CN116904100A - 一种双层防护涂层及其制备方法 - Google Patents
一种双层防护涂层及其制备方法 Download PDFInfo
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- CN116904100A CN116904100A CN202310652898.XA CN202310652898A CN116904100A CN 116904100 A CN116904100 A CN 116904100A CN 202310652898 A CN202310652898 A CN 202310652898A CN 116904100 A CN116904100 A CN 116904100A
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Classifications
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Abstract
本发明涉及一种双层防护涂层,其具有低的固化温度,涂层的热固化过程不会对基材的力学性能例如冲击强度产生不利影响,将该双层防护涂层用于聚碳酸酯基材上能够使基材保持高的冲击强度。另外,本发明还涉及所述双层防护涂层的制备方法。
Description
技术领域
本发明涉及基材防护技术领域,具体涉及一种双层防护涂层及其制备方法。
背景技术
相较于聚甲基丙烯酸甲酯、PET膜、透明PU材料等基材,聚碳酸酯基材的综合性能优异,弹性系数高,冲击强度高,透光率亦是工程塑料中的佼佼者,是最为理想的工程塑料之一。但聚碳酸酯基材的耐磨性、耐溶剂性能差,使用前需要使用涂层涂覆等方法对其进行表面防护。聚碳酸基材的耐温性较高,传统聚碳酸防护材料的固化温度高,多为120-130℃。但涂层固化时基材受热,聚碳酸酯分子链重排导致其自由体积分数和空隙尺寸减小,基材内部产生残余应力,使得聚碳酸酯材料的力学性能如冲击强度降低。
基于聚碳酸酯基材的冲击性能和现有的高温固化防护涂层相悖的现状,如果能够实现低温固化防护涂层的,就能够使聚碳酸酯基材保持高的力学性能如高的冲击强度。因此,开发一种低温固化防护涂层成为亟待解决的问题。
发明内容
本发明的目的是克服现有技术中存在的问题,提供一种双层防护涂层,其具有低的固化温度,涂层的热固化过程不会对基材的力学性能例如冲击强度产生不利影响,将该双层防护涂层用于聚碳酸酯基材上能够使基材保持高的冲击强度。
本发明的另一目的是提供上述双层防护涂层的制备方法。
为了实现以上目的,本发明提供如下技术方案。
一种双层防护涂层,包括:
底涂层,所述底涂层的材料包括聚氨酯;以及
面涂层,所述面涂层设置在所述底涂层上,所述面涂层的材料包括有机硅树脂。
在一些实施例中,所述双层防护涂层的固化温度可为70-90℃。低温固化不会破坏基材的内部微观结构,使基材保持高的冲击强度。在一些具体实施例中,所述双层防护涂层的固化温度可为70℃、75℃、80℃、85℃或90℃。
在一些实施例中,所述聚氨酯的重均分子量可为1.5-2.0万Da。所述聚氨酯的玻璃化转变温度可为75-90℃。所述有机硅树脂的重均分子量可为1200-2500Da。通过优化聚氨酯和有机硅树脂的重均分子量和玻璃转化温度,有利于降低固化温度。
在一些具体实施例中,所述聚氨酯的重均分子量可为1.6-1.9万Da。所述聚氨酯的玻璃化转变温度可为80-90℃。所述有机硅树脂的重均分子量可为1300-2000Da。
在一些优选实施例中,所述聚氨酯的重均分子量为1.8万Da。所述聚氨酯的玻璃化转变温度为85℃。所述有机硅树脂的重均分子量可为1700Da。
在一些实施例中,所述双层防护涂层可用于聚碳酸酯基材。涂覆有所述双层防护涂层的聚碳酸酯基材能够兼具优异的理化性能、光学性能、力学性能、耐环境性能等。
本发明还提供所述双层防护涂层的制备方法,包括以下步骤:
在基材上涂覆聚氨酯涂料;
表干后,在所形成的涂层上涂覆有机硅树脂涂料;以及
表干后,进行固化。
在一些实施例中,表干时间可为10min以上,例如可为10min、30min、1h、1.5h或2h。表干温度通常为18-30℃。在一些具体实施例中,可将基材倾斜放置表干,使基材表面的涂料在重力作用流平。在一些具体实施例中,将聚氨酯涂料涂覆在基材表面,将基材倾斜放置表干,使基材表面的涂料在重力作用流平;之后,继续涂覆有机硅树脂涂料,涂覆时基材倾斜放置表干,使基材表面的树脂在重力作用流平。
在一些实施例中,固化温度可为70-90℃,例如可为70℃、75℃、80℃、85℃或90℃。固化时间可为2-6h,例如可为2h、3h、4h、5h或6h。低温固化不会破坏基材的内部微观结构,使基材保持高的冲击强度。通过降低涂层的固化温度、减少涂层的固化时间,可以为涂料的使用方如车辆、镜片、头盔等制造商,节省大量的经济成本。
在一些实施例中,所述聚氨酯涂料的制备方法包括:将聚多元醇、脂肪族多异氰酸酯、催化剂、扩链剂、交联剂、成盐剂和溶剂混合,反应后,制得所述聚氨酯涂料。
在一些具体实施例中,聚氨酯涂料的固含量可为8%-10%,例如8.1%、8.2%、8.3%、8.4%、8.5%、8.6%、8.7%、8.8%、8.9%、9%、9.1%、9.2%、9.3%、9.4%、9.5%、9.6%、9.7%、9.8%、9.9%或10%。
在一些具体实施例中,聚氨酯涂料的PH值可为8-10,例如8.0、8.1、8.2、8.3、8.4、8.5、8.6、8.7、8.8、8.9、9.0、9.1、9.2、9.3、9.4、9.5、9.6、9.7、9.8、9.9或10。
在一些具体实施例中,所述聚多元醇包括聚酯多元醇和聚醚多元醇中的一种或多种。优选地,所述聚多元醇的分子量可为500-10000,优选地,所述聚多元醇的分子量可为1000-5000。
在一些具体实施例中,所述脂肪族多异氰酸酯包括脂肪族二异氰酸酯,例如可为六亚甲基二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)、二环己基甲烷二异氰酸酯(HMDI)中的一种或多种,最优选为HMDI。
在一些具体实施例中,所述催化剂包括有机锡金属类催化剂、叔胺类催化剂中的一种或多种。优选地,所述催化剂包括二月桂酸二丁基锡、辛酸亚锡、亚乙基二胺、N,N’-二甲基氨基吡啶中的一种或多种。
在一些具体实施例中,所述扩链剂包括羧酸类扩链剂、醇类扩链剂和胺类扩链剂中的一种或多种。优选地,所述扩链剂包括二羟甲基丙酸、三羟甲基丙烷、N,N-二羟基(二异丙基)苯胺中的一种或多种。
在一些具体实施例中,所述成盐剂包括三乙胺、二甲基乙醇胺、二乙基乙醇胺、氨水、氢氧化钠中的一种或多种。
在一些具体实施例中,所述溶剂可为甲醇、乙醇、异丙醇、乙二醇丁醚、丙二醇甲醚、N-甲基吡咯烷酮、水中的一种或多种。最优选地,所述溶剂可为异丙醇、丙二醇甲醚、N-甲基吡咯烷酮和水中的一种或多种。本发明选用的溶剂对基材的腐蚀能力较弱。
聚氨酯涂料的制备方法是阴离子聚合聚氨酯的常规制备方法,不同的是合成过程使用的原料与常规方法略有不同,本发明的交联剂使用了乙二胺和氨基树脂。优选地,所述氨基树脂为甲基醚化亚氨基三聚氰胺树脂;最优选,所述氨基树脂为六甲氧基甲基三聚氰胺。
优选地,脂肪族多异氰酸酯(其为固化剂)为二环己基甲烷二异氰酸酯,二环己基甲烷二异氰酸酯与乙二胺的质量比为23∶(0.6-1.5);二环己基甲烷二异氰酸酯与氨基树脂的质量比为23∶(1.0-2.3),如使用其它固化剂,需要根据-NCO含量换算质量比。在添加适量的乙二胺和氨基树脂之后,能有效控制涂料固化后的交联度。当乙二胺和氨基树脂的添加量在本专利控制的添加范围内时,涂层涂覆后,附着力为0级。且经各项环境试验考核后,附着力不发生降低、膜层表面质量未发现异常。
在一些实施例中,所述有机硅树脂涂料的制备方法包括:向甲基硅树脂溶液中加入硅烷偶联剂和催化剂,反应后制得所述有机硅树脂涂料。
在一些具体实施例中,甲基硅树脂、硅烷偶联剂、催化剂的质量比为(18-22)∶(3-5)∶(2_4),优选为(19-21)∶(3.5-4.5)∶(2.5-3.5),最优选为20∶4∶3。
在一些具体实施例中,所述硅烷偶联剂为环氧烃基硅烷偶联剂、烯烃基硅烷偶联剂、巯烃基硅烷偶联剂中的一种或多种,优选为环氧烃基硅烷偶联剂。使用上述硅烷偶联剂的优势:提高聚氨酯树脂和有机硅树脂的附着力。
在一些具体实施例中,所述催化剂为1,8-二氮杂二环、十一碳-7-烯催化剂、1,4-二氮杂环[2,2,2]辛烷、4-二甲基氨基吡啶中的一种或多种,优选为1,8-二氮杂二环。使用上述催化剂的优势:在较低的固化温度下具备较高的催化活性,有效控制固化反应速度和固化时间,提高聚氨酯树脂和有机硅树脂的附着力。
在一个具体实施例中,所述有机硅树脂涂料的制备方法包括:向甲基硅树脂溶液中加入环氧烃基硅烷偶联剂和1,8-二氮杂二环,反应后制得所述有机硅树脂涂料。
在本发明中,可采用淋涂、浸涂或喷涂的方式进行涂覆。
在本发明中,所述基材可为平板件、曲面件或其它异形面制件。
在一些实施例中,所述甲基硅树脂溶液的制备方法包括:将甲基三氯硅烷加入到溶剂中,再加入白炭黑和水,水解完成后,得到甲基硅树脂溶液。
在一些具体实施例中,所述溶剂可为甲醇、乙醇、异丙醇、乙二醇丁醚、丙二醇甲醚、N-甲基吡咯烷酮、水中的一种或多种。最优选地,所述溶剂可为异丙醇、丙二醇甲醚、N-甲基吡咯烷酮和水中的一种或多种。本发明选用的溶剂对基材的腐蚀能力较弱。
相比现有技术,本发明的有益效果:
1、本发明提供了一种双层防护涂层,其具有低的固化温度,涂层的热固化过程不会对基材的力学性能例如冲击强度产生不利影响,将该双层防护涂层用于聚碳酸酯基材上能够使基材保持高的冲击强度。此外,涂覆有该双层防护涂层的聚碳酸酯基材还兼具优异的理化性能(如附着力、耐磨性)、光学性能、耐环境性能(如耐湿热性能、耐盐雾性能、耐温度冲击性能、耐太阳辐射性能、耐紫外老化性能)等,使基材应用多样化。
本发明的双层防护涂层普适性高,与各类基材例如由热塑性聚烯烃、丙烯腈-丁二烯-苯乙烯(ABS)共聚物、EPDM橡胶、聚氨酯、丙烯酸类聚合物、聚酰胺、聚酯、乙烯基聚合物及其共聚物及混合物制备的基材等,具备高的附着匹配性和良好的流平性,适用范围广,尤其涂覆于透明基材如聚甲基丙烯酸甲酯玻璃、聚碳酸酯玻璃、PET膜、PU膜等基材上,膜层质量高且光学性能优异,对汽车制造等行业而言,可以增加基材甚至是透明材料选择的广度,有利于实现车体减重。
本发明的双层防护涂层,经由两种单组份涂料先后涂覆并固化而成,涂料涂覆前无需进行配料,避免了由于计算或称量的不准确性,导致因涂层固化过快或固化不充分问题引起的膜层开裂或分层问题,也无需为确保计量准确、混合均匀而使用昂贵的计量设备、混合设备,单组份涂料的设计也有利于实现“流水线”作业,施工效率较高。
2、本发明还提供了双层防护涂层的制备方法,涂覆聚氨酯涂料后,只需进行表干即可涂覆有机硅树脂涂料,再次表干后只需进行一次热固化,便可得到双层防护涂层,涂固工艺简单,所需涂覆设备成本低,适用于“流水线”作业,施工效率较高,非常具有工业利用价值。
附图说明
图1为本发明一个实施例的双层防护涂层的结构示意图。
图2为本发明一个实施例的双层防护涂层的制备流程图。
具体实施方式
为了使本发明要解决的技术问题、技术方案及有益效果更加清楚明白,以下结合具体实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
除有定义外,以下实施例中所用的技术术语具有与本发明所属领域技术人员普遍理解的相同含义。以下实施例中所用的实验试剂,如无特殊说明,均为常规生化试剂;以下实施例中所用的原材料、仪器和设备等,均可通过市场购买获得或者可通过现有方法获得;所述实验试剂用量,如无特殊说明,均为常规实验操作中试剂用量;所述实验方法,如无特殊说明,均为常规方法。
本发明通过下面的实施例来进一步阐述本发明。应该正确理解的是:本发明的实施例是为了说明本发明而做出,而不是限制本发明,所以在本发明的方法前提下对本发明的简单改造也属于本发明的范围。
实施例1
首先,制备聚氨酯涂料:
(1)在反应瓶中通氮气置换掉其中的空气,依次加入37g己二酸、23.3g己二醇、7.65g新戊二醇、5g聚醚二元醇、0.6g三羟甲基丙烷和0.01g有机锡催化剂,用1h升温至140℃,保温0.5h,用1h升温至150℃,保温1h,用1h升温至180℃,保温2h,继续升温至220℃,真空蒸馏0.5h脱水;持续通氮气,保温1h;其中,聚醚二元醇为江苏海安石油化工厂生产的聚乙二醇1000。
(2)降温至95℃,搅拌下加入85gN-甲基吡咯烷酮,混合搅拌0.5h。降温至50℃;
(3)在氮气保护、强力搅拌下逐滴滴加23g二环己基甲烷二异氰酸酯,升温至80℃进行反应,保温1h,加入0.02g辛酸亚锡催化剂;继续保温反应;间隔时间测试体系的NCO含量,在NCO含量降低至2.5%时,停止反应;
(4)高速搅拌下,加入6.4g二羟甲基丙酸的N-甲基吡咯烷酮(二羟甲基丙酸和N-甲基吡咯烷酮的质量比为1∶1)溶液进行扩链,80℃继续反应3h;
(5)降温至60℃,加入2.5g三乙胺,继续搅拌15min,加强搅拌,将混合溶剂(混合溶剂为N-甲基吡咯烷酮、异丙醇、丙二醇甲醚和水的混合物,混合溶剂中各组分的质量比为1∶14∶28∶5)960g加入反应瓶,搅拌5min,调节体系粘度;
(6)降温至20℃以下,在快速搅拌下加入0.8g乙二胺,强力搅拌20min,慢速搅拌2h;
(7)强力搅拌下滴加1.5g六甲氧基甲基三聚氰胺(氨基树脂),然后慢速搅拌2h,得到固含量为8.7%、PH值为8.4、重均分子量为1.8万Da的聚氨酯涂料,聚氨酯的玻璃化转变温度为85℃。
然后,制备有机硅树脂涂料:
(1)将25g甲基三氯硅烷缓慢加入到74g混合溶剂(混合溶剂为甲醇、乙醇、异丙醇、乙酸丁酯、二甲苯和乙二醇丁醚的混合物,混合溶剂中各组分的质量比为12∶20∶25∶1∶3∶13)中,逐渐加入白炭黑和水,水解完成后,室温下静置3h,得到甲基硅树脂溶液;
(2)继续在反应瓶中加入4.5g硅烷偶联剂KH560(环氧烃基硅烷偶联剂)和3.5g 1,8-二氮杂二环(催化剂),常温下缓慢搅拌20min后,得到有机硅涂料,其中有机硅树脂分子量为1800。硅烷偶联剂KH560采购自上海源叶生物科技有限公司。
最后,进行涂覆,形成双层防护涂层:
(1)清洗聚碳酸酯基材,去除基材涂覆区域的胶液、脱模剂残余物等;
(2)使用淋涂方法,将所制备的聚氨酯涂料涂覆在聚碳酸酯基材表面,基材倾斜放置表干,使基材表面的涂料在重力作用流平;
(3)底漆表干1h左右,使用淋涂方法,涂覆所制备的有机硅树脂涂料。淋涂时基材倾斜放置,使基材表面的树脂在重力作用下流平;
(4)面漆表干后,放入烘箱进行固化,固化条件为75℃,2h,所得双层防护涂层如图1所示。
实施例2
首先,制备聚氨酯涂料:
(1)在反应瓶中通氮气置换掉其中的空气,依次加入37g己二酸、3.2g二羟甲基丙酸、23.3g己二醇、7.65g新戊二醇、5g聚醚二元醇、0.6g三羟甲基丙烷和0.01g辛酸亚锡催化剂,用1h升温至140℃,保温0.5h,用1h升温至150℃,保温1h,用1h升温至180℃,保温2h,继续升温至220℃,真空蒸馏0.5h脱水;持续通氮气,保温1h;其中,聚醚二元醇为江苏海安石油化工厂生产的聚乙二醇1000。
(2)降温至95℃,搅拌下加入85gN-甲基吡咯烷酮,混合搅拌0.5h。降温至50℃;
(3)在氮气保护、强力搅拌下逐滴滴加23g二环己基甲烷二异氰酸酯,升温至80℃进行反应,保温1h,加入0.02g辛酸亚锡催化剂;继续保温反应;间隔时间测试体系的NCO含量,在NCO含量降低至2.0%时,停止反应;
(4)降温至60℃,加入2.5g三乙胺,继续搅拌15min,加强搅拌,将混合溶剂(混合溶剂为N-甲基吡咯烷酮、异丙醇、丙二醇甲醚和水,混合溶剂中各组分的质量比为1∶14∶28∶5)960g加入反应瓶,搅拌5min,调节体系粘度;
(5)降温至20℃以下,在快速搅拌下加入0.8g乙二胺,强力搅拌20min,后慢速搅拌2h,得到固含量为9.2%、PH值为8.3、重均分子量为1.6万Da的聚氨酯涂料,玻璃化转变温度为83℃。
然后,制备有机硅树脂涂料:
(1)将25g甲基三氯硅烷缓慢加入到74g(混合溶剂为甲醇、乙醇、异丙醇、乙酸丁酯、二甲苯和乙二醇丁醚的混合物,混合溶剂中各组分的质量比为12∶20∶25∶1∶3∶13)中,逐渐加入白炭黑和水,水解完成后,室温下静置3h,得到低分子量的甲基硅树脂溶液,分子量为1800;
(2)继续在反应瓶中加入硅烷偶联剂4.5gKH560和3.5g 1,8-二氮杂二环,常温下缓慢搅拌20min后,得到有机硅树脂涂料。
最后,进行涂覆,形成双层防护涂层:
(1)清洗聚碳酸酯基材,去除基材涂覆区域的胶液、脱模剂残余物等;
(2)使用喷涂的方法,将所制备的聚氨酯涂料涂覆在聚碳酸酯基材表面,基材倾斜放置表干,使基材表面的树脂在重力作用流平;
(3)底漆表干1h左右,使用喷涂的方法,涂覆所制备的有机硅树脂,喷涂时基材倾斜放置,使基材表面的树脂在重力作用流平;
(4)面漆表干后,放入烘箱进行固化,固化条件为75℃,2h。
实施例3
首先,制备聚氨酯涂料:
(1)在反应瓶中通氮气置换掉其中的空气,将37g己二酸、29g新戊二醇、0.6g三羟甲基丙烷和0.01g辛酸亚锡催化剂加入到反应瓶中,用1h升温至140℃,保温0.5h,用1h升温至150℃,保温1h,用1h升温至180℃,保温2h,继续升温至220℃,真空蒸馏0.5h脱水;持续通氮气,保温1h。
(2)降温至95℃,强力搅拌下加入85gN-甲基吡咯烷酮,混合搅拌0.5h。降温至50℃;
(3)在氮气保护、强力搅拌下逐滴滴加23g二环己基甲烷二异氰酸酯,升温至80℃进行反应,间隔时间测试体系的NCO含量,在NCO含量降低至2.5%时,停止反应;
(4)降温至60℃后,加入2.5g成盐剂三乙胺,搅拌15min,继续加强搅拌,将混合溶剂(N-甲基吡咯烷酮、异丙醇、丙二醇甲醚的质量比为1∶14∶28)960g加入反应瓶中,调节混合体系粘度,继续搅拌5min;
(5)降温至20℃以下,在快速搅拌下加入0.8g乙二胺,强力搅拌20min,慢速搅拌2h后得到固含量为9.3%、PH值为8.3、重均分子量为1.4万Da的聚氨酯涂料,玻璃化转变温度为87℃。
然后,制备有机硅树脂涂料:
(1)将25g甲基三氯硅烷缓慢加入到79g混合溶剂(混合溶剂为甲醇、乙醇、异丙醇、乙酸丁酯、二甲苯和乙二醇丁醚的混合物,混合溶剂中各组分的质量比为12∶20∶25∶1∶3∶13)中,加入白炭黑和水,水解完成后,室温下静置3h,得到甲基硅树脂溶液,分子量为1800;
(2)在反应瓶中加入4.5g硅烷偶联剂KH560和3.5g 1,8-二氮杂二环,常温下缓慢搅拌20min后,得到有机硅树脂涂料。
最后,进行涂覆,形成双层防护涂层:
(1)清洗聚碳酸酯基材,去除基材涂覆区域的胶液、脱模剂残余物等;
(2)使用浸涂的方法,将所制备的聚氨酯涂料涂覆在聚碳酸酯基材表面,基材倾斜放置表干,使基材表面的树脂在重力作用流平;
(3)底漆表干1h左右,使用浸涂的方法,涂覆所制备的有机硅树脂涂料,浸涂时基材倾斜放置,使基材表面的树脂在重力作用流平;
(4)面漆表干后,放入烘箱进行固化,固化条件为75℃,2h。
实施例4
按照实施例1的方法制备双层防护涂层,不同之处在于,在制备聚氨酯涂料时,没有进行步骤6,即没有使用交联剂乙二胺。所得到的聚氨酯涂料的固含量为9.2%、PH值为8.8值、聚氨酯的重均分子量为1.3万Da的聚氨酯涂料,聚氨酯的玻璃化转变温度为76℃。
实施例5
按照实施例1的方法制备双层防护涂层,不同之处在于,在制备聚氨酯涂料时,没有进行步骤7,即没有使用交联剂六甲氧基甲基三聚氰胺(氨基树脂)。所得到的聚氨酯涂料的固含量为10%、PH值为8.3值、聚氨酯树脂重均分子量为1.2万Da的聚氨酯涂料,聚氨酯的玻璃化转变温度为73℃。
实施例6
首先,按照实施例1的方法制备聚氨酯涂料。
然后,制备有机硅树脂涂料:
(1)将25g甲基三氯硅烷缓慢加入到74g混合溶剂(混合溶剂为N-甲基吡咯烷酮、异丙醇、丙二醇甲醚和水的混合物,混合溶剂中各组分的质量比为1∶14∶28∶5)中,逐渐加入白炭黑和水,水解完成后,室温下静置3h,得到甲基硅树脂溶液,分子量为1800;
(2)继续在反应瓶中加入硅烷偶联剂4.5g KH560,常温下缓慢搅拌20min后,得到有机硅涂料;
最后,按照实施例1的方法进行涂覆,形成双层防护涂层。
实施例7
首先,按照实施例1的方法制备聚氨酯涂料。
然后,制备有机硅树脂涂料:
(1)将25g甲基三氯硅烷缓慢加入到74g混合溶剂(混合溶剂为N-甲基吡咯烷酮、异丙醇、丙二醇甲醚和水的混合物,混合溶剂中各组分的质量比为1∶14∶28∶5)中,逐渐加入白炭黑和水,水解完成后,室温下静置3h,得到甲基硅树脂溶液,分子量为1800;
(2)继续在反应瓶中加入3.8g 1,8-二氮杂二环,常温下缓慢搅拌20min后,得到有机硅涂料;
最后,按照实施例1的方法进行涂覆,形成双层防护涂层。
实施例8
按照实施例1的方法制备双层防护涂层,不同之处在于,乙二胺的添加量为0.6g。所得到的聚氨酯涂料的固含量为9.1%、PH值为8.3、聚氨酯的重均分子量为1.4万Da的聚氨酯涂料,聚氨酯的玻璃化转变温度为75℃。
实施例9
按照实施例1的方法制备双层防护涂层,不同之处在于,乙二胺的添加量为1.5g。所得到的聚氨酯涂料的固含量为9.3%、PH值为9.2值、聚氨酯的重均分子量为1.6万Da的聚氨酯涂料,聚氨酯的玻璃化转变温度为77℃。
实施例10
按照实施例1的方法制备双层防护涂层,不同之处在于,氨基树脂的添加量为1.0g。所得到的聚氨酯涂料的固含量为9.1%、PH值为8.7、聚氨酯的重均分子量为1.2万Da的聚氨酯涂料,聚氨酯的玻璃化转变温度为73℃。
实施例11
按照实施例1的方法制备双层防护涂层,不同之处在于,氨基树脂的添加量为2.3g。所得到的聚氨酯涂料的固含量为9.4%、PH值为8.6、聚氨酯的重均分子量为1.6万Da的聚氨酯涂料,聚氨酯的玻璃化转变温度为77℃。
实施例12
按照实施例1的方法制备双层防护涂层,不同之处在于,乙二胺的添加量为0.3g。所得到的聚氨酯涂料的固含量为9.0%、PH值为8.0、聚氨酯的重均分子量为1.1万Da的聚氨酯涂料,聚氨酯的玻璃化转变温度为74℃。
实施例13
按照实施例1的方法制备双层防护涂层,不同之处在于,乙二胺的添加量为1.8g。所得到的聚氨酯涂料的固含量为9.8%、PH值为9.7值、聚氨酯的重均分子量为1.7万Da的聚氨酯涂料,聚氨酯的玻璃化转变温度为78℃。
实施例14
按照实施例1的方法制备双层防护涂层,不同之处在于,氨基树脂的添加量为0.8g。所得到的聚氨酯涂料的固含量为9.1%、PH值为8.7、聚氨酯的重均分子量为1.1万Da的聚氨酯涂料,聚氨酯的玻璃化转变温度为73℃。
实施例15
按照实施例1的方法制备双层防护涂层,不同之处在于,氨基树脂的添加量为2.6g。所得到的聚氨酯涂料的固含量为9.5%、PH值为8.6、聚氨酯的重均分子量为1.7万Da的聚氨酯涂料,聚氨酯的玻璃化转变温度为77℃。
对比例1
首先,按照实施例1的方法制备聚氨酯涂料。
然后,进行涂覆:
(1)清洗聚碳酸酯基材,去除基材涂覆区域的胶液、脱模剂残余物等;
(2)使用淋涂的方法,将所制备的聚氨酯涂料涂覆在聚碳酸酯基材表面,基材倾斜放置表干,使基材表面的树脂在重力作用流平;
(3)聚氨酯涂料表干成膜1h后,放入烘箱进行固化,固化条件为75℃,6h。
对比例2
首先,按照实施例1的方法制备有机硅树脂涂料。
然后,进行涂覆:
(1)清洗聚碳酸酯基材,去除基材涂覆区域的胶液、脱模剂残余物等;
(2)使用淋涂方法,将所制备的有机硅树脂涂料涂覆在聚碳酸酯基材表面,基材倾斜放置表干,使基材表面的树脂在重力作用流平;
(3)有机硅树脂涂料表干成膜1h后,放入烘箱进行固化,固化条件为75℃,6h。
对比例3
按照对比例2的方法进行,不同之处在于,固化条件为120℃,2h。
性能测试
测试实施例1-15和对比例1-3制得的修饰有涂层的基材的理化性能、光学性能、力学性能和耐环境性能,各项测试均按照现行有效的标准进行测试,测试标准和要求如下:
(1)冲击试验的测试方法参考标准GJB 1043-2006
(2)附着力测试参考,GB/T 9286-2021
(3)耐磨性测试参考,ASTM F735-2006,测试100冲程前后的雾度变化
(4)湿热试验参考标准GB/T 1740-2007,10d
(5)盐雾试验参考标准GB/T 1771-2007,48h
(6)太阳辐射参考标准GJB 150.7A-2009,光效应,按程序2进行56次循环
(7)紫外性能参考标准,ASTM D4587-2005,UVA-340nm,0.89W/(m2nm),8h UV((60±2.5)℃)+4h冷凝((50±2.5)℃)为1个循环
(8)成膜后膜层外观质量,目视检查
(9)环境试验后膜层质量检验,GB/T 1766-2008,检查膜层的变色、粉化、开裂、起泡、剥落情况
测试结果见下表:
“/”表示未测定。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应以所述权利要求的保护范围为准。
Claims (10)
1.一种双层防护涂层,其特征在于,包括:
底涂层,所述底涂层的材料包括聚氨酯;以及
面涂层,所述面涂层设置在所述底涂层上,所述面涂层的材料包括有机硅树脂。
2.根据权利要求1所述的双层防护涂层,其特征在于,其固化温度为70-90℃。
3.根据权利要求1或2所述的双层防护涂层,其特征在于,所述聚氨酯的重均分子量为1.5-2.0万Da,玻璃化转变温度为75-90℃;所述有机硅树脂的重均分子量为1200-2500Da。
4.根据权利要求1或2所述的双层防护涂层,其特征在于,所述双层防护涂层用于聚碳酸酯基材。
5.权利要求1-4中任一项所述的双层防护涂层的制备方法,其特征在于,包括以下步骤:
在基材上涂覆聚氨酯涂料;
表干后,在所形成的涂层上涂覆有机硅树脂涂料;以及
表干后,进行固化。
6.根据权利要求5所述的制备方法,其特征在于,
表干时间为10min以上;
固化温度为70-90℃,固化时间为2-6h。
7.根据权利要求5或6所述的制备方法,其特征在于,所述聚氨酯涂料的制备方法包括:
将聚多元醇、脂肪族多异氰酸酯、催化剂、扩链剂、交联剂、成盐剂和溶剂混合,反应后,制得所述聚氨酯涂料。
8.根据权利要求7所述的制备方法,其特征在于,
所述聚多元醇包括聚酯多元醇和聚醚多元醇中的一种或多种;
所述脂肪族多异氰酸酯包括脂肪族二异氰酸酯;
所述催化剂包括有机锡金属类催化剂、叔胺类催化剂中的一种或多种;优选地,所述催化剂包括二月桂酸二丁基锡、辛酸亚锡、亚乙基二胺、N,N’-二甲基氨基吡啶中的一种或多种;
所述扩链剂包括羧酸类扩链剂、醇类扩链剂和胺类扩链剂中的一种或多种;优选地,所述扩链剂包括二羟甲基丙酸、三羟甲基丙烷、N,N-二羟基(二异丙基)苯胺中的一种或多种;
所述交联剂包括乙二胺和氨基树脂;优选地,所述氨基树脂为甲基醚化亚氨基三聚氰胺树脂;最优选,所述氨基树脂为六甲氧基甲基三聚氰胺;
所述成盐剂包括三乙胺、二甲基乙醇胺、二乙基乙醇胺、氨水、氢氧化钠中的一种或多种。
9.根据权利要求5或6所述的制备方法,其特征在于,所述有机硅树脂涂料的制备方法包括:
向甲基硅树脂溶液中加入硅烷偶联剂和催化剂,反应后制得所述有机硅树脂涂料。
10.根据权利要求9所述的制备方法,其特征在于,所述硅烷偶联剂为环氧烃基硅烷偶联剂、烯烃基硅烷偶联剂、巯烃基硅烷偶联剂中的一种或多种,优选为环氧烃基硅烷偶联剂;
所述催化剂为1,8-二氮杂二环、十一碳-7-烯催化剂、1,4-二氮杂环[2,2,2]辛烷、4-二甲基氨基吡啶中的一种或多种,优选为1,8-二氮杂二环。
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