CN112726273A - 一种水性高光涂料及其制备方法 - Google Patents

一种水性高光涂料及其制备方法 Download PDF

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CN112726273A
CN112726273A CN202110131816.8A CN202110131816A CN112726273A CN 112726273 A CN112726273 A CN 112726273A CN 202110131816 A CN202110131816 A CN 202110131816A CN 112726273 A CN112726273 A CN 112726273A
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郑少琴
谢进标
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Shantou Xinyuan Chemical Technology Co ltd
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Abstract

一种水性高光涂料,其特征在于由下述重量配比的原料制成:水40-60%,异氰酸酯8‑40%,扩链树脂5‑15%,交联树脂5‑10%,活性聚硅氧烷1‑10%,磺酸盐亲水扩链剂2‑5%,后扩链剂0.5‑3%,后交联剂0.02‑0.2%,前催化剂0.01‑0.1%,后催化剂0.02‑0.2%,羟基丙烯酸酯0.5‑5%,甲基丙烯酸甲酯2‑20%,苯乙烯2‑10%,乳化剂0.1‑0.4%,引发剂0.1‑0.4%,增稠剂0.01‑0.05%,流平剂0.05‑0.2%,消泡剂0.1‑0.3%,防腐剂0.1‑0.3%。本发明还提供上述水性高光涂料的一种制备方法。本发明的水性高光涂料用于复合转移工艺生产高光纸,纸张表面光泽度高,耐热性好,耐折性好,涂层与纸张附着力好,与模压膜有良好的剥离性,超低VOC含量,符合节能环保和安全卫生要求。

Description

一种水性高光涂料及其制备方法
技术领域
本发明涉及涂料组合物,具体涉及一种水性高光涂料及其制备方法。
背景技术
航空玻璃卡纸也叫铸涂纸,传统的加工方法是将涂有涂料的原纸,贴压在加热的,经过高度抛光具有镜面光泽的镀铬烘缸表面上,再经干燥剥离下来的加工纸。由于纸面平滑,光亮如玻璃,故也称玻璃卡纸,俗称高光纸。高光纸作为高端的包装材料广泛应用于化妆品、药品、保健品、高档烟酒等高端产品的外包装,市场需求潜力非常大。
目前国内外生产高光纸有传统的铸涂工艺和复合转移工艺。
传统的铸涂工艺存在工艺比较复杂、设备投资大、控制精度要求很高、涂层厚、生产线速低、生产成本高等缺点,而且生产出来的高光纸的光泽度、耐折性、附着力、印刷和烫金性能还存在一定的不足。
复合转移工艺是国内近几年出现的一种高光纸生产新工艺,它是将高光涂料涂布在纸上,然后与表面光滑的膜(如PET膜、OPP膜等)复合,固化后剥离回收膜,利用膜的光滑表面模压涂层而使纸张表面平滑光亮,形成高光纸。该工艺具有设备简单、容易操作、涂层薄、生产速度快的优点。适用于复合转移工艺生产高光纸的高光涂料性能要求高,既要求有高的光泽度,又要有较高的耐热耐压性能,还要满足较好的耐折性、与纸张有良好的附着力且与模压膜有良好的剥离性,以及达到医药、食品、烟草等行业的安全卫生要求。因此,市场至今还没有符合复合转移工艺生产高端高光纸的水性高光涂料,阻碍了该工艺的应用和快速发展。
发明内容
本发明所要解决的技术问题是提供一种水性高光涂料及其制备方法,这种水性高光涂料用于复合转移工艺生产高光纸,纸张表面光泽度高,耐热性好,耐折性好,涂层与纸张附着力好,与模压膜有良好的剥离性,超低VOC含量,符合节能环保和安全卫生要求。采用的技术方案如下:
一种水性高光涂料,其特征在于由下述重量配比的原料制成:水40-60%,异氰酸酯8-40%,扩链树脂5-15%,交联树脂5-10%,活性聚硅氧烷1-10%,磺酸盐亲水扩链剂2-5%,后扩链剂0.5-3%,后交联剂0.02-0.2%,前催化剂0.01-0.1%,后催化剂0.02-0.2%,羟基丙烯酸酯0.5-5%,甲基丙烯酸甲酯2-20%,苯乙烯2-10%,乳化剂0.1-0.4%,引发剂0.1-0.4%,增稠剂0.01-0.05%,流平剂0.05-0.2%,消泡剂0.1-0.3%,防腐剂0.1-0.3%。
上述水作为高光涂料的分散剂,优选去离子水。
上述异氰酸酯作为高光涂料的硬段部分,赋予高光涂料的强度、耐温性等性能。优选方案中,上述异氰酸酯是甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、异佛尔酮二异氰酸酯(IPDI)、4,4′-二环己基甲烷二异氰酸酯(HMDI)、六亚甲基二异氰酸酯(HDI)和HDI三聚体中的一种或其中多种的组合。更优选上述异氰酸酯是异佛尔酮二异氰酸酯(IPDI)和六亚甲基二异氰酸酯(HDI)中的一种或两者的组合。IPDI和HDI可以降低聚氨酯的反应速度,保证预聚体分子量一致性和规整性。
上述扩链树脂作为高光涂料的软段组分,赋予高光涂料的柔韧性。优选上述扩链树脂可以是聚醚二元胺(如聚氧化乙烯醚二胺、聚氧化丙烯醚二胺,其分子量为200-2000),聚醚二元醇(如聚氧化乙烯醚二醇、聚四氢呋喃醚二醇,其分子量为1000-4000),或聚酯二元醇(如聚碳酸酯二醇、聚己内酯二醇,其分子量为1000-4000),或聚天门冬氨酸酯(如广州齐翔Q440、珠海飞扬F520等)。聚醚如德信联邦的DDL-400、DDL-1000、DDL-220等牌号,聚酯二元醇有华峰基团的PE-3010、PE-3020、PE-3030等。更优选上述扩链树脂为聚醚二元胺,其分子量为2000。
上述交联树脂作为交联型软段组分,能够增加软段含量和交联点,提高高光涂料的强度、硬度和光泽度。优选上述交联树脂是分子量为200-1000的聚醚多元醇,如丙三醇、季戊四醇、山梨醇或蔗糖为起始剂的聚醚多元醇(如一诺威的YNW-6205、YNW-305、YNW-380等牌号)。更优选上述交联树脂是分子量为400,官能度为3.5的山梨醇聚醚多元醇。
上述活性聚硅氧烷赋予高光涂料的膜可剥离性能,并提高耐热性,减少剥离时的静电产生而损伤涂层及模压膜。优选上述活性聚硅氧烷是氨丙基封端聚二甲基硅氧烷或醇羟基封端二甲基硅氧烷,其分子量为500-4000。更优选优选上述活性聚硅氧烷是α,ω-二羟烃基聚硅氧烷,其分子量为1000。
上述磺酸盐亲水扩链剂赋予聚氨酯的自乳化性能和强度。亲水性扩连剂在聚氨酯预聚体分子的分子链上引入亲水基团,将聚氨酯分子变成具有亲水和亲油性能的内乳化剂。上述磺酸盐亲水扩链剂可以是乙二胺基乙磺酸钠(AAS盐)或1,2-二羟基-3-丙磺酸钠(DHPA)的水溶液,其重量百分比浓度为40-60%。
上述后扩链剂和后交联剂在乳化时加入反应物料中,用于提高聚合物分子量及硬段含量。后扩链剂和后交联剂采用小分子胺类。优选后扩链剂为异氟尔酮二胺(IPDA)或乙二胺,后交联剂为二乙烯三胺。
上述前催化剂用于催化异氰酸酯和扩链树脂、交联树脂、活性聚硅氧烷及羟基丙烯酸酯的反应。上述前催化剂可以是二月桂酸二丁基锡、辛酸亚锡、异辛酸钾催化剂或铋类催化剂,优选辛酸亚锡。
上述后催化剂用于促进残留的异氰酸基(NCO)与体系中的水完全扩链反应,防止体系中残留的异氰酸基在后滴加聚合过程中爆聚或产生渣。上述后催化剂可以是溶于水的胺类,如三乙醇胺、二甲基乙醇胺、双吗啉基二乙基醚等,优选双吗啉基二乙基醚。
上述羟基丙烯酸酯是聚氨酯和单体(甲基丙烯酸甲酯和苯乙烯)的桥接树脂,端羟基和聚氨酯预聚体的NCO反应而介入不饱和树脂。上述羟基丙烯酸酯可以是甲基丙烯酸羟乙酯或丙烯酸羟乙酯,优选甲基丙烯酸羟乙酯。
上述甲基丙烯酸甲酯和苯乙烯能够降低预聚体粘度、降低高光涂料成本,提高高光涂料的耐候性、强度及附着力等性能。
上述乳化剂能够增加体系乳化性能,提高乳液稳定性,减少聚合反应过程中产生渣。上述乳化剂可以是烷基醇醚硫酸钠和壬基酚聚氧乙烯醚硫酸铵中的一种或两者的组合。优选上述乳化剂是烷基醇醚硫酸钠。
上述引发剂作为丙烯酸树脂聚合反应催化剂。上述引发剂可以是过硫酸钾、过硫酸钠、过硫酸铵或过氧化苯甲酰,优选过硫酸钾。
优选上述增稠剂是聚氨酯类增稠剂,如亚乐顺 RM-2020NPR。
优选上述流平剂是聚醚硅氧烷共聚物,如TEGO Glide 410。
优选上述消泡剂是聚醚型消泡剂,如迪高的TEGOFoamex 825的消泡剂。
优选上述防腐剂是异噻唑啉酮类防腐剂,有效成分是2-甲基-4-异噻唑啉-3-酮和5-氯-2-甲基-4-异噻唑啉-3-酮的混合物。
本发明采用水性聚氨酯改性丙烯酸的合成工艺,首先异氰酸酯与扩链树脂、交联树脂、活性聚硅氧烷、羟基丙烯酸酯分步反应生成聚氨酯预聚体,反应过程中加入溶剂甲基丙烯酸甲酯和苯乙烯来调节粘度,降温后加入磺酸盐亲水扩链剂反应使聚氨酯预聚体具有亲水性能;然后在高速搅拌下加入水进行乳化,加入后扩链剂和后交联剂进一步提高分子量,得水性聚氨酯预乳液;最后在引发剂作用下,采用滴加法将含有不饱和单体的水性聚氨酯预乳液聚合反应,再加入助剂得高光涂料。
本发明还提供上述水性高光涂料的一种制备方法,其特征在于包括下述步骤:
(1)按重量计,配备下述原料:水40-60%,异氰酸酯8-40%,扩链树脂5-15%,交联树脂5-10%,活性聚硅氧烷1-10%,磺酸盐亲水扩链剂2-5%,后扩链剂0.5-3%,后交联剂0.02-0.2%,前催化剂0.01-0.1%,后催化剂0.02-0.2%,羟基丙烯酸酯0.5-5%,甲基丙烯酸甲酯2-20%,苯乙烯2-10%,乳化剂0.1-0.4%,引发剂0.1-0.4%,增稠剂0.01-0.05%,流平剂0.05-0.2%,消泡剂0.1-0.3%,防腐剂0.1-0.3%;
所述水分成四份:第一份水占总水量的10-15%,用于溶解后催化剂,得到后催化剂水溶液,待用;第二份水占总水量的10-15%,用于溶解后扩链剂和后交联剂,得到后扩链剂后交联剂水溶液,待用;第三份水占总水量的10-15%,用于溶解引发剂,得到引发剂水溶液,待用;剩余的水作为第四份水(占总水量的55-70%),在预乳化时使用;
(2)将扩链树脂、交联树脂分别加入带有搅拌器及真空除水系统的除水反应釜中,除去其中所含的水分;
(3)将已除水的扩链树脂加入带有搅拌器的第一聚合反应釜中,然后在搅拌的情况下滴加入异氰酸酯,并加热至70-85℃,反应0.5-1.5小时;然后加入已除水的交联树脂,在70-85℃下反应1-3小时;
(4)将第一聚合反应釜中的温度调节至55-70℃,再加入活性聚硅氧烷,在65-70℃下反应0.5-2小时;
(5)将第一聚合反应釜中的温度调节至55-70℃,再加入羟基丙烯酸酯和前催化剂,加热至70-80℃,反应1-3小时;
(6)将第一聚合反应釜中的温度调节至55-65℃,再加入甲基丙烯酸甲酯和苯乙烯;然后降温至40℃以下,30分钟内滴加完磺酸盐亲水扩链剂,搅拌5-30min;
(7)将第一聚合反应釜的搅拌速度设定为1000-3000rmp,在10-40min内将第四份水加入第一聚合反应釜中,乳化5-30min后滴加后扩链剂后交联剂水溶液,再继续搅拌5-30min;然后将第一聚合反应釜的搅拌速度降至50-300rmp,将后催化剂水溶液加入到第一聚合反应釜中,搅拌10-30min,得到预乳液;
(8)取占总量10-30%的预乳液加入到带有回流装置的第二聚合反应釜中,加入乳化剂,再加入占总量10-30%的引发剂水溶液,搅拌加热至回流管中有回流产生(通常加热至85℃),再同时滴加剩下的引发剂水溶液和剩下的预乳液,在3小时内滴加完毕;滴加完毕后加热至80-90℃,保温20-60min后降温至35-40℃;
(9)向第二聚合反应釜中加入消泡剂、增稠剂、流平剂和防腐剂,并搅拌均匀,得到水性高光涂料。
优选步骤(2)中,将扩链树脂、交联树脂分别加入带有搅拌器及真空除水系统的除水反应釜中后,在搅拌的情况下加热至100-130℃,在真空度为-0.01MPa至-0.02MPa下进行抽水1-3小时,除去其中所含的水分。
步骤(9)得到水性高光涂料后过滤出料。
采用上述工艺合成的高光涂料是以丙烯酸酯为核,以聚氨酯为壳的核壳结构涂料,该结构的涂料具有高亮度、附着力强、耐折、耐温、耐磨耐擦、单位涂量少、成本低、安全环保、耐老化、无毒无害等优点。
本发明的水性高光涂料用于复合转移工艺生产高光纸,纸张表面光泽度高,耐热性好,耐折性好,涂层与纸张附着力好,与模压膜有良好的剥离性。本发明的水性高光涂料超低VOC含量,无毒无害,对环境污染小,符合节能环保和安全卫生要求。制成高光纸后及后续加工(如印刷、烫金等)具有抗压花、耐溶剂、耐水、耐折耐爆、附着力强,平整度、流平性好等优点,同时成本低,无毒、无害、无味,是一种理想的环保型高光包装材料,适用任何固物包装,更符合国家烟草、食品、医药等行业要求。
具体实施方式
实施例1
本实施例中,水性高光涂料的制备方法包括下述步骤:
(1)按重量计,配备下述原料:水40%,异氰酸酯20%(均为异佛尔酮二异氰酸酯),扩链树脂10%(均为聚醚二元胺(商品名:德信联邦ZD-1200)),交联树脂6%(均为山梨醇为起始剂的聚醚多元醇(商品名:一诺威YNW-6205)),活性聚硅氧烷6%(均为分子量为1000的α,ω-二羟烃基聚硅氧烷),磺酸盐亲水扩链剂3%(均为重量百分比浓度为50%的乙二胺基乙磺酸钠水溶液(商品名:赢创A95)),后扩链剂1%(均为乙二胺),后交联剂0.1%(均为二乙烯三胺),前催化剂0.05%(均为辛酸亚锡),后催化剂0.05%(均为双吗啉基二乙基醚),羟基丙烯酸酯3%(均为丙烯酸羟乙酯),甲基丙烯酸甲酯4.8%,苯乙烯5%,乳化剂0.2%(均为烷基醇醚硫酸钠),引发剂0.3%(均为过硫酸钾),增稠剂0.03%(均为聚氨酯类增稠剂,亚乐顺 RM-2020NPR),流平剂0.07%(均为聚醚硅氧烷共聚物,TEGO Glide 410),消泡剂0.2%(均为聚醚型消泡剂,迪高的TEGOFoamex 825的消泡剂),防腐剂0.2%(均为异噻唑啉酮类防腐剂);
所述水分成四份:第一份水占总水量的12.5%,用于溶解后催化剂,得到后催化剂水溶液,待用;第二份水占总水量的12.5%,用于溶解后扩链剂和后交联剂,得到后扩链剂后交联剂水溶液,待用;第三份水占总水量的12.5%,用于溶解引发剂,得到引发剂水溶液,待用;剩余的水作为第四份水(占总水量的62.5%),在预乳化时使用;
(2)将扩链树脂、交联树脂分别加入带有搅拌器及真空除水系统的除水反应釜中,除去其中所含的水分(将扩链树脂、交联树脂分别加入带有搅拌器及真空除水系统的除水反应釜中后,在搅拌的情况下加热至120℃,在真空度为-0.01MPa下进行抽水2小时,除去其中所含的水分);
(3)将已除水的扩链树脂加入带有搅拌器的第一聚合反应釜中,然后在搅拌的情况下滴加入异氰酸酯,并加热至70-85℃,反应1小时;然后加入已除水的交联树脂,在70-85℃下反应2小时;
(4)将第一聚合反应釜中的温度调节至65℃,再加入活性聚硅氧烷,在65-70℃下反应1小时;
(5)将第一聚合反应釜中的温度调节至65℃,再加入羟基丙烯酸酯和前催化剂,加热至70-80℃,反应2小时;
(6)将第一聚合反应釜中的温度调节至60℃,再加入甲基丙烯酸甲酯和苯乙烯;然后降温至40℃以下,30分钟内滴加完磺酸盐亲水扩链剂,搅拌10min;
(7)将第一聚合反应釜的搅拌速度设定为2000rmp,在30min内将第四份水加入第一聚合反应釜中,乳化10min后滴加后扩链剂后交联剂水溶液,再继续搅拌10min;然后将第一聚合反应釜的搅拌速度降至100rmp,将后催化剂水溶液加入到第一聚合反应釜中,搅拌20min,得到预乳液;
(8)取占总量10%的预乳液加入到带有回流装置的第二聚合反应釜中,加入乳化剂,再加入占总量10%的引发剂水溶液,搅拌加热至回流管中有回流产生(加热至85℃),再同时滴加剩下的引发剂水溶液和剩下的预乳液,在3小时内滴加完毕;滴加完毕后加热至85℃,保温30min后降温至35℃;
(9)向第二聚合反应釜中加入消泡剂、增稠剂、流平剂和防腐剂,并搅拌均匀,得到水性高光涂料。
步骤(9)得到水性高光涂料后过滤出料。
实施例2
本实施例中,水性高光涂料的制备方法包括下述步骤:
(1)按重量计,配备下述原料:水53%,异氰酸酯8.4%(均为六亚甲基二异氰酸酯),扩链树脂5%(均为分子量为560的聚天冬氨酸酯(商品名:广州齐翔NQ420)),交联树脂5%(均为分子量为400,官能度为3.5的山梨醇聚醚多元醇),活性聚硅氧烷10%(均为分子量为1000的氨丙基封端聚二甲基硅氧烷),磺酸盐亲水扩链剂2%(均为重量百分比浓度为50%的乙二胺基乙磺酸钠水溶液(商品名:赢创A95)),后扩链剂3%(均为乙二胺),后交联剂0.2%(均为二乙烯三胺),前催化剂0.02%(均为辛酸亚锡),后催化剂0.2%(均为双吗啉基二乙基醚),羟基丙烯酸酯0.5%(均为甲基丙烯酸羟乙酯),甲基丙烯酸甲酯10%,苯乙烯2%,乳化剂0.1%(均为烷基醇醚硫酸钠),引发剂0.1%(均为过硫酸钾),增稠剂0.02%(均为聚氨酯类增稠剂,亚乐顺 RM-2020NPR),流平剂0.06%(均为聚醚硅氧烷共聚物,TEGO Glide 410),消泡剂0.3%(均为聚醚型消泡剂,迪高的TEGOFoamex 825的消泡剂),防腐剂0.1%(均为异噻唑啉酮类防腐剂);
所述水分成四份:第一份水占总水量的10%,用于溶解后催化剂,得到后催化剂水溶液,待用;第二份水占总水量的15%,用于溶解后扩链剂和后交联剂,得到后扩链剂后交联剂水溶液,待用;第三份水占总水量的15%,用于溶解引发剂,得到引发剂水溶液,待用;剩余的水作为第四份水(占总水量的60%),在预乳化时使用;
(2)将扩链树脂、交联树脂分别加入带有搅拌器及真空除水系统的除水反应釜中,除去其中所含的水分(将扩链树脂、交联树脂分别加入带有搅拌器及真空除水系统的除水反应釜中后,在搅拌的情况下加热至130℃,在真空度为-0.02MPa下进行抽水1.5小时,除去其中所含的水分);
(3)将已除水的扩链树脂加入带有搅拌器的第一聚合反应釜中,然后在搅拌的情况下滴加入异氰酸酯,并加热至70-85℃,反应0.6小时;然后加入已除水的交联树脂,在70-85℃下反应2.5小时;
(4)将第一聚合反应釜中的温度调节至60℃,再加入活性聚硅氧烷,在65-70℃下反应0.6小时;
(5)将第一聚合反应釜中的温度调节至60℃,再加入羟基丙烯酸酯和前催化剂,加热至70-80℃,反应1.5小时;
(6)将第一聚合反应釜中的温度调节至55℃,再加入甲基丙烯酸甲酯和苯乙烯;然后降温至40℃以下,30分钟内滴加完磺酸盐亲水扩链剂,搅拌30min;
(7)将第一聚合反应釜的搅拌速度设定为1000rmp,在40min内将第四份水加入第一聚合反应釜中,乳化15min后滴加后扩链剂后交联剂水溶液,再继续搅拌15min;然后将第一聚合反应釜的搅拌速度降至50rmp,将后催化剂水溶液加入到第一聚合反应釜中,搅拌30min,得到预乳液;
(8)取占总量20%的预乳液加入到带有回流装置的第二聚合反应釜中,加入乳化剂,再加入占总量20%的引发剂水溶液,搅拌加热至回流管中有回流产生(加热至85℃),再同时滴加剩下的引发剂水溶液和剩下的预乳液,在3小时内滴加完毕;滴加完毕后加热至80℃,保温60min后降温至40℃;
(9)向第二聚合反应釜中加入消泡剂、增稠剂、流平剂和防腐剂,并搅拌均匀,得到水性高光涂料。
步骤(9)得到水性高光涂料后过滤出料。
实施例3
本实施例中,水性高光涂料的制备方法包括下述步骤:
(1)按重量计,配备下述原料:水40%,异氰酸酯28.2%(均为二苯甲烷二异氰酸酯),扩链树脂6%(均为分子量为2000的聚氧化乙烯醚二醇(商品名:一诺威YNW-220)),交联树脂10%(均为分子量为1000,官能度为3的聚氧化乙烯醚三醇),活性聚硅氧烷1%(均为分子量为1000的α,ω-二羟烃基聚硅氧烷),磺酸盐亲水扩链剂4%(均为重量百分比浓度为50%的 1,2-二羟基-3-丙磺酸钠水溶液),后扩链剂0.5%(均为异氟尔酮二胺),后交联剂0.03%(均为二乙烯三胺),前催化剂0.1%(均为二月桂酸二丁基锡),后催化剂0.02%(均为三乙醇胺),羟基丙烯酸酯4%(均为甲基丙烯酸羟乙酯),甲基丙烯酸甲酯2%,苯乙烯3%,乳化剂0.4%(均为壬基酚聚氧乙烯醚硫酸铵),引发剂0.1%(均为过硫酸铵),增稠剂0.05%(均为聚氨酯类增稠剂,亚乐顺 RM-2020NPR),流平剂0.2%(均为聚醚硅氧烷共聚物,TEGO Glide 410),消泡剂0.1%(均为聚醚型消泡剂,迪高的TEGOFoamex 825的消泡剂),防腐剂0.3%(均为异噻唑啉酮类防腐剂);
所述水分成四份:第一份水占总水量的10%,用于溶解后催化剂,得到后催化剂水溶液,待用;第二份水占总水量的15%,用于溶解后扩链剂和后交联剂,得到后扩链剂后交联剂水溶液,待用;第三份水占总水量的10%,用于溶解引发剂,得到引发剂水溶液,待用;剩余的水作为第四份水(占总水量的65%),在预乳化时使用;
(2)将扩链树脂、交联树脂分别加入带有搅拌器及真空除水系统的除水反应釜中,除去其中所含的水分(将扩链树脂、交联树脂分别加入带有搅拌器及真空除水系统的除水反应釜中后,在搅拌的情况下加热至110℃,在真空度为-0.01MPa下进行抽水3小时,除去其中所含的水分);
(3)将已除水的扩链树脂加入带有搅拌器的第一聚合反应釜中,然后在搅拌的情况下滴加入异氰酸酯,并加热至70-85℃,反应1.5小时;然后加入已除水的交联树脂,在70-85℃下反应3小时;
(4)将第一聚合反应釜中的温度调节至55℃,再加入活性聚硅氧烷,在65-70℃下反应1小时;
(5)将第一聚合反应釜中的温度调节至55℃,再加入羟基丙烯酸酯和前催化剂,加热至70-80℃,反应3小时;
(6)将第一聚合反应釜中的温度调节至55℃,再加入甲基丙烯酸甲酯和苯乙烯;然后降温至40℃以下,30分钟内滴加完磺酸盐亲水扩链剂,搅拌15min;
(7)将第一聚合反应釜的搅拌速度设定为3000rmp,在15min内将第四份水加入第一聚合反应釜中,乳化6min后滴加后扩链剂后交联剂水溶液,再继续搅拌6min;然后将第一聚合反应釜的搅拌速度降至300rmp,将后催化剂水溶液加入到第一聚合反应釜中,搅拌10min,得到预乳液;
(8)取占总量15%的预乳液加入到带有回流装置的第二聚合反应釜中,加入乳化剂,再加入占总量15%的引发剂水溶液,搅拌加热至回流管中有回流产生(加热至85℃),再同时滴加剩下的引发剂水溶液和剩下的预乳液,在3小时内滴加完毕;滴加完毕后加热至90℃,保温25min后降温至40℃;
(9)向第二聚合反应釜中加入消泡剂、增稠剂、流平剂和防腐剂,并搅拌均匀,得到水性高光涂料。
步骤(9)得到水性高光涂料后过滤出料。
将实施例1-3的水性高光涂料和现有市场高光涂料产品,分别均匀涂布在卡纸上,与OPP膜复合,烘干固化后剥离回收OPP膜,检测指标与现有市场产品对比见下表。从表中可知,本发明制造的高光涂料表面光泽度、附着力、耐折性、耐热性及印刷适应性都高于现有市场产品。
Figure DEST_PATH_IMAGE001

Claims (10)

1.一种水性高光涂料,其特征在于由下述重量配比的原料制成:水40-60%,异氰酸酯8-40%,扩链树脂5-15%,交联树脂5-10%,活性聚硅氧烷1-10%,磺酸盐亲水扩链剂2-5%,后扩链剂0.5-3%,后交联剂0.02-0.2%,前催化剂0.01-0.1%,后催化剂0.02-0.2%,羟基丙烯酸酯0.5-5%,甲基丙烯酸甲酯2-20%,苯乙烯2-10%,乳化剂0.1-0.4%,引发剂0.1-0.4%,增稠剂0.01-0.05%,流平剂0.05-0.2%,消泡剂0.1-0.3%,防腐剂0.1-0.3%。
2.根据权利要求1所述的水性高光涂料,其特征是:所述异氰酸酯是甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、4,4′-二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯和HDI三聚体中的一种或其中多种的组合。
3.根据权利要求1所述的水性高光涂料,其特征是:所述扩链树脂是聚醚二元胺、聚醚二元醇、聚酯二元醇或聚天门冬氨酸酯。
4.根据权利要求1所述的水性高光涂料,其特征是:所述交联树脂是分子量为200-1000的聚醚多元醇。
5.根据权利要求1所述的水性高光涂料,其特征是:所述活性聚硅氧烷是氨丙基封端聚二甲基硅氧烷或醇羟基封端二甲基硅氧烷,其分子量为500-4000。
6.根据权利要求1所述的水性高光涂料,其特征是:所述磺酸盐亲水扩链剂是乙二胺基乙磺酸钠或1,2-二羟基-3-丙磺酸钠的水溶液,其重量百分比浓度为40-60%。
7.根据权利要求1所述的水性高光涂料,其特征是:所述后扩链剂为异氟尔酮二胺或乙二胺,后交联剂为二乙烯三胺。
8.根据权利要求1所述的水性高光涂料,其特征是:所述前催化剂是二月桂酸二丁基锡、辛酸亚锡、异辛酸钾催化剂或铋类催化剂,所述后催化剂是三乙醇胺、二甲基乙醇胺或双吗啉基二乙基醚。
9.根据权利要求1所述的水性高光涂料,其特征是:所述羟基丙烯酸酯是甲基丙烯酸羟乙酯或丙烯酸羟乙酯;
所述乳化剂是烷基醇醚硫酸钠和壬基酚聚氧乙烯醚硫酸铵中的一种或两者的组合;
所述引发剂是过硫酸钾、过硫酸钠、过硫酸铵或过氧化苯甲酰;
所述增稠剂是聚氨酯类增稠剂;
所述流平剂是聚醚硅氧烷共聚物;
所述消泡剂是聚醚型消泡剂;
所述防腐剂是异噻唑啉酮类防腐剂。
10.权利要求1所述的水性高光涂料的制备方法,其特征在于包括下述步骤:
(1)按重量计,配备下述原料:水40-60%,异氰酸酯8-40%,扩链树脂5-15%,交联树脂5-10%,活性聚硅氧烷1-10%,磺酸盐亲水扩链剂2-5%,后扩链剂0.5-3%,后交联剂0.02-0.2%,前催化剂0.01-0.1%,后催化剂0.02-0.2%,羟基丙烯酸酯0.5-5%,甲基丙烯酸甲酯2-20%,苯乙烯2-10%,乳化剂0.1-0.4%,引发剂0.1-0.4%,增稠剂0.01-0.05%,流平剂0.05-0.2%,消泡剂0.1-0.3%,防腐剂0.1-0.3%;
所述水分成四份:第一份水占总水量的10-15%,用于溶解后催化剂,得到后催化剂水溶液,待用;第二份水占总水量的10-15%,用于溶解后扩链剂和后交联剂,得到后扩链剂后交联剂水溶液,待用;第三份水占总水量的10-15%,用于溶解引发剂,得到引发剂水溶液,待用;剩余的水作为第四份水,在预乳化时使用;
(2)将扩链树脂、交联树脂分别加入带有搅拌器及真空除水系统的除水反应釜中,除去其中所含的水分;
(3)将已除水的扩链树脂加入带有搅拌器的第一聚合反应釜中,然后在搅拌的情况下滴加入异氰酸酯,并加热至70-85℃,反应0.5-1.5小时;然后加入已除水的交联树脂,在70-85℃下反应1-3小时;
(4)将第一聚合反应釜中的温度调节至55-70℃,再加入活性聚硅氧烷,在65-70℃下反应0.5-2小时;
(5)将第一聚合反应釜中的温度调节至55-70℃,再加入羟基丙烯酸酯和前催化剂,加热至70-80℃,反应1-3小时;
(6)将第一聚合反应釜中的温度调节至55-65℃,再加入甲基丙烯酸甲酯和苯乙烯;然后降温至40℃以下,30分钟内滴加完磺酸盐亲水扩链剂,搅拌5-30min;
(7)将第一聚合反应釜的搅拌速度设定为1000-3000rmp,在10-40min内将第四份水加入第一聚合反应釜中,乳化5-30min后滴加后扩链剂后交联剂水溶液,再继续搅拌5-30min;然后将第一聚合反应釜的搅拌速度降至50-300rmp,将后催化剂水溶液加入到第一聚合反应釜中,搅拌10-30min,得到预乳液;
(8)取占总量10-30%的预乳液加入到带有回流装置的第二聚合反应釜中,加入乳化剂,再加入占总量10-30%的引发剂水溶液,搅拌加热至回流管中有回流产生,再同时滴加剩下的引发剂水溶液和剩下的预乳液,在3小时内滴加完毕;滴加完毕后加热至80-90℃,保温20-60min后降温至35-40℃;
(9)向第二聚合反应釜中加入消泡剂、增稠剂、流平剂和防腐剂,并搅拌均匀,得到水性高光涂料。
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