CN109988273A - 一种3d打印用长波紫外光固化树脂组合物的制备方法 - Google Patents
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Abstract
本发明公开了一种3D打印用长波紫外光固化树脂组合物的制备方法,将各原料组分按如下比例称重后加入到反应器中,并加入磁转子进行搅拌;将搅拌后的混合物放入超声波清洗器中震动后取出;然后将震动后的混合物放入真空干燥箱中于20~30℃下抽真空消泡处理;再将步骤3处理后得到的液体倒入402nm紫外光3D打印机树脂槽中流平进行3D打印,再取出打印好的制品,并将其放入紫外固化箱中照射后得到长波紫外光固化树脂组合物。该方法可以扩大UV光固化树脂的种类,使制得的长波紫外光固化树脂组合物具有高性能、低收缩、耐黄变的性能。
Description
技术领域
本发明涉及3D打印及高分子材料技术领域,尤其涉及一种3D打印用长波紫外光固化树脂组合物的制备方法。
背景技术
UV光固化树脂的种类和用途多种多样,其中以3D打印用UV光固化树脂引起了广大科学研究者的兴趣。3D打印技术发展迅猛,其中,SLA型3D打印技术是采用激光紫外线进行光固化树脂的层层打印,紫外光固化树脂是一种由预聚体、活性稀释剂、光引发剂、助剂及填料等混合后通过UV光固化技术能够交联固化的材料,因而具有高效、环保、节能、优质、投资少等优点,同时对它有着液态树脂稳定性好、粘度低、固化速度快、一次固化程度高、固化收缩率小、固化物机械性能好等要求,未来可以在电子电器、机械制造、工程建筑、医疗卫生、航空航天等方面发挥重要作用。通用的3D打印用UV光固化树脂是在365nm左右紫外光下固化的,长波(400nm以上)固化的3D打印用光固化树脂还较为少见,而采用长波的3D打印机价格低,体积小,可做成桌面型SLA新3D打印机,大大促进了3D打印技术的发展。
为了克服传统UV光固化树脂在长波下不能固化的缺点,急需开发一种可长波固化的、混杂型光固化的3D打印用UV光固化树脂的制备工艺。
发明内容
本发明的目的是提供一种3D打印用长波紫外光固化树脂组合物的制备方法,该方法可以扩大UV光固化树脂的种类,使制得的长波紫外光固化树脂组合物具有高性能、低收缩、耐黄变的性能。
本发明的目的是通过以下技术方案实现的:
一种3D打印用长波紫外光固化树脂组合物的制备方法,所述方法包括:
步骤1、将各原料组分按如下比例称重后加入到反应器中,并加入磁转子进行搅拌;其中,各原料组分的质量份数具体为:15~25份的阳离子型预聚物、1~5份的阳离子型光引发剂、0.1~1份的光敏增感剂、10-20份的自由基型预聚物、5~15份的阳离子型活性稀释剂、10~30份的自由基型活性稀释剂和1~2份的自由基型光引发剂,且上述各原料组分的总和为100;
步骤2、将搅拌后的混合物放入超声波清洗器中震动后取出;
步骤3、然后将震动后的混合物放入真空干燥箱中于20~30℃下抽真空消泡处理;
步骤4、再将步骤3处理后得到的液体倒入402nm紫外光3D打印机树脂槽中流平进行3D 打印,再取出打印好的制品,并将其放入紫外固化箱中照射后得到长波紫外光固化树脂组合物。
由上述本发明提供的技术方案可以看出,上述方法可以扩大UV光固化树脂的种类,使制得的长波紫外光固化树脂组合物具有高性能、低收缩、耐黄变的性能,适用于长波紫外光固化3D打印快速成型。
附图说明
为了更清楚地说明本发明实施例的技术方案,下面将对实施例描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域的普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他附图。
图1为本发明实施例提供的3D打印用长波紫外光固化树脂组合物的制备方法流程示意图。
具体实施方式
下面结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明的保护范围。
下面将结合附图对本发明实施例作进一步地详细描述,如图1所示为本发明实施例提供的3D打印用长波紫外光固化树脂组合物的制备方法流程示意图,所述方法包括:
步骤1、将各原料组分按如下比例称重后加入到反应器中,并加入磁转子进行搅拌;
其中,各原料组分的质量份数具体为:15~25份的阳离子型预聚物、1~5份的阳离子型光引发剂、0.1~1份的光敏增感剂、10-20份的自由基型预聚物、5~15份的阳离子型活性稀释剂、10~30份的自由基型活性稀释剂和1~2份的自由基型光引发剂,且上述各原料组分的总和为100。
具体实现中,所采用的阳离子型预聚物包括环氧当量为100~400g/eg、黏度为1000- 5000mPa·s的环氧树脂和环氧丙烯酸酯,具体为:
环氧当量200~400g/eg、黏度为1000-3000mPa·s的双酚A型环氧树脂和氢化双酚A型环氧树脂。
所采用的阳离子型光引发剂包括芳香硫鎓盐和碘鎓盐类以及茂铁盐类,具体为:
混合型三芳基六氟磷酸硫鎓盐和η6-异丙苯茂铁(Ⅱ)六氟磷酸盐的混合液,可以大大提高阳离子对长波紫外线的开环聚合速度。
所采用的光敏增感剂包括噻吩衍生物、蒽醌衍生物或羟基多元醇,优选噻吩衍生物 (PAS-50),可以提高对长波的光敏性。
所采用的阳离子型活性稀释剂为环氧环己基酯及氧杂环丁烷的混合物,或者二—(3,4—环氧环己基)己二酸酯环状苯基硅氧烷。具体包括单环氧基脂环族环氧化合物、4-羟丁基乙烯基醚、乙二醇二乙烯基醚、乙二醇丁基乙烯基醚或1,4-环己基二甲醇二乙烯基醚,优选3,4-环氧环己基甲酸-3,4-环氧环己基甲酯。
所采用的自由基型预聚物包括超支化聚氨酯丙烯酸酯,优选超支化聚酯型聚氨酯丙烯酸酯,黏度为500~1000mPa·s。通过引入超支化聚氨酯丙烯酸酯可以提高材料的光敏性和对支撑平台的附着力,同时体系黏度较低,适合于3D快速打印成型。
所采用的自由基型活性稀释剂包括脂肪族聚氨酯六丙烯酸酯、1,6-己二醇二丙烯酸酯、脂肪族聚氨酯丙烯酸酯、乙氧化三羟甲基丙烷三丙烯酸酯、丙烯酸异冰片酯或二缩三丙二醇二丙烯酸酯,室温黏度为50~500mPa·s,优选乙氧化三羟甲基丙烷三丙烯酸酯。
所采用的自由基型光引发剂包括安息香醚类、苯偶酰缩酮、苯乙酮、二苯甲酮类或硫杂蒽酮类,优选1-羟基环己基苯甲酮和TPO。
步骤2、将搅拌后的混合物放入超声波清洗器中震动后取出;
步骤3、然后将震动后的混合物放入真空干燥箱中于20~30℃下抽真空消泡处理;
步骤4、再将步骤3处理后得到的液体倒入402nm紫外光3D打印机树脂槽中流平进行3D 打印,再取出打印好的制品,并将其放入紫外固化箱中照射后得到长波紫外光固化树脂组合物。
下面结合具体实例对本发明所述方法得到的产物性能进行详细说明,如下表1所示为本实施例所列举的对比例及实施例1-3的配方表:
表1
然后按照上述方法实施例提供的工艺步骤制备得到相应的长波紫外光固化树脂组合物,下表2所示为对比例及实施例1-3的长波紫外光固化树脂组合物的测试结果对比示意:
表2
其中,对比例在402nm长波紫外光下不能发生固化,而其在表中的数据是其在365nm 紫外光下的固化数据,其余3个实施例均为在402nm长波紫外光下发生固化。由此可见:加入不同的光引发剂会使得组合物在不同的紫外光下固化,而且光敏增感剂的加入会缩短固化诱导期,提高固化程度,收缩率降低,从而获得高模量产品。
值得注意的是,本发明实施例中未作详细描述的内容属于本领域专业技术人员公知的现有技术。
综上所述,本发明实施例所述方法在传统的UV光固化树脂中引入新的对长波紫外光具有响应的光引发剂,因此光固化树脂的固化波长向长波方向移动,从而可以扩大UV光固化树脂的种类;同时结合自由基和阳离子固化的优点,弥补各自缺点,从而达到高性能、低收缩、耐黄变的性能,弥补国内空白,打破国外垄断,降低生产成本。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明披露的技术范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应该以权利要求书的保护范围为准。
Claims (8)
1.一种3D打印用长波紫外光固化树脂组合物的制备方法,其特征在于,所述方法包括:
步骤1、将各原料组分按如下比例称重后加入到反应器中,并加入磁转子进行搅拌;其中,各原料组分的质量份数具体为:15~25份的阳离子型预聚物、1~5份的阳离子型光引发剂、0.1~1份的光敏增感剂、10-20份的自由基型预聚物、5~15份的阳离子型活性稀释剂、10~30份的自由基型活性稀释剂和1~2份的自由基型光引发剂,且上述各原料组分的总和为100;
步骤2、将搅拌后的混合物放入超声波清洗器中震动后取出;
步骤3、然后将震动后的混合物放入真空干燥箱中于20~30℃下抽真空消泡处理;
步骤4、再将步骤3处理后得到的液体倒入402nm紫外光3D打印机树脂槽中流平进行3D打印,再取出打印好的制品,并将其放入紫外固化箱中照射后得到长波紫外光固化树脂组合物。
2.根据权利要求1所述3D打印用长波紫外光固化树脂组合物的制备方法,其特征在于,所采用的阳离子型预聚物包括环氧当量200~400g/eg、黏度为1000-3000mPa·s的双酚A型环氧树脂和氢化双酚A型环氧树脂。
3.根据权利要求1所述3D打印用长波紫外光固化树脂组合物的制备方法,其特征在于,所采用的阳离子型光引发剂包括混合型三芳基六氟磷酸硫鎓盐和η6-异丙苯茂铁(Ⅱ)六氟磷酸盐的混合液。
4.根据权利要求1所述3D打印用长波紫外光固化树脂组合物的制备方法,其特征在于,所采用的光敏增感剂包括噻吩衍生物、蒽醌衍生物或羟基多元醇。
5.根据权利要求1所述3D打印用长波紫外光固化树脂组合物的制备方法,其特征在于,所采用的阳离子型活性稀释剂包括单环氧基脂环族环氧化合物、4-羟丁基乙烯基醚、乙二醇二乙烯基醚、乙二醇丁基乙烯基醚或1,4-环己基二甲醇二乙烯基醚。
6.根据权利要求1所述3D打印用长波紫外光固化树脂组合物的制备方法,其特征在于,所采用的自由基型预聚物包括超支化聚酯型聚氨酯丙烯酸酯,黏度为500~1000mPa·s。
7.根据权利要求1所述3D打印用长波紫外光固化树脂组合物的制备方法,其特征在于,所采用的自由基型活性稀释剂包括脂肪族聚氨酯六丙烯酸酯、1,6-己二醇二丙烯酸酯、脂肪族聚氨酯丙烯酸酯、乙氧化三羟甲基丙烷三丙烯酸酯、丙烯酸异冰片酯或二缩三丙二醇二丙烯酸酯,室温黏度为50~500mPa·s。
8.根据权利要求1所述3D打印用长波紫外光固化树脂组合物的制备方法,其特征在于,所采用的自由基型光引发剂包括安息香醚类、苯偶酰缩酮、苯乙酮、二苯甲酮类或硫杂蒽酮类。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111234662A (zh) * | 2020-03-20 | 2020-06-05 | 宁波野山羊新材料科技有限公司 | 光固化组合物、光固化产物以及基材涂层的制备方法 |
CN112029236A (zh) * | 2020-08-06 | 2020-12-04 | 东南大学 | 一种光固化3d打印树脂及其制备方法和应用、3d打印产品 |
CN114986902A (zh) * | 2022-06-07 | 2022-09-02 | 丽水学院 | 一种应用于口腔医学领域的高性能dlp-3d打印材料制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0566801B1 (en) * | 1992-04-24 | 1998-12-30 | Borden Chemical, Inc. | Organic solvent and water resistant, thermally, oxidatively and hydrolytically stable radiation-curable coatings for optical fibers, optical fibers coated therewith and processes for making same |
CN106632895A (zh) * | 2016-10-09 | 2017-05-10 | 王璟 | 环氧化柠檬烯促进的3d打印光固化树脂组合物 |
CN108440688A (zh) * | 2018-01-31 | 2018-08-24 | 北京化工大学 | 一类姜黄素衍生物在可见光固化领域的应用 |
-
2019
- 2019-04-03 CN CN201910266536.0A patent/CN109988273B/zh not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0566801B1 (en) * | 1992-04-24 | 1998-12-30 | Borden Chemical, Inc. | Organic solvent and water resistant, thermally, oxidatively and hydrolytically stable radiation-curable coatings for optical fibers, optical fibers coated therewith and processes for making same |
CN106632895A (zh) * | 2016-10-09 | 2017-05-10 | 王璟 | 环氧化柠檬烯促进的3d打印光固化树脂组合物 |
CN108440688A (zh) * | 2018-01-31 | 2018-08-24 | 北京化工大学 | 一类姜黄素衍生物在可见光固化领域的应用 |
Non-Patent Citations (2)
Title |
---|
刘海涛: "光固化三维打印成形材料的研究与应用", 《中国博士学位论文全文数据库 信息科技辑》 * |
周功耀等: "《3D打印基础教程》", 29 February 2016, 东方出版社 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111234662A (zh) * | 2020-03-20 | 2020-06-05 | 宁波野山羊新材料科技有限公司 | 光固化组合物、光固化产物以及基材涂层的制备方法 |
CN112029236A (zh) * | 2020-08-06 | 2020-12-04 | 东南大学 | 一种光固化3d打印树脂及其制备方法和应用、3d打印产品 |
CN114986902A (zh) * | 2022-06-07 | 2022-09-02 | 丽水学院 | 一种应用于口腔医学领域的高性能dlp-3d打印材料制备方法 |
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