517503 A7 ___m________ 五、發明說明（/ ) 技術頜域 本發明係關於用以形成印刷配線板之永久保護膜之防 焊油墨。更明白地說，本發明係關於受到紫外線照射會硬 化之防焊油墨。 尤其，本發明係關於在微鹼性水溶液會顯像之光防焊 油墨與非顯像型之紫外線硬化型防焊油墨。這種防焊油墨 可顯著地減低燃燒時之有毒氣體之產生量。 技術背景 電氣製品所用印4ι配線基板，是在銅面積層板等之基 板上形成既定配線之產品。此印刷配線基板，爲了防止進 行焊接時對非必要之部分附著焊料，以避免電路之短路， 且爲了防止其壽命之縮短，一般乃在基板上形成導體配線/ 後，依既定圖案來形成由防焊油墨之硬化物所構成之永久 保護膜。 構成此種印刷配線基板之基板或防焊油墨，以往係含 有溴化物等之鹵化物，其於燃燒時會產生有毒氣體，而成 爲一大問題。 不過’隨著近年來對於環保問題及人體之女全性之思 識高漲，乃要求燃燒時不會產生有毒氣體之印刷配線基板 之開發。回應此類要求，雖有例如去鹵化之玻璃環氧銅面 積層板等之基板被開發，但關於防焊油墨，則仍未達成充 分地降低鹵素含量之目標。 一般而言，在印刷配線基板上所形成之防焊油墨之永 久保護膜，於目視檢查時其辨視性需優良，此外也需注意 3 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 517503 A7 _ B7 _ 五、發明說明（上） 不傷眼力。因此，所用之永久保護膜必須爲綠色。 因而，習用之防焊油墨，係配合有酞菁綠等之著色顏 料，而呈綠色。不過，此酞菁綠之化學結構式中所含氯及 溴之比例很高。具體言之，例如比色指數(color index)爲顏 料綠7之駄菁綠每一分子中含有47重量％之氯，又顏料36 之肽菁綠之一分子中含有約5重量％之氯及約60重量％之 溴。 因此，像酞菁綠般的含有高比例之鹵素之著色顏料所 調配成之習知防焊油墨，於其燃燒時，將產生大量之有毒 氣體。 本發明即以提供不含鹵素或鹵素含有量很低之防焊油 墨爲解決之課題。 發明之揭示 本第一發明係一種防焊油墨，其特徵爲，含有： (A) 紫外線硬化性成分； (B) 光聚合起始劑；以及 (C) 著色顏料，係由化學結構式中不含鹵素之橙色顏料 及化學結構式中不含鹵素之藍色顏料以呈現綠色的方式所 配合而成者。此防焊油墨尤具有光防焊油墨之用途。 本第二發明之光防焊油墨之紫外線硬化性成分，以含 (A-4)乙烯性不飽和單體者最理想。 又，此防焊油墨，若再含有(D)有機溶劑爲更佳。 又’此防焊油墨，若再含有(E)多官能環氧化合物更佳 4 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -------I---· I I I I--1 ^ · I I I-----^^^^1 (請先閱讀背面之注意事項再填寫本頁) 517503 A7 _ B7__ 五、發明說明（$ ) Ο 又，此防焊油墨之硬化物中之含鹵素量以500ppm以 下爲更佳。 又，上述之防焊油墨中所配合之作爲(A-1)成分之紫外 線硬化性樹脂及作爲(E)成分之多官能環氧化合物係例如以 過酸法所合成之不含鹵素之環氧化合物、或是實施過用以 減低鹵素之處理之環氧化合物所調製而成，若使用以此方 式調整之(A-1)成分與/或(E)成分，則本發明之光防焊油墨 之硬化物中之鹵素含量可在150ppm以下。 又，做爲(C)成分之著色顏色，以重量比1:10〜10:1所 配合之橙色顏料及上述藍色顏料爲佳。 又，本第三發明係一種防焊油墨，其特徵爲含有： (A-3)環氧（甲基)丙烯酸酯及/或多元酚之聚醚化物及（甲 基)丙烯酸所成之酯化物； 前述(A-3)成分以外之(A-4)乙烯性不飽和化合物； (B) 光聚合起始劑；以及 (C) 者色顏料，係由化學結構式中不含鹵素之撥色顏料 及化學結構式中不含鹵素之藍色顏料以呈現綠色的方式所 配合而成者。 7 本第三發明之紫外線硬化型之防焊油墨之硬化物中鹵 素含有量以500ppm以下爲佳。 又，該著色顏料，化學結構式中不含鹵素之橙色著色 顏料與化學結構式中不含鹵素之藍色著色顏料以重量比 1:10〜10:1來組合爲佳。 5 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 x 297公爱） " ---------------------------- (請先閱讀背面之注意事項再填寫本頁) 517503 A7 ____B7 五、發明說明（士） 以下對本發明進一步詳細說明。 用以實旆發明之最佳形熊 本發明之防焊油墨，含有(A)紫外線硬化性成分、（B) 光聚合起始劑、（C)化學結構式中不含鹵素之模色顏料及化 學結構式中不含鹵素之藍色顏料。 (A) 紫外線硬化性成分： 本發明中之防焊油墨，配合做爲(A)成分之紫外線硬化 性成分。此紫外線硬化性成分，爲有紫外線硬化性之機能 之成分，其與做爲後述之(C)成分之光聚合起始劑一起所搭 配而成之本發明之防焊油墨，經紫外線照射，即硬化。 且，在含有後述之(D)有機溶劑時，除去此有機溶劑外 ，本發明之防焊油墨之全成分中之(A)紫外線硬化性成分較 佳爲含有20〜80重量％爲佳。 在本發明中所配合之(A)紫外線硬化性成分，只要經由 紫外線照射而硬化即可，並無特別限定，例如，可自具有 光反應性之雙鍵之紫外線硬化性樹脂或光聚合性之單體等 習知的紫外線硬化性成分任意選擇。 (B) 光聚合起始劑 在本發明之防焊油墨中，除了上述之(A)紫外線硬化性 成分之外，尙含有(B)成分之光聚合起始劑。 本發明中所含上述之光聚合起始劑，雖無特別限定， 但在本發明中較適合之光聚合起始劑，可舉例如下： 苯偶因；苯偶因甲醚、苯偶因乙醚及苯偶因丙醚等之 苯偶因之烷醚類；乙醯苯，2,2-二甲氧基-2-苯基乙醯苯 6 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 517503 A7 _B7_ 五、發明說明（f ) ，2,2-二乙氧基-2-苯基乙醯苯，及1-羥基環己基苯酮等之乙酿 苯類；2-甲基憩醌，2-乙基憩輥，及2-氨基憩醌等之蔥醌類； 2,4-二甲基噻噸酮，及2,4-二乙基噻噸酮，及2.4-二異丙基噻 噸酮等之噻噸酮類；乙醯苯二甲基縮酮及苄基二甲基縮酮 等之縮酮類；二苯甲酮，3,3-二甲基-4-甲氧基二苯甲酮， 3,3’，4,4’-四-(特丁基過氧羰基）二苯甲酮及4-苯甲醯-4-甲基 二苯基硫化物等之二苯甲酮類或氧雜憩酮類；2-羥基-2-甲 基小苯基丙烷小酮及1-羥基-環已基-苯基酮等之α -羥基酮 類；2-甲基小[4-(甲硫基）苯基]-2-嗎琳-丙烷-1-酮，2-苯甲 醯-2-二甲胺基-1-(4-嗎啉苯基)-丁酮-1，4,4’-雙一二乙胺基二 苯甲酮等之含氮原子者；2,4,6-三甲基苯甲醯二苯基膦氧化 物等。 上述這些(B)光聚合起始劑，可分別單獨或以適當組合 調配，來調製本發明之防焊油墨。 又，這些光聚合起始劑，也可與苯甲酸系，對二甲胺 苯甲酸乙酯，對二甲胺苯甲酸異戊酯，2-二甲胺基乙基苯 甲酸酯等之第三級胺系等習知之光聚合促進劑或增感劑倂 用。 作爲此(B)成分之光聚合起始劑，於含有後述(D)成分 之有機溶劑時，除了此有機溶劑外，在本發明之防焊油墨 之全成分中以含有0.1〜30重量％爲佳，0.1〜10重量％更 佳，而最佳是0.1〜7重量％。含有前述範圍之配合量之光 聚合起始劑時，本發明之防焊油墨將顯示極優之光硬化性 ，所得到之永久保護膜之物性也十分良好。 7 ------------^^裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 517503 A7 ____ B7___ 五、發明說明（心） (C)著色顏料 此外，在本發明之防焊油墨中，配合有作爲(C)成分之 著色顏料。在本發明所配合之著色顏料，是由在化學結構 式中不含鹵素之橙色顏料、及在化學結構式中不含鹵素之 藍色顏料所構成者，是以所得之本發明之防焊油墨或其硬 化皮膜呈現實質的綠色的比例來配合。在此所謂呈現實質 的綠色之顏料比例，係指以肉眼觀察防焊油墨或其硬化皮 膜時，具有使觀看者能識別出其爲綠色之相當程度之色相 或色調的比例。藉此，用本發明之防焊油墨所製作之印刷 配線基板上之圖案，於目視檢查時具有優良之辨識性，而 且不傷視力。 作爲構成前述(C)成分之在化學結構式中不含鹵素之橙 色著色顏料，以舉出比色指數分類爲C.I·顏料橙者爲佳。 又，在前述之比色指數之C.I.顏料橙當中’特別是 一以比色指數(C.I.)顏料橙1，2,3,5,6，17,62及64等表示 之單偶氮系顏料， -以比色指數(C.I.)顏料橙40及41等表示之吡憩系之 顏料， 一以比色指數(C.I.)顏料橙14，15，16,50及63等表示之 一重氮系顏料， -以比色指數(C.I.)顏料橙75等表示之硫化鈽’ 一以比色指數(C.I.)顏料橙43等表示之？??系之顏料’ -以比色指數(C.I.)顏料橙71，73等所表示之二酮吡咯 并吡咯系顏料， 8 -----------—I—訂--------- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 517503 A7 _B7_ 五、發明說明（1 ) -以比色指數(C.I.)顏料橙48,49等所表示之喹吖酮系 顏料，及 (請先閱讀背面之注意事項再填寫本頁) 一以比色指數(C.I.)顏料橙65,68，17:1等所表示之金屬 錯合物系等。此類顏料，可各自單獨或以適當組合來使用 〇 此外，前述(C)成分之化學結構式中不含鹵素之藍色著 色顏料有如下各種： -以比色指數(C.I.)顏料藍15所表示之化學結構式中 不含鹵素之銅酞菁藍， -以比色指數(C.I.)顏料藍16所表示不含金屬之肽菁 藍， -以比色指數(C.I.)顏料藍63及66所表示之靛藍， -以比色指數(C.I.)顏料藍65等所表示之縮合多環系 之顏料， -以比色指數(C.I.)顏料藍60等所表示之憩醌系之顏 料， 一以比色指數(C.I·)顏料藍 1，2,3，10，14，18，19,24,56,57 及 61所表示之鹼性藍， -以比色指數(C.I.)顏料藍27所表示之紺青， -以比色指數(C.I.)顏料藍28所表示之鈷藍，以及 -以比色指數(C.I.)顏料藍29所表示之群青等。 這些顏料，係單獨分別使用或者以適當比例組合混合 使用。而上述所舉各例中，最適合的顏料以銅肽菁藍爲最 佳。 9 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 517503 A7 B7 一 五、發明說明（§ ) 又，橙色顏料及藍色顏料，以1:10〜10:1之比例爲佳 ，甚至以1··5〜5]之比例更好；最佳是以2:5〜5:2之比例 範圍爲最佳。若將橙色顏料及藍色顏料以上述之比例範圍 組合’所得之防焊油墨或其硬化皮膜即呈現實質的綠色。 且本發明之防焊油墨本身之顏色就算非綠色的情形，只要 本發明之防焊油墨之硬化物在青銅色之銅面積層板上呈現 綠色即可。 以上述之範圍配合之橙色顏料及藍色顏料所構成之(C) 著色顏料，對本發明之防焊油墨之其他成分之分散性良好 ，而且所得之防焊油墨形成少有顏色不均勻且顏色鮮明之 綠色永久保護膜。 又，本發明之防焊油墨中之前述(C)著色顏料之配合量 雖無特定限制，但此(C)著色顏料含有(D)有機溶劑時，除 去此有機溶劑不計，在本發明之防焊油墨之全成分中，其 所含重量以0.01〜20重量％爲佳，0.1〜10重量％更好，最 好是0.2〜5重量％。著色顏料之配合量於前述之範圍時， 可抑制因紫外線之透過率減少所造成之樹脂硬化性之降低 ，可形成在目視檢查時辨視性良好之永久保護膜。 而，以往使用之肽菁綠顏料，其粒子較不易被微細化 ，分散性較差。因此，爲了要使塗膜之表面狀態、電氣特 性及耐濕性等免於受到不良影響，於調製防焊油墨時’必 需費長時間進行混練製程。惟，前述之著色顏料(c)，與跃 菁綠顏料比較，在其他成分中之分散性良好，較易混練配 合，所以可容易地調製本發明之防焊油墨。 10 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -------------------訂--------« (請先閱讀背面之注意事項再填寫本頁) 517503 A7 ____B7____ 五、發明說明（？） (1)光防焊油墨 本發明之防焊油墨被用爲光防焊油墨時，含有能以有 機溶劑或微鹼性水溶液等使油墨顯像之紫外線硬化性樹脂 。尤其此油墨若能以微鹼性水溶液來顯像時，（A)成分之紫 外線硬化性成分，以(A-1)側鏈有乙烯性不飽和基及羧基之 紫外線硬化性樹脂較適用。 尤其是上述光防焊油墨之情形下，由（A-1)於側鏈具有 乙烯性不飽和基及羧基之紫外線型硬化性樹脂(B)光聚合起 始劑及(C)著色顏料所構成者較佳。 又，在本發明中，所謂「光防焊油墨」即是顯像型之 防焊油墨，例如，對應於··於基板上所塗佈之防焊油墨上 選擇性地以紫外線曝光，將此被曝光之部分之防焊油墨硬 化，然後將未曝光部分之防焊油墨在微鹼性水溶液之類的 溶液中洗淨除去，而得到既定圖案之永久保護膜之類型的 防焊油墨。 (A-1)側鏈有乙烯性不飽和基及羧基之紫外線硬化性樹 脂 本發明之光防焊油墨中，（A-1)成分是配合著側鏈有乙 烯性不飽和基及羧基之紫外線硬化樹脂。此(A-1)成分之化 學結構式中由於含有光硬化性之乙烯性不飽和基及羧基， 一旦因紫外線等之曝光而吸收一定之能量，則曝光部分會 硬化，對微鹼性水溶液之分散性及溶解性會降低。因此， 將塗布於基板上之含有前述(A-1)成分之本發明之光防焊油 .墨經選擇性地曝光，使曝光部分之光防焊油墨硬化，然後 11 衣紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------------------訂--------- (請先閱讀背面之注意事項再填寫本頁) 517503 A7 ____ B7 五、發明說明（f。） 將此基板以微鹼性水溶液洗淨，使得未曝光部分之未硬化 光防焊油墨被微鹼性水溶液溶解去除，即於基板上形成既 定之圖案。 在此，（A-1)成分之紫外線硬化樹脂其化學結構式中含 有光聚合性之乙烯性不飽和基。此類光聚合性之乙烯型不 飽和基，可舉（甲基)丙烯醯基及乙烯基等之不飽和基。此 光聚合性之乙烯性不飽和基之含有量雖無特定限制，但紫 外線硬化樹脂中之不飽和基之含有量在0.01〜10莫耳/公斤 (紫外線硬化樹脂)範圍爲佳，更適合以0.1〜5莫耳/公斤爲 更佳。紫外線硬化性樹脂中之不飽和基含有量在前述之範 圍時，可調製得兼具優異之曝光感度與顯像性之光防焊油 ma 墨。 又，（A-1)成分之紫外線硬化性樹脂，其酸價（acid valve)適合於30〜200mgK〇H/g、尤以40〜160 mgK〇H/g爲佳 。紫外線硬化性樹脂之酸價於前述之範圍時，其與其他成 分之相溶性變得良好，同時可調製特別具有良好之曝光感 度、顯像性及解析性之光防焊油墨。 此外，（A-1)成分之紫外線硬化性樹脂之平均重量分子 量，雖無特定限制，但以3,000〜400,000爲佳，5,000〜 100,000更佳，最佳是5,000〜50,000範圍。當紫外線硬化 性樹脂之平均重量分子量在前述之範圍內時，本發明之光 防焊油墨之解析性及曝光感度之平衡特別優異。 前述(A-1)成分，可舉出例如於「側鏈有環氧基之聚合 物」中之前述環氧基加成「具有羧基之乙烯性不飽和化合 12 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 517503 A7 B7 五、發明說明（丨丨） .物」及「多元羧酸酐」而製成之紫外線硬化性樹脂。 用以調製前述之(A-1)成分所例示之紫外線硬化性樹脂 ，所用之「於側鏈含有環氧基氧基之聚合物（骨架聚合物） 」可使用列舉如下之環氧化合物與乙烯性不飽和單體之共 聚物。 即，上述之環氧化合物可舉例如下：環氧丙基（甲基） 丙烯酸酯或2-甲基環氧丙基（甲基)丙稀酸酯等之環氧丙基（ 甲基)丙烯酸酯類，及(3,4-環氧基環己基）甲基（甲基)丙烯酸 酯等之（甲基)丙烯酸之環氧基環己基衍生物類。 又，上述之乙烯性不飽和單體，可舉例如下：脂肪族 或脂環族之烷基（甲基)丙烯酸酸酯；苄基（甲基)丙烯酸酯等 之芳香族系（甲基)丙烯酸酯；羥乙基（甲基)丙烯酸酯或甲氧 基乙基（甲基)丙烯酸酯等之乙二醇酯系（甲基)丙烯酸酯，聚 乙二醇酯（甲基）丙烯酸酯及丙二醇系（甲基)丙烯酸酯；（甲 基)丙烯醯胺系化合物；N-取代馬來酸酐縮亞胺；乙烯卩比略 烷酮；（甲基)丙烯腈；醋酸乙烯；苯乙烯；α 一甲基苯乙 烯；及乙烯醚等。 又，在本說明書中，（甲基)丙烯酸係丙烯酸與甲基丙 烯酸之總稱，而（甲基）丙烯酸酯係丙烯酸酯與甲基丙烯酸 酯之總稱。 又，用以調製作爲前述(Α-1)成分所列之紫外線硬化性 樹脂之「於側鏈具有環氧基之聚合物(骨架聚合物）」，除 了前述之環氧化合物與乙烯性不飽和單體之共聚合物以外 ，尙可舉例如下：酚醛線性型環氧樹脂，甲酚線性型環氧 (請先閱讀背面之注意事項再填寫本頁) _裝--------訂---------' 13 517503 A7 ___B7___ 五、發明說明（A ) 樹脂，雙酚A型環氧樹脂，雙酚F型環氧樹脂，雙酚A— 線性型環氧樹脂、脂環式環氧樹脂（例如代謝爾化學工業 公司所製造之「EHPE-3150」），及三（羥苯基）甲烷之衍 生物之多官能環氧樹脂（例如日本化藥（股份有限）公司 製造之EPPN-502H，及陶氏化學公司製造之742及XD-9053等）等之環氧樹脂。 又，用以調製作爲前述(A-1)成分所例示之紫外線硬化 性樹脂之「含有羧基之乙烯性不飽和單體」，例如可舉出 :於（甲基)丙烯酸，丁烯酸，桂皮酸，2-(甲基)丙烯醯基羥 乙基琥珀酸，2-(甲基)丙烯醯基羥乙基苯二酸，羧乙基 丙烯酸酯，丙烯醯基羥乙基琥珀酸酯，2-丙烯酸，3-(2-羧 基乙氧基)-3-羥基丙酯，2-(甲基)丙烯醯基羥乙基四氫苯二 酸，及2-(甲基)丙烯醯基羥乙基六氫苯二酸等之含有丨個 乙烯性不飽和基；以及於戊赤蘚醇三（甲基）丙烯酸酯、三 羥甲基丙烷二（甲基)丙烯酸酯、二戊赤蘚醇五（甲基)丙烯酸 酯等之具有羥基之多官能丙烯酸酯中，讓二元酸酐反應而 得之具有複數乙烯性不飽和基之化合物。 其中，又以含有1個羧基者爲佳，特別是使用（甲基） 丙烯酸或以（甲基)丙烯酸爲主成分者較佳。此乃由於藉由（ 甲基)丙烯酸所導入之乙烯性不飽和基係具有優良之光反應 性之故。 這些「含有羧基之乙烯性不飽和單體」可單獨分別使 用，亦可以適當比例組合來使用。 又，用以調製作爲前述(A-1)成分所例示之紫外線硬化 14 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 517503 A7 ___B7 五、發明說明（β ) 性樹脂之「多元羧酸酐」例如可舉出：無水號拍酸，無水 甲基琥珀酸，無水馬來酸，無水檸康酸，無水戊二酸，無 水衣康酸，無水苯二酸，四氫無水苯二酸，甲基四氫無水 苯二酸，無水甲基酸，六氫無水苯二酸及甲基六氫無水苯 二酸等之2兀酸酐，以及無水偏苯三酸，無水均苯四甲酸 ，無水二苯甲酮四竣酸及甲基環己烯四竣酸酐等之3元酸 以上之酸酐。 這些「多元羧酸酐」，可單獨分別地或以適當地組合 使用。 如前述’於側鏈有環氧基之聚合物的前述環氧基加成 具有羧基之乙烯性不飽和化合物及多元羧酸酐來調製做爲 (A-1)成分所例示之用以調製紫外線硬化性樹脂之加成反應 ，係例如在熱聚合抑制劑及加成觸媒之存在下，在60〜 150°C之溫度範圍進行加熱。 又，上述之加成反應，於「側鏈有環氧基之聚合物」 加成「有羧基之乙烯性不飽和化合物」後加成「多元竣酸 酐」、或於「側鏈有環氧基之聚合物」加成「多元竣酸酐 」後加成「有竣基之乙稀性不飽和化合物」皆可，但以前 者較佳。 在本發明之光防焊油墨之全成分中，除去以下所述及 之有機溶劑，上述(A-1)成分之配合量，雖無特定限制但以 10〜80重量％爲宜，20〜70重量％更佳’而以25〜60重量 %爲最佳。（A-1)成分之配合量若在前述之範圍內，則可得 到鹼性顯像性、感度及解析性皆佳之光防焊油墨。 15 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------------------^--------- (請先閱讀背面之注意事項再填寫本頁) 517503 A7 _________B7 ___— 一 五、發明說明（W ) (A-4)乙烯性不飽和單體 又，本發明之光防焊油墨，除了前述(A-1)成分，尙可 配合作爲(A)紫外線硬化性成分之(A-4)乙烯性不飽和單體’ 使塗佈性、耐熱性及絕緣性等之特性提昇。而此(A-4)重聚 合性乙烯不飽和單體，除爲有效之稀釋劑之外，同時也有 調節曝光感度之功能。 此類乙烯性不飽和單體，可以下列各種（甲基）丙烯酸 酯單體爲例：2-羥乙基（甲基)丙烯酸酯、2-羥丙基（甲基)丙 烯酸酯，N-乙烯基吡咯烷酮、（甲基)丙烯醯嗎咐、甲氧基 四乙二醇（甲基)丙烯酸酯、甲氧基聚乙二醇（甲基)丙烯酸酯 、聚乙二醇二（甲基)丙烯酸酯、N，N-二甲基（甲基)丙烯醯胺 、N-羥甲基（甲基)丙烯醯胺、N，N-二甲基氨丙基（甲基)丙烯 醯胺、N，N-二甲基氨乙基（甲基)丙烯酸酯、三聚氰胺（甲基) 丙烯酸酯、二乙二醇二（甲基)丙烯酸酯、三乙二醇二（甲基) 丙烯酸酯、丙二醇二（甲基)丙烯酸酯、苯氧基乙基（甲基)丙 烯酸酯、四氫呋喃（甲基)丙烯酸酯、環己基（甲基)丙烯酸酯 、三羥甲基丙烷二（甲基)丙烯酸酯、三羥甲基丙烷三（甲基) 丙烯酸酯、戊赤蘚醇三（甲基)丙烯酸酯、戊赤蘚四（甲基)丙 烯酸酯、二戊赤蘚醇六（甲基)丙烯酸酯、異坎基（甲基)丙烯 酸酯、環戊烯單（甲基)丙烯酸酯及環戊炔單（甲基)丙烯酸酯 ;多元酸及羥烷基（甲基)丙烯酸酯之單酯、二酯、三酯， 或多酯；多酯（甲基)丙烯酸酯，氨酯（甲基)丙烯酸酯等。 此類乙烯性不飽和單體，於用以調製本發明之光防焊 油墨時，可分別單獨使用或適當組合使用。 16 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -------------------訂--------- C請先閱讀背面之注意事項再填寫本頁) 517503 A7 ___B7___ 五、發明說明（〖r ) 在光防焊油墨之全成分中，除了有機溶劑之外，前述 之(A-4)乙烯性不飽和單體之配合量，雖無特殊限制，而以 1〜50重量％爲宜，1〜40重量％更佳，1〜30重量％最佳。 藉由配合前述範圍之光聚合性乙烯不飽和單體，一方面可 使乾燥塗膜具有適度之表面黏著性，一方面將繪有圖案之 負光罩放在乾燥塗膜上曝光時，可防止負光阻之污損問題 〇 又，本發明之光防焊油墨，也可依需要而與環氧（甲基 )丙烯酸酯等之紫外線硬化性高分子、（甲基)丙烯酸酯共聚 物、苯乙烯一馬來酸樹脂等之乙烯性不飽和化合物之共聚 物，或對這些進一步導入乙烯性不飽和基所得之紫外線硬 化性聚合物等配合。 (B)光聚合起始劑 本發明之光防焊油墨，進一步配合(B)成分之光聚合起 始劑。 (B) 成分以使用上述所列舉之光起始劑爲佳。 又，除去有機溶劑不計，本發明之光防焊油墨之全成 分中，（B)成分之光聚合起始劑，以0.1〜30重量％爲宜，1 〜10重量％更佳，1〜7重量％最佳。在前述範圍之配合量 來含有光聚合起始劑時，本發明之光防焊油墨將具有優良 之光硬化性，且所得之永久保護膜之物性也極優良。 (C) 著色顏料 在本發明之光防焊油墨，係配合有作爲(C)成分之著色 顏料。在本發明所配合之著色顏料，如前所述地，係由化 π 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -------------------1---------^^_wl (請先閱讀背面之注意事項再填寫本頁) 517503 A7 B7 一 Γ---—- 五、發明說明（〖心） 學結構式中不含鹵素之橙色顏料及化學結構式中不含鹵素 之藍色顏料所構成，而且這兩種顏料是以足使本發明之光 防焊油墨或其硬化皮膜實質上呈現綠色的比例來配合的。 藉此，使用本發明之光防焊油墨製作之印刷配線基板之圖 案，於目視檢查時其辨視性極佳，且不傷視力。 又，最適當之橙色顏料及藍色顏料與前面所列舉者相 同。 在此，橙色顏料與藍色顏料之重量比也如前所述，以 1:10〜10:1之比例爲佳，1:5〜5:1更好，最佳之比例爲2:5 〜5:2。根據上述之比例範圍來配合橙色顏料與藍色顏料， 所得之光防焊油墨或其硬化皮膜，實質上呈現綠色。 又，以前述範圍來配合之橙色顏料與藍色顏料，對本 發明之光防焊油墨之各成分之分散性良好，而且可得到形 成有顏色不均少且呈現鮮綠色之永久保護膜之光防焊油墨 〇 又，雖然前述(C)著色顏料之配合量無特定限制，在本 發明之光防焊油墨之全成分中，除去後面將述及之有機溶 劑不計，（C)著色顏料之重量比，以0.1〜20重量％爲宜’ 0.1〜10重量％更佳，而以0.2〜1.5重量％爲最佳。著色顏 料之配合量在前面所述之範圍內時，一方面可抑制因紫外 線透過率之降低所造成之樹脂硬化性之下降，另方面可形 成目視檢查時其辨視性良好之永久保護膜。 (D)有機溶劑 本發明之光防焊油墨，亦可另配合(D)成分之有機溶劑 18 本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 517503 A7 ____B7___ 五、發明說明（β ) Ο 在本發明中較適合的有機溶劑，有下列各種，例如： 乙醇、丙醇、異丙醇、丁醇、異丁醇、2-丁醇、己醇及乙 二醇等之具有直鏈或有支鏈狀之碳鏈的1級、2級或多元 醇類；甲乙酮及環己酮等之酮類；甲苯及二甲苯等之芳香 族烴類；蘇瓦所魯系列（九善石油化學公司製造）及所魯 別蘇系列（愛克森化學公司製造）等之石油系芳香族系混 合溶劑；溶纖劑及丁基溶纖劑等之溶纖劑類；卡必醇及丁 基卡必醇等之卡必醇類；丙二醇甲醚等之丙二醇烷醚類； 二丙二醇甲醚等之多丙二醇烷醚類；乙酸乙酯、乙酸丁酯 ，溶纖劑乙酸酯，丁基溶纖劑乙酸酯，丁基卡必醇乙酸酯 及丙二醇單甲醚乙酸酯等之乙酸酯類；以及二烷基二醇醚 類等等皆是；此類之有機溶劑，爲調製本發明之光防焊油 墨，可分別單獨使用或以適當組合搭配使用。 前述之(D)成分之有機溶劑，在本發明中之光防焊油墨 中，以佔1〜95重量％，或進而以5〜95重量％，或最佳以 20〜95重量％配合爲最佳。依前述範圍配合有機溶劑，則 所得之本發明之光防焊油墨，對於基板上之塗佈性優良。 (E)多官能環氧化合物 本發明之光防焊油墨，除了前述(A-1)紫外線硬化性樹 脂，亦可再與任意成分之(E)之多官能環氧化合物配合亦佳 〇 前述之多官能環氧化合物雖無特定限制，例如雙^ a 型壞氧樹脂、雙酚F型環氧樹脂、酚醛線性型環氧樹脂、 19 -----------0^ 裝--------訂---------^9. (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 517503 A7 _____Β7__ 五、發明說明（β ) 甲酚線性型環氧樹脂、雙酚A—線性型環氧樹脂、N-環氧 丙基型環氧樹脂或脂環式環氧樹脂(例如代謝爾化學公司製 造之「EHPE-3150」）、「YX-4000」（油化殼牌環氧公司製 造之環氧樹脂）、加氫雙酚A型環氧樹脂及三環氧丙基異氰 酸酯、及由三(羥苯基）甲烷所衍生之多官能環氧樹脂（曰本 化藥公司製造之EPPN-502H陶氏化學公司製造之達克題克 斯-742及XD-9053等)是爲此類例子。 又，做爲本發明中所用之多官能基環氧樹脂，亦可使 用含有環氧基之乙烯性不飽和單體之單獨聚合物或共聚物 。又使用前述之共聚物時，在構成共聚物之單體中，具環 氧基之乙烯性不飽和單體以含有40莫耳％以上較適合。藉 此可獲得之良好之熱硬化性。 又，雖無特定限制，當前述之多官能基環氧化合物爲 含有環氧基之乙烯性不飽和單體之單獨聚合物或共聚物時 ，其重量平均分子量以2,000〜200,000範圍較適宜。藉此 ，可調製形成有硬化皮膜（具優良之熱硬化性）之光防焊油 墨。 前述之(E)成分之多官能環氧化合物，於本發明之光防 焊油墨之全成分中，除去後面將述及之有機溶劑不計，其 配合量以0.1〜50重量％爲宜，0.1〜40重量％更佳，而5〜 40重量％則最佳。當多官能環氧化合物之固形分的配合量 在上述範圍時，可得到顯像性與熱硬化性之平衡良好之光 防焊油墨。 進一步之任意成分 20 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ------------------訂---------- (請先閱讀背面之注意事項再填寫本頁) 517503 A7 ___B7__ 五、發明說明（i?) 本發明之光防焊油墨，爲了進一步提昇塗佈性、耐熱 性及絕緣性等，可進一步配合任意成分。 此類任意成分，可舉以下各種爲例：滑石、二氧化矽 、硫酸鋇、氧化鋁、碳酸鈣及雲母等之塡充顏料、無機顏 料、密著性賦予劑、平整劑、矽烷偶合劑、觸變劑、聚合 抑制劑、光暈防止劑、消泡劑、氧化防止劑、界面活性劑 及高分子分散劑。 本發明之光防焊油墨，係使用三輥、球磨機以及砂磨 機等習用公知之混練手法來調製。 又，本發明之光防焊油墨，其各成分不需要事先完全 均一地混合。例如個別調製出由（E)成分與(D)成分所構成 之混合液1、由(A-1)成分、（B)成分、（C)成分及(D)成分所 構成之混合液2，於要使用時將混合液1與混合液2混合 再使用也無妨。 本發明之光防焊油墨，若於銅面積層板等之基板上塗 布、乾燥，將所得之乾燥塗膜上之特定部分以紫外線照射 ，使該部分之光防焊油墨硬化。然後於微鹼性溶液中除去 未曝光部分以使顯像，其後經後段烘烤將未除去之殘留光 防焊油墨變成永久保護膜。 前述用做顯像液之微鹼溶液，以水溶液態較適合，但 如爲洒精等之親水性有機溶劑亦可。 以上述方式所得之永久保護膜，其含鹵量，以500ppm 以下爲宜(實際上〇·1〜500ppm)，300ppm以下(實際上爲0·1 〜300ppm)更佳，而以150ppm以下(實際上爲〇·1〜150ppm) 21 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------*t--------tr--------- (請先閱讀背面之注意事項再填寫本頁) 517503 A7 _B7_ 五、發明說明（/ ) 爲最佳。以此等含鹵量，燃燒時所產生之鹵素量顯著地降 低。 根據本發明，由於使用不含鹵素之著色顏料，故(A-1) 成分中之「側鏈有環氧基之聚合物」或其製造時所用之含 環氧基之乙烯性不飽和單體，及(E)多官能環氧化合物或其 製造所使用之含環氧基之乙烯性不飽和單體無特定限制， 使用在工業上可取得之物，即可使硬化皮膜中之含鹵量在 前述之500ppm以下(實際上是0.1〜500ppm)。 又，傳統上，爲調製光防焊油墨所用之上述環氧化合 物，特別是由多環酚系化合物所衍生之環氧樹脂或環氧丙 基甲基丙烯酸酯等之含環氧丙基之乙烯性不飽和單體等被 廣爲使用，但這些在工業上皆是以環氧氯丙烷之加成反應 及氯化氫(HC1)之脫離反應來製造，在製品中有許多反應副 產物或雜質，含有高濃度之鹵素。 因此，以如此製造所得之環氧化合物來調製光防焊油 墨，則在基板上形成之硬化皮膜中之含鹵素量很難達成 150ppm以下之目標。 另一方面，根據本發明，製造(A-1)成分所用之環氧化 合物，以及(E)成分或製造(E)成分所用之環氧化合物’須使 用其含鹵素量在50ppm以下者才適當。使用這類的(A-1)成 分及/或(E)成分的話，則從本發明的光防焊油墨所形成的 永久保護膜中之含鹵量，較傳統習用的有顯著的降低’可 低至150ppm以下。 爲調製本發明之光防焊油墨所用之前述之含鹵量 22 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------------------訂--------- (請先閱讀背面之注意事項再填寫本頁) 517503 A7 _______B7_____ 五、發明說明（ >丨） (請先閱讀背面之注意事項再填寫本頁) 50ppm以下之環氧化合物，可以例如過酸物（例如，過蟻 酸、過醋酸、過苯甲酸等）之環氧化反應而合成之環氧樹 脂及含有環氧基之乙烯性不飽和單體。 這些在其製造過程中並無使用環氧氯丙烷，因此是不 含鹵素的。這些環氧樹脂，可舉出例如「EHPE-3150」（代 謝爾化學工業(股份有限)公司所製之脂環式環氧樹脂），又 作爲含環氧基之乙烯性不飽和單體，例如有賽可洛瑪-A-200(代謝爾化學工業(股份有限)公司所製之含脂環式環氧基 之乙烯性不飽和單體）。賽可洛瑪-M-100，M-101(代謝爾化學 (股份有限）公司所製之含脂環式之環氧基之乙烯性不飽和 單體)等。 又’雖非以過酸之環氧化反應所合成者，惟例如經去 氯處理所製得之含有環氧基之乙烯性不飽和單體之布雷瑪 GS(日本油脂(股份有限)公司所製之無氯、環氧丙基甲基丙 烯酸酯)等之情形，其鹵素濃度也爲l〇ppm以下適宜使用。 (II)紫外線硬化型之防焊油墨 另一方面，將本發明之防焊油墨當成紫外線硬化型防 焊油墨來利用時，做爲(A)成分之紫外線硬化型成分，雖無 特定限制，惟以：（A-3)環氧（甲基)丙烯酸酯及/或多元酚之 聚醚化物與（甲基)丙烯酸所成之酯化物；（A-3)成分以外之 (A-4)乙烯性不飽和化合物；所組成者爲宜。 亦即’此紫外線硬化型防焊油墨係由：（A-3)環氧（甲基 )丙烯酸酯及/或多元酚之聚醚化合物及（甲基)丙烯酸所成之 酯化物、（A-3)成分以外之(A-4)乙烯性不飽和化合物、（B) 23 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 517503 A7 _—— — —_ B7—_ 五、發明說明（·>> ) 光聚合起始劑及(C)著色顏料所構成。 又’在本發明之「紫外線硬化型防焊油墨」係指藉印 刷法而形成既定之圖案來形成永久保護膜者，例如在基板 上使用網版印刷等習用公知之印刷手法所印刷之防焊油墨 上，經紫外線全面曝光而使被曝光部分之防焊油墨硬化， 而得到既定圖案之永久保護膜之類型的防焊油墨。 (A-3)環氧（甲基)丙烯酸酯及/或多元酚之聚醚化物及（甲 基)丙烯酸所成之酯化物 本發明之紫外線硬化型之防焊油墨，其(A-3)成分，含 有環氧（甲基)丙烯酸酯及/或多元酚之聚醚化物與（甲基）丙 烯酸所成之酯化物。 在本發明，（A-3)成分之上述環氧（甲基)丙烯酸酯，係 謂環氧化合物與（甲基)丙烯酸之酯化反應所生成得到之環 氧基之全酯化物或部分酯化物。 在本發明，此(A-3)環氧（甲基)丙烯酸酯，可單獨分別 使用習用公知之各種，或以適當組合來使用亦可。 又，生成上述之環氧（甲基)丙烯酸酯之上述環氧化合 物，具體言之，可舉出由雙酚A'雙酚F、雙酚A樹脂、 雙酚F樹脂、線性酚醛樹脂及甲酚線性樹脂等之多元酚類 與環氧氯丙烷之反應所得者，以及脂環式環氧樹脂(例如代 謝爾化學工業公司所製之實質上不含鹵素之過醋酸法環氧 樹脂「EHPE-3150」）等。 另一方面，上述之(A-3)成分中，多元酚之聚醚化物與( 甲基)丙烯酸所成之酯化物，係由多元酚之聚醚化物與（甲 24 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ' '^- --------^--------- (請先閱讀背面之注意事項再填寫本頁) 517503 A7 —_ B7___ 五、發明說明（/ ) 基)丙烯酸之酯化反應所生成得到之全酯化物或部分酯化物 Ο 又，上述之多元酚之聚醚化物，可於多元酚中，加成 例如環氧乙烷、環氧丙烷、環氧丁烷或ε —己內酯而得到 〇 本發明之紫外線硬化型防焊油墨中之(Α-3)成分之配合 物雖無特定限制，但較適宜之(Α-3)成分則是於本發明之紫 外線硬化型防焊油墨中含有10〜70重量％，更佳是15〜65 重量％，最佳則是含有15〜60重量％。含(Α-3)成分在上述 之範圍之本發明之紫外線硬化型防焊油墨，經紫外線照射 而硬化，可獲得具有所希望之強度之硬化物。 (Α-4) Α-3成分以外之乙烯性不飽和化合物 又，本發明之紫外線硬化型防焊油墨中，除了上述(Α-3) 成分外尙含有作爲 (Α-4) 成分之 (Α-3)成分以外之乙烯性不 飽和化合物。 上述(Α-3)成分以外之乙烯性不飽和化合物，可舉出有 關於前面所提及之光防焊油墨的說明中所例示者。 本發明之紫外線硬化型防焊油墨中之(Α-4)成分之配合 物雖無特定限制，但較適宜之(Α-4)成分則是於本發明之油 墨中含有10〜70重量％，更佳是15〜65重量％，最佳則是 含有20〜60重量％。含(Α-4)成分在上述之範圍之本發明之 紫外線硬化型防焊油墨，經紫外線照射而硬化，可獲得具 有所希望之強度之硬化物。 又’構成紫外線硬化性成分之上述(Α_3)成分及(Α-4)成 25 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 X 297公爱) " «t--------tl--------- (請先閱讀背面之注意事項再填寫本頁) 517503 A7 ____B7__ 五、發明說明（^ ) 分之組成比例，無特殊限定。然而(A-3)成分及(A-4)成分之 合計100重量份中，（A-3)成分之配合量以10〜70重量％爲 宜，10〜60重量％更佳，最佳則是15〜50重量％。（A)成分 及(B)成分若依前述之範圍的配合量來配合時，則可調製之 紫外線硬化型防焊油墨，其形成之永久保護膜具有優良印 刷性，且硬化性及耐熱性倶佳。> (B) 光聚合起始劑 本發明之防焊油墨’除則述之(A-3)成分及(A-4)成分之 外，還含有(B)成分之光聚合起始劑。 在本發明所含之適宜之光聚合起始劑，與先前所列舉 者相同。 又，本發明中之(B)光聚合起始劑之配合量，如同前已 述及地，在本發明之紫外線硬化型防焊油墨中，以0.1〜30 重量％爲宜，進而以1〜10重量％更佳，1〜7重量％則最佳 。若所含光聚合起始劑之配合量在上述之範圍，則本發明 之防焊油墨將顯示優良之光硬化性，且所得到之永久保護 膜之物性也十分良好。 (C) 著色顏料 進一步，在本發明之防焊油墨中，配合有(Q成分之著 色顏料。在本發明所配合之著色顏料，如前所述，爲化學 結構式中不含鹵素之橙色顏料及化學結構式中不含鹵素之 藍色顏料所構成者，此外此等橙色顏料及藍色顏料係以所 製得本發明之光防焊油墨或其硬化皮膜實質上呈現綠色之 比例來配合。從而，使用本發明之光防焊油墨製作之印刷 26 ------------裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 517503 A7 _____ B7____ 五、發明說明（W ) 配線基板之圖案，於目視檢查之際，具有優良之辨識性， 而且較不傷視力。 (請先閱讀背面之注意事項再填寫本頁) 構成上述(C)成分之化學結構式中不含鹵素之橙色顏料 及藍色顏料，與前面所列舉者同。 又，橙色顏料與藍色顏料之重量比，如同前述，以 1:10〜10:1爲宜，1:5〜5:1更佳，而2:5〜5:2貝[j最佳。以上 述之範圍來配合橙色顏料與藍色顏料，所得之光防焊油墨 或其硬化皮膜，實質上呈現綠色。 又，依前述範圍配合之橙色顏料與藍色顏料，對其他 成分之分散性良好，而且所得之防焊油墨形成少有顏色不 均勻且顔色鮮明之綠色永久保護膜。 又，本發明之紫外線硬化型防焊油墨中，前述之(C)成 分之著色顏料的配合量雖無特殊規定，但著色顏料佔本發 明之紫外線硬化劑防焊油墨中〇.〇1〜20重量％爲宜，0.1〜 10重量％更佳，0.2〜5重量％則最佳。依前述配合量來含 有著色顏料，則本發明之紫外線硬化型防焊油墨，可抑制 因紫外線透過率之減少所造成之樹脂硬化性之降低，可形 成目視檢查時具良好辨視性之永久保護膜。 本發明之紫外線硬化型防焊油墨，雖含有(A-3)、（A-4) 、（B)及(C)成分等作爲必要成分，但在不致對印刷性、耐 熱性、及絕緣性等特性造成不良影響之前提下，含有其他 成分亦無妨。 這類成分，可舉滑石、二氧化矽、硫酸鋇、氧化鋁、 碳酸鈣及雲母等之塡充顏料，無機顏料，密著性提昇劑， 27 本紙張尺度適用中國國家標準(CNS)A4規格X 297公髮) " 517503 A7 ______B7 五、發明說明（>0 .平整劑，觸變劑及聚合抑制劑等爲其例。 本發明之紫外線硬化型防焊油墨，採用例如網版印刷 或膠版印刷等習用公知之印刷方法，印刷於銅面積層板等 基板上。 本發明之紫外線硬化型防焊油墨，由於使用不含鹵素 之著色顏料(C)，因此紫外線硬化型防焊油墨中之鹵素含量 顯著地減低。具體而言，本發明之紫外線硬化型防焊油墨 之鹵素含量爲500ppm以下(現實中0.1〜5〇〇ppm)，較佳者 爲400ppm以下(現實中爲〇.1〜4〇〇ppm)，最佳者爲300ppm 以下(現實情形是0.1〜300ppm)。因此，由本發明之紫外線 硬化型防焊油墨所形成之永久保護膜，其燃燒時所發生之 鹵素氣體量可顯著地減少。 另一方面，使用環氧化合物製造(A-3)成分時，此環氧 化合物也可選擇鹵素含量50ppm以下者。從而，本發明之 防焊油墨所形成之永久保護膜中鹵素含量，乃可較以往顯 著地減低，可低至150ppm，此與前述之光防焊油墨情形相 同。 實施例 以下爲基於實施例對本發明做進一步闡明，但不意謂 本發明僅限於下列實施例。 又，下列各例中，以「份」及「％」表示者，皆係重 量基準。 實施例1 . (I)光防焊油墨 28 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） -------------------二π·------—I (請先閱讀背面之注意事項再填寫本頁) 517503 A7 _______________B7 ___ 五、發明說明（>7 ) 以表1所述之組成比例，調製本發明之試樣1-1〜8。 又’爲了將本發明之光防焊油墨之性能做比較，乃依 表1所記載之配合組成來調製試樣卜丨丨〜^。 又’表1所記載之紫外線硬化性樹脂之(A-1-1)，（A-1-2) ’（A-1-3)，及(A-1-4)係如下述方法調製而成。 [A-Μ之合成] 於安裝有回流冷卻器、溫度計、氮置換用玻璃管及攪 拌機之四口燒瓶中，添加布雷瑪GS(日本油脂公司製，含 氯低之環氧丙基甲基丙烯酸酯，鹵素含量lppm以下)70份 、甲基甲基丙烯酸酯30份、乙酸卡必醇酯100份、偶氮二 異丁腈3份，一邊攪拌一邊以氮氣流下在80°C加熱5小時 ，來聚合得到50%共聚物溶液。於所得50%共聚合物溶液 中，加入對苯二酚0.05份，丙烯酸37份及二甲基苄胺0.2 份，以100°C進行24小時之加成反應。接著，加入四氫化 鄰苯二甲酸酐45份及乙酸卡必醇酯79份，以100°C反應3 小時得到紫外線硬化性樹脂之50%溶液(A-Μ)。 [A-1-2]之合成 將EHPE3150(脂環式環氧樹脂，代謝爾化學工業(株份 有限)公司製造，環氧當量179，不含鹵素（未檢測出鹵素 ))179份溶解於乙酸卡必醇酯60份中，再一邊攪拌一邊 加入丙烯酸74份、對苯二酚0.1份、及二甲基苄胺0.7份 ，依一般方法，於90〜100°C反應24小時。於此反應液加 入乙酸卡必醇酯95份，攪摔之，而得到環氧丙烯酸酯溶液 。接著加入四氫化鄰苯二甲酸酐76份及乙酸卡必醇酯64 29 (請先閱讀背面之注意事項再填寫本頁) -裝 -----訂---------- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） 517503 A7 _ B7 """"" 一 " "--" —--- — 五、發明說明（β ) 份，以100°C反應3小時，得到紫外線硬化性樹脂之6〇% 溶液(A-1-2)。 [A-1-3]之合成 取代於前述之(A-Μ)之合成所用之布雷瑪gs，改用丙 烯酯G(三菱人造纖維(股份有限)公司製造，使用環氧氯丙 烷所得之含有雜質之鹵之環氧丙基甲基丙燦酸酯，； 含量160ppm)70份，餘皆仿(A-1-1)之合成法，製得紫外j泉 硬化性樹脂之50%溶液(A-1-3)。 [A-1 -4]之合成 取代前述之(A-1-2)之合成所用之EHPE3150，改:用 克龍N-680(大日本油墨化學工業(股份有限)公司製造之甲 酚線性型環氧樹脂，環氧當量214，鹵素含有量105〇ppm) 21份，且於添加酸酐時，所配合之乙酸卡必醇酯之組成變 更爲78份外，餘皆仿(A-1-2)之合成方法，製得紫外線硬化 性樹脂之60%溶液(A-1-4)。 又，於表1所記載之多官能環氧化合物所用之 EHPE3150爲代謝爾化學工業(股份有限)公司所製之環氧樹 脂’而愛皮克龍N-680爲大日本油墨化學工業(股份有限) 公司所製造之甲酚線性型環氧樹脂，TEPIOS爲日產化學 工業(股份有限)公司製造之三環氧丙基異氫酸酯（鹵素含量 800ppm)。 [E-1之合成] 又，表1所記載之(E-1)係依下述之方法調製而得。 亦即，於安裝有回流冷卻器、溫度計、氮置換用玻璃 30 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) ---------訂-------- 517503 A7 ___B7___ 五、發明說明（J ) ‘管及攪拌機之四口燒瓶中，加入布雷瑪GS(日本油脂(股份 有限)公司製造，含氯低之環氧丙基甲基丙烯酸酯）80份、 丁基丙烯酸酯20份、乙酸卡必醇酯67份、及偶氮二異丁 腈3份，一邊攪拌一邊以氮氣流下在85°C聚合5小時，而 得到多官能環氧化合物之60%溶液(E-1)。 在本發明中，化學結構式中不含鹵素之橙色顏料，使 用謝卡法斯特橙3064(比色指數(C.L)顏料橙5(大日精化(股 份有限)公司製造之單偶氮系橙色顏料），及2900珮利卡法 斯特橙GR(比色指數(C.I.)顏料橙16)(大日精化(股份有限) 公司製造之單偶氮顏料）、CROMOPHTAL DDP Orange TR(( 比色指數(C.I.)顏料橙71)(吉巴特用化學(股份有限)公司製 造之二氧代吡咯并吡咯系橙色顏料）、IRGAZIN DDP Orange RA((比色指數(C.I.)顏料橙73)(吉巴特用化學(股份 有限)公司製造之二氧代吡咯并吡咯系橙色顏料）。 在本發明中，化學結構式中不含鹵素之藍色顏料，使 用克羅馬法因藍5008(比色指數(C.I.)顏料藍15(大日精化(股 份有限)公司製造之肽氰藍顏料）、克羅馬法因藍4927(比色 指數(C.I.)顏料藍15)(大日精化(股份有限)公司製造之酞氰 藍顏料）、及D-7565(比色指數(C.I.)顏料藍16)(BASF公司製 之無金屬肽氰藍顏料）。 作爲以往所使用之綠色有機顏料，係使用2GN((比色 指數(C.I.)顏料綠7(大日精化(股份有限)公司製造之酞氰綠 顏料）、以及D-8605(比色指數(C.I.)顏料綠7)(BASF公司製 之酞氰綠顏料）。 31 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) ^--------^------ 517503 A7 ___B7_____ 五、發明說明（） 所使用之光聚合起始劑依魯佳吉亞907爲吉巴蓋吉公 司所製造之產品，而卡雅吉亞DETX-S則爲日本化藥(股份 有限)公司所製造之產品。 墨達福羅爲孟山都公司製造之平整劑。 二氧化矽則使用平均粒徑l//m者。 將前述所得到之光防焊油墨1-1〜8及1-11〜12，以網 版印刷塗佈於印刷配線基板之全面(在銅箔35/zm之玻璃環 氧基材所構成之銅面積層板事先鈾刻而形成圖案），爲使溶 劑揮發，乃以80°C進行20分鐘預固化，而得到膜厚20/zm 之乾燥塗膜。然後，將繪有圖案之光罩直接抵於塗膜面， 以150m；i/cm2之紫外線照射，接著以1%碳酸鈉水溶液做爲 顯像液使之顯像而形成圖案，繼之以150°C加熱60分鐘進 行硬化，以製作根據本發明之試樣片1-1〜8及超出本發明 範圍之試樣片1-11〜12。 實施例2 (II)紫外線硬化型防焊油墨 爲調製實施例之紫外線硬化型防焊油墨，首先調製如 下之環氧丙烯酸酯(A-3-1)〜（A-3-6)。 環氧丙烯酸酯(A-3-1) 此爲愛皮克特154(油化殻牌(股份有限)公司製造之酚 醛線性型環氧樹脂)與丙烯酸進行酯化反應所調製成。此係 環氧基之全酯化物。 環氧丙烯酸酯(A-3-2) 此爲愛皮克特828(油化殼牌(股份有限)公司製造之雙 32 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) --------^--------- 517503 A7 ____ Β7___ 五、發明說明（Μ ) •酚Α型環氧樹脂)與丙烯酸經酯化反應所調製的。此係環氧 基之全酯化物。 環氧丙烯酸酯(A-3-3) 此爲EPPN-20K日本化藥(股份有限)公司製造之酚醛線 性型環氧樹脂)與丙烯酸經酯化反應所調製的，此係環氧基 之全酯化物。 環氧丙烯酸酯(A-3-4) 此爲愛皮克特695(大日本油墨化學工業(股份有限)公 司製造的甲酚線性型環氧樹脂)與丙烯酸經酯化反應所調製 。此係環氧基之全酯化物。 環氧丙烯酸酯(A-3-5) 此爲愛皮克特152(油化殼牌(股份有限)公司製造之酚 醛線性型環氧樹脂)與丙烯酸經酯化反應所調製的。此爲環 氧基之全酯化物。 環氧丙烯酸酯(A-3-6) 此爲愛皮克龍680(大日本油墨化學工業(股份有限)公 司製造之甲酣線性型環氧樹脂)與丙稀酸經酯化反應所調製 的。此爲環氧基之全酯化物。 2-丙烯醯基乙基酸磷酸酯係使用共榮社化學(股份有限) 公司製造之來特酯PA。又，2-甲基丙烯醯基羥基乙基酸隣 酸酯係使用共榮社化學(股份有限)公司製造之來特酯PM。 又，在本發明中，化學結構式中不含鹵素之橙色顏料 及藍色顏料，使用與實施例1相同之顏料。 又，做爲比較例所用之以往之綠色有機顏料，也與實 33 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） " (請先閱讀背面之注意事項再填寫本頁) 一裝--------訂---- 517503 A7 _____B7 _ 五、發明說明（p ) 施例1中所用顏料相同。 將前述所準備之各成分，依表2所記載之配合比例均 勻地混合，使用井上製作所（股份有限）公司製作之三輥 機充分地混練，而得到本發明之紫外線硬化型防焊油墨1-；1 7 〇 又，爲評估本發明之紫外線硬化型防焊油墨之性能， 調製不屬本發明範圍之紫外線硬化型防焊油墨Π-ll〜12。 接著，以上述方式所得之紫外線硬化型防焊油墨，係 印刷塗佈至印刷配線板上(分別使用225網孔板藉網版印刷 形成了圖案）。之後，使用120W/cm(或是80W/cm)之金屬 鹵化物(或局壓水銀燈)以光量1000mJ/cm2之光來照射使之 硬化，得到根據本發明之試樣片II -1〜7及超出本發明範 圍之試樣片Π-ll〜12。 對前述所得之(I)光防焊油墨及(II)紫外線硬化型防焊油 墨調整得到之試片，進行鉛筆硬度試驗、棋盤格密接性試 驗、焊料耐熱性試驗、耐溶劑性試驗、耐藥品性試驗、絕 緣電阻試驗及鹵素含量等相關之特性評估。所得結果，一 倂記載於表1。 又，以下簡單說明此類之特性評估試驗之做法。 鉛筆硬度試驗，依日本工業規格〗IS K-5400,8,4進行。 使用鉛筆（三菱尤尼）測定其不致出現傷痕之最高硬度。 棋盤格緊密接著性試驗，依日本工業規格JIS Κ-5400,8.5進行。使用埃氏交叉切割(Erichsen cr〇ss-cut)試驗 機，將硬化皮膜分別往縱橫方向割11道，進行膠帶剝離試 34 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ^ Μ 裝--------訂---------^^1 (請先閱讀背面之注意事項再填寫本頁) 517503 A7 _____ B7 ___ 五、發明說明（η ) 驗。計算100棋盤格中殘餘數。 焊料耐熱試驗，依日本工業規格〗SK6481，5.5進行。焊 劑使用LONCD· CF-350(倫敦化學公司製造之水溶性焊劑) ，首先在試片上塗佈焊劑，接著將之浸漬於260°C之熔融 焊浴10秒鐘，然後立即加入冷水中。於試驗後立即觀察基 板表面，確認有無膨起或剝離。 在耐溶劑性試驗，係於室溫下浸漬於2-丙醇及1，1，1- 三氯乙烷中1小時，觀察基板表面，確認有無膨起或剝離 〇 耐化學藥品性試驗，係將基板在室溫下浸漬於l〇wt% 鹽酸及10wt%氫氧化鈉水溶液中1小時後，觀察基板表面 ’確認有無膨起或剝離。 絕緣電阻試驗，係測定有本發明之硬化塗膜之IPC-B-25梳形圖案之對向電極間之電阻。 鹵素含量係藉由以下之方法來定量：於實施例1之光 防焊油墨之情形，從油墨揮發去除有機溶劑後，將所得之 殘留成分及硬化後之塗膜分別稱重做爲試料，於燃燒燒瓶 內燃燒這些試料，以吸收液吸收所發生之氣體，再以離子 色譜法分析測定吸收液中之氯、溴及氟之含量。 另一方面，於實施例2之紫外線硬化型之防焊油墨之 仪形，則將硬化前之油墨及已被硬化之塗膜分別做爲試料 來稱重，依前述實施例1之相同方法測定鹵素之含量。 本發明之光防焊油墨及紫外線硬化型防焊油墨所形成 之塗膜，根據表1所記載之結果，與不屬本發明範圍之以 35 本紙張尺度適用中國國家標準（cns)A4規格（21〇 x 297公釐）— ----- *t--------tr--------- (請先閱讀背面之注意事項再填寫本頁) 517503 A7 ---5Z---^ 五、發明說明（外） 往之光防焊油墨及紫外線硬化型防焊油墨所形成之塗膜具 有約略相同之硬度、耐剝離性、耐熱性及絕綠性。 又，由本發明之光防焊油墨及紫外線硬化型防焊油墨 所形成之塗膜，其鹵素含量遠比以往之油墨所形成之塗膜 低。從而，此塗膜燃燒時所發生之鹵素量，被認爲比習知 者有顯著之降低。 又，在本發明所使用之著色顏料，具良好分散性，因 此可與各成分配合混合，來輕易地調製。 表1 ----η-------_裝— (請先閲讀背面之注意事項再填寫本頁) 實施例 比較例 光 試樣編號 1-1 VI 1-3 1-4 1-5 1-6 1-7 1-8 Ml M2 防 紫外線硬化性樹脂溶液(A-1-1) 50 50 - - - - 50 焊 紫外線硬化性樹脂溶液(A-1-2) - - 50 - - • 50 油 紫外線硬化性樹脂溶液(A-1-3) - - - 50 - - 墨 紫外線硬化性樹脂溶液(A-1-4) - - - - 50 50 50 50 之 EHPE3150 10 - 10 - - • 10 10 配 多官能環氧化合物溶液(E-1) - 10 - - - - 轉 . 愛皮克龍N-680 - - - 10 10 - 鳴 10 組 TEPIC-S - - - - - 10 10 成 謝卡法斯特橙3064 0.4 0.4 0.4 - - 0.5 — • . 2900珮利卡法斯特橙 - - - 0.3 0.5 - 觸 - • 重 量 CROMOPHTAL DDP Orange TR - - - - - - 0.4 IRGAZIN DDP Orange RA - - - - - - 0.4 . 1ΖΓ 克羅馬法因藍5008 0.4 - - 0.5 - 0.5 克羅馬法因藍4927 - 0.4 0.4 - - • 0.4 0.4 D-7565 - - - - 0.3 • 2GN(酞氰綠） 0.6 0.3 D-8605(肽氰綠） - - - - - • • 0.3 依魯佳吉亞907 4 4 4 4 4 4 4 4 4 4 卡雅吉亞DETX-S 0.5 0.5 0.5 0.5 0.5 0,5 0.5 0.5 0.5 0.5 乙酸卡必醇酯 5 5 5 5 5 5 5 5 5 5 墨達福羅(平整劑） 1 1 1 1 1 1 1 1 1 1 二氧化矽 10 10 10 10 10 10 10 10 10 10 硫酸鋇 20 20 17 20 17 17 20 17 20 20 36 ----訂--------- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 517503 A7 ___B7 五、發明說明（β ) 三聚氰胺 1 1 1 1 1 1 1 1 1 1 二戊赤蘚醇六丙烯酸酯 7 7 7 7 7 7 7 7 7 7 硬 顏色 緣 緣 緣 緣 緣 緣 緣 緣 緣 緣 化 鉛筆硬度(H) 5 5 5 5 5 5 5 5 5 5 皮 棋盤格密著接試驗(個/100個） 100 100 100 100 100 100 100 100 100 100 膜 焊料耐熱性(有/無） 無 Μ j\\\ M 姐 j\\\ M j\\\ 無 赫 J\\\ 並 jw\ M Se j\\\ 之 耐溶劑性(有/無） 無 4rrr m ^TTT ΠΤΓ JW\ Μ. j\\\ j\\\ 無 j\\\ M 無 M >1 特 耐藥品性(有/無） Μ 無 111 il 並 j\\\ 姐 4xrr m 4rrr M j\\\ 4]jr. m 性 絕緣電阻(Χ1013Ω) 2.5 2.6 2.6 2.8 2.8 2.8 2.5 2.6 2.4 2.4 訐 估 鹵素含有 除去有機溶劑之油墨 成分中 90 100 90 300 400 400 90 90 4000 4000 試 驗 量（ppm) 硬化塗膜 90 100 90 300 400 400 90 90 4000 4000 表2 紫外 實施例 比較例 線硬 化型 試樣編號 II-1 II-2 II-3 II-4 II-5 II-6 II-7 11-11 11-12 防焊 環氧丙烯酸酯(A-3-1) 40 - 40 - • • - - - 油墨 環氧丙烯酸酯(A-3-2) - 25 之配 環氧丙烯酸酯(A-3-3) - - - 30 - 30 30 • 合組 環氧丙烯酸酯(A-3-4) ^0 成^ 環氧丙烯酸酯(A-3-5) 30 - 重量 環氧丙烯酸酯(A-3-6) 30 份比 三羥甲基丙烷三丙烯酸酯 40 45 40 50 50 50 50 50 40 2-羥基乙基甲基丙烯酸酯 20 20 20 20 20 20 20 20 15 1,6-己烷二醇二丙烯酸酯 • 10 乙二醇二甲基丙烯酸酯 15 2-丙烯醯基羥基乙基酸磷酸酯 1 - - - - 1 1 - - 2-甲基丙烯醯基羥基乙基酸磷 酸酯 - 1.5 1 1 0.5 - - 1 1 謝卡法斯特橙3064 0.5 0.4 0.4 - 靖 - - 2900珮利卡法斯特橙 - - - 0.5 0.5 - - - - CROMOPHTAL DDP Orange TR • - - - - 0.5 - - • IRGAZIN DDP Orange RA 0.5 - • 克羅馬法因藍5008 0.5 - - 0.5 - - - - - 克羅馬法因藍4927 - 0.4 - - - 0.5 0,5 - - D-7565 - - 0.4 - 0.5 - - - 2GN(酞氰綠） 1 - D-8605(酞氰綠） - 1.2 滑石 40 30 30 30 30 30 30 50 30 37 --------^--------- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 517503 A7 B7 五、發明說明（U ) 戀海8驗 二氧化矽 20 20 20 20 20 20 20 10 30 2-乙基葱酲 1 - 1 1 1 1 1 1 2,4-二乙基噻噸酮 铸 1 苄基二甲基縮酮 1 - 2 1 2 1 1 1 2-羥基-2-甲基小苯基-丙烷小 酮 - - - - - - - - 1 二苯甲酮 1 2-甲基小[4-(甲硫基）苯基]-2-嗎咐基·丙烷-1-酮 - 2 - 1 顏色 緣 緣 緣 緣 緣 緣 緣 緣 緣 鉛筆硬度(H) 5 5 5 5 5 5 5 5 5 棋盤格密接性試驗(個） 100 100 100 100 100 100 100 100 100 絕緣電阻(X] ί013Ω) 2.0 2.4 3.0 5.0 3.6 5.0 5.0 2.5 2.5 鹵素含有量 (ppm) 油墨 240 200 220 260 290 260 260 3600 4300 硬化塗膜 240 200 220 260 290 260 260 3600 4300 焊料浸漬後之膨起或剝離（〇/ X) 〇 〇 〇 〇 〇 〇 〇 〇 〇 — LI — l·------•裝---- (請先閱讀背面之注意事項再填寫本頁)517503 A7 ___m________ V. Description of the Invention (/) Technical Jaw Field This invention relates to solder resist inks used to form permanent protective films for printed wiring boards. More specifically, the present invention relates to a solder resist ink which hardens when exposed to ultraviolet rays. In particular, the present invention relates to a light-shielding ink which develops in a slightly alkaline aqueous solution and a non-image-type ultraviolet curing type solder-resistant ink. This solder resist ink can significantly reduce the amount of toxic gases generated during combustion. Technical background A printed wiring board for printed products used for electrical products is a product in which predetermined wiring is formed on a substrate such as a copper area laminate. In order to prevent solder from being attached to non-essential parts during soldering to avoid short circuiting of the printed wiring board, and in order to prevent shortening of its life, conductor wiring is generally formed on the board, and then formed in accordance with a predetermined pattern. Permanent protective film made of hardened material of solder ink. The substrate or solder resist ink constituting such a printed wiring board has conventionally been a halide containing bromide or the like, which generates a toxic gas during combustion, which has become a major problem. However, with the increasing awareness of environmental issues and the integrity of the human body in recent years, the development of printed wiring boards that do not generate toxic gases during combustion is required. In response to such requests, although substrates such as dehalogenated glass epoxy copper laminates have been developed, the goal of sufficiently reducing the halogen content of solder resist inks has not yet been achieved. Generally speaking, the permanent protective film of the solder resist ink formed on the printed wiring board needs to have good visibility when visually inspected. In addition, it should also be noted that 3 This paper size applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) ----------- Installation -------- Order --------- (Please read the precautions on the back before filling this page) 517503 A7 _ B7 _ V. Description of the Invention (Top) Does not hurt eyesight. Therefore, the permanent protective film used must be green. Therefore, the conventional solder resist ink is green with phthalocyanine green and other pigments. However, the chemical structural formula of this phthalocyanine green contains a high proportion of chlorine and bromine. Specifically, for example, cyanine green with a color index of pigment green 7 contains 47% by weight of chlorine in each molecule, and one molecule of peptide cyanine green with pigment 36 contains about 5% by weight of chlorine and About 60% by weight of bromine. Therefore, a conventional solder resist ink formulated with a high proportion of a halogen-containing coloring pigment like phthalocyanine green will generate a large amount of toxic gas when it is burned. The present invention solves the problem of providing a solder resist ink which is halogen-free or has a low halogen content. Disclosure of the Invention The first invention is a solder resist ink, which comprises: (A) an ultraviolet curable component; (B) a photopolymerization initiator; and (C) a coloring pigment, which is obtained from Halogen-containing orange pigments and blue pigments that do not contain halogens in the chemical structural formula are formulated in a green way. This solder resist ink is especially useful for photo solder resist ink. The ultraviolet-curable component of the photo-soldering ink of the second invention is preferably one containing (A-4) an ethylenically unsaturated monomer. It is more preferable that the solder resist ink further contains (D) an organic solvent. Also, 'This solder mask ink is better if it contains (E) polyfunctional epoxy compound. 4 This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ------- I-- -· III I--1 ^ · II I ----- ^^^^ 1 (Please read the precautions on the back before filling out this page) 517503 A7 _ B7__ V. Description of the invention ($) 〇 Also, this prevention The halogen content in the hardened material of the solder ink is preferably 500 ppm or less. The ultraviolet curable resin as the component (A-1) and the multifunctional epoxy compound as the component (E) added to the solder resist ink are halogen-free epoxy compounds synthesized by the peracid method, for example. Compound, or an epoxy compound that has been treated to reduce halogen, if the (A-1) component and / or (E) component adjusted in this way is used, the photomask of the present invention The halogen content in the hardened material can be below 150 ppm. The coloring color of the component (C) is preferably an orange pigment and the above-mentioned blue pigment in a weight ratio of 1:10 to 10: 1. In addition, the third invention is a solder resist ink, which comprises: (A-3) a polyetherate of an epoxy (meth) acrylate and / or a polyphenol and an esterified product of (meth) acrylic acid (A-4) ethylenically unsaturated compounds other than the aforementioned (A-3) components; (B) photopolymerization initiators; and (C) color pigments, which are colored by a halogen-free chemical structure formula Pigments and blue pigments that do not contain halogen in the chemical structural formula are formulated in a green way. 7 The halogen content in the hardened material of the ultraviolet curable solder resist ink of the third invention is preferably 500 ppm or less. The coloring pigment is preferably a combination of an orange coloring pigment having no halogen in the chemical structural formula and a blue coloring pigment having no halogen in the chemical structural formula in a weight ratio of 1:10 to 10: 1. 5 This paper size applies to China National Standard (CNS) A4 (21〇x 297 public love) " --------------------------- -(Please read the notes on the back before filling out this page) 517503 A7 ____B7 V. Description of the Invention (J) The invention will be described in further detail below. The solder mask of the present invention, which is the best form of the invention, contains (A) an ultraviolet curable component, (B) a photopolymerization initiator, and (C) a mold color pigment containing no halogen in the chemical structural formula and a chemical Blue pigment without halogen in the structural formula. (A) UV-curable component: The solder resist ink in the present invention is blended with the UV-curable component as the component (A). This ultraviolet curable component is a component having a function of ultraviolet curability, and the solder resist ink of the present invention, which is combined with a photopolymerization initiator as a component (C) described later, is irradiated with ultraviolet rays, that is, hardening. When the organic solvent (D) described later is contained, the ultraviolet curable component (A) in all the components of the solder resist ink of the present invention is preferably 20 to 80% by weight, except for the organic solvent. The (A) ultraviolet-curable component to be blended in the present invention is not particularly limited as long as it is cured by ultraviolet irradiation. For example, the ultraviolet-curable resin may have a photoreactive double bond or a photopolymerizable resin. A conventional ultraviolet curable component such as a monomer is arbitrarily selected. (B) Photopolymerization initiator In the solder resist ink of the present invention, a photopolymerization initiator containing (B) component in addition to the (A) ultraviolet curable component described above. Although the above-mentioned photopolymerization initiator contained in the present invention is not particularly limited, suitable photopolymerization initiators in the present invention can be exemplified as follows: Benzoin; Benzoin methyl ether, Benzoin ether And benzoin alkane ethers such as benzoin propyl ether; acenaphthylbenzene, 2,2-dimethoxy-2-phenylacetophenone 6 This paper is in accordance with China National Standard (CNS) A4 specifications ( 210 X 297 mm) ----------- Installation -------- Order --------- (Please read the precautions on the back before filling this page) 517503 A7 _B7_ 5. Description of the invention (f), 2,2-diethoxy-2-phenylacetophenone, and ethyl alcohol benzenes such as 1-hydroxycyclohexyl benzophenone; 2-methyl quinone, 2 -Ethylrestorone, and onionquinones such as 2-aminoquinone; 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone, and 2. Thioxanthone, such as 4-diisopropylthioxanthone; ketal, such as acetophenone ketal and benzyl dimethyl ketal; benzophenone, 3,3-dimethyl 4-methoxybenzophenone, 3,3 ', 4,4'-tetra- (tert-butylperoxycarbonyl) benzophenone and 4-benzidine-4-methyldiphenylsulfide Substances such as benzophenones or oxalone; 2-hydroxy-2-methyl small phenylpropane small ketones and 1-hydroxy-cyclohexyl-phenyl ketones, etc .; α-hydroxy ketones; 2 -Methyl small [4- (methylthio) phenyl] -2-morpholin-propane-1-one, 2-benzidine-2-dimethylamino-1- (4-morpholinyl) -Butanone-1,4,4'-bis-diethylaminobenzophenone and other nitrogen-containing atoms; 2,4,6-trimethylbenzidine diphenylphosphine oxide and the like. These (B) photopolymerization initiators can be formulated individually or in an appropriate combination to prepare the solder resist ink of the present invention. In addition, these photopolymerization initiators can be used with benzoic acid, ethyl p-dimethylamine benzoate, iso-p-dimethylamine benzoate, 2-dimethylamino ethyl benzoate, and the like. Tertiary amines and other conventional photopolymerization accelerators or sensitizers are used. As the (B) component of the photopolymerization initiator, when the organic solvent containing the component (D) described later, in addition to the organic solvent, the entire composition of the solder resist ink of the present invention contains 0. 1 ~ 30% by weight is preferred, 0. 1 to 10% by weight is more preferred, and the most preferred is 0. 1 to 7% by weight. When the photopolymerization initiator containing the compounding amount in the foregoing range is used, the solder resist ink of the present invention will exhibit excellent photo-hardening properties, and the physical properties of the obtained permanent protective film are also very good. 7 ------------ ^^ Packing -------- Order --------- (Please read the precautions on the back before filling this page) This paper size Applicable to China National Standard (CNS) A4 (210 X 297 mm) 517503 A7 ____ B7___ V. Description of the invention (heart) (C) Colored pigments In addition, the solder resist ink of the present invention is compounded as (C) component Colored pigments. The coloring pigment compounded in the present invention is composed of an orange pigment containing no halogen in the chemical structural formula and a blue pigment containing no halogen in the chemical structural formula. The solder resist ink of the present invention is obtained. Or its hardened film has a substantially green ratio to match. The pigment ratio exhibiting a substantially green color here refers to a ratio having a hue or hue that allows a viewer to recognize that the solder resist ink or its hardened film is green to a considerable degree when viewed with the naked eye. Thereby, the pattern on the printed wiring board made with the solder resist ink of the present invention has excellent visibility during visual inspection without damaging eyesight. As an orange coloring pigment which does not contain halogen in the chemical structural formula as the component (C), the colorimetric index is classified as C. I. Pigment orange is preferred. Also, in the aforementioned colorimetric index C. I. Among the pigment orange ’, especially the colorimetric index (C. I. ) Pigment orange 1, 2, 3, 5, 6, 17, 62, 64 and other monoazo pigments,-with colorimetric index (C. I. ) Pigment Orange pigments such as Pigment Orange 40 and 41, one with colorimetric index (C. I. ) A diazo pigment represented by Pigment Orange 14, 15, 16, 50, 63, etc.,-with a color index (C. I. ) Sulfur sulfide 'represented by pigment orange 75, etc. I. ) Pigment orange 43 and so on? ?? series of pigments'-with colorimetric index (C. I. ) Pigment orange 71, 73 and other diketopyrrolopyrrole pigments, 8 ------------ I-order --------- (Please read the note on the back first Please fill in this page again for this matter) This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 517503 A7 _B7_ V. Description of the invention (1)-Colorimetric index (C. I. ) Quinacridone pigments represented by Pigment Orange 48, 49, etc., and (please read the precautions on the back before filling this page) I. ) Metal complexes represented by pigment orange 65, 68, 17: 1 and the like. These pigments can be used individually or in appropriate combinations. In addition, the blue colored pigments containing no halogen in the chemical structural formula of the component (C) are as follows: I. ) Pigment Blue 15 has a chemical structural formula of copper phthalocyanine blue which does not contain halogen,-with a color index (C. I. ) Pigment Blue 16 represented by metal-free peptide cyanine blue,-by colorimetric index (C. I. ) Indigo represented by Pigment Blue 63 and 66,-by colorimetric index (C. I. ) Condensed polycyclic pigments represented by Pigment Blue 65, etc.-by colorimetric index (C. I. The pigments of the quinone series represented by pigment blue 60, etc., have a colorimetric index (C. I ·) Pigment blue Basic blue represented by 1,2,3,10,14,18,19,24,56,57 and 61,-with the colorimetric index (C. I. ) Cyan, represented by Pigment Blue 27,-by colorimetric index (C. I. ) Cobalt Blue represented by Pigment Blue 28, and-by colorimetric index (C. I. ) Ultramarine Blue represented by Pigment Blue 29. These pigments are used singly or in combination at an appropriate ratio. Among the examples mentioned above, the most suitable pigment is copper peptide cyanine blue. 9 This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 517503 A7 B7. V. Description of the invention (§) In addition, the orange pigment and blue pigment are in a ratio of 1: 10 ~ 10: 1 Preferably, even a ratio of 1 ·· 5 ~ 5] is better; the best is a ratio range of 2: 5 ~ 5: 2. If the orange pigment and the blue pigment are combined in the above-mentioned ratio range, the solder resist ink or its hardened film exhibits a substantially green color. In addition, the color of the solder resist ink of the present invention is not green, as long as the hardened material of the solder resist ink of the present invention is green on the bronze-colored copper area laminate. The (C) colored pigment composed of the orange pigment and the blue pigment blended in the above range has good dispersibility to the other components of the solder resist ink of the present invention, and the resulting solder resist ink has few uneven colors and bright colors. Green permanent protective film. In addition, although the compounding amount of the aforementioned (C) coloring pigment in the solder resist ink of the present invention is not particularly limited, when the (C) coloring pigment contains (D) an organic solvent, the organic solvent is not taken into account. The total composition of the solder ink contains 0. 01 ~ 20% by weight is preferred, 0. 1 to 10% by weight is more preferable, and most preferably 0. 2 to 5% by weight. When the blending amount of the coloring pigment is within the foregoing range, it is possible to suppress a decrease in the hardenability of the resin due to a decrease in the transmittance of ultraviolet rays, and it is possible to form a permanent protective film with good visibility during visual inspection. However, the peptide cyanine green pigment used in the past is less likely to be miniaturized and has poor dispersibility. Therefore, in order to prevent the surface state, electrical characteristics, and moisture resistance of the coating film from being adversely affected, it takes a long time to perform the kneading process when preparing the solder mask ink. However, the aforementioned colored pigment (c) has better dispersibility in other components than the cyanine green pigment, and is easier to mix and mix, so the solder resist ink of the present invention can be easily prepared. 10 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ------------------- Order -------- «( (Please read the precautions on the back before filling this page) 517503 A7 ____B7____ 5. Description of the invention (?) (1) Photosoldering ink When the soldermask of the present invention is used as a photosolder, it contains organic solvents or Ultraviolet curable resin that develops inks such as slightly alkaline aqueous solutions. In particular, if the ink can be developed with a slightly alkaline aqueous solution, the ultraviolet curable component of the component (A) is preferably an ultraviolet curable resin having an ethylenically unsaturated group and a carboxyl group in the (A-1) side chain. Especially in the case of the above-mentioned photosolder ink, it is composed of (A-1) an ultraviolet-curable resin having an ethylenically unsaturated group and a carboxyl group in a side chain (B) a photopolymerization initiator and (C) a coloring pigment. Those are better. In the present invention, the "photosoldering ink" is a development type solderless ink. For example, the photomask is selectively exposed to ultraviolet light on the solderless ink applied on the substrate, and The solder mask of the exposed part is hardened, and then the solder mask of the unexposed part is washed and removed in a solution such as a slightly alkaline aqueous solution to obtain a solder mask of the type with a permanent protective film of a predetermined pattern. (A-1) Ultraviolet curable resin having ethylenically unsaturated groups and carboxyl groups on the side chain In the photo-soldering ink of the present invention, the component (A-1) is a combination of ultraviolet rays having ethylenically unsaturated groups and carboxyl groups on the side chain. Hardened resin. Since the chemical structural formula of the component (A-1) contains a photo-hardenable ethylenically unsaturated group and a carboxyl group, once a certain amount of energy is absorbed due to exposure to ultraviolet light or the like, the exposed portion will be hardened. Dispersibility and solubility will decrease. Therefore, the light solder resist oil of the present invention containing the aforementioned (A-1) component will be coated on the substrate. The ink is selectively exposed to harden the light solder mask of the exposed part, and then the size of the 11 paper is adapted to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ------------ -------- Order --------- (Please read the notes on the back before filling this page) 517503 A7 ____ B7 V. Description of the invention (f.) Make this substrate slightly alkaline The aqueous solution is washed, so that the unhardened photo-soldering ink in the unexposed part is dissolved and removed by the slightly alkaline aqueous solution, that is, a predetermined pattern is formed on the substrate. Here, the ultraviolet curing resin of the component (A-1) contains a photopolymerizable ethylenically unsaturated group in its chemical structural formula. Examples of such photopolymerizable ethylenically unsaturated groups include unsaturated groups such as (meth) acrylfluorenyl and vinyl. Although the content of the photopolymerizable ethylenically unsaturated group is not particularly limited, the content of the unsaturated group in the ultraviolet curing resin is 0. The range of 01 ~ 10 mol / kg (ultraviolet curing resin) is better, more suitable for 0. 1 to 5 moles / kg is more preferred. When the content of the unsaturated group in the ultraviolet curable resin is within the above range, a light solder oil ma ink having excellent exposure sensitivity and developability can be prepared. The ultraviolet curable resin of the component (A-1) has an acid valve suitable for 30 to 200 mgKOH / g, and more preferably 40 to 160 mgKOH / g. When the acid value of the ultraviolet curable resin is within the aforementioned range, the compatibility with other components becomes good, and at the same time, a light-shielding ink having particularly excellent exposure sensitivity, developability, and resolution can be prepared. The average molecular weight of the ultraviolet curable resin of the component (A-1) is not particularly limited, but is preferably 3,000 to 400,000, more preferably 5,000 to 100,000, and most preferably 5,000 to 50,000. When the average weight molecular weight of the ultraviolet curable resin is within the aforementioned range, the balance of the resolution and exposure sensitivity of the photomask of the present invention is particularly excellent. The aforementioned (A-1) component may be, for example, the aforementioned epoxy group addition "the ethylenically unsaturated compound having a carboxyl group" in "a polymer having an epoxy group in a side chain". CNS) A4 specification (210 X 297 mm) ----------- installation -------- order --------- (Please read the precautions on the back before (Fill in this page) 517503 A7 B7 V. Description of the invention (丨 丨). Materials "and" polycarboxylic anhydrides ". In order to prepare the ultraviolet curable resin exemplified for the aforementioned (A-1) component, the "polymer containing an epoxy group in the side chain (skeletal polymer)" can be used as the epoxy compound and ethylene listed below. Copolymer of unsaturated monomers. That is, the above-mentioned epoxy compound can be exemplified as follows: glycidyl (meth) acrylate such as glycidyl (meth) acrylate or 2-methylglycidyl (meth) acrylate And (3,4-epoxycyclohexyl) meth (meth) acrylate and other (meth) acrylic epoxycyclohexyl derivatives. Examples of the above ethylenically unsaturated monomers include the following: aliphatic or cycloaliphatic alkyl (meth) acrylates; aromatic (meth) acrylic acids such as benzyl (meth) acrylate Esters; glycol (meth) acrylates such as hydroxyethyl (meth) acrylate or methoxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, and propylene glycol (Meth) acrylic acid esters; (meth) acrylamide compounds; N-substituted maleic anhydride imines; ethylene-pyrrolidone; (meth) acrylonitrile; vinyl acetate; styrene; α- Methylstyrene; and vinyl ether. In addition, in this specification, a general term for (meth) acrylic acrylic acid and methacrylic acid, and a general term for (meth) acrylic acid ester acrylate and methacrylic acid ester. In addition, it is used to prepare the "polymer (framework polymer) having an epoxy group on the side chain" of the ultraviolet curable resin listed as the component (A-1), except for the aforementioned epoxy compound and ethylenic unsaturated In addition to the copolymers of monomers, 尙 can be exemplified as follows: phenolic linear epoxy resin, cresol linear epoxy (please read the precautions on the back before filling this page) _ 装 -------- Order --------- '13 517503 A7 ___B7___ 5. Description of the invention (A) Resin, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol A — linear epoxy resin, grease Cyclic epoxy resins (such as "EHPE-3150" manufactured by Metabol Chemical Co., Ltd.), and trifunctional epoxy resins derived from tris (hydroxyphenyl) methane derivatives (such as manufactured by Nippon Kayaku Co., Ltd.) EPPN-502H, and 742 and XD-9053 made by The Dow Chemical Company). In addition, the "carboxyl-containing ethylenically unsaturated monomer" used to prepare the ultraviolet curable resin exemplified as the component (A-1) includes, for example, (meth) acrylic acid, butenoic acid, and cinnamon Acid, 2- (meth) acrylfluorenyl hydroxyethyl succinic acid, 2- (meth) acrylfluorenyl hydroxyethyl succinic acid, carboxyethyl acrylate, acrylammonium hydroxyethyl succinate, 2 -Acrylic acid, 3- (2-carboxyethoxy) -3-hydroxypropyl ester, 2- (meth) propenylhydroxyethyltetrahydrophthalic acid, and 2- (meth) propenylhydroxyethyl Hexahydrophthalic acid and other ethylenically unsaturated groups; and penterythritol tri (meth) acrylate, trimethylolpropane di (meth) acrylate, dipenterythritol five Among polyfunctional acrylates having a hydroxyl group such as (meth) acrylates, a compound having a plurality of ethylenically unsaturated groups is obtained by reacting a dibasic acid anhydride. Among them, those containing one carboxyl group are more preferable, and those using (meth) acrylic acid or (meth) acrylic acid as a main component are more preferable. This is because the ethylenically unsaturated group introduced by (meth) acrylic acid has excellent photoreactivity. These "carboxyl group-containing ethylenically unsaturated monomers" may be used individually or in combination in an appropriate ratio. In addition, it is used to modulate the UV-curing 14 exemplified as the aforementioned (A-1) component. This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm). -------- Order --------- (Please read the precautions on the back before filling out this page) 517503 A7 ___B7 V. Description of the invention (β) "Polycarboxylic anhydride" for example resin Examples include anhydrous phthalic acid, anhydrous methylsuccinic acid, anhydrous maleic acid, anhydrous citraconic acid, anhydrous glutaric acid, anhydrous itaconic acid, anhydrous phthalic acid, tetrahydroanhydrophthalic acid, methyl tetra Hydrogen anhydrous anhydrous phthalic acid, anhydrous methyl acid, anhydrous hexahydrophthalic acid and methylhexahydroanhydrophthalic acid, etc., and anhydrous trimellitic acid, anhydrous pyromellitic acid, anhydrous benzophenone Tetracarboxylic acid and methylcyclohexene tetracarboxylic acid anhydrides, etc. These "polycarboxylic anhydrides" can be used individually or in appropriate combinations. The aforementioned epoxy group of the polymer having an epoxy group in the side chain is added to an ethylenically unsaturated compound having a carboxyl group and a polycarboxylic acid anhydride to prepare the component (A-1). The addition reaction of the basic resin is, for example, heating in a temperature range of 60 to 150 ° C in the presence of a thermal polymerization inhibitor and an addition catalyst. In addition, in the above-mentioned addition reaction, "a polymer having an epoxy group in a side chain" is added to "an ethylenically unsaturated compound having a carboxyl group", followed by addition of "a polybasic anhydride" or "an epoxy group in a side chain" "Polymer" can be added to "multi-component dianhydride" and then "ethylene-based unsaturated compound with quinone" can be added, but the former is better. In all the components of the photo-soldering ink of the present invention, except for the organic solvents mentioned below, the compounding amount of the component (A-1) is preferably 10 to 80% by weight, although it is not particularly limited, 20 to 70 The weight% is more preferable, and 25 to 60 weight% is the most preferable. If the blending amount of the component (A-1) is within the foregoing range, a light solder resist ink having excellent alkali developability, sensitivity, and resolvability can be obtained. 15 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -------------------- ^ --------- (Please read the precautions on the back before filling in this page) 517503 A7 _________B7 ___— 15. Description of the invention (W) (A-4) Ethylene unsaturated monomer In addition, the light solder resist ink of the present invention, in addition to the above ( A-1) component, 尙 can be blended with (A-4) an ethylenically unsaturated monomer which is (A) an ultraviolet curable component, to improve properties such as coating properties, heat resistance, and insulation properties. This (A-4) heavy polymerizable ethylenically unsaturated monomer, in addition to being an effective diluent, also has the function of adjusting exposure sensitivity. Examples of such ethylenically unsaturated monomers include the following (meth) acrylate monomers: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N-ethylene Pyrrolidone, (meth) acrylamide, methoxytetraethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylic acid Ester, N, N-dimethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, melamine (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di ( (Meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofuran (meth) acrylate, cyclohexyl (meth) acrylate, trimethylolpropane di (meth) acrylate, trihydroxy Methylpropane tri (meth) acrylate, penterythritol tri (meth) acrylate, penterythr tetra (meth) acrylate, dipenterythritol hexa (meth) propane Esters, isocampyl (meth) acrylates, cyclopentene mono (meth) acrylates and cyclopentyne mono (meth) acrylates; monoesters of polybasic acids and hydroxyalkyl (meth) acrylates , Diester, triester, or polyester; polyester (meth) acrylate, urethane (meth) acrylate, and the like. These ethylenically unsaturated monomers can be used alone or in appropriate combination when preparing the light solder resist ink of the present invention. 16 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ------------------- Order --------- C (Please read the precautions on the back before filling this page) 517503 A7 ___B7___ 5. Description of the invention (〖r) In the full composition of the photo-solder ink, except for the organic solvent, the aforementioned (A-4) ethylenic unsaturated Although the compounding amount of the monomer is not particularly limited, it is preferably 1 to 50% by weight, more preferably 1 to 40% by weight, and most preferably 1 to 30% by weight. By combining the photopolymerizable ethylene unsaturated monomer in the aforementioned range, on the one hand, the dry coating film can have a moderate surface adhesion, and on the other hand, when a negative mask with a pattern is placed on the dry coating film, it can be prevented. Negative photoresistance fouling problem. Furthermore, the photo-soldering ink of the present invention can also be combined with an ultraviolet curing polymer such as epoxy (meth) acrylate, (meth) acrylate copolymer, benzene, etc., as required. A copolymer of an ethylenically unsaturated compound such as ethylene-maleic acid resin, or an ultraviolet-curable polymer obtained by further introducing an ethylenically unsaturated group. (B) Photopolymerization initiator The photosoldering ink of the present invention is further blended with a photopolymerization initiator of the component (B). (B) It is preferable to use the photoinitiator listed above. In addition, excluding organic solvents, the photopolymerization initiator of the present invention, (B) component of the photopolymerization initiator in the entire component, to 0. It is preferably 1 to 30% by weight, more preferably 1 to 10% by weight, and most preferably 1 to 7% by weight. When the photopolymerization initiator is contained in a compounding amount within the aforementioned range, the photo-soldering ink of the present invention will have excellent photo-hardening properties, and the resulting permanent protective film will also have excellent physical properties. (C) Coloring pigment The photo-soldering ink of the present invention contains a coloring pigment as a component (C). As mentioned above, the coloring pigments used in the present invention are made of π. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ------------ ------- 1 --------- ^^ _ wl (Please read the precautions on the back before filling out this page) 517503 A7 B7 A Γ -------- V. Description of the invention (〖Heart ) An orange pigment containing no halogen in the chemical structural formula and a blue pigment containing no halogen in the chemical structural formula, and these two pigments are sufficient to make the light solder resist ink or the hardened film of the present invention substantially green To match. With this, the pattern of the printed wiring board made using the photo-soldering ink of the present invention has excellent visibility during visual inspection and does not damage eyesight. The most suitable orange pigments and blue pigments are the same as those listed above. Here, the weight ratio of the orange pigment to the blue pigment is also as described above. A ratio of 1:10 to 10: 1 is preferable, 1: 5 to 5: 1 is more preferable, and an optimal ratio is 2: 5 to 5: 2. The orange pigment and the blue pigment are blended according to the above-mentioned ratio range, and the obtained solder resist ink or the hardened film thereof is substantially green. In addition, the orange pigment and the blue pigment blended in the aforementioned range have good dispersibility of each component of the photo-soldering ink of the present invention, and can obtain a photo-protection formed with a permanent protective film with less color unevenness and bright green. Welding inks: Although the compounding amount of the aforementioned (C) coloring pigment is not specifically limited, the weight ratio of the (C) coloring pigment is not included in the total composition of the light solder resist ink of the present invention, excluding the organic solvent to be described later. To 0. 1 ~ 20% by weight is preferred ’0. 1 ~ 10% by weight is more preferred, and 0. 2 ~ 1. 5% by weight is optimal. When the blending amount of the coloring pigment is within the aforementioned range, on the one hand, it is possible to suppress a decrease in the hardening of the resin due to a decrease in the ultraviolet transmittance, and on the other hand, it can form a permanent protective film with good visibility during visual inspection. (D) Organic solvent The light solder resist ink of the present invention can also be mixed with the organic solvent of (D) component. 18 The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ----- ------ Installation -------- Order --------- (Please read the precautions on the back before filling this page) 517503 A7 ____B7___ V. Description of the invention (β) 〇 In The suitable organic solvents in the present invention include the following, for example: ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol, and ethylene glycol, etc. Chain-like carbon chain grades 1, 2 or polyols; ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; Suva Solu series (made by Jiushan Petrochemical Company) And Lubesu series (manufactured by Exxon Chemical Company) and other petroleum-based aromatic mixed solvents; cellulolytic agents such as cellosolve and butyl cellosolve; cards such as carbitol and butylcarbitol Bis alcohols; propylene glycol alkyl ethers such as propylene glycol methyl ether; polypropylene glycol alkyl ethers such as dipropylene glycol methyl ether; ethyl acetate, butyl acetate, cellosolve acetate, butane Cellulose based acetates, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and other acetates; and dialkyl glycol ethers, etc .; these organic solvents are The light solder resist ink prepared by the present invention can be used individually or in a proper combination. The organic solvent of the aforementioned component (D) accounts for 1 to 95% by weight, or 5 to 95% by weight, or most preferably 20 to 95% by weight in the light solder resist ink of the present invention. good. When the organic solvent is blended within the foregoing range, the obtained photo-soldering ink of the present invention is excellent in coatability on a substrate. (E) Multifunctional epoxy compound In addition to the aforementioned (A-1) ultraviolet curable resin, the photo-soldering ink of the present invention may be blended with an optional multifunctional epoxy compound of (E). Although there are no specific restrictions on polyfunctional epoxy compounds, such as bis ^ a-type bad oxygen resin, bisphenol F-type epoxy resin, phenolic linear epoxy resin, 19 ----------- 0 ^ ------- Order --------- ^ 9. (Please read the precautions on the back before filling this page) This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) 517503 A7 _____ Β7__ 5. Description of the invention (β) Cresol linear epoxy resin, Bisphenol A—linear epoxy resin, N-glycidyl epoxy resin or alicyclic epoxy resin (such as “EHPE-3150” manufactured by Metabol Chemical Co., Ltd.), “YX-4000” (oily Epoxy resins manufactured by Shell Epoxy Co., Ltd.), hydrogenated bisphenol A epoxy resins and triglycidyl isocyanates, and polyfunctional epoxy resins derived from tris (hydroxyphenyl) methane The company's EPPN-502H, Dow Chemical Co., Ltd. (Daxtax-742 and XD-9053, etc.) are examples of this type. Further, as the polyfunctional epoxy resin used in the present invention, a separate polymer or copolymer of an ethylenically unsaturated monomer containing an epoxy group may also be used. When the above-mentioned copolymer is used, the monomer constituting the copolymer preferably contains an ethylene-based unsaturated monomer having an epoxy group in an amount of 40 mol% or more. Thereby, good thermosetting properties can be obtained. In addition, although not particularly limited, when the aforementioned multifunctional epoxy compound is a separate polymer or copolymer of an ethylenically unsaturated monomer containing an epoxy group, its weight average molecular weight is preferably in the range of 2,000 to 200,000. With this, it is possible to prepare a light solder resist ink having a hardened film (with excellent thermosetting property). The aforementioned multifunctional epoxy compound of the (E) component is not included in the entire composition of the photo-soldering ink of the present invention, excluding the organic solvent to be described later, and the compounding amount thereof is 0. 1 ~ 50% by weight is suitable, 0. 1 to 40% by weight is more preferable, and 5 to 40% by weight is most preferable. When the blending amount of the solid content of the polyfunctional epoxy compound is within the above range, a light-shielding ink having a good balance between developability and thermosetting property can be obtained. Further optional components 20 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ------------------ Order ------- --- (Please read the precautions on the back before filling out this page) 517503 A7 ___B7__ V. Description of the invention (i?) In order to further improve the coating, heat resistance and insulation properties of the present invention, Further, an arbitrary component is blended. Examples of such optional components include the following: talc, silica, barium sulfate, alumina, calcium carbonate, mica, and other pigments, inorganic pigments, adhesion-imparting agents, leveling agents, silane coupling agents, Thixotropic agent, polymerization inhibitor, halo inhibitor, defoamer, oxidation inhibitor, surfactant and polymer dispersant. The light solder resist ink of the present invention is prepared by a conventionally well-known kneading method such as a three-roller, a ball mill and a sand mill. Further, in the photo-soldering ink of the present invention, the components need not be completely and uniformly mixed in advance. For example, a mixed liquid 1 composed of (E) component and (D) component 1 is separately prepared, and a mixed liquid 2 composed of (A-1) component, (B) component, (C) component, and (D) component, It is not necessary to mix the mixed liquid 1 and the mixed liquid 2 before use. When the photo-soldering ink of the present invention is coated and dried on a substrate such as a copper area laminate, a specific portion of the obtained dry coating film is irradiated with ultraviolet rays to harden the photo-soldering ink of the portion. Then, the unexposed portion is removed in a slightly alkaline solution for development, and then the unremoved residual photomask is changed into a permanent protective film by post-baking. The aforesaid slightly alkaline solution used as a developing solution is more suitable in the form of an aqueous solution, but it may be a hydrophilic organic solvent such as sperm spray. The halogen content of the permanent protective film obtained in the above manner is preferably 500 ppm or less (actually 0.1 to 500 ppm), more preferably 300 ppm or less (actually 0.1 to 300 ppm), and 150 ppm or less (actually The value is from 0.1 to 150 ppm. 21 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ----------- * t -------- tr --------- (Please read the notes on the back before filling out this page) 517503 A7 _B7_ 5. The invention description (/) is the best. With such a halogen content, the amount of halogen generated during combustion is significantly reduced. According to the present invention, since a halogen-free coloring pigment is used, the "polymer having an epoxy group in a side chain" in the component (A-1) or an epoxy-containing ethylenically unsaturated monomer used in the production thereof (E) and (E) polyfunctional epoxy compounds or epoxy-containing ethylenically unsaturated monomers used in the production thereof are not particularly limited. The use of commercially available materials can make the halogen content in the hardened film Below the aforementioned 500ppm (actually 0. 1 ~ 500ppm). In addition, conventionally, the above-mentioned epoxy compounds used for the modulation of solder mask inks, in particular, epoxy-group-containing ethylene such as epoxy resins or epoxy-propyl methacrylates derived from polycyclic phenol-based compounds, etc. Unsaturated unsaturated monomers are widely used, but these are manufactured industrially by the addition reaction of epichlorohydrin and the release reaction of hydrogen chloride (HC1). There are many reaction by-products or impurities in the product. High concentration of halogen. Therefore, it is difficult to achieve a target of 150 ppm or less in the halogen content of the hardened film formed on the substrate by using the epoxy compound thus produced to prepare a photo-solder-proof ink. On the other hand, according to the present invention, the epoxy compound used in the production of the component (A-1) and the epoxy compound used in the production of the component (E) or the production of the component (E) must be performed using a halogen content of 50 ppm or less. . If such (A-1) component and / or (E) component are used, the halogen content in the permanent protective film formed from the photo-soldering ink of the present invention is significantly reduced compared with the conventional ones. As low as 150ppm. The aforementioned halogen content of 22 used for the preparation of the light solder resist ink of the present invention 22 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -------------- ------ Order --------- (Please read the precautions on the back before filling out this page) 517503 A7 _______B7_____ V. Description of the invention (> 丨) (Please read the precautions on the back before Fill in this page) Epoxy compounds below 50ppm can be epoxy resins synthesized by epoxidation of peracids (for example, peracid, peracetic acid, perbenzoic acid, etc.) and epoxy unsaturated ethylenic unsaturated monomer. These do not use epichlorohydrin during their manufacture and are therefore halogen-free. Examples of these epoxy resins include "EHPE-3150" (alicyclic epoxy resin manufactured by Metabol Chemical Co., Ltd.) and epoxy-containing ethylenically unsaturated monomers, such as There is Seccoloma-A-200 (aliphatic epoxy group-containing ethylenically unsaturated monomer made by Metabolic Chemical Industry Co., Ltd.). Seccoloma-M-100, M-101 (alicyclic epoxy-containing ethylenically unsaturated monomers made by Metabol Chemical Co., Ltd.), etc. Also 'Although it is not synthesized by peracid epoxidation reaction, it is, for example, a Brema GS (made by Nippon Oil & Fats Co., Ltd.) containing an epoxy-containing ethylenically unsaturated monomer prepared by dechlorination. In the case of chlorine-free, epoxypropyl methacrylate), etc., the halogen concentration thereof is also preferably 10 ppm or less. (II) Ultraviolet-curable solder resist ink On the other hand, when the solder-proof ink of the present invention is used as an ultraviolet-curable solder mask, the ultraviolet-curable component as the component (A) is not specifically limited, but With: (A-3) epoxy (meth) acrylate and / or polyether phenol polyetherate and (meth) acrylic acid esters; (A-3) components other than (A-4) ethylene Sexually unsaturated compounds; In other words, 'This UV-curable solder resist ink is composed of (A-3) epoxy (meth) acrylate and / or polyether compound of polyphenol and (meth) acrylic acid ester, (A- 3) (A-4) ethylenically unsaturated compounds other than ingredients, (B) 23 This paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 517503 A7 _—— — —_ B7—_ V. Description of the invention (> >) Photopolymerization initiator and (C) color pigment. In the present invention, the "ultraviolet-curable solder resist ink" refers to a person who forms a predetermined pattern by a printing method to form a permanent protective film, for example, a solder mask printed on a substrate by using a conventionally well-known printing method such as screen printing. On the ink, the solder resist ink of the exposed part is hardened by the full exposure of ultraviolet rays, and a solder resist of the type of a permanent protective film of a predetermined pattern is obtained. (A-3) Polyetherate of epoxy (meth) acrylate and / or polyphenol and esterification of (meth) acrylic acid The ultraviolet-curable solder resist of the present invention, (A-3) Ingredients, containing polyetherate of epoxy (meth) acrylate and / or polyphenol and esterification of (meth) acrylic acid. In the present invention, the above-mentioned epoxy (meth) acrylate of the component (A-3) refers to a full ester or a partial ester of an epoxy group obtained by an esterification reaction of an epoxy compound and (meth) acrylic acid. Compound. In the present invention, these (A-3) epoxy (meth) acrylates may be used individually and conventionally, or may be used in appropriate combinations. Moreover, the said epoxy compound which produces the said epoxy (meth) acrylate is mentioned specifically, from bisphenol A 'bisphenol F, bisphenol A resin, bisphenol F resin, novolac resin, and formazan Resin obtained from the reaction of polyphenols such as phenolic linear resins with epichlorohydrin, and alicyclic epoxy resins (such as peracetic acid epoxy resins substantially free of halogen manufactured by Metabol Chemical Co., Ltd. "EHPE- 3150 ") and so on. On the other hand, in the component (A-3), the polyetherate of polyphenols and the esterification of (meth) acrylic acid are the polyetherate of polyphenols and (A24) This paper is applicable to China Standard (CNS) A4 specification (210 X 297 mm) '' ^--------- ^ --------- (Please read the precautions on the back before filling this page) 517503 A7 —_ B7___ 5. Description of the invention (/) Group) Full or partial esters obtained by the esterification reaction of acrylic acid. Furthermore, the polyether compounds of the above polyphenols can be added to the polyphenols, such as cyclic Oxygen oxide, propylene oxide, butylene oxide, or ε-caprolactone to obtain the complex of the component (A-3) in the ultraviolet-curable solder resist ink of the present invention is not particularly limited, but it is more suitable. The component (A-3) contains 10 to 70% by weight, more preferably 15 to 65% by weight, and most preferably 15 to 60% by weight in the ultraviolet-curable solder resist of the present invention. The ultraviolet-curable solder resist of the present invention containing the component (A-3) in the above-mentioned range is cured by irradiation with ultraviolet rays to obtain a cured product having a desired strength. (A-4) An ethylenically unsaturated compound other than the A-3 component. In addition to the above-mentioned (A-3) component, the ultraviolet-curable solder resist of the present invention contains (A) as (A-4) component. -3) ethylenically unsaturated compounds other than the components. Examples of the ethylenically unsaturated compounds other than the component (A-3) include those exemplified in the description of the above-mentioned photomask. Although there is no particular limitation on the complex of the component (A-4) in the ultraviolet-curable solder resist ink of the present invention, a more suitable component (A-4) contains 10 to 70% by weight in the ink of the present invention. It is more preferably 15 to 65% by weight, and most preferably 20 to 60% by weight. The ultraviolet-curable solder resist of the present invention containing the component (A-4) in the above-mentioned range is cured by ultraviolet irradiation to obtain a cured product having a desired strength. Also 'The above-mentioned (Α_3) component and (Α-4) component constituting the ultraviolet-curable component are applied to the paper standard of 25 Chinese paper (CNS) A4 (21〇X 297 public love) " «t ----- --- tl --------- (Please read the precautions on the back before filling out this page) 517503 A7 ____B7__ 5. Description of the invention (^) The composition ratio is not particularly limited. However, in the total of 100 parts by weight of the components (A-3) and (A-4), the compounding amount of the component (A-3) is preferably from 10 to 70% by weight, more preferably from 10 to 60% by weight, and most preferably It is 15 to 50% by weight. When the components (A) and (B) are blended in the above-mentioned range, the UV-curable solder resist ink can be prepared. The permanent protective film formed has excellent printability, and has excellent hardenability and heat resistance. . > (B) Photopolymerization initiator In addition to the components (A-3) and (A-4) described above, the solder resist ink of the present invention also contains a photopolymerization initiator (B). Suitable photopolymerization initiators contained in the present invention are the same as those previously listed. Also, the blending amount of the (B) photopolymerization initiator in the present invention is, as already mentioned, in the ultraviolet-curable solder resist of the present invention, with 0. It is preferably 1 to 30% by weight, more preferably 1 to 10% by weight, and most preferably 1 to 7% by weight. If the blending amount of the photopolymerization initiator contained is within the above range, the solder resist ink of the present invention will exhibit excellent photohardenability, and the physical properties of the obtained permanent protective film will also be very good. (C) Coloring pigment Further, the solder resist ink of the present invention is compounded with a coloring pigment of the Q component. The coloring pigment compounded in the present invention is, as described above, an orange pigment containing no halogen in the chemical structural formula. And a blue pigment containing no halogen in the chemical structural formula, and in addition, these orange pigments and blue pigments are blended in a proportion of the green solder resist ink or the hardened film thereof of the present invention which is substantially green. Therefore, the printing made using the light solder resist ink of the present invention 26 ------------ install -------- order --------- (please read the back first Please pay attention to this page, please fill in this page) This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 517503 A7 _____ B7____ V. Description of the invention (W) The pattern of the wiring substrate has a visual inspection. Excellent recognizability and less damage to eyesight. (Please read the precautions on the back before filling this page) Orange pigments and blue pigments that do not contain halogen in the chemical structural formula of component (C) above, as listed above The weight ratio of orange pigment to blue pigment, such as In the foregoing, 1:10 to 10: 1 is preferable, 1: 5 to 5: 1 is more preferable, and 2: 5 to 5: 2 [j is the best. The orange pigment and the blue pigment are mixed within the above range, The obtained solder mask ink or its hardened coating film is substantially green. In addition, the orange pigment and the blue pigment blended in the foregoing range have good dispersibility to other components, and the resulting solder mask ink has little color unevenness. It has a bright green permanent protective film. In addition, in the ultraviolet curable solder resist ink of the present invention, although the compounding amount of the color pigment of the component (C) is not particularly specified, the color pigment occupies the ultraviolet curing agent of the present invention. In solder ink. 〇1 ~ 20% by weight is suitable, 0. 1 ~ 10% by weight is more preferable, 0. 2 to 5% by weight is optimal. If a coloring pigment is contained according to the aforementioned blending amount, the ultraviolet-curable solder resist of the present invention can suppress the decrease in resin hardening caused by the decrease in ultraviolet transmittance, and can form a permanent protection with good visibility during visual inspection. membrane. Although the UV-curable solder resist ink of the present invention contains (A-3), (A-4), (B), and (C) as essential components, it does not affect printability, heat resistance, and insulation. Before the characteristics cause adverse effects, it may be good to include other ingredients. Such ingredients can be filled with talc, silica, barium sulfate, alumina, calcium carbonate, and mica, etc., pigments, inorganic pigments, adhesion promoters, etc. 27 This paper size applies to China National Standard (CNS) A4 specifications X 297) " 517503 A7 ______B7 V. Description of the invention (> 0. Leveling agents, thixotropic agents, and polymerization inhibitors are examples. The ultraviolet-curable solder resist of the present invention is printed on a substrate such as a copper area laminate by a conventionally known printing method such as screen printing or offset printing. Since the ultraviolet-curable solder mask of the present invention uses a halogen-free coloring pigment (C), the halogen content in the ultraviolet-curable solder mask is significantly reduced. Specifically, the halogen content of the UV-curable solder resist of the present invention is 500 ppm or less (in reality, 0. 1 to 500 ppm), more preferably 400 ppm or less (in reality, it is 0. 1 ~ 4〇〇ppm), the best is 300ppm or less (the actual situation is 0. 1 ~ 300ppm). Therefore, the permanent protective film formed by the ultraviolet-curable solder resist of the present invention can significantly reduce the amount of halogen gas generated during combustion. On the other hand, when the component (A-3) is produced using an epoxy compound, the epoxy compound may be selected to have a halogen content of 50 ppm or less. Therefore, the halogen content in the permanent protective film formed by the solder resist ink of the present invention can be significantly reduced compared to the past, and can be as low as 150 ppm, which is the same as the aforementioned situation of the photo solder resist ink. Examples The present invention will be further explained based on the following examples, but it is not intended that the present invention is limited to the following examples. In addition, in the following examples, "parts" and "%" are weight basis. Example 1. (I) Light solder resist ink 28 This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 public love) ------------------- Two π ·- -----— I (Please read the notes on the back before filling out this page) 517503 A7 _______________B7 ___ V. Description of the invention (> 7) Prepare the sample of the present invention with the composition ratio described in Table 1- 1 ~ 8. In addition, in order to compare the performance of the photo-soldering ink of the present invention, samples were prepared according to the compounding composition described in Table 1. (A-1-1), (A-1-2), (A-1-3), and (A-1-4) of the ultraviolet curable resins described in Table 1 are prepared as follows: to make. [Synthesis of A-M] In a four-necked flask equipped with a reflux cooler, a thermometer, a glass tube for nitrogen replacement, and a stirrer, Brema GS (Nippon Fats and Oils Co., Ltd., epoxy methacrylic acid containing low chlorine) Ester, halogen content below 1 ppm) 70 parts, 30 parts of methmethacrylate, 100 parts of carbitol acetate, 3 parts of azobisisobutyronitrile, and heating at 80 ° C for 5 hours under nitrogen flow while stirring, To polymerize to obtain a 50% copolymer solution. In the resulting 50% copolymer solution, hydroquinone 0 was added. 05 parts, 37 parts acrylic acid and dimethyl benzylamine 0. Addition of 2 parts at 100 ° C for 24 hours. Next, 45 parts of tetrahydrophthalic anhydride and 79 parts of carbitol acetate were added and reacted at 100 ° C for 3 hours to obtain a 50% solution (A-M) of an ultraviolet curable resin. [A-1-2] Synthesis of 179 parts of EHPE3150 (alicyclic epoxy resin, manufactured by Metabol Chemical Industry Co., Ltd., epoxy equivalent 179, halogen-free (halogen not detected)) was dissolved in In 60 parts of carbitol acetate, 74 parts of acrylic acid and hydroquinone 0 were added while stirring. 1 part and dimethyl benzylamine 0. 7 parts, reacted at 90 ~ 100 ° C for 24 hours according to the general method. 95 parts of carbitol acetate was added to this reaction solution, and stirred to obtain an epoxy acrylate solution. Then add 76 parts of tetrahydrophthalic anhydride and carbitol acetate 64 29 (please read the precautions on the back before filling this page) -pack ----- order ------------- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love) 517503 A7 _ B7 " " " " " one " "-" ------5. Invention The (β) part is explained, and the reaction is performed at 100 ° C. for 3 hours to obtain a 60% solution (A-1-2) of the ultraviolet curable resin. The synthesis of [A-1-3] replaced the Brema gs used in the aforementioned (A-M) synthesis, and replaced it with propylene ester G (manufactured by Mitsubishi Artificial Fibers (Limited) Co., Ltd.), and the content obtained using epichlorohydrin 70 parts of epoxypropylmethylpropionate containing halogen as an impurity; content of 160ppm), and a method of synthesizing (A-1-1) to obtain a 50% solution of ultraviolet spring-curing resin (A -1-3). The synthesis of [A-1 -4] replaces the EHPE3150 used in the synthesis of (A-1-2) described above, and it is changed to use a cresol linear type manufactured by Kron N-680 (Dai Nihon Ink Chemical Industry Co., Ltd.) Epoxy resin, epoxy equivalent 214, halogen content 1050 ppm) 21 parts, and when the anhydride is added, the composition of the carbitol acetate compound is changed to 78 parts, and the rest are imitated (A-1-2 ), A 60% solution (A-1-4) of an ultraviolet curable resin was prepared. In addition, the EHPE3150 used in the multifunctional epoxy compounds described in Table 1 is an epoxy resin manufactured by Metabol Chemical Co., Ltd. and Epicon N-680 is Dainippon Ink Chemical Industry Co., Ltd. ) The cresol linear epoxy resin manufactured by the company, TEPIOS is a triglycidyl isohydroxide (halogen content of 800 ppm) manufactured by Nissan Chemical Industry Co., Ltd. [Synthesis of E-1] In addition, (E-1) described in Table 1 was prepared by the following method. That is, a paper cooler, a thermometer, and a glass for nitrogen replacement are installed on this paper. The paper size is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)- -------- Order -------- 517503 A7 ___B7___ V. Description of the invention (J) 'Four-necked flask with tube and mixer, add Brema GS (manufactured by Japan Oils and Fats Co., Ltd.) , Low chlorine-containing epoxy propyl methacrylate) 80 parts, butyl acrylate 20 parts, carbitol acetate 67 parts, and azobisisobutyronitrile 3 parts, while stirring under nitrogen flow at 85 Polymerization was performed at ° C for 5 hours to obtain a 60% solution (E-1) of a polyfunctional epoxy compound. In the present invention, an orange pigment containing no halogen in its chemical structural formula uses Shekafast Orange 3064 (color index (C. L) Pigment Orange 5 (a monoazo-based orange pigment manufactured by Dainichi Seika (Limited) Co., Ltd.), and 2900 Likafast Orange GR (color index (C. I. ) Pigment Orange 16) (Mono-azo pigment manufactured by Daiichi Seika (Limited) Co., Ltd.), CROMOPHTAL DDP Orange TR ((Color Index (C. I. ) Pigment Orange 71) (Dioxopyrrolopyrrole-based orange pigment manufactured by Jibate Chemical Co., Ltd.), IRGAZIN DDP Orange RA ((color index (C. I. ) Pigment Orange 73) (A dioxopyrrolopyrrole-based orange pigment manufactured by Gibbott Chemical (Stock Co., Ltd.)). In the present invention, the blue pigment containing no halogen in the chemical structural formula uses Cromfain Blue 5008 (color index (C. I. ) Pigment Blue 15 (Peptide Cyan Blue Pigment manufactured by Daiichi Refinery (Limited) Co., Ltd.), Cromfain Blue 4927 (color index (C. I. ) Pigment Blue 15) (Phthalocyanine Blue Pigment manufactured by Dainichi Seika Chemical Co., Ltd.), and D-7565 (Color Index (C. I. ) Pigment Blue 16) (metal-free peptide cyanine blue pigment manufactured by BASF). As a green organic pigment used in the past, 2GN ((colorimetric index (C. I. ) Pigment Green 7 (Phthalocyanine Green Pigment manufactured by Daiichi Refinery Co., Ltd.), and D-8605 (Color Index (C. I. ) Pigment Green 7) (phthalocyanine green pigment manufactured by BASF). 31 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) ^ -------- ^ ------ 517503 A7 ___B7_____ V. Description of the invention () The photopolymerization initiator Ilujagiya 907 used is a product manufactured by Jibagagi Company, and Kayagiya DETX-S is manufactured by Nippon Kayaku Co., Ltd. Manufactured products. Modafor is a levelling agent manufactured by Monsanto. For silicon dioxide, the average particle size is 1 // m. The light-shielding inks 1-1 to 8 and 1-11 to 12 obtained above were screen-coated on the entire surface of a printed wiring board (copper made of a glass epoxy substrate with a copper foil of 35 / zm). The area laminate was patterned in advance with uranium engraving to form a pattern). In order to volatilize the solvent, it was pre-cured at 80 ° C for 20 minutes to obtain a dry coating film with a film thickness of 20 / zm. Then, the mask with the pattern drawn directly against the coating film surface, and was irradiated with ultraviolet light of 150m; i / cm2, and then developed with a 1% sodium carbonate aqueous solution as a developing solution to form a pattern, followed by 150 It is hardened by heating at 60 ° C for 60 minutes to prepare sample pieces 1-1 to 8 according to the present invention and sample pieces 1-11 to 12 beyond the scope of the present invention. Example 2 (II) Ultraviolet-curable solder resist In order to prepare the ultraviolet-curable solder resist of the embodiment, the following epoxy acrylates (A-3-1) to (A-3-6) were prepared. Epoxy Acrylate (A-3-1) This is prepared by the esterification reaction of Apictor 154 (a phenolic linear epoxy resin made by Petrochemical Shell (Stock Co., Ltd.)) with acrylic acid. This is a full ester of epoxy groups. Epoxy acrylate (A-3-2) This is a double 32 made by Apictor 828 (Petrochemical Shell (Stock Co., Ltd.). The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm)) (Please read the precautions on the back before filling out this page) -------- ^ --------- 517503 A7 ____ Β7 ___ 5. Description of the invention (M) • Phenol A epoxy resin) It is prepared by esterification with acrylic acid. This is an epoxy-based full ester. Epoxy acrylate (A-3-3) This is a phenolic linear epoxy resin made by EPPN-20K Nippon Kayaku Co., Ltd.) and acrylic acid is prepared by esterification reaction. Esters. Epoxy acrylate (A-3-4) This is prepared by the esterification reaction of Apictor 695 (cresol linear epoxy resin manufactured by Dainippon Ink Chemical Industry (Limited) Co., Ltd.) and acrylic acid. This is a full ester of epoxy groups. Epoxy Acrylate (A-3-5) This is an esterification reaction of Epicste 152 (a phenolic linear epoxy resin manufactured by Petrochemical Shell Co., Ltd.) and acrylic acid. This is a full ester of epoxy groups. Epoxy acrylate (A-3-6) This is prepared by the esterification reaction of Apicron 680 (formaldehyde linear epoxy resin manufactured by Dainippon Ink Chemical Industry (Stock Co., Ltd.)) and acrylic acid. . This is a full ester of epoxy groups. 2-propenylethyl ethyl phosphate is a special ester PA manufactured by Kyoeisha Chemical Co., Ltd. In addition, 2-methacryl fluorenyl hydroxyethyl acid phthalate was used as a special ester PM manufactured by Kyoeisha Chemical Co., Ltd. In the present invention, an orange pigment and a blue pigment which do not contain a halogen in their chemical structural formula are the same pigments as in Example 1. In addition, the conventional green organic pigment used as a comparative example is also compatible with the actual Chinese paper standard (CNS) A4 (210 X 297 mm). The paper size is the same as that used in the comparative example. Page) One pack -------- Order ---- 517503 A7 _____B7 _ V. Description of the invention (p) The pigments used in Example 1 are the same. Each of the ingredients prepared above was uniformly mixed according to the mixing ratios described in Table 2, and thoroughly mixed using a three-roller machine manufactured by Inoue Manufacturing Co., Ltd. to obtain the UV-curable solder resist 1- of the present invention. 170. In order to evaluate the performance of the UV-curable solder mask ink of the present invention, the UV-curable solder mask inks Π-11 to 12 which are not within the scope of the present invention were prepared. Next, the UV-curable solder resist ink obtained in the above-mentioned manner was applied to a printed wiring board by printing (each pattern was formed by screen printing using a 225 mesh plate). After that, a metal halide (or a local pressure mercury lamp) of 120 W / cm (or 80 W / cm) is used to irradiate the light with a light amount of 1000 mJ / cm2 to harden it to obtain a sample piece II-1 to 7 and Sample pieces Π-11 ~ 12 which are beyond the scope of the present invention. The pencil test, the checkerboard adhesion test, the solder heat resistance test, the solvent resistance test, and the chemical resistance were performed on the test pieces obtained by adjusting the (I) light solder resist ink and (II) ultraviolet curable solder resist ink obtained above. Performance test, insulation resistance test and halogen content evaluation. The results obtained are summarized in Table 1. In addition, the method of such a characteristic evaluation test is briefly described below. The pencil hardness test is performed according to Japanese Industrial Standards IS K-5400,8,4. Use a pencil (Mitsubishi Uni) to determine the highest hardness that will not cause scratches. Checkerboard close adhesion test, according to Japanese industrial standard JIS KK-5400, 8. 5 proceed. Using an Erichsen cross-cut test machine, the hardened film was cut 11 times in the vertical and horizontal directions, and the tape peeling test was performed. 34 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ） ^ 装 -------- Order --------- ^^ 1 (Please read the precautions on the back before filling this page) 517503 A7 _____ B7 ___ 5. Description of the invention (η) Check. Calculate the number of residuals in 100 checkers. Solder heat resistance test according to Japanese Industrial Standards SK6481, 5. 5 proceed. The flux used was LONCD · CF-350 (a water-soluble flux manufactured by the London Chemical Company). First, the test piece was coated with flux, and then immersed in a molten solder bath at 260 ° C for 10 seconds, and then immediately added to cold water. Immediately after the test, the surface of the substrate was observed to confirm the swelling or peeling. In the solvent resistance test, it is immersed in 2-propanol and 1,1,1-trichloroethane at room temperature for 1 hour, and the surface of the substrate is observed to confirm whether there is swelling or peeling. After the substrate was immersed in 10 wt% hydrochloric acid and 10 wt% sodium hydroxide aqueous solution at room temperature for 1 hour, the surface of the substrate was observed to confirm whether there was swelling or peeling. The insulation resistance test is to measure the resistance between the counter electrodes of the IPC-B-25 comb pattern of the hardened coating film of the present invention. The halogen content was quantified by the following method: In the case of the photo-soldering ink of Example 1, after the organic solvent was removed from the ink by evaporation, the remaining components and the cured coating film were weighed as samples, and These samples were burned in a combustion flask, and the generated gas was absorbed by the absorption liquid, and the content of chlorine, bromine and fluorine in the absorption liquid was determined by ion chromatography analysis. On the other hand, in the shape of the UV-curable solder resist ink of Example 2, the ink before curing and the cured coating film were weighed as samples, and measured according to the same method as in Example 1. Content of halogen. According to the results described in Table 1, the coating film formed by the photo-soldering ink and the UV-curable solder-resistant ink of the present invention is in accordance with the Chinese National Standard (cns) A4 specification (35 paper sizes) outside the scope of the present invention. 21〇x 297 mm) — ----- * t -------- tr --------- (Please read the notes on the back before filling this page) 517503 A7- -5Z --- ^ V. Description of the invention (outside) The coating film formed by the conventional light solder resist ink and ultraviolet curing solder resist has approximately the same hardness, peel resistance, heat resistance, and green opacity. In addition, the coating film formed by the photo-soldering ink and the UV-curable solder resist of the present invention has a halogen content much lower than that of a coating film formed by a conventional ink. Therefore, the amount of halogens generated when the coating film is burned is considered to be significantly lower than that of the conventional one. In addition, since the coloring pigment used in the present invention has good dispersibility, it can be blended with various components and easily prepared. Table 1 ---- η -------_ equipment— (Please read the precautions on the back before filling this page) Example Comparative Example Light Sample Number 1-1 VI 1-3 1-4 1- 5 1-6 1-7 1-8 Ml M2 UV curable resin solution (A-1-1) 50 50----50 UV curable resin solution (A-1-2)--50-- • 50 oil UV curable resin solution (A-1-3)---50--ink UV curable resin solution (A-1-4)----50 50 50 50 EHPE3150 10-10--• 10 10 with polyfunctional epoxy compound solution (E-1)-10---- Epicon N-680---10 10-Naruto 10 sets TEPIC-S-----10 10% Shekafast Orange 3064 0. 4 0. 4 0. 4--0. 5 — •. 2900 Likafast Orange---0. 3 0. 5-Touch-• Weight CROMOPHTAL DDP Orange TR------0. 4 IRGAZIN DDP Orange RA------0. 4. 1ZΓ Cromaine Blue 5008 0. 4--0. 5-0. 5 Cromfain Blue 4927-0. 4 0. 4--• 0. 4 0. 4 D-7565----0. 3 • 2GN (phthalocyanine green) 0. 6 0. 3 D-8605 (Peptide Cyanide Green)-----• • 0. 3 Iruga Gia 907 4 4 4 4 4 4 4 4 4 4 Cajagia DETX-S 0. 5 0. 5 0. 5 0. 5 0. 5 0, 5 0. 5 0. 5 0. 5 0. 5 Carbitol acetate 5 5 5 5 5 5 5 5 5 5 Modaline (leveling agent) 1 1 1 1 1 1 1 1 1 1 1 Silicon dioxide 10 10 10 10 10 10 10 10 10 10 Barium sulfate 20 20 17 20 17 17 20 17 20 20 36 ---- Order --------- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 517503 A7 ___B7 V. Description of the invention (Β) Melamine 1 1 1 1 1 1 1 1 1 1 1 Dipenterythritol hexaacrylate 7 7 7 7 7 7 7 7 7 7 Hard color edge edge edge edge edge edge edge edge edge pencil hardness (H) 5 5 5 5 5 5 5 5 5 5 Skin checkerboard adhesion test (pcs / 100 pcs) 100 100 100 100 100 100 100 100 100 100 100 Film solder heat resistance (yes / no) No Μ j \\\ M sister j \\\ M j \\\ solventless J \\\ and jw \ M Se j \\\ solvent resistance (with / without) none 4rrr m ^ TTT ΠΤΓ JW \ Μ. j \\\ j \\\ no j \\\ M no M > 1 special chemical resistance (yes / no) Μ no 111 il and j \\\ sister 4xrr m 4rrr M j \\\ 4] jr. m Insulation resistance (X1013Ω) 2. 5 2. 6 2. 6 2. 8 2. 8 2. 8 2. 5 2. 6 2. 4 2. 4 Estimated halogen content of the ink component removed from organic solvents 90 100 90 300 400 400 90 90 4000 4000 Test amount (ppm) Hardened coating film 90 100 90 300 400 400 90 90 4000 4000 Table 2 UV Examples Comparative Examples Sample No. II-1 II-2 II-3 II-4 II-5 II-6 II-7 11-11 11-12 Solder resist epoxy acrylate (A-3-1) 40-40-• •- --Ink epoxy acrylate (A-3-2)-25 with epoxy acrylate (A-3-3)---30-30 30 • Combined epoxy acrylate (A-3-4) ^ 0 to ^ epoxy acrylate (A-3-5) 30-weight epoxy acrylate (A-3-6) 30 parts by weight trimethylolpropane triacrylate 40 45 40 50 50 50 50 50 40 2 -Hydroxyethyl methacrylate 20 20 20 20 20 20 20 20 15 1,6-hexanediol diacrylate • 10 ethylene glycol dimethacrylate 15 2-propenyl hydroxyethyl acid phosphate 1----1 1--2-Methacrylamidohydroxyethyl acid phosphate-1. 5 1 1 0. 5--1 1 Shekafast Orange 3064 0. 5 0. 4 0. 4-Jing--2900 珮 Likafast Orange---0. 5 0. 5----CROMOPHTAL DDP Orange TR •----0. 5--• IRGAZIN DDP Orange RA 0. 5-• Cromaine Blue 5008 0. 5--0. 5-----Cromfain Blue 4927-0. 4---0. 5 0,5--D-7565--0. 4-0. 5---2GN (phthalocyanine green) 1-D-8605 (phthalocyanine green)-1. 2 Talc 40 30 30 30 30 30 30 50 50 30 37 -------- ^ --------- (Please read the precautions on the back before filling this page) This paper size applies to Chinese national standards (CNS) A4 specification (210 X 297 mm) 517503 A7 B7 V. Description of the invention (U) Love sea 8 test silicon dioxide 20 20 20 20 20 20 20 10 10 2-Ethyl onion 1-1 1 1 1 1 1 2,4-Diethylthioxanthone cast 1 Benzyldimethylketal 1-2 1 2 1 1 1 2-Hydroxy-2-methyl small phenyl-propane small ketone------ --1 Benzophenone 1 2-Methyl small [4- (methylthio) phenyl] -2-macroylpropane-1-one Pencil hardness (H) 5 5 5 5 5 5 5 5 5 Checkboard adhesion test (pcs) 100 100 100 100 100 100 100 100 100 Insulation resistance (X) 013) 2. 0 2. 4 3. 0 5. 0 3. 6 5. 0 5. 0 2. 5 2. 5 Halogen content (ppm) Ink 240 200 220 260 290 260 260 3600 4300 Hardened coating film 240 200 220 260 290 260 260 3600 4300 Bulging or peeling after solder dipping (〇 / X) 〇— LI — l · ------ • Install ---- (Please read the precautions on the back before filling this page)
本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)