CN105694582A - 一种光固化阻焊油墨 - Google Patents

一种光固化阻焊油墨 Download PDF

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CN105694582A
CN105694582A CN201410708692.5A CN201410708692A CN105694582A CN 105694582 A CN105694582 A CN 105694582A CN 201410708692 A CN201410708692 A CN 201410708692A CN 105694582 A CN105694582 A CN 105694582A
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CN105694582B (zh
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赵文超
王辰龙
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Yingli Science And Technology Development Co Ltd Beijing
Insight High Technology Beijing Co Ltd
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Abstract

本发明涉及一种光固化阻焊油墨，其含有：(A)碱溶性树脂，(B)至少一种式(Ⅰ)的光引发剂化合物，(C)分子中具有烯键式不饱和基团的化合物，(D)颜料

Description

一种光固化阻焊油墨
技术领域
本发明涉及一种光固化阻焊油墨的组成及阻焊膜的形成方法，将光固化组合物涂布到基材上使其干燥后，通过掩膜板对该干燥涂膜照射紫外光后，通过碱性水溶液显影而形成阻焊膜图案。
背景技术
在印刷线路板中，电子元件安装在其上预先形成有导电电路图案的印刷电路基材的焊接区上，而焊接区外的所有电路区域都被作为永久保护膜的阻焊膜覆盖。这样，在将电子元件焊接到印刷电路板上时，就可避免焊料粘在无需被焊料覆盖的区域上，并防止构成电路图案的导体因直接暴露于空气中而氧化。
目前，阻焊膜中应用较多的是光固化阻焊油墨。光固化阻焊油墨的使用方法一般为首先将涂膜层在较低温度下烘烤以使溶剂挥发，再利用紫外光照射使其预固化，然后通过稀的碱性水溶液显影，形成图案，之后对涂膜进行高温热固化，最终形成阻焊膜。
现有阻焊油墨中普遍使用的光引发剂如：907、DETX、IRGACUREOXE02或其组合物，它们在图案尺寸的精准度和图案边缘的齐整度方面仍存在欠缺，需要改进。
发明内容
本发明的目的在于，提供一种光固化阻焊油墨，涂布后经曝光和显影得到了图案尺寸更精准、图案边缘更加齐整的阻焊膜。
本发明的光固化阻焊油墨，含有：
(A)碱溶性树脂
(B)光引发剂
(C)分子中具有烯键式不饱和基团的化合物
(D)颜料，
另外可含有(E)溶剂及(F)表面活性剂和(G)填料等非特征性的常规组分。
碱溶性树脂是具有一定酸值特性的树脂，酸值范围一般是30-300mg/gKOH，重均分子量范围在2000-150000。在组合物中质量份数为100份。
一种碱溶性树脂的制备：将甲基丙烯酸苄酯180g、甲基丙烯酸60g、甲基丙烯酸羟乙酯60g、偶氮二异丁腈15g、十二硫醇6g与甲苯1000ml混匀并放入恒压滴液漏斗中；将1000ml甲苯放入三口烧瓶，安装搅拌、恒压滴液漏斗和温度计，开启搅拌，用氮气置换烧瓶中气体；加热烧瓶使溶剂温度达到80‐85℃，保温，开始滴加引发剂溶液，约1h滴完；继续反应6h；自然冷却降温，停止搅拌，等树脂沉降后，吸取上部澄清溶液，过滤下部含溶剂的树脂，并用500ml甲苯淋洗树脂滤饼；减压烘干滤饼，得到白色粉末状固体树脂250g。
光引发剂是吸收光能引起膜层固化的关键组分，其中至少含有一种选自式(Ⅰ)所示的环戊二酮肟酯光引发剂，
其中，
Ar1为取代的邻亚芳基或邻亚杂芳基，该邻亚芳基或邻亚杂芳基以相邻的两个原子与Y1和羰基相连构成并环结构，除R18X取代基外其余原子上的取代基各自独立地为：
氢原子，卤素原子，C1‐C12烷基，C5‐C7环烷基，被C5‐C7环烷基取代的C1‐C4烷基，苯基，任意被一个或多个C1‐C4烷基、羧基、C1‐C12烷基酰基、芳基甲酰基、杂芳基甲酰基、苯基、卤素原子、CN取代的苯基，C1‐C4烷基苄氧基，R1C(O)O取代的C1‐C4烷氧基，C1‐C3亚烷基二氧基，R1C(O)O，C1‐C12烷基硫基，C1‐C4烷基苯硫基，R1C(O)O取代的C1‐C4烷基硫基，CN，羧基，C1‐C12烷氧基甲酰基，芳基甲酰基，杂芳基甲酰基，XR18；
或Ar1的上述取代基中相邻的两个取代基之间或者取代基与Ar1之间通过直键、碳原子、羰基相连构成环状结构；
X为O，S或NR19；
Y1为O，S，NR20，BR20，CR15R16，SiR15R16；
R1为氢原子，C1‐C18烷基或C1‐C18烷氧基，任意被一个或多个卤素原子、C1‐C4烷基、C5‐C7环烷基、杂环烷基、苯基、杂芳基、CN、C1‐C4烷酰氧基、芳酰氧基取代和/或被C5‐C7环亚烷基、亚苯基、O、S、NR17插入的C2‐C18烷基，C2‐C18烯基，任意被一个或多个卤素原子、C1‐C4烷基、C5‐C7环烷基、杂环烷基、苯基、杂芳基、CN、C1‐C4烷酰氧基、芳酰氧基取代和/或被C5‐C7环亚烷基、亚苯基、O、S、NR17插入的C2‐C18烯基；
或R1为C5‐C7环烷基，任意被一个或多个C1‐C4烷基、苯基、卤素原子、CN取代的C5‐C7环烷基；或R1为苯基，任意被一个或多个C1‐C4烷基、C1‐C4烷氧基、苯基、卤素原子、CN取代的苯基；或R1为萘基；或R1为苯甲酰基，苯氧基羰基，其中苯基任意被一个或两个以上卤素原子、R17、C5或C6环烷基、CN、OH、XR17取代；
R17为C1‐C4烷基；
R18为氢原子，C1‐C18烷基，C1‐C4烷氧基酰基取代的C1‐C5烷基，R1C(O)O取代的C1‐C4烷基，任意被一个或多个卤素原子、C1‐C4烷基、C5‐C7环烷基、杂环烷基、苯基、杂芳基、CN、C1‐C4烷酰氧基、芳酰氧基取代或被C5‐C7亚环烷基、亚苯基、O、S、NR17插入的C2‐C18烷基；或R18为C5‐C7环烷基，或任意被一个或多个C1‐C4烷基、苯基、卤素原子、CN取代的C5‐C7环烷基；或R18为苯基，任意被一个或多个C1‐C12烷基、羧基、C1‐C12烷基酰基、有亚苯基、O、S、NR17插入的C2‐C12烷基酰基、C5‐C6环烷基甲酰基、C5‐C6环烷基取代的C2‐C4烷基酰基、芳基甲酰基、杂芳基甲酰基、XR17、苯基、卤素原子、CN、NO2取代的苯基；
或R18为C1‐C4烷基酰基、C1‐C4共轭烯酰基、苯甲酰基、苯氧基羰基，其中苯基任意被一个或两个以上卤素原子、R17、C5或C6环烷基、CN、OH、XR17取代；
或上述R18通过直键、碳原子、羰基与Ar1或Ar2中的芳环相连构成新的环。
上述式(Ⅰ)所示环戊二酮肟酯光引发剂具体为式(Ⅱ)或式(Ⅲ)化合物。
该光固化阻焊油墨中还可以含有作为共引发剂的其他市售产品，例如选自α‐氨基酮类、硫杂蒽酮类、酰基氧化膦类、二苯甲酮类、咔唑肟酯类、芳基‐1,2‐二酮‐2‐肟酯类光引发剂；这些类光引发剂具体的化合物可以为：
2‐甲基‐2‐(4‐吗啉基)‐1‐[4‐(甲硫基)苯基]‐1‐丙酮，2‐二甲基氨基‐2‐苄基‐1‐(4‐吗啉基苯基)‐1‐丁酮，2‐异丙基噻吨酮，2,4‐二乙基噻吨酮，2,4,6‐三甲基苯甲酰基二苯基氧化膦，二(2,4,6‐三甲基苯甲酰基)苯基氧化膦，4,4’‐二(二甲氨基)二苯甲酮，9‐乙基‐6‐(2‐甲基苯甲酰基)咔唑‐3‐乙酮肟‐O‐乙酸酯，9‐乙基‐6‐(2‐甲基苯甲酰基)咔唑‐3‐(3‐环戊基)丙酮肟‐O‐乙酸酯，1‐(4‐苯硫基)苯基‐1,2‐辛二酮‐2‐肟‐O‐苯甲酸酯，
该光固化阻焊油墨中还含有成分(C)，即分子中具有烯键式不饱和基团的化合物，例如丙烯酸酯类化合物，具体的例子有新戊二醇二丙烯酸酯，二季戊四醇六丙烯酸酯，季戊四醇三丙烯酸酯，季戊四醇四丙烯酸酯，三羟甲基丙烷三丙烯酸酯，乙氧基化三羟甲基丙烷三丙烯酸酯，丙氧基化三羟甲基丙烷三丙烯酸酯，三甘醇二丙烯酸酯，二缩三丙二醇二丙烯酸酯，1,6‐己二醇二丙烯酸酯，新戊二醇二丙烯酸酯，1,4‐丁二醇二丙烯酸酯及环氧丙烯酸酯等。
该光固化阻焊油墨中的成分还有：
(D)颜料，例如酞青绿等颜料及颜料分散体；
(E)溶剂，例如丙二醇甲醚醋酸酯，二丙二醇甲醚醋酸酯，乙二醇乙醚醋酸酯，甲苯，二甲苯，四甲基苯，甲基异丁酮，环己酮，乙酸乙酯，乙酸丁酯，γ‐丁内酯，丙二醇单甲醚，二丙二醇二乙醚等；
(F)表面活性剂，例如含硅消泡剂，颜料分散剂。
(G)填料，例如碳酸钡，硫酸钡，滑石粉，高岭土，石英粉，碳酸镁，碳酸钙，氢氧化铝，钛酸钡，
硅酸铝，硅酸钙，锌白，二氧化钛等。
光固化阻焊油墨中组分(A)碱溶性树脂用量100份质量；(B)光引发剂用量10‐50份质量；(C)分子中具有烯键式不饱和基团的化合物用量40‐200份质量；(D)颜料，用量2‐50份质量。
其他成分(E)溶剂，用量100‐300份质量；(F)表面活性剂和(G)填料用量为适合组合物应用的常规用量。
光固化阻焊油墨适合用作厚度为15‐100μm的干燥涂膜。还可以制成一种干膜，即是将光固化阻焊油墨涂布到基材上后进行干燥而得到的。
干燥的涂膜上覆盖掩膜板，经紫外光曝光后，在碱性显影液中显影，洗去未曝光部分，得到保留的阻焊膜。
紫外线光源一般的是高压汞灯，常用具有365nm发射波长的汞灯或经过光栅过滤的365nm光线。
具体的碱性显影液是氨水、氢氧化钠溶液、氢氧化钾溶液、碳酸钠溶液或碳酸钾溶液等，可以将未曝光的膜层溶解清洗掉。
采用本发明阻焊油墨得到的阻焊膜，具有如下优点：图案尺寸更精准，显影后图案边缘更洁净整齐。
具体实施方式
实施例1
1)阻焊油墨配制：
用表1所示的量(质量份)配合表1所示的成分，并搅拌，混合使其分散，分别得到光固化阻焊油墨配方A-E。
表1
2)阻焊膜成膜过程：
将各个光固化阻焊油墨配方丝网印刷至经去氧化处理的覆铜板上，使用热风循环干燥箱，在75℃下干燥40min，干燥后，缓慢冷却至室温，在其上固定描绘有线宽为20μm及150μm线宽图案的光掩膜，用汞灯以150mJ/cm2的曝光量进行正面曝光，利用1wt％的Na2CO3水溶液以喷压0.25MPa、温度30℃显影90s后，水洗吹干。
3)阻焊膜性能评价：
边缘整齐度评价：
用100倍体式显微镜观察样板图案边缘整齐度。其结果示于表2。判定基准如下：
◎边缘整齐、无破损及多余物、清晰；
○边缘较整齐、边缘有少量锯齿；
△边缘较不整齐、边缘有较多锯齿；
×边缘不整齐或边缘不清晰。
图案精准度评价
用100倍体式显微下测量样板显影图像线宽，并与掩膜图案线宽进行比较。其结果示于表2。判定基准如下：
150μm图案精准度评价：
◎图像尺寸在掩膜尺寸±10％之内；
○图像尺寸在掩膜尺寸±15％之内；
△图像尺寸在掩膜尺寸±20％之内；
×图像尺寸<掩膜尺寸-20％或图像尺寸>掩膜尺寸+20％。20μm图案精准度评价：
◎图像尺寸在掩膜尺寸±5％之内；
○图像尺寸在掩膜尺寸±10％之内；
△图像尺寸在掩膜尺寸±15％之内；
×图像尺寸<掩膜尺寸-15％或图像尺寸>掩膜尺寸+15％。
表2
结论：使用了5-(4-异丙基苯硫基)茚满-1,2-二酮-2-肟-O-乙酸酯的配方A及5-(正丁氧基)茚满-1,2-二酮-2-肟-O-乙酸酯的配方B，边缘齐整度和图案精准度是最优的。
实施例2
更换曝光光源为365nmLED灯，其他过程与实施例1相同，结果列于表3
表3
结论：使用了5-(4-异丙基苯硫基)茚满-1,2-二酮-2-肟-O-乙酸酯的配方A及5-(正丁氧基)茚满-1,2-二酮-2-肟-O-乙酸酯的配方B，在测试中的综合效果较配方C、D、E更好。

Claims (7)

1.一种光固化阻焊油墨，含有：
(A)碱溶性树脂，重量比例是100份；
(B)光引发剂，重量比例是10‐50份；
(C)分子中具有烯键式不饱和基团的化合物，重量比例是40‐200份；
(D)颜料，重量比例是2‐50份；
其特征在于，光引发剂(B)至少含有一种选自式(Ⅰ)所示的环戊二酮肟酯光引发剂，
其中，
Ar1为取代的邻亚芳基或邻亚杂芳基，该邻亚芳基或邻亚杂芳基以相邻的两个原子与Y1和羰基相连构成并环结构，除R18X取代基外其余原子上的取代基各自独立地为：
氢原子，卤素原子，C1‐C12烷基，C5‐C7环烷基，被C5‐C7环烷基取代的C1‐C4烷基，苯基，任意被一个或多个C1‐C4烷基、羧基、C1‐C12烷基酰基、芳基甲酰基、杂芳基甲酰基、苯基、卤素原子、CN取代的苯基，C1‐C4烷基苄氧基，R1C(O)O取代的C1‐C4烷氧基，C1‐C3亚烷基二氧基，R1C(O)O，C1‐C12烷基硫基，C1‐C4烷基苯硫基，R1C(O)O取代的C1‐C4烷基硫基，CN，羧基，C1‐C12烷氧基甲酰基，芳基甲酰基，杂芳基甲酰基，XR18；
或Ar1的上述取代基中相邻的两个取代基之间或者取代基与Ar1之间通过直键、碳原子、羰基相连构成环状结构；
X为O，S或NR19；
Y1为O，S，NR20，BR20，CR15R16，SiR15R16；
R1为氢原子，C1‐C18烷基或C1‐C18烷氧基，任意被一个或多个卤素原子、C1‐C4烷基、C5‐C7环烷基、杂环烷基、苯基、杂芳基、CN、C1‐C4烷酰氧基、芳酰氧基取代和/或被C5‐C7环亚烷基、亚苯基、O、S、NR17插入的C2‐C18烷基，C2‐C18烯基，任意被一个或多个卤素原子、C1‐C4烷基、C5‐C7环烷基、杂环烷基、苯基、杂芳基、CN、C1‐C4烷酰氧基、芳酰氧基取代和/或被C5‐C7环亚烷基、亚苯基、O、S、NR17插入的C2‐C18烯基；
或R1为C5‐C7环烷基，任意被一个或多个C1‐C4烷基、苯基、卤素原子、CN取代的C5‐C7环烷基；或R1为苯基，任意被一个或多个C1‐C4烷基、C1‐C4烷氧基、苯基、卤素原子、CN取代的苯基；或R1为萘基；或R1为苯甲酰基，苯氧基羰基，其中苯基任意被一个或两个以上卤素原子、R17、C5或C6环烷基、CN、OH、XR17取代；
R17为C1‐C4烷基；
R18为氢原子，C1‐C18烷基，C1‐C4烷氧基酰基取代的C1‐C5烷基，R1C(O)O取代的C1‐C4烷基，任意被一个或多个卤素原子、C1‐C4烷基、C5‐C7环烷基、杂环烷基、苯基、杂芳基、CN、C1‐C4烷酰氧基、芳酰氧基取代或被C5‐C7亚环烷基、亚苯基、O、S、NR17插入的C2‐C18烷基；或R18为C5‐C7环烷基，或任意被一个或多个C1‐C4烷基、苯基、卤素原子、CN取代的C5‐C7环烷基；或R18为苯基，任意被一个或多个C1‐C12烷基、羧基、C1‐C12烷基酰基、有亚苯基、O、S、NR17插入的C2‐C12烷基酰基、C5‐C6环烷基甲酰基、C5‐C6环烷基取代的C2‐C4烷基酰基、芳基甲酰基、杂芳基甲酰基、XR17、苯基、卤素原子、CN、NO2取代的苯基；
或R18为C1‐C4烷基酰基、C1‐C4共轭烯酰基、苯甲酰基、苯氧基羰基，其中苯基任意被一个或两个以上卤素原子、R17、C5或C6环烷基、CN、OH、XR17取代；
或上述R18通过直键、碳原子、羰基与Ar1或Ar2中的芳环相连构成新的环。
2.根据权利要求1所述的光固化阻焊油墨，其特征在于，所述式(Ⅰ)环戊二酮肟酯光引发剂为式(Ⅱ)或式(Ⅲ)化合物。
3.根据权利要求1所述的光固化阻焊油墨，其中组分B还含其他光引发剂作为共同引发剂，其他光引发剂选自α‐氨基酮类、硫杂蒽酮类、酰基氧化膦类、二苯甲酮类、咔唑肟酯类或芳基‐1,2‐二酮‐2‐肟酯。
4.根据权利要求3所述的光固化阻焊油墨，其他光引发剂的具体化合物为：
2‐甲基‐2‐(4‐吗啉基)‐1‐[4‐(甲硫基)苯基]‐1‐丙酮，2‐二甲基氨基‐2‐苄基‐1‐(4‐吗啉基苯基)‐1‐丁酮，2‐异丙基噻吨酮，2,4‐二乙基噻吨酮，2,4,6‐三甲基苯甲酰基二苯基氧化膦，二(2,4,6‐三甲基苯甲酰基)苯基氧化膦，4,4’‐二(二甲氨基)二苯甲酮，9‐乙基‐6‐(2‐甲基苯甲酰基)咔唑‐3‐乙酮肟‐O‐乙酸酯，9‐乙基‐6‐(2‐甲基苯甲酰基)咔唑‐3‐(3‐环戊基)丙酮肟‐O‐乙酸酯或1‐(4‐苯硫基)苯基‐1,2‐辛二酮‐2‐肟‐O‐苯甲酸酯。
5.权利要求1‐4所述的光固化阻焊油墨，其特征在于，还含有：
(E)溶剂，用量100‐300份质量。
6.权利要求1所述的光固化阻焊油墨，用作干燥后厚度为15～100μm的涂膜，该涂膜在经过掩膜曝光后通过稀碱溶液显影形成图案。
7.一种干膜，其是将权利要求1所述的光固化阻焊油墨涂布到基材上后进行干燥而得到的。
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WO2015027702A1 (zh) 2015-03-05
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