200836005 (1) 九、發明說明 【發明所屬之技術領域】 本發明係關於一種感光性樹脂之製造方法、以該製造 方法所製得之感光性樹脂、以及感光性樹脂組成物。更詳 細言之，本發明係關於一種在稀鹼中可溶、具高感度、且 熱安定性優良之印刷電路板阻焊劑、高密度多層板相間絕 緣膜、半導體封裝基板用阻焊劑等電子材料領域上使用之 感光性樹脂及感光性樹脂組成物。 【先前技術】 近年來，各種印刷電路板之防焊油墨，由生產面至稀 鹼顯像型之液狀防焊油墨被廣泛地使用著。舉例而言，有 提出含有在側鏈上具有羧基之酚醛清漆型環氧（甲基）丙 烯酸酯之樹脂組成物，現在並已成爲主流（專利文獻1 ) 〇 又近年來，電子機器繼續朝向小型化、輕量化、高功 能化發展。進而爲使半導體能高密度構裝起見，半導體封 裝則朝向小型化、多針化且實用化、並量產化發展。基於 此等之背景，阻焊劑之圖型變得微細化，相對應於此，高 感度化就有必要。此外，隨著半導體之塑膠封裝或近年來 汽車之電子化進展，即使在汽車裝載用途上亦使用電子材 料。在此等之用途上，電子機器被用於較傳統更爲嚴苛之 環境，並被要求能具有高度之長期可信賴性。然而，在傳 統之技術上，對於上述要求並不能完全滿足，而被要求須 -4- 200836005 (2) 加以改善。其中，所採取之一種對應策略即係藉由樹脂之 高感度化以提升硬化塗膜之交聯密度’從而提升其等之可 信賴性。 有提出在具有自由基聚合性不飽合基或羧基之樹脂上 ，使具有1個環氧基及1個以上之自由基聚合性不飽合基 之化合物進行反應，而製得樹脂’該樹脂即具有高感度者 (舉例而言，專利文獻2及3 )。然而，通常此種樹脂雖 具有高感度，惟熱安定性卻顯著地降低之故，因此不只樹 脂本身之貯藏安定性變差，其作爲防焊油墨而對於稀鹼溶 液之顯像時之安定性（即所謂的乾燥管理幅度）亦變差。 舉例而言，在兩面基板上進行印刷時先加以塗佈，而溶劑 乾燥面容易因爲另一面在溶劑乾燥時之熱，而難以在稀鹼 中顯像之問題；或者，在週末進行至溶劑乾燥爲止之步驟 ，而在次週進行顯像時同樣地難以在稀鹼中顯像等操作性 變差之問題。此外，爲獲得更高感度起見，如增加具有1 個環氧基及1個以上之自由基聚合性不飽合基之化合物之 附加量時，結果會造成樹脂中羧基量減少而產生樹脂之酸 價降低，其對於稀鹼之溶解性變差之問題。在該文獻中， 並未記載上述問題。 另有提案藉由在多官能環氧樹脂及不飽和丨價酸之反 應物上，使多價酸酐發生反應，從而再於所生成之羧基上 ，使具有不飽和雙鍵之單環氧化合物及水溶性單環氧化合 物發生反應，而製得感光性樹脂，該樹脂即具有優良之高 感度且熱安定性者（專利文獻4)。然而，業界仍要求要 -5- 200836005 (3) 更高之熱安定性。 專利文獻1 :特公平1-54390號公報 專利文獻2:特許第2900137號公報 專利文獻3:特許第2963069號公報 專利文獻4:特開2001-264977號公報 【發明內容】 發明所欲解決之問題 本發明之目的，係提供一種可以紫外線曝光及稀鹼水 溶液進行顯像，其爲高感度，且具優良之熱安定性及顯像 管理幅度，並顯示有優良塗膜功能而作爲防焊油墨之理想 感光性樹脂之製造方法；以該製造方法所得到之感光性樹 脂；以及含有該感光性樹脂之組成物。 用以解決課題之方法 本發明者們對於前述問題點進行努力檢討之結果，發 現於3價之有機磷化合物及特定之金屬鹽觸媒之存在下， 使不飽和1價酸及具有1級之醇性羥基之飽和1價酸對於 酚醛清漆型多官能環氧樹脂發生反應，所製得之樹脂上， 使多價酸酐再對其發生反應，進而使具有自由基聚合性不 飽和基及環氧基之化合物以及水溶性單環氧化合物發生反 應，可製得感光性樹脂；該感光性樹脂係高感度，且具優 良之熱安定性及顯像管理幅度，並顯示有優良塗膜功能而 作爲防焊油墨之理想感光性樹脂，從而完成本發明。 -6- 200836005 (4) 亦即，本發明係 (1 ) 一種感光性樹脂（A )之製造方法，其特徵爲 包含z 步驟I :於含有（a ) 3價之有機磷化合物、及（b ) 選自環烷酸鉻、環烷酸銷、或辛酸鉻之觸媒化合物1種或 2種以上之其等混合物之存在下， 使（c)酚醛清漆型環氧樹脂、（d)不飽和 1價酸、及（e )具有1級之醇性羥基之飽和丨價酸發生 反應，而製得樹脂（反應物I )， 步驟Π :進而使（f)多價酸酐對於該反應物〗發生 反應，而製得樹脂（反應物II )，以及 步驟III :進而使（g )具有自由基聚合性不飽和基之 單環氧化合物、及（h )水溶性單環氧化合物對於該反應 物II發生反應，而製得感光性樹脂（A )。 (2) 如（1)之製造方法，其中在該步驟I中係進而 含有（i )聚合抑制劑。 (3) 如（1)或（2)之製造方法，其中該（a) 3價 之有機磷化合物係三苯基膦，且在該步驟I中係以吹入空 氣使其發生反應。 (4 )如（1 )〜（3 )中任一者之感光性樹脂之製造 方法，其中相對於該感光性樹脂（A ) 1 〇〇質量份’該（a )3價之有機磷化合物之使用量係0.03〜0.33質量份，且 該（b)觸媒化合物之使用量係0.1〜1·〇質量份。 (5 ) —種感光性樹脂（A )，其特徵係以如（1 ) 200836005 (5) (4)中任一者之製造方法所製造者 (6 ) —種感光性樹脂組成物，其特徵係含有如（5 ) 之（A)感光性樹脂、（B)環氧樹脂、（C)光聚合起始 劑、以及（D )反應性稀釋劑。 發明之效果 含有以本發明之製造方法製得之感光性樹脂之感光性 樹脂組成物，其可以紫外線曝光及稀鹼水溶液進行顯像， 其爲高感度，且具優良之熱安定性及顯像管理幅度，並顯 示有優良塗膜功能而適合作爲防焊油墨。 實施發明之最佳型態 以下，茲詳細說明本發明。 本發明之反應物I所使用之（a ) 3價之有機磷化合物 ，可使用習知者。具體而言，有三苯基膦、三丁基膦、三 乙基膦、三一 〇—甲苯醯基膦、三一 m —甲苯醯基膦、三 一 p-甲苯醯基膦、三（p-甲氧基苯基）膦等。其中，一 般基於優良之容易獲得性、經濟性、甚至於後述所謂之觸 摸乾燥性等觀點，係以三苯基膦爲較佳。其等可1種或2 種以上組合使用。 與前述（a ) 3價之有機磷化合物倂用者，可使用選 自環烷酸鉻、辛酸鉻、環烷酸鉻、或辛酸錐之（b )觸媒 化合物。 一般而言，本發明之感光性樹脂之物性，係在合成時 -8- 200836005 (6) 使用之觸媒影響大，即所謂乾燥管理幅度有受到觸媒影響 之傾向。再者，使用不同觸媒時，其特性爲二者之較差物 性容易出現。 (a ) 3價之有機磷化合物，在溶劑乾燥後之乾燥塗 膜之沾黏性（所謂觸摸乾燥性）優良惟熱安定性有略爲惡 化之傾向。在反應中有一部分會熱氧化而成爲不活性之5 價磷化合物。爲得到充分熱安定性起見，如減少3價之有 機磷化合物之使用量，或在充分熱氧化前進行反應時，其 結果會造成反應時間非常長之傾向，並不具經濟性。另一 方面，如使用上述（b )觸媒化合物作爲觸媒時，雖可製 得熱安定性非常優良之感光性樹脂，惟卻有觸摸乾燥性變 差之傾向。如將此作爲防焊油墨使用時，在紫外線曝光時 所使用之圖型薄膜有容易黏貼之傾向，容易造成作業性上 之問題。 通常，如倂用具有不同特性之觸媒時，會有二者之缺 點皆發生之傾向，惟如倂用本發明之（a ) 3價之有機磷 化合物及上述（b )觸媒化合物時，卻與預期相反地，可 獲得同時發揮二者優點即優良之熱安定性及觸摸乾燥性之 結果。 此等反應觸媒之使用量，只要能發揮本發明之效果者 即可，並無特別之限制，惟較佳係相對於感光性樹脂1 〇 〇 質量份，爲（a) 3價之有機磷化合物係〇.〇3〜0.33質量 份，（b )觸媒化合物係0 · 1〜1 · 0質量份。（a ) 3價之有 機磷化合物之使用量如較〇· 〇3重量份爲少時，其作爲反 -9- 200836005 (7) 應觸媒之使用效果變低，又如超過〇 . 3 3重量份時，有熱 安定性降低之傾向。另一方面，（b )觸媒化合物之使用 量如較〇. 1質量份爲少時，其作爲反應觸媒之使用效果會 降低，又如超過1 . 〇質量份時，要達到效果之使用量就會 不經濟。 本發明之步驟I中所使用之（c )酚醛清漆型環氧樹 月旨，例如有苯酚酚醛清漆型、甲酚酚醛清漆型、雙酚A 酚醛清漆型、二環戊二烯-苯酚酚醛清漆型、萘酚酚醛清 漆型、芳烷變性苯酚酚醛清漆型、烷基變性苯酚酚醛清漆 型等。其等中，又以使用甲酚酚醛清漆型環氧樹脂及苯酚 酚醛清漆型環氧樹脂爲較佳。（c)酚醛清漆型環氧樹脂 可以1種單獨使用或者2種以上組合使用。該酚醛清漆型 環氧樹脂之分子量，只要能發揮本發明之效果者即可，並 無特別之限制，惟較佳係8 0 0〜1 0 0 0 0。 (d )不飽和1價酸，係具有1個羧基及1個以上之 聚合性不飽和結合基之1價酸，具體而言，例如有（甲基 )丙烯酸、順丁烯酸、桂皮酸、山梨酸、丙烯酸二聚物、 2-羥基乙基（甲基）丙烯酸酯之無水琥珀酸附加物等。 爲得到更高活性能量光硬化性起見，係以使用丙烯酸、2 一經基乙基丙烯酸酯之無水號拍酸附加物爲較佳。（d ) 不飽和1價酸，亦可2種以上倂用。 (e )具有1級之醇性羥基之飽和1價酸，係不具有 聚合性之不飽合基之1價酸。具體而言，有乙醇酸、羥基 丙酸、甘油酸、二羥甲基丙酸、二羥甲基丁酸等具有1個 -10- 200836005 (8) 以上1級之醇性羥基之飽和1價酸。其等中，較佳係使用 乙醇酸、二羥甲基丙酸、二羥甲基丁酸。此等可以1種單 獨使用，亦可2種以上倂用。 如使用具有1級之醇性羥基之飽和1價酸時，一般相 較於以環氧基及1價酸之反應所生之2級羥基而言，其與 步驟II之多價酸酐之反應性高，且附加所生之羧基之運 動性高之故，其鹼溶解性獲得提升。因此，如與特公平 1 -543 90號公報所示之在側鏈上具有羧基之酚醛清漆型（ 甲基）丙烯酸酯相較，可在低酸價而賦予同樣之鹼溶解性 。因此，在本發明之步驟III進行反應之具有自由基聚合 性不飽和基之單環氧化合物，其附加量可增加之故，從而 感光性樹脂（A )就可達到更高之感度。 本發明之反應物II，係進而使（f )多價酸酐對於步 驟I所生之反應物I之羥基發生反應而製得。此種多價酸 酐，例如有馬來酸酐、琥珀酸酐、衣康酸酐、苯二酸酐、 四氫苯二酸酐、六氫苯二酸酐、甲橋四氫苯二酸酐、甲基 四氫苯二酸酐等之2價酸酐、三苯六酸酐、焦苯六酸酐、 二苯甲酮四羧酸酐、聯苯基四羧酸酐等之多價酸酐，其中 並以使用四氫苯二酸酐、琥珀酸酐、六氫苯二酸酐爲較佳 〇 本發明之步驟III，係進而使（g )具有自由基聚合性 不飽和基之單環氧化合物、及（h )水溶性單環氧化合物 對於該反應物II發生反應。（g)具有自由基聚合性不飽 和基之單環氧化合物，可使用習知者，例如環氧丙基甲基 -11 - 200836005 (9) 丙烯酸酯、環氧丙基丙烯酸酯、烯丙基環氧丙醚、苯乙烯 - P-環氧丙醚、具有脂環式環氧基之（甲基）丙烯酸酯 (商品名稱：「賽克洛馬」（登錄商標）A200、M100( dai cel化學工業（股）製））等。其中，係以使用環氧丙 基（甲基）丙烯酸酯爲較佳。另一方面，（h)水溶性單 環氧化合物，係下述一般式所示之化合物（η = 4〜6，例 如商品名稱：「戴納克爾」（登錄商標）ΕΧ-145 ( nagasechemtex (股）製）)°[Technical Field] The present invention relates to a method for producing a photosensitive resin, a photosensitive resin obtained by the production method, and a photosensitive resin composition. More specifically, the present invention relates to a printed circuit board solder resist, a high-density multilayer inter-phase insulating film, a solder resist for a semiconductor package substrate, and the like which are soluble in a dilute alkali, have high sensitivity, and have excellent thermal stability. A photosensitive resin and a photosensitive resin composition used in the field. [Prior Art] In recent years, solder resist inks of various printed circuit boards have been widely used from a production surface to a liquid solder resist ink of a thin alkali developing type. For example, there has been proposed a resin composition containing a novolac type epoxy (meth) acrylate having a carboxyl group in a side chain, and has now become a mainstream (Patent Document 1). In recent years, electronic devices have continued to be small. Development, lightweight, and high functional development. Further, in order to make the semiconductor high-density structure, the semiconductor package has been developed in a compact and multi-needle manner, and has been put into practical use and mass production. Based on these backgrounds, the pattern of the solder resist is made finer, and correspondingly, high sensitivity is necessary. In addition, with the plastic packaging of semiconductors or the advancement of electronic electronics in automobiles, electronic materials have been used even in automotive loading applications. In these applications, electronic machines are used in more demanding environments and are required to have a high degree of long-term reliability. However, in the conventional technology, the above requirements are not fully satisfied, and are required to be improved -4- 200836005 (2). Among them, a corresponding strategy adopted is to increase the crosslinking density of the cured coating film by the high sensitivity of the resin, thereby improving the reliability thereof. It is proposed to react a compound having one epoxy group and one or more radical polymerizable unsaturated groups on a resin having a radical polymerizable unsaturated group or a carboxyl group to obtain a resin. That is, those having high sensitivity (for example, Patent Documents 2 and 3). However, although such a resin generally has high sensitivity, but the thermal stability is remarkably lowered, not only the storage stability of the resin itself is deteriorated, but also the stability of the development of a dilute alkali solution as a solder resist ink. (the so-called dry management range) also deteriorated. For example, when printing on a double-sided substrate, the coating is first applied, and the solvent-dried surface is liable to be difficult to develop in a dilute alkali because the other side is hot when the solvent is dried; or, at the weekend, to solvent drying. In the case of the next step, it is difficult to develop the image in the next week, and it is difficult to develop the image in a thin alkali. Further, in order to obtain higher sensitivity, for example, when an additional amount of a compound having one epoxy group and one or more radical polymerizable unsaturated groups is added, the result is that the amount of carboxyl groups in the resin is decreased to produce a resin. The acid value is lowered, and its solubility to a dilute alkali is deteriorated. In this document, the above problem is not described. It is also proposed to make a monovalent epoxy compound having an unsaturated double bond and reacting a polyvalent acid anhydride on a reaction product of a polyfunctional epoxy resin and an unsaturated hydrazine acid to further form a monovalent epoxy compound having an unsaturated double bond. The water-soluble monoepoxy compound reacts to obtain a photosensitive resin which is excellent in high sensitivity and heat stability (Patent Document 4). However, the industry still requires -5- 200836005 (3) higher thermal stability. Patent Document 1: Japanese Unexamined Patent Application Publication No. Publication No. Publication No. Publication No. Publication No. Publication No. Publication No. Publication No. Publication No. Publication No. Publication No. Publication No. Publication No. Publication No. The object of the present invention is to provide an ultraviolet light exposure and a dilute alkali aqueous solution for development, which is high in sensitivity, has excellent thermal stability and development management range, and exhibits excellent coating function as a solder resist ink. A method for producing an ideal photosensitive resin; a photosensitive resin obtained by the production method; and a composition containing the photosensitive resin. Means for Solving the Problem As a result of an effort to review the above problems, the present inventors have found that in the presence of a trivalent organic phosphorus compound and a specific metal salt catalyst, an unsaturated monovalent acid and a level 1 are obtained. The saturated monovalent acid of the alcoholic hydroxyl group reacts with the novolac type polyfunctional epoxy resin, and the polyvalent acid anhydride is further reacted on the obtained resin to further have a radical polymerizable unsaturated group and an epoxy group. A photosensitive resin can be obtained by reacting a compound with a water-soluble monoepoxy compound; the photosensitive resin is high in sensitivity, has excellent thermal stability and development management, and exhibits excellent coating function as An ideal photosensitive resin for solder resist ink, thereby completing the present invention. -6- 200836005 (4) The present invention relates to a method for producing a photosensitive resin (A), which comprises z step I: containing (a) a trivalent organic phosphorus compound, and (b) (c) a novolac type epoxy resin, (d) unsaturated in the presence of one or a mixture of two or more kinds of a catalyst compound selected from the group consisting of chromium naphthenate, naphthenic acid, or chromium octoate A monovalent acid, and (e) a saturated valence acid having an alcoholic hydroxyl group of a first order is reacted to obtain a resin (reactant I), step Π: further causing (f) a polyvalent acid anhydride to occur for the reactant Reacting to obtain a resin (Reactant II), and Step III: further (g) a monoepoxy compound having a radical polymerizable unsaturated group, and (h) a water-soluble monoepoxy compound for the reactant II The reaction was carried out to obtain a photosensitive resin (A). (2) The production method according to (1), wherein in the step I, the (i) polymerization inhibitor is further contained. (3) The production method according to (1) or (2), wherein the (a) trivalent organic phosphorus compound is triphenylphosphine, and in the step I, a reaction is carried out by blowing air. (4) The method for producing a photosensitive resin according to any one of (1) to (3), wherein the (a) trivalent organic phosphorus compound is relative to the photosensitive resin (A) The amount used is 0.03 to 0.33 parts by mass, and the amount of the (b) catalyst compound used is 0.1 to 1 part by mass. (5) A photosensitive resin (A) characterized by being produced by the method of any one of (1) 200836005 (5) (4), wherein the photosensitive resin composition is characterized by The photosensitive resin (A), (B) epoxy resin, (C) photopolymerization initiator, and (D) reactive diluent are contained in (5). Advantageous Effects of Invention The photosensitive resin composition containing the photosensitive resin obtained by the production method of the present invention can be developed by ultraviolet exposure and a dilute aqueous alkali solution, which is high in sensitivity and has excellent thermal stability and development. It manages the amplitude and shows excellent film function and is suitable as a solder resist ink. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The (a) trivalent organic phosphorus compound used in the reactant I of the present invention can be used by a conventional one. Specifically, there are triphenylphosphine, tributylphosphine, triethylphosphine, trimethylsulfonyl-tolylphosphine, trimethyl-tolylphosphine, tris-p-tolylphosphine, and tris(p- Methoxyphenyl) phosphine and the like. Among them, triphenylphosphine is preferred because of its excellent availability, economy, and even the so-called touch drying property described later. These may be used in combination of one type or two or more types. As the above-mentioned (a) trivalent organic phosphorus compound, a (b) catalyst compound selected from chromium naphthenate, chromium octoate, chromium naphthenate or octanoic acid cone can be used. In general, the physical properties of the photosensitive resin of the present invention are largely affected by the catalyst used in the synthesis at -8-200836005 (6), that is, the so-called dry management range tends to be affected by the catalyst. Furthermore, when a different catalyst is used, its characteristic is that the poor physical properties of the two are likely to occur. (a) The trivalent organic phosphorus compound is excellent in the tackiness (so-called touch drying property) of the dried coating film after the solvent is dried, but the thermal stability tends to be slightly deteriorated. A part of the reaction is thermally oxidized to become an inactive 5-valent phosphorus compound. For the purpose of obtaining sufficient thermal stability, such as reducing the amount of organic phosphorus compound used in the trivalent state or performing the reaction before sufficient thermal oxidation, the result is a tendency to have a very long reaction time and is not economical. On the other hand, when the above-mentioned (b) catalyst compound is used as a catalyst, a photosensitive resin having excellent thermal stability can be obtained, but the touch drying property tends to be deteriorated. When this is used as a solder resist ink, the pattern film used in the ultraviolet exposure tends to be easily attached, which tends to cause workability problems. In general, if a catalyst having different characteristics is used, there is a tendency that both of them have a disadvantage, but when the (a) trivalent organic phosphorus compound of the present invention and the above (b) catalyst compound are used, Contrary to expectations, it is possible to obtain both the advantages of both, namely, excellent thermal stability and dry touch. The amount of the reaction catalyst used is not particularly limited as long as the effect of the present invention can be exerted, but is preferably (a) trivalent organic phosphorus relative to 1 part by mass of the photosensitive resin. The compound is 〜. 3 to 0.33 parts by mass, and (b) the catalyst compound is 0 · 1 to 1 · 0 parts by mass. (a) When the amount of the trivalent organic phosphorus compound is less than 〇·〇3 parts by weight, it is used as anti--9-200836005 (7) The effect of the catalyst is low, and if it exceeds 〇. 3 3 When the parts are parts by weight, there is a tendency that the heat stability is lowered. On the other hand, (b) when the amount of the catalyst compound used is less than 1 part by mass, the use effect as a reaction catalyst may be lowered, and if it exceeds 1. 〇 by mass, the effect is to be achieved. The amount will not be economical. (c) a novolac type epoxy resin used in the step I of the present invention, for example, a phenol novolak type, a cresol novolak type, a bisphenol A novolak type, a dicyclopentadiene-phenol novolac Type, naphthol novolak type, aralkyl modified phenol novolak type, alkyl modified phenol novolak type, and the like. Among them, a cresol novolac type epoxy resin and a phenol novolak type epoxy resin are preferably used. (c) The novolac type epoxy resin may be used alone or in combination of two or more. The molecular weight of the novolac type epoxy resin is not particularly limited as long as it can exert the effects of the present invention, but is preferably 800 to 1 0 0 0 0. (d) an unsaturated monovalent acid, which is a monovalent acid having one carboxyl group and one or more polymerizable unsaturated bonding groups, and specific examples thereof include (meth)acrylic acid, methacrylic acid, and cinnamic acid. Sorbic acid, acrylic acid dimer, 2-hydroxyethyl (meth) acrylate anhydrous succinic acid addenda, and the like. For the purpose of obtaining higher activity energy photohardenability, it is preferred to use an anhydrous acepicric acid addendum of acrylic acid and 2-monoethyl acrylate. (d) Unsaturated monovalent acid, or two or more types. (e) A saturated monovalent acid having an alcoholic hydroxyl group of the first order, which is a monovalent acid having no polymerizable unsaturated group. Specifically, there are saturated monovalent valences of alcoholic hydroxyl groups having one -10-200836005 (8) or higher, such as glycolic acid, hydroxypropionic acid, glyceric acid, dimethylolpropionic acid, or dimethylolbutanoic acid. acid. Among them, glycolic acid, dimethylolpropionic acid, and dimethylolbutanoic acid are preferably used. These can be used alone or in combination of two or more. When a saturated monovalent acid having a 1st alcoholic hydroxyl group is used, its reactivity with the polyvalent acid anhydride of the step II is generally higher than that of the secondary hydroxyl group produced by the reaction of an epoxy group and a monovalent acid. It is high, and the alkali solubility of the added carboxyl group is increased, and the alkali solubility is improved. Therefore, the same alkali solubility can be imparted at a low acid value as compared with the novolak type (meth) acrylate having a carboxyl group in the side chain as shown in Japanese Patent Publication No. Hei. 1-54390. Therefore, the addition amount of the monoepoxy compound having a radical polymerizable unsaturated group which is reacted in the step III of the present invention can be increased, so that the photosensitive resin (A) can achieve higher sensitivity. The reactant II of the present invention is further obtained by reacting (f) a polyvalent acid anhydride with the hydroxyl group of the reactant I produced in the step I. Such polyvalent acid anhydrides include, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alpha-tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and the like. a polyvalent acid anhydride such as divalent anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, biphenyltetracarboxylic anhydride, or the like, wherein tetrahydrophthalic anhydride, succinic anhydride, and hexahydrogen are used. The phthalic anhydride is preferably the step III of the present invention, which further causes (g) a monoepoxy compound having a radical polymerizable unsaturated group, and (h) a water-soluble monoepoxy compound to react with the reactant II. . (g) a monoepoxy compound having a radical polymerizable unsaturated group, which can be used, for example, a glycidylmethyl-11 - 200836005 (9) acrylate, a epoxypropyl acrylate, an allyl group Glycidyl ether, styrene-P-glycidyl ether, (meth) acrylate with alicyclic epoxy group (trade name: "Secrock" (registered trademark) A200, M100 (dai cel chemistry Industrial (share) system)) and so on. Among them, it is preferred to use a glycidyl (meth) acrylate. On the other hand, (h) a water-soluble monoepoxy compound is a compound represented by the following general formula (η = 4 to 6, for example, trade name: "Danaker" (registered trademark) ΕΧ-145 (nagasechemtex (share) ))))°
具有自由基聚合性不飽和基之單環氧化合物，由於位 於感光性樹脂（A )骨架之最外部之故，自由基聚合性不 飽和基之運動性高而可以達到高感度化。另一方面，水溶 性單環氧化合物亦同樣地位於樹脂骨架之最外部之故，具 有前述自由基聚合性不飽和基之單環氧化合物之不飽合基 運動性會被適度地抑制，從而使貯藏時或作業步驟時之安 定性提升，且對於在樹脂骨架上具有適度親水性之鹼性溶 液之溶解性亦可獲得提升。 其次，說明感光性樹脂（A )之製造方法。爲在步驟 I合成反應物I之故，係將（d )不飽和1價酸及（e )具 有1級之醇性羥基之飽和1價酸，以習知之方法對於（c -12- 200836005 (10) )酚醛清漆型環氧樹脂發生反應。環氧樹脂如係液狀時’ 雖可以無溶劑使其發生反應，惟如（c )酚醛清漆型環氧 樹脂爲固態時，係以在溶劑中發生反應者爲較佳。 所使用之溶劑可使用習知者，舉例而言，有甲乙酮、 環己酮之酮類、甲苯、二甲苯等之芳香族烴類、二丙二醇 二甲醚等之乙二醇醚類、乙酸乙酯、丁基溶纖劑乙酸酯、 卡必醇乙酸酯、乙基卡必醇乙酸酯、丁基卡必醇乙酸酯、 二丙二醇單甲醚乙酸酯等之酯類、石油酯、石油腦、溶劑 石腦油等之石油系溶劑等。 又在步驟I之反應溫度，較佳係60°C〜150°C。反應 時間較佳爲5〜20小時。 相對於（c)酚醛清漆型環氧樹脂之環氧基1莫爾， (d )不飽和1價酸及（e )具有1級之醇性羥基之飽和1 價酸之總量，係以添加至〇 . 9〜1 . 1莫爾爲較佳。 此外，具有1級之醇性羥基之飽和1價酸之使用量， 如以不飽和1價酸及具有1級之醇性羥基之飽和1價酸爲 1莫爾計，係以〇.〇5〜0.4莫爾爲較佳。具有1級之醇性 羥基之飽和1價酸之使用量，如較0.05莫爾爲少時，其 使用之效果會降低，又如較〇. 4莫爾爲多時，衍生自不飽 和1價酸之聚合性不飽合基之濃度會降低，即使附加後述 步驟II之自由基聚合性不飽合基與具有環氧基之化合物 ，亦難以使其高感度化，從而可能無法充分達成本發明之 效果。 步驟III，係對於前述步驟II之反應物II之羧基，使 -13- (11) (11)200836005 (g)具有自由基聚合性不飽和基之單環氧化合物及（h) 水溶性單環氧化合物發生反應而製得。反應觸媒，可使用 與在反應物I之合成時使用者相同’在合成反應物Π後 ，可不另外追加觸媒而直接進行步驟111之合成，或另行 追加觸媒亦可。 具有自由基聚合性不飽和基及環氧基之化合物之使用 量，較佳係相對於前述反應物II中之羧基1莫爾，以（g )具有自由基聚合性不飽和基之單環氧化合物及（h)水 溶性單環氧化合物之總量計，係0.15〜0.4莫爾。如較 〇. 1 5爲低時，光感度提升之效果有劣化之傾向，又如在 0.4莫爾以上時，樹脂中之羧基量會變得過少，從而鹼顯 像性有劣化之傾向。另一方面，水溶性單環氧化合物之使 用量，相對於前述反應物II中之羧基1莫爾，係0.01〜 〇 . 1莫爾。如在0 . 〇 1莫爾以下時，無法得到充分之效果； 如添加至0.1莫爾以上時，不只無法獲得配合之效果，前 述具有自由基聚合性不飽和基之單環氧化合物之運動性被 過度地抑制之故，其結果將造成光感度之降低。反應溫度 ，較佳係60°c〜15(TC。反應時間較佳爲0.5〜20小時。 本發明之感光性樹脂組成物，其特徵係進而含有上述 之（A)感光性樹脂、（B)環氧樹脂、（C)光聚合起始 劑、以及（D )反應性稀釋劑。該感光性樹脂組成物，係 作爲鹼顯像型感光性樹脂組成物而使用。 在本發明之鹼顯像型感光性樹脂組成物上使用之（B )環氧樹脂，例如有三環氧丙基異氰尿酸酯或在前述之步 -14- (12) (12)200836005 驟I使用之（c)酚醛清漆型環氧樹脂。此等環氧樹脂可 單獨使用1種或2種以上倂用。再者’爲確保Tg並進而 提升韌性起見，基於異氰尿酸酯變性環氧樹脂之使用或賦 予難燃性之觀點，使用含磷之環氧樹脂等亦爲有效。 前述（B )環氧樹脂，爲提升密接性、耐熱性、耐電 鍍性等作爲阻焊劑之各種特性’可在組成物中配合熱硬化 成分。在製造印刷電路板等時’在以稀鹼水溶液顯像後， 藉由加熱使樹脂硬化，就可賦予電路板更佳之密接性、耐 熱性、耐電鍍性等。 (B )環氧樹脂，可單獨使用1種或2種以上之混合 物倂用。本發明之（B )環氧樹脂之使用量，相對於感光 性樹脂（A ) 1 00質量份，係5〜1 00質量％。如較5質量 %爲少時，難以獲得優良之硬化塗膜特性，又如較1 〇〇質 量％，將有鹼溶解性劣化之傾向。 爲進一步提升前述（B )環氧樹脂之密接性、耐熱性 、耐電鍍性等特性，係以倂用環氧硬化劑爲較佳。此種環 氧硬化劑，例如有咪唑衍生物、苯酚衍生物、二氰二醯胺 、二氰二醯胺衍生物、三聚氰胺、三聚氰胺樹脂、醯肼衍 生物、胺類、酸酐等。上述硬化劑，可單獨使用1種類或 2種以上混合使用。上述硬化劑之使用量，相對於該環氧 樹脂之環氧基1莫爾，係以硬化劑之活性氫量成爲〇 · 5〜 1.2莫爾之比例爲較佳。 本發明之感光性樹脂組成物中使用之（C )光聚合起 始劑，其具體例子有苯偶因類、乙醯苯類、蒽醌類、噻噸 -15- 200836005 (13) 酮類、二苯甲酮類等。舉例而言，苯偶因類有苯偶因、苯 偶因甲醚、苯偶因異丙醚等衍生物；乙醯苯類有乙醯苯、 2,2-二甲氧基一 2-苯基乙醯苯等衍生物；蒽醌類有2 — 甲基蒽醌、2 —氯蒽醌、2 -乙基蒽醌、2 - t 一丁基蒽醌等 衍生物；噻噸酮有噻噸酮、2，4 -二甲基噻噸酮等衍生物 ;二苯甲酮類有二苯甲酮、4 一苯醯一 4’ 一甲基二苯基硫 化物、4,4’ 一二氯二苯甲酮、N，N —二甲基胺基二苯甲酮 等衍生物、2,4,6—三甲基苯醯二苯基膦氧化物等，可單 獨使用或2種類以上組合使用。進而，（C )光聚合起始 劑，亦可倂用三級胺等習知之光增感劑。具體而言，有三 乙醇胺、三丙醇胺、三乙基胺、N，N -二甲基胺基酸安息 香酸乙酯、N，N —二甲基胺基安息香酸異戊酯、戊一 4 一 二甲基胺基苯甲酸酯等。 上述（C)光聚合起始劑，可單獨使用1種類或2種 以上混合使用，或甚至倂用習知之光增感劑而使用。（C )光聚合起始劑之使用比例，相對於（A )感光性樹脂 1〇〇質量份，係0.5〜30質量份。其如在0.5質量份以下 . 時，使用之效果會降低，且導致光感度降低。即使使用 3 G質量份以上，所達到之添加效果亦低。 本發明之感光性樹脂組成物中，使用（D )反應性稀 釋劑。（D )反應性稀釋劑，係基於提升對於活性能量光 線之硬化性，及/或將感光性樹脂組成物作爲防焊油墨使 用時之塗佈性之目的而使用。 此種聚合性不飽和化合物’係以具有活性能量光線硬 -16- (14) (14)200836005 化性之單體類爲較佳，例如有2 -羥基乙基丙烯酸酯、2 一羥基丙基丙烯酸酯、N —吡咯烷酮、N -丙烯醯基嗎啉 、N，N -二甲基丙烯基醯胺、n，N —二乙基丙烯基醯胺、 N，N —二甲基胺基乙基丙烯酸酯、n，N —二甲基胺基丙基 丙烯酸酯、甲氧基聚乙二醇丙烯酸酯、乙氧基聚乙二醇丙 儲酸酯、三聚氰胺丙嫌酸酯、苯氧基乙基丙燒酸酯、苯氧 基丙基丙烯酸酯、乙二醇二丙烯酸酯、二丙二醇二丙烯酸 酯、聚二丙二醇二丙烯酸酯、三羥甲基丙烷三丙烯酸酯、 季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇 六丙烯酸酯、丙三醇二丙烯酸酯、異佛爾酮基丙烯酸酯、 二環戊烯氧基乙基丙烯酸酯及其等所對應之各種甲基丙烯 酸酯。此等聚合性不飽和化合物可單獨1種或2種以上倂 用。 反應性稀釋劑（D )，可使用單獨1種或2種以上之 混合物。其使用量，相對於前述感光性樹脂（A ) 1 0 0質 量份，係10〜200質量份，較佳係20〜150質量份。使用 量如未達1〇質量份時，光感度會變得過低，且黏度變高 其塗佈性可能變差。另一方面，如超過200質量份時，將 感光性樹脂組成物作爲防焊油墨使用時，黏度會變得過低 ，其作爲硬化塗膜之特性將可能不足。 又爲調整塗佈性起見，可與上述（D )反應性稀釋劑 倂用而使用溶劑。此等溶劑，例如有甲乙酮、甲基異丁酮 、環己酮等之酮類、甲苯、二甲苯等之芳香族烴、乙基溶 纖劑、丁基溶纖劑、卡必醇、丁基卡必醇等之卡必醇類、 -17- (15) (15)200836005 乙酸乙酯、乙酸丁酯、溶纖劑乙酸酯、丁基溶纖劑乙酸酯 、乙基卡必醇乙酸酯等。此等溶劑可以單獨1種或2種以 上倂用。 此外，如將本發明之感光性樹脂組成物作爲液狀防焊 油墨使用時，亦可進而根據需要，而使用二氧化砂、碳酸 鈣、硫酸鋇、黏土、滑石等無機塡充劑、酞菁綠、酞菁藍 、氧化鈦、碳黑等之着色顏料、消泡劑、整平劑等各種添 加劑外，尙可使用對苯二酚、間苯二酚、鄰苯二酚、焦掊 酚、對苯二酚單甲醚、t 一丁基鄰苯二酚、吩噻嗪、等之 聚合抑制劑。 本發明之感光性樹脂組成物，可將前述之各配合成分 ，較佳係依前述之比例加以配合，再以三輥輾機等使其均 一混合而製得。此外，本發明之感光性樹脂組成物係液狀 組成物，舉例而言，可如下所示使其硬化，而製得硬化物 。亦即，在印刷電路板上以網版印刷法、噴墨印刷法、滾 輥塗佈法、靜電塗裝法、簾幕塗佈法等方法，而以1 0〜 1 6 0 // m之膜厚度塗佈本發明之組成物。其後，將該塗膜 以60〜110°C進行乾燥。將負軟片直接接觸於該塗膜上， 或在未接觸之情況下放置於塗膜上後，照射紫外線而使組 成物曝光。將未曝光部分以稀鹼水溶液溶解除去進行顯像 後’進而爲提升各種物性之故，再以紫外線照射及/或加 熱（例如以1 〇 〇〜2 0 0 °c，0 · 5〜1 · 0小時）進行充分之硬 化，而製得硬化塗膜。 -18- 200836005 (16) 【實施方式】 實施發明之最佳型態 以下茲舉出實施例、比較例詳細地說明本發明，爲各 例中之「份」及「％」，除有特別限制外皆係質量基準。 又本發明並不受這些實施例之任何限制。 合成例1 (樹脂1之合成例） 在具有攪拌機、氣體導入管、還流管之燒瓶內，裝入 乙基卡必醇乙酸酯92份，於其中使0-甲酚酚醛清漆型 環氧樹脂（商品名稱：「愛普特多」（登錄商標） YDCN704，東都化成株式會社製，環氧當量210) 210份 (1·〇當量）溶解。進而，加入丙烯酸69.84份（0.97莫 爾）、乙醇酸2·16份（0.03莫爾）、聚合抑制劑2,6-二 一 t一丁基—4 —甲氧基苯酚2.17份及三苯基膦0.45份、 環烷酸鉻（金屬含量3 % ) 0 · 8 5份，由液體下部之氣體導 入管吹入空氣，同時加溫至1 3 0 °C繼續反應1 0小時，而 製得酸價0.5 mgKOH/g之反應物（反應物I)。於其上再 加入乙基卡必醇乙酸酯98份、四氫苯二酸酐106.4份（ 0.7莫爾），於120°C進一步反應2小時，製得固態成分 酸價101.1 mgKOH/g之反應物（反應物II)。進而，再 加入環氧丙基甲基丙烯酸酯21.3份（0.15莫爾）、「戴 納克爾」（登錄商標）EX-145 ( nagasechemtex (股）製 ，環氧當量450:苯酚（EO)5環氧丙基醚）13·5份（〇·〇3 莫爾），於120 °C進一步反應3小時，製得固態成分酸價 -19- 200836005 (17) 68.9 mgKOH/g 之樹脂 1。 合成例2 (樹脂2之合成例） 入 型 ) 份 莫 導 而 再 ( 分 再 戴 製 • 03 價 入 在具有攪拌機、氣體導入管、還流管之燒瓶內，裝 乙基卡必醇乙酸酯92份，於其中使〇 —甲酚酚醛清漆 環氧樹脂（商品名稱：「愛普特多」（登錄商標 YDCN704，東都化成株式會社製，環氧當量210 ) 210 (1.0當量）溶解。進而，加入丙烯酸69.84份（0.97 爾）、乙醇酸2.16份（0.03莫爾）、聚合抑制劑2,6-一 t 一 丁基一 4 一甲氧基苯酣2.17份及三苯基膦0.45份 環烷酸鉻（金屬含量6%) 0.85份，由液體下部之氣體 入管吹入空氣，同時加溫至130°C繼續反應10小時， 製得酸價〇·5 mgKOH/g之反應物（反應物I)。於其上 加入乙基卡必醇乙酸酯98份、四氫苯二酸酐106.4份 〇·7莫爾），於12(TC進一步反應2小時，製得固態成 酸價101.1 mgKOH/g之反應物（反應物II )。進而， 加入環氧丙基甲基丙烯酸酯21.3份（0.15莫爾）、「 納克爾」（登錄商標）EX-145 ( nagasechemtex (股） ，環氧當量450:苯酚（EO) 5環氧丙基醚）13.5份（0 莫爾），於120°C進一步反應3小時，製得固態成分酸 68.9 mgKOH/g 之樹脂 2。 合成例3 (樹脂3之合成例） 在具有攪拌機、氣體導入管、還流管之燒瓶內，裝 -20- 200836005 (18) 乙基卡必醇乙酸酯92份，於其中使〇-甲酚酚醛清漆型 環氧樹脂（商品名稱·· 「愛普特多」（登錄商標） YDCN704，東都化成株式會社製，環氧當量210) 210份 (1.0當量）溶解。進而，加入丙烯酸69.84份（〇·97莫 爾）、乙醇酸2.16份（〇·〇3莫爾）、聚合抑制劑2,6 —二 —t — 丁基一 4 一甲氧基苯酚2.17份及三苯基膦〇·45份、 辛酸鉻（金屬含量12%) 〇·85份，由液體下部之氣體導 入管吹入空氣，同時加溫至1 3 0 °C繼續反應1 〇小時，而 製得酸價0.5 mgKOH/g之反應物（反應物I)。於其上再 加入乙基卡必醇乙酸酯98份、四氫苯二酸酐106.4份（ 0.7莫爾），於120°C進一步反應2小時，製得固態成分 酸價101.1 mgKOH/g之反應物（反應物II )。進而，再 加入環氧丙基甲基丙烯酸酯21.3份（0.15莫爾）、「戴 納克爾」（登錄商標）EX-145 ( nagasechemtex (股）製 ，環氧當量450:苯酚（EO)5環氧丙基醚）13.5份（0.03 莫爾），於120°C進一步反應3小時，製得固態成分酸價 68.9 mgKOH/g 之樹脂 3。 合成例4 (樹脂4之合成例） 在具有攪拌機、氣體導入管、還流管之燒瓶內，裝入 乙基卡必醇乙酸酯92份，於其中使〇 -甲酚酚醛清漆型 環氧樹脂（商品名稱：「愛普特多」（登錄商標） YDCN704，東都化成株式會社製，環氧當量210 ) 210份 (1·〇當量）溶解。進而，加入丙烯酸69.84份（0.97莫 -21 - (19) 200836005 導 而 再 ( 分 再 戴 製 .03 價 入 型 ) 份 莫 環 導 而 爾）、乙醇酸2 · 1 6份（〇 · 〇 3莫爾）、聚合抑制劑2，6 — 一 t — 丁基一 4 一甲氧基苯酚2.17份及三苯基膦0.12份 環烷酸鉻（金屬含量3%) 0.85份’由液體下部之氣體 入管吹入空氣，同時加溫至1 3 0 °C繼續反應1 〇小時， 製得酸價0.5 mgKOH/g之反應物（反應物I)。於其上 加入乙基卡必醇乙酸酯9 8份、四氫苯二酸酐1 0 6.4份 0.7莫爾），於120°C進一步反應2小時，製得固態成 酸價101.1 mgKOH/g之反應物（反應物II)。進而， 加入環氧丙基甲基丙烯酸酯21.3份（0.15莫爾）、「 納克爾」（登錄商標）EX-145 ( nagasechemtex (股） ，環氧當量450:苯酚（E 0)5環氧丙基醚）13.5份（0 莫爾），於120 °C進一步反應3小時，製得固態成分酸 68.9 mgKOH/g 之樹脂 4。 合成例5 (樹脂5之合成例） 在具有攪拌機、氣體導入管、還流管之燒瓶內，裝 乙基卡必醇乙酸酯92份，於其中使〇 -甲酚酚醛清漆 環氧樹脂（商品名稱：「愛普特多」（登錄商標 YDCN704，東都化成株式會社製，環氧當量210) 210 (1.0當量）溶解。進而，加入丙烯酸69.84份（0.97 爾）、乙醇酸2 · 1 6份（0 · 03莫爾）、聚合抑制劑2,6 -一 t 一丁基一 4 一甲氧基苯酚2.17份及三苯基膦1.5份、 烷酸鉻（金屬含量12%) 0.85份，由液體下部之氣體 入管吹入空氣，同時加溫至1 3 0 °C繼續反應1 〇小時， -22- (20) (20)200836005 製得酸價〇·5 mgKOH/g之反應物（反應物I )。於其上再 加入乙基卡必醇乙酸酯98份、四氫苯二酸酐106.4份（ 〇 . 7莫爾），於1 2 0 °C進一步反應2小時，製得固態成分 酸價101.1 mgKOH/g之反應物（反應物II)。進而，再 加入環氧丙基甲基丙烯酸酯21.3份（0.15莫爾）、「戴 納克爾」（登錄商標）EX-145 ( nagasechemtex (股）製 ，環氧當量450:苯酚（EO)5環氧丙基醚）13.5份（0.03 莫爾），於120 °C進一步反應3小時，製得固態成分酸價 68.9 mgKOH/g 之樹脂 5。 合成例6 (樹脂6之合成例） 在具有攪拌機、氣體導入管、還流管之燒瓶內，裝入 乙基卡必醇乙酸酯92份，於其中使〇 -甲酚酚醛清漆型 環氧樹脂（商品名稱：「愛普特多」（登錄商標） YDCN704，東都化成株式會社製，環氧當量210 ) 210份 (1.0當量）溶解。進而，加入丙烯酸69.84份（〇·97莫 爾）、乙醇酸2.16份（0·03莫爾）、聚合抑制劑2,6-二 一 t 一丁基一 4 —甲氧基苯酚2.17份及三苯基膦0.45份、 環烷酸鉻（金屬含量12% ) 0.4份，由液體下部之氣體導 入管吹入空氣，同時加溫至13 0°C繼續反應1〇小時’而 製得酸價0.5 mgKOH/g之反應物（反應物I )。於其上再 加入乙基卡必醇乙酸酯98份、四氫苯二酸酐106.4份（ 〇 · 7莫爾），於1 2 0 °C進一步反應2小時，製得固態成分 酸價 101.1 mgKOH/g之反應物（反應物II)。進而’再 -23- 200836005 (21) 戴 製 .03 :價 入 型 ) 份 莫 導 而 再 ( 分 再 戴 製 .03 價 加入環氧丙基甲基丙烯酸酯21.3份（0.15莫爾）、「 納克爾」（登錄商標）EX-145 ( nagasechemtex (股） ，環氧當量450:苯酚（EO)5環氧丙基醚）13.5份（〇 莫爾），於1 2 0 °C進一步反應3小時’製得固態成分酸 68.9 mgKOH/g 之樹脂 6。 合成例7 (樹脂7之合成例） 在具有攪拌機、氣體導入管、還流管之燒瓶內，裝 乙基卡必醇乙酸酯92份，於其中使〇 一甲酚酚醛清漆 環氧樹脂（商品名稱：「愛普特多」（登錄商標 YDCN704，東都化成株式會社製，環氧當量210 ) 210 (1·〇當量）溶解。進而，加入丙烯酸69.84份（0.97 爾）、乙醇酸2.16份（0·03莫爾）、聚合抑制劑2,6 -一 t — 丁基—4 一甲氧基苯酚2.17份及三苯基膦0.45份 環烷酸鉻（金屬含量12%) 5.0份，由液體下部之氣體 入管吹入空氣，同時加溫至1 3 (TC繼續反應1 0小時， 製得酸價0.5 mgKOH/g之反應物（反應物I)。於其上 加入乙基卡必醇乙酸酯98份、四氫苯二酸酐106.4份 〇·7莫爾），於120°C進一步反應2小時，製得固態成 酸價101.1 mgKOH/g之反應物（反應物II)。進而， 加入環氧丙基甲基丙烯酸酯21.3份（0.15莫爾）、「 納克爾」（登錄商標）EX-145 ( nagasechemtex (股） ，環氧當量450:苯酚（EO)5環氧丙基醚）13.5份（0, 莫爾），於120 °C進一步反應3小時，製得固態成分酸 -24- 200836005 (22) 68.9 mgKOH/g 之樹脂 7。 比較合成例1 (樹脂8之合成例） 在具有攪拌機、氣體導入管、還流管之燒瓶內，裝入 乙基卡必醇乙酸酯92份，於其中使〇 —甲酚酚醛清漆型 環氧樹脂（商品名稱：「愛普特多」（登錄商標） YDCN704，東都化成株式會社製，環氧當量210 ) 210份 (1.0當量）溶解。進而，加入丙烯酸69.84份（0.97莫 爾）、乙醇酸2.16份（0.03莫爾）、聚合抑制劑2,6-二 一 t 一丁基一 4 一甲氧基苯酚2.17份及三苯基膦0.85份， 由液體下部之氣體導入管吹入空氣，同時加溫至130°C繼 續反應1〇小時，而製得酸價0.5 mgKOH/g之反應物（反 應物I )。於其上再加入乙基卡必醇乙酸酯98份、四氫 苯二酸酐106.4份（0.7莫爾），於120°C進一步反應2 小時，製得固態成分酸價101.1 mgKOH/g之反應物（反 應物II)。進而，再加入環氧丙基甲基丙烯酸酯21.3份 (0.15莫爾）、「戴納克爾」（登錄商標）EX_145 ( nagasechemtex (股）製，環氧當量450:苯酣（E0)5環氧 丙基醚）13.5份（0.03莫爾），於120°C進一步反應3小 時，製得固態成分酸價68.9 mgKOH/g之樹脂8。 比較合成例2 (樹脂9之合成例） 在具有攪拌機、氣體導入管、還流管之燒瓶內，裝入 乙基卡必醇乙酸酯92份，於其中使〇 -甲酚酚醛清漆型 -25· 200836005 (23) 環氧樹脂（商品名稱：「愛普特多」（登錄商標） YDCN704，東都化成株式會社製，環氧當量210 ) 210份 (1·〇當量）溶解。進而，加入丙烯酸69.84份（0.97莫 爾）、乙醇酸2·16份（0.03莫爾）、聚合抑制劑2,6-二 一 t — 丁基一 4 一甲氧基苯酚2.17份及環烷酸鉻（金屬含 量3%) 1.4份，由液體下部之氣體導入管吹入空氣，同 時加溫至 130 °C繼續反應 10小時，而製得酸價 0.5 mgKOH/g之反應物（反應物I)。於其上再加入乙基卡必 醇乙酸酯98份、四氫苯二酸酐106.4份（0.7莫爾），於 1 20 °C進一步反應 2小時，製得固態成分酸價 1 0 1 . 1 mgKOH/g之反應物（反應物II)。進而，再加入環氧丙 基甲基丙烯酸酯21.3份（0.15莫爾）、「戴納克爾」（ 登錄商標）EX-145 ( nagasechemtex (股）製，環氧當量 450 :苯酚（EO)5環氧丙基醚）13.5份（0.03莫爾），於 120 °C進一步反應 3 小時，製得固態成分酸價 68.9 mgKOH/g之樹月旨9。 比較合成例3 (樹脂1 〇之合成例） 在具有攪拌機、氣體導入管、還流管之燒瓶內，裝入 乙基卡必醇乙酸酯92份，於其中使〇 -甲酚酚醛清漆型 環氧樹脂（商品名稱：「愛普特多」（登錄商標） YDCN704，東都化成株式會社製，環氧當量210) 210份 (1·〇當量）溶解。進而，加入丙烯酸69.84份（0.97莫 爾）、乙醇酸2.16份（0.03莫爾）、聚合抑制劑2,6-二 -26- 200836005 (24) —t — 丁基一4 —甲氧基苯酚2.17份及苄基二甲基胺〇·85 份，由液體下部之氣體導入管吹入空氣，同時加溫至130 。(：繼續反應1〇小時’而製得酸價〇·5 mgKOH/g之反應物 (反應物I )。於其上再加入乙基卡必醇乙酸酯98份、 四氫苯二酸酐106.4份（0.7莫爾），於120 °C進一步反 應2小時，製得固態成分酸價101.1 mgKOH/g之反應物 (反應物II)。進而’再加入環氧丙基甲基丙烯酸酯21.3 份（0.15莫爾）、「戴納克爾」（登錄商標）EX-145 ( nagasechemtex (股）製，環氧當量450:苯酣（EO)5環氧 丙基醚）13.5份（0.03莫爾），於120 °C進一步反應3小 時，製得固態成分酸價68.9 mgKOH/g之樹脂10。 比較合成例4 (樹脂1 1之合成例） 在具有攪拌機、氣體導入管、還流管之燒瓶內，裝入 乙基卡必醇乙酸酯92份，於其中使〇 -甲酚酚醛清漆型 環氧樹脂（商品名稱：「愛普特多」（登錄商標） YDCN704，東都化成株式會社製，環氧當量210 ) 210份 (1·〇當量）溶解。進而，加入丙烯酸69.84份（0.97莫 爾）、乙醇酸2.16份（0.03莫爾）、聚合抑制劑2,6-二 一 t 一丁基—4 一甲氧基苯酚2.17份及苄基二甲基胺0.45 份、環烷酸鉻（金屬含量3%) 0.85份，由液體下部之氣 體導入管吹入空氣，同時加溫至1 3 0 °C繼續反應1 〇小時 ，而製得酸價0.5 mgKOH/g之反應物（反應物I )。於其 上再加入乙基卡必醇乙酸酯98份、四氫苯二酸酐1〇6·4 -27- (25) (25)200836005 份（0.7莫爾），於120°C進一步反應2小時，製得固態 成分酸價101.1 mgKOH/g之反應物（反應物II)。進而 ，再加入環氧丙基甲基丙烯酸酯21.3份（0.15莫爾）、 「戴納克爾」（登錄商標）EX-145 ( nagasechemtex (股 )製，環氧當量450:苯酚（EO)5環氧丙基醚）13.5份（ 〇.〇3莫爾），於120 °C進一步反應3小時，製得固態成分 酸價68.9 mgKOH/g之樹脂11。 比較合成例5 (樹脂1 2之合成例） 在具有攪拌機、氣體導入管、還流管之燒瓶內，裝入 乙基卡必醇乙酸酯92份，於其中使〇 -甲酚酚醛清漆型 環氧樹脂（商品名稱：「愛普特多」（登錄商標） YDCN704，東都化成株式會社製，環氧當量210) 210份 (1.0當量）溶解。進而，加入丙烯酸72份（1.0莫爾） 、聚合抑制劑2,6-二一 t 一丁基一 4 一甲氧基苯酚2.17份 及三苯基膦〇·85份，由液體下部之氣體導入管吹入空氣 ，同時加溫至130 °C繼續反應10小時，而製得酸價0.5 mgKOH/g之反應物（反應物I )。於其上再加入乙基卡必 醇乙酸酯98份、四氫苯二酸酐72·0份（0.5莫爾），於 120 °C進一步反應 2小時，製得固態成分酸價 78.4 mgKOH/g之樹月旨12。 比較合成例6 (樹脂1 3之合成例） 在具有攪拌機、氣體導入管、還流管之燒瓶內，裝入 -28- (26) (26)200836005 乙基卡必醇乙酸酯92份，於其中使〇-甲酚酚醛清漆型 環氧樹脂（商品名稱：「愛普特多」（登錄商標） YDCN704，東都化成株式會社製，環氧當量210) 210份 (1.0當量）溶解。進而，加入丙烯酸72份（1·〇莫爾） 、聚合抑制劑2,6-二—t一丁基—4 一甲氧基苯酚2.17份 及三苯基膦0.85份，由液體下部之氣體導入管吹入空氣 ，同時加溫至1 3 0 °C繼續反應1 0小時，而製得酸價〇 · 5 mgKOH/g之反應物（反應物I)。於其上再加入乙基卡必 醇乙酸酯9 8份、四氫苯二酸酐1 0 6.4份（〇 · 7莫爾），於 1 20 °C進一步反應 2小時，製得固態成分酸價 1 〇 1 · 1 mgKOH/g之反應物（反應物II)。進而，再加入環氧丙 基甲基丙烯酸酯2 1 . 3份（0 · 1 5莫爾）、「戴納克爾」（ 登錄商標）EX-145 ( nagasechemtex (股）製，環氧當量 450:苯酚（EO)5環氧丙基醚）13.5份（0.03莫爾），於 120 °C進一步反應 3小時，製得固態成分酸價 68.9 mgKOH/g之樹月旨14。 比較合成例7 (樹脂1 4之合成例） 在具有攪拌機、氣體導入管、還流管之燒瓶內，裝入 乙基卡必醇乙酸酯92份，於其中使〇 -甲酚酚醛清漆型 環氧樹脂（商品名稱：「愛普特多」（登錄商標） YDCN704，東都化成株式會社製，環氧當量210) 210份 (1·〇當量）溶解。進而，加入丙烯酸72份（1·〇莫爾） 、聚合抑制劑2,6-二—t 一 丁基一 4 一甲氧基苯酚2.17份 -29- 200836005 (27) 及苄基二甲基胺0.85份，由液體下部之氣體導入管吹入 空氣，同時加溫至1 3 0 °C繼續反應1 0小時’而製得酸價 0.5 mgKOH/g之反應物（反應物！）。於其上再加入乙基 卡必醇乙酸酯98份、四氫苯二酸酐106·4份（〇·7莫爾） ，於1 2 0 °C進一步反應2小時，製得固態成分酸價1 〇 1 · 1 mgKOH/g之反應物（反應物II )。進而，再加入環氧丙 基甲基丙烯酸酯21.3份（〇·15莫爾），於120 °C進一步 反應3小時，製得固態成分酸價75.3mgKOH/g之樹脂15 比較合成例8 (合成失敗例） 以與比較合成例6相同之裝置，不使用聚合抑制劑及 合成觸媒，以及不吹入空氣以外，其餘均與比較合成例3 同樣地進行反應，惟反應物I之步驟在第4小時變得凝膠 化。經再度確認後，反應中之酸價幾乎未降低而同樣地凝 膠化。 實施例1〜7及比較例1〜7 根據表1所示之配合比率配合各成分，以三輥輾機使 其充分混練，而製得本發明之感光性樹脂組成物。此外， 表1中之樹脂質量係表示樹脂固態成分之値。 其次’於事先將表面處理過之印刷電路板上，將上述 之感光性樹脂組成物以網版印刷法塗佈成爲乾燥塗膜3 0 〜40 # m者。於80 °C乾燥20分鐘後，冷卻至室溫而製得 -30- 200836005 (28) 乾燥塗膜（以下稱爲「預備乾燥塗膜」）。將該預備乾燥 塗膜利用超高水銀燈以25 0 mJ/cm2進行曝光。其後，於 1 5 0°C下進行30分鐘之後硬化，而製得硬化塗膜。就所製 得之硬化塗膜及預備乾燥塗膜，進行下述之各種物性評價 。其寺之結果不於表2中。 感度 於預備乾燥塗膜上設置階段表面（step tablet )(柯 達14段），利用超高水銀燈以250 mJ/cm2進行曝光。其 後，使用1%碳酸鈉水溶液進行噴射壓爲2.0 kgf/mm2之 60秒顯像後，測定曝光部分未被除去之段數。 觸摸乾燥性 在測定上述感度時，就曝光後之階段表面（step tablet )剝落時之剝落容易度加以評價。 ◎:剝落時無問題可剝落。 〇：剝落時略有沾黏情形惟尙無問題可剝落。 X :剝落時階段表面（step tablet )會沾黏。 乾燥管理幅度 將預備乾燥塗膜之80°C之乾燥時間變更爲20分及40 分、50分、60分、70分之預備乾燥塗膜，使用1%碳酸 鈉水溶液，進行噴射壓爲2.0 kgf/mm2之60秒顯像後，觀 察顯像後之塗膜’並依下述基準進行評價。 -31 - 200836005 (29) ◎:顯像時間60秒後，以目視觀察無塗膜。 〇：顯像時間120秒後，以目視觀察無塗膜。 X :顯像時間1 20秒後，以目視觀察有殘餘膜 焊錫耐熱性 將硬化塗膜依據 JIS C648 1，在260°C之焊錫液中以 1 〇秒使其浮起3次，觀察取出後該塗膜之膨脹或剝落等 ，變少® 態無有fM 0¾ 形 觀顴 — 之外外fi 觀·· ·· 1 外 ◎ 〇 X 膜 塗 價 評 行 進 準 基 述 下 。 據化 依。變 並化許 化 耐溶劑性 將硬化塗膜浸漬於二氯甲烷中3 0分鐘後，評價該塗 膜之狀態。 ◎:外觀無變化。 〇：外觀有少許變化。 X :外觀有變化。 P C T (壓力鍋試驗）耐性 將硬化塗膜於121 °C、2氣壓、飽和蒸汽環境下，放 置50小時、1 〇〇小時後，評價其塗膜之狀態。 ◎:外觀無變化。 〇：外觀有少許變化。 -32- 200836005 (30) x :外觀有變化。 鍍金耐性 硬化塗膜之前處理，係進行：於3 0 °〇 中浸漬—浸漬水洗θ軟蝕刻處理·^浸漬水洗 於3 (TC之鍍鎳觸媒液中浸漬7分鐘）—浸 其次，無電解鎳步驟，係進行：於鍍鎳液 4.6)中浸漬20分鐘—浸漬酸1分鐘（室溫 酸水溶液）—浸漬水洗。最後，無電解金電 行：於金電鍍液（95 t：，pH二6，氰化金鉀 )中浸漬10分鐘—浸漬水洗—於60°C之溫 ->充分水洗後，完全漘乾後乾燥。就該處理 目視評價塗膜之狀態並使用玻璃紙帶進行剝 〇 ◎:外觀無變化，全無剝離。 〇：外觀無變化，惟可見少許之剝離。 X :外觀有變化，可見少許之剝離。 熱安定性 對於樹脂1、樹脂1 3、樹脂14，充分ft 三羥甲基丙烷三丙烯酸酯，並加入試管。在 其達到無流動性之時間，並將之作爲凝膠化 示於第3表中。 之酸性脫脂液 賦予觸媒（ 漬水洗步驟。 (85 °C ，pH = 1 0 ν ο 1 % 硫 鍍步驟，係進 ί V ο 1 %水溶液 水中浸漬水洗 後之塗膜，以 離試驗之評價 混合1 0份之 120°C下評價 時間。其結果 -33- (31)200836005 比較例 卜 2 Ο τ-Η Ο 00 (N τ-Η m Ο ο oo (N r-H yr) in (N Ο τ-Η ο oo (N r—H 寸 Ο r-H ο 00 (N ▼-H m 〇 Ο Η ο 00 (N i-H (N Ο ο 00 (N r-H r-H 00 Ο ο oo (N r-H 實施例 卜 卜 Ο 1—Η ο 00 CN VO Ό Ο 1—Η ο 00 (N ▼—H Ο 1—Η ο 00 CN 寸 寸 Ο τ—Η ο 00 <N (Τ) ro Ο τ-Η ο 00 (N t-H (N (N Ο τ—Η ο 00 (N ^T) 1—H Ο ο 00 (N r-H ^Ti 樹脂 重量份 乙基溶纖劑 S ^ 勸f in in 2,2-_^甲氧基-2- 苯基丙酮 硫酸鋇 微粉二氧化矽 酉太菁綠 IlD^ ^ 'l1 it a瞰 二氰二醯胺 樹脂 (固態 成分） -34- (32)200836005 比較例 卜 ◎ ◎ ◎ 〇 X X X ◎ ◎ ◎ ◎ ◎ VO ON O ◎ ◎ ◎ ◎ 〇 X ◎ ◎ ◎ ◎ ◎ VO ◎ ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ 〇 〇 寸 o f—H ◎ ◎ ◎ 〇 〇 X X ◎ ◎ ◎ ◎ ◎ cn r-H ◎ ◎ ◎ 〇 〇 X X ◎ ◎ ◎ ◎ ◎ (N 〇> X ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ r—H o r-H ◎ ◎ ◎ ◎ ◎ 〇 〇 ◎ ◎ ◎ ◎ ◎ 實施例 卜 ON 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇\ ◎ ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ ◎ ^Τ) 1—H t—H ◎ ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ ◎ 寸 00 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ m 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ (N ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ r-H ON ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 感度 觸摸乾燥性 20分 40分 50分 60分 70分 80分 焊錫耐熱性 耐溶劑性 七 ο 鍍金耐性 乾燥 管理 幅度 Η Μ ^ ife -35- 200836005 (33) [表3] 樹脂 樹脂1 樹脂13 樹脂14 凝膠化 45 0分以上 3 60分 1 90分Since the monoepoxy compound having a radical polymerizable unsaturated group is located at the outermost portion of the photosensitive resin (A) skeleton, the radical polymerizable unsaturated group has high mobility and can be highly sensitive. On the other hand, the water-soluble monoepoxy compound is also located at the outermost portion of the resin skeleton, and the unsaturated group motility of the monoepoxy compound having the radical polymerizable unsaturated group is moderately suppressed. The stability at the time of storage or work can be improved, and the solubility in an alkaline solution having moderate hydrophilicity on the resin skeleton can be improved. Next, a method of producing the photosensitive resin (A) will be described. In order to synthesize the reactant I in the step I, (d) an unsaturated monovalent acid and (e) a saturated monovalent acid having an alcoholic hydroxyl group of a first order, by a conventional method for (c -12-200836005 ( 10)) The novolac type epoxy resin reacts. When the epoxy resin is in the form of a liquid, it can be reacted without a solvent. However, if the (c) novolak-type epoxy resin is in a solid state, it is preferred to react in a solvent. The solvent to be used may, for example, be a methyl ethyl ketone, a ketone of cyclohexanone, an aromatic hydrocarbon such as toluene or xylene, a glycol ether such as dipropylene glycol dimethyl ether or the like. Ester, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, dipropylene glycol monomethyl ether acetate, esters, petroleum esters, A petroleum solvent such as petroleum brain or solvent naphtha. Further, in the reaction temperature of the step I, it is preferably 60 ° C to 150 ° C. The reaction time is preferably from 5 to 20 hours. Compared with (c) the epoxy group 1 Mohr of the novolac type epoxy resin, (d) the unsaturated monovalent acid and (e) the total amount of the saturated monovalent acid having the alcoholic hydroxyl group of the first order, added As for . 9~1. 1 Moore is preferred. Further, the amount of the saturated monovalent acid having the alcoholic hydroxyl group of the first order is, for example, the unsaturated monobasic acid and the saturated monovalent acid having the alcoholic hydroxyl group of the first order, which is 1 mole. 〇5~0. 4 Moore is better. The amount of saturated monovalent acid having a grade 1 alcoholic hydroxyl group, such as 0. When 05 Mohr is small, the effect of its use will be reduced, and it will be more embarrassing. When the molar ratio is 4, the concentration of the polymerizable unsaturated group derived from the unsaturated monovalent acid is lowered, and it is difficult to add the radical polymerizable unsaturated group of the step II described later and the compound having an epoxy group. The sensitivity is made high, and the effects of the present invention may not be sufficiently achieved. Step III is a monoepoxy compound having a radical polymerizable unsaturated group and (h) a water-soluble monocyclic ring for the carboxyl group of the reactant II of the above step II, 13-(11) (11)200836005 (g) The oxygen compound is reacted to obtain. The reaction catalyst can be used in the same manner as in the case of the synthesis of the reactant I. After the reaction product is synthesized, the synthesis in the step 111 can be carried out without adding a catalyst, or a catalyst can be additionally added. The compound having a radical polymerizable unsaturated group and an epoxy group is preferably used in an amount of (g) a monoepoxy group having a radical polymerizable unsaturated group with respect to the carboxyl group 1 mole in the above reactant II. The total amount of the compound and (h) water-soluble monoepoxy compound, is 0. 15~0. 4 Moore. If it is more ambiguous. When 1 5 is low, the effect of improving the light sensitivity tends to deteriorate, as in 0. When the amount is 4 or more, the amount of the carboxyl group in the resin is too small, and the alkali developability tends to be deteriorated. On the other hand, the amount of the water-soluble monoepoxy compound is 0, compared with the carboxyl group 1 in the aforementioned reactant II. 01~ 〇 . 1 Moore. As in 0. 〇 1 below Moore, can not get sufficient effect; such as added to 0. When it is 1 or more, the effect of blending is not obtained, and the motility of the monoepoxy compound having a radical polymerizable unsaturated group is excessively suppressed, and as a result, the light sensitivity is lowered. The reaction temperature is preferably 60 ° C to 15 (TC. The reaction time is preferably 0. 5 to 20 hours. The photosensitive resin composition of the present invention further comprises the above-mentioned (A) photosensitive resin, (B) epoxy resin, (C) photopolymerization initiator, and (D) a reactive diluent. This photosensitive resin composition is used as a base developing type photosensitive resin composition. The (B) epoxy resin used in the alkali-developing photosensitive resin composition of the present invention, for example, triethoxypropyl isocyanurate or in the aforementioned step-14-(12) (12) 200836005 I (c) a novolac type epoxy resin. These epoxy resins may be used alone or in combination of two or more. Further, in order to secure Tg and further improve the toughness, it is also effective to use a phosphorus-containing epoxy resin or the like from the viewpoint of use of an isocyanurate-modified epoxy resin or imparting flame retardancy. The epoxy resin (B) described above can be used as a solder resist to improve adhesion, heat resistance, and electroplating resistance, and a thermosetting component can be blended in the composition. When a printed circuit board or the like is produced, the resin is cured by heating with a dilute aqueous alkali solution, whereby the circuit board can be provided with better adhesion, heat resistance, plating resistance, and the like. (B) The epoxy resin may be used singly or in combination of one or more kinds. The amount of the epoxy resin (B) of the present invention is 5 to 100% by mass based on 100 parts by mass of the photosensitive resin (A). When the amount is less than 5% by mass, it is difficult to obtain excellent properties of the cured coating film, and if it is more than 1% by mass, the alkali solubility tends to deteriorate. In order to further improve the properties of the (B) epoxy resin, such as adhesion, heat resistance, and electroplating resistance, an epoxy curing agent is preferably used. Examples of such an epoxy hardener include an imidazole derivative, a phenol derivative, dicyandiamide, a dicyandiamide derivative, a melamine, a melamine resin, a hydrazine derivative, an amine, an acid anhydride, and the like. The above-mentioned curing agent may be used singly or in combination of two or more kinds. The amount of the hardener used is 1 mol to the epoxy group of the epoxy resin, and the amount of active hydrogen of the hardener is 〇 5 to 1. The ratio of 2 Mohr is better. The (C) photopolymerization initiator used in the photosensitive resin composition of the present invention, specific examples thereof are benzoin, acetophenone, anthracene, thioxan-15-200836005 (13) ketone, Benzophenones and the like. For example, benzoin is a derivative of benzoin, benzoin methyl ether, benzoin isopropyl ether, etc.; acetophenone is acetophenone, 2,2-dimethoxy-2-phenyl Derivatives such as acetophenone; oximes are 2-methyl hydrazine, 2-chloro hydrazine, 2-ethyl hydrazine, 2-t-butyl hydrazine and the like; thioxanthone has thioxanthene Derivatives such as ketones, 2,4-dimethylthioxanthone; benzophenones with benzophenone, 4-benzoquinone-4'-methyldiphenyl sulfide, 4,4'-dichloro Derivatives such as benzophenone and N,N-dimethylaminobenzophenone, and 2,4,6-trimethylphenylhydrazine diphenylphosphine oxide may be used singly or in combination of two or more kinds. . Further, as the (C) photopolymerization initiator, a conventional photosensitizer such as a tertiary amine may be used. Specifically, there are triethanolamine, tripropanolamine, triethylamine, N,N-dimethylamino acid benzoic acid ethyl ester, N,N-dimethylamino benzoic acid isoamyl ester, pentane 4 Monomethylamino benzoate and the like. The above (C) photopolymerization initiator may be used singly or in combination of two or more kinds, or even a conventional photo sensitizer. (C) The ratio of use of the photopolymerization initiator is 0.1% by mass relative to (A) photosensitive resin. 5 to 30 parts by mass. It is at 0. 5 parts by mass or less. When used, the effect of use is lowered and the light sensitivity is lowered. Even if you use more than 3 G parts by mass, the added effect is low. In the photosensitive resin composition of the present invention, (D) a reactive diluent is used. (D) The reactive diluent is used for the purpose of improving the hardenability to the active energy ray and/or applying the photosensitive resin composition as a coating property when the solder resist ink is used. Such a polymerizable unsaturated compound is preferably a monomer having an active energy light hard-16-(14)(14)200836005, for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl group. Acrylate, N-pyrrolidone, N-propenylmorpholine, N,N-dimethylpropenylamine, n,N-diethylpropenylamine, N,N-dimethylaminoethyl Acrylate, n,N-dimethylaminopropyl acrylate, methoxy polyethylene glycol acrylate, ethoxylated polyethylene glycol acrylate, melamine propionate, phenoxyethyl Propionate, phenoxypropyl acrylate, ethylene glycol diacrylate, dipropylene glycol diacrylate, polydipropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylic acid Ester, dipentaerythritol hexaacrylate, glycerol diacrylate, isophorone acrylate, dicyclopentenyloxyethyl acrylate, and the like, and various methacrylates thereof. These polymerizable unsaturated compounds may be used alone or in combination of two or more. The reactive diluent (D) may be used alone or in a mixture of two or more. The amount of use is 10 to 200 parts by mass, preferably 20 to 150 parts by mass, based on 100 parts by mass of the photosensitive resin (A). When the amount used is less than 1 part by mass, the light sensitivity may become too low, and the viscosity may become high, and the coatability may be deteriorated. On the other hand, when it is more than 200 parts by mass, when the photosensitive resin composition is used as a solder resist ink, the viscosity may become too low, and the characteristics as a cured coating film may be insufficient. Further, in order to adjust the coatability, a solvent may be used in combination with the above (D) reactive diluent. Examples of such solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, ethyl cellosolve, butyl cellosolve, carbitol, and butyl carbene. Carbitol such as alcohol, -17-(15) (15)200836005 Ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, ethyl carbitol acetate, and the like. These solvents may be used alone or in combination of two or more. Further, when the photosensitive resin composition of the present invention is used as a liquid solder resist ink, an inorganic chelating agent such as silica sand, calcium carbonate, barium sulfate, clay or talc, or phthalocyanine may be used as needed. In addition to various additives such as green, phthalocyanine blue, titanium oxide, carbon black and other coloring pigments, defoamers, leveling agents, etc., hydroquinone, resorcinol, catechol, pyrogallol, A polymerization inhibitor of hydroquinone monomethyl ether, t-butyl catechol, phenothiazine, and the like. The photosensitive resin composition of the present invention can be obtained by blending each of the above-mentioned components, preferably in the above-described ratio, and uniformly mixing them by a three-roll mill or the like. Further, the photosensitive resin composition of the present invention is a liquid composition which can be cured, for example, as shown below to obtain a cured product. That is, on the printed circuit board, the screen printing method, the inkjet printing method, the roll coating method, the electrostatic coating method, the curtain coating method, and the like, and the method is 10 to 1 60 0 m. The film thickness is applied to the composition of the present invention. Thereafter, the coating film was dried at 60 to 110 °C. The negative film is directly contacted with the coating film, or placed on the coating film without being exposed, and then irradiated with ultraviolet rays to expose the composition. The unexposed portion is dissolved in a dilute alkali aqueous solution to be removed for development. Further, in order to enhance various physical properties, ultraviolet rays are irradiated and/or heated (for example, at 1 〇〇 to 2 0 0 °c, 0 · 5 to 1 · 0 hours) sufficient hardening was carried out to obtain a hardened coating film. -18-200836005 (16) [Embodiment] BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail by way of examples and comparative examples, which are "parts" and "%" in each example unless otherwise limited. The external quality standards. Further, the present invention is not limited by these examples. Synthesis Example 1 (Synthesis Example of Resin 1) In a flask equipped with a stirrer, a gas introduction tube, and a reflux tube, 92 parts of ethyl carbitol acetate was placed, and a 0-cresol novolac type epoxy resin was added thereto. (product name: "Aptutuo" (registered trademark) YDCN704, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 210) 210 parts (1·〇 equivalent) dissolved. Further, acrylic acid was added. 84 copies (0. 97 Moll), 2·16 parts of glycolic acid (0. 03 Mohr), polymerization inhibitor 2,6-di-t-butyl-4-methoxyphenol 2. 17 parts and triphenylphosphine 0. 45 parts, chromium naphthenate (metal content 3%) 0 · 8 5 parts, air is blown from the gas introduction pipe in the lower part of the liquid, and heated to 130 ° C to continue the reaction for 10 hours, and the acid value is obtained. 0. 5 mg KOH / g of reactant (Reactant I). Further, 98 parts of ethyl carbitol acetate and tetrahydrophthalic anhydride 106 were added thereto. 4 copies (0. 7 Mohr), further reacted at 120 ° C for 2 hours to obtain a solid content of acid value 101. 1 mg KOH / g of reactant (Reactant II). Further, a further addition of epoxypropyl methacrylate 21. 3 copies (0. 15 Moore), "Danaker" (registered trademark) EX-145 (made by nagasechemtex (equipment), epoxy equivalent 450: phenol (EO) 5 epoxy propyl ether) 13. 5 parts (〇·〇3 Mo Further, the reaction was further carried out at 120 ° C for 3 hours to obtain a solid component acid value -19-200836005 (17) 68. 9 mg KOH / g of resin 1. Synthesis Example 2 (Synthesis Example of Resin 2) Inclusion type) Mo-derivative and re-doping (re-dosing • 03 price in a flask having a stirrer, a gas introduction tube, and a reflow tube, and containing ethyl carbitol acetate 92 parts, in which a cresol novolac varnish epoxy resin (trade name: "Epteto" (registered trademark YDCN704, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 210) 210 (1. 0 equivalents) dissolved. Further, acrylic acid was added. 84 copies (0. 97 er), glycolic acid 2. 16 copies (0. 03 Mohr), polymerization inhibitor 2,6-one t-butyl- 4-methoxybenzoquinone 2. 17 parts and triphenylphosphine 0. 45 parts of chromium naphthenate (metal content 6%) 0. For 85 parts, air was blown from the gas inlet pipe of the lower portion of the liquid while heating to 130 ° C for 10 hours to obtain a reactant (reactant I) having an acid value of mg 5 mg KOH / g. 98 parts of ethyl carbitol acetate and tetrahydrophthalic anhydride 106 were added thereto. 4 parts 〇·7 Mohr), at 12 (TC further reaction for 2 hours, to obtain a solid acid value of 101. 1 mg KOH / g of reactant (Reactant II). Further, epoxypropyl methacrylate was added 21. 3 copies (0. 15 Mohr), "Nacker" (registered trademark) EX-145 (nagasechemtex (strand), epoxy equivalent 450: phenol (EO) 5 epoxy propyl ether) 13. 5 parts (0 moir), further reacted at 120 ° C for 3 hours to obtain a solid component acid 68. 9 mg KOH / g of resin 2 . Synthesis Example 3 (Synthesis Example of Resin 3) In a flask having a stirrer, a gas introduction tube, and a reflux tube, 92 parts of -20-200836005 (18) ethyl carbitol acetate was placed, and ruthenium-cresol was added thereto. Novolac type epoxy resin (trade name · "Epteto" (registered trademark) YDCN704, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 210) 210 parts (1. 0 equivalents) dissolved. Further, acrylic acid was added. 84 parts (〇·97 Moll), glycolic acid 2. 16 parts (〇·〇3 Mohr), polymerization inhibitor 2,6-di-t-butyl- 4-methoxyphenol 2. 17 parts and triphenylphosphine 〇·45 parts, chromic octoate (12% metal content) 〇·85 parts, air is blown from the gas introduction pipe in the lower part of the liquid, and heated to 130 ° C for 1 hour. And the acid value is 0. 5 mg KOH / g of reactant (Reactant I). Further, 98 parts of ethyl carbitol acetate and tetrahydrophthalic anhydride 106 were added thereto. 4 copies (0. 7 Mohr), further reacted at 120 ° C for 2 hours to obtain a solid content of acid value 101. 1 mg KOH / g of reactant (Reactant II). Further, a further addition of epoxypropyl methacrylate 21. 3 copies (0. 15 Moore), "Danaker" (registered trademark) EX-145 (nagasechemtex (manufactured by the company), epoxy equivalent 450: phenol (EO) 5 epoxy propyl ether) 13. 5 copies (0. 03 Mohr), further reacted at 120 ° C for 3 hours to obtain the solid content acid value 68. 9 mg KOH / g of resin 3. Synthesis Example 4 (Synthesis Example of Resin 4) In a flask having a stirrer, a gas introduction tube, and a reflow tube, 92 parts of ethyl carbitol acetate was placed, and a cresol-cresol novolak type epoxy resin was added thereto. (product name: "Aptutuo" (registered trademark) YDCN704, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 210) 210 parts (1·〇 equivalent) dissolved. Further, acrylic acid was added. 84 copies (0. 97 Mo - 21 - (19) 200836005 Guided and then re-sold. 03 valence type) Momo ring derivative), glycolic acid 2 · 16 parts (〇 · 〇 3 Mohr), polymerization inhibitor 2,6 - a t - butyl 4-methoxyphenol 2. 17 parts and triphenylphosphine 0. 12 parts of chromium naphthenate (metal content 3%) 0. 85 parts 'Blow air from the lower part of the liquid into the tube, while heating to 130 ° C to continue the reaction for 1 〇 hours, the acid value of 0. 5 mg KOH / g of reactant (Reactant I). 9 8 parts of ethyl carbitol acetate and 10 0 of tetrahydrophthalic anhydride were added thereto. 4 copies 0. 7 Mohr), further reacted at 120 ° C for 2 hours to obtain a solid acid value of 101. 1 mg KOH / g of reactant (Reactant II). Further, epoxypropyl methacrylate was added 21. 3 copies (0. 15 Moore), "Nacker" (registered trademark) EX-145 (nagasechemtex (strand), epoxy equivalent 450: phenol (E 0) 5 epoxy propyl ether) 13. 5 parts (0 moir), further reacted at 120 ° C for 3 hours to obtain a solid component acid 68. 9 mg KOH / g of resin 4 . Synthesis Example 5 (Synthesis Example of Resin 5) In a flask equipped with a stirrer, a gas introduction tube, and a reflow tube, 92 parts of ethyl carbitol acetate was placed, and ruthenium-cresol novolac epoxy resin was used therein. Name: "Epteto" (registered trademark YDCN704, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 210) 210 (1. 0 equivalents) dissolved. Further, acrylic acid was added. 84 copies (0. 97 Å), glycolic acid 2 · 16 parts (0 · 03 mole), polymerization inhibitor 2,6 -1 t-butyl- 4 -methoxy phenol 2. 17 parts and triphenylphosphine 1. 5 parts, chromium alkanoate (12% metal content) 0. 85 parts, the air from the lower part of the liquid into the tube into the air, while heating to 130 ° C to continue the reaction for 1 〇 hours, -22- (20) (20) 200836005 to obtain the acid value of mg · 5 mgKOH / g reaction (Reactant I). Further, 98 parts of ethyl carbitol acetate and tetrahydrophthalic anhydride 106 were added thereto. 4 copies ( 〇 . 7 Mohr), further reacted at 120 ° C for 2 hours to obtain a solid content of acid value 101. 1 mg KOH / g of reactant (Reactant II). Further, a further addition of epoxypropyl methacrylate 21. 3 copies (0. 15 Moore), "Danaker" (registered trademark) EX-145 (nagasechemtex (manufactured by the company), epoxy equivalent 450: phenol (EO) 5 epoxy propyl ether) 13. 5 copies (0. 03 Mohr), further reacted at 120 °C for 3 hours to obtain the solid content acid value. 9 mg KOH / g of resin 5 . Synthesis Example 6 (Synthesis Example of Resin 6) In a flask equipped with a stirrer, a gas introduction tube, and a reflux tube, 92 parts of ethyl carbitol acetate was placed, and a cresol-cresol novolak type epoxy resin was added thereto. (Product name: "Epteto" (registered trademark) YDCN704, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 210) 210 parts (1. 0 equivalents) dissolved. Further, acrylic acid was added. 84 parts (〇·97 Moll), glycolic acid 2. 16 parts (0·03 moir), polymerization inhibitor 2,6-di-t-t-butyl- 4-methoxyphenol 2. 17 parts and triphenylphosphine 0. 45 parts, chromium naphthenate (12% metal content) 0. 4 parts, air is blown from the gas introduction tube at the lower part of the liquid, and heated to 130 ° C to continue the reaction for 1 ’ hour to obtain an acid value of 0. 5 mg KOH / g of reactant (reactant I). Further, 98 parts of ethyl carbitol acetate and tetrahydrophthalic anhydride 106 were added thereto. 4 parts (〇 · 7 moles), further reacted at 120 ° C for 2 hours to obtain a solid content of acid value 101. 1 mg KOH / g of reactant (Reactant II). And then ‘ -23- 200836005 (21) wearing system. 03 : Price type ) Mo Gui and then re - wear . 03 valence added to epoxy propyl methacrylate 21. 3 copies (0. 15 Mohr), "Nacker" (registered trademark) EX-145 (nagasechemtex (strand), epoxy equivalent 450: phenol (EO) 5 epoxy propyl ether) 13. 5 parts (〇 莫尔), further reacted at 120 ° C for 3 hours to produce a solid component acid 68. 9 mg KOH / g of resin 6. Synthesis Example 7 (Synthesis Example of Resin 7) In a flask equipped with a stirrer, a gas introduction tube, and a reflow tube, 92 parts of ethyl carbitol acetate was placed, and decyl phenol novolac epoxy resin was used therein. Name: "Aptutuo" (registered trademark YDCN704, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 210) 210 (1·〇 equivalent) dissolved. Further, acrylic acid was added. 84 copies (0. 97 er), glycolic acid 2. 16 parts (0·03 moor), polymerization inhibitor 2,6-t-t-butyl-4 monomethoxyphenol 2. 17 parts and triphenylphosphine 0. 45 parts of chromium naphthenate (12% metal content) 5. 0 parts, air is blown into the tube from the lower part of the liquid, and heated to 1 3 (TC continues to react for 10 hours to obtain an acid value of 0. 5 mg KOH / g of reactant (Reactant I). 98 parts of ethyl carbitol acetate and tetrahydrophthalic anhydride 106 were added thereto. 4 parts 〇·7 Mohr), further reacted at 120 ° C for 2 hours to obtain a solid acid value of 101. 1 mg KOH / g of reactant (Reactant II). Further, epoxypropyl methacrylate was added 21. 3 copies (0. 15 Mohr), "Nacker" (registered trademark) EX-145 (nagasechemtex (strand), epoxy equivalent 450: phenol (EO) 5 epoxy propyl ether) 13. 5 parts (0, Mohr), further reacted at 120 ° C for 3 hours to obtain a solid component acid -24- 200836005 (22) 68. 9 mg KOH / g of resin 7. Comparative Synthesis Example 1 (Synthesis Example of Resin 8) In a flask having a stirrer, a gas introduction tube, and a reflow tube, 92 parts of ethyl carbitol acetate was placed, and a cresol novolac type epoxy was added thereto. Resin (trade name: "Aptut" (registered trademark) YDCN704, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 210) 210 parts (1. 0 equivalents) dissolved. Further, acrylic acid was added. 84 copies (0. 97 Moll), glycolic acid 2. 16 copies (0. 03 Mohr), polymerization inhibitor 2,6-di-t-t-butyl- 4-methoxyphenol 2. 17 parts and triphenylphosphine 0. 85 parts, air was blown from the gas introduction pipe at the lower part of the liquid, and heated to 130 ° C for 1 hour, and the acid value was 0. 5 mg KOH/g of reactant (Reactant I). Further, 98 parts of ethyl carbitol acetate and tetrahydrophthalic anhydride 106 were added thereto. 4 copies (0. 7 Mohr), further reacted at 120 ° C for 2 hours to obtain a solid component acid price of 101. 1 mg KOH/g of reactant (Reactor II). Further, add propylene methacrylate 21. 3 copies (0. 15 Moore), "Danaker" (registered trademark) EX_145 (made by nagasechemtex (equipment), epoxy equivalent 450: benzoquinone (E0) 5 epoxy propyl ether) 13. 5 copies (0. 03 Mohr), further reacted at 120 ° C for 3 hours to obtain a solid component acid value of 68. 9 mg KOH / g of resin 8. Comparative Synthesis Example 2 (Synthesis Example of Resin 9) In a flask having a stirrer, a gas introduction tube, and a reflux tube, 92 parts of ethyl carbitol acetate was placed, and a cresol novolak type -25 was placed therein. · 200836005 (23) Epoxy resin (product name: "Aptut" (registered trademark) YDCN704, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 210) 210 parts (1·〇 equivalent) dissolved. Further, acrylic acid was added. 84 copies (0. 97 Moll), 2·16 parts of glycolic acid (0. 03 Mohr), polymerization inhibitor 2,6-di-t-t-butyl- 4-methoxyphenol 2. 17 parts and chromium naphthenate (3% metal content) 1. 4 parts, air was blown from the gas introduction pipe at the lower part of the liquid, and the reaction was further heated to 130 ° C for 10 hours to obtain an acid value of 0. 5 mg KOH / g of reactant (Reactant I). Further, 98 parts of ethyl carbitol acetate and tetrahydrophthalic anhydride 106 were added thereto. 4 copies (0. 7 Mohr), further reacted at 1 20 ° C for 2 hours to obtain a solid component acid value of 1 0 1 . 1 mg KOH / g of reactant (Reactant II). Further, an additional epoxy methacrylate 21. 3 copies (0. 15 Moore), "Danaker" (registered trademark) EX-145 (made by nagasechemtex), epoxy equivalent 450: phenol (EO) 5 epoxy propyl ether. 5 copies (0. 03 Mohr), further reacted at 120 °C for 3 hours to obtain the solid component acid value. 9 mg KOH / g tree month 9. Comparative Synthesis Example 3 (Synthesis Example of Resin 1 〇) In a flask equipped with a stirrer, a gas introduction tube, and a reflow tube, 92 parts of ethyl carbitol acetate was placed, and a cresol novolac novolac type ring was placed therein. Oxygen resin (trade name: "Aptut" (registered trademark) YDCN704, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 210) 210 parts (1·〇 equivalent) dissolved. Further, acrylic acid was added. 84 copies (0. 97 Moll), glycolic acid 2. 16 copies (0. 03 Mohr), polymerization inhibitor 2,6-di-26- 200836005 (24) —t — butyl 4-methoxyphenol 2. 17 parts and 85 parts of benzyldimethylamine oxime, air was blown from the gas introduction tube at the lower part of the liquid, and heated to 130 liters. (: Continue the reaction for 1 hr.) to obtain a reactant (reaction I) having an acid value of mg·5 mgKOH/g. Further, 98 parts of ethyl carbitol acetate and tetrahydrophthalic anhydride 106 were added thereto. . 4 copies (0. 7 Mohr), further reacted at 120 °C for 2 hours to obtain a solid component acid price of 101. 1 mg KOH / g of reactant (Reactant II). Further 'addition of epoxypropyl methacrylate 21. 3 copies (0. 15 Moore), "Danaker" (registered trademark) EX-145 (made by nagasechemtex (equipment), epoxy equivalent 450: benzoquinone (EO) 5 epoxy propyl ether) 13. 5 copies (0. 03 Mohr), further reacted at 120 °C for 3 hours to obtain a solid component acid value of 68. 9 mg KOH / g of resin 10. Comparative Synthesis Example 4 (Synthesis Example of Resin 1 1) In a flask equipped with a stirrer, a gas introduction tube, and a reflow tube, 92 parts of ethyl carbitol acetate was placed, and a cresol-cresol novolak type ring was placed therein. Oxygen resin (trade name: "Aptut" (registered trademark) YDCN704, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 210) 210 parts (1·〇 equivalent) dissolved. Further, acrylic acid was added. 84 copies (0. 97 Moll), glycolic acid 2. 16 copies (0. 03 Mohr), polymerization inhibitor 2,6-di-t-butyl-4-ylmethoxyphenol 2. 17 parts and benzyldimethylamine 0. 45 parts, chromium naphthenate (metal content 3%) 0. 85 parts were blown into the air by the gas introduction tube at the lower part of the liquid, and heated to 130 ° C for further 1 hour, and the acid value was 0. 5 mg KOH / g of reactant (reactant I). Further, 98 parts of ethyl carbitol acetate, and tetrahydrophthalic anhydride 1 〇 6·4 -27- (25) (25) 200836005 parts (0. 7 Mohr), further reacted at 120 ° C for 2 hours to obtain a solid component acid price of 101. 1 mg KOH / g of reactant (Reactant II). Further, add propylene methacrylate 21. 3 copies (0. 15 Moore), "Dana Kerr" (registered trademark) EX-145 (made by nagasechemtex (manufactured by the company), epoxy equivalent 450: phenol (EO) 5 epoxy propyl ether) 13. 5 copies ( 〇. 〇3 Mohr), further reacted at 120 ° C for 3 hours to obtain a solid content of acid value 68. 9 mg KOH / g of resin 11. Comparative Synthesis Example 5 (Synthesis Example of Resin 1 2) In a flask equipped with a stirrer, a gas introduction tube, and a reflow tube, 92 parts of ethyl carbitol acetate was placed, and a cresol-cresol novolak type ring was placed therein. Oxygen resin (trade name: "Aptut" (registered trademark) YDCN704, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 210) 210 parts (1. 0 equivalents) dissolved. Further, 72 parts of acrylic acid was added (1. 0 Mohr), polymerization inhibitor 2,6-di-t-t-butyl- 4-methoxyphenol 2. 17 parts and 85 parts of triphenylphosphine ruthenium were blown into the air by a gas introduction tube at the lower part of the liquid, and heated to 130 ° C for further 10 hours to obtain an acid value of 0. 5 mg KOH / g of reactant (reactant I). Further, 98 parts of ethyl carbitol acetate and 7·0 parts of tetrahydrophthalic anhydride were added thereto (0. 5 Mohr), further reacted at 120 ° C for 2 hours to obtain the solid content acid value 78. 4 mg KOH / g tree month 12. Comparative Synthesis Example 6 (Synthesis Example of Resin 13) In a flask having a stirrer, a gas introduction tube, and a reflux tube, 92 parts of -28-(26)(26)200836005 ethyl carbitol acetate was placed in Among them, a cresol-cresol novolac type epoxy resin (trade name: "Aptut" (registered trademark) YDCN704, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 210) 210 parts (1. 0 equivalents) dissolved. Further, 72 parts of acrylic acid (1·〇mol) and a polymerization inhibitor 2,6-di-t-butyl-4-methoxyphenol were added. 17 parts and triphenylphosphine 0. For 85 parts, air was blown from the gas introduction pipe at the lower portion of the liquid, and the reaction was further carried out until the temperature was maintained at 130 ° C for 10 hours to obtain a reactant (reactant I) having an acid value of mg 5 mgKOH/g. Further, 9 parts of ethyl carbitol acetate and 19 parts of tetrahydrophthalic anhydride were added thereto. 4 parts (〇 · 7 moles) were further reacted at 1 20 ° C for 2 hours to obtain a reactant (Reactant II) having a solid content of 1 〇 1 · 1 mgKOH/g. Further, a glycidyl methacrylate 2 1 was further added. 3 parts (0 · 15 Moore), "Dana Kerr" (registered trademark) EX-145 (made by nagasechemtex), epoxy equivalent 450: phenol (EO) 5 epoxy propyl ether. 5 copies (0. 03 Mohr), further reacted at 120 ° C for 3 hours to obtain the solid content acid value 68. 9 mg KOH / g tree month 14. Comparative Synthesis Example 7 (Synthesis Example of Resin 14) In a flask having a stirrer, a gas introduction tube, and a reflow tube, 92 parts of ethyl carbitol acetate was placed, and a cresol-cresol novolak type ring was placed therein. Oxygen resin (trade name: "Aptut" (registered trademark) YDCN704, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 210) 210 parts (1·〇 equivalent) dissolved. Further, 72 parts of acrylic acid (1·〇mol) and a polymerization inhibitor 2,6-di-t-butyl-4-methoxyphenol were added. 17 parts -29- 200836005 (27) and benzyl dimethylamine 0. 85 parts were blown into the air by a gas introduction pipe at the lower part of the liquid, and heated to 130 ° C to continue the reaction for 10 hours' to obtain an acid value of 0. 5 mg KOH / g of reactant (reactant!). Further, 98 parts of ethyl carbitol acetate and 106. 4 parts of tetrahydrophthalic anhydride (〇·7 moor) were further added thereto, and further reacted at 120 ° C for 2 hours to obtain a solid component acid value. 1 〇1 · 1 mgKOH/g of reactant (Reactant II). Further, an additional epoxy methacrylate 21. 3 parts (〇·15 Mohr), further reacted at 120 °C for 3 hours to obtain a solid content acid value of 75. 3 mg KOH/g of resin 15 Comparative Synthesis Example 8 (Synthesis failure example) The same apparatus as Comparative Synthesis Example 6 was used in the same manner as in Comparative Synthesis Example 3 except that the polymerization inhibitor and the synthetic catalyst were not used, and air was not blown. The reaction was carried out while the step of the reactant I became gelled at the 4th hour. After reconfirmation, the acid value in the reaction was similarly gelled without substantially decreasing the acid value. Examples 1 to 7 and Comparative Examples 1 to 7 Each component was blended according to the blending ratio shown in Table 1, and sufficiently kneaded by a three-roll mill to obtain a photosensitive resin composition of the present invention. Further, the quality of the resin in Table 1 indicates the enthalpy of the solid content of the resin. Next, the above-mentioned photosensitive resin composition is applied by a screen printing method to a dried coating film 3 0 to 40 # m on a printed circuit board which has been subjected to surface treatment in advance. After drying at 80 ° C for 20 minutes, it was cooled to room temperature to obtain a dry coating film (hereinafter referred to as "pre-dried coating film") of -30-200836005 (28). The preliminary dried coating film was exposed at 25 0 mJ/cm 2 using an ultrahigh mercury lamp. Thereafter, it was hardened after being dried at 150 ° C for 30 minutes to obtain a hardened coating film. The following physical properties were evaluated for the hardened coating film and the preliminary dried coating film which were obtained. The results of its temple are not in Table 2. Sensitivity A step tablet (Koda 14-segment) was placed on the preliminary dried coating film, and exposure was performed at 250 mJ/cm2 using an ultra-high mercury lamp. Thereafter, the spray pressure was 2. using a 1% aqueous sodium carbonate solution. After 60 seconds of development of 0 kgf/mm2, the number of segments in which the exposed portion was not removed was measured. Touch Dryness When the above sensitivity was measured, the ease of peeling at the time of peeling off the stage after exposure was evaluated. ◎: No problem can be peeled off when peeling off. 〇: There is a slight stickiness when peeling off, but there is no problem to peel off. X: The step tablet will stick when peeling off. Drying management range The drying time of the dried coating film at 80 ° C was changed to 20 minutes and 40 minutes, 50 minutes, 60 minutes, 70 minutes of the preliminary dry coating film, using a 1% sodium carbonate aqueous solution, the injection pressure was 2. After 60 seconds of development of 0 kgf/mm2, the film after development was observed and evaluated according to the following criteria. -31 - 200836005 (29) ◎: After 60 seconds of development time, no coating film was observed by visual observation. 〇: After 120 seconds of development time, no coating film was visually observed. X: After the development time of 1 20 seconds, the residual film solder heat resistance was visually observed. The hardened coating film was floated 3 times in a solder bath at 260 ° C for 1 time in accordance with JIS C648 1, and observed after removal. The expansion or flaking of the coating film, etc., is reduced to the state of the product. There is no fM 03⁄4 shape 颧 之外 之外 之外 之外 之外 之外 之外According to the chemical. The change of the solvent resistance was obtained by immersing the hardened coating film in methylene chloride for 30 minutes, and then evaluating the state of the coating film. ◎: No change in appearance. 〇: There is a slight change in appearance. X: The appearance has changed. P C T (pressure cooker test) resistance The cured film was placed at 121 ° C, 2 atmospheres, and saturated steam for 50 hours and 1 hour, and the state of the coating film was evaluated. ◎: No change in appearance. 〇: There is a slight change in appearance. -32- 200836005 (30) x : The appearance has changed. The gold-plated resistant hard coating film is treated before: immersion in 30 ° — - immersion washing θ soft etching treatment · immersion washing in 3 (immersion of TC nickel plating catalyst for 7 minutes) - dip, electroless The nickel step is carried out: in a nickel plating solution 4. 6) Immersion for 20 minutes - impregnation of acid for 1 minute (room temperature aqueous acid solution) - immersion washing. Finally, electroless gold wire: immersed in gold plating solution (95 t:, pH 2.6, gold potassium cyanide) for 10 minutes - immersion washing - at 60 ° C -> fully washed, completely dried After drying. The state of the coating film was visually evaluated by this treatment, and peeling was performed using a cellophane tape. ◎: There was no change in appearance, and no peeling was observed at all. 〇: There is no change in appearance, but a little peeling can be seen. X: There is a change in appearance, and a little peeling can be seen. Thermal stability For Resin 1, Resin 13 and Resin 14, fully ft trimethylolpropane triacrylate was added to the test tube. At the time when it reached no fluidity, it was shown as gelatinized in Table 3. The acidic degreasing solution is given to the catalyst (staining water washing step. (85 °C, pH = 1 0 ν ο 1 % sulfur plating step, after immersion in ί V ο 1 % aqueous solution, the coating after immersion in water, to evaluate the test from the test Mix 10 times of the evaluation time at 120 ° C. The result is -33- (31) 200836005 Comparative Example 2 Ο τ-Η Ο 00 (N τ-Η m Ο ο oo (N rH yr) in (N Ο τ -Η ο oo (N r - H Ο rH ο 00 (N ▼-H m 〇Ο Η ο 00 (N iH (N Ο ο 00 (N rH rH 00 Ο ο oo (N rH 实施 卜 Ο 1 —Η ο 00 CN VO Ό Ο 1—Η ο 00 (N ▼—H Ο 1—Η ο 00 CN 寸 inchΟ τ—Η ο 00 <N (Τ) ro Ο τ-Η ο 00 (N tH (N N τ Η ο 00 (N ^T) 1 -H Ο ο 00 (N rH ^Ti resin parts by weight ethyl cellosolve) S ^ advised f in in 2,2-_^methoxy-2-phenylacetone barium sulfate micropowder cerium oxide phthalocyanine green IlD^ ^ 'l1 it a dicyanodiamide resin (solid component) -34 - (32)200836005 Comparative Example ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ ◎ ◎ VO ○ ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ of of — H ◎ ◎ ◎ 〇〇 XX ◎ ◎ ◎ ◎ ◎ cn H 〇〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ r H r ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ^ Τ 1 1 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ (N ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Sense sensibility Touch dryness 20 minutes 40 minutes 50 minutes 60 minutes 70 minutes 80 minutes solder heat resistance solvent resistance Seven o Gold-plated resistant dry management range Μ ^ ife -35- 200836005 (33) [Table 3] Resin resin 1 Resin 13 Resin 14 Gelation 45 0 or more 3 60 points 1 90 points