201132663 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種取得溶液或乾膜之形態的光硬化性. 熱硬化性樹脂組合物及其硬化物，更詳細而言係關於適 於形成民生用乃至產業用印刷配線板、特別是可撓性印刷 配線板用焊料抗蝕劑或導體電路層間之絕緣層等的光硬化 性·熱硬化性樹脂組合物及其硬化物。又，本發明亦係關 於一種由該等組合物之硬化物形成絕緣層而成之印刷配線 板。 【先前技術】 印刷配線基板根據其用途，有利用剛性玻璃環氧基板者 至利用薄且具有可撓性之配線版（可撓性印刷配線板）者。 特別是近年來，為了加工步驟之簡略化或封裝面積之小型 化'高密度化等，可撓性印刷配線板之使用增加。先前之 將以酚醛清漆型環氧化合物為基礎之含羧基之感光性樹脂 作為主成分的焊料抗蝕劑組合物難以滿足上述使用時之要 求’而提出具有胺基甲酸酯骨架之樹脂（專利文獻丨）。 又，於專利文獻2中提出有一種感光性樹脂組合物，其 特徵在於：包含具有2個以上羥基與1個以上羧基之化合 物、具有ό員環結構之2官能以上之聚異氰酸酯、具有羥基 之丙烯酸胺基曱酸酯、光聚合起始劑及稀釋劑。 [先前技術文獻] [專利文獻] [專利文獻1]曰本專利特開平9-52925號公報 § 152180.doc 201132663 [專利文獻2]曰本專利第4057721號公報 【發明内容】 [發明所欲解決之問題] 本發明之目的在於提供一種柔軟且強韌之焊料抗钱劑組 合物。 [解決問題之技術手段] 本發明者等為了解決上述課題而銳意研究，結果完成了 本發明。 即，本發明係關於以下（1)〜（8)。 (1) 一種可鹼顯影之印刷配線板用感光性樹脂組合物，其特 徵在於.包含具有聯苯紛路清漆結構之含缓基之胺基甲酸 酯樹脂（A)及光聚合起始劑（b)。 (2) 如上述（1)之可鹼顯影之印刷配線基板用感光性樹脂組 合物，其中含羧基之胺基甲酸酯樹脂（A)係使一元酸（(：）與 下述式（I)所示之具有聯苯酚醛清漆結構之環氧樹脂⑴反 應’並使所得之含羥基之環氧羧酸酯化合物（D)與具有羧 基之二醇化合物（E)以及二異氰酸酯化合物（F)反應而得 者。 [化1]BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocuring property in which a solution or a dry film is obtained. A thermosetting resin composition and a cured product thereof, and more particularly, are suitable for formation. A photocurable thermosetting resin composition and a cured product thereof, such as a printed wiring board for industrial use, a solder resist for a flexible printed wiring board, or an insulating layer between conductor circuit layers. Further, the present invention relates to a printed wiring board in which an insulating layer is formed of a cured product of the compositions. [Prior Art] The printed wiring board has a rigid glass epoxy substrate and a flexible wiring board (flexible printed wiring board). In particular, in recent years, the use of flexible printed wiring boards has increased in order to simplify the processing steps or to miniaturize the package area. A solder resist composition having a carboxyl group-containing photosensitive resin based on a novolak-type epoxy compound as a main component is difficult to satisfy the above requirements, and a resin having a urethane skeleton is proposed (patent Literature 丨). Further, Patent Document 2 proposes a photosensitive resin composition comprising a compound having two or more hydroxyl groups and one or more carboxyl groups, a polyfunctional isocyanate having two or more functional groups having a oxime ring structure, and a hydroxyl group. Amino phthalic acid acrylate, photopolymerization initiator and diluent. [PRIOR ART DOCUMENT] [Patent Document 1] [Patent Document 1] Japanese Patent Laid-Open No. Hei 9-52925 § 152180.doc 201132663 [Patent Document 2] Japanese Patent No. 4057721 [Invention] [Invented Problem] An object of the present invention is to provide a soft and strong solder resist composition. [Means for Solving the Problem] The inventors of the present invention have intensively studied in order to solve the above problems, and as a result, have completed the present invention. That is, the present invention relates to the following (1) to (8). (1) A photosensitive resin composition for an alkali-developable printed wiring board, comprising a slow-setting urethane resin (A) having a biphenyl varnish structure and a photopolymerization initiator (b). (2) The photosensitive resin composition for an alkali-developable printed wiring board according to the above (1), wherein the carboxyl group-containing urethane resin (A) is a monobasic acid ((:) and the following formula (I) The epoxy resin (1) having a biphenyl novolac structure is shown to react 'and the resulting hydroxyl group-containing epoxy carboxylate compound (D) and the diol compound (E) having a carboxyl group and the diisocyanate compound (F) The reaction is obtained. [Chemical 1]
152180.doc 201132663 (式中，η表示平均值，為ίο!〜5) (,)如上述⑴至⑺中任一項之可驗顯影之印刷配線板用感 光杜树月日組σ物’其中二異氰酸3旨化合物（F)為脂肪族系 一異氰酸醋化合物。 (4)如上述⑴至（3)中任—項之可驗顯影之印刷配線板用感 光性樹脂組合物，其中包含熱硬化性樹脂（G)。 ()如上述（1)至（4)中任—項之可驗顯影之印刷配線板用感 光性樹脂組合物，其中包含著色劑（Η)。 (6) 如上述（1)至（5)中任一項之可鹼顯影之印刷配線板用感 光性樹脂組合物，其為乾膜之形態。 (7) —種硬化物，其係如上述（丨）至（5)中任一項之感光性樹 脂組合物之硬化物。 (8) —種印刷配線板，其具有硬化皮膜，該硬化皮膜係使如 上述（1)至（5)中任一項之感光性樹脂組合物或如（6)之乾膜 於圖案上光硬化後，進行熱硬化而得者。 [發明之效果] 本發明之可用作焊料抗蝕劑墨水之感光性樹脂組合物之 硬化物藉由包含由具有聯苯酚醛清漆結構之環氧樹脂而得 之胺基曱酸酯化合物’而表現優異之柔軟性、強韌性，特 別是最適合作為可驗顯影之印刷配線板用感光性樹脂組合 物。 【實施方式】 本發明之感光性樹脂組合物所含之具有聯苯酚醛清漆結 構之含羧基之胺基甲酸酯樹脂（Α)並無特別限定，較佳為 s 152180.doc -5- 201132663 使上述式(1)所示之環氧樹脂⑴與-元酸(c)之反應物的含 減之環氧㈣S旨化合物⑼、與具有絲之：醇化合物 (E)以及一異氰酸酯化合物（F)反應而得之化合物。 該環氧樹脂⑴中，n以平均值計為1Gi〜5e；^超過$ 時’所得之胺基甲酸㈣脂⑷之分子量變大，製成組合 物時之相溶性降低，於樹脂合成時有可能凝踢化等。於n 未達1.01時，所得之胺基甲㈣黯（A)無法獲得作為組合 物中之黏合劑之性能。但為了突出作為本樹脂之特徵的低 彈性，較佳為於不損及作為黏合劑之性能的程度下^較 小。特佳為η為1.01M.5之範圍。該環氧樹脂（1)可藉由公 知之文獻記載之方法而製造，又，以NC3〇〇〇系列（日本化 藥製造）之商品市售。 作為一元酸（C)，較佳為於分子中具有乙烯性不飽和雙 鍵者，就光硬化性之方面而言，特佳為可列舉丙烯酸、甲 基丙烯酸或源自該等之衍生物之化合物。 作為具有羧基之二醇化合物之具體例，可列舉：二 羥甲基丙酸、二羥甲基丁酸、二醇化合物與多元酸酐之反 應產物等’就作為胺基曱酸蜎樹脂（A)之溶劑溶解性或硬 化物之柔軟性的觀點而言，較佳為二羥甲基丁酸。該等可 單獨使用，或者亦可將2種以上加以組合而使用。 二異氰酸醋化合物（F)可使用先前公知之各種二.異氰酸 酯化合物，就柔軟性之觀點而言，較佳為脂肪族系二異氰 酸酯化合物。具體可列舉：1，6-六亞甲基二異氰酸醋、 1，4·四亞甲基二異氰酸酯、^2-十二亞甲基二異氰酸g旨、 152180.doc -6 - 201132663 2,2,4-三曱基六亞甲基二異氰酸酯、異佛爾酮二異氰酸 醋、2,4,4-三甲基六亞曱基二異氰酸酯等。該等可單獨使 用，或者亦可將2種以上加以組合而使用。 又’視需要亦可使用使多元酸酐與胺基曱酸酯樹脂（A) 反應而得之酸改性型反應性胺基甲酸酯樹脂。其目的係不 僅附加具有綾基之二醇化合物（E)，而且根據所要求之樹 脂之特性’附加鹼顯影所需要之酸值。 本發明中，將該反應步驟稱為加酸步驟。 作為多元酸酐之具體例，例如若為於一分子中具有酸酐 結構之化合物，則可全部使用，特佳為鹼水溶液顯影性、 耐熱性、耐水解性等優異之琥珀酸酐、鄰苯二甲酸酐、四 氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、衣康酸酐、3-甲基- 四氫鄰苯二甲酸酐、4-甲基-六氫鄰笨二甲酸酐、偏苯三甲 酸酐或順丁婦二酸酐。 如上述之胺基甲酸酯樹脂（A)由於直接鍵結於主鏈之羧 基，而於光阻劑製程令，可藉由稀鹼水溶液進行顯影。此 時，胺基甲酸酯樹脂之酸值較佳為2〇〜15〇 ，更 佳為 40〜1 〇〇 mgKOH/g。 又，上述胺基甲酸酯樹脂（A)之重量平均分子量亦因樹 脂骨架而不同，通常為處於2_〜2_之範圍者更佳為 處於4000〜15_之範圍者。重量平均分子量為應以下 時’存在不黏著性能差之情況，曝光後因顯影液所致之膜 縮小亦往往變Λ。另—方面，若重量平均分子量超過 20000，則存在顯影性明顯降低之情況。 152180.doc 5 201132663 作為上述光聚合起始_)，可使用藉由曝光而產生自 由基之先前公知的各種光聚合起始劑。料料光聚合起 始劑’可列舉：安息香或安息香烷基醚系、二苯曱酮或咄 酮系、9-氧硫咄P星系、苯乙酮系、胺基苯乙酮系、蒽醌 系、有機過氧化物、三畊系、肟酯系等。具體可列舉：安 息香、安息香醚、安息香丁醚、安息香丙醚、二苯曱酮、 3,3·-二曱基-4-甲氧基二苯甲酮、苯曱醯苯甲酸苯曱醯苯 曱酸之酯化物、4-笨甲醯基_4，_甲基二苯基硫醚、苯偶醯 二曱基縮酮、2- 丁氧基乙基-4·甲基胺基苯甲酸酯、氣_9_ 氧硫咄蠖、甲基·9·氧硫咄喵、乙基_9_氧硫咄嗤、異丙基_ 9-氧硫咕u星、一曱基-9-氧硫ρ山ρ星、二乙基-9-氧硫υ山ρ星、 二異丙基-9-氧硫tr山蠖、苯甲酸二曱基胺基曱酯、二甲基胺 基苯甲酸異戊酯、1-(4-十二烷基苯基）-2-羥基_2_曱基丙 烷-1-酮、1-羥基環己基苯基嗣、2-羥基-2-曱基-1-苯基丙 烷-1-酮、1-(4-異丙基苯基）-2-羥基-2-甲基丙烷-1-酮、苯 甲醯曱酸甲酯、2-曱基-1-(4-曱硫基苯基）-2-嗎啉基丙烷-1-嗣、基-2 - 一曱基胺基-1-(4 -嗎淋基苯基）-丁炫-1-酿j、 2,2·-雙（2-氯苯基^，^，，-四苯基雙咪唑〜之”-雙⑺氯苯 基）-4,4·，5,5·-四_(4_曱氧基苯基）雙咪唑、2,4-雙（三氣曱基）-Μ4-甲氧基苯基）-1，3,5-均三畊、2,4,6-三（三氯甲基）-1，3,5-均三畊、2,4-雙（三溴甲基）-6-(4，-曱氧基苯基）-1，3,5-均三畊、2,4,6-三（三溴曱基）-1，3,5-均三畊、2,4-雙（三氣甲 基）-6-(1,3-苯并二氧戊環_5·基）-1，3,5-均三畊、二苯曱酮、 苯曱醯苯甲酸、1-(4-苯硫基苯基）丁烷-1,2-二酮-2-肟-0-笨 152180.doc -8 - 201132663 甲酸酯、1-(4-甲硫基苯基）丁烷二酮_2_肟_〇_乙酸酯、 1 -(4-甲硫基笨基）丁燒_丨_酮將乙酸酯、2_(乙醯氧基亞 胺基甲基）硫咕p星-9-綱等，但並不限定於該等。 作為熱硬化性樹脂（G)，較佳為使用作為於活性能量線 下不表現反應性之樹脂類而公知一般的具有環狀醚之樹 脂、特別是環氧樹脂。其原因在於：若藉由活性能量線而 反應、硬化後亦殘留源自胺基甲酸酯樹脂（A)之羧基，則 結果導致其硬化物之耐水性或水解性較差。因此，較佳為 藉由使用環氧樹脂而使殘留之羧基進一步羧酸酯化，進而 形成牢固之交聯結構。 作為著色劑(H) ’可列舉：駄菁系、偶氮系、喹吖啶酮 系等有機顏料，碳黑、氧化鈦等無機顏料。 該製造中可使用稀釋劑。作為可用作稀釋劑之有機溶 劑，例如可列舉：甲基乙基酮、環己酮等酮類，甲苯、二 甲苯等芳香族烴類，環己烷、甲基環己烷等脂環式烴類， 石油醚、石油腦等石油系溶劑，乙酸乙酯、乙酸丁酯、溶 纖劑乙鲅S曰、卡必醇乙酸酯、丙二醇單甲醚乙酸酯等酯系 溶劑等。該等可單獨使用，或者亦可將2種以上加以組合 而使用。 所明乾膜，係指將本發明之感光性樹脂組合物暫時塗佈 於剝離性基材並膜化後，與本來目標之基材貼合而形成皮 膜之材料。乾膜化時，藉由刮刀式塗佈機、刮板塗佈機、 模唇塗佈機、棒式塗佈機、擠壓式塗佈機、反向塗佈機、 傳送輥塗佈機、凹板印刷塗佈機、喷霧塗佈機等，將本發 152180.doc •9· 201132663 明之感光性樹脂組合物於支持體（載體膜）上塗佈成均勻之 厚度’並進行乾燥而獲得膜。塗佈膜厚並無特別限制，通 常於塗佈後之膜厚為10〜150 μπι、較佳為20〜6〇 μιη之範圍 内適當選擇。 載體膜可使用塑膠膜，可列舉：聚對苯二甲酸乙二酯等 聚醋膜、聚醯亞胺膜、聚醯胺醯亞胺膜、聚丙烯膜、聚苯 乙烯膜等。 於載體膜上成膜後，為了進一步防止灰塵附著於膜表 面，較理想為於膜表面積層可剝離之覆蓋膜。作為可剝離 之覆蓋膜，例如可使用聚乙烯膜、聚四氟乙烯膜、聚丙烯 膜等，於將覆蓋膜剝離時，膜與覆蓋膜之黏接力小於膜與 支持體之黏接力即可。 將本發明之感光性樹脂組合物視需要進行稀釋，調整成 適於塗佈方法之黏度後，於經電路形成之印刷配線板上， 藉由網版印刷法、簾塗法、喷塗法、輥塗法等方法進行塗 佈’於例如約60〜100ec之溫度下使組合物中所含之有機溶 劑揮發乾燥，藉此可形成不黏著之塗膜。 本發明之感光性樹脂組合物為乾膜形態時，於經電路形 成之印刷配線板上層壓後，以不剝離支持體之狀態形成與 上述不黏著之塗膜同樣之狀態。 然後’使雷射光等活性能量線對圖案直接曝光，或者通 過形成圖案之光罩進行曝光，藉由稀驗水溶液將未曝光部 進行顯影而形成抗蝕劑圖案（為乾膜時，於曝光後剝離支 持體進行顯影）。 152180.doc -10- 201132663 進而進行加熱硬化，或於活性能量線照射後進行加熱硬 化，藉此亦可獲得電絕緣性、密接性、焊錫耐熱性、耐藥 品性、無電解鍍金性、柔軟性優異之硬化膜。 顯影後之加熱硬化溫度較佳為l4〇〜24〇〇c左右。藉由該 步驟，本發明之胺基甲酸酯樹脂（A)之羧基與印刷配線基 板用感光性樹脂組合物中所含之具有環狀醚之熱硬化性樹 月曰（G)發生反應，可形成耐熱性 '耐藥品性、对吸濕性、 密接性、電氣特性等各特性優異之硬化塗膜。 作為印刷配線板之基材，可列舉：使用紙_酚樹脂、紙_ 環氧樹脂、玻璃布-環氧樹脂、玻璃_聚醯亞胺、玻璃布/不 織布-環氧樹脂、玻璃布/紙-環氧樹脂、合成纖維_環氧樹 脂、氟樹脂-聚乙稀-氰酸酯等複合材料之所有等級（FR_4 等）之銅箔積層板、聚醯亞胺膜、PET膜、玻璃基板、陶竟 基板、晶圓基板等。若考慮到本發明之感光性樹脂組合物 之特性，則作為基板’可以說具有柔軟性者更佳。 [實施例] 以下，藉由實施例對本發明進行更詳細說明，但本發明 並不限定於下述實施例。再者，於實施例中，％係指質量 %。 合成例1 於安裝有撥拌裝置、回流管之燒瓶中，投入作為具有聯 苯酚醛清漆結構之環氧樹脂（1)的日本化藥製造之 NC-3000(環氧當量255 g/eq.)300.0 g'作為一元酸（c)的丙 稀酸84.7 g、作為熱聚合抑制劑的2,6-二第三丁基_4_甲基152180.doc 201132663 (where η represents the average value, ίο!~5) (,) The photosensitive Dushu Yueri Group σ object of the printed wiring board according to any one of the above (1) to (7) The compound (F) of cyanate 3 is an aliphatic monoisocyanate compound. (4) The photosensitive resin composition for a printed wiring board according to any one of the above (1) to (3), wherein the thermosetting resin (G) is contained. (A) The photosensitive resin composition for a printed wiring board which can be developed by any of the above (1) to (4), which contains a coloring agent. (6) The photosensitive resin composition for an alkali-developable printed wiring board according to any one of the above (1) to (5), which is in the form of a dry film. (7) A cured product which is a cured product of the photosensitive resin composition according to any one of the above (A) to (5). (8) A printed wiring board having a hardened film which is obtained by patterning a photosensitive resin composition according to any one of the above (1) to (5) or a dry film such as (6) After hardening, it is obtained by thermal hardening. [Effects of the Invention] The cured product of the photosensitive resin composition which can be used as the solder resist ink of the present invention is composed of an amino phthalate compound which is obtained from an epoxy resin having a biphenyl aldehyde varnish structure. It is excellent in flexibility and toughness, and is particularly suitable as a photosensitive resin composition for a printed wiring board which can be developed. [Embodiment] The carboxyl group-containing urethane resin having a biphenyl novolak structure contained in the photosensitive resin composition of the present invention is not particularly limited, and is preferably s 152180.doc -5 - 201132663 The epoxy (IV) S-containing compound (9) and the silk-containing: alcohol compound (E) and monoisocyanate compound (F) having the reaction product of the epoxy resin (1) and the -acid acid (c) represented by the above formula (1) a compound obtained by the reaction. In the epoxy resin (1), n is 1 Gi to 5 e on the average; when the amount exceeds $, the molecular weight of the obtained aminocarboxylic acid (tetra) lipid (4) becomes large, and the compatibility at the time of preparation of the composition is lowered, and there is a case where the resin is synthesized. It may be condensed and so on. When n is less than 1.01, the resulting aminomethyl(tetra)phosphonium (A) cannot obtain the properties as a binder in the composition. However, in order to emphasize the low elasticity which is characteristic of the present resin, it is preferable to be small to the extent that the performance as a binder is not impaired. It is particularly preferable that η is in the range of 1.01 M.5. The epoxy resin (1) can be produced by a method known in the literature, and is commercially available as a product of the NC3 series (manufactured by Nippon Kayaku Co., Ltd.). As the monobasic acid (C), it is preferred to have an ethylenically unsaturated double bond in the molecule, and in terms of photohardenability, particularly preferred are acrylic acid, methacrylic acid or derivatives derived therefrom. Compound. Specific examples of the diol compound having a carboxyl group include dimethylolpropionic acid, dimethylolbutanoic acid, a reaction product of a diol compound and a polybasic acid anhydride, etc., as an amino bismuth ruthenate resin (A). From the viewpoint of solvent solubility or flexibility of the cured product, dimethylolbutanoic acid is preferred. These may be used singly or in combination of two or more. As the diisocyanate compound (F), various conventionally known diisocyanate compounds can be used, and from the viewpoint of flexibility, an aliphatic diisocyanate compound is preferred. Specific examples thereof include 1,6-hexamethylene diisocyanate, 1,4, tetramethylene diisocyanate, ^2-dodecyl diisocyanate, 152180.doc -6 - 201132663 2,2,4-trimethyl hexamethylene diisocyanate, isophorone diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the like. These may be used singly or in combination of two or more. Further, an acid-modified reactive urethane resin obtained by reacting a polybasic acid anhydride with an amino phthalate resin (A) may be used as needed. The purpose is not only to add a diol compound (E) having a mercapto group, but also to add an acid value required for alkali development depending on the characteristics of the desired resin. In the present invention, this reaction step is referred to as an acid addition step. As a specific example of the polybasic acid anhydride, for example, a compound having an acid anhydride structure in one molecule can be used in its entirety, and particularly preferred is an succinic anhydride or phthalic anhydride excellent in alkali developability, heat resistance, hydrolysis resistance, and the like. , tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, trimellitic acid Anhydride or cis-butanic anhydride. The urethane resin (A) as described above can be developed by a dilute aqueous alkali solution because it is directly bonded to the carboxyl group of the main chain in the photoresist process. At this time, the acid value of the urethane resin is preferably from 2 Torr to 15 Torr, more preferably from 40 to 1 〇〇 mgKOH/g. Further, the weight average molecular weight of the urethane resin (A) varies depending on the resin skeleton, and is usually in the range of 2 to 2 or more preferably in the range of 4000 to 15 mm. When the weight average molecular weight is below □, there is a case where the adhesiveness is poor, and the film shrinkage due to the developer after the exposure tends to be abrupt. On the other hand, if the weight average molecular weight exceeds 20,000, the developability is remarkably lowered. 152180.doc 5 201132663 As the above photopolymerization start-), various photopolymerization initiators previously known to produce a radical by exposure can be used. The material photopolymerization initiator can be exemplified by benzoin or benzoin alkyl ether, benzophenone or anthrone, 9-oxopurine P, acetophenone, aminoacetophenone, anthracene Department, organic peroxide, three tillage, oxime ester and so on. Specific examples thereof include benzoin, benzoin ether, benzoin butyl ether, benzoin propyl ether, dibenzophenone, 3,3·-dimercapto-4-methoxybenzophenone, benzoquinone benzoquinone benzoate Ester ester of citric acid, 4-benzoyl ketone-4, _methyl diphenyl thioether, benzoin decyl ketal, 2-butoxyethyl-4·methylaminobenzoic acid Ester, gas _9_ oxysulfuron, methyl -9 oxa sulfonium, ethyl _9 oxa thiopurine, isopropyl -9 oxa thiopurine, fluorenyl-9-oxosulfur ρ山ρ星, diethyl-9-oxosulfonium ruthenium, diisopropyl-9-oxothiotrifene, dimercaptoalkyl benzoate, isoamyl dimethylaminobenzoate Ester, 1-(4-dodecylphenyl)-2-hydroxy-2-hydrazinopropan-1-one, 1-hydroxycyclohexylphenylhydrazine, 2-hydroxy-2-indolyl-1-phenyl Propane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, methyl benzoate, 2-mercapto-1-(4- Indylthiophenyl)-2-morpholinylpropane-1-indole,yl-2-indenylamino-1-(4-pipelinylphenyl)-butan-1-ol j, 2, 2·-bis(2-chlorophenyl^,^,,-tetraphenylbisimidazole~"-bis(7)chlorophenyl)-4 ,4·,5,5·-tetra-(4-methoxyphenyl)biimidazole, 2,4-bis(trimethylsulfonyl)-fluorene 4-methoxyphenyl)-1,3,5- Three tillage, 2,4,6-tris(trichloromethyl)-1,3,5-all three tillage, 2,4-bis(tribromomethyl)-6-(4,-decyloxybenzene Base)-1,3,5-all three tillage, 2,4,6-tris(tribromoindolyl)-1,3,5-all three tillage, 2,4-bis(trismethyl)-6 -(1,3-benzodioxolan-5(yl)-1,3,5-all three tillage, dibenzophenone, benzoquinone benzoic acid, 1-(4-phenylthiophenyl) Butane-1,2-dione-2-indole-0-stupid 152180.doc -8 - 201132663 Formate, 1-(4-methylthiophenyl)butanedione_2_肟_〇_ Acetate, 1-(4-methylthiophenyl)butanyl ketone ketone, acetate, 2-((ethoxylated imidomethyl) sulfonium p--9-class, etc. The thermosetting resin (G) is preferably a resin having a cyclic ether, particularly an epoxy resin, which is generally used as a resin which does not exhibit reactivity under an active energy ray. The reason is that if the carboxyl group derived from the urethane resin (A) remains after being reacted and hardened by the active energy ray, the result is The cured product is inferior in water resistance or hydrolyzability. Therefore, it is preferred to further carboxylic acid esterify the remaining carboxyl group by using an epoxy resin to form a strong crosslinked structure. As a coloring agent (H) ' Examples include organic pigments such as phthalocyanine, azo, and quinacridone, and inorganic pigments such as carbon black and titanium oxide. A diluent can be used in the production. Examples of the organic solvent usable as the diluent include, for example, Ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; petroleum solvents such as petroleum ether and petroleum brain; An ester solvent such as ethyl ester, butyl acetate, cellosolve acetamidine S, carbitol acetate or propylene glycol monomethyl ether acetate. These may be used singly or in combination of two or more. The dry film of the present invention is a material which is formed by temporarily applying a photosensitive resin composition of the present invention to a release substrate and then laminating it, and bonding the substrate to the original target substrate to form a film. In the case of dry film formation, a knife coater, a blade coater, a lip coater, a bar coater, a squeeze coater, a reverse coater, a transfer roll coater, A gravure coater, a spray coater, or the like is obtained by applying a photosensitive resin composition of the present invention to a support (carrier film) to a uniform thickness, and drying it. membrane. The coating film thickness is not particularly limited, and is usually appropriately selected within the range of 10 to 150 μm, preferably 20 to 6 μm, after coating. As the carrier film, a plastic film can be used, and examples thereof include a polyacetate film such as polyethylene terephthalate, a polyimide film, a polyimide film, a polypropylene film, and a polystyrene film. After the film formation on the carrier film, in order to further prevent dust from adhering to the surface of the film, a cover film which is detachable from the film surface area layer is preferable. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film or the like can be used. When the cover film is peeled off, the adhesion between the film and the cover film is smaller than the adhesion between the film and the support. The photosensitive resin composition of the present invention is diluted as necessary, adjusted to a viscosity suitable for the coating method, and then subjected to screen printing, curtain coating, spray coating, or the like on a printed wiring board formed by a circuit. The organic solvent contained in the composition is volatilized and dried by a method such as a roll coating method at a temperature of, for example, about 60 to 100 ec, whereby a non-adhesive coating film can be formed. When the photosensitive resin composition of the present invention is in the form of a dry film, after laminating on a printed wiring board formed by a circuit, the same state as that of the non-adhered coating film is formed without peeling off the support. Then, 'the active energy line such as laser light is directly exposed to the pattern, or exposed by a patterned mask, and the unexposed portion is developed by a rare aqueous solution to form a resist pattern (for dry film, after exposure) The support is peeled off for development). 152180.doc -10- 201132663 Further heat-hardening or heat-hardening after irradiation with active energy rays, thereby obtaining electrical insulation, adhesion, solder heat resistance, chemical resistance, electroless gold plating, and flexibility Excellent hardened film. The heat curing temperature after development is preferably about 14 〇 24 24 ° c. In this step, the carboxyl group of the urethane resin (A) of the present invention reacts with the thermosetting dendritic (G) having a cyclic ether contained in the photosensitive resin composition for a printed wiring board. A cured coating film excellent in heat resistance, chemical resistance, moisture absorption, adhesion, and electrical properties can be formed. Examples of the substrate of the printed wiring board include paper phenol resin, paper _ epoxy resin, glass cloth - epoxy resin, glass ray polyimide, glass cloth / non-woven fabric - epoxy resin, glass cloth / paper - Copper foil laminates, polyimide films, PET films, glass substrates, all grades (FR_4, etc.) of composite materials such as epoxy resin, synthetic fiber _ epoxy resin, fluororesin-polyethylene-cyanate ester, etc. Ceramic substrate, wafer substrate, etc. In consideration of the characteristics of the photosensitive resin composition of the present invention, it can be said that the substrate 'is more flexible. [Examples] Hereinafter, the present invention will be described in more detail by way of examples, but the invention should not be construed as limited. Further, in the examples, % means mass%. Synthesis Example 1 In a flask equipped with a mixing device and a reflux tube, NC-3000 (epoxy equivalent: 255 g/eq.) manufactured by Nippon Chemical Co., Ltd. as an epoxy resin (1) having a biphenyl novolak structure was introduced. 300.0 g' of 84.7 g of acrylic acid as monobasic acid (c), 2,6-di-t-butyl-4-methyl as a thermal polymerization inhibitor
S 152180.doc 201132663 苯紛1.8 g、作為反應觸媒的三苯基膦i.8g、作為反應溶劑 的丙二醇單曱醚乙酸酯（PGMEA)207_2 g，於反應溫度98。〇 下反應直至反應液酸值為1 mgKOH/g以下為止，而獲得含 羥基之環氧羧酸酯化合物（D-1) » 繼而，投入含有所得之含羥基之環氧羧酸酯化合物 (D-1)的反應液335.5 g、作為具有羧基之二醇化合物斤）的 二羥曱基丁酸60.7 g、作為二異氰酸酯化合物（1?)的2,4,4_ 二甲基六亞甲基二異氰酸酯104.1 g、作為反應溶劑的 PGMEA 88.7 g，於反應溫度8(TC下反應，將NCO含量為 0.1 °/〇以下之時刻作為反應之終點，而獲得胺基曱酸酯化合 物（A-1) 〇 合成例2 投入含有合成例1中所得之含羥基之環氧羧酸酯化合物 (D-1)的反應液335.5 g、作為具有羧基之二醇化合物（E)的 二羥甲基丙酸54.9 g、作為二異氰酸酯化合物（F)的2,4 4_ 二甲基六亞甲基二異氰酸酯104.1 g、作為反應溶劑的 PGMEA 85.6 g，於反應溫度8〇°C下反應，將NCO含量為 0.1 %以下之時刻作為反應之終點，而獲得胺基曱酸酯化合 物（A-2) 〇 合成例3 投入含有合成例1中所得之含羥基之環氧羧酸酯化合物 (D-1)的反應液335.5 g、作為具有羧基之二醇化合物（E)的 二羥曱基丁酸60.7 g、作為二異氰酸酯化合物的異佛爾 酮二異氰酸酯100.1 g、作為反應溶劑的PGMEA87.1 g，於 152180.doc •12· 201132663 反應溫度80°C下反應，將NCO含量為〇·ι%以下之時刻作為 反應之終點’而獲得胺基甲酸醋化合物（八_3)。 比較合成例1 於安裝有攪拌裝置、回流管之燒瓶中’投入作為1分子 中具有2個以上環氧基之環氧樹脂的日本化藥製造之 RE-310S(環氧當量184 g/eq.)300.0 g、作為一元酸（C)的丙 烯酸117.5 g、作為熱聚合抑制劑的2,6_二第三丁基_4甲基 本紛1.9 g、作為反應觸媒的三苯基膦1.9 g、作為反應溶劑 的PGMEA 224.8 g ’於反應溫度98。(：下反應直至反應液酸 值為1 mgKOH/g以下為止，而獲得含羥基之環氧羧酸酯化 合物（D-2)。 繼而’投入含有所得之含羥基之環氧羧酸酯化合物 (D-2)的反應液300.0 g、作為具有羧基之二醇化合物（E)的 二羥曱基丁酸64.0 g、作為二異氰酸酯化合物（F)的2,4,4_ 三甲基六亞曱基二異氰酸酯113.4 g、作為反應溶劑的 PGMEA 95.8 g，於反應溫度80〇c下反應，將NCO含量為 0· 1 %以下之時刻作為反應之終點，而獲得胺基甲酸酯化合 物（A-4)。 比較合成例2 於安裝有攪拌裝置 '回流管之燒瓶中，投入作為1分子 中具有2個以上環氧基之環氧樹脂的日本化藥製造之 RE-303S(環氧當量168 g/eq.)300.0 g、作為一元酸（C)的丙 烯酸128.7 g、作為熱聚合抑制劑的2,6_二第三丁基_4_甲基 苯酚2.0 g、作為反應觸媒的三苯基膦2·〇 g、作為反應溶劑 5 152180.doc -13· 201132663 的PGMEA 23 0.9 g，於反應溫度98°C下反應直至反應液酸 值為1 mgKOH/g以下為止，而獲得含羥基之環氧羧酸酯化 合物（D-3)。 繼而，投入含有所得之含羥基之環氧羧酸酯化合物 (D-3)的反應液300.0 g、作為具有羧基之二醇化合物（E)的 二羥甲基丁酸57.7 g、作為二異氰酸酯化合物（F)的2,4,4-三曱基六亞曱基二異氰酸酯111.5 g、作為反應溶劑的 PGMEA 91.1 g，於反應溫度80°C下反應，將NCO含量為 0· 1 %以下之時刻作為反應之終點，而獲得胺基甲酸酯化合 物（A-5) 〇 樹脂物性評價樣品之製作 於合成例1〜3、比較合成例1〜2中所合成之各感光性樹脂 溶液中，混合140°/〇之日本化藥製造之KAYARAD PEG400DA、40%之日本化藥製造之RE-306、3%之汽巴精 化製造之Irgacure 184(光聚合起始劑），而製成樹脂物性評 價用樣品。將該樹脂物性評價用樣品於電解鉻酸處理鋼板 上塗佈成膜厚約200 μηι後，以600 mJ/cm2之光量進行照射 並使其硬化。然後，將硬化膜自基板上取出而於1 50°C下 乾燥1小時。再者，KAYARAD PEG400DA係光硬化性單 體、RE-306係環氧樹脂。 繼而，進行以下試驗，將結果示於表1。 (Tg之測定方法） 將藉由上述方法製作之硬化膜以寬度5 mm切出。然 後，設置於Seiko instruments製造之黏彈性測定裳置 152180.doc -14· 201132663 DMS6100上，於空氣環境中，以頻率10 Hz、升溫速度 2°C /min.測定tan5，將tan5之最大值之溫度作為Tg。 (伸長率、楊氏模量、彈性模數之測定方法） 將硬化膜以寬度10 mm、長度120 mm切出。然後，設置 於Orientec製造之全自動拉伸試驗機TENSILON上，於 20°C下進行測定。 (趣曲量） 於厚度25 μηι之聚醯亞胺膜（DU PONT-TORAY製造， Kapton 100Η)上，將樹脂物性評價用樣品塗佈成厚度25 μιη，以600 mJ/cm2之光量進行照射並使其硬化。然後，與 聚醯亞胺膜一起製成試驗片並切取50 mmx50 mm，於 15 0°C下乾燥1小時而獲得所製作之試驗片。切割後，以硬 化皮膜層為上而於室溫下靜置30分鐘後，測定試驗片之4 角距離水平面的輕曲量，將其平均值作為翹(曲量。 [表1] A-1 A-2 A-3 A-4 A-5 Tg(0C) 62 62 85 59 58 伸長率(％) 11 11 5 8 7 楊氏模量(Mpa) 1133 1190 1415 1090 1105 彈性模數(kgf/mm2) 114 119 141 142 143 翹曲量(mm) 5.1 5.5 10.1 9.9 9.5 根據以上結果可知：本發明之胺基曱酸酯化合物（A-1、 A-2、A-3)與比較例化合物（A-4、A-5)相比，按揚氏模量 相比，彈性模數較低，具有柔軟且強勃之膜物性。又，此 種硬化物物性係作為印刷配線基板用感光性樹脂組合物、 特別是作為可撓性基板用而較為重要之膜物性。 5 152180.doc -15- 201132663 實施例（印刷配線基板用感光性樹脂組合物） 使用合成例1〜3、比較合成例1〜2中所得之各胺基甲酸醋 化合物，按表2所示之調配比例進行混合’藉由三親磨機 混練後，而獲得感光性樹脂組合物。將其藉由網版印刷法 以乾燥膜厚為15〜25 μιη之厚度之方式塗佈於聚酿亞胺膜 (Kapton 100ΕΝ、DU PONT-TORAY製造）上’藉由 80°C 之 熱風乾燥機將塗膜乾燥30分鐘。繼而，使用紫外線曝光裝 置（ORC MANUFACTURING(股）、型號 HMW-680GW)，通 過描畫了電路圖案之遮罩或用以估計感度之Kodak製造之 階段式曝光表No. 2，照射500 mJ/cm2之紫外線。然後，以 1%碳酸鈉水溶液進行喷霧顯影而去除紫外線未照射部之 樹脂。進行水洗乾燥後，將印刷基板於150°C之熱風乾燥 器中進行60分鐘加熱硬化而獲得硬化膜。 [表2] 感光性樹脂組合物之組成 組合物1 組合物2 組合物3 組合物4 樹脂溶液 A-1 A-2 52 *52~~ 〇 nyj 〇 A-3 ^2_ ~52— A-4 A-5 52 — 光聚合起始劑 Irgacure 907 4 1 4 4 4 DETX-S 0.4 "〇4 反應性交聯劑 DPEA-12 4.4 4.4 4.4 4.4 4.4 硬化成分 RE-306 17.5 17.5 17.5 17.5 17.5 熱硬化觸媒 三聚氰胺 1 1 1 1 ~~ 1 填料等 硫酸鋇 15 15 15 15 15 献普藍 0.5 ^05 0.5 0.5 0 5 添加劑 KS-66 0.4 0.4 0.4 3 0.4 τ~~~-- 0.4 3 稀釋劑 DPM 3 1 132180.doc • 16. 201132663S 152180.doc 201132663 Benzene 1.8 g, triphenylphosphine i. 8 g as a reaction catalyst, propylene glycol monoterpene ether acetate (PGMEA) 207_2 g as a reaction solvent, at a reaction temperature of 98. The reaction is carried out until the acid value of the reaction liquid is 1 mgKOH/g or less to obtain a hydroxyl group-containing epoxy carboxylate compound (D-1). Then, the obtained hydroxyl group-containing epoxy carboxylate compound (D) is introduced. -1) a reaction liquid of 335.5 g, 60.7 g of dihydroxymercaptobutyric acid as a diol compound having a carboxyl group, and 2,4,4-dimethylhexamethylene 2 as a diisocyanate compound (1?) 104.1 g of isocyanate and 88.7 g of PGMEA as a reaction solvent were reacted at a reaction temperature of 8 (TC, and the NCO content was 0.1 °/〇 or less as the end point of the reaction to obtain an amino phthalate compound (A-1). Synthesis Example 2 335.5 g of a reaction liquid containing the hydroxyl group-containing epoxy carboxylate compound (D-1) obtained in Synthesis Example 1 and dimethylolpropionic acid 54.9 as a diol compound (E) having a carboxyl group were charged. g, 104.1 g of 2,4 4 -dimethylhexamethylene diisocyanate as the diisocyanate compound (F), 85.6 g of PGMEA as a reaction solvent, reacted at a reaction temperature of 8 ° C, and the NCO content was 0.1%. The following time is taken as the end point of the reaction to obtain the amino phthalate compound (A-2) Synthesis Example 3 335.5 g of a reaction liquid containing the hydroxyl group-containing epoxy carboxylate compound (D-1) obtained in Synthesis Example 1 and dihydroxymercaptobutyric acid 60.7 as a diol compound (E) having a carboxyl group were charged. g, 100.1 g of isophorone diisocyanate as a diisocyanate compound, and PGMEA 87.1 g as a reaction solvent, reacted at a reaction temperature of 80 ° C at 152180.doc •12·201132663, and the NCO content is 〇·ι% or less. At the time of the reaction, the amino carboxylic acid vinegar compound (eight _3) was obtained. Comparative Synthesis Example 1 In a flask equipped with a stirring device and a reflux tube, 'into a ring having two or more epoxy groups in one molecule Oxygen resin manufactured by Nippon Chemical Co., Ltd., RE-310S (epoxy equivalent 184 g/eq.) 300.0 g, 117.5 g of acrylic acid as monobasic acid (C), 2,6_di-t-butyl group as thermal polymerization inhibitor _4 methyl 1.9 g, 1.9 g of triphenylphosphine as a reaction catalyst, and PGMEA 224.8 g as a reaction solvent at a reaction temperature of 98. (: The reaction is continued until the acid value of the reaction solution is 1 mgKOH/g or less. And a hydroxyl group-containing epoxy carboxylate compound (D-2) is obtained. 300.0 g of a reaction liquid containing the obtained hydroxyl group-containing epoxy carboxylate compound (D-2), 64.0 g of dihydroxymercaptobutyric acid as a diol compound (E) having a carboxyl group, as a diisocyanate compound (F) 113.4 g of 2,4,4_trimethylhexamethylenediisocyanate, 95.8 g of PGMEA as a reaction solvent, reacted at a reaction temperature of 80 〇c, and reacted at a time when the NCO content was 0.1% or less. At the end point, a urethane compound (A-4) was obtained. Comparative Synthesis Example 2 In a flask equipped with a stirring device 'return tube, RE-303S (epoxy equivalent 168 g/eq.) manufactured by Nippon Kayman Co., Ltd. having an epoxy resin having two or more epoxy groups in one molecule was charged. 300.0 g, 128.7 g of acrylic acid as a monobasic acid (C), 2.0 g of 2,6-di-tert-butyl-4-methylphenol as a thermal polymerization inhibitor, and triphenylphosphine as a reaction catalyst 〇g, PGMEA 23 0.9 g as a reaction solvent 5 152180.doc -13· 201132663, reacted at a reaction temperature of 98 ° C until the acid value of the reaction liquid is 1 mg KOH / g or less, thereby obtaining a hydroxyl group-containing epoxy carboxylic acid Ester compound (D-3). Then, 300.0 g of a reaction liquid containing the obtained hydroxyl group-containing epoxy carboxylate compound (D-3) and 57.7 g of dimethylolbutyric acid as a diol compound (E) having a carboxyl group were introduced as a diisocyanate compound. 111.5 g of 2,4,4-tridecylhexamethylenediisocyanate of (F), 91.1 g of PGMEA as a reaction solvent, reacted at a reaction temperature of 80 ° C, and the NCO content is 0. 1 % or less. The end point of the reaction was obtained, and the urethane resin (A-5) oxime resin property evaluation sample was prepared and mixed in each of the photosensitive resin solutions synthesized in Synthesis Examples 1 to 3 and Comparative Synthesis Examples 1 to 2, and mixed. KAYARAD PEG400DA manufactured by Nippon Kayaku Co., Ltd., 40% of RE-306 manufactured by Nippon Kayaku Co., Ltd., and Irgacure 184 (photopolymerization initiator) manufactured by Ciba Specialty Chemicals at 140°/〇 Use the sample. This resin property evaluation sample was applied onto an electrolytic chromic acid-treated steel sheet to a thickness of about 200 μm, and then irradiated with a light amount of 600 mJ/cm 2 to be cured. Then, the cured film was taken out from the substrate and dried at 150 ° C for 1 hour. Further, KAYARAD PEG400DA is a photocurable monomer or an RE-306 epoxy resin. Then, the following test was conducted, and the results are shown in Table 1. (Measurement Method of Tg) The cured film produced by the above method was cut out at a width of 5 mm. Then, it was set on the viscoelasticity measuring skirt manufactured by Seiko Instruments, 152180.doc -14·201132663 DMS6100, and the tan5 was measured at a frequency of 10 Hz and a temperature rising rate of 2 ° C /min in an air environment, and the maximum value of tan 5 was determined. The temperature is taken as Tg. (Method for Measuring Elongation, Young's Modulus, and Elastic Modulus) The cured film was cut out to have a width of 10 mm and a length of 120 mm. Then, it was set on a fully automatic tensile tester TENSILON manufactured by Orientec, and measured at 20 °C. (Fun) The sample for evaluation of the physical properties of the resin was applied to a thickness of 25 μm on a polyimide film of a thickness of 25 μm (manufactured by DU PONT-TORAY, Kapton 100®), and irradiated with a light amount of 600 mJ/cm 2 . Make it harden. Then, a test piece was prepared together with a polyimide film and cut into 50 mm x 50 mm, and dried at 150 ° C for 1 hour to obtain a test piece prepared. After the dicing, the film was allowed to stand at room temperature for 30 minutes with the hardened film layer as the upper layer, and then the light amount of the four angles of the test piece from the horizontal plane was measured, and the average value was taken as the warp (volume. [Table 1] A-1 A-2 A-3 A-4 A-5 Tg(0C) 62 62 85 59 58 Elongation (%) 11 11 5 8 7 Young's modulus (Mpa) 1133 1190 1415 1090 1105 Elastic modulus (kgf/mm2 114 119 141 142 143 Warpage amount (mm) 5.1 5.5 10.1 9.9 9.5 Based on the above results, it is understood that the amino phthalate compound (A-1, A-2, A-3) of the present invention and the comparative compound (A) -4, A-5), compared with the Young's modulus, the elastic modulus is low, and it has a soft and strong film property. Moreover, the cured physical property is used as a photosensitive resin combination for a printed wiring board. In particular, it is a film material property which is important as a flexible substrate. 5 152180.doc -15-201132663 Example (Photosensitive resin composition for printed wiring board) Synthesis Examples 1 to 3 and Comparative Synthesis Example 1 were used. The respective amino carboxylic acid vinegar compounds obtained in 2 were mixed according to the mixing ratio shown in Table 2, and the photosensitive resin combination was obtained by kneading by a three-parent mill. It was applied to a poly-imine film (Kapton 100®, manufactured by DU PONT-TORAY) by screen printing in a dry film thickness of 15 to 25 μm by 'hot air drying at 80 ° C. The film was dried for 30 minutes, and then, using an ultraviolet exposure apparatus (ORC MANUFACTURING, model HMW-680GW), a mask of a circuit pattern or a staged exposure meter manufactured by Kodak for estimating sensitivity was used. 2. Ultraviolet rays of 500 mJ/cm2 were irradiated. Then, the resin of the ultraviolet non-irradiated portion was removed by spray development with a 1% sodium carbonate aqueous solution. After washing with water, the printed substrate was dried in a hot air dryer at 150 °C. The cured film was obtained by heat curing in a minute. [Table 2] Composition of photosensitive resin composition Composition 1 Composition 2 Composition 3 Composition 4 Resin solution A-1 A-2 52 *52~~ 〇nyj 〇A-3 ^2_ ~52— A-4 A-5 52 — Photopolymerization initiator Irgacure 907 4 1 4 4 4 DETX-S 0.4 "〇4 Reactive crosslinker DPEA-12 4.4 4.4 4.4 4.4 4.4 Hardening component RE-306 17.5 17.5 17.5 17.5 17.5 Thermal hardening catalyst trimeric Cyanamide 1 1 1 1 ~~ 1 Filler and other barium sulfate 15 15 15 15 15 Zhepulan 0.5 ^05 0.5 0.5 0 5 Additive KS-66 0.4 0.4 0.4 3 0.4 τ~~~-- 0.4 3 Thinner DPM 3 1 132180.doc • 16. 201132663
Irgacure 907 :汽巴精化製造之2-甲基-1-(4-甲硫基苯基）-2-嗎啉基丙烷-1-酮 DETX-S :日本化藥製造之2,4-二曱基-9-氧硫咄喵 DPEA12 :日本化藥製造之多官能丙烯酸酯 RE306 :日本化藥製造之雙酚A系環氧樹脂 三聚氰胺：2,4,6-三胺基-1,3,5-三畊 硫酸鋇：堺化學製造之B30 酞菁藍：大曰精化製造之雷奥諾爾綠（Lionol Green)2YS KS-66 :信越化學製造之KS-66 DPM :協和醱酵化學製造之二丙二醇單甲醚 繼而，對試驗方法進行記載。 感度 感度係對透過階段式曝光表之曝光部，藉由至第幾級之 濃度部分為止會於顯影時殘存來判定。級數（值）較大則根 據曝光表之濃部判定為高感度。（單位：級） 顯影性 曝光後，使用液溫30°C之1 wt%碳酸鈉水溶液以喷霧壓 0.2 MPa進行60秒顯影，目視測定直至去除未曝光部之樹 脂組合物為止之時間。 ◎:未達25秒 〇：25秒以上、未達45秒 X : 45秒以上 黏性 塗佈後，接觸藉由80°C之熱風乾燥機乾燥30分鐘之基 152180.doc 17 201132663 板’藉由塗膜上是否附有接觸之痕跡來判斷 ◎:塗膜上無痕跡 〇：接觸時有黏性 χ:塗膜上附有接觸之痕跡 解像性 通過光罩進行曝光， 寸確認解像性。 糟由所得之1/1 之線與間隙 之線尺 ◎:未達 80 μιη 〇 : 80 μιη以上、未達 15〇 μιη X : 15 0 μιη 以上 [表3]Irgacure 907: 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one DETX-S manufactured by Ciba Specialty Chemicals: 2,4-II manufactured by Nippon Kayaku Mercapto-9-oxopurine DPEA12: Polyfunctional acrylate RE306 manufactured by Nippon Kayaku Co., Ltd.: Bisphenol A epoxy resin manufactured by Nippon Kayaku Co., Ltd. Melamine: 2,4,6-triamino-1,3, 5-Three-plowed barium sulfate: B30 made from 堺Chemical Blue: Lionol Green 2YS KS-66 manufactured by Daewoo Refinery: KS-66 DPM manufactured by Shin-Etsu Chemical Co., Ltd. Dipropylene glycol monomethyl ether was followed by a test method. Sensitivity The sensitivity is determined by the exposure portion that has passed through the stage exposure meter, which remains at the time of development until the concentration portion of the first stage. When the number of stages (value) is large, it is judged to be high sensitivity based on the rich portion of the exposure meter. (Unit: grade) Developability After exposure, development was carried out for 60 seconds at a spray pressure of 0.2 MPa using a 1 wt% sodium carbonate aqueous solution having a liquid temperature of 30 ° C, and the time until the resin composition of the unexposed portion was removed was visually observed. ◎: less than 25 seconds 〇: 25 seconds or more, less than 45 seconds X: 45 seconds or more after viscous coating, contact with a hot air dryer dried at 80 ° C for 30 minutes. 152180.doc 17 201132663 Judging by whether or not there is a trace of contact on the coating film ◎: no trace on the coating film: viscous 接触 when in contact: the trace of the contact on the coating film is exposed by the reticle, and the resolution is confirmed. . The ruler of the line and gap obtained by the 1/1 line ◎: less than 80 μm 〇 : 80 μιη or more, less than 15 〇 μιη X : 15 0 μιη or more [Table 3]
組合物1 組合物2 |,| 組合物3 — 組合物4 感度 7 7 ----- —-—— 6 、、;tL 〇 J 6 顯影性 ◎ ◎ ◎ 〇 X 黏性 〇 ◎ ◎ X X 解像性 「◎ X 〇 〇 X 根據上述表3之結果，特別是組合物丄於感度、顯影性 黏性、解像性方面表現優異之性能，組合物卜3可用作印 刷配線基板用感光性樹脂組合物。 併根據該等表1、表3，藉由使用合成例丨〜3之樹脂， 可以說能獲得柔軟且_之焊料抗關組合物。 152180.doc -18·Composition 1 Composition 2 |,| Composition 3 - Composition 4 Sensitivity 7 7 -------- 6 , ,; tL 〇J 6 developability ◎ ◎ ◎ 〇X Viscosity 〇 ◎ ◎ XX solution According to the results of Table 3 above, the composition exhibits excellent performance in terms of sensitivity, developability, and resolution, and composition 3 can be used as a photosensitive substrate for printed wiring. The resin composition can be obtained by using the resin of Synthesis Example 丨3 according to Tables 1 and 3, and it can be said that a soft solder resist composition can be obtained. 152180.doc -18·