JP2014019831A - Electron-conducting polymers, methods of producing the same, paints and antistatic coatings comprising the electron-conducting polymer, and conductive polymer compositions - Google Patents
Electron-conducting polymers, methods of producing the same, paints and antistatic coatings comprising the electron-conducting polymer, and conductive polymer compositions Download PDFInfo
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- JP2014019831A JP2014019831A JP2012162034A JP2012162034A JP2014019831A JP 2014019831 A JP2014019831 A JP 2014019831A JP 2012162034 A JP2012162034 A JP 2012162034A JP 2012162034 A JP2012162034 A JP 2012162034A JP 2014019831 A JP2014019831 A JP 2014019831A
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- Prior art keywords
- conductive polymer
- electron
- salt
- electron conductive
- anion
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- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 86
- 238000000576 coating method Methods 0.000 title claims abstract description 31
- 239000000203 mixture Substances 0.000 title claims description 44
- 239000002322 conducting polymer Substances 0.000 title abstract description 6
- 238000000034 method Methods 0.000 title description 14
- 239000003973 paint Substances 0.000 title description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 41
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims abstract description 30
- 239000011248 coating agent Substances 0.000 claims abstract description 29
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 29
- 150000001450 anions Chemical class 0.000 claims abstract description 27
- 239000000126 substance Substances 0.000 claims abstract description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 21
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- 239000002253 acid Substances 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 150000003577 thiophenes Chemical class 0.000 claims abstract description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 11
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- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 4
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- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
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- Paints Or Removers (AREA)
- Conductive Materials (AREA)
Abstract
Description
本発明は、一般に電子伝導性重合体に関するものであり、より特定的には、塗膜及び制電性被覆物として適用する場合、塗布基体との密着性にすぐれ、滑らかな膜質を形成し、膜のヒビ割れや光散乱などを起こさないように改良された電子伝導性重合体及びその製造方法に関する。この発明は、また、そのような電子伝導性重合体を含む塗料、制電性被覆物に関する。この発明はさらに、そのような電子伝導性重合体が分散されてなる導電性重合体組成物に関する。 The present invention generally relates to an electron conductive polymer, and more specifically, when applied as a coating film and an antistatic coating, it has excellent adhesion with a coating substrate, and forms a smooth film quality. The present invention relates to an electron conductive polymer improved so as not to cause cracking of the film and light scattering, and a method for producing the same. The present invention also relates to paints and antistatic coatings containing such electron conductive polymers. The present invention further relates to a conductive polymer composition in which such an electron conductive polymer is dispersed.
近年、樹脂に制電性を付与することが重要になってきており、これを達成するために、従来より、界面活性剤等の帯電防止剤を樹脂成形品の表面に塗布したり、帯電防止剤を樹脂中に練り込む方法が知られている。しかしながら、前者の方法では、長時間経過すると制電性が著しく低下するため、持続性を有する高制電性樹脂として、実用化には供し難い。一方、後者の方法では、帯電防止剤と樹脂との相溶性が悪く、帯電防止剤が成形品の表面から剥離したり、ブリ-ディングやブル-ミングして、制電効果が低下するという課題があった。 In recent years, it has become important to impart antistatic properties to resins. To achieve this, antistatic agents such as surfactants have been conventionally applied to the surface of resin molded products, or antistatic properties have been achieved. A method of kneading an agent into a resin is known. However, in the former method, the antistatic property is remarkably lowered after a long time, so that it is difficult to put it into practical use as a highly antistatic resin having durability. On the other hand, in the latter method, the compatibility between the antistatic agent and the resin is poor, and the antistatic agent is peeled off from the surface of the molded product, or the antistatic effect is reduced due to bleeding or blooming. was there.
また、界面活性剤などの帯電防止剤は、湿度依存性があり、低湿度下では、制電効果が失活する、あるいは、樹脂を成形した後に、帯電防止効果が発現するまでに最低１〜３日掛かり、遅効性であるという課題があった。 Antistatic agents such as surfactants are dependent on humidity, and at low humidity, the antistatic effect is deactivated, or after molding the resin, the antistatic effect is at least 1 to It took 3 days and there was a problem that it was slow-acting.
また、カ-ボンブラックやカ-ボンファイバ-などを樹脂に練り込む方法が提案されている。この方法によると、帯電防止性にすぐれ、帯電防止性に持続性がある樹脂組成物が得られる。しかし、この方法では、透明な成形品が得られなかったり、成形品の色の選択が制限されるなどの課題があった。 In addition, a method of kneading carbon black or carbon fiber into a resin has been proposed. According to this method, a resin composition having excellent antistatic properties and durability in antistatic properties can be obtained. However, this method has a problem that a transparent molded product cannot be obtained, and selection of the color of the molded product is restricted.
本発明者らは、上記の課題を解決する方法として、アルカリ金属またはアルカリ土類金属であるカチオンによって構成される金属塩類を溶解した溶液を、ポリアミド樹脂、ポリエ-テルエステルアミド樹脂、脂肪族ポリエステル、ポリ乳酸系樹脂、熱可塑性エラストマ-及びゴムに添加してなる制電性組成物を提案した(たとえば、特許文献１参照)。 As a method for solving the above problems, the present inventors have prepared a solution in which a metal salt composed of a cation that is an alkali metal or an alkaline earth metal is dissolved in a polyamide resin, a polyetheresteramide resin, an aliphatic polyester. An antistatic composition formed by adding to a polylactic acid resin, a thermoplastic elastomer and rubber has been proposed (for example, see Patent Document 1).
また、ポリウレタンからなる塩改質静電気散逸型重合体(Salt-modified electrostatic dissipative polymers)の製造方法として、リチウムビス(フルオロアルキルスルホニル)イミドを補助溶剤(co-solvents)に溶解して添加する方法が提案されている(特許文献２参照)。 In addition, as a method for producing salt-modified electrostatic dissipative polymers made of polyurethane, there is a method in which lithium bis (fluoroalkylsulfonyl) imide is dissolved in a co-solvent and added. It has been proposed (see Patent Document 2).
また、導電性重合体しては、ポリアニリン系、ポリピロール系やポリチオフェン系の導電性高分子がよく知られている。特に透明性がすぐれているのは、導電性ポリ（３，４−エチレンジオキシチオフェン）（ＰＥＤＯＴ）である。そして、すでにＰＥＤＯＴコロイド水溶液として商品化されており（商品名パイロンＰ，バイエル社製）、導電性コーティング剤として電子部品分野などで広く用いられている。 As the conductive polymer, polyaniline-based, polypyrrole-based, and polythiophene-based conductive polymers are well known. In particular, conductive poly (3,4-ethylenedioxythiophene) (PEDOT) has excellent transparency. And it has already been commercialized as a PEDOT colloid aqueous solution (trade name Pylon P, manufactured by Bayer), and is widely used in the field of electronic components as a conductive coating agent.
また、３，４−エチレジオキシチオフェン（ＥＤＯＴ）をビス（パーフルオロアルカンスルホニル）イミド又はその塩を含有する溶液中で、電解重合させて電極基体表面上に多孔性材料を形成する方法も提案されている（特許文献３参照）。 Also proposed is a method of forming a porous material on the surface of an electrode substrate by electrolytic polymerization of 3,4-ethylene dioxythiophene (EDOT) in a solution containing bis (perfluoroalkanesulfonyl) imide or a salt thereof. (See Patent Document 3).
また、ＥＤＯＴをポリスチレンスルホン酸（ＰＳＳ）の存在下、水性媒体中で過硫酸塩を用いて化学酸化重合を行い、ＰＥＤＯＴ−ＰＳＳを製造する方法も提案されている（特許文献４参照）。 There has also been proposed a method for producing PEDOT-PSS by subjecting EDOT to chemical oxidative polymerization using persulfate in an aqueous medium in the presence of polystyrene sulfonic acid (PSS) (see Patent Document 4).
しかしながら、特許文献１に記載の方法において、制電性組成物に添加する金属塩類の種類によっては、制電性能が十分でない場合があった。また、過塩素酸等の金属塩類を用いると、この制電性組成物から成るフィルムやシ-トを用いて金属類を包装する場合、金属表面を腐食、発錆あるいは汚染するという課題があった。 However, in the method described in Patent Document 1, the antistatic performance may not be sufficient depending on the type of metal salt added to the antistatic composition. In addition, when metal salts such as perchloric acid are used, there is a problem that the metal surface is corroded, rusted or contaminated when the metal is packaged using a film or sheet made of this antistatic composition. It was.
また、特許文献２に記載の方法では、金属塩類を溶解するための補助溶剤(エチレンカ-ボネ-ト、ジメチルスルホキシド、テトラメチレンスルホン、Ｎ-メチル-２-ピロリドン等)が制電性組成物の成形品の表面にブリ-ディングやブル-ミングし、製品を汚染する。また、成形品の表面を払拭することなどにより制電性が低下し、帯電防止性の耐久性が十分でない。特に、高温高湿度の雰囲気下では、ブリ-ディングやブル-ミングが促進されるため、制電性の低下が著しいという課題があった。 In addition, in the method described in Patent Document 2, an auxiliary solvent (ethylene carbonate, dimethyl sulfoxide, tetramethylene sulfone, N-methyl-2-pyrrolidone, etc.) for dissolving metal salts is used as the antistatic composition. The product surface is contaminated by bleeding or blooming on the surface. Further, the antistatic property is lowered by wiping the surface of the molded product, and the durability of the antistatic property is not sufficient. In particular, in an atmosphere of high temperature and high humidity, since bleeding and blooming are promoted, there is a problem that the antistatic property is remarkably lowered.
また、特許文献４の開示する上記ＰＥＤＯＴ−ＰＳＳはすぐれた導電性を示すが、その製造条件の制約から、特性上、工業上の適用に際して次のような制約がある。すなわち、強酸性、塗布基材への密着性が不十分、耐湿性・耐光性が低い、汎用樹脂との相溶性が低いなどの制約である。特許文献３の開示する電解重合法も、製造条件の制約がある。 Moreover, although the said PEDOT-PSS which patent document 4 discloses shows the outstanding electroconductivity, there exists the following restrictions on the industrial application from the restrictions of the manufacturing conditions on the characteristic. That is, there are constraints such as strong acidity, insufficient adhesion to the coated substrate, low moisture resistance and light resistance, and low compatibility with general-purpose resins. The electrolytic polymerization method disclosed in Patent Document 3 is also limited in manufacturing conditions.
本発明は、上記課題に鑑みてなされたものであり、塗膜及び制電性被覆物として適用する場合、塗布基体との密着性にすぐれ、滑らかな膜質を形成し、膜のヒビ割れや光散乱などを起こさない電子伝導性重合体を提供することを目的とする。 The present invention has been made in view of the above problems, and when applied as a coating film and an antistatic coating, it has excellent adhesion to a coated substrate, forms a smooth film quality, and is free from cracks and light of the film. An object is to provide an electron conductive polymer which does not cause scattering.
本発明の他の目的は、イオン伝導型の制電特性と電子伝導型の制電特性の両者を合わせ持つ電子伝導性重合体を提供することにある。 Another object of the present invention is to provide an electron conductive polymer having both ion conduction type antistatic characteristics and electron conduction type antistatic characteristics.
本発明の他の目的は、透明な電子伝導性重合体を提供することにある。 Another object of the present invention is to provide a transparent electron conducting polymer.
この発明の他の目的は、そのような電子伝導性重合体の製造方法を提供することにある。 Another object of the present invention is to provide a method for producing such an electron conductive polymer.
本発明のさらに他の目的は、そのような電子伝導性重合体を用いた塗料及び制電性被覆物を提供することにある。 Still another object of the present invention is to provide a paint and an antistatic coating using such an electron conductive polymer.
本発明の他の目的は、熱安定性にすぐれ、ブリ-ディング、ブル-ミング及び移行汚染が発生せず、湿度に依存せずに、即効性にすぐれ、物性の低下を招かず、かつ、すぐれた制電性が持続する導電性重合体組成物を提供することを目的とする。 Another object of the present invention is to provide excellent thermal stability, no bleeding, blooming and migration contamination, no dependence on humidity, high immediate effect, no deterioration of physical properties, and It is an object of the present invention to provide a conductive polymer composition that maintains excellent antistatic properties.
本発明に係る電子伝導性重合体は、チオフェンの３位又は４位の水素原子をエーテル酸素で置換したチオフェン誘導体を、フルオロ基及びスルホニル基を備える陰イオンを有する酸又はその塩を含有する媒体中で、化学酸化重合してなる。 An electron conductive polymer according to the present invention includes a medium containing an acid having an anion having a fluoro group and a sulfonyl group, or a salt thereof, a thiophene derivative in which a hydrogen atom at the 3-position or 4-position of thiophene is substituted with ether oxygen. It is formed by chemical oxidative polymerization.
チオフェンの３位又は４位の水素原子をエーテル酸素で置換したチオフェン誘導体を、フルオロ基及びスルホニル基を備える陰イオンを有する酸又はその塩を含有する媒体中で化学酸化重合させて得た電子伝導性重合体は、上記酸又はその塩を含有しない媒体中で化学酸化重合させたものより、伝導度が高くなることを見出し、本発明に到達した。 Electronic conduction obtained by chemical oxidative polymerization of a thiophene derivative in which the hydrogen atom at the 3-position or 4-position of thiophene is replaced with ether oxygen in a medium containing an acid having an anion having a fluoro group and a sulfonyl group or a salt thereof. The conductive polymer has been found to have higher conductivity than that obtained by chemical oxidative polymerization in a medium containing no acid or salt thereof, and has reached the present invention.
イオン伝導はバトンを手渡しするようにイオンが分子内及び分子間を移動するイメージであるのに対し、電子伝導はボールを筒中に転がすように電子が分子内及び分子間を移動するイメージである。後者の方が静電気の流れは速く、帯電防止剤としての効果も高い。本発明に係る電子伝導性重合体は、本来の電子伝導の特性を持ちながら、イオン伝導の特性も合わせ持つので、帯電防止剤としての効果が高くなることが見出された。 Ion conduction is an image in which ions move within and between molecules to hand baton, whereas electron conduction is an image in which electrons move within and between molecules as a ball rolls into a cylinder. The latter is faster in static electricity and more effective as an antistatic agent. It has been found that the electron conductive polymer according to the present invention has the original electron conduction characteristics and also has the ion conduction characteristics, so that the effect as an antistatic agent is enhanced.
上記チオフェン誘導体としては、３，４−エチレンジオキシチオフェンが好ましい。フルオロ基及びスルホニル基を備える陰イオンを有する酸又はその塩の存在下で化学酸化重合して得られたポリ(３，４−エチレンジオキシチオフェン)は、自由に動くことのできるキャリアを生じるため、有機物でありながら電子伝導型の導電性を有するようになる。このポリ（３，４−エチレンジオキシチオフェン）は、塗布基体との密着性にすぐれ、低結晶であることから滑らかな膜質を形成し、膜のヒビ割れや光散乱などを起こさない、さらに透明性を有する被膜を与える。 As the thiophene derivative, 3,4-ethylenedioxythiophene is preferable. Poly (3,4-ethylenedioxythiophene) obtained by chemical oxidative polymerization in the presence of an acid having an anion having a fluoro group and a sulfonyl group or a salt thereof produces a carrier that can move freely. Even though it is an organic material, it has electron conductivity type conductivity. This poly (3,4-ethylenedioxythiophene) has excellent adhesion to the coated substrate, and since it is a low crystal, it forms a smooth film quality and does not cause cracking or light scattering of the film. A film having properties is provided.
上記フルオロ基及びスルホニル基を備える陰イオンを有する酸は、ビス（フルオロスルホニル）イミド、ビス（トリフルオロメタンスルホニル）イミド又はトリフルオロメタンスルホン酸を含み、上記フルオロ基及びスルホニル基を備える塩は、リチウムビス（フルオロスルホニル）イミド、リチウムビス（トリフルオロメタンスルホニル）イミド又はトリフルオロメタンスルホン酸リチウムを含む。 The acid having an anion having a fluoro group and a sulfonyl group includes bis (fluorosulfonyl) imide, bis (trifluoromethanesulfonyl) imide or trifluoromethanesulfonic acid, and the salt having the fluoro group and the sulfonyl group is lithium bis (Fluorosulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide or lithium trifluoromethanesulfonate.
本発明の他の局面に従う電子伝導性重合体の製造方法は、チオフェンの３位又は４位の水素原子をエーテル酸素で置換したチオフェン誘導体を、フルオロ基及びスルホニル基を備える陰イオンを有する酸又はその塩を含有する媒体中で、化学酸化重合することを特徴とする。 According to another aspect of the present invention, there is provided a method for producing an electron conductive polymer comprising: a thiophene derivative in which a hydrogen atom at the 3-position or 4-position of thiophene is substituted with ether oxygen; an acid having an anion having a fluoro group and a sulfonyl group; It is characterized by chemical oxidative polymerization in a medium containing the salt.
３，４−エチレンジオキシチオフェンの酸化重合は、電極反応等によっても行うことができるが、工業的生産に適した方法として、化学酸化重合が選ばれた。化学酸化重合の触媒としては、過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩が好ましく、その他、塩化第二鉄、塩化アルミニウム、塩化第二銅などの金属塩、過酸化ナトリウム、過酸化バリウムなどの過酸化物、塩素酸塩、次亜塩素酸塩、ヨウ素酸塩、臭素酸塩などのハロゲン酸塩も用いることができる。 Oxidative polymerization of 3,4-ethylenedioxythiophene can be performed by an electrode reaction or the like, but chemical oxidative polymerization was selected as a method suitable for industrial production. As the catalyst for chemical oxidative polymerization, persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate are preferable. In addition, metal salts such as ferric chloride, aluminum chloride, and cupric chloride, sodium peroxide, Peroxides such as barium oxide, halogenates such as chlorates, hypochlorites, iodates and bromates can also be used.
本発明のさらに他の局面に従う導電性重合体組成物は、チオフェンの３位又は４位の水素原子をエーテル酸素で置換したチオフェン誘導体を、フルオロ基及びスルホニル基を備える陰イオンを有する酸又はその塩（第１の塩）を含有する媒体中で、化学酸化重合して得られた電子伝導性重合体を含む。上記電子伝導性重合体が、フルオロ基及びスルホニル基を備える陰イオンを有する第２の塩を溶解した、重合性モノマー、オリゴマー又はプレポリマーの中に分散している。 According to still another aspect of the present invention, there is provided a conductive polymer composition comprising an acid having an anion having a fluoro group and a sulfonyl group, or a thiophene derivative in which a hydrogen atom at the 3-position or 4-position of thiophene is substituted with ether oxygen. An electron conductive polymer obtained by chemical oxidative polymerization in a medium containing a salt (first salt) is included. The electron conductive polymer is dispersed in a polymerizable monomer, oligomer, or prepolymer in which a second salt having an anion having a fluoro group and a sulfonyl group is dissolved.
上記電子伝導性重合体は、フルオロ基及びスルホニル基を備える陰イオンを有する第２の塩を溶解した重合性モノマー、オリゴマー又はプレポリマーとの相溶性にすぐれる。イオン伝導の特性と電子伝導の特性を合わせ持ち、帯電防止剤としての効果が高い上記電子伝導性重合体が、フルオロ基及びスルホニル基を備える陰イオンを有する第２の塩を溶解した重合性モノマー、オリゴマー又はプレポリマーの中に分散されているので、高い制電効果を有する導電性重合体組成物となる。 The electron conductive polymer is excellent in compatibility with a polymerizable monomer, oligomer or prepolymer in which the second salt having an anion having a fluoro group and a sulfonyl group is dissolved. A polymerizable monomer in which the above-mentioned electron-conductive polymer having both ion-conducting characteristics and electron-conducting characteristics and having a high effect as an antistatic agent dissolves a second salt having an anion having a fluoro group and a sulfonyl group Since it is dispersed in the oligomer or prepolymer, it becomes a conductive polymer composition having a high antistatic effect.
本明細書で、「分散」とは、電子伝導性重合体が、組成物中に微液滴状になって散在あるいは溶込んでいる状態をいう。電子伝導性重合体は、単独又は揮発性溶剤（水を含む）に溶解させて分散される。 In this specification, “dispersion” refers to a state in which the electron conductive polymer is dispersed or dissolved in the composition in the form of fine droplets. The electron conductive polymer is dispersed alone or dissolved in a volatile solvent (including water).
揮発性溶媒とは、常温で液体が気化する溶媒をいい、水、メタノール、エタノール、イソプロパノール、１−ブタノール、２−ブタノール、シクロヘキサノールなどのアルコール類、アセトン、メチルエチルケトン、メチルブチルケトン、メチルイソブチルケトン、シクロヘキサノンなどのケトン類、テトラヒドロフラン、エチレングリコールモノエチルエーテル、プロピレングリコールモノエチルエーテルなどのエーテル類、酢酸メチル、酢酸エチル、酢酸ブチルなどのエステル類からなる群から選ばれた揮発性溶媒を挙げることができる。揮発性の溶媒を選ぶのは、当該組成物を被塗布物に塗布した後、乾燥しやすくするためである。揮発性を有するものなら、上記のものに限定されず、いずれも使用できる。 Volatile solvent means a solvent that vaporizes at room temperature. Water, methanol, ethanol, isopropanol, 1-butanol, 2-butanol, cyclohexanol and other alcohols, acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone A volatile solvent selected from the group consisting of ketones such as cyclohexanone, ethers such as tetrahydrofuran, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, and esters such as methyl acetate, ethyl acetate, and butyl acetate Can do. The reason why the volatile solvent is selected is to facilitate drying after the composition is applied to the object. As long as it has volatility, it is not limited to the above, and any can be used.
上記重合性モノマーとは、重合する官能基を有する化合物をいい、例えばアクリロイル基、メタクリロイル基、ビニル基などを有する重合性モノマーが挙げられる。態様としては、モノマー、オリゴマー、あるいは活性エネルギー線硬化性官能基を分子内に３つ以上有するものが挙げられる。 The polymerizable monomer means a compound having a functional group to be polymerized, and examples thereof include a polymerizable monomer having an acryloyl group, a methacryloyl group, a vinyl group and the like. Examples of the mode include monomers, oligomers, and those having three or more active energy ray-curable functional groups in the molecule.
重合性モノマーとしては、例えば、単官能性のもの：２−エチルヘキシル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、２−エトキシエチル(メタ)アクリレート、２−エトキシエトキシエチル(メタ)アクリレート、２−ヒドロキシエチル(メタ)アクリレート、２−ヒドロキシプロピル(メタ)アクリレート、ポリカプロラクトン変性ヒドロキシエチル(メタ)アクリレート、ジシクロペンテニルオキシエチル(メタ)アクリレート、Ｎ−ビニルピロリドン、アクリロイルモルホリン、イソボルニル(メタ)アクリレート、酢酸ビニル、スチレンなど、二官能性のもの：ネオペンチルグリコールジ(メタ)アクリレート、１，９−ノナンジオールジ(メタ)アクリレート、１，６−ヘキサンジオールジ(メタ)アクリレート、１，４−ブタンジオールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、グリコールジ(メタ)アクリレート、ジプロピレングリコールジ(メタ)アクリレート、プロピレンなど、多官能性のもの：トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、トリメチロールプロパンの３モルプロピレンオキサイド付加物のトリ(メタ)アクリレート、トリメチルプロパンの６モルエチレンオキサイド付加物のトリ(メタ)アクリレート、グリセリンプロポキシトリ(メタ)アクリレート、ジペンタンエリスリトールヘキサ(メタ)アクリレート、ジペンタエリスリトールのカプロラクトン付加物のヘキサ(メタ)アクリレートなどが挙げられる。 Examples of the polymerizable monomer include monofunctional monomers: 2-ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-ethoxyethoxyethyl (meth) acrylate, 2- Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polycaprolactone-modified hydroxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, N-vinylpyrrolidone, acryloylmorpholine, isobornyl (meth) acrylate, Bifunctional compounds such as vinyl acetate and styrene: neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,4-butane Diol di ( Multifunctional ones such as (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, propylene: trimethylolpropane tri ( (Meth) acrylate, pentaerythritol tri (meth) acrylate, tri (meth) acrylate of 3 mol propylene oxide adduct of trimethylolpropane, tri (meth) acrylate of 6 mol ethylene oxide adduct of trimethylpropane, glycerin propoxytri (meta ) Acrylate, dipentane erythritol hexa (meth) acrylate, hexa (meth) acrylate of a caprolactone adduct of dipentaerythritol, and the like.
さらに、活性化エネルギー線硬化性の(メタ)アクリレート系化合物として、(メタ)アクリル酸２−ビニロキシエチル、(メタ)アクリル酸３−ビニロキシプロピル、(メタ)アクリル酸１−メチル−２−ビニロキシエチル、(メタ)アクリル酸２−ビニロキシプロピル、(メタ)アクリル酸４−ビニロキシブチル、(メタ)アクリル酸４−ビニロキシシクロヘキシル、(メタ)アクリル酸５−ビニロキシペンチル、(メタ)アクリル酸６−ビニロキシシクロヘキシル、(メタ)アクリル酸４−ビニロキシメチルシクロヘキシル、(メタ)アクリル酸ｐ−ビニロキシメチルフェニルメチル、(メタ)アクリル酸２−(ビニロキシエトキシ)エチル、(メタ)アクリル酸２−(ビニロキシエトキシエトキシ)エチル、(メタ)アクリル酸２−(ビニロキシエトキシエトキシエトキシ)エチル等を挙げることができる。 Furthermore, as the activated energy ray-curable (meth) acrylate-based compound, 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, 1-methyl-2-vinyloxyethyl (meth) acrylate, (Meth) acrylic acid 2-vinyloxypropyl, (meth) acrylic acid 4-vinyloxybutyl, (meth) acrylic acid 4-vinyloxycyclohexyl, (meth) acrylic acid 5-vinyloxypentyl, (meth) acrylic acid 6-vinyl Roxycyclohexyl, 4-vinyloxymethylcyclohexyl (meth) acrylate, p-vinyloxymethylphenylmethyl (meth) acrylate, 2- (vinyloxyethoxy) ethyl (meth) acrylate, 2- (meth) acrylic acid 2- ( Vinyloxyethoxyethoxy) ethyl, 2- (vinyloxyethoxyethoxyethoxy) ethyl (meth) acrylate, etc. Can be mentioned.
オリゴマーとは、有限個（一般的には１０個から１００個）のモノマーが結合した比較的分子量が低い重合体を指す。オリゴマーに対してポリマーは非常に多数（数100個以上）のモノマーが結合した状態のことをいう。オリゴマーとしては、例えば、不飽和ポリエステル、ポリエステル（メタ）アクリレート、ポリエーテル（メタ）アクリレート、アクリル（メタ）アクリレート、ウレタン（メタ）アクリレート、エポキシ（メタ）アクリレートなどが挙げられる。この中でも、ポリエチレングリコールのモノ又はジ（メタ）アクリレートは好ましく用いられる。その中でもオキシエチレン単位を少なくとも６個有するポリエチレングリコールのモノ又はジ（メタ）アクリレートが好ましく用いられる。 An oligomer refers to a polymer having a relatively low molecular weight to which a finite number of monomers (generally 10 to 100) are bonded. A polymer means a state in which a very large number (several hundreds or more) of monomers are bonded to an oligomer. Examples of the oligomer include unsaturated polyester, polyester (meth) acrylate, polyether (meth) acrylate, acrylic (meth) acrylate, urethane (meth) acrylate, and epoxy (meth) acrylate. Among these, polyethylene glycol mono- or di (meth) acrylate is preferably used. Among them, polyethylene glycol mono- or di (meth) acrylate having at least 6 oxyethylene units is preferably used.
プレポリマー (prepolymer) は、モノマーの重合または縮合反応を適当な所で止めた中間生成物である。ポリマーとなる前段階にあり、硬化剤などを使用することにより容易に重合や架橋反応を起こす事ができる。ウレタン樹脂系プレポリマー、シリコン樹脂系プレポリマーを含む。３つ以上の官能基を有するプレポリマーとしては、例えば、ジイソシアネート：ヘキサメチレンジイソシアネート、イソホロンジシアネート、トリレンジイソシアネート、ナフタレンジイソシアネート、ジフェニルメタンジイソシアネート、キシリレンジイソシアネートジシクロヘキシルメタンジイソシアネート、２，２，４−トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート、ノルボルナンジイソシアネートなどと、水酸基含有(メタ)アクリレート：２−ヒドロキシエチル(メタ)アクリレート、２−ヒドロキシプロピル(メタ)アクリレートなどの単官能のもの、ペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレートなどの３官能以上のものとを反応してなるものなどが挙げられる。 A prepolymer is an intermediate product that stops the polymerization or condensation reaction of the monomer at an appropriate point. It is in the pre-stage of becoming a polymer, and it can easily cause polymerization or crosslinking reaction by using a curing agent or the like. Includes urethane resin-based prepolymers and silicon resin-based prepolymers. Examples of the prepolymer having three or more functional groups include diisocyanate: hexamethylene diisocyanate, isophorone dicyanate, tolylene diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate dicyclohexylmethane diisocyanate, and 2,2,4-trimethylhexacene. Methylene diisocyanate, lysine diisocyanate, norbornane diisocyanate and the like, and hydroxyl group-containing (meth) acrylate: monofunctional ones such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, Examples include those obtained by reacting trifunctional or higher functional groups such as dipentaerythritol penta (meth) acrylate. It is.
上記フルオロ基及びスルホニル基を備える酸は、ビス（フルオロスルホニル）イミド、ビス（トリフルオロメタンスルホニル）イミド又はトリフルオロメタンスルホン酸が好ましい。上記フルオロ基及びスルホニル基を備える塩は、リチウムビス（フルオロスルホニル）イミド（（ＦＳＯ２）２ＮＬｉ）、リチウムビス（トリフルオロメタンスルホニル）イミド（（ＣＦ３ＳＯ２）２ＮＬｉ）又はトリフルオロメタンスルホン酸リチウム（ＣＦ３ＳＯ３Ｌｉ）が好ましい。 The acid having the fluoro group and the sulfonyl group is preferably bis (fluorosulfonyl) imide, bis (trifluoromethanesulfonyl) imide or trifluoromethanesulfonic acid. The salt having a fluoro group and a sulfonyl group is lithium bis (fluorosulfonyl) imide ((FSO 2 ) 2 NLi), lithium bis (trifluoromethanesulfonyl) imide ((CF 3 SO 2 ) 2 NLi) or trifluoromethanesulfonic acid. Lithium (CF 3 SO 3 Li) is preferred.
対になる陽イオンは、リチウム以外にも、アルカリ金属、２Ａ族元素、遷移金属及び両性金属からなる群の陽イオンからも好ましく選ばれる。 The cations to be paired are preferably selected from cations of the group consisting of alkali metals, group 2A elements, transition metals and amphoteric metals in addition to lithium.
上記電子伝導性重合体を、上記第２の塩を溶解した上記重合性モノマー、オリゴマー又はプレポリマー１００質量部に対して、０．００５〜５０．０質量部含むのが好ましい。 The electron conductive polymer is preferably contained in an amount of 0.005 to 50.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer, oligomer or prepolymer in which the second salt is dissolved.
上記電子伝導性重合体を分散させる前の、上記重合性モノマー、オリゴマー又はプレポリマー中において、上記フルオロ基及びスルホニル基を備える陰イオン有する第２の塩は、上記重合性モノマー、オリゴマー、プレポリマー、樹脂、エラストマー又は粘着性樹脂を含む組成物１００質量部に対して、０．０１質量部以上３０質量部以下含まれる。この組成物はイオン伝導性組成物である。 In the polymerizable monomer, oligomer or prepolymer before dispersing the electron conductive polymer, the second salt having an anion having the fluoro group and the sulfonyl group is the polymerizable monomer, oligomer or prepolymer. , 0.01 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the composition containing resin, elastomer or adhesive resin. This composition is an ion conductive composition.
上記電子伝導性重合体は、イオン液体に溶解させて、上記重合性モノマー、オリゴマー又はプレポリマーの中に分散させるのが好ましい。イオン液体を、上記電子伝導性重合体を溶解させる媒体として用いることができる。イオン液体とは、液体で存在する塩（えん）をいうが、基本的には、陽イオンの種類で、ピリジン系、脂環肪族アミン系、脂肪族アミン系の３つに大別される。分散性の良好なイオン液体としては、ビス（トリフルオロメタンスルホニルイミド）メチルトリブチルアンモニウム塩（（ＣＦ３ＳＯ２）２Ｎ-・Ｎ+（ＣＨ３）（Ｃ４Ｈ９）３）（第３の塩）を挙げることができる。 It is preferable that the electron conductive polymer is dissolved in an ionic liquid and dispersed in the polymerizable monomer, oligomer or prepolymer. An ionic liquid can be used as a medium for dissolving the electron conductive polymer. An ionic liquid refers to a salt (en) present in the liquid. Basically, the ionic liquid is classified into three types: pyridine, alicyclic amine, and aliphatic amine. . As an ionic liquid with good dispersibility, bis (trifluoromethanesulfonylimide) methyltributylammonium salt ((CF 3 SO 2 ) 2 N − .N + (CH 3 ) (C 4 H 9 ) 3 ) (third Salt).
本発明の導電性重合体組成物には、さらに酸化防止剤、熱安定剤、紫外線吸収剤、難燃剤、難燃助剤、着色剤、顔料、抗菌・抗カビ剤、耐光剤、可塑剤、粘着付与剤、分散剤、消泡剤、硬化触媒、硬化剤、レベリング剤、撥水剤、カップリング剤、フィラ−、加硫剤、キレート剤、加硫促進剤などの公知の添加剤を必要に応じて添加することができる。 The conductive polymer composition of the present invention further includes an antioxidant, a heat stabilizer, an ultraviolet absorber, a flame retardant, a flame retardant aid, a colorant, a pigment, an antibacterial / antifungal agent, a light fastener, a plasticizer, Requires known additives such as tackifiers, dispersants, antifoaming agents, curing catalysts, curing agents, leveling agents, water repellents, coupling agents, fillers, vulcanizing agents, chelating agents, vulcanization accelerators It can be added depending on.
本発明の導電性重合体組成物を用いて、フィルム、塗料等を得ることができる。また、本発明の制電性組成物を成形表面で硬化させて、制電性の被覆物とすることもできる。本発明の組成物は、膜、塗料あるいは被覆物として使用する場合に特に有効に作用する。 A film, a paint, etc. can be obtained using the conductive polymer composition of the present invention. Further, the antistatic composition of the present invention can be cured on the molding surface to form an antistatic coating. The composition of the present invention works particularly effectively when used as a film, paint or coating.
硬化のための、(メタ)アクリロイル基、アルケニル基の重合は、加熱、紫外線、可視光、電子線などのエネルギーによってなされるが、適宜、公知の重合開始剤を使用してもよい。 Polymerization of the (meth) acryloyl group and alkenyl group for curing is performed by energy such as heating, ultraviolet light, visible light, and electron beam, and a known polymerization initiator may be used as appropriate.
チオフェンの３位又は４位の水素原子をエーテル酸素で置換したチオフェン誘導体を、フルオロ基及びスルホニル基を備える陰イオンを有する酸又はその塩を含有する媒体中で、化学酸化重合してなる電子伝導性重合体は、塗膜及び制電性被覆物として適用する場合、塗布基体との密着性にすぐれ、低結晶性であることから滑らかな膜質を形成し、膜のヒビ割れや光散乱などを起こさない、かつ静電気の流れが速いので、帯電防止剤としての効果が高く、電子デバイス用途に有用に適用することができる。また、この電子伝導性重合体を、フルオロ基及びスルホニル基を備える陰イオンを有する第２の塩を溶解した重合性モノマー、オリゴマー又はプレポリマーの中に分散させることによって、制電性の高い導電性重合体組成物が得られた。 Electron conduction obtained by chemical oxidative polymerization of a thiophene derivative in which a hydrogen atom at the 3-position or 4-position of thiophene is substituted with ether oxygen in a medium containing an anion having a fluoro group and a sulfonyl group or a salt thereof. When the polymer is applied as a coating film or antistatic coating, it has excellent adhesion to the coated substrate and low crystallinity, thus forming a smooth film quality, and preventing film cracking and light scattering. Since it does not occur and the flow of static electricity is fast, it is highly effective as an antistatic agent and can be usefully applied to electronic device applications. Further, by dispersing this electron conductive polymer in a polymerizable monomer, oligomer or prepolymer in which a second salt having an anion having a fluoro group and a sulfonyl group is dissolved, a highly antistatic conductive property is obtained. A functional polymer composition was obtained.
塗布基体との密着性にすぐれ、滑らかな膜質を形成し、膜のヒビ割れや光散乱などを起こさない電子伝導性重合体を得るという目的を、チオフェンの３位又は４位の水素原子をエーテル酸素で置換したチオフェン誘導体を、フルオロ基及びスルホニル基を備える陰イオンを有する酸又はその塩を含有する媒体中で、化学酸化重合することによって実現した。 For the purpose of obtaining an electron conductive polymer that has excellent adhesion to the coated substrate, forms a smooth film quality, and does not cause cracking or light scattering of the film, the hydrogen atom at the 3-position or 4-position of thiophene is converted to ether. The oxygen-substituted thiophene derivative was realized by chemical oxidative polymerization in a medium containing an acid having an anion having a fluoro group and a sulfonyl group or a salt thereof.
電子伝導性重合体は、下記化１に示す反応によって得られる。式（Ａ）は、フルオロ基及びスルホニル基を備える陰イオンを有する酸又はその塩を含有する媒体中で、３，４−エチレンジオキシチオフェンを化学酸化重合して得られた電子伝導性重合体の化学構造式を示す。式（Ｂ）は、フルオロ基及びスルホニル基を備える陰イオンを有する酸又はその塩を含有しない媒体中で、３，４−エチレンジオキシチオフェン（ＥＤＯＴ）を化学酸化重合して得られた電子伝導性重合体の化学構造式を示す。
式（Ａ）に示す、フルオロ基及びスルホニル基を備える陰イオンを有する酸又はその塩を含有する媒体中で３，４−エチレンジオキシチオフェンを化学酸化重合させたものは、式（Ｂ）で示すものより、伝導度が高くなることを見出した。 A compound obtained by chemical oxidative polymerization of 3,4-ethylenedioxythiophene in a medium containing an acid having an anion having a fluoro group and a sulfonyl group or a salt thereof represented by formula (A) is represented by formula (B). It has been found that the conductivity is higher than that shown.
伝導度が高まる理由について考察すると、式（Ａ）に示すように、超強酸のアニオンであり高い求核性を有する陰イオン（（ＣＦ３ＳＯ２）２Ｎ-）は、酸化状態で生成するポリ(３，４−エチレンジオキシチオフェン)と強く相関し、カチオンラジカル性を帯びさせ、安定化する。一方、陽イオンであるＬｉイオンは、エーテル酸素とイオウ原子に取り囲まれ、キレートを形成し安定化する。式（Ａ）のような高分子鎖の電荷を帯びた単位（ポーラロン（ラジカルカチオン）あるいはバイポーラロン（ジカチオン））の中を電子が移動することによって導電性が発現すると推定される。また、式（Ａ）において、ＥＤＯＴが６個以上連結される場合に、高い伝導度を示すことが判っている。この状態で、リチウムビス（トリフルオロメタンスルホニル）イミド（（ＣＦ３ＳＯ２）２ＮＬｉ）は、ＰＥＤＯＴ中に分散している。 Considering the reason why the conductivity is increased, as shown in the formula (A), an anion ((CF 3 SO 2 ) 2 N-) which is an anion of a super strong acid and has high nucleophilicity is generated in an oxidized state. It strongly correlates with poly (3,4-ethylenedioxythiophene), has a cationic radical property, and is stabilized. On the other hand, Li ions, which are cations, are surrounded by ether oxygen and sulfur atoms to form chelates and stabilize. It is presumed that the conductivity is developed by the movement of electrons in the charged unit (polaron (radical cation) or bipolaron (dication)) of the polymer chain as in formula (A). Moreover, in Formula (A), when six or more EDOT is connected, it turns out that a high conductivity is shown. In this state, lithium bis (trifluoromethanesulfonyl) imide ((CF 3 SO 2 ) 2 NLi) is dispersed in PEDOT.
そして、この電子伝導性重合体に外部より電場が印加されると、硬化膜中において、Ｌｉイオン種は、相応する極(膜表面)に向って、エーテル酸素原子及びイオウ原子の分子運動を利用して移動(イオン輸送)し、イオン伝導型の制電特性を発現する。すなわち、バトンを手渡しするようにＬｉイオンが分子内及び分子間を移動するイメージである。他方、カチオンラジカル性を帯びた電子伝導性重合体が電子伝導型の制電特性を発現する。すなわち、ボールを筒中に転がすようにラジカル（電子）が分子内及び分子間を移動するイメージである。 When an electric field is applied to the electron conductive polymer from the outside, the Li ion species use the molecular motion of ether oxygen atoms and sulfur atoms toward the corresponding pole (film surface) in the cured film. It moves (ion transport) and develops ion conduction type antistatic characteristics. That is, it is an image in which Li ions move within and between molecules so as to hand baton. On the other hand, an electron-conducting polymer having a cationic radical property exhibits an electron-conducting antistatic property. That is, it is an image in which radicals (electrons) move in and between molecules so as to roll the ball into the cylinder.
このように本発明で得られた電子伝導性重合体は、イオン伝導型の制電特性と電子伝導型の制電特性の両者を合わせ持ち、これらの相乗効果により、制電性の大きい電子伝導性重合体となる。この電子伝導性重合体は、透明性が高いという特徴も有する。なお、「イオン伝導型」、「電子伝導型」の概念については、小長谷重次、科学と工業、７５（１０）、ｐ.４８３〜４９３（２００１）に詳述されている。 As described above, the electron conductive polymer obtained in the present invention has both an ion conduction type antistatic property and an electron conduction type antistatic property. It becomes a conductive polymer. This electron conductive polymer is also characterized by high transparency. The concepts of “ion conduction type” and “electron conduction type” are described in detail in Shigeji Konagaya, Kagaku to Kogyo, 75 (10), p. 483 to 493 (2001).
また、この電子伝導性重合体を、フルオロ基及びスルホニル基を備える陰イオンを有する第２の塩を溶解した、重合性モノマー、オリゴマー又はプレポリマーの中に分散させることにより、制電剤のブリーディング、ブル-ミング及び移行汚染が生じない導電性重合体組成物を与える。 Further, this electron conductive polymer is dispersed in a polymerizable monomer, oligomer or prepolymer in which a second salt having an anion having a fluoro group and a sulfonyl group is dissolved, whereby bleeding of the antistatic agent is performed. Providing a conductive polymer composition free from blooming and migration contamination.
以下、本発明の実施例を説明する。なお、文中、指数表示する場合があり、たとえば「１．６Ｅ+０４」と表示すると、１．６×１０４を意味するものとする。 Examples of the present invention will be described below. In the text, an index may be displayed. For example, “1.6E + 04” means 1.6 × 10 4 .
（電子伝導性重合体の合成）
水５０ｍｌに、ビス(トリフルオロメタンスルホニル)イミド（（ＣＦ３ＳＯ２）２ＮＨ）１４．０質量部、過硫酸ナトリウム４．８質量部を溶解し、常温で攪拌しながら、３，４−エチレンジオキシチオフェン２ｍｌを徐々に滴下（滴下時間、１時間）し、滴下終了後、さらに２４時間反応させた。得られた反応液をアンモニア水（２５％）でｐＨ７．５とした後、メタノールで再沈殿し、濾過、乾燥を行い、ポリ(３，４−エチレンジオキシチオフェン)からなる電子伝導性重合体（Ａ）を得た。
(Synthesis of electron conductive polymer)
In 50 ml of water, 14.0 parts by mass of bis (trifluoromethanesulfonyl) imide ((CF 3 SO 2 ) 2 NH) and 4.8 parts by mass of sodium persulfate are dissolved, and 3,4-ethylene is stirred at room temperature. 2 ml of dioxythiophene was gradually dropped (dropping time, 1 hour), and after completion of the dropping, the reaction was further continued for 24 hours. The obtained reaction solution was adjusted to pH 7.5 with aqueous ammonia (25%), then reprecipitated with methanol, filtered and dried, and an electron conductive polymer composed of poly (3,4-ethylenedioxythiophene). (A) was obtained.
（導電性重合体組成物の調整）
次いで、メチルメタクリレート単量体１００質量部に、イオン伝導性単量体組成物（ポリエチレングリコールジメタクリレートにリチウムビス（トリフルオロメタンスルホニル）イミドを５０質量部％溶解してなる組成物（サンコノール（登録商標）Ａ６００−５０Ｒ，三光化学工業（社）製、オキシエチレン単位１４））５質量部と、光開始剤Ｌｕｎａ１００（日本シィベルヘグナー製）５質量部とを配合したイオン伝導性単量体体組成物１００質量部に対して、上記電子伝導性重合体（Ａ）１．５質量部を添加し、２時間攪拌して、液状導電性重合体組成物を得た。この液状導電性重合体組成物を、ポリエチレンテレフタレート（ＰＥＴ）フィルム（厚さ６０μｍ）上に、バーコータを用いて、乾燥時の塗膜の厚さが６μｍになるように塗布し、乾燥後、水銀ランプを用いて、紫外線（積算３００ｍＪ／ｃｍ２、１５秒）を照射した。得られた塗膜の表面抵抗率は、１．６Ｅ+０４Ω／ｓｑであった。なお、上記電子伝導性重合体（Ａ）を含まないイオン伝導性単量体組成物を単独に塗布し、紫外線硬化した塗膜の表面抵抗率は、１．０Ｅ+０９Ω／ｓｑであった。
(Preparation of conductive polymer composition)
Next, an ion conductive monomer composition (a composition obtained by dissolving 50 parts by mass of lithium bis (trifluoromethanesulfonyl) imide in polyethylene glycol dimethacrylate) (100% by mass of methyl methacrylate monomer) ) A600-50R, manufactured by Sanko Chemical Co., Ltd., oxyethylene unit 14)) Ion conductive monomer composition containing 5 parts by mass and 5 parts by mass of photoinitiator Luna100 (Nihon Siebel Hegner) To 100 parts by mass of the product, 1.5 parts by mass of the electron conductive polymer (A) was added and stirred for 2 hours to obtain a liquid conductive polymer composition. This liquid conductive polymer composition was applied onto a polyethylene terephthalate (PET) film (thickness 60 μm) using a bar coater so that the thickness of the coating film when dried was 6 μm, and after drying, mercury Using a lamp, ultraviolet rays (integrated 300 mJ / cm 2 , 15 seconds) were irradiated. The surface resistivity of the obtained coating film was 1.6E + 04Ω / sq. In addition, the surface resistivity of the coating film obtained by coating the ion conductive monomer composition not containing the electron conductive polymer (A) alone and curing with ultraviolet rays was 1.0E + 09Ω / sq.
なお、上記電子伝導性重合体（Ａ）は、それ単独で、塗布基体との密着性にすぐれ、低結晶性であることから滑らかな膜質を形成し、膜のヒビ割れや光散乱などを起こさない、透明なフィルムを与えた。 The electron conductive polymer (A) alone is excellent in adhesion to the coated substrate and has low crystallinity, thereby forming a smooth film quality and causing cracks and light scattering of the film. Not gave a clear film.
実施例１において、水５０ｍｌに、ビス（フルオロスルホニル）イミド９．０質量部を溶解した以外は、実施例１と同様な操作を行い、ポリ(３，４−エチレンジオキシチオフェン)からなる電子伝導性重合体（Ｂ）を得た。次いで、ビス（トリフルオロメタンスルホニルイミド）メチルトリブチルアンモニウム塩に、この電子伝導性重合体（Ｂ）５．０質量部を添加して、５０℃、２時間攪拌後、コロイド状液体の電子伝導性重合体を得た。この電子伝導性重合体に、エポキシアクリレート５質量部、トリメチロールプロパントリアクリレート２５質量部、ネオペンチルグリコールジアクリレート２０質量部、ポリエチレングリコールジアクリレート（オキシエチレン単位９）４５質量部を混合し、得られた混合物に、イオン伝導性単量体組成物（ペンタエリスリトールトリアクリレートにリチウムビス（トリフルオロメタンスルホニル）イミドを２０質量部％溶解してなる組成物（サンコノール（登録商標）ＰＥＴＡ−２０Ｒ，三光化学工業（社）製）５質量部を添加し、さらに、２―メチル−２−ヒドロキシプロピルフェノン４質量部を添加したものを、ディスク基板上にスピンナによって塗布した。次いで、紫外線硬化させて、導電性重合体組成物からなる樹脂被覆体を得た。この樹脂被覆体に、印加電圧８ｋＶとして、帯電減衰を測定した。帯電圧１００Ｖ以下で、半減期は、０．３秒以下であった。なお、上記電子伝導性重合体（Ｂ）を含まないイオン伝導性単量体組成物を塗布した樹脂被覆体に対して、印加電圧８ｋＶとして、帯電減衰を測定した。帯電圧４００Ｖで、半減期は、３秒以下であった。 In Example 1, an electron consisting of poly (3,4-ethylenedioxythiophene) was prepared in the same manner as in Example 1 except that 9.0 parts by mass of bis (fluorosulfonyl) imide was dissolved in 50 ml of water. A conductive polymer (B) was obtained. Next, 5.0 parts by mass of this electron conductive polymer (B) is added to bis (trifluoromethanesulfonylimide) methyltributylammonium salt, and the mixture is stirred at 50 ° C. for 2 hours. Coalescence was obtained. To this electron conductive polymer, 5 parts by mass of epoxy acrylate, 25 parts by mass of trimethylolpropane triacrylate, 20 parts by mass of neopentyl glycol diacrylate, 45 parts by mass of polyethylene glycol diacrylate (oxyethylene unit 9) were mixed to obtain. An ion conductive monomer composition (a composition obtained by dissolving 20 parts by mass of lithium bis (trifluoromethanesulfonyl) imide in pentaerythritol triacrylate (Sanconol (registered trademark) PETA-20R, Sanko Chemical Co., Ltd.)) 5 parts by mass (manufactured by Kogyo Kogyo Co., Ltd.) and 4 parts by mass of 2-methyl-2-hydroxypropylphenone were added onto the disk substrate with a spinner, and then cured with ultraviolet rays to conduct electricity. A resin coating comprising a conductive polymer composition was obtained. The resin coating was measured for charge decay at an applied voltage of 8 kV, with a charged voltage of 100 V or less and a half-life of 0.3 seconds or less, not including the electron conductive polymer (B). The charge decay was measured for an applied voltage of 8 kV on the resin coating coated with the ion conductive monomer composition, and the half-life was 3 seconds or less at a charged voltage of 400 V.
水１００ｍｌに、トリフルオロスルホン酸７．５０質量部、過硫酸アンモニウム６．５質量部を溶解し、常温で攪拌しながら、３，４−エチレンジオキシチオフェン２ｍｌを滴下した（滴下時間、１．５時間）。滴下終了後、さらに２４時間反応させた。得られた反応液をアンモニア水（２５％）でｐＨ７．０とした後、メタノールで再沈殿、濾過した。濾過物を水１００ｍｌに再分散させ、ポリ(３，４−エチレンジオキシチオフェン)からなる電子伝導性重合体（Ｃ）を得た。次いで、メチルメタクリレート単量体１００質量部に、イオン伝導性単量体組成物（ポリエチレングリコールジアクリレートにリチウムビス（トリフルオロメタンスルホニル）イミドを５０質量部％溶解した組成物（サンコノール（登録商標）Ａ４００−５０Ｒ，三光化学工業（社）製、オキシエチレン単位９））５質量部と、光開始剤Ｌｕｎａ１００（日本シィベルヘグナー製）５質量部とを添加したイオン伝導性単量体体組成物１００質量部に対して、上記電子伝導性重合体（Ｃ）１．５質量部を添加し、２時間攪拌して、液状導電性重合体組成物を得た。この液状導電性重合体組成物を、ポリカーボネート（ＰＣ）フィルム（厚さ６０μｍ）上に、バーコータを用いて、乾燥時の塗膜の厚さが３μｍになるように塗布し、乾燥後、水銀ランプを用いて、紫外線を照射した（積算３００ｍＪ／ｃｍ２、１５秒）を照射した。得られた塗膜の表面抵抗率は、１．０Ｅ+０５Ω／ｓｑであった。なお、上記電子伝導性重合体（Ｃ）を含まないイオン伝導性単量体組成物を単独に塗布し、紫外線硬化した塗膜の表面抵抗率は、１．０Ｅ+１１Ω／ｓｑであった。 In 100 ml of water, 7.50 parts by mass of trifluorosulfonic acid and 6.5 parts by mass of ammonium persulfate were dissolved, and 2 ml of 3,4-ethylenedioxythiophene was added dropwise with stirring at room temperature (dropping time, 1.5 time). After completion of dropping, the reaction was further continued for 24 hours. The resulting reaction solution was adjusted to pH 7.0 with aqueous ammonia (25%), reprecipitated with methanol, and filtered. The filtrate was redispersed in 100 ml of water to obtain an electron conductive polymer (C) composed of poly (3,4-ethylenedioxythiophene). Next, an ion conductive monomer composition (a composition in which 50 parts by mass of lithium bis (trifluoromethanesulfonyl) imide is dissolved in polyethylene glycol diacrylate (Sanconol (registered trademark) A400) in 100 parts by mass of the methyl methacrylate monomer. -50R, Sanko Chemical Industry Co., Ltd., oxyethylene unit 9)) 5 parts by mass and photoinitiator Luna100 (Nihon Siebel Hegner) 5 parts by mass added ion conductive monomer composition 100 1.5 parts by mass of the electron conductive polymer (C) was added to parts by mass and stirred for 2 hours to obtain a liquid conductive polymer composition. This liquid conductive polymer composition was applied onto a polycarbonate (PC) film (thickness 60 μm) using a bar coater so that the thickness of the coating film when dried was 3 μm, and after drying, a mercury lamp Was irradiated with ultraviolet rays (integrated 300 mJ / cm 2 , 15 seconds). The surface resistivity of the obtained coating film was 1.0E + 05Ω / sq. In addition, the surface resistivity of the coating film obtained by coating the ion conductive monomer composition not containing the electron conductive polymer (C) alone and curing with ultraviolet rays was 1.0E + 11Ω / sq.
実施例１において、水５０ｍｌに、上記３，４−エチレンジオキシチオフェンの替わりに３−（２−（２−（２−ブトキシエトキシ）エトキシ）エトキシ）−４−メチルチオフェン、上記ビス(トリフルオロメタンスルホニル)イミドの替わりにリチウムビス（フルオロスルホニル）イミド１４．４質量部を溶解した以外は、実施例１と同様な操作を行い、ポリ(３−（２−（２−（２−ブトキシエトキシ）エトキシ）エトキシ）−４−メチルチオフェン)からなる電子伝導性重合体（Ｄ）を得た。次いで、実施例１と同様な方法で、上記電子伝導性重合体（Ｄ）２．０質量部を含有する重合体組成物を調整して、ＰＥＴフィルム上に塗布して、紫外線照射後、導電性重合体組成物からなる塗膜被覆フィルムを得た。この塗膜被覆フィルムの表面抵抗率は、１．０Ｅ+０４Ω／ｓｑであった。 In Example 1, 3- (2- (2- (2-butoxyethoxy) ethoxy) ethoxy) -4-methylthiophene, bis (trifluoromethane), instead of 3,4-ethylenedioxythiophene, in 50 ml of water Poly (3- (2- (2- (2-butoxyethoxy)) was prepared in the same manner as in Example 1 except that 14.4 parts by mass of lithium bis (fluorosulfonyl) imide was dissolved instead of sulfonyl) imide. An electron conductive polymer (D) consisting of ethoxy) ethoxy) -4-methylthiophene) was obtained. Next, in the same manner as in Example 1, a polymer composition containing 2.0 parts by mass of the electron conductive polymer (D) was prepared, applied on a PET film, irradiated with ultraviolet rays, and then conductive. A film-coated film made of a conductive polymer composition was obtained. The surface resistivity of this coated film was 1.0E + 04Ω / sq.
なお、上記実施例では、ポリ（３，４−エチレンジオキシチオフェン）、ポリ(３−（２−（２−（２−ブトキシエトキシ）エトキシ）エトキシ）−４−メチルチオフェン)を例示したが、この発明はこれらに限られるものでない。例えば特開平２００５−１５４４８１号公報に開示されている、下記一般式に示す、エーテル結合を含むチオフェン誘導体を、フルオロ基及びスルホニル基を備える陰イオンを有する酸又はその塩を含有する媒体中で、過硫酸塩を用いて化学酸化重合して得た電子伝導性重合体も好ましく使用できる。Ｌｉイオンはエーテル酸素に配位して安定化する。化２において、Ｒ１がメチル基、Ｒ２がブチル基の場合、この化合物は、３−（２−（２−（２−ブトキシエトキシ）エトキシ）エトキシ）−４−メチルチオフェンと読むが、これに限られるものでなく、式中、Ｒ１は水素、アルキル基又はエーテル酸素を表し，Ｒ２はアルキル基を表し、あるいはＲ１とＲ２がつながってリングを形成していてもよい。エーテル酸素の数も、例示される４個の場合に限られない。
また、本発明において用いられるフルオロ基及びスルホニル基を備える陰イオンを有する塩としては、上述したもの以外にも、たとえば、ＬｉＮ（Ｃ２Ｆ５ＳＯ２）２、ＬｉＮ（Ｃ４Ｆ９ＳＯ２）（ＣＦ３ＳＯ２）、ＬｉＮ（Ｃ８Ｆ１７ＳＯ２）（ＣＦ３ＳＯ２）、ＬｉＮ（ＣＦ３ＣＨ２ＯＳＯ２）２、ＬｉＮ（ＣＦ３ＣＦ２ＣＨ２ＯＳＯ２）２、ＬｉＮ（ＨＣＦ２ＣＦ２ＣＨ２ＯＳＯ２）２、ＬｉＮ（（ＣＦ３）２ＣＨＯＳＯ２）２、トリス(フルオロアルキルスルホニル)メチドリチウム Ｌｉ(ＣＦ３ＳＯ２)３Ｃなども使用できる。 As the salt having an anion having a fluoro group and the sulfonyl group used in the present invention, in addition to those described above, for example, LiN (C 2 F 5 SO 2) 2, LiN (C 4 F 9 SO 2 ) (CF 3 SO 2 ), LiN (C 8 F 17 SO 2 ) (CF 3 SO 2 ), LiN (CF 3 CH 2 OSO 2 ) 2 , LiN (CF 3 CF 2 CH 2 OSO 2 ) 2, LiN ( HCF 2 CF 2 CH 2 OSO 2 ) 2 , LiN ((CF 3 ) 2 CHOSO 2 ) 2 , tris (fluoroalkylsulfonyl) methidolithium Li (CF 3 SO 2 ) 3 C, and the like can also be used.
今回開示された実施例はすべての点で例示であって制限的なものではないと考えられるべきである。本発明の範囲は上記した説明ではなくて特許請求の範囲によって示され、特許請求の範囲と均等の意味及び範囲内でのすべての変更が含まれることが意図される。 It should be understood that the embodiments disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.
本発明に係る電子伝導性重合体は、塗膜及び制電性被覆物として適用する場合、塗布基体との密着性にすぐれ、低結晶性であることから滑らかな膜質を形成し、膜のヒビ割れや光散乱などを起こさない。この電子伝導性重合体は、帯電防止および導電性コーティング、コンデンサ、タッチスクリーン、有機ＬＥＤ、透明導電性インクジェット印刷用インク、フィルムへの塗布・印刷などによる半導体包装材料や液晶保護フィルム向け、タッチパネル、有機ＥＬ．有機ＴＦＴ，有機半導体、色素増感太陽電池、導電性ポリマー電極、固体電解コンデンサー、導電性有機薄膜、電子デバイス用途など広範囲に使用できる。 When applied as a coating film or an antistatic coating, the electron conductive polymer according to the present invention is excellent in adhesion to a coated substrate and has low crystallinity, thereby forming a smooth film quality and cracking of the film. Does not cause cracking or light scattering. This electronic conductive polymer is used for antistatic and conductive coatings, capacitors, touch screens, organic LEDs, transparent conductive ink jet printing inks, semiconductor packaging materials by coating and printing on films, liquid crystal protective films, touch panels, Organic EL. It can be used in a wide range of applications, including organic TFTs, organic semiconductors, dye-sensitized solar cells, conductive polymer electrodes, solid electrolytic capacitors, conductive organic thin films, and electronic device applications.
Claims (10)
前記フルオロ基及びスルホニル基を備える塩は、リチウムビス（フルオロスルホニル）イミド、リチウムビス（トリフルオロメタンスルホニル）イミド又はトリフルオロメタンスルホン酸リチウムを含む請求項１又は２に記載の電子伝導性重合体。 The acid having an anion having a fluoro group and a sulfonyl group includes bis (fluorosulfonyl) imide, bis (trifluoromethanesulfonyl) imide or trifluoromethanesulfonic acid,
The electron conductive polymer according to claim 1 or 2, wherein the salt having a fluoro group and a sulfonyl group includes lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, or lithium trifluoromethanesulfonate.
前記電子伝導性重合体が、フルオロ基及びスルホニル基を備える陰イオンを有する第２の塩を溶解した、重合性モノマー、オリゴマー又はプレポリマーの中に分散している導電性重合体組成物。 A thiophene derivative in which the hydrogen atom at the 3-position or 4-position of thiophene is substituted with ether oxygen is chemically oxidized in a medium containing an acid having an anion having a fluoro group and a sulfonyl group or a salt thereof (first salt). Including an electron conductive polymer obtained by polymerization,
A conductive polymer composition in which the electron conductive polymer is dispersed in a polymerizable monomer, oligomer or prepolymer in which a second salt having an anion having a fluoro group and a sulfonyl group is dissolved.
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