CN112226108A - 一种用于pp无纺布上印刷油墨及其制备方法 - Google Patents

一种用于pp无纺布上印刷油墨及其制备方法 Download PDF

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CN112226108A
CN112226108A CN202010883480.6A CN202010883480A CN112226108A CN 112226108 A CN112226108 A CN 112226108A CN 202010883480 A CN202010883480 A CN 202010883480A CN 112226108 A CN112226108 A CN 112226108A
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printing ink
polyester polyol
polyol
woven fabric
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任宝东
赵亚娟
晁国库
朱青松
郑丽雅
杜鸿儒
宋小芳
李新华
张权
任佳
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Wenzhou University
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Abstract

针对现有技术中存在的上述问题，本发明目的在于提供一种用于PP无纺布上印刷油墨及其制备方法的技术方案，实现PP无纺布上印刷油墨零VOCs的排放。所述的一种用于PP无纺布上印刷油墨，其特征在于包括以下组份：水性聚氨酯树脂10‑40份；分散剂1‑5份；消泡剂0.1‑0.5份；碳酸钙0‑10份；钛白粉10‑25份；膨润土5‑15份；增稠剂15‑30份。

Description

一种用于PP无纺布上印刷油墨及其制备方法
技术领域
本发明属于丝网印刷油墨的技术领域，具体涉及一种用于PP无纺布上印刷油墨及其制备方法。
背景技术
丝网印刷属于四大印刷技术（凸版印刷，凹版印刷，平版印刷，孔版印刷）中的孔版印刷。丝网印刷的印版是孔板，油墨通过印版上的网孔漏至承印物上，在承印物上形成图文，而非孔部分不能透过油墨，在承印物上形成空白。丝网印刷承印物比较广泛，如塑料、纺织品、金属、玻璃、陶瓷等材料都可以作为承印物，丝网印刷又称为万能印刷，广泛的应用于商业、广告业、装潢业、美术业、建筑业、出版业、印染业、电子等领域。
PP无纺布是常用的丝网印刷承印物。丝网印刷PP无纺布的油墨是由连接料，颜料、助剂、水等溶剂组成，其中连接料是特殊的水性聚丙烯酸酯。为了增加水性聚丙烯酸酯的水溶性，常常在水性聚丙烯酸酯的乳液中加入胺类等形成胺盐，氨类物质在油墨干燥过程中挥发到环境中，增加了丝网印刷油墨VOCs的排放，给环境带来污染，影响人体健康。
发明内容
针对现有技术中存在的上述问题，本发明目的在于提供一种用于PP无纺布上印刷油墨及其制备方法的技术方案，实现PP无纺布上印刷油墨零VOCs的排放。
所述的一种用于PP无纺布上印刷油墨，其特征在于包括以下组份：
水性聚氨酯树脂 10-40份；
分散剂 1-5份；
消泡剂 0.1-0.5份；
碳酸钙 0-10份；
钛白粉 10-25份；
膨润土 5-15份；
增稠剂 15-30份。
所述的一种用于PP无纺布上印刷油墨，其特征在于所述的水性聚氨酯树脂包括以下组份：
聚酯多元醇 10-30份；
水性聚酯多元醇 1-10份；
聚醚多元醇 30-50份；
异佛尔酮二异氰酸酯 10-30份；
多元醇扩链剂 1-8份；
戊二酸甲酯 1-5份；
磺酸型水性扩链剂乙二胺基乙磺酸钠 0.5-2.5份；
乙二胺 0.1-3份。
所述的一种用于PP无纺布上印刷油墨，其特征在于所述的聚酯多元醇的分子量为2000-3000的磺酸型水性聚酯多元醇、二聚酸聚酯多元醇一种或二种的混合。
所述的一种用于PP无纺布上印刷油墨，其特征在于所述的二聚酸聚酯多元醇与磺酸型水性聚酯多元醇的混合比例为1:2。
所述的一种用于PP无纺布上印刷油墨的制备方法，其特征在于包括如下步骤：
1）按照重量份数计：分别称取10-30份的聚酯多元醇，1-10份水性聚酯多元醇，30-50份聚醚多元醇，加入反应釜中搅拌并升温至80℃，加入10-30份异佛尔酮二异氰酸酯，反应2h后，加入1-8份多元醇扩链剂，反应2h后，加入1-5份的戊二酸甲酯，降温至45-55℃，加入0.5-2.5份的磺酸型水性扩链剂乙二胺基乙磺酸钠（AAS），反应1h，加入水，搅拌30min后，加入0.1-3份乙二胺，反应2h，制得固含量为50%的丝网印刷油墨专用的水性聚氨酯树脂；
2）按照重量份数计：取10-40份步骤1）中制得的丝网印刷油墨专用的水性聚氨酯树脂，加入1-5份分散剂、0.1-0.5份消泡剂，搅拌均匀，加入0-10份碳酸钙、10-25份钛白粉、5-15份膨润土，砂磨机研磨至指定细度20μm以下，加入15-30份增稠剂，调整粘度，制得到丝网印刷油墨。
所述的一种用于PP无纺布上印刷油墨的制备方法，其特征在于步骤1）中加入的水量为1000g，且水温为25℃。
所述的一种用于PP无纺布上印刷油墨的制备方法，其特征在于步骤1）中所述的聚醚多元醇的分子量为1000-2000的聚乙二醇或聚胺醚多元醇，所述的多元醇扩链剂为乙二醇、1,4-丁二醇、1,6己二醇、一缩二乙二醇的一种。
所述的一种用于PP无纺布上印刷油墨的制备方法，其特征在于步骤2）中所述的分散剂为超分子分散剂，所述的润滑剂为液体石蜡、尿素或石蜡油中的一种，所述的消泡剂为水性，所述的增稠剂为缔合型水性聚氨酯增稠剂。
与现有技术相比，上述方案具有如下有益效果：
1）采用特殊的二聚酸多元醇结构，使油墨在pp无纺布上具有优异的附着力，耐水解和耐折性能；
2）利用磺酸型水性聚酯多元醇，提高水性聚氨酯树脂的水溶性；
3）在反应过程中，不用加入三乙胺中和，在使用过程中，无有机物挥发，所制备的丝网印刷油墨的VOCs排放为零。
具体实施方式
以下结合实施例对本发明作进一步说明。
一种用于PP无纺布上印刷油墨包括：水性聚氨酯树脂，10-40份；分散剂，1-5份；消泡剂，0.1-0.5份；碳酸钙，0-10份；钛白粉，10-25份；膨润土，5-15份；增稠剂，15-30份。其中水性聚氨酯树脂包括：聚酯多元醇，10-30份；水性聚酯多元醇，1-10份；聚醚多元醇，30-50份；异佛尔酮二异氰酸酯，10-30份；多元醇扩链剂，1-8份；戊二酸甲酯，1-5份；磺酸型水性扩链剂乙二胺基乙磺酸钠，0.5-2.5份；乙二胺，0.1-3份。所述的聚酯多元醇的分子量为2000-3000的磺酸型水性聚酯多元醇、二聚酸聚酯多元醇的一种或二种的混合。所述的二聚酸聚酯多元醇与磺酸型水性聚酯多元醇的混合比例为1:2。
上述用于PP无纺布上印刷油墨通过以下步骤进行制备的：1）按照重量份数计：分别称取10-30份的聚酯多元醇，1-10份水性聚酯多元醇，30-50份聚醚多元醇，加入反应釜中搅拌并升温至80℃，加入10-30份异佛尔酮二异氰酸酯，反应2h后，加入1-8份多元醇扩链剂，反应2h后，加入1-5份的戊二酸甲酯，降温至45-55℃，加入0.5-2.5份的磺酸型水性扩链剂乙二胺基乙磺酸钠（AAS），反应1h，加入水，搅拌30min后，加入0.1-3份乙二胺，反应2h，制得固含量为50%的丝网印刷油墨专用的水性聚氨酯树脂；2）按照重量份数计：取10-40份步骤1）中制得的丝网印刷油墨专用的水性聚氨酯树脂，加入1-5份分散剂、0.1-0.5份消泡剂，搅拌均匀，加入0-10份碳酸钙、10-25份钛白粉、5-15份膨润土，砂磨机研磨至指定细度20μm以下，加入15-30份增稠剂，调整粘度，制得到丝网印刷油墨。在步骤1）中加入的水量为1000g，且水温为25℃，所述的聚醚多元醇的分子量为1000-2000的聚乙二醇或聚胺醚多元醇，所述的多元醇扩链剂为乙二醇、1,4-丁二醇、1,6己二醇、一缩二乙二醇的一种。在步骤2）中所述的分散剂为超分子分散剂，该分散剂优选为SRE-F001AW的水性分散剂，由广州侗富贵化工原材料有限公司生产；所述的润滑剂为液体石蜡、尿素或石蜡油中的一种；所述的消泡剂为水性，优选为德国毕克化学有限公司生产的BYK-028水性消泡剂；所述的增稠剂为缔合型水性聚氨酯增稠剂，优选为广州恒宇化工有限公司生产的TT-935水性聚氨酯增稠剂。
本发明利用二聚酸聚酯多元醇为原料，利用预聚体法，制备了自乳化的丝网印刷专用连接料。二聚酸是二个不饱和脂肪酸的二聚体。二聚酸分子具有一个长的非极性主链、两个非极性支链和两个极性羧基，部分分子还含有l～2个不饱和六元环。其结构如下：
Figure 280571DEST_PATH_IMAGE001
上述特殊的二聚酸多元醇结构，使其具有在pp无纺布上具有优异的附着力，耐水解性能，耐折性能。
在本发明中，还利用磺酸型水性聚酯多元醇，提高水性聚氨酯的水溶性。磺酸型水性聚酯多元醇是已二酸和1,4丁二酸的聚酯多元醇分子链中引入间苯二甲酸-5-磺酸钠，其结构如下：
Figure 371892DEST_PATH_IMAGE002
在本发明中的丝网印刷油墨的连接料是磺酸型水性聚氨酯树脂，在反应过程中，不用加入三乙胺中和，在使用过程中，无有机物挥发，所制备的丝网印刷油墨的VOCs排放为零。
作为优选，取253.37g的聚酯多元醇（具体为二聚酸聚酯多元醇，有北京佰源化工有限公司生产，BY-3026,Mn为2500），67.56g水性聚酯多元醇（具体为自制的磺酸型水性聚酯多元醇，WB4-2000,Mn为2000）,405.39g聚醚多元醇（具体为PEG聚醚多元醇PEG-220，分子量Mn为2000），加入反应釜中，开动搅拌，升温至80℃，加入222.98g异佛尔酮二异氰酸酯（IPDI）,反应2h后，加入32.84g多元醇扩链剂【具体为1,4-丁二醇（BDO）扩链剂】，反应2h，加入50g的戊二酸甲酯，降温至50℃，加入15.4g磺酸型水性扩链剂乙二胺基乙磺酸钠（AAS），反应1h，加入1000g（25℃）水，搅拌反应30min，加入10.15g乙二胺，反应2h，得到丝网印刷油墨专用的水性聚氨酯树脂。
所述的磺酸型水性聚酯多元醇是这样自制的：取600kg的丙二醇甲醚醋酸酯于反应釜中，开动搅拌，加入已二酸（AA）522.5kg，41.8kg间苯二甲酸二甲酯-5-磺酸钠，435.7kg新戊二醇的投入反应釜中，升温至145℃，反应开始有水析出，温度继续升温至155℃恒定，有大量的水析出，温度不变直至反应6h，继续升温至180℃，恒温2h，加入钛酸异已酯催化剂2.8g，再继续升温至200℃,4h，再继续升温至220℃,3h，开始抽真空，0.02MPa抽真空4h，0.06MPa,抽真空3h，0.09MPa抽真空2h,得到磺酸型聚酯多元醇，分子量为2000，测定羟值和酸值，羟值为55.76mgKOH/g，酸值0.2mgKOH/g。
实施例1
取10份上述优选方案制备的丝网印刷油墨专用水性聚氨酯树脂，加入10份水，搅拌。5份分散剂、0.5份消泡剂，搅拌均匀，加入10份碳酸钙、25份钛白粉、15份膨润土，研磨机研磨至指定细度20μm以下，加入30份增稠剂，调整粘度，制得丝网印刷油墨。
实施例2
取40份实施例1制备的丝网印刷油墨专用水性聚氨酯树脂，加入10份水，搅拌。1份分散剂、0.1份消泡剂，搅拌均匀，加入5份碳酸钙、10份钛白粉、5份膨润土，研磨机研磨至指定细度20μm以下，加入15份增稠剂，调整粘度，制得丝网印刷油墨。
实施例3
取20份实施例1制备的丝网印刷油墨专用水性聚氨酯树脂，加入15份水，搅拌。2份分散剂、0.3份消泡剂，搅拌均匀，加入5份碳酸钙、20份钛白粉、10份膨润土，研磨机研磨至指定细度20μm以下，加入23份增稠剂，调整粘度，制得丝网印刷油墨。
对实施例2-4制备的丝网印刷油墨性能与市售丝网印刷油墨性能的检测结果如下表：
检测指标 实施2 实施例3 实施例4 检测标准
粘度（mPaˑs） 3782 4125 4356 GB/T 13217.4-2008
表干时间（min） ≦20 ≦25 ≦30 GB1728-89(79)
剥离强度（N/cm） 6.7 8.0 8.3 GB/T13217.7-2009
附着力 0 0 0 GB1720-89(79)划圈法
VCOs 未检出 未检出 未检出 GB/T23986-2009
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施方法的限制，其他的任何未背离本发明的改变、修饰、替代、简化均应为等效的置换方式，都包括在本发明的保护范围内。

Claims (8)

1.一种用于PP无纺布上印刷油墨，其特征在于包括以下组份：
水性聚氨酯树脂 10-40份；
分散剂 1-5份；
消泡剂 0.1-0.5份；
碳酸钙 0-10份；
钛白粉 10-25份；
膨润土 5-15份；
增稠剂 15-30份。
2.如权利要求1所述的一种用于PP无纺布上印刷油墨，其特征在于所述的水性聚氨酯树脂包括以下组份：
聚酯多元醇 10-30份；
水性聚酯多元醇 1-10份；
聚醚多元醇 30-50份；
异佛尔酮二异氰酸酯 10-30份；
多元醇扩链剂 1-8份；
戊二酸甲酯 1-5份；
磺酸型水性扩链剂乙二胺基乙磺酸钠 0.5-2.5份；
乙二胺 0.1-3份。
3.如权利要求2所述的一种用于PP无纺布上印刷油墨，其特征在于所述的聚酯多元醇的分子量为2000-3000的磺酸型水性聚酯多元醇、二聚酸聚酯多元醇的一种或二种的混合。
4.如权利要求3所述的一种用于PP无纺布上印刷油墨，其特征在于所述的二聚酸聚酯多元醇与磺酸型水性聚酯多元醇的混合比例为1:2。
5.如权利要求2-3所述的任一一种用于PP无纺布上印刷油墨的制备方法，其特征在于包括如下步骤：
按照重量份数计：分别称取10-30份的聚酯多元醇，1-10份水性聚酯多元醇，30-50份聚醚多元醇，加入反应釜中搅拌并升温至80℃，加入10-30份异佛尔酮二异氰酸酯，反应2h后，加入1-8份多元醇扩链剂，反应2h后，加入1-5份的戊二酸甲酯，降温至45-55℃，加入0.5-2.5份的磺酸型水性扩链剂乙二胺基乙磺酸钠（AAS），反应1h，加入水，搅拌30min后，加入0.1-3份乙二胺，反应2h，制得固含量为50%的丝网印刷油墨专用的水性聚氨酯树脂；
按照重量份数计：取10-40份步骤1）中制得的丝网印刷油墨专用的水性聚氨酯树脂，加入1-5份分散剂、0.1-0.5份消泡剂，搅拌均匀，加入0-10份碳酸钙、10-25份钛白粉、5-15份膨润土，砂磨机研磨至指定细度20μm以下，加入15-30份增稠剂，调整粘度，制得到丝网印刷油墨。
6.如权利要求5所述的一种用于PP无纺布上印刷油墨的制备方法，其特征在于步骤1）中加入的水量为1000g，且水温为25℃。
7.如权利要求5所述的一种用于PP无纺布上印刷油墨的制备方法，其特征在于步骤1）中所述的聚醚多元醇的分子量为1000-2000的聚乙二醇或聚胺醚多元醇，所述的多元醇扩链剂为乙二醇、1,4-丁二醇、1,6己二醇、一缩二乙二醇的一种。
8.如权利要求5所述的一种用于PP无纺布上印刷油墨的制备方法，其特征在于步骤2）中所述的分散剂为超分子分散剂，所述的润滑剂为液体石蜡、尿素或石蜡油中的一种，所述的消泡剂为水性，所述的增稠剂为缔合型水性聚氨酯增稠剂。
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