CN107513345A - 一种不饱和型聚氨酯涂层的制备方法 - Google Patents

一种不饱和型聚氨酯涂层的制备方法 Download PDF

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CN107513345A
CN107513345A CN201710844616.0A CN201710844616A CN107513345A CN 107513345 A CN107513345 A CN 107513345A CN 201710844616 A CN201710844616 A CN 201710844616A CN 107513345 A CN107513345 A CN 107513345A
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申立全
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Abstract

一种不饱和型聚氨酯涂层的制备方法，先将多元醇预先脱水，在加入催化剂和稀释剂情况下，加入二异氰酸酯，然后加热至60～80℃保温至NCO含量为0.1～0.3％，得到聚氨酯预聚体，然后依次加入阻聚剂、混合均匀后加入羟基丙烯酸酯封端，搅拌混合后至NCO含量为0，再加入光引发剂、抗氧剂、紫外光吸收剂、流平剂、消泡剂，然后悬涂于基底材料上，光固成膜后得到不饱和型聚氨酯涂层。本发明将丙烯酸酯的不饱和双键引入聚氨酯体系中，并以预聚的方法将涂层组分中的树脂分子量提高到5000‑20000，通过光固化使得涂层良好的附着在透明基材表面。缩短了涂层固化时间，从而提高成品合格率降低生产成本。

Description

一种不饱和型聚氨酯涂层的制备方法
技术领域
本发明涉及化工领域，尤其涉及聚氨酯涂料，特别是一种不饱和型聚氨酯涂层及其制备方法。
背景技术
国内塑料涂层种类繁多，不同塑料基材针对的涂层也不同，针对透明度要求严格的塑料涂层，主要以聚氨酯居多，而这种涂层的固化温度需要120℃，固化时间长达2-3小时，太高的温度和太长的固化时间严重降低成品的合格率，透明基材容易发黄，同时增加生产成本。
发明内容
本发明的目的在于提供一种不饱和型聚氨酯涂层的制备方法，所述的这种不饱和型聚氨酯涂层的制备方法要解决现有技术中的塑料涂层固化温度太高和固化时间太长，导致产品的合格率降低的技术问题。
本发明提供了一种不饱和型聚氨酯涂层的制备方法，包括如下步骤：
1)按照重量份数称取多元醇、催化剂、二异氰酸酯、稀释剂、阻聚剂、羟基丙烯酸酯、光引发剂、抗氧剂、紫外光吸收剂、流平剂和消泡剂，上述原料的重量份数如下：
2)先将多元醇预先脱水，在加入催化剂和稀释剂情况下，在45～55℃的条件下加入二异氰酸酯，然后加热至60～80℃保温，至NCO含量为0.1～0.3％，得到聚氨酯预聚体，然后加入阻聚剂、混合均匀后加入羟基丙烯酸酯封端，搅拌混合后，在60～80℃的条件下保温，至NCO含量为0，再加入光引发剂、抗氧剂、紫外光吸收剂、流平剂、消泡剂，然后悬涂于基底材料上，100～140℃烘烤2～4分钟，光固成膜后得到不饱和型聚氨酯涂层。
进一步的，所述的多元醇为聚醚多元醇、聚碳酸酯多元醇、聚己内酯多元醇、聚酯多元醇、二元醇或者二元硫醇中的任意一种或者两种以上的组合。
进一步的，所述的二异氰酸酯为XDI、HDI、MDI、IPDI或者HMDI中的任意一种或者两种以上的组合。
进一步的，所述的催化剂为乙基己酸锡、二月桂酸二丁基锡或者辛酸亚锡中的任意一种。
进一步的，所述的阻聚剂为对苯二酚、2-叔丁基对苯二酚、甲基对苯二酚、4-甲氧基苯酚中的任意一种。
进一步的，所述的稀释剂为醋酸乙酯、醋酸丁酯、碳酸二甲酯、甲苯、二甲苯、丙二醇甲醚醋酸酯中的任意一种。
进一步的，所述的羟基丙烯酸酯为甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、丙烯酸己内酯中的任意一种或者两种以上的组合。
进一步的，所述的抗氧剂为2，6-二叔丁基对甲酚、双(3，5-三级丁基-4-羟基苯基)硫醚、四〔β-(3，5-三级丁基-4-羟基苯基)丙酸〕季戊四醇酯、硫代二丙酸双酯种的一种。
进一步的，所述的紫外光吸收剂为UV531、UV-9、UVP327或者UV-O中的任意一种。
进一步的，所述的光引发剂为184、TPO、127或者1173中的任意一种或者两种以上的组合。
进一步的，所述的流平剂为BYK-358N、BYK-370、BYK-333或者BYK-306中的任意一种或者两种以上的组合。
进一步的，所述的消泡剂为BYK-A550、BKY-A560、BKY-A555或者BYK-A530中的任意一种或者两种以上的组合。
进一步的，所述的基底材料为聚碳酸酯材料、聚氨酯材料、丙烯酸材料、聚氯乙烯材料、聚对苯二甲酸乙二醇酯材料中的任意一种或者两种以上的组合。
进一步的，在上述的产物中还可以添加光致变色粉。
本发明的原理是：本发明将丙烯酸酯的不饱和双键引入聚氨酯体系中，并以预聚的方法将涂层组分中的树脂分子量提高到5000-20000，通过光固化使得涂层良好的附着在透明基材表面。缩短了涂层固化时间，从而提高成品合格率降低生产成本。
本发明喝已有技术相比，其技术效果是积极和明显的。本发明的这种不饱和型聚氨酯涂层的制备方法使得不饱和聚氨酯涂层组合物在基材上具有透明好、高折射率、良好的牢固度和耐老化性能。
具体实施方式
下述实施例采用的化合物的名称(下述化合物均为市售原料)：
PCD1000：聚碳酸酯二元醇(分子量1000)
PPG400：聚丙二醇(分子量400)
BSA-F30:双酚A聚醚二元醇(含3个PO)
XDI：苯二亚甲基二异氰酸酯
BEPD:2-乙基，2-丁基丙二醇
PCL1000：聚己内酯二元醇(分子量1000)
IPDI:异佛尔酮二异氰酸酯
PDA1000：聚酯二元醇(分子量1000)
HDI:六亚甲基二异氰酸酯
PTMEG1000：聚四氢呋喃二元醇(分子量1000)
PNA1000:聚酯二元醇(分子量1000)
CHDM:环己烷二甲醇
毕克消泡剂 BYK-A550
毕克流平剂 BYK-358N
巴斯夫紫外光吸收剂 UV531
光引发剂 1173:2-羟基-2-甲基-1-苯基-1-丙酮
抗氧剂BHT:2，6-二叔丁基对甲酚
实施例1：
在四口烧瓶中，加入1g 2-巯基乙醇、5g PCD1000、1g PPG400、2gBSA-F30搅拌均匀后，在120℃下抽真空1h，降温至50℃，加入0.02g二月桂酸二丁基锡和100g二甲苯，然后加入5.02g的XDI，70℃保温至NCO含量为0.2％，然后加入0.002g 4-甲氧基苯酚，搅拌均匀后加入0.69g甲基丙烯酸羟乙酯，70℃保温至NCO为0,，得到产物，测得分子量为12000左右，取产物10g，加入0.02gBHT、0.01g UV531、0.01g BYK-358N、0.01gBYK-A550、0.05g1173，混合均匀后得到不饱和型聚氨酯涂层组合物。
实施例2：
在四口烧瓶中，加入1g BEPD、2g BSA F-30、1g PPG400、5gPCL1000搅拌均匀后，在120℃下抽真空1h，降温至50℃，加入0.02g二月桂酸二丁基锡和100g二甲苯，然后加入4.98g的IPDI，70℃保温至NCO含量为0.2％，然后加入0.002g 4-甲氧基苯酚，搅拌均匀后加入0.70g的甲基丙烯酸羟丙酯，70℃保温至NCO为0,，得到产物测得分子量为13000左右，取产物10g，加入0.02gBHT、0.01g UV531、0.01g BYK-358N、0.01gBYK-A550、0.05g1173，混合均匀后得到不饱和型聚氨酯涂层组合物。
实施例3：
在四口烧瓶中，加入1g CHDM、2g BSA F-30、1g PPG400、5gPDA1000搅拌均匀后，在120℃下抽真空1h，降温至50℃，加入0.02g二月桂酸二丁基锡和100g二甲苯，然后加入3.26g的HDI，70℃保温至NCO含量为0.2％，然后加入0.002g 4-甲氧基苯酚，搅拌均匀后加入0.70g的甲基丙烯酸羟丙酯，70℃保温至NCO为0,，得到产物，测得分子量为12000左右，取产物10g，加入0.02gBHT、0.01g UV531、0.01g BYK-358N、0.01gBYK-A550、0.05g1173，混合均匀后得到不饱和型聚氨酯涂层组合物。
实施例4：
在四口烧瓶中，加入1g BEPD、2g BSA F-30、1g PPG400、5gPTMEG1000搅拌均匀后，在120℃下抽真空1h，降温至50℃，加入0.02g二月桂酸二丁基锡和100g二甲苯，然后加入4.98g的IPDI，70℃保温至NCO含量为0.2％，然后加入0.002g 4-甲氧基苯酚，搅拌均匀后加入0.69g的甲基丙烯酸羟丙酯，70℃保温至NCO为0,，得到产物，测得分子量为12000左右，取产物10g，加入0.02gBHT、0.01g UV531、0.01g BYK-358N、0.01gBYK-A550、0.05g1173，混合均匀后得到不饱和型聚氨酯涂层组合物。
实施例5：
在四口烧瓶中，加入1gCHDM、2g BSA F-30、1g PPG400、5gPNA1000搅拌均匀后，在120℃下抽真空1h，降温至50℃，加入0.02g二月桂酸二丁基锡和100g二甲苯，然后加入3.22g的XDI，70℃保温至NCO含量为0.2％，然后加入0.002g 4-甲氧基苯酚，搅拌均匀后加入1.83g的丙烯酸己内酯，70℃保温至NCO为0,，得到产物，测得分子量为13000左右，取产物10g，加入0.02gBHT、0.01g UV531、0.01g BYK-358N、0.01gBYK-A550、0.05g1173，混合均匀后得到不饱和型聚氨酯涂层组合物。
实施例6：
上述实施例不饱和型聚氨酯涂层组合物的牢固度测试方法包含：
a)将不饱和型聚氨酯涂层组合物涂敷到基底的至少一个表面，彻底固化后，将涂布的基材在沸水中浸泡1小时，在冷却和干燥后，用刀片在基材的涂层上作出交叉影线图案，随后将胶带施用到涂布的基材的交叉影线区域。在使用胶带后，将胶带从涂层出除去，重复胶带的施用和除去三次。若在胶带的重复施用和除去期间没有涂层从基材除去，那么涂层组合物以100％通过试验。若由于胶带的重复施用和除去，有任何涂层从透镜除去，那么涂层组合物试验失败。
b)将不饱和型聚氨酯涂层组合物涂敷到基材的至少一个表面，彻底固化后，通过在60℃下将塑料基材进入水性10％(按重量计)的NaOH溶液中经历10分钟来将基材浸蚀，将浸蚀的基材用去离子水冲洗，然后烘干，使基材在6英寸/分钟的牵引速度下在硬涂层组合物中浸涂，随后使浸涂的基材在110℃下固化2小时后降温至室温。用刀片在透镜的涂层上做出交叉影线图案，随后将胶带施用到涂布的基材的交叉影线区域。在使用胶带后，将胶带从涂层出除去，重复胶带的施用和除去三次。若在胶带的重复施用和除去期间没有涂层从基材除去，那么涂层组合物以100％通过试验。若由于胶带的重复施用和除去，有任何涂层从基材除去，那么涂层组合物试验失败。
具体的，所述的硬涂层组分为有机硅氧烷涂层组合物。

Claims (9)

1.一种不饱和型聚氨酯涂层的制备方法，其特征在于包括以下步骤：
1)按照重量份数称取多元醇、催化剂、二异氰酸酯、稀释剂、阻聚剂、羟基丙烯酸酯、光引发剂、抗氧剂、紫外光吸收剂、流平剂和消泡剂，上述原料的重量份数如下：
2)先将多元醇预先脱水，在加入催化剂和稀释剂情况下，在45～55℃的条件下加入二异氰酸酯，然后加热至60～80℃保温，至NCO含量为0.1～0.3％，得到聚氨酯预聚体，然后加入阻聚剂，混合均匀后加入羟基丙烯酸酯封端，搅拌混合后，在60～80℃的条件下保温，至NCO含量为0，再加入光引发剂、抗氧剂、紫外光吸收剂、流平剂、消泡剂，然后悬涂于基底材料上，100～140℃烘烤2～4分钟，光固成膜后得到不饱和型聚氨酯涂层。
2.根据权利要求1所述的一种不饱和型聚氨酯涂层的制备方法，其特征在于：所述的多元醇为聚醚多元醇、聚碳酸酯多元醇、聚己内酯多元醇、聚酯多元醇、二元醇或者二元硫醇中的任意一种或者两种以上的组合；所述的二异氰酸酯为XDI、HDI、MDI、IPDI或者HMDI中的任意一种或者两种以上的组合。
3.根据权利要求1所述的一种不饱和型聚氨酯涂层的制备方法，其特征在于：所述的催化剂为乙基己酸锡、二月桂酸二丁基锡或者辛酸亚锡中的任意一种；所述的阻聚剂为对苯二酚、2-叔丁基对苯二酚、甲基对苯二酚、4-甲氧基苯酚中的任意一种。
4.根据权利要求1所述的一种不饱和型聚氨酯涂层的制备方法，其特征在于：所述的稀释剂为醋酸乙酯、醋酸丁酯、碳酸二甲酯、甲苯、二甲苯、丙二醇甲醚醋酸酯中的任意一种；所述的羟基丙烯酸酯为甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、丙烯酸己内酯中的任意一种或者两种以上的组合。
5.根据权利要求1所述的一种不饱和型聚氨酯涂层的制备方法，其特征在于：所述的抗氧剂为2，6-二叔丁基对甲酚、双(3，5-三级丁基-4-羟基苯基)硫醚、四〔β-(3，5-三级丁基-4-羟基苯基)丙酸〕季戊四醇酯、硫代二丙酸双酯种的一种。
6.根据权利要求1所述的一种不饱和型聚氨酯涂层的制备方法，其特征在于：所述的紫外光吸收剂为UV531、UV-9、UVP327或者UV-O中的任意一种；所述的光引发剂为184、TPO、127或者1173中的任意一种或者两种以上的组合。
7.根据权利要求1所述的一种不饱和型聚氨酯涂层的制备方法，其特征在于：所述的流平剂为BYK-358N、BYK-370、BYK-333或者BYK-306中的任意一种或者两种以上的组合；所述的消泡剂为BYK-A550、BKY-A560、BKY-A555或者BYK-A530中的任意一种或者两种以上的组合。
8.根据权利要求1所述的一种不饱和型聚氨酯涂层的制备方法，其特征在于：所述的基底材料为聚碳酸酯材料、聚氨酯材料、丙烯酸材料、聚氯乙烯材料、聚对苯二甲酸乙二醇酯材料中的任意一种或者两种以上的组合。
9.根据权利要求1所述的一种不饱和型聚氨酯涂层的制备方法，其特征在于：在上述的产物中添加光致变色粉。
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