TW200424764A - Positive photoresist composition for manufacturing LCD and method for forming resist pattern - Google Patents
Positive photoresist composition for manufacturing LCD and method for forming resist pattern Download PDFInfo
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- TW200424764A TW200424764A TW093101885A TW93101885A TW200424764A TW 200424764 A TW200424764 A TW 200424764A TW 093101885 A TW093101885 A TW 093101885A TW 93101885 A TW93101885 A TW 93101885A TW 200424764 A TW200424764 A TW 200424764A
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- photoresist composition
- photoresist
- pattern
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- carbon atoms
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Classifications
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/14—Modified phenol-aldehyde condensates
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
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- G—PHYSICS
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
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- G—PHYSICS
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
- G03F7/0236—Condensation products of carbonyl compounds and phenolic compounds, e.g. novolak resins
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials For Photolithography (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Description
200424764 (1) 玖、發明說明 【發明所屬之技術領域】 本發明有關製造LCD用之正型光阻組成物及光阻圖型 之形成方法。 【先前技術】 至今，在製造玻璃基板上形成液晶顯示部分的液晶顯 示器（LCD )時，由於比較廉價，或能形成靈敏度、解像 性以及形狀優異之故，多在利用爲半導體元件之製造所使 用的由酚醛淸漆樹脂一含苯醌二疊氮基之化合物之系列所 成正型光阻組成物。 但，例如，在半導體元件之製造上，係最大採用直徑 8吋（約200mm )至12吋（約3 00mm )之圓盤型矽晶圓， 惟相對於此，在LCD之製造上，則最小亦有採用3 60mm x460mm程度之四方型玻璃基板。 如此，在L C D之製造領域中，將塗佈光阻材料的基板 當然在材質或形狀方面有所不同’惟在其尺寸方面，則與 半導體元件之製造所用者大有不同。 因此，LCD製造用之光阻材料，需要能對廣闊的基 板面全面形成形狀及尺寸安定性等特性良好的光阻圖型。 又，在LCD之製造上，由於消耗很多光阻材料之故， LCD製造用之光阻材料，除上述特性以外，尙需要成本 低廉的考量。 至今，關於LCD製造用之光阻材料，有多數報告（例 (2) (2)200424764 如，下述專利文獻1至6 )。專利文獻1至6所記載之光阻材 料係廉價，且對例如，3 60mm x 4 6 0 m m程度之小型基板 ，能形成塗佈性、靈敏度、解像性、形狀以及尺寸安定性 優異的光阻圖型。因此，在製造比較小型之L C D的目的上 ，很適合採用。 [專利文獻1 ] 日本專利特開平9-丨602 3 1號公報 [專利文獻2] 曰本專利特開平9 _ 2 1 1 8 5 5號公報 [專利文獻3] 日本專利特開2000-112120號公報 [專利文獻4] 日本專利特開2 0 0 0 - 1 3 1 8 3 5號公報 [專利文獻5] 日本專利特開2 0 0 0 - 1 8 1 0 5 5號公報 [專利文獻6] 曰本專利特開2 0 0 1 - 7 5 2 7 2號公報 【發明內容】 [發明所欲解決的課題] 然而’近年來，隨著個人電腦之顯示器之大型化或液 晶電視之普及等，較從前對大型L C D的需求增大。又，由 於有LCD之低價格化之要求，需要改善LCD之製造效率。 因此，在LCD之製造領域中，從產率（每單位時間之 (3) (3)200424764 處理量）之提升及處理管制性之觀點來看，需要具有3〇至 5 0 m J程度之靈敏度的光阻材料。又，從產率（每單位時間 之處理重）之提升之觀點來看’需要儘量擴大曝光面積爲 至少1 0 0 m m ▲程度。一般’ L C D製造上，認爲最好採用N A (透鏡之開口數）例如在〇 . 3以下，特別是在〇 · 2以下之低 ΝΑ條件之曝光過程。 然而’如採用低Ν Α條件之曝光過程時，在以往之 LCD製造用之光阻材料，例如，在0.3以下之低ΝΑ條件 下’以高解像度形成形狀優異的光阻圖型，有其困難存在 〇 亦即’ 一'般’解像度（解像界限）可以下式所示雷利 氏之式： R = k 1 X λ /ΝΑ [式中，R爲解像界限，1^爲因光阻或過程，像形成法所決 定的比例常數，λ爲曝光過程中所用的光之波長，N A表 示透鏡之開口數]表示，由於採用波長λ短的光源，或採 用高ΝΑ之曝光過程，而可提升解像度。例如，不用在來 L C D製造所用的g線（4 3 6 n m )，而使用更短波長之i線（ 3 6 5 nm)曝光的光刻術（photolitho graphy)，即可提升 解像度。 然而，在LCD之製造上，如上述，曝光面積會變狹小 的高NA化並不合適，而希望能採用低NA條件下的曝光過 程。因而，難於獲得高解像度。 再者，現在，作爲新世代之LCD而盛行在1片玻璃基 (4) 200424764 板上與顯示器部分同時形成驅動器，DAC ( I Analog Converter，數位類比轉換器、影像處理器 控制器、RAM (隨機存取記憶體）之稱爲所謂「系 」的對高功能L C D的技術開發（半導體平板顯示器 )世界200 1年9月出版第50至67頁）。 此時，基板上，由於除顯示器部分以外，尙會 體電路部分之故，基板有更大型化的傾向。因此， 通常之LCD製造時更爲低的NA條件下的曝光。 再者’在此種系統LCD中，例如，顯示器部分 尺寸爲2至10 μιη程度，相對地，積體電路部分則| 至2·0 μιη程度之微細的尺寸所形成。因此，較佳爲 0.5至2.0 μηι程度之微細的光阻圖型，故需要較在來 製造用光阻材料爲高解像度的光阻材料。 但，由於在來之LCD製造用之光阻材料，係難 NA條件下，以高解像者形成之故，難於用爲系統 製造。例如，在0.3以下之低ΝΑ條件下，難於形成 異的例如，2·0 μιη以下之微細的光阻圖型，而有所 圖型爲非矩形而呈現錐形的傾向。 具體而言，例如，日本專利特開2001-75272號 ，記載有含有鹼可溶性樹脂及感光性成分，而不含 (Sensitizer )的液晶用光阻。 然而，該液晶用光阻，存有不適合於i g曝光 形成系統LCD製造所需要的2.0 μιη以下之光阻圖型 )i g i t a 1 - 、視訊 統LCD (fpd 形成積 需要較 之圖型 至以0.5 能形成 之LCD 於在低 LCD之 形狀優 得光阻 公報中 增感劑 ，難於 等問題 (5) (5)200424764 因而，爲系統LCD之製造過程，希望出現一種適合於 i線曝光，例如即使在0.3以下之低N A條件下仍能形成形狀 優異的微細的光阻圖型的光阻材料。 亦即，本發明係以提供具有3 0至5 0 m *1程度之敏感度， 在低N A條件下的解像性優異，作爲於1個基板上形成積體 電路與液晶顯示器部分的LCD製造用很合適之作爲光阻材 料的正型光阻組成物及光阻圖型之形成方法爲課題者。 [爲解決課題的手段] 爲解決前述課題，本發明之LCD用正型光阻組成物之 特徵爲：含有 (A ) 鹼可溶性樹脂， (2) 聚苯乙烯換算質量平均分子量在300至1300之 低分子量酚醛淸漆樹脂與萘醌二疊氮磺酸化合物的平均酯 化率在30至90%之酯化反應生成物， (C ) 分子量在1 0 0 0以下之含酚性羥基之化合物， (〇) 有機溶劑。 該LCD用正型光阻組成物，係作爲i線曝光過程用LCD 用正型光阻組成物很適用者。 又，係NA在0.3以下之曝光過程用LCD用正型光阻組 成物很適用者。 再者，係作爲於1個基板上形成有集積電路與液晶顯 示器部分的LCD製造用之LCD用正型光阻組成物很適用者 (6) (6)200424764 在此，本發明之說明中’系統L c D係指在此「於1個 基板上形成有積體電路與液晶顯示器部分的LCD」之意。 又，本發明之光阻圖型之形成方法之特徵爲：含有 (1 ) 於基板上塗佈上述本發明之正型光阻組成物 ，以形成塗膜的過程， (2 ) 將形成有上述塗膜的基板實施加熱處理（ P r e b a k e，預焙），以形成光阻被膜於基板上的過程， (3 ) 使甩描繪有遮罩圖型（mask pattern )的光罩 ，對上述光阻被膜實施選擇性曝光的過程， (4 ) 對上述選擇性曝光後之光阻被膜，實施加熱 處理（post-exposure bake，曝光後焙燒）的過程， (5 ) 對上述加熱處理後之光阻被膜，實施使用鹼 水溶液的顯像處理，以形成光阻圖型於上述基板上的過程 (6 ) 將殘留於上述光阻圖型表面的顯像液加以沖 去的漂洗（rinse )過程。 並且’在實施上述（3 )選擇性曝光的過程中，作爲 上述光罩，而使用描繪用2.0 μπι以下之光阻圖型形成用遮 罩圖型’及2·0 μηι以上之光阻圖型形成用遮罩圖型之兩者 的光罩’藉以同時形成上述（5 )光阻圖型的過程中，可 於上述基板上同時形成圖型尺寸2〇μηι以下之積體電路用 之光阻圖型’及2.0 μηι以下之液晶顯示器部分用之光阻圖 型。 200424764 [發明之效果] 如採用本發明之LCD用正型光阻組成物及光阻圖型之 製造方法時，即使在低N A條件下仍可獲得良好的解像度 之故，可作爲系統L C D之製造用很合適。 【實施方式】 [發明之實施形態] [LCD用正型光阻組成物] 〈（A )成分〉 (A )成分，並不特別限定，而可從正型光阻組成物 中通常可用爲被膜形成物質之中任選1種或2種以上使用。 可例舉：使酚類（苯酚、間甲酚、對甲酚、二甲苯酚 、三甲基苯酚等）、醛類（甲醛、甲醛先驅物、2—羥基 苯甲醛、3 —羥基苯甲醛、4一羥基苯甲醛等）及/或酮類（ 甲基乙基甲酮、丙酮等），在酸性觸媒存在下進行縮合所 得酚醛淸漆樹脂； 羥基苯乙烯之單獨聚合物、或羥基苯乙烯與其他苯乙 烯系單體的共聚物、羥基苯乙烯與丙烯酸或甲基丙烯酸或 者與其衍生物的共聚物等之羥基苯乙烯系樹脂； 本身爲丙嫌酸或甲基丙烯酸與其衍生物的共聚物的丙 烯酸或甲基丙烯酸系樹脂等。 特別是’使含有間甲酚及對甲酚的酚類與含有甲醛的 醛類縮合反應所得酚醛淸漆樹脂，在高敏感度而解像性優 異的光阻材料之調整方面很合適。 -11 - (8) (8)200424764 (A )成分，可依常法製造。 (A )成分之依凝膠滲透色譜法的聚苯乙烯換算質量 平均分子量，雖視其種類而異，惟由敏感度或圖型形成方 面來看，爲2000至100000，較佳爲3000至20000。 < (B )成分> (B)成分，係聚苯乙烯換算質量平均分子量（以下 ，簡稱M w )在3 0 0至1 3 0 0之低分子量酚醛淸漆樹脂與萘醌 二疊氮磺酸化合物的平均酯化率爲3 0至9 0 %之酯化反應生 成物，而可任選1種或2種以上之屬於此等酯化反應生成物 者使用。在此，聚苯乙烯換算質量平均分子量係依例如 GPC (凝膠滲透色譜法）測定者。 該低分子量酚醛淸漆樹脂而言，可使用例如與上述（ A )成分所用者同樣的鹼可溶性酚醛淸漆樹脂中經調整質 量平均分子量爲上述範圍者等。 此種低分子量酚醛淸漆樹脂之Mw爲3 00至1300，下限 値較佳爲3 5 0以上，上限値較佳爲7 00以上。 如將質量平均分子量調整爲此範圍，即可提供高敏感 度而解像性優異，適合於低NA條件下的i線曝光過程的光 阻材料。 如欲調整質量平均分子量爲前述範圍時，可例舉如下 3種手段。 (i ) 將由所希望之酚類與醛類及/或酮類間的縮合 反應所得Mw爲2000至3 0000程度之酚醛淸漆樹脂，使用分 -12- (9) (9)200424764 選低分子量區域與高分子量區域的周知之分選操作以取出 低分子量區域部分，即可製得。 另外，在（A )成分之鹼可溶性酚醛淸漆樹脂之合成 時’一般技術常識係採用分選操作以選擇性取出高分子量 領域者，而在爲製得此種低分子量酚醛淸漆樹脂之用的分 選操作，亦僅在所選擇性取出的對象爲低分子量領域有所 不同而已，其餘則可適用同樣操作。 (ii ) 在所希望之酚類與醛類及/或酮類間的縮合反 應時，在反應途中，逐次測定反應溶液中之縮合物之Mw ’如Mw到達3 00至1 3 00之範圍時終止反應，即可製得。 另外，如合成所用各種原料、觸媒種類、或其量及比 例、反應條件（溶液濃度、反應溫度、各種原料之調配手 段等）相同時，如測定反應中之M w —次，則在下次合成 同樣的低分子量酚醛樹脂時，僅需控制反應時間即可製得 所希望之Mw者。 (iii ) 將所希望之酚類與醛類及/或酮類，在酸性觸 媒或鹼性觸媒之存在下縮合反應，以合成2至4核種之低分 子酚化合物或此化合物之二羥甲基物（簡稱爲「苯酚A」 )，對此使含羥甲基之酚類或不含羥甲基之酚類（簡稱爲 「苯酚B」）反應即可製得。 苯酚A與苯酚B間的反應，需要將Mw能成爲300至 1 3 0 0之範圍之方式加以控制，例如控制上述反應時間即可 進行。 在此，如對含有苯酚A的高濃度之溶液中，按每次非 -13- 200424764 常微量添加含有苯酚B的低濃度之溶液，即可容易上述控 制。 另外，酚類與醛類及/或酮類的比例，雖視作爲目的 之化合物及合成手段之不同而可適當調整，惟例如可作咬 1 ·· 1至2 : 1 (莫耳比）。 (B )成分而言，特別是下述2種（（i ) 、 （ i i )之 中含有1種以上者，從效果來看，較合適。 (i ) 作爲酚類而僅使用2官能苯酚化合物，作爲縮 合劑而使用醛類及/或酮類（較佳爲僅甲醛）以合成者。 (ϋ ) 作爲酚類而僅使用2官能苯酚化合物及1官能 苯酚化合物，作爲縮合劑而使用醛類及/或酮類（較佳爲 僅甲醛）以合成者。 上述「官能基」係指於酚類之會與醛類及/或酮類反 應之部位（2、4、6位）所存在的氫原子（該氫原子即與 醛類及/或酮類反應）之數之意。 前述2官能苯酌化合物，可以下述一般式（I)表示。200424764 (1) 发明. Description of the invention [Technical field to which the invention belongs] The present invention relates to a positive type photoresist composition for manufacturing LCD and a method for forming a photoresist pattern. [Prior art] Until now, when manufacturing liquid crystal displays (LCDs) with a liquid crystal display portion formed on a glass substrate, they have been used in semiconductor device manufacturing facilities because they are relatively inexpensive or can form sensitivity, resolution, and excellent shape. A positive photoresist composition formed from a series of phenolic lacquer resins and compounds containing a benzoquinonediazide group. However, for example, in the manufacture of semiconductor devices, a disc-type silicon wafer with a diameter of 8 inches (about 200 mm) to 12 inches (about 300 mm) can be used at the maximum. However, in contrast, in the manufacture of LCDs, the smallest Square glass substrates with a size of 3 60mm x 460mm are also available. In this way, in the manufacturing field of LC, the substrates coated with photoresist materials are of course different in material or shape ', but in terms of size, they are very different from those used in the manufacture of semiconductor elements. Therefore, the photoresist material for LCD manufacturing needs a photoresist pattern that can form a wide range of substrates with good characteristics such as shape and dimensional stability. In addition, in the manufacture of LCDs, a lot of photoresist materials are consumed. In addition to the above characteristics, the photoresist materials used in LCD manufacture require low-cost considerations. So far, there have been many reports on photoresist materials for LCD manufacturing (Example (2) (2) 200424764, for example, the following Patent Documents 1 to 6). The photoresist materials described in Patent Documents 1 to 6 are inexpensive, and can form light with excellent coatability, sensitivity, resolvability, shape, and dimensional stability to a small substrate of about 3 60 mm x 4 60 mm, for example. Resistive pattern. Therefore, it is very suitable for the purpose of manufacturing relatively small LC. [Patent Document 1] Japanese Patent Laid-Open No. 9- 丨 602 3 No. 1 [Patent Document 2] Japanese Patent Laid-Open No. 9 _ 2 1 1 8 5 5 [Patent Document 3] Japanese Patent Laid-Open No. 2000-112120 Gazette [Patent Document 4] Japanese Patent Laid-Open No. 2 0 0 0-1 3 1 8 3 [Patent Document 5] Japanese Patent Laid-Open No. 2 0 0 0-1 8 1 0 5 [Patent Document 6] Japanese Patent Laid-Open Publication No. 2000-1-7 5 2 7 2 [Summary of the Invention] [Problems to be Solved by the Invention] However, in recent years, with the enlargement of the display of personal computers or the popularity of liquid crystal televisions, The demand for large LCDs is greater than before. In addition, due to the demand for lower price of LCD, it is necessary to improve the manufacturing efficiency of LCD. Therefore, in the field of LCD manufacturing, from the standpoint of improvement in productivity ((3) (3) 200424764 throughput per unit time) and processing control, it is necessary to have a sensitivity of about 30 to 50 m J Photoresist material. Moreover, from the viewpoint of improvement in productivity (heavy processing weight per unit time), it is necessary to maximize the exposure area to at least 100 mm. Generally, in the manufacture of L C D, it is considered that it is best to use an exposure process in which NA (the number of openings of the lens) is, for example, 0.3 or less, and in particular, a low NA condition of 0.2 or less. However, it is difficult to form a photoresist pattern with excellent resolution at a high resolution when using a photoresist material for LCD manufacturing in the past, such as when using an exposure process with a low NA condition, for example, under a low NA condition below 0.3. Existence 〇, that is, 'one'-like' resolution (resolution limit) can be expressed by Rayleigh's formula: R = k 1 X λ / ΝΑ [where R is the resolution limit and 1 ^ is due to photoresistance Or the process, like the proportionality constant determined by the formation method, λ is the wavelength of light used in the exposure process, and NA is the number of openings of the lens. Improve resolution. For example, instead of using the g-line (4 3 6 nm) used in the manufacture of the LCD, a photolitho graphy using a shorter-wavelength i-line (36.5 nm) exposure can improve the resolution. However, in the manufacture of LCDs, as described above, it is not appropriate to increase the NA with a narrow exposure area, and it is desirable to use an exposure process under low NA conditions. Therefore, it is difficult to obtain a high resolution. Furthermore, now, as a new generation of LCD, it is popular to form a driver on a glass substrate (4) 200424764 board and the display part at the same time, DAC (I Analog Converter, digital analog converter, image processor controller, RAM (random) Access to memory), the so-called "system," the development of high-performance LCD technology (semiconductor flat panel display), published in September 2001, pages 50 to 67). At this time, the substrate tends to be larger in size because of the fact that the circuit portion is not the display portion. Therefore, the exposure under the lower NA condition is usually made in the LCD manufacturing. Furthermore, in such a system LCD, for example, the display part has a size of about 2 to 10 μm, and the integrated circuit part is formed by a fine size of about 2.0 μm. Therefore, a fine photoresist pattern with a thickness of about 0.5 to 2.0 μm is preferred, so a photoresist material for manufacturing is required to be a high-resolution photoresist material. However, since the photoresist materials used in the manufacture of LCDs are difficult to form under high NA conditions, they are difficult to use for system manufacturing. For example, under a low NA condition of 0.3 or less, it is difficult to form a fine photoresist pattern of, for example, 2.0 μm or less, and the pattern tends to be non-rectangular and tapered. Specifically, for example, Japanese Patent Laid-Open No. 2001-75272 describes a photoresist for a liquid crystal that contains an alkali-soluble resin and a photosensitive component and does not contain (Sensitizer). However, the photoresist for the liquid crystal has a photoresist pattern of 2.0 μm or less, which is not suitable for the manufacture of the ig exposure formation system LCD. Igita 1-, video system LCD (fpd formation product needs to be 0.5 The formed LCD is a sensitizer in the photoresistance bulletin of the low LCD shape, which is difficult to wait. (5) (5) 200424764 Therefore, for the manufacturing process of the system LCD, it is desirable to have a suitable i-line exposure. A photoresist material having a fine photoresist pattern can be formed even under a low NA condition of 0.3 or less. That is, the present invention is to provide a sensitivity having a degree of 30 to 50 m * 1 under low NA conditions. It has excellent resolution, and is suitable for the manufacture of LCDs in which integrated circuits and liquid crystal display parts are formed on one substrate. Positive photoresist compositions and photoresist pattern formation methods that are suitable as photoresist materials are the subject of the project. [Means for solving problems] In order to solve the foregoing problems, the positive-type photoresist composition for LCDs of the present invention is characterized by containing (A) an alkali-soluble resin, and (2) a polystyrene-equivalent mass average molecular weight of 300 to 1300. Low score Phenolic lacquer resin and naphthoquinonediazidesulfonic acid compound having an average esterification rate of 30 to 90%, (C) a phenolic hydroxyl-containing compound having a molecular weight of 1000 or less, ( 〇) Organic solvent. The positive photoresist composition for LCD is suitable as a positive photoresist composition for LCD for i-line exposure process. Also, it is positive photoresist for LCD for exposure process with NA below 0.3. Resistive composition is very suitable. Furthermore, it is suitable as a positive photoresist composition for LCD used in the manufacture of LCDs with integrated circuits and liquid crystal display parts formed on one substrate. (6) (6) 200424764 Here In the description of the present invention, the “system L c D” means “the LCD with the integrated circuit and the liquid crystal display portion formed on one substrate”. Also, the features of the method for forming the photoresist pattern of the present invention The process includes (1) a process of coating the positive photoresist composition of the present invention on a substrate to form a coating film, and (2) subjecting the substrate on which the coating film is formed to a heat treatment (prebake). To form a photoresist film on the substrate, (3) making The process of selectively exposing the photoresist film to a photomask of a mask pattern, (4) performing post-exposure bake on the photoresist film after the selective exposure, and post-exposure baking ), (5) the photoresist film after the heat treatment is subjected to a development process using an alkaline aqueous solution to form a photoresist pattern on the substrate (6) will remain on the photoresist pattern surface The developing solution is rinsed (rinse). And 'in the implementation of the above (3) selective exposure, as the photomask, a photoresist pattern forming mask pattern of 2.0 μm or less is used and a photoresist pattern of 2.0 μm or more is used as the photomask. In the process of forming the above (5) photoresist pattern at the same time, a photomask for both the mask patterns for forming can be used to simultaneously form photoresists for integrated circuits with a pattern size of less than 20 μηι on the above substrate. Patterns' and photoresistive patterns for liquid crystal display parts below 2.0 μηι. 200424764 [Effect of the invention] If the positive photoresist composition for the LCD and the photoresist pattern manufacturing method of the present invention are used, it can be used as a system LCD to manufacture a good resolution even under low NA conditions. Very suitable. [Embodiment] [Embodiments of the invention] [Positive photoresist composition for LCD] <(A) component> The (A) component is not particularly limited, and can be generally used as a coating film from a positive photoresist composition Among the forming substances, one kind or two or more kinds are optionally used. Examples include: phenols (phenol, m-cresol, p-cresol, xylenol, trimethylphenol, etc.), aldehydes (formaldehyde, formaldehyde precursors, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, etc.) and / or ketones (methyl ethyl ketone, acetone, etc.), obtained by condensation in the presence of an acidic catalyst; a phenolic lacquer resin; a separate polymer of hydroxystyrene or hydroxystyrene Copolymers with other styrenic monomers, copolymers of hydroxystyrene with acrylic acid or methacrylic acid, or derivatives thereof; hydroxystyrene resins such as copolymers of propionic acid or methacrylic acid and their derivatives Acrylic or methacrylic resins. In particular, a phenolic lacquer resin obtained by condensing a phenol containing m-cresol and p-cresol with an aldehyde containing formaldehyde is suitable for adjustment of a photoresist material having high sensitivity and excellent resolution. -11-(8) (8) 200424764 (A) component, which can be manufactured by ordinary methods. (A) The polystyrene-equivalent mass average molecular weight of the component according to gel permeation chromatography, although it varies depending on its type, but from the aspect of sensitivity or pattern formation, it is 2,000 to 100,000, preferably 3,000 to 20,000 . < (B) component > (B) component is a low molecular weight phenolic lacquer resin and naphthoquinonediazide with a polystyrene equivalent mass average molecular weight (hereinafter referred to as Mw) of 300 to 1300. The sulfonic acid compound has an average esterification rate of 30 to 90% of the esterification reaction product, and may be used by one or more of these esterification reaction products. Here, the polystyrene equivalent mass average molecular weight is measured by, for example, GPC (gel permeation chromatography). As the low-molecular-weight phenolic lacquer resin, for example, the same alkali-soluble phenolic lacquer resin as that used for the component (A) can be used. The Mw of such a low-molecular-weight phenolic lacquer resin is from 300 to 1300, and the lower limit 値 is preferably 3 50 or more, and the upper limit 値 is preferably 7 or more. If the mass average molecular weight is adjusted to this range, a photoresist material having high sensitivity and excellent resolvability and suitable for i-line exposure process under low NA conditions can be provided. When the mass average molecular weight is to be adjusted to the aforementioned range, the following three methods can be exemplified. (i) A phenolic lacquer resin having a Mw of about 2000 to 30,000 obtained by the condensation reaction between the desired phenols and aldehydes and / or ketones, using a low molecular weight of -12- (9) (9) 200424764 A well-known sorting operation of a region and a high-molecular-weight region can be obtained by taking out a portion of the low-molecular-weight region. In addition, in the synthesis of the alkali-soluble phenolic lacquer resin of the component (A), 'general technical common sense' uses a sorting operation to selectively take out high-molecular-weight fields, and is used to prepare such low-molecular-weight phenolic lacquer resin The sorting operation is different only in the case where the selected object is a low molecular weight area, and the rest can be applied to the same operation. (ii) In the desired condensation reaction between phenols and aldehydes and / or ketones, during the reaction, the Mw 'of the condensate in the reaction solution is measured one by one, such as when Mw reaches the range of 3 00 to 1 3 00 It can be obtained by stopping the reaction. In addition, if the various raw materials used in the synthesis, the types of catalysts, or their amounts and ratios, and the reaction conditions (solution concentration, reaction temperature, and the preparation methods of various raw materials, etc.) are the same, if the Mw in the reaction is measured, the next time When synthesizing the same low molecular weight phenolic resin, the desired Mw can be obtained by controlling the reaction time only. (iii) Condensation of the desired phenols with aldehydes and / or ketones in the presence of acidic catalysts or basic catalysts to synthesize low molecular phenolic compounds of 2 to 4 cores or the dihydroxy groups of the compounds Methyl compounds (referred to as "phenol A") can be prepared by reacting methylol-containing phenols or methylol-free phenols (referred to as "phenol B"). The reaction between phenol A and phenol B needs to be controlled in such a manner that Mw can be in the range of 300 to 13,000, for example, by controlling the above reaction time. Here, for a solution containing a high concentration of phenol A, the above-mentioned control can be easily performed by adding a solution containing a low concentration of phenol B in a very small amount every time. In addition, although the ratio of phenols to aldehydes and / or ketones can be appropriately adjusted depending on the target compound and the synthesis method, it can be bite 1 ·· 1 to 2: 1 (Molar ratio), for example. (B) As for the component, in particular, it is more suitable to contain one or more of the following two kinds ((i), (ii)). (I) As a phenol, only a bifunctional phenol compound is used. Synthesizers using aldehydes and / or ketones (preferably only formaldehyde) as a condensing agent. (Ϋ) As a phenol, only a bifunctional phenol compound and a monofunctional phenol compound are used, and as a condensing agent, aldehydes are used. And / or ketones (preferably only formaldehyde) are synthesized. The above "functional group" refers to the presence of phenols at positions (positions 2, 4, and 6) where they will react with aldehydes and / or ketones. The meaning of the number of hydrogen atoms (this hydrogen atom is reacted with aldehydes and / or ketones). The aforementioned bifunctional benzene compound can be represented by the following general formula (I).
r ^r4 R3 (式中，R1至R5爲分別獨立之氫原子，或碳原子數1至5之 烷基，而R1、R3、m以及R5中之2個爲氫原子，而1個爲碳 原子數1至5之烷基。） 2官能苯酣化合物中，前述碳原子數1至5 (較佳爲1至 -14- 200424764 3，更佳爲甲基）之烷基，可爲直鏈狀、分枝鏈狀。 又，R1、R3以及R5中，烷基將結合之位置，並無優劣 之分。 2 官能苯酚化合物而言，因廉價且特性優異之故， 較佳爲鄰甲酚、對甲酚、2，5—二甲苯酚、3，4一二甲苯 酚、2，3，5 —三甲基酚。 前述1官能苯酚化合物，可以下述一般式（Π )表示r ^ r4 R3 (where R1 to R5 are independent hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, and two of R1, R3, m, and R5 are hydrogen atoms, and one is carbon An alkyl group having 1 to 5 atoms.) In the bifunctional phenylhydrazone compound, the aforementioned alkyl group having 1 to 5 carbon atoms (preferably 1 to -14-200424764 3, more preferably methyl) may be a straight chain. Shaped, branched chain. In R1, R3, and R5, there is no difference between the positions at which alkyl groups are bonded. 2-functional phenol compounds are preferred because of their low cost and excellent properties. Ortho-cresol, p-cresol, 2,5-xylenol, 3,4-xylenol, 2,3,5-trimethylol Based phenol. The monofunctional phenol compound can be represented by the following general formula (Π)
(式中，R11至R15爲分別獨立之氫原子，或碳原子數1至5 之烷基，而R11、R13，以及R15中之1個爲氫原子，而2個 爲碳原子數1至5之烷基。） 1官能苯酚化合物中，前述碳原子數1至5(較佳爲1 至3，更佳爲甲基）之烷基，可爲直鏈狀、分枝鏈狀。 又，R11、R13、以及R15中，烷基將結合之位置，並 無優劣之分。 1官能苯酚化合物而言，因廉價且特性優異之故， 較佳爲2，4 -二甲苯酚、2，6 -二甲苯酚。 另外，前述（i )中，因特性優異之故，2官能苯酚 化合物：醛類及/或酮類（較佳爲甲醛），係按1 : 1至2 ·· 1 ( 莫耳比）使用。 -15- (12) (12)200424764 前述（i i )中，因特性優異之故，2官能苯酚化合物 :1官能苯酚化合物，係按1 〇 : 1至1 : 1 〇，較佳爲5 Μ至1 : 5 ( 莫耳比）使用。因特性優異之故，酚類之合計：醛類及/ 或酮類（較佳爲甲醛），係按1 : 1至2 : 1 (莫耳比）使用。 前述（Π )之低分子量酚醛淸漆樹脂之合成的方法而 言，可舉：①對依常法所得2官能苯酚化合物之二羥甲 基溶液，調配1官能苯酚化合物之溶液，在酸觸媒之存 在下進行縮合反應的方法，②對2官能苯酚化合物，與 醛類及/或酮類的縮合反應物，調配1官能苯酚化合物之 溶液，在酸觸媒之存在下進行縮合反應的方法，等。 前述①，係對含有苯環3個以下的低分子量酚醛樹脂 之合成很合適，而前述②，係對含有苯環4個以上的低分 子量酚醛樹脂之合成很合適。 接著，由此種低分子量酚醛淸漆樹脂與萘醌二疊氮磺 酸化合物的酯化反應之進行，可製得平均酯化率爲3 0至 90%之酯化反應生成物[(Β )成分]。 萘醌二疊氮磺酸化合物，可從正型光阻組成物中一般 所用者任選1種或2種以上使用。 酯化反應之方法而言，並無特別限定，而可利用在來 周知之反應。 例如，使萘醌二疊氮磺醯氯與低分子量酚醛淸漆樹脂 縮合反應。具體而言，使萘醌一1，2—二疊氮一4 (或5 )一磺醯氯、與低分子量酚醛淸漆樹脂縮合反應。具體而 言，將萘醌一1，2—二疊氮一4 (或5 ) —磺醯氯、與低分 -16· (13) (13)200424764 子量酚醛樹脂既定量溶解於二噁烷、正甲基哦略院酮、二 甲基乙醯胺、四氫呋喃等之有機溶劑中’對此添加三乙胺 、三乙醇胺、吡啶、碳酸鹼、碳酸氫鹼等鹼性觸媒以使其 反應，將所得生成物水洗、乾燥即可得。 如此方式所得酯化反應生成物之平均酯化率爲3 0至 9 0 %，較佳爲4 0至7 0 %程度。如作成3 0 %以上’則可形成 對比（contrast )優異的光阻圖型。另一方面’如作成 9 0 %以下，則可防止敏感度之降低。如超過9 0 %以上’則 可能會引起顯著的敏感度低落’可能不適合爲LCD用正型 光阻組成物，甚至於系統LCD用。 酯化率，可藉由低分子量酚醛淸漆樹脂與萘醌二疊氮 磺酸化合物的量性比例’或酯化反應之反應時間等之變更 ，而可加以調整。 在此，低分子量酚醛淸漆樹脂、與萘醌二疊氮磺酸化 合物之比例，從酯化率之調整等來看，係對低分子量酚醛 淸漆樹脂中之羥基1莫耳，作成萘醌二疊氮磺酸化合物 爲〇·3至0.9莫耳，較佳爲0.4至0.7莫耳。 在此，此種（B )成分，即所謂感光性成分。 爲本發明之正型光阻組成物，除此種（B )成分之外 ，尙可使用一般在正型光阻組成物所用之其他萘醌二疊氮 酯化合物。 例如，聚羰基二苯甲酮或五倍子酸烷酯等之苯酚化合 物與萘醌二疊氮磺酸化合物的酯化反應生成物亦可使用。 但，爲防止影響本發明之效果起見，此等之使用量係 -17- (14) (14)200424764 包含（B )成分的全感光性成分中’爲5 0質量％以下，較 佳爲20質量。/。以下。 正型光阻組成物中，包含（B )成分的感光性成分之 全體調配量，係在對（A )成分的驗可溶性樹脂與下述（ C)成分的合計量爲10至70質量％’較佳爲20至60質量％之 範圍選擇爲宜° 並且，感光性成分中之（B )成分之調配量’係作成 爲5 0質量％以上，較佳爲8 0至1 0 0質量％。 如將（B )成分之調配量作成下限値以上’即可製得 對圖型真空描繪的影像，亦能提升轉錄性（transcriPtion )。如將（B )成分之調配量作成上限値以上’則可防止 敏感度之劣化，又’可提升從正型光阻組成物所形成的光 阻膜之均質性，以改善解像性。 < (C )成分〉 (C)成分，較佳爲非二苯甲酮系之含酚性羥基之化 合物。使用此種（C )成分’即可製得敏感度改善效果優 異，即使在低NA條件下之i線曝光過程中，仍然係高敏度 、高解像度，而適合於系統LCD的材料。 (C)成分之分子量，由上述效果來看，爲1000以下 ，較佳爲700以下，實質上爲200以上，較佳爲3 00以上。 (C)成分而言，一般祗要是本身爲用以光阻組成物 的含酚性羥基之化合物，較佳爲能符合上述分子量之條件 者，則並不特別限定，而可任選1種或2種以上使用。而且 -18- (15) 200424764 ，其中較佳爲下述一般式（I v )(In the formula, R11 to R15 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and one of R11, R13, and R15 is a hydrogen atom, and two are 1 to 5 carbon atoms. In the monofunctional phenol compound, the aforementioned alkyl group having 1 to 5 carbon atoms (preferably 1 to 3, more preferably methyl) may be linear or branched. In R11, R13, and R15, there is no difference in the position where the alkyl group is bonded. The monofunctional phenol compound is preferably 2,4-xylenol and 2,6-xylenol because it is inexpensive and has excellent characteristics. In addition, in the aforementioned (i), because of excellent characteristics, the bifunctional phenol compound: aldehydes and / or ketones (preferably formaldehyde) are used in a ratio of 1: 1 to 2 ·· 1 (molar ratio). -15- (12) (12) 200424764 In the aforementioned (ii), because of excellent characteristics, the bifunctional phenol compound: the monofunctional phenol compound is in the range of 10: 1 to 1:10, preferably 5M to 1: 5 (Murbi) use. Due to its excellent characteristics, the total of phenols: aldehydes and / or ketones (preferably formaldehyde) is used in a ratio of 1: 1 to 2: 1 (Molar ratio). For the method for synthesizing the low molecular weight phenolic lacquer resin of (Π), the following can be mentioned: ① A solution of a bifunctional phenol compound obtained by a conventional method, a solution of a monofunctional phenol compound, and an acid catalyst A method of performing a condensation reaction in the presence of ②, a method of preparing a solution of a monofunctional phenol compound with a bifunctional phenol compound, a condensation reaction product of aldehydes and / or ketones, and performing a condensation reaction in the presence of an acid catalyst, Wait. The above ① is suitable for the synthesis of low molecular weight phenolic resins containing 3 or less benzene rings, while the above ② is suitable for the synthesis of low molecular weight phenolic resins containing 4 or more benzene rings. Next, the esterification reaction of such a low-molecular-weight phenolic lacquer resin with a naphthoquinonediazidesulfonic acid compound can be performed to obtain an esterification reaction product with an average esterification rate of 30 to 90% [(B) ingredient]. The naphthoquinonediazidesulfonic acid compound may be used singly or in combination of two or more kinds among those generally used in positive photoresist compositions. The method for the esterification reaction is not particularly limited, and a reaction known in the future can be used. For example, naphthoquinonediazidesulfonyl chloride is condensed with a low molecular weight phenolic lacquer resin. Specifically, the naphthoquinone-1,2-diazide-4 (or 5) -sulfonyl chloride is condensed with a low molecular weight phenolic lacquer resin. Specifically, naphthoquinone-1,2-diazide-4 (or 5) -sulfonyl chloride and low-scoring -16 · (13) (13) 200424764 sub-quantity phenolic resin were dissolved in dioxane. In organic solvents such as n-methyl, ketamine, dimethylacetamide, tetrahydrofuran, etc., basic catalysts such as triethylamine, triethanolamine, pyridine, alkali carbonate, and hydrogen carbonate are added to make it react. The obtained product can be washed with water and dried. The average esterification rate of the esterification reaction product obtained in this way is 30 to 90%, preferably about 40 to 70%. If it is 30% or more, a photoresist pattern with excellent contrast can be formed. On the other hand, if it is 90% or less, the decrease in sensitivity can be prevented. If it is more than 90%, it may cause a significant decrease in sensitivity. It may not be suitable for a positive photoresist composition for LCD, or even for a system LCD. The esterification rate can be adjusted by changing the quantitative ratio of the low molecular weight phenolic lacquer resin and naphthoquinonediazidesulfonic acid compound or the reaction time of the esterification reaction. Here, the ratio of the low-molecular-weight phenolic lacquer resin and the naphthoquinonediazide sulfonic acid compound is adjusted from the esterification rate, etc., to make 1 naphthoquinone to the hydroxyl group in the low-molecular-weight phenolic lacquer resin. The diazidesulfonic acid compound is from 0.3 to 0.9 mol, preferably from 0.4 to 0.7 mol. Here, such a (B) component is what is called a photosensitive component. As the positive photoresist composition of the present invention, in addition to this (B) component, other naphthoquinonediazide ester compounds generally used in positive photoresist compositions can be used. For example, an esterification reaction product of a phenol compound such as polycarbonylbenzophenone or alkyl gallic acid ester with a naphthoquinonediazidesulfonic acid compound can also be used. However, in order to prevent the effect of the present invention from being affected, the amount used is -17- (14) (14) 200424764. Among the total photosensitive components including the component (B), the content is 50% by mass or less, preferably 20 quality. /. the following. The total amount of the photosensitive component including the component (B) in the positive photoresist composition is based on the total amount of the soluble resin of the component (A) and the following component (C) being 10 to 70% by mass' A range of preferably 20 to 60% by mass is selected as appropriate, and the blending amount of the (B) component in the photosensitive component is 50% by mass or more, and preferably 80 to 100% by mass. If the blending amount of the (B) component is set to the lower limit 値 or more ', an image of vacuum drawing of the pattern can be prepared, and transcriPtion can also be improved. If the blending amount of the (B) component is set to the upper limit 値 or more, 'the sensitivity can be prevented from deteriorating, and the homogeneity of the photoresist film formed from the positive photoresist composition can be improved to improve the resolution. < Component (C) > The component (C) is preferably a non-benzophenone-based compound containing a phenolic hydroxyl group. The use of such (C) component 'can produce excellent sensitivity improvement effects. Even in the i-line exposure process under low NA conditions, it is still a material with high sensitivity and high resolution, which is suitable for system LCDs. The molecular weight of the component (C) is 1,000 or less, preferably 700 or less, substantially 200 or more, and preferably 300 or more from the above effects. (C) In general, if the compound is a phenolic hydroxyl-containing compound used for a photoresist composition, and preferably meets the above molecular weight requirements, it is not particularly limited, and one or Use more than 2 types. Moreover, -18- (15) 200424764, of which the following general formula (I v) is preferred
(IV) [式中，R31至R38表示分別獨立之氫原子、鹵原子、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；R4G、R41表示分別獨立之氫原子或碳原子 數1至6之院基；如R39爲氫原子或碳原子數1至6之院基時 ，卩爲氫原子，碳原子數1至6之烷基或可以下述化學式（ V )所表示殘基(IV) [wherein R31 to R38 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 ring having 3 to 6 carbon atoms Alkyl; R4G and R41 represent independent hydrogen atoms or radicals with 1 to 6 carbon atoms; for example, when R39 is a hydrogen atom or a radical with 1 to 6 carbon atoms, 卩 is a hydrogen atom and 1 to 6 carbon atoms The alkyl group of 6 may be a residue represented by the following chemical formula (V)
(式中，R4 2及R4 3表示分別獨立之氫原子、鹵原子、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，Q係與R3 9末端 結合而與R39及Q與R39之間之碳原子一起，形成碳鏈3至6 之環烷基者；a、b表示1至3之整數；d表示0至3之整數；η 表示〇至3之整數] 在此，如與Q與R39之間之碳原子一起，形成碳鏈3至6 -19- (16) (16)200424764 之環烷基時，則Q與R3 9即結合，而形成有碳原子數2至5之 亞烷基。 相當於前述一般式（IV )的苯酚化合物而言，可舉： 參（4一羥基苯基）甲烷、雙（4一羥基一3—甲基苯基）一 2—羥基苯基甲烷、雙（4一羥基一2，3，5—三甲基苯基 )一2-羥基苯基甲烷、雙（4一羥基一3，5—二甲基苯基 )一4一羥基苯基甲烷、雙（4一羥基一3，5—二甲基苯基 )一3 —羥基苯基甲烷、雙（4一羥基一3，5—二甲基苯基 )一 2—羥基苯基甲烷、雙（4一羥基一2，5—二甲基苯基 )一4一羥基苯基甲烷、雙（4一羥基一2，5—二甲基苯基 )一3 —羥基苯基甲烷、雙（4一羥基一2，5—二甲基苯基 )一2 —羥基苯基甲烷、雙（4一羥基一3，5—二甲基苯基 )一3，4一二羥基苯基甲烷、雙（4一羥基一2，5 —二甲基 苯基）一3，4一二羥基甲基甲烷、雙（4一羥基一2，5—二 甲基苯基）一2，4一二羥基苯基甲烷、雙（4一羥基苯基 )一3—甲氧基-4一羥基苯基甲烷、雙（4一羥基苯基）一 4一羥基一2—甲基苯基）一4一羥基苯基甲烷、雙（5—環己 基一4一羥基一2—甲基苯基）一2 —羥基苯基甲烷、雙（5 — 環己基一4一羥基一2—甲基苯基）一2 —羥基苯基甲烷、雙 (5 —環己基—4 —翔基—2 —甲基本基）—3，4 — 一.禅基本 基甲烷等之參酚型化合物； 2，4 —雙（3，5 一二甲基一4一羥基苄基）一5 一羥基苯 酚、2，6—雙（2，5 —二甲基一4一羥基苄基）一4 一甲酚等 之線型3核種苯酚化合物；1，1一雙[3 —（ 2 —羥基一5—甲 -20- (17) (17)200424764 基；基）一 4 一經基一 5 -環己基苯基]異丙；(¾、雙[2，5 — 一 甲基一3 —（4一羥基一 5-甲基苄基）一4一羥基苯基]甲烷、 雙[2，5 一二甲基一3 一（4一羥基苄基）一4一羥基苯基]甲 烷、雙[3—（3，5-二甲基一4一羥基；基）一4一羥基·5 — 甲基苯基]甲烷、雙[3 —（3，5—二甲基一4一羥基苄基）一 4 一經基一 5 —乙基苯基]甲院、雙[3 —（3’ 5 — _•乙基一 4 一 羥基苄基）一4一羥基一5—甲基苯基]甲烷、雙[3—（ 3， 5 一 _•乙基一 4 一經基爷基）一 4 一經基一 5 —乙基本基]甲院 、雙[2 —經基—3 — ( 3 ’ 5 — _•甲基—4 —經基卡基)—5 —甲 基苯基]甲烷、雙[2—羥基一3 —（ 2—羥基-5—甲基苄基 )一5 一甲基苯基]甲烷、雙[4一羥基一3 —（ 2 —羥基一5—甲 基苄基）一5—甲基苯基]甲烷、雙[2，5—二甲基一3 2 —羥基一5—甲基苄基）一4一羥基苯基]甲烷等之線型4核 種苯酚化合物；2，4一雙[2 —羥基一3 —（ 4一羥基苄基）一 5 —甲基苄基]一6—環己酚、2，4一雙[4 —羥基一3— ( 4 —羥 基苄基）一5—甲基苄基]一6—環己酚、2，6—雙[2，5 —二 甲基一3 —（2 —羥基一 5—甲基苄基）一4 一羥基苄基]一4 一 甲酚等之線型5核種苯酚化合物等之線型多酚化合物；雙 (2，3，4一三羥基苯基）甲烷、雙（2，4一二羥基苯基 )甲烷、2，3，4 —三羥基苯基一4’-羥基苯基甲烷、2-(2 ，3，4—三羥基苯基）一 2— (2’，3，，4’一三羥基苯基） 丙烷、2— ( 2，4一二羥基苯基）一2—（ 2’，4’一二羥基苯 基）丙烷、2— ( 3 —氟代一4一羥基苯基）一2—（ 3’一氟 代一4’一羥基苯基）丙烷、2—（ 2，4一二羥基苯基）一2 — -21 - (18) (18)200424764 (4·一羥基苯基）甲烷、2— ( 2，3，4一三羥基苯基）一 2 —（4· —羥基苯基）丙烷、2—（2，3，4一三羥基苯基 )一2一（ 4’一羥基一3’，5’一二甲基苯基）丙烷等之雙酚 型化合物；1一Π —（ 4一羥基苯基）異丙基]一4一[1，1 — 雙（4一羥基苯基）乙基]苯、1一[1一（3—甲基一4一羥基 苯基）異丙基]一4 一 [1，1 一雙（3 —甲基一4 一羥基苯基） 乙基]苯，等之多核分枝型化合物；1，1一雙（4 一羥基苯 基）環己烷等之縮合型化合物。 此等可以1種或組合2種以上使用。 其中，較佳爲1一[1 一（ 4一羥基苯基）異丙基]一4一[1 ，1 一雙（4一羥基苯基）乙基]苯。 (C )成分之調配量，從效果來看，係作成對（A ) 成分爲10至70質量％，較佳爲15至60質量％之範圍。 < (D )成分> (D )成分，祗要是光阻組成物所用的一般性者，則 並不特別限定而可選擇1種或2種以上，惟從塗佈性優異， 在大型玻璃基板上的光阻被膜之膜厚均勻性優異來看，較 佳爲含有丙二醇一烷基醚乙酸酯、及/或乳酸烷酯者。 丙二醇一院基醚乙酸醋’係例如碳原子數1至3之具有 直鏈或分枝鏈狀之烷基者，其中，由於在大型玻璃基板上 的光阻被膜之膜厚均勻性非常優異之故，特佳爲丙二醇一 甲基醚乙酸酯（以下，簡稱PGMEA )。 乳酸烷酯而言，可舉：乳酸甲酯、乳酸乙酯（以下， -22- (19) 200424764 簡稱EL )等。其中較佳爲乳酸乙酯，惟如使 6 0 0mm以上之大型玻璃基板時，有產生塗佈斑 因此，較佳爲以能抑制此種缺點之與其他溶齊 用c 丙二醇一烷基醚乙酸酯之調配量，從上述 較佳爲（D )成分中，作成2 0至1 0 0質量％。 乳酸烷酯之調配量，從上述效果來看， 成分中，作成爲2 0至1 0 0質量％。 又，如使用含有丙二醇一烷基醚乙酸酯及 方的（D )成分，則可得光阻被膜之膜均勻性 狀優異的光阻圖型，又在耐熱性之提升，浮渣 產生之抑制方面亦較佳。 如係丙二醇一烷基醚乙酸酯與乳酸烷酯之 則對丙二醇一烷基醚乙酸酯，按質量比，使, 量，較佳爲1至5倍量之乳酸烷酯。 又，2—庚酮（以下，簡稱HE )亦爲合適 。雖並不特別限定，如上述般，係當與非二苯 光性成分組合時很合適的溶劑。 2—庚酮，係較PGMEA之耐熱性爲優異， 降低浮渣產生的光阻組成物的特性，而非常合 2—庚酮，從上述效果來看，較佳爲在（I： 作成20至100質量。/〇。 另外，其他尙能調配的有機溶劑而言’具 舉如下述者。 用 5 0 0 m m χ 紋的傾向。 的混合系使 效果來看， 2佳爲（D ) 乳酸烷酯雙 優異，且形 (scum)之 混合系時， 闬〇 · 1至1 0倍 的有機溶劑 甲酮系之感 具有賦與經 適的溶劑。 》）成分中， 體上，可例 -23- (20) (20)200424764 亦即，^ 一丁內酯；丙二醇一丁醚；丙酮、甲基乙基 甲酮、環己酮、甲基異戊基甲酮等之酮類；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、或者此等之一甲醚、一乙醚、一丙醚、一 丁醚或一苯醚等之多元醇類及其衍生物；如二噁烷等的環 狀醚類；以及乙酸甲酯、乙酸乙酯、乙酸丁酯、丙酮酸甲 酯、丙酮酸乙酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯等之 酯類。 如使用此等溶劑時，在（D )成分中，較佳爲5 0質量 %以下。 本發明之正型光阻組成物中，在不影響本發明之目的 之範圍內，可含有視需要之具有相容性的添加物，例如爲 改良光阻膜之性能等用的附加性樹脂、可塑劑、儲存安定 劑、表面活性劑，使經顯像的影像更能可視性之用的著色 料，爲更提升增感效果之用的增感劑或光暈（halation ) 防止用染料、密接性改善劑、等習用之添加物。 光暈防止用染料而言，可使用紫外線吸收劑（例如， 2，2，，4，4’一四羥基二苯甲酮、4一二甲基胺基一 2’， 4’一二羥基二苯甲酮、5 —胺基一3 —甲基一 1 一苯基一4 一（ 4一羥基苯基偶氮基）吡唑、4-二甲基胺基一4’一羥基偶氮 基苯、4一二乙基胺基一4’一乙氧基偶氮基苯、4 一二乙基 胺基偶氮苯、薑黃素（curcumin)等）等。 表面活性劑，係例如可爲光條放電（s t r i a t i ο η )防止 等所添加者，例如可使用氟羅拉特FC-43 0、FC-431 (商品 (21) (21)200424764 名，住友3M (股）製）、埃佛特補EF 122A、EF 122B、 EF 122C、EF 126 (商品名、東化學產品（股）製）等之 氟系表面活性劑、R - 0 8 (商品名、大日本油墨化學工業（ 股）製）等。 本發明之正型光阻組成物，較佳爲將（A )成分、（ B )成分、（C )成分以及視需要之其他成分，溶解於（d )有機溶劑中，即可調製。 在此，（D )成分之使用量，係較佳爲將（A )至（C )成分以及視需要所用的其他成分加以溶解，可按能得均 勻的正型光阻組成物的方式適當調整。較佳爲按全固體成 分濃度能成爲10至40質量％，更佳爲20至30質量。/〇之方 式使用。 [光阻圖型之形成方法] 以下，表示LCD製造中的光阻圖型之很合適的形成 方式之一例。 首先，使用離心式撒佈器（spinner)等將上述之本發 明之正型光阻組成物塗佈於基板上以形成塗膜。基板較佳 爲玻璃基板。玻璃基板，通常使用非晶形氧化矽（ a m 〇 r p h 〇 u s s i 1 i c a )，惟在系統L C D之領域中，係認爲低溫 聚矽等較佳。此種基板，係由於本發明之正型光阻組成物 在低NA條件下的解像性優異之故，可使用5 00mm x 600mm以上，特別是550mm x650mm以上之大型基板。(In the formula, R4 2 and R4 3 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 cycloalkane having 3 to 6 carbon atoms. Group; c represents an integer from 1 to 3) 'or Q is bonded to the 9-terminus of R3 and together with the carbon atom between R39 and Q and R39 to form a cycloalkyl group of carbon chain 3 to 6; a, b represents An integer of 1 to 3; d represents an integer of 0 to 3; η represents an integer of 0 to 3] Here, if together with the carbon atom between Q and R39, a carbon chain 3 to 6 -19- (16) ( 16) In the case of a cycloalkyl group of 200424764, Q and R3 9 are combined to form an alkylene group having 2 to 5 carbon atoms. For the phenol compound corresponding to the aforementioned general formula (IV), there may be mentioned: (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis ( 4-monohydroxy-2,3,5-trimethylphenyl) 2-hydroxyphenylmethane, bis (4-monohydroxy-3,5-dimethylphenyl) 4-bihydroxyphenylmethane, bis ( 4-hydroxy- 3,5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4- Hydroxy-2,5-dimethylphenyl) -4 4-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-1 2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy -2,5-Dimethylphenyl) -3,4-Dihydroxymethylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2,4-Dihydroxyphenylmethane, bis (4-hydroxyphenyl) -3-methoxy-4-hydroxyphenylmethane, bis (4-hydroxyphenyl) Phenyl)-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane, Bis (5-Cyclohexyl-4Hydroxy-2Methylphenyl) -2Hydroxyphenylmethane, Bis (5-Cyclohexyl-4 4-Shenyl-2Methylbenzyl) -3,4-A .Phenol-based compounds such as zen-based methane; 2,4-bis (3,5-dimethyl-4-hydroxybenzyl) -5 monohydroxyphenol, 2,6-bis (2,5-dimethyl) -4-hydroxybenzyl)-4- 3-cresol and other linear 3-nuclear phenol compounds; 1,1-bis [3- — 2-hydroxy-5 —methyl-20- (17) (17) 200424764 group; group ) A 4-Cycloyl-5 -cyclohexylphenyl] isopropyl; (¾, bis [2,5-monomethyl-3-(4-hydroxy-5-methylbenzyl)-4-hydroxyphenyl] Methane, bis [2,5-dimethyl-1,3- (4-hydroxybenzyl) -4,4-hydroxyphenyl] methane, bis [3- (3,5-dimethyl-1,4-hydroxy; yl) -1 4-monohydroxy · 5-methylphenyl] methane, bis [3- (3,5-dimethyl-4-hydroxybenzyl One 4-one via a 5-ethylphenyl] methylamine, bis [3- — (3 '5 — — • ethyl-4 4-hydroxybenzyl) — 4-hydroxy — 5-methylphenyl] methane, bis [3— (3, 5—Ethyl-4—Cycloyl) —4—Cycloyl—5—Ethylbenzyl] Aiyuan, Bis [2—Cyclo-3— (3 '5 — _ • A -4-via kikayl) -5 -methylphenyl] methane, bis [2-hydroxy-1-(2-hydroxy-5 -methylbenzyl) -5 -methylphenyl] methane, bis [4-Hydroxy-3— (2-Hydroxy-5-methylbenzyl) -5-Methylphenyl] methane, bis [2,5-dimethyl-1 3 2-Hydroxy-5methylbenzyl ) 4- 4-hydroxyphenyl] linear 4-nuclear phenol compounds such as methane; 2, 4-bis [2-hydroxy-1-(4-hydroxybenzyl)-5-methylbenzyl]-6-cyclohexylphenol , 2,4-bis [4-hydroxy-3- (4-hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol, 2,6-bis [2,5-dimethyl-2-3 — (2-Hydroxy-5methylbenzyl) —4—Hydroxybenzyl] —4—Lines of cresol, etc. 5-core phenol compounds, etc. Compounds; bis (2,3,4-trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) methane, 2,3,4-trihydroxyphenyl-4'-hydroxyphenylmethane, 2 -(2,3,4-trihydroxyphenyl) -2- (2 ', 3,, 4'-trihydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl)-2- (2 ', 4'-dihydroxyphenyl) propane, 2- (3-fluoro-4-hydroxyphenyl) -2- (3'-fluoro-4'-hydroxyphenyl) propane, 2- (2, 4-dihydroxyphenyl)-2--21-(18) (18) 200424764 (4 · monohydroxyphenyl) methane, 2- (2,3,4-trihydroxyphenyl)-2-(4 · —Bisphenol-type compounds such as —hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) —2— (4′-hydroxy-3 ′, 5′-dimethylphenyl) propane; 1-Π- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene, 1- [1- (3-methyl-4-hydroxy) Phenyl) isopropyl] -4 [1,1 bis (3-methyl-4 4-hydroxyphenyl) ethyl] benzene, and other polynuclear branched compounds; Condensation compounds such as 1,1-bis (4-hydroxyphenyl) cyclohexane. These can be used singly or in combination of two or more kinds. Among these, 1- [1- (4-hydroxyphenyl) isopropyl] -4-[[1,1-bis (4-hydroxyphenyl) ethyl] benzene is preferred. The amount of the (C) component to be blended is in the range of 10 to 70% by mass, and preferably 15 to 60% by mass from the viewpoint of the effect. < (D) component > The (D) component, if it is a general one used in a photoresist composition, is not particularly limited, and one or two or more types may be selected, but it has excellent coating properties and is suitable for large glass. From the standpoint of excellent uniformity of the thickness of the photoresist film on the substrate, those containing propylene glycol monoalkyl ether acetate and / or alkyl lactate are preferred. Propylene glycol monoethyl ether acetate is, for example, those having a linear or branched chain alkyl group having 1 to 3 carbon atoms. Among them, the uniformity of the film thickness of the photoresist film on a large glass substrate is very excellent. Therefore, particularly preferred is propylene glycol monomethyl ether acetate (hereinafter, referred to as PGMEA). Examples of the alkyl lactate include methyl lactate and ethyl lactate (hereinafter, -22- (19) 200424764 is simply referred to as EL). Among them, ethyl lactate is preferred. However, if large glass substrates of 600 mm or more are used, coating spots may be generated. Therefore, it is preferred to use c propylene glycol monoalkyl ether ethyl in order to suppress such disadvantages. The blending amount of the acid ester is 20 to 100% by mass from the above-mentioned preferable (D) component. The amount of the alkyl lactate to be blended is 20 to 100% by mass based on the above effects. In addition, if propylene glycol monoalkyl ether acetate and a square (D) component are used, a photoresist pattern having excellent uniformity of the film of the photoresist film can be obtained, and heat resistance can be improved, and scum generation can be suppressed. Aspects are also better. In the case of propylene glycol monoalkyl ether acetate and alkyl lactate, for propylene glycol monoalkyl ether acetate, the amount is preferably 1 to 5 times the amount of alkyl lactate in a mass ratio. In addition, 2-heptanone (hereinafter referred to as HE) is also suitable. Although not particularly limited, as described above, it is a suitable solvent when it is combined with a non-diphenyl optical component. 2-heptanone is superior to PGMEA in terms of heat resistance and reduces the characteristics of the photoresist composition caused by scum. It is very suitable for 2-heptanone. From the above effects, it is preferably at (I: 20 to 100 mass /%. In addition, other organic solvents that can be blended have the following examples. The tendency is to use 500 mm χ streaks. The blending system shows the effect. 2 is (D) alkyl lactate Ester double is excellent, and in the form of a scum mixed system, the organic solvent ketone system of 闬 0.1 to 10 times has a suitable solvent.》) Among the ingredients, in vivo, exemplified -23 -(20) (20) 200424764 That is, ^ monobutyrolactone; propylene glycol monobutyl ether; acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone and other ketones; ethylene glycol , Propylene glycol, diethylene glycol, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate, or one of these methyl ethers, monoethyl ether, monopropyl ether, monobutyl ether, or Polyols such as monophenyl ether and their derivatives; cyclic ethers such as dioxane; and methyl acetate, ethyl acetate, butyl acetate, pyruvate Ester, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, etc. esters. When such solvents are used, the component (D) is preferably 50% by mass or less. The positive-type photoresist composition of the present invention may contain an additive having compatibility as needed, as long as the object of the present invention is not affected, such as an additional resin for improving the performance of the photoresist film, Plasticizers, storage stabilizers, surfactants, colorants used to make the developed image more visible, sensitizers or halation to improve the sensitization effect, to prevent the use of dyes, adhesion Sex improver, and other conventional additives. For the halo prevention dye, an ultraviolet absorber (for example, 2, 2, 4, 4, 4'-tetrahydroxybenzophenone, 4-dimethylamino- 2 ', 4'-dihydroxydi) can be used. Benzophenone, 5-amino- 3 -methyl- 1 -phenyl- 4-(4-hydroxyphenylazo) pyrazole, 4-dimethylamino- 4'-hydroxyazobenzene , 4-diethylamino-4'-ethoxyazobenzene, 4-diethylaminoazobenzene, curcumin, etc.). Surfactants can be added, for example, to prevent stripe discharge (striati ο η). For example, florat FC-43 0, FC-431 (product (21) (21) 200424764, Sumitomo 3M ( Stock)), EF 122A, EF 122B, EF 122C, EF 126 (trade name, Tohoku Chemicals Co., Ltd.) and other fluorine-based surfactants, R-0 8 (trade name, Dainippon Ink chemical industry (stock) system). The positive type photoresist composition of the present invention is preferably prepared by dissolving (A) component, (B) component, (C) component, and other components as needed in (d) an organic solvent. Here, the use amount of the (D) component is preferably to dissolve the (A) to (C) components and other components used as needed, and can be appropriately adjusted in a manner to obtain a uniform positive-type photoresist composition. . It is preferably 10 to 40% by mass, and more preferably 20 to 30% by mass, based on the total solids concentration. / 〇 the way to use. [Method for Forming Photoresist Pattern] An example of a very suitable method for forming a photoresist pattern in the manufacture of an LCD is shown below. First, a positive-type photoresist composition of the present invention described above is coated on a substrate using a spinner or the like to form a coating film. The substrate is preferably a glass substrate. Glass substrates are usually made of amorphous silicon oxide (a m 〇 r p h 〇 s s i 1 i c a), but in the field of system LC, it is considered that low temperature polysilicon is preferred. Such a substrate is because the positive photoresist composition of the present invention is excellent in resolution under low NA conditions, and a large substrate of 500 mm x 600 mm or more, especially 550 mm x 650 mm or more can be used.
接著，將形成有此種塗膜的基板在例如1 0 0至1 4 0 °C -25- (22) (22)200424764 下進行加熱處理（預焙）以去除殘存溶劑並形成光阻被膜 。預焙方法而言，較佳爲實施使加熱板與基板之間，隔著 間隙的近接焙烤（ρ Γ ο X i m i t y b a k i n g )。 再者，對上述光阻被膜，使用描繪有遮罩圖型的光罩 以實施選擇性曝光。 光源而言，爲形成微細的圖型起見，較佳爲採用丨線 (3 6 5 nm )。又，在此曝光所採用的曝光過程，係N A在 0 · 3以下，較佳爲0 · 2以下，更佳爲0 . 1 5以下之低N A條件之 曝光過程者爲宜。 接著’對經選擇性曝光後之光阻被膜，實施加熱處理 (曝光後焙烤：PEB ) 。PEB方法而言，較佳爲實施使加 熱板與基板之間，隔著間隔的近接焙烤。 如對上PEB後之光阻被膜，實施使用顯像液，例如使 用如1至1 〇質量％氫氧化四甲基銨水溶液的鹼水溶液的顯 像處理’則曝光部分將被溶解去除，而基板上將同時形成 集體電路用之光阻圖型及液晶顯示器部分用之光阻圖型。 再者’將殘留於上述光阻圖型表面的顯像液使用純水 等漂洗液加以沖去，即可形成光阻圖型。 在此光阻圖型之形成方法而言，如製造系統L C D時， 在實施上述選擇性曝光的過程中，作爲上述光罩，較佳爲 使用經描繪有2·0 μπι以下之光阻圖型形成用遮罩圖型，及 2 ·〇 μηι以上之光阻圖型形成用遮罩圖型之兩者的光罩。 於是，由於本發明LCD用正型光阻組成物係解像性優 異之故’可得經真空再現光阻圖型之微細的圖型的光阻圖 -26- (23) (23)200424764 型。因而，在同時形成上述光阻圖型的過程中，可於上述 基板上同時形成圖型尺寸2.0 μ m以下之積體電路用之光阻 圖型，及2.0 μ m以上之液晶顯示器部分用之光阻圖型。 如上所說明，本發明之正型光阻組成物係適合於在低 N A條件下之曝光過程。又，亦適合於i線曝光過程。因此 ，在LCD之製造時，可以高解像度製得至少顯示器部分之 光阻圖型。 再者，由於本發明之正型光阻組成物，即使在低NA 條件下的解像性亦優異之故，可於1個基板上以同一曝光 條件形成粗糙的圖型與微細的圖型。因此，即使在低NA 條件下仍能同時以高解像度製得系統LCD之顯示器部分， 與較此爲微細的積體電路部分之光阻圖型，而可作爲系統 LCD之製造用很合適。 LCD用正型光阻組成物，從製造效率之提升、產率之 提升等來看’一般認爲係局敏感化較佳者’在此方面亦可 製得有實用性者。 又，亦具有浮渣之產生較少的效果。 又，如採用使用低NA條件下的解像度優異的上述正 型光阻組成物的本發明之光阻圖型之形成方法’則可提升 LCD製造上的產率。 再者，如採用本發明之光阻圖型之形成方法，則在適 合於LCD製造的低NA條件之曝光過程中’亦能形成高解 像度之光阻圖型。特別是’由於能於基板上同時形成例如 圖型尺寸2.0 μηι以下之積體電路用之光阻’與例如2.0 μίΏ -27- (24) (24)200424764 以上之液晶顯示器部分用之光阻圖型之故，很合適用於系 統L C D之製造。 [實施例] 接著，舉出實施例以更詳細說明本發明，惟本發明並 不因下列實施例所限定。 [正型光阻組成物之評估方法] 就下述之實施例或比較例之正型光阻組成物’將下列 之各物性（1 )至（3 )之評估方法加以說明如下。 (1 ) 敏感度評估： 使用大型四方基板用光阻塗佈裝置（裝置名： TR 3 6 0 00，東京應化工業（股）製），將正型光阻組成物 塗佈於形成有Cr膜的玻璃基板（ 550mmx650mm)上之後 ’將加熱板溫度作成1 3 0 °C，藉由隔著約1 mm之間隔的近 接焙烤實施60秒鐘之第一次乾燥，接著作成加熱板溫度爲 120 °C，並實施藉由隔著0.5mm之間隔的近接焙烤的第2 次之60秒鐘之乾燥，以形成膜厚5 μπ1之光阻被膜。 接著，介由同時描繪有爲再現0.3 μηι線及空間（L&S )及1·5 μιη L&S之光阻圖型之用的遮罩圖型之測試圖表遮 罩（test chart mask ) ( r e t i c u 1 e，標線片），而使用 i線 曝光裝置（裝置名：FX-702J，尼康社製；ΝΑ = 0·14)，按 能真實再現3·0μΐΏ L&S的曝光量（Ε〇ρ曝光量），實施選 -28- (25) (25)200424764 擇性曝光。 接著，使用具有長條式塗佈器噴嘴的顯像裝置（裝置 名：T D - 3 9 0 0示範機，東京應化工業（股）製），將2 · 3 8質 量。/。T M A Η (氫氧化四甲基銨）水溶液，按第1圖所示方 式從基板端部X經過Υ而往Ζ，耗費1 〇秒鐘舖滿於基板上， 保持55秒鐘後水洗30秒鐘並自旋乾燥（spin drying)，以 同時於基板上形成3·0μηι L&S之光阻圖型與1.5μπι L&S之 光阻圖型。 將此時之上述Εορ曝光量作爲敏感度，以單位表示 (2 ) 解像性評估： 求出在上述Εορ曝光量下的界限解像度。 (3 ) 浮渣評估： 在上述Εορ曝光量下，使用SEM (掃瞄式電子顯微鏡 )觀察描繪有1.5 μηι L&S的基板表面，以檢查有無浮渣。 依下列記號表示其評估結果。 〇：殆無確認浮渣之存在。 △:經確認稍有浮渣之存在。 X :經確認大量浮渣之存在。 (實施例1 ) 作爲（A )至（D )成分，製備下列者。 -29- (26) (26)200424764 (A ) 鹼可溶性酚醛淸漆樹脂 I 〇 〇質量份 A1 :對於間甲酚/對甲酚（莫耳比7/3 )之混合苯酚1 莫耳，使用甲醛0.8莫耳依常法合成所得之Mw = 6000， Mw/Mn = 4.0之酚醛淸漆樹脂。 (B ) 酯化反應生成物（PAC1/PAC3 = 2/1 (質量比） ) 30質量份 P A C 1 :作爲五倍子酚（pyrogallol )與丙酮的聚縮物 所製造的Mw 1300之五倍子酚一丙酮樹脂與1，2 —萘醌二 疊氮一5 —磺醯氯（5—NQD )的酯化率78%之酯化反應生 成物。 PAC3:作爲2，3，6 —三甲基苯酚與2 —羥基苯甲醛的 縮合物所製造的雙（2，3，5—三甲基一4一羥基苯基）一 2—羥基苯基甲烷（M(分子量）=3 76 ) 1 莫耳，與5 — NQD 2.02莫耳的酯化率67.3%之酯化反應生成物。 (C )含酚性羥基之化合物 2 0質量份 1 一[1 一（4一羥基苯基）異丙基]一4一[1，1一雙（4一 羥基苯基）乙基]苯 (〇) 有機溶劑Next, the substrate on which such a coating film is formed is subjected to a heat treatment (prebaking) at, for example, 100 to 140 ° C -25- (22) (22) 200424764 to remove the residual solvent and form a photoresist film. For the pre-baking method, it is preferable to perform close-baking (ρ Γ ο X i m i t y b a k i n g) with a gap between the heating plate and the substrate. The photoresist film was subjected to selective exposure using a mask with a mask pattern. For the light source, in order to form a fine pattern, it is preferable to use a line (3 6 5 nm). In addition, the exposure process used in this exposure is an exposure process with a low NA condition of N A below 0.3, preferably below 0.2, and more preferably below 0.1. Next, the photoresist film after the selective exposure is subjected to a heat treatment (baking after exposure: PEB). In the PEB method, it is preferable to perform proximity baking with a space between the heating plate and the substrate. For example, if the photoresist film after PEB is applied, a developing solution is used, for example, an alkaline aqueous solution such as a 1 to 10% by mass tetramethylammonium hydroxide aqueous solution is used. The exposed portion will be dissolved and removed, and the substrate The photoresist pattern for collective circuits and the photoresist pattern for liquid crystal display parts will be formed at the same time. Furthermore, the developing solution remaining on the surface of the photoresist pattern is washed away with a rinsing solution such as pure water to form a photoresist pattern. In terms of this photoresist pattern formation method, for example, when manufacturing a system LCD, in the process of implementing the above-mentioned selective exposure, as the photomask, it is preferable to use a photoresist pattern that is depicted as less than 2.0 μm. A mask for both the mask pattern for forming and the mask pattern for forming a photoresist pattern having a size of 2.0 μm or more. Therefore, since the positive photoresist composition system for LCD of the present invention is excellent in resolvability, a photoresist pattern of a fine pattern that can be reproduced in a vacuum can be obtained. -26- (23) (23) 200424764 . Therefore, in the process of simultaneously forming the above-mentioned photoresist pattern, a photoresist pattern for an integrated circuit with a pattern size of 2.0 μm or less and a liquid crystal display part of 2.0 μm or more can be simultaneously formed on the substrate. Photoresistive pattern. As explained above, the positive photoresist composition of the present invention is suitable for the exposure process under low NA conditions. It is also suitable for i-line exposure. Therefore, at the time of manufacturing the LCD, a photoresist pattern of at least a portion of the display can be obtained with high resolution. Furthermore, since the positive-type photoresist composition of the present invention is excellent in resolvability even under low NA conditions, rough patterns and fine patterns can be formed on one substrate under the same exposure conditions. Therefore, even under low NA conditions, the display portion of the system LCD can be made with high resolution at the same time, and the photoresist pattern of the finer integrated circuit portion is more suitable for the manufacture of the system LCD. A positive type photoresist composition for LCDs, from the viewpoints of improvement in manufacturing efficiency and improvement in yield, etc. 'Generally considered to be better sensitized by the bureau' can also be made practical in this respect. In addition, it has the effect of generating less scum. In addition, if the photoresist pattern forming method of the present invention using the above-mentioned positive type photoresist composition having excellent resolution under low NA conditions is used, the yield in LCD manufacturing can be improved. Furthermore, if the photoresist pattern forming method of the present invention is adopted, a high-resolution photoresist pattern can also be formed during the exposure process suitable for the low NA conditions of LCD manufacturing. In particular, 'because a photoresist for a integrated circuit having a pattern size of 2.0 μηι or less can be formed on a substrate at the same time' and a photoresist pattern for a liquid crystal display portion of more than 2.0 μίΏ-27- (24) (24) 200424764 Because of the type, it is very suitable for the manufacture of system LCD. [Examples] Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. [Evaluation method of positive photoresist composition] The following methods for evaluating the respective physical properties (1) to (3) will be described with respect to the positive photoresist composition of the following examples or comparative examples. (1) Sensitivity evaluation: Using a large-scale tetragonal substrate photoresist coating device (device name: TR 3 6 00, manufactured by Tokyo Chemical Industry Co., Ltd.), a positive-type photoresist composition was coated on a layer formed with Cr After the film was placed on a glass substrate (550mmx650mm), the temperature of the heating plate was made 130 ° C, and the first drying was performed for 60 seconds by proximity baking at intervals of about 1 mm, and the temperature of the heating plate was 120. ° C, and drying was performed for 60 seconds for the second time by proximity baking at intervals of 0.5 mm to form a photoresist film with a film thickness of 5 μπ1. Next, a test chart mask (a test chart mask) for simultaneously depicting a photoresist pattern of 0.3 μηι lines and space (L & S) and 1.5 μLη L & S reticu 1 e, reticle), and using an i-ray exposure device (device name: FX-702J, manufactured by Nikon Corporation; Ν = 0 · 14), the exposure amount (Eo) that can realistically reproduce 3.0 μΐΏ L & S ρ exposure amount), selective 28- (25) (25) 200424764 selective exposure. Next, a developing device (device name: T D-3900 demonstration machine, manufactured by Tokyo Chemical Industry Co., Ltd.) with a long applicator nozzle was used to produce a quality of 2.38. /. The TMA Η (tetramethylammonium hydroxide) aqueous solution passes from the substrate end X through Ζ to Z in the manner shown in Figure 1. It takes 10 seconds to cover the substrate, and it is held for 55 seconds and washed for 30 seconds Spin drying is performed to form a photoresist pattern of 3.0 μm L & S and a photoresist pattern of 1.5 μm L & S on the substrate at the same time. Let the above-mentioned exposure amount of Eορ be used as the sensitivity, and be expressed in units. (2) Resolution evaluation: Determine the limit resolution at the above exposure amount of Eορ. (3) Evaluation of dross: Under the above-mentioned exposure dose, the surface of the substrate on which 1.5 μm L & S was drawn was observed using a SEM (scanning electron microscope) to check for the presence of dross. The evaluation results are indicated by the following symbols. 〇: No existence of scum was confirmed. △: Slight presence of scum was confirmed. X: The existence of a large amount of scum was confirmed. (Example 1) As components (A) to (D), the following were prepared. -29- (26) (26) 200424764 (A) Alkali-soluble phenolic lacquer resin I 0.00 parts by mass A1: 1 mol of mixed phenol for m-cresol / p-cresol (Molar ratio 7/3), use A phenolic lacquer resin with Mw = 6000 and Mw / Mn = 4.0 obtained by conventional synthesis of formaldehyde 0.8 mol. (B) Esterification reaction product (PAC1 / PAC3 = 2/1 (mass ratio)) 30 parts by mass of PAC1: Mw 1300 gallic phenol-acetone resin produced as a polycondensation product of gallophenol and acetone An esterification reaction product with an esterification rate of 78% of 1,2-naphthoquinonediazide-5-sulfonyl chloride (5-NQD). PAC3: Bis (2,3,5-trimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane produced as a condensate of 2,3,6-trimethylphenol and 2-hydroxybenzaldehyde (M (molecular weight) = 3 76) 1 mole, an esterification reaction product with an esterification rate of 67.3% with 5-NQD 2.02 mole. (C) 20 parts by mass of a phenolic hydroxyl-containing compound 1 [[1 ((4-hydroxyphenyl) isopropyl]] 4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene ( 〇) Organic solvents
Dl: PGMEA (丙二醇一甲基醚乙酸酯） 將上述（A)至（C)成分，及對此等（A)至（C) 成分之合計質量相當於3 5 0PPm的量之表面活性劑（製品 名「R-08」：大日本油墨工業（股）製），溶解於本身爲 (D)成分的PGMEA中，按固體成分[(A)至（C)成分 之合計]濃度能成爲25至28質量之方式調整，使用〇.2用 -30- (27) 200424764 μπι之膜濾器加以過濾，以調製正型光阻組成物。 (實施例2至9 )、（比較例1至4 ) 除將（Β ) 、 （ C )成分改換爲下述表1所記載者以外 ，其餘則按與實施例1同樣方式，以調製正型光阻組成物 [表1 ]Dl: PGMEA (propylene glycol monomethyl ether acetate) is a surfactant in which the total mass of the above components (A) to (C) and the components (A) to (C) is equivalent to 350 ppm (Product name "R-08": Dainippon Ink Industry Co., Ltd.), dissolved in PGMEA which is the component (D) itself, the concentration of the solid component [total of (A) to (C)] can be 25 Adjust to a quality of 28, and filter with a membrane filter of -30- (27) 200424764 μm using 0.2 to modulate the positive photoresist composition. (Examples 2 to 9) and (Comparative Examples 1 to 4) Except that the components (B) and (C) were changed to those described in Table 1 below, the rest were modulated in the same manner as in Example 1 to modulate the positive type. Photoresist composition [Table 1]
(Β) (D) (質量比） 1 PAC1/PAC3(2/1) PGMEA 2 P AC2/PAC3(2/1 ) PGMEA 實 3 PAC2/PAC3(l/2) PGMEA 施 4 PAC1/PAC3(2/1) EL 例 5 PAC1/PAC3(2/1) EL/PGMEA(7/3) 6 P AC 1 /PAC3(2/1 ) HE 7 PAC8/PAC3(2/1 ) PGMEA 8 PAC9/PAC3(2/1 ) PGMEA 9 PAC 1 0/PAC3(2/l ) PGMEA 比 1 P AC4 PGMEA 較 2 PAC5 PGMEA 例 3 P AC6 PGMEA 4 P AC7 PGMEA 在此，表1中，（D)成分中之EL/PGMEA ( 7/3 ) ’ (28)200424764(B) (D) (mass ratio) 1 PAC1 / PAC3 (2/1) PGMEA 2 P AC2 / PAC3 (2/1) PGMEA Real 3 PAC2 / PAC3 (l / 2) PGMEA Application 4 PAC1 / PAC3 (2 / 1) EL example 5 PAC1 / PAC3 (2/1) EL / PGMEA (7/3) 6 P AC 1 / PAC3 (2/1) HE 7 PAC8 / PAC3 (2/1) PGMEA 8 PAC9 / PAC3 (2 / 1) PGMEA 9 PAC 1 0 / PAC3 (2 / l) PGMEA is more than 1 P AC4 PGMEA than 2 PAC5 PGMEA Example 3 P AC6 PGMEA 4 P AC7 PGMEA Here, in Table 1, EL / PGMEA in (D) component ( 7/3) '(28) 200424764
/ p G Μ E A按質量比：7 / 3加以混合之 又，PAC2至10係如下所示。 ，4 一二羥基苯 P AC2 :/ p G Μ E A is mixed at a mass ratio of 7/3. In addition, PAC2 to 10 are shown below. , 4-dihydroxybenzene P AC2:
苯基）一3 ， 4— PAC2:作爲3__甲基—6_環己酚，與 姐Z雙（2 —甲基一 4 一羥基一 5 —環己基 經基苯基甲院（M = 500) 1 莫耳，與5- NQ〇 211莫耳的酯化率52· 75%之酯化反應生成物。 PAC3:作爲2，3，6 —三甲基苯酚、與2—羥基苯甲醛 2，3，5—三甲基一4一羥基苯基 的縮合物所製造之雙（ —2 —經基苯基甲烷（M = 376) 1莫耳，與5-NQD 2.02 旲耳的醋化率6 7.3 %之酯化反應生成物。 PAC4:作爲間甲酚/對甲酚/2，3，5—三甲基苯酚 = 35:40:25 (莫耳比），與甲醛的聚縮物所製造的Mw 1500 之醛淸漆樹脂，與5-NQD的酯化率8%之酯化反應生成物 〇 PAC5:雙（2，4 —二羥基苯基）甲烷（M = 232) 1莫 耳，與5-NQD 3.76莫耳的酯化率9 4 %之酯化反應生成物 〇 PAC6:參（4一羥基苯基）甲烷= 292) 1莫耳， 與5-NQD 2莫耳的酯化率66.7%之酯化反應生成物。 PAC7:五倍子酸甲酯1莫耳，與5-NQD 3莫耳的酯 化率100%之酯化反應生成物。 P A C 8 :將2，5 -二甲苯酚/對甲酚（莫耳比2/1)，與 甲醛作爲原料所合成之M = 376之2，6—雙（2，5—二甲 -32- (29) (29)200424764 基一4一羥基苄基）一4一甲基苯酚 1莫耳，與5-NQD 2莫 耳的酯化率66%之酯化反應生成物。 PAC9:將2，6 —二甲苯酚/對甲酚（莫耳比2/1)，與 甲醛作爲原料所合成之M = 3 7 6之2，6—雙（3，5—二甲 基一4 一羥基苄基）一4 一甲基苯酚 1莫耳，與5-NQD 2莫 耳的酯化率6 6 %之酯化反應生成物。 PAC10:將2 —環己酚/對甲酚（莫耳比1/1 )，與甲醛 /丙酮（莫耳比2/1)作爲原料所合成之M = 6 3 2之雙[3 —（ 2 —羥基一 5—甲基苄基）一4 一羥基一 5 —環己基苯基]異丙 烷 1莫耳，與5-NQD 2莫耳，與酯化率50%之酯化反應生 成物。 -33- (30) 200424764 [表2] 敏感度評估 (m J) 解像性評估 (μπ〇 浮渣評估 1 3 0 1 .3 〇 2 30 1 .3 — 〇 實 3 42.5 1 .2 〇 施 4 35.0 1 .3 〇 例 5 32.5 1.3 〇 6 37.5 1.3 〇 7 37.5 1 . 1 〇 8 40.0 1.1 〇 9 47.5 1.3 Δ 比 1 30 1.6 X 較 2 37.5 1.5 X 例 3 30 1 .5 X 4 25 1 .6 〇Phenyl) -3, 4-PAC2: as 3_methyl-6_cyclohexylphenol, and Z-bis (2-methyl-1, 4-hydroxy-1, 5-cyclohexyl) ) 1 mole, the product of an esterification reaction with 5-NQ〇211 mole with an esterification rate of 52.75%. PAC3: 2,3,6-trimethylphenol, and 2-hydroxybenzaldehyde 2, The bis (—2 — via phenylphenylmethane (M = 376) 1 mol, and the acetic acid conversion rate of 5-NQD 2.02 旲 6 7.3% product of esterification reaction. PAC4: Made as polycondensate of m-cresol / p-cresol / 2,3,5-trimethylphenol = 35:40:25 (molar ratio) with formaldehyde Aldehyde lacquer resin of Mw 1500, an esterification reaction product with an esterification rate of 8% with 5-NQD. 0PAC5: bis (2,4-dihydroxyphenyl) methane (M = 232) 1 mole, and 5-NQD 3.76 Molar esterification rate 94. 4% of the esterification reaction product 0PAC6: Ginseng (4-monohydroxyphenyl) methane = 292) 1 Molar, and 5-NQD 2 Molar esterification rate 66.7 % Of esterification reaction product. PAC7: Ester of gallic acid methyl ester 1 mole, 5-NQD 3 mole of ester Product of the reaction: PAC 8: 2,6-bis (2,5--2) synthesized by using 2,5-xylenol / p-cresol (molar ratio 2/1) and formaldehyde as raw materials An esterification reaction product of methyl-32- (29) (29) 200424764 group 4- 4-hydroxybenzyl)-4-methylphenol 1 mole, and 5-NQD 2 mole having an esterification rate of 66%. PAC9 : Mixed with 2,6-xylenol / p-cresol (Molar ratio 2/1) and formaldehyde as raw material M = 3 7 6-2,6-bis (3,5-dimethyl-1 4 Monohydroxybenzyl) -4 methylol 1 mole, an esterification reaction product with an esterification rate of 66% with 5-NQD 2 mole. PAC10: 2-Cyclohexol / p-cresol (Mole Ear ratio 1/1), with M = 6 3 2 bis [3 -— (2-hydroxy-5methylmethylbenzyl) —4-hydroxy] synthesized with formaldehyde / acetone (Molar ratio 2/1) as raw material -5-Cyclohexylphenyl] isopropane 1 mole, 5-NQD 2 mole, and esterification reaction product of 50% esterification rate. -33- (30) 200424764 [Table 2] Sensitivity evaluation ( m J) Resolvability evaluation (μπ〇 scum evaluation 1 3 0 1 .3 0 2 30 1 .3 — 0 3 32.5 1 .2 0 4 45.0 1. 3 〇 Example 5 32.5 1.3 〇 6 37.5 1.3 〇 7 37.5 1.1.1 〇 8 40.0 1.1 〇 9 47.5 1.3 Δ ratio 1 30 1.6 X than 2 37.5 1.5 X Example 3 30 1.5 .4 X 4 25 1.6
L C D用正型光阻組成物，需要具有在低N A條件下的 高解像性。 從表2所示結果可知’實施例之組成均爲解像性良好 者。 又，敏感度亦能實用的程度之良好，無浮渣之產生’ 在此等方面良好者。 相對於此，由於比較例1之組成的分子量過高之故’ -34- (31) (31)200424764 解像性爲不良。且發生有浮渣。 由於比較例2之組成之酯化率超過9 0 %之故，解像性 爲不良。又，浮渣亦稍爲不良。 由於比較例3之組成之分子量低之故，解像性爲不良 。又，亦發生有浮渣。 由於比較例4之組成不具有低分子量酚醛淸漆樹脂之 骨架之故，敏感度過快，解像性亦較劣。 [發明之效果] 由於本發明之LCD用正型光阻組成物及光阻圖型之製 造方法，即使在低NA條件下仍能賦與良好的解像度之故 ，作爲系統LCD之製造用很合適而產業上極爲有用。 【圖式簡單說明】 第1圖：將正型光阻組成物塗佈於玻璃基板上’焙燒 以乾燥並圖型曝光後，使用具有長條式塗佈器（slit c 〇 a t e r )的顯像裝置從基板端部X往Z舖滿液體的意思之說 明圖。 -35-A positive photoresist composition for L C D is required to have high resolution under low NA conditions. From the results shown in Table 2, it can be seen that the compositions of the examples are those having good resolvability. In addition, the sensitivity can be practically good, and no scum is generated 'in these respects. On the other hand, since the molecular weight of the composition of Comparative Example 1 is too high, the resolvability is inferior. '-34- (31) (31) 200424764. And scum occurred. Since the esterification rate of the composition of Comparative Example 2 exceeded 90%, the resolvability was poor. The scum was also slightly defective. Since the molecular weight of the composition of Comparative Example 3 was low, the resolvability was poor. Also, scum occurred. Since the composition of Comparative Example 4 does not have the skeleton of a low-molecular-weight phenolic lacquer resin, the sensitivity is too fast, and the resolution is also poor. [Effect of the invention] Since the positive photoresist composition and photoresist pattern manufacturing method for LCD of the present invention can provide good resolution even under low NA conditions, it is very suitable for the manufacture of system LCD The industry is extremely useful. [Schematic description] Figure 1: A positive photoresist composition is coated on a glass substrate, 'fired to dry and pattern-exposed, and developed using a slit coater. An explanatory diagram of the meaning of the device filled with liquid from the substrate end X to Z. -35-
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| KR101351311B1 (en) * | 2006-03-08 | 2014-01-14 | 주식회사 동진쎄미켐 | Photosensitive resin composition |
| JP2009222733A (en) * | 2008-01-25 | 2009-10-01 | Rohm & Haas Electronic Materials Llc | Photoresist comprising novolak resin blend |
| KR101430962B1 (en) * | 2008-03-04 | 2014-08-18 | 주식회사 동진쎄미켐 | Photoresist composition and method of manufacturing array substrate using the same |
| KR101632965B1 (en) * | 2008-12-29 | 2016-06-24 | 삼성디스플레이 주식회사 | Photoresist composition and method of fabricating thin film transistor substrate |
| CN101907827B (en) * | 2009-06-08 | 2011-11-23 | 奇美实业股份有限公司 | Positive-type photosensitive resin composition and protrusion for liquid crystal orientation control prepared from same |
| JP6138067B2 (en) * | 2014-02-03 | 2017-05-31 | ローム アンド ハース エレクトロニック マテリアルズ エルエルシーＲｏｈｍ ａｎｄ Ｈａａｓ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ ＬＬＣ | Photoresist containing novolac resin blend |
| CN107844028B (en) * | 2017-11-07 | 2021-04-30 | 潍坊星泰克微电子材料有限公司 | Photoresist, preparation method and photoetching process thereof |
| JP6691203B1 (en) * | 2018-12-26 | 2020-04-28 | 東京応化工業株式会社 | Chemically amplified positive photosensitive resin composition, photosensitive dry film, method of manufacturing photosensitive dry film, method of manufacturing patterned resist film, method of manufacturing substrate with template, and method of manufacturing plated object |
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