JP6901158B2 - Conductive Polymer Composition and Its Applications - Google Patents
Conductive Polymer Composition and Its Applications Download PDFInfo
- Publication number
- JP6901158B2 JP6901158B2 JP2019137465A JP2019137465A JP6901158B2 JP 6901158 B2 JP6901158 B2 JP 6901158B2 JP 2019137465 A JP2019137465 A JP 2019137465A JP 2019137465 A JP2019137465 A JP 2019137465A JP 6901158 B2 JP6901158 B2 JP 6901158B2
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- Prior art keywords
- polymer composition
- conductive polymer
- conductive
- sulfonic acid
- dispersion liquid
- Prior art date
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- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical group CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 description 1
- ADTJPOBHAXXXFS-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]prop-2-enamide Chemical compound CN(C)CCCNC(=O)C=C ADTJPOBHAXXXFS-UHFFFAOYSA-N 0.000 description 1
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920003214 poly(methacrylonitrile) Polymers 0.000 description 1
- 229920006350 polyacrylonitrile resin Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol 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
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
Description
本発明は、導電性高分子組成物およびそれらの用途、すなわち、前記導電性高分子組成物を電解質として用いた電解コンデンサ、前記導電性高分子組成物からなる導電性フィルムや前記導電性高分子組成物を基布に保持させた導電性布などに関する。 The present invention relates to a conductive polymer composition and its use, that is, an electrolytic capacitor using the conductive polymer composition as an electrolyte, a conductive film composed of the conductive polymer composition, and the conductive polymer. The present invention relates to a conductive cloth or the like in which the composition is held on a base cloth.
導電性高分子組成物は、その高い導電性により、タンタル電解コンデンサ、ニオブ電解コンデンサ、アルミニウム電解コンデンサなどの電解コンデンサの電解質として用いられている。 Due to its high conductivity, the conductive polymer composition is used as an electrolyte for electrolytic capacitors such as tantalum electrolytic capacitors, niobium electrolytic capacitors, and aluminum electrolytic capacitors.
そして、この用途における導電性高分子組成物としては、チオフェンまたはその誘導体、ピロールまたはその誘導体およびアニリンまたはその誘導体よりなる群から選ばれる少なくとも１種のモノマーを酸化重合することによって合成したものが用いられている。 As the conductive polymer composition in this application, one synthesized by oxidative polymerization of at least one monomer selected from the group consisting of thiophene or a derivative thereof, pyrrole or a derivative thereof and aniline or a derivative thereof is used. Has been done.
上記モノマーの酸化重合、特に化学酸化重合を行う際のドーパントとしては、主として有機スルホン酸が用いられ、その中でも、芳香族スルホン酸が適しているといわれており、酸化剤としては遷移金属が用いられ、その中でも、第二鉄が適しているといわれていて、通常、芳香族スルホン酸の第二鉄塩がチオフェンまたはその誘導体などの重合性モノマーの化学酸化重合にあたっての酸化剤兼ドーパント剤として用いられている。 Organic sulfonic acid is mainly used as a dopant when performing oxidative polymerization of the above monomer, particularly chemical oxidative polymerization, and among them, aromatic sulfonic acid is said to be suitable, and a transition metal is used as an oxidizing agent. Among them, ferric is said to be suitable, and the ferrous salt of aromatic sulfonic acid is usually used as an oxidizing agent and a dopant in the chemical oxidative polymerization of a polymerizable monomer such as thiophene or a derivative thereof. It is used.
そして、その芳香族スルホン酸の第二鉄塩の中でも、トルエンスルホン酸第二鉄やメトキシベンゼンスルホン酸第二鉄などが特に有用であるとされていて、それらを用いた導電性高分子組成物の製造は、それらの酸化剤兼ドーパントを前記の重合性モノマーと混合することにより行うことができ、簡単で、工業化に向いていると報告されている（特許文献１〜２）。 Among the ferric salts of the aromatic sulfonic acid, ferric toluenesulfonic acid, ferric methoxybenzenesulfonic acid and the like are said to be particularly useful, and a conductive polymer composition using them. Can be produced by mixing these oxidizing agents and dopants with the above-mentioned polymerizable monomer, and it is reported that they are simple and suitable for industrialization (Patent Documents 1 and 2).
しかしながら、トルエンスルホン酸第二鉄を酸化剤兼ドーパントとして用いて得られた導電性高分子組成物は、導電性や耐熱性が充分とはいえず、また、メトキシベンゼンスルホン酸第二鉄を酸化剤兼ドーパントとして用いて得られた導電性高分子組成物は、トルエンスルホン酸第二鉄を用いた導電性高分子組成物に比べれば、導電性が高く、耐熱性も優れているが、それでも充分に満足できる特性は得られなかった。 However, the conductive polymer composition obtained by using ferric toluenesulfonic acid as an oxidizing agent and dopant does not have sufficient conductivity and heat resistance, and oxidizes ferric methoxybenzenesulfonic acid. The conductive polymer composition obtained by using it as an agent and a dopant has higher conductivity and heat resistance than the conductive polymer composition using ferric toluenesulfonic acid, but it is still excellent. Sufficiently satisfactory characteristics could not be obtained.
また、スチレンスルホン酸と、メタクリル酸ヒドロキシアルキル、メタクリル酸グリシジル、アクリル酸ヒドロキシアルキル、アクリル酸グリシジルおよび不飽和炭化水素含有アルコキシシランまたはその加水分解物よりなる群から選ばれる少なくとも１種の非スルホン酸系モノマーとの共重合体の存在下で、チオフェンまたはその誘導体を酸化重合することにより得た導電性高分子組成物も提案されている（特許文献３）。 Further, at least one non-sulfonic acid selected from the group consisting of styrene sulfonic acid and hydroxyalkyl methacrylate, glycidyl methacrylate, hydroxyalkyl acrylate, glycidyl acrylate and unsaturated hydrocarbon-containing alkoxysilane or a hydrolyzate thereof. A conductive polymer composition obtained by oxidatively polymerizing thiophene or a derivative thereof in the presence of a copolymer with a system monomer has also been proposed (Patent Document 3).
しかしながら、上記特許文献３の導電性高分子組成物も、導電性が高いものの、高温高湿下での使用に際しては必ずしも充分な特性を有しているとはいえず、今後、高温高湿下での使用に際しても高い特性が要求される用途に対しては、その要求に応えていくことが難しいと考えられる。 However, although the conductive polymer composition of Patent Document 3 is also highly conductive, it does not necessarily have sufficient properties when used under high temperature and high humidity, and it cannot be said that it has sufficient properties in the future under high temperature and high humidity. It is considered difficult to meet the demands for applications that require high characteristics even when used in.
本発明は、上記のような事情に鑑み、導電性が高く、かつ、耐熱性が優れ、耐湿熱性が優れた導電性高分子組成物を提供し、その導電性高分子組成物を電解質として用いて、ＥＳＲが低く（小さく）、かつ、耐熱性、耐湿熱性が優れていて高温高湿下での使用に際して信頼性が高い電解コンデンサを提供し、また、上記導電性高分子組成物を用いて、導電性が高く、かつ耐熱性が優れ、耐湿熱性が優れた導電性フィルムや導電性布を提供することを目的とする。 In view of the above circumstances, the present invention provides a conductive polymer composition having high conductivity, excellent heat resistance, and excellent moist heat resistance, and the conductive polymer composition is used as an electrolyte. Further, an electrolytic capacitor having a low (small) ESR, excellent heat resistance and moisture heat resistance, and high reliability when used under high temperature and high humidity is provided, and the above-mentioned conductive polymer composition is used. An object of the present invention is to provide a conductive film or a conductive cloth having high conductivity, excellent heat resistance, and excellent moisture and heat resistance.
本発明者らは、上記課題を解決すべく鋭意研究を重ねた結果、スチレンスルホン酸と、アクリルアミド基またはメタクリルアミド基を含む重合性モノマーとの共重合体の存在下で、チオフェンおよびその誘導体よりなる群から選ばれる少なくとも１種を水中または水と水混和性溶剤との混合物からなる水性液中で酸化重合することにより得られた導電性高分子組成物が、前記目的を達成するのに適していることを見出し、それに基づいて本発明を完成するにいたった。 As a result of intensive studies to solve the above problems, the present inventors have obtained thiophene and its derivatives in the presence of a copolymer of styrene sulfonic acid and a polymerizable monomer containing an acrylamide group or a methacrylic amide group. A conductive polymer composition obtained by oxidatively polymerizing at least one selected from the above group in water or an aqueous solution consisting of a mixture of water and a water-miscible solvent is suitable for achieving the above object. Based on this, the present invention was completed.
すなわち、本願の第１の発明は、スチレンスルホン酸と、アクリルアミド基またはメタクリルアミド基を含む重合性モノマーとの共重合体が、チオフェンおよびその誘導体よりなる群から選ばれる少なくとも１種をモノマー成分とするπ共役系高分子にドーピングしてなることを特徴とする導電性高分子組成物に関する。 That is, in the first invention of the present application, a copolymer of styrene sulfonic acid and a polymerizable monomer containing an acrylamide group or a methacrylicamide group contains at least one selected from the group consisting of thiophene and its derivatives as a monomer component. The present invention relates to a conductive polymer composition, which is obtained by doping a π-conjugated polymer.
また、本願の第２の発明は、下記（I）と(II)とが、チオフェンおよびその誘導体よりなる群から選ばれる少なくとも１種をモノマー成分とするπ共役系高分子にドーピングしてなることを特徴とする導電性高分子組成物に関する。
（I）：スチレンスルホン酸と、アクリルアミド基またはメタクリルアミド基を含む重合性モノマーとの共重合体
（II）：ポリスチレンスルホン酸
Further, in the second invention of the present application, the following (I) and (II) are doped into a π-conjugated polymer containing at least one selected from the group consisting of thiophene and its derivatives as a monomer component. The present invention relates to a conductive polymer composition characterized by.
(I): Copolymer of styrene sulfonic acid and polymerizable monomer containing acrylamide group or methacrylamide group (II): Polystyrene sulfonic acid
本願の第３の発明は、下記（I）と(II)と（III）とが、チオフェンおよびその誘導体よりなる群から選ばれる少なくとも１種をモノマー成分とするπ共役系高分子にドーピングしてなることを特徴とする導電性高分子組成物に関する。
（I）：スチレンスルホン酸と、アクリルアミド基またはメタクリルアミド基を含む重合性モノマーとの共重合体
（II）：ポリスチレンスルホン酸
（III）：スルホン化ポリエステルおよびフェノールスルホン酸ノボラック樹脂よりなる群から選ばれる少なくとも１種のポリマーアニオン
In the third invention of the present application, the following (I), (II) and (III) are doped into a π-conjugated polymer containing at least one selected from the group consisting of thiophene and its derivatives as a monomer component. The present invention relates to a conductive polymer composition.
(I): A copolymer of styrene sulfonic acid and a polymerizable monomer containing an acrylamide group or a methacrylic amide group (II): Polystyrene sulfonic acid (III): Selected from the group consisting of sulfonated polyester and novolak phenol sulfonic acid. At least one polymer anion
本願の第４の発明は、下記（I）が、チオフェンおよびその誘導体よりなる群から選ばれる少なくとも１種をモノマー成分とするπ共役系高分子にドーピングしてなる導電性高分子組成物と、下記(III)が、チオフェンおよびその誘導体よりなる群から選ばれる少なくとも１種をモノマー成分とするπ共役系高分子にドーピングしてなる導電性高分子組成物との混合物からなることを特徴とする混合系の導電性高分子組成物に関する。
（I）：スチレンスルホン酸と、アクリルアミド基またはメタクリルアミド基を含む重合性モノマーとの共重合体
（III）：スルホン化ポリエステルおよびフェノールスルホン酸ノボラック樹脂よりなる群から選ばれる少なくとも１種のポリマーアニオン
The fourth invention of the present application is a conductive polymer composition in which the following (I) is doped with a π-conjugated polymer containing at least one selected from the group consisting of thiophene and its derivatives as a monomer component. The following (III) is characterized by comprising a mixture with a conductive polymer composition obtained by doping a π-conjugated polymer containing at least one selected from the group consisting of thiophene and its derivatives as a monomer component. The present invention relates to a mixed conductive polymer composition.
(I): Copolymer of styrene sulfonic acid and polymerizable monomer containing acrylamide group or methacrylic amide group (III): At least one polymer anion selected from the group consisting of sulfonated polyester and phenol sulfonic acid novolak resin.
本願の第５の発明は、下記(I)と(II)とが、チオフェンおよびその誘導体よりなる群から選ばれる少なくとも１種をモノマー成分とするπ共役系高分子にドーピングしてなる導電性高分子組成物と、下記(III)が、チオフェンおよびその誘導体よりなる群から選ばれる少なくとも１種をモノマー成分とするπ共役系高分子にドーピングしてなる導電性高分子組成物との混合物からなることを特徴とする混合系の導電性高分子組成物に関する。
（I）：スチレンスルホン酸と、アクリルアミド基またはメタクリルアミド基を含む重合性モノマーとの共重合体
（II）：ポリスチレンスルホン酸
（III）：スルホン化ポリエステルおよびフェノールスルホン酸ノボラック樹脂よりなる群から選ばれる少なくとも１種のポリマーアニオン
The fifth invention of the present application is a highly conductive polymer obtained by doping the following (I) and (II) into a π-conjugated polymer containing at least one selected from the group consisting of thiophene and its derivatives as a monomer component. The molecular composition comprises a mixture of a conductive polymer composition in which (III) below is doped with a π-conjugated polymer containing at least one selected from the group consisting of thiophene and its derivatives as a monomer component. The present invention relates to a mixed conductive polymer composition.
(I): A copolymer of styrene sulfonic acid and a polymerizable monomer containing an acrylamide group or a methacrylic amide group (II): Polystyrene sulfonic acid (III): Selected from the group consisting of sulfonated polyester and novolak phenol sulfonic acid. At least one polymer anion
さらに、本発明は、上記導電子高分子組成物と金属ナノワイヤーとの混合物からなる複合導電性組成物、上記導電性高分子組成物を電解質として用いた電解コンデンサ、上記導電性高分子組成物からなる電解質と電解液とを併用した電解コンデンサ、上記導電性高分子組成物または複合導電性組成物からなる導電性フィルム、基材上に形成した金属ナノワイヤーフィルム上に上記導電性高分子組成物を積層した導電性積層フィルム、基布に上記導電性高分子組成物または複合導電性組成物を保持させた導電性布などの導電性高分子組成物の用途に関する。 Further, the present invention comprises a composite conductive composition composed of a mixture of the conductor polymer composition and a metal nanowire, an electrolytic capacitor using the conductive polymer composition as an electrolyte, and the conductive polymer composition. An electrolytic capacitor in which an electrolyte composed of an electrolyte and an electrolytic solution are used in combination, a conductive film composed of the conductive polymer composition or the composite conductive composition, and the conductive polymer composition on a metal nanowire film formed on a base material. The present invention relates to an application of a conductive polymer composition such as a conductive laminated film in which objects are laminated, or a conductive cloth in which the above-mentioned conductive polymer composition or composite conductive composition is held on a base cloth.
本願の第１の発明による導電性高分子組成物は、導電性が高く、かつ耐熱性、耐湿熱性が優れているので、電解コンデンサの電解質として用いるのに適しており、それを電解質として用いることにより、ＥＳＲが低く（小さく）、かつ耐熱性、耐湿熱性が優れていて高温高湿下の使用での信頼性が高い電解コンデンサを提供することができる。しかも、上記導電性高分子組成物は、上記の導電性が高く、かつ耐熱性、耐湿熱性が優れているという特性に加えて、透明性も優れているので、導電性が高く、かつ耐熱性、耐湿性が優れ、しかも、透明性が高い導電性フィルムを提供することができる。 Since the conductive polymer composition according to the first invention of the present application has high conductivity and excellent heat resistance and moisture heat resistance, it is suitable for use as an electrolyte of an electrolytic capacitor, and it is used as an electrolyte. Therefore, it is possible to provide an electrolytic capacitor having a low (small) ESR, excellent heat resistance and moisture heat resistance, and high reliability in use under high temperature and high humidity. Moreover, the conductive polymer composition has high conductivity and excellent heat resistance and moisture heat resistance, and also has excellent transparency, so that the conductive polymer composition has high conductivity and heat resistance. It is possible to provide a conductive film having excellent moisture resistance and high transparency.
そして、上記のような特性に基づき、前記した複合導電性組成物、導電性積層フィルム、導電性布などの用途においても、導電性が高く、かつ耐熱性、耐湿熱性が優れているという特性を発揮させることができる。 Then, based on the above-mentioned characteristics, even in the above-mentioned applications such as the composite conductive composition, the conductive laminated film, and the conductive cloth, the characteristics of high conductivity and excellent heat resistance and moisture heat resistance are exhibited. It can be demonstrated.
本願の第２の発明による導電性高分子組成物は、第１の発明による導電性高分子組成物の特性を有しつつ、さらに導電性が向上しているので、それを用いることによって、前記の各種用途において、その特性を生かした電解コンデンサ、導電性フィルム、導電性布などを提供することができる。 The conductive polymer composition according to the second invention of the present application has the characteristics of the conductive polymer composition according to the first invention and is further improved in conductivity. In various applications of the above, it is possible to provide an electrolytic capacitor, a conductive film, a conductive cloth, etc., which make the best use of the characteristics.
本願の第３の発明による導電性高分子組成物は、第２の発明による導電性高分子組成物の特性を有しつつ、第２の発明による導電性高分子組成物より密着性が良好であり、第４の発明による導電性高分子組成物は、第１の発明による導電性高分子組成物の特性を有しつつ、第１の発明による導電性高分子組成物より密着性が良好であり、また、第５の発明による導電性高分子組成物は、第２の発明による導電性高分子組成物の特性を有しつつ、第２の発明による導電性高分子組成物より密着性が良好なので、それらを前記した用途に用いることにより、それらの特性を生かした電解コンデンサ、導電性フィルム、導電性布などを提供することができる。 The conductive polymer composition according to the third invention of the present application has the characteristics of the conductive polymer composition according to the second invention, and has better adhesion than the conductive polymer composition according to the second invention. The conductive polymer composition according to the fourth invention has the characteristics of the conductive polymer composition according to the first invention, and has better adhesion than the conductive polymer composition according to the first invention. Also, the conductive polymer composition according to the fifth invention has the characteristics of the conductive polymer composition according to the second invention, and has better adhesion than the conductive polymer composition according to the second invention. Since it is good, by using them in the above-mentioned applications, it is possible to provide an electrolytic capacitor, a conductive film, a conductive cloth, etc. that make the best use of these characteristics.
上記本願の第１の発明の導電性高分子組成物は、スチレンスルホン酸と、アクリルアミド基またはメタクリルアミド基を含む重合性モノマーとの共重合体の存在下で、チオフェンおよびその誘導体よりなる群から選ばれる少なくとも１種を水中または水と水混和性溶剤との混合物からなる水性液中で酸化重合することにより得られる導電性高分子組成物の分散液を乾燥することによって製造される。 The conductive polymer composition of the first invention of the present application comprises a group consisting of thiophene and a derivative thereof in the presence of a copolymer of styrene sulfonic acid and a polymerizable monomer containing an acrylamide group or a methacrylic amide group. It is produced by drying a dispersion of a conductive polymer composition obtained by oxidatively polymerizing at least one selected in water or an aqueous solution consisting of a mixture of water and a water-miscible solvent.
すなわち、上記のような酸化重合によりチオフェンおよびその誘導体よりなる群から選ばれる少なくとも１種が酸化重合されてπ共役系高分子が合成されるが、そのπ共役系高分子の合成時に、上記のスチレンスルホン酸と、アクリルアミド基またはメタクリルアミド基を含む重合性モノマーとの共重合体が、上記π共役系高分子にドーピングして、π共役系高分子に高い導電性が付与され、それによって、導電性高分子組成物が構成される。つまり、上記のπ共役系高分子とそれにドーピングした共重合体とで導電性高分子組成物が構成される。そして、この導電性高分子組成物には、後述するように、導電性付与剤やバインダを含有させるようにしてもよい。 That is, at least one selected from the group consisting of thiophene and its derivatives is oxidatively polymerized by the above-mentioned oxidative polymerization to synthesize a π-conjugated polymer. A copolymer of styrene sulfonic acid and a polymerizable monomer containing an acrylamide group or a methacrylamide group is doped into the π-conjugated polymer to impart high conductivity to the π-conjugated polymer, thereby imparting high conductivity. A conductive polymer composition is formed. That is, the conductive polymer composition is composed of the above-mentioned π-conjugated polymer and the copolymer doped with the above-mentioned π-conjugated polymer. Then, as will be described later, the conductive polymer composition may contain a conductivity-imparting agent or a binder.
そして、本願の第２の発明などにおけるスチレンスルホン酸も、第３の発明などにおけるスルホン化ポリエステルおよびフェノールスルホン酸ノボラック樹脂よりなる群から選ばれる少なくとも１種のポリマーアニオンも、上記共重合体と同様に、チオフェンおよびその誘導体よりなる群から選ばれる少なくとも１種をモノマー成分とするπ共役系高分子の合成時に、該π共役系高分子にドーピングしていく。 The styrene sulfonic acid in the second invention of the present application and at least one polymer anion selected from the group consisting of the sulfonated polyester and the phenol sulfonic acid novolak resin in the third invention are the same as the above-mentioned copolymer. In addition, when synthesizing a π-conjugated polymer containing at least one selected from the group consisting of thiophene and its derivatives as a monomer component, the π-conjugated polymer is doped.
本願の第２の発明の導電性高分子組成物は、下記（I）と（II）との存在下で、チオフェンおよびその誘導体よりなる群から選ばれる少なくとも１種を水中または水と水混和性溶剤との混合物からなる水性液中で酸化重合することにより得られる導電性高分子組成物の分散液を乾燥することによって製造される。
（I）：スチレンスルホン酸と、アクリルアミド基またはメタクリルアミド基を含む重合性モノマーとの共重合体
（II）：ポリスチレンスルホン酸
The conductive polymer composition of the second invention of the present application is miscible with water or water at least one selected from the group consisting of thiophene and its derivatives in the presence of the following (I) and (II). It is produced by drying a dispersion liquid of a conductive polymer composition obtained by oxidative polymerization in an aqueous liquid consisting of a mixture with a solvent.
(I): Copolymer of styrene sulfonic acid and polymerizable monomer containing acrylamide group or methacrylamide group (II): Polystyrene sulfonic acid
本願の第３の発明の導電性高分子組成物は、下記（I）と（II）と（III）との存在下で、チオフェンおよびその誘導体よりなる群から選ばれる少なくとも１種を水中または水と水混和性溶剤との混合物からなる水性液中で酸化重合することにより得られる導電性高分子組成物の分散液を乾燥することによって製造される。
（I）：スチレンスルホン酸と、アクリルアミド基またはメタクリルアミド基を含む重合性モノマーとの共重合体
（II）：ポリスチレンスルホン酸
（III）：スルホン化ポリエステルおよびフェノールスルホン酸ノボラック樹脂よりなる群から選ばれる少なくとも１種のポリマーアニオン
The conductive polymer composition of the third invention of the present application contains at least one selected from the group consisting of thiophene and its derivatives in water or water in the presence of the following (I), (II) and (III). It is produced by drying a dispersion liquid of a conductive polymer composition obtained by oxidative polymerization in an aqueous liquid consisting of a mixture of water and a water-miscible solvent.
(I): A copolymer of styrene sulfonic acid and a polymerizable monomer containing an acrylamide group or a methacrylic amide group (II): Polystyrene sulfonic acid (III): Selected from the group consisting of sulfonated polyester and novolak phenol sulfonic acid. At least one polymer anion
本願の第４の発明の混合系の導電性高分子組成物は、下記（I）の存在下で、チオフェンおよびその誘導体よりなる群から選ばれる少なくとも１種を水中または水と水混和性溶剤との混合物からなる水性液中で酸化重合することによって得られる導電性高分子組成物の分散液と、下記（III）の存在下で、チオフェンおよびその誘導体よりなる群から選ばれる少なくとも１種を水中または水と水混和性溶剤との混合物からなる水性液中で酸化重合することによって得られる導電性高分子組成物の分散液とを混合し、得られた混合系の導電性高分子組成物の分散液を乾燥することによって製造される。
（I）：スチレンスルホン酸と、アクリルアミド基またはメタクリルアミド基を含む重合性モノマーとの共重合体
（III）：スルホン化ポリエステルおよびフェノールスルホン酸ノボラック樹脂よりなる群から選ばれる少なくとも１種のポリマーアニオン
In the mixed conductive polymer composition of the fourth invention of the present application, at least one selected from the group consisting of thiophene and its derivatives is mixed with water or a water-miscible solvent in the presence of (I) below. In the presence of a dispersion of a conductive polymer composition obtained by oxidative polymerization in an aqueous solution consisting of a mixture of thiophene and the following (III), at least one selected from the group consisting of thiophene and its derivatives is placed in water. Alternatively, the conductive polymer composition of the mixed system obtained by mixing with the dispersion liquid of the conductive polymer composition obtained by oxidative polymerization in an aqueous solution consisting of a mixture of water and a water-miscible solvent. Manufactured by drying the dispersion.
(I): Copolymer of styrene sulfonic acid and polymerizable monomer containing acrylamide group or methacrylic amide group (III): At least one polymer anion selected from the group consisting of sulfonated polyester and phenol sulfonic acid novolak resin.
本願の第５の発明の混合系の導電性高分子組成物は、下記（I）と（II）との存在下で、チオフェンおよびその誘導体よりなる群から選ばれる少なくとも１種を水中または水と水混和性溶剤との混合物からなる水性液中で酸化重合することによって得られる導電性高分子組成物の分散液と、下記（III）の存在下で、チオフェンおよびその誘導体よりなる群から選ばれる少なくとも１種を水中または水と水混和性溶剤との混合物からなる水性液中で酸化重合することによって得られる導電性高分子組成物の分散液とを混合し、得られた混合系の導電性高分子組成物の分散液を乾燥することによって製造される。
（I）：スチレンスルホン酸と、アクリルアミド基またはメタクリルアミド基を含む重合性モノマーとの共重合体
（II）：ポリスチレンスルホン酸
（III）：スルホン化ポリエステルおよびフェノールスルホン酸ノボラック樹脂よりなる群から選ばれる少なくとも１種のポリマーアニオン
In the mixed conductive polymer composition of the fifth invention of the present application, in the presence of the following (I) and (II), at least one selected from the group consisting of thiophene and its derivatives is mixed with water or water. It is selected from the group consisting of a dispersion liquid of a conductive polymer composition obtained by oxidative polymerization in an aqueous liquid consisting of a mixture with a water-miscible solvent, and thiophene and a derivative thereof in the presence of (III) below. The conductivity of the mixed system obtained by mixing at least one type with a dispersion liquid of a conductive polymer composition obtained by oxidative polymerization in water or an aqueous liquid consisting of a mixture of water and a water-miscible solvent. It is produced by drying a dispersion of a polymer composition.
(I): A copolymer of styrene sulfonic acid and a polymerizable monomer containing an acrylamide group or a methacrylic amide group (II): Polystyrene sulfonic acid (III): Selected from the group consisting of sulfonated polyester and novolak phenol sulfonic acid. At least one polymer anion
本発明の基礎をなす第１の発明においては、導電性高分子組成物の製造にあたって、スチレンスルホン酸と、アクリルアミド基またはメタクリルアミド基を含む重合性モノマーとの共重合体をドーパントとして用いている。このアクリルアミド基またはメタクリルアミド基を含む重合性モノマーに属するものとしては、例えば、アクリルアミド、Ｎ−（ヒドロキシメチル）アクリルアミド、Ｎ−（２−ヒドロキシエチル）アクリルアミド、Ｎ−tert−ブチルアクリルアミド、Ｎ−イソプロピルアクリルアミド、Ｎ−ドデシルアクリルアミド、ジアセトンアクリルアミド、３−アクリロイル−２−オキサゾリジノン、６−アクリルアミドヘキサン酸、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ，Ｎ−ジエチルアクリルアミド、Ｎ−（３−ジメチルアミノプロピル）アクリルアミド、Ｎ−ドデシルアクリルアミド、Ｎ−(ブトキシメチル)アクリルアミド、Ｎ−フェニルアクリルアミド、４−アクリロイルモルホリン、２−アクリルアミド−２−メチルプロパンスルホン酸などのアクリル基を含む重合性モノマー、メタクリルアミド、Ｎ−メチルメタクリルアミド、Ｎ−（３−ジメチルアミノプロピル）メタクリルアミド、Ｎ−フェニルメタクリルアミド）、Ｎ−（４−ヒドロキシフェニル）メタクリルアミドなどのメタクリル基を含む重合性モノマーなどが挙げられ、このアクリルアミド基またはメタクリルアミド基を含む重合性モノマーとしては、特にＮ−（２−ヒドロキシエチル）アクリルアミド、Ｎ−（ヒドロキシメチル）アクリルアミド、Ｎ−メチルメタクリルアミド、Ｎ−（４−ヒドロキシフェニル）メタクリルアミド、Ｎ−フェニルアクリルアミド、Ｎ−フェニルメタクリルアミドなどが好ましい。 In the first invention, which is the basis of the present invention, a copolymer of styrene sulfonic acid and a polymerizable monomer containing an acrylamide group or a methacrylamide group is used as a dopant in the production of the conductive polymer composition. .. Examples of those belonging to the polymerizable monomer containing an acrylamide group or a methacrylamide group include acrylamide, N- (hydroxymethyl) acrylamide, N- (2-hydroxyethyl) acrylamide, N-tert-butylacrylamide, and N-isopropyl. Acrylamide, N-dodecylacrylamide, diacetoneacrylamide, 3-acrylloyl-2-oxazolidinone, 6-acrylamidehexanoic acid, N, N-dimethylacrylamide, N, N-diethylacrylamide, N- (3-dimethylaminopropyl) acrylamide, Polymerizable monomers containing acrylic groups such as N-dodecylacrylamide, N- (butoxymethyl) acrylamide, N-phenylacrylamide, 4-acrylloylmorpholin, 2-acrylamide-2-methylpropanesulfonic acid, methacrylamide, N-methylmethacryl Examples thereof include polymerizable monomers containing a methacrylic group such as amide, N- (3-dimethylaminopropyl) methacrylicamide, N-phenylmethacrylicamide) and N- (4-hydroxyphenyl) methacrylicamide, and the acrylamide group or methacrylamide. Examples of the polymerizable monomer containing an amide group include N- (2-hydroxyethyl) acrylamide, N- (hydroxymethyl) acrylamide, N-methylmethacrylamide, N- (4-hydroxyphenyl) methacrylamide, and N-phenylacrylamide. , N-Phenylmethacrylamide and the like are preferable.
本願の第１の発明において、上記のようなスチレンスルホン酸と、アクリルアミド基またはメタクリルアミド基を含む重合性モノマーとの共重合体をドーパントとして用いるのは、前記のように、ＥＳＲが低く、かつ耐熱性、耐湿熱性が優れていて高温高湿下における信頼性が高い電解コンデンサを製造するのに適した導電性高分子組成物や、導電性が高く、かつ耐熱性、耐湿熱性が優れた導電性フィルムを製造するのに適した導電性高分子組成物を得るためであるが、ドーパントとして用いる上記共重合体を合成するためのモノマーの一方の成分としてスチレンスルホン酸を用いるのは、そのスルホン酸部分でドーパントとして必要なアニオンを提供するためと共重合体に酸性を付与するためである。 In the first invention of the present application, using a copolymer of the above-mentioned styrene sulfonic acid and a polymerizable monomer containing an acrylamide group or a methacrylic amide group as a dopant has a low ESR and as described above. A conductive polymer composition suitable for producing an electrolytic capacitor having excellent heat resistance and moisture heat resistance and high reliability under high temperature and high humidity, and conductivity having high conductivity and excellent heat resistance and moisture heat resistance. This is to obtain a conductive polymer composition suitable for producing a sex film, but it is the sulfone that uses styrene sulfonic acid as one component of the monomer for synthesizing the above-mentioned copolymer used as a dopant. This is to provide the anion required as a dopant in the acid moiety and to impart acidity to the copolymer.
そして、このスチレンスルホン酸と共重合させるモノマーとして、前記アクリルアミド基またはメタクリルアミド基を含む重合性モノマーを用いるが、このアクリルアミド基またはメタクリルアミド基を含む重合性モノマーは、スチレンスルホン酸が文字通りスルホン酸系モノマーであるのに対して、非スルホン酸系モノマーであり、スルホン酸系モノマーとそれらの非スルホン酸系モノマーとを共重合させるのは、それによって得られる共重合体の方が、スチレンスルホン酸のホモポリマー（つまり、ポリスチレンスルホン酸）より、ドーパントとして用いたときに、導電性が高く、かつ耐熱性、耐湿熱性が優れた導電性高分子組成物が得られるようになるからである。そして、スチレンスルホン酸をモノマー状態で用いるのではなく、高分子化して用いるのは、高分子ドーパントを用いて導電性高分子組成物を製造した場合は、水または溶剤に対する分散性または溶解性が良好で、また、脱ドープされにくい特性が得られるからである。 Then, as the monomer copolymerized with the styrene sulfonic acid, the polymerizable monomer containing the acrylamide group or the methacrylicamide group is used, and in the polymerizable monomer containing the acrylamide group or the methacrylicamide group, the styrene sulfonic acid is literally a sulfonic acid. While it is a system monomer, it is a non-sulfonic acid type monomer, and it is the styrene sulfone that copolymerizes the sulfonic acid type monomer and those non-sulfonic acid type monomers. This is because, when used as a dopant, a conductive polymer composition having high conductivity and excellent heat resistance and moisture heat resistance can be obtained from the acid homopolymer (that is, polystyrene sulfonic acid). Then, styrene sulfonic acid is not used in a monomer state but is polymerized and used because, when a conductive polymer composition is produced using a polymer dopant, it has dispersibility or solubility in water or a solvent. This is because it is possible to obtain properties that are good and difficult to be dedoped.
これまでにも、スチレンスルホン酸と、ヒドロキシメタクリレートやヒドロキシアクリレートとを共重合させて得られる共重合体を、導電性高分子組成物を製造する際のドーパントとして用いた例があるが、本発明のスチレンスルホン酸と、アクリルアミド基またはメタクリルアミド基を含む重合性モノマーとの共重合体をドーパントして製造した導電性高分子組成物の方が、それら先行技術の共重合体をドーパントとして製造した導電性高分子組成物より、例えば、耐湿熱性が優れるなど、周囲の環境に対する抵抗性が優れていて、周囲の環境による特性低下が少ないという長所を有している。 There have been examples of using a copolymer obtained by copolymerizing styrene sulfonic acid with hydroxymethacrylate or hydroxyacrylate as a dopant in producing a conductive polymer composition. The conductive polymer composition produced by using a copolymer of the styrene sulfonic acid of No. 1 and a polymerizable monomer containing an acrylamide group or a methacrylic amide group as a dopant was produced by using the copolymer of the prior art as a dopant. Compared to the conductive polymer composition, it has an advantage that it has excellent resistance to the surrounding environment, such as excellent moisture and heat resistance, and that the characteristics are less likely to deteriorate due to the surrounding environment.
このスチレンスルホン酸と、アクリルアミド基またはメタクリルアミド基を含む重合性モノマーとの共重合体におけるスチレンスルホン酸と、アクリルアミド基またはメタクリルアミド基を含む重合性モノマーとの比率としては、モル比で、９．９：０．１〜０．１：９．９であることが好ましく、９．５：０．５〜４：６がより好ましく、９．５：０．５〜５：５がさらに好ましく、とりわけ９：１〜７：３が好ましい。これは、スチレンスルホン酸の比率が上記より少なくなると、導電性高分子組成物の導電性が低下するおそれがあり、逆にスチレンスルホン酸の比率が上記より多くなると、導電性高分子組成物の耐熱性、耐湿熱性が悪くなるおそれがあるためである。 The ratio of the styrene sulfonic acid in the copolymer of the styrene sulfonic acid and the polymerizable monomer containing an acrylamide group or a methacrylic amide group to the polymerizable monomer containing an acrylamide group or a methacrylic amide group is 9 in molar ratio. It is preferably 9.9: 0.1 to 0.1: 9.9, more preferably 9.5: 0.5 to 4: 6, still more preferably 9.5: 0.5 to 5: 5. Especially, 9: 1 to 7: 3 is preferable. This is because if the ratio of styrene sulfonic acid is lower than the above, the conductivity of the conductive polymer composition may decrease, and conversely, if the ratio of styrene sulfonic acid is higher than the above, the conductive polymer composition may be reduced in conductivity. This is because the heat resistance and the moisture heat resistance may deteriorate.
そして、上記スチレンスルホン酸と、アクリルアミド基またはメタクリルアミド基を含む重合性モノマーとの共重合体は、その分子量が、重量平均分子量で５，０００〜５００，０００程度のものが、水溶性およびドーパントとしての特性上から好ましく、重量平均分子量で４０，０００〜２００，０００程度のものがより好ましい。すなわち、上記共重合体の重量平均分子量が上記より小さい場合は、ドーパントとしての機能が低下し、その結果、導電性が高く、かつ耐熱性が優れた導電性高分子組成物が得られにくくなるおそれがあり、重量平均分子量が上記より大きくなると、水溶性が低下して、取扱性が悪くなるおそれがある。 The copolymer of the styrene sulfonic acid and the polymerizable monomer containing an acrylamide group or a methacrylamide group has a molecular weight of about 5,000 to 500,000 in terms of weight average molecular weight, and is water-soluble and a dopant. It is preferable from the viewpoint of the above-mentioned characteristics, and a weight average molecular weight of about 40,000 to 200,000 is more preferable. That is, when the weight average molecular weight of the copolymer is smaller than the above, the function as a dopant is lowered, and as a result, it becomes difficult to obtain a conductive polymer composition having high conductivity and excellent heat resistance. If the weight average molecular weight is larger than the above, the water solubility may be lowered and the handleability may be deteriorated.
導電性高分子組成物の製造にあたって、ドーパントとして使用する上記スチレンスルホン酸と、アクリルアミド基またはメタクリルアミド基を含む重合性モノマーとの共重合体の使用量は、チオフェンおよびその誘導体よりなる群から選ばれる少なくとも１種に対して質量比で１：０．０１〜１：２０であることが好ましく、１：０．０１〜１：２０であることがより好ましく、１：０．１〜１：２であることがさらに好ましい。つまり、スチレンスルホン酸と、アクリルアミド基またはメタクリルアミド基を含む重合性モノマーとの共重合体の使用量が上記より少ない場合は、上記共重合体のドーパントとしての機能が充分に発揮できなくなるおそれがあり、また、上記共重合体の使用量が上記より多くなっても、その使用量の増加に伴う効果の増加がほとんど見られなくなるだけでなく、逆に得られる導電性高分子組成物の導電性が低下するおそれがある。 In the production of the conductive polymer composition, the amount of the copolymer of the above-mentioned styrene sulfonic acid used as a dopant and the polymerizable monomer containing an acrylamide group or a methacrylic amide group is selected from the group consisting of thiophene and its derivatives. The mass ratio is preferably 1: 0.01 to 1:20, more preferably 1: 0.01 to 1:20, and 1: 0.1 to 1: 2 in terms of mass ratio. Is more preferable. That is, if the amount of the copolymer of the styrene sulfonic acid and the polymerizable monomer containing the acrylamide group or the methacrylamide group is smaller than the above, the function of the copolymer as a dopant may not be sufficiently exhibited. Yes, even if the amount of the copolymer used is larger than the above, not only the increase in the effect due to the increase in the amount used is hardly observed, but also the conductivity of the obtained conductive polymer composition is conversely observed. There is a risk of reduced sex.
一般に、導電性高分子組成物を酸化重合によって製造するための重合性モノマーとしては、チオフェンまたはその誘導体、ピロールまたはその誘導体およびアニリンまたはその誘導体よりなる群から選ばれる少なくとも１種のモノマーが用いられるが、本発明において、それらの中からチオフェンおよびその誘導体よりなる群から選ばれる少なくとも１種を用いるのは、それがドーパントとなる上記スチレンスルホン酸と、アクリルアミド基またはメタクリルアミド基を含む重合性モノマーとの共重合体との相性が良く、特に導電性の高い導電性高分子組成物を製造することができるからである。 Generally, as the polymerizable monomer for producing a conductive polymer composition by oxidative polymerization, at least one monomer selected from the group consisting of thiophene or a derivative thereof, pyrrole or a derivative thereof and aniline or a derivative thereof is used. However, in the present invention, at least one selected from the group consisting of thiophene and its derivatives is used as a polymerizable monomer containing the above-mentioned styrene sulfonic acid as a dopant and an acrylamide group or a methacrylic amide group. This is because it is possible to produce a conductive polymer composition having good compatibility with the copolymer of and having particularly high conductivity.
上記チオフェンおよびその誘導体よりなる群から選ばれる少なくとも１種におけるチオフェンの誘導体としては、例えば、３，４−エチレンジオキシチオフェン、３−アルキルチオフェン、３−アルコキシチオフェン、３−アルキル−４−アルコキシチオフェン、３，４−アルキルチオフェン、３，４−アルコキシチオフェンや、上記の３，４−エチレンジオキシチオフェンをアルキル基で修飾したアルキル化エチレンジオキシチオフェンなどが挙げられ、そのアルキル基やアルコキシ基の炭素数は１〜１６が好ましく、特に１〜４が好ましい。上記チオフェンやその誘導体は、それぞれ単独で用いることができるし、また、２種類以上を併用することもできる。 Examples of the thiophene derivative in at least one selected from the group consisting of the above thiophene and its derivatives include 3,4-ethylenedioxythiophene, 3-alkylthiophene, 3-alkoxythiophene, and 3-alkyl-4-alkoxythiophene. , 3,4-alkylthiophene, 3,4-alkoxythiophene, alkylated ethylenedioxythiophene obtained by modifying the above 3,4-ethylenedioxythiophene with an alkyl group, and the like. The number of carbon atoms is preferably 1 to 16, and particularly preferably 1 to 4. The above-mentioned thiophene and its derivatives can be used individually, or two or more kinds can be used in combination.
上記の３，４−エチレンジオキシチオフェンをアルキル基で修飾したアルキル化エチレンジオキシチオフェンについて詳しく説明すると、上記３，４−エチレンジオキシチオフェンやアルキル化エチレンジオキシチオフェンは、下記の一般式（１）で表される化合物に該当する。 The alkylated ethylenedioxythiophene obtained by modifying the above 3,4-ethylenedioxythiophene with an alkyl group will be described in detail. The above-mentioned 3,4-ethylenedioxythiophene and the alkylated ethylenedioxythiophene have the following general formulas ( It corresponds to the compound represented by 1).
そして、上記一般式（１）中のＲが水素の化合物が、３，４−エチレンジオキシチオフェンであり、これをＩＵＰＡＣ名称で表示すると、「２，３−ジヒドロ−チエノ〔３，４−ｂ〕〔１，４〕ジオキシン（２，３−Ｄｉｈｙｄｒｏ−ｔｈｉｅｎｏ〔３，４−ｂ〕〔１，４〕ｄｉｏｘｉｎｅ）」であるが、この化合物は、ＩＵＰＡＣ名称で表示されるよりも、一般名称の「３，４−エチレンジオキシチオフェン」で表示されることが多いので、本書では、この「２，３−ジヒドロ−チエノ〔３，４−ｂ〕〔１，４〕ジオキシン」を「３，４−エチレンジオキシチオフェン」と表示したり、さらに簡略化して「エチレンジオキシチオフェン」と表示している。そして、上記一般式（１）中のＲがアルキル基の場合、該アルキル基としては、炭素数が１〜４のもの、つまり、メチル基、エチル基、プロピル基、ブチル基が好ましく、それらを具体的に例示すると、一般式（１）中のＲがメチル基の化合物は、ＩＵＰＡＣ名称で表示すると、「２−メチル−２，３−ジヒドロ−チエノ〔３，４−ｂ〕〔１，４〕ジオキシン（２−Ｍｅｔｈｙｌ−２，３−ｄｉｈｙｄｒｏ−ｔｈｉｅｎｏ〔３，４−ｂ〕〔１，４〕ｄｉｏｘｉｎｅ）」であるが、以下、これを簡略化して「メチル化エチレンジオキシチオフェン」と表示する。一般式（１）中のＲがエチル基の化合物は、ＩＵＰＡＣ名称で表示すると、「２−エチル−２，３−ジヒドロ−チエノ〔３，４−ｂ〕〔１，４〕ジオキシン（２−Ｅｔｈｙｌ−２，３−ｄｉｈｙｄｒｏ−ｔｈｉｅｎｏ〔３，４−ｂ〕〔１，４〕ｄｉｏｘｉｎｅ）」であるが、以下、これを簡略化して「エチル化エチレンジオキシチオフェン」と表示する。一般式（１）中のＲがプロピル基の化合物は、ＩＵＰＡＣ名称で表示すると、「２−プロピル−２，３−ジヒドロ−チエノ〔３，４−ｂ〕〔１，４〕ジオキシン（２−Ｐｒｏｐｙｌ−２，３−ｄｉｈｙｄｒｏ−ｔｈｉｅｎｏ〔３，４−ｂ〕〔１，４〕ｄｉｏｘｉｎｅ）」であるが、以下、これを簡略化して「プロピル化エチレンジオキシチオフェン」と表示する。そして、一般式（１）中のＲがブチル基の化合物は、ＩＵＰＡＣ名称で表示すると、「２−ブチル−２，３−ジヒドロ−チエノ〔３，４−ｂ〕〔１，４〕ジオキシン（２−Ｂｕｔｙｌ−２，３−ｄｉｈｙｄｒｏ−ｔｈｉｅｎｏ〔３，４−ｂ〕〔１，４〕ｄｉｏｘｉｎｅ）」であるが、以下、これを簡略化して「ブチル化エチレンジオキシチオフェン」と表示する。また、「２−アルキル−２，３−ジヒドロ−チエノ〔３，４−ｂ〕〔１，４〕ジオキシン」を、以下、簡略化して「アルキル化エチレンジオキシチオフェン」で表わす。そして、これらのアルキル化エチレンジオキシチオフェンの中でも、メチル化エチレンジオキシチオフェン、エチル化エチレンジオキシチオフェン、プロピル化エチレンジオキシチオフェン、ブチル化エチレンジオキシチオフェンが好ましい。 The compound in which R is hydrogen in the above general formula (1) is 3,4-ethylenedioxythiophene, and when this is represented by the IUPAC name, "2,3-dihydro-thieno [3,4-b] ] [1,4] dioxin (2,3-Dihydro-thieno [3,4-b] [1,4] dioxin) ", but this compound has a more general name than indicated by the IUPAC name. Since it is often displayed as "3,4-ethylenedioxythiophene", in this document, this "2,3-dihydro-thieno [3,4-b] [1,4] dioxin" is referred to as "3,4". -It is displayed as "ethylenedioxythiophene" or, further simplified, as "ethylenedioxythiophene". When R in the general formula (1) is an alkyl group, the alkyl group preferably has 1 to 4 carbon atoms, that is, a methyl group, an ethyl group, a propyl group, or a butyl group. Specifically, the compound in which R is a methyl group in the general formula (1) is represented by the IUPAC name as "2-methyl-2,3-dihydro-thieno [3,4-b] [1,4". ] Dioxin (2-Methyl-2,3-dihydro-thiono [3,4-b] [1,4] dioxin) ”, but this is abbreviated below and is referred to as“ methylated ethylenedioxythiophene ”. To do. The compound in which R is an ethyl group in the general formula (1) is represented by the IUPAC name as "2-ethyl-2,3-dihydro-thieno [3,4-b] [1,4] dioxin (2-Ethyl). −2,3-dihydro-thiono [3,4-b] [1,4] dioxin) ”, but this will be abbreviated below and will be referred to as“ ethylated ethylenedioxythiophene ”. The compound in which R is a propyl group in the general formula (1) is represented by the IUPAC name as "2-propyl-2,3-dihydro-thieno [3,4-b] [1,4] dioxin (2-Propyl). −2,3-dihydro-thiono [3,4-b] [1,4] dioxin) ”, but this will be abbreviated below and will be referred to as“ propylated ethylenedioxythiophene ”. The compound in which R is a butyl group in the general formula (1) is represented by the IUPAC name as "2-butyl-2,3-dihydro-thieno [3,4-b] [1,4] dioxin (2). -Butyl-2,3-dihydro-thio [3,4-b] [1,4] dioxin) ”, but this will be abbreviated below and will be referred to as“ butylated ethylenedioxythiophene ”. Further, "2-alkyl-2,3-dihydro-thieno [3,4-b] [1,4] dioxine" is hereinafter abbreviated as "alkylated ethylenedioxythiophene". Among these alkylated ethylenedioxythiophenes, methylated ethylenedioxythiophene, ethylated ethylenedioxythiophene, propylated ethylenedioxythiophene, and butylated ethylenedioxythiophene are preferable.
これらのアルキル化エチレンジオキシチオフェンも、それぞれ単独で用いることができるし、また、２種類以上を併用することもできる。さらに、これらのアルキル化エチレンジオキシチオフェンと３，４−エチレンジオキシチオフェンとを併用することもできる。 These alkylated ethylenedioxythiophenes can also be used alone or in combination of two or more. Furthermore, these alkylated ethylenedioxythiophenes and 3,4-ethylenedioxythiophenes can also be used in combination.
上記スチレンスルホン酸と、アクリルアミド基またはメタクリルアミド基を含む重合性モノマーとの共重合体を用いてのチオフェンおよびその誘導体よりなる群から選ばれる少なくとも１種の酸化重合は、水中または水と水混和性溶剤との水溶液中で行われる。 At least one oxidative polymerization selected from the group consisting of thiophene and its derivatives using a copolymer of the above styrene sulfonic acid and a polymerizable monomer containing an acrylamide group or a methacrylic amide group is mixed with water or water. It is carried out in an aqueous solution with a sex solvent.
上記水性液を構成する水混和性溶剤としては、例えば、メタノール、エタノール、プロパノール、アセトン、アセトニトリルなどが挙げられ、これらの水混和性溶剤の水との混合割合としては、水性液全体中の５０質量％以下が好ましい。 Examples of the water-miscible solvent constituting the aqueous solution include methanol, ethanol, propanol, acetone, acetonitrile, and the like, and the mixing ratio of these water-miscible solvents with water is 50 in the entire aqueous solution. It is preferably mass% or less.
導電性高分子組成物を製造するにあたっての酸化重合は、化学酸化重合、電解酸化重合のいずれも採用することができる。 As the oxidative polymerization for producing the conductive polymer composition, either chemical oxidative polymerization or electrolytic oxidative polymerization can be adopted.
化学酸化重合を行うにあたっての酸化剤としては、例えば、過硫酸塩が用いられるが、その過硫酸塩としては、例えば、過硫酸アンモニウム、過硫酸ナトリウム、過硫酸カリウム、過硫酸カルシウム、過硫酸バリウムなどが用いられる。 For example, persulfate is used as an oxidizing agent in performing chemical oxidative polymerization, and examples of the persulfate include ammonium persulfate, sodium persulfate, potassium persulfate, calcium persulfate, barium persulfate and the like. Is used.
化学酸化重合において、その重合時の条件は、特に限定されることはないが、化学酸化重合時の温度としては、５℃〜９５℃が好ましく、１０℃〜３０℃がより好ましく、また、重合時間としては、１時間〜７２時間が好ましく、８時間〜２４時間がより好ましい。 In the chemical oxidative polymerization, the conditions at the time of the polymerization are not particularly limited, but the temperature at the time of the chemical oxidative polymerization is preferably 5 ° C. to 95 ° C., more preferably 10 ° C. to 30 ° C., and the polymerization. The time is preferably 1 hour to 72 hours, more preferably 8 hours to 24 hours.
電解酸化重合は、定電流でも定電圧でも行い得るが、例えば、定電流で電解酸化重合を行う場合、電流値としては０．０５ｍＡ／ｃｍ２〜１０ｍＡ／ｃｍ２が好ましく、０．２ｍＡ／ｃｍ２〜４ｍＡ／ｃｍ２がより好ましく、定電圧で電解酸化重合を行う場合は、電圧としては０．５Ｖ〜１０Ｖが好ましく、１．５Ｖ〜５Ｖがより好ましい。電解酸化重合時の温度としては、５℃〜９５℃が好ましく、１０℃〜３０℃がより好ましい。また、重合時間としては、１時間〜７２時間が好ましく、８時間〜２４時間がより好ましい。なお、電解酸化重合にあたっては、触媒として硫酸第一鉄または硫酸第二鉄を添加してもよい。 Electrolytic oxidation polymerization is be carried out even at a constant voltage at a constant current, for example, when performing electrolytic oxidation polymerization at a constant current, preferably 0.05mA / cm 2 ~10mA / cm 2 as the current value, 0.2 mA / cm 2 to 4 mA / cm 2 is more preferable, and when electrolytic oxidation polymerization is performed at a constant voltage, the voltage is preferably 0.5 V to 10 V, more preferably 1.5 V to 5 V. The temperature during electrolytic oxidative polymerization is preferably 5 ° C to 95 ° C, more preferably 10 ° C to 30 ° C. The polymerization time is preferably 1 hour to 72 hours, more preferably 8 hours to 24 hours. In electrolytic oxidation polymerization, ferrous sulfate or ferric sulfate may be added as a catalyst.
上記のようにして得られる導電性高分子組成物は、重合直後、水中または水性液中に分散した状態で得られ、酸化剤としての過硫酸塩や触媒として用いた硫酸鉄塩やその分解物などを含んでいる。そこで、その不純物を含んでいる導電性高分子組成物の分散液を超音波ホモジナイザー、高圧ホモジナイザー、遊星ボールミルなどの分散機にかけて不純物を分散させた後、カチオン交換樹脂で金属成分を除去することが好ましい。このときの導電性高分子組成物の粒径としては、動的光散乱法により測定した粒径で、１００μｍ以下が好ましく、特に１０μｍ以下が好ましく、１０ｎｍ以上が好ましく、特に１００ｎｍ以上が好ましい。その後、エタノール沈殿法、限外濾過法、陰イオン交換樹脂などにより、酸化剤や触媒の分解により生成したものを除去し、後述するように、必要に応じて、導電性向上剤やバインダを添加してもよい。 The conductive polymer composition obtained as described above is obtained in a state of being dispersed in water or an aqueous solution immediately after polymerization, and is a persulfate as an oxidizing agent, an iron sulfate used as a catalyst, or a decomposition product thereof. Etc. are included. Therefore, it is possible to disperse the impurities in a dispersion of the conductive polymer composition containing the impurities by using a disperser such as an ultrasonic homogenizer, a high-pressure homogenizer, or a planetary ball mill, and then remove the metal components with a cation exchange resin. preferable. The particle size of the conductive polymer composition at this time is a particle size measured by a dynamic light scattering method, preferably 100 μm or less, particularly preferably 10 μm or less, preferably 10 nm or more, and particularly preferably 100 nm or more. Then, by ethanol precipitation method, ultrafiltration method, anion exchange resin, etc., those generated by decomposition of the oxidizing agent and catalyst are removed, and as described later, a conductivity improver and a binder are added as necessary. You may.
上記の導電性高分子組成物の分散液には、沸点が１５０℃以上の高沸点有機溶剤または糖類を導電性向上剤として含有させてもよい。このように、導電性高分子組成物の分散液中に導電性向上剤を含有させておくと、該導電性高分子組成物の分散液を乾燥して得られる導電性高分子組成物の被膜などの導電性を向上させることができる。 The dispersion liquid of the above conductive polymer composition may contain a high boiling point organic solvent or saccharide having a boiling point of 150 ° C. or higher as a conductivity improver. As described above, when the conductivity improver is contained in the dispersion liquid of the conductive polymer composition, the coating film of the conductive polymer composition obtained by drying the dispersion liquid of the conductive polymer composition is obtained. It is possible to improve the conductivity such as.
これは、導電性向上剤を導電性高分子組成物の分散液に含有させておくことによって、導電性高分子組成物の分散液を乾燥して得られる導電性高分子組成物の被膜などの導電性を向上させるので、上記導電性高分子組成物を電解質として用いて製造した電解コンデンサのＥＳＲをより低くしたり、上記導電性高分子組成物を用いて製造した導電性フィルムや導電性布の表面抵抗値をより低くさせるものと考えられる。 This is because the coating of the conductive polymer composition obtained by drying the dispersion liquid of the conductive polymer composition by containing the conductivity improver in the dispersion liquid of the conductive polymer composition, etc. In order to improve the conductivity, the ESR of the electrolytic capacitor manufactured by using the conductive polymer composition as an electrolyte can be lowered, or the conductive film or the conductive cloth manufactured by using the conductive polymer composition can be lowered. It is considered that the surface resistance value of the above is lowered.
上記の導電性向上剤としては、沸点が１５０℃以上の高沸点有機溶剤または糖類が用いられるが、その沸点が１５０℃以上の高沸点有機溶剤としては、例えば、ジメチルスルホキシド、ブタンジオール、γ一ブチロラクトン、スルホラン、Ｎ−メチルピロリドン、ジメチルスルホン、エチレングリコール、ジエチレングリコール、ポリエチレングリコールなどが好ましく、また、糖類としては、例えば、エリスリトール、グルコース、マンノース、プルランなどが挙げられるが、この導電性向上剤としては、特にジメチルスルホキシドやブタンジオールが好ましい。なお、上記沸点が１５０℃以上の有機溶剤における沸点とは、常圧（つまり、１ａｔｍ＝１０１３.２５ｈＰａ）下での沸点をいう。 As the above-mentioned conductivity improver, a high-boiling organic solvent or saccharide having a boiling point of 150 ° C. or higher is used, and examples of the high-boiling organic solvent having a boiling point of 150 ° C. or higher include dimethyl sulfoxide, butanediol, and γ-1. Butyrolactone, sulfolane, N-methylpyrrolidone, dimethyl sulfoxide, ethylene glycol, diethylene glycol, polyethylene glycol and the like are preferable, and examples of the saccharide include erythritol, glucose, mannose and purulan, and examples of the saccharide include erythritol, glucose, mannose and purulan. Is particularly preferably dimethyl sulfoxide or butanediol. The boiling point of an organic solvent having a boiling point of 150 ° C. or higher means a boiling point under normal pressure (that is, 1 atm = 1013.25 hPa).
このような導電性向上剤の添加量としては、分散液中の導電性高分子組成物に対して質量基準で５〜３，０００％（すなわち、導電性高分子組成物１００質量部に対して導電性向上剤が５〜３，０００質量部）が好ましく、特に２０〜７００％が好ましい。導電性向上剤の添加量が上記より少ない場合は、導電性を向上させる作用が充分に発揮されなくなるおそれがあり、導電性向上剤の添加量が上記より多い場合は、分散液の乾燥に時間を要するようになり、また、かえって、導電性の低下を引き起こすおそれがある。 The amount of such a conductivity improver added is 5 to 3,000% by mass with respect to the conductive polymer composition in the dispersion liquid (that is, with respect to 100 parts by mass of the conductive polymer composition). The conductivity improver is preferably 5 to 3,000 parts by mass), and particularly preferably 20 to 700%. If the amount of the conductivity improver added is less than the above, the effect of improving the conductivity may not be sufficiently exhibited, and if the amount of the conductivity improver added is more than the above, it takes time to dry the dispersion. On the contrary, there is a risk of causing a decrease in conductivity.
分散液中における導電性高分子組成物の含有量は、電解コンデンサや導電性フィルムなどの製造時における作業性に影響を与えるので、通常、０．５〜１５質量％程度が好ましい。つまり、導電性高分子組成物の含有量が上記より少ない場合は、乾燥に時間を要するようになるおそれがあり、また、導電性高分子組成物の含有量が上記より多い場合は、分散液の粘度が高くなって、電解コンデンサや導電性フィルムなどの製造にあたっての作業性が低下するおそれがある。 Since the content of the conductive polymer composition in the dispersion liquid affects the workability at the time of manufacturing the electrolytic capacitor, the conductive film and the like, it is usually preferably about 0.5 to 15% by mass. That is, if the content of the conductive polymer composition is lower than the above, it may take time to dry, and if the content of the conductive polymer composition is higher than the above, the dispersion liquid may be required. There is a risk that the viscosity of the product will increase and workability in manufacturing electrolytic capacitors, conductive films, etc. will decrease.
また、導電性高分子組成物の分散液にバインダを添加しておくと、特に導電性フィルムや導電性布などの製造にあたって、基材や基布に対する導電性高分子組成物の親和性（なじみ性）や密着性を向上させることができるので好ましい。 Further, if a binder is added to the dispersion liquid of the conductive polymer composition, the affinity (familiarity) of the conductive polymer composition with the base material and the base cloth is particularly high in the production of the conductive film and the conductive cloth. It is preferable because it can improve the property) and adhesion.
上記バインダとしては、例えば、ポリビニルアルコール、ポリウレタン、ポリエステル、アクリル樹脂、ポリアミド、ポリイミド、エポキシ樹脂、ポリアクリロニトリル樹脂、ポリメタクリロニトリル樹脂、ポリスチレン樹脂、ノボラック樹脂、スルホン化ポリエステル、スルホン化ポリアリル、スルホン化ポリビニル、スルホン化ポリスチレン、シランカップリング剤などが挙げられ、ポリエステル、ポリウレタン、アクリル樹脂、スルホン化ポリエステル、スルホン化ポリアリル、スルホン化ポリビニル、スルホン化ポリスチレンなどが好ましい。 Examples of the binder include polyvinyl alcohol, polyurethane, polyester, acrylic resin, polyamide, polyimide, epoxy resin, polyacrylonitrile resin, polymethacrylonitrile resin, polystyrene resin, novolak resin, sulfonated polyester, sulfonated polyallyl, and sulfonated. Examples thereof include polyvinyl, sulfonated polystyrene, and silane coupling agents, and polyester, polyurethane, acrylic resin, sulfonated polyester, sulfonated polyallyl, sulfonated polyvinyl, sulfonated polystyrene and the like are preferable.
上記のように、導電性高分子組成物の分散液にバインダを添加し、それを乾燥した場合、バインダも導電性高分子組成物中に含まれることになるが、導電性フィルムや導電性布などを製造した際に、その導電性は導電性高分子組成物に基づいて発現し、バインダは補助的なものにすぎないので、本書においては、用途上における要求特性の関係から、上記のように導電性高分子組成物の分散液に添加したバインダに基づいてバインダを含むようになった導電性高分子組成物もバインダを含まない導電性高分子組成物も厳密に区別することなく、同じ導電性高分子組成物という表現で取り扱っている。 As described above, when the binder is added to the dispersion liquid of the conductive polymer composition and dried, the binder is also contained in the conductive polymer composition, but the conductive film or the conductive cloth When the above is manufactured, its conductivity is developed based on the conductive polymer composition, and the binder is only an auxiliary one. The conductive polymer composition that now contains a binder based on the binder added to the dispersion of the conductive polymer composition and the conductive polymer composition that does not contain a binder are the same without strict distinction. It is treated as a conductive polymer composition.
本願に第２の発明においては、ドーパントとして、前記のように、(I)で示した上記スチレンスルホン酸と、アクリルアミド基またはメタクリルアミド基を含む重合性モノマーとの共重合体と、(II)で示したポリスチレンスルホン酸とを併用するが、このポリスチレンスルホン酸としては、重量平均分子量が１０，０００〜１，０００，０００のものが好ましい。 In the second invention of the present application, as the dopant, as described above, a copolymer of the above-mentioned styrene sulfonic acid shown in (I) and a polymerizable monomer containing an acrylamide group or a methacrylamide group, and (II). Although the polystyrene sulfonic acid shown in the above is used in combination, the polystyrene sulfonic acid preferably has a weight average molecular weight of 10,000 to 1,000,000.
すなわち、上記ポリスチレンスルホン酸の重量平均分子量が１０，０００より小さい場合は、得られる導電性高分子組成物の導電性が低くなるおそれがある。また、上記ポリスチレンスルホン酸の重量平均分子量が１，０００，０００より大きい場合は、導電性高分子組成物の分散液の粘度が高くなり、使用しにくくなるおそれがある。そして、上記ポリスチレンスルホン酸としては、その重量平均分子量が上記範囲内で、２０，０００以上のものが好ましく、４０，０００以上のものがより好ましく、また、８００，０００以下のものが好ましく、３００，０００以下のものがより好ましい。 That is, when the weight average molecular weight of the polystyrene sulfonic acid is less than 10,000, the conductivity of the obtained conductive polymer composition may be lowered. Further, when the weight average molecular weight of the polystyrene sulfonic acid is larger than 1,000,000, the viscosity of the dispersion liquid of the conductive polymer composition becomes high, which may make it difficult to use. The polystyrene sulfonic acid having a weight average molecular weight within the above range is preferably 20,000 or more, more preferably 40,000 or more, and preferably 800,000 or less, 300. Those of 000 or less are more preferable.
上記のように、ドーパントとして、スチレンスルホン酸と、アクリルアミド基またはメタクリルアミド基を含む重合性モノマーとの共重合体と、ポリスチレンスルホン酸とを併用することによって、上記共重合体の奏する特性に加えて、導電性高分子組成物の導電性をさらに向上させることができるが、それらの併用にあたって、上記共重合体と、ポリスチレンスルホン酸との比率としては、質量比１：０．０１〜１：１が好ましい。 As described above, by using a copolymer of styrene sulfonic acid, a polymerizable monomer containing an acrylamide group or a methacrylamide group, and polystyrene sulfonic acid in combination as a dopant, in addition to the characteristics exhibited by the copolymer. Therefore, the conductivity of the conductive polymer composition can be further improved, but when they are used in combination, the ratio of the above-mentioned copolymer to polystyrene sulfonic acid is a mass ratio of 1: 0.01 to 1: 1. 1 is preferable.
そして、このスチレンスルホン酸とアクリルアミド基またはメタクリルアミド基を含む重合性モノマーとの共重合体と、ポリスチレンスルホン酸とを併用する場合も、それらの使用量は、両者の合計でチオフェンおよびその誘導体よりなる群から選ばれる少なくとも１種に対して、質量比で１：０．０１〜１：２０であることが好ましく、１：０．０１〜１：２であることがより好ましい。 When polystyrene sulfonic acid is used in combination with a copolymer of styrene sulfonic acid and a polymerizable monomer containing an acrylamide group or a methacrylic amide group, the total amount of both used is higher than that of thiophene and its derivatives. The mass ratio is preferably 1: 0.01 to 1:20, and more preferably 1: 0.01 to 1: 2 with respect to at least one selected from the group.
上記のように、(I)で示したスチレンスルホン酸と、アクリルアミド基またはメタクリルアミド基を含む重合性モノマーとの共重合体と(II)で示したポリスチレンスルホン酸と存在下で、チオフェンおよびその誘導体よりなる群から選ばれる少なくとも１種を酸化重合して導電性高分子組成物を製造する場合も、前記の第１の発明の場合、すなわち、スチレンスルホン酸と、アクリルアミド基またはメタクリルアミド基を含む重合性モノマーとの共重合体の存在下で、チオフェンおよびその誘導体よりなる群から選ばれる少なくとも１種を酸化重合する場合と同様に、水中または水性液中で行われ、同様に、化学酸化重合、電解酸化重合のいずれも採用でき、それらの重合時の条件も上記共重合体を用いてチオフェンおよびその誘導体よりなる群から選ばれる少なくとも１種を酸化重合する場合と同様の条件を採用することができえる。 As described above, in the presence of a copolymer of the styrene sulfonic acid shown in (I) and a polymerizable monomer containing an acrylamide group or a methacrylicamide group and the polystyrene sulfonic acid shown in (II), thiophene and its thereof. Also in the case of producing a conductive polymer composition by oxidatively polymerizing at least one selected from the group consisting of derivatives, the case of the first invention described above, that is, styrene sulfonic acid and an acrylamide group or a methacrylic group. It is carried out in water or an aqueous solution in the same manner as in the case of oxidatively polymerizing at least one selected from the group consisting of thiophene and its derivatives in the presence of a copolymer with a polymerizable monomer containing thiophene, and similarly, chemical oxidation. Both polymerization and electrolytic oxidation polymerization can be adopted, and the conditions at the time of polymerization are the same as in the case of oxidative polymerization of at least one selected from the group consisting of thiophene and its derivatives using the above-mentioned copolymer. Can be done.
そして、前記第１の発明の場合と同様に、得られた導電性高分子組成物の分散液に導電性向上剤やバインダを添加することも好適に採用される。 Then, as in the case of the first invention, it is also suitably adopted to add a conductivity improver or a binder to the dispersion liquid of the obtained conductive polymer composition.
本願の第３の発明の導電性高分子組成物は、下記(I)と(II)と(III)
（I）：スチレンスルホン酸と、アクリルアミド基またはメタクリルアミド基を含む重合性モノマーとの共重合体
（II）：ポリスチレンスルホン酸
（III）：スルホン化ポリエステルおよびフェノールスルホン酸ノボラック樹脂よりなる群から選ばれる少なくとも１種のポリマーアニオン
との存在下で、チオフェンおよびその誘導体よりなる群から選ばれる少なくとも１種を水中または水と水混和性溶剤との混合物からなる水性液中で酸化重合することにより得られる導電性高分子の分散液を乾燥することによって製造される。そして、本願の第４の導電性高分子組成物は、上記(I)をドーパントとして用いて得られた導電性高分子組成物の分散液と、上記(III)をドーパントとして用いて得られた導電性高分子組成物の分散液とを混合し、本願の第５の導電性高分子組成物は、上記(I)と (II)とをドーパントとして用いて得られた導電性高分子組成物の分散液と、上記(III)をドーパントとして用いて得られた導電性高分子の分散液とを混合し、得られた混合系の導電性高分子組成物の分散液を乾燥することによって製造される。
The conductive polymer composition of the third invention of the present application is described in (I), (II) and (III) below.
(I): Copolymer of styrene sulfonic acid and polymerizable monomer containing acrylamide group or methacrylic amide group (II): Polystyrene sulfonic acid (III): Selected from the group consisting of sulfonated polyester and novolak phenol sulfonic acid. Obtained by oxidatively polymerizing at least one selected from the group consisting of thiophene and its derivatives in water or an aqueous solution consisting of a mixture of water and a water-miscible solvent in the presence of at least one polymer anion. It is produced by drying a dispersion of a conductive polymer. The fourth conductive polymer composition of the present application was obtained by using the dispersion liquid of the conductive polymer composition obtained by using the above (I) as a dopant and the above (III) as a dopant. The fifth conductive polymer composition of the present application is obtained by mixing the dispersion liquid of the conductive polymer composition and using the above (I) and (II) as dopants. Is produced by mixing the dispersion liquid of the above (III) with the dispersion liquid of the conductive polymer obtained by using the above (III) as a dopant, and drying the dispersion liquid of the obtained mixed system conductive polymer composition. Will be done.
そこで、上記(III)のスルホン化ポリエステルとフェノールスルホン酸ノボラック樹脂について説明すると、まず、上記スルホン化ポリエステルは、スルホイソフタル酸エステルやスルホテレフタル酸エステルなどのジカルボキシベンゼンスルホン酸ジエステルとアルキレングリコールとを酸化アンチモンや酸化亜鉛などの触媒の存在下で縮重合させたものであり、このスルホン化ポリエステルとしては、その重量平均分子量が５，０００〜３００，０００のものが好ましい。 Therefore, the sulfonated polyester and the phenol sulfonic acid novolak resin of the above (III) will be described. First, the sulfonated polyester is composed of a dicarboxybenzene sulfonic acid diester such as a sulfoisophthalic acid ester or a sulfoterephthalic acid ester and an alkylene glycol. It is condensed and polymerized in the presence of a catalyst such as antimony oxide or zinc oxide, and the sulfonated polyester preferably has a weight average molecular weight of 5,000 to 300,000.
すなわち、スルホン化ポリエステルの重量平均分子量が５，０００より小さい場合は、得られる導電性高分子組成物の導電性が低くなるおそれがある。また、スルホン化ポリエステルの重量平均分子量が３００，０００より大きい場合は、導電性高分子組成物の分散液の粘度が高くなり、導電性フィルムなどの作製にあたって使用しにくくなるおそれがある。そして、このスルホン化ポリエステルとしては、その重量平均分子量が上記範囲内で、１０，０００以上のものが好ましく、２０，０００以上のものがより好ましく、また、１００，０００以下のものが好ましく、８０，０００以下のものがより好ましい。 That is, when the weight average molecular weight of the sulfonated polyester is less than 5,000, the conductivity of the obtained conductive polymer composition may be lowered. Further, when the weight average molecular weight of the sulfonated polyester is larger than 300,000, the viscosity of the dispersion liquid of the conductive polymer composition becomes high, which may make it difficult to use in producing a conductive film or the like. The sulfonated polyester having a weight average molecular weight within the above range is preferably 10,000 or more, more preferably 20,000 or more, and preferably 100,000 or less, 80. Those of 000 or less are more preferable.
また、上記フェノールスルホン酸ノボラック樹脂としては、例えば、次の一般式（２）
で表される繰り返し単位を有するものが好ましく、このようなフェノールスルホン酸ノボラック樹脂としては、その重量平均分子量が５，０００〜５００，０００のものが好ましい。
Further, as the above-mentioned phenol sulfonic acid novolak resin, for example, the following general formula (2)
Those having a repeating unit represented by (1) are preferable, and as such a phenol sulfonic acid novolak resin, those having a weight average molecular weight of 5,000 to 500,000 are preferable.
すなわち、上記フェノールスルホン酸ノボラック樹脂の重量平均分子量が５，０００より小さい場合は、得られる導電性高分子組成物の導電性が低くなるおそれがある。また、上記フェノールスルホン酸ノボラック樹脂の重量平均分子量が５００，０００より大きい場合は、導電性高分子組成物の分散液の粘度が高くなり、電解コンデンサの作製にあたって使用しにくくなるおそれがある。そして、このフェノールスルホン酸ノボラック樹脂としては、その重量平均分子量が上記範囲内で、１０，０００以上のものがより好ましく、また、４００，０００以下のものが好ましく、８０，０００以下のものがより好ましい。 That is, when the weight average molecular weight of the phenol sulfonic acid novolak resin is less than 5,000, the conductivity of the obtained conductive polymer composition may be lowered. Further, when the weight average molecular weight of the phenol sulfonic acid novolak resin is larger than 500,000, the viscosity of the dispersion liquid of the conductive polymer composition becomes high, which may make it difficult to use in manufacturing an electrolytic capacitor. The phenol sulfonic acid novolak resin having a weight average molecular weight within the above range is more preferably 10,000 or more, preferably 400,000 or less, and more preferably 80,000 or less. preferable.
そして、上記スルホン化ポリエステルおよびフェノールスルホン酸ノボラック樹脂よりなる群から選ばれる少なくとも１種のポリマーアニオンを用いてのチオフェンおよびその誘導体よりなる群から選ばれる少なくとも１種の酸化重合は、前記第１の発明における共重合体をドーパントとして用いての酸化重合と同様に、水中または水と水混和性溶剤との混合物からなる水性液中で行われ、同様に、化学酸化重合、電解酸化重合のいずれも採用でき、それらの重合時の条件も、前記第１の発明における共重合体をドーパントとして用いてチオフェンおよびその誘導体よりなる群から選ばれる少なくとも１種を酸化重合する場合と同様の条件を採用することができる。 Then, at least one oxidative polymerization selected from the group consisting of thiophene and its derivatives using at least one polymer anion selected from the group consisting of the sulfonated polyester and the phenol sulfonate novolak resin is the first type of oxidative polymerization. Similar to the oxidative polymerization using the copolymer in the present invention as a dopant, the oxidative polymerization is carried out in water or in an aqueous solution consisting of a mixture of water and a water-miscible solvent. Similarly, both chemical oxidative polymerization and electrolytic oxidative polymerization are carried out. It can be adopted, and the conditions at the time of polymerization thereof are the same as those in the case where at least one selected from the group consisting of thiophene and its derivatives is oxidatively polymerized using the copolymer in the first invention as a dopant. be able to.
そして、前記第１の発明の場合と同様に、得られた導電性高分子組成物の分散液に導電性向上剤やバインダを添加することも好適に採用することができる。 Then, as in the case of the first invention, it is also possible to preferably add a conductivity improver or a binder to the dispersion liquid of the obtained conductive polymer composition.
本願の第３の導電性高分子組成物の製造にあたっては、前記のように、(I)で示した「スチレンスルホン酸と、アクリルアミド基またはメタクリルアミド基を含む重合性モノマーとの共重合体」と、(II)で示した「ポリスチレンスルホン酸」と、(III)で示した「スルホン化ポリエステルおよびフェノールスルホン酸ノボラック樹脂よりなる群から選ばれる少なくとも１種のポリマーアニオン」との存在下で、チオフェンおよびその誘導体よりなる群から選ばれる少なくとも１種を酸化重合するが、その場合、それら(I)と(II)と(III)との使用割合としては、(I)が５〜６０質量％、(II)が１０〜４０質量％、(III)が１０〜７０質量％が好ましい。 In the production of the third conductive polymer composition of the present application, as described above, "a copolymer of styrene sulfonic acid and a polymerizable monomer containing an acrylamide group or a methacrylic amide group" shown in (I). In the presence of "polystyrene sulfonic acid" shown in (II) and "at least one polymer anion selected from the group consisting of sulfonated polyester and novolak phenol sulfonic acid resin" shown in (III). At least one selected from the group consisting of thiophene and its derivatives is oxidatively polymerized. In that case, (I) is 5 to 60% by mass as the usage ratio of (I), (II) and (III). , (II) is preferably 10 to 40% by mass, and (III) is preferably 10 to 70% by mass.
本願の第３の発明と、第５の発明の場合とは、基本的に同じ導電性高分子組成物が得られるが、第５の発明のように、(I)と(II)とをドーパントとして導電性高分子組成物を得る工程と、(III)をドーパントとして導電性高分子組成物を得る工程とを分けて行う方が、第３の発明の場合より、多少、特性の良い導電性高分子組成物が得られる可能性がある。 In the case of the third invention and the fifth invention of the present application, basically the same conductive polymer composition can be obtained, but as in the fifth invention, (I) and (II) are doped. It is better to separate the step of obtaining the conductive polymer composition using (III) as a dopant and the step of obtaining the conductive polymer composition using (III) as a dopant, as compared with the case of the third invention. Polymer compositions may be obtained.
次に、上記の導電性高分子組成物を電解質として用いて電解コンデンサを製造する例を説明する。上記導電性高分子組成物は、そのまま、つまり、固体状で電解コンデンサの製造に当って用いることができるが、水または水性液への分散液として用いる方が電解コンデンサの製造にあたっては適している。この導電性高分子組成物の分散液は、導電性高分子組成物を水または水性液に分散させてもよいが、導電性高分子組成物の製造が水中または水性液中で行われ、分散液の状態で得られるので、その導電性高分子組成物の分散液をそのまま用いればよい。 Next, an example of manufacturing an electrolytic capacitor using the above conductive polymer composition as an electrolyte will be described. The above-mentioned conductive polymer composition can be used as it is, that is, in a solid state in the production of an electrolytic capacitor, but it is more suitable in the production of an electrolytic capacitor to be used as a dispersion liquid in water or an aqueous liquid. .. In the dispersion liquid of the conductive polymer composition, the conductive polymer composition may be dispersed in water or an aqueous liquid, but the conductive polymer composition is produced in water or an aqueous liquid and dispersed. Since it is obtained in the form of a liquid, the dispersion liquid of the conductive polymer composition may be used as it is.
まず、上記の導電性高分子組成物の分散液をタンタル電解コンデンサ、ニオブ電解コンデンサ、積層型アルミニウム電解コンデンサなどの製造にあたって用いる場合、例えば、タンタル、ニオブ、アルミニウムから選択される弁金属の多孔体からなる陽極と、それらの弁金属の酸化被膜からなる誘電体層を有するコンデンサ素子を、上記導電性高分子組成物の分散液に浸漬し、取り出した後、乾燥して、導電性高分子組成物からなる電解質の層を形成するか、または、必要に応じて、上記の分散液への浸漬と乾燥する工程を繰り返すことによって、導電性高分子組成物からなる電解質の層を形成した後、カーボンペースト、銀ペーストを塗布し、乾燥した後、外装することによって、タンタル電解コンデンサ、ニオブ電解コンデンサ、積層型アルミニウム電解コンデンサなどを製造することができる。 First, when the dispersion liquid of the above conductive polymer composition is used in the production of a tantalum electrolytic capacitor, a niobical electrolytic capacitor, a laminated aluminum electrolytic capacitor, or the like, for example, a porous valve metal selected from tantalum, niobium, and aluminum. A capacitor element having an anode composed of an anode and a dielectric layer composed of an oxide film of a valve metal thereof is immersed in a dispersion liquid of the above conductive polymer composition, taken out, and then dried to form a conductive polymer composition. After forming the electrolyte layer made of the conductive polymer composition, or by repeating the steps of dipping in the dispersion liquid and drying as necessary, the electrolyte layer made of the conductive polymer composition is formed. By applying carbon paste or silver paste, drying it, and then exteriorizing it, a tantalum electrolytic capacitor, a niobular electrolytic capacitor, a laminated aluminum electrolytic capacitor, or the like can be manufactured.
また、非鉄塩系の有機スルホン酸塩をドーパントとして用い、重合性モノマー、酸化剤を含む液に、上記のコンデンサ素子を浸漬し、取り出した後、乾燥して重合を行い、その後、水に浸漬し、取り出し、洗浄した後、乾燥することによって、いわゆる「その場重合」で導電性高分子組成物を製造した後、それら全体を上記の導電性高分子組成物の分散液に浸漬し、取り出して乾燥する操作を繰り返して上記の導電性高分子組成物からなる電解質の層を形成してもよく、また、その逆の形態にしてもよい。 Further, using a non-iron salt-based organic sulfonate as a dopant, the above-mentioned condenser element is immersed in a liquid containing a polymerizable monomer and an oxidizing agent, taken out, dried and polymerized, and then immersed in water. Then, the conductive polymer compositions are produced by so-called "in-situ polymerization" by taking out, washing, and then drying, and then the whole of them is immersed in the dispersion liquid of the above conductive polymer composition and taken out. The operation of drying and drying may be repeated to form an electrolyte layer made of the above-mentioned conductive polymer composition, or vice versa.
そして、そのようにして導電性高分子組成物で覆われたコンデンサ素子をカーボンペースト、銀ペーストで覆った後、外装することによって、タンタル電解コンデンサ、ニオブ電解コンデンサ、積層型アルミニウム電解コンデンサなどを製造することもできる。 Then, the capacitor element covered with the conductive polymer composition is covered with carbon paste and silver paste, and then the exterior is used to manufacture a tantalum electrolytic capacitor, a niobium electrolytic capacitor, a laminated aluminum electrolytic capacitor, and the like. You can also do it.
また、上記の導電性高分子組成物の分散液を巻回型アルミニウム電解コンデンサの製造にあたって用いる場合、例えば、アルミニウム箔の表面をエッチング処理した後、化成処理を行って誘電体層を形成した陽極にリード端子を取り付け、また、アルミニウム箔からなる陰極にリード端子を取り付け、それらのリード端子付き陽極と陰極とをセパレータを介して巻回して作製したコンデンサ素子を上記の導電性高分子組成物の分散液に浸漬し、取り出した後、乾燥して、導電性高分子組成物からなる電解質の層を形成するか、または、必要に応じて、上記の分散液への浸漬と乾燥する工程を繰り返すことによって、導電性高分子組成物からなる電解質の層を形成した後、外装材で外装して、巻回型アルミニウム電解コンデンサを製造することができる。 Further, when the dispersion liquid of the above conductive polymer composition is used in the production of a wound type aluminum electrolytic capacitor, for example, an anode having a dielectric layer formed by etching the surface of an aluminum foil and then performing a chemical conversion treatment. A capacitor element produced by attaching a lead terminal to a cathode made of aluminum foil, attaching the lead terminal to the anode, and winding the anode and the anode with the lead terminal via a separator is formed by the above-mentioned conductive polymer composition. Immerse in the dispersion, take out, and then dry to form an electrolyte layer made of the conductive polymer composition, or, if necessary, repeat the steps of dipping in the dispersion and drying. This makes it possible to manufacture a wound aluminum electrolytic capacitor by forming an electrolyte layer made of a conductive polymer composition and then exteriorizing it with an exterior material.
本発明の電解コンデンサの製造にあたっては、上記のように導電性高分子組成物のみを電解質とする以外に、上記導電性高分子組成物からなる電解質と電解液とを併用することができる。 In the production of the electrolytic capacitor of the present invention, in addition to using only the conductive polymer composition as an electrolyte as described above, an electrolyte composed of the conductive polymer composition and an electrolytic solution can be used in combination.
上記電解液としては、特に特定のものに限られることなく、例えば、１０質量％アジピン酸トリメチルアミンのエチレングリコール溶液（アジピン酸トリメチルアミンが１０質量％溶解しているエチレングリコール溶液）などの従来から電解コンデンサの電解液として用いられているものをはじめ、各種のものを用いることができる。 The electrolytic solution is not particularly limited, and is a conventional electrolytic capacitor such as, for example, an ethylene glycol solution of 10% by mass of trimethylamine adipate (an ethylene glycol solution in which 10% by mass of trimethylamine adipate is dissolved). Various types can be used, including those used as the electrolytic solution of.
そして、この電解液を導電性高分子組成物からなる電解質と併用して電解コンデンサを製造するときは、通常、コンデンサ素子に導電性高分子組成物からなる電解質層を形成した後、その導電性高分子組成物からなる電解質層を形成したコンデンサ素子を電解液に浸漬するか、あるいは電解液を上記電解質層を有するコンデンサ素子にスプレーなどで塗布する工程を経ることによって電解コンデンサが製造される。 When an electrolytic capacitor is manufactured by using this electrolytic solution in combination with an electrolyte made of a conductive polymer composition, usually, after forming an electrolyte layer made of the conductive polymer composition on the capacitor element, the conductivity thereof. An electrolytic capacitor is manufactured by immersing a capacitor element having an electrolyte layer made of a polymer composition in an electrolytic solution, or by applying the electrolytic solution to the capacitor element having an electrolyte layer by spraying or the like.
前記のように、本発明の導電性高分子組成物は、高い導電性と優れた耐熱性、耐湿熱性を有している上に、透明性も高いので、電解コンデンサの電解質として用いる以外に、透明導電性フィルムや導電性布などの製造にあたって用いることができる。 As described above, the conductive polymer composition of the present invention has high conductivity, excellent heat resistance, and moisture heat resistance, and also has high transparency. Therefore, in addition to being used as an electrolyte for an electrolytic capacitor, It can be used in the production of transparent conductive films, conductive cloths, and the like.
例えば、本発明の導電性高分子組成物で導電性フィルムを製造するには、シート状の基材に前記の導電性高分子組成物の分散液を塗布するか、基材を導電性高分子組成物の分散液に浸漬し、取り出した後、乾燥して、導電性フィルムを形成し、その導電性フィルムを基材から剥離すればよい。 For example, in order to produce a conductive film from the conductive polymer composition of the present invention, the dispersion liquid of the conductive polymer composition is applied to a sheet-shaped base material, or the base material is made of a conductive polymer. The composition may be immersed in a dispersion liquid, taken out, and then dried to form a conductive film, and the conductive film may be peeled off from the substrate.
本発明の導電性高分子組成物を用いて導電性フィルムを製造するには、上記のように、シート状の基材に前記の導電性高分子組成物の分散液を塗布するか、基材を導電性高分子組成物の分散液に浸漬し、取り出した後、乾燥して、導電性フィルムを形成し、そのフィルムを基材から剥離すればよいが、むしろ、基材の一方の面または両面に形成した導電性フィルムを基材から剥がさずに、基材を支持材とした導電性シートとして使用に供する方が適している場合がある。 In order to produce a conductive film using the conductive polymer composition of the present invention, as described above, the dispersion liquid of the conductive polymer composition is applied to the sheet-shaped base material, or the base material is used. Is immersed in a dispersion liquid of a conductive polymer composition, taken out, and then dried to form a conductive film, and the film may be peeled off from the base material, but rather, one surface of the base material or In some cases, it is more suitable to use the conductive film formed on both sides as a conductive sheet with the base material as a support material without peeling it off from the base material.
上記のような導電性フィルムや導電性布の製造にあたって、導電性高分子組成物の分散液に前記のようなバインダが添加されていると、基材や基布に対する導電性高分子組成物の密着性や親和性（なじみ性）を向上させることができるので好ましい。 In the production of the above-mentioned conductive film or conductive cloth, if the above-mentioned binder is added to the dispersion liquid of the conductive polymer composition, the conductive polymer composition with respect to the base material or the base cloth is added. It is preferable because it can improve adhesion and affinity (familiarity).
また、本発明の導電性高分子組成物を用いて導電性フィルムや導電性布を製造する際、導電性金属材料の一種である金属ナノワイヤーと併用することも可能である。 Further, when producing a conductive film or a conductive cloth using the conductive polymer composition of the present invention, it can be used in combination with a metal nanowire which is a kind of conductive metal material.
併用の態様としては、導電性フィルムの場合、例えば、導電性高分子組成物と金属ナノワイヤーとを混合して複合導電性組成物とし、その複合導電性組成物で導電性フィルムを構成するか、または基材上に金属ナノワイヤーによるフィルムを形成し、その金属ナノワイヤーフィルム上に本発明の導電性高分子組成物を積層して導電性積層フィルムとする態様が採用できる。 In the case of a conductive film, for example, a conductive polymer composition and a metal nanowire are mixed to form a composite conductive composition, and the composite conductive composition constitutes the conductive film. Alternatively, an embodiment in which a film made of metal nanowires is formed on a base material and the conductive polymer composition of the present invention is laminated on the metal nanowire film to form a conductive laminated film can be adopted.
金属ナノワイヤーとしては、例えば、銀ナノワイヤー、金ナノワイヤー、銅ナノワイヤーなどを用いることができ、特に銀ナノワイヤーが好ましい。 As the metal nanowires, for example, silver nanowires, gold nanowires, copper nanowires and the like can be used, and silver nanowires are particularly preferable.
上記のような複合導電性組成物とするには、例えば、本発明の導電性高分子組成物の分散液に金属ナノワイヤーを混合して導電性高分子組成物と金属ナノワイヤーとを含む分散液にし、それを乾燥すればよい。また、金属ナノワイヤーに関しても、分散液としたものが市販されているので、それを利用すればよい。 In order to obtain the above-mentioned composite conductive composition, for example, a metal nanowire is mixed with the dispersion liquid of the conductive polymer composition of the present invention to disperse the conductive polymer composition and the metal nanowire. Just make it into a liquid and dry it. Further, as for the metal nanowire, a dispersion liquid is commercially available, and it may be used.
上記のような複合導電性組成物とする場合の導電性高分子組成物と金属ナノワイヤーとの比率は、金属ナノワイヤーに基づく高い導電性を低下させすぎない範囲が好ましく、質量比で０．０１：１〜１０：１が好ましく、０．１：１〜５：１がより好ましい。 The ratio of the conductive polymer composition to the metal nanowires in the case of forming the composite conductive composition as described above is preferably in a range that does not excessively reduce the high conductivity based on the metal nanowires, and has a mass ratio of 0. 01: 1 to 10: 1 is preferable, and 0.1: 1 to 5: 1 is more preferable.
上記のような複合導電性組成物のフィルム化は、例えば、ポリエステルシートなどのシート状の基材に、複合導電性組成物を含む分散液を塗布し、乾燥することによって行うのが好ましい。 The film formation of the composite conductive composition as described above is preferably carried out by applying a dispersion liquid containing the composite conductive composition to a sheet-like base material such as a polyester sheet and drying it.
上記の複合導電性組成物からなる導電性フィルムは、導電性高分子組成物の高い導電性に加えて、金属ナノワイヤーの有するさらに高い導電性が付加されているので、導電性高分子組成物のみで構成される導電性フィルムより導電性が高く、したがって、表面抵抗値がより低いという特性を有している。 The conductive film made of the above-mentioned composite conductive composition has, in addition to the high conductivity of the conductive polymer composition, the higher conductivity of the metal nanowires, so that the conductive polymer composition It has the property of being more conductive than a conductive film composed of only and therefore having a lower surface resistance value.
上記のような複合導電性組成物とする場合、本発明の導電性高分子組成物は、導電性が高いことから、従来の導電性高分子組成物を用いていた場合に比べて、導電性がより高い複合導電性組成物が得られる。 In the case of the composite conductive composition as described above, since the conductive polymer composition of the present invention has high conductivity, it is more conductive than the case where the conventional conductive polymer composition is used. A higher composite conductive composition is obtained.
また、基材上に形成した金属ナノワイヤーフィルム上に本発明の導電性高分子組成物を積層する導電性積層フィルムの製造にあたり、その金属ナノワイヤーフィルムの形成にあたっては、金属ナノワイヤーの分散液を使用することができる。すなわち、基材上に金属ナノワイヤーの分散液を塗布し、乾燥することによって、金属ナノワイヤーフィルムを形成することができる。 Further, in the production of a conductive laminated film in which the conductive polymer composition of the present invention is laminated on a metal nanowire film formed on a base material, in forming the metal nanowire film, a dispersion liquid of metal nanowires is produced. Can be used. That is, a metal nanowire film can be formed by applying a dispersion liquid of metal nanowires on a base material and drying it.
このようにして得られる導電性積層フィルムの場合も、本発明の導電性高分子組成物の導電性が高いことから、金属ナノワイヤーの有する高い導電性を大きく低下させることがないので、導電性が高く、かつフレキシブルなフィルムとすることができる。そして、このようにして製造される本発明の導電性積層フィルムは、その導電性が高く、かつフレキシブルであるという特性を生かして、タッチセンサーやタッチパネルなどに使用される透明電極フィルムなどとして好適に使用することができ、そのような透明電極フィルムにおいて、従来からのものに対して、より低抵抗なものにすることができる。 Even in the case of the conductive laminated film thus obtained, since the conductive polymer composition of the present invention has high conductivity, the high conductivity of the metal nanowire is not significantly reduced, so that the conductivity is conductive. It can be a high-quality and flexible film. The conductive laminated film of the present invention produced in this manner is suitable as a transparent electrode film used for a touch sensor, a touch panel, or the like, taking advantage of its high conductivity and flexibility. It can be used, and in such a transparent electrode film, the resistance can be made lower than that of the conventional one.
本発明の導電性高分子組成物や複合導電性組成物を用いて、導電性布を製造する場合、その基布としては、例えば、織布、不織布、マイクロファイバーなどが用いられる。そして、その導電性布の製造にあたっては、例えば、上記の基布に導電性高分子組成物の分散液または複合導電性組成物の分散液を含浸させ、それを乾燥することによって行われる。そのように得られる導電性布においては、導電性高分子組成物や複合導電性組成物は基布に保持されることになる。そして、そのようにして得られる導電性布は、本発明の導電性高分子組成物や複合導電性組成物の有する高い導電性と優れた耐熱性、耐湿熱性に基づき、導電性が高く、耐熱性、耐湿熱性が優れている。そして、上記導電性布は、そのような特性を生かして、例えば、生体認証用の電極などとして有効に使用することができる。 When a conductive cloth is produced using the conductive polymer composition or the composite conductive composition of the present invention, for example, a woven cloth, a non-woven fabric, a microfiber or the like is used as the base cloth. Then, the production of the conductive cloth is carried out, for example, by impregnating the above-mentioned base cloth with a dispersion liquid of a conductive polymer composition or a dispersion liquid of a composite conductive composition and drying it. In the conductive cloth thus obtained, the conductive polymer composition and the composite conductive composition are held by the base cloth. The conductive cloth thus obtained has high conductivity and heat resistance based on the high conductivity, excellent heat resistance, and moisture heat resistance of the conductive polymer composition and composite conductive composition of the present invention. Has excellent properties and moisture and heat resistance. The conductive cloth can be effectively used as, for example, an electrode for biometric authentication by taking advantage of such characteristics.
次に実施例を挙げて本発明をより具体的に説明するが、本発明はそれらの実施例に例示のもののみに限定されることはない。なお、以下の実施例などにおいて、濃度や使用量を示す際の％は特にその基準を付記しないかぎり、質量基準による％である。 Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to those exemplified in those Examples. In the following examples and the like,% when indicating the concentration and the amount used is% based on the mass standard unless the standard is specifically added.
また、実施例に先立ち、実施例でドーパントとして用いるスチレンスルホン酸とアクリルアミド基またはメタクリルアミド基を含む重合性モノマーとの共重合体の合成例を合成例１〜１２で示す。そして、比較例でドーパントとして用いる共重合体の合成例については、比較合成例１〜４で示す。 Further, prior to Examples, Synthesis Examples 1 to 12 show examples of synthesizing a copolymer of styrene sulfonic acid used as a dopant in Examples and a polymerizable monomer containing an acrylamide group or a methacrylamide group. Then, the synthesis example of the copolymer used as a dopant in the comparative example is shown in Comparative Synthesis Examples 1 to 4.
合成例１
共重合体〔スチレンスルホン酸：Ｎ−（２−ヒドロキシエチル）アクリルアミド＝９：１（モル比)〕の合成
この合成例１では、使用開始時のモノマーがスチレンスルホン酸とＮ−（２−ヒドロキシエチル）アクリルアミドとであって、それらの比率がモル比で９：１の共重合体の合成について説明する。なお、以下の合成例などにおいても、共重合体の組成の表示にあたっては、使用開始時のモノマーのモル比で表示する。
Synthesis example 1
Synthesis of copolymer [styrene sulfonic acid: N- (2-hydroxyethyl) acrylamide = 9: 1 (molar ratio)] In this synthesis example 1, the monomers at the start of use are styrene sulfonic acid and N- (2-hydroxy). The synthesis of copolymers of ethyl) acrylamide and their ratio of 9: 1 in molar ratio will be described. In addition, also in the following synthesis examples and the like, when displaying the composition of a copolymer, it is expressed by the molar ratio of the monomer at the start of use.
２Ｌの攪拌機付セパラブルフラスコに１Ｌの純水を添加し、そこにスチレンスルホン酸ナトリウム１１１．３ｇ（スチレンスルホン酸として９８．９ｇであって、０．５４モル）とＮ−（２−ヒドロキシエチル）アクリルアミド６．９ｇ（０．０６モル）とを添加した。そして、その溶液に酸化剤として、過硫酸アンモニウムを６ｇ添加して、スチレンスルホン酸とＮ−（２−ヒドロキシエチル）アクリルアミドとの重合反応を１２時間行った。 1 L of pure water was added to a 2 L separable flask with a stirrer, and 111.3 g of sodium styrene sulfonate (98.9 g of styrene sulfonic acid, 0.54 mol) and N- (2-hydroxyethyl) were added thereto. ) 6.9 g (0.06 mol) of acrylamide was added. Then, 6 g of ammonium persulfate was added to the solution as an oxidizing agent, and the polymerization reaction of styrenesulfonic acid and N- (2-hydroxyethyl) acrylamide was carried out for 12 hours.
その後、その反応液にオルガノ社のカチオン交換樹脂［アンバーライト１２０Ｂ(商品名)］を１００ｇ添加して、１時間攪拌機で攪拌し、次いで、東洋濾紙社製の濾紙Ｎｏ．１３１で濾過し、このカチオン交換樹脂による処理と濾過を３回繰り返して、液中のカチオン成分をすべて除去した。 Then, 100 g of Organo's cation exchange resin [Amberlite 120B (trade name)] was added to the reaction solution, and the mixture was stirred with a stirrer for 1 hour, and then the filter paper No. The mixture was filtered through 131, and the treatment with the cation exchange resin and the filtration were repeated three times to remove all the cation components in the liquid.
得られたスチレンスルホン酸とＮ−（２−ヒドロキシエチル）アクリルアミドとの共重合体について、ＧＰＣ（Ｇｅｌ Ｐｅｒｍｅａｔｉｏｎ Ｃｈｒｏｍａｔｏｇｒａｐｈｙ：ゲル濾過クロマトグラフィーであるが、以下、「ＧＰＣ」のみで示す）カラムを用いたＨＰＬＣ（Ｈｉｇｈ Ｐｅｒｆｏｒｍａｎｃｅ Ｌｉｑｕｉｄ Ｃｈｒｏｍａｔｏｇｒａｐｈｙ：高速液体クロマトグラフィーであるが、以下、「ＨＰＬＣ」のみで示す）システムを用いて分析を行った結果、上記共重合体のデキストランを標品として見積もった重量平均分子量は、９６，０００であった。 For the obtained copolymer of styrene sulfonic acid and N- (2-hydroxyethyl) acrylamide, a GPC (Gel Permeation Chromatography: gel filtration chromatography, hereinafter referred to only as “GPC”) column was used. As a result of analysis using an HPLC (High Performance Liquid Chromatography: high performance liquid chromatography, hereinafter referred to only as "HPLC") system, the weight average molecular weight estimated using the above copolymer dextran as a standard is , 96,000.
合成例２
共重合体〔スチレンスルホン酸：Ｎ−（２−ヒドロキシエチル）アクリルアミド＝７：３（モル比)〕の合成）
この合成例２では、スチレンスルホン酸とＮ−（２−ヒドロキシエチル）アクリルアミドとのモル比が７：３の共重合体の合成について説明する。
Synthesis example 2
Synthesis of copolymer [styrene sulfonic acid: N- (2-hydroxyethyl) acrylamide = 7: 3 (molar ratio)])
In this Synthesis Example 2, the synthesis of a copolymer having a molar ratio of styrene sulfonic acid and N- (2-hydroxyethyl) acrylamide of 7: 3 will be described.
２Ｌの攪拌機付セパラブルフラスコに１Ｌの純水を添加し、そこにスチレンスルホン酸ナトリウム８６．６ｇ（スチレンスルホン酸として７６．９ｇであって、０．４２モル）とＮ−（２−ヒドロキシエチル）アクリルアミド２０．７ｇ（０．１８モル）とを添加した。そして、その溶液に酸化剤として、過硫酸アンモニウムを６ｇ添加して、スチレンスルホン酸とＮ−（２−ヒドロキシエチル）アクリルアミドとの重合反応を１２時間行った。 1 L of pure water was added to a 2 L separable flask with a stirrer, and 86.6 g of sodium styrene sulfonate (76.9 g as styrene sulfonic acid, 0.42 mol) and N- (2-hydroxyethyl) were added thereto. ) 20.7 g (0.18 mol) of acrylamide was added. Then, 6 g of ammonium persulfate was added to the solution as an oxidizing agent, and the polymerization reaction of styrenesulfonic acid and N- (2-hydroxyethyl) acrylamide was carried out for 12 hours.
その後、その反応液にオルガノ社のカチオン交換樹脂［アンバーライト１２０Ｂ(商品名)］を１００ｇ添加して、１時間攪拌機で攪拌し、次いで、東洋濾紙社製の濾紙Ｎｏ．１３１で濾過し、このカチオン交換樹脂による処理と濾過を３回繰り返して、液中のカチオン成分をすべて除去した。 Then, 100 g of Organo's cation exchange resin [Amberlite 120B (trade name)] was added to the reaction solution, and the mixture was stirred with a stirrer for 1 hour, and then the filter paper No. The mixture was filtered through 131, and the treatment with the cation exchange resin and the filtration were repeated three times to remove all the cation components in the liquid.
得られたスチレンスルホン酸とＮ−（２−ヒドロキシエチル）アクリルアミドとの共重合体について、ＧＰＣカラムを用いたＨＰＬＣシステムを用いて分析を行った結果、上記共重合体のデキストランを標品として見積もった重量平均分子量は、９８，０００であった。 As a result of analyzing the obtained copolymer of styrene sulfonic acid and N- (2-hydroxyethyl) acrylamide using an HPLC system using a GPC column, the dextran of the above copolymer was estimated as a standard. The weight average molecular weight was 98,000.
合成例３
共重合体〔スチレンスルホン酸：Ｎ−（２−ヒドロキシエチル）アクリルアミド＝５：５（モル比)〕の合成
この合成例３では、スチレンスルホン酸とＮ−（２−ヒドロキシエチル）アクリルアミドとのモル比が５：５の共重合体の合成について説明する。
Synthesis example 3
Synthesis of Copolymer [Styrene Sulfonic Acid: N- (2-Hydroxyethyl) Acrylamide = 5: 5 (Mole Ratio)] In this Synthesis Example 3, the molars of styrene sulfonic acid and N- (2-hydroxyethyl) acrylamide are obtained. The synthesis of a copolymer having a ratio of 5: 5 will be described.
２Ｌの攪拌機付セパラブルフラスコに１Ｌの純水を添加し、そこにスチレンスルホン酸ナトリウム６１．９ｇ（スチレンスルホン酸として５５．０ｇであって、０．３０モル）とＮ−（２−ヒドロキシエチル）アクリルアミド３４．５ｇ（０．３０モル）とを添加した。そして、その溶液に酸化剤として、過硫酸アンモニウムを６ｇ添加して、スチレンスルホン酸とＮ−（２−ヒドロキシエチル）アクリルアミドとの重合反応を１２時間行った。 1 L of pure water was added to a 2 L separable flask with a stirrer, and 61.9 g of sodium styrene sulfonate (55.0 g of styrene sulfonic acid, 0.30 mol) and N- (2-hydroxyethyl) were added thereto. ) 34.5 g (0.30 mol) of acrylamide was added. Then, 6 g of ammonium persulfate was added to the solution as an oxidizing agent, and the polymerization reaction of styrenesulfonic acid and N- (2-hydroxyethyl) acrylamide was carried out for 12 hours.
その後、その反応液にオルガノ社のカチオン交換樹脂［アンバーライト１２０Ｂ(商品名)］を１００ｇ添加して、１時間攪拌機で攪拌し、次いで、東洋濾紙社製の濾紙Ｎｏ．１３１で濾過し、このカチオン交換樹脂による処理と濾過を３回繰り返して、液中のカチオン成分をすべて除去した。 Then, 100 g of Organo's cation exchange resin [Amberlite 120B (trade name)] was added to the reaction solution, and the mixture was stirred with a stirrer for 1 hour, and then the filter paper No. The mixture was filtered through 131, and the treatment with the cation exchange resin and the filtration were repeated three times to remove all the cation components in the liquid.
得られたスチレンスルホン酸とＮ−（２−ヒドロキシエチル）アクリルアミドとの共重合体について、ＧＰＣカラムを用いたＨＰＬＣシステムを用いて分析を行った結果、上記共重合体のデキストランを標品として見積もった重量平均分子量は、９０，０００であった。 As a result of analyzing the obtained copolymer of styrene sulfonic acid and N- (2-hydroxyethyl) acrylamide using an HPLC system using a GPC column, the dextran of the above copolymer was estimated as a standard. The weight average molecular weight was 90,000.
合成例４
共重合体〔スチレンスルホン酸：Ｎ−（ヒドロキシメチル）アクリルアミド＝９：１（モル％)）の合成
この合成例４では、スチレンスルホン酸とＮ−（ヒドロキシメチル）アクリルアミドとのモル比が９：１の共重合体の合成について説明する。
Synthesis example 4
Synthesis of copolymer [styrene sulfonic acid: N- (hydroxymethyl) acrylamide = 9: 1 (mol%)) In this synthesis example 4, the molar ratio of styrene sulfonic acid to N- (hydroxymethyl) acrylamide is 9 :. The synthesis of the copolymer of No. 1 will be described.
２Ｌの攪拌機付セパラブルフラスコに１Ｌの純水を添加し、そこにスチレンスルホン酸ナトリウム１１１．３ｇ（スチレンスルホン酸として９８．９ｇであって、０．５４モル）とＮ−（ヒドロキシメチル）アクリルアミド６．１ｇ（０．０６モル）とを添加した。そして、その溶液に酸化剤として、過硫酸アンモニウムを６ｇ添加して、スチレンスルホン酸とＮ−（ヒドロキシメチル）アクリルアミドとの重合反応を１２時間行った。 1 L of pure water was added to a 2 L separable flask with a stirrer, and 111.3 g of sodium styrene sulfonate (98.9 g of styrene sulfonic acid, 0.54 mol) and N- (hydroxymethyl) acrylamide were added thereto. 6.1 g (0.06 mol) was added. Then, 6 g of ammonium persulfate was added to the solution as an oxidizing agent, and the polymerization reaction of styrenesulfonic acid and N- (hydroxymethyl) acrylamide was carried out for 12 hours.
その後、その反応液にオルガノ社のカチオン交換樹脂［アンバーライト１２０Ｂ(商品名)］を１００ｇ添加して、１時間攪拌機で攪拌し、次いで、東洋濾紙社製の濾紙Ｎｏ．１３１で濾過し、このカチオン交換樹脂による処理と濾過を３回繰り返して、液中のカチオン成分をすべて除去した。 Then, 100 g of Organo's cation exchange resin [Amberlite 120B (trade name)] was added to the reaction solution, and the mixture was stirred with a stirrer for 1 hour, and then the filter paper No. The mixture was filtered through 131, and the treatment with the cation exchange resin and the filtration were repeated three times to remove all the cation components in the liquid.
得られたスチレンスルホン酸とＮ−（ヒドロキシメチル）アクリルアミドとの共重合体について、ＧＰＣカラムを用いたＨＰＬＣシステムを用いて分析を行った結果、上記共重合体のデキストランを標品として見積もった重量平均分子量は、９６，０００であった。 As a result of analyzing the obtained copolymer of styrene sulfonic acid and N- (hydroxymethyl) acrylamide using an HPLC system using a GPC column, the weight estimated using the dextran of the above copolymer as a standard. The average molecular weight was 96,000.
合成例５
共重合体〔スチレンスルホン酸：Ｎ−（ヒドロキシメチル）アクリルアミド＝７：３（モル比)〕の合成
この合成例５では、スチレンスルホン酸とＮ−（ヒドロキシメチル）アクリルアミドとのモル比が７：３の共重合体の合成について説明する。
Synthesis example 5
Synthesis of copolymer [styrene sulfonic acid: N- (hydroxymethyl) acrylamide = 7: 3 (molar ratio)] In this Synthesis Example 5, the molar ratio of styrene sulfonic acid to N- (hydroxymethyl) acrylamide is 7 :. The synthesis of the copolymer of No. 3 will be described.
２Ｌの攪拌機付セパラブルフラスコに１Ｌの純水を添加し、そこにスチレンスルホン酸ナトリウム８６．６ｇ（スチレンスルホン酸として７６．９ｇであって、０．４２モル）とＮ−（ヒドロキシメチル）アクリルアミド１８．２ｇ（０．１８モル）とを添加した。そして、その溶液に酸化剤として、過硫酸アンモニウムを６ｇ添加して、スチレンスルホン酸とＮ−（ヒドロキシメチル）アクリルアミドとの重合反応を１２時間行った。 1 L of pure water was added to a 2 L separable flask with a stirrer, and 86.6 g of sodium styrene sulfonate (76.9 g of styrene sulfonic acid, 0.42 mol) and N- (hydroxymethyl) acrylamide were added thereto. 18.2 g (0.18 mol) was added. Then, 6 g of ammonium persulfate was added to the solution as an oxidizing agent, and the polymerization reaction of styrenesulfonic acid and N- (hydroxymethyl) acrylamide was carried out for 12 hours.
その後、その反応液にオルガノ社のカチオン交換樹脂［アンバーライト１２０Ｂ(商品名)］を１００ｇ添加して、１時間攪拌機で攪拌し、次いで、東洋濾紙社製の濾紙Ｎｏ．１３１で濾過し、このカチオン交換樹脂による処理と濾過を３回繰り返して、液中のカチオン成分をすべて除去した。 Then, 100 g of Organo's cation exchange resin [Amberlite 120B (trade name)] was added to the reaction solution, and the mixture was stirred with a stirrer for 1 hour, and then the filter paper No. The mixture was filtered through 131, and the treatment with the cation exchange resin and the filtration were repeated three times to remove all the cation components in the liquid.
得られたスチレンスルホン酸とＮ−（ヒドロキシメチル）アクリルアミドとの共重合体について、ＧＰＣカラムを用いたＨＰＬＣシステムを用いて分析を行った結果、上記共重合体のデキストランを標品として見積もった重量平均分子量は、９１，０００であった。 As a result of analyzing the obtained copolymer of styrene sulfonic acid and N- (hydroxymethyl) acrylamide using an HPLC system using a GPC column, the weight estimated using the dextran of the above copolymer as a standard. The average molecular weight was 91,000.
合成例６
共重合体〔スチレンスルホン酸：Ｎ−メチルメタクリルアミド＝９：１（モル比)〕の合成
この合成例６では、スチレンスルホン酸とＮ−メチルメタクリルアミドとのモル比が９：１の共重合体の合成について説明する。
Synthesis example 6
Synthesis of copolymer [styrene sulfonic acid: N-methylmethacrylamide = 9: 1 (molar ratio)] In this synthesis example 6, the molar ratio of styrene sulfonic acid to N-methylmethacrylamide is 9: 1. The synthesis of coalescence will be described.
２Ｌの攪拌機付セパラブルフラスコに１Ｌの純水を添加し、そこにスチレンスルホン酸ナトリウム１１１．３ｇ（スチレンスルホン酸として９８．９ｇであって、０．５４モル）とＮ−メチルメタクリルアミド５．９ｇ（０．０６モル）とを添加した。そして、その溶液に酸化剤として、過硫酸アンモニウムを６ｇ添加して、スチレンスルホン酸とＮ−メチルメタクリルアミドとの重合反応を１２時間行った。 1. Add 1 L of pure water to a 2 L separable flask with a stirrer, and add 111.3 g of sodium styrene sulfonate (98.9 g of styrene sulfonic acid, 0.54 mol) and N-methylmethacrylamide. 9 g (0.06 mol) was added. Then, 6 g of ammonium persulfate was added to the solution as an oxidizing agent, and the polymerization reaction of styrene sulfonic acid and N-methylmethacrylamide was carried out for 12 hours.
その後、その反応液にオルガノ社のカチオン交換樹脂［アンバーライト１２０Ｂ(商品名)］を１００ｇ添加して、１時間攪拌機で攪拌し、次いで、東洋濾紙社製の濾紙Ｎｏ．１３１で濾過し、このカチオン交換樹脂による処理と濾過を３回繰り返して、液中のカチオン成分をすべて除去した。 Then, 100 g of Organo's cation exchange resin [Amberlite 120B (trade name)] was added to the reaction solution, and the mixture was stirred with a stirrer for 1 hour, and then the filter paper No. The mixture was filtered through 131, and the treatment with the cation exchange resin and the filtration were repeated three times to remove all the cation components in the liquid.
得られたスチレンスルホン酸とＮ−メチルメタクリルアミドとの共重合体について、ＧＰＣカラムを用いたＨＰＬＣシステムを用いて分析を行った結果、上記共重合体のデキストランを標品として見積もった重量平均分子量は、１０２，０００であった。 As a result of analyzing the obtained copolymer of styrene sulfonic acid and N-methylmethacrylamide using an HPLC system using a GPC column, the weight average molecular weight estimated using the dextran of the above copolymer as a standard. Was 102,000.
合成例７
共重合体〔スチレンスルホン酸：Ｎ−メチルメタクリルアミド＝７：３（モル比)〕の合成
この合成例７では、スチレンスルホン酸とＮ−メチルメタクリルアミドとのモル比が７：３の共重合体の合成について説明する。
Synthesis example 7
Synthesis of copolymer [styrene sulfonic acid: N-methylmethacrylamide = 7: 3 (molar ratio)] In this synthesis example 7, the copolymer weight of styrene sulfonic acid and N-methylmethacrylamide having a molar ratio of 7: 3 The synthesis of coalescence will be described.
２Ｌの攪拌機付セパラブルフラスコに１Ｌの純水を添加し、そこにスチレンスルホン酸ナトリウム８６．６ｇ（スチレンスルホン酸として７６．９ｇであって、０．４２モル）とＮ−メチルメタクリルアミド１７．８ｇ（０．１８モル）とを添加した。そして、その溶液に酸化剤として、過硫酸アンモニウムを６ｇ添加して、スチレンスルホン酸とＮ−メチルメタクリルアミドとの重合反応を１２時間行った。 1 L of pure water was added to a 2 L separable flask with a stirrer, and 86.6 g of sodium styrene sulfonate (76.9 g of styrene sulfonic acid, 0.42 mol) and N-methylmethacrylamide 17. 8 g (0.18 mol) was added. Then, 6 g of ammonium persulfate was added to the solution as an oxidizing agent, and the polymerization reaction of styrene sulfonic acid and N-methylmethacrylamide was carried out for 12 hours.
その後、その反応液にオルガノ社のカチオン交換樹脂［アンバーライト１２０Ｂ(商品名)］を１００ｇ添加して、１時間攪拌機で攪拌し、次いで、東洋濾紙社製の濾紙Ｎｏ．１３１で濾過し、このカチオン交換樹脂による処理と濾過を３回繰り返して、液中のカチオン成分をすべて除去した。 Then, 100 g of Organo's cation exchange resin [Amberlite 120B (trade name)] was added to the reaction solution, and the mixture was stirred with a stirrer for 1 hour, and then the filter paper No. The mixture was filtered through 131, and the treatment with the cation exchange resin and the filtration were repeated three times to remove all the cation components in the liquid.
得られたスチレンスルホン酸とＮ−メチルメタクリルアミドとの共重合体について、ＧＰＣカラムを用いたＨＰＬＣシステムを用いて分析を行った結果、上記共重合体のデキストランを標品として見積もった重量平均分子量は、９７，０００であった。 As a result of analyzing the obtained copolymer of styrene sulfonic acid and N-methylmethacrylamide using an HPLC system using a GPC column, the weight average molecular weight estimated using the dextran of the above copolymer as a standard. Was 97,000.
合成例８
共重合体〔スチレンスルホン酸：Ｎ−（４−ヒドロキシフェニル）メタクリルアミド＝９：１（モル比)〕の合成
この合成例８では、スチレンスルホン酸とＮ−（４−ヒドロキシフェニル）メタクリルアミドとのモル比が９：１の共重合体の合成について説明する。
Synthesis example 8
Synthesis of copolymer [styrene sulfonic acid: N- (4-hydroxyphenyl) methacrylamide = 9: 1 (molar ratio)] In this Synthesis Example 8, styrene sulfonic acid and N- (4-hydroxyphenyl) methacrylamide were used. The synthesis of a copolymer having a molar ratio of 9: 1 will be described.
２Ｌの攪拌機付セパラブルフラスコに１Ｌの純水を添加し、そこにスチレンスルホン酸ナトリウム１１１．３ｇ（スチレンスルホン酸として９８．９ｇであって、０．５４モル）とＮ−（４−ヒドロキシフェニル）メタクリルアミド１０．６ｇ（０．０６モル）とを添加した。そして、その溶液に酸化剤として、過硫酸アンモニウムを６ｇ添加して、スチレンスルホン酸とＮ−（４−ヒドロキシフェニル）メタクリルアミドとの重合反応を１２時間行った。 1 L of pure water was added to a 2 L separable flask with a stirrer, and 111.3 g of sodium styrene sulfonate (98.9 g as styrene sulfonic acid, 0.54 mol) and N- (4-hydroxyphenyl) were added thereto. ) Methacrylamide with 10.6 g (0.06 mol) was added. Then, 6 g of ammonium persulfate was added to the solution as an oxidizing agent, and the polymerization reaction of styrenesulfonic acid and N- (4-hydroxyphenyl) methacrylamide was carried out for 12 hours.
その後、その反応液にオルガノ社のカチオン交換樹脂［アンバーライト１２０Ｂ(商品名)］を１００ｇ添加して、１時間攪拌機で攪拌し、次いで、東洋濾紙社製の濾紙Ｎｏ．１３１で濾過し、このカチオン交換樹脂による処理と濾過を３回繰り返して、液中のカチオン成分をすべて除去した。 Then, 100 g of Organo's cation exchange resin [Amberlite 120B (trade name)] was added to the reaction solution, and the mixture was stirred with a stirrer for 1 hour, and then the filter paper No. The mixture was filtered through 131, and the treatment with the cation exchange resin and the filtration were repeated three times to remove all the cation components in the liquid.
得られたスチレンスルホン酸とＮ−（４−ヒドロキシフェニル）メタクリルアミドとの共重合体について、ＧＰＣカラムを用いたＨＰＬＣシステムを用いて分析を行った結果、上記共重合体のデキストランを標品として見積もった重量平均分子量は、１００，０００であった。 The obtained copolymer of styrene sulfonic acid and N- (4-hydroxyphenyl) methacrylamide was analyzed using an HPLC system using a GPC column. As a result, the above copolymer dextran was used as a standard. The estimated weight average molecular weight was 100,000.
合成例９
共重合体〔スチレンスルホン酸：Ｎ−（４−ヒドロキシフェニル）メタクリルアミド＝７：３（モル比)〕の合成
この合成例９では、スチレンスルホン酸とＮ−（４−ヒドロキシフェニル）メタクリルアミドとのモル比が７：３の共重合体の合成について説明する。
Synthesis example 9
Synthesis of copolymer [styrene sulfonic acid: N- (4-hydroxyphenyl) methacrylamide = 7: 3 (molar ratio)] In this Synthesis Example 9, styrene sulfonic acid and N- (4-hydroxyphenyl) methacrylamide were used. The synthesis of a copolymer having a molar ratio of 7: 3 will be described.
２Ｌの攪拌機付セパラブルフラスコに１Ｌの純水を添加し、そこにスチレンスルホン酸ナトリウム８６．６ｇ（スチレンスルホン酸として７６．９ｇであって、０．４２モル）とＮ−（４−ヒドロキシフェニル）メタクリルアミド３１．９ｇ（０．１８モル）とを添加した。そして、その溶液に酸化剤として、過硫酸アンモニウムを６ｇ添加して、スチレンスルホン酸とＮ−（４−ヒドロキシフェニル）メタクリルアミドとの重合反応を１２時間行った。 1 L of pure water was added to a 2 L separable flask with a stirrer, and 86.6 g of sodium styrene sulfonate (76.9 g as styrene sulfonic acid, 0.42 mol) and N- (4-hydroxyphenyl) were added thereto. ) 31.9 g (0.18 mol) of methacrylamide was added. Then, 6 g of ammonium persulfate was added to the solution as an oxidizing agent, and the polymerization reaction of styrenesulfonic acid and N- (4-hydroxyphenyl) methacrylamide was carried out for 12 hours.
その後、その反応液にオルガノ社のカチオン交換樹脂［アンバーライト１２０Ｂ(商品名)］を１００ｇ添加して、１時間攪拌機で攪拌し、次いで、東洋濾紙社製の濾紙Ｎｏ．１３１で濾過し、このカチオン交換樹脂による処理と濾過を３回繰り返して、液中のカチオン成分をすべて除去した。 Then, 100 g of Organo's cation exchange resin [Amberlite 120B (trade name)] was added to the reaction solution, and the mixture was stirred with a stirrer for 1 hour, and then the filter paper No. The mixture was filtered through 131, and the treatment with the cation exchange resin and the filtration were repeated three times to remove all the cation components in the liquid.
得られたスチレンスルホン酸とＮ−（４−ヒドロキシフェニル）メタクリルアミドとの共重合体について、ＧＰＣカラムを用いたＨＰＬＣシステムを用いて分析を行った結果、上記共重合体のデキストランを標品として見積もった重量平均分子量は、９７，０００であった。 The obtained copolymer of styrene sulfonic acid and N- (4-hydroxyphenyl) methacrylamide was analyzed using an HPLC system using a GPC column. As a result, the above copolymer dextran was used as a standard. The estimated weight average molecular weight was 97,000.
合成例１０
共重合体〔スチレンスルホン酸：Ｎ−フェニルアクリルアミド＝９.５：０.５（モル比)〕の合成
この合成例１０では、スチレンスルホン酸とＮ−フェニルアクリルアミドとのモル比が９．５：０．５の共重合体の合成について説明する。
Synthesis example 10
Synthesis of copolymer [styrene sulfonic acid: N-phenylacrylamide = 9.5: 0.5 (molar ratio)] In this synthesis example 10, the molar ratio of styrene sulfonic acid to N-phenylacrylamide is 9.5 :. The synthesis of 0.5 copolymer will be described.
２Ｌの攪拌機付セパラブルフラスコに１Ｌの純水を添加し、そこにスチレンスルホン酸ナトリウム１１７．５ｇ（スチレンスルホン酸として１０４．４ｇであって、０．５７モル）とＮ−フェニルアクリルアミド４．４ｇ（０．０３モル）とを添加した。そして、その溶液に酸化剤として、過硫酸アンモニウムを６ｇ添加して、スチレンスルホン酸とＮ−フェニルアクリルアミドとの重合反応を１２時間行った。 1 L of pure water was added to a 2 L separable flask with a stirrer, and 117.5 g of sodium styrene sulfonate (104.4 g of styrene sulfonic acid, 0.57 mol) and 4.4 g of N-phenylacrylamide were added thereto. (0.03 mol) and was added. Then, 6 g of ammonium persulfate was added to the solution as an oxidizing agent, and the polymerization reaction of styrene sulfonic acid and N-phenylacrylamide was carried out for 12 hours.
その後、その反応液にオルガノ社のカチオン交換樹脂［アンバーライト１２０Ｂ(商品名)］を１００ｇ添加して、１時間攪拌機で攪拌し、次いで、東洋濾紙社製の濾紙Ｎｏ．１３１で濾過し、このカチオン交換樹脂による処理と濾過を３回繰り返して、液中のカチオン成分をすべて除去した。 Then, 100 g of Organo's cation exchange resin [Amberlite 120B (trade name)] was added to the reaction solution, and the mixture was stirred with a stirrer for 1 hour, and then the filter paper No. The mixture was filtered through 131, and the treatment with the cation exchange resin and the filtration were repeated three times to remove all the cation components in the liquid.
得られたスチレンスルホン酸とＮ−フェニルアクリルアミドとの共重合体について、ＧＰＣカラムを用いたＨＰＬＣシステムを用いて分析を行った結果、上記共重合体のデキストランを標品として見積もった重量平均分子量は、９９，０００であった。 As a result of analyzing the obtained copolymer of styrene sulfonic acid and N-phenylacrylamide using an HPLC system using a GPC column, the weight average molecular weight estimated using the dextran of the above copolymer as a standard was obtained. , 99,000.
合成例１１
共重合体〔スチレンスルホン酸：Ｎ−フェニルアクリルアミド＝９：１（モル比)〕の合成
この合成例１１では、スチレンスルホン酸とＮ−フェニルアクリルアミドとのモル比が９：１の共重合体の合成について説明する。
Synthesis example 11
Synthesis of copolymer [styrene sulfonic acid: N-phenylacrylamide = 9: 1 (molar ratio)] In this synthesis example 11, a copolymer having a molar ratio of styrene sulfonic acid to N-phenylacrylamide of 9: 1 is used. Synthesis will be described.
２Ｌの攪拌機付セパラブルフラスコに１Ｌの純水を添加し、そこにスチレンスルホン酸ナトリウム１１１．３ｇ（スチレンスルホン酸として９８．９ｇであって、０．５４モル）とＮ−フェニルアクリルアミド８．８ｇ（０．０６モル）とを添加した。そして、その溶液に酸化剤として、過硫酸アンモニウムを６ｇ添加して、スチレンスルホン酸とＮ−フェニルアクリルアミドとの重合反応を１２時間行った。 1 L of pure water was added to a 2 L separable flask with a stirrer, and 111.3 g of sodium styrene sulfonate (98.9 g of styrene sulfonic acid, 0.54 mol) and 8.8 g of N-phenylacrylamide were added thereto. (0.06 mol) and was added. Then, 6 g of ammonium persulfate was added to the solution as an oxidizing agent, and the polymerization reaction of styrene sulfonic acid and N-phenylacrylamide was carried out for 12 hours.
その後、その反応液にオルガノ社のカチオン交換樹脂［アンバーライト１２０Ｂ(商品名)］を１００ｇ添加して、１時間攪拌機で攪拌し、次いで、東洋濾紙社製の濾紙Ｎｏ．１３１で濾過し、このカチオン交換樹脂による処理と濾過を３回繰り返して、液中のカチオン成分をすべて除去した。 Then, 100 g of Organo's cation exchange resin [Amberlite 120B (trade name)] was added to the reaction solution, and the mixture was stirred with a stirrer for 1 hour, and then the filter paper No. The mixture was filtered through 131, and the treatment with the cation exchange resin and the filtration were repeated three times to remove all the cation components in the liquid.
得られたスチレンスルホン酸とＮ−フェニルアクリルアミドとの共重合体について、ＧＰＣカラムを用いたＨＰＬＣシステムを用いて分析を行った結果、上記共重合体のデキストランを標品として見積もった重量平均分子量は、１０３，０００であった。 As a result of analyzing the obtained copolymer of styrene sulfonic acid and N-phenylacrylamide using an HPLC system using a GPC column, the weight average molecular weight estimated using the dextran of the above copolymer as a standard was obtained. , 103,000.
合成例１２
共重合体〔スチレンスルホン酸：Ｎ−フェニルアクリルアミド＝７：３（モル比)〕の合成
この合成例１２では、スチレンスルホン酸とＮ−フェニルアクリルアミドとのモル比が７：３の共重合体の合成について説明する。
Synthesis example 12
Synthesis of copolymer [styrene sulfonic acid: N-phenylacrylamide = 7: 3 (molar ratio)] In this synthesis example 12, a copolymer having a molar ratio of styrene sulfonic acid and N-phenylacrylamide of 7: 3 is used. Synthesis will be described.
２Ｌの攪拌機付セパラブルフラスコに１Ｌの純水を添加し、そこにスチレンスルホン酸ナトリウム８６．６ｇ（スチレンスルホン酸として７６．９ｇであって、０．４２モル）とＮ−フェニルアクリルアミド２６．５ｇ（０．１８モル）とを添加した。そして、その溶液に酸化剤として、過硫酸アンモニウムを６ｇ添加して、スチレンスルホン酸とＮ−フェニルアクリルアミドとの重合反応を１２時間行った。 1 L of pure water was added to a 2 L separable flask with a stirrer, and 86.6 g of sodium styrene sulfonate (76.9 g of styrene sulfonic acid, 0.42 mol) and 26.5 g of N-phenylacrylamide were added thereto. (0.18 mol) and was added. Then, 6 g of ammonium persulfate was added to the solution as an oxidizing agent, and the polymerization reaction of styrene sulfonic acid and N-phenylacrylamide was carried out for 12 hours.
その後、その反応液にオルガノ社のカチオン交換樹脂［アンバーライト１２０Ｂ(商品名)］を１００ｇ添加して、１時間攪拌機で攪拌し、次いで、東洋濾紙社製の濾紙Ｎｏ．１３１で濾過し、このカチオン交換樹脂による処理と濾過を３回繰り返して、液中のカチオン成分をすべて除去した。 Then, 100 g of Organo's cation exchange resin [Amberlite 120B (trade name)] was added to the reaction solution, and the mixture was stirred with a stirrer for 1 hour, and then the filter paper No. The mixture was filtered through 131, and the treatment with the cation exchange resin and the filtration were repeated three times to remove all the cation components in the liquid.
得られたスチレンスルホン酸とＮ−フェニルアクリルアミドとの共重合体について、ＧＰＣカラムを用いたＨＰＬＣシステムを用いて分析を行った結果、上記共重合体のデキストランを標品として見積もった重量平均分子量は、８８，０００であった。 As a result of analyzing the obtained copolymer of styrene sulfonic acid and N-phenylacrylamide using an HPLC system using a GPC column, the weight average molecular weight estimated using the dextran of the above copolymer as a standard was obtained. , 88,000.
比較合成例１
共重合体〔スチレンスルホン酸：メタクリル酸ヒドロキシエチル＝９：１（モル比)〕の合成
この比較合成例１では、スチレンスルホン酸とメタクリル酸ヒドロキシエチルとのモル比が９：１の共重合体の合成について説明する。
Comparative synthesis example 1
Synthesis of copolymer [styrene sulfonic acid: hydroxyethyl methacrylate = 9: 1 (molar ratio)] In this comparative synthesis example 1, a copolymer having a molar ratio of styrene sulfonic acid and hydroxyethyl methacrylate of 9: 1 is used. The synthesis of is described.
２Ｌの攪拌機付セパラブルフラスコに１Ｌの純水を添加し、そこにスチレンスルホン酸ナトリウム１１１．３ｇ（スチレンスルホン酸として９８．９ｇであって、０．５４モル）とメタクリル酸ヒドロキシエチル７．８ｇ（０．０６モル）とを添加した。そして、その溶液に酸化剤として、過硫酸アンモニウムを６ｇ添加して、スチレンスルホン酸とメタクリル酸ヒドロキシエチルとの重合反応を１２時間行った。 1 L of pure water was added to a 2 L separable flask with a stirrer, and 111.3 g of sodium styrene sulfonate (98.9 g of styrene sulfonic acid, 0.54 mol) and 7.8 g of hydroxyethyl methacrylate were added thereto. (0.06 mol) and was added. Then, 6 g of ammonium persulfate was added to the solution as an oxidizing agent, and the polymerization reaction of styrenesulfonic acid and hydroxyethyl methacrylate was carried out for 12 hours.
その後、その反応液にオルガノ社のカチオン交換樹脂［アンバーライト１２０Ｂ(商品名)］を１００ｇ添加して、１時間攪拌機で攪拌し、次いで、東洋濾紙社製の濾紙Ｎｏ．１３１で濾過し、このカチオン交換樹脂による処理と濾過を３回繰り返して、液中のカチオン成分をすべて除去した。 Then, 100 g of Organo's cation exchange resin [Amberlite 120B (trade name)] was added to the reaction solution, and the mixture was stirred with a stirrer for 1 hour, and then the filter paper No. The mixture was filtered through 131, and the treatment with the cation exchange resin and the filtration were repeated three times to remove all the cation components in the liquid.
得られたスチレンスルホン酸とメタクリル酸ヒドロキシエチルとの共重合体について、ＧＰＣカラムを用いたＨＰＬＣシステムを用いて分析を行った結果、上記共重合体のデキストランを標品として見積もった重量平均分子量は、９３，０００であった。 As a result of analyzing the obtained copolymer of styrene sulfonic acid and hydroxyethyl methacrylate using an HPLC system using a GPC column, the weight average molecular weight estimated using the dextran of the above copolymer as a standard was obtained. , 93,000.
なお、この「比較合成例１」における「比較合成例」とは、前記のように、比較例でドーパントとして用いる共重合体の合成例を示すものであって、正確には、「比較例用合成例」とすべきであるが、本書では、一部簡略化して、「比較合成例」で示す。これは以下に示す「比較合成例」に関しても同様である。 The "comparative synthesis example" in this "comparative synthesis example 1" indicates, as described above, a synthesis example of the copolymer used as the dopant in the comparative example, and to be exact, "for comparative synthesis". Although it should be referred to as "synthesis example", in this document, it is shown as "comparative synthesis example" with some simplification. This also applies to the "comparative synthesis example" shown below.
比較合成例２
共重合体〔スチレンスルホン酸：メタクリル酸ヒドロキシエチル＝７：３（モル比)〕の合成
この比較合成例２では、スチレンスルホン酸とメタクリル酸ヒドロキシエチルとのモル比が７：３の共重合体の合成について説明する。
Comparative synthesis example 2
Synthesis of copolymer [styrene sulfonic acid: hydroxyethyl methacrylate = 7: 3 (molar ratio)] In this comparative synthesis example 2, a copolymer having a molar ratio of styrene sulfonic acid and hydroxyethyl methacrylate of 7: 3 is used. The synthesis of is described.
２Ｌの攪拌機付セパラブルフラスコに１Ｌの純水を添加し、そこにスチレンスルホン酸ナトリウム８６．６ｇ（スチレンスルホン酸として７６．９ｇであって、０．４２モル）とメタクリル酸ヒドロキシエチル２０．９ｇ（０．１８モル）とを添加した。そして、その溶液に酸化剤として、過硫酸アンモニウムを６ｇ添加して、スチレンスルホン酸とメタクリル酸ヒドロキシエチルとの重合反応を１２時間行った。 1 L of pure water was added to a 2 L separable flask with a stirrer, and 86.6 g of sodium styrene sulfonate (76.9 g of styrene sulfonic acid, 0.42 mol) and 20.9 g of hydroxyethyl methacrylate were added thereto. (0.18 mol) and was added. Then, 6 g of ammonium persulfate was added to the solution as an oxidizing agent, and the polymerization reaction of styrenesulfonic acid and hydroxyethyl methacrylate was carried out for 12 hours.
その後、その反応液にオルガノ社のカチオン交換樹脂［アンバーライト１２０Ｂ(商品名)］を１００ｇ添加して、１時間攪拌機で攪拌し、次いで、東洋濾紙社製の濾紙Ｎｏ．１３１で濾過し、このカチオン交換樹脂による処理と濾過を３回繰り返して、液中のカチオン成分をすべて除去した。 Then, 100 g of Organo's cation exchange resin [Amberlite 120B (trade name)] was added to the reaction solution, and the mixture was stirred with a stirrer for 1 hour, and then the filter paper No. The mixture was filtered through 131, and the treatment with the cation exchange resin and the filtration were repeated three times to remove all the cation components in the liquid.
得られたスチレンスルホン酸とメタクリル酸ヒドロキシエチルとの共重合体について、ＧＰＣカラムを用いたＨＰＬＣシステムを用いて分析を行った結果、上記共重合体のデキストランを標品として見積もった重量平均分子量は、８９，０００であった。 As a result of analyzing the obtained copolymer of styrene sulfonic acid and hydroxyethyl methacrylate using an HPLC system using a GPC column, the weight average molecular weight estimated using the dextran of the above copolymer as a standard was obtained. , 89,000.
比較合成例３
共重合体〔スチレンスルホン酸：３−アクリロキシプロピルトリメトキシシラン＝９：１（モル比)〕の合成
この比較合成例３では、スチレンスルホン酸と３−メタクリロキシプロピルトリエトキシシラン-アクリロキシプロピルトリメトキシシランとのモル比が９：１の共重合体の合成について説明する。
Comparative synthesis example 3
Synthesis of copolymer [styrene sulfonic acid: 3-acryloxypropyltrimethoxysilane = 9: 1 (molar ratio)] In this comparative synthesis example 3, styrene sulfonic acid and 3-methacryloxypropyltriethoxysilane-acryloxypropyl The synthesis of a copolymer having a molar ratio of 9: 1 with trimethoxysilane will be described.
２Ｌの攪拌機付セパラブルフラスコに１Ｌの純水を添加し、そこにスチレンスルホン酸ナトリウム１１１．３ｇ（スチレンスルホン酸として９８．９ｇであって、０．５４モル）と３−アクリロキシプロピルトリメトキシシラン１４．１ｇ（０．０６モル）とを添加した。そして、その溶液に酸化剤として、過硫酸アンモニウムを６ｇ添加して、スチレンスルホン酸と３−アクリロキシプロピルトリメトキシシランとの重合反応を１２時間行った。 1 L of pure water was added to a 2 L separable flask with a stirrer, and 111.3 g of sodium styrene sulfonate (98.9 g as styrene sulfonic acid, 0.54 mol) and 3-acryloxypropyltrimethoxy were added thereto. 14.1 g (0.06 mol) of silane was added. Then, 6 g of ammonium persulfate was added to the solution as an oxidizing agent, and the polymerization reaction of styrene sulfonic acid and 3-acryloxypropyltrimethoxysilane was carried out for 12 hours.
その後、その反応液にオルガノ社のカチオン交換樹脂［アンバーライト１２０Ｂ(商品名)］を１００ｇ添加して、１時間攪拌機で攪拌し、次いで、東洋濾紙社製の濾紙Ｎｏ．１３１で濾過し、このカチオン交換樹脂による処理と濾過を３回繰り返して、液中のカチオン成分をすべて除去した。 Then, 100 g of Organo's cation exchange resin [Amberlite 120B (trade name)] was added to the reaction solution, and the mixture was stirred with a stirrer for 1 hour, and then the filter paper No. The mixture was filtered through 131, and the treatment with the cation exchange resin and the filtration were repeated three times to remove all the cation components in the liquid.
得られたスチレンスルホン酸と３−アクリロキシプロピルトリメトキシシランとの共重合体について、ＧＰＣカラムを用いたＨＰＬＣシステムを用いて分析を行った結果、上記共重合体のデキストランを標品として見積もった重量平均分子量は、８２，０００であった。 As a result of analyzing the obtained copolymer of styrene sulfonic acid and 3-acryloxypropyltrimethoxysilane using an HPLC system using a GPC column, the dextran of the above copolymer was estimated as a standard. The weight average molecular weight was 82,000.
比較合成例４
共重合体〔スチレンスルホン酸：３−アクリロキシプロピルトリメトキシシラン＝７：３（モル比)〕の合成
この比較合成例４では、スチレンスルホン酸と３−アクリロキシプロピルトリメトキシシランとのモル比が７：３の共重合体の合成について説明する。
Comparative synthesis example 4
Synthesis of copolymer [styrene sulfonic acid: 3-acryloxypropyltrimethoxysilane = 7: 3 (molar ratio)] In this comparative synthesis example 4, the molar ratio of styrene sulfonic acid to 3-acryloxypropyltrimethoxysilane The synthesis of a 7: 3 copolymer will be described.
２Ｌの攪拌機付セパラブルフラスコに１Ｌの純水を添加し、そこにスチレンスルホン酸ナトリウム８６．６ｇ（スチレンスルホン酸として７６．９ｇであって、０．４２モル）と３−アクリロキシプロピルトリメトキシシラン４２．２ｇ（０．１８モル）とを添加した。そして、その溶液に酸化剤として、過硫酸アンモニウムを６ｇ添加して、スチレンスルホン酸と３−アクリロキシプロピルトリメトキシシランとの重合反応を１２時間行った。 1 L of pure water was added to a 2 L separable flask with a stirrer, and 86.6 g of sodium styrene sulfonate (76.9 g as styrene sulfonic acid, 0.42 mol) and 3-acryloxypropyltrimethoxy were added thereto. 42.2 g (0.18 mol) of silane was added. Then, 6 g of ammonium persulfate was added to the solution as an oxidizing agent, and the polymerization reaction of styrene sulfonic acid and 3-acryloxypropyltrimethoxysilane was carried out for 12 hours.
その後、その反応液にオルガノ社のカチオン交換樹脂［アンバーライト１２０Ｂ(商品名)］を１００ｇ添加して、１時間攪拌機で攪拌し、次いで、東洋濾紙社製の濾紙Ｎｏ．１３１で濾過し、このカチオン交換樹脂による処理と濾過を３回繰り返して、液中のカチオン成分をすべて除去した。 Then, 100 g of Organo's cation exchange resin [Amberlite 120B (trade name)] was added to the reaction solution, and the mixture was stirred with a stirrer for 1 hour, and then the filter paper No. The mixture was filtered through 131, and the treatment with the cation exchange resin and the filtration were repeated three times to remove all the cation components in the liquid.
得られたスチレンスルホン酸と３−アクリロキシプロピルトリメトキシシランとの共重合体について、ＧＰＣカラムを用いたＨＰＬＣシステムを用いて分析を行った結果、上記共重合体のデキストランを標品として見積もった重量平均分子量は、８０，０００であった。 As a result of analyzing the obtained copolymer of styrene sulfonic acid and 3-acryloxypropyltrimethoxysilane using an HPLC system using a GPC column, the dextran of the above copolymer was estimated as a standard. The weight average molecular weight was 80,000.
次に、実施例の電解コンデンサの電解質を構成するにあたって用いる導電性高分子組成物の分散液の製造を製造例１〜３０で示し、比較例の電解コンデンサの電解質を構成するにあたって用いる導電性高分子組成物の製造を比較製造例１〜３で示す。 Next, the production of the dispersion liquid of the conductive polymer composition used for constructing the electrolyte of the electrolytic capacitor of the example is shown in Production Examples 1 to 30, and the high conductivity used for constructing the electrolyte of the electrolytic capacitor of the comparative example is shown. The production of the molecular composition is shown in Comparative Production Examples 1 to 3.
製造例１
合成例１で得たスチレンスルホン酸とＮ−（２−ヒドロキシエチル）アクリルアミドとのモル比が９：１の共重合体の４％水溶液６００ｇを内容積１Ｌのステンレス鋼製容器に入れ、そこに触媒として硫酸第一鉄・７水和物を０．３ｇ添加して溶解した。その中にエチレンジオキシチオフェンを４ｍｌゆっくり滴下した。ステンレス鋼製の攪拌バネで攪拌し、容器に陽極を取り付け、攪拌バネに陰極を取り付け、１ｍＡ／ｃｍ２の定電流で１８時間電解酸化重合して、導電性高分子組成物を製造した。上記電解酸化重合後、水で４倍希釈した後、超音波ホモジナイザー［日本精機社製、ＵＳ−Ｔ３００（商品名）］で３０分間分散処理を行った。
Manufacturing example 1
600 g of a 4% aqueous solution of a copolymer having a molar ratio of styrene sulfonic acid and N- (2-hydroxyethyl) acrylamide obtained in Synthesis Example 1 of 9: 1 was placed in a stainless steel container having an internal volume of 1 L and placed therein. As a catalyst, 0.3 g of ferrous sulfate heptahydrate was added and dissolved. 4 ml of ethylenedioxythiophene was slowly added dropwise thereto. A conductive polymer composition was produced by stirring with a stirring spring made of stainless steel, attaching an anode to the container, attaching a cathode to the stirring spring, and electrolytically oxidatively polymerizing at a constant current of 1 mA / cm 2 for 18 hours. After the above electrolytic oxidative polymerization, it was diluted 4-fold with water, and then dispersed with an ultrasonic homogenizer [US-T300 (trade name) manufactured by Nippon Seiki Co., Ltd.] for 30 minutes.
その後、オルガノ社のカチオン交換樹脂［アンバーライト１２０Ｂ（商品名）］を１００ｇ添加して、１時間攪拌機で撹拌し、次いで、東洋濾紙社製の濾紙Ｎｏ．１３１で濾過し、このカチオン交換樹脂による処理と濾過を３回繰り返して、液中のカチオン成分をすべて除去した。 Then, 100 g of Organo's cation exchange resin [Amberlite 120B (trade name)] was added and stirred with a stirrer for 1 hour, and then the filter paper No. 1 manufactured by Toyo Filter Paper Co., Ltd. was added. The mixture was filtered through 131, and the treatment with the cation exchange resin and the filtration were repeated three times to remove all the cation components in the liquid.
上記処理後の液を孔径が１μｍのフィルターに通し、その通過液を限外濾過装置［ザルトリウス社製Ｖｉｖａｆｌｏｗ２００（商品名）、分子量分画５万］で処理して、液中の遊離の低分子成分を除去した。この処理後の液を水で希釈して導電性高分子組成物の濃度を３％に調整し、その３％液４０ｇに対し、導電性向上剤としてブタンジオールを４ｇ添加して、導電性向上剤としてのブタンジオールを添加した導電性高分子組成物の分散液を得た。次いで、２８％アンモニア水溶液でｐＨ４．０に調整した。上記ブタンジオールの添加量は導電性高分子組成物に対して３３３％であった。 The liquid after the above treatment is passed through a filter having a pore size of 1 μm, and the passing liquid is treated with an ultrafiltration device [Vivaflow200 (trade name) manufactured by Sartorius, molecular weight fraction 50,000] to release low molecules in the liquid. The component was removed. The liquid after this treatment is diluted with water to adjust the concentration of the conductive polymer composition to 3%, and 4 g of butanediol as a conductivity improver is added to 40 g of the 3% liquid to improve the conductivity. A dispersion liquid of a conductive polymer composition to which butanediol as an agent was added was obtained. Then, the pH was adjusted to 4.0 with a 28% aqueous ammonia solution. The amount of butanediol added was 333% with respect to the conductive polymer composition.
製造例２
合成例１で得た共重合体に代えて、合成例２で得たスチレンスルホン酸とＮ−（２−ヒドロキシエチル）アクリルアミドとのモル比が７：３の共重合体を用いた以外は、すべて製造例１と同様の操作を行って、導電性高分子組成物の分散液を得た。なお、この製造例２では、すべて製造例１と同様の操作を行って導電性高分子組成物の分散液を得ていることから、この製造例２の導電性高分子組成物の分散液には、製造例１の場合と同様に、ブタンジオールと２８％アンモニア水溶液とが添加されている。そして、このようなブタンジオールと２８％アンモニア水溶液との添加は、以下に示す製造例３〜３０および比較製造例１〜３の導電性高分子組成物の分散液に対しても同様に行われる。
Manufacturing example 2
A copolymer having a molar ratio of styrene sulfonic acid and N- (2-hydroxyethyl) acrylamide of 7: 3 obtained in Synthesis Example 2 was used instead of the copolymer obtained in Synthesis Example 1. The same operation as in Production Example 1 was carried out to obtain a dispersion liquid of the conductive polymer composition. In addition, in this Production Example 2, since the dispersion liquid of the conductive polymer composition is obtained by performing the same operation as in Production Example 1, the dispersion liquid of the conductive polymer composition of Production Example 2 is used. However, butanediol and a 28% aqueous ammonia solution are added as in the case of Production Example 1. Then, such addition of butanediol and a 28% aqueous ammonia solution is also carried out in the same manner for the dispersion liquids of the conductive polymer compositions of Production Examples 3 to 30 and Comparative Production Examples 1 to 3 shown below. ..
製造例３
合成例１で得た共重合体に代えて、合成例３で得たスチレンスルホン酸とＮ−（２−ヒドロキシエチル）アクリルアミドとのモル比が５：５の共重合体を用いた以外は、すべて製造例１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Manufacturing example 3
A copolymer having a molar ratio of styrene sulfonic acid and N- (2-hydroxyethyl) acrylamide of 5: 5 obtained in Synthesis Example 3 was used instead of the copolymer obtained in Synthesis Example 1. The same operation as in Production Example 1 was carried out to obtain a dispersion liquid of the conductive polymer composition.
製造例４
合成例１で得た共重合体に代えて、合成例４で得たスチレンスルホン酸とＮ−（ヒドロキシメチル）アクリルアミドとのモル比が９：１の共重合体を用いた以外は、すべて製造例１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Manufacturing example 4
All were produced except that the copolymer obtained in Synthesis Example 1 was replaced with the copolymer obtained in Synthesis Example 4 in which the molar ratio of styrene sulfonic acid to N- (hydroxymethyl) acrylamide was 9: 1. The same operation as in Example 1 was carried out to obtain a dispersion liquid of the conductive polymer composition.
製造例５
合成例１で得た共重合体に代えて、合成例５で得たスチレンスルホン酸とＮ−（ヒドロキシメチル）アクリルアミドとのモル比が７：３の共重合体を用いた以外は、すべて製造例１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Production example 5
All were produced except that the copolymer obtained in Synthesis Example 1 was replaced with the copolymer obtained in Synthesis Example 5 in which the molar ratio of styrene sulfonic acid to N- (hydroxymethyl) acrylamide was 7: 3. The same operation as in Example 1 was carried out to obtain a dispersion liquid of the conductive polymer composition.
製造例６
合成例１で得た共重合体に代えて、合成例６で得たスチレンスルホン酸とＮ−メチルメタクリルアミドとのモル比が９：１の共重合体を用いた以外は、すべて製造例１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Production example 6
Production Example 1 except that a copolymer obtained in Synthesis Example 6 having a molar ratio of styrene sulfonic acid and N-methylmethacrylamide of 9: 1 was used instead of the copolymer obtained in Synthesis Example 1. The same operation as in the above was carried out to obtain a dispersion liquid of the conductive polymer composition.
製造例７
合成例１で得た共重合体に代えて、合成例７で得たスチレンスルホン酸とＮ−メチルメタクリルアミドとのモル比が７：３の共重合体を用いた以外は、すべて製造例１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Production example 7
Production Example 1 except that a copolymer obtained in Synthesis Example 7 having a molar ratio of styrene sulfonic acid and N-methylmethacrylamide of 7: 3 was used instead of the copolymer obtained in Synthesis Example 1. The same operation as in the above was carried out to obtain a dispersion liquid of the conductive polymer composition.
製造例８
合成例１で得た共重合体に代えて、合成例８で得たスチレンスルホン酸とＮ−（４−ヒドロキシフェニル）メタクリルアミドとのモル比が９：１の共重合体を用いた以外は、すべて製造例１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Production Example 8
Instead of the copolymer obtained in Synthesis Example 1, a copolymer having a molar ratio of styrene sulfonic acid and N- (4-hydroxyphenyl) methacrylamide obtained in Synthesis Example 8 of 9: 1 was used. The same operation as in Production Example 1 was carried out to obtain a dispersion liquid of the conductive polymer composition.
製造例９
合成例１で得た共重合体に代えて、合成例９で得たスチレンスルホン酸とＮ−（４−ヒドロキシフェニル）メタクリルアミドとのモル比が７：３の共重合体を用いた以外は、すべて製造例１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Manufacturing example 9
Instead of the copolymer obtained in Synthesis Example 1, a copolymer having a molar ratio of styrene sulfonic acid and N- (4-hydroxyphenyl) methacrylamide obtained in Synthesis Example 9 of 7: 3 was used. The same operation as in Production Example 1 was carried out to obtain a dispersion liquid of the conductive polymer composition.
製造例１０
合成例１で得た共重合体に代えて、合成例１０で得たスチレンスルホン酸とＮ−フェニルアクリルアミドとのモル比が９．５：０．５の共重合体を用いた以外は、すべて製造例１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Production Example 10
All except the copolymer obtained in Synthesis Example 10 having a molar ratio of styrene sulfonic acid to N-phenylacrylamide of 9.5: 0.5 was used instead of the copolymer obtained in Synthesis Example 10. The same operation as in Production Example 1 was carried out to obtain a dispersion liquid of the conductive polymer composition.
製造例１１
合成例１で得た共重合体に代えて、合成例１１で得たスチレンスルホン酸とＮ−フェニルアクリルアミドとのモル比が９：１の共重合体を用いた以外は、すべて製造例１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Production Example 11
In place of the copolymer obtained in Synthesis Example 1, a copolymer obtained in Synthesis Example 11 having a molar ratio of styrene sulfonic acid to N-phenylacrylamide of 9: 1 was used, but all of them were in accordance with Production Example 1. The same operation was carried out to obtain a dispersion liquid of the conductive polymer composition.
製造例１２
合成例１で得た共重合体に代えて、合成例１２で得たスチレンスルホン酸とＮ−フェニルアクリルアミドとのモル比が７：３の共重合体を用いた以外は、すべて製造例１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Production Example 12
All of the same as Production Example 1 except that the copolymer obtained in Synthesis Example 12 was used instead of the copolymer obtained in Synthesis Example 12 in which the molar ratio of styrene sulfonic acid to N-phenylacrylamide was 7: 3. The same operation was carried out to obtain a dispersion liquid of the conductive polymer composition.
製造例１３
製造例１で使用したエチレンジオキシチオフェン４ｍｌに代えて、エチル化エチレンジオキシチオフェン４ｍｌを用いた以外は、すべて製造例１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Production Example 13
Except for the fact that 4 ml of ethylenedethylenedioxythiophene was used instead of 4 ml of ethylenedioxythiophene used in Production Example 1, the same operations as in Production Example 1 were carried out to prepare a dispersion of the conductive polymer composition. Obtained.
製造例１４
製造例１で使用したエチレンジオキシチオフェン４ｍｌに代えて、エチレンジオキシチオフェン２ｍｌとエチル化エチレンジオキシチオフェン２ｍｌとを用いた以外は、すべて製造例１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Production example 14
Except for the fact that 2 ml of ethylenedioxythiophene and 2 ml of ethylened ethylenedioxythiophene were used instead of 4 ml of ethylenedioxythiophene used in Production Example 1, the same operations as in Production Example 1 were carried out to achieve high conductivity. A dispersion of the molecular composition was obtained.
製造例１５
製造例１で使用したエチレンジオキシチオフェン４ｍｌに代えて、エチレンジオキシチオフェン２ｍｌとブチル化エチレンジオキシチオフェン２ｍｌとを用いた以外は、すべて製造例１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Production example 15
Except for the fact that 2 ml of ethylenedioxythiophene and 2 ml of butylated ethylenedioxythiophene were used instead of 4 ml of ethylenedioxythiophene used in Production Example 1, the same operations as in Production Example 1 were carried out to achieve high conductivity. A dispersion of the molecular composition was obtained.
製造例１６
製造例１１で使用したエチレンジオキシチオフェン４ｍｌに代えて、エチル化エチレンジオキシチオフェン４ｍｌを用いた以外は、すべて製造例１１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Production example 16
All the same operations as in Production Example 11 were carried out except that 4 ml of ethylenedethylenedioxythiophene was used instead of 4 ml of ethylenedioxythiophene used in Production Example 11, and the dispersion liquid of the conductive polymer composition was prepared. Obtained.
製造例１７
製造例１１で使用したエチレンジオキシチオフェン４ｍｌに代えて、エチレンジオキシチオフェン２ｍｌとエチル化エチレンジオキシチオフェン２ｍｌとを用いた以外は、すべて製造例１１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Production example 17
Except for the fact that 2 ml of ethylenedioxythiophene and 2 ml of ethylened ethylenedioxythiophene were used instead of 4 ml of ethylenedioxythiophene used in Production Example 11, the same operations as in Production Example 11 were carried out to achieve high conductivity. A dispersion of the molecular composition was obtained.
製造例１８
製造例１１で使用したエチレンジオキシチオフェン４ｍｌに代えて、エチレンジオキシチオフェン２ｍｌとブチル化エチレンジオキシチオフェン２ｍｌとを用いた以外は、すべて製造例１１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Production Example 18
Except for the fact that 2 ml of ethylenedioxythiophene and 2 ml of butylated ethylenedioxythiophene were used instead of 4 ml of ethylenedioxythiophene used in Production Example 11, the same operations as in Production Example 11 were carried out to achieve high conductivity. A dispersion of the molecular composition was obtained.
製造例１９
合成例１で得た共重合体の４％水溶液６００ｇに代えて、合成例１で得たスチレンスルホン酸とＮ−（２−ヒドロキシエチル）アクリルアミドとのモル比が９：１の共重合体の４％水溶液３００ｇとテイカ社製ポリスチレンスルホン酸（重量平均分子量１００，０００）の４％水溶液３００ｇとの混合液を用いた以外は、すべて製造例１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Production example 19
Instead of 600 g of a 4% aqueous solution of the copolymer obtained in Synthesis Example 1, a copolymer having a molar ratio of styrene sulfonic acid and N- (2-hydroxyethyl) acrylamide obtained in Synthesis Example 1 of 9: 1 was used. Except for using a mixed solution of 300 g of a 4% aqueous solution and 300 g of a 4% aqueous solution of Teika polystyrene sulfonic acid (weight average molecular weight 100,000), all the same operations as in Production Example 1 were carried out to carry out the conductive polymer. A dispersion of the composition was obtained.
製造例２０
合成例１で得た共重合体の４％水溶液６００ｇに代えて、合成例１１で得たスチレンスルホン酸とＮ−フェニルアクリルアミドとのモル比が９：１の共重合体の４％水溶液３００ｇとテイカ社製ポリスチレンスルホン酸（重量平均分子量１００，０００）の４％水溶液３００ｇとの混合液を用いた以外は、すべて製造例１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Production example 20
Instead of 600 g of the 4% aqueous solution of the copolymer obtained in Synthesis Example 1, 300 g of the 4% aqueous solution of the copolymer obtained in Synthesis Example 11 having a molar ratio of styrene sulfonic acid and N-phenylacrylamide of 9: 1 was used. A dispersion liquid of the conductive polymer composition was carried out in the same manner as in Production Example 1 except that a mixed solution of 300 g of a 4% aqueous solution of polystyrene sulfonic acid (weight average molecular weight 100,000) manufactured by Teika Co., Ltd. was used. Got
製造例２１
合成例１で得た共重合体の４％水溶液６００ｇに代えて、合成例１で得たスチレンスルホン酸とＮ−（２−ヒドロキシエチル）アクリルアミドとのモル比が９：１の共重合体の４％水溶液３００ｇとテイカ社製ポリスチレンスルホン酸（重量平均分子量１００，０００）の４％水溶液２２５ｇとフェノールスルホン酸ノボラック樹脂［小西化学工業社製、重量平均分子量６０，０００で、一般式（２）におけるＲ１が水素のもの］の４％水溶液７５ｇとの混合液を用いた以外は、すべて製造例１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Production Example 21
Instead of 600 g of a 4% aqueous solution of the copolymer obtained in Synthesis Example 1, a copolymer having a molar ratio of styrene sulfonic acid and N- (2-hydroxyethyl) acrylamide obtained in Synthesis Example 1 of 9: 1 was used. 300 g of 4% aqueous solution, 225 g of 4% aqueous solution of polystyrene sulfonic acid (weight average molecular weight 100,000) manufactured by Teika, and novolak resin phenol sulfonate [manufactured by Konishi Chemical Industry Co., Ltd., weight average molecular weight 60,000, general formula (2) except that R 1 is using a mixture of 4% aqueous solution 75g of those hydrogen] in are all working in the same manner as in production example 1, to obtain a dispersion liquid of the conductive polymer composition.
製造例２２
この製造例２２では、まず、製造例１で得た導電性高分子組成物の分散液と混合するためのスルホン化ポリエステルをドーパントとする導電性高分子組成物の分散液を次に示すようにして得た。
Production example 22
In Production Example 22, first, the dispersion liquid of the conductive polymer composition using the sulfonated polyester as a dopant for mixing with the dispersion liquid of the conductive polymer composition obtained in Production Example 1 is shown below. I got it.
スルホン化ポリエステル［互応化学工業社製プラスコートＺ−５６１（商品名）、重量平均分子量２７，０００］の４％水溶液２００ｇを内容積１Ｌの容器に入れ、酸化剤として過硫酸アンモニウムを２ｇ添加した後、攪拌機で攪拌して溶解した。次いで、硫酸第二鉄の４０％水溶液を０．４ｇ添加し、攪拌しながら、その中にエチレンジオキシチオフェン３ｍｌを滴下し、２４時間かけて、エチレンジオキシチオフェンの化学酸化重合を行って、導電性高分子組成物を製造した。 200 g of a 4% aqueous solution of sulfonated polyester [Plus Coat Z-561 (trade name) manufactured by GOO CHEMICAL CO., LTD., Weight average molecular weight 27,000] is placed in a container having an internal volume of 1 L, and 2 g of ammonium persulfate is added as an oxidizing agent. , Stirred with a stirrer to dissolve. Next, 0.4 g of a 40% aqueous solution of ferric sulfate was added, and 3 ml of ethylenedioxythiophene was added dropwise thereto with stirring, and chemical oxidative polymerization of ethylenedioxythiophene was carried out over 24 hours. A conductive polymer composition was produced.
上記重合後、水で４倍に希釈した後、超音波ホモジナイザーで３０分間分散処理を行った。その後、オルガノ社のカチオン交換樹脂［アンバーライトＩＲ１２０Ｂ（商品名）］を１００ｇ添加して、１時間攪拌機で撹拌し、次いで、東洋濾紙社製の濾紙Ｎｏ．１３１で濾過し、このカチオン交換樹脂による処理と濾過を３回繰り返して、液中のカチオン成分をすべて除去した。 After the above polymerization, it was diluted 4-fold with water and then dispersed with an ultrasonic homogenizer for 30 minutes. Then, 100 g of Organo's cation exchange resin [Amberlite IR120B (trade name)] was added and stirred with a stirrer for 1 hour, and then the filter paper No. The mixture was filtered through 131, and the treatment with the cation exchange resin and the filtration were repeated three times to remove all the cation components in the liquid.
上記処理後の液を孔径が１μｍのフィルターに通し、その通過液を限外濾過装置［ザルトリウス社製Ｖｉｖａｆｌｏｗ２００（商品名）、分子量分画５万］で処理して、液中の遊離の低分子成分を除去した。この処理後の液を水で希釈して導電性高分子組成物の濃度を３％に調整し、その３％液４０ｇに対し、導電性向上剤としてブタンジオールを４ｇ添加して、導電性向上剤としてのブタンジオールを添加した導電性高分子組成物の分散液を得た。上記ブタンジオールの添加量は導電性高分子組成物に対して３３３％であった。 The liquid after the above treatment is passed through a filter having a pore size of 1 μm, and the passing liquid is treated with an ultrafiltration device [Vivaflow200 (trade name) manufactured by Sartorius, molecular weight fraction 50,000] to release low molecules in the liquid. The component was removed. The liquid after this treatment is diluted with water to adjust the concentration of the conductive polymer composition to 3%, and 4 g of butanediol as a conductivity improver is added to 40 g of the 3% liquid to improve the conductivity. A dispersion liquid of a conductive polymer composition to which butanediol as an agent was added was obtained. The amount of butanediol added was 333% with respect to the conductive polymer composition.
このスルホン化ポリエステルをドーパントとする導電性高分子組成物の分散液４０ｇと製造例１で得た導電性高分子組成物の分散液４０ｇとを混合して、異なるドーパントを用いた導電性高分子組成物の分散液の混合液を得た。 40 g of the dispersion liquid of the conductive polymer composition using this sulfonated polyester as a dopant and 40 g of the dispersion liquid of the conductive polymer composition obtained in Production Example 1 are mixed, and the conductive polymer using different dopants is mixed. A mixed solution of the dispersion liquid of the composition was obtained.
製造例２３
製造例１で得た導電性高分子組成物の分散液４０ｇに代えて、製造例２で得た導電性高分子組成物の分散液４０ｇを用いた以外は、すべて製造例２２と同様の操作を行って、異なるドーパントを用いた導電性高分子組成物の分散液の混合液を得た。
Production Example 23
The same operation as in Production Example 22 except that 40 g of the dispersion liquid of the conductive polymer composition obtained in Production Example 2 was used instead of 40 g of the dispersion liquid of the conductive polymer composition obtained in Production Example 2. Was carried out to obtain a mixed solution of dispersions of conductive polymer compositions using different dopants.
製造例２４
製造例１で得た導電性高分子組成物の分散液４０ｇに代えて、製造例４で得た導電性高分子組成物の分散液４０ｇを用いた以外は、すべて製造例２２と同様の操作を行って、異なるドーパントを用いた導電性高分子組成物の分散液の混合液を得た。
Production example 24
The same operation as in Production Example 22 except that 40 g of the dispersion liquid of the conductive polymer composition obtained in Production Example 4 was used instead of 40 g of the dispersion liquid of the conductive polymer composition obtained in Production Example 1. Was carried out to obtain a mixed solution of dispersions of conductive polymer compositions using different dopants.
製造例２５
製造例１で得た導電性高分子組成物の分散液４０ｇに代えて、製造例６で得た導電性高分子組成物の分散液４０ｇを用いた以外は、すべて製造例２２と同様の操作を行って、異なるドーパントを用いた導電性高分子組成物の分散液の混合液を得た。
Production example 25
The same operation as in Production Example 22 except that 40 g of the dispersion liquid of the conductive polymer composition obtained in Production Example 6 was used instead of 40 g of the dispersion liquid of the conductive polymer composition obtained in Production Example 1. Was carried out to obtain a mixed solution of dispersions of conductive polymer compositions using different dopants.
製造例２６
製造例１で得た導電性高分子組成物の分散液４０ｇに代えて、製造例８で得た導電性高分子組成物の分散液４０ｇを用いた以外は、すべて製造例２２と同様の操作を行って、異なるドーパントを用いた導電性高分子組成物の分散液の混合液を得た。
Production example 26
The same operation as in Production Example 22 except that 40 g of the dispersion liquid of the conductive polymer composition obtained in Production Example 8 was used instead of 40 g of the dispersion liquid of the conductive polymer composition obtained in Production Example 1. Was carried out to obtain a mixed solution of dispersions of conductive polymer compositions using different dopants.
製造例２７
製造例１で得た導電性高分子組成物の分散液４０ｇに代えて、製造例１１で得た導電性高分子組成物の分散液４０ｇを用いた以外は、すべて製造例２２と同様の操作を行って、異なるドーパントを用いた導電性高分子組成物の分散液の混合液を得た。
Production example 27
The same operation as in Production Example 22 except that 40 g of the dispersion liquid of the conductive polymer composition obtained in Production Example 11 was used instead of 40 g of the dispersion liquid of the conductive polymer composition obtained in Production Example 1. Was carried out to obtain a mixed solution of dispersions of conductive polymer compositions using different dopants.
製造例２８
製造例１で得た導電性高分子組成物の分散液４０ｇに代えて、製造例１２で得た導電性高分子組成物の分散液４０ｇを用いた以外は、すべて製造例２２と同様の操作を行って、異なるドーパントを用いた導電性高分子組成物の分散液の混合液を得た。
Production Example 28
All operations were the same as in Production Example 22 except that 40 g of the dispersion liquid of the conductive polymer composition obtained in Production Example 12 was used instead of 40 g of the dispersion liquid of the conductive polymer composition obtained in Production Example 12. Was carried out to obtain a mixed solution of dispersions of conductive polymer compositions using different dopants.
製造例２９
製造例１で得た導電性高分子組成物の分散液４０ｇに代えて、製造例１４で得た導電性高分子組成物の分散液４０ｇを用いた以外は、すべて製造例２２と同様の操作を行って、異なるドーパントを用いた導電性高分子組成物の分散液の混合液を得た。
Production example 29
The same operation as in Production Example 22 except that 40 g of the dispersion liquid of the conductive polymer composition obtained in Production Example 14 was used instead of 40 g of the dispersion liquid of the conductive polymer composition obtained in Production Example 1. Was carried out to obtain a mixed solution of dispersions of conductive polymer compositions using different dopants.
製造例３０
製造例１で得た導電性高分子組成物の分散液４０ｇに代えて、製造例１７で得た導電性高分子組成物の分散液４０ｇを用いた以外は、すべて製造例２２と同様の操作を行って、異なるドーパントを用いた導電性高分子組成物の分散液の混合液を得た。
Production example 30
The same operation as in Production Example 22 except that 40 g of the dispersion liquid of the conductive polymer composition obtained in Production Example 17 was used instead of 40 g of the dispersion liquid of the conductive polymer composition obtained in Production Example 1. Was carried out to obtain a mixed solution of dispersions of conductive polymer compositions using different dopants.
比較製造例１
合成例１で得たスチレンスルホン酸とＮ−（２−ヒドロキシエチル）アクリルアミドとのモル比９：１の共重合体の４％水溶液６００ｇに代えて、ポリスチレンスルホン酸（テイカ社製、重量平均分子量１００，０００）の４％水溶液６００ｇを用いた以外は、すべて製造例１と同様の操作を行って、導電性向上剤としてのブタンジオールを添加した導電性高分子組成物の分散液を得た。なお、この比較製造例１やそれに続く比較製造例２〜３は、比較例の電解コンデンサの電解質を構成するにあたって使用する導電性高分子組成物の分散液の製造例を示すものであり、正確には、比較例用製造例というべきであるが、簡略化して、上記のように、比較製造例１、比較製造例２〜３という。
Comparative manufacturing example 1
Instead of 600 g of a 4% aqueous solution of a copolymer of 9: 1 molar ratio of styrene sulfonic acid and N- (2-hydroxyethyl) acrylamide obtained in Synthesis Example 1, polystyrene sulfonic acid (manufactured by Teika Co., Ltd., weight average molecular weight) The same operation as in Production Example 1 was carried out except that 600 g of a 4% aqueous solution of 100,000) was used to obtain a dispersion liquid of a conductive polymer composition to which butanediol as a conductivity improver was added. .. It should be noted that Comparative Production Example 1 and subsequent Comparative Production Examples 2 and 3 show examples of production of a dispersion liquid of the conductive polymer composition used for forming the electrolyte of the electrolytic capacitor of the comparative example, and are accurate. Although it should be referred to as a production example for a comparative production example, for simplification, it is referred to as a comparative production example 1 and a comparative production example 2 to 3 as described above.
比較製造例２
合成例１で得たスチレンスルホン酸とＮ−（２−ヒドロキシエチル）アクリルアミドとのモル比９：１の共重合体の４％水溶液６００ｇに代えて、ポリスチレンスルホン酸（テイカ社製、重量平均分子量１００，０００）の４％水溶液３００ｇとフェノールスルホン酸ノボラック樹脂［小西化学工業社製、重量平均分子量６０，０００で、一般式（２）におけるＲ１が水素のもの］の４％水溶液３００ｇとの混合液６００ｇを用いた以外は、すべて製造例１と同様の操作を行って、導電性向上剤としてのブタンジオールを添加した導電性高分子組成物の分散液を得た。
Comparative manufacturing example 2
Instead of 600 g of a 4% aqueous solution of a copolymer of 9: 1 molar ratio of styrene sulfonic acid and N- (2-hydroxyethyl) acrylamide obtained in Synthesis Example 1, polystyrene sulfonic acid (manufactured by Teika Co., Ltd., weight average molecular weight) a 4% aqueous solution 300g and phenolsulfonic acid novolac resin 100,000) [Konishi chemical industry Co., Ltd., a weight average molecular weight 60,000, R 1 in the general formula (2) those hydrogen] with a 4% aqueous solution 300g of The same operation as in Production Example 1 was carried out except that 600 g of the mixed solution was used to obtain a dispersion of a conductive polymer composition to which butanediol as a conductivity improver was added.
比較製造例３
合成例１で得た共重合体に代えて、比較合成例１で得たスチレンスルホン酸とメタクリル酸ヒドロキシエチルとのモル比が９：１の共重合体を用いた以外は、すべて製造例１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Comparative manufacturing example 3
Production Example 1 except that a copolymer obtained in Comparative Synthesis Example 1 having a molar ratio of styrene sulfonic acid and hydroxyethyl methacrylate of 9: 1 was used instead of the copolymer obtained in Synthesis Example 1. The same operation as in the above was carried out to obtain a dispersion liquid of the conductive polymer composition.
次に電解コンデンサの実施例を示すが、その実施例のうちの実施例１〜４０は巻回型アルミニウム電解コンデンサに関し、実施例４１〜５０はタンタル電解コンデンサに関し、実施例５１〜６０は積層型アルミニウム電解コンデンサに関するものである。 Next, examples of electrolytic capacitors will be shown. Among the examples, Examples 1 to 40 relate to a wound aluminum electrolytic capacitor, Examples 41 to 50 relate to a tantalum electrolytic capacitor, and Examples 51 to 60 relate to a laminated type. It relates to an aluminum electrolytic capacitor.
［巻回型アルミニウム電解コンデンサでの評価（１）］
実施例１〜２０および比較例１〜３
この実施例１〜２０および比較例１〜３では、以下に示すように巻回型アルミニウム電解コンデンサを製造して、その特性を評価する。
[Evaluation with a wound aluminum electrolytic capacitor (1)]
Examples 1 to 20 and Comparative Examples 1 to 3
In Examples 1 to 20 and Comparative Examples 1 to 3, wound aluminum electrolytic capacitors are manufactured and their characteristics are evaluated as shown below.
アルミニウム箔の表面をエッチング処理した後、化成処理を行って誘電体層を形成した陽極にリード端子を取り付け、また、アルミニウム箔からなる陰極にリード端子を取り付け、それらのリード端子付き陽極と陰極とをセパレータを介して巻回して、コンデンサ素子を作製した。 After etching the surface of the aluminum foil, lead terminals are attached to the anode on which the dielectric layer is formed by chemical conversion treatment, and lead terminals are attached to the cathode made of aluminum foil. Was wound through a separator to prepare a capacitor element.
上記コンデンサ素子を実施例１〜２０および比較例１〜３用にそれぞれ２０個ずつ用意し、それらコンデンサ素子を製造例１〜２０および比較製造例１〜３の導電性高分子組成物の分散液にそれぞれ別々に１０分間浸漬し、取り出した後、１５０℃で３０分間乾燥した。これらの操作を３回繰り返すことにより導電性高分子組成物からなる電解質の層を形成した。これを外装材で外装して、実施例１〜２０および比較例１〜３の巻回型アルミニウム電解コンデンサを計２０個ずつ製造した。 Twenty capacitor elements are prepared for Examples 1 to 20 and Comparative Examples 1 to 3, and these capacitor elements are used as dispersions of the conductive polymer compositions of Production Examples 1 to 20 and Comparative Production Examples 1 to 3. Each was immersed separately for 10 minutes, taken out, and then dried at 150 ° C. for 30 minutes. By repeating these operations three times, an electrolyte layer made of the conductive polymer composition was formed. This was exteriorized with an exterior material, and a total of 20 wound type aluminum electrolytic capacitors of Examples 1 to 20 and Comparative Examples 1 to 3 were manufactured.
上記のようにして製造した実施例１〜２０および比較例１〜３の巻回型アルミニウム電解コンデンサについて、ＥＳＲおよび静電容量を測定し、かつ、漏れ電流を測定し、漏れ電流不良の発生を調べた。その結果を使用した導電性高分子組成物の分散液の種類と共に表１に示す。なお、ＥＳＲ，静電容量および漏れ電流の測定方法ならびに漏れ電流不良の発生の評価方法は次の通りである。 With respect to the wound aluminum electrolytic capacitors of Examples 1 to 20 and Comparative Examples 1 to 3 manufactured as described above, the ESR and the capacitance are measured, and the leakage current is measured to prevent the occurrence of leakage current failure. Examined. The results are shown in Table 1 together with the types of dispersions of the conductive polymer composition using the results. The method for measuring ESR, capacitance and leakage current, and the method for evaluating the occurrence of leakage current failure are as follows.
ＥＳＲ：
ＨＥＷＬＥＴＴ ＰＡＣＫＡＲＤ社製のＬＣＲメーター（４２８４Ａ）を用い、２５℃の条件下で、１００ｋＨｚで測定する。
静電容量：
ＨＥＷＬＥＴＴ ＰＡＣＫＡＲＤ社製のＬＣＲメーター（４２８４Ａ）を用い、２５℃の条件下で、１２０Ｈｚで測定する。
漏れ電流：
巻回型アルミニウム電解コンデンサに、２５℃で３５Ｖの定格電圧を６０秒間印加した後、デジタルオシロスコープにて漏れ電流を測定する。
漏れ電流不良の発生：
上記漏れ電流測定で、漏れ電流が１００μＡ以上のものは、漏れ電流不良が発生していると判断する。
ESR:
It is measured at 100 kHz under the condition of 25 ° C. using an LCR meter (4284A) manufactured by Hewlett-Packard.
Capacitance:
It is measured at 120 Hz under the condition of 25 ° C. using an LCR meter (4284A) manufactured by Hewlett-Packard.
Leak current:
A rated voltage of 35 V at 25 ° C. is applied to the wound aluminum electrolytic capacitor for 60 seconds, and then the leakage current is measured with a digital oscilloscope.
Occurrence of leakage current failure:
In the above leakage current measurement, if the leakage current is 100 μA or more, it is determined that a leakage current defect has occurred.
上記の測定は、各試料とも、２０個ずつについて行い、ＥＳＲに関して表１に示す数値は、それら２０個の平均値を求め、小数点第２位を四捨五入して示したものであり、静電容量に関して表１に示す数値は、それら２０個の平均値を求め、小数点以下を四捨五入して示したものである。また、漏れ電流不良の発生の有無を調べた結果の表１および表２への表示にあたっては、試験に供した全コンデンサ個数を分母に示し、漏れ電流不良の発生があったコンデンサ個数を分子に示す態様で「漏れ電流不良発生個数」として表示する。 The above measurement was performed for 20 samples for each sample, and the numerical values shown in Table 1 for ESR are the average values of these 20 samples, rounded to the first decimal place, and the capacitance. The numerical values shown in Table 1 are obtained by calculating the average value of these 20 values and rounding off to the nearest whole number. In addition, when displaying the results of examining the presence or absence of leakage current failure in Tables 1 and 2, the total number of capacitors used in the test is shown in the denominator, and the number of capacitors in which leakage current failure has occurred is used as the numerator. In the manner shown, it is displayed as "the number of leakage current defects".
また、上記特性評価後の実施例１〜２０および比較例１〜３の巻回型アルミニウム電解コンデンサ（それぞれ１０個ずつ）に３５Ｖの定格電圧をかけながら、８５℃／８５％（上記の８５％は相対湿度が８５％であることを示しており、これは以下においても同様である）の恒温槽中に静電状態で貯蔵し、３００時間後に、前記と同様に、ＥＳＲおよび静電容量の測定を行った。その貯蔵期間中に、漏れ電流が５００μＡを超えたものに関しては、ショート不良（短絡発生不良）とした。その結果を表２に前記表１の場合と同様の態様で示す。ただし、ショート不良に関しては、試験に供した全コンデンサ個数を分母に示し、ショート不良が発生したコンデンサ個数を分子に示す態様で表示した。 Further, while applying a rated voltage of 35 V to the wound aluminum electrolytic capacitors (10 each) of Examples 1 to 20 and Comparative Examples 1 to 3 after the above characteristic evaluation, 85 ° C./85% (85% above). Indicates that the relative humidity is 85%, which is also the case below) and stored in a constant temperature bath in an electrostatic state, and after 300 hours, the ESR and capacitance as described above. Measurements were made. If the leakage current exceeds 500 μA during the storage period, it is regarded as a short-circuit defect (short-circuit occurrence defect). The results are shown in Table 2 in the same manner as in Table 1 above. However, regarding short-circuit defects, the total number of capacitors used in the test is shown in the denominator, and the number of capacitors in which short-circuit defects occur is shown in the numerator.
前記の表１に示すように、実施例１〜２０の巻回型アルミニウム電解コンデンサ（以下、巻回型アルミニウム電解コンデンサを簡略化して、「コンデンサ」と表示する場合がある）は、比較例１〜３のコンデンサに比べて、ＥＳＲが低かった（つまり、ＥＳＲが小さかった）。また、表２に示すように、８５℃８５％の恒温槽中で３００時間貯蔵後も、実施例１〜２０のコンデンサは、比較例１〜３のコンデンサに比べて、ＥＳＲが低く、高温高湿下での貯蔵によるＥＳＲの増加が少なく、高温高湿下の使用での信頼性が高いことを示していた。 As shown in Table 1 above, the wound aluminum electrolytic capacitors of Examples 1 to 20 (hereinafter, the wound aluminum electrolytic capacitors may be abbreviated and referred to as “capacitors”) are used in Comparative Example 1. The ESR was low (ie, the ESR was small) compared to the capacitors of ~ 3. Further, as shown in Table 2, even after storage for 300 hours in a constant temperature bath at 85 ° C. and 85%, the capacitors of Examples 1 to 20 have lower ESR and higher temperature than the capacitors of Comparative Examples 1 to 3. The increase in ESR due to storage under wet conditions was small, indicating high reliability in use under high temperature and high humidity.
［巻回型アルミニウム固体電解コンデンサでの評価（２）］
実施例２１〜４０および比較例４〜６
この実施例２１〜４０および比較例４〜６では、導電性高分子組成物からなる電解質と電解液とを併用した巻回型アルミニウム電解コンデンサを製造して、その特性を評価する。
[Evaluation with a wound aluminum solid electrolytic capacitor (2)]
Examples 21-40 and Comparative Examples 4-6
In Examples 21 to 40 and Comparative Examples 4 to 6, wound aluminum electrolytic capacitors in which an electrolyte made of a conductive polymer composition and an electrolytic solution are used in combination are manufactured, and their characteristics are evaluated.
アルミニウム箔の表面をエッチング処理した後、化成処理を行って誘電体層を形成した陽極にリード端子を取り付け、また、アルミニウム箔からなる陰極にリード端子を取り付け、それらのリード端子付き陽極と陰極とをセパレータを介して巻回して、コンデンサ素子を作製した。 After etching the surface of the aluminum foil, lead terminals are attached to the anode on which the dielectric layer is formed by chemical conversion treatment, and lead terminals are attached to the cathode made of aluminum foil. Was wound through a separator to prepare a capacitor element.
上記コンデンサ素子を実施例２１〜４０および比較例４〜６用にそれぞれ２０個ずつ用意し、それらコンデンサ素子を製造例１〜２０および比較製造例１〜３の導電性高分子組成物の分散液にそれぞれ別々に１０分間浸漬し、取り出した後、１５０℃で３０分間乾燥した。これらの操作を２回繰り返すことにより導電性高分子組成物からなる電解質の層を形成した。その後、電解液としての１０％アジピン酸トリメチルアミンのエチレングリコール溶液（アジピン酸トリメチルアミンが１０％溶解しているエチレングリコール溶液）に上記コンデンサ素子を１０分間浸漬し、取り出した後、これを外装材で外装して、実施例２１〜４０および比較例４〜６の巻回型アルミニウム電解コンデンサを計２０個ずつ製造した。 Twenty of the above capacitor elements were prepared for Examples 21 to 40 and Comparative Examples 4 to 6, respectively, and these capacitor elements were used as dispersions of the conductive polymer compositions of Production Examples 1 to 20 and Comparative Production Examples 1 to 3. Each was immersed separately for 10 minutes, taken out, and then dried at 150 ° C. for 30 minutes. By repeating these operations twice, an electrolyte layer made of the conductive polymer composition was formed. Then, the capacitor element is immersed in an ethylene glycol solution of 10% trimethylamine adipate (ethylene glycol solution in which 10% trimethylamine adipate is dissolved) as an electrolytic solution for 10 minutes, taken out, and then exteriorized with an exterior material. Then, a total of 20 wound aluminum electrolytic capacitors of Examples 21 to 40 and Comparative Examples 4 to 6 were manufactured.
上記のようにして製造した実施例２１〜４０および比較例４〜６の巻回型アルミニウム電解コンデンサについて、実施例１と同様に、ＥＳＲおよび静電容量を測定し、かつ、漏れ電流を測定し、漏れ電流不良の発生を調べた。その結果を表３に前記表１の場合と同様の態様で示す。 For the wound aluminum electrolytic capacitors of Examples 21 to 40 and Comparative Examples 4 to 6 manufactured as described above, the ESR and the capacitance were measured and the leakage current was measured in the same manner as in Example 1. , The occurrence of leakage current failure was investigated. The results are shown in Table 3 in the same manner as in Table 1 above.
また、上記特性評価後の実施例２１〜４０および比較例４〜６の巻回型アルミニウム電解コンデンサ（それぞれ１０個ずつ）に３５Ｖの定格電圧をかけながら、８５℃８５％の恒温槽中に静電状態で貯蔵し、５００時間後に、前記と同様に、ＥＳＲおよび静電容量の測定を行った。その貯蔵期間中に、漏れ電流が５００μＡを超えたものに関しては、ショート不良とした。その結果を表４に前記表２の場合と同様の態様で示す。 Further, while applying a rated voltage of 35 V to the wound aluminum electrolytic capacitors (10 each) of Examples 21 to 40 and Comparative Examples 4 to 6 after the above characteristic evaluation, they are static electricity in a constant temperature bath at 85 ° C. and 85%. It was stored in an electric state, and after 500 hours, ESR and capacitance were measured in the same manner as described above. If the leakage current exceeds 500 μA during the storage period, it is regarded as a short-circuit defect. The results are shown in Table 4 in the same manner as in Table 2 above.
前記の表３に示すように、実施例２１〜４０の巻回型アルミニウム電解コンデンサ（以下、巻回型アルミニウム電解コンデンサを簡略化して、「コンデンサ」と表示する場合がある）は、比較例４〜６のコンデンサに比べて、ＥＳＲが低かった（つまり、ＥＳＲが小さかった）。また、表４に示すように、８５℃８５％の恒温槽中に５００時間貯蔵後も、実施例２１〜４０のコンデンサは、比較例４〜６のコンデンサに比べて、ＥＳＲが低く、高温高湿下での貯蔵によるＥＳＲの増加が少なく、高温高湿下の使用での信頼性が高いことを示していた。 As shown in Table 3 above, the wound aluminum electrolytic capacitors of Examples 21 to 40 (hereinafter, the wound aluminum electrolytic capacitors may be abbreviated and referred to as “capacitors”) are used in Comparative Example 4. The ESR was low (ie, the ESR was small) compared to the capacitors of ~ 6. Further, as shown in Table 4, even after storage in a constant temperature bath at 85 ° C. and 85% for 500 hours, the capacitors of Examples 21 to 40 have lower ESR and higher temperature than the capacitors of Comparative Examples 4 to 6. The increase in ESR due to storage under wet conditions was small, indicating high reliability in use under high temperature and high humidity.
［タンタル電解コンデンサでの評価］
実施例４１
この実施例４１やそれに続く実施例４２〜５０および比較例７〜９では、タンタル電解コンデンサを製造して、その特性を評価する。
[Evaluation with tantalum electrolytic capacitors]
Example 41
In this Example 41 and subsequent Examples 42 to 50 and Comparative Examples 7 to 9, tantalum electrolytic capacitors are manufactured and their characteristics are evaluated.
タンタル焼結体を濃度が１％のリン酸水溶液に浸漬した状態で、３５Ｖの電圧を印加することによって化成処理を行い、タンタル焼結体の表面に酸化被膜を形成して誘電体層を構成して、コンデンサ素子を作製した。 A tantalum sintered body is immersed in a phosphoric acid aqueous solution having a concentration of 1%, and a chemical conversion treatment is performed by applying a voltage of 35 V to form an oxide film on the surface of the tantalum sintered body to form a dielectric layer. Then, a capacitor element was manufactured.
上記コンデンサ素子を濃度が３５％のエチレンジオキシチオフェン溶液のエタノール溶液に浸漬し、１分後に取り出し、５分間放置した。その後、あらかじめ用意しておいた濃度が５０％のフェノールスルホン酸ブチルアミン水溶液（ｐＨ５）と濃度が３０％の過硫酸アンモニウム水溶液とを質量比１：１で混合した混合物からなる酸化剤兼ドーパント溶液中に浸漬し、３０秒後に取り出し、室温で３０分間放置した後、５０℃で１０分間加熱して、重合を行った。重合後、水中に上記コンデンサ素子を浸漬し、３０分間放置した後、取り出して７０℃で３０分間乾燥した。この操作を６回繰り返して、コンデンサ素子上にエチレンジオキシチオフェンをモノマー成分とするπ共役系高分子にドーパントのフェノールスルホン酸ブチルアミンがドーピングしてなる導電性高分子組成物からなる電解質の層を形成した。 The capacitor element was immersed in an ethanol solution of an ethylenedioxythiophene solution having a concentration of 35%, taken out after 1 minute, and left to stand for 5 minutes. Then, in an oxidizing agent / dopant solution consisting of a mixture of a butylamine phenol sulfonate aqueous solution (pH 5) having a concentration of 50% and an ammonium persulfate aqueous solution having a concentration of 30% mixed at a mass ratio of 1: 1 prepared in advance. The mixture was immersed, taken out after 30 seconds, left at room temperature for 30 minutes, and then heated at 50 ° C. for 10 minutes to carry out polymerization. After the polymerization, the capacitor element was immersed in water, left for 30 minutes, taken out, and dried at 70 ° C. for 30 minutes. This operation is repeated 6 times to form an electrolyte layer composed of a conductive polymer composition obtained by doping a π-conjugated polymer containing ethylenedioxythiophene as a monomer component with a dopant butylamine phenol sulfonate on a capacitor element. Formed.
上記のようにして、いわゆる「その場重合」による導電性高分子組成物からなる電解質の層を形成したコンデンサ素子を製造例２１で得た導電性高分子組成物の分散液に浸漬し、３０秒後に取り出し、１５０℃で３０分間乾燥した。この操作を３回繰り返した後、１５０℃で６０分間放置して、本発明に係る導電性高分子組成物からなる電解質の層を形成した。その後、カーボンペースト、銀ペーストで上記電解質層を覆ってタンタル電解コンデンサを製造した。 As described above, the capacitor element in which the electrolyte layer made of the conductive polymer composition by so-called "in-situ polymerization" is formed is immersed in the dispersion liquid of the conductive polymer composition obtained in Production Example 21 and 30 After seconds, it was taken out and dried at 150 ° C. for 30 minutes. After repeating this operation three times, the mixture was left at 150 ° C. for 60 minutes to form an electrolyte layer made of the conductive polymer composition according to the present invention. Then, the tantalum electrolytic capacitor was manufactured by covering the electrolyte layer with carbon paste and silver paste.
実施例４２
製造例２１の導電性高分子組成物の分散液に代えて、製造例２２の導電性高分子組成物の分散液を用いた以外は、すべて実施例４１と同様の操作を行って、タンタル電解コンデンサを製造した。
Example 42
Tantalum electrolysis was carried out in the same manner as in Example 41 except that the dispersion liquid of the conductive polymer composition of Production Example 22 was used instead of the dispersion liquid of the conductive polymer composition of Production Example 22. Manufactured a capacitor.
実施例４３
製造例２１の導電性高分子組成物の分散液に代えて、製造例２３の導電性高分子組成物の分散液を用いた以外は、すべて実施例４１と同様の操作を行って、タンタル電解コンデンサを製造した。
Example 43
Tantalum electrolysis was carried out in the same manner as in Example 41 except that the dispersion liquid of the conductive polymer composition of Production Example 23 was used instead of the dispersion liquid of the conductive polymer composition of Production Example 23. Manufactured a capacitor.
実施例４４
製造例２１の導電性高分子組成物の分散液に代えて、製造例２４の導電性高分子組成物の分散液を用いた以外は、すべて実施例４１と同様の操作を行って、タンタル電解コンデンサを製造した。
Example 44
Tantalum electrolysis was carried out in the same manner as in Example 41 except that the dispersion liquid of the conductive polymer composition of Production Example 24 was used instead of the dispersion liquid of the conductive polymer composition of Production Example 24. Manufactured a capacitor.
実施例４５
製造例２１の導電性高分子組成物の分散液に代えて、製造例２５の導電性高分子組成物の分散液を用いた以外は、すべて実施例４１と同様の操作を行って、タンタル電解コンデンサを製造した。
Example 45
Tantalum electrolysis was carried out in the same manner as in Example 41 except that the dispersion liquid of the conductive polymer composition of Production Example 25 was used instead of the dispersion liquid of the conductive polymer composition of Production Example 21. Manufactured a capacitor.
実施例４６
製造例２１の導電性高分子組成物の分散液に代えて、製造例２６の導電性高分子組成物の分散液を用いた以外は、すべて実施例４１と同様の操作を行って、タンタル電解コンデンサを製造した。
Example 46
Tantalum electrolysis was carried out in the same manner as in Example 41 except that the dispersion liquid of the conductive polymer composition of Production Example 26 was used instead of the dispersion liquid of the conductive polymer composition of Production Example 26. Manufactured a capacitor.
実施例４７
製造例２１の導電性高分子組成物の分散液に代えて、製造例２７の導電性高分子組成物の分散液を用いた以外は、すべて実施例４１と同様の操作を行って、タンタル電解コンデンサを製造した。
Example 47
Tantalum electrolysis was carried out in the same manner as in Example 41 except that the dispersion liquid of the conductive polymer composition of Production Example 27 was used instead of the dispersion liquid of the conductive polymer composition of Production Example 21. Manufactured a capacitor.
実施例４８
製造例２１の導電性高分子組成物の分散液に代えて、製造例２８の導電性高分子組成物の分散液を用いた以外は、すべて実施例４１と同様の操作を行って、タンタル電解コンデンサを製造した。
Example 48
Tantalum electrolysis was carried out in the same manner as in Example 41 except that the dispersion liquid of the conductive polymer composition of Production Example 28 was used instead of the dispersion liquid of the conductive polymer composition of Production Example 28. Manufactured a capacitor.
実施例４９
製造例２１の導電性高分子組成物の分散液に代えて、製造例２９の導電性高分子組成物の分散液を用いた以外は、すべて実施例４１と同様の操作を行って、タンタル電解コンデンサを製造した。
Example 49
Tantalum electrolysis was carried out in the same manner as in Example 41 except that the dispersion liquid of the conductive polymer composition of Production Example 29 was used instead of the dispersion liquid of the conductive polymer composition of Production Example 21. Manufactured a capacitor.
実施例５０
製造例２１の導電性高分子組成物の分散液に代えて、製造例３０の導電性高分子組成物の分散液を用いた以外は、すべて実施例４１と同様の操作を行って、タンタル電解コンデンサを製造した。
Example 50
Tantalum electrolysis was carried out in the same manner as in Example 41 except that the dispersion liquid of the conductive polymer composition of Production Example 30 was used instead of the dispersion liquid of the conductive polymer composition of Production Example 21. Manufactured a capacitor.
比較例７
製造例２１の導電性高分子組成物の分散液に代えて、比較製造例１の導電性高分子組成物の分散液を用いた以外は、すべて実施例４１と同様の操作を行って、タンタル電解コンデンサを製造した。
Comparative Example 7
Tantalum was operated in the same manner as in Example 41 except that the dispersion liquid of the conductive polymer composition of Comparative Production Example 1 was used instead of the dispersion liquid of the conductive polymer composition of Production Example 21. Manufactured electrolytic capacitors.
比較例８
製造例２１の導電性高分子組成物の分散液に代えて、比較製造例２の導電性高分子組成物の分散液を用いた以外は、すべて実施例４１と同様の操作を行って、タンタル電解コンデンサを製造した。
Comparative Example 8
Tantalum was operated in the same manner as in Example 41 except that the dispersion liquid of the conductive polymer composition of Comparative Production Example 2 was used instead of the dispersion liquid of the conductive polymer composition of Production Example 21. Manufactured electrolytic capacitors.
比較例９
製造例２１の導電性高分子組成物の分散液に代えて、比較製造例３の導電性高分子組成物の分散液を用いた以外は、すべて実施例４１と同様の操作を行って、タンタル電解コンデンサを製造した。
Comparative Example 9
All the same operations as in Example 41 were performed except that the dispersion liquid of the conductive polymer composition of Comparative Production Example 3 was used instead of the dispersion liquid of the conductive polymer composition of Production Example 21. Manufactured electrolytic capacitors.
上記のように製造した実施例４１〜５０および比較例７〜９のタンタル電解コンデンサについて、前記と同様に、そのＥＳＲおよび静電容量を測定した。その結果を使用した導電性高分子組成物の分散液の種類と共に表５に示す。なお、ＥＳＲおよび静電容量の測定においては、いずれの試料も、１０個ずつを用い、表５に示すＥＳＲ値は、それら１０個の平均値を求め、小数点第２位を四捨五入して示したものであり、表５に静電容量値は、それら１０個の平均値を求め、小終点以下を四捨五入して示したものである。 The ESR and capacitance of the tantalum electrolytic capacitors of Examples 41 to 50 and Comparative Examples 7 to 9 manufactured as described above were measured in the same manner as described above. The results are shown in Table 5 together with the types of dispersions of the conductive polymer composition using the results. In the measurement of ESR and capacitance, 10 samples were used for each sample, and the ESR values shown in Table 5 were obtained by calculating the average value of these 10 samples and rounding off to the second decimal place. Table 5 shows the capacitance values obtained by calculating the average value of these 10 values and rounding off to the nearest whole number.
また、上記実施例４１〜５０および比較例７〜９のタンタル電解コンデンサをそれぞれ１０個ずつ、８５℃８５％で３００時間貯蔵した後、前記と同様に、ＥＳＲおよび静電容量を測定した。その結果を表６に前記表５と同様の態様で示す。 In addition, 10 tantalum electrolytic capacitors of Examples 41 to 50 and Comparative Examples 7 to 9 were stored at 85 ° C. and 85% for 300 hours, and then the ESR and capacitance were measured in the same manner as described above. The results are shown in Table 6 in the same manner as in Table 5.
前記の表５に示すように、実施例４１〜５０のタンタル電解コンデンサ（以下、タンタル電解コンデンサを、簡略化して「コンデンサ」と表示する場合がある）は、比較例７〜９のコンデンサに比べて、ＥＳＲが低く、コンデンサとしての特性が優れていた。また、表６に示すように、８５℃８５％で３００時間貯蔵後も、実施例４１〜５０のコンデンサは、比較例７〜９のコンデンサに比べて、ＥＳＲが低く、高温高湿下での貯蔵によるＥＳＲの増加が少なく、高温高湿下の使用での信頼性が高いことを示していた。 As shown in Table 5 above, the tantalum electrolytic capacitors of Examples 41 to 50 (hereinafter, the tantalum electrolytic capacitors may be abbreviated as "capacitors") are compared with the capacitors of Comparative Examples 7 to 9. Therefore, the ESR was low and the characteristics as a capacitor were excellent. Further, as shown in Table 6, even after storage at 85 ° C. and 85% for 300 hours, the capacitors of Examples 41 to 50 have a lower ESR than the capacitors of Comparative Examples 7 to 9, and are under high temperature and high humidity. The increase in ESR due to storage was small, indicating high reliability in use under high temperature and high humidity.
［積層型アルミニウム電解コンデンサでの評価］
実施例５１〜６０および比較例１０〜１２
この実施例５１〜６０および比較例１０〜１２では、以下に示すように積層型アルミニウム電解コンデンサを製造して、その特性を評価する。
[Evaluation with laminated aluminum electrolytic capacitors]
Examples 51-60 and Comparative Examples 10-12
In Examples 51 to 60 and Comparative Examples 10 to 12, multilayer aluminum electrolytic capacitors are manufactured and their characteristics are evaluated as shown below.
実施例５１
縦１０ｍｍ×横３．３ｍｍのアルミニウムエッチド箔について、縦方向の一方の端から４ｍｍの部分と、他方の端から５ｍｍの部分とに分けるように、上記箔の横方向に幅１ｍｍでポリイミド溶液を塗布し、乾燥した。次に、上記アルミニウムエッチド箔の縦方向の片端（だだし、前記他方の端）から５ｍｍの部分の、該片端から２ｍｍの箇所に、陽極としての銀線を取り付けた。また、上記箔の縦方向の片端（だだし、前記一方の端）から４ｍｍの部分（４ｍｍ×３．３ｍｍ）を、濃度が１０％のアジピン酸アンモニウム水溶液を用いて化成処理を行って誘電体層を形成し、設定静電容量が２５μＦ以上、設定ＥＳＲが１０ｍΩ以下のコンデンサ素子を作製した。
Example 51
A polyimide solution having a width of 1 mm in the horizontal direction of the foil so as to divide an aluminum-etched foil having a length of 10 mm and a width of 3.3 mm into a portion 4 mm from one end in the vertical direction and a portion 5 mm from the other end. Was applied and dried. Next, a silver wire as an anode was attached to a portion of the aluminum-etched foil 5 mm from one end in the vertical direction (dashi, the other end) and 2 mm from the one end. Further, a portion (4 mm × 3.3 mm) of the foil 4 mm from one end in the vertical direction (the one end) is subjected to chemical conversion treatment using an aqueous solution of ammonium adipate having a concentration of 10% to form a dielectric material. A layer was formed to prepare a capacitor element having a set capacitance of 25 μF or more and a set ESR of 10 mΩ or less.
次に、上記コンデンサ素子を製造例１の導電性高分子組成物の分散液に浸漬し、１分後に取り出し、１２０℃で１０分間乾燥する操作を３回繰り返した。その後、酸化防止剤として販売されているテイカトロンＫＡ１００（フェノールスルホン酸塩）をエタノールと水を容量比で等量混合した混合液に濃度５％になるように溶解した溶液に上記コンデンサ素子を浸漬し、１分後に取り出し、１２０℃で５分間乾燥した。その後、製造例２２の導電性高分子組成物の分散液に上記コンデンサ素子を浸漬し、１分後に取り出し、１２０℃で３０分間乾燥した。その後、カーボンペーストおよび銀ペーストで導電性高分子組成物層からなる電解質層を覆い、縦方向の端部から３ｍｍの箇所に陰極としての銀線を取り付け、さらにエポキシ樹脂で外装し、エージング処理を行って、積層型アルミニウム電解コンデンサを製造した。 Next, the operation of immersing the capacitor element in the dispersion liquid of the conductive polymer composition of Production Example 1, taking it out after 1 minute, and drying it at 120 ° C. for 10 minutes was repeated three times. Then, the condenser element is immersed in a solution prepared by dissolving Teikatron KA100 (phenol sulfonate), which is sold as an antioxidant, in a mixture of ethanol and water in equal amounts in a volume ratio so as to have a concentration of 5%. After 1 minute, it was taken out and dried at 120 ° C. for 5 minutes. Then, the capacitor element was immersed in the dispersion liquid of the conductive polymer composition of Production Example 22, taken out after 1 minute, and dried at 120 ° C. for 30 minutes. After that, the electrolyte layer composed of the conductive polymer composition layer is covered with carbon paste and silver paste, a silver wire as a cathode is attached at a position 3 mm from the end in the vertical direction, and the surface is further covered with epoxy resin for aging treatment. A monolithic aluminum electrolytic capacitor was manufactured.
実施例５２
製造例１の導電性高分子組成物の分散液に代えて、製造例２の導電性高分子組成物の分散液を用いた以外は、すべて実施例５１と同様の操作を行って、積層型アルミニウム電解コンデンサを製造した。
Example 52
The same operation as in Example 51 was performed except that the dispersion liquid of the conductive polymer composition of Production Example 2 was used instead of the dispersion liquid of the conductive polymer composition of Production Example 1, and the laminated type was used. Manufactured aluminum electrolytic capacitors.
実施例５３
製造例１の導電性高分子組成物の分散液に代えて、製造例４の導電性高分子組成物の分散液を用いた以外は、すべて実施例５１と同様の操作を行って、積層型アルミニウム電解コンデンサを製造した。
Example 53
The same operation as in Example 51 was performed except that the dispersion liquid of the conductive polymer composition of Production Example 4 was used instead of the dispersion liquid of the conductive polymer composition of Production Example 1, and the laminated type was used. Manufactured aluminum electrolytic capacitors.
実施例５４
製造例１の導電性高分子組成物の分散液に代えて、製造例６の導電性高分子組成物の分散液を用いた以外は、すべて実施例５１と同様の操作を行って、積層型アルミニウム電解コンデンサを製造した。
Example 54
The same operation as in Example 51 was performed except that the dispersion liquid of the conductive polymer composition of Production Example 6 was used instead of the dispersion liquid of the conductive polymer composition of Production Example 1, and the laminated type was used. Manufactured aluminum electrolytic capacitors.
実施例５５
製造例１の導電性高分子組成物の分散液に代えて、製造例８の導電性高分子組成物の分散液を用いた以外は、すべて実施例５１と同様の操作を行って、積層型アルミニウム電解コンデンサを製造した。
Example 55
The same operation as in Example 51 was performed except that the dispersion liquid of the conductive polymer composition of Production Example 8 was used instead of the dispersion liquid of the conductive polymer composition of Production Example 1, and the laminated type was used. Manufactured aluminum electrolytic capacitors.
実施例５６
製造例１の導電性高分子組成物の分散液に代えて、製造例１１の導電性高分子組成物の分散液を用い、かつ、製造例２２の導電性高分子組成物の分散液に代えて、製造例２３の導電性高分子組成物の分散液を用いた以外は、すべて実施例５１と同様の操作を行って、積層型アルミニウム電解コンデンサを製造した。
Example 56
Instead of the dispersion liquid of the conductive polymer composition of Production Example 1, the dispersion liquid of the conductive polymer composition of Production Example 11 is used, and instead of the dispersion liquid of the conductive polymer composition of Production Example 22. The laminated aluminum electrolytic capacitor was manufactured by carrying out the same operations as in Example 51 except that the dispersion liquid of the conductive polymer composition of Production Example 23 was used.
実施例５７
製造例１の導電性高分子組成物の分散液に代えて、製造例１２の導電性高分子組成物の分散液を用い、かつ、製造例２２の導電性高分子組成物の分散液に代えて、製造例２５の導電性高分子組成物の分散液を用いた以外は、すべて実施例５１と同様の操作を行って、積層型アルミニウム電解コンデンサを製造した。
Example 57
Instead of the dispersion liquid of the conductive polymer composition of Production Example 1, the dispersion liquid of the conductive polymer composition of Production Example 12 is used, and instead of the dispersion liquid of the conductive polymer composition of Production Example 22. The laminated aluminum electrolytic capacitor was manufactured by carrying out the same operations as in Example 51 except that the dispersion liquid of the conductive polymer composition of Production Example 25 was used.
実施例５８
製造例１の導電性高分子組成物の分散液に代えて、製造例１４の導電性高分子組成物の分散液を用い、かつ、製造例２２の導電性高分子組成物の分散液に代えて、製造例２６の導電性高分子組成物の分散液を用いた以外は、すべて実施例５１と同様の操作を行って、積層型アルミニウム電解コンデンサを製造した。
Example 58
Instead of the dispersion liquid of the conductive polymer composition of Production Example 1, the dispersion liquid of the conductive polymer composition of Production Example 14 is used, and instead of the dispersion liquid of the conductive polymer composition of Production Example 22. The laminated aluminum electrolytic capacitor was manufactured by carrying out the same operations as in Example 51 except that the dispersion liquid of the conductive polymer composition of Production Example 26 was used.
実施例５９
製造例１の導電性高分子組成物の分散液に代えて、製造例１７の導電性高分子組成物の分散液を用い、かつ、製造例２２の導電性高分子組成物の分散液に代えて、製造例２７の導電性高分子組成物の分散液を用いた以外は、すべて実施例５１と同様の操作を行って、積層型アルミニウム電解コンデンサを製造した。
Example 59
Instead of the dispersion liquid of the conductive polymer composition of Production Example 1, the dispersion liquid of the conductive polymer composition of Production Example 17 is used, and instead of the dispersion liquid of the conductive polymer composition of Production Example 22. The laminated aluminum electrolytic capacitor was manufactured by carrying out the same operations as in Example 51 except that the dispersion liquid of the conductive polymer composition of Production Example 27 was used.
実施例６０
製造例１の導電性高分子組成物の分散液に代えて、製造例２０の導電性高分子組成物の分散液を用い、かつ、製造例２２の導電性高分子組成物の分散液に代えて、製造例２９の導電性高分子組成物の分散液を用いた以外は、すべて実施例５１と同様の操作を行って、積層型アルミニウム電解コンデンサを製造した。
Example 60
Instead of the dispersion liquid of the conductive polymer composition of Production Example 1, the dispersion liquid of the conductive polymer composition of Production Example 20 is used, and instead of the dispersion liquid of the conductive polymer composition of Production Example 22. The laminated aluminum electrolytic capacitor was manufactured by carrying out the same operations as in Example 51 except that the dispersion liquid of the conductive polymer composition of Production Example 29 was used.
比較例１０
製造例１の導電性高分子組成物の分散液に代えて、比較製造例１の導電性高分子組成物の分散液を用い、かつ、製造例２２の導電性高分子組成物の分散液に代えて、比較製造例１の導電性高分子組成物の分散液を用いた以外は、すべて実施例５１と同様の操作を行って、積層型アルミニウム電解コンデンサを製造した。
Comparative Example 10
Instead of the dispersion liquid of the conductive polymer composition of Production Example 1, the dispersion liquid of the conductive polymer composition of Comparative Production Example 1 is used, and the dispersion liquid of the conductive polymer composition of Production Example 22 is used. Instead, the same operation as in Example 51 was carried out except that the dispersion liquid of the conductive polymer composition of Comparative Production Example 1 was used to produce a laminated aluminum electrolytic capacitor.
比較例１１
製造例１の導電性高分子組成物の分散液に代えて、比較製造例２の導電性高分子組成物の分散液を用い、かつ、製造例２２の導電性高分子組成物の分散液に代えて、比較製造例２の導電性高分子組成物の分散液を用いた以外は、すべて実施例５１と同様の操作を行って、積層型アルミニウム電解コンデンサを製造した。
Comparative Example 11
Instead of the dispersion liquid of the conductive polymer composition of Production Example 1, the dispersion liquid of the conductive polymer composition of Comparative Production Example 2 is used, and the dispersion liquid of the conductive polymer composition of Production Example 22 is used. Instead, the same operation as in Example 51 was carried out except that the dispersion liquid of the conductive polymer composition of Comparative Production Example 2 was used to produce a laminated aluminum electrolytic capacitor.
比較例１２
製造例１の導電性高分子組成物の分散液に代えて、比較製造例３の導電性高分子組成物の分散液を用い、かつ、製造例２２の導電性高分子組成物の分散液に代えて、比較製造例３の導電性高分子組成物の分散液を用いた以外は、すべて実施例５１と同様の操作を行って、積層型アルミニウム電解コンデンサを製造した。
Comparative Example 12
Instead of the dispersion liquid of the conductive polymer composition of Production Example 1, the dispersion liquid of the conductive polymer composition of Comparative Production Example 3 is used, and the dispersion liquid of the conductive polymer composition of Production Example 22 is used. Instead, the same operation as in Example 51 was carried out except that the dispersion liquid of the conductive polymer composition of Comparative Production Example 3 was used to produce a laminated aluminum electrolytic capacitor.
上記のように製造した実施例５１〜６０および比較例１０〜１２の積層型アルミニウム電解コンデンサについて、前記と同様に、そのＥＳＲおよび静電容量を測定した。その結果を使用した導電性高分子組成物の分散液の種類と共に表７に示す。ただし、使用した導電性高分子組成物の分散液の表７への表示にあたっては、スペース上の関係で、「導電性高分子組成物の分散液」を簡略化して「分散液」で表示する。また、ＥＳＲおよび静電容量の測定においては、いずれの試料も、１０個ずつを用い、表７に示すＥＳＲ値および静電容量値は、それら１０個の平均値を求め、小数点第２位を四捨五入して示したものである。 The ESR and capacitance of the laminated aluminum electrolytic capacitors of Examples 51 to 60 and Comparative Examples 10 to 12 manufactured as described above were measured in the same manner as described above. The results are shown in Table 7 together with the types of dispersions of the conductive polymer composition using the results. However, in displaying the dispersion liquid of the conductive polymer composition used in Table 7, due to space limitations, the "dispersion liquid of the conductive polymer composition" is simply displayed as "dispersion liquid". .. In the measurement of ESR and capacitance, 10 samples were used for each sample, and the ESR value and capacitance value shown in Table 7 were obtained by calculating the average value of these 10 samples and setting the second decimal place. It is rounded off.
また、上記実施例５１〜６０および比較例１０〜１２の積層型アルミニウム電解コンデンサをそれぞれ１０個ずつ、８５℃８５％で１００時間貯蔵した後、前記と同様に、ＥＳＲおよび静電容量を測定した。その結果を表８に前記表７と同様の態様で示す。 In addition, 10 laminated aluminum electrolytic capacitors of Examples 51 to 60 and Comparative Examples 10 to 12 were stored at 85 ° C. and 85% for 100 hours, and then the ESR and capacitance were measured in the same manner as described above. .. The results are shown in Table 8 in the same manner as in Table 7.
前記の表７に示すように、実施例５１〜６０の積層型アルミニウム電解コンデンサ（以下、積層型アルミニウム電解コンデンサを、簡略化して「コンデンサ」と表示する場合がある）は、比較例１０〜１２のコンデンサに比べて、ＥＳＲが低く、コンデンサとしての特性が優れていた。また、実施例５１〜６０のコンデンサは、表８に示すように、８５℃８５％で１００時間貯蔵後も、比較例１０〜１２のコンデンサに比べて、ＥＳＲが低く、高温高湿下での貯蔵によるＥＳＲの増加が少なく、高温高湿下の使用での信頼性が高いことを示していた。 As shown in Table 7 above, the laminated aluminum electrolytic capacitors of Examples 51 to 60 (hereinafter, the laminated aluminum electrolytic capacitors may be abbreviated as "capacitors") are used in Comparative Examples 10 to 12. ESR was low and the characteristics as a capacitor were excellent as compared with the capacitor of. Further, as shown in Table 8, the capacitors of Examples 51 to 60 have a lower ESR than the capacitors of Comparative Examples 10 to 12 even after being stored at 85 ° C. and 85% for 100 hours, and are under high temperature and high humidity. The increase in ESR due to storage was small, indicating high reliability in use under high temperature and high humidity.
次に、実施例の導電性フィルムを構成するにあたって用いる導電性高分子組成物の分散液の製造を製造例３１〜３８で示し、比較例の導電性フィルムを構成するにあたって用いる導電性高分子組成物の分散液の製造を比較製造例４〜８で示す。 Next, the production of the dispersion liquid of the conductive polymer composition used for forming the conductive film of Examples is shown in Production Examples 31 to 38, and the conductive polymer composition used for forming the conductive film of Comparative Example is shown. The production of the dispersion liquid of the product is shown in Comparative Production Examples 4 to 8.
製造例３１
合成例１で得たスチレンスルホン酸とＮ−（２−ヒドロキシエチル）アクリルアミドとのモル比が９：１の共重合体の４％水溶液６００ｇを内容積１Ｌのステンレス鋼製容器に入れ、そこに触媒として硫酸第一鉄・７水和物を０．３ｇ添加して溶解した。その中にエチレンジオキシチオフェンを４ｍｌゆっくり滴下した。ステンレス鋼製の攪拌バネで攪拌し、容器に陽極を取り付け、攪拌バネに陰極を取り付け、１ｍＡ／ｃｍ２の定電流で１８時間電解酸化重合して、導電性高分子組成物を製造した。上記電解酸化重合後、水で４倍希釈した後、超音波ホモジナイザー［日本精機社製、ＵＳ−Ｔ３００（商品名）］で３０分間分散処理を行った。
Production Example 31
600 g of a 4% aqueous solution of a copolymer having a molar ratio of styrene sulfonic acid and N- (2-hydroxyethyl) acrylamide obtained in Synthesis Example 1 of 9: 1 was placed in a stainless steel container having an internal volume of 1 L and placed therein. As a catalyst, 0.3 g of ferrous sulfate heptahydrate was added and dissolved. 4 ml of ethylenedioxythiophene was slowly added dropwise thereto. A conductive polymer composition was produced by stirring with a stirring spring made of stainless steel, attaching an anode to the container, attaching a cathode to the stirring spring, and electrolytically oxidatively polymerizing at a constant current of 1 mA / cm 2 for 18 hours. After the above electrolytic oxidative polymerization, it was diluted 4-fold with water, and then dispersed with an ultrasonic homogenizer [US-T300 (trade name) manufactured by Nippon Seiki Co., Ltd.] for 30 minutes.
その後、オルガノ社のカチオン交換樹脂［アンバーライト１２０Ｂ（商品名）］を１００ｇ添加して、１時間攪拌機で撹拌し、次いで、東洋濾紙社製の濾紙Ｎｏ．１３１で濾過し、このカチオン交換樹脂による処理と濾過を３回繰り返して、液中のカチオン成分をすべて除去した。 Then, 100 g of Organo's cation exchange resin [Amberlite 120B (trade name)] was added and stirred with a stirrer for 1 hour, and then the filter paper No. 1 manufactured by Toyo Filter Paper Co., Ltd. was added. The mixture was filtered through 131, and the treatment with the cation exchange resin and the filtration were repeated three times to remove all the cation components in the liquid.
上記処理後の液を孔径が１μｍのフィルターに通し、その通過液を限外濾過装置［ザルトリウス社製Ｖｉｖａｆｌｏｗ２００（商品名）、分子量分画５万］で処理して、液中の遊離の低分子成分を除去した。この処理後の液を水で希釈して導電性高分子組成物の濃度を１．５％に調整し、その１．５％液４０ｇに対し、導電性向上剤として１，３−プロパンジオールを４ｇ添加して、導電性向上剤としての１，３−プロパンジオールを添加した導電性高分子の分散液を得た。上記１，３−プロパンジオールの添加量は導電性高分子に対して６６６％であった。このような１，３−プロパンジオールの添加は、以下に示す製造例３１〜３８及び比較製造例７〜１１の導電性高分子組成物の分散液に対しても同様に行われる。 The liquid after the above treatment is passed through a filter having a pore size of 1 μm, and the passing liquid is treated with an ultrafiltration device [Vivaflow200 (trade name) manufactured by Sartorius, molecular weight fraction 50,000] to release low molecules in the liquid. The component was removed. The liquid after this treatment is diluted with water to adjust the concentration of the conductive polymer composition to 1.5%, and 1,3-propanediol is added as a conductivity improver to 40 g of the 1.5% liquid. By adding 4 g, a dispersion liquid of a conductive polymer to which 1,3-propanediol as a conductivity improver was added was obtained. The amount of 1,3-propanediol added was 666% with respect to the conductive polymer. Such addition of 1,3-propanediol is also carried out in the same manner for the dispersion liquids of the conductive polymer compositions of Production Examples 31 to 38 and Comparative Production Examples 7 to 11 shown below.
製造例３２
合成例１で得た共重合体に代えて、合成例２で得たスチレンスルホン酸とＮ−（２−ヒドロキシエチル）アクリルアミドとのモル比が７：３の共重合体を用いた以外は、すべて製造例３１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Production example 32
A copolymer having a molar ratio of styrene sulfonic acid and N- (2-hydroxyethyl) acrylamide of 7: 3 obtained in Synthesis Example 2 was used instead of the copolymer obtained in Synthesis Example 1. The same operation as in Production Example 31 was carried out to obtain a dispersion liquid of the conductive polymer composition.
製造例３３
合成例１で得た共重合体に代えて、合成例４で得たスチレンスルホン酸とＮ−（ヒドロキシメチル）アクリルアミドとのモル比が９：１の共重合体を用いた以外は、すべて製造例３１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Production example 33
All were produced except that the copolymer obtained in Synthesis Example 1 was replaced with the copolymer obtained in Synthesis Example 4 in which the molar ratio of styrene sulfonic acid to N- (hydroxymethyl) acrylamide was 9: 1. The same operation as in Example 31 was carried out to obtain a dispersion liquid of the conductive polymer composition.
製造例３４
合成例１で得た共重合体に代えて、合成例６で得たスチレンスルホン酸とＮ−メチルメタクリルアミドとのモル比が９：１の共重合体を用いた以外は、すべて製造例３１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Production example 34
Production Example 31 except that a copolymer obtained in Synthesis Example 6 having a molar ratio of styrene sulfonic acid and N-methylmethacrylamide of 9: 1 was used instead of the copolymer obtained in Synthesis Example 1. The same operation as in the above was carried out to obtain a dispersion liquid of the conductive polymer composition.
製造例３５
合成例１で得た共重合体に代えて、合成例８で得たスチレンスルホン酸とＮ−（４−ヒドロキシフェニル）メタクリルアミドとのモル比が９：１の共重合体を用いた以外は、すべて製造例３１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Production example 35
Instead of the copolymer obtained in Synthesis Example 1, a copolymer having a molar ratio of styrene sulfonic acid and N- (4-hydroxyphenyl) methacrylamide obtained in Synthesis Example 8 of 9: 1 was used. The same operation as in Production Example 31 was carried out to obtain a dispersion liquid of the conductive polymer composition.
製造例３６
合成例１で得た共重合体に代えて、合成例１０で得たスチレンスルホン酸とＮ−フェニルアクリルアミドとのモル比が９．５：０．５の共重合体を用いた以外は、すべて製造例３１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Production example 36
All except the copolymer obtained in Synthesis Example 10 having a molar ratio of styrene sulfonic acid to N-phenylacrylamide of 9.5: 0.5 was used instead of the copolymer obtained in Synthesis Example 10. The same operation as in Production Example 31 was carried out to obtain a dispersion liquid of the conductive polymer composition.
製造例３７
合成例１で得た共重合体に代えて、合成例１１で得たスチレンスルホン酸とＮ−フェニルアクリルアミドとのモル比が９：１の共重合体を用いた以外は、すべて製造例３１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Production example 37
Except for the copolymer obtained in Synthesis Example 1 in which the molar ratio of styrene sulfonic acid and N-phenylacrylamide obtained in Synthesis Example 11 was 9: 1, all of the copolymers were the same as those of Production Example 31. The same operation was carried out to obtain a dispersion liquid of the conductive polymer composition.
製造例３８
合成例１で得た共重合体に代えて、合成例１２で得たスチレンスルホン酸とＮ−フェニルアクリルアミドとのモル比が７：３の共重合体を用いた以外は、すべて製造例３１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Production example 38
In place of the copolymer obtained in Synthesis Example 1, a copolymer having a molar ratio of styrene sulfonic acid and N-phenylacrylamide obtained in Synthesis Example 12 of 7: 3 was used, but all of the copolymers were the same as those of Production Example 31. The same operation was carried out to obtain a dispersion liquid of the conductive polymer composition.
比較製造例４
合成例１で得た共重合体に代えて、ポリスチレンスルホン酸（テイカ社製、重量平均分子量１００，０００）を用いた以外は、すべて製造例３１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Comparative manufacturing example 4
Except for the use of polystyrene sulfonic acid (manufactured by Teika Co., Ltd., weight average molecular weight of 100,000) instead of the copolymer obtained in Synthesis Example 1, the same operations as in Production Example 31 were carried out to carry out the same operation as in Production Example 31. A dispersion of the composition was obtained.
比較製造例５
合成例１で得た共重合体に代えて、比較合成例１で得たスチレンスルホン酸とメタクリル酸ヒドロキシエチルとのモル比が９：１の共重合体を用いた以外は、すべて製造例３１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Comparative manufacturing example 5
Production Example 31 except that a copolymer obtained in Comparative Synthesis Example 1 having a molar ratio of styrene sulfonic acid and hydroxyethyl methacrylate of 9: 1 was used instead of the copolymer obtained in Synthesis Example 1. The same operation as in the above was carried out to obtain a dispersion liquid of the conductive polymer composition.
比較製造例６
合成例１で得た共重合体に代えて、比較合成例２で得たスチレンスルホン酸とメタクリル酸ヒドロキシエチルとのモル比が７：３の共重合体を用いた以外は、すべて製造例３１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Comparative manufacturing example 6
Production Example 31 except that a copolymer obtained in Comparative Synthesis Example 2 having a molar ratio of styrene sulfonic acid and hydroxyethyl methacrylate of 7: 3 was used instead of the copolymer obtained in Synthesis Example 1. The same operation as in the above was carried out to obtain a dispersion liquid of the conductive polymer composition.
比較製造例７
合成例１で得た共重合体に代えて、比較合成例３で得たスチレンスルホン酸と３−アクリロキシプロピルトリメトキシシランとのモル比が９：１の共重合体を用いた以外は、すべて製造例３１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Comparative manufacturing example 7
Instead of the copolymer obtained in Synthesis Example 1, a copolymer having a molar ratio of styrene sulfonic acid and 3-acryloxypropyltrimethoxysilane obtained in Comparative Synthesis Example 3 of 9: 1 was used, except that the copolymer was used. The same operation as in Production Example 31 was carried out to obtain a dispersion liquid of the conductive polymer composition.
比較製造例８
合成例１で得た共重合体に代えて、比較合成例４で得たスチレンスルホン酸と３−アクリロキシプロピルトリメトキシシランとのモル比が７：３の共重合体を用いた以外は、すべて製造例３１と同様の操作を行って、導電性高分子組成物の分散液を得た。
Comparative manufacturing example 8
A copolymer obtained in Comparative Synthesis Example 4 having a molar ratio of styrene sulfonic acid to 3-acryloxypropyltrimethoxysilane of 7: 3 was used instead of the copolymer obtained in Synthesis Example 1. The same operation as in Production Example 31 was carried out to obtain a dispersion liquid of the conductive polymer composition.
〔透明導電性フィルムでの評価〕
実施例６１
この透明導電性フィルムでの評価では、上記製造例３１に記載の１，３−プロパンジオール添加後の導電性高分子組成物の分散液４４ｇにバインダとしてスルホン化ポリエステル〔互応化学工業社製プラスコートＺ−５６５(商品名)〕の２０％水溶液を９ｇ、メタノールを２０ｇ添加して、１時間攪拌機で撹拌し、次いで、東洋濾紙社製の濾紙No.１３１で濾過して、製造例３１の導電性高分子組成物の分散液をベースとする透明導電性フィルム製造用塗料を調製した。なお、この透明導電性フィルム製造用塗料を簡略化して「透明導電性フィルム用塗料」という場合がある。本書では、製造例３１〜３８などの導電性高分子組成物の分散液とそれにバインダを添加したものとを区別するために、後者を「透明導電性フィルム用塗料」という表現で表しているが、この「透明導電性フィルム用塗料」も導電性高分子組成物の分散液の一種であることには変わりはない。
[Evaluation with transparent conductive film]
Example 61
In the evaluation with this transparent conductive film, sulfonated polyester as a binder in 44 g of the dispersion liquid of the conductive polymer composition after addition of 1,3-propanediol described in Production Example 31 [Plus Coat manufactured by Mutual Chemical Industry Co., Ltd.] Add 9 g of a 20% aqueous solution of Z-565 (trade name)] and 20 g of methanol, stir with a stirrer for 1 hour, and then filter with filter paper No. 131 manufactured by Toyo Filter Paper Co., Ltd. to conduct conductivity of Production Example 31. A coating material for producing a transparent conductive film based on a dispersion liquid of a polymer composition was prepared. In addition, this paint for producing a transparent conductive film may be simplified and referred to as "paint for transparent conductive film". In this document, in order to distinguish the dispersion liquid of the conductive polymer composition such as Production Examples 31 to 38 from the one to which a binder is added, the latter is expressed by the expression "paint for transparent conductive film". , This "paint for transparent conductive film" is still a kind of dispersion liquid of conductive polymer composition.
透明導電性フィルム製造時の基材となる透明ポリエステルシートとしては、東洋紡績社製コスモシャインＡ４３００（商品名、厚さ１８８μｍ、両面易接着処理、全光線透過率９２．３％、Ｈａｚｅ０．９％）を用い、この透明ポリエステルシートに上記製造例３１の導電性高分子組成物の分散液をベースとする透明導電性フィルム製造用塗料をバーコーターＮｏ.０６（膜厚１３．７４μｍ）で塗布し、１３０℃で９０秒間乾燥して、透明導電性フィルムを製造した。 As a transparent polyester sheet used as a base material in the production of a transparent conductive film, Cosmo Shine A4300 (trade name, thickness 188 μm, double-sided easy adhesion treatment, total light transmittance 92.3%, Haze 0.9%) manufactured by Toyo Spinning Co., Ltd. ), A paint for producing a transparent conductive film based on the dispersion liquid of the conductive polymer composition of Production Example 31 is applied to this transparent polyester sheet with Barcoater No. 06 (thickness 13.74 μm). , 130 ° C. for 90 seconds to produce a transparent conductive film.
実施例６２〜６８
まず、製造例３２〜３８の導電性高分子組成物の分散液のそれぞれに、実施例６１の場合と同様にバインダとしてスルホン化ポリエステルを添加して、製造例３２〜３８の導電性高分子組成物の分散液をベースとする透明導電性フィルム製造用塗料を調製した。
Examples 62-68
First, sulfonated polyester is added as a binder to each of the dispersions of the conductive polymer compositions of Production Examples 32 to 38 as in the case of Example 61, and the conductive polymer compositions of Production Examples 32 to 38 are added. A paint for producing a transparent conductive film based on a dispersion of a substance was prepared.
そして、その上で、実施例６１の導電性高分子組成物の分散液をベースとする透明導電性フィルム製造用塗料に代えて、製造例３２〜３８の導電性高分子組成物の分散液をベースとする透明導電性フィルム製造用塗料をそれぞれ別々に用いた以外は、実施例６１と同様にして、実施例６３〜６８の透明導電性フィルムを製造した。 Then, instead of the coating material for producing a transparent conductive film based on the dispersion liquid of the conductive polymer composition of Example 61, the dispersion liquid of the conductive polymer compositions of Production Examples 32 to 38 is used. The transparent conductive films of Examples 63 to 68 were produced in the same manner as in Example 61, except that the coating materials for producing a transparent conductive film as a base were used separately.
比較例１３〜１７
この比較例１３〜１７においても、比較製造例４〜８の導電性高分子組成物の分散液のそれぞれに、実施例６１と同様にバインダとしてスルホン化ポリエステルを添加して、比較製造例４〜８の導電性高分子組成物の分散液をベースとする透明導電性フィルム製造用塗料を調製した。
Comparative Examples 13 to 17
Also in Comparative Production Examples 13 to 17, sulfonated polyester was added as a binder to each of the dispersions of the conductive polymer compositions of Comparative Production Examples 4 to 8 in the same manner as in Example 61, and Comparative Production Examples 4 to 4 to A paint for producing a transparent conductive film based on the dispersion liquid of the conductive polymer composition of No. 8 was prepared.
そして、その上で、製造例３１の導電性高分子組成物の分散液をベースとする透明導電性フィルム製造用塗料に代えて、比較製造例４〜８の導電性高分子組成物の分散液をベースとする透明導電性フィルム製造用塗料をそれぞれ別々に用いた以外は、実施例６１と同様にして、比較例１３〜１７の透明導電性フィルムを製造した。 Then, instead of the coating material for producing a transparent conductive film based on the dispersion liquid of the conductive polymer composition of Production Example 31, the dispersion liquid of the conductive polymer composition of Comparative Production Examples 4 to 8 is used. The transparent conductive films of Comparative Examples 13 to 17 were produced in the same manner as in Example 61, except that the coating materials for producing a transparent conductive film based on the above were used separately.
上記のようにして製造した実施例６１〜６８の透明導電性フィルム（簡略化して、「導電性フィルム」という場合がある）および比較例１３〜１７の導電性フィルムについて、表面抵抗値、全光線透過率およびＨａｚｅ(曇価)を測定し、その結果を初期特性値として後記の表９に使用した透明導電性フィルム製造用塗料の種類と共に示す。ただし、上記透明導電性フィルム製造用塗料の種類はそれらのベースとして使用した導電性高分子組成物の分散液の製造例番号や比較製造例番号で示す。これは後記の表１０においても同様である。なお、表面抵抗値、全光線透過率、Ｈａｚｅの測定は、それぞれの導電性フィルムを４ｃｍ×８ｃｍの長方形に切り出し、全光線透過率、Ｈａｚｅの測定は次に示す通りに行った。 The surface resistance value and total light beam of the transparent conductive films of Examples 61 to 68 (sometimes referred to as “conductive films” for short) and the conductive films of Comparative Examples 13 to 17 produced as described above. The permeability and Haze (cloudiness value) are measured, and the results are shown as initial characteristic values together with the type of the coating material for producing a transparent conductive film used in Table 9 below. However, the types of the coating materials for producing the transparent conductive film are indicated by the production example number and the comparative production example number of the dispersion liquid of the conductive polymer composition used as the base thereof. This also applies to Table 10 below. The surface resistance value, the total light transmittance, and the haze were measured by cutting each conductive film into a rectangle of 4 cm × 8 cm, and the total light transmittance and the haze were measured as shown below.
表面抵抗値：
三菱化学アナリテック社製ロレスタ−ＧＰ〔ＭＣＰ−Ｔ６１０型、直列４探針プローブ（ＡＳＰ）〕を用いて温度２５℃で測定した。
測定にあたっては、各試料とも１０個ずつ用い、表９に示す表面抵抗値は、それら１０個の平均値を求め、小数点以下を四捨五入して示したものである。
Surface resistance value:
The measurement was performed at a temperature of 25 ° C. using a Loresta-GP [MCP-T610 type, in-line 4-probe probe (ASP)] manufactured by Mitsubishi Chemical Analytech.
In the measurement, 10 samples were used for each sample, and the surface resistance values shown in Table 9 were obtained by calculating the average value of these 10 samples and rounding off to the nearest whole number.
全光線透過率：
スガ試験機株式会社製ＨＺ−２Ｐ型〔ダブルビ−ム形式（Ｃ光・Ｄ６５光）〕を用い、温度２５℃で測定した。測定にあたっては、各試料とも１０個ずつ用い、表９に示す全光線透過率値は、それら１０個の平均値を求め、小数点第二位を四捨五入して示したものである。
Total light transmittance:
The measurement was performed at a temperature of 25 ° C. using an HZ-2P type [double beam type (C light / D 65 light)] manufactured by Suga Test Instruments Co., Ltd. In the measurement, 10 samples were used for each sample, and the total light transmittance values shown in Table 9 were obtained by calculating the average value of these 10 samples and rounding off to the second decimal place.
Ｈａｚｅ：
スガ試験機株式会社製ＨＺ−２Ｐ型〔ダブルビ−ム形式（Ｃ光・Ｄ６５光）〕を用い、温度２５℃で測定した。測定にあたっては、各試料とも１０個ずつ用い、表２に示すＨａｚｅ値は、それら１０個の平均値を求め、小数点第二位を四捨五入して示したものである。そして、このＨａｚｅは、値が小さいほど、透明性が高いことを示す。
Haze:
The measurement was performed at a temperature of 25 ° C. using an HZ-2P type [double beam type (C light / D 65 light)] manufactured by Suga Test Instruments Co., Ltd. In the measurement, 10 samples were used for each sample, and the Haze values shown in Table 2 were obtained by calculating the average value of these 10 samples and rounding off the second decimal place. And, this Haze shows that the smaller the value, the higher the transparency.
上記のようにして測定した実施例６１〜６８および比較例１３〜１７のフィルムの初期特性値を前記のように表９に示すが、これらの実施例６１〜６８および比較例１３〜１７のフィルムについては、耐湿熱性試験および耐熱性試験を行って、それらの評価をしているので、その耐湿熱性試験や耐熱性試験の条件、評価方法を表９の表示に先立って〔透明導電性フィルムの耐湿熱性評価および耐熱性評価〕という項目で示す The initial characteristic values of the films of Examples 61 to 68 and Comparative Examples 13 to 17 measured as described above are shown in Table 9 as described above, and the films of Examples 61 to 68 and Comparative Examples 13 to 17 are shown in Table 9 as described above. Since the moist heat resistance test and the heat resistance test are carried out and evaluated, the conditions and the evaluation method of the moist heat resistance test and the heat resistance test are described before the display in Table 9 [Transparent conductive film. Moisture resistance evaluation and heat resistance evaluation]
〔透明導電性フィルムの耐湿熱性評価および耐熱性評価〕
上記表面抵抗値や全光線透過率などの初期特性値の測定に使用したものとは別途製造した実施例６１〜６８の導電性フィルムおよび比較例１３〜１７の透明導電性フィルム（以下、これらの「透明導電性フィルム」を簡略化して「フィルム」という場合がある）について、前記と同様に、表面抵抗値を測定した後、耐湿熱性試験については、それらのフィルムを下記の（Ａ）および（Ｂ）の条件
（Ａ）６５℃で相対湿度９５％の恒温恒湿機中
（Ｂ）８５℃で相対湿度８５％の恒温恒湿機中
という条件下において静置状態でそれぞれ別々に２５０時間貯蔵し、その貯蔵後、１３０℃で９０秒間乾燥し、その後、前記と同様に、表面抵抗値（以下、簡略化して、「抵抗値」という場合がある）を測定した。その抵抗値の測定結果に基づき、次の式により、耐湿熱性試験下での貯蔵による抵抗値の変化率を求めた。
(抵抗値変化率) ＝ (耐湿熱性試験後の抵抗値) ÷ (耐湿熱性試験前の抵抗値)
[Evaluation of moisture resistance and heat resistance of transparent conductive film]
The conductive films of Examples 61 to 68 and the transparent conductive films of Comparative Examples 13 to 17 manufactured separately from those used for measuring the initial characteristic values such as the surface resistance value and the total light transmittance (hereinafter, these). For the "transparent conductive film", which may be abbreviated as "film"), after measuring the surface resistance value in the same manner as above, for the moisture and heat resistance test, those films are referred to as (A) and (A) below. Conditions of B) (A) In a constant temperature and humidity chamber at 65 ° C. and a relative humidity of 95% (B) In a constant temperature and humidity chamber at 85 ° C. and a relative humidity of 85%, each is stored separately for 250 hours in a stationary state. Then, after the storage, it was dried at 130 ° C. for 90 seconds, and then the surface resistance value (hereinafter, may be abbreviated as “resistance value”) was measured in the same manner as described above. Based on the measurement result of the resistance value, the rate of change of the resistance value due to storage under the moisture resistance test was calculated by the following formula.
(Ratio of change in resistance value) = (Resistance value after moisture resistance test) ÷ (Resistance value before moisture resistance test)
また、耐熱性試験に関しては、上記耐湿熱性試験に供したものとは別途製造した実施例６１〜６８および比較例１３〜１７のフィルムを下記（Ｃ）の条件
（Ｃ）８５℃のオーブン中
という条件下において静置状態でそれぞれ別々に２５０時間貯蔵した後、前記と同様に、抵抗値を測定し、その貯蔵による抵抗値の変化率を次の式により求めた。
(抵抗値変化率) ＝ (耐熱性試験後の抵抗値) ÷ (耐熱性試験前の抵抗値)
Regarding the heat resistance test, the films of Examples 61 to 68 and Comparative Examples 13 to 17 manufactured separately from those subjected to the above-mentioned moisture and heat resistance test are referred to as being in an oven under the following conditions (C) (C) at 85 ° C. After storing each separately in a stationary state for 250 hours under the conditions, the resistance value was measured in the same manner as described above, and the rate of change of the resistance value due to the storage was calculated by the following formula.
(Ratio of change in resistance value) = (Resistance value after heat resistance test) ÷ (Resistance value before heat resistance test)
そして、上記のようにして求めた耐湿熱性試験および耐熱性試験によるフィルムの抵抗値の変化率を表１０に示す。ただし、表１０への耐湿熱性試験や耐熱性試験の条件の表示にあたっては、スペース上の関係で、次のように簡略化して示す。
（Ａ）「６５℃相対湿度９５％の恒温恒湿機中」→「６５℃／９５％」
（Ｂ）「８５℃相対湿度８５％の恒温恒湿機中」→「８５℃／８５％」
（Ｃ）「８５℃のオーブン中」→「８５℃」
Table 10 shows the rate of change in the resistance value of the film obtained by the moisture resistance test and the heat resistance test obtained as described above. However, when the conditions for the moisture resistance test and the heat resistance test are displayed in Table 10, they are simply shown as follows due to space limitations.
(A) "In a constant temperature and humidity chamber with a relative humidity of 95% at 65 ° C" → "65 ° C / 95%"
(B) "In a constant temperature and humidity chamber with a relative humidity of 85% at 85 ° C" → "85 ° C / 85%"
(C) "In an oven at 85 ° C" → "85 ° C"
上記実施例６１〜６８のフィルムは、表９に示すように、初期の表面抵抗値に関しては、比較例１３〜１７のフィルムと同程度であるが、表１０に示すように、耐湿熱性試験での抵抗値変化率が比較例１３〜１７のフィルムに比べて小さく、耐湿熱性が優れていた。 As shown in Table 9, the films of Examples 61 to 68 are similar to the films of Comparative Examples 13 to 17 in terms of initial surface resistance value, but as shown in Table 10, in the moisture and heat resistance test. The rate of change in resistance value was smaller than that of the films of Comparative Examples 13 to 17, and the moisture and heat resistance was excellent.
また、実施例６１〜６８のフィルムは、初期の表面抵抗値が比較例１３〜１７のフィルムと同等であるものの、この種の導電性高分子組成物のみで構成される透明導電性フィルムとしては充分に低い表面抵抗値を示しており、透明性の指標となるＨａｚｅ値も小さく、耐熱性試験での抵抗値変化率も小さく、透明性が優れ、かつ導電性が高く、しかも耐熱性が優れた透明導電性フィルムであることを示していた。 Further, although the films of Examples 61 to 68 have the same initial surface resistance values as the films of Comparative Examples 13 to 17, the transparent conductive film composed of only this kind of conductive polymer composition is used. It shows a sufficiently low surface resistance value, has a small Haze value as an index of transparency, has a small rate of change in resistance value in a heat resistance test, has excellent transparency, high conductivity, and excellent heat resistance. It was shown that it was a transparent conductive film.
また、導電性フィルムについては、耐湿熱性試験に関して、（Ａ）の６５℃／９５％の条件下２５０時間の貯蔵で、抵抗値変化率が１．３以下、（Ｂ）の８５℃／８５％の条件下２５０時間の貯蔵で、抵抗値変化率が１．３以下、耐熱性試験に関して、（Ｃ）の８５℃の条件下２５０時間の貯蔵で、抵抗値変化率が１．３以下であることが要求されるが、表１０に示すように、実施例６１〜６８のフィルムは、抵抗値変化率に関する上記（Ａ）から（Ｃ）における１．３以下という要求をいずれも満たしていた。 Regarding the conductive film, regarding the moisture and heat resistance test, the resistance value change rate was 1.3 or less and 85 ° C./85% of (B) after storage for 250 hours under the condition of 65 ° C./95% of (A). The resistance value change rate is 1.3 or less after 250 hours of storage under the above conditions, and the resistance value change rate is 1.3 or less after 250 hours of storage under the 85 ° C. condition of (C) for the heat resistance test. However, as shown in Table 10, the films of Examples 61 to 68 satisfied all of the requirements of 1.3 or less in (A) to (C) above regarding the rate of change in resistance value.
〔透明導電性複合フィルムでの評価〕
この透明導電性複合フィルムでの評価では、上記実施例６１〜６８で調製した製造例３１〜３８の導電性高分子組成物の分散液をベースとする透明導電性フィルム製造用塗料とシグマアルドリッチ社製の銀ナノワイヤーの分散液（製品番号７３０７８５、銀ナノワイヤーの直径１０ｎｍ、濃度０，０２ｍｇ／ｍｌの水分散液）を用いて実施例６９〜７６の透明導電性複合フィルムを製造し、それらとの比較のため、比較例１３〜１７で調製した比較例製造例４〜８の導電性高分子組成物の分散液をベースとする透明導電性フィルム製造用塗料と上記銀ナノワイヤーの分散液とを用いて比較例１８〜２２の透明導電性複合フィルムを製造して、それらの特性を評価する。なお、ここでは、導電性高分子組成物と銀ナノワイヤーとの混合物からなる複合導電性組成物を用いてフィルムを形成しているので、形成されたフィルムを導電性複合フィルムと表現しているが、この導電性複合フィルムも導電性フィルムの範疇に属するものである。
[Evaluation with transparent conductive composite film]
In the evaluation of this transparent conductive composite film, a coating material for producing a transparent conductive film based on the dispersion liquid of the conductive polymer composition of Production Examples 31 to 38 prepared in Examples 61 to 68 and Sigma Aldrich Co., Ltd. The transparent conductive composite films of Examples 69 to 76 were produced using the silver nanowire dispersion liquid (product number 730785, silver nanowire diameter 10 nm, concentration 0.02 mg / ml aqueous dispersion). For comparison with, the coating material for producing a transparent conductive film based on the dispersion liquid of the conductive polymer composition of Comparative Example Production Examples 4 to 8 prepared in Comparative Examples 13 to 17 and the dispersion liquid of the silver nanowires. The transparent conductive composite films of Comparative Examples 18 to 22 are produced using and, and their characteristics are evaluated. Here, since the film is formed by using a composite conductive composition composed of a mixture of the conductive polymer composition and silver nanowires, the formed film is expressed as a conductive composite film. However, this conductive composite film also belongs to the category of conductive film.
実施例６９
シグマアルドリッチ社製の銀ナノワイヤーの分散液（製品番号７３０７８５、銀ナノワイヤーの直径１０ｎｍ、濃度０，０２ｍｇ／ｍＬの水分散液）と実施例６１で調製した製造例３１の導電性高分子組成物の分散液をベースとする透明導電性フィルム製造用塗料とを混合し、銀ナノワイヤー：導電性高分子組成物の比率が２．５：１に調製した複合導電性組成物の分散液を基材となる東洋紡績社製の透明ポリエステルシート〔コスモシャインＡ４３００（商品名）、厚さ１８８μｍ、両面易接着処理、全光線透過率９２．３％、Ｈａｚｅ０．９％〕にバーコーターＮｏ.０６（膜厚１３．７４μｍ）で塗布し、１３０℃で９０秒間乾燥して、透明ポリエステルシートからなる基材上に、上記複合導電性組成物からなる透明導電性複合フィルムを製造した。
Example 69
A dispersion of silver nanowires manufactured by Sigma Aldrich (product number 730785, an aqueous dispersion of silver nanowires with a diameter of 10 nm and a concentration of 0.02 mg / mL) and the conductive polymer composition of Production Example 31 prepared in Example 61. A dispersion liquid of a composite conductive composition prepared by mixing with a coating material for producing a transparent conductive film based on a dispersion liquid of a substance and preparing a silver nanowire: conductive polymer composition ratio of 2.5: 1. Barcoater No. 06 on a transparent polyester sheet manufactured by Toyo Spinning Co., Ltd. [Cosmo Shine A4300 (trade name), thickness 188 μm, double-sided easy-adhesion treatment, total light transmittance 92.3%, Haze 0.9%] The film was applied at (thickness: 13.74 μm) and dried at 130 ° C. for 90 seconds to produce a transparent conductive composite film made of the above composite conductive composition on a substrate made of a transparent polyester sheet.
実施例７０〜７６
実施例６１で調製した製造例３１の導電性高分子組成物の分散液をベースとする透明導電性フィルム製造用塗料に代えて、実施例６２〜６８で調製した製造例３２〜３８の導電性高分子組成物の分散液をベースとする透明導電性フィルム製造用塗料をそれぞれ別々に用いた以外は、実施例６９と同様にして、実施例７０〜７６の透明導電性複合フィルムを製造した。
Examples 70-76
Instead of the coating material for producing a transparent conductive film based on the dispersion liquid of the conductive polymer composition of Production Example 31 prepared in Example 61, the conductivity of Production Examples 32 to 38 prepared in Examples 62 to 68 The transparent conductive composite films of Examples 70 to 76 were produced in the same manner as in Example 69, except that the coating materials for producing a transparent conductive film based on the dispersion liquid of the polymer composition were used separately.
比較例１８〜２２
実施例６１で調製した製造例３１の導電性高分子組成物の分散液塗料をベースとする透明導電性フィルム製造用塗料に代えて、比較例１３〜１７で調製した比較製造例４〜８の導電性高分子組成物の分散液をベースとする透明導電性フィルム製造用塗料をそれぞれ別々に用いた以外は、実施例６９と同様にして、比較例１８〜２２の透明導電性複合フィルムを製造した。
Comparative Examples 18 to 22
Comparative Production Examples 4 to 8 prepared in Comparative Examples 13 to 17 instead of the coating material for producing a transparent conductive film based on the dispersion liquid coating material of the conductive polymer composition of Production Example 31 prepared in Example 61. The transparent conductive composite films of Comparative Examples 18 to 22 were produced in the same manner as in Example 69, except that the paints for producing a transparent conductive film based on the dispersion liquid of the conductive polymer composition were used separately. did.
上記のようにして製造した実施例６９〜７６の透明導電性複合フィルム（簡略化して、「複合フィルム」という場合がある）および比較例１８〜２２の複合フィルムについて、表面抵抗値、全光線透過率およびＨａｚｅ(曇価)を測定した。その結果を初期特許性値として表１１に使用した透明導電性フィルム製造用塗料の種類と共に示す。ただし、上記透明導電性フィルム製造用塗料の種類はそれらのベースとして使用した導電性高分子組成物の製造例番号や比較製造例番号などで示す。これは後記の表１２においても同様である。なお、表面抵抗値、全光線透過率、Ｈａｚｅの測定は、それぞれの複合フィルムを４ｃｍ×８ｃｍの長方形に切り出し、前記実施例６１の透明導電性フィルムの場合と同様に行った。 The transparent conductive composite films of Examples 69 to 76 (sometimes referred to as “composite films” for short) and the composite films of Comparative Examples 18 to 22 produced as described above have a surface resistance value and total light transmittance. The rate and Haze (cloudiness) were measured. The results are shown as initial patentability values together with the types of paints for producing transparent conductive films used in Table 11. However, the types of the above-mentioned coating materials for producing a transparent conductive film are indicated by production example numbers, comparative production example numbers, etc. of the conductive polymer composition used as their base. This also applies to Table 12 below. The surface resistance value, total light transmittance, and haze were measured by cutting each composite film into a rectangle of 4 cm × 8 cm and performing the same as in the case of the transparent conductive film of Example 61.
また、上記表面抵抗値や全光線透過率などの測定に使用したものとは別途製造した実施例６９〜７６の複合フィルムおよび比較例１８〜２２の複合フィルムについて、前記実施例６１の透明導電性フィルムと同様に、表面抵抗値を測定した後、耐湿熱性試験、耐熱性試験をし、複合フィルムの抵抗値変化率を調べた。その結果を表１２に示す。 Further, with respect to the composite films of Examples 69 to 76 and the composite films of Comparative Examples 18 to 22 manufactured separately from those used for measuring the surface resistance value and the total light transmittance, the transparent conductivity of the above-mentioned Example 61 was obtained. Similar to the film, after measuring the surface resistance value, a moist heat resistance test and a heat resistance test were performed to examine the rate of change in the resistance value of the composite film. The results are shown in Table 12.
上記実施例６９〜７６の複合フィルムは、表１１に示すように、初期の表面抵抗値に関しては、比較例１８〜２２の複合フィルムと同等であるが、表１２に示すように、耐湿熱性試験での抵抗値変化率が比較例１８〜２２の複合フィルムに比べて小さく、耐湿熱性が優れていた。 As shown in Table 11, the composite films of Examples 69 to 76 are equivalent to the composite films of Comparative Examples 18 to 22 in terms of the initial surface resistance value, but as shown in Table 12, the moisture and heat resistance test The rate of change in resistance value was smaller than that of the composite films of Comparative Examples 18 to 22, and the moisture and heat resistance was excellent.
また、実施例６９〜７６の複合フィルムは、初期の表面抵抗値が比較例１８〜２２の複合フィルムと同等であるものの、この種の複合フィルムとしては充分に低い表面抵抗値を示しており、透明性の指標となるＨａｚｅ値も小さく、耐熱性試験での抵抗値変化率も小さく、透明性が優れ、かつ、導電性が高く、しかも耐熱性が優れた透明導電性複合フィルムであることを示していた。 Further, although the initial surface resistance values of the composite films of Examples 69 to 76 are equivalent to those of the composite films of Comparative Examples 18 to 22, the surface resistance values of the composite films of this type are sufficiently low. The transparent conductive composite film has a small Haze value, which is an index of transparency, a small rate of change in resistance value in a heat resistance test, excellent transparency, high conductivity, and excellent heat resistance. Was showing.
〔透明導電性積層フィルムでの評価〕
この透明導電性積層フィルムでの評価では、上記実施例６１〜６８で調製した製造例３１〜３８の導電性高分子組成物の分散液をベースとする透明導電性フィルム製造用塗料と前記導電性複合フィルムの製造にあたって用いたものと同様のシグマアルドリッチ社製の銀ナノワイヤーの分散液（前出の製品番号７３０７８５）とを用いて実施例７７〜８４の透明導電性積層フィルムを製造し、それらとの比較のため、比較例１３〜１７で調製した比較製造例４〜８の導電性高分子組成物の分散液をベースとする透明導電性フィルム製造用塗料と上記銀ナノワイヤーの分散液とを用いて比較例２３〜２７の透明導電性積層フィルムを製造して、それらの特性を評価する。
[Evaluation with transparent conductive laminated film]
In the evaluation of this transparent conductive laminated film, the coating material for producing a transparent conductive film based on the dispersion liquid of the conductive polymer composition of Production Examples 31 to 38 prepared in Examples 61 to 68 and the conductivity. The transparent conductive laminated films of Examples 77 to 84 were produced using a dispersion liquid of silver nanowires manufactured by Sigma Aldrich Co., Ltd. (product number 730785 described above) similar to that used in the production of the composite film, and they were produced. For comparison with, the coating material for producing a transparent conductive film based on the dispersion liquid of the conductive polymer composition of Comparative Production Examples 4 to 8 prepared in Comparative Examples 13 to 17 and the dispersion liquid of the silver nanowires were used. The transparent conductive laminated films of Comparative Examples 23 to 27 are produced using the above, and their characteristics are evaluated.
実施例７７
上記シグマアルドリッチ社製の銀ナノワイヤーの分散液（前出の製品番号７３０７８５）を東洋紡績社製の透明ポリエステルシート〔コスモシャインＡ４３００（商品名）、厚さ１８８μｍ、両面易接着処理、全光線透過率９２．３％、Ｈａｚｅ０．９％〕にバーコーターＮｏ．０６（膜厚１３．７４μｍ）で塗布し、１３０℃で９０秒間乾燥して、透明ポリエステルシートからなる基材上に透明銀ナノワイヤーフィルムを形成した。次いで、この透明銀ナノワイヤーフィルム上に、上記製造例３１の導電性高分子組成物の分散液をベースとする透明導電性フィルム製造用塗料をクリアランス２５μｍのアプリケーターバーで塗布し、１３０℃で９０秒間乾燥して、銀ナノワイヤーフィルム上に導電性高分子組成物フィルムを積層することによって、透明導電性積層フィルムを製造した。
Example 77
The above-mentioned dispersion liquid of silver nanowires manufactured by Sigma-Aldrich (product number 730785 mentioned above) is applied to a transparent polyester sheet manufactured by Toyobo Co., Ltd. [Cosmo Shine A4300 (trade name), thickness 188 μm, double-sided easy adhesion treatment, total light transmittance. Rate 92.3%, Haze 0.9%] and Bar Coater No. It was applied at 06 (thickness 13.74 μm) and dried at 130 ° C. for 90 seconds to form a transparent silver nanowire film on a substrate made of a transparent polyester sheet. Next, on the transparent silver nanowire film, a coating material for producing a transparent conductive film based on the dispersion liquid of the conductive polymer composition of Production Example 31 was applied with an applicator bar having a clearance of 25 μm, and 90 at 130 ° C. A transparent conductive laminated film was produced by drying for a second and laminating a conductive polymer composition film on a silver nanowire film.
実施例７８〜８４
製造例３１の導電性高分子組成物の分散液をベースとする透明導電性フィルム製造用塗料に代えて、製造例３２〜３８の導電性高分子組成物の分散液をベースとする透明導電性フィルム製造用塗料をそれぞれ別々に用いた以外は、実施例７７と同様にして、実施例７８〜８４の透明導電性積層フィルムを製造した。
Examples 78-84
Instead of the coating material for producing a transparent conductive film based on the dispersion liquid of the conductive polymer composition of Production Example 31, the transparent conductivity based on the dispersion liquid of the conductive polymer composition of Production Examples 32 to 38 The transparent conductive laminated films of Examples 78 to 84 were produced in the same manner as in Example 77, except that the film-producing paints were used separately.
比較例２３〜２７
製造例３１の導電性高分子組成物の分散液をベースとする透明導電性フィルム製造用塗料に代えて、比較製造例４〜８の導電性高分子組成物の分散液をベースとする透明導電性フィルム製造用塗料をそれぞれ別々に用いた以外は、実施例７７と同様にして、比較例２３〜２７の透明導電性積層フィルムを製造した。
Comparative Examples 23 to 27
Instead of the coating material for producing a transparent conductive film based on the dispersion liquid of the conductive polymer composition of Production Example 31, transparent conductivity based on the dispersion liquid of the conductive polymer composition of Comparative Production Examples 4 to 8 The transparent conductive laminated films of Comparative Examples 23 to 27 were produced in the same manner as in Example 77 except that the paints for producing a sex film were used separately.
上記のようにして製造した実施例７７〜８４の透明導電性積層フィルム（簡略化して、「導電性積層フィルム」という場合がある）および比較例２３〜２７の導電性積層フィルムについて、表面抵抗値、全光線透過率およびＨａｚｅ(曇価)を測定した。その結果を初期特性値として表１３に使用した透明導電性フィルム製造用塗料の種類と共に示す。ただし、上記透明導電性フィルム製造用塗料の種類はそれらのベースとして使用した導電性高分子組成物の分散液の製造例番号や比較製造例番号などで示す。これは後記の表１４においても同様である。なお、表面抵抗値、全光線透過率、Ｈａｚｅの測定は、それぞれの導電性積層フィルムを４ｃｍ×８ｃｍの長方形に切り出し、前記実施例６１の透明導電性フィルムの場合と同様に行った。 The surface resistance values of the transparent conductive laminated films of Examples 77 to 84 (sometimes referred to as "conductive laminated films" for simplification) and the conductive laminated films of Comparative Examples 23 to 27 produced as described above. , Total light transmittance and Haze (cloud value) were measured. The results are shown as initial characteristic values together with the types of paints for producing transparent conductive films used in Table 13. However, the types of the coating materials for producing the transparent conductive film are indicated by the production example number, the comparative production example number, and the like of the dispersion liquid of the conductive polymer composition used as the base thereof. This also applies to Table 14 below. The surface resistance value, the total light transmittance, and the haze were measured by cutting each conductive laminated film into a rectangle of 4 cm × 8 cm and performing the same as in the case of the transparent conductive film of Example 61.
上記表面抵抗値や全光線透過率などの測定に使用したものとは別途製造した実施例７７〜８４の導電性積層フィルムおよび比較例２３〜２７の導電性積層フィルムについて、前記実施例６１の透明導電性フィルムと同様に、表面抵抗値を測定した後、耐湿熱性試験、耐熱性試験をし、導電性積層フィルム（簡略化して、「積層フィルム」という場合がある）の抵抗値の変化率を調べた。その結果を表１４に示す。 Regarding the conductive laminated films of Examples 77 to 84 and the conductive laminated films of Comparative Examples 23 to 27, which were manufactured separately from those used for measuring the surface resistance value and the total light transmittance, the transparency of Example 61 was obtained. Similar to the conductive film, after measuring the surface resistance value, a moist heat resistance test and a heat resistance test are performed to determine the rate of change in the resistance value of the conductive laminated film (sometimes referred to as "laminated film" for short). Examined. The results are shown in Table 14.
上記実施例７７〜８４の積層フィルムは、表１３に示すように、初期の表面抵抗値に関しては、比較例２３〜２７の積層フィルムと同等であるが、表１４に示すように、耐湿熱性試験での抵抗値変化率が比較例２３〜２７の積層フィルムに比べて小さく、耐湿熱性が優れていた。 As shown in Table 13, the laminated films of Examples 77 to 84 are equivalent to the laminated films of Comparative Examples 23 to 27 in terms of initial surface resistance value, but as shown in Table 14, the moisture and heat resistance test The rate of change in resistance value was smaller than that of the laminated films of Comparative Examples 23 to 27, and the moisture and heat resistance was excellent.
また、実施例７７〜８４の積層フィルムは、初期の表面抵抗値が比較例２３〜２７の積層フィルムと同等であるものの、この種の積層フィルムとしては充分に低い表面抵抗値を示しており、また、透明性の指標となるＨａｚｅ値も小さく、耐熱性試験での抵抗値変化率も小さく、透明性が優れ、かつ導電性が高く、しかも耐熱性が優れた透明導電性積層フィルムであることを示していた。 Further, although the initial surface resistance values of the laminated films of Examples 77 to 84 are equivalent to those of the laminated films of Comparative Examples 23 to 27, they show a sufficiently low surface resistance value for this type of laminated film. In addition, the Haze value, which is an index of transparency, is small, the rate of change in resistance value in the heat resistance test is small, the transparency is excellent, the conductivity is high, and the heat resistance is excellent. Was shown.
〔導電性不織布での評価〕
この導電性不識布での評価では、実施例６１〜６８で調製した製造例３１〜３８の導電性高分子組成物の分散液をベースとする塗料を用いて実施例８５〜９２の導電性不織布を製造し、それらとの比較のため、比較例１３〜１７で調製した比較製造例４〜８の導電性高分子組成物の分散液をベースとする塗料を用いて比較例２８〜３２の導電性不織布を製造して、それらの特性を評価する。
[Evaluation with conductive non-woven fabric]
In the evaluation using this conductive non-woven fabric, the conductivity of Examples 85 to 92 was evaluated by using a coating material based on the dispersion liquid of the conductive polymer composition of Production Examples 31 to 38 prepared in Examples 61 to 68. Nonwoven fabrics are produced, and for comparison with them, the coating materials based on the dispersion liquid of the conductive polymer compositions of Comparative Production Examples 4 to 8 prepared in Comparative Examples 13 to 17 are used in Comparative Examples 28 to 32. Conductive non-woven fabrics are manufactured and their properties are evaluated.
実施例８５
導電性不織布の製造時の基布となる不織布としては、目付け１００ｇ/ｍ２のポリエステル不織布を用い、この不織布に製造例３１の導電性高分子組成物の分散液をベースとする塗料を含浸し、ピックアップ量を不織布重量の２００％量に調整し、１３０℃で９０秒間乾燥して、基布となる不織布に導電性高分子組成物を保持させることによって、導電性不織布を製造した。
Example 85
As the non-woven fabric used as the base cloth during the production of the conductive non-woven fabric, a polyester non-woven fabric having a texture of 100 g / m 2 is used, and the non-woven fabric is impregnated with a paint based on the dispersion liquid of the conductive polymer composition of Production Example 31. The amount of pick-up was adjusted to 200% of the weight of the non-woven fabric, and the non-woven fabric was dried at 130 ° C. for 90 seconds to hold the conductive polymer composition in the non-woven fabric as the base cloth, thereby producing the conductive non-woven fabric.
実施例８６〜９２
製造例３１の導電性高分子組成物の分散液をベースとする塗料に代えて、製造例３２〜３８の導電性高分子組成物の分散をベースとする塗料をそれぞれ別々に用いた以外は、実施例８５と同様にして、実施例８６〜９２の導電性不織布を製造した。
Examples 86-92
Except that, instead of the coating material based on the dispersion liquid of the conductive polymer composition of Production Example 31, the coating materials based on the dispersion of the conductive polymer composition of Production Examples 32 to 38 were used separately. The conductive non-woven fabrics of Examples 86 to 92 were produced in the same manner as in Example 85.
比較例２８〜３２
製造例３１の導電性高分子組成物の分散液をベースとする塗料に代えて、比較製造例４〜８の導電性高分子組成物の分散液をベースとする塗料をそれぞれ別々に用いた以外は、実施例８５と同様にして、比較例２８〜３２の導電性不織布を製造した。
Comparative Examples 28 to 32
Instead of the coating material based on the dispersion liquid of the conductive polymer composition of Production Example 31, the coating materials based on the dispersion liquid of the conductive polymer composition of Comparative Production Examples 4 to 8 were used separately. Produced the conductive non-woven fabrics of Comparative Examples 28 to 32 in the same manner as in Example 85.
上記のようにして製造した実施例８５〜９２の導電性不織布および比較例２８〜３２の導電性不織布について、表面抵抗値を測定した。その結果を初期特性値として表１５に使用した塗料の種類と共に示す。ただし、上記塗料の種類はそれらのベースとして使用した導電性高分子組成物の分散液の製造例番号や比較製造例番号で示す。なお、表面抵抗値は、それぞれの導電性不織布を４ｃｍ×８ｃｍの長方形に切り出し、前記実施例６１の透明導電性フィルムの場合と同様に測定した。 The surface resistance values of the conductive non-woven fabrics of Examples 85 to 92 and the conductive non-woven fabrics of Comparative Examples 28 to 32 produced as described above were measured. The results are shown as initial characteristic values together with the types of paints used in Table 15. However, the types of the above-mentioned coating materials are indicated by the production example number and the comparative production example number of the dispersion liquid of the conductive polymer composition used as the base thereof. The surface resistance value was measured in the same manner as in the case of the transparent conductive film of Example 61 by cutting out each conductive non-woven fabric into a rectangle of 4 cm × 8 cm.
また、上記表面抵抗値の測定に使用したものとは別途製造した実施例８５〜９２の導電性不織布および比較例２８〜３２の導電性不織布について、前記実施例６１の透明導電性フィルムと同様に、表面抵抗値を測定した後、耐湿熱性試験、耐熱性試験をし、その抵抗値の変化率を調べた。その結果を表１６に示す。 Further, the conductive non-woven fabrics of Examples 85 to 92 and the conductive non-woven fabrics of Comparative Examples 28 to 32, which were manufactured separately from those used for measuring the surface resistance value, were similarly the same as the transparent conductive film of Example 61. After measuring the surface resistance value, a moist heat resistance test and a heat resistance test were performed, and the rate of change of the resistance value was examined. The results are shown in Table 16.
上記実施例８５〜９２の導電性不織布は、表１５に示すように、初期の表面抵抗値に関しては、比較例２８〜３２の導電性不織布と同等であるが、表１６に示すように、耐湿熱性試験での抵抗値変化率が比較例２８〜３２の導電性不織布に比べて小さく、耐湿熱性が優れていた。 As shown in Table 15, the conductive nonwoven fabrics of Examples 85 to 92 are equivalent to the conductive nonwoven fabrics of Comparative Examples 28 to 32 in terms of initial surface resistance value, but as shown in Table 16, they are moisture resistant. The rate of change in resistance value in the thermal test was smaller than that of the conductive non-woven fabrics of Comparative Examples 28 to 32, and the moisture and heat resistance was excellent.
また、実施例８５〜９２の導電性不織布は、初期の表面抵抗値が比較例２８〜３２の導電性不織布と同等であるものの、この種の導電性不織布としては充分に低い表面抵抗値を示しており、また、耐熱性試験での抵抗値変化率も小さく、導電性が高く、かつ耐熱性が優れた導電性不織布であることを示していた。 Further, although the conductive nonwoven fabrics of Examples 85 to 92 have the same initial surface resistance values as the conductive nonwoven fabrics of Comparative Examples 28 to 32, they show a sufficiently low surface resistance value as this type of conductive nonwoven fabric. In addition, the rate of change in resistance value in the heat resistance test was small, indicating that the conductive non-woven fabric had high conductivity and excellent heat resistance.
Claims (13)
（I）：スチレンスルホン酸と、Ｎ−（２−ヒドロキシルエチル）アクリルアミド、Ｎ−（ヒドロキシメチル）アクリルアミド、Ｎ−メチルメタクリルアミド、Ｎ−（４−ヒドロキシフェニル）メタクリルアミド、Ｎ−フェニルアクリルアミドまたはＮ−フェニルメタクリルアミドからなる重合性モノマーとのモル比が９．５：０．５〜４：６の共重合体
（II）：ポリスチレンスルホン酸 The following (I) and (II) are characterized in that they are doped into a π-conjugated polymer containing at least one selected from the group consisting of ethylenedioxythiophene and alkylated ethylenedioxythiophene as a monomer component. Conductive polymer composition.
(I): Styrene sulfonic acid and N- (2-hydroxyethyl) acrylamide, N- (hydroxymethyl) acrylamide, N-methylmethacrylamide, N- (4-hydroxyphenyl) methacrylamide, N-phenylacrylamide or N Copolymer (II): polystyrene sulfonic acid having a molar ratio of 9.5: 0.5 to 4: 6 with a polymerizable monomer composed of -phenylmethacrylamide.
（I）：スチレンスルホン酸と、Ｎ−（２−ヒドロキシルエチル）アクリルアミド、Ｎ−（ヒドロキシメチル）アクリルアミド、Ｎ−メチルメタクリルアミド、Ｎ−（４−ヒドロキシフェニル）メタクリルアミド、Ｎ−フェニルアクリルアミドまたはＮ−フェニルメタクリルアミドからなる重合性モノマーとのモル比が９．５：０．５〜４：６の共重合体
（II）：ポリスチレンスルホン酸
（III）：スルホン化ポリエステルおよびフェノールスルホン酸ノボラック樹脂よりなる群から選ばれる少なくとも１種のポリマーアニオン The following (I), (II) and (III) are doped into a π-conjugated polymer containing at least one selected from the group consisting of ethylenedioxythiophene and alkylated ethylenedioxythiophene as a monomer component. A conductive polymer composition characterized by the above.
(I): Sulfonic acid and N- (2-hydroxyethyl) acrylamide, N- (hydroxymethyl) acrylamide, N-methylmethacrylate, N- (4-hydroxyphenyl) methacrylamide, N-phenylacrylamide or N From a copolymer (II): polystyrene sulfonic acid (III): sulfonated polyester and phenol sulfonic acid novolac resin having a molar ratio of 9.5: 0.5 to 4: 6 with a polymerizable monomer composed of phenylmethacrylate. At least one polymer anion selected from the group
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