CN110515269A - 感光树脂组合物及其制备方法、高分子膜及覆铜板 - Google Patents

感光树脂组合物及其制备方法、高分子膜及覆铜板 Download PDF

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CN110515269A
CN110515269A CN201810495434.1A CN201810495434A CN110515269A CN 110515269 A CN110515269 A CN 110515269A CN 201810495434 A CN201810495434 A CN 201810495434A CN 110515269 A CN110515269 A CN 110515269A
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颜振锋
向首睿
吴佩蓉
苏赐祥
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Zhending Technology Co Ltd
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Abstract

一种感光树脂组合物,按重量份数计,包括100份的化学结构式为的改性的聚酰亚胺类聚合物、10~40份的感光单体、10~25份的双酚A型环氧树脂、1~10份的光起始剂以及1~5份的色料,其中,该改性的聚酰亚胺类聚合物由化学结构式为的聚酰亚胺类聚合物中与R基团键接的羧基与甲基丙烯酸缩水甘油酯中的环氧基反应制得,该聚酰亚胺类聚合物由含有A基团的双酐单体与含有R基团的二胺单体、含有R1基团的二胺单体及含有R2基团的二胺单体反应而成,该含有R基团的二胺单体为在R基团上键接有羧基的二胺化合物,该含有R1基团的二胺单体为柔软的长链状的二胺单体,R2基团包含至少一仲胺基团或叔胺基团,x、y及z分别为大于或等于1的自然数。

Description

感光树脂组合物及其制备方法、高分子膜及覆铜板
技术领域
本发明涉及一种树脂组合物,尤其涉及一种感光树脂组合物及其制备方法,以及应用该感光树脂组合物的高分子膜及覆铜板。
背景技术
目前,现有技术中的感光树脂组合物大部分以PU亚克力树脂为主,而以PU亚克力树脂为主的感光树脂组合物形成的高分子膜并不耐热,往往需要在感光树脂组合物中添加环氧树脂来提高形成的高分子膜的耐热性,然而,所述高分子膜的挠曲性将因环氧树脂的添加而呈明显下降趋势。另外,将感光树脂组合物应用于光刻技术中时,为了使感光树脂组合物形成的高分子膜膜面稳固不易被碱液侵蚀,需要利用化学增幅法来改善此问题,因此,制程流程中会增加曝光后烘焙(PEB)的流程,从而使得感光树脂组合物的应用上有所限制,并且增加了成本。
发明内容
有鉴于此,有必要提供一种成膜后耐碱性、耐热性及挠曲性好的感光树脂组合物,从而解决以上问题。
另,还有必要提供一种所述感光树脂组合物的制备方法。
另,还有必要提供一种应用所述感光树脂组合物的高分子膜及覆铜板。
本发明实施方式提供一种感光树脂组合物,按重量份数计,包括100份的改性的聚酰亚胺类聚合物、10~40份的感光单体、10~25份的双酚A型环氧树脂、1~10份的光起始剂以及1~5份的色料,其中,所述改性的聚酰亚胺类聚合物的化学结构式为
其由化学结构式为
的聚酰亚胺类聚合物中与R基团键接的羧基与甲基丙烯酸缩水甘油酯中的环氧基反应制得,所述聚酰亚胺类聚合物由含有A基团的双酐单体与含有R基团的二胺单体、含有R1基团的二胺单体以及含有R2基团的二胺单体反应聚合而成,所述含有R基团的二胺单体为在R基团上键接有羧基的二胺化合物,所述含有R1基团的二胺单体为柔软的长链状的二胺单体,R2基团包含至少一仲胺基团或叔胺基团,其中,x、y及z分别为大于等于1的自然数。
本发明实施方式还提供一种如上所述的感光树脂组合物的制备方法,其包括如下步骤:
将所述改性的聚酰亚胺类聚合物、所述感光单体、所述双酚A型环氧树脂、所述光起始剂以及所述色料按所述重量分数混合溶解,或将所述改性的聚酰亚胺类聚合物、所述感光单体、所述双酚A型环氧树脂、所述光起始剂、所述色料以及所述无机填充颗粒按所述重量分数混合,从而制得所述感光树脂组合物。
本发明实施方式还提供一种利用如上所述的感光树脂组合物的高分子膜,所述高分子膜由上述感光树脂组合物经烘烤固化后制得。
本发明实施方式还提供一种覆铜板,其包括至少一铜箔及结合于所述铜箔至少一表面的高分子膜,所述高分子膜由如上所述的感光树脂组合物经烘烤固化后制得。
本发明实施例的感光树脂组合物中含有上述改性的聚酰亚胺类聚合物及所述双酚A型环氧树脂,使得其制备的高分子膜具有良好的耐碱性、耐热性及挠曲性。
附图说明
图1为本发明实施方式的覆铜板的剖视示意图。
主要元件符号说明
覆铜板 10
铜箔 11
高分子膜 13
具体实施方式
本发明一较佳实施方式提供一种感光树脂组合物,其可用于制备油墨涂料、干膜或印刷电路板的感光绝缘层。所述感光树脂组合物,按重量份数计,包括100份的改性的聚酰亚胺类聚合物、10~40份的感光单体、10~25份的双酚A型环氧树脂
1~10份的光起始剂以及1~5份的色料。
所述改性的聚酰亚胺类聚合物的化学结构式为
所述改性的聚酰亚胺类聚合物由化学结构式为
的聚酰亚胺类聚合物中与R基团键接的羧基与甲基丙烯酸缩水甘油酯(化学结构式为)中的环氧基反应制得。其中,所述聚酰亚胺类聚合物由含有A基团的双酐单体与含有R基团的二胺单体、含有R1基团的二胺单体以及含有R2基团的二胺单体反应聚合而成。其中,x、y及z分别为大于等于1的自然数。
其中,所述含有A基团的双酐单体可选自但不仅限于4,4'-硫双邻苯二甲酸酐4,4'-氧双邻苯二甲酸酐
双环[2.2.2]辛-7-烯-2,3,5,6-四羧酸二酐CAS号为223255-30-9的双酐单体以及CAS号为223255-30-9的双酐单体中的至少一种。
所述含有R基团的二胺单体为在R基团上键接有羧基的二胺化合物。优选的,R基团包含苯基,且所述羧基键接于苯基上。本实施方式中,所述含有R基团的二胺单体可选自但不仅限于6,6'-双氨基-3,3'-甲叉基二苯甲酸3,5-二氨基苯甲酸、CAS号为1620566-43-9的1,3-二(4-氨基-2-苯甲酸氧基)苯、3,5-二(4-氨基苯氧基)苯甲酸、CAS号为135209-70-0的2-(4-氨基苯氧基)-5-氨基苯甲酸、CAS号为1071762-58-7的N,N-二(4-氨基苯基)-4-羧酸苯胺、CAS号为177960-30-4的3,5-二氨基-4-甲氧基苯甲酸及3,4-二氨基苯甲酸中的至少一种。
所述含有R1基团的二胺单体为柔软的长链状的二胺单体,其可选自但不仅限于CAS号为97917-34-5的二胺单体、三乙烯四胺四亚乙基五胺及聚醚胺(如CAS号为400760-04-5、796093-55-5及9046-10-0的聚醚胺等)中的至少一种。
所述含有R2基团的二胺单体中的R2基团包含至少一仲胺基团或叔胺基团。优选的,所述含有R2基团的二胺单体可选自但不仅限于CAS号为14303-59-4的二胺单体
CAS号为14071-33-1的二胺单体
CAS号为34066-75-6的二胺单体
4,4'-二氨基苯酰替苯胺CAS号为2362-26-7的二胺单体
及3,4’-二氨基苯酰替苯胺
中的至少一种。
本实施方式中,所述改性的聚酰亚胺类聚合物的分子量为5000~20000g/mol。
所述感光单体为水溶性感光单体及水分散性感光单体中的至少一种。所述感光单体为含乙氧基的丙烯酸酯化合物。本实施方式中,所述感光单体中乙氧基的数量大于或等于10,用以提高所述感光树脂组合物形成的高分子膜的亲水性及挠曲性。
所述感光单体具有多个反应官能基,用于在所述感光脂组合物受到紫外光照射时,与所述改性的聚酰亚胺类聚合物发生交联反应。本实施方式中,所述感光单体的反应官能基的数量大于或等于2。
所述感光单体可选自但不仅限于聚乙二醇二(甲基)丙烯酸酯、乙氧基化1,6-己二醇二丙烯酸酯、乙氧基化联苯茀、乙氧基化双酚A二(甲基)丙烯酸酯、乙氧基化三羟甲基丙烷三(甲基)丙烯酸酯、乙氧基化季戊四醇四丙烯酸酯及乙氧基化二季戊四醇六丙烯酸酯中的至少一种。
本实施方式中,所述双酚A型环氧树脂的环氧当量为180~2000g/Eq。
所述光起始剂用于在所述感光树脂组合物受到紫外光照射时,吸收紫外光而形成自由基或阳离子,引发所述环氧丙烯酸酯与丙烯酸脂单体以及丙烯酸脂寡聚物发生聚合和交联反应。所述光起始剂可选自α-羟基酮类化合物、酰基膦氧化物、α-氨基酮类化合物及肟酯类化合物等中的至少一种。更具体的,所述光起始剂可选自2-羟基-2-甲基-1-苯基-1-丙酮、1-羟基环己基苯基酮、2,4,6(三甲基苯甲酰基)二苯基氧化膦、2-甲基-1-(4-甲硫基苯基)-2-吗啉基-1-丙酮、苯基双(2,4,6-三甲基苯甲酰基)氧化膦、2-芐基-2-二甲基氨基-1-(4-吗啉代苯基)-1-丁酮、安息香双甲醚、二苯甲酮、异丙基硫杂蒽酮及咔唑肟酯中的至少一种。
所述色料用于使所述感光树脂组合物呈现所需的颜色,其可选自颜料及染料中的至少一种。所述颜料可选自无机颜料及有机颜料中至少一种。在本实施例中,所述颜料可选自酞菁蓝、酞菁绿、结晶紫、永固黄、二氧化钛、碳黑、氧化铁黑以及苯氨黑等中的一种。所述染料可为有机染料,更具体的,所述染料可为天然有机染料和合成有机染料中的至少一种。在本实施例中,所述染料可选自日本化药株式会社生产的Kayase Red-B、Black-AN、Blue-N(化工行业标准型号)、巴斯夫有限公司生产的Neozapon Red 355、Orasol Black-X55、Oracet Yellow-144FE(化工行业标准型号)等中的一种。所述染料也可选自永光公司销售的Everzol Black N、Evercion Red H-E3B、Evercion Yellow He4R、AS Black 8905B、ASBlack 8A316等中的一种。
本实施方式中,所述感光树脂组合物还可包括5~30重量份的无机填充颗粒。所述无机填充颗粒可选自但不仅限于二氧化硅、氧化铝、氢氧化铝、氧化镁、氢氧化镁、碳酸钙、氮化铝、氮化硼、碳化铝硅、碳化硅、碳酸钠、二氧化钛、氧化锌、氧化锆、石英、石墨、碳酸镁、钛酸钾、云母、磷酸钙、滑石、氮化硅、高岭土及硫酸钡中的至少一种。
本发明一较佳实施方式还提供一种上述感光树脂组合物的制备方法,其包括如下步骤:按重量份数计,将100份的改性的聚酰亚胺类聚合物、10~40份的感光单体、10~25份的双酚A型环氧树脂、1~10份的光起始剂以及1~5份的色料混合溶解,或将100份的改性的聚酰亚胺类聚合物、10~40份的感光单体、10~25份的双酚A型环氧树脂、1~10份的光起始剂、1~5份的色料以及5~30重量份的无机填充颗粒混合,从而制得所述感光树脂组合物。
本发明一较佳实施方式还提供一种高分子膜,其由上述感光树脂组合物烘烤固化制得。
请参阅图1,本发明一较佳实施方式还提供一种的覆铜板10,其包括至少一铜箔11以及结合于所述铜箔11至少一表面的上述高分子膜13。
由于所述感光树脂组合物含有上述改性的聚酰亚胺类聚合物及所述双酚A型环氧树脂,使得其制备的高分子膜具有良好的耐碱性、耐热性及挠曲性。
下面通过实施例及比较例来对本发明进行具体说明。
实施例1
于反应瓶中依次加入100g的改性的聚酰亚胺类聚合物(分子量为5000g/mol)、40g的乙氧基化三羟甲基丙烷三(甲基)丙烯酸酯、10g的1-羟基环己基苯基酮、2g的酞菁蓝、30g的硫酸钡及25g的双酚A型环氧树脂,搅拌混合制得所述感光树脂组合物。
实施例2
于反应瓶中依次加入100g的改性的聚酰亚胺类聚合物(分子量为5000g/mol)、20g的乙氧基化三羟甲基丙烷三(甲基)丙烯酸酯、10g的1-羟基环己基苯基酮、2g的酞菁蓝、5g的硫酸钡及12.5g的双酚A型环氧树脂,搅拌混合制得所述感光树脂组合物。
比较例1
于反应瓶中依次加入100g的PU亚克力树脂(分子量为20000g/mol)、20g的乙氧基化三羟甲基丙烷三(甲基)丙烯酸酯、10g的1-羟基环己基苯基酮、2g的酞菁蓝、15g的硫酸钡及30g的N-甲基吡咯烷酮,搅拌混合制得一感光树脂组合物。
比较例2
于反应瓶中依次加入100g的环氧亚克力树脂(分子量为10000g/mol)、20g的乙氧基化三羟甲基丙烷三(甲基)丙烯酸酯、10g的1-羟基环己基苯基酮、2g的酞菁蓝、15g的硫酸钡、30g的N-甲基吡咯烷酮及18.5g的双酚A型环氧树脂,搅拌混合制得一感光树脂组合物。
比较例3
于反应瓶中依次加入100g的改性的聚酰亚胺类聚合物(分子量为5000g/mol)、20g的乙氧基化三羟甲基丙烷三(甲基)丙烯酸酯及10g的1-羟基环己基苯基酮,搅拌混合制得一感光树脂组合物。
使用实施例1~2所制备的感光树脂组合物以及比较例1~3所制备的感光树脂组合物分别制备一结合于铜箔并完成曝光显影的高分子膜,从而依次形成实验样品1~5。
对上述5中实验样品进行氯化铜测试、百格附着力测试、耐碱性测试、耐热性测试、挠曲性测试以及常温存储性测试。其中,氯化铜测试为将上述实验样品浸入氯化铜溶液中,观察铜箔层表面是否变色,从而测试是否存在显影不净(即测试显影性)。耐碱性测试为将上述实验样品进入质量浓度为10%NaOH溶液中浸泡30分钟,观察实验样品上的高分子膜是否从铜箔上脱落,若未脱落则再次进行百格附着力测试。挠曲性测试为测试上述实验样品弯折360度不断的次数。耐热性测试为测试上述实验样品在测试温度为288℃且测试时间为30秒时,高分子膜不产生起泡、剥离等现象则视为“通过”,否则视为“不通过”。常温存储性测试为将上述实施例1~2所制备的感光树脂组合物以及比较例1~3所制备的树脂组合物分别存放1个月后再制备实验样品,并重复上述百格附着力测试以及耐热性测试,分析测试结果是否有差异,若测试结果无差异,则表明存放过程中无质变;否则,则表明存放过程产生了质变。测试结果请参照表1中的数据。
表1关于上述各个高分子膜的测试结果
由表1可以看出,相较于比较例1使用PU亚克力树脂且未使用双酚A环氧树脂制备的感光树脂组合物,实施例1~2采用改性的聚酰亚胺类聚合物及双酚A环氧树脂制备的感光树脂组合物,其形成的高分子膜层具有更好的显影性、百格附着力、耐碱性、耐热性和挠曲性。相较于比较例2使用环氧亚克力树脂及双酚A环氧树脂制备的感光树脂组合物,实施例1~2制备的感光树脂组合物,其形成的高分子膜层具有更好的显影性、百格附着力、耐碱性及挠曲性,且在常温下存储较长时而不质变。相较于比较例3未使用色料、填料及双酚A环氧树脂,实施例1~2制备的感光树脂组合物,其形成的高分子膜层具有更好的耐热性。
另外,对于本领域的普通技术人员来说,可以根据本发明的技术构思做出其它各种相应的改变与变形,而所有这些改变与变形都应属于本发明权利要求的保护范围。

Claims (15)

1.一种感光树脂组合物,按重量份数计,包括100份的改性的聚酰亚胺类聚合物、10~40份的感光单体、10~25份的双酚A型环氧树脂、1~10份的光起始剂以及1~5份的色料,其中,所述改性的聚酰亚胺类聚合物的化学结构式为
其由化学结构式为
的聚酰亚胺类聚合物中与R基团键接的羧基与甲基丙烯酸缩水甘油酯中的环氧基反应制得,所述聚酰亚胺类聚合物由含有A基团的双酐单体与含有R基团的二胺单体、含有R1基团的二胺单体以及含有R2基团的二胺单体反应聚合而成,所述含有R基团的二胺单体为在R基团上键接有羧基的二胺化合物,所述含有R1基团的二胺单体为柔软的长链状的二胺单体,R2基团包含至少一仲胺基团或叔胺基团,其中,x、y及z分别为大于等于1的自然数。
2.如权利要求1所述的感光树脂组合物,其特征在于,所述含有A基团的双酐单体选自4,4'-硫双邻苯二甲酸酐、4,4'-氧双邻苯二甲酸酐、双环[2.2.2]辛-7-烯-2,3,5,6-四羧酸二酐、CAS号为223255-30-9的双酐单体以及CAS号为223255-30-9的双酐单体中的至少一种。
3.如权利要求1所述的感光树脂组合物,其特征在于,R基团包含苯基,且所述羧基键接于苯基上。
4.如权利要求3所述的感光树脂组合物,其特征在于,所述含有R基团的二胺单体选自6,6'-双氨基-3,3'-甲叉基二苯甲酸、3,5-二氨基苯甲酸、1,3-二(4-氨基-2-苯甲酸氧基)苯、3,5-二(4-氨基苯氧基)苯甲酸、CAS号为135209-70-0的2-(4-氨基苯氧基)-5-氨基苯甲酸、CAS号为1071762-58-7的N,N-二(4-氨基苯基)-4-羧酸苯胺、CAS号为177960-30-4的3,5-二氨基-4-甲氧基苯甲酸及3,4-二氨基苯甲酸中的至少一种。
5.如权利要求1所述的感光树脂组合物,其特征在于,所述含有R1基团的二胺单体选自CAS号为97917-34-5的二胺单体、三乙烯四胺、四亚乙基五胺及聚醚胺中的至少一种。
6.如权利要求1所述的感光树脂组合物,其特征在于,所述含有R2基团的二胺单体选自CAS号为14303-59-4的二胺单体、CAS号为14071-33-1的二胺单体、CAS号为34066-75-6的二胺单体、4,4'-二氨基苯酰替苯胺、CAS号为2362-26-7的二胺单体及3,4’-二氨基苯酰替苯胺中的至少一种。
7.如权利要求1所述的感光树脂组合物,其特征在于,所述改性的聚酰亚胺类聚合物的分子量为5000~20000g/mol。
8.如权利要求1所述的感光树脂组合物,其特征在于,所述感光单体为含乙氧基的丙烯酸酯化合物。
9.如权利要求8所述的感光树脂组合物,其特征在于,所述感光单体中乙氧基的数量大于或等于10,所述感光单体具有多个反应官能基且所述反应官能基的数量大于或等于2。
10.如权利要求9所述的感光树脂组合物,其特征在于,所述感光单体选自聚乙二醇二(甲基)丙烯酸酯、乙氧基化1,6-己二醇二丙烯酸酯、乙氧基化联苯茀、乙氧基化双酚A二(甲基)丙烯酸酯、乙氧基化三羟甲基丙烷三(甲基)丙烯酸酯、乙氧基化季戊四醇四丙烯酸酯及乙氧基化二季戊四醇六丙烯酸酯中的至少一种。
11.如权利要求1所述的感光树脂组合物,其特征在于,所述双酚A型环氧树脂的环氧当量为180~2000g/Eq。
12.如权利要求1所述的感光树脂组合物,其特征在于,所述感光树脂组合物还包括5~30重量份的无机填充颗粒。
13.一种如权利要求1-12任意一项所述的感光树脂组合物的制备方法,其包括如下步骤:
将所述改性的聚酰亚胺类聚合物、所述感光单体、所述双酚A型环氧树脂、所述光起始剂以及所述色料按所述重量分数混合溶解,或将所述改性的聚酰亚胺类聚合物、所述感光单体、所述双酚A型环氧树脂、所述光起始剂、所述色料以及所述无机填充颗粒按所述重量分数混合,从而制得所述感光树脂组合物。
14.一种利用如权利要求1-12任意一项所述的感光树脂组合物的高分子膜,所述高分子膜由上述感光树脂组合物经烘烤固化后制得。
15.一种覆铜板,其包括至少一铜箔及结合于所述铜箔至少一表面的高分子膜,其特征在于,所述高分子膜由如权利要求1-12任意一项所述的感光树脂组合物经烘烤固化后制得。
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111072962A (zh) * 2019-12-20 2020-04-28 上海维凯光电新材料有限公司 耐高温光纤涂料用光敏聚酰亚胺的合成与应用
CN111393379A (zh) * 2020-04-22 2020-07-10 深圳先进电子材料国际创新研究院 二胺化合物及感光性树脂
CN115490852A (zh) * 2022-06-21 2022-12-20 广东鸿翔瑞材料科技有限公司 改性聚酰亚胺及其制备方法、聚酰亚胺膜

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113185653A (zh) * 2021-06-17 2021-07-30 江西金石三维智能制造科技有限公司 一种高强高韧的立体光造型树脂及其制备方法
CN116693745A (zh) * 2022-02-28 2023-09-05 华为技术有限公司 树脂、树脂的制备方法、及树脂的应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004062057A (ja) * 2002-07-31 2004-02-26 Showa Denko Kk 感光性熱硬化性樹脂組成物及びその硬化物
CN102361913A (zh) * 2009-08-28 2012-02-22 株式会社Lg化学 新型聚酰胺酸、聚酰亚胺、包含其的感光树脂组合物以及由其制备的干燥膜
CN107226983A (zh) * 2016-03-25 2017-10-03 鹏鼎控股(深圳)股份有限公司 树脂组合物及应用该树脂组合物的胶片及电路板
US20170362361A1 (en) * 2016-06-16 2017-12-21 Zhen Ding Technology Co., Ltd. Photosensitive resin composition, and film and printed circuit board using same

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101657482B (zh) 2007-04-19 2014-04-16 Kaneka株式会社 新型聚酰亚胺前体组合物及其利用
US9285680B2 (en) * 2014-07-16 2016-03-15 Taiflex Scientific Co., Ltd. Photosensitive polyimide composition, base agent thereof, method of making the base agent, and solder-resistant polyimide thin film made from the composition
KR101682006B1 (ko) * 2014-08-13 2016-12-02 주식회사 엘지화학 감광성 수지 조성물
TWI728137B (zh) 2016-06-29 2021-05-21 日商富士軟片股份有限公司 負型感光性樹脂組成物、硬化膜、硬化膜的製造方法、半導體裝置、積層體的製造方法、半導體裝置的製造方法及聚醯亞胺前驅物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004062057A (ja) * 2002-07-31 2004-02-26 Showa Denko Kk 感光性熱硬化性樹脂組成物及びその硬化物
CN102361913A (zh) * 2009-08-28 2012-02-22 株式会社Lg化学 新型聚酰胺酸、聚酰亚胺、包含其的感光树脂组合物以及由其制备的干燥膜
CN107226983A (zh) * 2016-03-25 2017-10-03 鹏鼎控股(深圳)股份有限公司 树脂组合物及应用该树脂组合物的胶片及电路板
US20170362361A1 (en) * 2016-06-16 2017-12-21 Zhen Ding Technology Co., Ltd. Photosensitive resin composition, and film and printed circuit board using same
CN107522822A (zh) * 2016-06-16 2017-12-29 臻鼎科技股份有限公司 感光性树脂组合物、覆盖膜及电路板

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111072962A (zh) * 2019-12-20 2020-04-28 上海维凯光电新材料有限公司 耐高温光纤涂料用光敏聚酰亚胺的合成与应用
CN111072962B (zh) * 2019-12-20 2022-11-04 上海维凯光电新材料有限公司 耐高温光纤涂料用光敏聚酰亚胺的合成与应用
CN111393379A (zh) * 2020-04-22 2020-07-10 深圳先进电子材料国际创新研究院 二胺化合物及感光性树脂
CN115490852A (zh) * 2022-06-21 2022-12-20 广东鸿翔瑞材料科技有限公司 改性聚酰亚胺及其制备方法、聚酰亚胺膜

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