CN112852286A - 水性聚氨酯丙烯酸酯乳液及其制备方法和水性哑光漆 - Google Patents
水性聚氨酯丙烯酸酯乳液及其制备方法和水性哑光漆 Download PDFInfo
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- CN112852286A CN112852286A CN202110040384.XA CN202110040384A CN112852286A CN 112852286 A CN112852286 A CN 112852286A CN 202110040384 A CN202110040384 A CN 202110040384A CN 112852286 A CN112852286 A CN 112852286A
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- polyurethane acrylate
- acrylate emulsion
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
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- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 2
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- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 2
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
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- NCCTVAJNFXYWTM-UHFFFAOYSA-N 2-tert-butylcyclohexa-2,5-diene-1,4-dione Chemical compound CC(C)(C)C1=CC(=O)C=CC1=O NCCTVAJNFXYWTM-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
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- 241001417518 Rachycentridae Species 0.000 description 1
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- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
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- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
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- 230000014759 maintenance of location Effects 0.000 description 1
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Classifications
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Abstract
本申请提供了水性聚氨酯丙烯酸酯乳液及其制备方法和水性哑光漆，按重量份计，所述水性聚氨酯丙烯酸酯乳液包括以下原料组分：非乳化型聚氨酯丙烯酸酯预聚体20～80；聚氨酯丙烯酸酯低聚物0～70；第一紫外光固化单体0～50；水50～70。本申请的水性聚氨酯丙烯酸酯乳液的性能佳，其制备的水性哑粉漆表观光滑，哑粉细腻度高，耐磨性好。
Description
技术领域
本申请涉及涂料技术领域，特别是涉及水性聚氨酯丙烯酸酯乳液及其制备方法和水性哑光漆。
背景技术
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、化妆品等高端领域得到重要而广泛应用，高耐磨哑光漆成为了消费者们追求的需求方向。环保力度的加大，催生了高耐磨水性哑光漆的进一步发展。高耐磨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，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。将水性聚氨酯丙烯酸酯乳液应用于哑光漆领域，不仅满足哑光漆的性能需求，而且减轻了环保压力。
传统水性聚氨酯丙烯酸酯主要通过预聚体分散法和丙酮法合成，而后中和乳化得到乳液，但是其制得水性哑粉漆表观粗糙，哑粉细腻度不佳，限制其应用。公开号为CN108531042A和CN107446484A专利文献都公开了通过引入二氧化硅无机物成分提高漆膜耐磨性，但二氧化硅无机物与高分子组分之间的相容性隐患，限制了该类耐磨哑粉漆的应用范围。
发明内容
针对现有技术问题，本申请提供了水性聚氨酯丙烯酸酯乳液，具有良好的耐磨性，且挥发性有机物含量低，符合环保要求。
本申请的水性聚氨酯丙烯酸酯乳液，按重量份计，包括以下原料组分：
上述各组分之间能够产生协同作用或增效作用，所述非乳化型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；在此基础上，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。
此外，水性聚氨酯丙烯酸酯乳液采用有机溶剂含量少的非乳化型聚氨酯丙烯酸酯预聚体，绿色环保。
可选的，按重量份计，所述非乳化型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。
上述原料合成的非乳化型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。
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。
优选的，所述丙烯酸酯为季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、双季戊四醇五丙烯酸酯、双季戊四醇六丙烯酸酯、丙烯酸羟乙酯中的一种或多种。
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。
可选的，所述非乳化型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。
可选的，按重量份计，所述水性聚氨酯丙烯酸酯乳液包括以下原料组分：
可选的，按重量份计，所述水性聚氨酯丙烯酸酯乳液包括以下原料组分：
可选的，按重量份计，所述水性聚氨酯丙烯酸酯乳液包括以下原料组分：
为了兼顾耐磨性能与细腻度，可选的，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。
可选的，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0.3～0.75:1。
可选的，所述低聚物二元醇为聚氧化丙烯二醇、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；
所述多异氰酸酯为二异氰酸酯，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；
所述丙烯酸酯为季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、双季戊四醇五丙烯酸酯、双季戊四醇六丙烯酸酯、丙烯酸羟乙酯中的一种或多种。
本申请还提供了水性聚氨酯丙烯酸酯乳液的制备方法，包括以下步骤：
将低聚物二元醇和多异氰酸酯混合反应，至残余-NCO≤7.5wt％，制得非离子型聚氨酯；
所述非离子型聚氨酯和丙烯酸酯混合反应，至残余-NCO≤0.2wt％，得到非乳化型聚氨酯丙烯酸酯预聚体；
将所述非乳化型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。
本申请还提供了一种水性哑光漆，包括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：
(1)采用非乳化型聚氨酯丙烯酸酯预聚体，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；
(2)利用水性聚氨酯丙烯酸酯乳液制备的水性哑光漆的粉细腻度高和耐磨性能好。
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
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二月桂酸二丁基锡，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、二月桂酸二丁基锡和对羟基苯甲醚，升温至料温为80℃，保温120min至残余-NCO为0.1wt％，制得非乳化型聚氨酯丙烯酸酯预聚体
按表2中的原料组分配比，将非乳化型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，测试其理化性质，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和水性丙烯酸树脂于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；喷涂在透明PC板上，膜厚10-15μm，60℃烘烤10min，800mj/cm2光固机能量固化后，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光固机能量固化后，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。
对比例1～2
分别采用水性聚氨酯分散体
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，性能测试结果见表4。
表1非乳化型聚氨酯丙烯酸酯预聚体的原料组分
表2水性聚氨酯丙烯酸酯乳液的原料组分
表3水性聚氨酯丙烯酸酯乳液的理化性能
| 乳液指标 | 乳液参数 |
| 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 |
表4水性哑光漆的测试结果
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 (10)
1.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：
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，按重量份计，所述非乳化型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。
3.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，所述非乳化型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。
4.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，按重量份计，包括以下原料组分：
5.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，按重量份计，包括以下原料组分：
6.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低聚物与第一紫外光固化单体的摩尔比为0.03～1.05:1。
7.根据权利要求6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。
8.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，所述低聚物二元醇为聚氧化丙烯二醇、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；
所述多异氰酸酯为二异氰酸酯，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。
9.权利要求1～8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，至残余-NCO≤7.5wt％，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，至残余-NCO≤0.2wt％，得到非乳化型聚氨酯丙烯酸酯预聚体；
将所述非乳化型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。
10.一种水性哑光漆，其特征在于，包括权利要求1～8任一项所述的水性聚氨酯丙烯酸酯乳液。
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