CN107814905A - 一种用于木器漆的无溶剂自交联改性水性聚氨酯树脂 - Google Patents

一种用于木器漆的无溶剂自交联改性水性聚氨酯树脂 Download PDF

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CN107814905A
CN107814905A CN201711167061.7A CN201711167061A CN107814905A CN 107814905 A CN107814905 A CN 107814905A CN 201711167061 A CN201711167061 A CN 201711167061A CN 107814905 A CN107814905 A CN 107814905A
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刘巧
黄军波
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Heshan River Ben Polyfat Chemical Co Ltd
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Abstract

本发明公开了一种用于木器漆的无溶剂自交联改性水性聚氨酯树脂，包括以下重量份数的组分：50‑80份多异氰酸酯，100‑150份多元醇，30‑60份高玻璃化温度醛酮树脂，10‑20份第一扩链剂，3‑5份第二扩链剂，0.05‑0.1份有机铋催化剂，50‑150份乙烯基单体，10‑15份三乙胺和400‑600份水。本发明的无溶剂自交联改性水性聚氨酯树脂能够用于木器涂料，其涂层硬度可以达到1H以上，具有好的打磨性，高的剥离强度、优良的耐水性能等特点，该水性聚氨酯树脂干燥成膜的硬度完全达到木器涂料的要求，同时改善了常规聚氨酯打磨性差的缺陷；在水性聚氨酯树脂的合成过程中无需任何溶剂，直接以乙烯基单体为溶剂，乳化后引发交联，大大简化了真空脱除溶剂的工艺，缩短了生产时间。

Description

一种用于木器漆的无溶剂自交联改性水性聚氨酯树脂
技术领域
本发明涉及高分子聚合物领域，具体涉及一种用于木器漆的无溶剂自交联改性水性聚氨酯树脂及其制备方法。
背景技术
随着人们生活水平的提高，对生活质量的要求也要求越来越高，例如对用于涂覆木器的水性漆也有了更高的要求。木器漆要求附着力强、硬度大、光泽度高、耐久、耐磨、耐水、耐油、耐溶剂、耐高温，这样不仅能增加木制品的审美价值，而且能使木制品经久耐用，提高了其使用价值。
水性聚氨酯树脂由于具有各项优异的性能，其广泛应用于皮革涂饰、涂料、黏合剂等领域。但是，水性聚氨酯树脂在硬度、耐水、耐溶剂方面仍达不到木器漆的性能要求，因此有必要研发一种改性水性聚氨酯树脂，其成膜具有优异的硬度、耐水性、耐溶剂性，可以克服现有聚氨酯成膜耐水性差，成膜硬度不够高的缺陷。
酮醛树脂是酮醛缩聚而成的中性无毒硬树脂，其在缩合期形成了饱和的环状结构，不含酯键，因此酮醛树脂具有高光泽、硬度、抗降解、耐候性、耐水性和耐热性，以及具有良好的颜料润湿性和附着力。因此，将酮醛树脂添加于水性聚氨酯树脂中，可以提水性聚氨酯树脂的快干性、光泽度、附着力、流平性、颜料润湿性、耐候性、硬度、耐水、耐溶剂性。
发明内容
本发明的目的在于提供一种光泽度高、附着力大，硬度大，具有优异的耐候性、耐水性、耐溶剂性和耐酸碱性的用于木器漆的无溶剂自交联改性水性聚氨酯树脂。
本发明的另一目的在于提供该无溶剂自交联改性水性聚氨酯树脂的制备方法和其在涂料中的应用。
本发明采用的技术方案是：一种用于木器漆的无溶剂自交联改性水性聚氨酯树脂，包括以下重量份数的组分：
优选的，用于木器漆的无溶剂自交联改性水性聚氨酯树脂，包括以下重量份数的组分：
优选的，所述多异氰酸酯选自甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、1,6-己二异氰酸酯、苯二亚甲基二异氰酸酯、萘-1,5-二异氰酸酯、多亚甲基多苯基异氰酸酯、四甲基苯二亚甲基二异氰酸酯、甲基环己基二异氰酸酯和二环己基甲烷二异氰酸酯中的一种或几种。
优选的，所述多元醇选自聚己内酯多元醇、聚碳酸酯多元醇、聚四氢呋喃醚多元醇、聚环氧乙烷多元醇、聚环氧丙烷多元醇和端羟基聚丁二烯和聚硅氧烷多元醇和聚酯醚多元醇中的一种或几种。
优选的，所述多元醇选自二元醇。
优选的，所述二元醇为己内酯二元醇、聚碳酸酯二元醇、聚四氢呋喃醚二元醇、聚环氧乙烷二元醇、聚环氧丙烷二元醇和端羟基聚丁二烯和聚硅氧烷二元醇中的一种或几种。
添加多元醇，可以使水性聚氨酯树脂的结晶性和机械强度间达到最佳平衡。
优选的，多异氰酸酯中多异氰酸酯基团与多元醇中羟基基团的摩尔数之比为0.97-0.98:1。
优选的，所述高玻璃化温度醛酮树脂的玻璃化温度是80-120℃，分子量是250-1000。
酮醛树脂具有高光泽、硬度、抗降解、耐候性、耐水性和耐热性，以及具有良好的颜料润湿性和附着力。因此，将具有高玻璃化温度、一定分子量的酮醛树脂添加于水性聚氨酯树脂中，可以提水性聚氨酯树脂的快干性、光泽度、附着力、流平性、颜料润湿性、耐候性、硬度、耐水、耐溶剂性，从而赋予木器漆优异的硬度、附着力、光泽度和耐水、耐溶剂性。添加醛酮树脂可以调节形成的漆膜的玻璃化温度和提升漆膜的耐溶剂性。
优选的，所述第一扩链剂选自二羟甲基丙酸、二羟甲基丁酸、二羟甲基戊酸和二羟甲基辛酸中的一种或几种。
优选的，所述第二扩链剂选自乙二醇、一缩二乙二醇、1,4-丁二醇、2,3-丁二醇、1,6-己二醇、新戊二醇、二甘醇、甘油、山梨醇、三羟甲基丙烷和二羟甲基环己烷中的一种或几种。
优选的，所述有机铋催化剂选自Coscat83、有机铋1610、有机铋2010、有机铋2810和有机铋2808中的一种或几种。
优选的，所述乙烯基单体选自甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸乙酯、羟丙酯、羟乙酯、丙烯酸、AAEM、DAAM、NMA和GMA中的一种或几种。乙烯基单体的作用为调整反应溶液的粘度。乙烯基单体的添加量可根据反应需要酌情添加。
本发明还提供了用于木器漆的无溶剂自交联改性水性聚氨酯树脂的制备方法，包括以下步骤：
1)将多元醇、醛酮树脂和多异氰酸酯在85-95℃下反应2-3h；
2)再加入第一扩链剂和第二扩链剂在75-85℃下反应1-3h；
3)再加入有机铋催化剂在65-75℃下反应2-3h；加入乙烯基单体，降温至35-45℃加入三乙胺中和；
4)加入水，经85-95℃下反应2-3h，获得用于木器漆的无溶剂自交联改性水性聚氨酯树脂。
优选的，可以在步骤2)中加入第一扩链剂和第二扩链剂的同时加入乙烯基单体。
本发明还提供了该无溶剂自交联改性水性聚氨酯树脂在木器涂料中的应用。
应用的方法为：将无溶剂自交联改性水性聚氨酯树脂增稠、润湿、消泡处理后，用于直接涂布。
上述所述增稠、润湿、消泡处理步骤均采用现有技术中常用方式进行。
本发明的有益技术效果是：本发明的无溶剂自交联改性水性聚氨酯树脂能够用于木器涂料，其涂层硬度可以达到1H以上，具有好的打磨性，高的剥离强度、优良的耐水性能等特点，该水性聚氨酯树脂干燥成膜的硬度完全达到木器涂料的要求，同时改善了常规聚氨酯打磨性差的缺陷；在水性聚氨酯树脂的合成过程中无需任何溶剂，直接以乙烯基单体为溶剂，乳化后引发交联，大大简化了真空脱除溶剂的工艺，缩短了生产时间。
具体实施方式
实施例1
一种用于木器漆的无溶剂自交联改性水性聚氨酯树脂，包括以下重量份数的组分：
其中，甲苯二异氰酸酯中二异氰酸酯基团与聚碳酸酯多元醇中羟基基团的摩尔数之比为0.97:1；高玻璃化温度醛酮树脂的玻璃化温度是120℃，分子量是250。
一种用于木器漆的无溶剂自交联改性水性聚氨酯树脂的制备方法，包括以下步骤：
1)将多元醇(聚碳酸酯多元醇)、醛酮树脂和多异氰酸酯(甲苯二异氰酸酯)在85℃下反应2h；
2)再加入第一扩链剂(二羟甲基丙酸)、第二扩链剂(乙二醇)和乙烯基单体(甲基丙烯酸甲酯)在75℃下反应2h；
3)再加入有机铋催化剂(甲基丙烯酸甲酯)在65℃下反应2h，降温至35℃加入三乙胺中和；
4)加入水，经85℃下反应2h，获得用于木器漆的无溶剂自交联改性水性聚氨酯树脂。
实施例2
一种用于木器漆的无溶剂自交联改性水性聚氨酯树脂，包括以下重量份数的组分：
其中，1,6-己二异氰酸酯中二异氰酸酯基团与聚碳酸酯二元醇中羟基基团的摩尔数之比为0.98:1；高玻璃化温度醛酮树脂的玻璃化温度是90℃，分子量是300。
一种用于木器漆的无溶剂自交联改性水性聚氨酯树脂的制备方法，包括以下步骤：
1)将多元醇(聚碳酸酯二元醇)、醛酮树脂和多异氰酸酯(1,6-己二异氰酸酯)在95℃下反应2h；
2)再加入第一扩链剂(二羟甲基丁酸)和第二扩链剂(甘油+山梨醇)在85℃下反应1h；
3)再加入有机铋催化剂(有机铋2810)在75℃下反应3h；加入乙烯基单体(丙烯酸乙酯)，降温至45℃加入三乙胺中和；
4)加入水，经95℃下反应3h，获得用于木器漆的无溶剂自交联改性水性聚氨酯树脂。
实施例3
一种用于木器漆的无溶剂自交联改性水性聚氨酯树脂，包括以下重量份数的组分：
其中，萘-1,5-二异氰酸酯中二异氰酸酯基团与聚四氢呋喃醚多元醇中羟基基团的摩尔数之比为0.98:1；高玻璃化温度醛酮树脂的玻璃化温度是100℃，分子量是350。
一种用于木器漆的无溶剂自交联改性水性聚氨酯树脂的制备方法，包括以下步骤：
1)将多元醇(聚四氢呋喃醚多元醇)、醛酮树脂和多异氰酸酯(萘-1,5-二异氰酸酯)在90℃下反应2.5h；
2)再加入第一扩链剂(二羟甲基戊酸+二羟甲基辛酸)和第二扩链剂(2,3-丁二醇)在80℃下反应2h；
3)再加入有机铋催化剂(有机铋1610)在70℃下反应2h；加入乙烯基单体(AAEM+DAAM)，降温至40℃加入三乙胺中和；
4)加入水，经90℃下反应2.5h，获得用于木器漆的无溶剂自交联改性水性聚氨酯树脂。
实施例4
一种用于木器漆的无溶剂自交联改性水性聚氨酯树脂，包括以下重量份数的组分：
其中，多亚甲基多苯基异氰酸酯中异氰酸酯基团与聚环氧乙烷多元醇中羟基基团的摩尔数之比为0.97:1；高玻璃化温度醛酮树脂的玻璃化温度是105℃，分子量是500。
用于木器漆的无溶剂自交联改性水性聚氨酯树脂的制备方法与实施例3的用于木器漆的无溶剂自交联改性水性聚氨酯树脂的制备方法相同。
实施例5
一种用于木器漆的无溶剂自交联改性水性聚氨酯树脂，包括以下重量份数的组分：
其中，甲基环己基二异氰酸酯中二异氰酸酯基团与聚硅氧烷二元醇中羟基基团的摩尔数之比为0.98:1；高玻璃化温度醛酮树脂的玻璃化温度是120℃，分子量是600。
用于木器漆的无溶剂自交联改性水性聚氨酯树脂的制备方法与实施例3的用于木器漆的无溶剂自交联改性水性聚氨酯树脂的制备方法相同。
1-5制备的用于木器漆的无溶剂自交联改性水性聚氨酯树脂能够用于木器涂料，其涂层硬度可以达到1H以上，具有好的打磨性，高的剥离强度、优良的耐水性能等特点。

Claims (10)

1.一种用于木器漆的无溶剂自交联改性水性聚氨酯树脂，其特征在于，包括以下重量份数的组分：
2.根据权利要求1所述的用于木器漆的无溶剂自交联改性水性聚氨酯树脂，其特征在于，包括以下重量份数的组分：
3.根据权利要求1或2所述的用于木器漆的无溶剂自交联改性水性聚氨酯树脂，其特征在于，所述多异氰酸酯选自甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、1,6-己二异氰酸酯、苯二亚甲基二异氰酸酯、萘-1,5-二异氰酸酯、多亚甲基多苯基异氰酸酯、四甲基苯二亚甲基二异氰酸酯、甲基环己基二异氰酸酯和二环己基甲烷二异氰酸酯中的一种或几种。
4.根据权利要求1或2所述的用于木器漆的无溶剂自交联改性水性聚氨酯树脂，其特征在于，所述多元醇选自聚己内酯多元醇、聚碳酸酯多元醇、聚四氢呋喃醚多元醇、聚环氧乙烷多元醇、聚环氧丙烷多元醇和端羟基聚丁二烯和聚硅氧烷多元醇和聚酯醚多元醇中的一种或几种。
5.根据权利要求1或2所述的用于木器漆的无溶剂自交联改性水性聚氨酯树脂，其特征在于，所述多元醇为二元醇；多异氰酸酯中多异氰酸酯基团与多元醇中羟基基团的摩尔数之比为0.97-0.98:1。
6.根据权利要求5所述的用于木器漆的无溶剂自交联改性水性聚氨酯树脂，其特征在于，所述二元醇为己内酯二元醇、聚碳酸酯二元醇、聚四氢呋喃醚二元醇、聚环氧乙烷二元醇、聚环氧丙烷二元醇和端羟基聚丁二烯和聚硅氧烷二元醇中的一种或几种；所述高玻璃化温度醛酮树脂的玻璃化温度是80-120℃，分子量是250-1000。
7.根据权利要求1或2所述的用于木器漆的无溶剂自交联改性水性聚氨酯树脂，其特征在于，所述第一扩链剂选自二羟甲基丙酸、二羟甲基丁酸、二羟甲基戊酸和二羟甲基辛酸中的一种或几种；所述第二扩链剂选自乙二醇、一缩二乙二醇、1,4-丁二醇、2,3-丁二醇、1,6-己二醇、新戊二醇、二甘醇、甘油、山梨醇、三羟甲基丙烷和二羟甲基环己烷中的一种或几种。
8.根据权利要求1或2所述的用于木器漆的无溶剂自交联改性水性聚氨酯树脂，其特征在于，所述有机铋催化剂选自Coscat83、有机铋1610、有机铋2010、有机铋2810和有机铋2808中的一种或几种；所述乙烯基单体选自甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸乙酯、羟丙酯、羟乙酯、丙烯酸、AAEM、DAAM、NMA和GMA中的一种或几种。
9.权利要求1-8中任一项所述的用于木器漆的无溶剂自交联改性水性聚氨酯树脂的制备方法，其特征在于，包括以下步骤：
1)将多元醇、醛酮树脂和多异氰酸酯在85-95℃下反应2-3h；
2)再加入第一扩链剂和第二扩链剂在75-85℃下反应1-3h；
3)再加入有机铋催化剂在65-75℃下反应2-3h；加入乙烯基单体，降温至35-45℃加入三乙胺中和；
4)加入水，经85-95℃下反应2-3h，获得用于木器漆的无溶剂自交联改性水性聚氨酯树脂。
10.权利要求1-8中任一项所述的用于木器漆的无溶剂自交联改性水性聚氨酯树脂在木器涂料中的应用。
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Publication number Priority date Publication date Assignee Title
CN109111559A (zh) * 2018-07-25 2019-01-01 禾丰新材料科技有限公司 水性聚酮树脂乳液及其制备方法和应用
CN112194769A (zh) * 2020-09-28 2021-01-08 广州科苑新型材料有限公司 一种水性聚氨酯/聚丙烯酸酯改性酮醛树脂复合乳液及其制备方法与应用
CN112898884A (zh) * 2021-01-25 2021-06-04 深圳市彩田化工有限公司 一种耐磨聚脲涂料及其制备方法和应用
CN114032047A (zh) * 2021-12-13 2022-02-11 宁波惠之星新材料科技有限公司 一种柔性折叠屏抗冲保护膜及其制备方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109111559A (zh) * 2018-07-25 2019-01-01 禾丰新材料科技有限公司 水性聚酮树脂乳液及其制备方法和应用
CN112194769A (zh) * 2020-09-28 2021-01-08 广州科苑新型材料有限公司 一种水性聚氨酯/聚丙烯酸酯改性酮醛树脂复合乳液及其制备方法与应用
CN112898884A (zh) * 2021-01-25 2021-06-04 深圳市彩田化工有限公司 一种耐磨聚脲涂料及其制备方法和应用
CN112898884B (zh) * 2021-01-25 2021-12-07 深圳市彩田化工有限公司 一种耐磨聚脲涂料及其制备方法和应用
CN114032047A (zh) * 2021-12-13 2022-02-11 宁波惠之星新材料科技有限公司 一种柔性折叠屏抗冲保护膜及其制备方法

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