JP3640638B2 - Method for forming resist pattern for liquid crystal display device manufacturing - Google Patents

Description

【００１６】
〔式中、Ｒ¹〜Ｒ⁸はそれぞれ独立に水素原子、ハロゲン原子、炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、又は炭素原子鎖３〜６のシクロアルキル基を表し；Ｒ⁹〜Ｒ¹¹はそれぞれ独立に水素原子又は炭素原子数１〜６のアルキル基を表し；Ｑは水素原子、炭素原子数１〜６のアルキル基、Ｒ⁹と結合して炭素原子鎖３〜６のシクロアルキル基を形成する基、又は下記の化学式（II）で表される基
【００１７】
【化１０】

【００１８】
（式中、Ｒ¹²及びＲ¹³はそれぞれ独立に水素原子、ハロゲン原子、炭素原子数１〜６のアルキル基、炭素原子数１〜６のアルコキシ基、又は炭素原子鎖３〜６のシクロアルキル基を表し；ｃは１〜３の整数を示す）を表し；ａ、ｂは１〜３の整数を表し；ｄは０〜３の整数を表し；ｎは０〜３の整数を表す〕
で表されるフェノール化合物を５〜２５質量部含有し、（Ａ）成分と（Ｂ）成分の総質量１００質量部に対し、（Ｃ）下記一般式（III）
【００１９】
【化１１】

【００２０】
（式中、Ｒ¹⁴は、独立に炭素原子数１〜５のアルキル基を表わし、Ｄは、独立に水素原子、又は１，２−ナフトキノンジアジド−５−スルホニル基を表し、Ｄの少なくとも１つは１，２−ナフトキノンジアジド−５−スルホニル基を表し、ｌ、ｍは、それぞれ独立に１又は２を表わす）
で表されるキノンジアジドエステル化物（感光性成分１）、及び下記一般式（IV）
【００２１】
【化１２】

【００２２】
（式中、Ｄは、独立に水素原子、又は１，２−ナフトキノンジアジド−５−スルホニル基を表し、Ｄの少なくとも１つは１，２−ナフトキノンジアジド−５−スルホニル基である。）
で表されるキノンジアジドエステル化物（感光性成分２）からなる感光性成分の混合物を１５〜４０質量部の範囲で含有し、更に（Ｄ）有機溶媒を含有することを特徴とするポジ型ホトレジスト組成物である。
【００２３】
上記本発明によれば、安価であって、５００×６００ｍｍ²以上の大型ガラス基板を用いたプロセスにおいても、マクロ的な特性（塗布性、加熱ムラ特性、現像ムラ特性）に優れたレジスト材料を提供することができる。更に、システムＬＣＤの製造に好適な、リニアリティに優れ、ｉ線露光に適したレジスト材料を提供することができる。
このようにして形成された液晶表示素子製造用レジストパターンは、５００×６００ｍｍ ² 以上の大型ガラス基板を用いて作られたものであっても、寸法精度の高いものとすることができる。
【００２４】
前記（Ｂ）成分は、下記式（Ｖ）又は（VI）
【００２５】
【化１３】

【００２６】
で表されるフェノール化合物であることが好ましい。これら化合物は、ホトレジスト膜に高感度化、高残膜率化、及びリニアリティの向上効果に特に優れる。
【００２７】
前記（Ａ）成分は、全フェノール系繰り返し単位中、ｐ−クレゾール系繰り返し単位を６０モル％以上含有し、かつｍ−クレゾール系繰り返し単位を３０モル％以上含有し、ポリスチレン換算重量平均分子量（Ｍｗ）が２０００〜８０００のノボラック樹脂であることが好ましい。このような樹脂は、特に感度が良好であり、かつ、加熱処理時の温度ムラに対する感度変化が起こりにくい。
【００２８】
前記感光性成分１は、下記式（VII）
【００２９】
【化１４】

【００３０】
で表わされるフェノール化合物と１，２−ナフトキノンジアジド−５−スルホニル化合物との平均エステル化率４０〜６０％のキノンジアジドエステル化物であり、感光性成分２は、下記式（VIII）
【００３１】
【化１５】

【００３２】
で表わされるフェノール化合物と１，２−ナフトキノンジアジド−５−スルホニル化合物との平均エステル化率５０〜７０％のキノンジアジドエステル化物であることが好ましい。
このような２種の感光成分を用いることにより、本発明のポジ型ホトレジストに、マクロ的な特性（塗布性、加熱ムラ特性、現像ムラ特性）に優れ、残膜率が高く、感度が良好であり、かつ保存安定性のよいレジスト材料を提供することができる。
【００３３】
本発明レジスト組成物は、（Ｄ）成分としてプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）を含有することが好ましい。ＰＧＭＥＡを含有することにより、本発明レジスト組成物は、塗布性に優れ、大型ガラス基板上でのレジスト被膜の膜厚均一性に優れるものとなる。
【００３４】
前記（Ａ）、（Ｂ）及び（Ｃ）成分の総質量が前記ポジ型ホトレジスト組成物の全質量に対して３０質量％以下であることが好ましい。このように前記ポジ型ホトレジスト組成物中の有機溶媒の含量を多くし、（Ａ）、（Ｂ）及び（Ｃ）成分の総量を少なくすることにより、特に前記ポジ型ホトレジスト組成物の塗布性に優れるものとすることができる。
【００３５】
本発明のポジ型ホトレジスト組成物は、液晶表示素子の製造用のものであることが特に好ましい。本発明のポジ型ホトレジスト組成物は、マクロ的な特性（塗布性、加熱ムラ特性、現像ムラ特性）に優れ、残膜率が高く、感度が良好であるからである。
【００３６】
また、前記液晶表示素子は、５００×６００ｍｍ²以上の大型ガラス基板を用いて作られるものであることが好ましい。
【００３７】
本発明のポジ型ホトレジスト組成物は、システムＬＣＤの製造用のものであることが特に好ましい。本発明のポジ型ホトレジスト組成物は、リニアリティに優れ、ｉ線露光によって小さなパターンと大きなパターンとを同時に露光し、レジストパターンを形成することができるからである。
【００３８】
前記システムＬＣＤは、５００×６００ｍｍ²以上の大型ガラス基板を用いて作られるものであることが好ましい。
【００３９】
前記システムＬＣＤは、ｉ線（３６５ｎｍ）露光プロセスを用いて作られるものであることが好ましい。０．５〜２．５μｍ程度の微細なレジストパターンをも良好に形成することができるからである。
【００４２】
本発明は、また、上記（３）選択的露光を行う工程が、パターン寸法の異なるレジストパターン形成用マスクパターンが描かれたマスクを用いて行われるものであり、前記ガラス基板上にパターン寸法の異なるレジストパターンを同時に形成することを特徴とする液晶表示素子製造用レジストパターンの形成方法である。
前記パターン寸法の異なるレジストパターン形成用マスクパターンが描かれたマスクは、パターン寸法０．５パターン寸法０．５〜２．５μｍのレジストパターン形成用マスクパターンとパターン寸法３〜１０μｍのレジストパターン形成用マスクパターンが少なくとも混在して描かれたマスク（レチクル）を用いて行われるものであることが好ましい。この場合、上記ガラス基板上にパターン寸法０．５〜２．５μｍのレジストパターンとパターン寸法３〜１０μｍのレジストパターンを同時に形成することが更に好ましい。
【００４３】
本発明のポジ型ホトレジスト組成物は、このように寸法の異なるパターンを同時に形成することが出来る。
【００４４】
上記（３）選択的露光を行う工程は、ｉ線（３６５ｎｍ）を光源に用いた露光プロセスにより行うことが好ましい。
ｉ線を用いることにより寸法精度の高いパターンを形成することができるからであり、本発明のポジ型ホトレジスト組成物は、このようなｉ線を用いる露光及びその後の現像を可能にする。
【００４５】
【発明の実施の形態】
（Ａ）成分（アルカリ可溶性樹脂）について：
（Ａ）成分としてのアルカリ可溶性樹脂は、特に制限されるものでなく、ポジ型ホトレジスト組成物において被膜形成物質として通常用いられ得るものの中から任意に選ぶことができる。例えば、ポジ型ホトレジスト組成物の被膜形成用樹脂として知られているフェノール樹脂、アクリル樹脂、スチレンとアクリル酸との共重合体、ヒドロキシスチレンの重合体、ポリビニルフェノール、ポリα−メチルビニルフェノール等が挙げられる。これらの中でも特にフェノール樹脂が好ましく用いられ、中でも膨潤することなくアルカリ水溶液に容易に溶解し現像性に優れるノボラック樹脂が好適である。
【００４６】
フェノール樹脂の例としては、フェノール類とアルデヒド類との縮合反応生成物、フェノール類とケトン類との縮合反応生成物、ビニルフェノール系重合体、イソプロペニルフェノール系重合体、これらのフェノール樹脂の水素添加反応生成物等が挙げられる。
【００４７】
前記フェノール樹脂を形成するフェノール類としては、例えばフェノール、ｍ−クレゾール、ｐ−クレゾール、ｏ−クレゾール、２，３−キシレノール、２，５−キシレノール、３，５−キシレノール、３，４−キシレノール等のキシレノール類；ｍ−エチルフェノール、ｐ−エチルフェノール、ｏ−エチルフェノール、２，３，５−トリメチルフェノール、２，３，５−トリエチルフェノール、４−ｔｅｒｔ−ブチルフェノール、３−ｔｅｒｔ−ブチルフェノール、２−ｔｅｒｔ−ブチルフェノール、２−ｔｅｒｔ−ブチル−４−メチルフェノール、２−ｔｅｒｔ−ブチル−５−メチルフェノール等のアルキルフェノール類；ｐ−メトキシフェノール、ｍ−メトキシフェノール、ｐ−エトキシフェノール、ｍ−エトキシフェノール、ｐ−プロポキシフェノール、ｍ−プロポキシフェノール等のアルコキシフェノール類；ｏ−イソプロペニルフェノール、ｐ−イソプロペニルフェノール、２−メチル−４−イソプロペニルフェノール、２−エチル−４−イソプロペニルフェノール等のイソプロペニルフェノール類；フェニルフェノール等のアリールフェノール類；４，４’−ジヒドロキシビフェニル、ビスフェノールＡ、レゾルシノール、ヒドロキノン、ピロガロール等のポリヒドロキシフェノール類等を挙げることができる。これらは単独で用いてもよいし、また２種以上を組み合わせて用いてもよい。これらのフェノール類の中では、特にｍ−クレゾール、ｐ−クレゾール、２，５−キシレノール、３，５−キシレノール、２，３，５−トリメチルフェノールが好ましい。
【００４８】
前記アルデヒド類としては、例えばホルムアルデヒド、パラホルムアルデヒド、トリオキサン、アセトアルデヒド、プロピオンアルデヒド、ブチルアルデヒド、トリメチルアセトアルデヒド、アクロレイン、クロトンアルデヒド、シクロヘキサンアルデヒド、フルフラール、フリルアクロレイン、ベンズアルデヒド、テレフタルアルデヒド、フェニルアセトアルデヒド、α−フェニルプロピルアルデヒド、β−フェニルプロピルアルデヒド、ｏ−ヒドロキシベンズアルデヒド、ｍ−ヒドロキシベンズアルデヒド、ｐ−ヒドロキシベンズアルデヒド、ｏ−メチルベンズアルデヒド、ｍ−メチルベンズアルデヒド、ｐ−メチルベンズアルデヒド、ｏ−クロロベンズアルデヒド、ｍ−クロロベンズアルデヒド、ｐ−クロロベンズアルデヒド、ケイ皮アルデヒド等が挙げられる。これらは単独で用いてもよいし、また２種以上を組み合わせて用いてもよい。これらのアルデヒド類の中では、入手のしやすさからホルムアルデヒドが好ましいが、特に耐熱性を向上させるためにはヒドロキシベンズアルデヒド類とホルムアルデヒドを組み合わせて用いるのが好ましい。
【００４９】
前記ケトン類としては、例えばアセトン、メチルエチルケトン、ジエチルケトン、ジフェニルケトン等が挙げられる。これらは単独で用いてもよいし、また２種以上を組み合わせて用いてもよい。フェノール類とケトン類との組み合わせにおいては、ピロガロールとアセトンとの組み合わせが特に好ましい。
【００５０】
フェノール類とアルデヒド類又はケトン類との縮合反応生成物は、酸性触媒の存在下公知の方法で製造することができる。その際の酸性触媒としては、塩酸、硫酸、ギ酸、シュウ酸、パラトルエンスルホン酸等を使用することができる。このようにして得られた縮合生成物は、分別等の処理を施すことによって低分子領域をカットしたものが耐熱性に優れているので好ましい。分別等の処理は、縮合反応により得られた樹脂を良溶媒、例えばメタノール、エタノール等のアルコール、アセトン、メチルエチルケトン等のケトンや、エチレングリコールモノエチルエーテルアセテート、テトラヒドロフラン等に溶解し、次いで水中に注ぎ沈殿させる等の方法により行われる。
【００５１】
本発明においては、上記のものの中でも特に全フェノール系繰り返し単位中、ｐ−クレゾール系繰り返し単位を６０モル％以上含有し、かつｍ−クレゾール系繰り返し単位を３０モル％以上含有し、ポリスチレン換算重量平均分子量（Ｍｗ）が２０００〜８０００のノボラック樹脂が好ましい。
【００５２】
ｐ−クレゾール系繰り返し単位が６０モル％未満では加熱処理時の温度ムラに対する感度変化が起こりやすく、またｍ−クレゾール系繰り返し単位が３０モル％未満では、感度が劣る傾向があるため好ましくない。
【００５３】
なお、本発明のアルカリ可溶性樹脂には、キシレノール系繰り返し単位や、トリメチルフェノール系繰り返し単位などの、他のフェノール系繰り返し単位を含有していても良いが、最も好ましくは、ｐ−クレゾール系繰り返し単位６０〜７０モル％、ｍ−クレゾール系繰り返し単位４０〜３０モル％とからなる２成分系のノボラック樹脂であり、フェノール類の２核体（２個のフェノール核を有する縮合体分子）
含有量がＧＰＣ（ゲル・パーミエーション・クロマトグラフィー）法において１０％以下であるようなフェノール類の低分子量体含有量が少ないノボラック樹脂が好ましい。前記２核体は高温（例えば１３０℃）のプリべークやポストベーク中に昇華して炉の天板などを汚し、更にはレジストを塗布したガラス基板を汚してその歩留まりを下げる原因となるからである。
【００５４】
（Ｂ）成分（感度向上剤）について：
本発明の組成物には、（Ｂ）成分として、上記一般式（Ｉ）で表されるフェノール化合物を用いる。
【００５５】
（Ｂ）成分の例としては、トリス（４−ヒドロシキフェニル）メタン、ビス（４−ヒドロキシ−３−メチルフェニル）−２−ヒドロキシフェニルメタン、ビス（４−ヒドロキシ−２，３，５−トリメチルフェニル）−２−ヒドロキシフェニルメタン、ビス（４−ヒドロキシ−３，５−ジメチルフェニル）−４−ヒドロキシフェニルメタン、ビス（４−ヒドロキシ−３，５−ジメチルフェニル）−３−ヒドロキシフェニルメタン、ビス（４−ヒドロキシ−３，５−ジメチルフェニル）−２−ヒドロキシフェニルメタン、ビス（４−ヒドロキシ−２，５−ジメチルフェニル）−４−ヒドロキシフェニルメタン、ビス（４−ヒドロキシ−２，５−ジメチルフェニル）−３−ヒドロキシフェニルメタン、ビス（４−ヒドロキシ−２，５−ジメチルフェニル）−２−ヒドロキシフェニルメタン、ビス（４−ヒドロキシ−３，５−ジメチルフェニル）−３，４−ジヒドロキシフェニルメタン、ビス（４−ヒドロキシ−２，５−ジメチルフェニル）−３，４−ジヒドロキシフェニルメタン、ビス（４−ヒドロキシ−２，５−ジメチルフェニル）−２，４−ジヒドロキシフェニルメタン、ビス（４−ヒドロキシフェニル）−３−メトキシ−４−ヒドロキシフェニルメタン、ビス（５−シクロヘキシル−４−ヒドロキシ−２−メチルフェニル）−４−ヒドロキシフェニルメタン、ビス（５−シクロヘキシル−４−ヒドロキシ−２−メチルフェニル）−３−ヒドロキシフェニルメタン、ビス（５−シクロヘキシル−４−ヒドロキシ−２−メチルフェニル）−２−ヒドロキシフェニルメタン、ビス（５−シクロヘキシル−４−ヒドロキシ−２−メチルフェニル）−３，４−ジヒドロキシフェニルメタン、１−［１−（４−ヒドロキシフェニル）イソプロピル］−４−［１，１−ビス（４−ヒドロキシフェニル）エチル］ベンゼン、１−［１−（３−メチル−４−ヒドロキシフェニル）イソプロピル］−４−［１，１−ビス（３−メチル−４−ヒドロキシフェニル）エチル］ベンゼン、２−（２，３，４−トリヒドロキシフェニル）−２−（２’，３’，４’−トリヒドロキシフェニル）プロパン、２−（２，４−ジヒドロキシフェニル）−２−（２’，４’−ジヒドロキシフェニル）プロパン、２−（４−ヒドロキシフェニル）−２−（４’−ヒドロキシフェニル）プロパン、２−（３−フルオロ−４−ヒドロキシフェニル）−２−（３’−フルオロ−４’−ヒドロキシフェニル）プロパン、２−（２，４−ジヒドロキシフェニル）−２−（４’−ヒドロキシフェニル）プロパン、２−（２，３，４−トリヒドロキシフェニル）−２−（４’−ヒドロキシフェニル）プロパン、２−（２，３，４−トリヒドロキシフェニル）−２−（４’−ヒドロキシ−３’，５’−ジメチルフェニル）プロパン、ビス（２，３，４−トリヒドロキシフェニル）メタン、ビス（２，４−ジヒドロキシフェニル）メタン、２，３，４−トリヒドロキシフェニル−４’−ヒドロキシフェニルメタン、１，１−ジ（４−ヒドロキシフェニル）シクロヘキサン、２，４−ビス［１−（４−ヒドロキシフェニル）イソプロピル］−５−ヒドロキシフェノール等が挙げられる。
【００５６】
これらの中でも、感度向上効果に特に優れることから、ビス（４−ヒドロキシ−３−メチルフェニル）−２−ヒドロキシフェニルメタン、ビス（４−ヒドロキシ−２，３，５−トリメチルフェニル）−２−ヒドロキシフェニルメタン、２，４−ビス［１−（４−ヒドロキシフェニル）イソプロピル］−５−ヒドロキシフェノール、１，１−ジ（４−ヒドロキシフェニル）シクロヘキサン、１−［１−（４−ヒドロキシフェニル）イソプロピル］−４−［１，１−ビス（４−ヒドロキシフェニル）エチル］ベンゼン等が好ましい。
【００５７】
液晶表示素子製造の分野においては、スループットの向上が非常に大きい問題であるが、当該フェノール化合物を配合することにより、高感度化が達成されスループットの向上に寄与するので好ましい。
また、当該フェノール化合物を配合することにより、レジスト膜に表面難溶化層が強く形成されるため、現像時に未露光部分のレジスト膜の膜減り量が少なく、現像時間の差から生じる現像ムラの発生が抑えられて好ましい。
【００５８】
当該フェノール化合物の中でも、上記式（Ｖ）で示される化合物（１−［１−（４−ヒドロキシフェニル）イソプロピル］−４−［１，１−ビス（４−ヒドロキシフェニル）エチル］ベンゼン）と上記式（VI）で示される化合物（ビス（２，３，５―トリメチル―４−ヒドロキシフェニル）−２−ヒドロキシフェニルメタン）は、高感度化、高残膜率化、及びリニアリティの向上効果に優れる点で特に好ましい。
【００５９】
（Ｂ）成分を本発明の組成物に配合する場合、その含有量は（Ａ）成分であるアルカリ可溶性樹脂１００質量部に対し５〜２５質量部、好ましくは１０〜２０質量部の範囲で選ばれる。
この範囲を下回ると高感度化、高残膜率化の向上効果が十分に得られず、この範囲を上回ると現像後の基板表面に残渣物が発生しやすく、また原料コストも高くなる点で好ましくない。
【００６０】
なお、システムＬＣＤ用のレジスト組成物を調整する場合には、（Ａ）成分であるアルカリ可溶性樹脂１００質量部に対し（Ｂ）成分の割合を５〜２０質量部、好ましくは７〜１５質量部の範囲で選ぶのがよい。寸法の異なるパターン形成においても、この範囲であれば、高感度化、高残膜率化の向上効果が十分に得られるからである。
【００６１】
（Ｃ）成分（感光性成分）について：
上記一般式（III）で表されるキノンジアジドエステル化物（感光性成分１）と、上記一般式（IV）で表されるキノンジアジドエステル化物（感光性成分２）とを混合して用いることにより、５００×６００ｍｍ²以上の大型ガラス基板を用いたプロセスにおいても、マクロ的な特性（塗布性、加熱ムラ特性、現像ムラ特性）に優れたレジスト材料を提供することができ、また、システムＬＣＤの製造に好適な、リニアリティに優れ、ｉ線露光に適したレジスト材料を提供することができる。
【００６２】
なお、感光性成分１の平均エステル化率は４０〜６０％が好ましく、更に好ましくは４５〜５５％である。４０％未満では現像後の膜減りが発生し易く、残膜率が低くなりやすい。６０％を超えると、著しく感度が劣る傾向がある。
【００６３】
当該感光性成分１としては、上記式（VII）で示される化合物（ビス（２−メチル−４−ヒドロキシ−５−シクロヘキシルフェニル）−３，４−ジヒドロキシフェニルメタン）の１，２−ナフトキノンジアジト−５−スルホニル化合物によるキノンジアジドエステル化物が比較的安価で、感度、解像性、リニアリティに優れたレジスト組成物を調整できる点で好ましい。この内エステル化率５０％が最も好ましい。
【００６４】
一方、感光性成分２としては、上記式（VIII）で示される２，３，４，４′−テトラヒドロキシベンゾフェノンの１，２−ナフトキノンジアジト−５−スルホニル化合物によるキノンジアジドエステル化物が好ましい。その内平均エステル化率５０〜７０％のものが好ましく、更に好ましくは５５〜６５％である。５０％未満では現像後の膜減りが発生し易く、残膜率が低くなりやすい。一方、７０％を超えると、保存安定性が低下する傾向にある。当該感光性成分２は、非常に安価で、感度に優れたレジスト組成物を調整できる点で好ましい。この内、エステル化率５９％のものが最も好ましい。
【００６５】
（Ｃ）感光性成分は、上記感光性成分１，２の他に、他のキノンジアジドエステル化物、例えば上記一般式（Ｉ）で表されるフェノール化合物と１，２−ナフトキノンジアジド−５（４）−スルホニル化合物とのエステル化物も用いることができる。
【００６６】
上記一般式（Ｉ）で表される化合物のフェノール性水酸基の全部又は一部をナフトキノンジアジドスルホン酸エステル化する方法は、常法により行うことができ、例えば、ナフトキノンジアジドスルホニルクロライドを上記一般式（Ｉ）で表される化合物と縮合させることにより得ることができる。具体的には、上記一般式（Ｉ）で表される化合物とナフトキノン−１，２−ジアジド−４（又は５）−スルホニルクロライドとを、ジオキサン、ｎ−メチルピロリドン、ジメチルアセトアミド、テトラヒドロフラン等の有機溶媒に所定量溶解し、ここにトリエチルアミン、トリエタノールアミン、ピリジン、炭酸アルカリ、炭酸水素アルカリ等の塩基性触媒を加えて反応させ、得られた生成物を水洗、乾燥して調製することができる。
【００６７】
上記他のキノンジアジドエステル化物の使用量は（Ｃ）感光性成分中、３０質量％以下、特には２５質量％以下であることが、本発明の効果を損なわない点で好ましい。
【００６８】
感光性成分１と２との混合割合は、感光性成分１の５０質量部に対して感光性成分２を４０〜６０質量部、特には４５〜５５質量部の範囲であることが望ましい。
感光性成分２の配合量がこの範囲より少ないと感度が劣る傾向があり、この範囲より多いとレジスト組成物の解像性、リニアリティが劣る傾向がある。
【００６９】
本発明の組成物において、（Ｃ）成分の配合量は、（Ａ）成分であるアルカリ可溶性樹脂と（Ｂ）成分との合計量１００質量部に対し１５〜４０質量部、好ましくは２０〜３０質量部の範囲で選ぶのがよい。（Ｃ）成分の配合量が上記範囲を下回るとパターンに忠実な画像が得られず、転写性も低下する。一方、（Ｃ）成分の配合量が上記範囲を上回ると、感度や解像性が劣化し、また現像処理後に残渣物が発生する傾向がある。
【００７０】
なお、システムＬＣＤ用のレジスト組成物を調整する場合には、（Ａ）成分であるアルカリ可溶性樹脂と（Ｂ）成分との合計量１００質量部に対し２０〜４０質量部、好ましくは２５〜３５質量部の範囲で選ばれる。
【００７１】
本発明組成物は、（Ａ）〜（Ｃ）成分及び各種添加成分とを、有機溶媒である下記（Ｄ）成分に溶解して溶液の形で用いるのが好ましい。
【００７２】
（Ｄ）成分（有機溶媒）について：
本発明に用いられる有機溶媒の例としては、アセトン、メチルエチルケトン、シクロヘキサノン、メチルイソアミルケトン、２−ヘプタノン等のケトン類；エチレングリコール、プロピレングリコール、ジエチレングリコール、エチレングリコールモノアセテート、プロピレングリコールモノアセテート、ジエチレングリコールモノアセテート、あるいはこれらのモノメチルエーテル、モノエチルエーテル、モノプロピルエーテル、モノブチルエーテルまたはモノフェニルエーテル等の多価アルコール類およびその誘導体；ジオキサンのような環式エーテル類；および乳酸エチル、酢酸メチル、酢酸エチル、酢酸ブチル、ピルビン酸メチル、ピルビン酸エチル、メトキシプロピオン酸メチル、エトキシプロピオン酸エチル等のエステル類を挙げることができる。これらは単独で用いてもよいし、２種以上を混合して用いてもよい。
【００７３】
それらの内でもプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）が、本発明レジスト組成物に優れた塗布性を与え、大型ガラス基板上でのレジスト被膜に優れた膜厚均一性を与える点で好ましい。
ＰＧＭＥＡは単独溶媒で用いることが最も好ましいが、ＰＧＭＥＡ以外の溶媒もこれと混合して用いることができる。そのような溶媒としては、例えば乳酸エチル、γ−ブチロラクトン、プロピレングリコールモノブチルエーテルなどが挙げられる。
【００７４】
乳酸エチルを用いる場合は、ＰＧＭＥＡに対して質量比で０．１〜１０倍量、好ましくは１〜５倍量の範囲で配合することが望ましい。
また、γ−ブチロラクトンを用いる場合は、ＰＧＭＥＡに対して質量比で０．０１〜１倍量、好ましくは０．０５〜０．５倍量の範囲で配合することが望ましい。
【００７５】
液晶表示素子製造の分野においては、通常レジスト被膜を０．５〜２．５μｍ、特には１．０〜２．０μｍの膜厚でガラス基板上に形成する必要があるが、そのためには、これら有機溶媒を使用して、組成物中の上記（Ａ）〜（Ｃ）成分の総量が、組成物の全質量に対して３０質量％以下、好ましくは２０〜２８質量％になるように調整することが、塗布性に優れる液晶表示素子製造用レジスト材料として好ましい。
この場合任意に用いられる下記（Ｅ）成分の量も勘案して、溶媒（Ｄ）の使用量は、組成物の全質量に対して６５〜８５質量％、好ましくは７０〜７５質量％であることが好ましい。
【００７６】
（Ｅ）成分（その他の添加剤）について
本発明においては、本発明の目的を損なわない範囲において、ハレーション防止のための紫外線吸収剤、例えば２，２′，４，４’−テトラヒドロキシベンゾフェノン、４−ジメチルアミノ−２′，４′−ジヒドロキシベンゾフェノン、５−アミノ−３−メチル−１−フェニル−４−（４−ヒドロキシフェニルアゾ）ピラゾール、４−ジメチルアミノ−４’−ヒドロキシアゾベンゼン、４−ジエチルアミノ−４’−エトキシアゾベンゼン、４−ジエチルアミノアゾベンゼン、クルクミン等や、またストリエーション防止のための界面活性剤、例えばフロラードＦＣ−４３０、ＦＣ４３１（商品名、住友３Ｍ（株）製）、エフトップＥＦ１２２Ａ、ＥＦ１２２Ｂ、ＥＦ１２２Ｃ、ＥＦ１２６（商品名、トーケムプロダクツ（株）製）等のフッ素系界面活性剤、ベンゾキノン、ナフトキノン、ｐ−トルエンスルホン酸等の保存安定化剤、さらに必要に応じて付加的樹脂、可塑剤、安定化剤、コントラスト向上剤等の慣用の添加剤を本発明の目的に支障のない範囲で添加含有させることができる。
【００７７】
本発明の組成物を用いた液晶表示素子製造用レジストパターンの好適な形成方法について一例を示す。まず、ガラス角基板上に、（Ａ）〜（Ｃ）成分、および必要に応じて用いられる添加成分（Ｅ）を前記したような適当な溶媒（Ｄ）に溶かした溶液をスピンナー等で塗布し、塗膜を形成する。このとき用いるガラス基板は５００×６００mm²以上、特には、５５０〜６５０mm²以上の大型板であることができる。
【００７８】
本発明の組成物を用いれば、このように大型のガラス基板を用いた液晶表示素子（システムＬＣＤを含む）の製造においても、マクロ的（塗布性、加熱ムラ特性、現像ムラ特性）に優れ、リニアリティにも優れたレジストパターンを得ることができる。
【００７９】
次いで、この塗膜が形成されたガラス基板を１００〜１４０℃程度で加熱乾燥（プリべーク）して感光層を形成させる。次いで紫外線を発光する光源、例えば低圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプ等を用い、所望のマスクパターンを介して選択的露光を行う。
【００８０】
なお、システムＬＣＤ等の製造において、この選択的露光はパターン寸法の異なるレジストパターン形成用マスクパターンが描かれたマスクを用いて行われるものであり、前記ガラス基板上にパターン寸法の異なるレジストパターンを同時に形成することができる。例えば、この選択的露光はパターン寸法０．５〜２．５μｍのレジストパターン形成用マスクパターンと、パターン寸法３〜１０μｍのレジストパターン形成用マスクパターンとが描かれたマスク（レチクル）を用いて行うことが出来る。このような寸法の異なるパターンを同時に形成するときも、本発明レジスト組成物は優れたリニアリティの効果を発揮する。
このとき、微細なパターンを形成するために、ｉ線（３６５nm）を用いることが好ましい。
【００８１】
次にこの露光済みレジスト被覆ガラス基板を現像液、例えば１〜１０質量％テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）水溶液のようなアルカリ性水溶液を基板の一方の端部から他方の端部に液盛りし、又は中心付近の上部に設置された現像液滴下ノズルより基板表面全体に現像液を行き渡らせる。
上記基板の一方の端部から他方の端部にアルカリ性水溶液を液盛りする方法は大型のガラス基板を用いたレジストパターンの形成の場合に装置をコンパクトにすることができて、極めて有用であるが、一方の端部から他方の端部に液盛りしたとき、それぞれの端部での液盛りの時期にずれがあるから、それら端部でのレジスト組成物とアルカリ性水溶液の接触の時間が異なり、現像ムラの原因となる。
本発明レジスト組成物を用いると、この現像ムラが極めて小さく実用上問題とならない程にすることができる。
【００８２】
そして５０〜６０秒間程度静置して現像し、上記ガラス基板上にレジストパターンを形成する。その後、このレジストパターン表面に残った現像液を純水などのリンス液を用いて洗い落とすリンス工程を行う。
【００８３】
【実施例】
ポジ型ホトレジスト組成物の諸物性は次のようにして求めた。
（１）加熱ムラ評価：
試料をスピンナーを用いてＣｒ膜が形成されたガラス基板（５５０×６５０ｍｍ²）上に塗布したのち、ホットプレートの温度を１３０℃とし、約１ｍｍの間隔をあけたプロキシミティベークにより６０秒間の第１回目の乾燥を行い、次いでホットプレートの温度を１２０℃とし、０．５ｍｍの間隔をあけたプロキシミティベークにより６０秒間の第２回目の乾燥を施し、膜厚１．５μｍのレジスト被膜を形成した。
【００８４】
なお第２回目の乾燥工程において、基板周縁部Ａでは基板温度は約１０５℃であり、基板中心部Ｂでは基板温度は約１１０℃であり、基板コア部Ｃでは基板温度は約１１５℃であった（図１参照）。
【００８５】
次いで３．０μｍＬ＆Ｓ（ラインアンドスペース）のレジストパターンを再現するためのマスクパターンが描かれたテストチャートマスク（レチクル）を介してミラープロジェクション・アライナーＭＰＡ−６００ＦＡ（商品名、キャノン社製）を用い、基板中心部Ｂにおいて３．０μｍＬ＆Ｓを寸法通りに再現することのできる露光量で選択的露光を行った。但し、露光量は３０ｍＪ以下の条件で行った。
次いで、２３℃、２．３８質量％テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）水溶液に６０秒間接触させ、３０秒間水洗し、スピン乾燥した。
【００８６】
その後、得られたレジストパターンの断面形状を、上記基板周縁部Ａ、中心部Ｂ、コア部ＣについてＳＥＭ（走査型電子顕微鏡）写真にて観察し、パターン寸法が２．９０〜３．１０μｍであったものを○、２．９０μｍ未満であったものを×、３．１０μｍ超であったものを××として表し、その結果を表２に示す。
【００８７】
（２）現像ムラ評価：
試料をスピンナーを用いてＣｒ膜が形成されたガラス基板（５５０×６５０ｍｍ²）上に塗布したのち、ホットプレートの温度を１３０℃とし、約１ｍｍの間隔をあけたプロキシミティベークにより６０秒間の第１回目の乾燥を行い、次いでホットプレートの温度を１２０℃とし、０．５ｍｍの間隔をあけたプロキシミティベークにより６０秒間の第２回目の乾燥を施し、膜厚１．５μｍのレジスト被膜を形成した。
【００８８】
次いで３．０μｍＬ＆Ｓのレジストパターンを再現するためのマスクパターンが描かれたテストチャートマスク（レチクル）を介してミラープロジェクション・アライナーＭＰＡ−６００ＦＡ（キャノン社製）を用い、基板中心部Ｙにおいて３．０μｍＬ＆Ｓを寸法通りに再現することのできる露光量で選択的露光を行った。但し、露光量は３０ｍＪ以下の条件で行った。
【００８９】
次いで、２３℃、２．３８質量％ＴＭＡＨ水溶液をスリットコータノズルを有する現像装置（装置名：ＴＤ−３９０００デモ機、東京応化工業（株）製）を用いて、基板端部ＸからＺ（図２参照）にかけて、１０秒間を掛けて基板上に液盛りし、５５秒間保持した後、３０秒間水洗し、スピン乾燥した。
なお基板と現像液との接触時間は、基板端部Ｘでは６５秒間、基板中心部Ｙでは６０秒間、基板端部Ｚでは５５秒間であった。
【００９０】
その後、得られたレジストパターンの断面形状を、上記基板端部Ｘ、中心部Ｙ、端部ＺについてＳＥＭ（走査型電子顕微鏡）写真にて観察し、パターン寸法が２．８０〜３．２０μｍであったものを○、２．８０μｍ未満であったものを×、３．２０μｍ超であったものを××として表し、その結果を表２に示す。
【００９１】
（３）リニアリティ評価：
試料をスピンナーを用いてＣｒ膜が形成されたガラス基板（５５０×６５０ｍｍ²）上に塗布したのち、ホットプレートの温度を１３０℃とし、約１ｍｍの間隔をあけたプロキシミティベークにより６０秒間の第１回目の乾燥を行い、次いでホットプレートの温度を１２０℃とし、０．５ｍｍの間隔をあけたプロキシミティベークにより６０秒間の第２回目の乾燥を施し、膜厚１．５μｍのレジスト被膜を形成した。
【００９２】
次いで３．０μｍＬ＆Ｓ、２．０μｍＬ＆Ｓ、及び１．５μｍＬ＆Ｓのレジストパターンを再現するためのマスクパターンが一つのマスク上に描かれたテストチャートマスク（レチクル）を介してｉ線露光装置（装置名：ＦＸ−７０２Ｊ、ニコン社製）を用い、３．０μｍＬ＆Ｓを寸法通りに再現することのできる露光量にて選択的露光を行った。
【００９３】
次いで、２３℃、２．３８質量％ＴＭＡＨ水溶液をスリットコータノズルを有する現像装置（装置名：ＴＤ−３９０００デモ機、東京応化工業（株）製）を用いて、基板端部ＸからＺ（図２参照）にかけて、１０秒間を掛けて基板上に液盛りし、５５秒間保持した後、３０秒間水洗し、スピン乾燥した。
【００９４】
その後、得られたレジストパターンの断面形状をＳＥＭ（走査型電子顕微鏡）写真にて観察し、３．０μｍＬ＆Ｓ、２．０μｍＬ＆Ｓ、及び１．５μｍＬ＆Ｓのレジストパターンの再現性を実際にレジストパターン寸法を求めることにより評価した。その結果を表３に示す。
【００９５】
(実施例１)
（Ａ）成分：
アルカリ可溶性樹脂 １００質量部
[ｍ−クレゾール３５モル％とｐ−クレゾール６５モル％の混合物にシュウ酸とホルムアルデヒドを加え縮合反応して得られた重量平均分子量（Ｍｗ）４０００のクレゾールノボラック樹脂に分別処理を施して得られた、Ｍｗ＝４５００、フェノール類の２核体含有量が約６％のクレゾールノボラック樹脂（製品名：ＧＴＲ−Ｍ２、群栄化学社製）を使用した。なお、フェノール類の２核体含有量は、下記の装置と条件によるＧＰＣ測定で行った。]
【００９６】
装置名：ＳＹＳＴＥＭ １１（昭和電工社製）
プレカラム：ＫＦ−Ｇ（ＳＨＯＤＥＸ社製）
カラム：ＫＦ−８０２（ＳＨＯＤＥＸ社製）
検出器：ＵＶ４１（２８０ｎｍで測定）
溶媒等の条件：流量１．０ｍｌ／ｍｉｎでテトラヒドロフランを流し、３５℃にて測定した。
【００９７】
（Ｂ）成分：
感度向上剤（Ｂ１：上記式（Ｖ）で表されるフェノール化合物）：１５質量部
（Ｃ）成分：
感光性成分１／感光性成分２[５０／５０（質量比）]：２６質量部
（感光性成分１：Ｃ１：上記式（VII）で示される化合物１モルと１，２−ナフトキノンジアジド−５−スルホン酸クロリド（以下「５−ＮＱＤ」と記述する）２モルとのエステル化物（エステル化率５０％）；感光性成分２：Ｃ２：上記式（VIII）で示される化合物１モルと５−ＮＱＤ２．３４モルとのエステル化物（エステル化率５９％）
（Ｄ）成分：
溶媒（ＰＧＭＥＡ）：４２３質量部
【００９８】
上記（Ａ）〜（Ｄ）成分を均一に溶解した後、これを孔径０．２μｍのメンブランフィルターを用いてろ過し、ポジ型ホトレジスト組成物を調製した。この組成物について、上記加熱ムラ及び現像ムラを測定した。その結果を上述のように表２に示す。
【００９９】
（実施例２〜６、比較例１〜１０）
（Ａ）〜（Ｄ）の各成分を下記表１に記載したものに代えた以外は実施例１と同様にして各種ポジ型ホトレジスト組成物を調製した。この組成物について、上記加熱ムラ、現像ムラ、及びリニアリティを測定した。その結果を上述のように表２、３に示す。
【０１００】
各実施例及び比較例において用いた化合物の略号及びその内容については、Ｂ１，Ｃ１，Ｃ２は上記のとおりであるが、Ｂ２，Ｃ２’，Ｃ３，Ｃ４及びＥＬは次の通りである。
【０１０１】
【化１６】

（但し、Ｃ２’，Ｃ３及びＣ４のエステル化率はそれぞれ７５％、６６％、及び６６％である。）
【０１０２】
【表１】

【０１０３】
【表２】

【０１０４】
表２から明らかなように、本発明で特定される成分を用いないときはホトレジスト組成物膜の現像ムラの良い場合はあるが、加熱ムラが悪いことが明らかである。
【０１０５】
【表３】

【０１０６】
表３から明らかなように、本発明で特定される成分を用いないときはホトレジスト組成物膜のリニアリティが悪いことが明らかである。
【０１０７】
【発明の効果】
本発明によれば、安価であって、５００×６００ｍｍ²以上の大型ガラス基板を用いたプロセスにおいても、マクロ的な特性（塗布性、加熱ムラ特性、現像ムラ特性）に優れたレジスト材料および液晶表示素子製造用レジストパターンの形成方法を提供することができる。更に、本発明によれば、システムＬＣＤの製造に好適な、リニアリティに優れ、ｉ線露光に適したレジスト材料および液晶表示素子製造用レジストパターンの形成方法を提供することができる。
【図面の簡単な説明】
【図１】 加熱ムラ評価のために、ポジ型ホトレジスト組成物をガラス基板に塗布し、べークし乾燥したときの基板周辺部Ａ、基板中心部Ｂ、及び基板コア部Ｃの各領域を表す図。
【図２】 現像ムラ評価及びリニアリティ評価のために、ポジ型ホトレジスト組成物をガラス基板に塗布し、べークし乾燥し、パターン露光した後、スリットコーターを有する現像装置で現像液を基板端部ＸからＺにかけて液盛りする旨の説明図。[0001]
[Field of the Invention]
  The present inventionMethod for forming resist pattern for liquid crystal display device manufacturingIn particular, liquid crystal display elements, especially 500 × 600 mm²Suitable for manufacturing liquid crystal display elements using the above large glass substratesMethod for forming resist pattern for liquid crystal display device manufacturingAnd suitable for the production of system LCDMethod for forming resist pattern for liquid crystal display device manufacturingAbout.
[0002]
[Prior art]
In the field of manufacturing liquid crystal display elements using glass substrates, novolaks are used in the manufacture of semiconductor elements because they are relatively inexpensive and can form resist patterns with excellent sensitivity, resolution, and shape. Many positive photoresist materials comprising a resin-quinonediazide group-containing compound system are used.
[0003]
However, in the manufacture of a semiconductor device, a disk type silicon wafer having a maximum diameter of 8 inches (about 200 mm) to 12 inches (about 300 mm) is used, whereas in the manufacture of a liquid crystal display device, 500 × 600 mm.²The above square glass substrate is used.
As described above, in the field of manufacturing liquid crystal display elements, the substrate to which the resist composition is applied is naturally different in terms of material and shape, but is greatly different from the silicon wafer in terms of its size.
Therefore, a resist material for manufacturing a liquid crystal display element has been focused on improving macro characteristics rather than micro characteristics required in the semiconductor element manufacturing field.
[0004]
Such macroscopic characteristics include the formation of a coating film with no coating unevenness over the entire surface of a wide substrate, and the shape and dimensional stability against heating unevenness during heat treatment caused by the large substrate. Examples thereof include forming a good resist pattern, and forming a resist pattern with less shape unevenness due to a large substrate and good shape and dimensional stability during development. In addition, since a large amount of resist material is consumed in the production of the liquid crystal display element, it is desired that the material be an inexpensive material in addition to these characteristics.
[0005]
Such a characteristic cannot be sufficiently obtained by a conventional resist material for manufacturing a semiconductor element. For example, a material specifically described in Japanese Patent Laid-Open No. 10-14283 has the above-mentioned macro characteristic. It cannot be fully expressed.
[0006]
On the other hand, there have been many reports as resist materials for producing liquid crystal elements. For example, JP-A-9-160231, JP-A-9-21855, JP-A-2000-112120, JP-A-2000-131835. And JP-A-2000-181055 and 2001-75272.
[0007]
These materials are inexpensive and 360x460mm²A resist pattern having excellent coating properties, sensitivity, resolution, shape, and dimensional stability can be formed on a relatively small substrate. However, the board size is 500x600mm²For the above large substrates, there is a problem in coating properties, and development occurs due to changes in pattern dimensions due to heating unevenness at the peripheral and central portions of the substrate and differences in development time between the end portions and the end portions of the substrate. There is a problem that unevenness increases.
[0008]
Therefore, in the field of liquid crystal display element manufacturing, which is increasing in size every day, 500 × 600 mm²Even in the process using the above glass substrate, it has been desired to realize a resist material having excellent macro characteristics.
[0009]
On the other hand, as a next-generation LCD (liquid crystal display element), an integrated circuit such as a driver, a DAC, an image processor, a video controller, and a RAM is formed on a single glass substrate at the same time as the display portion. Technological development for high-performance LCDs is actively underway (Semiconductor FPD World 2001.9, pp.50-67).
[0010]
However, since the pattern size of the display portion is about 3 to 10 μm, the pattern size of the integrated portion needs to be formed as fine as about 0.5 to 2.5 μm. Linearity [Characteristics that reproduce the mask dimensions on the reticle when exposed under the same exposure conditions (the mask dimensions on the reticle are different, but the same exposure) under the same conditions) Is desired to be excellent.
[0011]
In addition, when forming a fine resist pattern of about 0.5 to 2.5 μm, a photolithographic technique using a shorter wavelength i-line (365 nm) exposure than the conventional g-line (436 nm) exposure is necessary. It becomes.
However, conventional resist materials for manufacturing liquid crystal display elements have excellent linearity and are not suitable for i-line exposure, and it has been desired to develop materials that can solve these problems.
[0012]
[Problems to be solved by the invention]
  One of the objects of the present invention is inexpensive and 500 × 600 mm²Resist material with excellent macro characteristics (applicability, uneven heating characteristics, uneven development characteristics) even in the above process using large glass substratesAnd method for forming resist pattern for manufacturing liquid crystal display elementIs to provide.
  Another object of the present invention is to provide a resist material suitable for the production of a system LCD, excellent in linearity and suitable for i-line exposure.And method for forming resist pattern for manufacturing liquid crystal display elementIs to provide.
[0013]
[Means for Solving the Problems]
As a result of diligent research to solve the above problems, the present inventors have obtained a specific compounding ratio, an alkali-soluble resin, a specific phenol compound (sensitivity improver), and two specific quinonediazide esterified products (photosensitive components). ) Has been found to be a material that can solve the above problems, and has led to the present invention.
[0014]
The present invention provides (1) the following positive photoresist composition of 500 × 600 mm ² Applying on the above large glass substrate and forming a coating film,
(2) a step of heat-treating (pre-baking) the glass substrate on which the coating film has been formed to form a resist coating on the glass substrate;
(3) a step of selectively exposing the resist film;
(4) performing a development process using an alkaline aqueous solution on the resist film after the selective exposure to form a resist pattern on the glass substrate; and
(5) A method for forming a resist pattern for manufacturing a liquid crystal display element, comprising a rinsing step of washing off the developer remaining on the surface of the resist pattern.
  The positive resist composition used in the present invention (hereinafter sometimes referred to as “the positive photoresist composition of the present invention”, “the resist composition of the present invention” or “the composition of the present invention”)(A) For 100 parts by mass of the alkali-soluble resin, (B) the following general formula (I)
[0015]
[Chemical 9]

[0016]
[In the formula, R¹~ R⁸Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms; R⁹~ R¹¹Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Q is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, R⁹Or a group represented by the following chemical formula (II):
[0017]
[Chemical Formula 10]

[0018]
(Wherein R¹²And R¹³Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms; A and b represent an integer of 1 to 3; d represents an integer of 0 to 3; n represents an integer of 0 to 3]
5 to 25 parts by mass of a phenol compound represented by the formula (C) with respect to 100 parts by mass of the total mass of the component (A) and the component (B): (C) the following general formula (III)
[0019]
Embedded image

[0020]
(Wherein R¹⁴Independently represents an alkyl group having 1 to 5 carbon atoms, D independently represents a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group, and at least one of D is 1,2-naphtho A quinonediazide-5-sulfonyl group, l and m each independently represent 1 or 2)
A quinonediazide esterified product (photosensitive component 1) represented by formula (IV):
[0021]
Embedded image

[0022]
(In the formula, D independently represents a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group, and at least one of D is a 1,2-naphthoquinonediazide-5-sulfonyl group.)
A positive photoresist composition comprising a mixture of photosensitive components consisting of a quinonediazide esterified product (photosensitive component 2) represented by the formula: in an amount of 15 to 40 parts by mass, and further containing (D) an organic solvent. It is a thing.
[0023]
  According to the present invention, it is inexpensive and has a size of 500 × 600 mm.²Even in the process using the above large glass substrate, a resist material having excellent macro characteristics (coating property, heating unevenness characteristic, development unevenness characteristic) can be provided. Furthermore, it is possible to provide a resist material excellent in linearity and suitable for i-line exposure, which is suitable for manufacturing a system LCD.
  The liquid crystal display element manufacturing resist pattern thus formed has a size of 500 × 600 mm. ² Even those made using the above-described large glass substrate can have high dimensional accuracy.
[0024]
The component (B) is represented by the following formula (V) or (VI)
[0025]
Embedded image

[0026]
It is preferable that it is a phenol compound represented by these. These compounds are particularly excellent in the effect of increasing the sensitivity, increasing the residual film ratio, and improving the linearity of the photoresist film.
[0027]
The component (A) contains 60 mol% or more of p-cresol repeating units and 30 mol% or more of m-cresol repeating units in all phenolic repeating units, and has a polystyrene-equivalent weight average molecular weight (Mw). ) Is preferably a novolak resin of 2000 to 8000. Such a resin has particularly good sensitivity and hardly changes in sensitivity to temperature unevenness during the heat treatment.
[0028]
The photosensitive component 1 has the following formula (VII)
[0029]
Embedded image

[0030]
A quinonediazide esterified product having an average esterification rate of 40 to 60% between a phenol compound represented by the formula (1) and a 1,2-naphthoquinonediazide-5-sulfonyl compound, and photosensitive component 2 is represented by the following formula (VIII):
[0031]
Embedded image

[0032]
A quinonediazide esterified product having an average esterification rate of 50 to 70% between the phenol compound represented by the formula (1) and a 1,2-naphthoquinonediazide-5-sulfonyl compound is preferable.
By using these two types of photosensitive components, the positive photoresist of the present invention has excellent macro characteristics (coating properties, heating unevenness characteristics, development unevenness characteristics), a high residual film ratio, and good sensitivity. It is possible to provide a resist material having good storage stability.
[0033]
The resist composition of the present invention preferably contains propylene glycol monomethyl ether acetate (PGMEA) as the component (D). By containing PGMEA, this invention resist composition is excellent in applicability | paintability, and becomes excellent in the film thickness uniformity of the resist film on a large sized glass substrate.
[0034]
The total mass of the components (A), (B) and (C) is preferably 30% by mass or less based on the total mass of the positive photoresist composition. In this way, by increasing the content of the organic solvent in the positive photoresist composition and reducing the total amount of the components (A), (B) and (C), the coatability of the positive photoresist composition is particularly improved. It can be excellent.
[0035]
The positive photoresist composition of the present invention is particularly preferably used for the production of a liquid crystal display element. This is because the positive photoresist composition of the present invention is excellent in macro characteristics (coating properties, heating unevenness characteristics, development unevenness characteristics), has a high residual film ratio, and has good sensitivity.
[0036]
The liquid crystal display element has a size of 500 × 600 mm.²It is preferable that the large glass substrate is used.
[0037]
It is particularly preferred that the positive photoresist composition of the present invention is for the production of a system LCD. This is because the positive photoresist composition of the present invention is excellent in linearity and can form a resist pattern by simultaneously exposing a small pattern and a large pattern by i-line exposure.
[0038]
The system LCD is 500x600mm²It is preferable that the large glass substrate is used.
[0039]
The system LCD is preferably made using an i-line (365 nm) exposure process. This is because a fine resist pattern of about 0.5 to 2.5 μm can be formed satisfactorily.
[0042]
In the present invention, the step (3) of performing the selective exposure is performed using a mask on which a resist pattern forming mask pattern having a different pattern dimension is drawn. A resist pattern forming method for producing a liquid crystal display element, wherein different resist patterns are formed simultaneously.
The masks on which the resist pattern forming mask patterns having different pattern dimensions are drawn include a resist pattern forming mask pattern having a pattern dimension of 0.5 and a pattern dimension of 0.5 to 2.5 μm and a resist pattern forming pattern having a pattern dimension of 3 to 10 μm. It is preferable that the etching is performed using a mask (reticle) drawn with at least a mixture of mask patterns. In this case, it is more preferable to simultaneously form a resist pattern having a pattern size of 0.5 to 2.5 μm and a resist pattern having a pattern size of 3 to 10 μm on the glass substrate.
[0043]
Thus, the positive photoresist composition of the present invention can simultaneously form patterns having different dimensions.
[0044]
The step (3) of performing selective exposure is preferably performed by an exposure process using i-line (365 nm) as a light source.
This is because a pattern with high dimensional accuracy can be formed by using i-line, and the positive photoresist composition of the present invention enables exposure using such i-line and subsequent development.
[0045]
DETAILED DESCRIPTION OF THE INVENTION
About component (A) (alkali-soluble resin):
The alkali-soluble resin as the component (A) is not particularly limited, and can be arbitrarily selected from those that can be usually used as a film-forming substance in a positive photoresist composition. For example, a phenolic resin, an acrylic resin, a copolymer of styrene and acrylic acid, a polymer of hydroxystyrene, polyvinylphenol, poly α-methylvinylphenol, etc., known as a film forming resin for a positive photoresist composition Can be mentioned. Among these, a phenol resin is particularly preferably used, and among them, a novolak resin that is easily dissolved in an alkaline aqueous solution without swelling and excellent in developability is preferable.
[0046]
Examples of phenol resins include condensation reaction products of phenols and aldehydes, condensation reaction products of phenols and ketones, vinyl phenol polymers, isopropenyl phenol polymers, and hydrogen of these phenol resins. Examples include addition reaction products.
[0047]
Examples of phenols that form the phenol resin include phenol, m-cresol, p-cresol, o-cresol, 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, and the like. Xylenols; m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol, 2 Alkylphenols such as tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol; p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol , P-p Alkoxyphenols such as poxyphenol and m-propoxyphenol; isopropenylphenols such as o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol and 2-ethyl-4-isopropenylphenol Arylphenols such as phenylphenol; polyhydroxyphenols such as 4,4′-dihydroxybiphenyl, bisphenol A, resorcinol, hydroquinone, pyrogallol, and the like. These may be used alone or in combination of two or more. Among these phenols, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, and 2,3,5-trimethylphenol are particularly preferable.
[0048]
Examples of the aldehydes include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, butyraldehyde, trimethylacetaldehyde, acrolein, crotonaldehyde, cyclohexanealdehyde, furfural, furylacrolein, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, α-phenylpropyl. Aldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p- Chlorobenzaldehyde, cinnamon Examples include aldehyde. These may be used alone or in combination of two or more. Among these aldehydes, formaldehyde is preferable because it is easily available. In particular, in order to improve heat resistance, it is preferable to use a combination of hydroxybenzaldehydes and formaldehyde.
[0049]
Examples of the ketones include acetone, methyl ethyl ketone, diethyl ketone, and diphenyl ketone. These may be used alone or in combination of two or more. In the combination of phenols and ketones, the combination of pyrogallol and acetone is particularly preferable.
[0050]
The condensation reaction product of phenols and aldehydes or ketones can be produced by a known method in the presence of an acidic catalyst. In this case, hydrochloric acid, sulfuric acid, formic acid, oxalic acid, paratoluenesulfonic acid, etc. can be used as the acidic catalyst. The condensation product obtained in this manner is preferably a product obtained by cutting a low molecular region by performing a treatment such as fractionation, because it is excellent in heat resistance. In the treatment such as fractionation, the resin obtained by the condensation reaction is dissolved in a good solvent, for example, alcohol such as methanol or ethanol, ketone such as acetone or methyl ethyl ketone, ethylene glycol monoethyl ether acetate, tetrahydrofuran or the like, and then poured into water. It is carried out by a method such as precipitation.
[0051]
In the present invention, among all the above-mentioned phenolic repeating units, the p-cresol repeating unit is contained in an amount of 60 mol% or more, and the m-cresol repeating unit is contained in an amount of 30 mol% or more. A novolak resin having a molecular weight (Mw) of 2000 to 8000 is preferred.
[0052]
If the p-cresol repeating unit is less than 60 mol%, the sensitivity is likely to change due to temperature unevenness during the heat treatment, and if the m-cresol repeating unit is less than 30 mol%, the sensitivity tends to be inferior.
[0053]
The alkali-soluble resin of the present invention may contain other phenol-based repeating units such as a xylenol-based repeating unit and a trimethylphenol-based repeating unit, but most preferably a p-cresol-based repeating unit. It is a two-component novolak resin composed of 60 to 70 mol% and m-cresol repeating units 40 to 30 mol%, and is a binuclear phenol (condensate molecule having two phenol nuclei).
A novolak resin having a low content of low molecular weight phenols such that the content is 10% or less in the GPC (gel permeation chromatography) method is preferred. The dinuclear body sublimates during pre-baking or post-baking at a high temperature (for example, 130 ° C.) to contaminate the top plate of the furnace, and further stains the glass substrate coated with the resist, thereby reducing the yield. Because.
[0054]
Regarding component (B) (sensitivity improver):
In the composition of the present invention, the phenol compound represented by the general formula (I) is used as the component (B).
[0055]
Examples of the component (B) include tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, and bis (4-hydroxy-2,3,5-trimethyl). Phenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethyl) Phenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenol) ) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxy Phenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2,4-dihydroxyphenylmethane, bis (4-hydroxyphenyl) -3-methoxy-4-hydroxyphenylmethane, bis (5-cyclohexyl-4) -Hydroxy-2-methylphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methyl) Phenyl) -2-hydroxyphenylmethane, bis (5-si Rohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenylmethane, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] Benzene, 1- [1- (3-methyl-4-hydroxyphenyl) isopropyl] -4- [1,1-bis (3-methyl-4-hydroxyphenyl) ethyl] benzene, 2- (2,3,4 -Trihydroxyphenyl) -2- (2 ', 3', 4'-trihydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (2 ', 4'-dihydroxyphenyl) propane, 2 -(4-hydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 2- (3-fluoro-4-hydroxyphenyl) -2- (3'-fluoro B-4'-hydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (4 '-Hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (4'-hydroxy-3', 5'-dimethylphenyl) propane, bis (2,3,4-trihydroxy) Phenyl) methane, bis (2,4-dihydroxyphenyl) methane, 2,3,4-trihydroxyphenyl-4′-hydroxyphenylmethane, 1,1-di (4-hydroxyphenyl) cyclohexane, 2,4-bis [1- (4-hydroxyphenyl) isopropyl] -5-hydroxyphenol and the like.
[0056]
Among these, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxy are particularly excellent in sensitivity improvement effect. Phenylmethane, 2,4-bis [1- (4-hydroxyphenyl) isopropyl] -5-hydroxyphenol, 1,1-di (4-hydroxyphenyl) cyclohexane, 1- [1- (4-hydroxyphenyl) isopropyl ] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene and the like are preferable.
[0057]
In the field of liquid crystal display device manufacture, improvement in throughput is a very large problem, but blending the phenol compound is preferable because high sensitivity is achieved and contribution to improvement in throughput.
Also, by blending the phenol compound, a poorly surface-solubilized layer is strongly formed on the resist film, so that the amount of unexposed resist film loss during development is small, and development unevenness occurs due to differences in development time. Is preferable.
[0058]
Among the phenol compounds, the compound represented by the above formula (V) (1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene) and the above The compound represented by the formula (VI) (bis (2,3,5-trimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane) is excellent in high sensitivity, high residual film ratio, and linearity improvement effect. Particularly preferred in terms.
[0059]
(B) When mix | blending a component with the composition of this invention, the content is 5-25 mass parts with respect to 100 mass parts of alkali-soluble resin which is (A) component, Preferably it selects in the range of 10-20 mass parts. It is.
Below this range, the effect of improving sensitivity and high residual film ratio cannot be obtained sufficiently, and above this range, residues are likely to be generated on the substrate surface after development, and the cost of raw materials increases. It is not preferable.
[0060]
In addition, when preparing the resist composition for system LCD, the ratio of (B) component is 5-20 mass parts with respect to 100 mass parts of alkali-soluble resin which is (A) component, Preferably 7-15 mass parts It is better to choose in the range. This is because, in the pattern formation with different dimensions, the effect of improving the sensitivity and the remaining film ratio can be sufficiently obtained within this range.
[0061]
Regarding component (C) (photosensitive component):
By mixing and using the quinonediazide esterified product (photosensitive component 1) represented by the general formula (III) and the quinonediazide esterified product (photosensitive component 2) represented by the general formula (IV), 500 × 600mm²Even in the process using the above large glass substrate, it is possible to provide a resist material having excellent macro characteristics (coating properties, heating unevenness characteristics, development unevenness characteristics), and suitable for the production of system LCDs. A resist material that is excellent in linearity and suitable for i-line exposure can be provided.
[0062]
In addition, the average esterification rate of the photosensitive component 1 is preferably 40 to 60%, more preferably 45 to 55%. If it is less than 40%, film loss after development tends to occur and the remaining film ratio tends to be low. If it exceeds 60%, the sensitivity tends to be remarkably inferior.
[0063]
The photosensitive component 1 includes 1,2-naphthoquinonediazite of a compound represented by the above formula (VII) (bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) -3,4-dihydroxyphenylmethane). A quinonediazide esterified product with a -5-sulfonyl compound is preferable because it is relatively inexpensive and can adjust a resist composition excellent in sensitivity, resolution, and linearity. Of these, an esterification rate of 50% is most preferred.
[0064]
On the other hand, the photosensitive component 2 is preferably a quinonediazide esterified product of 1,3,4-naphthoquinonediazito-5-sulfonyl compound of 2,3,4,4′-tetrahydroxybenzophenone represented by the above formula (VIII). Among them, those having an average esterification rate of 50 to 70% are preferred, and more preferably 55 to 65%. If it is less than 50%, film loss after development tends to occur and the remaining film ratio tends to be low. On the other hand, when it exceeds 70%, the storage stability tends to decrease. The photosensitive component 2 is preferable because it is very inexpensive and can adjust a resist composition having excellent sensitivity. Of these, those having an esterification rate of 59% are most preferred.
[0065]
(C) In addition to the photosensitive components 1 and 2, the photosensitive component includes other quinonediazide esterified products, for example, the phenol compound represented by the above general formula (I) and 1,2-naphthoquinonediazide-5 (4). An esterified product with a sulfonyl compound can also be used.
[0066]
The method for converting all or part of the phenolic hydroxyl group of the compound represented by the general formula (I) into a naphthoquinone diazide sulfonic acid ester can be performed by a conventional method. For example, naphthoquinone diazide sulfonyl chloride is converted into the above general formula ( It can be obtained by condensation with the compound represented by I). Specifically, the compound represented by the above general formula (I) and naphthoquinone-1,2-diazide-4 (or 5) -sulfonyl chloride are mixed with organic compounds such as dioxane, n-methylpyrrolidone, dimethylacetamide, and tetrahydrofuran. It can be prepared by dissolving a predetermined amount in a solvent, adding a basic catalyst such as triethylamine, triethanolamine, pyridine, alkali carbonate, alkali hydrogen carbonate, and reacting, and washing the resulting product with water and drying. .
[0067]
The amount of the other quinonediazide esterified product used in the photosensitive component (C) is preferably 30% by mass or less, particularly 25% by mass or less, from the viewpoint of not impairing the effects of the present invention.
[0068]
The mixing ratio of the photosensitive components 1 and 2 is desirably 40 to 60 parts by mass, particularly 45 to 55 parts by mass of the photosensitive component 2 with respect to 50 parts by mass of the photosensitive component 1.
When the blending amount of the photosensitive component 2 is less than this range, the sensitivity tends to be inferior, and when it exceeds the range, the resolution and linearity of the resist composition tend to be inferior.
[0069]
In the composition of the present invention, the compounding amount of the component (C) is 15 to 40 parts by mass, preferably 20 to 30 parts per 100 parts by mass of the total amount of the alkali-soluble resin (A) and the component (B). It is better to select in the range of parts by mass. When the blending amount of the component (C) is below the above range, an image faithful to the pattern cannot be obtained, and the transferability is also lowered. On the other hand, when the blending amount of the component (C) exceeds the above range, sensitivity and resolution deteriorate, and a residue tends to be generated after development processing.
[0070]
In addition, when preparing the resist composition for system LCD, it is 20-40 mass parts with respect to 100 mass parts of total amounts of (A) component alkali-soluble resin and (B) component, Preferably it is 25-35. It is selected in the range of parts by mass.
[0071]
The composition of the present invention is preferably used in the form of a solution by dissolving the components (A) to (C) and various additive components in the following component (D) which is an organic solvent.
[0072]
Regarding component (D) (organic solvent):
Examples of organic solvents used in the present invention include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone; ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol mono Acetate or polyhydric alcohols such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether and derivatives thereof; cyclic ethers such as dioxane; and ethyl lactate, methyl acetate, ethyl acetate Esters such as butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate and ethyl ethoxypropionate. Rukoto can. These may be used alone or in combination of two or more.
[0073]
Among them, propylene glycol monomethyl ether acetate (PGMEA) is preferable in that it provides excellent coating properties to the resist composition of the present invention and excellent film thickness uniformity on a resist film on a large glass substrate.
PGMEA is most preferably used as a single solvent, but solvents other than PGMEA can also be used as a mixture. Examples of such a solvent include ethyl lactate, γ-butyrolactone, propylene glycol monobutyl ether and the like.
[0074]
In the case of using ethyl lactate, it is desirable to blend in an amount of 0.1 to 10 times, preferably 1 to 5 times the mass ratio of PGMEA.
Moreover, when using (gamma) -butyrolactone, it is desirable to mix | blend in 0.01-1 times amount by mass ratio with respect to PGMEA, Preferably it is 0.05-0.5 times amount.
[0075]
In the field of liquid crystal display device production, it is usually necessary to form a resist film on a glass substrate with a film thickness of 0.5 to 2.5 μm, particularly 1.0 to 2.0 μm. Using an organic solvent, the total amount of the components (A) to (C) in the composition is adjusted to 30% by mass or less, preferably 20 to 28% by mass with respect to the total mass of the composition. Is preferable as a resist material for producing a liquid crystal display element having excellent coating properties.
In consideration of the amount of the following component (E) optionally used in this case, the amount of the solvent (D) used is 65 to 85% by mass, preferably 70 to 75% by mass, based on the total mass of the composition. It is preferable.
[0076]
About component (E) (other additives)
In the present invention, ultraviolet absorbers for preventing halation such as 2,2 ', 4,4'-tetrahydroxybenzophenone, 4-dimethylamino-2', 4'- are used as long as the object of the present invention is not impaired. Dihydroxybenzophenone, 5-amino-3-methyl-1-phenyl-4- (4-hydroxyphenylazo) pyrazole, 4-dimethylamino-4′-hydroxyazobenzene, 4-diethylamino-4′-ethoxyazobenzene, 4-diethylamino Azobenzene, curcumin and the like, and surfactants for preventing striation, such as Florard FC-430, FC431 (trade name, manufactured by Sumitomo 3M Co., Ltd.), Ftop EF122A, EF122B, EF122C, EF126 (trade name, TO Fluorine such as Chem Products Co., Ltd. The purpose of the present invention is a storage stabilizer such as a surfactant, benzoquinone, naphthoquinone and p-toluenesulfonic acid, and, if necessary, conventional additives such as additional resins, plasticizers, stabilizers and contrast improvers. Can be added and contained within a range that does not interfere with the above.
[0077]
An example of a preferred method for forming a resist pattern for producing a liquid crystal display element using the composition of the present invention will be described. First, a solution prepared by dissolving the components (A) to (C) and the additive component (E) used as necessary in a suitable solvent (D) as described above is applied onto a glass square substrate with a spinner or the like. To form a coating film. The glass substrate used at this time is 500x600mm²Above, especially 550-650mm²It can be a large plate as described above.
[0078]
If the composition of the present invention is used, even in the production of liquid crystal display elements (including system LCDs) using such a large glass substrate, it is excellent in macro (applicability, heating unevenness characteristics, development unevenness characteristics), A resist pattern having excellent linearity can be obtained.
[0079]
Next, the glass substrate on which the coating film is formed is heated and dried (prebaked) at about 100 to 140 ° C. to form a photosensitive layer. Next, selective exposure is performed through a desired mask pattern using a light source that emits ultraviolet light, such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, or a xenon lamp.
[0080]
In the manufacture of a system LCD or the like, this selective exposure is performed using a mask on which a resist pattern forming mask pattern having a different pattern size is drawn. A resist pattern having a different pattern size is formed on the glass substrate. They can be formed simultaneously. For example, this selective exposure is performed using a mask (reticle) on which a resist pattern forming mask pattern having a pattern size of 0.5 to 2.5 μm and a resist pattern forming mask pattern having a pattern size of 3 to 10 μm are drawn. I can do it. The resist composition of the present invention also exhibits an excellent linearity effect when simultaneously forming patterns having different dimensions.
At this time, in order to form a fine pattern, it is preferable to use i line (365 nm).
[0081]
Next, this exposed resist-coated glass substrate is swelled with a developing solution, for example, an alkaline aqueous solution such as an aqueous solution of 1 to 10% by mass of tetramethylammonium hydroxide (TMAH) from one end of the substrate to the other end, Alternatively, the developing solution is spread over the entire surface of the substrate from the developing droplet lower nozzle installed near the center.
The method of depositing an alkaline aqueous solution from one end of the substrate to the other end can be made compact in the case of forming a resist pattern using a large glass substrate, and is extremely useful. When the liquid is accumulated from one end portion to the other end portion, there is a difference in the time of liquid accumulation at each end portion, so the contact time of the resist composition and the alkaline aqueous solution at those end portions is different, It causes development unevenness.
When the resist composition of the present invention is used, this development unevenness can be made extremely small and does not cause a practical problem.
[0082]
And it develops by leaving still for about 50 to 60 seconds, and forms a resist pattern on the said glass substrate. Thereafter, a rinsing process is performed in which the developer remaining on the resist pattern surface is washed away with a rinse solution such as pure water.
[0083]
【Example】
Various physical properties of the positive photoresist composition were determined as follows.
(1) Heating unevenness evaluation:
A glass substrate (550 × 650 mm) on which a Cr film was formed using a spinner²) After the above coating, the temperature of the hot plate is set to 130 ° C., the first drying is performed for 60 seconds by proximity baking with an interval of about 1 mm, and the temperature of the hot plate is set to 120 ° C. A second drying for 60 seconds was performed by proximity baking with an interval of 5 mm to form a resist film having a thickness of 1.5 μm.
[0084]
In the second drying process, the substrate temperature at the substrate peripheral portion A is about 105 ° C., the substrate temperature at the substrate center B is about 110 ° C., and the substrate temperature at the substrate core portion C is about 115 ° C. (See FIG. 1).
[0085]
Next, using a mirror projection aligner MPA-600FA (trade name, manufactured by Canon Inc.) through a test chart mask (reticle) on which a mask pattern for reproducing a 3.0 μmL & S (line and space) resist pattern was drawn, In the central part B of the substrate, selective exposure was performed with an exposure amount capable of reproducing 3.0 μmL & S according to the dimensions. However, the exposure amount was 30 mJ or less.
Subsequently, it was brought into contact with an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution at 23 ° C. for 60 seconds, washed with water for 30 seconds, and spin-dried.
[0086]
Then, the cross-sectional shape of the obtained resist pattern was observed with the SEM (scanning electron microscope) photograph about the said board peripheral part A, the center part B, and the core part C, and a pattern dimension was 2.90-3.10 micrometers. What was present was indicated as ◯, what was less than 2.90 μm, ×, what was greater than 3.10 μm was represented as xx, and the results are shown in Table 2.
[0087]
(2) Development unevenness evaluation:
A glass substrate (550 × 650 mm) on which a Cr film was formed using a spinner²) After the above coating, the temperature of the hot plate is set to 130 ° C., the first drying is performed for 60 seconds by proximity baking with an interval of about 1 mm, and the temperature of the hot plate is set to 120 ° C. A second drying for 60 seconds was performed by proximity baking with an interval of 5 mm to form a resist film having a thickness of 1.5 μm.
[0088]
Next, a mirror projection aligner MPA-600FA (manufactured by Canon Inc.) is used through a test chart mask (reticle) on which a mask pattern for reproducing a 3.0 μmL & S resist pattern is drawn. Was selectively exposed with an exposure amount that can be reproduced according to dimensions. However, the exposure amount was 30 mJ or less.
[0089]
Next, using a developing device (device name: TD-39000 demo machine, manufactured by Tokyo Ohka Kogyo Co., Ltd.) having a 2.38 mass% TMAH aqueous solution at 23 ° C., the substrate edge X to Z (FIG. 2), the liquid was deposited on the substrate for 10 seconds, held for 55 seconds, washed with water for 30 seconds, and spin-dried.
The contact time between the substrate and the developer was 65 seconds at the substrate end X, 60 seconds at the substrate center Y, and 55 seconds at the substrate end Z.
[0090]
Then, the cross-sectional shape of the obtained resist pattern was observed with the SEM (scanning electron microscope) photograph about the said board | substrate edge part X, center part Y, and edge part Z, and a pattern dimension was 2.80-3.20 micrometers. What was present was indicated as ◯, what was less than 2.80 μm was indicated as x, and what was greater than 3.20 μm was indicated as xx, and the results are shown in Table 2.
[0091]
(3) Linearity evaluation:
A glass substrate (550 × 650 mm) on which a Cr film was formed using a spinner²) After the above coating, the temperature of the hot plate is set to 130 ° C., the first drying is performed for 60 seconds by proximity baking with an interval of about 1 mm, and the temperature of the hot plate is set to 120 ° C. A second drying for 60 seconds was performed by proximity baking with an interval of 5 mm to form a resist film having a thickness of 1.5 μm.
[0092]
Next, an i-line exposure apparatus (apparatus name: FX) is passed through a test chart mask (reticle) in which mask patterns for reproducing resist patterns of 3.0 μmL & S, 2.0 μmL & S, and 1.5 μmL & S are drawn on one mask. -702J, manufactured by Nikon Corporation), and selective exposure was performed with an exposure amount capable of reproducing 3.0 μmL & S according to the dimensions.
[0093]
Next, using a developing device (device name: TD-39000 demo machine, manufactured by Tokyo Ohka Kogyo Co., Ltd.) having a 2.38 mass% TMAH aqueous solution at 23 ° C., the substrate edge X to Z (FIG. 2), the liquid was deposited on the substrate for 10 seconds, held for 55 seconds, washed with water for 30 seconds, and spin-dried.
[0094]
Thereafter, the cross-sectional shape of the obtained resist pattern is observed with a SEM (scanning electron microscope) photograph, and the resist pattern dimensions are actually obtained for the reproducibility of the resist pattern of 3.0 μmL & S, 2.0 μmL & S, and 1.5 μmL & S. It was evaluated by. The results are shown in Table 3.
[0095]
(Example 1)
(A) component:
100 parts by weight of alkali-soluble resin
[A product obtained by subjecting a mixture of 35 mol% of m-cresol and 65 mol% of p-cresol to a cresol novolac resin having a weight average molecular weight (Mw) of 4000 obtained by subjecting oxalic acid and formaldehyde to a condensation reaction. Mw = 4500, and a cresol novolak resin (product name: GTR-M2, manufactured by Gunei Chemical Co., Ltd.) having a phenolic dinuclear content of about 6% was used. The dinuclear content of phenols was measured by GPC measurement using the following equipment and conditions. ]
[0096]
Device name: SYSTEM 11 (manufactured by Showa Denko)
Precolumn: KF-G (manufactured by SHODEX)
Column: KF-802 (manufactured by SHODEX)
Detector: UV41 (measured at 280 nm)
Conditions such as solvent: Tetrahydrofuran was allowed to flow at a flow rate of 1.0 ml / min, and measurement was performed at 35 ° C.
[0097]
(B) component:
Sensitivity improver (B1: phenol compound represented by the above formula (V)): 15 parts by mass
(C) component:
Photosensitive component 1 / photosensitive component 2 [50/50 (mass ratio)]: 26 parts by mass
(Photosensitive component 1: C1: esterified product of 1 mol of the compound represented by the formula (VII) and 2 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride (hereinafter referred to as “5-NQD”) Esterification rate 50%); Photosensitive component 2: C2: esterified product of 1 mol of the compound represented by the above formula (VIII) and 2.34 mol of 5-NQD (esterification rate: 59%)
(D) component:
Solvent (PGMEA): 423 parts by mass
[0098]
After the components (A) to (D) were uniformly dissolved, this was filtered using a membrane filter having a pore size of 0.2 μm to prepare a positive photoresist composition. About this composition, the said heating nonuniformity and image development nonuniformity were measured. The results are shown in Table 2 as described above.
[0099]
(Examples 2-6, Comparative Examples 1-10)
Various positive photoresist compositions were prepared in the same manner as in Example 1 except that the components (A) to (D) were changed to those described in Table 1 below. About this composition, the said heating nonuniformity, image development nonuniformity, and linearity were measured. The results are shown in Tables 2 and 3 as described above.
[0100]
Regarding the abbreviations and the contents of the compounds used in each Example and Comparative Example, B1, C1, and C2 are as described above, while B2, C2 ', C3, C4, and EL are as follows.
[0101]
Embedded image

(However, the esterification rates of C2 ', C3, and C4 are 75%, 66%, and 66%, respectively.)
[0102]
[Table 1]

[0103]
[Table 2]

[0104]
As is apparent from Table 2, when the components specified in the present invention are not used, the development unevenness of the photoresist composition film may be good but the heating unevenness is bad.
[0105]
[Table 3]

[0106]
As is apparent from Table 3, it is clear that the linearity of the photoresist composition film is poor when the components specified in the present invention are not used.
[0107]
【The invention's effect】
      According to the present invention, it is inexpensive and 500 × 600 mm²Resist material with excellent macro characteristics (applicability, uneven heating characteristics, uneven development characteristics) even in the above process using large glass substratesAnd method for forming resist pattern for manufacturing liquid crystal display elementCan be provided. Furthermore, according to the present invention, a resist material that is suitable for the manufacture of a system LCD, has excellent linearity, and is suitable for i-line exposure.And method for forming resist pattern for manufacturing liquid crystal display elementCan be provided.
[Brief description of the drawings]
FIG. 1 shows the regions of a substrate peripheral portion A, a substrate central portion B, and a substrate core portion C when a positive photoresist composition is applied to a glass substrate, baked and dried for evaluation of heating unevenness. Figure representing.
[Fig. 2] For development unevenness evaluation and linearity evaluation, a positive photoresist composition is applied to a glass substrate, baked and dried, and after pattern exposure, the developer is applied to the edge of the substrate with a developing device having a slit coater. Explanatory drawing to the effect of liquid accumulation from part X to Z.

Claims (10)

(1) With respect to 100 parts by mass of (A) alkali-soluble resin, (B) the following general formula (I)

[Wherein, R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms. R ^{9 to} R ¹¹ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Q is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon atom bonded to R ^9. A group which forms a cycloalkyl group having a chain of 3 to 6, or a group represented by the following chemical formula ( II )

Wherein R ¹² and R ¹³ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms. C represents an integer of 1 to 3); a and b represent an integer of 1 to 3; d represents an integer of 0 to 3; and n represents an integer of 0 to 3. The phenol compound represented by formula (5) is contained in an amount of 5 to 25 parts by mass, and (C) the following general formula ( III ) with respect to 100 parts by mass of the total mass of the component (A) and the component (B ).

Wherein R ¹⁴ independently represents an alkyl group having 1 to 5 carbon atoms; D independently represents a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group, and at least one of D Represents a 1,2-naphthoquinonediazide-5-sulfonyl group; l and m each independently represents 1 or 2, and a quinonediazide esterified product (photosensitive component 1) represented by formula ( IV): )

(Wherein D independently represents a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group, and at least one of D is a 1,2-naphthoquinonediazide-5-sulfonyl group). Containing a mixture of photosensitive components comprising a quinonediazide esterified product (photosensitive component 2) in an amount of 15 to 40 parts by mass, and (D) a positive photoresist composition containing an organic solvent at least 500 × 600 mm ² Coating on a large glass substrate and forming a coating film,
(2) a step of heat-treating (pre-baking) the glass substrate on which the coating film has been formed to form a resist coating on the glass substrate;
(3) a step of selectively exposing the resist film;
(4) The resist film after the selective exposure is subjected to a development process using an alkaline aqueous solution to form a resist pattern on the glass substrate, and (5) the developer remaining on the resist pattern surface is washed away. A method for forming a resist pattern for manufacturing a liquid crystal display element, comprising a rinsing step. The component (B) is represented by the following formula (V)

The method for forming a resist pattern for producing a liquid crystal display element according to claim 1, wherein the phenolic compound is represented by the formula: The component (B) has the following formula ( VI )

The method for forming a resist pattern for producing a liquid crystal display element according to claim 1, wherein the phenolic compound is represented by the formula: Component (A) contains 60 mol% or more of p-cresol-based repeating units and 30 mol% or more of m-cresol-based repeating units in all phenolic repeating units, and has a polystyrene equivalent weight average molecular weight (Mw). Novolak with 2000-8000 4. The method for forming a resist pattern for manufacturing a liquid crystal display element according to claim 1, wherein the resist pattern is a resin. The photosensitive component 1 has the following formula ( VII )

A quinonediazide esterified product having an average esterification rate of 40 to 60% between a phenol compound represented by the formula (1) and a 1,2-naphthoquinonediazide-5-sulfonyl compound, and photosensitive component 2 is represented by the following formula ( VIII ):

The liquid crystal according to any one of claims 1 to 4, which is a quinonediazide esterified product having an average esterification rate of 50 to 70% between a phenol compound represented by formula (1) and a 1,2-naphthoquinonediazide-5-sulfonyl compound. A method for forming a resist pattern for manufacturing a display element . The method for forming a resist pattern for producing a liquid crystal display element according to claim 1, wherein a positive resist composition containing propylene glycol monomethyl ether acetate as component (D) is used. The positive resist composition in which the total amount of the components (A), (B) and (C) is 30% by mass or less based on the total mass of the composition is used. A method for forming a resist pattern for producing a liquid crystal display element according to the item . (3) The step of performing selective exposure is performed using a mask on which a resist pattern forming mask pattern having different pattern dimensions is drawn, and simultaneously forming resist patterns having different pattern dimensions on the glass substrate. the liquid crystal display element forming method for producing a resist pattern according to claim 1, characterized in that. The mask on which the resist pattern forming mask patterns having different pattern dimensions are drawn includes at least a resist pattern forming mask pattern having a pattern dimension of 0.5 to 2.5 μm and a resist pattern forming mask pattern having a pattern dimension of 3 to 10 μm. The method for forming a resist pattern for manufacturing a liquid crystal display element according to claim 8 , wherein the mask is a mask (reticle) drawn as described above. (3) a step of performing selective exposure, i-line liquid crystal display device manufactured according to any one of claims 1 to 9, characterized in that is performed by an exposure process using a (365 nm) light source A method for forming a resist pattern.

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