1357536 九、發明說明 【發明所屬之技術領域】 本發明係適用於作爲印刷配線板之永久光罩的使用， 曝光後，藉由以鹼水溶液進行顯像俾形成圖型，其後，藉 由加熱硬化，可形成高反射率之抗焊阻劑膜的光硬化性及 熱硬化性抗焊阻劑組成物，及於形成電路之印刷配線板表 面上，使用該組成物而形成抗焊阻劑圖型所得到之印刷配 線板。 【先前技術】 印刷配線板一般係藉蝕刻除去貼合於層合板之銅箱的 不用部分以形成電路配線者，藉由電子零件焊接以配置於 特定之處。亦即，抗焊阻劑膜係使用來作爲焊接電子零件 時之電路的保護膜。抗焊阻劑膜係焊接時，防止焊錫附著 於不需要的部分，同時並防止電路導體直接曝露於空氣 中’而與氧或濕氣反應。進一步’亦發揮作用爲電路基板 之永久保護膜。因此，要求密接性、電絕緣性、焊錫耐熱 性、耐溶劑性、耐藥品性等之各特性。 又，印刷配線板係爲實現高密度化，邁向微細化 (Fine化）、多層化及一次黏著化之一途，封裝方式亦推 展至表面封裝技術（SMT)。因此，抗焊阻劑膜係微細 化、高解析性、高精度、高信賴性之要求漸高漲。 形成如此之抗焊阻劑的圖型之技術，可正確地形成微 細圖型之光阻法尤其從環境面之考量等，鹼顯像型之光^^ -5- 1357536 法成爲主流。 例如，於專利文獻1及專利文獻2中係揭示一種酚醛 清漆型環氧樹脂與不飽和單羧酸反應，進一步以加成多鹼 酸酐之反應生成物作爲基材聚合物之鹼水溶液可顯像之液 狀光阻油墨組成物。 另外，近年，攜帶終端、個人電腦、電視等之液晶顯 示器的背光。又照明器具之光源等以低電力進行發光之發 光二極體（LED )直接封裝於被覆形成抗焊阻劑膜之印刷 配線板上的用途已漸增。 是故，爲有效地利用 LED之光，遂尋求一種印刷配 線板，其係具有高反射率、並可使LED封裝於印刷配線 板時可全體提昇照度之抗焊阻劑膜。 [專利文獻1]特公平1- 5439〇號 [專利文獻2]特公平7 - 1 773 7號。 【發明內容】 (發明之揭示） (發明欲解決之問題） 爲有效率地利用直接封裝印刷配線板之LED的光， 如上述般，抗焊阻劑膜爲高反射率，同時地必須使用LED 作爲光源之期間而維持此高反射率。然而，一般之抗焊阻 劑組成物係含有具有芳香環之成分作爲用以提高耐熱性之 一個手段。此處，芳香環係藉光或熱具有徐緩地反應之性 質，以如此之抗焊阻劑組成物所形成之抗焊阻劑膜，係封 -6 - 1357536 裝LED之期間，徐緩地受芳香環之反應招致黃變等劣化 之問題仍存在。 因此，本發明之目的在於提供一種可形成不易受光劣 化及熱劣化之高反射率的抗焊阻劑膜之白色的光硬化性及 熱硬化性抗焊阻劑組成物，以及使用此白色的光硬化性及 熱硬化性抗焊阻劑組成物所形成之高反射率的抗焊阻劑膜 之印刷配線板。 (用以解決問題之手段） 本發明人等經專心硏究之結果，發現藉由使用不具有 芳香環之含羧基樹脂、氫化環氧化合物及作爲白色顏料之 金紅石型氧化鈦，俾可抑制抗焊阻劑膜之劣化（黃變）， 可經長期間而達成高反射率。 亦即，若依本發明之第1態樣，提供一種白色之光硬 化性及熱硬化性抗焊阻劑組成物，其特徵在於：含有 (A)不具有芳香環之含羧基樹脂、（B)光聚合起始劑、 (C)氫化環氧化合物、（D)金紅石型氧化鈦、及（E) 稀釋劑。 若依本發明之另一態樣，提供一種印刷配線板，係於 形成電路之印刷配線板表面使用第1態樣的白色之光硬化 性及熱硬化性抗焊阻劑組成物而形成抗焊阻劑膜所得到 者。 若依本發明，可得到一種抗焊阻劑組成物，其係可抑 制起用於含羧基樹脂與環氧化合物中之芳香環、及氧化鈦 1357536 之光與熱所造成的抗焊阻劑膜之劣化（黃變），並 間而維持抗焊阻劑膜之高反射率。使用此抗焊阻劑 而形成高反射率之抗焊阻劑膜，將led封裝於印 板時，可提昇全體照度。 (用以實施發明之最佳形態） 以下，更詳細說明本發明。 本發明之白色的抗焊阻劑組成物，其係含有（ 具有芳香環之含羧基樹脂、（B)光聚合起始劑、< 化環氧化合物、（D)金紅石型氧化鈦、及（E )稀 不具有芳香環之含羧基樹脂（A)若爲具有不 環之羧基的樹脂，其本身具有感光性不飽和雙鍵1 之感光性的含羧基樹脂、及不具有感光性不飽和雙 羧基樹脂之任一者均可使用，並無特別限定。尤其 宜使用列舉於以下之樹脂中不具有芳香環者（寡聚 合物之任一者）。亦即， (1) 含羧基樹脂，其係依脂肪族不飽和羧酸與 〜20之脂肪族聚合性單體（具體上可舉例如脂肪 .基）丙烯醯基化合物、脂肪族乙烯基醚、脂肪酸之 酯等）之共聚合而得到者： (2) 感光性的含羧基樹脂，其係於由碳數 脂肪族聚合性單體所生成之含羧基的（甲基）丙烯 聚合樹脂上，使於一分子中具有環氧乙烷與乙烯性 基之碳數4〜20的脂肪族聚合性單體反應所得到者 可長期 組成物 刷配線 :A )不 〔C)氫 釋劑。 含芳香 個以上 鍵之含 ，可適 物或聚 碳數2 族（甲 乙烯基 -20之 基系共 不飽和 1357536 (3) 感光性的含羧基樹脂，其係於1分子中分別具 有1個環氧基與不飽和雙鍵之碳數4〜20之脂肪族聚合性 單體（例如縮水甘油基（甲基）丙烯酸酯等）、具有不飽 和雙鍵之碳數2〜20之脂肪族聚合性單體（具體上係可舉 例如脂肪族（甲基）丙烯醯基化合物、脂肪族乙烯基醚、 脂肪酸之乙烯基酯等）的共聚物上，使脂肪族不飽和單羧 酸反應，於所生成之第2級羥基與飽和或不飽和之脂肪族 多鹼酸酐反應所得到者： (4) 感光性的羥基及含羧基樹脂，其係於含有脂肪 族羥基的聚合物上使飽和或不飽和之脂肪族多鹼酸酐反應 後，於所生成之羧酸上使1分子中分別具有！個環氧基與 不飽和雙鍵之碳數4〜20之脂肪族聚合性單體（例如縮水 甘油基（甲基）丙烯酸酯等）反應所得到者。 又，在本說明書中’脂肪族係亦包括於分子內含有環 己烷環或環己烯環等之環的化合物。 此等之中宜爲感光性的含羧基樹脂，其係上述（2) 之感光性的含羧基樹脂即（a)於由碳數2〜2〇之脂肪族 聚合性單體所生成之含羧基的（甲基）丙烯基系共聚合樹 脂上’使（b)於一分子中具有環氧乙烷環與乙烯性不飽 和基之碳數4〜20的脂肪族聚合性單體反應所得到者。 由（a)之碳數2〜20之脂肪族聚合性單體所生成之 含羧基的（甲基）丙烯基系共聚合樹脂，係碳數4〜2〇之 (甲基）丙稀酸醋 '與於1分子中具有1個不飽和基與至 少一個之羧基的脂肪族化合物共聚合所得到。構成共聚合 -9- 1357536 樹脂（a)之（甲基）丙烯酸酯係可舉例如甲基（甲基） 丙烯酸酯、乙基（甲基）丙烯酸酯、丙基（甲基）丙烯酸 酯、丁基（甲基）丙烯酸酯、戊基（甲基）丙烯酸酯、己 基（甲基）丙烯酸酯等之（甲基）丙烯酸酯烷酯類、2-羥乙基（甲基）丙烯酸酯、羥丙基（甲基）丙烯酸酯、羥 丁基（甲基）丙烯酸酯、己內酯改性2-羥乙基（甲基） 丙烯酸酯等之含羥基的（甲基）丙烯酸酯類、甲氧基二乙 二醇（甲基）丙烯酸酯、乙氧基二乙二醇（甲基）丙烯酸 酯、異辛基氧二乙二醇（甲基）.丙烯酸酯、甲氧基三乙二 醇（甲基）丙烯酸酯、甲氧基聚乙二醇（甲基）丙烯酸酯 等之甘醇改性（甲基）丙烯酸酯類等。此等可單獨使用， 亦可混合2種以上而使用。又，在本說明書中，（甲基） 丙烯酸酯係丙烯酸酯及甲基丙烯酸酯之總稱用語，有關其 他之類似的表現亦相同。 又，於1分子中具有1個不飽和基與至少一個之羧基 的脂肪族化合物係可舉例如丙烯酸、甲基丙烯酸、不飽和 基與羧酸之間鏈延長之改性不飽和單羧酸、例如-羧乙 基（甲基）丙烯酸酯、2 -丙烯醯氧乙基琥珀酸、2 -丙烯 醯氧乙基琥珀酸六氫酞酸、藉內酯改性等具有酯鍵之不飽 和單羧酸、具有醚鍵之改性不飽和單羧酸、進一步係於分 子中含有馬來酸等之羥基2個以上者。此等係可單獨使用 或混合兩種以上而使用。 (b)於一分子中具有環氧乙烷環與乙烯性不飽和基 之碳數4〜20的脂肪族聚合性單體係可舉例如縮水甘油基 -10 - 1357536 (甲基）丙烯酸酯、α -甲基縮水甘油基（甲基）丙烯酸 酯、3,4 -環氧基環己基甲基（甲基）丙烯酸酯、3,4 -環 氧基環己基乙基（甲基）丙烯酸酯、3，4 -環氧基環己基 丁基（甲基）丙烯酸酯、3，4 -環氧基環己基甲基胺基丙 烯酸酯等。其中宜爲3，4_環氧基環己基甲基（甲基）丙 烯酸酯。此等（b)於一分子中具有環氧乙烷環與乙烯性 不飽和基之碳數4〜20的脂肪族聚合性單體係可單獨使用 亦可混合兩種以上而使用。 不具有芳香環之含羧基樹脂（A)係其酸價必須在於 50〜200mgKOH/g之範圍。酸價不足50mgKOH/g時，在弱 鹼水溶液之未曝光部分很難除去。若超過200mgKOH/g， 有硬化被膜之耐水性、電氣特性差等之問題。又，含羧基 樹脂（A)之重量平均分子量宜在於5000〜1 00000的範 圍。若重量平均分子量不足5 000，有指觸乾燥性明顯差之 問題的傾向。又，若重量平均分子量超過1 00000，因產生 顯像性、貯存安定性明顯惡化之問題·，故不佳。 本發明所使用之光聚合起始劑（B )可舉例如苯偶 因、苯偶因甲基醚、苯偶因乙基醚、苯偶因異丙基醚等之 苯偶因與苯偶因烷基醚類；乙醯苯、2，2-二甲氧基- 2-苯基乙醯苯、2,2 -二乙氧基-2-苯基乙醯苯、2,2 -二乙 氧基-2-苯基乙醯苯、1,1-二氯乙醯苯等之乙醯苯類； 2 -甲基-1 - [4 -(甲基硫）苯基]-2 -嗎啉基丙烷-i _ 丁酮、2 -苯甲基-2-二甲基胺基-1- (4-(嗎啉基苯 基）-丁酮-1，2-(二甲基胺基）- 2- [(4 -甲基苯 -11 - 1357536 基）甲基]-1 - [4 - ( 4-嗎啉基）苯基]-1 - 丁酮等之胺 基烷基酚類；2 -甲基蔥酮、2 -乙基蔥酮、2 -第三丁基 蔥酮、1-氯蔥酮等之蔥酮類；2,4-二甲基硫雜蔥酮、 2,4 -二乙基硫雜蔥酮、2 -氯硫雜蔥酮、2,4 -二異丙基硫 雜蔥酮等之硫雜蔥酮類；乙醯苯二甲基縮醛、苯甲基二甲 基縮醛等之縮醛類；二苯甲酮等之二苯甲酮類；或蔥酮 類；（2,6-二甲氧基苯甲醯基）-2,4,4 -戊基氧化磷、 雙（2,4,6 -三甲基苯甲醯基）-苯基氧化磷、2,4,6 -三 甲基苯甲醯基二苯基氧化磷、乙基-2,4,6 -三甲基苯甲醯 基苯基磷酸酯等之氧化磷類；各種過氧化物類、二茂鈦系 起始劑等，此等係亦可與N，N -二甲基胺基安息香酸乙 酯、N，N -二甲基胺基安息香酸異戊酯、戊基-4 -二甲基 胺基苯甲酸酯、三乙胺、三乙醇胺等之三級胺類的光增感 劑等。此等之光聚合起劑係可單獨使用亦可混合兩種以上 而使用。 光聚合起劑（B)之調配量係相對於不具有芳香環之 含羧基樹脂（A) 100質量份宜爲1〜30質量份、更宜爲2 〜25質量份。光聚合起劑（B)之調配量不足1質量份 時，光硬化性降低，曝光/顯像後之圖型形成變困難，故 不佳。另外，超過3 0質量份時，厚膜硬化性會降低，成 爲成本高的原因，故不佳。 其次，氫化環氧化合物（C)係使具有芳香環之化合 物進行核加氫後，進行環氧化之化合物、及使芳香族環氧 化合物之芳香環選擇性地進行核加氫所得到之環氧化合物 -12- 1357536 之任一者均可使用。可使用例如氫化雙酚A型環氧樹脂、 氫化雙酚F型環氧樹脂、氫化雙酚S型環氧樹脂、氫化雙 酚型環氧樹脂、氫化雙二甲苯酚型環氧樹脂、氫化酌酿醛 清漆型環氧樹脂、氫化甲酚醛清漆型環氧樹脂、氫化雙酣 A型酚醛清漆型環氧樹脂等之氫化芳香族系縮水甘油基醚 化合物，氫I化Θ酞酸一縮水甘油基醋等之氫化芳香族系縮 水甘油基酯化合物；氫化N，N，N’，N’ -四縮水甘油基間二 甲苯二胺、氫化N，N -二縮水甘油基苯胺等之氫化芳香族 系縮水甘油基胺化合物等已知者。此等之中，使用使雙酚 A型環氧樹脂之芳香環選擇性核加氫所得到之氫化雙酚a 型環氧樹脂（例如Japan Epoxy Resin製之商品名 YX-8 034等）’從電氣特性、耐熱性而言，更佳。此等之添加 氫環氧化合物係可單獨使用亦可混合兩種以上而使用。 又，如前述般，使芳香族環氧化合物之芳香環選擇性 進行核加氫所得到之環氧化合物時，可控制氫添加率，依 氫添加率而結晶性、耐熱性、熱劣化性等相異》 本發明之抗焊阻劑組成物中的氫化環氧化合物之平均 氫添加率係考慮抑制抗焊阻劑膜之熱所造成的劣化、與維 持良好的耐熱性來決定。具體上，平均氫添加率宜爲50〜 1 0 0 %，更宜爲8 0〜1 0 0 % » 氫化環氧化合物（C)之調配量係相對於不具有芳香 環之含羧基樹脂（A) 100質量份宜爲5〜70質量份、更 宜爲5〜60質量份。氫化環氧化合物（C)之調配量若超 過70質量份，在顯像液之未曝光部分的溶解性會降低， -13- 1357536 易產生顯像殘留，實用上很難使用。另外，若不足5質量 份，含羧基樹脂（A )之羧基會以未反應之狀態殘留’故 有很難充分得到硬化塗膜之電氣特性、焊錫耐熱性、耐藥 品性之傾向。 不具有芳香環之含羧基樹脂（A)之羧基、與氫化環 氧化合物（C)之環氧基係藉開環聚合進行反應。 在本發明中係使用金紅石型氧化鈦（D)作爲白色顏 料亦爲特徵之一。銳鈦礦型氧化鈦係與金紅石型比較而白 色度高，故常使用。但銳鈦礦型氧化鈦因具有光觸媒活 性，有時引起抗焊阻劑組成物中之樹脂的變色。然而，金 紅石型氧化鈦係白色度與銳鈦礦型比較而略差，但幾乎不 具有光活性，故可得到安定之抗焊阻劑膜。金紅石型氧化 鈦（D )係可使用公知之金紅石型氧化鈦者。具體上係可 使用富士鈦工業（股）製 TR - 600、TR - 700、TR -750、TR - 840、石原產業（股）製 R - 550、R - 5 80 ' R -630、R - 820、CR - 50、CR - 60、CR - 90、鈦工業 (股）製 KR - 270、KR - 310、KR - 380 等。 金紅石型氧化鈦（D )之調配量係相對於不具有芳香 環之含羧基樹脂（A) 100質量份，宜爲 50〜300質量 份，更宜爲60〜260質量份。若調配量超過3 00質量份， 光硬化性降低，硬化深度變低，故不佳。另外，若不足50 質量份，遮蔽力小，無法得到高反射率之抗焊阻劑膜。 又，在本發明中，若倂用二氧化矽粒子（F )，可得 到具有更深之硬化深度之抗焊阻劑組成物。認爲此係二氧 -14- 1357536 化矽的折射率與含羧基樹脂（A )比較接近。 如此之二氧化矽粒子（F )係可使用公知者。可舉例 如球狀二氧化砂（Admatechs公司製 Admafine SO - E1、 SO - E2、SO - E5等）、微粉狀二氧化矽、無定形二氧化 矽、結晶性二氧化矽、熔融二氧化矽等。此等二氧化矽粒 子係可單獨使用亦可組合兩種以上而使用。二氧化矽粒子 (F)之調配量係相對於不具有芳香環之含羧基樹脂（A) 1〇〇質量份，宜爲50〜200質量份。 本發明所使用之稀釋劑（E )可舉例如光聚合性單體 及/或有機溶劑。光聚合性單體可舉例如2 -羥乙基丙烯酸 酯、2 -羥丁基丙烯酸酯等之羥烷基丙烯酸酯類；乙二 醇、甲氧基四乙二醇、聚乙二醇、丙二醇等之甘醇的單或 二丙烯酸酯類：N，N -二甲基丙烯醯胺、N -羥甲基丙烯醯 胺等之丙烯醯胺類；N，N -二甲基胺基乙基丙烯酸酯等之 胺基烷基丙烯酸酯類；己二醇、三羥甲基丙烷、季戊四 醇、二季戊四醇、三-羥乙基三聚異氰酸酯等之多元醇或 此等之環氧乙烷或環氧丙烷加成物的多元醇類；苯氧基丙 烯酸酯、雙酚A二丙烯酸酯及、此等酚類之環氧乙烷或環 氧丙烷加成物的多元醇類；甘油二縮水甘油基醚、三羥甲 基丙烷三縮水甘油基醚等之縮水甘油基醚的丙烯酸酯類； 三聚氰胺丙烯酸酯；及/或對應於上述丙烯酸酯類之甲基 丙烯酸酯類等。 另外’有機溶劑可舉例如甲乙酮、環己酮等之酮類； 甲苯、二甲苯、四甲基苯等之芳香族烴類；甲基溶纖劑、 -15- 1357536 乙基溶纖劑、丁基溶纖劑、甲基卡必醇、丁基卡必醇、丙 二醇單甲基醚、二乙二醇單乙基醚類；二丙二醇單乙基 醚、三乙二醇單乙基醚等之甘醇醚類：醋酸乙酯、醋酸丁 酯、溶纖劑乙酸酯、二乙二醇單乙基醚乙酸酯、及上述甘 醇醚類之酯化物等的酯類；乙醇、丙醇、乙二醇、丙二醇 等之醇類；辛烷、癸烷等之脂肪族烴類；石油醚、石油 腦、氫化石油腦等之石油系溶劑等。 如上述之稀釋劑（E)係可單獨使用亦可混合兩種以 上而使用。相對於不具有芳香環之含羧基樹脂（A) 100 質量份，宜使用2〇〜3〇〇質量份的稀釋劑（E )。前述稀 釋劑之使用目的係光聚合性單體不僅亦形成塗佈之狀態， 稀釋活性能量線硬化性樹脂，增強光聚合性者，另外，有 機溶劑係藉乾燥以進行造膜。因此，依照所使用之稀釋 劑，可使用使光罩接觸於塗膜之接觸方式或非接觸方式之 任一者的曝光方式。1357536 IX. Description of the Invention [Technical Fields of the Invention] The present invention is applicable to the use of a permanent mask as a printed wiring board. After exposure, a pattern is formed by developing an aqueous solution with an aqueous solution, and thereafter, by heating. The composition of the photocurable and thermosetting solder resist which forms a high reflectance solder resist film, and forms a solder resist resist pattern on the surface of the printed wiring board on which the circuit is formed. Type of printed wiring board obtained. [Prior Art] A printed wiring board is generally formed by etching to remove unnecessary portions of a copper box attached to a laminate to form a circuit wiring, and is placed in a specific place by soldering electronic parts. That is, the solder resist film is used as a protective film for a circuit when soldering electronic parts. The solder resist film is soldered to prevent solder from adhering to unnecessary portions while preventing the circuit conductor from being directly exposed to the air and reacting with oxygen or moisture. Further, it also functions as a permanent protective film for the circuit substrate. Therefore, various characteristics such as adhesion, electrical insulation, solder heat resistance, solvent resistance, and chemical resistance are required. Further, in order to achieve high density, the printed wiring board is moving toward miniaturization (Fineization), multilayering, and primary adhesion, and the package method is also advanced to surface mount technology (SMT). Therefore, the requirements for miniaturization, high resolution, high precision, and high reliability of the solder resist film are increasing. The technique of forming such a pattern of the anti-solder resist can correctly form a micro-pattern of the photoresist method, especially from the environmental side, and the alkali-developing type of light ^^ -5 - 1357536 becomes the mainstream. For example, Patent Document 1 and Patent Document 2 disclose that a novolac type epoxy resin is reacted with an unsaturated monocarboxylic acid, and further, an alkali aqueous solution of a base polymer can be imaged by reacting a reaction product of a polybasic acid anhydride. Liquid photoresist ink composition. In addition, in recent years, backlights of liquid crystal displays such as terminals, personal computers, and televisions have been carried. Further, the use of a light-emitting diode (LED) that emits light with low power, such as a light source of a lighting fixture, is directly packaged on a printed wiring board coated with a solder resist film. Therefore, in order to effectively utilize the light of LEDs, a printing wiring board having a high reflectance and a solder resist film which can enhance the illumination at the time of packaging the printed wiring board can be sought. [Patent Document 1] Special Fair 1 - 5439 [ [Patent Document 2] Special Fair 7 - 1 773 No. 7. [Disclosure of the Invention] (Disclosure of the Invention) In order to efficiently utilize light of an LED directly encapsulating a printed wiring board, as described above, the solder resist film is highly reflective, and at the same time, an LED must be used. This high reflectance is maintained as a period of the light source. However, a general solder resist composition contains a component having an aromatic ring as a means for improving heat resistance. Here, the aromatic ring is a property of reacting slowly by light or heat, and the anti-solder film formed by such a resist resist composition is slowly scented during the period of sealing the LED of -6 - 1357536. The problem of deterioration of the ring caused by the reaction of the ring still exists. Accordingly, an object of the present invention is to provide a white light-curable and thermosetting solder resist composition which can form a high-reflectance resist film which is less susceptible to photodegradation and thermal deterioration, and a white light-reducing composition. A printed wiring board of a high reflectance solder resist film formed of a hardenable and thermosetting solder resist composition. (Means for Solving the Problem) As a result of intensive investigation, the present inventors have found that ruthenium can be suppressed by using a carboxyl group-containing resin having no aromatic ring, a hydrogenated epoxy compound, and rutile-type titanium oxide as a white pigment. The deterioration of the solder resist film (yellowing) can achieve high reflectance over a long period of time. That is, according to the first aspect of the present invention, there is provided a white photocurable and thermosetting solder resist composition comprising (A) a carboxyl group-containing resin having no aromatic ring, (B) a photopolymerization initiator, (C) a hydrogenated epoxy compound, (D) rutile-type titanium oxide, and (E) a diluent. According to another aspect of the present invention, a printed wiring board is provided which is formed by using a white light-curing and thermosetting solder resist composition of a first aspect on a surface of a printed wiring board on which a circuit is formed. The film obtained by the resist film. According to the present invention, there can be obtained a solder resist composition which can suppress the anti-solder film which is caused by the light and heat of the aromatic ring in the carboxyl group-containing resin and the epoxy compound, and the titanium oxide 1357536. Deterioration (yellowing), and maintaining high reflectivity of the solder resist film. The use of this solder resist to form a high reflectance solder resist film improves the overall illumination when the LED is packaged on a printed board. (Best Mode for Carrying Out the Invention) Hereinafter, the present invention will be described in more detail. The white solder resist composition of the present invention contains (a carboxyl group-containing resin having an aromatic ring, (B) a photopolymerization initiator, a <an epoxy compound, (D) a rutile type titanium oxide, and (E) a carboxyl group-containing resin having a rare aromatic ring (A), if it is a resin having an acyclic carboxyl group, itself has a photosensitive carboxyl group-containing resin having a photosensitive unsaturated double bond 1, and does not have photosensitive unsaturated Any of the dicarboxyl resins may be used without particular limitation. It is particularly preferred to use any of the following resins which do not have an aromatic ring (any of the oligopolymers). That is, (1) a carboxyl group-containing resin, It is obtained by copolymerization of an aliphatic unsaturated carboxylic acid with an aliphatic polymerizable monomer of -20 (specifically, for example, a fat-based acryl-based compound, an aliphatic vinyl ether, or an ester of a fatty acid). (2) A photosensitive carboxyl group-containing resin which is bonded to a carboxyl group-containing (meth) propylene polymer resin produced from a carbon number aliphatic polymerizable monomer to have ethylene oxide in one molecule. Aliphatic polymerization of ethylene groups having 4 to 20 carbon atoms The monomers obtained by the reaction composition may be long brush lines: A) [not C) a hydrogen diluent. Containing more than one aromatic bond, conjugate or polycarbon number 2 (methylvinyl-20-based co-unsaturated 1357536 (3) photosensitive carboxyl-containing resin, which has 1 in each molecule An aliphatic polymerizable monomer having an epoxy group and an unsaturated double bond of 4 to 20 carbon atoms (for example, glycidyl (meth) acrylate or the like), and an aliphatic polymerization having a carbon number of 2 to 20 having an unsaturated double bond The monomer (specifically, for example, an aliphatic (meth) acrylonitrile compound, an aliphatic vinyl ether, a vinyl ester of a fatty acid, or the like) is reacted with an aliphatic unsaturated monocarboxylic acid. The resulting second-stage hydroxyl group is reacted with a saturated or unsaturated aliphatic polybasic acid anhydride: (4) a photosensitive hydroxyl group and a carboxyl group-containing resin which are saturated or not attached to a polymer containing an aliphatic hydroxyl group. After reacting a saturated aliphatic polybasic acid anhydride, an aliphatic polymerizable monomer having a carbon number of 4 to 20 each having an epoxy group and an unsaturated double bond in one molecule (for example, glycidol) is formed on the produced carboxylic acid. Base (meth) acrylate, etc.) Further, in the present specification, the 'aliphatic system' also includes a compound containing a ring such as a cyclohexane ring or a cyclohexene ring in the molecule. Among these, a photosensitive carboxyl group-containing resin is preferable, which is the above (2). The photosensitive carboxyl group-containing resin (a) is (b) on the carboxyl group-containing (meth)acryl-based copolymer resin produced from the aliphatic polymerizable monomer having 2 to 2 carbon atoms. An aliphatic polymerizable monomer having an oxirane ring and an ethylenically unsaturated group having 4 to 20 carbon atoms in one molecule. An aliphatic polymerizable monomer having 2 to 20 carbon atoms (a) The resulting carboxyl group-containing (meth) propylene-based copolymerized resin is a (meth) acrylate vinegar having a carbon number of 4 to 2 Å and has one unsaturated group and at least one carboxyl group in one molecule. The aliphatic compound is obtained by copolymerization of the aliphatic compound. The (meth) acrylate constituting the copolymerized-9-1357536 resin (a) may, for example, be methyl (meth) acrylate, ethyl (meth) acrylate or propyl. Base (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, (meth) acrylate alkyl esters such as (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, Caprolactone-modified hydroxyl group-containing (meth) acrylate such as 2-hydroxyethyl (meth) acrylate, methoxy diethylene glycol (meth) acrylate, ethoxy diethylene glycol (Meth) acrylate, isooctyloxy diethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate Glycol-modified (meth) acrylates, etc. These may be used singly or in combination of two or more. Further, in the present specification, (meth) acrylate-based acrylate and methacrylic acid The general term for esters is similar for other similar performances. Further, the aliphatic compound having one unsaturated group and at least one carboxyl group in one molecule may, for example, be an acrylic acid, methacrylic acid, a modified unsaturated monocarboxylic acid having a chain extended between an unsaturated group and a carboxylic acid, For example, carboxyethyl (meth) acrylate, 2-propenyl oxyethyl succinic acid, 2-propenyl oxyethyl succinic acid hexahydro decanoic acid, ester-modified unsaturated monocarboxylic acid modified by lactone The acid, the modified unsaturated monocarboxylic acid having an ether bond, and further preferably two or more hydroxyl groups containing maleic acid or the like in the molecule. These may be used singly or in combination of two or more. (b) an aliphatic polymerizable single system having an oxirane ring and an ethylenically unsaturated group in a molecule and having a carbon number of 4 to 20, for example, glycidyl-10-1357536 (meth) acrylate, --methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylbutyl (meth) acrylate, 3,4-epoxycyclohexylmethyl acrylate, and the like. Among them, 3,4-epoxycyclohexylmethyl (meth) acrylate is preferred. (b) The aliphatic polymerizable single system having 4 to 20 carbon atoms and having an oxirane ring and an ethylenically unsaturated group in one molecule may be used singly or in combination of two or more. The carboxyl group-containing resin (A) having no aromatic ring must have an acid value in the range of 50 to 200 mgKOH/g. When the acid value is less than 50 mgKOH/g, it is difficult to remove the unexposed portion of the weak alkali aqueous solution. When it exceeds 200 mgKOH/g, there is a problem that water resistance and electrical properties of the cured film are poor. Further, the weight average molecular weight of the carboxyl group-containing resin (A) is preferably in the range of 5,000 to 1,000 00000. If the weight average molecular weight is less than 5,000, there is a tendency that the dryness is markedly poor. Further, when the weight average molecular weight exceeds 1,000, the problem of developmental visibility and deterioration in storage stability is deteriorated, which is not preferable. The photopolymerization initiator (B) used in the present invention may, for example, be a benzoin, a benzoin methyl ether, a benzoin ethyl ether or a benzoin isopropyl ether; Alkyl ethers; acetophenone, 2,2-dimethoxy-2-phenylethenzene, 2,2-diethoxy-2-phenylethylbenzene, 2,2-diethoxy Ethylene benzene such as phenyl-2-phenyl acetonide or 1,1-dichloroacetamidine; 2-methyl-1 -[4-(methylthio)phenyl]-2- morpholinyl Propane-i-butanone, 2-benzyl-3-dimethylamino-1-(4-(morpholinophenyl)-butanone-1,2-(dimethylamino)-2 - [(4-methylphenyl-11-1357536)methyl]-1 - [4-(4-morpholinyl)phenyl]-1-butanone and the like aminoalkylphenols; 2-A Onion ketones such as ketone, 2-ethyl onion ketone, 2-tert-butyl onion ketone, 1-chlorolone, etc.; 2,4-dimethylthiane, 2,4-diethyl Thiolene ketone, 2-chlorothianicone, 2,4-diisopropylthionone, etc.; acetophene acetal, benzyl dimethyl acetal An acetal; a benzophenone such as benzophenone; or an onion ketone; (2,6-dimethoxybenzamide) )-2,4,4-pentylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, 2,4,6-trimethylbenzhydrylbiphenyl Phosphorus oxides such as phosphorus oxide and ethyl-2,4,6-trimethylbenzimidyl phosphate; various peroxides, titanocene initiators, etc. With N,N-dimethylamino benzoic acid ethyl ester, N,N-dimethylamino benzoic acid isoamyl ester, pentyl-4 -dimethylaminobenzoic acid ester, triethylamine, three A photo-sensitizer such as a tertiary amine such as ethanolamine, etc. These photopolymerization initiators may be used singly or in combination of two or more kinds. The amount of the photopolymerization initiator (B) is relative to no fragrance. 100 parts by mass of the carboxyl group-containing resin (A) is preferably 1 to 30 parts by mass, more preferably 2 to 25 parts by mass. When the amount of the photopolymerization agent (B) is less than 1 part by mass, photocurability is lowered, and exposure is performed. In the case of more than 30 parts by mass, thick film hardenability is lowered, which is a cause of high cost, which is not preferable. Next, hydrogenated epoxy compound (C) Aromatic ring Any one of the epoxy compound -12-1357536 obtained by subjecting the compound to epoxidation and optionally hydrogenating the aromatic ring of the aromatic epoxy compound may be used. For example, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated bisphenol S type epoxy resin, hydrogenated bisphenol type epoxy resin, hydrogenated bisxylenol type epoxy resin, hydrogenation type Hydrogenated aromatic glycidyl ether compound such as aldehyde varnish type epoxy resin, hydrogenated cresol novolak type epoxy resin, hydrogenated biguanide type A novolak type epoxy resin, hydrogen phthalic acid monoglycidyl vinegar Hydrogenated aromatic glycidyl ester compound; hydrogenated aromatic shrinkage of hydrogenated N, N, N', N'-tetraglycidyl m-xylene diamine, hydrogenated N, N-diglycidyl aniline Glycerylamine compounds and the like are known. Among these, a hydrogenated bisphenol a type epoxy resin (for example, trade name YX-8 034 manufactured by Japan Epoxy Resin) obtained by selective nuclear hydrogenation of an aromatic ring of a bisphenol A type epoxy resin is used. It is more preferable in terms of electrical characteristics and heat resistance. These hydrogen-added epoxy compounds may be used singly or in combination of two or more. In the case of the epoxy compound obtained by selectively hydrogenating the aromatic ring of the aromatic epoxy compound, the hydrogen addition rate can be controlled, and the crystallinity, heat resistance, thermal deterioration property, etc. depending on the hydrogen addition ratio can be controlled. The average hydrogen addition rate of the hydrogenated epoxy compound in the solder resist composition of the present invention is determined in consideration of the deterioration caused by the heat of the solder resist film and the maintenance of good heat resistance. Specifically, the average hydrogen addition rate is preferably from 50 to 100%, more preferably from 80 to 100%. The hydrogenated epoxy compound (C) is formulated in an amount relative to the carboxyl group-containing resin having no aromatic ring (A). 100 parts by mass is preferably 5 to 70 parts by mass, more preferably 5 to 60 parts by mass. When the amount of the hydrogenated epoxy compound (C) is more than 70 parts by mass, the solubility in the unexposed portion of the developing solution is lowered, and -13 to 1357536 is liable to cause development residue, which is practically difficult to use. In addition, when it is less than 5 parts by mass, the carboxyl group of the carboxyl group-containing resin (A) remains in an unreacted state. Therefore, it is difficult to sufficiently obtain the electrical properties, solder heat resistance, and drug resistance of the cured coating film. The carboxyl group of the carboxyl group-containing resin (A) having no aromatic ring and the epoxy group of the hydrogenated epoxy compound (C) are reacted by ring opening polymerization. The use of rutile-type titanium oxide (D) as a white pigment in the present invention is also one of the characteristics. The anatase type titanium oxide system is often used because it has a higher whiteness than the rutile type. However, anatase type titanium oxide sometimes causes discoloration of the resin in the solder resist composition due to photocatalytic activity. However, the rutile-type titanium oxide whiteness is slightly inferior to that of the anatase type, but has little photoactivity, so that a stable anti-solder film can be obtained. As the rutile-type titanium oxide (D), a known rutile-type titanium oxide can be used. Specifically, it is possible to use TR-600, TR-700, TR-750, TR-840, Ishihara Sho (R) 550, R-580 'R-630, R-820 manufactured by Fujitsu Industries Co., Ltd. , CR-50, CR-60, CR-90, KR-270, KR-310, KR-380, etc. made by Titanium Industry Co., Ltd. The amount of the rutile-type titanium oxide (D) is preferably 50 to 300 parts by mass, more preferably 60 to 260 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (A) having no aromatic ring. When the blending amount exceeds 300 parts by mass, the photocurability is lowered and the hardening depth is lowered, which is not preferable. On the other hand, if it is less than 50 parts by mass, the shielding force is small, and a high reflectance resist film cannot be obtained. Further, in the present invention, if the cerium oxide particles (F) are used, a solder resist composition having a deeper depth of hardening can be obtained. The refractive index of this dioxin-14- 1357536 ruthenium is considered to be close to that of the carboxyl group-containing resin (A). Such a cerium oxide particle (F) can be used by a known one. For example, spherical silica sand (Admafine SO-E1, SO-E2, SO-E5, etc., manufactured by Admatech Co., Ltd.), finely powdered cerium oxide, amorphous cerium oxide, crystalline cerium oxide, molten cerium oxide Wait. These cerium oxide particles may be used singly or in combination of two or more. The amount of the cerium oxide particles (F) is preferably 50 to 200 parts by mass based on 1 part by mass of the carboxyl group-containing resin (A) having no aromatic ring. The diluent (E) used in the present invention may, for example, be a photopolymerizable monomer and/or an organic solvent. Examples of the photopolymerizable monomer include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate; ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol. Mono- or diacrylates of iso-glycol: N,N-dimethyl decylamine, propylene oxime amines such as N-methylol acrylamide; N,N-dimethylaminoethyl acrylate Aminoalkyl acrylates such as esters; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyltrimeric isocyanate or the like, or such ethylene oxide or propylene oxide Polyhydric alcohols of adducts; phenoxy acrylates, bisphenol A diacrylates, and polyols of such phenolic ethylene oxide or propylene oxide adducts; glycerol diglycidyl ether, An acrylate of a glycidyl ether such as trimethylolpropane triglycidyl ether; a melamine acrylate; and/or a methacrylate corresponding to the above acrylate. Further, the organic solvent may, for example, be a ketone such as methyl ethyl ketone or cyclohexanone; an aromatic hydrocarbon such as toluene, xylene or tetramethylbenzene; methyl cellosolve, -15-1357536 ethyl cellosolve or butyl solution; Fibrin, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether; dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, etc. Ethers: esters of ethyl acetate, butyl acetate, cellosolve acetate, diethylene glycol monoethyl ether acetate, and esterified esters of the above glycol ethers; ethanol, propanol, B An alcohol such as a diol or a propylene glycol; an aliphatic hydrocarbon such as octane or decane; or a petroleum solvent such as petroleum ether, petroleum brain or hydrogenated petroleum brain. The diluent (E) as described above may be used singly or in combination of two or more. The diluent (E) is preferably used in an amount of from 2 to 3 parts by mass based on 100 parts by mass of the carboxyl group-containing resin (A) having no aromatic ring. The purpose of use of the above-mentioned diluent is that the photopolymerizable monomer is not only coated, but also the active energy ray-curable resin is diluted to enhance photopolymerization, and the organic solvent is dried to form a film. Therefore, depending on the diluent to be used, an exposure method in which either the contact method of the photomask is brought into contact with the coating film or the non-contact method can be used.
進一步，在本發明之白色之光硬化性及熱硬化性抗焊 阻劑組成物中，藉由含有抗氧化劑及抗阻胺系光安定劑， 俾可更減少熱劣化或光劣化。抗氧化劑並無特別限定，但 宜爲抗阻酚系化合物。抗阻酚系化合物可舉例如Nocrac 200、Nocrac Μ - 17' Nocrac SP、Nocrac S P - N、Nocrac NS- 5 ' Nocrac NS- 6、Nocrac NS - 30、Nocrac 3 00、 Nocrac NS - 7、Nocrac DAH (以上任一者均爲大內新興化 學工業（股）製）；MARK AO - 30、MARK AO - 40、 MARK AO - 50、MARK AO - 60、MARK AO - 616、MARK -16- 1357536 AO- 635 ' MARK AO- 658 ' MARK AO- 15 ' MARK AO -18、MARK AO - 328、MARK AO - 37 (以上任一者均爲 Adeka Argus 化學（股）製）；Irganox 245、Irganox 259 、 Irganox 565 、 Irganox 1010 、 Irganox 1035 、 Irganox 1 0 7 6、 Irganox 10 8 1 、 Irganox 1 0 9 8、 Irganox 1 2 2 2、 Irganox 1330、Irganox 1425WL (以上任一者均爲 Ciba Specialty Chemical 公司製）等。 又，抗阻胺系光安定劑可舉例如 Tinubin 622LD、 Tinubin 144 ： C ΗIM A S S O R B 9 4 4 LD、C ΗIM A S S O R B 1 1 9 F L (以上均爲 Ciba Specialty Chemical 公司製）；MARK LA - 57、LA - 62、LA - 67、L A - 6 3、LA - 6 8 (以上任一 者均爲 Adeka Argus 化學（股）製）；Sanol LS- 770、 LS - 765、LS - 292、LS - 2626、LS - 1114、LS - 744 (以 上任一者均爲三共Lifetech (股）製）等。 上述抗氧化劑及光安定劑係相對於不具有芳香環之含 羧基樹脂（A) 1〇〇質量份，宜添加〇.1〜1〇質量份。 進一步，依需要而可使用硬化劑促進劑、熱聚合抑制 劑、增黏劑、消泡劑、流平劑、偶合劑、耐燃助劑等。 本發明之白色之光硬化性及熱硬化性抗焊阻劑組成物 係可以液狀、糊料狀之形態提供。 使本發明之白色之光硬化性及熱硬化性抗焊阻劑組成 物依需要而稀釋以調整成適於塗佈方法之黏度。再於電路 形成之印刷配線板上，藉網版印刷法、簾塗法、噴塗法、 輥塗法等之方法進行塗佈’以例如7 0〜9 0。(：之溫度使組成 -17- 1357536 物中所含有之有機溶劑揮發乾燥，可形成不沾黏之塗膜。 其後，經由光罩而藉選擇性活性能量線進行曝光，使未曝 光部藉鹼水溶液進行顯像而形成光阻圖型，俾可得到本發 明之印刷配線板。此處所使用之鹼水溶液係一般爲0.5〜5 質量％的碳酸鈉水溶液，但亦可使用其他之鹼水溶液。其 他之鹼水溶液係可舉例如氫氧化鉀、氫氧化鈉、碳酸鉀、 磷酸鈉、矽酸鈉、氨、胺類等之鹼水溶液。又，用以曝光 之照射光源係可使用低壓水銀燈、中壓水銀燈、高壓水銀 燈、超高壓水銀燈、氙燈或金屬鹵素燈等。其他雷射光線 等亦可利用來作爲活性光線。 爲提昇如此做法所得到之抗焊阻劑膜的耐熱性，可藉 100〜2 00 °c之熱、紫外線或遠紅外線，使抗焊阻劑膜二次 硬化。 使用本發明之抗焊阻劑組成物所形成之抗焊阻劑膜係 具有高反射率、又，於抗焊阻劑所尋求之良好的密著性、 耐熱性、耐溶劑性以及電氣特性。又，以本發明所形成之 抗焊阻劑膜係加速劣化試驗後亦具有高的反射率。 【實施方式】 [實施例] 以下，依實施例說明本發明，但本發明係不限定於 此。 不具有芳香環之含羧基樹脂之合成 於具備攪拌機、溫度計、回流冷卻器、滴下漏斗及氮 -18- 1357536 氣導入管之2升分離式燒瓶中，加入作爲溶劑之二乙二醇 二甲基醚900g、及作爲聚合起始劑之第三丁基過氧化2-乙基己酸酯（日本油脂（股）製Perbutyl 0) 21.4g而加 熱至 90 °C »加熱後，再花 3小時滴下甲基丙烯酸 309.9g、甲基丙烯酸甲酯116.4g及內酯改性2 -羥乙基甲 基丙烯酸酯（Daicel化學工業（股）製Plaxel FM1 ) 109.8 g與聚合起始劑之雙（4 -第三丁基環己基）過氧化 二碳酸酯（曰本油脂（股）製Peroil TCP ) 21.4g而加 入。再進一步熟成6小時，俾得到含羧基之共聚合樹脂。 又，反應係在氮氣環境下實施。 然後，於所得到之含羧基共聚合樹脂中，加入3,4-環氧基環已基甲基丙烯酸酯（Daicel化學（股）製 Cyclomer A200 ) 3 63.9g、作爲開環觸媒之二甲苯甲基胺 3.6g、作爲聚合抑制劑之氫醌單甲基醚1.8 0g，加熱至100 °C，藉攪拌，進行環氧基的開環加成反應。1 6小時後，得 到含有固形分之酸價爲108.9 mgKOH/g、重量平均分子量 爲25000之不具有芳香環之含羧基樹脂 53.8質量％ (不 揮發成分）之溶液。以下，稱此反應溶液爲A - 1凡立 水。 實施例1〜3、比較例1〜4 依表1而調配攪拌各成分而以3根輥進行分散而分別 形成抗焊阻劑組成物。表中之數字表示質量份。 -19 - 1357536 [表i] 實施例1 實施例2 實施例3 比較例1 比較例2 比較例3 比較例4 A-1 凡立水 186 186 186 186 186 186 186 R820 180 180 180 180 180 180 KA-15 180 YX-8034 37 37 HBPA 37 YX-8300 37 TEPIC-H 19 TEPIC-S 19 828 37 SO-E5 110 110 110 110 110 110 110 起始劑 19 19 19 19 19 19 19 增感劑 0.3 0.3 0.3 0.3 0.3 0.3 0.3 單體 15 15 15 15 15 15 15 KS-66 3 3 3 3 3 3 3 溶劑 20 20 20 20 20 20 20 R820 :石原產業公司製金紅石型氧化鈦 KA- 15 :鈦工業公司製銳鈦礦型氧化鈦 YX - 8034 : Japan Epoxy Resin製 '氬化雙酣A型環氧樹月旨Further, in the white light-curable and thermosetting solder resist composition of the present invention, by containing an antioxidant and an amine-resistant light stabilizer, ruthenium can further reduce thermal deterioration or photodegradation. The antioxidant is not particularly limited, but is preferably an anti-resistance phenol compound. The hindered phenol-based compound may, for example, be Nocrac 200, Nocrac® 17' Nocrac SP, Nocrac SP-N, Nocrac NS-5' Nocrac NS-6, Nocrac NS-30, Nocrac 3 00, Nocrac NS-7, Nocrac DAH (Either of them are manufactured by Ou Nei Emerging Chemical Industry Co., Ltd.); MARK AO - 30, MARK AO - 40, MARK AO - 50, MARK AO - 60, MARK AO - 616, MARK -16 - 1357536 AO- 635 'MARK AO- 658 ' MARK AO- 15 ' MARK AO -18, MARK AO - 328, MARK AO - 37 (all of which are Adeka Argus Chemicals); Irganox 245, Irganox 259, Irganox 565 Irganox 1010, Irganox 1035, Irganox 1 0 7 6 , Irganox 10 8 1 , Irganox 1 0 9 8 , Irganox 1 2 2 2, Irganox 1330, Irganox 1425WL (all of which are manufactured by Ciba Specialty Chemical Co., Ltd.) and the like. Further, as the hindered amine light stabilizer, for example, Tinubin 622LD, Tinubin 144: C ΗIM ASSORB 9 4 4 LD, C ΗIM ASSORB 1 1 9 FL (all of which are manufactured by Ciba Specialty Chemical Co., Ltd.); MARK LA - 57, LA - 62, LA - 67, LA - 6 3, LA - 6 8 (all of which are manufactured by Adeka Argus Chemical Co., Ltd.); Sanol LS-770, LS-765, LS-292, LS-2626, LS - 1114, LS - 744 (all of the above are the three products of Lifetech). The antioxidant and the photosensitizer are preferably added in an amount of 0.1 part by mass to 1 part by mass based on 1 part by mass of the carboxyl group-containing resin (A) having no aromatic ring. Further, a hardener accelerator, a thermal polymerization inhibitor, a tackifier, an antifoaming agent, a leveling agent, a coupling agent, a flame resistant auxiliary agent, or the like can be used as needed. The white light-curing and thermosetting solder resist composition of the present invention can be provided in the form of a liquid or a paste. The white light-curable and thermosetting solder resist composition of the present invention is diluted as needed to adjust the viscosity suitable for the coating method. Further, on the printed wiring board formed by the circuit, coating is performed by a method such as screen printing, curtain coating, spray coating, roll coating, or the like, for example, 70 to 90. (The temperature is such that the organic solvent contained in the composition -17-1357536 is volatilized and dried to form a non-stick coating film. Thereafter, exposure is performed by a selective active energy ray through a photomask, so that the unexposed portion is borrowed. The aqueous alkali solution is developed to form a photoresist pattern, and the printed wiring board of the present invention can be obtained. The aqueous alkali solution used herein is generally a 0.5 to 5% by mass aqueous solution of sodium carbonate, but other aqueous alkali solutions can also be used. The other aqueous alkali solution may, for example, be an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium phosphate, sodium citrate, ammonia or an amine. Further, a low-pressure mercury lamp may be used for the illumination source for exposure. Pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, xenon lamp or metal halide lamp, etc. Other laser light can also be used as active light. To improve the heat resistance of the solder resist film obtained by this method, you can borrow 100~ 2 00 °c heat, ultraviolet light or far infrared ray to make the solder resist film secondary hardening. The solder resist film formed by using the solder resist composition of the present invention has high reflection Moreover, the excellent adhesion, heat resistance, solvent resistance and electrical properties sought for the solder resist. Moreover, the solder resist film formed by the present invention has high reflectance after accelerated degradation test. [Embodiment] [Examples] Hereinafter, the present invention will be described by way of Examples, but the present invention is not limited thereto. The synthesis of a carboxyl group-containing resin having no aromatic ring is provided with a stirrer, a thermometer, a reflux cooler, and a dropping funnel. And a 2 liter separation flask of a nitrogen-18-1357536 gas introduction tube, 900 g of diethylene glycol dimethyl ether as a solvent, and a third butyl peroxy 2-ethylhexanoate as a polymerization initiator Ester (Perbutyl 0, manufactured by Nippon Oil & Fats Co., Ltd.) 21.4g and heated to 90 °C. After heating, 309.9g of methacrylic acid, 116.4g of methyl methacrylate and lactone modified 2-hydroxyl were added for 3 hours. Base methacrylate (Plaxel FM1 manufactured by Daicel Chemical Industry Co., Ltd.) 109.8 g of bis(4-t-butylcyclohexyl)peroxydicarbonate with a polymerization initiator (Peroil TCP manufactured by 曰本油有限公司) ) 21.4g and added. Further matured into 6 small In the meantime, a carboxyl group-containing copolymer resin is obtained. Further, the reaction is carried out under a nitrogen atmosphere. Then, 3,4-epoxycyclohexyl methacrylate is added to the obtained carboxyl group-containing copolymer resin ( Daicel Chemical Co., Ltd. Cyclomer A200 ) 3 63.9 g, 3.6 g of xylene methylamine as a ring-opening catalyst, and 1.80 g of hydroquinone monomethyl ether as a polymerization inhibitor, heated to 100 ° C, stirred, The ring-opening addition reaction of the epoxy group was carried out. After 16 hours, a carboxyl group-containing resin having a solid content of 108.9 mgKOH/g and a weight average molecular weight of 25,000 and having no aromatic ring was obtained in an amount of 53.8 mass% (nonvolatile matter). ) a solution. Hereinafter, the reaction solution is referred to as A-1 vanilla water. Examples 1 to 3 and Comparative Examples 1 to 4 Each component was stirred and mixed according to Table 1, and dispersed by three rolls to form a solder resist composition. The numbers in the table indicate parts by mass. -19 - 1357536 [Table i] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 A-1 Fan Lishui 186 186 186 186 186 186 186 R820 180 180 180 180 180 180 KA -15 180 YX-8034 37 37 HBPA 37 YX-8300 37 TEPIC-H 19 TEPIC-S 19 828 37 SO-E5 110 110 110 110 110 110 110 Starting agent 19 19 19 19 19 19 19 Sensitizer 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Monomer 15 15 15 15 15 15 15 KS-66 3 3 3 3 3 3 3 Solvent 20 20 20 20 20 20 20 R820 : Rutile titanium oxide KA- 15 manufactured by Ishihara Sangyo Co., Ltd. Anatase-type titanium oxide YX - 8034 : Japan Epoxy Resin's 'argonized biguanide A type epoxy tree
HBPA :九善石油化學製、氫化雙酚A型環氧樹脂HPBA - DGE YX - 8300 : Japan Epoxy Resin製、氫化雙苯基型環氧樹月旨 TEPIC-H :日產化學（股）製召體三縮水甘油基三聚異氰酸酯 TEPIC-S :日產化學（股）製α體及/3體混合三縮水甘油基三聚異氰酸酯 828 : Japan Epoxy Resin 製、雙酣 Α 型 SO _ E5 : Admatech製球狀二氧化砂 起始劑：Ciba Specialty Chemicals 製 Irgacure 907HBPA: Jiushan Petrochemical, hydrogenated bisphenol A epoxy resin HPBA - DGE YX - 8300 : Japan Epoxy Resin, hydrogenated bisphenyl epoxy tree TEPIC-H: Nissan Chemical Co., Ltd. Triglycidyl trimeric isocyanate TEPIC-S: Nissan and /3 body mixed triglycidyl trimeric isocyanate 828 : Japan Epoxy Resin system, double 酣Α type SO _ E5 : Admatech spherical Sand dioxide starter: Irgacure 907 by Ciba Specialty Chemicals
增感劑：日本化藥製DETX 單體：二季戊四醇六丙烯酸酯 KS - 66 :信越Silicone製聚砂氧油 溶劑：卡必醇乙酸酯 使用各抗焊阻劑組成物所形成之抗焊阻劑膜的諸性 -20- 1357536 質，以如下般做法進行試驗，進行評估。 (1 )耐光性 使各抗焊阻劑組成物以1 〇〇mm X 1 50mm之大小於 1.6mm厚之FR - 4銅箱積層板以網板印刷法成爲膜厚40 之方式，使用100網目聚酯Bias製之版而以全面進 行印刷，以80°C於熱風循環式乾燥爐乾燥30分鐘。使用 印刷配線板用曝光機Oak製作所製HMW - 68 OGW，以殘 留30mm角之負圖型的方式，以500m J/cm2之積分光量進 行紫外線曝光，於30°C下使1 %之碳酸鈉水溶液作爲顯像 液，而以印刷配線板用顯像機顯像6 0秒，繼而，以1 5 0 T： 於熱風循環式乾燥爐熱硬化60分鐘，製作特性試驗用的 試驗片》 以M i η ο 11 a製色彩色差計C R - 4 0 0測定所得到之試驗 片。其後’照射UV輸送爐（輸出150 W/cm金屬鹵素燈 冷卻鏡）150J/cm2之光而加速光劣化。結果表示於表2 中〇 -21 - 1357536 [表2] 實施例1 實施例2 實施例3 比較例1 比較例2 比較例3 比較例4 初 期 値 Y 79.17 76.82 78.29 76.45 66.77 72.11 83.45 L* 91.31 90.24 90.91 90.07 85.37 88.02 93.21 a* -0.53 -0.52 -0.47 -0.31 -0.20 -0.82 -0.55 b* 4.26 3.46 3.02 4.57 4.05 4.42 0.36 150J /cm2 照射 Y 78.37 74.57 77.15 75.27 66.09 72.17 70.87 L* 90.95 89.19 90.39 89.52 85.04 88.05 87.42 a* 0.08 0.39 0.50 0.82 0.48 -2.13 0.87 b* 3.16 3.50 4.12 4.18 5.07 6.74 1.26 △E*ab 1.31 1.39 1.56 1.32 1.27 2.66 6.03 巨視評估 ◎ ◎ ◎ ◎ ◎ ◎ Δ 於表2中，Y表示 XYZ表色系之反射率，1/表示 表色系之亮度。〆表示紅方向、-a’表示綠方向， 表示黃方向，-1/表示藍方向，愈接近零，愈無彩度。 △ E、b表示顏色之變化。此値愈小，顏色之變化愈小。有 關目視評估項目係雙重圓圈表示感覺不到變色，圓符號表 示幾乎無變色，三角符號表示略變色，X符號表示有明顯 的變色。 比較例4係含有銳鈦礦型氧化鈦以取代金紅石型氧化 鈦者。銳鈦礦型氧化鈦從表2明顯地，初期之反射率高， 但加速光劣化後，反射率Y及亮度L*均大大地降低，顏 色之變化即△ E、b値變大。又，在目視評估中亦可看到變 色。從此事可知，金紅石型氧化鈦較銳鈦礦型氧化鈦作爲 高反射率之抗焊阻劑組成物成分優。 (2 )耐熱性 -22- 1357536 以Minolta製色彩色差計CR - 400測定與（1 )同樣 地製作之各試驗片。然後，在熱風循環式乾燥爐中，在 1 5 0°c加熱500小時、1 000小時而加速劣化。結果表示於 表3中。 [表3] 實施例1 實施例2 實施例3 比較例1 比較例2 比較例3 比較例4 初 期 値 Y 79.17 76.82 78.29 76.45 66.77 72.11 83.45 L* 91.31 90.24 90.91 90.07 85.39 88.02 93.21 a* -0.53 -0.52 -0.47 -0.31 -0.20 -0.82 -0.55 b* 4.26 3.46 3.02 4.57 4.05 4.42 0.36 150 Y 78.70 74.06 73.49 69.50 51.73 63.95 79.01 °c L* 91.10 88.95 88.68 86.75 77.12 83.94 91.24 500 a* -0.33 1.09 0.67 5.77 4.56 -1.10 -0.52 小 b* 6.58 5.05 4.39 15.99 12.20 10.72 3.46 時 △E*ab 2.34 2.60 2.85 13.36 12.55 7.51 3.67 後 巨視評估 ◎ ◎ ◎ X X X ◎ 150 Υ 74.97 71.55 71.28 63.3 48.47 60.13 74.57 °c L* 89.38 87.75 87.62 83.60 75.12 81.91 89.19 1000 a* -0.07 1.60 0.87 6.46 5.93 -1.25 1.39 小 b* 7.36 6.21 5.74 16.34 15.41 15.12 3.50 時 △E*ab 3.68 4.27 4.47 15.06 16.50 12.33 5.46 後 巨視評估 ◎ ◎ ◎ X X X 〇 從表3明顯可知，在使用本發明之組成物的實施例1 〜3中，加速劣化後，反射率亦不降低，亮度之變化亦 小，及顏色之變化即△ E # ab之値小。又，即使目視評估亦 完全無變色，或幾乎無。 比較例1〜3係使用氫化環氧化合物以外的環氧化合 -23- 1357536 物者。從表3可知，於抗焊阻劑組成物中含有氫化環氧化 合物以外的環氧化合物之組成物係加速熱劣化後，反射率 Y及亮度1/均大大地降低，及顏色之變化即△ E、b値亦 大。又’即使在目視評估亦可看到變色。從此事可知若於 抗焊阻劑組成物之樹脂中使用氫化環氧化合物以外的環氧 化合物’抗焊阻劑膜會受熱劣化。 (3 )耐溶劑性 將與（1 )同樣地製作之各試驗片浸漬於丙二醇單甲 基醚乙酸酯30分鐘，乾燥後，以賽珞吩黏著膠帶進行剝 離測試，評估有關塗膜之剝離與變色。結果一倂表示於表 4中。此處，圓符號係無塗膜之剝離或變色，X符號係有 塗膜之剝離或變色。 (4 )鉛筆硬度試驗 在與（1)同樣地製作之各試驗片中，以筆芯之前端 變平之方式從被硏磨之B至9H之鉛筆以約45°之角度押 抵，而記錄不產生塗膜剝離之鉛筆的硬度。結果一倂表示 於表4中。 (5 )絕緣電阻試驗 除使用IP C B - 25測試圖型的梳型電極B金屬片取代 FR - 4銅箔積層板以外，其餘係與（1 )同樣的條件製作 試驗片。對此試驗片施加DC500V之偏壓，測定絕緣電阻 -24 - 1357536 値。結果一倂表示於表4中。 [表4] 實施例1 實施例2 實施例3 比較例1 比較例2 比較例3 比較例4 耐溶劑性 〇 〇 〇 〇 〇 〇 〇 鉛筆硬 度試驗 7H 7H 7H 7H 7H 7H 7H 絕緣電 阻試驗 (Ω ) lxlO13 以上 lxlO13 以上 lxlO13 以上 lxlO13 以上 5xl012 lxlO12 lxlO13 以上 從表4明顯可知，在使用本發明之抗焊阻劑組成物的 實施例1〜3中，具有抗焊阻劑膜所要求之良好的耐熱 性、耐溶劑性、密著性及電絕緣性。 如以上詳述般，若依本發明，可得到能形成高反射率 之抗焊阻劑膜的光硬化性及熱硬化性之白色抗焊阻劑組成 物。藉本發明之抗焊阻劑組成物所形成之高反射率的抗焊 阻劑膜，不易受光劣化及熱劣化，並可承受長期間之使 用。 -25-Sensitizer: DETX monomer made from Nippon Kayaku Co., Ltd.: Dipentaerythritol hexaacrylate KS-66: Synthetic Silicone Solvent made by Shinco Silicone: Anti-weld resistance formed by each anti-solder resist composition of carbitol acetate The properties of the film were -20-1357536, and the test was carried out as follows. (1) Light resistance: Each of the solder resist compositions is used in a manner of 1 〇〇mm X 1 50 mm in a 1.6 mm thick FR - 4 copper box laminate by screen printing to a film thickness of 40, using 100 mesh The polyester Bias plate was printed in full and dried in a hot air circulating drying oven at 80 ° C for 30 minutes. HMW-68 OGW manufactured by the exposure machine Oak was produced by using a printed wiring board, and ultraviolet light exposure was performed at an integrated light amount of 500 mJ/cm2 in a negative pattern of a residual angle of 30 mm, and a 1% sodium carbonate aqueous solution was made at 30 ° C. As a developing liquid, it was developed by a developing machine for a printed wiring board for 60 seconds, and then thermally cured in a hot air circulating drying oven for 60 minutes at 150 °T to prepare a test piece for characteristic test. η ο 11 a chromatic color difference meter CR-400 measured the obtained test piece. Thereafter, the light was irradiated to a UV transfer furnace (output 150 W/cm metal halide lamp cooling mirror) at 150 J/cm 2 to accelerate photodegradation. The results are shown in Table 2 〇-21 - 1357536 [Table 2] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Initial 値Y 79.17 76.82 78.29 76.45 66.77 72.11 83.45 L* 91.31 90.24 90.91 90.07 85.37 88.02 93.21 a* -0.53 -0.52 -0.47 -0.31 -0.20 -0.82 -0.55 b* 4.26 3.46 3.02 4.57 4.05 4.42 0.36 150J /cm2 Irradiation Y 78.37 74.57 77.15 75.27 66.09 72.17 70.87 L* 90.95 89.19 90.39 89.52 85.04 88.05 87.42 a* 0.08 0.39 0.50 0.82 0.48 -2.13 0.87 b* 3.16 3.50 4.12 4.18 5.07 6.74 1.26 △E*ab 1.31 1.39 1.56 1.32 1.27 2.66 6.03 Ju Vision Evaluation ◎ ◎ ◎ ◎ ◎ ◎ Δ In Table 2, Y indicates XYZ color The reflectance of the system, 1 / represents the brightness of the color system. 〆 indicates the red direction, -a' indicates the green direction, indicates the yellow direction, and -1/ indicates the blue direction. The closer to zero, the less chroma. △ E, b represent the change in color. The smaller the sputum, the smaller the change in color. Regarding the visual evaluation item, the double circle indicates that no discoloration is felt, the circle symbol indicates almost no discoloration, the triangular symbol indicates slight discoloration, and the X symbol indicates significant discoloration. Comparative Example 4 contains an anatase type titanium oxide in place of rutile type titanium oxide. The anatase type titanium oxide is apparent from Table 2, and the initial reflectance is high. However, after the accelerated photodegradation, the reflectance Y and the luminance L* are greatly lowered, and the change in color, that is, Δ E and b 値 becomes large. Also, the color change can be seen in the visual evaluation. From this, it is known that rutile-type titanium oxide is superior to anatase-type titanium oxide as a composition of a high reflectance anti-solder resist composition. (2) Heat resistance -22 - 1357536 Each test piece prepared in the same manner as (1) was measured with a Minolta colorimeter CR-400. Then, in a hot air circulating type drying furnace, heating was performed at 150 ° C for 500 hours and 1,000 hours to accelerate deterioration. The results are shown in Table 3. [Table 3] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Initial 値Y 79.17 76.82 78.29 76.45 66.77 72.11 83.45 L* 91.31 90.24 90.91 90.07 85.39 88.02 93.21 a* -0.53 -0.52 -0.47 -0.31 -0.20 -0.82 -0.55 b* 4.26 3.46 3.02 4.57 4.05 4.42 0.36 150 Y 78.70 74.06 73.49 69.50 51.73 63.95 79.01 °c L* 91.10 88.95 88.68 86.75 77.12 83.94 91.24 500 a* -0.33 1.09 0.67 5.77 4.56 -1.10 -0.52 small b* 6.58 5.05 4.39 15.99 12.20 10.72 3.46 △E*ab 2.34 2.60 2.85 13.36 12.55 7.51 3.67 Posterior assessment ◎ ◎ ◎ XXX ◎ 150 Υ 74.97 71.55 71.28 63.3 48.47 60.13 74.57 °c L* 89.38 87.75 87.62 83.60 75.12 81.91 89.19 1000 a* -0.07 1.60 0.87 6.46 5.93 -1.25 1.39 small b* 7.36 6.21 5.74 16.34 15.41 15.12 3.50 △E*ab 3.68 4.27 4.47 15.06 16.50 12.33 5.46 Post-Giant evaluation ◎ ◎ ◎ XXX 〇 From Table 3, it is obvious that In Examples 1 to 3 in which the composition of the present invention is used, after the deterioration is accelerated, the reflectance is not lowered, the change in brightness is small, and the change in color is Small E # ab of Zhi. Moreover, even if the visual assessment is completely discolored, or almost nothing. In Comparative Examples 1 to 3, those of the epoxidized -23- 1357536 other than the hydrogenated epoxy compound were used. As is clear from Table 3, the composition of the epoxy compound other than the hydrogenated epoxy compound in the solder resist composition accelerates thermal deterioration, and the reflectance Y and the luminance 1 are greatly lowered, and the change in color is Δ. E, b is also big. Also, discoloration can be seen even in visual evaluation. From this, it is understood that if the epoxy compound other than the hydrogenated epoxy compound is used as the resin of the solder resist composition, the solder resist film is thermally deteriorated. (3) Solvent resistance Each test piece prepared in the same manner as (1) was immersed in propylene glycol monomethyl ether acetate for 30 minutes, and after drying, a peeling test was performed with a celesta adhesive tape to evaluate peeling of the coating film. With discoloration. The results are shown in Table 4. Here, the circle symbol is free from peeling or discoloration of the coating film, and the X symbol is peeling or discoloration of the coating film. (4) Pencil hardness test In each test piece prepared in the same manner as (1), the pencil of the honed B to 9H was taken at an angle of about 45° in such a manner that the front end of the refill was flattened, and the recording was performed. The hardness of the pencil which does not peel off the film is produced. The results are shown in Table 4. (5) Insulation resistance test A test piece was produced under the same conditions as (1) except that the comb-shaped electrode B metal piece of the IP C B-25 test pattern was used instead of the FR-4 copper foil laminated plate. A bias voltage of DC500V was applied to the test piece, and the insulation resistance was measured to be -24 - 1357536 値. The results are shown in Table 4. [Table 4] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Solvent Resistance 〇〇〇〇〇〇〇 Pencil Hardness Test 7H 7H 7H 7H 7H 7H 7H Insulation Resistance Test (Ω lxlO13 or more lxlO13 or more lxlO13 or more lxlO13 or more 5xl012 lxlO12 lxlO13 From the above, it is apparent from Table 4 that in Examples 1 to 3 using the solder resist composition of the present invention, the heat resistance required for the solder resist film is good. Properties, solvent resistance, adhesion and electrical insulation. As described in detail above, according to the present invention, a photohardenability and thermosetting white solder resist composition capable of forming a high reflectance solder resist film can be obtained. The high reflectance solder resist film formed by the solder resist composition of the present invention is less susceptible to photodegradation and thermal deterioration and can be used for a long period of time. -25-