JP2004146478A - Wiring board and its formation method, display device and its formation method, and color filter for display device and its formation method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a wiring board, a display device, and a color filter that are manufactured by forming repellent/hydrophilic patterns by the radiation of light having at least a wavelength of 250 nm, and by forming metal wiring, an electrode or a semiconductor layer, an insulating layer, and the like at a hydrophilic portion. <P>SOLUTION: The wiring board has the wiring comprising a metal member on a surface, and illuminates a portion where the wiring on the board is formed with the light having the wavelength of at least 250 nm for forming the pattern of the wiring. In the board, a layer made of a fluoric polymer containing amorphous is provided on the non-wiring portion of the wiring board, and a layer for absorbing light used to form the wiring pattern is provided, thus providing the wiring board, display device, and color filter that are manufactured by forming the repellent/hydrophilic patterns by the radiation of the light having at least the wavelength of 250 nm, and by forming the metal wiring, the electrode, the semiconductor layer, the insulating layer, or the like at a hydrophilic portion. <P>COPYRIGHT: (C)2004,JPO

Description

【００１４】
（４）表面に金属部材からなる配線を有し、且つ基板上の配線を形成する部分に２５０ｎｍ以上の波長の光を照射して配線のパターン形成することを特徴とする配線基板において、該基板の非配線部分上に非晶質含フッ素重合体からなる層を有し、且つ該非晶質含フッ素重合体が分子中に該配線パターンを形成する際に用いる光を吸収する部位を有することを特徴とする配線基板。
【００１５】
（５）表面に金属部材からなる配線を有し、且つ基板上の配線を形成する部分に２５０ｎｍ以上の波長の光を照射して配線のパターン形成することを特徴とする配線基板において、該基板の非配線部分上に非晶質含フッ素重合体からなる層を有し、且つ該非晶質含フッ素重合体が分子中に該配線パターンを形成する際に用いる光を吸収する部位を有し、且つ該非晶質含フッ素重合体が分子内にパーフルオロポリエーテル鎖とアルコキシシラン残基を有するか、あるいはフルオロアルキル鎖とアルコキシシラン残基を有する化合物から形成されることを特徴とする配線基板。
【００１６】
（６）表面に金属部材からなる配線を有し、且つ基板上の配線を形成する部分に２５０ｎｍ以上の波長の光を照射して配線のパターン形成することを特徴とする配線基板において、該基板の非配線部分上に非晶質含フッ素重合体からなる層を有し、且つ該非晶質含フッ素重合体が分子中に該配線パターンを形成する際に用いる光を吸収する部位を有し、且つ該非晶質含フッ素重合体が分子内にパーフルオロポリエーテル鎖とアルコキシシラン残基を有するか、あるいはフルオロアルキル鎖とアルコキシシラン残基を有する下記構造の化合物から形成されることを特徴とする配線基板。
【００１７】
【化４】

【００１８】
（７）表面に金属部材からなる配線を有する配線基板の製造方法において、少なくとも以下の▲１▼，▲２▼，▲３▼の工程を用いて製造されることを特徴とする配線基板の製造方法。
▲１▼基板の表面に▲２▼の工程で用いる撥水性を低下させる２５０ｎｍ以上の波長の光を吸収する層、及びその上に非晶質含フッ素重合体からなる層を設ける工程。
▲２▼配線を形成する部分に２５０ｎｍ以上の波長の光の照射を行い、光照射部分の撥水性を低下させる工程。
▲３▼上記光照射によって撥水性の低下した部分に対して配線を形成するための部材が溶解または分散した液を付着する工程。
【００１９】
（８）基板の上にゲート電極、その上に絶縁層、その上に半導体層とソース電極とドレイン電極，半導体層とソース電極とドレイン電極の上に保護層を有するＴＦＴ素子において、基板とゲート電極の間，ゲート電極と絶縁層の間，絶縁層と半導体層の間，ソース電極と保護層の間、或いはドレイン電極と保護層の間に含フッ素化合物層を有することを特徴とするＴＦＴ素子。
【００２０】
（９）透明基板表面の上に透明電極、その上に正孔輸送層、その上に発光層を有し、透明基板表面上の透明電極がない部分に絶縁層を有し、発光層と絶縁層の上に金属電極を有し、金属電極の上に封止層を有する有機ＥＬ素子において、透明電極と正孔輸送層の間、透明基板と絶縁層の間、或いは絶縁層と金属電極の間に含フッ素化合物層を有することを特徴とする有機ＥＬ素子。
【００２１】
（１０）透明基板表面上にＲ、及びＧ，Ｂのカラーフィルター部を有し、透明基板表面上のカラーフィルター部の無い部分にブラックマトリクスを有し、Ｒ、及びＧ，Ｂのカラーフィルター部とブラックマトリクスの上に保護層を有するカラーフィルターパネルにおいて、透明基板とブラックマトリクスの間、或いは透明基板とＲ、及びＧ，Ｂのカラーフィルター部の間とブラックマトリクスの上の保護層の間に含フッ素化合物層を有することを特徴とする有機ＥＬ素子。
【００２２】
（１１）基板の上にゲート電極、その上に絶縁層、その上に半導体層とソース電極とドレイン電極，半導体層とソース電極とドレイン電極の上に保護層を有するＴＦＴ素子の製造方法において、少なくとも下記▲１▼〜▲５▼のどれかの工程を用いてＴＦＴ素子を製造することを特徴とするＴＦＴ素子の方法。
▲１▼ゲート電極形成予定部分に２５０ｎｍ以上の波長の光を吸収する部位を持つ含フッ素化合物からなる撥水層を形成し、２５０ｎｍ以上の波長の光を照射した後にゲート電極の形成を行う工程。
▲２▼絶縁層形成予定部分に２５０ｎｍ以上の波長の光を吸収する部位を持つ含フッ素化合物からなる撥水層を形成し、２５０ｎｍ以上の波長の光を照射した後に絶縁層の形成を行う工程。
▲３▼ソース電極とドレイン電極形成予定部分に２５０ｎｍ以上の波長の光を吸収する部位を持つ含フッ素化合物からなる撥水層を形成し、２５０ｎｍ以上の波長の光を照射した後にソース電極とドレイン電極の形成を行う工程。
▲４▼半導体層形成予定部分に２５０ｎｍ以上の波長の光を吸収する部位を持つ含フッ素化合物からなる撥水層を形成し、２５０ｎｍ以上の波長の光を照射した後に半導体層の形成を行う工程。
▲５▼保護層形成予定部分に２５０ｎｍ以上の波長の光を吸収する部位を持つ含フッ素化合物からなる撥水層を形成し、２５０ｎｍ以上の波長の光を照射した後に保護層の形成を行う工程。
【００２３】
（１２）透明基板表面の上に透明電極、その上に正孔輸送層、その上に発光層を有し、透明基板表面上の透明電極がない部分に絶縁層を有し、発光層と絶縁層の上に金属電極を有し、金属電極の上に封止層を有する有機ＥＬ素子の製造方法において、少なくとも下記▲１▼〜▲３▼のどれかの工程を用いて有機ＥＬ素子を製造することを特徴とする有機ＥＬ素子の方法。
▲１▼絶縁層形成予定部分に２５０ｎｍ以上の波長の光を吸収する部位を持つ含フッ素化合物からなる撥水層を形成し、２５０ｎｍ以上の波長の光を照射した後に絶縁層の形成を行う工程。
▲２▼透明電極に２５０ｎｍ以上の波長の光を吸収する部位を持つ含フッ素化合物からなる撥水層を形成し、２５０ｎｍ以上の波長の光を照射した後に正孔輸送層と発光層の形成を行う工程。
▲３▼絶縁層に２５０ｎｍ以上の波長の光を吸収する部位を持つ含フッ素化合物からなる撥水層を形成し、２５０ｎｍ以上の波長の光を照射した後に金属電極と封止層の形成を行う工程。
【００２４】
（１３）透明基板表面上にＲ、及びＧ，Ｂのカラーフィルター部を有し、透明基板表面上のカラーフィルター部の無い部分にブラックマトリクスを有し、Ｒ、及びＧ，Ｂのカラーフィルター部とブラックマトリクスの上に保護層を有するカラーフィルターパネルの製造方法において、少なくとも下記▲１▼〜▲３▼のどれかの工程を用いてカラーフィルターパネルを製造することを特徴とするカラーフィルターパネルの方法。
▲１▼透明基板のブラックマトリクス形成予定部分に２５０ｎｍ以上の波長の光を吸収する部位を持つ含フッ素化合物からなる撥水層を形成し、２５０ｎｍ以上の波長の光を照射した後にブラックマトリクスの形成を行う工程。
▲２▼透明基板のＲ、及びＧ，Ｂのカラーフィルター部形成予定部分に２５０ｎｍ以上の波長の光を吸収する部位を持つ含フッ素化合物からなる撥水層を形成し、
２５０ｎｍ以上の波長の光を照射した後にＲ、及びＧ，Ｂのカラーフィルター部の形成を行う工程。
▲３▼ブラックマトリクスの上に２５０ｎｍ以上の波長の光を吸収する部位を持つ含フッ素化合物からなる撥水層を形成し、２５０ｎｍ以上の波長の光を照射した後に保護層の形成を行う工程。
【００２５】
【発明の実施の形態】
本発明の配線基板の種類は大きく分けて２つある。１つ目は基板表面に光吸収層と撥水層を有するもの（｛Ａ｝で表示）である。２つ目は基板表面に光吸収部位を持つ撥水層を有するもの（｛Ｂ｝で表示）である。これらを分けて説明する。［１］本発明の原理、［２］光照射前の基板作製に用いる部材の（１），（２）の部分は｛Ａ｝に、（３）は｛Ｂ｝に関係する内容である。それ以外の部分
（［２］の（４）と［３］，［４］）は｛Ａ｝，｛Ｂ｝とも共通の内容である。
【００２６】
また表示デバイス作製に関しては、配線基板作製の際に用いられる「配線を形成するための金属部材が溶解または分散した液」の代わりに「絶縁層，半導体層，発光層等を形成する液」を用いることで作製可能である。
【００２７】
［１］本発明の原理
｛Ａ｝光吸収層と撥水層を有する基板の場合
図１を用いて本発明の原理を記述する。まず基板１の表面に光を吸収する層
（光吸収層２）と非晶質含フッ素重合体からなる層（撥水層３）を形成する。非晶質含フッ素重合体からなる層は撥水性であり、後述する配線を形成するための金属部材が溶解または分散した液を弾く。
【００２８】
次に光を基板の金属配線を形成したい部分に照射する。照射光４は、光吸収層で吸収される。するとこの光のエネルギーが熱エネルギーに変換し、光を照射された部分が発熱する。この熱によって撥水層が分解する。場合によっては光吸収層も表面が変形する。これにより光を照射された部分は撥水性が失われ、親水部分になる。
【００２９】
なお図１では光照射部分は撥水層がなくなっているように描かれているが、実際には撥水層が変性したもの（一種の含フッ素化合物からなる層）が残っている。
【００３０】
この状態で配線を形成するための金属部材が溶解または分散した液５を接触させると光を照射された部分、即ち親水部分にのみこの液が付着する。溶媒あるいは分散媒が揮発することで金属の配線６が形成される。
【００３１】
以上が配線形成の概略である。用いる光の波長が長波長であっても、光吸収層の材料（いわば色材）を変えることによって対応可能である。光吸収層中の色材が光を吸収し、吸収したエネルギーが熱エネルギーに変わり、撥水層を熱分解して親水部分を形成すれば本発明の目的は達せられる。
【００３２】
なお撥水層を消失するまで分解するには２５０ｎｍ未満の、しかもかなりの光量の光エネルギーを照射する必要がある。上記光照射条件では消失するまでエネルギーが与えられるわけではない。消失するまで分解されなくても撥水性を低下させることが可能である。その場合、光照射後の撥水層の表面には非晶質含フッ素重合体の構成元素であるフッ素が検出できる（ＴＯＦ−ＳＩＭＳで表面を分析すれば、フッ素原子由来の質量数１９のシグナルが検出可能である）。よって図１では撥水層の光照射部分はなくなっているように描かれているが、実際には非晶質含フッ素重合体が変性したものが残っている。
【００３３】
また表示デバイス作製に関しては、配線基板作製の際に用いられる「配線を形成するための金属部材が溶解または分散した液」の代わりに「絶縁層，半導体層，発光層等を形成する液」を用いることで作製可能である。この場合も例えば画像デバイスの１つであるＴＦＴでは電極と基板の間や絶縁層と基板の間等に非晶質含フッ素重合体が変性したものが残っており、有機のＥＬでは電極と絶縁層の間や絶縁層と基板の間等に非晶質含フッ素重合体が変性したものが残っている。またカラーフィルターパネルではカラーフィルター部と基板の間やブラックマトリクス部基板の間等に非晶質含フッ素重合体が変性したものが残っている。
【００３４】
｛Ｂ｝光吸収部位を持つ撥水層を有する基板の場合
図２を用いて本発明の原理を記述する。まず基板表面に光吸収部位を持つ撥水層７を形成する。この撥水層は後述する配線を形成するための金属部材が溶解または分散した液を弾く。
【００３５】
次に光を基板の金属配線を形成したい部分に照射する。照射光８は、撥水層の光吸収部位で吸収される。するとこの光のエネルギーが熱エネルギーに変換し、光を照射された部分が発熱する。この熱によって撥水層は分解する。これにより光を照射された部分は撥水性が失われ、親水部分になる。
【００３６】
なお図２では光照射部分は光吸収部位を持つ撥水層がなくなっているように描かれているが、実際には光吸収部位を持つ撥水層が変性したもの（一種の含フッ素化合物からなる層）が残っている。
【００３７】
この状態で配線を形成するための金属部材が溶解または分散した液９を接触させると光を照射された部分、即ち親水部分にのみこの液が付着する。溶媒あるいは分散媒が揮発することで金属の配線１０が形成される。
【００３８】
なお｛Ａ｝と同様、光吸収部位を持つ撥水層を消失するまで分解するには２５０ｎｍ未満の、しかもかなりの光量の光エネルギーを照射する必要がある。消失するまで分解されなくても撥水性を低下させることが可能である。その場合、光照射後の光吸収部位を持つ撥水層の表面には構成元素であるフッ素が検出できる
（ＴＯＦ−ＳＩＭＳで表面を分析すれば、フッ素原子由来の質量数１９のシグナルが検出可能である）。よって図２では光吸収部位を持つ撥水層の光照射部分はなくなっているように描かれているが、実際には光吸収部位を持つ撥水層が変性したものが残っている。
【００３９】
また表示デバイス作製に関しては、配線基板作製の際に用いられる「配線を形成するための金属部材が溶解または分散した液」の代わりに「絶縁層，半導体層，発光層等を形成する液」を用いることで作製可能である。この場合も例えば画像デバイスの１つであるＴＦＴでは電極と基板の間や絶縁層と基板の間等に光吸収部位を持つ撥水層が変性したものが残っており、有機のＥＬでは電極と絶縁層の間や絶縁層と基板の間等に光吸収部位を持つ撥水層が変性したものが残っている。またカラーフィルターパネルではカラーフィルター部と基板の間やブラックマトリクス部基板の間等には光吸収部位を持つ撥水層が変性したものが残っている。
【００４０】
以上が概略である。｛Ａ｝と同様、用いる光の波長が長波長であっても、光吸収部位の構造を変えることによって対応可能である。光吸収部位が光を吸収し、吸収したエネルギーが熱エネルギーに変わり、撥水層を熱分解して親水部分を形成すれば本発明の目的は達せられる。
【００４１】
［２］光照射前の基板作製に用いる部材、及び作製方法
以下に基板作製に用いる部材を記述する。
【００４２】
（１）撥水層形成材料とその処理方法
この項は「｛Ａ｝光吸収層と撥水層を有する基板の場合」の説明である。
【００４３】
撥水層形成材料は分子内に撥水性を高めるフッ素原子を含むものを用いる。これら材料を溶解することのできる溶媒に溶解し、この溶液を光吸収層に塗布する。その後乾燥し溶媒を揮発させ、撥水層形成材料からなる薄膜を形成する。その際形成される撥水層表面は、配線を形成するための部材が溶解または分散した液を付着する場合、或いはその上への保護膜形成を行う工程等で光吸収層との密着性が高まるよう、また撥水層の上に保護膜等を塗布する際の膜の均一性を高めるためにも平坦であることが望ましい。平坦化するためには撥水層形成材料が非晶質であることが望まれる。また膜としての物理的耐久性を持つためには重合体構造が望ましい。なお世の中には含シリコン撥水材料もあるが、液を弾く能力は一般に含フッ素材料の方が優れているので本発明では含フッ素材料を用いる。
【００４４】
以上より撥水層形成材料としては非晶質含フッ素重合体が望ましい。これにあたる材料としては具体的にはポリジパーフルオロアルキルフマレート，テフロンＡＦ（登録商標）（Ｄｕｐｏｎｔ社製），サイトップ（旭硝子製），フマライト（日本油脂製）が挙げられる。またポリジパーフルオロアルキルフマレートとスチレンの共重合体、３−フッ化塩化エチレンとビニルエーテルの共重合体、４−フッ化エチレンとビニルエステルの共重合体のような含フッ素エチレンと炭化水素系エチレンの共重合体等も挙げられる。
【００４５】
なお撥水層形成材料によっては塗布後加熱することにより光吸収層表面と化学結合させる材料もある。このような材料の方が撥水層形成材料が次第に親水性の画像パターンに移動し、そのパターンを消失させるおそれが少ないので好適である。このような材料としては次に示すようなものが挙げられる。これら化合物は塗布後加熱することで光吸収層表面の水酸基等と反応し、表面に化学結合を形成するので光吸収層表面を移動する心配が無く、親水性の画像パターンを消失させるおそれが低い。
【００４６】
【化５】

【００４７】
具体的には以下の化合物１〜１２等が挙げられる。
【００４８】
【化６】

【００４９】
【化７】

【００５０】
【化８】

【００５１】
【化９】

【００５２】
【化１０】

【００５３】
【化１１】

【００５４】
【化１２】

【００５５】
【化１３】

【００５６】
【化１４】

【００５７】
【化１５】

【００５８】
【化１６】

【００５９】
【化１７】

【００６０】
このうち化合物１〜８は以下に示す合成方法を実行することで得られる。化合物９〜１２は化合物名がそれぞれ１Ｈ，１Ｈ，２Ｈ，２Ｈ−パーフルオロオクチルトリメトキシシラン、１Ｈ，１Ｈ，２Ｈ，２Ｈ−パーフルオロオクチルトリエトキシシラン、１Ｈ，１Ｈ，２Ｈ，２Ｈ−パーフルオロデシルトリメトキシシラン、１Ｈ，１Ｈ，２Ｈ，２Ｈ−パーフルオロデシルトリエトキシシランとしてヒドラス化学社より上市されている。またその他の市販材料としてはダイキン工業社製オプツールＤＳＸが挙げられる。
【００６１】
また化合物１〜４はフッ素鎖がパーフルオロポリエーテルと呼ばれるものであり、このフッ素鎖を有する化合物から形成される撥水膜は水以外にアルコール系溶媒、或いはハイドロカーボン系溶媒等に長期（１０００時間）にわたって浸漬しても撥水性がほとんど低下しない（低下量は５°以下）という特徴がある。
【００６２】
化合物５〜１２はアルコール系溶媒、或いはハイドロカーボン系溶媒に長期
（１０００時間）にわたって浸漬すると、水との接触角が浸漬前（約１１０°）から基材の接触角とほぼ同レベルまで低下する。
【００６３】
（化合物１の合成）
デュポン社製クライトックス１５７ＦＳ−Ｌ（平均分子量２５００）（２５重量部）を３Ｍ社製ＰＦ−５０８０（１００重量部）に溶解し、これに塩化チオニル（２０重量部）を加え、撹拌しながら４８時間還流する。塩化チオニルとＰＦ−５０８０をエバポレーターで揮発させクライトックス１５７ＦＳ−Ｌの酸クロライド（２５重量部）を得る。これにＰＦ−５０８０（１００重量部）、チッソ（株）製サイラエースＳ３３０（３重量部）、トリエチルアミン（３重量部）を加え、室温で２０時間撹拌する。反応液を昭和化学工業製ラジオライト　ファインフローＡでろ過し、ろ液中のＰＦ−５０８０をエバポレーターで揮発させ、化合物１（２０重量部）を得た。
【００６４】
（化合物２の合成）
チッソ（株）製サイラエースＳ３３０（３重量部）の代わりにチッソ（株）製サイラエースＳ３６０（３重量部）を用いる以外は化合物１の合成と同様にして化合物２（２０重量部）を得た。
【００６５】
（化合物３の合成）
デュポン社製クライトックス１５７ＦＳ−Ｌ（平均分子量２５００）（２５重量部）の代わりにダイキン工業社製デムナムＳＨ（平均分子量３５００）（３５重量部）を用いる以外は化合物１の合成と同様にして化合物３（３０重量部）を得た。
【００６６】
（化合物４の合成）
チッソ（株）製サイラエースＳ３３０（３重量部）の代わりにチッソ（株）製サイラエースＳ３６０（３重量部）を用い、デュポン社製クライトックス１５７ＦＳ−Ｌ（平均分子量２５００）（２５重量部）の代わりにダイキン工業社製デムナムＳＨ（平均分子量３５００）（３５重量部）を用いる以外は化合物１の合成と同様にして化合物４（３０重量部）を得た。
【００６７】
（化合物５の合成）
デュポン社製クライトックス１５７ＦＳ−Ｌ（平均分子量２５００）（２５重量部）の代わりにダイキン工業社製７Ｈ−ドデカフルオロヘプタン酸（分子量
３４６．０６）（３．５重量部）を用いる以外は化合物１の合成と同様にして化合物５（３．５重量部）を得た。
【００６８】
（化合物６の合成）
デュポン社製クライトックス１５７ＦＳ−Ｌ（平均分子量２５００）（２５重量部）の代わりにダイキン工業社製７Ｈ−ドデカフルオロヘプタン酸（分子量
３４６．０６）（３．５重量部）を用い、チッソ（株）製サイラエースＳ３３０
（３重量部）の代わりにチッソ（株）製サイラエースＳ３６０（３重量部）を用いる以外は化合物１の合成と同様にして化合物６（３．５重量部）を得た。
【００６９】
（化合物７の合成）
デュポン社製クライトックス１５７ＦＳ−Ｌ（平均分子量２５００）（２５重量部）の代わりにダイキン工業社製９Ｈ−ヘキサデカフルオロノナン酸（分子量４４６．０７）（４．５重量部）を用いる以外は化合物１の合成と同様にして化合物７（４．５重量部）を得た。
【００７０】
（化合物８の合成）
デュポン社製クライトックス１５７ＦＳ−Ｌ（平均分子量２５００）（２５重量部）の代わりにダイキン工業社製９Ｈ−ヘキサデカフルオロノナン酸（分子量４４６．０７）（４．５重量部）を用い、チッソ（株）製サイラエースＳ３３０（３重量部）の代わりにチッソ（株）製サイラエースＳ３６０（３重量部）を用いる以外は化合物１の合成と同様にして化合物８（４．５重量部）を得た。
【００７１】
これらの化合物をフッ素系の溶媒に溶解し、光吸収層に塗布する。その後、加熱することで光吸収層の水酸基やカルボキシル基等と反応し化学結合を形成する。こうして撥水処理が終了する。撥水層形成材料の濃度は平均分子量の大きい材料ほど高濃度に設定する。平均分子量が３０００前後では濃度は０．３　重量％程度が好ましい。フッ素系の溶媒として具体的には３Ｍ社製のＦＣ−７２，ＦＣ−７７，ＰＦ−５０６０，ＰＦ−５０８０，ＨＦＥ−７１００，ＨＦＥ−７２００、デュポン社製バートレルＸＦ等が挙げられる。加熱温度は１００℃以上が望ましい。できれば１２０℃以上のほうが敏速に製膜の反応が進行する。加熱時間は１００℃の場合は１時間程度、１２０℃の場合は１５分間、１４０℃の場合は１０分間程度が望ましい。但し２５０℃以上の場合は撥水層形成材料が熱分解するおそれがある。光吸収層の基材に水酸基等が存在しない場合は、酸素プラズマ処理を行うことで表面に水酸基を持たせることが可能である。この処理を行った後に撥水処理を行うことで上記撥水層形成材料と光吸収層と化学結合を持つことが可能になる。
【００７２】
なお撥水層形成材料の塗布はハケ塗り，ディップコート法，スピンコート，スプレーコート法等で製膜する。
【００７３】
（２）光吸収層
この項は「｛Ａ｝光吸収層と撥水層を有する基板の場合」の説明である。
【００７４】
光吸収層は層中に光を吸収する部位を有する化合物が存在することが必要である。このような化合物としては一般に知られている色素が用いられる。色素が非晶質であれば色素のみで光吸収層を形成可能である。しかし結晶性の場合は平坦な光吸収層を形成しにくい。そのため光吸収層が結晶化した場合、照射した光が散乱する等の問題を生じる。この場合は別の何らかの物質を溶解・或いは混合することによって結晶性を低下させ平坦な光吸収層を形成する等の手段を嵩じる。上記別の何らかの物質として有効なのが樹脂である。樹脂は色素の保持体としても機能し、膜の物理的強度を高める効果もある。そこで結晶性の色素を用いる場合は色素を樹脂で保持することによって光吸収層を形成することが有効である。なおこの場合、樹脂自身に光吸収部位を設けることによっても達成される。
【００７５】
照射光の波長が近紫外領域（波長としてはおおむね２５０〜４００ｎｍ）であれば、色素ではなくても、ベンゼン環，ナフタレン環，アントラセン環等を有する化合物、或いはアミド等の結合基を有する化合物も挙げられる。また樹脂でも芳香環を有するポリエチレンテレフタレート，ポリスチレン，スチレン−アクリル樹脂，フェノール樹脂等も近紫外光領域に吸収を有する。
【００７６】
照射光の波長が可視光領域（波長としてはおおむね４００〜７００ｎｍ）であれば世の中で色素として用いられているものを樹脂に分散し製膜することで光吸収層を作製できる。また照射光の波長が近赤外光領域（波長としてはおおむね
７００〜１１００ｎｍ）の場合もシアニン色素やフタロシアニン系，ナフタロシアニン系色素を用いることで対応可能である。
【００７７】
色素を樹脂で保持する構造の場合、撥水層への熱の伝達が均一になるように色素は樹脂に溶解またはなるべく細かく均一に分散された状態にする。また照射された光を有効に熱に変換するため、用いる光源の出力波長になるべく大きな吸収を有していることが望ましい。色素としては染料，顔料の限定は特に無い。樹脂への分散性が高いという点では染料のほうが望ましい。ただ染料の場合は吸収した光を熱に変える以外に自らの光分解エネルギーに変えてしまう傾向もある。そのため光エネルギーの熱エネルギーへの変換効率が低い。その点では一般に耐光性の高い顔料は吸収した光のかなりの割合を熱に変えるので好適である。
【００７８】
染料としてはフラバントロン・イエロー，インダンスレン・レッド５ＧＫ，インダンスレン・バイオレットＢＮ等のインダンスレン染料。またオレンジＩＩ，Ｃ．Ｉ．ダイレクト・イエロー１２（クリソフェニン），Ｃ．Ｉ．アシッド・イエロー２３（タートラジン），Ｃ．Ｉ．モルダント・オレンジ１，Ｃ．Ｉ．リアクティブ・イエロー３（プロシオン・イエローＨＡ），Ｃ．Ｉ．ディスパーズ・イエロー３，ナフトール・ブルーブラックＢ等のアゾ染料。マラカイトグリーン系，パラローズアニリン系，オーリン系のトリフェニルメタン染料。インドール環にキノリン環やピリジン環等を結合させたシアニン染料。サフラニンＴ，フルオッセン，メチレン・ブルー等の複素環染料。その他キナクリドン・キノン等のアントラキノン系染料，ポリメチン染料，アゾメチン染料等も挙げられる。
【００７９】
顔料としてはアゾ顔料，フタロシアニン顔料，縮合多環顔料，酸性または塩基性染料のレーキが挙げられる。アゾ顔料の中では具体的にはアセト酢酸アニリド系，ピラゾロン系，βナフトール系，βオキシナフトエ酸系，βオキシナフトエ酸アニリド系等の溶性アゾ顔料，アセト酢酸アニリド系，ピラゾロン系，βナフトール系，βオキシナフトエ酸アニリド系の不溶性アゾ顔料，アセト酢酸アニリド系，βオキシナフトエ酸アニリド系の縮合アゾ顔料が挙げられる。フタロシアニン顔料の中では銅フタロシアニン，ハロゲン化銅フタロシアニン，スルホン化フタロシアニンレーキ等の銅フタロシアニン顔料，無金属フタロシアニン顔料，銅ナフタロシアニン顔料，珪素ナフタロシアニン顔料，ゲルマニウムナフタロシアニン顔料等が挙げられる。縮合多環顔料としてはアミノアントラキノン，アントラピリミジン，フラバントロン，アントアントロン，インダントロン，ピラントロン，ビオラントロン等のアントラキノン系顔料，ペリレン，ペリノン，キナクリドン，チオインジゴ，ジオキサジン，イソインドリン，キノフタロン、種々の金属錯体等が挙げられる。
【００８０】
顔料は分散を均一にするため遊星ボールミル等の粉砕装置で微粒子にする、或いは若干の分散剤を添加することで分散性を向上させる等の手段を採ることが望ましい。
【００８１】
これら色素を保持するため用いられる樹脂は特に限定は無いが、光吸収層をディップ法やスピンコート法といった簡便な方法で形成するため、モノマー、或いは樹脂自身が有機溶媒、あるいは水に溶解するものが望ましい。このような樹脂としてはエチレン・酢酸ビニル共重合体，ポリエチレンテレフタレート，ポリ塩化ビニル，ポリ塩化ビニリデン，ポリ酢酸ビニル，ポリビニルアルコール，ポリビニルブチラール，ポリメチルメタクリレート，ポリエチルメタクリレート，ポリスチレン，スチレン・アクリロニトリル共重合体，アクリロニトリル・ブタジエン・スチレン共重合体，ポリアセタール，ポリカーボネート，酢酸セルロース，二酢酸セルロース，三酢酸セルロース，酢酸酪酸セルロース，プロピオン酸セルロース，エチルセルロース，メチルセルロース，カルボキシメチルセルロース，フェノール樹脂，エポキシ樹脂，ポリエステル樹脂，アルキド樹脂，メラミン樹脂，珪素樹脂，ポリウレタン，ジアリルフタレート樹脂，ポリフェニレンオキシド，ポリイミド，ポリスルホン等が挙げられる。
【００８２】
また光吸収層の上に形成される撥水層が光吸収層と化学結合するタイプの物を用いる場合は撥水層の耐久性が向上するという点でフェノール樹脂やポリビニルアルコールのように水酸基を有する樹脂が望ましい。
【００８３】
（３）光吸収部位を持つ撥水層を形成する材料
この項は「｛Ｂ｝光吸収部位を持つ撥水層を有する基板の場合」の説明である。
【００８４】
▲１▼光を吸収する材料を溶解または分散した撥水材料
光吸収部位を持つ撥水層は撥水層を形成する撥水材料に光吸収する材料、いわゆる色材を溶解または分散する方法が挙げられる。これにあたる撥水材料としてはポリジパーフルオロアルキルフマレート，テフロンＡＦ（Ｄｕｐｏｎｔ社製），サイトップ（旭硝子製），フマライト（日本油脂製）が挙げられる。またポリジパーフルオロアルキルフマレートとスチレンの共重合体、３−フッ化塩化エチレンとビニルエーテルの共重合体、４−フッ化エチレンとビニルエステルの共重合体のような含フッ素エチレンと炭化水素系エチレンの共重合体等も挙げられる。
【００８５】
色材としては上述の染料，顔料、その他汎用の色材が挙げられる。いずれも撥水材料に溶解または微粒子で分散する必要がある。
【００８６】
なお撥水層形成材料の塗布はハケ塗り，ディップコート法，スピンコート，スプレーコート法等で製膜する。
【００８７】
▲２▼分子内に撥水部分と光吸収部位を持った撥水材料
分子内に光吸収部位を有する撥水材料がこの範疇に入る。ただ基板との結合部位を持たない場合は高粘性の液体として基板表面で拡散する可能性があるため、光照射後に金属部材を分散、或いは溶解した液体を付着させる間に光照射部分の撥水性が回復してしまう恐れがある。そのため、この撥水材料を用いる場合は基板との結合部位も有することが望ましい。具体的には下記の化学構造の撥水材料が望ましい。
【００８８】
【化１８】

【００８９】
これら材料の光吸収部位としては２５０ｎｍの光を吸収するアミド結合等も挙げられる。すでに示した化合物１〜８はこの範疇の化合物に入る。
【００９０】
また分子内に色素骨格を持たせることで、この色素骨格が光吸収部位として機能する。具体的な例としては以下の化合物１３〜２７が挙げられる。
【００９１】
【化１９】

【００９２】
【化２０】

【００９３】
【化２１】

【００９４】
【化２２】

【００９５】
【化２３】

【００９６】
【化２４】

【００９７】
【化２５】

【００９８】
【化２６】

【００９９】
【化２７】

【０１００】
【化２８】

【０１０１】
【化２９】

【０１０２】
【化３０】

【０１０３】
【化３１】

【０１０４】
【化３２】

【０１０５】
【化３３】

【０１０６】
これらの化合物の合成方法を以下に示す。
【０１０７】
（化合物１３の合成）
化合物１３は下記の（ｉ）〜（ｉｉｉ）の反応により合成される。
【０１０８】
（ｉ）撥水材料の還元
デュポン社製クライトックス１５７ＦＳ−Ｌ（平均分子量２５００）（５０重量部）を３Ｍ社製ＰＦ−５０８０（１００重量部）に溶解し、これに水素化リチウムアルミニウム（２重量部）を加え、４８時間８０℃で加熱・攪拌する。反応液を氷水に注ぎ、下層を分取し１％塩酸で洗った後、洗浄液の液性が中性になるまで水洗する。ろ紙でろ過することで洗浄後の液中の水分を除いた後、ＰＦ−５０８０をエバポレーターで揮発させクライトックス１５７ＦＳ−Ｌの末端がＣＨ_２ＯＨに変換された化合物２８（４５重量部）を得る。
【０１０９】
【化３４】

【０１１０】
（ｉｉ）色素骨格の導入反応
化合物２８（４５重量部）を３Ｍ社製ＨＦＥ−７２００（１００重量部）に溶解し、これにリアクティブ・イエロー３（別名プロシオン・イエローＨＡ）（１２重量部），エタノール（１００重量部），炭酸ナトリウム（２重量部）を加え、３０時間還流する。なおリアクティブ・イエロー３の構造を下記に示す。
【０１１１】
【化３５】

【０１１２】
反応液中の溶媒（ＨＦＥ−７２００とエタノール）をエバポレーターで揮発させ、残渣にＨＦＥ−７２００（１００重量部），３５重量％の塩酸（１００重量部）に氷水（１００重量部）を合わせたものを加え、激しく攪拌した後静置する。下層を分取し、洗浄液の液性が中性になるまで水洗する。ろ紙でろ過することで洗浄後の液中の水分を除いた後、ＨＦＥ−７２００をエバポレーターで揮発させ化合物２８にリアクティブ・イエロー３が結合した化合物２９（４５重量部）を得る。
【０１１３】
【化３６】

【０１１４】
（ｉｉｉ）結合部位の導入反応
化合物２９（４５重量部）をＨＦＥ−７２００（１００重量部）に溶解後、０℃前後に冷却時、チッソ（株）製サイラエースＳ３３０（１０重量部）、Ｎ，Ｎ−ジシクロヘキシルカルボジイミド（１０重量部），ジクロルメタン（２０重量部）を加え、３時間攪拌する。更に反応液を常温に戻し、３０時間攪拌する。反応液を静置後、反応液がおおよそ２層に分かれたら下層を分取する。なお上層と下層の間に濁りを生じるがこれは下層に加えない。下層をジクロルメタン（２０重量部）で数回洗った後、ろ紙でろ過する。この後液中の溶媒（ＨＦＥ−７２００）をエバポレーターで揮発させ目的の化合物１３（４０重量部）を得た。
【０１１５】
（化合物１４の合成）
リアクティブ・イエロー３（１２重量部）の代わりにミカシオン・ブリリアント・ブルーＲＳ（７重量部）を用いる以外は化合物１３の合成と同様にして化合物１４（４０重量部）を得た。
【０１１６】
なおミカシオン・ブリリアント・ブルーＲＳの化学構造は下記の通りである。
【０１１７】
【化３７】

【０１１８】
場合によってスルホン酸ナトリウムの部分がスルホン酸になっているものもあるので、その場合は水酸化ナトリウム等でスルホン酸ナトリウムに変換した後に使用する。
【０１１９】
（化合物１５の合成）
チッソ（株）製サイラエースＳ３３０（１０重量部）の代わりにチッソ（株）製サイラエースＳ３６０（１０重量部）を用いる以外は化合物１３の合成と同様にして化合物１５（３５重量部）を得た。
【０１２０】
（化合物１６の合成）
チッソ（株）製サイラエースＳ３３０（１０重量部）の代わりにチッソ（株）製サイラエースＳ３６０（１０重量部）を用い、リアクティブ・イエロー３（１２重量部）の代わりにミカシオン・ブリリアント・ブルーＲＳ（７重量部）を用いる以外は化合物１３の合成と同様にして化合物１６（３６重量部）を得た。
【０１２１】
（化合物１７の合成）
化合物２８（４５重量部）の代わりにダイキン工業社製デムナムＳＡ（平均分子量３５００）（６５重量部）を用いる以外は化合物１３の合成と同様にして化合物１７（５６重量部）を得た。
【０１２２】
（化合物１８の合成）
化合物２８（４５重量部）の代わりにダイキン工業社製デムナムＳＡ（平均分子量３５００）（６５重量部）を用い、リアクティブ・イエロー３（１２重量部）の代わりにミカシオン・ブリリアント・ブルーＲＳ（７重量部）を用いる以外は化合物１３の合成と同様にして化合物１８（５０重量部）を得た。
【０１２３】
（化合物１９の合成）
化合物２８（４５重量部）の代わりにダイキン工業社製デムナムＳＡ（平均分子量３５００）（６５重量部）を用い、チッソ（株）製サイラエースＳ３３０
（１０重量部）の代わりにチッソ（株）製サイラエースＳ３６０（１０重量部）を用いる以外は化合物１３の合成と同様にして化合物１９（４８重量部）を得た。
【０１２４】
（化合物２０の合成）
化合物２８（４５重量部）の代わりにダイキン工業社製デムナムＳＡ（平均分子量３５００）（６５重量部）を用い、リアクティブ・イエロー３（１２重量部）の代わりにミカシオン・ブリリアント・ブルーＲＳ（７重量部）を用い、チッソ（株）製サイラエースＳ３３０（１０重量部）の代わりにチッソ（株）製サイラエースＳ３６０（１０重量部）を用いる以外は化合物１３の合成と同様にして化合物２０（４４重量部）を得た。
【０１２５】
（化合物２１の合成）
化合物２８（４５重量部）の代わりにアウジモント社製ＤＯＬ４０００（平均分子量４０００）（４０重量部）を用いる以外は化合物１３の合成と同様にして化合物２１（４０重量部）を得た。
【０１２６】
（化合物２２の合成）
化合物２８（４５重量部）の代わりにアウジモント社製ＤＯＬ４０００（平均分子量４０００）（４０重量部）を用い、チッソ（株）製サイラエースＳ３３０（１０重量部）の代わりにチッソ（株）製サイラエースＳ３６０（１０重量部）を用いる以外は化合物１３の合成と同様にして化合物２２（３８重量部）を得た。
【０１２７】
（化合物２３の合成）
化合物２８（４５重量部）の代わりに１Ｈ，１Ｈ，２Ｈ，２Ｈ−パーフルオロデカノール（４重量部）を用い、リアクティブ・イエロー３（１２重量部）の代わりにミカシオン・ブリリアント・ブルーＲＳ（７重量部）を用いる以外は化合物１３の合成と同様にして化合物２３（１１重量部）を得た。
【０１２８】
（化合物２４の合成）
化合物２８（４５重量部）の代わりに１Ｈ，１Ｈ，２Ｈ，２Ｈ−パーフルオロデカノール（４重量部）を用い、リアクティブ・イエロー３（１２重量部）の代わりにミカシオン・ブリリアント・ブルーＲＳ（７重量部）を用い、チッソ（株）製サイラエースＳ３３０（１０重量部）の代わりにチッソ（株）製サイラエースＳ３６０（１０重量部）を用いる以外は化合物１３の合成と同様にして化合物
２４（９重量部）を得た。
【０１２９】
（化合物２５の合成）
化合物２８（４５重量部）の代わりに１Ｈ，１Ｈ，２Ｈ，２Ｈ−パーフルオロデカノール（４重量部）を用い、チッソ（株）製サイラエースＳ３３０（１０重量部）の代わりにチッソ（株）製サイラエースＳ３６０（１０重量部）を用いる以外は化合物１３の合成と同様にして化合物２５（１０重量部）を得た。
【０１３０】
（化合物２６の合成）
化合物２８（４５重量部）の代わりに１Ｈ，１Ｈ，２Ｈ，２Ｈ，１０Ｈ−パーフルオロデカノール（４重量部）を用い、リアクティブ・イエロー３（１２重量部）の代わりにミカシオン・ブリリアント・ブルーＲＳ（７重量部）を用い、チッソ（株）製サイラエースＳ３３０（１０重量部）の代わりにチッソ（株）製サイラエースＳ３６０（１０重量部）を用いる以外は化合物１３の合成と同様にして化合物２６（８重量部）を得た。
【０１３１】
（化合物２７の合成）
化合物２８（４５重量部）の代わりに１Ｈ，１Ｈ，２Ｈ，２Ｈ，１０Ｈ−パーフルオロデカノール（４重量部）を用い、チッソ（株）製サイラエースＳ３３０（１０重量部）の代わりにチッソ（株）製サイラエースＳ３６０（１０重量部）を用いる以外は化合物１３の合成と同様にして化合物２７（９重量部）を得た。
【０１３２】
これらの化合物をフッ素系の溶媒に溶解し、基板に塗布する。その後、加熱することで基板の水酸基やカルボキシル基等と反応し化学結合を形成する。こうして光吸収部位を持つ撥水層の形成が終了する。分子内に撥水部分と光吸収部位を持った撥水材料の濃度は平均分子量の大きい材料ほど高濃度に設定する。平均分子量が３０００前後では濃度は０．３　重量％程度が好ましい。フッ素系の溶媒として具体的には３Ｍ社製のＦＣ−７２，ＦＣ−７７，ＰＦ−５０６０，ＰＦ−
５０８０，ＨＦＥ−７１００，ＨＦＥ−７２００，デュポン社製バートレルＸＦ等が挙げられる。加熱温度は１００℃以上が望ましい。できれば１２０℃以上のほうが敏速に製膜の反応が進行する。加熱時間は１００℃の場合は１時間程度、１２０℃の場合は１５分間、１４０℃の場合は１０分間程度が望ましい。但し
２５０℃以上の場合は撥水層形成材料が熱分解するおそれがある。基板に水酸基等が存在しない場合は、酸素プラズマ処理を行うことで表面に水酸基を持たせることが可能である。この処理を行った後に処理を行うことで分子内に撥水部分と光吸収部位を持った撥水材料と基板とが化学結合を持つことが可能になる。
【０１３３】
なお分子内に撥水部分と光吸収部位を持った撥水材料の塗布はハケ塗り，ディップコート法，スピンコート法等で製膜する。
【０１３４】
（４）基板材料、及びその表面の親水化
この項に関しては上記｛Ａ｝，｛Ｂ｝とも内容は共通である。
【０１３５】
光吸収層，撥水層，光吸収部位を持つ撥水層を形成する前にあらかじめ基板表面を親水性にしておくことで、その表面への物質の付着が容易になり光吸収層や光吸収部位を持つ撥水層を平坦に形成しやすくなる。特に塗布法で光吸収層を形成する場合は、形成するための塗料の濡れ性を向上させることで、高密着性の光吸収層が形成可能となる。また光吸収部位を持つ撥水層に光を照射することで撥水層が分解された後、金属部材を溶解または分散した液を付着しやすくするために基板を親水化しておくことが望ましい。
【０１３６】
基板としてはガラス，石英，シリコン，樹脂、或いはガラス粒子を含んだ樹脂等、種々の材料が考えられる。
【０１３７】
▲１▼基材がガラス，石英，シリコンの場合に適用する方法
基材がガラス，石英，シリコンの場合は酸素プラズマで処理したり、塩基性の溶液に浸漬する等の方法により親水性を向上させることが可能である。酸素プラズマの場合、酸素分圧１Ｔｏｒｒ、高周波電源の出力３００Ｗ、処理時間３分間で水との接触角が１０°以下になった。
【０１３８】
また紫外線を照射することにより基板近傍の酸素をオゾンに変え、そのオゾンによって基板表面を親水性に変えることも可能である。オゾン発生装置を用いて基板をオゾン雰囲気に曝す事も親水性を向上させる手段として有効である。
【０１３９】
その他、塩基性の溶液として１重量％の水酸化ナトリウムの水溶液を用いた場合、５分間浸漬後、水との接触角は皆２０°以下になった。
【０１４０】
▲２▼基材が樹脂の場合に適用する方法
基材が樹脂の場合は酸素プラズマで処理したり、酸・塩基性の溶液に浸漬する等の方法により親水性を向上させることが可能である。
【０１４１】
酸素プラズマを用いる場合、例えばポリスチレン，アクリル樹脂，スチレン／アクリル樹脂，ポリエステル樹脂，アセタール樹脂，ポリカーボネート，ポリエーテルスルホン，ポリサルホン，ポリエーテルサルホン等では、酸素分圧１Ｔｏｒｒ、高周波電源の出力１００Ｗ、処理時間１分間の条件で水との接触角が２０°以下になった。
【０１４２】
またガラス同様、紫外線を照射することにより基板近傍の酸素をオゾンに変え、そのオゾンによって基板表面を親水性に変えることも可能である。オゾン発生装置を用いて基板をオゾン雰囲気に曝す事も親水性を向上させる手段として有効である。
【０１４３】
その他の方法として塩基性の溶液への浸漬はアクリル樹脂，スチレン／アクリル樹脂，ポリエステル樹脂，アセタール樹脂，ポリカーボネート等のように分子内にエステル結合を有する材料の場合に特に有効である。これは表面、及びその近傍にあるエステル結合を切断することで親水性の高いカルボン酸塩残基、及び／或いは水酸基が生成することで総じて表面の親水性が高まるためである。またポリイミドやポリアミド等のアミノ基とカルボキシル基の縮合により重合する樹脂の場合は、塩酸等の酸に浸漬することで重合時に反応せず残ったアミノ基を親水性の高いアンモニウム塩構造にしたり、水酸化ナトリウム水溶液に浸漬することで重合時に反応せず残ったカルボキシル基を親水性の高いカルボン酸塩にすることで総じて表面の親水性を高めることができる。酸・塩基性の溶液への浸漬は溶液の温度が高いほど、また濃度が高い親水化が敏速に進行する傾向がある。しかし高温・高濃度化は基材へのダメージを与えやすいので注意が必要である。
【０１４４】
▲３▼種々の基材に適用する方法
基材が金属，ガラス、あるいは樹脂であっても処理可能な親水化方法としては親水性を発揮させる塗料を塗布する方法が挙げられる。これら材料は一般にａ）〜ｄ）に示すものが挙げられるがこれ以外も特に限定は受けない。
【０１４５】
ａ）水溶性高分子材料の溶液
水溶性の高分子としてはポリエチレングリコール，ポリビニルアルコール，ポリアクリル酸，ポリアクリル酸塩，ポリアリルアミン，ポリアリルアミンの塩酸塩，デンプン等が挙げられる。分子内に水酸基，アミノ基，カルボキシル基，塩構造の残基等親水性の残基を有しているものが挙げられる。これらの水溶液、あるいは有機溶媒の溶液を調製し塗料とする。これをセルの基材に塗布し、乾燥させることで親水塗膜を形成する。これら水溶性高分子の中では特にポリエチレングリコールを塗布した表面の接触角を低下させる傾向が強い。用いる高分子は分子量が大きいほど光散乱の少ない平滑な親水膜が形成できるので好ましい。また処理する表面の撥水性が高い場合は塗料が弾かれてしまうため、結果として平坦な膜を形成できない。これは溶媒が水の場合は用いる高分子の溶液の表面張力が大きくなるためである。そこでこれら塗料を塗布する前に予め酸素プラズマ処理をしておくと、平坦な塗膜が形成しやすい。ところでポリエチレングリコールはテトラヒドロフラン等の有機溶媒に溶解する。そのためこの溶液の表面張力は同じポリエチレングリコールの水溶液に比べて小さく、撥水性の高いアルミ等の表面にも塗布しやすい。
【０１４６】
ｂ）親水性粒子を含んだ塗料
親水性アルミナ粒子や親水性シリカ粒子を含んだ分散液とアルコキシシランの溶液を混ぜたものを塗料として用いる。この塗料を用いる場合、セルの基材に塗布後に加熱することで製膜が完了する。この塗料で主に親水性を発揮するのは親水性アルミナ粒子や親水性シリカ粒子であり、アルコキシシランは主にこれら粒子の保持体として機能する。そのため親水性を高めるには親水性アルミナ粒子や親水性シリカ粒子の割合を大きくすることで対処することができる。またアルコキシシランの割合を大きくすることで膜の物理的強度は向上する。アルコキシシランはある程度分子間で架橋していた方が、塗布後の加熱で揮発する割合が減るので好ましい。またアルコキシシランには分子間の重合を促進させるために塩酸等を加えることがあるが、親水性シリカの場合は分散を良好にするため、その分散液は塩基性になっている場合がある。そのため両者を混ぜた場合、親水性シリカが凝集することがあるので混合した場合の液性と親水性シリカの分散の状況には注意する。この点アルミナの場合は分散液は主に酸性であるため混合の際のトラブルが少ない。アルコキシシランとしてはメチルトリメトキシシラン，エチルトリメトキシシラン，ブチルトリメトキシシラン，メチルトリエトキシシラン，エチルトリエトキシシラン，ブチルトリエトキシシラン，テトラメトキシシラン，テトラエトキシシラン等が挙げられる。なお液性や溶媒が合えばアルコキシシランの代わりにアルコキシチタンを用いても良い。アルコキシチタンとしてはテトラ−ｉ−プロピルチタネート，テトラ−ｎ−ブチルチタネート，テトラステアリルチタネート，トリエタノールアミンチタネート，チタニウムアセチルアセトネート，チタニウムエチルアセトアセテート，チタニウムラクテート，テトラオクチレングリコールチタネート等が挙げられる。またこれらの化合物が数分子重合したものも用いることが可能である。
【０１４７】
ｃ）水溶性高分子とその架橋剤を含んだ塗料
ａ）に挙げたような水溶性高分子に架橋剤としてｂ）に挙げたアルコキシシランやアルコキシチタンを混ぜることによって親水表面を形成する塗料とすることも可能である。この場合、溶媒は水であっても良いが、セル基材の撥水性が高い場合は塗料を弾いてしまうため、メタノールやエタノール等のアルコール系溶媒が好適である。
【０１４８】
ｄ）アルコキシシラン溶液とアルカリ溶液の併用
ｂ）に挙げたアルコキシシランの溶液を基材に塗布後、１２０〜１８０℃程度で数分間加熱すると基材表面に酸化ケイ素の被膜が形成する。その後アルカリ性の溶液に浸漬すると表面の親水性が高まる。最後にアルカリ性の溶液を水洗することで親水処理が終了する。アルカリ性の溶液は水酸化ナトリウム，水酸化カリウム等の水酸化物の水溶液、あるいはアルコール溶液，含水アルコール溶液を用いる。濃度は高いほど浸漬時間は短くできるが、用いる水酸化物の種類によっても異なる。水酸化ナトリウムを用いた場合、溶液濃度１重量％では浸漬時間は１〜５分間、５重量％では１０〜３０秒間程度が好適である。またアルコキシシランの溶液に用いる溶媒としてケトン系のもの（アセトンやメチルエチルケトン等）はアルコキシシランが二酸化ケイ素に変化しやすいので、アルコール系，エステル系、あるいはエーテル系の溶媒が好適である。特にアルコール系は基材が樹脂の場合、樹脂を溶解し難いので特に好適である。
［３］光源
本発明で金属配線予定部分に光照射するため用いる光源は光吸収層、或いは光吸収部位の吸収波長の光を発している必要がある。それがランプであってもレーザーであっても特に問題は無い。ただ望ましくは照射された光がなるべく高効率で吸収され、熱に変換し、撥水層を形成する部材に熱を与えられれば良い。光吸収層、或いは光吸収部位の吸収スペクトルが近紫外〜近赤外あたりまで広くブロードにある場合は、特定の波長の光を照射するレーザーや水銀ランプよりもキセノンランプのように広い波長の光を発する光源の方が望ましい。それとは逆に吸収スペクトルが狭い場合は、その吸収波長の光を発するレーザーが望ましい。なお近紫外の場合はレーザーと同様に特定の波長の光を発する水銀ランプも有効である。具体的には水銀ランプは２５４ｎｍ，３６５ｎｍ（Ｉ線）、そして可視領域の４３５ｎｍ（Ｇ線）の光を発する。
【０１４９】
低圧水銀ランプの場合は１８５ｎｍの光も発する。しかしこの波長の光は酸素等で吸収されるため光照射の際は基板を減圧状態の場所に置く必要があり、真空プロセスを用いず配線基板を作製するという本発明の思想から外れる。
【０１５０】
レーザーの場合はアルゴンレーザーの４１５ｎｍ，４８８ｎｍ，５１５ｎｍ。ＹＡＧレーザーの２倍波の５３２ｎｍ，３倍波の３５５ｎｍ，４倍波の２６６ｎｍ。窒素レーザーの３３７ｎｍ。ヘリウム／ネオンレーザーの６３３ｎｍ。エキシマレーザー（ＸｅＣｌ）の３０８ｎｍ。半導体レーザーの６７０ｎｍ，７８０ｎｍ，８３０ｎｍ，ＹＡＧレーザーの１０６４ｎｍ等が挙げられる。またレーザー発信用色素を用いることによって広範囲の波長の光を発信可能となる。そのため色素の選択範囲が広がる。例えばレーザー発信用色素としてクマリン系の色素である７−（エチルアミノ）−４，６−ジメチル−２Ｈ−１−ベンゾピラン−２−オンを用いることで４３０〜４９０ｎｍの光を発信可能である。それより長波長を発信させる場合はクマリン系の色素である２，３，６，７−テトラハイドロ−１１−オキソ−１Ｈ，５Ｈ，１１Ｈ−［１］ベンゾピラノ［６，７，８−ｉｊ］キノリジン−１０−カルボン酸エチルエステルを用いることで４８４〜５４４ｎｍの光を発信可能である。それより長波長を発信させる場合はローダミン系の色素である９−［２−（エトキシカルボニル）フェニル］−３，６−ビス（エチルアミノ）−２，７−ジメチルアンスリウムクロライドを用いることで５５０〜６３３ｎｍの光を発信可能である。それより長波長を発信させる場合は２−［４−｛４−（ジメチルアミノ）フェニル｝−１，３−ブタジエニル］−１−エチルピリジニウムパークロレートを用いることで６４５〜８０８ｎｍの光を発信可能である。それより長波長を発信させる場合は５−クロロ−２−［２−［３−｛２−（５−クロロ−３−エチル−２（３Ｈ）−ベンゾチアゾリリデン）エチリデン｝−２−ジフェニルアミノ−１−シクロペンテン−１−リル］エテニル］−３−エチル−ベンゾチアゾリウムパークロレートを用いることで８０５〜１０３０ｎｍの光を発信可能である。それより長波長を発信させる場合は３−エチル−２−［［３−［３−［３−｛（３−エチルナフソ［２，１−ｄ］チアゾール−２（３Ｈ）−イリデン）メチル｝−５，５−ジメチル−２−シクロヘキセン−１−イリデン］−１−プロペニル］−５，５−ジメチル−２−シクロヘキセン−１−イリデン］メチル］ナフソ［２，１−ｄ］チアゾリウムパークロレートを用いることで１０７６〜１２００ｎｍの光を発信可能である。
【０１５１】
［４］金属部材を溶解または分散した液
金属部材を分散した液としては金，銀，白金を分散した液が挙げられる。これらは凝集して大きな粒子にならないよう、分散剤，分散安定剤が必要となる。１次粒子としては数十ｎｍの大きさであることが望ましい。銅は空気中の酸素によって腐食しやすいので分散液中に酸化防止剤を添加することが望ましい。
【０１５２】
金属部材を溶解した液としてはメッキ液が挙げられる。例えば無電解銅メッキ用の銅含有液が挙げられる。これはあらかじめ塩化パラジウムの液を親水パターニングを行う部分に付着させた後に銅含有液を付着させる。これにより形成される銅の配線の基板に対する密着性が向上する。なお銅含有液を付着させる前に金の含有液を付着する操作を行うことで密着性がさらに向上する。
【０１５３】
［５］表示デバイス作製への適用方法
前述したように表示デバイス作製に関しては、配線基板作製の際に用いられる「配線を形成するための金属部材が溶解または分散した液」の代わりに「絶縁層，半導体層，発光層等を形成する液」を用いることで作製可能である。作製の詳細に関しては実施例で示す。
【０１５４】
【実施例】
以下、実施例により本発明を更に具体的に説明するが、本発明の範囲はこれらの実施例に限定されるものではない。
【０１５５】
実施例１〜２２に本発明の配線基板のうち、光吸収層と撥水層を有する配線基板の作製方法、及び性能評価結果を示す。また実施例２３〜３８に本発明の配線基板のうち、光吸収部位を持つ撥水層を有する配線基板の作製方法、及び性能評価結果を示す。実施例３９は両者に関係する実施例である。実施例４１以降にＴＦＴ，有機のＥＬ基板等の表示素子及びカラーフィルターの作製方法、及び性能評価結果を示す。
【０１５６】
【実施例１】
（１）光吸収層形成工程
ガラス製基板に低圧水銀ランプで紫外光を照射した。ランプは５００Ｗ、照射時間は５分間である。その結果ガラス製基板の水との接触角は照射前の３０〜３５°から照射後には１０°以下となった。この処理は光吸収層を形成するため塗布する色素が均一に塗れるよう、濡れ性を向上させる操作である。
【０１５７】
林原生物化学研究所社製色素ＮＫ−２０１４の１重量％メチルエチルケトン溶液と丸善石油化学社製のフェノール樹脂であるマルカリンカーＭの１重量％メチルエチルケトン溶液を調製する。なおＮＫ−２０１４をガラスやクオーツ等の透明基板に塗布した際に形成される色素薄膜の吸収極大波長は約７８０ｎｍである。これら２液を同重量混合後、この混合液を上記処理を行ったアルミ製基板の上にスピンコート法（回転数：２０００ｒｐｍ　，回転時間：３０秒間）で塗布する。更に８０℃で２分間加熱する。こうして光吸収層が形成される。
【０１５８】
（２）撥水層形成工程
次に、化合物１の０．１　重量％ＰＦ−５０８０溶液に１０分間浸漬後、１２０℃で１０分間加熱する。こうして撥水層が形成される。
【０１５９】
（３）光照射工程
出力２ｍＷ，発信波長７８０ｎｍの半導体レーザーを用い、レーザースポット径２μｍ，スキャン速度１０ｍｍ／秒で基板表面の配線形成予定部分に光を照射する。すると照射した光が熱に変わり、化合物１により形成された撥水層がこの熱で変性を起こし、結果として変性部分（即ち光照射部分）の撥水性が低下する。
【０１６０】
（４）属配線形成工程
０．５　重量％の銀微粒子分散液（溶媒は水、液の表面張力は６９ｍＮ／ｍ、銀微粒子の一次粒子の平均粒径は約２０ｎｍ）が深さ５ｍｍになるよう入っているバットを用意する。バットは基板が入るだけの大きさがある。光照射後の基板の光照射面を下にしてバットの中に入れた後、すぐに引き上げる。光の非照射部分には銀微粒子分散液が付着しないが、光の照射部分に銀微粒子分散液が付着する。基板の銀微粒子分散液が付着した側を上にして１２０℃で１５分間加熱する。銀微粒子分散液の付着した部分は溶媒の水が揮発し、銀の配線が形成された。
【０１６１】
（５）導通確認試験
形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０１６２】
【実施例２】
林原生物化学研究所社製色素ＮＫ−２０１４の代わりに林原生物化学研究所社製色素ＮＫ−４を用いる以外は実施例１と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０１６３】
なおＮＫ−４をガラスやクオーツ等の透明基板に塗布した際に形成される色素薄膜の吸収極大波長は約７８０ｎｍである。
【０１６４】
【実施例３】
林原生物化学研究所社製色素ＮＫ−２０１４の代わりに林原生物化学研究所社製色素ＮＫ−２２６８を用い、光照射に用いる半導体レーザーの発信波長を７８０ｎｍから８３０ｎｍに変更する以外は実施例１と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０１６５】
なおＮＫ−２２６８をガラスやクオーツ等の透明基板に塗布した際に形成される色素薄膜の吸収極大波長は約８３０ｎｍである。
【０１６６】
【実施例４】
林原生物化学研究所社製色素ＮＫ−２０１４の代わりに林原生物化学研究所社製色素ＮＫ−３９８７を用い、光照射に用いる半導体レーザーの発信波長を７８０ｎｍから６７０ｎｍに変更する以外は実施例１と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０１６７】
なおＮＫ−３９８７をガラスやクオーツ等の透明基板に塗布した際に形成される色素薄膜の吸収極大波長は約６７０ｎｍである。
【０１６８】
【実施例５】
林原生物化学研究所社製色素ＮＫ−２０１４の代わりに林原生物化学研究所社製色素ＮＫ−２９２９を用い、光照射に用いる半導体レーザーの発信波長を７８０ｎｍから６７０ｎｍに変更する以外は実施例１と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０１６９】
なおＮＫ−２９２９をガラスやクオーツ等の透明基板に塗布した際に形成される色素薄膜の吸収極大波長は約６７０ｎｍである。
【０１７０】
【実施例６】
林原生物化学研究所社製色素ＮＫ−２０１４の代わりに林原生物化学研究所社製色素ＮＫ−１８８６を用い、光照射に用いるレーザーをアルゴンレーザーに代え、発信波長を７８０ｎｍから４１５ｎｍに変更する以外は実施例１と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０１７１】
なおＮＫ−１８８６をガラスやクオーツ等の透明基板に塗布した際に形成される色素薄膜の吸収極大波長は約４１５ｎｍである。
【０１７２】
またＮＫ−１８８６の代わりに林原生物化学研究所社製色素ＮＫ−７２３を用い、発信波長を４１５ｎｍから４８８ｎｍに変更する以外は上記と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０１７３】
なおＮＫ−７２３をガラスやクオーツ等の透明基板に塗布した際に形成される色素薄膜の吸収極大波長は約４９０ｎｍである。
【０１７４】
またＮＫ−１８８６の代わりに林原生物化学研究所社製色素ＮＫ−１４２０を用い、発信波長を４１５ｎｍから５１５ｎｍに変更する以外は上記と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０１７５】
なおＮＫ−１４２０をガラスやクオーツ等の透明基板に塗布した際に形成される色素薄膜の吸収極大波長は約５１５ｎｍである。
【０１７６】
【実施例７】
林原生物化学研究所社製色素ＮＫ−２０１４の代わりに林原生物化学研究所社製色素ＮＫ−５２９を用い、光照射に用いるレーザーをヘリウム／ネオンレーザーに代え、結果として発信波長を７８０ｎｍから６３３ｎｍに変更される以外は実施例１と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０１７７】
なおＮＫ−５２９をガラスやクオーツ等の透明基板に塗布した際に形成される色素薄膜の吸収極大波長は約６３５ｎｍである。
【０１７８】
【実施例８】
林原生物化学研究所社製色素ＮＫ−２０１４の代わりに林原生物化学研究所社製色素ＮＫ−３５０８を用い、光照射に用いるレーザーをＹＡＧレーザーに代え、結果として発信波長が７８０ｎｍから１０６４ｎｍに変更される以外は実施例１と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０１７９】
なおＮＫ−３５０８をガラスやクオーツ等の透明基板に塗布した際に形成される色素薄膜の吸収極大波長は約１０６０ｎｍである。
【０１８０】
またＮＫ−３５０８の代わりに林原生物化学研究所社製色素ＮＫ−１０４６を用い、用いるＹＡＧレーザーの光学系に２次の非線形素子を組み合わせ、発信波長を１０６４ｎｍから５３２ｎｍに変更する以外は上記と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０１８１】
なおＮＫ−１０４６をガラスやクオーツ等の透明基板に塗布した際に形成される色素薄膜の吸収極大波長は約５３０ｎｍである。
【０１８２】
またＮＫ−３５０８の代わりに林原生物化学研究所社製色素ＮＫＸ−１３１７を用い、用いるＹＡＧレーザーの光学系に３次の非線形素子を組み合わせ、発信波長を１０６４ｎｍから３５５ｎｍに変更する以外は上記と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０１８３】
なおＮＫＸ−１３１７をガラスやクオーツ等の透明基板に塗布した際に形成される色素薄膜の吸収極大波長は約３６０ｎｍである。
【０１８４】
またＮＫ−３５０８を加えず、用いるＹＡＧレーザーの光学系に４次の非線形素子を組み合わせ、発信波長を１０６４ｎｍから２６６ｎｍに変更する以外は上記と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０１８５】
なおＮＫ−３５０８を加えない場合は光吸収層はマルカリンカーＭのみで形成される薄膜になる。マルカリンカーＭをガラスやクオーツ等の透明基板に塗布した際に形成される色素薄膜の吸収は４５０ｎｍ近傍から観測され、短波長ほど吸収が大きくなり、波長２５０ｎｍ以上では明確な極大波長は観測されなかった。ただ光吸収層の２６６ｎｍにおける吸光度は２．０以上あるため、吸収率は９９％以上であることが確認された。即ち照射された光のほとんどが吸収され、熱エネルギーに変わっていると判断される。
【０１８６】
【実施例９】
林原生物化学研究所社製色素ＮＫ−２０１４の代わりに林原生物化学研究所社製色素ＮＫ−３２１２を用い、光照射に用いる光源を超高圧水銀ランプに代え、４００ｎｍ以下の光をカットするフィルター、及び非配線部分だけ光が遮蔽されるマスクを介して光照射を行う以外は実施例１と同様の操作で配線基板を形成する。この場合、照射される光の波長は４３５ｎｍになる。なお照射光の単位時間あたりのエネルギーは実施例１と同様に調整する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０１８７】
なおＮＫ−３２１２をガラスやクオーツ等の透明基板に塗布した際に形成される色素薄膜の吸収極大波長は約４３５ｎｍである。
【０１８８】
またＮＫ−３２１２の代わりに林原生物化学研究所社製色素ＮＫＸ−１３１７を用い、４００ｎｍ以下の光をカットするフィルターの代わりに３５０ｎｍをカットするフィルターを用いる以外は上記と同様の操作で配線基板を形成する。この場合、照射される光の波長は３６５ｎｍになる。なお照射光の単位時間あたりのエネルギーはこの場合も実施例１と同様に調整する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０１８９】
なおＮＫＸ−１３１７をガラスやクオーツ等の透明基板に塗布した際に形成される色素薄膜の吸収極大波長は約３６０ｎｍである。
【０１９０】
またＮＫ−３２１２を加えず、用いるランプを超高圧水銀ランプから高圧水銀ランプに代え、４００ｎｍ以下の光をカットするフィルターの代わりに３００ｎｍをカットするフィルターを用いる以外は上記と同様の操作で配線基板を形成する。この場合、照射される光の波長は２５４ｎｍになる。なお照射光の単位時間あたりのエネルギーはこの場合も実施例１と同様に調整する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０１９１】
なおＮＫ−３５０８を加えない場合は光吸収層はマルカリンカーＭのみで形成される薄膜になる。マルカリンカーＭをガラスやクオーツ等の透明基板に塗布した際に形成される色素薄膜の吸収は４５０ｎｍ近傍から観測され、短波長ほど吸収が大きくなり、波長２５０ｎｍ以上では明確な極大波長は観測されなかった。ただ光吸収層の２５４ｎｍにおける吸光度は１．０　以上あるため、吸収率は９０％以上であることが確認された。即ち照射された光のほとんどが吸収され、熱エネルギーに変わっていると判断される。
【０１９２】
【実施例１０】
撥水層形成工程で化合物１の０．１　重量％ＰＦ−５０８０溶液の代わりに、化合物２の０．１　重量％ＰＦ−５０８０溶液を用いる以外は実施例１と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０１９３】
【実施例１１】
撥水層形成工程で化合物１の０．１　重量％ＰＦ−５０８０溶液の代わりに、化合物３の０．１　重量％ＰＦ−５０８０溶液を用いる以外は実施例１と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０１９４】
【実施例１２】
撥水層形成工程で化合物１の０．１　重量％ＰＦ−５０８０溶液の代わりに、化合物４の０．１　重量％ＰＦ−５０８０溶液を用いる以外は実施例１と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０１９５】
【実施例１３】
撥水層形成工程で化合物１の０．１　重量％ＰＦ−５０８０溶液の代わりに、化合物５の０．１　重量％ＰＦ−５０８０溶液を用いる以外は実施例１と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０１９６】
【実施例１４】
撥水層形成工程で化合物１の０．１　重量％ＰＦ−５０８０溶液の代わりに、化合物６の０．１　重量％ＰＦ−５０８０溶液を用いる以外は実施例１と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０１９７】
【実施例１５】
撥水層形成工程で化合物１の０．１　重量％ＰＦ−５０８０溶液の代わりに、化合物７の０．１　重量％ＰＦ−５０８０溶液を用いる以外は実施例１と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０１９８】
【実施例１６】
撥水層形成工程で化合物１の０．１　重量％ＰＦ−５０８０溶液の代わりに、化合物８の０．１　重量％ＰＦ−５０８０溶液を用いる以外は実施例１と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０１９９】
【実施例１７】
撥水層形成工程で化合物１の０．１　重量％ＰＦ−５０８０溶液の代わりに、化合物９の０．１　重量％ＰＦ−５０８０溶液を用いる以外は実施例１と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０２００】
【実施例１８】
撥水層形成工程で化合物１の０．１　重量％ＰＦ−５０８０溶液の代わりに、化合物１０の０．１　重量％ＰＦ−５０８０溶液を用いる以外は実施例１と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０２０１】
【実施例１９】
撥水層形成工程で化合物１の０．１　重量％ＰＦ−５０８０溶液の代わりに、化合物１１の０．１　重量％ＰＦ−５０８０溶液を用いる以外は実施例１と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０２０２】
【実施例２０】
撥水層形成工程で化合物１の０．１　重量％ＰＦ−５０８０溶液の代わりに、化合物１２の０．１　重量％ＰＦ−５０８０溶液を用いる以外は実施例１と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０２０３】
【実施例２１】
撥水層形成工程で化合物１の０．１　重量％ＰＦ−５０８０溶液の代わりに、オプツールＤＳＸ（ダイキン工業社製）の０．１　重量％ＰＦ−５０６０溶液（ＰＦ−５０６０は３Ｍ社製）を用いる以外は実施例１と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０２０４】
【実施例２２】
撥水層形成工程で化合物１の０．１　重量％ＰＦ−５０８０溶液の代わりに、サイトップＣＴＬ−１０７Ｍ（旭硝子社製）７重量％溶液をＰＦ−５０８０で０．１重量％に希釈した溶液を用いる以外は実施例１と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０２０５】
【実施例２３】
撥水層形成工程で化合物１の０．１　重量％ＰＦ−５０８０溶液の代わりに、
ＩＮＴ−３０４ＶＣ（ＩＮＴスクリーン社製）２重量％溶液をＰＦ−５０８０で０．１　重量％に希釈した溶液を用いる以外は実施例１と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０２０６】
【実施例２４】
（１）光吸収部位を有する撥水層形成工程
ガラス製基板に化合物１３の０．１　重量％ＨＦＥ−７２００溶液（ＨＦＥ−７２００は３Ｍ社製）に１０分間浸漬後、１２０℃で１０分間加熱する。こうして光吸収部位を持つ撥水層が形成される。
【０２０７】
なお化合物１３をガラスやクオーツ等の透明基板に塗布した際に形成される色素薄膜の吸収極大波長は約５００ｎｍである。
【０２０８】
（２）光照射工程
出力３ｍＷ，発信波長４８８ｎｍのアルゴンレーザーを用い、レーザースポット径２μｍ，スキャン速度１０ｍｍ／秒で基板表面の配線形成予定部分に光を照射する。
【０２０９】
すると照射した光が熱に変わり、化合物１３により形成された撥水層がこの熱で変性を起こし、結果として変性部分（即ち光照射部分）の撥水性が低下する。
【０２１０】
（３）金属配線形成工程
０．５　重量％の銀微粒子分散液（溶媒は水、液の表面張力は６９ｍＮ／ｍ、銀微粒子の一次粒子の平均粒径は約２０ｎｍ）が深さ５ｍｍになるよう入っているバットを用意する。バットは基板が入るだけの大きさがある。光照射後の基板の光照射面を下にしてバットの中に入れた後、すぐに引き上げる。光の非照射部分には銀微粒子分散液が付着しないが、光の照射部分に銀微粒子分散液が付着する。基板の銀微粒子分散液が付着した側を上にして１２０℃で１５分間加熱する。銀微粒子分散液の付着した部分は溶媒の水が揮発し、銀の配線が形成された。
【０２１１】
（４）導通確認試験
形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０２１２】
【実施例２５】
化合物１３の代わりに化合物１４を用い、光照射に用いるレーザーをアルゴンレーザーからヘリウム／ネオンレーザーに代え、結果として発信波長を４８８
ｎｍから６３３ｎｍに変更される以外は実施例２４と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０２１３】
なお化合物１４をガラスやクオーツ等の透明基板に塗布した際に形成される色素薄膜の吸収極大波長は約６００ｎｍである。
【０２１４】
【実施例２６】
化合物１３の代わりに化合物１５を用いる以外は実施例２４と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０２１５】
なお化合物１５をガラスやクオーツ等の透明基板に塗布した際に形成される色素薄膜の吸収極大波長は約５００ｎｍである。
【０２１６】
【実施例２７】
化合物１３の代わりに化合物１６を用い、光照射に用いるレーザーをアルゴンレーザーからヘリウム／ネオンレーザーに代え、結果として発信波長を４８８ｎｍから６３３ｎｍに変更される以外は実施例２４と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０２１７】
なお化合物１６をガラスやクオーツ等の透明基板に塗布した際に形成される色素薄膜の吸収極大波長は約６００ｎｍである。
【０２１８】
【実施例２８】
化合物１３の代わりに化合物１７を用いる以外は実施例２４と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０２１９】
なお化合物１７をガラスやクオーツ等の透明基板に塗布した際に形成される色素薄膜の吸収極大波長は約５００ｎｍである。
【０２２０】
【実施例２９】
化合物１３の代わりに化合物１８を用い、光照射に用いるレーザーをアルゴンレーザーからヘリウム／ネオンレーザーに代え、結果として発信波長を４８８ｎｍから６３３ｎｍに変更される以外は実施例２４と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０２２１】
なお化合物１８をガラスやクオーツ等の透明基板に塗布した際に形成される色素薄膜の吸収極大波長は約６００ｎｍである。
【０２２２】
【実施例３０】
化合物１３の代わりに化合物１９を用いる以外は実施例２４と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０２２３】
なお化合物１９をガラスやクオーツ等の透明基板に塗布した際に形成される色素薄膜の吸収極大波長は約５００ｎｍである。
【０２２４】
【実施例３１】
化合物１３の代わりに化合物２０を用い、光照射に用いるレーザーをアルゴンレーザーからヘリウム／ネオンレーザーに代え、結果として発信波長を４８８ｎｍから６３３ｎｍに変更される以外は実施例２４と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０２２５】
なお化合物２０をガラスやクオーツ等の透明基板に塗布した際に形成される色素薄膜の吸収極大波長は約６００ｎｍである。
【０２２６】
【実施例３２】
化合物１３の代わりに化合物２１を用いる以外は実施例２４と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０２２７】
なお化合物２１をガラスやクオーツ等の透明基板に塗布した際に形成される色素薄膜の吸収極大波長は約５００ｎｍである。
【０２２８】
【実施例３３】
化合物１３の代わりに化合物２２を用いる以外は実施例２４と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０２２９】
なお化合物２２をガラスやクオーツ等の透明基板に塗布した際に形成される色素薄膜の吸収極大波長は約５００ｎｍである。
【０２３０】
【実施例３４】
化合物１３の代わりに化合物２３を用い、光照射に用いるレーザーをアルゴンレーザーからヘリウム／ネオンレーザーに代え、結果として発信波長を４８８ｎｍから６３３ｎｍに変更される以外は実施例２４と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０２３１】
なお化合物２３をガラスやクオーツ等の透明基板に塗布した際に形成される色素薄膜の吸収極大波長は約６００ｎｍである。
【０２３２】
【実施例３５】
化合物１３の代わりに化合物２４を用い、光照射に用いるレーザーをアルゴンレーザーからヘリウム／ネオンレーザーに代え、結果として発信波長を４８８ｎｍから６３３ｎｍに変更される以外は実施例２４と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０２３３】
なお化合物２４をガラスやクオーツ等の透明基板に塗布した際に形成される色素薄膜の吸収極大波長は約６００ｎｍである。
【０２３４】
【実施例３６】
化合物１３の代わりに化合物２５を用いる以外は実施例２４と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０２３５】
なお化合物２５をガラスやクオーツ等の透明基板に塗布した際に形成される色素薄膜の吸収極大波長は約５００ｎｍである。
【０２３６】
【実施例３７】
化合物１３の代わりに化合物２６を用い、光照射に用いるレーザーをアルゴンレーザーからヘリウム／ネオンレーザーに代え、結果として発信波長を４８８ｎｍから６３３ｎｍに変更される以外は実施例２４と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０２３７】
なお化合物２６をガラスやクオーツ等の透明基板に塗布した際に形成される色素薄膜の吸収極大波長は約６００ｎｍである。
【０２３８】
【実施例３８】
化合物１３の代わりに化合物２７を用いる以外は実施例２４と同様の操作で配線基板を形成する。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０２３９】
なお化合物２７をガラスやクオーツ等の透明基板に塗布した際に形成される色素薄膜の吸収極大波長は約５００ｎｍである。
【０２４０】
【実施例３９】
化合物１３の代わりに化合物１を用い、光照射に用いるレーザーをアルゴンレーザーから低圧水銀ランプに代え、３００ｎｍ以上の光をカットするフィルターを介することで結果として発信波長を４８８ｎｍから２５４ｎｍに変更される以外は実施例２４と同様の操作で配線基板を形成する。なお光の出力、および照射面積は同様になるように光学系を調整した。この配線基板も形成された配線の端と端にテスターの検知針を接触させると、電気の導通が確認された。また、配線の形成されていない場所の絶縁性も確認された。
【０２４１】
なお化合物１はアミド結合があるため、２７０ｎｍ近傍から吸収が観測され、そこから２５０ｎｍまでは短波長になるほどその吸収が大きくなる。ガラスやクオーツ等の透明基板に塗布した際の２５４ｎｍの吸光度は０．５３以上であった。吸収率としては７０％以上である。
【０２４２】
【実施例４０】
各実施例で形成された配線の幅を計測したところ、実施例１〜２０、及び２３〜３８で形成された配線の幅は３μｍ以下であった。しかし実施例２２，２３で形成された配線の幅は５μｍであった。光照射の際のスポット径は２μｍであるから、照射時の光の幅は２μｍとなる。実施例２２と２３では光のエネルギーから変換された熱エネルギーの拡散が起こったものと推定される。実施例２２，２３では用いた撥水層形成材料がフッ素系の樹脂材料サイトップＣＴＬ−１０７Ｍ、或いはＩＮＴ３０４−ＶＣである。そこで伝わり方を改善を図る目的で撥水層を薄膜化するため、サイトップＣＴＬ−１０７Ｍ、或いはＩＮＴ３０４−ＶＣの溶液濃度を１／２にして実験したが配線幅は５μｍであった。それ以外の実施例で用いた撥水層形成材料はパーフルオロポリエーテル鎖またはフルオロアルキル鎖とアルコキシシラン残基を有する含フッ素化合物である。以上より光照射の幅に対応した幅の配線が得られる点で撥水層形成材料はパーフルオロポリエーテル鎖またはフルオロアルキル鎖とアルコキシシラン残基を有する含フッ素化合物を用いることが効果的であることが示された。
【０２４３】
【実施例４１】
本発明の技術を用いて表示素子用のＴＦＴの作製を試みた。図３にその作製の工程の模式図を示す。
【０２４４】
（１）光吸収部位を持つ撥水層形成工程
大きさ１００×１００ｍｍ，厚さ１ｍｍのガラス製基板１１に化合物１４の０．１　重量％ＨＦＥ−７２００溶液（ＨＦＥ−７２００は３Ｍ社製）に１０分間浸漬後、１２０℃で１０分間加熱する。こうして光吸収部位を持つ撥水層１２が形成される。
【０２４５】
（２）光照射工程
出力３ｍＷ，発信波長６３３ｎｍのヘリウム／ネオンレーザーを用い、レーザースポット径２μｍ，スキャン速度１０ｍｍ／秒で基板表面のゲート電極形成予定部分に６３３ｎｍの光１３を照射する。
【０２４６】
なお図３では光照射部分は光吸収部位を持つ撥水層がなくなっているように描かれているが、実際には光吸収部位を持つ撥水層が変性したもの（一種の含フッ素化合物からなる層）が残っている。ＴＯＦ−ＳＩＭＳで撥水層が変性した表面を分析するとフッ素原子のシグナルが観測された。このことから光照射を受けた部分は撥水性の低下は認められるものの、含フッ素化合物からなる層としては存在することが確かめられた。
【０２４７】
（３）ゲート電極形成工程
０．５　重量％の銀微粒子分散液（溶媒は水、液の表面張力は６９ｍＮ／ｍ、銀微粒子の一次粒子の平均粒径は約２０ｎｍ）が深さ５ｍｍになるよう入っているバットを用意する。バットは基板が入るだけの大きさがある。光照射後の基板の光照射面を下にしてバットの中に入れた後、すぐに引き上げる。光の非照射部分には銀微粒子分散液が付着しないが、光の照射部分に銀微粒子分散液が付着する。基板の銀微粒子分散液が付着した側を上にして１２０℃で１５分間加熱する。銀微粒子分散液の付着した部分は溶媒の水が揮発し、銀のゲート電極１４が形成される。
【０２４８】
（４）全面光照射工程
２０００Ｗのキセノンランプを用いて基板全面に１０分間光照射する。照射光１５にはフィルターは特に介さない。この光照射により表面の撥水性が失われる。
【０２４９】
なお図３では光照射面の光吸収部位を持つ撥水層がなくなっているように描かれているが、実際には光吸収部位を持つ撥水層が変性したもの（一種の含フッ素化合物からなる層）が残っている。
【０２５０】
（５）絶縁層形成
銀の配線が形成された上にポリ（ビニルフェノール）の１％メチルエチルケトン溶液をスピンコート法（回転数２００ｒｐｍ　，回転時間：６０秒間）で塗布後、１００℃で１０分間乾燥しメチルエチルケトンを揮発させる。ポリ（ビニルフェノール）の化学構造は以下の通りである。
【０２５１】
【化３８】

【０２５２】
こうしてポリ（ビニルフェノール）からなる絶縁層１６が形成される。
【０２５３】
（６）光吸収部位を持つ撥水層形成工程
絶縁層を形成した基板を化合物１４の０．１　重量％ＨＦＥ−７２００溶液（ＨＦＥ−７２００は３Ｍ社製）に１０分間浸漬後、１２０℃で１０分間加熱する。こうして絶縁層の上に光吸収部位を持つ撥水層１７が形成される。
【０２５４】
（７）光照射工程
出力３ｍＷ，発信波長６３３ｎｍのヘリウム／ネオンレーザーを用い、レーザースポット径２μｍ，スキャン速度１０ｍｍ／秒で基板表面のソース電極とドレイン電極の形成予定部分に６３３ｎｍの光１８を照射する。
【０２５５】
なお図３では光照射部分は光吸収部位を持つ撥水層がなくなっているように描かれているが、実際には光吸収部位を持つ撥水層が変性したもの（一種の含フッ素化合物からなる層）が残っている。
【０２５６】
（８）金属電極形成工程
（２）で用いたものと同じ０．５　重量％の銀微粒子分散液が深さ５ｍｍになるよう入っているバットを用意する。光照射後の基板の光照射面を下にしてバットの中に入れた後、すぐに引き上げる。光の非照射部分には銀微粒子分散液が付着しないが、光の照射部分に銀微粒子分散液が付着する。基板の銀微粒子分散液が付着した側を上にして１２０℃で１５分間加熱する。銀微粒子分散液の付着した部分は溶媒の水が揮発し、ソース電極とドレイン電極１９が形成される。
【０２５７】
（９）光吸収部位を持つ撥水層形成工程
電極を形成した基板を化合物１４の０．１　重量％ＨＦＥ−７２００溶液（ＨＦＥ−７２００は３Ｍ社製）に１０分間浸漬後、１２０℃で１０分間加熱する。こうして基板の電極を形成した面の全面に光吸収部位を持つ撥水層２０が形成される。
【０２５８】
（１０）光照射工程
出力３ｍＷ，発信波長６３３ｎｍのヘリウム／ネオンレーザーを用い、レーザースポット径２μｍ，スキャン速度１０ｍｍ／秒で基板表面の半導体部位形成予定部分に６３３ｎｍの光２１を照射する。
【０２５９】
なお図３では光照射部分は光吸収部位を持つ撥水層がなくなっているように描かれているが、実際には光吸収部位を持つ撥水層が変性したもの（一種の含フッ素化合物からなる層）が残っている。
【０２６０】
（１１）半導体部位形成
ポリ−（９，９−ジオクチルフルオレン−ビスチオフェン）の１％キシレン溶液が深さ５ｍｍになるよう入っているバットを用意する。ポリ−（９，９−ジオクチルフルオレン−ビスチオフェン）の化学構造を下記に示す。
【０２６１】
【化３９】

【０２６２】
光照射後の基板の光照射面を下にしてバットの中に入れた後、すぐに引き上げる。光の非照射部分にはポリ−（９，９−ジオクチルフルオレン−ビスチオフェン）の１％キシレン溶液が付着しないが、光の照射部分にポリ−（９，９−ジオクチルフルオレン−ビスチオフェン）の１％キシレン溶液が付着する。基板のポリ−（９，９−ジオクチルフルオレン−ビスチオフェン）の１％キシレン溶液が付着した側を上にして１２０℃で１０分間加熱する。ポリ−（９，９−ジオクチルフルオレン−ビスチオフェン）の１％キシレン溶液の付着した部分は溶媒のキシレンが揮発し、ポリ−（９，９−ジオクチルフルオレン−ビスチオフェン）からなる半導体部位２２が形成される。
【０２６３】
（１２）光照射工程
出力３ｍＷ，発信波長６３３ｎｍのヘリウム／ネオンレーザーを用い、レーザースポット径２μｍ，スキャン速度１０ｍｍ／秒で基板表面の半導体部位形成部分以外に６３３ｎｍの光２３を照射する。
【０２６４】
なお図３では光照射部分は光吸収部位を持つ撥水層がなくなっているように描かれているが、実際には光吸収部位を持つ撥水層が変性したもの（一種の含フッ素化合物からなる層）が残っている。
【０２６５】
（１３）絶縁層形成
半導体部位が形成された表面上にポリ（ビニルフェノール）の１％メチルエチルケトン溶液をスピンコート法（回転数２００ｒｐｍ　，回転時間：６０秒間）で塗布後、１００℃で１０分間乾燥しメチルエチルケトンを揮発させる。こうしてポリ（ビニルフェノール）からなる保護層２４が形成される。
【０２６６】
以上の工程でＴＦＴを作製できた。作製したＴＦＴに配線を施しディスプレイ作成後、画像の出力試験を行ったところ、画像出力が可能であった。よって本発明によって、真空工程を経ずにＴＦＴの作製が可能であることが確かめられた。
【０２６７】
【実施例４２】
化合物１４の代わりに化合物１３を用い、光照射に用いるレーザーをヘリウム／ネオンレーザーからアルゴンレーザーに代え、結果として発信波長を６３３ｎｍから４８８ｎｍに変更される以外は実施例４１と同様の操作でＴＦＴを作製する。作製したＴＦＴに配線を施しディスプレイ作成後、画像の出力試験を行ったところ、画像出力が可能であった。よって本発明によって、真空工程を経ずにＴＦＴの作製が可能であることが再度確かめられた。
【０２６８】
【実施例４３】
本発明の技術を用いて有機のＥＬ基板の作製を試みた。図４にその作製の工程を模式的に表したものを示す。
【０２６９】
（１）光吸収部位を持つ撥水層形成工程
大きさ１００×１００ｍｍ，厚さ１ｍｍで表面にＩＴＯ製の透明電極２５が形成されているガラス製基板２６を化合物１４の０．１　重量％ＨＦＥ−７２００溶液（ＨＦＥ−７２００は３Ｍ社製）に１０分間浸漬後、１２０℃で１０分間加熱する。こうして光吸収部位を持つ撥水層２７が形成される。
【０２７０】
（２）光照射工程
出力３ｍＷ，発信波長６３３ｎｍのヘリウム／ネオンレーザーを用い、レーザースポット径２μｍ，スキャン速度１０ｍｍ／秒で基板表面の絶縁層形成予定部分に６３３ｎｍの波長の光２８を照射する。
【０２７１】
なお図４では光照射部分は光吸収部位を持つ撥水層がなくなっているように描かれているが、実際には光吸収部位を持つ撥水層が変性したもの（一種の含フッ素化合物からなる層）が残っている。
【０２７２】
（３）絶縁層形成
ポリ（ビニルフェノール）の１％メチルエチルケトン溶液が深さ５ｍｍになるよう入っているバットを用意する。バットは基板が入るだけの大きさがある。光照射後の基板の光照射面を下にしてバットの中に入れた後、すぐに引き上げる。光の非照射部分にはポリ（ビニルフェノール）の１％メチルエチルケトン溶液が付着しないが、光の照射部分にはポリ（ビニルフェノール）の１％メチルエチルケトン溶液が付着する。基板の溶液が付着した側を上にして１００℃で１０分間加熱する。こうしてポリ（ビニルフェノール）からなる絶縁層２９が形成される。
【０２７３】
（４）光吸収部位を持つ撥水層形成工程
絶縁層を形成した基板を化合物１４の０．１　重量％ＨＦＥ−７２００溶液（ＨＦＥ−７２００は３Ｍ社製）に１０分間浸漬後、１２０℃で１０分間加熱する。こうして絶縁層の上に光吸収部位を持つ撥水層３０が形成される。
【０２７４】
（５）光照射工程
出力３ｍＷ，発信波長６３３ｎｍのヘリウム／ネオンレーザーを用い、レーザースポット径２μｍ，スキャン速度１０ｍｍ／秒で基板表面の透明電極形成部分に６３３ｎｍの波長の光３１を照射する。
【０２７５】
なお図４では光照射部分は光吸収部位を持つ撥水層がなくなっているように描かれているが、実際には光吸収部位を持つ撥水層が変性したもの（一種の含フッ素化合物からなる層）が残っている。
【０２７６】
（６）正孔輸送層形成工程
０．１　重量％の銅フタロシアニンのクロロホルム分散液（銅フタロシアニンの一次粒子の大きさは平均約５０ｎｍ）が深さ５ｍｍになるよう入っているバットを用意する。バットは基板が入るだけの大きさがある。光照射後の基板の光照射面を下にしてバットの中に入れた後、すぐに引き上げる。光の非照射部分には銅フタロシアニンのクロロホルム分散液が付着しないが、光の照射部分には銅フタロシアニンのクロロホルム分散液が付着する。基板の分散液が付着した側を上にして７０℃で１５分間加熱する。銅フタロシアニンのクロロホルム分散液の付着した部分は分散媒のクロロホルムが揮発し、正孔輸送層３２が形成される。
【０２７７】
（７）発光層形成工程
０．１　重量％のパラフルオレンのシクロヘキサノン溶液が深さ５ｍｍになるよう入っているバットを用意する。バットは基板が入るだけの大きさがある。正孔輸送層形成後の基板の正孔輸送層形成面を下にしてバットの中に入れた後、すぐに引き上げる。正孔輸送層の非形成部分にはパラフルオレンのシクロヘキサノン溶液が付着しないが、正孔輸送層の形成部分にはパラフルオレンのシクロヘキサノン溶液が付着する。基板を溶液の付着した側を上にして１２０℃で１５分間加熱する。パラフルオレンのシクロヘキサノン溶液の付着した部分は溶媒のシクロヘキサノンが揮発し、発光層３３が形成される。
【０２７８】
（８）光照射工程
出力３ｍＷ，発信波長６３３ｎｍのヘリウム／ネオンレーザーを用い、レーザースポット径２μｍ，スキャン速度１０ｍｍ／秒で絶縁層部分に６３３ｎｍの波長の光３４を照射する。これにより絶縁層の上の撥水性が低下する。
【０２７９】
なお図４では光照射部分は光吸収部位を持つ撥水層がなくなっているように描かれているが、実際には光吸収部位を持つ撥水層が変性したもの（一種の含フッ素化合物からなる層）が残っている。
【０２８０】
（９）金属電極形成工程
０．５　重量％の銀微粒子分散液（溶媒は水とエタノールの混合溶媒、液の表面張力は３０ｍＮ／ｍ、銀微粒子の一次粒子の平均粒径は約２０ｎｍ）をスピンコート法（回転数２００ｒｐｍ　，回転時間：６０秒間）で塗布後、１２０℃で１０分間乾燥し溶媒を揮発させる。こうして銀製の金属電極３５が形成される。
【０２８１】
（１０）封止層形成
金属電極が形成された上にポリ（ビニルフェノール）の１％メチルエチルケトン溶液をスピンコート法（回転数２００ｒｐｍ　，回転時間：６０秒間）で塗布後、１００℃で１０分間乾燥しメチルエチルケトンを揮発させる。こうして封止層３６が形成される。
【０２８２】
以上の工程で有機のＥＬ基板を作製できた。作製した有機のＥＬ基板に配線を施し発光デバイス作成後、発光するか否か試験を行ったところ、発光することが確認された。よって本発明の方法によって有機のＥＬ基板の作製が可能であることが確かめられた。
【０２８３】
【実施例４４】
化合物１４の代わりに化合物１３を用い、光照射に用いるレーザーをヘリウム／ネオンレーザーからアルゴンレーザーに代え、結果として発信波長を６３３ｎｍから４８８ｎｍに変更される以外は実施例４３と同様の操作で有機のＥＬ基板を作製する。作製した有機のＥＬ基板に配線を施し発光デバイス作成後、発光するか否か試験を行ったところ、発光することが確認された。よって本発明の方法によって有機のＥＬ基板の作製が可能であることが再度確かめられた。
【０２８４】
【実施例４５】
本発明の技術を用いてディスプレイ用カラーフィルターパネルの作製を試みた。図５にその作製の工程を示す。
【０２８５】
（１）光吸収部位を持つ撥水層形成工程
大きさ２５０×１９０ｍｍ、厚さ１ｍｍのガラス製基板３７を化合物１４の０．１　重量％ＨＦＥ−７２００溶液（ＨＦＥ−７２００は３Ｍ社製）に１０分間浸漬後、１２０℃で１０分間加熱する。こうして光吸収部位を持つ撥水層３８が形成される。
【０２８６】
（２）光照射工程
出力３ｍＷ，発信波長６３３ｎｍのヘリウム／ネオンレーザーを用い、レーザースポット径２μｍ，スキャン速度１０ｍｍ／秒で基板表面のブラックマトリクス形成予定部分に６３３ｎｍの波長の光３９を照射する。
【０２８７】
なお図５では光照射部分は光吸収部位を持つ撥水層がなくなっているように描かれているが、実際には光吸収部位を持つ撥水層が変性したもの（一種の含フッ素化合物からなる層）が残っている。
【０２８８】
（３）ブラックマトリクス形成
カーボンブラック（一次粒子の平均粒径は約５０ｎｍ）（１０重量部），花王製の粒子分散剤ゲラニオールＬ−９５（１重量部）をシクロヘキサノン（１０００重量部）に加え、遊星ボールミルで攪拌してカーボンブラックを分散させた後、ポリ（ビニルフェノール）（５０重量部）とエポキシ樹脂ＥＰ１００１（５０重量部），ベンゾイミダゾール（１重量部）を加え、攪拌する。こうしてブラックマトリクス形成部材を溶解，懸濁させた液を調製する。この液を今後ブラックマトリクス形成液と記述する。
【０２８９】
ブラックマトリクス形成液が深さ５ｍｍになるよう入っているバットを用意する。バットは基板が入るだけの大きさがある。光照射後の基板の光照射面を下にしてバットの中に入れた後、すぐに引き上げる。光の非照射部分にはブラックマトリクス形成液が付着しないが、光の照射部分にはブラックマトリクス形成液が付着する。基板の液が付着した側を上にして１２０℃で１０分間加熱する。こうしてブラックマトリクス４０が形成される。
【０２９０】
（４）光吸収部位を持つ撥水層形成工程
ブラックマトリクスを形成した基板を化合物１４の０．１　重量％ＨＦＥ−７２００溶液（ＨＦＥ−７２００は３Ｍ社製）に１０分間浸漬後、１２０℃で１０分間加熱する。こうしてブラックマトリクスの上に光吸収部位を持つ撥水層４１が形成される。
【０２９１】
（５）光照射工程
出力３ｍＷ，発信波長６３３ｎｍのヘリウム／ネオンレーザーを用い、レーザースポット径２μｍ，スキャン速度１０ｍｍ／秒で基板表面のカラーフィルターのＲを形成する部分に６３３ｎｍの波長の光４２を照射する。
【０２９２】
なお図５では光照射部分は光吸収部位を持つ撥水層がなくなっているように描かれているが、実際には光吸収部位を持つ撥水層が変性したもの（一種の含フッ素化合物からなる層）が残っている。
【０２９３】
（６）カラーフィルターのＲ部分形成工程
Ｒ用の赤色色素Ｃ．Ｉ．ピグメントレッド１７７（１０重量部），花王製の粒子分散剤ゲラニオールＬ−９５（１重量部）をエタノール（１００重量部）に加え、遊星ボールミルで攪拌してＣ．Ｉ．ピグメントレッド１７７を分散させた後、６重量％のシリカゾル溶液（平均分子量２０００〜４０００。溶媒はエタノールが７０％、それ以外は水が主成分。液性はリン酸でｐＨ３前後に制御）（２０重量部）を加える。これを今後カラーフィルターのＲ部分形成液と記述する。
【０２９４】
カラーフィルターのＲ部分形成液が深さ５ｍｍになるよう入っているバットを用意する。バットは基板が入るだけの大きさがある。光照射後の基板の光照射面を下にしてバットの中に入れた後、すぐに引き上げる。光の非照射部分にはカラーフィルターのＲ部分形成液が付着しないが、光の照射部分にはカラーフィルターのＲ部分形成液が付着する。基板の液が付着した側を上にして１２０℃で１０分間加熱する。こうしてカラーフィルターのＲ部分４３が形成される。
【０２９５】
（７）光吸収部位を持つ撥水層形成工程
カラーフィルターのＲ部分を形成した基板を化合物１４の０．１　重量％ＨＦＥ−７２００溶液（ＨＦＥ−７２００は３Ｍ社製）に１０分間浸漬後、１２０℃で１０分間加熱する。こうしてカラーフィルターのＲ部分の上に光吸収部位を持つ撥水層４４が形成される。
【０２９６】
（８）光照射工程
出力３ｍＷ，発信波長６３３ｎｍのヘリウム／ネオンレーザーを用い、レーザースポット径２μｍ，スキャン速度１０ｍｍ／秒で基板表面のカラーフィルターのＧを形成する部分に６３３ｎｍの波長の光４５を照射する。
【０２９７】
なお図５では光照射部分は光吸収部位を持つ撥水層がなくなっているように描かれているが、実際には光吸収部位を持つ撥水層が変性したもの（一種の含フッ素化合物からなる層）が残っている。
【０２９８】
（９）カラーフィルターのＧ部分形成工程
Ｇ用の緑色色素Ｃ．Ｉ．ピグメントグリーン７（１０重量部）、花王製の粒子分散剤ゲラニオールＬ−９５（１重量部）をエタノール（１００重量部）に加え、遊星ボールミルで攪拌してＣ．Ｉ．ピグメントグリーン７を分散させた後、６重量％のシリカゾル溶液（平均分子量２０００〜４０００。溶媒はエタノールが７０％、それ以外は水が主成分。液性はリン酸でｐＨ３前後に制御）（２０重量部）を加える。これを今後カラーフィルターのＧ部分形成液と記述する。
【０２９９】
カラーフィルターのＧ部分形成液が深さ５ｍｍになるよう入っているバットを用意する。バットは基板が入るだけの大きさがある。光照射後の基板の光照射面を下にしてバットの中に入れた後、すぐに引き上げる。光の非照射部分にはカラーフィルターのＧ部分形成液が付着しないが、光の照射部分にはカラーフィルターのＧ部分形成液が付着する。基板の液が付着した側を上にして１２０℃で１０分間加熱する。こうしてカラーフィルターのＧ部分４６が形成される。
【０３００】
（１０）光吸収部位を持つ撥水層形成工程
カラーフィルターのＧ部分を形成した基板を化合物１４の０．１　重量％ＨＦＥ−７２００溶液（ＨＦＥ−７２００は３Ｍ社製）に１０分間浸漬後、１２０℃で１０分間加熱する。こうしてカラーフィルターのＧ部分の上に光吸収部位を持つ撥水層４７が形成される。
【０３０１】
（１１）光照射工程
出力３ｍＷ，発信波長６３３ｎｍのヘリウム／ネオンレーザーを用い、レーザースポット径２μｍ，スキャン速度１０ｍｍ／秒で基板表面のカラーフィルターのＢを形成する部分に６３３ｎｍの波長の光４８を照射する。
【０３０２】
なお図５では光照射部分は光吸収部位を持つ撥水層がなくなっているように描かれているが、実際には光吸収部位を持つ撥水層が変性したもの（一種の含フッ素化合物からなる層）が残っている。
【０３０３】
（１２）カラーフィルターのＢ部分形成工程
Ｂ用の青色色素Ｃ．Ｉ．ピグメントブルー１５（１０重量部）、花王製の粒子分散剤ゲラニオールＬ−９５（１重量部）をエタノール（１００重量部）に加え、遊星ボールミルで攪拌してＣ．Ｉ．ピグメントブルー１５を分散させた後、６重量％のシリカゾル溶液（平均分子量２０００〜４０００。溶媒はエタノールが７０％、それ以外は水が主成分。液性はリン酸でｐＨ３前後に制御）（２０重量部）を加える。これを今後カラーフィルターのＢ部分形成液と記述する。
【０３０４】
カラーフィルターのＢ部分形成液が深さ５ｍｍになるよう入っているバットを用意する。バットは基板が入るだけの大きさがある。光照射後の基板の光照射面を下にしてバットの中に入れた後、すぐに引き上げる。光の非照射部分にはカラーフィルターのＢ部分形成液が付着しないが、光の照射部分にはカラーフィルターのＢ部分形成液が付着する。基板の液が付着した側を上にして１２０℃で１０分間加熱する。こうしてカラーフィルターのＢ部分４９が形成される。
【０３０５】
（１３）光照射工程
出力３ｍＷ，発信波長６３３ｎｍのヘリウム／ネオンレーザーを用い、レーザースポット径２μｍ，スキャン速度１０ｍｍ／秒で基板表面のカラーフィルターのＢが形成された部分以外に６３３ｎｍの波長の光５０を照射する。
【０３０６】
なお図５では光照射部分は光吸収部位を持つ撥水層がなくなっているように描かれているが、実際には光吸収部位を持つ撥水層が変性したもの（一種の含フッ素化合物からなる層）が残っている。
【０３０７】
（１４）保護層形成工程
６重量％のシリカゾル溶液（平均分子量２０００〜４０００。溶媒はエタノールが７０％、それ以外は水が主成分。液性はリン酸でｐＨ３前後に制御）をスピンコート法（回転数２００ｒｐｍ　，回転時間：６０秒間）で塗布後、１２０℃で１０分間加熱する。こうしてブラックマトリクス，カラーフィルターのＲ，Ｇ，Ｂ上にＳｉＯ_２の保護層５１が形成される。
【０３０８】
以上の工程でカラーフィルターパネルを作製できた。作製したカラーフィルターパネルをディスプレイに組み込み画像出力試験を行ったところ、クリアな画像を形成することが確認された。よって本発明の方法によってカラーフィルターパネルの作製が可能であることが確かめられた。
【０３０９】
【実施例４６】
化合物１４の代わりに化合物１３を用い、光照射に用いるレーザーをヘリウム／ネオンレーザーからアルゴンレーザーに代え、結果として発信波長を６３３ｎｍから４８８ｎｍに変更される以外は実施例４５と同様の操作でカラーフィルターパネルを作製する。作製したカラーフィルターパネルをディスプレイに組み込み画像出力試験を行ったところ、クリアな画像を形成することが確認された。よって本発明の方法によってカラーフィルターパネルの作製が可能であることが再度確かめられた。
【０３１０】
【発明の効果】
本発明により２５０ｎｍ以上の長波長の光照射により撥水・親水のパターンを形成し、親水部分に金属配線を行うことで作製される配線基板を提供すること可能になった。
【図面の簡単な説明】
【図１】本発明の原理（光吸収層と撥水層を有する基板の場合）。
【図２】本発明の原理（光吸収部位を持つ撥水層を有する基板の場合）。
【図３】本発明の技術を用いた表示素子用のＴＦＴの作製工程の模式図。
【図４】本発明の技術を用いた有機のＥＬ素子の作製工程の模式図。
【図５】本発明の技術を用いたディスプレイ用カラーフィルターパネルの作製工程の模式図。
【符号の説明】
１，１１…基板、２…光吸収層、３…撥水層、４…照射光、５，９…金属部材が溶解または分散した液、６…金属の配線、７，１２，１７，２０，２７，３０，３８，４１，４４，４７…光吸収部位を持つ撥水層、８，１５…照射光、１０…金属の配線、１３，１８，２１，２３，２８，３１，３４，３９，４２，４５，４８，５０…６３３ｎｍの波長の光、１４…ゲート電極、１６，２９…絶縁層、１９…ソース電極或いはドレイン電極、２２…半導体部位、２４…保護層、２５…ＩＴＯ製の透明電極、２６，３７…ガラス製基板、３２…正孔輸送層、３３…発光層、３５…金属電極、３６…封止層、４０…ブラックマトリクス、４３…カラーフィルターのＲ部分、４６…カラーフィルターのＧ部分、４９…カラーフィルターのＢ部分、５１…保護層。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a wiring board used for a circuit of an electronic device such as a television, a radio, and a personal computer. The present invention also relates to a display such as a TFT and an organic EL, and a color filter panel used for the display.
[0002]
[Prior art]
In a conventional wiring board, wiring is formed of metal such as copper or aluminum on the surface of epoxy resin or the like containing epoxy or glass filler. Components such as a transistor, a diode, a capacitor, and a resistor are set thereon. The completed module serves to convert various input signals into desired output signals.
[0003]
There are several methods for fabricating a wiring board. Generally, a metal such as chromium is sputtered, and then a resist is applied, and then the wiring board is generally fabricated through processes such as exposure, etching, and cleaning. Therefore, a large amount of electric power is required for the high-vacuum deposition process, and there is a problem that a large amount of acid / alkali waste liquid is generated, which hinders cost reduction. Therefore, the water repellency of the light-irradiated portion is reduced by partially irradiating the surface of the substrate with water-repellency in advance (this portion is hereinafter referred to as a hydrophilic portion). A method is proposed in which a liquid in which a member for forming a liquid is dissolved or dispersed is attached (a portion not irradiated with light does not adhere because of water repellency), and a solvent or a dispersion medium is volatilized to form a wiring. Have been.
[0004]
In addition, this method uses not only wiring but also thin-film field-effect transistors ( T hin F field effect T Transistor TFT), organic electroluminescence ( E electro L (luminance EL) element or the like, or a color filter panel used therefor.
[0005]
For example, Patent Literatures 1 to 3 disclose techniques relating to these.
[0006]
[Patent Document 1]
JP-A-2000-147792
[Patent Document 2]
JP-A-2000-282240
[Patent Document 3]
JP 2001-324816 A
[0007]
[Problems to be solved by the invention]
However, the light used in the proposed method is 172 nm in the vacuum ultraviolet region, which is the same as the conventional method in that a vacuum process is required. Therefore, a method of patterning with light having a long wavelength that does not require a vacuum process, specifically, light having a wavelength of 250 nm or more has been studied.
[0008]
[Means for Solving the Problems]
As a result of investigations to solve the above problems, the present inventors have found that the above problems can be solved by providing a light-absorbing layer below the water-repellent layer, and have reached the present invention.
[0009]
The specific contents of the means are described below.
[0010]
(1) A wiring board having a wiring formed of a metal member on its surface, and irradiating a portion of the substrate where a wiring is to be formed with light having a wavelength of 250 nm or more to form a wiring pattern. A wiring substrate comprising: a layer made of an amorphous fluoropolymer on a non-wiring portion of the substrate; and a layer under the layer for absorbing light used when forming a wiring pattern.
[0011]
(2) A wiring board having a wiring formed of a metal member on its surface, and irradiating a portion of the substrate where a wiring is to be formed with light having a wavelength of 250 nm or more to form a wiring pattern. A layer having an amorphous fluoropolymer on a non-wiring portion of the substrate, and a layer for absorbing light used for forming a wiring pattern thereunder, and a layer for absorbing the light. A wiring comprising a resin having a hydroxyl group and a layer comprising the amorphous fluorinated polymer formed of a fluorinated compound having a perfluoropolyether chain or a fluoroalkyl chain and an alkoxysilane residue. substrate.
[0012]
(3) A wiring board having a wiring formed of a metal member on a surface and irradiating a portion of the substrate on which a wiring is to be formed with light having a wavelength of 250 nm or more to form a wiring pattern. A layer having an amorphous fluoropolymer on a non-wiring portion of the substrate, and a layer for absorbing light used for forming a wiring pattern thereunder, and a layer for absorbing the light. It contains a resin having a hydroxyl group, and the layer made of the amorphous fluorine-containing polymer is made of a fluorine-containing compound having a perfluoropolyether chain and an alkoxysilane residue or a fluorine-containing compound having a fluoroalkyl chain and an alkoxysilane residue. A wiring substrate formed, wherein the fluorine-containing compound has the following structure.
[0013]
Embedded image

[0014]
(4) A wiring substrate, which has a wiring formed of a metal member on its surface and forms a wiring pattern by irradiating light having a wavelength of 250 nm or more to a portion on the substrate where the wiring is to be formed. Having a layer made of an amorphous fluoropolymer on the non-wiring portion, and having a site in the molecule for absorbing light used when forming the wiring pattern in the molecule. Characteristic wiring board.
[0015]
(5) A wiring board having wiring on a surface formed of a metal member, and irradiating a portion of the substrate on which wiring is formed with light having a wavelength of 250 nm or more to form a wiring pattern. Having a layer made of an amorphous fluoropolymer on the non-wiring portion, and having a site for absorbing light used when the wiring pattern is formed in the molecule of the amorphous fluoropolymer, And a wiring substrate, wherein the amorphous fluorinated polymer has a perfluoropolyether chain and an alkoxysilane residue in the molecule, or is formed from a compound having a fluoroalkyl chain and an alkoxysilane residue.
[0016]
(6) A wiring substrate, which has a wiring formed of a metal member on the surface and forms a wiring pattern by irradiating light having a wavelength of 250 nm or more to a portion on the substrate where the wiring is to be formed. Having a layer made of an amorphous fluoropolymer on the non-wiring portion, and having a site for absorbing light used when the wiring pattern is formed in the molecule of the amorphous fluoropolymer, The amorphous fluorine-containing polymer has a perfluoropolyether chain and an alkoxysilane residue in the molecule, or is formed from a compound having the following structure having a fluoroalkyl chain and an alkoxysilane residue. Wiring board.
[0017]
Embedded image

[0018]
(7) A method of manufacturing a wiring board having a wiring made of a metal member on the surface, wherein the manufacturing is performed using at least the following steps (1), (2), and (3). Method.
(1) A step of providing, on the surface of the substrate, a layer that absorbs light having a wavelength of 250 nm or more and reduces the water repellency used in the step (2), and a layer made of an amorphous fluoropolymer thereon.
(2) a step of irradiating a portion where a wiring is to be formed with light having a wavelength of 250 nm or more to reduce the water repellency of the light-irradiated portion;
{Circle around (3)} A step of applying a liquid in which a member for forming wiring is dissolved or dispersed to a portion where water repellency is reduced by the light irradiation.
[0019]
(8) A TFT device having a gate electrode on a substrate, an insulating layer thereon, a semiconductor layer, a source electrode, and a drain electrode thereon, and a protective layer on the semiconductor layer, a source electrode, and a drain electrode. A TFT device having a fluorine-containing compound layer between electrodes, between a gate electrode and an insulating layer, between an insulating layer and a semiconductor layer, between a source electrode and a protective layer, or between a drain electrode and a protective layer. .
[0020]
(9) A transparent electrode is provided on the surface of the transparent substrate, a hole transport layer is provided thereon, and a light emitting layer is provided thereon. In an organic EL device having a metal electrode on a layer and a sealing layer on the metal electrode, between the transparent electrode and the hole transport layer, between the transparent substrate and the insulating layer, or between the insulating layer and the metal electrode. An organic EL device comprising a fluorine-containing compound layer between the organic EL devices.
[0021]
(10) R, G, and B color filter portions on the surface of the transparent substrate, and a black matrix in a portion of the transparent substrate surface where no color filter portion exists, and R, G, and B color filter portions And a color filter panel having a protective layer on the black matrix, between the transparent substrate and the black matrix, or between the transparent substrate and the R, G, and B color filter portions and between the protective layer on the black matrix. An organic EL device comprising a fluorine-containing compound layer.
[0022]
(11) In a method of manufacturing a TFT device having a gate electrode on a substrate, an insulating layer thereon, a semiconductor layer, a source electrode, and a drain electrode thereon, and a protective layer on the semiconductor layer, the source electrode, and the drain electrode, A method of manufacturing a TFT element, comprising manufacturing a TFT element using at least one of the following steps (1) to (5).
{Circle around (1)} A step of forming a water-repellent layer made of a fluorine-containing compound having a portion absorbing light having a wavelength of 250 nm or more on a portion where a gate electrode is to be formed, and forming a gate electrode after irradiating light having a wavelength of 250 nm or more. .
{Circle over (2)} A step of forming a water-repellent layer made of a fluorine-containing compound having a portion absorbing light having a wavelength of 250 nm or more on a portion where the insulating layer is to be formed, and forming the insulating layer after irradiating light having a wavelength of 250 nm or more. .
{Circle around (3)} A water-repellent layer made of a fluorine-containing compound having a site for absorbing light having a wavelength of 250 nm or more is formed on a portion where a source electrode and a drain electrode are to be formed, and after irradiating light having a wavelength of 250 nm or more, the source electrode and the drain are formed. A step of forming electrodes.
(4) A step of forming a water-repellent layer made of a fluorine-containing compound having a portion absorbing light having a wavelength of 250 nm or more on a portion where a semiconductor layer is to be formed, and forming the semiconductor layer after irradiating light having a wavelength of 250 nm or more. .
(5) A step of forming a water-repellent layer made of a fluorine-containing compound having a portion absorbing light having a wavelength of 250 nm or more on a portion where a protective layer is to be formed, and forming a protective layer after irradiating light having a wavelength of 250 nm or more. .
[0023]
(12) a transparent electrode on the transparent substrate surface, a hole transport layer on the transparent electrode, a light emitting layer on the transparent electrode, and an insulating layer on the transparent substrate surface where there is no transparent electrode; In a method for manufacturing an organic EL device having a metal electrode on a layer and a sealing layer on the metal electrode, the organic EL device is manufactured using at least one of the following steps (1) to (3). A method for an organic EL device, comprising:
(1) A step of forming a water-repellent layer made of a fluorine-containing compound having a portion absorbing light having a wavelength of 250 nm or more on a portion where the insulating layer is to be formed, and forming the insulating layer after irradiating light having a wavelength of 250 nm or more. .
{Circle around (2)} A water-repellent layer made of a fluorine-containing compound having a site for absorbing light having a wavelength of 250 nm or more is formed on a transparent electrode, and after irradiating light having a wavelength of 250 nm or more, a hole transport layer and a light emitting layer are formed. Steps to perform.
{Circle around (3)} A water-repellent layer made of a fluorinated compound having a portion absorbing light having a wavelength of 250 nm or more is formed on the insulating layer, and a metal electrode and a sealing layer are formed after irradiation with light having a wavelength of 250 nm or more. Process.
[0024]
(13) R, G, and B color filter portions on the transparent substrate surface, and a black matrix in a portion of the transparent substrate surface without the color filter portion, and R, G, and B color filter portions And a method of manufacturing a color filter panel having a protective layer on a black matrix, wherein the color filter panel is manufactured using at least one of the following steps (1) to (3). Method.
{Circle around (1)} A water-repellent layer made of a fluorine-containing compound having a portion absorbing light having a wavelength of 250 nm or more is formed on a portion of the transparent substrate where a black matrix is to be formed, and the black matrix is formed after irradiating light having a wavelength of 250 nm or more. Step of performing.
(2) forming a water-repellent layer made of a fluorine-containing compound having a site for absorbing light having a wavelength of 250 nm or more on portions of the transparent substrate where R, G, and B color filter portions are to be formed;
A step of forming R, G, and B color filter portions after irradiating light having a wavelength of 250 nm or more.
{Circle around (3)} A step of forming a water-repellent layer made of a fluorine-containing compound having a site for absorbing light having a wavelength of 250 nm or more on a black matrix, and forming a protective layer after irradiating light having a wavelength of 250 nm or more.
[0025]
BEST MODE FOR CARRYING OUT THE INVENTION
The types of the wiring board of the present invention are roughly classified into two types. The first one has a light absorbing layer and a water repellent layer on the substrate surface (indicated by {A}). The second one has a water-repellent layer having a light absorbing portion on the substrate surface (indicated by {B}). These will be described separately. [1] The principle of the present invention, [2] The parts (1) and (2) of the members used for manufacturing the substrate before light irradiation relate to {A}, and (3) relates to {B}. Other parts
([4] and [3], [4] of [2]) have the same contents as {A} and {B}.
[0026]
As for the production of display devices, instead of the "solution in which a metal member for forming wiring is dissolved or dispersed" used in the production of a wiring board, a "solution for forming an insulating layer, a semiconductor layer, a light emitting layer, etc." It can be manufactured by using.
[0027]
[1] Principle of the present invention
{A} In the case of a substrate having a light absorbing layer and a water repellent layer
The principle of the present invention will be described with reference to FIG. First, a layer that absorbs light on the surface of the substrate 1
(Light-absorbing layer 2) and a layer (water-repellent layer 3) made of an amorphous fluoropolymer are formed. The layer made of the amorphous fluoropolymer is water repellent, and repels a liquid in which a metal member for forming a wiring described later is dissolved or dispersed.
[0028]
Next, light is applied to a portion of the substrate where the metal wiring is to be formed. The irradiation light 4 is absorbed by the light absorbing layer. Then, the energy of the light is converted into heat energy, and the irradiated portion generates heat. This heat causes the water-repellent layer to decompose. In some cases, the surface of the light absorbing layer also deforms. As a result, the portion irradiated with light loses water repellency and becomes a hydrophilic portion.
[0029]
In FIG. 1, the light-irradiated portion is depicted as if the water-repellent layer has been removed, but actually a modified water-repellent layer (a layer made of a kind of fluorine-containing compound) remains.
[0030]
In this state, when the liquid 5 in which the metal member for forming the wiring is dissolved or dispersed is brought into contact, the liquid adheres only to the portion irradiated with light, that is, only to the hydrophilic portion. The metal wiring 6 is formed by the volatilization of the solvent or the dispersion medium.
[0031]
The above is the outline of the wiring formation. Even if the wavelength of the light used is long, it can be dealt with by changing the material of the light absorbing layer (so-called coloring material). The object of the present invention can be achieved if the coloring material in the light absorbing layer absorbs light, the absorbed energy is converted into heat energy, and the water repellent layer is thermally decomposed to form a hydrophilic portion.
[0032]
In order to decompose the water-repellent layer until it disappears, it is necessary to irradiate a light energy of less than 250 nm and a considerable amount of light. Under the above light irradiation conditions, energy is not applied until the light disappears. Even if it is not decomposed until it disappears, the water repellency can be reduced. In that case, fluorine, which is a constituent element of the amorphous fluoropolymer, can be detected on the surface of the water-repellent layer after light irradiation. (If the surface is analyzed by TOF-SIMS, a signal having a mass number of 19 derived from a fluorine atom is obtained. Is detectable). Therefore, in FIG. 1, the light-irradiated portion of the water-repellent layer is depicted as missing, but in reality, a modified amorphous fluoropolymer remains.
[0033]
As for the production of display devices, instead of the "solution in which a metal member for forming wiring is dissolved or dispersed" used in the production of a wiring board, a "solution for forming an insulating layer, a semiconductor layer, a light emitting layer, etc." It can be manufactured by using. Also in this case, for example, a TFT which is one of the image devices has a modified amorphous fluoropolymer remaining between the electrode and the substrate or between the insulating layer and the substrate. Those in which the amorphous fluoropolymer has been modified remain between the layers or between the insulating layer and the substrate. Further, in the color filter panel, a modified amorphous fluoropolymer remains between the color filter portion and the substrate, between the black matrix portion substrate and the like.
[0034]
In the case of a substrate having a water-repellent layer with a {B} light absorbing part
The principle of the present invention will be described with reference to FIG. First, a water-repellent layer 7 having a light absorbing portion is formed on the substrate surface. The water-repellent layer repels a liquid in which a metal member for forming a wiring described later is dissolved or dispersed.
[0035]
Next, light is applied to a portion of the substrate where the metal wiring is to be formed. The irradiation light 8 is absorbed by the light absorbing portion of the water repellent layer. Then, the energy of the light is converted into heat energy, and the irradiated portion generates heat. This heat causes the water-repellent layer to decompose. As a result, the portion irradiated with light loses water repellency and becomes a hydrophilic portion.
[0036]
In FIG. 2, the light-irradiated portion is depicted as if the water-repellent layer having the light-absorbing portion has been removed, but in fact, the water-repellent layer having the light-absorbing portion has been modified (from a kind of fluorine-containing compound). Layer) remains.
[0037]
In this state, when the liquid 9 in which the metal member for forming the wiring is dissolved or dispersed is brought into contact, the liquid adheres only to the portion irradiated with light, that is, only to the hydrophilic portion. The metal wiring 10 is formed by the volatilization of the solvent or the dispersion medium.
[0038]
As in {A}, in order to decompose the water-repellent layer having the light-absorbing site until it disappears, it is necessary to irradiate a considerable amount of light energy of less than 250 nm and moreover. Even if it is not decomposed until it disappears, the water repellency can be reduced. In that case, fluorine as a constituent element can be detected on the surface of the water-repellent layer having a light absorption portion after light irradiation.
(If the surface is analyzed by TOF-SIMS, a signal having a mass number of 19 derived from a fluorine atom can be detected). Therefore, in FIG. 2, the light-irradiated portion of the water-repellent layer having the light-absorbing portion is depicted as missing, but in reality, the modified water-repellent layer having the light-absorbing portion remains.
[0039]
As for the production of display devices, instead of the "solution in which a metal member for forming wiring is dissolved or dispersed" used in the production of a wiring board, a "solution for forming an insulating layer, a semiconductor layer, a light emitting layer, etc." It can be manufactured by using. Also in this case, for example, in a TFT which is one of the image devices, a modified water-repellent layer having a light absorbing portion remains between an electrode and a substrate or between an insulating layer and a substrate. A modified water-repellent layer having a light absorbing portion remains between the insulating layers or between the insulating layer and the substrate. In the color filter panel, a modified water-repellent layer having a light absorbing portion remains between the color filter portion and the substrate or between the black matrix portion substrates.
[0040]
The above is the outline. As in the case of {A}, even if the wavelength of the light used is long, it can be handled by changing the structure of the light absorbing portion. The object of the present invention can be attained if the light absorbing portion absorbs light, the absorbed energy is converted into heat energy, and the water repellent layer is thermally decomposed to form a hydrophilic portion.
[0041]
[2] Members used for manufacturing a substrate before light irradiation and manufacturing method
The members used for manufacturing the substrate are described below.
[0042]
(1) Water-repellent layer forming material and processing method
This section is an explanation of “in the case of a substrate having a {A} light absorbing layer and a water repellent layer”.
[0043]
As the material for forming the water-repellent layer, a material containing a fluorine atom for increasing water repellency in a molecule is used. These materials are dissolved in a solvent capable of dissolving, and this solution is applied to the light absorbing layer. Thereafter, drying is performed to evaporate the solvent, and a thin film made of a water-repellent layer forming material is formed. The surface of the water-repellent layer formed at this time has an adhesive property with the light-absorbing layer when a liquid in which a member for forming wiring is dissolved or dispersed adheres or a step of forming a protective film thereon. It is desirable that the surface be flat so as to increase the uniformity of the film when a protective film or the like is applied on the water-repellent layer. It is desired that the material for forming the water-repellent layer be amorphous for flattening. Further, a polymer structure is desirable in order to have physical durability as a film. Although there are silicon-containing water-repellent materials in the world, fluorine-containing materials are generally superior in their ability to repel liquids, and therefore, fluorine-containing materials are used in the present invention.
[0044]
From the above, an amorphous fluorinated polymer is desirable as the material for forming the water-repellent layer. Specific examples of such materials include polydiperfluoroalkyl fumarate, Teflon AF (registered trademark) (manufactured by Dupont), Cytop (manufactured by Asahi Glass), and fumalite (manufactured by NOF Corporation). Fluorinated ethylene and hydrocarbon ethylene such as a copolymer of polydiperfluoroalkyl fumarate and styrene, a copolymer of 3-fluoroethylene chloride and vinyl ether, and a copolymer of 4-fluoroethylene and vinyl ester And the like.
[0045]
Some materials for forming the water-repellent layer are chemically bonded to the surface of the light absorbing layer by heating after coating. Such a material is preferable because the water-repellent layer forming material gradually moves to the hydrophilic image pattern and the pattern is less likely to disappear. Examples of such materials include the following. These compounds react with hydroxyl groups and the like on the surface of the light absorbing layer by heating after coating and form a chemical bond on the surface, so there is no need to worry about moving on the surface of the light absorbing layer, and there is a low possibility of losing the hydrophilic image pattern. .
[0046]
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[0047]
Specific examples include the following compounds 1 to 12.
[0048]
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[0049]
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[0050]
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[0051]
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[0052]
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[0053]
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[0054]
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[0055]
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[0056]
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[0057]
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[0058]
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[0059]
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[0060]
Among them, compounds 1 to 8 can be obtained by executing the following synthesis method. Compounds 9 to 12 have the compound names 1H, 1H, 2H, 2H-perfluorooctyltrimethoxysilane, 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyl, respectively. It is marketed by Hydras Chemical Company as trimethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane. Another commercially available material is Optool DSX manufactured by Daikin Industries, Ltd.
[0061]
Compounds 1 to 4 have a fluorine chain called perfluoropolyether, and the water-repellent film formed from the compound having a fluorine chain can be used for a long time (1000 times) in addition to water to an alcohol-based solvent or a hydrocarbon-based solvent. For a period of time), the water repellency hardly decreases (the amount of reduction is 5 ° or less).
[0062]
Compounds 5 to 12 can be used in alcohol solvents or hydrocarbon solvents for a long time
(1000 hours), the contact angle with water decreases from before the immersion (about 110 °) to almost the same level as the contact angle of the substrate.
[0063]
(Synthesis of Compound 1)
Krytox 157FS-L (average molecular weight 2500) (25 parts by weight) manufactured by DuPont was dissolved in PF-5080 (100 parts by weight) manufactured by 3M, and thionyl chloride (20 parts by weight) was added thereto. Reflux for hours. Thionyl chloride and PF-5080 are volatilized by an evaporator to obtain Krytox 157FS-L acid chloride (25 parts by weight). To this are added PF-5080 (100 parts by weight), Silaace S330 (3 parts by weight) manufactured by Chisso Corporation, and triethylamine (3 parts by weight), and the mixture is stirred at room temperature for 20 hours. The reaction solution was filtered with Showa Chemical Industry's Radiolite Fine Flow A, and PF-5080 in the filtrate was volatilized with an evaporator to obtain Compound 1 (20 parts by weight).
[0064]
(Synthesis of Compound 2)
Compound 2 (20 parts by weight) was obtained in the same manner as in the synthesis of compound 1, except that Sisla Ace S330 (3 parts by weight) manufactured by Chisso Corp. was used instead of Silaace S360 (3 parts by weight).
[0065]
(Synthesis of Compound 3)
Compound was prepared in the same manner as in the synthesis of compound 1 except that Deynam SH (average molecular weight: 3500) (35 parts by weight) manufactured by Daikin Industries, Ltd. was used instead of Krytox 157FS-L (average molecular weight 2500) (25 parts by weight) manufactured by DuPont 3 (30 parts by weight) was obtained.
[0066]
(Synthesis of Compound 4)
Instead of Chisso Ace S330 (3 parts by weight), Chisso Ace S360 (3 parts by weight) was used instead of Chisso Ace S330 (3 parts by weight). Compound 4 (30 parts by weight) was obtained in the same manner as in the synthesis of compound 1, except that Demnum SH (average molecular weight: 3500) (35 parts by weight) manufactured by Daikin Industries, Ltd. was used.
[0067]
(Synthesis of Compound 5)
Instead of Dupont's Krytox 157FS-L (average molecular weight 2500) (25 parts by weight), Daikin Industries, Ltd. 7H-dodecafluoroheptanoic acid (molecular weight)
Compound 5 (3.5 parts by weight) was obtained in the same manner as in the synthesis of compound 1 except that 346.06) (3.5 parts by weight) was used.
[0068]
(Synthesis of Compound 6)
Instead of Dupont's Krytox 157FS-L (average molecular weight 2500) (25 parts by weight), Daikin Industries, Ltd. 7H-dodecafluoroheptanoic acid (molecular weight)
346.06) (3.5 parts by weight), using a Silas Ace S330 manufactured by Chisso Corporation.
Compound 6 (3.5 parts by weight) was obtained in the same manner as in the synthesis of compound 1, except that Silas Ace S360 (3 parts by weight) manufactured by Chisso Corporation was used instead of (3 parts by weight).
[0069]
(Synthesis of Compound 7)
Compound except that 9H-hexadecafluorononanoic acid (molecular weight 446.07) (4.5 parts by weight) manufactured by Daikin Industries, Ltd. is used instead of Krytox 157FS-L (average molecular weight 2500) (25 parts by weight) manufactured by DuPont. Compound 7 (4.5 parts by weight) was obtained in the same manner as in the synthesis of Compound 1.
[0070]
(Synthesis of Compound 8)
Using 9H-hexadecafluorononanoic acid (molecular weight 446.07) (4.5 parts by weight) manufactured by Daikin Industries, Ltd. instead of Krytox 157FS-L (average molecular weight 2500) (25 parts by weight) manufactured by DuPont, using nitrogen ( Compound 8 (4.5 parts by weight) was obtained in the same manner as in the synthesis of compound 1 except that Silaace S360 (3 parts by weight) manufactured by Chisso Corporation was used instead of Silaace S330 (3 parts by weight) manufactured by Co., Ltd.
[0071]
These compounds are dissolved in a fluorine-based solvent and applied to the light absorbing layer. Then, by heating, it reacts with a hydroxyl group, a carboxyl group or the like of the light absorbing layer to form a chemical bond. Thus, the water-repellent treatment ends. The concentration of the water-repellent layer forming material is set to be higher as the material having a higher average molecular weight. When the average molecular weight is around 3000, the concentration is preferably about 0.3% by weight. Specific examples of the fluorine-based solvent include FC-72, FC-77, PF-5060, PF-5080, HFE-7100, HFE-7200 manufactured by 3M and Bertrel XF manufactured by DuPont. The heating temperature is desirably 100 ° C. or higher. If possible, the film formation reaction proceeds more rapidly at 120 ° C. or higher. The heating time is preferably about 1 hour at 100 ° C., 15 minutes at 120 ° C., and about 10 minutes at 140 ° C. However, when the temperature is higher than 250 ° C., the water-repellent layer forming material may be thermally decomposed. When a hydroxyl group or the like does not exist in the base material of the light absorption layer, it is possible to give the surface a hydroxyl group by performing oxygen plasma treatment. By performing the water-repellent treatment after performing this treatment, it becomes possible to have a chemical bond between the material for forming the water-repellent layer and the light absorbing layer.
[0072]
The water-repellent layer forming material is applied by brush coating, dip coating, spin coating, spray coating, or the like.
[0073]
(2) Light absorption layer
This section is an explanation of “in the case of a substrate having a {A} light absorbing layer and a water repellent layer”.
[0074]
The light-absorbing layer requires the presence of a compound having a site for absorbing light in the layer. As such compounds, generally known dyes are used. If the dye is amorphous, the light absorbing layer can be formed only by the dye. However, in the case of crystallinity, it is difficult to form a flat light absorption layer. For this reason, when the light absorbing layer is crystallized, problems such as scattering of irradiated light occur. In this case, additional measures such as dissolving or mixing some other substance to lower the crystallinity and forming a flat light absorbing layer are required. Resin is effective as the above-mentioned another substance. The resin also functions as a support for the dye, and has the effect of increasing the physical strength of the film. Therefore, when a crystalline dye is used, it is effective to form the light absorbing layer by holding the dye with a resin. In this case, this can also be achieved by providing a light absorbing portion in the resin itself.
[0075]
If the wavelength of the irradiation light is in the near-ultraviolet region (approximately 250 to 400 nm in wavelength), a compound having a benzene ring, a naphthalene ring, an anthracene ring or the like, or a compound having a bonding group such as an amide may be used instead of a dye. No. As a resin, polyethylene terephthalate having an aromatic ring, polystyrene, styrene-acrylic resin, phenol resin, and the like also have an absorption in the near ultraviolet region.
[0076]
If the wavelength of the irradiation light is in the visible light region (approximately 400 to 700 nm in wavelength), a light absorbing layer can be produced by dispersing a material used as a pigment in the world in a resin and forming a film. In addition, the wavelength of the irradiation light is in the near-infrared light region (the wavelength is generally
(700-1100 nm) can be dealt with by using a cyanine dye, a phthalocyanine dye, or a naphthalocyanine dye.
[0077]
In the case of a structure in which the dye is held by the resin, the dye is dissolved in the resin or is dispersed as finely and uniformly as possible so that the heat transfer to the water-repellent layer becomes uniform. Further, in order to convert the irradiated light into heat effectively, it is desirable that the light source has absorption as large as possible at the output wavelength of the light source used. There is no particular limitation on dyes and pigments as pigments. Dyes are preferred in that they have high dispersibility in resins. However, in the case of dyes, in addition to converting absorbed light into heat, there is a tendency to convert the absorbed light into its own photolysis energy. Therefore, the conversion efficiency of light energy to heat energy is low. In that regard, pigments with high lightfastness are generally preferred because they convert a significant proportion of the absorbed light into heat.
[0078]
Examples of the dye include indanthrene dyes such as flavantron yellow, indanthrene red 5GK, and indanthrene violet BN. Orange II, C.I. I. Direct Yellow 12 (chrysophenin), C.I. I. Acid Yellow 23 (tartrazine), C.I. I. Mordant Orange 1, C.I. I. Reactive Yellow 3 (Procion Yellow HA), C.I. I. Azo dyes such as Disperse Yellow 3 and Naphthol Blue Black B. Malachite green, pararose aniline and aurin triphenylmethane dyes. A cyanine dye in which a quinoline ring or pyridine ring is bonded to an indole ring. Heterocyclic dyes such as Safranin T, fluossen, and methylene blue. Other examples include anthraquinone dyes such as quinacridone and quinone, polymethine dyes, and azomethine dyes.
[0079]
Examples of pigments include azo pigments, phthalocyanine pigments, condensed polycyclic pigments, and lakes of acidic or basic dyes. Among the azo pigments, specifically, soluble azo pigments such as acetoacetic anilide, pyrazolone, β-naphthol, β-oxynaphthoic acid, β-oxynaphthoic acid anilide, acetoacetic anilide, pyrazolone, β-naphthol And insoluble azo pigments based on .beta.-oxynaphthoic acid anilide, condensed azo pigments based on anilide acetoacetate and anilide .beta.-oxynaphthoic acid. Examples of the phthalocyanine pigments include copper phthalocyanine pigments such as copper phthalocyanine, copper phthalocyanine halide, and sulfonated phthalocyanine lake, metal-free phthalocyanine pigments, copper naphthalocyanine pigments, silicon naphthalocyanine pigments, and germanium naphthalocyanine pigments. Examples of the condensed polycyclic pigments include aminoanthraquinone, anthrapyrimidine, anthraquinone pigments such as flavanthrone, anthantrone, indanthrone, pyranthrone, and biolanthrone, perylene, perinone, quinacridone, thioindigo, dioxazine, isoindoline, quinophthalone, and various metal complexes. Is mentioned.
[0080]
In order to make the dispersion uniform, it is desirable to employ means such as making fine particles with a pulverizing device such as a planetary ball mill, or improving the dispersibility by adding a slight dispersant.
[0081]
The resin used to hold these dyes is not particularly limited. However, since the light absorbing layer is formed by a simple method such as a dip method or a spin coating method, the monomer or the resin itself is dissolved in an organic solvent or water. Is desirable. Examples of such a resin include ethylene-vinyl acetate copolymer, polyethylene terephthalate, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyethyl methacrylate, polystyrene, and styrene-acrylonitrile copolymer. Coalescence, acrylonitrile-butadiene-styrene copolymer, polyacetal, polycarbonate, cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose propionate, ethyl cellulose, methyl cellulose, carboxymethyl cellulose, phenolic resin, epoxy resin, polyester resin, Alkyd resin, melamine resin, silicon resin, polyurethane, diallyl phthalate resin, polyphenylene oxide Polyimides, polysulfones, and the like.
[0082]
When a water-repellent layer formed on the light-absorbing layer is of a type that chemically bonds to the light-absorbing layer, a hydroxyl group such as a phenol resin or polyvinyl alcohol is used in that the durability of the water-repellent layer is improved. Is preferred.
[0083]
(3) Material for forming a water-repellent layer having a light absorbing portion
This section describes "in the case of a substrate having a water-repellent layer having a {B} light absorbing portion".
[0084]
(1) Water-repellent material in which light absorbing material is dissolved or dispersed
As the water-repellent layer having a light-absorbing portion, a method of dissolving or dispersing a material that absorbs light in a water-repellent material forming the water-repellent layer, that is, a so-called coloring material can be used. Examples of the water-repellent material include polydiperfluoroalkyl fumarate, Teflon AF (manufactured by Dupont), Cytop (manufactured by Asahi Glass), and Fumalite (manufactured by NOF Corporation). Fluorinated ethylene and hydrocarbon ethylene such as a copolymer of polydiperfluoroalkyl fumarate and styrene, a copolymer of 3-fluoroethylene chloride and vinyl ether, and a copolymer of 4-fluoroethylene and vinyl ester And the like.
[0085]
Examples of the coloring material include the above-mentioned dyes, pigments, and other general-purpose coloring materials. All of them need to be dissolved or dispersed in fine particles in the water repellent material.
[0086]
The water-repellent layer forming material is applied by brush coating, dip coating, spin coating, spray coating, or the like.
[0087]
(2) Water-repellent material having a water-repellent part and a light absorbing part in the molecule
Water-repellent materials having a light absorption site in the molecule fall into this category. However, if it does not have a bonding site with the substrate, it may diffuse on the substrate surface as a highly viscous liquid. May recover. Therefore, when using this water-repellent material, it is desirable to also have a bonding site with the substrate. Specifically, a water-repellent material having the following chemical structure is desirable.
[0088]
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[0089]
Examples of the light absorption site of these materials include an amide bond absorbing 250 nm light. Compounds 1 to 8 already shown fall into this category of compounds.
[0090]
By providing a dye skeleton in the molecule, the dye skeleton functions as a light absorption site. Specific examples include the following compounds 13 to 27.
[0091]
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[0092]
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[0093]
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[0094]
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[0095]
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[0096]
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[0097]
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[0098]
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[0099]
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[0100]
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[0101]
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[0102]
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[0103]
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[0104]
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[0105]
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[0106]
The method for synthesizing these compounds is shown below.
[0107]
(Synthesis of Compound 13)
Compound 13 is synthesized by the following reactions (i) to (iii).
[0108]
(I) Reduction of water repellent material
Crytox 157FS-L (average molecular weight 2500) (50 parts by weight) manufactured by DuPont was dissolved in PF-5080 (100 parts by weight) manufactured by 3M, and lithium aluminum hydride (2 parts by weight) was added thereto, and the mixture was added for 48 hours. Heat and stir at 80 ° C. The reaction solution is poured into ice water, the lower layer is separated, washed with 1% hydrochloric acid, and then washed with water until the washing solution becomes neutral. After removing water in the liquid after washing by filtration through filter paper, PF-5080 was volatilized by an evaporator, and the terminal of Krytox 157FS-L was CH. ₂ Compound 28 (45 parts by weight) converted to OH is obtained.
[0109]
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[0110]
(Ii) Introduction reaction of dye skeleton
Compound 28 (45 parts by weight) was dissolved in 3M HFE-7200 (100 parts by weight), to which Reactive Yellow 3 (also known as Procion Yellow HA) (12 parts by weight), ethanol (100 parts by weight), Add sodium carbonate (2 parts by weight) and reflux for 30 hours. The structure of Reactive Yellow 3 is shown below.
[0111]
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[0112]
The solvent (HFE-7200 and ethanol) in the reaction solution was volatilized by an evaporator, and the residue was mixed with HFE-7200 (100 parts by weight), 35% hydrochloric acid (100 parts by weight) and ice water (100 parts by weight). And vigorously stirred and then allowed to stand. The lower layer is separated and washed with water until the cleaning solution becomes neutral. After removing water in the liquid after washing by filtration through filter paper, HFE-7200 is volatilized by an evaporator to obtain compound 29 (45 parts by weight) in which reactive yellow 3 is bound to compound 28.
[0113]
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[0114]
(Iii) Introduction reaction of binding site
After dissolving Compound 29 (45 parts by weight) in HFE-7200 (100 parts by weight) and cooling to about 0 ° C., Silaace S330 (10 parts by weight) manufactured by Chisso Corporation, N, N-dicyclohexylcarbodiimide (10 parts by weight) ) And dichloromethane (20 parts by weight) are added and stirred for 3 hours. Further, the reaction solution is returned to room temperature and stirred for 30 hours. After allowing the reaction solution to stand, when the reaction solution is roughly divided into two layers, the lower layer is separated. Turbidity occurs between the upper and lower layers, but this is not added to the lower layer. The lower layer is washed several times with dichloromethane (20 parts by weight), and then filtered with filter paper. Thereafter, the solvent (HFE-7200) in the liquid was volatilized by an evaporator to obtain a target compound 13 (40 parts by weight).
[0115]
(Synthesis of Compound 14)
Compound 14 (40 parts by weight) was obtained in the same manner as in the synthesis of compound 13, except that Micasion Brilliant Blue RS (7 parts by weight) was used instead of Reactive Yellow 3 (12 parts by weight).
[0116]
The chemical structure of Mikasion Brilliant Blue RS is as follows.
[0117]
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[0118]
In some cases, a portion of sodium sulfonate is converted to sulfonic acid. In such a case, it is used after being converted to sodium sulfonate with sodium hydroxide or the like.
[0119]
(Synthesis of Compound 15)
Compound 15 (35 parts by weight) was obtained in the same manner as in the synthesis of compound 13 except that Silaace S360 (10 parts by weight) manufactured by Chisso Corporation was used instead of Silaace S330 (10 parts by weight) manufactured by Chisso Corporation.
[0120]
(Synthesis of Compound 16)
Instead of Sila Ace S330 (10 parts by weight) manufactured by Chisso Corporation, Sila Ace S360 (10 parts by weight) manufactured by Chisso Corporation was used, and instead of Reactive Yellow 3 (12 parts by weight), Mikasion Brilliant Blue RS ( Compound 16 (36 parts by weight) was obtained in the same manner as in the synthesis of compound 13 except that 7 parts by weight was used.
[0121]
(Synthesis of Compound 17)
Compound 17 (56 parts by weight) was obtained in the same manner as in the synthesis of compound 13 except that Demnum SA (average molecular weight: 3500) (65 parts by weight) was used instead of compound 28 (45 parts by weight).
[0122]
(Synthesis of Compound 18)
Compound 28 (45 parts by weight) was replaced by Daikin Industries, Ltd.'s Demnum SA (average molecular weight 3500) (65 parts by weight), and instead of Reactive Yellow 3 (12 parts by weight), Micasion Brilliant Blue RS (7 parts) was used. Compound 18 (50 parts by weight) was obtained in the same manner as in the synthesis of Compound 13 except for using Compound 3 (parts by weight).
[0123]
(Synthesis of Compound 19)
Instead of compound 28 (45 parts by weight), Demnum SA (average molecular weight: 3500) (65 parts by weight) manufactured by Daikin Industries, Ltd. was used, and Shiraace S330 manufactured by Chisso Corporation was used.
Compound 19 (48 parts by weight) was obtained in the same manner as in the synthesis of compound 13, except that Silas Ace S360 (10 parts by weight) manufactured by Chisso Corporation was used instead of (10 parts by weight).
[0124]
(Synthesis of Compound 20)
Compound 28 (45 parts by weight) was replaced by Daikin Industries, Ltd.'s Demnum SA (average molecular weight 3500) (65 parts by weight), and instead of Reactive Yellow 3 (12 parts by weight), Micasion Brilliant Blue RS (7 parts) was used. Parts by weight) and using Compound 20 (44 parts by weight) in the same manner as in the synthesis of Compound 13 except that Chisla Ace S360 (10 parts by weight) instead of Chisso Ace S330 (10 parts by weight) is used. Part).
[0125]
(Synthesis of Compound 21)
Compound 21 (40 parts by weight) was obtained in the same manner as in the synthesis of compound 13 except that DOL4000 (average molecular weight 4000) (40 parts by weight) manufactured by Ausimont was used instead of compound 28 (45 parts by weight).
[0126]
(Synthesis of Compound 22)
Audimont DOL4000 (average molecular weight 4000) (40 parts by weight) was used in place of compound 28 (45 parts by weight), and Chisso Corporation Siraace S360 (10 parts by weight) was used instead of Chisso Corporation Silaace S330 (10 parts by weight). Compound 22 (38 parts by weight) was obtained in the same manner as in the synthesis of compound 13 except that 10 parts by weight was used.
[0127]
(Synthesis of Compound 23)
1H, 1H, 2H, 2H-perfluorodecanol (4 parts by weight) was used in place of compound 28 (45 parts by weight), and Micasion Brilliant Blue RS (in place of Reactive Yellow 3 (12 parts by weight) ( Compound 23 (11 parts by weight) was obtained in the same manner as in the synthesis of compound 13 except that 7 parts by weight was used.
[0128]
(Synthesis of Compound 24)
1H, 1H, 2H, 2H-perfluorodecanol (4 parts by weight) was used in place of compound 28 (45 parts by weight), and Micasion Brilliant Blue RS (in place of Reactive Yellow 3 (12 parts by weight) ( 7 parts by weight) and the use of Chilaso S360 (10 parts by weight) instead of Chisso Ace S330 (10 parts by weight) in place of Chisso Corporation Siraace S330 (10 parts by weight).
24 (9 parts by weight) was obtained.
[0129]
(Synthesis of Compound 25)
1H, 1H, 2H, 2H-perfluorodecanol (4 parts by weight) was used in place of compound 28 (45 parts by weight), and Chisso Corporation was used instead of Chisla Ace S330 (10 parts by weight) manufactured by Chisso Corporation. Compound 25 (10 parts by weight) was obtained in the same manner as in the synthesis of compound 13, except that Saila Ace S360 (10 parts by weight) was used.
[0130]
(Synthesis of Compound 26)
1H, 1H, 2H, 2H, 10H-perfluorodecanol (4 parts by weight) was used in place of Compound 28 (45 parts by weight), and Mikasion Brilliant Blue was used in place of Reactive Yellow 3 (12 parts by weight). Compound 26 was prepared in the same manner as in the synthesis of compound 13, except that RS (7 parts by weight) was used and Silases S360 (10 parts by weight) manufactured by Chisso Corporation was used instead of Silaace S330 (10 parts by weight) manufactured by Chisso Corporation. (8 parts by weight).
[0131]
(Synthesis of Compound 27)
1H, 1H, 2H, 2H, 10H-perfluorodecanol (4 parts by weight) was used in place of compound 28 (45 parts by weight), and Chisso Corporation (10 parts by weight) was used in place of Silaace S330 (10 parts by weight) manufactured by Chisso Corporation. Compound 27 (9 parts by weight) was obtained in the same manner as in the synthesis of Compound 13 except that Sila Ace S360 (10 parts by weight) was used.
[0132]
These compounds are dissolved in a fluorine-based solvent and applied to a substrate. Then, by heating, it reacts with a hydroxyl group, a carboxyl group or the like of the substrate to form a chemical bond. Thus, the formation of the water-repellent layer having the light absorbing portion is completed. The concentration of a water-repellent material having a water-repellent portion and a light-absorbing portion in a molecule is set to be higher for a material having a larger average molecular weight. When the average molecular weight is around 3000, the concentration is preferably about 0.3% by weight. Specific examples of the fluorinated solvent include FC-72, FC-77, PF-5060, and PF- manufactured by 3M.
5080, HFE-7100, HFE-7200, Vertrel XF manufactured by DuPont, and the like. The heating temperature is desirably 100 ° C. or higher. If possible, the film formation reaction proceeds more rapidly at 120 ° C. or higher. The heating time is preferably about 1 hour at 100 ° C., 15 minutes at 120 ° C., and about 10 minutes at 140 ° C. However
If the temperature is higher than 250 ° C., the water-repellent layer forming material may be thermally decomposed. When a hydroxyl group or the like does not exist on the substrate, the surface can be provided with a hydroxyl group by performing oxygen plasma treatment. By performing the processing after performing this processing, the water-repellent material having a water-repellent portion and a light absorbing portion in the molecule and the substrate can have a chemical bond.
[0133]
The application of a water-repellent material having a water-repellent portion and a light-absorbing portion in the molecule is performed by brush coating, dip coating, spin coating, or the like.
[0134]
(4) Substrate material and hydrophilization of its surface
Regarding this term, the contents are common to the above {A} and {B}.
[0135]
Before forming the light-absorbing layer, the water-repellent layer, and the water-repellent layer having the light-absorbing portion, the surface of the substrate is made hydrophilic in advance, so that the substance can be easily attached to the surface, and the light-absorbing layer and the light-absorbing layer can be easily absorbed. It becomes easy to form a water-repellent layer having portions flat. In particular, when the light absorbing layer is formed by a coating method, a light absorbing layer having high adhesion can be formed by improving the wettability of the paint to be formed. After the water-repellent layer is decomposed by irradiating light to the water-repellent layer having the light-absorbing site, it is desirable that the substrate is made hydrophilic so that a liquid in which the metal member is dissolved or dispersed is easily attached.
[0136]
Various materials such as glass, quartz, silicon, resin, and resin containing glass particles can be considered as the substrate.
[0137]
(1) Method applied when the base material is glass, quartz, or silicon
When the substrate is glass, quartz or silicon, the hydrophilicity can be improved by a method such as treatment with oxygen plasma or immersion in a basic solution. In the case of oxygen plasma, the contact angle with water became 10 ° or less in an oxygen partial pressure of 1 Torr, an output of a high frequency power supply of 300 W, and a processing time of 3 minutes.
[0138]
It is also possible to change oxygen in the vicinity of the substrate to ozone by irradiating ultraviolet rays, and change the surface of the substrate to hydrophilicity by the ozone. Exposing the substrate to an ozone atmosphere using an ozone generator is also effective as means for improving hydrophilicity.
[0139]
In addition, when a 1% by weight aqueous solution of sodium hydroxide was used as the basic solution, the contact angles with water were all 20 ° or less after immersion for 5 minutes.
[0140]
(2) Method applied when the base material is resin
When the substrate is a resin, the hydrophilicity can be improved by a method such as treatment with oxygen plasma or immersion in an acid / basic solution.
[0141]
When oxygen plasma is used, for example, in the case of polystyrene, acrylic resin, styrene / acrylic resin, polyester resin, acetal resin, polycarbonate, polyether sulfone, polysulfone, polyethersulfone, etc., the oxygen partial pressure is 1 Torr, the output of the high frequency power supply is 100 W, and the processing is performed. The contact angle with water became 20 ° or less under the condition of time 1 minute.
[0142]
Similarly to glass, it is also possible to change oxygen in the vicinity of the substrate to ozone by irradiating ultraviolet rays, and change the substrate surface to hydrophilic by the ozone. Exposing the substrate to an ozone atmosphere using an ozone generator is also effective as means for improving hydrophilicity.
[0143]
As another method, immersion in a basic solution is particularly effective for a material having an ester bond in a molecule such as an acrylic resin, a styrene / acrylic resin, a polyester resin, an acetal resin, and a polycarbonate. This is because the carboxylate residue having high hydrophilicity and / or the hydroxyl group are generated by cleaving the ester bond on the surface and in the vicinity thereof, thereby generally increasing the hydrophilicity of the surface. In the case of a resin that is polymerized by condensation of an amino group and a carboxyl group, such as polyimide or polyamide, the amino group remaining unreacted during polymerization by immersing in an acid such as hydrochloric acid has a highly hydrophilic ammonium salt structure, By immersing in a sodium hydroxide aqueous solution, a carboxyl group remaining without reacting during polymerization is converted into a carboxylate having a high hydrophilicity, whereby the hydrophilicity of the surface can be generally improved. When immersing in an acid / basic solution, the higher the temperature of the solution, and the higher the concentration, the more the hydrophilization tends to proceed rapidly. Care must be taken, however, because increasing the temperature and concentration tends to damage the substrate.
[0144]
(3) Method for applying to various substrates
A method of applying a coating material exhibiting hydrophilicity can be cited as a hydrophilizing method that can be treated even if the base material is metal, glass, or resin. These materials generally include those shown in a) to d), but other materials are not particularly limited.
[0145]
a) Solution of water-soluble polymer material
Examples of the water-soluble polymer include polyethylene glycol, polyvinyl alcohol, polyacrylic acid, polyacrylate, polyallylamine, hydrochloride of polyallylamine, and starch. Those having a hydrophilic residue such as a hydroxyl group, an amino group, a carboxyl group, and a residue having a salt structure in the molecule are exemplified. A coating solution is prepared by preparing an aqueous solution or a solution of an organic solvent. This is applied to a cell substrate and dried to form a hydrophilic coating film. Among these water-soluble polymers, there is a strong tendency particularly to lower the contact angle of the surface coated with polyethylene glycol. The higher the molecular weight of the polymer used, the better the smooth hydrophilic film with less light scattering can be formed. If the surface to be treated has high water repellency, the paint is repelled, and as a result, a flat film cannot be formed. This is because when the solvent is water, the surface tension of the polymer solution used becomes large. Therefore, if an oxygen plasma treatment is performed before applying these paints, a flat coating film is easily formed. Incidentally, polyethylene glycol is dissolved in an organic solvent such as tetrahydrofuran. Therefore, the surface tension of this solution is smaller than that of the same aqueous solution of polyethylene glycol, and the solution is easily applied to a surface of aluminum or the like having high water repellency.
[0146]
b) Paint containing hydrophilic particles
A mixture of a dispersion containing hydrophilic alumina particles or hydrophilic silica particles and a solution of alkoxysilane is used as a paint. In the case of using this paint, the film is completed by heating after applying it to the base material of the cell. In this coating, hydrophilic alumina particles and hydrophilic silica particles mainly exhibit hydrophilicity, and alkoxysilane mainly functions as a support for these particles. Therefore, the hydrophilicity can be increased by increasing the proportion of the hydrophilic alumina particles or hydrophilic silica particles. The physical strength of the film is improved by increasing the proportion of the alkoxysilane. It is preferable that the alkoxysilane is crosslinked to some extent between molecules because the rate of volatilization by heating after coating is reduced. Hydrochloric acid or the like may be added to the alkoxysilane to promote intermolecular polymerization. In the case of hydrophilic silica, the dispersion may be basic in order to improve the dispersion. Therefore, when both are mixed, the hydrophilic silica may agglomerate. Therefore, attention should be paid to the liquidity and the state of dispersion of the hydrophilic silica when mixed. In this case, in the case of alumina, since the dispersion is mainly acidic, there is little trouble during mixing. Examples of the alkoxysilane include methyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, butyltriethoxysilane, tetramethoxysilane, tetraethoxysilane and the like. If the liquidity and the solvent are compatible, alkoxytitanium may be used instead of alkoxysilane. Examples of the alkoxy titanium include tetra-i-propyl titanate, tetra-n-butyl titanate, tetrastearyl titanate, triethanolamine titanate, titanium acetylacetonate, titanium ethyl acetoacetate, titanium lactate, and tetraoctylene glycol titanate. Further, those obtained by polymerizing several molecules of these compounds can also be used.
[0147]
c) Paint containing water-soluble polymer and its crosslinking agent
A coating that forms a hydrophilic surface by mixing the water-soluble polymer described in a) with the alkoxysilane or alkoxytitanium described in b) as a crosslinking agent can also be used. In this case, the solvent may be water, but if the water repellency of the cell base material is high, the paint is repelled. Therefore, an alcohol solvent such as methanol or ethanol is preferable.
[0148]
d) Combined use of alkoxysilane solution and alkali solution
When the solution of the alkoxysilane described in b) is applied to the substrate and heated at about 120 to 180 ° C. for several minutes, a silicon oxide film is formed on the surface of the substrate. Thereafter, immersion in an alkaline solution increases the hydrophilicity of the surface. Finally, the hydrophilic treatment is completed by washing the alkaline solution with water. As the alkaline solution, an aqueous solution of a hydroxide such as sodium hydroxide or potassium hydroxide, or an alcohol solution or a hydroalcoholic solution is used. The higher the concentration, the shorter the immersion time, but it also depends on the type of hydroxide used. When sodium hydroxide is used, the immersion time is preferably about 1 to 5 minutes at a solution concentration of 1% by weight and about 10 to 30 seconds at 5% by weight. Ketone solvents (acetone, methyl ethyl ketone, etc.) used as the solvent for the alkoxysilane solution are preferably alcohol, ester, or ether solvents since the alkoxysilane is easily changed to silicon dioxide. In particular, an alcohol-based material is particularly preferable when the base material is a resin, since it is difficult to dissolve the resin.
[3] Light source
In the present invention, the light source used to irradiate the metal wiring planned portion needs to emit light having an absorption wavelength of the light absorbing layer or the light absorbing portion. There is no particular problem whether it is a lamp or a laser. However, it is preferable that the irradiated light be absorbed as efficiently as possible, converted into heat, and given heat to the member forming the water-repellent layer. If the absorption spectrum of the light absorption layer or light absorption site is broad from near ultraviolet to near infrared, the light with a wider wavelength such as a xenon lamp than a laser or a mercury lamp that emits light of a specific wavelength Are preferred. Conversely, when the absorption spectrum is narrow, a laser that emits light of the absorption wavelength is desirable. In the case of near-ultraviolet light, a mercury lamp that emits light of a specific wavelength is also effective, similarly to a laser. Specifically, a mercury lamp emits light of 254 nm, 365 nm (I line), and 435 nm (G line) in the visible region.
[0149]
In the case of a low-pressure mercury lamp, light of 185 nm is also emitted. However, since light of this wavelength is absorbed by oxygen or the like, it is necessary to place the substrate in a place under reduced pressure during light irradiation, which departs from the idea of the present invention of manufacturing a wiring substrate without using a vacuum process.
[0150]
In the case of a laser, 415 nm, 488 nm, and 515 nm of an argon laser are used. YAG laser 2nd harmonic 532 nm, 3rd harmonic 355 nm, 4th harmonic 266 nm. 337 nm with nitrogen laser. 633 nm for helium / neon laser. 308 nm of excimer laser (XeCl). Examples include 670 nm, 780 nm, and 830 nm of a semiconductor laser, and 1064 nm of a YAG laser. Further, by using the dye for laser transmission, light of a wide range of wavelengths can be transmitted. For this reason, the range of choice of the dye is expanded. For example, by using 7- (ethylamino) -4,6-dimethyl-2H-1-benzopyran-2-one which is a coumarin-based dye as a dye for laser emission, light of 430 to 490 nm can be emitted. When transmitting a longer wavelength than that, 2,3,6,7-tetrahydro-11-oxo-1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolidine which is a coumarin-based dye By using -10-carboxylic acid ethyl ester, light of 484 to 544 nm can be transmitted. When a longer wavelength is to be transmitted, the rhodamine-based dye 9- [2- (ethoxycarbonyl) phenyl] -3,6-bis (ethylamino) -2,7-dimethylanthurium chloride is used to obtain 550 to 550. 633 nm light can be transmitted. In the case of transmitting a longer wavelength, light of 645 to 808 nm can be transmitted by using 2- [4- {4- (dimethylamino) phenyl} -1,3-butadienyl] -1-ethylpyridinium perchlorate. is there. For transmitting a longer wavelength, 5-chloro-2- [2- [3- {2- (5-chloro-3-ethyl-2 (3H) -benzothiazolylidene) ethylidene} -2-diphenylamino Light of 805 to 1030 nm can be transmitted by using -1-cyclopenten-1-yl] ethenyl] -3-ethyl-benzothiazolium perchlorate. When transmitting a longer wavelength, 3-ethyl-2-[[3- [3- [3-{(3-ethylnaphtho [2,1-d] thiazole-2 (3H) -ylidene) methyl} -5} is used. , 5-dimethyl-2-cyclohexene-1-ylidene] -1-propenyl] -5,5-dimethyl-2-cyclohexene-1-ylidene] methyl] naphtho [2,1-d] thiazolium perchlorate Thus, light of 1076 to 1200 nm can be transmitted.
[0151]
[4] A liquid in which a metal member is dissolved or dispersed
Examples of the liquid in which the metal member is dispersed include a liquid in which gold, silver, and platinum are dispersed. These require a dispersant and a dispersion stabilizer so that they do not aggregate into large particles. It is desirable that the primary particles have a size of several tens nm. Since copper is easily corroded by oxygen in the air, it is desirable to add an antioxidant to the dispersion.
[0152]
Examples of the solution in which the metal member is dissolved include a plating solution. For example, a copper-containing liquid for electroless copper plating may be used. In this method, a palladium chloride solution is previously applied to a portion where hydrophilic patterning is to be performed, and then a copper-containing solution is applied. This improves the adhesion of the formed copper wiring to the substrate. The adhesion is further improved by performing the operation of applying the gold-containing liquid before the copper-containing liquid is applied.
[0153]
[5] Application method to display device fabrication
As described above, regarding the production of a display device, instead of “a liquid in which a metal member for forming a wiring is dissolved or dispersed” used in producing a wiring board, “an insulating layer, a semiconductor layer, a light emitting layer, and the like are formed. It can be manufactured by using "liquid". Details of the fabrication will be described in Examples.
[0154]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples, but the scope of the present invention is not limited to these Examples.
[0155]
Examples 1 to 22 show a method of manufacturing a wiring board having a light absorbing layer and a water-repellent layer among the wiring boards of the present invention, and the performance evaluation results. Further, in Examples 23 to 38, among the wiring boards of the present invention, a method for manufacturing a wiring board having a water-repellent layer having a light absorbing part and performance evaluation results are shown. Embodiment 39 is an embodiment relating to both. Example 41 and subsequent examples show a method for producing a display element such as a TFT and an organic EL substrate and a color filter, and the performance evaluation results.
[0156]
Embodiment 1
(1) Light absorbing layer forming step
The glass substrate was irradiated with ultraviolet light by a low-pressure mercury lamp. The lamp is 500 W and the irradiation time is 5 minutes. As a result, the contact angle of the glass substrate with water decreased from 30 to 35 ° before irradiation to 10 ° or less after irradiation. This treatment is an operation for improving the wettability so that the dye to be applied for forming the light absorbing layer can be uniformly applied.
[0157]
A 1% by weight methyl ethyl ketone solution of Hayashibara Biochemical Laboratory Co., Ltd. dye NK-2014 and a 1% by weight methyl ethyl ketone solution of Marukalinker M, a phenolic resin manufactured by Maruzen Petrochemical Co., Ltd., are prepared. The absorption maximum wavelength of the dye thin film formed when NK-2014 is applied to a transparent substrate such as glass or quartz is about 780 nm. After mixing the two liquids by the same weight, the mixed liquid is applied onto the aluminum substrate subjected to the above-mentioned treatment by a spin coating method (rotation speed: 2000 rpm, rotation time: 30 seconds). Further heat at 80 ° C. for 2 minutes. Thus, a light absorbing layer is formed.
[0158]
(2) Water repellent layer forming step
Next, it is immersed in a 0.1 wt% PF-5080 solution of Compound 1 for 10 minutes, and then heated at 120 ° C. for 10 minutes. Thus, a water-repellent layer is formed.
[0159]
(3) Light irradiation step
A semiconductor laser having an output of 2 mW and a transmission wavelength of 780 nm is used to irradiate a portion of the substrate surface on which wiring is to be formed with a laser spot diameter of 2 μm and a scanning speed of 10 mm / sec. Then, the irradiated light is converted into heat, and the water-repellent layer formed by the compound 1 is denatured by this heat. As a result, the water repellency of the denatured portion (that is, the light-irradiated portion) is reduced.
[0160]
(4) Metal wiring forming step
A vat containing a 0.5% by weight silver fine particle dispersion liquid (the solvent is water, the surface tension of the liquid is 69 mN / m, and the average primary particle size of the silver fine particles is about 20 nm) is prepared to a depth of 5 mm. I do. The bat is large enough to accommodate the board. The light-irradiated surface of the substrate after light irradiation is placed in a bat with the light-irradiated surface facing down, and then immediately pulled up. The silver fine particle dispersion does not adhere to the non-irradiated part, but the silver fine particle dispersion adheres to the light irradiated part. The substrate is heated at 120 ° C. for 15 minutes with the side to which the silver fine particle dispersion is attached facing up. The solvent water was volatilized at the portion where the silver fine particle dispersion was attached, and silver wiring was formed.
[0161]
(5) Continuity confirmation test
When the detection needle of the tester was brought into contact with the end of the formed wiring, conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0162]
Embodiment 2
A wiring board is formed in the same manner as in Example 1 except that dye NK-4 manufactured by Hayashibara Biochemical Laboratory is used instead of dye NK-2014 manufactured by Hayashibara Biochemical Laboratory. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0163]
Note that a dye thin film formed when NK-4 is applied to a transparent substrate such as glass or quartz has an absorption maximum wavelength of about 780 nm.
[0164]
Embodiment 3
Example 1 was repeated except that the dye NK-22014 manufactured by Hayashibara Biochemical Laboratory was used instead of the dye NK-22014 manufactured by Hayashibara Biochemical Laboratory, and the emission wavelength of the semiconductor laser used for light irradiation was changed from 780 nm to 830 nm. A wiring board is formed by the same operation. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0165]
The absorption maximum wavelength of the dye thin film formed when NK-2268 is applied to a transparent substrate such as glass or quartz is about 830 nm.
[0166]
Embodiment 4
Example 1 was repeated except that the dye NK-3987 manufactured by Hayashibara Biochemical Laboratory was used instead of the dye NK-2014 manufactured by Hayashibara Biochemical Laboratory, and the emission wavelength of the semiconductor laser used for light irradiation was changed from 780 nm to 670 nm. A wiring board is formed by the same operation. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0167]
The absorption maximum wavelength of the dye thin film formed when NK-3987 is applied to a transparent substrate such as glass or quartz is about 670 nm.
[0168]
Embodiment 5
Example 1 was repeated except that the emission wavelength of the semiconductor laser used for light irradiation was changed from 780 nm to 670 nm, using the dye NK-2929 manufactured by Hayashibara Biochemical Laboratory instead of the dye NK-2014 manufactured by Hayashibara Biochemical Laboratory. A wiring board is formed by the same operation. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0169]
The absorption maximum wavelength of the dye thin film formed when NK-2929 is applied to a transparent substrate such as glass or quartz is about 670 nm.
[0170]
Embodiment 6
Except for using the dye NK-1886 manufactured by Hayashibara Biochemical Laboratory instead of the dye NK-2014 manufactured by Hayashibara Biochemical Laboratory and replacing the laser used for light irradiation with an argon laser and changing the emission wavelength from 780 nm to 415 nm. A wiring board is formed by the same operation as in the first embodiment. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0171]
The absorption maximum wavelength of the dye thin film formed when NK-1886 is applied to a transparent substrate such as glass or quartz is about 415 nm.
[0172]
A wiring board is formed by the same operation as described above except that the dye NK-723 manufactured by Hayashibara Biochemical Laboratory is used instead of NK-1886 and the emission wavelength is changed from 415 nm to 488 nm. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0173]
Note that a dye thin film formed when NK-723 is applied to a transparent substrate such as glass or quartz has an absorption maximum wavelength of about 490 nm.
[0174]
Also, a dye NK-1420 manufactured by Hayashibara Biochemical Laboratory Co., Ltd. is used instead of NK-1886, and a wiring board is formed by the same operation as described above except that the emission wavelength is changed from 415 nm to 515 nm. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0175]
The absorption maximum wavelength of the dye thin film formed when NK-1420 is applied to a transparent substrate such as glass or quartz is about 515 nm.
[0176]
Embodiment 7
Using a dye NK-529 manufactured by Hayashibara Biochemical Laboratory instead of the dye NK-2014 manufactured by Hayashibara Biochemical Laboratory, the laser used for light irradiation was changed to a helium / neon laser, and as a result, the emission wavelength was changed from 780 nm to 633 nm. A wiring board is formed by the same operation as in the first embodiment except that the wiring board is changed. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0177]
The absorption maximum wavelength of the dye thin film formed when NK-529 is applied to a transparent substrate such as glass or quartz is about 635 nm.
[0178]
Embodiment 8
The dye NK-3508 manufactured by Hayashibara Biochemical Laboratory was used instead of the dye NK-32014 manufactured by Hayashibara Biochemical Laboratory, and the laser used for light irradiation was changed to YAG laser. As a result, the transmission wavelength was changed from 780 nm to 1064 nm. A wiring board is formed in the same manner as in the first embodiment except that the wiring board is formed. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0179]
The absorption maximum wavelength of the dye thin film formed when NK-3508 is applied to a transparent substrate such as glass or quartz is about 1060 nm.
[0180]
Same as above except that NK-1046 was used instead of NK-3508, and a secondary nonlinear element was combined with the optical system of the YAG laser to be used, and the emission wavelength was changed from 1064 nm to 532 nm. To form a wiring board. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0181]
The maximum absorption wavelength of a dye thin film formed when NK-1046 is applied to a transparent substrate such as glass or quartz is about 530 nm.
[0182]
The same as above, except that NKX-1317 manufactured by Hayashibara Biochemical Laboratory was used instead of NK-3508, and the tertiary nonlinear element was combined with the optical system of the YAG laser to be used, and the emission wavelength was changed from 1064 nm to 355 nm. To form a wiring board. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0183]
The maximum absorption wavelength of the dye thin film formed when NKX-1317 is applied to a transparent substrate such as glass or quartz is about 360 nm.
[0184]
Further, a wiring board is formed by the same operation as described above except that NK-3508 is not added, a fourth-order nonlinear element is combined with the optical system of the YAG laser to be used, and the emission wavelength is changed from 1064 nm to 266 nm. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0185]
When NK-3508 is not added, the light absorbing layer becomes a thin film formed of only Marcalinker M. Absorption of the dye thin film formed when the Markerlinker M is applied to a transparent substrate such as glass or quartz is observed from around 450 nm, the absorption increases as the wavelength becomes shorter, and no clear maximum wavelength is observed above 250 nm. Was. However, since the absorbance of the light absorbing layer at 266 nm was 2.0 or more, the absorption was confirmed to be 99% or more. That is, it is determined that most of the irradiated light is absorbed and converted into heat energy.
[0186]
Embodiment 9
Using a dye NK-3212 manufactured by Hayashibara Biochemical Laboratory instead of the dye NK-2014 manufactured by Hayashibara Biochemical Laboratory, and replacing the light source used for light irradiation with an ultra-high pressure mercury lamp, a filter that cuts light of 400 nm or less, A wiring substrate is formed by the same operation as in the first embodiment except that light irradiation is performed through a mask that blocks light only in a non-wiring portion. In this case, the wavelength of the irradiated light is 435 nm. The energy per unit time of the irradiation light is adjusted in the same manner as in the first embodiment. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0187]
The maximum absorption wavelength of a dye thin film formed when NK-3212 is applied to a transparent substrate such as glass or quartz is about 435 nm.
[0188]
Also, instead of using NK-3212, a dye NKX-1317 manufactured by Hayashibara Biochemical Laboratories, and using a filter that cuts light at 400 nm or less and a filter that cuts light at 350 nm instead of a filter that cuts light of 400 nm or less, a wiring board was formed in the same manner as described above. Form. In this case, the wavelength of the irradiated light is 365 nm. In this case, the energy per unit time of the irradiation light is adjusted in the same manner as in the first embodiment. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0189]
The maximum absorption wavelength of the dye thin film formed when NKX-1317 is applied to a transparent substrate such as glass or quartz is about 360 nm.
[0190]
In addition, except that NK-3212 was not added, the lamp to be used was changed from an ultra-high pressure mercury lamp to a high pressure mercury lamp, and a wiring board that cuts light of 400 nm or less was used instead of a filter that cuts 300 nm, in the same operation as described above. To form In this case, the wavelength of the irradiated light is 254 nm. In this case, the energy per unit time of the irradiation light is adjusted in the same manner as in the first embodiment. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0191]
When NK-3508 is not added, the light absorbing layer becomes a thin film formed of only Marcalinker M. Absorption of the dye thin film formed when the Markerlinker M is applied to a transparent substrate such as glass or quartz is observed from around 450 nm, the absorption increases as the wavelength becomes shorter, and no clear maximum wavelength is observed above 250 nm. Was. However, since the absorbance of the light absorbing layer at 254 nm was 1.0 or more, it was confirmed that the absorptance was 90% or more. That is, it is determined that most of the irradiated light is absorbed and converted into heat energy.
[0192]
Embodiment 10
A wiring board was formed in the same manner as in Example 1 except that a 0.1 wt% PF-5080 solution of Compound 2 was used instead of the 0.1 wt% PF-5080 solution of Compound 1 in the water-repellent layer forming step. I do. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0193]
Embodiment 11
A wiring board was formed in the same manner as in Example 1 except that a 0.1 wt% PF-5080 solution of Compound 3 was used instead of the 0.1 wt% PF-5080 solution of Compound 1 in the water-repellent layer forming step. I do. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0194]
Embodiment 12
A wiring board was formed in the same manner as in Example 1 except that a 0.1 wt% PF-5080 solution of Compound 4 was used instead of the 0.1 wt% PF-5080 solution of Compound 1 in the water-repellent layer forming step. I do. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0195]
Embodiment 13
A wiring board was formed in the same manner as in Example 1 except that a 0.1 wt% PF-5080 solution of Compound 5 was used instead of the 0.1 wt% PF-5080 solution of Compound 1 in the water-repellent layer forming step. I do. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0196]
Embodiment 14
A wiring board was formed in the same manner as in Example 1 except that a 0.1% by weight PF-5080 solution of Compound 6 was used instead of the 0.1% by weight PF-5080 solution of Compound 1 in the water-repellent layer forming step. I do. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0197]
Embodiment 15
A wiring board was formed in the same manner as in Example 1 except that a 0.1 wt% PF-5080 solution of the compound 7 was used instead of the 0.1 wt% PF-5080 solution of the compound 1 in the water-repellent layer forming step. I do. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0198]
Embodiment 16
A wiring board was formed in the same manner as in Example 1 except that a 0.1 wt% PF-5080 solution of compound 8 was used instead of the 0.1 wt% PF-5080 solution of compound 1 in the water-repellent layer forming step. I do. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0199]
Embodiment 17
A wiring board was formed in the same manner as in Example 1 except that a 0.1 wt% PF-5080 solution of compound 9 was used instead of the 0.1 wt% PF-5080 solution of compound 1 in the water-repellent layer forming step. I do. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0200]
Embodiment 18
A wiring board was formed in the same manner as in Example 1 except that a 0.1% by weight PF-5080 solution of the compound 10 was used instead of the 0.1% by weight PF-5080 solution of the compound 1 in the water-repellent layer forming step. I do. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0201]
Embodiment 19
A wiring board was formed in the same manner as in Example 1 except that a 0.1 wt% PF-5080 solution of compound 11 was used instead of the 0.1 wt% PF-5080 solution of compound 1 in the water-repellent layer forming step. I do. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0202]
Embodiment 20
A wiring substrate was formed in the same manner as in Example 1 except that a 0.1 wt% PF-5080 solution of Compound 12 was used instead of the 0.1 wt% PF-5080 solution of Compound 1 in the water-repellent layer forming step. I do. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0203]
Embodiment 21
In the water-repellent layer forming step, a 0.1% by weight PF-5060 solution (PF-5060 manufactured by 3M) of Optool DSX (manufactured by Daikin Industries, Ltd.) was used instead of the 0.1% by weight PF-5080 solution of compound 1. A wiring board is formed in the same manner as in Example 1 except that the wiring board is used. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0204]
Embodiment 22
A solution obtained by diluting a 7% by weight solution of Cytop CTL-107M (manufactured by Asahi Glass Co., Ltd.) to 0.1% by weight with PF-5080 instead of the 0.1% by weight PF-5080 solution of compound 1 in the water-repellent layer forming step. A wiring board is formed by the same operation as in the first embodiment except that is used. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0205]
Embodiment 23
In the step of forming a water-repellent layer, instead of the 0.1 wt% PF-5080 solution of compound 1,
A wiring board is formed in the same manner as in Example 1, except that a 2% by weight solution of INT-304VC (manufactured by INT Screen) is diluted to 0.1% by weight with PF-5080. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0206]
Embodiment 24
(1) Step of forming a water-repellent layer having a light absorbing portion
A glass substrate is immersed in a 0.1% by weight solution of compound 13 in HFE-7200 (HFE-7200 manufactured by 3M) for 10 minutes, and then heated at 120 ° C. for 10 minutes. Thus, a water-repellent layer having a light absorbing portion is formed.
[0207]
Note that a dye thin film formed when the compound 13 is applied to a transparent substrate such as glass or quartz has an absorption maximum wavelength of about 500 nm.
[0208]
(2) Light irradiation step
Using an argon laser with an output of 3 mW and a transmission wavelength of 488 nm, light is irradiated onto a portion of the substrate surface where wiring is to be formed at a laser spot diameter of 2 μm and a scan speed of 10 mm / sec.
[0209]
Then, the irradiated light is converted to heat, and the water-repellent layer formed by the compound 13 is denatured by the heat, and as a result, the water repellency of the denatured portion (that is, the light-irradiated portion) is reduced.
[0210]
(3) Metal wiring forming step
A vat containing a 0.5% by weight silver fine particle dispersion liquid (the solvent is water, the surface tension of the liquid is 69 mN / m, and the average primary particle size of the silver fine particles is about 20 nm) is prepared to a depth of 5 mm. I do. The bat is large enough to accommodate the board. The light-irradiated surface of the substrate after light irradiation is placed in a bat with the light-irradiated surface facing down, and then immediately pulled up. The silver fine particle dispersion does not adhere to the non-irradiated part, but the silver fine particle dispersion adheres to the light irradiated part. The substrate is heated at 120 ° C. for 15 minutes with the side to which the silver fine particle dispersion is attached facing up. The solvent water was volatilized at the portion where the silver fine particle dispersion was attached, and silver wiring was formed.
[0211]
(4) Continuity confirmation test
When the detection needle of the tester was brought into contact with the end of the formed wiring, conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0212]
Embodiment 25
Compound 14 was used in place of compound 13, and the laser used for light irradiation was changed from an argon laser to a helium / neon laser.
A wiring board is formed by the same operation as in Example 24 except that the thickness is changed from nm to 633 nm. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0213]
Note that a dye thin film formed when the compound 14 is applied to a transparent substrate such as glass or quartz has an absorption maximum wavelength of about 600 nm.
[0214]
Embodiment 26
A wiring board is formed in the same manner as in Example 24 except that Compound 15 is used instead of Compound 13. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0215]
Note that a dye thin film formed when the compound 15 is applied to a transparent substrate such as glass or quartz has an absorption maximum wavelength of about 500 nm.
[0216]
Embodiment 27
Compound 16 was used in place of compound 13, and the laser used for light irradiation was changed from an argon laser to a helium / neon laser. As a result, the wiring substrate was operated in the same manner as in Example 24 except that the emission wavelength was changed from 488 nm to 633 nm. To form When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0217]
Note that a dye thin film formed when the compound 16 is applied to a transparent substrate such as glass or quartz has an absorption maximum wavelength of about 600 nm.
[0218]
Embodiment 28
A wiring board is formed in the same manner as in Example 24 except that Compound 17 is used instead of Compound 13. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0219]
Note that a dye thin film formed when the compound 17 is applied to a transparent substrate such as glass or quartz has an absorption maximum wavelength of about 500 nm.
[0220]
Embodiment 29
Compound 18 was used in place of compound 13, and the laser used for light irradiation was changed from an argon laser to a helium / neon laser, and as a result, the wiring board was operated in the same manner as in Example 24 except that the emission wavelength was changed from 488 nm to 633 nm. To form When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0221]
Note that a dye thin film formed when the compound 18 is applied to a transparent substrate such as glass or quartz has an absorption maximum wavelength of about 600 nm.
[0222]
Embodiment 30
A wiring board is formed in the same manner as in Example 24 except that Compound 19 is used instead of Compound 13. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0223]
Note that a dye thin film formed when the compound 19 is applied to a transparent substrate such as glass or quartz has an absorption maximum wavelength of about 500 nm.
[0224]
Embodiment 31
Compound 20 was used in place of compound 13, and the laser used for light irradiation was changed from an argon laser to a helium / neon laser. As a result, the wiring substrate was changed in the same manner as in Example 24 except that the emission wavelength was changed from 488 nm to 633 nm. To form When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0225]
Note that a dye thin film formed when the compound 20 is applied to a transparent substrate such as glass or quartz has an absorption maximum wavelength of about 600 nm.
[0226]
Embodiment 32
A wiring board is formed in the same manner as in Example 24 except that Compound 21 is used instead of Compound 13. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0227]
Note that a dye thin film formed when the compound 21 is applied to a transparent substrate such as glass or quartz has an absorption maximum wavelength of about 500 nm.
[0228]
Embodiment 33
A wiring board is formed in the same manner as in Example 24 except that Compound 22 is used instead of Compound 13. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0229]
Note that a dye thin film formed when the compound 22 is applied to a transparent substrate such as glass or quartz has an absorption maximum wavelength of about 500 nm.
[0230]
Embodiment 34
Compound 23 was used in place of compound 13, and the laser used for light irradiation was changed from an argon laser to a helium / neon laser, and as a result, the emission wavelength was changed from 488 nm to 633 nm. To form When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0231]
Note that a dye thin film formed when the compound 23 is applied to a transparent substrate such as glass or quartz has an absorption maximum wavelength of about 600 nm.
[0232]
Embodiment 35
Compound 24 was used in place of compound 13, and the laser used for light irradiation was changed from an argon laser to a helium / neon laser. As a result, the emission wavelength was changed from 488 nm to 633 nm. To form When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0233]
Note that a dye thin film formed when the compound 24 is applied to a transparent substrate such as glass or quartz has an absorption maximum wavelength of about 600 nm.
[0234]
Embodiment 36
A wiring board is formed in the same manner as in Example 24 except that Compound 25 is used instead of Compound 13. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0235]
Note that a dye thin film formed when the compound 25 is applied to a transparent substrate such as glass or quartz has an absorption maximum wavelength of about 500 nm.
[0236]
Embodiment 37
Compound 26 was used in place of Compound 13, and the laser used for light irradiation was changed from an argon laser to a helium / neon laser, and as a result, the wiring substrate was changed in the same manner as in Example 24 except that the emission wavelength was changed from 488 nm to 633 nm. To form When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0237]
Note that a dye thin film formed when the compound 26 is applied to a transparent substrate such as glass or quartz has an absorption maximum wavelength of about 600 nm.
[0238]
Embodiment 38
A wiring board is formed in the same manner as in Example 24 except that Compound 27 is used instead of Compound 13. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0239]
Note that a dye thin film formed when the compound 27 is applied to a transparent substrate such as glass or quartz has an absorption maximum wavelength of about 500 nm.
[0240]
Embodiment 39
Compound 1 was used instead of compound 13, and the laser used for light irradiation was changed from an argon laser to a low-pressure mercury lamp, and the transmission wavelength was changed from 488 nm to 254 nm by passing through a filter that cuts light of 300 nm or more. Forms a wiring board by the same operation as in Example 24. The optical system was adjusted so that the light output and the irradiation area were the same. When the detection needle of the tester was brought into contact with the end of the wiring on which the wiring board was also formed, the conduction of electricity was confirmed. In addition, the insulating property in a place where no wiring was formed was also confirmed.
[0241]
Since Compound 1 has an amide bond, absorption is observed at around 270 nm, and from 250 nm to 250 nm, the absorption increases as the wavelength becomes shorter. The absorbance at 254 nm when applied to a transparent substrate such as glass or quartz was 0.53 or more. The absorptance is 70% or more.
[0242]
Embodiment 40
When the width of the wiring formed in each example was measured, the width of the wiring formed in Examples 1 to 20 and 23 to 38 was 3 μm or less. However, the width of the wiring formed in Examples 22 and 23 was 5 μm. Since the spot diameter at the time of light irradiation is 2 μm, the width of light at the time of irradiation is 2 μm. In Examples 22 and 23, it is estimated that diffusion of thermal energy converted from light energy occurred. In Examples 22 and 23, the water-repellent layer forming material used was a fluorine-based resin material Cytop CTL-107M or INT304-VC. Therefore, in order to reduce the thickness of the water-repellent layer in order to improve the way of transmission, an experiment was performed with the solution concentration of CYTOP CTL-107M or INT304-VC reduced to １ ／, but the wiring width was 5 μm. The water-repellent layer forming material used in the other examples is a fluorine-containing compound having a perfluoropolyether chain or a fluoroalkyl chain and an alkoxysilane residue. From the above, it is effective to use a fluorine-containing compound having a perfluoropolyether chain or a fluoroalkyl chain and an alkoxysilane residue as the water-repellent layer forming material in that a wiring having a width corresponding to the width of light irradiation can be obtained. It was shown.
[0243]
Embodiment 41
An attempt was made to fabricate a TFT for a display element using the technique of the present invention. FIG. 3 shows a schematic diagram of the manufacturing process.
[0244]
(1) Water repellent layer forming step having a light absorbing part
A glass substrate 11 having a size of 100 × 100 mm and a thickness of 1 mm is immersed in a 0.1% by weight solution of compound 14 in HFE-7200 (HFE-7200 manufactured by 3M) for 10 minutes, and then heated at 120 ° C. for 10 minutes. Thus, a water-repellent layer 12 having a light absorbing portion is formed.
[0245]
(2) Light irradiation step
A helium / neon laser having an output of 3 mW and a transmission wavelength of 633 nm is used to irradiate a 633 nm light 13 onto a portion of the substrate surface where a gate electrode is to be formed at a laser spot diameter of 2 μm and a scan speed of 10 mm / sec.
[0246]
In FIG. 3, the light-irradiated portion is depicted as if the water-repellent layer having the light-absorbing portion has been removed. However, in actuality, the water-repellent layer having the light-absorbing portion has been modified (from a kind of fluorine-containing compound). Layer) remains. When the surface where the water-repellent layer was modified was analyzed by TOF-SIMS, a signal of a fluorine atom was observed. From this fact, it was confirmed that the portion irradiated with light showed a decrease in water repellency but was present as a layer made of a fluorine-containing compound.
[0247]
(3) Step of forming gate electrode
A vat containing a 0.5% by weight silver fine particle dispersion liquid (the solvent is water, the surface tension of the liquid is 69 mN / m, and the average primary particle size of the silver fine particles is about 20 nm) is prepared to a depth of 5 mm. I do. The bat is large enough to accommodate the board. The light-irradiated surface of the substrate after light irradiation is placed in a bat with the light-irradiated surface facing down, and then immediately pulled up. The silver fine particle dispersion does not adhere to the non-irradiated part, but the silver fine particle dispersion adheres to the light irradiated part. The substrate is heated at 120 ° C. for 15 minutes with the side to which the silver fine particle dispersion is attached facing up. The solvent water is volatilized in the portion where the silver fine particle dispersion is attached, and the silver gate electrode 14 is formed.
[0248]
(4) Overall light irradiation step
The entire surface of the substrate is irradiated with light for 10 minutes using a 2000 W xenon lamp. The filter does not pass through the irradiation light 15 in particular. Due to this light irradiation, the water repellency of the surface is lost.
[0249]
Although FIG. 3 shows that the water-repellent layer having the light-absorbing portion on the light-irradiated surface has been removed, the water-repellent layer having the light-absorbing portion is actually modified (from a kind of fluorine-containing compound). Layer) remains.
[0250]
(5) Insulation layer formation
After a silver wiring is formed, a 1% methyl ethyl ketone solution of poly (vinyl phenol) is applied by a spin coating method (rotation speed: 200 rpm, rotation time: 60 seconds), and dried at 100 ° C. for 10 minutes to volatilize methyl ethyl ketone. The chemical structure of poly (vinyl phenol) is as follows.
[0251]
Embedded image

[0252]
Thus, the insulating layer 16 made of poly (vinylphenol) is formed.
[0253]
(6) Water-repellent layer forming step having a light absorbing portion
The substrate on which the insulating layer is formed is immersed in a 0.1% by weight solution of compound 14 in HFE-7200 (HFE-7200 manufactured by 3M) for 10 minutes, and then heated at 120 ° C. for 10 minutes. Thus, a water-repellent layer 17 having a light absorbing portion is formed on the insulating layer.
[0254]
(7) Light irradiation step
A helium / neon laser having an output of 3 mW and a transmission wavelength of 633 nm is used to irradiate 633 nm light 18 on a portion of the substrate surface where a source electrode and a drain electrode are to be formed at a laser spot diameter of 2 μm and a scanning speed of 10 mm / sec.
[0255]
In FIG. 3, the light-irradiated portion is depicted as if the water-repellent layer having the light-absorbing portion has been removed. However, in actuality, the water-repellent layer having the light-absorbing portion has been modified (from a kind of fluorine-containing compound). Layer) remains.
[0256]
(8) Metal electrode forming step
A vat containing the same 0.5 wt% silver fine particle dispersion as used in (2) so as to have a depth of 5 mm is prepared. The light-irradiated surface of the substrate after light irradiation is placed in a bat with the light-irradiated surface facing down, and then immediately pulled up. The silver fine particle dispersion does not adhere to the non-irradiated part, but the silver fine particle dispersion adheres to the light irradiated part. The substrate is heated at 120 ° C. for 15 minutes with the side to which the silver fine particle dispersion is attached facing up. The solvent water is volatilized in the portion where the silver fine particle dispersion adheres, and the source electrode and the drain electrode 19 are formed.
[0257]
(9) Water repellent layer forming step having a light absorbing part
The substrate on which the electrodes are formed is immersed in a 0.1% by weight solution of compound 14 in HFE-7200 (HFE-7200 manufactured by 3M) for 10 minutes, and then heated at 120 ° C. for 10 minutes. In this way, the water-repellent layer 20 having a light absorbing portion is formed on the entire surface of the substrate on which the electrodes are formed.
[0258]
(10) Light irradiation step
Using a helium / neon laser having an output of 3 mW and a transmission wavelength of 633 nm, a 633 nm light 21 is applied to a portion where a semiconductor portion is to be formed on the substrate surface at a laser spot diameter of 2 μm and a scan speed of 10 mm / sec.
[0259]
In FIG. 3, the light-irradiated portion is depicted as if the water-repellent layer having the light-absorbing portion has been removed. However, in actuality, the water-repellent layer having the light-absorbing portion has been modified (from a kind of fluorine-containing compound). Layer) remains.
[0260]
(11) Semiconductor part formation
A vat containing a 1% xylene solution of poly- (9,9-dioctylfluorene-bisthiophene) to a depth of 5 mm is prepared. The chemical structure of poly- (9,9-dioctylfluorene-bisthiophene) is shown below.
[0261]
Embedded image

[0262]
The light-irradiated surface of the substrate after light irradiation is placed in a bat with the light-irradiated surface facing down, and then immediately pulled up. The 1% xylene solution of poly- (9,9-dioctylfluorene-bisthiophene) does not adhere to the non-irradiated portion, but 1-poly (9,9-dioctylfluorene-bisthiophene) does not adhere to the irradiated portion. % Xylene solution adheres. The substrate is heated at 120 ° C. for 10 minutes with the side on which the 1% xylene solution of poly- (9,9-dioctylfluorene-bisthiophene) is attached facing up. The xylene of the solvent is volatilized at the portion where the 1% xylene solution of poly- (9,9-dioctylfluorene-bisthiophene) adheres, and the semiconductor site 22 composed of poly- (9,9-dioctylfluorene-bisthiophene) is formed. Is done.
[0263]
(12) Light irradiation step
A helium / neon laser having an output of 3 mW and a transmission wavelength of 633 nm is used to irradiate 633 nm light 23 at a laser spot diameter of 2 μm and a scanning speed of 10 mm / sec to portions other than the semiconductor portion formation portion on the substrate surface.
[0264]
In FIG. 3, the light-irradiated portion is depicted as if the water-repellent layer having the light-absorbing portion has been removed. However, in actuality, the water-repellent layer having the light-absorbing portion has been modified (from a kind of fluorine-containing compound). Layer) remains.
[0265]
(13) Insulation layer formation
A 1% methyl ethyl ketone solution of poly (vinyl phenol) is applied on the surface on which the semiconductor portion is formed by a spin coating method (rotation speed: 200 rpm, rotation time: 60 seconds), and dried at 100 ° C. for 10 minutes to volatilize methyl ethyl ketone. Thus, a protective layer 24 made of poly (vinyl phenol) is formed.
[0266]
Through the above steps, a TFT was manufactured. After wiring was applied to the produced TFT and a display was produced, an image output test was performed. As a result, image output was possible. Therefore, it was confirmed that a TFT can be manufactured according to the present invention without going through a vacuum process.
[0267]
Embodiment 42
Compound 13 was used in place of compound 14, and the laser used for light irradiation was changed from a helium / neon laser to an argon laser. As a result, the TFT was operated in the same manner as in Example 41 except that the emission wavelength was changed from 633 nm to 488 nm. Make it. After wiring was applied to the produced TFT and a display was produced, an image output test was performed. As a result, image output was possible. Therefore, it was again confirmed that the present invention enables a TFT to be manufactured without a vacuum step.
[0268]
Embodiment 43
An attempt was made to produce an organic EL substrate using the technique of the present invention. FIG. 4 schematically shows the manufacturing process.
[0269]
(1) Water repellent layer forming step having a light absorbing part
A glass substrate 26 having a size of 100 × 100 mm, a thickness of 1 mm, and a transparent electrode 25 made of ITO formed on the surface thereof was converted into a 0.1% by weight solution of compound 14 in HFE-7200 (HFE-7200 is manufactured by 3M). After immersion for 10 minutes, it is heated at 120 ° C. for 10 minutes. Thus, a water-repellent layer 27 having a light absorbing portion is formed.
[0270]
(2) Light irradiation step
A helium / neon laser having an output of 3 mW and a transmission wavelength of 633 nm is used to irradiate a portion of the substrate surface on which an insulating layer is to be formed with light 633 nm at a laser spot diameter of 2 μm and a scanning speed of 10 mm / sec.
[0271]
In FIG. 4, the light-irradiated portion is depicted as if the water-repellent layer having the light-absorbing portion has been removed. However, in actuality, the water-repellent layer having the light-absorbing portion has been modified (from a kind of fluorine-containing compound). Layer) remains.
[0272]
(3) Formation of insulating layer
A vat containing a 1% solution of poly (vinylphenol) in methyl ethyl ketone to a depth of 5 mm is prepared. The bat is large enough to accommodate the board. The light-irradiated surface of the substrate after light irradiation is placed in a bat with the light-irradiated surface facing down, and then immediately pulled up. The 1% methyl ethyl ketone solution of poly (vinyl phenol) does not adhere to the light non-irradiated portion, but the 1% methyl ethyl ketone solution of poly (vinyl phenol) adheres to the light irradiated portion. The substrate is heated at 100 ° C. for 10 minutes with the solution attached side up. Thus, an insulating layer 29 made of poly (vinyl phenol) is formed.
[0273]
(4) Water-repellent layer forming step having a light absorbing portion
The substrate on which the insulating layer is formed is immersed in a 0.1% by weight solution of compound 14 in HFE-7200 (HFE-7200 manufactured by 3M) for 10 minutes, and then heated at 120 ° C. for 10 minutes. Thus, a water-repellent layer 30 having a light absorbing portion is formed on the insulating layer.
[0274]
(5) Light irradiation step
Using a helium / neon laser having an output of 3 mW and a transmission wavelength of 633 nm, a light 31 having a wavelength of 633 nm is applied to the transparent electrode forming portion on the substrate surface at a laser spot diameter of 2 μm and a scanning speed of 10 mm / sec.
[0275]
In FIG. 4, the light-irradiated portion is depicted as if the water-repellent layer having the light-absorbing portion has been removed. However, in actuality, the water-repellent layer having the light-absorbing portion has been modified (from a kind of fluorine-containing compound). Layer) remains.
[0276]
(6) Hole transport layer forming step
A vat containing a 0.1% by weight of a copper dispersion of copper phthalocyanine in chloroform (primary particles of copper phthalocyanine having an average size of about 50 nm) is prepared to have a depth of 5 mm. The bat is large enough to accommodate the board. The light-irradiated surface of the substrate after light irradiation is placed in a bat with the light-irradiated surface facing down, and then immediately pulled up. The chloroform dispersion of copper phthalocyanine does not adhere to the non-irradiated portion, but the chloroform dispersion of copper phthalocyanine adheres to the portion irradiated with light. The substrate is heated at 70 ° C. for 15 minutes with the side to which the dispersion liquid is attached facing up. The chloroform as the dispersion medium is volatilized at the portion where the chloroform dispersion of copper phthalocyanine adheres, and the hole transport layer 32 is formed.
[0277]
(7) Light emitting layer forming step
A vat containing a 0.1% by weight solution of parafluorene in cyclohexanone to a depth of 5 mm is prepared. The bat is large enough to accommodate the board. After the hole transport layer is formed, the substrate is placed in a bat with the surface on which the hole transport layer is formed facing down, and then immediately pulled up. The cyclohexanone solution of parafluorene does not adhere to the portion where the hole transport layer is not formed, but the cyclohexanone solution of parafluorene adheres to the portion where the hole transport layer is formed. The substrate is heated at 120 ° C. for 15 minutes with the solution attached side up. At the portion where the cyclohexanone solution of parafluorene is attached, the solvent cyclohexanone volatilizes, and the light emitting layer 33 is formed.
[0278]
(8) Light irradiation step
Using a helium / neon laser having an output of 3 mW and a transmission wavelength of 633 nm, the insulating layer is irradiated with light having a wavelength of 633 nm at a laser spot diameter of 2 μm and a scanning speed of 10 mm / sec. This lowers the water repellency on the insulating layer.
[0279]
In FIG. 4, the light-irradiated portion is depicted as if the water-repellent layer having the light-absorbing portion has been removed. However, in actuality, the water-repellent layer having the light-absorbing portion has been modified (from a kind of fluorine-containing compound). Layer) remains.
[0280]
(9) Metal electrode forming step
A silver fine particle dispersion of 0.5% by weight (the solvent is a mixed solvent of water and ethanol, the surface tension of the liquid is 30 mN / m, and the average primary particle size of the silver fine particles is about 20 nm) is applied by spin coating (at 200 rpm). (Rotation time: 60 seconds), and then dried at 120 ° C. for 10 minutes to evaporate the solvent. Thus, a silver metal electrode 35 is formed.
[0281]
(10) Formation of sealing layer
After a metal electrode is formed, a 1% solution of poly (vinylphenol) in methyl ethyl ketone is applied by spin coating (rotation speed: 200 rpm, rotation time: 60 seconds), and dried at 100 ° C. for 10 minutes to volatilize methyl ethyl ketone. Thus, the sealing layer 36 is formed.
[0282]
Through the above steps, an organic EL substrate was manufactured. After wiring was applied to the organic EL substrate thus prepared and a light emitting device was prepared, a test was performed to determine whether or not to emit light. As a result, light emission was confirmed. Therefore, it was confirmed that an organic EL substrate can be manufactured by the method of the present invention.
[0283]
Embodiment 44
Compound 13 was used in place of compound 14, and the laser used for light irradiation was changed from a helium / neon laser to an argon laser. As a result, the organic light emission was changed in the same manner as in Example 43 except that the emission wavelength was changed from 633 nm to 488 nm. An EL substrate is manufactured. After wiring was applied to the organic EL substrate thus prepared and a light emitting device was prepared, a test was performed to determine whether or not to emit light. As a result, light emission was confirmed. Therefore, it was confirmed again that the organic EL substrate can be manufactured by the method of the present invention.
[0284]
Embodiment 45
An attempt was made to produce a color filter panel for a display using the technology of the present invention. FIG. 5 shows the manufacturing process.
[0285]
(1) Water repellent layer forming step having a light absorbing part
A glass substrate 37 having a size of 250 × 190 mm and a thickness of 1 mm is immersed in a 0.1% by weight solution of compound 14 in HFE-7200 (HFE-7200 is manufactured by 3M) for 10 minutes, and then heated at 120 ° C. for 10 minutes. Thus, a water-repellent layer 38 having a light absorbing portion is formed.
[0286]
(2) Light irradiation step
A helium / neon laser with an output of 3 mW and a transmission wavelength of 633 nm is used to irradiate a portion of the substrate surface where black matrix is to be formed with light 633 nm at a laser spot diameter of 2 μm and a scanning speed of 10 mm / sec.
[0287]
In FIG. 5, the light-irradiated portion is depicted as if the water-repellent layer having the light-absorbing site has been removed. However, in actuality, the water-repellent layer having the light-absorbing site has been modified (from a kind of fluorine-containing compound). Layer) remains.
[0288]
(3) Black matrix formation
Carbon black (average particle size of the primary particles is about 50 nm) (10 parts by weight) and a particle dispersant geraniol L-95 (1 part by weight) manufactured by Kao are added to cyclohexanone (1000 parts by weight), and the mixture is stirred by a planetary ball mill. After dispersing the carbon black, poly (vinylphenol) (50 parts by weight), epoxy resin EP1001 (50 parts by weight), and benzimidazole (1 part by weight) are added and stirred. Thus, a liquid in which the black matrix forming member is dissolved and suspended is prepared. This liquid is hereinafter referred to as a black matrix forming liquid.
[0289]
A bat containing a black matrix forming liquid at a depth of 5 mm is prepared. The bat is large enough to accommodate the board. The light-irradiated surface of the substrate after light irradiation is placed in a bat with the light-irradiated surface facing down, and then immediately pulled up. The black matrix forming liquid does not adhere to the light non-irradiated part, but the black matrix forming liquid adheres to the light irradiated part. The substrate is heated at 120 ° C. for 10 minutes with the side to which the liquid has adhered facing up. Thus, the black matrix 40 is formed.
[0290]
(4) Water-repellent layer forming step having a light absorbing portion
The substrate on which the black matrix is formed is immersed in a 0.1% by weight solution of compound 14 in HFE-7200 (HFE-7200 manufactured by 3M) for 10 minutes, and then heated at 120 ° C. for 10 minutes. Thus, a water-repellent layer 41 having a light absorbing portion is formed on the black matrix.
[0291]
(5) Light irradiation step
Using a helium / neon laser with an output of 3 mW and a transmission wavelength of 633 nm, a portion of the substrate surface where the R of the color filter is formed is irradiated with light having a wavelength of 633 nm at a laser spot diameter of 2 μm and a scanning speed of 10 mm / sec.
[0292]
In FIG. 5, the light-irradiated portion is depicted as if the water-repellent layer having the light-absorbing site has been removed. However, in actuality, the water-repellent layer having the light-absorbing site has been modified (from a kind of fluorine-containing compound). Layer) remains.
[0293]
(6) Step of forming R portion of color filter
Red dye for R. C. I. Pigment Red 177 (10 parts by weight) and a particle dispersing agent geraniol L-95 (1 part by weight) manufactured by Kao are added to ethanol (100 parts by weight), and the mixture is stirred with a planetary ball mill to obtain C.I. I. After dispersing Pigment Red 177, a 6% by weight silica sol solution (average molecular weight: 2,000 to 4,000; ethanol is 70% as a solvent, water is the main component, and the liquidity is controlled to about pH 3 with phosphoric acid) (20) Parts by weight). This is hereinafter referred to as a color filter R forming liquid.
[0294]
A vat containing the liquid for forming the R portion of the color filter so as to have a depth of 5 mm is prepared. The bat is large enough to accommodate the board. The light-irradiated surface of the substrate after light irradiation is placed in a bat with the light-irradiated surface facing down, and then immediately pulled up. The R part forming liquid of the color filter does not adhere to the non-irradiated portion, but the R part forming liquid of the color filter adheres to the light irradiated portion. The substrate is heated at 120 ° C. for 10 minutes with the side to which the liquid has adhered facing up. Thus, the R portion 43 of the color filter is formed.
[0295]
(7) Water-repellent layer forming step having a light absorbing portion
The substrate on which the R portion of the color filter is formed is immersed in a 0.1% by weight solution of compound 14 in HFE-7200 (HFE-7200 manufactured by 3M) for 10 minutes, and then heated at 120 ° C. for 10 minutes. Thus, a water-repellent layer 44 having a light absorbing portion is formed on the R portion of the color filter.
[0296]
(8) Light irradiation step
Using a helium / neon laser with an output of 3 mW and a transmission wavelength of 633 nm, light 45 having a wavelength of 633 nm is irradiated on a portion of the substrate surface where a color filter G is to be formed at a laser spot diameter of 2 μm and a scan speed of 10 mm / sec.
[0297]
In FIG. 5, the light-irradiated portion is depicted as if the water-repellent layer having the light-absorbing site has been removed. However, in actuality, the water-repellent layer having the light-absorbing site has been modified (from a kind of fluorine-containing compound). Layer) remains.
[0298]
(9) Step of forming G portion of color filter
Green pigment for G; I. Pigment Green 7 (10 parts by weight) and a particle dispersing agent geraniol L-95 (1 part by weight) manufactured by Kao were added to ethanol (100 parts by weight), and the mixture was stirred with a planetary ball mill to obtain C.I. I. After dispersing Pigment Green 7, a 6% by weight silica sol solution (average molecular weight: 2,000 to 4,000; ethanol is 70% as a solvent, water is the main component, and the liquidity is controlled to about pH 3 with phosphoric acid) (20) Parts by weight). This will be referred to as a color filter G forming liquid hereinafter.
[0299]
A bat containing the liquid for forming the G portion of the color filter so as to have a depth of 5 mm is prepared. The bat is large enough to accommodate the board. The light-irradiated surface of the substrate after light irradiation is placed in a bat with the light-irradiated surface facing down, and then immediately pulled up. The G part forming liquid of the color filter does not adhere to the light non-irradiated part, but the G part forming liquid of the color filter adheres to the light irradiated part. The substrate is heated at 120 ° C. for 10 minutes with the side to which the liquid has adhered facing up. Thus, the G portion 46 of the color filter is formed.
[0300]
(10) Step of forming a water-repellent layer having a light absorbing portion
The substrate on which the portion G of the color filter is formed is immersed in a 0.1% by weight solution of compound 14 in HFE-7200 (HFE-7200 manufactured by 3M) for 10 minutes, and then heated at 120 ° C. for 10 minutes. Thus, a water-repellent layer 47 having a light absorbing portion is formed on the G portion of the color filter.
[0301]
(11) Light irradiation step
Using a helium / neon laser having an output of 3 mW and a transmission wavelength of 633 nm, a portion of the substrate surface where a color filter B is to be formed is irradiated with light 48 having a wavelength of 633 nm at a laser spot diameter of 2 μm and a scanning speed of 10 mm / sec.
[0302]
In FIG. 5, the light-irradiated portion is depicted as if the water-repellent layer having the light-absorbing site has been removed. However, in actuality, the water-repellent layer having the light-absorbing site has been modified (from a kind of fluorine-containing compound). Layer) remains.
[0303]
(12) Step of forming B portion of color filter
B. Blue dye for B I. Pigment Blue 15 (10 parts by weight) and a particle dispersing agent geraniol L-95 (1 part by weight) manufactured by Kao are added to ethanol (100 parts by weight), and the mixture is stirred with a planetary ball mill to obtain C.I. I. After dispersing Pigment Blue 15, a 6% by weight silica sol solution (average molecular weight: 2,000 to 4,000; ethanol is 70% as a solvent, water is the main component, and the liquidity is controlled around pH 3 with phosphoric acid) (20) Parts by weight). This is hereinafter referred to as a color filter B forming liquid.
[0304]
A vat containing the liquid for forming the part B of the color filter so as to have a depth of 5 mm is prepared. The bat is large enough to accommodate the board. The light-irradiated surface of the substrate after light irradiation is placed in a bat with the light-irradiated surface facing down, and then immediately pulled up. The portion B forming solution of the color filter does not adhere to the non-irradiated portion, but the portion forming solution B of the color filter adheres to the portion irradiated with light. The substrate is heated at 120 ° C. for 10 minutes with the side to which the liquid has adhered facing up. Thus, the B portion 49 of the color filter is formed.
[0305]
(13) Light irradiation step
Using a helium / neon laser with an output of 3 mW and a transmission wavelength of 633 nm, a laser spot diameter of 2 μm and a scanning speed of 10 mm / sec.
[0306]
In FIG. 5, the light-irradiated portion is depicted as if the water-repellent layer having the light-absorbing site has been removed. However, in actuality, the water-repellent layer having the light-absorbing site has been modified (from a kind of fluorine-containing compound). Layer) remains.
[0307]
(14) Protective layer forming step
A 6% by weight silica sol solution (average molecular weight: 2,000 to 4,000; ethanol is 70% for the solvent, water is the main component, and the liquid property is controlled to around pH 3 with phosphoric acid) by spin coating (rotation speed: 200 rpm, rotation time) : 60 seconds), and then heated at 120 ° C for 10 minutes. In this way, the SiO on the black matrix and the color filters R, G, B ₂ Is formed.
[0308]
Through the above steps, a color filter panel was manufactured. When an image output test was conducted by incorporating the produced color filter panel into a display, it was confirmed that a clear image was formed. Therefore, it was confirmed that a color filter panel can be manufactured by the method of the present invention.
[0309]
Embodiment 46
Compound 13 was used in place of compound 14, and the laser used for light irradiation was changed from a helium / neon laser to an argon laser. As a result, the color filter was operated in the same manner as in Example 45 except that the emission wavelength was changed from 633 nm to 488 nm. Make a panel. When an image output test was conducted by incorporating the produced color filter panel into a display, it was confirmed that a clear image was formed. Therefore, it was again confirmed that a color filter panel can be manufactured by the method of the present invention.
[0310]
【The invention's effect】
According to the present invention, it is possible to provide a wiring substrate manufactured by forming a water-repellent / hydrophilic pattern by irradiating light having a long wavelength of 250 nm or more and performing metal wiring on the hydrophilic portion.
[Brief description of the drawings]
FIG. 1 illustrates the principle of the present invention (in the case of a substrate having a light absorbing layer and a water repellent layer).
FIG. 2 shows the principle of the present invention (in the case of a substrate having a water-repellent layer having a light absorbing portion).
FIG. 3 is a schematic view of a manufacturing process of a TFT for a display element using the technique of the present invention.
FIG. 4 is a schematic view of a process for manufacturing an organic EL element using the technique of the present invention.
FIG. 5 is a schematic view of a process for manufacturing a color filter panel for a display using the technique of the present invention.
[Explanation of symbols]
Reference numerals 1, 11: substrate, 2: light absorption layer, 3: water repellent layer, 4: irradiation light, 5, 9: liquid in which a metal member is dissolved or dispersed, 6: metal wiring, 7, 12, 17, 20, 20, 27, 30, 38, 41, 44, 47: a water-repellent layer having a light absorbing portion; 8, 15, irradiation light; 10: metal wiring, 13, 18, 21, 23, 28, 31, 34, 39, 42, 45, 48, 50... Light having a wavelength of 633 nm, 14... Gate electrode, 16, 29... Insulating layer, 19... Source electrode or drain electrode, 22. Electrodes, 26, 37: glass substrate, 32: hole transport layer, 33: light emitting layer, 35: metal electrode, 36: sealing layer, 40: black matrix, 43: R portion of color filter, 46: color filter G portion of 49, B portion of color filter, 5 ... protection layer.

Claims (14)

A wiring board having a wiring made of a metal member on its surface, and irradiating a portion of the substrate on which a wiring is formed with light having a wavelength of 250 nm or more to form a wiring pattern. A wiring substrate comprising: a layer made of an amorphous fluoropolymer on a wiring portion; and a layer under the layer for absorbing light used when forming a wiring pattern. A wiring board having a wiring made of a metal member on its surface, and irradiating a portion of the substrate on which a wiring is formed with light having a wavelength of 250 nm or more to form a wiring pattern. A layer made of an amorphous fluoropolymer is provided on the wiring portion, and a light absorbing layer used for forming a wiring pattern is formed therebelow, and the light absorbing layer has a hydroxyl group. A wiring board comprising a resin and wherein the layer comprising the amorphous fluoropolymer is formed of a fluorine-containing compound having a perfluoropolyether chain or a fluoroalkyl chain and an alkoxysilane residue. A wiring pattern formed by irradiating light having a wavelength of 250 nm or more to a portion on the substrate where a wiring is to be formed, and forming a wiring pattern; A layer made of an amorphous fluoropolymer is provided on the wiring portion, and a light absorbing layer used for forming a wiring pattern is formed therebelow, and the light absorbing layer has a hydroxyl group. Containing a resin, and a layer comprising the amorphous fluoropolymer is formed of a fluorine-containing compound having a perfluoropolyether chain and an alkoxysilane residue or a fluorine-containing compound having a fluoroalkyl chain and an alkoxysilane residue, And a wiring board, wherein the fluorine-containing compound has the following structure.

A wiring board having a wiring made of a metal member on its surface, and irradiating light having a wavelength of 250 nm or more to a portion on the substrate where the wiring is to be formed to form a wiring pattern. Having a layer made of an amorphous fluoropolymer on the portion, and having a site in the molecule for absorbing light used in forming the wiring pattern in the molecule. Wiring board. A wiring board having a wiring made of a metal member on its surface, and irradiating light having a wavelength of 250 nm or more to a portion on the substrate where the wiring is to be formed to form a wiring pattern. A layer comprising an amorphous fluorine-containing polymer on a portion thereof, wherein the amorphous fluorine-containing polymer has a portion in a molecule thereof for absorbing light used for forming the wiring pattern, and the amorphous A wiring board, characterized in that the polyfluoropolymer has a perfluoropolyether chain and an alkoxysilane residue in the molecule or is formed from a compound having a fluoroalkyl chain and an alkoxysilane residue in the molecule. A wiring substrate having wiring formed of a metal member on its surface, and irradiating a portion of the substrate on which wiring is formed with light having a wavelength of 250 nm or more to form a wiring pattern. A layer made of an amorphous fluoropolymer on a portion thereof, wherein the amorphous fluoropolymer has a portion in a molecule for absorbing light used when forming the wiring pattern, and the amorphous A wiring substrate, characterized in that the polyfluoropolymer has a perfluoropolyether chain and an alkoxysilane residue in the molecule, or is formed from a compound having the following structure having a fluoroalkyl chain and an alkoxysilane residue.

A method of manufacturing a wiring board having a wiring made of a metal member on the surface, wherein the manufacturing method is performed using at least the following steps (1), (2), and (3).
(1) A step of providing, on the surface of the substrate, a layer that absorbs light having a wavelength of 250 nm or more and reduces the water repellency used in the step (2), and a layer made of an amorphous fluoropolymer thereon.
(2) a step of irradiating a portion where a wiring is to be formed with light having a wavelength of 250 nm or more to reduce the water repellency of the light-irradiated portion;
{Circle around (3)} A step of applying a liquid in which a member for forming wiring is dissolved or dispersed to a portion where water repellency is reduced by the light irradiation. In a TFT device having a gate electrode on a substrate, an insulating layer thereon, a semiconductor layer, a source electrode, and a drain electrode thereon, and a protective layer on the semiconductor layer, a source electrode, and a drain electrode, between the substrate and the gate electrode A TFT element having a fluorine-containing compound layer between a gate electrode and an insulating layer, between an insulating layer and a semiconductor layer, between a source electrode and a protective layer, or between a drain electrode and a protective layer. A transparent electrode is provided on the surface of the transparent substrate, a hole transport layer is provided thereon, a light emitting layer is provided thereon, and an insulating layer is provided on a portion of the transparent substrate surface where the transparent electrode is not provided. In an organic EL device having a metal electrode and a sealing layer on the metal electrode, the organic EL device includes between the transparent electrode and the hole transport layer, between the transparent substrate and the insulating layer, or between the insulating layer and the metal electrode. An organic EL device comprising a fluorine compound layer. R, G, and B color filter portions on the surface of the transparent substrate, and a black matrix in a portion of the transparent substrate surface where no color filter portion exists, and R, G, and B color filter portions and a black matrix A color filter panel having a protective layer on the black substrate, between the transparent substrate and the black matrix, or between the transparent substrate and the R, G, and B color filter portions and between the protective layer on the black matrix. A color filter panel comprising a layer. In a method for manufacturing a TFT device having a gate electrode on a substrate, an insulating layer thereon, a semiconductor layer, a source electrode, and a drain electrode thereon, and a protective layer on the semiconductor layer, the source electrode, and the drain electrode, at least the following ( A method of manufacturing a TFT element, comprising manufacturing the TFT element by using any one of the steps (1) to (5).
(1) A step of forming a water-repellent layer made of a fluorine-containing compound having a portion absorbing light having a wavelength of 250 nm or more on a portion where a gate electrode is to be formed, and forming a gate electrode after irradiating light having a wavelength of 250 nm or more. .
(2) A step of forming a water-repellent layer made of a fluorine-containing compound having a portion absorbing light having a wavelength of 250 nm or more in a portion where the insulating layer is to be formed, and forming the insulating layer after irradiating light having a wavelength of 250 nm or more. .
(3) A water-repellent layer made of a fluorine-containing compound having a portion absorbing light having a wavelength of 250 nm or more is formed on a portion where a source electrode and a drain electrode are to be formed, and after irradiating light having a wavelength of 250 nm or more, the source electrode and the drain are formed. A step of forming electrodes.
(4) A step of forming a water-repellent layer made of a fluorine-containing compound having a portion absorbing light having a wavelength of 250 nm or more on a portion where a semiconductor layer is to be formed, and forming a semiconductor layer after irradiating light having a wavelength of 250 nm or more. .
(5) A step of forming a water-repellent layer made of a fluorine-containing compound having a portion absorbing light having a wavelength of 250 nm or more on a portion where a protective layer is to be formed, and forming the protective layer after irradiating light having a wavelength of 250 nm or more. . It has a transparent electrode on the transparent substrate surface, a hole transport layer on it, a light emitting layer on it, and an insulating layer on the transparent substrate surface where there is no transparent electrode. In a method for manufacturing an organic EL element having a metal electrode and a sealing layer on the metal electrode, it is preferable to manufacture the organic EL element by using at least one of the following steps (1) to (3). Characteristic method of an organic EL device.
(1) A step of forming a water-repellent layer made of a fluorine-containing compound having a portion absorbing light having a wavelength of 250 nm or more on a portion where an insulating layer is to be formed, and forming the insulating layer after irradiating light having a wavelength of 250 nm or more. .
(2) forming a water-repellent layer made of a fluorine-containing compound having a site for absorbing light having a wavelength of 250 nm or more on a transparent electrode, forming a hole transport layer and a light emitting layer after irradiating light having a wavelength of 250 nm or more; Steps to perform.
(3) Forming a water-repellent layer made of a fluorine-containing compound having a portion absorbing light having a wavelength of 250 nm or more on the insulating layer, and forming a metal electrode and a sealing layer after irradiating light having a wavelength of 250 nm or more. Process. R, G, and B color filter portions on the surface of the transparent substrate, and a black matrix in a portion of the transparent substrate surface where no color filter portion exists, and R, G, and B color filter portions and a black matrix A method of manufacturing a color filter panel having a protective layer on the color filter panel, wherein the color filter panel is manufactured using at least one of the following steps (1) to (3).
(1) Forming a water-repellent layer made of a fluorine-containing compound having a portion absorbing light having a wavelength of 250 nm or more on a portion where a black matrix is to be formed on a transparent substrate, and forming a black matrix after irradiating light having a wavelength of 250 nm or more. Step of performing.
(2) The R, G, and B color filter portions of the transparent substrate
a step of forming a water-repellent layer made of a fluorine-containing compound having a portion that absorbs light having a wavelength of at least nm and irradiating light having a wavelength of at least 250 nm to form R, G, and B color filter portions.
(3) A step of forming a water-repellent layer made of a fluorine-containing compound having a site for absorbing light having a wavelength of 250 nm or more on a black matrix, and forming a protective layer after irradiating light having a wavelength of 250 nm or more. In a display device having at least an anti-reflection layer, an image light-emitting portion or a color filter layer and an image forming portion, the substrate in the image light-emitting portion or the image forming portion has a wiring made of a metal member, and the wiring of the substrate is formed. A portion of the wiring substrate is irradiated with light having a wavelength of 250 nm or more to form a wiring pattern, a non-wiring portion of the wiring substrate has a layer made of an amorphous fluoropolymer, and a wiring pattern thereunder. A display device having a layer for absorbing light used for formation.

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