200530353 (1) 九、發明說明 【發明所屬之技術領域】 本發明係有關一種製造印刷配線板時有用的光硬化 性·熱硬化性樹脂組成物，更詳言之，係有關具有經時安 定性優異的塗覆性，且耐熱性·密接性·電氣特性優異的 刷配線板用光硬化性•熱硬化性組成物，及使用其之印刷 配線板。 【先前技術】 由於最近半導體零件急速進步，故有電子機器小型輕 量化、高性能化、多功能化的傾向，伴隨此等要求進行印 刷配線板之高密度化。該印刷配線板所使用的阻焊劑，係 使用以紫外線圖案曝光、顯像以形成畫像，且以熱及光照 射加工硬化（本硬化）的液狀顯像型阻焊劑。此外，就考慮 環境問題而言，以使用稀鹼水溶液之鹼顯像型液狀阻焊劑 Φ 作爲顯像液（例如專利文獻1)爲主流。 該液狀阻焊劑，係在印刷配線板上藉由篩網印刷法、 簾幕塗覆法、噴霧塗覆法、輥塗覆法等全面塗覆光阻劑， 且爲使可接觸曝光時進行使有機溶劑揮發之假乾燥，然 後，曝光•顯像形成圖案，予以熱硬化，製得耐熱性•電 絕緣性優異的硬化塗膜。 然而，液狀阻焊劑對印刷配線板之塗覆性，會有經時 變化的問題。藉由該塗覆性之變化，銅箔端部變薄，電鍍 或焊接時產生剝落，引起外觀不佳情形。 -4- 200530353 (2) 一般而言，塗覆性可藉由配合二氧化矽、硫酸鋇、滑 石等之無機塡充劑或超微粉二氧化砂、有機皂土、鱲類等 之觸變性賦予劑（例如專利文獻2 )予以調整。然而，無機 塡充劑或超微粉二氧化矽，與有機溶劑或樹脂之親和性會 經時提高，且觸變性（以下稱爲觸變性）降低的問題。另 外，有機皂土雖經時變化情形少，惟多量使用時會有電絕 緣性降低的問題。此外，蠟類亦有含二甲苯等之有害有機 溶劑的問題。 [專利文獻1]日本特開平1 - 1 4 1 904號公報（申請專利 範圍） [專利文獻2 ]日本特開2 0 0 3 - 9 6 3 6 8號公報（申請專利 範圍） 【發明內容】 因此，本發明係爲解決習知技術具有的上述問題者， 其主要目的係提供一種對篩網印刷法、簾幕塗覆法、噴霧 塗覆法、輥塗覆法等而言，具有經時安定性的塗覆性，且 耐熱性·密接性•電絕緣性優異的印刷配線板用光硬化 性·熱硬化性組成物’及使用其之印刷配線板。 另外，提供一種可減少造成環境污染原因之有害物質 的光硬化性·熱硬化性組成物。 本發明人等爲達成上述目的，再三深入硏究檢討的結 果’發現在含有（A)—分子中具有1個以上羧基之含羧基 樹脂、（B)光聚合起始劑、（D)稀釋劑、（E)塡充劑、及（F) 200530353 (3) 環氧樹脂之組成物中，配合（c)聚羥基殘酸酯系添加劑之 光硬化性·熱硬化性樹脂組成物，對篩網印刷法、簾幕塗 覆法、噴霧塗覆法、輥塗覆法等而言，具有經時安定性之 塗覆性，且不會使耐熱性·密接性•電絕緣性等降低，遂 而完成本發明。 另外’發現上述（c)聚羥基羧酸酯系添加劑，沒有使 用二甲苯等有害的有機溶劑之必要性。 [發明效果] 本發明之光硬化性•熱硬化性組成物，對篩網印刷 法、簾幕塗覆法、噴霧塗覆法、輥塗覆法等而言，具有經 時安定性之塗覆性，且於製造印刷配線板時之電鍍處理時 或焊接時可防止塗膜剝落的不良品或塗膜下垂之外觀不良 品等情形，以及可在沒有含環境污染原因之有害有機溶劑 的揮發性有機化合物（VOC)下予以油墨化。 而且，由於具有經時安定的塗覆性，故可大量生產本 發明之光硬化性·熱硬化性樹脂組成物，降低成本。此 外’對降低製造印刷配線板時之不良率極有貢獻，且可使 製品低價格化。 [爲實施發明之最佳形態] 本發明之光硬化性·熱硬化性樹脂組成物的基本形 態’係提供一種光硬化性•熱硬化性樹脂組成物，其特徵 爲含有（A)—分子中具有1個以上羧基之含羧基樹脂、（B) 200530353 (4) 光聚合起始劑、（c)聚羥基殘酸醋系添加劑、（D)稀釋劑、 (E)塡充劑、及（F)環氧樹脂。較佳的形態係提供一種組成 物’其特徵爲上述（C)聚經基殘酸酯系添加劑不含二甲苯 (以下簡稱爲無二甲苯）之添加劑。而且，提供一種組成 物’其特徵爲上述光硬化性·熱硬化性樹脂組成物另含有 (G)非鹵素系有機顏料。 此外’另一形態係提供一種印刷配線板，其特徵爲使 上述光硬化性•熱硬化性樹脂組成物具有藉由活性能量線 照射及/或加熱、硬化所得的阻焊層及/或樹脂絕緣層。 於下述中’詳細說明有關本發明之光硬化性·熱硬化 性樹脂組成物之各構成成份。 首先’在上述（A)—分子中含有1個以上羧基之含羧 基樹脂，可使用具有羧基之樹脂，具體而言可使用（A，）本 身具有乙烯性不飽和雙鍵之含羧基的感光性樹脂及（A)不 含乙烯性不飽和雙鍵之含羧基的樹脂，沒有特別限制，惟 以使用下述列舉的樹脂（可爲寡聚物及聚合物）較佳。 (1) 藉由不飽和羧酸與具有不飽和雙鍵之化合物共聚 合，製得的含羧基之樹脂， (2) 藉由在不飽和羧酸與具有不飽和雙鍵之化合物的 共聚物中加成作爲側基之乙烯性不飽和基（例如加成甲基 丙烯酸環氧丙酯），製得的含羧基之感光性樹脂’ (3) 藉由在一分子中具有環氧基與不飽和雙鍵之化合 物及具有不飽和雙鍵之化合物的共聚物中，使不飽和單羧 酸反應，在生成的二級羧基中使飽和或不飽和多元酸酐反 200530353 (5) 應，製得的含羧基之感光性樹脂， (4) 在具有不飽和雙鍵之酸酐，與具有其他不飽和雙 鍵的化合物之共聚物中，使在一分子中具有羧基與不飽和 雙鍵之化合物反應，製得的含羧基之感光性樹脂， (5) 使多官能環氧化合物與不飽和單羧酸反應，在生 成的羧基中使飽和或不飽和多元酸酐反應，製得的含羧基 之感光性樹脂， (6) 在含羧基之聚合物中使飽和或不飽和多元酸酐反 應後，在生成的羧酸中使一分子中具有環氧基與不飽和雙 鍵之化合物反應，製得的含羥基及羧基之感光性樹脂， (7) 在多官能環氧化合物、與不飽和單羧酸、與在一 分子中至少具有1個醇性羥基、及具有1個除與環氧基反 應的醇性羥基以外之反應性基的反應生成物中，使飽和或 不飽和多元酸酐反應製得的含羧基之感光性樹脂， (8) 對在一分子中至少具有2個氧雜環丁烷環之多官 能氧雜環丁烷化合物中使不飽和單羧酸反應所得的改性氧 雜環丁烷樹脂中之一級羥基而言，使飽和或不飽和多元酸 酐反應製得的含羧基之感光性樹脂等。 於此等之中，以在一分子中具有2個以上感光性不飽 和雙鍵的含羧基之感光性樹脂，尤以上述（5)含羧基之感 光性樹脂較佳。 上述（A)含竣基之樹脂，由於主鍵（backbone)·聚合物 之側鏈上具有多數游離的羧基，故可藉由稀鹼水溶液顯 像。 - 8- 200530353 (6) 此外，上述（A)含羧基之樹脂的酸價爲 40〜 200mgKOH/g，較佳者爲 45〜120mgKOH/g。含羧基之樹 脂的酸價小於40mgKOH/g時不容易鹼顯像，另外，大於 2 00mgKOH/g時由於藉由顯像進行曝光部之溶解，致使線 條較必要以上者爲細，視其所需在沒有區別曝光部與未曝 光部下以顯像液溶解剝離，不易描繪正常的光阻圖案，故 不爲企求。 該（A)含羧基之樹脂的配合量，在全部組成物中爲20 〜60質量％，較佳者爲 3 0〜5 0質量％。小於上述範圍 時，塗膜強度降低，不爲企求。另外，大於上述範圍時， 黏性增高且印刷性等降低，不爲企求。 本發明所使用的（B)光聚合起始劑，例如有苯偶因、 苯偶因甲醚、苯偶因***、苯偶因異丙醚等之苯偶因與苯 偶因烷醚類；苯乙酮、2，2·二甲氧基-2-苯基苯乙酮、2，2-二乙氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、 1，1-二氯化苯乙酮等之苯乙酮類；2-甲基-卜[4-(甲基硫化） 苯基：1-2-嗎啉基丙-1-酮、2-苯甲基-2-二甲基胺基-1-(4-嗎 啉基苯基）-丁酮-1等之胺基苯乙酮類；2-甲基蒽醌、2-乙 基蒽醌、2-第3-丁基蒽醌、1·氯化蒽醌等之蒽醌類；2,4-二甲基噻噸酮、2,4·二乙基噻噸酮、2-氯化噻噸酮、2,4-二異丙基噻噸酮等之噻噸酮類；苯乙酮二甲縮醛、苯甲基 二甲基縮醛等之縮醛類；二苯甲酮等之二苯甲酮類；或咕 噸酮類；（2,6-二甲氧基苯甲醯基）-2,4,4-戊基氧化膦、雙 (2,4,6-三甲基苯甲醯基）-苯基氧化膦、2,4,6-三甲基苯甲 200530353 (7) 醯基二苯基氧化膦、乙基-2，4,6-三甲基苯甲醯基苯基磷酸 酯等之氧化膦類；各種過氧化物類等，此等習知慣用的光 聚合起始劑可單獨使用或2種以上組合使用。此等（B)光 聚合起始劑之配合量，在全部組成物中爲0.2〜10質量 %，較佳者爲0.5〜5質量％。上述配合量小於組成物全體 量之0.2質量％時，光硬化性降低且於曝光•顯像後不易 形成圖案，故不爲企求。另外，大於1 〇質量％時，藉由 | 光游離聚合起始劑本身之光吸收，造成厚膜硬化性降低且 爲成本提高的原因，故不爲企求。 上述（B)光聚合起始劑，可與N，N-二甲基胺基苯甲酸 乙酯、N，N-二甲基胺基苯甲酸異戊酯、戊基-4-二甲基胺 基苯甲酸酯、三乙胺、三乙醇胺等之三級胺類的光增感劑 單獨或2種以上組合使用。 此外，可組合在可視光範圍內以游離基聚合爲開始的 千葉•特殊•化學公司製衣魯卡奇亞（音譯）7 84等之吉塔 φ 羅仙（音譯）系光聚合起始劑、羅衣克（音譯）染料等作爲硬 化助劑使用。 本發明特徵之（C)聚羥基羧酸酯系添加劑，例如由二 羧酸二甲酯等之二羧酸二烷酯與鏈烷醇胺類之酯交換反應 所合成者，具體例如比克（音譯）化學·日本公司製之 BYK-R606 等。 該聚羥基羧酸酯與習知的聚羧酸醯胺系添加劑不同， 係藉由含有羥基（例如第1圖中約3 4 3 0 c m ·1的吸收）及酯鍵 (例如第1圖中約1 74 0 cm·1的吸收），可溶於異丁醇等之醇 -10 - 200530353 (8) 類，不需使用如二甲苯等之有害揮發性有機化合物 (VOC)。另外，可使用較習知的聚羧酸醯胺爲少量（約1/5 〜1 /3之量），賦予經時安定性優異的觸變性。此係習知的 聚羧酸醯胺爲蠟狀，對沒有均勻分散而言，本發明之聚羥 基羧酸酯由於在組成物中可均勻分散，故可以少量賦予優 異的觸變性。 而且，該聚羥基羧酸酯不僅可作爲觸變性賦予劑，且 g 可藉由控制配合量（例如在組成物中約配合0.2質量％以 上），亦可使用作爲無光澤化劑（消艷劑）。 該（C)聚羥基羧酸酯系添加劑之配合量，在全部組成 物中爲0.01〜1 ·00質量％、較佳者爲〇.〇5〜0.8質量％。 (C)聚羥基羧酸酯系添加劑之配合量小於上述範圍時，無 法得到充分的觸變性。另外大於上述範圍時，由於會產生 針孔或間斷情形，不爲企求。 此外’該聚羥基羧酸酯系添加劑，藉由倂用親水性二 φ 氧化矽’可形成網目構造且提高觸變性，更爲提高效果之 安定性。 本發明所使用的（D)稀釋劑，係爲調整該組成物之黏 度、提高作業性’且提高交聯密度、提高密接性等時所使 用者’可使用光聚合性單體等之反應性稀釋劑或習知慣用 的有機溶劑。 上述光聚合性單體例如有2 -乙基己基（甲基）丙烯酸 醋、環己基（甲基）丙烯酸酯等之烷基（甲基）丙烯酸酯類； 2-羥基乙基（甲基）丙烯酸酯、2_羥基丙基（甲基）丙烯酸酯 -11 - 200530353 (9) 等之羥基烷基（甲基）丙烯酸酯類；乙二醇、丙二醇、二乙 二醇、二丙二醇等之環氧烷基衍生物的單或二（甲基）丙烯 酸酯類；己二醇、三羥甲基丙烷、季戊四醇、二三羥甲基 丙烷、二季戊四醇、參羥基乙基異氰酸酯等之多元醇或此 等之環氧乙烷或環氧丙烷加成物的多元（甲基）丙烯酸酯 類；苯氧基乙基（甲基）丙烯酸酯、雙酚 A之聚乙氧基二 (甲基）丙烯酸酯等之苯酚類的環氧乙烷或環氧丙烷加成物 之（甲基）丙烯酸酯類；丙三醇二環氧丙醚、三羥甲基丙烷 三環氧丙醚、三環氧丙基異氰酸酯等之環氧丙醚的（甲基） 丙烯酸酯類；以及蜜胺（甲基）丙烯酸酯等。 此等可以單獨使用或2種以上組合使用，就組成物之 液體安定性而言以含親水性基之（甲基）丙烯酸酯類較佳， 另就光硬化性而言以多官能性之（甲基）丙烯酸酯類較佳。 此等光聚合單體之使用範圍在全部組成物中爲20質量％ 以下，較佳者爲1 〇質量％以下。大於該範圍時，指觸乾 燥性不佳，故不爲企求。 而且，於本說明書中（甲基）丙烯酸酯係爲丙烯酸酯、 甲基丙烯酸酯及此等之混合物的總稱，有關其他類似的表 示亦相同。 上述有機溶劑可使用甲基乙酮、環己酮等之酮類；甲 苯、二甲苯、四甲苯等之芳香族烴類；溶纖劑、甲基溶纖 劑、丁基溶纖劑、卡必醇、甲基卡必醇、丁基卡必醇、丙 二醇單甲醚、二丙二醇單甲醚、二丙二醇二***、三丙二 醇單甲醚等之醇醚類；醋酸乙酯、醋酸丁酯、乳酸丁酯' -12 - 200530353 (ίο) 溶纖劑乙酸酯、丙二醇單甲醚乙酸酯、二丙二醇單甲醚乙 酸酯、碳酸丙二酯等之酯類；辛烷、癸烷等之脂肪族烴 類；石油醚、石腦油、溶劑石腦油等之石油系溶劑等習知 的有機溶劑。此等有機溶劑可以單獨使用或二種以上組合 使用。 該有機溶劑之使用量係視塗覆方法或使用的有機溶劑 之沸點而不同’沒有特別的限制，一般而言在全部組成物 中爲50質量％以下’較佳者爲30質量％以下，更佳者爲 2 0質量％以下。含有多量的高沸點有機溶劑時，指觸乾燥 性降低且於塗覆後直至假乾燥前會產生皺摺情形，故不爲 企求。 本發明所使用的（E)塡充劑，可使用習知的無機塡充 劑或有機塡充劑，以倂用上述（C)聚羥基羧酸酯系添加劑 時，具有形成網目構造且提高觸變性、提高效果安定性作 用之親水性二氧化矽較佳。 而且，此處之親水性二氧化矽係爲使一般的二氧化矽 所粉碎者，除使粒子表面以有機化合物疏水化處理者（疏 水性二氧化矽）以外者。 除親水性二氧化矽以外之無機塡充物，可使用硫酸 鋇、滑石、黏土、疏水性二氧化矽、氧化鋁、氫氧化鋁、 碳酸鈣、有機皂土、雲母粉等之習知慣用者。此等具有提 高塗膜之強度或硬度的效果，可視其所需使用。 另外，上述有機塡充物例如聚乙烯、聚丙烯、聚苯乙 烯、丙烯腈-苯乙烯共聚物、丙烯腈-丁二烯-苯乙烯共聚 -13- 200530353 (11) 物、聚碳酸酯、聚甲基丙烯酸甲酯等之各種丙烯酸酯、聚 醯亞胺、聚醯胺、聚酯、聚氯化乙烯基、聚氯化次乙烯 基、聚二乙烯苯、氟系樹脂、聚氧化亞苯基、聚硫化亞苯 基、聚甲基戊烯 '尿素樹脂、蜜胺樹脂、苯并鳥糞胺樹 脂、聚縮醛樹脂、呋喃樹脂、聚矽氧烷樹脂、環氧樹脂硬 化物等。 此等（E)塡充劑之配合量，在全部組成物中爲40質量 %以下、較佳者爲5〜3 0質量％。塡充劑之配合比例大於 上述範圍時，塗膜特性降低且不易得到充分的印刷性，故 不爲企求。該（E)塡充劑亦具有防止銅箔端部等之塗膜變 爲極薄的作用，以適量配合具有1 〇 μπι以下粒徑者較佳。 本發明之（F)環氧樹脂可使用習知的各種環氧樹脂， 例如雙酚Α型環氧樹脂、雙酚F型環氧樹脂、雙酚S型 環氧樹脂、溴化雙酚A型環氧樹脂、加氫雙酚A型環氧 樹脂、雙酚型環氧樹脂、雙二甲苯酚型環氧樹脂、苯酚酚 醛淸漆型環氧樹脂、甲酚酚醛淸漆型環氧樹脂、溴化苯酚 酚醛淸漆型環氧樹脂、雙酚A之酚醛淸漆型環氧樹脂、 三羥基苯基甲烷型環氧樹脂、四羥苯基乙烷型環氧樹脂、 含萘架構之苯酚酚醛淸漆型環氧樹脂、含二環戊二烯架構 之苯酚酚醛淸漆型環氧樹脂等之環氧丙醚化合物；對酞酸 二環氧丙酯、六氫酞酸二環氧丙酯、二聚酸二環氧丙酯等 之環氧丙酯化合物；賴西魯（音譯）化學公司製之Ε Η P E -3 1 5 0等脂環式環氧樹脂；三環氧丙基異氰酸酯等之雜環 式環氧樹脂；Ν;Ν，Ν’，Ν’ -四環氧丙基間二甲苯二胺、 -14 - 200530353 (12) N，N，N’，N5-四環氧丙基雙胺基甲基環己烷、N，N-二環氧丙 基苯胺等之環氧丙胺類、或環氧丙基（甲基）丙烯酸酯與具 有乙烯性不飽和雙鍵之化合物的共聚物等習知之環氧化合 物，就指觸乾燥性、耐熱性而言由以苯酚酚醛淸漆型環氧 樹脂、甲酚酚醛淸漆型環氧樹脂、雙酚型或雙二甲苯酚型 環氧樹脂或此等之混合物或三環氧丙基異氰酸酯更佳。此 等之（F)環氧樹脂可以單獨使用或2種以上組合使用。 $ 此等之（F)環氧樹脂與上述（A)含羧基之樹脂熱硬化， 可提高耐熱性、密接性等。此等（F)環氧樹脂之配合量， 對上述（A)含羧基之樹脂的1當量羧基而言，環氧基爲〇.8 〜2.0當量、較佳者爲1.0〜1.8當量。（F)環氧樹脂之配合 量於環氧基小於< 0 · 8當量時，殘留有未反應的羧基，且硬 化被膜之吸濕性增高，P C T耐性容易降低，且焊接耐熱性 或耐無電鍍性亦容易降低。此外，（F)環氧樹脂之配合量 於環氧基大於2 · 0當量時，塗膜之顯像性或硬化被膜之耐 φ 無電鍍性不佳，且pct耐性亦不佳。 本發明之光硬化性·熱硬化性樹脂組成物，可視其所 需以無機顏料、有機顏料、有機染料等著色，由於有機染 料爲引起感度降低的原因’故以使用無機顏料或有機顏料 較佳。具體而言，例如酞菁·藍、酞菁•綠、碘·綠、二 重氮黃、結晶紫、氧化鈦、碳黑、萘黑等。另外，就環境 問題而言以使用（G)非鹵素系有機顏料較佳。 此等顏料類之配合量除氧化鈦外，一般而言在組成物 中爲5質量％以下。若大於上述範圍時，光硬化性降低， -15- (13) (13)200530353 不爲企求。而且，使用氧化鈦時，一般在組成物中使用 1 5質量％以下。 另外’本發明之光硬化性·熱硬化性樹脂組成物，可 添加咪唑鹽類或三氟化硼複合物、有機金屬鹽等作爲潛在 性硬化觸媒。此外，就防止印刷配線板之電路、即銅之氧 化爲目的時，可添加腺嘌呤、乙烯基三嗪、二氰基二醯 胺、正甲苯基縮二胍、蜜胺等之化合物、或此等之鹽。一 般而言，此等化合物之配合比例在組成物中爲5質量％以 下，藉由添加此等，可提高硬化塗膜之耐藥品性或與銅箔 之黏合性。 此外，本發明之光硬化性·熱硬化性樹脂組成物，在 不會降低塗膜特性之範圍內，視其所需可添加氫醌、氫醌 單甲醚、第3 -丁基兒茶酚、焦培酚、吩噻嗪等習知之熱 聚合禁止劑、聚矽氧烷系、氟系、高分子系等之消泡劑及 /或水平劑、咪唑系、噻唑系、***系等之矽烷偶合劑等 習知的添加劑類。 具有上述組成之本發明光硬化性•熱硬化性樹脂組成 物，視其所需予以稀釋調整成適合塗覆方法的黏度，使其 藉由篩網印刷法、簾幕塗覆法、分布塗覆法、輥塗覆法等 之方法塗覆於例如形成有電路的印刷配線板上，藉由在例 如6 0〜1 0 0 t之溫度下使組成物中所含的有機溶劑揮發乾 燥，形成沒有皺摺的塗膜。 然後，使形成有所定圖案的光罩通過，藉由選擇性活 性能量線曝光，使未曝光部藉由稀鹼水溶液顯像，形成光 -16- 200530353 (14) 阻圖案，然後，照射活性能量線後加熱硬化，或加熱硬化 後照射活性能量線，或僅以加熱硬化予以最後的加工硬化 (本硬化），可形成密接性、硬度、焊接耐熱性、耐藥品 牲、耐溶劑性、電絕緣性、耐電蝕性、解像性、耐電鍍 牲、pct耐性、及耐吸濕性優異的硬化被膜（阻焊被膜）。 特別是藉由照射活性能量線後加熱硬化，或加熱硬化後照 射活性能量線之步驟，使未反應的感光基反應，可製得耐 電蝕性、耐電鍍性、耐吸濕性優異的硬化被膜。 上述顯像所使用的鹼水溶液可使用氫氧化鉀、氫氧化 鈉、碳酸鈉、碳酸鉀、磷酸鈉、矽酸鈉、銨、胺類等之鹼 水溶液。而且，爲使光硬化時之照射光源以低壓水銀燈、 中壓水銀燈、高壓水銀燈、超高壓水銀燈、氙氣燈、金屬 •鹵化燈等爲宜。其他可利用雷射光線等作爲活性能量線。 【實施方式】 [實施例] 於下述中以實施例及比較例具體說明有關本發明，惟 本發明不受下述實施例所限制。而且，於下述中沒有特別 限制時，「份」係全部表示「質量份」。 合成例 使215份甲酚酚醛淸漆型環氧樹脂之N-680(大日本 油墨化學工業公司製、環氧當量=2 1 5)加入附有攬拌機及 回流冷卻器之四口燒瓶中，再加入196份丙二.醇單甲醚乙 -17- 200530353 (15) 酸酯予以加熱熔融。然後，加入0.46份作爲聚合禁止劑 之甲基氫醒、1 . 3 8份作爲反應觸媒之三苯基膦。使該混合 物在9 5〜1 0 5 t：下加熱，慢慢地滴入7 2.0份（1 · 0當量）丙 烯酸，製得酸價爲〇.9mgKOH/g之反應生成物。使該反應 生成物（羥基：1當量）冷卻至80〜90 °C，加入76.0份（0.5 當量）四氫酞酸酐，約反應8小時，冷卻後取出。如此所 得的（A)含羧基之樹脂係不揮發份爲65%、固成分之酸價 爲7 7mgKOH/g。於下述中，該淸漆稱爲A-1淸漆。 使上述合成例所得的含羥基之樹脂淸漆（A-1淸漆）使 用的表1所示配合比例，以3條輥磨混練，製得光硬化 性•熱硬化性樹脂組成物之各主劑。另外，使表2所示之 配合比例以3條輥磨混練，製得上述光硬化性•熱硬化性 樹脂組成物之硬化劑。 而且’所得的光硬化性·熱硬化性樹脂組成物，以丙 二醇單甲醚乙酸酯調整成黏度約爲200dPa · s。200530353 (1) IX. Description of the invention [Technical field to which the invention belongs] The present invention relates to a photocurable and thermosetting resin composition useful in the manufacture of printed wiring boards, and more specifically, it relates to stability with time. Photocurable and thermosetting composition for brush wiring boards having excellent coating properties and heat resistance, adhesion, and electrical characteristics, and printed wiring boards using the same. [Prior art] Due to recent rapid advances in semiconductor components, there is a tendency to reduce the size, weight, performance, and versatility of electronic equipment, and to increase the density of printed wiring boards with these requirements. The solder resist used in this printed wiring board is a liquid development type solder resist that is exposed and developed with an ultraviolet pattern to form an image, and processed and hardened (this hardening) by heat and light. In consideration of environmental issues, an alkali developing type liquid solder resist Φ using a dilute aqueous alkali solution is used as a developing solution (for example, Patent Document 1). This liquid solder resist is applied on the printed wiring board by screen printing method, curtain coating method, spray coating method, roll coating method and the like, and is applied when the exposure is possible. After the organic solvent is volatilized and dried, it is exposed and developed to form a pattern, and then heat-cured to obtain a cured coating film having excellent heat resistance and electrical insulation. However, there is a problem that the coating property of the liquid solder resist to the printed wiring board changes with time. Due to this change in coatability, the end of the copper foil becomes thinner, and peeling occurs during plating or soldering, resulting in poor appearance. -4- 200530353 (2) Generally speaking, the coating properties can be imparted by the thixotropy of inorganic fillers such as silicon dioxide, barium sulfate, and talc, or ultra-fine powdered sand dioxide, organic bentonite, and concrete. Agent (for example, Patent Document 2). However, the inorganic rhenium filler or ultra-fine powdered silica has a problem that the affinity with organic solvents or resins increases over time and the thixotropy (hereinafter referred to as thixotropy) decreases. In addition, although organic bentonite has few changes over time, there is a problem that the electrical insulation is reduced when it is used in a large amount. In addition, waxes have the problem of harmful organic solvents containing xylene and the like. [Patent Document 1] Japanese Patent Laid-Open No. 1-1 4 1 904 (Scope of Patent Application) [Patent Literature 2] Japanese Patent Laid-Open No. 2 0 3-9 6 3 6 8 (Scope of Patent Application) [Contents of the Invention] Therefore, the present invention is to solve the above-mentioned problems of the conventional technology, and its main object is to provide a screen printing method, a curtain coating method, a spray coating method, a roll coating method, etc. Photocurable and thermosetting composition for printed wiring boards having stable coating properties and excellent heat resistance, adhesion, and electrical insulation, and printed wiring boards using the same. In addition, it provides a photocurable and thermosetting composition that can reduce harmful substances that cause environmental pollution. In order to achieve the above-mentioned object, the present inventors have repeatedly studied the results of the review and found that the carboxyl group-containing resin containing (A) -molecules having more than one carboxyl group, (B) a photopolymerization initiator, and (D) a diluent , (E) Rhenium Filler, and (F) 200530353 (3) Photocuring and thermosetting resin composition of (c) polyhydroxy residual acid ester type additive in epoxy resin composition. The printing method, curtain coating method, spray coating method, roll coating method, etc. have stable coating properties over time without reducing heat resistance, adhesion, and electrical insulation. The present invention has been completed. In addition, it was found that the (c) polyhydroxycarboxylic acid ester-based additive does not require the use of harmful organic solvents such as xylene. [Effects of the Invention] The photo-curable and thermo-curable composition of the present invention has a stable coating over time for screen printing, curtain coating, spray coating, and roll coating. In addition, it can prevent the defective products such as peeling of the coating film or the appearance of the drooping coating film during the electroplating process or soldering during the manufacture of printed wiring boards, and the volatility of harmful organic solvents without environmental pollution causes. Ink is applied under organic compounds (VOC). In addition, since it has stable coating properties over time, the photocurable and thermosetting resin composition of the present invention can be mass-produced and the cost can be reduced. In addition, it greatly contributes to reducing the defective rate in the manufacture of printed wiring boards, and can reduce the price of products. [The best form for carrying out the invention] The basic form of the photocurable and thermosetting resin composition of the present invention is to provide a photocurable and thermosetting resin composition, which is characterized by containing (A)-in the molecule A carboxyl group-containing resin having one or more carboxyl groups, (B) 200530353 (4) a photopolymerization initiator, (c) a polyhydroxy acid residue vinegar-based additive, (D) a diluent, (E) a filler, and (F ) Epoxy resin. A preferred aspect is to provide a composition 'characterized in that the (C) polyacrylic acid residue-based additive does not contain xylene (hereinafter referred to as xylene-free) additive. Furthermore, there is provided a composition 'characterized in that the photocurable and thermosetting resin composition further contains (G) a non-halogen-based organic pigment. In addition, another aspect provides a printed wiring board characterized in that the photocurable and thermosetting resin composition has a solder resist layer and / or resin insulation obtained by irradiation with active energy rays and / or heating and curing. Floor. Each component of the photocurable and thermosetting resin composition of the present invention will be described in detail below. First, the carboxyl group-containing resin containing one or more carboxyl groups in the above (A) -molecule. A resin having a carboxyl group can be used, and specifically, (A,) a carboxyl group-containing photosensitivity having an ethylenically unsaturated double bond can be used. The resin and (A) a carboxyl group-containing resin not containing an ethylenically unsaturated double bond are not particularly limited, but the resins listed below (which may be oligomers and polymers) are preferably used. (1) A carboxyl group-containing resin prepared by copolymerizing an unsaturated carboxylic acid and a compound having an unsaturated double bond, (2) By using a copolymer of an unsaturated carboxylic acid and a compound having an unsaturated double bond Addition of an ethylenically unsaturated group as a side group (for example, addition of propylene methacrylate) to a carboxyl group-containing photosensitive resin '(3) By having an epoxy group and an unsaturated group in one molecule In a copolymer of a compound having a double bond and a compound having an unsaturated double bond, an unsaturated monocarboxylic acid is reacted, and a saturated or unsaturated polybasic acid anhydride is reacted in the secondary carboxyl group formed. Carboxyl photosensitive resin, (4) In a copolymer of an acid anhydride having an unsaturated double bond and a compound having another unsaturated double bond, a compound having a carboxyl group and an unsaturated double bond in one molecule is reacted to obtain (5) a carboxyl group-containing photosensitive resin, (5) reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid and reacting a saturated or unsaturated polybasic acid anhydride in the generated carboxyl group, ( 6) Polymerization with carboxyl groups After reacting a saturated or unsaturated polybasic acid anhydride, a compound having an epoxy group and an unsaturated double bond in one molecule is reacted in the generated carboxylic acid to prepare a photosensitive resin containing a hydroxyl group and a carboxyl group. (7) in A polyfunctional epoxy compound, a reaction product with an unsaturated monocarboxylic acid, a reaction product having at least one alcoholic hydroxyl group in one molecule, and a reactive group other than an alcoholic hydroxyl group that reacts with an epoxy group , A carboxyl group-containing photosensitive resin prepared by reacting a saturated or unsaturated polybasic acid anhydride, (8) Unsaturation in a polyfunctional oxetane compound having at least two oxetane rings in one molecule As for the primary hydroxyl group in the modified oxetane resin obtained by the reaction of a monocarboxylic acid, a carboxyl group-containing photosensitive resin or the like obtained by reacting a saturated or unsaturated polybasic acid anhydride. Among these, a carboxyl group-containing photosensitive resin having two or more photosensitive unsaturated double bonds in one molecule is preferable, and the above (5) carboxyl group-containing photosensitive resin is more preferable. The above (A) radical-containing resin has a plurality of free carboxyl groups on the side chain of the backbone and the polymer, and thus can be imaged by a dilute aqueous alkali solution. -8- 200530353 (6) In addition, the acid value of the (A) carboxyl group-containing resin is 40 to 200 mgKOH / g, preferably 45 to 120 mgKOH / g. When the acid value of the carboxyl-containing resin is less than 40 mgKOH / g, alkali development is not easy. In addition, when the acid value is more than 200 mgKOH / g, the exposure portion is dissolved by development, which makes the line more necessary. There is no difference between the exposed part and the unexposed part by dissolving and peeling in the developing solution, and it is not easy to draw a normal photoresist pattern, so it is not desirable. The compounding amount of the (A) carboxyl group-containing resin is 20 to 60% by mass, and more preferably 30 to 50% by mass in the entire composition. If it is smaller than the above range, the strength of the coating film is reduced, which is not desirable. Moreover, when it is larger than the said range, viscosity will increase and printability etc. will fall, and it is not desirable. (B) Photopolymerization initiators used in the present invention include, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin alkyl ethers; Acetophenone, 2,2 · dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-benzene Acetophenones such as acetophenone, 1,1-dichloroacetophenone; 2-methyl-bu [4- (methylsulfide) phenyl: 1-2-morpholinylpropan-1- Ketones, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butanone-1 and other aminoacetophenones; 2-methylanthraquinone, 2- Anthraquinones such as ethyl anthraquinone, 2-three-butylanthraquinone, and 1. · anthraquinone chloride; 2,4-dimethylthioxanthone, 2,4 · diethylthioxanthone, 2 -Thioxanthone, such as thioxanthone chloride, 2,4-diisopropylthioxanthone; acetals such as acetophenone dimethyl acetal, benzyl dimethyl acetal, etc; Ketones and other benzophenones; or Gutanones; (2,6-dimethoxybenzyl) -2,4,4-pentylphosphine oxide, bis (2,4,6-tri Methyl benzamidine) -phenylphosphine oxide, 2,4,6-trimethylbenzyl 200530353 (7) fluorenyl diphenyl phosphine oxide, -2,4,6-trimethylbenzylidenephenyl phosphate and other phosphine oxides; various peroxides, etc. These conventional photopolymerization initiators can be used alone or in combination of two or more kinds. Use in combination. The blending amount of these (B) photopolymerization initiators is 0.2 to 10% by mass, and more preferably 0.5 to 5% by mass in the entire composition. When the above-mentioned compounding amount is less than 0.2% by mass of the total amount of the composition, the photocurability is lowered and it is difficult to form a pattern after exposure and development, so it is not desirable. In addition, if it is more than 10% by mass, it is not desirable because the light absorption of the photo-free polymerization initiator itself reduces the thick film hardenability and increases the cost. The above (B) photopolymerization initiator can be used with ethyl N, N-dimethylaminobenzoate, isoamyl N, N-dimethylaminobenzoate, and pentyl-4-dimethylamine. Tertiary amine photosensitizers such as benzoate, triethylamine, and triethanolamine are used alone or in combination of two or more. In addition, Chiba • Specialty • Chemical Co., Ltd. Lukachia (Transliteration) 7 84 can be combined in combination with Chita φ Luoxian (transliteration) photopolymerization initiator, Royco dyes are used as hardening aids. The (C) polyhydroxycarboxylic acid ester-based additive, which is a feature of the present invention, is synthesized by a transesterification reaction of a dicarboxylic acid dialkyl ester such as dimethyl dicarboxylic acid and an alkanolamine. Transliteration) Chemicals, BYK-R606, etc. made by a Japanese company. This polyhydroxycarboxylic acid ester is different from the conventional polycarboxylic acid ammonium-based additives by containing a hydroxyl group (for example, absorption of about 3 4 3 0 cm · 1 in the first figure) and an ester bond (for example, in the first figure Absorption of about 174 0 cm · 1), soluble in alcohols such as isobutanol-10-200530353 (8), without using harmful volatile organic compounds (VOC) such as xylene. In addition, a small amount (about 1/5 to 1/3) of a conventional polycarboxylic acid ammonium amine can be used to impart thixotropy with excellent stability over time. The conventional polycarboxylic acid ammonium amine is waxy. As far as it is not uniformly dispersed, the polyhydroxycarboxylic acid ester of the present invention can be uniformly dispersed in the composition, so it can impart a small amount of excellent thixotropy. In addition, the polyhydroxycarboxylic acid ester can be used not only as a thixotropy-imparting agent, but also by controlling the blending amount (for example, about 0.2% by mass or more in the composition), and it can also be used as a matting agent (brightening agent). ). The compounding amount of the (C) polyhydroxycarboxylic acid ester-based additive is 0.01 to 1.00% by mass, and more preferably 0.05 to 0.8% by mass in the entire composition. (C) When the blending amount of the polyhydroxycarboxylic acid ester-based additive is smaller than the above range, sufficient thixotropy cannot be obtained. If it is larger than the above range, pinholes or discontinuities may occur, which is not desirable. In addition, 'the polyhydroxycarboxylic acid ester-based additive, by using a hydrophilic di φ silica', can form a mesh structure, improve thixotropy, and further improve the stability of the effect. The (D) diluent used in the present invention is used to adjust the viscosity of the composition, improve workability, and increase the crosslinking density, adhesion, etc. The user can use the reactivity of photopolymerizable monomers, etc. Diluents or conventional organic solvents. Examples of the photopolymerizable monomer include alkyl (meth) acrylates such as 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate; 2-hydroxyethyl (meth) acrylic acid Ester, 2-hydroxypropyl (meth) acrylate 11-200530353 (9) and other hydroxyalkyl (meth) acrylates; ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, etc. epoxy Mono- or di (meth) acrylates of alkyl derivatives; hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, parahydroxyethyl isocyanate, etc., or these Poly (meth) acrylates of ethylene oxide or propylene oxide adducts; phenoxyethyl (meth) acrylate, polyethoxydi (meth) acrylate of bisphenol A, etc. (Meth) acrylates of phenolic ethylene oxide or propylene oxide adduct; glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanate Glycidyl (meth) acrylates; and melamine (meth) acrylic acid Wait. These can be used singly or in combination of two or more kinds. In terms of liquid stability of the composition, (meth) acrylic acid esters containing a hydrophilic group are preferred, and in terms of photohardenability, polyfunctional ( Methacrylates are preferred. The use range of these photopolymerizable monomers is 20% by mass or less, and more preferably 10% by mass or less in the entire composition. Above this range, the dryness of the fingers is not good, so it is not desirable. Moreover, in this specification, (meth) acrylate is a generic term for acrylate, methacrylate, and mixtures thereof, and other similar expressions are also the same. As the organic solvent, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetra toluene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, Alcohol ethers such as methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, and tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate '-12-200530353 (ίο) Cellulose acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene carbonate and other esters; octane, decane and other aliphatic Hydrocarbons; conventional organic solvents such as petroleum solvents such as petroleum ether, naphtha, solvent naphtha, etc. These organic solvents may be used alone or in combination of two or more. The amount of the organic solvent used is different depending on the coating method or the boiling point of the organic solvent used. “There is no particular limitation, but it is generally 50% by mass or less in the entire composition.” Preferably it is 30% by mass or less. It is preferably 20% by mass or less. When a large amount of a high-boiling-point organic solvent is contained, it is not desirable to reduce the dryness to the touch and to wrinkle after coating and before false drying. The (E) samarium filler used in the present invention may be a conventional inorganic or organic samarium filler, and when the above (C) polyhydroxycarboxylic acid ester-based additive is used, it has a mesh structure and improves contact. Hydrophilic silica with better denaturation and stabilization effect is preferred. In addition, the hydrophilic silica here is the one that pulverizes ordinary silica, except that the surface of the particles is hydrophobized with an organic compound (hydrophobic silica). For inorganic fillers other than hydrophilic silica, it is possible to use those who are familiar with barium sulfate, talc, clay, hydrophobic silica, alumina, aluminum hydroxide, calcium carbonate, organic bentonite, mica powder, etc. . These have the effect of improving the strength or hardness of the coating film, and can be used as required. In addition, the above organic filler is, for example, polyethylene, polypropylene, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer-13-200530353 (11), polycarbonate, poly Various acrylates such as methyl methacrylate, polyimide, polyimide, polyester, polyvinyl chloride, polychlorinated vinylidene, polydivinylbenzene, fluorine resin, polyoxyphenylene , Polyphenylene sulfide, polymethylpentene 'urea resin, melamine resin, benzoguanamine resin, polyacetal resin, furan resin, polysiloxane resin, hardened epoxy resin, and the like. The compounding amount of these (E) gadolinium fillers is 40% by mass or less, preferably 5 to 30% by mass in the entire composition. When the mixing ratio of the filler is larger than the above range, the coating film characteristics are lowered and sufficient printability is not easily obtained, so it is not desirable. This (E) concrete filler also has the effect of preventing the coating film of copper foil ends and the like from becoming extremely thin, and it is preferable to mix a suitable amount with a particle size of 10 μm or less. The (F) epoxy resin of the present invention can use various conventional epoxy resins, such as bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and brominated bisphenol A epoxy resin. Epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol epoxy resin, bisxylenol epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bromine Phenol novolac lacquer type epoxy resin, bisphenol A novolac lacquer type epoxy resin, trihydroxyphenylmethane type epoxy resin, tetrahydroxyphenylethane type epoxy resin, phenol novolac with naphthalene structure Lacquer-type epoxy resin, phenol novolac lacquer-type epoxy resin containing dicyclopentadiene structure, etc. Glycidyl ether compounds; diglycidyl phthalate, diglycidyl hexahydrophthalate, Polypropylene oxide compounds such as polyglycidyl; alicyclic epoxy resins such as E Η PE -3 1 50 by Laixiro Chemical Co., Ltd .; miscellaneous materials such as triglycidyl isocyanate Cyclic epoxy resin; N; N, N ', N'-tetraepoxypropyl-m-xylylenediamine, -14-200530353 (12) N, N, N', N5 -Tetra-glycidyl diaminomethylcyclohexane, N, N-glycidyl aniline, etc., or glycidyl (meth) acrylate and ethylenically unsaturated bis Conventional epoxy compounds such as copolymers of bonded compounds are made of phenol novolac lacquer type epoxy resin, cresol novolac lacquer type epoxy resin, bisphenol type or bisphenol type in terms of touch dryness and heat resistance. A cresol-type epoxy resin or a mixture thereof or a triglycidyl isocyanate is more preferable. These (F) epoxy resins can be used alone or in combination of two or more. (These (F) epoxy resins and the (A) carboxyl group-containing resins are thermally cured to improve heat resistance and adhesion.) The compounding amount of these (F) epoxy resins is, for one equivalent of the carboxyl group of the above (A) carboxyl group-containing resin, an epoxy group of 0.8 to 2.0 equivalents, preferably 1.0 to 1.8 equivalents. (F) When the compounding amount of epoxy resin is less than < 0 · 8 equivalents, unreacted carboxyl groups remain, and the hygroscopicity of the cured film is increased, the PCT resistance is easily reduced, and the soldering heat resistance or resistance Plating properties are also easily reduced. In addition, when the compounding amount of (F) epoxy resin is greater than 2 · 0 equivalents, the developability of the coating film or the resistance of the hardened film φ is not good, and the resistance to pct is also poor. The photocurable and thermosetting resin composition of the present invention may be colored with inorganic pigments, organic pigments, organic dyes, etc. as required. Since organic dyes cause the sensitivity to decrease, it is preferable to use inorganic pigments or organic pigments. . Specific examples include phthalocyanine · blue, phthalocyanine · green, iodine · green, diazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black. In addition, in terms of environmental issues, it is preferable to use (G) a non-halogen-based organic pigment. Except for titanium oxide, the amount of these pigments is generally 5% by mass or less in the composition. If it is larger than the above range, the photohardenability will decrease, and -15- (13) (13) 200530353 is not desirable. When titanium oxide is used, it is generally used at 15 mass% or less in the composition. In addition, the photocurable and thermosetting resin composition of the present invention may contain imidazole salts, boron trifluoride composites, organic metal salts, and the like as potential curing catalysts. In addition, for the purpose of preventing the oxidation of copper in printed circuit boards, that is, oxidation of copper, compounds such as adenine, vinyltriazine, dicyandiamine, n-tolylbiguanide, melamine, or the like may be added. Wait for the salt. In general, the compounding ratio of these compounds is 5% by mass or less in the composition. By adding these, the chemical resistance of the cured coating film or the adhesion to the copper foil can be improved. In addition, the photocurable and thermosetting resin composition of the present invention may be added with hydroquinone, hydroquinone monomethyl ether, and 3-butylcatechol as long as it does not reduce the characteristics of the coating film. , Pyrophenol, phenothiazine and other conventional thermal polymerization inhibitors, polysiloxane-based, fluorine-based, polymer-based antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based, etc. Conventional additives such as silane coupling agents. The photocurable and thermosetting resin composition of the present invention having the above-mentioned composition is diluted as necessary to adjust the viscosity suitable for the coating method, so that it is applied by the screen printing method, curtain coating method, and distribution coating. Method, roll coating method and the like are applied to a printed wiring board on which a circuit is formed, for example, the organic solvent contained in the composition is volatilized and dried at a temperature of 60 to 100 t to form Crumpled coating. Then, a photomask having a predetermined pattern is passed through, and selective active energy ray exposure is performed, and an unexposed portion is developed with a dilute alkali aqueous solution to form a photo-16-200530353 (14) resist pattern. Then, active energy is irradiated. Heat hardening after the wire, or irradiation of active energy rays after the heat hardening, or final work hardening (this hardening) only with heat hardening, can form adhesion, hardness, welding heat resistance, chemical resistance, solvent resistance, electrical insulation Hardened film (solder resistance film) with excellent properties, electrical corrosion resistance, resolution, plating resistance, pct resistance, and moisture absorption. In particular, the step of heating and curing after irradiating the active energy ray, or irradiating the active energy ray after the heating and hardening, reacts the unreacted photosensitive group, and a hardened film having excellent resistance to galvanic corrosion, plating, and moisture can be obtained. As the alkaline aqueous solution used for the development, an aqueous alkaline solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonium, or amines can be used. Furthermore, in order to make the light source for the light hardening, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, and a metal halide lamp are suitable. Others can use laser rays as active energy rays. [Embodiments] [Examples] The present invention will be specifically described in the following examples and comparative examples, but the present invention is not limited by the following examples. In addition, when there is no particular limitation in the following, "part" means all "mass parts". Synthesis Example: 215 parts of cresol novolac varnish type epoxy resin N-680 (made by Dainippon Ink Chemical Industry Co., Ltd., epoxy equivalent weight = 2 1 5) was added to a four-necked flask equipped with a stirrer and a reflux cooler. Then, add 196 parts of propylene glycol monomethyl ether ethyl-17-200530353 (15) acid ester and heat to melt. Then, 0.46 parts of methyl hydrogen as a polymerization inhibitor and 1.38 parts of triphenylphosphine as a reaction catalyst were added. The mixture was heated at 95 to 105 t: 72.0 parts (1.0 equivalent) of acrylic acid was slowly added dropwise to obtain a reaction product having an acid value of 0.9 mgKOH / g. The reaction product (hydroxyl: 1 equivalent) was cooled to 80 to 90 ° C, 76.0 parts (0.5 equivalent) of tetrahydrophthalic anhydride was added, and the reaction was performed for about 8 hours. After cooling, the reaction product was taken out. The carboxyl group-containing resin (A) thus obtained had a nonvolatile content of 65%, and an acid value of a solid content of 77 mgKOH / g. In the following, this lacquer is called A-1 lacquer. The mixing ratio shown in Table 1 using the hydroxyl-containing resin varnish (A-1 varnish) obtained in the above synthesis example was kneaded with three rolls to obtain each main component of the photocurable and thermosetting resin composition. Agent. In addition, the blending ratios shown in Table 2 were kneaded with three rolls to prepare the hardener of the photocurable / thermosetting resin composition. The obtained photocurable and thermosetting resin composition was adjusted to have a viscosity of about 200 dPa · s with propylene glycol monomethyl ether acetate.
-18- 200530353-18- 200530353
(16) 表1 實施例主劑 比較例主劑 1 2 3 1 2 A-1淸漆 60.0 60.0 60.0 60.0 60.0 Irg-369*1 4.0 4.0 4.0 4.0 4.0 BYK-R606*2 0.04 0.14 0.3 一 BYK-405*3 麵 0.5 BYK-354*4 4.0 4.0 4.0 4.0 4.0 DPHA*5 4.0 4.0 4.0 4.0 4.0 PMA*6 1.0 1.0 1.0 1.0 1.0 尼普希魯 (音譯）L-300*7 1.0 1.0 1.0 1.0 1.0 衣姆希魯 (音譯)A-8*8 10.0 10.0 10.0 10.0 10.0 硫酸鋇 20.0 20.0 20.0 20.0 20.0 銅酞菁 0.5 0.5 0.5 0.5 0.5 二重氮黃 0.1 0.1 0.1 0.1 0.1 二氰基二醯胺 0.1 0.1 0.1 0.1 0.1 蜜胺 0.8 0.8 0.8 0.8 0.8 備註 *1 :千葉特殊化公司製光聚合起始劑、2-苯甲基-2-二甲基胺基-1_(4_嗎啉基苯基)-丁-1-酮 *2 :日本比克(音譯)化學公司製、聚羥基羧酸酯系添加劑 *3 :日本比克(音譯)化學公司製、聚羧酸醯胺系添加劑 *4 :日本比克(音譯)化學公司製、丙烯酸系水平劑·消泡劑 *5 :日本化藥製、二季戊四醇六丙烯酸酯 *6 :丙二醇單甲醚乙酸酯 *7 :東曹(音譯）·二氧化矽公司製、親水性超微粉二氧化矽 *8 :龍森工業公司製、結晶性二氧化矽 -19- 200530353 (17) 表2 硬化劑 E-157CA75*9 5.0 耶皮克頓（音譯） 828*10 35.0 TEPIC-H*11 10.0 DPHA*5 15.0 PMA*6 15.0 備註 *9 :日本環氧樹脂公司製、耶皮克頓(音譯)157S70以固成份70% 溶解於卡必醇乙酸酯之淸漆 *10 :日本環氧樹脂公司製、雙酚A型環氧樹月旨 *11 :日產化學公司製、高熔點型三環氧丙基異氰酸酯 *5 :日本化藥製、二季戊四醇六丙烯酸酯 *6 :丙二醇單甲醚乙酸酯 性能評估： (1 )保存安定性（黏度、觸變性） 使上述實施例1〜3及比較例1，2之光硬化性•熱硬 化性樹脂組成物的主劑之初期黏度、與在5 0 °C之恆溫槽 中放置1，2,3,4,7日之經時黏度，以下述條件測定。 黏度計：克布雷頓（音譯）型黏度計（頓齊梅克（音譯）公 司製）(16) Table 1 Example main agent Comparative example Main agent 1 2 3 1 2 A-1 lacquer 60.0 60.0 60.0 60.0 60.0 Irg-369 * 1 4.0 4.0 4.0 4.0 4.0 BYK-R606 * 2 0.04 0.14 0.3-BYK-405 * 3 side 0.5 BYK-354 * 4 4.0 4.0 4.0 4.0 4.0 DPHA * 5 4.0 4.0 4.0 4.0 4.0 PMA * 6 1.0 1.0 1.0 1.0 1.0 Nephiru L-300 * 7 1.0 1.0 1.0 1.0 1.0 Emuhi Lu (transliteration) A-8 * 8 10.0 10.0 10.0 10.0 10.0 Barium sulfate 20.0 20.0 20.0 20.0 20.0 Copper phthalocyanine 0.5 0.5 0.5 0.5 0.5 Diazo yellow 0.1 0.1 0.1 0.1 0.1 Dicyanodiamidate 0.1 0.1 0.1 0.1 0.1 Honey Amine 0.8 0.8 0.8 0.8 0.8 Remarks * 1: Photopolymerization initiator manufactured by Chiba Specialty Chemicals, 2-benzyl-2-dimethylamino-1_ (4_morpholinylphenyl) -but-1- Ketone * 2: Polyhydroxycarboxylic acid ester-based additive manufactured by Japan BAK Chemical Co., Ltd. * 3: Polycarboxylic acid ammonium-based additive manufactured by Japan BAK Chemical Co., Ltd. * 4: Japanese BAK Chemical Co., Ltd. Chemical company, acrylic leveling and defoaming agent * 5: manufactured by Nippon Kayaku, dipentaerythritol hexaacrylate * 6: propylene glycol monomethyl ether acetate * 7: Tosoh (Transliteration), Silicon Dioxide Corporation Hydrophilic ultrafine silicon dioxide * 8: Crystalline silica-19-200530353 (17) manufactured by Longsen Industries Co., Ltd. Table 2 Hardener E-157CA75 * 9 5.0 Yepicton 828 * 10 35.0 TEPIC-H * 11 10.0 DPHA * 5 15.0 PMA * 6 15.0 Remarks * 9: Made by Japan Epoxy Resin Company, Yepicton 157S70, 70% solid paint dissolved in carbitol acetate * 10: Bisphenol A epoxy resin made by Japan Epoxy Resin Co., Ltd. * 11: High melting point type triglycidyl isocyanate manufactured by Nissan Chemical Co., Ltd. * 5: Dipentaerythritol hexaacrylate manufactured by Nihon Kasei Corporation : Propylene glycol monomethyl ether acetate performance evaluation: (1) Storage stability (viscosity, thixotropy) The main agent for making the photocurable and thermosetting resin compositions of Examples 1 to 3 and Comparative Examples 1,2 above. The initial viscosity and the viscosity over time of 1, 2, 3, 4, and 7 days in a thermostatic bath at 50 ° C were measured under the following conditions. Viscometer: Kebretton (transliteration) viscometer (Donzimek)
測定溫度：2 5 °C 錐回轉數：5rpm/min、及 50rpm/min -20- 200530353 (18) τ · I(觸變性之參考値） =(上述 5rpm/min 値）/(上述 50rpm/min 値） (2 )保存安定性（塗覆性） 使上述實施例1〜3及比較例1，2之光硬化性•熱硬 化性樹脂組成物的主劑、與硬化劑各以重量比4 : 1混 合，調整各光硬化性·熱硬化性樹脂組成物。而且，同樣 地使用在50°C之恆溫槽中放置1，2,3,4,7曰之主劑，觀察 塗覆性之經時變化。 使上述各組成物以隙縫式簾幕塗覆器，以乾燥膜厚約 爲20μηι塗覆於形成有電路之銅箔基板，在室溫下平置、 乾燥1 〇分鐘後，懸掛於專用紫膠，在熱風循環式乾燥爐 內、80 °C下乾燥1 5分鐘後，如下述評估塗覆性。 〇：沒有皺摺、均勻塗覆 △:有皺摺產生、上部與下部之膜厚有差別 X :有顯著皺摺產生、且會看見銅箔 (3)感度 與上述相同地調整的各光硬化性•熱硬化性樹脂組成 物以隙縫式簾幕塗覆器、以乾燥膜厚約爲20μηι塗覆於基 板上’在室溫下平置、乾燥1 〇分鐘後，懸掛於專用紫 膠’在熱風循環式乾燥爐內、8 〇 t：下乾燥1 5分鐘後，使 克拉古（音譯）Νο·2之階段式小平板密接，以累計光量爲 3 00mJ/cm2曝光，藉由1 w t % N a2 C Ο 3水溶液、以噴霧壓 0 · 2 Μ P a顯像1分鐘後，由階段式小平板所得的段數評估 -21 - 200530353 (19) 感度。 (4) 顯像線 與上述相同地調整的各光硬化性•熱硬化性樹脂組成 物以隙縫式簾幕塗覆器、以乾燥膜厚約爲2 0 μ m塗覆於形 成有電路之銅箔基板上，在室溫下平置、乾燥1 0分鐘 後’懸掛於專用紫膠，在熱風循環式乾燥爐內、8 0 °C下使 φ 乾燥時間各以5分鐘間隔變化的基板。在該基板上塗覆負 薄膜’使阻焊圖案曝光，且藉由1 wt%Na2C03水溶液、以 噴霧壓〇.2MPa顯像1分鐘後，觀察假乾燥後之顯像線（可 顯像之最長乾燥時間）。 (5) 表面狀態 與上述相同地調整的各光硬化性•熱硬化性樹脂組成 物以隙縫式簾幕塗覆器、以乾燥膜厚約爲20μιη塗覆於形 φ 成有電路之銅箔基板上，在室溫下平置、乾燥10分鐘 後’懸掛於專用紫膠，在熱風循環式乾燥爐內、8 0 〇c下使 乾燥時間各以5分鐘間隔變化的基板。在該基板上塗覆負 薄0旲’使阻焊圖案曝光，且藉由1 w t % N a 2 C Ο 3水溶液、以 噴霧壓0 · 2 Μ P a顯像1分鐘後，在熱風循環式乾燥爐中、 150°C下熱硬化60分鐘。 所得硬化塗膜之表面狀態以目視評估。 (6)焊接耐熱性 -22- 200530353 (20) 與上述同樣地調整的各光硬化性•熱硬化性樹脂組成 物’以隙縫式簾幕塗覆器塗覆乾燥膜厚約爲20μηι塗覆於 形成有電路之銅箔基板上，在室溫下平置、乾燥1 〇分鐘 後’在熱風循環式乾燥爐內、8 (TC下乾燥1 5分鐘。在該 基板上塗覆負薄膜，使阻焊圖案曝光，且藉由 1 wt%Na2C03水溶液、以噴霧壓0.2MPa顯像1分鐘後， 在熱風循環式乾燥爐內、150 °C下乾燥60分鐘。使該基板 ^ 塗覆松香系助焊劑，在預先加熱至260°C之焊接槽中浸漬 3 0秒，以丙二醇單甲醚洗淨助焊劑後，藉由目視評估光 阻層之膨脹•剝落•變色情形。 〇：完全沒有變化者 △:稍有變化者 X :塗膜膨脹且剝落者 如此所得的實施例1〜3及比較例1，2之光硬化性· I 熱硬化性樹脂組成物的評估結果如表3所示。 -23- 200530353 (21)Measuring temperature: 2 5 ° C Cone rotation number: 5rpm / min and 50rpm / min -20- 200530353 (18) τ · I (reference for thixotropy 値) = (above 5rpm / min 値) / (above 50rpm / min値) (2) Storage stability (coatability) The main components of the photocurable and thermosetting resin compositions of the above Examples 1 to 3 and Comparative Examples 1,2 and the curing agent were each in a weight ratio of 4: 1 is mixed, and each photocurable and thermosetting resin composition is adjusted. In the same manner, a main agent of 1, 2, 3, 4, 7 was placed in a constant temperature bath at 50 ° C, and the change in coating properties was observed over time. The above-mentioned compositions are coated with a slit curtain coater with a dry film thickness of about 20 μm on a copper foil substrate on which a circuit is formed, placed flat at room temperature, dried for 10 minutes, and hung on a special shellac. After drying in a hot-air circulation drying oven at 80 ° C for 15 minutes, the applicability was evaluated as described below. 〇: No wrinkles, uniform coating △: Wrinkles are generated, there is a difference in film thickness between the top and bottom X: Significant wrinkles are generated, and the copper foil (3) sensitivity is adjusted in the same manner as described above Properties • The thermosetting resin composition is coated on a substrate with a slit curtain coater with a dry film thickness of about 20 μm. 'Place flat at room temperature, dry for 10 minutes, and then hang on a special shellac.' In a circulating drying furnace, 80 ° C: After 15 minutes of drying, the stage small plate of Cragou (transliteration) No. 2 was brought into close contact, exposed at a cumulative light amount of 300 mJ / cm2, and 1 wt% N a2 After the C 0 3 aqueous solution was developed at a spray pressure of 0.2 M Pa for 1 minute, the number of segments obtained from the stepped plate was evaluated by -21-200530353 (19) sensitivity. (4) Each photocurable and thermosetting resin composition with the imaging line adjusted in the same manner as described above was coated with a slit-type curtain coater and a dry film thickness of about 20 μm on copper on which the circuit was formed. On a foil substrate, the substrate was placed flat at room temperature and dried for 10 minutes. The substrate was hung from a special shellac, and the substrate was changed in a hot-air circulation drying oven at 80 ° C, each having a φ drying time interval of 5 minutes. A negative film was coated on the substrate to expose the solder resist pattern, and the image was developed with a spray pressure of 0.2 MPa for 1 minute by using a 1 wt% Na2C03 aqueous solution, and then the imaging line after the pseudo-drying (the longest drying time that can be developed) was observed. time). (5) Each photocurable / thermosetting resin composition whose surface condition is adjusted in the same manner as described above is coated on a copper foil substrate having a circuit shape with a slit-type curtain coater and a dry film thickness of about 20 μm. On the substrate, the substrates were placed flat and dried at room temperature for 10 minutes, and were hung on a dedicated shellac, and the drying time was changed at 5 minute intervals in a hot air circulation drying oven at 800 ° C. This substrate was coated with a negative thin film to expose the solder resist pattern, and it was developed with a 1 wt% Na 2 C 0 3 aqueous solution at a spray pressure of 0.2 Mpa for 1 minute, and then dried in a hot air cycle. Heat hardened in a furnace at 150 ° C for 60 minutes. The surface state of the obtained hardened coating film was evaluated visually. (6) Welding heat resistance-22- 200530353 (20) Each photocurable / thermosetting resin composition adjusted in the same manner as above was applied with a slit curtain coater and a dry film thickness of about 20 μm was applied to The copper foil substrate on which the circuit is formed is laid flat at room temperature and dried for 10 minutes. 'Dried in a hot air circulation drying oven at 8 ° C for 15 minutes. A negative film is coated on the substrate to make a solder resist pattern. After exposure to light and development with a 1 wt% Na2C03 aqueous solution at a spray pressure of 0.2 MPa for 1 minute, the substrate was dried in a hot air circulation drying oven at 150 ° C for 60 minutes. The substrate was coated with a rosin-based flux, and Immerse in a solder bath heated to 260 ° C for 30 seconds, and then clean the flux with propylene glycol monomethyl ether, and then visually evaluate the expansion, peeling, and discoloration of the photoresist layer. 〇: No change at all △: Slightly Changes X: The results of the evaluation of the photocurability and I thermosetting resin composition of Examples 1 to 3 and Comparative Examples 1 and 2 obtained by the coating film expanding and peeling are shown in Table 3. -23- 200530353 (twenty one)
表3 實施例 比較例 1 2 3 1 2 (1)黏度σ·ι値） 初期値 204(1.37) 210(1.44) 204(1.55) 204(1.12) 201(1.42) 50〇C、1 日 210(1.36) 207(1.42) 210(1.53) 192(1.06) 207(1.40) 50〇C、2 日 204(1.37) 201(1.42) 207(1.53) 186(1.02) 201(1.40) 50〇C、3 日 204(1.35) 207(1.39) 207(1.51) 189(1.02) 195(1.39) 50〇C、4 日 198(1.32) 207(1.37) 201(1.50) 189(1.01) 195(1.36) 50〇C、7 日 198(1.28) 201(1.33) 204(1.45) 195(1.01) 198(1.29) (2)塗覆性 初期値 〇 〇 〇 Δ 〇 50〇C、1 日 〇 〇 〇 X 〇 50〇C、2 日 〇 〇 〇 X 〇 50°C、3 日 〇 〇 〇 X 〇 50〇C、4 日 Δ 〇 〇 X 〇. 50°C、7 日 Δ Δ 〇 X Δ (3)感度(300mJ/cm2) 6段 6段 6段 6段 6段 (4)顯像線(80。〇 80分鐘 80分鐘 80分鐘 80分鐘 80分鐘 (5)表面狀態 有光澤 有光澤 無光澤 有光澤 有光澤 (6)焊接耐熱性 〇 〇 〇 〇 〇 組成物中有無二甲苯 Μ Μ y\\\ Μ 並 有 如上所述可知，使用聚羥基羧酸酯系添加劑之B YK-R6 06的實施例，不含二甲苯，黏度、觸變性之經時安定 性優異，塗覆性變化情形亦少。另外，以配合量約1 /3量 -24- 200530353 (22) 之實施例2可得與添加約0.5 % 一般所使用的聚錢酸薩胺 系添加劑之B YK_4〇5的比較例2同等的觸變性。 此外，可知即使配合該聚羥基羧酸酯系添加劑之 BYK-R606時，感度、顯像線、焊接耐熱性等之塗膜特性 不會降低。 【圖面之簡單說明1 [第1圖] 係表示實施例1〜3所使用的聚羥基羧酸酯系添加劑 BYK-R606 之 IR 光譜。 -25-Table 3 Examples Comparative Examples 1 2 3 1 2 (1) Viscosity σ · ι 値) Initial stage 204 (1.37) 210 (1.44) 204 (1.55) 204 (1.12) 201 (1.42) 50 ° C, 1 day 210 ( 1.36) 207 (1.42) 210 (1.53) 192 (1.06) 207 (1.40) 50 ° C, 2 days 204 (1.37) 201 (1.42) 207 (1.53) 186 (1.02) 201 (1.40) 50 ° C, 3 days 204 (1.35) 207 (1.39) 207 (1.51) 189 (1.02) 195 (1.39) 50 ° C, 4th 198 (1.32) 207 (1.37) 201 (1.50) 189 (1.01) 195 (1.36) 50 ° C, 7 days 198 (1.28) 201 (1.33) 204 (1.45) 195 (1.01) 198 (1.29) (2) Initial coating properties 値 〇〇〇 △ 〇〇〇〇〇〇, 〇〇〇〇〇〇〇〇〇〇〇〇〇〇 〇〇〇〇〇 °° C on the 2nd, 〇〇〇〇〇〇〇〇〇〇 3 〇 〇〇〇 。。。 50 ° C, 7 Δ △ 〇 × Δ (3) sensitivity (300mJ / cm2) 6 steps 6 steps 6 steps 6 steps 6 steps (4) Imaging line (80.80 minutes 80 minutes 80 minutes 80 minutes 80 minutes 80 minutes (5) Surface state shiny glossy matte shiny glossy (6) welding heat resistance Properties: Does the composition contain xylene Μ Μ y \\\ Μ, and it is known as described above that B YK-R6 using a polyhydroxycarboxylic acid ester-based additive is used? Example 06 does not contain xylene, and has excellent stability over time with viscosity and thixotropy, and there is little change in coatability. In addition, Example 2 with a compounding amount of about 1/3 amount-24- 200530353 (22) The same thixotropy as that of Comparative Example 2 in which B YK_405, which is a commonly used polysalenic acid-based additive, is added at about 0.5%. It is also known that even when BYK-R606 is blended with the polyhydroxycarboxylic acid-based additive, The coating film characteristics such as sensitivity, display line, soldering heat resistance, etc. will not be reduced. [Simplified description of the drawing 1 [Fig. 1] shows the polyhydroxycarboxylic acid ester additive BYK- used in Examples 1 to 3. IR spectrum of R606. -25-