CN113927983B - 一种单面高热封双向拉伸聚丙烯基材及其制备方法和聚丙烯镀铝膜及其制备方法 - Google Patents
一种单面高热封双向拉伸聚丙烯基材及其制备方法和聚丙烯镀铝膜及其制备方法 Download PDFInfo
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- -1 polypropylene Polymers 0.000 title claims abstract description 22
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 12
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 35
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Abstract
本发明提供一种单面高热封双向拉伸聚丙烯基材及其制备方法和聚丙烯镀铝膜及其制备方法;聚丙烯镀铝膜包括上述技术方案所述基材、氧化铝层和自粘性聚乙烯醇层,使得薄膜具有高热封强度高阻隔;还具有优异的机械性能。聚丙烯镀铝膜的氧气透过率为0.7~1.0cm3/(m2.24h);水蒸汽透过率0.7~1.0g/(m2.24h);纵向拉伸强度为162~165MPa;横向拉伸强度为221~225MPa;纵向断裂延伸率为130~134%,横向断裂延伸率为56~59%;纵向热收缩率为1.1~1.4%,横向热收缩率为1.0~1.1%;雾度为2.0~2.4%。
Description
技术领域
本发明属于高分子薄膜技术领域,尤其涉及一种单面高热封双向拉伸聚丙烯基材及其制备方法和聚丙烯镀铝膜及其制备方法。
背景技术
传统的BOPP阻隔涂布膜主要用于跟CPP或CPE或PE复合后用于食品药品等包装,为多层结构,产品结构中,CPP或CPE或PE主要起高热封强度的作用。传统的BOPP涂布膜不能直接用于物品包装的主要原因是其热封型双向拉伸聚丙烯的热封强度较小,一般小于4N/15mm,包装的食品在包装或搬运过程中容易造成破包。传统的双向拉伸聚丙烯高阻隔涂布膜复合CPP或CPE或PP 膜,会增加生产成本和引起环保问题。
发明内容
有鉴于此,本发明的目的在于提供一种单面高热封双向拉伸聚丙烯基材及其制备方法和聚丙烯镀铝膜及其制备方法,该基材具有较高热封强度。
本发明提供了一种单面高热封双向拉伸聚丙烯基材,包括依次接触的热封层、中间层和非热封层;
以质量分数计,所述热封层的原料包括71~89%乙烯-丙烯-丁烯三元共聚物、10~25%聚烯烃弹性体POE改性的超低密度聚乙烯VLDPE和2~4%二氧化硅;
所述中间层的原料为均聚聚丙烯;
所述非热封层的原料包括98~99%均聚聚丙烯和1~2%二氧化硅。
在本发明中,所述热封层的厚度为2~5μm;
中间层的厚度为15~42μm;
非热封层的厚度为1~3μm。
在本发明中,VLDPE为超低密度聚丙烯,POE为聚烯烃弹性体。在本发明中,所述均聚聚丙烯的等规度为96-98%。在热封温度130℃,热封时间0.3s 的条件下,热封面对热封面的热封强度值为9~15N/15mm,达到食品包装的要求,且还具有良好的物理机械性能。
本发明提供了一种上述技术方案所述单面高热封双向拉伸聚丙烯基材的制备方法,包括以下步骤:
配料,挤出,铸片,纵向拉伸和横向拉伸,电晕处理,收卷,得到单面高热封双向拉伸聚丙烯基材;
所述铸片的冷却温度为18~40℃;所述纵向拉伸的拉伸倍率为480~535%;纵向拉伸的预热温度为105~135℃,拉伸温度为90~115℃;横向拉伸的拉伸倍率为850~960%,横向拉伸的预热温度为160~180℃,拉伸温度为145~160℃,定型温度为140~170℃;挤出的温度为200~250℃。
在本发明中,将不同层的原料投入不同的料罐,按照设定的比例进行混料,混料可人工混料或设备混料。
本发明将中间层原料经混料后流入双螺杆挤出机或单螺杆串联挤出机,非热封层和热封层的原料混料后各自流入辅助挤出机,三层物料在模头汇聚后流出;挤出机的作用是:熔融、塑化、混炼和均匀定量挤出;挤出机的温度为200~250℃。
本发明采用本领域技术人员熟知的铸片机进行铸片;铸片机将挤出机模头流出的树脂冷却成片材,使树脂的结晶度、晶体形态、晶体的大小达到理想状态,从而提高基材的物理性能,有利于纵向和横向的拉伸。铸片的冷却温度为18~40℃。
在本发明中,所述纵向拉伸的作用是将从铸片机过来的片材进行预热,并在一定的速度下,将片材纵向拉长,使聚合物分子进行纵向取向。为保证纵向收缩率,纵向拉伸的预热温度和拉伸温度尽可能低,拉伸倍率尽可能高。
在本发明中,横向拉伸作用是将纵向拉伸过的片材通过设定的链条导轨在有较大的扩张角的拉伸区进行横向拉伸,同样使聚合物分子在横向取向。为保证横向收缩率,横向拉伸的预热温度和拉伸温度尽可能低,但温度过低容易出现脱夹和破膜的问题;预热温度为:160~180℃、拉伸温度为: 145~160℃、定型温度为140~170℃、拉伸倍率为850~960%。
横向拉伸得到的薄膜经过切边后对其非热封面进行经过电晕处理,使其表面的张力达到38达因以上,后再经过收卷机进行收卷。收卷工艺跟薄膜的性能有关,可跟据收卷情况设定收卷张力、衰减率、压辊压力调整,拉伸比100±2%。
本发明提供了一种高热封强度高阻隔双向拉伸聚丙烯镀铝膜,包括单面高热封双向拉伸聚丙烯基材;所述基材为上述技术方案所述的单面高热封双向拉伸聚丙烯基材或上述技术方案所述方法制备的单面高热封双向拉伸聚丙烯基材;
设置在所述单面高热封双向拉伸聚丙烯基材的非热封层表面上的氧化铝层;
及设置在所述氧化铝层上的自粘性聚乙烯醇层。
本发明提供的高热封强度高阻隔双向拉伸聚丙烯镀铝膜包括单面高热封双向拉伸聚丙烯基材;所述基材为上述技术方案所述的单面高热封双向拉伸聚丙烯基材或上述技术方案所述方法制备的单面高热封双向拉伸聚丙烯基材。在本发明中,所述基材的厚度优选为18~45μm。
本发明提供的高热封强度高阻隔双向拉伸聚丙烯镀铝膜包括设置在所述单面高热封双向拉伸聚丙烯基材的非热封层表面上的氧化铝层;所述氧化铝层的厚度优选为0.1~0.3μm。
本发明提供的高热封强度高阻隔双向拉伸聚丙烯镀铝膜包括设置在所述氧化铝层上的自粘性聚乙烯醇层。在本发明中,所述自粘性聚乙烯醇层的制备原料包括:固含量5%~15%的自粘性聚乙烯醇、固含量5%~15%的二氧化硅分散液和固含量15%~30%的蜡乳液;所述二氧化硅和与自粘性聚乙烯醇的固体比为0.1%~0.8%,蜡乳液与自粘性聚乙烯醇的固体比为0.5%~8%。所述自粘性聚乙烯醇购买于海南必凯水性新材料有限公司;自粘性聚乙烯醇固含量9.0%,表面张力38mn/m,粘度90mpa.s,pH 值9.6。
在本发明中,所述自粘性聚乙烯醇层的厚度优选为0.5~1.5μm。
在本发明中,所述高热封强度高阻隔双向拉伸聚丙烯镀铝膜优选按照以下方法制得:
将单面高热封双向拉伸聚丙烯基材的非热封层上蒸镀氧化铝层,再在氧化铝层上涂布自粘性聚乙烯醇涂布液,烘干,收卷,固化,得到高热封强度高阻隔双向拉伸聚丙烯镀铝膜。
本发明在镀氧化铝机上蒸镀氧化铝层。将单面高热封双向拉伸聚丙烯基材在真空室内抽真空,真空度达到0.04Pa以上,将蒸发舟升温至1400~1600℃;将铝丝置于蒸发舟上连续熔化形成铝蒸汽,同时通入纯度为99.9%且加入量为 380~420sccm的高纯度氧,在运行速度为450~550m/min的单面热封膜的非热封层上形成氧化铝层。
在本发明中,所述铝丝的纯度为99.9%。
在本发明中,烘干的温度为105~115℃,优选为110℃;固化的温度为 30~50℃,时间为20~30h;具体实施例中,固化的温度为40℃,时间为24h。
本发明提供的双向拉伸聚丙烯镀铝膜包括上述技术方案所述基材、氧化铝层和自粘性聚乙烯醇层,使得薄膜具有高热封强度高阻隔。实验结果表明:聚丙烯镀铝膜的氧气透过率为0.7~1.0cm3/(m2.24h);水蒸汽透过率0.7~1.0g/ (m2.24h)。
附图说明
图1为本发明提高的聚丙烯镀铝膜的结构示意图。
具体实施方式
为了进一步说明本发明,下面结合实施例对本发明提供的一种单面高热封双向拉伸聚丙烯基材及其制备方法和聚丙烯镀铝膜进行详细地描述,但不能将它们理解为对本发明保护范围的限定。
实施例1
生产厚度30μm薄膜。配料:热封层厚5μm,其中乙烯-丙烯-丁烯三元共聚物85%、及POE改性的VLDPE13%和二氧化硅2%;中间层厚度为22μm,其中,均聚聚丙烯100%,非热封层的厚度为3μm,其中,均聚聚丙烯98%和 2%二氧化硅。
制膜:采用双向拉伸共挤工艺制得本发明的双向拉伸聚丙烯膜,其中挤出机温度:230℃;铸片机温度:25℃;纵向拉伸倍率:495%,纵拉预热温度:115℃,纵拉拉伸温度:104℃;横向拉伸倍率:940%,横拉预热温度:175℃,横拉拉伸温度:159℃,横拉定型温度:160℃;收卷拉伸比:100%。下层双极电晕处理10KW。
实施例1制备的单面高热封双向拉伸聚丙烯基材的性能测试结果见表1:
表1实施例1制备的基材的测试结果
实施例2
生产厚度35μm薄膜。配料:热封层厚度为4μm,乙烯-丙烯-丁烯三元共聚物81%、及POE改性的VLDPE15%和二氧化硅4%;中间层厚度为30μm,其中均聚聚丙烯100%;非热封层厚度为1μm,其中,均聚丙烯99%和二氧化硅1%。
制膜:采用双向拉伸共挤工艺制得本发明的双向拉伸聚丙烯膜,其中挤出机温度:235℃;铸片机温度:21℃;纵向拉伸倍率:500%,纵拉预热温度: 117℃,纵拉拉伸温度:106℃;横向拉伸倍率:850%,横拉预热温度:180℃,横拉拉伸温度:155℃,横拉定型温度:160℃;收卷拉伸比:100%。下层双极电晕处理9KW。
实施例2制备的单面高热封双向拉伸聚丙烯基材的性能测试结果见表2:
表2实施例2制备的基材的测试结果
实施例3
生产厚度40μm薄膜。配料:热封层厚4μm,其中乙烯-丙烯-丁烯三元共聚物79%及20%POE改性的VLDPE和二氧化硅1%;中间层厚34μm,其中均聚聚丙烯100%;非热封层厚度为2μm,其中,均聚聚丙烯98%和二氧化硅 2%。
制膜:采用双向拉伸共挤工艺制得本发明的双向拉伸聚丙烯膜,其中挤出机温度:240℃;铸片机温度:20℃;纵向拉伸倍率:510%,纵拉预热温度: 120℃,纵拉拉伸温度:110℃;横向拉伸倍率:910%,横拉预热温度:180℃,横拉拉伸温度:160℃,横拉定型温度:155℃;收卷拉伸比:100%。下层双极电晕处理8KW。
实施例3制备的单面高热封双向拉伸聚丙烯基材的性能测试结果见表3:
表3实施例3制备的基材的测试结果
实施例4
在镀氧化铝机上,将实施例1制备的单面热封膜基材放置在真空室内进行抽真空操作,真空度达到0.04Pa 以上,将蒸发舟升温至1450℃,然后再把纯度为99.9%铝丝连续送至蒸发舟上,使铝丝在蒸发舟上连续熔化、蒸发形成铝蒸汽,同时通入纯度为99.9%且加入量为380sccm的高纯度氧,使铝蒸汽和高纯度氧发生反应生成氧化铝,从而在运行速度为450m/min的单面热封膜上的电晕面冷却后形成一层透明的氧化铝层;氧化铝层的厚度为0.2μm;
在涂布机上,单面热封镀氧化铝膜放卷出来,机器速度为200米每分钟,在镀氧化铝膜面涂布由9%固含量自粘性聚乙烯醇中加入10%固含量的二氧化硅分散液和25%固含量的蜡乳液,二氧化硅与自粘性聚乙烯醇的固体比为 0.2%,蜡乳液与自粘性聚乙烯醇的固体比为5%,然后烘干,温度为110℃,然后收卷,在固化室固化24小时和40℃,自粘性聚乙烯醇层的厚度为0.8μm,高热封强度高阻隔双向拉伸聚丙烯涂布膜。
表4实施例4制备的聚丙烯涂布膜的性能测试结果
实施例5
在镀氧化铝机上,将实施例2制备的单面热封膜基材放置在真空室内进行抽真空操作,真空度达到0.04Pa 以上,将蒸发舟升温至1500℃,然后再把纯度为99.9%铝丝连续送至蒸发舟上,使铝丝在蒸发舟上连续熔化、蒸发形成铝蒸汽,同时通入纯度为99.9%且加入量为400sccm的高纯度氧,使铝蒸汽和高纯度氧发生反应生成氧化铝,从而在运行速度为500m/min的单面热封膜上的电晕面冷却后形成一层透明的氧化铝层;氧化铝层的厚度为0.3μm;
在涂布机上,单面热封镀氧化铝膜放卷出来,机器速度为180米每分钟,在镀氧化铝膜面涂布由9%固含量自粘性聚乙烯醇中加入10%固含量的二氧化硅分散液和25%固含量的蜡乳液,二氧化硅与自粘性聚乙烯醇的固体比为 0.2%,蜡乳液与自粘性聚乙烯醇的固体比为6%,然后烘干,温度为105℃,然后收卷,在固化室固化24小时和40℃,自粘性聚乙烯醇层的厚度为0.7μm,得到高热封强度高阻隔双向拉伸聚丙烯涂布膜。
表5实施例5制备的聚丙烯涂布膜的性能测试结果
实施例6
在镀氧化铝机上,将实施例3制备的单面热封膜基材放置在真空室内进行抽真空操作,真空度达到0.04Pa 以上,将蒸发舟升温至1550摄氏度,然后再把纯度为99.9%铝丝连续送至蒸发舟上,使铝丝在蒸发舟上连续熔化、蒸发形成铝蒸汽,同时通入纯度为99.9%且加入量为410sccm的高纯度氧,使铝蒸汽和高纯度氧发生反应生成氧化铝,从而在运行速度为520m/min的单面热封膜上的电晕面冷却后形成一层透明的氧化铝层,制得单面热封镀氧化铝膜,厚度为0.3μm;
在涂布机上,单面热封镀氧化铝膜放卷出来,机器速度为160米/min,在镀氧化铝膜面涂布由9%固含量自粘性聚乙烯醇中加入10%固含量的二氧化硅分散液和25%固含量的蜡乳液,二氧化硅与自粘性聚乙烯醇的固体比为 0.2%,蜡乳液与自粘性聚乙烯醇的固体比为4%,然后烘干,温度为100℃,然后收卷,在固化室固化24小时和40℃,自粘性聚乙烯醇层的厚度为0.7μm,高热封强度高阻隔双向拉伸聚丙烯涂布膜。
表6实施例6制备的聚丙烯涂布膜的性能测试结果
由以上实施例可知,本发明提供的双向拉伸聚丙烯镀铝膜包括上述技术方案所述基材、氧化铝层和自粘性聚乙烯醇层,使得薄膜具有高热封强度高阻隔;还具有优异的机械性能。实验结果表明:聚丙烯镀铝膜的氧气透过率为0.7~1.0cm3/(m2.24h);水蒸汽透过率0.7~1.0g/(m2.24h);纵向拉伸强度为 162~165MPa;横向拉伸强度为221~225MPa;纵向断裂延伸率为130%~134%,横向断裂延伸率为56~59%;纵向热收缩率为1.1~1.4%,横向热收缩率为 1.0~1.1%;雾度为2.0~2.4%。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (2)
1.一种高热封强度高阻隔双向拉伸聚丙烯镀铝膜的制备方法,包括以下步骤:
将单面高热封双向拉伸聚丙烯基材的非热封层上蒸镀氧化铝层,再在氧化铝层上涂布自粘性聚乙烯醇涂布液,烘干,收卷,固化,得到高热封强度高阻隔双向拉伸聚丙烯镀铝膜;
所述单面高热封双向拉伸聚丙烯基材的非热封层上蒸镀氧化铝层具体包括:
将单面高热封双向拉伸聚丙烯基材在真空室内抽真空,真空度达到0.04Pa以上,将蒸发舟升温至1400~1600℃;将铝丝置于蒸发舟上连续熔化形成铝蒸汽,同时通入纯度为99.9%且加入量为380~420sccm的高纯度氧,在运行速度为450~550m/min的单面热封膜的非热封层上形成氧化铝层;
所述高热封强度高阻隔双向拉伸聚丙烯镀铝膜,包括单面高热封双向拉伸聚丙烯基材;设置在所述单面高热封双向拉伸聚丙烯基材的非热封层表面上的氧化铝层;
及设置在所述氧化铝层上的自粘性聚乙烯醇层;
所述单面高热封双向拉伸聚丙烯基材包括依次接触的热封层、中间层和非热封层;所述热封层的厚度为2~5μm;中间层的厚度为15~42μm;非热封层的厚度为1~3μm;
以质量分数计,所述热封层的原料包括71~89%乙烯-丙烯-丁烯三元共聚物、10~25%POE改性的VLDPE和2~4%二氧化硅;
所述中间层的原料为均聚聚丙烯;
所述非热封层的原料包括98~99%均聚聚丙烯和1~2%二氧化硅;
所述自粘性聚乙烯醇层的制备原料包括:
固含量5%~15%的自粘性聚乙烯醇、固含量5%~15%的二氧化硅分散液和固含量15%~30%的蜡乳液;
所述二氧化硅和与自粘性聚乙烯醇的固体比为0.1%~0.5%,蜡乳液与自粘性聚乙烯醇的固体比为0.5%~8%;
所述氧化铝层的厚度为0.1~0.3μm;
所述自粘性聚乙烯醇层的厚度为0.5~1.5μm。
2.根据权利要求1所述的制备方法,其特征在于,所述单面高热封双向拉伸聚丙烯基材的制备方法,包括以下步骤:
配料,挤出,铸片,纵向拉伸和横向拉伸,电晕处理,收卷,得到单面高热封双向拉伸聚丙烯基材;
所述铸片的冷却温度为18~40℃;所述纵向拉伸的拉伸倍率为490~535%;纵向拉伸的预热温度为105~135℃,拉伸温度为90~115℃;横向拉伸的拉伸倍率为850~960%,横向拉伸的预热温度为160~180℃,拉伸温度为145~160℃,定型温度为140~170℃;挤出的温度为200~250℃。
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