A7 1237531 ___B7 _ 五、發明說明（丨） [技術領域] 本發明係關於用以形成印刷配線板之永久保護膜的防 焊油墨。更詳細地說’本發明係關於受到紫外線照射會硬 化之防焊油墨，其包含可進行顯像之光防焊油墨、以及非 顯像類型之紫外線硬化型防焊油墨兩者。 又，此防焊油墨在燃燒時之有毒氣體產生量可被顯著 地壓低。 ^ [背景技術] 於電氣製品所使用之印刷配線基板，係在銅面積層板 等之基板上形成有既定之配線者。此印刷配線基板爲了防 止在進行焊接之際於不需之部分附著上焊料，來避免電氣 短路等，且爲了防止其使用壽命的縮短，所以一般的做法 係在基板上形成導體配線之後，讓防焊油墨之硬化物所構 成之永久保護膜以既定之圖案來形成。 以往，構成上述印刷配線基板之基板、防焊油墨係含 Φ 有溴化物等之鹵化物，在燃燒時有產生有毒氣體之情事， 此爲問題所在。 惟，伴隨著近年來對於環境問題與人體安全性的關切 日益升高，乃希望開發出於燃燒時不會產生有毒氣體的印 刷配線基板。對應於此種要求，已有例如經脫鹵化之玻璃 環氧銅面積層板等之基板被開發出來，但是在防焊油墨方 面，目前並未達成將鹵素含有量予以充分降低之目標。 一般而言，於印刷配線基板上所形成之防焊油墨的永 久保護膜，必須爲於目視檢查時在辨識性上優異、且對於 3 (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公釐） A7 1237531 ___B7_____ 五、發明說明（> ) 眼睛不致造成損傷之物，是以，此永久保護膜必須呈現綠 色或藍色。 是以，以往有配合酞氰綠等之著色顏料所成之綠色的 防焊油墨。惟，此酞氰綠之化學結構式中含有高比例之氯 或溴。具體而言，例如色指數(C.I·)爲顏料綠7之酞氰綠在 1分子中含有約47重量％之氯，又爲顏料綠36之肽氰綠在 1分子中含有約5重量％之氯與約60重量％之溴。 Ο 是以，配合上含有高比例之酞氰綠類鹵素的著色顏料 所構成之以往的防焊油墨，在燃燒時會產生大量的有毒氣 體。 另一方面，配合不含鹵素之著色顏料，來謀求永久保 護膜之低鹵素化的防焊油墨也被提出。 以其一例來說，可舉出配合在化學結構式中不含鹵素 之藍色顏料所得之藍色的防焊油墨。此處所配合之藍色顏 料，可舉出例如呈現C.I·顏料藍15之物的當中，化學結構 • 式中不含鹵素之銅酞氰藍；呈現C.I·顏料藍16之物的當中 ，化學結構式中不含鹵素之無金屬酞氰藍等。 又，尙提出有讓化學結構式中不含鹵素之藍色顏料與 化學結構式中不含鹵素之黃色顏料搭配組合所成、用以形 成綠色之永久保護膜的防焊油墨。 惟，此等化學結構式中不含鹵素之著色顏料、尤其是 藍色顏料，其不僅粒子之粉碎性、分散性不佳，且配合此 顏料所成之防焊油墨的永久保護膜受到焊接等之加熱處理 的情況下容易褪色。 4 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐1 - --------^--------- (請先閱讀背面之注意事項再填寫本頁) 1237531 A7 B7 Φ 五、發明說明（ 是以，本發明之課題在於提供一種使用粉碎性與分散 性優異之藍色顏料而有效率地調製出之防焊油墨。尤其， 本發明之課題在於提供一種燃燒時之鹵素氣體的產生量少 、且受到焊接等之加熱處理的情況下可形成不易褪色之永 久保護膜的防焊油墨。 [發明之揭示] 本發明係一種防焊油墨，其特徵在於，含有： (A) 紫外線硬化性成分； (B) 光聚合起始劑；以及 (C) 銅酞氰顏料，其化學結構式中具有至少1個之鹵素 原子，且於分子量中鹵素含有量佔25%以下。 作爲前述(A)成分，若使用（A — 1)於側鏈具有乙烯性不 飽和基與羧基之紫外線硬化性樹脂之情形下，可得到作爲 光防焊油墨爲有用之製品。 再者，於(A)成分中含有(A — 4)乙烯性不飽和單體乃爲 所希望的。 又，通常，此防焊油墨進一步含有(D)有機溶劑乃爲所 希望者。 作爲(A)成分使用了 (A—1)紫外線硬化性樹脂之防焊油 墨，以進一步含有(E)多官能環氧化合物爲佳。 又，此防焊油墨之硬化物中之鹵素的含有量以500ppm 以下爲佳。 又，於上述之防焊油墨中所配合之作爲(A — 1)成分的 紫外線硬化性樹脂以及作爲(E)成分之多官能環氧化合物， 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} a 1237531 A7 ___Bl_ 五、發明說明（W ) 以利用例如過氧法所合成之不含鹵素的環氧化合物、或是 施行過用以降低鹵素含有量之處理的環氧化合物所調製者 爲佳，若使用以此方式調整過之(A — 1)成分以及/或是(E)成 分，可將本發明之光防焊油墨之硬化物中的鹵素含有量控 制在150ppm以下。 上述之防焊油墨，以進一步含有分子量中之鹵素含有 量在25%以下之第二著色顏料爲佳。 又，作爲前述(A)成分，亦可使用（A — 3)環氧（甲基)丙 烯酸酯以及/或是多元酚類之聚醚化物與（甲基)丙烯酸所成 之酯化物、以及前述(A — 3)成分以外之(A — 4)乙烯性不飽 和化合物，此時，可得到作爲紫外線硬化型之防焊油墨爲 有用之製品。 此時，將防焊油墨之硬化物中的鹵素含有量控制在 500ppm以下爲佳。 又，於此防焊油墨中所含之(A — 3)成分’以利用過氧 法所合成之不含鹵素的環氧化合物、或是施行過用以降低 鹵素含有量之處理的環氧化合物所調製者爲佳’此時，防 焊油墨之硬化物中的鹵素含有量控制在150PPm以下爲佳 又，上述之防焊油墨，以進一步含有分子量中之鹵素 含有量在25%以下之第二著色顏料爲佳。 以下針對本發明之防焊油墨中所含之(A)紫外線硬化性 成分、（B)光聚合起始劑；以及(C)銅酞氰顏料(化學結構式 中具有至少1個之鹵素原子，且於分子量中鹵素含有量佔 --------^--------- (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） 1237531 A7 B7 五、發明說明（ 25%以下）來說明。 (A)糸外線硬化性成分 (A) 成分爲具有紫外線硬化性機能之成分，若與(c)成 分一光聚合起始劑一倂用，可使得防焊油墨受到紫外線照 射時會硬化。 又，防焊油墨亦可含有(D)成分一有機溶劑一，除此有 機溶劑，於本發明之防焊油墨中所含之成分的量以 20〜80重量％左右爲佳。 於本發明中所配合之(A)成分只要受到紫外線照射可硬 化之物即可並無特別限定，例如可自具有光反應性雙鍵的 紫外線硬化性樹脂或光聚合性之單體等之習知的紫外線硬 化性成分當中任意地選擇。 (B) 光聚合起始劑 於本發明所使用之光聚合起始劑並無特別之限定，較 佳者可舉出例如：苯偶因、苯偶因甲醚、苯偶因乙醚以及 苯偶因異丙醚等之苯偶因的烷醚類；乙醯苯、2,2一二甲氧 基一2 —苯基乙酿苯、2,2 —一乙氧基一2—苯基乙驢苯以及 1一羥基環己基苯酮等之乙醯苯類；2—甲基憩醌、2—乙基 恩酸以及2 —戊基急醒等之恩醒類；2,4一二甲基瞳順酮、 2,4一二乙基噻噸酮、2—異丙基噻噸酮、4一異丙基噻噸酮 以及2,4一二異丙基噻噸酮等之噻噸酮類；苄基二甲基酮縮 醇等之酮縮醇類；二苯甲嗣、3,3〜二甲基一4—甲氧基二 苯甲酮、3,3’，4,4’一四（特丁基過氧基羰基)二苯甲酮以及4 一苯醯一4一甲基二苯基硫化物等之二苯甲酮類或是2,4一 -----------裝--------訂---------^^1 (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） A7 B7 1237531 $、發明說明（b ) 二異丙基咕噸酮等之咕噸酮類；2 —羥基一2一甲基一 i —苯 基一丙烷一 1 一酮以及1 一羥基一環己基一苯基一酮等之α 一羥基酮類；2—甲基一1 一[4一（甲硫基)苯基]一2一嗎咐一 1 一丙酮、2 —苄基一2—二甲胺基—i_(4一嗎啉苯基）一丁 醇一丨、4,4’一雙（二乙胺基）二苯甲酮等之含氮原子者； (2,4,6—三甲基苯醯基）二苯基膦氧化物等。該等之光聚合 起始劑可單獨使用亦可組合至少兩種來使用。 4 又，該等之光聚合起始劑亦可與對二甲胺基苯甲酸乙 酯、對二甲胺基苯甲酸異戊酯、2—二甲胺基乙基苯甲酸酯 等之三級胺系等之眾知的光聚合促進劑或增感劑等倂用。 又，亦可使用可見光、近紅外線曝光用等之光聚合起 始劑。 相關之(B)成分一光聚合起始劑一除了任意所含之有機 溶劑，在防焊油墨之全成分中只要含有0.1〜30重量％左右 即可，又以含0.1〜10重量％、尤其是0.1〜7重量％爲佳。 若以上述範圍之配合量來含有光聚合起始劑，本發明之防 焊油墨可展現優異之光硬化性，所得之永久保護膜的物性 也良好。 (C)著色顏料 本發明之防焊油墨中除了上述(A)與(B)成分以外所含 有之(C)成分，係化學結構式中具有至少1個之鹵素原子， 且於分子量中鹵素含有量佔25%以下之銅软氰顏料。 作爲此種銅肽氰顏料，可舉出以C.I.顏料藍15(含有 15 : 1等)表示者當中，在化學結構式中作爲鹵素含有1〜3 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 裝--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 1237531 A7 B7 ❿ 五、發明說明（ 個氯者。 此種銅肽氰顏料，相較於不含鹵素之肽氰顏料在混練 時之粉碎性與分散性良好，又在耐熱性方面也優異。又， 將配合有上述著色顏料所成之本發明的光防焊油墨之永久 保護膜加以燃燒，鹵素氣體之產生量少，又即使受到焊接 般之加熱處理的情況或是長時間暴露於光的情況下，永久 保護膜也不易褪色。 又’於本發明之防焊油墨中，除了上述之銅跃氰顏料 以外，亦可配合其他之著色顏料（以下稱爲「第二顏料」） 。此種第二顏料並無特別之限定，惟以鹵素在分子量中所 佔之量爲25%以下者、或是在化學結構式中不含鹵素原子 者爲佳’藉此’可讓所形成之永久保護膜之鹵素含有量充 分地降低。 做爲本發明之墨水中可配合的上述第二顏料可列舉如 下。 (藍色顏料） 作爲化學結構式中不含鹵素原子之藍色顏料，可舉出 以C.I·顏料藍15表示者當中，在化學結構式中不含鹵素之 銅肽氰藍； 以C.I.顏料藍Ιό表示之無金屬酞氰藍； 以C.I·顏料藍63與66表示之靛藍； 以C.I·顏料藍65等表示之縮合多環系之顏料； 以C.I·顏料藍6〇等表示之憩醌系之顏料； 以 C.I·顏料藍 1、2、3、10、14、18、19、24、56、 衣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) --------^------^. 1237531 A7 _B7_ 五、發明說明（，？） 57以及61等表示之鹼性藍； 以C.I.顏料藍27表示之深藍； 以C.I.顏料藍28表示之鈷藍； 以C.I.顏料藍29表示之群藍等。該等之顏料可單獨使 用亦可適當組合來使用。 (黃色顏料） 作爲化學結構式中不含鹵素原子之黃色顏料，在色指 數被分類爲C.I.顏料黃所舉出之顏料皆可適用。作爲此種 黃色顏料，尤其以 以C.I.顏料黃139與185等表示之異吲哚啉系之顏料 以 C.I.顏料黃 120、151、175、180、181 以及 194 等 表示之苯咪唑啉系之顏料； 以C.I.顏料黃148、182以及192等表示之縮合多環系 之顏料； 以C.I.顏料黃101等表示之雙偶氮甲川系之顏料； 以 C.I·顏料黃 1、4、5、7、9、65、74、150、154 以 及167等表示之單偶氮系之顏料； 以C.I.顏料黃24、108、123、147以及193等表示之 憩醌系之顏料； 以C.I.顏料黃155等表示之雙偶氮系之顏料； 以C.I.顏料黃117、129、153、177以及179等表示之 金屬錯合物系之顏料； 以C.I·顏料黃24等表示之黃憩酮； 10 (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公釐） 1237531 B7 五、發明說明（6丨） 以C丄顏料黃42等表示之氧化鐵系之顏料；以及 以 C.I·顏料黃 61、62、100、104、133、168 以及 169 等表示之可溶性偶氮系之顏料等。 又，作爲在化學結構式中具有至少一個之鹵素原子之 胃色^顏料，且鹵素在分子量中所佔之量爲25%以下者，更 佳者可舉出 以C.I·顏料黃3表示之單偶氮系之顏料； Φ 以C.I.顏料黃12、13、14以及17表示之重氮系之顏 料； 其他之以C.I·顏料黃55表示之顏料等。 該等之黃色顏料可單獨使用亦可適宜地組合使用。 (橙色顏料） 作爲化學結構式中不含鹵素原子之橙色顏料，在色指 數被分類爲C.I·顏料橙所舉出之顏料皆可適用。作爲此種 橙色顏料，尤其以 ^ 以C.I·顏料橙1、2、3、5、6、17、62以及64等表示 之單偶氮系之顏料； 以C.I·顏料橙40以及41等表示之憩酮系之顏料； 以C_I·顏料橙14、15、16、50以及63等表示之二重 氮系之顏料； 以C.I·顏料橙75等表示之铈硫化物之顏料； 以C.I.顏料橙43等表示之北酮(perylone)之顏料； 以C.I·顏料橙71以及73等表示之吡咯并吡咯系之顏 料； 11 一0 家標準（CNS)A4 規格（210 X 297 公釐) ' "" --------^---------線 (請先閱讀背面之注意事項再填寫本頁) 1237531 Φ A7 B7 五、發明說明（p ) 以C.I.顏料橙48以及49等表示之·吖酮之顏料； 以C.I·顏料橙65、68、17 : 1等表示之金屬錯合物系 之顏料等。 另一方面，作爲在化學結構式中具有至少一個之鹵素 原子之橙色顏料，且鹵素在分子量中所佔之量爲25%以下 者，更佳者可舉出 以C.I.顏料橙36表示之單偶氮系之顏料； 以C.I.顏料橙13以及34表示之單偶氮系之顏料。 該等橙色顏料可單獨使用亦可適宜地組合使用。 一般而言，形成永久保護膜之防焊油墨，其以上述方 式所形成之永久保護膜，較佳爲著色成爲於目視檢查時在 辨識性上優異、且對於眼睛不致造成損傷之綠色。 如上所述，本發明之油墨，係配合有作爲必要成分之 在化學結構式中具有至少一個之鹵素原子、且鹵素在分子 量中所佔之量爲25%以下之(C)成分的銅肽氰顏料，惟除了 此銅肽氰顏料以外，藉由進一步配合擇自上述藍色顏料、 黃色顏料以及橙色顏料之至少1種類的顏料，可得到綠色 或藍色（尤其是綠色）的永久保護膜。且此種綠色之永久保 護膜之鹵素含量少。 又，在特開2000-232264號公報所記載之發明雖具有 低鹵素化之優點，但所使用之顏料的粉碎性與分散性未必 良好；相對地本發明中所配合之顏料在粉碎性與分散性也 良好，可減少著色顏料的使用量。又，此種本發明之防焊 油墨的永久保護膜於燃燒時之鹵素氣體的產生量少、且受 12 --------^--------- (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） 1237531 A7 ____B7_ 五、發明說明（) 到焊接等之加熱處理的情況下也不易褪色。 又，爲了得到可形成色斑少而鮮豔的綠色永久保護膜 之防焊油墨，作爲（C)成分之銅酞氰顏料與第二顔料之重量 比以銅酞氰：第二顏料=1 : 10〜10 : 1爲佳，尤以1 : 5〜5 :1爲佳。 於本發明中，在化學結構式中具有至少一個之鹵素原 子、且鹵素在分子量中所佔之量爲25%以下之(C)成分的銅 ^ 酞氰顏料的配合量並無特別之限定，惟除了任意含有之有 機溶劑，於本發明之墨水的全成分中含有0.1〜20重量％左 右爲佳，又以含有0.1〜10重量％、尤以0.2〜5重量％乃爲 更佳者。銅酞氰顏料之配合量在上述範圍內時，可抑制因 紫外線透過率之減少所導致之光反應性的降低同時可得到 目視檢查時辨識性良好之永久保護膜。 又，上述銅酞氰顏料與上述第二顏料之合計量並無特 別之限定，惟除了任意含有之有機溶劑，於本發明之墨水 φ 全成分中含有1〜20重量％左右爲佳，又以含有0·1〜10重 量％、尤以〇·2〜5重量％爲佳。上述銅狀氰顏料與上述第二 顏料之合計的配合量在上述範圍內時，可抑制因紫外線透 過率之減少所導致之光反應性的降低同時可得到目視檢查 時辨識性良好之永久保護膜。 (I )光防焊油墨 本發明之防焊油墨作爲光防焊油墨來利用之情況，以 讓墨水可藉由有機溶劑或稀鹼性水溶液等而進行顯像爲佳 ，作爲(Α)成分可使用紫外線硬化性樹脂。 13 --------^--------- (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） 1237531 A7 ______B7____ 五、發明說明（P ) 尤其’在讓墨水藉稀鹼性水溶液而可進行顯像方面， 作爲（A)成分以使用前述(A — 1)成分、亦即於側鏈具有乙嫌 性不飽和基與羧基之紫外線硬化性樹脂爲佳。 又，於本發明中所說的「光防焊油墨」也就是所謂的 顯像型之防焊油墨，例如對應於：對於在基板上所塗佈之 防焊油墨以紫外線進行選擇性曝光讓此受曝光之部分的防 焊油墨硬化，而後將未曝光部分之防焊油墨在稀鹼性水溶 1 液中洗淨去除所得之既定圖案的永久保護膜之類型之防焊 油墨。 前述(A — 1)成分，由於其化學結構式中具有光硬化性 之乙烯性不飽和基與羧基，所以一旦其受到紫外線等之曝 光而吸收既定之能量，受曝光部分即會硬化從而對於稀鹼 性水溶液之分散性與溶解性降低。是以，將含有(A — 1)成 分之本發明的光防焊油墨塗佈在基板上、進行選擇性曝光 ’讓曝光部分的光防焊油墨硬化，而後將此基板在稀鹼性 4 水溶液中洗淨，來將未曝光部分之未硬化的光防焊油墨以 稀驗性水溶液溶解去除，即可於基板上形成既定之圖案。 此(A — 1)成分之紫外線硬化性樹脂，於化學結構式中 具有光聚合性之乙烯性不飽和基。作爲此種光聚合性之乙 稀性不飽和基，可舉出例如（甲基）丙烯醯基與乙烯基等之 不飽和基。此種光聚合性之乙烯性不飽和基的含有量並無 特別之限定’一般在紫外線硬化性樹脂中之不飽和基的含 有量爲0.01〜10莫爾/公斤(紫外線硬化性樹脂），尤以〇·1〜5 莫爾/公斤爲佳。當紫外線硬化性樹脂中之不飽和基的含有 14 私纸張尺度適用中國國家標準（CNS)A4規格_(2i〇 X 297公釐） 裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 1237531 A7 Φ B7 五、發明說明（Ο ) 量在上述範圍時，可特別調製出兼具優異曝光感度與顯像 性之光防焊油墨。 又作爲(A-1)成分之紫外線硬化性樹脂較佳係酸價爲 30〜200 mgKOH/g、尤以S夂價爲40〜160 mgKOH/g爲佳。當 紫外線硬化性樹脂之酸價在上述範圍，不僅與其他成分之 相溶性變得良好，且可特別調製出具有良好之曝光感度、 顯像性與解析性之光防焊油墨。 1 再者，作爲(A — 1)成分之紫外線硬化性樹脂之重量平 均分子量並無特別之限定，惟一般係3,〇〇()〜400,000、尤以 5,000〜100,000爲佳、更佳爲5,000〜5〇,〇〇〇。當紫外線硬化 性樹脂之重量平均分子量在上述範圍時，本發明之光防焊 油墨之解析性與曝光感度的平衡尤其優異。 作爲(A—D成分，可舉出例如「側鏈具有環氧基之聚 合物」中之在前述環氧基加成「具有羧基之乙烯性.不飽和 化合物」與「多元羧酸酐」所成之紫外線硬化性樹脂。 作爲用以調製上述(A — 1)成分所舉例之紫外線硬化性 樹脂所用的「側鏈具有環氧基之聚合物（骨架聚合物)， 可舉出以下般之環氧化合物與乙烯性不飽和單體=所^赴 聚物。 〃 亦即，作爲環氧化合物，可舉出縮水甘油基（甲基）丙 烯酸酯或2—甲基縮水甘油基（甲基)丙烯酸酯等之縮水甘油 基（甲基)丙烯酸酯類；以及(3,4一環氧基環己基）甲基（甲基） 丙烯酸酯等之（甲基)丙烯酸的環氧基環己基衍生物類等。 又，作爲乙烯性不飽和單體，可舉出脂肪族^脂環族 15 ------------•裝--- (請先閱讀背面之注意事項再填寫本頁) I n H ϋ “δ，I ϋ I an 1 n n I · 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1237531 A7 B7 五、發明說明（a 之烷基（甲基)丙烯酸酯；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 系（甲基)丙烯酸酯以及丙二醇系（甲基)丙烯酸酯；（甲基)丙 烯醯胺系化合物；N—取代順丁烯二醯抱亞胺系化合物； 乙烯基吡咯烷酮；（甲基）丙烯腈；醋酸乙烯酯；苯乙烯； α—甲基苯乙烯；以及乙烯醚等。 又，在本說明書中所謂的（甲基）丙烯酸係丙烯酸與甲 基丙烯酸之總稱，所謂的（甲基）丙烯酸酯係丙烯酸酯與甲 基丙烯酸酯之總稱。 作爲用以調製上述(Α-1)成分所舉例之紫外線硬化性 樹脂所用的「側鏈具有環氧基之聚合物（骨架聚合物）」， 除了上述之環氧化合物與乙烯性不飽和單體所成之共聚物 ，尙可舉出例如酚醛淸漆型環氧樹脂、甲酚淸漆型環氧樹 脂、雙酚Α型環氧樹脂、雙酚F型環氧樹脂、雙酚Α—淸 漆型環氧樹脂、脂環式環氧樹脂(例如代謝爾化學工業公司 製造「EHPE — 3150」）、以及三(羥苯基）甲烷之衍生物的多 官能環氧樹脂（例如日本化藥（股份有限公司）製造EPPN-502H、以及道爾化學公司製造達克特克斯一742以及XD 一9053等)等之環氧樹脂。 又’作爲用以調製(A — 1)成分所舉例之紫外線硬化性 樹脂所用的「具有羧基之乙烯性不飽和單體」，可舉出例 如（甲基）丙烯酸、巴豆酸、桂皮酸、2 —（甲基）丙烯醯基羥 基乙基琥珀酸、2—（甲基)丙烯醯基羥基乙基肽酸、/3—羧 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 1237531 A7 ___B7_ 五、發明說明（八） 基乙基丙烯酸酯、丙烯醯基羥基乙基琥珀酸酯、2 —丙烯酸 、3一（2 一羧基環氧基）一 3 一羥基丙酯、2-(甲基)丙烯醯基 羥基乙基四氫酞酸以及2—（甲基)丙烯醯基羥基乙基六氫故 酸等之具有1個乙烯性不飽和基者；以及，對於戊赤蘚醇 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基丙烯酸 酯讓二元酸酐反應所得般之具有複數個乙烯性不飽和基者 該等當中又以具有1個羧基者爲佳，尤其以使用（甲基 )丙烯酸或使用以（甲基)丙烯酸做爲主成分者爲佳。其理由 在於，藉（甲基)丙烯酸所導入之乙烯性不飽和基在光反應 性優異之故。 該等之「具有羧基之乙烯性不飽和單體」可單獨使用 或適當組合來使用。 又，作爲用以調製(A — 1)成分所舉例之紫外線硬化性 樹脂所用的「多元羧酸酐」可舉出例如無水琥珀酸、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、無水肽酸、四氫無水肽酸、甲基四氫無水社酸 、無水甲基萘酚二胺酸、六氫無水酞酸及甲基六氫無水跃 酸等之2元酸酐；以及無水苯六酸、無水焦苯六酸、無水 苯酚四羧酸以及甲基環己烯四羧酸酐等之3元酸以上之酸 酐。 該等之「多元羧酸酐」可個別單獨使用或適宜組合來 使用。 17 (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公釐） 1237531 A7 ---- B7 五、發明說明（) 對於上述般之在側鏈具有環氧基之聚合物之前述環氧 基加成具有羧基之乙烯性不飽和化合物與多元羧酸酐來調 製作爲（A — 1)成分所舉例之紫外線硬化性樹脂的加成反應 方面’係例如在熱聚合抑制劑以及加成觸媒之存在下加熱 到60〜150°C左右來進行。 又，上述加成反應，可對「側鏈具有環氧基之聚合物 」加成「具有羧基之乙烯性不飽和化合物」後再加成「多 ^ 元羧酸酐」，又，亦可對「側鏈具有環氧基之聚合物」加 成「多元羧酸酐」後再加成「具有羧基之乙烯性不飽和化 合物」，其中以前者爲佳。 除了後述之有機溶劑之本發明的光防焊油墨之全成分 中的上述(A — 1)成分的配合量並無特別之限定，惟較佳爲 10〜80重量％、更佳爲20〜70重量％、最佳爲25〜60重量％ 。當(A^l)成分之配合量在上述範圍的情況，可得到在鹼 顯像性、感度以及解析性良好之光防焊油墨。 ) (A — 4)乙烯性不飽和單體 又，本發明之光防焊油墨，除了上述(A — 1)成分，亦 可進一步配合作爲(A)成分之(A-4)乙烯性不飽和單體，來 提昇塗佈性、耐熱性與絕緣性等之特性。又，此(A — 4)光 聚合性乙烯性不飽和單體除了扮演稀釋劑之角色，也扮演 調節曝光感度之角色。 作爲此種乙烯性不飽和單體，可舉出2 —羥乙基（甲基) 丙烯酸酯、2 —羥丙基（甲基)丙烯酸酯、N —乙烯基毗咯烷 酮、（甲基)丙烯醯基嗎咐、（甲基)丙烯醯基嗎啉、甲氧基四 18 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) 1237531 A7 _______B7 五、發明說明（j ) 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—二甲基胺基丙基（甲基 )丙烯醯胺、N，N—二甲基胺基乙基（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、四氫糠基（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 蘚醇四（甲基)丙烯酸酯、二戊赤蘚醇五（甲基)丙烯酸酯、二 戊赤蘚醇六（甲基)丙烯酸酯、異乙烯基（甲基)丙嫌酸酯、環 戊基單（甲基)丙烯酸酯以及環戊烯基單（甲基)丙烯酸酯；多 元酸與羥烷基（甲基）丙烯酸酯的單酯、二酯、三酯或是聚 酯；聚酯（甲基)丙烯酸酯、氨酯（甲基)丙烯酸酯等之（甲基) 丙烯酸酯單體等。 該等之乙烯性不飽和單體在調製本發明之光防焊油墨 之時可分別單獨使用或適宜地組合使用。 除了有機溶劑之光防焊油墨中的上述(A — 4)乙烯性不 飽和單體的配合量並無特別之限定，惟較佳爲1〜5〇重量％ 、更佳爲1〜40重量％、最佳爲1〜30重量％。藉由配合上 述範圍之光聚合性乙烯性不飽和單體，可對乾燥塗膜賦予 適當的表面黏著性，並可防止將描繪有圖案之負型光罩壓 附於乾燥塗膜進行曝光之際的負型光罩污損之問題。 又，本發明之光防焊油墨可依必要性進一步配合環氧 19 請 先 閱 讀 背A7 1237531 ___B7 _ V. Description of the Invention (丨) [Technical Field] The present invention relates to solder resist ink used to form a permanent protective film for printed wiring boards. More specifically, the present invention relates to a solder resist ink which is hardened when irradiated with ultraviolet rays, and includes both a solder resist ink capable of developing and a UV curing solder resist ink of a non-developing type. In addition, the amount of toxic gas generated by this solder resist ink during combustion can be significantly reduced. ^ [Background Art] Printed wiring boards used in electrical products are those in which predetermined wiring is formed on a substrate such as a copper area laminate. In order to prevent solder from being attached to unnecessary parts during soldering to avoid electrical short circuits, etc., and to prevent its service life from shortening, the general practice is to prevent the The permanent protective film composed of the hardened material of the solder ink is formed in a predetermined pattern. Conventionally, the substrates and solder masks constituting the above-mentioned printed wiring boards contain halogenated compounds such as bromine and the like, which may generate toxic gases during combustion. This is a problem. However, as concerns about environmental issues and human safety have increased in recent years, it has been desired to develop printed wiring boards that do not generate toxic gases during combustion. In response to such requirements, substrates such as dehalogenated glass epoxy copper area laminates have been developed, but in terms of solder resist inks, the goal of sufficiently reducing the halogen content has not yet been achieved. Generally speaking, the permanent protective film of the solder resist ink formed on the printed wiring board must be excellent in visibility during visual inspection and must be 3 (please read the precautions on the back before filling this page) ▼ -------- Order ---------. This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) A7 1237531 ___B7_____ V. Description of the invention (>) Eyes What does not cause damage is that this permanent protective film must be green or blue. Therefore, conventionally, green solder resist inks have been prepared by combining pigments such as phthalocyanine green. However, the chemical structural formula of this phthalocyanine green contains a high proportion of chlorine or bromine. Specifically, for example, phthalocyanine green whose color index (CI ·) is pigment green 7 contains about 47% by weight of chlorine in one molecule, and peptide cyano green which is pigment green 36 contains about 5% by weight in one molecule. Chlorine and about 60% by weight of bromine. 〇 It is a conventional solder resist ink composed of a coloring pigment containing a high proportion of phthalocyanine green halogens, which generates a large amount of toxic gases during combustion. On the other hand, a halogen-free solder resist ink which is formulated with a halogen-free color pigment to achieve a permanent protective film has also been proposed. One example is a blue solder resist ink obtained by blending a blue pigment containing no halogen in the chemical structural formula. For the blue pigment compounded here, for example, the chemical structure of the substance exhibiting CI · Pigment Blue 15 and the chemical structure of the copper phthalocyanine blue containing no halogen; the chemical structure of the substance exhibiting CI · Pigment Blue 16 In the formula, there is no metal phthalocyanine blue which does not contain halogen. In addition, I have proposed a solder resist ink formed by combining a blue pigment containing no halogen in the chemical structural formula and a yellow pigment containing no halogen in the chemical structural formula to form a green permanent protective film. However, coloring pigments that do not contain halogen in these chemical structural formulas, especially blue pigments, not only have poor pulverizability and dispersibility of the particles, but also the permanent protective film of the solder resist ink formed with the pigment is subjected to welding, etc. It is easy to discolor in the case of heat treatment. 4 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm 1--------- ^ --------- (Please read the precautions on the back before filling in this Page) 1237531 A7 B7 Φ 5. Description of the invention (The purpose of the present invention is to provide a solder resist ink which is efficiently prepared by using a blue pigment with excellent pulverization and dispersibility. In particular, the subject of the present invention is Provided is a solder resist ink that generates a small amount of halogen gas during combustion and forms a permanent protective film that is not easily discolored when subjected to heat treatment such as welding. [Disclosure of the Invention] The present invention is a solder resist ink, which is characterized in that It contains: (A) an ultraviolet curable component; (B) a photopolymerization initiator; and (C) a copper phthalocyanine pigment having at least one halogen atom in its chemical structural formula, and a halogen content in the molecular weight 25% or less. As the component (A), if (A-1) an ultraviolet curable resin having an ethylenically unsaturated group and a carboxyl group in a side chain is used, a product useful as a photo-soldering ink can be obtained. In addition, it is contained in the component (A) (A-4) An ethylenically unsaturated monomer is desirable. Usually, it is desirable that the solder resist further contains (D) an organic solvent. (A-1) is used as the (A) component. It is preferable that the solder resist ink of the ultraviolet curable resin further contains (E) a polyfunctional epoxy compound. The halogen content in the hardened material of the solder resist ink is preferably 500 ppm or less. The ultraviolet curable resin (A-1) component and the multifunctional epoxy compound (E) component are used in the solder ink. The paper size is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm). Equipment -------- Order --------- (Please read the notes on the back before filling out this page} a 1237531 A7 ___Bl_ V. Description of the invention (W) It can be synthesized by using peroxy method, for example A halogen-free epoxy compound or an epoxy compound that has been treated to reduce the halogen content is preferred. If (A-1) components adjusted in this way and / or ( E) The component can control the halogen content in the hardened material of the photo-solder ink of the present invention. It is preferably 150 ppm or less. The above solder resist ink preferably further contains a second coloring pigment having a halogen content of 25% or less in the molecular weight. In addition, as the component (A), a ring (A-3) may also be used. Oxy (meth) acrylate and / or polyether phenolic polyetherates and (meth) acrylic acid esters, and (A-4) ethylenically unsaturated compounds other than the aforementioned (A-3) component At this time, useful products can be obtained as ultraviolet curing type solder resist ink. At this time, it is better to control the halogen content in the hardened material of the solder resist ink to 500 ppm or less. The (A-3) component contained in the solder mask ink is a halogen-free epoxy compound synthesized by a peroxy method or an epoxy compound that has been treated to reduce the halogen content. It is better to prepare it. At this time, it is better to control the halogen content in the hardened material of the solder resist ink to 150 PPm or less. The above solder resist ink further contains a halogen content in the molecular weight of 25% or less. Colored pigments are preferred. The following is directed to (A) an ultraviolet curable component, (B) a photopolymerization initiator contained in the solder resist ink of the present invention, and (C) a copper phthalocyanine pigment (having at least one halogen atom in the chemical structural formula, And the halogen content in the molecular weight accounts for -------- ^ --------- (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 Specifications (210 X 297 mm) 1237531 A7 B7 5. The description of the invention (less than 25%). (A) 糸 External hardening component (A) The component is a component with ultraviolet curing properties. A photopolymerization initiator can be used at once to make the solder resist ink harden when it is exposed to ultraviolet rays. In addition, the solder resist ink may also contain (D) component-an organic solvent-in addition to the organic solvent, in the solder resist of the present invention The amount of the component contained in the ink is preferably about 20 to 80% by weight. The component (A) compounded in the present invention is not particularly limited as long as it can be cured by ultraviolet radiation, and for example, it can have a photoreaction UV curing resin or photopolymerizable monomers (B) Photopolymerization initiator The photopolymerization initiator used in the present invention is not particularly limited, and preferred examples include benzoin and benzoin. Ethers, benzoin ethers, and benzoin isopropyl ethers; acetoin ethers; acetophenone, 2,2-dimethoxy-2-phenylethylbenzene, 2,2-ethyl Acetylbenzenes such as oxy 2-phenylethanylbenzene and 1-hydroxycyclohexyl benzophenone; 2 methylmethylquinone, 2-ethylenic acid, and 2-pentyl emergency wake up, etc. ; 2,4-Dimethylstilbone, 2,4-Diethylthioxanthone, 2-Isopropylthioxanthone, 4-Isopropylthioxanthone, and 2,4-Diisopropylthioxanthone Thioxanthone such as ton ketone; ketal such as benzyl dimethyl ketal; benzophenone, 3,3 ~ dimethyl-4-methoxybenzophenone, 3,3 ', 4,4'-tetrakis (tert-butylperoxycarbonyl) benzophenone and 4-benzophenone-4-methyldiphenyl sulfide or 2,4-one- ---------- Loading -------- Order --------- ^^ 1 (Please read the precautions on the back before filling this page) This paper ruler Degree Applicable to Chinese National Standard (CNS) A4 Specification (210 X 297 mm) A7 B7 1237531 $, Description of Invention (b) Dixanthones such as diisopropylxanthones; 2-hydroxy-1 2-methyl-1 i —Phenyl-propane- 1-one and α-hydroxy-ketones such as 1-hydroxy-cyclohexyl-phenyl-one; 2-methyl-1 1- [4-((methylthio) phenyl] —2—1 What is a 1-acetone, 2-benzyl-2-dimethylamine-i_ (4-morpholinophenyl) -butanol-1, 4,4'-bis (diethylamino) benzophenone Those who have a nitrogen atom; (2,4,6-trimethylphenylfluorenyl) diphenylphosphine oxide, etc. These photopolymerization initiators may be used alone or in combination of at least two. 4 Moreover, these photopolymerization initiators can also be used with three of p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, 2-dimethylaminoethylbenzoate, etc. A well-known photopolymerization accelerator or a sensitizer such as a grade amine is used. Further, a photopolymerization initiator for visible light, near-infrared light exposure, or the like may be used. The related component (B)-a photopolymerization initiator-except for any organic solvent contained, may only contain about 0.1 to 30% by weight in all the components of the solder resist ink, and further contains 0.1 to 10% by weight, especially It is preferably 0.1 to 7% by weight. When the photopolymerization initiator is contained in a compounded amount within the above range, the solder resist ink of the present invention can exhibit excellent photohardening properties, and the physical properties of the obtained permanent protective film are also good. (C) Colored pigment The component (C) contained in the solder resist ink of the present invention in addition to the components (A) and (B) described above has a halogen atom of at least one in the chemical structural formula, and the halogen contained in the molecular weight Copper soft cyanine pigments with an amount of less than 25%. Examples of such copper peptide cyano pigments include those represented by CI Pigment Blue 15 (containing 15: 1, etc.), which contains 1 to 3 as halogen in the chemical structural formula. This paper is compliant with the Chinese National Standard (CNS) A4 standard. (210 X 297 mm) installed -------- order --------- line (please read the precautions on the back before filling this page) 1237531 A7 B7 ❿ V. Description of the invention (a Chlorine. Compared with halogen-free peptide cyanide pigments, this copper peptide cyanide pigment has better pulverizability and dispersibility during kneading, and is also excellent in heat resistance. In addition, it is made by blending the above-mentioned colored pigments. The permanent protective film of the photo-soldering ink of the invention is burned, the amount of halogen gas generated is small, and even if it is subjected to welding-like heat treatment or exposed to light for a long time, the permanent protective film is not easy to fade. 'In the solder resist ink of the present invention, in addition to the copper cyanide pigment described above, other coloring pigments (hereinafter referred to as "second pigments") may be blended. Such a second pigment is not particularly limited, but it is based on The amount of halogen in the molecular weight is 25% or less, It is better to have no halogen atom in the chemical structural formula. By doing so, the halogen content of the formed permanent protective film can be sufficiently reduced. The above-mentioned second pigment that can be blended in the ink of the present invention can be listed as follows (Blue pigment) Examples of blue pigments that do not contain halogen atoms in the chemical structural formula include those represented by CI · Pigment Blue 15 and copper peptide cyanide blue that does not contain halogen in the chemical structural formula; CI pigments Blue Ιό Metal-free phthalocyanine blue; Indigo blue represented by CI · Pigment Blue 63 and 66; Condensed polycyclic pigments represented by CI · Pigment Blue 65 and the like; Diquinone represented by CI · Pigment Blue 60 and the like Department of pigments; CI · Pigment Blue 1, 2, 3, 10, 14, 18, 19, 24, 56, and paper size applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read first Note on the back, please fill in this page) -------- ^ ------ ^. 1237531 A7 _B7_ V. Basic blue shown in the description of the invention (,?) 57 and 61; CI pigment Deep blue represented by blue 27; cobalt blue represented by CI pigment blue 28; group blue represented by CI pigment blue 29 These pigments can be used singly or in combination as appropriate. (Yellow pigment) As a yellow pigment containing no halogen atom in the chemical structural formula, any pigment listed in the color index as CI Pigment Yellow can be used. Such yellow pigments are, in particular, isoindoline-based pigments represented by CI Pigment Yellow 139 and 185, and benzimidazoline-based pigments represented by CI Pigment Yellow 120, 151, 175, 180, 181, and 194; CI Pigment Yellow 148, 182, and 192, etc. Condensed polycyclic pigments; CI Pigment Yellow 101 and other bisazomethanine pigments; CI · Pigment Yellow 1, 4, 5, 7, 9, 65 , 74, 150, 154, and 167 are monoazo pigments; CI Pigment Yellow 24, 108, 123, 147, and 193 are quinone pigments; CI Pigment Yellow 155 and the like are dual Nitrogen pigments; metal complex pigments represented by CI Pigment Yellow 117, 129, 153, 177, and 179; progesterone represented by CI · Pigment Yellow 24; 10 (Please read the notes on the back first (Please fill in this page for matters) ▼ Install -------- Order ------- -. This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) 1237531 B7 V. Description of the invention (6 丨) Iron oxide pigments represented by C 丄 Pigment Yellow 42 etc .; and CI · Pigment yellow 61, 62, 100, 104, 133, 168, and 169 are soluble azo-based pigments. In addition, as a gastric color pigment having at least one halogen atom in the chemical structural formula, and the amount of halogen in the molecular weight is 25% or less, the more preferable one is represented by CI · Pigment Yellow 3. Azo pigments; Φ diazo pigments represented by CI Pigment Yellow 12, 13, 14, and 17; other pigments represented by CI · Pigment Yellow 55. These yellow pigments may be used alone or in a suitable combination. (Orange pigment) As an orange pigment that does not contain a halogen atom in its chemical structural formula, any of the pigments listed in the color index as C.I. Pigment Orange can be used. As such an orange pigment, in particular, ^ monoazo pigments represented by CI · Pigment Orange 1, 2, 3, 5, 6, 17, 62, 64, and the like; and CI · Pigment Orange 40 and 41, etc. Restorone pigments; Diazo pigments represented by C_I · Pigment Orange 14, 15, 16, 50, and 63; pigments of cerium sulfide represented by CI · Pigment Orange 75; CI pigment orange 43 Pigments such as perylone, etc .; pyrrolopyrrole-based pigments such as CI · Pigment Orange 71, 73, etc .; 11-10 Standards (CNS) A4 (210 X 297 mm) '" " -------- ^ --------- line (please read the notes on the back before filling this page) 1237531 Φ A7 B7 V. Description of the invention (p) CI Pigment Orange 48 and Pigments of acetone represented by 49, etc .; metal complex pigments represented by CI · Pigment Orange 65, 68, 17: 1 etc. On the other hand, as an orange pigment having at least one halogen atom in the chemical structural formula, and the amount of halogen in the molecular weight is 25% or less, a more preferable one is a single couple represented by CI pigment orange 36 Nitrogen based pigments; Monoazo based pigments represented by CI Pigment Orange 13 and 34. These orange pigments may be used alone or in a suitable combination. Generally speaking, the solder resist ink that forms a permanent protective film, and the permanent protective film formed in the above-mentioned manner, is preferably colored to a green color that is excellent in visibility during visual inspection and does not cause damage to the eyes. As described above, the ink of the present invention is a copper peptide cyanide containing the (C) component having at least one halogen atom in the chemical structural formula as an essential component, and a halogen content in the molecular weight of 25% or less. In addition to the copper peptide cyanine pigment, a green or blue (especially green) permanent protective film can be obtained by further blending at least one type of pigment selected from the above-mentioned blue pigment, yellow pigment, and orange pigment. And the halogen content of this green permanent protective film is small. In addition, although the invention described in Japanese Patent Application Laid-Open No. 2000-232264 has the advantage of reducing halogenation, the pulverizability and dispersibility of the pigment used may not be good; relatively, the pulverizability and dispersion of the pigment compounded in the present invention It also has good properties and can reduce the amount of colored pigments used. In addition, the permanent protective film of the solder resist ink of the present invention has a small amount of halogen gas generated during combustion and is affected by 12 -------- ^ --------- (Please read first Note on the back, please fill out this page again) This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 1237531 A7 ____B7_ 5. Description of the invention () It is not easy to fade even under the heat treatment such as welding. In addition, in order to obtain a solder resist ink that can form a bright green permanent protective film with few stains, the weight ratio of the copper phthalocyanine pigment to the second pigment as the component (C) is copper phthalocyanine: the second pigment = 1: 10 ~ 10: 1 is preferred, especially 1: 5 ~ 5: 1. In the present invention, the blending amount of the copper ^ phthalocyanine pigment having (C) component having at least one halogen atom in the chemical structural formula and the halogen content in the molecular weight is 25% or less, Except for the organic solvent contained arbitrarily, it is preferable that the total content of the ink of the present invention is about 0.1 to 20% by weight, and it is more preferable to contain 0.1 to 10% by weight, especially 0.2 to 5% by weight. When the blending amount of the copper phthalocyanine pigment is within the above range, a reduction in photoreactivity due to a decrease in ultraviolet transmittance can be suppressed, and a permanent protective film having good visibility during visual inspection can be obtained. In addition, the total amount of the copper phthalocyanine pigment and the second pigment is not particularly limited, but it is preferable that it contains about 1 to 20% by weight in the total component φ of the ink of the present invention except for any organic solvent contained therein. It is preferably from 0.1 to 10% by weight, and more preferably from 0.2 to 5% by weight. When the total blending amount of the copper-like cyan pigment and the second pigment is within the above range, a reduction in photoreactivity due to a decrease in ultraviolet transmittance can be suppressed, and a permanent protective film having good visibility during visual inspection can be obtained. . (I) Photosol-proof ink When the solder-proof ink of the present invention is used as a photo-solder, it is preferable that the ink can be developed by an organic solvent or a dilute alkaline aqueous solution, etc. Use UV-curable resin. 13 -------- ^ --------- (Please read the notes on the back before filling out this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ) 1237531 A7 ______B7____ 5. Description of the invention (P) In particular, in terms of allowing the ink to be developed by dilute alkaline aqueous solution, as the (A) component, the aforementioned (A-1) component is used, that is, it has a Ultraviolet curable resins which are suspected of unsaturated unsaturated groups and carboxyl groups are preferred. In addition, the "photosoldering ink" referred to in the present invention is also a so-called development type solderless ink, which corresponds to, for example, selective exposure of the solderless ink applied on a substrate with ultraviolet rays to allow this. The solder mask of the exposed part is hardened, and then the solder mask of the unexposed part is washed in a dilute alkaline aqueous solution to remove the solder mask of the type with a permanent protective film of a predetermined pattern. The aforementioned (A-1) component has a photo-hardenable ethylenically unsaturated group and a carboxyl group in its chemical structural formula. Therefore, once it is exposed to ultraviolet rays and the like and absorbs a predetermined energy, the exposed portion will harden, thereby reducing The dispersibility and solubility of the alkaline aqueous solution are reduced. Therefore, the photomask of the present invention containing the component (A-1) was coated on a substrate and subjected to selective exposure to 'harden the photomask of the exposed portion, and then this substrate was diluted in a dilute alkaline 4 aqueous solution. Medium cleaning to dissolve and remove the unhardened photo-soldering ink in the unexposed part with a dilute aqueous solution, and a predetermined pattern can be formed on the substrate. The ultraviolet curable resin of the component (A-1) has a photopolymerizable ethylenically unsaturated group in the chemical structural formula. Examples of such photopolymerizable ethylenically unsaturated groups include unsaturated groups such as (meth) acrylfluorenyl and vinyl. The content of such photopolymerizable ethylenically unsaturated groups is not particularly limited. 'Generally, the content of the unsaturated group in the ultraviolet curable resin is 0.01 to 10 mol / kg (ultraviolet curable resin). It is preferably from 0.1 to 5 Moore / kg. When the unsaturated group in the ultraviolet curable resin contains 14 private paper, the standard of China National Standards (CNS) A4 is applicable to _ (2io × 297 mm). -------- Order ----- ---- (Please read the precautions on the back before filling this page) 1237531 A7 Φ B7 V. Description of the invention (〇) When the amount is in the above range, it can be specially adjusted to have light exposure with excellent exposure sensitivity and developability Welding ink. The ultraviolet curable resin as the component (A-1) preferably has an acid value of 30 to 200 mgKOH / g, and more preferably an S value of 40 to 160 mgKOH / g. When the acid value of the ultraviolet curable resin is in the above range, not only does the compatibility with other components become good, but also a light-shielding ink having excellent exposure sensitivity, developability, and resolution can be specially prepared. 1 In addition, the weight-average molecular weight of the ultraviolet curable resin as the component (A-1) is not particularly limited, but it is generally 3,000 (400) to 400,000, particularly preferably 5,000 to 100,000, and more preferably 5,000. ~ 50,000,00. When the weight-average molecular weight of the ultraviolet curable resin is in the above range, the balance between the resolution and exposure sensitivity of the photo-soldering ink of the present invention is particularly excellent. Examples of the (A-D component) include the "polymer having an epoxy group in a side chain", which is formed by adding "the ethylenic group having a carboxyl group, an unsaturated compound" and a "polycarboxylic anhydride" to the aforementioned epoxy group. The ultraviolet curable resin. As the "polymer having an epoxy group in a side chain (skeletal polymer)" used for the ultraviolet curable resin exemplified for preparing the component (A-1), the following epoxy resins may be mentioned. Compounds and ethylenically unsaturated monomers = polymers. 〃 That is, examples of epoxy compounds include glycidyl (meth) acrylate or 2-methylglycidyl (meth) acrylate. Glycidyl (meth) acrylates, etc .; and (3,4-epoxycyclohexyl) meth (meth) acrylates, etc. (meth) acrylic epoxy cyclohexyl derivatives, etc. As an ethylenically unsaturated monomer, aliphatic alicyclic 15 can be cited ------------ • equipment --- (Please read the precautions on the back before filling out this page ) I n H ϋ "δ, I ϋ I an 1 nn I · This paper size applies to China National Standard (CNS) A4 specifications (21 0 X 297 mm) 1237531 A7 B7 V. Description of the invention (alkyl (meth) acrylates of a; aromatic (meth) acrylates such as benzyl (meth) acrylates; hydroxyethyl (methyl (Meth) acrylate, methoxyethyl (meth) acrylate, and other glycol ester (meth) acrylates, polyethylene glycol (meth) acrylates, and propylene glycol (meth) acrylic acid Esters; (meth) acrylamidonium compounds; N-substituted maleimide compounds; vinylpyrrolidone; (meth) acrylonitrile; vinyl acetate; styrene; α-methylstyrene And vinyl ether, etc. In this specification, the so-called (meth) acrylic acrylic acid and methacrylic acid are collectively referred to as the so-called (meth) acrylic acid ester-based acrylic acid and methacrylic acid ester. The "polymer having an epoxy group in the side chain (skeletal polymer)" used for the preparation of the ultraviolet-curable resin exemplified by the above-mentioned (A-1) component, in addition to the above-mentioned epoxy compound and an ethylenically unsaturated monomer Copolymers, examples Such as phenolic lacquer type epoxy resin, cresol lacquer type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A-lacquer type epoxy resin, alicyclic epoxy resin Resin (such as "EHPE-3150" manufactured by Metabol Chemical Co., Ltd.), and polyfunctional epoxy resins derived from tris (hydroxyphenyl) methane derivatives (such as EPPN-502H manufactured by Nippon Kayaku Co., Ltd.), and Chemical Co., Ltd. manufactures epoxy resins such as Dakotex-1742 and XD-19053, etc. It is also used as a UV-curable resin exemplified for the preparation of (A-1) components. "Unsaturated monomers" include, for example, (meth) acrylic acid, crotonic acid, cinnamic acid, 2- (meth) acrylfluorenylhydroxyethylsuccinic acid, and 2- (meth) acrylfluorenylhydroxyethyl peptide. Acid, / 3-carboxyl paper size applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) -------- Order --------- Line (Please read the Note for this page, please fill in this page) 1237531 A7 ___B7_ V. Description of the invention Ethyl ethyl succinate, 2-acrylic acid, 3-((2-carboxyepoxy) -3-monohydroxypropyl ester, 2- (meth) acrylfluorenylhydroxyethyltetrahydrophthalic acid, and 2- (methyl ) Those having one ethylenically unsaturated group, such as propenyl hydroxyethyl hexahydroacid; and penterythritol tri (meth) acrylate, trimethylolpropane di (meth) acrylate , Dipentyl erythritol penta (meth) acrylate and other polyfunctional acrylates having a hydroxyl group, such as those obtained by reacting a dibasic acid anhydride with a plurality of ethylenically unsaturated groups, among which one has a carboxyl group It is better to use (meth) acrylic acid or (meth) acrylic acid as the main component. The reason is that the ethylenically unsaturated group introduced by (meth) acrylic acid is excellent in photoreactivity. These "ethylenically unsaturated monomers having a carboxyl group" may be used alone or in an appropriate combination. Examples of the "polycarboxylic anhydride" used in the ultraviolet curable resin exemplified for preparing the component (A-1) include anhydrous succinic acid, anhydrous methylsuccinic acid, anhydrous maleic acid, anhydrous citraconic acid, Anhydrous glutaric acid, anhydrous itaconic acid, anhydrous peptidic acid, tetrahydroanhydropeptidic acid, methyltetrahydroanhydro acid, anhydrous methylnaphthol diamino acid, hexahydroanhydrophthalic acid, and methylhexahydroanhydride And other dibasic anhydrides; and anhydrides of tribasic acids such as anhydrous pyromellitic acid, anhydrous pyromellitic acid, anhydrous phenol tetracarboxylic acid, and methylcyclohexene tetracarboxylic anhydride. These "polycarboxylic anhydrides" can be used individually or in appropriate combination. 17 (Please read the precautions on the back before filling out this page) ▼ Packing -------- Order --------- · This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 1237531 A7 ---- B7 V. Description of the invention () For the above epoxy group-added polymer having an epoxy group in a side chain, the aforementioned epoxy group is added to an ethylenically unsaturated compound having a carboxyl group and a polycarboxylic acid anhydride The addition reaction aspect of the ultraviolet curable resin exemplified as the component (A-1) is performed by heating to about 60 to 150 ° C. in the presence of a thermal polymerization inhibitor and an addition catalyst, for example. In addition, the above-mentioned addition reaction can add "polyethylenically unsaturated compounds having carboxyl groups" to "polymers having epoxy groups in side chains" and then add "polycarboxylic acid anhydrides". A "polymer having an epoxy group in its side chain" is added to a "polycarboxylic anhydride" and then an "ethylenically unsaturated compound having a carboxyl group" is added, and the former is preferred. The compounding amount of the component (A-1) in all the components of the photo-soldering ink of the present invention other than the organic solvent described later is not particularly limited, but it is preferably 10 to 80% by weight, and more preferably 20 to 70. The weight is preferably 25 to 60% by weight. When the compounding amount of the (A ^ l) component is in the above range, a light solder resist ink having good alkali developability, sensitivity, and resolution can be obtained. ) (A-4) ethylenically unsaturated monomer In addition to the above-mentioned (A-1) component, the photo-soldering ink of the present invention can be further blended with (A-4) ethylenically unsaturated component as component (A) Monomer to improve coating properties, heat resistance and insulation properties. In addition, this (A-4) photopolymerizable ethylenically unsaturated monomer plays a role not only as a diluent, but also as a function of adjusting exposure sensitivity. Examples of such ethylenically unsaturated monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N-vinylpyrrolidone, and (meth) Acrylic fluorenyl molybdenum, (meth) acrylic fluorenyl morpholine, methoxytetra 18 This paper is sized for China National Standard (CNS) A4 (210 X 297 mm) -------- ^- -------- (Please read the precautions on the back before filling this page) 1237531 A7 _______B7 V. Description of the invention (j) Ethylene glycol (meth) acrylate, methoxypolyethylene glycol (a Base) acrylate, polyethylene glycol di (meth) acrylate, n, n-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-di Methylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, melamine (meth) acrylate, diethylene glycol di (meth) acrylic acid Ester, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, cyclohexyl (methyl ) Acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, penterythritol tri (meth) acrylate, penterythritol tetrakis (methyl) ) Acrylate, dipenterythritol penta (meth) acrylate, dipenterythritol hexa (meth) acrylate, isovinyl (meth) propionate, cyclopentyl mono (methyl) Acrylates and cyclopentenyl mono (meth) acrylates; monoesters, diesters, triesters, or polyesters of polybasic acids and hydroxyalkyl (meth) acrylates; polyester (meth) acrylates, (Meth) acrylate monomers such as urethane (meth) acrylate. These ethylenically unsaturated monomers can be used individually or appropriately in combination when preparing the light solder resist ink of the present invention. The compounding amount of the above (A-4) ethylenically unsaturated monomer in the photosolder ink except for organic solvents is not particularly limited, but it is preferably 1 to 50% by weight, and more preferably 1 to 40% by weight. The best is 1 to 30% by weight. By blending the photopolymerizable ethylenically unsaturated monomer in the above range, appropriate surface adhesion can be imparted to the dry coating film, and a patterned negative mask can be prevented from being pressed onto the dry coating film for exposure. The problem of smeared negative mask. In addition, the light solder resist ink of the present invention can be further matched with epoxy 19 as necessary.
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本纸張尺度適用中國國家標準（CNS)A4規格（21〇 χ 297公1 ) 1237531 A7 _____B7____ 五、發明說明（（(f ) 基（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 之聚合物、或是於該等物質當中進一步導入乙烯性不飽和 基所成之紫外線硬化性聚合物等。 本發明之光防焊油墨，除了有上述之(A)成分’且兼含 有前述之(B)成分與(C)成分；藉由（C)成分之銅酞氰顏料的 配合，光防焊油墨之永久保護膜由於如前述般實質上呈現 ' 綠色或藍色，所以使用本發明之光防焊油墨所製作之印刷 配線基板的圖案在目視檢查之際的辨識性佳’且對於眼睛 不會造成不良影響。 又，本發明之光防焊油墨除了上述銅酞氰顏料以外’ 亦可進一步配合其他之著色顏料「第二顏料」一事也如前 述一般。又，銅肽氰顏料與第二顏料之配合比例等亦如前 述一般。 (D)有機溶劑 # 於本發明之防焊油墨中可進一步配合作爲(D)成&之有* 機溶劑，在光防焊油墨之情況，尤以配合有機溶劑爲佳° 作爲適於本發明之有機溶劑，可舉出例如乙醇 '丙醇 、異丙醇、丁醇、異丁醇、2—丁醇、己醇以及乙二醇等之 具有直鏈或支鏈狀之碳鏈的1級、2級或多元之醇類；甲 乙酮以及環己酮等之酮類；甲苯以及二甲苯等之芳香"族烴 類；史瓦所魯系列（九善石油化學公司製造）以及所魯貝索 系列（愛克森化學公司製造）等之石油系芳香族系混合溶劑 :溶纖劑以及丁基溶纖劑等之溶纖劑類；卡必醇以^丁® 20 (請先閱讀背面之注意事項再填寫本頁) -裝--------tr---------. 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1237531 B7 五、發明說明（β ) 卡必醇等之卡必醇類；丙二醇甲醚等之丙一醇院酸類；二 丙二醇甲醚等之多丙二醇院醚類；醋酸乙酯、醋酸丁酯、 溶纖劑乙酸酯、丁基溶纖劑乙酸酯'丁基卡必醇乙酸酯以 及丙二醇單甲醚乙酸酯等之醋酸酯類；以及二院基二醇醚 類等。爲了調製本發明之光防焊油墨，該等之有機溶劑可 個別單獨使用或適宜地組合使用。 該等之有機溶劑在本發明之防焊油墨中能以任意的比 〇 例來配合，例如多以1〜95重量％、較佳以5〜95重量。/(>、 最佳以20〜95重量％的比例來配合。配合有機溶劑所得之 本發明之光防焊油墨對於基板上之塗佈性佳。 (E)多官能環氧化合物 於本發明之光防焊油墨中，除了上述(A—1)紫外線硬 化性樹脂以外，尙可配合作爲任意成分之(E)多官能環氧化 合物。 作爲上述多官能環氧化合物並無特別之限定’可舉出 φ 例如雙酚A型環氧樹脂、雙酚F型環氧樹脂、酚醛淸漆型 環氧樹脂、甲酚淸漆型環氧樹脂、雙酚A—淸漆型環氧樹 脂、N—縮水甘油基型環氧樹脂或是脂環式環氧樹脂(例如 代謝爾化學公司製造「EHPE — 3150」）、「YX— 4000」（油 化殻牌公司製造環氧樹脂）、加氫雙酚A型環氧樹脂以及三 縮水甘油基異氰酸酯、以及三（羥苯基）甲烷所衍生之多官 能環氧樹脂（日本化藥公司製造EPPN — 502H，道爾化學公 司製造達克特克斯一742以及XD — 9053等）。 又，作爲多官能環氧化合物，亦可使用具有環氧基之 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) ^^裝--------訂---------線秦 1237531 A7 一 _ _____ 五、發明說明（户） 乙烯性不飽和單體之單聚物或共聚物等。又，使用前述共 聚物之情況下，構成共聚物之單體中，具有環氧基之乙稀 性不飽和單體以含有40莫爾％以上爲佳。藉此可得到良好 之熱固性。 又，雖未特別限定，上述之多官能環氧化合物爲具有 環氧基之乙烯性不飽和單體之單聚物或共聚物的情況下， 其重量平均分子量以2,000〜200,000較佳。藉此，可調製 出用以形成具優異熱固性之硬化皮膜的光防焊油墨。 作爲上述(E)成分之多官能環氧化合物除了有機溶劑以 外在本發明之光防焊油墨的全成分中能以0.1〜50重量％左 右、較佳爲0.1〜40重量％、更佳爲5〜40重量％的比例來配 合。當多官能環氧化合物之固形分之配合量位於上述範圍 中，可得到在顯像性與熱固性的均衡良好的光防焊油墨。 進一步之任意成分 本發明之光防焊油墨，爲了進一步提昇其塗佈性、耐 熱性以及絕緣性等之特性，亦可配合進一步之任意成分。 作爲此種任意成分可舉出例如滑石、二氧化矽、硫酸 鋇、氧化鋁、碳酸鈣以及雲母等之骨架原料、無機顏料、 密接性賦予劑、均平劑、矽烷偶合劑、觸變劑、抑制聚合 劑、抑制光暈劑、消泡劑、防氧化劑、界面活性劑乃至於 高分子分散劑。 本發明之光防焊油墨可使用三輥機、球磨機以及砂磨 機等眾知之混練做法來調製。 又，本發明之光防焊油墨的各成分無須事先完全均一 22 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---------% 1237531 A7 _____B7__________ 五、發明說明（v\) 混合。例如，可個別調製出由例如(E)成分與(D)成分所成 之混合液1、由（A — 1)成分、（B)成分、（C)成分以及(D)成 分所構成之混合液2，在要使用時在將混合液1與混合液2 加以混合來使用之形態。 本發明之光防焊油墨係例如塗佈於銅面積層板等之基 板上後乾燥之，對所得之乾燥塗膜上的既定部分照射紫外 線來讓此部份之光防焊油墨硬化。之後在稀鹼溶液中去除 ^ 掉非曝光部分進而顯像，之後以後烘烤未被去除而殘留之 光防焊油墨即成爲永久保護膜。 作爲顯像液所使用之烯鹼溶液以水溶液爲佳，又例如 亦可爲含有醇類等之親水性有機溶劑的水性溶液。 以上述方式所得之永久保護膜，其鹵素含有量較佳爲 500ppm以下（實際上爲0.1〜500ppm)，更佳爲300ppm以下 (實際上爲〇·1〜300 ppm)，最佳爲150ppm以下（實際上爲 0.1〜150 ppm)。藉此，燃燒時之有毒鹵素的產生可顯著地 ii 降低。 又，依據本發明，於(A — 1)成分之「於側鏈具有環氧 基之聚合物」及其製造上所使用之具有環氧基之乙烯性不 飽和單體、又(E)多官能環氧化合物其及製造上所使用之具 有環氧基之乙烯性不飽和單體並無特別之限定，可藉由在 工業上所取得者讓硬化皮膜中之鹵素含有量成爲上述般之 500ppm以下（實際上爲0.1〜500ppm)。 又，以往作爲用以調製光防焊油墨之環氧化合物，尤 其多採用自多環酚醛系之化合物所衍生之環氧樹脂或縮水 23 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--------!^^wi . 1237531 A7 ________B7___ 五、發明說明） 甘油基甲基丙烯酸酯等之具有縮水甘油基之乙烯性不飽和 單體等，惟該等物質在工業上是利用環氧氯丙烷之加成以 及HC1之脫離所製造者，在製品中含有高濃度之成爲反應 副產物或雜質等的鹵素。 是以’若使用以此種方式所製造之環氧化合物來調製 光防焊油墨’則要將形成於基板上之硬化皮膜中之鹵素的 含有量控制在150ppm以下是困難的。 # 另一方面’若依據本發明，以使用在(A — 1)成分之製 造上所使用之環氧化合物、以及(E)成分或於(E)成分之製 造上所使用之環氧化合物的鹵素含有量在50ppm以下者爲 佳。一旦使用此種(A—1)成分以及/或是(E)成分，則由本發 明之光防焊油墨所形成之永久保護膜中之鹵素的含有量可The size of this paper is applicable to the Chinese National Standard (CNS) A4 (21〇χ 297 公 1) 1237531 A7 _____B7____ 5. Description of the invention (((f) UV curable polymer such as (meth) acrylate, etc. Based) acrylic acid copolymers, polymers of ethylenically unsaturated compounds such as styrene-maleic acid resins, or ultraviolet curable polymers formed by further introducing ethylenically unsaturated groups into these materials. The light-shielding ink of the invention, in addition to the above-mentioned (A) component ', also contains the above-mentioned (B) component and (C) component; by the combination of the copper phthalocyanine pigment of the (C) component, The permanent protective film is substantially green or blue as described above, so the pattern of the printed wiring board produced using the photo-soldering ink of the present invention has good recognizability during visual inspection, and it does not cause damage to the eyes. In addition, in addition to the above copper phthalocyanine pigment, the photo-soldering ink of the present invention can also be mixed with other coloring pigments, such as the "second pigment". The copper peptide cyanide pigment and the second (D) Organic solvent # In the solder resist ink of the present invention, it can be further blended with organic solvent as (D) component &, especially in the case of light solder resist ink. The organic solvent is preferably blended. Examples of the organic solvent suitable for the present invention include ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol, and ethylene glycol. Alcohols of grade 1, 2 or polyalcohols with branched or branched carbon chains; ketones such as methyl ethyl ketone and cyclohexanone; aromatics such as toluene and xylene; group hydrocarbons; Shivazuru series (9 (Manufactured by Sun Petrochemical Co., Ltd.) and Sorbube series (manufactured by Exxon Chemical Co., Ltd.) and other petroleum-based aromatic mixed solvents: cellosolve and butyl cellosolve; ® 20 (Please read the precautions on the back before filling out this page)-Install -------- tr ---------. This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 1237531 B7 V. Description of the Invention (β) Carbitols such as carbitol; Propylene glycol methyl ether and other glycerol acids Polypropylene glycol ethers such as dipropylene glycol methyl ether; ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate 'butylcarbitol acetate, and propylene glycol monomethyl ether acetate Acetic acid esters such as esters; and diethyl ether glycol ethers, etc. In order to prepare the light solder resist ink of the present invention, these organic solvents can be used individually or in combination as appropriate. The organic solvents in the present invention The solder resist ink can be mixed at any ratio, for example, it is usually 1 to 95% by weight, and preferably 5 to 95% by weight. / (≫, preferably 20 to 95% by weight). The photo-soldering ink of the present invention obtained by blending an organic solvent has good coatability on a substrate. (E) Polyfunctional epoxy compound In the photo-soldering ink of the present invention, in addition to the above-mentioned (A-1) ultraviolet hardening resin, rhenium may be compounded with (E) a polyfunctional epoxide as an optional component. The polyfunctional epoxy compound is not particularly limited. Examples include bisphenol A epoxy resin, bisphenol F epoxy resin, phenolic epoxy resin, and cresol epoxy resin. , Bisphenol A-lacquer type epoxy resin, N-glycidyl type epoxy resin or alicyclic epoxy resin (such as "EHPE-3150" manufactured by Metabol Chemical Co., Ltd.), "YX-4000" (oil Epoxy resin manufactured by Kasei Corporation), hydrogenated bisphenol A epoxy resin, triglycidyl isocyanate, and polyfunctional epoxy resin derived from tris (hydroxyphenyl) methane (EPPN manufactured by Nippon Kayaku Co., Ltd. — 502H, Dow Chemical Company made Daxtex-1742 and XD-9053 etc.). Also, as a multifunctional epoxy compound, this paper with epoxy groups can also be used in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling out this page) ^ ^ Equipment -------- Order --------- Xinqin 1237531 A7 I _ _____ V. Description of the Invention (household) Monomers or copolymers of ethylenically unsaturated monomers, etc. 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. This gives good thermosetting properties. Although not particularly limited, when the above-mentioned polyfunctional epoxy compound is a monopolymer or copolymer of an ethylenically unsaturated monomer having an epoxy group, the weight average molecular weight is preferably 2,000 to 200,000. This makes it possible to prepare a photomask for forming a hardened film having excellent thermosetting properties. The polyfunctional epoxy compound as the component (E) described above can contain about 0.1 to 50% by weight, preferably 0.1 to 40% by weight, and more preferably 5 in all components of the photo-soldering ink of the present invention, in addition to an organic solvent. ~ 40% by weight. When the blending amount of the solid content of the polyfunctional epoxy compound is in the above range, a photo-soldering ink with good balance between developability and thermosetting property can be obtained. Further optional components The light solder resist ink of the present invention may be further combined with optional components in order to further improve the characteristics of coating properties, heat resistance, and insulation properties. Examples of such optional components include skeletal materials such as talc, silicon dioxide, barium sulfate, alumina, calcium carbonate, and mica, inorganic pigments, adhesion-imparting agents, leveling agents, silane coupling agents, thixotropic agents, Polymerization inhibitors, halo inhibitors, defoamers, antioxidants, surfactants and even polymeric dispersants. The light solder resist ink of the present invention can be prepared using well-known kneading methods such as a three-roller, a ball mill, and a sand mill. In addition, the components of the light solder resist ink of the present invention do not need to be completely uniform in advance. 22 This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page). Order ---------% 1237531 A7 _____B7__________ V. Description of invention (v \) Mix. For example, a mixed liquid composed of (E) component and (D) component 1, and a mixture of (A-1) component, (B) component, (C) component, and (D) component can be individually prepared. The liquid 2 is in a form in which the mixed liquid 1 and the mixed liquid 2 are mixed and used when they are to be used. The photo-soldering ink of the present invention is, for example, coated on a substrate such as a copper area laminate and dried, and then irradiates a predetermined portion of the obtained dried coating film with ultraviolet rays to harden the photo-soldering ink in this portion. After that, the non-exposed part is removed in a dilute alkali solution to develop the image. After that, the photoresist ink remaining after the baking is not removed becomes a permanent protective film. The olefinic alkali solution used as the developing solution is preferably an aqueous solution, and for example, it may be an aqueous solution containing a hydrophilic organic solvent such as an alcohol. 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 most preferably 150 ppm or less ( (Actually 0.1 to 150 ppm). As a result, the generation of toxic halogens during combustion can be significantly reduced. In addition, according to the present invention, the "polymer having an epoxy group on a side chain" in the component (A-1) and the ethylenically unsaturated monomer having an epoxy group used in its production, and (E) The functional epoxy compound and the ethylenically unsaturated monomer having an epoxy group used in the production are not particularly limited, and the halogen content in the cured film can be 500 ppm as described above by an industrially obtained person The following (actually 0.1 to 500 ppm). In addition, in the past, epoxy resins used to modulate photo-soldering inks, especially epoxy resins or shrinkages derived from polycyclic phenolic compounds were used. 23 This paper standard is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back before filling out this page) -------- Order --------! ^^ wi. 1237531 A7 ________B7___ V. Description of the invention Glycidyl ethylenically unsaturated monomers, etc., but these materials are manufactured industrially by the addition of epichlorohydrin and the release of HC1, and contain high concentrations in products. Halogens such as reaction by-products or impurities. It is difficult to control the content of the halogen in the hardened film formed on the substrate to 150 ppm or less if "the photoresist ink is prepared using the epoxy compound manufactured in this way". # On the other hand, if according to the present invention, the use of the epoxy compound used in the manufacture of the component (A-1) and the use of the epoxy compound used in the manufacture of the component (E) or (E) The halogen content is preferably 50 ppm or less. Once such (A-1) component and / or (E) component are used, the halogen content in the permanent protective film formed by the light solder resist ink of the present invention can be
I 較以往獲得顯著的減低，而可控制在150ppm以下。 作爲用以調製本發明之光防焊油墨之上述的鹵素含有 量在50ppm以下之環氧化合物，可舉出例如以過酸(例如 過犠酸、過醋酸、過苯甲酸等)進行環氧化反應所合成之環 氧樹脂以及含有環氧基之乙烯性不飽和單體。 該等物質由於在製程中並未使用環氧氯丙烷，所以爲 無鹵素者。作爲此種之環氧樹脂，可舉出例如「EHPE-315〇」（代謝爾化學工業(股份有限)公司製造，脂環式環氧 樹脂），又作爲含有環氧基之乙烯性不飽和單體，可舉出例 如賽克羅馬一 A—200(代謝爾化學工業(股份有限)公司製造 ，含有脂環式環氧基之乙烯性不飽和單體）、賽克羅馬一 Μ —1〇〇、M—101(代謝爾化學工業（股份有限）公司製造， 24 (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公釐） 1237531 A7 B7 Φ 五、發明說明（ 含有脂環式環氧基之乙烯性不飽和單體)等。 又，雖非藉過酸進行環氧化反應所合成者，但例如經 過氯減低處理所成之含有環氧基之乙烯性不飽和單體的布 雷嗎GS(日本油脂(股份有限)公司製造，無氯之縮水甘油基 甲基丙烯酸酯）等之情況也在鹵素濃度爲lOppm以下時可 適宜地使用。 (Π )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作紫外線硬化型防 焊油墨來利用之時，作爲(A)成分之紫外線硬化性成分雖無 特別之限定，但由（A — 3)環氧基（甲基）丙烯酸酯以及/或是 多元酚之聚醚化物與（甲基)丙烯酸所成之酯化物以及(A—3) 成分以外之(A — 4)乙烯性不飽和化合物所構成者爲佳。 亦即，此紫外線硬化型防焊油墨係由：（A — 3)環氧基( 甲基)丙烯酸酯以及/或是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、（B)光聚合起始劑、以及(C)銅酞氰顏料(化學結構式 中具有至少1個之鹵素原子，且於分子量中鹵素含有量佔 25%以下)所構成。 又，於本發明中，所謂的「紫外線硬化型防焊油墨」 意指藉由印刷法形成既定之圖案而形成永久保護膜者’例 如對於在基板上藉由網版印刷等之以往眾知之印刷方式所 印刷之防焊油墨，以紫外線進行全面曝光讓受曝光部分之 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。 25 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 1237531 A7 B7 Φ 五、發明說明（4) (A~ 3)環氧基（甲基）丙烯酸酯以及/或是多元酚之聚醚 化物與（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中所使用之(A — 3) 成分之環氧基（甲基)丙烯酸酯，係環氧化合物與（甲基)丙烯 酸進行酯化反應所產生之環氧基的全酯化物或部分酯化物 ，作爲相關之環氧基（甲基）丙烯酸酯，可單獨使用以往習 知之各種物質或將其適當組合來使用。 又，作爲用以產生上述環氧基（甲基）丙烯酸酯的環氧 化合物，具體上可舉出讓雙酚A、雙酚F、雙酚A樹脂、 雙酚F樹脂、甲酚淸漆樹脂以及酚醛淸漆樹脂等之多元酚 類與環氧氯丙烷進行反應所得者，以及脂環式環氧樹脂(例 如代謝爾化學工業公司製造之實質上不含鹵素之過醋酸法 環氧樹脂「EHPE — 3150」）等。 另一方面，作爲(A — 3)成分之多元酚之聚醚化物與（甲 基)丙烯酸所成之酯化物，係多元酚之聚醚化物與（甲基)丙 烯酸進行酯化反應所產生之全酯化物或部分酯化物。 又’上述之多元酚之聚醚化物可藉由例如對於多元酚 加成環氧乙烷、環氧丙烷、環氧丁烷或是ε —己內酯等來 得到。 本發明之紫外線硬化型防焊油墨中之(Α — 3)成分的配 合量並無特別之限定，較佳爲(Α — 3)成分在本發明之紫外 線硬化型防焊油墨中佔10〜70重量％、較佳爲15〜65重量 %、更佳爲15〜60重量％。含有上述範圍之(Α — 3)成分的本 發明之紫外線硬化型防焊油墨，經由紫外線之照射而硬化 26 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） -------------------訂---------線 0^· (請先閲讀背面之注意事項再填寫本頁) 1237531 A7 ______B7 五、發明說明（） 可得到具有既定強度之硬化物。 (A — 4) A—3成分以外之乙烯性不飽和化合物 於本發明之紫外線硬化型之防焊油墨中，除了（a〜3) 成分，亦可含有作爲（A — 4)成分之(A—3)成分以外之乙燦 性不飽和化合物，相關之(A — 4)成分如前所提及般。 本發明之紫外線硬化型防焊油墨中之(A — 4)成分的配 合量並無特別之限定，較佳爲(A —4)成分在本發明之油墨 中佔10〜70重量％、較佳爲15〜65重量％、更佳爲20〜6〇 重量％。含有上述範圍之(A —4)成分的本發明之紫外線硬 化型防焊油墨，經由紫外線之照射而硬化可得到具有既定 強度之硬化物。 又，構成紫外線硬化性成分之(A — 3)成分與(A — 4)成 分之組成比並無特別之限定，惟(A — 3)成分與(A—4)成分 之合計100重量份中(A — 3)成分的配合量以10〜70重量份 左右爲佳、以10〜60重量份爲更佳、以15〜50重量份爲最 佳。當(A — 3)成分與(A—4)成分以上述之範圍的配合量來 配合時，可調製出用以形成在印刷性方面優異且具有優異 之硬化性與耐熱性之永久保護膜的紫外線硬化型之防焊油 墨。 當倂用（A — 3)成分與(A — 4)成分的情況，所使用之(B) 成分以及(C)著色顏料的種類與配合比例係如前述般，又於 (C)成分中亦可如前述般倂用第二顏料。 於相關之本發明之紫外線硬化型防焊油墨中，只要不 至於對印刷性、耐熱性以及絕緣性等之特性造成不良影饗 27 (請先閱讀背面之注意事項再填寫本頁) --------訂--------- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1237531 B7 五、發明說明（八） ’亦可含有其他成分，作爲此種成分可舉出例如滑石、二 氧化砂 '硫酸鋇、氧化鋁、碳酸鈣以及雲母等之骨架原料 、無機顏料、密接性提昇劑、均平劑、觸變劑、消泡劑以 及抑制聚合劑等。 月之紫外線硬化型防焊油墨可藉由例如採用網版 印刷法或偏心印刷法等之以往習知之印刷方法來於銅面積 層板等之基板上進行印刷。 本發明之紫外線硬化型防焊油墨，藉由使用上述般之 顏料’可顯著地減少於紫外線硬化型防焊油墨中之鹵素的 含有量。具體而言，本發明之紫外線硬化型防焊油墨之鹵 素含有量一般爲50〇ppm以下(實際上爲0.1〜500ppm)，較 佳爲4〇〇ppm以下(實際上爲〇·ι〜4〇〇 ppm)，更佳爲300ppm 以下(實際上爲0·1〜300 ppm)。從而，由本發明之紫外線硬 化型防焊油墨所形成之永久保護膜，燃燒時之有毒鹵素的 產生量可顯著地降低。 另一方面，於(A — 3)成分之製造上使用環氧化合物的 情況，作爲此環氧化合物可選擇鹵素含有量在50ppm以下 者。藉此，由本發明之紫外線硬化型防焊油墨所形成之永 久保護膜中之鹵素含有量可較以往顯著地降低，可成爲 150ppm以下，此與先前所記載之光防焊油墨的情況也相同 〇 [用以實施發明之最佳形態] 其次，基於實施例更詳細地說明本發明’惟本發明並 不侷限於以下之實施例中。 28 --------^--------- (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）^ 一 " 1237531 Α7 Β7 五、發明說明（、Ί) 又，以下所表示之「份」與「％」全爲重量基準。 實施例1 (I )光防焊油墨 以表1所記載之配合組成來調製出參照本發明之樣品 —1〜I — 11以及比較例之樣品I 一 12〜I —14。 又，於表1所記載之紫外線硬化性樹脂(Α—丨一丨）、（Α 1 一2)、（Α— 1 一3)以及(Α-1 — 4)係以下述的方法來調製 [Α一 1 一 1之合成] 於安裝有回流冷卻器、溫度計、氮置換用玻璃管以及 攪拌機之四口燒瓶添加布雷嗎GS(日本油脂製造，氯減低 之縮水甘油基甲基丙烯酸酯，鹵素含有量爲lppm以下)7C 份、甲基丙烯酸甲酯30份、卡必醇乙酸酯1〇0份、偶氮二 異丁腈3份，一邊攪拌一邊在氮氣流下於8(rc加熱5小時 ，藉以進行聚合來得到50%共聚物溶液。對所得之50%共 聚物溶液加入氫醌0.05份、丙烯酸37份以及二甲基苄胺 〇·2份，於l〇〇°C進行24小時之加成反應。接著加入四氫 砍酸酐45份以及卡必醇乙酸酯79份在i〇〇°c反應3小時 ’得到紫外線硬化性樹脂之50%溶液(A— 1 一 1)。 [A—1 一2之合成] 將EHPE—3150(脂環式環氧樹脂，代謝爾化學工業(股 份有限)公司製造，環氧當量179，不含鹵素(未檢測出鹵素 ))179份溶解於卡必醇乙酸酯6〇份中，進一步一邊攪拌一 邊加入丙烯酸74份、氫醌〇·；[份以及二甲基苄胺〇.7份， 29 (請先閱讀背面之注意事項再填寫本頁) ---------訂---------線赢 本紙巧度適財酬€標準（CNSU4規格⑽X 297公爱） 1237531 A7 _______B7 五、發明說明（>/ ) 以一般方法在90〜10(TC反應24小時。對此反應液加入卡 必醇乙酸酯95份進行攪拌來得到環氧基丙烯酸酯溶液。接 著’加入四氫肽酸酐76份以及卡必醇乙酸酯64份，於 l〇〇°C反應3小時，得到紫外線硬化性樹脂之60%溶液(A —1 一 2)〇 [A—1 一3之合成] 取代在上述(A-1 — 1)之合成中所使用之布雷嗎GS， ^ 改用丙烯酸酯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素的縮水甘油基甲基丙烯 酸酯，鹵素含有量爲1600ppm)70份以外，其餘與(A — 1—· 1)之合成同樣來得到紫外線硬化性樹脂之50%溶液(A— 1 一 3)。 [A—1—4之合成] 取代在上述(A— 1 一2)之合成中所使用之EHPE3150, 改用愛皮克龍N—680(大日本油墨化學工業股份有限公司 φ 製造之甲酚淸漆型環氧樹脂，環氧當量214，鹵素含有量 爲1050ppm)214份，且將在酸酐添加時所倂用配合之卡必 醇乙酸酯的配合量變更爲78份以外，其餘與(A— 1 一2)之 合成同樣來得到紫外線硬化性樹脂之60%溶液(A— 1 一4)。 又，表1所記載之EHPE3150爲代謝爾化學工業(股份 有限)公司製造之環氧樹脂，愛皮克龍N—680爲大日本油 墨化學工業（股份有限）公司製造之甲酚淸漆型環氧樹脂， TEPIC—S爲日產化學工業(股份有限)公司製造之三縮水甘 油基異氰酸酯（鹵素含有量800ppm)，任一者皆爲多官能環 30 --------訂---------線 (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） 1237531 A7 B7 五、發明說明（ή ) 氧化合物。 又，多官能環氧化合物溶液(E — 1)係以下述的方法來 調製。 [E — 1之合成] 於安裝有回流冷卻器、溫度計、氮置換用玻璃管以及 攪拌機之四口燒瓶添加布雷嗎GS(日本油脂(股份有限)公司 製造，氯減低之縮水甘油基甲基丙烯酸酯）8〇份' 丙烯酸 丁酯20份、卡必醇乙酸酯67份、以及偶氮二異丁腈3份 ，一邊攪拌一邊在氮氣流下於85°C聚合5小時，得到多官 能環氧化合物之60%溶液。 其次，作爲本發明之(C)成分的銅肽氰顏料(化學結構 式中具有至少1個之鹵素原子，且於分子量中鹵素含有量 佔25%以下），係使用氰藍5025(大日精化工業股份有限公 司製造之化學結構式中作爲鹵素僅有1個氯之銅酞氰顏料 ，C.I.顏料藍 15 : 1)。 作爲於化學結構式中不含鹵素之黃色顏料，係使用鉻 肽黃2RF(吉巴特用化學(股份有限)公司製造之C.i.顏料黃 139) 〇 作爲於化學結構式中具有至少1個鹵素原子之黃色顏 料，於分子量中鹵素含有量佔25%以下者，係使用謝卡法 斯特黃l〇GH(大日精化工業股份有限公司製造之c.I.顏料 黃3)。 作爲於化學結構式不含鹵素之橙色顏料，係使用謝卡 法斯特橙3064(大日精化工業股份有限公司製造之c.i·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） --------------------^---------線 0^- (請先閲讀背面之注意事項再填寫本頁) 1237531 A7 ____B7______ 五、發明說明（) 橙5)。 作爲於化學結構式中具有至少1個鹵素原子之橙色顏 料，於分子量中鹵素含有量佔25%以下者，係使用謝卡法 斯特橙900(大日精化工業股份有限公司製造之C.I.顏料橙 13) 〇 作爲本發明之於化學結構式不含鹵素之藍色顏料，係 使用克羅母法因藍5008(C.I·顏料藍15 ··大日精化工業股份 ^ 有限公司製造之酞氰藍）。 作爲含有高量鹵素之綠色顏料，係使用2GN(C.I·顏料 綠7 :大日精化工業股份有限公司製造之酞氰綠）。 作爲光聚合起始劑係使用依魯卡及亞907(吉巴•蓋吉 公司製造）以及卡亞克亞DETX — S(日本化藥(股份有限)公 司製造），作爲均平劑係使用摩達氟羅（莫三特公司製造）。 又，二氧化矽係使用平均粒徑1/zm者。 將以上述方式所調製之各成分以表1所記載之配合比 丨 例來均一地混合，藉由（股份有限）井上製作所製造之三輥 來充分混合，調製出依據本發明之光防焊油墨I 一 1〜I — U以及比較例之光防焊油墨I 一 12〜I 一 14。 將上述所得之光防焊油墨I 一 1〜I 一 11以及I 一 12〜 I 一 14藉網版印刷塗佈於一在銅箔35/zm之玻璃環氧基材 所構成之銅面積層板事先以蝕刻形成有圖案之印刷配線基 板的全面上，於80°C進行20分鐘之預乾燥，使得溶劑揮 發，得到厚度20/zm之乾燥塗膜。之後，將描繪有圖案之 光罩直接貼附於塗膜面，照射15〇mJ/cm2之紫外線，其次 32 --------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） A7 1237531 五、發明說明（W ) 以1%碳酸鈉水溶液作爲顯像液進行顯像來形成圖案，進一 步於150°C進行60分鐘之加熱硬化，製作依據本發明之試 (請先閱讀背面之注意事項再填寫本頁) 驗片1一1〜I 一11以及超出本發明之範圍的試驗片 12〜I —14 〇 實施例2 (Π)紫外線硬化型防焊油墨 爲了調製作爲實施例之紫外線硬化型防焊油墨，首先 調製出以下之環氧基丙烯酸酯(A—3 — 1HA—。 環氧基丙烯酸酯(A— 3 — 1) 此爲愛皮克特154(油化殼牌環氧(股份有限)公司製造 之酚醛淸漆型環氧樹脂)與丙烯酸經酯化反應所調製者。此 爲環氧基之全酯化物。 環氧基丙烯酸酯(A— 3 — 2) 此爲愛皮克特828(油化殻牌環氧(股份有限)公司製造 之雙酚A型環氧樹脂)與丙烯酸經酯化反應所調製者。此爲 環氧基之全酯化物。 環氧基丙烯酸酯(A—3 — 3) 此爲EPPN-201(曰本化藥(股份有限)公司製造之酚醛 清漆型環氧樹脂)與丙烯酸經酯化反應所調製者。此爲環氧 基之全酯化物。 環氧基丙烯酸酯(A— 3 — 4) 此爲愛皮克龍N—695(大日本油墨化學工業(股份有限） 公司製造之甲酚淸漆型環氧樹脂)與丙烯酸經酯化反應所調 製者。此爲環氧基之全酯化物。 33 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1237531 Α7 Β7 Φ 五、發明說明（π) 環氧基丙烯酸酯(Α— 3 — 5) 此爲愛皮克特152(油化殻牌環氧（股份有限)公司製造 之酚醛淸漆型環氧樹脂)與丙烯酸經酯化反應所調製者。此 爲環氧基之全酯化物。 環氧基丙烯酸酯(A—3 — 6) 此爲愛皮克龍N—680(大日本油墨化學工業(股份有限) 公司製造之甲酚淸漆型環氧樹脂)與丙烯酸經酯化反應所調 製者。此爲環氧基之全酯化物。 2—丙烯醯基羥基乙酸磷酸酯係使用共榮社化學(股份 有限)製造之來特酯PA。又，2—甲基丙烯醯基羥基乙酸磷 酸酯係使用共榮社化學(股份有限)製造之來特酯PM。 又，在化學結構式中不含鹵素之橙色顏料與藍色顏料 係使用與實施例1同樣之顏料。又，作爲比較例所使用之 以往的綠色之有機著色顏料亦使用與實施例1所使用之顏 料爲相同者。 將以上述方式所調製之各成分以表2所記載之配合比 例來均一地混合，藉由（股份有限）井上製作所製造之三輥 來充分混練，調製出依據本發明之紫外線硬化型防焊油墨 Π — 1〜π —11以及比較例之紫外線硬化型防焊油墨Π〜 12 〜Π—14。 其次，使用225網孔網版、藉網版印刷法將上述所得 之紫外線硬化型防焊油墨分別印刷塗佈到形成有圖案之印 刷配線板上，之後使用120W/cm(或80W/cm)之金屬鹵化物 燈(或高壓水銀燈)以光量l〇〇〇mJ/cm2的光來照射使其硬化 34 --------訂---------線 (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） 1237531 A7 ____—__B7_ 五、發明說明（4 ) ’製作依據本發明之試驗片Π — 1〜Π —11以及超出本發明 之範圍的試驗片Π —12〜Π —14。 針對各實施例與比較例所得之（I )光防焊油墨以及（Π) 紫外線硬化型防焊油墨所調製之試驗片，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、絕緣電阻試驗以及有關鹵素含有量之特 性評價試驗。將所得之結果一倂記載於表1與表2中。 又，該等之特性評價方法係如下所述。 鉛筆硬度試驗··依據JIS K-5400,8.4來進行。使用鉛 筆(三菱尤尼)來測定不致造成刮傷之最高硬度。 棋盤格密接性試驗：依據JIS Κ-5400,8.5來進行。使 用艾里克森(Erichsen)交叉切割試驗器將硬化皮膜往縱•橫 方向各切割11條，進行透明膠帶剝離試驗。計算在100之 棋盤格中殘存之數量。 焊料耐熱性試驗：依據JIS C-6481，5.5來進行。作爲 助焊劑係使用LONCO · CF—350(倫敦化學公司製造之水溶 性助焊劑），首先在試驗片塗佈助焊劑，其次將其浸漬於 260°C之熔融焊浴中10秒，之後立即丟入水中。在此試驗 之完成後立即觀察基板表面，來確認膨起與剝落之有無。 耐溶劑性試驗：於室溫下浸漬於2—丙醇以及1，1，1 一 三氯乙烷中1小時，觀察基板表面，確認膨起或剝落之有 〇I is significantly lower than before, and can be controlled below 150ppm. Examples of the epoxy compound having a halogen content of 50 ppm or less for preparing the photo-soldering ink of the present invention include, for example, an epoxidation reaction with a peracid (such as peracetic acid, peracetic acid, perbenzoic acid, etc.) Synthetic epoxy resin and ethylenically unsaturated monomer containing epoxy group. These substances are halogen-free because epichlorohydrin is not used in the process. Examples of such an epoxy resin include "EHPE-315〇" (alicyclic epoxy resin manufactured by Metabol Chemical Co., Ltd.), and an ethylenically unsaturated monomer containing an epoxy group. Examples of the compound include Sycromax A-200 (made by Metabol Chemical Co., Ltd., an ethylenically unsaturated monomer containing an alicyclic epoxy group), and Sycromax M-100. 、 M-101 (Metabol Chemical Industry Co., Ltd.), 24 (Please read the precautions on the back before filling in this page) ▼ Install -------- Order --------- . This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 1237531 A7 B7 Φ 5. Description of the invention (Ethylene unsaturated monomer containing alicyclic epoxy group) etc. Synthesized by an epoxidation reaction with an acid, but, for example, a bleached epoxy-containing ethylenically unsaturated monomer made of chlorine-reduced GS (manufactured by Nippon Oil & Fats Co., Ltd.) without chlorine Methyl methacrylate) and the like are also suitable when the halogen concentration is 10 ppm or less. (Π) Ultraviolet-curable solder mask ink On the other hand, when the solder-curable ink of the present invention is used as an ultraviolet-curable solder mask ink, the ultraviolet-curable component as the component (A) is not particularly specific. Limited, but (A-3) epoxy ester (meth) acrylate and / or polyether phenol polyetherate and (meth) acrylic acid esters and (A-3) components other than (A — 4) An ethylenically unsaturated compound is preferred. That is, the UV-curable solder resist is composed of (A-3) epoxy (meth) acrylate and / or polyether polyether. (A-4) ethylenically unsaturated compounds other than (A-3) components, (B) photopolymerization initiators, and (C) copper phthalocyanine pigments ( It has at least one halogen atom in the chemical structural formula, and the halogen content in the molecular weight is 25% or less). In the present invention, the so-called "ultraviolet-curable solder resist" means by a printing method. Forming a predetermined pattern to form a permanent protective film ', for example, by The solder mask ink printed by the conventionally known printing methods, such as plate printing, is fully exposed with ultraviolet rays to harden the solder mask ink of the exposed part, and a solder mask ink of the type with a permanent protective film of a predetermined pattern is obtained. 25 Paper Size Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -------- Order --------- line (Please read the precautions on the back before filling this page) 1237531 A7 B7 Φ V. Description of the invention (4) (A ~ 3) epoxy (meth) acrylate and / or polyether phenol and (meth) acrylic acid ester formed by the ultraviolet curing type of the present invention The epoxy (meth) acrylate of the component (A-3) used in the solder resist ink is a fully-esterified epoxy group produced by an esterification reaction between an epoxy compound and (meth) acrylic acid, or Part of the esterified product, as the related epoxy (meth) acrylic acid ester, can be used alone or in combination as appropriate. Specific examples of the epoxy compound for producing the epoxy (meth) acrylate include bisphenol A, bisphenol F, bisphenol A resin, bisphenol F resin, and cresol varnish resin. And polyphenols such as phenolic lacquer resin and 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, the polyetherate of polyhydric phenol (A-3) and the esterification of (meth) acrylic acid are produced by the esterification reaction between polyetherate of polyphenol and (meth) acrylic acid. Fully esterified or partially esterified. The polyetherate of the above-mentioned polyphenol can be obtained, for example, by adding ethylene oxide, propylene oxide, butylene oxide, or ε-caprolactone to the polyphenol. The compounding amount of the (A-3) component in the UV-curable solder resist ink of the present invention is not particularly limited, and the (A-3) component preferably accounts for 10 to 70 of the UV-curable solder mask ink of the present invention. It is preferably 15 to 65% by weight, and more preferably 15 to 60% by weight. The UV-curable solder resist ink of the present invention containing the component (A-3) in the above range is hardened by the irradiation of ultraviolet rays. 26 The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love) --- ---------------- Order --------- line 0 ^ · (Please read the notes on the back before filling this page) 1237531 A7 ______B7 V. Description of the invention () A hardened product with a given strength can be obtained. (A-4) The ethylenically unsaturated compound other than the A-3 component In the ultraviolet-curable solder resist ink of the present invention, in addition to the component (a ~ 3), it may contain (A-4) as the component (A-4) —3) An ethylenically unsaturated compound other than the component, and the related (A—4) component is as mentioned above. The compounding amount of the (A-4) component in the UV-curable solder resist ink of the present invention is not particularly limited, and the (A-4) component preferably accounts for 10 to 70% by weight of the ink of the present invention, preferably It is 15 to 65% by weight, and more preferably 20 to 60% by weight. The ultraviolet-curable solder resist of the present invention containing the component (A-4) in the above range can be cured by irradiation with ultraviolet rays to obtain a cured product having a predetermined strength. In addition, the composition ratio of the (A-3) component and the (A-4) component constituting the ultraviolet-curable component is not particularly limited, but the total of the (A-3) component and the (A-4) component is 100 parts by weight. (A-3) The blending amount of the component is preferably about 10 to 70 parts by weight, more preferably 10 to 60 parts by weight, and most preferably 15 to 50 parts by weight. When the (A-3) component and the (A-4) component are blended in a blending amount within the above range, it is possible to prepare a permanent protective film that is excellent in printability and has excellent hardenability and heat resistance. UV-curable solder mask. When (A-3) and (A-4) components are used, the types and blending ratios of (B) component and (C) coloring pigment used are as described above, and also in (C) component. The second pigment may be used as described above. In the UV-curable solder resist ink of the present invention, as long as it does not adversely affect the printability, heat resistance, and insulation properties 27 (Please read the precautions on the back before filling out this page) --- ----- Order --------- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 1237531 B7 V. Description of the invention (8) 'May also contain other ingredients, Examples of such components include skeletal raw materials such as talc, sand dioxide, barium sulfate, alumina, calcium carbonate, and mica, inorganic pigments, adhesion promoters, leveling agents, thixotropic agents, defoamers, and inhibitors. Polymerization agent and so on. The UV-curable solder resist of the month can be printed on a substrate such as a copper-clad laminate by a conventionally known printing method such as a screen printing method or an eccentric printing method. The ultraviolet-curable solder mask of the present invention can significantly reduce the halogen content in the ultraviolet-curable solder mask by using the pigment as described above. Specifically, the halogen content of the UV-curable solder resist ink of the present invention is generally 50 ppm or less (actually 0.1 to 500 ppm), and preferably 400 ppm or less (actually 0.00 to 4). 〇ppm), more preferably 300 ppm or less (actually 0.1 to 300 ppm). Therefore, the permanent protective film formed by the ultraviolet hardening type solder resist ink of the present invention can significantly reduce the amount of toxic halogens generated during combustion. On the other hand, when an epoxy compound is used in the production of the component (A-3), as the epoxy compound, a halogen content of 50 ppm or less can be selected. As a result, the halogen content in the permanent protective film formed by the UV-curable solder resist ink of the present invention can be significantly reduced compared with the past, and can be 150 ppm or less, which is the same as the case of the photo solder resist ink described previously. [Best Mode for Carrying Out the Invention] Next, the present invention will be described in more detail based on examples. However, the present invention is not limited to the following examples. 28 -------- ^ --------- (Please read the notes on the back before filling out this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ) ^ 一 " 1237531 Α7 Β7 5. Description of the Invention (, Ί) In addition, the "parts" and "%" shown below are all based on weight. Example 1 (I) Photosoldering ink The samples of the present invention—1 to I—11 and the samples I to 12 to I-14 of the comparative example were prepared with the compounding composition described in Table 1. In addition, the ultraviolet curable resins (A- 丨 -1 丨), (A1-1-2), (A-1-13), and (A-1-4) described in Table 1 were prepared by the following method [ Α-11-1 Synthesis] Add a bleacher to a four-necked flask equipped with a reflux cooler, a thermometer, a glass tube for nitrogen replacement, and a stirrer. GS (Glycidyl methacrylate made by Japan Oil and Fat Co., Ltd., halogen-containing) The amount is 1 ppm or less) 7C parts, 30 parts of methyl methacrylate, 100 parts of carbitol acetate, and 3 parts of azobisisobutyronitrile, and heated at 8 (rc for 5 hours under nitrogen flow while stirring, Polymerization was performed to obtain a 50% copolymer solution. 0.05 parts of hydroquinone, 37 parts of acrylic acid, and 0.2 parts of dimethylbenzylamine were added to the obtained 50% copolymer solution, and the mixture was added at 100 ° C for 24 hours. Reaction. Then 45 parts of tetrahydroanhydride and 79 parts of carbitol acetate were added and reacted at 100 ° C for 3 hours to obtain a 50% solution of ultraviolet curable resin (A-1 to 1). [A— 1 to 2 Synthesis] EHPE-3150 (alicyclic epoxy resin, manufactured by Metabol Chemical Industry (Stock Co., Ltd.) 179 equivalents, containing no halogen (halogen was not detected)) 179 parts were dissolved in 60 parts of carbitol acetate, and 74 parts of acrylic acid and hydroquinone were added while stirring; [parts and dimethylbenzylamine 〇07 copies, 29 (please read the notes on the back before filling this page) --------- Order --------- Online Winning Paper Skillfulness and Financial Compensation € Standard (CNSU4 Specification ⑽X 297 public love) 1237531 A7 _______B7 V. Description of the invention (> /) General reaction at 90 ~ 10 (TC for 24 hours. Add 95 parts of carbitol acetate to this reaction solution and stir to obtain epoxy Acrylate solution. Then, 76 parts of tetrahydropeptide anhydride and 64 parts of carbitol acetate were added, and reacted at 100 ° C for 3 hours to obtain a 60% solution of ultraviolet curable resin (A 1-2) 〇 [Synthesis of A-1 to 3] Instead of the Bray GS used in the synthesis of the above (A-1 — 1), ^ Use acrylate G (manufactured by Mitsubishi Artificial Fibers (Stock Co., Ltd.), using epoxy The glycidyl methacrylate of halogen containing impurities contained in chloropropane, the halogen content is 1600 ppm), and the rest is the same as (A — 1— · 1 The synthesis of) also obtained a 50% solution of ultraviolet curable resin (A—1-3). [Synthesis of A—1-4] Instead of EHPE3150 used in the synthesis of (A—1-2) above, modify 214 parts of Epicalon N-680 (cresol lacquer type epoxy resin manufactured by Dainippon Ink Chemical Industry Co., Ltd. φ, epoxy equivalent 214, halogen content 1050 ppm), and will be added when the anhydride is added以外 The amount of carbitol acetate used was changed to 78 parts, and the rest was the same as the synthesis of (A-12) to obtain a 60% solution (A-1-4) of ultraviolet curable resin. In addition, EHPE3150 described in Table 1 is an epoxy resin manufactured by Metabol Chemical Industry Co., Ltd., and Epicon N-680 is a cresol lacquer type ring manufactured by Dainippon Ink Chemical Industry Co., Ltd. Oxygen resin, TEPIC-S is a triglycidyl isocyanate (halogen content of 800ppm) manufactured by Nissan Chemical Industry Co., Ltd., each of which is a multifunctional ring 30 -------- order --- ------ Line (Please read the notes on the back before filling this page) This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 1237531 A7 B7 V. Description of the invention (price) Oxygen Compounds. The polyfunctional epoxy compound solution (E-1) was prepared by the following method. [Synthesis of E-1] In a four-necked flask equipped with a reflux cooler, a thermometer, a glass tube for nitrogen replacement, and a stirrer, add a mine? GS (manufactured by Nippon Oil & Fats Co., Ltd.) with reduced glycidyl methacrylic acid (Ester) 80 parts' 20 parts of butyl acrylate, 67 parts of carbitol acetate, and 3 parts of azobisisobutyronitrile, and polymerized at 85 ° C for 5 hours under nitrogen flow while stirring to obtain a polyfunctional epoxy 60% solution of the compound. Next, as the copper peptide cyanine pigment (C) component of the present invention (has at least one halogen atom in the chemical structural formula, and the halogen content in the molecular weight is 25% or less), cyano blue 5025 (Dainichi Chemical Co., Ltd.) is used. The copper phthalocyanine pigment with only one chlorine as the halogen in the chemical structural formula manufactured by Industrial Co., Ltd., CI Pigment Blue 15: 1). As a yellow pigment containing no halogen in the chemical structural formula, Chromopeptide Yellow 2RF (Ci Pigment Yellow 139 manufactured by Jibate Chemicals (Limited) Co., Ltd.) is used. 〇 As a pigment having at least one halogen atom in the chemical structural formula For yellow pigments, those with a halogen content of 25% or less in the molecular weight are used Shekafast Yellow 10GH (cI Pigment Yellow 3 manufactured by Daiichi Fine Chemical Industry Co., Ltd.). As an orange pigment that does not contain halogen in its chemical structural formula, it uses Shekafast Orange 3064 (ci · Pigment 31 manufactured by Dainichi Fine Chemical Industry Co., Ltd.) This paper applies Chinese National Standard (CNS) A4 (210 X 297 mm) -------------------- ^ --------- line 0 ^-(Please read the precautions on the back before filling this page ) 1237531 A7 ____B7______ 5. Description of the invention () Orange 5). As an orange pigment having at least one halogen atom in the chemical structural formula, and the halogen content in the molecular weight is less than 25%, it is used Shekafast Orange 900 (CI Pigment Orange manufactured by Dainichi Chemical Industry Co., Ltd.) 13) 〇 As the blue pigment containing no halogen in the chemical structure of the present invention, it is based on Cromell Blue 5008 (CI · Pigment Blue 15 ·· Phthalocyanine Blue manufactured by Dainichi Fine Chemical Industry Co., Ltd.) . As a green pigment containing a high amount of halogen, 2GN (C.I. Pigment Green 7: Phthalocyanine Green manufactured by Daiichi Fine Chemical Industry Co., Ltd.) is used. As photopolymerization initiators, use Iruka and Ya 907 (made by Jiba Geji) and Kayakya DETX — S (made by Nippon Kayaku Co., Ltd.), as a leveling agent. Dafluro (Mozent Corporation). In addition, as the silicon dioxide, an average particle diameter of 1 / zm is used. The components prepared in the above manner are uniformly mixed with the mixing ratios described in Table 1 and thoroughly mixed by the three rollers (limited stock) manufactured by Inoue Manufacturing Co., Ltd. to prepare a light solder resist ink according to the present invention. I-1 to I-U and the light-shielding ink I-12 to I-14 of the comparative example. The above-mentioned light solder resist inks I-1, I-11, and I-12-12 I-14 were applied by screen printing to a copper area laminate composed of a glass epoxy substrate on a copper foil of 35 / zm. On the entire surface of the printed wiring board with a pattern formed by etching in advance, pre-drying was performed at 80 ° C for 20 minutes, so that the solvent was volatilized to obtain a dry coating film having a thickness of 20 / zm. After that, the mask with the pattern is directly attached to the coating film surface, and it is irradiated with ultraviolet rays of 15mJ / cm2, followed by 32 -------- Order --------- (Please read first Note on the back, please fill in this page again) This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) A7 1237531 V. Description of the invention (W) Use 1% sodium carbonate aqueous solution as the developing solution for development To form a pattern, and then heat-harden at 150 ° C for 60 minutes to make a test according to the present invention (please read the precautions on the back before filling in this page). Inspection sheet 1-11 ~ I-11 and beyond the scope of the present invention Test pieces 12 to I-14. Example 2 (Π) UV-curable solder mask In order to prepare the UV-curable solder mask as an example, the following epoxy acrylate (A-3-1HA —. Epoxy Acrylate (A—3 — 1) This is prepared by the esterification reaction of Epicste 154 (Phenolic Shell Lacquer Type Epoxy Resin made by Petrochemical Shell Epoxy Co., Ltd.) and acrylic acid. This is a full ester of epoxy group. Epoxy acrylate (A—3—2) This is Pictet 828 (a bisphenol A epoxy resin made by Petrochemical Shell Epoxy (Stock Co., Ltd.)) is prepared by esterification with acrylic acid. This is a full ester of epoxy groups. Epoxy acrylic acid Esters (A-3-3) This is a product of EPPN-201 (a novolac epoxy resin manufactured by Benhua Pharmaceutical Co., Ltd.) and acrylic acid through esterification reaction. This is a full ester of epoxy groups Epoxy acrylate (A—3—4) This is Epicron N—695 (cresol lacquer type epoxy resin made by Dainippon Ink Chemical Industry (Limited) Co., Ltd.) and acrylic acid is esterified Modified by the reaction. This is a full ester of epoxy group. 33 This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) 1237531 Α7 Β7 Φ 5. Description of the invention (π) Epoxy acrylic acid Esters (Α— 3—5) This is a product of Epictor 152 (a phenolic lacquer type epoxy resin made by Petrochemical Shell Epoxy Co., Ltd.) and acrylic acid. This is a ring Fully esters of oxygen. Epoxy acrylate (A—3 — 6) This is Epicron N—680 (Da Nihon Ink The cresol lacquer-type epoxy resin manufactured by Xuexue Industry Co., Ltd. and acrylic acid are prepared by esterification reaction. This is a full ester of epoxy group. Laite ester PA manufactured by Rongshe Chemical Co., Ltd. is used. Also, 2-methacryl fluorenyl glycolic acid phosphate is based on Laite ester PM manufactured by Kyoeisha Chemical Co., Ltd. Also, the chemical structural formula is As the orange pigment and the blue pigment which do not contain halogen, the same pigments as in Example 1 were used. The conventional green organic coloring pigment used as a comparative example was the same as the pigment used in Example 1. The ingredients prepared in the above manner were uniformly mixed at the mixing ratios described in Table 2. The three rollers manufactured by Inoue Manufacturing Co., Ltd. (limited stock) were fully kneaded to prepare the ultraviolet-curable solder resist ink according to the present invention. Π — 1 to π — 11 and the UV-curable solder resist ink of the comparative example Π to 12 to Π-14. Next, using the 225 mesh screen and the screen printing method, the UV-curable solder resist ink obtained above was printed and coated on the patterned printed wiring board, respectively, and then 120 W / cm (or 80 W / cm) was used. Metal halide lamps (or high-pressure mercury lamps) are irradiated with light of 1000 mJ / cm2 to harden them. 34 -------- Order --------- Line (Please read the back first Please note this page before filling in this page} This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1237531 A7 ____—__ B7_ V. Description of the invention (4) 'Making test piece according to the invention Π — 1 ~ Π-11 and test pieces Π-12 ~ Π-14 which are out of the scope of the present invention. (I) Photomasks and (Π) UV-curable soldermasks prepared in Examples and Comparative Examples were prepared. The test piece was subjected to a pencil hardness test, a checkerboard adhesion test, a solder heat resistance test, a solvent resistance test, a chemical resistance test, an insulation resistance test, and a characteristic evaluation test related to the halogen content. The results obtained are described in a batch. Table 1 and Table 2. Also, the special The evaluation method is as follows. Pencil hardness test: It is performed in accordance with JIS K-5400, 8.4. A pencil (Mitsubishi Uni) is used to measure the highest hardness that does not cause scratches. Checkerboard adhesion test: JIS K-5400 8.5. Use an Erichsen cross-cut tester to cut 11 pieces of hardened film in each of the vertical and horizontal directions to perform a transparent tape peeling test. Calculate the amount remaining in a checkerboard of 100. Solder heat resistance Test: According to JIS C-6481, 5.5. As the flux, LONCO · CF-350 (water-soluble flux manufactured by London Chemical Co., Ltd.) was used. First, a flux was applied to the test piece, and then immersed at 260 °. C was melted in the solder bath for 10 seconds, and then immediately dropped into water. Immediately after the completion of this test, the surface of the substrate was observed to confirm the presence of swelling and peeling. Solvent resistance test: Dipping in 2-propanol at room temperature And in 1,1,1 trichloroethane for 1 hour, observe the surface of the substrate and confirm that there is swelling or peeling.
J i NN 耐藥品性試驗：將基板分別浸漬於室溫下之10重量％ 之鹽酸、10重量％之氫氧化鈉水溶液中各1小時之後，觀 35 本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 1237531 A7 _ —____B7__ 五、發明說明（）7Ψ) 察基板表面，確認膨起或剝落之有無。 絕緣電阻試驗：測定具有本發明之硬化皮膜的IPC — Β 一25梳型圖案之對向電極間之電阻。 鹵素的含有量，在實施例1之光防焊油墨的情況下， 係將自油墨揮發去除有機溶劑所得之殘餘物以及硬化後塗 膜分別作爲試料來秤取，讓該等試料在燃燒燒瓶內進行燃 燒，對於將產生之氣體加以吸收之吸收液中之氯、溴以及 Φ 氟之含有量以離子色層分析測定來加以定量。 另一方面，若爲實施例2之紫外線硬化型防焊油墨的 情況，則是將硬化前之油墨與硬化後之塗膜分別作爲試料 來秤取，與上述實施例1同樣來進行鹵素含有量之定量。 Φ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------tr'---------線 (請先閱讀背面之注意事項再填寫本頁) 1237531 A7B7 五、發明說明（，>7<) [表1] 實施例 比較例 樣品編號 1-1 1-2 r -3 I -4 1-5 1-6 I -7 1-8 I -9 1 -10 I -II I -12 1-13 1-14 光防焊 油瞾之 配合組 成（重量 份） 紫外線硬化性樹脂溶液(A-1 -1) 50 50 50 50 50 紫外線硬化性樹脂溶液(A—丨一2) 50 50 紫外線硬化性樹脂溶液(A_ 1 -3) 50 50 紫外線硬化性樹脂溶液(A— 1 —4) 50 50 50 50 50 EHPE3150 10 10 10 10 10 多官能環氧化合物溶液(E— 1) 10 10 愛皮克龍N-680 10 10 10 TEPIC-S 10 10 10 10 氰藍5025 1.2 0.8 0.6 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 銘狀黃2RF 0.4 0.4 0.4 謝卡法斯特黃10GH 0.4 0.4 謝卡法斯特橙3064 0.4 0.4 謝卡法斯特橙900 0.4 0.4 克羅母法因藍5008 1.2 0.6 2GN(fckiUNfc) 0.8 依魯卡及亞907 4 4 4 4 4 4 4 4 4 4 4 4 4 4 卡亞麵DETX-S 0.5 0.5 0.5 0.5 0.5 0.5 Ό.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 卡必醇乙酸醋 5 5 5 5 5 5 5 5 5 5 5 5 5 5 摩達氟羅(均平觸 1 1 1 1 1 1 1 1 1 1 1 1 1 1 二氧化矽 10 10 10 10 10 10 10 10 10 10 10 10 10 10 mmm 20 20 20 17 17 18 18 17 17 18 18 20 17 20 三聚氰胺 1 1 1 1 1 1 1 1 t 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 7 7 7 7 硬化皮 膜之特 性評價 試驗 顔色 藍 m 藍 綠 綠 綠 綠 綠 綠 綠 綠 藍 綠 綠 麟雌(H) 5 5 5 5 5 5 5 5 5 5 5 5 5 5 棋盤格密接性試驗(個/100個） 100 100 100 100 100 100 100 100 100 100 100 100 100 100 焊料耐熱性(有/無） 膨起或剝落之有無 無 無 無 無 無 無 無 無 無 無 無 無丨 無 無 硬化被膜之變色程度 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 X Δ △ _劑性(有/無） 無 無 無 無 無 無 無 無 無 無 無 無 無 無 耐藥品性(有/無） 無 無 無 無 無 無 無 無 無 無 無 無 無 無 絕緣電阻(χ1〇"Ω) 2.5 2.5 2.5 2.5 2.6 2.6 2.6 2.8 2.8 2.8 2.8 2.8 2.8 2.4 鹵素含有l：(ppm) 除了有機成分之油里成分中 90 90 90 90 90 100 100 300 400 300 400 400 400 4000 硬化塗膜 90 90 90 90 90 100 100 300 400 300 400 400 400 4000 --------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 37 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1237531 B7 五、發明說明（ [表2] 樣品編號 寅施例 Π-1 Π-2 Π-5 Π-6 Π-7 Π-8 Π-9 Π-10 Π-11 比較例 Π-Ι2 H-I3 Π-14 紫外線 硬化型 防焊油 里之配 合組成（ 重童份） 環氧基丙烯酸醋(A—3—1) 環氧基丙烯酸酯(A—3—2> 環氧基丙烯酸酯(A—3—3) 環氧基丙烯酸酯(A-3-4) 環氧基丙烯酸醋(A—3—5) 環氧基丙烯酸酯(A—3—6> 三羥甲基丙烷三丙烯酸醋 40 30 40 50 2-羥基乙基甲基丙烯酸酯 1，6-己二醉二丙烯酸酯 乙二醇二甲基丙烯酸酿 2—丙嫌釅基翔基乙酸供酸酯 氰藍5025J i NN Chemical resistance test: After immersing the substrate in 10% by weight hydrochloric acid and 10% by weight sodium hydroxide aqueous solution at room temperature for 1 hour each, the paper size is subject to Chinese National Standard (CNS) A4 specifications (210 X 297 mm) -------- Order --------- line (please read the precautions on the back before filling this page) 1237531 A7 _ —____ B7__ V. Description of the invention () 7Ψ) Check the surface of the substrate to see if it is bulging or peeling. Insulation resistance test: The resistance between the opposed electrodes of the IPC-B-25 comb pattern with the hardened film of the present invention was measured. The content of halogen in the case of the photo-soldering ink of Example 1 was determined by weighing the residue obtained by removing the organic solvent from the ink volatilization and the cured coating film as samples, and letting these samples be in a combustion flask. Combustion is performed, and the contents of chlorine, bromine, and Φ fluorine in the absorption liquid that absorbs the generated gas are quantified by ion chromatography analysis. On the other hand, in the case of the ultraviolet curing type solder resist ink of Example 2, the ink before curing and the coating film after curing are respectively weighed as samples, and the halogen content is carried out in the same manner as in Example 1. The quantitative. Φ This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -------- tr '--------- line (please read the precautions on the back before filling This page) 1237531 A7B7 V. Description of the invention (> 7 <) [Table 1] Examples Comparative Examples Sample No. 1-1 1-2 r -3 I -4 1-5 1-6 I -7 1-8 I -9 1 -10 I -II I -12 1-13 1-14 Compounding composition (parts by weight) of light-resistant soldering oil and ultraviolet curing resin solution (A-1 -1) 50 50 50 50 50 UV curing Resin solution (A- 丨 -2) 50 50 UV-curable resin solution (A_ 1 -3) 50 50 UV-curable resin solution (A- 1-4) 50 50 50 50 50 EHPE3150 10 10 10 10 10 Multifunctional ring Oxygen compound solution (E— 1) 10 10 Epicon N-680 10 10 10 TEPIC-S 10 10 10 10 Cyan Blue 5025 1.2 0.8 0.6 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Inscription Yellow 2RF 0.4 0.4 0.4 Sheka Fast Yellow 10GH 0.4 0.4 Shekafast Orange 3064 0.4 0.4 Shekafast Orange 900 0.4 0. 4 Crom Fain Blue 5008 1.2 0.6 2GN (fckiUNfc) 0.8 Iruca and Asia 907 4 4 4 4 4 4 4 4 4 4 4 4 4 4 Cayenne surface DETX-S 0.5 0.5 0.5 0.5 0.5 0.5 Ό. 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 5 5 5 5 Modafluro (all flat touch 1 1 1 1 1 1 1 1 1 1 1 1 1 1 dioxide Silicon 10 10 10 10 10 10 10 10 10 10 10 10 10 10 mmm 20 20 20 17 17 18 18 17 17 18 18 20 17 20 Melamine 1 1 1 1 1 1 1 1 t 1 1 1 1 1 Dipenterythritol Hexacrylate 7 7 7 7 7 7 7 7 7 7 7 7 7 7 Characteristic evaluation test of hardened film Color blue m blue green green green green green green green blue green green female (H) 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Checkerboard adhesion test (pcs / 100 pcs.) 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Solder heat resistance (yes / no) Whether there is bulging or flaking? No? No? No? No? No? No? No No No 丨 No No Discoloration of the hardened film 〇〇〇〇〇〇〇〇〇〇〇〇X △ △ _ Dosage (yes / no) No no no no no no no no no no no no Chemical resistance (Yes / No) No No No No No No No No No No No No No No No Insulation resistance (χ1〇 " Ω) 2.5 2.5 2.5 2.5 2.6 2.6 2.6 2.8 2.8 2.8 2.8 2.8 2.8 2.4 Halogen contains l: (ppm) 90 90 90 90 90 100 100 300 400 300 400 400 400 4000 hardened coating film 90 90 90 90 90 100 100 300 400 300 400 400 400 4000 ------ --Order --------- line (please read the precautions on the back before filling this page) 37 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 1237531 B7 V. Description of the invention ([Table 2] Sample number Yin Example Π-1 Π-2 Π-5 Π-6 Π-7 Π-8 Π-9 Π-10 Π-11 Comparative Example Π-Ι2 H-I3 Π-14 Compounding composition in UV-curable solder resist (heavy weight) Epoxy Acrylate (A-3-1) Epoxy Acrylate (A-3-2 > Epoxy Acrylate (A-3-3 ) Epoxy acrylate (A-3-4) Epoxy acrylate (A-3-5) Epoxy acrylate (A-3-6) Trimethylolpropane triacrylate 40 30 40 50 2 -Hydroxyethyl methacrylate 1,6- Diethylene glycol diacrylate, ethylene glycol dimethacrylic acid, 2-propanthyl succinyl acetic acid ester, cyano blue 5025
;2RF; 2RF
謝卡法麟黃10GH 謝卡法麟橙3064 謝卡法麟橙900 克屜母法因藍5008 2GN(fifctUS|) 滑石 二氧化矽 2—乙基願 2,4-二乙基睡曜Ϊ 苄基二甲基嗣除醇 -2—甲基一 I 一苯基一丙烷一 1 一酮 二苯甲酮 2—甲基一1—[4 一 (甲硫基)苯基]—2—嗯林一丙烷一 -酮 0.6 0.4 20 20 0.5 0.5 0.3 0.5 0.5 30 30 20 30 20 20 30 50 20 硬化皮 膜之特 性評價 mt 顔色 藍 藍 藍 綠 綠 綠 綠 綠 綠 綠 綠 藍 綠 綠 鮮硬度(H) 棋盤格密接性試驗(個） 2.5 2.5 100 100 100 100 100 100 100 100 2.5 2.6 3.6 5.0 5.0 2.5 2.5 2.5 2.5 鹵索含有置(ppm)油墨 390 350 340 350 360 370 360 360 360 360 360 --------^--------- (請先閱讀背面之注意事項再填寫本頁) 硬傾膜 390 350 350 360 360 360 360 360 360 焊料耐熱性 焊料浸漬後之膨起或剝落(〇/ X) 〇 〇 〇 〇 〇 〇 〇 〇 0 0 〇 〇 0 〇 硬化纏之變色酿 〇 0 〇 〇 〇 〇 〇〇 0 〇 〇 Δ 本發明之光防焊油墨以及紫外線硬化型防焊油墨所形 成之塗膜，由表1之記載的結果可知，其相較於超出本發 明之範圍的習知之光防焊油墨以及紫外線硬化型防焊油墨 所形成之塗膜具有大致同等之硬度、耐剝離性、耐熱性以 及絕緣性。 38 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1237531 A7 B7 五、發明說明（ 再者，本發明之光防焊油墨以及紫外線硬化型防焊油 墨所形成之塗膜，相較於習知之油墨所形成之塗膜在鹵素 含有量極低。是以，此塗膜在燃燒時之鹵素氣體的產生量 被認爲較以往顯著地爲低。 又，本發明所使用之著色顏料因具有良好之分散性， 所以可配合各成分進行混合來輕易地調製。 尤其，於表1與表2中，實施例I 一2、I 一3、Π — 2以及Π —3、以及比較例I 一 12與Π — 12中，作爲著色 顏料皆僅使用藍色顏料而使得永久被膜呈現藍色。 惟，在實施例I 一2、1—3、Π—2以及Π —3中， 儘管所使用之著色顏料(C)(化學結構式中具有至少1個鹵 素原子之銅肽氰著色顏料)的配合量僅0.8份、0.6份如此 的少，惟仍可呈現出與配合有藍色著色顏料(於化學結構式 中不含鹵素原子）1·2份之比較例I 一 π與Π —12同等程度 的藍色。又，即使是搭配著色顏料而呈現綠色之情況，儘 管本發明實施例1一4〜Ι-ll以及π—4〜Π—11中之著 色顏料的總量僅〇·8份如此的少，惟仍可呈現出與僅配合 有無鹵素著色顏料1·〇份之比較例I 一 13與Π — 13同等程 度的綠色。 39 --------^--------- (請先閲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（21〇 X 297公楚）Shekafarin Yellow 10GH Shekafarin Orange 3064 Shekafarin Orange 900 Gram Mother Fain Blue 5008 2GN (fifctUS |) Talc Silicon Dioxide 2-Ethyl 2,4-Diethyl Sleeping Benzyl Dimethyl sulfonyl alcohol-2-methyl-1 I-phenyl-propane-1 1-ketobenzophenone 2-methyl-1— [4 mono (methylthio) phenyl] -2—umlin Monopropane-one 0.6 0.4 20 20 0.5 0.5 0.3 0.5 0.5 30 30 20 30 20 20 30 50 20 Evaluation of the characteristics of the hardened film mt color blue blue green green green green green green green blue green green fresh hardness (H) checkerboard adhesion test ( Pcs) 2.5 2.5 100 100 100 100 100 100 100 100 2.5 2.6 3.6 5.0 5.0 2.5 2.5 2.5 2.5 2.5 Halogen cable (ppm) ink 390 350 340 350 360 370 360 360 360 360 360 -------- ^- -------- (Please read the precautions on the back before filling in this page) Hard tilting film 390 350 350 360 360 360 360 360 360 Solder heat-resistant swelling or peeling after dipping (〇 / X) 〇 〇〇〇〇〇〇〇００００ 〇 〇 〇 〇 The discoloration of the hardening entanglement 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 △ The light solder resist ink and ultraviolet curing type of the present invention From the results shown in Table 1, the coating film formed by the solder ink shows that the coating film has approximately the same hardness as the coating film formed by the conventional photo-soldering ink and ultraviolet-curable soldering ink which are beyond the scope of the present invention. , Peel resistance, heat resistance and insulation. 38 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 1237531 A7 B7 V. Description of the invention (Further, the coating film formed by the light solder resist ink and the UV-curable solder resist ink of the present invention Compared with the conventional ink, the coating film formed by the ink contains extremely low halogen content. Therefore, the amount of halogen gas generated during combustion of this coating film is considered to be significantly lower than in the past. In addition, the invention is used in the present invention. Because the colored pigment has good dispersibility, it can be easily prepared by mixing with each component. In particular, in Tables 1 and 2, Examples I-12, I-3, Π-2, and Π-3, And in Comparative Examples I-12 and Π-12, only the blue pigment was used as the coloring pigment to make the permanent film appear blue. However, in Examples I1-2, 1-3, Π-2, and Π-3 Although the coloring pigment (C) (a copper peptide cyanine pigment with at least one halogen atom in the chemical structural formula) is only 0.8 parts and 0.6 parts, the amount of the pigment is still blue. Color pigments (halogen-free in chemical formula) (A) 1.2 parts of Comparative Example I—π is blue to the same degree as Π-12. Even in the case of a green color with a coloring pigment, although Examples 1 to 4 to 11-11 and π- The total amount of colored pigments in 4 to Π-11 is only 0.8 parts so small, but it can still exhibit the same degree of comparison with that of Comparative Example I-13 and Π-13 only with 1.0 parts of halogen-free coloring pigments. Green. 39 -------- ^ --------- (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (21〇X 297 Gongchu)