201211684 六、發明說明： 【發明所屬之技術領域】 本發明係關於具有優良解析度的黑色硬化性樹脂組成 物，且關於例如作爲印刷配線板之抗焊劑使用時，能夠適 應電極的微距化與微細化，再者黑色之色調優良，即使經 熱處理後亦能夠防止色調變化之黑色硬化性樹脂組成物。 【先前技術】 印刷配線板係使用於在基板上形成導體電路之圖型， 且在該圖型之焊地藉由焊接來搭載電子零件，除了該焊地 以外的電路部分係以抗焊膜被覆而作爲永久保護皮膜。藉 此，可防止於印刷配線板焊接電子零件時，焊料附著於不 必要的部分，並且防止電路導體直接暴露於空氣中，因氧 化或濕度而腐蝕。 再者，近年來隨著技術進步，電子學領域中對於小型 化、輕量化的要求更爲增加，伴隨於此，爲了以高密度配 置更爲小型化之電子零件，係要求印刷配線板之導體電路 圖型的微距化、微細化、高精度性。因應於此，對於抗焊 膜’於解析度、尺寸精度性、耐熱性等種種特性上亦要求 有更高性能，如此之抗焊膜其一即爲黑色抗焊膜。 作爲形成黑色抗焊膜的材料者，提出一種抗焊劑組成 物（專利文獻1)，其中摻合於含羧基樹脂之著色劑爲黑色 著色劑與黑色著色劑以外之1種以上的著色劑。但是，專 利文獻1之黑色抗焊劑組成物因爲具有黑色，故曝光時之 -5- 201211684 光吸收增多，光難以到達特別是抗焊劑塗膜的深部。因此 ，抗焊劑塗膜的深部中光硬化並不充分，會有顯像後抗焊 劑塗膜深部的尺寸變得過小，硬化塗膜會由印刷配鱗板剝 離等的解析度或線殘留不良之問題。 因而，有提出一種黑色抗焊劑組成物（專利文獻2)， 其係藉由將含羧基樹脂中摻合之著色劑設爲黃色著色劑與 紫色著色劑、黃色著色劑與藍色著色劑與紅色著色劑、綠 色著色劑與紫色著色劑、及綠色著色劑與紅色著色劑之群 組中所選出之任意組合而經黑色化者。但是，專利文獻2 中，爲了將黑色著色劑以外之著色劑黑色化，會有難以調 整爲黑色、繁雜、或是爲了提高黑色度則著色劑的含有率 變高，使解析性能仍舊無法充分之問題。 [先前技術文獻] [專利文獻] 專利文獻1日本特開2008-257045 專利文獻2日本特開20 1 0-9 1 8 7 6 【發明內容】 [發明所欲解決之課題] 有鑑於上述情形，本發明的目的爲提供具有優良解析 度，同時容易調整爲黑色、且能夠防止熱處理後的色調變 化之黑色硬化性樹脂組成物。 [用以解決課題之手段] -6- 201211684 本發明之態樣，爲一種黑色硬化性樹脂組成物，其係 含有（A)含羧基感光性樹脂、（B)光聚合起始劑、（C)稀釋劑 、（D)環氧化合物及（E)黑色著色劑之黑色硬化性樹脂組成 物，其特徵爲前述（E)黑色著色劑含有（E_l)碳黑系黑色著 色劑與（E-2)茈系黑色著色劑，且前述（E)黑色著色劑之中 ，前述（E-2)茈系黑色著色劑的含量爲53質量％以上。 上述態樣中，係藉由於黑色硬化性樹脂組成物之著色 劑中摻合碳黑系黑色著色劑與茈系黑色著色劑，且將全部 黑色著色劑中，茈系黑色著色劑的摻合比例設爲53質量％ 以上，使得爲了光硬化而用於曝光之光會到達黑色硬化性 樹脂組成物的塗膜深部，而自塗膜的表面部至深部均充分 地光硬化。碳黑系黑色著色劑係將黑色硬化性樹脂組成物 之明度降低，而補充、提高黑色度者。 本發明之態樣，爲一種黑色硬化性樹脂組成物，其特 徵爲，前述（E-2)茈系黑色著色劑之波長300〜400nm之光 的透射率爲3%以上。上述態樣中，因摻合了波長3 00〜 40 0nm之光透射率爲3%以上之茈系黑色著色劑，故光硬 化所需光量之紫外光可確實到達塗佈於基板上之黑色硬化 性樹脂組成物的深部。 本發明之態樣，爲一種黑色硬化性樹脂組成物，其特 徵爲，前述（E-2)茈系黑色著色劑之波長400〜700nm之光 的透射率爲20%以下。本發明之態樣，爲一種黑色硬化性 樹脂組成物，其特徵爲，前述（E-2)茈系黑色著色劑於紅外 線吸收光譜測定中，至少在1669〜1671cm·1之間、1548 201211684 〜1 5 5 0cm·1 之間、1 49 8 〜1 500cm·1 之間、1 402 〜1 404cm·1 之間、1 2 83 〜1 2 8 5 cm·1 之間、822 〜824cm·1 之間、763 〜 765CHT1之間、73 9〜741(::^1之間的吸收位置具有紅外線 吸收峰。 本發明之態樣，爲一種黑色硬化性樹脂組成物，其特 徵爲進一步含有（F)藍色著色劑。在上述各黑色著色劑以 外，進一步摻合藍色著色劑，藉以將以色差計測定之明度 (L*値）降低的同時，將色彩度指數（a*値）由正値側向0附 近調整。再者，本發明之態樣，爲一種黑色硬化性樹脂組 成物，其特徵爲，前述（F)藍色著色劑爲酞青素系藍色著 色劑。 本發明之態樣，爲一種黑色硬化性樹脂組成物，其特 徵爲進一步含有（G)黃色著色劑。在上述各黑色著色劑以 外’進一步摻合黃色著色劑，藉以將以色差計測定之L* 値降低的同時，將色彩度指數（b*値）由負値側向0附近調 整。再者，本發明之態樣，爲一種黑色硬化性樹脂組成物 ’其特徵爲，前述（G)黃色著色劑爲蒽醌系黃色著色劑。 本發明之態樣，爲一種硬化物，其係由上述黑色硬化 性樹脂組成物硬化而得。再者，本發明之態樣爲一種硬化 物，其特徵在於，L*値爲25以下、a*値及b*値均在-2〜2 之範圍內。本發明之態樣，爲一種硬化物，其特徵在於， 膜厚2(^111時波長40〇11111之光的透射率爲7.0%以上。再者 ’本發明之態樣爲一種印刷配線板，其特徵爲係以上述黑 色硬化性樹脂組成物作爲抗焊劑來塗佈。 -8- 201211684 [發明之效果] 依照本發明之態樣，摻合之黑色著色劑總量中，茈系 黑色著色劑之摻合比例設爲53質量％以上，藉此，爲了光 硬化而用於曝光之光會到達黑色硬化性樹脂組成物之塗膜 深部，因此自塗膜的表面部至深部會充分光硬化。如此， 光硬化充分地進行至塗膜的深部，因此即使塗佈於具有微 距之電路圖型的印刷配線板等基板，亦可防止深部之光硬 化不足而造成塗膜的脫落或缺損等，提高解析度。又，因 爲光硬化充分地進行至塗膜的深部，因此能夠防止顯像後 硬化塗膜深部之寬度尺寸減少。從而，硬化塗膜深部之寬 度尺寸係接近於硬化塗膜表層部之寬度尺寸，硬化塗膜的 尺寸精度會提高。 依照本發明之態樣，摻合了波長300〜400nm之光的 透射率爲3 %以上的茈系黑色著色劑，因此可確實防止塗 膜深部之光硬化不足而造成之塗膜脫落或欠損等，解析度 與尺寸精度更加提高。 依照本發明之態樣，藉由進一步按照需要來摻合藍色 著色劑，能夠使在以色差計測定之L *値降低的同時，將 a *値由正値側向0値附近調整’因此黑色的濃度及色調容 易調整。 依照本發明之態樣，藉由進一步摻合黃色著色劑，能 夠使在以色差計測定之LM直降低的同時，將b*値由負値 側向0値附近調整，因此黑色的濃度及色調容易調整。 -9 - 201211684 【實施方式】 接著，說明本發明之黑色硬化性樹脂組成物的各成分 。本發明之黑色硬化性樹脂組成物係含有（A)含羧基感光 性樹脂、（B)光聚合起始劑、（C)稀釋劑、（D)環氧化合物、 (E)黑色著色劑之黑色硬化性樹脂組成物，其中前述（E)黑 色著色劑係含有（E-1)碳黑系黑色著色劑與（E-2)茈系黑色 著色劑，且前述（E)黑色著色劑當中，前述（E-2)茈系黑色 著色劑之含量爲5 3質量％以上。 (A)含羧基感光性樹脂 含羧基感光性樹脂並無特殊限定，可使用具有1個以 上之感光性不飽和雙鍵的感光性含羧基樹脂、不具有感光 性不飽和雙鍵之含羧基樹脂之任一者。作爲（A)成分之例 者，可列舉分子中具有2個以上環氧基之多官能環氧樹脂 之環氧基的至少一部分，與丙嫌酸或甲基丙嫌酸等自由基 聚合性不飽和單羧酸反應所得到之（甲基）丙烯酸環氧酯， 且令生成之羥基與多元酸或其酸酐反應而得之多元酸改質 (甲基）丙稀酸環氧酯。 前述多官能性環氧樹脂只要係2官能以上之環氧樹脂 均可使用，雖無環氧當量之特殊限制，但通常使用1000 以下、較佳爲使用100〜500者。多官能性環氧樹脂係可 列舉聯苯型環氧樹脂、萘型環氧樹脂、二環戊二烯型環氧 樹脂、聚矽氧改質環氧樹脂等橡膠改質環氧樹脂；ε -己 -10- 201211684 內酯改質環氧樹脂、雙酚A型、雙酚F型 '雙酚AD型等 酚酚醛清漆型環氧樹脂；鄰甲酚酚醛清漆型等甲酚酚醛清 漆型環氧樹脂；雙酚A酚醛清漆型環氧樹脂；環狀脂肪族 多官能環氧樹脂；縮水甘油酯型多官能環氧樹脂；縮水甘 油胺型多官能環氧樹脂；雜環式多官能環氧樹脂；雙酚改 質酚醛清漆型環氧樹脂；多官能改質酚醛清漆型環氧樹脂 ;具有酚類與酚性羥基之與芳香族醛的縮合物型環氧樹脂 等爲例。再者，亦可使用將Br、C1等鹵素原子導入該等 樹脂者。該等之中，尤其從塗膜可撓性的觀點而言，較佳 爲聚矽氧故質環氧樹脂等橡膠改質環氧樹脂。該等環氧樹 脂可單獨使用，亦可混合2種以上來使用。 所使用之自由基聚合性不飽和單羧酸並無特殊限定， 可列舉丙烯酸、甲基丙烯酸、巴豆酸、桂皮酸等爲例，較 佳爲丙烯酸及甲基丙烯酸之至少一者（以下亦稱爲（甲基）丙 烯酸），特佳爲丙烯酸。令（甲基）丙烯酸經反應者係爲（甲 基）丙烯酸環氧酯。環氧樹脂與自由基聚合性不飽和單羧 酸之反應方法並無特殊限制，例如可藉由將環氧樹脂與丙 烯酸在適當的稀釋劑中加熱來反應。 多元酸或多元酸酐，係爲與前述環氧樹脂與自由基聚 合性不飽和單羧酸之反應中生成之羥基反應，使其帶有與 樹脂游離的竣基者。作爲所使用之多元酸或其酸酐者並無 特殊限定’飽和、不飽和均可使用。多元酸可列舉琥珀酸 、馬來酸、己二酸、檸檬酸、鄰苯二甲酸、四氫化鄰苯二 甲酸、3 -甲基四氫化鄰苯二甲酸、4_甲基四氫化鄰苯二甲 -11 - 201211684 酸、3_乙基四氫化鄰苯二甲酸、4 -乙基四氫化鄰苯二甲酸 、六氫鄰苯二甲酸、3-甲基六氫鄰苯二甲酸、4_甲基六氫 鄰苯二甲酸、3-乙基六氫鄰苯二甲酸、4_乙基六氫鄰苯二 甲酸、甲基四氫化鄰苯二甲酸、甲基六氫鄰苯二甲酸、內 亞甲基四氫化鄰苯二甲酸、甲基內亞甲基四氫化鄰苯二甲 酸、偏苯三甲酸、苯均四酸及氧代二乙醇酸等爲例，多元 酸酐可列舉該等之酸酐。該等化合物可單獨使用，亦可混 合2種以上來使用。 本發明中’上述多元酸改質不飽和單羧酸化環氧樹脂 雖亦可使用作爲感光性樹脂，但亦可使用令上述多元酸改 質不飽和單羧酸化環氧樹脂所具有之羧基，與具有1個以 上之自由基聚合性不飽和基與環氧基的縮水甘油化合物反 應，藉以進一步導入自由基聚合性不飽和基，而感光性進 一步提高之感光性樹脂。 該感光性經提高之感光性樹脂，因最後之縮水甘油化 合物的反應，自由基聚合性不飽和基係與其前驅物之感光 性樹脂的高分子骨架側鏈鍵結’因此光聚合反應性高、且 能夠具有優良的感光特性。作爲具有1個以上之自由基聚 合性不飽和基與環氧基的化合物者，可列舉丙烯酸縮水甘 油酯、甲基丙烯酸縮水甘油酯、烯丙基縮水甘油醚、季戊 四醇三丙烯酸酯單縮水甘油醚等爲例。另外，1分子中亦 可具有複數個的縮水甘油基。上述之具有1個以上之自由 基聚合性不飽和基與環氧基之化合物係可單獨使用、亦可 混合2種以上來使用。 -12- 201211684 含羧基感光性樹脂之酸價的下限値，由確實的進行鹼 顯像之觀點而言係爲30mgKOH/g，較佳爲40mgKOH/g。 另一方面，酸價的上限値，以用鹼顯像液來防止曝光部溶 解的觀點而言係爲200mgKOH/g，由防止硬化物之耐濕性 與電氣特性劣化的觀點而言，較佳爲150mgKOH/g。 再者，含羧基感光性樹脂之重量平均分子量的下限値 ，由硬化物之強韌性及指觸乾燥性的觀點而言爲3000,較 佳爲5000。另一方面，重量平均分子量之上限値，由與 (C)成分之稀釋劑等的相溶性及易於鹼顯像性的觀點而言 爲 200000，較佳爲 50000。 作爲含羥基感光性樹脂之市售者，可列舉ZFR-11 24 、FLX-2089(以上、日本化藥（股）製）、Cyclomer-P(ACA)Z-250(Daicel化學工業（股）製）、Ripoxy SP-4621 (昭和高分子 (股）製）等爲例。該等樹脂可單獨使用，亦可混合2種以上 來使用。 (B)光聚合起始劑 光聚合起始劑只要係一般所使用者即無特殊限定’可 列舉肟系起始劑、苯偶姻、苯偶姻甲醚、苯偶姻乙醚、苯 偶姻異丙醚、苯偶姻正丁醚、苯偶姻異丁醚、苯乙酮、二 甲基胺基苯乙酮、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-羥基·2·甲基-1-苯基丙烷-1-酮、1-羥基環己基苯基酮、2-甲基-1-[4-(甲硫基）苯基]-2-嗎啉基-丙烷-卜酮、4-(2-羥基乙氧基）苯基-2-(羥基-2-丙基）酮、二 -13- 201211684 .苯甲酮、p-苯基二苯甲酮、4，4'-二乙基胺基二笨甲酮、二 氯二苯甲酮、2-甲基蒽醌、2-乙基蒽醌、2-第三丁基恵醒 、2-胺基蒽醌、2-甲基噻吨酮、2-乙基噻吨酮、2_氯噻吨 酮、2,4 -二甲基噻吨酮、2,4二乙基噻吨酮、苄基二甲基 縮酮、苯乙酮二甲基縮酮、P-二甲基胺安息香酸乙酯等爲 例。該等可單獨使用，亦可混合2種以上來使用。相對於 含羧基感光性樹脂1〇〇質量份，光聚合起始劑的接合量爲 5〜20質量份，較佳爲8〜15質量份。 (C)稀釋劑 稀釋劑爲例如反應性稀釋劑之光聚合性單體，係用以 充分進行含羧基感光性樹脂之光硬化，而得到具有耐酸性 、耐熱性、耐鹼性等的硬化物。作爲光聚合性單體者，可 列舉1，4-丁二醇二（甲基）丙烯酸酯、1，6-己二醇二（甲基）丙 烯酸酯、新戊二醇二（甲基）丙烯酸酯、聚乙二醇二（甲基） 丙烯酸酯、新戊二醇己二酸酯二（甲基）丙烯酸酯、羥基三 甲基乙酸新戊二醇二（甲基）丙烯酸酯、二環戊烷基二（甲基 )丙烯酸酯、己內酯改質二環戊烯基二（甲基）丙烯酸酯、環 氧乙烷改質燐酸二（甲基）丙烯酸酯、烯丙基化環己基二（甲 基）丙烯酸酯、三聚異氰酸酯二（甲基）丙烯酸酯、三羥甲基 丙烷三（甲基）丙烯酸酯、二季戊四醇三（甲基）丙烯酸酯、 丙酸改質二季戊四醇三（甲基）丙烯酸酯、季戊四醇三（甲基 )丙條酸酯、環氧丙烷改質三羥甲基丙烷三（甲基）丙烯酸酯 、參（丙烯醯氧基乙基）三聚異氰酸酯、丙酸改質二季戊四 -14- 201211684 醇五（甲基）丙烯酸酯、二季戊四醇六（甲基）丙烯酸酯、己 內酯改質二季戊四醇六（甲基）丙烯酸酯等反應性稀釋劑爲 例。該等係可單獨使用，亦可混合2種以上來使用。上述 之反應性稀釋劑的摻合量，相對於含羧基感光性樹脂1 00 質量份爲2.0〜40質量份，較佳爲1〇〜25質量份。 再者，作爲稀釋劑者，爲了調節黑色硬化性組成物之 黏度或乾燥性，亦可使用非反應性稀釋劑之有機溶劑，來 取代上述反應性稀釋劑、或合倂使用上述反應性稀釋劑。 作爲有機溶劑者，可列舉甲乙酮、環己酮等酮類；甲苯、 二甲苯等芳香族烴類；甲醇、異丙醇、環己醇等醇類；環 己烷、甲基環己烷等脂環式烴類；石油醚、石油腦等石油 系溶劑類：2-乙氧基乙醇（賽珞蘇）、丁基2-乙氧基乙醇等 2-乙氧基乙醇類；卡必醇、丁基卡必醇等之卡必醇類；醋 酸乙酯、醋酸丁酯、醋酸2-乙氧基乙醇酯、醋酸丁基2-乙 氧基乙醇酯、醋酸卡必醇酯、醋酸丁基卡必醇酯等之醋酸 酯類等爲例。使用有機溶媒時的摻合量，相對於含羧基感 光性樹脂1〇〇重量份’較佳爲40〜500重量份。 (D)環氧化合物[Technical Field] [Technical Field] The present invention relates to a black curable resin composition having excellent resolution, and can be adapted to the micronization of an electrode when used as a solder resist for a printed wiring board, for example. Further, the black curable resin composition which is excellent in color tone and which is excellent in color tone and which can prevent color tone change even after heat treatment. [Prior Art] A printed wiring board is used for forming a conductor circuit on a substrate, and an electronic component is mounted by soldering on the soldering land of the pattern, and a circuit portion other than the soldering land is covered with a solder resist film. And as a permanent protective film. Thereby, it is possible to prevent the solder from adhering to an unnecessary portion when the printed wiring board is soldered to the electronic component, and to prevent the circuit conductor from being directly exposed to the air and being corroded by oxidation or humidity. In addition, in recent years, with the advancement of technology, the demand for miniaturization and weight reduction has increased in the field of electronics. Accordingly, in order to arrange more compact electronic parts at a high density, it is required to conductors of printed wiring boards. Macrotype, miniaturization, and high precision of circuit patterns. In response to this, the solder resist film is required to have higher performance in various characteristics such as resolution, dimensional accuracy, and heat resistance, and such a solder resist film is a black solder resist film. As a material for forming a black solder resist film, a solder resist composition is proposed (Patent Document 1), in which a coloring agent blended with a carboxyl group-containing resin is one or more kinds of coloring agents other than a black coloring agent and a black coloring agent. However, since the black solder resist composition of Patent Document 1 has a black color, the light absorption at -5 - 201211684 is increased at the time of exposure, and it is difficult for light to reach the deep portion of the solder resist film in particular. Therefore, in the deep portion of the solder resist coating film, photohardening is not sufficient, and the size of the deep portion of the solder resist coating film after development may be too small, and the resolution of the cured coating film may be peeled off from the printed scale, or the line may be poor. problem. Thus, there has been proposed a black solder resist composition (Patent Document 2) which is characterized in that a coloring agent blended in a carboxyl group-containing resin is used as a yellow coloring agent and a purple coloring agent, a yellow coloring agent, a blue coloring agent, and a red color. The colorant, the green colorant and the purple colorant, and any combination selected among the group of the green colorant and the red colorant are blackened. However, in Patent Document 2, in order to blacken the coloring agent other than the black coloring agent, it may be difficult to adjust to black, complicated, or to increase the blackness, the content of the coloring agent becomes high, and the analytical performance is still insufficient. problem. [Prior Art Document] [Patent Document] Patent Document 1 Japanese Laid-Open Patent Publication No. 2008-257045 Patent Document 2 Japanese Patent Application Laid-Open No. 20 1 0-9 1 8 7 6 [Problems to be Solved by the Invention] In view of the above circumstances, An object of the present invention is to provide a black curable resin composition which has excellent resolution and is easily adjusted to black and which can prevent color tone change after heat treatment. [Means for Solving the Problem] -6-201211684 The present invention relates to a black curable resin composition comprising (A) a carboxyl group-containing photosensitive resin, (B) a photopolymerization initiator, (C) a black curable resin composition of a diluent, (D) epoxy compound, and (E) black colorant, characterized in that the (E) black colorant contains (E-1) carbon black black colorant and (E-2) The lanthanum black coloring agent, and the content of the (E-2) lanthanum black coloring agent in the black coloring agent (E) is 53% by mass or more. In the above aspect, the carbon black-based black colorant and the lanthanide-based black colorant are blended in the coloring agent of the black curable resin composition, and the blending ratio of the lanthanide black colorant in all the black colorants is When it is 53% by mass or more, the light for exposure for photocuring reaches the deep portion of the coating film of the black curable resin composition, and is sufficiently photocured from the surface portion to the deep portion of the coating film. The carbon black black colorant reduces the brightness of the black curable resin composition, and supplements and improves the blackness. The aspect of the invention is a black curable resin composition characterized in that the transmittance of light having a wavelength of 300 to 400 nm of the (E-2) fluorene-based black colorant is 3% or more. In the above aspect, since the lanthanum black coloring agent having a light transmittance of 30,000 or more at a wavelength of 30,000 to 40 nm is blended, the ultraviolet light of the light amount required for photohardening can surely reach the black hardening applied to the substrate. The deep part of the resin composition. The aspect of the invention is a black curable resin composition characterized in that the transmittance of light having a wavelength of 400 to 700 nm of the (E-2) fluorene-based black colorant is 20% or less. The aspect of the present invention is a black curable resin composition characterized in that the (E-2) fluorene-based black colorant is at least 1669 to 1671 cm·1 and 1548 201211684 〜 in the infrared absorption spectrum measurement. Between 1 5 5 0cm·1, 1 49 8 to 1 500 cm·1, 1 402 ～1 404 cm·1, 1 2 83 〜1 2 8 5 cm·1, 822 ～824 cm·1 The absorption position between 763 and 765CHT1 and between 73 9 and 741 (:: ^1 has an infrared absorption peak. The aspect of the present invention is a black curable resin composition characterized by further containing (F) a blue colorant. In addition to the above black colorants, a blue colorant is further blended to reduce the brightness (L*値) measured by the color difference meter, and the color index (a*値) is from the positive side Further, the aspect of the present invention is a black curable resin composition characterized in that the blue colorant (F) is an indigo blue coloring agent. Is a black curable resin composition characterized by further containing (G) yellow colorant In addition to the above-described black colorants, the yellow colorant is further blended, whereby the L* 测定 measured by the color difference meter is lowered, and the chromaticity index (b*値) is adjusted from the negative side to the vicinity of 0. According to an aspect of the invention, a black curable resin composition is characterized in that the (G) yellow colorant is an anthraquinone yellow colorant. The aspect of the invention is a cured product which is hardened by the above black. Further, the aspect of the present invention is a cured product characterized in that L*値 is 25 or less, and a*値 and b*値 are both in the range of -2 to 2. An aspect of the invention is a cured product characterized by having a film thickness of 2 (wherein a transmittance of light having a wavelength of 40 〇 11111 of 7.0% or more. Further, the aspect of the invention is a printed wiring board, It is characterized in that the black curable resin composition described above is applied as a solder resist. -8- 201211684 [Effects of the Invention] According to the aspect of the present invention, among the total amount of the black colorant blended, the lanthanide black colorant is The blending ratio is set to 53% by mass or more, whereby The light that is hardened and used for exposure reaches the deep portion of the coating film of the black curable resin composition, so that it is sufficiently photohardened from the surface portion to the deep portion of the coating film. Thus, the photocuring proceeds sufficiently to the deep portion of the coating film, so even if it is coated A substrate such as a printed wiring board having a macro circuit pattern can prevent the film from being detached or damaged due to insufficient light hardening in the deep portion, thereby improving the resolution. Further, since the photohardening is sufficiently performed to the deep portion of the coating film Therefore, it is possible to prevent the width dimension of the deep portion of the cured coating film from being reduced. Therefore, the width dimension of the deep portion of the cured coating film is close to the width dimension of the surface layer portion of the cured coating film, and the dimensional accuracy of the cured coating film is improved. According to the aspect of the present invention, the lanthanum black coloring agent having a transmittance of light having a wavelength of 300 to 400 nm and having a transmittance of 3% or more is blended, so that it is possible to surely prevent the coating film from falling off or being damaged due to insufficient light hardening in the deep portion of the coating film. The resolution and dimensional accuracy are further improved. According to the aspect of the present invention, by further blending the blue colorant as needed, it is possible to adjust a** from the positive side to the vicinity of 0値 while reducing the L*値 measured by the color difference meter. The concentration and color tone are easy to adjust. According to the aspect of the present invention, by further blending the yellow colorant, it is possible to adjust the LM straightness measured by the color difference meter while adjusting the b*値 from the negative side to the vicinity of 0値, so that the black density and the color tone are easy. Adjustment. -9 - 201211684 [Embodiment] Next, each component of the black curable resin composition of the present invention will be described. The black curable resin composition of the present invention contains (A) a carboxyl group-containing photosensitive resin, (B) a photopolymerization initiator, (C) a diluent, (D) an epoxy compound, and (E) a black colorant. The curable resin composition, wherein the (E) black colorant contains (E-1) a carbon black-based black colorant and (E-2) an anthraquinone-based black colorant, and among the aforementioned (E) black colorants, the aforementioned (E-2) The content of the lanthanum black colorant is 53% by mass or more. (A) Carboxyl group-containing photosensitive resin The carboxyl group-containing photosensitive resin is not particularly limited, and a photosensitive carboxyl group-containing resin having one or more photosensitive unsaturated double bonds and a carboxyl group-containing resin having no photosensitive unsaturated double bond can be used. Either. Examples of the component (A) include at least a part of an epoxy group of a polyfunctional epoxy resin having two or more epoxy groups in the molecule, and a radical polymerization property such as a acrylic acid or a methyl propyl succinic acid is not The (meth)acrylic acid epoxy ester obtained by the reaction of a saturated monocarboxylic acid, and the polybasic acid modified (meth)acrylic acid epoxy ester obtained by reacting the produced hydroxyl group with a polybasic acid or an anhydride thereof. The above-mentioned polyfunctional epoxy resin may be used as long as it is a bifunctional or higher epoxy resin. Although it has no particular limitation on the epoxy equivalent, it is usually used in an amount of 1,000 or less, preferably 100 to 500. Examples of the polyfunctional epoxy resin include a modified epoxy resin such as a biphenyl type epoxy resin, a naphthalene type epoxy resin, a dicyclopentadiene type epoxy resin, or a polyfluorene modified epoxy resin; ε -己-10- 201211684 Lactone modified epoxy resin, bisphenol A type, bisphenol F type bisphenol AD type phenol novolak type epoxy resin; o-cresol novolac type cresol novolac type epoxy Resin; bisphenol A novolac type epoxy resin; cyclic aliphatic polyfunctional epoxy resin; glycidyl ester type multifunctional epoxy resin; glycidylamine type multifunctional epoxy resin; heterocyclic polyfunctional epoxy resin Bisphenol modified novolac type epoxy resin; polyfunctional modified novolac type epoxy resin; condensed epoxy resin having phenolic and phenolic hydroxyl groups and aromatic aldehydes as an example. Further, a halogen atom such as Br or C1 may be used as the resin. Among these, a rubber-modified epoxy resin such as a polyfluorene-based epoxy resin is preferable from the viewpoint of flexibility of the coating film. These epoxy resins may be used singly or in combination of two or more. The radically polymerizable unsaturated monocarboxylic acid to be used is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and the like, and at least one of acrylic acid and methacrylic acid is preferable (hereinafter also referred to as It is (meth)acrylic acid), and particularly preferably acrylic acid. The (meth)acrylic acid is reacted with (meth)acrylic acid epoxy ester. The reaction method of the epoxy resin and the radically polymerizable unsaturated monocarboxylic acid is not particularly limited, and for example, it can be reacted by heating an epoxy resin and acrylic acid in a suitable diluent. The polybasic acid or polybasic acid anhydride is a compound which reacts with a hydroxyl group formed in the reaction of the above epoxy resin and a radically polymerizable unsaturated monocarboxylic acid to carry a radical which is free from the resin. The polybasic acid or the anhydride thereof to be used is not particularly limited. Both saturated and unsaturated can be used. Examples of the polybasic acid include succinic acid, maleic acid, adipic acid, citric acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, and 4-methyltetrahydrophthalic acid. A-11 - 201211684 Acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4_A Hexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, Nea Examples of the methyl tetrahydrophthalic acid, methyl endethylenetetrahydrophthalic acid, trimellitic acid, pyromellitic acid, and oxydiglycolic acid, and the polybasic acid anhydrides include the acid anhydrides. These compounds may be used singly or in combination of two or more. In the present invention, the polybasic acid-modified unsaturated monocarboxylic acid epoxy resin may be used as a photosensitive resin, but a carboxyl group having the polybasic acid-modified unsaturated monocarboxylic acid epoxy resin may be used. A photosensitive resin having a photopolymerization property in which a radically polymerizable unsaturated group is reacted with an epoxy group-containing glycidyl compound to further introduce a radical polymerizable unsaturated group. In the photosensitive resin having improved photosensitivity, the radically polymerizable unsaturated group is bonded to the polymer skeleton side chain of the photosensitive resin of the precursor by the reaction of the final glycidyl compound, and thus the photopolymerization reactivity is high. And can have excellent photosensitive properties. Examples of the compound having one or more radical polymerizable unsaturated groups and an epoxy group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, and pentaerythritol triacrylate monoglycidyl ether. Wait for example. Further, a plurality of glycidyl groups may be present in one molecule. The above-mentioned compound having one or more free radically polymerizable unsaturated groups and an epoxy group may be used singly or in combination of two or more. -12- 201211684 The lower limit 酸 of the acid value of the carboxyl group-containing photosensitive resin is 30 mgKOH/g, preferably 40 mgKOH/g from the viewpoint of confirming alkali imaging. On the other hand, the upper limit of the acid value is 200 mgKOH/g from the viewpoint of preventing the exposure of the exposed portion by the alkali developing solution, and it is preferable from the viewpoint of preventing deterioration of moisture resistance and electrical properties of the cured product. It is 150 mgKOH/g. Further, the lower limit 重量 of the weight average molecular weight of the carboxyl group-containing photosensitive resin is 3,000, more preferably 5,000, from the viewpoint of the toughness of the cured product and the dryness of the touch. On the other hand, the upper limit 重量 of the weight average molecular weight is 200,000, preferably 50,000, from the viewpoint of compatibility with a diluent of the component (C) or the like and ease of alkali developability. As a commercially available person of the hydroxyl group-containing photosensitive resin, ZFR-11 24 , FLX-2089 (above, manufactured by Nippon Kayaku Co., Ltd.), and Cyclomer-P (ACA) Z-250 (Daicel Chemical Industry Co., Ltd.) can be cited. ), Ripoxy SP-4621 (Showa Polymer Co., Ltd.) and the like as an example. These resins may be used singly or in combination of two or more. (B) Photopolymerization initiator The photopolymerization initiator is not particularly limited as long as it is generally used by the user. The oxime initiator, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin are exemplified. Isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone' 2, 2-Diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4-(Methylthio)phenyl]-2-morpholinyl-propane-butanone, 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)one, di- 13- 201211684 . benzophenone, p-phenylbenzophenone, 4,4'-diethylaminodibenzophenone, dichlorobenzophenone, 2-methylindole, 2-ethyl Bismuth, 2-t-butyl oxime, 2-amino hydrazine, 2-methyl thioxanthone, 2-ethyl thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthene Examples of the ketone, 2,4-diethylthioxanthone, benzyldimethylketal, acetophenone dimethyl ketal, and P-dimethylamine benzoic acid ethyl ester are exemplified. These may be used alone or in combination of two or more. The amount of the photopolymerization initiator to be bonded is 5 to 20 parts by mass, preferably 8 to 15 parts by mass, per part by mass of the carboxyl group-containing photosensitive resin. (C) The diluent diluent is, for example, a photopolymerizable monomer of a reactive diluent, which is used for sufficiently photocuring a carboxyl group-containing photosensitive resin to obtain a cured product having acid resistance, heat resistance, alkali resistance, and the like. . Examples of the photopolymerizable monomer include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylic acid. Ester, polyethylene glycol di(meth) acrylate, neopentyl glycol adipate di(meth) acrylate, hydroxytrimethyl acetic acid neopentyl glycol di(meth) acrylate, dicyclopentan Alkyl di(meth) acrylate, caprolactone modified dicyclopentenyl di(meth) acrylate, ethylene oxide modified bis (meth) acrylate, allylated cyclohexyl (Meth) acrylate, trimeric isocyanate di(meth) acrylate, trimethylolpropane tri(meth) acrylate, dipentaerythritol tri(meth) acrylate, propionic acid modified dipentaerythritol tris (A) Acrylate, pentaerythritol tris(methyl)propane acrylate, propylene oxide modified trimethylolpropane tri(meth) acrylate, ginseng (propylene oxyethyl) trimeric isocyanate, propionic acid Divalent pentaerythritol tetra-14-201211684 Alcohol penta (meth) acrylate, dipentaerythritol Yl) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate reactive diluent as an example. These systems may be used singly or in combination of two or more. The amount of the reactive diluent to be added is 2.0 to 40 parts by mass, preferably 1 to 25 parts by mass, per 100 parts by mass of the carboxyl group-containing photosensitive resin. Further, as a diluent, in order to adjust the viscosity or dryness of the black curable composition, an organic solvent of a non-reactive diluent may be used instead of the above reactive diluent, or the above reactive diluent may be used in combination. . Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, isopropanol and cyclohexanol; and lipids such as cyclohexane and methylcyclohexane. Cyclic hydrocarbons; petroleum ethers such as petroleum ether and petroleum brain; 2-ethoxyethanols such as 2-ethoxyethanol (Cesare) and butyl 2-ethoxyethanol; carbitol and butyl Carbitol such as carbitol; ethyl acetate, butyl acetate, 2-ethoxyethanol acetate, butyl 2-ethoxyethanol acetate, carbitol acetate, butyl acetate An example of an acetate or the like of an alcohol ester or the like is exemplified. The blending amount in the case of using an organic solvent is preferably 40 to 500 parts by weight based on 1 part by weight of the carboxyl group-containing photosensitive resin. (D) epoxy compound
環氧化合物係爲用以提高硬化物之交聯密度，且得到 具有充分機械強度之硬化塗膜者。環氧化合物係爲例如環 氧樹脂。作爲環氧樹脂者’可列舉雙酚A型環氧樹脂；酚 醛清漆型環氧樹脂（酚酚醛清漆型環氧樹脂、鄰甲酚酚醛 清漆型環氧樹脂、對第三丁基酚酚醛清漆型等）；令雙酚F •15- 201211684 或雙酚S與表氯醇反應而得之雙酚F型或雙酚s型環氧樹 脂；進一步具有環氧環己烷基、環氧三環癸烷基、環氧環 戊烷基等之脂環式環氧樹脂；具有參（2,3-環氧丙基）三聚 異氰酸酯、三縮水甘油參（2-羥基乙基）三聚異氰酸酯等三 嗪環的三縮水甘油三聚異氰酸酯；二環戊二烯型環氧樹脂 :金剛烷型環氧樹脂爲例。該等化合物可單獨使用，亦可 混合2種以上來使用。環氧化合物之摻合量，由硬化後得 到有充分機械強度之塗膜的觀點而言，相對於含羧基感光 性樹脂100質量份，爲含有〗〇〜50質量份，較佳爲20〜 3 〇質量份。 (E)黑色著色劑 本發明中，係摻合（E-1)碳黑系黑色著色劑與（E-2)茈 系黑色著色劑作爲黒色著色劑。 (E-1)碳黑系黑色著色劑 碳黑系黑色著色劑係爲賦予硬化物隱蔽力與漆黑性者 。碳黑系黑色著色劑可列舉出碳黑。碳黑之種類並無特殊 限定，可列舉爐黑、槽黑、乙炔黑等爲例。再者’碳黑系 之顔料可列舉C.I.顏料黑6、7、9、18等的色指數號碼者 爲例。該等係可單獨使用，亦可混合2種以上來使用。 (E-2)茈系黑色著色劑 茈系黑色著色劑係賦予由本發明之黑色硬化性樹脂組 -16 - 201211684 成物形成之硬化物隱蔽力與黑色度，而且賦予黑色硬化性 樹脂組成物紫外光之透過性者。茈系黑色著色劑之種類雖 無特殊限定，但由塗膜深部之光硬化性的觀點而言，較佳 爲波長3 00〜400nm之光的透射率爲3%以上之茈系黑色著 色劑。由黑色色調之調整，亦即降低黑色中所含之紅色等 之色調，容易賦予漆黑性，且抑制焊接耐熱後變色的觀點 而言，於具有上述光之透射率特性之外，更佳爲進一步在 波長400〜700nm之光的透射率爲20%以下之茈系黑色著 色劑。進一步，由更容易賦予漆黑性的觀點而言，於上述 在波長3 00〜400nm及波長400〜700nm之光的透射率特 性之外，特佳爲至少在 1 669〜1671cm·1之間、1 548〜 1550cm·1 之間、1498 〜1500cm·1 之間、1402 〜1404cm-1 之 間、1 28 3 〜1 2 85cm·1 之間、822 〜824cm·1 之間、763 〜 765(:1^1之間及739〜741cm·1之間的吸收位置具有紅外線 吸收峰之菲系黑色著色劑。 作爲波長3 00〜400nm之光的透射率爲3%以上之茈系 黑色著色劑者，可列舉BASF Aktiengesellschaft公司製之 「Paliogen Black S 0084」、「Lumogen Black FK 4280」 、「Lumogen Black FK 4281」等爲例。其中，波長300〜 40011111之光的透射率爲3%以上、且波長400〜70011111之光 的透射率爲20%以下之茈系黑色著色劑可列舉「Lumogen Black FK 4280」、「Lumogen Black FK 4281」。另外， 「Paliogen Black S 0084」雖然在比波長6 8 0nm更短波長 之側的光透射率爲20%以下，但波長68 Onm以上之光的透 -17- 201211684 射率超過20%。「Lumogen Black’FK 4280」於波長300〜 750nm之光的透射率爲 20%以下。「Lumogen Black FK 4281」於波長300〜900nm之光的透射率爲20 %以下。 其中，於上述之波長3 00〜400nm及波長400〜700nm 之光的透射率特性之外，進一步地至少在1669〜167101^1 之間、1548 〜1550cm·1 之間、1498 〜1500cm·1 之間、1402 〜1404cm·1 之間、1283 〜1285cm·1 之間、82 2 〜824cm·1 之 間、7 63〜765CHT1之間及 73 9〜741CHT1之間的吸收位置 具有紅外線吸收峰的茈系黑色著色劑，可列舉「Lumogen Black FK 428 1」。另外，「Lumogen Black FK 4280」在 上述各吸收位置並無紅外線吸收峰，其至少在1 542〜 1 544cm-1 之間、1 502 〜1 504cnTi 之間、1 284 〜1 286cm·1 之 間及748〜75 OcnT1之間的吸收位置具有紅外線吸收峰。 該等茈系黑色著色劑係可單獨使用，亦可混合2種以上來 使用。 再者，於上述之各黑色著色劑之外，亦可按照需要， 進一步摻合苯胺黑、鈦黑、偶氮系黑、石墨系等公知之黑 色著色劑。 由賦予硬化物隱蔽力與黑色度之觀點而言，黑色著色 劑摻合量之下限値，相對於含羧基感光性樹脂1 00質量份 爲0.1質量份，由作爲黑色之外觀的觀點而言較佳爲0.2 質量份。由形成微細之硬化塗膜線的觀點而言，黑色著色 劑摻合量之上限値，相對於含羧基感光性樹脂100質量份 爲20質量，由得到硬化物解析度與尺寸精度的觀點而言 -18- 201211684 ，較佳爲10質量份。又’關於茈系黑色著色劑之含量佔 黑色著色劑總量，由紫外光之透過性的觀點而言，其下限 値爲5 3質量％，由塗膜深部之光硬化性的觀點而言，較佳 爲60質量％，由解析度的觀點而言，特佳爲65質量份。 另一方面，關於茈系黑色著色劑之含量佔黑色著色劑總量 ，由使a*値接近0而賦予漆黑性的觀點而言，其上限値爲 90質量％，由降低L*値，亦即得到黑色度的觀點而言較 佳爲85質量％，由作爲黑色之外觀的觀點而言，特佳爲 8 0質量％。 (F)藍色著色劑 爲了對本發明之黑色硬化性樹脂組成物所形成之硬化 物，使色差計之L*値降低、提高黑色度，並且使色差計 之a*値由正値側向0値方向接近，而賦予漆黑性，會摻合 藍色著色劑。摻合碳黑系黑色著色劑與茈系黑色著色劑時 ，硬化物之色調可能會顯現紅色，而具有正的a*値。由此 ，藉由添加藍色著色劑，來使硬化物之a*値向0値接近而 抑制紅色，使硬化物具有漆黑性。 藍色著色劑之種類並無特殊限定，可列舉酞青素系、 蒽醌系、雙噁嗪系之顏料。作爲藍色著色劑之具體例子者 ，可歹1J 舉 Pigment Blue 15、Pigment Blue 15: 1、 Pigment Blue 15: 2、Pigment Blue 15: 3、Pigment Blue 15: 4、 Pigment Blue 15: 6、Pigment Blue 16、Pigment Blue 60 等色指數號碼者。其中，由容易調整黑色之濃度及色調， -19- 201211684 容易顯出漆黑性的觀點而言，較佳爲酞青素系。該等係可 單獨使用，亦可混合2種以上來使用。 藍色著色劑之摻合量，能夠在使硬化物的a*値向0値 方向接近而抑制紅色的範圍內作適當選擇。只要指定厚度 之硬化物的a*値在0値附近（例如，-2〜2之範圍內），亦 可不添加藍色著色劑，即使在〇値附近，爲了更接近〇値 而顯出漆黑性，亦可添加指定量之藍色著色劑。在調整黑 色之濃度與摻雜紅色之色調的情況，例如，由抑制硬化物 之紅色而顯出漆黑性的觀點而言，相對於黑色著色劑100 質量份，摻合量之下限値爲較佳爲5質量份，由黑色度之 觀點而言特佳爲10質量份。又，由使硬化物之a*値向0 値接近的觀點而言，其上限値相對於黑色著色劑1 〇〇質量 份，較佳爲5 0質量份，由解析度的觀點而言，特佳爲3 0 質量份。 (G)黃色著色劑 爲了對由本發明之黑色硬化性樹脂組成物形成之硬化 物、使色差計之L*値降低、提高黑色度，並且使色差計 之b*値由負側向0値方向接近而賦予漆黑性，係摻合黃色 著色劑。摻合碳黑系黑色著色劑與茈系黑色著色劑時，硬 化物之色調可能會顯現紫色，而具有負的b *値。·由此，藉 由添加黃色著色劑，使硬化物之b*値向0値接近而抑制紫 色，使硬化物具有漆黑性。 黃色著色劑之種類並無特殊限定，可列舉蒽醌系、單 -20- 201211684 偶氮系、重氮化系'縮合偶氮系、苯并咪唑酮系、異吲哚啉 酮系等。作爲黃色著色劑之具體例子者，可列舉Solvent Yellow 163 ' Pigment Yellow 24 ' Pigment Yellow 108 ' Pigment Yellow 193 ' Pigment Yellow 147 ' Pigment Yellow 199、Pigment Yellow 202(以上爲葱醒系）；Pigment Yellow 1、 2、 3、 4、 5、 6、 9、 10、 12、 61、 62、 62: 1、 65、 73 、74、 75、 97、 100、 104、 105、 111、 116、 167、 168、 169、182、183(以上爲單偶氮系）；Pigment Yellow 12、13 、14、 16、 17、 55、 63、 81、 83、 87、 126、 127、 152、 170 、172 、 174 、 176 、 188 、 198(以上爲重氮化系）；Pigment Yellow 93 ' Pigment Yellow 94 ' Pigment Yellow 95 ' Pigment Yellow 128 、 Pigment Yellow 155 、 PigmentThe epoxy compound is used to increase the crosslinking density of the cured product and to obtain a cured coating film having sufficient mechanical strength. The epoxy compound is, for example, an epoxy resin. As the epoxy resin, bisphenol A type epoxy resin; novolak type epoxy resin (phenol novolac type epoxy resin, o-cresol novolak type epoxy resin, p-tert-butylphenol novolak type) Et.); a bisphenol F or bisphenol s type epoxy resin obtained by reacting bisphenol F •15-201211684 or bisphenol S with epichlorohydrin; further having an epoxycyclohexane group or an epoxy tricyclic oxime An alicyclic epoxy resin such as an alkyl group or an epoxycyclopentane group; having a bis(2,3-epoxypropyl)trimeric isocyanate or a triglycidyl ginate (2-hydroxyethyl)trimeric isocyanate; Triglycidyl trimeric isocyanate of a azine ring; dicyclopentadiene type epoxy resin: an adamantane type epoxy resin is exemplified. These compounds may be used singly or in combination of two or more. The blending amount of the epoxy compound is from 50 to 3 parts by mass, preferably from 20 to 3, based on 100 parts by mass of the carboxyl group-containing photosensitive resin, from the viewpoint of obtaining a coating film having sufficient mechanical strength after curing. 〇 mass parts. (E) Black coloring agent In the present invention, (E-1) carbon black-based black coloring agent and (E-2) lanthanum black coloring agent are blended as a coloring agent for coloring. (E-1) Carbon Black Black Colorant The carbon black black colorant is a one that imparts a concealing power and a blackening property to a cured product. Examples of the carbon black-based black colorant include carbon black. The type of the carbon black is not particularly limited, and examples thereof include furnace black, channel black, and acetylene black. Further, the pigment of the carbon black type may be exemplified by the color index numbers of C.I. Pigment Black 6, 7, 9, 18 and the like. These systems may be used singly or in combination of two or more. (E-2) lanthanide black colorant lanthanide black coloring agent imparts a hiding power and blackness to a cured product formed of the black curable resin group-16 - 201211684 of the present invention, and imparts a black curable resin composition to ultraviolet light. Transparency of light. The type of the lanthanum black coloring agent is not particularly limited, but from the viewpoint of photocurability in the deep portion of the coating film, a lanthanum black coloring agent having a transmittance of light of 30,000 to 400 nm and having a transmittance of 3% or more is preferable. It is more preferable to adjust the black color tone, that is, to reduce the color tone such as red contained in black, to impart blackiness, and to suppress discoloration after soldering heat resistance, and to have the above-described light transmittance characteristics. A fluorene-based black colorant having a transmittance of light having a wavelength of 400 to 700 nm of 20% or less. Further, from the viewpoint of more easily imparting blackness, it is particularly preferably at least 1 669 to 1671 cm·1, in addition to the transmittance characteristics of light having a wavelength of 300 to 400 nm and a wavelength of 400 to 700 nm. Between 548~1550cm·1, 1498~1500cm·1, 1402~1404cm-1, 1 28 3~1 2 85cm·1, 822~824cm·1, 763~ 765(:1 A phenanthrene-based black colorant having an infrared absorption peak at an absorption position between ^1 and 739 to 741 cm·1. As a lanthanum black colorant having a transmittance of 3% or more of light having a wavelength of 00 to 400 nm, Examples of "Paliogen Black S 0084", "Lumogen Black FK 4280", and "Lumogen Black FK 4281" manufactured by BASF Aktiengesellschaft, etc., wherein the transmittance of light having a wavelength of 300 to 40011111 is 3% or more and the wavelength is 400 to 70011111. "Lumogen Black FK 4280" and "Lumogen Black FK 4281" are exemplified as the black coloring agent having a light transmittance of 20% or less. Further, "Paliogen Black S 0084" has a shorter wavelength than the wavelength of 680 nm. The side light transmittance is 20% or less, but the wavelength is 68 O The transmittance of light above nm is -17-201211684, and the transmittance of "Lumogen Black'FK 4280" is less than 20% at a wavelength of 300 to 750 nm. "Lumogen Black FK 4281" is at a wavelength of 300 to 900 nm. The transmittance of light is 20% or less. In addition to the transmittance characteristics of the above-mentioned wavelengths of 300 to 400 nm and wavelengths of 400 to 700 nm, further at least between 1669 and 167101^1, and 1548 to 1550 cm·1. Between 1498 ～1500cm·1, 1402~1404cm·1, 1283~1285cm·1, 82 2 ～824cm·1, 7 63~765CHT1 and 73 9~741CHT1 The lanthanide black coloring agent having an infrared absorption peak at the absorption position is exemplified by "Lumogen Black FK 428 1". Further, "Lumogen Black FK 4280" has no infrared absorption peak at each of the above absorption positions, and it is at least 1 542 to 1 544 cm. The absorption position between -1, between 1 502 〜1 504cnTi, between 1 284 〜1 286 cm·1 and between 748 〜75 OcnT1 has an infrared absorption peak. These oxime-based black coloring agents may be used singly or in combination of two or more. Further, in addition to the respective black colorants described above, a known black colorant such as aniline black, titanium black, azo black or graphite may be further blended as needed. The lower limit of the blending amount of the black colorant is 0.1 part by mass based on 100 parts by mass of the carboxyl group-containing photosensitive resin, from the viewpoint of the appearance of black, from the viewpoint of the concealing power and the blackness of the cured product. Good is 0.2 parts by mass. From the viewpoint of forming a fine hard coating film line, the upper limit 掺 of the black colorant blending amount is 20 masses per 100 parts by mass of the carboxyl group-containing photosensitive resin, from the viewpoint of obtaining the cured product resolution and dimensional accuracy. -18- 201211684, preferably 10 parts by mass. Further, the content of the lanthanum black coloring agent accounts for the total amount of the black coloring agent, and the lower limit 値 is 53% by mass from the viewpoint of the transparency of the ultraviolet light, from the viewpoint of the photocurability of the deep portion of the coating film. It is preferably 60% by mass, and particularly preferably 65 parts by mass from the viewpoint of resolution. On the other hand, the content of the lanthanum black colorant accounts for the total amount of the black colorant, and the upper limit 値 is 90% by mass from the viewpoint of imparting blackness to a* 値 close to 0, and the L* 降低 is also lowered. That is, it is preferably 85% by mass from the viewpoint of obtaining a blackness, and particularly preferably 80% by mass from the viewpoint of the appearance of black. (F) Blue coloring agent In order to improve the cured product of the black curable resin composition of the present invention, the color difference meter L*値 is lowered, the blackness is increased, and the color difference meter is a*値 from the positive side to the zero side. The 値 direction is close, and the blackness is imparted, and the blue colorant is blended. When blending a carbon black-based black colorant with a lanthanide black colorant, the color tone of the cured product may appear red with a positive a*値. Thus, by adding a blue coloring agent, a*値 of the cured product is brought close to 0値 to suppress red color, and the cured product has blackness. The type of the blue coloring agent is not particularly limited, and examples thereof include pigments of anthracycline, anthraquinone, and bisoxazine. As a specific example of the blue coloring agent, Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60 color index number. Among them, from the viewpoint of easily adjusting the concentration and color tone of black, -19-201211684 is easy to show blackness, and it is preferably an anthracycline system. These systems may be used singly or in combination of two or more. The blending amount of the blue colorant can be appropriately selected within a range in which the a*値 of the cured product approaches the 0値 direction and the red color is suppressed. As long as the a*値 of the hardened material of the specified thickness is in the vicinity of 0値 (for example, in the range of -2 to 2), it is also possible to add no blue coloring agent, even in the vicinity of the crucible, to show darkness in order to be closer to the crucible. A specified amount of blue colorant can also be added. In the case of adjusting the concentration of black and the color of red doping, for example, from the viewpoint of suppressing the black color of the cured product, the lower limit of the blending amount is preferably the same with respect to 100 parts by mass of the black colorant. It is 5 parts by mass, and particularly preferably 10 parts by mass from the viewpoint of blackness. Further, from the viewpoint of bringing the a*値 of the cured product closer to 0 値, the upper limit 値 is preferably 50 parts by mass with respect to 1 part by mass of the black colorant, and from the viewpoint of resolution, Good for 30 parts by mass. (G) Yellow coloring agent, in order to reduce the L*値 of the color difference meter, and to improve the blackness of the cured product formed of the black curable resin composition of the present invention, and to make the b*値 of the color difference meter from the negative side to the 0値 direction Adjacent to give blackness, a yellow colorant is blended. When a carbon black-based black colorant and a lanthanide black colorant are blended, the color tone of the hardening may appear purple and have a negative b*値. - Thus, by adding a yellow coloring agent, b* of the hardened material is brought close to 0 而 to suppress purple color, and the cured product has blackness. The type of the yellow coloring agent is not particularly limited, and examples thereof include an anthraquinone system, a mono--20-201211684 azo system, a diazotization system, a condensed azo system, a benzimidazolone system, and an isoindolinone. Specific examples of the yellow coloring agent include Solvent Yellow 163 ' Pigment Yellow 24 ' Pigment Yellow 108 ' Pigment Yellow 193 ' Pigment Yellow 147 ' Pigment Yellow 199, Pigment Yellow 202 (above, onion); Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, 183 (above is a monoazo system); Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198 (above is diazotization); Pigment Yellow 93 ' Pigment Yellow 94 ' Pigment Yellow 95 ' Pigment Yellow 128 , Pigment Yellow 155 , Pigment
Yellow 166、Pigment Yellow 180(以上爲縮合偶氮系）； Pigment Yellow 120 、 Pigment Yellow 15 1 、 PigmentYellow 166, Pigment Yellow 180 (above condensed azo); Pigment Yellow 120, Pigment Yellow 15 1 , Pigment
Yellow 154、Pigment Yellow 156、Pigment Yellow 175、 Pigment Yellow 181(以上爲苯并咪唑酮系）；Pigment Yellow 110、Pigment Yellow 109、Pigment Yellow 139、 Pigment Yellow 179、Pigment Yellow 185(以上爲異吲哚 啉酮系）等色指數號碼者。其中，由黑色濃度及容易調整 色調而容易顯現出漆黑性的觀點而言，較佳爲蒽醌系。該 等可單獨使用，亦可混合2種以上來使用。 黃色著色劑之摻合量可在使硬化物之b*値向0値方向 接近而抑制紫色的範圔內作適當選擇。只要指定厚度之硬 化物的b*値在0値附近（例如，-2〜2之範圍內），亦可不 -21 - 201211684 添加黃色著色劑，即使在〇値附近，爲了更接近〇値而顯 出漆黑性，亦可添加指定量之黃色著色劑。在調整黑色之 濃度與帶有紫色之色調的情況，例如，由抑制硬化物之紫 色而顯出漆黑性的觀點而言，相對於黑色著色劑100質量 份，摻合量之下限値爲較佳爲5質量份，由黑色度之觀點 而言特佳爲10質量份。又，由使硬化物之b*値向0値接 近的觀點而言，其上限値相對於黑色著色劑1 00質量份， 較佳爲50質量份，由解析度的觀點而言，特佳爲30質量 份。 關於本發明之黑色硬化性樹脂組成物的硬化物之色調 ，色差計之L*値，由黑色度之觀點而言較佳爲30以下、 特佳爲25以下。又，色差計之a*値及b*値，由漆黑性之 觀點而言較佳均爲-3〜3、特佳爲-2〜2。再者，膜厚2 0 μηι 之硬化物中，波長400nm之光的透射率，由塗膜深部之光 硬化性的觀點而言較佳爲7%以上、特佳爲8%以上。因此 ，本發明之黑色硬化性樹脂組成物，在一邊考慮上述硬化 物之L*値、a*値、b*値、透射率，一邊以適當的摻合比 例來摻合上述之（A)〜（D)成分、下述之任意成分、還有上 述（E)〜（G)成分之著色劑。 本發明之黑色硬化性樹脂組成物，在上述成分之外， 能夠按照需要適當地摻合各種添加成分，例如消泡劑、各 種添加劑、顏料增量劑、增黏劑等。 | 消泡劑能夠使用公知者，可列舉聚矽氧烷系、烴系、 丙烯酸系等爲例。添加劑可列舉矽烷系、鈦酸鹽/酯系、 -22- 201211684 氧化鋁系等之偶合劑等分散劑；三氟化硼-胺錯合物、二 氰二胺（DICY)及其衍生物、有機酸醯肼、二胺順丁烯二腈 (DAMN)及其衍生物、三聚氰胺及其衍生物、胍胺及其衍 生物、胺基醯亞胺（AI)及多胺等潛在性硬化劑、乙醯丙酮 Zn及乙醯丙酮Cr等乙醯丙酮之金屬鹽、烯胺、辛酸錫、 4級锍鹽、三苯基膦、咪唑、咪唑鹽及三乙醇胺硼酸酯等 硬化促進劑爲例。顏料增量劑係爲用以提高硬化物之物理 強度者，可列舉矽石、硫酸鋇、氧化鋁、氫氧化鋁、滑石 、雲母等爲例。又，增黏劑可列舉有機膨潤土等。 上述之本發明的黑色硬化性樹脂組成物之製造方法， 其不限於特定的方法，但可例如爲將上述各成分以指定比 例摻合後，於室溫以三支輥混合分散而製造。 接著，說明上述之本發明的黑色硬化性樹脂組成物之 塗佈方法。此處，係以本發明之黑色硬化性樹脂組成物作 爲抗焊劑而塗佈於印刷配線板的情況爲例來說明。 將如上述而製造之本發明的黑色硬化性樹脂組成物， 於例如具有經蝕刻銅箔而形成之電路圖型的印刷配線板上 ，使用以網版印刷法、輥塗法、桿塗法、噴塗法、淋幕流 塗（curtain flow coating)法、凹版塗佈法等塗佈期望的厚 度，爲了使黑色硬化性樹脂組成物中之溶劑揮發，係進行 在60〜80°C左右之溫度加熱15〜60分鐘左右之預備乾燥 ’以形成無黏性之塗膜。之後，將具有令前述電路圖型焊 地以外帶透光性之圖型的負片，密著在經塗佈之黑色硬化 性樹脂組成物上’自上方照射紫外線。然後以稀鹼水溶液 -23- 201211684 去除對應於前述焊地之非曝光區域，藉以使塗膜顯像。顯 像方法係使用噴霧法、淋灑法等，所使用之稀鹼水溶液者 ，一般爲0.5〜5%之碳酸鈉水溶液，但亦可使用其他之鹼 。接著，以130〜170°C之熱風循環式乾燥機等，進行20 〜80分鐘的後硬化（post cure)，藉以使其熱硬化，而可在 印刷配線板上形成目標之黑色硬化性樹脂組成物之硬化塗 膜。 藉由噴流焊接方法、回流焊接方法等，於以如此而得 之硬化塗膜所被覆之印刷配線板，焊接電子零件，藉以形 成電子電路單元。 本發明之黑色硬化性樹脂組成物，除了作爲抗焊劑而 塗佈於印刷配線板之用途以外，以適宜的塗佈方法，亦能 夠利用於街燈用背光、重視美感的太陽電池用背板表面、 LED之背板表面等。 [實施例] 接著說明本發明之實施例，然在不超越本發明之主旨 之下，並不限定於該等例子。 實施例1〜1 3、比較例1〜5 以下述表1所示之摻合比例來摻合下述表1所示之各 成分，以攪拌機進行預備混合之後，使用3支輥於室溫混 合分散，以調製實施例1〜13、比較例1〜5中使用之黑色 硬化性樹脂組成物。接著，將調製後之黑色硬化性樹脂組 -24- 201211684 成物使用後述之試驗片製作步驟塗佈於基板上，而作成試 驗片。下述表1所示之各成分的摻合量，沒有特別說明的 話係指質量份。 -25- 201211684Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181 (above is benzimidazolone); Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185 (above isoporphyrin) Ketone system) is the color index number. Among them, from the viewpoint of black concentration and easy adjustment of color tone, it is preferable to be a enamel. These may be used singly or in combination of two or more. The blending amount of the yellow coloring agent can be appropriately selected within a range in which the b* 硬化 of the hardened material approaches the 0 而 direction and the purple color is suppressed. As long as the b*値 of the hardened material of the specified thickness is in the vicinity of 0値 (for example, in the range of -2 to 2), the yellow coloring agent may be added instead of - 21 - 201211684, even in the vicinity of the crucible, in order to be closer to the crucible In the case of blackness, a specified amount of yellow colorant may also be added. In the case of adjusting the concentration of black and the hue with a purple color, for example, from the viewpoint of suppressing the blackness of the cured product, the lower limit of the blending amount is preferably 100 parts by mass of the black colorant. It is 5 parts by mass, and particularly preferably 10 parts by mass from the viewpoint of blackness. In addition, the upper limit 値 is preferably 50 parts by mass with respect to 100 parts by mass of the black colorant from the viewpoint of the b* 硬化 of the cured product being close to 0 ,, and particularly preferably from the viewpoint of resolution. 30 parts by mass. The color tone of the cured product of the black curable resin composition of the present invention, L*値 of the color difference meter, is preferably 30 or less, and particularly preferably 25 or less from the viewpoint of blackness. Further, a*値 and b*値 of the color difference meter are preferably -3 to 3 and particularly preferably -2 to 2 from the viewpoint of blackness. Further, in the cured product having a thickness of 20 μm, the transmittance of light having a wavelength of 400 nm is preferably 7% or more, and particularly preferably 8% or more from the viewpoint of light hardenability in the deep portion of the coating film. Therefore, the black curable resin composition of the present invention blends the above (A) with an appropriate blending ratio while considering L*値, a*値, b*値, and transmittance of the cured product. The component (D), any of the following components, and the coloring agent of the above (E) to (G) components. In addition to the above components, the black curable resin composition of the present invention may be appropriately blended with various additives such as an antifoaming agent, various additives, a pigment extender, and a tackifier. The antifoaming agent can be a known one, and examples thereof include polyoxyalkylene-based, hydrocarbon-based, and acrylic-based. Examples of the additive include dispersants such as a decane-based, titanate-based, -22-201211684 alumina-based coupling agent; boron trifluoride-amine complex, dicyandiamide (DICY) and derivatives thereof, Organic acid bismuth, diamine maleimonitrile (DAMN) and its derivatives, melamine and its derivatives, guanamine and its derivatives, amine quinone imine (AI) and polyamines and other potential hardeners, A hardening accelerator such as a metal salt of acetamidine such as acetonitrile acetin or acetonitrile acetone Cr, an enamine, a tin octylate, a quaternary phosphonium salt, a triphenylphosphine, an imidazole, an imidazole salt or a triethanolamine borate is exemplified. The pigment extender is used to increase the physical strength of the cured product, and examples thereof include vermiculite, barium sulfate, alumina, aluminum hydroxide, talc, and mica. Further, examples of the tackifier include organic bentonite and the like. The method for producing the black curable resin composition of the present invention is not limited to a specific method, and may be produced, for example, by blending the above components in a predetermined ratio and then mixing and dispersing them in three rolls at room temperature. Next, a method of applying the black curable resin composition of the present invention described above will be described. Here, a case where the black curable resin composition of the present invention is applied as a solder resist to a printed wiring board will be described as an example. The black curable resin composition of the present invention produced as described above is used, for example, by a screen printing method, a roll coating method, a rod coating method, or a spray coating on a printed wiring board having a circuit pattern formed by etching a copper foil. The desired thickness is applied by a method, a curtain flow coating method, a gravure coating method, or the like, and is heated at a temperature of about 60 to 80 ° C in order to volatilize the solvent in the black curable resin composition. ~60 minutes of pre-drying 'to form a non-stick coating. Thereafter, a negative film having a pattern in which the above-mentioned circuit pattern soldering is light-transmissive is adhered to the applied black curable resin composition, and ultraviolet rays are irradiated from above. Then, the non-exposed area corresponding to the foregoing soldering land is removed with a dilute aqueous solution -23-201211684, whereby the coating film is developed. For the development method, a spray method, a shower method, or the like is used, and a dilute alkali aqueous solution used is generally a 0.5 to 5% sodium carbonate aqueous solution, but other bases may be used. Then, a post-curing is performed for 20 to 80 minutes by a hot air circulating dryer at 130 to 170 ° C to thermally cure the target, and a target black curable resin can be formed on the printed wiring board. Hardened coating of the object. The electronic component is formed by soldering the electronic component to the printed wiring board covered with the cured coating film thus obtained by a jet welding method, a reflow soldering method, or the like. The black curable resin composition of the present invention can be applied to a printed wiring board in addition to a solder resist, and can be used for a backlight for a street lamp, a surface of a back sheet for a solar cell that emphasizes aesthetics, and an appropriate coating method. The back surface of the LED, etc. [Examples] Next, examples of the present invention will be described, but they are not limited to the examples without departing from the gist of the present invention. Examples 1 to 1 3, Comparative Examples 1 to 5 The components shown in the following Table 1 were blended at the blending ratios shown in Table 1 below, and after preliminary mixing by a stirrer, the mixture was mixed at room temperature using 3 rolls. The black curable resin compositions used in Examples 1 to 13 and Comparative Examples 1 to 5 were prepared by dispersion. Next, the prepared black curable resin group -24 - 201211684 was applied to a substrate by using a test piece preparation step described later to prepare a test piece. The blending amount of each component shown in the following Table 1 means a part by mass unless otherwise specified. -25- 201211684
另外，關於表1中之各成分的詳述’係如以下所示。 -26- 201211684 (A) 含羧基感光性樹脂 .Ripoxy SP-4621 :昭和高分子（股）製、多元酸改質甲 酚酚醛清漆型環氧丙烯酸酯樹脂 (B) 光聚合起始劑 •IRGACURE 907 : Ciba Specialty Chemicals(股）製、 2-甲基- l-[4-(甲硫基）苯基]-2-嗎啉基丙烷-1-酮 •IRGACURE 3 69 : Ciba Specialty Chemicals(股）製、 2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基）-丁酮-1 (C) 稀釋劑 • EDGAC :三洋化成（股）製、二伸乙甘醇乙醚醋酸酯 (D) 環氧化合物 •EPCRON 860:大日本油墨化學工業（股）製、雙酚A 型環氧樹脂 (E) 黑色著色劑 .碳黑：電氣化學工業（股）製、「Denka Black」 •LUMOGEN BLACK FK428 1: BASF Aktiengesellschaft 公司製 •LUMOGEN BLACK FK4280: BASF Aktiengesellschaft 公司製 •Paliogen Black S 0084: BASF Aktiengesellschaft ^ 司製 (F) 藍色著色劑 •Lionol Blue FG-73 5 1 :東洋油墨製造（股）製、酞青素 -27- 201211684 系之顏料 (G)黃色著色劑 •Chromophtal Yellow AGR: Ciba Specialty Chemicals(股 )製、蒽醌系之顏料 其他，DICY-7係Japan Epoxy Resin(股）製之硬化促 進劑。 試驗片製作步驟 將形成電路圖型之玻璃環氧基板（FR-4)，以拋光硏磨 進行表面處理後，以網版印刷法分別塗佈實施例1〜1 3及 比較例1〜5之黑色硬化性樹脂組成物後，在B OX爐進行 80°C、20分鐘之預備乾燥。預備乾燥後，於塗膜上以曝光 裝置（Oak公司製 HMW-680GW)曝光 500mJ/cm2後，以 3 0°C、1%之碳酸鈉水溶液顯像後，在BOX爐進行150°C、 60分鐘之硬化，而在玻璃環氧基板上形成黑色硬化性樹脂 組成物之硬化塗膜，以作成試驗片。硬化塗膜之厚度爲 2 0 μηι 〇 評估 (1)解析度 以目視確認、評估透過指定之光罩（線3 0〜1 3 0 μηι)而 形成之曝光部的殘存之線與空出的間距。 (2)底切 -28- 201211684 對於使用寬度ΙΟΟμπι之光罩以形成硬化塗膜之線後的 基板，切斷基板並由切斷面觀察該線，並測定線之表面側 的寬度（X)與底部側（深部側）的寬度（y)，由（x-y)/2評估底 切。 (3)L* 値、a*値、b* 値 以色差計SE2000(日本電色工業（股））測定。 (4) 透射率 對於形成硬化塗膜後之玻璃環氧基板，測定波長 400nm之光的透射率，將另外測定之玻璃環氧基板單體之 波長400nm光之透射率用於基準線，藉以測定硬化塗膜之 透射率。透射率之測定係使用UV分光光度計U-3310(日 立 High Technology(股））。 (5) 焊接耐熱後變色 將試驗片浸漬於260°C之焊接槽20秒後，以目視觀察 硬化塗膜之狀態，評估變色的程度。 將實施例1〜13、比較例1〜5之解析度、底切、L* 値、a*値、b*値、透射率、焊接耐熱後變色的結果示於表 2 ° -29 - 201211684 【截In addition, the detailed description of each component in Table 1 is as follows. -26- 201211684 (A) Carboxyl group-containing photosensitive resin. Ripoxy SP-4621: Showa polymer (stock), polyacid modified cresol novolak type epoxy acrylate resin (B) Photopolymerization initiator · IRGACURE 907 : Ciba Specialty Chemicals Co., Ltd., 2-methyl-l-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one • IRGACURE 3 69 : Ciba Specialty Chemicals , 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1 (C) thinner • EDGAC: Sanyo Chemical Co., Ltd. Alcohol Ether Acetate (D) Epoxy Compound • EPCRON 860: Dainippon Ink Chemical Industry Co., Ltd., Bisphenol A Epoxy Resin (E) Black Colorant. Carbon Black: Electrochemical Industry (Stock), Denka Black" • LUMOGEN BLACK FK428 1: manufactured by BASF Aktiengesellschaft • LUMOGEN BLACK FK4280: manufactured by BASF Aktiengesellschaft • Paliogen Black S 0084: BASF Aktiengesellschaft ^ Division (F) Blue colorant • Lionol Blue FG-73 5 1 : Toyo Ink manufacturing (stock), cordierin-27- 201211684 pigment (G) yellow colorant • Chromophta l Yellow AGR: Ciba Specialty Chemicals, a pigment based on lanthanide. Other, DICY-7 is a hardening accelerator made by Japan Epoxy Resin. In the test piece production step, a glass epoxy substrate (FR-4) having a circuit pattern was formed, and after surface treatment by polishing honing, the blacks of Examples 1 to 13 and Comparative Examples 1 to 5 were respectively applied by screen printing. After the curable resin composition, it was preliminarily dried at 80 ° C for 20 minutes in a B OX furnace. After preliminary drying, the film was exposed to 500 mJ/cm 2 by an exposure apparatus (HMW-680GW manufactured by Oak Co., Ltd.), and then developed at 30 ° C and 1% sodium carbonate aqueous solution, and then subjected to 150 ° C, 60 in a BOX furnace. After hardening for a minute, a hard coating film of a black curable resin composition was formed on a glass epoxy substrate to prepare a test piece. The thickness of the hardened coating film is 20 μηι 〇 Evaluation (1) Resolution The visually confirmed and evaluated the residual line and the vacant pitch of the exposed portion formed by the specified mask (line 30 to 1 30 μm) . (2) Undercut -28-201211684 For a substrate which is formed by using a mask having a width of ΙΟΟμπι to form a line of the cured coating film, the substrate is cut and observed by the cut surface, and the width (X) of the surface side of the line is measured. With the width (y) of the bottom side (deep side), the undercut is evaluated by (xy)/2. (3) L* 値, a*値, b* 测定 Measured by a color difference meter SE2000 (Nippon Denshoku Industries Co., Ltd.). (4) Transmittance The transmittance of light having a wavelength of 400 nm is measured for a glass epoxy substrate on which a cured coating film is formed, and the transmittance of light having a wavelength of 400 nm of a glass epoxy substrate alone measured is used for a reference line, thereby measuring The transmittance of the hardened coating film. The transmittance was measured by using a UV spectrophotometer U-3310 (Hitachi High Technology Co., Ltd.). (5) Discoloration after heat resistance of the solder After the test piece was immersed in a solder bath at 260 ° C for 20 seconds, the state of the cured film was visually observed to evaluate the degree of discoloration. The resolutions, undercuts, L* 値, a*値, b*値, transmittance, and discoloration of the heat resists of Examples 1 to 13 and Comparative Examples 1 to 5 are shown in Table 2 ° -29 - 201211684 [ cut
比？例 I I CO ci 00 00 o -0.56 csl 無變化 比較例 4 〇 〇 2 CM 〇 00 CM d CO 無變化 比較例 3 〇 <〇 00 CM 40 CM CNi 無變化 比較例 2 〇 <〇 〇 5 -0.11 o C5 CO 無變化 比較例 1 〇 ΙΑ CO 5 -1.88 «Ν OJ 兮 變色爲 茶褐色 實施例 13 〇 r- 16.13 CM 5 ΪΛ <〇 00 <71 無變化 實施例 12 〇 CD OJ 14.72 K CO O) 〇 O) to 無變化 實施例 11 § 卜 O) to CO σ» OI OI 無變化 實施例 10 § CO 00 n 00 ? -0.12 ια 诹¢3 Φ辑 i實施例 I. 9 〇 <〇 OI 〇> 00 σ> -0.56 CO o 無變化 實施例 8 S esi cd CM -0.16 CO 产 無變化 S施例 7 S <〇 ca 14.55 -1.21 T e> 無變化 S施例 6 S w CM 13.27 -0.42 ai iq 無變化 實施例 5 g CO 14.79 r-» o C5 to o 5 無變化 實施例 4 S GO 15.39 00 CO o iO 00 ai 無變化 K施例 3 S S 13.65 g 丁 CO ? 無變化 實施例 2 S CO to ui O) o <〇 o o CM CO 無變化 實施例 1 导 r* 1627 Γ*· CO 00 O) Of ai 無變化 解析度 (Um) 底切 (Um) 普 * {〇 « •O 於400nm之 透射率(％) 11 ®p II 钿激震濉|(* 由表2之實施例1〜1 3與比較例1〜4，可知碳黑與_花 系黑色著色劑之混合物中，使用菲系黑色著色劑之摻合比 -30- 201211684 例超過52質量％之黑色著色劑時，波長400nm之光的透 射率會提高，能夠得到具有優良解析度與低底切的硬化物 。進一步地，a*値在0値附近（例如-2〜2的範圍），或即 使不在〇値附近時，能夠抑制由〇値大幅偏離。如此，本 發明之黑色硬化性樹脂組成物，於硬化塗膜之膜厚20μχη 時，波長400nm之光的透射率爲7.5%以上，因此光硬化 能夠到達塗膜的深部。再者，由於光硬化能夠到達塗膜的 深部而具有70μηι以下的解析度，因此亦能夠因應微距的 電路圖型。進一步地，因爲能夠將底切抑制在26μιη以下 ，即使微距的電路圖型亦能夠防止線的剝離或缺損等，並 提高線的尺寸精度。然後，因爲能夠抑制a*値在較低的水 準，故容易進行黑色調之調整，亦即降低黑色中之紅色或 紫色等的色調、產生漆黑性。 又，由實施例2、8與實施例10，波長300〜400nm 之光的透射率爲3%以上' 且波長400〜700nm之光的透射 率爲20%以下的茈系黑色著色劑亦即「Lumogen Black FK 428 1」（實施例 2)及「Lumogen Black FK 4280」（實施例 8)，其相較於波長680〜700nm之光的透射率超過2〇%的 「Paliogen Black S 0084」（實施例10)，其L*値能夠抑制 在更低的水準，再者能夠使a*値與b*値更接近0値附近 ，因此更容易提高黑色度同時抑制紅色或紫色等色調’以 產生漆黑性。 又，由實施例2、8’在 1669〜1671cm·1之間、1548 〜1 550cm·1 之間、1498 〜1 500cm·1 之間、1402 〜1404cm-1 -31 - 201211684 之間、1 2 8 3 〜1 2 8 5 cm·1 之間、8 22 〜824cm·1 之間、763 〜 765CHT1之間、739〜741CIXT1之間的吸收位置具有紅外線 吸收峰的茈系黑色著色劑亦即「Lumogen Black FK 428 1 」（實施例2)，相較於「Lumogen Black FK 4280」（實施例 8)，其L*値能夠抑制在更低的水準，再者能夠使a*値與 b*値更接近0値附近，因此更容易產生漆黑性。 再者，使用波長300〜400nm之光的透射率爲3 %以上 、且波長400〜700nm之光的透射率爲20%以下之茈系黑 色著色劑時，能夠抑制焊接耐熱後變色。 又，由實施例1〜9，藉由摻合相對於黑色著色劑100 質量份之藍色著色劑9〜19質量份、與黃色著色劑30質 量份以下，能夠使a*値及b*値均落在-2〜2的範圍內，且 抑制黑色中之紅色等色調，賦予硬化物漆黑性。 由比較例5，將黑色著色劑之摻合量設爲相對於含羧 基感光性樹脂100質量份，爲21.8質量份以上時，硬化 物之線消失，解析度會劣化。 [產業上之可利用性] 本發明之黑色硬化性樹脂組成物，具有優良的解析度 ，又，容易調整爲黑色，且能夠防止熱處理後之色調變化 ，故例如在抗焊劑的領域有高利用價値。 -32-ratio? Example II CO ci 00 00 o -0.56 csl No change Comparative Example 4 〇〇2 CM 〇00 CM d CO No change Comparative Example 3 〇<〇00 CM 40 CM CNi No change Comparative Example 2 〇<〇〇5 - 0.11 o C5 CO No change Comparative Example 1 〇ΙΑ CO 5 -1.88 «Ν OJ 兮color is brownish brown Example 13 〇r- 16.13 CM 5 ΪΛ <〇00 <71 No change Example 12 〇CD OJ 14.72 K CO O) 〇O) to no change Example 11 § Ob O) to CO σ» OI OI No change Example 10 § CO 00 n 00 ? -0.12 ια 诹¢3 Φ I Example I. 9 〇<〇 OI 〇 > 00 σ> -0.56 CO o No change Example 8 S esi cd CM -0.16 CO production no change S Example 7 S <〇ca 14.55 -1.21 T e> No change S Example 6 S w CM 13.27 -0.42 ai iq No change Example 5 g CO 14.79 r-» o C5 to o 5 No change Example 4 S GO 15.39 00 CO o iO 00 ai No change K Example 3 SS 13.65 g D CO ? No change implementation Example 2 S CO to ui O) o <〇oo CM CO No change Example 1 Introduction r* 1627 Γ*· CO 00 O) Of ai No change resolution (Um) Undercut (Um) ** {〇« •O Transmittance at 400 nm (%) 11 ® p II 钿Shocking 濉|(* From Examples 1 to 13 of Table 2 and Comparative Examples 1 to 4, it is known that carbon black and _ flower black When a blending ratio of phenanthrene black colorant is used in a mixture of colorants of more than 52% by mass of a black colorant, the transmittance of light having a wavelength of 400 nm is improved, and excellent resolution and low bottom can be obtained. Further, a*値 is in the vicinity of 0値 (for example, in the range of −2 to 2), or even when it is not in the vicinity of the crucible, it is possible to suppress a large deviation from the crucible. Thus, the black curable resin of the present invention In the composition, when the film thickness of the cured coating film is 20 μχη, the transmittance of light having a wavelength of 400 nm is 7.5% or more, and thus the photocuring can reach the deep portion of the coating film. Further, since the light hardening can reach the deep portion of the coating film and has a resolution of 70 μm or less, it is also possible to respond to the circuit pattern of the macro. Further, since the undercut can be suppressed to 26 μm or less, even a macro circuit pattern can prevent peeling or chipping of the wire, and the dimensional accuracy of the wire can be improved. Then, since it is possible to suppress a* 値 at a low level, it is easy to adjust the black tone, that is, to reduce the hue of red or purple in black, and to produce blackness. Further, in Examples 2, 8 and 10, the transmittance of light having a wavelength of 300 to 400 nm is 3% or more and the transmittance of light having a wavelength of 400 to 700 nm is 20% or less. Lumogen Black FK 428 1" (Example 2) and "Lumogen Black FK 4280" (Example 8), which is equivalent to "Paliogen Black S 0084" having a transmittance of light exceeding 280% to 280% at a wavelength of 680 to 700 nm. In Example 10), L*値 can be suppressed to a lower level, and a*値 and b*値 can be closer to 0値, so it is easier to increase the blackness while suppressing the hue of red or purple to produce black. Sex. Further, the examples 2 and 8' are between 1669 and 1671 cm·1, between 1548 and 1 550 cm·1, between 1498 and 1 500 cm·1, between 1402 and 1404 cm-1 to 31 to 201211684, and 1 2 "Lumogen" is a lanthanide black colorant having an infrared absorption peak at an absorption position between 8 3 and 1 2 8 5 cm·1, between 8 22 and 824 cm·1, between 763 and 765 CHT1, and between 739 and 741 CIXT1. Black FK 428 1 ” (Example 2), compared to “Lumogen Black FK 4280” (Example 8), its L*値 can be suppressed at a lower level, and can further make a*値 and b*値It is close to 0値, so it is more likely to produce blackness. When the transmittance of light having a wavelength of 300 to 400 nm is 3 % or more and the transmittance of light having a wavelength of 400 to 700 nm is 20% or less, it is possible to suppress discoloration after solder heat resistance. Further, in Examples 1 to 9, by blending 9 to 19 parts by mass of the blue coloring agent with respect to 100 parts by mass of the black coloring agent and 30 parts by mass or less with the yellow coloring agent, a*値 and b*値 can be obtained. They all fall within the range of -2 to 2, and suppress the color tone such as red in black, giving the cured product blackness. In the case of the comparative example 5, when the blending amount of the black coloring agent is 21.8 parts by mass or more based on 100 parts by mass of the carboxyl group-containing photosensitive resin, the line of the cured product disappears and the resolution deteriorates. [Industrial Applicability] The black curable resin composition of the present invention has excellent resolution, is easily adjusted to black, and can prevent color change after heat treatment, so that it is highly utilized in the field of solder resist, for example. Price. -32-