JP2013020943A - Electronic element, conductive polymer composition, and method for producing the same - Google Patents
Electronic element, conductive polymer composition, and method for producing the same Download PDFInfo
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- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 73
- 239000000203 mixture Substances 0.000 title claims abstract description 70
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 37
- 229920005610 lignin Polymers 0.000 claims abstract description 37
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims abstract description 26
- 229940005642 polystyrene sulfonic acid Drugs 0.000 claims abstract description 26
- 229920000620 organic polymer Polymers 0.000 claims abstract description 17
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 16
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 239000003990 capacitor Substances 0.000 claims description 38
- 239000000178 monomer Substances 0.000 claims description 21
- 239000007800 oxidant agent Substances 0.000 claims description 12
- 230000005684 electric field Effects 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- -1 propylidene group Chemical group 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 125000001118 alkylidene group Chemical group 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 claims description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims 1
- 239000000243 solution Substances 0.000 description 31
- 238000005259 measurement Methods 0.000 description 18
- 239000002019 doping agent Substances 0.000 description 10
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000000502 dialysis Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- 239000013638 trimer Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000004815 dispersion polymer Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229930192474 thiophene Natural products 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 229910000358 iron sulfate Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- FYMCOOOLDFPFPN-UHFFFAOYSA-K iron(3+);4-methylbenzenesulfonate Chemical compound [Fe+3].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 FYMCOOOLDFPFPN-UHFFFAOYSA-K 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- MRYMYQPDGZIGDM-UHFFFAOYSA-L copper;4-methylbenzenesulfonate Chemical compound [Cu+2].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 MRYMYQPDGZIGDM-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
Abstract
Description
本発明は、電子素子、導電性高分子組成物およびその製造方法に関するものであって、特に、優れた電気的性質を有する電子素子、導電性高分子組成物およびその製造方法に関するものである。 The present invention relates to an electronic device, a conductive polymer composition, and a method for producing the same, and particularly relates to an electronic device having excellent electrical properties, a conductive polymer composition, and a method for producing the same.
導電性高分子（例えば、ポリアニリン、ポリピロール、ポリチオフェン）は、導電性と塗布可能な性質を有するので、幅広く、静電気防止コーティング、電界コンデンサ、太陽電池および電界発光ディスプレイ等の領域に応用されている。例えば、特許文献１には、ポリ（３，４−ジアルコキシチオフェン）の分散体およびその製造方法、それを用いた静電防止コーティングなどが記載されている。一方、ポリ（３，４−エチレンジオキシチオフェン）（ＰＥＤＯＴ）は、現在、導電性高分子のうちで導電性が高い導電性高分子の一つである。高導電度、高熱安定性、薄膜時の透明性がよいので、ポリ３，４−エチレンジオキシチオフェンは最も注目されている導電性高分子である。 Conductive polymers (for example, polyaniline, polypyrrole, polythiophene) have conductivity and properties that can be applied, and thus have been widely applied to areas such as antistatic coatings, electric field capacitors, solar cells, and electroluminescent displays. For example, Patent Document 1 describes a dispersion of poly (3,4-dialkoxythiophene), a production method thereof, an antistatic coating using the same, and the like. On the other hand, poly (3,4-ethylenedioxythiophene) (PEDOT) is one of conductive polymers having high conductivity among conductive polymers. Poly 3,4-ethylenedioxythiophene is a conductive polymer that has attracted the most attention because of its high conductivity, high thermal stability, and good transparency in thin films.
ポリ３，４−エチレンジオキシチオフェンを製造する際には、一般に、スルホン酸化分子ドーパントを加えて、分散性を増加させている。ドーパントは、低分子ドーパントと高分子ドーパントに分けられる。低分子ドーパントは、例えば、ベンゼンスルホン酸、ｐ−トルエンスルホン酸、ナフタリンスルホン酸等である。高分子ドーパントは、例えば、ポリスチレンスルホン酸、ポリエチレンスルホン酸等である。ポリスチレンスルホン酸を例とすると、ドイツのバイエル社（Ｂａｙｅｒ）が、まず、１９９１年に、ポリスチレンスルホン酸をポリ３，４−エチレンジオキシチオフェン中にドープしている。ポリスチレンスルホン酸は、この導電性高分子中で二種の作用があり、一つは、電荷平衡のドーパントとなること、もう一つは、ポリ３，４−エチレンジオキシチオフェンの分散を助けることである。バイエル社が開発したポリ３，４−エチレンジオキシチオフェン／ポリスチレンスルホン酸は、ポリ３，４−エチレンジオキシチオフェンの分散性を高め、加工性が増加する。しかし、ポリ３，４−エチレンジオキシチオフェン／ポリスチレンスルホン酸を固体電界コンデンサの電極とする場合、得られた固体電界コンデンサのキャパシタンスは低く、高いキャパシタンスを有するコンデンサを製造することができない。 When producing poly 3,4-ethylenedioxythiophene, a sulfonated molecular dopant is generally added to increase dispersibility. The dopant is divided into a low molecular dopant and a high molecular dopant. Examples of the low molecular dopant include benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, and the like. Examples of the polymer dopant include polystyrene sulfonic acid and polyethylene sulfonic acid. Taking polystyrene sulfonic acid as an example, Bayer, Germany, first doped polystyrene sulfonic acid in poly3,4-ethylenedioxythiophene in 1991. Polystyrene sulfonic acid has two functions in this conductive polymer, one is a charge-balanced dopant, and the other is to help disperse poly 3,4-ethylenedioxythiophene. It is. Poly 3,4-ethylenedioxythiophene / polystyrene sulfonic acid developed by Bayer increases the dispersibility of poly 3,4-ethylenedioxythiophene and increases processability. However, when poly 3,4-ethylenedioxythiophene / polystyrene sulfonic acid is used as an electrode of a solid electric field capacitor, the capacitance of the obtained solid electric field capacitor is low, and a capacitor having a high capacitance cannot be manufactured.
よって、新規の導電性高分子組成物を提供し、従来の技術による問題を解決することが、現在、導電性高分子技術研究における重要な課題である。 Therefore, providing a novel conductive polymer composition and solving the problems caused by the conventional technology is an important issue in conducting polymer research.
本発明は、電子素子、導電性高分子組成物およびその製造方法を提供することを目的とする。 An object of this invention is to provide an electronic device, a conductive polymer composition, and its manufacturing method.
本発明は、導電性高分子組成物を提供する。導電性高分子組成物は、有機ポリマー、ポリスチレンスルホン酸およびリグニンスルホン酸を含む。有機ポリマーは、式（Ｉ）： The present invention provides a conductive polymer composition. The conductive polymer composition includes an organic polymer, polystyrene sulfonic acid, and lignin sulfonic acid. The organic polymer has the formula (I):
［式中、Ｘ１およびＸ２は、それぞれ独立して、ＯまたはＳ、ＹはＣ１−４アルキレン基またはＣ２−４アルキリデン基、Ｒ１はＨまたはＣ１−１８アルキル基、Ｃ５−１２シクロアルキル基またはアリール基である］
で示される繰り返し単位を有する。
[Wherein, X 1 and X 2 are each independently O or S, Y is a C 1-4 alkylene group or C 2-4 alkylidene group, R 1 is H or a C 1-18 alkyl group, C 5 -12 is a cycloalkyl group or an aryl group]
It has a repeating unit represented by
本発明は、上記導電性高分子組成物の製造方法をも提供する。導電性高分子組成物の製造方法は、以下の工程を含む：（ａ）リグニンスルホン酸、ポリスチレンスルホン酸、水および酸化剤の存在下で、モノマーに重合反応を実行する。モノマーは、式（ＩＩ）： The present invention also provides a method for producing the conductive polymer composition. The method for producing a conductive polymer composition includes the following steps: (a) A monomer is subjected to a polymerization reaction in the presence of lignin sulfonic acid, polystyrene sulfonic acid, water and an oxidizing agent. The monomer has the formula (II):
［式中、Ｘ１およびＸ２は、それぞれ独立して、ＯまたはＳ、ＹはＣ１−４アルキレン基またはＣ２−４アルキリデン基、Ｒ１はＨまたはＣ１−１８アルキル基、Ｃ５−１２シクロアルキル基またはアリール基である］で示される構造を有する；（ｂ）純化工程を実行して、酸化剤（さらに、未反応のモノマー、モノマーの二量体、モノマーの三量体、またはモノマーのオリゴマー）を除去して、導電性高分子組成物を得る。 [Wherein, X 1 and X 2 are each independently O or S, Y is a C 1-4 alkylene group or C 2-4 alkylidene group, R 1 is H or a C 1-18 alkyl group, C 5 -12 is a cycloalkyl group or an aryl group]; (b) performing a purification step to carry out an oxidizing agent (in addition, an unreacted monomer, a monomer dimer, a monomer trimer, Alternatively, the monomer oligomer) is removed to obtain a conductive polymer composition.
本発明のある態様によると、本発明は、基板および基板上に形成された導電層を含む電子素子を提供する。導電層は、上記導電性高分子組成物を基板上に塗布して得られる。本発明の別の態様によると、電子素子は、静電気防止塗膜、電界コンデンサ、太陽電池または電界発光ディスプレイである。 According to one aspect of the present invention, the present invention provides an electronic device comprising a substrate and a conductive layer formed on the substrate. The conductive layer is obtained by applying the conductive polymer composition onto a substrate. According to another aspect of the invention, the electronic device is an antistatic coating, an electric field capacitor, a solar cell or an electroluminescent display.
本発明による導電性高分子組成物は、リグニンスルホン酸およびポリスチレンスルホン酸を導電性高分子のドーパントとし、導電性高分子組成物の電荷平衡およびチオフェン高分子分散を促進する以外に、導電性高分子組成物は、固体電界コンデンサへの応用に非常に適し、キャパシタンスを増加させる。 The conductive polymer composition according to the present invention uses lignin sulfonic acid and polystyrene sulfonic acid as dopants for the conductive polymer, and promotes charge balance and thiophene polymer dispersion of the conductive polymer composition. The molecular composition is very suitable for applications in solid state electric capacitors and increases capacitance.
本発明は、導電性高分子組成物、その製造方法およびその応用を提供する。導電性高分子組成物の特徴は、リグニンスルホン酸およびポリスチレンスルホン酸を、導電性高分子のドーパントとし、導電性高分子組成物の電荷平衡およびチオフェン高分子分散を促進する以外に、導電性高分子組成物は、固体電界コンデンサへの応用に非常に適し、キャパシタンスを増加させる。 The present invention provides a conductive polymer composition, a production method thereof, and an application thereof. The characteristics of the conductive polymer composition are that, in addition to using lignin sulfonic acid and polystyrene sulfonic acid as dopants for the conductive polymer to promote charge balance and thiophene polymer dispersion of the conductive polymer composition, The molecular composition is very suitable for applications in solid state electric capacitors and increases capacitance.
本発明の導電性高分子組成物は、有機ポリマー、ポリスチレンスルホン酸およびリグニンスルホン酸を含む。本発明のある態様によると、有機ポリマーは、式（Ｉ）： The conductive polymer composition of the present invention contains an organic polymer, polystyrene sulfonic acid and lignin sulfonic acid. According to one embodiment of the present invention, the organic polymer has the formula (I):
［式中、Ｘ１およびＸ２は、それぞれ独立して、ＯまたはＳ、ＹはＣ１−４アルキレン基またはＣ２−４アルキリデン基、Ｒ１はＨまたはＣ１−１８アルキル基、Ｃ５−１２シクロアルキル基またはアリール基である］で示される繰り返し単位を有する。本発明の別の態様によると、Ｙはメチレン基、エチリデン基、プロピリデン基またはブチリデン基である。リグニンスルホン酸は、木材を処理した後（例えば、硝酸やアルカリ）、外皮物質を除去して、分離したリグニンを、さらに、亜硫酸塩でスルホン酸化して得られるものである。本発明のある態様によると、使用するリグニンスルホン酸の重量平均分子量は、好ましくは１，０００〜１，０００，０００（より好ましくは２，０００〜２５，０００、さらに好ましくは２，５００〜２０，０００、さらにより好ましくは５，０００〜１５，０００）である。リグニンスルホン酸の硫黄含量は、好ましくは１％〜２０％である。本発明の導電性高分子組成物において、ポリスチレンスルホン酸と有機ポリマーとの質量比は、好ましくは０．６〜１３である。リグニンスルホン酸と有機ポリマーとの質量比は、好ましくは０．１〜１７である。 [Wherein, X 1 and X 2 are each independently O or S, Y is a C 1-4 alkylene group or C 2-4 alkylidene group, R 1 is H or a C 1-18 alkyl group, C 5 A -12 cycloalkyl group or an aryl group]. According to another aspect of the present invention, Y is a methylene group, an ethylidene group, a propylidene group or a butylidene group. Lignin sulfonic acid is obtained by treating wood (for example, nitric acid or alkali), removing the skin material, and further sulfonating the separated lignin with sulfite. According to an embodiment of the present invention, the weight average molecular weight of the lignin sulfonic acid used is preferably 1,000 to 1,000,000 (more preferably 2,000 to 25,000, still more preferably 2,500 to 20). 5,000, even more preferably 5,000 to 15,000). The sulfur content of lignin sulfonic acid is preferably 1% to 20%. In the conductive polymer composition of the present invention, the mass ratio of polystyrene sulfonic acid to organic polymer is preferably 0.6 to 13. The mass ratio of lignin sulfonic acid to organic polymer is preferably 0.1-17.
本発明の別の態様では、本発明による導電性高分子組成物の製造方法は、以下の工程を含む。リグニンスルホン酸、ポリスチレンスルホン酸、水（または、さらに、その他の水溶性溶剤（例えば、メタノール、エタノール、エチレングリコール、アセトン、テトラヒドロフランまたは混合溶剤）を含む）、および酸化剤の存在下で、モノマーに重合反応を実行し、モノマーを有機ポリマーに合成する。モノマーは、式（ＩＩ）： In another aspect of the present invention, the method for producing a conductive polymer composition according to the present invention includes the following steps. In the presence of lignin sulfonic acid, polystyrene sulfonic acid, water (or in addition, other water-soluble solvents (eg, methanol, ethanol, ethylene glycol, acetone, tetrahydrofuran or mixed solvents)), and in the presence of an oxidizing agent, the monomer A polymerization reaction is performed to synthesize monomers into organic polymers. The monomer has the formula (II):
［式中、Ｘ１およびＸ２は、それぞれ独立して、ＯまたはＳ、ＹはＣ１−４アルキレン基またはＣ２−４アルキリデン基、Ｒ１はＨまたはＣ１−１８アルキル基、Ｃ５−１２シクロアルキル基またはアリール基である］で示される。続いて、得られた反応液に純化工程を実行して、酸化剤、未反応のモノマー、モノマーの二量体、モノマーの三量体、またはモノマーのオリゴマーを除去して、導電性高分子組成物を得る。モノマーとリグニンスルホン酸およびポリスチレンスルホン酸との当量比は、好ましくは１：０．５〜１：１０である。モノマーと酸化剤との当量比は、好ましくは１：０．５〜１：５である。重合反応の温度は、好ましくは−５℃〜７０℃である。使用する酸化剤は、例えば、過硫酸塩（例えば、過硫酸ナトリウム、過硫酸カリウムまたは過硫酸アンモニウム）、三価鉄塩（例えば、ｐ−トルエンスルホン酸鉄（ＩＩＩ）、硫酸鉄（ＩＩＩ）、塩化鉄（ＩＩＩ）または硝酸鉄（ＩＩＩ））、二価銅塩（例えば、ｐ−トルエンスルホン酸銅）またはそれらの組み合わせ（例えば、過硫酸ナトリウムとｐ−トルエンスルホン酸鉄（ＩＩＩ）との混合物または過硫酸アンモニウムと硫酸鉄（ＩＩＩ）との混合物）である。純化工程は、イオン交換樹脂、遠心分離法、透析法、限外ろ過、ろ過、またはこれらの組み合わせで実行する。このほか、重合反応実行時、同時に、分散工程を実行してもよく、例えば、従来の攪拌機、乳化機、ホモジナイザー、超音波または高圧ホモジナイザーにより実行する。 [Wherein, X 1 and X 2 are each independently O or S, Y is a C 1-4 alkylene group or C 2-4 alkylidene group, R 1 is H or a C 1-18 alkyl group, C 5 -12 is a cycloalkyl group or an aryl group]. Subsequently, a purification step is performed on the obtained reaction liquid to remove the oxidizing agent, unreacted monomer, monomer dimer, monomer trimer, or monomer oligomer, and the conductive polymer composition. Get things. The equivalent ratio of monomer to lignin sulfonic acid and polystyrene sulfonic acid is preferably 1: 0.5 to 1:10. The equivalent ratio of monomer to oxidizing agent is preferably 1: 0.5 to 1: 5. The temperature of the polymerization reaction is preferably −5 ° C. to 70 ° C. Examples of the oxidizing agent used include persulfates (for example, sodium persulfate, potassium persulfate or ammonium persulfate), trivalent iron salts (for example, iron (III) p-toluenesulfonate, iron (III) sulfate, chloride) Iron (III) or iron (III) nitrate), divalent copper salts (for example copper p-toluenesulfonate) or combinations thereof (for example a mixture of sodium persulfate and iron (III) p-toluenesulfonate) A mixture of ammonium persulfate and iron (III) sulfate). The purification step is performed by ion exchange resin, centrifugation, dialysis, ultrafiltration, filtration, or a combination thereof. In addition, the dispersion step may be performed simultaneously with the polymerization reaction. For example, the dispersion step is performed by a conventional stirrer, emulsifier, homogenizer, ultrasonic wave, or high-pressure homogenizer.
このほか、本発明は、基板および基板上に形成された導電層を含む電子素子をも提供する。導電層は、本発明の導電性高分子組成物を基板上に塗布して得られる。電子素子は、例えば、静電気防止塗膜、電界コンデンサ、太陽電池または電界発光ディスプレイである。例えば、図１を参照すると、電子素子は電界コンデンサ１０であり、基板は金属酸化物層１４である。電界コンデンサ１０は、第一金属電極（例えば、アルミニウム）１２と、導電層１６（本発明の導電性高分子組成物を塗布して得られる）上に設置された第二金属電極（例えば、アルミニウム）１８とを含む。第一金属電極１２は、その上に金属酸化物層１４（例えば、酸化アルミニウム（Ａｌ２Ｏ３））が形成されている。金属酸化物層１４は、複数の凹部２０を含んでもよい。金属酸化物層１４は、金属電極１２に酸化工程を実行して得られる。このほか、導電層１６を金属酸化物層１４上に形成すると共に、複数の凹部２０を充填してもよい。
In addition, the present invention also provides an electronic device including a substrate and a conductive layer formed on the substrate. The conductive layer is obtained by applying the conductive polymer composition of the present invention on a substrate. The electronic element is, for example, an antistatic coating, an electric field capacitor, a solar cell, or an electroluminescent display. For example, referring to FIG. 1, the electronic element is an
本発明の上記説明およびその他の目的、特徴、長所を理解しやすくするため、以下で幾つかの実施例により、本発明の導電性高分子組成物、その製造方法、およびそれを含む電子装置を説明する。 In order to facilitate understanding of the above description and other objects, features, and advantages of the present invention, a conductive polymer composition of the present invention, a method for producing the same, and an electronic device including the same will be described below according to some examples. explain.
実施例１
３，４−エチレンジオキシチオフェン（ＥＤＯＴ）１４．２ｇ（０．１ｍｏｌ）を準備し、１，３６２．２５ｍＬの脱イオン水、ポリスチレンスルホン酸（ＰＳＳ）１０２．２４ｇ（０．１ｍｏｌ、分子量約７５，０００、１８％水溶液）、および１２．０７ｇのリグニンスルホン酸（製品番号ＢＧ−ＮＨ４、Ｂｏｒｒｅｇａａｒｄにより製造販売、スルホン酸形式はＳＯ３ＮＨ４、重量平均分子量は２３，２８１、硫黄含量は５．１９％）を加えた。続いて、上記溶液を２０℃下で均一に攪拌後、窒素を溶液中に送り、少なくとも３０分攪拌し続けた。ここで、溶液中に、過硫酸アンモニウム１８．２４７ｇ（０．０８ｍｏｌ）および硫酸鉄０．５６８ｇ（０．００２ｍｏｌ）を加え、２０℃下で、１６時間反応させた。
Example 1
3.42 g (0.1 mol) of 3,4-ethylenedioxythiophene (EDOT) was prepared, and 1,362.25 mL of deionized water, 102.24 g of polystyrene sulfonic acid (PSS) (0.1 mol, molecular weight of about 75). 1,000, 18% aqueous solution), and 12.07 g of lignin sulfonic acid (product number BG-NH4, manufactured and sold by Borregaard, sulfonic acid form is SO 3 NH 4 , weight average molecular weight is 23,281, sulfur content is 5. 19%). Subsequently, after the solution was uniformly stirred at 20 ° C., nitrogen was fed into the solution and stirring was continued for at least 30 minutes. Here, 18.247 g (0.08 mol) of ammonium persulfate and 0.568 g (0.002 mol) of iron sulfate were added to the solution and reacted at 20 ° C. for 16 hours.
反応後の溶液は、透析膜（ＭＷＣＯ：１２，０００〜１４，０００）により、透析純化を実行し、未反応のモノマー、二量体、三量体、オリゴマーおよび酸化剤を除去した。純化後の溶液を、さらに、ホモジナイザーで処理し、導電性高分子組成物（ＰＥＤＯＴ−ＰＳＳ−ＬＧＮ）溶液（１）を得た。 The solution after the reaction was subjected to dialysis purification using a dialysis membrane (MWCO: 12,000 to 14,000) to remove unreacted monomers, dimers, trimers, oligomers and oxidizing agents. The purified solution was further treated with a homogenizer to obtain a conductive polymer composition (PEDOT-PSS-LGN) solution (1).
続いて、３個のコンデンサを用意し、上記で得られた導電性高分子組成物溶液（１）に５分間浸漬した。取り出した後、１１０℃で６０分間乾燥させた。得られたコンデンサは、それぞれ、ＬＣＲメータ（Ａｇｉｌｅｎｔ ４２６３Ｂ）で測定した（測定条件：電圧１，０００ｍＶ、周波数１２０Ｈｚ）。測定結果を表１に示す。 Subsequently, three capacitors were prepared and immersed in the conductive polymer composition solution (1) obtained above for 5 minutes. After taking out, it was dried at 110 ° C. for 60 minutes. Each of the obtained capacitors was measured with an LCR meter (Agilent 4263B) (measurement conditions: voltage 1,000 mV, frequency 120 Hz). The measurement results are shown in Table 1.
実施例２
リグニンスルホン酸をＢＧ−ＮＨ４からＢＧ−Ｃａ（Ｂｏｒｒｅｇａａｒｄにより製造販売、スルホン酸形式はＳＯ３Ｃａ、重量平均分子量は１３，６４７、硫黄含量は４．６６％）に変更したこと以外は、実施例１と同様の製造工程を実行し、導電性高分子組成物（ＰＥＤＯＴ−ＰＳＳ−ＬＧＮ）溶液（２）を得た。
Example 2
Except that lignin sulfonic acid was changed from BG-NH4 to BG-Ca (manufactured and sold by Borregaard, sulfonic acid form is SO 3 Ca, weight average molecular weight is 13,647, sulfur content is 4.66%) The manufacturing process similar to 1 was performed and the electroconductive polymer composition (PEDOT-PSS-LGN) solution (2) was obtained.
３個のコンデンサを用意し、上記で得られた導電性高分子組成物溶液（２）に５分間浸漬した。取り出した後、１１０℃で６０分間乾燥させた。得られたコンデンサは、それぞれ、ＬＣＲメータ（Ａｇｉｌｅｎｔ ４２６３Ｂ）で測定した（測定条件：電圧１，０００ｍＶ、周波数１２０Ｈｚ）た。測定結果を表１に示す。 Three capacitors were prepared and immersed in the conductive polymer composition solution (2) obtained above for 5 minutes. After taking out, it was dried at 110 ° C. for 60 minutes. Each of the obtained capacitors was measured with an LCR meter (Agilent 4263B) (measurement conditions: voltage 1,000 mV, frequency 120 Hz). The measurement results are shown in Table 1.
実施例３
リグニンスルホン酸をＢＧ−ＮＨ４からＢＧ−Ｎａ（Ｂｏｒｒｅｇａａｒｄにより製造販売、そのスルホン酸形式はＳＯ３Ｎａ、重量平均分子量は１２，１５１、硫黄含量は４．７０％）に変更したこと以外は、実施例１と同様の製造工程を実行し、導電性高分子組成物（ＰＥＤＯＴ−ＰＳＳ−ＬＧＮ）溶液（３）を得た。
Example 3
Except that lignin sulfonic acid was changed from BG-NH4 to BG-Na (manufactured and sold by Borregaard, the sulfonic acid form is SO 3 Na, the weight average molecular weight is 12,151, the sulfur content is 4.70%) The manufacturing process similar to Example 1 was performed, and the conductive polymer composition (PEDOT-PSS-LGN) solution (3) was obtained.
３個のコンデンサを用意し、上記で得られた導電性高分子組成物溶液（３）に５分間浸漬した。取り出した後、１１０℃で６０分間乾燥させた。得られたコンデンサは、それぞれ、ＬＣＲメータ（Ａｇｉｌｅｎｔ ４２６３Ｂ）で測定した（測定条件：電圧１，０００ｍＶ、周波数１２０Ｈｚ）。測定結果を表１に示す。 Three capacitors were prepared and immersed in the conductive polymer composition solution (3) obtained above for 5 minutes. After taking out, it was dried at 110 ° C. for 60 minutes. Each of the obtained capacitors was measured with an LCR meter (Agilent 4263B) (measurement conditions: voltage 1,000 mV, frequency 120 Hz). The measurement results are shown in Table 1.
実施例４
リグニンスルホン酸をＢＧ−ＮＨ４からＭＣＬ−Ｈ（ＩＴＲＩにより製造、そのスルホン酸形式はＳＯ３Ｈ、重量平均分子量は２，０７１、硫黄含量は６．１２％、リグニンスルホン酸ＭＣＬ−Ｈの製造方法は：リグニンスルホン酸１００質量部を準備し、３０質量部のＮａ２ＳＯ３、および１００質量部の１Ｎ ＮａＯＨを加えると共に、オートクレーブに入れて、１５０℃下で４時間反応させた。反応完成後、２０質量部の硫酸を加え、イオン交換樹脂により、溶液中のイオンを除去する）に変更したこと以外は、実施例１と同様の製造工程を実行し、導電性高分子組成物（ＰＥＤＯＴ−ＰＳＳ−ＬＧＮ）溶液（４）を得た。
Example 4
Lignin sulfonic acid is produced from BG-NH4 with MCL-H (produced by ITRI, the sulfonic acid form is SO 3 H, the weight average molecular weight is 2,071, the sulfur content is 6.12%, and the production method of lignin sulfonic acid MCL-H Ha: 100 parts by weight of lignin sulfonic acid was prepared, 30 parts by weight of Na 2 SO 3 and 100 parts by weight of 1N NaOH were added, and the mixture was placed in an autoclave and reacted at 150 ° C. for 4 hours. , Except that 20 parts by mass of sulfuric acid was added and the ion exchange resin was used to remove ions in the solution, and the same manufacturing process as in Example 1 was performed, and the conductive polymer composition (PEDOT- PSS-LGN) solution (4) was obtained.
３個のコンデンサを用意し、上記で得られた導電性高分子組成物溶液（４）に５分間浸漬した。取り出した後、１１０℃で６０分間乾燥させた。得られたコンデンサは、それぞれ、ＬＣＲメータ（Ａｇｉｌｅｎｔ ４２６３Ｂ）で測定した（測定条件：電圧１，０００ｍＶ、周波数１２０Ｈｚ）。測定結果を表１に示す。 Three capacitors were prepared and immersed in the conductive polymer composition solution (4) obtained above for 5 minutes. After taking out, it was dried at 110 ° C. for 60 minutes. Each of the obtained capacitors was measured with an LCR meter (Agilent 4263B) (measurement conditions: voltage 1,000 mV, frequency 120 Hz). The measurement results are shown in Table 1.
実施例５
リグニンスルホン酸を１２．０７ｇから１．２０７ｇに変更したこと以外は、実施例４と同様の製造工程を実行し、導電性高分子組成物（ＰＥＤＯＴ−ＰＳＳ−ＬＧＮ）溶液（５）を得た。
Example 5
Except having changed lignin sulfonic acid from 12.07g to 1.207g, the manufacturing process similar to Example 4 was performed, and the conductive polymer composition (PEDOT-PSS-LGN) solution (5) was obtained. .
３個のコンデンサ（コンデンサはコンデンサメーカーから用意し、陽極電蝕アルミ箔、隔離紙および陰極アルミ箔を含み、陽極アルミ箔と陰極アルミ箔は、それぞれ、導電用のピンを接続している）を準備し、上記で得られた導電性高分子組成物溶液（５）に５分間浸漬した。取り出した後、１１０℃で６０分間乾燥させた。得られたコンデンサは、それぞれ、ＬＣＲメータ（Ａｇｉｌｅｎｔ ４２６３Ｂ）で測定した（測定条件：電圧１，０００ｍＶ、周波数１２０Ｈｚ）。測定結果を表１に示す。 3 capacitors (capacitors prepared from capacitor manufacturers, including anode electro-corrosion aluminum foil, separator paper and cathode aluminum foil, each of which is connected to conductive pins) Prepared and immersed in the conductive polymer composition solution (5) obtained above for 5 minutes. After taking out, it was dried at 110 ° C. for 60 minutes. Each of the obtained capacitors was measured with an LCR meter (Agilent 4263B) (measurement conditions: voltage 1,000 mV, frequency 120 Hz). The measurement results are shown in Table 1.
実施例６
リグニンスルホン酸を１２．０７ｇから６０ｇに変更したこと以外は、実施例４と同様の製造工程を実行し、導電性高分子組成物（ＰＥＤＯＴ−ＰＳＳ−ＬＧＮ）溶液（６）を得た。
Example 6
Except having changed lignin sulfonic acid from 12.07g to 60g, the manufacturing process similar to Example 4 was performed, and the conductive polymer composition (PEDOT-PSS-LGN) solution (6) was obtained.
３個のコンデンサを用意し、上記で得られた導電性高分子組成物溶液（６）に５分間浸した。取り出した後、１１０℃で６０分間乾燥させた。得られたコンデンサは、それぞれ、ＬＣＲメータ（Ａｇｉｌｅｎｔ ４２６３Ｂ）で測定した（測定条件：電圧１，０００ｍＶ、周波数１２０Ｈｚ）。測定結果を表１に示す。 Three capacitors were prepared and immersed in the conductive polymer composition solution (6) obtained above for 5 minutes. After taking out, it was dried at 110 ° C. for 60 minutes. Each of the obtained capacitors was measured with an LCR meter (Agilent 4263B) (measurement conditions: voltage 1,000 mV, frequency 120 Hz). The measurement results are shown in Table 1.
実施例７
リグニンスルホン酸を１２．０７ｇから１２０ｇに変更したこと以外は、実施例４と同様の製造工程を実行し、導電性高分子組成物（ＰＥＤＯＴ−ＰＳＳ−ＬＧＮ）溶液（７）を得た。
Example 7
Except having changed lignin sulfonic acid from 12.07g to 120g, the manufacturing process similar to Example 4 was performed, and the conductive polymer composition (PEDOT-PSS-LGN) solution (7) was obtained.
３個のコンデンサを用意し、上記で得られた導電性高分子組成物溶液（７）に５分間浸漬した。取り出した後、１１０℃で６０分間乾燥させた。得られたコンデンサは、それぞれ、ＬＣＲメータ（Ａｇｉｌｅｎｔ ４２６３Ｂ）で測定した（測定条件：電圧１，０００ｍＶ、周波数１２０Ｈｚ）。測定結果を表１に示す。 Three capacitors were prepared and immersed in the conductive polymer composition solution (7) obtained above for 5 minutes. After taking out, it was dried at 110 ° C. for 60 minutes. Each of the obtained capacitors was measured with an LCR meter (Agilent 4263B) (measurement conditions: voltage 1,000 mV, frequency 120 Hz). The measurement results are shown in Table 1.
実施例８
リグニンスルホン酸を１２．０７ｇから２４０ｇに変更したこと以外は、実施例４と同様の製造工程を実行し、導電性高分子組成物（ＰＥＤＯＴ−ＰＳＳ−ＬＧＮ）溶液（８）を得た。
Example 8
Except having changed lignin sulfonic acid from 12.07g to 240g, the manufacturing process similar to Example 4 was performed, and the conductive polymer composition (PEDOT-PSS-LGN) solution (8) was obtained.
３個のコンデンサを用意し、上記で得られた導電性高分子組成物溶液（８）に５分間浸漬した。取り出した後、１１０℃で６０分間乾燥させた。得られたコンデンサは、それぞれ、ＬＣＲメータ（Ａｇｉｌｅｎｔ ４２６３Ｂ）で測定した（測定条件：電圧１，０００ｍＶ、周波数１２０Ｈｚ）。測定結果を表１に示す。 Three capacitors were prepared and immersed in the conductive polymer composition solution (8) obtained above for 5 minutes. After taking out, it was dried at 110 ° C. for 60 minutes. Each of the obtained capacitors was measured with an LCR meter (Agilent 4263B) (measurement conditions: voltage 1,000 mV, frequency 120 Hz). The measurement results are shown in Table 1.
比較例１
３，４−エチレンジオキシチオフェン１４．２ｇ（０．１ｍｏｌ）を準備し、２，２００ｍＬの脱イオン水、ポリスチレンスルホン酸３６．７ｇ（０．２ｍｏｌ、分子量約７５，０００）を加え、この溶液を２０℃で均一に攪拌後、窒素を溶液中に送り、少なくとも３０分攪拌し続けた。この溶液中に、過硫酸アンモニウム２２．８ｇ（０．１ｍｏｌ）および硫酸鉄２ｇ（０．００５ｍｏｌ）を加え、２０℃で１６時間反応させた。
Comparative Example 1
Prepare 14.2 g (0.1 mol) of 3,4-ethylenedioxythiophene, add 2,200 mL of deionized water, 36.7 g of polystyrene sulfonic acid (0.2 mol, molecular weight of about 75,000), and add this solution. After stirring uniformly at 20 ° C., nitrogen was fed into the solution and stirring was continued for at least 30 minutes. To this solution, 22.8 g (0.1 mol) of ammonium persulfate and 2 g (0.005 mol) of iron sulfate were added and reacted at 20 ° C. for 16 hours.
反応後の溶液は、透析膜（ＭＷＣＯ：１２，０００〜１４，０００）により透析純化し、未反応のモノマー、二量体、三量体、オリゴマーおよび酸化剤を除去した。純化後の溶液を、さらに、ホモジナイザーで処理して、導電性高分子組成物（ＰＥＤＯＴ−ＰＳＳ）溶液（９）を得た。 The solution after the reaction was purified by dialysis using a dialysis membrane (MWCO: 12,000 to 14,000) to remove unreacted monomers, dimers, trimers, oligomers and oxidizing agents. The purified solution was further treated with a homogenizer to obtain a conductive polymer composition (PEDOT-PSS) solution (9).
３個のコンデンサを用意し、上記で得られた導電性高分子組成物溶液（９）に５分間浸漬した。取り出した後、１１０℃で６０分間乾燥させた。得られたコンデンサは、それぞれ、ＬＣＲメータ（Ａｇｉｌｅｎｔ ４２６３Ｂ）で測定した（測定条件：電圧１，０００ｍＶ、周波数１２０Ｈｚ）。測定結果を表１に示す。 Three capacitors were prepared and immersed in the conductive polymer composition solution (9) obtained above for 5 minutes. After taking out, it was dried at 110 ° C. for 60 minutes. Each of the obtained capacitors was measured with an LCR meter (Agilent 4263B) (measurement conditions: voltage 1,000 mV, frequency 120 Hz). The measurement results are shown in Table 1.
表１から分かるように、本発明による導電性高分子組成物（リグニンスルホン酸およびポリスチレンスルホン酸を含む）溶液（１）〜（８）で製造されるコンデンサのキャパシタンスは、比較例で得られる導電性高分子組成物（ＰＥＤＯＴ−ＰＳＳ）溶液（９）で製造されるコンデンサのキャパシタンス（０．１７〜０．２２μＦ）の２倍以上（本発明の実施例６で得られるコンデンサは１５〜１７倍に達するものもある）である。 As can be seen from Table 1, the capacitances of the capacitors produced by the conductive polymer composition (including lignin sulfonic acid and polystyrene sulfonic acid) solutions (1) to (8) according to the present invention are the conductivity obtained in the comparative example. 2 times or more of the capacitance (0.17 to 0.22 μF) of the capacitor produced with the conductive polymer composition (PEDOT-PSS) solution (9) (the capacitor obtained in Example 6 of the present invention is 15 to 17 times) Some of them reach this level).
総合すると、本発明による導電性高分子組成物は、リグニンスルホン酸およびポリスチレンスルホン酸を導電性高分子のドーパントとし、導電性高分子組成物の電荷平衡およびチオフェン高分子分散を促進する以外に、導電性高分子組成物は、固体電界コンデンサへの応用に非常に適し、キャパシタンスを増加させる。 In summary, the conductive polymer composition according to the present invention uses lignin sulfonic acid and polystyrene sulfonic acid as dopants for the conductive polymer, and promotes the charge balance and thiophene polymer dispersion of the conductive polymer composition. The conductive polymer composition is very suitable for application in solid state electric capacitors and increases capacitance.
本発明では、好ましい実施例を前述の通り開示したが、これらは例示として、および好ましい実施形態という観点から開示されたものであり、決して開示された実施例に限定するものではない。したがって、本発明の範囲は、添付の特許請求の範囲で示されるものであり、当業者にとっては、本発明の精神と範囲を逸脱することなく、記載された実施形態に様々な変更や修正を行うことができることは明らかである。 In the present invention, preferred examples have been disclosed as described above, but these are disclosed as examples and from the viewpoint of preferred embodiments, and are not limited to the disclosed examples in any way. The scope of the invention is, therefore, indicated by the appended claims, and various changes and modifications can be made to the described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Obviously it can be done.
１０：電界コンデンサ
１２：第一金属電極
１４：金属酸化物層
１６：導電層
１８：第二金属電極
２０：凹部
10: Electric field capacitor 12: First metal electrode 14: Metal oxide layer 16: Conductive layer 18: Second metal electrode 20: Recess
Claims (22)
前記導電性高分子組成物が、有機ポリマーと、ポリスチレンスルホン酸と、リグニンスルホン酸とを含み、
前記有機ポリマーが、式（Ｉ）：
で示される繰り返し単位を有することを特徴とする電子素子。 An electronic device having a substrate and a conductive layer formed by applying a conductive polymer composition on the substrate,
The conductive polymer composition includes an organic polymer, polystyrene sulfonic acid, and lignin sulfonic acid,
Said organic polymer is of formula (I):
An electronic device comprising a repeating unit represented by:
前記有機ポリマーが、式（Ｉ）：
で示される繰り返し単位を有することを特徴とする導電性高分子組成物。 An organic polymer, polystyrene sulfonic acid, and lignin sulfonic acid,
Said organic polymer is of formula (I):
It has a repeating unit shown by the conductive polymer composition characterized by the above-mentioned.
純化工程を実行して、前記酸化剤を除去し、前記導電性高分子組成物を得る工程と、
を含み、
前記モノマーが、式（ＩＩ）：
で示される構造を有することを特徴とする導電性高分子組成物の製造方法。 Performing a polymerization reaction on the monomers in the presence of lignin sulfonic acid, polystyrene sulfonic acid, water and an oxidizing agent;
Performing a purification step to remove the oxidizing agent to obtain the conductive polymer composition; and
Including
The monomer is represented by formula (II):
The manufacturing method of the conductive polymer composition characterized by having the structure shown by these.
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