CN106459305B - 可光固化的树脂组合物 - Google Patents
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Abstract
本申请涉及一种树脂组合物,特别是涉及一种可光固化的树脂组合物。已知通过添加无机添加剂(例如热解法二氧化硅)可实现粘合剂组合物的触变行为。添加无机添加剂导致显著的颗粒问题,因为热解法二氧化硅是固体颗粒且影响粘合剂组合物的光学性能。根据本发明,提供了一种具有触变行为的不含颗粒的树脂组合物。本发明的组合物包含a)30‑90wt%的具有大于15000的分子量的氨基甲酸酯丙烯酸酯低聚物、b)2‑40wt%的具有苯环的(甲基)丙烯酸酯单体、和c)0.2‑10wt%的光引发剂。
Description
技术领域
本申请涉及一种树脂组合物,特别是涉及一种可光固化的树脂组合物。
背景技术
如果可光固化的树脂组合物具有相应的光学特性,其可以用在光学组件应用中,如用在用于触摸面板组件的液体光学透明粘合剂中。液体光学透明粘合剂(LOCA,liquidoptically-clear adhesive)是这样一种基于液体的粘合技术,该基于液体的粘合技术用在触摸面板和显示装置中以将玻璃盖板(cover lens)、塑料或其它光学材料粘合到主要传感单元上或使其彼此粘合。粘合剂被用来改善装置的光学性质以及改善其它属性例如耐久性。
为了生产率,在涂覆时需要低粘度的粘合剂;但是为了更好的层合效果,需要较高的粘度。
WO 2012/036980 A2公开了一种具有触变行为的粘合剂组合物。触变性是一种剪切稀化性质。在静态条件下浓稠(粘稠)的某些凝胶和流体在摇动、搅拌或其它应力下将随着时间过去而流动(变得稀释,粘稠度较小)。然后需要固定时间来恢复到较粘稠的状态。根据上述文献,粘合剂组合物的触变行为是通过添加无机添加剂例如热解法二氧化硅来实现的。但是,添加无机添加剂导致显著的颗粒问题,因为热解法二氧化硅是固体颗粒且影响粘合剂组合物的光学性能。
发明内容
因此,本申请的一个目的是提供一种具有触变行为的不含颗粒的液体组合物。
该目的通过一种可光固化的树脂组合物来实现,所述可光固化的树脂组合物包含:
a)30-90wt%的具有大于15000的分子量的氨基甲酸酯丙烯酸酯低聚物,
b)2-40wt%的具有苯环的(甲基)丙烯酸酯单体,和
c)0.2-10wt%的光引发剂,
其中重量百分比涉及本发明的可光固化的树脂组合物的总重量。
令人惊讶的是,已经发现上述可光固化的树脂组合物在不添加触变引发剂(例如热解法二氧化硅)的情况下也显示出触变行为。因为不需要使用所述触变剂,本发明的可光固化的树脂组合物不具有任何颗粒问题,且具有非常优异的光学性能。本发明的组合物由于其优异的光学性质而适合用在光学组件应用中,例如用在用于触摸面板组件的液体光学透明粘合剂中。
具体实施方式
本文使用的术语(甲基)丙烯酸酯是指丙烯酸酯或甲基丙烯酸酯。
(甲基)丙烯酸酯的苯环可包括一个或多个除了氢之外的取代基/基团。
氨基甲酸酯丙烯酸酯是本领域技术人员公知的,其例如可通过二异氰酸酯(优选脂肪族二异氰酸酯)与羟基丙烯酸酯的反应来获得,或例如可通过二异氰酸酯(优选脂肪族二异氰酸酯)与羟基丙烯酸酯和多元醇的反应来获得。
根据本发明可使用的优选的氨基甲酸酯丙烯酸酯例如是来自大阪有机化学工业株式会社(Osaka Organic Chemical Co.,Ltd)的UVA-002和UVA-004。可以使用其它氨基甲酸酯丙烯酸酯,只要它们的分子量大于15000。
优选的氨基甲酸酯丙烯酸酯的性质如下:
UVA-002 | UVA-004 | |
Mw | 20000 | 20000 |
粘度(m*Pa*s) | 200000 | 170000 |
透射率(%) | 99 | 99 |
雾度(%) | 0.1 | 0.1 |
具有苯环的(甲基)丙烯酸酯单体可选自丙烯酸苄酯、丙烯酸苯氧基乙酯、壬基苯氧基聚乙二醇丙烯酸酯、乙氧基化双酚A二丙烯酸酯、甲基丙烯酸苯氧基乙酯、乙氧基化双酚A二甲基丙烯酸酯、甲基丙烯酸苄酯、甲基丙烯酸1-苯乙酯、甲基丙烯酸2-苯氧基乙酯、甲基丙烯酸2-苯乙酯、甲基丙烯酸3-苯丙酯、丙烯酸3-苯丙酯和丙烯酸2-苯氧基乙酯及它们的组合。使用丙烯酸苄酯作为(甲基)丙烯酸酯单体是优选的。
特别是,具有苯环的(甲基)丙烯酸酯单体可选自
(结构式I)
(结构式II)
(结构式III)
(结构式IV)
(结构式V)
(结构式VI)
(结构式VII)
虽然本发明的组合物必须含有至少一种具有苯环的(甲基)丙烯酸酯单体,但是根据本发明的组合物可包括一种或多种额外的单体,例如,丙烯酸异冰片酯、丙烯酸4-羟丁酯和三环癸烷二甲醇二丙烯酸酯,其中额外的单体可用于微调所得经固化的组合物的性质。
根据本发明的组合物包含至少一种光引发剂。光引发剂引发反应,且对组合物的固化具有很大影响,其中不同种类的光引发剂具有不同的问题和优点。例如,一些光引发剂导致经固化的组合物褪色,而另一些光引发剂特别良好地适合于着色体系。
根据本发明,优选光引发剂选自苯基乙醛酸酯、α-羟基酮、α-氨基酮、苯偶酰二甲基缩酮、单酰基氧化膦、双酰基氧化膦、二苯甲酮、肟酯、二茂钛及它们的组合。
优选可光固化的树脂组合物包含
a)40-80wt%的具有大于15000的分子量的氨基甲酸酯丙烯酸酯低聚物,
b)5-30wt%的具有苯环的(甲基)丙烯酸酯单体,和
c)0.5-6wt%的光引发剂。
更优选可光固化的树脂组合物包含
a)45-80wt%的具有大于15000的分子量的氨基甲酸酯丙烯酸酯低聚物,
b)5-28wt%的具有苯环的(甲基)丙烯酸酯单体,和
c)0.5-6wt%的光引发剂。
最优选可光固化的树脂组合物包含
a)50-80wt%的具有大于15000的分子量的氨基甲酸酯丙烯酸酯低聚物,
b)5-25wt%的具有苯环的(甲基)丙烯酸酯单体,和
c)0.5-6wt%的光引发剂。
可光固化的树脂组合物可包含0-40wt%、优选0-30wt%的其它组分,如变形剂(deformer)、紫外线吸收剂、光稳定剂、硅烷偶联剂、抗氧化剂或它们的组合。
关于其它组分,优选变形剂(消泡剂或防泡沫剂)基于硅氧烷和聚合物。抗氧化剂优选地选自酚类抗氧化剂、胺类抗氧化剂、基于硫的抗氧化剂和多功能抗氧化剂(multifunctional antioxidant)或它们的组合。紫外线吸收剂优选是苯并三唑类紫外线吸收剂,特别是2-(5-叔丁基-2-羟基苯基)苯并三唑。
本发明的另一个方面涉及所述可光固化的树脂组合物用于粘合光学组件中的部件的用途。
本发明的另一个方面涉及所述可光固化的树脂组合物用于触摸面板传感组件的用途。
本发明的另一个方面涉及所述可光固化的树脂组合物用于玻璃盖板粘合的用途。
本发明的另一个方面涉及所述可光固化的树脂组合物用于直接将玻璃盖板粘合到LCD模块的用途。
最后,本发明的另一个方面涉及所述可光固化的树脂组合物用于液晶显示器上以将触摸屏幕固定在基材上的用途,其中,所述基材可以是显示面板,优选地选自液晶显示器、等离子显示器、发光二极管显示器(LED)、电泳显示器和阴极射线管显示器。
实施例:
下表1示出通过在避光下混合所有组分以获得均匀混合物而制备的4种组合物。
第一个实施例包含本发明组合物的所有必要组分,即30-90wt%(67.7wt%)的具有大于15000的分子量的氨基甲酸酯丙烯酸酯低聚物(具有20000的分子量的UVA-002)、2-40wt%(15.0wt%)的具有苯环的(甲基)丙烯酸酯单体(丙烯酸苄酯)和0.2-10wt%(共3.5wt%)的光引发剂(TPO和Irgacure 184的组合)。
该表也包括三种不包含所有必要组分的比较组合物。
从表2可以看出,只有根据本发明的组合物显示出1.7的显著提高的触变比。根据现有技术的组合物均显示出1.0的触变比。
表1:不同的可光固化的树脂组合物
表2:可光固化的树脂组合物的特性
*UC203:具有5000-8000的Mw的异戊二烯丙烯酸酯低聚物,来自可乐丽株式会社(Kuraray Co.Ltd.)
*UT5141:具有6000-10000的Mw的氨基甲酸酯丙烯酸酯低聚物,来自日本合成化工株式会社(Nipon Gosei Co.Ltd.)
*UVA002:具有20000的Mw的氨基甲酸酯丙烯酸酯低聚物,来自大阪有机化学工业株式会社(Osaka Organic Chemical Ind.,Ltd)
*BYK-088:来自BYK
*Irganox 1520L、TINUVIN PS、TPO和Irgacure:全部来自巴斯夫(BASF)
对于粘度和触变比(粘度@1sec-1剪切速率与粘度@10sec-1剪切速率的比),根据ASTM D1084使用HAAKE Reometer。
分别根据ASTM E903和ASTM D1003,用UV-可见光光谱仪测量透射率和Y.I(b*)。
根据ASTM D 1003,用雾度检测仪测量雾度。
Claims (14)
1.可光固化的树脂组合物,包含:
a)30-90wt%的具有大于15000的分子量的氨基甲酸酯丙烯酸酯低聚物,
b)2-40wt%的具有苯环的(甲基)丙烯酸酯单体,
c)0.2-10wt%的光引发剂,
其中所述具有苯环的(甲基)丙烯酸酯单体选自:
2.根据权利要求1的可光固化的树脂组合物,其中所述氨基甲酸酯丙烯酸酯低聚物是脂肪族氨基甲酸酯丙烯酸酯。
3.根据权利要求1或2的可光固化的树脂组合物,其中所述光引发剂选自苯基乙醛酸酯、α-羟基酮、α-氨基酮、苯偶酰二甲基缩酮、单酰基氧化膦、双酰基氧化膦、二苯甲酮、肟酯、二茂钛及它们的组合。
4.根据权利要求1或2的可光固化的树脂组合物,包含:
a)40-80wt%的具有大于15000的分子量的氨基甲酸酯丙烯酸酯低聚物,
b)5-30wt%的具有苯环的(甲基)丙烯酸酯单体,和
c)0.5-6wt%的光引发剂。
5.根据权利要求1或2的可光固化的树脂组合物,其中所述组合物进一步包含不多于40wt%的变形剂、紫外线吸收剂、光稳定剂、硅烷偶联剂、抗氧化剂或它们的组合。
6.根据权利要求5的可光固化的树脂组合物,其中所述变形剂基于硅氧烷和聚合物。
7.根据权利要求5的可光固化的树脂组合物,其中所述抗氧化剂选自酚类抗氧化剂、胺类抗氧化剂、基于硫的抗氧化剂和多功能抗氧化剂或它们的组合。
8.根据权利要求5的可光固化的树脂组合物,其中所述紫外线吸收剂是苯并三唑类紫外线吸收剂。
9.根据权利要求8的可光固化的树脂组合物,其中所述紫外线吸收剂是2-(5-叔丁基-2-羟基苯基)苯并三唑。
10.根据权利要求1-9中任一项的所述可光固化的树脂组合物用于粘合光学组件中的部件的用途。
11.根据权利要求1-9中任一项的所述可光固化的树脂组合物用于触摸面板传感组件的用途。
12.根据权利要求1-9中任一项的所述可光固化的树脂组合物用于玻璃盖板粘合的用途。
13.根据权利要求1-9中任一项的所述可光固化的树脂组合物用于直接将玻璃盖板粘合到LCD模块的用途。
14.根据权利要求1-9中任一项的所述可光固化的树脂组合物用于液晶显示器上以将触摸屏幕固定在基材上的用途,其中,所述基材可以是选自液晶显示器、等离子显示器、发光二极管(LED)显示器、电泳显示器和阴极射线管显示器的显示面板。
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