1298731 玖、發明說明： 【發明所屬之技術領域】 本發明係關於感光性樹脂組成物及使用其之印刷佈線 基板之製造方法。 【先前技術】 為了可以簡便且高可靠度地製造具有細微且高密度之 導體圖案的印刷佈線板，將本質上具優良解析度等性能之 感光性光阻液直接塗佈於絕緣基板表面之金屬導體層以形 成蝕刻光阻層，並使此蝕刻光阻層以指定的光阻圖案形成 之浸鍍法（d i p )是廣為人知的。本方法簡便且因於所形成之 蝕刻光阻層上不會發生針孔之現象，故在必須做成數μ m〜2 0 // m之較薄膜厚的情況下，為一有效之方法。 但是藉由使用至今之感光性光阻液所形成之蝕刻光阻 層，特別是在使用具有三個以上之乙烯性不飽和基，且於 25°C、1大氣壓下之黏度為2000mPa· s以上之感光性化合 物的情況，蝕刻光阻層彼此之間變得不會貼合，但曝光敏 感度低，必須使用大量的光量。若需要大量的光量，則有 曝光時間變長導致生產性不佳而難以實用化之問題。 【發明内容】 本發明係有鑑於上述問題，目的在於提供一種蝕刻光阻 層彼此之間不會貼合，且形成曝光敏感度良好之蝕刻光阻 層的材料。 本發明人等經深入檢討，結果達成本發明。 即，第一發明係一種感光性樹脂組成物，其特徵為，分 5 312/發明說明書(補件)/93-09/93117916 1298731 子中含有至少一種類之於側鏈上具有可光聚合之乙烯性不 飽和基之樹脂、與具有三個以上之乙稀性不飽和基且於2 5 °C、1大氣壓下之黏度為2000mPa*s以上之感光性化合物。 較佳之態樣為上述感光性樹脂組成物含有之分子中，於 側鏈上具有可光聚合之乙烯性不飽和基之樹脂的乙烯性不 飽和基當量為100〜1000g/eq。 又，本發明之樹脂組成物係為可進一步於鹼性水溶液中 溶解之樹脂，其含有重量平均分子量為5 0 0 0〜2 0萬且酸價 為20mgKOH/g〜300mgKOH/g之樹脂，從驗顯影性之觀點而 言，其為良好之態樣。 此外，上述感光性樹脂組成物中含有之溶劑含量為3 0 重量％〜9 5重量％，為良好之態樣。 第二發明係一種印刷佈線基板之製造方法，其特徵為， 將在絕緣基板表面上形成有金屬導體層之基板浸潰於前述 之感光性樹脂組成物中後，藉由從感光性樹脂組成物中拉 起，使基板表面上塗佈感光性樹脂組成物，經由光罩曝光、 顯影，形成光阻圖案的餘刻光阻層後，對基板施以钮刻處 理，藉以將金屬導體層形成為指定之導體圖案。 本發明之特徵係含有於2 5 °C 、1大氣壓之下之黏度為 2 0 0 0 m P a · s以上之感光性化合物分子、及至少一種類之於 側鏈上具有可光聚合之乙烯性不飽和基之樹脂，可形成無 黏性且曝光敏感度良好之蝕刻光阻層。 【實施方式】 以下，針對本發明進行詳細之說明。 6 312/發明說明書(補件)/93-09/93117916 1298731 本發明之感光性樹脂組成物，係含有於分子中之側鏈上 具有可光聚合之乙烯性不飽和基之樹脂、與具有三個以上 之乙烯性不飽和基且於25 °C、1大氣壓下之黏度為 2 0 0 0 m P a · ε以上之感光性化合物所構成之感光性樹月旨組成 物。較佳為進一步含有可溶解於鹼性水溶液之樹脂與光聚 合起始劑及溶劑而構成之感光性樹脂組成物。 作為可溶解於鹼性水溶液之樹脂，可列舉苯乙烯順丁烯 二酸酐樹脂等順丁烯二酸酐共聚合體：或（曱基）丙烯酸甲 酯、（曱基）丙烯酸乙酯、（曱基）丙烯酸丙酯等之具有乙烯 性不飽和基之酯化合物與（曱基）丙烯酸等具有羧基之乙烯 性不飽和單體的共聚合物；苯乙烯等之不具有羧基之乙烯 性不飽和單體與（曱基）丙烯酸曱酯、（甲基）丙烯酸乙酯、 (曱基）丙烯酸丙酯等之具有乙烯性不飽和基之酯化合物與 (曱基）丙烯酸等具有羧基之乙烯性不飽和單體的共聚合物 等。此等共聚合樹脂可單獨或混合使用。 可溶解於驗性水溶液之樹脂的重量平均分子量，通常係 & 5000〜20萬為適當，較佳為1萬〜10萬。重量平均分子 量未滿5 0 0 0之情況，作為顯影液之碳酸鈉水溶液或矽酸鈉 水溶液等之弱鹼性水溶液之耐顯影液性不佳，為了利用顯 影液使曝光部之溶解可持續進行，需使佈線（電路）細至某 一程度以上，依情況之不同，會有因顯影液而不分曝光部 及未曝光部皆使之溶解剝離，導致光阻圖案之描晝變得困 難之情況。另一方面，若重量平均分子量超過20萬，作為 顯影液之弱鹼性水溶液對未曝光部之溶解變得困難，有無 7 312/發明說明書(補件)/93-09/93117916 1298731 法顯影之情況。若重量平均分子量再進一步超過2 0萬，於 蝕刻後之氫氧化鈉水溶液等之強鹼性水溶液中剝離曝光部 光阻之步驟中，光阻膜之剝離將變得極為遲缓，會有先前 所經常使用的剝離線（s t r i p p e r 1 i n e )變得無法使用之情 況。 此外，可溶解於此等驗性水溶液之樹脂的酸價，通常以 20〜300mgKOH/g為適當，而以50〜200mgKOH/g較佳。於酸 價未滿20mgKOH/g之情況，作為顯影液之碳酸鈉水溶液或 石夕酸納水溶液等之弱驗性水溶液中，對未曝光部之溶解變 得困難，有無法顯影之情況。又，於剝離步驟中，會有光 阻膜之剝離變得極為遲緩之情況。另一方面，若酸價超過 300mgKOH/g，與上述重量平均分子量低之情況同樣地，弱 鹼性水溶液之耐顯影液性不佳，為了利用顯影液使曝光部 之溶解可持續進行，需使佈線（電路）細至某一程度以上， 依情況之不同，會有因顯影液而不分曝光部及未曝光部皆 使之溶解剝離，導致光阻圖案之描晝變得困難之情況。酸 價的測定係利用例如0. 1 N之KOH無水曱醇滴定單位重量之 試料，並使用紛酿等指示劑即可測定之。 可溶解於鹼性水溶液之分子中不具有可光聚合之乙烯 性不飽和基的樹脂，於組成物之固體成分中含有1 0〜8 0重 量％為佳，而以2 0〜6 0重量％更佳。 作為於側鏈上具有乙烯性不飽和基之樹脂，可列舉雙酚 A型環氧樹脂、雙酚F型環氧樹脂、酚-酚醛清漆型環氧樹 脂或甲酚-酚醛清漆型環氧樹脂等之於環氧樹脂加成（甲基） 8 312/發明說明書(補件)/93-09/93117916 1298731 丙烯酸等之乙烯性不飽和單羧酸及不飽和多元酸 之樹脂；於苯乙烯順丁烯二酸酐樹脂等之順丁烯 聚合體中加成羥基乙基（曱基）丙烯酸酯或縮水甘 基）丙烯酸酯之樹脂等。或於（曱基）丙烯酸甲酯， 丙烯酸乙酯、（曱基）丙烯酸丙酯等之具有乙烯性 之酯化合物與（曱基）丙烯酸等具有羧基之乙烯性 體的共聚合物中，加成具有羥基之羥基乙基（曱I 酯等之具有羥基之具有乙烯性不飽和基之化合物 物；於（曱基）丙烯酸甲酯、（曱基）丙烯酸乙酯、 稀酸丙S旨等之具有乙烤性不飽和基之酯化合物與 基丙烯酸酯之共聚合樹脂中，加成羥基乙基（曱I 酯或具有叛基之化合物的具有乙婦性不飽和基之 物；或於（甲基）丙烯酸等具有羧基之乙烯性不飽 (甲基）丙烯酸曱酯、（曱基）丙烯酸乙酯、（曱基） 酯等之具有乙烯性不飽和基之酯化合物與縮水甘 酸酯之共聚合樹脂中，加成羥基乙基（曱基）丙烯 有羧基之化合物的具有乙烯性不飽和基之共聚合 或可列舉對於具有羧基之共聚合物加成縮水甘 基）丙烯酸酯等之含有縮水甘油基之乙稀性不飽牙 構成之樹脂等。此等樹脂及共聚合物皆可單獨或g 於側鏈上具有乙烯性不飽和基之樹脂的乙烯性 基當量係以100〜lOOOg/eq為適當。若乙烯性不飽 較1000g/eq大，會有無法提昇曝光敏感度之情況 200〜700g/eq 〇 312/發明說明書(補件)/93-09/93117916 酐所構成 二酸酐共 油基（曱 (曱基） 不飽和基 不飽和單 ^ )丙烯酸 的共聚合 (曱基）丙 縮水甘油 ^ )丙烯酸 共聚合 和單體與 丙烯酸丙 油基丙稀 酸S旨或具 物等。 油基（曱 7單體所 L合使用。 不飽和 和基當量 。較佳為 9 1298731 成 構 所0 酸 元 多 和 飽 不 及 酸 绫 單 和 飽 不 性 烯 乙 之 等 酸 烯 丙 共 曱 sf 酸基 二 油 烯 甘 丁 水 順縮 之 或 等SI 脂酸 樹烯 酐丙 酸 U 二基 曱 烯 C 丁基 順 乙 烯基 乙 羥 苯成 於加 ., 1^— 旨 豐 樹合 之 聚 基 曱 /(\ 、 酯 曱 酸 烯 丙 \)/ 基 曱 /(\ 於 或 ο 等 脂 樹 之 酯 酸 烯 丙 基 基 單 和 和 飽飽 不 不 性性 烯烯 乙 乙 有之 具 基 之 羧 等 有 酯 具 丙等 酸酸 烯烯 丙 丙 基基 曱 曱 、 與 酯物 乙 合 酸化 烯酯 丙 之 酸 烯 丙 \ί/ 基 曱 基 乙 基 經 之 基0 有 具 成 加 中 物 合 聚 共 的 體 合 聚 共 的 物 合 化 之 基 和 飽 不 性 烯 乙 有 具 之 基 、ην\ 有 具 之 等 酯 基 曱 \1/ 基 丙油酸 甘烯 水丙 縮> 、 與 酯物 乙合基 酸化乙 烯酯基 丙之羥 丨基成 和 加 飽 ’ 、 不 中 酯性脂 甲烯樹 酸乙合 烯有聚 丙 具 共 t)之之 基 等酯 (f_ 酸 於丙烯 ; 酸丙 物烯基 基 曱 曱 合 聚 共 之 基 和 飽 不 性 烯 乙 有 具 的 物 合 化 之 基 叛 有 具 或 酯 與 體 單 和 飽 不 性 烯 乙 之 基 羧 有 具 等 酸 烯 丙 基 甲 /IV 於 或 物 基 曱 基 曱 和 飽 、 不 酯性 曱烯 酸乙 烯有 丙 具 >之 等 酯 縮 、 與 酯物 乙 合 酸化 烯酯 丙 之 基 基 曱 水 丙烯 酸丙 烯基 丙 油 甘 具 或 酯 酸 烯 丙 基 甲 /IV 基 乙 基 經 成 加 中 脂 樹 合 聚 共 之 酯 酸 等 物 合 聚 共 之 基 和 飽 不 性 烯 乙 有 具 的 物 合 化 之 基 羧 有 曱 基 油 甘 水 縮 成 加 物 合 聚 共 之 基 羧 有 具 於 對 舉 列 可 或 所 用 體使 單 合 和混 飽或 不獨 性 單 烯可 乙 皆 之物 基 合 油聚 甘 共 水及 縮脂 有樹 含 等 之此 等。 等 酯 酸 烯 丙 C } 成 基構 樹 之 和 飽 不 性 烯 乙 的 脂 樹 之 基 和 飽 不 性 烯 乙 有 具 上 J-ai/ 側 於 以 係 量 當 基 量 當 基 和 飽 不 性 烯 乙 若 Ο 當 適 為 為 佳 較 ο 況 青 之 度 感 敏 光 曝 昇 提 法 無 有 會 大 200〜700g/eq ° 312/發明說明書(補件)/93-09/93117916 1298731 乙烯性不飽和基當量為1 Ο 0〜1 Ο Ο 0 g / e q之樹脂的使用 量，係於組成物之固體成分中含有5〜6 0重量％為佳，而以 1 0〜5 0重量％更佳。 又，使用於本發明之感光性樹脂組成物的感光性化合 物，係具有藉由曝光而引起交聯、聚合或二聚化等反應， 經由將由感光性樹脂組成物所形成之感光性樹脂組成物的 乾燥膜予以曝光，與相對於顯影液不溶之物形成蝕刻光阻 層之性質者。感光性化合物之主成份的黏度於1大氣壓、 2 5 °C下，未滿2 0 0 0 m P a · s時，若將所製作之蝕刻光阻層彼 此重疊且施以重量，則感光性化合物向塗膜表面移動，會 發生蝕刻光阻層彼此貼合之情況。以2 0 0 0 m P a · s以上為 佳，4 0 0 0 m P a · s以上更佳，為固狀亦可。 作為較佳之具有三個以上乙烯性不飽和基之感光性化 合物，可列舉三烯丙基異三聚氰酸酯、異三聚氰酸EO改質 三丙烯酸酯、多官能胺基曱酸乙酯加成體、多官能聚酯丙 烯酸酯、季戊四醇四（甲基）丙烯酸酯、二-季戊四醇五（曱 基）丙烯酸酯、二-季戊四醇六（曱基）丙烯酸酯等。 乙烯性不飽和基兩個以下之感光性化合物，因有使曝光 敏感度降低之虞，故為不佳。 使用25°C 、1大氣壓下之黏度未滿2000mPa· s之感光 性化合物之情況，以感光性化合物之使用總量的3 0重量％ 以下為佳，2 0重量％以下更佳。作為上述具有乙烯性不飽 和基之化合物之具有一個乙烤性不飽和化合物之不飽和化 合物，可列舉例如2 -經基乙基（曱基）丙烯酸酯、2 -經基丙 10 312/發明說明書(補件)/93-09/93117916 1298731 基（曱基）丙烯酸酯、4 _羥基丁基（曱基）丙烯酸酯、N -乙烯 基吼咯啶酮、（曱基）丙烯醯嗎啉、曱氧基四乙二醇（曱基） 丙烯酸酯、甲氧基聚乙二醇（曱基）丙烯酸酯、N，N -二曱基 (曱基）丙烯醯胺、N -羥曱基（曱基）丙烯醯胺、N，N -二曱基 胺基丙基（甲基）丙烯醯胺、N，N -二曱基胺基乙基（曱基）丙 烯酸酯、N，N -二甲基胺基丙基（甲基）丙烯酸酯、苯氧基乙 基（甲基）丙烯酸酯、環己基（甲基）丙烯酸酯、異硼烷基丙 烯酸酯等。又，作為具有兩個乙烯性不飽和化合物之不飽 和化合物，可列舉二乙二醇二（甲基）丙烯酸酯、三乙二醇 二（曱基）丙烯酸酯、三丙二醇二（曱基）丙烯酸酯、三羥曱 基丙烷二（曱基）丙烯酸酯、雙酚A之E0加成物二（甲基） 丙烯酸酯等。作為具有三個乙烯性不飽和化合物之不飽和 化合物，可列舉三羥甲基丙烷三（曱基）丙烯酸酯、三羥甲 基丙烷P0改質三（曱基）丙烯酸酯、三羥曱基丙烷E0改質 三（甲基）丙烯酸酯、季戊四醇三丙烯酸酯等，該等可與具 有三個以上乙烯性不飽和基且於2 5 °C 、1大氣壓下之黏度 在2 0 0 0 m P a · s以上之感光性化合物組合使用之。 對於本發明之感光性樹脂組成物之感光性化合物之比 例，係為該組成物之固形份中的5〜6 0重量％，較佳為7〜5 0 重量％。未滿5重量％之情況，曝光時之硬化會變得不充分， 而有於顯影時溶解之傾向。若超過6 0重量％，則會有光阻 膜重疊時引起貼合之情況。 本發明之感光性樹脂組成物的固形份濃度，以未滿7 0 重量％為佳。若為7 0重量％以上，因感光性光阻液之黏度變 11 312/發明說明書(補件)/93-09/93117916 1298731 高，會有無法形成均勻之蝕刻光阻層之情況，未滿5重量％ 之情況因曝光時之硬化會變得不充分，而有於顯影時溶解 之情況。以7〜5 0重量％為佳。 作為使用於本發明之有機溶劑成分，可列舉如甲醇、乙 醇、丙醇、異丙醇、2 -丁醇、己醇、乙二醇等之直鏈、分 支、二級或多元之醇類；及丙酮、曱基乙基酮、環己酮、 異佛爾酮等之酮類；及甲苯、二曱苯等之芳香族烴類；及 赛珞蘇、丁基赛珞蘇等之赛珞蘇類；及卡必醇、丁基卡必 醇等之卡必醇類；及丙二醇曱基醚類等之丙二醇烷基醚 類；及二丙二醇曱基醚等之聚丙二醇烷基醚類；及醋酸乙 酯、醋酸丁酯、赛珞蘇醋酸酯、丁基赛珞蘇醋酸酯、丁基 卡必醇醋酸酯、丙二醇單曱基醚醋酸酯等之醋酸酯類；乳 酸乙酯、乳酸丁酯等之乳酸酯類；丙酸酯類、丙酮酸酯類、 乙氧基丙酸酯類及二烷基乙二醇醚類、及正己烷、環己烷、 四氫呋喃等，可將此等以複數種組合使用。 作為光聚合起始劑，只要為藉由紫外線、可見光等之活 性光線之照射可使不飽和化合物開始聚合之起始劑，皆可 使用。可列舉如二苯基酮、米荷拉酮（Michler’s ketone) 等之二苯基酮類；苯偶姻、苯偶姻異丁醚等之苯偶姻烷基 醚類；2,2 -二甲氧基-2-苯基苯乙酮、2, 2 -二乙氧基苯乙 酮、2, 2 -環-4-苯氧基苯乙酮等之苯乙酮類；2 -羥基-2-甲 基苯丙銅、4 -異丙基-2-經基-2-曱基苯丙銅等之乙基苯基 酮類；2 -乙基蔥醌、2 -第三丁基蔥醌等之蔥醌類；二乙基 - 9 -氧二苯并硫旅喃、二異丙基-9 -氧二苯并硫17底喃、氯化 12 312/發明說明書(補件)/93-09/93117916 1298731 -9 -氧二苯并硫旅喃等之-9 -氧二苯并硫哌喃類；其他之苯 偶醯（B e n z i 1 )、· 1 -羥基環己基苯基酮、2 -曱基[4 -（曱基硫 基）苯基]-2-嗎啉基-丙烷-1-酮、對二曱基胺基苯曱酸乙基 酯、對二曱基胺基苯曱酸異戊酯等。此等光聚合起始劑可 單獨或混合使用。相對於本發明之感光性樹脂組成物，光 聚合起始劑之比例以該組成物之固形份中的0. 2〜2 0重量°/〇 為佳，更佳為1〜1 0重量％。 又，本發明之感光性樹脂組成物中，可進一步視需要添 加均染劑、消泡劑、搖變劑（t h i X 〇 t r 〇 p i c a g e n t)、發色劑、 染料、顏料、無機填充劑、有機填充劑等。 藉由浸鍍法塗佈本發明之感光性光阻液之蝕刻光阻 層，於顯影步驟及蝕刻處理步驟中，由於對於搬送時之接 觸及顯影液或蝕刻液之喷射的強度充分保持，故基板平面 部之光阻層的厚度以3//m以上為佳且5/zm以上時會成為 特別強韌且蝕刻適性優越之光阻層。又，為達成特別高之 解析性及蝕刻精度，光阻層之厚度於基板平面部為3 0 // m 以下較佳，2 0 // m以下特佳。 本發明之感光性樹脂組成物，可於在一般之硬質（剛性） 佈線基板及撓性佈線基板、金屬基板等之表面上形成有金 屬導體層之基板，藉由輥塗法或浸潰法而形成薄膜且均勻 之感光性光阻膜。本發明之樹脂組成物，特別適合以浸潰 法形成感光性光阻膜。通常，係於基板導體表面上以硫酸 等酸進行處理、或使用刷子等研磨金屬表面，藉以將表面 清淨後，於基板之導體層上以輥塗法或浸潰法塗佈本發明 13 312/發明說明書(補件)/93-09/93117916 1298731 之感光性樹脂組成物，接著乾燥溶劑，形成為膜厚3〜2 Ο // m ( 8〜1 5 // m為佳）之薄膜均勻的感光性光阻膜後，透過光 罩以紫外光或可見光將指定之電路圖案進行曝光使之硬 化，並於0 . 5〜3 . 0重量％左右之碳酸鈉水溶液等弱鹼性水溶 液中溶解除去未曝光部分。其次，將露出之導體層以蝕刻 處理除去後，對殘留下來之導體層表面的已硬化之感光性 光阻膜以1 . 0〜5 . 0重量％左右之氫氧化鈉水溶液等強鹼性 水溶液進行剝離去除，以得到目的物之導體電路。 使用本發明之感光性樹脂組成物所製作之蝕刻光阻 層，彼此之間不會貼合且曝光敏感度良好，可形成曝光部 之耐顯影液性、耐蝕刻液性、剝離性優越之蝕刻光阻層。 (實施例） 以下藉由實施例詳述本發明。若特別無特別註明，「份」 為「重量份」之意。 (測定及評估方法） 樹脂分子量：以GPC測定，求得重量平均分子量。 樹脂酸價··以0 . 1 N之Κ Ο Η無水甲醇滴定試料1 g，使用酚 酞等指示劑測定，以KOH之毫克數表示。 溶劑量：感光性樹脂組成物溶液中之溶劑含有量以重量％ 表示。 膜厚：使用渦電流式簡易膜厚計（ISOS COPE MP30 ;費雪儀 器公司製）測定。 顯影性：使用3 0 °C、1. 0重量％之碳酸鈉水溶液，於0 . 1 8 P a 之壓力下進行6 0秒之噴霧顯影，對未曝光部分進行以下判 14 312/發明說明書(補件)/93-09/93117916 1298731 定。 〇為無殘渣之情況，X為有殘渣之情況。 曝光敏感度：藉由光阻曝光用雙面同時曝光機 「HMW - 5 3 2 D」（（股）歐克製作所製），以積分光量 1 0 0 m J之紫外線進行曝光，其後以 3 0 °C之1 . 0重量％ 的碳酸鈉水溶液，於喷霧壓為2 k g / c m 2之條件下，確 認進行 6 0秒之喷射時之步驟段數（思托發2 1段之塗 膜殘存段數）。 敏感度為2段以下：X ，3〜4段：〇，5段以上：◎。 黏性：將塗佈基板切成匚]1 0 c m X 1 0 c m，重疊塗膜面施 以 20kg/cm2之重量放置一天，將無貼合者標示為 ◎，稍有貼合者標示為〇，大量貼合者標示為X 。 塗佈性：於感光性光阻液中浸潰基板，拉起時，無塗 膜表面之厚度不均者標示為〇，有厚度不均者標示為 X ° (樹脂溶液A之合成） 將曱基丙烯酸曱酯5 5. 0份、2 -羥基乙基丙烯酸酯1 0 . 0 份、正丙烯酸丁酯1 8. 1份、以及甲基丙烯酸1 6. 9份，於 曱基乙基酮150.0份中溶解，於氮氣環境中，在攪拌、回 流條件下使用聚合起始劑進行聚合，得到以聚苯乙烯換算 重量平均分子量為2 8 0 0 0、酸價為1 1 OmgKOH/g、固形份濃 度為4 0 . 0重量％之樹脂溶液A。 (樹脂溶液B之合成） 將曱基丙烯酸甲酯55.0份、2 -乙基己基丙烯酸酯10.0 15 312/發明說明書(補件)/93-09/93117916 1298731 份、基甲基丙烯酸苄酯1 5 . 0份、以及甲基丙烯酸2 Ο · 0份， 於甲基乙基酮150.0份中溶解，於氮氣環境中，在揽拌、 回流條件下使用聚合起始劑進行聚合，得到以聚苯乙烯換 算重量平均分子量為63000、酸價為130mgKOH/g、固形份 濃度為4 0 . 0重量％之樹脂溶液B。 (樹脂溶液C之合成） 將曱基丙烯酸甲酯 58.0份、2 -乙基己基丙烯酸酯 9 . 0份、甲基丙烯酸¥酯1 0 . 0份、以及曱基丙烯酸 2 3 . 0份，於曱基乙基酮1 5 0 . 0份中溶解，於氮氣環 境中，在攪拌、回流條件下使用聚合起始劑進行聚 合，得到以聚苯乙烯換算重量平均分子量為 107000、酸價為150mgKOH/g、固形份濃度為 40.0重 量％之樹脂溶液C。 1 (感光性光阻原液E之調製） 將樹脂溶液A 3 0. 0份、異三聚氰酸E 0改質三丙烯酸酯 3.0份（固體/ 25 °C)、二季戊四醇六丙烯酸酯4.0份（黏度： 4 2 0 0 in P a · s / 2 5 °C )、於側鏈上具有乙烯性不飽和基之樹脂 (分子量：1 5 0 0 0，不飽和基當量：3 5 0 (g / e q )，固形份：6 0 重量％)10份、2 -甲基[4-(曱基硫基）苯基]-2 -嗎啉基-丙烷 - 1-酮1.5份、二乙基-9-氧二苯并硫旅喃0,5份、以及 U V - B 1 u e 2 3 6 (三井化學公司製）0 . 1份予以混合，調製固形 份濃度5 5 . 2重量％之感光性光阻原液E。 (感光性光阻原液F之調製） 將樹脂溶液B 3 0. 0份、二季戊四醇六丙烯酸酯4. 0份（黏 16 312/發明說明書(補件)/93-09/93117916 1298731 度：4200mPa· s/25°C )、季戊四醇四丙烯酸酯3.0长 / 2 5 °C )、於側鏈上具有乙烯性不飽和基之化合物（分 1 5 0 0 0，乙烯性不飽和基當量：3 5 0 ( g / e q )，固形份 量％ ) 1 0份、2 -甲基[4 -（甲基硫基）苯基]- 2 -嗎啉基--1 -酮1 . 5份、二乙基-9 -氧二苯并硫哌喃硫0 . 5份 U V - B 1 u e 2 3 6 (三井化學公司製）0 · 1份予以混合，調！ 份濃度5 5 . 2重量％之感光性光阻原液F。 (感光性光阻原液G之調製） 將樹脂溶液C 3 0 . 0份、二季戊四醇六丙烯酸酯3 . 0 度：4200mPa· s/25°C)、季戊四醇四丙烯酸酯4.0伤 / 2 5 °C )、於側鏈上具有乙烯性不飽和基之化合物（分 15000，乙稀性不飽和基當量·· 450(g/eq)，固形份 量％)10份、2-甲基[4-（甲基硫基）苯基]- 2 -嗎啉基--1*~8同1.5份、二乙基-9-氧二苯并硫®底喃0.5份、 UV-Blue 2 3 6 (三井化學公司製）0· 1份予以混合，調ί 份濃度5 5 . 2重量％之感光性光阻原液G。 (感光性光阻原液Η之調製） 將樹脂溶液Β 4 0. 0份、二季戊四醇六丙烯酸酯 (黏度：4200mPa· s/25°C )、2-甲基[4-（甲基硫基）苯 嗎琳基-丙烧-1-酮1.5份、二乙基-9-氧二苯并硫旅 份、以及U V - Β 1 u e 2 3 6 (三井化學公司製）0 . 1份予以 調製固形份濃度5 1 . 1重量％之感光性光阻原液Η。 (感光性光阻原液I之調製） 將樹脂溶液Β 3 0 · 0份、三羥曱基丙烷三丙烯酸酯 312/發明說明書(補件)/93-09/93117916 ' (固體 子量： ·· 60 重 丙烧 、以及 贫固形 |份（黏 r (固體 子量： :60重 •丙烧 以及 良固形 7 · 0份 基]-2-喃0· 5 混合， 7· 0份 17 1298731 (黏度：65mPa· s/25°C)、於側鏈上具有乙稀性不飽和基之 化合物（分子量：15000，乙烤性不飽和基當量：350(g/eq)， 固形份：6 0重量°/〇 ) 1 0份、2 -曱基[4 -(曱基硫基）苯基]- 2 -嗎琳基-丙烧-1 - S同1 . 5份、二乙基-9 -氧二苯并硫旅喃0 . 5 份、以及U V - B 1 u e 2 3 6 (三井化學公司製）0 . 1份予以混合， 調製固形份濃度5 5. 2重量％之感光性光阻原液I。 (感光性光阻原液Z之調製） 將樹脂溶液A 3 0 . 0份、二季戊四醇六丙烯酸酯2. 0份（黏 度：4500mPa*s/25°C)、季戊四醇四丙烯酸酯5.0份（固體 / 2 5 °C )、於側鏈上具有乙烯性不飽和基之化合物（乙烯性不 飽和基當量：86(g/eq))10份、2 -甲基[4-(曱基硫基）苯 基]-2 -嗎琳基-丙烧-1_8同1.5份、二乙基-9 -氧二苯并硫旅 喃0. 5份、以及UV-Blue 2 3 6 (三井化學公司製）0· 1份予以 混合，調製固形份濃度6 3. 3重量％之感光性光阻原液Z。 (感光性光阻原液AA之調製） 將樹脂溶液B 3 0 . 0份、二季戊四醇六丙烯酸酯5. 0份（黏 度：4500mPa*s/25°C)、季戊四醇四丙烯酸酯2·0份（固體 / 2 5 °C )、於侧鏈上具有乙烯性不飽和基之化合物（乙烯性不 飽和基當量：1260(g/eQ))10份、2-甲基[4 -（曱基硫基）苯 基]-2-嗎琳基-丙烧-1-酮1.5份、二乙基-9 -氧二苯并硫派 喃0. 5份、以及UV-Blue 2 3 6 (三井化學公司製）0· 1份予以 混合，調製固形份濃度5 5 . 2重量％之感光性光阻原液A A。 (實施例1 ) (感光性光阻液K之調製） 18 312/發明說明書(補件)/93-09/93117916 1298731 將Μ E Κ 3 5 . 0份及丙二醇單甲基醚醋酸酯1 5 . 9份混入感 光性光阻原液E中，進行攪拌以調製感光性光阻液K。 (實施例2 ) (感光性光阻液L之調製） 直接使用感光性光阻原液E。 (實施例3 ) (感光性光阻液Μ之調製） 將Μ Ε Κ 3 5 . 0份及丙二醇單曱基醚醋酸酯1 5 . 9份混入感 光性光阻原液F中，進行攪拌以調製感光性光阻液Μ。 (實施例4 ) (感光性光阻液Ν之調製） 直接使用感光性光阻原液F。 (實施例5 ) (感光性光阻液0之調製） 將Μ Ε Κ 3 5. 0份及丙二醇單曱基醚醋酸酯1 5. 9份混入感 光性光阻原液G中，進行攪拌以調製感光性光阻液0。 (實施例6 ) (感光性光阻液Ρ之調製） 直接使用感光性光阻原液G。 (比較例1 ) (感光性光阻液Q之調製） 將Μ Ε Κ 3 5. 0份及丙二醇單曱基醚醋酸酯1 5. 9份混入感 光性光阻原液Η中，進行攪拌以調製感光性光阻液Q。 (比較例2 ) 19 312/發明說明書(補件)/93-09/93117916 1298731 (感光性光阻液R之調製） 將Μ E K 3 5 . 0份及丙二醇單曱基醚醋酸酯1 5 · 9份混入感 光性光阻原液I中，進行攪拌以調製感光性光阻液R。 (實施例7 ) (感光性光阻液A Ε之調製） 將Μ E K 4 6 . 2份及丙二醇單曱基醚醋酸酯1 9 . 8份混入感 光性光阻原液Ζ中，進行攪拌以調製感光性光阻液ΑΕ。 (實施例8 ) (感光性光阻液A F之調製） 將Μ Ε K 3 5 . 0份及丙二醇單曱基醚醋酸酯1 5 . 9份混入感 光性光阻原液ΑΑ中，進行攪拌以調製感光性光阻液AF。 (比較例3 ) (感光性光阻液A G之調製） 將感光性光阻原液F中之二季戊四醇六丙烯酸酯4. 0份 (黏度：4 2 0 0 m P a · s / 2 5 °C )、季戊四醇四丙烯酸酯3 · 0份（固 體/ 25°C )改為聚乙二醇二丙烯酸酯（50mPa· s/25°C )3.0份 加入，進一步將ΜΕΚ35. 0份與丙二醇單曱基醚醋酸S旨15.9 份混合，進行攪拌以調製感光性光阻液AG。 (印刷佈線基板之製造方法） 準備玻璃環氧雙面覆銅積層板（板厚0 . 2 m m、銅厚1 8 /zm，基板尺寸370mmx 260mm)之印刷基板。 接著，於不鏽鋼製之容器中，貯存感光性光阻液及原液 (G )，製作浸潰浴。然後將如上述所準備之印刷佈線基板， 相對於液面呈垂直，以5 0 c m /分之速度進行浸漬，使基板 20 312/發明說明書(補件)/93-09/93117916 1298731 上端突出於液面以上1 c ιτι之狀態浸潰，待停止後，以拉起 速度50cm/分將基板全體由液面上方拉起，塗佈感光性光 阻液，並於熱風式乾燥機中以8 0 °C乾燥1 0分鐘後，冷卻 至室溫。 使用描晝有可形成導體圖案之圖案的遮罩膜兩張，以各 遮罩膜之佈線圖案的方向相互垂直之方式，使遮罩膜接觸 於基板兩面，藉由光阻曝光用雙面同時曝光機「HMW - 532D」 ((股）歐克製作所製），以積分光量1 0 〇〜5 0 0 m J之紫外線進 行曝光，其後以3 0 °C之1 . 0重量％的碳酸鈉水溶液，於喷 霧壓為2 k g / c m2下進行噴射並顯影，形成指定之光阻圖案 之#刻光阻層。 接著，藉由4 0 °C之氯化銅（I I )餘刻液，將銅露出部分餘 刻除去，水洗後以4 0 °C之3 . 0重量％的氫氧化鈉水溶液， 於喷霧壓為2kg/cm2下進行喷射，除去蝕刻光阻層，形成 導體圖案之金屬導體層，以製作印刷佈線基板。 將如上述般所得到之印刷佈線基板之試驗結果示於表 21 312/發明說明書(補件)/93-09/93117916 1298731 ττ 膜厚 [β^] ο ◦ r-H ◦ σϊ ◦ CJi <〇 ◦ 塗佈性 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 黏性 ◎ ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ X X 曝光敏 感度 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 X ◎ X 顯影性 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 感光性化合 物黏度 [mPa · s/25°C ] 固體4200 !固體4200 固體4200 固體4200 固體4200 固體4200 固體4200 固體4200 4200 LO CO g 溶劑量 [%] CO LO 寸 CO LO 寸 CO LO 寸 CO CO LO CO CO 乙婦性不飽 和基當量 (g/eq) 〇> LO 〇〇 CD LO CO ◦ LO CO ◦ LO CO CD LO 寸 CO oo 1260 1 o LO OO o LO CO 光阻液 原液 ω ω o ο CS3 >—1 1 驗性溶解性 樹脂酸價 [mgKOH/g] CD i—i r-H CD t—H t—H CD CO »—1 ◦ CO r-H LO r-H c=> LO r—i O H r—H 〇> CO r-H ◦ CO r—H 〇> CO r-H o CO 鹼性溶解性樹 脂分子量 1 28000 28000 63000 63000 107000 107000 28000 63000 ! 63000 63000 63000 樹脂溶液 PQ PQ o o < PQ PQ CQ PQ 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 比較例1 比較例2 比較例3 916卜 11 £6/60.£6/(分}«)_^舔&&微/31 e 1298731 (產業上之利用可能性） 根據本發明，因可形成無黏性、曝光敏感度良好之蝕刻 光阻層，故為產業上極為重要之發明。 23 312/發明說明書(補件)/93-09/93117916[Technical Field] The present invention relates to a photosensitive resin composition and a method of producing a printed wiring board using the same. [Prior Art] In order to easily and highly reliably manufacture a printed wiring board having a fine and high-density conductor pattern, a photosensitive photoresist having an excellent resolution and the like is directly applied to the surface of the insulating substrate. The immersion plating method (dip) in which the conductor layer is formed to form an etch photoresist layer and the etched photoresist layer is formed in a prescribed photoresist pattern is widely known. This method is simple and does not cause pinholes on the formed etching resist layer. Therefore, it is an effective method in the case where it is necessary to form a film thickness of several μ m to 2 0 // m. However, by using the etching photoresist layer formed by the photosensitive photoresist solution hitherto, in particular, three or more ethylenically unsaturated groups are used, and the viscosity at 25 ° C and 1 atm is 2000 mPa·s or more. In the case of the photosensitive compound, the etching photoresist layers do not adhere to each other, but the exposure sensitivity is low, and a large amount of light must be used. If a large amount of light is required, there is a problem that the exposure time becomes long and the productivity is poor and it is difficult to put it into practical use. SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object thereof is to provide a material for etching an etched photoresist layer which does not adhere to each other and which has excellent exposure sensitivity. The inventors of the present invention conducted an in-depth review and as a result, achieved the present invention. That is, the first invention is a photosensitive resin composition characterized in that it has at least one kind of photopolymerizable on a side chain, in accordance with the specification of 5 312 / invention specification (supplement) / 93-09/93117916 1298731 A resin having an ethylenically unsaturated group and a photosensitive compound having three or more ethylenically unsaturated groups and having a viscosity of not more than 2000 mPa*s at 25 ° C and 1 atm. In a preferred embodiment, the resin having a photopolymerizable ethylenically unsaturated group in the side chain of the molecule contained in the photosensitive resin composition has an ethylenically unsaturated group equivalent of 100 to 1000 g/eq. Further, the resin composition of the present invention is a resin which can be further dissolved in an alkaline aqueous solution, and contains a resin having a weight average molecular weight of 50,000 to 20,000 and an acid value of from 20 mgKOH/g to 300 mgKOH/g. From the viewpoint of developability, it is a good aspect. Further, the solvent content of the photosensitive resin composition is from 30% by weight to 9% by weight, which is a good condition. According to a second aspect of the invention, in a method of manufacturing a printed wiring board, a substrate having a metal conductor layer formed on a surface of an insulating substrate is impregnated into the photosensitive resin composition, and a photosensitive resin composition is used. Pulling up, coating the photosensitive resin composition on the surface of the substrate, exposing and developing through the mask, forming a photoresist layer of the photoresist pattern, and then applying a button treatment to the substrate, thereby forming the metal conductor layer into The specified conductor pattern. The present invention is characterized in that the photosensitive compound molecule having a viscosity of 2 00 m P a · s or more at 25 ° C and 1 atm is at least one kind of photopolymerizable ethylene on the side chain. The unsaturated unsaturated resin can form an etch resist layer which is non-sticky and has good exposure sensitivity. [Embodiment] Hereinafter, the present invention will be described in detail. 6 312 / invention specification (supplement) / 93-09/93117916 1298731 The photosensitive resin composition of the present invention contains a resin having a photopolymerizable ethylenically unsaturated group in a side chain in a molecule, and has three A photosensitive resin composition comprising at least one of the ethylenically unsaturated groups and a photosensitive compound having a viscosity of not more than 2,000 m P a · ε at 25 ° C and 1 atm. It is preferable to further contain a photosensitive resin composition which is soluble in a resin of an alkaline aqueous solution, a photopolymerization initiator and a solvent. Examples of the resin which can be dissolved in the alkaline aqueous solution include maleic anhydride copolymers such as styrene maleic anhydride resin: methyl (meth)acrylate, ethyl (meth)acrylate, and mercapto. a copolymer of an ethylenically unsaturated group-containing ester compound such as propyl acrylate and a carboxyl group-containing ethylenically unsaturated monomer such as (meth)acrylic acid; an ethylenically unsaturated monomer having no carboxyl group such as styrene; An ester compound having an ethylenically unsaturated group such as decyl acrylate, ethyl (meth)acrylate or propyl (mercapto)acrylate, and an ethylenically unsaturated monomer having a carboxyl group such as (mercapto)acrylic acid Copolymers, etc. These copolymerized resins may be used singly or in combination. The weight average molecular weight of the resin which can be dissolved in the aqueous test solution is usually from 5,000 to 200,000, preferably from 10,000 to 100,000. When the weight average molecular weight is less than 50,000, the development of the weakly alkaline aqueous solution such as the sodium carbonate aqueous solution or the sodium citrate aqueous solution of the developer is not good, and the dissolution of the exposed portion is continued by the developer. It is necessary to make the wiring (circuit) fine to a certain extent or more. Depending on the situation, the developer may be dissolved and peeled off regardless of the exposed portion and the unexposed portion, resulting in difficulty in depicting the photoresist pattern. Happening. On the other hand, if the weight average molecular weight exceeds 200,000, it is difficult to dissolve the unexposed portion as a weakly alkaline aqueous solution of the developer, and it is developed by the method of the invention (Supplement) / 93-09/93117916 1298731 Happening. If the weight average molecular weight further exceeds 200,000, in the step of peeling off the exposure portion photoresist in a strong alkaline aqueous solution such as an aqueous sodium hydroxide solution after etching, the peeling of the photoresist film becomes extremely sluggish, and there may be a previous The often used stripping line (stripper 1 ine) becomes unusable. Further, the acid value of the resin which can be dissolved in the aqueous test solution is usually 20 to 300 mgKOH/g, and preferably 50 to 200 mgKOH/g. When the acid value is less than 20 mgKOH/g, in the weak aqueous solution such as the sodium carbonate aqueous solution or the aqueous solution of the aqueous solution of the aqueous solution of the developer, it is difficult to dissolve the unexposed portion, and development may not be possible. Further, in the peeling step, the peeling of the resist film may be extremely delayed. On the other hand, when the acid value is more than 300 mgKOH/g, as in the case where the weight average molecular weight is low, the development resistance of the weakly alkaline aqueous solution is not good, and in order to continue the dissolution of the exposed portion by the developer, it is necessary to The wiring (circuit) is fine to a certain extent or more, and depending on the case, the developer may be dissolved and peeled off regardless of the exposed portion and the unexposed portion, resulting in difficulty in drawing the photoresist pattern. The acid value is measured by titrating a unit weight of a sample using, for example, 0.1 N of KOH anhydrous decyl alcohol, and measuring it using an indicator such as a mixture. The resin which is soluble in the molecule of the alkaline aqueous solution and which does not have a photopolymerizable ethylenically unsaturated group, preferably contains 10 to 80% by weight, and 2 to 60% by weight, based on the solid content of the composition. Better. Examples of the resin having an ethylenically unsaturated group in the side chain include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, or a cresol novolac type epoxy resin. Equivalent to epoxy resin addition (methyl) 8 312 / invention specification (supplement) / 93-09/93117916 1298731 Acrylic unsaturated monocarboxylic acid and unsaturated polybasic acid resin; A hydroxyethyl (mercapto) acrylate or glycidyl acrylate resin or the like is added to a homopolymer of a butylene anhydride resin or the like. Or a copolymer of an ethylenic ester compound having a vinyl group such as ethyl acrylate, ethyl acrylate or propyl (mercapto) acrylate, and a vinyl group having a carboxyl group such as (meth)acrylic acid. a hydroxyethyl group having a hydroxyl group (a compound having an ethylenically unsaturated group having a hydroxyl group, such as a hydrazine I ester; having a methyl group of (mercapto) acrylate, ethyl (meth) acrylate, a dilute acid C, etc. a hydroxyethyl group (an oxime ester or a compound having a tethered compound having an ethylenically unsaturated group; or a (methyl group) in a copolymerized resin of an ethylenically unsaturated group ester compound and a acrylate-based ester Copolymerization of an ester compound having an ethylenically unsaturated group such as an ethylenic unsaturated ethyl (meth)acrylate having a carboxyl group such as an acrylic acid, an ethyl (meth) acrylate or a (mercapto) ester with a glycidyl ester In the resin, a copolymer having an ethylenically unsaturated group in which a hydroxyethyl (fluorenyl) propylene has a carboxyl group is added, or a glycidol containing a copolymer of a carboxyl group and a glycidyl acrylate or the like is exemplified. a resin composed of a vinyl-rich, non-saturated tooth, etc. The resin and the copolymer may each have an ethylenic group equivalent of 100 to 100 g/eq, which may have an ethylenically unsaturated group in the side chain. Appropriate. If the ethylene content is not more than 1000g/eq, there will be a situation in which the exposure sensitivity cannot be improved. 200~700g/eq 〇312/Inventive Manual (Supplement)/93-09/93117916 The anhydride consists of the dianhydride co-oil base. (曱(fluorenyl) unsaturated group unsaturated mono()) copolymerization of acrylic acid (fluorenyl) propylene glycidol ^) acrylic acid copolymerization and monomer and acrylic acid propyl acrylate acid S or the like. Oil-based (曱7 monomer used in combination. Unsaturated and base equivalent. It is preferably 9 1298731. The structure of the acid is more than the acid and the acid cumene and the saturated olefinic acid sf Acid-based dimethylene succinic acid condensed or equal SI fatty acid phylloic anhydride propionic acid U-didecene C butyl cis-vinyl hydroxy benzene is added to the addition., 1^— 丰丰树合聚基曱/(\ , ester phthalic acid allyl \) / 曱 / (\ or ο such as the fatty acid allyl mono- and succinic acid and the carboxylic acid Acetyl allylic propionylpropyl hydrazine, and ethyl ester acrylated acrylate acrylate acrylate acrylate acrylate acrylate acrylate acrylate The base of the complexation and the base of the fully unsaturated ethylene, ην\ has the same ester group 曱\1/ propyl glyceryl acrylate, and acidification with the ester group Vinyl ester-based hydroxy hydroxy group formation and addition of ', not esterified lipid metene Ethyl ethoxylate has an ester such as a base of polyethylene with a total of t) (f_acid in propylene; an acid propyl alkenyl group condensed with a co-based group and a saturated olefinic group The carboxylic acid having an ester or a mono- and a monoethylidene group has an isopropenyl group/IV or an thiol group and a saturated, non-esteric decenoic acid having a propylene group> Ester condensation, with esters, acidified ethyl esters, acrylic groups, water-based acrylic acid, propylene-based propylene oil, or ester acid, allyl groups, methyl group, ethyl group, ethyl sulphate, sulphuric acid, etc. a combination of a conjugated base and a conjugated olefin having a sulfonate-based condensate-based condensate-addition conjugated carboxy group having a combination of Mixed or non-individual monoolefins can be combined with oils, polyglycols and reduced fats, such as trees, etc. Equivalent esters, allyl C, and hydroxylates The base of the tree and the lack of Ethylene B has a J-ai/ side on the basis of the amount of the base as the base and the fullness of the ethylene Ο Ο Ο Ο Ο Ο Ο ο ο ο 之 之 之 之 之 之 之 之 之 之 之 之 无 无 无 无 无 无 无 无 无 无700g/eq ° 312/Invention Manual (Supplement)/93-09/93117916 1298731 Ethylene unsaturated group equivalent is 1 Ο 0~1 Ο Ο 0 g / eq of resin used in the solid content of the composition It is preferably 5 to 60% by weight, more preferably 10 to 50% by weight. In addition, the photosensitive compound used in the photosensitive resin composition of the present invention has a reaction such as crosslinking, polymerization, or dimerization by exposure, and a photosensitive resin composition formed of a photosensitive resin composition. The dried film is exposed to form a property of etching the photoresist layer with respect to the insoluble matter with respect to the developer. When the viscosity of the main component of the photosensitive compound is at 1 atm, 25 ° C, and less than 20,000 m P a · s, if the produced etching resist layers are overlapped with each other and the weight is applied, the photosensitivity When the compound moves toward the surface of the coating film, the etching photoresist layers are bonded to each other. It is preferably 2,0 0 m P a · s or more, and more preferably 4 0 0 m P a · s or more. Preferred examples of the photosensitive compound having three or more ethylenically unsaturated groups include triallyl isocyanurate, isomeric cyanuric acid EO modified triacrylate, and polyfunctional amine decanoic acid ethyl ester. An adduct, a polyfunctional polyester acrylate, pentaerythritol tetra(meth)acrylate, di-pentaerythritol penta(indenyl)acrylate, di-pentaerythritol hexa(indenyl)acrylate, or the like. Two or less photosensitive compounds having an ethylenically unsaturated group are not preferable because of the reduction in exposure sensitivity. When a photosensitive compound having a viscosity of less than 2000 mPa·s at 25 ° C and 1 atm is used, it is preferably 30% by weight or less based on the total amount of the photosensitive compound used, and more preferably 20% by weight or less. The unsaturated compound having an ethylenically unsaturated compound as the above compound having an ethylenically unsaturated group may, for example, be 2-ethylideneethyl (meth) acrylate, 2-cyanopropyl 10 312 / invention specification (supplement)/93-09/93117916 1298731 base (fluorenyl) acrylate, 4-hydroxybutyl (mercapto) acrylate, N-vinyl fluorenyl ketone, (mercapto) propylene morpholine, hydrazine Oxytetraethylene glycol (fluorenyl) acrylate, methoxypolyethylene glycol (mercapto) acrylate, N,N-dimercapto(fluorenyl) acrylamide, N-hydroxyl decyl Acrylamide, N,N-didecylaminopropyl (meth) acrylamide, N,N-didecylaminoethyl (decyl) acrylate, N,N-dimethylamine Propyl (meth) acrylate, phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isoboroalkyl acrylate, and the like. Further, examples of the unsaturated compound having two ethylenically unsaturated compounds include diethylene glycol di(meth)acrylate, triethylene glycol di(decyl)acrylate, and tripropylene glycol di(decyl)acrylic acid. Ester, trishydroxypropyl propane bis(indenyl) acrylate, E0 adduct di(meth) acrylate of bisphenol A, and the like. Examples of the unsaturated compound having three ethylenically unsaturated compounds include trimethylolpropane tris(mercapto) acrylate, trimethylolpropane P0 modified tris(fluorenyl) acrylate, and trishydroxypropyl propane. E0 is modified by tris(meth)acrylate, pentaerythritol triacrylate, etc., and may have a viscosity of more than three ethylenically unsaturated groups at 25 ° C and 1 atm of 2 000 m P a · A combination of photosensitive compounds above s. The ratio of the photosensitive compound of the photosensitive resin composition of the present invention is 5 to 60% by weight, preferably 7 to 50% by weight, based on the solid content of the composition. When it is less than 5% by weight, the hardening at the time of exposure may become insufficient, and there is a tendency to dissolve at the time of development. If it exceeds 60% by weight, there is a case where the photoresist film overlaps. The solid content concentration of the photosensitive resin composition of the present invention is preferably less than 70% by weight. If it is 70% by weight or more, the viscosity of the photosensitive photoresist liquid is changed to 11 312 / the invention manual (supplement) / 93-09/93117916 1298731 is high, there may be a case where a uniform etching photoresist layer cannot be formed, which is not full. In the case of 5% by weight, the hardening at the time of exposure may become insufficient, and it may be dissolved at the time of development. It is preferably 7 to 50% by weight. The organic solvent component to be used in the present invention may, for example, be a linear, branched, secondary or polyhydric alcohol such as methanol, ethanol, propanol, isopropanol, 2-butanol, hexanol or ethylene glycol; And ketones such as acetone, mercaptoethyl ketone, cyclohexanone, and isophorone; and aromatic hydrocarbons such as toluene and diphenylbenzene; and celecoxibs such as celecoxib and butyl acesulfame And carbitol alcohols such as carbitol and butyl carbitol; and propylene glycol alkyl ethers such as propylene glycol decyl ether; and polypropylene glycol alkyl ethers such as dipropylene glycol decyl ether; and acetic acid; Ethyl acetate, butyl acetate, cyproterone acetate, butyl cyproteril acetate, butyl carbitol acetate, propylene glycol monodecyl ether acetate, etc.; ethyl lactate, butyl lactate, etc. Lactic acid esters; propionates, pyruvates, ethoxypropionates and dialkyl glycol ethers, and n-hexane, cyclohexane, tetrahydrofuran, etc. Used in combination. The photopolymerization initiator can be used as long as it is an initiator capable of starting polymerization of an unsaturated compound by irradiation with active light such as ultraviolet rays or visible light. Examples thereof include diphenyl ketones such as diphenyl ketone and meicholone (Michler's ketone); benzoin alkyl ethers such as benzoin and benzoin isobutyl ether; 2,2-dimethyl Acetophenones such as oxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2,2-cyclo-4-phenoxyacetophenone; 2-hydroxy-2- Ethyl phenyl ketones such as methyl phenyl propyl acrylate, 4-isopropyl-2-carbenyl phenyl phenyl propyl acrylate, etc.; 2-ethyl onion 醌, 2-tert-butyl onion, etc. Onion scorpion; diethyl- 9-oxodibenzosulfan sulphate, diisopropyl-9-oxodibenzo sulfonate 17 chlorination, chlorination 12 312/invention specification (supplement)/93-09/93117916 1298731 -9-oxobenzothiazepine -9-oxodibenzothiopyran; other benzoin (B enzi 1 ), · 1-hydroxycyclohexyl phenyl ketone, 2- fluorenyl [ 4-(indolylthio)phenyl]-2-morpholinyl-propan-1-one, p-didecylaminobenzoic acid ethyl ester, p-didecylaminobenzoic acid isoamyl ester, etc. . These photopolymerization initiators can be used singly or in combination. The ratio of the photopolymerization initiator to the photosensitive resin composition of the present invention is preferably from 0.2 to 2 0 weight%/〇, more preferably from 1 to 10% by weight, based on the solid content of the composition. Further, in the photosensitive resin composition of the present invention, a leveling agent, an antifoaming agent, a shaker (thi X 〇tr 〇picagent), a color former, a dye, a pigment, an inorganic filler, and an organic substance may be further added as needed. Filler, etc. The etching resist layer of the photosensitive photoresist of the present invention is applied by the immersion plating method, and in the developing step and the etching step, since the contact at the time of conveyance and the ejection of the developer or the etching liquid are sufficiently maintained, the strength is sufficiently maintained. When the thickness of the photoresist layer in the planar portion of the substrate is preferably 3/m or more and 5/zm or more, the photoresist layer is particularly strong and has excellent etching suitability. Further, in order to achieve particularly high resolution and etching precision, the thickness of the photoresist layer is preferably 3 0 // m or less on the plane of the substrate, and more preferably 2 0 // m or less. In the photosensitive resin composition of the present invention, a substrate having a metal conductor layer formed on a surface of a general hard (rigid) wiring substrate, a flexible wiring board, a metal substrate or the like can be formed by a roll coating method or a dipping method. A film and a uniform photosensitive photoresist film are formed. The resin composition of the present invention is particularly suitable for forming a photosensitive resist film by a dipping method. Usually, the surface of the substrate conductor is treated with an acid such as sulfuric acid or a metal surface is polished with a brush or the like, whereby the surface is cleaned, and the present invention is applied by a roll coating method or a dipping method on the conductor layer of the substrate 13 312 / The photosensitive resin composition of the invention specification (supplement)/93-09/93117916 1298731, followed by drying the solvent to form a film having a film thickness of 3 to 2 Ο // m (8 to 1 5 // m is preferable) After the photosensitive photoresist film, the specified circuit pattern is exposed to ultraviolet light or visible light through a mask to be hardened, and dissolved in a weakly alkaline aqueous solution such as a sodium carbonate aqueous solution of about 0.5% by weight to about 0.5% by weight. Unexposed part. Then, after the exposed conductive layer is removed by an etching treatment, the hardened photosensitive resist film on the surface of the remaining conductor layer is a strong alkaline aqueous solution such as a sodium hydroxide aqueous solution of about 1.0% by weight to about 0.5% by weight. Stripping removal is performed to obtain a conductor circuit of the object. The etching resist layer produced by using the photosensitive resin composition of the present invention does not adhere to each other and has excellent exposure sensitivity, and can form an etching excellent in developer liquid resistance, etching liquid resistance, and releasability of the exposed portion. Photoresist layer. (Examples) Hereinafter, the present invention will be described in detail by way of examples. Unless otherwise specified, "parts" means "parts by weight". (Measurement and Evaluation Method) Resin Molecular Weight: Determined by GPC to obtain a weight average molecular weight. Resin acid price·1 Κ Κ Η Anhydrous methanol titration sample 1 g, measured with an indicator such as phenolphthalein, expressed in milligrams of KOH. Solvent amount: The solvent content in the photosensitive resin composition solution is expressed by weight%. Film thickness: Measured using an eddy current type simple film thickness meter (ISOS COPE MP30; manufactured by Fisher Scientific). Developability: 30 ° C spray solution development was carried out under a pressure of 0.18 P a using a sodium carbonate aqueous solution of 30 ° C and 1.0% by weight, and the unexposed portion was subjected to the following judgment 14 312 / invention specification ( Supplement) /93-09/93117916 1298731 fixed. In the case of no residue, X is a residue. Exposure sensitivity: Exposure by ultraviolet light with an integrated light amount of 100 mJ by a double-sided simultaneous exposure machine "HMW - 5 3 2 D" (manufactured by Ouke Manufacturing Co., Ltd.) for photoresist exposure, followed by exposure to 3 0 °C of 1.0% by weight of sodium carbonate aqueous solution, under the condition of spray pressure of 2 kg / cm 2 , confirm the number of steps in the injection of 60 seconds (Study hair 2 1 film coating) Number of remaining segments). The sensitivity is below 2 segments: X, 3~4 segments: 〇, 5 segments or more: ◎. Viscosity: The coated substrate was cut into 匚]10 cm X 10 cm, and the surface of the overlapping coating film was placed at a weight of 20 kg/cm2 for one day. The unattached person was marked as ◎, and the slightly conformed person was marked as 〇. A large number of fitters are marked as X. Coating property: the substrate is impregnated in the photosensitive photoresist solution. When the film is pulled up, the thickness of the surface without the coating film is marked as 〇, and the thickness unevenness is marked as X ° (synthesis of resin solution A). 5 parts of methacrylate, 5 parts of 2-hydroxyethyl acrylate, 1 part of butyl acrylate, 8.1 parts of butyl acrylate, and 6.9 parts of methacrylic acid, fluorenyl ethyl ketone 150.0 The solution was dissolved in a nitrogen atmosphere, and polymerization was carried out under stirring and reflux conditions using a polymerization initiator to obtain a weight average molecular weight of 2,800 in terms of polystyrene, an acid value of 1 1 OmgKOH/g, and a solid content. The resin solution A having a concentration of 40.0% by weight. (Synthesis of Resin Solution B) 55.0 parts of methyl methacrylate, 2-ethylhexyl acrylate 10.0 15 312 / invention specification (supplement) / 93-09/93117916 1298731 parts, benzyl methacrylate 1 5 0 parts, and 2 parts of methacrylic acid · 0 parts, dissolved in 150.0 parts of methyl ethyl ketone, polymerized under a nitrogen atmosphere with a polymerization initiator under stirring and reflux conditions to obtain polystyrene The resin solution B having a weight average molecular weight of 63,000, an acid value of 130 mgKOH/g, and a solid content of 40.0% by weight was converted. (Synthesis of Resin Solution C) 58.0 parts of methyl methacrylate, 9.0 parts of 2-ethylhexyl acrylate, 10 parts of methacrylic acid ester, and 2 parts of methacrylic acid were used. The thioglycol ketone was dissolved in 1 part by weight, and the polymerization was carried out under stirring in a nitrogen atmosphere using a polymerization initiator to obtain a weight average molecular weight of 107,000 in terms of polystyrene and an acid value of 150 mgKOH/ g. Resin solution C having a solid concentration of 40.0% by weight. 1 (modulation of photosensitive photoresist solution E) Resin solution A 3 0. 0 parts, iso-cyanuric acid E 0 modified triacrylate 3.0 parts (solid / 25 ° C), dipentaerythritol hexaacrylate 4.0 parts (Viscosity: 4 2 0 0 in P a · s / 2 5 °C), a resin having an ethylenically unsaturated group in the side chain (molecular weight: 1 500), unsaturated base equivalent: 3 5 0 (g / eq ), solid content: 60% by weight) 10 parts, 2-methyl[4-(decylthio)phenyl]-2-morpholinyl-propane-1-one 1.5 parts, diethyl- 9-oxydibenzothiazepine, 0,5 parts, and UV-B 1 ue 2 3 6 (manufactured by Mitsui Chemicals, Inc.) 0.1 parts were mixed to prepare a solid concentration of 55.2% by weight of photosensitive photoresist Stock solution E. (Preparation of photosensitive photoresist solution F) Resin solution B 3 0. 0 parts, dipentaerythritol hexaacrylate 4. 0 parts (viscosity 16 312 / invention specification (supplement) / 93-09/93117916 1298731 degrees: 4200 mPa · s / 25 ° C), pentaerythritol tetraacrylate 3.0 long / 2 5 ° C), a compound having an ethylenically unsaturated group in the side chain (minute 1 500, ethylenically unsaturated group equivalent: 3 5 0 ( g / eq ), solid part %) 10 parts, 2-methyl [4-(methylthio)phenyl]-2-morpholinyl-1-1-one 1.5 parts, diethyl -9-Oxodibenzothiopyranose 0. 5 parts UV-B 1 ue 2 3 6 (manufactured by Mitsui Chemicals, Inc.) 0 · 1 part to be mixed, adjusted! A photosensitive photoresist solution F having a concentration of 55.2% by weight. (Preparation of photosensitive photoresist solution G) Resin solution C 3 0. 0, dipentaerythritol hexaacrylate 3. 0 degrees: 4200 mPa·s / 25 ° C), pentaerythritol tetraacrylate 4.0 injury / 25 ° C a compound having an ethylenically unsaturated group in a side chain (a fraction of 15,000, an ethylenically unsaturated group equivalent of 450 (g/eq), a solid part by weight) of 10 parts, 2-methyl [4-(A) Thiophenyl)phenyl]-2-morpholino--1*~8 with 1.5 parts, diethyl-9-oxodibenzosulfone® 0.5 part, UV-Blue 2 3 6 (Mitsui Chemical Co., Ltd. 0) 1 part is mixed, and the concentration of 55.2% by weight of the photosensitive photoresist solution G is adjusted. (Preparation of photosensitive photoresist raw material )) Resin solution Β 4 0., dipentaerythritol hexaacrylate (viscosity: 4200 mPa·s / 25 ° C), 2-methyl [4-(methylthio) 1.5 parts of phenylinyl-propan-1-one, diethyl-9-oxodibenzothione, and UV-Β1 ue 2 3 6 (manufactured by Mitsui Chemicals Co., Ltd.) 0.1 parts of the solid content A photosensitive photoresist residue Η having a concentration of 51. 1% by weight. (Preparation of photosensitive photoresist solution I) Resin solution Β 3 0 · 0 parts, trishydroxypropyl propane triacrylate 312 / invention specification (supplement) / 93-09/93117916 ' (solid amount: ·· 60 propylene, and lean | parts (viscosity r (solids: 60 weights • propylene and good solids 7 · 0 bases) -2- ane 0 · 5 mixed, 7 · 0 parts 17 1298731 (viscosity : 65 mPa·s / 25 ° C), a compound having an ethylenically unsaturated group in a side chain (molecular weight: 15,000, ethyl bromide unsaturated equivalent: 350 (g/eq), solid content: 60 weight % /〇) 10 parts, 2 -fluorenyl [4 -(decylthio)phenyl]- 2 -morphinyl-propanone-1 - S with 1. 5 parts, diethyl-9-oxygen 0.1 parts of benzothiazepine, and UV-B 1 ue 2 3 6 (manufactured by Mitsui Chemicals, Inc.) 0.1 parts were mixed to prepare a photosensitive photoresist solution I having a solid concentration of 55.2% by weight. Preparation of photosensitive photoresist solution Z) Resin solution A 3 0. 0 parts, dipentaerythritol hexaacrylate 2. 0 parts (viscosity: 4500 mPa * s / 25 ° C), pentaerythritol tetraacrylate 5.0 parts (solid / 2 5 °C), with ethylene deficiency on the side chain Base compound (ethylenically unsaturated group equivalent: 86 (g/eq)) 10 parts, 2-methyl[4-(fluorenylthio)phenyl]-2-morphinyl-propane--1_8 with 1.5 5 parts, and UV-Blue 2 3 6 (manufactured by Mitsui Chemicals, Inc.) 0. 1 part is mixed, and the solid content concentration is adjusted to 3.3.3% by weight. Photosensitive photoresist stock solution Z. (Preparation of photosensitive photoresist raw material AA) Resin solution B 3 0. 0 parts, dipentaerythritol hexaacrylate 5. 0 parts (viscosity: 4500 mPa * s / 25 ° C), pentaerythritol IV Acetic acid ester 2·0 parts (solid / 25 ° C), compound having an ethylenically unsaturated group in the side chain (ethylenically unsaturated group equivalent: 1260 (g/eQ)) 10 parts, 2-methyl [ 5 parts, and UV-Blue 2, 4-(mercaptothio)phenyl]-2-morphinyl-propan-1-one 1.5 parts, diethyl-9-oxydibenzothiazepine 0. 5 parts, and UV-Blue 2 3 6 (manufactured by Mitsui Chemicals Co., Ltd.) 0 parts of the mixture was mixed to prepare a photosensitive resist solution AA having a solid concentration of 55.2% by weight. (Example 1) (Modulation of photosensitive photoresist K) 18 312 /Invention Manual (Repair)/93-09/93117916 1298731 Will Μ E Κ 3 5 . 0 and C Glycol monomethyl ether acetate. 1 5.9 parts of a photosensitive resist liquid is mixed in E, stirring to modulate photosensitive photoresists K. (Example 2) (Preparation of photosensitive photoresist liquid L) Photosensitive photoresist stock solution E was used as it is. (Example 3) (Preparation of photosensitive photoresist liquid )) Μ Ε Κ 3-5 parts and propylene glycol monodecyl ether acetate 9.5 parts were mixed in photosensitive photoresist raw material F, and stirred to prepare Photosensitive photoresist liquid Μ. (Example 4) (Preparation of photosensitive photoresist liquid) The photosensitive photoresist raw material F was used as it is. (Example 5) (Preparation of photosensitive photoresist liquid 0) Μ Ε Κ 3 5. 0 parts and propylene glycol monodecyl ether acetate 1 5. 9 parts were mixed in photosensitive photoresist raw material solution G, and stirred to prepare Photosensitive photoresist 0. (Example 6) (Preparation of photosensitive photoresist liquid) The photosensitive photoresist raw material G was used as it is. (Comparative Example 1) (Preparation of photosensitive photoresist Q) Μ Ε Κ 3 0.5 parts and propylene glycol monodecyl ether acetate 1 5.9 parts were mixed in a photosensitive photoresist mash and stirred to prepare Photosensitive photoresist Q. (Comparative Example 2) 19 312/Invention Manual (Supplement)/93-09/93117916 1298731 (Preparation of photosensitive photoresist R) Μ EK 3 5.0 parts and propylene glycol monodecyl ether acetate 1 5 · 9 parts were mixed in the photosensitive photoresist stock solution I, and stirred to prepare the photosensitive photoresist liquid R. (Example 7) (Preparation of photosensitive photoresist A) Μ EK 4 6 . 2 parts and propylene glycol monodecyl ether acetate 19. 9 parts were mixed in a photosensitive photoresist stock solution, and stirred to prepare Photosensitive photoresist liquid ΑΕ. (Example 8) (Preparation of photosensitive photoresist AF) Μ Ε K 3 5.0 parts and propylene glycol monodecyl ether acetate 9.5 parts were mixed in a photosensitive photoresist mash and stirred to prepare Photosensitive photoresist AF. (Comparative Example 3) (Preparation of photosensitive photoresist AG) 4 parts of dipentaerythritol hexaacrylate in photosensitive photoresist solution F (viscosity: 4 2 0 0 m P a · s / 2 5 ° C 5份和丙醇单曱基。 The pentaerythritol tetraacrylate 3 · 0 parts (solid / 25 ° C) was changed to polyethylene glycol diacrylate (50mPa · s / 25 ° C) 3.0 parts, further ΜΕΚ35. 0 parts with propylene glycol monodecyl Ethyl acetate S was mixed in 15.9 parts and stirred to prepare a photosensitive photoresist AG. (Manufacturing Method of Printed Wiring Substrate) A printed circuit board of a glass epoxy double-sided copper clad laminate (having a thickness of 0.2 m, a copper thickness of 18/zm, and a substrate size of 370 mm x 260 mm) was prepared. Next, a photosensitive photoresist liquid and a stock solution (G) were stored in a stainless steel container to prepare a dipping bath. Then, the printed wiring board prepared as described above was immersed at a speed of 50 cm / min with respect to the liquid surface, so that the upper end of the substrate 20 312 / invention manual (supplement) / 93-09/93117916 1298731 protruded The surface of the liquid surface is immersed in the state of 1 c ιτι, and after stopping, the entire substrate is pulled up from the liquid surface at a pulling speed of 50 cm/min, and a photosensitive photoresist liquid is applied, and in a hot air dryer, 80 After drying at ° C for 10 minutes, it was cooled to room temperature. Two mask films having a pattern in which a conductor pattern can be formed are used, and the mask film is brought into contact with both sides of the substrate such that the direction of the wiring pattern of each mask film is perpendicular to each other, and the both sides of the photoresist are simultaneously exposed by the photoresist The exposure machine "HMW-532D" (manufactured by Ouke Manufacture) was exposed to ultraviolet light with an integrated light amount of 10 〇 to 50,000 m J, followed by a sodium carbonate of 30 ° C at 1.0% by weight. The aqueous solution was sprayed and developed under a spray pressure of 2 kg / c m2 to form a photoresist layer of the specified photoresist pattern. Then, the exposed portion of the copper is removed by a copper (II) chloride residue at 40 ° C, and washed with water at 40 ° C of 3.0% by weight aqueous sodium hydroxide solution at a spray pressure. The metal wiring layer of the conductor pattern was formed by spraying at 2 kg/cm 2 to remove the etching photoresist layer to form a printed wiring board. The test results of the printed wiring board obtained as described above are shown in Table 21 312 / Invention specification (supplement) / 93-09/93117916 1298731 ττ film thickness [β^] ο ◦ rH ◦ σϊ ◦ CJi <〇◦ Coating 〇〇〇〇〇〇〇〇〇〇〇 〇〇〇〇〇〇〇〇〇〇〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ XX Exposure sensitivity ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 X ◎ X Developability 〇〇〇〇〇〇〇〇 〇〇〇Photosensitive compound viscosity [mPa · s/25°C ] Solid 4200 ! Solid 4200 Solid 4200 Solid 4200 Solid 4200 Solid 4200 Solid 4200 Solid 4200 4200 LO CO g Solvent amount [%] CO LO Inch CO LO Inch CO LO Inch CO CO LO CO CO Ethylene Unsaturated Equivalent (g/eq) 〇> LO 〇〇CD LO CO ◦ LO CO ◦ LO CO CD LO Inch CO oo 1260 1 o LO OO o LO CO Photoresist Liquid ω ω o ο CS3 >—1 1 Acid value of the test solubility resin [mgKOH/g] CD i—i rH CD t—H t—H CD CO »—1 ◦ CO rH LO rH c=> LO r —i OH r—H 〇> CO rH ◦ CO r—H 〇> CO rH o CO Alkaline soluble resin molecular weight 1 28000 28000 6 3000 63000 107000 107000 28000 63000 ! 63000 63000 63000 Resin solution PQ PQ oo < PQ PQ CQ PQ Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 916 Bu 11 £6/60. £6/(minutes}«)_^舔&&micro/31 e 1298731 (industrial use possibility) According to the present invention, non-stickiness can be formed An etched photoresist layer with good exposure sensitivity is an extremely important invention in the industry. 23 312/Invention Manual (supplement)/93-09/93117916