CN112726272B - 一种无溶剂高光涂料及其制备方法 - Google Patents
一种无溶剂高光涂料及其制备方法 Download PDFInfo
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Abstract
一种无溶剂高光涂料,其特征在于由下述重量配比的原料制成:异氰酸酯30‑70%,扩链树脂10‑30%,交联树脂5‑20%,活性聚硅氧烷5‑25%,羟基丙烯酸酯1‑5%,扩链剂1‑5%,交联剂0.1‑0.5%,前催化剂0.02‑0.2%,后催化剂0.02‑0.2%,分子筛活化粉1‑5%,流平剂0.05‑1%,消泡剂0.05-1%,抗静电剂0.5-5%。本发明还提供上述无溶剂高光涂料的一种制备方法。本发明的无溶剂高光涂料用于复合转移工艺生产高光卡纸,具有常温自固化功能,不用加热或射线固化,纸张变形率小,且纸张表面光泽度高、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。
Description
技术领域
本发明涉及涂料组合物,具体涉及一种无溶剂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。但是目前应用于复合转移法的高光涂料大多是水性丙烯酸乳液产品,应用过程中需要烘干工序,能耗大,生产设备复杂,存在纸张变形大、光泽度不足等缺点。
发明内容
本发明所要解决的技术问题是提供一种无溶剂高光涂料及其制备方法,这种无溶剂高光涂料用于复合转移工艺生产高光卡纸,具有常温自固化功能,不用加热或射线固化,纸张变形率小,且纸张表面光泽度高、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。采用的技术方案如下:
一种无溶剂高光涂料,其特征在于由下述重量配比的原料制成:异氰酸酯30-70%,扩链树脂10-30%,交联树脂5-20%,活性聚硅氧烷5-25%,羟基丙烯酸酯1-5%,扩链剂1-5%,交联剂0.1-0.5%,前催化剂0.02-0.2%,后催化剂0.02-0.2%,分子筛活化粉1-5%,流平剂0.05-1%,消泡剂0.05-1%,抗静电剂0.5-5%。
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(如聚氧化丙烯二醇、聚氧化乙烯二醇、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,其数均分子量为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。
上述羟基丙烯酸酯用于少量封端聚氨酯和调节分子量,使高光涂料体系总带上少量的不饱和键,以在应用中可以提高印刷适应性。上述羟基丙烯酸酯可以是丙烯酸羟乙酯和甲基丙烯酸羟乙酯中的一种或两者的组合。优选上述羟基丙烯酸酯为甲基丙烯酸羟乙酯。
上述扩链剂用于提高聚合物分子量及硬段含量。上述扩链剂可采用小分子二元醇或二元胺。优选上述扩链剂是1,4-丁二醇、新戊二醇、一缩二乙二醇、双酚A、对苯二酚二羟乙基醚、异氟尔酮二胺、乙二胺和苯二胺中的一种或其中多种的组合。更优选上述扩链剂是对苯二酚二羟乙基醚。
上述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。交联剂可采用小分子多元醇类。优选上述交联剂是丙三醇、季戊四醇和三羟甲基丙烷中的一种或其中多种的组合。更优选上述交联剂是三羟甲基丙烷。
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)与纸张或空气中的水分或其他活性物质完全扩链反应而提高强度,防止涂层中残留的活性异氰酸酯。上述后催化剂可以是胺类,如三乙醇胺、二甲基乙醇胺或双吗啉基二乙基醚等,优选双吗啉基二乙基醚。
上述分子筛活化粉是一种除水剂,防止产品存放过程中性能变化,防止施工阶段产生泡沫,改善产品开放稳定性和提高产品强度。分子筛活化粉可选用洛阳建龙微纳新材料有限公司的分子筛活化粉JLH-PU。
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 805消泡剂。
上述抗静电剂在产品涂布固化后,用于减少剥离模压膜时产生静电,提高产品质量和生产安全性。上述抗静电剂可以是阳离子抗静电剂、阴离子抗静电剂、非离子抗静电剂或高分子抗静电剂。优选上述抗静电剂是聚氨酯高分子抗静电剂(JL-WT)。
本发明采用多步法合成聚氨酯预聚体。首先是将扩链树脂、交联树脂在一定温度和真空度下除水,然后异氰酸酯分别与扩链树脂、交联树脂、活性聚硅氧烷、羟基丙烯酸酯、扩链剂和交联剂逐步反应,反应完成后冷却再加入分子筛活化粉、抗静电剂、流平剂、消泡剂和后催化剂,混合均匀后过滤出料。
本发明还提供上述无溶剂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:异氰酸酯30-70%,扩链树脂10-30%,交联树脂5-20%,活性聚硅氧烷5-25%,羟基丙烯酸酯1-5%,扩链剂1-5%,交联剂0.1-0.5%,前催化剂0.02-0.2%,后催化剂0.02-0.2%,分子筛活化粉1-5%,流平剂0.05-1%,消泡剂0.05-1%,抗静电剂0.5-5%;
(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0.5-3小时;然后加入已除水的交联树脂,在70-85℃下反应1-4小时;
(4)将聚合反应釜中的温度调节至50-70℃,再加入活性聚硅氧烷,在65-70℃下反应0.5-3小时;
(5)将聚合反应釜中的温度调节至50-70℃,再加入羟基丙烯酸酯和前催化剂,加热至70-80℃,反应0.5-3小时;
(6)将聚合反应釜中的温度调节至50-70℃,再加入扩链剂和交联剂,升温至70-80℃,反应1-4小时;
(7)将聚合反应釜中的温度调节至50-70℃,再加入分子筛活化粉、抗静电剂、流平剂、消泡剂和后催化剂,混合均匀后得到无溶剂高光涂料。
步骤(2)中,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(7)得到无溶剂高光涂料后过滤出料,密封遮光保存。
本发明的无溶剂高光涂料用于复合转移工艺生产高光卡纸,具有常温自固化功能(产品涂布后,常温下涂层的活性组分与纸张或空气中的水分、活性物质反应扩链而固化),不用加热或射线固化,纸张变形率小,且纸张表面光泽度高、耐热性好、耐折性好,适合烫金加工要求,且涂层与纸张附着力好,与模压膜有良好的剥离性。
采用本发明的无溶剂高光涂料用于复合转移法涂布,单位涂量少,成本较低。
本发明的无溶剂高光涂料无毒无害,对环境污染小,符合环保要求。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、附着力强等优点,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,无溶剂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:异氰酸酯50%(均为二苯基甲烷二异氰酸酯),扩链树脂20%(均为分子量为1000的聚已内酯二元醇(商品名:PCL-1000)),交联树脂10%(均为分子量为595的蔗糖为起始剂的聚醚多元醇(商品名:一诺威YNW-8343)),活性聚硅氧烷10%(均为分子量为1000的α,ω-二羟烃基聚硅氧烷),羟基丙烯酸酯2%(均为丙烯酸羟乙酯),扩链剂2%(均为对苯二酚二羟乙基醚),交联剂0.3%(均为三羟甲基丙烷),前催化剂0.1%(均为辛酸亚锡),后催化剂0.1%(均为双吗啉基二乙基醚),分子筛活化粉2.5%(均为洛阳建龙微纳新材料有限公司的分子筛活化粉JLH-PU),流平剂0.5%(均为聚醚硅氧烷共聚物,TEGOGlide 410),消泡剂0.5%(均为聚醚型消泡剂,迪高的TEGOFoamex 805消泡剂),抗静电剂2%(均为聚氨酯高分子抗静电剂(JL-WT));
(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(步骤(2)中,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1小时;
(6)将聚合反应釜中的温度调节至65℃,再加入扩链剂和交联剂,升温至70-80℃,反应2小时;
(7)将聚合反应釜中的温度调节至60℃,再加入分子筛活化粉、抗静电剂、流平剂、消泡剂和后催化剂,混合均匀后得到无溶剂高光涂料。
步骤(7)得到无溶剂高光涂料后过滤出料,密封遮光保存。
实施例2
本实施例中,无溶剂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:异氰酸酯36%(均为异氟尔酮二异氰酸酯),扩链树脂30%(均为分子量为2000的聚氧化丙烯醚二胺(商品名:ZD-1400)),交联树脂20%(均为分子量为650的山梨醇为起始剂的聚醚多元醇(商品名:联创LC-260S)),活性聚硅氧烷6%(均为分子量为1000的氨丙基封端聚二甲基硅氧烷),羟基丙烯酸酯1.5%(均为丙烯酸羟乙酯),扩链剂1.5%(均为1,4-丁二醇),交联剂0.1%(均为三羟甲基丙烷),前催化剂0.05%(均为辛酸亚锡),后催化剂0.05%(均为三乙醇胺),分子筛活化粉1%(均为洛阳建龙微纳新材料有限公司的分子筛活化粉JLH-PU),流平剂0.05%(均为聚醚硅氧烷共聚物,TEGO Glide 410),消泡剂0.05%(均为聚醚型消泡剂,迪高的TEGOFoamex 805消泡剂),抗静电剂3.7%(均为聚氨酯高分子抗静电剂(JL-WT));
(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(步骤(2)中,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℃,在真空度为-0.02MPA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2小时;
(5)将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2小时;
(6)将聚合反应釜中的温度调节至55℃,再加入扩链剂和交联剂,升温至70-80℃,反应2.5小时;
(7)将聚合反应釜中的温度调节至55℃,再加入分子筛活化粉、抗静电剂、流平剂、消泡剂和后催化剂,混合均匀后得到无溶剂高光涂料。
步骤(7)得到无溶剂高光涂料后过滤出料,密封遮光保存。
实施例3
本实施例中,无溶剂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:异氰酸酯63.5%(均为六亚甲基二异氰酸酯三聚体),扩链树脂11%(均为分子量为2000的聚氧化丙烯二醇(商品名:YNW-220)),交联树脂5%(均为分子量为350的丙三醇为起始剂的聚醚多元醇(商品名:NJ-303)),活性聚硅氧烷8%(均为分子量为1000的氨丙基封端聚二甲基硅氧烷),羟基丙烯酸酯1.5%(均为甲基丙烯酸羟乙酯),扩链剂3%(均为一缩二乙二醇),交联剂0.2%(均为丙三醇),前催化剂0.1%(均为二月桂酸二丁基锡),后催化剂0.2%(均为二甲基乙醇胺),分子筛活化粉5%(均为洛阳建龙微纳新材料有限公司的分子筛活化粉JLH-PU),流平剂0.8%(均为聚醚硅氧烷共聚物,TEGO Glide410),消泡剂0.8%(均为聚醚型消泡剂,迪高的TEGOFoamex 805消泡剂),抗静电剂0.9%(均为聚氨酯高分子抗静电剂(JL-WT));
(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(步骤(2)中,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2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3小时;
(5)将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2小时;
(6)将聚合反应釜中的温度调节至60℃,再加入扩链剂和交联剂,升温至70-80℃,反应3.5小时;
(7)将聚合反应釜中的温度调节至60℃,再加入分子筛活化粉、抗静电剂、流平剂、消泡剂和后催化剂,混合均匀后得到无溶剂高光涂料。
步骤(7)得到无溶剂高光涂料后过滤出料,密封遮光保存。
将实施例1-3无溶剂高光涂料和现有市场高光涂料产品,分别涂布在卡纸上,与OPP膜复合,常温熟化4小时,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,本发明制造的无溶剂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。
Claims (5)
1.一种无溶剂高光涂料,其特征在于由下述重量配比的原料制成:异氰酸酯30-70%,扩链树脂10-30%,交联树脂5-20%,活性聚硅氧烷5-25%,羟基丙烯酸酯1-5%,扩链剂1-5%,交联剂0.1-0.5%,前催化剂0.02-0.2%,后催化剂0.02-0.2%,分子筛活化粉1-5%,流平剂0.05-1%,消泡剂0.05-1%,抗静电剂0.5-5%;
所述扩链剂是1,4-丁二醇、新戊二醇、一缩二乙二醇、双酚A、对苯二酚二羟乙基醚、异氟尔酮二胺、乙二胺和苯二胺中的一种或其中多种的组合;
所述交联剂是丙三醇、季戊四醇和三羟甲基丙烷中的一种或其中多种的组合;
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;
所述交联树脂是分子量为200-1000的聚醚多元醇;
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;
所述无溶剂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:异氰酸酯30-70%,扩链树脂10-30%,交联树脂5-20%,活性聚硅氧烷5-25%,羟基丙烯酸酯1-5%,扩链剂1-5%,交联剂0.1-0.5%,前催化剂0.02-0.2%,后催化剂0.02-0.2%,分子筛活化粉1-5%,流平剂0.05-1%,消泡剂0.05-1%,抗静电剂0.5-5%;
(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0.5-3小时;然后加入已除水的交联树脂,在70-85℃下反应1-4小时;
(4)将聚合反应釜中的温度调节至50-70℃,再加入活性聚硅氧烷,在65-70℃下反应0.5-3小时;
(5)将聚合反应釜中的温度调节至50-70℃,再加入羟基丙烯酸酯和前催化剂,加热至70-80℃,反应0.5-3小时;
(6)将聚合反应釜中的温度调节至50-70℃,再加入扩链剂和交联剂,升温至70-80℃,反应1-4小时;
(7)将聚合反应釜中的温度调节至50-70℃,再加入分子筛活化粉、抗静电剂、流平剂、消泡剂和后催化剂,混合均匀后得到无溶剂高光涂料。
2.根据权利要求1所述的无溶剂高光涂料,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所述的无溶剂高光涂料,其特征是:所述羟基丙烯酸酯是丙烯酸羟乙酯和甲基丙烯酸羟乙酯中的一种或两者的组合。
4.根据权利要求1所述的无溶剂高光涂料,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;
所述后催化剂是胺类,如三乙醇胺、二甲基乙醇胺或双吗啉基二乙基醚;
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;
所述抗静电剂是阳离子抗静电剂、阴离子抗静电剂、非离子抗静电剂或高分子抗静电剂。
5.权利要求1所述的无溶剂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:异氰酸酯30-70%,扩链树脂10-30%,交联树脂5-20%,活性聚硅氧烷5-25%,羟基丙烯酸酯1-5%,扩链剂1-5%,交联剂0.1-0.5%,前催化剂0.02-0.2%,后催化剂0.02-0.2%,分子筛活化粉1-5%,流平剂0.05-1%,消泡剂0.05-1%,抗静电剂0.5-5%;
(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0.5-3小时;然后加入已除水的交联树脂,在70-85℃下反应1-4小时;
(4)将聚合反应釜中的温度调节至50-70℃,再加入活性聚硅氧烷,在65-70℃下反应0.5-3小时;
(5)将聚合反应釜中的温度调节至50-70℃,再加入羟基丙烯酸酯和前催化剂,加热至70-80℃,反应0.5-3小时;
(6)将聚合反应釜中的温度调节至50-70℃,再加入扩链剂和交联剂,升温至70-80℃,反应1-4小时;
(7)将聚合反应釜中的温度调节至50-70℃,再加入分子筛活化粉、抗静电剂、流平剂、消泡剂和后催化剂,混合均匀后得到无溶剂高光涂料。
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