CN114032023A - 一种水性聚氨酯丙烯酸酯乳液及其应用 - Google Patents

一种水性聚氨酯丙烯酸酯乳液及其应用 Download PDF

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CN114032023A
CN114032023A CN202111341921.0A CN202111341921A CN114032023A CN 114032023 A CN114032023 A CN 114032023A CN 202111341921 A CN202111341921 A CN 202111341921A CN 114032023 A CN114032023 A CN 114032023A
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polyurethane acrylate
aqueous
acrylate emulsion
oligomer
emulsion according
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CN114032023B (zh
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吕波
王玉平
余立刚
彭富亮
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Zhejiang Uvchem Special Coatings Co ltd
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Abstract

本发明提供一种水性聚氨酯丙烯酸酯乳液，其特征在于，包括以下原料组分：聚氨酯丙烯酸酯预聚体，以及，聚氨酯丙烯酸酯低聚物。经紫外线固化后，本发明的水性聚氨酯丙烯酸酯乳液具有较好的机械强度，耐磨性能好，所制成的哑光涂料固化后细腻度好。

Description

一种水性聚氨酯丙烯酸酯乳液及其应用
技术领域
本发明涉及涂料技术领域，特别涉及水性聚氨酯丙烯酸酯乳液及其制成的水性哑光漆。
背景技术
在涂料中，哑光漆是相对高光漆相比较而言，光泽度相对降低的漆，通常哑光漆60度角的光泽度在20以下。哑光漆具有外观柔和、质感性强等特点，在3C电子领域、化妆品等高端领域受到重要并得到广泛应用，其中，高耐磨哑光漆更是受到市场的青睐。此外，随着近年来环保力度的加大，加快了高耐磨水性哑光漆的发展。
水性聚氨酯丙烯酸酯乳液是用水代替溶剂进行分散得到的水性树脂。因为用水代替了溶剂，这种乳液的环保性好。用水性聚氨酯丙烯酸酯乳液制备哑光漆，可以减轻环保压力，此外，这种哑光漆可以兼具聚氨酯优异的耐磨性、粘接性和柔韧性，同时又拥有丙烯酸酯的耐候性和保光性。但是，使用常规水性聚氨酯丙烯酸酯制得的水性哑粉漆，其表观粗糙，哑粉细腻度不佳，限制了其应用。
另一方面，为了提高哑光漆膜的耐磨性，有些现有技术(例如中国专利申请公开CN108531042A和CN107446484A等)提出，在制备哑光漆的过程中向其中引入二氧化硅无机物成分。然而，作为无机物的二氧化硅与高分子组分之间有相容性隐患，限制了该类耐磨哑粉漆在更多项目中的应用。
因此，现有的水性哑光漆技术，无论是从哑光细腻度、还是在耐磨性上，都尚不能满足漆膜产品的外观要求和实用性(例如耐磨)的要求，存在很大的待改进空间。
发明内容
本发明的目的是改进现有技术的不足之处，为了实现这个技术目的，本发明提出了一种水性聚氨酯丙烯酸酯乳液，该乳液所用原料均为高分子组分因而相容性好，用该乳液制备的哑光漆具备足够的硬度，耐磨性好，同时哑粉漆的细腻度好。
根据本发明的一个方面，一种水性聚氨酯丙烯酸酯乳液，其特征在于，按重量份计，包括以下原料组分：聚氨酯丙烯酸酯预聚体，以及，聚氨酯丙烯酸酯低聚物。
根据本发明的第二方面的水性聚氨酯丙烯酸酯乳液，其特征在于，所述聚氨酯丙烯酸酯预聚体包括以下原料组分：低聚物二元醇，多异氰酸酯，以及，第二紫外光固化单体。
上述各组分之间能够产生协同作用或增效作用，聚氨酯丙烯酸酯预聚体和聚氨酯丙烯酸酯低聚物均具有一定的链长和分子结构，经紫外线固化后的水性聚氨酯丙烯酸酯乳液具有较好的机械强度，耐磨性能好。
此外，水性聚氨酯丙烯酸酯乳液采用有机溶剂含量少的聚氨酯丙烯酸酯预聚体，提供亲水性且绿色环保。
根据本发明的第三方面的水性聚氨酯丙烯酸酯乳液，其特征在于，按重量份计，所述聚氨酯丙烯酸酯预聚体包括以下原料组分：
低聚物二元醇 30～60
多异氰酸酯 5～20
第二紫外光固化单体 40～60。
上述原料合成的聚氨酯丙烯酸酯预聚体未经自乳化或分散于互不相溶的液体中，与聚氨酯丙烯酸酯低聚物和第一紫外光固化单体的相溶性好。
根据本发明的第四方面的水性聚氨酯丙烯酸酯乳液，其特征在于，还包括以下原料组分：第一紫外光固化单体，以及，水。
第一紫外光固化单体能够提供较多的官能度，保证水性聚氨酯丙烯酸酯乳液固化的交联度，进一步提升耐磨性。
可选的，所述第一紫外光固化单体和所述第二紫外光固化单体均为丙烯酸酯。
不饱和丙烯酸酯化合物包括：三羟甲基丙烷丙烯酸酯、季戊四醇三或四丙烯酸酯(PETA)、双季戊四醇五或六丙烯酸酯(DPHA)及其改性化合物，丙烯酸羟乙酯(HEA)、丙烯酸羟丙酯(HPA)、丙烯酸羟丁酯(HBA)、甲基丙烯酸羟乙酯(HEMA)、甲基丙烯酸羟丙酯(HMPA)中的至少一种。
优选的，所述丙烯酸酯为季戊四醇三丙烯酸酯或季戊四醇四丙烯酸酯(PETA)、双季戊四醇五丙烯酸酯(DPHA)及其改性化合物、双季戊四醇六丙烯酸酯、丙烯酸羟乙酯(HEA)中的一种或多种。
可选的，所述聚氨酯丙烯酸酯低聚物的原料组分包括二异氰酸酯和丙烯酸酯。
根据本发明的第五方面的水性聚氨酯丙烯酸酯乳液，其特征在于，
所述聚氨酯丙烯酸酯预聚体的数均分子量为2000～5000，官能度为6～10；
所述聚氨酯丙烯酸酯低聚物的数均分子量为1000～2000，官能度为3～10；
所述第一紫外光固化单体的官能度为3～6。
所述官能度指参与紫外光固化反应的官能团数目，即不饱和双键，其影响涂漆的固化交联度；官能度越大，固化交联度越高，有利于提升固化后漆膜的耐磨性，但官能度过大的涂料不适用于厚涂，其厚涂的漆膜容易开裂，因此，选择具有适宜官能度的聚合物与单体且控制各组分的比例，有助于提高水性聚氨酯丙烯酸酯乳液的使用性能。
根据本发明的第六方面的水性聚氨酯丙烯酸酯乳液，其特征在于，按重量份计，包括以下原料组分：
Figure BDA0003352447490000031
根据本发明的第七方面的水性聚氨酯丙烯酸酯乳液，其特征在于，按重量份计，包括以下原料组分：
Figure BDA0003352447490000032
为了兼顾耐磨性能与细腻度，根据本发明的第八方面的水性聚氨酯丙烯酸酯乳液，其特征在于，所述聚氨酯丙烯酸酯低聚物与第一紫外光固化单体的摩尔比为0.03～1.05:1。
根据本发明的第九方面的水性聚氨酯丙烯酸酯乳液，其特征在于，所述聚氨酯丙烯酸酯低聚物与第一紫外光固化单体的摩尔比为0.30～0.75:1。
根据本发明的第十方面的水性聚氨酯丙烯酸酯乳液，其特征在于，
所述低聚物二元醇选自聚氧化丙烯二醇、聚氧化乙烯二醇、聚己二酸二元醇、聚四氢呋喃醚醇、聚碳酸脂二元醇、聚酯二元醇中的一种或多种；以及
所述多异氰酸酯选自二异氰酸酯，异佛尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)、4,4'-二环己基甲烷二异氰酸酯(HMDI)、二苯甲烷二异氰酸酯(MDI)、甲苯二异氰酸酯(TDI)、4,4'-二环己基甲烷二异氰酸酯(HMDI)三聚体中的一种或多种。
作为优选，非离子低聚物二元醇中必须包含聚氧化乙烯二醇及其衍生物，分子量为200-2000g/mol；更为优选分子量为1000g/mol的聚氧化乙烯二醇。
作为优选，多异氰酸酯选用二异氰酸酯，更优选异佛尔酮二异氰酸酯(IPDI)、4,4'-二环己基甲烷二异氰酸酯(HMDI)中的一种或两种。
根据本发明的第十一方面，一种水性聚氨酯丙烯酸酯乳液的制备方法，其特征在于，包括以下步骤：
将低聚物二元醇和多异氰酸酯混合反应，制得非离子型聚氨酯；
所述非离子型聚氨酯和第二紫外光固化单体混合反应，得到聚氨酯丙烯酸酯预聚体；
将所述聚氨酯丙烯酸酯预聚体、聚氨酯丙烯酸酯低聚物与第一紫外光固化单体混合后分散在水中，得到水性聚氨酯丙烯酸酯乳液。
可选的，在所述非离子型聚氨酯和丙烯酸酯反应过程中加入阻聚剂。阻聚剂可以防止合成的聚氨酯丙烯酸酯胶化。
可选的，所述的阻聚剂为对甲氧基苯酚、对羟基苯甲醚、对叔丁基邻苯二酚、特丁基对苯醌中的一种或多种。
根据本发明的第十二方面，一种水性哑光漆，其特征在于，包括权利要求1～11任一项所述的水性聚氨酯丙烯酸酯乳液。
与现有技术相比，本申请至少具有以下技术效果之一：
与现有技术相比，本发明的水性聚氨酯丙烯酸酯乳液，该乳液为水性紫外光固化非离子聚氨酯丙烯酸酯乳液，减少有机溶剂的使用量，制得低VOCs含量的水性聚氨酯丙烯酸酯乳液，赋予了乳液优异的哑粉包裹性能，制得的哑粉漆哑粉细腻度佳；该乳液同时从树脂合成、乳化组分两个角度提升了乳液的高耐磨特性，解决了乳液相容性差的问题。
一种非离子聚氨酯丙烯酸酯预聚体的制备方法：
步骤1：将非离子低聚物二元醇在70～140℃温度下真空脱水30～180min，并测试低聚物二元醇的水分，保证其水分≤0.2wt％；降温至料温温度为40～70℃，加入多异氰酸酯和催化剂，升温至料温为60～85℃，保温60～180min至达到指定量的NCO，得到非离子聚氨酯；
步骤2：降温至料温为40～70℃，向步骤1中得到的非离子聚氨酯中加入不饱和丙烯酸酯、阻聚剂和催化剂，升温至料温为60～85℃，保温60～240min后，得到非离子聚氨酯丙烯酸酯预聚体。
一种水性聚氨酯丙烯酸酯乳液，该乳液的制备方法如下：
步骤1：将水性紫外光固化聚氨酯丙烯酸酯预聚体、紫外光固化低聚物、紫外光固化稀释单体等混合，在200～1000r/min下搅拌分散至混合均匀，得到混合物；
步骤2：在600～2500r/min搅拌分散的条件下，加入指定质量的去离子水进行乳化，得到该耐磨水性聚氨酯丙烯酸酯乳液。
具体实施方式
下面结合具体实施方式对本申请所述的技术方案做进一步的说明，但本申请不仅限于此。
实施例1～3
1、水性聚氨酯丙烯酸酯乳液的制备
(1)聚氨酯丙烯酸酯预聚体的制备
按重量份计，原料组分配比如表1所示，将聚氧乙烯二醇和聚碳酸酯二醇加入到带有机械搅拌、温度计及真空装置的玻璃反应釜中，在100℃料温、0.09Mpa真空条件下脱水60min，并测试低聚物二元醇的水分，保证其水分≤0.2wt％；降温至料温温度为50℃，加入异佛尔酮二异氰酸酯和有机铋，升温至料温为80℃，保温120min至指定残余-NCO为7.5wt％；降温至料温为50℃，继续加入不饱和丙烯酸酯、有机铋和对羟基苯甲醚，升温至料温为80℃，保温120min至残余-NCO为0.1wt％，制得聚氨酯丙烯酸酯预聚体。
(2)水性聚氨酯丙烯酸酯乳液的制备
按表2中的原料组分配比，将聚氨酯丙烯酸酯预聚体、聚氨酯丙烯酸酯低聚物、三羟甲基丙烷三丙烯酸酯在1000r/min下搅拌分散30min至混合均匀；设置转速为1500r/min，加入水进行搅拌乳化，得到水性聚氨酯丙烯酸酯乳液。测试得到的水性聚氨酯丙烯酸酯乳液的理化性质，结果见表3。
2、水性哑光漆的制备
按重量份计，将44份水性聚氨酯丙烯酸酯乳液置于PE杯中，开启分散机，转速调整为1500r/min，边分散边往乳液中加入8份水开稀，然后依次加入1份光引发剂1173、0.1份润湿剂BYK346、0.1份流平剂BYK162和2份丙二醇甲醚，最后在1500r/min条件下继续搅拌分散15min后，400目滤布过滤得到水性高光涂料。
将得到的水性高光涂料喷涂在透明PC板上，膜厚10-15μm，60℃烘烤10min，800mj/cm2光固机能量进行固化成膜。测试漆膜的RCA(耐磨)，结果如表4所示。
在上述水性高光涂料中加入2.2份哑粉(东曹1011)，在1500r/min条件下继续搅拌分散15min后，200目滤布过滤得到水性哑光涂料。
将得到的水性哑光涂料喷涂在黑色ABS或黑色PC+ABS板上，膜厚15-20μm，60℃烘烤10min，800mj/cm2光固机能量，进行固化。观察漆膜附着力、哑粉细腻度、发花状况和硬度，结果如表4所示。
本发明选用的催化剂为有机铋。
对比例1～2
分别采用水性聚氨酯分散体
Figure BDA0003352447490000061
7230(美国湛新树脂有限公司)和水性聚氨酯分散体RA7011(日本三井树脂有限公司)替代实施例1～3中的水性聚氨酯丙烯酸酯乳液，制备水性高光涂料和水性哑光漆，并将其喷涂在相同基材上进行固化，进行性能测试，结果见表4。
表1、本发明实施例的聚氨酯丙烯酸酯预聚体的原料组分
组分 实施例1 实施例2 实施例3
1000g/moL分子量聚氧化乙烯二醇 20 16 16
1000g/mol聚碳酸酯二元醇 20 16 16
异佛尔酮二异氰酸酯 13 11 11
季戊四醇三丙烯酸酯 0 16 0
双季戊四醇五丙烯酸酯 47 41 57
有机铋 0.1 0.1 0.1
对羟基苯甲醚 0.05 0.05 0.05
表2、本发明的水性聚氨酯丙烯酸酯乳液的原料组分
组分 实施例1 实施例2 实施例3
聚氨酯丙烯酸酯预聚体 26 26 26
聚氨酯丙烯酸酯低聚物 6 12 20
季戊四醇三丙烯酸酯 18 12 4
水 50 50 50
表3、本发明水性聚氨酯丙烯酸酯乳液的理化性能
理化性能 测试结果
外观 乳白泛蓝光
固含 45～50％
粘度(cP@25℃) 50～500
pH值 5～8
粒径(nm) 80～200
所用测试方法为：
乳液外观：目测
固含：国标
粘度：国标布鲁斯仪器16#转子@200rpm
pH值：国标pH计
粒径：DLS散射
表4、本发明实施例及对比例的水性哑光漆的性能测试结果
测试项目 实施例1 实施例2 实施例3 对比例1 对比例2
附着力 5B 5B 5B 5B 5B
哑光细腻度 优 优 优 一般 一般
漆膜发花状况 无 无 无 轻微 轻微
三菱铅笔硬度 H 2H 3H 2H H
摆杆硬度(次) 235 241 249 229 215
RCA次数(次) 101 159 230 89 75
所用测试方法为：
附着力：百格法
哑粉细腻度、漆膜发花状况：目视
三菱铅笔硬度：国标
摆杆硬度：摆杆硬度计
RCA：纸带摩擦测试仪(对于测试RCA的试样制备，在水性哑光漆的制备中，按重量份计，将44份水性聚氨酯丙烯酸酯乳液和一定量水性丙烯酸树脂置于PE杯中，后续操作与前文所述相同。加入水性丙烯酸树脂是为了减少RCA的测试次数，如果不加水性丙烯酸树脂，单独测乳液的RCA次数太高)。
通过表4可以看出，与采用市售水性聚氨酯分散体制成的对比例1-2相比，本发明实施例1-3的水性聚氨酯丙烯酸酯乳液在制成哑光漆膜后，哑光细腻度好，不发花，硬度高。
上述对实施例的描述是为了便于该技术领域的普通技术人员能理解和使用发明，本申请所属领域的技术人员还可以对上述实施方式进行适当的变更和修改。因此，本申请并不局限于上面揭示和描述的具体实施方式，对本发明的一些修改和变更也应当落入本申请的权利要求的保护范围内。

Claims (12)

1.一种水性聚氨酯丙烯酸酯乳液，其特征在于，包括以下原料组分：聚氨酯丙烯酸酯预聚体，以及，聚氨酯丙烯酸酯低聚物。
2.根据权利要求1所述的水性聚氨酯丙烯酸酯乳液，其特征在于，所述聚氨酯丙烯酸酯预聚体包括以下原料组分：低聚物二元醇，多异氰酸酯，以及，第二紫外光固化单体。
3.根据权利要求2所述的水性聚氨酯丙烯酸酯乳液，其特征在于，按重量份计，所述聚氨酯丙烯酸酯预聚体包括以下原料组分：
低聚物二元醇 30～60
多异氰酸酯 5～20
第二紫外光固化单体 40～60。
4.根据权利要求2所述的水性聚氨酯丙烯酸酯乳液，其特征在于，还包括以下原料组分：第一紫外光固化单体，以及，水。
5.根据权利要求4所述的水性聚氨酯丙烯酸酯乳液，其特征在于，
所述聚氨酯丙烯酸酯预聚体的数均分子量为2000～5000，官能度为6～10；
所述聚氨酯丙烯酸酯低聚物的数均分子量为1000～2000，官能度为3～10；
所述第一紫外光固化单体的官能度为3～6。
6.根据权利要求4所述的水性聚氨酯丙烯酸酯乳液，其特征在于，按重量份计，包括以下原料组分：
Figure FDA0003352447480000011
Figure FDA0003352447480000021
7.根据权利要求4所述的水性聚氨酯丙烯酸酯乳液，其特征在于，按重量份计，包括以下原料组分：
Figure FDA0003352447480000022
8.根据权利要求4所述的水性聚氨酯丙烯酸酯乳液，其特征在于，所述聚氨酯丙烯酸酯低聚物与第一紫外光固化单体的摩尔比为0.03～1.05:1。
9.根据权利要求8所述的水性聚氨酯丙烯酸酯乳液，其特征在于，所述聚氨酯丙烯酸酯低聚物与第一紫外光固化单体的摩尔比为0.30～0.75:1。
10.根据权利要求2所述的水性聚氨酯丙烯酸酯乳液，其特征在于，
所述低聚物二元醇选自聚氧化丙烯二醇及其衍生物、聚氧化乙烯二醇及其衍生物、聚己二酸二元醇、聚四氢呋喃醚醇、聚碳酸脂二元醇、聚酯二元醇中的一种或多种；以及
所述多异氰酸酯选自二异氰酸酯，异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、二苯甲烷二异氰酸酯、甲苯二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯三聚体中的一种或多种。
11.权利要求1～10任一项所述的水性聚氨酯丙烯酸酯乳液的制备方法，其特征在于，包括以下步骤：
将低聚物二元醇和多异氰酸酯混合反应，制得非离子型聚氨酯；
所述非离子型聚氨酯和第二紫外光固化单体混合反应，得到具有亲水特征的聚氨酯丙烯酸酯预聚体；
将所述聚氨酯丙烯酸酯预聚体、聚氨酯丙烯酸酯低聚物与第一紫外光固化单体混合后分散在水中，得到水性聚氨酯丙烯酸酯乳液。
12.一种水性哑光漆，其特征在于，包括权利要求1～11任一项所述的水性聚氨酯丙烯酸酯乳液。
CN202111341921.0A 2021-01-13 2021-11-12 一种水性聚氨酯丙烯酸酯乳液及其应用 Active CN114032023B (zh)

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