CN1159626C - 含有可光聚合的粘合剂低聚物的可光成像的组合物 - Google Patents
含有可光聚合的粘合剂低聚物的可光成像的组合物 Download PDFInfo
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- CN1159626C CN1159626C CNB001348817A CN00134881A CN1159626C CN 1159626 C CN1159626 C CN 1159626C CN B001348817 A CNB001348817 A CN B001348817A CN 00134881 A CN00134881 A CN 00134881A CN 1159626 C CN1159626 C CN 1159626C
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- composition
- oligomer
- adds
- alkylidene
- scolding tin
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Classifications
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Abstract
本发明提供了具有四丙烯酸酯官能团以及羧酸官能团的低聚物。该低聚物用作形成印刷电路的抗光蚀剂中的可光聚合的粘合剂。该低聚物特别的优点在于必须在耐受镍/金镀条件下形成焊锡掩模的组合物。
Description
本发明涉及在形成电路系统中用作抗光蚀剂的可光成像的组合物。本发明特别有利的方面涉及用作焊锡掩模的抗光蚀剂,特别是经受粗糙加工条件如在镍/金无电镀中遇到的焊锡掩模的抗光蚀剂。
本发明新的粘合剂低聚物给光成像的抗光蚀剂提供了挠性并且当暴露于镍/金镀条件下时显著地改进了形成焊锡掩模的抗蚀剂的性能。虽然粘合剂低聚物最重要的好处在于形成焊锡掩模的光抗蚀剂,但挠性在所有抗光蚀剂组合物中是需要的,包括原像抗光蚀剂。
形成焊锡掩模的抗光蚀剂在印刷电路板上形成硬的、永久性的层。焊锡掩模必须硬,持久和抗化学物质如有机溶剂及强酸和强碱。在这方面,焊锡掩模应该满足IPC/ANSI SM-840B表12试验的标准,Summary ofCriteria for Qualification/Conformance(Institute forInterconnecting Circuits)。在此,焊锡掩模被定义为满足那些试验的层。在碱性水溶液中显影的形成焊锡掩模组合物的实例是美国专利5229252和5364736,这两篇文献的教导在此引入作为参考。
先前,焊锡直接应用在和表面固定件等电连接的铜电路轨迹的暴露焊接点上。直接焊接至电路轨迹的问题包括焊锡的费用、焊锡的毒性、铜迁移进入焊锡中和焊锡的锈蚀。改进的方法包括在制备电连接中焊接点的镍/金镀。暴露的焊接点首先通过无电镀方法用镍电镀至2.54×10-4-7.62×10-4厘米(约100-约300微英寸)厚。然后通过无电镀方法在镍上电镀例如6微英寸的薄层金。镍/金电镀是有利的:电镀层是平的以及镍金使铜免于迁移。另外,金不会锈蚀。
但是,无电镀方法是粗糙的,需要焊锡掩模符合电镀条件。特别地,镍无电镀典型地在约90℃下进行15分钟。经常发现在焊接点附近的区域中焊锡掩模升高。
形成焊锡掩模的可成像组合物的低分子量粘合剂聚合物趋于在加工过程中较少收缩,导致焊锡掩模较少升高。但是,低分子量粘合剂聚合物趋于发粘,是不受欢迎的特性,因为接触成像即图形和可光成像组合物之间的直接接触需要最大的分辨率。
较高分子量粘合剂聚合物降低粘性但收缩较多,导致了在镍/金电镀过程中大量焊锡掩模的升高。
目前许多形成焊锡掩模的抗光蚀剂是基于苯乙烯-马来酸酐粘合剂聚合物。因为苯乙烯/马来酸酐聚合物的刚性,基于该聚合物的形成焊锡掩模的抗光蚀剂趋于在镍/金镀条件下支撑差。
本发明涉及挠性可光聚合的粘合剂低聚物,该低聚物降低了特性协调的影响,例如粘性相对暴露于镍/金电镀的焊锡掩模组合物的升高。
本发明提供了具有四-丙烯酸酯官能团以有效光聚合以及具有挠性的粘合剂低聚物。该粘合剂低聚物还具有充分的酸官能度,从而掺入其中的可光成像的组合物在碱性水溶液中显影。丙烯酸酯和酸官能的粘合剂低聚物可有利地用在原像抗蚀剂中。但是粘合剂低聚物最显著的优点目前在于在形成焊锡掩模的可光成像的组合物中的用途,特别是在形成随后暴露于镍/金镀或类似的粗糙加工条件下的焊锡掩模的组合物中的用途。
本发明的粘合剂低聚物具有通式(I):
(CH2=CH(H或CH3)-CO-X-R-CH(OZ)-CH2-O-φ-)2-C(CH3)2
其中R是1-40个碳的亚烷基;
X不存在或选自分子量在50-2000之间的由亚烷基二醇、聚酯二醇和聚醚二醇组成的二醇;和
Z是式:
-CO-NH-Y-NH-CO-O(-VW1-5-O-CO-NH-Y-NH-CO-O)n-Q-O-CO-CH(H或 CH3)=CH2;
其中Y是亚烷基或芳香烃基团;
V是亚烷基,芳香基,烷芳基或芳烷基烃基;W是相同的或不同的,且每个是选自COOH,SO2H和PO4H(H或C1-18烷基)的酸基团,
n=1-4,优选1;
Q是2-6个碳原子的亚烷基。
本发明的原像光抗蚀剂包括,基于(A)和(B)之和的重量:
(A)具有充分羧酸官能度的约50-约100wt%粘合剂分子,以便抗光蚀剂在碱性水溶液中显影,约5-100wt.%的组合物(基于(A)加(B)的总重)是(A1)式(I)的低聚物,和O-约50wt.%含(A2)附加的酸官能的粘合剂聚合物的组合物,优选至少约10wt.%含有所述的附加的酸官能的粘合剂聚合物(A2);
(B)0-50wt.%,优选至少2wt.%的可光聚合的非酸官能的组分,含有α,β-烯不饱和单体和/或除了式(I)低聚物以外的α,β-烯不饱和低聚物,
(C)约0.1-约10wt%的光引发剂化学体系。
意在提供永久性层例如焊锡掩模的可光成像的组合物进一步含有与(A)分独立的(D)部分,即约5-约40wt%环氧树脂,基于(A)加(B)的总重量。含(D)的组合物优选还含有约1-约10wt%的环氧交联剂和/或环氧固化催化剂(E),基于(A)加(B)的总重量。
本文中,百分数是重量百分数,除非另外说明。分子量是重均分子量。术语“低聚物”是指重均分子量为500-5000的聚合的分子。术语“聚合物”是指重均分子量为5000以上的聚合的分子。
本发明新的粘合剂低聚物(A1)方便地从可商购得到的双酚A环氧丙烯酸酯制备,该丙烯酸酯具有通式(II):
(CH2=CH(H或CR3)-CO-X-R-CH(OH)-CH2-0-φ-)2-C(CH3)2,其中X和R是如上定义的。该类双酚A环氧丙烯酸酯的分子量是约500-约1500。该类化合物的商购实例包括Novacure3701,Ebecryl600和ECN117。虽然这些商购的化合物具有二丙烯酸酯的官能团,但它们目前不被喜欢用于可光成像的组合物中,主要因为它们每个丙烯酸酯官能团具有相对高的分子量,如果用于可光成像的组合物中,就会提供不充分的感光速度。根据本发明,改进这些双酚A环氧丙烯酸酯以在低聚物分子中提供附加的丙烯酸酯官能团,使丙烯酸酯官能团进入光聚合反应中而没有硬脂的阻碍,以便提供充足的感光速度。此时,本发明的粘合剂低聚物是挠性的,给光成像的组合物提供挠性。特别地,该挠性帮助在粗糙的加工条件下如镍/金镀中降低焊锡掩模的升高。本发明的焊锡掩模组合物是完全非粘性的,它们可接触成像,具有充足的感光速度,能耐受镍/金镀的条件。
粘合剂聚合物(A1)还具有充分的酸官能度以使可光成像的组合物在粘性水溶液中显影。本发明粘合剂低聚物的酸价是约50-约200。
在式(II)注意到除了双酚A环氧丙烯酸酯的两个丙烯酸酯官能团外,化合物还具有两个羟基官能团,通过它们式(I)的基团Z被连接,增加两个附加的丙烯酸酯官能团。
在当前优选的合成路径中,双酚A环氧丙烯酸酯和二异氰酸酯反应,两个摩尔的二异氰酸酯反应以便在每个羟基官能团的一端连接并且提供两个异氰酸酯部分以进一步反应。二异氰酸酯可以是任何通用的二异氰酸酯,例如1,6-己二异氰酸酯(HDI),异氟尔酮二异氰酸酯(IPDI),亚甲基二异氰酸酯(MDI),亚甲基双环己基异氰酸酯,三甲基六甲基二异氰酸酯,己烷二异氰酸酯,六甲基胺二异氰酸酯,亚甲基双环己基异氰酸酯,甲苯二异氰酸酯,1,2-二苯乙烷二异氰酸酯,1,3-二苯丙烷二异氰酸酯,二苯甲烷二异氰酸酯,二环己基甲基二异氰酸酯等。对于最大挠性的低聚物,优选二异氰酸酯是脂肪族的二异氰酸酯如HDI。在此,该分子具有二异氰酸酯官能团。
然后通过分子和两摩尔具有二羟基官能团以及一个或多个酸基的分子反应来延长链。该类分子的实例包括但不限于二甲醇丙酸(DMPA)。
在该合成步骤中,分子再一次具有二羟基官能团。
然后通过使其两摩尔二异氰酸酯反应进一步延长链,再一次得到分子二异氰酸酯官能团。
在该步骤,或者通过使酸官能二醇和二异氰酸酯反应进一步延长链。但是,一般不希望进一步增加分子量,因为这趋于降低感光速度而没有相应提高低聚物的挠性。
更确切些,在该步骤,二异氰酸酯官能低聚物是通过和两摩尔羟基官能的(甲基)丙烯酸酯如羟基乙基异丁烯酸酯或4-羟基丁基丙烯酸酯(4HBA)反应而被丙烯酸酯封端的。由此合成的低聚物具有4个丙烯酸酯官能度,能充分地彼此相互隔开以便能够在光聚合反应中自由地反应。粘合剂低聚物还具有两个或多个酸基团,提供约50-约200的酸价。完成的低聚物的分子量是约2000-约100000。
附加的酸官能的粘合剂聚合物(A2)如果和式(I)的粘合剂低聚物结合使用,可一般由α,β-烯不饱和单体制备。适合的酸官能的单体的一些具体实例是丙烯酸,异丁烯酸,马来酸,富马酸,柠康酸,2-羟基乙基丙烯酰基磷酸酯,2-羟基丙基丙烯酰基磷酸酯,2-羟基-α-丙烯酰基磷酸酯等。可以使用一种或多种这样的酸官能单体以形成粘合剂聚合物。酸官能单体可以和非酸官能单体共聚合以提供所需的酸价,例如丙烯酸的酯,例如丙烯酸甲酯,异丁烯酸甲酯,羟基乙基丙烯酸酯,异丁烯酸丁酯,丙烯酸辛酯,2-乙氧基乙基异丁烯酸酯,丙烯酸叔丁酯,1,5-戊二醇二丙烯酸酯,N,N-二乙基氨基乙基丙烯酸酯,乙二醇二丙烯酸酯,1,3-丙二醇二丙烯酸酯,1,10-癸二醇二丙烯酸酯,1,10-癸二醇二异丁烯酸酯,1,4-环己烷二醇二丙烯酸酯,2,2-二羟甲基丙烷二丙烯酸酯,丙三醇二丙烯酸酯、三丙二醇二丙烯酸酯,三丙烯酸甘油酯,2,2-二(对羟基苯基)丙烷二异丁烯酸酯,三甘醇二丙烯酸酯,聚氧化乙烯-2-2-(二对羟基苯基)丙烷二异丁烯酸酯,三甘醇二异丁烯酸酯,聚氧化丙基三羟甲基丙烷三丙烯酸酯,乙二醇二异丁烯酸酯,丁二醇二异丁烯酸酯,1,3-丙二醇二异丁烯酸酯,丁二醇二异丁烯酸酯,1,3-丙二醇二异丁烯酸酯,1,2,4-丁二醇三异丁烯酸酯,2,2,4-三甲基-1,3-戊二醇二异丁烯酸酯,季戊四醇三异丁烯酸酯,1-苯乙烯-1,2-二异丁烯酸酯,季戊四醇四异丁烯酸酯,三羟甲基丙烷三异丁烯酸酯,1,5-戊二醇二异丁烯酸酯,和1,4-苯二醇二异丁烯酸酯;苯乙烯和取代的苯乙烯,例如2-甲基苯乙烯,乙烯基甲苯和乙酰基酯,例如丙烯酸乙烯酯和异丁烯酸乙烯酯。
如果需要较高交联强度的光成像的组合物,向附加的粘合剂聚合物(A2)提供丙烯酸酯官能团,如美国专利5698370所描述的。在该专利中,聚合物骨架中马来酸酐部分和羟基官能的丙烯酸酯半酯化,例如羟基乙基(甲基)丙烯酸酯或4-羟基丁基(甲基)丙烯酸酯。
任何附加的粘合剂聚合物(A2)的分子量(重均)约20000-约200000。对于原像抗蚀剂,平均分子量优选约80000-约150000。对于形成焊锡掩模的组合物,优选的重均分子量是约2000-约100000。为了组合物在碱性水溶液中显影,酸价应是约120-约300,优选约150-约250。
由于式(I)的粘合剂低聚物(A1)具有四丙烯酸酯官能团,所以它易于在光聚合反应中形成交联网络。因此,在一些配方中粘合剂完全取决于光聚合反应而没有附加的可光聚合的单体或低聚物(B)。将低分子量可光聚合的单体(B)减少到最低或除去是有利的,因为该类单体趋于给可光成像的组合物增加粘性。但是,为了在本发明的一些配方中获得充分的交联密度,使用可光聚合的单体或低聚物。
可和式(I)的粘合剂低聚物(A1)结合使用的用以提高暴露的光抗蚀剂的交联密度的有用的可光聚合的单体(B)包括那些上述用来形成粘合剂聚合物的非酸的多官能的单体。一些特别适合的多官能丙烯酸单体是四乙二醇二丙烯酸酯(TEGDA),三羟甲基丙烷三丙烯酸酯(TMPTA),丁二醇二异丁烯酸酯(BDDMA)和季戊四醇三丙烯酸酯(PETA)。
另外,可光聚合的组分(B)含有附加的多官能低聚物,例如先前描述的环氧丙烯酸酯低聚物。这些例如在美国专利5229252中有描述,其教导在此引入作为参考。
为了在暴露于光化辐射时引发单体和/或低聚物的聚合反应,可光成像的组合物含有(C)适当的光引发剂或光引发剂化学体系。适合的光引发剂包括苯偶姻醚,苯偶酰酮缩醇,苯乙酮,二苯酮和与胺有关的化合物。优选的引发剂是噻吨酮,例如2-异丙基噻吨酮,特别是和胺结合的噻吨酮。
本发明的原像抗蚀剂的组分一般在适合的溶剂如甲基乙基酮中稀释。同样,在焊锡掩模组合物中,作为两部分系统提供,含粘合剂(A),可光聚合的组分(B)和光引发剂化学体系(C)的部分溶解于有机溶剂中。对于形成焊锡掩模的组合物,是液体并且具有充分低的粘度的环氧树脂一般是可得的,这样可以使用它们而不用在有机溶剂中稀释,尽管溶剂可和环氧树脂一起使用来调节粘度。
对于形成焊锡掩模的组合物,组合物进一步包括D)环氧树脂或树脂。环氧树脂在显影和环氧树脂或环氧树脂的混合物的最终固化后,赋予涂层优异的硬度和耐久性。
许多环氧树脂适用于本发明中。典型地,使用双酚A,Novalac和酚甲酚型环氧树脂。其它适合的环氧树脂例如在美国专利4092443中有描述,其教导在此引入作为参考。环状脂肪族的环氧化物例如那些在商标CyanacureUVR-6100和UVR-6110下销售的(由Union Carbide,Danbury,Conn.生产)也是有用的。用于本发明的环氧树脂优选具有环氧化物当量重量为100-约700。
本发明的可光成像的组合物暴露于光化辐射和在碱性水溶液(例如1%碳酸钠)中显影后,环氧树脂被固化以使可光成像的层变硬和持久。尽管环氧树脂在实际应用中是自交联的以获得充足快速的热固化,但它一般需要包括E)环氧固化剂(epoxy curative),即进入交联反应和/或环氧固化催化剂的化合物。
环氧固化剂的实例是多官能羧酸和保护的异氰酸酯的酸酐,例如ε-己内酰胺保护的异佛尔酮。环氧固化催化剂的实例包括胺,例如三亚乙基胺和二氰基二酰胺。
为了环氧树脂不用过早地固化,一般情况下,提供本发明的组合物作为两部分组合物。酸官能的粘合剂组合物和环氧固化剂和/或固化催化剂刚好在使用之前以和环氧分开的形式提供的。目前的实际应用是除了环氧树脂以外的所有组分是第一部分,环氧树脂作为第二部分提供。
该组合物也可含有附加的材料,例如颜料和助溶剂,如现有技术中常规使用的。该类型的许多组合物是着色的,典型地,相对于(A)加(B)的总重量,含有最多约3.0wt%量的分散的颜料。
本发明的组合物作为液体组合物以常规的方式直接应用与印刷电路板中。涂布后,干燥组合物以除去水和还除去挥发物,例如助溶剂用作聚结剂。当可光成像的组合物干燥时,系统聚结成为连续的膜。干燥优选在稍微升高的温度下进行,都是为了赶快除去水和其它挥发物。优选干燥在约65℃-约80℃下进行。
加工以常规方式进行。在一典型的程序中,由液体组合物形成的可光成像的组合物层被涂在印刷电路板上。可光成像的组合物层通过适当的图形暴露于光化辐射中。在曝光区域中暴露于光化辐射使单体或低聚物聚合,导致了耐显影剂的交联结构。接下来,组合物在稀释的碱性水溶液中显影,例如1%碳酸钠溶液。碱性溶液造成与粘合剂聚合物的酸基团形成盐,使得它们可溶解和可除去。
如果该组合物是形成焊锡掩模的组合物,显影后,以充足的时间加热印刷电路板,典型地加热至约140-约160℃以实现环氧树脂的固化,由此使层变硬和耐久。
目前的配方特别适用于喷涂。其它涂布手段,例如帘膜式涂布需要较高的粘度。为此目的,可加增稠剂,例如聚氨酯增稠剂,如在美国专利5364737中所描述的,其教导在此引入作为参考。
现在通过具体的实施例详细描述本发明。
实施例1(粘合剂低聚物的形成)
用商购的环氧丙烯酸酯Novacure-3701(用来生产称为R-M929的低聚物)开始,该分子逐次和2摩尔的HDI、2摩尔的二甲醇丙酸、2摩尔的HDI和2摩尔的HEMA反应,由此生产具有二羧酸官能团和四丙烯酸酯官能团的粘合剂低聚物。
实施例2
按下表配制称为#2415-23和#2415-8b的两个焊锡掩模制剂。焊锡掩模制剂是液体的并可通过帘涂法而涂布。
#2415-23
A部分(g) 250.00总和A+B(g) 333.33 |
%固体 60.00混合比A∶B 3.00 |
化学物质 固体% 化学物质 总重% 重量% 溶剂 数量
(A+B) %固体 (A+B部分) (A部分) (g) (g)
A部分
R-M929 29.56 73.78 24.04 32.05 21.01 80.13
R-M945 9.36 41.40 13.57 18.09 26.50 45.22
BB-3056 0.50 100.00 0.30 0.40 0.00 1.00
SR-454 2.00 100.00 1.20 1.60 0.00 4.00
Modaflow 3.00 100.00 1.80 2.40 0.00 6.00
I-907 4.00 100.00 2.40 3.20 0.00 8.00
ITX 1.28 100.00 0.77 1.02 0.00 2.56
Sun Green 1.98 100.00 1.19 1.58 0.00 3.96
Huber 90C 19.50 100.00 11.70 15.60 0.00 39.00
MY24 0.22 100.00 0.13 0.18 0.00 0.44
CG1400 1.10 100.00 0.66 0.88 0.00 2.20
HP-270 5.00 100.00 3.00 4.00 0.00 10.00
3-MB 0.00 0.00 14.25 19.00 47.49 47.49
75.00 100.00 250.00
B部分
DER 331 11.25 100.00 6.75 27.00 0.00 22.50
ECN-1299 11.25 50.00 13.50 54.00 22.50 45.00
DBE 0.00 0.00 4.75 19.00 15.83 15.83
总和 100.00 25.00 100.00 133.33 83.33
R-M945 异丁烯酸甲酯50摩尔%,异丁烯酸50摩尔%,异丁烯酸25%和HEMA羟基乙基丙烯酸酯酯化;酸价125-150。
SR-454 异丁烯酸酯化的三羟甲基丙烷三丙烯酸酯
BB-3056 碎泡机
Modaflow 流动控制剂
Irgacure-907 光引发剂
ITX 光引发剂
Sun Green 颜料
Huber 90C 填料
MY24 固化剂
CG1400 二氰基二酰胺,固化剂
HP-270 热解法二氧化硅,填料
3-MB 3-甲氧基丁醇,溶剂
DER 331 双酚A环氧树脂(液体)
ECN-1299 Novlac环氧树脂
DBE -#2415-8b
A部分(g) 300.00总和A+B(g) 450.00 |
%固体 65.00混合比A∶B 2.00 |
化学物质 固体% 化学物质 总重% 重量% 溶剂 数量
(A+B) %固体 (A+B部分) (A部分) (g) (g)
A部分
R-M929 29.56 73.78 26.04 39.06 30.73 117.19
R-0915 9.49 56.02 10.91 16.36 21.59 49.08
BB-3056 0.50 100.00 0.33 0.49 0.00 1.46
SR-454 2.00 100.00 1.30 1.95 0.00 5.85
Modaflow 3.00 100.00 1.95 2.93 0.00 8.78
I-907 4.00 100.00 2.60 3.90 0.00 11.70
ITX 1.28 100.00 0.83 1.25 0.00 3.74
Sun Green 1.98 100.00 1.29 1.93 0.00 5.79
Huber 90C 19.46 100.00 12.65 18.97 0.00 56.92
MY24 0.22 100.00 0.14 0.21 0.00 0.64
CG1400 1.10 100.00 0.72 1.07 0.00 3.22
HP-270 5.00 100.00 3.25 4.88 0.00 14.63
PMA 0.00 0.00 4.67 7.00 21.00 21.00
66.67 100.00 300.00
B部分
DER 331 0.00 100.00 0.00 0.00 0.00 0.00
ECN-1299 22.50 50.00 29.25 87.75 65.81 131.63
DBE 0.00 0.00 4.08 12.25 18.38 18.38
总和 100.00 33.33 100.00 157.50 150.00
R-0915 由Morton International Organic Synthesis department生产的粘合剂,具有酸和丙烯酸酯官能度。R-095是4-羟基丁基丙烯酸酯和苯乙烯-马来酸酐(SMA-1000)以1.05∶1.00摩尔比(4-HBA5%过量)的酯化反应的结果。粘合剂是在含约55%固体的EEP溶剂中制备的,平均分子量Mw是15000。
PMA 丙二醇一甲基醚醋酸酯,溶剂
Claims (7)
1.具有下式的低聚物:
(CH2=CH(H或CH3)-CO-X-R-CH(OZ)-CH2-O-φ-)2-C(CH3)2
其中R是1-40个碳的亚烷基;
X不存在或选自分子量在50-2000之间的亚烷基二醇、聚酯二醇和聚醚二醇的二醇;和
Z是式:
-CO-NH-Y-NH-CO-O(-VW1-5-O-CO-NH-Y-NH-CO-O)n-Q-O-CO-CH(H或CH3)=CH2;
其中Y是亚烷基或芳香烃基团;
n=1-4;
V是亚烷基,芳香基,烷芳基或芳烷基烃基;W是相同的或不同的,且每个选自COOH,SO2H和PO4H(H或C1-18烷基)的酸基,
Q是2-6个碳原子的亚烷基。
2.权利要求1的低聚物,其中n=1。
3.可光成像的组合物,以(A)+(B)的固体为基准,含有:
(A)具有充分羧酸官能团的50-100wt%粘合剂分子,以便抗光蚀剂在碱性水溶液中显影,基于(A)加(B)的总重,5-100wt%的组合物是(A1)权利要求1的低聚物,和0-50wt%的组合物是(A2)附加的酸官能的粘合剂聚合物;
(B)0-50wt%的可光聚合的非酸官能的组分,含有α,β-烯不饱和单体和/或除了权利要求1的低聚物以外的α,β-烯不饱和低聚物,
(C)0.1-10wt%的光引发剂化学体系。
4.权利要求3的组合物,含至少10wt%的附加的酸官能的粘合剂聚合物(A2),基于(A)加(B)的总重量。
5.权利要求3的组合物,含至少2wt%的(B),基于(A)加(B)的总重量。
6.权利要求5的组合物,进一步含有5-40wt%的(D)环氧树脂,基于(A)加(B)的总重量。
7.权利要求6的组合物,含有1-10wt%的(E)环氧交联剂和/或环氧固化剂,基于(A)加(B)的总重量。
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EP (1) | EP1094364A1 (zh) |
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JP2004151691A (ja) * | 2002-09-30 | 2004-05-27 | Rohm & Haas Electronic Materials Llc | 改良フォトレジスト |
JP2004163904A (ja) * | 2002-09-30 | 2004-06-10 | Rohm & Haas Electronic Materials Llc | 改善された光開始剤 |
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JP4587865B2 (ja) | 2004-04-22 | 2010-11-24 | 昭和電工株式会社 | 感光性樹脂組成物及びその硬化物並びにそれらを使用するプリント配線基板の製造方法 |
TW200613903A (en) * | 2004-05-26 | 2006-05-01 | Showa Denko Kk | Photosensitive resin composition, and cured product and use thereof |
US7375144B2 (en) * | 2005-06-16 | 2008-05-20 | Eastman Chemical Company | Abrasion resistant coatings |
CN104730862B (zh) * | 2013-12-19 | 2020-06-19 | 乐凯华光印刷科技有限公司 | 阴图感光组合物及用该组合物制成的热敏板 |
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US4092443A (en) | 1976-02-19 | 1978-05-30 | Ciba-Geigy Corporation | Method for making reinforced composites |
US4153778A (en) | 1978-03-30 | 1979-05-08 | Union Carbide Corporation | Acrylyl capped urethane oligomers |
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US4762902A (en) | 1985-12-16 | 1988-08-09 | The B. F. Goodrich Company | Electron curable polyurethanes |
US5364736A (en) | 1987-12-07 | 1994-11-15 | Morton International, Inc. | Photoimageable compositions |
US5229252A (en) | 1989-06-09 | 1993-07-20 | Morton International, Inc. | Photoimageable compositions |
US5290663A (en) | 1991-03-01 | 1994-03-01 | W. R. Grace & Co.-Conn. | Photocurable polyurethane-acrylate ionomer compositions for aqueous developable printing plates |
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TW418346B (en) * | 1993-03-05 | 2001-01-11 | Ciba Sc Holding Ag | Photopolymerisable compositions containing tetraacrylates |
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US6207346B1 (en) * | 1997-04-09 | 2001-03-27 | Advanced Coatings International | Waterborne photoresists made from urethane acrylates |
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