201222154 、發明說明： 【發明所屬之技術領域】 祕明係種正型感光性細旨組成物及使用該組 成物形成_的方法。特別是提供—種使財半導 迴路元件及薄膜電晶體（以下_TFT)之液晶顯示元种 ^中，耐㈣雑之正職絲樹驗錢及朗該組成 物形成圖案的方法。 【先前技術】201222154, invention description: [Technical Field of the Invention] The secret type is a positive photosensitive composition and a method of forming the composition using the composition. In particular, it provides a method for forming a pattern of a liquid crystal display element of a semiconductor semi-conducting circuit element and a thin film transistor (hereinafter referred to as _TFT), and is resistant to (4) 正. [Prior Art]
在基板上形成如液晶顯示元件迴路或半導體積體迴路 等微細迴路__緣膜或者導雜金_上，均勾地塗 佈光阻組成物，並於蚊形狀的光罩下進行曝光顯影，可 製得所需的形狀圖案。接著，將形成圖案的光阻膜作為光 罩除去金屬膜或絕緣膜後，絲去前的光崎，即可在 基板上形成微細迴路。根據光阻組成物於曝光部分或光阻 膜部分之可溶或不溶，光阻域物可分為正型光阻和 光阻兩類。 ' 日本特公平2-51·專敝獻揭露—種正贱光性樹 脂組成物，触成物包含—由間_情、對_甲騎二甲苯十 酴之混合物與_嫌合而得之紛酸清漆樹脂及—蛾二疊氮 化合物，於朗上具有絲度及高賴料伽，然$·， 就近幾年之需求而言，其所形成之圖案树熱性差的問題 且已無法達到標準。 因此，相較於前述之感光性樹脂組成物，日本特開 2007-30搬專利讀娜使用如下列結構式所表示的紛 酸清漆樹脂作域紐樹脂組成物，可於基板上形成财熱 201222154 不佳的 =圖案，然而，其所形成的圖案卻有耐裂縫性Forming a thin circuit such as a liquid crystal display element circuit or a semiconductor integrated circuit on the substrate, or coating the photoresist composition, and performing exposure and development under a mosquito-shaped mask. The desired shape pattern can be produced. Next, after the patterned photoresist film is removed from the metal film or the insulating film as a mask, the light is removed, and a fine circuit can be formed on the substrate. Depending on whether the photoresist composition is soluble or insoluble in the exposed portion or the photoresist portion, the photoresist species can be classified into two types: positive photoresist and photoresist. 'Japan special fair 2-51 · special offer to expose - a kind of positive twilight resin composition, the touch contains - from the mixture of _ love, on the _ A riding xylene ten 酴 mixture and _ suspected Acid varnish resin and moth-diazide compound have a high degree of silkness and high gamma on the lang, but in recent years, the pattern tree formed by it has poor heat quality and can not meet the standard. . Therefore, compared with the above-mentioned photosensitive resin composition, the Japanese Laid-Open Patent Application No. 2007-30 uses the acid varnish resin represented by the following structural formula as a domain resin composition, and can form a heat on the substrate 201222154 Poor = pattern, however, the pattern formed is resistant to cracking
(式中’ R表示Η、-0H或-ch3，n為3〜2數 【發明内容】 〈登數。）(wherein 'R' denotes Η, -0H or -ch3, and n is 3 to 2 number. [Summary of the Invention]
本發明主要目的在妙供—種正 '特別是提供一種使用在半導體集積迴路元件 曰曰體（以下_和錢晶_元㈣种 性 之正型感光性樹脂組成物。 衣噠性佳 2明另—目的在於提供—種使用前述正型感光性樹 月曰組成物形成圖案的方法。 為滿足前述目的，本發_—種正型感光性樹脂組成 物’包含祕清漆樹脂(A)、含環氧丙烧基(贈如⑴之環 氧樹脂⑻、㈣醒二疊氮鑛類之@旨化物(C)以及溶劑 ⑼其巾’該祕清漆翻旨⑷包含經基型咖^清漆樹脂 (A-1)，該羥基型酚醛清漆樹脂W l)係由羥基苯甲醛類化 合物與芳香族祕化合物縮合而得，且基於祕清漆樹脂 (A)100重量份，該羥基型酚醛清漆樹脂(A-1)的使用量為 30〜100重量份。 如前所述之正型感光性樹脂組成物，其中，該羥基苯 甲酸類化合物係選自於雜苯甲㈣合物、二絲苯甲盤 化合物、二羥基苯，醛化合物及羥基烷基苯甲醛化合物所 4 201222154 組成的群組。 如刖所述之正型感光性樹脂物 歹工基本甲酸所組成的群組。 如前所述之正型感光性樹脂組成物，其中，該二經基 苯甲魏合物係選自於2,3_:織苯得、24二經= 2 2, 5-—祕苯情、3,4_二絲苯情及& 5—二經 基苯甲醛所組成的群組。The main object of the present invention is to provide a positive photosensitive resin composition for use in a semiconductor integrated circuit element body (hereinafter, hereinafter, and Qianjing_yuan (4). Further, it is an object of the invention to provide a method for forming a pattern by using the above-mentioned positive-type photosensitive dendrimer composition. In order to satisfy the above object, the present invention has a positive-type varnish resin (A), including Epoxy propyl ketone (available as epoxy resin (8) of (1), (4) awake nitrile ore @契化(C), and solvent (9) of the towel. The secret varnish (4) contains a base type varnish resin ( A-1), the hydroxy novolac resin W l) is obtained by condensing a hydroxybenzaldehyde compound and an aromatic secret compound, and based on 100 parts by weight of the secret varnish resin (A), the hydroxy novolac resin (A) -1) is used in an amount of 30 to 100 parts by weight. The positive photosensitive resin composition as described above, wherein the hydroxybenzoic acid compound is selected from the group consisting of a polybenzoic acid (tetra) compound and a second wire benzopyrene disk. Compound, dihydroxybenzene, aldehyde compound and hydroxyalkylbenzaldehyde compound 4 201222154 A group consisting of a positive photosensitive resin as described above, which is composed of a basic formic acid. The positive photosensitive resin composition as described above, wherein the di-based benzoic acid The compound is selected from the group consisting of 2,3_: woven benzene, 24 bis = 2 2, 5-- benzophene, 3,4 bis-benzene, and & 5-di-benzaldehyde group.
如&所述之正$感光性樹脂組成物，其中，該三經基 苯甲酿化合物係選自於2, 3,4_三織苯帽、2, 4,=三經 基苯甲盤、2,4, 6-三織苯情、3,4, 5—三雜苯甲騎 組成的群組。 如則所述之正型感光性樹脂組成物，其巾，該經基烧 基笨甲搭化合物係選自於鄰H甲基苯㈣、間-經甲基苯 甲醛及對-羥甲基苯甲醛所組成的群組。 如前所述之正型感光性樹脂組成物，其中，基於酚醛 清f樹脂⑷1GG重量份，含環制絲之魏細旨⑻的使 用量為5〜40重量份’鄰萘藏二疊氮續酸類之醋化物⑹的 使用量為1〜1GG 4量份，賴⑼的使用量為5⑼〜誦 重量份。 本發明一種圖案形成方法，係將如前所述之正型感光 性樹脂組成物塗佈於一基板，再依序施予一預烤、一曝光、 一顯影及一後烤處理，據此於該基板形成圖案。 本發明一種薄膜電晶體陣列基板，包含如前所述之圖 201222154 本發明-魏晶_元件，包麵叙脑電晶體陣 列基板。 本發明中’以（甲基）丙雜絲丙烯酸及/或甲基丙稀 酉夂同樣地’以（甲基）丙埽酸酉旨表示丙稀酸醋及/或甲基丙 烯w曰，以（甲基）丙烯醯基表示丙烯醯基及/或甲基丙婦酿 以（甲基）丙烯醯氧基表示丙烯醯氧基及/或甲基丙稀醯 氧基。 以下逐一對本發明各組成做詳細的說明。 籲 < 正型感光性樹脂組成物> [紛酸清漆樹脂(A)] 本發明正型感光性樹脂組成物之紛酸清漆樹脂⑷包 含羥基型酚醛清漆樹脂(A-1)，並可選擇性地進一步包含其 他紛醛清漆樹脂(A-2)。 該起基型酌·路清漆樹脂(A-i)係由經基苯甲盤類化合 物與芳香族經基化合物’在酸性觸媒存在下經縮合反應而 得。 “ .其中，羥基苯甲醛類化合物的具體例為：鄰-羥基苯甲 醛 '間-羥基苯甲醛、對一羥基苯甲醛等之羥基笨曱醛化合 物；2, 3-二羥基苯甲醛、2,4-二羥基苯甲醛、2, 5-二羥基 苯甲醛、3’4-二羥基苯曱醛、3, 5_二羥基苯甲醛等之二羥 基苯曱醛化合物；2, 3,4-三羥基苯甲醛、2, 4, 5-三羥基苯 甲醛、2,4, 6-三羥基苯曱醛、3,4, 5-三羥基苯甲醛等之三 羥基苯甲醛化合物；鄰-羥曱基苯甲醛、間-羥甲基苯曱醛、 對-羥甲基苯甲醛等之羥基烷基苯曱醛化合物。該羥基苯曱 酸類化合物可單獨一種使用或混合複數種使用。其中，以 6 201222154 鄰-羥基苯甲醛、間-羥基笨曱醛、對_羥基苯甲醛、2, 3一二 羥基苯曱醛、2, 4_二羥基笨甲醛、3, 4-二羥基苯曱醛、 2, 3,4-三羥基苯曱醛為較佳。 本發明與該羥基苯甲醛類化合物縮合反應之芳香族羥 基化合物的具體例為：苯酚（phen〇1);間-甲酚 (m-cresol)、對-甲酚(p-cres〇1)、鄰一曱酚(〇_cres〇1)等 之甲紛(cresol)類；2, 3-二甲苯酚、2, 5-二甲苯酚、3,5- 一曱本紛、3, 4-一甲苯紛等之二甲酌(咖㈤以）類；間_乙 基苯酚、對-乙基苯酚、鄰-乙基苯酚、2, 3, 5-三曱基苯酚、 2, 3, 5-三乙基苯酚、4-第三丁基苯酚、3_第三丁基苯酚、 2-第三丁基苯酚、2-第三丁基—4—曱基苯酚、2-第三丁基一5_ 甲基苯酚、6-第三丁基-3-甲基苯酚等之烷基苯酚(aikyl phenol)類；對-甲氧基苯酚、間_甲氧基苯酚、對_乙氧基 笨酚、間-乙氧基苯酚、對丙氧基苯酚、間_丙氧基苯酚等 之烷氧基笨酚(alkoxy phenol)類；鄰-異丙烯基苯酚、對一 異丙烯基苯酚、2-甲基-4-異丙烯基苯酚、2-乙基-4-異丙 稀基本酚專之異丙烯基苯盼（iS〇pr〇penyl phen〇l)類；笨 基苯酚(phenyl phenol)之芳基苯酚（aryl phen〇1)類； 4, 4 _一經基聯本、雙酌' A、間-苯二紛(resorcin〇i)、對_ 本一紛(hydroquinone)、1，2,3-苯三盼(pyrogallol)等之 多經基苯(polyhydroxyphenol)類等。前述芳香族羥基化合 物可單獨一種使用或混合複數種使用。其_，.以鄰—甲酚、 間-甲酚、對-甲酚、2, 5-二曱苯酚、3, 5-二甲苯齡、2, 3, 5- 三曱基苯紛等為較佳。 前述酸性觸媒之具體例如：鹽酸、硫酸、甲酸、醋酸、 7 201222154 草酸、對甲苯續酸等。 基於酚醛清漆樹脂(A)100重量份，羥基型酚醛清漆樹 脂(A-1)的使用量通常為30〜100重量份，較佳為4〇〜100 重量份，更佳為50〜100重量份。若羥基型酚醛清漆樹脂 (A-1)使用量低於30重量份時，則感光性樹脂組成物所形 成之圖案容易有裂縫產生及殘膜率低下的問題。 其他紛酸清漆樹脂(A-2)，一般係由前述之芳香族經基 化合物及非羥基苯甲醛類之醛類，在前述之酸性觸媒存在 Φ 下經縮合反應而得。 其中，非羥基苯曱醛類之醛類的具體例為：甲搭、多 聚甲醛(paraformaldehyde)、三聚甲醛(tri〇xane)、乙盤、 丙酿、丁路、三曱基乙酸、丙嫦路（acr〇lein)、丁婦酸 (crotonaldehyde)、環己醛（cyclo hexanealdehyde)、呋 喃甲醛（furfural)、呋喃基丙烯醛（furyiacrolein)、苯甲 搭、對本二甲路（terephthai aldehyde)、苯乙酸：、α—苯 基丙醛、/3-苯基丙醛、鄰-曱基苯曱醛、間_甲基苯甲醛、 •對-甲基苯曱醛、鄰-氯苯甲醛、間一氯苯甲醛、對一氯苯甲 醛、肉桂醛等。前述醛類可單獨一種使用或混合複數種使 用。其中，以甲醛為較佳。 前述之羥基型酚醛清漆樹脂(A—D與其他酚醛清漆樹 脂(A-2)，皆可使用單一種類之酚醛清漆樹脂，亦可混合兩 '種或兩種以上不同種類之酚醛清漆樹脂。 [含環氧丙烷基之環氧樹脂(B)] 本發明正型感光性樹脂之含環氧丙烷基之環氧樹脂③） 係由不飽和驗單體⑽、含環氧丙絲化合物⑽及盆 '、[S] 8 201222154 他不飽和單體(b3)共聚合而得。其中： 不飽和羧酸單體(bl)的具體例為：丙烯酸、曱基丙烯 酸、丁烯酸、α-氣丙_&、乙基丙烯及肉桂酸等不飽和 一元羧酸類，馬來酸、馬來酸酐、富馬酸、衣康酸、衣康 酸酐、檸康酸、檸康酸酐等不飽和二元羧酸（酐）類；3價以 上之不飽和多價羧酸（酐）類等等。其中，以丙烯酸、曱基 丙烯酸為較佳。該不飽和羧酸單體(bl)可單獨一種使用或 混合複數種使用。 • 含環氧丙烷基化合物(b2)的具體例為：3-(甲基）丙烯 1 氧曱基環氧丙烧（3-[(meth)aCryl〇yl〇Xy-methyl] oxetane)、3-(曱基）丙烯醯氧曱基_3_乙基環氧丙烷、3_(曱 基）丙烯醯氧甲基-2-甲基環氧丙烷、3_(甲基）丙烯醯氧曱 基三氟甲基環氧丙烷、3-(甲基）丙烯醯氧甲基-2-五氟 乙基環氧丙烧、3-(曱基）丙烯醯氧甲基_2—苯基環氧丙烷、 3-（曱基）丙烯醯氧曱基一2, 2-二氟環氧丙烷、3_(甲基）丙烯 醯氧甲基-2, 2,4-三氟環氧丙烷、3-(甲基）丙烯醯氧曱基 _ _2,2’4,4-四氟環氧丙烷、3_(甲基）丙烯醯氧乙基環氧丙 烷、3-(曱基）丙烯醯氧乙基_3_乙基環氧丙烷、2_乙基 -3-(甲基）丙烯醯氧乙基環氧丙烷、3_(曱基）丙烯醯氧乙基 2 一氟甲基環氧丙烧、3-(甲基）丙烯酿氧乙基-2-五敦乙 基環氧丙燒、3-(甲基）丙烯醯氧乙基-2-苯基環氧丙烧、 2, L二敦-3-(甲基）丙烯醯氧乙基環氧丙烷、3_(甲基）丙婦 醯氧乙基-2, 2,4-三氟環氧丙烷、3-(甲基）丙烯醯氧乙基 -2’2, 4,4-四氟環氧丙烷、2一（甲基）丙烯醯氧曱基環氧丙 烷、2-曱基一2-(甲基）丙烯醯氧甲基環氧丙烷、3甲基 9 201222154 =(甲基）丙烯醯氧甲基環氧丙烧、4_甲基_2_(甲基）丙稀 醯氧甲基環氧丙烧、2-(甲基)丙烯醯氧甲基_2_三氟甲基環 氧丙燒、2-(甲基）丙觸氧甲基_3_三氟甲基環氧丙燒、 2-（甲基)丙烯醯氧甲基_4_三氟甲基環氧丙院、2_(甲基)丙 烯醯氧友甲基-2-五氟乙基環氧丙烧、2_(甲基）丙稀酿氧甲基 一3-五氟乙基環氧丙烷、2一（甲基）丙烯醯氧甲基_4一五氟乙 基裱氧丙貌、2-(甲基）丙婦醯氧甲基—2_苯基環氧丙院、 2-（甲基)丙烯酿氧甲基I苯基環氧丙烧、2_(甲基)丙稀酿 # 氧:基~4一苯基環氧丙院、2, 3-二氟-2-(甲基）丙稀醢氧甲 基環氧丙燒、2,4-二氟-2-(甲基)丙烯喊f基環氧丙烧、 3, 3-二氟一2-(甲基）丙烯醯氧甲基環氧丙烷、2,4一二氟 一2-（甲基）丙烯醯氧甲基環氧丙烷、3,4_二氟_2_(甲基）丙 烯酿氧甲基環氧丙烧、4, 4-二氟-2-(甲基）丙婦醯氧甲基環 氧丙院、2-(甲基）丙烯醯氧甲基—3, 3, 4_三氟環氧丙院、 2_(甲基）丙烯醯氧甲基一3,4,4_三氟環氧丙烷、2一（甲基）丙 烯1氧甲基-3, 3,4,4-四氟環氧丙院、2一（甲基)丙稀酿氧乙 基核氧丙烷、2-(甲基）丙烯醯氧乙基_2_甲基環氧丙烷、 2:(甲基）丙烯醯氧乙基-4-甲基環氧丙烷、2一（甲基）丙烯醯 氧乙基-2-二氟甲基環氧丙烧、2—(甲基）丙烯醯氧乙基_3_ 三氟甲基環氧丙烷、2-(甲基）丙稀醯氧乙基_4_三氟甲基環 氧丙烷、2-(甲基）丙烯醯氧乙基_2_五氟乙基環氧丙烷、 2-(甲基）丙烯醯氧乙基-3-五氟乙基環氧丙烷、2_(甲基）丙 烯醯氧乙基-4-五氟乙基環氧丙烷、2-(甲基）丙烯醯氧乙基 一2-笨基環氧丙烷、2-(甲基）丙烯醯氧乙基_3_苯基環氧丙 烷、2-(甲基）丙烯醯氧乙基-4-苯基環氧丙烷、2 3_二氟 10 201222154 -2-(曱基）丙烯醯氧乙基環氧丙烷、2, 4一二氟_2_(甲基）丙 烯醯氧乙基環氧丙烧、3, 3-二氟甲基）丙稀崎乙基環 氧丙烷、3’ 4-二氟-2-(曱基）丙烯醯氧乙基環氧丙烷、4,4_ 二氟-2-(甲基）丙烯醯氧乙基環氧丙烷、2_(甲基）丙烯醯氧 乙基-3, 3,4-三氟環氧丙烷、2-(甲基）丙烯醯氧乙基 _3, 4, 4-二氟環氧丙烧、2-(甲基）丙稀酿氧乙基一& 3, 4, 4_ 四氟環氧丙烷、（甲基）丙烯酸環丁酯等。含環氧丙烷基化 合物(b2)可單獨一種使用或混合複數種使用。 其他不飽和單體（b3)的具體例為：（甲基）丙烯酸甲 酉曰、（甲基）丙稀酸乙酯、（曱基）丙烯酸正丁酯、（甲基）丙 烯酸二級丁酯、（甲基）丙烯酸三級丁酯、（甲基）丙烯酸異 丙酯、（曱基）丙稀酸環己酯、（曱基）丙烯酸_2_曱基環己 醋、（曱基）丙烯酸二環戊酯、（甲基）丙烯酸二環戊氧基乙 酯、（曱基）丙烯酸異冰片酯、馬來酸二乙酯（diethyl maleate)、富馬酸二乙酯（diethyl fumarate)、衣康酸二 乙酯（di ethy 1 i taconate)、（曱基）丙烯酸-2-羥基乙酯、（曱 基）丙烯酸-2-經基丙酯、苯乙稀、α_曱基苯乙稀、間一曱 基笨乙烯、對-曱基苯乙烯、對—曱氧基苯乙烯等。其中， 以苯乙烯、甲基丙烯酸三級丁酯、曱基丙烯酸二環戊酯、 丙烯酸二環戊氧基乙酯、對—曱氧基苯乙稀較佳。其他不飽 和單體(b3)可單獨一種使用或混合複數種使用。 本發明之含環氧丙烷基之環氧樹脂(B)，於合成時所使 用的溶劑’一般較常用者為乙二醇單丙基醚、二乙二醇二 曱基醚、四氫呋喃、乙二醇單曱基醚、乙二醇單乙基醚、 乙酸甲氧基乙酯、乙酸乙氧基乙酯、二乙二醇單甲基醚、 11 201222154 二乙二醇單乙基醚、二乙二醇單丁基醚、丙二醇單甲基醚 醋西文自曰、丙一醇單乙基鱗醋酸酯、丙二醇單丙基醚醋酸酯、 甲乙酮與丙鲷。其中，以二乙二醇二甲基喊、丙二醇單甲 基趟醋酸自旨為較佳。前述溶劑可單獨—種使践混合複數 種使用。 本發明之含環氧丙烷基之環氧樹脂(B)，於合成時所使 用之起始劑，一般為自由基形聚合起始劑，其具體例如 ，偶氮雙異丁猜（2, 2’-azobisisobutyronitrile)、 2, 2’-偶氮雙（2,4_ 二甲基戊腈）[2, 2，_az〇bis(2,4一 dimethylvaleronitrile)] ' 一甲基戊腈）等偶氮（azo)化合物；過氧化二苯甲醯 (benzoy1perox i de) 等之過氧化合物。 基於盼酸清漆樹脂(A)l〇〇重量份，含環氧丙炫基之環 氧樹脂(B)的使用量通常為5〜40重量份，較佳為7〜35重 量伤’更佳為10〜30重量份。由於含環氧丙燒基之環氧樹 月曰（B)可與經基型紛酿清漆樹脂(A-i)於後烤時形成較緊密 的結構，故不易產生裂縫或起皺。當含環氧丙烷基之環氧 樹脂(B)的使用量介於5〜40重量份時，則可於基板上形成 耐裂縫性佳的圖案。 [鄰萘醌二疊氣績酸類之酯化物(C)] 本發明正型感光性樹脂組成物的感光性物質係使用鄰 萘醌二疊氮磺酸之酯化物(〇，該酯化物（C)沒有特別的限 制，可選用經常使用者，其中’較佳者為鄰萘醌二疊氮磺 酸與羥基化合物的酯化物’更佳者為鄰萘醌二疊氮確酸與 201222154 多^經基化合物_旨化物，且前義化物可完錢化或部 伤酉曰化’該鄰萘㊃二疊氮確酸的具體例為：鄰萘酿二疊氣 4碩I、鄰萘醌二疊氮-5-磺酸、鄰萘醌二疊氮-6-磺酸 等。前述化合物之_如下所列：And a positive photosensitive resin composition as described in &, wherein the tri-based benzoic acid-based compound is selected from the group consisting of 2, 3, 4_triphenyl benzene caps, 2, 4, = tri-vinyl benzophenone , 2,4, 6-three-woven benzene, 3,4,5-tri-phenylene riding group. The positive photosensitive resin composition as described in the invention, wherein the base-based compound is selected from the group consisting of o-H-methylbenzene (tetra), m-methylbenzaldehyde and p-hydroxymethylbenzene. A group of formaldehyde. The positive photosensitive resin composition as described above, wherein, based on 1 GG by weight of the phenolic resin (4), the amount of the ring-containing filament (8) is 5 to 40 parts by weight, and the o-naphthalene diazide continues. The acid acetate (6) is used in an amount of 1 to 1 GG 4 parts, and the lye (9) is used in an amount of 5 (9) to 诵 by weight. A pattern forming method of the present invention is to apply a positive photosensitive resin composition as described above to a substrate, and then sequentially apply a pre-bake, an exposure, a development, and a post-baking treatment. The substrate is patterned. A thin film transistor array substrate according to the present invention comprises the above-mentioned figure 201222154. The present invention - Wei Jing_element, a surface-mounted crystal array substrate. In the present invention, '(meth)acrylic acid acrylic acid and/or methyl propyl hydrazine is similarly represented by (meth)propionic acid hydrazine to acrylic acid vinegar and/or methacrylic acid hydrazine to The (meth)acrylonitrile group means an acrylonitrile group and/or a methyl propyl group. The (meth) propylene oxime group represents an acryl oxime group and/or a methyl propylene fluorenyloxy group. The components of the present invention will be described in detail below. <Positive type photosensitive resin composition> [Sour acid varnish resin (A)] The acid varnish resin (4) of the positive photosensitive resin composition of the present invention contains a hydroxy novolak resin (A-1), and Optionally, further aldehyde varnish resin (A-2) is further included. The basal-type varnish resin (A-i) is obtained by a condensation reaction of a benzyl group-based compound with an aromatic thiol compound in the presence of an acidic catalyst. " Among them, specific examples of the hydroxybenzaldehyde compound are: o-hydroxybenzaldehyde 'm-hydroxybenzaldehyde, p-hydroxybenzaldehyde and the like hydroxy quinone aldehyde compound; 2,3-dihydroxybenzaldehyde, 2, Dihydroxybenzaldehyde compound such as 4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 3'4-dihydroxybenzaldehyde, 3,5-dihydroxybenzaldehyde; 2, 3,4-three a hydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde or the like, a trihydroxybenzaldehyde compound; o-hydroxyindole a hydroxyalkyl benzoquinone compound such as benzaldehyde, m-hydroxymethyl benzofural or p-hydroxymethylbenzaldehyde. The hydroxybenzoic acid compound may be used alone or in combination of plural kinds. Among them, 6 201222154 o-Hydroxybenzaldehyde, m-hydroxyindole aldehyde, p-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 2, 3,4-trihydroxybenzaldehyde is preferred. Specific examples of the aromatic hydroxy compound in the condensation reaction of the hydroxybenzaldehyde compound of the present invention are: phenol (phen〇1); (m-cresol), p-cres (p-cres〇1), ortho-phenol (〇_cres〇1), etc.; cresol; 2, 3-xylenol, 2, 5- Dimethylphenol, 3,5-one oxime, 3, 4-toluene, etc. (Cai (5)); m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-tridecylphenol, 2,3,5-triethylphenol, 4-tert-butylphenol, 3_t-butylphenol, 2-tert-butylphenol, 2-third Alkyl phenols such as butyl-4-nonylphenol, 2-tert-butyl-5-methylphenol, 6-t-butyl-3-methylphenol; p-methoxyphenol , alkoxy phenols such as m-methoxyphenol, p-ethoxylated phenol, m-ethoxy phenol, p-propoxy phenol, m-propoxy phenol, etc.; Isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol, 2-ethyl-4-isopropyl essential phenol, isopropenylbenzene (iS〇pr〇penyl phen) 〇l); phenyl phenol aryl phen〇1; 4, 4 _ once basal, double discretion ' A, m-benzene bis (resorcin〇i) For example, polyhydroxyphenols such as hydroquinone, pyrogallol, etc. The above aromatic hydroxy compounds may be used alone or in combination of plural kinds. It is preferred to use o-cresol, m-cresol, p-cresol, 2,5-dinonylphenol, 3,5-xylene, 2,3,5-trimethylbenzene. Specific examples of the acidic catalyst include hydrochloric acid, sulfuric acid, formic acid, acetic acid, 7 201222154 oxalic acid, p-toluene acid, and the like. The hydroxy novolak resin (A-1) is used in an amount of usually 30 to 100 parts by weight, preferably 4 to 100 parts by weight, more preferably 50 to 100 parts by weight, based on 100 parts by weight of the novolak resin (A). . When the amount of the hydroxy novolak resin (A-1) used is less than 30 parts by weight, the pattern formed by the photosensitive resin composition is liable to cause cracks and a problem that the residual film ratio is lowered. The other acid varnish resin (A-2) is generally obtained by a condensation reaction of the above aromatic radical compound and non-hydroxybenzaldehyde aldehyde in the presence of Φ in the above-mentioned acidic catalyst. Specific examples of the aldehydes of the non-hydroxybenzaldehyde are: methadone, paraformaldehyde, tri 〇xane, ethene, propylene, butyl, tridecyl acetic acid, Acr〇lein, crotonaldehyde, cyclohexanealdehyde, furfural, furyiacrolein, benzoquinone, terephthai aldehyde, Phenylacetic acid: α-phenylpropanal, /3-phenylpropanal, o-mercaptophenylfurfural, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, Monochlorobenzaldehyde, p-chlorobenzaldehyde, cinnamaldehyde, and the like. The above aldehydes may be used singly or in combination of plural kinds. Among them, formaldehyde is preferred. For the above-mentioned hydroxy novolac resin (A-D and other novolak resins (A-2), a single type of novolac resin may be used, or two or more types of different types of novolak resins may be mixed. Epoxy propylene group-containing epoxy resin (B)] The propylene oxide group-containing epoxy resin of the positive photosensitive resin of the present invention 3) is composed of an unsaturated monomer (10), a propylene oxide containing compound (10) and a pot ', [S] 8 201222154 The addition of its unsaturated monomer (b3). Wherein: specific examples of the unsaturated carboxylic acid monomer (bl) are: unsaturated monocarboxylic acids such as acrylic acid, mercaptoacrylic acid, crotonic acid, α-aluminum propylene & propyl acrylate, acrylic acid and cinnamic acid, maleic acid , unsaturated male dicarboxylic acids (anhydrides) such as maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and unsaturated polyvalent carboxylic acids (anhydrides) of three or more valences and many more. Among them, acrylic acid and mercaptoacrylic acid are preferred. The unsaturated carboxylic acid monomer (b1) may be used singly or in combination of plural kinds. • Specific examples of the propylene oxide-containing compound (b2) are: 3-(meth) propylene methoxy oxime (3-[(meth)aCryl〇yl〇Xy-methyl] oxetane), 3- (fluorenyl) propylene oxime oxime _3_ethyl propylene oxide, 3_(indenyl) propylene oxime oxymethyl-2-methyl propylene oxide, 3_(meth) propylene oxime fluorenyl trifluoromethyl Propylene oxide, 3-(meth)acryloyloxymethyl-2-pentafluoroethyl epoxy, 3-(indenyl) propylene fluorenyloxy-2-phenyl propylene oxide, 3- (fluorenyl) propylene oxime oxime-2,2-difluoro propylene oxide, 3-(meth) propylene oxiranyl-2, 2,4-trifluoroepoxypropane, 3-(methyl) propylene醯 曱 _ _ _2, 2' 4, 4-tetrafluoro propylene oxide, 3-(meth) propylene oxiranyl ethoxide, 3-(indenyl) propylene oxiranyl _ 3 - ethyl ring Oxypropane, 2-ethyl-3-(methyl)propenyloxyethyl propylene oxide, 3-(indenyl) propylene oxyethyl 2 monofluoromethyl epoxy, 3-(methyl) propylene Oxygen ethyl-2-pentaethyl ethyl propylene acrylate, 3-(methyl) propylene oxirane ethyl-2-phenyl epoxy propylene, 2, L ditun-3-(methyl) propylene Ethoxyethyl propylene oxide, 3-(Methyl)- propyl ethyl oxyethyl-2, 2,4-trifluoroepoxypropane, 3-(methyl) propylene oxiranyl-2'2, 4,4-tetrafluoro propylene oxide, 2-(Methyl) propylene oxiranyl propylene oxide, 2-mercapto- 2-(methyl) propylene oxiranoxymethyl propylene oxide, 3 methyl 9 201222154 = (meth) propylene oxime methyl Glycidil, 4-methyl-2-(methyl) propylene oxime oxymethyl propylene acrylate, 2-(methyl) propylene oxymethyl 2 _ trifluoromethyl epoxy, 2 -(Methyl)propenyloxymethyl_3_trifluoromethylepoxypropane, 2-(methyl)propenyloxymethyl-4_trifluoromethylepoxypropyl, 2_(methyl) Propylene oxime o-methyl-2-pentafluoroethyl epoxide, 2_(methyl) propylene oxymethyl 1-trifluoroethyl epoxide, 2-(methyl) propylene oxime _4-pentafluoroethyl oxime, 2-(methyl) propyl sulfonyloxymethyl 2-phenyl epoxide, 2-(methyl) propylene oxymethyl I phenyl ring Oxypropane, 2_(methyl) propylene ## Oxygen: ～4-phenyl epoxide, 2, 3-difluoro-2-(methyl) propyl oxirane methyl epoxide, 2,4-difluoro-2-(methyl) propylene shouting f-based propylene-propylene, 3, 3-two 2-(Meth)acryloyloxymethyl propylene oxide, 2,4-difluoro-2-(meth) propylene oxiranoxymethyl propylene oxide, 3,4-difluoro-2-(methyl) Propylene oxymethyl ketone, 4, 4-difluoro-2-(methyl) propyl methoxymethyl epoxide, 2-(methyl) propylene oxymethyl-3, 3, 4_Trifluoroepoxypropyl, 2_(meth)acryloyloxymethyl-3,4,4-trifluoroepoxypropane, 2-(methyl)propene 1 oxymethyl-3, 3,4, 4-tetrafluoroepoxypropyl, 2-(methyl)propene oxyethyl oxypropane, 2-(methyl) propylene oxiranyloxy-2-methyl propylene oxide, 2: (methyl ) propylene oxiranyl ethyl-4-methyl propylene oxide, 2-(methyl) propylene oxirane ethyl 2-difluoromethyl epethane, 2-(methyl) propylene oxirane _ 3_trifluoromethyl propylene oxide, 2-(methyl) propylene oxiranyl ethyl 4-1,4-trifluoromethyl propylene oxide, 2-(methyl) propylene oxiranyl 2- 2 pentafluoroethyl Propylene oxide, 2-(meth)acryloyloxyethyl-3-pentafluoroethyl propylene oxide, 2-(methyl) propylene oxyethyl-4-pentafluoroethyl propylene oxide, 2-( Methyl) propylene oxiranyl ethyl 1-phenyl propylene oxide, 2 -(Meth)acryloyloxyethyl-3-phenylpropane oxide, 2-(meth)acryloyloxyethyl-4-phenylepoxypropane, 2 3_difluoro 10 201222154 -2-( Mercapto) propylene oxiranyl ethyl propylene oxide, 2, 4-difluoro-2-(methyl) propylene oxiranyl ethyl epoxide, 3, 3-difluoromethyl) propyl succinyl ethyl propylene oxide , 3' 4-difluoro-2-(indenyl) propylene oxiranyl oxirane, 4,4-difluoro-2-(methyl) propylene oxiranyl propylene oxide, 2_(meth) propylene Ethoxyethyl-3,3,4-trifluoroepoxypropane, 2-(methyl)propene oxiranyl_3,4,4-difluoroepoxypropane, 2-(methyl) propylene Oxygenated ethyl one & 3, 4, 4_ tetrafluoropropylene oxide, cyclobutyl (meth)acrylate, and the like. The propylene oxide-containing compound (b2) may be used singly or in combination of plural kinds. Specific examples of the other unsaturated monomer (b3) are: (meth)acrylic acid, methyl (meth) acrylate, n-butyl (meth) acrylate, and butyl (meth) acrylate. , (butyl) (meth) acrylate, isopropyl (meth) acrylate, cyclohexyl (meth) acrylate, ( 2 - decyl hexyl acrylate) Dicyclopentyl ester, dicyclopentyloxyethyl (meth)acrylate, isobornyl (mercapto)acrylate, diethyl maleate, diethyl fumarate, clothing Di ethy 1 i taconate, 2-hydroxyethyl (meth) acrylate, 2-propyl propyl (meth) acrylate, styrene, α-mercaptostyrene, A sulphur-based ethylene, p-nonyl styrene, p-nonyloxy styrene, and the like. Among them, styrene, butyl methacrylate, dicyclopentanyl acrylate, dicyclopentyloxyethyl acrylate, and p-nonyloxystyrene are preferred. The other unsaturated monomers (b3) may be used singly or in combination of plural kinds. The epoxy group-containing epoxy resin (B) of the present invention is generally used as a solvent for the synthesis of ethylene glycol monopropyl ether, diethylene glycol didecyl ether, tetrahydrofuran, and ethylene. Alcohol monodecyl ether, ethylene glycol monoethyl ether, methoxyethyl acetate, ethoxyethyl acetate, diethylene glycol monomethyl ether, 11 201222154 diethylene glycol monoethyl ether, diethyl Glycol monobutyl ether, propylene glycol monomethyl ether vinegar, succinyl alcohol, monoethyl sulphate, propylene glycol monopropyl ether acetate, methyl ethyl ketone and propyl hydrazine. Among them, diethylene glycol dimethyl ketone and propylene glycol monomethyl hydrazine acetic acid are preferred. The foregoing solvents may be used alone or in combination. The propylene oxide group-containing epoxy resin (B) of the present invention is used as a starter for the synthesis, and is generally a radical-type polymerization initiator, which is specifically, for example, azobisisobutyl (2, 2) '-azobisisobutyronitrile, 2, 2'-azobis(2,4-dimethylvaleronitrile)[2, 2,_az〇bis(2,4-dimethylvaleronitrile)]-monomethylvaleronitrile Azo) a compound; a peroxy compound such as benzoy1perox i de. The epoxy propylene group-containing epoxy resin (B) is usually used in an amount of 5 to 40 parts by weight, preferably 7 to 35 parts by weight, based on the weight of the acid varnish resin (A). 10 to 30 parts by weight. Since the epoxy epoxide-containing epoxy resin (B) can form a tight structure with the base-type varnish resin (A-i) after baking, it is less likely to cause cracks or wrinkles. When the epoxy group-containing epoxy resin (B) is used in an amount of 5 to 40 parts by weight, a pattern having excellent crack resistance can be formed on the substrate. [Esteryl ester of o-naphthoquinone gas-based acid ester (C)] The photosensitive material of the positive-type photosensitive resin composition of the present invention is an ester of o-naphthoquinonediazidesulfonic acid (〇, the esterified product (C) There are no special restrictions, and it can be used by regular users, among which 'the preferred one is the esterified product of o-naphthoquinonediazidesulfonic acid with a hydroxy compound'. The better one is o-naphthoquinone diazide acid and 201222154 The base compound is a compound, and the pre-synthesis compound can be completely or partially damaged. The specific example of the ortho-naphthalene tetra-diazide acid is: o-naphthalene-stirred gas 4, I, o-naphthoquinone Nitro-5-sulfonic acid, o-naphthoquinonediazide-6-sulfonic acid, etc. The aforementioned compounds are listed below:
(一）經基二笨曱酮類化合物，其具體例為：2, 3, 4-三 經基二苯甲_、2,4, 4’ -三經基二苯甲酮、2,4, 6-三經基二 苯甲嗣、2, 3,4’ 4’ -四絲二苯甲酮、2, 2’，4,4’ -四經基二 苯曱酮、2’3’，4,4，，6-五羥基二苯甲酮、2,2，，3,4,4，-五 羥基二苯甲酮、2, 2,，3,4, 5, _五羥基二苯曱酮、 2, 3’ ’ 4, 5, 5’ -五羥基二苯甲 _、2, 3, 3,，4,4’，5, _六羥基二 苯曱酮等。 (二)一般式（I )所表示的羥基芳基化合物(1) A quinone ketone ketone compound, and specific examples thereof are: 2, 3, 4-trisylbiphenyl _, 2,4, 4'-trisyl benzophenone, 2, 4, 6-trisyldibenzoguanidine, 2,3,4' 4'-tetraose benzophenone, 2, 2',4,4'-tetra-tetrabenzophenone, 2'3', 4 ,4,6-pentahydroxybenzophenone, 2,2,3,4,4,-pentahydroxybenzophenone, 2, 2,3,4,5,pentahydroxydibenzophenone , 2, 3' '4, 5, 5'-pentahydroxydiphenyl-, 2, 3, 3,, 4, 4', 5, hexahydroxydibenzophenone and the like. (2) a hydroxyaryl compound represented by the general formula (I)
(〇H)x ‘般式（I ) [S1 式中’ R1〜R3為氫原子或低級之烷基，R4〜R9為氫原子、 鹵素原子、低級之烷基、低級之烷氧基(alk〇Xy)、低級之 脂烯基(alkenyl)或環烷基(CyCl〇alkyl)，R1。及R11為氫原 子 '鹵素原子或低級之烧基，X、y及z為1〜3的整數，η 為0或1。一般式（I )所表示的羥基芳基化合物之具體例 為：三(4-羥基苯基）曱烷、雙(4-羥基-3, 5-二甲基苯基)-4-羥基苯基曱烷、雙(4-羥基-3, 5-二曱基苯基)-3-羥基苯基 13 201222154 甲烷、雙(4-羥基-3, 5-二曱基苯基)-2-羥基苯基曱烷、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-經基苯基甲炫、雙（4-經基-3, 5-二甲基苯 基）-3,4-二羥基笨基曱烷、雙（4-羥基-2, 5-二甲基苯 基）-3,4-二羥基苯基曱烷、雙（4-羥基-3, 5-二甲基苯 基）-2,4-二羥基苯基曱烷、雙（4-羥基-2, 5-二甲基苯 基)-2,4-二羥基苯基曱烷、雙(4-羥基苯基)-3-曱氧基-4-羥基苯基甲烷、雙(3-環己基-4-羥基苯基)-3-羥基苯基曱 烷、雙(3-環己基-4-羥基苯基)-2-羥基苯基甲烷、雙(3-環 己基-4-羥基苯基)-4-羥基苯基甲烷、雙(3-環己基-4-羥基 -6-甲基芳基)-2-羥基苯基甲烷、雙(3-環己基-4-羥基-6-曱基苯基)-3-經基苯基甲燒、雙(3-環己基-4-齡基-6-曱基 苯基)-4-羥基苯基甲烷、雙(3-環己基-4-羥基-6-甲基苯 基)-3,4-二羥基苯基f烷、雙(3-環己基-6-羥基苯基)一3-羥基苯基甲烷、雙(3-環己基-6-羥基苯基)-4-羥基苯基甲 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)-2一羥基苯基甲烷、雙(3-環己基 -6-羥基-4-甲基苯基)-4-羥基苯基甲烷、雙(3_環己基一6_ 羥基-4-曱基苯基)-3,4-二羥基苯基甲烷、丨_[卜以-羥基苯 基)異丙基]-4-[1，1-雙(4-羥基苯基）乙基]苯、丨-以^一甲 基-4-羥基苯基）異丙基]-^[丨，丨_雙(3_甲基_4_羥基苯基） 乙基]苯等。 (二)一般式（Π )所表示的（羥基苯基)烴類化合物 201222154(〇H)x ' General formula (I ) [S1 where R1 to R3 are a hydrogen atom or a lower alkyl group, R4 to R9 are a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group (alk) 〇Xy), lower alkenyl or CyCl〇alkyl, R1. And R11 is a hydrogen atom 'halogen atom or a lower alkyl group, X, y and z are integers of 1 to 3, and η is 0 or 1. Specific examples of the hydroxyaryl compound represented by the general formula (I) are: tris(4-hydroxyphenyl)decane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenyl Decane, bis(4-hydroxy-3, 5-dimercaptophenyl)-3-hydroxyphenyl 13 201222154 methane, bis(4-hydroxy-3, 5-dimercaptophenyl)-2-hydroxybenzene Baseline, bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3-hydroxyphenyl Methane, bis(4-hydroxy-2, 5-dimethylphenyl)-2-phenylphenylmethyl, bis(4-carbazhen-3, 5-dimethylphenyl)-3,4- Dihydroxyphenyl decane, bis(4-hydroxy-2, 5-dimethylphenyl)-3,4-dihydroxyphenyl decane, bis(4-hydroxy-3, 5-dimethylphenyl) -2,4-dihydroxyphenyl decane, bis(4-hydroxy-2, 5-dimethylphenyl)-2,4-dihydroxyphenyl decane, bis(4-hydroxyphenyl)- 3-decyloxy-4-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-3-hydroxyphenyldecane, bis(3-cyclohexyl-4-hydroxyphenyl)-2 -hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-methylaryl)-2- Hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-mercaptophenyl)-3-perphenylene, bis(3-cyclohexyl-4-indolyl-6-mercaptobenzene 4-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)-3,4-dihydroxyphenylfane, bis(3-cyclohexyl-6-hydroxyl) Phenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxyphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxyphenyl)-2-hydroxybenzene Methane, bis(3-cyclohexyl-6-hydroxy-4-methylphenyl)-2-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxy-4-methylphenyl)-4- Hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxy-4-mercaptophenyl)-3,4-dihydroxyphenylmethane, 丨[[Bu-hydroxyphenyl)isopropyl]-4- [1,1-bis(4-hydroxyphenyl)ethyl]benzene, hydrazine-methyl-1-hydroxyphenyl)isopropyl]-^[丨,丨_double (3_methyl_ 4_hydroxyphenyl)ethyl]benzene and the like. (2) (hydroxyphenyl) hydrocarbon compounds represented by the general formula (Π) 201222154
式中’ R及Rl3為氫原子或低級烷基，X，及y’為1〜3 的整數。一般式（Π)所表示的（羥基苯基）烴類之具體例 為：2-(2’ 3, 4-三羥基苯基)_2_ (2’，3,，4, _三羥基苯基）丙 烷、2-(2,4-二羥基苯基)_2_(2，，4，_二羥基苯基）丙烷、 2-(4-經基苯基)-2-(4,-羥基苯基）丙烷、雙(2, 3, 4-三羥基 苯基）甲烷、雙(2, 4-二羥基苯基）甲烷等。 (四）其他芳香族羥基化合物，具體例為：苯酚、對一甲 氧基本盼、一甲基苯紛、對苯二盼、雙酴A、萘紛 (naphthol)、鄰苯二紛(pyrocatech〇i)、ι，2,3-苯三酴曱 醚(pyrogallol monomethyl ether)、1，2,3-苯三酚-1，3-二甲基謎(pyrogallol-1，3-dimethyl ether)、3,4, 5-三經 基苯甲酸(gallie acid)、部份酯化或部份醚化之3,4,5-三羥基苯甲酸等。 前述羥基化合物以2, 3, 4-三羥基二苯甲酮、2, 3, 4, 4’ -四羥氧基二苯曱酮為較佳。前述羥基化合物可單獨一種使 用或混合數種使用。 本發明樹脂組成物中的感光性物質鄰萘醌二疊氮磺酸 類之酯化物(C)，可使用含有醌二疊氮基的化合物’例如： 鄰萘醌二疊氮-4(或5)磺酸鹵鹽與前述（一）〜（四）所示的 經基化合物經過縮合反應完全酯化或部份酯化而得，前述 縮合反應通常在二氧雜環己烧（dioxane)、卜°比咯烷_ 201222154 (N-pyrrolidone)、乙醯胺（acetamide)等有機溶媒中進 行，同時，縮合反應在三乙醇胺(triethan〇lamine)、鹼金 屬碳酸鹽或鹼金屬碳酸氫鹽等鹼性縮合劑存在下進行較有 利。 此時，基於羥基化合物中之羥基總量1〇〇莫耳％，較佳 為50莫耳％以上，更佳為6〇莫耳％以上與鄰萘醌二疊氮 -4(或5)-續酸鹵鹽縮合而成醋化物，亦即，醋化度在5〇% 以上為較佳’最好是在6〇%以上。 基於酴酸清漆樹脂(A)100重量份，本發明之鄰萘g昆二 疊氮磺酸類之酯化物(C)的使用量通常為丨〜丨⑼重量份， 較佳為10〜50重量份，更佳為20〜40重量份，當鄰萘醌 二疊氮磺酸類之酯化物(C)的使用量介於ι〜1〇〇重量份 時’可提高樹脂組成物之感度。 [溶劑(D)] 本發明所使用之溶劑（D)需選用較易和其他有機成分 互相溶解之有機溶劑。 本發明所使用之溶劑（D)之具體例為：乙二醇單甲基 喊、乙一醇單乙基鱗、二乙二醇單乙基鍵、二乙二醇單正 丙基醚'二乙二醇單正丁基醚、三乙二醇單曱基醚、三乙 二醇單乙基醚、丙二醇單甲基醚、丙二醇單乙基醚、二丙 二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單正丙基醚、 一丙一醇單正丁基喊、三丙二醇單曱基喊、三丙二醇單乙 基喊荨之（D亞烧基一醇早烧趟類；乙二醇單曱基峻醋酸 酯、乙二醇單乙基醚醋酸酯、丙二醇單甲基醚醋酸酯、丙 一醇單乙基趟醋酸酯等之（聚）亞烧基二醇單烧醚醋酸酯 16 201222154 ;、頁’ 一乙—醇二甲基越、二乙二醇甲基乙基驗、二乙二醇 一乙基鍵四氫咬喃等之其他醚類；甲乙嗣、環己嗣、2一 庚_、3-庚_等之_員；2_經基丙酸甲醋、2_經基丙酸乙 酉曰等礼酸絲類；2-經基—2__甲基丙酸甲醋、2_經基_2_甲 基丙酸乙自旨、3-曱氧基丙酸曱g旨、3_曱氧基丙酸乙醋、3_ 乙氧基丙酸甲⑽、3~乙氧基丙酸乙δ旨、乙氧基醋酸乙醋、 羥基醋酸乙酯、2-羥基-3-甲基丁酸甲酯、3_曱基_3_曱氧 基丁__旨、3m曱氧基丁基丙酸g旨、醋酸乙酿、 醋酸正_旨、醋酸異醜、醋酸正丁g|、醋酸異丁醋、醋 酸正戊S旨、醋gt異摘、峨正丁酯、丁酸乙g旨、丁酸正 丙醋、丁酸異丙醋、丁酸正丁酯、丙酮酸曱酯、丙酮酸乙 酉曰、丙酮酸正丙酯、乙醯醋酸曱酯、乙醯醋酸乙酯、2_氧 基丁酸乙醋等之其他賴；甲苯、二甲苯等之芳香族烴類； N-曱基吡咯烷_、N，N_二曱基曱醯胺、N，N_二甲基乙醯胺 等之羧酸胺類。其中，以丙二醇單甲基醚醋酸酯以及乳酸 乙酯為較佳。前述溶劑可單獨一種使用或混合複數種使用。 基於盼酸清漆樹脂(A) 1〇〇重量份，本發明感光性樹脂 組成物之溶劑(D)的使用量通常為500〜2, 000重量份，較 佳為600〜1，800重量份，更佳為7〇〇〜1，500重量份。 [添加劑(E)] 本發明之正型感光性樹脂組成物，可進一步添加芳香 族羥基化合物，藉以調整組成物之感度或黏度。適合於本 發明之芳香族經基化合物的具體例如：TPPA-1000P、 TPPA-100-2C > TPPA-1100-3C > TPPA-1100-4C > TPPA-1200- 24X、TPPA-1200-26X、TPPA-1300-235T、TPPA-1600-3M6C、 201222154 TPPA MF等市售品（日本本州化學工業製），並中，以 =_M6G、T_F馳佳，前料麵祕化合物 二Γ種細或者混合複數種使用。基於祕清漆樹脂 ⑷100重量份，芳香族經基化合物之_ 本發明之正型感光性樹脂組成物，可視需要進一步添 加密著助劑、表面平坦劑、稀釋劑及相容性佳之染料。 本發明之密著助劑包含三聚氰胺(melaraine)化合物、 矽烷系（silane)化合物，其作用在於增加正型感光性樹脂 組成物與附著基板間的密著性。其中，三聚氰胺之具體例 如：Cymel-300、Cyme卜303(三井化學製）、MW-30MH、MW-30、 MS-11、MS-001、MX-750、MX-706(三和化學製）等市售品。 而矽烷系化合物之具體例如：乙烯基三甲氧基矽烷、乙烯 基二乙氧基石夕烧、3-(甲基）丙烯醯氧基丙基三甲氧基石夕 烷、乙烯基三(2-曱氧基乙氧基)矽烷、N-(2-氨基乙基)一3_ 氨基丙基甲基二甲氧基矽烷、N-(2-氨基乙基)-3-氨基丙基 二甲氧基梦烧、3-氣基丙基三乙氧基碎烧、3-環氧丙氧基 丙基三曱氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基石夕 院、2-(3,4-環氧環己基）乙基三甲氧基矽烧、3-氣丙基甲 基二甲氧基矽烧、3-氯丙基三甲氧基石夕烧、3-甲基丙埽氧 基丙基三甲氧基矽烷、3-硫醇基丙基三甲氧基矽烷、雙 -1,2-(三曱氧基矽基）乙烷等。基於酚醛清漆樹脂（a)i〇〇 重量份，三聚氰胺化合物之密著助劑的使用量通常為〇〜20 重量份，較佳為〇· 5〜18重量份，更佳為1. 0〜15重量份； 矽烷系化合物之密著助劑的使用量通常為0〜2重量份，較 18 201222154 佳為0· 001〜1重量份，更佳為〇 005〜〇. 8重量份。 本發明之表面平坦劑包含氟系界面活性劑、石夕系界面 活性劑。其中，氟系界面活性劑之具體例如：Flourate FC-430、FC-43K3M 製），F-t〇P EF122A、122B、122C、126、 BL20(T〇chem product製）等市售品。而矽系界面活性劑之 具體例如：SF8427、SH29PA (Tomy Dow Corning Silicon 製）等市售品。基於酚醛清漆樹脂(A)1〇〇重量 活性劑之使用量通常為〇M.2重量份，較佳為〇 〇^ • 重量份，更佳為〇. 050〜〇. 8重量份。 適合於本發明之稀釋劑如貺8〇1、RE8〇2(帝國丨浊 等市售品。 適合於本發明之相容性佳之染料的具體例如：墓黃素 (cumnnin)、香豆素(c〇umarin)系、偶氮(az〇)染料等，此 外，本發明亦可依需要再添加其他的添加劑，例如：可塑 劑、安定劑等。 <正型感光性樹脂組成物形成圖案的方法〉 I 、 f發明使用前述正型感光性樹脂組成物形成圖案的方 法，是藉域触佈、流延_她式塗料塗佈方法， 將該感光性樹敝成餘基板上，並於塗佈後以預烤 (prebake)方式將溶劑去除而形成一預烤塗膜。其中，預烤 之條件，依各成分之種類、配合比率而異，通常為溫度在 70〜1 l〇°C間’進行1〜π分鐘。 爾後’將該_純定之鮮下進行曝光，然後於 23±2C的溫度下浸潰於顯影液中，歷時15秒〜5分鐘，藉 此將不要之部分除去而形成特定的圖案。曝光所使用之^ 201222154 線’以g線、h線、i線等之紫外線為佳，而紫外線照 置可為(超）高壓水銀燈及金屬鹵素燈。 、 本發明所使用顯影液的具體例如：氫氧化納、氣氧化 鉀、碳酸鈉、碳酸氫鈉、碳酸鉀、碳 基石夕酸納、氨水、乙胺、脸田甘幾納甲 紙八乙妝一乙胺、二甲基乙醇胺、氫氧化 四伙、氫氧化四乙铵、膽驗、对、錢及^ 8_二 一％_〔5,4, 0〕-7-十一烯等之鹼性化合物。 ”Wherein R and Rl3 are a hydrogen atom or a lower alkyl group, and X and y' are integers of 1 to 3. Specific examples of the (hydroxyphenyl) hydrocarbon represented by the general formula (Π) are: 2-(2' 3, 4-trihydroxyphenyl)_2_ (2',3,4, _trihydroxyphenyl) Propane, 2-(2,4-dihydroxyphenyl)_2_(2,4,-dihydroxyphenyl)propane, 2-(4-phenylphenyl)-2-(4,-hydroxyphenyl) Propane, bis(2,3,4-trihydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)methane, and the like. (4) Other aromatic hydroxy compounds, specific examples are: phenol, p-methoxy methoxy, monomethyl benzene, benzophenone, bismuth A, naphthol, pyrocatech 〇 i), pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, 3 , 4, 5-trimethyl benzoic acid (gallie acid), partially esterified or partially etherified 3,4,5-trihydroxybenzoic acid, and the like. The above hydroxy compound is preferably 2,3,4-trihydroxybenzophenone or 2,3,4,4'-tetrahydroxyoxybenzophenone. The above hydroxy compounds may be used singly or in combination of several kinds. The ester material of the ortho-naphthoquinonediazide sulfonic acid (C), which is a photosensitive material in the resin composition of the present invention, may be a compound containing a quinonediazide group, for example: o-naphthoquinonediazide-4 (or 5) The sulfonic acid halide salt is obtained by completely esterifying or partially esterifying the mercapto compound represented by the above (1) to (4) by a condensation reaction, and the condensation reaction is usually carried out in a dioxane or a dioxane. The rhodamine _ 201222154 (N-pyrrolidone), acetamide and other organic solvents are carried out, and the condensation reaction is alkaline condensation such as triethanolamine (triethan〇lamine), alkali metal carbonate or alkali metal hydrogencarbonate. It is advantageous to carry out the presence of the agent. At this time, based on the total amount of hydroxyl groups in the hydroxy compound, 1% by mole, preferably 50% by mole or more, more preferably 6% by mole or more and o-naphthoquinonediazide-4 (or 5)- The acid halide salt is condensed to form an acetate, that is, the degree of acetification is preferably 5% or more, preferably more than 6%. The ester of the o-naphthalene g-quinonediazidesulfonic acid ester (C) of the present invention is usually used in an amount of from 丨 to 丨 (9) parts by weight, preferably from 10 to 50 parts by weight, based on 100 parts by weight of the phthalic acid varnish resin (A). More preferably, it is 20 to 40 parts by weight, and when the ester of the o-naphthoquinonediazidesulfonic acid ester (C) is used in an amount of from 1 to 1 part by weight, the sensitivity of the resin composition can be improved. [Solvent (D)] The solvent (D) used in the present invention requires an organic solvent which is more soluble in other organic components. Specific examples of the solvent (D) used in the present invention are: ethylene glycol monomethyl ketone, ethyl alcohol monoethyl scale, diethylene glycol monoethyl bond, diethylene glycol mono-n-propyl ether 'two Glycol mono-n-butyl ether, triethylene glycol monodecyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl Ether, dipropylene glycol mono-n-propyl ether, mono-propanol mono-n-butyl shunt, tripropylene glycol monodecyl shunt, tripropylene glycol monoethyl sulfonate (D-alkylene-alcohol early burnt oxime; ethylene glycol (poly)alkylene diol monoether ether acetate 16 such as monoterpenyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene monoethyl hydrazine acetate 201222154;, page 'Ethyl ether, dimethyl dimethyl group, diethylene glycol methyl ethyl test, diethylene glycol monoethyl bond tetrahydroanthene and other ethers; methyl ethyl hydrazine, cyclohexane, 2 a g- _, 3- g _ _ _ _; 2 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 2_trans-base_2_methylpropionic acid 、, 3-曱oxypropionic acid 曱g, 3_methoxypropionic acid ethyl acetonate, 3_ ethoxypropionic acid methyl (10), 3-ethoxypropyl propionate B δ, ethoxyacetic acid ethyl vinegar, Ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-mercapto-3-indolyl __, 3m methoxy butyl propionic acid g, acetic acid, acetic acid _, acetic acid, ugly acetate, n-butyl acetate, acetic acid, isobutyl vinegar, acetic acid, pentane s, vinegar gt, butyl butyl acrylate, butyric acid, butyl butyl acrylate Vinegar, n-butyl butyrate, decyl pyruvate, acetonyl pyruvate, n-propyl pyruvate, decyl acetate, ethyl acetate, 2-ethoxybutyric acid, etc.; An aromatic hydrocarbon such as xylene; a carboxylic acid amine such as N-mercaptopyrrolidine, N,N-didecylguanamine or N,N-dimethylacetamide; Monomethyl ether acetate and ethyl lactate are preferred. The above solvents may be used singly or in combination of plural kinds. Based on 1 part by weight of the acid varnish resin (A), the solvent of the photosensitive resin composition of the present invention ( D) is usually used in the amount of 500~2, 000 The portion is preferably 600 to 1,800 parts by weight, more preferably 7 to 1,500 parts by weight. [Additive (E)] The positive photosensitive resin composition of the present invention may further contain an aromatic hydroxy compound To adjust the sensitivity or viscosity of the composition. Specific examples of the aromatic mercapto compound suitable for the present invention are, for example, TPPA-1000P, TPPA-100-2C > TPPA-1100-3C > TPPA-1100-4C > TPPA -1200- 24X, TPPA-1200-26X, TPPA-1300-235T, TPPA-1600-3M6C, 201222154 TPPA MF and other commercial products (made by Japan Honshu Chemical Industry Co., Ltd.), and in the middle, =_M6G, T_F is good, before The secret compound of the material surface is fine or mixed and used in combination. Based on 100 parts by weight of the secret varnish resin (4), the aromatic base-based compound _ the positive-type photosensitive resin composition of the present invention may further contain an auxiliary agent, a surface flat agent, a diluent, and a dye having good compatibility as needed. The adhesion aid of the present invention comprises a melaraine compound or a silane compound which acts to increase the adhesion between the positive photosensitive resin composition and the attached substrate. Among them, specific examples of melamine are: Cymel-300, Cyme Bu 303 (manufactured by Mitsui Chemicals), MW-30MH, MW-30, MS-11, MS-001, MX-750, MX-706 (manufactured by Sanwa Chemical Co., etc.) Commercial products. Specific examples of the decane-based compound are, for example, vinyltrimethoxydecane, vinyldiethoxylate, 3-(meth)acryloxypropyltrimethoxy-naphthene, vinyltris(2-oxime) Ethyloxy)decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyldimethoxymethane , 3-air propyl triethoxy pulverization, 3-glycidoxypropyl trimethoxy decane, 3-glycidoxy propyl methyl dimethoxy sylvestre, 2- ( 3,4-epoxycyclohexyl)ethyltrimethoxysulfonium, 3-apropylmethyldimethoxysulfonium, 3-chloropropyltrimethoxyxanthine, 3-methylpropoxylated Propyltrimethoxydecane, 3-thiolpropyltrimethoxydecane, bis-1,2-(tridecyloxyindenyl)ethane, and the like. 〜5〜18重量份,优选为1. 0〜15。 The amount of the adhesive agent of the melamine compound is usually 〇~20 parts by weight, preferably 〇·5~18 parts by weight, more preferably 1. 0~15. The amount of the adhesion aid of the decane-based compound is usually 0 to 2 parts by weight, more preferably 0. 001 to 1 part by weight, more preferably 〇005 to 〇. 8 parts by weight. The surface flat agent of the present invention contains a fluorine-based surfactant and a Shiyue surfactant. Among them, specific examples of the fluorine-based surfactant are, for example, Flourate FC-430 and FC-43K3M, and F-t〇P EF122A, 122B, 122C, 126, and BL20 (manufactured by T〇chem product). Specific examples of the lanthanoid surfactants include commercially available products such as SF8427 and SH29PA (manufactured by Tomy Dow Corning Silicon). The amount of the active agent used is usually 〇M. 2 parts by weight, preferably 〇 • ^ • parts by weight, more preferably 〇. 050 〇. 8 parts by weight, based on the weight of the phenol varnish resin (A). Suitable diluents for the present invention are commercially available products such as 贶8〇1, RE8〇2 (emperor turbidity, etc. Specific examples of compatible dyes suitable for the present invention are, for example, cumnnin, coumarin ( C〇umarin), azo (az〇) dye, etc. Further, in the present invention, other additives such as a plasticizer, a stabilizer, etc. may be added as needed. <The positive photosensitive resin composition is patterned. Method 〉 I, f Inventively, the method for forming a pattern by using the positive photosensitive resin composition described above is a method of coating a photosensitive tree with a touch coating and a casting method, and coating the photosensitive tree on a substrate. After the cloth is removed in a prebake manner to form a pre-baked coating film, wherein the pre-baking conditions vary depending on the type of the components and the blending ratio, and the temperature is usually between 70 and 1 l ° ° C. 'Perform 1 to π minutes. Then, _ purely set the exposure to fresh, and then immersed in the developer at a temperature of 23 ± 2 C for 15 seconds to 5 minutes, thereby removing unnecessary portions. Specific pattern. ^201222154 line used for exposure 'g line, h line, i The ultraviolet light is preferably a (ultra) high pressure mercury lamp and a metal halide lamp. Specific examples of the developer used in the present invention include sodium hydroxide, potassium oxyhydroxide, sodium carbonate, sodium hydrogencarbonate, and potassium carbonate. , carbon-based stone sodium sulphate, ammonia, ethylamine, face kanjana nail paper eight acetyl makeup one ethylamine, dimethylethanolamine, oxidized four groups, tetraethylammonium hydroxide, biliary test, right, money and ^ Basic compound such as 8_2%_[5,4,0]-7-undecene."
較佳地’顯驗的濃度是介於_重量%〜1G重量％ ’間’更佳地是介於〇· 〇〇5重量％〜5重量%之間，又更佳地° 是介於0.01重量％〜1重量％之間。 使用前述鹼性化合物所構成之顯影液時，通常於顯影 後以水洗淨，再以壓縮空氣或壓魏氣風乾缝臈。接著^ 使用熱板或烘箱等加絲置賴細進行麟(_b邮 處理。後烤溫度通常為100〜25{rc，其中，使用熱板之加 熱時間為1分鐘〜60分鐘，使用烘箱之加熱_為5分鐘 〜90分鐘。經過以上之處理步驟後即可於基板形成圖案。 <薄膜電晶體陣列基板> 本發明之薄膜電晶體陣列基板（簡稱TFT陣列基板)之 製造方法，乃根據前述形成圖案的方法而構成。亦即，將 本發明之JE型感光性獅旨纟减物以旋轉塗佈、流延塗佈或 報式塗佈等塗佈方式塗佈於-含抽、鉻、氮切或非結 晶矽等之薄膜的玻璃基板或塑膠基板上.而形成一正型光阻 劑層，接著經過預烤、曝光、顯影及後烤處理形成感光性 樹脂圖案之後，進行_及紐重複上述步驟即可 製得一含多數薄膜電晶體或電極之薄膜電晶體陣列基板。 201222154 在此’參照圖一對LCD用TFT陣列基板加以說明。 圖一係例示LCD用TFT陣列基板的剖視示意圖。（1)首 先，於玻璃基板101上的鋁薄膜等處設置閘極102a及儲存 電容Cs電極l〇2b; (2)其次，於閘極i〇2a上覆蓋氧化矽膜 (SiOx)103或氮化矽膜(SiNx)104等而形成絕緣膜，並於此 絕緣膜上，（3)形成作為半導體活性層的非結晶石夕層 (a-Si)105 ; (4)接著，為了降低接面阻抗設置了摻雜氮不 純物的非結晶矽層106 ; (5)然後，使用鋁等金屬形成集極 107a及源極107b ’該集極1 〇7a連接於資料訊號線（圖中未 示）上，而該源極l〇7b則連接於晝素電極（或子畫素電 極)109上；（6)最後，為保護作為半導體活性層的非結晶矽 層（a-Si)105、集極l〇7a或源極l〇7b等，設置氮化石夕膜等 作為保護膜108。 <液晶顯示元件> 本發明之液晶顯示元件，包含了如前所述的本發明之 TFT陣列基板’該TFT陣列基板乃根據本發明之圖案形成方 法而構成者。另外’依需要亦可含有其他的部材。 前述液晶顯示元件的基本構成形態之具體例如\丨）將 TFT等之驅動元件與晝素電極（導電層）經排列所形成的本 發明之TFT陣列基板(驅動基板），與由彩色據光片及對電 極（導電層）所構成的彩色濾光片基板間介入間隔體並且對 向配置，最後於間隙部份封入液晶材料而構成。或者，（2) 將於本發明之TFT陣列基板上直接形成彩色濾光片之彩色 /慮光片一體型TFT陣列基板，與配置了對電極（導電層）之 對向基板間介人間隔體並且對向目&置，最後於間隙部份封 201222154 入液晶材料而構成等。 前述導電層之具體例如ΙΊΌ膜；銘、鋅、銅、鐵、錦、 鉻鉬等之金屬膜，二氧化石夕等之金屬氧化膜等。其中， 以具透明性的膜層絲佳，又以ITQ膜為最佳。 ，述本發明之TFT陣列基板、彩色渡光片基板及對向 基板等所使用之基材’其具體例如：納辦玻璃、低膨服玻 璃、無驗玻璃、石英玻璃等之公知的玻璃，另外，也可採 用由塑膠膜等構成的基板。 • 【實施方式】 本發明將就以下實施例及比較例進一步說明，但應瞭 解的是’該等實施讎為例示說明之用，而不應被轉為 本發明實施之限制。 [合成例1] 。在-容積1000毫升之四頸錐瓶上設置氮氣入口、授拌 器、加熱ϋ、冷凝管及溫度計，導人氮氣後添加間甲齡 64. 89g(0. 6 莫耳）、對-曱盼 43· 26g(〇· 4 莫耳）、3, 4-二羥 基苯甲醛55. 25g(0· 4莫耳)及草酸h 8〇g(〇. 〇2莫耳）。緩 L攪拌使反應溶液昇溫至l〇〇°c，並於此溫度下聚合5小 時。然後，將反應溶液昇溫至18(rc，以1〇mmHg之壓力進 行減壓乾燥，將溶劑脫揮後可得羥基型酚醛清漆樹脂 (A-1-1)。 [合成例2] . 以相同於前述合成例1的步驟製備羥基型酚醛清漆樹 脂(A-1-2)’不同處在於以鄰-羥基苯曱醛48. 85g(〇. 4莫耳） 取代3, 4-二羥基苯曱醛。 m 22 201222154 [合成例3] j处牡7、MZ，d，4-二羥基笨曱醛61.65 (〇 莫耳)取代3,4-二羥基苯曱醛。· [合成例4] 以相同於前述合成例1的步驟製備祕清漆樹脂 (A-2-υ ’不同處在於以37重量％之甲醛32· 43g(〇. 4 取代3,4-二經基苯甲酸。Preferably, the 'visual concentration is between _% by weight and 1% by weight' is more preferably between 5% and 5% by weight, and more preferably between 0.01 and 5% by weight. Between % and 1% by weight. When the developer composed of the above basic compound is used, it is usually washed with water after development, and then air-dried with compressed air or compressed air. Then ^ using a hot plate or oven, etc., the wire is placed on the lining (_b mail processing. The post-baking temperature is usually 100~25{rc, wherein the heating time of the hot plate is 1 minute to 60 minutes, using the heating of the oven _ is 5 minutes to 90 minutes. After the above processing steps, a pattern can be formed on the substrate. <Thin-film transistor array substrate> The method for manufacturing a thin film transistor array substrate (abbreviated as TFT array substrate) according to the present invention is based on The method for forming a pattern is formed by applying a coating method such as spin coating, cast coating, or newspaper coating to a coating method of spin coating, cast coating, or newspaper coating. Forming a positive photoresist layer on a glass substrate or a plastic substrate of a film such as a nitrogen cut or an amorphous germanium, followed by prebaking, exposing, developing, and post-baking to form a photosensitive resin pattern, and then performing _ and By repeating the above steps, a thin film transistor array substrate containing a plurality of thin film transistors or electrodes can be obtained. 201222154 Here, a pair of TFT array substrates for LCD will be described. Fig. 1 is a cross-sectional view showing a TFT array substrate for LCD. (1) First, a gate electrode 102a and a storage capacitor Cs electrode l〇2b are provided on an aluminum film or the like on the glass substrate 101; (2) Next, a yttrium oxide film (SiOx) is coated on the gate electrode i〇2a. 103 or a tantalum nitride film (SiNx) 104 or the like to form an insulating film, and on the insulating film, (3) forms a non-crystalline austenite layer (a-Si) 105 as a semiconductor active layer; (4) Next, The junction resistance is reduced to form an amorphous germanium layer 106 doped with nitrogen impurities; (5) Then, a collector 107a and a source 107b are formed using a metal such as aluminum. The collector 1 〇7a is connected to the data signal line (not shown) In the above, the source 10b is connected to the halogen electrode (or sub-pixel electrode) 109; (6) Finally, to protect the amorphous germanium layer (a-Si) 105 as a semiconductor active layer, A collector 〇7a or a source 〇7b or the like is provided with a nitride film or the like as the protective film 108. <Liquid Crystal Display Element> The liquid crystal display element of the present invention comprises the TFT array of the present invention as described above. The substrate 'the TFT array substrate is constructed according to the pattern forming method of the present invention. Further, 'other parts may be included as needed. Specifically, the basic configuration of the liquid crystal display device is, for example, a TFT array substrate (drive substrate) of the present invention in which a driving element such as a TFT and a halogen electrode (conductive layer) are arranged, and a color light is used. A color filter substrate composed of a sheet and a counter electrode (conductive layer) is interposed between the color filter substrates and disposed opposite to each other, and finally a liquid crystal material is sealed in the gap portion. Alternatively, (2) a color/light-insulation-integrated TFT array substrate in which a color filter is directly formed on the TFT array substrate of the present invention, and a counter-substrate intervening spacer disposed with a counter electrode (conductive layer) And the opposite direction is set, and finally the liquid crystal material is sealed in the gap portion 201222154 to form and the like. Specific examples of the conductive layer include a ruthenium film; a metal film such as zinc, copper, iron, brocade, chromium molybdenum or the like; a metal oxide film such as sulphur dioxide or the like. Among them, the film with transparency is good, and the ITQ film is the best. The substrate used in the TFT array substrate, the color light-receiving sheet substrate, and the counter substrate of the present invention is specifically known as, for example, a glass of a glass, a low-expansion glass, a glass without a glass, or a quartz glass. Further, a substrate made of a plastic film or the like can also be used. The present invention will be further described in the following examples and comparative examples, but it should be understood that the embodiments are intended to be illustrative and not restrictive. [Synthesis Example 1]. In the four-necked flask with a volume of 1000 ml, a nitrogen inlet, a stirrer, a heating crucible, a condensing tube and a thermometer were placed, and after introducing nitrogen, the inter-age age was 64.89 g (0.6 mol), and the 43·26g(〇·4 mol), 3, 4-dihydroxybenzaldehyde 55. 25g (0.4 m mole) and oxalic acid h 8〇g (〇. 〇2 mol). The reaction solution was heated to l ° ° C with stirring, and polymerized at this temperature for 5 hours. Then, the reaction solution was heated to 18 (rc, dried under reduced pressure at a pressure of 1 〇 mmHg, and the solvent was devolatilized to obtain a hydroxy novolak resin (A-1-1). [Synthesis Example 2] The hydroxy novolak resin (A-1-2) was prepared in the same manner as in the above-mentioned Synthesis Example 1 except that the 3,4-dihydroxybenzoquinone was replaced by o-hydroxybenzaldehyde 48.85 g (〇. 4 mol). Aldehyde. m 22 201222154 [Synthesis Example 3] j, 7, M, d, 4-dihydroxyindole aldehyde 61.65 (mole) substituted 3,4-dihydroxybenzaldehyde. [Synthesis Example 4] The same procedure as in the above Synthesis Example 1 was carried out to prepare a secret varnish resin (A-2-υ ' differs in that 37% by weight of formaldehyde 32·43 g (〇. 4 is substituted for 3,4-di-benzoic acid).
[合成例5] 以相同於則述合成例i的步驟製備紛酸清漆樹脂 (A-2-2) ’不同處在於以笨甲醛42伽取代3,4—二絲 曱醛。 [合成例6] 在一容積酬毫升之四頸錐瓶上設置氮氣人口、游 器加熱器、冷凝管及溫度計，導入氮氣後添加丙二醇單 甲基醚醋酸自旨2(%、3-(曱基）丙_氧甲基_2_苯基環氧丙 院30g、曱基丙稀酸25g、甲基丙烯酸二環戊35g及苯乙 烯i〇g。緩慢擾拌使反應驗昇溫至8(rc，然後將2 2,— 偶氮雙=丁腈2g溶於丙二醇單f基_醋酸㈣g，並以五 等伤之畺在小時間隔添力口在四頸錐瓶中。聚合過程的反 應溫度維持8(TC，聚合時間4小時。完成聚合後，將溶劑 脫揮，可得含環氧丙烷基之環氧樹脂(Β_υ。 [合成例7] [S] 以相同於前述合成例6的步驟製備含魏丙絲之環 氧樹脂(Β-2)，不同處在於改變進料組成，以3 (甲基）丙稀 23 201222154 酿氧曱基-3-乙基環氧丙燒3Qg取代3_(甲基)丙_氧甲 基-2-苯基環氧丙院。 [合成例8] 以相同於前述合成例6的步驟製備含環氧丙烧基之環 氧樹脂(B-3) ’不同處在於改變進料組成，以2 (甲基）丙稀 醯氧甲基-4-三氟甲基環氧丙燒3〇g取代3_(甲基）丙稀酿 氧甲基-2-笨基環氧丙燒。 [合成例9] 在一容積1000毫升之四頸錐瓶上設置氮氣入口、攪拌 器、加熱器、冷凝管及溫度計，導入氮氣後添加二乙二醇 二甲基醚200g、甲基丙烯酸3〇g、甲基丙烯酸環氧丙酯 (glycidyl methacrylate)25g、苯乙烯 20g 及甲基丙烯酸 三級丁酯25g。緩慢攪拌使反應溶液昇溫至85°c，然後將 2’2’-偶氮雙異丁腈2g溶於二乙二醇二曱基醚，並以五等 份之量在一小時間隔添加在四頸錐瓶中。聚合過程的反應 溫度維持85°C，聚合時間6小時。完成聚合後，將溶劑脫 揮’可得環氧樹脂(B，-l)。 [合成例10] 以相同於前述合成例9的步驟製備環氧樹脂(B，-2)， 不同處在於改變進料組成，以鄰-乙烯基苯曱基環氧丙醚 2¾取代甲基丙烯酸環氧丙酯。 <感光性樹脂組成物之實施例及比較例> [實施例1 ] 將100重量份的羥基型酚醛清漆樹脂(A-l-l)、15重量 份的含環氧丙烷基之環氧樹脂(B-1)及25重量份的2, 3, 4- 24 201222154 二經基二苯甲酮與1，2-萘酿二疊氮-5-績酸之酯化物 (c-i)(平均酯化度85%)所組成的混合物，加入75〇重量份 的丙二醇單甲基醚醋酸酯的溶劑(D-1)中，以搖動式攪拌器 擾拌使該混合物溶解於溶劑中，進行聚合反應3小時，即 可製得本發明的正型感光性樹脂組成物。以下記的各檢測 項目進行檢測，所得結果如表1所示。 [實施例2〜8] 相同於實施例1的操作方法，不同的地方在於：改變原 料的種類及其使用量，其配方及檢測結果如表1所示。 [比較例1〜6] 相同於實施例1的操作方法，不同的地方在於：改變原 料的種類及其使料，其配方及制結果如表1所示。、 【檢測項目】 <耐裂縫性> 將正型感光性樹脂組成物以旋轉塗佈的方式，塗佈在 6时之石夕晶圓上’然後於丨赃溫度下預烤⑽秒形成一 的麟塗膜。接著’於指定之光罩T，以紫外光(曝 光機i 號為 AG5GG-4N ;臟 Nano Technology 製)6mJ/cm2 的光，照射後’接著將塗膜浸潰於23ΐ之顯影液(2. 38%四 =醜化銨)6〇秒，將曝光部分的塗膜除去，然後以純水 士 再於160 C的溫度後烤5分鐘，使正型感光性樹脂組 成物形成圖案。 將圖案的-部分在Ν_甲基轉姻( 鐘後’藉由絲顯微鏡觀細絲_狀態。 〇：圖案沒有變化 m 25 201222154 X:圖案有裂縫產生 <殘膜率> 於檢測項目 <耐裂縫性> 中所得之預烤塗膜上任取一 測定點測得-膜厚⑷。接著將魏浸潰於航之顯影液 (2.38%四甲基氫氧化銨）1分鐘後，在相同的測定點測得另 一膜厚（(5d)。最後經下式計算即可得到殘膜率。 殘膜率(％)=[Ud)/U)] X 100 〇：殘膜率290% • △ : 90%>殘膜率280% X :殘膜率<80% 惟以上所述者，僅為本發明之較佳實施例而已，當不 能以此限定本發明實施之範圍，即大凡依本發明申請專利 範圍及發明說明書内容所作之簡單的等效變化與修飾，皆 應仍屬本發明專利涵蓋之範圍内。 【圖式簡單說明】 圖一係例示LCD用TFT陣列基板的剖視示意圖。 # 【主要元件符號說明】 101 玻璃基板 102a閘極 102b Cs電極 103氧化矽膜(SiOx) 104 氮化石夕膜(Si Nx) 105 非結晶碎層（a-Si) 106 摻雜氮不純物之非結晶石夕層 107a集極 [si 26 201222154 107b 108 109 源極 保護膜 畫素電極 201222154 比較例 | VO o o vn CN X 〇 vn o i—1 un CN 〇 JO X 〇 寸 § m m CNI ο JO X X m o m rsj r- X X CO 8 ι—Η υη 1 < CO 卜 X X i—H Ο vn CO r- X X 實施例 I 〇0 Ο Ο 〇 1200 CO f1 i 〇 〇 r- ο r- 〇 〇 \〇 ο ο ο ON 〇 〇 ο <Ν ο v〇 I ( ο s ro 〇 〇 寸 ο 卜 〇 〇 CO 〇 ο 〇 ο ο 〇 〇 〇 〇 C<J 〇 1—Η 卜 ΙΟ 〇 〇 I H o T·^ ν〇 τ-Η 1〇 Οί 卜 〇 〇 成份 Ί重量份） 1 i Ή 1 c Α-1-2 A-l-3 lA-2-l ；Α-2-2 * 1 i CO 〇ΝΪ ώ cn PQ _1 ^z2_I I CJ C<1 1 〇 ϊ—Η ώ C0 Q CO 1 Q i—H 1 PJ C<J ώ 耐裂縫性 殘膜率 酚醛清漆樹脂(A) (重量份） 含環氧丙烷基之環氧樹脂(Β) (重量份） 環氧樹脂(B’） (重量份） 鄰萘醌二疊氮磺酸類之酯化物 _(C)_ 溶劑(D) (重量份） 添加劑(E) (重量份） 檢測項目 (δίεδροι 18¾ iIAdsdpq30d> _gK]酹aHrCN-α 著329占3 §li Ills —lldvsod)謹讓«frSHEI _α 28[Synthesis Example 5] The acid varnish resin (A-2-2) was prepared in the same manner as in the above-mentioned Synthesis Example i. The difference was that the 3,4-di-furfural was substituted with a paraformaldehyde 42 gamma. [Synthesis Example 6] A nitrogen population, a heater heater, a condenser tube, and a thermometer were placed on a four-necked flask of a volume of milliliters. After introducing nitrogen gas, propylene glycol monomethyl ether acetate was added from the purpose 2 (%, 3-(曱) Base) propylene-oxymethyl-2-phenyl epoxide 30g, mercapto acrylate 25g, dicyclopentan methacrylate 35g and styrene i〇g. Slowly stir the reaction to raise the temperature to 8 (rc Then, 2 2, azobis = butyronitrile 2g was dissolved in propylene glycol monof-group-acetic acid (iv) g, and the nucleus was added at the hour interval in the four-necked flask with the fifth-injury. The reaction temperature of the polymerization process was maintained. 8 (TC, polymerization time 4 hours. After the completion of the polymerization, the solvent was devolatilized to obtain an epoxy resin containing propylene oxide group (Β_υ. [Synthesis Example 7] [S] was prepared in the same manner as in the above Synthesis Example 6. Weipropan-containing epoxy resin (Β-2), the difference is in changing the feed composition, replacing 3_(methyl) with 3 (methyl) propylene 23 201222154 oxomethoxy-3-ethyl epoxypropyl 3Qg Propyl-oxymethyl-2-phenylepoxypropene. [Synthesis Example 8] The epoxy group-containing epoxy resin (B-3) was prepared in the same manner as in the above Synthesis Example 6. Variable feed composition, replacing 3_(methyl) propylene oxymethyl-2-phenyl epoxy with 2 (methyl) propyl sulfoxymethyl-4-trifluoromethyl propylene oxide 3 〇g [Synthesis Example 9] A nitrogen inlet, a stirrer, a heater, a condenser, and a thermometer were placed on a four-necked flask having a volume of 1000 ml, and after introducing nitrogen gas, diethylene glycol dimethyl ether 200 g and methyl group were added. 3〇g of acrylic acid, 25g of glycidyl methacrylate, 20g of styrene and 25g of butyl methacrylate. Slowly stir the reaction solution to 85°C, then 2'2'-even 2 g of nitrogen bisisobutyronitrile was dissolved in diethylene glycol dimethyl ether and added to the four-necked flask at an hour interval in five equal portions. The reaction temperature during the polymerization was maintained at 85 ° C, and the polymerization time was 6 hours. After completion of the polymerization, the solvent was devolatilized to obtain an epoxy resin (B, -1). [Synthesis Example 10] An epoxy resin (B, -2) was prepared in the same manner as in the above Synthesis Example 9, except that Change the feed composition and replace the glycidyl methacrylate with o-vinylphenylhydrazine epoxidized propyl ether. <Photosensitive resin composition EXAMPLES AND COMPARATIVE EXAMPLES [Example 1] 100 parts by weight of a hydroxy novolak resin (All), 15 parts by weight of an epoxy group containing propylene oxide group (B-1), and 25 parts by weight of 2, 3, 4- 24 201222154 Mixture of di-based benzophenone with 1,2-naphthalene diazide-5-acid acid ester (ci) (average degree of esterification 85%), add 75〇 In a solvent (D-1) of propylene glycol monomethyl ether acetate in a weight fraction, the mixture is dissolved in a solvent by a stirring stirrer, and the polymerization reaction is carried out for 3 hours to obtain the positive photosensitive film of the present invention. Resin composition. The test items described below were tested and the results are shown in Table 1. [Examples 2 to 8] The same operation method as in Example 1 was carried out except that the kind of the raw material and the amount thereof were changed, and the formulation and test results are shown in Table 1. [Comparative Examples 1 to 6] The same operation method as in Example 1 was carried out except that the kind of the raw material and the materials thereof were changed, and the formulation and production results are shown in Table 1. [Test item] <Fracture resistance> The positive photosensitive resin composition was applied by spin coating on a 6 hr Wafer wafer and then pre-baked at a 丨赃 temperature for 10 seconds. A lining film. Then, in the specified mask T, ultraviolet light (exposure machine i is AG5GG-4N; manufactured by Dirty Nano Technology) 6 mJ/cm2 of light, after irradiation, then the coating film was immersed in a 23-inch developer (2. 38% of four = ugly ammonium) 6 seconds, the exposed portion of the coating film was removed, and then baked at a temperature of 160 C for 5 minutes with pure water to form a pattern of the positive photosensitive resin composition. The part-part of the pattern is transferred to the Ν_methyl group (after the clock) by the wire microscope to view the filament _ state. 〇: the pattern has no change m 25 201222154 X: the pattern has a crack generation < residual film rate><FractureResistance> The pre-baked coating film obtained on the pre-baked coating film was measured at a measurement point - film thickness (4). Then, Wei was immersed in a developing solution (2.38% tetramethylammonium hydroxide) for 1 minute. Another film thickness was measured at the same measurement point ((5d). The residual film rate was obtained by the following formula. Residual film rate (%) = [Ud) / U)] X 100 〇: residual film rate 290 % △: 90%> residual film rate 280% X: residual film rate < 80% However, the above is only a preferred embodiment of the present invention, and the scope of the present invention is not limited thereto. That is, the simple equivalent changes and modifications made by the present invention in the scope of the invention and the contents of the invention are still within the scope of the invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a TFT array substrate for LCD. # [Main component symbol description] 101 Glass substrate 102a Gate 102b Cs electrode 103 Oxide film (SiOx) 104 Nitride film (Si Nx) 105 Amorphous layer (a-Si) 106 Non-crystalline nitrogen-doped impurities Shixia layer 107a collector [si 26 201222154 107b 108 109 source protective film pixel electrode 201222154 comparative example | VO oo vn CN X 〇vn oi-1 un CN 〇JO X 〇 inch § mm CNI ο JO XX mom rsj r - XX CO 8 ι—Η υη 1 < CO 卜 i—H Ο vn CO r- XX Example I 〇0 Ο Ο 〇1200 CO f1 i 〇〇r- ο r- 〇〇\〇ο ο ο ON 〇〇ο <Ν ο v〇I ( ο s ro 〇〇 ο 〇〇 〇〇 CO 〇ο 〇ο ο 〇〇〇〇C<J 〇1—Η ΙΟ 〇〇 IH o T·^ ν〇τ -Η 1〇Οί 〇〇 〇〇 Ί 〇〇 1 1 Α 1 c Α-1-2 Al-3 lA-2-l ;Α-2-2 * 1 i CO 〇ΝΪ ώ cn PQ _1 ^z2_I I CJ C<1 1 〇ϊ-Η ώ C0 Q CO 1 Q i-H 1 PJ C<J ώ Crack-resistant residual film rate Novolak resin (A) (parts by weight) Epoxy epoxide-based epoxy resin (Β) (parts by weight) Epoxy resin (B') (parts by weight) Ester of o-naphthoquinonediazidesulfonic acid _(C)_ Solvent (D) (parts by weight) Additive (E) (parts by weight) Test item (δίεδροι 183⁄4 iIAdsdpq30d> _gK]酹aHrCN-α with 329 占3 §li Ills —lldvsod) Jean «frSHEI _α 28