CN107201077A - 一种改良的胶印油墨的制备方法 - Google Patents
一种改良的胶印油墨的制备方法 Download PDFInfo
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Abstract
本发明公开了一种改良的胶印油墨的制备方法，该油墨的制备方法先利用聚酯或聚醚二元醇与聚合物多元醇、小分子二元醇或二元胺反应得到性质比较稳定的醇酯型聚氨酯树脂溶液，再利用环氧树脂和有机硅制得耐热性的树脂，最后将聚氨酯树脂溶液与耐热性的树脂混合后与颜料、催干剂、抗乳化剂、抗氧化剂混合得到改良的胶印油墨。本发明方法合成聚氨酯不仅效率高且绿色环保，将其与耐热树脂以及耐酸颜料混合制备胶印油墨，不是使得油墨更为绿色环保，同时还显著的加强了油墨耐酸，耐热性。
Description
技术领域
本发明涉及精细化学品技术领域，更具体地说，本发明涉及一种改良的胶印油墨的制备方法。
背景技术
随着现代印刷业的飞速发展，对印刷品的质量要求在不断提高，对油墨的质量要求也随之提高。而油墨更新换代的关键在于进一步提高树脂的性能。目前平版胶印油墨用树脂仍以松香改性酚醛树脂为主。近年来，人们根据胶印油墨发展的新目标和要求，需要在在生产配方和工艺上做出进一步的创新发展和改进，以获得各种规格的树脂产品，满足新型高速、高精细，及对环境有利的印刷技术的发展需要。
丙烯酸酯类树脂是一种共聚物，通过选择合适的单体，可以得到综合性能优良并且可调控性强的油墨树脂，能较好地满足目前印刷行业对于油墨的要求。 醇溶油墨使用乙醇作为溶剂，环保性好，乙醇与塑料表面的润湿性较好，乙醇挥发性也好于水。此外，醇溶油墨印刷工艺与苯溶油墨类似，可以在现有的任何设备上使用，因此醇溶油墨是最适合代替苯溶油墨进入工业生产的产品，兼具良 好的使用性能和环保性能，受到了广泛的关注。
专利CN 104031467A《一种环保溶剂型聚氨酯油墨的制备方法》中利用顺丁烯二酸酐、乙二酸、甲乙丙二醇、二异氰酸酯等合成了聚氨酯树脂，并将其应用于油墨的配方中得到了环保型聚氨酯油墨。专利CN 106280693 A《一种聚氨酯油墨》利用短链的多元醇脂制备了聚氨酯乳液后，将乳液于油墨的配方中得到了环保型聚氨酯油墨，该方法和彻骨聚氨酯更为简单。但是尽管聚氨酯类树脂粘性好，且环保，但是该类树脂耐热性较不强，可以胶印后容易脱落，因此开发一种耐热的聚氨酯油墨具有重要的意义。
发明内容
为了解决上述问题，本发明提供一种改良的胶印油墨的制备方法，具体制备方法包括以下步骤：
（1）将聚酯或聚醚二元醇真空脱气后加入聚合物多元醇和二异氰酸酯，升温至70～90℃后加入催化剂，进行预聚反应2-4小时后冷却至室温，用溶剂稀释后滴加小分子二元醇或二元胺溶液进行扩链反应1-2小时，扩链末期可适当加入5-8%交联剂，继续反应0.5-1小时后用醇酯混合溶剂溶解，得到性质比较稳定的醇酯型聚氨酯树脂溶液；
（2）称取一定量的环氧树脂 E20和醋酸纤维素混合后，环氧树脂溶解在溶剂中，加热，加入催化剂和有机硅中间体，然后减压脱去缩合反应生成的水，40-60℃恒温后交联反应4-6h后，过滤后将得到的树脂用乙醇洗涤后干燥，制得环氧改性有机硅树脂；
（3）醇酯型聚氨酯树脂溶液和环氧改性有机硅树脂按一定比例混合后，升温到50-80℃搅拌均匀后，加入凝胶剂后升温到150-180℃后保温30 min再加入矿物油混合均匀后得到连结料；
（4）将制得的连结料和耐酸钢化颜料、催干剂、抗氧化剂、抗乳化剂混合均匀后，置于三辊机上，10-20MPa的压力和 30-50℃的温度下轧制 2-3 道，然后将三辊机压力降至 3-6MPa 后，用矿物油调整黏性至设定范围后，得到改良的胶印油墨。
优选的，步骤（1）中所述的聚酯或聚醚二元醇为聚四氢呋喃醚(PTMG)、聚碳酸酯(PCD)、聚环氧丙烷(PPG)、聚酯775和轻度支化聚酯670BA聚合物多元醇中的一种；所述的聚合物多元醇和二异氰酸酯的加入量为1:0.5-1.5；所述的催化剂为辛酸亚锡、二月桂酸二丁锡中的一种；所述的催化剂的加入量为1-2%。
优选的，步骤（1）中所述的溶剂为乙酸乙酯、石油醚、丙酮中的中一种；所述的小分子二元醇或二元胺为1，4-丁二醇(BDO)、1,4-环己烷二甲醇(CHDM)、新戊二醇(NPG)、异佛尔酮二胺(IPDA)、乙二胺(EDA)中的一种；所述的小分子二元醇或二元胺加入量为5-10%。
优选的，步骤（1）中所述的交联剂为量三羟甲基丙烷(TMP)。
优选的，步骤（2）中所述的环氧树脂 E20和醋酸纤维素质量比为1:1-2；所述的溶剂为石油醚、乙酸乙酯中的一种；所述的有机硅中间体为Z-6018，加入量为15-35%；所述的催化剂为异辛酸、正辛酸中的一种；所述催化剂的加入量为1.5-3%。
优选的，步骤（3）中所述的醇酯型聚氨酯树脂和环氧改性有机硅树脂的加入量为1:0.8-1.2；所述的凝胶剂为乙酸乙酯基铝二异丙酯或XP148的二烷基铝鳌合物，凝胶剂的加入量为0.2-1.0%。
优选的，步骤（4）中所述的耐酸钢化颜料由低熔点玻璃粉和高温陶瓷黑色素组成；所述的抗乳化剂为甲基硅油或蜡粉；所述的催干剂为异辛酸锰和异辛酸钴的混合物；所述的抗氧化剂为茶多酚、枸橼酸、丁基羟基茴香醚、二丁基羟基甲苯中的一种；所述的油墨的黏度为11-13Pa.s。
本发明所述的一种改良的胶印油墨的制备方法与传统胶印油墨制备方法相比，采用了聚酯或聚醚二元醇与二异氰酸酯等化合物合成了绿色环保的醇酯型聚氨酯油墨，加强了油墨的环境友好性；利用环氧树脂和有机硅形成混合树脂，提高了树脂的耐热性，提高油墨的内热性；此外，在制备油墨的过程中加入催干剂，使得油墨在胶印时能快速干燥，提高印刷效率。
具体实施方式
以下将结合具体实施例对本发明所述的一种天然芳香快干型胶印油墨做进一步的阐述，以帮助本领域的技术人员对本发明的发明构思、技术方案有更完整、准确和深入的理解。
实施例1
将聚四氢呋喃醚真空脱后加入1:1的聚合物多元醇和二异氰酸酯，升温至80℃后加入1%的辛酸亚锡，进行预聚反应2小时后冷却至室温，用乙酸乙酯稀释后滴加8%的1，4-丁二醇进行扩链反应1.5小时后，加入5%的三羟甲基丙烷，继续反应0.1小时后用醇酯混合溶剂溶解，得到性质比较稳定的醇酯型聚氨酯树脂溶液；称取1:1的环氧树脂 E20和醋酸纤维素，混合后加入乙酸乙酯加热溶解后，加入2%的正辛酸和20%的Z-6018后减压脱去缩合反应生成的水60℃恒温后交联反应4h后，过滤后将得到的树脂用乙醇洗涤后干燥，制得环氧改性有机硅树脂；将醇酯型聚氨酯树脂溶液和环氧改性有机硅树脂按按1:1质量比混合后，升温到80℃搅拌均匀后，加入0.5%乙酸乙酯基铝二异丙酯后升温到170℃后保温30 min再加入矿物油混合均匀后得到连结料；将制得的连接料和5%的低熔点玻璃粉和高温陶瓷黑色素、1%的异辛酸锰和异辛酸钴的混合物，2%的茶多酚、2%的甲基硅混合均匀后，置于三辊机上，15MPa的压力和45℃的温度下轧制 3 道，然后将三辊机压力降至4MPa 后，用矿物油调整黏度至11.5-12.5Pa.s范围后，得到改良的胶印油墨。
实施例2
将聚环氧丙烷真空脱后加入1:1的聚合物多元醇和二异氰酸酯，升温至85℃后加入1.5%的二月桂酸二丁锡中，进行预聚反应1.5小时后冷却至室温，用石油醚稀释后滴加9%的1,4-环己烷二甲醇行扩链反应1.5小时后，加入5%的三羟甲基丙烷，继续反应0.1小时后用醇酯混合溶剂溶解，得到性质比较稳定的醇酯型聚氨酯树脂溶液；称取1:1的环氧树脂 E20和醋酸纤维素，混合后加入石油醚加热溶解后，加入2%的异辛酸和20%的Z-6018后减压脱去缩合反应生成的水60℃恒温后交联反应4h后，过滤后将得到的树脂用乙醇洗涤后干燥，制得环氧改性有机硅树脂; 将醇酯型聚氨酯树脂溶液和环氧改性有机硅树脂按按1:1.2的质量比混合后，升温到85℃搅拌均匀后，加入0.5%XP148的二烷基铝鳌合物后升温到160℃后保温25 min再加入矿物油混合均匀后得到连结料；将制得的连接料和5%的低熔点玻璃粉和高温陶瓷黑色素、1.2%的异辛酸锰和异辛酸钴的混合物，2%的枸橼酸、2%的甲基硅混合均匀后，置于三辊机上，15MPa的压力和 45℃的温度下轧制3道，然后将三辊机压力降至4MPa后，用矿物油调整黏度至11.5-12.5Pa.s范围后，得到改良的胶印油墨。
对于本领域的普通技术人员而言，具体实施例只是对本发明进行了示例性描述，显然本发明具体实现并不受上述方式的限制，只要采用了本发明的方法构思和技术方案进行的各种非实质性的改进，或未经改进将本发明的构思和技术方案直接应用于其它场合的，均在本发明的保护范围之内。
Claims (7)
1.一种改良的胶印油墨的制备方法，其特征在于，包括如下步骤：
（1）将聚酯或聚醚二元醇真空脱气后加入聚合物多元醇和二异氰酸酯，升温至70～90℃后加入催化剂，进行预聚反应2-4小时后冷却至室温，用溶剂稀释后滴加小分子二元醇或二元胺溶液进行扩链反应1-2小时，扩链末期可适当加入5-8%交联剂，继续反应0.5-1小时后用醇酯混合溶剂溶解，得到性质比较稳定的醇酯型聚氨酯树脂溶液；
（2）称取一定量的环氧树脂 E20和醋酸纤维素混合后，环氧树脂溶解在溶剂中，加热，加入催化剂和有机硅中间体，然后减压脱去缩合反应生成的水，40-60℃恒温后交联反应4-6h后，过滤后将得到的树脂用乙醇洗涤后干燥，制得环氧改性有机硅树脂；
（3）醇酯型聚氨酯树脂溶液和环氧改性有机硅树脂按一定比例混合后，升温到50-80℃搅拌均匀后，加入凝胶剂后升温到150-180℃后保温30 min再加入矿物油混合均匀后得到连结料；
（4）将制得的连结料和耐酸钢化颜料、催干剂、抗氧化剂、抗乳化剂混合均匀后，置于三辊机上，10-20MPa的压力和 30-50℃的温度下轧制 2-3 道，然后将三辊机压力降至 3-6MPa 后，用矿物油调整黏性至设定范围后，得到改良的胶印油墨。
2.根据权利要求1所述的一种改良的胶印油墨的制备方法，其特征在于，步骤（1）中所述的聚酯或聚醚二元醇为聚四氢呋喃醚(PTMG)、聚碳酸酯(PCD)、聚环氧丙烷(PPG)、聚酯775和轻度支化聚酯670BA聚合物多元醇中的一种；所述的聚合物多元醇和二异氰酸酯的加入量为1:0.5-1.5；所述的催化剂为辛酸亚锡、二月桂酸二丁锡中的一种；所述的催化剂的加入量为1-2%。
3.根据权利要求1所述的一种改良的胶印油墨的制备方法，其特征在于，步骤（1）中所述的溶剂为乙酸乙酯、石油醚、丙酮中的中一种；所述的小分子二元醇或二元胺为1，4-丁二醇(BDO)、1,4-环己烷二甲醇(CHDM)、新戊二醇(NPG)、异佛尔酮二胺(IPDA)、乙二胺(EDA)中的一种；所述的小分子二元醇或二元胺加入量为5-10%。
4.根据权利要求1所述的一种改良的胶印油墨的制备方法，其特征在于，步骤（1）中所述的交联剂为量三羟甲基丙烷(TMP)。
5.根据权利要求1所述的一种改良的胶印油墨的制备方法，其特征在于，步骤（2）中所述的环氧树脂 E20和醋酸纤维素质量比为1:1-2；所述的溶剂为石油醚、乙酸乙酯中的一种；所述的有机硅中间体为Z-6018，加入量为15-35%；所述的催化剂为异辛酸、正辛酸中的一种；所述催化剂的加入量为1.5-3%。
6.根据权利要求1所述的一种改良的胶印油墨的制备方法，其特征在于，步骤（3）中所述的醇酯型聚氨酯树脂和环氧改性有机硅树脂的加入量为1:0.8-1.2；所述的凝胶剂为乙酸乙酯基铝二异丙酯或XP148的二烷基铝鳌合物，凝胶剂的加入量为0.2-1.0%。
7.根据权利要求1所述的一种改良的胶印油墨的制备方法，其特征在于，步骤（4）中所述的耐酸钢化颜料由低熔点玻璃粉和高温陶瓷黑色素组成；所述的抗乳化剂为甲基硅油或蜡粉；所述的催干剂为异辛酸锰和异辛酸钴的混合物；所述的抗氧化剂为茶多酚、枸橼酸、丁基羟基茴香醚、二丁基羟基甲苯中的一种；所述的油墨的黏度为11-13Pa.s。
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| CN114057980A (zh) * | 2020-07-30 | 2022-02-18 | 万华化学（北京）有限公司 | 一种可自分散酯溶聚氨酯油墨树脂、制备方法及油墨 |
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| CN105802344A (zh) * | 2014-12-30 | 2016-07-27 | 中国科学院化学研究所 | 一种抗氧化纳米铜导电油墨 |
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| CN105802344A (zh) * | 2014-12-30 | 2016-07-27 | 中国科学院化学研究所 | 一种抗氧化纳米铜导电油墨 |
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| CN108944112A (zh) * | 2018-07-28 | 2018-12-07 | 黄智慧 | 一种免醇润版液的制备方法 |
| CN114057980A (zh) * | 2020-07-30 | 2022-02-18 | 万华化学（北京）有限公司 | 一种可自分散酯溶聚氨酯油墨树脂、制备方法及油墨 |
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