1326801 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係有關於LCD製造用正型光阻組成物，及使 用上述正型光阻組成物的光阻圖型之形$ $、法。 【先前技術】 向來’薄膜電晶體（TFT)等半導體元件、液晶顯示 元件（LCD)的製造中之阻劑材料’由於適合於g線、h線 及i線曝光’相對廉價而靈敏度高，多係利用驗可溶性樹 脂用淸漆型酚醛樹脂，感光性成分（以下或簡稱PAC )用 含萘醌二疊氮基之化合物的淸漆酚醛-蔡醒二疊氮系正型 光阻組成物物（參考例如專利文獻1至4 ：)。 又’目前之新世代LCD ’於一片坡璃基板上，驅動器 、DAC (數位類比轉換器）、影像處理器、視訊控制器、 RAM等積體電路部份與顯示部份同時形成的所謂「系統 LCD」之高功能LCD之技術開發正活躍進行（參考例如非專 利文獻1 )。 以下，本說明書中，如此之於一基板上形成積體電路 及液晶顯示部份的LCD，簡稱爲系統LCD。 專利文獻1日本專利特開2000 — 131 835號公報 專利文獻2特開200 1 — 75272號公報 專利文獻3特開2000 — 18 1055號公報 專利文獻4特開2000— 1 1 2120號公報 非專利文獻 1 Semiconductor FPD World 2001.9，ρρ·50- 67 · (2) 1326801 【發明內容】 發明所欲解決之課題 LCD之製造領域及系統LCD之製造領域中，相對於用 在半導體之製造的矽晶圓等，基板表面平滑性差，並因係 使用大面積之玻璃基板，焦點深度（Depth of focus; DOF )特性之提升已係重要課題。 本發明之課題即在提供，可達成D OF特性之提升的正 型光阻組成物，及光阻圖型之形成方法。 用以解決課題之手段 本發明人等精心硏討結果發現，添加特定之含酚式羥 基的化合物上述課題即可解決’而完成本發明。 亦即，本發明提供’其特徵爲：含有（A)鹼可溶性 樹脂，（B)萘醌二疊氮酯化物，（C)下述一般式（in )之分子量1 000以下的含酚式羥基之化合物，以及（D) 有機溶劑而成之LCD製造用正型光阻組成物。1326801 (1) Field of the Invention The present invention relates to a positive-type photoresist composition for LCD manufacturing, and a photoresist pattern shape using the above-described positive-type photoresist composition. . [Prior Art] The semiconductor material such as thin film transistor (TFT) and the resist material in the manufacture of liquid crystal display (LCD) are relatively inexpensive and sensitive because they are suitable for g-line, h-line, and i-line exposure. A lacquer-type phenolic resin using a lacquer-type phenolic resin for a soluble resin, and a lacquer phenolic-cao azide-diazide-type positive-resistance composition containing a naphthoquinonediazide-based compound as a photosensitive component (hereinafter abbreviated as PAC) Reference is made, for example, to Patent Documents 1 to 4:). The 'current new generation LCD' is a so-called "system" formed on a single substrate, a driver, a DAC (digital analog converter), an image processor, a video controller, a RAM, and the like. The development of technology for high-performance LCDs of LCDs is actively being carried out (see, for example, Non-Patent Document 1). Hereinafter, in the present specification, an LCD in which an integrated circuit and a liquid crystal display portion are formed on a substrate is simply referred to as a system LCD. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2000-131835 (Patent Document No. JP-A No. 2000-75272) Patent Document No. JP-A No. 2000-1818 1 Semiconductor FPD World 2001.9, ρρ·50-67 · (2) 1326801 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The field of manufacturing of LCD and the field of manufacturing of LCDs are related to the use of germanium wafers for semiconductor manufacturing. The smoothness of the surface of the substrate is poor, and the use of a large-area glass substrate, the improvement of the depth of focus (Depth of focus; DOF) has been an important issue. SUMMARY OF THE INVENTION An object of the present invention is to provide a positive resist composition which can improve DOF characteristics and a method of forming a photoresist pattern. Means for Solving the Problem As a result of careful examination by the present inventors, it has been found that the above problem can be solved by adding a specific phenolic hydroxyl group-containing compound. That is, the present invention provides a feature comprising: (A) an alkali-soluble resin, (B) a naphthoquinonediazide compound, (C) a phenolic hydroxyl group having a molecular weight of 1 000 or less of the following general formula (in) A positive photoresist composition for LCD manufacturing, which is a compound and (D) an organic solvent.
23 R28 (〇H)h R R (HO)e R -6- 132680123 R28 (〇H)h R R (HO)e R -6- 1326801
(式中，R12及R13係各自獨立表示氫原子、鹵素原子、碳 原子數1至6之烷基’碳原子數1至6之烷氧基或碳原子數3 至6之環烷基；C表示1至3之整數）’或者Q1可係與R9之末 端結合，此時Q1連同R9及Q1與R9間之碳原子’表示碳鏈3 至6之環烷基；a、b表示1至3之整數；d表0至3之整數；a 、b.d係3時，無R3、R6或R8; η表示0至3之整數] 本發明之LCD製造用正型光阻組成物適用於在一基 板上形成積體電路及液晶顯示部份之基板製程。 又，本發明提供，其特徵爲：包含（1)將上述正型 光阻組成物塗敷於基板上，形成塗膜之過程，（2 )將上 述形成塗膜之基板加熱處理（預烘烤），於基板上形成光 阻被膜之過程，（3)對於上述光阻被膜進行選擇性曝光 之過程，（4 )對於上述選擇性曝光後之光阻被膜施以加 熱處理（曝光後烘烤）之過程，以及（5)對於上述加熱 處理後之光阻被膜，用鹼水溶液施行顯像處理之過程的光 阻圖型之形成方法。 【實施方式】 以下詳細說明本發明 -8- (5) (5)1326801 [正型光阻組成物] < (A)成分> (A )成分係鹼可溶性樹脂。 (A )成分無特殊限制，可任意選用正型光阻組成物 Φ通常可用作被膜形成物質者中之一種或二種以上。 有例如，酚類（酚、間甲酚、對甲酚、二甲酚 '三甲 酌等）與醛類（甲醛、甲醛前驅物、丙醛、2 -羥苯甲醛 ' 3~羥苯甲醛、4_羥苯甲醛等）及/或酮類（丁酮、丙 等）於酸性觸媒存在下縮合得之淸漆酚醛樹脂； 羥苯乙烯之單聚物，羥苯乙烯與其它苯乙烯系單體之 共聚物，羥苯乙基與丙烯酸或甲基丙烯酸或其衍生物之共 聚物等羥苯乙烯系樹脂； 丙烯酸或甲基丙烯酸與其衍生物之共聚物丙烯酸或甲 基丙烯酸系樹脂等。 尤以含選自間甲酚、對甲酚、3,4—二甲酚及2,3,5_ 三甲酚中之至少二種酚類，與含有甲醛之醛類縮合反應得 之淸漆酚醛樹脂，適於調製高靈敏度，解析度優之光阻材 料。 (A)成分可依一般方法製造。 (A)成分經凝膠滲透層析法之聚苯乙烯換算質量平 均分子量（Mw)取決於其種類，但爲靈敏度、圖型之形 成宜係2000至100000，以3000至30000較佳。 (A)成分可依一般方法製造。 -9- (6) (6)1326801 < (B )成分> (B)成分若係一般正型光阻組成物中，用作感光性 成分之萘醌二疊氮酯化物即無特殊限制，可任意選用一種 或二種以上。 其中尤以上述一般式（I)之酚化合物，與萘醌二疊 氮磺酸化合物之酯化物，適合於尤以使用i線之微影術° 亦適於低NA條件下，形成形狀良好之2.0微米以下的微細 光阻圖型。 上述一般式（1)之該酚化合物中較佳者爲， • Q1不與R9之末端結合，R9表氫原子或碳原子數1至6 之烷基，Q1表上述化學式（II)之餘基，η表0之參酚型化 合物， • Q1不與R9之末端結合，R9表氫原子或碳原子數1至6 之烷基，Q1表氫原子或碳原子數1至6之烷基’ η表1至3之 整數的線型聚酣化合物。 上述參酚型化合物，更具體而言，有參（4 一羧苯基 )甲烷、雙（4 —羥—3 —甲苯基）一2 —羥苯基甲烷、雙 (4~羥~~2,3,5 —三甲苯基）—2—羥苯基甲烷、雙（4 — 羥一3,5~二甲苯基）—4 —羥苯基甲烷 '雙（4 —羥一 3,5 —二甲苯基）一 3 —羥苯基甲烷、雙（4_羥一 3;5〆二甲 苯基）~2_羥苯基甲烷、雙（4一羥一 2,5 —二甲笨基） —4~羥苯基甲烷、雙（4一羥一 2,5—二甲苯基）一 3 —羥 苯基甲烷、雙（4 -羥一 2,5—二甲苯基）一2—羥笨基甲 -10- (7) (7)1326801 烷、雙（4_羥基_3,5_二甲苯基）_3,4_二羥苯基甲 烷、雙（4 一羥_ 2,5 _二甲苯基）_ 3,4 —二羥苯基甲烷 、雙（4 _羥_ 2,5 —二甲苯基）一2,4 _二羥苯基甲烷、 雙（4 一羥苯基）_3_甲氧一 4_羥苯基甲烷、雙（5—環 己_4_羥一2 —甲苯基）_4 一羥苯基甲烷、雙（5—環己 一 4一羥_2_甲苯基）_3_羥苯基甲烷、雙（5_環己-4_羥一 2 —甲苯基）_2_羥苯基甲烷、雙（5_環己一 4 一羥_2_甲苯基）_3，4_二羥苯基甲烷等。 上述線型聚酚化合物，更具體而言有，2,4-雙（3,5 —二甲一4_羥苯甲基）一5 —羥酚、2,6_雙（2,5 —二甲 —4 一羥苯甲基）_4_甲酚等線型三核體酚化合物；1,1 —雙[3_ (2_羥一5_甲苯甲基）一4一羥一5_環己苯基 ]異丙烷、雙[2,5 —二甲_3_ (4_羥_5_甲苯甲基）一4 _羥苯基]甲烷、雙[2,5_二甲_3_ (4_羥苯甲基）一 4 一羥苯基]甲烷、雙[3— （3,5 —二甲_4_羥苯甲基）_4 _羥_5_甲苯基]甲烷、雙[3—（3,5—二甲一4_羥苯甲 基）_4_羥_5_乙苯基]甲烷、雙[3_3,5—二甲_4_羥 苯甲基）—4_羥_5_甲苯基]甲烷、雙[3_ (3,5_二乙 —4_羥苯甲基）一4 一羥_5_乙苯基）甲烷、雙[2_羥 —3 — (3,5——甲一 4_經苯甲基）一 5_甲苯基]甲院、 雙[2 —羥一3_ (2—羥_5_甲苯甲基）_5 —甲苯基]甲 烷 '雙[4 一羥_3_ (2 —羥_5_甲苯甲基）一5_甲苯基 ]甲烷 '雙[2,5_二甲一3— (2 —羥一5 —甲苯甲基）一4- 羥苯基]甲烷等線型四核體酚化合物；2,4-雙[2—羥-3 - (8) (8)1326801 (4 一羥苯甲基）—5—甲苯甲基]—6 -環己酚、2,4 —雙[4 —羥—3— (4 —羥苯甲基）_5_甲苯甲基]_6_環己酚 、2,6_ 雙[2,5 —二甲一3— (2 —經一5— 甲苯甲基）一4一 羥苯甲基]~4_甲酚等線型五核體酚化合物等。 又’上述參酚型化合物及上述線型聚酚化合物以外， 一般式（I)之該酚化合物有，雙（2,3,4-三羥苯基）甲 烷、雙（2,4_二羥苯基）甲烷、2,3,4 —三羥苯基_4·— 羥苯基甲烷、2— (2,3,4_三羥苯基）—2— (2，，3，，4，— 三羥苯基）丙烷、2(2,4_二羥苯基）一2_ (2，，4，_二 羥苯基）丙烷、2_ (4 —羥苯基）一 2— (4,一羥苯基） 丙烷、2— (3_氟_4 —羥苯基）一 2一（3，_氟—4，_羥 苯基）丙烷、2—（2,4 —二羥苯基）—2— (4' —羥苯基） 丙烷'2— (2,3,4_三羥苯基）_3— (4，一羥苯基）丙烷 、2_ (2,3,4—三羥苯基）一2— (4，-羥—3，，5，一二甲苯 基）丙烷等雙酚型化合物；1_[1— (4 —羥苯基）異丙基 ]—4-[]，1—雙（4 —羥苯基）乙基]苯、1— [}_ (3 —甲 —4 —羥苯基）異丙基]—4— [1，1—雙（3~甲—4 —羥苯基 )乙基]苯等多核分枝型化合物；1，1一雙（4_羥苯基） 環己烷等縮合型酚化合物等。 這些酚化合物可用一種或組合二種以上使用。 其中，以參酚型化合物爲主要成分，於高靈敏度化及 解析度較佳，尤以雙[5 -環己一 4 一羥—2—甲苯基）一 3,4 —二羥苯基甲烷[以下略作（B1·) 。：I、雙（4 一羥— 2,3,5_三甲苯基）—2—羥苯基甲烷[以下略作（B3，）。] -12- 1326801 Ο) 爲佳。又爲調製解析度、靈敏度、耐熱性、DOF特性、線 性等光阻特性之整體均衡優之光阻組成物，較佳者爲以線 型聚酚化合物、雙酚型化合物、多核分枝型化合物及縮合 型酚化合物等，與上述參酚型化合物倂用。尤以倂用雙酚 型化合物中之雙（2,4 一二羥苯基）丙烷[以下略作（B2·) 。]，可調製整體均衡優之光阻組成物。 而以下，上述（ΒΓ) 、 ( B2- ) 、 （B3')之各萘醌 二疊氮酯化物略作（Bl) 、（B2) 、（B3)。 使用（Bl) 、 （B3)時，（B)成分中之配合量係各 10質量％以上，15質量％以上更佳。 萘醌二疊氮磺酸化合物以1，2 _萘醌二疊氮- 4 -磺醯 化合物’或1，2 —萘醌二疊氮- 5 -磺醯化合物爲佳，具體 例有1，2 —萘醌二疊氮_4 一磺醯氯、1，2_蔡醌二疊氮_5 -購酸氯等。 (B)成分含上述一般式（I)之化合物的酚式羥基之 全部或一部分，用1，2-萘醌二疊氮磺醯化合物酯化之萘 醌二疊氮酯化物。 一般式（I)之化合物的酚式羥基之全部或一部份的 蔡醒一璺氮醋化方法可用一般方法。 例如’可使1，2~萘醌二疊氮磺醯氯與上述一般式（I )之化合物縮合而得。 具體而言’可係如將上述一般式（I)之化合物，及 152 —萘醌二疊氮磺醯氯以特定量溶解於二哼仙、n -甲吡 咯烷酮、二甲乙醯胺、四氫呋喃等有機溶劑，於其加三乙 -13- (10) (10)1326801 胺、三乙醇胺、吡啶、碳酸鹼金屬鹽、碳酸氫鹼金屬鹽等 鹼性觸媒一種以上使之反應，所得產物經水洗、乾燥而調 製。 (B )成分除如上述例示之這些較佳萘醌二疊氮酯化 物以外，亦可使用一般用在正型光阻組成物中作爲感光性 成分之其它萘醌二疊氮酯化物。例如，聚羥二苯基酮、五 倍子酸烷基酯等酚化合物與萘醌二疊氮磺酸化合物之酯化 反應產物等亦可使用。這些其它萘醌二疊氮酯化物可任意 選用一種或二種以上。 這些其它萘醌二疊氮酯化物之使用量係（B)成分中 8 0質量％以下’尤以5 0質量％以下’於本發明效果之提升 上較佳。 本發明之正型光阻組成物中（B )成分之配合量係使 之爲相對於（A)成分與下述（C)成分及下述（X)成分 合計量20至70質量％，25至60質量％更佳。 使用（B)成分之配合量超出上述下限値以上，可得 圖型之忠實圖像，提升轉印性。使之在上述上限値以下， 可防靈敏度之劣化，形成之光阻膜均勻度提升，得解析度 提升之效果。 < (C )成分> (C)成分係上述一般式（III)之含酣式經基之化合 物’分子量係1000以下，700以下更佳。實質上係2〇〇以上 ，3 0 0以上更佳。 -14- (11) (11)1326801 上述一般式（III )之含酚式羥基的化合物有，m係1 之線型三核體酚化合物，m係2之線型四核體酚化合物，m 係3之線型五核體酚化合物’ m係4之線型六核體酚化合物 ，及m係5之線型七核體酚化合物。 這些之具體例，除可構成上述（B)成分之線型聚酚 化合物之具體例的線型三核體酚化合物之外，有2,6 ~雙 (3，5 -二甲一4 —羥苯甲）一4 —甲酚、2,4 -雙（3,5 -二 甲一 4_羥苯甲基）一 6 —甲酚、2,4 —雙[1— (4_羥苯基 )異丙基]- 5 -羥酚等線型三核體酚化合物；可構成前敘 之（B)成分的線型聚酚化合物之具體例的線型四核體酚 化合物及線型五核體酚化合物；特開平6 - 1 67 8 05號公報 記載之’可構成醌二疊氮系感光劑醌二疊氮磺酸酯之酣化 合物、四至七核體的酚化合物等。 (C )成分係以可溶於調製光阻組成物之際的溶劑者 爲佳’爲此’以用選自上述一般式（III)之上述m係1或2 ，末端苯環之取代羥基係結合在對位的三核體或四核體之 含酚式羥基的化合物所成群之一種以上爲佳。 該溶解性優之四核體’含酚或羥基的化合物之例有， 雙[3_ (3,5 —二甲一4 —羥苯甲基）—4 —羥一 甲苯基] 甲院[以下略作（C1)]。又，三核體之含酚式羥基的化合 物之例有’ 2,6 —雙（2,5 —二甲一 4 —羥苯甲基）一4 —甲 酚[以下略作（C2) ]、2,6 —雙（3,5 —二甲_4 一羥苯甲基 )—4 —甲酣[以下略作（C3) ]、2,4 — （3,5 —二甲一4 — 羥苯甲基）—6 —甲酚[以下略作（C4) ]、24一雙[丨一（4 -15- (12) (12)1326801 —羥苯基）異丙基]一 5—羥酚[以下略作（C5)]。 這些之中以（C2 )至（C5 )爲較佳，（C2 )尤佳。 (C)成分可單獨使用一種，亦可倂用二種以上。 本發明中（C)成分之配合量，爲得上述成分之添加 效果，以相對於（A )成分5質量％以上爲佳，1 0質量％以 上更佳。又（C)成分之配合量過多則其它構成成分之均 衡變差，故以50質量％以下爲佳，40質量％以下更佳。 < (X )成分> 本發明之正型光阻組成物亦可含（C )成分以外的（ X)其它含酚式羥基之化合物。尤以（C)成分係使用’ 於調製光阻組成物之際的溶劑之溶解度低者時，上述（C )成分與（X)成分之倂用，可得（C)成分之添加效果 故較佳。 該（X)成分較佳者爲，作爲靈敏度提升劑或增感劑 —般用於光阻組成物之分子量1 00 0以下的含酚式羥基化合 物，而不含於（C)成分者。上述（X)成分之更佳分子 量係700以下，實質上200以上，300以上更佳。 具體而言，可構成前敘之（B)成分的酯化合物者之 中，不含於上述（C)成分，分子量在上述範圍內者’即 可用作（X )成分。 合適之（X)成分，具體例有參（4 一羥苯基）甲烷 、雙（4_羥—3 -甲苯基）—2 —羥苯甲烷、雙（4 一羥一 2,3,5 —三甲苯基）一2_羥苯甲烷、雙（4 —羥一 3,5 —二 -16- (13) (13)1326801 甲苯基）_4 —羥苯甲烷、雙（4_羥一 3,5_二甲苯基） _3_羥苯甲烷、雙（4_羥_3,5_二甲苯基）一2—羥苯 甲烷、雙（4 一羥一2,5 _二甲苯基）一 4 _羥苯甲烷、雙 (4_羥_2,5_二甲苯基）_3_羥苯甲烷、雙（4_羥一 2,5 —二甲苯）_2_羥苯甲烷、雙（4 一羥一3,5_二甲苯 基）_3,4 —二羥苯甲烷、雙（4_羥一 2,5_二甲苯基） _3,4_二羥苯甲烷、雙（4_羥_2,5 —二甲苯基）一2,4 —二經苯甲院、雙（4_經苯基）一3_甲氧基一4 —經苯 甲烷、雙（5_環己_4_羥_2_甲苯基）一4一羥苯甲烷 、雙（5_環己一4 —羥—2_甲苯基）_3_羥苯甲烷、雙 (5_環己一4_羥_2_甲苯基）_2—羥苯甲烷、雙（5 —環己一4_羥一2 —甲苯基）一 3,4 -二羥苯甲烷等參酚 型化合物； 雙（2,3,4_三羥苯基）甲烷、雙（2,4 一二羥苯基） 甲烷、2,3,4_三羥苯一 4'_羥苯甲烷、2_ (2,3,4 一三羥 苯基）一2— (2'，3’，4·—三羥苯基）丙烷、2_ (2,4_二 羥苯基）_ 2 _ ( 2、4'—二羥苯基）丙烷、2 — ( 4 _羥苯 基）_2_ (4’_羥苯基）丙烷、2_ (3_氟_4_羥苯基 )—2-（31—氣一 4'—經苯基）丙垸、2_ (2,4_ 一經苯 基）_2_ (4’一羥苯基）丙烷、2_ (2,3,4_三羥苯基） —2_ (4'—羥苯基）丙烷、2_ (2，3，4 —三羥苯基） —2_ ( 4'—羥一 3、5’_二甲苯基）丙烷等雙酚型化合物 ;1_[1一（4一羥苯基）異丙基]_4— [1，1_雙（4一羥苯 基）乙基]苯、1_[1_ (3 —甲一4 —羥苯基）異丙基]—4 -17- (14)1326801 -[1 合物 2,3一 羥二 四羥 羥二 羥二 之， ，雙 -4 - 、雙 羥苯 2 - E 苯基 羥苯 [M 分之 佳， ，1 一雙（3 —甲〜4_羥苯基）乙基]苯等多核分枝型化 ;1，1 一雙（4~羥苯基）環己烷等縮合型酚化合物； 丨—二經二苯基酮、2,4，4,一三羥二苯基銅、2,4,6一三 苯基酮、2,3,4~三羥_2__甲二苯基酮' 2,3:4,4,一 一苯基酮、2,2,4,4,一四羥二苯基酮、2,4,6,3，，4，一五 * 苯基酮、2,3,4,2，，4, _ 五羥二苯基酮、2,3,4,2'，5, 一五 · 苯基酮、2,4,6,3，，4，，5，_ 六羥二苯基酮、2,3,4,3，，4’，5’ 經二苯基酮等多羥基二苯基酮類等。 φ 較佳（X)成分之具體例有，於上述（B)成分例示 用於0»化合物的萘醌二疊氮酯化物之酚化合物以外的 (3 一甲—4 —羥苯基）一4 —異丙苯甲烷、雙（3—甲 -羥苯基）苯甲烷、雙（2_甲—4 —羥苯基）苯甲垸 (3 —甲—2 —羥苯基）苯甲烷 '雙（3,5 —二甲一 4 一 基）苯甲烷、雙（3_乙-4 一羥苯基）苯甲烷 '雙（ 3— 4 —羥苯基）苯甲烷 '雙（2 —三級丁 _4,5_二羥 )苯甲烷等參苯基型化合物。其中以雙（2 一甲_4 一 φ 基）苯甲烷、1— [1_ (4_羥苯基）異丙基]一 4一 -雙（4 一羥苯基）乙基]苯爲較佳。 本發明之正型光阻組成物中，（C)成分與（X)成 配合量合計係以相對於（A )成分1 0至7 0質量％爲較 ‘ 2 0至6 0質量％更佳。 < (D )成分〉 (D )成分若係一般用於光阻組成物者即無特殊限制 -18- (15) (15)1326801 ，可選用一種或二種以上，而含丙二醇一烷基醚乙酸酯， 及/或2-庚酮者因塗敷性優，於大型玻璃基板上光阻被膜 之膜厚均勻度優而較佳。 而，亦可兼用丙二醇-烷基醚乙酸酯及2—庚酮二者 ，但各自單獨，或與其它有機溶劑混合使用者，大多於以 旋塗法等塗敷時膜厚均勻度較佳。 丙二醇_烷基醚乙酸酯，於（D)成分中係以含50至 1 0 0質量％爲較佳。 丙二醇-烷基醚乙酸酯係具有例如，碳原子數1至3之 直鏈或分枝鏈狀烷基之物，其中丙二醇-甲醚乙酸酯（以 下或略作PGMEA)因於大型玻璃基板上光阻被膜之膜厚均 勻度極優，而尤佳。 另一方面，2 —庚酮係，尤以（B )萘醌二疊氮醌化物 乃使用非二苯基酮系感光性成分，具體而言上述一般式（ I )之酚化合物，與萘醌二疊氮磺酸化合物之酯化反應產 物時之合適溶劑。 2 -庚酮耐熱性優於PGME A，具有可得浮渣之產生減 少的光阻組成物之特性，係非常好的溶劑。 以2-庚酮單獨，或與其它有機溶劑混合使用時，以 於（D)成分中含50至100質量％爲佳。 又，這些良好溶劑亦可混合以其它溶劑使用。 例如以乳酸甲酯、乳酸乙酯等（較佳者爲乳酸乙酯） 乳酸烷基酯配合，因光阻被膜之膜厚均勻度優，可形成形 狀優良之光阻圖型而較佳。 -19- (16) (16)1326801 以丙二醇-烷基醚乙酸酯與乳酸烷基酯混合使用時， 相對於丙二醇-烷基醚乙酸酯，宜配合乳酸烷基酯質量比 0.1至10倍量，1至5倍量爲較佳。 又’亦可用7 — 丁內酯、丙二醇-丁醚等有機溶劑。 使用7 _ 丁內酯時，配合範圍宜係相對於丙二醇-烷 基醚乙酸酯質量比0·01至1倍量，0.0 5至0.5倍量較佳。 而，其它可配合之有機溶劑具體有以下溶劑。 亦即’丙酮、丁酮、環己酮、甲基異戊基酮等酮類； 乙二醇、丙二醇、二乙二醇 '乙二醇一乙酸酯 '丙二醇一 乙酸酯、二乙二醇一乙酸酯，或這些之一甲醚、一乙醚、 一丙醚、一 丁醚或一苯醚等多元醇類及其衍生物；如二吗 Ρ山之環醚類；及乙酸甲酯、乙酸乙酯、乙酸丁酯、丙_酸 甲酯 '丙酮酸乙酯、甲氧丙酸甲酯、乙氧丙酸乙酯等醋類 等。 使用這些溶劑時，宜係（D )成分中5 0質量％以下。 本發明之正型光阻組成物，在無損於本發明目的之範 圍內，必要時可含具相容性之添加物，例如用以改良光阻 膜之性能等的附加樹脂' 塑化劑、保存安定劑、界面活性 劑，用以使經顯像之圖像更爲顯眼之著色劑，用以提升增 感效果之增感劑、防暈光用染料、密合性促進劑等常用添 加物。 防暈光用染料可用紫外線吸收劑（例如2,2’54:4·—四 羥二苯基酮、4 -二甲胺—2 ·:4·-二羥二苯基酮、5_胺— 3—甲—1—苯一4- (4 —羥苯偶氮）吡唑、4 —二甲胺— -20- (17) (17)1326801 4'—羥偶氮苯、4 —二乙胺— 41—乙氧偶氮苯、4_二乙胺 偶氮苯、薑黃素等）等。 界面活性劑可爲例如防輝紋等而添加，可用例如， FLUORADFC— 430、FC— 431 (商品名，住友 3M (股） 製）’ EFTOP EF 122A、EF122B、EF122C、EF126 (商品 名’ TOCHEM PRODUCT (股）製）等氟系界面活性劑' XR — 104、MEGAFACR— 08(商品名，大日本油墨化學 工業（股）製）等。 <本發明正型光阻組成物之調製> 本發明之正型光阻組成物，較佳者爲，將（A )成分 、（B)成分、（C)成分及必要時之其它成分溶解於 )有機溶劑而調製。（D)成分之使用量較佳者爲，溶解（ A)至（C)成分及必要時所用之其它成分時，適當調整以 得均勻之正型光阻組成物。較佳者爲使固體成分濃度成爲1〇 至50質量％ ’ 20至35質量％更佳。而，正型光阻組成物之固 體成分係相當於（A)至（C)成分及必要時所用之其它成 分的合計。 本發明之正型光阻組成物係以調製成上述光阻組成物 所含固體成分之Mw (下稱光阻分子量）在5000至30000之範 圍內爲佳，6000至10000更佳。使上述光阻分子量在上述範 圍內，即無靈敏度之下降，可達高解析度，同時可得線性及 D0F特性優良，而且耐熱性亦優之正型光阻組成物。 光阻分子量小於上述範圍，則解析度、線性、DOF特性 -21 - (18) (18)1326801 及耐熱性不足，超過上述範圍則靈敏度顯著下降，有損及光 阻組成物的塗敷性之虞。 而本說明書中’光阻分子量係用，以下之使用GPC系統 測定之値。 裝置名稱：SYSTEM 1 1 (產品名，昭和電工公司製）前 管柱：KF— G(產品名，Shodex公司製）管柱：KF— 805、 KF — 8 03、KF - 802 (產品名，Sh〇dex公司製）偵測器： UV41 (產品名’ Shodex公司製），於280奈米測定。 溶劑等：以流量1 · 0毫升/分鐘流通四氫呋喃，於3 5。(：測 定。測定試樣調製方法：將欲予測定之光阻組成物調整爲 固體成分濃度30質量％，以四氫呋喃稀釋，製作固體成分濃 度0.1質量％之測定試樣。將上述測定試樣20微升打入上述 裝置進行測定。 本發明正型光阻組成物之調製當中，調製光阻分子量 使之落入上述合適範圍之方法有例如，（1 )爲使混合所用 成分後之Mw落入上述範圍，混合前對於（A)成分進行分 離操作等，預先調整（A)成分之Mw於適當範圍之方法， (2 )準備多種Mw不同之（A)成分，以之適當配合調整 上述固體成分之Mw於上述範圍之方法等。 這些調製方法中，尤以上述（2)之調製方法，因光 阻分子量之調整，及靈敏度調整容易而較佳。 <光阻圖型之形成方法> 以下呈示LCD之製造中，光阻圖型的合適形成方法之 -22- (19) (19)1326801 —例。 首先，將上述本發明之正型光阻組成物，以旋塗機等 塗敷於基板形成塗膜。基板係以玻璃基板爲較佳。玻璃基 板通常係用非晶質氧化矽，而在系統LCD領域係以用低溫 多晶矽等爲佳。該玻璃基板，因本發明之正型光阻組成物 於低NA條件下解析度優，可用500毫米X 600毫米以上， 尤以550毫米X 650毫米以上之大型基板。 繼之，將形成該塗膜之玻璃基板於例如100至140 °C加 熱處理（預烘烤）去除殘留溶劑，形成光阻被膜。預烘烤 方法係以於熱板與基板間保有間隙作鄰近烘烤處理爲佳。 又，對於上述光阻被膜，用描繪有光罩圖型之光罩作 選擇性曝光。 爲形成微細圖型，光源以用i線（365奈米）爲佳。又 ，用於該曝光之曝光程序係，NA在0.3以下，0.2以下較佳 ，〇 · 1 5以下更佳’以低N A條件下曝光程序爲佳。 其次’對於選擇性曝光後之光阻被膜施以加熱處理（ 曝光後烘烤：PEB) 。PEB方法有，熱板與基板之間保有 間隙的鄰近烘烤處理’無間隙之直接烘烤處理；爲免基板 發生翹曲’得PEB之擴散效果，以作鄰近烘烤後進行直接烘 烤之方法爲佳。而’加熱溫度係90至150°C，尤以100至140 °C爲佳。 上述PEB後之光阻被膜，用顯像液，例如1至1〇質量％氫 氧化四甲銨水溶液等之鹼水溶液施以顯像處理，則曝光部份 溶解去除’同時於基板上形成積體電路用之光阻圖型，及液 -23- (20) (20)1326801 晶顯示部份用之光阻圖型。 又，殘留於光阻圖型表面之顯像液，以純水等淋洗液 洗糠，可形成光阻圖型。 該光阻圖型之形成方法中，製造系統LCD時，上述進行 選擇性曝光之過程中，上述光罩係以使用描繪有’形成2.0 微米以下之光阻圖型用光罩圖型，及形成超過2.0微米之光 阻圖型用的光罩圖型二者之光罩爲較佳。 於是，本發明LCD用正型光阻組成物因解析度優，得光 罩圖型之微細圖型忠實重現之光阻圖型。因此，上述同時形 成光阻圖型之過程中，於上述基板上，圖型尺寸2.0微米以 下之積體電路用光阻圖型，及超過2.0微米之液晶顯示部份 用之光阻圖型可同時形成。 在此於LCD之製造領域，因使用大於半導體製造用之矽 晶圓的方形玻璃基板，得良好DOF特性以外，從提升生產力 之觀點，曝光面積宜層可能擴大。爲此，LCD之製造一般係 以採用低NA (透鏡之開口數）條件之曝光程序爲佳。其中 之系統LCD者，因於基板上除顯示部份以外亦形成積體電路 部份，基板有更大型化之傾向，宜採用比通常的LCD製造 時更低NA條件之曝光。 尤以系統LCD中，例如，相對於顯示部份圖型尺寸之2 至10微米左右，積體電路部份係以0.5至2.0微米左右之微細 尺寸形成。因之，宜可形成0.5至2.0微米左右之微細光阻圖 型’並且，亦希有良好的，能同時正確形成尺寸大大不同之 顯示部份及積體電路部份之光阻圖型的線性特性。又，系統 -24- (21) 1326801 LCD製造中，取代習知LCD製造用之g線（436奈米）曝光 ，改用更短波長之i線（ 365奈米）曝光的微影技術之使用， 亦有提升解析度之傾向。 根據本發明，因於正型光阻組成物添加（C )成分，得 DOF特性之提升效果以外，可得解析度之提升效果、靈敏度 之提升效果。又，於低NA條件亦可得高靈敏度、高解析度 。又’於系統LCD之製造中亦可達良好之線性。又再，（B )成分採用非二苯基酮系化合物時，亦適用於i線曝光。 因此’本發明之正型光阻組成物適用於LCD及系統LCD 之製造。 並且根據使用本發明之正型光阻組成物的光阻圖型形 成方法’可於良好重現性得形狀良好之光阻圖型，生產力 也變得良好。 而特開平8 — 137100號公報、特開平9 — 244231號公報雖 記載’使光阻組成物含聚酚化合物，以得提升靈敏度之效 果’但本發明之添加特定的（C )成分以得d〇F提升效果、 解析度提升效果則未見提示。 實施例 以下舉實施例詳細說明本發明。 使用下述實施例1、2及比較例1至3中調製之正型光阻 組成物’依下述順序形成光阻圖型，進行評估。 評估方法（1 )線性評估： ：TR 36000 ， 使用大型基板用光阻塗敷裝置（裝置名 -25- (22) (22)1326801 東京應化工業（股）製，將正型光阻組成物塗敷於經形成 Ti膜之玻璃基板（ 550毫米X 650毫米）上後，使熱板溫度 爲100 °C，以約1毫米之間隔的鄰近烘烤作第一次乾燥90秒 。其次使熱板溫度爲9 0 °C，以〇 . 5毫米之間隔的鄰近烘烤 作第二次乾燥90秒，形成膜厚1.5微米之光阻被膜。 其次對於光阻被膜，透過同時描繪用以重現3.0微米 線條與間隔（L & S )及1 . 5微米L & S之光阻圖型的測試圖光 罩（標線），使用i線曝光裝置（裝置名：FX-702J， Nikon公司製；ΝΑ = 0·14)，以能忠實重現1.5微米L&S之 曝光量（Εορ曝光量）作選擇性曝光。 其次，對於選擇性曝光後之光阻被膜，使熱板溫度爲 12 0°C ’以0.5毫米間隔的鄰近烘烤施以加熱處理30秒，其 次於同溫度以無間隔之直接烘烤作加熱處理6 0秒。 其次’將23°C，2.38質量％之TMAH水溶液（氫氧化四 甲銨水溶液）以具有隙縫塗敷噴嘴之顯像裝置（裝置名： TD — 39000示範機，東京應化工業（股）製），如第1圖 自基板端部X經Y至Z，以1 〇秒湧液於基板（加熱處理後之 光阻被膜）上，保持5 5秒後，水洗3 0秒，旋轉乾燥。 然後以SEM (掃描式電子顯微鏡）照片觀察所得光阻 圖型之截面形狀’評估3.0微米L&S光阻圖型之重現性。 尺寸變化率± 10%以內者爲A (優），超過10%至15 %以內 爲B (可），超過15%爲C (劣）。 (2 ) 靈敏度評估： 上述（1 )線性評估中，1 . 5微米L& S光阻圖型可忠實 -26- (23) (23)1326801 重現之曝光量（Εορ)以毫焦耳單位求出。 (3 ) DOF測定： 上述（2)靈敏度評估之曝光量（Εορ)下，將焦點適 當上下滑移’ 1.5微米L&S之尺寸變化率在± 1〇 %範圍內的 焦點深度（D Ο F )之寬，以微米單位求出。 (4 ) 解析度評估： 上述（2)靈敏度評估之曝光量（Εορ )下求出極限解 析度。 (5 ) 殘膜率評估： 上述（1 )線性評估中，以SEM照片觀察I·5微米L&S 光阻圖型之截面形狀，光阻圖型之膜厚超過1.3至1.5微米 者爲Α (優），超過1.0至1.3微米者爲B (可），1.〇微米 以下者爲C (劣）。 (6 ) 光阻圖型形狀評估： 上述（1 )線性評估中’以SEM照片觀察1.5微米L&s 光阻圖型之截面形狀’光阻圖型呈矩形者爲A (優），呈 錐狀者爲C (劣）。 (實施例1、2，比較例1至3 ) 準備以下成分用作（A)至（D)成分及（X)成分。 (A ) 成分： (A1)使用間甲酚/3,4_二甲酚=8/ 2(莫耳比）之混 合酚類1莫耳，及甲醛〇·82莫耳以一般方法合成的 -27- (24) (24)1326801(wherein R12 and R13 each independently represent 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; An integer representing 1 to 3) or Q1 may be bonded to the end of R9, in which case Q1 together with R9 and a carbon atom between Q1 and R9 ' represents a cycloalkyl group having a carbon chain of 3 to 6; a, b represents 1 to 3 Integer; d is an integer from 0 to 3; a, bd is 3, no R3, R6 or R8; η represents an integer from 0 to 3) The positive photoresist composition for LCD manufacturing of the present invention is suitable for use on a substrate A substrate process for forming an integrated circuit and a liquid crystal display portion. Moreover, the present invention provides a process comprising: (1) applying the positive-type photoresist composition to a substrate to form a coating film, and (2) heat-treating the substrate on which the coating film is formed (pre-baking) a process of forming a photoresist film on a substrate, (3) a process of selectively exposing the photoresist film, and (4) applying a heat treatment to the photoresist film after the selective exposure (post-exposure baking) And a process for forming a photoresist pattern in the process of performing development processing with an aqueous alkali solution for the photoresist film after the heat treatment. [Embodiment] Hereinafter, the present invention -8-(5)(5)1326801 [positive photoresist composition] <(A) component> (A) component is an alkali-soluble resin. The component (A) is not particularly limited, and a positive photoresist composition can be optionally used. Φ It is usually used as one or more of those which are formed into a film. For example, phenols (phenol, m-cresol, p-cresol, xylenol 'three-way, etc.) and aldehydes (formaldehyde, formaldehyde precursor, propionaldehyde, 2-hydroxybenzaldehyde' 3 ~ hydroxybenzaldehyde, 4 _ hydroxybenzaldehyde, etc. and/or ketones (butanone, propyl, etc.) are condensed in the presence of an acidic catalyst; phenolic phenolic resin; hydroxystyrene monomer, hydroxystyrene and other styrene monomers a copolymer, a hydroxystyrene resin such as a copolymer of hydroxyphenethyl group and acrylic acid or methacrylic acid or a derivative thereof; a copolymer of acrylic acid or methacrylic acid and a derivative thereof, an acrylic acid or a methacrylic resin. In particular, a lacquer phenolic resin obtained by condensation reaction of at least two phenols selected from the group consisting of m-cresol, p-cresol, 3,4-xylenol and 2,3,5-trimethylphenol with formaldehyde-containing aldehydes It is suitable for modulating high sensitivity and excellent resolution of photoresist materials. The component (A) can be produced by a general method. The polystyrene-converted mass average molecular weight (Mw) of the component (A) by gel permeation chromatography depends on the kind thereof, but the sensitivity and pattern formation are preferably from 2,000 to 100,000, preferably from 3,000 to 30,000. The component (A) can be produced by a general method. -9- (6) (6) 13268001 < (B) Component> (B) If the component is a general positive resist composition, the naphthoquinonediazide ester used as a photosensitive component is not particularly limited. Any one or two or more may be used. Among them, the phenol compound of the above general formula (I) and the esterified product of the naphthoquinonediazide sulfonic acid compound are suitable for lithography using i-line, and are also suitable for forming a good shape under low NA conditions. A fine photoresist pattern of 2.0 microns or less. Preferably, in the phenol compound of the above general formula (1), Q1 is not bonded to the terminal of R9, and R9 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Q1 represents a residue of the above formula (II). , η Table 0 phenolic compound, • Q1 does not bind to the end of R9, R9 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Q1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Linear polyfluorene compounds of the integers of Tables 1 to 3. The above phenolic compound, more specifically, ginseng (4-carboxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(4~hydroxy~~2, 3,5-trimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane' bis(4-hydroxy-3,5-xylene Base) 3-hydroxyphenylmethane, bis(4_hydroxy-3; 5〆dimethylphenyl)~2_hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-4~ Hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethyl-10 - (7) (7)1326801 alkane, bis(4-hydroxy-3-3,5-dimethylphenyl)_3,4-dihydroxyphenylmethane, bis(4-hydroxy- 2,5-dimethylphenyl)_ 3 , 4-dihydroxyphenylmethane, bis(4_hydroxy-2,5-dimethylphenyl)-2,4-dihydroxyphenylmethane, bis(4-hydroxyphenyl)_3_methoxy-4-hydroxyl Phenylmethane, bis(5-cyclohexyl-4-hydroxyl-2-tolyl)_4 hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)_3_hydroxyphenylmethane, Double (5_cyclohex-4-hydroxyl) 2-(Tolyl)_2_hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)_3,4-dihydroxyphenylmethane, and the like. The above linear polyphenol compound, more specifically, 2,4-bis(3,5-dimethyl-4-hydroxybenzyl)-5-hydroxyphenol, 2,6-bis(2,5-dimethyl —4 —Hydroxybenzyl”_4—cresol, a linear trinuclear phenol compound; 1,1 —bis[3—(2-hydroxy-5-tolylmethyl)-4-hydroxy-5-cyclohexyl] Isopropane, bis[2,5-dimethyl-3-(4_hydroxy-5-toluomethyl)-4-hydroxyphenyl]methane, bis[2,5-dimethyl-3-yl (4-hydroxybenzyl) ) 4-tetrahydroxyphenyl]methane, bis[3-(3,5-dimethyl-4-hydroxybenzyl)_4_hydroxy-5-tolyl]methane, bis[3-—3,5-di A 4-hydroxyphenylmethyl)_4_hydroxy-5_ethylphenyl]methane, bis[3_3,5-dimethyl-4-hydroxybenzyl)-4-hydroxy-5-methylphenyl]methane, double [3_(3,5_diethyl-4-hydroxybenzyl)-4-hydroxy-5-ethylphenyl)methane, bis[2-hydroxy-3-(3,5-methyl-4-phenylene) Methyl)-5-tolyl], bis[2-hydroxy-3_(2-hydroxy-5-toluomethyl)-5-tolyl]methane[4 [hydroxyl_3_ (2-hydroxy-5) _Toluenemethyl)-5-tolyl]methane 'bis[2,5-dimethyl-3-(2-hydroxy-5-toluomethyl)- 4-hydroxyphenyl]methane Tetranucleotide phenolic compound; 2,4-bis[2-hydroxy-3-(8)(8)1326801 (4-hydroxybenzyl)-5-toluomethyl]-6-cyclohexanol, 2,4 —bis[4-hydroxy-3-(4-hydroxybenzyl)_5-toluomethyl]_6_cyclohexanol, 2,6_bis[2,5-dimethyl-3-(2— via a 5- A linear pentanucleoside phenol compound such as toluylmethyl)-tetramethylol benzyl]~4-cresol. Further, in addition to the above-mentioned phenolic compound and the above linear polyphenol compound, the phenol compound of the general formula (I) is bis(2,3,4-trihydroxyphenyl)methane or bis(2,4-dihydroxybenzene). Methane, 2,3,4-trihydroxyphenyl_4-hydroxyphenylmethane, 2-(2,3,4-trihydroxyphenyl)-2- (2,3,,4,- Trishydroxyphenyl)propane, 2(2,4-dihydroxyphenyl)-2-(2,4,-dihydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(4-hydroxyl) Phenyl)propane, 2-(3_fluoro-4-hydroxyphenyl)-2-iso(3,-fluoro-4-, hydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2 —(4'-Hydroxyphenyl)propane '2-(2,3,4-trihydroxyphenyl)_3-(4,monohydroxyphenyl)propane, 2_(2,3,4-trihydroxyphenyl) a bisphenol type compound such as 2-(4,-hydroxy-3,5,1-dimethylphenyl)propane; 1_[1-(4-hydroxyphenyl)isopropyl]-4-[], 1-double (4-hydroxyphenyl)ethyl]benzene, 1-[}_(3-methyl-4-hydroxyphenyl)isopropyl]-4-[1,1-bis(3~methyl-4-hydroxybenzene) Polynuclear branched compound such as ethyl) benzene; 1,1 bis(4-hydroxyphenyl) ring Alkoxy and other condensation type phenol compounds and the like. These phenol compounds may be used alone or in combination of two or more. Among them, the phenolic compound is the main component, and the sensitivity and resolution are better, especially bis[5-cyclohexyl-4-hydroxy-2-phenyl)-3,4-dihydroxyphenylmethane [ The following is abbreviated (B1·). : I, bis(4-hydroxy-2,3,5-trimethylphenyl)-2-hydroxyphenylmethane [hereinafter abbreviated as (B3,). ] -12- 1326801 Ο) is better. Further, it is a photoresist composition having an overall balance of modulation resolution, sensitivity, heat resistance, DOF characteristics, linearity, and the like, and is preferably a linear polyphenol compound, a bisphenol compound, a multinuclear branched compound, and A condensed phenol compound or the like is used in combination with the above phenolic compound. In particular, bis(2,4-dihydroxyphenyl)propane in the bisphenol type compound is used [hereinafter (B2·). ], can modulate the overall balanced excellent photoresist composition. Hereinafter, each of the naphthoquinonediazide esters of the above (ΒΓ), (B2-), and (B3') is slightly (Bl), (B2), and (B3). When (B1) or (B3) is used, the amount of the component (B) is preferably 10% by mass or more and 15% by mass or more. The naphthoquinonediazidesulfonic acid compound is preferably a 1,2-naphthoquinonediazide-4-sulfonate compound or a 1,2-naphthoquinonediazide-5-sulfonate compound, and the specific examples are 1,2. - naphthoquinone diazide _4 sulfonium chloride, 1, 2 _ 醌 醌 diazide _ 5 - acid chloride and the like. The component (B) contains all or a part of the phenolic hydroxyl group of the compound of the above general formula (I), and a naphthoquinonediazide compound esterified with a 1,2-naphthoquinonediazidesulfonium compound. A general method can be used for the whole or a part of the phenolic hydroxyl group of the compound of the formula (I). For example, '1,2-naphthoquinonediazidesulfonyl chloride can be obtained by condensing the compound of the above general formula (I). Specifically, it can be such that the compound of the above general formula (I) and 152-naphthoquinonediazidesulfonium chloride are dissolved in a specific amount in organic materials such as dioxan, n-methylpyrrolidone, dimethylacetamide, tetrahydrofuran, and the like. The solvent is reacted with one or more kinds of basic catalysts such as triethyl-13-(10)(10)1326801 amine, triethanolamine, pyridine, alkali metal carbonate or alkali metal hydrogencarbonate, and the obtained product is washed with water. Dry and modulate. (B) Component In addition to the above preferred naphthoquinonediazide esters exemplified above, other naphthoquinonediazide compounds which are generally used as a photosensitive component in a positive resist composition can be used. For example, an esterification reaction product of a phenol compound such as polyhydroxydiphenyl ketone or an alkyl arylate with a naphthoquinonediazidesulfonic acid compound or the like can also be used. These other naphthoquinonediazide compounds may be used singly or in combination of two or more. The amount of the other naphthoquinone diazide compound used is preferably 80% by mass or less by weight of the component (B), particularly preferably 50% by mass or less, which is preferable in the improvement of the effect of the present invention. The amount of the component (B) in the positive resist composition of the present invention is 20 to 70% by mass based on the total amount of the component (A) and the following component (C) and the following component (X). More preferably 60% by mass. When the blending amount of the component (B) exceeds the above lower limit ,, a faithful image of the pattern can be obtained, and the transfer property can be improved. When the temperature is below the upper limit ,, the sensitivity can be prevented from deteriorating, and the uniformity of the formed photoresist film is improved, and the resolution is improved. <(C) Component> The component (C) is a compound having a fluorene-containing base group of the above general formula (III), and has a molecular weight of 1,000 or less, more preferably 700 or less. In essence, it is more than 2 inches, and more preferably 300 or more. -14- (11) (11)1326801 The phenolic hydroxyl group-containing compound of the above general formula (III) includes a linear trinuclear phenol compound of m system 1 and a linear tetranuclear phenol compound of m system 2, m system 3 The linear penta-nuclear phenol compound 'm-line 4 type hexa-nuclear phenol compound, and m-type 5 linear hexa-nuclear phenol compound. Specific examples of these are, in addition to the linear trinuclear phenol compound which can constitute a specific example of the linear polyphenol compound of the above component (B), there are 2,6-bis(3,5-dimethyl-4-hydroxybenzoate). ) 4- 4-cresol, 2,4-bis(3,5-dimethyl-4-hydroxybenzyl)-6-cresol, 2,4-bis[1-(4-hydroxyphenyl)isopropyl a linear trinuclear phenol compound such as a 5-hydroxyphenol; a linear tetranuclear phenol compound and a linear pentanucleoside phenol compound which are specific examples of the linear polyphenol compound which constitutes the component (B); - 1 8 67 05 ' ' ' ' ' ' ' ' 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 It is preferable that the component (C) is a solvent which is soluble in the composition of the photoresist, and the above-mentioned m-type 1 or 2, a substituted hydroxy group of the terminal benzene ring selected from the above general formula (III) is preferably used. It is preferred to combine one or more groups of the phenolic hydroxyl group-containing compound of the trinuclear or tetranuclear compound in the para position. An example of a compound having a phenol or a hydroxyl group which is excellent in solubility is a bis[3_(3,5-dimethyl-4-hydroxyphenylmethyl)-4-hydroxymethylphenyl] compound [hereinafter abbreviated (C1)]. Further, examples of the phenolic hydroxyl group-containing compound of the trinuclear body are '2,6-bis(2,5-dimethyl-4-hydroxyphenylmethyl)-4-methylphenol [hereinafter abbreviated as (C2)], 2,6 —bis(3,5-dimethyl-4-hydroxybenzyl)-4-formamidine [hereinafter abbreviated as (C3)], 2,4 — (3,5-dimethyl-4-hydroxybenzene Methyl)-6-cresol [hereinafter abbreviated as (C4)], 24-double [丨一(4 -15-(12) (12)1326801-hydroxyphenyl)isopropyl] 5-hydroxyphenol [ The following is a brief (C5)]. Among these, (C2) to (C5) are preferred, and (C2) is particularly preferred. The component (C) may be used alone or in combination of two or more. In the present invention, the amount of the component (C) is preferably 5 mass% or more with respect to the component (A), and more preferably 10 mass% or more. Further, when the amount of the component (C) is too large, the balance of the other components is deteriorated, so that it is preferably 50% by mass or less, more preferably 40% by mass or less. <(X) component> The positive resist composition of the present invention may contain (X) other phenolic hydroxyl group-containing compound other than the component (C). In particular, when the component (C) is used in a case where the solubility of the solvent at the time of modulating the photoresist composition is low, the above-mentioned components (C) and (X) are used, and the addition effect of the component (C) can be obtained. good. The component (X) is preferably used as a sensitivity improving agent or a sensitizer as a phenolic hydroxyl group-containing compound having a molecular weight of 100 Å or less as a photoresist composition, and is not contained in the component (C). The more preferable molecular weight of the above (X) component is 700 or less, substantially 200 or more, and more preferably 300 or more. Specifically, among the ester compounds which constitute the component (B) described above, those which are not contained in the above component (C) and whose molecular weight is within the above range can be used as the component (X). Suitable (X) components, specific examples are ginseng (4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,3,5- Trimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-di-16-(13)(13)1326801 tolyl)_4-hydroxyphenylmethane, bis(4-hydroxy-3,5 _Xylphenyl) _3_hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)- 4 hydroxy Benzene, bis(4_hydroxy-2,5-dimethylphenyl)_3_hydroxyphenylmethane, bis(4-hydroxy-2,5-xylene)_2-hydroxyphenylmethane, bis(4-hydroxyl-3, 5_Dimethylphenyl)_3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)_3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-xylene Base 2,4,4-di-benzaldehyde, bis(4-phenyl)- 3_methoxy-4, phenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methyl) 4-tetrahydroxybenzene methane, bis(5-cyclohexyl-4-hydroxy-2-phenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane , bis(5-cyclohexyl-4-hydroxy-2-phenyl)-3,4 - Dihydroxyphenylmethane isophenolic compound; bis(2,3,4-trihydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)methane, 2,3,4-trihydroxybenzene-4 '_Hydroxyphenylmethane, 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 -(31-gas-4'-phenyl)propanoid, 2_(2,4_ phenyl)_2_(4'-hydroxyphenyl)propane, 2_(2,3,4-trihydroxyphenyl)- Bisphenolic compound such as 2_(4'-hydroxyphenyl)propane, 2_(2,3,4-trihydroxyphenyl)-2_(4'-hydroxy-3,5'-dimethylphenyl)propane; 1_[ 1-(4-hydroxyphenyl)isopropyl]_4-(1,1-bis(4-hydroxyphenyl)ethyl]benzene, 1-[1_(3-methyl-4-hydroxyphenyl)isopropyl ]—4 -17- (14)1326801 -[1 compound 2,3-hydroxyditetrahydroxy hydroxy dihydroxy, bis-4, bishydroxybenzene 2 - E phenyl hydroxybenzene [M is the best , , 1 double (3 - methyl 4 - hydroxyphenyl) ethyl benzene and other multinuclear branching; 1, 1 pair ( a condensed phenolic compound such as 4-hydroxyphenyl)cyclohexane; bis-diphenyl ketone, 2,4,4,tris-dihydroxydiphenyl copper, 2,4,6-triphenyl ketone, 2 , 3,4~trihydroxy_2__methyldiphenyl ketone' 2,3:4,4,monophenyl ketone, 2,2,4,4,tetrahydrodiphenyl ketone, 2,4, 6,3,,4,15* phenyl ketone, 2,3,4,2,,4, _ pentahydroxydiphenyl ketone, 2,3,4,2',5, penta-phenyl ketone , 2,4,6,3,,4,,5,_hexahydroxydiphenyl ketone, 2,3,4,3,,4',5' polyhydroxydiphenyl ketones such as diphenyl ketone Wait. Specific examples of the component (X) of φ are (3) a 4- 4-hydroxyphenyl group other than the phenol compound of the naphthoquinonediazide compound of the 0» compound. - cumene, bis(3-methyl-hydroxyphenyl)phenylmethane, bis(2-methyl-4-hydroxyphenyl)benzhydrazide (3-methyl-2-hydroxyphenyl)phenylmethane 'double ( 3,5-dimethyl-4-yl)phenylmethane, bis(3_ethyl-4-hydroxyphenyl)phenylmethane 'bis(3-tetrahydroxyphenyl)phenylmethane' double (2-three-stage _ 4,5-dihydroxy)phenylmethane isoparaphenyl type compound. Among them, bis(2-methyl-4-indolyl)phenylmethane, 1-[1_(4-hydroxyphenyl)isopropyl]-tetra-bis(4-hydroxyphenyl)ethyl]benzene is preferred. . In the positive resist composition of the present invention, the total amount of the component (C) and the component (X) is preferably from 20 to 60% by mass based on the (A) component of from 10 to 70% by mass. . <(D) Component> (D) If the component is generally used for a photoresist composition, there is no special limitation. -18- (15) (15) 13268001, one or more kinds may be used, and a propylene glycol monoalkyl group may be used. Ether acetate, and/or 2-heptanone are excellent in coating property, and the film thickness uniformity of the photoresist film on a large glass substrate is excellent. Further, both propylene glycol-alkyl ether acetate and 2-heptanone may be used in combination, but each of them may be used alone or in combination with other organic solvents, and the film thickness is preferably uniform when applied by spin coating or the like. . The propylene glycol-alkyl ether acetate is preferably contained in the component (D) in an amount of from 50 to 100% by mass. The propylene glycol-alkyl ether acetate has, for example, a linear or branched chain alkyl group having 1 to 3 carbon atoms, wherein propylene glycol-methyl ether acetate (hereinafter or slightly PGMEA) is derived from large glass. The uniformity of the film thickness of the photoresist film on the substrate is excellent, and is particularly preferable. On the other hand, 2-heptanone, especially (B) naphthoquinonediazide telluride, uses a non-diphenylketone-based photosensitive component, specifically, the phenolic compound of the above general formula (I), and naphthoquinone A suitable solvent for the esterification reaction product of the azide sulfonic acid compound. 2-Heptanone is superior to PGME A in heat resistance, and has a characteristic of a photoresist composition which can reduce the occurrence of scum, and is a very good solvent. When 2-heptanone is used alone or in combination with other organic solvents, it is preferably 50 to 100% by mass in the component (D). Also, these good solvents may be mixed and used in other solvents. For example, a combination of methyl lactate, ethyl lactate or the like (preferably ethyl lactate) and an alkyl lactate is preferred because the film thickness of the photoresist film is excellent, and a photoresist pattern having an excellent shape can be formed. -19- (16) (16)1326801 When propylene glycol-alkyl ether acetate is used in combination with alkyl lactate, it is preferably combined with propylene glycol-alkyl ether acetate in an amount of 0.1 to 10 by mass ratio of alkyl lactate. A multiple of 1 to 5 times is preferred. Further, an organic solvent such as 7-butyrolactone or propylene glycol-butyl ether may be used. When 7-butyrolactone is used, the compounding range is preferably from 0. 01 to 1 times the mass ratio of propylene glycol-alkyl ether acetate, and preferably from 0.05 to 0.5 times. However, other organic solvents which can be blended specifically include the following solvents. That is, ketones such as acetone, methyl ethyl ketone, cyclohexanone, and methyl isoamyl ketone; ethylene glycol, propylene glycol, diethylene glycol 'ethylene glycol monoacetate', propylene glycol monoacetate, and diethylene glycol Alcohol monoacetate, or a polyhydric alcohol such as methyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether; and derivatives thereof; such as cyclic ethers of diammonium; and methyl acetate Ethyl acetate, butyl acetate, methyl propionate 'ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate and the like. When these solvents are used, it is preferred to be 50% by mass or less of the component (D). The positive-type photoresist composition of the present invention may contain a compatible additive such as an additional resin 'plasticizer for improving the performance of the photoresist film, etc., if it is not detrimental to the object of the present invention, Preservatives and surfactants are used to make the image of the developed image more conspicuous, the sensitizer for enhancing the sensitizing effect, the dye for anti-glare, and the adhesion promoter. . The anti-corona dye can be used as a UV absorber (for example, 2,2'54:4·-tetrahydroxydiphenyl ketone, 4-dimethylamine-2::4-dihydroxydiphenyl ketone, 5-amine- 3-methyl-1-phenyl- 4-(4-hydroxyphenylazo)pyrazole, 4-dimethylamine--20- (17) (17)1326801 4'-hydroxyazobenzene, 4-diethylamine — 41—Ethoxyazobenzene, 4-diethylamine azobenzene, curcumin, etc.). The surfactant may be added, for example, to anti-glare or the like, and may be, for example, FLUORADFC-430, FC-431 (trade name, Sumitomo 3M Co., Ltd.) EFTOP EF 122A, EF122B, EF122C, EF126 (trade name 'TOCHEM PRODUCT' (Fly) system and other fluorine-based surfactants 'XR-104, MEGAFACR- 08 (trade name, manufactured by Dainippon Ink Chemicals Co., Ltd.). <Preparation of Positive-Type Photoresist Composition of the Present Invention> The positive-type photoresist composition of the present invention preferably contains (A) component, (B) component, (C) component, and other components as necessary. It is prepared by dissolving in an organic solvent. The component (D) is preferably used in such a manner that when the components (A) to (C) and other components used as necessary are dissolved, a uniform positive resist composition is appropriately adjusted. More preferably, the solid content concentration is from 1 至 to 50% by mass '20 to 35% by mass. Further, the solid content of the positive resist composition corresponds to the total of the components (A) to (C) and other components used as necessary. The positive resist composition of the present invention preferably has a Mw (hereinafter referred to as a resist molecular weight) in a range of from 5,000 to 30,000, more preferably from 6,000 to 10,000, in terms of the solid content of the resist composition. When the molecular weight of the above-mentioned photoresist is within the above range, that is, the decrease in sensitivity is not obtained, high resolution can be obtained, and a positive resist composition having excellent linearity and D0F characteristics and excellent heat resistance can be obtained. When the molecular weight of the photoresist is less than the above range, the resolution, linearity, and DOF characteristics are -21 (18), and the heat resistance is insufficient. When the molecular weight exceeds the above range, the sensitivity is remarkably lowered, which impairs the coating property of the photoresist composition. Hey. In the present specification, the term "resistance molecular weight" is used, and the following is determined by the GPC system. Device name: SYSTEM 1 1 (product name, manufactured by Showa Denko Co., Ltd.) Front column: KF-G (product name, manufactured by Shodex) Column: KF-805, KF — 8 03, KF-802 (product name, Sh Detector: 41dex company: UV41 (product name 'Shodex), measured at 280 nm. Solvent, etc.: Circulate tetrahydrofuran at a flow rate of 1 · 0 ml / min, at 35. (Measurement: Measurement sample preparation method: The photoresist composition to be measured was adjusted to have a solid concentration of 30% by mass, and diluted with tetrahydrofuran to prepare a measurement sample having a solid concentration of 0.1% by mass. The measurement sample was 20 μm. The above apparatus is used for the measurement. In the preparation of the positive-type photoresist composition of the present invention, the molecular weight of the photoresist is adjusted to fall within the above-mentioned suitable range, for example, (1) the Mw after mixing the components used falls into the above. In the range, the separation operation of the component (A) before mixing, the method of adjusting the Mw of the component (A) in an appropriate range, and (2) preparing a plurality of components (A) having different Mw, and appropriately adjusting the solid component. The method of Mw is in the above range, etc. Among these modulation methods, the modulation method of the above (2) is preferable because of adjustment of the molecular weight of the photoresist and sensitivity adjustment. <Method of Forming Photoresist Pattern> In the manufacture of LCD, a suitable method for forming a photoresist pattern is -22-(19)(19)1326801. First, the positive-type photoresist composition of the present invention described above is a spin coater or the like. A coating film is formed on the substrate. The substrate is preferably a glass substrate. The glass substrate is usually made of amorphous yttrium oxide, and the system LCD is preferably made of low-temperature polysilicon or the like. The photoresist composition has excellent resolution under low NA conditions, and can be used as a large substrate of 500 mm X 600 mm or more, especially 550 mm X 650 mm or more. Then, the glass substrate on which the coating film is formed is, for example, 100 to 140. °C heat treatment (prebaking) to remove the residual solvent to form a photoresist film. The prebaking method is preferably to maintain a gap between the hot plate and the substrate for the adjacent baking treatment. Further, for the photoresist film described above, A photomask with a reticle pattern is used for selective exposure. To form a fine pattern, the light source is preferably i-line (365 nm). Also, the exposure program for the exposure is NA below 0.3, below 0.2. Preferably, 〇·15 or less is better. The exposure procedure is preferably performed under low NA conditions. Secondly, the photoresist is subjected to heat treatment after selective exposure (exposure baking after exposure: PEB). The PEB method has heat. Between the board and the substrate Adjacent baking treatment of the gap 'direct baking treatment without gap; in order to avoid warping of the substrate, the diffusion effect of PEB is better, and the method of direct baking after baking is preferred. The heating temperature is 90 to 150 ° C, particularly preferably 100 to 140 ° C. The photoresist film after the PEB is subjected to development treatment using a developing solution such as a 1 to 1 〇 mass% aqueous solution of tetramethylammonium hydroxide or the like. Then, the exposed portion is dissolved and removed, and the photoresist pattern for forming the integrated circuit on the substrate is simultaneously formed, and the photoresist pattern for the liquid portion of the liquid -23-(20) (20)1326801 is displayed. The image-forming liquid on the surface of the pattern is washed with a rinse solution such as pure water to form a photoresist pattern. In the method of forming the photoresist pattern, in the process of selectively performing the exposure of the LCD, the photomask is formed by using a photomask pattern formed by forming a photoresist pattern of 2.0 micrometers or less. A reticle with a reticle pattern of more than 2.0 micrometers is preferred. Therefore, the positive-type photoresist composition for LCD of the present invention is excellent in resolution, and the photoresist pattern of the reticle pattern is faithfully reproduced. Therefore, in the process of simultaneously forming the photoresist pattern, the photoresist pattern for the integrated circuit having a pattern size of 2.0 μm or less and the photoresist pattern for the liquid crystal display portion exceeding 2.0 μm are available on the substrate. At the same time formed. Here, in the field of manufacturing of LCDs, the use of a square glass substrate larger than that of a semiconductor wafer for semiconductor manufacturing has a good DOF characteristic, and the area of the exposed area may be enlarged from the viewpoint of improving productivity. For this reason, LCDs are generally manufactured by an exposure procedure using a low NA (number of apertures of the lenses). Among the system LCDs, since the integrated circuit portion is formed on the substrate in addition to the display portion, the substrate has a tendency to be larger, and it is preferable to use an exposure of a lower NA condition than that in the conventional LCD manufacturing. In particular, in the system LCD, for example, the integrated circuit portion is formed in a fine size of about 0.5 to 2.0 μm with respect to about 2 to 10 μm of the size of the display portion. Therefore, it is desirable to form a micro-resistance pattern of about 0.5 to 2.0 micrometers, and it is also desirable to correctly form linear characteristics of the photoresist pattern of the display portion and the integrated circuit portion which are greatly different in size at the same time. . In addition, the system-24-(21) 1326801 LCD manufacturing replaces the g-line (436 nm) exposure used in the conventional LCD manufacturing, and uses the lithography technology of the shorter-wavelength i-line (365 nm) exposure. There is also a tendency to improve the resolution. According to the present invention, since the (C) component is added to the positive resist composition, the effect of improving the DOF characteristics and the effect of improving the sensitivity can be obtained. Moreover, high sensitivity and high resolution can be obtained under low NA conditions. In addition, good linearity can be achieved in the manufacture of system LCDs. Further, when the component (B) is a non-diphenyl ketone compound, it is also suitable for i-line exposure. Therefore, the positive resist composition of the present invention is suitable for the manufacture of LCDs and system LCDs. Further, according to the photoresist pattern forming method using the positive-type photoresist composition of the present invention, a good-resistance photoresist pattern can be obtained with good reproducibility, and productivity is also improved. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 9-244231. 〇F lifting effect, resolution improvement effect is not prompted. EXAMPLES Hereinafter, the present invention will be described in detail by way of examples. The photoresist patterns prepared in the following Examples 1 and 2 and Comparative Examples 1 to 3 were formed in the following order and evaluated. Evaluation method (1) Linear evaluation: :TR 36000, using a photoresist coating device for large substrates (device name -25-(22) (22)1326801 made by Tokyo Chemical Industry Co., Ltd., the positive photoresist composition After being applied to a glass substrate (550 mm X 650 mm) formed with a Ti film, the hot plate temperature was set to 100 ° C, and the first drying was performed for 90 seconds at a spacing of about 1 mm. The temperature of the plate is 90 ° C, and the adjacent baking at intervals of 毫米 5 mm is used for the second drying for 90 seconds to form a photoresist film having a film thickness of 1.5 μm. Next, for the photoresist film, the film is simultaneously reproduced for reproduction. Test pattern mask (line) of 3.0 micron lines and spaces (L & S) and 1.5 μm L & S photoresist pattern, using i-line exposure device (device name: FX-702J, Nikon Corporation) ΝΑ = 0·14), in order to faithfully reproduce the exposure of 1.5 μm L & S exposure (Εορ exposure) for selective exposure. Secondly, for the selective exposure of the photoresist film, the hot plate temperature is 12 0 °C 'The adjacent baking at 0.5 mm intervals is heat treated for 30 seconds, followed by the same temperature without interval Direct baking for heat treatment for 60 seconds. Next '23 ° C, 2.38 mass% of TMAH aqueous solution (tetramethylammonium hydroxide aqueous solution) as a developing device with a slit coating nozzle (device name: TD - 39000 demonstration Machine, Tokyo Chemical Industry Co., Ltd.), as shown in Figure 1 from the end of the substrate X through Y to Z, with 1 〇 seconds of liquid on the substrate (heat treated photoresist film), after 5 5 seconds , washed for 30 seconds, spin-dried. Then observe the cross-sectional shape of the obtained photoresist pattern by SEM (Scanning Electron Microscope) photograph to evaluate the reproducibility of the 3.0 μm L&S photoresist pattern. Dimensional change rate ± 10% The inside is A (excellent), more than 10% to 15% is B (may), and more than 15% is C (bad). (2) Sensitivity evaluation: In the above (1) linear evaluation, 1.5 μm L& S-resistance pattern can be faithful -26- (23) (23)1326801 The amount of exposure (Εορ) reproduced is obtained in millijoules. (3) DOF measurement: (2) Sensitivity evaluation exposure (Εορ) Next, the focus is appropriately shifted down to the depth of focus of the 1.5 μm L&S size change rate within ± 1〇% (D Ο The width of F) is obtained in micrometers. (4) Resolution evaluation: The above (2) sensitivity evaluation exposure amount (Εορ) is used to obtain the limit resolution. (5) Residual film rate evaluation: (1) linear In the evaluation, the cross-sectional shape of the I·5 μm L&S photoresist pattern was observed by SEM photograph. The film thickness of the photoresist pattern was more than 1.3 to 1.5 μm, which was Α (excellent), and those exceeding 1.0 to 1.3 μm were B ( Yes, 1. Less than 〇 micron is C (inferior). (6) Evaluation of the shape of the photoresist pattern: In the above (1) linear evaluation, the cross-sectional shape of the 1.5 μm L&s photoresist pattern is observed by SEM photograph. The photoresist pattern is rectangular (A), which is a cone. The person is C (inferior). (Examples 1, 2, and Comparative Examples 1 to 3) The following components were prepared for use as the components (A) to (D) and (X). (A) Ingredients: (A1) Mixed phenols 1 mol using m-cresol/3,4- xylenol = 8/ 2 (mole ratio), and formaldehyde oxime 82 mol are synthesized by a general method - 27- (24) (24)1326801
Mw = 20000 , Mw/Mn = 5.2之酚醛淸漆樹脂。 (B) 成分： (B1 ) :雙（5 —環己一4 —羥—2 —甲苯基）_3，4 —二羥苯甲烷（B 1，）1莫耳，與1 , 2 —萘醌二疊氮—5 _磺 醯氯[以下略作（5 - NQD) 。：I2莫耳之酯化反應產物。 (B2):雙（2,4 —二羥苯基）甲烷（Β2·) 1莫耳與5 —NQD 2莫耳之酯化反應產物。 (B3 ):雙（4_羥一2,3,5 —三甲苯基一 2 —羥苯甲 烷（B31) 1莫耳與5— NQD2莫耳之酯化反應產物。 (C ) 成分： (C2 ) 甲酚 :2,6 —雙（2,5 —二甲一 4 —羥苯甲基）—4_ (X) 成分： (XI) : 1 — [1_ (4_ 羥苯基）異丙基]—4_[M_ 雙（4 一羥苯基）乙基]苯Phenolic enamel resin with Mw = 20000 and Mw/Mn = 5.2. (B) Ingredients: (B1): bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)_3,4-dihydroxyphenylmethane (B 1,) 1 mol, with 1, 2 -naphthoquinone Azide-5 sulfonium chloride [hereinafter abbreviated as (5 - NQD). : I2 molar esterification reaction product. (B2): bis(2,4-dihydroxyphenyl)methane (Β2·) 1 molar and 5-NQD 2 molar esterification reaction product. (B3): bis(4_hydroxy-2,3,5-trimethylphenyl-2-hydroxyphenylmethane (B31) 1 molar and 5-NQD2 molar esterification reaction product. (C) Component: (C2 Cresol: 2,6-bis(2,5-dimethyl-4-hydroxybenzyl)-4_ (X) Component: (XI) : 1 — [1_ (4-hydroxyphenyl)isopropyl]- 4_[M_bis(4-hydroxyphenyl)ethyl]benzene
(XI ) :2，2·，4,4’一四羥二苯基酮 (〇 ) 成分： (D1 ) ：PGMEA 上述（A)至（C)成分及（X)成分依下述表丨之配 合量（質量份）使用，同時使用相對於這些（A)至（c -28- (25) (25)1326801 )成分及（X)成分之合計質量相當於45 0ppm之量的界面 活性劑（產品名'' R - 〇8 〃 ；大日本油墨化學工業（股） 製），將此等溶解於下述表1之（D)成分，更用孔徑0.2 微米之濾膜過濾，調製正型光阻組成物。所得正型光阻組 成物之光阻分子量倂列於表1。 就所得正型光阻組成物，各作上述（1 )至（6 )各項 目之評估。其結果列於下述表2。 表1 (A)成分 (配合量） (B)成分 (混合比） (配合量） (C)成分 (配合量） (X)成分 (配合量） (D)成分 (配合量） 光阻分 子量 實施例1 A1 (100) B1/B2/B3 (混合比6/11) (35) C2(25) D1 (455) 9000 實施例2 同上 同上 C2 (12.5) XI (12.5) 同上 同上 比較例1 同上 同上 — XI (25) 同上 同上 比較例2 同上 同上 — X2 (25) 同上 同上 比較例3 同上 同上 — _ 同上 9300 -29- (26) 1326801 表2(XI) : 2,2·,4,4'-tetrahydroxydiphenyl ketone (〇) Ingredients: (D1) :PGMEA The above components (A) to (C) and (X) are expressed in the following table. The amount of the compound (parts by mass) is used together with a surfactant having an amount equivalent to 45 0 ppm based on the total mass of the components (A) to (c -28- (25) (25) 13260801) and (X) ( Product name '' R - 〇8 〃 ; Dainippon Ink Chemical Industry Co., Ltd.), these are dissolved in the component (D) in Table 1 below, and filtered with a filter having a pore size of 0.2 μm to prepare positive light. Blocking composition. The photoresist molecular weight of the resulting positive resist composition is shown in Table 1. The obtained positive-type photoresist compositions were each evaluated for the above items (1) to (6). The results are shown in Table 2 below. Table 1 (A) component (mixing amount) (B) component (mixing ratio) (combination amount) (C) component (mixing amount) (X) component (mixing amount) (D) component (mixing amount) Photoresist molecular weight implementation Example 1 A1 (100) B1/B2/B3 (mixing ratio 6/11) (35) C2(25) D1 (455) 9000 Example 2 Same as above C2 (12.5) XI (12.5) Same as above Comparative Example 1 Same as above — XI (25) Same as above. Comparative example 2 Same as above—X2 (25) Same as above. Comparative example 3 Same as above— _ Ibid. 9300 -29- (26) 1326801 Table 2
線性 靈敏度 Λ焦耳） DOF (微米） 解析度 (微米） 殘膜率 圖型形狀 實施例1 A 100 25 1.2 A A 實施例2 A 75 23 1.25 A A 比較例1 A 50 20 1.3 B A 比較例2 A 65 15 1.5 C C 比較例3 A 100 15 1.5 B C 發明之效果 如以上說明，根據本發明可得，不僅D Ο F特性，能達 成解析度及殘膜率之提升的正型光阻組成物，及形成光阻 圖型之方法。 【圖式簡單說明】 第1圖用以評估線性，將正型光阻組成物塗敷於玻璃 基板、烘烤乾燥、圖型曝光後，以具有隙縫塗敷器之顯像 裝置使顯像液自基板端部X至Z湧液的要旨說明圖。Linear sensitivity Λ Joule) DOF (micron) resolution (micron) residual film rate pattern shape Example 1 A 100 25 1.2 AA Example 2 A 75 23 1.25 AA Comparative Example 1 A 50 20 1.3 BA Comparative Example 2 A 65 15 1.5 CC Comparative Example 3 A 100 15 1.5 BC Effect of the Invention As described above, according to the present invention, a positive resist composition capable of achieving an improvement in resolution and residual film ratio, and light formation can be obtained not only by D Ο F characteristics. The method of blocking the pattern. [Simple description of the drawing] Figure 1 is used to evaluate the linearity. After applying the positive photoresist composition to the glass substrate, baking and drying, and pattern exposure, the developing solution is provided by a developing device with a slit applicator. A schematic view of the liquid from the end of the substrate X to Z.