CN114316660A - 一种水性紫外光固化阴极电泳涂料及其制备方法 - Google Patents
一种水性紫外光固化阴极电泳涂料及其制备方法 Download PDFInfo
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- CN114316660A CN114316660A CN202111568121.2A CN202111568121A CN114316660A CN 114316660 A CN114316660 A CN 114316660A CN 202111568121 A CN202111568121 A CN 202111568121A CN 114316660 A CN114316660 A CN 114316660A
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Abstract
本发明公开了一种水性紫外光固化阴极电泳涂料及其制备方法,属于高分子材料领域。本发明所述聚氨酯基电泳涂料是以异氰酸酯单体,聚酯多元醇,扩链剂,封端剂,中和剂、阻聚剂、催化剂和光引发剂为原料,利用异氰酸酯单体上的异氰酸根基团和多元醇,扩链剂与封端剂中的羟基之间的反应,将光固化活性基团(碳碳双键),亲水基团接枝到聚氨酯长链上制得。本发明涂料的乳液稳定性好、涂层具有较高的硬度、良好附着力和优良耐水耐溶剂性能。本发明的制备方法简单、原料易得、绿色环保、易于工业化和大规模推广使用。
Description
技术领域
本发明属于高分子材料领域,具体涉及一种水性紫外光固化阴极电泳涂料及其制备方法。
背景技术
金属的腐蚀氧化会给实际生活中的很多方面带来困扰,而金属镀膜为解决这个问题提供了有效的方法。金属镀膜形成主要分为两种方法:第一种为化学镀法,其原理是利用化学还原法,将膜材配制成溶液,使其迅速参加还原反应,还原后沉积在被加工零件表面的一种加工方法。化学镀法存在的问题是镀膜不易控制,容易导致不均匀,且与基材结合强度差,同时还会产生大量的废液,造成严重的环境污染;第二种方法为电泳法,利用胶体粒子在电场作用下能产生电泳现象的原理,使电泳涂料中的基体树脂在水中离解成带电荷的离子聚合物,在电场作用下各自向与其极性相反的电极移动,并沉积在电极表面,形成漆膜。相比之下,电泳涂料具有很多优点,如涂料的大部分溶剂为水,从安全性和国家对环保的要求来看,涂料水性化具有很大的成长空间。另外,由于是电沉积成膜,因此可以在复杂形状的元器件上涂装,成膜均匀,附着力强。电泳涂料包括阳极电泳涂料和阴极电泳涂料。阳极电泳涂料存在的问题是容易腐蚀阳极材料,且电解液不稳定。与阳极电泳漆相比,阴极电泳涂料不会腐蚀电极,且具有优良的防锈能力。因此,对于阴极电泳漆的研究较多,如在专利CN104945590A中,利用以封端型异氰酸酯三聚体为交联剂,将其与阳离子型端羟基聚氨酯树脂混合后,制备出端羟基改性聚氨酯电泳漆。但该电泳漆后处理需要热固化交联,烘干温度高,能耗较高。日本公开专利No.sho63(1988)-69882采用含有羟酸基或磺酸基的多元醇作为亲水性扩链剂制备出自乳化的阴离子水基聚氨酯树脂,由其制备的聚氨酯涂料的硬度较低、综合性能仍然不尽人意。在专利US6232364中,通过使用合成主链结构上含有叔胺二元醇为成盐基团的聚氨酯型阳离子电沉积的紫外线固化型涂料,但此类聚氨酯电泳涂料的预聚体在分散时,由于聚氨酯分子的缠绕,容易将部分亲水基包裹在聚氨酯颗粒内部,影响水分散效果,需要使用较多含叔胺的单体,不仅味道大,其漆膜性能也较差。电泳涂料作为一种绿色环保型涂料,同样需要向低成本、无重金属、低固化温度、高存储稳定性等方向发展,而现有技术并不能满足克服上述缺点,满足产业的需要。此外,紫外光固化技术固化温度不高,特别适用于热敏基材;固化速率快,能显著提高了生产效率;无需溶剂,对环境污染小,能耗低;并且可通过调节树脂与活性单体稀释剂的比例来改变涂膜的性质,正好可以弥补电泳漆的缺点。
因此,开发一种兼具阴极电泳漆和紫外光固化涂料二者优点的光固化阴极电泳漆,不仅能进一步拓宽电泳漆的应用范围,而且可以顺应环境友好的发展趋势,已成为电泳漆发展的新方向。
发明内容
本发明的目的在于克服现有技术存在的不足之处而提供一种水性紫外光固化阴极电泳涂料及其制备方法。本发明实现了高效的紫外光固化,与热固化相比,具有高效、低能耗和极低VOC排放的优势。同时,制得的漆膜具有良好的柔顺性和硬度。
为实现上述目的,本发明采取的技术方案为:一种水性紫外光固化阴极电泳涂料,所述涂料包括聚氨酯基光敏树脂和光引发剂组分;所述制备聚氨酯基光敏树脂的原料包括以下组分:异氰酸酯单体、聚醚多元醇、多元醇扩链剂、封端剂、中和剂、阻聚剂和催化剂。
本技术方案用异氰酸酯单体、聚醚多元醇、多元醇扩链剂、封端剂、中和剂、阻聚剂、催化剂和光引发剂为原料,通过异氰酸酯单体上的异氰酸根基团和聚醚多元醇、多元醇扩链剂与封端剂中的羟基之间的反应,将光固化活性基团碳碳双键,亲水基团接枝到聚氨酯长链上,得到聚氨酯基光敏树脂。聚氨酯基光敏树脂与引发剂混和后的涂料,具有良好的导电性和水溶性满足电泳涂装的要求。同时,本发明涂料与普通水性涂料相比,聚合速度快,通过UV固化,固化过程更加节能环保。聚氨酯基光敏树脂中的叔胺基团呈碱性,当将冰醋酸等酸类中和剂加入体系后,进行中和成盐的反应,使所合成的聚氨酯预聚物具有良好的水溶性和稳定性。本发明涂料兼具UV固化涂料和电泳涂料的优点,施工时先通过电泳方式镀膜,后通过UV光迅速固化,制备出的涂层具有较高的硬度、良好附着力和优良耐水耐溶剂性能,对金属基材起到良好的保护作用,在金属用涂料领域展现了良好的应用前景。
作为本发明的优选实施方式,这种水性紫外光固化阴极电泳涂料中,所述异氰酸酯单体为2官能度的异氰酸酯单体,包括异佛尔酮二异氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯和二苯甲烷二异氰酸酯中的至少一种。
发明人经过研究发现,用不同单体合成出来的聚氨酯性能上有一定差异,特别是作为电泳涂料进行应用时,对漆膜的平整度影响大。使用本发明优选单体制备出的涂料平整度良好,漆膜平整,其中甲苯二异氰酸酯漆膜表现最好。
作为本发明的优选实施方式,这种水性紫外光固化阴极电泳涂料中,所述聚醚多元醇包括聚四氢呋喃二醇和/或聚乙二醇。
作为本发明的更加优选的实施方式,这种水性紫外光固化阴极电泳涂料中,所述聚醚多元醇包括PTMG-1000、PTMG-2000、PEG-600、PEG-1000中的至少一种。
作为本发明的优选实施方式,这种水性紫外光固化阴极电泳涂料中,所述多元醇扩链剂包括聚酯型二元醇扩链剂和/或N-甲基二乙醇胺。
作为本发明的优选实施方式,这种水性紫外光固化阴极电泳涂料中,所述多元醇扩链剂包括3-二甲胺基-1,2-丙二醇。
发明人经过研究发现,本发明使用的多元醇扩链剂使用3-二甲胺基-1,2-丙二醇,与常用的侧链含胺基的扩链剂相比,本发明采用主链含胺基扩链剂得到涂料的水溶性良好,乳液粒径分布窄且均一,粒径较小,均小于30nm,具有良好的分散均一性和水溶性。
作为本发明的优选实施方式,这种水性紫外光固化阴极电泳涂料中,所述封端剂为丙烯酸羟乙酯和/或甲基丙烯酸羟乙酯。
发明人经过研究发现,使用丙烯酸羟乙酯和/或甲基丙烯酸羟乙酯为封端剂可在聚氨酯预聚体中引入可光聚合的乙烯基基团,制备出聚氨酯基光敏树脂。该聚氨酯基光敏树脂与普通水性聚氨酯相比,固化更环保节能,聚合速度快,在30mW/cm2的光强下辐照25~60s即可实现完全固化,能大大提高施工效率。
作为本发明更加优选的实施方式,这种水性紫外光固化阴极电泳涂料中,所述异氰酸酯单体与封端剂的摩尔比为(5.5~1.5):1。
发明人经过研究发现,抗冲击强度、硬度、耐腐蚀性能与组分中封端剂添加量有关,在本发明优选的范围内封端剂加入越多,交联密度越大,抗冲击、硬度与耐腐蚀强度越大。
作为本发明的优选实施方式,这种水性紫外光固化阴极电泳涂料中,所述中和剂为冰乙酸和/或丙烯酸。
发明人经过研究发现,利用与冰乙酸、丙烯酸的中和反应,使该光敏树脂聚氨酯具有良好的水溶性和存储稳定性,可稳定储存一个月以上。
作为本发明的优选实施方式,这种水性紫外光固化阴极电泳涂料中,所述中和剂和多元醇扩链剂的摩尔比为1:1。
发明人经过研究发现,当中和剂和多元醇扩链剂的摩尔比为1:1时,叔胺基团与酸中和反应完全,形成的聚氨酯预聚物表现出良好的水溶性。
作为本发明的优选实施方式,这种水性紫外光固化阴极电泳涂料中,所述异氰酸酯单体的摩尔量与聚醚多元醇和多元醇扩链剂摩尔量之和的比为:异氰酸酯单体:(聚醚多元醇+多元醇扩链剂)=(1.1~1.6):1。
作为本发明的优选实施方式,这种水性紫外光固化阴极电泳涂料中,所述聚醚多元醇和多元醇扩链剂摩尔比为:聚醚多元醇:多元醇扩链剂=(0.8~1.5):1。
发明人经过研究发现,导电性能和亲水性与涂料中二元醇扩链剂的含量相关,二元醇扩链剂越多,导电性能与亲水性能越好,相反耐水性能就越差。发明人经过研究发现,多元醇扩链剂上的叔胺基团呈碱性,与冰醋酸等酸类中和剂进行中和成盐的反应,可以使所合成的聚氨酯预聚物具有良好的水溶性。
作为本发明的优选实施方式,所述阻聚剂为对羟基苯甲醚、对苯二酚、叔丁基邻苯二酚中的至少一种。
作为本发明的优选实施方式,所述催化剂为二月桂酸二丁基锡或/和有机铋。
作为本发明的优选实施方式,所述光引发剂为Darocur1173、TOPL、TPO、光引发剂819中的至少一种。
本发明还提供了上述任一项水性紫外光固化阴极电泳涂料的制备方法,所述方法包括以下步骤:(1)将聚醚多元醇真空蒸馏,得到预处理的聚醚多元醇;(2)将预处理的聚醚多元醇和催化剂混合后,加入到异氰酸酯单体中,反应至NCO含量达到理论值时为反应终点A;(3)到达反应终点A后,在步骤(1)产物中加入多元醇扩链剂,反应至NCO含量再次达到理论值时为反应终点B;(4)到达反应终点B后,在步骤(3)产物加入封端剂与阻聚剂,反应至NCO含量降至0时为反应终点C;(5)到达反应终点C后,在步骤(4)产物中加入中和剂反应后终止反应;(6)在步骤(5)产物中加入去离子水搅拌得到聚氨酯基光敏树脂;(7)将步骤(6)中的聚氨酯基水性光敏树脂和光引发剂混合均匀得到水性紫外光固化阴极电泳涂料。
作为本发明的优选实施方式,制备方法的步骤(1)中,所述真空蒸馏的条件为:将聚醚多元醇在80~100℃、300~500r/min的条件下真空蒸馏2~3h。
作为本发明的优选实施方式,制备方法的步骤(2)中,所述聚醚多元醇和催化剂加入恒压漏斗中,在50~100℃、200~600r/min的条件下以每秒2~3滴的速率滴入异氰酸酯单体中进行接枝反应。
作为本发明的优选实施方式,制备方法的步骤(2)中,所述有机铋为有机铋DY-20。
作为本发明的优选实施方式,制备方法的步骤(2)中,所述催化剂的质量占步骤(2)体系总质量的0.05~0.3%。
作为本发明的优选实施方式,制备方法的步骤(3)中,反应在50~80℃、200~500r/min下进行。
作为本发明的优选实施方式,制备方法的步骤(4)中,步骤(3)的反应产物中利用恒压漏斗以每秒2~3滴的速率滴入封端剂与阻聚剂的混合物并在60~70℃、300~500r/min的条件下进行反应。
作为本发明的优选实施方式,制备方法的步骤(4)中,所述阻聚剂的质量占步骤(4)体系总质量的0.005~0.008%。
作为本发明的优选实施方式,制备方法的步骤(2-4)中,反应过程中用二正丁胺法进行NCO含量的滴定。
作为本发明的优选实施方式,制备方法的步骤(5)中,加入中和剂后在60~70℃、300~500r/min下反应10min后终止反应。
作为本发明的优选实施方式,制备方法的步骤(6)中,在2000~3000r/min的高速搅拌下加入去离子水搅拌30min。
作为本发明的优选实施方式,制备方法的步骤(6)中,最终得到固含量为10~20%的聚氨酯基光敏树脂。
作为本发明的优选实施方式,这种水性紫外光固化阴极电泳涂料中,所述光引发剂和聚氨酯基光敏树脂的质量比为:(1~5):(90~100)。
发明人经过研究发现,光引发剂和聚氨酯基光敏树脂的质量比为:(1~5):(90~100)时形成的涂料UV固化速度快,涂料施工效率高。
本发明还提供了上述任一项水性紫外光固化阴极电泳涂料的应用,所述应用包括以下步骤:(1)将聚氨酯基光敏树脂和光引发剂混合均匀得到水性紫外光固化阴极电泳涂料;(2)将被镀金属基材作为阴极,使用步骤(1)涂料电泳涂装,得到镀膜的金属基材;(3)将步骤(2)中镀膜的金属基材水洗、干燥、烘烤后,使用UV光双面辐照固化。
作为本发明的优选实施方式,应用的步骤(2)中,将步骤(1)涂料置于电泳槽中,以马口铁作为阳极,以需要被镀金属基材作为阴极,在100V的直流电压下进行电泳涂装,电极极距为10cm、电泳时间为3~5min,得到镀有不溶性漆膜的金属基材。
作为本发明的优选实施方式,应用的步骤(2)中,所述金属基材包括马口铁、铜、铝、锌、银中的至少一种。
作为本发明的优选实施方式,应用的步骤(3)中,将步骤(2)中镀有不溶性漆膜的金属基材水洗、干燥、80~100℃下烘烤3min后,在UV光固化机中双面辐照固化。
与现有技术相比,本发明的有益效果在于:
(1)本发明涂料电导率优良,完全满足电泳要求,可用于电泳涂装。
(2)本发明涂料在30mW/cm2的光强下辐照25~60s即可实现完全固化,固化过程更加环保节能,聚合速度快,大大提高了施工效率。
(3)本发明兼具电泳涂装技术和紫外光固化技术的优点,制备出的金属用涂层具有较高的硬度、良好附着力和优良耐水耐溶剂性能,对金属基材起到保护作用,使金属具有明显的耐腐蚀性和抗冲击性能,在金属用涂层领域展现了良好的应用前景。
(4)本发明利用叔胺基团和中和剂的酸碱中和成盐反应,使涂料具有良好的水溶性和导电性。同时,涂料的存储稳定性良好,可稳定储存一个月以上。本发明涂料环保无污染,有利于可持续发展
附图说明
图1为本发明制备聚氨酯基水性光敏树脂的化学反应示意图。
图2为实施例1-3乳液粒径分布图。
图3为效果例1抗冲击性能表征图。
图4为效果例2耐腐蚀性能表征图。
具体实施方式
为更好的说明本发明的目的、技术方案和优点,下面将结合具体实施例和对比例对本发明作进一步说明。本发明实施例中所述实验方法如无特殊说明,均为常规方法;如无特殊说明,所述试剂和材料,均可从商业途径获得。
本发明实施例中采用的原材料信息如表1所示。
表1实施例1-5的原材料信息
实施例1
作为本发明聚氨酯基水性紫外光固化阴极电泳涂料的一种实施例。将52.38g的预处理后的聚四氢呋喃二醇(PTMG-1000)与0.488g的催化剂二月桂酸二丁基锡(DBTDL)加入恒压漏斗中,在60~70℃、300~500r/min的条件下以每秒2~3滴的速率滴入30.28g异佛尔酮二异氰酸酯(IPDI)中充分反应1h,反应过程中用二正丁胺法进行NCO含量的滴定,当NCO含量达到理论值时为反应终点A;到达反应终点A后,在反应产物中加入6.24g多元醇扩链剂3-二甲胺基-1,2-丙二醇(DMAD)60~70℃、300~500r/min进行反应,反应过程中用二正丁胺法进行NCO含量的滴定,当NCO含量再次达到理论值时为反应终点B;到达反应终点B后,在反应产物中利用恒压漏斗以每秒2~3滴的速率滴入7.20g封端剂丙烯酸羟乙酯(HEA)与0.053g阻聚剂羟基苯甲醚的混合物60~70℃、300~500r/min进行反应,反应过程中用二正丁胺法进行NCO含量的滴定,当NCO含量降至0时为反应终点C。到达反应终点后,在反应产物中加入与多元醇扩链剂摩尔比1:1的中和剂冰醋酸60~70℃、在300~500r/min条件下保持5~10min终止反应;最后在2000~3000r/min的高速搅拌下加入去离子水搅拌30min,最终得到固含量为10~20%的聚氨酯基光敏树脂。
实施例2
作为本发明聚氨酯基水性紫外光固化阴极电泳涂料的一种实施例。将52.38g的预处理后的聚四氢呋喃二醇(PTMG-1000)与0.452g的催化剂二月桂酸二丁基锡(DBTDL)加入恒压漏斗中,在60~70℃、300~500r/min的条件下以每秒2~3滴的速率滴入23.72g甲苯二异氰酸酯(TDI)中充分反应1h,反应过程中用二正丁胺法进行NCO含量的滴定,当NCO含量达到理论值时为反应终点A;到达反应终点A后,在反应产物中加入6.24g多元醇扩链剂3-二甲胺基-1,2-丙二醇(DMAD)60~70℃、300~500r/min进行反应,反应过程中用二正丁胺法进行NCO含量的滴定,当NCO含量再次达到理论值时为反应终点B;到达反应终点B后,在反应产物中利用恒压漏斗以每秒2~3滴的速率滴入7.20g封端剂丙烯酸羟乙酯(HEA)与0.049g阻聚剂羟基苯甲醚的混合物,在60~70℃、300~500r/min条件下反应,反应过程中用二正丁胺法进行NCO含量的滴定,当NCO含量降至0时为反应终点C。到达反应终点后,在反应产物中加入与多元醇扩链剂摩尔比1:1的中和剂冰醋酸,在60~70℃、300~500r/min条件下保持5~10min终止反应;最后在2000~3000r/min的高速搅拌下加入去离子水搅拌30min,最终得到固含量为10~20%的聚氨酯基光敏树脂。
实施例3
作为本发明聚氨酯基水性紫外光固化阴极电泳涂料的一种实施例。将52.38g预处理后的聚四氢呋喃二醇(PTMG-1000)与0.487g的催化剂二月桂酸二丁基锡(DBTDL)加入恒压漏斗中,在60~70℃、300~500r/min的条件下以每秒2~3滴的速率滴入30.28g异佛尔酮二异氰酸酯(IPDI)中充分反应1h,反应过程中用二正丁胺法进行NCO含量的滴定,当NCO含量达到理论值时为反应终点A;到达反应终点A后,在反应产物中加入6.24g多元醇扩链剂3-二甲胺基-1,2-丙二醇(DMAD)60~70℃、300~500r/min进行反应,反应过程中用二正丁胺法进行NCO含量的滴定,当NCO含量再次达到理论值时为反应终点B;到达反应终点B后,在反应产物中利用恒压漏斗以每秒2~3滴的速率滴入8.14g封端剂甲基丙烯酸羟乙酯(HEMA)与0.058g阻聚剂羟基苯甲醚的混合物60~70℃、300~500r/min进行反应,反应过程中用二正丁胺法进行NCO含量的滴定,当NCO含量降至0时为反应终点C。到达反应终点后,在反应产物中加入与多元醇扩链剂摩尔比1:1的中和剂冰醋酸,在60~70℃、300~500r/min条件下保持5~10min终止反应;最后在2000~3000r/min的高速搅拌下加入去离子水搅拌30min,最终得到固含量为10~20%的聚氨酯基光敏树脂。
实施例4
作为本发明聚氨酯基水性紫外光固化阴极电泳涂料的一种实施例。将52.38g预处理后的聚四氢呋喃二醇(PTMG-1000)与0.442g的催化剂二月桂酸二丁基锡(DBTDL)加入恒压漏斗中,在60~70℃、300~500r/min的条件下以每秒2~3滴的速率滴入36.05g二苯甲烷二异氰酸酯(MDI)中充分反应1h,反应过程中用二正丁胺法进行NCO含量的滴定,当NCO含量达到理论值时为反应终点A;到达反应终点A后,在反应产物中加入9.36g多元醇扩链剂3-二甲胺基-1,2-丙二醇(DMAD)60~70℃、300~500r/min进行反应,反应过程中用二正丁胺法进行NCO含量的滴定,当NCO含量再次达到理论值时为反应终点B;到达反应终点B后,在反应产物中利用恒压漏斗以每秒2~3滴的速率滴入2.43g封端剂丙烯酸羟乙酯(HEA)与0.05g阻聚剂羟基苯甲醚的混合物60~70℃、300~500r/min进行反应,反应过程中用二正丁胺法进行NCO含量的滴定,当NCO含量降至0时为反应终点C。到达反应终点后,在反应产物中加入与多元醇扩链剂摩尔比1:1的中和剂丙烯酸,在60~70℃、300~500r/min条件下保持5~10min终止反应;最后在2000~3000r/min的高速搅拌下加入去离子水搅拌30min,最终得到固含量为10~20%的聚氨酯基光敏树脂。
实施例5
作为本发明聚氨酯基水性紫外光固化阴极电泳涂料的一种实施例。将52.38g预处理后的聚四氢呋喃二醇(PTMG-1000)与0.256g的催化剂有机铋DY-20加入恒压漏斗中,在60~70℃、300~500r/min的条件下以每秒2~3滴的速率滴入33.03g六亚甲基二异氰酸酯(HDI)中充分反应1h,反应过程中用二正丁胺法进行NCO含量的滴定,当NCO含量达到理论值时为反应终点A;到达反应终点A后,在反应产物中加入9.36g多元醇扩链剂3-二甲胺基-1,2-丙二醇(DMAD)60~70℃、300~500r/min进行反应,反应过程中用二正丁胺法进行NCO含量的滴定,当NCO含量再次达到理论值时为反应终点B;到达反应终点B后,在反应产物中利用恒压漏斗以每秒2~3滴的速率滴入15.21g封端剂丙烯酸羟乙酯(HEA)与0.092g阻聚剂叔丁基邻苯二酚的混合物60~70℃、300~500r/min进行反应,反应过程中用二正丁胺法进行NCO含量的滴定,当NCO含量降至0时为反应终点C。到达反应终点后,在反应产物中加入与多元醇扩链剂摩尔比1:1的中和剂冰醋酸,在60~70℃、300~500r/min条件下保持5~10min终止反应;最后在2000~3000r/min的高速搅拌下加入去离子水搅拌30min,最终得到固含量为10~20%的聚氨酯基光敏树脂。
对比例1
作为本发明聚氨酯基水性紫外光固化阴极电泳涂料的一种对比例。将52.38g的预处理后的聚四氢呋喃二醇(PTMG-1000)与0.488g的催化剂二月桂酸二丁基锡(DBTDL)加入恒压漏斗中,在60~70℃、300~500r/min的条件下以每秒2~3滴的速率滴入30.28g异佛尔酮二异氰酸酯(IPDI)中充分反应1h,反应过程中用二正丁胺法进行NCO含量的滴定,当NCO含量达到理论值时为反应终点A;到达反应终点A后,在反应产物中加入6.24g多元醇扩链剂N-甲基二乙醇胺(MDEA)60~70℃、300~500r/min进行反应,反应过程中用二正丁胺法进行NCO含量的滴定,当NCO含量再次达到理论值时为反应终点B;到达反应终点B后,在反应产物中利用恒压漏斗以每秒2~3滴的速率滴入7.20g封端剂丙烯酸羟乙酯(HEA)与0.053g阻聚剂羟基苯甲醚的混合物60~70℃、300~500r/min进行反应,反应过程中用二正丁胺法进行NCO含量的滴定,当NCO含量降至0时为反应终点C。到达反应终点后,在反应产物中加入与多元醇扩链剂摩尔比1:1的中和剂冰醋酸60~70℃、在300~500r/min条件下保持5~10min终止反应;最后在2000~3000r/min的高速搅拌下加入去离子水搅拌30min,最终得到固含量为10~20%的聚氨酯基光敏树脂。
对比例2
作为本发明聚氨酯基水性紫外光固化阴极电泳涂料的一种对比例。将52.38g的预处理后的聚四氢呋喃二醇(PTMG-1000)与0.488g的催化剂二月桂酸二丁基锡(DBTDL)加入恒压漏斗中,在60~70℃、300~500r/min的条件下以每秒2~3滴的速率滴入30.28g异佛尔酮二异氰酸酯(IPDI)中充分反应1h,反应过程中用二正丁胺法进行NCO含量的滴定,当NCO含量达到理论值时为反应终点A;到达反应终点A后,在反应产物中加入6.24g多元醇扩链剂3-二甲胺基-1,2-丙二醇(DMAD)60~70℃、300~500r/min进行反应,反应过程中用二正丁胺法进行NCO含量的滴定,当NCO含量再次达到理论值时为反应终点B;到达反应终点B后,在反应产物中利用恒压漏斗以每秒2~3滴的速率滴入7.20g封端剂丙烯酸羟乙酯(HEA)与0.053g阻聚剂羟基苯甲醚的混合物60~70℃、300~500r/min进行反应,反应过程中用二正丁胺法进行NCO含量的滴定,当NCO含量降至0时为反应终点C。到达反应终点后,在反应产物中加入与多元醇扩链剂摩尔比1:0.5的中和剂冰醋酸60~70℃、在300~500r/min条件下保持5~10min终止反应;最后在2000~3000r/min的高速搅拌下加入去离子水搅拌30min,最终得到固含量为10~20%的聚氨酯基光敏树脂。
如图1所示为制备聚氨酯基水性光敏树脂的化学反应示意图。发明人经过研究发现,聚醚二元醇起到增加链长,提高树脂柔韧性的作用。扩链剂可以增加其亲水基团含量,增加亲水性,同时作为硬段调节硬度,含量越多,亲水性越好,硬度越高。封端剂的作用为增加光固化基团含量,增加越多,交联度越高,硬度越高。中和剂加入量越高中和度越高,成盐越多,水溶性越好。
实施例1-3的乳液粒径如图2所示,由图2可知,实施例1-3乳液粒径分布窄且均一,粒径较小,均小于30nm,证明本技术路线采用侧链含胺基的扩链剂较主链含胺基扩链剂水溶性良好,且分散均一。
实施例1-5和对比例1-2漆膜的基本性能表征结果如表2所示。由表2可知,实施例1-3乳液的电导率均大于0.003,满足电泳的需求;同时,采用不同单体合成出来的聚氨酯性能上有一定差异,特别是作为电泳涂料进行应用时,对漆膜的平整度影响最大,实施例1的漆膜外观最好,平整而光滑,实施例2漆膜表面有少量堆积,实施例3的漆膜表面有缩孔,而漆膜表面的平整度将影响其在电泳涂料中的应用,所以实施例1是相对较优的方案;对比实施例1-3漆膜的其他性能,变化并不明显,都有较好的力学、耐水耐溶剂性能。对比例1-2漆膜由于分别采用了叔胺基团在主链上的二元醇扩链剂和50%的中和度的配方,导致乳液水溶性差,出现乳液不稳定,分层现象,且力学性能,如硬度等均达不到所需要求。
表2实施例1-5和对比例1-2的基本性能表征结果
效果例1
发明人将一块马口铁将表面处理后,一半置于实施例1所述聚氨酯基光敏树脂和3wt.%光引发剂(Darocur1173)均匀混合的电泳槽中,在100V的直流电压下进行电泳涂装,电极极距为10cm、电泳时间为3~5min,得到不溶性漆膜,后经水洗、干燥、在80~100℃下烘烤3min,在UV光固化机中双面辐照固化,即得金属用阴极电泳涂层。另一半未经涂装漆膜的马口铁作为空白对照。将一半带有金属涂层而另一半未涂装的同一块马口铁,利用国家标准GB/T1732-1993薄膜冲击检测方法测试抗冲击性。试验结果如图3所示,结果显示落锤在50cm出下落,左侧漆膜无裂痕,皱纹及剥落现象产生,而右侧未经涂装的空白对照出现明显凹坑。
效果例2
发明人将一块马口铁将表面处理后,一半置于实施例1所述聚氨酯基光敏树脂和3wt.%光引发剂(Darocur1173)均匀混合的电泳槽中,在100V的直流电压下进行电泳涂装,电极极距为10cm、电泳时间为3~5min,得到不溶性漆膜,后经水洗、干燥、在80~100℃下烘烤3min,在UV光固化机中双面辐照固化,即得金属用阴极电泳涂层。另一半未经涂装漆膜的马口铁作为空白对照。利用国家标准GB 10124-88《金属材料实验室均匀腐蚀全浸试验方法》中详细规定的试验方法和要求进行腐蚀试验,利用交互浸渍试验。将一半带有金属涂层另一半未涂装的同一块马口铁试样交替地浸入液态腐蚀介质和暴露在空气中。试验结果如图4所示,左侧未涂膜的金属基材出现生锈腐蚀现象,右侧涂有涂层的部分,对金属基材具有保护现象,未有腐蚀现象产生。
效果例1-2的测试结果表明本发明涂层对马口铁基材防腐蚀效果良好,且抗冲击性强。
最后所应当说明的是,以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和范围。
Claims (10)
1.一种水性紫外光固化阴极电泳涂料,其特征在于,所述涂料包括聚氨酯基光敏树脂和光引发剂组分;所述聚氨酯基光敏树脂的制备原料包括以下组分:异氰酸酯单体、聚醚多元醇、多元醇扩链剂、封端剂、中和剂、阻聚剂和催化剂。
2.根据权利要求1所述涂料,其特征在于,所述异氰酸酯单体的摩尔量与聚醚多元醇和多元醇扩链剂摩尔量之和的比为:异氰酸酯单体:(聚醚多元醇+多元醇扩链剂)=(1.1~1.6):1。
3.根据权利要求1所述涂料,其特征在于,所述聚醚多元醇和多元醇扩链剂的摩尔比为:聚醚多元醇:多元醇扩链剂=(0.8~1.5):1。
4.根据权利要求1所述涂料,其特征在于,所述中和剂和多元醇扩链剂的摩尔比为1:1。
5.根据权利要求1所述涂料,其特征在于,所述异氰酸酯单体为2官能度的异氰酸酯单体,包括异佛尔酮二异氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯和二苯甲烷二异氰酸酯中的至少一种。
6.根据权利要求1所述涂料,其特征在于,所述聚醚多元醇包括聚四氢呋喃二醇和/或聚乙二醇。
7.根据权利要求1所述涂料,其特征在于,所述多元醇扩链剂包括聚酯型二元醇扩链剂和/或N-甲基二乙醇胺。
8.根据权利要求1所述涂料,其特征在于,所述封端剂为丙烯酸羟乙酯和/或甲基丙烯酸羟乙酯。
9.一种水性紫外光固化阴极电泳涂料的制备方法,其特征在于,所述方法包括以下步骤:(1)将聚醚多元醇真空蒸馏,得到预处理的聚醚多元醇;(2)将经过预处理的聚醚多元醇和催化剂混合后,加入到异氰酸酯单体中反应至NCO含量达到理论值时为反应终点A;(3)到达反应终点A后,在步骤(1)产物中加入多元醇扩链剂,反应至NCO含量再次达到理论值时为反应终点B;(4)到达反应终点B后,在步骤(3)产物加入封端剂与阻聚剂,反应至NCO含量降至0时为反应终点C;(5)到达反应终点C后,在步骤(4)产物中加入中和剂反应;(6)在步骤(5)产物中加入去离子水搅拌得到聚氨酯基光敏树脂;(7)将步骤(6)中的聚氨酯基光敏树脂和光引发剂混合均匀得到聚氨酯基水性紫外光固化阴极电泳涂料。
10.一种水性紫外光固化阴极电泳涂料的应用,其特征在于,所述应用包括以下步骤:(1)将聚氨酯基光敏树脂和光引发剂混合均匀得到水性紫外光固化阴极电泳涂料;(2)将被镀金属基材作为阴极,使用步骤(1)涂料电泳涂装,得到镀膜的金属基材;(3)将步骤(2)中镀膜的金属基材水洗、干燥、烘烤后,使用UV光双面辐照固化。
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