JP4300012B2 - Multilayer wiring board - Google Patents

Description

【００７２】
ただし、ｎは２以上の整数であり、Ｒ^１，Ｒ^２はそれぞれ炭素数１〜１０の置換もしくは非置換のアルキル、アルケニル、アリールあるいはシアノアルキル基であり、モル比で全体の４０％以下がビニル、フェニル、ハロゲン化フェニルである。また、Ｒ^１、Ｒ^２がメチル基のものが表面エネルギーが最も小さくなるので好ましく、モル比でメチル基が６０％以上であることが好ましい。また、鎖末端もしくは側鎖には、分子鎖中に少なくとも１個以上の水酸基等の反応性基を有する。
【００７３】
また、上記のオルガノポリシロキサンとともに、ジメチルポリシロキサンのような架橋反応をしない安定なオルガノシリコン化合物をバインダに混合してもよい。
【００７４】
ｃ．分解物質
上記第２の形態および第３の形態においては、さらにエネルギー照射による光触媒の作用により分解され、これにより光触媒濡れ性変化層上の濡れ性を変化させることができる分解物質を光触媒濡れ性変化層に含有させる必要がある。すなわち、バインダ自体に光触媒濡れ性変化層上の濡れ性を変化させる機能が無い場合、およびそのような機能が不足している場合に、上述したような分解物質を添加して、上記光触媒濡れ性変化層上の濡れ性の変化を起こさせる、もしくはそのような変化を補助させるようにするのである。
【００７５】
このような分解物質としては、光触媒の作用により分解し、かつ分解されることにより光触媒濡れ性変化層表面の濡れ性を変化させる機能を有する界面活性剤を挙げることができる。具体的には、日光ケミカルズ（株）製ＮＩＫＫＯＬ ＢＬ、ＢＣ、ＢＯ、ＢＢの各シリーズ等の炭化水素系、デュポン社製ＺＯＮＹＬ ＦＳＮ、ＦＳＯ、旭硝子（株）製サーフロンＳ−１４１、１４５、大日本インキ化学工業（株）製メガファックＦ−１４１、１４４、ネオス（株）製フタージェントＦ−２００、Ｆ２５１、ダイキン工業（株）製ユニダインＤＳ−４０１、４０２、スリーエム（株）製フロラードＦＣ−１７０、１７６等のフッ素系あるいはシリコーン系の非イオン界面活性剤を挙げることができ、また、カチオン系界面活性剤、アニオン系界面活性剤、両性界面活性剤を用いることもできる。
【００７６】
また、界面活性剤の他にも、ポリビニルアルコール、不飽和ポリエステル、アクリル樹脂、ポリエチレン、ジアリルフタレート、エチレンプロピレンジエンモノマー、エポキシ樹脂、フェノール樹脂、ポリウレタン、メラミン樹脂、ポリカーボネート、ポリ塩化ビニル、ポリアミド、ポリイミド、スチレンブタジエンゴム、クロロプレンゴム、ポリプロピレン、ポリブチレン、ポリスチレン、ポリ酢酸ビニル、ナイロン、ポリエステル、ポリブタジエン、ポリベンズイミダゾール、ポリアクリルニトリル、エピクロルヒドリン、ポリサルファイド、ポリイソプレン等のオリゴマー、ポリマー等を挙げることができる。
【００７７】
ｄ．フッ素の含有
また、本態様においては、光触媒濡れ性変化層がフッ素を含有し、さらにこの光触媒濡れ性変化層表面のフッ素含有量が、光触媒濡れ性変化層に対しエネルギーを照射した際に、上記光触媒の作用によりエネルギー照射前に比較して低下するように上記光触媒濡れ性変化層が形成されていることが好ましい。
【００７８】
このような特徴を有する光触媒濡れ性変化層であれば、エネルギーをパターン照射することにより、後述するように容易にフッ素の含有量の少ない部分からなるパターンを形成することができる。ここで、フッ素は極めて低い表面エネルギーを有するものであり、このためフッ素を多く含有する物質の表面は、臨界表面張力がより小さくなる。したがって、フッ素の含有量の多い部分の表面の臨界表面張力に比較してフッ素の含有量の少ない部分の臨界表面張力は大きくなる。これはすなわち、フッ素含有量の少ない部分はフッ素含有量の多い部分に比較して親液性領域となっていることを意味する。よって、周囲の表面に比較してフッ素含有量の少ない部分からなるパターンを形成することは、撥液性域内に親液性領域のパターンを形成することとなる。
【００７９】
したがって、このような光触媒濡れ性変化層を用いた場合は、エネルギーをパターン照射することにより、撥液性領域内に親液性領域のパターンを容易に形成することができるので、例えばインクジェット法等により、導電性パターン組成物を塗布した場合に、高精細な導電性パターンを形成することが可能となるからである。
【００８０】
上述したような、フッ素を含む光触媒濡れ性変化層中に含まれるフッ素の含有量としては、エネルギーが照射されて形成されたフッ素含有量が低い親液性領域におけるフッ素含有量が、エネルギー照射されていない部分のフッ素含有量を１００とした場合に１０以下、好ましくは５以下、特に好ましくは１以下であることが好ましい。
【００８１】
このような範囲内とすることにより、エネルギー照射部分と未照射部分との親液性に大きな違いを生じさせることができる。したがって、このような光触媒濡れ性変化層に、例えば導電性パターン組成物を付着させることにより、フッ素含有量が低下した親液性領域のみに正確に導電性パターンを形成することが可能となり、精度の良い配線基板を得ることができるからである。なお、この低下率は重量を基準としたものである。
【００８２】
このような光触媒濡れ性変化層中のフッ素含有量の測定は、一般的に行われている種々の方法を用いることが可能であり、例えばＸ線光電子分光法（X-ray Photoelectron Spectroscopy, ESCA(Electron Spectroscopy for Chemical Analysis)とも称される。）、蛍光Ｘ線分析法、質量分析法等の定量的に表面のフッ素の量を測定できる方法であれば特に限定されるものではない。
【００８３】
また、本態様においては、光触媒として上述したように二酸化チタンが好適に用いられるが、このように二酸化チタンを用いた場合の、光触媒濡れ性変化層中に含まれるフッ素の含有量としては、Ｘ線光電子分光法で分析して定量化すると、チタン（Ｔｉ）元素を１００とした場合に、フッ素（Ｆ）元素が５００以上、このましくは８００以上、特に好ましくは１２００以上となる比率でフッ素（Ｆ）元素が光触媒濡れ性変化層表面に含まれていることが好ましい。
【００８４】
フッ素（Ｆ）が光触媒濡れ性変化層にこの程度含まれることにより、光触媒濡れ性変化層上における臨界表面張力を十分低くすることが可能となることから表面における撥液性を確保でき、これによりエネルギーをパターン照射してフッ素含有量を減少させたパターン部分における表面の親液性領域との濡れ性の差異を大きくすることができ、最終的に得られる配線基板の精度を向上させることができるからである。
【００８５】
さらに、このような配線基板においては、エネルギーをパターン照射して形成される親インク領域におけるフッ素含有量が、チタン（Ｔｉ）元素を１００とした場合にフッ素（Ｆ）元素が５０以下、好ましくは２０以下、特に好ましくは１０以下となる比率で含まれていることが好ましい。
【００８６】
光触媒濡れ性変化層中のフッ素の含有率をこの程度低減することができれば、配線基板を形成するためには十分な親液性を得ることができ、上記エネルギーが未照射である部分の撥液性との濡れ性の差異により、配線基板を精度良く形成することが可能となり、利用価値の高い多層配線基板を得ることができる。
【００８７】
ｅ．光触媒濡れ性変化層の製造方法
上述したようにオルガノポリシロキサンをバインダとして用いた場合は、上記光触媒濡れ性変化層は、光触媒とバインダであるオルガノポリシロキサンとを必要に応じて他の添加剤とともに溶剤中に分散して塗布液を調製し、この塗布液を基材上に塗布することにより形成することができる。使用する溶剤としては、エタノール、イソプロパノール等のアルコール系の有機溶剤が好ましい。塗布はスピンコート、スプレーコート、ディッブコート、ロールコート、ビードコート等の公知の塗布方法により行うことができる。バインダとして紫外線硬化型の成分を含有している場合、紫外線を照射して硬化処理を行うことにより、光触媒濡れ性変化層を形成することができる。
【００８８】
（２）第二の態様
次に、本実施態様の特性変化層における第二の態様について説明する。本態様における特性変化層は、エネルギー照射に伴う光触媒の作用により、密着性が変化する層であり、かつ少なくとも光触媒およびバインダを含有する光触媒密着性変化層である場合である。
【００８９】
本態様に用いられる光触媒密着性変化層は、エネルギー照射に伴い、光触媒密着性変化層自体に含有される光触媒の作用により、密着性が変化する層であり、かつ少なくとも光触媒およびバインダを含有する層であれば特に限定されるものではないが、その光触媒密着性変化層表面における物との密着性が向上するように密着性が変化する層であることが好ましい。
【００９０】
このように、エネルギー照射により物との密着性が向上するように密着性が変化する光触媒密着性変化層とすることにより、エネルギーが照射された部分を密着性良好領域、エネルギーが照射されていない部分を密着阻害領域とすることが可能となるのである。この密着性の差を利用して、例えば、全面に導電性パターンを形成する導電性パターン組成物を蒸着した場合に、密着性良好領域のみに導電性パターン組成物が密着し、密着阻害領域には導電性パターン組成物が密着しないことから、密着阻害領域における導電性パターン組成物を容易に除去することが可能となり、後述する導電性パターンを密着性領域のみに容易に形成することが可能となるのである。
【００９１】
ここで、密着性良好領域とは、物との密着性が良好な領域であり、後述する導電性パターンを形成する導電性パターン組成物に対する密着性の良好な領域をいうこととする。また、密着阻害領域とは、物との密着性が悪い領域であり、導電性パターン組成物に対する密着性が悪い領域をいうこととする。
【００９２】
本実施態様における光触媒密着性変化層は、密着性阻害物質を含有し、エネルギー照射に伴う光触媒の作用により、密着性阻害物質が除去される層である場合（第一の形態）と、エネルギー照射に伴う光触媒の作用により光触媒密着性変化層上に凹凸が形成され、物理的に密着性が向上する場合（第二の形態）とがある。以下、それぞれの形態についてわけて説明する。
【００９３】
まず、第一の形態について説明する。本形態の光触媒密着性変化層は、密着性を阻害する物質が含有されており、この密着性阻害物質により、エネルギー照射されていない密着阻害領域においては、例えば蒸着法等により塗布された導電性パターン組成物が密着することを阻害することが可能である。また、エネルギー照射に伴う光触媒の作用により、この密着性阻害物質が除去されることによって密着性が向上し、密着性良好領域を形成することが可能となるのである。
【００９４】
この光触媒密着性変化層の第一の形態として具体的には、光触媒およびバインダ等、上述した第一の態様の光触媒濡れ性変化層の項で説明したものと同様のものを用いることが可能である。
【００９５】
次に、第二の形態について説明する。本形態の光触媒密着性変化層は、エネルギー照射に伴う光触媒の作用により、表面に凹凸が形成される層であり、この表面の凹凸によるアンカー効果により導電性パターン組成物の密着性を向上させることが可能となるのである。また、エネルギー照射されていない密着阻害領域においては、凹凸が形成されていないことから、導電性パターン組成物が密着することが困難であり、この密着性の差を利用して、特性変化パターンを容易に形成することが可能となるのである。
【００９６】
この光触媒密着性変化層の第二の態様に用として具体的には、ポリエチレンテレフタレート、ポリビニルアルコール、ポリカーボネート、メチルメタクリレート単重合体または共重合体、ポリスチレン、ポリエチレン、ポリプロピレン、ポリエステル、ＰＴＦＥ等を用いることが可能である。
【００９７】
（３）第三の態様
次に、本実施態様の特性変化層における第三の態様について説明する。本態様の特性変化層は、少なくとも光触媒を含有する光触媒処理層と、上記光触媒処理層上に形成されたエネルギー照射に伴う光触媒の作用により液体との接触角が低下する層である濡れ性変化層とからなる層である。
【００９８】
本態様において、特性変化層が上記光触媒処理層と上記濡れ性変化層とから構成されることにより、エネルギー照射に伴い、上記光触媒処理層中の光触媒が活性化され、その光触媒処理層上に形成された上記濡れ性変化層表面の濡れ性を変化させるのである。以下、この濡れ性変化層および光触媒処理層について説明する。
【００９９】
ａ．光触媒処理層
本態様に用いられる光触媒処理層は、少なくとも光触媒を含有するものであり、光触媒処理層がバインダを有する場合は、上記第一の態様で説明した光触媒処理層と同様であるので、ここでの説明は省略する。ただし、本態様においては、光触媒処理層上の濡れ性は特に変化する必要がないことから、バインダ自体に光触媒が作用することによる濡れ性の変化が生じない場合であっても、第一の態様のように分解物質を光触媒処理層に含有させる必要がない。また、バインダを有する場合の光触媒処理層の製造方法は、上述した第一の態様と同様であるので、これについての説明も省略する。
【０１００】
一方、バインダを有さない場合の光触媒処理層の形成方法としては、例えば、スパッタリング法、ＣＶＤ法、真空蒸着法等の真空製膜法を用いる方法を挙げることができる。真空製膜法により光触媒処理層を形成することにより、均一な膜でかつ光触媒のみを含有する光触媒処理層とすることが可能であり、これにより濡れ性変化層上の濡れ性を均一に変化させることが可能であり、かつ光触媒のみからなることから、バインダを用いる場合と比較して効率的に濡れ性変化層上の濡れ性を変化させることが可能となる。
【０１０１】
また、光触媒のみからなる光触媒処理層の他の形成方法としては、例えば光触媒が二酸化チタンの場合は、基材上に無定形チタニアを形成し、次いで焼成により結晶性チタニアに相変化させる方法等が挙げられる。ここで用いられる無定形チタニアとしては、例えば四塩化チタン、硫酸チタン等のチタンの無機塩の加水分解、脱水縮合、テトラエトキシチタン、テトライソプロポキシチタン、テトラ−ｎ−プロポキシチタン、テトラブトキシチタン、テトラメトキシチタン等の有機チタン化合物を酸存在下において加水分解、脱水縮合によって得ることができる。次いで、４００℃〜５００℃における焼成によってアナターゼ型チタニアに変性し、６００℃〜７００℃の焼成によってルチル型チタニアに変性することができる。
【０１０２】
ｂ．濡れ性変化層
次に、本態様に用いられる濡れ性変化層について説明する。
【０１０３】
本態様に用いられる濡れ性変化層は、エネルギー照射に伴う光触媒の作用により、液体との接触角が低下するような層であれば、特に限定されるものではないが、中でも、エネルギー照射していない部分、すなわち撥液性領域においては、４０ｍＮ／ｍの液体との接触角が、１０°以上、好ましくは表面張力３０ｍＮ／ｍの液体との接触角が１０°以上、特に表面張力２０ｍＮ／ｍの液体との接触角が１０°以上であることが好ましい。これは、エネルギー照射していない部分が撥液性が要求される部分であることから、上記液体との接触角が小さい場合は、撥液性が十分でなく、後述する導電性パターンを例えば、導電性パターン組成物をインクジェット方式等により塗布し、硬化させて形成する場合等に、撥液性領域にも導電性パターン組成物が付着する可能性があることから、高精細に導電性パターンを形成することが困難となるからである。
【０１０４】
また、上記濡れ性変化層は、エネルギー照射された部分、すなわち親液性領域においては、４０ｍＮ／ｍの液体との接触角が９°未満、好ましくは表面張力５０ｍＮ／ｍの液体との接触角が１０°以下、特に表面張力６０ｍＮ／ｍの液体との接触角が１０°以下となるような層であることが好ましい。エネルギー照射された部分、すなわち親液性領域における液体との接触角が高い場合は、例えば導電性パターンを形成する導電性パターン組成物を、親液性領域においてもはじいてしまう可能性があり、例えばインクジェット法により導電性パターン組成物を塗布した際に、導電性パターン組成物が十分に塗れ広がらず、導電性パターンを形成することが難しくなる可能性があるからである。
【０１０５】
なお、ここでいう液体との接触角は、第一の態様において説明した方法と同様に測定した値である。
【０１０６】
この濡れ性変化層は、上記光触媒処理層の作用により濡れ性が変化する層であれば特に限定されるものではないが、上述した第一の態様の光触媒処理層中のバインダと同様の材料で形成することが好ましい。なお、このように上記第一の態様の光触媒処理層中のバインダと同様の材料で形成した場合の濡れ性変化層の材料および形成方法に関しては、上記第一の態様と同様であるので、ここでの説明は省略する。
【０１０７】
本態様において、この濡れ性変化層の厚みは、光触媒による濡れ性の変化速度等の関係より、０．００１μｍから１μｍであることが好ましく、特に好ましくは０．０１〜０．１μｍの範囲内である。
【０１０８】
本態様において上述した成分の濡れ性変化層を用いることにより、隣接する光触媒処理層中の光触媒の作用により、上記成分の一部である有機基や添加剤の酸化、分解等の作用を用いて、エネルギー照射部分の濡れ性を変化させて親液性とし、エネルギー未照射部との濡れ性に大きな差を生じさせることができる。
【０１０９】
なお、この濡れ性変化層には、上記第一の態様における光触媒処理層の説明中「フッ素の含有」の項で記載したものと同様にして同様のフッ素を含有させることができる。
【０１１０】
なお、本態様においては、濡れ性変化層中に光触媒を含有する必要がなく、この場合には、経時的に導電性パターンが光触媒の影響を受ける可能性を少なくすることが可能である。
【０１１１】
（４）第四の態様
次に、本実施態様における特性変化層の第四の態様について説明する。本態様における特性変化層は、少なくとも光触媒を含有する光触媒処理層と、上記光触媒処理層上に形成された光触媒の作用により密着性が変化する密着性変化層とからなる層である。
【０１１２】
本態様によれば、上記特性変化層が、上記光触媒処理層および上記密着性変化層により構成されることにより、エネルギー照射に伴い、上記光触媒処理層中の光触媒が励起され、これにより上記密着性変化層の密着性が変化するのである。
【０１１３】
なお、本態様に用いられる光触媒処理層については、上述した第三の態様における光触媒処理層と同様であるので、ここでの説明は省略し、密着性変化層について以下説明する。
【０１１４】
本態様に用いられる密着性変化層は、上記光触媒処理層の作用により密着性が変化する層であれば特に限定されるものではないが、中でもエネルギー照射に伴う光触媒の作用により密着性が向上する層であることが好ましい。この密着性変化層としては、上述した第二の態様の光触媒密着性変化層中のバインダと同様の材料で形成することが好ましい。なお、このように上記第二の態様の光触媒密着性変化層中のバインダと同様の材料で形成した場合の密着性変化層の材料および形成方法に関しては、上記第二の態様と同様であるので、ここでの説明は省略する。
【０１１５】
本態様において、この密着性変化層の厚みは、光触媒による密着性の変化速度等の関係より、０．００１μｍから１μｍであることが好ましく、特に好ましくは０．０１〜０．１μｍの範囲内である。
【０１１６】
（５）第五の態様
次に、本実施態様の特性変化層における第五の態様について説明する。本態様における特性変化層は、少なくとも光触媒を含有する光触媒処理層と、上記光触媒処理層上に形成された光触媒の作用により分解除去される分解除去層とからなる層である場合である。
【０１１７】
本態様の特性変化層は、上記光触媒処理層と、上記分解除去層とから構成されることにより、エネルギー照射に伴い、光触媒処理層中の光触媒が励起され、上記分解除去層が分解除去されることにより、上記光触媒処理層上に、凹凸を有するパターンを形成することが可能となるのである。
【０１１８】
本態様に用いられる光触媒処理層は、上述した第三の態様で述べたものと同様であるので、ここでの説明は省略し、以下、分解除去層について説明する。
【０１１９】
本態様に用いられる分解除去層は、エネルギー照射された際に光触媒処理層中の光触媒の作用により、エネルギー照射された部分の分解除去層が分解除去される層であれば、特に限定されるものではない。
【０１２０】
このように分解除去層は、エネルギー照射した部分が光触媒の作用により分解除去されることから、現像工程や洗浄工程を行うことなく分解除去層のある部分と無い部分からなるパターン、すなわち凹凸を有するパターンを形成することができる。
【０１２１】
なお、この分解除去層は、エネルギー照射による光触媒の作用により酸化分解され、気化等されることから、現像・洗浄工程等の特別な後処理なしに除去されるものであるが、分解除去層の材質によっては、洗浄工程等を行ってもよい。
【０１２２】
また、本態様に用いられる分解除去層は、凹凸を形成するのみならず、この分解除去層が、上記露出した部材表面と比較して、液体との接触角が高いことが好ましい。これにより、分解除去層が分解除去された領域を親液性領域、上記分解除去層が残存する領域を撥液性領域とすることが可能となり、種々の導電性パターンを形成することが可能となるからである。この際、分解除去層が分解除去されて露出する部材は、光触媒処理層である。
【０１２３】
ここで、本態様の分解除去層、すなわち撥液性領域においては、４０ｍＮ／ｍの液体との接触角が、１０°以上、好ましくは表面張力５０ｍＮ／ｍの液体との接触角が１０°以下、特に表面張力６０ｍＮ／ｍの液体との接触角が１０°以下となるような層であることが好ましい。これは、エネルギー照射していない部分は、本態様においては撥液性が要求される部分であることから、液体との接触角が小さい場合は、撥液性が十分でなく、例えばインクジェット法等により、導電性パターン組成物を塗布した際に、撥液性領域にまで導電性パターン組成物が付着する可能性が生じることから、高精細な配線基板とすることが困難となるからである。
【０１２４】
また、エネルギー照射により露出した光触媒処理層、すなわち親液性領域においては、４０ｍＮ／ｍの液体との接触角が、４０ｍＮ／ｍの液体との接触角が９°未満、好ましくは表面張力５０ｍＮ／ｍの液体との接触角が１０°以下、特に表面張力６０ｍＮ／ｍの液体との接触角が１０°以下となるような層であることが好ましい。エネルギー照射された部分、すなわち親液性領域における導電性パターン組成物との接触角が高い場合は、導電性パターン組成物を塗布した場合に、親液性領域においても導電性パターン組成物をはじいてしまう可能性があり、例えばインクジェット法等により親液性領域上に導電性パターンを形成することが難しくなる可能性があるからである。ここで、液体との接触角は、第一実施態様において説明した方法により測定した値である。
【０１２５】
本態様の分解除去層に用いることができる膜としては、具体的にはフッ素系や炭化水素系の撥液性を有する樹脂等による膜を挙げることができる。これらのフッ素系や炭化水素系の樹脂は、撥液性を有するものであれば、特に限定されるものではなく、これらの樹脂を溶媒に溶解させ、例としてスピンコート法等の一般的な成膜方法により形成することが可能である。
【０１２６】
また、本態様においては、機能性薄膜、すなわち、自己組織化単分子膜、ラングミュア−ブロケット膜、および交互吸着膜等を用いることにより、欠陥のない膜を形成することが可能であることから、このような成膜方法を用いることがより好ましいといえる。
【０１２７】
ここで、本態様に用いられる自己組織化単分子膜、ラングミュア−ブロケット膜、および交互吸着膜について具体的に説明する。
【０１２８】
（ｉ）自己組織化単分子膜
自己組織化単分子膜(Self-Assembled Monolayer)の公式な定義の存在を発明者らは知らないが、一般的に自己組織化膜として認識されているものの解説文としては、例えばAbraham Ulmanによる総説“Formation and Structure of Self-Assembled Monolayers”, Chemical Review, 96, 1533-1554 (1996)が優れている。本総説を参考にすれば、自己組織化単分子膜とは、適当な分子が適当な基材表面に吸着・結合（自己組織化）した結果生じた単分子層のことと言える。自己組織化膜形成能のある材料としては、例えば、脂肪酸などの界面活性剤分子、アルキルトリクロロシラン類やアルキルアルコキシド類などの有機ケイ素分子、アルカンチオール類などの有機イオウ分子、アルキルフォスフェート類などの有機リン酸分子などが挙げられる。分子構造の一般的な共通性は、比較的長いアルキル鎖を有し、片方の分子末端に基材表面と相互作用する官能基が存在することである。アルキル鎖の部分は分子同士が２次元的にパッキングする際の分子間力の源である。もっとも、ここに示した例は最も単純な構造であり、分子のもう一方の末端にアミノ基やカルボキシル基などの官能基を有するもの、アルキレン鎖の部分がオキシエチレン鎖のもの、フルオロカーボン鎖のもの、これらが複合したタイプの鎖のものなど様々な分子から成る自己組織化単分子膜が報告されている。また、複数の分子種から成る複合タイプの自己組織化単分子膜もある。また、最近では、デンドリマーに代表されるような粒子状で複数の官能基（官能基が一つの場合もある）を有する高分子や直鎖状（分岐構造のある場合もある）の高分子が一層基材表面に形成されたもの（後者はポリマーブラシと総称される）も自己組織化単分子膜と考えられる場合もあるようである。本態様は、これらも自己組織化単分子膜に含める。
【０１２９】
（ii）ラングミュア−ブロジェット膜
本態様に用いられるラングミュア−ブロジェット膜(Langmuir-Blodgett Film)は、基材上に形成されてしまえば形態上は上述した自己組織化単分子膜との大きな相違はない。ラングミュア−ブロジェット膜の特徴はその形成方法とそれに起因する高度な２次元分子パッキング性（高配向性、高秩序性）にあると言える。すなわち、一般にラングミュア−ブロジェット膜形成分子は気液界面上に先ず展開され、その展開膜がトラフによって凝縮されて高度にパッキングした凝縮膜に変化する。実際は、これを適当な基材に移しとって用いる。ここに概略を示した手法により単分子膜から任意の分子層の多層膜まで形成することが可能である。また、低分子のみならず、高分子、コロイド粒子なども膜材料とすることができる。様々な材料を適用した最近の事例に関しては宮下徳治らの総説“ソフト系ナノデバイス創製のナノテクノロジーへの展望” 高分子 50巻 9月号 644-647 (2001)に詳しく述べられている。
【０１３０】
（iii）交互吸着膜
交互吸着膜(Layer-by-Layer Self-Assembled Film)は、一般的には、最低２個の正または負の電荷を有する官能基を有する材料を逐次的に基材上に吸着・結合させて積層することにより形成される膜である。多数の官能基を有する材料の方が膜の強度や耐久性が増すなど利点が多いので、最近ではイオン性高分子（高分子電解質）を材料として用いることが多い。また、タンパク質や金属や酸化物などの表面電荷を有する粒子、いわゆる“コロイド粒子”も膜形成物質として多用される。さらに最近では、水素結合、配位結合、疎水性相互作用などのイオン結合よりも弱い相互作用を積極的に利用した膜も報告されている。比較的最近の交互吸着膜の事例については、静電的相互作用を駆動力にした材料系に少々偏っているがPaula T. Hammondによる総説“Recent Explorations in Electrostatic Multilayer Thin Film Assembly”Current Opinion in Colloid & Interface Science, 4, 430-442 (2000)に詳しい。交互吸着膜は、最も単純なプロセスを例として説明すれば、正（負）電荷を有する材料の吸着−洗浄−負（正）電荷を有する材料の吸着−洗浄のサイクルを所定の回数繰り返すことにより形成される膜である。ラングミュア−ブロジェット膜のように展開−凝縮−移し取りの操作は全く必要ない。また、これら製法の違いより明らかなように、交互吸着膜はラングミュア−ブロジェット膜のような２次元的な高配向性・高秩序性は一般に有さない。しかし、交互吸着膜及びその作製法は、欠陥のない緻密な膜を容易に形成できること、微細な凹凸面やチューブ内面や球面などにも均一に成膜できることなど、従来の成膜法にない利点を数多く有している。
【０１３１】
また、分解除去層の膜厚としては、後述するエネルギーの照射の際に、照射されるエネルギーにより分解除去される程度の膜厚であれば特に限定されるものではない。具体的な膜厚としては、照射されるエネルギーの種類や分解除去層の材料等により大きく異なるものではあるが、一般的には、０．００１μｍ〜１μｍの範囲内、特に０．０１μｍ〜０．１μｍの範囲内とすることが好ましい。
【０１３２】
（特性変化層の特性が変化したパターン）
次に、上記特性変化層の特性が変化したパターンについて説明する。本実施態様においては、上記特性変化層の特性が変化したパターンに沿って後述する導電性パターンを形成するために、上記特性変化層の特性が変化したパターンを形成するのである。
【０１３３】
本実施態様における特性変化層の特性が変化したパターンの形成方法は、上記特性変化層に、所定の方向からエネルギーをパターン照射することにより、上記特性変化層表面に特性の変化したパターンを形成する方法が用いられる。
【０１３４】
なお、本発明でいうエネルギー照射（露光）とは、上記特性変化層の特性を変化させることが可能ないかなるエネルギー線の照射をも含む概念であり、可視光の照射に限定されるものではない。
【０１３５】
通常このようなエネルギー照射に用いる光の波長は、４００ｎｍ以下の範囲、好ましくは３８０ｎｍ以下の範囲から設定される。これは、上述したように光触媒に二酸化チタンが好ましく用いられ、この二酸化チタンにより光触媒作用を活性化させるエネルギーとして、上述した波長の光が好ましいからである。
【０１３６】
このようなエネルギー照射に用いることができる光源としては、水銀ランプ、メタルハライドランプ、キセノンランプ、エキシマランプ、その他種々の光源を挙げることができる。
【０１３７】
上述したような光源を用い、フォトマスクを介したパターン照射により行う方法の他、エキシマ、ＹＡＧ等のレーザを用いてパターン状に描画照射する方法を用いることも可能である。
【０１３８】
また、エネルギー照射に際してのエネルギーの照射量は、特性変化層が光触媒の作用により特性が変化するのに必要な照射量とする。
【０１３９】
この際、光触媒を加熱しながらエネルギー照射することにより、感度を上昇させことが可能となり、効率的な濡れ性の変化を行うことができる点で好ましい。具体的には３０℃〜８０℃の範囲内で加熱することが好ましい。
【０１４０】
（導電性パターン）
次に、本実施態様に用いられる導電性パターンについて説明する。本実施態様に用いられる導電性パターンは、上述した特性変化層の特性が変化したパターンに沿って形成された導電性を有するパターンであれば、そのパターンの形状や材料等は特に限定されるものではない。本実施態様における導電性パターンに用いられる材料として、具体的には、銅、金、銀、ニッケル、アルミニウム、パラジウム、鉛、スズおよびこれらのなかの金属を一種以上含む粉末状の金属または合金と、バインダ樹脂、分散材、有機溶剤からなる金属インキを挙げることができ、中でも銅および銀を用いた金属インキであることが好ましい。
【０１４１】
また、本実施態様の導電性パターンの形成方法は、上述した特性変化層の特性の変化により適宜選択されるものであるが、具体的には、蒸着法、無電界めっき、ディップコート、ロールコート、ブレードコート、スピンコート等の塗布手段、インクジェット、電解ジェット等を含むノズル吐出手段等の手段等が挙げられる。
【０１４２】
例えば上記特性変化層が光触媒濡れ性変化層または濡れ性変化層である場合には、親液性領域および撥液性領域が形成されており、この濡れ性の差を利用して、親液性領域のみに、金属コロイド溶液をインクジェット法やロールコート法により塗布する方法や、金属ペーストを電解ジェット法により塗布する方法等が挙げられる。
【０１４３】
また、上記特性変化層が光触媒密着性変化層または密着性変化層である場合には、密着性良好領域および密着阻害領域が形成されており、例えば蒸着法等により全面に金属を付着させ、金属が密着していない密着阻害領域上の金属を除去することにより、密着性良好領域上のみに導電性パターンを形成することが可能となるのである。
【０１４４】
さらに、上記特性変化層が分解除去層である場合には、表面に形成された凹凸を利用して、金属コロイド溶液をインクジェット法により塗布する方法や、金属ペーストを電解ジェット法により塗布する方法等が挙げられる。
【０１４５】
（配線基板）
次に、本実施態様における配線基板について説明する。本実施態様における配線基板とは、上記特性変化層と、上記特性変化層の特性が変化したパターンに沿って形成された上記導電性パターンとを有するものであり、その配線パターン等は特に限定されるものではない。
【０１４６】
（多層配線基板）
次に、本実施態様の多層配線基板について説明する。本実施態様の多層配線基板は、上記配線基板が少なくとも２層以上積層されたものであり、中でも３層から５層積層されたものであることが好ましい。
【０１４７】
本実施態様においては、上述した高精細な導電性パターンを有する配線基板を積層することにより、高精細な導電性パターンを有する多層配線基板とすることが可能となるのである。
【０１４８】
また、本実施態様の多層配線基板においては、光触媒を含有する光触媒処理層および基体を有する光触媒処理層側基板を、上記光触媒処理層が２００μｍ以下となるように間隙をおいて配置された後、所定の方向からエネルギー照射されることにより特性が変化する特性反応層（後で記述する）と、上記特性反応層の特性が変化したパターンに沿って形成された導電性パターンとからなる配線基板が、少なくとも１層積層されていてもよい。
【０１４９】
また、隣接する配線基板の導電性パターン間に、後述するような導電性コネクタを有していてもよく、また最下層部の特性変化層に自己支持性がない場合や、多層配線基板に強度が必要とされる場合等には、多層配線基板が後述する基材上に形成されたものであってもよい。以下、各構成について説明する。
【０１５０】
（基材）
ここで、本実施態様に用いられる基材について説明する。本実施態様においては、例えば多層配線基板の最下層部に形成される特性変化層に自己支持性のない場合や、多層配線基板に強度が必要とされる場合に基材が用いられ、例として図２に示すように、基材４上に多層配線基板における最下層部の配線基板の特性変化層１が設けられる。
【０１５１】
このような基材としては、最終的に得られる多層配線基板の用途等に応じて適宜選択されるものであり、例えば通常のプリント配線板等の場合においては、一般的に用いられている材料、具体的には紙基材の樹脂積層板、ガラス布・ガラス不織布基材の樹脂積層板、セラミック、金属等を用いることができる。また、フレキシブル配線板においては、可撓性を有する樹脂製フィルムを基材として用いることも可能である。
【０１５２】
（導電性コネクタ）
次に、本実施態様における導電性コネクタについて説明する。本実施態様の多層配線基板においては、隣接する配線基板または後述する特性反応層を有する配線基板の導電性パターン同士を電気的に接続するために設けられる、導電性の材料により形成された部位である導電性コネクタを有していてもよく、例えば図３に示すように、配線基板３における導電性部２と、隣接する配線基板３′における導電性部２′間に、導電性の材料によって形成されたものである。本実施態様においては、この導電性コネクタは、電気的に接続可能なものであれば、その形成方法等は特に限定されるものではないが、本実施態様においては、上述した特性変化層または後述する特性反応層に形成されたスルーホールに導電性材料が充填されることにより、形成されたものであることが好ましい。
【０１５３】
ここで、本実施態様におけるスルーホールとは、導電性パターンと、この導電性パターンと特性変化層をはさんだ直下に存在する導電性パターンとを、電気的に接続する導電性コネクタを形成するために、特性変化層または後述する特性反応層に設けられた孔部のことをいう。
【０１５４】
ここで、本実施態様においては、配線基板中に上述した特性変化層または特性反応層を有することから、これらの特性の変化を利用して、容易にスルーホールを形成することが可能である。
【０１５５】
例えば、上記特性変化層が光触媒濡れ性変化層または濡れ性変化層である場合には、スルーホールを形成するパターン状にエネルギーを照射してパターン状に親液性領域を形成し、その親液性領域上に例えばアルカリ溶液等を塗布することによって、エッチングをすることができ、容易に高精細なスルーホールを形成することが可能となるのである。
【０１５６】
なお、本実施態様の導電性コネクタに用いられる材料および形成方法は、上述した導電性パターンと同様のものを用いることが可能であるので、ここでの説明は省略する。
【０１５７】
（特性反応層を有する配線基板）
次に、特性反応層を有する配線基板について説明する。本実施態様における上記多層配線基板は、光触媒を含有する光触媒処理層および基体を有する光触媒処理層側基板を、上記光触媒処理層が２００μｍ以下となるように間隙をおいて配置された後、所定の方向からエネルギー照射されることにより特性が変化する特性反応層と、上記特性反応層の特性が変化したパターンに沿って形成された導電性パターンとからなる配線基板が、少なくとも１層積層されていてもよい。
【０１５８】
以下、この特性反応層を有する配線基板について、各構成ごとに説明する。
【０１５９】
（１）特性反応層
まず、本実施態様の特性反応層を有する配線基板に用いられる特性反応層について説明する。本実施態様の特性反応層を有する配線基板に用いられる特性反応層とは、触媒を含有する光触媒処理層および基体を有する光触媒処理層側基板を、上記光触媒処理層が２００μｍ以下となるように間隙をおいて配置された後、所定の方向からエネルギー照射されることにより特性が変化する層であり、この特性の変化したパターンに沿って導電性パターンが形成することが可能な層である。
【０１６０】
本実施態様における特性反応層を有する配線基板については、例えば図４に示すように、基体６および光触媒処理層５を有する光触媒処理層側基板７を、上記特性反応層１５と光触媒処理層５とが所定の間隙となるように配置された後、例えばフォトマスク８等を用いて、所定の方向からエネルギー９をパターン状に照射されることにより、特性反応層１５上の特性が変化する層である。
【０１６１】
本実施態様においては、上記特性反応層の電気抵抗が１×１０^８Ω・ｃｍ〜１×１０^１８Ω・ｃｍの、中でも１×１０^１５Ω・ｃｍ〜１×１０^１８Ω・ｃｍの範囲内であることが好ましい。特性反応層の電気抵抗が、上記範囲内より低い場合には、多層配線基板を形成した際に、後述する導電性パターンを電気配線として用いることが困難となるからである。
【０１６２】
また、本実施態様においては、上記特性反応層が、液体によりエッチングされる層であることが好ましく、中でもアルカリ溶液によりエッチングされる層であることが好ましい。これにより、例えば多層配線基板中に、隣接する導電性パターン間を接続する導電性コネクタを有する場合に、この導電性コネクタを形成するためのスルーホールを形成する際に、特性が変化したパターンに沿って、液体を作用させることにより、容易にエッチングを行うこと等が可能となり、またそのエッチングに用いられる液体がアルカリ溶液であれば、より効率的にエッチングを行うことが可能となるからである。
【０１６３】
本実施態様において、上記特性反応層は、中でも導電性パターンを形成する観点から、エネルギー照射に伴う光触媒の作用により、液体との接触角が低下するように濡れ性が変化する濡れ性変化層である場合、またはエネルギー照射に伴う光触媒の作用により、密着性が変化する密着性変化層である場合が好ましい。
【０１６４】
上記特性反応層が、上記濡れ性変化層である場合には、エネルギー照射に伴う光触媒の作用により、濡れ性の低下したパターンを形成することが可能となり、この濡れ性の差を利用して、例えばインクジェット法等により導電性パターン組成物を親液性領域のみに、高精細に塗布することが可能となるからである。また、上記特性反応層が、上記密着性変化層である場合には、エネルギー照射に伴う光触媒の作用により形成された密着性を変化させることが可能となり、例えば蒸着法等により、全面に導電性パターン組成物を成膜後、密着性の差を利用して、密着性が良好な領域以外の密着性の悪い部分の導電性パターン組成物を除去することにより、高精細な導電性パターン部を形成することが可能となるのである。
【０１６５】
なお、上記濡れ性変化層および上記密着性変化層については、上述した特性反応層における第三の態様で説明した濡れ性変化層および第四の態様で説明した密着性変化層と同様であるので、ここでの説明は省略する。
【０１６６】
（２）光触媒処理層側基板
次に上記特性反応層の特性が変化したパターンを形成するために用いられる光触媒処理層側基板について以下説明する。
【０１６７】
本実施態様に用いられる光触媒処理層側基板は、少なくとも光触媒処理層と基体とを有するものであり、通常は基体上に所定の方法で形成された薄膜状の光触媒処理層が形成されてなるものである。また、この光触媒処理層側基板には、パターン状に形成された光触媒処理層側遮光部やプライマー層が形成されたものも用いることができる。
【０１６８】
本実施態様においては、エネルギーを照射する際に、上記特性反応層と、上記光触媒処理層側基板における光触媒処理層とを所定の間隙をおいて対向させ、光触媒処理層側基板の光触媒処理層の作用により、特性反応層の濡れ性を変化させ、エネルギー照射後、光触媒処理層側基板を取り外すことにより濡れ性パターンが形成されるのである。以下、この光触媒処理層側基板の各構成について説明する。
【０１６９】
ａ．光触媒処理層
本実施態様に用いられる光触媒処理層は、少なくとも光触媒を含有するものであり、バインダを有していても、有していなくてもよく、上述した特性変化層の第二の態様で説明した光触媒処理層と同様であるので、ここでの説明は省略する。
【０１７０】
ここで、本実施態様において用いられる光触媒処理層は、例えば図４に示すように、光触媒処理層側基体６上に全面に形成されたものであってもよいが、例えば図５に示すように、基体６上に光触媒処理層５がパターン状に形成されたものであってもよい。
【０１７１】
このように光触媒処理層をパターン状に形成することにより、エネルギーを照射する際に、フォトマスク等を用いてパターン照射をする必要がなく、全面に照射することにより、特性反応層上に親液性領域と撥液性領域とからなる濡れ性パターンを形成することができる。
【０１７２】
この光触媒処理層のパターニング方法は、特に限定されるものではないが、例えばフォトリソグラフィー法等により行うことが可能である。
【０１７３】
また、光触媒処理層と特性反応層とを例えば密着させてエネルギー照射を行う場合には、実際に光触媒処理層の形成された部分のみの特性が変化するものであるので、エネルギーの照射方向は上記光触媒処理層と特性反応層とが対向する部分にエネルギーが照射されるものであれば、いかなる方向から照射されてもよく、さらには、照射されるエネルギーも特に平行光等の平行なものに限定されないという利点を有するものとなる。
【０１７４】
ｂ．基体
本実施態様においては、図４に示すように、光触媒処理層側基板７は、少なくとも基体６とこの基体６上に形成された光触媒処理層５とを有するものである。
【０１７５】
この際、用いられる基体を構成する材料は、後述するエネルギーの照射方向や、得られる多層配線基板が透明性を必要とするか等により適宜選択される。
【０１７６】
また本実施態様に用いられる基体は、可撓性を有するもの、例えば樹脂製フィルム等であってもよいし、可撓性を有さないもの、例えばガラス基板等であってもよい。これは、エネルギー照射方法により適宜選択されるものである。
【０１７７】
なお、基体表面と光触媒処理層との密着性を向上させるために、基体上にアンカー層を形成するようにしてもよい。このようなアンカー層としては、例えば、シラン系、チタン系のカップリング剤等を挙げることができる。
【０１７８】
ｃ．光触媒処理層側遮光部
本実施態様に用いられる光触媒処理層側基板には、パターン状に形成された光触媒処理層側遮光部が形成されたものを用いても良い。このように光触媒処理層側遮光部を有する光触媒処理層側基板を用いることにより、エネルギー照射に際して、フォトマスクを用いたり、レーザ光による描画照射を行う必要がない。したがって、光触媒処理層側基板とフォトマスクとの位置合わせが不要であることから、簡便な工程とすることが可能であり、また描画照射に必要な高価な装置も不必要であることから、コスト的に有利となるという利点を有する。
【０１７９】
このような光触媒処理層側遮光部を有する光触媒処理層側基板は、光触媒処理層側遮光部の形成位置により、下記の二つの態様とすることができる。
【０１８０】
一つが、例えば図６に示すように、基体６上に光触媒処理層側遮光部１１を形成し、この光触媒処理層側遮光部１１上に光触媒処理層５を形成して、光触媒処理層側基板７とする態様である。もう一つは、例えば図７に示すように、基体６上に光触媒処理層５を形成し、その上に光触媒処理層側遮光部１１を形成して光触媒処理層側基板７とする態様である。
【０１８１】
いずれの態様においても、フォトマスクを用いる場合と比較すると、光触媒処理層側遮光部が、上記光触媒処理層と特性反応層との配置部分の近傍に配置されることになるので、基体内等におけるエネルギーの散乱の影響を少なくすることができることから、エネルギーのパターン照射を極めて正確に行うことが可能となる。
【０１８２】
さらに、上記光触媒処理層上に光触媒処理層側遮光部を形成する態様においては、光触媒処理層と特性反応層とを所定の位置に配置する際に、この光触媒処理層側遮光部の膜厚をこの間隙の幅と一致させておくことにより、上記光触媒処理層側遮光部を上記間隙を一定のものとするためのスペーサとしても用いることができるという利点を有する。
【０１８３】
すなわち、所定の間隙をおいて上記光触媒処理層と特性反応層とを対向させた状態で配置する際に、上記光触媒処理層側遮光部と特性反応層とを密着させた状態で配置することにより、上記所定の間隙を正確とすることが可能となり、そしてこの状態で光触媒処理層側基板からエネルギーを照射することにより、特性反応層上に特性変化パターンを精度良く形成することが可能となるのである。
【０１８４】
このよう光触媒処理層側遮光部の形成方法は、特に限定されるものではなく、光触媒処理層側遮光部の形成面の特性や、必要とするエネルギーに対する遮蔽性等に応じて適宜選択されて用いられる。
【０１８５】
例えば、スパッタリング法、真空蒸着法等により厚み１０００〜２０００Å程度のクロム等の金属薄膜を形成し、この薄膜をパターニングすることにより形成されてもよい。このパターニングの方法としては、スパッタ等の通常のパターニング方法を用いることができる。
【０１８６】
また、樹脂バインダ中にカーボン微粒子、金属酸化物、無機顔料、有機顔料等の遮光性粒子を含有させた層をパターン状に形成する方法であってもよい。用いられる樹脂バインダとしては、ポリイミド樹脂、アクリル樹脂、エポキシ樹脂、ポリアクリルアミド、ポリビニルアルコール、ゼラチン、カゼイン、セルロース等の樹脂を１種または２種以上混合したものや、感光性樹脂、さらにはＯ／Ｗエマルジョン型の樹脂組成物、例えば、反応性シリコーンをエマルジョン化したもの等を用いることができる。このような樹脂製遮光部の厚みとしては、０．５〜１０μｍの範囲内で設定することができる。このよう樹脂製遮光部のパターニングの方法は、フォトリソ法、印刷法等一般的に用いられている方法を用いることができる。
【０１８７】
なお、上記説明においては、光触媒処理層側遮光部の形成位置として、基体と光触媒処理層との間、および光触媒処理層表面の二つの場合について説明したが、その他、基体の光触媒処理層が形成されていない側の表面に光触媒処理層側遮光部を形成する態様も採ることが可能である。この態様においては、例えばフォトマスクをこの表面に着脱可能な程度に密着させる場合等が考えられ、特性変化パターンを小ロットで変更するような場合に好適に用いることができる。
【０１８８】
ｄ．プライマー層
次に、本実施態様の光触媒処理層側基板に用いられるプライマー層について説明する。本実施態様において、上述したように基体上に光触媒処理層側遮光部をパターン状に形成して、その上に光触媒処理層を形成して光触媒処理層側基板とする場合においては、上記光触媒処理層側遮光部と光触媒処理層との間にプライマー層を形成してもよい。
【０１８９】
このプライマー層の作用・機能は必ずしも明確なものではないが、光触媒処理層側遮光部と光触媒処理層との間にプライマー層を形成することにより、プライマー層は光触媒の作用による特性反応層の特性変化を阻害する要因となる光触媒処理層側遮光部および光触媒処理層側遮光部間に存在する開口部からの不純物、特に、光触媒処理層側遮光部をパターニングする際に生じる残渣や、金属、金属イオン等の不純物の拡散を防止する機能を示すものと考えられる。したがって、プライマー層を形成することにより、高感度で特性変化の処理が進行し、その結果、高解像度のパターンを得ることが可能となるのである。
【０１９０】
なお、本実施態様においてプライマー層は、光触媒処理層側遮光部のみならず光触媒処理層側遮光部間に形成された開口部に存在する不純物が光触媒の作用に影響することを防止するものであるので、プライマー層は開口部を含めた光触媒処理層側遮光部全面にわたって形成されていることが好ましい。
【０１９１】
本実施態様におけるプライマー層は、光触媒処理層側基板の光触媒処理層側遮光部と光触媒処理層とが接触しないようにプライマー層が形成された構造であれば特に限定されるものではない。
【０１９２】
このプライマー層を構成する材料としては、特に限定されるものではないが、光触媒の作用により分解されにくい無機材料が好ましい。具体的には無定形シリカを挙げることができる。このような無定形シリカを用いる場合には、この無定形シリカの前駆体は、一般式ＳｉＸ_４で示され、Ｘはハロゲン、メトキシ基、エトキシ基、またはアセチル基等であるケイ素化合物であり、それらの加水分解物であるシラノール、または平均分子量３０００以下のポリシロキサンが好ましい。
【０１９３】
また、プライマー層の膜厚は、０．００１μｍから１μｍの範囲内であることが好ましく、特に０．００１μｍから０．１μｍの範囲内であることが好ましい。
【０１９４】
（３）特性反応層の特性が変化したパターン
次に、特性反応層の特性が変化したパターンについて説明する。本実施態様の特性反応層の特性が変化したパターンを形成する方法としては、上記光触媒処理層および上記特性反応層を所定の位置に配置した後、所定の方向からエネルギーを照射することにより、上記特性反応層表面にパターンを形成する工程が行われる。以下、この特性変化パターンの形成について説明する。
【０１９５】
ａ．光触媒処理層および特性反応層の配置
本実施態様の特性変化パターン形成工程においては、まずエネルギー照射時に光触媒処理層と特性反応層とを光触媒の作用が及ぶように所定の間隔をおいて配置する必要があり、本実施態様においては、上述した光触媒処理層および特性反応層を２００μｍ以下の間隙をおいて配置した後、所定の方向からエネルギーを照射する。この際、光触媒処理層および特性反応層を密着させてもよい。
【０１９６】
本実施態様において上記間隙は、パターン精度が極めて良好であり、光触媒の感度も高く、したがって特性反応層の特性変化の効率が良好である点を考慮すると特に０．２μｍ〜１０μｍの範囲内、好ましくは１μｍ〜５μｍの範囲内とすることが好ましい。このような間隙の範囲は、特に間隙を高い精度で制御することが可能である小面積の特性反応層に対して特に有効である。
【０１９７】
一方、例えば３００ｍｍ×３００ｍｍといった大面積の特性反応層に対して処理を行う場合は、接触することなく、かつ上述したような微細な間隙を光触媒処理層側基板と特性反応層との間に形成することは極めて困難である。したがって、特性反応層が比較的大面積である場合は、上記間隙は、１０〜１００μｍの範囲内、特に５０〜７５μｍの範囲内とすることが好ましい。間隙をこのような範囲内とすることにより、パターンがぼやける等のパターン精度の低下の問題や、光触媒の感度が悪化して特性変化の効率が悪化する等の問題が生じることなく、さらに特性反応層上の特性変化にムラが発生しないといった効果を有するからである。
【０１９８】
このように比較的大面積の特性反応層をエネルギー照射する際には、エネルギー照射装置内の光触媒処理層側基板と特性反応層との位置決め装置における間隙の設定を、１０μｍ〜２００μｍの範囲内、特に２５μｍ〜７５μｍの範囲内に設定することが好ましい。設定値をこのような範囲内とすることにより、パターン精度の大幅な低下や光触媒の感度の大幅な悪化を招くことなく、かつ光触媒処理層側基板と特性反応層とが接触することなく配置することが可能となるからである。
【０１９９】
このように光触媒処理層と特性反応層表面とを所定の間隔で離して配置することにより、酸素と水および光触媒作用により生じた活性酸素種が脱着しやすくなる。すなわち、上記範囲より光触媒処理層と特性反応層との間隔を狭くした場合は、上記活性酸素種の脱着がしにくくなり、結果的に特性変化速度を遅くしてしまう可能性があることから好ましくない。また、上記範囲より間隔を離して配置した場合は、生じた活性酸素種が特性反応層に届き難くなり、この場合も特性変化の速度を遅くしてしまう可能性があることから好ましくない。
【０２００】
本実施態様においては、このような配置状態は、少なくともエネルギー照射の間だけ維持されればよい。
【０２０１】
このような極めて狭い間隙を均一に形成して光触媒処理層と特性反応層とを配置する方法としては、例えばスペーサを用いる方法を挙げることができる。そして、このようにスペーサを用いることにより、均一な間隙を形成することができると共に、このスペーサが接触する部分は、光触媒の作用が特性反応層表面に及ばないことから、このスペーサを上述した特性変化パターンと同様のパターンを有するものとすることにより、特性反応層上に所定の特性変化パターンを形成することが可能となる。
【０２０２】
本実施態様においては、このようなスペーサを一つの部材として形成してもよいが、工程の簡略化等のため、上記光触媒処理層側基板の欄で説明したように、光触媒処理層側基板の光触媒処理層表面に形成することが好ましい。なお、上記光触媒処理層側基板における説明においては、光触媒処理層側遮光部として説明したが、本実施態様においては、このようなスペーサは特性反応層表面に光触媒の作用が及ばないように表面を保護する作用を有すればよいものであることから、特に照射されるエネルギーを遮蔽する機能を有さない材料で形成されたものであってもよい。
【０２０３】
ｂ．エネルギー照射
次に、上述したような配置を維持した状態で、対向する部分へのエネルギー照射が行われる。なお、このエネルギー照射については、上述した特性変化層の特性が変化したパターンの項で説明したものと同様であるので、ここでの説明は省略する。
【０２０４】
ここで、光触媒処理層側遮光部が形成されている場合は、光触媒処理層側基板側からエネルギー照射が行なわれる必要があり、かつこの場合は光触媒処理層側基板が照射されるエネルギーに対して透明である必要がある。なお、この場合、光触媒処理層上に光触媒処理層側遮光部が形成され、かつこの光触媒処理層側遮光部を上述したようなスペーサとしての機能を有するように用いた場合においては、多層配線基板の種類によっては、エネルギー照射方向は光触媒処理層側基板側からでも多層配線基板側からであってもよい。
【０２０５】
また、光触媒処理層がパターン状に形成されている場合におけるエネルギー照射方向は、上述したように、光触媒処理層と特性反応層とが対向する部分にエネルギーが照射されるのであれば、多層配線基板の種類によっては、いかなる方向から照射されてもよい。
【０２０６】
同様に、上述したスペーサを用いる場合も、対向する部分にエネルギーが照射されるのであれば、多層配線基板の種類によっては、いかなる方向から照射されてもよい。
【０２０７】
フォトマスクを用いる場合は、フォトマスクが配置された側からエネルギーが照射される。この場合は、フォトマスクが配置された側の基板、すなわち光触媒処理層側基板もしくは多層配線基板のいずれかが透明である必要がある。
【０２０８】
ｃ．光触媒処理層側基板の取り外し
上述したようなエネルギー照射が終了すると、光触媒処理層側基板が特性反応層との配置位置から離され、特性反応層の特性が変化したパターンが特性反応層上に形成される。
【０２０９】
（４）導電性パターン
次に、特性反応層を有する配線基板における導電性パターンについて説明する。本実施態様における特性反応層上に形成される導電性パターンについては、上述した特性反応層上の、特性が変化したパターンに沿って形成される導電性を有するパターンであれば、そのパターンの形状や材料等は特に限定されるものではない。
【０２１０】
なお、上記特性反応層上に形成される導電性パターンについては、上述した特性変化層上に形成される導電性パターンと同様であるので、ここでの説明は省略する。
【０２１１】
２．第二実施態様
次に、本発明における多層配線基板の第二実施態様について説明する。本発明における多層配線基板の第二実施態様は、少なくとも光触媒を含有し、かつ光触媒の作用により特性が変化する特性変化層と、上記特性変化層の特性が変化したパターンに沿って形成された導電性パターンとからなる配線基板と、光触媒を含有する光触媒処理層および基体を有する光触媒処理層側基板を、上記光触媒処理層が２００μｍ以下となるように間隙をおいて配置された後、所定の方向からエネルギー照射されることにより特性が変化する特性反応層と、上記特性反応層の特性が変化したパターンに沿って形成された導電性パターンとからなる配線基板とが積層されたことを特徴とするものである。
【０２１２】
本実施態様によれば、上記特性変化層および特性反応層を有することにより、これらの層の特性が変化したパターンに沿って、容易に導電性パターンを形成することが可能となることから、高精細な多層配線基板を形成することが可能となるのである。
【０２１３】
ここで、上記特性変化層、特性反応層、導電性パターン、配線基板、光触媒処理層側基板等は、第一実施態様で説明したものと同様であるので、ここでの説明は省略する。
【０２１４】
Ｂ．多層配線基板の製造方法
次に、本発明の多層配線基板の製造方法について説明する。本発明の多層配線基板の製造方法は、
光触媒を含有し、かつエネルギー照射に伴う光触媒の作用により特性が変化する特性変化層を調製する特性変化層調製工程と、
上記特性変化層上にパターン状にエネルギーを照射することにより、上記特性変化層表面に特性の変化した特性変化パターンを形成する特性変化パターン形成工程と、
上記特性変化パターンに沿って、導電性パターンを形成する導電性パターン形成工程と、
を有する配線基板形成工程を少なくとも２回以上、好ましくは３回から５回行うことを特徴とするものである。
【０２１５】
この配線基板形成工程を、図８を例として用いて説明する。
【０２１６】
本発明の配線基板形成工程においてはまず、特性変化層１を調製する特性変化層調整工程を行う（図８（ａ））。次に、例えばフォトマスク８等を用いて、所定の方向から上記特性変化層上に、エネルギー９をパターン状に照射する特性変化パターン形成工程を行う（図８（ｂ））。これにより、上記特性変化層１上に特性の変化した特性変化パターン１０が形成されるのである。次に、この特性変化パターン１０に沿って、例えばインクジェット法等により、導電性パターン２を形成する導電性パターン形成工程を行い、配線基板３を形成する（図８（ｄ））。この際、上記特性変化層１上の特性が変化した特性変化パターン１０のみに、導電性パターン２を形成する導電性パターン組成物を付着させることが可能となり、高精細な導電性パターン２を形成した配線基板とすることが可能となるのである。
【０２１７】
また、この配線基板形成工程を少なくとも２回以上行うことにより、多層配線基板を形成することから、得られる多層配線基板を高精細な導電性パターンを有するものとすることが可能となるのである。
【０２１８】
また、本発明においては、図９に示すように、上記特性変化層調整工程後（図９（ａ））、例えばフォトマスク８等を用いて、所定の方向から特性変化層１上に、エネルギー９を照射することにより（図９（ｂ））、上記特性変化層１表面に特性の変化したスルーホール特性変化パターン１３を形成するスルーホール特性変化パターン形成工程（図９（ｃ））を行い、そのスルーホール特性変化パターン１３に沿って、液体を塗布することにより、スルーホール１４を形成するスルーホール形成工程（図９（ｄ））を行ってもよい。これにより、上記導電性パターン形成工程において、導電性パターンを形成するのと同時に、スルーホールにも導電性材料を充填することが可能となり、導電性パターン間を電気的に接続する導電性コネクタを容易に形成することが可能となるのである。以下、本発明の多層配線基板の製造方法について各工程ごとに説明する。
【０２１９】
（１）特性変化層調製工程
まず、本発明の特性変化層調製工程について説明する。本発明における特性変化層調製工程は光触媒を含有し、かつエネルギー照射に伴う光触媒の作用により特性が変化する特性変化層を調製する工程であれば、その方法等は特に限定されるものではないが、少なくとも２回目以降の配線基板形成工程においては、塗布法により行なわれることが好ましい。上記特性変化層調製工程が塗布法であることにより、直前の配線基板形成工程により形成された導電性パターンの周囲にも特性変化層を形成することが可能となり、これにより導電性パターンを酸素や水蒸気から保護することが可能となるのである。また、製造効率やコストの面からも好ましい。
【０２２０】
また、本発明に用いられる多層配線基板の最下層部に位置する配線基板の特性変化層が自己支持性を有しない場合は、その最下層部の特性変化層は、基材上に形成されることが必要である。
【０２２１】
なお、本発明に用いられる特性変化層、特性変化層の形成方法および基材等については、上述した「Ａ．多層配線基板」で説明したものと同様であるので、ここでの説明は省略する。
【０２２２】
（２）特性変化パターン形成工程
次に、本発明における特性変化パターン形成工程について説明する。本発明における特性変化パターン形成工程は、所定の方向からエネルギーを照射することにより、上記特性変化層表面に特性の変化した特性変化パターンを形成する工程である。
【０２２３】
本発明の特性変化パターン形成工程は、後述するスルーホール特性変化パターン形成工程およびスルーホール形成工程を行った配線基板について行ってもよく、またスルーホール特性変化パターン形成工程およびスルーホール形成工程を行っていない配線基板について行ってもよい。
【０２２４】
本工程は、後述する導電性パターン形成工程において形成される導電性パターンのパターン状にエネルギーを照射し、後述する導電性パターン形成工程において形成する導電性パターンのパターン状に、上記特性変化層の特性を変化させる工程である。これにより、後述する導電性パターン形成工程において、容易に導電性パターンを形成することが可能となるのである。
【０２２５】
なお、本工程に用いられるエネルギーやエネルギーの照射については、上述した「Ａ．多層配線基板」における特性変化層の特性が変化したパターンの項で説明したものと同様であるので、ここでの説明は省略する。
【０２２６】
（３）導電性パターン形成工程
次に、本発明の導電性パターン形成工程について説明する。本発明の導電性パターン形成工程は、上記特性変化パターン形成工程で形成された特性変化パターンに沿って、導電性パターンを形成する工程であり、後述するスルーホール特性変化パターン形成工程およびスルーホール形成工程が行われた配線基板については、導電性パターンを形成することと同時にスルーホールを充填して、導電性コネクタを形成してもよい。
【０２２７】
本発明の導電性パターン形成工程は、上記特性変化パターン上に導電性パターンを形成することが可能な方法であれば、特に限定されるものではなく、上記特性変化層の特性により適宜選択されるものであるが、例えば上記特性変化層が濡れ性変化層である場合には、ディップコート、ロールコート、ブレードコート、スピンコート等の塗布手段、インクジェット、電解ジェット等を含むノズル吐出手段等の手段を用いることが可能である。本発明においては中でも、ノズル吐出手段を用いることが好ましい。上記ノズル吐出手段においては、目的とするパターン状に導電性パターンを形成する導電性パターン組成物を塗布することが可能となり、より高精細に導電性パターンを形成することが可能となるからである。
【０２２８】
また、上記特性変化層が密着変化層である場合には、上記方法の他に、蒸着法、無電界めっき等も用いることが可能であり、導電性パターン組成物を成膜後、密着阻害領域に付着した導電性パターン組成物を除去することにより、密着性良好領域にのみ導電性パターン組成物を密着させることができ、導電性パターンを形成することが可能となるのである。
【０２２９】
ここで、上記スルーホールを充填し、導電性コネクタを形成する場合にも、同様の方法を用いることができることから、この導電性コネクタは、上記導電性パターンの形成と同時に行うことが可能である。
【０２３０】
（４）スルーホール特性変化パターン形成工程
次に、本発明のスルーホール特性変化パターン形成工程について説明する。本発明におけるスルーホール特性変化パターン形成工程とは、上記特性変化層調整工程後、上記特性変化層にエネルギーを照射することにより、上記特性変化層表面に特性の変化したスルーホール特性変化パターンを形成する工程である。
【０２３１】
本発明において、隣接する配線基板の導電性パターン間に導電性コネクタを形成する場合には、この導電性コネクタを形成するためのスルーホールを、特性変化層に形成するスルーホール特性変化層形成工程およびスルーホール形成工程を有していてもよい。この際、スルーホール特性変化パターン形成工程により、上記特性変化層上に、特性の変化したスルーホール特性変化パターンを形成することにより、後述するスルーホール形成工程において、このスルーホール特性パターンの特性の差を利用して、例えば液体を滴下すること等により、容易にスルーホールを形成することが可能となるからである。
【０２３２】
このスルーホール形成工程におけるエネルギーの照射等は、上述した特性変化パターン形成工程と同様であるので、ここでの説明は省略する。
【０２３３】
（５）スルーホール形成工程
次に、スルーホール形成工程について説明する。本発明におけるスルーホール形成工程は、上記スルーホール特性変化パターンに沿って、液体を塗布することにより、スルーホールを形成する工程である。
【０２３４】
上記液体の塗布は、スルーホールを形成することが可能な方法であれば、特に方法等は限定されるものではないが、本発明においては、他の部材と接触させることなくスルーホール特性変化領域のみに選択的に液体を塗布できる点から、ノズル吐出による方法を用いることが好ましい。このようなノズル吐出法としては、例えばマイクロシリンジ、ディスペンサー、インクジェット等を用いた方法、または針先より電解等の外部刺激により吐出する方法、針先に付着させた液体を特性変化領域に付着させる方法等を用いることができる。本発明においては、中でもディスペンサーまたはインクジェットを用いた方法であることが好ましい。
【０２３５】
また、本発明のスルーホール形成工程に用いられる液体は、アルカリ溶液であることが好ましく、具体的には有機アルカリと無機アルカリの水溶液を上げることができる。好ましいアルカリ溶液としては、水酸化ナトリウム水溶液および水酸化カリウム水溶液を挙げることができ、ｐＨとしては、ｐＨ７〜１４、中でもｐＨ１０〜１４、特にｐＨ１２〜１４であることが好ましい。
【０２３６】
本発明においては、上記配線基板中に上述した特性変化層または特性反応層を有することから、これらの特性の変化を利用して、容易にスルーホールを形成することが可能となるのである。
【０２３７】
例えば、上記特性変化層が濡れ性変化層である場合には、スルーホールを形成するパターン状にエネルギーを照射してパターン状に親液性領域を形成し、その親液性領域上に例えばアルカリ溶液等を塗布することによって、エッチングをすることが可能となり、スルーホールを形成することが可能となるのである。
【０２３８】
また、上記特性変化層が分解除去層である場合には、スルーホールを形成するパターン状にエネルギーを照射してパターン状に凹凸を形成し、その凹凸を利用して、例えば上記アルカリ溶液等を塗布することによって、エッチングをすることが可能となり、スルーホールを容易に形成することが可能となるのである。
【０２３９】
本発明に用いられる導電性パターンおよび導電性コネクタの材料は、上記「Ａ．多層配線基板」で説明したものと同様であるので、ここでの説明は省略する。
【０２４０】
なお、本発明は上記実施形態に限定されるものではない。上記実施形態は、例示であり、本実施態様の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本実施態様の技術的範囲に包含される。
【０２４１】
【実施例】
以下、本実施態様について、実施例を通じてさらに詳述する。
【０２４２】
（特性変化層の形成・一層目）
イソプロピルアルコール３ｇ、フルオロアルキルシラン（トーケムプロダクツ（株）製；ＭＦ−１６０Ｅ（商品名））、Ｎ−[３−（トリメトキシシリル）プロピル]−Ｎ−エチルパーフルオロオクタンスルホンアミドのイソプロピルエーテル５０重量％溶液０．０７ｇ、酸化チタンゾル（石原産業（株）製；ＳＴＫ−０１（商品名））３ｇ、シリカゾル（日本合成ゴム（株）製；グラスカＨＰＣ７００２（商品名））０．６ｇ、およびアルキルアルコキシシラン（日本合成ゴム（株）製；ＨＰＣ４０２Ｈ（商品名））０．２ｇを混合し、１００℃で２０分間攪拌した。この溶液を膜厚０．７ｍｍのガラス基板上にスピンコーティングし、１５０℃で２０分間乾燥した。これにより、基板上に撥液性を有する膜厚１μｍの特性変化層が形成された。このとき、特性変化層の電気抵抗は１×１０^１０Ω・ｃｍであった。
【０２４３】
（特性変化パターン形成・一層目）
次に、上記特性変化層表面に、回路パターン形成用のフォトマスクを介して、超高圧水銀ランプにて露光した。これにより、特性変化層表面の露光された部分のみが親液性領域となった。
【０２４４】
この際の露光量は３６５ｎｍにて１５００ｍＪであった。フォトマスクはクロム製であり、膜厚０．４μｍのブラックマトリックスが２０μｍの幅でライン状に形成されたものを使用した。ラインはフォトマスクの開口部が配線基板の回路パターンとなるように設計した。
【０２４５】
（導電性材料の付与・一層目）
次に、銀微粒子分散体インキ（真空冶金製 Ａｇ００１Ｔ）を用い、インクジェットヘッドより特性変化層上の親液性領域のみに着弾するように吐出した。このインキの特性変化層に対する接触角は撥液性部分で５５°、親液性部分で１０°であった。着弾したインキは撥液性部分に付着することなく、親液性領域のみに濡れ広がった。
【０２４６】
１００℃、３分間の乾燥後、２５０℃、１５分間の焼成を行うことにより、上記フォトマスクの開口部と同様のパターン形状を有する、幅２０μｍ、膜厚０．６μｍの導電性パターンが形成された。導電性パターンの電気抵抗は６×１０^−６Ω・ｃｍであった。
【０２４７】
（特性変化層の形成・二層目）
上記特性変化層の一層目の形成と同様の材料、塗布手法により、上記の導電性パターンが形成された配線基板上に二層目の特性変化層を形成した。
【０２４８】
（スルーホール特性変化パターンの形成）
次に、二層目の特性変化層を形成した基板上に、スルーホール形成用のフォトマスクを介し、超高圧水銀ランプにて露光した。これにより、特性変化層表面の露光された部分（直径１５μｍの円形状のパターン）のみ親液性領域であるスルーホール特性変化パターンが形成された。この際、露光量は３６５ｎｍにて１５００ｍＪであった。フォトマスクは、露光時に直径１５μｍの、円形状の複数の開口部が、上記金属パターン部分に重なるように配置されたものを使用した。
【０２４９】
（スルーホールの形成）
次に、上記複数の直径１５μｍのスルーホール特性変化パターンに、耐アルカリ処理を施したインクジェットヘッドから水酸化カリウム水溶液を塗布した。上記水酸化カリウム水溶液は撥液性部分に付着することなく、親液性領域のみに濡れ広がった。この際、水酸化カリウム水溶液はｐＨ１３であり、撥液性部分に対する接触角は５５°、親液性部分に対する接触角は５°であった。
【０２５０】
これを１分間室温にて放置し、純水にてリンス後、乾燥することにより、親液性部分のみ特性変化層が分解除去され、金属配線部分が露出したスルーホールが形成された。
【０２５１】
（特性変化パターン形成・二層目）
上記スルーホールを形成した基板上に、一層目の特性変化パターン形成に用いたフォトマスクを用い、一層目と同様の手法により露光した。これにより、二層目の特性変化層表面の露光された部分のみ親液性領域となった。
【０２５２】
このとき、スルーホールの位置は、フォトマスクの開口部の位置と重なるため、スルーホール周辺およびスルーホール側面は親液性となった。
【０２５３】
（導電性材料の付与・二層目）
一層目の導電性材料の付与と同様の材料および手法にて、導電性材料を付与した。着弾したインキは、撥液性部分に付着することなく、親液性部分のみに濡れ広がり、またスルーホールにも充填された。
【０２５４】
１００℃、３分間の乾燥後、２５０℃、１５分間の焼成を行うことにより、幅２０μｍ、膜厚０．６μｍの二層目の導電性パターンおよび導電性コネクタが形成された。
【０２５５】
（三層目以降）
二層目までの手法と同様の手法にて、配線基板が四層積層された多層配線基板を作成した。各配線パターンの電気的導通および、導電性コネクタによる各層回路パターン間の電気的導通が良好に取れる多層配線基板を形成することができた。
【０２５６】
【発明の効果】
本発明によれば、上記特性変化層を有することにより、上記導電性パターンをその特性の変化したパターンに沿って容易に高精細に形成することが可能となり、その配線基板を積層することにより、高品質な多層配線基板とすることが可能となるのである。
【図面の簡単な説明】
【図１】本発明の多層配線基板の一例を示す概略断面図である。
【図２】本発明の多層配線基板の他の例を示す概略断面図である。
【図３】本発明の多層配線基板の他の例を示す概略断面図である。
【図４】本発明に用いられる光触媒処理層側基板の一例を示す概略断面図である。
【図５】本発明に用いられる光触媒処理層側基板の他の例を示す概略断面図である。
【図６】本発明に用いられる光触媒処理層側基板の他の例を示す概略断面図である。
【図７】本発明に用いられる光触媒処理層側基板の他の例を示す概略断面図である。
【図８】本発明の多層配線基板の製造方法の一例を示す工程図である。
【図９】本発明の多層配線基板の製造方法のスルーホール形成工程を示す工程図である。
【符号の説明】
１ … 特性変化層
２ … 導電性パターン
３ … 配線基板
４ … 基材
５ … 光触媒処理層
６ … 基体
７ … 光触媒処理層側基板
８ … フォトマスク
９ … エネルギー
１０… 特性変化パターン
１１… 光触媒処理層側遮光部
１２… プライマー層
１３… スルーホール特性変化パターン
１４… スルーホール
１５… 特性反応層
１６… 導電性コネクタ[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for manufacturing a multilayer wiring board that can be used for various high-definition electric circuits such as printed boards.
[0002]
[Prior art]
Conventionally, a method for manufacturing a multilayer wiring board has been performed by forming an insulating film or a metal wiring on the substrate. At this time, an insulating material such as polyimide resin is used as the insulating film. However, since it is difficult to directly pattern these insulating films, the entire surface is plated with metal, and a photoresist such as a dry film is laminated, followed by pattern exposure using a photomask or the like. Many processes such as development are required. In addition, the waste liquid generated during development is harmful, and there has been a problem in terms of the environment, such as the need to perform processing in order to discharge it to the environment.
[0003]
In addition, when opening a through hole in an insulating film, generally, an insulating material such as polyimide resin is applied on a metal wiring, a through hole pattern is formed with a photoresist, etching is performed, and a through hole is opened. Using a photosensitive insulating material, exposure and development are performed to open a through hole, and a through hole shape pattern is formed with a photoresist by overexposure at a portion where the through hole is to be opened. There is a method of opening a through hole by covering with resin and etching until the resist pattern is exposed with oxygen plasma or the like, and then removing the exposed resist (for example, see Patent Document 1).
[0004]
However, even in these cases, since the patterning of the insulating film is difficult, the process of removing the resist after the formation of the through hole is necessary, and the manufacturing process is complicated, which causes problems in terms of manufacturing efficiency and cost. was there.
[0005]
[Patent Document 1]
Japanese Patent Application Laid-Open No. 5-198687
[0006]
[Problems to be solved by the invention]
From the above, it is desired to provide a multilayer wiring board that can form a pattern with high definition by a simple process and that does not have a problem of waste liquid treatment.
[0007]
[Means for Solving the Problems]
  The present inventionSmallAt least a first wiring board comprising at least a characteristic change layer containing a photocatalyst and having a characteristic changed by the action of the photocatalyst, and a conductive pattern formed along a pattern in which the characteristic of the characteristic change layer has changed, Laminate two or more layersA conductive connector between conductive patterns of adjacent wiring boardsA multilayer wiring board is provided.
[0008]
  According to the present invention, by having the characteristic change layer, the conductive pattern can be easily and precisely formed along the pattern whose characteristic has changed, and by laminating the wiring board, This makes it possible to obtain a high-quality multilayer wiring board.In addition, by having a conductive connector between the conductive patterns of adjacent wiring boards, it becomes possible to form a more complicated wiring pattern on the multilayer wiring board, and the multilayer wiring that can be used for various applications. A substrate can be obtained.
[0009]
  UpMemorandumIn the morning,UpOn the first wiring board, there is provided a characteristic reaction layer whose characteristic is changed by the action of a photocatalyst included in another layer, and a conductive pattern formed along the pattern in which the characteristic of the characteristic reaction layer is changed. Two wiring boards may be laminated at least one layer. This is because it is possible to use the characteristic reaction layer whose characteristics change when the multilayer wiring board is irradiated with energy using the substrate on the photocatalyst processing layer side.
[0010]
  The present invention also providesSmallA first wiring board comprising a characteristic change layer containing at least a photocatalyst and having characteristics changed by the action of the photocatalyst, and a conductive pattern formed along a pattern in which the characteristics of the characteristic change layer have changed; A characteristic reaction layer whose characteristics are changed by the action of the photocatalyst contained in the layer, and a second wiring substrate comprising a conductive pattern formed along the pattern in which the characteristics of the characteristic reaction layer have changed.And have a conductive connector between the conductive patterns of adjacent wiring boardsA multilayer wiring board is provided.
[0011]
  According to the present invention, by having the characteristic change layer and the characteristic reaction layer, it is possible to easily form a pattern with changed characteristics, and the conductive pattern can be formed in a high definition along the pattern with changed characteristics. It becomes possible to form an excellent multilayer wiring board.ofIt is.In addition, by having a conductive connector between the conductive patterns of adjacent wiring boards, it becomes possible to form a more complicated wiring pattern on the multilayer wiring board, and the multilayer wiring that can be used for various applications. A substrate can be obtained.
[0013]
  UpMemorandumIn the morning,UpIt is preferable that the conductive connector is formed by filling a through hole formed in the characteristic change layer or the characteristic reaction layer with a conductive material. This is because the conductive connector can be easily formed, which is preferable in terms of cost and manufacturing efficiency.
[0014]
  UpMemorandumIn the morning, GroupThe first wiring board or the first wiring board and the second wiring board may be formed on any one surface of the material. When the characteristic change layer in the lowermost layer portion of the multilayer wiring board is not self-supporting or when the multilayer wiring board needs strength, the multilayer wiring board may be formed on the base material. Because.
[0015]
  UpMemorandumIn the morning,UpThe electric resistance of the characteristic change layer or characteristic reaction layer is 1 × 10⁸Ω · cm to 1 × 10¹⁸It is preferably within the range of Ω · cm. Since the characteristic change layer and the characteristic reaction layer are formed around the conductive pattern, by setting the electric resistance of the characteristic change layer or the characteristic reaction layer within the above range, only the conductive pattern portion is formed. This is because a conductive member can be obtained, and an excellent multilayer wiring board can be obtained.
[0016]
  UpMemorandumIn the morning,UpIt is preferable that the characteristic change layer or the characteristic reaction layer is a layer etched by a liquid. Thereby, for example, a through hole or the like can be easily formed by dropping a liquid onto the characteristic change layer or the characteristic reaction layer.
[0017]
  UpMemorandumIn the morning,UpThe liquid is preferably an alkaline solution. This is because the etching can be performed more efficiently, which is preferable in terms of manufacturing efficiency and cost.
[0018]
  UpMemorandumIn the morning,UpAt least one of the characteristic change layers may be a layer in which a contact angle with a liquid is lowered by the action of a photocatalyst accompanying energy irradiation, and may be a photocatalyst wettability change layer containing at least a photocatalyst and a binder. Since the property change layer is the photocatalyst wettability change layer, it is possible to form a pattern with reduced wettability due to the action of the photocatalyst contained in the photocatalyst wettability change layer itself with energy irradiation. In other words, the portion irradiated with energy can be made a lyophilic region, and the portion not irradiated with energy can be made a lyophobic region. This is because it is possible to form a conductive pattern with high definition by using the difference in wettability, for example, by an inkjet method or the like.
[0019]
  UpMemorandumIn the morning,UpIt is preferable that the photocatalyst wettability changing layer includes a decomposition substance that can be decomposed by the action of the photocatalyst accompanying energy irradiation and thereby change the wettability on the photocatalyst wettability changing layer. In the present invention, the change in wettability of the photocatalyst wettability changing layer due to the action of the photocatalyst may be due to the material of the binder. This is because the wettability of the surface may be changed into a pattern by containing it in the wettability changing layer.
[0020]
  UpMemorandumIn the morning,UpAt least one of the property changing layers may be a layer in which the adhesiveness is changed by the action of the photocatalyst accompanying the energy irradiation, and may be a photocatalyst adhesiveness changing layer containing at least a photocatalyst and a binder. When the characteristic change layer is the photocatalyst adhesiveness change layer, a pattern whose surface adhesiveness is easily changed by the action of the photocatalyst contained in the photocatalyst adhesiveness change layer itself with energy irradiation is formed. This is because the conductive pattern can be formed with high definition by using, for example, a vapor deposition method or the like using the difference in adhesion.
[0021]
  UpMemorandumIn the morning,UpThe wettability change in which at least one of the characteristic change layers is a layer in which the contact angle between the photocatalyst treatment layer containing at least the photocatalyst and the liquid is reduced by the action of the photocatalyst associated with energy irradiation formed on the photocatalyst treatment layer. The layer which consists of a layer may be sufficient. Since the property change layer is composed of the photocatalyst treatment layer and the wettability change layer, the surface of the wettability change layer can be easily wetted by the action of the photocatalyst in the photocatalyst treatment layer accompanying energy irradiation. Thus, it is possible to form a pattern with reduced properties, and to make the portion irradiated with energy a lyophilic region and the portion not irradiated with energy a liquid repellent region. This is because a conductive pattern can be formed by utilizing the difference in wettability by, for example, an ink jet method.
[0022]
  UpMemorandumIn the morning,UpAt least one of the characteristic change layers is a layer composed of a photocatalyst treatment layer containing at least a photocatalyst and an adhesion change layer whose adhesion changes due to the action of the photocatalyst associated with energy irradiation formed on the photocatalyst treatment layer. There may be. When the characteristic change layer is composed of the photocatalyst treatment layer and the adhesion change layer, the surface of the adhesion change layer can be easily adhered by the action of the photocatalyst in the photocatalyst treatment layer accompanying energy irradiation. This is because a pattern with changed properties can be formed, and the conductive pattern can be formed by, for example, vapor deposition using the difference in adhesion.
[0023]
  UpMemorandumIn the morning,UpAt least one of the characteristic change layers is a layer composed of a photocatalyst treatment layer containing at least a photocatalyst and a decomposition removal layer that is decomposed and removed by the action of the photocatalyst associated with energy irradiation formed on the photocatalyst treatment layer. Also good. Since the characteristic change layer includes the photocatalyst treatment layer and the decomposition / removal layer, the photocatalyst treatment layer easily has irregularities due to the action of the photocatalyst in the photocatalyst treatment layer accompanying energy irradiation. This is because a pattern can be formed, and the conductive pattern can be formed by using, for example, an ink jet method using the unevenness.
[0024]
  UpMemorandumIn the morning,UpThe characteristic reaction layer may be a wettability changing layer in which the wettability changes so that the contact angle with the liquid is lowered by the action of the photocatalyst accompanying energy irradiation. When the characteristic reaction layer is the wettability changing layer, a pattern in which the wettability of the surface of the wettability changing layer is lowered by the action of the photocatalyst on the photocatalyst processing layer side substrate accompanying energy irradiation is formed. This makes it possible to make a portion irradiated with energy a lyophilic region and a portion not irradiated with energy a liquid repellent region. This is because a conductive pattern can be formed by utilizing the difference in wettability, for example, by an ink jet method or the like.
[0025]
  UpMemorandumIn the morning,UpThe characteristic reaction layer may be an adhesion changing layer in which adhesion changes due to the action of a photocatalyst accompanying energy irradiation. When the characteristic reaction layer is the adhesion changing layer, a pattern in which the wettability of the surface of the wettability changing layer is changed by the action of the photocatalyst on the photocatalyst processing layer side substrate accompanying energy irradiation is formed. This is because the conductive pattern can be formed, for example, by vapor deposition using the difference in wettability.
[0026]
  In addition, the present inventionIsA characteristic change layer preparation step for preparing a characteristic change layer that contains a photocatalyst and changes its characteristics due to the action of the photocatalyst upon energy irradiation, and the characteristic change by irradiating energy in a pattern on the characteristic change layer At least two wiring board forming steps including a characteristic change pattern forming step for forming a characteristic change pattern having a changed characteristic on the surface of the layer and a conductive pattern forming step for forming a conductive pattern along the characteristic change pattern. More than onceA through-hole characteristic change pattern forming step for forming a through-hole characteristic change pattern having changed characteristics on the surface of the characteristic change layer by irradiating energy on the characteristic change layer after the characteristic change layer preparation step; A through hole forming step of forming a through hole by applying a liquid along the through hole characteristic changing pattern.A method for manufacturing a multilayer wiring board is provided.
[0027]
According to the present invention, since the wiring board forming step includes the characteristic changing pattern forming step, a characteristic changing pattern having changed characteristics can be formed, and the characteristic changing pattern can be formed by the conductive pattern forming step. Accordingly, it is possible to easily manufacture a wiring board on which a conductive pattern is formed.
[0028]
  Furthermore, a high-definition multilayer wiring board can be manufactured by performing the wiring board forming step at least twice.Also, through holes for forming conductive connectors can be efficiently formed by performing the through hole characteristic change pattern forming step and the through hole forming step.
[0029]
  UpMemorandumIn the morning2It is preferable that the characteristic change layer preparing step in the wiring substrate forming step performed after the first time is performed by a coating method. This makes it possible to form the characteristic change layer also around the conductive pattern formed in the previous wiring board formation process, and to prevent the influence of oxygen and water vapor. This is because a multilayer wiring board can be obtained, and it is preferable from the viewpoint of manufacturing efficiency.
[0031]
  UpMemorandumIn the morning,UpThe through hole forming step is preferably performed by applying an alkaline solution. This is because the through hole forming step can be performed easily and efficiently.
[0032]
  UpMemorandumIn the morning1The characteristic change layer may be formed on the base material in the characteristic change layer preparation step in the wiring board formation step performed a second time. Thus, when the characteristic changing layer of the lowermost wiring board in the multilayer wiring board does not have self-supporting property, or when the multilayer wiring board requires strength, it is formed on the base material. It may be.
[0033]
  UpMemorandumIn the morning,UpAt least one of the characteristic change layers may be a layer in which a contact angle with a liquid is lowered by the action of a photocatalyst accompanying energy irradiation, and may be a photocatalyst wettability change layer containing at least a photocatalyst and a binder. Since the property change layer is the photocatalyst wettability change layer, in the property change pattern formation step, it is possible to form a pattern with reduced wettability on the surface of the photocatalyst wettability change layer. The irradiated part can be a lyophilic area, and the non-energy irradiated part can be a liquid repellent area. This is because the conductive pattern can be easily formed by the conductive pattern forming step using the difference in wettability.
[0034]
  UpMemorandumIn the morning,UpIt is preferable that at least one of the characteristic change layers is a photocatalyst adhesiveness change layer in which the adhesiveness changes due to the action of the photocatalyst accompanying energy irradiation. Since the characteristic change layer is the photocatalyst adhesiveness change layer, in the characteristic change pattern formation step, it is possible to form a pattern with changed adhesiveness on the photocatalyst adhesiveness change layer, and the conductivity This is because it is possible to easily form a high-definition conductive pattern using the difference in adhesion in the pattern forming step.
[0035]
  UpMemorandumIn the morning,UpThe wettability change in which at least one of the characteristic change layers is a layer in which the contact angle between the photocatalyst treatment layer containing at least the photocatalyst and the liquid is reduced by the action of the photocatalyst accompanying the energy irradiation formed on the photocatalyst treatment layer. The layer which consists of a layer may be sufficient. By forming the property change layer from the photocatalyst treatment layer and the wettability change layer, a pattern with reduced wettability can be easily formed on the surface of the wettability change layer in the property change pattern forming step. This is because, by the conductive pattern forming step, it is possible to easily form a high-definition conductive pattern using the difference in wettability.
[0036]
  UpMemorandumIn the morning,UpAt least one of the characteristic change layers is a layer composed of a photocatalyst treatment layer containing at least a photocatalyst and an adhesion change layer whose adhesion changes due to the action of the photocatalyst accompanying energy irradiation formed on the photocatalyst treatment layer. There may be. By forming the characteristic change layer from the photocatalyst treatment layer and the adhesion change layer, in the characteristic change pattern formation step, a pattern with a change in adhesion can be easily formed on the surface of the wettability change layer. This is because the conductive pattern can be easily formed using the difference in adhesion by the conductive pattern forming step.
[0037]
  UpMemorandumIn the morning,UpAt least one of the characteristic change layers is a layer composed of a photocatalyst treatment layer containing at least a photocatalyst and a decomposition removal layer that is decomposed and removed by the action of the photocatalyst associated with energy irradiation formed on the photocatalyst treatment layer. Also good. When the property change layer is composed of the photocatalyst treatment layer and the decomposition and removal layer, in the property change pattern formation step, it is possible to easily form a pattern having irregularities on the photocatalyst treatment layer. This is because the conductive pattern can be easily formed using the irregularities by the conductive pattern forming step.
[0038]
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a multilayer wiring board and a method for manufacturing the multilayer wiring board. Each will be described separately below.
[0039]
A. Multilayer wiring board
First, the multilayer wiring board of the present invention will be described. The multilayer wiring board in the present invention has two embodiments. Hereinafter, these embodiments will be described separately.
[0040]
1. First embodiment
The first embodiment of the multilayer wiring board of the present invention includes a characteristic change layer containing at least a photocatalyst and having characteristics changed by the action of the photocatalyst, and a conductive formed along a pattern in which the characteristics of the characteristic change layer have changed. The wiring board is formed by laminating at least two layers of wiring boards made of a conductive pattern.
[0041]
For example, as shown in FIG. 1, the multilayer wiring board according to this embodiment includes at least two layers of wiring boards 3 each including a characteristic change layer 1 and a conductive pattern 2 formed on the characteristic change layer 1. As shown in FIG. 2, a multilayer wiring board may be formed on the base material 4.
[0042]
In addition, the photocatalyst treatment layer side substrate having a photocatalyst treatment layer and a substrate containing the photocatalyst is disposed with a gap so that the photocatalyst treatment layer is 200 μm or less, and then irradiated with energy from a predetermined direction. At least one layer of a wiring board comprising a characteristic reaction layer whose characteristics change and a conductive pattern formed along a pattern whose characteristics change in the characteristic reaction layer may be laminated.
[0043]
Further, for example, as shown in FIG. 3, a wiring board 3 ′ similar to the wiring board 3 is formed on a wiring board 3 composed of a characteristic changing layer 1 and a conductive pattern 2 formed on the characteristic changing layer 1. And a conductive connector 16 may be provided between the conductive pattern 2 on the wiring board 3 and the conductive pattern 2 'on the adjacent wiring board 3'.
[0044]
According to this embodiment, since the wiring board has the characteristic change layer containing a photocatalyst, it is possible to change the characteristic into a pattern shape that forms a conductive pattern by energy irradiation. Therefore, it is possible to easily form a high-definition pattern along a pattern whose characteristics have changed. Further, by stacking the wiring boards, a high-quality multilayer wiring board can be obtained. Hereinafter, each configuration of the multilayer wiring board as described above will be described.
[0045]
(Characteristic change layer)
First, the characteristic change layer used in this embodiment will be described. The characteristic change layer used in this embodiment is a layer that contains at least a photocatalyst and whose characteristics change due to the action of the photocatalyst.
[0046]
In this embodiment, the electrical resistance of the characteristic change layer is 1 × 10¹⁵Ω · cm to 1 × 10¹⁸It is preferably within the range of Ω · cm. By setting the electric resistance of the characteristic change layer within the above range, when a multilayer wiring board is formed, it becomes possible to use only a conductive pattern described later as an electric wiring having conductivity, and an excellent multilayer wiring board. This is because it becomes possible.
[0047]
Moreover, in this embodiment, it is preferable that the said characteristic change layer is a layer etched with a liquid, and it is especially preferable that it is a layer etched with an alkaline solution. Thus, for example, when a multilayer wiring board has a conductive connector for connecting between adjacent conductive patterns, when forming a through hole for forming this conductive connector, the pattern has changed in characteristics. This is because it is possible to easily perform etching or the like by adhering a liquid along the surface, and to perform etching more efficiently if the liquid used for the etching is an alkaline solution.
[0048]
In addition, if the characteristic change layer used in this embodiment has the characteristics as described above, the type and configuration of the characteristic change is not particularly limited, but the characteristic change layer used in this embodiment is not limited. In particular, the layer is a layer in which the contact angle with the liquid is lowered by the action of the photocatalyst accompanying energy irradiation, and is a photocatalyst wettability changing layer containing at least a photocatalyst and a binder (hereinafter referred to as a first aspect). ), A layer in which the adhesion changes due to the action of the photocatalyst accompanying energy irradiation, and a photocatalyst adhesion changing layer containing at least a photocatalyst and a binder (hereinafter referred to as a second embodiment), at least a photocatalyst Change in wettability, which is a layer in which the contact angle between the photocatalyst treatment layer and the liquid decreases due to the action of the photocatalyst accompanying the energy irradiation formed on the photocatalyst treatment layer A photocatalyst-treated layer containing at least a photocatalyst, and an adhesion-changing layer in which the adhesiveness is changed by the action of the photocatalyst formed on the photocatalyst-treated layer. A photocatalyst treatment layer containing at least a photocatalyst, and a decomposition removal layer that is decomposed and removed by the action of the photocatalyst formed on the photocatalyst treatment layer. It is preferable that the layer is made of (hereinafter referred to as the fifth aspect).
[0049]
Hereinafter, each of the above aspects will be described separately.
[0050]
(1) First aspect
First, the first aspect in the characteristic change layer of this embodiment will be described. The first aspect of the characteristic change layer of this embodiment is a layer in which the contact angle with the liquid decreases due to the action of the photocatalyst accompanying energy irradiation, and is a photocatalyst wettability change layer containing at least a photocatalyst and a binder. .
[0051]
The photocatalyst wettability changing layer used in this embodiment is a layer in which the contact angle with the liquid decreases due to the action of the photocatalyst accompanying energy irradiation, and is at least limited as long as it contains at least a photocatalyst and a binder. Instead, this makes it possible to make the portion irradiated with energy a lyophilic region and the portion not irradiated with energy a lyophobic region.
[0052]
Among the photocatalyst wettability changing layers used in the present embodiment, in a portion not irradiated with energy, that is, in a liquid repellent region, the contact angle with a liquid of 40 mN / m is 10 ° or more, preferably a surface tension of 30 mN / m. The contact angle with the liquid is preferably 10 ° or more, particularly preferably the contact angle with the liquid having a surface tension of 20 mN / m is 10 ° or more. This is because the part that is not irradiated with energy is a part that requires liquid repellency, so when the contact angle with the liquid is small, the liquid repellency is not sufficient, for example, a conductive pattern described later, When the conductive pattern composition is applied by an ink jet method or the like and cured to form the conductive pattern composition, the conductive pattern composition may adhere to the liquid repellent region. This is because it becomes difficult to form.
[0053]
Further, the photocatalyst wettability changing layer has a contact angle with a liquid of 40 mN / m of less than 9 °, preferably a liquid with a surface tension of 50 mN / m, in a portion irradiated with energy, that is, a lyophilic region. A layer having an angle of 10 ° or less, particularly a contact angle with a liquid having a surface tension of 60 mN / m is preferably 10 ° or less. When the contact angle with the energy irradiated part, that is, the liquid in the lyophilic region is high, for example, the conductive pattern composition forming the conductive pattern may be repelled in the lyophilic region, For example, when the conductive pattern composition is applied by an inkjet method, the conductive pattern composition may not be sufficiently spread and spread, and it may be difficult to form a conductive pattern.
[0054]
In addition, the contact angle with the liquid here is measured using a contact angle measuring instrument (Kyowa Interface Science Co., Ltd. CA-Z type) with a liquid having various surface tensions (from the microsyringe to the liquid. 30 seconds after dropping), and the result was obtained or the result was graphed. In this measurement, as a liquid having various surface tensions, a wetting index standard solution manufactured by Pure Chemical Co., Ltd. was used.
[0055]
The photocatalyst wettability changing layer used in this embodiment contains fluorine in the photocatalyst wettability changing layer, and the fluorine content on the surface of the photocatalyst wettability changing layer is irradiated with energy to the photocatalyst wettability changing layer. In this case, the photocatalyst wettability change layer may be formed so as to be lower than that before energy irradiation due to the action of the photocatalyst, and is decomposed by the action of the photocatalyst due to energy irradiation, thereby changing the photocatalyst wettability. It may be formed to include a degrading material that can change the wettability on the layer.
[0056]
The action mechanism of the photocatalyst typified by titanium dioxide as described below in the photocatalyst wettability changing layer as described above is not necessarily clear, but carriers generated by light irradiation are not directly in contact with nearby compounds. It is considered that the chemical structure of organic matter is changed by reaction or reactive oxygen species generated in the presence of oxygen and water. In this embodiment, it is considered that this carrier acts on the binder compound in the photocatalyst wettability changing layer to change the wettability of the surface.
[0057]
Hereinafter, the photocatalyst, the binder, and other components constituting such a photocatalyst wettability changing layer will be described.
[0058]
a. photocatalyst
First, the photocatalyst used in this embodiment will be described. Examples of the photocatalyst used in this embodiment include titanium dioxide (TiO 2), which is known as an optical semiconductor.₂), Zinc oxide (ZnO), tin oxide (SnO)₂), Strontium titanate (SrTiO)₃), Tungsten oxide (WO₃), Bismuth oxide (Bi₂O₃), And iron oxide (Fe₂O₃1) or a mixture of two or more selected from these.
[0059]
In this embodiment, titanium dioxide is particularly preferably used because it has a high band gap energy, is chemically stable, has no toxicity, and is easily available. Titanium dioxide includes anatase type and rutile type, and both can be used in this embodiment, but anatase type titanium dioxide is preferable. Anatase type titanium dioxide has an excitation wavelength of 380 nm or less.
[0060]
Examples of such anatase type titanium dioxide include hydrochloric acid peptizer type anatase type titania sol (STS-02 manufactured by Ishihara Sangyo Co., Ltd. (average particle size 7 nm), ST-K01 manufactured by Ishihara Sangyo Co., Ltd.), nitric acid solution An anatase type titania sol (TA-15 manufactured by Nissan Chemical Co., Ltd. (average particle size 12 nm)) and the like can be mentioned.
[0061]
The smaller the particle size of the photocatalyst, the more effective the photocatalytic reaction occurs. The average particle size is preferably 50 nm or less, and it is particularly preferable to use a photocatalyst of 20 nm or less.
[0062]
The content of the photocatalyst in the photocatalyst wettability changing layer used in this embodiment can be set in the range of 5 to 60% by weight, preferably 20 to 40% by weight. The thickness of the photocatalyst wettability changing layer is preferably in the range of 0.05 to 10 μm.
[0063]
b. Binder
Next, the binder used in this embodiment will be described. In this embodiment, when the wettability change on the photocatalyst wettability change layer is performed by the photocatalyst acting on the binder itself (first form), it is decomposed by the action of the photocatalyst by energy irradiation, and thereby the photocatalyst wettability. When changing by incorporating a decomposition substance capable of changing the wettability on the property change layer into the photocatalyst wettability change layer (second embodiment) and combining them (third embodiment) It can be divided into three forms. The binder used in the first and third embodiments must have a function capable of changing the wettability on the photocatalyst wettability changing layer by the action of the photocatalyst. Such a function is not particularly necessary.
[0064]
Hereinafter, the binder used in the second embodiment, that is, the binder that does not particularly require the function of changing the wettability on the photocatalyst wettability changing layer by the action of the photocatalyst will be described, and then the first and third embodiments will be described. The binder used in the embodiment, that is, the binder having a function of changing the wettability on the photocatalyst wettability changing layer by the action of the photocatalyst will be described.
[0065]
The binder that does not particularly require the function of changing the wettability on the photocatalyst wettability changing layer by the action of the photocatalyst used in the second embodiment has a high binding energy such that the main skeleton is not decomposed by photoexcitation of the photocatalyst. If it has, it will not specifically limit. Specific examples include polysiloxanes that have no organic substituents or have some organic substituents, and these can be obtained by hydrolysis and polycondensation of tetramethoxysilane, tetraethoxysilane, and the like. .
[0066]
When such a binder is used, a decomposed substance that can be decomposed by the action of the photocatalyst by energy irradiation as an additive and thereby change the wettability on the photocatalyst wettability changing layer is incorporated into the photocatalyst wettability changing layer. It is essential to contain it.
[0067]
Next, the binder used in the first and third embodiments, which requires the function of changing the wettability on the photocatalyst wettability changing layer by the action of the photocatalyst, will be described. As such a binder, one having a high binding energy such that the main skeleton is not decomposed by photoexcitation of the photocatalyst and having an organic substituent that is decomposed by the action of the photocatalyst is preferable. (1) An organopolysiloxane that exerts great strength by hydrolyzing and polycondensing chloro or alkoxysilane by sol-gel reaction, etc. (2) An organopolysiloxane crosslinked with a reactive silicone excellent in water repellency and oil repellency Etc.
[0068]
In the case of (1) above, the general formula:
Y_nSiX_(4-n)
(Here, Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, X represents an alkoxyl group, an acetyl group or a halogen. N is an integer from 0 to 3. )
It is preferable that it is the organopolysiloxane which is a 1 type, or 2 or more types of hydrolysis condensate or cohydrolysis condensate of the silicon compound shown by these. Here, the number of carbon atoms of the group represented by Y is preferably in the range of 1 to 20, and the alkoxy group represented by X is a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. preferable.
[0069]
As the binder, polysiloxane containing a fluoroalkyl group can be particularly preferably used. Specifically, one or more of the following hydrocondensation condensates and cohydrolysis condensates of fluoroalkylsilanes can be used. And those generally known as fluorine-based silane coupling agents can be used.
CF₃(CF₂)₃CH₂CH₂Si (OCH₃)₃;
CF₃(CF₂)₅CH₂CH₂Si (OCH₃)₃;
CF₃(CF₂)₇CH₂CH₂Si (OCH₃)₃;
CF₃(CF₂)₉CH₂CH₂Si (OCH₃)₃;
(CF₃)₂CF (CF₂)₄CH₂CH₂Si (OCH₃)₃;
(CF₃)₂CF (CF₂)₆CH₂CH₂Si (OCH₃)₃;
(CF₃)₂CF (CF₂)₈CH₂CH₂Si (OCH₃)₃;
CF₃(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₃(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₅(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₇(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₃CH₂CH₂SiCH₃(OCH₃)₂;
CF₃(CF₂)₅CH₂CH₂SiCH₃(OCH₃)₂;
CF₃(CF₂)₇CH₂CH₂SiCH₃(OCH₃)₂;
CF₃(CF₂)₉CH₂CH₂SiCH₃(OCH₃)₂;
(CF₃)₂CF (CF₂)₄CH₂CH₂SiCH₃(OCH₃)₂;
(CF₃)₂CF (CF₂)₆CH₂CH₂Si CH₃(OCH₃)₂;
(CF₃)₂CF (CF₂)₈CH₂CH₂Si CH₃(OCH₃)₂;
CF₃(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₃(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₅(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₇(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₃CH₂CH₂Si (OCH₂CH₃)₃;
CF₃(CF₂)₅CH₂CH₂Si (OCH₂CH₃)₃;
CF₃(CF₂)₇CH₂CH₂Si (OCH₂CH₃)₃;
CF₃(CF₂)₉CH₂CH₂Si (OCH₂CH₃)₃;
CF₃(CF₂)₇SO₂N (C₂H₅) C₂H₄CH₂Si (OCH₃)₃
By using a polysiloxane containing a fluoroalkyl group as described above as a binder, the liquid repellency of the non-irradiated part of the photocatalyst wettability changing layer is greatly improved, and a conductive pattern composition for forming a conductive pattern is obtained. Expresses the function of preventing adhesion.
[0070]
Examples of the reactive silicone (2) include compounds having a skeleton represented by the following general formula.
[0071]
[Chemical 1]

[0072]
However, n is an integer greater than or equal to 2, R¹, R²Each represents a substituted or unsubstituted alkyl, alkenyl, aryl or cyanoalkyl group having 1 to 10 carbon atoms, and 40% or less of the total is vinyl, phenyl or phenyl halide in a molar ratio. R¹, R²Is preferably a methyl group because the surface energy becomes the smallest, and the methyl group is preferably 60% or more by molar ratio. In addition, the chain end or side chain has at least one reactive group such as a hydroxyl group in the molecular chain.
[0073]
In addition to the above organopolysiloxane, a stable organosilicon compound that does not undergo a crosslinking reaction, such as dimethylpolysiloxane, may be mixed in the binder.
[0074]
c. Decomposition substance
In the second and third embodiments, the photocatalyst wettability changing layer is further decomposed by a photocatalyst wettability changing layer which is further decomposed by the action of the photocatalyst by energy irradiation and can change the wettability on the photocatalyst wettability changing layer. It is necessary to contain. That is, when the binder itself does not have a function of changing the wettability on the photocatalyst wettability changing layer, and when such a function is insufficient, the above-described photocatalyst wettability is added by adding a decomposition substance as described above. It causes a change in wettability on the change layer or assists such a change.
[0075]
Examples of such a decomposing substance include a surfactant having a function of decomposing by the action of the photocatalyst and changing the wettability of the photocatalyst wettability changing layer surface by being decomposed. Specifically, hydrocarbons such as NIKKOL BL, BC, BO, BB series manufactured by Nikko Chemicals Co., Ltd., ZONYL FSN, FSO manufactured by DuPont, Surflon S-141, 145 manufactured by Asahi Glass Co., Ltd., Dainippon Megafac F-141, 144 manufactured by Ink Chemical Industry Co., Ltd., Footgent F-200, F251 manufactured by Neos Co., Ltd., Unidyne DS-401, 402 manufactured by Daikin Industries, Ltd., Fluorard FC-170 manufactured by 3M Co., Ltd. Fluorine-based or silicone-based nonionic surfactants such as 176, and cationic surfactants, anionic surfactants, and amphoteric surfactants can also be used.
[0076]
Besides surfactants, polyvinyl alcohol, unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene diene monomer, epoxy resin, phenol resin, polyurethane, melamine resin, polycarbonate, polyvinyl chloride, polyamide, polyimide Styrene butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, nylon, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, polyisoprene, oligomers, polymers, and the like.
[0077]
d. Fluorine content
Further, in this embodiment, the photocatalyst wettability changing layer contains fluorine, and the fluorine content on the surface of the photocatalyst wettability changing layer is effective when the photocatalyst wettability changing layer is irradiated with energy. Thus, it is preferable that the photocatalyst wettability changing layer is formed so as to be lower than that before energy irradiation.
[0078]
If it is a photocatalyst wettability change layer which has such a characteristic, the pattern which consists of a part with little content of fluorine can be easily formed by irradiating energy with a pattern so that it may mention later. Here, fluorine has an extremely low surface energy. Therefore, the surface of a substance containing a large amount of fluorine has a smaller critical surface tension. Therefore, the critical surface tension of the portion having a small fluorine content is larger than the critical surface tension of the surface of the portion having a large fluorine content. This means that the portion with a low fluorine content is a lyophilic region compared to the portion with a high fluorine content. Therefore, forming a pattern composed of a portion having a lower fluorine content than the surrounding surface forms a pattern of a lyophilic region in the liquid repellent region.
[0079]
Therefore, when such a photocatalyst wettability changing layer is used, the pattern of the lyophilic region can be easily formed in the liquid repellent region by irradiating the pattern with energy. This is because, when a conductive pattern composition is applied, a high-definition conductive pattern can be formed.
[0080]
As described above, the fluorine content contained in the photocatalyst wettability change layer containing fluorine is the fluorine content in the lyophilic region formed by irradiation of energy and having a low fluorine content. When the fluorine content of the unexposed portion is 100, it is preferably 10 or less, preferably 5 or less, particularly preferably 1 or less.
[0081]
By setting it within such a range, it is possible to make a large difference in lyophilicity between the energy-irradiated portion and the unirradiated portion. Therefore, for example, by attaching a conductive pattern composition to such a photocatalyst wettability changing layer, it becomes possible to accurately form a conductive pattern only in a lyophilic region having a reduced fluorine content. This is because a good wiring board can be obtained. This rate of decrease is based on weight.
[0082]
The fluorine content in such a photocatalytic wettability changing layer can be measured by various commonly used methods, such as X-ray photoelectron spectroscopy (ESCA). Electron Spectroscopy for Chemical Analysis)), and any method that can quantitatively measure the amount of fluorine on the surface, such as X-ray fluorescence analysis and mass spectrometry, is not particularly limited.
[0083]
In this embodiment, titanium dioxide is preferably used as the photocatalyst as described above. When titanium dioxide is used in this manner, the content of fluorine contained in the photocatalytic wettability changing layer is X When analyzed and quantified by means of linear photoelectron spectroscopy, the fluorine (F) element is 500 or more, preferably 800 or more, particularly preferably 1200 or more when the titanium (Ti) element is 100. (F) It is preferable that the element is contained in the surface of the photocatalyst wettability changing layer.
[0084]
By including fluorine (F) in the photocatalyst wettability changing layer to such a degree, it becomes possible to sufficiently reduce the critical surface tension on the photocatalyst wettability changing layer, thereby ensuring liquid repellency on the surface. It is possible to increase the difference in wettability with the lyophilic region on the surface of the pattern portion where the fluorine content is reduced by pattern irradiation with energy, and the accuracy of the finally obtained wiring board can be improved. Because.
[0085]
Further, in such a wiring substrate, the fluorine content in the parent ink region formed by pattern irradiation with energy is 50 or less, preferably when the titanium (Ti) element is 100, preferably It is preferably contained in a ratio of 20 or less, particularly preferably 10 or less.
[0086]
If the fluorine content in the photocatalyst wettability changing layer can be reduced to this extent, sufficient lyophilicity can be obtained for forming a wiring board, and the liquid repellency of the portion where the energy is not irradiated is obtained. Due to the difference in wettability, the wiring board can be formed with high accuracy, and a multilayer wiring board with high utility value can be obtained.
[0087]
e. Method for producing photocatalytic wettability changing layer
As described above, when the organopolysiloxane is used as a binder, the photocatalyst wettability changing layer is formed by dispersing the photocatalyst and the binder organopolysiloxane in a solvent together with other additives as necessary. Can be formed by applying the coating solution onto a substrate. As the solvent to be used, alcohol-based organic solvents such as ethanol and isopropanol are preferable. The coating can be performed by a known coating method such as spin coating, spray coating, dip coating, roll coating or bead coating. When an ultraviolet curable component is contained as a binder, the photocatalytic wettability changing layer can be formed by irradiating with ultraviolet rays and performing a curing treatment.
[0088]
(2) Second aspect
Next, the second aspect in the characteristic change layer of this embodiment will be described. The characteristic change layer in this embodiment is a layer in which the adhesion changes due to the action of the photocatalyst accompanying energy irradiation, and is a photocatalyst adhesion change layer containing at least a photocatalyst and a binder.
[0089]
The photocatalyst adhesiveness change layer used in this embodiment is a layer whose adhesiveness changes due to the action of the photocatalyst contained in the photocatalyst adhesiveness change layer itself upon energy irradiation, and a layer containing at least a photocatalyst and a binder. If it is, it will not specifically limit, However, It is preferable that it is a layer from which adhesiveness changes so that the adhesiveness with the thing in the photocatalyst adhesiveness change layer surface may improve.
[0090]
Thus, by using a photocatalyst adhesiveness change layer in which the adhesiveness changes so that the adhesiveness with an object is improved by energy irradiation, the energy irradiated part is a region with good adhesiveness, and no energy is irradiated. This makes it possible to make the portion a close contact inhibition region. Taking advantage of this difference in adhesion, for example, when a conductive pattern composition for forming a conductive pattern is deposited on the entire surface, the conductive pattern composition adheres only to the good adhesion region, and the adhesion inhibition region is formed. Since the conductive pattern composition does not adhere, it is possible to easily remove the conductive pattern composition in the adhesion-inhibiting region, and it is possible to easily form the conductive pattern described later only in the adhesive region. It becomes.
[0091]
Here, the region having good adhesion refers to a region having good adhesion to an object, and refers to a region having good adhesion to a conductive pattern composition for forming a conductive pattern described later. Further, the adhesion-inhibiting region is a region having poor adhesion to an object, and refers to a region having poor adhesion to the conductive pattern composition.
[0092]
The photocatalyst adhesiveness change layer in the present embodiment contains an adhesion inhibitory substance, and is a layer from which the adhesiveness inhibitory substance is removed by the action of the photocatalyst accompanying the energy irradiation (first form), and energy irradiation. In some cases, irregularities are formed on the photocatalyst adhesiveness change layer by the action of the photocatalyst, and the adhesiveness is physically improved (second form). Hereinafter, each form will be described separately.
[0093]
First, the first embodiment will be described. The photocatalyst adhesiveness change layer of this embodiment contains a substance that inhibits the adhesiveness, and in this adhesion inhibitory substance that is not irradiated with energy, the conductivity applied by, for example, vapor deposition is used. It is possible to inhibit the pattern composition from adhering. In addition, by the action of the photocatalyst accompanying the energy irradiation, the adhesion-inhibiting substance is removed, whereby the adhesion is improved and it is possible to form a region with good adhesion.
[0094]
Specifically, as the first form of the photocatalyst adhesiveness change layer, it is possible to use a photocatalyst and a binder similar to those described in the above-mentioned photocatalyst wettability change layer section of the first aspect. is there.
[0095]
Next, the second form will be described. The photocatalyst adhesiveness change layer of this embodiment is a layer in which irregularities are formed on the surface by the action of the photocatalyst accompanying energy irradiation, and improves the adhesion of the conductive pattern composition by the anchor effect due to the irregularities on the surface. Is possible. In addition, in the adhesion-inhibiting region that is not irradiated with energy, since the unevenness is not formed, it is difficult for the conductive pattern composition to adhere. It can be easily formed.
[0096]
Specifically, polyethylene terephthalate, polyvinyl alcohol, polycarbonate, methyl methacrylate homopolymer or copolymer, polystyrene, polyethylene, polypropylene, polyester, PTFE, etc. are used for the second embodiment of the photocatalyst adhesion changing layer. Is possible.
[0097]
(3) Third aspect
Next, a third aspect in the characteristic change layer of this embodiment will be described. The characteristic change layer of this embodiment includes a photocatalyst treatment layer containing at least a photocatalyst, and a wettability change layer in which a contact angle with a liquid is lowered by the action of the photocatalyst accompanying energy irradiation formed on the photocatalyst treatment layer. It is a layer consisting of
[0098]
In this aspect, since the characteristic change layer is composed of the photocatalyst treatment layer and the wettability change layer, the photocatalyst in the photocatalyst treatment layer is activated and formed on the photocatalyst treatment layer with energy irradiation. The wettability of the surface of the wettability changing layer is changed. Hereinafter, the wettability changing layer and the photocatalyst processing layer will be described.
[0099]
a. Photocatalyst treatment layer
The photocatalyst treatment layer used in this embodiment contains at least a photocatalyst, and when the photocatalyst treatment layer has a binder, the photocatalyst treatment layer is the same as the photocatalyst treatment layer described in the first embodiment. Is omitted. However, in this embodiment, since the wettability on the photocatalyst treatment layer does not need to change, the first embodiment can be used even when the wettability does not change due to the photocatalyst acting on the binder itself. Thus, it is not necessary to include a decomposition substance in the photocatalyst processing layer. Moreover, since the manufacturing method of the photocatalyst processing layer when it has a binder is the same as that of the 1st aspect mentioned above, the description about this is also abbreviate | omitted.
[0100]
On the other hand, examples of the method for forming the photocatalyst processing layer without the binder include a method using a vacuum film forming method such as a sputtering method, a CVD method, and a vacuum deposition method. By forming the photocatalyst treatment layer by the vacuum film formation method, it is possible to obtain a photocatalyst treatment layer that is a uniform film and contains only the photocatalyst, thereby uniformly changing the wettability on the wettability changing layer. In addition, since it consists of only a photocatalyst, it is possible to efficiently change the wettability on the wettability changing layer as compared with the case where a binder is used.
[0101]
In addition, as another method for forming a photocatalyst treatment layer composed only of a photocatalyst, for example, when the photocatalyst is titanium dioxide, amorphous titania is formed on a base material, and then a phase change is made to crystalline titania by firing. Can be mentioned. As the amorphous titania used here, for example, hydrolysis, dehydration condensation, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-propoxytitanium, tetrabutoxytitanium, titanium inorganic salts such as titanium tetrachloride and titanium sulfate, An organic titanium compound such as tetramethoxytitanium can be obtained by hydrolysis and dehydration condensation in the presence of an acid. Next, it can be modified to anatase titania by baking at 400 ° C. to 500 ° C. and modified to rutile type titania by baking at 600 ° C. to 700 ° C.
[0102]
b. Wetting change layer
Next, the wettability changing layer used in this embodiment will be described.
[0103]
The wettability changing layer used in this embodiment is not particularly limited as long as the contact angle with the liquid is reduced by the action of the photocatalyst accompanying the energy irradiation, but the energy irradiation layer is not particularly limited. In a portion where there is no liquid repellency, that is, a contact angle with a liquid of 40 mN / m is 10 ° or more, preferably a contact angle with a liquid with a surface tension of 30 mN / m is 10 ° or more, particularly a surface tension of 20 mN / m. The contact angle with the liquid is preferably 10 ° or more. This is because the part that is not irradiated with energy is a part that requires liquid repellency, so when the contact angle with the liquid is small, the liquid repellency is not sufficient, for example, a conductive pattern described later, When the conductive pattern composition is applied by an ink jet method or the like and cured to form the conductive pattern composition, the conductive pattern composition may adhere to the liquid repellent region. This is because it becomes difficult to form.
[0104]
The wettability changing layer has a contact angle with a liquid with a surface tension of less than 9 °, preferably with a liquid with a surface tension of 50 mN / m, in a portion irradiated with energy, that is, in a lyophilic region. Is preferably a layer such that the contact angle with a liquid having a surface tension of 60 mN / m is 10 ° or less. When the contact angle with the energy irradiated part, that is, the liquid in the lyophilic region is high, for example, the conductive pattern composition forming the conductive pattern may be repelled in the lyophilic region, For example, when the conductive pattern composition is applied by an inkjet method, the conductive pattern composition may not be sufficiently spread and spread, and it may be difficult to form a conductive pattern.
[0105]
In addition, the contact angle with the liquid here is the value measured similarly to the method demonstrated in the 1st aspect.
[0106]
The wettability changing layer is not particularly limited as long as the wettability is changed by the action of the photocatalyst treatment layer, but is the same material as the binder in the photocatalyst treatment layer of the first aspect described above. It is preferable to form. Since the material and the forming method of the wettability changing layer when formed with the same material as the binder in the photocatalyst treatment layer of the first aspect are the same as those of the first aspect, The description in is omitted.
[0107]
In this embodiment, the thickness of the wettability changing layer is preferably 0.001 μm to 1 μm, particularly preferably in the range of 0.01 to 0.1 μm, in consideration of the change rate of wettability by the photocatalyst. is there.
[0108]
By using the wettability changing layer of the component described above in this aspect, the action of the photocatalyst in the adjacent photocatalyst treatment layer is used to oxidize, decompose, etc. the organic groups and additives that are part of the component. By changing the wettability of the energy-irradiated part to make it lyophilic, it is possible to make a large difference in wettability with the non-energy-irradiated part.
[0109]
The wettability changing layer can contain the same fluorine in the same manner as described in the section “Fluorine content” in the description of the photocatalyst treatment layer in the first aspect.
[0110]
In this embodiment, it is not necessary to contain a photocatalyst in the wettability changing layer. In this case, the possibility that the conductive pattern is influenced by the photocatalyst over time can be reduced.
[0111]
(4) Fourth aspect
Next, a fourth aspect of the characteristic change layer in this embodiment will be described. The characteristic change layer in this embodiment is a layer composed of a photocatalyst treatment layer containing at least a photocatalyst and an adhesion change layer whose adhesion changes due to the action of the photocatalyst formed on the photocatalyst treatment layer.
[0112]
According to this aspect, since the characteristic change layer is constituted by the photocatalyst treatment layer and the adhesion change layer, the photocatalyst in the photocatalyst treatment layer is excited by energy irradiation, and thereby the adhesion property is increased. The adhesiveness of the change layer changes.
[0113]
Since the photocatalyst treatment layer used in this embodiment is the same as the photocatalyst treatment layer in the third embodiment described above, the description thereof is omitted here, and the adhesion changing layer will be described below.
[0114]
The adhesiveness changing layer used in this embodiment is not particularly limited as long as the adhesiveness is changed by the action of the photocatalyst treatment layer, but the adhesiveness is improved by the action of the photocatalyst accompanying energy irradiation. A layer is preferred. The adhesion changing layer is preferably formed of the same material as the binder in the photocatalyst adhesion changing layer of the second aspect described above. In addition, since the material and the forming method of the adhesion changing layer when formed of the same material as the binder in the photocatalyst adhesion changing layer of the second aspect are the same as those of the second aspect. Explanation here is omitted.
[0115]
In this embodiment, the thickness of the adhesion changing layer is preferably from 0.001 μm to 1 μm, particularly preferably in the range of 0.01 to 0.1 μm, in consideration of the rate of change in adhesion by the photocatalyst. is there.
[0116]
(5) Fifth aspect
Next, a fifth aspect in the characteristic change layer of this embodiment will be described. The characteristic change layer in this embodiment is a layer composed of a photocatalyst treatment layer containing at least a photocatalyst and a decomposition removal layer that is decomposed and removed by the action of the photocatalyst formed on the photocatalyst treatment layer.
[0117]
The characteristic change layer of this aspect is composed of the photocatalyst treatment layer and the decomposition removal layer, whereby the photocatalyst in the photocatalyst treatment layer is excited with energy irradiation, and the decomposition removal layer is decomposed and removed. This makes it possible to form a pattern having irregularities on the photocatalyst treatment layer.
[0118]
Since the photocatalyst treatment layer used in this embodiment is the same as that described in the third embodiment, description thereof will be omitted and the decomposition removal layer will be described below.
[0119]
The decomposition / removal layer used in this embodiment is particularly limited as long as the decomposition / removal layer of the portion irradiated with energy is decomposed and removed by the action of the photocatalyst in the photocatalyst treatment layer when irradiated with energy. is not.
[0120]
As described above, since the portion irradiated with energy is decomposed and removed by the action of the photocatalyst, the decomposition / removal layer has a pattern composed of a portion with and without the decomposition / removal layer without performing a development process or a washing step, that is, has an unevenness A pattern can be formed.
[0121]
This decomposition / removal layer is oxidatively decomposed and vaporized by the action of the photocatalyst by energy irradiation, and is therefore removed without any special post-treatment such as development / washing process. Depending on the material, a cleaning process or the like may be performed.
[0122]
Moreover, it is preferable that the decomposition / removal layer used in this embodiment not only forms irregularities, but also the contact angle with the liquid is higher than that of the exposed member surface. As a result, the region where the decomposition / removal layer is decomposed and removed can be defined as a lyophilic region, and the region where the decomposition / removal layer remains can be defined as a liquid-repellent region, and various conductive patterns can be formed. Because it becomes. At this time, the member exposed by the decomposition removal layer being decomposed and removed is the photocatalyst treatment layer.
[0123]
Here, in the decomposition / removal layer of this embodiment, that is, the liquid repellent region, the contact angle with a liquid of 40 mN / m is 10 ° or more, preferably the contact angle with a liquid with a surface tension of 50 mN / m is 10 ° or less. In particular, a layer having a contact angle with a liquid having a surface tension of 60 mN / m of 10 ° or less is preferable. This is because the portion that is not irradiated with energy is a portion that requires liquid repellency in this embodiment, and therefore, when the contact angle with the liquid is small, the liquid repellency is not sufficient, for example, an ink jet method or the like As a result, when the conductive pattern composition is applied, there is a possibility that the conductive pattern composition adheres to the liquid-repellent region, which makes it difficult to obtain a high-definition wiring board.
[0124]
Further, in the photocatalyst treatment layer exposed by energy irradiation, that is, the lyophilic region, the contact angle with the liquid of 40 mN / m is less than 9 °, preferably the surface tension is 50 mN / m. It is preferable that the layer has a contact angle with a liquid of m of 10 ° or less, particularly a contact angle with a liquid with a surface tension of 60 mN / m of 10 ° or less. When the contact angle with the conductive pattern composition in the portion irradiated with energy, that is, the lyophilic region is high, the conductive pattern composition is repelled even in the lyophilic region when the conductive pattern composition is applied. This is because, for example, it may be difficult to form a conductive pattern on the lyophilic region by an inkjet method or the like. Here, the contact angle with the liquid is a value measured by the method described in the first embodiment.
[0125]
Specific examples of the film that can be used for the decomposition removal layer of this embodiment include a film made of a fluorine-based or hydrocarbon-based resin having liquid repellency. These fluorine-based and hydrocarbon-based resins are not particularly limited as long as they have liquid repellency, and these resins are dissolved in a solvent, for example, a general composition such as a spin coating method. It can be formed by a film method.
[0126]
In addition, in this embodiment, since a functional thin film, that is, a self-assembled monomolecular film, a Langmuir-Brocket film, an alternating adsorption film, and the like can be used, a film without defects can be formed. It can be said that it is more preferable to use such a film forming method.
[0127]
Here, the self-assembled monomolecular film, the Langmuir-Brocket film, and the alternating adsorption film used in this embodiment will be specifically described.
[0128]
(I) Self-assembled monolayer
Although the inventors do not know the existence of an official definition of self-assembled monolayer, a commentary on what is generally recognized as a self-assembled membrane is, for example, a review by Abraham Ulman. “Formation and Structure of Self-Assembled Monolayers”, Chemical Review, 96, 1533-1554 (1996) is excellent. Referring to this review, a self-assembled monolayer can be said to be a monolayer formed as a result of adsorbing and binding (self-organizing) appropriate molecules to the appropriate substrate surface. Examples of materials capable of forming a self-assembled film include surfactant molecules such as fatty acids, organosilicon molecules such as alkyltrichlorosilanes and alkylalkoxides, organic sulfur molecules such as alkanethiols, and alkyl phosphates. And organic phosphoric acid molecules. The common commonality of the molecular structure is that there is a functional group that has a relatively long alkyl chain and interacts with the substrate surface at one molecular end. The portion of the alkyl chain is a source of intermolecular force when molecules are packed two-dimensionally. However, the example shown here has the simplest structure, having a functional group such as an amino group or a carboxyl group at the other end of the molecule, an alkylene chain part having an oxyethylene chain, or a fluorocarbon chain. Self-assembled monolayers composed of various molecules such as those of complex type chains have been reported. There is also a composite type self-assembled monolayer composed of a plurality of molecular species. In addition, recently, a polymer having a plurality of functional groups (which may have one functional group) or a linear polymer (which may have a branched structure) as represented by dendrimers has been developed. One layer formed on the surface of the substrate (the latter is collectively referred to as a polymer brush) may be considered as a self-assembled monolayer. In this embodiment, these are also included in the self-assembled monolayer.
[0129]
(Ii) Langmuir-Blodgett membrane
If the Langmuir-Blodgett film used in this embodiment is formed on a substrate, there is no significant difference in form from the above-described self-assembled monolayer. It can be said that the Langmuir-Blodgett film is characterized by its formation method and the advanced two-dimensional molecular packing properties (high orientation and high order). That is, in general, Langmuir-Blodgett film-forming molecules are first developed on the gas-liquid interface, and the developed film is condensed by the trough to change into a highly packed condensed film. In practice, this is transferred to a suitable substrate and used. It is possible to form a monomolecular film to a multilayer film of an arbitrary molecular layer by the method outlined here. Further, not only low molecules but also polymers and colloidal particles can be used as the film material. Recent examples of the application of various materials are described in detail in the review by Tokuharu Miyashita et al. “Prospects for Nanotechnology for the Creation of Soft Nanodevices” Polymer Vol. 50, September, 644-647 (2001).
[0130]
(Iii) Alternate adsorption film
In general, an alternating adsorption film (Layer-by-Layer Self-Assembled Film) is made by adsorbing and bonding a material having at least two functional groups with positive or negative charges sequentially onto a substrate. It is a film formed by stacking. Since a material having a large number of functional groups has many advantages such as increased strength and durability of the membrane, recently, an ionic polymer (polymer electrolyte) is often used as a material. Further, particles having surface charges such as proteins, metals and oxides, so-called “colloid particles” are also frequently used as film-forming substances. More recently, membranes that actively utilize weaker interactions than ionic bonds such as hydrogen bonds, coordination bonds, and hydrophobic interactions have been reported. A relatively recent example of alternating adsorption films is slightly biased towards materials with electrostatic interaction as the driving force, but a review by Paula T. Hammond “Recent Explorations in Electrostatic Multilayer Thin Film Assembly” Current Opinion in Colloid & Interface Science, 4, 430-442 (2000). The alternate adsorption film can be described by taking the simplest process as an example, by repeating the adsorption-washing of a material having a positive (negative) charge-adsorption-washing of a material having a negative (positive) charge a predetermined number of times. It is a film to be formed. As with Langmuir-Blodgett membranes, no development-condensation-transfer operations are required. Further, as apparent from the difference in these production methods, the alternate adsorption film generally does not have a two-dimensional high orientation / high order like the Langmuir-Blodgett film. However, the alternate adsorption film and its manufacturing method have advantages over conventional film formation methods, such as the ability to easily form a dense film without defects and the ability to form even fine irregular surfaces, tube inner surfaces, and spherical surfaces. Have many.
[0131]
Further, the film thickness of the decomposition removal layer is not particularly limited as long as it is a film thickness that can be decomposed and removed by the energy applied upon irradiation of energy described later. The specific film thickness varies greatly depending on the type of energy to be irradiated, the material of the decomposition removal layer, and the like, but is generally within the range of 0.001 μm to 1 μm, particularly 0.01 μm to 0.001. It is preferable to be within the range of 1 μm.
[0132]
(Pattern whose characteristics of the characteristic change layer have changed)
Next, a pattern in which the characteristics of the characteristic change layer have changed will be described. In this embodiment, in order to form a conductive pattern, which will be described later, along a pattern in which the characteristics of the characteristic change layer have changed, a pattern in which the characteristics of the characteristic change layer have changed is formed.
[0133]
In the method for forming a pattern in which the characteristics of the characteristic change layer in the present embodiment are changed, the pattern having a characteristic changed on the surface of the characteristic change layer is formed by irradiating the characteristic change layer with energy from a predetermined direction. The method is used.
[0134]
The energy irradiation (exposure) referred to in the present invention is a concept including irradiation of any energy beam capable of changing the characteristics of the characteristic change layer, and is not limited to visible light irradiation. .
[0135]
Usually, the wavelength of light used for such energy irradiation is set in the range of 400 nm or less, preferably in the range of 380 nm or less. This is because, as described above, titanium dioxide is preferably used for the photocatalyst, and light having the above-described wavelength is preferable as energy for activating the photocatalytic action by the titanium dioxide.
[0136]
Examples of light sources that can be used for such energy irradiation include mercury lamps, metal halide lamps, xenon lamps, excimer lamps, and various other light sources.
[0137]
In addition to the method of performing pattern irradiation through a photomask using the light source as described above, it is also possible to use a method of drawing and irradiating in a pattern using a laser such as excimer or YAG.
[0138]
Further, the energy irradiation amount at the time of the energy irradiation is an irradiation amount necessary for the characteristic change layer to change its characteristics by the action of the photocatalyst.
[0139]
In this case, it is preferable in that the energy can be increased while heating the photocatalyst, so that the sensitivity can be increased and the wettability can be changed efficiently. Specifically, it is preferable to heat within a range of 30 ° C to 80 ° C.
[0140]
(Conductive pattern)
Next, the conductive pattern used in this embodiment will be described. As long as the conductive pattern used in this embodiment is a pattern having conductivity formed along the pattern in which the characteristics of the characteristic change layer have changed, the shape and material of the pattern are particularly limited. is not. Specifically, as a material used for the conductive pattern in the present embodiment, copper, gold, silver, nickel, aluminum, palladium, lead, tin, and a powdered metal or alloy containing one or more of these metals In addition, a metal ink composed of a binder resin, a dispersion material, and an organic solvent can be used, and among these, a metal ink using copper and silver is preferable.
[0141]
In addition, the method for forming the conductive pattern of the present embodiment is appropriately selected according to the change in the characteristics of the characteristic change layer described above. Specifically, the vapor deposition method, electroless plating, dip coating, roll coating, and the like. Examples thereof include coating means such as blade coating and spin coating, and means such as nozzle ejection means including ink jet and electrolytic jet.
[0142]
For example, when the property change layer is a photocatalyst wettability change layer or a wettability change layer, a lyophilic region and a lyophobic region are formed. A method of applying a metal colloid solution by an ink jet method or a roll coating method, a method of applying a metal paste by an electrolytic jet method, and the like only in the region.
[0143]
In addition, when the characteristic change layer is a photocatalyst adhesion change layer or an adhesion change layer, a good adhesion region and an adhesion inhibition region are formed. For example, a metal is attached to the entire surface by vapor deposition or the like. By removing the metal on the adhesion-inhibiting region that is not in close contact, it is possible to form a conductive pattern only on the region with good adhesion.
[0144]
Further, when the property change layer is a decomposition removal layer, a method of applying a metal colloid solution by an ink jet method using a concavity and convexity formed on the surface, a method of applying a metal paste by an electrolytic jet method, etc. Is mentioned.
[0145]
(Wiring board)
Next, the wiring board in this embodiment will be described. The wiring board in this embodiment includes the characteristic change layer and the conductive pattern formed along the pattern in which the characteristic of the characteristic change layer is changed. The wiring pattern and the like are particularly limited. It is not something.
[0146]
(Multilayer wiring board)
Next, the multilayer wiring board of this embodiment will be described. The multilayer wiring board of this embodiment is one in which at least two layers of the above wiring boards are laminated, and among them, it is preferable that three to five layers are laminated.
[0147]
In this embodiment, a multilayer wiring board having a high-definition conductive pattern can be obtained by stacking the wiring boards having the above-described high-definition conductive pattern.
[0148]
Further, in the multilayer wiring board of the present embodiment, after the photocatalyst treatment layer side substrate having the photocatalyst treatment layer containing the photocatalyst and the substrate is disposed with a gap so that the photocatalyst treatment layer is 200 μm or less, A wiring board comprising a characteristic reaction layer (characterized later) whose characteristics are changed by energy irradiation from a predetermined direction and a conductive pattern formed along a pattern whose characteristics of the characteristic reaction layer are changed. At least one layer may be laminated.
[0149]
In addition, a conductive connector as described later may be provided between the conductive patterns of adjacent wiring boards, and when the characteristic change layer in the lowermost layer has no self-supporting property, the multilayer wiring board has a strength. For example, when a multilayer wiring board is required, the multilayer wiring board may be formed on a base material to be described later. Each configuration will be described below.
[0150]
(Base material)
Here, the base material used for this embodiment is demonstrated. In this embodiment, for example, the base material is used when the characteristic change layer formed in the lowermost layer portion of the multilayer wiring board is not self-supporting or when the multilayer wiring board requires strength, As shown in FIG. 2, the characteristic changing layer 1 of the lowermost wiring board in the multilayer wiring board is provided on the base material 4.
[0151]
Such a substrate is appropriately selected according to the use of the finally obtained multilayer wiring board, for example, in the case of a normal printed wiring board or the like, a generally used material Specifically, a paper laminate resin laminate, a glass cloth / glass nonwoven fabric resin laminate, ceramic, metal or the like can be used. Moreover, in a flexible wiring board, it is also possible to use the resin-made film which has flexibility as a base material.
[0152]
(Conductive connector)
Next, the conductive connector in this embodiment will be described. In the multilayer wiring board of this embodiment, at a portion formed of a conductive material provided to electrically connect conductive patterns of adjacent wiring boards or wiring boards having characteristic reaction layers described later. There may be a certain conductive connector. For example, as shown in FIG. 3, between the conductive part 2 in the wiring board 3 and the conductive part 2 'in the adjacent wiring board 3', a conductive material is used. It is formed. In this embodiment, as long as the conductive connector can be electrically connected, the formation method and the like are not particularly limited. Preferably, the through hole formed in the characteristic reaction layer is formed by filling a conductive material.
[0153]
Here, the through hole in the present embodiment is for forming a conductive connector that electrically connects the conductive pattern and the conductive pattern directly below the conductive pattern and the characteristic change layer. In addition, it refers to a hole provided in the characteristic change layer or the characteristic reaction layer described later.
[0154]
Here, in this embodiment, since the above-described characteristic change layer or characteristic reaction layer is included in the wiring board, it is possible to easily form a through hole by utilizing these characteristic changes.
[0155]
For example, when the property change layer is a photocatalyst wettability change layer or a wettability change layer, energy is applied to the pattern forming the through hole to form a lyophilic region in the pattern, and the lyophilic liquid For example, by applying an alkaline solution or the like on the conductive region, etching can be performed, and a high-definition through hole can be easily formed.
[0156]
In addition, since the material and formation method used for the conductive connector of this embodiment can use the same thing as the conductive pattern mentioned above, description here is abbreviate | omitted.
[0157]
(Wiring board with characteristic reaction layer)
Next, a wiring board having a characteristic reaction layer will be described. In the present embodiment, the multilayer wiring board includes a photocatalyst treatment layer containing a photocatalyst and a photocatalyst treatment layer side substrate having a substrate, which are arranged with a gap so that the photocatalyst treatment layer has a thickness of 200 μm or less. At least one layer of a wiring board comprising a characteristic reaction layer whose characteristics change when irradiated with energy from a direction and a conductive pattern formed along a pattern whose characteristics change in the characteristic reaction layer is laminated. Also good.
[0158]
Hereinafter, the wiring board having this characteristic reaction layer will be described for each configuration.
[0159]
(1) Characteristic reaction layer
First, the characteristic reaction layer used for the wiring board having the characteristic reaction layer of this embodiment will be described. The characteristic reaction layer used for the wiring board having the characteristic reaction layer of the present embodiment is a gap between the photocatalyst treatment layer containing the catalyst and the photocatalyst treatment layer side substrate having the substrate so that the photocatalyst treatment layer is 200 μm or less. In this layer, the characteristics change when irradiated with energy from a predetermined direction, and a conductive pattern can be formed along the pattern with the changed characteristics.
[0160]
For the wiring board having the characteristic reaction layer in this embodiment, for example, as shown in FIG. 4, the photocatalyst treatment layer side substrate 7 having the base 6 and the photocatalyst treatment layer 5 is replaced with the characteristic reaction layer 15 and the photocatalyst treatment layer 5. Is a layer in which characteristics on the characteristic reaction layer 15 change by irradiating energy 9 in a pattern from a predetermined direction using, for example, a photomask 8 or the like. is there.
[0161]
In this embodiment, the electrical resistance of the characteristic reaction layer is 1 × 10.⁸Ω · cm to 1 × 10¹⁸Ω · cm, especially 1 × 10¹⁵Ω · cm to 1 × 10¹⁸It is preferably within the range of Ω · cm. This is because, when the electric resistance of the characteristic reaction layer is lower than the above range, it becomes difficult to use a conductive pattern, which will be described later, as the electric wiring when the multilayer wiring board is formed.
[0162]
In this embodiment, the characteristic reaction layer is preferably a layer etched with a liquid, and more preferably a layer etched with an alkaline solution. As a result, for example, when a multilayer wiring board has a conductive connector for connecting between adjacent conductive patterns, when forming a through hole for forming this conductive connector, the pattern has changed in characteristics. In addition, it is possible to perform etching easily by applying a liquid, and more efficiently if the liquid used for the etching is an alkaline solution. .
[0163]
In this embodiment, the characteristic reaction layer is a wettability changing layer in which the wettability changes so that the contact angle with the liquid is lowered by the action of the photocatalyst accompanying energy irradiation from the viewpoint of forming a conductive pattern. In some cases, the adhesive layer is preferably an adhesive change layer in which the adhesiveness is changed by the action of the photocatalyst accompanying energy irradiation.
[0164]
When the characteristic reaction layer is the wettability changing layer, it becomes possible to form a pattern with reduced wettability by the action of the photocatalyst accompanying energy irradiation, and using this wettability difference, This is because, for example, the conductive pattern composition can be applied with high definition only to the lyophilic region by an inkjet method or the like. In addition, when the characteristic reaction layer is the adhesion changing layer, it is possible to change the adhesion formed by the action of the photocatalyst accompanying the energy irradiation. After depositing the pattern composition, by utilizing the difference in adhesion, removing the conductive pattern composition in the poor adhesion area other than the good adhesion area, the high-definition conductive pattern portion is obtained. It can be formed.
[0165]
The wettability changing layer and the adhesiveness changing layer are the same as the wettability changing layer described in the third aspect of the characteristic reaction layer and the adhesiveness changing layer described in the fourth aspect. Explanation here is omitted.
[0166]
(2) Photocatalyst processing layer side substrate
Next, the photocatalyst processing layer side substrate used for forming a pattern in which the characteristics of the characteristic reaction layer are changed will be described below.
[0167]
The photocatalyst treatment layer side substrate used in this embodiment has at least a photocatalyst treatment layer and a substrate, and is usually formed by forming a thin-film photocatalyst treatment layer formed by a predetermined method on the substrate. It is. Further, as the photocatalyst processing layer side substrate, a substrate in which a photocatalyst processing layer side light-shielding portion or primer layer formed in a pattern shape is formed can be used.
[0168]
In this embodiment, when irradiating energy, the characteristic reaction layer and the photocatalyst treatment layer in the photocatalyst treatment layer side substrate are opposed to each other with a predetermined gap, and the photocatalyst treatment layer of the photocatalyst treatment layer side substrate The wettability pattern of the characteristic reaction layer is changed by the action, and the wettability pattern is formed by removing the photocatalyst processing layer side substrate after energy irradiation. Hereinafter, each structure of this photocatalyst processing layer side board | substrate is demonstrated.
[0169]
a. Photocatalyst treatment layer
The photocatalyst treatment layer used in the present embodiment contains at least a photocatalyst and may or may not have a binder. The photocatalyst described in the second aspect of the characteristic change layer described above. Since it is the same as that of the processing layer, description here is omitted.
[0170]
Here, the photocatalyst treatment layer used in this embodiment may be formed on the entire surface of the photocatalyst treatment layer side substrate 6 as shown in FIG. 4, for example, but as shown in FIG. The photocatalyst processing layer 5 may be formed in a pattern on the substrate 6.
[0171]
By forming the photocatalyst treatment layer in a pattern like this, when irradiating energy, it is not necessary to irradiate the pattern using a photomask or the like, and by irradiating the entire surface, a lyophilic solution is formed on the characteristic reaction layer. It is possible to form a wettability pattern composed of a property region and a liquid repellent region.
[0172]
The patterning method of the photocatalyst processing layer is not particularly limited, but can be performed by, for example, a photolithography method.
[0173]
In addition, when energy irradiation is performed with, for example, the photocatalyst treatment layer and the characteristic reaction layer being in close contact with each other, the characteristics of only the portion where the photocatalyst treatment layer is actually formed are changed. As long as the energy is applied to the portion where the photocatalyst treatment layer and the characteristic reaction layer are opposed to each other, the irradiation may be performed from any direction, and the irradiation energy is also limited to parallel light such as parallel light. Has the advantage of not being.
[0174]
b. Substrate
In this embodiment, as shown in FIG. 4, the photocatalyst processing layer side substrate 7 has at least a base 6 and a photocatalyst processing layer 5 formed on the base 6.
[0175]
In this case, the material constituting the substrate to be used is appropriately selected depending on the energy irradiation direction to be described later, whether the resulting multilayer wiring board requires transparency, and the like.
[0176]
The substrate used in this embodiment may be a flexible substrate such as a resin film, or may be a non-flexible substrate such as a glass substrate. This is appropriately selected depending on the energy irradiation method.
[0177]
In order to improve the adhesion between the substrate surface and the photocatalyst treatment layer, an anchor layer may be formed on the substrate. Examples of such an anchor layer include silane-based and titanium-based coupling agents.
[0178]
c. Photocatalyst treatment layer side shading part
As the photocatalyst processing layer side substrate used in this embodiment, a substrate on which a photocatalyst processing layer side light-shielding portion formed in a pattern is formed may be used. By using the photocatalyst processing layer side substrate having the photocatalyst processing layer side light-shielding portion in this way, it is not necessary to use a photomask or perform drawing irradiation with laser light when irradiating energy. Therefore, since alignment between the photocatalyst processing layer side substrate and the photomask is unnecessary, it is possible to make a simple process, and an expensive apparatus necessary for drawing irradiation is also unnecessary, so that the cost is reduced. Has the advantage of being advantageous.
[0179]
The photocatalyst processing layer side substrate having such a photocatalyst processing layer side light shielding part can be set to the following two modes depending on the formation position of the photocatalyst processing layer side light shielding part.
[0180]
For example, as shown in FIG. 6, a photocatalyst processing layer side light-shielding part 11 is formed on a substrate 6, and a photocatalyst processing layer 5 is formed on the photocatalyst processing layer side light-shielding part 11. 7 is an embodiment. For example, as shown in FIG. 7, the photocatalyst processing layer 5 is formed on the substrate 6 and the photocatalyst processing layer side light-shielding portion 11 is formed thereon to form the photocatalyst processing layer side substrate 7. .
[0181]
In any aspect, compared to the case where a photomask is used, the photocatalyst treatment layer side light shielding portion is arranged in the vicinity of the arrangement portion of the photocatalyst treatment layer and the characteristic reaction layer. Since the influence of energy scattering can be reduced, energy pattern irradiation can be performed very accurately.
[0182]
Furthermore, in the aspect in which the photocatalyst treatment layer side light shielding portion is formed on the photocatalyst treatment layer, when the photocatalyst treatment layer and the characteristic reaction layer are arranged at predetermined positions, the film thickness of the photocatalyst treatment layer side light shielding portion is set. By making it coincide with the width of the gap, there is an advantage that the photocatalyst processing layer side light shielding portion can be used as a spacer for making the gap constant.
[0183]
That is, when the photocatalyst treatment layer and the characteristic reaction layer are arranged facing each other with a predetermined gap, the photocatalyst treatment layer side light-shielding portion and the characteristic reaction layer are arranged in close contact with each other. Since the predetermined gap can be made accurate, and by irradiating energy from the photocatalyst processing layer side substrate in this state, it is possible to accurately form the characteristic change pattern on the characteristic reaction layer. is there.
[0184]
The method for forming the photocatalyst treatment layer side light shielding part is not particularly limited, and is appropriately selected and used depending on the characteristics of the formation surface of the photocatalyst treatment layer side light shielding part, the shielding property against the required energy, and the like. It is done.
[0185]
For example, it may be formed by forming a metal thin film of chromium or the like having a thickness of about 1000 to 2000 mm by a sputtering method, a vacuum deposition method, or the like, and patterning the thin film. As this patterning method, a normal patterning method such as sputtering can be used.
[0186]
Alternatively, a method may be used in which a layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in a resin binder is formed in a pattern. As the resin binder to be used, polyimide resin, acrylic resin, epoxy resin, polyacrylamide, polyvinyl alcohol, gelatin, casein, cellulose, or a mixture of one or more kinds, photosensitive resin, or O / A W emulsion type resin composition, for example, an emulsion of a reactive silicone can be used. The thickness of such a resin light-shielding portion can be set within a range of 0.5 to 10 μm. As a method for patterning the resin light-shielding portion, a generally used method such as a photolithography method or a printing method can be used.
[0187]
In the above description, the two positions of the photocatalyst treatment layer side light shielding portion between the substrate and the photocatalyst treatment layer and on the surface of the photocatalyst treatment layer have been described as the formation position of the photocatalyst treatment layer side. It is also possible to adopt a mode in which the photocatalyst processing layer side light shielding portion is formed on the surface that is not provided. In this aspect, for example, a case where the photomask is brought into close contact with the surface so as to be detachable can be considered, and it can be preferably used when the characteristic change pattern is changed in a small lot.
[0188]
d. Primer layer
Next, the primer layer used for the photocatalyst processing layer side substrate of this embodiment will be described. In this embodiment, as described above, when the photocatalyst treatment layer side light-shielding portion is formed in a pattern on the substrate and the photocatalyst treatment layer is formed thereon to form the photocatalyst treatment layer side substrate, the photocatalyst treatment is performed. A primer layer may be formed between the layer-side light shielding portion and the photocatalyst treatment layer.
[0189]
The action and function of this primer layer are not always clear, but by forming a primer layer between the photocatalyst treatment layer-side light-shielding part and the photocatalyst treatment layer, the primer layer is characterized by the action of the photocatalyst. Impurities from the openings existing between the photocatalyst processing layer side light shielding part and the photocatalyst processing layer side light shielding part, which are factors that hinder the change, in particular, residues generated when patterning the photocatalyst processing layer side light shielding part, metal, metal It is considered that it has a function of preventing diffusion of impurities such as ions. Therefore, by forming the primer layer, the characteristic change process proceeds with high sensitivity, and as a result, a high-resolution pattern can be obtained.
[0190]
In this embodiment, the primer layer prevents the impurities present in the opening formed between the photocatalyst processing layer side light-shielding part as well as the photocatalyst treatment layer side light-shielding part from affecting the action of the photocatalyst. Therefore, it is preferable that the primer layer is formed over the entire surface of the photocatalyst processing layer side light shielding portion including the opening.
[0191]
The primer layer in the present embodiment is not particularly limited as long as the primer layer is formed so that the photocatalyst treatment layer side light-shielding portion of the photocatalyst treatment layer side substrate and the photocatalyst treatment layer are not in contact with each other.
[0192]
The material constituting the primer layer is not particularly limited, but an inorganic material that is not easily decomposed by the action of the photocatalyst is preferable. Specific examples include amorphous silica. When such amorphous silica is used, the precursor of amorphous silica is represented by the general formula SiX.₄X is a silicon compound such as halogen, methoxy group, ethoxy group, or acetyl group, and a hydrolyzate thereof, silanol, or polysiloxane having an average molecular weight of 3000 or less is preferable.
[0193]
The thickness of the primer layer is preferably in the range of 0.001 μm to 1 μm, particularly preferably in the range of 0.001 μm to 0.1 μm.
[0194]
(3) Pattern in which the characteristics of the characteristic reaction layer have changed
Next, a pattern in which the characteristics of the characteristic reaction layer have changed will be described. As a method for forming a pattern in which the characteristics of the characteristic reaction layer of the present embodiment are changed, the photocatalyst treatment layer and the characteristic reaction layer are arranged at predetermined positions, and then irradiated with energy from a predetermined direction. A step of forming a pattern on the surface of the characteristic reaction layer is performed. Hereinafter, the formation of the characteristic change pattern will be described.
[0195]
a. Arrangement of photocatalyst treatment layer and characteristic reaction layer
In the characteristic change pattern forming step of the present embodiment, first, it is necessary to dispose the photocatalyst treatment layer and the characteristic reaction layer at a predetermined interval so that the action of the photocatalyst is applied at the time of energy irradiation. After the photocatalyst processing layer and the characteristic reaction layer described above are arranged with a gap of 200 μm or less, energy is irradiated from a predetermined direction. At this time, the photocatalyst treatment layer and the characteristic reaction layer may be adhered to each other.
[0196]
In the present embodiment, the above gap is particularly preferably within the range of 0.2 μm to 10 μm in consideration of the point that the pattern accuracy is very good, the photocatalyst sensitivity is high, and the characteristic change efficiency of the characteristic reaction layer is good. Is preferably in the range of 1 μm to 5 μm. Such a gap range is particularly effective for a characteristic reaction layer with a small area that can control the gap with high accuracy.
[0197]
On the other hand, when processing a characteristic reaction layer having a large area of, for example, 300 mm × 300 mm, a fine gap as described above is formed between the photocatalyst processing layer side substrate and the characteristic reaction layer without contact. It is extremely difficult to do. Therefore, when the characteristic reaction layer has a relatively large area, the gap is preferably in the range of 10 to 100 μm, particularly in the range of 50 to 75 μm. By setting the gap within such a range, there is no problem of pattern accuracy deterioration such as blurring of the pattern, or problems such as deterioration of the sensitivity of the photocatalyst and deterioration of the efficiency of characteristic change. This is because there is an effect that unevenness does not occur in the characteristic change on the layer.
[0198]
When the characteristic reaction layer having a relatively large area is irradiated with energy as described above, the setting of the gap in the positioning device between the photocatalyst processing layer side substrate and the characteristic reaction layer in the energy irradiation device is within a range of 10 μm to 200 μm, In particular, it is preferable to set within a range of 25 μm to 75 μm. By setting the set value within such a range, the pattern accuracy and the photocatalyst sensitivity are not greatly deteriorated, and the photocatalyst processing layer side substrate and the characteristic reaction layer are not in contact with each other. Because it becomes possible.
[0199]
Thus, by disposing the photocatalyst treatment layer and the surface of the characteristic reaction layer at a predetermined interval, oxygen, water, and active oxygen species generated by the photocatalytic action are easily desorbed. That is, when the distance between the photocatalyst treatment layer and the characteristic reaction layer is narrower than the above range, it is difficult to desorb the active oxygen species, and as a result, the characteristic change rate may be slowed. Absent. In addition, it is not preferable that the active oxygen species generated are difficult to reach the characteristic reaction layer, and in this case as well, the speed of the characteristic change may be slowed if they are arranged apart from the above range.
[0200]
In this embodiment, such an arrangement state only needs to be maintained at least during energy irradiation.
[0201]
An example of a method for uniformly forming such an extremely narrow gap and arranging the photocatalyst processing layer and the characteristic reaction layer is a method using a spacer. By using the spacer in this way, a uniform gap can be formed, and the portion in contact with the spacer is not affected by the photocatalyst action on the surface of the characteristic reaction layer. By having a pattern similar to the change pattern, a predetermined characteristic change pattern can be formed on the characteristic reaction layer.
[0202]
In this embodiment, such a spacer may be formed as one member. However, for simplification of the process, as described in the column of the photocatalyst treatment layer side substrate, the photocatalyst treatment layer side substrate It is preferable to form on the surface of the photocatalyst treatment layer. In the description of the photocatalyst processing layer side substrate, the photocatalyst processing layer side light shielding portion has been described. However, in this embodiment, such a spacer has a surface so that the photocatalytic action does not reach the surface of the characteristic reaction layer. Since what is necessary is just to have the effect | action which protects, it may be formed with the material which does not have a function which shields especially the energy irradiated.
[0203]
b. Energy irradiation
Next, energy irradiation is performed on the opposing portions while maintaining the above-described arrangement. Since this energy irradiation is the same as that described in the section of the pattern in which the characteristics of the characteristic change layer have changed, description thereof is omitted here.
[0204]
Here, when the photocatalyst processing layer side light shielding portion is formed, it is necessary to irradiate energy from the photocatalyst processing layer side substrate side, and in this case, with respect to the energy irradiated to the photocatalyst processing layer side substrate It needs to be transparent. In this case, in the case where the photocatalyst treatment layer side light shielding portion is formed on the photocatalyst treatment layer and this photocatalyst treatment layer side light shielding portion is used so as to function as a spacer as described above, a multilayer wiring board is used. Depending on the type, the energy irradiation direction may be from the photocatalyst processing layer side substrate side or from the multilayer wiring substrate side.
[0205]
In addition, when the photocatalyst processing layer is formed in a pattern shape, the energy irradiation direction is, as described above, if the energy is irradiated to the portion where the photocatalyst processing layer and the characteristic reaction layer face each other, the multilayer wiring board Irradiation from any direction may be performed depending on the type of.
[0206]
Similarly, in the case of using the above-described spacer, as long as energy is irradiated to the facing portion, irradiation may be performed from any direction depending on the type of the multilayer wiring board.
[0207]
In the case of using a photomask, energy is irradiated from the side where the photomask is arranged. In this case, the substrate on which the photomask is arranged, that is, either the photocatalyst processing layer side substrate or the multilayer wiring substrate needs to be transparent.
[0208]
c. Removing the photocatalyst treatment layer side substrate
When the energy irradiation as described above is completed, the photocatalyst processing layer side substrate is separated from the arrangement position with the characteristic reaction layer, and a pattern in which the characteristic of the characteristic reaction layer is changed is formed on the characteristic reaction layer.
[0209]
(4) Conductive pattern
Next, the conductive pattern in the wiring board having the characteristic reaction layer will be described. As for the conductive pattern formed on the characteristic reaction layer in the present embodiment, if the pattern has the conductivity formed along the pattern on the characteristic reaction layer described above having changed characteristics, the shape of the pattern There are no particular limitations on the materials and materials.
[0210]
The conductive pattern formed on the characteristic reaction layer is the same as the conductive pattern formed on the characteristic change layer described above, and a description thereof is omitted here.
[0211]
2. Second embodiment
Next, a second embodiment of the multilayer wiring board in the present invention will be described. The second embodiment of the multilayer wiring board according to the present invention includes a characteristic change layer containing at least a photocatalyst and having characteristics changed by the action of the photocatalyst, and a conductive formed along a pattern in which the characteristics of the characteristic change layer have changed. A wiring substrate composed of a conductive pattern, a photocatalyst processing layer containing a photocatalyst and a photocatalyst processing layer side substrate having a substrate are disposed with a gap so that the photocatalyst processing layer is 200 μm or less, and then in a predetermined direction. A wiring board comprising a characteristic reaction layer whose characteristics change when irradiated with energy and a conductive pattern formed along a pattern whose characteristics change in the characteristic reaction layer is laminated. Is.
[0212]
According to this embodiment, since the characteristic change layer and the characteristic reaction layer are included, it is possible to easily form a conductive pattern along a pattern in which the characteristics of these layers have changed. This makes it possible to form a fine multilayer wiring board.
[0213]
Here, the characteristic change layer, the characteristic reaction layer, the conductive pattern, the wiring substrate, the photocatalyst processing layer side substrate, and the like are the same as those described in the first embodiment, and thus description thereof is omitted here.
[0214]
B. Manufacturing method of multilayer wiring board
Next, the manufacturing method of the multilayer wiring board of this invention is demonstrated. The method for producing a multilayer wiring board according to the present invention includes:
A property change layer preparation step for preparing a property change layer containing a photocatalyst and whose properties change due to the action of the photocatalyst associated with energy irradiation;
A characteristic change pattern forming step of forming a characteristic change pattern having a changed characteristic on the surface of the characteristic change layer by irradiating energy on the characteristic change layer in a pattern;
A conductive pattern forming step of forming a conductive pattern along the characteristic change pattern,
The wiring board forming step having the above is performed at least twice or more, preferably 3 to 5 times.
[0215]
This wiring board forming process will be described with reference to FIG.
[0216]
In the wiring board formation process of the present invention, first, a characteristic change layer adjustment process for preparing the characteristic change layer 1 is performed (FIG. 8A). Next, for example, using a photomask 8 or the like, a characteristic change pattern forming step of irradiating energy 9 in a pattern on the characteristic change layer from a predetermined direction is performed (FIG. 8B). As a result, a characteristic change pattern 10 having a changed characteristic is formed on the characteristic change layer 1. Next, a conductive pattern forming step for forming the conductive pattern 2 is performed along the characteristic change pattern 10 by, for example, an ink jet method to form the wiring board 3 (FIG. 8D). At this time, it becomes possible to attach the conductive pattern composition for forming the conductive pattern 2 only to the characteristic change pattern 10 in which the characteristic on the characteristic change layer 1 has changed, thereby forming the high-definition conductive pattern 2. Thus, the wiring board can be made.
[0217]
In addition, since the multilayer wiring board is formed by performing this wiring board forming step at least twice, the resulting multilayer wiring board can have a high-definition conductive pattern.
[0218]
In the present invention, as shown in FIG. 9, after the characteristic change layer adjustment step (FIG. 9A), energy is applied onto the characteristic change layer 1 from a predetermined direction using, for example, a photomask 8 or the like. 9 (FIG. 9B), a through-hole characteristic change pattern forming step (FIG. 9C) is performed to form a through-hole characteristic change pattern 13 having changed characteristics on the surface of the characteristic change layer 1. A through hole forming step (FIG. 9D) for forming the through hole 14 by applying a liquid along the through hole characteristic changing pattern 13 may be performed. As a result, in the conductive pattern forming step, it is possible to fill the through holes with a conductive material at the same time as forming the conductive pattern, and a conductive connector for electrically connecting the conductive patterns is formed. It can be easily formed. Hereafter, the manufacturing method of the multilayer wiring board of this invention is demonstrated for every process.
[0219]
(1) Characteristic change layer preparation process
First, the characteristic change layer preparation process of this invention is demonstrated. The property changing layer preparation step in the present invention is not particularly limited as long as it includes a photocatalyst and is a step of preparing a property changing layer whose properties change due to the action of the photocatalyst accompanying energy irradiation. In at least the second and subsequent wiring substrate forming steps, it is preferable to carry out the coating method. Since the characteristic change layer preparation step is a coating method, it is possible to form a characteristic change layer around the conductive pattern formed in the immediately preceding wiring board formation step. It is possible to protect from water vapor. It is also preferable from the viewpoint of manufacturing efficiency and cost.
[0220]
Moreover, when the characteristic change layer of the wiring board located in the lowermost layer portion of the multilayer wiring board used in the present invention does not have self-supporting property, the lowermost characteristic change layer is formed on the substrate. It is necessary.
[0221]
The characteristic change layer, the method for forming the characteristic change layer, the base material, and the like used in the present invention are the same as those described in the above-mentioned “A. Multilayer wiring board”, and thus the description thereof is omitted here. .
[0222]
(2) Characteristic change pattern forming process
Next, the characteristic change pattern forming process in the present invention will be described. The characteristic change pattern forming step in the present invention is a step of forming a characteristic change pattern having changed characteristics on the surface of the characteristic change layer by irradiating energy from a predetermined direction.
[0223]
The characteristic change pattern formation process of the present invention may be performed on a wiring board that has been subjected to a through hole characteristic change pattern formation process and a through hole formation process, which will be described later, and the through hole characteristic change pattern formation process and the through hole formation process are performed. You may carry out about the wiring board which is not.
[0224]
In this step, energy is applied to the pattern shape of the conductive pattern formed in the conductive pattern forming step described later, and the pattern of the conductive pattern formed in the conductive pattern forming step described later is applied to the pattern of the characteristic change layer. This is a step of changing the characteristics. As a result, the conductive pattern can be easily formed in the conductive pattern forming step described later.
[0225]
The energy and energy irradiation used in this step are the same as those described in the section of the pattern in which the characteristics of the characteristic change layer in “A. Multilayer Wiring Board” described above are changed. Is omitted.
[0226]
(3) Conductive pattern formation process
Next, the conductive pattern forming process of the present invention will be described. The conductive pattern formation step of the present invention is a step of forming a conductive pattern along the characteristic change pattern formed in the characteristic change pattern formation step. A through hole characteristic change pattern formation step and a through hole formation described later are performed. For the wiring board on which the process has been performed, the conductive connector may be formed by filling the through hole simultaneously with forming the conductive pattern.
[0227]
The conductive pattern forming step of the present invention is not particularly limited as long as it is a method capable of forming a conductive pattern on the characteristic change pattern, and is appropriately selected depending on the characteristic of the characteristic change layer. However, for example, when the property change layer is a wettability change layer, means such as dip coating, roll coating, blade coating, spin coating and the like, nozzle discharge means including ink jet, electrolytic jet, etc. Can be used. In the present invention, it is preferable to use nozzle discharge means. This is because, in the nozzle discharge means, it is possible to apply a conductive pattern composition that forms a conductive pattern in a target pattern, and it is possible to form a conductive pattern with higher definition. .
[0228]
In addition, when the characteristic change layer is an adhesion change layer, in addition to the above method, an evaporation method, electroless plating, or the like can be used. After forming the conductive pattern composition, the adhesion inhibition region By removing the conductive pattern composition adhering to the conductive pattern composition, the conductive pattern composition can be brought into close contact only with a good adhesion region, and a conductive pattern can be formed.
[0229]
Here, since the same method can be used also when filling the said through hole and forming a conductive connector, this conductive connector can be performed simultaneously with formation of the said conductive pattern. .
[0230]
(4) Through-hole characteristic change pattern formation process
Next, the through hole characteristic change pattern forming process of the present invention will be described. In the present invention, the through hole characteristic change pattern forming step is to form a through hole characteristic change pattern having a changed characteristic on the surface of the characteristic change layer by irradiating the characteristic change layer with energy after the characteristic change layer adjustment step. It is a process to do.
[0231]
In the present invention, when forming a conductive connector between conductive patterns of adjacent wiring boards, a through hole characteristic changing layer forming step for forming a through hole for forming the conductive connector in the characteristic changing layer And you may have a through-hole formation process. At this time, by forming a through-hole characteristic change pattern having changed characteristics on the characteristic change layer by the through-hole characteristic change pattern forming process, in the through-hole forming process described later, the characteristics of the through-hole characteristic pattern are changed. This is because it is possible to easily form a through hole by, for example, dropping a liquid using the difference.
[0232]
The energy irradiation and the like in this through-hole forming step are the same as those in the above-described characteristic change pattern forming step, and thus description thereof is omitted here.
[0233]
(5) Through-hole formation process
Next, the through hole forming process will be described. The through hole forming step in the present invention is a step of forming a through hole by applying a liquid along the through hole characteristic change pattern.
[0234]
The method of applying the liquid is not particularly limited as long as it is a method capable of forming a through hole. In the present invention, the through hole characteristic changing region is not brought into contact with other members. It is preferable to use a method by nozzle discharge from the viewpoint that the liquid can be selectively applied only to the surface. As such a nozzle discharge method, for example, a method using a micro syringe, a dispenser, an ink jet, or the like, or a method of discharging from a needle tip by an external stimulus such as electrolysis, a liquid attached to the needle tip is attached to the characteristic change region. A method or the like can be used. In the present invention, a method using a dispenser or an inkjet is particularly preferable.
[0235]
Moreover, it is preferable that the liquid used for the through-hole formation process of this invention is an alkaline solution, specifically, the aqueous solution of an organic alkali and an inorganic alkali can be raised. Preferable alkaline solutions include sodium hydroxide aqueous solution and potassium hydroxide aqueous solution, and the pH is preferably pH 7 to 14, particularly pH 10 to 14, particularly pH 12 to 14.
[0236]
In the present invention, since the above-described characteristic change layer or characteristic reaction layer is included in the wiring substrate, it is possible to easily form a through hole by utilizing these characteristic changes.
[0237]
For example, when the characteristic change layer is a wettability change layer, energy is applied to the pattern forming the through hole to form a lyophilic region in the pattern, and an alkali, for example, is formed on the lyophilic region. By applying a solution or the like, etching can be performed and a through hole can be formed.
[0238]
In addition, when the characteristic change layer is a decomposition removal layer, energy is applied to the pattern forming the through hole to form irregularities in the pattern, and the irregularity is used to make, for example, the alkaline solution or the like. By applying, it becomes possible to perform etching, and it is possible to easily form a through hole.
[0239]
The materials of the conductive pattern and the conductive connector used in the present invention are the same as those described in the above “A. Multilayer wiring board”, and thus description thereof is omitted here.
[0240]
The present invention is not limited to the above embodiment. The above embodiment is an exemplification, and any structure that has substantially the same configuration as the technical idea described in the claims of the present embodiment and has the same effect can be used. It is included in the technical scope of this embodiment.
[0241]
【Example】
Hereinafter, this embodiment will be described in more detail through examples.
[0242]
(Characteristic change layer formation-first layer)
Isopropyl alcohol 3 g, fluoroalkylsilane (manufactured by Tochem Products Co., Ltd .; MF-160E (trade name)), N- [3- (trimethoxysilyl) propyl] -N-ethylperfluorooctanesulfonamide isopropyl ether 50 0.07 g by weight% solution, titanium oxide sol (Ishihara Sangyo Co., Ltd .; STK-01 (trade name)) 3 g, silica sol (Nippon Synthetic Rubber Co., Ltd .; Glasca HPC7002 (trade name)) 0.6 g, and alkyl 0.2 g of alkoxysilane (manufactured by Nippon Synthetic Rubber Co., Ltd .; HPC402H (trade name)) was mixed and stirred at 100 ° C. for 20 minutes. This solution was spin-coated on a glass substrate having a thickness of 0.7 mm and dried at 150 ° C. for 20 minutes. As a result, a 1 μm-thick characteristic change layer having liquid repellency was formed on the substrate. At this time, the electrical resistance of the characteristic change layer is 1 × 10.¹⁰It was Ω · cm.
[0243]
(Characteristic change pattern formation, first layer)
Next, the surface of the characteristic change layer was exposed with an ultrahigh pressure mercury lamp through a photomask for forming a circuit pattern. Thereby, only the exposed part of the surface of the characteristic change layer became a lyophilic region.
[0244]
The exposure amount at this time was 1500 mJ at 365 nm. The photomask was made of chromium, and a black matrix having a thickness of 0.4 μm formed in a line shape with a width of 20 μm was used. The line was designed so that the opening of the photomask was a circuit pattern on the wiring board.
[0245]
(Conducting conductive material, first layer)
Next, using a silver fine particle dispersion ink (Ag001T manufactured by Vacuum Metallurgy), the ink was ejected from the inkjet head so as to land only on the lyophilic region on the property change layer. The contact angle of the ink with respect to the property change layer was 55 ° in the liquid-repellent portion and 10 ° in the lyophilic portion. The landed ink did not adhere to the liquid-repellent part and spread only in the lyophilic area.
[0246]
After drying at 100 ° C. for 3 minutes and baking at 250 ° C. for 15 minutes, a conductive pattern having a pattern shape similar to the opening of the photomask having a width of 20 μm and a thickness of 0.6 μm is formed. It was. The electrical resistance of the conductive pattern is 6 × 10^-6It was Ω · cm.
[0247]
(Formation of characteristic change layer, second layer)
A second characteristic change layer was formed on the wiring substrate on which the conductive pattern was formed by the same material and coating method as those for forming the first characteristic change layer.
[0248]
(Formation of through-hole characteristic change pattern)
Next, the substrate on which the second characteristic change layer was formed was exposed with an ultrahigh pressure mercury lamp through a photomask for forming a through hole. As a result, a through-hole characteristic change pattern, which is a lyophilic region, was formed only on the exposed part of the surface of the characteristic change layer (a circular pattern having a diameter of 15 μm). At this time, the exposure amount was 1500 mJ at 365 nm. The photomask used was a plurality of circular openings having a diameter of 15 μm arranged so as to overlap the metal pattern portion during exposure.
[0249]
(Through hole formation)
Next, a potassium hydroxide aqueous solution was applied to the plurality of through hole characteristic change patterns having a diameter of 15 μm from an inkjet head subjected to alkali resistance treatment. The potassium hydroxide aqueous solution did not adhere to the lyophobic part and spread only in the lyophilic region. At this time, the aqueous potassium hydroxide solution had a pH of 13, the contact angle with respect to the liquid repellent part was 55 °, and the contact angle with respect to the lyophilic part was 5 °.
[0250]
This was allowed to stand at room temperature for 1 minute, rinsed with pure water, and then dried, whereby the characteristic change layer was decomposed and removed only in the lyophilic portion, and a through hole in which the metal wiring portion was exposed was formed.
[0251]
(Characteristic change pattern formation, second layer)
On the substrate on which the through hole was formed, exposure was performed by the same method as that for the first layer, using the photomask used for forming the first layer characteristic change pattern. As a result, only the exposed portion of the surface of the second property changing layer became a lyophilic region.
[0252]
At this time, since the position of the through hole overlaps with the position of the opening of the photomask, the periphery of the through hole and the side surface of the through hole became lyophilic.
[0253]
(Conducting conductive material, second layer)
The conductive material was applied by the same material and method as the application of the first-layer conductive material. The landed ink did not adhere to the lyophobic part, spread only to the lyophilic part, and filled the through hole.
[0254]
After drying at 100 ° C. for 3 minutes and baking at 250 ° C. for 15 minutes, a second conductive pattern and a conductive connector having a width of 20 μm and a film thickness of 0.6 μm were formed.
[0255]
(After the third layer)
A multilayer wiring board in which four wiring boards were laminated was prepared by the same technique as that up to the second layer. It was possible to form a multilayer wiring board in which the electrical continuity of each wiring pattern and the electrical continuity between each layer circuit pattern by the conductive connector can be satisfactorily taken.
[0256]
【The invention's effect】
According to the present invention, by having the characteristic change layer, the conductive pattern can be easily and precisely formed along the pattern whose characteristic has changed, and by laminating the wiring board, This makes it possible to obtain a high-quality multilayer wiring board.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing an example of a multilayer wiring board of the present invention.
FIG. 2 is a schematic sectional view showing another example of the multilayer wiring board of the present invention.
FIG. 3 is a schematic cross-sectional view showing another example of the multilayer wiring board of the present invention.
FIG. 4 is a schematic cross-sectional view showing an example of a photocatalyst processing layer side substrate used in the present invention.
FIG. 5 is a schematic cross-sectional view showing another example of the photocatalyst processing layer side substrate used in the present invention.
FIG. 6 is a schematic sectional view showing another example of the photocatalyst processing layer side substrate used in the present invention.
FIG. 7 is a schematic cross-sectional view showing another example of the photocatalyst processing layer side substrate used in the present invention.
FIG. 8 is a process diagram showing an example of a method for producing a multilayer wiring board according to the present invention.
FIG. 9 is a process diagram showing a through hole forming process of the method for manufacturing a multilayer wiring board according to the present invention.
[Explanation of symbols]
1 ... Characteristic change layer
2 ... Conductive pattern
3 ... Wiring board
4 ... Base material
5 ... Photocatalyst treatment layer
6 ... Base
7 ... Photocatalyst treatment layer side substrate
8… Photomask
9… Energy
10 ... Characteristic change pattern
11 ... Photocatalyst processing layer side light shielding part
12 ... Primer layer
13 ... Through-hole characteristic change pattern
14 ... Through hole
15 ... Characteristic reaction layer
16 ... Conductive connector

Claims (9)

A property change layer preparation step for preparing a property change layer containing a photocatalyst and whose properties change due to the action of the photocatalyst associated with energy irradiation;
A characteristic change pattern forming step of forming a characteristic change pattern having a changed characteristic on the surface of the characteristic change layer by irradiating energy on the characteristic change layer in a pattern,
A conductive pattern forming step of forming a conductive pattern along the characteristic change pattern;
Performing the wiring board forming step having at least twice,
After the characteristic change layer preparation step, by irradiating energy on the characteristic change layer, a through hole characteristic change pattern forming step for forming a through hole characteristic change pattern having a characteristic change on the surface of the characteristic change layer, and the through A method of manufacturing a multilayer wiring board, comprising: a through hole forming step of forming a through hole by applying a liquid along a hole characteristic change pattern. The method for producing a multilayer wiring board according to claim 1 , wherein the characteristic change layer preparing step in the wiring substrate forming step performed after the second time is performed by a coating method. The through hole forming step, a method for manufacturing a multilayer wiring board according to claim 1 or claim 2, characterized in that is carried out by applying an alkaline solution. The claim according to any one of claims 1 to 3 , wherein the characteristic change layer is formed on a base material in the characteristic change layer preparation step in the wiring board formation step performed for the first time. The manufacturing method of the multilayer wiring board as described in 2 .. At least one of the property change layers is a layer in which a contact angle with a liquid is lowered by the action of a photocatalyst accompanying energy irradiation, and is a photocatalyst wettability change layer containing at least a photocatalyst and a binder. method for manufacturing a multilayer wiring board according to any one of claims of claims 1 to 4. At least one of the characteristic change layer is, by the action of the photocatalyst accompanied by the energy irradiation, to any of the claims from claim 1 to claim 4, wherein the adhesion is a photocatalyst adhesion change layer that changes The manufacturing method of the multilayer wiring board as described. Change in wettability in which at least one of the characteristic change layers is a layer in which a contact angle between the photocatalyst treatment layer containing at least a photocatalyst and a liquid decreases due to the action of the photocatalyst associated with energy irradiation formed on the photocatalyst treatment layer. method for manufacturing a multilayer wiring board according to any one of claims of claims 1 to 4, characterized in that a layer consisting of a layer. At least one of the property change layers is a layer composed of a photocatalyst treatment layer containing at least a photocatalyst and an adhesion change layer whose adhesion changes due to the action of the photocatalyst accompanying energy irradiation formed on the photocatalyst treatment layer. method for manufacturing a multilayer wiring board according to any one of claims of claims 1 to 4, characterized in that. At least one of the characteristic change layers is a layer composed of a photocatalyst treatment layer containing at least a photocatalyst and a decomposition removal layer that is decomposed and removed by the action of the photocatalyst associated with energy irradiation formed on the photocatalyst treatment layer. method for manufacturing a multilayer wiring board according to any one of claims of claims 1 to 4, characterized in.

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