JP3943385B2 - Method for manufacturing reflector forming transfer material and method for manufacturing liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reflective liquid crystal display device having a reflection electrode having satisfactory reflection characteristics, a production method therefor with simple processes, transfer materials for forming a reflector plate to be used therefor and a production method therefor. <P>SOLUTION: The transfer materials for forming the reflector plate and having at least one thermoplastic resin layer, at least one intermediate layer and a photosensitive resin layer on a temporary support in this order and ruggedness formed on the interface of the photosensitive resin layer on the side of the temporary support at least, and the production method therefor are provided. The liquid crystal display device is provide with a first substrate partially with a first electrode having a light reflection function formed on a surface opposite to a second substrate at least, the second substrate located while facing the first substrate and a liquid crystal layer sealed between the first and second substrates are provided and between the first substrate and the first electrode, a resin layer is provided while having ruggedness on a surface to be formed by processes including transfer by using the transfer materials for forming the reflector plate, and the production method therefor is also provided. <P>COPYRIGHT: (C)2003,JPO

Description

【００６９】
前記一般式（ＩＩ）中、Ｒ^２及びＲ^３は、それぞれ独立に、置換基を有していてもよく、不飽和結合を有していてもよい炭化水素基、ヘテロ環基を表し、互いに同一でも異なっていてもよい。
Ｒ^４及びＲ^５は、それぞれ独立に水素原子、置換基を有していてもよく、不飽和結合を有していてもよい炭化水素基、ヘテロ環基、ヒドロキシル基、置換オキシ基、メルカプト基、置換チオ基を表し、互いに同一でも異なっていてもよい。なお、Ｒ^４及びＲ^５は互いに結合して環を形成していてもよく、この場合、該環が−Ｏ−、−ＮＲ^６−、−Ｏ−ＣＯ−、−ＮＨ−ＣＯ−、−Ｓ−及び−ＳＯ_２−より選択される少なくとも一種の２価の基を環の連結主鎖として含んでいてもよい炭素数２〜８のアルキレン基を表す。
Ｒ^６及びＲ^７は、それぞれ独立に水素原子、置換基を有していてもよく、不飽和結合を含んでいてもよい炭化水素基、置換カルボニル基を表す。
【００７０】
前記一般式（ＩＩ）で表される化合物の具体例を以下に示す。但し、本発明においては、これらに限定されるものではない。
例えば、ｐ−メトキシフェニル−２−Ｎ，Ｎ−ジメチルアミノプロピルケトンオキシム−Ｏ−アリルエーテル、ｐ−メチルチオフェニル−２−モルフォリノプロピルケトンオキシム−Ｏ−アリルエーテル、ｐ−メチルチオフェニル−２−モルフォリノプロピルケトンオキシム−Ｏ−ベンジルエーテル、ｐ−メチルチオフェニル−２−モルフォリノプロピルケトンオキシム−Ｏ−ｎ−ブチルエーテル、ｐ−モルフォリノフェニル−２−モルフォリノプロピルケトンオキシム−Ｏ−アリルエーテル、ｐ−メトキシフェニル−２−モルフォリノプロピルケトンオキシム−Ｏ−ｎ−ドデシルエーテル、ｐ−メチルチオフェニル−２−モルフォリノプロピルケトンオキシム−Ｏ−メトキシエトキシエチルエーテル、ｐ−メチルチオフェニル−２−モルフォリノプロピルケトンオキシム−Ｏ−ｐ−メトキシカルボニルベンジルエーテル、ｐ−メチルチオフェニル−２−モルフォリノプロピルケトンオキシム−Ｏ−メトキシカルボニルメチルエーテル、ｐ−メチルチオフェニル−２−モルフォリノプロピルケトンオキシム−Ｏ−エトキシカルボニルメチルエーテル、ｐ−メチルチオフェニル−２−モルフォリノプロピルケトンオキシム−Ｏ−４−ブトキシカルボニルブチルエーテル、ｐ−メチルチオフェニル−２−モルフォリノプロピルケトンオキシム−Ｏ−２−エトキシカルボニルエチルエーテル、ｐ−メチルチオフェニル−２−モルフォリノプロピルケトンオキシム−Ｏ−メトキシカルボエル−３−プロペニルエーテル、ｐ−メチルチオフェニル−２−モルフォリノプロピルケトンオキシム−Ｏ−ベンジルオキシカルボニルメチルエーテルなどが挙げられる。
【００７１】
前記ヘキサアリールビイミダゾールとしては、例えば、２，２'−ビス（ｏ−クロロフェニル）−４，４'，５，５'−テトラフェニルビイミダゾール、２，２'−ビス（ｏ−ブロモフェニル）−４，４'，５，５'−テトラフェニルビイミダゾール、２，２'−ビス（ｏ，ｐ−ジクロロフェニル）−４，４'，５，５'−テトラフェニルビイミダゾール、２，２'−ビス（ｏ−クロロフェニル）−４，４'，５，５'−テトラ（ｍ−メトキシフェニル）ビイミダゾール、２，２'−ビス（ｏ，ｏ'ジクロロフェニル）−４，４'，５，５'−テトラフェニルビイミダゾール、２，２'−ビス（ｏ−ニトロフェニル）−４，４'，５，５'−テトラフェニルビイミダゾール、２，２'−ビス（ｏ−メチルフェニル）−４，４'，５，５'−テトラフェニルビイミダゾール、２，２'−ビス（ｏ−トリフルオロメチルフェニル）−４，４'，５，５'−テトラフェニルビイミダゾールなどが挙げられる。
これらのビイミダゾール類は、例えば、Ｂｕｌｌ．Ｃｈｅｍ．Ｓｏｃ．Ｊａｐａｎ，３３，５６５（１９６０）及びＪ．Ｏｒｇ．Ｃｈｅｍ，３６（１６）２２６２（１９７１）に記載の方法により容易に合成することができる。
【００７２】
前記ケトオキシムエーテルとしては、例えば、３−ベンゾイロキシイミノブタン−２−オン、３−アセトキシイミノブタン−２−オン、３−プロピオニルオキシイミノブタン−２−オン、２−アセトキシイミノペンタン−３−オン、２−アセトキシイミノ−１−フェニルプロパン−１−オン、２−ベンゾイロキシイミノ−１−フェニルプロパン−１−オン、３−ｐ−トルエンスルホニルオキシイミノブタン−２−オン、２−エトキシカルボニルオキシイミノ−１−フェニルプロパン−１−オンなどが挙げられる。
【００７３】
前記重合開始剤は、一種単独で用いてもよいし、二種以上を併用してもよく、また異種間で数個の化合物を併用することも可能である。
前記重合開始剤の含有量としては、感光性樹脂組成物の全固形分の０．１〜５０質量％が好ましく、０．５〜３０質量％がより好ましい。
【００７４】
また、前記感光性樹脂層には、表面に凹凸部を形成する目的で透明微粒子を含有することが好ましい。
前記透明微粒子としては、球状で、アルカリ可溶性であり、現像液で溶解するものが好ましい。
また、透明微粒子の平均粒径が０．５〜５０μｍであることが好ましく、１〜３０μｍであることがより好ましい。
【００７５】
前記透明微粒子としては、アクリル系樹脂、ポリウレタン系樹脂等の樹脂製微粒子、シリカ等の無機化合物の微粒子などが挙げられる。
透明微粒子の添加量は、感光性樹脂層組成物１００質量部に対して１〜５０質量部であることが好ましく、５〜３０質量部であることがより好ましい。
【００７６】
−染料、顔料等の着色剤−
本発明の反射板形成用転写材料を着色する場合には、感光性樹脂層に有機顔料、無機顔料、又は染料等の着色剤を含有させることができる。
黄色顔料として、例えば、Ｃ．Ｉ．ピグメントイエロー２０，Ｃ．Ｉ．ピグメントイエロー２４，Ｃ．Ｉ．ピグメントイエロー８３，Ｃ．Ｉ．ピグメントイエロー８６，Ｃ．Ｉ．ピグメントイエロー９３，Ｃ．Ｉ．ピグメントイエロー１０９，Ｃ．Ｉ．ピグメントイエロー１１０，Ｃ．Ｉ．ピグメントイエロー１１７，Ｃ．Ｉ．ピグメントイエロー１２５，Ｃ．Ｉ．ピグメントイエロー１３７，Ｃ．Ｉ． ピグメントイエロー１３８，Ｃ．Ｉ．ピグメントイエロー１３９，Ｃ．Ｉ．ピグメントイエロー１８５，Ｃ．Ｉ．ピグメントイエロー１４７，Ｃ．Ｉ．ピグメントイエロー１４８，Ｃ．Ｉ．ピグメントイエロー１５３，Ｃ．Ｉ．ピグメントイエロー，Ｃ．Ｉ．ピグメントイエロー１５４，Ｃ．Ｉ．ピグメントイエロー１６６，Ｃ．Ｉ．ピグメントイエロー１６８，モノライト・イエローＧＴ（Ｃ．Ｉ．ピグメントイエロー１２），パーマネント・イエローＧＲ（Ｃ．Ｉ．ピグメントイエロー１７）などが挙げられる。
【００７７】
オレンジ色顔料として、例えば、Ｃ．Ｉ．ピグメントオレンジ３６，Ｃ．Ｉ．ピグメントオレンジ４３，Ｃ．Ｉ．ピグメントオレンジ５１，Ｃ．Ｉ．ピグメントオレンジ５５，Ｃ．Ｉ．ピグメントオレンジ５９，Ｃ．Ｉ．ピグメントオレンジ６１などが挙げられる。
【００７８】
赤色顔料として、例えば、Ｃ．Ｉ．ピグメントレッド９，Ｃ．Ｉ．ピグメントレッド９７，Ｃ．Ｉ．ピグメントレッド１２２，Ｃ．Ｉ．ピグメントレッド１２３，Ｃ．Ｉ．ピグメントレッド１４９，Ｃ．Ｉ．ピグメントレッド１６８，Ｃ．Ｉ．ピグメントレッド１７７，Ｃ．Ｉ．ピグメントレッド１８０，Ｃ．Ｉ．ピグメントレッド１９２，Ｃ．Ｉ．ピグメントレッド２０９，Ｃ．Ｉ．ピグメントレッド２１５，Ｃ．Ｉ．ピグメントレド２１６，Ｃ．Ｉ．ピグメントレッド２１７，Ｃ．Ｉ．ピグメントレッド２２０，Ｃ．Ｉ．ピグメントレッド２２３，Ｃ．Ｉ．ピグメントレッド２２４，Ｃ．Ｉ．ピグメントレッド２２６，Ｃ．Ｉ．ピグメントレッド２２７，Ｃ．Ｉ．ピグメントレッド２２８，Ｃ．Ｉ．ピグメントレッド２４０，Ｃ．Ｉ．ピグメントレッド４８：１，パーマネント・カーミンＦＢＢ（Ｃ．Ｉ．ピグメントレッド１４６），パーマネント・ルビーＦＢＨ（Ｃ．Ｉ．ピグメントレッド１１），ファステル・ピンクＢスプラ（Ｃ．Ｉ．ピグメント・レッド８１）などが挙げられる。
【００７９】
バイオレット顔料として、例えば、Ｃ．Ｉ．ピグメントバイオレット１９，Ｃ．Ｉ．ピグメントバイオレット２３，Ｃ．Ｉ．ピグメントバイオレット２９，Ｃ．Ｉ．ピグメントバイオレット３０，Ｃ．Ｉ．ピグメントバイオレット３７，Ｃ．Ｉ．ピグメントバイオレット４０，Ｃ．Ｉ．ピグメントバイオレット５０などが挙げられる。
【００８０】
青色顔料として、例えば、Ｃ．Ｉ．ピグメントブルー１５，Ｃ．Ｉ．ピグメント・ブルー１５：１，Ｃ．Ｉ．ピグメント・ブルー１５：４，Ｃ．Ｉ．ピグメントブルー１５：６，Ｃ．Ｉ．ピグメントブルー２２，Ｃ．Ｉ．ピグメントブルー６０，Ｃ．Ｉ．ピグメントブルー６４，ビクトリア・ピュアーブルーＢＯ（Ｃ．Ｉ．４２５９５）などが挙げられる。
【００８１】
緑色顔料として、例えば、Ｃ．Ｉ．ピグメントグリーン７，Ｃ．Ｉ．ピグメントグリーン３６などが挙げられる。
【００８２】
ブラウン顔料として、例えば、Ｃ．Ｉ．ピグメントブラウン２３，Ｃ．Ｉ．ピグメントブラウン２５，Ｃ．Ｉ．ピグメントブラウン２６などが挙げられる。
【００８３】
また、黒色顔料として、例えば、モノライト・ファースト・ブラックＢ（Ｃ．Ｉ．ピグメント・ブラック１），Ｃ．Ｉ．ピグメントブラック７，ファット・ブラックＨＢ（Ｃ．Ｉ．２６１５０）などが挙げられる。
【００８４】
その他、カーボンブラック、オーラミン（Ｃ．Ｉ．４１０００）などを挙げることができる。
なお、上記有機顔料、無機顔料、又は染料等の着色剤は１種を単独で用いてもよく、又は２種以上を組み合わせて用いることもできる。
【００８５】
上記のような着色剤を用いる場合、顔料又は染料の粒径は、５μｍ以下であることが好ましく、１μｍ以下であることがより好ましい。感光性樹脂層は薄膜な層であるため、顔料等の粒径が上記の範囲にない場合には、樹脂層中に均一に分散することができず、好ましくない。
【００８６】
前記染料又は顔料等の着色剤の添加量としては、感光性樹脂組成物の全固形分の０．０１〜３０質量％が好ましい。
【００８７】
−他の成分−
前記感光性樹脂組成物には、他の成分として、熱可塑性の結合剤、相溶性の可塑剤等の成分を含有してもよい。
【００８８】
前記熱可塑性の結合剤としては、例えば、エチレン性不飽和化合物等の公知の結合剤が挙げられる。
【００８９】
前記相溶性の可塑剤としては、例えば、ポリプロピレングリコール、ポリエチレングリコール、ジオクチルフタレート、ジヘプチルフタレート、ジブチルフタレート、トリクレジルフォスフェート、クレジルジフェニルフォスフェートビフェニルジフェニルフォスフェートなどが挙げられる。
前記結合剤及び可塑剤の添加量としては、本発明の効果を損なわない範囲で加えることができる。
【００９０】
前記感光性樹脂層は、前記各成分を必要に応じて有機溶剤に溶解して塗布液（感光性樹脂層塗布用塗布液）を調製し、公知の塗布方法により、凹凸部を形成した仮支持体、中間層などを含む層の上に塗布等して形成することができる。
前記有機溶剤としては、特に制限はなく、前記熱可塑性樹脂層用塗布液の調製に使用可能なものと同様のものを用いることができる。
【００９１】
前記感光性樹脂層の層厚（凹凸部を有さない部分）としては、０．５〜１０μｍが好ましく、１〜６μｍがより好ましい。
前記感光性樹脂層の層厚が、０．５μｍ未満であると、感光性樹脂層用塗布液の塗布時にピンホールが発生しやすく、製造適性が低下することがあり、一方、１０μｍを超えると、現像時に未露光部を除去するのに長時間を要することがある。
また、感光性樹脂層の加熱硬化時（ベーク時）の体積収縮率が５０〜９０％であることが好ましく、７０〜９０％であることがより好ましい。これにより最終的に得られる樹脂層に表面粗さ（凹凸部）が反射板として有効な表面形状を形成することができる。
【００９２】
−カバーフィルム
前記感光性樹脂層上には、保管等の際の汚れや損傷から保護する目的で、カバーフィルムを設けることが好ましい。カバーフィルムは、感光性樹脂層から容易に剥離可能なものの中から選択でき、前記仮支持体と同一又は類似の材料からなるものであってもよい。
具体的には、シリコーン紙、ポリオレフィン又はポリテトラフルオロエチレンシート等が好ましく、中でも、ポリエチレン、ポリプロピレンフィルムがより好ましい。
【００９３】
前記カバーフィルムの厚みとしては、約５〜１００μｍが好ましく、１０〜３０μｍがより好ましい。
【００９４】
＜反射板形成用転写材料の製造方法＞
本発明の反射板形成用転写材料の製造方法は、第１の態様として、仮支持体上に少なくとも１層の熱可塑性樹脂層、少なくとも１層の中間層、感光性樹脂層をこの順に設けてなる本発明の反射板形成用転写材料を用いて、前記感光性樹脂層を塗布形成し乾燥させた後の巻き取り雰囲気を加湿状態とするか、又は巻き取り後の転写材料を加湿状態で保存することにより、前記中間層がレチキュレーションを起こして波打ち、前記感光性樹脂層の前記仮支持体側の界面に波型変形（凹凸部）を形成するものである。
前記加湿状態は温度３０〜５０℃で湿度６０〜９０％であることが好ましい。
【００９５】
本発明の反射板形成用転写材料の製造方法は、第２の態様として、仮支持体上に少なくとも１層の熱可塑性樹脂層、少なくとも１層の中間層、感光性樹脂層をこの順に設けてなる本発明の反射板形成用転写材料を用いて、前記感光性樹脂層を加熱硬化することにより前記感光性樹脂層の前記仮支持体側の界面に凹凸部を形成するものである。
この場合、前記反射板形成用転写材料としては、前記熱可塑性樹脂層、中間層及び感光性樹脂層から選ばれる少なくとも１層に透明微粒子を含有し、この透明微粒子が、球状で、アルカリ可溶性であり、前記感光性樹脂層の加熱硬化時の体積収縮率が５０〜９０％であるのが好ましく、７０〜９０％であるのがより好ましい。
【００９６】
なお、本発明の第１，２の態様の反射板形成用転写材料の製造方法は、上記の点以外は、公知方法により製造することができる。
【００９７】
具体的には、前記仮支持体上に、まず、熱可塑性樹脂を溶剤に溶解し調製した塗布液（熱可塑性樹脂層用塗布液）を塗布、乾燥して熱可塑性樹脂層を設け、続いて該熱可塑性樹脂層上に、熱可塑性樹脂層を溶解しない溶媒を用いてなる塗布液（中間層用塗布液）を塗布、乾燥して中間層を設け、この中間層上に、前記感光性樹脂組成物を中間層を溶解しない溶剤に溶解し調製した塗布液を塗布、乾燥して感光性樹脂層を設けることにより形成することができる。又は、前記カバーフィルム上に感光性樹脂層を設け、一方、仮支持体上に熱可塑性樹脂層と中間層とを設け、それぞれを中間層と感光性樹脂層とが接するように貼り合わせることにより、或いは、前記カバーフィルム上に感光性樹脂層と中間層とを設け、一方、仮支持体上に熱可塑性樹脂層を設け、それぞれを上記同様、中間層と感光性樹脂層とが接するように貼り合わせることにより、本発明の反射板形成用転写材料を製造することができる。
【００９８】
後述のように、転写材料を被転写体である基板上に密着させ、転写材料の仮支持体を剥離する過程では、仮支持体や基板等が帯電する結果、周囲のゴミ等を引き寄せ、剥離後の感光性樹脂層上にゴミ等が付着して、その後の露光過程で未露光部ができ、その部分がピンホールを形成する要因となることから、帯電を防止する目的で、仮支持体の少なくとも一方の表面に導電性層を設けたり、或いは導電性を付与した仮支持体を用いることにより、その表面電気抵抗を１０^１３Ω以下に下げることが好ましい。
【００９９】
仮支持体に導電性を付与するには、仮支持体中に導電性物質を含有させればよい。例えば、金属酸化物の微粒子や帯電防止剤を予め練り込んでおく方法が好適である。
前記金属酸化物としては、酸化亜鉛、酸化チタン、酸化錫、酸化アルミニウム、酸化インジウム、酸化珪素、酸化マグネシウム、酸化バリウム、酸化モリブデン等の結晶性金属酸化物、及び／又は、その複合酸化物の微粒子が挙げられる。
【０１００】
前記帯電防止剤としては、エレクトロストリッパーＡ（花王（株）製）、エレノンＮｏ．１９（第一工業製薬（株）製）等のアルキル燐酸塩系アニオン界面活性剤；アモーゲンＫ（第一工業製薬（株）製）等のベタイン系両性界面活性剤；ニッサンノニオンＬ（日本油脂（株）製）等のポリオキシエチレン脂肪酸エステル系非イオン界面活性剤；エマルゲン１０６、１２０、１４７、４２０、２２０、９０５、９１０（花王（株）製）やニッサンノニオンＥ（日本油脂（株）製）等のポリオキシエチレンアルキルエーテル系非イオン界面活性剤、等が好適である。その他、非イオン界面活性剤として、ポリオキシエチレンアルキルフェノールエーテル系、多価アルコール脂肪酸エステル系、ポリオキシエチレンソルビタン脂肪酸エステル系、ポリオキシエチレンアルキルアミン系等のものが挙げられる。
【０１０１】
仮支持体上に導電性層を設ける場合には、導電性層としては公知のものの中から、適宜選択して用いることができる。導電性層に用いる導電性物質として、ＺｎＯ、ＴｉＯ_２、ＳｎＯ_２、Ａｌ_２Ｏ_３、Ｉｎ_２Ｏ_３、ＳｉＯ_２、ＭｇＯ、ＢａＯ、ＭｏＯ_３等から選ばれる少なくとも１種の結晶性金属酸化物、及び／又は、その複合酸化物の微粒子等が挙げられる。これらを含有させて用いる方法が湿度環境に影響されない、安定した導電効果を有する点で好ましい。
【０１０２】
前記結晶性金属酸化物又はその複合酸化物の微粒子の体積抵抗値としては、１０^７Ω・ｃｍ以下が好ましく、１０^５Ω・ｃｍ以下がより好ましい。また、その粒子径としては、０．０１〜０．７μｍが好ましく、０．０２〜０．５μｍがより好ましい。
【０１０３】
上記結晶性金属酸化物及びその複合酸化物の微粒子の製造方法は、特開昭５６−１４３４３０号公報に詳細に記載されている。即ち、第１に、金属酸化物微粒子を焼成により作製し、導電性を向上させる異種原子の存在下で熱処理する方法、第２に、焼成により金属酸化物微粒子を製造する際に導電性を向上させるための異種原子を共存させる方法、第３に、焼成により金属微粒子を製造する際に雰囲気中の酸素濃度を下げて、酸素欠陥を導入する方法等が記載されている。異種原子を含む具体例としては、ＺｎＯに対してＡｌ、Ｉｎ等、ＴｉＯ_２に対してＮｂ、Ｔａ等、ＳｎＯ_２に対してＳｂ、Ｎｂ、ハロゲン元素等を存在させることが挙げられる。
【０１０４】
異種原子の添加量としては、０．０１〜３０ｍｏｌ％が好ましく、０．１〜１０ｍｏｌ％がより好ましい。導電性粒子の使用量としては、０．０５〜２０ｇ／ｍ^２が好ましく、０．１〜１０ｇ／ｍ^２がより好ましい。
【０１０５】
転写材料に設ける導電性層には、バインダーとして、ゼラチン、セルロースナイトレート、セルローストリアセテート、セルロースジアセテート、セルロースアセテートブチレート、セルロースアセテートプロピオネート等のセルロースエステル；塩化ビニリデン、塩化ビニル、スチレン、アクリロニトリル、酢酸ビニル、炭素数１〜４のアルキルアクリレート、ビニルピロリドン等を含むホモポリマー又は共重合体；可溶性ポリエステル、ポリカーボネート、可溶性ポリアミド等を使用することができる。
【０１０６】
これらのバインダー中に導電性粒子を分散する場合、チタン系分散剤又はシラン系分散剤等の分散液を添加してもよい。また、必要に応じて、バインダー架橋剤等を添加することもできる。
【０１０７】
前記チタン系分散剤としては、例えば、米国特許第４，０６９，１９２号公報、同第４，０８０，３５３号公報等に記載の、チタネート系カップリング剤、プレンアクト（味の素（株）製）などが挙げられる。
前記シラン系分散剤としては、例えば、ビニルトリクロルシラン、ビニルトリエトキシシラン、ビニルトリス（β−メトキシエトキシ）シラン、γ−グリシドキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン等が挙げられ、「シランカップリング剤」（信越化学工業（株）製）として市販されている。
前記バインダー架橋剤としては、例えば、エポキシ系架橋剤、イソシアネート系架橋剤、アジリジン系架橋剤、エポキシ系架橋剤などが挙げられる。
【０１０８】
前記導電性層は、導電性微粒子をバインダー中に分散させて仮支持体上に塗設したり、又は仮支持体上に下引処理（例えば、下塗り層等）を施した上に導電性微粒子を付着させることにより設けることができる。
【０１０９】
前記導電性層は、仮支持体の感光性樹脂層を塗設した面とは反対の表面上に設けてもよく、この場合には、十分な耐傷性を確保する目的で、導電性層上に更に疎水性重合体層を設けることが好ましい。この疎水性重合体層は、疎水性重合体を有機溶剤に溶解した状態又は水性ラテックスの状態で塗布すればよく、その塗布量としては、乾燥質量で０．０５〜１ｇ／ｍ^２程度が好ましい。
【０１１０】
前記疎水性重合体としては、例えば、ニトロセルロース、セルロースアセテート等のセルロースエステル；塩化ビニル、塩化ビニリデン、ビニルアクリレート等を含むビニル系ポリマー；有機溶剤可溶性ポリアミド、ポリエステル等のポリマーを挙げることができる。
【０１１１】
前記疎水性重合体層には、スベリ性を付与する目的で、例えば、特開昭５５−７９４３５号公報に記載の有機カルボン酸アミド等のスベリ剤を使用することができる。また、必要に応じて、マット剤等を使用することもできる。このような疎水性重合体層を設けても、導電性層の効果は実質的に影響を受けない。
【０１１２】
下塗り層を設ける場合、特開昭５１−１３５５２６号公報、米国特許第３，１４３，４２１号公報、同第３，５８６，５０８号公報、同第２，６９８，２３５号公報、同第３，５６７，４５２号公報等に記載の塩化ビニリデン系共重合体、特開昭５１−１１４１２０号公報、米国特許第３，６１５，５５６号公報等に記載のブタジエン等のジオレフイン系共重合体、特開昭５１−５８４６９号公報等に記載のグリシジルアクリレート又はグリシジルメタアクリレート含有共重合体、特開昭４８−２４９２３号公報等に記載のポリアミド・エピクロルヒドリン樹脂、特開昭５０−３９５３６号公報に記載の無水マレイン酸含有共重合体等を用いることができる。
【０１１３】
本発明においては、特開昭５６−８２５０４号公報、特開昭５６−１４３４４３号公報、特開昭５７−１０４９３１号公報、特開昭５７−１１８２４２号公報、特開昭５８−６２６４７号公報、特開昭６０−２５８５４１号公報等に記載の導電性層も必要に応じて用いることができる。
【０１１４】
仮支持体上に、導電性層を塗布する場合、ローラーコート、エアナイフコート、グラビアコート、バーコート、カーテンコート等の公知の方法により塗布することができる。十分な帯電防止効果を得るためには、導電性層又は導電性を付与した仮支持体の表面電気抵抗値を、１０^１３Ω以下とすることが好ましく、１０^１２Ω以下とすることがより好ましい。
【０１１５】
また、感光性樹脂層の仮支持体との強固な接着を防止するため、仮支持体面に公知の微粒子を含有する滑り剤組成物、シリコーン化合物を含有する離型剤組成物等を塗布することもできる。
【０１１６】
仮支持体の熱可塑性樹脂層を設けない側の表面に導電性層を設ける場合には、熱可塑性樹脂層と仮支持体との接着性を向上する目的で、仮支持体に、例えば、グロー放電処理、コロナ処理、紫外線照射処理等の表面処理、フェノール性物質、ポリ塩化ビニリデン樹脂、スチレンブタジエンゴム、ゼラチン等の下塗り処理又はこれらの処理を組み合わせた処理を施すことができる。
【０１１７】
仮支持体用のフィルムは押し出し形成により形成することが可能であるが、導電性物質又は導電性層を仮支持体と同一又は異質のプラスチック原料に含有させ、前記フィルムと同時に押し出し形成した場合には、接着性、耐傷性に優れた導電性層を容易に得ることができる。この場合、前記疎水性重合体層や下塗り層を設ける必要はなく、転写材料を構成する導電性付与仮支持体として最も好ましい実施形態である。
本発明の反射板形成用転写材料の主な用途としては、反射板の下地層、液晶セル内の反射電極形成用樹脂層など用途が好適である。
【０１１８】
＜反射板＞
次に、本発明の反射板は、前記反射板形成用転写材料を基板に転写し、露光を行い、現像、ベークして形成される表面に凹凸部を有する樹脂層上に光反射機能材料を形成してなる。
【０１１９】
まず、反射板形成用転写材料のカバーフィルムを取り除き、感光性樹脂層を加圧、加熱下で被転写体である基体上に貼り合わせる。貼り合わせには、従来公知のラミネーター、真空ラミネーター等を使用することができ、より生産性を高めるためには、オートカットラミネーターも使用することができる。その後、仮支持体を剥がし、所定のマスク、熱可塑性樹脂層及び中間層を介して感光性樹脂層を露光し、次いで現像する。現像は、公知の方法により行うことができ、溶剤若しくは水性の現像液、特に、アルカリ水溶液等を用いて、露光後の基体を浸漬するか、スプレー等により噴霧し、更にブラシ等で擦ったり、或いは、超音波を照射しながら処理することで行われる。
【０１２０】
前記反射板形成用転写材料の感光性樹脂層と被転写体である基体とを貼り合わせた後、仮支持体を熱可塑性樹脂層との界面で剥がし取り、該熱可塑性樹脂層の上方から熱可塑性樹脂層及び中間層を通して感光性樹脂層をパターン状に露光（パターニング）する。
前記露光は、３００〜５００ｎｍの波長光の照射により行え、光源としては、例えば、高圧水銀灯、超高圧水銀灯、メタルハライドランプ、Ｈｇ−Ｘｅランプ等が挙げられる。
【０１２１】
また、前記パターニングの方法としては、例えば、▲１▼フォトリソグラフィ法による方法、▲２▼熱可塑性樹脂層の上方に露光マスクを配置し、該マスク介してパターン状に露光する方法、▲３▼密着型のプロキシミティ露光装置等の露光手段を用いる方法等が挙げられる。
前記方法▲３▼によるパターニングでは、その露光量としては、感光性樹脂組成物が重合硬化を起こす最小露光量の３〜１０倍が好ましく、プロキシミティ量としては、４０〜１５０μｍが好ましい。
【０１２２】
前記露光の後、現像処理して、熱可塑性樹脂層、アルカリ可溶な中間層、及び不要部（未硬化部分）の感光性樹脂層を除去する。
【０１２３】
前記現像は、公知の方法により行え、溶剤若しくは水性の現像液、特にアルカリ水溶液等を用いて、例えば、（ａ）露光後の基板自体を現像浴中に浸漬する、（ｂ）露光後の基板にスプレー等により噴霧する等して、更に必要に応じて、溶解性を高める目的で、回転ブラシや湿潤スポンジ等で擦ったり、超音波を照射しながら行うことができる。
【０１２４】
前記アルカリ水溶液としては、アルカリ性物質の希薄水溶液が好ましく、更に水混和性のある有機溶剤を少量添加したものも好適に使用することができる。前記アルカリ性物質としては、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物類、炭酸ナトリウム、炭酸カリウム等のアルカリ金属炭酸塩類、炭酸水素ナトリウム、炭酸水素カリウム等のアルカリ金属重炭酸塩類、ケイ酸ナトリウム、ケイ酸カリウム等のアルカリ金属ケイ酸塩類、メタケイ酸ナトリウム、メタケイ酸カリウム等のアルカリ金属メタケイ酸塩類、トリエタノールアミン、ジエタノールアミン、モノエタノールアミン、モルホリン、テトラメチルアンモニウムヒドロキシド等のテトラアルキルアンモンニウムヒドロキシド類、燐酸三ナトリウム等が挙げられる。
【０１２５】
アルカリ水溶液中のアルカリ性物質の濃度としては、０．０１〜３０質量％が好ましく、更にｐＨとしては、８〜１４が好ましい。
【０１２６】
前記水混和性を有する有機溶剤としては、メタノール、エタノール、２−プロパノール、１−プロパノール、ブタノール、ジアセトンアルコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノｎ−ブチルエーテル、ベンジルアルコール、アセトン、メチルエチルケトン、シクロヘキサノン、ε−カプロラクトン、γ−ブチロラクトン、ジメチルホルムアミド、ジメチルアセトアミド、ヘキサメチルホスホルアミド、乳酸エチル、乳酸メチル、ε−カプロラクタム、Ｎ−メチルピロリドン等が挙げられる。
この有機溶剤の添加量としては、０．１〜３０質量％が好ましい。
【０１２７】
また、アルカリ水溶液には、公知の種々の界面活性剤を添加することもできる。界面活性剤の濃度としては、０．０１〜１０質量％が好ましい。
現像時の温度としては、通常、室温付近〜４０℃が好ましい。更に、現像処理した後に、水洗処理する工程を入れることもできる。なお、現像処理した後、更に２００〜２６０℃下でベークする。
【０１２８】
このようにして、表面に凹凸部を有する樹脂層が基板上に形成される。次に、この凹凸部に光反射機能材料層を形成する。
前記光反射機能材料としては、光反射性を有すれば特に制限されないが、反射電極を形成する観点から、Ａｌ，Ａｇ等の金属材料が好適である。このような金属膜の形成は、スパッタ法などにより行うことができる。
前記反射板を一方の反射電極として用いることにより液晶表示装置を形成することができる。
【０１２９】
前記反射板２０に形成される凹凸部は、図２に示したように、不規則に大小の凸部１０が形成されたり、図３に示したように、山部１１と谷部１２とを交互に有する波状に形成されたり、図４に示したように、山部１１と谷部１２とが交互に蒲鉾状に形成されたものであっても構わない。
この場合、直交する２方向（図２〜４においてＸＹ方向）の少なくともいずれか１つの凹凸部のピッチ（図５参照）が３〜５０μｍであることが好ましく、１０〜３０μｍであることがより好ましい。また、ＰＶ値（図５参照）が０．１〜２．０μｍであることが好ましく、０．２〜０．８μｍであることがより好ましい。なお、凹凸部の測定は表面粗さ計を用い、平均値で表される。
【０１３０】
＜液晶表示装置及びその製造方法＞
本発明の液晶表示装置は、光反射機能を有する第１の電極が第２の基板に対向する面に少なくとも一部形成されている第１の基板と、この第１の基板に対向配置されている第２の基板と、第１及び第２の基板の間に封入されている液晶層とを備え、前記第１の基板と第１の電極との間に、前記本発明の反射板形成用転写材料を用いて転写を含む工程で形成される表面に凹凸部を有する樹脂層を備えている。
前記第１及び第２の電極はそれぞれマトリクス状に形成されていても良い。また第１の電極は画素ごとにパターニングされ、第２の電極はベタ状に形成されても良い。
【０１３１】
前記樹脂層は、前記本発明反射板形成用転写材料を用いて、転写を含む工程により形成された凹凸部を表面に有しており、この凹凸部は連続的に波状の形状を有していることが、広い領域にわたって良好な反射特性を得ることができる上で好ましい。
前記凹凸部は、直径０．７〜３０μｍ（円又は楕円）、高さ０．１〜１．５μｍの凸部、又は凹凸部が多数形成される。この形状は、該液晶表示装置の用途により、適切な範囲が違う。完全にパーソナルユースの場合、直径５μｍ、高さ０．５μｍの、凹凸部を、画素面積の７割程度に敷き詰めた構成が良い。また、凹凸は略円形や円形のほか、楕円でも良い。またこれらの径は、ランダムに変化させて配置し、モアレの発生を防止する。また、凹凸は、円錐や角錐状であることもある。
【０１３２】
前記スイッチング素子を有する基板として、ＴＦＴアクティブマトリックス基板を用いることが好ましい。前記ＴＦＴアクティブマトリックス基板としては、常用のものを制限なく使用することができる。例えば、アクティブマトリクス基板（アレイ基板）に、ゲート信号線と付加容量電極を形成し、この上にゲート絶縁膜を形成した後、半導体層及びチャネル保護層を形成し、更にＴＦＴのソース及びドレインとなるｎ＋Ｓｉ層を形成し、次に金属層及びＩＴＯ膜をスパッタリング法によって形成し、これらをパターニングすることにより、ドレイン信号線及びソース信号線を形成する等によって作製することができる。
【０１３３】
前記ＴＦＴ（薄膜トランジスター）アクティブマトリックス層が、アモルファスシリコン又は低温ポリシリコン基材、コンティニュアスグレインシリコン基材で形成されているものが好ましい。
【０１３４】
本発明の液晶表示装置の製造方法は、光反射機能を有する第１の電極が第２の基板に対向する面に少なくとも一部形成されている第１の基板と、この第１の基板に対向配置されている第２の基板と、第１及び第２の基板の間に封入されている液晶層とを備える液晶表示装置の製造方法において、
前記第１の基板と第１の電極との間に、前記本発明の反射板形成用転写材料を用い、転写を含む工程で表面に凹凸部を有する樹脂層を形成するものである。
更に、具体的には、まず、ガラスから成る絶縁性基板上に複数の配線が設けられ、表面処理等を行った後、絶縁膜、半導体膜等を形成しアレイ状にスイッチング素子が形成される。
【０１３５】
次に、該基板のスイッチング素子が形成されている側のほぼ全面を覆うように、本発明の反射板形成用転写材料が転写される。この転写はラミネーターによって行われ、必要に応じて、基板表面はシランカップリングなどの前処理が施される。
その後、所定の露光マスクを用い、露光した後、ＴＭＡＨ水溶液などの現像液で現像し、コンタクトホールやアライメントマーク部分の樹脂層を除去する。この段階で該樹脂層の表面は凹凸に形成されている。また、ここで行う露光は２０ｍＪ／ｃｍ^２程度で良く、露光時間としては、３０秒より充分短く、製造ラインのタクトタイムは１分以下、３０前後に設定が可能である。
これを更にポスト露光および又はポストベークにより硬化させた後、その上にＡｌ及び又はＡｇ等から成る反射層が形成される。この時、コンタクトホールを介してスイッチング素子と接続されている。更にこの反射層をパターンエッチングし、画素ごとに独立し、画素ごとにスイッチング素子に接続された反射電極が形成される。この上に配向膜を形成し、ラビング処理等を施す。
【０１３６】
他方の基板上には、反射電極に対向する部分にカラーフィルタが形成され、（必要に応じてブラックマトリクスを形成）、ＩＴＯ（Ｉｎｄｉｕｍ Ｔｉｎ Ｏｘｉｄｅ）からなる透明電極が形成されている。両基板は前記反射電極とカラーフィルタが一致するように対向して貼り合わされ、間に液晶が注入され、反射型液晶表示装置が製造される。
【０１３７】
前記液晶表示装置としては、上記構成のもの以外にも、カラーフィルタ・オン・アレイ（ＣＯＡ）構造及び半透過型構造のいずれか又は両方を有するものを好適に用いることができる。
【０１３８】
前記ＣＯＡ構造は、例えば、特開平１０−２０６８８８号公報などに記載されているように、カラーフィルタが前記駆動側基板に直接形成されたカラーフィルタ一体型駆動基板と、対向電極（導電層）を備える対向基板とをスペーサを介在させて対向配置し、その間隙部に液晶材料を封入して構成されるものであり、カラーフィルタを反射電極の上に形成し、高精細時に貼り合わせマージンを広くして歩留まりや開口率を向上させることができる。
【０１３９】
前記半透過型構造とは、正面からの光を反射して表示させる機能と、背面からの光を透過して表示させる機能を併せ持った反射型液晶表示装置の一種である。光を反射するために設けられている反射層を薄膜化する等の方法で背面からの光も透過できるように構成した「ハーフミラー型」、と、１画素内に、光を反射する領域と、光を透過する領域とを兼ね備えた「画素内分割型」とがある。
【０１４０】
前記ハーフミラー型は、例えば、特開２００１−１００１９７号公報などに記述されている。構造がシンプルだが、光学濃度が低い反射用のカラーフィルタにバックライトの透過光を透過させるため、表示される色が薄い。
【０１４１】
前記「画素内分割型」は、図６に示したように、例えば、特開２００１−１７４７９７号公報などに記述されている。反射機能を有す画素内部分に対応するカラーフィルタを光学濃度が低い反射用のカラーフィルタに、透過機能を有す画素内部分に対応するカラーフィルタを光学濃度が高い透過用のカラーフィルタとすることで、反射型の場合、透過型の場合共に、良い色再現性を得ることができる。なお、図６中３０は感光性樹脂層、３１は基板である。
更に、前記「画素内分割型」では、反射機能を有す画素内部分に対応する液晶層が薄く、透過機能を有す画素内部分に対応する液晶層が厚くなるよう、ＴＦＴ基板側の絶縁膜の厚さや、カラーフィルタ厚さ、オーバーコート厚さなどを設定し、反射の場合、透過の場合共に、良いコントラストを得ることができる。
【０１４２】
【実施例】
以下、実施例及び比較例により本発明を更に具体的に説明するが、本発明はこれらの実施例に何ら限定されるものではない。
【０１４３】
〔参考例１〕
−転写用樹脂フィルムの作成−
厚さ７５μｍのポリエチレンテレフタレートフィルム仮支持体に下記の処方Ｈ１の塗布液を塗布して乾燥膜厚１４μｍの熱可塑性樹脂層を形成した。
＜熱可塑性樹脂層処方Ｈ１：＞
・メチルメタクリレート／２−エチルヘキシルアクリレート／ベンジル
メタクリレート／メタクリル酸共重合体（共重合組成比（モル比）＝５５／３０／１０／５、質量平均分子量＝１０万、Ｔｇ≒７０℃）
７質量部
・スチレン／アクリル酸共重合体（共重合組成比（モル比）＝６５／３５、
質量平均分子量＝１万、Ｔｇ≒１００℃）
７質量部
・ビスフェノールＡにオクタエチレングリコールモノメタクリレートを２当量脱水縮合した化合物（新中村化学（株）製ＢＰＥ−５００）
７質量部
メチルエチルケトン ５０質量部
【０１４４】
次に、上記熱可塑性樹脂層上に、下記組成の中間層用塗布液Ｐ１を塗布した後、１００℃で２分間乾燥して厚さ１．６μｍの中間層を形成した。この際、中間層用塗布液にはビーズが含有させており、このビーズはしなやかなので乾燥中に扁平に潰れ、中間層の表面に凹凸部が形成された。
＜中間層処方Ｐ１：＞

【０１４５】
次に、下記感光性樹脂層溶液Ｃ１を塗り付け乾燥させて乾燥膜厚３．３μｍの感光性樹脂層を設け、保護フィルムでカバーし、転写用樹脂フィルムを作成した。
この転写用樹脂フィルムの表面には、ＳＥＭ観察により、ピッチ１０〜４０μｍ、ＰＶ値０．１〜０．５μｍの凹凸部が形成されていた。
＜感光性樹脂層溶液Ｃ１＞
・ポリマー溶液 ２４０質量部
スチレン／マレイン酸共重合体ベンジルアミン変性物＝６８／３２（モル比）
・ジペンタエリスリトールヘキサアクリレート ２００質量部
・シクロヘキサノン ７３０質量部
・光重合開始剤 ＩＲＧ１８４（ＣＡＳ９４７−１９−３） １０質量部
（メチルエチルケトンを適宜添加）
【０１４６】
＜基板の洗浄＞
縦３２０ｍｍ×横４００ｍｍのＴＦＴ基板を、室温の超純水中で超音波洗浄１分後、エアーブローで水切り後、乾燥した。
【０１４７】
＜樹脂層の形成＞
前記転写用樹脂フィルムの保護フィルムを剥離後、温度１３０℃、線圧１００Ｎ／ｃｍ、搬送速度３．０ｍ／分でラミネートした。
仮支持体を剥離後、超高圧水銀灯で２０ｍＪ／ｃｍ^２のパターン露光した。この際の露光時間は３秒であった。
【０１４８】
次に、下記組成の現像液Ｐ１にて３８℃で３５秒シャワー現像し、熱可塑性樹脂層と中間層を除去した。
＜現像液Ｐ１の組成＞
・超純水 ９７質量部
・トリエタノールアミン ３質量部
（アルカリ金属濃度 ５０ｐｐｂ）
【０１４９】
引き続き、下記組成の現像液Ｄ１にて３３℃で２６秒シャワー現像し、感光性樹脂層を現像し、コンタクトホール部分（後述のＡｌ層とＴＦＴを接続するための穴）と、透過部分を除去したパターン画像を得た。
＜現像液Ｄ１＞
・モノエタノールアミン ０．２ｍｏｌｅ／Ｌ
・酢酸 ０．１ｍｏｌｅ／Ｌ
・ジポリオキシエチレンアルキルアミン １質量％
（アルカリ金属濃度 ５０ｐｐｂ）
【０１５０】
次に、光反射機能を有する第１の電極（反射電極と言う）を形成するため、Ａｌ層をスパッタ法により形成した。この時、Ａｌ層の膜厚は０．５μｍであり、成膜条件は基板温度１００℃、Ａｒ圧力０．５Ｐａ、ＲＦパワー３．４Ｗ／ｃｍ^２であった。つづいて、フォトリソグラフィー及びエッチングにより、所定の形状にＡｌ層をパターンニングし光反射機能を有する第１の電極を形成した。この光反射機能を有する第１の電極は、上記Ｃ１層の表面に形成されている凹凸形状を反映することにより、凹凸部を有する反射電極が得られた。
【０１５１】
次に、基板全面にポリイミドからなる配向膜（図示せず）を塗布し、１５０℃、２時間で焼成を行った後、ラビング処理を行った。次いで、対向側基板として、ガラス基板上に該反射電極に対向する位置にカラーフィルタ及びＩＴＯから成る透明電極を形成した対向側基板を作成し、配向膜塗布、焼成、ラビングを行った。
これら二つの基板を所定のセル厚になるようスペーサーを介して対向させ（図示せず）、シール部により貼り合わせた。つづいて、基板間に液晶を注入・封止して、液晶表示装置を作製した。
【０１５２】
〔実施例１〕
参考例１において、中間層処方Ｐ１から樹脂製ビーズを除いた以外同じ組成の転写用樹脂フィルムを４５℃で湿度８０％で１０時間保存した。中間層のレチキュレーションにより感光性樹脂層の前記仮支持体側の界面には、ＳＥＭ観察によりピッチ１０〜４０μｍ、ＰＶ値０．１〜０．５μｍの凹凸部が形成されていた。この転写用樹脂フィルムの保護フィルムを剥離後、温度１３０℃、線圧１００Ｎ／ｃｍ、搬送速度３．０ｍ／分でラミネートした。仮支持体を剥離後、超高圧水銀灯で２０ｍＪ／ｃｍ^２のパターン露光した。この際の露光時間は３秒であった。同様にして液晶表示装置を組み立てた。
【０１５３】
［比較例１］
ＴＦＴ基板に形成する凹凸部を有する樹脂層を特開平１１−１５３８０４号公報の記載に基づいて下記のように形成した以外は、参考例１と同様にして液晶表示装置を作製した。
【０１５４】
基板全面に光重合性オリゴマー、光重合性モノマー、光重合開始材を主成分とする光硬化性樹脂を塗布した。光重合性オリゴマーとしてはエステルアクリレートであるペンタエリスリトールと、光重合性モノマーとしてはネオペンチルグリコールジアクリレートを用い、これに２質量％の光重合開始剤を加えた。これを膜厚３μｍで基板全面に塗布した。
露光マスクの透過部分の光透過率を部分的に変化させた半透過型マスクを用い凸部を形成した。この時の照射エネルギーは１２００ｍＪ／ｃｍ^２〜１５００ｍＪ／ｃｍ^２であった。この際、露光時間は２４０秒を要した。
【０１５５】
参考例１と実施例１と比較例１とを対比すると、参考例１と実施例１では凹凸部を形成するための露光時間は３秒であるのに対して、比較例１では２４０秒もかかり、製造ラインのタクトタイムが３分以上と長くかかり、生産性が劣ることが明らかである。
【０１５６】
【発明の効果】
本発明によれば、前記問題を解決することができ、簡略な工程により、良好な反射特性を有する反射電極を有する、特に、ＯＡ機器、パーソナルコンピュータ、携帯型情報端末等に用いられる液晶表示装置のうち室内照明や太陽光などの外光を利用する反射型液晶表示装置を効率よく安価に製造することができる。
【図面の簡単な説明】
【図１】図１は、本発明の一例に係る反射板形成用転写材料を示す概略断面図である。
【図２】図２は、凹凸部の一例を示す概略図である。
【図３】図３は、凹凸部の一例を示す概略図である。
【図４】図４は、凹凸部の一例を示す概略図である。
【図５】図５は、凹凸部のピッチ及びＰＶ値を示す説明図である。
【図６】図６は、画素内分割型の半透過型ＬＣＤを示す概略断面図である。[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to a transfer material for reflecting plate formationManufacturing method andLiquid crystal displayManufacturing methodIn particular, a liquid crystal display device suitably used for OA equipment, personal computers, portable information terminals, etc.Manufacturing methodAnd transfer material for reflecting plate formation used thereforManufacturing methodAbout.
[0002]
[Prior art]
In recent years, a liquid crystal display (LCD) is most widely used or expected as a flat panel type display device replacing CRT. Among them, a thin film transistor (TFT) type LCD (TFT-LCD) is expected to further expand the market by application to personal computers, word processors, OA devices, portable televisions, and the like.
Especially in the field of notebook personal computers and portable information terminals as portable information tools as the multimedia society progresses, the power consumption is reduced for the purpose of making the device usable more thin and light. There are demands for a few liquid crystal display devices. Reflective liquid crystal display devices use outside light such as indoor lighting and sunlight, so there is little or no power consumption by backlights and front lights, and consumption compared to conventional transmissive liquid crystal display devices. The power can be reduced, and the thickness and weight can be reduced.
[0003]
Such reflection type liquid crystal display devices include TN (twisted nematic) method, STN (super twisted nematic) method, phase transition type guest host method as disclosed in Japanese Patent Laid-Open No. 5-173158, and the like. Is used.
[0004]
In these reflective liquid crystal display devices, in order to obtain a brighter display, it is necessary to increase the intensity of light scattered in the direction perpendicular to the display screen with respect to incident light from all angles. For this reason, Japanese Patent Laid-Open No. 6-75237 discloses that a reflecting plate is formed on an insulating glass substrate with a concavo-convex shape controlled and a metal film such as Al or Ag is formed thereon. Are listed. The proposed reflector is formed by forming a columnar convex portion using a polymer material on the glass substrate surface by photolithography or the like, and then thermally deforming the corner of the upper edge portion of the columnar structure by heat treatment. A shape in which the upper edge portion is rounded is manufactured, and further, a polymer resin film is laminated to fill a gap in the columnar structure to form a continuous wavy surface shape, and Al, Ag, etc. are formed on this wavy resin surface. A reflective plate having a continuous wavy surface is produced by forming a metal film.
[0005]
However, in the production of the reflector according to the above proposal, it is necessary to form a film structure of at least three layers, and three film forming steps and processing steps are required. . Furthermore, a heating step of at least 200 ° C. is necessary to make the upper edge of the columnar part round and have no corners. For this reason, when a polymer resin substrate is used as the substrate for the purpose of further reducing the thickness and weight of the liquid crystal display device, the substrate cannot be processed and used because the substrate is deformed or contracted during heating. There was a problem that the material was limited to high heat-resistant resin.
In order to solve this problem, Japanese Patent Application Laid-Open No. 11-153804 proposes a reflective liquid crystal display device having a reflective electrode that has a convex shape that is self-formed by light irradiation and does not require heat treatment. Has been.
[0006]
Control of the convex shape formed in a self-forming manner depends on the irradiated light energy, and the height of the convex portion is controlled within a range of up to about 2 μm by controlling the light irradiation time or light irradiation energy. be able to.
[0007]
However, the irradiation energy of the light is, for example, 1.2 J / cm.²~ 1.5J / cm²The irradiation time needs to be around 200 seconds. For this reason, the above method has a problem that the tact time of the production line is as long as 3 minutes or more and the productivity is inferior.
[0008]
On the other hand, transflective liquid crystal display devices (transflective LCDs) have begun to spread as systems optimal for mobile applications. This cell structure is complicated, and a transmissive LCD portion and a reflective LCD portion are provided in one pixel. If these two parts are designed with the same liquid crystal thickness, each switching can only be adjusted halfway, so a system has been proposed in which the liquid crystal thickness of the transmissive LCD part is twice that of the reflective LCD part ( JP-A-11-242226, JP-A-2000-187220).
[0009]
That is, in the dual structure transflective LCD, the cell gap formed by bonding the substrate glass is basically adjusted to the gap d1 of the transmissive LCD, but the reflective LCD portion halves the cell gap. An insulating film having a thickness of approximately 1 / 2d1 is formed by photolithography. Japanese Laid-Open Patent Publication No. 2000-187220 discloses that a coating film having a two-layer structure is used in order to obtain a reflection plate that diffusely reflects on the insulating film.
[0010]
However, this method requires a multi-step process, resulting in a problem that the cost of the resulting LCD is increased.
[0011]
[Problems to be solved by the invention]
  The present invention aims to solve the above-described problems and solve the following problems. That is, the present invention is a reflective liquid crystal display device having a reflective electrode having a good reflective characteristic in a simple process.Manufacturing methodAnd a reflector forming transfer material used thereforManufacturing methodThe purpose is to provide.
[0012]
[Means for Solving the Problems]
  Means for solving the above problems are as follows. That is,
<1> At least one thermoplastic resin layer, at least one intermediate layer, and a photosensitive resin layer are provided in this order on the temporary support.By using the transfer plate forming transfer material, the winding atmosphere after applying and forming the photosensitive resin layer and drying is made humid, or the transferred transfer material is stored in a humidified state. A method for producing a transfer material for forming a reflecting plate, characterized in that an uneven portion is formed at an interface of the photosensitive resin layer on the temporary support side by reticulation of an intermediate layer.
<2>The method for producing a transfer material for reflecting plate formation according to <1>, wherein transparent fine particles are contained in at least one layer selected from the thermoplastic resin layer, the intermediate layer, and the photosensitive resin layer.
<3>The method for producing a transfer plate-forming transfer material according to <2>, wherein the transparent fine particles are alkali-soluble.
<4>The method for producing a transfer material for forming a reflecting plate according to any one of <1> to <3>, wherein the humidified state is a temperature of 30 to 50 ° C. and a humidity of 60 to 90%.
<5>From the above <2>, an uneven portion is formed at the interface of the photosensitive resin layer on the temporary support side by heat-curing the photosensitive resin layer using the transfer plate forming transfer material. <3> A method for producing a transfer plate-forming transfer material according to any one of <3>.
<6>The method for producing a transfer material for reflecting plate formation according to any one of <1> to <5>, wherein the photosensitive resin layer does not contain a colorant.
<7>A first substrate in which a first electrode having a light reflecting function is at least partially formed on a surface facing the second substrate; a second substrate disposed opposite to the first substrate; In a method for manufacturing a liquid crystal display device comprising a liquid crystal layer sealed between a first substrate and a second substrate, the method described in <1> to <6> is provided between the first substrate and a first electrode. A method for producing a liquid crystal display device, comprising: using a transfer plate-forming transfer material produced by any one of the production methods, and forming a resin layer having a concavo-convex portion on a surface in a step including transfer.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail.
<Transfer material for reflecting plate formation>
The transfer plate-forming transfer material of the present invention comprises at least one thermoplastic resin layer, at least one intermediate layer, and a photosensitive resin layer provided in this order on a temporary support, at least of the photosensitive resin layer. Concave and convex portions are formed at the interface on the temporary support side.
[0014]
The uneven portion is at least the interface of the photosensitive resin layer on the temporary support side, specifically, the uneven portion is a layer adjacent to the photosensitive resin layer, a temporary support adjacent to the photosensitive resin layer, an intermediate layer, or a heat It is provided on the plastic resin layer.
In this case, it is preferable that at least one layer selected from the thermoplastic resin layer, the intermediate layer, and the photosensitive resin layer contains transparent fine particles in order to form irregularities.
FIG. 1 is a schematic cross-sectional view showing an embodiment of the transfer plate-forming transfer material, in which a thermoplastic resin layer 2, an intermediate layer 3, and a photosensitive resin layer 4 are provided in this order on a temporary support 1. The intermediate layer 3 contains the transparent fine particles 5, whereby the uneven portions 6 are formed at the interface of the photosensitive resin layer 4 on the temporary support side.
In addition, it is preferable that the photosensitive resin layer does not contain a colorant for use as a base of a reflective plate or a reflective electrode in a liquid crystal cell. However, the photosensitive resin layer may be colored for the purpose of removing stray light.
[0015]
-Shape, size and number of irregularities-
Although there is no restriction | limiting in particular in the shape of the bottom face of the said uneven | corrugated | grooved part, A square, a rectangle, circular, an ellipse etc. are suitable.
When the shape of the bottom surface of the concavo-convex portion is square or circular, one side (or diameter) is preferably 2 to 100 μm, more preferably about 5 to 50 μm.
When the shape of the bottom surface of the concavo-convex portion is a rectangle or an ellipse, the short side (or the short diameter) is preferably 2 to 100 μm, more preferably about 5 to 50 μm. A rectangle or an ellipse having a short side (minor axis) of 5 μm and a long side (major axis) of 100 μm is closer to a line than a figure, but in the present invention, all of the uneven portions having such a shape are included. It is.
Moreover, in this invention, it is preferable to prevent generation | occurrence | production of the coloring and fringe by diffraction by arrange | positioning changing the size, shape, etc. of an uneven | corrugated | grooved part at random.
Further, the number of the concavo-convex portions varies depending on the use of the liquid crystal display device, but is 1 to 100, more preferably 1 to 30 per pixel.
It is desirable from the viewpoint that the uneven portions are irregularly arranged and have a continuous wave shape to obtain good reflection characteristics. As will be described later, when the reflecting plate forming transfer material is formed on the reflecting plate, it has a predetermined pitch and PV value.
[0016]
The concavo-convex portion formed on the surface of the photosensitive resin layer is not particularly limited and is appropriately selected according to the purpose. From the viewpoint of forming the concavo-convex portion simply and efficiently, a transfer material for forming a reflector described later is used. With this manufacturing method, an uneven portion is formed at the interface of the photosensitive resin layer on the temporary support side simultaneously with the manufacture of the transfer plate forming transfer material.
[0017]
The reflection plate-forming transfer material is provided with at least one thermoplastic resin layer, at least one intermediate layer, and a photosensitive resin layer in this order on a temporary support, and further appropriately selected according to need. It has the layer of. Hereinafter, each constituent layer of the transfer material for reflecting plate formation and the constituent components included in these will be described.
[0018]
-Temporary support-
As the temporary support, those having releasability to the extent that does not hinder the transfer to the thermoplastic resin layer are preferable, and those that are chemically and thermally stable and flexible are preferable. Specifically, Teflon^(R)Preferable examples include thin film sheets such as polyethylene terephthalate, polycarbonate, polyethylene, and polypropylene, or laminates thereof.
[0019]
In order to ensure good releasability between the temporary support and the thermoplastic resin, it is preferable that surface treatment such as glow discharge is not performed and an undercoat layer such as gelatin is not provided.
[0020]
The thickness of the temporary support is suitably 5 to 300 μm, and preferably 20 to 150 μm.
[0021]
-Thermoplastic resin layer-
The thermoplastic resin layer is provided as a first layer on the temporary support and mainly contains a thermoplastic resin, and may contain other components as necessary.
The thermoplastic resin can be alkali-developed after transfer, or can be removed when the thermoplastic resin protrudes to the surroundings and contaminates the substrate to be transferred depending on the transfer conditions at the time of transfer. From the viewpoint of, a resin that is soluble in an alkaline aqueous solution is preferable. Furthermore, the thermoplastic resin layer also functions as a cushioning material that prevents transfer defects that may occur due to irregularities present on the conductive pattern film when transferred onto the conductive film of the substrate, which is the transfer target. From the point of view, it is preferable to have sufficient plasticity that can be deformed in accordance with the unevenness during heat adhesion.
[0022]
In addition, when the reflective plate forming transfer material is constituted by sequentially laminating an intermediate layer and a photosensitive resin layer, which will be described later, on the temporary support, in addition to the thermoplastic resin layer, It is desirable that the adhesive strength between the temporary support and the adhesive strength between the other layers is smaller than that, so that after the transfer, the temporary support can be removed easily and without breaking the thermoplastic resin layer. Moreover, the exposure to the photosensitive resin layer after removal of the temporary support can be performed uniformly.
[0023]
From the above points, the thermoplastic resin is preferably an alkali-soluble resin having a substantial softening point of 80 ° C. or lower.
Examples of thermoplastic resins having a softening point of 80 ° C. or lower include saponified products of ethylene and acrylate copolymers, saponified products of styrene and (meth) acrylate copolymers, vinyltoluene and (meth). Saponification products such as saponification products with acrylic ester copolymers, saponification products such as poly (meth) acrylic acid esters, (meth) acrylic acid ester copolymers of butyl (meth) acrylate and vinyl acetate, etc. Even what consists of individual may use what used 2 or more types together.
[0024]
Furthermore, as described in “Plastic Performance Handbook” (edited by the Japan Plastic Industry Federation, edited by the All Japan Plastics Molding Industry Association, published by the Industrial Research Council, published on October 25, 1968), the organic polymer having a softening point of about 80 ° C. Of these, those soluble in an alkaline aqueous solution can be used.
[0025]
Further, even if the organic polymer substance has a softening point of 80 ° C. or higher, by adding various plasticizers compatible with the organic polymer substance to the organic polymer substance, the substantial softening point can be reduced to 80. It can also be used at a temperature lower than ℃. Examples of the plasticizer include the same plasticizers that can be used in the above-described photocurable composition.
[0026]
When the organic polymer substance is used, various polymers, supercooling substances, adhesion improvers, interfaces, and the like within a range where the substantial softening point does not exceed 80 ° C. for the purpose of adjusting the adhesive force with the temporary support described later. An activator, a release agent and the like can also be added.
[0027]
The thermoplastic resin layer can contain transparent fine particles for the purpose of forming irregularities at the interface on the temporary support side of the photosensitive resin layer.
The transparent fine particles are preferably spherical, alkali-soluble, and soluble in a developer.
Moreover, it is preferable that the average particle diameter of transparent fine particles is 0.5-50 micrometers, and it is more preferable that it is 1-30 micrometers.
[0028]
Examples of the transparent fine particles include fine resin particles such as acrylic resins and polyurethane resins, and fine particles of inorganic compounds such as silica.
The addition amount of the transparent fine particles is preferably 1 to 50 parts by mass, and more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the thermoplastic resin layer composition.
[0029]
The thermoplastic resin layer is prepared by dissolving the thermoplastic resin and, if necessary, other components in an organic solvent to prepare a coating solution (a coating solution for a thermoplastic resin layer). It can be formed by coating on a temporary support by a coating method.
[0030]
Examples of the organic solvent include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol monoethyl ether; methyl cellosolve Ethylene glycol alkyl ether acetates such as acetate and ethyl cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; propylene glycol Propylene glycol alkyl ether acetates such as rumethyl ether acetate and propylene glycol ethyl ether acetate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone; Ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, 3-methoxy And esters such as methyl propionate, ethyl 3-methoquinpropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate; and the like.
These organic solvents may be used individually by 1 type, and may be used in combination of 2 or more type.
[0031]
Among these, in terms of solubility of each component and film forming property, glycol esters such as ethylene glycol dimethyl ether, ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate, ethyl 2-hydroxypropionate, 3-methoxypropion Particularly suitable are esters such as methyl acid and ethyl 3-ethoxypropionate and diethylene glycols such as diethylene glycol dimethyl ether.
[0032]
Further, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl ether, acetonylacetone , Isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. A high boiling point solvent can also be added.
[0033]
The thickness of the thermoplastic resin layer is preferably 6 to 100 μm, and more preferably 6 to 50 μm. When the layer thickness is less than 6 μm, unevenness of 1 μm or more on the conductive film may not be completely absorbed. On the other hand, when it exceeds 100 μm, developability and manufacturability may be deteriorated.
[0034]
-Intermediate layer-
The intermediate layer is provided on the photosensitive resin layer, and is provided between the photosensitive resin layer and the thermoplastic resin layer when the reflection plate forming transfer material has a thermoplastic resin layer. In the formation of the photosensitive resin layer and the thermoplastic resin layer, an organic solvent is used. Therefore, when the intermediate layer is positioned between the layers, the layers can be prevented from being mixed with each other.
In addition, when the oxygen barrier ability of the intermediate layer is lowered, the polymerization sensitivity of the photosensitive resin layer is lowered, so that it is necessary to increase the amount of light at the time of exposure or lengthen the exposure time, and the resolution is also lowered. Therefore, it is preferable that oxygen permeability is small.
[0035]
The intermediate layer is mainly composed of a resin component that can be dispersed and dissolved in water or an aqueous alkaline solution, and may contain other components such as a surfactant, if necessary.
As the resin component constituting the intermediate layer, known ones can be used. For example, the polyvinyl ether / maleic anhydride polymer described in JP-A No. 46-2121 and JP-B No. 56-40824 Water-soluble salts of carboxyalkyl cellulose, water-soluble cellulose ethers, water-soluble salts of carboxyalkyl starch, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamides, water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide heavy Examples include water-soluble salts of the group consisting of coalesce, various starches and the like, styrene / maleic acid copolymers, maleate resins, and the like.
These may be used alone or in combination of two or more. Among these, it is preferable to use a hydrophilic polymer, and among these hydrophilic polymers, it is preferable to use at least polyvinyl alcohol, and a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable.
[0036]
There is no restriction | limiting in particular as said polyvinyl alcohol, Although it can select suitably according to the objective, It is preferable that the saponification rate is 80% or more.
When the polyvinyl pyrrolidone is used, the content thereof is preferably 1 to 75% by volume, more preferably 1 to 60% by volume, and more preferably 10 to 50% by volume based on the solid content of the intermediate layer. % Is particularly preferred.
When the content is less than 1% by volume, sufficient adhesion to the photosensitive resin layer may not be obtained. On the other hand, when the content exceeds 75% by volume, the oxygen blocking ability may be lowered. It is not preferable.
[0037]
Moreover, it is preferable that the said intermediate | middle layer contains a transparent fine particle in order to form an uneven | corrugated | grooved part in the interface at the side of the temporary support body of the said photosensitive resin layer.
The transparent fine particles are preferably spherical, alkali-soluble, and soluble in a developer.
Moreover, it is preferable that the average particle diameter of transparent fine particles is 0.5-50 micrometers, and it is more preferable that it is 1-30 micrometers.
[0038]
Examples of the transparent fine particles include fine resin particles such as acrylic resins and polyurethane resins, and fine particles of inorganic compounds such as silica.
The addition amount of the transparent fine particles is preferably 1 to 50 parts by mass and more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the intermediate layer composition.
[0039]
The intermediate layer is prepared by dissolving and dispersing the resin component or the like in an aqueous solvent to prepare a coating solution (intermediate layer coating solution). For example, the intermediate layer is formed on the thermoplastic resin layer by a known coating method such as a spin coating method. It can be formed by coating or the like. Examples of the aqueous solvent include a solvent containing water such as distilled water as a main component and, if desired, a solvent having affinity with water such as alcohol, a salt, or the like as long as the effects of the present invention are not impaired.
[0040]
The thickness of the intermediate layer is preferably about 0.1 to 5 μm, and more preferably 0.5 to 2 μm. If the layer thickness is less than about 0.1 μm, the oxygen permeability may be too high and the polymerization sensitivity of the photosensitive resin layer may decrease. On the other hand, if the layer thickness exceeds about 5 μm, it may be long during development or removal of the intermediate layer. It may take time.
[0041]
-Photosensitive resin layer-
The said photosensitive resin layer can be suitably formed with the photosensitive resin composition demonstrated in detail below.
[0042]
((Photosensitive resin composition))
The photosensitive resin composition of the present invention contains a polymerizable monomer, a (meth) acrylic acid-containing polymer, and a polymerization initiator, and can use either a negative photopolymerization system or a positive photopolymerization system. .
This resin composition is a thermoplastic resin composition that is softened or tacky at least at a temperature of 150 ° C. or less, is easily soluble in an alkaline solution in an unirradiated portion, and contains a colorant. If necessary, it contains other components such as a thermoplastic binder and a compatible plasticizer.
[0043]
-Polymerizable monomer-
The polymerizable monomer is an addition-polymerizable compound having at least two ethylenically unsaturated bonds, and does not impair the alkali solubility of the (meth) acrylic acid-containing polymer described later, and is polymerized during light irradiation. ) It reduces the solubility in an aqueous alkali solution together with an acrylic acid-containing polymer.
[0044]
The polymerizable monomer can be appropriately selected from compounds having two or more terminal ethylenically unsaturated bonds in one molecule, for example, a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or those And those having a chemical structure such as a copolymer thereof.
[0045]
Specifically, for example, an ester of an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and an aliphatic polyhydric alcohol compound, an unsaturated carboxylic acid and a fatty acid And amides with an aromatic polyamine compound.
[0046]
Examples of the ester (monomer) of the unsaturated carboxylic acid and the aliphatic polyhydric alcohol compound include acrylic acid ester, methacrylic acid ester, itaconic acid ester, crotonic acid ester, isocrotonic acid ester, and maleic acid ester.
[0047]
Examples of the acrylic ester include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopenterglycol diacrylate, and trimethylolpropane triacrylate. Acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, penta Erythritol tetraacrylate, dipentaerythritol dia Relate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, and polyester acrylate oligomer.
[0048]
Examples of the methacrylic acid ester include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3- Methacryloxy-2-hi Rokishipuropokishi) phenyl] dimethyl methane, bis [p- (methacryloxyethoxy) phenyl] dimethyl methane, and the like.
[0049]
Examples of the itaconic acid ester include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, and pentaerythritol. Examples include diitaconate and sorbitol tetritaconate.
[0050]
Examples of the crotonic acid ester include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.
[0051]
Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.
[0052]
Examples of the maleic ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramale.
Furthermore, the mixture of the above-mentioned various ester can also be mentioned.
[0053]
Examples of the amide (monomer) of the unsaturated carboxylic acid and the aliphatic polyvalent amine compound include methylene bis-acrylamide, methylebis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis- Examples include methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.
[0054]
As another example, a hydroxyl group-containing vinyl monomer represented by the following general formula (I) is added to a polyisocyanate compound having two or more isocyanate groups per molecule described in JP-B-48-41708. In addition, vinyl urethane compounds containing two or more polymerizable vinyl groups in one molecule may be mentioned.
CH₂= C (R) COOCH₂CH (R¹) OH (I)
[Wherein R and R¹Is H or CH_ThreeRepresents. ]
[0055]
Further, urethane acrylates described in JP-A-51-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, etc., Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid. Further, those introduced as photo-curable monomers and oligomers in the Journal of Japan Adhesion Association (vo 1.20, No. 7, p. 300-308 (1984)) can also be used.
[0056]
The said polymerizable monomer may be used individually by 1 type, and may use 2 or more types together.
As content of the said polymerizable monomer, 10-60 mass% of the total solid of the photosensitive resin composition is preferable, and 20-50 mass% is more preferable.
[0057]
Moreover, mass ratio of the total amount of the said polymerizable monomer with respect to the total amount of the (meth) acrylic acid containing polymer mentioned later is 0.5-0.9.
When the mass ratio is less than 0.5, curing by photopolymerization is insufficient and the hardness is insufficient. On the other hand, when it exceeds 0.9, a preferable shape cannot be obtained.
[0058]
-(Meth) acrylic acid-containing polymer-
The (meth) acrylic acid-containing polymer is mainly contained as a binder component and can be developed with an alkaline solution.
The (meth) acrylic acid-containing polymer is generally a polymer having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, and JP-B-58-12777. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, croton described in JP-B-54-25957, JP-A-59-53836, and JP-A-59-71048. Examples include acid copolymers, maleic acid copolymers, and partially esterified maleic acid copolymers. Moreover, the cellulose derivative which has a carboxylic acid group in a side chain is also mentioned.
[0059]
In addition to the above, preferred are those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group. In particular, a copolymer of benzyl (meth) acrylate and (meth) acrylic acid or a multi-component copolymer of benzyl (meth) acrylate, (meth) acrylic acid and other monomers described in US Pat. No. 4,139,391 Can be mentioned. Furthermore, alcohol-soluble nylon can also be mentioned.
A plurality of (meth) acrylic acid-containing polymers may be used in combination.
[0060]
The (meth) acrylic acid-containing polymer is usually used by appropriately selecting from those having an acid value in the range of 50 to 300 mgKOH / 1 g and a mass average molecular weight in the range of 1000 to 300,000.
When the acid value is less than 50 mgKOH / 1 g, the alkali developability may be greatly lowered. On the other hand, when it exceeds 300 mgKOH / 1 g, the target structure may not be obtained.
[0061]
As above-mentioned, as a mass mean molecular weight of the said (meth) acrylic acid containing polymer, 1000-300000 are preferable, and especially 10000-250,000 are preferable.
When the mass average molecular weight is less than 1000, a target structure may not be obtained. On the other hand, when it exceeds 300,000, developability may be extremely lowered. In addition, a mass average molecular weight is a polystyrene conversion average molecular weight measured by GPC (gel permeation chromatography).
[0062]
As content of the said (meth) acrylic acid containing polymer, 20-60 mass% of the total solid of the photosensitive resin composition is preferable, and 30-55 mass% is more preferable.
When the content of the (meth) acrylic acid-containing polymer is less than 20% by mass, film formation may be difficult when the photosensitive resin composition is applied on a support or the like, while 60% by mass. If it exceeds 100%, the content ratio of the polymerizable monomer is decreased, which may cause poor polymerization.
[0063]
-Polymerization initiator-
The polymerization initiator is capable of substantially initiating photopolymerization of the polymerizable monomer, and any compound having the ability to initiate the polymerization reaction of the polymerizable monomer can be used. In particular, it is preferable that at least one component having a molecular extinction coefficient of at least about 50 is contained in a wavelength region of about 300 to 500 nm and is sensitive to light in the ultraviolet region.
[0064]
Examples of the polymerization initiator include halogenated hydrocarbon derivatives, ketone compounds, ketoxime compounds, organic peroxides, thio compounds, hexaarylbiimidazoles, aromatic onium salts, ketoxime ethers, and JP-A-2-48664. And aromatic ketones, lophine dimers, benzoin, benzoin ethers, polyhalogens, and combinations of two or more thereof described in JP-A-1-152449 and JP-A-2-153353. It is done.
[0065]
Among these, halogenated hydrocarbon compounds having a triazine skeleton, ketoxime compounds, hexaarylbiimidazole, 4,4′-bis (diethylamino) benzophenone and the like in terms of excellent photosensitivity, storage stability, adhesion to a substrate, etc. A combination of 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino) -3- A system using bromophenyl] -s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl) -2,6-di (trichloromethyl) -s-triazine] is preferred.
[0066]
Examples of the halogenated hydrocarbon compound having a triazine skeleton include, for example, Bull. Chem. Soc. Japan, 42, 2924 (Wakabayashi et al., 1969) [for example, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (2 ', 4'-dichlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2 -Methyl-4,6-bis (trichloromethyl) -s-triazine, 2-n-nonyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine and the like]; compounds described in British Patent No. 1388492 [for example, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2 -(P-methylstyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p- Methoxystyryl) -4-amino-6-trichloromethyl-s-triazine and the like]; compounds described in JP-A-53-133428 [for example, 2- (4-methoxy-naphth-1-yl) -4, 6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- [4- (2- Ethoxyethyl) -naphth-1-yl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -S-triazine, 2- (acenaphtho-5-yl) -4,6-bis (trichloromethyl) -s-triazine and the like]; a compound described in German Patent No. 3333724 [for example, 2- (4 -Styrylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-p-methoxystyrylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (1- Naphthylvinylenephenyl) -4,6-bis (trichloromethyl) -s-triazine, 2-chlorostyrylphenyl-4,6-bis (trichloromethyl) -s-triazine, 2- 4-thiophene-2-vinylenephenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-thiophene-3-vinylenephenyl) -4,6-bis (trichloromethyl) -s-triazine 2- (4-furan-2-vinylenephenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-benzofuran-2-vinylenephenyl) -4,6-bis (trichloromethyl) -S-triazine etc.]; Org. Chem. (FC Schaefer et al., 29, 1527 (1964)) [for example, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2,4,6-tris (tri Bromomethyl) -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2-amino-4-methyl-6-tribromomethyl-s-triazine, 2-methoxy-4-methyl- 6-trichloromethyl-s-triazine and the like]; compounds described in JP-A No. 62-58241 [eg, 2- (4-phenylacetylenephenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-Naphtyl-1-acetylenephenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-p-tolylacetylenephenyl) -4 6-bis (trichloromethyl) -s-triazine, 2- (4-p-methoxyphenylacetylenephenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-p-isopropylphenylacetylenephenyl) ) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-p-ethylphenylacetylenephenyl) -4,6-bis (trichloromethyl) -s-triazine, etc.]; [For example, 2- (4-trifluoromethylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2,6-difluorophenyl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (2,6-dichlorophenyl) -4,6-bis (trichloromethyl) -s-tria Emissions, 2- (2,6-dibromophenyl) -4,6-bis (trichloromethyl) -s-triazine, etc.], and the like.
[0067]
As said ketoxime compound, the compound represented by the following general formula (II) is mentioned, for example.
[0068]
[Chemical 1]

[0069]
In the general formula (II), R²And R³Each independently represents a hydrocarbon group or a heterocyclic group which may have a substituent and may have an unsaturated bond, and may be the same or different from each other.
R⁴And R⁵Each independently represents a hydrogen atom, a substituent, a hydrocarbon group, a heterocyclic group, a hydroxyl group, a substituted oxy group, a mercapto group, or a substituted thio group, which may have an unsaturated bond. May be the same or different. R⁴And R⁵May be bonded to each other to form a ring, in which case the ring is -O-, -NR.⁶-, -O-CO-, -NH-CO-, -S- and -SO.₂-Represents an alkylene group having 2 to 8 carbon atoms which may contain at least one divalent group selected from-as a linking main chain of the ring.
R⁶And R⁷Each independently represents a hydrogen atom, a substituent, or a hydrocarbon group or a substituted carbonyl group which may contain an unsaturated bond.
[0070]
Specific examples of the compound represented by the general formula (II) are shown below. However, the present invention is not limited to these.
For example, p-methoxyphenyl-2-N, N-dimethylaminopropylketone oxime-O-allyl ether, p-methylthiophenyl-2-morpholinopropylketone oxime-O-allyl ether, p-methylthiophenyl-2-morphol Linopropyl ketone oxime-O-benzyl ether, p-methylthiophenyl-2-morpholinopropyl ketone oxime-On-butyl ether, p-morpholinophenyl-2-morpholinopropyl ketone oxime-O-allyl ether, p- Methoxyphenyl-2-morpholinopropylketone oxime-O-n-dodecyl ether, p-methylthiophenyl-2-morpholinopropylketone oxime-O-methoxyethoxyethyl ether, p-methylthiophenyl-2-morph Linopropyl ketone oxime-Op-methoxycarbonylbenzyl ether, p-methylthiophenyl-2-morpholinopropyl ketone oxime-O-methoxycarbonyl methyl ether, p-methylthiophenyl-2-morpholinopropyl ketone oxime-O-ethoxy Carbonyl methyl ether, p-methylthiophenyl-2-morpholinopropylketone oxime-O-4-butoxycarbonylbutyl ether, p-methylthiophenyl-2-morpholinopropylketone oxime-O-2-ethoxycarbonylethyl ether, p-methylthio Phenyl-2-morpholinopropylketone oxime-O-methoxycarboyl-3-propenyl ether, p-methylthiophenyl-2-morpholinopropylketone oxime- - and the like benzyloxycarbonyl methyl ether.
[0071]
Examples of the hexaarylbiimidazole include 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl)- 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (O-chlorophenyl) -4,4 ′, 5,5′-tetra (m-methoxyphenyl) biimidazole, 2,2′-bis (o, o′dichlorophenyl) -4,4 ′, 5,5′- Tetraphenylbiimidazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′ , 5,5'-tetraphenylbiimidazole, 2 , 2′-bis (o-trifluoromethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and the like.
These biimidazoles are described, for example, in Bull. Chem. Soc. Japan, 33, 565 (1960) and J. Am. Org. Chem., 36 (16) 2262 (1971) can be easily synthesized.
[0072]
Examples of the ketoxime ether include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentane-3- ON, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-p-toluenesulfonyloxyiminotan-2-one, 2-ethoxycarbonyl And oximino-1-phenylpropan-1-one.
[0073]
The said polymerization initiator may be used individually by 1 type, may use 2 or more types together, and can also use several compounds together between different types.
As content of the said polymerization initiator, 0.1-50 mass% of the total solid of the photosensitive resin composition is preferable, and 0.5-30 mass% is more preferable.
[0074]
The photosensitive resin layer preferably contains transparent fine particles for the purpose of forming irregularities on the surface.
The transparent fine particles are preferably spherical, alkali-soluble, and soluble in a developer.
Moreover, it is preferable that the average particle diameter of transparent fine particles is 0.5-50 micrometers, and it is more preferable that it is 1-30 micrometers.
[0075]
Examples of the transparent fine particles include fine resin particles such as acrylic resins and polyurethane resins, and fine particles of inorganic compounds such as silica.
The addition amount of the transparent fine particles is preferably 1 to 50 parts by mass, and more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the photosensitive resin layer composition.
[0076]
-Colorants such as dyes and pigments-
When coloring the reflective plate-forming transfer material of the present invention, the photosensitive resin layer can contain a colorant such as an organic pigment, an inorganic pigment, or a dye.
Examples of yellow pigments include C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 86, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 117, C.I. I. Pigment yellow 125, C.I. I. Pigment yellow 137, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 148, C.I. I. Pigment yellow 153, C.I. I. Pigment Yellow, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 166, C.I. I. And CI Pigment Yellow 168, Monolite Yellow GT (CI Pigment Yellow 12), and Permanent Yellow GR (CI Pigment Yellow 17).
[0077]
Examples of orange pigments include C.I. I. Pigment orange 36, C.I. I. Pigment orange 43, C.I. I. Pigment orange 51, C.I. I. Pigment orange 55, C.I. I. Pigment orange 59, C.I. I. And CI Pigment Orange 61.
[0078]
Examples of red pigments include C.I. I. Pigment red 9, C.I. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 149, C.I. I. Pigment red 168, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 209, C.I. I. Pigment red 215, C.I. I. Pigment red 216, C.I. I. Pigment red 217, C.I. I. Pigment red 220, C.I. I. Pigment red 223, C.I. I. Pigment red 224, C.I. I. Pigment red 226, C.I. I. Pigment red 227, C.I. I. Pigment red 228, C.I. I. Pigment red 240, C.I. I. Pigment Red 48: 1, Permanent Carmine FBB (CI Pigment Red 146), Permanent Ruby FFB (CI Pigment Red 11), Fastel Pink B Spula (CI Pigment Red 81), etc. Is mentioned.
[0079]
Examples of violet pigments include C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 30, C.I. I. Pigment violet 37, C.I. I. Pigment violet 40, C.I. I. And CI Pigment Violet 50.
[0080]
Examples of blue pigments include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. Pigment Blue 64, Victoria Pure Blue BO (C.I. 42595), and the like.
[0081]
Examples of the green pigment include C.I. I. Pigment green 7, C.I. I. And CI Pigment Green 36.
[0082]
Examples of the brown pigment include C.I. I. Pigment brown 23, C.I. I. Pigment brown 25, C.I. I. And CI Pigment Brown 26.
[0083]
Examples of black pigments include Monolite First Black B (CI Pigment Black 1), C.I. I. And CI Pigment Black 7, Fat Black HB (C.I. 26150).
[0084]
Other examples include carbon black and auramine (C.I. 41000).
In addition, the said colorant, such as an organic pigment, an inorganic pigment, or dye, may be used individually by 1 type, or can also be used in combination of 2 or more type.
[0085]
When the colorant as described above is used, the particle size of the pigment or dye is preferably 5 μm or less, and more preferably 1 μm or less. Since the photosensitive resin layer is a thin layer, when the particle size of the pigment or the like is not in the above range, it cannot be uniformly dispersed in the resin layer, which is not preferable.
[0086]
As addition amount of coloring agents, such as the said dye or a pigment, 0.01-30 mass% of the total solid of the photosensitive resin composition is preferable.
[0087]
-Other ingredients-
The photosensitive resin composition may contain components such as a thermoplastic binder and a compatible plasticizer as other components.
[0088]
Examples of the thermoplastic binder include known binders such as ethylenically unsaturated compounds.
[0089]
Examples of the compatible plasticizer include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate biphenyl diphenyl phosphate, and the like.
As addition amount of the said binder and a plasticizer, it can add in the range which does not impair the effect of this invention.
[0090]
The photosensitive resin layer is prepared by preparing a coating solution (coating solution for coating a photosensitive resin layer) by dissolving each of the above components in an organic solvent as necessary, and forming a concavo-convex portion by a known coating method. It can be formed by coating on a layer including a body, an intermediate layer and the like.
There is no restriction | limiting in particular as said organic solvent, The thing similar to what can be used for preparation of the said coating liquid for thermoplastic resin layers can be used.
[0091]
The layer thickness of the photosensitive resin layer (the portion having no uneven portion) is preferably 0.5 to 10 μm, and more preferably 1 to 6 μm.
When the layer thickness of the photosensitive resin layer is less than 0.5 μm, pinholes are likely to occur during the application of the photosensitive resin layer coating solution, and the production suitability may be reduced. On the other hand, when the thickness exceeds 10 μm. In some cases, it takes a long time to remove the unexposed portion during development.
Moreover, it is preferable that the volumetric shrinkage rate at the time of heat-hardening (baking) of the photosensitive resin layer is 50 to 90%, and more preferably 70 to 90%. Thereby, the surface shape whose surface roughness (uneven portion) is effective as a reflector can be formed in the finally obtained resin layer.
[0092]
-Cover film
It is preferable to provide a cover film on the photosensitive resin layer for the purpose of protecting it from dirt and damage during storage. The cover film can be selected from those easily peelable from the photosensitive resin layer, and may be made of the same or similar material as the temporary support.
Specifically, silicone paper, polyolefin, polytetrafluoroethylene sheet or the like is preferable, and among them, polyethylene and polypropylene films are more preferable.
[0093]
The thickness of the cover film is preferably about 5 to 100 μm, and more preferably 10 to 30 μm.
[0094]
<Manufacturing method of transfer material for reflecting plate formation>
In the method for producing a transfer material for forming a reflector according to the present invention, as a first aspect, at least one thermoplastic resin layer, at least one intermediate layer, and a photosensitive resin layer are provided in this order on a temporary support. Using the transfer plate-forming transfer material of the present invention, the winding atmosphere after applying and drying the photosensitive resin layer is made humid, or the transferred transfer material is stored in a humidified state. By doing so, the intermediate layer undergoes reticulation and undulates, thereby forming a corrugated deformation (uneven portion) at the interface of the photosensitive resin layer on the temporary support side.
The humidified state is preferably a temperature of 30 to 50 ° C. and a humidity of 60 to 90%.
[0095]
In the method for producing a transfer plate forming transfer material of the present invention, as a second aspect, at least one thermoplastic resin layer, at least one intermediate layer, and a photosensitive resin layer are provided in this order on a temporary support. Using the transfer plate forming transfer material of the present invention, the photosensitive resin layer is heat-cured to form an uneven portion at the interface of the photosensitive resin layer on the temporary support side.
In this case, the transfer plate-forming transfer material contains transparent fine particles in at least one layer selected from the thermoplastic resin layer, the intermediate layer, and the photosensitive resin layer, and the transparent fine particles are spherical and alkali-soluble. In addition, the volume shrinkage ratio of the photosensitive resin layer upon heat curing is preferably 50 to 90%, and more preferably 70 to 90%.
[0096]
In addition, the manufacturing method of the transfer material for reflecting plate formation of the 1st, 2nd aspect of this invention can be manufactured by a well-known method except said point.
[0097]
Specifically, on the temporary support, first, a coating solution prepared by dissolving a thermoplastic resin in a solvent (a coating solution for a thermoplastic resin layer) is applied and dried to provide a thermoplastic resin layer. An application layer (intermediate layer application solution) using a solvent that does not dissolve the thermoplastic resin layer is applied on the thermoplastic resin layer and dried to provide an intermediate layer. The photosensitive resin is formed on the intermediate layer. It can be formed by applying a coating solution prepared by dissolving the composition in a solvent that does not dissolve the intermediate layer, and drying to provide a photosensitive resin layer. Alternatively, a photosensitive resin layer is provided on the cover film, and on the other hand, a thermoplastic resin layer and an intermediate layer are provided on a temporary support, and the intermediate layer and the photosensitive resin layer are bonded to each other so that they are in contact with each other. Alternatively, a photosensitive resin layer and an intermediate layer are provided on the cover film, while a thermoplastic resin layer is provided on the temporary support so that the intermediate layer and the photosensitive resin layer are in contact with each other as described above. By sticking together, the transfer plate-forming transfer material of the present invention can be produced.
[0098]
As will be described later, in the process of bringing the transfer material into close contact with the substrate to be transferred and peeling off the temporary support of the transfer material, the temporary support or the substrate is charged, and as a result, the surrounding dust is attracted and peeled off. For the purpose of preventing electrification, dust or the like adheres to the subsequent photosensitive resin layer, and an unexposed part is formed in the subsequent exposure process, which causes pinholes. By providing a conductive layer on at least one surface or using a temporary support with conductivity, the surface electrical resistance is 10¹³It is preferable to lower it to Ω or less.
[0099]
In order to impart conductivity to the temporary support, a conductive substance may be contained in the temporary support. For example, a method of kneading metal oxide fine particles and an antistatic agent in advance is suitable.
Examples of the metal oxide include zinc oxide, titanium oxide, tin oxide, aluminum oxide, indium oxide, silicon oxide, magnesium oxide, barium oxide, crystalline metal oxide such as molybdenum oxide, and / or a composite oxide thereof. Fine particles are mentioned.
[0100]
Examples of the antistatic agent include Electro Stripper A (manufactured by Kao Corporation), Elenon No. Alkyl phosphate anionic surfactants such as 19 (Daiichi Kogyo Seiyaku Co., Ltd.); Betaine amphoteric surfactants such as Amorgen K (Daiichi Kogyo Seiyaku Co., Ltd.); Nissan Nonion L (Nippon Yushi Polyoxyethylene fatty acid ester-based nonionic surfactants such as Emulgen 106, 120, 147, 420, 220, 905, 910 (made by Kao Corporation) and Nissan Nonion E (made by Nippon Oil & Fats Co., Ltd.) Polyoxyethylene alkyl ether type nonionic surfactants such as) are suitable. Other nonionic surfactants include polyoxyethylene alkylphenol ethers, polyhydric alcohol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamines, and the like.
[0101]
When the conductive layer is provided on the temporary support, the conductive layer can be appropriately selected from known ones. As a conductive substance used for the conductive layer, ZnO, TiO₂, SnO₂, Al₂O₃, In₂O₃, SiO₂, MgO, BaO, MoO₃And at least one crystalline metal oxide selected from the above, and / or fine particles of the composite oxide. The method of containing these is preferable in that it has a stable conductive effect that is not affected by the humidity environment.
[0102]
The volume resistance value of the fine particles of the crystalline metal oxide or composite oxide thereof is 10⁷Ω · cm or less is preferable 10⁵More preferably Ω · cm or less. Moreover, as the particle diameter, 0.01-0.7 micrometer is preferable and 0.02-0.5 micrometer is more preferable.
[0103]
The method for producing fine particles of the crystalline metal oxide and its composite oxide is described in detail in JP-A-56-143430. That is, firstly, metal oxide fine particles are produced by firing and heat treatment is performed in the presence of different atoms to improve conductivity, and secondly, conductivity is improved when producing metal oxide fine particles by firing. And a third method for introducing oxygen defects by reducing the oxygen concentration in the atmosphere when producing metal fine particles by firing. Specific examples containing different atoms include Zn, Al, In, etc., TiO, etc.₂Nb, Ta, etc., SnO₂In contrast, the presence of Sb, Nb, halogen elements and the like can be mentioned.
[0104]
As addition amount of a different atom, 0.01-30 mol% is preferable and 0.1-10 mol% is more preferable. The amount of conductive particles used is 0.05 to 20 g / m.²Is preferably 0.1 to 10 g / m²Is more preferable.
[0105]
In the conductive layer provided on the transfer material, as binder, cellulose ester such as gelatin, cellulose nitrate, cellulose triacetate, cellulose diacetate, cellulose acetate butyrate, cellulose acetate propionate; vinylidene chloride, vinyl chloride, styrene, acrylonitrile , Vinyl acetate, homopolymers or copolymers containing alkyl acrylates having 1 to 4 carbon atoms, vinyl pyrrolidone, etc .; soluble polyesters, polycarbonates, soluble polyamides, and the like can be used.
[0106]
When electrically conductive particles are dispersed in these binders, a dispersion such as a titanium-based dispersant or a silane-based dispersant may be added. Moreover, a binder crosslinking agent etc. can also be added as needed.
[0107]
Examples of the titanium dispersant include titanate coupling agents, preneact (manufactured by Ajinomoto Co., Inc.) and the like described in US Pat. Nos. 4,069,192 and 4,080,353. Is mentioned.
Examples of the silane dispersant include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and the like. "Silane coupling agent" (manufactured by Shin-Etsu Chemical Co., Ltd.).
Examples of the binder crosslinking agent include an epoxy crosslinking agent, an isocyanate crosslinking agent, an aziridine crosslinking agent, and an epoxy crosslinking agent.
[0108]
The conductive layer is formed by dispersing conductive fine particles in a binder and coating the temporary support or applying a subbing treatment (for example, an undercoat layer) on the temporary support. Can be provided by adhering.
[0109]
The conductive layer may be provided on the surface of the temporary support opposite to the surface on which the photosensitive resin layer is coated. In this case, the conductive layer is formed on the conductive layer for the purpose of ensuring sufficient scratch resistance. It is preferable to further provide a hydrophobic polymer layer. The hydrophobic polymer layer may be applied in a state in which the hydrophobic polymer is dissolved in an organic solvent or in the state of an aqueous latex, and the coating amount is 0.05 to 1 g / m in dry mass.²The degree is preferred.
[0110]
Examples of the hydrophobic polymer include cellulose esters such as nitrocellulose and cellulose acetate; vinyl polymers including vinyl chloride, vinylidene chloride, and vinyl acrylate; polymers such as organic solvent-soluble polyamide and polyester.
[0111]
For the purpose of imparting smoothness to the hydrophobic polymer layer, for example, a smoothing agent such as an organic carboxylic acid amide described in JP-A-55-79435 can be used. Moreover, a mat agent etc. can also be used as needed. Even if such a hydrophobic polymer layer is provided, the effect of the conductive layer is not substantially affected.
[0112]
In the case of providing an undercoat layer, JP-A Nos. 51-135526, U.S. Pat. Nos. 3,143,421, 3,586,508, 2,698,235, and 3, No. 567,452 etc., vinylidene chloride copolymers described in JP-A No. 51-114120, US Pat. No. 3,615,556 etc., and georefin copolymers such as butadiene, etc. Glycidyl acrylate or glycidyl methacrylate-containing copolymer described in JP-A-51-58469, polyamide / epichlorohydrin resin described in JP-A-48-24923, etc., anhydrous described in JP-A-50-39536 A maleic acid-containing copolymer or the like can be used.
[0113]
In the present invention, JP-A-56-82504, JP-A-56-143443, JP-A-57-104931, JP-A-57-118242, JP-A-58-62647, A conductive layer described in JP-A-60-258541 can be used as necessary.
[0114]
When the conductive layer is applied on the temporary support, it can be applied by a known method such as roller coating, air knife coating, gravure coating, bar coating, or curtain coating. In order to obtain a sufficient antistatic effect, the surface electrical resistance value of the conductive layer or the temporary support provided with conductivity is set to 10¹³Ω or less is preferable, 10¹²More preferably, it is Ω or less.
[0115]
In order to prevent strong adhesion of the photosensitive resin layer to the temporary support, a slip agent composition containing known fine particles, a release agent composition containing a silicone compound, etc. are applied to the temporary support surface. You can also.
[0116]
When the conductive layer is provided on the surface of the temporary support that is not provided with the thermoplastic resin layer, the temporary support is provided with, for example, a glow layer for the purpose of improving the adhesion between the thermoplastic resin layer and the temporary support. Surface treatment such as discharge treatment, corona treatment, ultraviolet irradiation treatment, undercoating treatment such as phenolic substance, polyvinylidene chloride resin, styrene butadiene rubber, gelatin, or a combination of these treatments can be applied.
[0117]
A film for a temporary support can be formed by extrusion, but when a conductive material or conductive layer is contained in the same or different plastic raw material as that of the temporary support and is extruded at the same time as the film. Can easily obtain a conductive layer excellent in adhesion and scratch resistance. In this case, it is not necessary to provide the hydrophobic polymer layer or the undercoat layer, and this is the most preferable embodiment as a conductivity-imparting provisional support constituting the transfer material.
As the main application of the transfer material for forming a reflecting plate of the present invention, uses such as a base layer of a reflecting plate and a resin layer for forming a reflecting electrode in a liquid crystal cell are suitable.
[0118]
<Reflector>
Next, the reflecting plate of the present invention is obtained by transferring the reflecting plate-forming transfer material onto a substrate, exposing, developing and baking the light reflecting functional material on the resin layer having a concavo-convex portion on the surface. Formed.
[0119]
First, the cover film of the reflection plate forming transfer material is removed, and the photosensitive resin layer is bonded onto a substrate as a transfer target under pressure and heating. A conventionally known laminator, a vacuum laminator, or the like can be used for bonding, and an auto-cut laminator can also be used to further increase productivity. Thereafter, the temporary support is peeled off, and the photosensitive resin layer is exposed through a predetermined mask, a thermoplastic resin layer, and an intermediate layer, and then developed. Development can be carried out by a known method, using a solvent or an aqueous developer, in particular, an alkaline aqueous solution, etc., soaking the substrate after exposure or spraying with a spray or the like, and further rubbing with a brush or the like, Alternatively, it is performed by processing while irradiating ultrasonic waves.
[0120]
After the photosensitive resin layer of the transfer material for reflecting plate formation and the substrate as a transfer target are bonded together, the temporary support is peeled off at the interface with the thermoplastic resin layer, and heat is applied from above the thermoplastic resin layer. The photosensitive resin layer is exposed (patterned) in a pattern through the plastic resin layer and the intermediate layer.
The exposure can be performed by irradiation with light having a wavelength of 300 to 500 nm, and examples of the light source include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, and an Hg-Xe lamp.
[0121]
Examples of the patterning method include (1) a method by photolithography, (2) a method in which an exposure mask is disposed above the thermoplastic resin layer, and pattern exposure is performed through the mask, and (3) For example, a method using an exposure means such as a close proximity proximity exposure apparatus may be used.
In the patterning by the method (3), the exposure amount is preferably 3 to 10 times the minimum exposure amount at which the photosensitive resin composition undergoes polymerization and curing, and the proximity amount is preferably 40 to 150 μm.
[0122]
After the exposure, development processing is performed to remove the thermoplastic resin layer, the alkali-soluble intermediate layer, and the unnecessary portion (uncured portion) of the photosensitive resin layer.
[0123]
The development can be performed by a known method. For example, (a) the exposed substrate itself is immersed in a developing bath using a solvent or an aqueous developer, particularly an alkaline aqueous solution, and (b) the exposed substrate. For the purpose of further improving the solubility, for example, by spraying with a spray or the like, rubbing with a rotating brush, a wet sponge or the like, or applying ultrasonic waves.
[0124]
As the alkaline aqueous solution, a dilute aqueous solution of an alkaline substance is preferable, and a solution obtained by adding a small amount of a water-miscible organic solvent can also be suitably used. Examples of the alkaline substance include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, silica Alkali metal silicates such as sodium silicate and potassium silicate, alkali metal metasilicates such as sodium metasilicate and potassium metasilicate, tetraalkyl such as triethanolamine, diethanolamine, monoethanolamine, morpholine and tetramethylammonium hydroxide Ammonium hydroxides, trisodium phosphate and the like can be mentioned.
[0125]
The concentration of the alkaline substance in the alkaline aqueous solution is preferably 0.01 to 30% by mass, and the pH is preferably 8 to 14.
[0126]
Examples of the water-miscible organic solvent include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether, benzyl alcohol, Examples include acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, and N-methylpyrrolidone.
The addition amount of the organic solvent is preferably 0.1 to 30% by mass.
[0127]
Various known surfactants can also be added to the alkaline aqueous solution. The concentration of the surfactant is preferably 0.01 to 10% by mass.
The temperature during development is usually preferably around room temperature to 40 ° C. Furthermore, after the development processing, a step of washing with water can be added. In addition, after developing, it is further baked at 200 to 260 ° C.
[0128]
In this way, a resin layer having an uneven portion on the surface is formed on the substrate. Next, a light reflection functional material layer is formed on the uneven portion.
The light reflective functional material is not particularly limited as long as it has light reflectivity, but from the viewpoint of forming a reflective electrode, a metal material such as Al or Ag is preferable. Such a metal film can be formed by sputtering or the like.
A liquid crystal display device can be formed by using the reflective plate as one reflective electrode.
[0129]
As shown in FIG. 2, the concave and convex portions formed on the reflecting plate 20 are irregularly formed with large and small convex portions 10, or as shown in FIG. Alternatively, the ridges 11 and the valleys 12 may be alternately formed in a corrugated shape as shown in FIG.
In this case, it is preferable that the pitch (see FIG. 5) of at least one uneven portion in two orthogonal directions (XY directions in FIGS. 2 to 4) is 3 to 50 μm, and more preferably 10 to 30 μm. . Moreover, it is preferable that PV value (refer FIG. 5) is 0.1-2.0 micrometers, and it is more preferable that it is 0.2-0.8 micrometer. In addition, the measurement of an uneven | corrugated | grooved part is represented by an average value using a surface roughness meter.
[0130]
<Liquid crystal display device and manufacturing method thereof>
The liquid crystal display device according to the present invention includes a first substrate having a first electrode having a light reflecting function formed at least partially on a surface facing the second substrate, and the first substrate facing the first substrate. And a liquid crystal layer sealed between the first and second substrates, and the reflector for forming the reflector according to the invention is formed between the first substrate and the first electrode. The resin layer which has an uneven | corrugated | grooved part is provided in the surface formed at the process including transcription | transfer using a transcription | transfer material.
Each of the first and second electrodes may be formed in a matrix. Further, the first electrode may be patterned for each pixel, and the second electrode may be formed in a solid shape.
[0131]
The resin layer has a concavo-convex portion formed by a process including transfer on the surface using the transfer material for forming a reflector of the present invention, and the concavo-convex portion has a continuous wavy shape. It is preferable that good reflection characteristics can be obtained over a wide area.
The concavo-convex portion is formed with a large number of convex portions or concavo-convex portions having a diameter of 0.7 to 30 μm (circle or oval) and a height of 0.1 to 1.5 μm. The appropriate range of this shape varies depending on the application of the liquid crystal display device. In the case of completely personal use, a configuration in which uneven portions having a diameter of 5 μm and a height of 0.5 μm are spread over about 70% of the pixel area is preferable. Further, the irregularities may be substantially circular or circular, and may be elliptical. Further, these diameters are arranged at random to prevent the occurrence of moire. The unevenness may be a cone or a pyramid.
[0132]
A TFT active matrix substrate is preferably used as the substrate having the switching element. As the TFT active matrix substrate, a conventional substrate can be used without limitation. For example, a gate signal line and an additional capacitor electrode are formed on an active matrix substrate (array substrate), a gate insulating film is formed thereon, a semiconductor layer and a channel protective layer are formed, and further, a TFT source and drain are formed. An n + Si layer to be formed is formed, and then a metal layer and an ITO film are formed by a sputtering method, and these are patterned to form a drain signal line and a source signal line.
[0133]
The TFT (thin film transistor) active matrix layer is preferably formed of an amorphous silicon, a low-temperature polysilicon base material, or a continuous grain silicon base material.
[0134]
The method for manufacturing a liquid crystal display device according to the present invention includes a first substrate on which a first electrode having a light reflecting function is formed at least partially on a surface facing the second substrate, and the first substrate facing the first substrate. In a method of manufacturing a liquid crystal display device comprising: a second substrate that is disposed; and a liquid crystal layer that is sealed between the first and second substrates.
Between the first substrate and the first electrode, the transfer plate forming transfer material of the present invention is used to form a resin layer having an uneven portion on the surface in a process including transfer.
More specifically, first, a plurality of wirings are provided on an insulating substrate made of glass, and after a surface treatment or the like, an insulating film, a semiconductor film, etc. are formed to form switching elements in an array. .
[0135]
Next, the transfer plate forming transfer material of the present invention is transferred so as to cover almost the entire surface of the substrate on which the switching elements are formed. This transfer is performed by a laminator, and if necessary, the substrate surface is subjected to a pretreatment such as silane coupling.
Then, after exposure using a predetermined exposure mask, development is performed with a developer such as a TMAH aqueous solution, and the resin layer in the contact hole and the alignment mark portion is removed. At this stage, the surface of the resin layer is uneven. The exposure performed here is 20 mJ / cm.²The exposure time is sufficiently shorter than 30 seconds, and the tact time of the production line can be set to 1 minute or less and around 30.
After this is further cured by post-exposure and / or post-baking, a reflective layer made of Al and / or Ag or the like is formed thereon. At this time, it is connected to the switching element through a contact hole. Further, this reflective layer is pattern-etched to form a reflective electrode that is independent for each pixel and connected to the switching element for each pixel. An alignment film is formed thereon, and a rubbing process or the like is performed.
[0136]
On the other substrate, a color filter is formed in a portion facing the reflective electrode (a black matrix is formed if necessary), and a transparent electrode made of ITO (Indium Tin Oxide) is formed. Both substrates are bonded to each other so that the reflective electrode and the color filter coincide with each other, and liquid crystal is injected therebetween to manufacture a reflective liquid crystal display device.
[0137]
As the liquid crystal display device, a device having one or both of a color filter on array (COA) structure and a transflective structure can be suitably used in addition to the above structure.
[0138]
The COA structure includes, for example, a color filter integrated driving substrate in which a color filter is directly formed on the driving side substrate and a counter electrode (conductive layer) as described in JP-A-10-206888. The counter substrate is arranged opposite to each other with a spacer interposed, and a liquid crystal material is sealed in the gap, and a color filter is formed on the reflective electrode to widen the bonding margin in high definition. Thus, the yield and the aperture ratio can be improved.
[0139]
The transflective structure is a kind of a reflective liquid crystal display device having a function of reflecting and displaying light from the front and a function of transmitting and displaying light from the back. A "half mirror type" configured to transmit light from the back surface by a method such as thinning a reflection layer provided to reflect light, and a region for reflecting light in one pixel In addition, there is an “intra-pixel division type” that also has a light transmitting region.
[0140]
The half mirror type is described in, for example, Japanese Patent Application Laid-Open No. 2001-100197. Although the structure is simple, the transmitted color of the backlight is transmitted through the reflective color filter having a low optical density, so that the displayed color is light.
[0141]
The “intra-pixel division type” is described in, for example, Japanese Patent Application Laid-Open No. 2001-174797, as shown in FIG. The color filter corresponding to the pixel inner part having the reflection function is a reflection color filter having a low optical density, and the color filter corresponding to the pixel inner part having the transmission function is the transmission color filter having a high optical density. Thus, in the case of the reflection type and the case of the transmission type, good color reproducibility can be obtained. In FIG. 6, 30 is a photosensitive resin layer, and 31 is a substrate.
Further, in the “intra-pixel division type”, the insulation on the TFT substrate side is made so that the liquid crystal layer corresponding to the inner part of the pixel having a reflection function is thin and the liquid crystal layer corresponding to the inner part of the pixel having a transmission function is thick. A film thickness, a color filter thickness, an overcoat thickness, and the like are set, and good contrast can be obtained in both reflection and transmission.
[0142]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples at all.
[0143]
[Reference example1]
-Creation of resin film for transfer-
A 75 μm thick polyethylene terephthalate film temporary support was coated with a coating solution having the following formulation H1 to form a thermoplastic resin layer having a dry film thickness of 14 μm.
<Thermoplastic resin layer formulation H1:>
・ Methyl methacrylate / 2-ethylhexyl acrylate / benzyl
Methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55/30/10/5, mass average molecular weight = 100,000, Tg≈70 ° C.)
                                                                7 parts by mass
Styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 65/35,
(Mass average molecular weight = 10,000, Tg≈100 ° C.)
                                                                7 parts by mass
・ A compound obtained by dehydration condensation of 2 equivalents of octaethylene glycol monomethacrylate to bisphenol A (BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.)
                                                                7 parts by mass
50 parts by mass of methyl ethyl ketone
[0144]
Next, an intermediate layer coating solution P1 having the following composition was applied on the thermoplastic resin layer, and then dried at 100 ° C. for 2 minutes to form an intermediate layer having a thickness of 1.6 μm. At this time, beads were contained in the coating solution for the intermediate layer, and since these beads were supple, they were flattened during drying, and uneven portions were formed on the surface of the intermediate layer.
<Intermediate layer prescription P1:>

[0145]
Next, the following photosensitive resin layer solution C1 was applied and dried to provide a photosensitive resin layer having a dry film thickness of 3.3 μm, covered with a protective film, and a transfer resin film was prepared.
On the surface of this resin film for transfer, asperities having a pitch of 10 to 40 μm and a PV value of 0.1 to 0.5 μm were formed by SEM observation.
<Photosensitive resin layer solution C1>
・ 240 parts by mass of polymer solution
Styrene / maleic acid copolymer benzylamine modified product = 68/32 (molar ratio)
・ 200 parts by mass of dipentaerythritol hexaacrylate
・ Cyclohexanone 730 parts by mass
Photopolymerization initiator IRG184 (CAS 947-19-3) 10 parts by mass
(Methyl ethyl ketone added as appropriate)
[0146]
<Washing substrate>
A TFT substrate having a length of 320 mm × width of 400 mm was subjected to ultrasonic cleaning in ultrapure water at room temperature for 1 minute, drained by air blow, and then dried.
[0147]
<Formation of resin layer>
The protective film of the transfer resin film was peeled off, and then laminated at a temperature of 130 ° C., a linear pressure of 100 N / cm, and a conveyance speed of 3.0 m / min.
After peeling the temporary support, 20 mJ / cm with an ultra-high pressure mercury lamp²Pattern exposure. The exposure time at this time was 3 seconds.
[0148]
Next, shower development was performed at 38 ° C. for 35 seconds with a developer P1 having the following composition to remove the thermoplastic resin layer and the intermediate layer.
<Composition of Developer P1>
・ 97 parts by mass of ultrapure water
・ Triethanolamine 3 parts by mass
(Alkali metal concentration 50ppb)
[0149]
Subsequently, the developer D1 having the following composition was shower-developed at 33 ° C. for 26 seconds to develop the photosensitive resin layer, and the contact hole portion (hole to connect the Al layer and TFT described later) and the transmission portion were removed. Pattern image was obtained.
<Developer D1>
・ Monoethanolamine 0.2mole / L
・ Acetic acid 0.1 mole / L
・ Dipolyoxyethylene alkylamine 1% by mass
(Alkali metal concentration 50ppb)
[0150]
Next, in order to form a first electrode (referred to as a reflective electrode) having a light reflecting function, an Al layer was formed by a sputtering method. At this time, the film thickness of the Al layer is 0.5 μm, and the film formation conditions are substrate temperature 100 ° C., Ar pressure 0.5 Pa, RF power 3.4 W / cm.²Met. Subsequently, the first layer having a light reflection function was formed by patterning the Al layer into a predetermined shape by photolithography and etching. The first electrode having the light reflecting function reflected the uneven shape formed on the surface of the C1 layer, whereby a reflective electrode having an uneven portion was obtained.
[0151]
Next, an alignment film (not shown) made of polyimide was applied to the entire surface of the substrate, baked at 150 ° C. for 2 hours, and then rubbed. Next, a counter-side substrate in which a transparent electrode made of a color filter and ITO was formed on a glass substrate at a position facing the reflective electrode was prepared as a counter-side substrate, and alignment film coating, baking, and rubbing were performed.
These two substrates were opposed to each other with a spacer so as to have a predetermined cell thickness (not shown), and were bonded together by a seal portion. Subsequently, liquid crystal was injected and sealed between the substrates to produce a liquid crystal display device.
[0152]
〔Example1]
  Reference example1, a transfer resin film having the same composition except that the resin beads were removed from the intermediate layer formulation P1 was stored at 45 ° C. and 80% humidity for 10 hours. As a result of reticulation of the intermediate layer, an uneven portion having a pitch of 10 to 40 μm and a PV value of 0.1 to 0.5 μm was formed on the interface of the photosensitive resin layer on the temporary support side by SEM observation. After the protective film of the transfer resin film was peeled off, it was laminated at a temperature of 130 ° C., a linear pressure of 100 N / cm, and a conveyance speed of 3.0 m / min. After peeling the temporary support, 20 mJ / cm with an ultra-high pressure mercury lamp²Pattern exposure. The exposure time at this time was 3 seconds. A liquid crystal display device was assembled in the same manner.
[0153]
[Comparative Example 1]
  Except that the resin layer having the concavo-convex portion formed on the TFT substrate was formed as follows based on the description of JP-A-11-153804,Reference exampleIn the same manner as in Example 1, a liquid crystal display device was produced.
[0154]
A photocurable resin mainly composed of a photopolymerizable oligomer, a photopolymerizable monomer, and a photopolymerization initiator was applied to the entire surface of the substrate. Pentaerythritol, which is an ester acrylate, was used as a photopolymerizable oligomer, and neopentyl glycol diacrylate was used as a photopolymerizable monomer, and 2% by mass of a photopolymerization initiator was added thereto. This was applied to the entire surface of the substrate with a film thickness of 3 μm.
A convex portion was formed using a transflective mask in which the light transmittance of the transmissive portion of the exposure mask was partially changed. The irradiation energy at this time is 1200 mJ / cm.²~ 1500mJ / cm²Met. At this time, the exposure time required 240 seconds.
[0155]
  Reference Example 1 and Example 1And Comparative Example 1Reference Example 1 and Example 1Then, while the exposure time for forming the concavo-convex portion is 3 seconds, in Comparative Example 1, it takes 240 seconds, and the tact time of the production line is as long as 3 minutes or more, so it is clear that the productivity is inferior. is there.
[0156]
【The invention's effect】
According to the present invention, the above-mentioned problems can be solved, and a liquid crystal display device having a reflective electrode having good reflective characteristics by a simple process, particularly used for OA equipment, personal computers, portable information terminals, etc. Among them, a reflective liquid crystal display device that uses outside light such as room lighting or sunlight can be manufactured efficiently and inexpensively.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing a reflection plate-forming transfer material according to an example of the present invention.
FIG. 2 is a schematic diagram illustrating an example of an uneven portion.
FIG. 3 is a schematic diagram illustrating an example of an uneven portion.
FIG. 4 is a schematic diagram illustrating an example of an uneven portion.
FIG. 5 is an explanatory diagram showing pitches and PV values of uneven portions.
FIG. 6 is a schematic cross-sectional view showing an intra-pixel division type transflective LCD.

Claims (7)

The thermoplastic resin layer of at least one layer on a temporary support, at least one intermediate layer, the photosensitive resin layer using a transfer material for reflector formed ing provided in this order, formed by coating the photosensitive resin layer The interface on the temporary support side of the photosensitive resin layer by reticulation of the intermediate layer by making the winding atmosphere after drying and drying into a humid state or storing the transfer material after winding in a humid state A method for producing a transfer plate-forming transfer material, wherein uneven portions are formed on the substrate. The method for producing a transfer material for forming a reflector according to claim 1, wherein transparent fine particles are contained in at least one layer selected from the thermoplastic resin layer, the intermediate layer, and the photosensitive resin layer. The method for producing a transfer plate-forming transfer material according to claim 2, wherein the transparent fine particles are alkali-soluble. The method for producing a reflecting plate forming transfer material according to any one of claims 1 to 3, wherein the humidified state is a temperature of 30 to 50 ° C and a humidity of 60 to 90%. 4. An uneven portion is formed at the interface of the photosensitive resin layer on the temporary support side by heat-curing the photosensitive resin layer using the transfer plate forming transfer material. The manufacturing method of the transfer material for reflecting plate formation in any one of. The manufacturing method of the transfer material for reflecting plate formation in any one of Claim 1 to 5 in which the said photosensitive resin layer does not contain a coloring agent. A first substrate in which a first electrode having a light reflecting function is formed at least partially on a surface facing the second substrate; a second substrate disposed opposite to the first substrate; A method for manufacturing a liquid crystal display device comprising a liquid crystal layer sealed between a first substrate and a second substrate, wherein the liquid crystal layer is between the first substrate and the first electrode. A method for producing a liquid crystal display device, comprising: forming a resin layer having a concavo-convex portion on a surface in a step including transfer, using a transfer plate-forming transfer material produced by the production method described above.

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