594393 A7 B7 五、發明説明（1 ) 【發明之內容】 【技術領域】 本發明係有關一種適合利用N A爲0 · 2以下之低N A條件下 的曝光製程之使用500 X 600mm2以上大型玻璃基板以製得 液晶顯不兀件之正型光阻組成物，與適合製造系統LCD ( Liquid Crystal Display)之正型光阻組成物。 目前爲止，於使用玻璃基板製造液晶顯示元件之領域 中，因較廉價，且可形成具有優良感度、解像性，及具有 優良形狀之光阻圖型，故多利用製造半導體元件所使用之 酚醛淸漆樹脂-含醌二疊氮基之化合物系所得之正型光阻組 成物。 但，於半導體製造中，最大爲使用直徑8英吋（約 200mm)〜12英吋（約300mm)之圓盤型矽晶圓，但於製造 液晶顯示元件中，常使用500 X 600mm2以上之方形玻璃基 板。於此液晶顯示元件之製造領域中，塗佈有光阻組成物 之基板，無論材質、形狀等面上皆與矽晶圓不同，就大小 觀點上亦與矽晶圓有著極大之不同。因此，製造液晶顯示 元件所使用之光阻材料，對於廣大基板面全面而言，常尋 求一種具有優良形狀與尺寸安定性之光阻圖型。 又’於液晶顯示元件之製造上，常需消耗許多光阻材 料’故除前述特性外，尙期待可開發出廉價之材料。 又，於下一世代之LCD，常需於1片玻璃基板上將驅動 電路、DAC、影像管理、影像控制、RAM等集積電路與顯像 部分同時形成，即，目前極盛行開發稱爲「系統LCD」之高 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -5 - (請先閲讀背面之注意事項再填寫本頁) 、11 經濟部智慈財產局員工消費合作社印製 594393 A7 B7 五、發明説明（2 ) 機能 LCD技術（Semiconductor FPD World 2001.9，pp.50-67) ο (請先閱讀背面之注意事項再填寫本頁) 但，相對於顯示器部分之圖型尺寸爲2至10 // m，集積 電路之尺寸則需形成0.5至2.0 // m左右之微細尺寸，故即使 於同一曝光條件下，欲形成前述集積電路與顯像部分時， 極需要具有優良之線性[同一曝光條件下（即使於光罩板（ Reticle )上之光罩尺寸不同時亦具有相同條件之曝光量） ，經曝光後使光罩板（Reticle)上之光罩尺寸重現之特性] 〇 欲提高解像度（解像界限）時，如下式所示雷利（ Rayleigh)式 R= ki>< λ / ΝΑ (式中，R爲解像界限，L爲光阻或製程、像形成法所 決定之比例參數，λ爲曝光製程中所使用之光的波長，NA 爲透鏡之開口數） 經濟部智慧財產局員工消費合作社印製 所示般，需使用短波長之光源，或必須使用高Ν Α之曝 光製程。因此，於形成2.0 // m以下微細光阻圖型時，需使 用較以往使用之g ( 436nm )射線曝光爲更短之i射線（ 365nm )曝光之光蝕刻印刷技術爲更有效。 但，就提昇產量之觀點而言，於液晶領域中之曝光區 域，以至少100mm2者爲較佳，因此欲形成高NA化係極爲困 難者。 於製造液晶顯示元件之領域中，如前記理由所述般， 一般係需在0.2以下低NA條件下進行，但於低NA條件下極不 -6 - 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 594393 A7 B7 五、發明説明（3 ) 易形成具有優良形狀之微細光阻圖型，而會造成光阻圖型 由矩形傾向錐形狀。因此，目前極需一種NA即使於0.2以下 之低NA條件下，亦可形成具有優良形狀之2.0// m以下微細 光阻圖型之製造液晶顯示元件用之光阻材料。 目前爲止已有許多報告提出對於製造液晶顯示元件用 之光阻材料。例如特開平9- 1 6023 1號公報、特開平9-211 855 號公報、特開2000- 1 121 20號公報、特開2000- 1 3 1 835號公報 、特開2000- 1 8 1055號公報與特開2001 -75272等。 前述材料，對於價廉之360 X 460mm2左右之較小型基 板’可形成具有優良塗佈性、感度、解像性、形狀與尺寸 安定性之光阻圖型，但於前述系統LCD製程中使用時，則極 需一種可再度提高其線性，NA爲0.2以下之低NA條件下亦可 形成微細光阻圖型，且適合i射線曝光製程之材料。 又，於特開2000-29208號公報與特開2000-29209號公報 中，雖記載有使用特定感光劑混合物之光阻組成物，但， 該公報中並未明確記載適合製造液晶顯示元件之組成內容 ，且未記載任何有關液晶顯示元件之製造步驟。 【發明之目的】 本發明之目的即是提供一種適合製造系統LCD之具有優 良線性、適合低NA條件下之曝光製程，且適合1射線曝光之 正型光阻組成物，及光阻圖型之形成方法。 【發明之內容】 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -------1I-- (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 594393 A7 B7 五、發明説明（4 ) 爲解決前述問題，經過深入硏究結果，本發明者們發 現使用含有鹼可溶性樹脂 '特定醌二疊氮酯化物、與特定 有機溶媒所構成之正型光·阻組成物，具有優良線性、適合 低N A條件下之曝光製程，且適合作爲1射線曝光之光阻材料 ’故極適合用於製造系統LCD使用，因而完成本發明。 申I靑項1之發明，爲一種製造液晶顯示元件用正型光阻 組成物，其係含有（A )驗可溶性樹脂、（B )酿二疊氮醋 化物、與（D )有機溶劑者； 其中，（B )成分係爲含有下記式（I )所示醌二疊氮 酯化物 (請先閲讀背面之注意事項再填寫本頁)594393 A7 B7 V. Description of the invention (1) [Content of the invention] [Technical field] The present invention relates to a large-sized glass substrate of 500 X 600 mm2 or more suitable for an exposure process under a low NA condition where NA is 0 or less A positive photoresist composition for a liquid crystal display device and a positive photoresist composition suitable for a manufacturing system LCD (Liquid Crystal Display) are obtained. So far, in the field of manufacturing liquid crystal display elements using glass substrates, because they are relatively inexpensive, and can form photoresist patterns with excellent sensitivity, resolution, and excellent shape, phenols used in the manufacture of semiconductor elements are mostly used. Lacquer resin-a quinonediazide-containing compound is a positive type photoresist composition. However, in semiconductor manufacturing, a disc-shaped silicon wafer with a diameter of 8 inches (about 200 mm) to 12 inches (about 300 mm) is used at the maximum. However, in the manufacture of liquid crystal display elements, squares with a size of 500 X 600 mm2 or more are often used. Glass base board. In the manufacturing field of this liquid crystal display element, a substrate coated with a photoresist composition is different from a silicon wafer in terms of material, shape, and the like, and is also very different from a silicon wafer in terms of size. Therefore, a photoresist material used for manufacturing a liquid crystal display element is generally required to have a photoresist pattern having excellent shape and dimensional stability for the entire substrate surface. In addition, in the manufacture of liquid crystal display elements, many photoresist materials are often consumed. Therefore, in addition to the aforementioned characteristics, it is expected that inexpensive materials can be developed. Moreover, in the next generation of LCD, it is often necessary to simultaneously form integrated circuits such as driving circuits, DACs, image management, image control, and RAM on a single glass substrate. LCD "high paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297mm) -5-(Please read the precautions on the back before filling out this page), 11 Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 594393 A7 B7 V. Description of the invention (2) Functional LCD technology (Semiconductor FPD World 2001.9, pp.50-67) ο (Please read the precautions on the back before filling this page) However, the size of the figure relative to the display is 2 to 10 // m, the size of the integrated circuit needs to form a fine size of about 0.5 to 2.0 // m, so even under the same exposure conditions, it is extremely necessary to have excellent linearity when forming the aforementioned integrated circuit and developing part [Under the same exposure conditions (even when the size of the reticle on the reticle is different, the exposure amount is the same under the same conditions). After exposure, the reticle size on the reticle is reproducible. ] 〇 If you want to increase the resolution (resolution limit), the following formula is Rayleigh (Rayleigh) formula R = ki > < λ / ΝΑ (where R is the resolution limit, L is the photoresist or process, image formation The ratio parameter determined by the law, λ is the wavelength of the light used in the exposure process, and NA is the number of openings of the lens. As shown by the printing by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, a short-wavelength light source must be used or must be used High Ν Α exposure process. Therefore, when forming a fine photoresist pattern below 2.0 // m, it is more effective to use a photo-etching printing technique that uses g (436 nm) ray exposure to be shorter than i-ray (365 nm) exposure used in the past. However, from the viewpoint of improving the yield, in the liquid crystal field, the exposure area is preferably at least 100mm2, so it is extremely difficult to form a high NA system. In the field of manufacturing liquid crystal display elements, as stated in the previous reasons, it is generally performed under the low NA condition of 0.2 or less, but it is extremely not -6 under the low NA condition.-This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 594393 A7 B7 V. Description of the invention (3) It is easy to form a fine photoresist pattern with excellent shape, which will cause the photoresist pattern to change from rectangular to tapered. Therefore, there is a great need for a photoresist material for manufacturing liquid crystal display elements with a fine photoresist pattern of 2.0 // m or less even under a low NA condition of 0.2 or less. Many reports so far have proposed photoresist materials for the manufacture of liquid crystal display elements. For example, Japanese Unexamined Patent Publication No. 9-1 6023 1, Japanese Unexamined Patent Publication No. 9-211 855, Japanese Unexamined Patent Publication 2000- 1 121 20, Japanese Unexamined Patent Publication 2000- 1 3 1 835, Japanese Unexamined Patent Publication 2000- 1 8 1055 With JP 2001-75272 and so on. The aforementioned materials can form a photoresist pattern with excellent coating properties, sensitivity, resolution, shape and size stability for the smaller substrates of about 360 X 460mm2, which are inexpensive, but when used in the LCD process of the aforementioned system, Therefore, there is a great need for a material that can increase its linearity again, and can form a fine photoresist pattern under low NA conditions of NA less than 0.2, and is suitable for i-ray exposure processes. Also, in JP-A-2000-29208 and JP-A-2000-29209, although a photoresist composition using a specific photosensitizer mixture is described, the publication does not explicitly describe a composition suitable for manufacturing a liquid crystal display element. Content, and does not record any manufacturing steps related to the liquid crystal display element. [Objective of the Invention] The purpose of the present invention is to provide a positive photoresist composition having excellent linearity suitable for manufacturing system LCDs, suitable for exposure processes under low NA conditions, and suitable for 1-ray exposure, and photoresist patterns. Formation method. [Contents of the invention] This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ------- 1I-- (Please read the precautions on the back before filling this page) Order the intellectual property of the Ministry of Economic Affairs Printed by the Bureau ’s Consumer Cooperatives 594393 A7 B7 5. Description of the Invention (4) In order to solve the aforementioned problems, after in-depth research, the inventors found that the use of alkali-soluble resin 'specific quinone diazide esters, and specific organic solvents The formed positive photoresist composition has excellent linearity, is suitable for the exposure process under low NA conditions, and is suitable as a photoresist material for 1-ray exposure. Therefore, it is extremely suitable for use in manufacturing system LCDs, and thus completed the present invention. The invention of claim 1 is a positive-type photoresist composition for manufacturing a liquid crystal display element, which contains (A) a soluble resin, (B) a diazide acetic acid compound, and (D) an organic solvent; Among them, the component (B) contains quinonediazide ester represented by the following formula (I) (please read the precautions on the back before filling this page)
經濟部智慧財產局員工消費合作社印製 (式中，D爲獨立之氫原子或1,2-萘醌二疊氮基-5-磺醯 基，且至少1個爲1，2-萘醌二疊氮基-5-磺醯基）。 申請項2之發明，爲如申請項1之正型光阻組成物，其 中有機溶劑係至少含有丙二醇單烷基醚乙酸酯。 申請項3之發明，爲如申請項1或2之正型光阻組成物， 其中有機溶劑係至少含有乳酸烷酯。 申請項4之發明，爲如申請項2之正型光阻組成物，其 中丙二醇單烷基醚乙酸酯係爲丙二醇單甲基醚乙酸酯（ PGMEA)。 申§靑項5之發明’爲如申請項3之正型光阻組成物，其 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -8 - 594393 A7 B7 五、發明説明（5 ) 中乳酸烷酯爲乳酸乙酯（EL)。 (請先閱讀背面之注意事項再填寫本頁) 申請項6之發明，爲如申請項1之正型光阻組成物，其 中鹼可溶性樹脂爲由含有m-甲酚與3,4-二甲酚之苯酚類與醛 類進行縮合反應所得之酚醛淸漆樹脂。 申請項7之發明，爲如申請項6之正型光阻組成物，其 中醛類係僅由丙醛與甲醛所得者。 申請項8之發明，爲如申請項1至7項中任一項之正型光 阻組成物，其中尙含有分子量1000以下之具有苯酚性羥基 之鹼可溶性低分子化合物所得之（C )感度提昇劑。 申請項9之發明，爲如申請項1至8項中任一項之正型光 阻組成物，其係用於系統LCD製造過程。 申請項10之發明，爲如申請項1至9項中任一項之正型 光阻組成物，其係用於使用500x 600mm2以上大型玻璃基板 的LCD製造過程。 申請項11之發明，爲如申請項1至1 〇項中任一項之正型 光阻組成物，其係用於i射線（365nm)曝光製程。 申請項1 2之發明，爲如申請項1至11項中任一項之正型 光阻組成物，其係用於NA爲0.2以下之曝光製程。 經濟部智慧財產局員工消費合作社印製 申請項1 3之發明，爲一種光阻圖型之形成方法，其係 包含 (1 )將申請項1至8項中任一項之正型光阻組成物塗佈 於500x 600mm2以上大型玻璃基板，以形成塗覆膜之步驟； (2 )將前記形成有塗覆膜之玻璃基板加熱處理（預熱 培），使其於玻璃基板上形成光阻被覆膜之步驟； 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） _ 9 - 594393 A7 B7 五、發明説明（6) (3 )對前記光阻被覆膜進行選擇性曝光之步驟； (請先閱讀背面之注意事項再填寫本頁) (4 )對前記選擇性曝光後之光阻被覆膜，以鹼水溶液 進行顯像處理，使其於玻璃基板上形成光阻圖型之步驟； 與 (5 )洗滌光阻圖型表面殘留之顯影液之洗淨步驟。 申請項14之發明，爲如申請項1 3之光阻圖型之形成方 法，其中（3)之選擇性曝光步驟，係使用同時描繪有2.0// m以下之形成光阻圖型用的光罩圖型與，超過2· 0//m之形成 光阻圖型的光罩圖型之光罩板，於玻璃基板上同時形成2.0 # m以下之光阻圖型與超過2.0// m之光阻圖型。 申請項15之發明，爲如申請項13或14之光阻圖型之形 成方法，其中（3)之選擇性曝光步驟係使用i射線（365nm )爲光源所進行之曝光製程。 申請項1 6之發明，爲如申請項1 3至1 5中任一項之光阻 圖型之形成方法，其中（3 )之選擇性曝光步驟係於N A爲 0.2以下之低NA條件下之曝光製程所進行者。 【發明之實施形態】 經濟部智慧財產局員工消費合作社印製 (A )成分（鹼可溶件樹脂） (A)成分之鹼可溶性樹脂，並未有特別之限定，只要 爲正型光阻組成物中作爲被膜形成物質之一般使用之物質 時皆可任意使用，較佳者例如芳香族羥基化合物與醛類或 酮類之縮合反應產物、聚羥基苯乙烯與及其衍生物等。 前記羥基化合物例如苯酚、m-甲酚、p-甲酚、〇-甲酚、 -10- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 594393 A7 B7 五、發明説明（7 ) 2,3-一甲苯酚、2,5-二甲苯酚、3,5-二甲苯酚、3,4-二甲苯酚 等二甲苯酚類，m-乙基苯酚、卜乙基苯酚、〇_乙基苯酚、 (請先閱讀背面之注意事項再填寫本頁} 2,3,5-三甲基苯酚' 2,3,5-三乙基苯酚、4-tert-丁基苯酚、3-iert-丁基苯酚、2-tert-丁基苯酚、2-tert-丁基-4-甲基苯酚、 2-tert-丁基-5-甲基苯酚等烷基苯酚類，p-甲氧基苯酚、^甲 氧基苯酚、P-乙氧基苯酚、m_乙氧基苯酚、[丙氧基苯酚、 m-丙氧基苯酚等焼氧基苯酣類，〇_異丙烯基苯酸、p_異丙烯 苯酚、2-甲基-4-異丙烯基苯酚、2-乙基-4-異丙烯基苯酚等 異丙烯基苯酚類，苯基苯酚等芳基苯酚類，4,4，_二羥基聯 苯、雙酚A、間苯二酚、對苯二酚、焦培酚等多羥基苯酚類 等。其可單獨使用或將2種以上組合使用皆可。 經濟部智慧財產局員工消費合作社印製 前記醛類，例如甲醛、對甲醛、三噁烷、乙醛、丙醛 、丁醛、三甲基乙醛、丙烯醛' 巴豆醛、環己醛、糖醛、 呋喃基丙烯醛、苯醛、對苯二甲醛、苯基乙醛、α —苯基丙 醛、石-苯基丙醛、〇-羥基苯醛、m_羥基苯醛、〇_甲基苯醛 、m-甲基苯醛、p-甲基苯醛、0_氯基苯醛、m_氯基苯醛、p_ 氯基苯醛、桂皮酸醛等。其可單獨使用或將2種以上組合使 用皆可。前述醛類中，就容易取得性而言，以甲醛爲佳， 特別是爲提高耐熱性時，以將羥基苯醛類與甲醛類組合使 用爲更佳。 前記酮類，例如丙酮、甲基乙基酮、二乙基酮、二苯 基酮等。其可單獨使用或將2種以上組合使用皆可。此外， 醛類與酮類亦可適當地組合使用。 前記芳香族羥基化合物與醛類或酮類之縮合反應產物 -11 - 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇χ；297公釐） 594393 A7 B7 五、發明説明（8 ) ，例如可於酸性觸媒之存在下以公知之方法製造。此時所 使用之酸性觸媒例如鹽酸、硫酸、甲酸、草酸、對苯磺酸 (請先閲讀背面之注意事項再填寫本頁) 等。 前記多羥基苯乙烯及其衍生物，例如乙烯基苯酚均聚 物、乙烯基苯酚與其共聚所得共聚用單體所得之共聚物等 。前述共聚用單體例如丙烯酸衍生物、丙烯腈、甲基丙烯 酸衍生物、甲基丙烯腈、苯乙烯、α-甲基苯乙烯、p-甲基苯 乙烯、〇-甲基苯乙烯、ρ-甲氧基苯乙烯、Ρ-氯基苯乙烯等苯 乙烯衍生物等。 其中最適合作爲本發明（A )成分使用之鹼可溶性樹脂 ，例如重量平均分子量（Mw )爲2000〜20000，特別是3000 〜1 2000之鹼可溶性酚醛淸漆樹脂爲佳，其中又以使用含有 m-甲酚、p-甲酚之苯酚類與丙醛與含有甲醛之醛類經縮合 反應所得之酚醛淸漆樹脂，極適合作爲高感度且具有優良 性線性之光阻材料。又，醛類可由丙醛與甲醛所構成者爲 佳。 (B )成分（醌二疊氮酯化物） 經濟部智慧財產局員工消費合作社印製 使用前述式（I )所示醌二疊氮酯化物即可製得具有優 良線性。且適合i射線曝光之光阻材料。 又，即使於NA爲0.2以下之低NA條件下時，特別是不會 造成預燒培條件、曝光後加熱（PEB )條件、顯影順序等之 變更，即可形成具有優良形狀之矩形且微細之光阻圖型。 又，該酯化物之平均酯化率爲20〜80% ，較佳爲35〜70 -12- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 594393 Α7 Β7 五、發明説明（9 ) % ，低於20%時其殘膜率與解像性將會降低，超過80%時 ，感度會顯著降低，又，會增加顯影殘留（殘渣）效果， 故爲不佳。 (B )感光性成分中，除前述醌二疊氮酯化物外，亦可 使用其他醌二疊氮酯化物。 例如下記式（II )所示醌二疊氮酯化物等（惟，不包含 式（I)所示化合物），Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (where D is an independent hydrogen atom or 1,2-naphthoquinonediazide-5-sulfonyl group, and at least one is 1,2-naphthoquinone di Azid-5-sulfonyl). The invention of claim 2 is the positive-type photoresist composition according to claim 1, wherein the organic solvent contains at least propylene glycol monoalkyl ether acetate. The invention of claim 3 is the positive-type photoresist composition according to claim 1 or 2, wherein the organic solvent contains at least an alkyl lactate. The invention of claim 4 is a positive-type photoresist composition according to claim 2, wherein the propylene glycol monoalkyl ether acetate is propylene glycol monomethyl ether acetate (PGMEA). The invention claimed in § 靑 Item 5 is a positive-type photoresist composition as in Item 3, and its paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -8-594393 A7 B7 V. Description of the invention ( 5) The alkyl lactate is ethyl lactate (EL). (Please read the precautions on the back before filling this page) The invention of application item 6 is the positive photoresist composition as in application item 1, wherein the alkali-soluble resin is composed of m-cresol and 3,4-dimethylformate. Phenolic lacquer resin obtained by the condensation reaction of phenol, phenols and aldehydes. The invention of claim 7 is the positive type photoresist composition as described in claim 6, wherein the aldehydes are obtained only from propionaldehyde and formaldehyde. The invention of claim 8 is a positive-type photoresist composition as described in any one of claims 1 to 7, wherein (C) sensitivity is improved by the addition of fluorene to an alkali-soluble low-molecular compound having a phenolic hydroxyl group having a molecular weight of 1,000 or less. Agent. The invention of claim 9 is a positive-type photoresist composition according to any one of claims 1 to 8 and is used in a system LCD manufacturing process. The invention of claim 10 is a positive-type photoresist composition according to any one of claims 1 to 9, which is used in an LCD manufacturing process using a large glass substrate of 500x600mm2 or more. The invention of claim 11 is a positive-type photoresist composition according to any one of claims 1 to 10, which is used for an i-ray (365 nm) exposure process. The invention of application item 12 is a positive-type photoresist composition according to any one of application items 1 to 11, which is used in an exposure process with NA of 0.2 or less. The invention of application item 13 printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economics is a method for forming a photoresist pattern, which includes (1) a positive photoresist composed of any one of application items 1 to 8. The process of coating the object on a large glass substrate with a size of 500x600mm2 or more to form a coating film; (2) heating (preheating) the glass substrate with the coating film previously described to form a photoresist on the glass substrate Laminating steps; This paper size applies Chinese National Standard (CNS) A4 (210X 297 mm) _ 9-594393 A7 B7 V. Description of the invention (6) (3) Selective exposure of the photoresist coating film Steps; (Please read the precautions on the back before filling this page) (4) Develop the photoresist coating film after selective exposure in the previous step with alkaline aqueous solution to form a photoresist pattern on the glass substrate And (5) a cleaning step of washing the developing solution remaining on the surface of the photoresist pattern. The invention of claim 14 is a method for forming a photoresist pattern as described in claim 13 in which the selective exposure step (3) uses light for forming a photoresist pattern with a thickness of 2.0 // m or less at the same time. Mask patterns and photomasks that form a photoresist pattern over 2 · 0 // m, and simultaneously form a photoresist pattern below 2.0 # m and a photo pattern over 2.0 // m on a glass substrate Photoresistive pattern. The invention of claim 15 is a method for forming a photoresist pattern according to claim 13 or 14, wherein the selective exposure step of (3) is an exposure process using i-rays (365 nm) as a light source. The invention of application item 16 is a method for forming a photoresist pattern according to any one of application items 13 to 15, wherein the selective exposure step of (3) is performed under a low NA condition where the NA is less than 0.2. Performed by the exposure process. [Implementation Mode of the Invention] The (A) component (alkaline soluble resin) (A) component alkali soluble resin printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is not particularly limited as long as it is a positive photoresist composition Any of the materials generally used as a film-forming substance can be arbitrarily used, and preferred examples thereof include condensation reaction products of aromatic hydroxy compounds with aldehydes or ketones, polyhydroxystyrene and derivatives thereof. The foregoing hydroxy compounds such as phenol, m-cresol, p-cresol, 0-cresol, -10- This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) 594393 A7 B7 V. Description of the invention ( 7) xylenols such as 2,3-monocresol, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, m-ethylphenol, ethyl ethylphenol, Ethylphenol, (Please read the notes on the back before filling out this page} 2,3,5-trimethylphenol '2,3,5-triethylphenol, 4-tert-butylphenol, 3-iert Alkyl phenols such as -butylphenol, 2-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol, p-methoxyphenol , ^ Methoxyphenol, P-ethoxyphenol, m_ethoxyphenol, [propoxyphenol, m-propoxyphenol and other ethoxybenzenes, etc., 0-isopropenyl benzoic acid, p _Isopropenol, 2-methyl-4-isopropenylphenol, 2-ethyl-4-isopropenylphenol and other isopropenylphenols, phenylphenol and other arylphenols, 4,4, Polyhydroxyphenols such as hydroxybiphenyl, bisphenol A, resorcinol, hydroquinone, pyrogenol, etc. It can be used alone or in combination of two or more types. The Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs print pre-printed aldehydes, such as formaldehyde, p-formaldehyde, trioxane, acetaldehyde, propionaldehyde, butyraldehyde, and trimethyl ethyl. Aldehyde, acrolein ', crotonaldehyde, cyclohexanal, sugar aldehyde, furyl acrolein, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, α-phenylpropanal, stone-phenylpropanal, 0-hydroxyl Benzoaldehyde, m_hydroxybenzaldehyde, 0_methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, 0_chlorobenzaldehyde, m_chlorobenzaldehyde, p_chlorobenzaldehyde, Cinnamaldehyde, etc. It can be used alone or in combination of two or more. Among the aforementioned aldehydes, formaldehyde is preferred in terms of easy accessibility, and especially for improving heat resistance, hydroxybenzaldehydes are used. It is more preferred to use it in combination with formaldehydes. Prescriptive ketones, such as acetone, methyl ethyl ketone, diethyl ketone, diphenyl ketone, etc. It can be used alone or in combination of two or more. In addition, aldehydes And ketones can also be used in appropriate combination. The condensation reaction product of the aromatic hydroxy compound with aldehydes or ketones-11-This The paper size applies the Chinese National Standard (CNS) A4 (21〇χ; 297 mm) 594393 A7 B7 5. Description of the invention (8), for example, it can be manufactured by known methods in the presence of acid catalysts. Used at this time Acidic catalysts such as hydrochloric acid, sulfuric acid, formic acid, oxalic acid, p-benzenesulfonic acid (please read the notes on the back before filling this page), etc. Preface Polyhydroxystyrene and its derivatives, such as vinylphenol homopolymer, Copolymers obtained by copolymerizing vinylphenol with comonomers, etc. The aforementioned comonomers are, for example, acrylic acid derivatives, acrylonitrile, methacrylic acid derivatives, methacrylonitrile, styrene, α-methylstyrene, Styrene derivatives such as p-methylstyrene, o-methylstyrene, p-methoxystyrene, and p-chlorostyrene, and the like. Among them, the alkali-soluble resin most suitable for use as the component (A) of the present invention, for example, an alkali-soluble phenolic lacquer resin having a weight average molecular weight (Mw) of 2,000 to 20,000, and especially of 3,000 to 1 2000 is preferred. -Cresol, p-cresol phenols and phenolic lacquer resins obtained by the condensation reaction of propionaldehyde and formaldehyde-containing aldehydes are very suitable as high-sensitivity and excellent linear photoresist materials. The aldehydes are preferably composed of propionaldehyde and formaldehyde. (B) Ingredient (quinonediazide ester) Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Using the quinonediazide ester represented by the above formula (I) can be obtained with excellent linearity. And it is suitable for i-ray exposure photoresist material. In addition, even under low NA conditions where NA is 0.2 or less, it is possible to form a rectangular and fine-shaped rectangle with excellent shape without changing the pre-baking conditions, post-exposure heating (PEB) conditions, and development order. Photoresistive pattern. In addition, the average esterification rate of the esterification is 20 ~ 80%, preferably 35 ~ 70 -12- This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) 594393 Α7 Β7 V. Description of the invention (9)%, the residual film rate and resolution will decrease when it is less than 20%. When it exceeds 80%, the sensitivity will be significantly reduced, and the development residual (residue) effect will be increased, so it is not good. (B) In addition to the quinonediazide, the other quinonediazide may be used in the photosensitive component. For example, a quinone diazide ester represented by the following formula (II), etc. (but not including a compound represented by the formula (I)),
[式中，R1至R8各自獨立爲氫原子、鹵素原子、碳數1至 6之烷基、碳數1至6之烷氧基、或碳數3至6之環烷基；R9至 R11各自獨立爲氫原子或碳數1至6之烷基；Q爲氫原子、碳數 1至6之烷基、與R9鍵結形成碳數3至6之環烷基，或下記式（ III)所示殘基 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製[Wherein R1 to R8 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; each of R9 to R11 Is independently 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, and R9 is bonded to form a cycloalkyl group having 3 to 6 carbon atoms, or the following formula (III) Residue indicated (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs
(式中，1^]2與1^3各自獨立爲氫原子、鹵素原子、碳數 1至6之院基、碳數1至6之院氧基’或碳數3至6之環院基，c 爲1至3之整數），0各自獨立爲氫原子、1，2-萘醌二疊氮基-5 -磺醯基，其中至少1個爲1,2-萘醌二疊氮基-5 -磺醯基；a， b爲1至3之整數；d爲0至3之整數；η爲0至3之整數] 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） -13- 594393 經濟部智慧財產局員工消費合作社印製 A7 B7五、發明説明（1〇) 其具體例如，2,4-雙（3,5-二甲基-4-羥基苄基）-5-羥基 苯酚、2,6-雙（2,5-二甲基-4-羥基苄基）-4-甲基苯酚等線性 3核化合物；雙[2,5-二甲基-3- ( 4-羥基-5-甲基苄基）-4-羥 基苯基]甲烷、雙[2,5-二甲基-3- (4-羥基苄基）-4-羥基苯基 ]甲烷、雙[3- (3，5-二甲基-4-羥基苄基）-4-羥基-5-甲基苯 基]甲烷、雙[3- ( 3,5-二甲基-4-羥基苄基）-4-羥基-5-乙基 苯基]甲烷 '雙[3- (3,5-二乙基-4-羥基苄基）-4-羥基-5-甲 基苯基]甲烷、雙[3- ( 3,5-二乙基-4-羥基苄基）-4-羥基- 5-乙基苯基]甲烷、雙[2-羥基-3- (3,5-二甲基-4-羥基苄基）-5-甲基苯基]甲烷、雙[2-羥基-3- ( 2-羥基-5-甲基苄基）-5-甲基苯基]甲烷、雙[4-羥基-3- ( 2-羥基-5-甲基苄基）-5-甲 基苯基]甲烷等線性4核化合物；2,4-雙[2-羥基-3- ( 4-羥基苄 基）-5-甲基苄基]-6·環己基苯酚、2,4-雙[4-羥基-3- ( 4_羥基 苄基）-5-甲基苄基]-6-環己基苯酚等線性5核化合物等線性 多苯酚化合物；三（4-羥基苯基）甲烷、雙（4-羥基-3,5-二 甲基苯基）-4-羥基苯基曱烷、雙（4-羥基-3,5-二甲基苯基 )-3-羥基苯基甲烷、雙（4-羥基-2,5-二甲基苯基）-4-羥基 苯基甲烷、雙（4-羥基-2,5-二甲基苯基）-3-羥基苯基甲烷 、雙（4-羥基-2,5-二甲基苯基）-2-羥基苯基甲烷、雙（4-羥基-2,5-二甲基苯基）-3,4-二羥基苯基甲烷、雙（4-羥基-3,5-二甲基苯基）-2,4-二羥基苯基甲烷、雙（4-羥基-2,5-二 甲基苯基）-2,4-二羥基苯基甲烷、雙（4-羥基苯基）-3-甲 氧基-4-羥基苯基甲烷、雙（3-環己基-4_羥基苯基）-3-羥基 苯基甲烷、雙（3-環己基-4-羥基苯基）-2-羥基苯基甲烷、 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -14 - (請先閱讀背面之注意事項再填寫本頁) 594393 五、發明説明（11) 雙（3-環己基-4-羥基苯基）_4-羥基苯基甲烷、雙（夂環己 基羥基_6-甲基苯基）_2_羥基苯基甲烷、雙（3_環己基 羥基-6-甲基苯基）-3-羥基苯基甲烷、雙（3_環己基_心羥 基-6«甲基苯基）_4_羥基苯基甲烷、雙（弘環己基_6_羥基苯 基）-3-羥基苯基甲烷、雙（3-環己基_6_羥基苯基）_扣羥基 本基甲烷、雙（3 -環己基-6-羥基苯基）-2 -羥基苯基甲烷、 雙（3-環己基-6-羥基-4-甲基苯基）羥基苯基甲烷、雙（ 環己基-6-羥基-4-甲基苯基）_4_羥基苯基甲烷、雙（3-環 己基-6-羥基-4-甲基苯基）_3,4-二羥基苯基甲烷、雙（4·羥 基- 2,3,5-三甲基苯基）_2-羥基苯基甲烷、雙（4_羥基_2,3,5_ 一甲基本基）-3 -經基苯基甲院、雙（4 -經基_2,3,5 -三甲基 本基）-4-羥基苯基甲烷、雙（4-羥基_2,3,5-三甲基苯基）-3,4-一經基苯基甲烷、雙（3,5_二甲基-4_羥基苯基）-2_羥基 苯基甲院等三苯酚狀多苯酚化合物等醌二疊氮酯化物等爲 佳。 但’前記其他醌二疊氮酯化物之使用量，於（B )感光 丨生成分中’以含有80重量％以下，特別是5〇重量％以下， 以無損於本發明之效果故爲較佳。 本發明之組成物中，（B )成分之添加量，以對（A ) 成分之鹼可溶性樹脂與必要時配合添加之下記（C )成分之 總量爲20〜70重量％ ，較佳爲40〜60重量％之範圍爲佳。（ B)成分之添加量低於上記範圍時，則未能忠實地得到畫像 ’造成轉印性降低。又，（Β )成分之添加量超過上述範圍 時，會造成感度劣化與使所形成之光阻膜之均質性降低， (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部智慈財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -15- 594393 A7 B7 五、發明説明（12) 而造成解像性劣化。 -I-ClAiLXji度提昇劑） 本發明之組成物，爲提昇感度時，以添加（c)成分之 分子量1000以下之具有苯酚性羥基之鹼可性的低分子化合 物（感度提昇劑）時具有增加感度之效果，故爲較佳。 (c )成分，並未有特別之限定，例如可使用前記式（ II)所示之多苯酚化合物（式中，D以Η替代），更具體而 言，可爲1-[1，1-雙（4-甲基苯基）乙基]-4-[1_ ( 4-羥基苯基 )異丙基]苯、雙（4-羥基-2,3,5-三甲基苯基）_2_羥基苯基 甲烷、1，4-雙[1-(3,5-二甲基-4-羥基苯基）異丙基]苯、2,4_ 雙（3,5-二甲基-4-羥基苯基曱基）-6-甲基苯酚、雙（4_羥 基- 3,5-二甲基苯基）-2-羥基苯基甲烷、雙（4-羥基- 2,5-二 甲基苯基）-2-羥基苯基甲烷、雙（4-羥基-3,5_二甲基苯基 )-3,4-二羥基苯基甲烷、1-[卜（3-甲基羥基苯基）異丙 基]-心[1，1-雙（3-甲基-4-羥基苯基）乙基]苯、2,6•雙[丨_ ( 2，心二羥基苯基）異丙基]-4-甲基苯酚、4,6-雙[1_ ( 4-羥基 苯基）異丙基]間苯二酚、4,6-雙（3,5-二甲氧基羥基苯 基甲基）焦培酚、4,6-雙（3,5-二甲基-4-羥基苯基甲基）焦 培醱、2,6 -雙（3 -甲基-4，6 -二羥基苯基甲基）-4 -甲基苯·、 2,6-雙（2,3,4-三羥基苯基甲基）-4-曱基苯酚、1，1_雙（4_經 基苯基）環己烷等爲佳。其中又以Ml，1-雙（4-甲基苯基） 乙基( 4-羥基苯基）異丙基]苯、雙（4-羥基_2,3,5-三 甲基苯基）-2-羥基苯基甲烷、雙（4-羥基-3,5-二甲基苯基 本紙張尺度適用中國國家標準（ CNS ) A4規格（210X297公釐) -16 (請先閲讀背面之注意事項再填寫本頁) I裝- 經濟部智慧財產局員工消費合作社印製 594393 經濟部智慧財產局員工消費合作社印製 kl五、發明説明（13) )-3,4-二羥基苯基甲烷、2,4-雙（3,5-二甲基-4-羥基苯基甲 基）-6-甲基苯酚、4,6-雙[1- ( 4-羥基苯基）異丙基]間苯二 酚等爲更佳。 (C )成分添加於本發明組成物中時，其含量以對（a )成分之驗可溶性樹脂爲5〜70重量％ ，較佳爲20〜60重量 %之範圍。 本發明之組成物，以使用將前述（A )至（C )與各種 添加成分溶解於有機溶劑之下記（D )成分所得溶液形式者 爲佳。 (D)成分（有機溶劑） 本發明所使用之有機溶劑，係含有丙二醇單烷基醚乙 酸酯或乳酸烷酯者，以其具有優良塗佈性，且可於大型玻 璃基板上形成厚度均勻的光阻被覆膜而爲較佳。 丙二醇單烷基醚乙酸酯中又以丙二醇單烷甲基醚乙酸 酯（PGMEA )爲最佳，其塗覆於基板上時具有極均勻之膜 厚。又，乳酸烷酯中，又以乳酸乙酯爲最佳，但其使用於 5 00x 600mm2以上大型玻璃基板時，因會產生塗覆斑紋，故 以使用與其他溶劑混合之混合系爲佳。 特別是使用同時含有丙二醇單烷基醚乙酸酯與乳酸烷 酯之組成成分時，可形成具有優良均勻厚度之光阻塗覆膜 ，與形狀極佳之光阻圖型，故爲較佳。 將丙二醇單烷基醚乙酸酯與乳酸烷酯混合使用時，對 於丙二醇單烷基醚乙酸酯而言，以添加重量比爲0.1至1 0倍 本紙張尺度適用中國國家標準（CNS )A4規格（210X297公釐） -17 - (請先閱讀背面之注意事項再填寫本頁) 594393 Α7 Β7 五、發明説明（14) i ’較佳爲1至5倍量之乳酸院酯爲佳。 (請先閱讀背面之注意事項再填寫本頁) 又，亦可使用r - 丁內酯或丙二醇單丁基醚等其他有機 溶劑，於使用7 - 丁內酯時，以添加對丙二醇單烷基醚乙酸 酉旨依重量比爲0.01至1倍量，較佳係爲添加Q.Q5至0.5倍量。 又，前記以外之有機溶劑，例如丙酮、甲基乙基酮、 環己酮、甲基異戊基酮、2-庚酮等酮類；乙二醇、丙二醇 、二乙二醇、乙二醇單乙酸酯、丙二醇單乙酸酯、二乙二 醇單乙酸酯或其單甲基醚、單乙基醚、單丙基醚、單丁基 酉迷或單苯基醚等多元醇類及其衍生物；二噁烷等環式醚類 ;與乙酸甲酯、乙酸乙酯、乙酸甲酯、丙酮酸乙酯、甲氧 基丙酸甲酯、乙氧基丙酸乙酯等酯類。其對於丙二醇單烷 δ醚乙酸酯、乳酸烷酯、與其混合物，以使用5〇重量％下 爲佳。 經濟部智慧財產局員工消費合作社印製 本發明之組成物中，必要時，可再添加具有相容性之 '添加物，防止光暈之紫外線吸收劑，例如2,2，，4,4，-四羥基二 苯甲酮、4-二甲基胺基-2，，4、二羥基二苯甲酮、5-胺基-3-甲 基-1-苯基-4- ( 4-羥基苯基偶氮基）吡唑、4-二甲基胺基-4，-經基偶氮苯、4-二乙基胺基- 4，-乙氧基偶氮苯、4-二乙基胺 基偶氮苯'薑黃素等。 又，爲使光阻塗膜之面內均勻性更向上提昇，其氟系 或矽系或氟-矽系界面活性劑，以對組成物中固體成份，較 佳爲添加0.01至〇.5重量％ ，更佳爲添加0.02至0.4重量％之 比例。 氣系界面活性劑，並未有特別之限制’其可使用以往 -18- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） 594393 A7 — _ B7 _ 五、發明説明（15) (請先閱讀背面之注意事項再填寫本頁) 公知之化合物。該氟系界面活性劑之例示，例如商品名福 來特FC-430、FC-431 (住友3M公司製）等具有氟化烷基或 全氟烷基之直鏈狀非離子性氟系界面活性劑等。矽系界面 活性劑，並未有特別之限定，其可使用以往公知之化合物 ’該矽系界面活性劑之例，如商品名SI-1 0系列（竹本油脂 公司製），美格福31 (大日本油墨化學工業公司製）等烷 基矽烷基與乙氧基與丙氧基鍵結所得之非離子性矽系界面 活性劑等。又，氟系-矽系界面活性劑，並未有特別之限定 ’其可使用以往公知之化合物。此氟系-矽系界面活性劑之 例，如商品名美格福R-08 (大日本油墨化學工業公司製） 等全氟烷基酯基與烷基矽烷基與乙氧基與丙氧基鍵結所得 之非離子性氟系-矽系界面活性劑，X-70-090、X-70-091、 X-70-09 2、X-70-093 (信越化學工業公司製）等具有全氟烷 基之矽氧烷與聚醚基鍵結所得之非離子性氟系-矽系界面活 性劑等。前述界面活性劑可單獨使用或將2種組合後使用皆 可 ° 經濟部智慧財產局員工消費合作社印製 本發明之組成物，特別是適合用於液晶顯示元件與製 造系統L C D使用。較適合使用本發明組成物之一方法例，首 先將（A )成分至（C )成分、與必要時使用之添加成分溶 解於（D )有機溶劑以製得溶液，再將其以旋轉塗佈器等塗 佈於500X 600mm2以上之大型坡璃四方基板上，以形成塗膜 ，並將形成塗膜之玻璃基板予以加熱處理（預燒培），以 於玻璃基板上形成光阻被覆膜，隨後對此光阻被覆膜，以 使用光源，例如低壓水銀燈、高壓水銀燈、超高壓水銀燈 -19- 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 594393 A7 B7 五、發明説明（侷） (請先閱讀背面之注意事項再填寫本頁) 、氙氣燈等，介著所需要之光罩圖型進行選擇性之曝光， 隨後使用例如1至1 〇重量％之四甲基銨氫氧化物（TMAH ) 水溶液等鹼性水溶液所構成之顯影液，其對基板表面全體 進行浸泡方式進行顯影處理，使其於玻璃基板上形成光阻 圖型，隨後將殘留於光阻圖型表面之顯影液洗淨，以形成 所需要形狀之光阻圖型。又，必要時可再進行後燒培。 依本發明之組成物，可對同時描繪有2.0 // m以下之形 成光阻圖型用的光罩圖型與，超過2· 0/zm之形成光阻圖型 的光罩圖型之光罩板進行選擇性曝光，以於玻璃基板上同 時形成具有具有優良形狀的圖型尺寸爲2.0 # m以下之光阻 圖型與超過2.0//m之光阻圖型。又，選擇性曝光步驟係使 用i射線（3 65 nm )爲光源所進行之曝光製程。其可達到更 高解像度。又，亦可對N A爲0 · 2以下之低N A條件下之曝光製 程進行選擇性曝光。即使於此低N A條件下，本發明之組成 物亦可形成具有優良形狀之2.0 // m以下之微細光阻圖型。 【實施例】 經濟部智慧財產局員工消費合作社印製 以下，將本發明以實施例與比較例作更明確之說明。 [合成例1](酚醛淸漆樹脂1之合成） (1次反應） 於備有機械攪拌器、迪姆羅冷卻器、300mm滴下漏斗、 氮氣導入管之i公升4 口燒瓶中，饋入m_甲酚86.4g ( 〇·8莫耳 )、卜甲苯磺酸2 · 0 g、與7 - 丁內酯8 6 · 4 g後，將反應溶液調 20 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） 594393 Μ —__Β7 _ 五、發明説明（17) 整至50重量％ 。 (請先閱讀背面之注意事項再填寫本頁) 隨後，於氮氣流通中，於機械攪拌器攪拌中使其於油 浴中加熱，當反應溶液之內部溫度到達100°C時，由滴下漏 斗將95重量％丙醛水溶液12.22g以30分鐘時間緩慢滴入其中 ’滴入後，再使其反應4小時。 對所得反應物進行採樣結果，得知其Mw爲250，Mw/Mn 爲 1.65 。 (2次反應） 隨後，將溶有3,4-二甲苯24.4g ( 0.2莫耳）之r -丁內酯 24.4g溶液，饋入前記1次反應後所得之反應溶液中，隨後， 將37重量％甲醛水溶液52.7g以30分鐘時間，緩緩滴入，滴 入後，再進行10小時之反應。 反應結束後，將反應容器充分冷卻至室溫後，反應溶 液使用Μ AK (甲基戊基酮），調整至20重量％濃度溶液後 ’使用3公升分液漏斗水洗3次，再以蒸發器濃縮。 經濟部智慧財產局員工消費合作社印製 隨後，使用ΜΑΚ與甲醇進行稀釋，而製得15重量％濃 度之ΜΑΚ/甲醇=4/1 (重量比）之溶液。 將該溶液置入3公升之分液漏斗中，再加入η _庚院後去 除含共聚單體之低分子量體，得目的之酚醛淸漆樹脂1 ( Mw 二 4000) 〇 [合成例2](酚醛淸漆樹脂2之合成） (1次反應） 本^張尺度適用中國國家標準（CNS ) A4規格（210Χ 297Αϋ '^21 -" = 594393 A7 B7 五、發明説明（18) (請先閱讀背面之注意事項再填寫本頁) 於合成例1之（1次反應）中，除將m-甲酚86.4g ( 0.8莫 耳）以m-甲酚97.2g ( 0.9莫耳）替代，r - 丁內酯86.4g以 97 · 2g替代外，其他皆依合成例1進行相同之反應，而製得 Mw爲210，Mw/Mn爲1.84之反應物。 (2次反應） 於合成例1之（2次反應）中，除將3,4-二甲苯24.4g ( 〇·2莫耳）以3,4 -二甲苯12.2g(0.1莫耳）替代，丁內酯 24.4g以I2.2g替代外，其他皆依合成例1相同方法進行反應 ’而製得Mw = 6000之酚酸淸漆樹脂2。 [合成例3](酚醛淸漆樹脂3之合成） (1次反應） 於合成例1之（1次反應）中，除將m-甲酚86.4g ( 0.8莫 耳）以m-甲酚97.2g(0.9莫耳）替代，7-丁內酯86.4g以 9 7.28替代，丙醛12.22£以9.15£替代外，其他皆依合成例1進 行相同之反應，而製得Mw爲180，Mw/Mn爲1.72之反應物。 經濟部智慧財產局員工消費合作社印製 (2次反應） 於合成例1之（2次反應）中，除將3,4-二甲苯24.4g ( 0·2莫耳）以3,4-二甲苯12.2g ( 0.1莫耳）替代，r -丁內酯 24.4g以I2.2g替代外，其他皆依合成例1相同方法進行反應 ’而製得Mw二6000之酚醛淸漆樹脂3。 -22- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X29?公釐） 594393 A7 B7 五、發明説明（19) [實施例1] (A )成分： 鹼可溶性樹脂 100重量份 (請先閱讀背面之注意事項再填寫本頁) (合成例1所製得之酚醛淸漆樹脂1 ) (B )成分： (Bl) / ( B2) = 1 : 1之混合物 38重量份 (Bl: 1莫耳之上記式（I)之苯酚化合物與2莫耳之5-NQD ( 1，2-萘醌二疊氮基-5-磺酸氯化物）之酯化物，（B2) :1莫耳雙（2-甲基-4-羥基-5·環己基苯基）-3,4·二羥基苯基 甲烷與2莫耳5-NQD之酯化物） (C )成分： 感度提昇劑 25重量份 (1-[1，1-雙（4-甲基苯基）乙基]-4-[1-(4-羥基苯基） 異丙基]苯） 經濟部智慧財產局g(工消費合作社印製 將上記（Α)〜（C)，與對（Α)〜（C)成分之合計 重量爲350ppm之界面活性劑（製品名「R-08」；大日本油 墨公司製）溶解於PGMEA中，並將固體成分[(A)〜（C) 成分之合計]濃度調整製25至28重量％後]使用孔徑0.2 // m 之膜過濾器過濾，以製得正型光阻組成物。 [實施例2〜5]與[比較例1〜4] 除將（A ) 、 （ B )與（D )成分以下記表1所示內容替 代外，其他皆依實施例1相同方法調製正型光阻組成物。 -23- 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 594393 A7 __B7__ 五、發明説明（20) 對上記各實施例與比較例所得之正型光阻組成物，調 查下記各物性。其結果如表2所示。 (請先閱讀背面之注意事項再填寫本頁) (1 )線件評估： 將樣品使用旋轉塗佈器塗佈於形成有Cr膜之玻璃基板 (5 50x 650mm2 )上，再將其於熱壓板上於13(TC、1mm間隔 使用電子冷卻熱壓板以60秒間進行第1次乾燥，隨後再於熱 壓板上以120°C、0.5mm間隔再使用電子冷卻熱壓板以60秒 間進行第2次乾燥，得膜厚1.5// m之光阻被覆膜。 爲使3.0 μηι L&S與1.5 μΐΉ L&S光阻圖型重現，而介由描 繪有樣品線路光罩（光罩板）使用i射線曝光裝置（裝置名 :FX-7 02J，理光公司製；NA二0.14)，選擇最適合重現3.0 μηι L&S之曝光量（Εορ曝光量）進行選擇性曝光。 經濟部智慧財產局員工消費合作社印製 隨後，於放置有23°(：、2.38重量％丁“八11水溶液之配有 噴嘴的顯影裝置（裝置名：TD-39000試驗機，東京應化公 司製），將基板由逐漸吊起一端部至另一端部之方式，使 基板浸泡於水溶液中10秒，再保持55秒後，進行30秒間之 水洗，隨後旋轉乾燥。圖1係爲本實施例與比較例中，說明 該顯影處理時之基板平面圖。即，由前記一端部χ經由¥而 至另一端部Ζ方式浸泡水溶液。 其後，將所得之光阻圖型之截面形狀以SEM (掃描型電 子顯微鏡）照片觀察，並評估1.5 μιη L&S光阻圖型之重現 性。其結果如表2所示。 ί 9,)感度評估： -24- 本纸張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） 594393 A7 — ____B7___ 五、發明説明（21 ) 前記Εορ曝光量之結果如表2所示。 _( 3 )解像性評估： 依Εορ曝光量求得臨界解像度，其結果如表2所示。 _( 4) DOF特性評估： 於前記Εορ曝光量下，將焦點適當地上下移動，觀察1.5 ^ m L&S ± 10%尺寸變化率範圍內所得到之聚焦伸度之寬 (// m )，其結果如表2所示。 (5 )殘渣評估： 於前記Εορ曝光量中，以SEM (掃描型電子顯微鏡）觀 察描繪有1 · 5 // m L & S之基板表面，並調查是否具有殘渣， 其結果如表2所示。 (請先閱讀背面之注意事項再填寫本頁) I裝- 訂 經濟部智慧財產局員工消費合作社印製 【表1】 實施例 (A) (B) (D) (混合重量比） (混合重量比） 1 酚醛淸漆樹脂1 Bl/B2=l/1 PGMEA 2 酚醛淸漆樹脂1 B1/B3 二 1/1 同上 3 酚醛淸漆樹脂1 Bl/B2=l/1 PGMEA/EL = 3/7 4 酚醛淸漆樹脂2 Bl/B2=l/1 PGMEA 5 酚醛淸漆樹脂3 Bl/B2=l/1 PGMEA 比較例1 酚醛淸漆樹脂1 B4/B2=l/1 PGMEA 2 酚醛淸漆樹脂1 B4/B3 = l/1 PGMEA 3 酚醛淸漆樹脂1 B5/B2-1/1 PGMEA 4 酚醛淸漆樹脂1 B5/B3 = l/1 PGMEA B3: 1莫耳2,3,4,4’ -四羥基二苯甲酮與2.34莫耳5-NQD之 Φ -25- 本紙張尺度適用中國國家標準（CNS ) A4規格（2⑴X297公釐） 594393 B5 ·· 1莫耳雙[4_經基-3- ( 2-羥基-5-甲基苄基）-5-甲基 Α7 Β7 五、發明説明（22 ) 酯化物 B4 ·· 1莫耳雙[2_經基_3_ ( 2-羥基-5-甲基苄基）-5-甲基 苯基]甲烷與2莫耳5_NQD之酯化物 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 【發明效果】 依本發明之內容，本發明可提供一種適合製造系統LCD ’具有優良線性、適合低ΝΑ條件下之曝光製程，且適合丨射 線曝光之液晶顯示元件製造用正型光阻組成物，及光阻圖 型之形成方法。 苯基]甲院與2莫耳5-NQD之酯化物 【表2】 _ 實施例 線性評估 感度評估 解像性評 DOF評估 殘渣評估 (f! m) (m J) 估（β m) (β m) 1 1.515 40 1.2 20 無 2 1.525 45 1.2 20 te j\w 3 1.515 3 5 1.2 20 te jw\ 4 1.515 40 1.2 20 M y\\\ 5 1.515 35 1.2 20 紐 比較例1 1.700 40 1.4 10 有 2 1.750 45 1.4 10 有 3 1.850 30 1.5 10 有 4 1.800 35 1.4 10 有 -26- 本紙張尺度適用中國國家慄準（CNS ) Α4規格（21〇χ 297公釐） 594393 A7 B7 五、發明説明（23 ) 【圖示之簡單說明】 【圖1】 本實施例與比較例中，說明該顯影處理時之 基板平面圖。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） · 27 -(In the formula, 1 ^] 2 and 1 ^ 3 are each independently a hydrogen atom, a halogen atom, a radical of 1 to 6 carbon atoms, a radical of 1 to 6 carbon atoms, or a radical of 3 to 6 carbon atoms. , C is an integer from 1 to 3), 0 is each independently a hydrogen atom, 1,2-naphthoquinonediazide-5 -sulfonyl, at least one of which is 1,2-naphthoquinonediazide- 5-Sulfonyl; a, b are integers from 1 to 3; d is an integer from 0 to 3; η is an integer from 0 to 3] This paper size applies to China National Standard (CNS) A4 specifications (210X 297 mm) -13- 594393 Printed by A7 B7, Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (1〇) The specific example is 2,4-bis (3,5-dimethyl-4-hydroxybenzyl) -5 -Linear 3-nuclear compounds such as hydroxyphenol, 2,6-bis (2,5-dimethyl-4-hydroxybenzyl) -4-methylphenol; bis [2,5-dimethyl-3- (4 -Hydroxy-5-methylbenzyl) -4-hydroxyphenyl] methane, bis [2,5-dimethyl-3- (4-hydroxybenzyl) -4-hydroxyphenyl] methane, bis [3 -(3,5-dimethyl-4-hydroxybenzyl) -4-hydroxy-5-methylphenyl] methane, bis [3- (3,5-dimethyl-4-hydroxybenzyl)- 4-hydroxy-5-ethylphenyl] methane'bis [3- (3,5-di 4-hydroxybenzyl) -4-hydroxy-5-methylphenyl] methane, bis [3- (3,5-diethyl-4-hydroxybenzyl) -4-hydroxy-5-ethyl Phenyl] methane, bis [2-hydroxy-3- (3,5-dimethyl-4-hydroxybenzyl) -5-methylphenyl] methane, bis [2-hydroxy-3- (2-hydroxy -5-methylbenzyl) -5-methylphenyl] methane, bis [4-hydroxy-3- (2-hydroxy-5-methylbenzyl) -5-methylphenyl] methane, etc. linear 4 Nuclear compounds; 2,4-bis [2-hydroxy-3- (4-hydroxybenzyl) -5-methylbenzyl] -6 · cyclohexylphenol, 2,4-bis [4-hydroxy-3- ( 4-hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol and other linear polynuclear compounds such as linear 5-nuclear compounds; tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5 -Dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-2,5- Dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethyl Phenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-3,5-di Phenyl) -2,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2,4-dihydroxyphenylmethane, bis (4-hydroxyphenyl) -3-methoxy-4-hydroxyphenylmethane, bis (3-cyclohexyl-4_hydroxyphenyl) -3-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -2 -Hydroxyphenylmethane, this paper size applies Chinese National Standard (CNS) A4 specification (210X 297mm) -14-(Please read the precautions on the back before filling this page) 594393 5. Description of the invention (11) Double ( 3-cyclohexyl-4-hydroxyphenyl) _4-hydroxyphenylmethane, bis (fluorenecyclohexylhydroxy_6-methylphenyl) _2_hydroxyphenylmethane, bis (3-cyclohexylhydroxy-6-formyl) Phenyl) -3-hydroxyphenylmethane, bis (3-cyclohexyl_cardiohydroxy-6 «methylphenyl) _4_hydroxyphenylmethane, bis (cyclocyclohexyl_6_hydroxyphenyl) -3 -Hydroxyphenylmethane, bis (3-cyclohexyl_6_hydroxyphenyl) _N-hydroxybenzyl methane, bis (3-cyclohexyl-6-hydroxyphenyl) -2 -hydroxyphenylmethane, bis (3 -Cyclohexyl-6-hydroxy-4-methylphenyl) hydroxyphenylmethane, bis (cyclohexyl-6-hydroxy-4-methyl Phenyl) _4_hydroxyphenylmethane, bis (3-cyclohexyl-6-hydroxy-4-methylphenyl) _3,4-dihydroxyphenylmethane, bis (4 · hydroxy-2,3,5- Trimethylphenyl) _2-hydroxyphenylmethane, bis (4-hydroxy_2,3,5_monomethylbenzyl) -3 -Cyclophenylmethylamine, bis (4-Cycloyl_2,3, 5-trimethylbenzyl) -4-hydroxyphenylmethane, bis (4-hydroxy_2,3,5-trimethylphenyl) -3,4-monylphenylmethane, bis (3,5_di Methyl-4_hydroxyphenyl) -2_hydroxyphenyl methylamine and other triphenol-like polyphenol compounds such as quinonediazide esters and the like are preferred. However, the amount of the other quinone diazide ester compound mentioned above (in the (B) photosensitive 丨 product component) should be 80% by weight or less, especially 50% by weight, so as not to detract from the effects of the present invention, so it is better. . In the composition of the present invention, the amount of the component (B) is 20 to 70% by weight, preferably 40 to the total weight of the component (C) added to the alkali-soluble resin of the component (A) and if necessary, 40 A range of ~ 60% by weight is preferred. (B) When the added amount of the component is lower than the above range, the image cannot be obtained faithfully, and the transferability is lowered. In addition, when the addition amount of (B) component exceeds the above range, it will cause sensitivity degradation and decrease the homogeneity of the formed photoresist film. (Please read the precautions on the back before filling this page) Order the intellectual property of the Ministry of Economic Affairs The paper size printed by the Bureau's Consumer Cooperatives applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) -15- 594393 A7 B7 V. Description of the invention (12) Degradation of resolution. -I-ClAiLXji degree enhancer) When the composition of the present invention is to increase sensitivity, it is increased by adding a low molecular weight compound (sensitivity enhancer) having a phenolic hydroxyl base and a molecular weight of (c) component of 1000 or less The effect of sensitivity is better. (c) The component is not particularly limited. For example, a polyphenol compound represented by the formula (II) (where D is replaced by Η) may be used. More specifically, it may be 1- [1,1- Bis (4-methylphenyl) ethyl] -4- [1_ (4-hydroxyphenyl) isopropyl] benzene, bis (4-hydroxy-2,3,5-trimethylphenyl) _2_ Hydroxyphenylmethane, 1,4-bis [1- (3,5-dimethyl-4-hydroxyphenyl) isopropyl] benzene, 2,4-bis (3,5-dimethyl-4-hydroxyl Phenylfluorenyl) -6-methylphenol, bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylbenzene Group) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, 1- [b (3-methylhydroxyphenyl) Isopropyl] -cardio [1,1-bis (3-methyl-4-hydroxyphenyl) ethyl] benzene, 2,6 • bis [丨 _ (2, cardiodihydroxyphenyl) isopropyl] 4-methylphenol, 4,6-bis [1_ (4-hydroxyphenyl) isopropyl] resorcinol, 4,6-bis (3,5-dimethoxyhydroxyphenylmethyl) Pyrophenol, 4,6-bis (3,5-dimethyl-4-hydroxyphenylmethyl) pyropyrene, 2,6-bis (3-methyl-4,6-dihydroxybenzene Methyl) -4-methylbenzene, 2,6-bis (2,3,4-trihydroxyphenylmethyl) -4-fluorenylphenol, 1,1-bis (4-merylphenyl) Cyclohexane and the like are preferred. Among them, Ml, 1-bis (4-methylphenyl) ethyl (4-hydroxyphenyl) isopropyl] benzene, bis (4-hydroxy_2,3,5-trimethylphenyl)- 2-Hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) The paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) -16 (Please read the precautions on the back before filling (In this page) I-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 594393 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Ⅴ. Description of the Invention (13)) -3,4-Dihydroxyphenylmethane, 2,4 -Bis (3,5-dimethyl-4-hydroxyphenylmethyl) -6-methylphenol, 4,6-bis [1- (4-hydroxyphenyl) isopropyl] resorcinol, etc. For the better. When the component (C) is added to the composition of the present invention, its content is 5 to 70% by weight, and preferably 20 to 60% by weight, based on the soluble resin of the component (a). The composition of the present invention is preferably in the form of a solution obtained by dissolving the aforementioned components (A) to (C) and various added components in an organic solvent, and the component (D). (D) Component (organic solvent) The organic solvent used in the present invention is one containing propylene glycol monoalkyl ether acetate or alkyl lactate. It has excellent coating properties and can be formed on a large glass substrate with a uniform thickness. The photoresist is preferably covered with a film. Among the propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl methyl ether acetate (PGMEA) is the best. It has an extremely uniform film thickness when coated on a substrate. Among the alkyl lactates, ethyl lactate is the most preferable. However, when it is used on a large glass substrate of 500x600mm2 or more, coating streaks may occur, so it is better to use a mixed system mixed with other solvents. In particular, when a composition containing both propylene glycol monoalkyl ether acetate and alkyl lactate is used, a photoresist coating film having an excellent uniform thickness and a photoresist pattern having an excellent shape are preferable, so it is preferable. When propylene glycol monoalkyl ether acetate is mixed with alkyl lactate, for propylene glycol monoalkyl ether acetate, the added weight ratio is 0.1 to 10 times. This paper size applies Chinese National Standard (CNS) A4. Specifications (210X297mm) -17-(Please read the precautions on the back before filling this page) 594393 Α7 Β7 V. Description of the invention (14) i 'It is better to use 1 to 5 times the amount of lactic acid ester. (Please read the precautions on the back before filling this page) Also, other organic solvents such as r-butyrolactone or propylene glycol monobutyl ether can be used. When 7-butyrolactone is used, p-propylene glycol monoalkyl is added. The purpose of ether acetate is 0.01 to 1 times the amount by weight ratio, and it is preferably to add Q.Q5 to 0.5 times the amount. In addition, organic solvents other than the foregoing, such as ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, propylene glycol, diethylene glycol, and ethylene glycol Polyols such as monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate or monomethyl ether, monoethyl ether, monopropyl ether, monobutyl hydrazone, or monophenyl ether, and their Derivatives; cyclic ethers such as dioxane; and esters such as methyl acetate, ethyl acetate, methyl acetate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate and the like. For propylene glycol monoalkane δ-ether acetate, alkyl lactate, and mixtures thereof, it is preferable to use 50% by weight. The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the composition of the present invention. If necessary, a compatible 'additive' can be added to prevent halo UV absorbers, such as 2,2,4,4, -Tetrahydroxybenzophenone, 4-dimethylamino-2,4, dihydroxybenzophenone, 5-amino-3-methyl-1-phenyl-4- (4-hydroxybenzene Azo) pyrazole, 4-dimethylamino-4, -mercaptoazobenzene, 4-diethylamino-4, -ethoxyazobenzene, 4-diethylamino Azobenzene 'curcumin and the like. In addition, in order to further improve the in-plane uniformity of the photoresist coating film, the fluorine-based or silicon-based or fluorine-silicon-based surfactants are preferably added to the composition in an amount of 0.01 to 0.5 weight. %, More preferably in a proportion of 0.02 to 0.4% by weight. There are no special restrictions on air-based surfactants. It can be used in the past. 18- This paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm) 594393 A7 — _ B7 _ V. Description of the invention (15 ) (Please read the notes on the back before filling out this page) Known compounds. Examples of such fluorine-based surfactants are, for example, straight-chain nonionic fluorine-based interfacial activities having a fluorinated alkyl group or a perfluoroalkyl group, such as the brand names Fleet FC-430, FC-431 (manufactured by Sumitomo 3M). Agent. The silicon-based surfactant is not particularly limited, and conventionally known compounds such as the examples of the silicon-based surfactant can be used, such as the trade name SI-1 0 series (manufactured by Takemoto Oil Co., Ltd.), Megford 31 ( Non-ionic silicon-based surfactants obtained by bonding of alkylsilyl groups, ethoxy groups, and propoxy groups, etc., made by Dainippon Ink Chemical Industry Co., Ltd.). The fluorine-silicon surfactant is not particularly limited. A conventionally known compound can be used. Examples of this fluorine-silicon surfactant are perfluoroalkyl ester groups, alkylsilyl groups, ethoxy groups, and propoxy groups such as the brand name Megford R-08 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.). Non-ionic fluorine-silicon surfactants obtained through bonding, including X-70-090, X-70-091, X-70-09 2, X-70-093 (made by Shin-Etsu Chemical Industry Co., Ltd.), etc. Non-ionic fluorine-silicon surfactants obtained by bonding fluoroalkyl siloxanes to polyether groups. The aforementioned surfactants can be used alone or in combination of two. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the composition of the present invention is particularly suitable for use in liquid crystal display elements and manufacturing systems L CD. One method is more suitable for using the composition of the present invention, firstly dissolving the components (A) to (C) and the additional components used when necessary in (D) organic solvent to obtain a solution, and then spin-coating the solution The device is coated on a large sloping glass square substrate of 500X 600mm2 or more to form a coating film, and the glass substrate forming the coating film is heated (pre-fired) to form a photoresist coating film on the glass substrate. This photoresist is then covered with a film to use light sources, such as low-pressure mercury lamps, high-pressure mercury lamps, and ultra-high-pressure mercury lamps. 19- This paper size applies to China National Standard (CNS) A4 (210X 297 mm) 594393 A7 B7 V. Description of the Invention (Bureau) (Please read the precautions on the back before filling this page), Xenon lamp, etc., for selective exposure through the required mask pattern, and then use, for example, 1 to 10% by weight of the top four A developer composed of an alkaline aqueous solution, such as a basic ammonium hydroxide (TMAH) aqueous solution, immerses the entire surface of the substrate and develops it to form a photoresist pattern on the glass substrate. The developer remaining on the surface of the photoresist pattern is washed to form a photoresist pattern of a desired shape. If necessary, post-firing may be performed. According to the composition of the present invention, a mask pattern for forming a photoresist pattern having a length of 2.0 // m or less and a mask pattern for forming a photoresist pattern exceeding 2 · 0 / zm can be simultaneously plotted. The mask plate is selectively exposed to simultaneously form a photoresist pattern having a pattern size of 2.0 # m or less and a photoresist pattern exceeding 2.0 // m on a glass substrate. The selective exposure step is an exposure process using i-rays (3 65 nm) as a light source. It can achieve higher resolution. Alternatively, selective exposure may be performed on an exposure process under a low NA condition where NA is 0 or less. Even under these low NA conditions, the composition of the present invention can form a fine photoresist pattern with a fine shape of 2.0 // m or less. [Example] Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs The present invention will be explained more specifically with examples and comparative examples below. [Synthesis example 1] (Synthesis of phenolic lacquer resin 1) (1 reaction) In an i-liter 4-neck flask equipped with a mechanical stirrer, a Dimro cooler, a 300 mm dropping funnel, and a nitrogen introduction tube, feed m _ After 86.4g of cresol (0.8 mole), 2.0 g of tolylene sulfonic acid, and 7 6-butyrolactone 8 6 · 4 g, adjust the reaction solution to 20 This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 594393 Μ — __Β7 _ 5. Description of the invention (17) is adjusted to 50% by weight. (Please read the precautions on the back before filling this page) Then, in a nitrogen flow, heat it in an oil bath while stirring with a mechanical stirrer. When the internal temperature of the reaction solution reaches 100 ° C, the dropping funnel will 12.22 g of a 95% by weight aqueous solution of propionaldehyde was slowly dropped into the solution over a period of 30 minutes. After the dropwise addition, the mixture was allowed to react for 4 hours. Sampling results of the obtained reactants revealed that their Mw was 250 and Mw / Mn was 1.65. (2 reactions) Subsequently, a solution of 24.4 g (0.2 mol) of 3,4-xylene in 24.4 g of r-butyrolactone was fed to the reaction solution obtained after the previous reaction, and then 37 52.7 g of a wt% aqueous formaldehyde solution was slowly dropped over a period of 30 minutes, and after the dropwise addition, a reaction was performed for another 10 hours. After the reaction was completed, the reaction container was sufficiently cooled to room temperature, and the reaction solution was adjusted to 20% by weight using AK (methylpentyl ketone). After washing the solution 3 times with a 3 liter separatory funnel, the reaction solution was evaporated. concentrate. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Then, MAK was diluted with methanol to prepare a 15% strength solution of MAK / methanol = 4/1 (weight ratio). The solution was placed in a 3 liter separatory funnel, and after adding η-geng Yuan, the low molecular weight body containing comonomer was removed to obtain the desired phenolic lacquer resin 1 (Mw 2 4000). [Synthesis Example 2] ( Synthesis of phenolic lacquer resin 2) (1 reaction) This standard is applicable to Chinese National Standard (CNS) A4 specification (210 × 297Αϋ '^ 21-" = 594393 A7 B7 V. Invention description (18) (Please read first Note on the back page, please fill in this page again) In Synthesis Example 1 (1 reaction), except that m-cresol 86.4 g (0.8 mol) was replaced with m-cresol 97.2 g (0.9 mol), r- Except that 86.4 g of butyrolactone was replaced by 97 · 2 g, the others were subjected to the same reaction as in Synthesis Example 1, and a reactant having Mw of 210 and Mw / Mn of 1.84 was prepared. (2 reactions) In Synthesis Example 1 ( In 2 reactions), except that 24.4 g (0.2 mole) of 3,4-xylene was replaced by 12.2 g (0.1 mole) of 3,4-xylene, and 24.4 g of butyrolactone was replaced by I2.2 g The others were reacted according to the same method as in Synthesis Example 1 to prepare a phenolic lacquer resin 2 with Mw = 6000. [Synthesis Example 3] (Synthesis of phenolic lacquer resin 3) (1 reaction) In Synthesis Example 1 (1 time Should), in addition to replacing m-cresol 86.4g (0.8 mole) with m-cresol 97.2g (0.9 mole), 7-butyrolactone 86.4g by 9 7.28, propionaldehyde 12.22 £ to 9.15 £ Except for the replacement, the other reactions were performed according to Synthesis Example 1, and reactants with Mw of 180 and Mw / Mn of 1.72 were prepared. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (2 reactions) In Synthesis Example 1 (2 reactions), except that 24.4g (0.2 mole) of 3,4-xylene was replaced by 12.2g (0.1 mole) of 3,4-xylene, and 24.4g of r-butyrolactone was replaced by I2. Except 2g substitution, others were reacted according to the same method as in Synthesis Example 1 to prepare Mw 2 6000 phenolic lacquer resin 3. -22- This paper size is applicable to China National Standard (CNS) A4 specification (210X29? Mm) 594393 A7 B7 5. Description of the invention (19) [Example 1] (A) Ingredients: 100 parts by weight of alkali-soluble resin (please read the precautions on the back before filling this page) (Phenolic lacquer resin prepared in Synthesis Example 1) 1) (B) Ingredients: (Bl) / (B2) = 1: 1 mixture 38 parts by weight (Bl: 1 mol of the phenol compound of formula (I) above and 2 mol of 5-NQD (1,2 -Naphthoquinonediazide-5- Ester of sulfonic acid chloride, (B2): 1 mole bis (2-methyl-4-hydroxy-5 · cyclohexylphenyl) -3,4 · dihydroxyphenylmethane and 2 mole 5- Ester of NQD) (C) Component: 25 parts by weight of a sensitivity enhancer (1- [1,1-bis (4-methylphenyl) ethyl] -4- [1- (4-hydroxyphenyl) iso (Propyl) benzene) Ministry of Economic Affairs Intellectual Property Bureau g (printed by the Industrial and Consumer Cooperatives, the surfactant (A) ~ (C), and the total weight of the components (A) ~ (C) is 350ppm, a surfactant (product name " R-08 "; manufactured by Dainippon Ink Co., Ltd.) was dissolved in PGMEA, and the solid content [total of (A) to (C) components] was adjusted to 25 to 28% by weight.] A film with a pore diameter of 0.2 // m The filter was filtered to obtain a positive photoresist composition. [Examples 2 to 5] and [Comparative Examples 1 to 4] Except replacing the components (A), (B), and (D) as shown in Table 1 below, the other methods were used to modulate the positive type in the same manner as in Example 1. Photoresist composition. -23- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 594393 A7 __B7__ V. Description of the invention (20) For the positive photoresist composition obtained in each of the above examples and comparative examples, investigate the following Various physical properties. The results are shown in Table 2. (Please read the precautions on the back before filling this page) (1) Evaluation of wire parts: Apply the sample to a glass substrate (5 50x 650mm2) with a Cr film using a spin coater, and then heat-press it The plate was dried for the first time at 60 ° C using an electronic cooling hot platen at 13 (TC, 1mm interval), and then again at 120 ° C, 0.5mm interval using an electronic cooling hot platen in 60 seconds. After drying for the second time, a photoresist coating with a film thickness of 1.5 // m was obtained. In order to reproduce the photoresist patterns of 3.0 μηι L & S and 1.5 μΐΉ L & S, a sample line mask (light The mask plate) uses an i-ray exposure device (device name: FX-7 02J, manufactured by Ricoh Corporation; NA II 0.14), and selects the exposure (Eoρ exposure) that is most suitable for reproducing 3.0 μηι L & S for selective exposure. Printed by the Consumer Cooperative of the Ministry of Intellectual Property, and placed at 23 ° (:, 2.38% by weight of Ding "Eight 11 aqueous solution with a developing device equipped with a nozzle (device name: TD-39000 test machine, manufactured by Tokyo Ino Chemical Co., Ltd.) , Soak the substrate by gradually lifting the substrate from one end to the other After being held in the aqueous solution for 10 seconds and then held for 55 seconds, it was washed with water for 30 seconds and then spin-dried. FIG. 1 is a plan view of the substrate during the development process in this example and comparative example. ¥ and soak the aqueous solution to the other end in the Z manner. Then, the cross-sectional shape of the obtained photoresist pattern was observed with a SEM (scanning electron microscope) photograph, and the reproducibility of the 1.5 μιη L & S photoresist pattern was evaluated. The results are shown in Table 2. ί 9,) Sensitivity evaluation: -24- This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) 594393 A7 — ____B7___ 5. Description of the invention (21) Preface Εορ The results of the exposure are shown in Table 2. _ (3) Evaluation of resolution: The critical resolution is obtained according to the exposure of Εορ, and the results are shown in Table 2. _ (4) Evaluation of the DOF characteristics: Under the exposure of Εορ , Move the focus appropriately up and down, observe the width of the focus extension (// m) obtained within the range of 1.5 ^ m L & S ± 10% dimensional change rate, and the results are shown in Table 2. (5) Residue evaluation : In the above exposure, the SEM (scan Type electron microscope) Observe the surface of the substrate on which 1 · 5 // m L & S is drawn and investigate whether there are residues. The results are shown in Table 2. (Please read the precautions on the back before filling this page) -Ordered by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs [Table 1] Example (A) (B) (D) (Mixed weight ratio) (Mixed weight ratio) 1 Phenolic resin lacquer resin 1 Bl / B2 = l / 1 PGMEA 2 Bakelite resin 1 B1 / B3 Two 1/1 Ibid. 3 Bakelite resin 1 Bl / B2 = l / 1 PGMEA / EL = 3/7 4 Bakelite resin 2 Bl / B2 = l / 1 PGMEA 5 Bakelite resin 3 Bl / B2 = l / 1 PGMEA Comparative Example 1 Bakelite resin 1 B4 / B2 = l / 1 PGMEA 2 Bakelite resin 1 B4 / B3 = l / 1 PGMEA 3 Bakelite resin 1 B5 / B2-1 / 1 PGMEA 4 Phenolic lacquer resin 1 B5 / B3 = l / 1 PGMEA B3: 1 mole 2,3,4,4 '-tetrahydroxybenzophenone and 2.34 mole 5-NQD Φ -25- This paper size applies to Chinese National Standard (CNS) A4 (2⑴X297mm) 594393 B5 ·· 1 Morse [4_Ceryl-3- (2-hydroxy-5-methylbenzyl) -5 -Methyl A7 B7 V. Description of the invention (22) Esterate B4 ·· 1 Morse [2_ 经_3_ (2-Hydroxy-5-methylbenzyl) -5-methylphenyl] Methane and 2 Molar 5_NQD esters (please read the precautions on the back before filling this page) Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Cooperative society printing [Invention effect] According to the content of the present invention, the present invention can provide a positive type light for liquid crystal display element manufacturing which is suitable for the manufacturing system LCD ', has excellent linearity, is suitable for the exposure process under low NA conditions, and is suitable for radiation exposure Resist composition, and method for forming photoresist pattern. Phenyl] Ester of 2A and 5-mole 5-NQD [Table 2] _ Examples Linear evaluation Sensitivity evaluation Resolution evaluation DOF evaluation Residue evaluation (f! M) (m J) Estimate (β m) (β m) 1 1.515 40 1.2 20 None 2 1.525 45 1.2 20 te j \ w 3 1.515 3 5 1.2 20 te jw \ 4 1.515 40 1.2 20 M y \\\ 5 1.515 35 1.2 20 New Zealand Comparative Example 1 1.700 40 1.4 10 Yes 2 1.750 45 1.4 10 Yes 3 1.850 30 1.5 10 Yes 4 1.800 35 1.4 10 Yes -26- This paper size applies to China National Chestnut Standard (CNS) A4 (21〇χ 297 mm) 594393 A7 B7 V. Description of the invention ( 23) [Brief description of the diagram] [Figure 1] In this embodiment and the comparative example, a plan view of the substrate during the development process will be described. (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) · 27-