CN102786631B - 光敏性碱可溶性树脂、其制备方法及彩色光刻胶 - Google Patents

光敏性碱可溶性树脂、其制备方法及彩色光刻胶 Download PDF

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CN102786631B
CN102786631B CN201210292588.3A CN201210292588A CN102786631B CN 102786631 B CN102786631 B CN 102786631B CN 201210292588 A CN201210292588 A CN 201210292588A CN 102786631 B CN102786631 B CN 102786631B
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CN102786631A (zh
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李琳
舒适
孙雯雯
赵明
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BOE Technology Group Co Ltd
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Abstract

本发明提供了一种光敏性碱可溶性树脂、其制备方法及彩色光刻胶。本发明的光敏性碱可溶性树脂的结构式如式I所示。该光敏性碱可溶性树脂的制备方法，包括使环氧乙烷与α-羟烷基苯酮发生共聚合得到第一中间产物，然后将所述第一中间产物与丙烯酸甘油酯、苯乙烯、马来酸酐共聚合的产物反应得到第二中间产物，将所述第二中间产物进行氧化处理，生成光敏性碱可溶性树脂。该光敏性碱可溶性树脂显影性能、柔性及反应活性均较高，用其制备的光刻胶，可用于制作彩色滤光片，所形成的图形具有较高的分辨率。式I

Description

光敏性碱可溶性树脂、其制备方法及彩色光刻胶
技术领域
本发明涉及碱可溶性树脂，尤其涉及一种光敏性碱可溶性树脂、其制备方法及利用该光敏性碱可溶性树脂制备的彩色光刻胶。
背景技术
随着液晶显示器的不断发展，高画质、高分辨率已经成为消费者的首选。在液晶显示器中，彩色滤光片是实现液晶显示器彩色显示的关键部分，因此对彩色滤光片的要求也越来越高。
彩色光刻胶是制作彩色滤光片的原料，彩色光刻胶主要由颜料、碱可溶性树脂、光固化树脂、光引发剂、溶剂及添加助剂组成。目前，颜料分散法是制作彩色滤光片的主流方法，在一些低世代线上仍然采用这种工艺。然而，应用颜料分散法在制备高画质、高分辨率的液晶显示器时，由于高分辨率、高色域、高色纯度的要求，增加了制备彩色光刻胶的难度。为了获得高色彩饱和度，高色纯度及高色域的光刻胶，需要增加颜料在光刻胶中的比例，然而在组分中颜料含量的不断提高影响了彩色光刻胶的显影性及感光性，从而使分辨率降低。
发明内容
为了解决上述问题，本发明提供了一种显影性能、柔性及反应活性均较高的光敏性碱可溶性树脂，提高液晶显示器的分辨率。
本发明所提供的光敏性碱可溶性树脂，包括如式I所示的化合物,
Figure BDA00002020442300011
式I
其中，n1为30~200；n2为1~8；R1为-H或-O(CH2)n3OH或-N(CH3)2或-CnH2n+1或-SCH3或-O(CH2)n4OCOCH=CH2；n3为1~6；n4为1~5；n为1~12；R2为-H或-CH3；R3为-H或-CH3。
优选地，R1为-H或-O(CH2)2OH或-O(CH2)2OCOCH=CH2或-N(CH3)2或-C12H25或-SCH3；
本发明的另一个目的是提供一种光敏性碱可溶性树脂的制备方法。
本发明所提供的光敏性碱可溶性树脂的制备方法，包括以下步骤：第一步、使环氧乙烷与α-羟烷基苯酮发生共聚合得到第一中间产物；第二步、将丙烯酸甘油酯、苯乙烯、马来酸酐共聚合的产物与所述第一中间产物反应，得到第二中间产物；第三步、所述第二中间产物进行氧化处理，生成光敏性碱可溶性树脂。
优选地，根据本发明的一个方面，所述环氧乙烷与所述α-羟烷基苯酮的摩尔比为1:1-8:1；所述丙烯酸甘油酯、所述苯乙烯和所述马来酸酐的摩尔比为（1-1.2）：（1-1.2）：（1-1.3）；所述环氧乙烷与所述丙烯酸甘油酯的摩尔比（0.5-6.1）：1。
优选地，根据本发明的一个方面，所述共聚合中使用3-巯基丙酸，所述3-巯基丙酸与所述环氧乙烷的摩尔比为（0-0.1）：1；所述共聚合中使用巯基类链转移剂，所述巯基类链转移剂与所述丙烯酸甘油酯的摩尔比为（0-0.4）：1。
优选地，根据本发明的一个方面，所述α-羟烷基苯酮为HMPP或HHMP。
优选地，根据本发明的一个方面，所述第一步的反应在70-120℃下进行；所述第二步的反应在70-100℃下进行。
优选地，根据本发明的一个方面，所述共聚合在丙二醇甲醚醋酸酯或3-乙氧基丙酸乙酯作溶剂的环境下进行。
优选地，根据本发明的一个方面，所述共聚合结束后用石油醚、甲苯或者环己烷沉降。
优选地，根据本发明的一个方面，所述巯基类链转移剂为十二硫醇或巯基乙醇。
本发明的另一个目的是提供一种光刻胶，该光刻胶显影性能优异。
本发明所提供的光刻胶，包含所述的光敏性碱可溶性树脂。
如本领域中已知的，本发明的光刻胶还包含颜料、光固化树脂、光引发剂、溶剂及添加助剂。
本发明的光敏性碱可溶性树脂，具有烷氧基链段，可提高碱可溶性树脂的显影性能；具有长的支链，增加了碱可溶性树脂的柔性，使得其在组分中的分布更加均匀；同时该光敏性碱可溶性树脂的支链中具有光敏基团-C(CH3)2COPhR1，赋予该光敏性碱可溶性树脂高的反应活性，减少小分子光引发剂的使用量。用本发明的光敏性碱可溶性树脂制备的光刻胶，可用于制作液晶显示器的彩色滤光片，所形成的图形具有较好的显影性能和较高的分辨率。
具体实施方式
以下结合优选实施例对本实施方式的技术方案进行详细地阐述。以下实施例仅用于说明和解释本发明，而不构成对本发明技术方案的限制。
本发明提供的光敏性碱可溶性树脂，包括式I所示的化合物,
式I
其中，
n1为30~200；
n2为1~8；
R1为-H或-O(CH2)n3OH或-O(CH2)n4OCOCH=CH2或-N(CH3)2或-CnH2n+1或-SCH3；n3为1~6；n4为1~5；n为1~12；
R2为-H或-CH3；
R3为-H或-CH3。
本发明的光敏性碱可溶性树脂的制备方法，包括以下步骤：
第一步、使环氧乙烷与α-羟烷基苯酮发生共聚合得到第一中间产物；
第一步的反应具体可以在70-120℃的温度环境下，使环氧乙烷与α-羟烷基苯酮发生共聚合得到第一中间产物。
所使用的α-羟烷基苯酮具体可以为HMPP或HHMP。
环氧乙烷与α-羟烷基苯酮的共聚合可以在丙二醇甲醚醋酸酯或3-乙氧基丙酸乙酯环境下进行。
所述环氧乙烷与α-羟烷基苯酮的共聚合结束后可以用石油醚、甲苯或者环己烷沉降。
第二步、将丙烯酸甘油酯、苯乙烯、马来酸酐共聚合的产物与所述第一中间产物反应，得到第二中间产物。
第二步的反应具体可以在70-100℃的温度环境下，将第一中间产物与丙烯酸甘油酯、苯乙烯、马来酸酐共聚合的产物反应得到第二中间产物。
丙烯酸甘油酯、苯乙烯、马来酸酐共聚合可以在丙二醇甲醚醋酸酯或3-乙氧基丙酸乙酯环境下进行。
丙烯酸甘油酯、苯乙烯、马来酸酐共聚合结束后可以用石油醚、甲苯或者环己烷沉降。
第三步、将所述第二中间产物进行氧化处理，生成光敏性碱可溶性树脂。
所述第二中间产物可以通过加入K2FeO4、二甲亚砜、二环己基碳二亚胺进行氧化处理。
本发明的光敏性碱可溶性树脂的制备方法中，所述环氧乙烷与所述α-羟烷基苯酮的摩尔比可以为1:1-8:1；所述丙烯酸甘油酯、所述苯乙烯和所述马来酸酐的摩尔比可以为（1-1.2）：（1-1.2）：（1-1.3）；所述环氧树脂与所述丙烯酸甘油酯的摩尔比可以为（0.5-6.1）：1。
本发明的光敏性碱可溶性树脂的制备方法中，所述共聚合中使用3-巯基丙酸，所述3-巯基丙酸与所述环氧乙烷的摩尔比可以为（0-0.1）:1；所述共聚合中使用巯基类链转移剂，所述巯基类链转移剂与所述丙烯酸甘油酯的摩尔比可以为（0-0.4）:1。所述巯基类链转移剂具体可以为十二硫醇或巯基乙醇。
本发明还提供一种彩色光刻胶，包含上述的光敏性碱可溶性树脂、颜料、光固化树脂、光引发剂、溶剂及添加助剂等。所述光敏性碱可溶性树脂可以是前文所述的任何一种，具体不再详述。
如下将结合具体实施例说明制备所述光敏性碱可溶性树脂的具体过程。
以下具体实施例中获得的第一中间产物和第二中间产物分别代表相似的结构，不同的第一中间产物之间，以及不同的第二中间产物之间的区别是具有不同的取代基R1。HMPP和HHMP统称为α-羟烷基苯酮，而R1基团为α-羟烷基苯酮中苯环所带的取代基，R1可以为-H或-O(CH2)n3OH或-N(CH3)2或-CnH2n+1或-O(CH2)n4OCOCH=CH2或-SCH3；n3为1~6；n4为1~5；n为1~12；
实施例1：
第一步的反应：
将30g（0.68mol）环氧乙烷、20g（0.12mol）HMPP（Darocur1173ciba）和3g（0.028mol）3-巯基丙酸及100ml丙二醇甲醚醋酸酯（PMA）（DOW公司）混合加入到三口烧瓶中，油浴加热到100℃，搅拌回流6个小时后，停止反应。然后用石油醚沉降，得到深棕色固体第一中间产物，将第一中间产物溶解于80mlPMA中，得到0.6mol/L的溶液。
第二步的反应：
将14g（0.112mol）丙烯酸甘油酯、10g（0.096mol）苯乙烯、12g（0.122mol）马来酸酐、2.02g（0.01mol）十二硫醇及210gPMA混合在四口瓶中，80℃油浴加热，搅拌下冷凝回流，当四口瓶中溶液的温度达到85℃时，以2滴/秒的速度滴加热引发剂偶氮二异丁腈（AIBN）溶液（50质量%），半小时滴加完毕。在反应3个小时以后，滴加第一步反应得到的浓度0.6mol/L的溶液（包含第一中间产物），半小时滴加完毕，保持85℃油浴加热，搅拌回流6个小时，反应结束后用甲苯沉降，干燥后得到固体第二中间产物。第三步的反应：
将第二中间产物溶于100g3-乙氧基丙酸乙酯（EEP）中，30℃搅拌条件下加入1.2gK2FeO4氧化剂，反应6小时，过滤，得到淡黄色固体，即光敏性碱可溶性树脂A1。
实施例2：
第一步的反应：
将50g（1.136mol）环氧乙烷、26g（0.152mol）HHMP（Darocure2959）和5g（0.047mol）3-巯基丙酸及150ml PMA混合加入到三口烧瓶中，油浴加热到100℃，搅拌回流6个小时后，停止反应。然后用石油醚沉降，得到深棕色固体第一中间产物，将第一中间产物溶解于150ml PMA中，得到0.6mol/L的溶液。
第二步的反应：
将30g（0.24mol）丙烯酸甘油酯、25g（0.24mol）苯乙烯、25g（0.255mol）马来酸酐、2g（0.01mol）十二硫醇及210gPMA混合在四口瓶中，80℃油浴加热，搅拌下冷凝回流，当四口瓶中溶液的温度达到85℃时，以2滴/秒的速度滴加热引发剂AIBN溶液（50%质量百分比），半小时滴加完毕。在反应3个小时以后，滴加第一步反应得到的浓度0.6mol/L的溶液（包含第一中间产物），半小时滴加完毕，保持85℃油浴加热，搅拌回流6个小时，反应结束后用甲苯沉降，干燥后得到第二中间产物。
第三步的反应：
将第二中间产物溶于100gEEP中，30℃搅拌条件下加入1.2gK2FeO4氧化剂，反应6小时，过滤，得到淡黄色固体，即光敏性碱可溶性树脂A2。
实施例3：
第一步的反应：
将4.4g（0.1mol）环氧乙烷和22.4g（0.1mol）HHMP（Darocure2959）及100ml3-乙氧基丙酸乙酯（EEP）混合加入到三口烧瓶中，油浴加热到70℃，搅拌回流8个小时后，停止反应。然后用甲苯沉降，得到深棕色固体第一中间产物，将第一中间产物溶解于80ml EEP中，得到0.6mol/L的溶液。
第二步的反应：
将25g（0.2mol）丙烯酸甘油酯、23g（0.221mol）苯乙烯、20g（0.204mol）马来酸酐、0.156g（0.002mol）巯基乙醇及200gEEP混合在四口瓶中，70℃油浴加热，搅拌下冷凝回流，当四口瓶中溶液的温度达到80℃时，以2滴/秒的速度滴加热引发剂过氧化二苯甲酰溶液（50质量%），半小时滴加完毕。在反应3个小时以后，滴加第一步反应得到的浓度0.6mol/L的溶液（包含第一中间产物），半小时滴加完毕，保持80℃油浴加热，搅拌回流8个小时，反应结束后用石油醚沉降，干燥后得到固体第二中间产物。
第三步的反应：
将第二中间产物溶于100gPMA中，30℃搅拌条件下加入1.2g二甲亚砜氧化剂，反应6小时，过滤，得到淡黄色固体，即光敏性碱可溶性树脂A3。
实施例4：
第一步的反应：
将35.2g（0.8mol）环氧乙烷、16.4g（0.1mol）HMPP和8.48g（0.08mol）3-巯基丙酸及100mlPMA混合加入到三口烧瓶中，油浴加热到120℃，搅拌回流4个小时后，停止反应。然后用环己烷沉降，得到深棕色固体第一中间产物，将第一中间产物溶解于80mlPMA中，得到0.6mol/L的溶液。
第二步的反应：
将25g（0.2mol）丙烯酸甘油酯、23g（0.221mol）苯乙烯、20g（0.204mol）马来酸酐、4.04g（0.02mol）十二硫醇及210gPMA混合在四口瓶中，100℃油浴加热，搅拌下冷凝回流，当四口瓶中溶液的温度达到90℃时，以2滴/秒的速度滴加热引发剂AIBN溶液（50质量%），半小时滴加完毕。在反应3个小时以后，滴加上述浓度0.6mol/L的溶液（包含第一中间产物），半小时滴加完毕，保持90℃油浴加热，搅拌回流4个小时，反应结束后用甲苯沉降，干燥后得到固体第二中间产物。
第三步的反应：
将第二中间产物溶于100gEEP中，30℃搅拌条件下加入1.2g二环己基碳二亚胺氧化剂，反应6小时，过滤，得到淡黄色固体，即光敏性碱可溶性树脂A4。
实施例5：
按照表1中的成分组成，将每组物质混合，各自搅拌均匀后制成编号1-5的彩色光刻胶，用spin-coater在400-700rpm转速下将它们分别旋涂到玻璃基板上1.5-2.0vm，95℃经过3min的预烘烤，用紫外光分别掩膜曝光8s、12s、16s、20s，再用0.05%的氢氧化钾溶液进行显影，形成像素图形。
表1中各物质可以由下述公司购买：
SB404:Sartomer公司
DPHA：双季戊四醇五/六丙烯酸酯Sartomer公司
环氧：DEN431环氧型酚醛树脂DOW公司
Figure BDA00002020442300081
369:BASF公司
流平剂：glide440  聚硅氧烷-聚醚共聚物  TEGO公司
消泡剂：Airex 920  TEGO公司
EEP:3-乙氧基丙酸乙酯  DOW公司
PMA:丙二醇甲醚醋酸酯  DOW公司
表1
Figure BDA00002020442300082
表2为按照表1制备的编号1-5彩色光刻胶形成的在不同曝光时间下显影后的像素图形的特性比较。
表2中：将显影后的像素图形放到显微镜下200倍观察，看不同曝光时间下图形的情况，
●代表边缘清晰整齐▲代表略有毛刺■代表边缘不整齐★代表图形不完全。
稳定性：在0~10℃环境下放置两周，对比其曝光时间的变化。
图形分辨率：在掩膜版线宽分别为20μm，15μm，12μm，10μm，8μm，6μm，3μm，2μm，1μm下曝光，显影，形成边缘清晰的线宽即为分辨率。
表2
Figure BDA00002020442300092
由表2可以看出，编号1-4的光刻胶，即采用本发明的光敏性碱可溶性树脂制备的光刻胶，在8s和12s的曝光时间下边缘清晰整齐，在0~10℃环境下放置两周曝光时间基本无变化，图形分辨率可达到3μm，而编号5的光刻胶，即采用现有技术中的感光树脂，在8s曝光时间下略有毛刺，在12s的曝光时间下边缘不整齐，在0~10℃环境下放置两周曝光时间有明显变化，图形分辨率仅达到10μm。
因此可以说明由实施例1-4的碱可溶性树脂制备的彩色光刻胶稳定性高，分辨率高，显影性能好。
以上说明对本发明而言只是说明性的，而非限制性的，本领域普通技术人员理解，在不脱离所附权利要求所限定的精神和范围的情况下，可做出许多修改、变化或等效，但都将落入本发明的保护范围内。

Claims (11)

1.一种光敏性碱可溶性树脂，包括式I所示的化合物, 
Figure FDA0000473775210000011
其中， 
n1为30～200； 
n2为1～8； 
R1为-H或-O(CH2)n3OH或-O(CH2)n4OCOCH=CH2或-N(CH3)2或-CnH2n+1
或-SCH3；n3为1～6；n4为1～5；n为1～12； 
R2为-H或-CH3； 
R3为-H或-CH3。 
2.根据权利要求1所述的光敏性碱可溶性树脂，其特征在于， 
R1为-H或-O(CH2)2OH或-O(CH2)2OCOCH=CH2或-N(CH3)2或-C12H25
或-SCH3。
3.一种光敏性碱可溶性树脂的制备方法，包括以下步骤： 
第一步、使环氧乙烷与α-羟烷基苯酮发生共聚合得到第一中间产物； 
第二步、将丙烯酸甘油酯、苯乙烯、马来酸酐共聚合的产物与所述第一中间产物反应，得到第二中间产物； 
第三步、将所述第二中间产物进行氧化处理，生成光敏性碱可溶性树脂； 
其中，所述环氧乙烷与所述α-羟烷基苯酮的摩尔比为（1:1）-（8:1）；所 述丙烯酸甘油酯、所述苯乙烯和所述马来酸酐的摩尔比为（1-1.2）：（1-1.2）：（1-1.3）；所述环氧乙烷与所述丙烯酸甘油酯的摩尔比（0.5-6.1）：1。 
4.根据权利要求3所述的制备方法，其特征在于，所述共聚合中使用3-巯基丙酸，所述3-巯基丙酸与所述环氧乙烷的摩尔比为（0-0.1）:1；所述共聚合中使用巯基类链转移剂，所述巯基类链转移剂与所述丙烯酸甘油酯的摩尔比为（0-0.4）:1。 
5.根据权利要求4所述的制备方法，其特征在于，所述α-羟烷基苯酮为HMPP或HHMP。 
6.根据权利要求4所述的制备方法，其特征在于，所述第一步的反应在70-120℃下进行；所述第二步的反应在70-100℃下进行。 
7.根据权利要求4所述的制备方法，其特征在于，所述第三步反应通过加入K2FeO4或二甲亚砜或二环己基碳二亚胺进行氧化处理。 
8.根据权利要求4所述的制备方法，其特征在于，所述共聚合在丙二醇甲醚醋酸酯或3-乙氧基丙酸乙酯环境下进行。 
9.根据权利要求4所述的制备方法，其特征在于，所述共聚合结束后用石油醚、甲苯或者环己烷沉降。 
10.根据权利要求4所述的制备方法，其特征在于，所述巯基类链转移剂为十二硫醇或巯基乙醇。 
11.一种彩色光刻胶，其特征在于，包含权利要求1或2所述的光敏性碱可溶性树脂。 
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