CN116253855A - 一种pet膜用耐丁酮水性聚氨酯树脂及其制备方法 - Google Patents
一种pet膜用耐丁酮水性聚氨酯树脂及其制备方法 Download PDFInfo
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 title claims abstract description 62
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
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- 238000006243 chemical reaction Methods 0.000 claims description 10
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Abstract
本发明涉及聚氨酯树脂技术领域,尤其是一种PET膜用耐丁酮水性聚氨酯树脂,其包括如下组分:多元醇90‑150份、扩链剂15‑30份、抗氧化剂1‑2份、异氰酸酯80‑120份、有机铋催化剂0.5‑2份、有机溶剂10‑30份、中和剂8‑12份、去离子水400‑600份,以上份数均为重量份数。本发明还公开了上述水性聚氨酯树脂的制备方法。本发明所得到的一种水性聚氨酯树脂及其制备方法,其为单组份水性聚氨酯,所成薄膜切变性佳,耐热性能优异,涂布与PET膜后剥离强度合适,是良好的PET膜用离型剂,可广泛应用于镀铝烫金工艺;且具有良好的耐丁酮擦拭性能,同时为图文层提供保护功能。
Description
技术领域
本发明涉及聚氨酯树脂技术领域,尤其是一种PET膜用耐丁酮水性聚氨酯树脂及其制备方法。
背景技术
PET膜具有优异的耐热、耐寒性,且拉伸强度高,表面张力低,价格相对低廉,是作为转移基膜的绝佳材料,被广泛应用在烫金等转印技术中。为了保证转印图文的完整性及使用过程中对外界环境的耐受性,离型层和保护层是不可或缺的。作为离型层,表面张力要低,在PET膜上可以形成连续均匀的涂层,转移时也能很好地从PET膜上脱离;同时,要具有良好的切变性以确保转移工作的顺利进行。
为了保护转印产品的表现性与耐久性,降低外界的溶剂、光照、空气等各种不利因素与图文层发生反应、造成磨耗,保护层通常设在离型层与图文层之间,能有效隔绝外界因素,来延缓图文层的消磨。根据功能需要且考虑到对产品的色泽影响,多为一道或两道功能涂层,在尽量小的影响图文层色泽的前提下起到保护作用。
耐丁酮测试也叫耐有机溶剂试验,不仅用来评测转印产品耐有机溶剂腐蚀性能的高低,也能从侧面评判涂层的应用物性,判断保护层对转印产品的保护能力,是对PET转印产品性能的一个重要评判标准。
现有的聚氨酯树脂的稳定性相对较差,同时耐高温、耐丁酮性能较差。
发明内容
本发明为了解决上述技术不足而提供一种PET膜用耐丁酮水性聚氨酯树脂及其制备方法,其性能稳定,具有耐高温和耐丁酮性质。
本发明公开了一种PET膜用耐丁酮水性聚氨酯树脂,其包括如下组分:多元醇90-150份、扩链剂15-30份、抗氧化剂1-2份、异氰酸酯80-120份、有机铋催化剂0.5-2份、有机溶剂10-30份、中和剂8-12份、去离子水400-600份,以上份数均为重量份数。
作为优化,所述多元醇为聚碳酸酯二元醇(PCDL),其分子量为1000-2500。
作为优化,所述扩链剂包括亲水扩链剂和多羟基扩链剂,所述亲水扩链剂为2,2-二羟甲基丙酸(DMPA),所述多羟基扩链剂包括1,4-丁二醇(BDO)和三羟甲基丙烷(TMP);其中亲水扩链剂和多羟基扩链剂质量比为1.2:1至1.5:1;多羟基扩链剂中BDO和TMP质量比为8:1至12:1。作为优化,所述异氰酸酯为4,4′-二环己基甲烷二异氰酸酯(HMDI)。
作为优化,所述有机溶剂为丙酮(AC)。
作为优化,所述中和剂为三乙胺(TEA)。
一种PET膜用耐丁酮水性聚氨酯树脂的制备方法,包括如下步骤:
步骤1,将90-150重量份多元醇、15-30重量份扩链剂及1-2重量份抗氧化剂加入反应釜中,在50-80℃下搅拌20min,其中,扩链剂包含亲水扩链剂和多羟基扩链剂;
步骤2,搅拌均匀后加入80-120重量份异氰酸酯,0.5-2重量份有机铋催化剂,10-30重量份有机溶剂,在75-100℃下进行预聚反应;
步骤3,加入8-12重量份中和剂继续搅拌15-30min,在45-55℃下完成中和反应,得到聚氨酯预聚体;
步骤4,把聚氨酯预聚体经高速分散到400-600重量份去离子水中,脱出有机溶剂,形成水性聚氨酯树脂。
其中步骤3中,中和反应的中和度为100%。
其中步骤4中,高速分散的搅拌速度为2000-3500r/min。
步骤4所得到的水性聚氨酯树脂的固含量为30%。
本发明在制备聚氨酯预聚体的过程中引入了多官能度扩链剂,使得制得的水性聚氨酯树脂具有轻微的网状结构,但不至于影响到聚氨酯分散体的稳定性。通过对基本原料的筛选组合,进而调整聚氨酯的分子内及分子间结构,使得制得的水性聚氨酯树脂具有优异的耐热性和耐溶剂性能。
所述步骤1中,多元醇为聚碳酸酯二元醇(PCDL),分子量在1000-2500之间。PCDL的结构规整,极性较高,帮助提高所合成的聚氨酯分子的规整度、调整离型结构,使得所合成的聚氨酯兼具耐热性、抗水解性和耐化学品性能。
所述亲水扩链剂为2,2-二羟甲基丙酸(DMPA),普通多羟基扩链剂包括1,4-丁二醇(BDO)和三羟甲基丙烷(TMP)。BDO结构规整,有助于提高聚氨酯的结晶性。
本发明的水性聚氨酯树脂以水为介质,用以调节粘度添加的有机溶剂丙酮后续可通过真空减压蒸馏脱出,因此产品不含有机溶剂,符合环保及可持续发展的理念。
本发明所得到的一种水性聚氨酯树脂及其制备方法,其为单组份水性聚氨酯,所成薄膜切变性佳,耐热性能优异,涂布与PET膜后剥离强度合适,是良好的PET膜用离型剂,可广泛应用于镀铝烫金工艺;且具有良好的耐丁酮擦拭性能,同时为图文层提供保护功能。相较于传统PET膜所使用的工艺,本发明的水性聚氨酯树脂将离型层色层合二为一,大大简化了PET膜加工工序,提高了生产效率,降低了加工成本。
具体实施方式
为更进一步阐述本发明为实现预定发明目的所采取的技术手段及功效,以下结合较佳实施例,对依据本发明的具体实施方式、结构、特征及其功效,详细说明如后。
实施例1:
本发明公开了一种PET膜用耐丁酮水性聚氨酯树脂的制备方法,将100重量份的PCDL-2000、0.6重量份TMP、6重量份BDO、12重量份DMPA、1重量份抗氧化剂在50℃下加入反应釜中,搅拌20min;搅拌均匀后加入100重量份HMDI,在75℃下反应0.5h,再95℃保温反应1.5h,加入25重量份AC,1重量份有机铋催化剂,继续反应2h至反应完全;降温至55℃,加入9.1重量份TEA,继续搅拌15min至完全中和,得到聚氨酯预聚体;在2500r/min的转速下,把聚氨酯预聚体分散到530重量份去离子水中,搅拌40min后脱出丙酮,静置熟化3天后得到稳定的30%固含的水性聚氨酯乳液,过滤后即得PET膜用耐丁酮水性聚氨酯树脂。
使用方法:将PET膜用耐丁酮水性聚氨酯树脂加入2重量份润湿剂(BYK345),使用缔合型增稠剂(BYK428)增至800cps/25℃,消泡后经30mm的线棒刮涂在未离型处理过的PET膜上,130℃保温3min,得到样品a。
实施例2:
本发明公开了一种PET膜用耐丁酮水性聚氨酯树脂的制备方法,将90重量份的PCDL-2000、5重量份的PCDL-1000、0.6重量份TMP、7重量份BDO、10.5重量份DMPA、1重量份抗氧化剂在50℃下加入反应釜中,搅拌20min;搅拌均匀后加入100重量份HMDI,在75℃下反应0.5h,再95℃保温反应1.5h,加入20重量份AC,1重量份有机铋催化剂,继续反应2h至反应完全;降温至55℃,加入7.93重量份TEA,继续搅拌15min至完全中和,得到聚氨酯预聚体;在2500r/min的转速下,把聚氨酯预聚体分散到520重量份去离子水中,搅拌40min后脱出丙酮,静置熟化3天后得到稳定的30%固含的水性聚氨酯乳液,过滤后即得PET膜用耐丁酮水性聚氨酯树脂。
使用方法:将PET膜用耐丁酮水性聚氨酯树脂加入2重量份润湿剂,使用缔合型增稠剂增至800cps/25℃,消泡后经30mm的线棒刮涂在未离型处理过的PET膜上,130℃保温3min,得到样品b。
实施例3:
本发明公开了一种PET膜用耐丁酮水性聚氨酯树脂的制备方法,将110重量份的PCDL-2000、0.7重量份TMP、6重量份BDO、11重量份DMPA、1重量份抗氧化剂在50℃下加入反应釜中,搅拌20min;搅拌均匀后加入100重量份HMDI,在75℃下反应0.5h,再95℃保温反应1.5h,加入30重量份AC,1重量份有机铋催化剂,继续反应2h至反应完全;降温至55℃,加入8.3重量份TEA,继续搅拌15min至完全中和,得到聚氨酯预聚体;在2500r/min的转速下,把聚氨酯预聚体分散到535重量份去离子水中,搅拌40min后脱出丙酮,静置熟化3天后得到稳定的30%固含的水性聚氨酯乳液,过滤后即得PET膜用耐丁酮水性聚氨酯树脂。
使用方法:将PET膜用耐丁酮水性聚氨酯树脂加入2重量份润湿剂,使用缔合型增稠剂增至800cps/25℃,消泡后经30mm的线棒刮涂在未离型处理过的PET膜上,130℃保温3min,得到样品c。
对上述实施例1-3进行性能测试:
测试方法如下:经镀铝机处理后评测涂层经高温镀铝后的剥离强度有无变化,论证样品的高温稳定性;根据GB/T 23989——2009A法,评测涂层的耐丁酮程度。
以上所述,仅是本发明的较佳实施例而已,并非对本发明作任何形式上的限制,虽然本发明已以较佳实施例揭示如上,然而并非用以限定本发明,任何本领域技术人员,在不脱离本发明技术方案范围内,当可利用上述揭示的技术内容做出些许更动或修饰为等同变化的等效实施例,但凡是未脱离本发明技术方案内容,依据本发明的技术实质对以上实施例所作的任何简化修改、等同变化与修饰,均仍属于本发明技术方案的范围内。
Claims (9)
1.一种PET膜用耐丁酮水性聚氨酯树脂,其特征是:其包括如下组分:多元醇90-150份、扩链剂15-30份、抗氧化剂1-2份、异氰酸酯80-120份、有机铋催化剂0.5-2份、有机溶剂10-30份、中和剂8-12份、去离子水400-600份,以上份数均为重量份数。
2.根据权利要求1所述的一种PET膜用耐丁酮水性聚氨酯树脂,其特征是:所述多元醇为聚碳酸酯二元醇,其分子量为1000-2500。
3.根据权利要求1所述的一种PET膜用耐丁酮水性聚氨酯树脂,其特征是:所述扩链剂包括亲水扩链剂和多羟基扩链剂,所述亲水扩链剂为2,2-二羟甲基丙酸,所述多羟基扩链剂包括1,4-丁二醇和三羟甲基丙烷。
4.根据权利要求1所述的一种PET膜用耐丁酮水性聚氨酯树脂,其特征是:所述异氰酸酯为4,4′-二环己基甲烷二异氰酸酯。
5.根据权利要求1所述的一种PET膜用耐丁酮水性聚氨酯树脂,其特征是:所述有机溶剂为丙酮。
6.根据权利要求1所述的一种PET膜用耐丁酮水性聚氨酯树脂,其特征是:中和剂为三乙胺。
7.一种PET膜用耐丁酮水性聚氨酯树脂的制备方法,其特征是:包括如下步骤:
步骤1,将90-150重量份多元醇、15-30重量份扩链剂及1-2重量份抗氧化剂加入反应釜中,在50-80℃下搅拌20min,其中,扩链剂包含亲水扩链剂和多羟基扩链剂;
步骤2,搅拌均匀后加入80-120重量份异氰酸酯,0.5-2重量份有机铋催化剂,10-30重量份有机溶剂,在75-100℃下进行预聚反应;
步骤3,加入8-12重量份中和剂继续搅拌15-30min,在45-55℃下完成中和反应,得到聚氨酯预聚体;
步骤4,把聚氨酯预聚体经高速分散到400-600重量份去离子水中,脱出有机溶剂,形成水性聚氨酯树脂。
8.根据权利要求7所述的一种PET膜用耐丁酮水性聚氨酯树脂的制备方法,其特征是:其中步骤3中,中和反应的中和度为100%。
9.根据权利要求7所述的一种PET膜用耐丁酮水性聚氨酯树脂的制备方法,其特征是:其中步骤4中,高速分散的搅拌速度为2000-3500r/min。
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