JP3836717B2 - Conductive pattern material and conductive pattern forming method - Google Patents

Description

【００４４】
（一般式（１）式中、Ｌはポリマー骨格に連結するのに必要な多価の非金属原子から成る有機基を表し、Ｒ¹、Ｒ²は置換もしくは非置換アルキル基を表す。また、Ｒ¹、Ｒ²はそれが結合している２級炭素原子（ＣＨ）と共に環を形成してもよい。）
【００４５】
前記一般式（１）のＲ¹、Ｒ²は置換もしくは非置換アルキル、置換もしくは非置換アリール基を表し、また、Ｒ¹、Ｒ²はそれが結合している２級炭素原子（ＣＨ）と共に環を形成してもよい。Ｒ¹、Ｒ²が置換もしくは非置換アルキル基を表すとき、アルキル基としてはメチル基、エチル基、イソプロピル基、ｔ−ブチル基、シクロヘキシル基などの直鎖状、分岐状もしくは環状のアルキル基が挙げられ、炭素数１から２５までのものが好適に用いられる。Ｒ¹、Ｒ²が置換もしくは非置換アリール基を表すとき、アリール基には炭素環式アリール基と複素環式アリール基が含まれる。炭素環式アリール基としてはフェニル基、ナフチル基、アントラセニル基、ピレニル基など炭素数６から１９のものが用いられる。また、複素環式アリール基としてはピリジル基、フリル基、その他ベンゼン環が縮環したキノリル基、ベンゾフリル基、チオキサントン基、カルバゾール基などの炭素数３〜２０、ヘテロ原子数１〜５を含むものが用いられる。
【００４６】
Ｒ¹、Ｒ²が置換アルキル基、置換アリール基であるとき、置換基としてはメトキシ基、エトキシ基などの炭素数１〜１０までのアルコキシ基、フッ素原子、塩素原子、臭素原子などのハロゲン原子、トリフルオロメチル基、トリクロロメチル基のようなハロゲン置換されたアルキル基、メトキシカルボニル基、エトキシカルボニル基、ｔ−ブチルオキシカルボニル基、ｐ−クロロフェニルオキシカルボニルなどの炭素数２から１５までのアルコキシカルボニル基またはアリールオキシカルボニル基；水酸基；アセチルオキシ、ベンゾイルオキシ、ｐ−ジフェニルアミノベンゾイルオキシなどのアシルオキシ基；ｔ−ブチルオキシカルボニルオキシ基などのカルボネート基；ｔ−ブチルオキシカルボニルメチルオキシ基、２−ピラニルオキシ基などのエーテル基；アミノ基、ジメチルアミノ基、ジフェニルアミノ基、モルフォリノ基、アセチルアミノ基などの置換、非置換のアミノ基；メチルチオ基、フェニルチオ基などのチオエーテル基；ビニル基、ステリル基などのアルケニル基；ニトロ基；シアノ基；ホルミル基、アセチル基、ベンゾイル基などのアシル基；フェニル基、ナフチル基のようなアリール基；ピリジル基のようなヘテロアリール基等を挙げることができる。また、Ｒ¹、Ｒ²が置換アリール基であるとき、置換基としては、前述したものの他にもメチル基、エチル基などのアルキル基を用いることができる。
【００４７】
上記のＲ¹、Ｒ²としては、感材の保存安定性に優れる点で、置換、非置換のアルキル基が好ましく、経時安定性の点で、アルコキシ基，カルボニル基，アルコキシカルボニル基、シアノ基、ハロゲン基などの電子吸引性基で置換されたアルキル基、もしくはシクロヘキシル基、ノルボルニル基などのアルキル基が特に好ましい。物性値としては、重クロロホルム中、プロトンＮＭＲにおける２級メチン水素のケミカルシフトが４．４ｐｐｍよりも低磁場に現れる化合物が好ましく、４．６ｐｐｍよりも低磁場に現れる化合物がより好ましい。このように、電子吸引性基で置換されたアルキル基が特に好ましいのは、熱分解反応時に中間体として生成していると思われるカルボカチオンが電子吸引性基により不安定化し、分解が抑制されるためであると考えられる。具体的には、−ＣＨＲ¹Ｒ²の構造としては、下記式で表される構造が特に好ましい。
【００４８】
【化２】

【００４９】
また、前記一般式（１）のＬで表される非金属原子からなる多価の連結基とは、１から６０個までの炭素原子、０個から１０個までの窒素原子、０個から５０個までの酸素原子、１個から１００個までの水素原子、及び０個から２０個までの硫黄原子から成り立つものである。より具体的な連結基としては下記の構造単位が組み合わさって構成されるものを挙げることができる。
【００５０】
【化３】

【００５１】
多価の連結基が置換基を有する場合、置換基としてはメチル基、エチル基等の炭素数１から２０までのアルキル基、フェニル基、ナフチル基等の炭素数６から１６までのアリール基、水酸基、カルボキシル基、スルホンアミド基、Ｎ−スルホニルアミド基、アセトキシ基のような炭素数１から６までのアシルオキシ基、メトキシ基、エトキシ基のような炭素数１から６までのアルコキシ基、塩素、臭素のようなハロゲン原子、メトキシカルボニル基、エトキシカルボニル基、シクロヘキシルオキシカルボニル基のような炭素数２から７までのアルコキシカルボニル基、シアノ基、ｔ−ブチルカーボネートのような炭酸エステル基等を用いることができる。
【００５２】
本発明（Ｂ）において、疎水性から親水性に変化する官能基として特に優れているアルコキシアルキルエステル基としては、下記一般式（２）で表されるものである。
【００５３】
【化４】

【００５４】
式中Ｒ³は水素原子を表し、Ｒ⁴は水素原子または炭素数１８個以下のアルキル基を表し、Ｒ⁵は炭素数１８個以下のアルキル基を表す。また、Ｒ³、Ｒ⁴およびＲ⁵の内の２つが結合して環を形成してもよい。特に、Ｒ⁴およびＲ⁵が結合して５または６員環を形成することが好ましい。
【００５５】
以上、本発明（Ｂ）における疎水性から親水性に変化する官能基としては、一般式（１）で表される２級のアルキルスルホン酸エステル基が特に好ましい。
前記一般式（１）〜（２）で表される官能基〔官能基（１）〜（１３）〕の具体例を以下に示す。
【００５６】
【化５】

【００５７】
【化６】

【００５８】
（ii）親水性から疎水性に変化する官能基
本発明（Ｂ）において、熱、酸または輻射線により親水性から疎水性に変化する官能基としては、公知の官能基、例えば、特開平１０−２９６８９５号及び米国特許第６，１９０，８３０号に記載のオニウム塩基を含むポリマー、特にアンモニウム塩を含むポリマーを挙げることができる。具体的なものとして、（メタ）アクリロルオキシアルキルトリメチルアンモニウムなどを挙げることができる。また、下記一般式（３）で示されるカルボン酸基およびカルボン酸塩基が好適なものとして挙げられるが、これらの例示に特に限定されるものではない。
【００５９】
【化７】

【００６０】
（式中、Ｘは−Ｏ−、−Ｓ−、−Ｓｅ−、−ＮＲ⁸−、−ＣＯ−、−ＳＯ−、−ＳＯ₂−、−ＰＯ−、−ＳｉＲ⁸Ｒ⁹−、−ＣＳ−を表し、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹は各々独立して１価の基を表し、Ｍは陽電荷を有するイオンを表す。）
Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹の具体例としては、−Ｆ、−Ｃｌ、−Ｂｒ、−Ｉ、−ＣＮ、−Ｒ¹⁰、−ＯＲ¹⁰、−ＯＣＯＲ¹⁰、−ＯＣＯＯＲ¹⁰、−ＯＣＯＮＲ¹⁰Ｒ¹¹、−ＯＳＯ₂Ｒ¹⁰、−ＣＯＲ¹⁰、−ＣＯＯＲ¹⁰、−ＣＯＮＲ¹⁰Ｒ¹⁴、−ＮＲ¹⁰Ｒ¹¹、−ＮＲ¹⁰−ＣＯＲ¹¹、−ＮＲ¹⁰−ＣＯＯＲ¹¹、−ＮＲ¹⁰−ＣＯＮＲ¹¹Ｒ¹²、−ＳＲ¹⁰、−ＳＯＲ¹⁰、−ＳＯ₂Ｒ¹⁰、−ＳＯ₃Ｒ¹⁰等が挙げられる。
Ｒ¹⁰、Ｒ¹¹、Ｒ¹²は、それぞれ水素原子、アルキル基、アリール基、アルケニル基、又はアルキニル基を表す。
【００６１】
これらのうち、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹として好ましいのは、具体的には、水素原子、アルキル基、アリール基、アルキニル基、アルケニル基である。
Ｍの具体例としては、前述のような陽電荷を有するイオンが挙げられる。
前記一般式（３）で表される官能基の具体例〔官能基（１４）〜（３１）〕を以下に示す。
【００６２】
【化８】

【００６３】
【化９】

【００６４】
本発明（Ｂ）における極性変換基を有する高分子化合物は、上記のような官能基を有するモノマー１種の単独重合体であっても、２種以上の共重合体であっても良い。また、本発明（Ｂ）の効果を損なわない限り、他のモノマーとの共重合体であっても良い。
なお、上記のような官能基を有するモノマーの具体例を以下に示す。
（前記一般式（１）〜（２）で表される官能基を有するモノマーの具体例〔例示モノマー（Ｍ−１）〜（Ｍ−１５）〕）
【００６５】
【化１０】

【００６６】
【化１１】

【００６７】
（前記一般式（３）で表される官能基を有するモノマーの具体例〔例示モノマー（Ｍ−１６）〜（Ｍ−３３）〕）
【００６８】
【化１２】

【００６９】
【化１３】

【００７０】
〔Ｂ−２：支持体〕
本発明（Ｂ）に用いられる支持体としては、前記親水性パターン形成方法（Ａ）で用いたものと同様の、支持体表面或いは中間層、支持体基板、を使用することができる。ただし、本態様においては、中間層は重合性開始能を有さなくてもよい。
また、本発明（Ｂ）においては、支持体として使用するアルミニウム板には必要に応じて粗面化処理、陽極酸化処理などの公知の表面処理を行なってもよい。
【００７１】
（Ｂ−２−１：光熱変換物質）
なお、本発明（Ｂ）における導電性パターン材料をＩＲレーザーなどで画像記録する場合には、該光エネルギーを熱エネルギーに変換するための光熱変換物質を導電性パターン材料のどこかに含有させておくことが好ましい。光熱変換物質を含有させておく部分としては、例えば、パターン形成層、中間層、支持体基板のいずれでもよく、さらには、中間層と支持体基板との間に光熱変換剤層を設け、そこに添加してもよい。
【００７２】
本発明（Ｂ）における導電性パターン材料に用い得る光熱変換物質としては、紫外線、可視光線、赤外線、白色光線等の光を吸収して熱に変換し得る物質ならば全て使用でき、例えば、カーボンブラック、カーボングラファイト、顔料、フタロシアニン系顔料、鉄粉、黒鉛粉末、酸化鉄粉、酸化鉛、酸化銀、酸化クロム、硫化鉄、硫化クロム等が挙げられる。本発明（Ｂ）において特に好ましいのは、書き込みに使用する赤外線レーザの露光波長である７６０ｎｍから１２００ｎｍに極大吸収波長を有する染料、顔料または金属微粒子である。
【００７３】
染料としては、市販の染料及び文献（例えば、「染料便覧」有機合成化学協会編集、昭和４５年刊）に記載されている公知のものが利用できる。具体的には、アゾ染料、金属錯塩アゾ染料、ピラゾロンアゾ染料、アントラキノン染料、フタロシアニン染料、カルボニウム染料、キノンイミン染料、メチン染料、シアニン染料、金属チオレート錯体等の染料が挙げられる。好ましい染料としては、例えば、特開昭５８−１２５２４６号、特開昭５９−８４３５６号、特開昭５９−２０２８２９号、特開昭６０−７８７８７号等に記載されているシアニン染料、特開昭５８−１７３６９６号、特開昭５８−１８１６９０号、特開昭５８−１９４５９５号等に記載されているメチン染料、特開昭５８−１１２７９３号、特開昭５８−２２４７９３号、特開昭５９−４８１８７号、特開昭５９−７３９９６号、特開昭６０−５２９４０号、特開昭６０−６３７４４号等に記載されているナフトキノン染料、特開昭５８−１１２７９２号等に記載されているスクワリリウム色素、英国特許４３４，８７５号記載のシアニン染料等を挙げることができる。
【００７４】
また、米国特許第５，１５６，９３８号記載の近赤外吸収増感剤も好適に用いられ、また、米国特許第３，８８１，９２４号記載の置換アリールベンゾ（チオ）ピリリウム塩、特開昭５７−１４２６４５号（米国特許第４，３２７，１６９号）記載のトリメチンチアピリリウム塩、特開昭５８−１８１０５１号、同５８−２２０１４３号、同５９−４１３６３号、同５９−８４２４８号、同５９−８４２４９号、同５９−１４６０６３号、同５９−１４６０６１号に記載されているピリリウム系化合物、特開昭５９−２１６１４６号記載のシアニン色素、米国特許第４，２８３，４７５号に記載のペンタメチンチオピリリウム塩等や特公平５−１３５１４号、同５−１９７０２号公報に開示されているピリリウム化合物も好ましく用いられる。また、好ましい別の染料の例として、米国特許第４，７５６，９９３号明細書中に式（Ｉ）、（II）として記載されている近赤外吸収染料を挙げることができる。これらの染料のうち特に好ましいものとしては、シアニン色素、スクワリリウム色素、ピリリウム塩、ニッケルチオレート錯体が挙げられる。
【００７５】
本発明（Ｂ）において使用される顔料としては、市販の顔料及びカラーインデックス（Ｃ．Ｉ．）便覧、「最新顔料便覧」（日本顔料技術協会編、１９７７年刊）、「最新顔料応用技術」（ＣＭＣ出版、１９８６年刊）、「印刷インキ技術」ＣＭＣ出版、１９８４年刊）に記載されている顔料が利用できる。顔料の種類としては、黒色顔料、黄色顔料、オレンジ色顔料、褐色顔料、赤色顔料、紫色顔料、青色顔料、緑色顔料、蛍光顔料、金属粉顔料、その他、ポリマー結合色素が挙げられる。具体的には、不溶性アゾ顔料、アゾレーキ顔料、縮合アゾ顔料、キレートアゾ顔料、フタロシアニン系顔料、アントラキノン系顔料、ペリレン及びペリノン系顔料、チオインジゴ系顔料、キナクリドン系顔料、ジオキサジン系顔料、イソインドリノン系顔料、キノフタロン系顔料、染付けレーキ顔料、アジン顔料、ニトロソ顔料、ニトロ顔料、天然顔料、蛍光顔料、無機顔料、カーボンブラック等が使用できる。これらの顔料のうち好ましいものはカーボンブラックである。
【００７６】
これらの染料又は顔料は、光熱変換物質含有層全固形分の０．０１〜５０重量％、好ましくは０．１〜１０重量％、染料の場合特に好ましくは０．５〜１０重量％、顔料の場合特に好ましくは３．１〜１０重量％の割合で使用することができる。顔料又は染料の添加量が０．０１重量％未満であると感度が低くなり、また５０重量％を越えると光熱変換物質含有層の膜強度が弱くなる。
【００７７】
〔Ｂ−３：パターン形成〕
本発明（Ｂ）のパターン形成機構では、上記（ｉ）の如く、疎水性から親水性に変化する官能基を用いた高分子化合物層では、加熱、酸または輻射線照射において極性変換した部分が親水性領域となり、この領域に導電性ポリマーを吸着させることで、該領域が導電性の領域となり、配線が形成されることになる。
一方、上記（ii）の如く、親水性から疎水性に変化する官能基を用いた高分子化合物層では、該層がもともと親水性表面を有しており、加熱、酸または輻射線照射において極性変換した部分が疎水性となる。この場合、未露光部分のみに導電性ポリマーが吸着するため、単一の回路形成、広い面積の導電性領域の形成、などに適する導電性パターン材料が得られる。
また、本発明（Ｂ）における導電性パターン材料にパターン形成を行う場合のエネルギー付与方法には、前記親水性パターン形成方法（Ａ）で用いたものと同様のものを使用することができる。
【００７８】
〔導電性ポリマー層の形成〕
本発明の導電性パターン材料においては、支持体上に、前記親水性ポリマーの親水性官能基に導電性ポリマーを吸着させて形成した導電性ポリマー層を有することを特徴とする。この導電性ポリマー層が導電性を有する。
本発明に用いられる導電性ポリマーとは、１０^-6ｓ・ｃｍ^-1以上、好ましくは、１０^-1ｓ・ｃｍ^-1以上の導電性を有する高分子化合物であれば、いずれのものも使用することができるが、具体的には、例えば、置換および非置換の導電性ポリアニリン、ポリパラフェニレン、ポリパラフェニレンビニレン、ポリチオフェン、ポリフラン、ポリピロール、ポリセレノフェン、ポリイソチアナフテン、ポリフェニレンスルフィド、ポリアセチレン、ポリピリジルビニレン、ポリアジン等が挙げられる。これらは１種のみを用いてもよく、また、目的に応じて２種以上を組み合わせて用いてもよい。また、所望の導電性を達成できる範囲であれば、導電性を有しない他のポリマーとの混合物として用いることもできるし、これらのモノマーと導電性を有しない他のモノマーとのコポリマーなども用いることができる。
【００７９】
このような導電性ポリマーを用いて、導電性ポリマー層を形成する方法には特に制限はないが、均一な薄膜を形成し得るという観点からは、以下に述べるような導電性を有するモノマーを用いる方法が好ましい。
まず、前記親水性グラフトポリマー鎖が存在する親水性表面を有する支持体を、過硫酸カリウムや、硫酸鉄（III）などの重合触媒や重合開始能を有する化合物を含有する溶液に浸漬し、この液を撹拌しながら導電性ポリマーを形成し得るモノマー、例えば、３、４−エチレンジオキシチオフェンなどを徐々に滴下する。このようにすると、グラフトポリマー鎖の親水性の官能基と導電性ポリマーを形成し得るモノマーとが相互作用により強固に吸着すると共に、モノマー同士の重合反応が進行し、親水性グラフトポリマー鎖が存在する親水性表面上に、導電性ポリマーの極めて薄い膜が形成され、これが導電性ポリマー層となる。
このように形成された導電性ポリマー層は、親水性表面上での重合反応により形成されているため、モノマーの供給速度などの条件を調整することで非常に薄い膜も形成することができ、さらに、薄膜であっても均質で、且つ、膜厚が均一であるという利点を有する。
【００８０】
支持体表面における重合反応を利用すれば、例えば、ＰＥＴの如き樹脂などの支持体表面に直接導電性ポリマーの薄膜を形成することもできるが、そのような支持体との相互作用を形成し得ないこのような膜は容易に剥離してしまい、実用上問題のないレベルの膜強度を有する薄膜を形成することはできない。
【００８１】
本発明においては、導電性モノマー自体がグラフトポリマー鎖の親水性基と静電気的に、或いは、極性的に相互作用を形成することで強固に吸着するため、それらが重合して形成されたポリマー膜は、親水性表面との間に強固な相互作用を形成しているため、薄膜であっても、擦りや引っ掻きに対しても充分な強度を有するものとなる。
さらに、導電性ポリマーと親水性の官能基とが、陽イオンと陰イオンの関係で吸着するような素材を選択することで、親水性の官能基が導電性ポリマーのカウンターアニオンとして吸着することになり、一種のドープ剤として機能するため、導電性パターン材料の導電性を一層向上させることができるという効果を得ることもできる。具体的には、例えば、親水性基としてスチレンスルホン酸を、導電性ポリマーの素材としてチオフェンを選択すると、両者の相互作用により、親水性表面と導電性ポリマー層との界面にはカウンターアニオンとしてスルホン酸基（スルホ基）を有するポリチオフェンが存在し、これが導電性ポリマーのドープ剤として機能することになる。
【００８２】
親水性パターン材料表面に形成された導電性ポリマー層の膜厚には特に制限はないが、０．０１μｍ〜１０μｍの範囲であることが好ましく、０．１μｍ〜５μｍの範囲であることがより好ましい。導電性ポリマー層の膜厚がこの範囲内であれば、充分な導電性と透明性とを達成することができる。０．０１μｍ以下であると導電性が不充分となる懸念があるため好ましくない。
【００８３】
以上の方法で、パターン形成された本発明の導電性パターン材料は、種々の回路形成に使用でき、パターン形成手段を選択することでナノスケールの導電性領域を形成することができるため、マイクロマシンや超ＬＳＩなどの回路形成を含む広い用途が期待される。
さらに、支持体にＰＥＴなどの透明フィルムを使用した場合には、パターン形成された透明導電性フィルムとして使用することができる。このような透明導電性フィルムの用途としては、ディスプレイ用透明電極、調光デバイス、太陽電池、タッチパネル、その他の透明導電膜が挙げられるが、ＣＲＴやプラズマディスプレイにつける電磁波シールドフィルターとして特に有用である。このような電磁波シールドフィルターは高い導電性と透明性とを必要とするため、導電性ポリマー層を格子状に設けることが好ましい。このような格子線幅は、２０〜１００μｍ、開口部は５０〜６００μｍ程度が好ましい。この格子は必ずしも規則正しく、直線で構成されていなくてもよく、曲線状で構成されていてもよい。本発明においては、このような任意のパターン形状の導電性ポリマー層を容易に形成しうるため、目的に応じた種々の設定が可能である。
【００８４】
【実施例】
以下、実施例により、本発明を詳細に説明するが、本発明はこれらに限定されるものではない。
〔参考例１〕
（親水性パターンの作成）
１８８μｍのコロナ処理された２軸延伸ポリエチレンテレフタレートフィルム（Ａ４１００、東洋紡（株）製）を用い、グロー処理として平版マグネトロンスパッタリング装置（ＣＦＳ−１０−ＥＰ７０、芝浦エレテック製）を使用し、下記条件で酸素グロー処理を行った。
初期真空：１．２×１０^−３Ｐａ
酸素圧力：０．９Ｐａ
ＲＦグロー：１．５ｋｗ
処理時間：６０ｓｅｃ
【００８５】
次に、グロー処理したフィルム上に、アクリル酸をロッドバー＃６を用いて塗布し、塗布面を２５μのＰＥＴフィルムでラミネートした。次にこの上にクロムを蒸着したマスクパターンを重ね、上からＵＶ光を照射（４００Ｗ高圧水銀灯：ＵＶＬ−４００Ｐ、理工科学産業（株）製 照射時間３０秒）した。光照射後、マスクとラミネートフィルムを取り除き、水洗することによりポリアクリル酸がパターン状にグラフトされた親水性パターン１を得た。
【００８６】
（導電性ポリマー層の形成）
前記親水性パターン１を有する支持体を、アントラキノン−２−スルホン酸ナトリウム・一水和物１．２３ｇ、５−スルフォサチリチル酸ナトリウム・水和物７．２０ｇ、及び、三塩化鉄・６水和物４．３８ｇ、を１２５ｍｌの水に溶解した溶液に浸漬し、撹拌しながらピロール０．７５ｍｌと水１２５ｍｌの溶液を加えた。一時間後、支持体を取り出し、水洗し、次にアセトンで洗浄することで支持体の表面に導電性ポリマーであるポリピロール層が形成された参考例１の導電性パターン材料１を得た。
【００８７】
〔導電性パターン材料の評価〕
１．導電性
得られた導電性パターン材料１の表面抵抗値を、ＬＯＲＥＳＴＡ−ＦＰ（三菱化学（株）製）を用いて四探針法により測定した。表面抵抗値は、１０００Ω／□であった。表面抵抗値が低いほど、導電性に優れるものであると評価する。
２．鉛筆硬度
得られた導電性パターン材料１の表面の皮膜強度を、ＪＩＳ Ｇ ０２０２に記載の方法に準じて測定した。鉛筆硬度は４Ｈ以上であった。試験に使用した鉛筆硬度が高い、即ち、１Ｈ→４ＨのようにＨの数値が高いほど、強度に優れると評価する。
【００８８】
〔参考例２〕
（親水性パターンの作成）
実施例１で用いられたものと同様のポリエチレンテレフタレートフィルム上に下記の重合性開始能を発現する層（重合性層）形成用の組成物をロッドバー＃１７を用いて塗布し、８０℃で２分間乾燥させた。次にこの塗布されたフィルムに、上からＵＶ光を照射（４００ｗ高圧水銀灯 照射時間１０分）し、予備硬化させた。
・アリルメタクリレート／メタクリル酸共重合体 ４ｇ
（モル比率８０／２０、分子量１０万）
・エチレンオキシド変性ビスフェノールＡジアクリレート ４ｇ
（東亞合成（株）Ｍ２１０）
・１−ヒドロキシシクロヘキシルフェニルケトン １．６ｇ
・１−メトキシ−２−プロパノール １６ｇ
【００８９】
次にこの支持体表面上にスチレンスルホン酸ナトリウムの水溶液（３０ｗｔ％）をロッドバー＃１２を用いて塗布し、乾燥することなく塗布面を２５μのＰＥＴフィルムでラミネートした。次にこの上にクロムを蒸着したマスクパターンを重ね、上からＵＶ光を照射（４００Ｗ高圧水銀灯 照射時間１０分）した。光照射後、マスクとラミネートフィルムを取り除き、水洗することによりポリスチレンスルホン酸ナトリウムがパターン状にグラフトされた親水性パターン２を得た。
【００９０】
（導電性ポリマー層の形成）
前記親水性パターン２を有する支持体を、過硫酸カリウム１３．０ｇ、及び、硫酸鉄（ＩＩＩ）５０ｍｇを溶かした２０００ｍｌの液に浸漬した。つぎにこの液を撹拌しながら３、４−エチレンジオキシチオフェン５．５ｇを徐々に滴下した。この液を室温で１０時間撹拌した。支持体を取り出し、水洗することで支持体の表面に導電性ポリマーであるポリチオフェン層が形成された参考例２の導電性パターン材料２を得た。
【００９１】
〔導電性パターン材料の評価〕
１．導電性
得られた導電性パターン材料２の表面抵抗値を、ＬＯＲＥＳＴＡ−ＦＰ（三菱化学（株）製）を用いて四探針法により測定した。表面抵抗値は、１３００Ω／□であり、実用に適する導電性を有していることがわかった。
２．鉛筆硬度
得られた導電性パターン材料２の表面の皮膜強度を、ＪＩＳ Ｇ ０２０２に記載の方法に準じて測定した。鉛筆硬度は４Ｈ以上であり、強度に優れていることがわかった。
【００９２】
〔実施例１〕
（親水性パターンの形成）
参考例１で用いられたものと同様のポリエチレンテレフタレートフィルム上に下記の中間層形成用塗布液をロッドバー＃１０を用いて塗布し、１００℃で１分間乾燥し、膜圧１．６μｍの赤外線吸収剤を含有する中間層を作成した。
・エポキシ樹脂（エピコート， Ｙｕｋａ−ｓｈｅｌｌ Ｃｏ，Ｌｔｄ．） ２ ｇ
・赤外線吸収剤（ＩＲ１２５ 和光純薬剤） ０．２ｇ
・１−メトキシ−２−プロパノール ９ ｇ
・メチルエチルケトン ９ ｇ
【００９３】
中間層を形成した支持体表面を次の条件にてプラズマ処理して表面グラフト重合によるパターン形成層の形成を行った。
島津製作所製ＬＣＶＤ−０１型プラズマ処理装置を用いて０．０４toorのアルゴンガス雰囲気下にて１０秒間処理後、空気に曝し、中間層表面にパーオキシド基を導入した。この膜を１０ｗｔ％のα（スチレン−４−スルホニル）酢酸Ｎａ塩水溶液に浸漬し、１５分間アルゴンガスをバブルしたのち、７時間６０℃に加温することによってグラフト重合を行った。グラフト重合後膜を３０００ｍｌのイオン交換水中につけ、グラフト重合以外のホモポリマーを除去することによりプラズマ処理により表面にグラフトされたパターン形成層を備えた導電性パターン形成材料３を得た。
得られた導電性パターン形成材料３を波長８３０ｎｍの赤外光を発する赤外線レーザ（ビーム径２０μｍ）にて像様に露光した。
【００９４】
（導電性ポリマー層の形成）
参考例１と同様にして、支持体上に導電性ポリマーであるポリピロ−ル層を形成し、実施例１の導電性パターン材料３を得た。
【００９５】
〔導電性パターン材料の評価〕
１．導電性
得られた導電性パターン材料３の表面抵抗値を、ＬＯＲＥＳＴＡ−ＦＰ（三菱化学（株）製）を用いて四探針法により測定した。表面抵抗値は、１０００Ω／□であり、実用に適する導電性を有していることがわかった。
２．鉛筆硬度
得られた導電性パターン材料３の表面の皮膜強度を、ＪＩＳ Ｇ ０２０２に記載の方法に準じて測定した。鉛筆硬度は４Ｈ以上であり、強度に優れていることがわかった。
【００９６】
【発明の効果】
本発明の導電性パターン材料は、強固で耐久性に優れ、且つ且つデジタルデータに基くレーザ露光により高解像度で、断線のない微細なパターン形成が可能であり、また、大面積化、導電性安定性、製造適正のなどの観点からも優れた導電性パターンを形成しうる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a conductive pattern material and a pattern forming method, and more particularly to a conductive pattern material that can easily form a fine conductive pattern and is useful for forming a fine wiring board, and a conductive pattern applicable thereto. It relates to a forming method.
[0002]
[Prior art]
Conventionally, various conductive pattern materials have been used for forming a wiring board. A typical example of these is that a thin film conductive material formed by a known method such as vacuum deposition is provided on an insulator, which is subjected to resist treatment, and a part of the resist prepared in advance is removed by pattern exposure. Then, an etching process is performed to form a desired pattern, and at least four processes are required. When wet etching is performed, a waste liquid processing process is also required. I had to take it.
As another pattern forming method, a conductive pattern material using a photoresist is also known. This method is a method in which a substrate coated with a photoresist polymer or a photoresist on a dry film is exposed to UV through an arbitrary photomask to form a pattern such as a lattice. It is useful for forming an electromagnetic wave shield that requires high performance.
In recent years, with the progress of micromachine development and the further miniaturization of VLSI, these wiring structures have been required to be fine in nano units, and there is a limit to miniaturization in conventional metal etching. There is also concern about disconnection during processing of the thin wire portion. For this reason, a method using a functional organic molecular thin film has been proposed as a method for forming a dense pattern with controlled orientation, but even in this method, image-like writing is performed like a conventional lithographic film. Since UV exposure is performed through a mask, the degree of freedom in circuit formation is not very high.
[0003]
On the other hand, in recent years, as a conductive pattern material, a method for directly forming a pattern from digitized data without using a mask or the like has attracted attention and various proposals have been made.
If such a digitized pattern forming method is used, it is expected that a fine pattern is arbitrarily formed. One of such methods is a method using a self-assembled monolayer. This utilizes a molecular assembly spontaneously formed when a substrate is immersed in an organic solvent containing a surface active molecule. For example, an organic silane compound and SiO₂, Al₂O_ThreeCombinations with substrates and combinations of alcohols and amines with platinum substrates can be mentioned, and pattern formation by an optical lithography method or the like is possible. Although such monomolecular films enable the formation of fine patterns, it is necessary to use a limited combination of substrates and materials, which makes it difficult to develop practical applications, and is suitable for practical use. The current pattern forming technology has not been established yet.
[0004]
Furthermore, organic transistors using conductive polymer patterns have been studied from the viewpoints of light weight, flexibility, and environmental friendliness, but the characteristics of supports using such organic materials are light, thin, and flexible. Therefore, an element having a large area can be easily produced (using a technique similar to printing at room temperature). Combining these features with the electrical and optical properties of newly developed organic semiconductors, the most needed technology for information personalization in current information technology, for example, simple information We can expect new developments in technology to make wearable mobile devices with processing functions and human-friendly input / output functions.
Specific examples of conductive polymer pattern forming techniques that have been studied so far include G.I. Whitesides et al., Langmuir 1997 vol13 page 6480 and T.W. Granlund et al., Advanced materials 2000 vol 12 page 269; M.M. Known are a photoinitiator reduction method of a conductive polymer described in de Leeuw et al., Applied Physics Letters vol 73 page 108, a photopolymerization formation method of a conductive polymer described in US Pat. No. 542784, and the like. However, none of them is sufficient from the practical viewpoints such as durability, enlargement of area, conductivity stability, and manufacturing suitability.
[0005]
[Problems to be solved by the invention]
The object of the present invention, which has been made in consideration of the above-mentioned drawbacks of the prior art, is to be able to form a fine pattern with high resolution and no disconnection by laser exposure based on digital data, which is strong and durable. Another object of the present invention is to provide a conductive pattern material and a conductive pattern forming method that are excellent from the viewpoints of area enlargement, conductive stability, manufacturing suitability, and the like.
[0006]
[Means for Solving the Problems]
  As a result of studying the strong ion adsorptivity of the graft polymer, the present inventors have found that the above object is achieved by a combination of a hydrophilic surface on which a hydrophilic polymer exists and a conductive polymer. The present invention has been completed.
  That is, the conductive pattern material of the present invention has the following on the support:In (B)By forming a hydrophilic pattern directly bonded to the surface of the support by the means described, a conductive polymer layer is formed on the hydrophilic pattern.
  Further, the conductive pattern forming method of the present invention includes a step of forming a hydrophilic pattern directly bonded to the surface of the support on the support, and adsorbing and polymerizing the conductive monomer on the hydrophilic pattern. And a step of forming a conductive polymer layer.
  As a particularly useful method for forming the hydrophilic pattern,Is
(B) On the support, a polymer compound-containing layer having a functional group whose hydrophilicity / hydrophobicity is changed by heat, acid or radiation is provided, and image-wise heating, acid supply or radiation irradiation is performed. Forming hydrophilic patterns by changing hydrophilicity / hydrophobicityLawCan be mentioned.
[0007]
  Since the conductive pattern material of the present invention selectively adsorbs the conductive polymer to the surface hydrophilic region formed by pattern exposure, a high-resolution pattern based on digital data can be obtained.
  Used as the pattern forming layer of the conductive pattern material of the present inventionAboveThe polymer compound having a functional group whose hydrophilicity / hydrophobicity is changed by heat, acid or radiation in (B) is chemically bonded directly to the support at the terminal or side chain or via the trunk polymer compound. In addition, since it has a highly mobile graft chain structure, the adsorption rate is extremely fast compared to the case where a conductive polymer is adsorbed on a general crosslinked polymer film, and the amount of polymer that can be adsorbed per unit area. Has the feature of increasing.
  In a preferred embodiment of the present invention, the conductive polymer for forming the wiring is a polymer layer in which the conductive monomer as a precursor thereof is ionically adsorbed on the surface of the pattern forming layer according to the polarity and is directly subjected to a polymerization reaction. Therefore, it is firmly fixed on the hydrophilic pattern. For this reason, it is considered that even a thin layer can form a fine wiring pattern having high strength and excellent flexibility.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
First, it is referred to when forming a polymer compound-containing layer having a functional group whose hydrophilicity / hydrophobicity is changed by heat, acid or radiation of the following (B), which is cited as a reference example in the present invention. ( A ) The method for forming the hydrophilic pattern will be described in detail. Instead of a compound having a polymerizable group and a hydrophilic group useful for forming this hydrophilic pattern, heat is used by using a compound having a functional group whose hydrophilicity / hydrophobicity is changed by heat or acid or radiation described below, A polymer compound-containing layer having a functional group whose hydrophilicity / hydrophobicity is changed by an acid or radiation can be formed.
[A-1: hydrophilic compound having a polymerizable group]
  First, (A) a method of forming a hydrophilic pattern by bringing a hydrophilic compound having a polymerizable group into contact with a support and irradiating radiation like an image will be described.
(A-1-1: Surface graft polymerization)
  The present inventionReference exampleIn the pattern forming layer in (A), a hydrophilic compound having a polymerizable group is brought into contact with the support and energy is applied thereto, whereby the polymerizable group of the hydrophilic compound and the support generate a chemical bond. It is possible to form a hydrophilic region which is strong and excellent in durability and has high hydrophilicity. Such bond formation is referred to as surface grafting.
  This contact may be performed by immersing the support in a liquid composition containing a polymerizable hydrophilic compound, but will be described later from the viewpoint of the handleability and production efficiency of the conductive pattern material. Thus, it is preferable to form a layer mainly composed of a composition containing a polymerizable hydrophilic compound on the support surface by a coating method.
[0009]
Below, formation of the surface graft by energy provision is demonstrated.
In the present invention (A), the hydrophilic region is formed by a method called surface graft polymerization. Graft polymerization gives active species on a polymer compound chain by applying energy by a conventionally known method such as light or electron beam, thereby further polymerizing another polymerizable compound that initiates polymerization, This is a method of synthesizing a graft (grafted) polymer, and is called surface graft polymerization, particularly when a polymer compound that gives active species forms a surface.
[0010]
Usually, the surface of a support such as PET constituting the substrate is directly treated with plasma or electron beam to generate radicals on the surface to express the polymerization initiating ability. A graft polymer surface layer, that is, a surface layer having a hydrophilic group can be obtained by reacting with a monomer having a group. In a preferred embodiment of the present invention (A), by adding a compound having a polymerization initiating ability to the support in advance, such active sites can be easily formed with low energy, and the generated active sites. Therefore, a surface having higher hydrophilicity can be formed by a simple method.
[0011]
A known method can be applied to the method of causing graft polymerization by light irradiation or the like. As a specific method of the photograft polymerization method, methods described in JP-A-63-92658, JP-A-10-296895, and JP-A-11-119413 can be used. Specifically, it is a method in which a polymerizable composition comprising a polymerization initiator and a polymerizable compound is preliminarily coated on a support, and a hydrophilic compound having a polymerizable group is contacted thereon and irradiated with light.
As another means for forming a hydrophilic compound in a pattern, T.W. Matsuda, Y .; As described in Nakayama Langmuir 1999 vol15 page 5560 and Macromolecules 1996 vol29 page8622, a polymer substrate having an N, N-diethylthiocarbamate group is used, and a hydrophilic monomer is brought into contact with this to cause surface graft polymerization. And a method of forming a hydrophilic pattern in which polyacrylic acid is fixed on the surface; As described in Ito Macromolecules 1997 vol30 page 7001, a method of obtaining a hydrophilic polymer pattern in which polyacrylic acid is fixed on the surface by applying polyacrylic acid having an azide group to a polymer substrate such as polysulylene and exposing to a pattern is also applied. be able to.
Among the methods for creating a surface graft, it is preferable to adopt a photografting method in which energy is imparted by light irradiation.
[0012]
(A-1-2: hydrophilic compound having a polymerizable group)
The hydrophilic compound having a polymerizable group used in the present invention (A) is a hydrophilic homopolymer or copolymer obtained by using at least one kind selected from a hydrophilic monomer described later or the hydrophilic monomer. As a group, it refers to a radically polymerizable group-containing hydrophilic compound into which an ethylene addition polymerizable unsaturated group such as a vinyl group, an allyl group, or a (meth) acryl group is introduced, and this compound has a polymerizable group at least at a terminal or a side chain. In particular, those having a polymerizable group at the terminal are preferable, and those having a polymerizable group at the terminal and side chain are more preferable.
[0013]
Such a radically polymerizable group-containing hydrophilic compound into which an ethylene addition polymerizable unsaturated group has been introduced can be synthesized as follows.
As a synthesis method, a hydrophilic monomer and a monomer having an ethylene addition polymerizable unsaturated group are copolymerized, a hydrophilic monomer and a monomer having a double bond precursor are copolymerized, and then treated by treatment with a base or the like. Examples thereof include a method of introducing a double bond and a method of reacting a functional group of a hydrophilic compound with a monomer having an ethylene addition polymerizable unsaturated group. Particularly preferred is a method of reacting a functional group of a hydrophilic compound with a monomer having an ethylene addition polymerizable unsaturated group from the viewpoint of synthesis suitability.
[0014]
Examples of the hydrophilic monomer used for the synthesis of the hydrophilic compound having the radical polymerizable group at the main chain terminal and / or side chain include (meth) acrylic acid or its alkali metal salt and amine salt, itaconic acid or its alkali metal. Salts and amine salts, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monomethylol (meth) acrylamide, N-dimethylol (meth) acrylamide, allylamine or a hydrohalide thereof, 3-vinylpropionic acid Or alkali metal salt and amine salt thereof, vinyl sulfonic acid or alkali metal salt and amine salt thereof, 2-sulfoethyl (meth) acrylate, polyoxyethylene glycol mono (meth) acrylate, 2-acrylamido-2-methylpropanesulfur Monomers having hydrophilic groups such as carboxyl groups, sulfonic acid groups, phosphoric acid groups, amino groups or their salts, hydroxyl groups, amide groups and ether groups such as acid and acid phosphooxypolyoxyethylene glycol mono (meth) acrylates Is mentioned.
[0015]
Examples of the allyl group-containing monomer copolymerized with the hydrophilic monomer include allyl (meth) acrylate and 2-allyloxyethyl methacrylate.
Examples of the monomer having a double bond precursor include 2- (3-chloro-1-oxopropoxy) ethyl methacrylate.
As a monomer having an addition-polymerizable unsaturated group used for introducing an unsaturated group by utilizing a reaction with a functional group such as a carboxyl group, an amino group or a salt thereof, a hydroxyl group and an epoxy group in a hydrophilic monomer (Meth) acrylic acid, glycidyl (meth) acrylate, allyl glycidyl ether, 2-isocyanatoethyl (meth) acrylate, and the like.
[0016]
A preferred example of the hydrophilic compound having a polymerizable group at the terminal and / or side chain is a hydrophilic macromonomer. The method for producing the macromonomer used in the present invention (A) is described in, for example, Chapter 2 “Macro Monomer” published by IPC Publishing Office on September 20, 1999 (Editor: Yuya Yamashita). Various production methods have been proposed in “Synthesis of Monomers”. Particularly useful hydrophilic macromonomers used in the present invention (A) include macromonomers derived from carboxyl group-containing monomers such as acrylic acid and methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid , Sulfonic acid macromonomer derived from monomers of vinyl styrene sulfonic acid, and salts thereof, amide macromolecule derived from (meth) acrylamide, N-vinylacetamide, N-vinylformamide, N-vinylcarboxylic acid amide monomer Monomers, macromonomers derived from hydroxyl-containing monomers such as hydroxyethyl methacrylate, hydroxyethyl acrylate, glycerol monomethacrylate, methoxyethyl acrylate, methoxypolyethylene glycol acrylate, poly Macromonomers derived from alkoxy group or ethylene oxide group-containing monomers such as Chi glycol acrylate. A monomer having a polyethylene glycol chain or a polypropylene glycol chain can also be usefully used as the macromonomer used in the present invention (A).
Among these macromonomers, a useful molecular weight is in the range of 250 to 100,000, and a particularly preferable range is 400 to 30,000.
[0017]
(A-1-3: hydrophilic monomer useful in combination with the hydrophilic macromonomer)
Further, a hydrophilic monomer may be further added to the hydrophilic macromonomer having a polymerizable group. The polymerization rate can be increased by adding a hydrophilic monomer.
The addition amount of the hydrophilic monomer is preferably 0 to 60% by weight in solid content in the hydrophilic compound having all polymerizable groups. If it is 60% by weight or more, the applicability is poor and uniform application is not possible.
As a hydrophilic monomer useful for use in combination with a hydrophilic compound having a polymerizable group at the terminal and / or side chain, a monomer having a positive charge such as ammonium or phosphonium, or a sulfonic acid group, a carboxyl group, Monomers having a negative charge or an acidic group that can dissociate into a negative charge, such as a phosphoric acid group and a phosphonic acid group, can also be mentioned, for example, a hydroxyl group, an amide group, a sulfonamide group, an alkoxy group, A hydrophilic monomer having a nonionic group such as a cyano group can also be used.
In the present invention (A), the following monomers can be mentioned as specific examples of particularly useful hydrophilic monomers in combination with the hydrophilic macromonomer.
[0018]
For example, (meth) acrylic acid or its alkali metal salt and amine salt, itaconic acid or its alkali metal salt and amine salt, allylamine or its hydrohalide salt, 3-vinylpropionic acid or its alkali metal salt and amine salt Vinyl sulfonic acid or its alkali metal salt and amine salt, vinyl styrene sulfonic acid or its alkali metal salt and amine salt, 2-sulfoethylene (meth) acrylate, 3-sulfopropylene (meth) acrylate or its alkali metal salt and Amine salts, 2-acrylamido-2-methylpropanesulfonic acid or alkali metal salts and amine salts thereof, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate, allylamine or its amines Carboxyl groups, sulfonic acid groups, such as hydrogenates, carboxyl groups, sulfonic acid groups, such as 2-trimethylaminoethyl (meth) acrylate or hydrohalates thereof, carboxyl groups, sulfonic acid groups, phosphoric acid, amino groups or salts thereof , Phosphoric acid, an amino group or a salt thereof, and the like can be used. Also, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monomethylol (meth) acrylamide, N-dimethylol (meth) acrylamide, N-vinylpyrrolidone, N-vinylacetamide, allylamine or a hydrohalide thereof , Monomers having an amino acid skeleton in the molecule such as polyoxyethylene glycol mono (meth) acrylate, N-methacryloyloxyethylcarbamic acid aspartic acid, monomers having a sugar skeleton in the molecule such as glycoxyethyl methacrylate are also useful. .
[0019]
The solvent used in the composition containing such a hydrophilic compound is not particularly limited as long as the hydrophilic macromonomer or the hydrophilic monomer as a main component can be dissolved, but water or an aqueous solution such as a water-soluble solvent can be used. A solvent is preferable, and a mixture thereof or a solvent obtained by adding a surfactant to the solvent is preferable.
The water-soluble solvent refers to a solvent miscible with water in an arbitrary ratio, and examples of such a water-soluble solvent include alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, and glycerin, acids such as acetic acid, Examples thereof include ketone solvents such as acetone, amide solvents such as formamide, and the like.
[0020]
The surfactant that can be added to the solvent as needed may be any that dissolves in the solvent. Examples of such surfactants include an anionic surfactant such as sodium n-dodecylbenzenesulfonate. Agents, cationic surfactants such as n-dodecyltrimethylammonium chloride, polyoxyethylene nonylphenol ether (commercially available products such as Emulgen 910, manufactured by Kao Corporation), polyoxyethylene sorbitan monolaurate (commercially available) Examples of the product include a trade name “Tween 20” and the like, and nonionic surfactants such as polyoxyethylene lauryl ether.
When the composition is brought into contact in a liquid state, it can be carried out arbitrarily, but the coating amount when forming the hydrophilic compound composition coating layer by a coating method is 0.1 to 10 g / m in terms of solid content.²Is preferred, in particular 1 to 5 g / m²Is preferred. 0.1 g / m²If it is less than 1, sufficient surface hydrophilicity cannot be obtained, and 10 g / m²If it exceeds 1, it is difficult to obtain a uniform coating film.
[0021]
[A-2: Support]
The support used in the present invention (A) has a support surface on which the terminal or side chain of the hydrophilic compound having a polymerizable group described above can be chemically bonded directly or via a trunk polymer compound. Is. The support itself may have such characteristics, and an intermediate layer having such characteristics may be provided on the support.
[0022]
(A-2-1: Support surface or intermediate layer)
Such a support surface may be either an inorganic layer or an organic layer as long as it has characteristics suitable for graft synthesis of the surface graft layer.
In particular, when a thin layer polymer is synthesized by a photograft polymerization method, a plasma irradiation graft polymerization method, or a radiation irradiation graft polymerization method, a layer having an organic surface is preferable, and an organic polymer layer is particularly preferable. . Organic polymers include epoxy resins, acrylic resins, urethane resins, phenol resins, styrene resins, vinyl resins, polyester resins, polyamide resins, melamine resins, formalin resins and other synthetic resins, gelatin, casein, cellulose, Any natural resin such as starch can be used. However, in the photograft polymerization method, plasma irradiation graft polymerization method, radiation irradiation graft polymerization method, etc., the start of graft polymerization proceeds from the extraction of hydrogen of the organic polymer. It is particularly preferable from the viewpoint of production suitability to use a polymer that is easily pulled out, particularly an acrylic resin, a urethane resin, a styrene resin, a vinyl resin, a polyester resin, a polyamide resin, and an epoxy resin.
Such a support surface may also serve as a substrate (support) described later, or may be an intermediate layer provided on the support as necessary.
[0023]
(A-2-2: Support substrate)
The support substrate used in the conductive pattern material of the present invention (A) and having a support surface having the above characteristics on its surface is preferably a dimensionally stable plate-like material such as paper, Paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, Cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), paper or plastic film on which a metal as described above is laminated or vapor-deposited. As the support substrate used in the present invention (A), a polyester film or an aluminum plate is preferable, and among them, a polyester film that can also serve as the intermediate layer is particularly preferable.
[0024]
In the conductive pattern material using the hydrophilic pattern of the present invention (A), the hydrophilic compound is directly chemically bonded from the viewpoint of the formability of the pattern forming layer and the adhesion to the pattern forming layer. It is preferable to use a support substrate having a roughened surface.
When using a roughened support substrate, it is preferable that the surface properties satisfy the following conditions.
As a preferable state of the roughened support substrate, the center line average roughness (Ra) of the two-dimensional roughness parameter is 0.1 to 1 μm, the maximum height (Ry) is 1 to 10 μm, and the ten-point average roughness. The height (Rz) is 1 to 10 μm, the average interval (Sm) of the irregularities is 5 to 80 μm, the average interval (S) of the local peaks is 5 to 80 μm, the maximum height (Rt) is 1 to 10 μm, the centerline peak height ( Rp) is 1 to 10 μm, and the centerline valley depth (Rv) is 1 to 10 μm. Those satisfying one or more of these conditions are preferable, and all of them are more preferable.
[0025]
(A-2-3: Layer expressing polymerization initiating ability)
In the present invention (A), it is preferable to add a polymerizable compound and a polymerization initiator as a compound that exhibits polymerization initiation ability by applying energy to the surface of the support.
The layer that expresses the polymerization initiating ability (hereinafter, appropriately referred to as a polymerizable layer) is prepared by dissolving necessary components in a solvent capable of dissolving them, and providing them on the surface of the support by a method such as coating. It can be hardened and formed by irradiation.
[0026]
(A) Polymerizable compound
The polymerizable compound used in the polymerizable layer has good adhesion to the support and is hydrophilic in the terminal layer and / or side chain which is contained in the upper layer by applying energy such as actinic ray irradiation. There is no particular limitation as long as the functional compound can be added, and among these, a hydrophobic polymer having a polymerizable group in the molecule is preferable.
Specific examples of such hydrophobic polymers include diene homopolymers such as polybutadiene, polyisoprene, and polypentadiene, and allyl groups such as allyl (meth) acrylates and 2-allyloxyethyl methacrylates. Monomer homopolymer;
Further, binary or multiple with styrene, (meth) acrylic acid ester, (meth) acrylonitrile, etc. containing diene monomers such as polybutadiene, polyisoprene, polypentadiene or allyl group-containing monomers as constituent units. Copolymer;
And linear polymers or three-dimensional polymers having a carbon-carbon double bond in the molecule such as unsaturated polyester, unsaturated polyepoxide, unsaturated polyamide, unsaturated polyacryl, and high-density polyethylene.
In this specification, when referring to both or one of “acrylic and methacrylic”, it may be expressed as “(meth) acrylic”.
The content of the polymerizable compound is preferably in the range of 0 to 100% by weight, particularly preferably in the range of 10 to 80% by weight in terms of solid content in the polymerizable layer.
[0027]
(B) Polymerization initiator
The polymerizable layer in the present invention (A) preferably contains a polymerization initiator for expressing the polymerization initiating ability by applying energy. The polymerization initiator used here is a known thermal polymerization initiator, photopolymerization initiator, or the like that can exhibit polymerization initiating ability by predetermined energy, for example, irradiation with actinic rays, heating, irradiation with electron beam, etc. Can be selected and used as appropriate. Among these, it is preferable from the viewpoint of production suitability to use photopolymerization having a higher reaction rate (polymerization rate) than thermal polymerization. For this reason, it is preferable to use a photopolymerization initiator.
The photopolymerization initiator that can be used in the present invention (A) is active with respect to irradiated actinic rays, and has a polymerizable compound contained in the polymerizable layer and a polymerizable group at the terminal or side chain contained in the upper layer. There is no particular limitation as long as it can be polymerized with the hydrophilic compound it has, and for example, a radical polymerization initiator, an anionic polymerization initiator, a cationic polymerization initiator and the like can be used.
[0028]
Specific examples of such a photopolymerization initiator include p-tert-butyltrichloroacetophenone, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one. Benzophenone (4,4'-bisdimethylaminobenzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, ketones; benzoin, benzoin methyl ether, benzoin isopropyl Examples thereof include benzoin ethers such as ether and benzoin isobutyl ether; benzyl ketals such as benzyl dimethyl ketal and hydroxycyclohexyl phenyl ketone, and the like.
The content of the polymerization initiator is preferably in the range of 0.1 to 70% by weight, particularly preferably in the range of 1 to 40% by weight in terms of solid content in the polymerizable layer.
[0029]
The solvent used when applying the polymerizable compound and the polymerization initiator is not particularly limited as long as these components can be dissolved. From the viewpoint of easy drying and workability, a solvent having a boiling point that is not too high is preferable. Specifically, a solvent having a boiling point of about 40 ° C to 150 ° C may be selected.
Specifically, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, methanol, Ethanol, 1-methoxy-2-propanol, 3-methoxypropanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, - such as methoxypropyl acetate.
These solvents can be used alone or in combination. The solid content in the coating solution is suitably 2 to 50% by weight.
[0030]
When the polymerizable layer is formed on the support, the coating amount is 0.1 to 20 g / m by weight after drying.²Is preferable, and further, 1 to 15 g / m.²Is preferred. Application amount 0.1g / m²If it is less than 1, sufficient polymerization initiating ability cannot be exhibited, grafting of the hydrophilic compound becomes insufficient, and there is a concern that the desired hydrophilicity cannot be obtained, and the coating amount is 20 g / m.²If it exceeds 1, the film property tends to be lowered, and film peeling tends to occur.
[0031]
As described above, the polymerizable layer forming composition is disposed on the support surface by coating or the like, and the solvent is removed to form a polymerizable layer to form a polymerizable layer. It is preferable that the film is hardened by light irradiation. In particular, if the film is dried by heating and then preliminarily cured by light irradiation, the polymerizable compound is cured to some extent in advance, so that the polymerizable layer falls off after achieving the grafting of the hydrophilic compound. Such a situation can be effectively suppressed. Here, the reason why light irradiation is used for pre-curing is the same as described in the section of the photopolymerization initiator.
The heating temperature and time may be selected under conditions that allow the coating solvent to be sufficiently dried, but from the viewpoint of production suitability, the temperature is 100 ° C. or less, the drying time is preferably within 30 minutes, It is more preferable to select heating conditions within a drying time of 10 minutes.
[0032]
Light irradiation performed as desired after heat drying can use a light source used for pattern formation to be described later, but the subsequent formation of the hydrophilic pattern and the active point and graft chain of the polymerizable layer performed by energy application From the viewpoint of not inhibiting the formation of a bond with the polymerizable layer, it is preferable to irradiate with light to such an extent that the polymerizable compound present in the polymerizable layer is not partially radically polymerized even if it is partially radically polymerized. Although it varies depending on the intensity of the light source, it is generally preferably within 30 minutes. As a standard for such pre-curing, it can be mentioned that the film remaining rate after solvent washing is 10% or more and the initiator remaining rate after pre-curing is 1% or more.
[0033]
[A-3: Pattern formation]
There is no restriction | limiting in particular in the energy provision method in the case of pattern-forming to the electroconductive pattern material in this invention (A), The energy which produces an active point on the support body surface and can couple | bond with the hydrophilic compound which has a polymeric group is possible. Any method can be used as long as it is capable of imparting actinic acid, but from the viewpoint of cost and simplicity of the apparatus, a method of irradiating actinic rays is preferred.
When actinic light irradiation is applied to image-like exposure, both scanning exposure based on digital data and pattern exposure using a lith film can be used.
Examples of the method used for pattern formation include a method of writing by irradiation of radiation such as heating and exposure, for example, irradiation of light by an infrared laser, ultraviolet lamp, visible light, irradiation of electron beam such as γ-ray, thermal head, etc. It is possible to make a thermal recording. Examples of the light source used here include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp. Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays. Also, g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are used.
As specific embodiments generally used, direct image-like recording with a thermal recording head, scanning exposure with an infrared laser, high-illuminance flash exposure such as a xenon discharge lamp, infrared lamp, ultraviolet lamp exposure, and the like are preferable. .
In order to perform direct pattern formation using digital data of a computer, a method of causing polarity conversion by laser exposure is preferable. Lasers include gas lasers such as carbon dioxide lasers, nitrogen lasers, Ar lasers, He / Ne lasers, He / Cd lasers, Kr lasers, solid state lasers such as liquid (pigment) lasers, ruby lasers, Nd / YAG lasers, GaAs / Semiconductor laser such as GaAlAs, InGaAs laser, KrF laser, XeCl laser, XeF laser, Ar₂An excimer laser or the like can be used. In particular, exposure with a solid-state high-power infrared laser such as a semiconductor laser or a YAG laser that emits infrared light with a wavelength of 700 to 1200 nm is preferable.
[0034]
By applying energy in this manner, the active sites generated on the surface of the support and the hydrophilic compound having a polymerizable group are polymerized to form a surface having a highly mobile hydrophilic graft chain. Further, as a preferred embodiment, a hydrophilic compound having a polymerizable group at at least one of a terminal or a side chain is added in excess, whereby a hydrophilic graft is further added to the side chain polymerizable group of the graft chain bonded to the support. By combining the chains or by connecting multiple graft chains to the active site, a branched graft chain structure is formed, and both the formation density and mobility of hydrophilic grafts with high mobility are dramatically increased. In order to improve, further high hydrophilicity is expressed.
[0035]
Next, (B) a polymer compound-containing layer having a functional group whose hydrophilicity / hydrophobicity is changed by heat, acid or radiation (hereinafter, referred to as a polar conversion group as appropriate) is provided on the support, and heated in an image-like manner. A method of forming a hydrophilic pattern by changing the hydrophilicity / hydrophobicity of the layer by supplying acid or irradiating with radiation will be described.
[B-1: Surface layer having polar conversion group]
The pattern forming layer according to the present invention (B) is also prepared by means generally called surface graft polymerization as in the case of (A). Graft polymerization is a method in which an active species is provided on a polymer compound chain, whereby another monomer that initiates polymerization is further polymerized to synthesize a graft (grafting) polymer. When the compound forms a solid surface, it is called surface graft polymerization.
[0036]
As the surface graft polymerization method for realizing the hydrophilic pattern forming method of the present invention (B), any known method described in the literature can be used. For example, New Polymer Experimental Science 10, edited by Polymer Society, 1994, published by Kyoritsu Shuppan Co., Ltd., P135 describes a photograft polymerization method and a plasma irradiation graft polymerization method as surface graft polymerization methods. In addition, the adsorption technique manual, NTS Co., Ltd., supervised by Takeuchi, 1999.2, p203, p695 describes radiation-induced graft polymerization methods such as γ rays and electron beams.
As a specific method of the photograft polymerization method, methods described in JP-A-10-296895 and JP-A-11-119413 can be used.
[0037]
In addition to these, means for preparing such a surface graft layer include a trialkoxysilyl group, an isocyanate group, an amino group, a hydroxyl group at the terminal and / or side chain of the polymer compound chain having a polar conversion group on one side. It can also be formed by adding a reactive functional group such as a carboxyl group and a coupling reaction between this and a functional group present on the support surface. Further, as a preferred embodiment, by adding an excessive amount of a polymer compound chain having a reactive functional group at at least one of a terminal or a side chain, the reactive group of the side chain of the graft chain bonded to the support is further increased. Both molecular compound chains are combined to form a branched graft chain structure, and reactive functional groups are connected to each other and branched graft chains. Therefore, higher hydrophilicity is manifested.
The support surface in the present invention (B) is a surface having a function of chemically bonding the terminal or side chain of a polymer compound having a polar conversion group directly or via a trunk polymer compound to the surface. The support itself may have such surface characteristics, and a separate intermediate layer may be provided on the support, and the intermediate layer has such characteristics. Also good.
[0038]
In addition, as a means for creating a surface in which the terminal or side chain of a polymer compound chain having a polarity converting group is chemically bonded via a trunk polymer compound, a coupling reaction with a support surface functional group is performed. A functional polymer group is added to the side chain of the trunk polymer compound, and a graft polymer compound incorporating a polymer compound chain having a functional group whose hydrophilicity / hydrophobicity changes as a graft chain is synthesized. It can also form by a coupling reaction.
[0039]
(B-1-1: Functional group whose hydrophilicity / hydrophobicity changes)
Next, a functional group (polarity conversion group) whose hydrophilicity / hydrophobicity is changed by heat, acid or radiation, which is one of the characteristics of the conductive pattern material in the present invention (B), will be described.
There are two types of polar conversion groups: functional groups that change from hydrophobic to hydrophilic and functional groups that change from hydrophilic to hydrophobic.
[0040]
(I) Functional group that changes from hydrophobic to hydrophilic
Examples of functional groups that change from hydrophobic to hydrophilic include known functional groups described in the literature.
Useful examples of these functional groups include alkylsulfonic acid esters, disulfones, sulfonimides described in JP-A No. 10-282672, alkoxyalkyl esters described in EP0652483 and WO92 / 9934, H.P. Ito et al., Macromolecules, vol. 21, pp. Examples thereof include t-butyl ester described in 1477, carboxylic acid ester protected with an acid-decomposable group described in literature such as silyl ester and vinyl ester.
[0041]
Also, Masahiro Tsunooka, “Surface” vol. 133 (1995), pp. 374, an iminosulfonate group described by Masahiro Tsunooka, Polymer preprints, Japan vol. 46 (1997), pp. Examples thereof include β-ketone sulfonate esters described in 2045, nitrobenzyl sulfonate compounds disclosed in Aoyama Yamaoka and JP-A 63-257750, but are not limited to these functional groups.
Of these, the secondary alkylsulfonic acid ester groups shown below, tertiary carboxylic acid ester groups, and alkoxyalkylester groups shown below are particularly excellent.
[0042]
In the present invention (B), the secondary alkylsulfonic acid ester group that is particularly excellent as a functional group that changes from hydrophobicity to hydrophilicity is represented by the following general formula (1).
[0043]
[Chemical 1]

[0044]
(In the general formula (1), L represents an organic group composed of polyvalent non-metallic atoms necessary for linking to the polymer skeleton;¹, R²Represents a substituted or unsubstituted alkyl group. R¹, R²May form a ring with the secondary carbon atom (CH) to which it is attached. )
[0045]
R in the general formula (1)¹, R²Represents a substituted or unsubstituted alkyl, substituted or unsubstituted aryl group, and R¹, R²May form a ring with the secondary carbon atom (CH) to which it is attached. R¹, R²When represents a substituted or unsubstituted alkyl group, examples of the alkyl group include linear, branched or cyclic alkyl groups such as a methyl group, an ethyl group, an isopropyl group, a t-butyl group, and a cyclohexyl group. Those from 1 to 25 are preferably used. R¹, R²When represents a substituted or unsubstituted aryl group, the aryl group includes a carbocyclic aryl group and a heterocyclic aryl group. As the carbocyclic aryl group, those having 6 to 19 carbon atoms such as phenyl group, naphthyl group, anthracenyl group and pyrenyl group are used. In addition, the heterocyclic aryl group includes a pyridyl group, a furyl group, other quinolyl group condensed with a benzene ring, a benzofuryl group, a thioxanthone group, a carbazole group, etc., containing 3 to 20 carbon atoms and 1 to 5 heteroatoms. Is used.
[0046]
R¹, R²Is a substituted alkyl group or a substituted aryl group, examples of the substituent include an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group, a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, and a trifluoromethyl group. A halogen-substituted alkyl group such as a trichloromethyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a t-butyloxycarbonyl group, a p-chlorophenyloxycarbonyl group or the like, or an alkoxycarbonyl group having 2 to 15 carbon atoms or an aryloxycarbonyl group Groups; hydroxyl groups; acyloxy groups such as acetyloxy, benzoyloxy and p-diphenylaminobenzoyloxy; carbonate groups such as t-butyloxycarbonyloxy group; and esters such as t-butyloxycarbonylmethyloxy group and 2-pyranyloxy group Ter group; substituted, unsubstituted amino group such as amino group, dimethylamino group, diphenylamino group, morpholino group and acetylamino group; thioether group such as methylthio group and phenylthio group; alkenyl group such as vinyl group and steryl group; Nitro group; cyano group; acyl group such as formyl group, acetyl group and benzoyl group; aryl group such as phenyl group and naphthyl group; heteroaryl group such as pyridyl group and the like. R¹, R²When is a substituted aryl group, as the substituent, an alkyl group such as a methyl group or an ethyl group can be used in addition to those described above.
[0047]
R above¹, R²Is preferably a substituted or unsubstituted alkyl group from the viewpoint of excellent storage stability of the light-sensitive material. From the viewpoint of stability over time, an electron withdrawing group such as an alkoxy group, a carbonyl group, an alkoxycarbonyl group, a cyano group, or a halogen group. An alkyl group substituted with a functional group, or an alkyl group such as a cyclohexyl group or a norbornyl group is particularly preferred. As a physical property value, a compound in which the chemical shift of secondary methine hydrogen in proton NMR in a deuterated chloroform appears in a magnetic field lower than 4.4 ppm is preferable, and a compound that appears in a magnetic field lower than 4.6 ppm is more preferable. Thus, an alkyl group substituted with an electron-withdrawing group is particularly preferred because the carbocation that appears to be formed as an intermediate during the thermal decomposition reaction is destabilized by the electron-withdrawing group and decomposition is suppressed. This is considered to be because of this. Specifically, -CHR¹R²As the structure, a structure represented by the following formula is particularly preferable.
[0048]
[Chemical 2]

[0049]
In addition, the polyvalent linking group composed of a non-metal atom represented by L in the general formula (1) is 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 It consists of up to 1 oxygen atom, 1 to 100 hydrogen atoms, and 0 to 20 sulfur atoms. More specific examples of the linking group include those formed by combining the following structural units.
[0050]
[Chemical Formula 3]

[0051]
When the polyvalent linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, A hydroxyl group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, an acyloxy group having 1 to 6 carbon atoms such as an acetoxy group, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group, chlorine, Use a halogen atom such as bromine, an alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, or a cyclohexyloxycarbonyl group, a cyano group, or a carbonate group such as t-butyl carbonate. Can do.
[0052]
In the present invention (B), an alkoxyalkyl ester group that is particularly excellent as a functional group that changes from hydrophobic to hydrophilic is represented by the following general formula (2).
[0053]
[Formula 4]

[0054]
  Where R^ThreeRepresents a hydrogen atom and R^FourRepresents a hydrogen atom or an alkyl group having 18 or less carbon atoms, and R^FiveRepresents an alkyl group having 18 or less carbon atoms. R^Three, R^FourAnd R^FiveTwo of theringMay be formed. In particular, R^FourAnd R^FiveAre preferably bonded to form a 5- or 6-membered ring.
[0055]
As described above, the secondary alkylsulfonic acid ester group represented by the general formula (1) is particularly preferable as the functional group changing from hydrophobic to hydrophilic in the present invention (B).
Specific examples of the functional groups [functional groups (1) to (13)] represented by the general formulas (1) to (2) are shown below.
[0056]
[Chemical formula 5]

[0057]
[Chemical 6]

[0058]
(Ii) Functional group that changes from hydrophilic to hydrophobic
In the present invention (B), the functional group that changes from hydrophilic to hydrophobic by heat, acid or radiation is a known functional group such as JP-A-10-296895 and US Pat. No. 6,190,830. And polymers containing onium bases, particularly polymers containing ammonium salts. Specific examples include (meth) acryloyloxyalkyltrimethylammonium. Moreover, although the carboxylic acid group and carboxylic acid group which are shown by the following general formula (3) are mentioned as a suitable thing, it is not specifically limited to these illustrations.
[0059]
[Chemical 7]

[0060]
(Wherein, X represents —O—, —S—, —Se—, —NR)⁸-, -CO-, -SO-, -SO₂-, -PO-, -SiR⁸R⁹-, -CS- represents R⁶, R⁷, R⁸, R⁹Each independently represents a monovalent group, and M represents an ion having a positive charge. )
R⁶, R⁷, R⁸, R⁹Specific examples of -F, -Cl, -Br, -I, -CN, -R^Ten, -OR^Ten, -OCOR^Ten, -OCOOR^Ten, -OCONR^TenR¹¹, -OSO₂R^Ten, -COR^Ten, -COOR^Ten, -CONR^TenR¹⁴, -NR^TenR¹¹, -NR^Ten-COR¹¹, -NR^Ten-COOR¹¹, -NR^Ten-CONR¹¹R¹², -SR^Ten, -SOR^Ten, -SO₂R^Ten, -SO_ThreeR^TenEtc.
R^Ten, R¹¹, R¹²Each represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, or an alkynyl group.
[0061]
Of these, R⁶, R⁷, R⁸, R⁹Specifically, a hydrogen atom, an alkyl group, an aryl group, an alkynyl group, and an alkenyl group are preferable.
Specific examples of M include ions having a positive charge as described above.
Specific examples [functional groups (14) to (31)] of the functional group represented by the general formula (3) are shown below.
[0062]
[Chemical 8]

[0063]
[Chemical 9]

[0064]
The polymer compound having a polarity converting group in the present invention (B) may be a homopolymer of one kind of monomer having the functional group as described above or two or more kinds of copolymers. Moreover, unless the effect of this invention (B) is impaired, the copolymer with another monomer may be sufficient.
In addition, the specific example of the monomer which has the above functional groups is shown below.
(Specific Examples of Monomers Having Functional Groups Represented by General Formulas (1) to (2) [Exemplary Monomers (M-1) to (M-15)])
[0065]
[Chemical Formula 10]

[0066]
Embedded image

[0067]
(Specific Examples of Monomers Having Functional Groups Represented by General Formula (3) [Exemplary Monomers (M-16) to (M-33)])
[0068]
Embedded image

[0069]
Embedded image

[0070]
[B-2: Support]
As the support used in the present invention (B), the same support surface or intermediate layer and support substrate as those used in the hydrophilic pattern forming method (A) can be used. However, in this embodiment, the intermediate layer does not have to have polymerizable initiating ability.
Moreover, in this invention (B), you may perform well-known surface treatments, such as a roughening process and an anodizing process, as needed to the aluminum plate used as a support body.
[0071]
(B-2-1: Photothermal conversion substance)
In the case of recording an image of the conductive pattern material in the present invention (B) with an IR laser or the like, a photothermal conversion substance for converting the light energy into heat energy is contained somewhere in the conductive pattern material. It is preferable to keep. The part to contain the photothermal conversion substance may be, for example, any of a pattern formation layer, an intermediate layer, and a support substrate, and further, a photothermal conversion agent layer is provided between the intermediate layer and the support substrate. You may add to.
[0072]
As the photothermal conversion substance that can be used for the conductive pattern material in the present invention (B), any substance that can be converted into heat by absorbing light such as ultraviolet rays, visible rays, infrared rays, and white rays can be used. Examples thereof include black, carbon graphite, pigment, phthalocyanine pigment, iron powder, graphite powder, iron oxide powder, lead oxide, silver oxide, chromium oxide, iron sulfide, and chromium sulfide. Particularly preferred in the present invention (B) is a dye, pigment or metal fine particle having a maximum absorption wavelength from 760 nm to 1200 nm, which is the exposure wavelength of an infrared laser used for writing.
[0073]
As the dye, commercially available dyes and known dyes described in literature (for example, “Dye Handbook” edited by the Society of Synthetic Organic Chemistry, published in 1970) can be used. Specific examples include azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, and metal thiolate complexes. Preferred dyes include, for example, cyanine dyes described in JP-A-58-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787, and the like. Methine dyes described in JP-A-58-173696, JP-A-58-181690, JP-A-58-194595, JP-A-58-112793, JP-A-58-224793, JP-A-59- 48187, JP-A-59-73996, JP-A-60-52940, JP-A-60-63744, etc., naphthoquinone dyes, JP-A-58-112792, etc. And cyanine dyes described in British Patent 434,875.
[0074]
Further, near infrared absorption sensitizers described in US Pat. No. 5,156,938 are also preferably used, and substituted arylbenzo (thio) pyrylium salts described in US Pat. Trimethine thiapyrylium salts described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A Nos. 58-181051, 58-220143, 59-41363, 59-84248, Pyryllium compounds described in JP-A-59-84249, JP-A-59-146063, JP-A-59-146061, cyanine dyes described in JP-A-59-216146, and U.S. Pat. No. 4,283,475 A pentamethine thiopyrylium salt or the like, or a pyrylium compound disclosed in Japanese Patent Publication Nos. 5-13514 and 5-19702 are also preferably used.Examples of other preferable dyes include near infrared absorbing dyes described as formulas (I) and (II) in US Pat. No. 4,756,993. Among these dyes, particularly preferred are cyanine dyes, squarylium dyes, pyrylium salts, and nickel thiolate complexes.
[0075]
Examples of the pigment used in the present invention (B) include commercially available pigments and color index (CI) manuals, “Latest Pigment Handbook” (edited by the Japan Pigment Technical Association, published in 1977), “Latest Pigment Applied Technology” ( CMC Publishing, published in 1986), “Printing Ink Technology”, published by CMC Publishing, published in 1984) can be used. Examples of the pigment include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and other polymer-bonded dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments In addition, quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like can be used. Among these pigments, carbon black is preferable.
[0076]
These dyes or pigments are 0.01 to 50% by weight, preferably 0.1 to 10% by weight of the total solid content of the photothermal conversion substance-containing layer, particularly preferably 0.5 to 10% by weight in the case of dyes. In this case, it can be particularly preferably used in a proportion of 3.1 to 10% by weight. When the added amount of the pigment or dye is less than 0.01% by weight, the sensitivity is low, and when it exceeds 50% by weight, the film strength of the photothermal conversion substance-containing layer is weakened.
[0077]
[B-3: Pattern formation]
In the pattern formation mechanism of the present invention (B), as in the above (i), in the polymer compound layer using the functional group that changes from hydrophobic to hydrophilic, the portion whose polarity has been changed by heating, acid or radiation irradiation is not present. By becoming a hydrophilic region and adsorbing the conductive polymer in this region, the region becomes a conductive region, and wiring is formed.
On the other hand, as described in (ii) above, in a polymer compound layer using a functional group that changes from hydrophilic to hydrophobic, the layer originally has a hydrophilic surface and is polar in heating, acid or radiation irradiation. The converted part becomes hydrophobic. In this case, since the conductive polymer is adsorbed only on the unexposed portions, a conductive pattern material suitable for forming a single circuit, forming a wide area conductive region, and the like can be obtained.
Moreover, the same thing as what was used by the said hydrophilic pattern formation method (A) can be used for the energy provision method in the case of patterning to the electroconductive pattern material in this invention (B).
[0078]
[Formation of conductive polymer layer]
The conductive pattern material of the present invention has a conductive polymer layer formed by adsorbing a conductive polymer on the hydrophilic functional group of the hydrophilic polymer on a support. This conductive polymer layer has conductivity.
The conductive polymer used in the present invention is 10^-6s · cm^-1Or more, preferably 10^-1s · cm^-1Any of the above-described polymer compounds having conductivity can be used. Specifically, for example, substituted and unsubstituted conductive polyaniline, polyparaphenylene, polyparaphenylene vinylene, and polythiophene. , Polyfuran, polypyrrole, polyselenophene, polyisothianaphthene, polyphenylene sulfide, polyacetylene, polypyridylvinylene, polyazine and the like. These may use only 1 type and may use it in combination of 2 or more type according to the objective. Moreover, as long as desired conductivity can be achieved, it can be used as a mixture with other polymers having no conductivity, or a copolymer of these monomers and other monomers without conductivity can be used. be able to.
[0079]
Although there is no restriction | limiting in particular in the method of forming a conductive polymer layer using such a conductive polymer, From the viewpoint that a uniform thin film can be formed, the monomer which has the following conductivity is used. The method is preferred.
First, the support having a hydrophilic surface in which the hydrophilic graft polymer chain is present is immersed in a solution containing a polymerization catalyst such as potassium persulfate or iron (III) sulfate or a compound having a polymerization initiating ability. While stirring the liquid, a monomer capable of forming a conductive polymer, such as 3,4-ethylenedioxythiophene, is gradually added dropwise. In this way, the hydrophilic functional group of the graft polymer chain and the monomer capable of forming the conductive polymer are strongly adsorbed by the interaction, the polymerization reaction between the monomers proceeds, and the hydrophilic graft polymer chain exists. A very thin film of conductive polymer is formed on the hydrophilic surface to become a conductive polymer layer.
Since the conductive polymer layer formed in this way is formed by a polymerization reaction on the hydrophilic surface, a very thin film can be formed by adjusting conditions such as the monomer supply rate, Furthermore, even a thin film has the advantages of being uniform and having a uniform film thickness.
[0080]
If the polymerization reaction on the surface of the support is used, for example, a conductive polymer thin film can be formed directly on the surface of the support such as a resin such as PET, but an interaction with such a support can be formed. Such a film is easily peeled off, and it is impossible to form a thin film having a level of film strength that does not cause any practical problems.
[0081]
In the present invention, the conductive monomer itself is strongly adsorbed by forming an electrostatically or polar interaction with the hydrophilic group of the graft polymer chain, so that they are polymerized to form a polymer film Since a strong interaction is formed with the hydrophilic surface, even a thin film has sufficient strength against rubbing and scratching.
Furthermore, by selecting a material that allows the conductive polymer and the hydrophilic functional group to adsorb in a cation-anion relationship, the hydrophilic functional group can be adsorbed as the counter anion of the conductive polymer. Thus, since it functions as a kind of dopant, it is possible to obtain an effect that the conductivity of the conductive pattern material can be further improved. Specifically, for example, when styrene sulfonic acid is selected as the hydrophilic group and thiophene is selected as the material of the conductive polymer, the interaction between the two causes sulfone as a counter anion at the interface between the hydrophilic surface and the conductive polymer layer. There exists a polythiophene having an acid group (sulfo group), which functions as a conductive polymer dopant.
[0082]
Although there is no restriction | limiting in particular in the film thickness of the conductive polymer layer formed in the hydrophilic pattern material surface, It is preferable that it is the range of 0.01 micrometer-10 micrometers, and it is more preferable that it is the range of 0.1 micrometer-5 micrometers. . If the film thickness of the conductive polymer layer is within this range, sufficient conductivity and transparency can be achieved. If the thickness is 0.01 μm or less, there is a concern that the conductivity may be insufficient.
[0083]
The conductive pattern material of the present invention patterned by the above method can be used for various circuit formation, and a nanoscale conductive region can be formed by selecting a pattern forming means. Wide applications including circuit formation such as VLSI are expected.
Furthermore, when a transparent film such as PET is used for the support, it can be used as a patterned transparent conductive film. Applications of such transparent conductive films include transparent electrodes for displays, light control devices, solar cells, touch panels, and other transparent conductive films, but are particularly useful as electromagnetic wave shielding filters for CRTs and plasma displays. . Since such an electromagnetic wave shielding filter requires high conductivity and transparency, it is preferable to provide a conductive polymer layer in a lattice shape. Such a lattice line width is preferably about 20 to 100 μm, and the opening is preferably about 50 to 600 μm. This lattice does not necessarily have to be regular and configured with straight lines, and may be configured with curved lines. In the present invention, since the conductive polymer layer having such an arbitrary pattern shape can be easily formed, various settings according to the purpose are possible.
[0084]
【Example】
  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
[Reference example1]
(Creation of hydrophilic pattern)
  A 188 μm corona-treated biaxially stretched polyethylene terephthalate film (A4100, manufactured by Toyobo Co., Ltd.) was used, and a lithographic magnetron sputtering apparatus (CFS-10-EP70, manufactured by Shibaura Eletech Co., Ltd.) was used as the glow treatment. Glow treatment was performed.
  Initial vacuum: 1.2 × 10^-3Pa
  Oxygen pressure: 0.9 Pa
  RF glow: 1.5 kW
  Processing time: 60 sec
[0085]
Next, acrylic acid was applied onto the glow-treated film using a rod bar # 6, and the coated surface was laminated with a 25 μm PET film. Next, the mask pattern which vapor-deposited chromium was piled up on this, and UV light was irradiated from the top (400W high pressure mercury lamp: UVL-400P, Riko Kagaku Sangyo Co., Ltd. irradiation time 30 seconds). After the light irradiation, the mask and the laminate film were removed and washed with water to obtain a hydrophilic pattern 1 in which polyacrylic acid was grafted in a pattern.
[0086]
(Formation of conductive polymer layer)
  The support having the hydrophilic pattern 1 was prepared by adding 1.23 g of sodium anthraquinone-2-sulfonate monohydrate, 7.20 g of sodium 5-sulfosalicylic acid hydrate, and iron trichloride-6 4.38 g of hydrate was immersed in a solution of 125 ml of water, and a solution of 0.75 ml of pyrrole and 125 ml of water was added with stirring. After one hour, the support was taken out, washed with water, and then washed with acetone to form a polypyrrole layer, which is a conductive polymer, on the surface of the support.Reference example1 conductive pattern material 1 was obtained.
[0087]
[Evaluation of conductive pattern material]
1. Conductivity
The surface resistance value of the obtained conductive pattern material 1 was measured by a four-point probe method using LORESTA-FP (manufactured by Mitsubishi Chemical Corporation). The surface resistance value was 1000Ω / □. It is evaluated that the lower the surface resistance value, the better the conductivity.
2. Pencil hardness
The film strength of the surface of the obtained conductive pattern material 1 was measured according to the method described in JIS G0202. The pencil hardness was 4H or higher. It is evaluated that the higher the pencil hardness used in the test, that is, the higher the numerical value of H, such as 1H → 4H, the better the strength.
[0088]
[Reference example 2]
(Creation of hydrophilic pattern)
  On the same polyethylene terephthalate film as used in Example 1, the following composition for forming a layer (polymerizable layer) that expresses the polymerization initiating ability was applied using rod bar # 17, and 2 at 80 ° C. Let dry for minutes. Next, the coated film was irradiated with UV light from the top (irradiation time of 400 w high-pressure mercury lamp for 10 minutes) to be precured.
  ・ Allyl methacrylate / methacrylic acid copolymer 4g
                      (Molar ratio 80/20, molecular weight 100,000)
  ・ Ethylene oxide modified bisphenol A diacrylate 4g
                                (Toagosei Co., Ltd. M210)
  ・ 1.6g of 1-hydroxycyclohexyl phenyl ketone
  ・ 16 g of 1-methoxy-2-propanol
[0089]
Next, an aqueous solution (30 wt%) of sodium styrenesulfonate was applied onto the surface of the support using a rod bar # 12, and the coated surface was laminated with a 25 μm PET film without drying. Next, the mask pattern which vapor-deposited chromium was piled up on this, and UV light was irradiated from the top (400W high pressure mercury lamp irradiation time 10 minutes). After the light irradiation, the mask and the laminate film were removed and washed with water to obtain a hydrophilic pattern 2 in which sodium polystyrene sulfonate was grafted in a pattern.
[0090]
(Formation of conductive polymer layer)
  The support having the hydrophilic pattern 2 was immersed in 2000 ml of a solution in which 13.0 g of potassium persulfate and 50 mg of iron (III) sulfate were dissolved. Next, 5.5 g of 3,4-ethylenedioxythiophene was gradually added dropwise while stirring this solution. The solution was stirred at room temperature for 10 hours. A polythiophene layer, which is a conductive polymer, was formed on the surface of the support by removing the support and washing with water.Reference example 2The conductive pattern material 2 was obtained.
[0091]
[Evaluation of conductive pattern material]
1. Conductivity
The surface resistance value of the obtained conductive pattern material 2 was measured by the four-probe method using LORESTA-FP (manufactured by Mitsubishi Chemical Corporation). The surface resistance value was 1300Ω / □, and it was found that the material had conductivity suitable for practical use.
2. Pencil hardness
The film strength of the surface of the obtained conductive pattern material 2 was measured according to the method described in JIS G0202. It was found that the pencil hardness was 4H or more and the strength was excellent.
[0092]
〔Example1]
(Formation of hydrophilic pattern)
  Reference example1. Apply the following intermediate layer forming coating solution on the same polyethylene terephthalate film as used in 1 using rod bar # 10, and dry at 100 ° C. for 1 minute to obtain an infrared absorber having a film pressure of 1.6 μm. An intermediate layer was prepared.
  ・ Epoxy resin (Epicoat, Yuka-shell Co, Ltd.) 2 g
  ・ Infrared absorber (IR125 Wako Pure Chemicals) 0.2g
  ・ 9 g of 1-methoxy-2-propanol
  ・ Methyl ethyl ketone 9 g
[0093]
The surface of the support on which the intermediate layer was formed was subjected to plasma treatment under the following conditions to form a pattern forming layer by surface graft polymerization.
Using a LCVD-01 type plasma processing apparatus manufactured by Shimadzu Corporation, the substrate was treated for 10 seconds in an argon gas atmosphere of 0.04 toor and then exposed to air to introduce peroxide groups on the surface of the intermediate layer. This film was immersed in 10 wt% α (styrene-4-sulfonyl) acetic acid Na salt aqueous solution, bubbled with argon gas for 15 minutes, and then heated to 60 ° C. for 7 hours for graft polymerization. After the graft polymerization, the membrane was placed in 3000 ml of ion-exchanged water, and a homopolymer other than the graft polymerization was removed to obtain a conductive pattern forming material 3 having a pattern forming layer grafted on the surface by plasma treatment.
The obtained conductive pattern forming material 3 was exposed imagewise with an infrared laser (beam diameter 20 μm) emitting infrared light having a wavelength of 830 nm.
[0094]
(Formation of conductive polymer layer)
  Reference exampleIn the same manner as in Example 1, a polypyrrole layer, which is a conductive polymer, is formed on a support.1The conductive pattern material 3 was obtained.
[0095]
[Evaluation of conductive pattern material]
1. Conductivity
The surface resistance value of the obtained conductive pattern material 3 was measured by a four-probe method using LORESTA-FP (manufactured by Mitsubishi Chemical Corporation). The surface resistance value was 1000Ω / □, and it was found that the material had conductivity suitable for practical use.
2. Pencil hardness
The film strength of the surface of the obtained conductive pattern material 3 was measured according to the method described in JIS G0202. It was found that the pencil hardness was 4H or more and the strength was excellent.
[0096]
【The invention's effect】
The conductive pattern material of the present invention is strong and excellent in durability, and can form a fine pattern without disconnection with high resolution by laser exposure based on digital data. An excellent conductive pattern can be formed from the viewpoints of property and manufacturing suitability.

Claims (5)

  A polymer compound having a functional group whose hydrophilicity / hydrophobicity is changed by heat, acid or radiation and a functional group capable of coupling reaction with the support surface functional group is brought into contact with the support surface and coupled on the support surface. A polymer compound-containing layer having a functional group that has a graft chain structure that is directly bonded to the support surface and has a hydrophilicity / hydrophobicity change by heat, acid, or radiation is provided, and image-wise heating, acid supply, or After forming a hydrophilic pattern by irradiating radiation and changing the hydrophilicity / hydrophobicity of the polymer-containing layer, the conductive monomer is adsorbed on the hydrophilic pattern, and the polymerization reaction of the conductive monomer A conductive pattern material comprising a formed conductive polymer layer. The heat, acid or functional group that hydrophilicity or hydrophobicity is changed by radiation is conductive pattern material according to claim 1, characterized by having a partial structure represented by the following general formula (1) to (3).

(In the general formula (1), L represents an organic group composed of a polyvalent nonmetallic atom necessary for linking to the polymer skeleton, and R ¹ and R ² represent a substituted or unsubstituted alkyl group. R ¹ and R ² may form a ring together with the secondary carbon atom (CH) to which R ¹ and R ² are bonded.

(Formula (2) Medium R ³ represents a hydrogen atom, R ⁴ represents a hydrogen atom or an alkyl group having 18 or less carbon, R ⁵ represents an alkyl group having not more than 18 carbon atoms. Also, R ³ , R ⁴ and R ⁵ may combine to form a ring.)

(In the general formula (3), X represents —O—, —S—, —Se—, —NR ⁸ —, —CO—, —SO—, —SO ₂ —, —PO—, —SiR ⁸ R ⁹ —. , -CS-, R ⁶ , R ⁷ , R ⁸ , and R ⁹ each independently represent a monovalent group, and M represents a positively charged ion.) The heat, the polymer-containing layer having a functional group that hydrophilicity or hydrophobicity is changed by an acid or radiation, further, a conductive pattern material according to claim 1, characterized in that it contains a photothermal conversion agent. A polymer compound having a functional group whose hydrophilicity / hydrophobicity is changed by heat, acid or radiation and a functional group capable of coupling reaction with the support surface functional group is brought into contact with the support surface and coupled on the support surface. Forms a polymer compound-containing layer that has a graft chain structure that is directly bonded to the surface of the support and has a functional group whose hydrophilicity / hydrophobicity changes by heat, acid, or radiation. Or irradiation with radiation to change the hydrophilicity / hydrophobicity of the layer, thereby forming a hydrophilic pattern having a graft chain structure directly bonded to the support surface;
Adsorbing a conductive monomer on the hydrophilic pattern and polymerizing the conductive monomer to form a conductive polymer layer;
A method for forming a conductive pattern, comprising: The step of adsorbing a conductive monomer on the hydrophilic pattern and polymerizing the conductive monomer to form a conductive polymer layer has a polymerization catalyst or a polymerization initiating ability for the support having the hydrophilic pattern. The method for forming a conductive pattern according to claim 4, comprising a step of immersing in a solution containing the compound and dropping the conductive monomer while stirring the solution.