CN1237720A - 具有改进的光引发剂体系的可光成象组合物 - Google Patents
具有改进的光引发剂体系的可光成象组合物 Download PDFInfo
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- CN1237720A CN1237720A CN99108303A CN99108303A CN1237720A CN 1237720 A CN1237720 A CN 1237720A CN 99108303 A CN99108303 A CN 99108303A CN 99108303 A CN99108303 A CN 99108303A CN 1237720 A CN1237720 A CN 1237720A
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- G—PHYSICS
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
本发明提供负片型可光成象组合物，含有A)大约30—80%(重量)的粘合剂聚合物，它有足够的酸官能度，使可光成象组合物在碱性水溶液中可显影，B)大约20—70%(重量)的可加成聚合的非气态α，β－烯不饱和化合物，它(们)能通过自由基引发的加成聚合反应形成高聚物，B)的至少约50%(摩尔)是甲基丙烯酸部分，和C)大约0.1—20%(重量)的光引发剂化学体系，它含约0.005—3%(重量)的三苯膦，和约0.005—2%(重量)的N－苯基甘氨酸。(所有重量百分数均以A)和B)的重量之和为基准)。
Description
本发明涉及负片型可光成象组合物，例如那些在印刷电路技术中用作光敏抗蚀剂的组合物。可光成象组合物含有光引发剂化学体系，包括N-苯基甘氨酸和三苯膦的混合物，可提供高的光速和其他性能特征。
本发明涉及可在碱性水溶液中显影的负片型可光成象组合物。本发明尤其适用于原色光成像抗蚀剂，也适用于凝固后形成焊接防护罩等的组合物。
种种这样的可光成象组合物已被描述。本发明所述类型的主要组份是A)粘合剂聚合物；B)一种或多种可光致聚合的α,β-不饱和烯化合物，和C)光引发剂化学体系。粘合剂聚合物A)具有足够的酸官能度，通常是羧酸官能度，粘合剂聚合物在碱性水溶液中可溶，因而赋予可光成象组合物在碱性水溶液中可显影的性能。可光致聚合化合物B)是单体和/或短链低聚物，其基本部分具有多重α,β-不饱和烯官能度。
光引发剂化学体系C)包括一经暴露于照射光就产生自由基的化合物。这些自由基使可光致聚合化合物B)的α,β-不饱和烯部分发生聚合的增长反应。这里，光引发剂体系C)被认为不仅包括产生自由基的化合物，还包括催化剂或促进自由基引发的可光致聚合化合物B)的α,β-不饱和烯部分的聚合反应的增感剂。
当可光致聚合化合物B)的α,β-不饱和烯部分的基本比例是甲基丙烯酸部分、即：占可光致聚合化合物B)的α,β-不饱和烯部分的至少大约50％(摩尔)时，当光引发剂体系C)包括占A)与B)重量之和的大约0.005％(重量)到大约3％(重量)的三苯膦时，发现可获得惊人高的光速。虽然光速的增加是很需要的，但三苯膦的加入会不利地影响其他的性能特征，包括体系的长期稳定性，即降低产品使用寿命和降低其使用有效性至最低限度。
此类可光成象组合物也常使用成色物质，可在曝光后产生浓色。这种成色物质在光敏抗蚀剂的曝光和未曝光部分之间产生对比度。这可达到一个实用的目的，让操作者知道抗蚀剂已经被曝光。另外，最近工业上的需求是在其他的加工过程开始以前，试图观测底板以发现明显的缺陷，例如光工具上的污点，以避免缺陷产品的进一步加工所伴生的材料成本和时间的浪费。虽然三苯膦增高光速，但趋向抑制颜色的形成，因而降低对比度，并使观察已曝光的光敏抗蚀剂层变得更加困难。
受到三苯膦不利影响的其他性能是粘合性(尤其对印刷电路板空格处对铜的粘合性)和空洞上方的绷紧强度。
因此，进行研究以发现可代替光引发剂体系的成份，它可提供高光速，还可避免三苯膦的某些缺点。
试图用于代替三苯膦的材料之一是N-苯基甘氨酸。N-苯基甘氨酸也提供优良的光速。然而，绷紧强度大大下降，细线粘合性极差。任何细线粘合性和绷紧强度的降低与电路板缺陷的增加呈正比例关系。
本发明涉及负片型可光成象组合物，包含A)具有足够的酸官能度的可使可光成象组合物在碱性水溶液中显影的有机的聚合粘合剂，B)可加成聚合的非气态的α,β-不饱和烯化合物，它(们)可以通过自由基引发的链增长加成聚合反应形成聚合物，B)的α,β-不饱和烯的至少大约50％(摩尔)来自甲基丙烯酸官能度，和C)占A)与B)总重量之和的大约0.1％(重量)到大约20％(重量)的可光活化的有机的对照射敏感而产生自由基的化学体系，以引发可加成聚合材料的链增长加成聚合反应。根据本发明，自由基化学体系C)包括占A)与B)总重量之和的大约0.005％(重量)到大约3％(重量)的三苯膦，和占A)与B)总重量之和的大约0.005％(重量)到大约2％(重量)的N-苯基甘氨酸。
除非另有说明，这里所有百分比都是重量百分比。成份A)(粘合剂聚合物)和成份B)(一种或多种光成象化合物)，这里认为等于100％(重量)，其他成份，包括光引发剂化学体系成份，均以A)与B)总重量之和为基准。
本发明指在碱性水溶液中可显影的具有足够酸官能度可光成象组合物。这样的可光成象组合物常含粘合剂A),A)含酸官能度，酸值通常至少大约80，优选至少大约100，更佳大约150或更多，最高大约250。酸官能度通常是羧酸官能度，但也可包括、例如磺酸官能度或磷酸官能度。用于可光成象组合物的粘合剂聚合物一般具有大约20,000到大约200,000、优选至少大约80,000的重均分子量。
聚合物一般来源于酸官能单体和非酸官能单体的混合物。合适的酸官能单体的某些具体例子是丙烯酸、甲基丙烯酸、马来酸、富马酸、柠康酸、2-丙烯酰基-2-甲基丙磺酸、磷酸丙烯酰2-羟乙酯、磷酸丙烯酰2-羟丙酯、2-羟基-α-丙烯酰基磷酸酯等。可用这些酸官能单体的一种或多种形成粘合剂聚合物。
酸官能单体和非酸官能单体可以通过共聚以提供所需的酸值，非酸官能单体的例子有丙烯酸和甲基丙烯酸的酯类，例如丙烯酸甲酯、丙烯酸2-乙基己酯、丙烯酸正-丁酯、丙烯酸正-己酯、甲基丙烯酸甲酯、丙烯酸羟乙酯、甲基丙烯酸丁酯、丙烯酸辛酯、甲基丙烯酸2-乙氧基乙酯、丙烯酸叔丁酯、二丙烯酸1,5-戊二醇酯、丙烯酸N,N-二乙氨基乙酯、二丙烯酸乙二醇酯、二丙烯酸1,3-丙二醇酯、二丙烯酸癸二醇酯、二甲基丙烯酸癸二醇酯、二丙烯酸1,4-环己二醇酯、2,2-二羟甲基丙烷二丙烯酸酯、二丙烯酸甘油酯、二丙烯酸三丙二醇酯、三丙烯酸甘油酯、2,2-二(对-羟基苯基)-丙烷二甲基丙烯酸酯、二丙烯酸三甘醇酯、聚氧乙基-2,2-二(对-羟基苯基)-丙烷二甲基丙烯酸酯、二甲基丙烯酸三甘醇酯、聚氧丙基三羟甲基丙烷三丙烯酸酯、二甲基丙烯酸乙二醇酯、二甲基丙烯酸丁二醇酯、二甲基丙烯酸1,3-丙二醇酯、二甲基丙烯酸丁二醇酯、二甲基丙烯酸1,3-丙二醇酯、三甲基丙烯酸1,2,4-丁三醇酯、二甲基丙烯酸2,2,4-三甲基-1,3-戊二醇酯、三甲基丙烯酸季戊四醇酯、1-苯基乙二醇1,2-二甲基丙烯酸酯、四甲基丙烯酸季戊四醇酯、三羟甲基丙烷三甲基丙烯酸酯、二甲基丙烯酸1,5-戊二醇酯、和二甲基丙烯酸1,4-苯二酚酯；苯乙烯和取代苯乙烯，例如2-甲基苯乙烯和乙烯基甲苯和乙烯基酯，例如丙烯酸乙烯酯和甲基丙烯酸乙烯酯。
粘合剂聚合物A)的用量可以在很宽的范围内变化，一般以A)与B)总重量之和为基准，占组合物的大约30％(重量)到大约80％(重量)。
这些聚合物和使用这些聚合物的可光成象组合物的例子在下列美国专利No.3,953,309,4,003,877,4,610,951,4,695,527中被发现，其内容列入这里以供参考。
可光致聚合成份B)一般是单体、二聚体或具有烯不饱和度、尤其是α,β-烯不饱和度的短链低聚体，包括单官能化合物和具有α,β-不饱和烯官能度2或更多的化合物。一般用单官能和多官能单体的混合物。合适的光成像化合物包括、而不局限于上述列举的适于形成粘合剂聚合物的单体，尤其是非酸官能化合物。光成像成份B)的用量通常占可光成象组合物的大约20％(重量)到大约70％(重量)，以A)与B)总重量之和为基准。
本发明的光引发剂化学体系尤其对于甲基丙烯酸和/或酯官能度有效。因此，本发明指可光致聚合成份B)的至少大约50％(摩尔)的α,β-烯不饱和度包含甲基丙烯酸官能度，酸或酯。
若曝光时要引发单体的聚合反应，可光成象组合物含有光引发剂化学体系。根据本发明，光引发剂化学体系含大约0.005％(重量)到大约3％(重量)的三苯基磷杂环戊二烯(TPPN)和大约0.005％(重量)到大约2％(重量)的N-苯基甘氨酸(NPG)，以A)与B)总重量之和为基准。
根据此体系的现今标准，在本发明所指的此类可光成象组合物中，发现无论是TPPN和还是NPG，缺少另一个都将丧失用途。而这里陈述的用量的TPPN和NPG混合物可产生优异的光速，同时避开单个每种材料的缺陷。这样，在对粘合性、绷紧强度或稳定性不产生负面影响情况下，就可获得较高的光速。
除了TPPN和NPG，其他光引发剂化学品也可以使用，一般作为光引发剂化学体系的一部分。通常，光引发剂化学体系占A)与B)总重量的大约0.1％(重量)到大约20％(重量)。其他光引发剂化学品包括、但不局限于9-苯基吖啶、芳香酮(二苯酮、N,N’-四甲基-4,4’-二氨基苯酮[米蚩酮]、N,N’-四乙基-4,4’-二氨基苯酮、4-甲氧基-4’-二甲氨基苯酮、3,3’-二甲基-4-甲氧基苯酮、p,p’-双(二甲氨基)苯酮、p,p’-双(二乙氨基)-苯酮、蒽醌、2-乙基蒽醌、萘醌、菲醌、苯偶姻类(苯偶姻、苯偶姻甲醚、苯偶姻乙醚、苯偶姻异丙醚、苯偶姻-正丁醚、苯偶姻苯醚、甲基苯偶姻、乙基苯偶姻等)，苄基衍生物(联苄基、二硫化苄基二苯、苄基二甲基缩酮、(SIC)等)，吖啶衍生物(9-苯基吖啶、1,7-双(9-吖啶基)庚烷等)，噻吨酮类(2-氯噻吨酮、2-甲基噻吨酮、2,4-二乙基噻吨酮、2,4-二甲基噻吨酮、2-异丙基噻吨酮等)，苯乙酮类(1,1-二氯苯乙酮、对-叔-丁基二氯苯乙酮、2,2-二乙氧基苯乙酮、2,2-二甲氧基2-苯基苯乙酮、2,2-二氯-4-苯氧基苯乙酮等)，等…。
虽然不要求，但优选的本发明的光引发剂化学体系包括占A)与B)总重量之和大约0.5％(重量)到大约6％(重量)洛粉碱二聚体(咪唑二聚体)。这样的洛粉碱二聚体的例子包括、但不局限于三苯基联咪唑，尤其是2,4,5-三苯基咪唑二聚体，例如2,2’-二(邻氯苯)-4,4’,5,5’-四苯基联咪唑、2,2’-二(邻氯苯)-4,4’,5,5’-四(间-甲氧苯基)联咪唑、2,2’-二(对羧苯基)-4,4’,5,5’-四苯基联咪唑、2,2’-二(对氯苯基)-4,4’,5,5’-四(对甲氧苯基)联咪唑、2,2’-二-邻-甲苯基-4,4’,5,5’-四苯基联咪唑、2,2’-二-对-甲苯基-4,4’-二-邻-甲苯基-5,5’-二苯基联咪唑等；这些可以以单个或两个或更多之组合使用。
可光成象组合物可以有利地含一种或更多的占A)与B)总重量之和的大约0.5％(重量)到大约10％(重量)的增塑剂。合适增塑剂的例子包括、但不局限于邻苯二甲酸酯类(例如邻苯二甲酸二丁酯、邻苯二甲酸二庚酯、邻苯二甲酸二辛酯、邻苯二甲酸二烯丙基酯)，二醇类(例如聚乙二醇，聚丙二醇)，二醇酯类(例如二乙酸三甘醇酯、二乙酸四乙二醇酯、二苯甲酸二丙二醇酯)，磷酸酯类(磷酸三甲苯酯、磷酸三苯酯)，酰胺类(对-甲苯磺酰胺、苯磺酰胺、N-正-丁基丙酮酰胺)，脂肪族二元酸酯类(己二酸二异丁酯、己二酸二辛酯、癸二酸二甲酯、壬二酸二辛酯、苹果酸二丁酯、柠檬酸三乙酯、柠檬酸三丁酯、乙酰柠檬酸三乙酯、乙酰柠檬酸三正丙酯、乙酰柠檬酸三正丁酯、月桂酸丁酯、二辛基4,5-二环氧环己烷-1,2-二羧酸酯、三乙酰甘油酯。
如上所述，本发明的组合物通常含一种成色物质，以向曝光的可光成象组合物提供对比度。TPPN和NPG混合物可避免单用TPPN不用NPG所产生的对比度的下降。成色物质用量通常占A)与B)总重量之和的大约0.1％(重量)到大约1.0％(重量)。成色物质的例子包括、但不局限于二苯基胺、二苄基苯胺、三苯基胺、二乙基苯胺、二苯基-对-苯二胺、对-甲苯胺、4,4’-联苯基二胺、邻-氯苯胺等，白色结晶紫，极淡孔雀石绿。
此外，可光成象组合物可以含有在本技术领域中已知的种种附加成份，包括附加的聚合物，例如那些可以用来实现焊接防护罩的最后凝固熟化的聚合物、染料、稳定剂、增韧剂、填料等。
可光成象组合物的加工是按常规的方式进行。在一般的工序中，一个可光成象组合物薄层，或由一种液体组合物形成、或由一个干燥膜转换而成，被安放到铜包覆板的铜表面上。可光成象组合物薄层以合适的图形暴露于照射光中。曝光使曝光区域中的单体发生聚合，产生阻止显影的交联结构。接着组合物在碱性水溶液中显影，例如1％碳酸钠溶液。碱性溶液导致与粘合剂聚合物中的羧酸基团形成盐，使它们变得可溶并可除去。显影以后，用腐蚀剂从抗蚀剂被除去的区域除去铜，由此形成一个印刷电路。然后留下的抗蚀剂用一种合适的洗提剂除去。
本发明提供细线(小于75微米)抗蚀剂侧壁，可与铜表面粘合得很好。
本发明将通过具体实施例更详细地进行说明。
对比实施例1和2和实施例3
一种基本的可光成象组合物按如下配方配制：
成 份 重量％ 重量％* 化学功能聚合物** 51.45 56.4 聚合物主要成分聚氧丙基单甲基丙烯酸酯 12 13.1 可聚合单体异氰脲酸酯，聚乙氧基，三甲基丙烯 15 16.4 可聚合低聚体酸低聚体双A，聚氧乙基二甲基丙烯酸酯 13 14.2 可聚合单体咪唑二聚体 3.5 3.8 光引发剂9-苯基吖啶 0.1 0.11 光引发剂白色结晶紫 0.4 0.44 成色物质孔雀石绿染料 0.05 0.055 背景染料对甲苯磺酰胺 4.5 4.9 增塑剂
*依据聚合物和聚合单体和低聚物的总重量100％进行归一化
**23％(重量)的甲基丙烯酸，66％(重量)的甲基丙烯酸甲酯，11％(重量)的丙烯酸丁酯。
对基本配方，加入NPG(对比实施例1)、TPPN(对比实施例2)和NPG与TPPN的组合物(实施例3)。测试条件表示在下表中。
| 性能标准 | 实施例10.05％*N-苯基甘氨酸(NPG) | 实施例20.3％三苯膦(TPPN) | 实施例30.01％NPG+0.02％TPPN | 目标性能 |
| 曝光(Stouffer 21 Step,40mJ) | 9.0 | 8.5 | 8.0 | ＞8.0 |
| 颜色对比度(15分钟后，40mJ) | 25％ | 25％ | 30％ | ＞30％ |
| 光速稳定性(Stouffer 41Step保持5天后变化) | 0-1 | 4.5-5.0 | 0-1 | 0-1 |
| 细线粘合效果(4次显影) | 44微米 | 40微米 | 32微米 | ＜35微米 |
| 绷紧强度 | 440克 | 580克 | 660克 | ＞600克 |
*重量百分比；对归一化的重量百分比乘1.094。
注释：
a)Stouffer 21 Step在暴露于紫外光后被记录，在1％的碳酸钠一水合物中于30℃下显影40秒。
b)颜色对比度使用一个UV/VIS分光光度计测量，在曝光前和曝光后15分钟后比较颜色。由于薄膜是向光的(形成颜色)，表中的百分比代表颜色的增强。
c)稳定性的测定是取一块抗蚀剂漆膜，漆膜保持1天后和5天后进行测试。在这2个不同的日子里记录下Stouffer 41 Step。一个稳定的体系会在保持期之后不显示出什么变化。
d)细线粘合性以400微米线固定间距用组合成逐渐减小的尺寸的线(从200-20微米)在成像图形上进行测量。在光抗蚀剂以此图形曝光并以多于建议的100％的线显影后，最细的线的粘合经受压力，引起粘合作用的下降。此工序结束后，检测线并记录保留的最细的线。
e)绷紧强度是曝光和显影后抗蚀剂的挠性的度量。在此测试中，光抗蚀剂叠压到一个6毫米洞的两边，接着在40毫焦下曝光，并在1％碳酸钠一水合物中于30℃下显影。将一个探针推进绷覆的洞，记录破裂绷布上此处力的克数。较高的数值反映较高的挠度。
Claims (3)
1．负片型可光成象组合物，包括：
A)占A)与B)重量之和的30％(重量)到80％(重量)的粘合剂聚合物，它具有足够的酸官能度，赋予所述可光成象组合物在碱性水溶液中可显影的性能，
B)占A)与B)重量之和的20％(重量)到70％(重量)的一种或多种可加成聚合的非气态α,β-烯不饱和化合物，所述化合物能通过自由基引发的链增长加成聚合反应形成高聚物，B)的α,β-烯不饱和部分的至少50％(摩尔)是甲基丙烯酸部分，和
C)占A)与B)重量之和的0.1％(重量)到20％(重量)的光引发剂化学体系，所述光引发剂化学体系含占A)与B)重量之和的0.005％(重量)到3％(重量)的三苯膦，和占A)与B)重量之和的0.005％到2％(重量)的N-苯基甘氨酸。
2．根据权利要求1所述的组合物，其特征在于还包括占A)与B)重量之和的0.1％(重量)到1.0％(重量)的成色物质。
3．根据权利要求1所述的组合物，其特征在于还包括占A)与B)重量之和的0.5％(重量)到6％(重量)的咪唑二聚体。
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| US09/088,561 US5939238A (en) | 1998-06-02 | 1998-06-02 | Photoimageable composition having improved photoinitiator system |
| US09/088,561 | 1998-06-02 |
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| US6004725A (en) * | 1997-12-01 | 1999-12-21 | Morton International, Inc. | Photoimageable compositions |
| JPH11167203A (ja) * | 1997-12-01 | 1999-06-22 | Nichigoo Mooton Kk | 感光性樹脂組成物及びそれを用いた感光性エレメント |
| ES2263291T3 (es) * | 1998-09-28 | 2006-12-01 | Kimberly-Clark Worldwide, Inc. | Quelatos que comprenden grupos quinoides como fotoiniciadores. |
| JP5129680B2 (ja) * | 2008-07-29 | 2013-01-30 | 富士フイルム株式会社 | 感光性組成物、並びに感光性フィルム、感光性積層体、永久パターン形成方法、及びプリント基板 |
| JP5393092B2 (ja) | 2008-09-30 | 2014-01-22 | 富士フイルム株式会社 | 染料含有ネガ型硬化性組成物、これを用いたカラーフィルタ及びその製造方法、並びに固体撮像素子 |
| JP2011105804A (ja) * | 2009-11-13 | 2011-06-02 | Sumitomo Bakelite Co Ltd | （メタ）アクリル系硬化性組成物、（メタ）アクリル系複合シート、ならびに（メタ）アクリル系硬化物およびその製造方法 |
| EP2950144B1 (en) | 2014-05-31 | 2016-12-14 | Rohm and Haas Electronic Materials LLC | Imaging process on substrates with aqueous alkaline soluble uv blocking compositions and aqueous soluble uv transparent films |
| US20160327861A1 (en) * | 2015-05-05 | 2016-11-10 | E I Du Pont De Nemours And Company | Photosensitive dry film compositions |
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| US3953309A (en) * | 1972-12-14 | 1976-04-27 | Dynachem Corporation | Polymerization compositions and processes having polymeric binding agents |
| US4003877A (en) * | 1974-05-24 | 1977-01-18 | Dynachem Corporation | Photopolymerizable screen printing inks for permanent coatings prepared from aryloxyalkyl compositions |
| US4245030A (en) * | 1979-05-23 | 1981-01-13 | Hoechst Aktiengesellschaft | Photopolymerizable mixture containing improved plasticizer |
| US4414312A (en) * | 1980-09-03 | 1983-11-08 | E. I. Du Pont De Nemours & Co. | Photopolymerizable polyamide ester resin compositions containing an oxygen scavenger |
| DE3136818C2 (de) * | 1980-09-19 | 1990-08-02 | Hitachi Chemical Co., Ltd., Tokio/Tokyo | Verwendung eines lichtempfindlichen Gemisches und eines lichtempfindlichen Aufzeichnungsmaterials zur Bildung einer Lötmaske |
| US4610951A (en) * | 1983-06-06 | 1986-09-09 | Dynachem Corporation | Process of using a flexible, fast processing photopolymerizable composition |
| DE3412992A1 (de) * | 1984-04-06 | 1985-10-24 | Hoechst Ag, 6230 Frankfurt | Durch strahlung polymerisierbares gemisch und verfahren zum aufbringen von markierungen auf eine loetstopresistschicht |
| US4876175A (en) * | 1988-05-09 | 1989-10-24 | Eastman Kodak Company | Dye sensitized photographic imaging systems |
| US5217845A (en) * | 1988-12-22 | 1993-06-08 | Hoechst Aktiengesellschaft | Photopolymerizable mixture and photopolymerizable copying material containing same |
| US5310862A (en) * | 1991-08-20 | 1994-05-10 | Toray Industries, Inc. | Photosensitive polyimide precursor compositions and process for preparing same |
| JP3220498B2 (ja) * | 1992-03-06 | 2001-10-22 | 岡本化学工業株式会社 | 光重合性組成物 |
| TW424172B (en) * | 1995-04-19 | 2001-03-01 | Hitachi Chemical Co Ltd | Photosensitive resin composition and photosensitive element using the same |
| EP0801328A1 (en) * | 1996-04-09 | 1997-10-15 | Morton International, Inc. | Photoimageable composition having an acrylic-functional UV stabilizer |
| CA2252240C (en) * | 1997-12-01 | 2002-02-26 | Daniel E. Lundy | Photoimageable compositions |
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| CN1103065C (zh) | 2003-03-12 |
| KR20000005718A (ko) | 2000-01-25 |
| CA2266607C (en) | 2002-02-26 |
| EP0962827A3 (en) | 2000-06-07 |
| EP0962827A2 (en) | 1999-12-08 |
| SG80032A1 (en) | 2001-04-17 |
| CA2266607A1 (en) | 1999-12-02 |
| KR100302049B1 (ko) | 2001-10-18 |
| TW562996B (en) | 2003-11-21 |
| US5939238A (en) | 1999-08-17 |
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| JP4244255B2 (ja) | 2009-03-25 |
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