JP2010245364A - Solid-state electrolytic capacitor and method of manufacturing the same - Google Patents
Solid-state electrolytic capacitor and method of manufacturing the same Download PDFInfo
- Publication number
- JP2010245364A JP2010245364A JP2009093672A JP2009093672A JP2010245364A JP 2010245364 A JP2010245364 A JP 2010245364A JP 2009093672 A JP2009093672 A JP 2009093672A JP 2009093672 A JP2009093672 A JP 2009093672A JP 2010245364 A JP2010245364 A JP 2010245364A
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- JP
- Japan
- Prior art keywords
- conductive polymer
- forming
- electrolytic capacitor
- group
- electropolymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000003990 capacitor Substances 0.000 title claims abstract description 81
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 40
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 155
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 63
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 10
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- 238000000034 method Methods 0.000 claims description 34
- 239000007787 solid Substances 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 28
- 239000007784 solid electrolyte Substances 0.000 claims description 20
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 239000003115 supporting electrolyte Substances 0.000 claims description 14
- 150000001768 cations Chemical class 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 150000003233 pyrroles Chemical class 0.000 claims description 2
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
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- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 30
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- 229910052794 bromium Inorganic materials 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- PCYQQSKDZQTOQG-NXEZZACHSA-N dibutyl (2r,3r)-2,3-dihydroxybutanedioate Chemical compound CCCCOC(=O)[C@H](O)[C@@H](O)C(=O)OCCCC PCYQQSKDZQTOQG-NXEZZACHSA-N 0.000 description 1
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- YSAVZVORKRDODB-WDSKDSINSA-N diethyl tartrate Chemical compound CCOC(=O)[C@@H](O)[C@H](O)C(=O)OCC YSAVZVORKRDODB-WDSKDSINSA-N 0.000 description 1
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- XOIWXJSPLXGSLZ-UHFFFAOYSA-L disodium;naphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].C1=CC(S([O-])(=O)=O)=CC2=CC(S(=O)(=O)[O-])=CC=C21 XOIWXJSPLXGSLZ-UHFFFAOYSA-L 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
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- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
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- 235000019253 formic acid Nutrition 0.000 description 1
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- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 229960001047 methyl salicylate Drugs 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
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- 210000003205 muscle Anatomy 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
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- HYFMZOAPNQAXHU-UHFFFAOYSA-N naphthalene-1,7-disulfonic acid Chemical group C1=CC=C(S(O)(=O)=O)C2=CC(S(=O)(=O)O)=CC=C21 HYFMZOAPNQAXHU-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical group C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- RBXVOQPAMPBADW-UHFFFAOYSA-N nitrous acid;phenol Chemical class ON=O.OC1=CC=CC=C1 RBXVOQPAMPBADW-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- AVFBYUADVDVJQL-UHFFFAOYSA-N phosphoric acid;trioxotungsten;hydrate Chemical compound O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O AVFBYUADVDVJQL-UHFFFAOYSA-N 0.000 description 1
- MQHNKCZKNAJROC-UHFFFAOYSA-N phthalic acid dipropyl ester Natural products CCCOC(=O)C1=CC=CC=C1C(=O)OCCC MQHNKCZKNAJROC-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
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- 238000005245 sintering Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/025—Solid electrolytes
- H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
本発明は、導電性高分子形成用の電解重合液を使用し形成した導電性高分子並びに、該導電性高分子からなる固体電解質層を形成させてなる固体電解コンデンサとその製造方法に関する。 The present invention relates to a conductive polymer formed by using an electrolytic polymerization solution for forming a conductive polymer, a solid electrolytic capacitor formed with a solid electrolyte layer made of the conductive polymer, and a method for manufacturing the same.
アルミニウムやタンタル等の弁作用金属表面に誘電体酸化皮膜を形成し、該誘電体酸化皮膜上に固体電解質として電気伝導度の高い導電性高分子を形成させてなる固体電解コンデンサは、静電容量が高く、等価直列抵抗（以下、「ＥＳＲ」と略記する。）が低い優れた特性を有することが知られている。 A solid electrolytic capacitor in which a dielectric oxide film is formed on the surface of a valve metal such as aluminum or tantalum, and a conductive polymer having a high electrical conductivity is formed on the dielectric oxide film as a solid electrolyte has a capacitance. It is known that it has an excellent characteristic that it has a high equivalent series resistance (hereinafter abbreviated as “ESR”).
上記固体電解コンデンサは一般的に、エッチング処理により表面積を拡大した弁作用金属箔、あるいは弁作用金属の粒子を焼結させることにより表面積を拡大した焼結体を、化成処理により該表面に誘電体酸化皮膜を形成させ、次いで、該誘電体酸化皮膜上に固体電解質層を形成し、カーボン及び銀ペーストからなる導電層を順次形成した後、リードフレームなどの外部端子に接続し、トランスファーモールド等による外装を施して製品化される。 In general, the solid electrolytic capacitor has a valve-acting metal foil whose surface area is enlarged by etching treatment or a sintered body whose surface area is enlarged by sintering particles of valve-acting metal, and a dielectric material on the surface by chemical conversion treatment. An oxide film is formed, then a solid electrolyte layer is formed on the dielectric oxide film, a conductive layer made of carbon and silver paste is sequentially formed, and then connected to an external terminal such as a lead frame, by transfer molding or the like It is commercialized with an exterior.
固体電解コンデンサのＥＳＲは、コンデンサを形成する各部材の固有抵抗と、コンデンサを形成する各部材間に発生する接触抵抗からなる、合成抵抗が主要な因子となっており、それらの改善によるＥＳＲのより一層の低減が望まれている。 The ESR of a solid electrolytic capacitor is mainly composed of a combined resistance consisting of the specific resistance of each member forming the capacitor and the contact resistance generated between each member forming the capacitor. Further reduction is desired.
固体電解コンデンサの劣化は、偶発的に発生する不具合の他は一般的に、コンデンサを形成する各部材の熱劣化と、コンデンサの外装部を介して浸入する水分等の酸素源に起因する各部材の酸化劣化が主要な因子となっており、これらの劣化要因に対し、コンデンサを形成する各部材、特に固体電解質層の熱耐久性能の向上と、外装部材を中心としたガスバリア性の向上等の対策が行われている。 Deterioration of solid electrolytic capacitors is generally due to thermal degradation of each member forming the capacitor and oxygen sources such as moisture entering through the exterior of the capacitor, in addition to accidents that occur accidentally. Oxidative degradation of these materials is a major factor, and against these degradation factors, improvement of the thermal durability performance of each member that forms the capacitor, especially the solid electrolyte layer, and improvement of gas barrier properties centering on exterior members, etc. Measures are being taken.
固体電解コンデンサに用いられる一般的な固体電解質としては、ポリピロールとポリエチレンジオキシチオフェンが挙げられ、さらに詳しくは、電解酸化重合によって形成されるポリピロールと、化学酸化重合によって形成されるポリエチレンジオキシチオフェンに大別される。 Typical solid electrolytes used for solid electrolytic capacitors include polypyrrole and polyethylene dioxythiophene. More specifically, polypyrrole formed by electrolytic oxidation polymerization and polyethylene dioxythiophene formed by chemical oxidation polymerization Broadly divided.
電解酸化重合によって形成される固体電解質は、緻密な膜を形成することができるため、導電性が優れる傾向があり、積層型のコンデンサの製造に用いられている。一方、化学酸化重合は、複雑な形状の素子にも対応できるため、巻回型のコンデンサの製造に多く用いられている。 Since the solid electrolyte formed by electrolytic oxidation polymerization can form a dense film, it tends to have excellent conductivity, and is used in the manufacture of multilayer capacitors. On the other hand, chemical oxidative polymerization can be used even for devices having complicated shapes, and is therefore often used in the manufacture of winding type capacitors.
前記、固体電解コンデンサを形成する固体電解質の固有の性能については、ポリピロールやポリエチレンジオキシチオフェン等の固体電解質の種類のみではなく、固体電解質形成時に使用する支持電解質によっても固体電解質の導電性や熱耐久性等の性能が変化することが知られている。 The inherent performance of the solid electrolyte forming the solid electrolytic capacitor is not limited to the type of solid electrolyte such as polypyrrole or polyethylenedioxythiophene, but also depending on the supporting electrolyte used when forming the solid electrolyte, the conductivity and heat of the solid electrolyte. It is known that performance such as durability changes.
特許文献１、特許文献２に開示されているように、積層型の固体電解コンデンサに用いられるポリピロールからなる固体電解質では、代表的な支持電解質として、パラトルエンスルホン酸、ナフタレンスルホン酸が挙げられるが、前記パラトルエンスルホン酸、ナフタレンスルホン酸を支持電解質として用いたポリピロールからなる固体電解質では、導電性や熱耐久性が十分ではなく、得られた固体電解コンデンサのＥＳＲが高く、高温下での耐久性が低いという欠点があった。 As disclosed in Patent Document 1 and Patent Document 2, in a solid electrolyte made of polypyrrole used for a multilayer solid electrolytic capacitor, paratoluenesulfonic acid and naphthalenesulfonic acid can be cited as typical supporting electrolytes. The solid electrolyte composed of polypyrrole using the above-mentioned paratoluenesulfonic acid and naphthalenesulfonic acid as a supporting electrolyte has insufficient conductivity and thermal durability, and the obtained solid electrolytic capacitor has high ESR and durability at high temperatures. There was a fault that the property was low.
本発明の目的は、高電導度かつ高熱耐久性の導電性高分子を与える導電性高分子形成用電解重合液を提供すること、また、上記電解重合液を用い、ＥＳＲが低く、高い熱耐久性を有する固体電解コンデンサとその製造方法を提供することである。 It is an object of the present invention to provide an electropolymerization liquid for forming a conductive polymer that gives a conductive polymer having high conductivity and high heat durability, and also uses the above electropolymerization liquid and has low ESR and high heat durability. It is providing the solid electrolytic capacitor which has the property, and its manufacturing method.
本発明者らは、鋭意検討した結果、上記問題を解決しうる導電性高分子形成用電解重合液、導電性高分子、固体電解コンデンサとその製造方法を完成するに至った。 As a result of intensive studies, the present inventors have completed an electrolytic polymerization solution for forming a conductive polymer, a conductive polymer, a solid electrolytic capacitor, and a method for manufacturing the same, which can solve the above problems.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
第一の発明は、導電性高分子単量体と支持電解質塩とが、溶媒に溶解されてなる導電性高分子形成用電解重合液において、
該支持電解質塩として、下記一般式（１）で示される化合物を少なくとも1種類含むことを特徴とする導電性高分子形成用電解重合液である。
The first invention is an electropolymerization liquid for forming a conductive polymer in which a conductive polymer monomer and a supporting electrolyte salt are dissolved in a solvent.
An electropolymerization liquid for forming a conductive polymer, comprising at least one compound represented by the following general formula (1) as the supporting electrolyte salt.
式（１）中、Ｒ１〜Ｒ８はそれぞれ同一であっても異なってもよい水素原子、炭素数１〜６の直鎖又は分岐鎖状アルキル基、炭素数１〜６の直鎖又は分岐鎖状アルコキシ基、アミノ基、ニトロ基、スルホン酸基のいずれかを示し、少なくとも２つはスルホン酸基を示す。Ｘ＋は対カチオンを示す。 In formula (1), R 1 to R 8 may be the same or different from each other, a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched chain having 1 to 6 carbon atoms. A chain alkoxy group, an amino group, a nitro group, or a sulfonic acid group is shown, and at least two of them are sulfonic acid groups. X + represents a counter cation.
第二の発明は、該支持電解質塩として、一般式（１）で表される化合物（Ｄ１）を少なくとも１種類以上含み、更に一般式（１）で表される化合物と同一ではない下記一般式（２）で表される化合物（Ｄ２）を少なくとも１種類以上含み、それぞれの化合物のモル比がＤ１：Ｄ２＝９９：１〜７０：３０であることを特徴とする第一の発明に記載の導電性高分子形成用電解重合液である。 The second invention includes at least one compound (D1) represented by the general formula (1) as the supporting electrolyte salt, and is not the same as the compound represented by the general formula (1). The compound according to (1), characterized in that it contains at least one compound (D2) represented by (2), and the molar ratio of each compound is D1: D2 = 99: 1 to 70:30. This is an electropolymerization liquid for forming a conductive polymer.
式（２）中、Ｒ９〜Ｒ１６はそれぞれ同一であっても異なってもよい水素原子、炭素数１〜６の直鎖又は分岐鎖状アルキル基、炭素数１〜６の直鎖又は分岐鎖状アルコキシ基、アミノ基、ニトロ基、スルホン酸基のいずれかを示し、少なくとも１つはスルホン酸基を示す。Ｘ＋は対カチオンを示す。 In formula (2), R 9 to R 16 may be the same or different from each other, a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched group having 1 to 6 carbon atoms. A chain alkoxy group, an amino group, a nitro group, or a sulfonic acid group is shown, and at least one of them represents a sulfonic acid group. X + represents a counter cation.
第三の発明は、下記一般式（３）〜（５）で示される少なくとも一つの化合物が添加剤として溶解されてなることを特徴とする第一又は第二の発明に記載の導電性高分子形成用電解重合液である。 According to a third aspect of the invention, there is provided the conductive polymer according to the first or second aspect, wherein at least one compound represented by the following general formulas (3) to (5) is dissolved as an additive. This is an electrolytic polymerization solution for formation.
式中、Ｒ１７〜Ｒ３２はそれぞれ同一でも異なっていてもよい、水素原子、炭素数１〜６の直鎖状又は分岐鎖状アルキル基又はフェニル基を示す。 In formula, R < 17 > -R < 32 > shows the hydrogen atom which may be same or different, respectively, a C1-C6 linear or branched alkyl group, or a phenyl group.
第四の発明は、前記導電性高分子単量体がピロール及び／又はピロール誘導体であることを特徴とする第一から第三の発明のいずれかに記載の導電性高分子形成用電解重合液である。 According to a fourth invention, the conductive polymer monomer for forming a conductive polymer according to any one of the first to third inventions, wherein the conductive polymer monomer is pyrrole and / or a pyrrole derivative. It is.
第五の発明は、第一から第四の発明のいずれかに記載の導電性高分子形成用電解重合液中にて電解重合することにより形成されたことを特徴とする導電性高分子である。 A fifth invention is a conductive polymer formed by electrolytic polymerization in the electropolymerization liquid for forming a conductive polymer according to any one of the first to fourth inventions. .
第六の発明は、弁作用金属に誘電体酸化被膜が形成され、該誘電体酸化被膜上に固体電解質を有する固体電解コンデンサにおいて、固体電解質に少なくとも第五の発明に記載の導電性高分子が含有されていることを特徴とする固体電解コンデンサである。 According to a sixth aspect of the present invention, in the solid electrolytic capacitor having a dielectric oxide film formed on the valve action metal and having a solid electrolyte on the dielectric oxide film, the conductive polymer according to at least the fifth aspect of the invention is provided on the solid electrolyte. It is a solid electrolytic capacitor characterized by containing.
第七の発明は、誘電体酸化被膜が形成された弁作用金属上に、第一から第四の発明のいずれかに記載の導電性高分子形成用電解重合液中で導電性高分子層を電解重合により形成する工程を少なくとも有する固体電解コンデンサの製造方法である。 In a seventh aspect of the present invention, a conductive polymer layer is formed in the electropolymerization liquid for forming a conductive polymer according to any one of the first to fourth aspects of the invention on the valve action metal on which the dielectric oxide film is formed. A method for producing a solid electrolytic capacitor having at least a step of forming by electrolytic polymerization.
第八の発明は、誘電体酸化被膜が形成された弁作用金属上に、導電性高分子層（Ａ）を形成する工程と、前記導電性高分子層（Ａ）上に第一から第五の発明のいずれかに記載の導電性高分子形成用電解重合液中で導電性高分子層（Ｂ）を電解重合により形成する工程とを有する固体電解コンデンサの製造方法である。 According to an eighth aspect of the present invention, there is provided a step of forming a conductive polymer layer (A) on the valve action metal on which the dielectric oxide film is formed, and a first to fifth steps on the conductive polymer layer (A). And forming a conductive polymer layer (B) by electrolytic polymerization in the electropolymerization liquid for forming a conductive polymer according to any one of the inventions.
第九の発明は、導電性高分子層（Ａ）が層構造を有していることを特徴とする第八の発明に記載の固体電解コンデンサの製造方法である。 A ninth invention is the method for producing a solid electrolytic capacitor according to the eighth invention, wherein the conductive polymer layer (A) has a layer structure.
第十の発明は、導電性高分子層（Ａ）の形成方法が、溶媒溶解性又は溶媒分散性の導電性高分子を含有した溶液を付着後乾燥させることにより形成する工程を含むことを特徴とする第八又は第九の発明に記載の固体電解コンデンサの製造方法である。 According to a tenth aspect of the invention, the method for forming the conductive polymer layer (A) includes a step of forming a solution containing a solvent-soluble or solvent-dispersible conductive polymer and then drying the solution. The method for producing a solid electrolytic capacitor according to the eighth or ninth invention.
第十一の発明は、導電性高分子層（Ａ）の形成方法が、導電性高分子単量体の化学重合により形成されることを特徴とする第八又は第九の発明に記載の固体電解コンデンサの製造方法である。 The eleventh invention is characterized in that the method for forming the conductive polymer layer (A) is formed by chemical polymerization of a conductive polymer monomer, and the solid according to the eighth or ninth invention This is a method of manufacturing an electrolytic capacitor.
本発明によれば、従来よりも高電導度かつ高熱耐久性の導電性高分子を与える導電性高分子形成用電解重合液を提供すること、並びに、従来の固体電解コンデンサと比較して著しく優れたＥＳＲ特性、高い熱耐久性を示す固体電解コンデンサとその製造方法を提供することができる。 According to the present invention, it is possible to provide an electropolymerization liquid for forming a conductive polymer that gives a conductive polymer having higher conductivity and higher heat durability than the conventional one, and it is remarkably superior to conventional solid electrolytic capacitors. It is possible to provide a solid electrolytic capacitor exhibiting high ESR characteristics and high thermal durability, and a method for manufacturing the same.
最初に、本発明の導電性高分子形成用電解重合液について説明する。 First, the electropolymerization liquid for forming a conductive polymer of the present invention will be described.
本発明の導電性高分子形成用電解重合液は、ドーパントを放出できる支持電解質塩及び導電性高分子単量体であるモノマーが、溶媒中に溶解されたものである。 The electropolymerization liquid for forming a conductive polymer of the present invention is a solution in which a supporting electrolyte salt capable of releasing a dopant and a monomer that is a conductive polymer monomer are dissolved in a solvent.
ドーパントとしては、例えば、ヨウ素、臭素、塩素等のハロゲンイオン、ヘキサフロロリン、ヘキサフロロヒ素、ヘキサフロロアンチモン、テトラフロロホウ素、過塩素酸等のハロゲン化物イオン、またはメタンスルホン酸、ドデシルスルホン酸等のアルキル置換有機スルホン酸イオン、カンファースルホン酸イオンなどの環状スルホン酸イオン、またはベンゼンスルホン酸、パラトルエンスルホン酸、ドデシルベンゼンスルホン酸、ベンゼンジスルホン酸等のアルキル置換もしくは無置換のベンゼンモノもしくはジスルホン酸イオン、２−ナフタレンスルホン酸、１，７−ナフタレンジスルホン酸等のスルホン酸基を１〜４個置換したナフタレンスルホン酸のアルキル置換もしくは無置換イオン、アントラセンスルホン酸イオン、アントラキノンスルホン酸イオン、アルキルビフェニルスルホン酸、ビフェニルジスルホン酸等のアルキル置換もしくは無置換のビフェニルスルホン酸イオン、ポリスチレンスルホン酸、ナフタレンスルホン酸ホルマリン縮合体等の高分子スルホン酸イオン等、に例示される置換または無置換の芳香族スルホン酸イオン、またはビスサルチレートホウ素、ビスカテコレートホウ素等のホウ素化合物イオン、またはモリブドリン酸、タングストリン酸、タングストモリブドリン酸等のヘテロポリ酸イオンなどが一般にあげられるが、本発明で用いる支持電解質塩は下記一般式（１）及び下記一般式（２）で示される化合物である。 Examples of the dopant include halogen ions such as iodine, bromine, and chlorine, halide ions such as hexafluoroline, hexafluoroarsenic, hexafluoroantimony, tetrafluoroboron, and perchloric acid, or methanesulfonic acid and dodecylsulfonic acid. Cyclic sulfonate ions such as alkyl-substituted organic sulfonate ions and camphor sulfonate ions, or alkyl-substituted or unsubstituted benzene mono- or disulfonate ions such as benzene sulfonic acid, paratoluene sulfonic acid, dodecyl benzene sulfonic acid, and benzene disulfonic acid Alkyl substituted or unsubstituted ions of naphthalenesulfonic acid substituted with 1 to 4 sulfonic acid groups such as 2-naphthalenesulfonic acid and 1,7-naphthalenedisulfonic acid, anthracenesulfonic acid ion, anthracene Substitutions exemplified by alkyl-substituted or unsubstituted biphenyl sulfonate ions such as non-sulfonate ions, alkylbiphenyl sulfonates and biphenyl disulfonates, and polymer sulfonate ions such as polystyrene sulfonate and naphthalene sulfonate formalin condensates In general, unsubstituted aromatic sulfonate ions, boron compound ions such as bissaltylate boron and biscatecholate boron, and heteropoly acid ions such as molybdophosphoric acid, tungstophosphoric acid, tungstomolybdophosphoric acid, etc. However, the supporting electrolyte salt used in the present invention is a compound represented by the following general formula (1) and the following general formula (2).
上記一般式（１）中のＲ１〜Ｒ８はそれぞれ同一であっても異なっていてもよい、水素原子、炭素数１〜６の直鎖状又は分岐鎖状アルキル基、炭素数１〜６の直鎖状又は分岐鎖状アルコキシル基、アミノ基、ニトロ基、スルホン酸基のいずれかを示し、それらの内、少なくとも二つがスルホン酸基であり、より好ましくはＲ２又はＲ３の内少なくとも１つはスルホン酸基であり、かつ、Ｒ６又はＲ７の内少なくとも１つはスルホン酸基である。Ｘ＋は対カチオンを示す。 R 1 to R 8 in the general formula (1) may be the same or different from each other, a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. A linear or branched alkoxyl group, an amino group, a nitro group, or a sulfonic acid group, at least two of which are sulfonic acid groups, more preferably at least one of R 2 or R 3 One is a sulfonic acid group, and at least one of R 6 or R 7 is a sulfonic acid group. X + represents a counter cation.
上記一般式（１）で示される化合物の具体例としては、好ましくは、アントラキノン−１，４−ジスルホン酸塩、アントラキノン−１，５−ジスルホン酸塩、アントラキノン−１，６−ジスルホン酸塩、アントラキノン−１，７−ジスルホン酸塩、アントラキノン−１，８−ジスルホン酸塩、アントラキノン−２，６−ジスルホン酸塩、アントラキノン−２，７−ジスルホン酸塩が挙げられ、より好ましくは、アントラキノン−２，６−ジスルホン酸塩、アントラキノン−２，７−ジスルホン酸塩が挙げられる。 Specific examples of the compound represented by the general formula (1) are preferably anthraquinone-1,4-disulfonate, anthraquinone-1,5-disulfonate, anthraquinone-1,6-disulfonate, anthraquinone. -1,7-disulfonate, anthraquinone-1,8-disulfonate, anthraquinone-2,6-disulfonate, anthraquinone-2,7-disulfonate, more preferably anthraquinone-2, Examples include 6-disulfonate and anthraquinone-2,7-disulfonate.
上記一般式（１）中の対カチオンとしては、アンモニウムカチオン、アルカリ金属カチオン、アルカリ土類金属カチオンが挙げられる。
前記アンモニウムカチオンとしては、ＮＨ４ ＋、ＮＨ３Ｒ＋、ＮＨ２Ｒ２ ＋、ＮＨＲ３ ＋、ＮＲ４ ＋等が挙げられる。Ｒは炭素数１〜８の直鎖状又は分岐鎖状のアルキル基であり、Ｒ同士で連結して環を形成してもよい。
前記アルカリ金属カチオンとしては、リチウム、ナトリウム、カリウム等が挙げられる。
前記アルカリ土類金属カチオンとしては、マグネシウム、カルシウム等が挙げられる。
また、カチオンが水素イオンである酸も使用できる。
これらカチオンは、１種若しくは２種以上を混合して用いることが出来る。
Examples of the counter cation in the general formula (1) include an ammonium cation, an alkali metal cation, and an alkaline earth metal cation.
Examples of the ammonium cation include NH 4 + , NH 3 R + , NH 2 R 2 + , NHR 3 + , NR 4 + and the like. R is a linear or branched alkyl group having 1 to 8 carbon atoms, and R may be linked together to form a ring.
Examples of the alkali metal cation include lithium, sodium, and potassium.
Examples of the alkaline earth metal cation include magnesium and calcium.
Moreover, the acid whose cation is a hydrogen ion can also be used.
These cations can be used alone or in combination of two or more.
上記一般式（１）により表される化合物は、１種類若しくは２種類以上を使用することができる。 The compound represented by the general formula (1) may be used alone or in combination of two or more.
上記一般式（１）中のアントラキノンスルホン酸誘導体から生じるアニオンは、導電性高分子中にドーパントとして取り込まれることによって高電導度の導電性高分子を与え、かつ該ドーパントを有する導電性高分子は該ドーパントの脱離が生じにくく、極めて熱耐久性に優れたものとなる。 The anion generated from the anthraquinone sulfonic acid derivative in the general formula (1) gives a conductive polymer having high conductivity by being incorporated as a dopant in the conductive polymer, and the conductive polymer having the dopant is Desorption of the dopant is unlikely to occur and the thermal durability is extremely excellent.
上記一般式（２）中のＲ９〜Ｒ１６はそれぞれ同一であっても異なっていてもよい、水素原子、炭素数１〜６の直鎖状又は分岐鎖状アルキル基、炭素数１〜６の直鎖状又は分岐鎖状アルコキシル基、アミノ基、ニトロ基、スルホン酸基のいずれかを示し、それらの内、少なくとも一つがスルホン酸基を示し、Ｘ＋は対カチオンを示す。 R 9 to R 16 in the general formula (2) may be the same as or different from each other, a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. Or a linear or branched alkoxyl group, an amino group, a nitro group, or a sulfonic acid group, at least one of which represents a sulfonic acid group, and X + represents a counter cation.
上記一般式（２）中のアントラキノンスルホン酸誘導体から生じるアニオンは、上記一般式（１）中のアントラキノンスルホン酸誘導体から生じるアニオンとともに、導電性高分子中にドーパントとして取り込まれることによってより高電導度の導電性高分子を与え、かつ該ドーパントを有する導電性高分子は該ドーパントの脱離が生じにくく、更に熱耐久性に優れたものとなる。 The anion generated from the anthraquinone sulfonic acid derivative in the general formula (2) is incorporated into the conductive polymer as a dopant together with the anion generated from the anthraquinone sulfonic acid derivative in the general formula (1). The conductive polymer having the above-described conductive polymer and having the dopant is less likely to cause the desorption of the dopant, and further has excellent thermal durability.
上記一般式（２）中のアントラキノンスルホン酸誘導体の具体例としては、好ましくは、アントラキノン−１−スルホン酸塩、アントラキノン−２−スルホン酸塩、１−ニトロアントラキノン−５-スルホン酸塩、５−ニトロアントラキノン−１−スルホン酸塩、１-アミノアントラキノン−５−スルホン酸塩、アントラキノン−１，４−ジスルホン酸塩、アントラキノン−１，５−ジスルホン酸塩、アントラキノン−１，６−ジスルホン酸塩、アントラキノン−１，７−ジスルホン酸塩、アントラキノン−１，８−ジスルホン酸塩、アントラキノン−２，６−ジスルホン酸塩、アントラキノン−２，７−ジスルホン酸塩、等が挙げられる。 Specific examples of the anthraquinone sulfonic acid derivative in the general formula (2) are preferably anthraquinone-1-sulfonate, anthraquinone-2-sulfonate, 1-nitroanthraquinone-5-sulfonate, 5- Nitroanthraquinone-1-sulfonate, 1-aminoanthraquinone-5-sulfonate, anthraquinone-1,4-disulfonate, anthraquinone-1,5-disulfonate, anthraquinone-1,6-disulfonate, Anthraquinone-1,7-disulfonate, anthraquinone-1,8-disulfonate, anthraquinone-2,6-disulfonate, anthraquinone-2,7-disulfonate, and the like.
上記一般式（２）中の対カチオンとしては、アンモニウムカチオン、アルカリ金属カチオン、アルカリ土類金属カチオンが挙げられる。
前記アンモニウムカチオンとしては、ＮＨ４ ＋、ＮＨ３Ｒ＋、ＮＨ２Ｒ２ ＋、ＮＨＲ３ ＋、ＮＲ４ ＋等が挙げられる。Ｒは炭素数１〜８の直鎖状又は分岐鎖状のアルキル基であり、Ｒ同士で連結して環を形成してもよい。
前記アルカリ金属カチオンとしては、リチウム、ナトリウム、カリウム等が挙げられる。
前記アルカリ土類金属カチオンとしては、マグネシウム、カルシウム等が挙げられる。
また、カチオンが水素イオンである酸も使用できる。
これらカチオンは、１種若しくは２種以上を混合して用いることが出来る。
Examples of the counter cation in the general formula (2) include an ammonium cation, an alkali metal cation, and an alkaline earth metal cation.
Examples of the ammonium cation include NH 4 + , NH 3 R + , NH 2 R 2 + , NHR 3 + , NR 4 + and the like. R is a linear or branched alkyl group having 1 to 8 carbon atoms, and R may be linked together to form a ring.
Examples of the alkali metal cation include lithium, sodium, and potassium.
Examples of the alkaline earth metal cation include magnesium and calcium.
Moreover, the acid whose cation is a hydrogen ion can also be used.
These cations can be used alone or in combination of two or more.
従って、上記一般式（２）により表される化合物の具体例としては、例えば、アントラキノン−２−スルホン酸ナトリウムが挙げられる。
上記一般式（２）により表される化合物は、１種類若しくは２種類以上を使用することができる。
Accordingly, specific examples of the compound represented by the general formula (2) include sodium anthraquinone-2-sulfonate.
The compound represented by the general formula (2) may be used alone or in combination of two or more.
上記一般式（１）により表される化合物Ｄ１と上記一般式（２）により表される化合物Ｄ２のモル比は、Ｄ１：Ｄ２＝６０：４０〜１００：０の間であればよく、より好ましくは７０：３０〜９９：１である。
上記モル比で混合させた電解重合液を用いることで優れたＥＳＲの電解コンデンサを得ることができる。
The molar ratio of the compound D1 represented by the general formula (1) and the compound D2 represented by the general formula (2) may be between D1: D2 = 60: 40 to 100: 0, and more preferably. Is 70:30 to 99: 1.
An excellent ESR electrolytic capacitor can be obtained by using an electrolytic polymerization solution mixed in the above molar ratio.
本発明の一般式（１）で表される化合物で表される少なくとも２つスルホン酸基を有するアントラキノンスルホン酸誘導体は、スルホン酸基が１つ置換したアントラキノンスルホン酸誘導体より水に対する溶解度が高い特徴を有する。
これにより、導電性高分子形成用電解重合液中の支持電解質塩の濃度を上げることができ、該導電性高分子形成用電解重合液を用いることで優れた電気特性の固体電解コンデンサを得ることができる。
The anthraquinone sulfonic acid derivative having at least two sulfonic acid groups represented by the compound represented by the general formula (1) of the present invention has higher water solubility than an anthraquinone sulfonic acid derivative substituted with one sulfonic acid group. Have
Thereby, the concentration of the supporting electrolyte salt in the electropolymerization liquid for forming a conductive polymer can be increased, and a solid electrolytic capacitor having excellent electrical characteristics can be obtained by using the electropolymerization liquid for forming a conductive polymer. Can do.
本発明の電解重合液中には添加剤を含有することができる。本発明にて使用される添加剤は、主に酸化防止剤、界面活性剤のいずれかの特性を有するものが好ましい。そのような添加剤としてより好ましくは下式（３）〜（５）で示される化合物である。 The electrolytic polymerization solution of the present invention may contain an additive. The additive used in the present invention is preferably one having mainly the characteristics of either an antioxidant or a surfactant. More preferred as such additives are compounds represented by the following formulas (3) to (5).
上記一般式（３）〜（５）中、Ｒ１７〜Ｒ３２はそれぞれ同一であっても異なっていてもよい、水素原子、炭素数１〜６の直鎖状又は分岐鎖状アルキル基又はフェニル基を示す。 In the general formulas (3) to (5), R 17 to R 32 may be the same as or different from each other, a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or phenyl. Indicates a group.
上記一般式（３）で表される化合物の具体例としては、例えば、４−ニトロフェノール、２−メチル−４−ニトロフェノール、３−メチル−４−ニトロフェノール、２−エチル−４−ニトロフェノール、３−エチル−４−ニトロフェノール、２−ヘキシル−４−ニトロフェノール、３−ヘキシル−４−ニトロフェノール等のニトロフェノール類が挙げられる。
上記一般式（４）で表される化合物の具体例としては、例えば、４−ニトロ−１−ナフトール等のニトロナフトール類が挙げられる。
上記一般式（５）で表される化合物の具体例としては、例えば、１−ヒドロキシ−４−ニトロアントラキノン等のニトロアントラキノン類を挙げることができる。
Specific examples of the compound represented by the general formula (3) include, for example, 4-nitrophenol, 2-methyl-4-nitrophenol, 3-methyl-4-nitrophenol, 2-ethyl-4-nitrophenol. , Nitrophenols such as 3-ethyl-4-nitrophenol, 2-hexyl-4-nitrophenol and 3-hexyl-4-nitrophenol.
Specific examples of the compound represented by the general formula (4) include nitronaphthols such as 4-nitro-1-naphthol.
Specific examples of the compound represented by the general formula (5) include nitroanthraquinones such as 1-hydroxy-4-nitroanthraquinone.
上記一般式（３）〜（５）により表される化合物は、１種若しくは２種以上を使用することができる。上記一般式（３）〜（５）により表される化合物は、得られる導電性高分子の熱耐久性の面から、４−ニトロフェノール、４−ニトロ−１−ナフトール、１−ヒドロキシ−４−ニトロアントラキノンであることが好ましい。 The compounds represented by the general formulas (3) to (5) can be used alone or in combination of two or more. The compounds represented by the above general formulas (3) to (5) are 4-nitrophenol, 4-nitro-1-naphthol, 1-hydroxy-4-phenyl from the viewpoint of thermal durability of the obtained conductive polymer. Nitroanthraquinone is preferred.
次いで本発明に使用できる導電性高分子単量体について説明する。 Next, the conductive polymer monomer that can be used in the present invention will be described.
本発明に使用されるモノマーとしては、ピロール、アニリン、フラン、チオフェン又はこれらの誘導体を用いることができる。該誘導体としては、３−アルキルピロール、３−アルキルチオフェン、３，４−アルキレンジオキシピロール、３，４−アルキレンジオキシチオフェンなどが挙げられる。前記モノマーは１種若しくは２種以上を同時に含有することができる。これらの中でも、得られる導電性高分子の電導度及び熱耐久性の面から、ピロール及び／又はその誘導体が好ましい。 As a monomer used in the present invention, pyrrole, aniline, furan, thiophene or a derivative thereof can be used. Examples of the derivatives include 3-alkylpyrrole, 3-alkylthiophene, 3,4-alkylenedioxypyrrole, 3,4-alkylenedioxythiophene. The said monomer can contain 1 type (s) or 2 or more types simultaneously. Among these, pyrrole and / or a derivative thereof are preferable from the viewpoint of the conductivity and thermal durability of the obtained conductive polymer.
本発明に使用する電解重合液の溶媒は、水、テトラヒドロフラン（ＴＨＦ）、ジオキサン、ジエチルエーテル等のエーテル類、或いはアセトン、メチルエチルケトン等のケトン類、ジメチルホルムアミド（ＤＭＦ）やアセトニトリル、ベンゾニトリル、Ｎ−メチルピロリドン（ＮＭＰ）、ジメチルスルホキシド（ＤＭＳＯ）等の非プロトン性極性溶媒、酢酸エチルや酢酸ブチル等のエステル類、クロロホルムや塩化メチレン等の非芳香族性の塩素系溶媒、ニトロメタンやニトロエタン、ニトロベンゼン等のニトロ化合物、あるいはメタノールやエタノール、プロパノール等のアルコール類、またはギ酸や酢酸、プロピオン酸等の有機酸または該有機酸の酸無水物（無水酢酸等）を０〜３０％以下の割合で水と混合した混合溶媒を挙げることができる。これらの中でも、環境負荷、安全性の面から、水を単独で使用したものが好ましい。 The solvent of the electrolytic polymerization solution used in the present invention is water, ethers such as tetrahydrofuran (THF), dioxane, diethyl ether, or ketones such as acetone and methyl ethyl ketone, dimethylformamide (DMF), acetonitrile, benzonitrile, N- Aprotic polar solvents such as methylpyrrolidone (NMP) and dimethyl sulfoxide (DMSO), esters such as ethyl acetate and butyl acetate, non-aromatic chlorinated solvents such as chloroform and methylene chloride, nitromethane, nitroethane, nitrobenzene, etc. Nitro compounds, or alcohols such as methanol, ethanol and propanol, organic acids such as formic acid, acetic acid and propionic acid or acid anhydrides of such organic acids (such as acetic anhydride) with water in a proportion of 0 to 30% or less Name mixed solvent Kill. Among these, those using water alone are preferable from the viewpoint of environmental load and safety.
次に本発明の導電性高分子形成用電解重合液の組成について説明する。 Next, the composition of the electropolymerization liquid for forming a conductive polymer of the present invention will be described.
本発明の導電性高分子形成用電解重合液については、導電性高分子単量体を０．０５〜０．７ｍｏｌ／Ｌ、好ましくは０．１〜０．３ｍｏｌ／Ｌの濃度で含有するものである。
また、前記支持電解質は０．００５〜０．３０ｍｏｌ／Ｌ、好ましくは０．０１〜０．１ｍｏｌ／Ｌの濃度で含有するものである。
添加剤を含有させる場合、前記添加剤を０．００２〜０．１ｍｏｌ／Ｌ、好ましくは０．００３ｍｏｌ／Ｌの濃度で含有するものである。
The electropolymerization liquid for forming a conductive polymer of the present invention contains a conductive polymer monomer at a concentration of 0.05 to 0.7 mol / L, preferably 0.1 to 0.3 mol / L. It is.
The supporting electrolyte is contained at a concentration of 0.005 to 0.30 mol / L, preferably 0.01 to 0.1 mol / L.
When the additive is contained, the additive is contained at a concentration of 0.002 to 0.1 mol / L, preferably 0.003 mol / L.
本組成の導電性高分子形成用電解重合液を用いることで著しく電導度、熱耐久性に優れた導電性高分子が得られるとともに、優れた電気特性を有する固体電解コンデンサを得ることができる。 By using the electropolymerization liquid for forming a conductive polymer of this composition, a conductive polymer having remarkably excellent conductivity and thermal durability can be obtained, and a solid electrolytic capacitor having excellent electrical characteristics can be obtained.
次に本発明の導電性高分子形成用電解重合液を用い、固体電解コンデンサを製造する方法について説明する。 Next, a method for producing a solid electrolytic capacitor using the electropolymerization liquid for forming a conductive polymer of the present invention will be described.
本発明は、誘電体酸化被膜が形成された弁作用金属上に、導電性高分子層（Ａ）を形成する工程と、前記導電性高分子層（Ａ）上に上記の導電性高分子形成用電解重合液中で導電性高分子層（Ｂ）を電解重合により形成する工程とを有する固体電解コンデンサの製造方法である。 The present invention includes a step of forming a conductive polymer layer (A) on a valve action metal on which a dielectric oxide film is formed, and the formation of the conductive polymer on the conductive polymer layer (A). And a step of forming a conductive polymer layer (B) by electrolytic polymerization in the electrolytic polymerization solution for use.
弁作用金属表面の誘電体酸化皮膜上にプレコート層として導電性高分子層を予め形成しておき、次に前記プレコート層上に新たな導電性高分子層を本発明の電解重合液を用いて電解重合により形成することで固体電解質層を形成した後、該固体電解質層にカーボンペースト、銀ペースト等の導電ペーストを塗布乾燥することによって陰極層を形成する。
プレコート層の導電性高分子の形成方法としては（１）化学重合による導電性高分子層を形成する方法、（２）導電性高分子溶液を塗布乾燥して導電性高分子層を形成する方法が挙げられる。
次に弁作用金属から陽極リード端子、陰極層から陰極リード端子を接続して電極を取り出して素子を形成し、この素子全体をエポキシ樹脂等の絶縁性樹脂、あるいはセラミック製や金属製の外装ケース等により封止することで固体電解コンデンサを得ることができる。
A conductive polymer layer is formed in advance as a precoat layer on the dielectric oxide film on the valve metal surface, and then a new conductive polymer layer is formed on the precoat layer using the electrolytic polymerization solution of the present invention. After forming a solid electrolyte layer by forming by electropolymerization, a cathode layer is formed by applying and drying a conductive paste such as carbon paste and silver paste on the solid electrolyte layer.
As a method for forming the conductive polymer of the precoat layer, (1) a method of forming a conductive polymer layer by chemical polymerization, (2) a method of forming a conductive polymer layer by applying and drying a conductive polymer solution Is mentioned.
Next, the anode lead terminal is connected from the valve action metal, the cathode lead terminal is connected from the cathode layer, and the electrode is taken out to form an element. The entire element is made of an insulating resin such as epoxy resin, or an exterior case made of ceramic or metal. A solid electrolytic capacitor can be obtained by sealing with, for example.
導電性高分子（Ａ）の形成方法として、溶媒溶解性又は溶媒分散性の導電性高分子を含有した溶液を付着後乾燥させることによる工程を含んでもよい。 The method of forming the conductive polymer (A) may include a step of drying after adhering a solution containing a solvent-soluble or solvent-dispersible conductive polymer.
前記溶媒溶解性導電性高分子としては、ポリアニリン、アルキルチオフェン又はそれらの誘導体が挙げられる。
前記溶媒分散性導電性高分子としては、ポリピロール、３，４−エチレンジオキシチオフェン又はそれらの誘導体が挙げられる。
溶媒溶解性又は溶媒分散性の導電性高分子に用いる溶媒としては、水、メタノール、エタノール、１−プロパノール、イソプロピルアルコール、ｎ−ブタノール、ｓ−ブタノール、ｔ−ブタノール、ｎ−アミルアルコール、ｓ−アミルアルコール、ｔ−アミルアルコール、アリルアルコール、アソアミルアルコール、イソブチルアルコール、２−エチルブタノール、２−オクタノール、ｎ−オクタノール、シクロヘキサノール、テトラヒドロフルフリルアルコール、フルフリルアルコール、ｎ−ヘキサノール、n-ヘプタノール、２−ヘプタノール、３−ヘプタノール、ベンジルアルコール、メチルシクロヘキサノール、エチレングリコール、エチレングリコールモノメチルエーテル、グリセリン、ジエチレングリコール、プロピレンカルボナート、プロピレングリコール等のアルコール類、アセトン、メチルエチルケトン、ジエチルケトン、シクロヘキサノン、メチルイソブチルケトン、メチル−ｎ−プロピルケトン等のケトン類、アセト酢酸エチル、安息香酸エチル、安息香酸メチル、蟻酸イソブチル、蟻酸エチル蟻酸プロピル、蟻酸メチル、酢酸イソブチル、酢酸エチル、酢酸プロピル、酢酸メチル、サリチル酸メチル、シュウ酸ジエチル、酒石酸ジエチル、酒石酸ジブチル、フタル酸エチル、フタル酸メチル、フタル酸ブチル等のエステル類が挙げられる。
Examples of the solvent-soluble conductive polymer include polyaniline, alkylthiophene, and derivatives thereof.
Examples of the solvent-dispersible conductive polymer include polypyrrole, 3,4-ethylenedioxythiophene, or derivatives thereof.
Solvents used for the solvent-soluble or solvent-dispersible conductive polymer include water, methanol, ethanol, 1-propanol, isopropyl alcohol, n-butanol, s-butanol, t-butanol, n-amyl alcohol, s- Amyl alcohol, t-amyl alcohol, allyl alcohol, asoamyl alcohol, isobutyl alcohol, 2-ethylbutanol, 2-octanol, n-octanol, cyclohexanol, tetrahydrofurfuryl alcohol, furfuryl alcohol, n-hexanol, n-heptanol , 2-heptanol, 3-heptanol, benzyl alcohol, methylcyclohexanol, ethylene glycol, ethylene glycol monomethyl ether, glycerin, diethylene glycol, propylene carbonate Alcohols such as propylene glycol, acetone, methyl ethyl ketone, diethyl ketone, cyclohexanone, methyl isobutyl ketone, ketones such as methyl-n-propyl ketone, ethyl acetoacetate, ethyl benzoate, methyl benzoate, isobutyl formate, ethyl formate Examples include propyl formate, methyl formate, isobutyl acetate, ethyl acetate, propyl acetate, methyl acetate, methyl salicylate, diethyl oxalate, diethyl tartrate, dibutyl tartrate, ethyl phthalate, methyl phthalate, and butyl phthalate.
前記導電性高分子形成用電解重合液を用いることによって、電導度に優れ、かつ、高温に暴露された際に特定の安定構造をとる導電性高分子が得られ、さらに前記導電性高分子を固体電解質とすることにより、従来よりも格段に優れたＥＳＲ特性、熱耐久性を有する固体電解コンデンサを得ることができる。 By using the electropolymerization liquid for forming the conductive polymer, a conductive polymer having excellent conductivity and taking a specific stable structure when exposed to high temperature can be obtained. By using a solid electrolyte, it is possible to obtain a solid electrolytic capacitor having ESR characteristics and thermal durability that are remarkably superior to conventional ones.
本発明に用いられる陽極弁作用金属としては、アルミニウム、タンタル、ニオブ又はチタンからなる群から選ばれた１種が挙げられ、焼結体又は箔の形状で用いられる。 The anode valve action metal used in the present invention includes one selected from the group consisting of aluminum, tantalum, niobium and titanium, and is used in the form of a sintered body or foil.
本発明の固体電解コンデンサは、用いられる陽極弁作用金属の種類、形状により、チップ型または巻回型のいずれとすることができる。 The solid electrolytic capacitor of the present invention can be either a chip type or a wound type depending on the type and shape of the anode valve action metal used.
本発明の固体電解コンデンサは、以下の方法により製造される。なお、本発明は以下の製造方法により、なんら限定されない。 The solid electrolytic capacitor of the present invention is manufactured by the following method. In addition, this invention is not limited at all by the following manufacturing methods.
以下、本発明について実施例を挙げより詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
（導電性高分子フィルムの評価）
（実施例１）
２０ｍｍ×２０ｍｍサイズのステンレス（ＳＵＳ）からなる透明導電膜付きの基板を用意し、これをアセトン、純水にて洗浄後、１０５℃乾燥機中で１０分間乾燥させた。つぎに、電解重合液（アントラキノン−１，５−ジスルホン酸二ナトリウム（東京化成工業（株）製）:１．４(ｍｍｏｌ)＋ピロール：０．６（ｇ）＋Ｈ２Ｏ：４５．８（ｇ）の混合液）中に浸漬し、透明導電膜側を陽極として、電流値を１０ｍＡに固定して電解重合を行い、基板上に導電性高分子層を形成した。
(Evaluation of conductive polymer film)
Example 1
A substrate with a transparent conductive film made of stainless steel (SUS) having a size of 20 mm × 20 mm was prepared, washed with acetone and pure water, and then dried in a dryer at 105 ° C. for 10 minutes. Next, electrolytic polymerization solution (anthraquinone-1,5-disulfonic acid disodium (manufactured by Tokyo Kasei Kogyo (Co.)): 1.4 (mmol) + pyrrole: 0.6 (g) + H 2 O: 45.8 ( The mixture was dipped in the mixed solution (g)), the transparent conductive film side was used as an anode, the current value was fixed at 10 mA, and electrolytic polymerization was performed to form a conductive polymer layer on the substrate.
次に、上記透明導電膜付き基板上に形成された導電性高分子層を剥離し、導電性高分子フィルムを完成させた。 Next, the conductive polymer layer formed on the substrate with the transparent conductive film was peeled off to complete a conductive polymer film.
（実施例２）
導電性高分子の製造方法を以下の方法に代えたこと以外は実施例１と同様にして、導電性高分子フィルムを得た。すなわち、電解重合液（アントラキノン−１，８−ジスルホン酸二カリウム（東京化成工業（株）製）:１．４(ｍｍｏｌ)＋ピロール：０．６（ｇ）＋Ｈ２Ｏ：４５．８（ｇ）の混合溶液）を用いて電解重合を行い、導電性高分子フィルムを形成した。
(Example 2)
A conductive polymer film was obtained in the same manner as in Example 1 except that the production method of the conductive polymer was changed to the following method. That is, electrolytic polymerization solution (anthraquinone-1,8-disulfonic acid dipotassium (manufactured by Tokyo Chemical Industry Co., Ltd.)): 1.4 (mmol) + pyrrole: 0.6 (g) + H 2 O: 45.8 (g ) Was used to conduct electropolymerization to form a conductive polymer film.
（実施例３）
導電性高分子の製造方法を以下の方法に代えたこと以外は実施例１と同様にして、導電性高分子フィルムを得た。すなわち、電解重合液（アントラキノン−２，６−ジスルホン酸二ナトリウム（東京化成工業（株）製）:１．４(ｍｍｏｌ)＋ピロール：０．６（ｇ）＋Ｈ２Ｏ：４５．８（ｇ）の混合溶液）を用いて電解重合を行い、導電性高分子フィルムを形成した。
Example 3
A conductive polymer film was obtained in the same manner as in Example 1 except that the production method of the conductive polymer was changed to the following method. That is, the electrolytic polymerization solution (anthraquinone-2,6-disulfonic acid disodium (manufactured by Tokyo Kasei Kogyo (Co.)): 1.4 (mmol) + pyrrole: 0.6 (g) + H 2 O: 45.8 (g ) Was used to conduct electropolymerization to form a conductive polymer film.
（実施例４）
導電性高分子の製造方法を以下の方法に代えたこと以外は実施例１と同様にして、導電性高分子フィルムを得た。すなわち、電解重合液（アントラキノン−２，７−ジスルホン酸二ナトリウム（東京化成工業（株）製）:１．４(ｍｍｏｌ)＋ピロール：０．６（ｇ）＋Ｈ２Ｏ：４５．８（ｇ）の混合溶液）を用いて電解重合を行い、導電性高分子フィルムを形成した。
Example 4
A conductive polymer film was obtained in the same manner as in Example 1 except that the production method of the conductive polymer was changed to the following method. That is, an electrolytic polymerization solution (anthraquinone-2,7-disulfonic acid disodium (manufactured by Tokyo Chemical Industry Co., Ltd.): 1.4 (mmol) + pyrrole: 0.6 (g) + H 2 O: 45.8 (g ) Was used to conduct electropolymerization to form a conductive polymer film.
（実施例５）
導電性高分子の製造方法を以下の方法に代えたこと以外は実施例１と同様にして、導電性高分子フィルムを得た。すなわち、電解重合液（アントラキノン−１，５−ジスルホン酸二ナトリウム（東京化成工業（株）製）:１．４(ｍｍｏｌ)＋ピロール：０．６（ｇ）＋４−ニトロフェノール：０．５（ｇ）＋Ｈ２Ｏ：４５．８（ｇ）の混合溶液）を用いて電解重合を行い、導電性高分子フィルムを形成した。
(Example 5)
A conductive polymer film was obtained in the same manner as in Example 1 except that the production method of the conductive polymer was changed to the following method. That is, electrolytic polymerization solution (anthraquinone-1,5-disulfonic acid disodium (manufactured by Tokyo Chemical Industry Co., Ltd.): 1.4 (mmol) + pyrrole: 0.6 (g) + 4-nitrophenol: 0.5 ( g) + H 2 O: 45.8 (g) mixed solution) was used for electrolytic polymerization to form a conductive polymer film.
（比較例１）
導電性高分子の製造方法を以下の方法に代えたこと以外は実施例１と同様にして、導電性高分子フィルムを得た。すなわち、電解重合液にブチルナフタレンスルホン酸ナトリウム：１．４（ｍｍｏｌ）＋ピロール：０．６（ｇ）＋Ｈ２Ｏ：４５．８（ｇ）の混合溶液を用いて電解重合を行い、導電性高分子フィルムを形成した。
(Comparative Example 1)
A conductive polymer film was obtained in the same manner as in Example 1 except that the production method of the conductive polymer was changed to the following method. That is, electropolymerization was performed using a mixed solution of sodium butylnaphthalenesulfonate: 1.4 (mmol) + pyrrole: 0.6 (g) + H 2 O: 45.8 (g) in the electrolytic polymerization solution, and the conductivity was increased. A polymer film was formed.
（比較例２）
導電性高分子の製造方法を以下の方法に代えたこと以外は実施例１と同様にして、導電性高分子フィルムを得た。すなわち、電解重合液に２，７−ナフタレンジスルホン酸二ナトリウム：１．４（ｍｍｏｌ）＋ピロール：０．６（ｇ）＋Ｈ２Ｏ：４５．８（ｇ）の混合溶液を用いて電解重合を行い、導電性高分子フィルムを形成した。
(Comparative Example 2)
A conductive polymer film was obtained in the same manner as in Example 1 except that the production method of the conductive polymer was changed to the following method. That is, electrolytic polymerization was performed using a mixed solution of disodium 2,7-naphthalenedisulfonate: 1.4 (mmol) + pyrrole: 0.6 (g) + H 2 O: 45.8 (g) as the electrolytic polymerization solution. And a conductive polymer film was formed.
実施例１〜５及び比較例１、２の導電性高分子フィルムについて、４端子法を用いて電導度を測定した。また、１０５℃大気中放置による熱耐久性試験を行い、１００時間経過後に電導度を評価した。結果を表１に示した。 For the conductive polymer films of Examples 1 to 5 and Comparative Examples 1 and 2, the conductivity was measured using a four-terminal method. In addition, a thermal durability test was performed by leaving it in the atmosphere at 105 ° C., and the electrical conductivity was evaluated after 100 hours. The results are shown in Table 1.
表１より、従来の電解重合液を用いた比較例１、２と比較して、実施例１〜５では高い電導度と熱耐久性を示した。特に、４−ニトロフェノールを添加した電解重合液では、高い熱耐久性が得られた。 From Table 1, compared with the comparative examples 1 and 2 using the conventional electrolytic polymerization liquid, in Examples 1-5, high electrical conductivity and thermal durability were shown. In particular, high thermal durability was obtained in the electrolytic polymerization solution to which 4-nitrophenol was added.
以上の結果より、ドーパントとして導電性高分子形成用電解重合液を使用することで、電導度及び熱耐久性に優れた導電性高分子を得られることを確認した。また、前記ドーパントを含む電解重合液において、添加剤として４−ニトロフェノールを含有せしめ、これを電解重合液として使用することで、得られる導電性高分子の熱耐久性が向上することを確認した。 From the above results, it was confirmed that a conductive polymer excellent in conductivity and thermal durability can be obtained by using an electropolymerization liquid for forming a conductive polymer as a dopant. Moreover, in the electrolytic polymerization liquid containing the said dopant, it was confirmed that the thermal durability of the resulting conductive polymer was improved by adding 4-nitrophenol as an additive and using this as the electrolytic polymerization liquid. .
（固体電解コンデンサの評価）
（実施例６）
表面に誘電体酸化皮膜が形成された３ｍｍ×５ｍｍサイズのエッチドアルミニウム化成箔を１０５℃乾燥機中で１０分間乾燥させた。これを、１８℃サーモプレート上に１０分間静置した。次に１８℃に冷却したモノマー液（ピロール：３（ｇ）＋エタノール：５（ｇ）＋Ｈ２Ｏ：１８．４（ｇ）の混合液）：４μｌを箔上に滴下し、１分間静置した。さらに、酸化剤液（ｐ−トルエンスルホン酸テトラエチルアンモニウム（ＰＴＳ−ＴＥＡ）：５．６（ｍｍｏｌ）＋ペルオキソ二硫酸アンモニウム：１．５６（ｇ）＋Ｈ２Ｏ：１０．６３（ｇ）の混合液）：１２μｌを箔上に滴下し、１０分間静置することで化学酸化重合しプレコート層を形成した。これを純水にて洗浄し、１０５℃乾燥機中で１０分間乾燥させた。
(Evaluation of solid electrolytic capacitors)
(Example 6)
A 3 mm × 5 mm size etched aluminum formed foil having a dielectric oxide film formed on the surface was dried in a 105 ° C. dryer for 10 minutes. This was left to stand on an 18 ° C. thermoplate for 10 minutes. Next, 4 μl of a monomer liquid (pyrrole: 3 (g) + ethanol: 5 (g) + H 2 O: 18.4 (g) mixed liquid) cooled to 18 ° C. was dropped on the foil and left for 1 minute. did. Furthermore, an oxidizing agent solution (p-toluenesulfonate tetraethylammonium (PTS-TEA): 5.6 (mmol) + ammonium peroxodisulfate: 1.56 (g) + H 2 O: 10.63 (g)) : 12 μl was dropped on the foil and left to stand for 10 minutes for chemical oxidative polymerization to form a precoat layer. This was washed with pure water and dried in a 105 ° C. dryer for 10 minutes.
次に、電解重合液（アントラキノン−１，５−ジスルホン酸二ナトリウム：１．４（ｍｍｏｌ）＋ピロール：０．６（ｇ）＋Ｈ２Ｏ：４５．８（ｇ）の混合液）を用意した。 Next, an electrolytic polymerization liquid (anthraquinone-1,5-disulfonic acid disodium: 1.4 (mmol) + pyrrole: 0.6 (g) + H 2 O: 45.8 (g) mixed liquid) was prepared. .
プレコート層形成済みエッチドアルミニウム化成箔を電解重合液中に浸漬し、プレコート層に接触させた外部電極を陽極として、電流値を０．４ｍＡに固定して電解重合を行い、導電性高分子層（固体電解質層）を形成した。 A conductive polymer layer is formed by immersing an etched aluminum formed foil with a precoat layer formed in an electrolytic polymerization solution, using the external electrode brought into contact with the precoat layer as an anode, fixing the current value to 0.4 mA, and performing electrolytic polymerization. (Solid electrolyte layer) was formed.
次に、上記アルミニウム箔の導電性高分子層を形成した部分にカーボンペーストと銀ペーストを順に塗布し、乾燥させて、合計２０個のコンデンサ素子を完成させた。 Next, a carbon paste and a silver paste were sequentially applied to the portion of the aluminum foil where the conductive polymer layer was formed and dried to complete a total of 20 capacitor elements.
これら２０個のコンデンサ素子について、１００ｋＨｚにおける等価直列抵抗（ＥＳＲ）を測定した。また、１５５℃大気中放置による熱耐久性試験を行い、１００時間経過後に１００ｋＨｚにおける等価直列抵抗（ＥＳＲ）を評価した。なお、熱耐久性試験において素子モールドは行わなかった。 For these 20 capacitor elements, the equivalent series resistance (ESR) at 100 kHz was measured. In addition, a thermal durability test was conducted by leaving in the atmosphere at 155 ° C., and the equivalent series resistance (ESR) at 100 kHz was evaluated after 100 hours. In the thermal durability test, element molding was not performed.
（実施例７）
導電性高分子の製造方法を以下の方法に代えたこと以外は実施例６と同様にして、２０個のコンデンサ素子を得た。すなわち、電解重合液にアントラキノン−１，８−ジスルホン酸二ナトリウム：１．４（ｍｍｏｌ）＋ピロール：０．６（ｇ）＋Ｈ２Ｏ：４５．８（ｇ）の混合溶液を用いて電解重合を行い、導電性高分子層を形成した。コンデンサ素子の特性評価を実施例６と同様に行った。
(Example 7)
Twenty capacitor elements were obtained in the same manner as in Example 6 except that the method for producing the conductive polymer was changed to the following method. That is, electrolytic polymerization using a mixed solution of anthraquinone-1,8-disulfonic acid disodium: 1.4 (mmol) + pyrrole: 0.6 (g) + H 2 O: 45.8 (g) as an electrolytic polymerization solution. To form a conductive polymer layer. The characteristics of the capacitor element were evaluated in the same manner as in Example 6.
（実施例８）
導電性高分子の製造方法を以下の方法に代えたこと以外は実施例６と同様にして、２０個のコンデンサ素子を得た。すなわち、電解重合液にアントラキノン−２，６−ジスルホン酸二ナトリウム：１．４（ｍｍｏｌ）＋ピロール：０．６（ｇ）＋Ｈ２Ｏ：４５．８（ｇ）の混合溶液を用いて電解重合を行い、導電性高分子層を形成した。コンデンサ素子の特性評価を実施例６と同様に行った。
(Example 8)
Twenty capacitor elements were obtained in the same manner as in Example 6 except that the method for producing the conductive polymer was changed to the following method. That is, electrolytic polymerization using a mixed solution of anthraquinone-2,6-disulfonic acid disodium: 1.4 (mmol) + pyrrole: 0.6 (g) + H 2 O: 45.8 (g) as an electrolytic polymerization solution. To form a conductive polymer layer. The characteristics of the capacitor element were evaluated in the same manner as in Example 6.
（実施例９）
導電性高分子の製造方法を以下の方法に代えたこと以外は実施例６と同様にして、２０個のコンデンサ素子を得た。すなわち、電解重合液にアントラキノン−２，７−ジスルホン酸二ナトリウム：１．４（ｍｍｏｌ）＋ピロール：０．６（ｇ）＋Ｈ２Ｏ：４５．８（ｇ）の混合溶液を用いて電解重合を行い、導電性高分子層を形成した。コンデンサ素子の特性評価を実施例６と同様に行った。
Example 9
Twenty capacitor elements were obtained in the same manner as in Example 6 except that the method for producing the conductive polymer was changed to the following method. That is, electrolytic polymerization using a mixed solution of anthraquinone-2,7-disulfonic acid disodium: 1.4 (mmol) + pyrrole: 0.6 (g) + H 2 O: 45.8 (g) as an electrolytic polymerization solution. To form a conductive polymer layer. The characteristics of the capacitor element were evaluated in the same manner as in Example 6.
（実施例１０）
導電性高分子の製造方法を以下の方法に代えたこと以外は実施例６と同様にして、２０個のコンデンサ素子を得た。すなわち、電解重合液にアントラキノン−１，５−ジスルホン酸二ナトリウム：１．２６（ｍｍｏｌ）＋アントラキノン−２−スルホン酸ナトリウム：０．１４（ｍｍｏｌ）＋ピロール：０．６（ｇ）＋Ｈ２Ｏ：４５．８（ｇ）の混合溶液を用いて電解重合を行い、導電性高分子層を形成した。コンデンサ素子の特性評価を実施例６と同様に行った。
(Example 10)
Twenty capacitor elements were obtained in the same manner as in Example 6 except that the method for producing the conductive polymer was changed to the following method. That is, anthraquinone-1,5-disulfonate disodium: 1.26 (mmol) + sodium anthraquinone-2-sulfonate: 0.14 (mmol) + pyrrole: 0.6 (g) + H 2 O : Electrolytic polymerization was performed using a mixed solution of 45.8 (g) to form a conductive polymer layer. The characteristics of the capacitor element were evaluated in the same manner as in Example 6.
（実施例１１）
導電性高分子の製造方法を以下の方法に代えたこと以外は実施例６と同様にして、２０個のコンデンサ素子を得た。すなわち、電解重合液にアントラキノン−１，８−ジスルホン酸二ナトリウム：１．２６（ｍｍｏｌ）＋アントラキノン−１，５−ジスルホン酸二ナトリウム：０．１４（ｍｍｏｌ）＋ピロール：０．６（ｇ）＋Ｈ２Ｏ：４５．８（ｇ）の混合溶液を用いて電解重合を行い、導電性高分子層を形成した。コンデンサ素子の特性評価を実施例６と同様に行った。
(Example 11)
Twenty capacitor elements were obtained in the same manner as in Example 6 except that the method for producing the conductive polymer was changed to the following method. That is, anthraquinone-1,8-disulfonic acid disodium: 1.26 (mmol) + anthraquinone-1,5-disulfonic acid disodium: 0.14 (mmol) + pyrrole: 0.6 (g) Electrolytic polymerization was performed using a mixed solution of + H 2 O: 45.8 (g) to form a conductive polymer layer. The characteristics of the capacitor element were evaluated in the same manner as in Example 6.
（実施例１２）
導電性高分子の製造方法を以下の方法に代えたこと以外は実施例６と同様にして、２０個のコンデンサ素子を得た。すなわち、電解重合液にアントラキノン−２，６−ジスルホン酸二ナトリウム：１．２６（ｍｍｏｌ）＋アントラキノン−２−スルホン酸ナトリウム：０．１４（ｍｍｏｌ）＋ピロール：０．６（ｇ）＋Ｈ２Ｏ：４５．８（ｇ）の混合溶液を用いて電解重合を行い、導電性高分子層を形成した。コンデンサ素子の特性評価を実施例６と同様に行った。
(Example 12)
Twenty capacitor elements were obtained in the same manner as in Example 6 except that the method for producing the conductive polymer was changed to the following method. That is, anthraquinone-2,6-disulfonic acid disodium: 1.26 (mmol) + sodium anthraquinone-2-sulfonic acid: 0.14 (mmol) + pyrrole: 0.6 (g) + H 2 O : Electrolytic polymerization was performed using a mixed solution of 45.8 (g) to form a conductive polymer layer. The characteristics of the capacitor element were evaluated in the same manner as in Example 6.
（実施例１３）
導電性高分子の製造方法を以下の方法に代えたこと以外は実施例６と同様にして、２０個のコンデンサ素子を得た。すなわち、電解重合液にアントラキノン−２，７−ジスルホン酸二ナトリウム：１．２６（ｍｍｏｌ）＋アントラキノン−２．６−ジスルホン酸二ナトリウム：０．１４（ｍｍｏｌ）＋ピロール：０．６（ｇ）＋Ｈ２Ｏ：４５．８（ｇ）の混合溶液を用いて電解重合を行い、導電性高分子層を形成した。コンデンサ素子の特性評価を実施例６と同様に行った。
(Example 13)
Twenty capacitor elements were obtained in the same manner as in Example 6 except that the method for producing the conductive polymer was changed to the following method. That is, anthraquinone-2,7-disulfonic acid disodium: 1.26 (mmol) + anthraquinone-2.6-disulfonic acid disodium: 0.14 (mmol) + pyrrole: 0.6 (g) Electrolytic polymerization was performed using a mixed solution of + H 2 O: 45.8 (g) to form a conductive polymer layer. The characteristics of the capacitor element were evaluated in the same manner as in Example 6.
（実施例１４）
導電性高分子の製造方法を以下の方法に代えたこと以外は実施例６と同様にして、２０個のコンデンサ素子を得た。すなわち、電解重合液にアントラキノン−１，５−ジスルホン酸二ナトリウム：１．４（ｍｍｏｌ）＋ピロール：０．６（ｇ）＋Ｈ２Ｏ：４５．８（ｇ）＋４−ニトロフェノール：０．２２９（ｍｍｏｌ）の混合溶液を用いて電解重合を行い、導電性高分子層を形成した。コンデンサ素子の特性評価を実施例６と同様に行った。
(Example 14)
Twenty capacitor elements were obtained in the same manner as in Example 6 except that the method for producing the conductive polymer was changed to the following method. That is, anthraquinone-1,5-disulfonic acid disodium: 1.4 (mmol) + pyrrole: 0.6 (g) + H 2 O: 45.8 (g) + 4-nitrophenol: 0.229 Electrolytic polymerization was performed using a mixed solution of (mmol) to form a conductive polymer layer. The characteristics of the capacitor element were evaluated in the same manner as in Example 6.
（実施例１５）
導電性高分子の製造方法を以下の方法に代えたこと以外は実施例６と同様にして、２０個のコンデンサ素子を得た。すなわち、電解重合液にアントラキノン−１，８−ジスルホン酸二ナトリウム：１．４（ｍｍｏｌ）＋ピロール：０．６（ｇ）＋Ｈ２Ｏ：４５．８（ｇ）＋４−ニトロ−１−ナフトール：０．２２９（ｍｍｏｌ）の混合溶液を用いて電解重合を行い、導電性高分子層を形成した。コンデンサ素子の特性評価を実施例６と同様に行った。
(Example 15)
Twenty capacitor elements were obtained in the same manner as in Example 6 except that the method for producing the conductive polymer was changed to the following method. That is, anthraquinone-1,8-disulfonic acid disodium: 1.4 (mmol) + pyrrole: 0.6 (g) + H 2 O: 45.8 (g) + 4-nitro-1-naphthol: Electrolytic polymerization was performed using a mixed solution of 0.229 (mmol) to form a conductive polymer layer. The characteristics of the capacitor element were evaluated in the same manner as in Example 6.
（実施例１６）
導電性高分子の製造方法を以下の方法に代えたこと以外は実施例６と同様にして、２０個のコンデンサ素子を得た。すなわち、電解重合液にアントラキノン−２，６−ジスルホン酸二ナトリウム：１．４（ｍｍｏｌ）＋ピロール：０．６（ｇ）＋Ｈ２Ｏ：４５．８（ｇ）＋１−ヒドロキシ−４−ニトロアントラキノン：０．２２９（ｍｍｏｌ）の混合溶液を用いて電解重合を行い、導電性高分子層を形成した。コンデンサ素子の特性評価を実施例６と同様に行った。
(Example 16)
Twenty capacitor elements were obtained in the same manner as in Example 6 except that the method for producing the conductive polymer was changed to the following method. That is, anthraquinone-2,6-disulfonic acid disodium: 1.4 (mmol) + pyrrole: 0.6 (g) + H 2 O: 45.8 (g) + 1-hydroxy-4-nitroanthraquinone : Electrolytic polymerization was performed using a mixed solution of 0.229 (mmol) to form a conductive polymer layer. The characteristics of the capacitor element were evaluated in the same manner as in Example 6.
（実施例１７）
導電性高分子の製造方法を以下の方法に代えたこと以外は実施例６と同様にして、２０個のコンデンサ素子を得た。すなわち、電解重合液にアントラキノン−２，７−ジスルホン酸二ナトリウム：１．４（ｍｍｏｌ）＋ピロール：０．６（ｇ）＋Ｈ２Ｏ：４５．８（ｇ）＋４−ニトロフェノール：０．２２９（ｍｍｏｌ）の混合溶液を用いて電解重合を行い、導電性高分子層を形成した。コンデンサ素子の特性評価を実施例６と同様に行った。
(Example 17)
Twenty capacitor elements were obtained in the same manner as in Example 6 except that the method for producing the conductive polymer was changed to the following method. That is, anthraquinone-2,7-disulfonic acid disodium: 1.4 (mmol) + pyrrole: 0.6 (g) + H 2 O: 45.8 (g) + 4-nitrophenol: 0.229 Electrolytic polymerization was performed using a mixed solution of (mmol) to form a conductive polymer layer. The characteristics of the capacitor element were evaluated in the same manner as in Example 6.
（実施例１８）
導電性高分子の製造方法を以下の方法に代えたこと以外は実施例６と同様にして、２０個のコンデンサ素子を得た。すなわち、電解重合液にアントラキノン−２，７−ジスルホン酸二ナトリウム：１．３８６（ｍｍｏｌ）＋アントラキノン−２．６−ジスルホン酸二ナトリウム：０．０１４（ｍｍｏｌ）＋ピロール：０．６（ｇ）＋Ｈ２Ｏ：４５．８（ｇ）の混合溶液を用いて電解重合を行い、導電性高分子層を形成した。コンデンサ素子の特性評価を実施例６と同様に行った。
(Example 18)
Twenty capacitor elements were obtained in the same manner as in Example 6 except that the method for producing the conductive polymer was changed to the following method. That is, anthraquinone-2,7-disulfonic acid disodium: 1.386 (mmol) + anthraquinone-2.6-disulfonic acid disodium: 0.014 (mmol) + pyrrole: 0.6 (g) Electrolytic polymerization was performed using a mixed solution of + H 2 O: 45.8 (g) to form a conductive polymer layer. The characteristics of the capacitor element were evaluated in the same manner as in Example 6.
（実施例１９）
導電性高分子の製造方法を以下の方法に代えたこと以外は実施例６と同様にして、２０個のコンデンサ素子を得た。すなわち、電解重合液にアントラキノン−２，７−ジスルホン酸二ナトリウム：０．９８（ｍｍｏｌ）＋アントラキノン−２．６−ジスルホン酸二ナトリウム：０．４２（ｍｍｏｌ）＋ピロール：０．６（ｇ）＋Ｈ２Ｏ：４５．８（ｇ）の混合溶液を用いて電解重合を行い、導電性高分子層を形成した。コンデンサ素子の特性評価を実施例６と同様に行った。
(Example 19)
Twenty capacitor elements were obtained in the same manner as in Example 6 except that the method for producing the conductive polymer was changed to the following method. That is, anthraquinone-2,7-disulfonic acid disodium: 0.98 (mmol) + anthraquinone-2.6-disulfonic acid disodium: 0.42 (mmol) + pyrrole: 0.6 (g) Electrolytic polymerization was performed using a mixed solution of + H 2 O: 45.8 (g) to form a conductive polymer layer. The characteristics of the capacitor element were evaluated in the same manner as in Example 6.
（比較例３）
導電性高分子の製造方法を以下の方法に代えたこと以外は実施例６と同様にして２０個のコンデンサ素子を得た。すなわち、電解重合液にブチルナフタレンスルホン酸ナトリウム：１．４（ｍｍｏｌ）＋ピロール：０．６（ｇ）＋Ｈ２Ｏ：４５．８（ｇ）の混合溶液を用いて電解重合を行い、導電性高分子層を形成した。コンデンサ素子の特性評価を実施例６と同様に行った。
(Comparative Example 3)
Twenty capacitor elements were obtained in the same manner as in Example 6 except that the method for producing the conductive polymer was changed to the following method. That is, electropolymerization was performed using a mixed solution of sodium butylnaphthalenesulfonate: 1.4 (mmol) + pyrrole: 0.6 (g) + H 2 O: 45.8 (g) in the electrolytic polymerization solution, and the conductivity was increased. A polymer layer was formed. The characteristics of the capacitor element were evaluated in the same manner as in Example 6.
（比較例４）
導電性高分子の製造方法を以下の方法に代えたこと以外は実施例６と同様にして２０個のコンデンサ素子を得た。すなわち、電解重合液に１，５−ナフタレンスルホン酸二ナトリウム：１．４（ｍｍｏｌ）＋ピロール：０．６（ｇ）＋Ｈ２Ｏ：４５．８（ｇ）の混合溶液を用いて電解重合を行い、導電性高分子層を形成した。コンデンサ素子の特性評価を実施例６と同様に行った。
(Comparative Example 4)
Twenty capacitor elements were obtained in the same manner as in Example 6 except that the method for producing the conductive polymer was changed to the following method. That is, electrolytic polymerization was performed using a mixed solution of disodium 1,5-naphthalenesulfonate: 1.4 (mmol) + pyrrole: 0.6 (g) + H 2 O: 45.8 (g) as an electrolytic polymerization solution. And a conductive polymer layer was formed. The characteristics of the capacitor element were evaluated in the same manner as in Example 6.
（比較例５）
導電性高分子の製造方法を以下の方法に代えたこと以外は実施例６と同様にして２０個のコンデンサ素子を得た。すなわち、電解重合液に２，７−ナフタレンスルホン酸二ナトリウム：１．４（ｍｍｏｌ）＋ピロール：０．６（ｇ）＋Ｈ２Ｏ：４５．８（ｇ）の混合溶液を用いて電解重合を行い、導電性高分子層を形成した。コンデンサ素子の特性評価を実施例６と同様に行った。
(Comparative Example 5)
Twenty capacitor elements were obtained in the same manner as in Example 6 except that the method for producing the conductive polymer was changed to the following method. That is, electrolytic polymerization was performed using a mixed solution of 2,7-naphthalenesulfonic acid disodium: 1.4 (mmol) + pyrrole: 0.6 (g) + H 2 O: 45.8 (g) as an electrolytic polymerization solution. And a conductive polymer layer was formed. The characteristics of the capacitor element were evaluated in the same manner as in Example 6.
実施例６〜１９及び比較例３〜５のコンデンサ素子の測定結果を表２、３に示す。 Tables 2 and 3 show the measurement results of the capacitor elements of Examples 6 to 19 and Comparative Examples 3 to 5.
表中の※１）は、Ｄ１とＤ２のモル比は実施例１０から実施例１３ではＤ１：Ｄ２＝９０：１０、実施例１８ではＤ１：Ｄ２＝９９：１、実施例１９ではＤ１：Ｄ２＝７０：３０を意味する。 * 1) in the table indicates that the molar ratio of D1 to D2 is D1: D2 = 90: 10 in Examples 10 to 13, D1: D2 = 99: 1 in Example 18, and D1: D2 in Example 19. = 70: 30.
実施例６〜１９と比較例３〜５を比較すると、実施例６〜１９の方がコンデンサのＥＳＲの低減及び優れた熱耐久性が得られた。実施例６〜９より実施例１０〜１３の方が、ＥＳＲが低いことより、Ｄ１とＤ２の混合した支持電解質を用いる方が優れたＥＳＲを得られることがわかった。
また、添加剤を加えた実施例１４〜１７では、大幅に熱耐久性が向上することがわかった。
When Examples 6 to 19 and Comparative Examples 3 to 5 were compared, Examples 6 to 19 obtained a reduction in ESR of the capacitor and excellent thermal durability. It turned out that the ESR which was excellent in the direction of using the supporting electrolyte which D1 and D2 mixed from Examples 10-13 from Examples 10-13 is lower than ESR.
Moreover, in Examples 14-17 which added the additive, it turned out that thermal durability improves significantly.
本発明の電解重合液により得られる導電性高分子は、固体電解コンデンサはもとより、有機ＥＬディスプレイ、有機トランジスタ、ポリマー電池、太陽電池、各種センサー材料、電磁波シールド材料、帯電防止材料、エレクトロクロミック材料、人工筋肉などに好適に使用できる。 The conductive polymer obtained by the electrolytic polymerization solution of the present invention is not only a solid electrolytic capacitor, but also an organic EL display, an organic transistor, a polymer battery, a solar battery, various sensor materials, an electromagnetic shielding material, an antistatic material, an electrochromic material, It can be suitably used for artificial muscles.
Claims (11)
該支持電解質塩として、下記一般式（１）で示される化合物を少なくとも1種類含むことを特徴とする導電性高分子形成用電解重合液。
An electropolymerization liquid for forming a conductive polymer, comprising at least one compound represented by the following general formula (1) as the supporting electrolyte salt.
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| JP2006128232A (en) * | 2004-10-27 | 2006-05-18 | Japan Carlit Co Ltd:The | Solid electrolytic capacitor |
| JP2007142070A (en) * | 2005-11-17 | 2007-06-07 | Tayca Corp | Dopant solution for conductive polymer, oxidizing agent also serving as dopant for conductive polymer, conductive composition, solid electrolytic capacitor, and method of manufacturing same |
| JP2007184317A (en) * | 2006-01-04 | 2007-07-19 | Shin Etsu Polymer Co Ltd | Method of manufacturing solid-state electrolytic capacitor |
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| JP2005011925A (en) * | 2003-06-18 | 2005-01-13 | Matsushita Electric Ind Co Ltd | Solid electrolytic capacitor and its manufacturing process |
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| JP2007142070A (en) * | 2005-11-17 | 2007-06-07 | Tayca Corp | Dopant solution for conductive polymer, oxidizing agent also serving as dopant for conductive polymer, conductive composition, solid electrolytic capacitor, and method of manufacturing same |
| JP2007184317A (en) * | 2006-01-04 | 2007-07-19 | Shin Etsu Polymer Co Ltd | Method of manufacturing solid-state electrolytic capacitor |
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