201106099 六、發明說明： 【發明所屬之技術領域】 本發明係有關於—種藉由驗性水溶液可顯影之感光性樹 脂組合物、及使用該組合物之乾骐光阻。更具體而言，本 發明係有關於一種於平板顯示器之顯示材料等之製造中進 行ITO(IndiUm Tin Oxide’氧化銦錫）電極形成或鐵系合金 之钮刻（化學銑切）時較合適之感光性樹脂組合物、及使用 該組合物之乾膜光阻。 【先前技術】 先前’印刷電路板或金屬之精密加卫等係藉由光微影法 而製造。所謂光微影法，係指如下之方法：將感光性樹脂 組合物塗佈於基板上，進行圖案曝光而使該感光性樹脂組 合物之曝光部聚合硬化，以顯影液去除未曝光部而於基板 上形成光阻圖案，實施蝕刻或鍍敷處理而形成導體圖案之 後，將該光阻圖案自該基板上剝離去除，藉此於基板上形 成導體圖案。 上述光微影法中，於將感光性樹脂組合物塗佈於基板上 時’使用如下方法之任一種：#光阻溶液塗佈於基板上並 加以乾燥之方法；或將依序積層有支持體、包含感光性樹 脂組合物之層(以下稱作「感光性樹脂層」）' 及視情況之 保護層而成的感光性樹脂積層體（以下稱作「乾膜光阻」） 積層於基板上。於印刷電路板之製造中’大多情況下使用 後者之乾膜光阻。 、下對使用乾膜光阻製造印刷電路板之方法加以簡單 I48467.doc 201106099 說明。 首先自乾膜光阻剝離聚乙烯膜等保護層。其次，使用貼 合機’於銅fg基板等基板上以成為該基板、感光性樹脂 層、支持體之順序的方式積層感光性樹脂層及支持體。繼 而，經由具有佈線圖案之光罩對該感光性樹脂層進行曝 光’藉此使曝光部分聚合硬化。然、後，剝離包含聚對苯二 曱酸乙二酯等之支持體。接著，#由具有弱鹼性之水溶液 等顯影液將感紐樹脂層之未曝光部分溶解或分散去除， 於基板上形成光阻圖案。繼而，將所形成之光阻圖案作為 保護遮罩進行公知之_處理或圖案㈣處理。最後，自 基板剝離該光阻圖帛，製造具有導體圖案之基板、即印刷 電路板。 另一方面，近年來各種平板顯示器等之顯示材料之開号 盛行’且今後其料將不_大。作為此種顯示材^ 例，有形成於玻璃或聚對苯二甲酸乙二醋基材上之⑽ 極’㈣⑽刻的該電極形成中開始利用上述乾膜光阻。 但是’對於先前之乾膜光阻而言，於上述之電極形^ 中’基材與鋼等通常之金屬不同而為平滑之叮⑽、^ 膜等，故密接性較差n由於_時暴露於強酸卜 下’故存在如下問題：光阻自基材剝離而進行旁側触刻， 無法進行高精度之蝕刻加工。為克服上述問題，而導入女 矽烷偶合劑般之密接助劑。 以下之專利文IU中揭示有：藉由含有G.G1〜G5重量心 矽烷偶合劑而使感光性樹脂組合物與IT0膜之密接㈣ 148467.doc 201106099 高。但是，由於該密接助劑自身不穩定，故有使感光性樹 脂組合物之保存穩定性劣化之傾向，不可謂已充分解決了 該問題。 .又，以下之專利文獻2中記載有含有〇 〇〇1〜5重量份之於 1分子内具有2個以上巯基之多官能硫醇化合物的感光性樹 脂組合物，但作為其用途，僅揭示了作為對銅基材之密接 助劑之效果，關於與IT0膜之密接性或保存穩定性提高效 果*未作任何揭示。 [先前技術文獻] [專利文獻] [專利文獻1]曰本專利特開平1〇_198〇32號公報 [專利文獻2]曰本專利特開昭58_1〇〇844號公報 【發明内容】 [發明所欲解決之問題] 本發明所欲解決之課題係提供一種耐化學品性、與ιτ〇 膜之密接性優異且保存穩定性優異之感光性樹脂組合物， 及使用其之感光性樹脂積層體。 [解決問題之技術手段] 本發明者等人為解決上述課題而潛^研究、反覆試驗， . 結果出人意料地發現’藉由以下構成可解決上述課題，從 而完成了本案發明。 即’本發明如下所述。 一種感光性樹脂組合物，其包含（Α)鹼溶性樹脂 40〜90質量％、具有乙烯性不飽和雙鍵之化合物$〜π質 148467.doc 201106099 量。/。、（C)光聚合起始劑1〜20質量。/。、（D)環氧矽烷化合物 0.001〜2.5質量％、及（E)硫醇化合物〇 0054 〇質量0/〇。 [2]如技術方案1之感光性樹脂組合物，其中上述（e)硫 醇化合物係下述通式（I): [化1] HS—R-| ···(!) {式中，R,為具有芳香族性之基}所表示之硫醇化合物。 [3] 如上述[2]之感光性樹脂組合物，其中上述（E)通式 ⑴所示之硫醇化合物係該式中R,具有芳香族性之雜環化合 物。 [4] 如上述[2]之感光性樹脂組合物，其中上述（e)通式 (I)所示之硫醇化合物係下述通式（π): [化2]201106099 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a photosensitive resin composition developable by an aqueous solution of an aqueous solution, and a dry photoresist using the composition. More specifically, the present invention relates to an ITO (IndiUm Tin Oxide Indium Tin Oxide) electrode formation or an iron-based alloy button engraving (chemical milling) in the manufacture of a display material or the like of a flat panel display. A photosensitive resin composition and a dry film photoresist using the composition. [Prior Art] The prior 'precision of printed circuit boards or metals is manufactured by photolithography. The photolithography method is a method in which a photosensitive resin composition is applied onto a substrate, and pattern exposure is performed to thermally cure the exposed portion of the photosensitive resin composition, and the unexposed portion is removed by the developer. A photoresist pattern is formed on the substrate, and after etching or plating is performed to form a conductor pattern, the photoresist pattern is peeled off from the substrate to form a conductor pattern on the substrate. In the photolithography method, when the photosensitive resin composition is applied onto a substrate, 'any of the following methods are used: # photoresist solution is applied onto the substrate and dried; or the laminated layer is supported. A photosensitive resin laminate (hereinafter referred to as "dry film photoresist") comprising a layer of a photosensitive resin composition (hereinafter referred to as "photosensitive resin layer") and optionally a protective layer is laminated on the substrate. on. In the manufacture of printed circuit boards, the latter's dry film photoresist is used in most cases. The method of manufacturing printed circuit boards using dry film photoresist is simple. I48467.doc 201106099 Description. First, a protective layer such as a polyethylene film is peeled off from the dry film photoresist. Then, the photosensitive resin layer and the support are laminated on the substrate such as a copper fg substrate by using a bonding machine in the order of the substrate, the photosensitive resin layer, and the support. Then, the photosensitive resin layer is exposed via a photomask having a wiring pattern, whereby the exposed portion is polymerized and cured. Then, a support containing polyethylene terephthalate or the like is peeled off. Next, the unexposed portion of the sensitized resin layer is dissolved or dispersed by a developing solution such as a weakly alkaline aqueous solution to form a photoresist pattern on the substrate. Then, the formed photoresist pattern is subjected to a well-known process or pattern (four) process as a protective mask. Finally, the photoresist pattern is peeled off from the substrate to fabricate a substrate having a conductor pattern, i.e., a printed circuit board. On the other hand, in recent years, the number of display materials for various flat panel displays and the like has prevailed and will not be large in the future. As such a display material, the above-mentioned dry film photoresist is used in the formation of the electrode formed on the glass or polyethylene terephthalate substrate at the (10) pole '(4) (10). However, in the case of the above-mentioned dry film photoresist, the above-mentioned electrode shape is different from the usual metal such as steel, and is smooth (10), film, etc., so the adhesion is poor. There is a problem in that the photoresist is peeled off from the substrate and the side is touched, and high-precision etching processing cannot be performed. In order to overcome the above problems, a contact auxiliaries such as a female decane coupling agent are introduced. The following Patent Document IU discloses that the photosensitive resin composition is intimately bonded to the IT0 film by a G.G1 to G5 weight cardinal coupling agent (IV) 148467.doc 201106099. However, since the adhesion aid itself is unstable, the storage stability of the photosensitive resin composition tends to be deteriorated, and this problem has not been sufficiently solved. In the following Patent Document 2, a photosensitive resin composition containing 1 to 5 parts by weight of a polyfunctional thiol compound having two or more fluorenyl groups in one molecule is described. However, as its use, only the photosensitive resin composition is disclosed. The effect of adhesion to the IT0 film or the improvement of storage stability*, which is an effect of the adhesion aid to the copper substrate, is not disclosed. [PRIOR ART DOCUMENT] [Patent Document 1] [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. The problem to be solved by the present invention is to provide a photosensitive resin composition which is excellent in chemical resistance, adhesion to an iota film, and excellent in storage stability, and a photosensitive resin laminate using the same . [Technical means for solving the problem] The inventors of the present invention have conducted research and repeated tests to solve the above problems. As a result, it has been unexpectedly found that the above-described problems can be solved by the following configuration, and the present invention has been completed. That is, the present invention is as follows. A photosensitive resin composition comprising 40 to 90% by mass of an alkali-soluble resin and a compound having an ethylenically unsaturated double bond of 0.001467.doc 201106099. /. And (C) photopolymerization initiator 1 to 20 mass. /. (D) epoxy decane compound 0.001 to 2.5% by mass, and (E) thiol compound 〇 0054 〇 mass 0 / 〇. [2] The photosensitive resin composition according to claim 1, wherein the (e) thiol compound is represented by the following formula (I): [Chemical Formula 1] HS-R-| (·) (in the formula, R is a thiol compound represented by an aromatic group}. [3] The photosensitive resin composition according to the above [2], wherein the thiol compound represented by the above formula (E) is an aromatic heterocyclic compound of R in the formula. [4] The photosensitive resin composition according to the above [2], wherein the thiol compound represented by the above formula (e) (I) is represented by the following formula (π): [Chemical 2]
{式中，112為選自由SH、SR3〇R4&NR3R4m組成之群中的 —種基，R3及R4分別獨立為選自由H、碳數〖〜12之烷基、 及芳基所組成之群中的一種基}所表示之化合物。 [5]如上述[2]之感光性樹脂組合物，其中上述（E)硫醇 化合物係下述通式（IH): 148467.doc …（III) …（III) 201106099 [化3]Wherein 112 is a group selected from the group consisting of SH, SR3〇R4&NR3R4m, and R3 and R4 are each independently selected from the group consisting of H, an alkyl group having a carbon number of ～12, and an aryl group. a compound represented by a base}. [5] The photosensitive resin composition according to [2] above, wherein the (E) thiol compound is represented by the following formula (IH): 148467.doc (III) (III) 201106099 [Chem. 3]
{式中，Rs為選自由碳數丨〜3之烷基、碳數卜3之烷氧基、 碳數1〜3之貌硫基、SH、及Nr6r7所組成之群中的一種 基’ Re及R?分別獨立為選自由H、碳數丨〜12之烷基、及芳 基所組成之群中的一種基丨所示之化合物。 [6]如上述[1]至⑸中任一項之感光性樹脂組合物，其 中上述（D)環氧矽烷化合物係下述通式（IV): [化4] (Re〇)3纽*Ά·Β · ·., (iv) {式中’ Rs為碳數1〜5之烷基，a為碳數1〜4之烷基或 0)n-，D為碳數1〜3之烷基，η為1〜5之整數，B為具有下述 通式（V): [化5]In the formula, Rs is a group selected from the group consisting of an alkyl group having a carbon number of 丨3, an alkoxy group having a carbon number of 3, a thio group having a carbon number of 1 to 3, SH, and Nr6r7. And R? are each independently a compound represented by a group selected from the group consisting of H, an alkyl group having a carbon number of -12 to 12, and an aryl group. [6] The photosensitive resin composition according to any one of the above [1] to (5) wherein the (D) epoxydecane compound is represented by the following formula (IV): [Chem. 4] (Re〇) 3 New Zealand* Iv·Β · ·., (iv) {wherein Rs is an alkyl group having 1 to 5 carbon atoms, a is an alkyl group having 1 to 4 carbon atoms or 0) n-, and D is an alkyl group having 1 to 3 carbon atoms. Base, η is an integer of 1 to 5, and B has the following general formula (V): [Chemical 5]
所示之官能基之基}所表示之化合物。 [7]如上述[1]至[6]中任一項之感光性樹脂組合物，其 中上述（Α)鹼溶性高分子與上述（Β)具有乙烯性不飽和雙鍵 之化合物之質量比為1.5〜1.8 : 1。 148467.doc 201106099 [8] —種感光性樹脂積層體，其係於支持膜上積層有包 含如上述[1]至[7]中任一項之感光性樹脂組合物之感光性 樹脂層者。 [9] 一種光阻圖案形成方法，其特徵在於包括：將如上 述[8]之感光性樹脂積層體貼合於透明電極上之貼合步驟、 對該積層體進行曝光之曝光步驟、及對該經曝光之積層體 進行顯影之顯影步驟。 [10] —種電極之製造方法，其特徵在於按照利用如上 述[9]之圖案形成方法而獲得之光阻圖案蝕刻上述透明電 極0 [11] 一種光阻圆案形成方法，其特徵在於包括：將如 上述[8]之感光性樹脂積層體貼合於鐵系合金上之貼合步 驟、對該積層體進行曝光之曝朵+明（„ ^, ^兀*心嚓尤步驟、及對該經曝光之積 層體進行顯影之顯影步驟。 [12] -種鐵系合金構造體之製造方法，其特徵在於按 照利用如上述[11]之圖案形成方法而獲得之光阻圖案姓刻 上述鐵系合金。 [發明之效果] 根據本發明’提供一種盘ITO胳+ — Λ* I丨 很/、uo膜之密接性良好、且保存 穩定性優異之感光性樹脂組合物 D物’及使用其之感光性樹脂 積層體。本發明之感光性樹脂組合物、及使用其之感光性 樹脂積層體係圖案形成性優異，可適合用於IT0膜之钮刻 用途。 【實施方式】 148467.doc 201106099 以下，對本發明加以詳細說明。 <(A)驗溶性樹脂〉 所謂驗溶性樹脂，係指含有緩基之乙稀系樹脂，❹ (甲基）丙稀酸、（曱基）丙_醋、（曱基）丙稀猜、（甲基）丙 烯醯胺等之共聚物。 (A)鹼溶性樹脂以含有羧基、且酸當量為100〜600為 宜。所謂酸當量，係指其中具有1#量之叛基之驗溶性樹 脂之質量。 酸當量更好的是25〇以上450以下。酸當量就提高顯㈣ 性、提高解析度及密接性之方面而言，宜為1〇〇以上，就 提高顯影性及剝離性之方面而言，宜為6〇〇以下。酸當量 之測定係使用平沼產業（股）製造之平沼自動滴定裝置 (COM-555) ’利用0.1 mol/L之氫氧化鈉藉由電位差滴定法 進行。 (A)鹼溶性樹脂之重量平均分子量宜為2〇,〇〇〇以上 8〇,〇〇0以下。鹼溶性樹脂之重量平均分子量就提高顯影性 之方面而言宜為80,000以下，就顯影凝聚物之性狀、製成 感光性樹脂積層體時之邊緣熔融性、切割碎片性等未曝光 膜之性狀之觀點而言，宜為20,000以上。所謂邊緣熔融 性’係指將感光性樹脂積層體捲繞成輥狀之情形時，感光 性樹脂組合物層自輥之端面滲出之現象。所謂切割碎片 性，係指於以切割器切割未曝光膜之情形時碎片飛散之現 象’若碎片附著於感光性樹脂積層體之上面等，則會於後 續之曝光步驟等中轉印至光罩而導致不良。鹼溶性樹脂之 148467.doc 201106099 重量平均分子量更好的是20,000以上60,000以下，進而好 的是40,〇〇〇以上6〇,〇〇〇以下。 重量平均分子量係藉由日本分光（股）製造之凝膠滲透層 析儀（GPC ’ Gel Permeation Chromatography)(系：Gulliver、 PU-1 580型’管柱：昭和電工（股）製造之sh〇dex(註冊商 標）（KF-807、KF-806M、KF-806M、KF-802.5)4根串聯， 移動床溶劑：四氫呋喃，使用聚苯乙烯標準樣品（昭和電 工（股）製造之Shodex STANDARD SM-105)之校準曲線）進 行聚苯乙烯換算而求出。 驗溶性樹脂係藉由自下述兩種單體中使各一種或—種以 上之單體進行共聚合而獲得。 第一單體係分子中具有一個聚合性不飽和基之缓酸或酸 針。例如可列舉··（曱基）丙烯酸、反丁烯二酸、肉桂酸、 丁烯酸、衣康酸、順丁烯二酸酐、.及順丁烯二酸半賴。其 中’特別好的是（甲基）丙烯酸。此處，所謂（罗基）丙稀酸 係表示丙烯酸及/或甲基丙稀酸。以下相同。 第二單體為非酸性、且分子中具有至少一個聚合性不飽 和基之單體。例如可列舉：（甲基）丙烯酸甲酯、（甲基）丙 稀酸乙酯、（曱基）丙烯酸正丙酯、（曱基）丙烯酸異丙酯、 (曱基）丙烯酸正丁酯、（甲基）丙烯酸異丁酯、（甲基）丙烯酸 第二丁醋、（甲基）丙稀酸2_經基乙酯 '(曱基）丙稀酸2_羥基 丙醋、（甲基）丙烯酸2-乙基己酯、（曱基）丙烯酸苄酯，乙 烯醇之醋類、例如乙酸乙烯酯，（曱基）丙烯腈、苯乙烯、 及苯乙烯衍生物。其中，以（甲基）丙烯酸甲酯、（曱基）丙 148467.doc •10· 201106099 烯酸正丁酯、笨乙烯、（甲基）丙烯酸苄酯為宜。就顯影後 之光阻殘足部之浮渣的觀點而言，以（曱基）丙烯酸苄酯為 宜。 第一單體與第二單體之共聚合比例宜為第一單體為 10〜60質量％、第二單體為4〇〜9〇質量％，更好的是第一單 體為15〜35質量。/。、第二單體為65〜85質量。/〇。 作為第一單體與第二單體之較好組合，可列舉以下般之 組合。即，丙烯酸丁酯、曱基丙烯酸曱酯、甲基丙烯酸之 共聚物’苯乙烯、曱基丙烯酸曱酯、曱基丙烯酸之共聚 物’苯乙烯、曱基丙烯酸苄酯、甲基丙烯酸之共聚物，甲 基丙烯酸苄酯、曱基丙烯酸之共聚物，甲基丙烯酸节酿、 丙烯酸-2-乙基己酯、甲基丙烯酸之共聚物等。 關於（Α)驗溶性高分子之感光性樹脂組合物之調配量， 於將感光性樹脂組合物之總固體成分質量設為丨〇〇質量％ 時’為40〜90質量。/〇之範圍，宜為50〜70質量％。就邊緣熔 融性之觀點而言為40質量。/。以上，就顯影時間之觀點而言 為7 0質量％以下。 <(Β)具有乙稀性不飽和雙鍵之化合物> 作為（Β)具有乙烯性不飽和雙鍵之化合物，係具有至少 一個末端乙稀性不飽和基之光聚合性單體，作為具體例， 可列舉：聚丙二醇二（曱基）丙烯酸酯、聚乙二醇（甲基）丙 烯酸酯、2-二（對羥基苯基）丙烷（曱基）丙烯酸酯、甘油三 (甲基）丙烯酸酯、三羥甲基三（曱基）丙烯酸酯、聚氧丙基 三羥甲基丙烷三（曱基）丙烯酸酯、聚氧乙基三羥甲基丙烧 148467.doc -II- 201106099 三（甲基）丙烯酸酯、季戊四醇四（曱基）丙稀酸酯、二季戊 四醇五（曱基）丙稀酸酯、三曱基丙院三縮水甘油謎三（曱 基）丙烯酸酯、雙酚A乙二醇加成二（曱基）丙烯酸酯、苯氧 基聚乙二醇（甲基）丙稀酸酯、壬基苯氧基聚乙二醇（曱基） 丙稀酸g旨等。 又’亦可列舉胺基曱酸醋化合物，例如有六亞曱基二異 氰酸醋、曱苯二異氰酸酯。該等物質可單獨使用，亦可併 用兩種以上。 關於（B)具有乙稀性不飽和雙鍵之化合物之調配量，於 將感光性樹脂組合物之總固體成分質量設為1〇〇質量％ 時，為5〜50質量％。就感度、解析性、密接性之觀點而言 為5質量❶/。以上，另一方面，就抑制冷流、及硬化光阻之 剝離延遲之觀點而言為60質量％以下，宜為25〜45質量％。 <(c)光聚合起始劑> 作為（C)光聚合起始劑，可使用眾所周知者。（c)光聚合 起始劑之含量為0.^20質量％之範圍，較好範圍為〇5〜ι〇 質量％。就獲得充分之感度之觀點而言，宜為〇· i質量％以 上另方面就使光充分透射至光阻底面為止、獲得良 好之咼解析性的觀點而言，宜為20質量％以下。 作為光聚合起始劑，可列舉：2_乙基蒽醌、八乙基芽 酿、1，2-苯并蒽醌、2,3_苯并蒽醌、2_苯基蒽醌、二苯 基恩醌、1-氣蒽醌、2-氣蒽醌、2-甲基蒽醌、1，4_萘醌、 9，1〇-菲醌、2-甲基_1，4_萘醌、9，1〇_菲醌、2_甲基_1，4，萘 酿、2,3-二甲基蒽醌、3_氯·2_甲基蒽醌等醌類；芳香族酮 148467.doc 12 201106099 類’例如二苯甲酮、米其勒酮（Michier，s ket〇ne)、4,4，_雙 (一甲基胺基）二苯曱酮、4,4'_雙（二乙基胺基）二苯甲酮； 安息香或安息香醚類，安息香、安息香乙醚、安息香笨 喊、曱基安息香、乙基安息香；二烷基縮酮類，苯偶醯二 曱基縮酮、苯偶醯二乙基縮酮；9氧硫咄p星類，二乙基 氧硫咄p星、氣-9-氧硫咄P星等；二烷基胺基苯甲酸酯類，二 甲基胺基苯曱酸乙酯；肟酯類，卜苯基」，；^丙二酮_2_〇_笨 甲醯肟、1-苯基-1，2-丙二酮_2-(〇-乙氧基羰基）肟；2-(鄰氣 苯基）-4,5-二苯基咪唑二聚物、2_(鄰氯苯基）_4,5_雙_(間甲 氧基苯基）咪唑二聚物、2-(對曱氧基苯基）-4,5-二苯基咪唑 二聚物；吖啶化合物，9-苯基吖啶；吡唑啉類，苯基_3、 笨乙烯基-5-苯基-α比唑琳、ι_(4_第三丁基_苯基）·3_苯乙烯 基-5-苯基-吼唑啉' 丨_苯基_3_(4_第三丁基_苯乙烯基）_5_(4_ 第三丁基-苯基）-吡唑啉等。該等化合物可單獨使用，亦可 併用兩種以上。 上述咯吩二聚物與米其勒酮、4,4，-雙（二曱基胺基）二笨 甲嗣或4,4·-雙（二乙基胺基）二苯甲酮之組合就感度及解析 度之觀點而言為較好組合。此時’咯吩二聚物可根據感度 或顯影凝聚性而適當調節調配量。於使用2-(鄰氯苯基）_ 4,5-二苯基咪唑二聚物之情形時’就感度之觀點而言宜為1 質量％以上，就凝聚性之觀點而言宜為5質量。/。以下。更好 的是2〜4質量。4,4，-雙（二乙胺基）二苯甲酮可考慮感度、 光阻圖案之矩形性、曝光波長之光線透射率而適當調整調 配量。於形成70 μιη以上之厚膜之感光性樹脂層時，考慮 148467.doc •13· 201106099 到圖案之密接性、矩形性’宜設定為0 05質量％以下。就 感度之觀點而言宜為0.01質量％以上。 <(D)環氧矽烷化合物> 所謂（D)環氧矽烷化合物’係指於分子内同時具有與有 機材料反應鍵結之環氧基、及與無機材料反應鍵結之水解 性烷氧基的有機矽化合物，其中就密接性之觀點而言，宜 為下述通式（IV): [化6] (RgO)3Si»A*B ·、· <IV} {式中，Rs為碳數1〜5之烷基，A為碳數之烷基或气d_ 〇)n-，D為碳數1〜3之烷基，11為1〜5之整數，B為具有下述 通式（V): [化7]A compound represented by the group of functional groups shown. The photosensitive resin composition of any one of the above-mentioned [1] to [6], wherein the mass ratio of the above (Α) alkali-soluble polymer to the above (Β) compound having an ethylenically unsaturated double bond is 1.5~1.8: 1. 148. The method of the photosensitive resin layer of the photosensitive resin composition of any one of the above [1] to [7] is laminated on the support film. [9] A method for forming a photoresist pattern, comprising: a bonding step of bonding a photosensitive resin laminate of the above [8] to a transparent electrode, an exposure step of exposing the laminate, and The development step of developing the exposed laminate. [10] A method of manufacturing an electrode, characterized in that the transparent electrode 0 is etched according to a photoresist pattern obtained by the pattern forming method of [9] above [11], which is characterized in that it comprises a step of bonding a photosensitive resin laminate according to the above [8] to an iron-based alloy, and exposing the laminate to exposure („^, ^兀*心嚓, and a development step of developing the laminated body by exposure. [12] A method for producing an iron-based alloy structure, characterized in that the above-mentioned iron system is surnamed according to a photoresist pattern obtained by the pattern forming method as described in [11] above. [Effects of the Invention] According to the present invention, there is provided a photosensitive resin composition D of a disk ITO — — 丨 丨 丨 、 、 、 、 、 、 、 、 、 uo uo uo 及 及 及 及 及 及 及 及 及The photosensitive resin composition of the present invention and the photosensitive resin layered system using the same are excellent in pattern formation property, and can be suitably used for buttoning applications of the IT0 film. [Embodiment] 148467.doc 201106099 Correct The present invention will be described in detail. <A> A solvent-soluble resin> A solvent-soluble resin is a vinyl resin containing a buffer base, ❹(methyl)acrylic acid, (mercapto)propyl vinegar, (曱) a copolymer of (meth) acrylamide or the like. (A) The alkali-soluble resin preferably contains a carboxyl group and has an acid equivalent of 100 to 600. The acid equivalent means that it has a quantity of 1#. The quality of the repellent resin of the rebel base. The acid equivalent is more preferably 25 〇 or more and 450 or less. The acid equivalent is improved in terms of (four) properties, and the resolution and adhesion are preferably 1 〇〇 or more. In terms of properties and releasability, it should be 6 〇〇 or less. The acid equivalent is determined by using the Pingyu automatic titrator (COM-555) manufactured by Hiranuma Industry Co., Ltd. 'Using 0.1 mol/L sodium hydroxide (A) The weight average molecular weight of the alkali-soluble resin is preferably 2 Torr, 8 〇〇〇 or more, and 〇〇0 or less. The weight average molecular weight of the alkali-soluble resin is preferably 80,000 in terms of improving developability. Hereinafter, the properties of the coagulum are developed to prepare a photosensitive resin. In view of the properties of the unexposed film such as the edge meltability and the dicing property of the layer, it is preferably 20,000 or more. The term "edge melting property" refers to a case where the photosensitive resin laminate is wound into a roll shape. The phenomenon that the layer of the resin composition oozes from the end surface of the roll. The term "cutting fragmentation" refers to a phenomenon in which the chip scatters when the unexposed film is cut by the cutter, and if the chip adheres to the surface of the photosensitive resin layered body, It will be transferred to the mask in the subsequent exposure step, etc., resulting in a defect. The alkali-soluble resin 148467.doc 201106099 The weight average molecular weight is more preferably 20,000 or more and 60,000 or less, and further preferably 40, 〇〇〇 or more. 〇〇〇The following. The weight average molecular weight is a GPC 'Gel Permeation Chromatography (manufactured by Gulliver, PU-1 580' column: sh〇dex manufactured by Showa Denko Co., Ltd. (registered trademark) (KF-807, KF-806M, KF-806M, KF-802.5) 4 in series, moving bed solvent: tetrahydrofuran, using polystyrene standard sample (Shodex STANDARD SM-105 manufactured by Showa Denko) The calibration curve is obtained by polystyrene conversion. The solvent-soluble resin is obtained by copolymerizing one or more monomers from the following two types of monomers. A slow acid or acid needle having a polymerizable unsaturated group in the first single system molecule. For example, (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid are used. Among them, '(meth)acrylic acid is particularly preferable. Here, the "robase" acrylic acid means acrylic acid and/or methacrylic acid. The same is true below. The second monomer is a monomer which is non-acidic and has at least one polymerizable unsaturated group in the molecule. For example, methyl (meth)acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, ( Isobutyl methacrylate, second butyl ketone (meth) acrylate, (meth) acrylate 2 _ propyl ethyl ketone '(mercapto) acrylic acid 2 hydroxy propyl vinegar, (meth) acrylic acid 2-ethylhexyl ester, benzyl (meth) acrylate, vinegar of vinyl alcohol, such as vinyl acetate, (mercapto) acrylonitrile, styrene, and styrene derivatives. Among them, methyl (meth)acrylate, (mercapto)propyl 148467.doc •10·201106099 n-butyl acrylate, stupid ethylene, benzyl (meth)acrylate is preferred. From the viewpoint of the scum of the residual portion of the photoresist after development, benzyl (meth) acrylate is preferred. The copolymerization ratio of the first monomer to the second monomer is preferably 10 to 60% by mass of the first monomer, 4 to 9% by mass of the second monomer, and more preferably 15% of the first monomer. 35 quality. /. The second monomer is 65 to 85 mass. /〇. As a preferable combination of the first monomer and the second monomer, the following combinations are exemplified. That is, a copolymer of butyl acrylate, decyl methacrylate, methacrylic acid copolymer 'styrene, decyl decyl acrylate, methacrylic acid copolymer' styrene, benzyl methacrylate, methacrylic acid , benzyl methacrylate, copolymer of methacrylic acid, methacrylic acid brewing, copolymer of 2-ethylhexyl acrylate, methacrylic acid, and the like. In the case where the total solid content of the photosensitive resin composition is 丨〇〇% by mass, the amount of the photosensitive resin composition of the photosensitive polymer composition is 40 to 90% by mass. / 〇 range, should be 50~70% by mass. It is 40 mass in terms of edge melting. /. The above is 70% by mass or less from the viewpoint of development time. <(Β) Compound having an ethylenically unsaturated double bond> A compound having an ethylenically unsaturated double bond as a photopolymerizable monomer having at least one terminal ethylenically unsaturated group as Specific examples thereof include polypropylene glycol bis(indenyl) acrylate, polyethylene glycol (meth) acrylate, 2-bis(p-hydroxyphenyl)propane (fluorenyl) acrylate, and tris(methyl) glycerol. Acrylate, trimethylol tris(mercapto) acrylate, polyoxypropyl trimethylolpropane tris(mercapto) acrylate, polyoxyethyl trimethylol propyl 148467.doc -II- 201106099 (meth) acrylate, pentaerythritol tetrakis(mercapto) acrylate, dipentaerythritol penta(indenyl) acrylate, trisyl propyl triglycidyl succinyl sulfonate, bisphenol A Ethylene glycol addition bis(indenyl) acrylate, phenoxy polyethylene glycol (meth) acrylate, nonyl phenoxy polyethylene glycol (mercapto) acrylic acid g. Further, an amino phthalic acid vinegar compound may be mentioned, for example, hexamethylene diisocyanate or benzene diisocyanate. These may be used singly or in combination of two or more. (B) The compounding amount of the compound having a ethylenically unsaturated double bond is 5 to 50% by mass based on the total solid content of the photosensitive resin composition of 1% by mass. It is 5 mass ❶ / in terms of sensitivity, analyticity, and adhesion. On the other hand, from the viewpoint of suppressing the cold flow and the peeling retardation of the cured photoresist, it is preferably 60% by mass or less, and preferably 25 to 45% by mass. <(c) Photopolymerization initiator> As the (C) photopolymerization initiator, those well known can be used. (c) Photopolymerization The content of the initiator is in the range of 0.20% by mass, preferably in the range of 〇5 to 〇5% by mass. From the viewpoint of obtaining sufficient sensitivity, it is preferably 20% by mass or less from the viewpoint of sufficiently transmitting light to the bottom surface of the photoresist and obtaining good analytical properties. Examples of the photopolymerization initiator include 2-ethyl oxime, octaethyl bud, 1,2-benzopyrene, 2,3-benzopyrene, 2-phenylhydrazine, and diphenyl. Keen, 1-gas, 2-gas, 2-methylindole, 1,4-naphthoquinone, 9,1〇-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 9,1〇_phenanthrenequinone, 2_methyl_1,4, naphthalene, 2,3-dimethylindole, 3_chloro·2_methylindole, etc.; aromatic ketone 148467.doc 12 201106099 Classes such as benzophenone, Michier, s ket〇ne, 4,4, bis(monomethylamino)benzophenone, 4,4'-double (diethyl Aminophene) benzophenone; benzoin or benzoin ether, benzoin, benzoin ethyl ether, benzoin stupid, sulfhydryl benzoin, ethyl benzoin; dialkyl ketals, benzoin decyl ketals, benzo Bismuth diethyl ketal; 9 oxopurine p star, diethyl oxysulfonate p star, gas-9-oxopurine P star, etc.; dialkylamino benzoate, dimethylamino Ethyl benzoate; oxime ester, phenyl phenyl), propylene glycol ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone Alkylcarbonyl)肟;2-( Phenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis-(m-methoxyphenyl)imidazole dimer, 2-(p-methoxyl) Phenyl)-4,5-diphenylimidazole dimer; acridine compound, 9-phenyl acridine; pyrazoline, phenyl _3, stupid vinyl-5-phenyl-α-biazole , ι_(4_Terbutyl-phenyl)·3_styryl-5-phenyl-oxazoline' 丨_phenyl_3_(4_t-butyl-styryl)_5_(4_ Third butyl-phenyl)-pyrazoline and the like. These compounds may be used singly or in combination of two or more. The combination of the above-mentioned oleo-dimer with micilerone, 4,4,-bis(didecylamino)dipyridamidine or 4,4·-bis(diethylamino)benzophenone From the viewpoint of sensitivity and resolution, it is a good combination. At this time, the amount of the compound can be appropriately adjusted depending on the sensitivity or the development cohesiveness. In the case of using 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, it is preferably 1% by mass or more from the viewpoint of sensitivity, and is preferably 5 mass from the viewpoint of cohesiveness. . /. the following. Better is 2 to 4 mass. The 4,4,-bis(diethylamino)benzophenone can be appropriately adjusted in consideration of the sensitivity, the squareness of the resist pattern, and the light transmittance of the exposure wavelength. In the case of forming a photosensitive resin layer of a thick film of 70 μm or more, it is preferable to set the adhesion to the pattern and the squareness of 148467.doc •13·201106099 to 0.05 mass% or less. It is preferably 0.01% by mass or more from the viewpoint of sensitivity. <(D) Epoxydecane compound> The term "(D) epoxydecane compound" means an epoxy group having a bond with an organic material in a molecule and a hydrolyzable alkoxy group bonded to an inorganic material. The organic hydrazine compound of the group, wherein from the viewpoint of adhesion, is preferably the following general formula (IV): [Chemical Formula 6] (RgO) 3Si»A*B ·, · <IV} {wherein, Rs is An alkyl group having 1 to 5 carbon atoms, A is an alkyl group having a carbon number or a gas d_ 〇) n-, D is an alkyl group having 1 to 3 carbon atoms, 11 is an integer of 1 to 5, and B is a compound having the following formula (V): [Chem. 7]
所示之官能基之基}所表示之化合物。 作為具體例，可列舉：2_(3,4_環氧環己基）乙基三曱氧 基矽烷、3'缩水甘油氧基甲基三甲乳基矽烷、3'缩水甘油 氧基乙基三甲氧基我、3_縮水甘油氧基丙基三曱氧基碎 烷、3一-縮水甘油氧基丙基三乙氧基矽烷、3'缩水甘油氧基 丙基三丙t基矽⑨、3'缩水甘油氧基丙基三丁氧基矽烷、 3-縮水甘油氧基丙基三戊氧基㈣、3_縮水甘油基甲基三 148467.doc 14 201106099 曱氧基矽烷、3'缩水甘油基乙基三甲氧基矽烷、3'缩水甘 油基丙基—甲氧基矽烷等。作為（D)環氧矽烷化合物就 密接性之觀點而言，上述中更好的是2_(3,4-環氧環己基） 乙基三甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、 3-縮水甘油氧基丙基三乙氧基矽烷。關於環氧矽烷化 δ物之調配置，於將感光性樹脂組合物之總固體成分質量 設為loot量％時’為0顧〜2 5f量。/。。就密接性之觀點而 言為0.0G1質量％以上，另—方面，就保存穩定性之觀點而 吕為2.5質量％以下。（D)環氧矽烷化合物之調配量宜為 0.03〜0.3質量％，更好的是〇 〇5〜〇 15質量％。 <(E)下述通式⑴所表示之硫醇化合物> 本發明所含之感光性樹脂組合物含有〇 0054 〇質量％之 (E)硫醇化合物，藉此可期待提高保存穩定性之效果。於 本案中，所s胃保存穩定性，係指已將感光性樹脂積層體曝 光時之對比度不會隨時間而變化。 作為（E)硫醇化合物，可列舉：巯基鍵結於不具芳香族 性之碳原子的化合物、疏基鍵結於具有芳香族性之基的化 合物。 作為巯基鍵結於不具芳香族性之碳原子的化合物，例如 可列舉.辛硫醇、己二硫醇、癸二硫醇、丨,4_丁二醇雙硫 代丙k g曰、1，4- 丁一醇雙硫基乙酸酯、乙二醇雙魏基乙酸 酯、乙二醇雙硫代丙酸酯、三羥曱基丙烷三酼基乙酸酯、 二羥甲基丙烷三硫代丙酸酯、三羥甲基丙烷三（3_巯基丁酸 西5 )、季戊四醇四巯基乙酸酯、季戊四醇四硫代丙酸酯、 148467.doc 15 201106099 季戊四醇四-3-疏 三毓基丙酸三（2-羥基乙基）異氰尿酸酯 基丁酸酯。 之基的化合物，可列舉下 作為毓基鍵結於具有芳香族性 述通式（I):A compound represented by the group of functional groups shown. Specific examples include 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, 3' glycidoxymethyl dimethyl methoxy decane, and 3' glycidoxyethyl trimethoxy group. I, 3_glycidoxypropyltrimethoxyoxycane, 3-glycidoxypropyltriethoxydecane, 3'glycidoxypropyltripropenylhydrazine 9,3' shrinkage Glycidoxypropyl tributoxy decane, 3-glycidoxy propyl tripentyloxy (tetra), 3-glycidylmethyl tri 148467.doc 14 201106099 decyloxydecane, 3' glycidylethyl Trimethoxydecane, 3' glycidylpropyl-methoxydecane, and the like. As the (D) epoxydecane compound, from the viewpoint of adhesion, 2_(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropyltrimethoxy is more preferable. Alkane, 3-glycidoxypropyltriethoxydecane. When the total solid content of the photosensitive resin composition is set to the amount of the loot amount, the amount of the epoxy group is adjusted to be 0 to 25%. /. . From the viewpoint of adhesion, it is 0.0 G1% by mass or more, and on the other hand, from the viewpoint of storage stability, it is 2.5% by mass or less. The compounding amount of the (D) epoxy decane compound is preferably 0.03 to 0.3% by mass, more preferably 〇5 to 〇 15% by mass. <(E) The thiol compound represented by the following formula (1)> The photosensitive resin composition contained in the present invention contains 〇0054% by mass of the (E) thiol compound, whereby storage stability can be expected The effect. In the present case, the stability of the stomach preservation means that the contrast when the photosensitive resin laminate is exposed is not changed with time. The (E) thiol compound may, for example, be a compound in which a thiol group is bonded to a carbon atom having no aromaticity, or a compound in which a thiol group is bonded to an aromatic group. Examples of the compound in which a thiol group is bonded to a carbon atom having no aromaticity include, for example, octyl mercaptan, hexanedithiol, decanedithiol, hydrazine, 4-butanediol bisthiopropyl ketone, 1,4. - Butanol dithioacetate, ethylene glycol diweit acetate, ethylene glycol dithiopropionate, trishydroxypropyl propane tridecyl acetate, dimethylolpropane trithiopropyl Acid ester, trimethylolpropane tris(3_mercaptobutyric acid West 5), pentaerythritol tetradecyl acetate, pentaerythritol tetrathiopropionate, 148467.doc 15 201106099 pentaerythritol tetrakis-3-diazepine propionic acid Tris(2-hydroxyethyl)isocyanurate butyl butyrate. The compound of the group can be exemplified as having a thiol group bonded to have an aromatic formula (I):
[化8J HS—Ri ...⑴ {式中’ Rl為具有芳香族性之基}所表示之硫醇化合物。 作為上述具有芳香族性之基，例如可列舉：苯基、蔡 基、蒽基、味唾基、三„坐基、四唾基、苯并味唾基、苯并 三唑基、苯并四唑基、呤唑基、苯并吟唑基、噻唑基、笨 并嗟。坐基、。塞二哇基、三，井基…比W各基、吱喃 基' 噻吩基、喹啉基。 R】就保存穩定性之觀點而言宜為具有芳香族性之雜環化 合物。本案中，解析度係指使用將線之線寬與間隙寬以ι〇 μηι〜50 μπι之等寬交替排列之底片作為解析度評價用底 片藉由顯影使未曝光部完全膨潤·溶解去除所得之間隙 之最小寬度。 作為此種上述通式（I)所表示之硫醇化合物，例如可列 舉.2-氣苯硫紛、3-氣苯硫酚、4-氣苯硫盼、2-胺基苯硫 驗、3 -胺基苯硫驗、4-胺基苯硫盼、2-漠苯硫紛、3-漠苯 硫酚、4·溴苯硫酚、2-氟苯硫酚、3-氟苯硫酚、4-氟苯硫 盼、1，2-二酼基苯、1，3-二巯基苯、1，4-二酼基苯、2,3-二 曱基苯硫酚、2,4-二曱基笨硫酚、2,5-二曱基苯硫酚、2,6_ 148467.doc -16- 201106099 二甲基苯硫酚、2,3-二氟苯硫酚、2,4-二氟苯硫酚、2,5-二 氟苯硫酚、2,6-二氟苯硫酚、2,3_二氣苯硫酚、2,4-二氣笨 硫酚、2,5-二氯苯硫酚、2,6-二氣苯硫酚、3,4-二甲氧基苯 硫酚、3-氯-4-氟苯硫酚、4-異丙基苯硫酚、3,5-(三氣甲 基）笨硫醇、2-疏基苯甲酸、2-胺基-4-氣苯硫齡、4-乙酿胺 苯硫酚、2-氯_4_氟笨硫酚、4-氣-2,5-二曱基笨硫盼、 1，3,5-三酼基苯、5-溴-1,3-二毓基苯、2,3,5,6-四氟苯硫 酚、2-巯基吡啶、3-毓基吡啶、4-巯基吡啶、2-巯基吡咬_ N-氧化物、5-曱氧基-2-苯并咪唑硫醇、5_胺基_2_巯基苯并 咪唑、2-巯基-1-甲基咪唑、2-酼基-5-曱基苯并咪唑、2-巯 基-5-硝基苯并咪唑、4_羥基-2-疏基-6-(三氟甲基）嘧啶、4-毓基吡唑幷[3,4d]嘧啶、4,6-二胺基-2_鲸基嘧啶、4,6_二羥 基-2-巯基嘧啶、2-巯基-4,6-二甲基嘧啶' 5_苯基4,3,4-噚 一坐-2-硫醇、4,5-一本基-2-疏基号β坐、2_苯并崎β坐琉醇、 3-苯基-1，2,4-三唑-5-硫醇、5-巯基_1_曱基四唑、卜苯基_5_ 毓基-1Η-四唑、2-巯基咪唑琳。 上述通式（I)所表示之硫醇化合物更好的是下述通式 (II): [化9][Chemical Formula 8J HS-Ri (1) where R1 is a thiol compound represented by an aromatic group}. Examples of the aromatic group include a phenyl group, a decyl group, a fluorenyl group, a sulphate group, a tris-sodium group, a tetrasyl group, a benzo-salt group, a benzotriazole group, and a benzotetrazole. Azolyl, oxazolyl, benzoxazolyl, thiazolyl, benzoxanthene, succinyl, sulphate, sylylene, sylylene, sylylene, quinolyl, quinolyl. R] is preferably an aromatic heterocyclic compound from the viewpoint of storage stability. In the present case, the resolution means that the line width and the gap width are alternately arranged in the same width as ι 〇 μηι to 50 μπι. The negative film is a minimum width of the gap obtained by the development of the film for the evaluation of the film, and the thiol compound represented by the above formula (I) is exemplified. Sulfur, 3-air thiophenol, 4-gas benzene thiophene, 2-aminophenyl thiosulfate, 3-aminophenyl thiosulfate, 4-aminophenylthione, 2-indisulfur sulphate, 3- Ruthenol, 4·Bromothiophenol, 2-fluorothiophenol, 3-fluorothiophenol, 4-fluorophenylthione, 1,2-dimercaptobenzene, 1,3-dioxylbenzene, 1,4-didecylbenzene 2,3-dimercaptothiophenol, 2,4-dimercaptothiophenol, 2,5-dimercaptothiophenol, 2,6_148467.doc -16- 201106099 dimethylthiophenol, 2,3-difluorothiophenol, 2,4-difluorothiophenol, 2,5-difluorothiophenol, 2,6-difluorothiophenol, 2,3-dioxathiophenol, 2,4-dioxathiophenol, 2,5-dichlorothiophenol, 2,6-dithiothiophenol, 3,4-dimethoxythiophenol, 3-chloro-4-fluorobenzene Thiol, 4-isopropylthiophenol, 3,5-(trimethylmethyl) thiol, 2-sulfobenzoic acid, 2-amino-4-gas benzoate, 4-ethylamine Thiophenol, 2-chloro-4_fluorothiophenol, 4-gas-2,5-dimercaptothiophene, 1,3,5-trimercaptobenzene, 5-bromo-1,3-di Nonylbenzene, 2,3,5,6-tetrafluorothiophenol, 2-mercaptopyridine, 3-mercaptopyridine, 4-mercaptopyridine, 2-mercaptopurine_N-oxide, 5-decyloxy -2-benzimidazole thiol, 5-amino-2-indolylbenzimidazole, 2-mercapto-1-methylimidazole, 2-mercapto-5-mercaptobenzimidazole, 2-mercapto-5- Nitrobenzimidazole, 4-hydroxy-2-pyridyl-6-(trifluoromethyl)pyrimidine, 4-mercaptopyrazolo[3,4d]pyrimidine, 4,6-diamino-2-whale Pyrimidine, 4,6-dihydroxy-2-mercaptopyrimidine, 2- Benzyl-4,6-dimethylpyrimidine '5-phenyl 4,3,4-indole-yl-2-thiol, 4,5-mono-yl-2-ylyl-β, 2-benzoyl Saki β-sitosterol, 3-phenyl-1,2,4-triazole-5-thiol, 5-mercapto-1_indolyltetrazole, phenyl _5_ decyl-1 Η-tetrazole, 2 - mercapto imidazole. The thiol compound represented by the above formula (I) is more preferably the following formula (II): [Chemical 9]
148467.doc •17· 201106099 {式中，R2為選自由SH、SR3〇R4及nr3r4所組成之群中的 種基，R3及R4分別獨立為選自由Η、碳數1〜12之烷基、 及芳基所組成之群中的一種基}所表示 之化合物。 作為上述通式（II)所表示之硫醇化合物，例如可列舉： 2’4,6·三疏基-均三畊、2-二-正丁基胺基-4,6-二巯基-均彡 口井、2-苯胺基_4,6_二巯基_均三啡、6_二烯丙基胺基- 二畊-2,4-二硫醇、2_二環己基胺基_4,6_二巯基-均三p井、 一曱基胺基-1，3,5-三口井_2,4_二硫醇。 又作為上述通式（I)所表示之硫醇化合物，下述通式 (III): [化 10]148467.doc •17· 201106099 {wherein, R2 is a group selected from the group consisting of SH, SR3〇R4, and nr3r4, and R3 and R4 are each independently selected from an alkyl group having a ruthenium and a carbon number of 1 to 12, And a compound represented by a group in the group consisting of aryl groups. Examples of the thiol compound represented by the above formula (II) include: 2'4,6·tris-salt-average three-till, 2-di-n-butylamino-4,6-diindenyl- Sakaguchi well, 2-anilino-4,6-dimercapto-s-trisyl, 6-diallylamino-secondic-2,4-dithiol, 2-dicyclohexylamino-4 6_Dimercapto-seven-p well, monodecylamine-1,3,5-three wells _2,4-dithiol. Further, as the thiol compound represented by the above formula (I), the following formula (III): [Chemical 10]
-18- 201106099 5-異丙氧基·㈣U3,4_H5•甲硫基⑭基 售-唾、5-乙硫基-2，基十认。塞二吐、5_正丙硫基韻 基-U4-嗟二吐、5·異丙硫基_2遏基_u，4“塞二唾、5_胺 基-2-魏基“塞二唾。 特別是5-胺基-2-疏基_；1，3,4“塞二σ坐、2_二_正了基胺基· 4,6-二疏基·均三呼由於維持保存穩定性之效果較高，故較 好。該等物質可單獨使用’亦可併用兩種以上。 關於⑻上述通式⑴所表示之硫醇化合物之感光性樹脂 組合物之調配量將感光性樹脂組合物之總固體成分質 量設為_質量％之時，為〇.〇〇5〜1〇質量％之範圍，宜為 〇·01〜0.1質量％之範圍’更好的是0.03〜0.08質量％之範 圍。就維持保存穩定性之觀點而言為0.005質量％以上，另 一方面，就解析度之觀點而言為1〇質量％以下。 <其他成分> 本發明之感光性樹脂組合物亦可含有隱色染料或熒烷染 料或者著色物質。藉由含有該等染料而曝光部分顯色故 就視覺確認性之方面而言較好。χ，含㈣些染料之情況 下，於檢查機等讀取用α進行曝光之對位標記日夺，曝光部 與未曝光部之對比度較大時容易識別而有利。 作為隱色染料，可列舉：三（4-二曱基胺基苯基）曱烧[隱 色、°曰曰务' ]雙（4_ 一曱基胺基苯基）苯基曱烧[隱色孔雀 綠]。其中，就對比度良好之觀點而言，作為隱色染料， 且使用隱色結晶紫。含有隱色染料時之含量宜為於感光性 树月曰組合物中含有〇 i〇質量。/(^該含量就曝光部分與未 148467.doc 19 201106099 本光邛刀之對比度之觀點而言宜為〇」質量。以上，又，就 維持保存穩定性之觀點而言，宜為⑽量％以下。 η 又’於感純樹脂組合物中組合使用隱色染料與下述齒 素化合物，就密接性及對比度之觀點而言係本發明之較好 實施形態。 作為著色物質，例如可列舉：品紅、酉太菁綠、金黃胺 鹼、對品紅、結晶紫、甲基橙、尼羅藍2Β、維多利亞藍、 孔雀綠（保土谷化學（股）製造之Aizen(註冊商標） mALACHITE GREEN)、驗性藍2〇、鑽石綠（保土谷化學 (股）製造之Aizen(註冊商標）DIAM〇ND green gh卜含有 著色物質時之添加量宜為於感光性樹脂組合物中含有 0.001〜1質量❶/。。就操作性提高之觀點而言，含量宜為 〇.〇〇!質量。/。以上，另外，就維持保存穩定性之觀點而言·， 含量宜為1質量％以下。 於感光性樹脂組合物中’就感度之觀點而言亦可含有N_ 芳基-ex-胺基酸化合物。作為N_芳基_α_胺基酸化合物，以 ^苯基甘胺酸為宜。含有Ν_芳基_α_胺基酸化合物時之含 1且為0. 〇 1質量％以上1質量％以下。 感光性樹脂組合物亦可含有函素化合物。作為齒素化合 物，例如可列舉：演戊烧、$異戊烧、演化異丁稀、漠化 乙烯一笨/臭代曱烧、苄基溴、二溴甲烷、三溴甲基苯基 風四溴化碳、磷酸二(2,3_二溴丙基)酯、三氣乙醯胺、 埃戊烷、異丁基蛾、U，1·三氣-2,2-雙（對氣苯基）乙院、氣 化三畊化合物等，纟中可特別好地使用三溴曱基苯基颯。 148467.doc 201106099 含有函素化合物時之含量於感光性樹脂組合物 .質量％。 又，為了提高感光性樹脂組合物之熱穩定性、 性，感光性樹脂組合物亦可進而含有選自由自由基聚= 制劑、笨并三唾類、及羧基苯并三崎類所組成之群中的至 少1種以上之化合物。 主 :為自由基聚合抑制劑，例如可列舉：對甲 :本二：、鄰苯三齡、蔡胺、第三丁基鄰笨二齡、氣化亞 :二一第三丁基州、2,2，_亞甲基雙("基_6·第 二丁基本齡）、2,2|_亞,基雙（4_乙基_6_第三丁基物、亞 蜗基苯縫基胺㈣、二苯基亞硝基胺等。 作為+苯并一三唾類，例如可列舉：i，2,3苯并三唾叫·氣_ 1’2’3·本并二唾、雙（N_2•乙基己基）胺基亞甲基十2,3_苯并 二唾、雙（N^乙基己基）胺基亞甲基曱苯三嗤、雙 (N-2-絲乙基）胺基亞甲基·苯并三唾等。-18- 201106099 5-Isopropoxy-(iv) U3,4_H5•Methylthio- 14-base Sale-Sal, 5-ethylthio-2, keidine.塞二吐,5_正丙硫基的基基-U4-嗟二吐,5·isopropylthio-2-inhibitor _u,4" stoppered two-salt, 5-amino-2-weiry" saliva. In particular, 5-amino-2-carbyl-; 1,3,4"-Sexy-sigma sitting, 2_di-n-ylamino- 4,6-di-s-based, all-three-hook due to maintaining storage stability The amount of the photosensitive resin composition of the thiol compound represented by the above formula (1) may be two or more. The photosensitive resin composition may be used in combination with the thiol compound represented by the above formula (1). When the total solid content is _ mass%, it is in the range of 〜. 5 to 1 〇 mass%, preferably in the range of 〇·01 to 0.1% by mass, and more preferably in the range of 0.03 to 0.08 mass%. The viewpoint of the storage stability is 0.005% by mass or more, and on the other hand, it is 1% by mass or less from the viewpoint of the resolution. <Other components> The photosensitive resin composition of the present invention may also be used. Containing a leuco dye or a fluoran dye or a coloring matter. It is better in terms of visual confirmation by exposing a part of the color by containing the dye. χ, containing (4) some dyes, reading in an inspection machine, etc. The alignment mark is taken by α, and the contrast between the exposed portion and the unexposed portion is large. It is easy to identify and is advantageous. As a leuco dye, tris(4-didecylaminophenyl) oxime [hidden color, 曰曰 ' ' ] bis (4 _ fluorenyl phenyl) phenyl曱 [ [hidden peacock green]. Among them, as a leuco dye, leuco crystal violet is used as a leuco dye, and the leuco dye is preferably contained in the photosensitive sapphire composition. 〇i〇 quality./(^ The content is preferably 〇 〇 〇 148 148 467 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 It is preferably (10)% or less. η "In combination with a leuco dye and a dentate compound as described below, it is a preferred embodiment of the present invention from the viewpoint of adhesion and contrast. For example, magenta, phthalocyanine green, golden amine base, rhodopsin, crystal violet, methyl orange, Nile blue 2, Victoria blue, malachite green (Aizen manufactured by Baotu Valley Chemical Co., Ltd.) ) mALACHITE GREEN), blue test 2, diamond (Aizen (registered trademark) DIAM 〇 ND green gh manufactured by Hodogaya Chemical Co., Ltd. is preferably added in an amount of 0.001 to 1 mass 于 / in the photosensitive resin composition when the coloring matter is contained. In view of the above, the content of the photosensitive resin composition is preferably 1% by mass or less. In view of the above, an N-aryl-ex-amino acid compound may also be contained. As the N-aryl_α-amino acid compound, it is preferred to use phenylglycine, which contains a Ν_aryl-α-amino group. The acid compound contains 1 and is 0. 〇1% by mass or more and 1% by mass or less. The photosensitive resin composition may also contain a functional element compound. Examples of the dentate compound include: executor, valence, evolution of isobutylene, desertified ethylene, stupid/odor, benzyl bromide, dibromomethane, tribromomethylphenyl tetrabromide. Carbon, di(2,3-dibromopropyl) phosphate, triethylene acetamide, pentane, isobutyl moth, U, 1 · tri-gas-2, 2-bis (p-phenyl) In the case of the hospital, the gasification of the three-till compound, etc., tribromodecylphenyl hydrazine can be used particularly well. 148467.doc 201106099 Content in the case of containing a functional compound in a photosensitive resin composition. Moreover, in order to improve the thermal stability and the properties of the photosensitive resin composition, the photosensitive resin composition may further contain a group selected from the group consisting of a radical poly-formulation, a stupid trisal, and a carboxybenzotris. At least one or more compounds. Main: It is a radical polymerization inhibitor, for example, it can be exemplified by: a pair: this two: phthalate, erbamine, butyl butyl, bismuth, gasification: two, third butyl, 2 , 2, _ methylene double (" base _6 · second butyl age), 2, 2 | _ sub, bis (4_ethyl _6_ third butyl, subvortex benzene The base amine (tetra), diphenyl nitrosamine, etc. As the + benzotrisole, for example, i, 2, 3 benzotrisole gas _ 1 '2' 3 · bis, Bis(N_2•ethylhexyl)aminomethylene-10-2,3-benzodiazepine, bis(N^ethylhexyl)aminomethylenesulfonium Benzene, bis(N-2-silylethyl) Aminomethylene, benzotrisene, and the like.
作為竣基本开三唾類，例如DU 5邊基切-苯并三唾W二-2-乙基己細 ί缓开三唾、Ν·(Ν，Ν〜經基乙基）胺基亞甲 苯并I唾等Γ坐、Ν·(Ν’Ν二2-乙基己基）胺基伸乙基緩基 總二抑制劑、笨并三唾類、及缓基苯并三。坐類之 Γ0^，3里且為相對於感光性樹脂組合物整體而為0.01〜3質 入物秘更子的疋〇 〇5〜1質量〇/〇。該含量就對感光性樹脂組 合物賦予保存穩定性之觀點而言宜為〇〇1質量％以上，另 148467.doc •21 · 201106099 -方面’就維持感度、抑制染料之脫色之觀點而古 的是3質量。/。以下。 σ更好 感光性樹脂組合物視需要亦可含有塑化劑 化劑，例如可列舉：聚乙-醢斯而^ 匕種塑 幻举聚乙_%'聚丙一醇、聚氧 乙烯醚、聚氧乙烯單甲醚、聚氧丙烯單甲醚、聚氧 氧丙烯單甲ϋ、聚氧乙稀單乙醚、聚氧丙稀單乙_、聚^ 乙烯聚氧丙烯單乙醚等二醇或酯類；鄰苯二甲酸二乙酽Υ 鄰苯二曱酸醋類；冑甲苯續醯胺、對甲苯項醯胺、捧^ 三丁醋、檸檬酸三乙醋、乙醯檸檬酸三乙醋、乙酿择樣^ 二-正丙酯、乙醯檸檬酸三-正丁酯等。 關於塑化劑之含量，以於感光性樹脂組合物中含有$〜 質量％為宜，更好的是5〜30質量。該含量就抑制顯影時 間之延遲、對硬化膜賦予柔軟性之觀點而言宜為5質量％ 以上另一方面’就抑制硬化不足或冷流之觀點而言，宜 為5 0質量％以下。 <感光性樹脂組合物調和液> 作為溶解感光性樹脂組合物之溶劑，可列舉：甲基乙美 酮（ΜΕΚ，Methyl Ethyl Ketone)所代表之酮類，甲醇、乙 醇或異丙醇所代表之醇類等。該溶劑以塗佈於支持膜上之 感光性樹脂組合物之溶液之黏度於25〇c下達到500〜4,〇〇〇 mPa_s之方式添加至感光性樹脂組合物中為宜。 <感光性樹脂積層體> 感光性樹脂積層體含有包含感光性樹脂組合物之感光性 樹脂層及支持膜。視需要亦可於感光性樹脂層之與支持膜 148467.doc -22- 201106099 側相反之側的表面具有保護層。作為此處所使用之支持 膜’較理想的是纟由曝光光源所發射t光透射的透明者。 作為此種支持膜’例如可列舉：聚對苯二甲酸乙二酯膜、 聚乙稀醇膜、聚氣乙稀膜、氣乙稀共聚物膜、聚偏氯乙稀 膜、偏氯乙烯共聚物膜、聚甲基丙稀酸甲醋共聚物膜、聚 苯乙烯膜、聚丙烯腈膜、苯乙烯共聚物膜、聚醯胺膜、纖 維素衍生物膜等。該等膜視需要亦可使用經延伸者。霧值 且為5以下。關於薄膜之厚度，較薄時於圖像形成性及經 濟性方面有利，為了維持強度，可較好地使用i〇〜3〇 pm 者。 感光性樹脂積層體所用之保護層之重要特性為，保護層 與感光性樹脂層之密接力與支持膜與感光性樹脂層之密接 力相比較足夠小，可容易地剝離。例如，聚乙烯膜、聚丙 烯膜可較好地用作保護層。又，亦可使用日本專利特開昭 59-202457號公報中揭示之剝離性優異之膜。保護層之膜 厚宜為10〜100 μιη，更好的是10〜50 μηι。感光性樹脂積層 體之感光性樹脂層之厚度係視用途而不同，宜為5〜1〇〇 μιη，更好的是7〜60 μπι，越薄則解析度越提高，另外，越 厚則膜強度越提高。 作為將支持膜 '感光性樹脂層、及視需要之保護層依序 積層而製作感光性樹脂積層體之方法，可採用公知之方 法。例如’可將感光性樹脂層所用之感光性樹脂組合物與 溶解該等感光性樹脂組合物之溶劑混合而製成均勻之溶 液’首先使用棒塗機或輥塗機塗佈於支持膜上，繼而進行 148467.doc -23- 201106099 乾燥’於支持膜上積層包含感光性樹脂組合物之感光性樹 脂層。 乾燥後之感光性樹脂層之厚度宜為丨〜丨〇〇 μιη，更好的是 2〜50 μιη，進而好的是3〜15 μπι。該厚度就蓋孔（tent)性之 觀點而言宜為3 μηι以上，就解析性之觀點而言宜為丨5 μηι 以下。 然後’視需要可於感光性樹脂層上貼合保護層，藉此製 作感光性樹脂積層體^ <使用本發明之感光性樹脂積層體的ΙΤ〇電極形成法> 以下’對使用本發明之感光性樹脂積層體的ΙΤ〇電極之 形成方法（圖案形成）加以說明。 又’本發明之感光性樹脂積層體除ΙΤ0以外亦可適用於 鐵系合金之蝕刻（化學銑切）。作為鐵系合金，可列舉鐵_ 鉻-鎳4合金、42合金、SUS(Stainless steel，不鏽鋼）等。 鐵系合金可用於導線架或電子設備軀體等。 (基材） 所謂ITO膜’係指銦與錫之氧化物之薄膜且可用作透明 電極。通常’藉由濺鍍或蒸鍍等方法，對玻璃基材或透明 樹脂基材例如聚對苯二曱酸乙二酯（PET)或聚萘二甲酸乙 二S旨（PEN)、聚碳酸酯（PC)進行製膜。膜厚通常為2〇 nm〜300 nm ’係視用途而適當調節。又’作為與IT〇類似 之用作透明電極之化合物，可列舉IZ〇(Indium以加 Oxide ’氧化銦鋅）、Sn〇2等。 (1)貼合步驟 148467.doc -24· 201106099 一邊剝離感光性樹脂組合物之保護層，一邊以貼合機將 感光性樹脂積層體之感光性樹脂層加熱壓接並貼合於玻璃 基板表面。此時之加熱溫度通常為40〜160。(：。又，藉由進 行兩次以上之該加熱壓接，所得之光阻圖案對基板之密接 性提高。此時，壓接可使用具有二連輥之二段式貼合機， 亦可數次反覆於輥間通過而壓接。 (2) 曝光步驟 使具有所需佈線圖案之光罩膜密接於支持體上，使用活 性光源進行曝光。作為所使用之活性光源線，可列舉高壓 水銀燈、超高壓水銀燈、紫外線螢光燈、碳弧燈、氙氣燈 4又為獲得更从細之光阻圖案，更好的是使用平行光 光源。於欲極力減少垃圾或異物之影響時，亦有於使光罩 自支持體上浮起數十μπι以上、數百μηι以上之狀態下進行 曝光（近接式曝光）之情況。 (3) 顯影步驟 曝光後，剝離感光性樹脂層上之支持體，繼而使用鹼性 水溶液之顯影液將未曝光部顯影去除而獲得光阻圖像。作 為鹼性水溶液，係使或ΚΑ〇3之水溶液。鹼性水 浴液係根據感光性樹脂層之特性而適當選擇，通常為約 0.2〜2質量％之濃度、約2〇〜机之叫⑽水溶液^於該驗 |·生水，谷液巾#可/¾人表面活性劑、消泡劑、用以促進顯 影之少量有機溶劑等《考慮到對基材之影響，亦可使用氫 氧化四甲基敍（TMAH)水溶液等胺系之驗性水溶液。可根 據顯影速度而適當選擇濃度。 148467.doc -25- 201106099 可經由上述之各步驟而獲得光阻圖案，視情況亦可進而 進行約100〜3〇〇°C之加熱步驟》藉由實施該加熱步驟，可 進一步提高耐化學品性。加熱時可使用熱風、紅外線、遠 紅外線之方式之加熱爐。 (4) 触刻步驟 對藉由顯影而露出之基板之ΙΤ〇膜進行蝕刻。通常使用 3 0 6 0 C之氣化銅-鹽酸水溶液或氣化鐵-鹽酸水溶液等酸 性蝕刻液，形成導體圖案。除上述蝕刻液以外，亦可根據 ΙΤΟ膜或基底之種類使用草酸水溶液。 (5) 剝離步驟 然後，使用具有強於顯影液之鹼性的水溶液自基板剝離 光阻圖案。剝離用之鹼性水溶液亦無特別限制，通常係使 用濃度約2〜5質量％、溫度約4〇〜7〇〇c 2Na〇H、κ〇η之水 溶液。亦可於剝離液中加入少量之水溶性溶劑。 [實施例] 以下，對本發明之實施形態之例加以具體說明。 (實施例1〜10、比較例1〜3 ) 首先，對實施例及比較例之評價用樣品之製作方法進行 說明，繼而示出所得樣品之評價方法及評價結果。/仃 1 ·評價樣品之製作 實施例及比較例之評價用樣品係如下述般製作。 <感光性樹脂積層體之製作> 將以下表！所示之組成（其中，各成分之數字表示以 成分計之調配量（質量份）)之感光性樹脂組合物及溶劑充分 148467.doc -26- 201106099 授拌、混合而製成感光性樹脂組合物料液，使用棒塗機 均勻塗佈於作為支持體之16 μιη厚之聚對苯二甲酸乙二酯 膜之表面，於95°C之乾燥機中乾燥2.5分鐘而形成感光^ 樹脂層。感光性樹脂組合層之厚度為25 繼而’於感光性樹脂層之未積層聚對苯二曱酸乙二酯膜 之表面上貼合作為保護層的21 pm厚之聚乙烯膜，獲得感 光性樹脂積層體。 以下之表2中，示出表丨中以簡稱表示之感光性樹脂組合 物調和液中之材料成分之名稱。 148467.doc -27· 201106099 【1<】 比較例3 I 〇 (N — 3 0.15 0.05 0.2 -2 o ◎ X 1比較例2 § ο (N — 3 0.15 j 0.05 0.2 0.08 00 〇s ◎ X 比較例1 Ο ^ CN — 3 0.15 0.05 0.2 0.05 00 Cn X ◎ 實施例10 O w-> <N 一 3 0.15 is 0.08 0.05 ON σ\ ◎ ◎ 實施例9 § O CN — 3 0.15 1 0.05 1 0.2 in — O ON as ◎ ◎ 實施例8 | § 〇 m (Ν — 3 0.15 d ° oo <n o o d cS 〇\ ◎ ◎ 實施例7 | § Ο iTi <Ν — 3 0.15 <=:° 0.08 0.05 〇\ ◎ ◎ 實施例6 | δ ο ίη (Ν 一 3 0.15 0.05 0.2 0.08 0.05 〇\ ◎ ◎ |實施例5 | § Ο <Ν — 3 0.15 0.05 0.2 0.08 0.09 as σ> ◎ ◎ 實施例4 § Ο (Ν 一 3 0.15 1 0.05 0.2 0.08 0.02 OS C\ ◎ 〇 實施例3 | § Ο Vi CN — 3 0.15 0.05 0.2 0.25 0.05 Os Os ◎ 〇 |實施例2 1 ο ^Τ) (Ν — 3 0.15 0.05 0.2 0.04 0.05 oo On 〇 ◎ 實施例1 | § ο们 CN 一 3 0.15 0.05 0.2 0.08 0.05 <7n G\ ◎ ◎ 1 < (Ν ΓΟ ώ ώ CN ·—· CN Q Q —CN ΓΛ 寸 Ό 1 1 1 1 ( 1 X X X X X X 總計 蝕刻密接性 保存穩定性 -28 - 148467.doc 201106099 [表2] A-1 ί 甲酿/甲基丙稀酸(重量比25/5〇/25)之共聚物之35%甲基乙 基酮溶液(酸當量34，重量平均分子量5萬） B-1 九乙二醇二丙烯酸酯 一 B-2 莫耳之氧化乙騎得之三丙雜(新 1-1 2-(鄰氯苯基)-4,5-二苯基咪唑基二聚物 ' 1-2 D-1 4,4·-雙(二乙基胺基)二苯甲酮 鑽石ΐ " 〜一''— D-2 隱色結晶紫 " X-1 3-縮水甘油氧基丙基三曱氧基矽烷(信越化學工業 X-2 2-(3,4-環氧環己基)乙基三甲氧基石夕烷(信越化學工業处^^3〇3) X-3 3-縮水甘油氧基丙基三乙氧基石夕烧(信越化學工業κβΕΜ^) ~~~ X-4 2·二-正丁基胺基-4,6-二酼基-均三畊（川口化學工業股份有限 Actor BSH) ^ X-5 5-胺基-2-酼基-1，3,4-噻二唑(大塚化學(股)製造） X-6 季戊四醇四-3-巯基丁酸酯 比較例1係不含（D)環氧矽烷化合物之組合物，比較例2 係不含（E)硫醇化合物之組合物，另外，比較例3係過量含 有（D)環氧矽烷化合物之組合物。 <基板> 準備積層有90 nm之ITO膜的0.7 mm厚之玻璃基材 (Geomatec(股）製造）。 <貼合> 一邊剝離感光性樹脂組成積層體之聚乙烯膜，一邊藉由 148467.doc -29- 201106099 熱輥貼合機（大成貼合機（股）製造，VA_4〇〇ni)於輥溫度 110°c下進行貼合。氣壓係設為請MPa，貼合速度係設 為 1 ·5 m/min。 <曝光> 使用絡玻璃光罩，藉由〇RC製作所製造之高精度曝光機 EXM-1066-H-01(ghi線、23 w、間隙曝光方式15〇㈣），以 15〇 mJ/cm2之曝光量進行曝光。再者，鉻玻璃光罩係使用 曝光部與未曝光部之寬度為丨：i之比率的線圖案光罩。 <顯影> 剝離聚對笨二甲酸乙二酯膜之後，喷射3〇。〇之丄質量 %Na2C〇3水溶液特定時間，將感光性樹脂層之未曝光部分 溶解去除。此時，將未曝光部分之感光性樹脂層完全溶解 所需要之最少時間設定為最小顯影時間，以其2倍之時間 於相同條件下進行顯影而製作硬化光阻圖案。 〈姓刻;> 將上述附有硬化光阻圖案之玻璃基板於已加熱至5〇t之 氣化鐵-鹽酸水溶液（ADEKA(股）製造，Adeka Chelumica ITO-400)中浸潰5分鐘而進行蝕刻加工，對蝕刻後之玻璃 基板進行水洗清洗。 <剝離> 繼而’將姓刻後之玻璃基板於已加熱至5(rc之3質量％ 之NaOH水溶液中浸潰3分鐘而剝離硬化光阻圖案。 2·評價方法 <密接性評價> 148467.doc -30- 201106099 於顯影後’測定硬化光阻圖案之線間寬度《進而，測定 蝕刻後之形成電路圖案之線間寬度。將硬化光阻圖案之線 間寬度與蝕刻後之形成電路圖案之線寬度加以比較，算出旁 側蝕刻寬度。根據旁側蝕刻寬度之值，如下述般劃分等級： ◎:旁側蝕刻寬度之值為8.5 μιη以下； 〇：旁側蝕刻寬度之值超過8.5 μηι且為12.0 μιη以下； X :旁側蝕刻寬度之值超過12.0 μηι 0 <保存穩定性評價> 自感光性樹脂積層體剝離聚乙烯膜，以上述曝光量進行 曝光後經過15分鐘後’使用光譜儀（曰本電色工業（股）、 NF333)自聚對苯二甲酸乙二酯側測定曝光部與未曝光部之 對比度。又’以相同順序測定於溫度23。(：、濕度75%下保 存了 3天的同一感光性樹脂積層體之對比度，根據對比度 之差如下述般劃分等級： ◎:對比度之差為0.8以下； 〇：對比度之差超過0.8且為1_5以下； X :對比度之差超過1.5。 3.評價結果 實施例卜10、及比較例1〜3之評價結果示於表j。 [產業上之可利用性] 本發明可提供一種用於平板顯示器之顯示材料的對玻璃 基材上之ITO膜、Sn〇2膜形成電極等之圖案形成中有用的 感光性樹脂組合物及感光性樹脂積層體，且於在平板顯示 器之顯示材料等之製造中進行ITO電極形成時有用。 148467.doc •31 ·As a quinone, it is basically a tris-salt, for example, DU 5 is cleavage-benzotris-W 2-2-ethylhexyl lanthanide, and the sputum is sputum, Ν·(Ν,Ν~ylethyl) aminoxylene And I saliva and other squats, Ν Ν Ν Ν Ν 2- 2- 2- 2- 2- 2- 2- 2- 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。坐 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 The content is preferably 〇〇1% by mass or more from the viewpoint of imparting storage stability to the photosensitive resin composition, and the other aspect is 148467.doc •21 · 201106099 -the aspect of maintaining the sensitivity and suppressing the discoloration of the dye. It is 3 quality. /. the following. The σ-bright photosensitive resin composition may further contain a plasticizing agent, for example, poly(ethylene bromide), 匕 塑 幻 幻 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ a diol or ester such as oxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxypropylene propylene monomethyl hydrazine, polyoxyethylene monoethyl ether, polyoxypropylene monoethyl _, poly propylene polyoxypropylene monoethyl ether ; phthalic acid diethyl phthalate phthalic acid vinegar; hydrazine toluene hydrazine, p-toluene decylamine, phthalate, tributyl vinegar, triacetic acid citrate, ethyl citrate triethyl vinegar, B Brewing samples ^ di-n-propyl ester, acetaminophen tri-n-butyl ester and the like. The content of the plasticizer is preferably from US$% by mass, more preferably from 5 to 30% by mass in the photosensitive resin composition. The content is preferably 5% by mass or more from the viewpoint of suppressing the development time and imparting flexibility to the cured film, and is preferably 50% by mass or less from the viewpoint of suppressing insufficient hardening or cold flow. <Photosensitive resin composition preparation liquid> As a solvent for dissolving the photosensitive resin composition, a ketone represented by methyl ethyl ketone (Methyl Ethyl Ketone), methanol, ethanol or isopropanol can be mentioned. Representative of alcohols and the like. The solvent is preferably added to the photosensitive resin composition so that the viscosity of the solution of the photosensitive resin composition coated on the support film is 500 to 4 at 25 ° C, and 〇〇〇 mPa_s. <Photosensitive Resin Laminate> The photosensitive resin laminate includes a photosensitive resin layer and a support film containing a photosensitive resin composition. A protective layer may be provided on the surface of the photosensitive resin layer opposite to the side of the support film 148467.doc -22-201106099 as needed. As the support film used herein, it is preferable that the 纟 is transparently transmitted by the t-light emitted from the exposure light source. Examples of such a support film include polyethylene terephthalate film, polyethylene film, polyethylene film, ethylene ethylene copolymer film, polyvinylidene chloride film, and vinylidene chloride copolymerization. A film, a polymethyl methacrylate copolymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, a cellulose derivative film, or the like. These films may also be used as extensions as needed. The fog value is 5 or less. When the thickness of the film is thin, it is advantageous in terms of image formation property and economy, and in order to maintain strength, it is preferable to use i 〇 3 〇 pm. An important characteristic of the protective layer for the photosensitive resin laminate is that the adhesion between the protective layer and the photosensitive resin layer is sufficiently small as compared with the adhesion between the support film and the photosensitive resin layer, and the film can be easily peeled off. For example, a polyethylene film or a polypropylene film can be preferably used as a protective layer. Further, a film excellent in peelability disclosed in Japanese Laid-Open Patent Publication No. SHO 59-202457 can also be used. The thickness of the protective layer film is preferably 10 to 100 μm, more preferably 10 to 50 μη. The thickness of the photosensitive resin layer of the photosensitive resin laminate is different depending on the application, and is preferably 5 to 1 μm, more preferably 7 to 60 μm, and the thinner the resolution is, the thicker the film is. The strength is increased. A known method of producing a photosensitive resin laminate by sequentially laminating a support film 'photosensitive resin layer and, if necessary, a protective layer, can be employed. For example, 'a photosensitive resin composition for a photosensitive resin layer can be mixed with a solvent for dissolving the photosensitive resin compositions to form a uniform solution. First, it is applied onto a support film by a bar coater or a roll coater. Then, 148467.doc -23-201106099 is dried to laminate a photosensitive resin layer containing a photosensitive resin composition on a support film. The thickness of the photosensitive resin layer after drying is preferably 丨~丨〇〇 μιη, more preferably 2 to 50 μηη, and further preferably 3 to 15 μπι. The thickness is preferably 3 μηι or more from the viewpoint of the tentability, and is preferably 丨5 μηι or less from the viewpoint of analytical properties. Then, a photosensitive resin laminated body can be produced by bonding a protective layer to the photosensitive resin layer as needed, and a tantalum electrode forming method using the photosensitive resin laminated body of the present invention will be described. A method (pattern formation) of forming a tantalum electrode of the photosensitive resin laminate will be described. Further, the photosensitive resin laminate of the present invention can be applied to etching (chemical milling) of an iron-based alloy in addition to ΙΤ0. Examples of the iron-based alloy include iron-chromium-nickel 4 alloy, 42 alloy, and SUS (stainless steel). Iron-based alloys can be used for lead frames or electronic device bodies. (Substrate) The ITO film means a film of an oxide of indium and tin and can be used as a transparent electrode. Usually, by means of sputtering or evaporation, a glass substrate or a transparent resin substrate such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), polycarbonate (PC) film formation. The film thickness is usually adjusted from 2 Å to 300 nm. Further, examples of the compound used as a transparent electrode similar to IT〇 include IZ〇 (Indium with Oxide® indium zinc oxide), Sn〇2, and the like. (1) Bonding step 148467.doc -24·201106099 The photosensitive resin layer of the photosensitive resin laminate is heat-compressed and bonded to the surface of the glass substrate by a bonding machine while peeling off the protective layer of the photosensitive resin composition. . The heating temperature at this time is usually 40 to 160. (: Further, by performing the thermocompression bonding twice or more, the adhesion of the obtained photoresist pattern to the substrate is improved. At this time, the two-stage laminating machine having two rollers can be used for the crimping, or (3) The exposure step is performed by attaching a mask film having a desired wiring pattern to the support and exposing it with an active light source. As the active light source line used, a high pressure mercury lamp can be cited. Ultra-high pressure mercury lamps, ultraviolet fluorescent lamps, carbon arc lamps, xenon lamps 4 are used to obtain a more fine photoresist pattern, and it is better to use parallel light sources. When trying to reduce the impact of garbage or foreign matter, there are also When the photomask is floated from the support by several tens of μm or more and several hundred μm or more, exposure (near exposure) is performed. (3) After the development step is exposed, the support on the photosensitive resin layer is peeled off, and then the support is removed. The unexposed portion is developed and removed using a developing solution of an alkaline aqueous solution to obtain a resist image. As the alkaline aqueous solution, an aqueous solution of ΚΑ〇3 is used. The alkaline water bath is based on the characteristics of the photosensitive resin layer. Suitably, it is usually about 0.2~2% by mass, about 2 〇~ machine called (10) aqueous solution ^ in the test|· raw water, gluten towel #可/3⁄4 human surfactant, defoaming agent, used A small amount of an organic solvent that promotes development, etc. "In view of the influence on the substrate, an amine-based aqueous solution such as an aqueous solution of tetramethyl hydride (TMAH) may be used. The concentration may be appropriately selected depending on the development speed. 148467.doc - 25- 201106099 A photoresist pattern can be obtained through the above steps, and a heating step of about 100 to 3 ° C can be further carried out as occasion demands. By performing the heating step, chemical resistance can be further improved. A hot air, infrared, or far infrared ray heating furnace can be used. (4) The etch process is performed on the ruthenium film of the substrate exposed by development. Usually, a vaporized copper-hydrochloric acid aqueous solution of 3 0 60 C or An acid etching solution such as a vaporized iron-hydrochloric acid aqueous solution is used to form a conductor pattern. In addition to the above etching liquid, an aqueous oxalic acid solution may be used depending on the type of the ruthenium film or the substrate. (5) Peeling step, then using a base having a stronger liquid than the developer The aqueous solution is stripped of the photoresist pattern from the substrate. The alkaline aqueous solution for peeling is also not particularly limited, and an aqueous solution having a concentration of about 2 to 5% by mass and a temperature of about 4 Torr to 7 〇〇 c 2 Na 〇 H and κ η is usually used. A small amount of a water-soluble solvent may be added to the stripping solution. [Examples] Hereinafter, examples of the embodiment of the present invention will be specifically described. (Examples 1 to 10, Comparative Examples 1 to 3) First, examples and comparisons are made. In the example, the method for producing the sample for evaluation is described, and the evaluation method and evaluation result of the obtained sample are shown. 仃1. Production of the evaluation sample The sample for evaluation of the comparative example and the comparative example was produced as follows. [Preparation of Resin Laminate] The photosensitive resin composition and solvent of the composition shown in the following Table (wherein the number of each component indicates the amount (parts by mass) in terms of composition) is sufficient 148467.doc -26-201106099 The photosensitive resin composite material liquid was mixed and mixed, and uniformly coated on the surface of a 16 μm thick polyethylene terephthalate film as a support by a bar coater in a dryer at 95 ° C. Dry ^ 2.5 minutes to form a photosensitive resin layer. The thickness of the photosensitive resin composite layer is 25, and then a 21 pm thick polyethylene film is bonded to the surface of the unstacked polyethylene terephthalate film of the photosensitive resin layer to obtain a protective layer, thereby obtaining a photosensitive resin. Laminated body. In the following Table 2, the names of the material components in the photosensitive resin composition adjusting liquid indicated by the abbreviation are shown in the table. 148467.doc -27·201106099 [1<] Comparative Example 3 I 〇(N — 3 0.15 0.05 0.2 -2 o ◎ X 1 Comparative Example 2 § ο (N — 3 0.15 j 0.05 0.2 0.08 00 〇s ◎ X Comparative Example 1 Ο ^ CN — 3 0.15 0.05 0.2 0.05 00 Cn X ◎ Example 10 O w-><N - 3 0.15 is 0.08 0.05 ON σ\ ◎ ◎ Example 9 § O CN — 3 0.15 1 0.05 1 0.2 in — O ON as ◎ ◎ Example 8 | § 〇m (Ν - 3 0.15 d ° oo <nood cS 〇 ◎ ◎ Example 7 | § Ο iTi < Ν — 3 0.15 <=:° 0.08 0.05 〇 ◎ ◎ Example 6 | δ ο ίη (Ν一3 0.15 0.05 0.2 0.08 0.05 〇 ◎ ◎ | Example 5 | § Ο <Ν - 3 0.15 0.05 0.2 0.08 0.09 as σ> ◎ ◎ Example 4 § Ο (Ν一3 0.15 1 0.05 0.2 0.08 0.02 OS C\ ◎ 〇 Example 3 | § Ο Vi CN — 3 0.15 0.05 0.2 0.25 0.05 Os Os ◎ 〇 | Example 2 1 ο ^Τ) (Ν — 3 0.15 0.05 0.2 0.04 0.05 oo On 〇 ◎ Example 1 | § ο CN CN A 3 0.15 0.05 0.2 0.08 0.05 <7n G\ ◎ ◎ 1 < (Ν ΓΟ ώ ώ CN ·—· CN QQ —CN ΓΛ Ό Ό 1 1 1 1 ( 1 X XXXXX Total etching adhesion stability -28 - 148467.doc 201106099 [Table 2] A-1 ί 35% methyl ethyl ketone / methyl methacrylate (weight ratio 25/5 〇 / 25) copolymer Ketone solution (acid equivalent weight 34, weight average molecular weight 50,000) B-1 Nine ethylene glycol diacrylate-B-2 Moly Oxidation E-ridden tripropene (new 1-1 2-(o-chlorobenzene) -4,5-diphenylimidazolyl dimer' 1-2 D-1 4,4·-bis(diethylamino)benzophenone diamond ΐ "~一''- D- 2 leuco crystal violet " X-1 3-glycidoxypropyltrimethoxy decane (Shin-Etsu Chemical Industry X-2 2-(3,4-epoxycyclohexyl)ethyltrimethoxy oxalate ( Shin-Etsu Chemical Industry Co., Ltd. ^^3〇3) X-3 3-glycidoxypropyl triethoxy zeshi (Shin-Etsu Chemical Industry κβΕΜ^) ~~~ X-4 2·di-n-butylamino- 4,6-dimercapto-average three-ploughing (Kawaguchi Chemical Industry Co., Ltd. Limited Actor BSH) ^ X-5 5-Amino-2-mercapto-1,3,4-thiadiazole (Otsuka Chemical Co., Ltd.) X-6 Pentaerythritol tetrakis-mercaptobutyrate Comparative Example 1 is a composition containing no (D) epoxy decane compound, and Comparative Example 2 is free of (E) sulfur The composition of the compound, Comparative Example 3 containing the excess line (D) of the composition of an alkoxy compound of silicon epoxy. <Substrate> A 0.7 mm thick glass substrate (manufactured by Geomatec) having a 90 nm ITO film laminated thereon was prepared. <Finishing> The polyethylene film of the laminated body of the photosensitive resin is peeled off, and the 148467.doc -29-201106099 hot roll laminator (manufactured by Dacheng Laminator Co., Ltd., VA_4〇〇ni) is used. The roll temperature was adjusted at 110 ° C. The air pressure system is set to MPa, and the bonding speed is set to 1 · 5 m/min. <Exposure> Using a glass reticle, a high-precision exposure machine EXM-1066-H-01 (ghi line, 23 w, gap exposure method 15 〇 (4)) manufactured by 〇RC, manufactured at 15 〇 mJ/cm 2 The exposure amount is exposed. Further, the chrome glass ray mask is a line pattern mask in which the width of the exposed portion and the unexposed portion is 丨:i. <Development> After the polyethylene terephthalate film was peeled off, 3 Å was sprayed. 〇 丄 丄 % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % At this time, the minimum time required to completely dissolve the photosensitive resin layer in the unexposed portion was set to the minimum development time, and development was carried out under the same conditions twice to prepare a hardened resist pattern. <Name of the last name;> The glass substrate with the hardened photoresist pattern described above was immersed in an aqueous solution of hydrogenated-hydrochloric acid (Adeka Chelumica ITO-400) which had been heated to 5 Torr for 5 minutes. The etching process is performed, and the etched glass substrate is washed with water. <Peeling> Then, the glass substrate after the last name was immersed in a 3% aqueous solution of 3% by mass of rc for 3 minutes to peel off the cured photoresist pattern. 2. Evaluation method <Adhesion evaluation> 148467.doc -30- 201106099 After the development, 'measuring the line width between the cured photoresist patterns', and further, measuring the line width between the formed circuit patterns after etching. The line width of the cured photoresist pattern and the formation after etching The width of the line pattern is compared to calculate the side etching width. According to the value of the side etching width, the level is classified as follows: ◎: the value of the side etching width is 8.5 μηη or less; 〇: the value of the side etching width exceeds 8.5 μηι and 12.0 μηη or less; X: side etching width value exceeds 12.0 μηι 0 <preservation stability evaluation> The polyethylene film is peeled off from the photosensitive resin laminate, and after 15 minutes after exposure with the above exposure amount, 'The spectrometer (Sakamoto Denshoku Industries Co., Ltd., NF333) was used to measure the contrast between the exposed portion and the unexposed portion from the polyethylene terephthalate side. It was also measured in the same order at a temperature of 23. The contrast of the same photosensitive resin laminate stored for 3 days under a humidity of 75% is classified according to the difference in contrast as follows: ◎: the difference in contrast is 0.8 or less; 〇: the difference in contrast is more than 0.8 and is 1 to 5 or less; X: The difference in contrast exceeds 1.5. 3. Evaluation results The evaluation results of Example 10 and Comparative Examples 1 to 3 are shown in Table J. [Industrial Applicability] The present invention can provide a display for a flat panel display. A photosensitive resin composition and a photosensitive resin laminate which are useful for pattern formation of an ITO film or a Sn 〇 2 film forming electrode on a glass substrate, and ITO is produced in the production of a display material such as a flat panel display. Useful when forming electrodes. 148467.doc •31 ·