JP3730897B2 - A method for preventing or purifying contamination by a conductive polymer film, and a structure having the ability to prevent or purify contamination. - Google Patents
A method for preventing or purifying contamination by a conductive polymer film, and a structure having the ability to prevent or purify contamination. Download PDFInfo
- Publication number
- JP3730897B2 JP3730897B2 JP2001305463A JP2001305463A JP3730897B2 JP 3730897 B2 JP3730897 B2 JP 3730897B2 JP 2001305463 A JP2001305463 A JP 2001305463A JP 2001305463 A JP2001305463 A JP 2001305463A JP 3730897 B2 JP3730897 B2 JP 3730897B2
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- Prior art keywords
- conductive polymer
- polymer film
- contamination
- conductive
- preventing
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- Filtering Materials (AREA)
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- Surface Treatment Of Glass (AREA)
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Description
【０００１】
【発明の属する技術分野】
本発明は、ポリアニリン等の導電性高分子を使用して、照明器具カバー、トンネル壁用パネル、複写機等の各種精密機器のケース及び内外装部材等に導電性高分子膜を形成することにより、その表面における汚染を防止又は浄化する技術に関する。より詳しくは、トンネル内に設置される照明器具のカバー、電球のガラス球、もしくは蛍光灯の蛍光管のように常時照明灯から発光される可視光線に照射されていると同時に自動車排ガスによる汚染にも常時さらされている部材に特に好ましく採用できる汚染を防止又は浄化する技術に関する。
【０００２】
【従来の技術】
ポリアニリンあるいはポリピロール等の導電性高分子については、携帯電話，テレビ，パソコン，家電製品等から発生する電磁波をシールドする電磁波シールド材、電池用電極、静電防止剤、キャパシター、ダイオード，トランジスタ等の各種電子デバイス、エレクトロクロミック素子、各種センサー等への利用が期待されて多くの研究開発が行われており、一部については実用化の段階に到達しているものもある。
【０００３】
この導電性高分子については、多くの物質が既に開発されており、それには、前記したポリアニリン、ポリピロールの外にも、ポリチオフェン、ポリチオフェンビニレン、ポリイソチアナフテン、ポリアセチレン、ポリアルキルピロール、ポリアルキルチオフェン、ポリ−ｐ−フェニレン、ポリフェニレンビニレン、ポリメトキシフェニレン、ポリフェニレンスルファイド、ポリフェニレンオキシド、ポリアントラセン、ポリナフタレン、ポリピレン、ポリアズレンあるいはこれらの誘導体の重合体があげられる。なお、これらの導電性高分子は、前記利用においては単独又は２種類以上の混合物として用いられる。
【０００４】
これらの導電性高分子は、ドーピングすることが好ましく、このドーピングにより導電性が向上し、その結果電磁波シールド性が向上する。そのドーパントとしては、Ｌｉ，Ｎａ，Ｋ等のアルカリ金属、Ｃａ等のアルカリ土類金属等のドナー型ドーパント、あるいはＣｌ2，Ｂｒ2，Ｉ2等のハロゲン、ＰＦ3，ＡｓＦ5，ＢＦ3等のルイス酸、ＨＦ，ＨＣｌ，ＨＮＯ3，Ｈ2ＳＯ4，ＨＣｌＯ4等のプロトン酸、ＦｅＣｌ3，ＦｅＯＣｌ2，ＴｉＣｌ4，ＷＣｌ3等の遷移金属化合物、Ｃｌ-，Ｂｒ-，Ｉ-，ＣｌＯ4 -，ＰＦ3 -，ＢＦ3 -，ＡｓＦ3 -等の電解質アニオンのアクセプター型ドーパントが用いられる。
【０００５】
これらの導電性高分子を用いる前記した利用は、もっぱらその高導電性という特性を活用するものであり、特に電磁波シールド材として利用する際には、その特性が重要であることは前記のとおりである。また、その特性は、酸化もしくは還元反応、特に電気的酸化還元反応、又は酸もしくは塩基との反応により変化することも知られている。特に電子供与体及び電子受容体の性能を持つ導電性高分子はこれらの反応により電気的特性変化を発現する。
【０００６】
例えば、ポリアニリンは、酸化もしくは還元反応、又は酸もしくは塩基との反応により下記（１）の反応式により変化することが知られている（「高分子新素材 Ｏｎｅ Ｐｏｉｎｔ−５ 導電性ポリマー」、吉村進著、高分子学会編１７〜１８頁）。その結果、ポリアニリンを酸化した場合には、電導度は金属状態で色は緑色になり、還元した場合には電導度は絶縁状態で青色から無色透明となる。また、酸と反応させ酸性化した場合には、電導度は向上し緑色になり、塩基と反応させ塩基性化した場合には、電導度は低下し色は青色となる。
【０００７】
【式１】
本発明者は、長年、光触媒、特にチタンの酸化物、中でも過酸化チタンの光触媒性能の向上、活用手段等の関連技術の研究開発に関与し、その成果を多数提案している。他方、導電性高分子は、前記したとおり従前は電気伝導特性がもっぱら注目されており、その特性に基づく利用のみが注目されていた。そのような状況の中で、本発明者は、導電性高分子にも導電性と共に光触媒性能が存在しないかと着目し、鋭意研究したところ、この導電性高分子が光触媒性能を発現することを見出すことができ、これに関する発明を既に特許出願した（特願２００１−４４５８６）。
【０００９】
その出願発明は、導電性高分子に、その吸収波長の電磁波を照射することにより、その表面の汚染の防止、汚染流体の浄化、又は浄化用活性ラジカル種もしくは過酸化物を生成する技術に関する。より詳しくは、導電性高分子体、又はガラス、タイル、金属もしくはプラスチック等の各種素材で製造された各種構造体表面に形成された導電性高分子膜等の導電性高分子にその吸収波長、好ましくは絶縁状態における吸収波長の電磁波を照射することにより、導電性高分子表面の汚染を抑制する技術、汚染気体もしくは汚染液体等の汚染流体を浄化する技術、又は浄化用活性ラジカル種もしくは過酸化物を生成する技術に関するものである。
【００１０】
【発明が解決しようとする課題】
その特許出願により提案された発明は、前述のとおり導電性高分子に、その吸収波長、特に絶縁状態における吸収波長の電磁波を照射することにより、導電性高分子体表面又は構造体表面に形成された導電性高分子膜表面における汚染の防止、汚染の浄化、又は浄化用活性ラジカル種もしくは過酸化物を生成する技術に関するものである。
【００１１】
そこで、本発明者は、このような絶縁状態における吸収波長の電磁波の照射の有無にかかわりなく、導電性高分子膜表面における汚染防止、又は汚染浄化の技術を開発すべく更に鋭意検討したところ、導電性高分子膜に直流又は交流電圧を印加することにより、該膜表面における汚染の防止、あるいは汚染の浄化を行うことができることを見出し、その結果開発に成功したのが本願発明である。
【００１２】
したがって、本発明は、導電性高分子膜にその絶縁状態における吸収波長の電磁波を照射することの有無にかかわりなく、導電性高分子膜に直流又は交流電圧を印加することにより、その表面における汚染の防止又は汚染の浄化ができることを見出し、その特性を利用して、構造体表面に導電性高分子膜を形成し、構造体表面の汚染の防止、又は汚染の浄化を行う技術を提供することを発明の解決すべき課題とするものである。すなわち、その汚染の防止又は汚染の浄化技術を提供することを発明の目的とするものである。
【００１３】
【課題を解決するための手段】
本発明は、前記課題を解決するために、導電性高分子膜による汚染を防止又は浄化する方法、及び導電性高分子膜を持つ汚染を防止又は浄化する性能を有する構造体を提供するものであり、特に好ましくは該性能を有する導電性高分子膜が形成された蛍光管又はガラス球を備えるトンネル用照明灯、並びに該性能を有する導電性高分子膜が形成された透明又は半透明のカバーを備えるトンネル用照明器具を提供するものである。
【００１４】
そのうちの前者の汚染を防止又は浄化する方法は、導電性高分子膜に、電圧を印加することにより、該膜表面における汚染の防止又は浄化を行うものである。また、後者の構造体は、構造体本体に導電性高分子膜を持ち、かつ該導電性高分子膜に直流又は交流の電圧が印加できるように、導電性高分子膜又は導電膜等に電極を備えることにより汚染の防止又は浄化性能を発現するものであり、両者いずれの場合においても可視光又はそれ以下の波長の電磁波を照射することにより汚染の防止又は浄化する性能が向上する。
【００１５】
さらに、構造体における特に好ましい態様であるトンネル用の汚染の防止性能又は浄化性能を有する照明器具は、カバー表面に導電性高分子膜を持ち、かつ該高分子膜に直流又は交流電圧を印加する電極を持つものであり、同様の性能を有する照明灯は、蛍光管又はガラス球表面に導電性高分子膜に持ち、かつ該高分子膜に直流又は交流電圧を印加する電極を持つものである。
【００１６】
そして、本発明では、ポリアニリン、ポリピロール等の導電性高分子を使用して、照明器具カバー、トンネル壁用パネル、複写機等の各種精密機器のケース及び内装部材等に導電性高分子膜を形成し、その高分子膜に直流又は交流電圧を印加することにより、前記各種精密機器のケース及び内装部材等の表面における汚染を防止することができると共に自動車排ガス等の各種排ガス中に含有される未燃焼もしくは不完全燃焼成分の炭化水素、一酸化炭素、又は燃焼に伴って生成した有害成分であるＳＯX又はＮＯXを分解又は酸化して浄化することができる。
【００１７】
また、直流又は交流電圧の印加と同時に可視光線又はそれ以下の波長の電磁波、好ましくは３００〜９００ｎｍの範囲の電磁波を照射することにより汚染防止性能及び汚染浄化性能は格段に向上する。さらに、導電性高分子膜中の導電性高分子は、半導電状態あるいは絶縁状態にあるのが好ましく、そのため導電性高分子膜に対し、導電状態において吸収波長の電磁波照射処理又は酸もしくはアルカリ処理することにより一層汚染浄化性能が向上する。
【００１８】
特に、交流又は直流電圧が印加される導電性高分子膜及び導電膜をトンネル内に設置する照明器具のカバー、蛍光灯の蛍光管、電球のガラス球等に採用した場合には、導電性高分子膜は、トンネル内に設置される前記蛍光灯等の照明灯により必然的に常時可視光又はそれ以下の波長の電磁波を照射されることになり、それら表面の汚染、特に自動車排ガスによる汚染が防止され、その結果該汚染による照明光の低減を効果的に防止できる。
【００１９】
また、それと同時にトンネル中に放出される自動車排ガス中の未燃焼有害成分あるいはＮＯX等の有害燃焼成分を分解又は酸化して無害化物質に変換することもできる。さらに、この導電性高分子膜をトンネル壁全面に設置し、かつ照明の光量を増加させた場合には、トンネル内が明るくなり、その結果安全運転上有益であるだけでなく、トンネル内の空気浄化にも大いに有効である。
【００２０】
【発明の実施の形態】
本発明は、前述したとおり、直流又は交流が印加される導電性高分子膜による汚染を防止又は浄化する方法、及び直流又は交流が印加される導電性高分子膜を備える汚染防止又は浄化性能を有する構造体を提供するものであり、両者いずれの場合においても可視光又はそれ以下の波長の電磁波を照射することにより汚染防止、汚染浄化性能とも向上させることができる。なお、本発明における汚染の防止又は浄化は、排ガス等の各種有害汚染成分が導電性高分子膜表面に付着し、その汚染成分が導電性高分子膜により分解あるいは酸化等により浄化され、その結果該表面の汚染が防止されるものである。その際には、大気中のＨ2Ｏ、Ｏ2からＯＨ-、・Ｏ2ラジカルが形成され浄化機能を発現する。
【００２１】
また、特に好ましくは汚染が著しい環境下にあるトンネル内で使用され、かつ可視光線が常時照射されている部材である、照明灯あるいは照明器具に該性能を有する導電性高分子膜を形成することにより汚染浄化性能に優れた照明器具等を提供するものである。具体的には、該性能を有する導電性高分子膜が表面に形成された蛍光管又はガラス球を備えるトンネル用照明灯、並びに該性能を有する導電性高分子膜が表面に形成された透明又は半透明のカバーを備えるトンネル用照明器具を提供するものである。
【００２２】
導電性高分子には、前記したポリアニリン、ポリピロールの外にも、ポリチオフェン、ポリチオフェンビニレン、ポリイソチアナフテン、ポリアセチレン、ポリアルキルピロール、ポリアルキルチオフェン、ポリ−ｐ−フェニレン、ポリフェニレンビニレン、ポリメトキシフェニレン、ポリフェニレンスルファイド、ポリフェニレンオキシド、、ポリアントラセン、ポリナフタレン、ポリピレン、ポリアズレンあるいはこれらの誘導体の重合体等の多くのものが存在する。
【００２３】
本発明において、導電性高分子膜を形成するために使用する導電性高分子としては、前述した各種のものが使用でき特に制限されるものではないが、金属−絶縁体移転が起きる共役ポリマー、ポリマー鎖内に結合交替の不整を有する共役ポリマー、又は一次元的連鎖を有する共役ポリマーで、かつドーパミン機能、いわゆる電子供与体及び電子受容体機能を有するものが好ましく使用できる。それにはポリアニリン、ポリフェニレン等があり、特にはイオン性ポリマーであるポリアニリンが好ましい。
【００２４】
本発明の導電性高分子膜を形成する対象構造体としては、汚染防止性能、汚染浄化性能が要求される各種素材の構造物あるいは各種形状の構造物が該当し、トンネル壁用パネル、天井板、内装板、風道材、空調用器材及びケース、監視用カメラレンズカバー、トイレ用器材、冷蔵庫ケース及び内装部材、照明器具収納ケース、空気浄化用フィルター、半導体製造ラインのような超精密機器製造ライン用カバー、ガス分解装置用部材、並びに複写機、プリンター及びその他の各種精密機器のケース及び内装部材等が例示できる。
【００２５】
また、それら以外にも、建築物,自動車等の窓ガラス、自動車等の車両外装材、タンク、観賞用等の各種水槽、金属,プラスチック等のパイプ、衛生陶器、眼鏡、レンズ、レンズフィルター、貯湯器、浴槽機器、洗面機器、流し台、ドア取手、水道用活栓、道路用ミラー、電磁シールド材、基板等の半導体材料、複写機内部部品等の各種のものも例示できるが、特に制限されることはない。さらに、特にテレビの映像表示面ガラス、液晶表示装置の画像表示面ガラス、複写機の画像読取面ガラス等も例示できる。
【００２６】
特に好ましい導電性高分子膜形成対象物としては、前述したとおり自動車排ガス等による汚染が著しい環境下のトンネル内に設置され、かつ可視光線が常時照射されている照明器具及びその関連部材、具体的には照明器具用の透明もしくは半透明のカバー、蛍光灯の蛍光管、又は白熱灯等の各種電球のガラス球等がある。なお、前述した各種部材に使用する素材としては、板ガラス、セラミック、ステンレス,アルミ等の金属板、アクリル,ポリカーボネート,ＰＥＴ等のプラスチック板、綿布あるいは繊維等が例示できる。
【００２７】
本発明者は、長年、過酸化チタン、すなわちペルオキソ基を有するチタン酸化物の固着性能や光触媒性能の向上、活用手段等の関連技術の研究開発に関与し、その成果を多数提案している。そこで、本発明においても、導電性高分子と過酸化チタンの併用、あるいはそれに加えて更に導電性向上物質との併用も試みたところ、以外にも導電性高分子を単独使用する場合に比し、一段と優れた汚染防止性能及び汚染浄化性能を発現することが判明した。
【００２８】
本発明において、構造体に導電性高分子膜を形成するには、導電性高分子を含有する分散液を使用し構造体表面に塗布することにより形成することができる。しかしながら、この場合には導電性高分子の構造体表面との結合力が十分なものとは言い難く、そのために結合力を向上せしめる助剤を併用するのがよい。それには、前記した過酸化チタンが優れた結合力向上のための助剤としての性能も有しており好ましく使用できる。
【００２９】
前記助剤としては、前記過酸化チタン以外の各種のものも制限されることなく使用でき、それには、シリカゾル、インジウム−スズ酸化物（ＩＴＯ）及びそれをを含有する無機系高分子樹脂、又はいわゆるアクリルシリコン樹脂やフッ素樹脂等が例示できる。かかる助剤及び導電性高分子膜を含有する分散液を形成するには、前記助剤の分散液に導電性高分子粉末を分散させるのがよい。例えば、過酸化チタン分散液に導電性高分子粉末を分散させることで形成できる。
【００３０】
その助剤成分の選択に当たっては、前記した各種の構造体材料との親和性を考慮して決定するのがよい。一般的には、例えば、ガラスにはシリカゾル又はチタン酸化物がよく、プラスチックには無機系高分子樹脂がよく、金属、ガラス、プラスチック、その他の素材にはチタン酸化物がよい。また、チタンの酸化物のうち過酸化チタンは、構造体表面との結合力を向上せしめる助剤としての機能と共に汚染の防止及び浄化性能を向上させることができ好ましく、特に導電性向上物質と併用した場合には導電性を一段と向上させることができ好ましい。
【００３１】
この過酸化チタンには、アモルファス型とアナターゼ型の２種があり、前者のアモルファス型過酸化チタンには、光触媒能がなく、高分子材料板に被膜を形成しても該材料の劣化あるいは分解させる恐れのない導電性高分子膜を造膜するのに適している。それに対して、アナターゼ型過酸化チタンには光触媒能があり、高分子材料に被膜を形成した場合には、劣化等を起こさせる恐れがあるものの、親水基を有する構造体との親和性が優れているので、無機材料を素材とする構造体表面に導電性高分子膜を形成する際使用するのに好ましい。
【００３２】
この過酸化チタンは、導電性高分子と併用して導電性高分子膜を形成した場合には、導電性高分子膜の導電性、特に絶縁状態における導電性を向上させることができる。さらに、導電性高分子膜に、過酸化チタンに加えて導電性向上物質も併せて含有させることにより、その絶縁状態における導電性を一層向上させることができる。また、過酸化チタンと導電性向上物質と含有する被膜は、導電性を有し、この膜を導電性高分子と構造体本体との間に導電膜として介在させることにより、導電性高分子膜、特に導電性高分子のみを含有する導電性高分子膜に電圧を印加する際の導電性膜として有効である。
【００３３】
かかる導電性向上物質としては、導電性高分子と過酸化チタンを含有する分散液により形成される被膜あるいは過酸化チタンを単独で含有する被膜に比し導電性を向上せしめることができるものであれば、特に制限されることはなく金属塩などの各種物質が使用可能である。その金属塩としては、例えば、アルミニウム、錫、クロム、ニッケル、アンチモン、鉄、銀、セシウム、インジウム、セリウム、セレン、銅、マンガン、カルシウム、白金、タングステン、ジルコニウム、亜鉛等の金属塩があり、それ以外にも一部の金属あるいは非金属等については水酸化物あるいは酸化物も使用可能である。
【００３４】
それら金属塩等の各種物質について具体的物質名で示すと、塩化アルミニウム、塩化第１及び第２錫、塩化クロム、塩化ニッケル、塩化第１及び第２アンチモン、塩化第１及び第２鉄、硝酸銀、塩化セシウム、三塩化インジウム、塩化第１セリウム、四塩化セレン、塩化第２銅、塩化マンガン、塩化カルシウム、塩化第２白金、四塩化タングステン、オキシ二塩化タングステン、タングステン酸カリウム、塩化第２金、オキシ塩化ジルコニウム、塩化亜鉛等の各種の金属塩が例示できる。また、金属塩以外の化合物としては、水酸化インジウム、ケイタングステン酸、シリカゾル、水酸化カルシウム等が例示できる。
【００３５】
本発明において構造体表面に導電性高分子膜を形成するために使用する導電性高分子含有分散液は、ポリアニリン等の導電性高分子粉末を水に分散することにより作製できる。その際には、界面活性剤等の分散剤あるいは超音波発生機能を有する分散装置を使用するのがよい。特に好ましい導電性高分子膜を形成するのに使用する導電性高分子と、過酸化チタン等とを併せ含有する分散液を製造するには、特願２００１−４４５８６あるいは特願２００１−１５９２６５に記載されているように、過酸化チタンを含有する分散液にポリアニリン粉末あるいは分散液を添加し混合するのがよい。
【００３６】
また、過酸化チタンを含有する分散液の製造も特願２００１−４４５８６あるいは特願２００１−１５９２６５に記載されているとおりに行えばよい。具体的には、図１に記載されているように行うことにより製造できる。例えば、アモルファス型過酸化チタン分散液の場合には、まず希薄四塩化チタン溶液を準備し、これに希薄アンモニア水等の希薄アルカリ溶液を添加し中和して水酸化チタンを沈殿させる。この沈殿物を純水で洗浄し、水酸化物の含有液を作製する。次いで、この含有液を冷却しながら過酸化水素を添加し攪拌することにより製造できる。さらに、アナターゼ型過酸化チタン分散液は、前記で製造されたアモルファス型過酸化チタン分散液を所定時間加熱することによりアモルファス型過酸化チタンがアナターゼ型に転位することで得られる。
【００３７】
そして、導電性高分子膜を形成するには、前述したとおり構造体表面に導電性高分子の分散液、好ましくは導電性高分子と過酸化チタンとを含有する分散液、より好ましくは導電性高分子と過酸化チタンと導電性向上物質とを含有する分散液を構造体表面に塗布することになるが、その際の塗布手段としては各種のものが制限されることなく採用でき、それには、スプレー工法、ローラ工法あるいはディップ工法等が例示できるが、経済性の点でスプレー工法あるいはディップ工法が好ましい。このようにして塗布膜を形成した後は常温〜２５０℃程度で加熱乾燥するがよい。それにより図３(ａ)に図示する構造の導電性高分子膜が形成される。
【００３８】
これとは別に、まず過酸化チタンと導電性向上物質との分散液を構造体表面に塗布して導電膜を形成し、ついで導電性高分子の分散液を塗布して導電性高分子膜を形成し、図３(ｂ)及び（ｃ)に図示する積層構造とせしめることもでき、これが本発明における好ましい形態である。さらに、構造体全体あるいはその表面だけが導電性の構造体に導電性高分子膜を形成することもできる。前記のような積層構造は、構造体表面が導電性を有しないか、又はより浄化性能を向上せしめる場合に採用するのが好ましい。その際の塗布手段としても前記の各種のものが使用できる。
【００３９】
なお、本明細書においては、本発明の構造体に関し、導電性高分子膜が形成された状態の全体構造（例えば該膜を備えるガラス板）と、該膜を除いた部分（例えば該膜を形成する前の膜なしのガラス板、あるいは該膜を形成した後の該膜を除いた基材となっているガラス板）とを区別するために、必要により後者を構造体本体ということがある。
【００４０】
本発明において導電性高分子膜に電圧を印加する電極については、該高分子膜に電圧が印加できるように取り付けられていればよく、導電性高分子膜に直接接続する必要はない。該電極の接続には、導電性高分子膜に電圧を印加できるものであれば、各種の電気的接続が特に制限されることなく使用可能である。例えば好ましい態様としては、図３(ａ)(ｂ)(ｃ)に図示する３種のものがある。すなわち、直流又は交流電圧印加用の両電極を導電性高分子膜に直接に接続するもの、一方の電極を導電性高分子膜に接続し、他方の電極を導電膜に接続するもの、両電極を導電膜に接続するものの３種がある。
【００４１】
また、電極の構造体等への取付構造についても特に制限はなく、１例を図示すると図２のような構造がある。すなわち図２左側に図示するようにリード線に接続する電極をまず構造体である平板表面に仮接合し、その上に導電性高分子膜を塗膜し更に乾燥した後にボルトとナットで平板にしっかりと固定する。また右側に図示するようにまず導電性高分子膜を塗膜し乾燥した後リード線に接続する電極を前記と同様にボルトとナットで平板にしっかりと固定してもよい。また、印加する電圧については、直流電圧の場合は、１〜１００Ｖがよく、好ましくは５〜５０Ｖがよい。
【００４２】
本発明では、前記したとおり直流又は交流電圧の印加と同時に可視光線又はそれ以下の波長の電磁波を照射することにより汚染防止性能及び汚染浄化性能が格段に向上するが、その照射光は３００〜９００ｎｍの範囲の電磁波が好ましい。前記した好ましい場合には電磁波の全てが前記範囲に入ることが必要であるというのではなく、この範囲に入る電磁波の量が多いほど汚染防止性能等が向上するということである。この範囲に入る電磁波を発光する光源としては、白熱灯、ハロゲンランプ、蛍光灯、ＨＩＤランプ、ナトリウムランプ、ＬＥＤランプあるいは水銀灯等の各種照明灯が該当するが、経済性の点で蛍光灯あるいは水銀灯が好ましい。
【００４３】
また、導電性高分子膜中の導電性高分子は、半導電状態あるいは絶縁状態にあるのが好ましく、そのためには導電性高分子の導電状態における吸収波長の電磁波照射処理又は導電性高分子に対する酸もしくはアルカリ処理がある。その電磁波照射処理は、造膜前の分散液あるいは造膜後の導電性高分子膜のいずれに行ってもよいが、造膜前の分散液に対して行うのが好ましい。その照射処理に使用する光源としては、可視光から長・中・短紫外線を発光する低圧もしくは高圧水銀灯、又は殺菌オゾン発生ランプ等がよい。
【００４４】
前記した酸又はアルカリ処理は、前記電磁波照射処理と同様造膜前の導電性高分子あるいは造膜後の導電性高分子膜の何れに対して行ってもよいが、構造体本体あるいは周辺材料を劣化させる恐れがある点から造膜前の導電性高分子に対して行うのがよい。その処理に使用する酸及びアルカリは特に制限されるわけではないが、酸としては、塩酸、硫酸、硝酸、クエン酸等がよく、アルカリとしては、アンモニア水、苛性ソーダ溶液等がよい。
【００４５】
【実施例】
以下に、本発明の実施例及びそれを使用した実験例を示すが、本発明はこれら実施例及び実験例によって何ら限定されるものではなく、特許請求の範囲の規定によって特定されるものであることは勿論である。また、本発明の実施例に該当する導電性高分子膜を被覆した板状体、及び比較例の板状体の製造に使用した分散液は以下のとおりのものである。
【００４６】
[分散液の調製等]
Ａ．[導電性向上物質含有過酸化チタン分散液]
この分散液の過酸化チタン含有量は０．８５wt％であり、その調製は以下のとおり行う。
純水５００ｇにシリカゲル（濃度３０wt％）２．５ｇと四塩化チタン溶液（濃度５０wt％、住友シチックス社製）１０ｇとを添加し、その後純水を加えて１０００ｇにした。これに２５％アンモニア水（高杉製薬（株）製）を１０倍に希釈して滴下しｐＨ６．９に調整して、シリカと水酸化チタンとの複合物を沈殿させた。
【００４７】
この沈殿物を純水で、上澄み液中の導電率が０．８ｍＳ／ｍになるまで洗浄を継続するようにし、それが０．６８８ｍＳ／ｍになったところで終了させたところ、濃度０．９６％の酸化チタンとシリカとの複合水酸化物の含有液が３５０ｇ作製された。次いで、この含有液を１〜５℃に冷却しながら３５wt％の過酸化水素（タイキ薬品工業（株）製）２５ｇを添加し、１６時間撹拌するとシリカがドープされた濃度１．５wt％のアモルファス型過酸化チタン分散液３５０ｇが得られた。この分散液の一部を希釈しアモルファス型過酸化チタン濃度０．８５wt％のものを６０ｇ作製し、これに更に硝酸銀溶液を濃度０．０００５ｍｏｌになるように０．０５ｇ添加し、シリカ及び銀がドープされたアモルファス型過酸化チタン濃度０．８５ｗｔ％の分散液を調製した。
【００４８】
Ｂ．[導電性高分子分散液（ドイツ、オルメコン社製ポリアニリン水分散液（商品名：D1005W）]
この分散液のポリアニリン濃度は３．０ｗｔ％である。
【００４９】
Ｃ．[導電性高分子＋過酸化チタン含有分散液]
前記Ａで調製したシリカ及び銀がドープされた過酸化チタン濃度０．８５ｗｔ％の分散液に、前記Ｂの導電性高分子分散液を添加し、ポリアニリンと、シリカ及び銀がドープされた過酸化チタンとを含有する分散液を調製した。その際の前記Ｂの高分子分散液と、前記Ａの過酸化チタン分散液との比率は１：１０とした。得られた分散液中のポリアニリン濃度は０．２７８wt％、過酸化チタン濃度は０．７７１wt％である。
【００５０】
[実験例１]
透明フロートガラス板（４×２１０×３００ｍｍ）に前記Ｂ、Ｃの分散液を使用して図３(ａ)に図示するように造膜し、各種の実施例ガラス板を製造した。各実施例ガラス板の具体的な製造方法は以下のとおりである。なお、比較試験例１には、造膜する前の造膜のないガラス板に電極を取り付け直流電圧の印加のみを行った。
【００５１】
(実施例１)
前記透明フロートガラス板に前記Ｂの分散液を１．０ｇ／１００ｃｍ2（wet）の量でスプレーし、その後１００℃、１５ｍｉｎで加熱乾燥して、厚さ０．９５μｍのポリアニリン含有高分子膜を被覆したガラス板を作製した。このガラス板の両端部に図４に図示するように電圧印加用の電極を取り付けた。
【００５２】
(実施例２)
前記透明フロートガラス板に前記Ｃの分散液を０．６ｇ／１００ｃｍ2（wet）の量でスプレーし、その後１００℃、１５ｍｉｎで加熱乾燥して、厚さ０．６μｍのポリアニリン及びチタン酸化物を含有する高分子膜を被覆したガラス板を作製した。実施例１と同様に電圧印加用電極を取り付けた。
【００５３】
(実施例１')
前記実施例１で作製したポリアニリン含有高分子膜を被覆したガラス板の高分子膜に塩酸（濃度１．０wt％）を、０．５ｇ／１００ｃｍ2（wet）の量でスプレーし乾燥して、酸性処理した高分子膜を被覆したガラス板を作製した。ついで、実施例１と同様に電圧印加用電極を取り付けた。
【００５４】
(実施例２')
前記実施例２で作製した高分子膜を被覆したガラス板の高分子膜に実施例１'と同様に塩酸をスプレーし乾燥して、酸性処理した高分子膜を被覆したガラス板を作製した。ついで、実施例１と同様に電圧印加用電極を取り付けた。
【００５５】
[実験例２]
透明フロートガラス板（４×２１０×３００ｍｍ）に、まず前記Ａの分散液を使用して造膜し、次いで、前記Ｂ又はＣの分散液を使用して造膜し、図３(ｃ)に図示する電極を備える積層構造を形成した各種の実施例ガラス板を製造した。各実施例ガラス板の具体的な製造方法は以下のとおりである。
【００５６】
(実施例３)
前記透明フロートガラス板に前記Ａの分散液を０．３ｇ／１００ｃｍ2（wet）の量でスプレーし、その後１００℃、１５ｍｉｎで加熱乾燥して、厚さ０．３μｍの被膜を形成した。次いで、２層目に前記Ｂの分散液を０．７２ｇ／１００ｃｍ2（wet）の量でスプレーし、その後１００℃、１５ｍｉｎで加熱乾燥して、厚さ０．４μｍのポリアニリン含有高分子膜を被覆した合計厚さ０．７μｍの積層被覆構造のガラス板を作製した。このガラス板の両端部には図４及び図３(ｃ)に図示するように電圧印加用の電極を取り付けた。
【００５７】
(実施例４)
前記透明フロートガラス板に前記Ａの分散液を０．３ｇ／１００ｃｍ2（wet）の量でスプレーし、その後１００℃、１５ｍｉｎで加熱乾燥して、厚さ０．３μｍの被膜を形成した。次いで、２層目に前記Ｃの分散液を０．７２ｇ／１００ｃｍ2（wet）の量でスプレーし、その後１００℃、１５ｍｉｎで加熱乾燥して、厚さ０．４μｍのポリアニリン及びチタン酸化物を含有する高分子膜を被覆した合計厚さ０．７μｍの積層被覆構造のガラス板を作製した。このガラス板の両端部には図４及び図３(ｃ)に図示するように電圧印加用の電極を取り付けた。
【００５８】
(実施例３')
前記実施例３で作製したポリアニリン含有高分子膜を被覆した積層被覆構造のガラス板の高分子膜に、塩酸（濃度０．５wt％）を０．５ｇ／１００ｃｍ2（wet）の量でスプレーし乾燥して、酸性処理した積層被覆構造のガラス板を作製した。ついで、実施例３と同様に電圧印加用電極を取り付けた。
【００５９】
(実施例４')
前記実施例４で作製したポリアニリン及びチタン酸化物を含有する高分子膜を被覆した積層被覆構造のガラス板の高分子膜に、実施例３'と同様に塩酸をスプレーし乾燥して、酸性処理した積層被覆構造のガラス板を作製した。ついで、実施例３と同様に電圧印加用電極を取り付けた。
【００６０】
(実施例３")
前記実施例３で作製したポリアニリン含有高分子膜を被覆した積層被覆構造のガラス板の高分子膜に、硫酸（濃度０．５wt％）を０．５ｇ／１００ｃｍ2（wet）の量でスプレーし乾燥して、酸性処理した積層被覆構造のガラス板を作製した。ついで、実施例３と同様に電圧印加用電極を取り付けた。
【００６１】
(実施例４")
前記実施例４で作製したポリアニリン及びチタン酸化物を含有する高分子膜を被覆した積層被覆構造のガラス板の高分子膜に、実施例３”と同様に硫酸をスプレーし乾燥して、酸性処理した積層被覆構造のガラス板を作製した。ついで、実施例３と同様に電圧印加用電極を取り付けた。
【００６２】
(比較試験例２．３)
比較試験例２では電圧印加用電極を取り付けたをガラス板した。有機染料退色実験は前記ガラス板に後記する希釈赤色インクを塗布してＤＣ１２Ｖを印加すると同時に蛍光灯を照射した。
比較例試験３では、前記実施例３及び４で作製した積層被覆構造のガラス板を使用した。有機染料退色実験は希釈赤色インクを塗布せずにＤＣ１２Ｖを印加すると同時に蛍光灯を照射した。
【００６３】
[有機染料退色実験]
汚染浄化性能を評価するために、有機染料退色試験を行った。その試験の概要は以下のとおりである。
すなわち、高分子膜を被覆したガラス板の下側に図５に図示するように水銀灯(100W)又は蛍光灯(32W)を設置して、それら照明灯が発する光をガラス板に照射し同時に電圧印加用電極に直流又は交流の所定の電圧を印加して、その後有機染料液を塗布し、ガラス板表面の色の変化を色彩計（ミノルタ ＣＲ−２００）で測定する。
【００６４】
[印加電圧及び電流、並びに使用照明灯]
実験例１では、直流１０Ｖを印加し、実験例２では、直流１２Ｖまたは交流１２Ｖをチタン酸化物膜に通電し、導電性高分子膜に電圧印加した。また、ガラス板を照射する照明灯は、実験例１では水銀灯(100W)と蛍光灯(32W)、実験例２では蛍光灯(32W)を使用した。なお、直流電圧の制御にはKENWOOD PA18-1.2A/LA、交流電圧の制御には「スライダーク(SD)」（YAMABISHI TYPE N-130-10）を使用した。また電流測定装置にはデジタルマルチメータ（YOKOGAWA MODEL 7552)を使用した。
【００６５】
[色彩計測手順]
色の変化の測定に使用する有機染料液は、パイロット社製赤インクを２０倍に希釈した液を使用する。その希釈液のガラス板あるいは導電性高分子膜への塗布は、照明灯の点灯及び導電性高分子膜への電圧印加の開始後で、かつそれらが正常作動した後に行う。色彩計による色の変化の測定は、塗布直後、１時間後及び４８時間後に行い、その測定時には、前記照明灯の作動及び電圧印加は停止し、その後前記測定を行う。
【００６６】
なお、色の変化の測定は前述のとおりに行われるから、その塗布直後の測定は、実際には照明灯及び電圧印加が正常作動後で、かつ有機染料液塗布後１分前後経過した後である。また、照明灯を導電性高分子膜が被覆されているガラス板の下側に設置しガラス基板を透過した光により導電性高分子膜を照射し、有機染料の退色性能を測定することにより、該膜を照明器具のカバーに形成した場合と同様の態様となり、その結果により照明器具におけるトンネル内の排ガス中の油分（有機物）の汚染浄化性能が評価できる。
【００６７】
[色彩変化の評価]
色彩計の測定値は、Ｌ*、ａ*、ｂ*及び△Ｅ*で表記され、それぞれ以下のことを表す。
Ｌ*：明度を示す。この数値が大きい場合には明るい
ａ*：赤と緑の間の色の変化を表す。数値が＋側にあるときは赤色であることを示す。その数値が大きい場合には赤色が濃いことを示す。
数値が−側にあるときは緑色で、その数値が大きい場合には緑色が濃いことを示す。
なお、数値が０の場合は無彩色であることを示す。
ｂ*：黄色と青の間の色の変化を表す。数値が＋側にあるときは黄色であること を示す。その数値が大きい場合には黄色が濃いことを示す。
数値が−側にあるときは青色で、その数値が大きい場合には青色が濃いことを示す。
△Ｅ*：色差（時間経過による色の変化量）を表す。
時間経過による色の変化量が大きい場合には、この数値が大きくなる。
なお、△Ｅ*は、以下の計算式によって求める。
△Ｅ*ａｂ＝[(△Ｌ*)2＋(△ａ*)2＋(△ｂ*)2]1/2
【００６８】
[実験例１の測定結果]
実験例１の測定結果は表１に示すとおりである。その表１によれば、直流電圧のみを印加した（「ＤＣ１０Ｖのみ」）場合においては、実施例１、２、１'、２'のいずれのガラス板を使用した場合にも、Ｌ*及び△Ｅ*の値が次第に大きくなり、明るくなっていることがわかる。かつａ*の値はいずれのガラス板を使用した場合にも次第に小さくなっており、これらのことから赤の色が次第に退色していることがわかる。なお、そのことはガラス板に造膜せずに直流電圧の印加のみを行った比較試験例１の場合と対比すると一層明確になる。
【００６９】
【表１】
そして、直流電圧の印加のみの場合に比し、直流電圧の印加と、水銀灯又は蛍光灯の照射とを併用した場合には、いずれのガラス板を使用した場合においてもＬ*値の増加及びａ*値の減少が急激であり、赤色が急激に退色していることがわかる。さらに、水銀灯併用の場合と、蛍光灯併用の場合とを対比すると、水銀灯併用の場合には、インク塗布直後のａ*値の低減が大きく使用したガラス板によっては極端に低減している場合もあり、かつ殆どのガラス板において１時間後と４８時間後の△Ｅ*の値が大きくなっていることから、赤色の退色効果が優れていることがわかる。
【００７１】
また、直流電圧の印加と水銀灯を照射した場合における、ガラス板に対する塩酸処理の有無による影響については、実施例２及び２'のガラス板を使用した４８時間後の場合を除き塩酸処理した場合の方が、１時間後及び４８時間後の△Ｅ*の値が大きくなっており、赤色の退色効果が大きいことがわかる。
【００７２】
さらに加えれば、実施例１及び１'のガラス板を使用し、ＤＣ１０Ｖを印加し、同時に水銀灯を照射した場合には、４８時間後のａ*の値が比較的大きなマイナスの数値になっているが、これは当初の赤色は消え導電性高分子膜中にポリアニリンが存在し、そのために膜自体の色が緑色になっていることを示す。それに比し実施例２及び２'のガラス板を使用し、前記の場合と同一条件で試験した場合には赤色が消えａ*値が小さなマイナス値であるが、それは導電性高分子膜中に存在するポリアニリンと、過酸化チタンの色が相殺し無色透明に近い色になっていることによると考えられる。
【００７３】
[実験例２の測定結果]
実験例２の測定結果は表２に示すとおりである。その測定に使用したガラス板は、いずれもガラス板上にチタン酸化物と導電性向上物質とを含有する導電膜と、ポリアニリンを含有する高分子膜とがこの順で積層された構造のものであり、電圧は直流と交流の両方が使用されたが、いずれも導電膜に通電され、導電性高分子膜に電圧が印加された。照明はいずれもの場合も蛍光灯が使用された。
【００７４】
【表２】
その実験結果によれば、交直いずれの電圧を印加した場合にも、優れた有機染料に対する退色性能を有することがわかる。また、実験例１の蛍光灯を照射した場合と、同様の傾向であることがわかる。実施例４のガラス板を使用した場合には、いずれもａ*の値が希釈赤インクを塗布した直後から、それを塗布しない比較試験例３とほぼ同じであり、塗布直後に有機染料がほぼ全量分解されていることを示している。さらに、実施例３の基板を使用した場合には、ａ*値の対比から、直流より交流を印加した場合の方が有機染料分解性能が優れている。なお、△Ｅ*値が、交流印加の場合の方が小さいのは後記する場合と同様である。
【００７６】
酸処理しない実施例３、４のガラス板を使用した場合と、酸処理した実施例３'、３"、４'、４"のガラス板を使用した場合とでは、ａ*の数値をみると、酸処理した場合の方がしない場合に比し赤インクの退色能に優れていることがわかる。それに対して△Ｅ*の数値をみると、酸処理しないガラス板の場合には時間経過にしたがって大きくなっていて、かつ酸処理したガラス板の場合に比較してもその数値は大きく前記理解には疑問があるようにも思われる。
【００７７】
しかしながら、酸処理したガラス板の場合には、その差がほとんどなく、しかもａ*値が急激に減少しており、これらのことからすると赤色有機染料が蛍光灯照射と同時にほぼ分解してしまうためと考えられる。以上のことからしても、酸処理した実施例のガラス板の方が、酸処理しない実施例のガラス板の場合に比し赤インクの退色能に優れているといえる。
【００７８】
【発明の効果】
本発明では、ポリアニリン、ポリピロール等の導電性高分子を使用して、照明器具カバー、トンネル壁用パネル、複写機等の各種精密機器のケース及び内装部材等に導電性高分子膜を形成し、その高分子膜に直流又は交流電圧を印加するという簡便な手段により、その各種精密機器のケース及び内装部材等の表面における汚染を防止することができると共に自動車排ガス等の各種排ガス中に含有される未燃焼もしくは不完全燃焼成分の炭化水素もしくは一酸化炭素、燃焼を生成する有害成分であるＳＯXもしくはＮＯX、又は各種有害有機化合物もしくは無機ガスを分解又は酸化して浄化することができる。
【００７９】
また、直流又は交流電圧の印加と同時に可視光線又はそれ以下の波長の電磁波、好ましくは３００〜９００ｎｍの範囲の電磁波を照射することにより汚染防止性能及び汚染浄化性能は向上する。さらに、導電性高分子膜中の導電性高分子は、半導電状態又は絶縁状態にあるのが好ましく、そのため導電性高分子膜又は導電性高分子分散液中の導電性高分子に対し、導電状態における吸収波長の電磁波照射処理、又は酸もしくはアルカリ処理することにより一層汚染浄化性能等が向上する。
【００８０】
以上のとおりであるから、特に交流又は直流電圧が印加される導電性高分子膜をトンネル内に設置する照明器具のカバー、蛍光灯の蛍光管、電球のガラス球等に採用した場合には、導電性高分子膜は、トンネル内に設置される前記照明灯により必然的に常時可視光又はそれ以下の波長の電磁波を照射されることになり、それら表面の汚染、特に自動車排ガスによる汚染が防止され、その結果該汚染による照明光の低減を防止できる。
【００８１】
また、それと同時にトンネル中に放出される自動車排ガス中の未燃焼有害成分あるいはＮＯX等の燃焼により生成する有害成分を分解又は酸化して無害化物質に変換することもできる。さらに、この導電性高分子膜をトンネル壁全面に設置し、かつ照明の光量を増加させた場合には、トンネル内が明るくなり、その結果安全運転上有益であるだけでなく、トンネル内の空気浄化にも大いに有効である。以上のとおり本発明は優れた作用効果を奏するものである。
【図面の簡単な説明】
【図１】本発明で使用する過酸化チタン分散液の製造プロセス概要を図示する。
【図２】電圧印加用電極の構造体への取付（固定）構造の一例を図示する。
【図３】導電性高分子膜を板状構造体表面に形成した状態の断面図を示す。(ａ)は構造体表面に導電性高分子膜を直接形成した場合の該膜及び電極配置構造を示す。(ｂ)及び(ｃ)は、チタン酸化物及び導電性向上物質を含有する導電膜を介して導電性高分子膜を構造体表面に形成した場合の積層及び電極配置構造を示す。
【図４】実施例で採用する導電性高分子膜を有するガラス板等の板状構造体における電圧印加用電極配置構造を図示する。
【図５】実験例で使用する導電性高分子膜を有するガラス板に対する照明灯の配置構造を図示する。[0001]
BACKGROUND OF THE INVENTION
The present invention uses a conductive polymer such as polyaniline to form a conductive polymer film on cases and interior / exterior members of various precision equipment such as lighting fixture covers, tunnel wall panels, and copying machines. The present invention relates to a technique for preventing or purifying contamination on the surface. More specifically, it is exposed to visible light emitted from the illuminating lamp at all times, such as a cover of a luminaire installed in a tunnel, a glass bulb of a light bulb, or a fluorescent tube of a fluorescent lamp, and at the same time, it is contaminated by automobile exhaust gas. The present invention also relates to a technique for preventing or purifying contamination that can be particularly preferably applied to members that are constantly exposed.
[0002]
[Prior art]
For conductive polymers such as polyaniline or polypyrrole, various types of electromagnetic shielding materials, battery electrodes, antistatic agents, capacitors, diodes, transistors, etc. that shield electromagnetic waves generated from mobile phones, TVs, personal computers, home appliances, etc. Much research and development has been carried out in anticipation of its use in electronic devices, electrochromic elements, various sensors, etc., and some have reached the stage of practical use.
[0003]
Many substances have already been developed for this conductive polymer. In addition to the polyaniline and polypyrrole described above, polythiophene, polythiophene vinylene, polyisothianaphthene, polyacetylene, polyalkylpyrrole, polyalkylthiophene are also included. , Poly-p-phenylene, polyphenylene vinylene, polymethoxyphenylene, polyphenylene sulfide, polyphenylene oxide, polyanthracene, polynaphthalene, polypyrene, polyazulene, and polymers of these derivatives. Note that these conductive polymers are used alone or as a mixture of two or more in the above-described use.
[0004]
These conductive polymers are preferably doped, and the conductivity is improved by this doping, and as a result, the electromagnetic wave shielding property is improved. As the dopant, donor-type dopants such as alkali metals such as Li, Na, and K, alkaline earth metals such as Ca, or Cl2, Br2, I2Halogen such as PFThree, AsFFive, BFThreeLewis acids such as HF, HCl, HNOThree, H2SOFour, HClOFourProtic acid such as FeClThree, FeOCl2, TiClFour, WClThreeTransition metal compounds such as Cl-, Br-, I-, ClOFour -, PFThree -, BFThree -, AsFThree -An acceptor dopant of an electrolyte anion such as is used.
[0005]
The above-described use using these conductive polymers exclusively utilizes the property of high conductivity, and particularly when used as an electromagnetic shielding material, the property is important as described above. is there. It is also known that its properties change due to oxidation or reduction reaction, particularly electrical redox reaction, or reaction with acid or base. In particular, a conductive polymer having the properties of an electron donor and an electron acceptor exhibits a change in electrical characteristics due to these reactions.
[0006]
For example, polyaniline is known to change according to the reaction formula (1) below by oxidation or reduction reaction, or reaction with acid or base (“Polymer New Material One Point-5 Conductive Polymer”, Yoshimura Sukin, edited by the Society of Polymer Science, 17-18). As a result, when polyaniline is oxidized, the conductivity is in a metallic state and the color is green, and when reduced, the conductivity is in an insulating state from blue to colorless and transparent. Further, when acidified by reacting with an acid, the conductivity is improved to become green, and when reacting with a base to be basified, the conductivity is lowered and the color is blue.
[0007]
[Formula 1]
For many years, the present inventor has been involved in research and development of related technologies such as photocatalysts, in particular, titanium oxide, especially titanium peroxide photocatalytic performance, and means for utilizing them, and has proposed many results. On the other hand, as described above, the conductive polymer has been mainly focused on the electric conduction characteristic as described above, and only the use based on the characteristic has been focused on. Under such circumstances, the present inventor has paid attention to whether the conductive polymer also has photocatalytic performance as well as conductivity, and as a result of intensive research, it has been found that the conductive polymer exhibits photocatalytic performance. A patent application has already been filed for this invention (Japanese Patent Application No. 2001-44586).
[0009]
The invention of the application relates to a technique for generating an active radical species or peroxide for prevention of contamination, purification of contaminated fluid, or purification by irradiating a conductive polymer with electromagnetic waves having the absorption wavelength. More specifically, the absorption wavelength of the conductive polymer, or a conductive polymer such as a conductive polymer film formed on the surface of various structures made of various materials such as glass, tile, metal or plastic, Technology that suppresses contamination of the surface of the conductive polymer by irradiating an electromagnetic wave with an absorption wavelength preferably in an insulating state, technology that purifies contaminated fluid such as contaminated gas or liquid, or active radical species or peroxide for purification The present invention relates to a technology for generating objects.
[0010]
[Problems to be solved by the invention]
The invention proposed by the patent application is formed on the surface of the conductive polymer body or the structure body by irradiating the conductive polymer with electromagnetic waves having an absorption wavelength, particularly an absorption wavelength in an insulating state, as described above. The present invention relates to a technique for preventing contamination on the surface of a conductive polymer film, purifying contamination, or generating active radical species or peroxides for purification.
[0011]
Therefore, the present inventor, even with or without irradiation of electromagnetic waves of an absorption wavelength in such an insulating state, and further earnestly examined to develop a pollution prevention or contamination purification technology on the conductive polymer film surface, It has been found that the present invention has succeeded in the development, as a result of finding that it is possible to prevent or purify the contamination on the surface of the film by applying a DC or AC voltage to the conductive polymer film.
[0012]
Therefore, the present invention can prevent contamination on the surface of a conductive polymer film by applying a DC or AC voltage to the conductive polymer film regardless of whether or not the conductive polymer film is irradiated with an electromagnetic wave having an absorption wavelength in its insulating state. To provide a technology to prevent contamination of the surface of the structure or to purify the contamination by forming a conductive polymer film on the surface of the structure by utilizing its characteristics. Is a problem to be solved by the invention. That is, an object of the present invention is to provide a technique for preventing or purifying the contamination.
[0013]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present invention provides a method for preventing or purifying contamination due to a conductive polymer film, and a structure having the performance of preventing or purifying contamination having a conductive polymer film. Especially preferably, a tunnel illumination lamp including a fluorescent tube or a glass bulb on which a conductive polymer film having the performance is formed, and a transparent or translucent cover on which the conductive polymer film having the performance is formed A lighting device for a tunnel comprising:
[0014]
The former method for preventing or purifying contamination is to prevent or purify contamination on the surface of the film by applying a voltage to the conductive polymer film. The latter structure has a conductive polymer film on the structure body, and an electrode on the conductive polymer film or the conductive film so that a DC or AC voltage can be applied to the conductive polymer film. In this case, the ability to prevent or purify the contamination is improved by irradiating with visible light or an electromagnetic wave having a wavelength shorter than that.
[0015]
Furthermore, a lighting fixture having a pollution prevention performance or a purification performance for tunnels, which is a particularly preferable aspect of the structure, has a conductive polymer film on the cover surface and applies a DC or AC voltage to the polymer film. An illuminating lamp having electrodes and having the same performance has a conductive polymer film on the surface of a fluorescent tube or a glass sphere, and has an electrode for applying a DC or AC voltage to the polymer film. .
[0016]
In the present invention, a conductive polymer film such as polyaniline and polypyrrole is used to form a conductive polymer film on cases and interior members of various precision equipment such as lighting equipment covers, tunnel wall panels, and copying machines. In addition, by applying a direct current or an alternating voltage to the polymer film, it is possible to prevent contamination on the surfaces of the cases and interior members of the various precision devices, and to be contained in various exhaust gases such as automobile exhaust gases. Combusted or incompletely combusted hydrocarbons, carbon monoxide, or SO that is a harmful component produced by combustionXOr NOXCan be purified by decomposition or oxidation.
[0017]
Further, by applying an electromagnetic wave having a wavelength of visible light or less, preferably an electromagnetic wave having a wavelength of 300 to 900 nm, simultaneously with application of a direct current or an alternating voltage, the pollution prevention performance and the pollution purification performance are remarkably improved. Furthermore, it is preferable that the conductive polymer in the conductive polymer film is in a semiconductive state or an insulating state. Therefore, the conductive polymer film is subjected to electromagnetic wave irradiation treatment of absorption wavelength or acid or alkali treatment in the conductive state. By doing so, the contamination purification performance is further improved.
[0018]
In particular, when a conductive polymer film to which an AC or DC voltage is applied and a conductive film are used for a cover of a lighting fixture that is installed in a tunnel, a fluorescent tube of a fluorescent lamp, a glass bulb of a bulb, etc. The molecular film is inevitably always irradiated with an electromagnetic wave having a wavelength of visible light or lower by an illumination lamp such as a fluorescent lamp installed in a tunnel, and contamination of the surface thereof, particularly contamination by automobile exhaust gas, is caused. As a result, the reduction of illumination light due to the contamination can be effectively prevented.
[0019]
At the same time, unburned harmful components or NO in automobile exhaust gas released into the tunnelXIt is also possible to decompose or oxidize harmful combustion components such as these to convert them into detoxified substances. Furthermore, when this conductive polymer film is installed on the entire tunnel wall and the amount of illumination light is increased, the inside of the tunnel becomes brighter, which is not only beneficial for safe operation, but also the air inside the tunnel. It is also very effective for purification.
[0020]
DETAILED DESCRIPTION OF THE INVENTION
As described above, the present invention provides a method for preventing or purifying contamination due to a conductive polymer film to which direct current or alternating current is applied, and a pollution prevention or purification performance including the conductive polymer film to which direct current or alternating current is applied. In both cases, both pollution prevention and contamination purification performance can be improved by irradiating visible light or electromagnetic waves having a wavelength shorter than that. Incidentally, the prevention or purification of contamination in the present invention is performed by various harmful pollutants such as exhaust gas adhering to the surface of the conductive polymer film, and the contaminated components are purified by decomposition or oxidation by the conductive polymer film. Contamination of the surface is prevented. In that case, H in the atmosphere2O, O2To OH-・ ・ O2Radicals are formed and the purification function is expressed.
[0021]
In addition, a conductive polymer film having the above performance is preferably formed on a lighting lamp or a lighting fixture that is a member that is preferably used in a tunnel in a highly contaminated environment and is always irradiated with visible light. Thus, it is intended to provide a lighting apparatus or the like having excellent contamination purification performance. Specifically, a tunnel illumination lamp including a fluorescent tube or a glass sphere having a conductive polymer film having the performance formed on the surface, and a transparent or transparent light having the conductive polymer film having the performance formed on the surface. A lighting device for a tunnel having a translucent cover is provided.
[0022]
In addition to the polyaniline and polypyrrole described above, the conductive polymer includes polythiophene, polythiophene vinylene, polyisothianaphthene, polyacetylene, polyalkylpyrrole, polyalkylthiophene, poly-p-phenylene, polyphenylene vinylene, polymethoxyphenylene, There are many such as polyphenylene sulfide, polyphenylene oxide, polyanthracene, polynaphthalene, polypyrene, polyazulene, and polymers of derivatives thereof.
[0023]
In the present invention, the conductive polymer used for forming the conductive polymer film can be any of the above-mentioned various polymers, and is not particularly limited, but a conjugated polymer in which metal-insulator transfer occurs, A conjugated polymer having a bond alternation in the polymer chain or a conjugated polymer having a one-dimensional chain and having a dopamine function, so-called electron donor and electron acceptor functions can be preferably used. Examples thereof include polyaniline and polyphenylene, and polyaniline which is an ionic polymer is particularly preferable.
[0024]
The target structure for forming the conductive polymer film of the present invention includes structures of various materials or structures of various shapes that require pollution prevention performance and pollution purification performance, such as tunnel wall panels and ceiling plates. , Interior panels, airway materials, air conditioning equipment and cases, surveillance camera lens covers, toilet equipment, refrigerator cases and interior materials, lighting fixture storage cases, air purification filters, semiconductor manufacturing lines Examples include line covers, gas decomposition apparatus members, and cases and interior members of copying machines, printers, and other precision devices.
[0025]
In addition to these, buildings, window glass for automobiles, exterior materials for automobiles, tanks, various tanks for ornamental use, pipes for metals, plastics, sanitary ware, glasses, lenses, lens filters, hot water storage Various examples such as bowls, bathtub equipment, washbasins, sinks, door handles, water stopcocks, road mirrors, electromagnetic shielding materials, semiconductor materials such as substrates, internal parts of copying machines, etc. can be exemplified, but are particularly limited There is no. Further, examples thereof include a video display surface glass of a television, an image display surface glass of a liquid crystal display device, and an image reading surface glass of a copying machine.
[0026]
Particularly preferable conductive polymer film formation objects include a lighting apparatus and its related members that are installed in a tunnel in an environment that is significantly contaminated with automobile exhaust gas as described above and that is always irradiated with visible light. There are transparent or translucent covers for lighting fixtures, fluorescent tubes for fluorescent lamps, glass bulbs for various light bulbs such as incandescent lamps, and the like. Examples of the material used for the above-described various members include plate glass, ceramic, stainless steel, aluminum and other metal plates, acrylic, polycarbonate, PET and other plastic plates, cotton cloth and fibers.
[0027]
For many years, the present inventor has been involved in research and development of related technologies such as fixing performance and photocatalytic performance of titanium peroxide, that is, titanium oxide having a peroxo group, and has proposed many results. Therefore, in the present invention, the combined use of the conductive polymer and titanium peroxide, or the combined use of the conductivity improving substance in addition to that, compared to the case where the conductive polymer is used alone in addition to that. As a result, it has been found that the present invention further exhibits excellent pollution prevention performance and pollution purification performance.
[0028]
In the present invention, the conductive polymer film can be formed on the structure by applying a dispersion containing the conductive polymer to the surface of the structure. However, in this case, it is difficult to say that the binding strength of the conductive polymer to the surface of the structure is sufficient, and therefore, it is preferable to use an auxiliary agent that improves the binding strength. For this purpose, the above-described titanium peroxide also has a performance as an auxiliary agent for improving the excellent bonding strength, and can be preferably used.
[0029]
As the auxiliary agent, various materials other than the titanium peroxide can be used without limitation. For example, silica sol, indium-tin oxide (ITO) and an inorganic polymer resin containing the same, or Examples include so-called acrylic silicon resin and fluorine resin. In order to form a dispersion containing such an auxiliary agent and a conductive polymer film, the conductive polymer powder is preferably dispersed in the auxiliary agent dispersion. For example, it can be formed by dispersing conductive polymer powder in a titanium peroxide dispersion.
[0030]
In selecting the auxiliary component, it is preferable to determine in consideration of the affinity with the various structural materials described above. In general, for example, silica sol or titanium oxide is preferable for glass, inorganic polymer resin is preferable for plastic, and titanium oxide is preferable for metal, glass, plastic, and other materials. Of the oxides of titanium, titanium peroxide is preferable because it can improve the ability to prevent and purify contamination as well as an auxiliary agent that improves the bonding force with the surface of the structure, particularly in combination with a conductivity improving substance. In this case, the conductivity can be further improved, which is preferable.
[0031]
There are two types of titanium peroxide, amorphous and anatase. The former amorphous titanium peroxide has no photocatalytic activity, and even if a film is formed on a polymer material plate, the material is deteriorated or decomposed. It is suitable for forming a conductive polymer film that has no fear of being formed. On the other hand, anatase-type titanium peroxide has a photocatalytic ability, and when a film is formed on a polymer material, it may cause deterioration, etc., but has an excellent affinity with a structure having a hydrophilic group. Therefore, it is preferable for use when forming a conductive polymer film on the surface of a structure made of an inorganic material.
[0032]
When this titanium peroxide is used in combination with a conductive polymer to form a conductive polymer film, the conductivity of the conductive polymer film, particularly the conductivity in an insulating state, can be improved. Furthermore, the electroconductivity polymer film can be further improved in conductivity in an insulating state by containing a conductivity enhancing substance in addition to titanium peroxide. Further, the coating containing titanium peroxide and the conductivity improving substance has conductivity, and the conductive polymer film is formed by interposing this film as a conductive film between the conductive polymer and the structure body. In particular, it is effective as a conductive film when a voltage is applied to a conductive polymer film containing only a conductive polymer.
[0033]
As such a conductivity improving substance, it is possible to improve conductivity as compared with a film formed of a dispersion containing a conductive polymer and titanium peroxide or a film containing titanium peroxide alone. For example, there are no particular limitations, and various substances such as metal salts can be used. Examples of the metal salt include metal salts such as aluminum, tin, chromium, nickel, antimony, iron, silver, cesium, indium, cerium, selenium, copper, manganese, calcium, platinum, tungsten, zirconium, and zinc. In addition, hydroxides or oxides can be used for some metals or nonmetals.
[0034]
The specific substance names of various substances such as metal salts are as follows: aluminum chloride, first and second tin chlorides, chromium chloride, nickel chloride, first and second antimony chlorides, first and second iron chlorides, silver nitrate , Cesium chloride, indium trichloride, cerium chloride, selenium tetrachloride, cupric chloride, manganese chloride, calcium chloride, platinum chloride, tungsten tetrachloride, tungsten oxydichloride, potassium tungstate, gallium chloride And various metal salts such as zirconium oxychloride and zinc chloride. Examples of compounds other than metal salts include indium hydroxide, silicotungstic acid, silica sol, and calcium hydroxide.
[0035]
In the present invention, the conductive polymer-containing dispersion used for forming the conductive polymer film on the surface of the structure can be prepared by dispersing conductive polymer powder such as polyaniline in water. In this case, it is preferable to use a dispersing agent such as a surfactant or a dispersing device having an ultrasonic wave generation function. To produce a dispersion containing both a conductive polymer used to form a particularly preferable conductive polymer film and titanium peroxide or the like, see Japanese Patent Application No. 2001-44586 or Japanese Patent Application No. 2001-159265. As described above, it is preferable to add and mix polyaniline powder or dispersion into a dispersion containing titanium peroxide.
[0036]
The dispersion containing titanium peroxide may be produced as described in Japanese Patent Application No. 2001-44586 or Japanese Patent Application No. 2001-159265. Specifically, it can be manufactured by carrying out as described in FIG. For example, in the case of an amorphous type titanium peroxide dispersion, a dilute titanium tetrachloride solution is first prepared, and a dilute alkaline solution such as dilute ammonia water is added thereto and neutralized to precipitate titanium hydroxide. The precipitate is washed with pure water to produce a hydroxide-containing liquid. Subsequently, it can manufacture by adding hydrogen peroxide and stirring this cooling liquid. Further, the anatase-type titanium peroxide dispersion is obtained by heating the amorphous-type titanium peroxide dispersion prepared above for a predetermined time, thereby rearranging the amorphous-type titanium peroxide to the anatase-type.
[0037]
In order to form a conductive polymer film, as described above, a conductive polymer dispersion on the surface of the structure, preferably a dispersion containing a conductive polymer and titanium peroxide, more preferably conductive. A dispersion containing a polymer, titanium peroxide, and a conductivity improving substance will be applied to the surface of the structure, but various application means can be used without limitation, The spray method, the roller method, the dip method, etc. can be exemplified, but the spray method or the dip method is preferable from the viewpoint of economy. Thus, after forming a coating film, it is good to heat-dry at normal temperature-about 250 degreeC. As a result, a conductive polymer film having the structure shown in FIG. 3A is formed.
[0038]
Separately, a dispersion of titanium peroxide and a conductivity enhancing substance is first applied to the surface of the structure to form a conductive film, and then a conductive polymer dispersion is applied to form a conductive polymer film. It can also be formed into a laminated structure as shown in FIGS. 3B and 3C, which is a preferred embodiment in the present invention. Furthermore, a conductive polymer film can be formed on a structure that is conductive on the entire structure or only on the surface thereof. The laminated structure as described above is preferably employed when the surface of the structure does not have electrical conductivity or when the purification performance is further improved. The various means described above can be used as the application means.
[0039]
In this specification, regarding the structure of the present invention, the entire structure in which a conductive polymer film is formed (for example, a glass plate provided with the film) and a portion excluding the film (for example, the film) In order to distinguish between a glass plate without a film before forming, or a glass plate which is a base material excluding the film after forming the film), the latter may be referred to as a structure body as necessary. .
[0040]
In the present invention, the electrode for applying a voltage to the conductive polymer film may be attached so that a voltage can be applied to the polymer film, and need not be directly connected to the conductive polymer film. For the connection of the electrodes, various electrical connections can be used without any particular limitation as long as a voltage can be applied to the conductive polymer film. For example, as a preferable embodiment, there are three types shown in FIGS. 3 (a), 3 (b) and 3 (c). That is, one in which both electrodes for DC or AC voltage application are directly connected to the conductive polymer film, one electrode is connected to the conductive polymer film, and the other electrode is connected to the conductive film, both electrodes There are three types for connecting the film to the conductive film.
[0041]
Also, there is no particular limitation on the structure for attaching the electrode to the structure or the like, and an example is shown in FIG. That is, as shown in the left side of FIG. 2, the electrode connected to the lead wire is first temporarily joined to the surface of the flat plate, which is a structural body, and a conductive polymer film is coated on it, and then dried, and then flattened with a bolt and nut Secure firmly. Alternatively, as shown on the right side, a conductive polymer film may be first coated and dried, and then the electrode connected to the lead wire may be firmly fixed to the flat plate with bolts and nuts as described above. Moreover, about the voltage to apply, in the case of a DC voltage, 1-100V is good, Preferably 5-50V is good.
[0042]
In the present invention, as described above, the contamination prevention performance and the contamination purification performance are remarkably improved by irradiating the electromagnetic wave having a wavelength of visible light or lower with the application of the direct current or alternating current voltage as described above, but the irradiation light is 300 to 900 nm. An electromagnetic wave in the range is preferred. In the preferred case described above, it is not necessary that all of the electromagnetic waves fall within the above range, but the greater the amount of electromagnetic waves that fall within this range, the better the pollution prevention performance. Various light sources such as incandescent lamps, halogen lamps, fluorescent lamps, HID lamps, sodium lamps, LED lamps or mercury lamps are applicable as light sources that emit electromagnetic waves falling within this range. Is preferred.
[0043]
In addition, the conductive polymer in the conductive polymer film is preferably in a semiconductive state or an insulating state. For this purpose, the electromagnetic wave irradiation treatment of the absorption wavelength in the conductive state of the conductive polymer or the conductive polymer is performed. There are acid or alkali treatments. The electromagnetic wave irradiation treatment may be performed on either the dispersion before film formation or the conductive polymer film after film formation, but is preferably performed on the dispersion before film formation. As a light source used for the irradiation treatment, a low-pressure or high-pressure mercury lamp that emits long, medium, or short ultraviolet rays from visible light, a sterilization ozone generation lamp, or the like is preferable.
[0044]
The acid or alkali treatment described above may be performed on either the conductive polymer before film formation or the conductive polymer film after film formation as in the electromagnetic wave irradiation treatment. It is good to carry out with respect to the conductive polymer before film formation from the point which may be deteriorated. The acid and alkali used for the treatment are not particularly limited, but as the acid, hydrochloric acid, sulfuric acid, nitric acid, citric acid and the like are good, and as the alkali, ammonia water, caustic soda solution and the like are good.
[0045]
【Example】
Examples of the present invention and experimental examples using the same are shown below, but the present invention is not limited by these examples and experimental examples, and is specified by the definition of the scope of claims. Of course. Moreover, the dispersion liquid used for manufacture of the plate-shaped body which coat | covered the conductive polymer film applicable to the Example of this invention, and the plate-shaped body of a comparative example is as follows.
[0046]
[Preparation of dispersion, etc.]
A. [Titanium peroxide dispersion containing conductivity enhancing substance]
The titanium peroxide content of this dispersion is 0.85 wt%, and its preparation is performed as follows.
To 500 g of pure water, 2.5 g of silica gel (concentration: 30 wt%) and titanium tetrachloride solution (concentration: 50 wt%, manufactured by Sumitomo Sitix) were added, and then pure water was added to make 1000 g. To this, 25% aqueous ammonia (manufactured by Takasugi Pharmaceutical Co., Ltd.) was diluted 10 times and added dropwise to adjust the pH to 6.9 to precipitate a composite of silica and titanium hydroxide.
[0047]
The precipitate was washed with pure water until the electrical conductivity in the supernatant reached 0.8 mS / m, and when it reached 0.688 mS / m, it was terminated. 350 g of a liquid containing a composite hydroxide of% titanium oxide and silica was produced. Next, 25 g of 35 wt% hydrogen peroxide (manufactured by Taiki Pharmaceutical Co., Ltd.) is added while cooling this containing liquid to 1 to 5 ° C., and stirred for 16 hours. 350 g of a type titanium peroxide dispersion was obtained. A part of this dispersion was diluted to prepare 60 g of amorphous titanium peroxide having a concentration of 0.85 wt%, and 0.05 g of a silver nitrate solution was further added to a concentration of 0.0005 mol. A dispersion having a doped amorphous titanium peroxide concentration of 0.85 wt% was prepared.
[0048]
B. [Conductive polymer dispersion (Polyaniline aqueous dispersion (trade name: D1005W) manufactured by Olmecon, Germany)]
The polyaniline concentration of this dispersion is 3.0 wt%.
[0049]
C. [Dispersion containing conductive polymer + titanium peroxide]
The conductive polymer dispersion of B is added to the dispersion of 0.85 wt% titanium peroxide doped with silica and silver prepared in A, and the peroxide is doped with polyaniline, silica and silver. A dispersion containing titanium was prepared. At that time, the ratio of the polymer dispersion of B to the titanium peroxide dispersion of A was 1:10. The polyaniline concentration in the obtained dispersion is 0.278 wt%, and the titanium peroxide concentration is 0.771 wt%.
[0050]
[Experiment 1]
Using a dispersion liquid of B and C on a transparent float glass plate (4 × 210 × 300 mm), a film was formed as shown in FIG. The specific manufacturing method of each Example glass plate is as follows. In Comparative Test Example 1, only a DC voltage was applied by attaching an electrode to a glass plate without film formation before film formation.
[0051]
(Example 1)
The dispersion liquid of B is 1.0 g / 100 cm on the transparent float glass plate.2(Wet) was sprayed and then heated and dried at 100 ° C. for 15 minutes to produce a glass plate coated with a polyaniline-containing polymer film having a thickness of 0.95 μm. As shown in FIG. 4, electrodes for applying voltage were attached to both ends of the glass plate.
[0052]
(Example 2)
0.6 g / 100 cm of the C dispersion on the transparent float glass plate2A glass plate coated with a polymer film containing polyaniline and titanium oxide having a thickness of 0.6 μm was produced by spraying in an amount of (wet) and then drying by heating at 100 ° C. for 15 minutes. A voltage application electrode was attached in the same manner as in Example 1.
[0053]
(Example 1 ')
Hydrochloric acid (concentration: 1.0 wt%) was added to the polymer film of the glass plate coated with the polyaniline-containing polymer film prepared in Example 1 at 0.5 g / 100 cm.2A glass plate coated with an acid-treated polymer film was prepared by spraying in an amount of (wet) and drying. Next, a voltage application electrode was attached in the same manner as in Example 1.
[0054]
(Example 2 ')
The polymer film of the glass plate coated with the polymer film prepared in Example 2 was sprayed with hydrochloric acid and dried in the same manner as in Example 1 ′ to prepare a glass plate coated with the acid-treated polymer film. Next, a voltage application electrode was attached in the same manner as in Example 1.
[0055]
[Experiment 2]
A film is first formed on a transparent float glass plate (4 × 210 × 300 mm) using the dispersion liquid A, and then formed using the dispersion liquid B or C, as shown in FIG. Various example glass plates having a laminated structure provided with the illustrated electrodes were produced. The specific manufacturing method of each Example glass plate is as follows.
[0056]
Example 3
The dispersion liquid of A is 0.3 g / 100 cm on the transparent float glass plate.2Sprayed with an amount of (wet), and then heat-dried at 100 ° C. for 15 minutes to form a coating having a thickness of 0.3 μm. Next, 0.72 g / 100 cm of the dispersion of B was added to the second layer.2Sprayed in the amount of (wet), and then heat-dried at 100 ° C. for 15 minutes to produce a laminated coating structure glass plate having a total thickness of 0.7 μm coated with a 0.4 μm-thick polyaniline-containing polymer film. . As shown in FIGS. 4 and 3 (c), voltage application electrodes were attached to both ends of the glass plate.
[0057]
Example 4
The dispersion liquid of A is 0.3 g / 100 cm on the transparent float glass plate.2It sprayed with the quantity of (wet), and it heat-dried at 100 degreeC and 15 minutes after that, and formed the film with a thickness of 0.3 micrometer. Next, 0.72 g / 100 cm of the C dispersion in the second layer2(Wet) sprayed, and then dried by heating at 100 ° C. for 15 minutes, and coated with a polymer film containing polyaniline and titanium oxide having a thickness of 0.4 μm and a total thickness of 0.7 μm. A glass plate was prepared. As shown in FIGS. 4 and 3 (c), voltage application electrodes were attached to both ends of the glass plate.
[0058]
(Example 3 ')
Hydrochloric acid (concentration: 0.5 wt%) was added to the polymer film of the laminated coating structure glass plate coated with the polyaniline-containing polymer film prepared in Example 3 at 0.5 g / 100 cm.2The glass plate was sprayed with an amount of (wet) and dried to produce an acid-treated laminated coating structure. Subsequently, a voltage application electrode was attached in the same manner as in Example 3.
[0059]
(Example 4 ')
In the same manner as in Example 3 ′, hydrochloric acid was sprayed and dried on the polymer film of the glass plate having a laminated coating structure in which the polymer film containing polyaniline and titanium oxide prepared in Example 4 was coated. A glass plate having a laminated coating structure was prepared. Subsequently, a voltage application electrode was attached in the same manner as in Example 3.
[0060]
(Example 3 ")
To the polymer film of the glass plate having a laminated coating structure coated with the polyaniline-containing polymer film produced in Example 3, sulfuric acid (concentration 0.5 wt%) was added at 0.5 g / 100 cm.2The glass plate was sprayed with an amount of (wet) and dried to produce an acid-treated laminated coating structure. Subsequently, a voltage application electrode was attached in the same manner as in Example 3.
[0061]
(Example 4 ")
The polymer film of the laminated coating structure coated with the polymer film containing polyaniline and titanium oxide prepared in Example 4 was sprayed with sulfuric acid and dried in the same manner as in Example 3 ″ to perform acid treatment. Then, a glass plate having a laminated coating structure was prepared, and then a voltage application electrode was attached in the same manner as in Example 3.
[0062]
(Comparative Test Example 2.3)
In Comparative Test Example 2, a glass plate with a voltage application electrode attached thereto was used. In the organic dye fading experiment, a diluted red ink, which will be described later, was applied to the glass plate, and DC 12 V was applied and simultaneously a fluorescent lamp was irradiated.
In the comparative example test 3, the glass plate of the laminated covering structure produced in the said Example 3 and 4 was used. In the organic dye fading experiment, DC 12 V was applied without applying diluted red ink, and at the same time, a fluorescent lamp was irradiated.
[0063]
[Organic dye fading experiment]
In order to evaluate the contamination purification performance, an organic dye fading test was conducted. The outline of the test is as follows.
That is, a mercury lamp (100 W) or a fluorescent lamp (32 W) is installed on the lower side of the glass plate coated with the polymer film as shown in FIG. A predetermined voltage of direct current or alternating current is applied to the application electrode, and then an organic dye solution is applied, and the color change on the surface of the glass plate is measured with a color meter (Minolta CR-200).
[0064]
[Applied voltage and current, and lighting used]
In Experimental Example 1, DC 10V was applied, and in Experimental Example 2, DC 12V or AC 12V was applied to the titanium oxide film, and voltage was applied to the conductive polymer film. As the illumination lamp for irradiating the glass plate, mercury lamp (100W) and fluorescent lamp (32W) were used in Experimental Example 1, and fluorescent lamp (32W) was used in Experimental Example 2. In addition, KENWOOD PA18-1.2A / LA was used for DC voltage control and “Slider (SD)” (YAMABISHI TYPE N-130-10) was used for AC voltage control. A digital multimeter (YOKOGAWA MODEL 7552) was used as the current measuring device.
[0065]
[Color measurement procedure]
As the organic dye liquid used for measuring the color change, a liquid obtained by diluting a pilot red ink 20 times is used. Application of the diluted solution to the glass plate or the conductive polymer film is performed after the lighting of the illumination lamp and the start of voltage application to the conductive polymer film and after their normal operation. The measurement of the color change by the colorimeter is performed immediately after application, 1 hour and 48 hours later. At the time of measurement, the operation of the illumination lamp and voltage application are stopped, and then the measurement is performed.
[0066]
Since the color change is measured as described above, the measurement immediately after the application is actually after the illumination lamp and the voltage application are normally operated and after about 1 minute has passed after the organic dye solution application. is there. In addition, by installing an illuminating lamp below the glass plate coated with the conductive polymer film, irradiating the conductive polymer film with light transmitted through the glass substrate, and measuring the fading performance of the organic dye, It becomes an aspect similar to the case where the film is formed on the cover of the lighting fixture, and as a result, the contamination purification performance of the oil (organic matter) in the exhaust gas in the tunnel of the lighting fixture can be evaluated.
[0067]
[Evaluation of color change]
The measured value of the colorimeter is L*, A*, B*And △ E*And represents the following respectively.
L*: Indicates brightness. Bright when this number is large
a*: Indicates the change in color between red and green. When the value is on the + side, it indicates red. If the value is large, the red color is dark.
When the numerical value is on the negative side, the color is green, and when the numerical value is large, the green color is dark.
A numerical value of 0 indicates an achromatic color.
b*: Indicates a change in color between yellow and blue. When the value is on the + side, it indicates yellow. When the value is large, yellow is dark.
When the numerical value is on the minus side, the color is blue, and when the numerical value is large, the blue color is dark.
△ E*: Color difference (color change amount with time).
This value increases when the amount of change in color over time is large.
△ E*Is obtained by the following formula.
△ E*ab = [(△ L*)2+ (△ a*)2+ (△ b*)2]1/2
[0068]
[Measurement result of Experimental Example 1]
The measurement results of Experimental Example 1 are as shown in Table 1. According to Table 1, when only a DC voltage was applied (“DC 10 V only”), L 1 was the same even when any one of the glass plates of Examples 1, 2, 1 ′, 2 ′ was used.*And △ E*It can be seen that the value of becomes gradually larger and brighter. And a*The value of becomes gradually smaller when any glass plate is used, and it is understood from these facts that the red color gradually fades. In addition, this becomes clearer when compared with the case of Comparative Test Example 1 in which only a DC voltage is applied without forming a film on a glass plate.
[0069]
[Table 1]
And, compared with the case where only the DC voltage is applied, when both the application of the DC voltage and the irradiation of the mercury lamp or the fluorescent lamp are used in combination, the L can be obtained regardless of which glass plate is used.*Increase in value and a*It can be seen that the decrease in value is abrupt and the red color is fading rapidly. Further, when the mercury lamp is used in combination with the fluorescent lamp, the mercury lamp is used together with a*The reduction of the value may be extremely reduced depending on the used glass plate, and ΔE after 1 hour and 48 hours in most glass plates.*Since the value of is large, it can be seen that the red fading effect is excellent.
[0071]
Moreover, about the influence by the presence or absence of the hydrochloric acid treatment with respect to the glass plate in the case of applying the DC voltage and irradiating the mercury lamp, the case of the hydrochloric acid treatment except for the case after 48 hours using the glass plate of Examples 2 and 2 ′. △ E after 1 hour and 48 hours later*It can be seen that the red color fading effect is large.
[0072]
In addition, when the glass plates of Examples 1 and 1 ′ were used and DC 10 V was applied and simultaneously irradiated with a mercury lamp, a after 48 hours.*However, this indicates that the initial red color disappears and polyaniline is present in the conductive polymer film, so that the color of the film itself is green. In contrast, when the glass plates of Examples 2 and 2 ′ were used and tested under the same conditions as above, the red color disappeared.*Although the value is a small negative value, it is considered that the color of polyaniline present in the conductive polymer film and the color of titanium peroxide cancel each other and the color is almost colorless and transparent.
[0073]
[Measurement result of Experimental Example 2]
The measurement results of Experimental Example 2 are as shown in Table 2. Each of the glass plates used for the measurement has a structure in which a conductive film containing titanium oxide and a conductivity enhancing substance and a polymer film containing polyaniline are laminated in this order on the glass plate. Yes, both direct current and alternating current were used, but both were applied to the conductive film, and the voltage was applied to the conductive polymer film. In all cases, fluorescent lights were used.
[0074]
[Table 2]
According to the experimental results, it can be seen that even when an alternating voltage is applied, it has excellent fading performance for organic dyes. Moreover, it turns out that it is the same tendency as the case where the fluorescent lamp of Experimental example 1 is irradiated. When the glass plate of Example 4 was used, both were a*This value is almost the same as that in Comparative Test Example 3 in which the diluted red ink was applied immediately after the application of the diluted red ink, indicating that almost all of the organic dye was decomposed immediately after the application. Further, when the substrate of Example 3 is used, a*From the comparison of values, the organic dye decomposition performance is superior when alternating current is applied rather than direct current. △ E*The value is smaller in the case of alternating current application as in the case described later.
[0076]
In the case of using the glass plate of Examples 3 and 4 without acid treatment and the case of using the glass plate of Examples 3 ′, 3 ″, 4 ′, and 4 ″ treated with acid, a*From this figure, it can be seen that the red ink is superior in fading ability when compared with the case where the acid treatment is not performed. In contrast, △ E*In the case of a glass plate that is not acid-treated, the value increases with the passage of time, and the numerical value is large even compared to the case of a glass plate that has been acid-treated. Seems also.
[0077]
However, in the case of an acid-treated glass plate, there is almost no difference, and a*The value is drastically decreased, and it is considered that the red organic dye is almost decomposed simultaneously with the fluorescent lamp irradiation. From the above, it can be said that the glass plate of the example treated with the acid is superior in the fading ability of the red ink as compared with the glass plate of the example not treated with the acid.
[0078]
【The invention's effect】
In the present invention, using a conductive polymer such as polyaniline and polypyrrole, a conductive polymer film is formed on cases and interior members of various precision equipment such as lighting fixture covers, tunnel wall panels, and copying machines, Contamination on the surface of various precision equipment cases and interior members can be prevented by simple means of applying a DC or AC voltage to the polymer film, and is contained in various exhaust gases such as automobile exhaust gas. Unburned or incompletely combusted hydrocarbons or carbon monoxide, and harmful components that generate combustion, SOXOr NOXAlternatively, various harmful organic compounds or inorganic gases can be decomposed or oxidized to be purified.
[0079]
Further, by applying an electromagnetic wave having a wavelength of visible light or less, preferably an electromagnetic wave having a wavelength of 300 to 900 nm, simultaneously with application of a direct current or an alternating voltage, the pollution prevention performance and the pollution purification performance are improved. Furthermore, it is preferable that the conductive polymer in the conductive polymer film is in a semiconductive state or an insulating state, so that the conductive polymer in the conductive polymer film or the conductive polymer dispersion is electrically conductive. Contamination purification performance and the like are further improved by the electromagnetic wave irradiation treatment of the absorption wavelength in the state or the acid or alkali treatment.
[0080]
Since it is as described above, especially when a conductive polymer film to which an alternating current or direct current voltage is applied is used for a cover of a lighting fixture that is installed in a tunnel, a fluorescent tube of a fluorescent lamp, a glass bulb of a bulb, etc. Conductive polymer films are inevitably irradiated with electromagnetic waves having a wavelength of visible light or lower by the above-mentioned illumination lamps installed in the tunnel, and contamination of those surfaces, particularly pollution by automobile exhaust gas, is prevented. As a result, reduction of illumination light due to the contamination can be prevented.
[0081]
At the same time, unburned harmful components or NO in automobile exhaust gas released into the tunnelXIt is also possible to decompose or oxidize harmful components generated by combustion, etc., and convert them into harmless substances. Furthermore, when this conductive polymer film is installed on the entire tunnel wall and the amount of illumination light is increased, the inside of the tunnel becomes brighter, which is not only beneficial for safe operation, but also the air inside the tunnel. It is also very effective for purification. As described above, the present invention has excellent operational effects.
[Brief description of the drawings]
FIG. 1 illustrates an outline of a manufacturing process for a titanium peroxide dispersion used in the present invention.
FIG. 2 illustrates an example of a structure for attaching (fixing) a voltage applying electrode to a structure.
FIG. 3 is a sectional view showing a state in which a conductive polymer film is formed on the surface of a plate-like structure. (a) shows the film and electrode arrangement structure when a conductive polymer film is directly formed on the surface of the structure. (b) and (c) show the stacking and electrode arrangement structure when a conductive polymer film is formed on the surface of the structure through a conductive film containing titanium oxide and a conductivity enhancing substance.
FIG. 4 illustrates a voltage application electrode arrangement structure in a plate-like structure such as a glass plate having a conductive polymer film employed in an example.
FIG. 5 illustrates an arrangement structure of an illumination lamp with respect to a glass plate having a conductive polymer film used in an experimental example.
Claims (12)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001305463A JP3730897B2 (en) | 2001-10-01 | 2001-10-01 | A method for preventing or purifying contamination by a conductive polymer film, and a structure having the ability to prevent or purify contamination. |
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| JP2001305463A JP3730897B2 (en) | 2001-10-01 | 2001-10-01 | A method for preventing or purifying contamination by a conductive polymer film, and a structure having the ability to prevent or purify contamination. |
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| JP3730897B2 true JP3730897B2 (en) | 2006-01-05 |
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| US8323385B2 (en) | 2003-04-30 | 2012-12-04 | Mikael Nutsos | Conducting air filter and filter assembly |
| SE525033C2 (en) * | 2003-04-30 | 2004-11-16 | Mikael Nutsos | Conductive air purification filters and aggregates including such filters |
| JP5410035B2 (en) * | 2008-05-14 | 2014-02-05 | 勝之 中野 | Photocathode anticorrosive and metal material coated with photocathode anticorrosive |
| KR101506528B1 (en) * | 2012-11-20 | 2015-03-30 | 오규봉 | Tunnel lamp |
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