200525295 (1) 九、發明說明 【發明所屬之技術領域】 本發明係有關用於印刷基板等製造之光阻組成物，特 別是水系溶液型或分散型光阻組成物、及使用其之光阻塗 佈基板的製造方法。 【先前技術】 先行技術中，製作印刷電路板時，於具銅箔類之導電 性金屬層之絕緣基板（含銅以外之金屬亦可，而，以下亦 可僅搞「貼銅基板」）上形成光阻塗佈後，介著具有所期 待圖案之光罩進行曝光後，以水或鹼水進行顯像處理後， 以蝕刻液進行未殘存光阻部份之導電性金屬層的蝕刻處理 後，藉由剝離光阻後，依所形成所期待配線圖案進行之。 形成光阻層於貼銅基板之方法有乾薄膜法、液狀光阻 塗佈法等者。液狀光阻塗佈法中除使液狀光阻藉由滾輥塗 佈、網版印刷塗佈於貼銅基板上之方法之外，公知者有浸 漬塗佈法（dip coating )者。此方法係浸漬貼銅基板於大量 光阻組成物（多半爲溶液）中後，拉出後，進行乾燥，使 溶媒揮發之後，於貼銅基板形成光阻塗膜。 浸漬塗佈法等所使用之液狀光阻組成物中做爲溶媒者 被使高度揮發性之有機溶劑者，惟，近年來由於擔心影響 人體、環境之慮，被揭示如：特開平05 -2 743 7號公報（專 利文獻1 )以水做爲溶媒含有之光阻組成物者。 惟’水性光阻組成物係以蒸發速度緩慢之水做爲溶劑 -5 - 200525295 (2) ，因此，光阻塗佈後之乾燥時間相當長。此，塗佈光阻溶液 於乾燥中出現「滴垂」、塗膜厚度不均之問題產生。 爲防止此「滴垂」，公知者以添加觸變劑（附與觸變 性劑）或增黏劑於光阻組成物者，如於特開2003 -23 3 1 8 3號 公報（專利文獻2 )中被揭示使用無機系增黏劑之組成物者 。其中塗膜厚度之均一性雖可保住，惟，其塗膜之平滑性、 密合強度卻不足。特別是塗膜之平滑性爲取得高精細之配線 圖案，更被期待進待進一步的改善。 另外，做爲有機系之解變劑、或增黏劑者被揭示使用 先行技術之羥烷基纖維素等纖維素衍生物者（如：特開昭 5 5 -04 5 725號公報（專利文獻3 )、特開平1 1 - 1 746 67號公報 (專利文獻4 ))。惟，此等纖維素衍生物之水溶液係以一 定溫度做爲境界之纖維素衍生物產生可逆性凝膠化者爲公 知者，因此，該溫度以上時，由溶液析出纖維素衍生物後 ，明顯降低水溶液之黏度。所以塗佈含有纖維素衍生物之 水性光阻後，於該凝膠化溫度以上進行乾燥時，乾燥時降低 黏度後明顯產生「滴垂」。更藉由乾燥時之降低黏度後，變 更組成物之分散狀態後，損及塗膜之平滑性。又，該凝膠化 溫度依其纖維素衍生物之種類而異，通常，明顯降低水沸 點之先行技術極不易解決該問題點。 特開2000-292922號公報（專利文獻5 )中被揭示疏水 性聚合物與水溶性聚合物之含有比例（疏水性聚合物/水溶 性聚合物）以重量比爲0.0 5〜4.0之感光性組成物者，做爲水 溶性聚合物者被記載可使用經院基纖維素者。惟，含多量 - 6 - 200525295 (3) 此纖維素衍生物之組成物中，單純做爲水性組成物時，由 於纖維素爲親水性，因此，塗佈面之乾燥不足，於塗佈面明 顯產生捲曲。又，藉由添加水後，降低塗佈面之平滑性，未 解決圖案解像度之降低問題點。 [專利文獻1]特開平05 -2743 7號公報 [專利文獻2]特開平2003 -23 3 1 83號公報 [專利文獻3]特開昭5 5-04 5 725號公報 [專利文獻4]特開平1 1 - 1 74667號公報 [專利文獻5]特開2000-292922號公報 【發明內容】 本發明之課題係提供一種做爲溶媒之含水光阻組成物 中，直接維持良好光阻之密合性、良好捲度，可達成高精細 之配線圖案之光阻組成物者。 本發明者鑑於上述情況，進行精密硏討後結果發現， 由水溶性或鹼可溶性樹脂及纖維素衍生物所成光阻組成物 之中，即使使用極少量纖維素衍生物時，使用特定量之水 及特定溶劑後，可有效解決該課題，進而完成本發明·。亦 即，本發明係有關下記[1]〜[9]者。 [1 ]該特徵係含有（A )可溶於水或鹼性水溶液之樹脂 、（B )纖維素衍生物、（C )水、及（D )含羥基有機溶 劑之水性光阻組成物者，該光阻組成物中該（B )纖維素 衍生物之含量爲0.001〜1.0質量％，該（C)含水量爲25〜65 質量％，而該（D )含羥基有機溶劑之含量爲1 5〜5 0質量％ 200525295 (4) 範圍之水性光阻組成物者。 [2 ]該特徵係含有（A )可溶於水或鹼性水溶液之樹脂 、（B )纖維素衍生物、（C )水、及（D )含經基有機溶 劑、（E )聚合性不飽和化合物、及（f )光聚合啓發劑之 水性光阻組成物者’該光阻組成物中之該（B )纖維素衍 生物含量爲0.001〜1.0質量％，該（C)含水量爲25〜65質量 m %，該（D )含羥基有機溶劑含量爲15〜50質量％範圍之水 性光阻組成物者。 φ [3 ]該特徵係（A )可溶於水或鹼性水溶液之樹脂與該 (B )纖維素衍生物之質量比（A ) / ( B )爲1〇〜1〇〇〇者之 [1]或[2]所載之水性光阻組成物。 [4 ]該特徵係該（A )可溶於水或鹼性水溶液之樹脂係 以（甲基）丙烯酸做爲一種構成單體之共聚物者之[丨卜口] 中任一項之水性光阻組成物者。 [5] 該特徵係該（B )纖維素衍生物爲羥烷基纖維素之 Π]〜[4]中任一項之水性光阻組成物者。 · [6] 該特徵係該（D )含羥基有機溶劑爲至少1種二醇 化合物之單烷基醚、二醇化合物與脂肪族羧酸之單酯、及 α -羥羧酸酯者之[1 ]〜[5 ]中任一項之水性光阻組成物。 · [7] [1]〜[6]中任一項之水性光阻組成物中浸漬具有導 嫌 電性金屬之絕緣基板者爲其特徵之光阻塗佈基板的製造方 法。 [8] 該特徵係使用[1]〜[6]中任一項之水性光阻組成物 之印刷電路板之製造方法。 200525295 (5) [9 ]使用[1 ]〜[6 ]中任一項之水性光阻組成物所製造之 印刷電路板。 本發明水性光阻組成物係可提供一種具良好密合性、 捲曲性、表面平滑性者’形成高精細配線圖案之印刷電路 板者。 【實施方式】 [發明實施之最佳形態] 以下針對本發明進行詳細說明。 [(A)可溶於水或鹼性水溶液之樹脂] 本發明光阻組成物所使用之（A )可溶於水或驗性水 溶液之樹脂（以下亦稱「水、鹼可溶性樹脂」。）係指溶 於水、碳酸鈉水溶液等鹼性水溶液之樹脂者。本發明之水 、鹼可溶性樹脂係具有可溶於顯像液、難溶於蝕刻液之性 質者，較佳者爲係於分子中含有具羧基或其無水物基之樹 脂成份者。做爲具羧基或其無水物基於分子中之樹脂者如 :含有做爲單體之（甲基）丙烯酸與（甲基）丙烯酸酯之 共聚物丙烯樹脂、（甲基）丙烯酸與乙烯之共聚物、無水 馬來酸與乙烯或苯乙烯之共聚物等例者，特別又以丙烯樹 脂其密合性、捲度等爲最佳者者。 又5 (甲基）丙烯酸係指丙烯酸酯及或丙烯酸之意。 該（A )水、鹼可溶性樹脂係於光聚合啓發劑之存在 下或不存在下，藉由紫外線、X線、電子線等之照射後可 冬 200525295 (6) 引起光聚合之光聚合性樹脂者宜，如：分子中具有複數個 乙傭性不飽和鍵類之聚合性基者爲其例者。 做爲該光聚合性樹脂例者可單獨或複數組合公知者之 使用，如：可選自下記（1 )〜（5 )之群者。 (1 )不飽和羥基化合物與具有1種以上官能基選自羧 基、羧酸無水物基、異氰酸酯基及環氧基中之樹脂之反應 物； (2 )不飽和環氧化合物與具有1種以上官能基選自羧 基、羧酸無水物基、異氰酸酯基、胺基、及羥基中之樹脂 之反應物； (3 )不飽和殘酸或不飽和羧酸無水物與具有1種以上 官能基選自羥基、胺基、異氰酸酯基及環氧基中之樹脂之 反應物； (4 )不飽和胺基化合物與具有1種以上官能基選自羧 基、羧酸無水物基、甲醯基、酮基、異氰酸酯基、及環氧 基中之樹脂之反應物； (5 )不飽和異氰酸酯化合物與具有1種以上官能基選 自羧基、羧酸無水物基、胺基、羥基及環氧基中之樹脂之 反應物。 此等光聚合性樹脂之重量平均分子量酸價（mgKOH /g)爲任意者，而，重量平均分子量以500〜100,000者宜， 特別以1，000〜50,000爲較佳，最佳者爲25000〜20,000，酸 價以20〜3 5 0者宜，特別以50〜2 5 0爲較佳，最佳者爲80〜200 -10- 200525295 (7) 重量平均分子量係藉由凝膠滲透色譜法，酸價係 JIS K 5 6 0].進行測定之。 做爲不飽和羥基化合物之具體例者可使用2 _經乙 甲基）丙烯酸酯、2 -羥丙基（甲基）丙烯酸醋 '二乙 單丙烯酸酯等之聚乙二醇單（甲基）丙烯酸酯、三乙 單（甲基）丙烯酸酯等之聚乙二醇單（甲基）丙嫌酸 1，4 -丁一醇單（甲基）丙燒酸酯、乙二醇單（甲基） 醚、一乙一醇單（甲基）嫌丙醚等聚乙二醇單（甲基 丙醚、N-羥甲基丙烯醯胺、烯丙醇、甲基烯丙醇、經 乙烯、羥甲基苯乙烯、烯丙基苯酚等。 做爲不飽和環氧化合物之具體例者如：縮水甘油 甲基）丙烯酸酯、烯丙基縮水甘油醚、3，4 -環氧基環 甲基（甲基）丙烯酸酯等例。 做爲不飽和羧酸及其無水物例者可使用如：（甲 丙烯酸、巴豆酸、衣康酸、馬來酸、延胡索酸、山梨 四氫呔酸、桂皮酸、那地酸、油酸、亞油酸、亞麻酸 酸、利坎酸、亞麻醇酸、花生烯酸及此等無水物等者 做爲不飽和胺基化合物例者如：烯丙胺、二烯丙 胺基苯乙烯、胺基甲基苯乙烯、丙烯醯胺、不飽和羧 其衍生物與乙烯二胺等聚胺之反應物等例。 做爲不飽和異氰酸酯化合物例者可使用如：2-異 酯乙基（甲基）丙烯酸酯、烯丙基異氰酸酯、不飽和 化合物與甲苯烯二異氰酸酯、苯二甲基二異氰酸酯等 氰酸酯之反應物等。 藉由 基（ 二醇 二醇 酯、 烯丙 )烯 基苯 基（ 己基 基） 酸、 、桐 〇 胺、 酸或 氰酸 羥基 聚異 -11 - 200525295 (8) 該（1 )〜（5 )所使用之具有1種以上官能基之樹脂係 指至少1種以上選自該不飽和羧酸、不飽和羧酸無水物、 不飽和異氰酸酯化合物、不飽和環氧化合物、不飽和羥基 化合物及不飽和胺基化合物中單獨被覆膜共聚物等者。 以具羧基做爲官能基之樹脂例者如：聚（甲基）丙烯 酸、（甲基）丙烯酸-甲基（甲基）丙烯酸酯共聚物、乙 烯-(甲基）丙烯酸共聚物、末端羧化聚丁二烯、末端羧 化丁二烯-丙烯腈共聚物、苯酚樹脂之（無水）多價羧酸 加成物等例。 做爲具有羥基之樹脂例者如：聚羥乙基（甲基）丙綠 酸酯、羥乙基（甲基）丙烯酸酯-苯乙烯共聚物、羥乙基 (甲基）丙烯酸酯-甲基丙烯酸酯共聚物、酚醛淸漆型苯酚 樹脂、聚乙烯醇、部份皂化乙烯-醋酸乙烯酯共聚物、聚甘 油、聚乙烯苯酚、環氧樹脂之羧酸加成物、聚乙二醇、聚 丙一醇、末师i經化（氣化）聚丁二燃、末端經化（氨化） 石油樹脂及多價醇與多價異氰酸酯之反應物等例者。 做爲具環氧基之樹脂例者如：聚縮水甘油基（甲基） 丙烯酸酯、縮水甘油基（甲基）丙烯酸酯-苯乙烯共聚物 、縮水甘油基（甲基）丙烯酸酯-甲基丙烯酸酯共聚物、 酚醛淸漆型苯酚樹脂與環氧氯丙烷之反應物、多價苯酚與 環氧氣丙烷之反應物及多價醇與環氧氯丙烷之反應物例者。 具胺基之樹脂例者如：聚丙烯醯胺、聚烯丙胺、聚乙 烯甲醯胺皂化物、聚乙烯乙醯胺皂化物、聚胺基苯乙烯、胺 基苯乙烯-苯乙烯共聚物、含羧基樹脂與多價胺之反應物、 -12 - 200525295 (9) 尿樹脂及蜜胺樹脂等例。 做爲具有異氰酸酯基之樹脂例者如：聚-2 -異氰酸酯乙 基（甲基）丙烯酸酯、2-異氰酸酯乙基（甲基）丙烯酸酯-甲基（甲基）丙烯酸酯共聚物、多價異氰酸酯化合物與多 價羥基化合物之反應物等例者。 更具體之該（1 )〜（5 )中理想例者爲 (1 - 1 )不飽和羥基化合物與具有羧酸無水物基之樹脂 的反應物，如：羥乙基丙烯酸酯與苯乙烯-無水馬來酸共聚 物之反應物，及該反應物更進行鹼之反應者； (1-2 )不飽和羥基化合物與具有異氰酸酯樹脂之反應 物（2-1 )不飽和環氧化合物與具有羧基樹脂之反應物者， 如：縮水甘油基丙烯酸酯與甲基丙烯酸酯-甲基甲基丙烯 酸酯共聚物之反應物、3,4-環氧基-環己基甲基丙烯酸酯與 甲基丙烯酸·甲基甲基丙烯酸酯共聚物之反應物及此等反 應物更進行鹼反應者； (3-1 )不飽和羧酸或不飽和羧酸無水物與具有環氧基 樹脂之反應物者，如：丙烯酸與聚縮水甘油基甲基丙烯酸 酯之反應物及丙烯酸與縮水甘油基甲基丙烯酸酯-甲基甲基 丙烯酸酯共聚物之反應物等； 者。 其中特別以做成（甲基）丙烯酸所構成單體之一種共 聚物者爲較佳、更佳者爲（甲基）丙烯酸及其酯之共聚物 或其改性物質所成之丙烯樹脂者。具體例如：縮水甘油基 丙烯酸酯與甲基丙烯酸-甲基甲基丙烯酸酯共聚物之反應 -13- 200525295 (10) 物、3,4-環氧基-環己基甲基丙烯酸酯與甲基丙燦酸 甲基丙烯酸酯共聚物之反應物及此等反應物更進行藏 者。 做爲光聚合性樹脂者除該（1 )〜（5 )之外，更 用下記者。 (6)聚丁二烯等之共軛二烯化合物之單獨或共 及其改性物質； (7 )環氧樹脂與不飽和脂肪酸之酯化物中之脂 鏈中的不飽和鍵中使不飽和二羧酸或其無水物進行加 成之聚合性不飽和樹脂； (8 )不飽和性脂肪酸改性高酸價醇酸樹脂所成 合性不飽和樹脂；以及.， (9 )馬來化油所成之聚合性不飽和樹脂與1分子 有1個以上聚合性不飽和鍵之乙燃性不飽和化合物之 物。 本發明水性光阻組成物中該（A )含量一般爲5〜 量％者宜，較佳者爲7〜3 0質量％，特別以9〜2 5質量％爲 者。當未達5質量％時塗於絕緣基板時之膜厚則太薄 生降低膜強度等問題。反之，超出40質量％時，膜厚 厚，明顯提高黏度，造成耗費乾燥時間等問題。 [(B )纖維素衍生物] 本發明中（B )纖維素衍生物可使用如：於纖維 基中導入烷基、羥烷基、羧烷基等者，並未受限於公 -甲基 t反應、 可使 聚物 肪酸 成所 之聚 中具 混合 40質 最佳 ，產 則太 素羥 知％ -14 - 200525295 (11) ，而又以羥烷基纖維素爲較佳者。做爲該烷基例考如：甲 基、乙基、丙基、丁基等者，做爲羥烷基例者如：羥乙基 、趨丙基、羥丁基等者，做爲羧院基例者如：殘甲基等者 。此等具體例如：甲基纖維素、乙基纖維素 '苄基纖維素 等纖維素之烷醚、羥乙基纖維素、羥丙基纖維素等羥烷醚 甲基L乙基纖維素、乙基趨乙基纖維素、甲基乙基声乙 基纖維素、甲基羥丙基纖維素、乙基羥丙基纖維素等之院 基經院_、羧甲基纖維素等羧烷基基纖維素、醋酸纖維素 等纖維素酯等者。此等烷基、羥烷基之導入量可依其目的進 行任意設定之，而，一般含於纖維素中之葡萄糖】單位爲 0.05〜2.5當量者。 其中又以甲基.纖維素、乙基羥基乙基纖維素、甲基經 基丙基纖維素、乙基羥丙基纖維素及羥丙基纖維素爲較佳 者’特別以羥丙基纖維素爲最佳。 此等可使用市售者，如：HEC Dai cell ( Dai cell股份 公司）、Be】mOC〇U ( Aczonobel股份公司）、fiEC：(住友 精化股份公司）、CuIuceH (三晶股份公司）、Metorose (倍越化學工業股份公司）、日曹HPC (日本曹達股份公 司）、t h 11 〇 s e ( c r a】丨a n t j a p a n股份公司）等可取得。 (B )纖維素衍生物之含量係本發明水性光阻組成物 中之0.001〜1.0質量％者，若不在此範圍時，則未能取得本 發明之效果。亦即，超出1 .0質量％時，則不僅降低塗膜表 面之平滑性’亦明顯產生捲度。反之，未達0.0 0 1質量％時 ’則塗膜厚度將不均，出現彈起、斑點等不良外觀，更降 -15- 200525295 (12) 低塗膜表面之平滑性。 又，本發明中，針對該（A )水溶性或鹼性水溶液之 (B )纖維素衍生物其質量比（A ) / ( B )爲10〜1 000者宜 ，當該（A ) / ( B )超出35 0時，貝IJ ( A )爲15質量％以上 者佳。 [(C )水] 本發明水性光阻組成物係以含（C )水做爲溶媒者。 藉由含（C )水後，可降低揮發性高之有機溶劑使用量， 且，光阻組成物之引火點提高、提昇保管、輸送時之安全 性。 本發明水性光阻組成物中之（C )水含量主要爲抑刖 纖維素衍生物之凝膠化後取得良好塗膜性狀者，水性光阻 組成物中以25〜65質量％爲宜，較佳者爲25〜60質量％，更 佳者爲30〜56質量％、35〜52質量％特別理想，最佳者爲 3 5〜5 0質量％者。當水含量超出該範圍時，則容易出現纖維 素衍生物之凝膠化，失去塗膜之平滑性，不易取得高精細 圖案。反之，水含量未達該範圍時，則將降低纖維素衍生 物之溶解性，也失去塗膜之平滑性、未能取得高精細之圖 案。 [(D )含羥基之有機溶劑] 本發明（D )羥基有機溶劑係分子中具有1以上羥基之 化合物者，此等不受限公知者可任意使用之，而又以醇化 -16- 200525295 (13) 合物、二醇化合物、二醇化合物之單烷基醚、二醇化合物 與脂肪族羧酸之單酯、α -羥羧酸酯爲較佳者。此等含經 基之有機溶劑可單獨使用，亦可複數合倂使用之。 本發明水性光阻組成物中（D )之含量爲本發明水性 光阻組成物中之1 5〜5 0質量％者宜，較佳者爲2 0〜5 5質量％ ，更佳者爲20〜45質量％，特別理想者爲25〜45質量％，最 佳者爲25〜40質量％。當（D )含量未達15質量％時，則不 易控制加熱後纖維素衍生物之凝膠化，失去塗膜平滑性’ 不易取得高精細圖案者。更於乾燥時產生「滴垂」後’降 低塗膜厚度之均勻性。反之，超出5 0質量％則降低纖維素 衍生物之溶解性，亦失去塗膜平滑性，仍未能取得高精糸田 之圖案。 做爲該（D )含羥基有機溶劑之具體例者如：@ ' 乙醇、1 -丙醇、異丙醇、1 - 丁醇、卜戊醇、乙二醇、丙一醇 、甘油、1，2 -丙二醇、二乙二醇、三乙二醇、四乙二醇、乙 二醇單甲醚、乙二醇單甲醚、乙二醇單丁醚、二乙二醇單 丁醚、二乙二醇單***、二乙二醇單丁醚、三乙二醇單甲 醚、三乙二醇單***、三乙二醇單丁醚、乙二醇單乙酸酉曰 、二乙二醇單乙酸酯、三乙二醇單乙酸酯、丙二醇單甲® 、丙二醇單***、丙二醇單丙醚、丙二醇單丁醚、二丙一醇 單甲醚、二丙二醇單***、二丙二醇單丙醚、二丙一醇單丁 醚、丙二醇單乙酸酯、二丙二醇單乙酸酯等例。 另外可使用].;3-丙二醇、丁二醇、甲基-1，3 醇、2 : 2 -二甲基-1 , 3 -丙二醇、2 -甲基 _ 1，3 - 丁二醇、3_ -17- 200525295 (14) 1，3-丁 二醇、1，3-戊二醇、2,4-戊二醇、1，3-己二醇、2,4-己 二醇、三羥甲基丙烷、季戊四醇、3-甲氧基-1-丙醇、2-甲 基-3·甲氧基-卜丙醇、2,2-二甲基-3-甲氧基-1-丙醇、3-甲氧 基-1-丁醇、3-甲氧基-3-甲基-1-丁醇、此等甲氧基以乙氧基 、其他烷氧基取代者、3-乙醯氧基-1-丙醇、2-甲基-3-乙醯 氧基-卜丙醇、2 5 2 -二甲基-3-乙醯氧基-1-丙醇、3-乙醯氧基一 卜丁醇、3-乙醯氧基-3-甲基-卜丁醇、此等乙醯氧基以其他 醯氧基取代使用之。 做爲該（D )含羥基有機溶劑者亦可使用α -羥羧酸酯 者、未限定公知者均可使用之。此等α -羥羧酸酯之具體例 如：二醇酸甲酯、二醇酸乙酯、二醇酸η -丙酯、二醇酸異丙 酯' 二醇酸η-丁酯、二醇酸異丁酯、二醇酸η_戊酯、二醇酸 η -己醋、二醇酸環己酯等二醇酸醋、乳酸甲醋、乳酸乙醋、 乳酸η -丙酯、乳酸異丙酯、乳酸η - 丁酯、乳酸異丁酯、乳酸 戊酯、乳酸異戊酯、乳酸η-己酯、乳酸環己酯、乳酸平醋等 乳酸酯、α _·羥基酪酸甲酯、α -羥基酪酸乙酯、^ —經基酪 酸η ·丙醋、α -羥基酪酸異丙醋、α -羥基酪酸η - 丁醋、α _經 基酪酸異丁酯、α ·羥基酪酸η-戊酯、α -羥基酪酸^己醋、 α -羥基酪酸環己酯等之α -羥基酪酸酯、α -羥基吉草酸甲 酯、α -羥基吉草酸乙酯、α -羥基吉草酸丙酯、α -經基 吉早酸異丙醋、α -經基吉草酸η - 丁醋、α -經基吉草酸異丁 酯、α -羥基吉草酸戊酯、α -羥基吉草酸心己酯、α _羥基 吉草酸環己酯等α -羥基吉草酸酯等例。 本發明光阻組成物中，必要時亦可添加其他公知之有 - 18- 200525295 (15) 機溶劑。該溶劑例如：丙酮、丁酮、環己酮等酮類；甲苯、 二甲苯、乙苯、四甲苯等芳香族烴類；乙二醇單甲醚乙酸酯 、乙二醇單***乙酸酯、乙二醇單丁醚乙酸酯、丙二醇單甲 醚乙酸酯、丙二醇單***乙酸酯、乙二醇二甲醚 '乙二醇二 ***、乙二醇二丁醚、二乙二醇二甲醚、二乙二醇二***、 二乙二醇二丁醚等二醇醚類、醋酸甲酯、醋酸乙酯、醋酸丁 酯等醋酸酯類、3 -甲氧基-丙酸甲酯、3 -甲氧基-丙酸乙酯、 3 -甲氧基-酪酸甲酯、3 -甲氧基-酪酸乙酯、3 -甲基-3-甲氧 基-酪酸甲酯、3 -甲基-3-甲氧基··酪酸乙酯、2 -甲氧基-環己 烷羧酸甲酯、3 -甲氧基-1-丙基乙酸酯、2 -甲基-3 -甲氧基-1-丙基乙酸酯、2,2-二甲基-3-甲氧基-卜丙基乙酸酯、3-甲氧 基-卜丁基乙酸酯、3-甲氧基-3-甲基-1-丁基乙酸酯、此等甲 氧基以乙氧基、其他烷氧基取代者、此等乙醯氧基以其他醯 氧基取代者、辛烷、癸烷、環己烷等脂肪族烴；石油醚、石 蠛油、氫化石蠘油、溶劑石蠟油等石油系溶劑等例。 [(E )聚合性不飽和化合物] 本發明水性光阻組成物除該（A )〜（D )之外，更以 含有（E )聚合性不飽和化合物爲理想者。（E )聚合性不 飽和化合物只要爲藉由（F )光聚合啓發劑進行聚合之化 合物即可無特別限定，可單獨使用公知者，或複數合倂使 用均可。本發明光阻組成物中該（E )聚合性不飽和化合 物含里爲本發明光阻水性組成物中之Q · 1〜1 Q質量％者宜， 0.5〜7質量％爲更佳，最佳者爲】〜5質量％。當（e)聚合性 >19- 200525295 (16) 不飽和化合物含量不足0.0 1質量％時，則光聚合進行將不 足，而不易維持做爲光阻性能之維持。反之，含量超出]〇 質量％則降低塗膜性狀，明顯產生捲度。 做爲（E )聚合性不飽和化合物例者如：該不飽和羥 基化合物、不飽和環氧化合物、不飽和羧酸或不飽和羧酸 酐、不飽和胺基化合物、不飽和異氰酸酯化合物、苯乙烯 、乙烯甲苯、二乙烯苯、甲基甲基丙烯酸酯等（甲基）丙 烯酸烷酯或芳基酯、多價醇之（甲基）丙烯酸酯、及多價 醇之烯丙醚等例。 做爲多價醇之（甲基）丙烯酸酯例者如：乙二醇二（ 甲基）丙烯酸酯、二乙二醇二（甲基）丙烯酸酯、三乙二 醇二（甲基）丙烯酸酯、聚乙二醇二（甲基）丙烯酸酯、 三羥甲基丙烷三（甲基）丙烯酸酯、乙氧基化三羥甲基丙 烷三（甲基）丙烯酸酯、甘油三（甲基）丙烯酸酯、季戊 四醇四（甲基）丙烯酸酯、乙氧基化季戊四醇四（甲基） 丙燒酸酯等例。又，做爲多價醇之烯丙醚例者如：乙二醇 二烯丙醚、二乙二醇二烯丙醚 '二烯丙醚、聚乙二醇二烯 丙酸、三羥甲基丙烷三烯丙醚、甘油三烯丙醚、季戊四醇 四烯丙醚等例。 [(F )光聚合啓發劑] 做爲（F )光聚合啓發劑者可使用公知者。具體例如 :苯偶因、苯偶因甲醚、苯偶因***、苄基、二苯基二硫 g迷、四甲基秋蘭姆單硫醚、二乙醯基、曙紅、硫僅、米 -20- 200525295 (17) 酮、蒽醌、氯蒽醌、甲基蒽醌、α ·羥基異丁苯酮、p -異丙 基-α-羥基異丁苯酮、α，α、二氯-4-苯氧基苯乙酮、卜趕 基-1-環己苯乙酮、2,2 -二甲氧基-2-苯基苯乙酮、甲基苯甲 醯甲酸酯、2-甲基-1-[4-(甲基硫代）苯基-嗎啉丙烷1 酮、二苯甲酮、噻噸酮、2 -氯噻噸酮、2,4 -二乙基噻噸g、 2-異丙基噻噸酮、4-苯甲醯-4’-甲基二苯硫醚、n，N-二甲胺 苯甲酸乙酯、N，N-二甲胺苯甲酸戊酯及三乙醇胺等例。此等 可單獨使用，惟，複數合倂使用爲較佳者。 此等光聚合啓發劑之含量爲本發明水性光阻組成物中 之0.01〜10質量％者宜，較佳者爲0.1〜5質量％，最佳爲0.5〜3 質量％者·當（F)光聚合啓發劑含量不足〇.〇1質量％時，則 未能充份進行光聚合，而不易維持光阻之性能、。反之，超 出1 0質量％則將降低塗膜性狀。 本發明感光性組成物中，爲維持保存、加工時之安定 性亦可適當倂用聚合停止劑。做爲此等聚合停止劑例者可 使用先行技術公知之聚合停止劑，如；苯酚類（3，5 _二第 二-丁基-4 ·羥甲苯等）、氫輥類（氫輥、氫輥單甲醚等） 、與茶酚類（與茶酚、第三_ 丁基與茶酚、集掊酚）等例 〇 更k必要時’可添加酸性藍、酞菁藍、酞菁綠、碘綠 、一重氣頁、龍膽紫、氧化鈦、碳黑、蔡黑等公知之著色 月！I外13夕氧水、氟系、高分子系等消泡劑及/或矯味劑、 咪唑¥、D卷U坐系、三η坐系、矽烷偶合劑等之附與密合劑者 -21 - 200525295 (18) 本發明光阻組成物中，爲調整表面張力等，可添加界 面活性劑。界面活性劑並未特別限定，可使用公知者。如 :陰離子性界面活性劑（如：月桂基苯磺酸鈉、月桂酸鈉 、聚環氧乙院烷醚硫酸鹽之銨鹽等）、非離子性界面活性 劑（如：聚環氧乙烷烷醚、聚環氧乙烷烷酯、聚環氧乙烷 山梨聚糖脂肪酸酯、聚環氧烷烷苯醚、聚環氧乙烷烷胺、 聚環氧乙烷烷醯胺等）及乙炔二醇系界面活性劑例者。本 發明中，此等界面活性劑可使用1種或2種以上者。 本發明光阻組成物之黏度於25 °C下爲5〜5 00mPa · s者 宜，較佳者爲10〜300mPa· s，更佳者爲15〜200mPa· s，最 佳者爲2 0〜1 5 0 m P a · s者。當黏度低時，則不易出現觸變性 ，反之，黏度太高則浸漬塗:佈時之膜厚調整不易：。做爲黏 度測定之方法者可使用市售之B型旋轉黏度計等。 本發明光阻組成物可藉由任意方法混合該成份後製造 之，如：於具有攪拌葉片之容器中進行攪拌同時加入各成 份之方法例者。各成份可於進行混合之容器中同時進行添 加，亦可漸次添加。又，各成份可將其全量一倂加入，亦 可分複數次進行添加。混合時之溫度爲任意者，一般爲 5〜5 0 °C ，較佳者爲1 0〜4 0 °C。且，混合可於一定溫度下 進行，亦可變更溫度進行之。 本發明光阻組成物可適用任意塗佈方法，惟，又0 g 漬塗佈爲特別理想者。浸漬塗佈方法爲公知之方法者，容 器中置入大量光阻組成物，於其中浸漬具有貼銅層合板等 導電性金屬層之絕緣基板後，以任意速度呈垂直提起後， -22 - 200525295 (19) 製造塗佈基板。此時，容器內光阻組成物可任意設定溫度 ，而又以10〜5 0 °C之溫度範圍者較佳。 浸漬塗佈方法所使用之裝置並未特別限定，可使用 公知者，惟，爲形成均勻膜，於提起時以可變更爲上昇速 度者之裝置爲較佳者。做爲市售之浸漬塗佈裝置例者如： 胃 全自動浸漬塗層AD-7200、Semi auto浸漬塗層SD-6200、纖 維塗層SZC- 72 0 (以上，Surthuma通訊工業公司製）等例 〇 由該浸漬塗佈法取得之貼銅基板通常經過乾燥、曝光 、顯像、蝕刻、及光阻膜剝離步驟，更於必要時經過其他 任意步驟後，製造具有所定配線圖案之印刷電路板。 [實施例] 做爲光阻各成份（a_)〜（f)者可使用下述者。 [(A )水或鹼可溶性樹脂] 甲基丙烯酸-甲基甲基丙烯酸酯共聚物之3 5 4 _環氧基— 環己基甲基丙烯酸酯改性樹脂（Daice】】化學工業股份公司 製’商品名 C y c 1· 〇 m e r - A C A - 2 0 0 Μ、酸價 1 0 0 m g Κ Ο H / g、重 量平均分子量17;000) ’ [(B )纖維素衍生物] (b- 1 )羥乙基纖維素（東京化成股份公司製） (b-2 )甲基纖維素（東京化成股份公司製） -23 - 200525295 (20) (b-3 )羥丙基纖維素（日本曹達股份公司製） (b-4 )甲基羥丙基纖維素（信越化學股份公司製） (b-5)乙基羥乙基纖維素（Aczonobell股份公司製） [(D )含羥基有機溶劑] (d-Ι)乙二醇單丁醚（東京化成股份公司製） (d-2)丙二醇單甲醚（東京化成股份公司製） (d-3 ) 3-甲氧基-3-甲基-1-丁醇（東京化成股份公司 製） [(E)聚合性不飽和化合物] (e-])聚乙二醇二丙烯酸酯（共榮社化學股份公司 製） (e-2 )三羥甲基丙烷三丙烯酸酯（共榮社化學股份 公司製） [(F )光聚合啓發劑] (f - 1 ) 2 -甲基-1 - ( 4 -甲基噻吩基）-2 -嗎啉丙烷-卜酮 (C h i b a s p e c i a 1 i t y C h e ni i c a 1 股份公司製） (f-2 )二乙基噻唑酮（Chibaspeciality Chemical股份 公司製） [(其他成份）] 三乙胺（TEA) -24 > 200525295 (21) N -甲基嗎啉（Ν Μ Μ ) [(含羥基有機溶劑以外之有機溶劑）] 丙二醇單甲醚乙酸酯（PGM A ) [(觸變劑）] 環氧丙烷銨改性蒙脫石（SMC ) <實施例1 > [1 )光阻組成物之調製] (B )除纖維素衍生物’及（c )水之外，將以下表1 所示各成份依表1所載量.比進行混合後，取得均勻溶液。 再將此混合物劇烈攪拌之同時以2小時之時間滴入表1所載 量之（C )水。更加入表1所載量之（b )纖維素衍生物， 進行攪拌1 5小時後，調製水性光阻組成物。 [2 )黏度測定] 利用東機產業股份公司製之B型黏度計（b L型，N 〇 .] 方疋轉益）’25 C下以S疋轉益S疋轉數6 r p m進行測定之。 [3 )光阻組成物之浸漬塗佈] · 該1 )所調製之光阻組成物維持於3 5 t之溫度下， 利用SUrthUma通訊工業公司製浸漬塗層（商品名fib c〇at FC- 7 5 00 ) ’於兩面貼銅層合板（基板厚]3〇 μ，銅箔厚i8 -25- 200525295 (22) μ m，4 0 0 in m x 5 1 0 m m )進丫了浸漬塗佈後’將此基板於8 0 。(：下進行1 5分鐘乾燥後取得具光阻組成物塗膜之塗佈基板 。又，塗佈時之提起速度變更後，調整塗膜呈約8 μπι之厚 度者 [4 )捲度之測定] 該3 )取得之乾燥後2片塗佈基板使其塗佈重疊後，將 此重疊之基板挾於2片400mm x510mm xlmm之不銹鋼板 中，呈水平靜置之。於此狀態下靜置2天（23 t，相對濕 度6 0 % )後，輕輕剝離2片基板。將此重疊塗佈面畫分呈 1 cm X 1 c m之餘號，藉由具剝離部份之網_數，依以下基 準判斷剝離狀態。結果如以下表1所示。 ◎:出現剝離網篩數爲未達總數之2%時 〇：出現剝離網篩數爲總數之2%以上、5 %以下時 △:出現剝離網篩數爲總數之5 %以上、1 0%以下時 X :出現剝離網篩數爲總數之1 〇%以上時 [5 )密合性之測定] 利用elco meter (非磁性塗膜測厚計）公司製之塗膜 附著力試驗器（Adohition tester F 106型、塗佈面黏合鋁 製圓筒、測定此拉開時之剝離強度之裝置），室溫下進行 測定塗膜之剝離強度。 [6 )光澤測定] •26 - 200525295 (23) 利用市售之光澤計（tester產業製，OP - 1 02 )進行測 定後，以實施例1之光澤度做爲1之相對値示之。結果示於 表1 〇 [7 )線形狀及解像度之測定] •顯像後之‘評定 於該3 )取得之塗佈基板上使線與空間（以下略稱L/S )至20 μπι/20 μιη〜80 μηι/80 μιπ、10 μηι刻度之圖案分別通 過各具5個之光罩後於紫外線進行曝光（超高壓水銀燈， 主波長3 6 5nm，80mJ /cm2 )後，於30 。(：之1 °/。碳酸鈉水溶 液中浸漬60秒後進行顯像，於25 °C下進行水洗。所取得 基板藉由掃描型電子顯微鏡照片，使光阻線之··直線性依以 下基準進行判斷。又，未出現缺線及顯像殘留下取得之圖 案中，做爲具最小L/S値之解像度。結果示於以下表1。 ◎:線側壁爲幾乎呈直線性者。 〇：線側壁之一部份呈蛇行者。 △:線側壁之大部份呈部份蛇行者。 X :線側壁之蛇行極明顯者。 •蝕刻後之評定 該顯像後，接著藉由氯化銅水溶液後，於4 5 °C下進 行蝕刻60秒後，水洗之。取得基板藉由掃描型電子顯微鏡 照片，觀察殘存5個L/S = 4 0/40之光阻線形狀，依以下基準 進行評定。結果示於以下表]。 -27- 200525295 (24) ◎:缺陷、反撓度出現之圖案爲5個圖I 〇：缺陷、反撓度出現之圖案爲5個圖| △:缺陷、反撓度出現之圖案爲5個圖_ X .缺1¾、反燒度出現之圖案爲5個圖案 •剝離後之評定 該蝕刻後，再藉由3質量％氫氧化鈉水淬 下剝離光阻膜，經過水洗、乾燥後，取得形 案之基板。取得基板藉由掃描型電子顯微鏡 L/S = 40/40之銅配線的線形狀，依以下基準 果示於以下表1。 ◎:於銅配線間出現殘銅之圖，案爲5個圖 〇：於銅配線間出現殘銅之圖案爲5個圖 △:於銅配線間出現殘銅之圖案爲5個圖 X :於銅配線間出現殘銅之圖案爲5個圖； <實施例2〜6 > 表]所載之各成份使用表1所示量後與瀆 造水性光阻組成物。與實施例1同法進行評定 所示。 <比較例1> 除使用羥乙基纖維素之外，與實施例1 光阻組成物。與實施例】同法進行評定之結果 ξ中有0〜]個 【中有2〜3個 【中有4個 中有5個 ί液後於45 °C 成銅的配線圖 照片後，觀察 進行判斷。結 案中有〇〜1個 案中有2〜3個 案中有4個 g中有5個 f施例1同法製 :之結果如表1 司法製造水性 示於表1。 -28- 200525295 (25) <比較例2 > 除使用2.0重量份之羥乙基纖維素之外，與實施例1同 法製造水性光阻組成物。同法進行評定後結果示於表1。 <比較例7〜16> 表2所載之各成份使用表2所載量後，製造水性光阻 組成物。與實施例1同法進行評定結果示於表2。 <比較例3〜7、實施例17〜21 > 表3所載各成份使用表3所載量後，製造水性光阻組 成物。與實施例1同法進行評定結果示於表3。 200525295 (26) 5 實施例6 r—^ 1 0.05 1 1 1 1 CO 5.05 1 1 (N »·〇 o 寸 (N 1 1 ο ο ◎ VO ο 〇〇 ο 60/60 〇 〇 〇 實施例5 r—( 1 0.05 1 1 1 1 r—K I 10.05 I 1 1 (N ^r\ 〇 寸 (N 1 1 ο ο ◎ r- ο ο ο 50/50 〇 〇 〇 實施例4 IT) τ—Η 1 0.05 1 1 I 1 jo in r—i 15.05 1 vy^ 1 (N 〇 寸 (N 1 i ο V ' Ή ◎ \D Ο r-H 1ί 50/50 〇 〇 〇 實施例3 VO τ—^ 1 0.05 1 1 1 1 〇 寸 ^T) r-H 20.05 1 1 (N to 〇 寸 (N 1 1 Ο ο ◎ 卜 Ο ο 50/50 〇 〇 〇 實施例2 ν〇 r—Η 1 0.05 1 1 1 1 in m ( | 25.05 | 1 1 (N to o 寸 1 1 ο r-H ◎ 卜 ο Ο) ο Γ 50/50 〇 〇 〇 比較例2 ΙΤ) r-H 1 ΓΝ| 1 1 1 1 to | 28.1 | 1 1 (N o 寸 <N 1 1 Ο r-H X σ\ ο ο 60/60 〇 <3 比較例1 i〇 * 1 1 1 1 1 1 30.1 | 1 1 (N o 寸 (Ν 1 1 Ο Τ Ή ◎ (Ν Ο ο 80/80 X X X 實施例1 ΙΟ 1 0.05 1 1 1 1 ο m cn 30.05 1 1 (N <n 〇 寸 (Ν 1 1 Ο s Η ◎ r-； ο ?—( 50/50 〇 〇 〇 質量％ BlBf, 質量％ 質量％ 質量％ i質量％ !質量％ 質量％ 質量％ 質量％ 質量％ ! 質量％ 質量％ 質量％ 質量％ 質量％ 質量％ 質量％ 質量％ MPa 光阻線直線性 g δ 骧 δ 骧 編 (a-1) (a-2) (b-1) (b-2) (b-3) « 3 1 (b-5) 1 (d-1) (d-2) Ί (d-3) ! /^N (e-2) -N • ^ TEA NMM PGMA 合計 捲度 密合強度 光澤 解像度 /s ^^/ ί ^s -30- 200525295 (27) rvl^ 實施例16 〇〇 1 1 1 (N 〇 1 1 oo 31.3 1 m 1 <N o 1 <N 1 O o ◎ o r—^ V·· 一 30/30 ◎ ◎ ◎ 實施例15 〇 1 1 1 0.15 1 1 寸 o r-H 30.35 1 寸 1 (N o 1 (N 1 o o ◎ oc o (N r—i 30/30 ◎ ◎ ◎ 實施例14 m 1 1 1 ψ i 1 1 P； m I 28.4 I 1 寸 1 (N ΚΓ) 〇 1 rs) 1 o H ◎ CTs o r—H ψ ^ 30/30 ◎ ◎ ◎ 實施例13 r—^ 1 1 1 0.05 1 1 cn m r*H 26.45 1 1 寸 (N o 1 Oi 1 o r—i ◎ On 〇 o y H 30/30 ◎ ◎ ◎ 實施例12 1 1 1 0.02 1 1 m 1 1 寸 CM o 1 CM 1.48 〇 o ◎ o o 30/30 ◎ ◎ ◎ 實施例11 r—^ 1 1 1 1 1 | 0.05 O ，'叫 20.05 1 1 (N in o 1 寸 (N 1 o i—l ◎ 卜 o 0 1 ' Ή 30/30 ◎ ◎ ◎ 實施例10 r—Η 1 1 1 1 0.05 1 o ，丨H 20.05 1 1 <N o 1 寸 (N 1 o Ψ ^ ◎ oo o o f 30/30 ◎ ◎ ◎ 實施例9 to ，— 1 1 1 0.05 1 1 o to r— 20.05 1 <n 1 <N o 1 寸 CN 1 o ( ◎ oo o f — 30/30 ◎ ◎ ◎ 實施例8 ΙΟ r—< 1 1 0.05 1 1 1 o 20.05 1 1 CN o 1 寸 (N 1 o H ◎ o o T—^ 40/40 ◎ ◎ ◎ 實施例7 t—H 1 0.05 1 1 1 1 o r_H 20.05 1 1 <N O 1 寸 1 〇 〇 ◎ oc o On 〇 50/50 〇 〇 〇 質量％ 質量％ 質量％ i質量％ 質量％ 質量％ 質量％ 質量％ 質量％ 質量％ 質量％ 質量％ 質量％ 質量％ 質量％ 質量％ 質量％ 質量％ MPa 光阻線直線性 8 g 鹱 銅線形狀(剝離後） (a-1) (a-2) (b-1) (N 1 I (b-3) 0>5) (d-1) (d-2) ! (d-3) /^N (e-2) /^\ g TEA NMM PGMA U_ niin <n 捲度 密合強度 光澤 解像度 g £ -31 - 200525295 (28) 實施例21 寸 ) 1 1 1 1 ▼—1 1 寸 1 1 寸 1 (Ν un Ο 寸 oi 1 O o ◎ oo ο r—( τ·— 40/40 ◎ ◎ ◎ 實施例20 1 m 1 1 1 1 r—Η 1 ο m (N 1 1 寸 1 (Ν to Ο 寸 (Ν 1 o o ◎ r- ο f < 40/40 ◎ ◎ ◎ 實施例19 1 1 1 1 1 1 0.05 I 1 ο 1 21.05 I 1 1 寸 1 (Ν CO Ο 寸 oi 1 o o ◎ oo ο τ—^ r—Η 40/40 ◎ ◎ ◎ 實施例18 〇 I 1 1 1 1 0.05 1 ο 〇 1 31.05 1 寸 1 (Ν ο 寸 oi 1 o o ◎ oo ο (Ν Τ—Η 40/40 ◎ ◎ ◎ 實施例Π 〇 ，Η 1 1 1 1 1 0.05 1 σ\ m 〇 oo CN 1 5.05 1 1 m 1 (Ν υο Ο oi 1 o o ◎ r- ο ψ 1 ▼—Η 50/50 ◎ ◎ ◎ 比較例7 m 1—< 1 1 1 1 1 1 ο 卜 m m | 28.4 1 1 1 寸 1 (Ν Ο 1 <N o o 〇 OJ ο rn ο 70/70 X X X 比較例6 m τ—( 1 1 1 r—Η 1 1 1 ο 1—Η 寸 rn 1 ο f i 1 ΓΝ1 ιη Ο 1 (N o o <] ο 60/60 <3 < <3 比較例5 m 1 1 1 * ' 1 ^ 1 1 1 m 38.4 1 1 寸 1 r-j m ο 1 CN o o 〇 ο ο 70/70 <] <3 <3 比較例4 » "·ί ψ ' 1 1 1 s 1 1 1 !〇 (Ν ν—^ 寸 寸· 1 1 m 1 Ο 1 1 o o <3 ο ο 70/70 <3 <3 <3 比較例3 m τ—Η 1 1 1 1 1 1 m <N m 35.4 i 1 卜 寸 1 ο 1 (N o o 〇 ο ο 60/60 <3 質量％ 質量％ 質量％ 質量％ 質量％ 質量％ 質量％ 質量％ 質量％ 質量％ 質量％ 1 質量％ 質量％ 質量％ 質量％ 質量％ 質量％ 質量％ 質量％ 質量％ MPa 光阻線直線性 S g SI δ 錶 骧 ，^Ν r—^ % t \ (b-2) SMC /^s ▼ Η 1 5 PGMA τ*-Η /S r? TEA NMM 合計 捲度 密合強度 光澤 解像度 、~^ S' u U 、 -32 -200525295 (1) IX. Description of the invention [Technical field to which the invention belongs] The present invention relates to a photoresist composition for printing substrate manufacturing, especially an aqueous solution type or dispersion type photoresist composition, and a photoresist using the same Manufacturing method of coated substrate. [Prior art] In the prior art, when manufacturing a printed circuit board, an insulating substrate having a conductive metal layer of copper foil (including metals other than copper may be used, and the following may also be referred to as "copper substrate" only). After the photoresist coating is formed, exposure is performed through a mask having a desired pattern, development is performed with water or alkaline water, and then the conductive metal layer with no remaining photoresist is etched with an etchant. After the photoresist is peeled off, it is performed according to the desired wiring pattern formed. Methods for forming a photoresist layer on a copper-clad substrate include a dry film method and a liquid photoresist coating method. In the liquid photoresist coating method, in addition to a method of applying liquid photoresist to a copper-clad substrate by roll coating or screen printing, a dip coating method is known. This method involves immersing a copper-clad substrate in a large amount of a photoresist composition (mostly a solution), pulling it out, and drying it to volatilize the solvent to form a photoresist coating film on the copper-clad substrate. The liquid photoresist composition used in the dip coating method or the like is used as a solvent, and a highly volatile organic solvent has been used. However, in recent years, due to concerns about affecting the human body and the environment, it has been disclosed as: Japanese Patent No. 2 743 7 (Patent Document 1) uses water as a photoresist composition contained in a solvent. However, the water-based photoresist composition uses water with a slow evaporation rate as a solvent -5-200525295 (2), so the drying time after photoresist coating is quite long. Therefore, the application of the photoresist solution causes problems such as "draping" and uneven coating thickness during drying. In order to prevent this “drip,” it is known to add a thixotropic agent (with a thixotropic agent) or a tackifier to the photoresist composition, such as in Japanese Patent Application Laid-Open No. 2003 -23 3 1 8 3 (Patent Document 2 ) It is disclosed that a composition using an inorganic thickener is used. Although the uniformity of the thickness of the coating film can be maintained, the smoothness and adhesion strength of the coating film are insufficient. In particular, the smoothness of the coating film is expected to be further improved in order to obtain a high-definition wiring pattern. In addition, those who use cellulose derivatives such as hydroxyalkylcellulose as the demutant or thickener of the organic system are disclosed (eg, Japanese Patent Laid-Open No. 5 5 -04 5 725 (Patent Literature) 3), Japanese Patent Application Laid-Open No. 1 1-1 746 67 (Patent Document 4)). However, the aqueous solution of these cellulose derivatives is known to produce reversible gelation of cellulose derivatives with a certain temperature as the boundary. Therefore, when the cellulose derivative is precipitated from the solution above this temperature, it is obvious that Reduce the viscosity of the aqueous solution. Therefore, when an aqueous photoresist containing a cellulose derivative is applied and dried above the gelatinization temperature, the "viscosity" is apparently generated after the viscosity is reduced during drying. Furthermore, by reducing the viscosity during drying, and changing the dispersion state of the composition, the smoothness of the coating film is impaired. In addition, the gelation temperature varies depending on the kind of the cellulose derivative. Generally, it is extremely difficult to solve the problem by the prior art that significantly lowers the boiling point of water. Japanese Patent Application Laid-Open No. 2000-292922 (Patent Document 5) discloses a photosensitive composition containing a hydrophobic polymer and a water-soluble polymer at a weight ratio of 0.0 5 to 4.0. It is recorded that those who use water-soluble polymer as the water-soluble polymer can use the cellulose-based polymer. However, it contains a large amount of-6-200525295 (3) When the cellulose derivative is simply used as an aqueous composition, since the cellulose is hydrophilic, the drying of the coating surface is insufficient, which is obvious on the coating surface. Causes curl. In addition, by adding water, the smoothness of the coating surface is reduced, and the problem of reducing the resolution of the pattern is not solved. [Patent Document 1] JP 05-2743 7 [Patent Document 2] JP 2003--23 3 1 83 [Patent Document 3] JP 5-5-04 5 725 [Patent Document 4] Special Kaiping No. 1 1-1 74667 [Patent Document 5] JP 2000-292922 [Summary of the Invention] The object of the present invention is to provide a water-containing photoresist composition as a solvent, and directly maintain good photoresist adhesion. And good curl, can achieve high-definition wiring pattern of the photoresist composition. In view of the above, the present inventors conducted detailed investigations and found that among the photoresist compositions formed from water-soluble or alkali-soluble resins and cellulose derivatives, even when a very small amount of cellulose derivatives is used, a specific amount of This problem can be effectively solved with water and a specific solvent, and the present invention has been completed. That is, the present invention relates to the following [1] to [9]. [1] This feature is an aqueous photoresist composition containing (A) a resin soluble in water or an alkaline aqueous solution, (B) a cellulose derivative, (C) water, and (D) a hydroxyl-containing organic solvent, The content of the (B) cellulose derivative in the photoresist composition is 0.001 to 1.0% by mass, the (C) water content is 25 to 65% by mass, and the content of the (D) hydroxyl-containing organic solvent is 1 5 ~ 50% by mass 200525295 (4) Water-based photoresist composition. [2] This feature contains (A) a resin soluble in water or an alkaline aqueous solution, (B) a cellulose derivative, (C) water, and (D) a radical-containing organic solvent, and (E) a polymerizable polymer. Saturated compounds and (f) water-based photoresist compositions of photopolymerization heuristics The content of the (B) cellulose derivative in the photoresist composition is 0.001 to 1.0% by mass, and the (C) water content is 25 ~ 65% by mass, and the (D) aqueous photoresist composition having a hydroxyl group-containing organic solvent content in the range of 15 ~ 50% by mass. φ [3] The characteristic ratio (A) of the mass ratio (A) / (B) of the resin (A) soluble in water or an alkaline aqueous solution to the cellulose derivative (A) / (B) is from 10 to 100 [ 1] or [2] water-based photoresist composition. [4] The feature is that the water-soluble light of [A] in (A) is a resin soluble in water or an alkaline aqueous solution using (meth) acrylic acid as a monomer copolymer. Those who block the composition. [5] This feature is that the cellulose derivative (B) is an aqueous photoresist composition according to any one of [II] to [4] of a hydroxyalkyl cellulose. [6] This feature is that the (D) hydroxyl-containing organic solvent is at least one monoalkyl ether of a diol compound, a monoester of a diol compound and an aliphatic carboxylic acid, and an [alpha] -hydroxycarboxylic acid ester [ 1] ~ [5] is an aqueous photoresist composition. [7] A method for producing a photoresist-coated substrate characterized by impregnating an insulating substrate having a conductive metal in an aqueous photoresist composition according to any one of [1] to [6]. [8] This feature is a method for manufacturing a printed circuit board using the water-based photoresist composition according to any one of [1] to [6]. 200525295 (5) [9] A printed circuit board manufactured using the water-based photoresist composition of any one of [1] to [6]. The water-based photoresist composition of the present invention can provide a printed circuit board having excellent adhesion, curlability, and surface smoothness to form a high-definition wiring pattern. [Embodiment] [Best Mode for Implementing Invention] The present invention will be described in detail below. [(A) Resin that is soluble in water or alkaline aqueous solution] (A) A resin that is soluble in water or an aqueous solution (hereinafter also referred to as "water and alkali-soluble resin") used in the photoresist composition of the present invention. Refers to resins that are soluble in alkaline aqueous solutions such as water and aqueous sodium carbonate. The water and alkali-soluble resins of the present invention are those which are soluble in the developing solution and hardly soluble in the etching solution, and are preferably those containing a resin component having a carboxyl group or an anhydrous substance group in the molecule. As a resin having a carboxyl group or an anhydrous substance based on the molecule, such as a copolymer containing (meth) acrylic acid and (meth) acrylate as a monomer, a propylene resin, and a copolymer of (meth) acrylic acid and ethylene And copolymers of anhydrous maleic acid with ethylene or styrene, especially those with the best adhesion and curl of acrylic resin. 5 (meth) acrylic acid means acrylate and / or acrylic acid. The (A) water and alkali soluble resin can be used in the presence or absence of a photopolymerization initiator, and can be irradiated by ultraviolet rays, X-rays, electron rays, etc. 200525295 (6) Photopolymerizable resin that causes photopolymerization It is suitable, for example, a polymerizable group having a plurality of ethylenic unsaturated bonds in the molecule is an example. Examples of the photopolymerizable resin may be used alone or in combination of known ones. For example, the photopolymerizable resin may be selected from a group of (1) to (5) below. (1) A reactant of an unsaturated hydroxy compound and a resin having more than one functional group selected from a carboxyl group, a carboxylic acid anhydrous group, an isocyanate group, and an epoxy group; (2) an unsaturated epoxy compound and a resin having one or more types The functional group is selected from reactants of resins in carboxyl group, carboxylic acid anhydrous group, isocyanate group, amine group, and hydroxyl group; (3) unsaturated unsaturated acid or unsaturated carboxylic acid anhydrous and one or more functional groups selected from Reactants of resins in hydroxyl, amine, isocyanate and epoxy groups; (4) Unsaturated amine compound and one or more functional groups selected from carboxyl group, carboxylic acid anhydrous group, formamyl group, keto group, Reactant of isocyanate group and resin in epoxy group; (5) Unsaturated isocyanate compound and resin with more than one functional group selected from carboxyl group, carboxylic acid anhydrous group, amine group, hydroxyl group and epoxy group. Reactant. The weight-average molecular weight acid value (mgKOH / g) of these photopolymerizable resins is arbitrary, and the weight-average molecular weight is preferably 500 to 100,000, particularly 1,000 to 50,000, and the most preferable is 25,000 to 20,000, the acid value is preferably 20 ~ 3 50, especially 50 ~ 2 50 is preferred, the most preferred is 80 ~ 200 -10- 200525295 (7) the weight average molecular weight is by gel permeation chromatography, The acid value is measured in accordance with JIS K 560]. As specific examples of the unsaturated hydroxy compound, polyethylene glycol mono (methyl) such as 2-methyl ethyl acrylate, 2-hydroxypropyl (meth) acrylate, diethylene monoacrylate, and the like can be used. Polyethylene glycol mono (meth) propanoic acid, such as acrylate, triethylmono (meth) acrylate, etc. 1,4-butanediol mono (meth) propionate, ethylene glycol mono (methyl) ) Polyethylene glycol mono (methyl propyl ether, N-hydroxymethyl acrylamide), allyl alcohol, methallyl alcohol, ethylene, methylol, etc. Styrene, allyl phenol, etc. Specific examples of unsaturated epoxy compounds include glycidyl methacrylate, allyl glycidyl ether, 3,4-epoxycyclomethyl (methyl Base) acrylate and other examples. As the unsaturated carboxylic acid and its anhydrous examples, it can be used such as: (methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, sorbic acid, cinnamic acid, naric acid, oleic acid, Oleic acid, linolenic acid, licanoic acid, linolenic acid, arachidonic acid, and these anhydrous substances are examples of unsaturated amine compounds such as: allylamine, diallylaminostyrene, aminomethyl Examples of reactants of styrene, acrylamide, unsaturated carboxylic derivatives, and polyamines such as ethylene diamine. Examples of unsaturated isocyanate compounds include 2-isoester ethyl (meth) acrylate , Allyl isocyanates, reactants of unsaturated compounds with cyanate esters such as tolyl diisocyanate, xylylene diisocyanate, etc. By the group (diol glycol ester, allyl) alkenylphenyl (hexyl group ) Acid, amine, amine, acid or cyanohydroxy polyiso-11-200525295 (8) the resins with one or more functional groups used in (1) to (5) means at least one or more selected from the group consisting of Unsaturated carboxylic acid, unsaturated carboxylic acid anhydrous, unsaturated isocyanate Ester compounds, unsaturated epoxy compounds, unsaturated hydroxy compounds, and unsaturated amine-based compounds are individually coated with a film copolymer, etc. Examples of resins having a carboxyl group as a functional group include poly (meth) acrylic acid, (Meth) acrylic acid-meth (meth) acrylate copolymer, ethylene- (meth) acrylic acid copolymer, terminal carboxylated polybutadiene, terminal carboxylated butadiene-acrylonitrile copolymer, phenol resin Examples of (anhydrous) polyvalent carboxylic acid adducts. Examples of resins having a hydroxyl group include polyhydroxyethyl (meth) propionate, hydroxyethyl (meth) acrylate-styrene copolymer. , Hydroxyethyl (meth) acrylate-methacrylate copolymer, phenolic lacquer type phenol resin, polyvinyl alcohol, partially saponified ethylene-vinyl acetate copolymer, polyglycerol, polyvinylphenol, epoxy resin Carboxylic acid adducts, polyethylene glycols, polypropylene glycols, end-products (gasification), polybutadiene combustion, end-treatments (amination), petroleum resins and reactants of polyvalent alcohols and polyvalent isocyanates Examples of epoxy resins such as : Polyglycidyl (meth) acrylate, glycidyl (meth) acrylate-styrene copolymer, glycidyl (meth) acrylate-methacrylate copolymer, phenolic lacquer type phenol resin Examples of reactants with epichlorohydrin, reactants of polyvalent phenol and epoxypropane, and examples of reactants of polyvalent alcohol and epichlorohydrin. Examples of resins with amine groups include polypropylene amidamine and polyolefin. Propylamine, polyethylene formamide saponification, polyethylene acetamide saponification, polyamine styrene, amine styrene-styrene copolymer, reactant of carboxyl-containing resin and polyvalent amine, -12-200525295 ( 9) Examples of urine resins and melamine resins. Examples of resins having isocyanate groups are: poly-2 -isocyanate ethyl (meth) acrylate, 2-isocyanate ethyl (meth) acrylate-methyl Examples of the (meth) acrylate copolymer, a reactant of a polyvalent isocyanate compound, and a polyvalent hydroxyl compound. More specifically, the ideal examples of (1) to (5) are (1-1) the reactant of an unsaturated hydroxy compound and a resin having a carboxylic acid anhydride group, such as hydroxyethyl acrylate and styrene-anhydrous Reactant of maleic acid copolymer, and the reactant is more alkaline; (1-2) Unsaturated hydroxy compound and isocyanate resin reactant (2-1) Unsaturated epoxy compound and carboxyl resin Reactants, such as: reactants of glycidyl acrylate and methacrylate-methmethacrylate copolymer, 3,4-epoxy-cyclohexyl methacrylate and methacrylic acid Reactants of methacrylic acid ester copolymers and those reacting more with alkali; (3-1) unsaturated carboxylic acid or unsaturated carboxylic acid anhydrous and reactant with epoxy resin, such as: Reactants of acrylic acid and polyglycidyl methacrylate and reactants of acrylic acid and glycidyl methacrylate-methmethacrylate copolymer, etc .; Among them, a copolymer made of a monomer composed of (meth) acrylic acid is particularly preferable, and a copolymer of (meth) acrylic acid and an ester thereof or a propylene resin made of a modified substance thereof is more preferable. Specific examples: the reaction of glycidyl acrylate and methacrylic acid-methmethacrylate copolymer-13- 200525295 (10) compounds, 3,4-epoxy-cyclohexyl methacrylate and methyl propyl Reactants of the brilliant acid methacrylate copolymers and these reactants are more advanced. As photopolymerizable resins, in addition to the above (1) to (5), reporters are also used. (6) Alone or co-modified conjugated diene compounds such as polybutadiene and their modified substances; (7) Unsaturation in the unsaturated bond in the aliphatic chain in the esterified product of epoxy resin and unsaturated fatty acid Polymerizable unsaturated resin with addition of dicarboxylic acid or its anhydrous substance; (8) Synthetic unsaturated resin formed by unsaturated fatty acid-modified high acid value alkyd resin; and (9) Malay Chemicals The polymerizable unsaturated resin and the ethylenic unsaturated compound having one or more polymerizable unsaturated bonds in one molecule. The content of the (A) in the aqueous photoresist composition of the present invention is generally 5 to 5% by weight, more preferably 7 to 30% by weight, and particularly 9 to 25% by weight. When it is less than 5% by mass, the film thickness when applied to an insulating substrate is too thin, causing problems such as reduction in film strength. Conversely, if it exceeds 40% by mass, the thickness of the film becomes thick, and the viscosity is remarkably increased, which causes problems such as waste of drying time. [(B) Cellulose Derivative] In the present invention, the (B) cellulose derivative can be used, for example, an alkyl group, a hydroxyalkyl group, a carboxyalkyl group, or the like is introduced into a fiber base, and is not limited to a male-methyl group. The t reaction can make the polymer fatty acid into a polymer with a mixed quality of 40, and the yield is too high. -14-200525295 (11), and hydroxyalkyl cellulose is preferred. Examples of the alkyl group include methyl, ethyl, propyl, and butyl, and those of the hydroxyalkyl group include hydroxyethyl, propyl, and hydroxybutyl. Basic examples are: residual methyl etc. Specific examples of these are: alkyl ethers of cellulose such as methyl cellulose, ethyl cellulose 'benzyl cellulose, hydroxyalkyl ethers such as hydroxyethyl cellulose, hydroxypropyl cellulose, methyl L ethyl cellulose, ethyl cellulose Basic chemical institutes such as ethyl cellulose, methyl ethyl cellulose, methyl hydroxypropyl cellulose, ethyl hydroxypropyl cellulose, and carboxyalkyl fibers such as carboxymethyl cellulose Cellulose esters such as cellulose and cellulose acetate. The introduction amount of these alkyl groups and hydroxyalkyl groups can be arbitrarily set according to the purpose, and generally, the glucose contained in cellulose is in the range of 0.05 to 2.5 equivalents. Among them, methyl, cellulose, ethyl hydroxyethyl cellulose, methyl propyl propyl cellulose, ethyl hydroxypropyl cellulose, and hydroxypropyl cellulose are preferred. 'Specially hydroxypropyl fibers Is best. These can be used by marketers, such as: HEC Dai cell (Dai cell), Be] mOC〇U (Aczonobel), fiEC: (Sumitomo Chemical Co., Ltd.), CuIuceH (Sanjing Co., Ltd.), Metorose (Beijing Chemical Industry Co., Ltd.), Nissho HPC (Japan Soda Co., Ltd.), th 11 〇se (cra) 丨 antjapan Co., Ltd., etc. are available. (B) The content of the cellulose derivative is 0.001 to 1.0% by mass in the aqueous photoresist composition of the present invention, and if it is not in this range, the effect of the present invention cannot be obtained. That is, when it exceeds 1.0% by mass, not only the smoothness of the surface of the coating film is reduced, but curling is also apparently generated. On the other hand, if it is less than 0.01% by mass, the thickness of the coating film will be uneven, resulting in poor appearance such as bounces, spots, and the like. -15- 200525295 (12) Low surface smoothness of the coating film. Moreover, in the present invention, the (A) / (B) cellulose derivative of the (A) water-soluble or alkaline aqueous solution has a mass ratio (A) / (B) of 10 to 1,000, and when the (A) / ( B) When it exceeds 350,000, it is preferable that IJ (A) is 15 mass% or more. [(C) Water] The aqueous photoresist composition of the present invention uses (C) water as a solvent. By using (C) water, the amount of organic solvents with high volatility can be reduced, and the ignition point of the photoresist composition can be increased, and the safety during storage and transportation can be improved. The (C) water content in the water-based photoresist composition of the present invention is mainly those having good coating film properties after gelation of the cellulose-inhibiting cellulose derivative. The water-based photoresist composition is preferably 25 to 65% by mass, which is more The best is 25 to 60% by mass, more preferably 30 to 56% by mass, and 35 to 52% by mass are particularly desirable, and the best is 35 to 50% by mass. When the water content exceeds this range, gelation of the cellulose derivative easily occurs, the smoothness of the coating film is lost, and it is difficult to obtain a high-definition pattern. Conversely, if the water content is below this range, the solubility of the cellulose derivative will be reduced, the smoothness of the coating film will be lost, and a high-definition pattern will not be obtained. [(D) Hydroxyl-containing organic solvent] The (D) hydroxyl organic solvent of the present invention is a compound having 1 or more hydroxyl groups in the molecule, and these are not limited to the publicly known ones, and can be used arbitrarily-16-200525295 ( 13) Compounds, diol compounds, monoalkyl ethers of diol compounds, monoesters of diol compounds and aliphatic carboxylic acids, and α-hydroxycarboxylic acid esters are preferred. These organic solvents containing a radical may be used singly or in combination. The content of (D) in the water-based photoresist composition of the present invention is preferably 15 to 50% by mass, more preferably 20 to 55% by mass, and more preferably 20 ~ 45 mass%, 25 ~ 45 mass% is particularly desirable, and 25 ~ 40 mass% is optimal. When the content of (D) is less than 15% by mass, it is difficult to control the gelation of the cellulose derivative after heating, and the smoothness of the coating film is lost 'It is difficult to obtain a high-definition pattern. Even after “drips” occur during drying, the uniformity of the thickness of the coating film is reduced. On the other hand, if it exceeds 50% by mass, the solubility of the cellulose derivative is reduced, and the smoothness of the coating film is lost, and the pattern of high-precision Putian has not been obtained. Specific examples of the (D) hydroxyl-containing organic solvent are: @ 'ethanol, 1-propanol, isopropanol, 1-butanol, pentyl alcohol, ethylene glycol, propanol, glycerol, 1, 2-propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethyl ether Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, ethylene glycol monoacetate, diethylene glycol monoethyl ether Acid esters, triethylene glycol monoacetate, propylene glycol monomethyl®, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, Examples of dipropylene glycol monobutyl ether, propylene glycol monoacetate, and dipropylene glycol monoacetate. Also available] .; 3-propanediol, butanediol, methyl-1,3 alcohol, 2: 2-dimethyl-1,3-propanediol, 2-methyl-1,3-butanediol, 3_ -17- 200525295 (14) 1,3-butanediol, 1,3-pentanediol, 2,4-pentanediol, 1,3-hexanediol, 2,4-hexanediol, trimethylol Propane, pentaerythritol, 3-methoxy-1-propanol, 2-methyl-3 · methoxy-propanol, 2,2-dimethyl-3-methoxy-1-propanol, 3-methoxy-1-butanol, 3-methoxy-3-methyl-1-butanol, those substituted with ethoxy, other alkoxy, 3-ethoxy -1-propanol, 2-methyl-3-ethoxyl-propanol, 2 5 2 -dimethyl-3-ethoxyl-1-propanol, 3-ethoxyl-propanol Butanol, 3-ethoxymethyl-3-methyl-butanol, and other ethoxy groups are substituted with other ethoxy groups. As the (D) hydroxy-containing organic solvent, an α-hydroxycarboxylic acid ester can also be used, and any known ones can be used without limitation. Specific examples of these α-hydroxycarboxylic acid esters are: methyl glycolate, ethyl glycolate, n-propyl glycolate, isopropyl glycolate 'n-butyl glycolate, glycolic acid Isobutyl esters, glycolic acid eta-pentyl esters, glycolic acid eta-hexanoic acid, cyclohexyl glycolic acid, and other glycolic acid vinegars, methyl lactate, ethyl lactate, eta-propyl lactate, and isopropyl lactate Lactate such as η-butyl lactate, isobutyl lactate, amyl lactate, iso-amyl lactate, η-hexyl lactate, cyclohexyl lactate, lactate, etc. Ethyl hydroxybutyrate, ^ -hydroxybutyric acid η · propionate, α-hydroxybutyric acid isopropyl vinegar, α-hydroxybutyric acid η-butyric acid, α-hydroxybutyric acid isobutyl ester, α-hydroxybutyric acid η-pentyl ester, α-Hydroxybutyric acid hexanoate, α-Hydroxybutyric acid cyclohexyl, etc., α-Hydroxybutyric acid ester, α-Hydroxyglycyrrhizinic acid methyl ester, α-Hydroxyglycyrrhizin ethyl ester, α-Hydroxyglycylate propyl, α- Isopropyl acetate, α-Isobutyl acetate, α-Isobutyl acetate, α-Isobutyl isopropyl ester, α-Hydroxygijiacetate, Amyl hexyl-Hydroxygijiate, α-hydroxyl Cyclohexyl Glycylate - hydroxyvaleric oxalate, etc. Examples. In the photoresist composition of the present invention, if necessary, other well-known organic solvents may be added. The solvent is, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone; aromatic hydrocarbons such as toluene, xylene, ethylbenzene, tetramethylbenzene; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate , Ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol dimethyl ether 'ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol Glycol ethers such as dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, acetates such as methyl acetate, ethyl acetate, butyl acetate, and 3-methoxy-propionic acid methyl ester , 3-methoxy-ethyl propionate, 3-methoxy-butyric acid methyl ester, 3-methoxy-butyric acid ethyl ester, 3-methyl-3-methoxy-butyric acid methyl ester, 3-methyl Methyl-3-methoxy · ethyl butyrate, 2-methoxy-cyclohexanecarboxylic acid methyl ester, 3-methoxy-1-propyl acetate, 2-methyl-3 -methoxy Propyl-1-propyl acetate, 2,2-dimethyl-3-methoxy-butylpropyl acetate, 3-methoxy-butylbutyl acetate, 3-methoxy-3-methyl -1-Butyl acetate, those methoxy groups are substituted by ethoxy groups, other alkoxy groups, these ethoxy groups are substituted by other groups Group substituted by, octane, decane, cyclohexane and the like; alicyclic hydrocarbons such as petroleum ether, minute fly stone oil, hydrogen Jie fossil oil, paraffin oil solvent and a petroleum solvent embodiments. [(E) Polymerizable unsaturated compound] The aqueous photoresist composition of the present invention preferably contains (E) a polymerizable unsaturated compound in addition to the compounds (A) to (D). The (E) polymerizable unsaturated compound is not particularly limited as long as it is a compound polymerized by a (F) photopolymerization heuristic, and a known one may be used alone or a combination of plural kinds may be used. The (E) polymerizable unsaturated compound in the photoresist composition of the present invention contains Q · 1 ~ 1 Q mass% in the photoresist aqueous composition of the present invention, and 0.5 ~ 7 mass% is more preferable, and the most preferable Those are] to 5% by mass. (E) Polymerizability > 19-200525295 (16) When the unsaturated compound content is less than 0.01% by mass, the photopolymerization will not proceed sufficiently and it will be difficult to maintain the photoresist performance. On the other hand, if the content exceeds [%] by mass, the coating film properties are reduced, and curl is noticeably generated. Examples of the (E) polymerizable unsaturated compound include: the unsaturated hydroxy compound, the unsaturated epoxy compound, the unsaturated carboxylic acid or the unsaturated carboxylic anhydride, the unsaturated amine compound, the unsaturated isocyanate compound, styrene, Examples of alkyl (meth) acrylates or aryl esters such as vinyl toluene, divinylbenzene, and methmethacrylate, (meth) acrylates of polyvalent alcohols, and allyl ethers of polyvalent alcohols. Examples of (meth) acrylates of polyvalent alcohols include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate , Polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate Esters, pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) propionate, and the like. Examples of allyl ethers of polyvalent alcohols include ethylene glycol diallyl ether, diethylene glycol diallyl ether 'diallyl ether, polyethylene glycol diallyl acid, and trimethylol. Examples of propane triallyl ether, glycerol triallyl ether, pentaerythritol tetraallyl ether, and the like. [(F) photopolymerization heuristic] As the (F) photopolymerization heuristic, a known one can be used. Specific examples: Benzoin, Benzoin methyl ether, Benzoin ethyl ether, benzyl, diphenyl disulfide, tetramethylthiuram monosulfide, diethylfluorenyl, eosin, sulfur only, Mi-20- 200525295 (17) ketone, anthraquinone, chloroanthraquinone, methylanthraquinone, α-hydroxyisobutyl ketone, p-isopropyl-α-hydroxyisobutyl ketone, α, α, dichloro -4-phenoxyacetophenone, phenoxy-1-cyclohexylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, methylbenzophenone carbamate, 2- Methyl-1- [4- (methylthio) phenyl-morpholine propane 1 ketone, benzophenone, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthine g, 2-isopropylthioxanthone, 4-benzidine-4'-methyldiphenyl sulfide, ethyl n, N-dimethylamine benzoate, amyl N, N-dimethylamine benzoate, and tris Examples of ethanolamine. These can be used alone, but a combination of plural is preferred. The content of these photopolymerization heuristics is preferably 0.01 to 10% by mass in the aqueous photoresist composition of the present invention, more preferably 0.1 to 5% by mass, and most preferably 0.5 to 3% by mass. · When (F) When the content of the photopolymerization initiator is less than 0.01% by mass, the photopolymerization cannot be performed sufficiently, and it is difficult to maintain the performance of the photoresist. Conversely, if it exceeds 10% by mass, the coating film properties will be reduced. In the photosensitive composition of the present invention, a polymerization stopper may be appropriately used in order to maintain stability during storage and processing. As examples of such polymerization stoppers, polymerization stoppers known in the prior art can be used, such as; phenols (3,5_di-second-butyl-4 · hydroxytoluene, etc.), hydrogen rollers (hydrogen rollers, hydrogen Monomethyl ether, etc.), and catechols (with catechol, tertiary butyl and catechol, acetol), etc. 〇 If necessary, you can add acid blue, phthalocyanine blue, phthalocyanine green, Iodine green, Yiqi gas sheet, gentian violet, titanium oxide, carbon black, Cai Hei and other well-known coloring months! I. External defoamers and / or flavoring agents such as oxygen water, fluorine-based, polymer-based, imidazole ¥, D roll U seat system, three η seat system, silane coupling agent, etc. 200525295 (18) In the photoresist composition of the present invention, a surfactant may be added to adjust the surface tension and the like. The surfactant is not particularly limited, and a known one can be used. Such as: anionic surfactants (such as: sodium laurylbenzene sulfonate, sodium laurate, ammonium salts of polyethylene oxide ether sulfate, etc.), non-ionic surfactants (such as polyethylene oxide Ethers, polyethylene oxide alkyl esters, polyethylene oxide sorbitan fatty acid esters, polyalkylene oxide phenyl ethers, polyethylene oxide alkylamines, polyethylene oxide alkylamines, etc.) and Examples of acetylene glycol-based surfactants. In the present invention, one or more of these surfactants can be used. The viscosity of the photoresist composition of the present invention is preferably 5 to 5,000 mPa · s at 25 ° C, more preferably 10 to 300 mPa · s, more preferably 15 to 200 mPa · s, and the most preferable is 2 0 to 1 50 m P a · s. When the viscosity is low, thixotropy is not easy to occur. On the contrary, if the viscosity is too high, it is difficult to adjust the film thickness when dipping: cloth. As a method for measuring viscosity, a commercially available B-type rotary viscometer or the like can be used. The photoresist composition of the present invention can be produced by mixing the ingredients by any method, such as a method of stirring the ingredients in a container with a stirring blade while adding the ingredients. The ingredients can be added simultaneously in the mixing container or gradually. In addition, each component can be added in one batch, or can be added several times. The temperature during mixing is arbitrary, generally 5 to 50 ° C, preferably 10 to 40 ° C. In addition, the mixing may be performed at a constant temperature, or the temperature may be changed. The photoresist composition of the present invention can be applied to any coating method, but 0 g stain coating is particularly desirable. The dip coating method is a well-known method. A large amount of a photoresist composition is placed in a container, and an insulating substrate having a conductive metal layer such as a copper-clad laminate is immersed in the container, and then it is lifted vertically at any speed. -22-200525295 (19) Manufacturing a coated substrate. At this time, the temperature of the photoresist composition in the container can be arbitrarily set, and a temperature range of 10 to 50 ° C is preferred. The device used for the dip coating method is not particularly limited, and a known one can be used, but a device capable of increasing the speed at the time of lifting to form a uniform film is preferred. Examples of commercially available dip coating devices include: gastric automatic dip coating AD-7200, semi auto dip coating SD-6200, and fiber coating SZC-720 (above, manufactured by Surthuma Communications Industries, Ltd.), etc. 〇The copper-clad substrate obtained by the dip coating method usually undergoes drying, exposure, development, etching, and photoresist film peeling steps, and after any other steps if necessary, a printed circuit board having a predetermined wiring pattern is manufactured. [Examples] As the components (a_) to (f) of the photoresist, the following can be used. [(A) Water or alkali soluble resin] 3 5 4 _Epoxy-Cyclohexyl Methacrylate Modified Resin (Daice) of Methacrylic Acid-Methyl Methacrylate Copolymer (made by Chemical Industry Co., Ltd.) Trade name C yc 1.0-mer-ACA-2 0 Μ, acid value 100 mg Κ Ο H / g, weight average molecular weight 17; 000) '[(B) cellulose derivative] (b- 1) Hydroxyethyl cellulose (manufactured by Tokyo Chemical Industry Co., Ltd.) (b-2) Methyl cellulose (manufactured by Tokyo Chemical Industry Co., Ltd.) -23-200525295 (20) (b-3) hydroxypropyl cellulose (Japan Soda Corporation) (B-4) methylhydroxypropyl cellulose (manufactured by Shin-Etsu Chemical Co., Ltd.) (b-5) ethyl hydroxyethyl cellulose (manufactured by Aczonobell Co., Ltd.) [(D) hydroxyl-containing organic solvents] (d -I) ethylene glycol monobutyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) (d-2) propylene glycol monomethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) (d-3) 3-methoxy-3-methyl-1- Butanol (manufactured by Tokyo Chemical Industry Co., Ltd.) [(E) Polymerizable unsaturated compound] (e-)) Polyethylene glycol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) (e-2) Trimethylolpropane Triacrylic (Manufactured by Kyoeisha Chemical Co., Ltd.) [(F) photopolymerization heuristic] (f-1) 2-methyl-1-(4-methylthienyl) -2 -morpholine propane-butanone (C hibaspecia 1 ity C he ni ica 1 (F-2) Diethylthiazolone (Chibaspeciality Chemical Co., Ltd.) [(Other ingredients)] Triethylamine (TEA) -24 > 200525295 (21) N- Methylmorpholine (NM) [(Organic solvents other than hydroxy-containing organic solvents)] Propylene glycol monomethyl ether acetate (PGM A) [(Thixotropic agent)] Ammonium oxide modified montmorillonite (SMC ) < Example 1 > [1) Preparation of photoresist composition] (B) Except cellulose derivative 'and (c) water, each component shown in Table 1 below was loaded according to Table 1. After mixing, a homogeneous solution was obtained. The mixture was then vigorously stirred while dripping (C) water in the amount shown in Table 1 over a period of 2 hours. The cellulose derivative (b) in the amount shown in Table 1 was further added, and after stirring for 15 hours, an aqueous photoresist composition was prepared. [2) Viscosity measurement] Using a type B viscosity meter (b L type, N 0.) made by Toki Sangyo Co., Ltd. at a temperature of 25 ° C, the measurement is performed at S 疋 turn benefit S 疋 rotation number 6 rpm . [3] Dip coating of photoresist composition] · The 1) The photoresist composition prepared was maintained at a temperature of 3 5 t, and an impregnation coating (trade name fib c〇at FC- 7 5 00) 'Laminate copper laminate (substrate thickness) 30μ on both sides, copper foil thickness i8 -25- 200525295 (22) μm, 4 0 in mx 5 1 0 mm) after dip coating 'Place this substrate at 80. (: The coated substrate with a photoresist composition coating film is obtained after drying for 15 minutes. After the lifting speed at the time of coating is changed, the coating film is adjusted to a thickness of about 8 μm [4]. ] 3) After the two coated substrates obtained after drying are overlapped, the overlapped substrates are placed in two 400 mm x 510 mm x 1 mm stainless steel plates and left to stand horizontally. After standing in this state for 2 days (23 t, relative humidity 60%), gently peel off the two substrates. This superimposed coated surface is divided into a number of 1 cm X 1 cm, and the peeling state is judged by the following criteria based on the number of nets with peeling parts. The results are shown in Table 1 below. ◎: When the number of peeling screens is less than 2% of the total number 〇: When the number of peeling screens is 2% or more and 5% or less of the total △: The number of peeling screens is 5% or more and 10% of the total When X: When the number of peeling screens is 10% or more of the total number [5) Adhesion measurement] Adcoition tester (Adohition tester made by Elco meter (non-magnetic coating film thickness gauge) company) Type F 106, an aluminum cylinder coated on the coating surface, and a device for measuring the peeling strength at the time of opening), and measuring the peeling strength of the coating film at room temperature. [6) Gloss measurement] • 26-200525295 (23) After the measurement was performed using a commercially available gloss meter (Tester Industrial Co., Ltd., OP-02), the relative glossiness of Example 1 was shown as 1. The results are shown in Table 1. 〇 [7) Measurement of line shape and resolution] • Evaluation after development was performed on the coated substrate obtained in 3) The line and space (hereinafter abbreviated as L / S) to 20 μπι / 20 The patterns with μιη ~ 80 μηι / 80 μιπ and 10 μηι scales were exposed to ultraviolet light after passing through 5 masks each (ultra-high pressure mercury lamp, dominant wavelength 36 5nm, 80mJ / cm2), and then 30 °. (: 1 ° /. Soaked in an aqueous solution of sodium carbonate for 60 seconds and developed, and washed at 25 ° C. The obtained substrate was scanned by a scanning electron microscope to make the photoresistance linearity according to the following standards Judgment. Among the patterns obtained with no missing lines and residual image development, the resolution with the minimum L / S 値 was obtained. The results are shown in the following Table 1. :: The side wall of the line is almost linear. 〇: A part of the side wall of the wire is snake-like. △: A large part of the side wall of the wire is partially snake-like. X: The meandering of the side wall of the wire is very obvious. • After the etching is evaluated, the development is followed by copper chloride. After the aqueous solution was etched at 45 ° C for 60 seconds, and then washed with water. Obtain the substrate and scan the electron microscope photograph to observe the shape of the remaining 5 photoresistance lines with L / S = 4 0/40. Evaluation. The results are shown in the following table.] -27- 200525295 (24) ◎: The pattern of defects and deflection appears in five figures I 〇: The pattern of defects and deflection appears in five figures | △: Defect and deflection The pattern that appears is 5 pictures. X. The pattern that appears when there is no 1¾ and the degree of anti-burn is 5 patterns. Evaluation after peeling After etching, the photoresist film was peeled off by quenching with 3% by mass sodium hydroxide water, washed with water, and dried to obtain a patterned substrate. The obtained substrate was scanned by a scanning electron microscope L / S = 40 The line shape of the copper wiring of / 40 is shown in the following table according to the following benchmarks. ◎: A picture of residual copper in the copper wiring room, the case is five. 0: A pattern of copper residual in the copper wiring room is 5 Figure △: 5 patterns of residual copper appear in the copper wiring room X: 5 patterns of residual copper appear in the copper wiring room; < Examples 2 to 6 > Each component contained in Table] was used in the amounts shown in Table 1 to produce a water-based photoresist composition. The evaluation was performed in the same manner as in Example 1 and shown. < Comparative Example 1 > A photoresist composition was the same as in Example 1 except that hydroxyethyl cellulose was used. The results are the same as those in the examples. 0 to 0 of ξ [2 to 3 of 4 [5 of 4 of 4] liquid solution of copper wiring diagram formed at 45 ° C after observing Judge. There are 0 to 1 in the case, 2 to 3 in the case, 4 in the case, 5 in the g, and f. Example 1 is the same as the legal system: the results are shown in Table 1. -28- 200525295 (25) < Comparative Example 2 > An aqueous photoresist composition was produced in the same manner as in Example 1 except that 2.0 parts by weight of hydroxyethyl cellulose was used. The results after evaluation in the same way are shown in Table 1. < Comparative Examples 7 to 16 > After using the amounts shown in Table 2 for each component described in Table 2, an aqueous photoresist composition was produced. The evaluation results obtained in the same manner as in Example 1 are shown in Table 2. < Comparative Examples 3 to 7, Examples 17 to 21 > After using the amounts shown in Table 3 for each of the components listed in Table 3, an aqueous photoresist composition was produced. The evaluation results obtained in the same manner as in Example 1 are shown in Table 3. 200525295 (26) 5 Example 6 r- ^ 1 0.05 1 1 1 1 CO 5.05 1 1 (N »· 〇o inch (N 1 1 ο ◎ VO ο 〇〇ο 60/60 〇〇〇 Example 5 r — (1 0.05 1 1 1 1 r—KI 10.05 I 1 1 (N ^ r \ 〇inch (N 1 1 ο ◎ ◎ r- ο ο 50/50 〇〇 Example 4 IT) τ—Η 1 0.05 1 1 I 1 jo in r—i 15.05 1 vy ^ 1 (N 〇 inch (N 1 i ο V 'Ή ◎ \ D Ο rH 1ί 50/50 〇〇 Example 3 VO τ— ^ 1 0.05 1 1 1 1 〇inch ^ T) rH 20.05 1 1 (N to 〇inch (N 1 1 〇 ο ◎ Ο ο 50/50 〇〇〇 Example 2 ν〇r—Η 1 0.05 1 1 1 1 in m (| 25.05 1 1 (N to o inch 1 1 ο rH ◎ ο ο Ο) ο Γ 50/50 〇〇〇 Comparative Example 2 ΙΤ) rH 1 ΓΝ | 1 1 1 1 to | 28.1 | 1 1 (N o inch < N 1 1 Ο r-H X σ \ ο ο 60/60 〇 < 3 Comparative Example 1 i〇 * 1 1 1 1 1 1 30.1 | 1 1 (N o inch (N 1 1 Ο Τ Ή ◎ (N Ο ο 80/80 XXX Example 1 ΙΟ 1 0.05 1 1 1 1 ο m cn 30.05 1 1 (N < n 〇inch (N 1 1 〇 s Η r-; ο? — (50/50 〇〇〇〇 Mass% BlBf, Mass% Mass% Mass% i Mass%! Mass% Mass% Mass% Mass% Mass% Mass% Mass% Mass% Mass% Mass% Mass% Mass% Mass% MPa Linearity of the photoresist line g δ 骧 δ 骧 (a-1) (a-2) (b-1) (b-2) ( b-3) «3 1 (b-5) 1 (d-1) (d-2) Ί (d-3)! / ^ N (e-2) -N • ^ TEA NMM PGMA Total volume tightness Intensity gloss resolution / s ^^ / ί ^ s -30- 200525295 (27) rvl ^ Example 16 〇〇1 1 1 (N 〇1 1 oo 31.3 1 m 1 < N o 1 < N 1 O o ◎ or- ^ V ·· 30/30 ◎ ◎ ◎ Example 15 〇1 1 1 0.15 1 1 inch o rH 30.35 1 inch 1 (N o 1 (N 1 oo ◎ oc o (N r—i 30/30 ◎ ◎ ◎ Example 14 m 1 1 1 ψ i 1 1 P; m I 28.4 I 1 inch 1 (N ΚΓ) 〇1 rs) 1 o H ◎ CTs or—H ψ ^ 30/30 ◎ ◎ Example 13 r— ^ 1 1 1 0.05 1 1 cn mr * H 26.45 1 1 inch (N o 1 Oi 1 or—i ◎ On 〇oy H 30/30 ◎ ◎ ◎ Example 12 1 1 1 1 0.02 1 1 m 1 1 inch CM o 1 CM 1.48 〇o ◎ oo 30/30 ◎ ◎ ◎ Example 11 r— ^ 1 1 1 1 1 | 0.05 O, 'called 20.05 1 1 (N in o 1 inch (N 1 oi—l ◎ Bu 0 1 'Ή 30/30 ◎ ◎ ◎ Example 10 r—Η 1 1 1 1 0.05 1 o, 丨 H 20.05 1 1 < N o 1 inch (N 1 o Ψ ^ ◎ oo o o f 30/30 ◎ ◎ ◎ Example 9 to, — 1 1 1 0.05 1 1 o to r— 20.05 1 < n 1 < N o 1 inch CN 1 o (◎ oo o f — 30/30 ◎ ◎ ◎ Example 8 ΙΟ r— < 1 1 0.05 1 1 1 o 20.05 1 1 CN o 1 inch (N 1 o H ◎ o o T— ^ 40/40 ◎ ◎ ◎ Example 7 t—H 1 0.05 1 1 1 1 r_H 20.05 1 1 < NO 1 inch 1 〇〇 ◎ oc o On 〇50 / 50 〇〇 Mass% Mass% Mass% i Mass% Mass% Mass% Mass% Mass% Mass% Mass% Mass% Mass% Mass% Mass% Mass% Mass% Mass% MPa Photoresist line linearity 8 g 鹱 Copper wire shape (after peeling) (a-1) (a-2) (b-1) (N 1 I (b-3) 0 > 5) (d-1) (d-2)! (d-3) / ^ N (e-2) / ^ \ g TEA NMM PGMA U_ niin < n Roll-close adhesion strength gloss resolution g £ -31-200525295 (28) Example 21 inch) 1 1 1 1 ▼ —1 1 inch 1 1 inch 1 (Νun Ο inch oi 1 O o ◎ oo ο r — (Τ · — 40/40 ◎ ◎ ◎ Example 20 1 m 1 1 1 1 r—Η 1 ο m (N 1 1 inch 1 (Ν to Ο inch (Ν 1 oo ◎ r- ο f < 40/40 ◎ ◎ ◎ Example 19 1 1 1 1 1 1 0.05 I 1 ο 1 21.05 I 1 1 inch 1 (ΝCO Ο inch oi 1 oo ◎ oo ο τ— ^ r—Η 40/40 ◎ ◎ ◎ Example 18 〇I 1 1 1 1 0.05 1 ο 〇1 31.05 1 inch 1 (N ο inch oi 1 oo ◎ oo ο (Ν Τ—Η 40/40 ◎ ◎ ◎ Example Π 〇, Η 1 1 1 1 1 0.05 1 σ \ m 〇oo CN 1 5.05 1 1 m 1 (N υο Ο oi 1 oo ◎ r- ο ψ 1 ▼ —Η 50/50 ◎ ◎ ◎ Comparative Example 7 m 1— < 1 1 1 1 1 1 ο BU m m | 28.4 1 1 1 inch 1 (Ν Ο 1 < N o o 〇 OJ ο rn ο 70/70 X X X Comparative Example 6 m τ— (1 1 1 r—Η 1 1 1 ο 1—Η inch rn 1 ο f i 1 ΓΝ1 ιη Ο 1 (N o o <] ο 60/60 < 3 < < 3 Comparative example 5 m 1 1 1 * '1 ^ 1 1 1 m 38.4 1 1 inch 1 r-j m ο 1 CN o o 〇 ο ο 70/70 <] < 3 < 3 Comparative Example 4 »" · ψ '1 1 1 s 1 1 1! 〇 (Ν ν— ^ inch inch · 1 1 m 1 Ο 1 1 o o < 3 ο ο 70/70 < 3 < 3 < 3 Comparative Example 3 m τ—Η 1 1 1 1 1 1 m < N m 35.4 i 1 Inches 1 ο 1 (N o o 〇 ο ο 60/60 < 3 mass% mass% mass% mass% mass% mass% mass% mass% mass% mass% mass% 1 mass% mass% mass% mass% mass% mass% mass% mass% MPa photoresistance linearity S g SI δ Table 骧, ^ Ν r— ^% t \ (b-2) SMC / ^ s ▼ Η 1 5 PGMA τ * -Η / S r? TEA NMM Total volume close adhesion strength gloss resolution, ~ ^ S 'u U, -32-