82 g of 3,4-ethylenedioxythiophene to 2.41 g, and the blending amount of sodium persulfate A conductive polymer composite dispersion liquid 2 was obtained in the same manner as in Preparation Example 1 except that it was 5.31 g and the blending amount of ferrous sulfate was changed to 1.50 g.

(調製例3) (Modulation example 3)

除了將12.5g的摻雜劑聚合物1變更成12.0g的摻雜劑聚合物3，將3.82g之3,4-乙烯二氧噻吩之調合量變更成2.72g、過硫酸鈉之調合量變更成6.00g、硫酸亞鐵之調合量變更成1.60g外，以與調製例1相同的方法來進行調製，得到導電性聚合物複合體分散液3。 In addition to changing 12.5 g of dopant polymer 1 to 12.0 g of dopant polymer 3, changing the blending amount of 3.82 g of 3,4-ethylenedioxythiophene to 2.72 g, and the blending amount of sodium persulfate A conductive polymer composite dispersion liquid 3 was obtained in the same manner as in Preparation Example 1 except that it was adjusted to 6.00 g and the blending amount of ferrous sulfate was changed to 1.60 g.

(調製例4) (Modulation example 4)

除了將12.5g的摻雜劑聚合物1變更成11.8g的摻雜劑聚合物4，將8.40g的過硫酸鈉變更成4.50g的過硫酸銨、3.82g之3,4-乙烯二氧噻吩之調合量變更成2.04g、硫酸亞鐵之調合量變更成1.23g外，以與調製例1相同之方法來進行調製，可得到導電性聚合物複合體分散液4。 In addition to changing 12.5g of dopant polymer 1 to 11.8g of dopant polymer 4, 8.40g of sodium persulfate was changed to 4.50g of ammonium persulfate, and 3.82g of 3,4-ethylenedioxythiophene The blending amount was changed to 2.04 g and the blending amount of ferrous sulfate was changed to 1.23 g. The conductive polymer composite dispersion liquid 4 was obtained in the same manner as in Preparation Example 1.

(調製例5) (Modulation example 5)

除了將12.5g的摻雜劑聚合物1變更成11.0g的摻雜劑聚合物5，將8.40g的過硫酸鈉變更成5.31g的過硫酸銨、3.82g之3,4-乙烯二氧噻吩之調合量變更成2.41g、硫酸亞鐵之調合量變更成1.50g外，以與調製例1相同之方法來進行調製，得到導電性聚合物複合體分散液5。 In addition to changing 12.5 g of dopant polymer 1 to 11.0 g of dopant polymer 5, 8.40 g of sodium persulfate was changed to 5.31 g of ammonium persulfate, and 3.82 g of 3,4-ethylenedioxythiophene The blending amount was changed to 2.41 g and the blending amount of ferrous sulfate was changed to 1.50 g. The same method as in Preparation Example 1 was used to prepare the conductive polymer composite dispersion liquid 5.

(調製例6) (Modulation example 6)

除了將12.5g的摻雜劑聚合物1變更成13.0g的摻雜劑聚合物6，將8.40g的過硫酸鈉變更成5.31g的過硫酸銨、3.82g之3,4-乙烯二氧噻吩之調合量變更成2.41g、硫酸亞鐵之調合量變更成1.50g以外，以與調製例1相同之方法來進行調製，得到導電性聚合物複合體分散液6。 In addition to changing 12.5g of dopant polymer 1 to 13.0g of dopant polymer 6, 8.40g of sodium persulfate was changed to 5.31g of ammonium persulfate and 3.82g of 3,4-ethylenedioxythiophene Except that the blending amount was changed to 2.41 g, and the blending amount of ferrous sulfate was changed to 1.50 g, it was prepared in the same manner as in Preparation Example 1 to obtain a conductive polymer composite dispersion liquid 6.

(調製例7) (Modulation Example 7)

除了將12.5g的摻雜劑聚合物1變更成12.8g的摻雜 劑聚合物7，將8.40g的過硫酸鈉變更成5.31g的過硫酸銨、3.82g之3,4-乙烯二氧噻吩之調合量變更成2.41g、硫酸亞鐵之調合量變更成1.50g以外，以與調製例1相同之方法來進行調製，得到導電性聚合物複合體分散液7。 In addition to changing 12.5g of dopant polymer 1 to 12.8g of doping Agent Polymer 7, changed 8.40 g of sodium persulfate to 5.31 g of ammonium persulfate, 3.82 g of 3,4-ethylenedioxythiophene to 2.41 g, and ferrous sulfate to 1.50 g Other than that, it was prepared in the same manner as in Preparation Example 1 to obtain a conductive polymer composite dispersion liquid 7.

(調製例8) (Modulation example 8)

除了將12.5g的摻雜劑聚合物1變更成11.0g的摻雜劑聚合物8，將8.40g的過硫酸鈉變更成5.31g的過硫酸銨、3.82g之3,4-乙烯二氧噻吩之調合量變更成2.41g、硫酸亞鐵之調合量變更成1.50g外，以與調製例1相同之方法來進行調製，得到導電性聚合物複合體分散液8。 In addition to changing 12.5 g of dopant polymer 1 to 11.0 g of dopant polymer 8, changing 8.40 g of sodium persulfate to 5.31 g of ammonium persulfate and 3.82 g of 3,4-ethylenedioxythiophene The blending amount was changed to 2.41 g, and the blending amount of ferrous sulfate was changed to 1.50 g. The same method as in Preparation Example 1 was used to prepare the conductive polymer composite dispersion liquid 8.

(調製例9) (Modulation Example 9)

除了將12.5g的摻雜劑聚合物1變更成10.8g的摻雜劑聚合物9，將8.40g的過硫酸鈉變更成5.31g的過硫酸銨、3.82g之3,4-乙烯二氧噻吩之調合量變更成2.41g、硫酸亞鐵之調合量變更成1.50g外，以與調製例1相同之方法來進行調製，得到導電性聚合物複合體分散液9。 In addition to changing 12.5 g of dopant polymer 1 to 10.8 g of dopant polymer 9, 8.40 g of sodium persulfate was changed to 5.31 g of ammonium persulfate and 3.82 g of 3,4-ethylenedioxythiophene The blending amount was changed to 2.41 g, and the blending amount of ferrous sulfate was changed to 1.50 g. The same method as in Preparation Example 1 was used to prepare the conductive polymer composite dispersion liquid 9.

(調製例10) (Modulation example 10)

除了將12.5g的摻雜劑聚合物1變更成11.5g的摻雜劑聚合物10，將8.40g的過硫酸鈉變更成5.31g的過硫酸銨、3.82g之3,4-乙烯二氧噻吩之調合量變更成2.41g、硫酸亞鐵之調合量變更成1.50g外，以與調製例1相同之方 法來進行調製，得到導電性聚合物複合體分散液10。 In addition to changing 12.5g of dopant polymer 1 to 11.5g of dopant polymer 10, 8.40g of sodium persulfate was changed to 5.31g of ammonium persulfate, and 3.82g of 3,4-ethylenedioxythiophene The blending amount was changed to 2.41 g, and the blending amount of ferrous sulfate was changed to 1.50 g. It prepared by the method, and the electroconductive polymer composite dispersion liquid 10 was obtained.

(調製例11) (Modulation Example 11)

除了將12.5g的摻雜劑聚合物1變更成12.8g的摻雜劑聚合物11，將8.40g的過硫酸鈉變更成5.31g的過硫酸銨、3.82g之3,4-乙烯二氧噻吩之調合量變更成2.41g、硫酸亞鐵之調合量變更成1.50g外，以與調製例1相同之方法來進行調製，得到導電性聚合物複合體分散液11。 In addition to changing 12.5g of dopant polymer 1 to 12.8g of dopant polymer 11, 8.40g of sodium persulfate was changed to 5.31g of ammonium persulfate, and 3.82g of 3,4-ethylenedioxythiophene The blending amount was changed to 2.41 g and the blending amount of ferrous sulfate was changed to 1.50 g. The same method as in Preparation Example 1 was used to prepare the conductive polymer composite dispersion liquid 11.

(調製例12) (Modulation Example 12)

除了將12.5g的摻雜劑聚合物1變更成12.0g的摻雜劑聚合物12，將8.40g的過硫酸鈉變更成5.31g的過硫酸銨、3.82g之3,4-乙烯二氧噻吩之調合量變更成2.41g、硫酸亞鐵之調合量變更成1.50g外，以與調製例1相同之方法來進行調製，得到導電性聚合物複合體分散液12。 In addition to changing 12.5g of dopant polymer 1 to 12.0g of dopant polymer 12, 8.40g of sodium persulfate was changed to 5.31g of ammonium persulfate, and 3.82g of 3,4-ethylenedioxythiophene The blending amount was changed to 2.41 g and the blending amount of ferrous sulfate was changed to 1.50 g. The same method as in Preparation Example 1 was used to prepare the conductive polymer composite dispersion liquid 12.

(調製例13) (Modulation Example 13)

除了將12.5g的摻雜劑聚合物1變更成11.9g的摻雜劑聚合物13，將8.40g的過硫酸鈉變更成5.31g的過硫酸銨、3.82g之3,4-乙烯二氧噻吩之調合量變更成2.41g、硫酸亞鐵之調合量變更成1.50g外，以與調製例1相同之方法來進行調製，得到導電性聚合物複合體分散液13。 In addition to changing 12.5g of dopant polymer 1 to 11.9g of dopant polymer 13, 8.40g of sodium persulfate was changed to 5.31g of ammonium persulfate and 3.82g of 3,4-ethylenedioxythiophene The blending amount was changed to 2.41 g and the blending amount of ferrous sulfate was changed to 1.50 g. The same method as in Preparation Example 1 was used to prepare the conductive polymer composite dispersion liquid 13.

(調製例14) (Modulation Example 14)

除了將12.5g的摻雜劑聚合物1變更成12.8g的摻雜劑聚合物14，將8.40g的過硫酸鈉變更成5.31g的過硫酸銨、3.82g之3,4-乙烯二氧噻吩之調合量變更成2.41g、硫酸亞鐵之調合量變更成1.50g外，以與調製例1相同之方法來進行調製，得到導電性聚合物複合體分散液14。 In addition to changing 12.5g of dopant polymer 1 to 12.8g of dopant polymer 14, 8.40g of sodium persulfate was changed to 5.31g of ammonium persulfate, and 3.82g of 3,4-ethylenedioxythiophene The blending amount was changed to 2.41 g and the blending amount of ferrous sulfate was changed to 1.50 g. The same method as in Preparation Example 1 was used to prepare the conductive polymer composite dispersion liquid 14.

(調製例15) (Modulation Example 15)

除了將12.5g的摻雜劑聚合物1變更成10.2g的摻雜劑聚合物15，將8.40g的過硫酸鈉變更成5.31g的過硫酸銨、3.82g之3,4-乙烯二氧噻吩之調合量變更成2.41g、硫酸亞鐵之調合量變更成1.50g外，以與調製例1相同之方法來進行調製，得到導電性聚合物複合體分散液15。 In addition to changing 12.5 g of dopant polymer 1 to 10.2 g of dopant polymer 15, 8.40 g of sodium persulfate was changed to 5.31 g of ammonium persulfate, and 3.82 g of 3,4-ethylenedioxythiophene The blending amount was changed to 2.41 g and the blending amount of ferrous sulfate was changed to 1.50 g. The same method as in Preparation Example 1 was used to prepare the conductive polymer composite dispersion liquid 15.

(調製例16) (Modulation Example 16)

除了將3.82g之3,4-乙烯二氧噻吩變更成3.87g之3,4-二甲氧基噻吩外，以與調製例1相同之方法來進行調製，得到導電性聚合物複合體分散液16。 A conductive polymer composite dispersion was obtained in the same manner as in Preparation Example 1, except that 3.82 g of 3,4-ethylenedioxythiophene was changed to 3.87 g of 3,4-dimethoxythiophene. 16.

(調製例17) (Modulation Example 17)

除了將3.82g之3,4-乙烯二氧噻吩變更成4.62g之2,3-二氫噻吩并[3,4-b][1,4]戴奧辛(dioxin)-2-基)甲醇外，以與調製例1相同之方法來進行調製，得到導電性聚合物複合體分散液17。 In addition to changing 3.82 g of 3,4-ethylenedioxythiophene to 4.62 g of 2,3-dihydrothieno [3,4-b] [1,4] dioxin-2-yl) methanol, Preparation was performed in the same manner as in Preparation Example 1, and a conductive polymer composite dispersion liquid 17 was obtained.

(調製例18) (Modulation example 18)

除了將3.82g之3,4-乙烯二氧噻吩變更成4.16g之3,4-丙烯二氧噻吩外，以與調製例1相同之方法來進行調製，得到導電性聚合物複合體分散液18。 A conductive polymer composite dispersion liquid 18 was prepared in the same manner as in Preparation Example 1 except that 3.82 g of 3,4-ethylenedioxythiophene was changed to 4.16 g of 3,4-propylene dioxythiophene. .

[實施例] [Example]

以下表示實施例使用的鋶鹽化合物1~8。 The sulfonium salt compounds 1 to 8 used in the examples are shown below.

(實施例1~18) (Examples 1 to 18)

將以調製例1~18所得之1.3質量%之導電性聚合物複合體分散液1~18(20g)、鋶鹽化合物1(0.2g)、二甲基亞碸5g、界面活性劑兼消泡劑的Surfynol465(0.5g)分別混合，然後，使用孔徑0.45μm的再生纖維素過濾器(ADVANTEC公司製)來過濾並調製導電性聚合物材料，使用孔徑0.45μm的再生纖維素過濾器(ADVANTEC公司製)來過濾，分別作為實施例1~18。所得之導電性聚合物材料之pH如表1所示。 1.3% by mass of the conductive polymer composite dispersion liquids 1 to 18 (20 g), sulfonium salt compound 1 (0.2 g), 5 g of dimethyl fluorene obtained in Preparation Examples 1 to 18, and surfactant and defoaming agent Surfynol 465 (0.5 g) of the agent was mixed separately, and then a conductive polymer material was filtered and prepared using a regenerated cellulose filter (manufactured by ADVANTEC) with a pore size of 0.45 μm, and a regenerated cellulose filter (ADVANTEC) with a pore size of 0.45 μm Filter), as examples 1-18. The pH of the obtained conductive polymer material is shown in Table 1.

(實施例19) (Example 19)

將以調製例1所得之1.3質量%之導電性聚合物複合體分散液1(20g)、鋶鹽化合物2(0.3g)、二甲基亞碸5g、界面活性劑兼消泡劑的Surfynol465(0.5g)分別混合，然後，使用孔徑0.45μm的再生纖維素過濾器(ADVANTEC公司製)來過濾並調製導電性聚合物材料，使用孔徑0.45μm的再生纖維素過濾器(ADVANTEC公司製)來過濾，作為實施例19。所得之導電性聚合物材料之pH為4.3。 1.3% by mass of the conductive polymer composite dispersion liquid 1 (20 g), sulfonium salt compound 2 (0.3 g), 5 g of dimethylsulfenium, Surfynol 465 (surfactant and antifoaming agent) obtained in Preparation Example 1 were prepared. 0.5g) were mixed separately, and then a conductive polymer material was filtered and prepared using a regenerated cellulose filter (manufactured by ADVANTEC) with a pore size of 0.45 μm, and filtered using a regenerated cellulose filter (manufactured by ADVANTEC) with a pore size of 0.45 μm. As embodiment 19. The pH of the obtained conductive polymer material was 4.3.

(實施例20) (Example 20)

將以調製例1所得之1.3質量%之導電性聚合物複合體分散液1(20g)、鋶鹽化合物3(0.2g)、二甲基亞碸5g、界面活性劑兼消泡劑的Surfynol465(0.5g)分別混 合，然後，使用孔徑0.45μm的再生纖維素過濾器(ADVANTEC公司製)來過濾並調製導電性聚合物材料，使用孔徑0.45μm的再生纖維素過濾器(ADVANTEC公司製)來過濾，作為實施例20。所得之導電性聚合物材料之pH為4.8。 1.3% by mass of conductive polymer composite dispersion liquid 1 (20 g), sulfonium salt compound 3 (0.2 g), 5 g of dimethylsulfenium, Surfynol 465 (surfactant and antifoaming agent) obtained in Preparation Example 1 were prepared. 0.5g) mixed separately Then, a conductive polymer material was filtered and prepared using a regenerated cellulose filter (manufactured by ADVANTEC) with a pore size of 0.45 μm, and filtered using a regenerated cellulose filter (manufactured by ADVANTEC) with a pore size of 0.45 μm, as an example. 20. The pH of the obtained conductive polymer material was 4.8.

(實施例21) (Example 21)

將以調製例1所得之1.3質量%之導電性聚合物複合體分散液1(20g)、鋶鹽化合物4(0.5g)、二甲基亞碸5g、界面活性劑兼消泡劑的Surfynol465(0.5g)分別混合，然後，使用孔徑0.45μm的再生纖維素過濾器(ADVANTEC公司製)來過濾並調製導電性聚合物材料，使用孔徑0.45μm的再生纖維素過濾器(ADVANTEC公司製)來過濾，作為實施例21。所得之導電性聚合物材料之pH為4.2。 1.3% by mass of the conductive polymer composite dispersion liquid 1 (20 g), sulfonium salt compound 4 (0.5 g), 5 g of dimethylsulfenium, Surfynol 465 (surfactant and antifoaming agent) obtained in Preparation Example 1 were prepared. 0.5g) were mixed separately, and then a conductive polymer material was filtered and prepared using a regenerated cellulose filter (manufactured by ADVANTEC) with a pore size of 0.45 μm, and filtered using a regenerated cellulose filter (manufactured by ADVANTEC) with a pore size of 0.45 μm. As embodiment 21. The pH of the obtained conductive polymer material was 4.2.

(實施例22) (Example 22)

將以調製例1所得之1.3質量%之導電性聚合物複合體分散液1(20g)、鋶鹽化合物5(0.4g)、二甲基亞碸5g、界面活性劑兼消泡劑的Surfynol465(0.5g)分別混合，然後，使用孔徑0.45μm的再生纖維素過濾器(ADVANTEC公司製)來過濾並調製導電性聚合物材料，使用孔徑0.45μm的再生纖維素過濾器(ADVANTEC公司製)來過濾，作為實施例22。所得之導電性聚合物 材料之pH為4.4。 1.3% by mass of the conductive polymer composite dispersion liquid 1 (20 g), sulfonium salt compound 5 (0.4 g), dimethylsulfinium sulfide 5 g, Surfynol 465 (surfactant and defoamer) obtained in Preparation Example 1 were prepared. 0.5g) were mixed separately, and then a conductive polymer material was filtered and prepared using a regenerated cellulose filter (manufactured by ADVANTEC) with a pore size of 0.45 μm, and filtered using a regenerated cellulose filter (manufactured by ADVANTEC) with a pore size of 0.45 μm. As embodiment 22. Resulting conductive polymer The pH of the material was 4.4.

(實施例23) (Example 23)

將以調製例1所得之1.3質量%之導電性聚合物複合體分散液1(20g)、鋶鹽化合物6(0.4g)、二甲基亞碸5g、界面活性劑兼消泡劑的Surfynol465(0.5g)分別混合，然後，使用孔徑0.45μm的再生纖維素過濾器(ADVANTEC公司製)來過濾並調製導電性聚合物材料，使用孔徑0.45μm的再生纖維素過濾器(ADVANTEC公司製)來過濾，作為實施例23。所得之導電性聚合物材料之pH為4.9。 The 1.3% by mass of conductive polymer composite dispersion liquid 1 (20 g), sulfonium salt compound 6 (0.4 g), dimethylsulfinium 5 g, surfactant, and defoamer Surfynol 465 ( 0.5g) were mixed separately, and then a conductive polymer material was filtered and prepared using a regenerated cellulose filter (manufactured by ADVANTEC) with a pore size of 0.45 μm, and filtered using a regenerated cellulose filter (manufactured by ADVANTEC) with a pore size of 0.45 μm As embodiment 23. The pH of the obtained conductive polymer material was 4.9.

(實施例24) (Example 24)

將以調製例1所得之1.3質量%之導電性聚合物複合體分散液1(20g)、鋶鹽化合物7(0.3g)、二甲基亞碸5g、界面活性劑兼消泡劑的Surfynol465(0.5g)分別混合，然後，使用孔徑0.45μm的再生纖維素過濾器(ADVANTEC公司製)來過濾並調製導電性聚合物材料，使用孔徑0.45μm的再生纖維素過濾器(ADVANTEC公司製)來過濾，作為實施例24。所得之導電性聚合物材料之pH為4.0。 1.3% by mass of the conductive polymer composite dispersion liquid 1 (20 g), sulfonium salt compound 7 (0.3 g), 5 g of dimethyl fluorene, Surfynol 465 (surfactant and antifoaming agent) obtained in Preparation Example 1 were prepared. 0.5g) were mixed separately, and then a conductive polymer material was filtered and prepared using a regenerated cellulose filter (manufactured by ADVANTEC) with a pore size of 0.45 μm, and filtered using a regenerated cellulose filter (manufactured by ADVANTEC) with a pore size of 0.45 μm. As embodiment 24. The resulting conductive polymer material had a pH of 4.0.

(實施例25) (Example 25)

將以調製例1所得之1.3質量%之導電性聚合物複合 體分散液1(20g)、鋶鹽化合物8(1.5g)、二甲基亞碸5g、界面活性劑兼消泡劑的Surfynol465(0.5g)分別混合，然後，使用孔徑0.45μm的再生纖維素過濾器(ADVANTEC公司製)來過濾並調製導電性聚合物材料，使用孔徑0.45μm的再生纖維素過濾器(ADVANTEC公司製)來過濾，作為實施例25。所得之導電性聚合物材料之pH為4.6。 1.3 mass% of the conductive polymer obtained in Preparation Example 1 was compounded Body dispersion 1 (20g), osmium salt compound 8 (1.5g), dimethyl sulfenium 5g, Surfynol 465 (0.5g), a surfactant and an antifoaming agent were mixed separately, and then regenerated cellulose with a pore diameter of 0.45 μm was used. A filter (manufactured by ADVANTEC) was used to filter and prepare a conductive polymer material, and a regenerated cellulose filter (manufactured by ADVANTEC) having a pore diameter of 0.45 μm was used for filtration as Example 25. The pH of the obtained conductive polymer material was 4.6.

[比較例] [Comparative example] (比較例1) (Comparative example 1)

將以調製例15所得之1.3質量%之導電性聚合物複合體分散液15(20g)、二甲基亞碸5g、界面活性劑兼消泡劑的Surfynol465(0.5g)分別混合，然後，使用孔徑0.45μm的再生纖維素過濾器(ADVANTEC公司製)來過濾並調製導電性聚合物材料，作為比較例1。所得之導電性聚合物材料之pH為2.0。 1.3% by mass of the conductive polymer composite dispersion liquid 15 (20 g) obtained in Preparation Example 15 and 5 g of dimethylsulfene and Surfynol 465 (0.5 g) as a surfactant and an antifoaming agent were mixed and used. A regenerated cellulose filter (manufactured by ADVANTEC) having a pore diameter of 0.45 μm was used as a comparative example 1 to filter and prepare a conductive polymer material. The pH of the obtained conductive polymer material was 2.0.

(比較例2) (Comparative example 2)

將以調製例15所得之1.3質量%之導電性聚合物複合體分散液15(20g)、三乙醇胺0.23g、二甲基亞碸5g、界面活性劑兼消泡劑的Surfynol465(0.5g)分別混合，然後，使用孔徑0.45μm的再生纖維素過濾器(ADVANTEC公司製)來過濾並調製導電性聚合物材料，作為比較例2。所得之導電性聚合物材料之pH為6.1。 The 1.3% by mass conductive polymer composite dispersion liquid 15 (20g), Triethanolamine 0.23g, dimethylsulfene 5g, Surfynol 465 (0.5g), a surfactant and an antifoaming agent, obtained in Preparation Example 15 were respectively prepared. After mixing, a conductive polymer material was filtered and prepared using a regenerated cellulose filter (manufactured by ADVANTEC) having a pore diameter of 0.45 μm as Comparative Example 2. The pH of the obtained conductive polymer material was 6.1.

(比較例3) (Comparative example 3)

將以調製例15所得之1.3質量%之導電性聚合物複合體分散液15(20g)、氫氧化鈉0.06g、二甲基亞碸5g、界面活性劑兼消泡劑的Surfynol465(0.5g)分別混合，然後，使用孔徑0.45μm的再生纖維素過濾器(ADVANTEC公司製)來過濾並調製導電性聚合物材料，作為比較例3。所得之導電性聚合物材料之pH為6.2。 Surfynol 465 (0.5 g), a 1.3% by mass conductive polymer composite dispersion liquid (20 g), 0.06 g sodium hydroxide, 5 g dimethyl sulfene, and surfactant and antifoaming agent obtained in Preparation Example 15 Each of them was mixed, and then a conductive polymer material was filtered and prepared using a regenerated cellulose filter (manufactured by ADVANTEC) having a pore diameter of 0.45 μm as Comparative Example 3. The pH of the obtained conductive polymer material was 6.2.

(剛過濾後之塗佈性評價) (Applicability evaluation immediately after filtration)

首先，使用1H-360S SPINCOATER(MIKASA製)使膜厚成為100±5nm，將導電性聚合物材料旋轉塗佈(spincoat)於Si晶圓上。接著，以精密高溫機進行以120℃、5分鐘烘烤，藉由除去溶劑而得到導電膜。對於此導電膜，以入射角度可變的分光橢圓測厚儀VASE(J.A.Woollam公司製)，求得在波長636nm中之折射率(n，k)。可形成均勻膜者以○表示，可進行折射率之測定，雖可測定折射率，但於膜中產生來自顆粒的缺陷或部分產生條紋(striation)者以×表示於表1中。 First, a 1H-360S SPINCOATER (manufactured by MIKASA) was used to achieve a film thickness of 100 ± 5 nm, and a conductive polymer material was spin-coated on a Si wafer. Next, it baked at 120 degreeC for 5 minutes with the precision high temperature machine, and removed the solvent, and obtained the conductive film. With respect to this conductive film, the refractive index (n, k) at a wavelength of 636 nm was obtained with a spectroscopic ellipsometry VASE (manufactured by J.A. Woollam) with a variable incident angle. Those who can form a uniform film are indicated by ○, and the refractive index can be measured. Although the refractive index can be measured, those that cause defects or partial striation from the particles in the film are indicated in Table 1 by x.

(導電率評價) (Electrical conductivity evaluation)

首先，在直徑4吋(100mm)的SiO2晶圓上，滴入導電性聚合物材料1.0mL後，10秒後使用旋轉器旋轉塗佈於整體上。旋轉塗佈條件係膜厚調節成為100±5nm。以 精密高溫機進行120℃、5分鐘烘烤，藉由除去溶劑而得到導電膜。 First, 1.0 mL of a conductive polymer material was dropped onto a SiO 2 wafer having a diameter of 4 inches (100 mm), and the whole was spin-coated with a spinner after 10 seconds. The spin coating conditions were adjusted to 100 ± 5 nm. Baking was performed in a precision high temperature machine at 120 ° C. for 5 minutes, and the conductive film was obtained by removing the solvent.

對於所得之導電膜，實施例1~20、22~25係將加速電壓1keV之電子線以30μC/cm2之曝光量照射，在100℃下烘烤90秒鐘，實施例21則是將低壓水銀燈之波長254nm的光照射50mJ/cm2，於100℃下烘烤90秒鐘。 For the obtained conductive films, Examples 1 to 20 and 22 to 25 were irradiated with electron beams having an acceleration voltage of 1 keV at an exposure of 30 μC / cm 2 and baked at 100 ° C. for 90 seconds. A mercury lamp having a wavelength of 254 nm was irradiated with 50 mJ / cm 2 and baked at 100 ° C for 90 seconds.

塗佈後之膜與光照射後之膜的導電率(S/cm)係由使用Hiresta-UP MCP-HT450、Loresta-GP MCP-T610(均為三菱化學公司製)所測定之表面電阻率(Ω/□)與膜厚的實測值來求得。其結果表示於表1。 The electrical conductivity (S / cm) of the film after coating and the film after light irradiation is the surface resistivity (measured by Hiresta-UP MCP-HT450, Loresta-GP MCP-T610 (both manufactured by Mitsubishi Chemical Corporation)) Ω / □) and the measured value of the film thickness. The results are shown in Table 1.

(在23℃下、1個月後之塗佈性評價) (Coatability evaluation after 1 month at 23 ° C)

將所得之導電性聚合物材料以溶液之狀態下，於23℃下保存1個月，確認有無產生凝聚物。又，使用保存後之導電性聚合物材料，以與上述剛過濾後之塗佈性評價同樣的方法進行評價。結果如表1所示。 The obtained conductive polymer material was stored in a solution state at 23 ° C. for one month, and it was confirmed whether or not an aggregate was generated. The conductive polymer material after storage was evaluated in the same manner as in the applicability evaluation immediately after filtration. The results are shown in Table 1.

[包含作為π共軛系聚合物之聚噻吩之導電性聚合物材料之評價] [Evaluation of a conductive polymer material containing polythiophene as a π-conjugated polymer]

如表1所示，包含含有作為π共軛系聚合物之聚噻吩，且具有重複單位a1~a4或b之摻雜劑聚合物與鋶鹽化合物的實施例1~25係酸性度降低，導電性良好，在溶液中之保存中未產生凝聚物，以溶液保存1個月後之製膜性良好。此外，藉由電子線或光照射，鋶鹽化合物產生分解，提高導電性。 As shown in Table 1, Examples 1 to 25 containing a dopant polymer containing a polythiophene as a π-conjugated polymer and having repeating units a1 to a4 or b and a sulfonium salt compound have reduced acidity and conductivity. Good performance, no agglomerates were generated during storage in solution, and film-forming properties were good after storage in solution for 1 month. In addition, by irradiation with electron beams or light, the sulfonium salt compound is decomposed, and conductivity is improved.

而不含鋶鹽化合物之比較例1，雖導電性高，但是為強酸性。又，不含鋶鹽化合物之比較例2、3，雖為酸性度低者，但是導電性比實施例1~25差。又，比較例1~3在保存1個月後之塗佈性均較差。 Comparative Example 1, which does not contain a sulfonium salt compound, has high conductivity but is strongly acidic. In addition, Comparative Examples 2 and 3 which do not contain a sulfonium salt compound have lower acidity, but have lower conductivity than Examples 1 to 25. In addition, the coating properties of Comparative Examples 1 to 3 were poor after one month of storage.

如上述，可知本發明之導電性聚合物材料時，酸性度低，且可抑制經過時間之粒子之凝聚，在溶液中之安定性良好者。 As described above, it can be seen that when the conductive polymer material of the present invention has a low acidity, it can suppress the aggregation of particles that have passed over time, and has good stability in a solution.

又，本發明不限定於上述實施形態者。上述實施形態為例示，只要是具有實質上與本發明申請專利範圍所記載之技術思想相同的構成，且發揮相同作用效果者，均包含在本發明的技術範圍內。 The present invention is not limited to the embodiments described above. The above-mentioned embodiment is an example, as long as it has a structure substantially the same as the technical idea described in the patent application scope of the present invention and exhibits the same effect, it is included in the technical scope of the present invention.

Claims (8)

一種導電性聚合物材料，其包含：(A)π共軛聚合物；(B)含有具磺基之重複單位且具有重量平均分子量於1,000至500,000範圍的摻雜劑聚合物；及(C)下述一般式(1-1)與(1-2)表示之鋶鹽化合物之任一者或二者， 式中，R1、R2及R3獨立表示鹵素原子；含有具1至4個碳原子之烷基的胺基；具1至12個碳原子之直鏈狀、分枝狀或環狀之烷基、烯基、側氧基烷基或側氧基烯基；具6至20個碳原子之芳基；或具7至12個碳原子之芳烷基或芳基側氧基烷基，其中這些基可含有烷氧基、羥基、羧基、硝基、氰基、胺基、鹵素原子、酯基、醚基或硫醚基；R1與R2可彼此一起形成環，且當形成前述環時，R1與R2表示碳數具1至6個碳原子之伸烷基；R4、R5及R6獨立表示具1至4個碳原子之烷基；K-係選自氫氧離子、氯離子、溴離子、碳酸根離子、碳酸氫根離子、硝酸根離子、羧酸根離子、磺酸根離子、亞磺酸根離子所組成群 組，且當K-為羧酸根離子時，K-取代於R1、R2及R3之任一者上而形成內鹽，其中前述成分(B)具有α位經氟化的磺基及/或鍵結於經氟化之芳香族基之磺基，其中前述成分(B)含有選自下述一般式(2)表示之一種或多種重複單位(2-1)至(2-4)， 式中，R7、R9、R12及R14各表示氫原子或甲基；R8、R10、R13各表示單鍵、酯基，或具1至12個碳原子且具有醚基及酯基之任一者或二者之直鏈狀、分枝狀、或環狀之烴基；R11表示具1至4個碳原子之直鏈狀或分枝狀之伸烷基，其中R11中之1或2個氫原子經氟原子取代；R15 表示氟原子或三氟甲基；Z1及Z2各表示伸苯基、伸萘基、或酯基；Z3表示單鍵、伸苯基、伸萘基、醚基、或酯基；Z4表示單鍵或酯基；限制條件為當Z2為伸苯基時，R10不含有醚基；“p”為1至4之整數；及“a1”、“a2”、“a3”、及“a4”各為滿足下列之數目：0≦a1≦1.0、0≦a2≦1.0、及0≦a3≦1.0、0≦a4≦1.0、及0<a1+a2+a3+a4≦1.0。 A conductive polymer material comprising: (A) a π conjugated polymer; (B) a dopant polymer containing repeating units having a sulfo group and having a weight average molecular weight ranging from 1,000 to 500,000; and (C) Either or both of the phosphonium salt compounds represented by the following general formulae (1-1) and (1-2), In the formula, R 1 , R 2 and R 3 independently represent a halogen atom; an amine group containing an alkyl group having 1 to 4 carbon atoms; a linear, branched or cyclic group having 1 to 12 carbon atoms Alkyl, alkenyl, oxyalkyl or oxyalkenyl; aryl having 6 to 20 carbon atoms; or aralkyl or aryl pendant oxyalkyl having 7 to 12 carbon atoms, Wherein these groups may contain an alkoxy group, a hydroxyl group, a carboxyl group, a nitro group, a cyano group, an amine group, a halogen atom, an ester group, an ether group or a thioether group; R 1 and R 2 may form a ring together with each other, and when the foregoing In the ring, R 1 and R 2 represent an alkylene group having 1 to 6 carbon atoms; R 4 , R 5 and R 6 independently represent an alkyl group having 1 to 4 carbon atoms; K - is selected from hydrogen A group of oxygen ion, chloride ion, bromide ion, carbonate ion, bicarbonate ion, nitrate ion, carboxylate ion, sulfonate ion, sulfinate ion, and when K - is a carboxylate ion, K - substituents on R 1, R 2 and the R 3 to any one of the inner salt is formed, wherein the component (B) having fluorinated α position sulfo group and / or an aromatic group bonded to the fluorination of the Sulfo Fraction (B) contains one kind selected from the following general formula (2) or more of repeating units represented by (2-1) to (2-4), In the formula, R 7 , R 9 , R 12, and R 14 each represent a hydrogen atom or a methyl group; R 8 , R 10 , and R 13 each represent a single bond, an ester group, or an ether group having 1 to 12 carbon atoms And one or both of the ester groups are linear, branched, or cyclic hydrocarbon groups; R 11 represents a linear or branched alkylene group having 1 to 4 carbon atoms, where R One or two hydrogen atoms in 11 are replaced by fluorine atoms; R 15 represents a fluorine atom or a trifluoromethyl group; Z 1 and Z 2 each represent a phenyl group, a naphthyl group, or an ester group; Z 3 represents a single bond, Phenylene, naphthyl, ether, or ester group; Z 4 represents a single bond or an ester group; the limitation is that when Z 2 is phenylene, R 10 does not contain an ether group; "p" is 1 to 4 Integers; and "a1", "a2", "a3", and "a4" are each a number satisfying the following: 0 ≦ a1 ≦ 1.0, 0 ≦ a2 ≦ 1.0, and 0 ≦ a3 ≦ 1.0, 0 ≦ a4 ≦ 1.0, and 0 <a1 + a2 + a3 + a4 ≦ 1.0. 如申請專利範圍第1項之導電性聚合物材料，其中前述成分(B)含有下述一般式(3)表示之重複單位， 式中，“b”為滿足0<b≦1.0之數目。 For example, in the conductive polymer material of the scope of application for a patent, wherein the aforementioned component (B) contains a repeating unit represented by the following general formula (3), In the formula, “b” is a number satisfying 0 <b ≦ 1.0. 如申請專利範圍第1項之導電性聚合物材料，其中前述成分(B)為嵌段共聚物。 For example, the conductive polymer material according to the first patent application range, wherein the aforementioned component (B) is a block copolymer. 如申請專利範圍第1項之導電性聚合物材料，其中前述成分(A)為藉由聚合選自由吡咯、噻吩、硒吩、碲吩、苯胺、多環式芳香族化合物、及其衍生物所組成群組之一或多種前驅物單體形成的聚合物。 For example, the conductive polymer material according to item 1 of the patent application, wherein the aforementioned component (A) is selected from the group consisting of pyrrole, thiophene, selenophene, tellurene, aniline, polycyclic aromatic compounds, and derivatives thereof by polymerization. A polymer formed from one or more precursor monomers in a group. 如申請專利範圍第1項之導電性聚合物材料，其中前述導電性聚合物材料具有於水中或有機溶劑中之分散性。 For example, the conductive polymer material according to the scope of patent application, wherein the aforementioned conductive polymer material has dispersibility in water or an organic solvent. 一種基板，其具有藉由使用如申請專利範圍第1 項之導電性聚合物材料形成於其上之導電膜。 A substrate has the following advantages: A conductive film on which a conductive polymer material is formed. 如申請專利範圍第6項之基板，其中前述導電膜係藉由將前述導電性聚合物材料塗佈於前述基板上，然後曝光於具有波長140至400nm之光或曝光於電子束而形成。 For example, the substrate of the patent application No. 6 wherein the aforementioned conductive film is formed by coating the aforementioned conductive polymer material on the aforementioned substrate and then exposing it to light having a wavelength of 140 to 400 nm or to an electron beam. 如申請專利範圍第6項之基板，其中前述導電膜為作為透明電極層。 For example, the substrate of the sixth scope of the patent application, wherein the aforementioned conductive film is used as a transparent electrode layer.
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