CN112500634A - 一种双向拉伸聚丙烯热封薄膜及其制备工艺 - Google Patents
一种双向拉伸聚丙烯热封薄膜及其制备工艺 Download PDFInfo
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- CN112500634A CN112500634A CN202011156127.4A CN202011156127A CN112500634A CN 112500634 A CN112500634 A CN 112500634A CN 202011156127 A CN202011156127 A CN 202011156127A CN 112500634 A CN112500634 A CN 112500634A
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Classifications
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Abstract
本发明公开了一种双向拉伸聚丙烯热封薄膜及其制备工艺，包括外表层、芯层和内表层，所述热封薄膜自上而下由外表层、芯层、内表层三层结构共挤制得，所述芯层包括以下重量组分：87～92份均聚聚丙烯、5～10份氢化石油树脂、0.8～1.2份纳米玻璃粉、0.4～0.8份碳酸钙、0.25～2.5份成核剂、0.2～0.5份稳定剂、0.01～0.2份抗氧剂。本发明通过对双向拉伸膜层结构、组分成分及其制备工艺的设置，实现所制烟膜性能的提高，提高了所制烟膜的强度和机械性能、光泽度，润湿度，并提高其耐磨性、水气阻隔能力，能够有效防止水气凝结、渗透，保持现有烟草品质和烟膜外观，适合广泛推广与使用。
Description
技术领域
本发明涉及烟膜技术领域，具体为一种双向拉伸聚丙烯热封薄膜及其制备工艺。
背景技术
烟草制造业是中国一个主要税源，对于其烟草包装的外表面薄膜，曾使用过包括玻璃纸、PVC涂布膜、PVDC涂布膜、BOPP烟膜等多种材料，其中BOPP烟膜又称双向拉伸聚丙烯烟膜，由多种聚丙烯功能性材料进行共挤、拉伸成型，具有良好的光学性能、较宽的热封范围、较高的热封强度、较强的水蒸气阻隔能力、均匀的厚度、较宽的收缩率调控范围以及良好的挺度等其他材料不可比拟的特性，是香烟包装的理想材料，但现有的一些烟膜耐磨性差，易出现划痕，影响使用效果和美观度，且水蒸气阻隔透过性差，易造成烟草变质，在湿度较高的环境下，潮湿的空气容易在烟膜表面凝结，呈现“水雾”状的外观缺陷，因此，我们提出一种双向拉伸聚丙烯热封薄膜及其制备工艺。
发明内容
本发明的目的在于提供一种双向拉伸聚丙烯热封薄膜及其制备工艺，以解决上述背景技术中提出的问题。
为了解决上述技术问题，本发明提供如下技术方案：一种双向拉伸聚丙烯热封薄膜，包括外表层、芯层和内表层，所述热封薄膜自上而下由外表层、芯层、内表层三层结构共挤制得，所述芯层包括以下重量组分：87～92份均聚聚丙烯、5～10份氢化石油树脂、 0.8～1.2份纳米玻璃粉、0.4～0.8份碳酸钙、0.25～2.5份成核剂、0.2～0.5份稳定剂、 0.01～0.2份抗氧剂。
进一步的，所述外表层包括以下重量组分：93～95份无规共聚聚丙烯、5～9份乙烯-1- 辛烯共聚物、0.3～0.6份水滑石、1～2份石英、0.8～1.2份纳米玻璃粉、0.1～0.3份聚醚改性硅油、0.5～1.2份水杨酸乙基己酯、0.25～2.5份成核剂、2～3.5份抗静电剂、0.05～0.3份爽滑剂。
进一步的，所述内表层包括以下重量组分：93～95份无规共聚聚丙烯、5～9份乙烯-1- 辛烯共聚物、0.1～0.3份聚醚改性硅油、0.5～1.5份柠檬酸三乙酯、0.2～0.5份月桂酸单甘油酯、0.1～1.0份纳米玻璃粉、0.2～1份乳酸钠、0.2～0.5份吡咯烷酮羧酸钠、 0.01～0.2份抗氧剂。
进一步的，所述纳米玻璃粉所需原料包括以下重量组分：2.9～6.0份硝酸锌、7.5～ 15.0份硝酸铝、12.5～37.6份碳酸锌、0.8～2.4份二氧化钛、7.8～15份氢氧化铝、25～27份长石、18～30份正硅酸乙酯。
一种双向拉伸聚丙烯热封薄膜的制备工艺，包括以下步骤：
1)原料配制：取外表层、芯层和内表层所需物料分别制得外表层原料、芯层原料和内表层原料；
2)三层共挤：取外表层原料、芯层原料和内表层原料利用三层共挤技术制得薄膜A；
3)纵向拉伸：取薄膜A进行纵向拉伸，制得薄膜B；
4)横向拉伸：取薄膜B进行横向拉伸，制得薄膜C；
5)加工处理：取薄膜C进行热处理并时效处理，分切制得成品热封薄膜。
进一步的，所述步骤1)原料配制包括以下步骤：
a)芯层原料制备：
取碳酸钠溶于去离子水，加入十二烷基硫酸钠、聚乙烯醇于40～60℃温度下，加热搅拌25～35min，制得混合溶液，取纳米玻璃粉置于氯化钙水溶液中进行搅拌，加入混合溶液持续搅拌45～75s，降低搅拌速度并超声处理21～27h，取产物洗涤除水后加入偶联剂溶液，搅拌并超声处理20～30min，然后置于100～120℃温度下进行烘干，烘干时间为 1～4h，制得负载有碳酸钙的纳米玻璃粉；
取均聚聚丙烯、氢化石油树脂加热熔融，并搅拌混合，再分别加入负载有碳酸钙的纳米玻璃粉、成核剂、稳定剂、抗氧剂混合均匀，制得芯层原料；
在上述技术方案中，碳酸钠与氯化钙反应生成碳酸钙，在十二烷基硫酸钠、聚乙烯醇的作用下形成尺寸较小的中空球状碳酸钙，降低碳酸钙颗粒的各向异性，提高所制芯层的表面规整度，并与纳米玻璃粉结合，提高光反射，达到提高表面光泽度的效果，所生成的碳酸钙具有较大的比表面积，在偶联剂的作用下提高物料在体系中的分散度，吸附成核剂与之互连，协同作用，诱导结晶；由于碳酸钙与纳米玻璃粉结合，使得以纳米玻璃粉为中心进行辐射结晶，能够增加成核中心的吸引力，加强对聚丙烯分子运动的限制，提高结构稳定性，降低表面能，促进结晶行为，使得所制芯层能够吸收并传递外界应力，达到增韧、增强、耐热稳定的效果，增加晶核密度，降低球晶尺寸，促进芯层透明度的提高；同时碳酸钙和纳米玻璃粉能够吸引通过芯层的水气，体积扩大堵塞微孔，防止水气持续通过对烟草造成损害；
氢化石油树脂选用C5石油树脂，能够提高所制芯层的韧性和表面平滑度，具有良好的相容性和增粘性，提高所制芯层与外表层、内表层的结合强度，且耐热性、稳定性好，促进所制芯层性能的提高；稳定剂选用邻羟基苯甲酸苯酯、2-羟基-4-正辛氧基二苯甲酮、 4-苯甲酰氧基-2，2，6，6-四甲基哌啶中的一种或多种，能够吸收紫外光、进行光温度，提高所制芯层抗紫外线能力。
b)外表层原料制备：
取纳米玻璃粉置于偶联剂溶液中浸渍20～30min，烘干后加入抗静电剂于45～65℃温度下搅拌15～25min，制得改性抗静电剂；
取石英缓慢加热至870～1050℃，保温10～20min，冷却至室温，加入水滑石充分研磨，过筛后加入偶联剂溶液，搅拌并超声处理20～30min，烘干后加入水杨酸乙基己酯，搅拌1～4h，制得改性水杨酸乙基己酯；
取无规共聚聚丙烯、乙烯-1-辛烯共聚物、聚醚改性硅油加热熔融，并搅拌混合，再分别加入改性水杨酸乙基己酯、改性抗静电剂、成核剂、爽滑剂混合均匀，制得外表层原料；
在上述技术方案中，纳米玻璃粉与抗静电剂结合，使得抗静电剂与纳米玻璃粉协同浮出，向外表层的表面迁移，防止抗静电剂磨蚀，提高所制外表层的光学性能和润滑性，并提高外表层的机械强度，防止外表层受损，影响烟膜的美观度；石英能够防止所制外表层与外界的粘连，水滑石能够对外表层进行增强，提高外表层的热稳定性，并提高所制烟膜的尺寸稳定性和挺度；水杨酸乙基己酯能够阻挡紫外线并提高所制外表层的光泽度；将石英缓慢加热并保温，促进石英的晶型转变，提高石英的体积，形成较为疏松的层片状石英，再与水滑石混合，在偶联剂的作用下与水杨酸乙基己酯键合、填充，提高所制外表层的柔韧性，降低所制外表层中的孔隙，所制外表层的机械强度；
使用无规共聚聚丙烯为主要树脂，能够改善所制外表层的光学性能，确保外表层的透明度、力学性能、化学稳定性和水气隔离性能，所添加的乙烯-1-辛烯共聚物能够提高所制外表层的柔韧性和机械强度，并提高外表层的热封性，所添加的聚醚改性硅油能够防止水气凝结，提高所制外表层的透光率。
c)内表层原料制备：
取乳酸钠、吡咯烷酮羧酸钠溶于去离子水，加入月桂酸单甘油酯于30～40℃温度下剪切乳化3～5min，制得改性月桂酸单甘油酯；
取纳米玻璃粉置于偶联剂溶液搅拌并超声处理20～30min，然后置于100～120℃温度下进行烘干，烘干时间为1～4h，制得改性纳米玻璃粉；
取无规共聚聚丙烯、乙烯-1-辛烯共聚物、聚醚改性硅油加热熔融，分别加入柠檬酸三乙酯、改性月桂酸单甘油酯、改性纳米玻璃粉和抗氧剂混合均匀，制得内表层原料。
在上述技术方案中，月桂酸单甘油酯、乳酸钠能够抗菌、抑菌，且乳酸钠、吡咯烷酮羧酸钠具有保鲜、抗氧化性、保湿性，能够阻隔水气向烟草渗透，利用月桂酸单甘油酯乳化，将乳酸钠、吡咯烷酮羧酸钠乳化包裹，添加入内表层后达到缓释的效果，提高内表层抗菌、隔绝水气的时限，达到长效防护效果；所添加的柠檬酸三乙酯通过柠檬酸和乙醇在催化剂的作用下于物料沸腾状态进行反应，保持体系中乙醇过量的状态，并去除反应生成的水，最后蒸馏制得无毒柠檬酸三乙酯，无有毒溶剂和物质的残留，安全可靠，能够提高所制内表层的耐光性和抗霉性，与其他物料协同作用，保护包装内的烟草品质稳定。
进一步的，所述纳米玻璃粉的制备包括以下步骤：
取氢氧化钠溶液加入聚山梨酯-80和植物油，剪切乳化并超声处理10～15min，制得乳化溶液；取硝酸锌、硝酸铝溶于乙醇水溶液，加入乳化溶液混合均匀，静置12～18h，水洗烘干后，制得铝酸锌胶体；取正硅酸乙酯和无水乙醇搅拌混合，并加入盐酸水溶液持续搅拌1～3h，静置18～24h，制得二氧化硅胶体；
取碳酸锌、氢氧化铝、长石、二氧化钛混合研磨，过筛后与二氧化硅胶体混合，置于1000～ 1200℃温度下进行烧结，烧结时间为1～2h，取出速冷，再次进行研磨，加入铝酸锌胶体置于245～270℃温度下保温1～2h，研磨过筛，制得纳米玻璃粉。
在上述技术方案中，碳酸锌烧结生成氧化锌，能够吸收和散射紫外线，达到抗紫外线的功能；氢氧化铝烧结生成氧化铝，耐压性能好，能够提高所制纳米玻璃粉的强度；长石烧结生成氧化钾、二氧化硅、氧化铝等，其中氧化钾溶解部分二氧化硅和氧化铝，生成玻璃相，填充烧结产物的骨架空隙，促进玻璃粉的烧结，提高所制产物的机械强度，提高所制玻璃粉的透明度，并降低玻璃粉的膨胀系数，增加弹性，提高所制纳米玻璃粉的热稳定性；二氧化钛烧结生成二氧化钛粉末，具有抗紫外线、抗菌作用；二氧化硅胶体烧结后生成二氧化硅，能够促进流动，达到润滑、抗黏的效果；铝酸锌胶体烧结后生成铝酸锌，能够阻隔紫外线，热稳定性、机械性能较好；
碳酸锌、氢氧化铝、长石、二氧化钛研磨后，与二氧化硅胶体混合，使得烧结产物表面均包裹、负载有二氧化硅，再与铝酸锌胶体混合烧结，使其表面均附着有铝酸锌，实现所制纳米玻璃粉的高透明性能，能够促进纳米玻璃粉中的成分均匀分布，消除物料团聚，制得的纳米玻璃粉表面具有多孔结构，能够达到除味、抗菌效果，保持包装内烟草的洁净，同时能够防止纳米玻璃粉在原料中的沉降，保证所制膜层的性状和尺寸的稳定性，且多孔结构能够提高所制膜层的亲水性，提高所制膜层的表面润湿性，避免水雾凝结，影响美观，因其表面的二氧化硅和铝酸锌，能够促进原料体系的黏度降低，防止所制烟膜与外界物质粘黏，提高原料体系流动性，降低加工难度，并提高拉伸强度、断裂伸长率等机械强度；
在芯层原料中，碳酸钙沉积于纳米玻璃粉表面的孔隙中，在碳酸钙与成核剂发挥作用时，能够提高对结晶晶体的吸收强度，降低所需自由能，达到促进结晶、降低温度依赖的效果，以纳米玻璃粉为中心进行辐射结晶，提高结晶晶体生长的紊乱度，促进晶体断裂分散形成新的球晶，提高结晶效果；
在外表层原料中，纳米玻璃粉通过偶联剂与抗静电剂结合，使得纳米玻璃粉的表面负载、填充有抗静电剂，形成球状体系向外表层的表面迁移，提高外表层表面强度，提高其耐磨性，在抗静电剂部分磨蚀时，纳米玻璃粉在抗静电剂的作用下偏转，同时降低了体系粘度，防止外表层与外界体系粘黏，提高其润滑性，避免抗静电剂的磨蚀殆尽，促进外表层抗静电功能的长久有效，同时提高外表层的透明度和光泽度，润湿度和粘度，防止水雾形成，提高烟膜的美观度；
在内表层原料中，纳米玻璃粉与偶联剂结合，能够促进其在物料体系中的分散均一性，在水气通过内表层时，能够对其进行吸引，防止水气渗透，同时抗菌、抑菌，杜绝细菌滋生环境，隔绝空气、水气，达到保持包装内烟草洁净的效果。
进一步的，所述步骤2)三层共挤的工艺参数为：共挤温度为175～195℃，冷却时降温速度为2～5℃/min。
进一步的，所述步骤3)纵向拉伸和步骤4)横向拉伸的工艺参数为：
纵向拉伸温度为90～120℃，纵向拉伸倍数为5.8～6.3倍，横向拉伸温度为120～135 ℃，横向拉伸倍数为6.5～8倍。
进一步的，所述步骤5)加工处理包括以下步骤：取薄膜C置于120～135℃温度下保温3～5min，松弛30～75s，并以10～30℃/min快速降温至36～56℃，避光静置3～11d，此时环境温度为20～28℃，相对湿度为55～65％，最后分切制得成品。
在上述技术方案中，在三层共挤工艺中以慢速冷却能够促进烟膜成核，有利于烟膜强度的提高；双向拉伸工艺中，横向和纵向的拉伸倍数相差不大，能够减少拉伸后造成的表面纹络；热处理及其参数设定能够消除膜层在拉伸时产生的微孔，并对晶核进行稳定，防止水气通过，然后松弛以降低热收缩率，冷却将结晶晶格固定，避免结晶过度，时效处理使得抗静电剂浮出，其他组分稳定，促进所制烟膜的性能均匀稳定。
与现有技术相比，本发明所达到的有益效果是：本发明双向拉伸聚丙烯热封薄膜及其制备工艺，通过对双向拉伸膜层结构、组分成分及其制备工艺的设置，实现所制烟膜性能的提高，提高了所制烟膜的强度和机械性能、光泽度，润湿度，并提高其耐磨性、水气阻隔能力，能够有效防止水气凝结、渗透，保持现有烟草品质和烟膜外观。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
1)原料配制：
取氢氧化钠溶液加入聚山梨酯-80和植物油，剪切乳化并超声处理10min，制得乳化溶液；取2.9重量份硝酸锌、7.5重量份硝酸铝溶于乙醇水溶液，加入乳化溶液混合均匀，静置12h，水洗烘干后，制得铝酸锌胶体；取18重量份正硅酸乙酯和无水乙醇搅拌混合，并加入盐酸水溶液持续搅拌1h，静置18h，制得二氧化硅胶体；取12.5重量份碳酸锌、7.8 重量份氢氧化铝、25重量份长石长石、0.8重量份二氧化钛混合研磨，过筛后与二氧化硅胶体混合，置于1000℃温度下进行烧结，烧结时间为1h，取出速冷，再次进行研磨，加入铝酸锌胶体置于245℃温度下保温1h，研磨过筛，制得纳米玻璃粉；
取碳酸钠溶于去离子水，加入十二烷基硫酸钠、聚乙烯醇于40℃温度下，加热搅拌25min，制得混合溶液，取纳米玻璃粉置于氯化钙水溶液中进行搅拌，加入混合溶液持续搅拌45s，降低搅拌速度并超声处理21h，取产物洗涤除水后加入偶联剂溶液，搅拌并超声处理20min，然后置于100℃温度下进行烘干，烘干时间为1h，制得负载有碳酸钙的纳米玻璃粉；取均聚聚丙烯、氢化石油树脂加热熔融，并搅拌混合，再分别加入负载有碳酸钙的纳米玻璃粉、成核剂、稳定剂、抗氧剂混合均匀，此时芯层包括以下重量组分：87 份均聚聚丙烯、5份氢化石油树脂、0.8份纳米玻璃粉、0.4份碳酸钙、0.25份成核剂、 0.2份稳定剂、0.01份抗氧剂，制得芯层原料；
取纳米玻璃粉置于偶联剂溶液中浸渍20min，烘干后加入抗静电剂于45℃温度下搅拌 15min，制得改性抗静电剂；取石英缓慢加热至870℃，保温10min，冷却至室温，加入水滑石充分研磨，过筛后加入偶联剂溶液，搅拌并超声处理20min，烘干后加入水杨酸乙基己酯，搅拌1h，制得改性水杨酸乙基己酯；取无规共聚聚丙烯、乙烯-1-辛烯共聚物、聚醚改性硅油加热熔融，并搅拌混合，再分别加入改性水杨酸乙基己酯、改性抗静电剂、成核剂、爽滑剂混合均匀，此时外表层包括以下重量组分：93份无规共聚聚丙烯、5份乙烯 -1-辛烯共聚物、0.3份水滑石、1份石英、0.8份纳米玻璃粉、0.1份聚醚改性硅油、0.5 份水杨酸乙基己酯、0.25份成核剂、2份抗静电剂、0.05份爽滑剂，制得外表层原料；
取乳酸钠、吡咯烷酮羧酸钠溶于去离子水，加入月桂酸单甘油酯于30℃温度下剪切乳化3min，制得改性月桂酸单甘油酯；取纳米玻璃粉置于偶联剂溶液搅拌并超声处理20min，然后置于100℃温度下进行烘干，烘干时间为1h，制得改性纳米玻璃粉；取无规共聚聚丙烯、乙烯-1-辛烯共聚物、聚醚改性硅油加热熔融，分别加入柠檬酸三乙酯、改性月桂酸单甘油酯、改性纳米玻璃粉和抗氧剂混合均匀，此时内表层包括以下重量组分： 93份无规共聚聚丙烯、5份乙烯-1-辛烯共聚物、0.1份聚醚改性硅油、0.5份柠檬酸三乙酯、0.2份月桂酸单甘油酯、0.1份纳米玻璃粉、0.2份乳酸钠、0.2份吡咯烷酮羧酸钠/ 脯氨酸、0.01份抗氧剂，制得内表层原料；
2)三层共挤：取外表层原料、芯层原料和内表层原料利用三层共挤技术制备薄膜，其中共挤温度为175℃，冷却时降温速度为2℃/min，得到薄膜A；
3)纵向拉伸：取薄膜A进行纵向拉伸，其中纵向拉伸温度为90℃，纵向拉伸倍数为5.8倍，制得薄膜B；
4)横向拉伸：取薄膜B进行横向拉伸，其中横向拉伸温度为120℃，横向拉伸倍数为6.5倍，制得薄膜C；
5)加工处理：取薄膜C置于120℃温度下保温3min，松弛30s，并以10℃/min快速降温至36℃，避光静置3d，此时环境温度为20℃，相对湿度为55％，最后分切制得成品热封薄膜。
实施例2
1)原料配制：
取氢氧化钠溶液加入聚山梨酯-80和植物油，剪切乳化并超声处理12min，制得乳化溶液；取4.5重量份硝酸锌、11重量份硝酸铝溶于乙醇水溶液，加入乳化溶液混合均匀，静置15h，水洗烘干后，制得铝酸锌胶体；取24重量份正硅酸乙酯和无水乙醇搅拌混合，并加入盐酸水溶液持续搅拌2h，静置21h，制得二氧化硅胶体；取25重量份碳酸锌、11 重量份氢氧化铝、26重量份长石长石、1.6重量份二氧化钛混合研磨，过筛后与二氧化硅胶体混合，置于1100℃温度下进行烧结，烧结时间为1.5h，取出速冷，再次进行研磨，加入铝酸锌胶体置于257℃温度下保温1.5h，研磨过筛，制得纳米玻璃粉；
取碳酸钠溶于去离子水，加入十二烷基硫酸钠、聚乙烯醇于20℃温度下，加热搅拌30min，制得混合溶液，取纳米玻璃粉置于氯化钙水溶液中进行搅拌，加入混合溶液持续搅拌60s，降低搅拌速度并超声处理24h，取产物洗涤除水后加入偶联剂溶液，搅拌并超声处理25min，然后置于110℃温度下进行烘干，烘干时间为2.5h，制得负载有碳酸钙的纳米玻璃粉；取均聚聚丙烯、氢化石油树脂加热熔融，并搅拌混合，再分别加入负载有碳酸钙的纳米玻璃粉、成核剂、稳定剂、抗氧剂混合均匀，此时芯层包括以下重量组分：90 份均聚聚丙烯、7份氢化石油树脂、1.0份纳米玻璃粉、0.6份碳酸钙、1.3份成核剂、0.3 份稳定剂、0.1份抗氧剂，制得芯层原料；
取纳米玻璃粉置于偶联剂溶液中浸渍25min，烘干后加入抗静电剂于55℃温度下搅拌 20min，制得改性抗静电剂；取石英缓慢加热至960℃，保温15min，冷却至室温，加入水滑石充分研磨，过筛后加入偶联剂溶液，搅拌并超声处理25min，烘干后加入水杨酸乙基己酯，搅拌2.5h，制得改性水杨酸乙基己酯；取无规共聚聚丙烯、乙烯-1-辛烯共聚物、聚醚改性硅油加热熔融，并搅拌混合，再分别加入改性水杨酸乙基己酯、改性抗静电剂、成核剂、爽滑剂混合均匀，此时外表层包括以下重量组分：94份无规共聚聚丙烯、7份乙烯-1-辛烯共聚物、0.4份水滑石、1.5份石英、1份纳米玻璃粉、0.2份聚醚改性硅油、 0.8份水杨酸乙基己酯、1.3份成核剂、2.7份抗静电剂、0.17份爽滑剂，制得外表层原料；
取乳酸钠、吡咯烷酮羧酸钠溶于去离子水，加入月桂酸单甘油酯于35℃温度下剪切乳化4min，制得改性月桂酸单甘油酯；取纳米玻璃粉置于偶联剂溶液搅拌并超声处理25min，然后置于110℃温度下进行烘干，烘干时间为2h，制得改性纳米玻璃粉；取无规共聚聚丙烯、乙烯-1-辛烯共聚物、聚醚改性硅油加热熔融，分别加入柠檬酸三乙酯、改性月桂酸单甘油酯、改性纳米玻璃粉和抗氧剂混合均匀，此时内表层包括以下重量组分： 94份无规共聚聚丙烯、7份乙烯-1-辛烯共聚物、0.2份聚醚改性硅油、1份柠檬酸三乙酯、0.3 份月桂酸单甘油酯、0.5份纳米玻璃粉、0.6份乳酸钠、0.3份吡咯烷酮羧酸钠/脯氨酸、 0.1份抗氧剂，制得内表层原料；
2)三层共挤：取外表层原料、芯层原料和内表层原料利用三层共挤技术制备薄膜，其中共挤温度为185℃，冷却时降温速度为3.5℃/min，得到薄膜A；
3)纵向拉伸：取薄膜A进行纵向拉伸，其中纵向拉伸温度为105℃，纵向拉伸倍数为6倍，制得薄膜B；
4)横向拉伸：取薄膜B进行横向拉伸，其中横向拉伸温度为127℃，横向拉伸倍数为7.7倍，制得薄膜C；
5)加工处理：取薄膜C置于127℃温度下保温4min，松弛52s，并以20℃/min快速降温至46℃，避光静置7d，此时环境温度为24℃，相对湿度为60％，最后分切制得成品热封薄膜。
实施例3
1)原料配制：
取氢氧化钠溶液加入聚山梨酯-80和植物油，剪切乳化并超声处理15min，制得乳化溶液；取6.0重量份硝酸锌、15.0重量份硝酸铝溶于乙醇水溶液，加入乳化溶液混合均匀，静置18h，水洗烘干后，制得铝酸锌胶体；取30重量份正硅酸乙酯和无水乙醇搅拌混合，并加入盐酸水溶液持续搅拌3h，静置24h，制得二氧化硅胶体；取37.6重量份碳酸锌、15重量份氢氧化铝、27重量份长石长石、2.4重量份二氧化钛混合研磨，过筛后与二氧化硅胶体混合，置于1200℃温度下进行烧结，烧结时间为2h，取出速冷，再次进行研磨，加入铝酸锌胶体置于270℃温度下保温2h，研磨过筛，制得纳米玻璃粉；
取碳酸钠溶于去离子水，加入十二烷基硫酸钠、聚乙烯醇于60℃温度下，加热搅拌35min，制得混合溶液，取纳米玻璃粉置于氯化钙水溶液中进行搅拌，加入混合溶液持续搅拌75s，降低搅拌速度并超声处理27h，取产物洗涤除水后加入偶联剂溶液，搅拌并超声处理30min，然后置于120℃温度下进行烘干，烘干时间为4h，制得负载有碳酸钙的纳米玻璃粉；取均聚聚丙烯、氢化石油树脂加热熔融，并搅拌混合，再分别加入负载有碳酸钙的纳米玻璃粉、成核剂、稳定剂、抗氧剂混合均匀，此时芯层包括以下重量组分：92 份均聚聚丙烯、10份氢化石油树脂、1.2份纳米玻璃粉、0.8份碳酸钙、2.5份成核剂、 0.5份稳定剂、0.2份抗氧剂，制得芯层原料；
取纳米玻璃粉置于偶联剂溶液中浸渍30min，烘干后加入抗静电剂于65℃温度下搅拌 25min，制得改性抗静电剂；取石英缓慢加热至1050℃，保温20min，冷却至室温，加入水滑石充分研磨，过筛后加入偶联剂溶液，搅拌并超声处理30min，烘干后加入水杨酸乙基己酯，搅拌4h，制得改性水杨酸乙基己酯；取无规共聚聚丙烯、乙烯-1-辛烯共聚物、聚醚改性硅油加热熔融，并搅拌混合，再分别加入改性水杨酸乙基己酯、改性抗静电剂、成核剂、爽滑剂混合均匀，此时外表层包括以下重量组分：95份无规共聚聚丙烯、9份乙烯-1-辛烯共聚物、0.6份水滑石、2份石英、1.2份纳米玻璃粉、0.3份聚醚改性硅油、 1.2份水杨酸乙基己酯、2.5份成核剂、3.5份抗静电剂、0.3份爽滑剂，制得外表层原料；
取乳酸钠、吡咯烷酮羧酸钠溶于去离子水，加入月桂酸单甘油酯于40℃温度下剪切乳化5min，制得改性月桂酸单甘油酯；取纳米玻璃粉置于偶联剂溶液搅拌并超声处理30min，然后置于120℃温度下进行烘干，烘干时间为4h，制得改性纳米玻璃粉；取无规共聚聚丙烯、乙烯-1-辛烯共聚物、聚醚改性硅油加热熔融，分别加入柠檬酸三乙酯、改性月桂酸单甘油酯、改性纳米玻璃粉和抗氧剂混合均匀，此时内表层包括以下重量组分： 95份无规共聚聚丙烯、9份乙烯-1-辛烯共聚物、0.3份聚醚改性硅油、1.5份柠檬酸三乙酯、0.5份月桂酸单甘油酯、1.0份纳米玻璃粉、1份乳酸钠、0.5份吡咯烷酮羧酸钠/脯氨酸、0.2份抗氧剂，制得内表层原料；
2)三层共挤：取外表层原料、芯层原料和内表层原料利用三层共挤技术制备薄膜，其中共挤温度为195℃，冷却时降温速度为5℃/min，得到薄膜A；
3)纵向拉伸：取薄膜A进行纵向拉伸，其中纵向拉伸温度为120℃，纵向拉伸倍数为6.3倍，制得薄膜B；
4)横向拉伸：取薄膜B进行横向拉伸，其中横向拉伸温度为135℃，横向拉伸倍数为8倍，制得薄膜C；
5)加工处理：取薄膜C置于135℃温度下保温5min，松弛75s，并以30℃/min快速降温至56℃，避光静置1d，此时环境温度为28℃，相对湿度为65％，最后分切制得成品热封薄膜。
对比例1
与实施例2相比，对比例1的芯层、外表层、内表层中均去除了组分纳米玻璃粉，其余步骤、参数与实施例2相同。
对比例2
与实施例2相比，对比例2中的纳米玻璃粉的制备工艺为：取氢氧化钠溶液加入聚山梨酯-80和植物油，剪切乳化并超声处理15min，制得乳化溶液；取6.0重量份硝酸锌、15.0重量份硝酸铝溶于乙醇水溶液，加入乳化溶液混合均匀，静置18h，水洗烘干后，制得铝酸锌胶体；取30重量份正硅酸乙酯和无水乙醇搅拌混合，并加入盐酸水溶液持续搅拌3h，静置24h，制得二氧化硅胶体；取37.6重量份碳酸锌、15重量份氢氧化铝、27重量份长石长石、2.4重量份二氧化钛混合研磨，过筛后与二氧化硅胶体、铝酸锌胶体混合，置于1200℃温度下进行烧结，烧结时间为2h，取出研磨过筛，制得纳米玻璃粉；其余步骤、参数与实施例2相同。
对比例3
与实施例2相比，对比例3中的原料直接添加，未对物料进行改性，即步骤1)中芯层、外表层、内表层原料配制工艺为：
取90份均聚聚丙烯、7份氢化石油树脂加热熔融，并搅拌混合，再分别加入1.0份纳米玻璃粉、0.6份碳酸钙、1.3份成核剂、0.3份稳定剂、0.1份抗氧剂混合均匀，制得芯层原料；
取94份无规共聚聚丙烯、7份乙烯-1-辛烯共聚物、0.2份聚醚改性硅油加热熔融，并搅拌混合，再分别加入0.4份水滑石、1.5份石英、1份纳米玻璃粉、0.8份水杨酸乙基己酯、1.3份成核剂、2.7份抗静电剂、0.17份爽滑剂混合均匀，制得外表层原料；
取94份无规共聚聚丙烯、7份乙烯-1-辛烯共聚物、0.2份聚醚改性硅油加热熔融，分别加入1份柠檬酸三乙酯、0.3份月桂酸单甘油酯、0.5份纳米玻璃粉、0.6份乳酸钠、0.3份吡咯烷酮羧酸钠/脯氨酸、0.1份抗氧剂混合均匀，制得内表层原料；其余步骤、参数与实施例2相同。
实验
取实施例1-3、对比例1-3中制备得到的烟膜和常规烟膜，分别对其雾度、光泽度、拉伸强度、断裂伸长率、热收缩率、水气渗透率、外表层的动摩擦系数进行测试，实验标准为YC/T266-2008，记录检测结果，得到如下数据：
其中光泽度的实验条件为45℃，水气渗透率的实验条件为38℃、90％RH。
根据上表中的数据，可以清楚得到以下结论：
实施例1-3、对比例1-3中制备得到的烟膜和常规烟膜形成对照实验，检测结果可知，实施例1-3中烟膜与常规烟膜相比，其雾度、光泽度、拉伸强度明显上升，断裂伸长率、热收缩率、水气渗透率、外表层的动摩擦系数明显下降，可知本发明实现了对光学性能、力学性能、水气阻隔性能和耐摩擦性能的提升；且实施例2与对比例1-3相比，其雾度、光泽度、拉伸强度、断裂伸长率、热收缩率、水气渗透率、外表层的动摩擦系数数值略有不同，整体呈性能改善趋势，可知纳米玻璃粉组分的设置及制备工艺、对芯层、外表层、内表层原料的改性均对烟膜性能的改善有着促进作用，这充分说明了本发明能够有效提高烟膜的光学性能、力学性能、水气阻隔性能和耐摩擦性能，具有较高实用性。
需要说明的是，在本文中，诸如第一和第二等之类的关系术语仅仅用来将一个实体或者操作与另一个实体或操作区分开来，而不一定要求或者暗示这些实体或操作之间存在任何这种实际的关系或者顺序。而且，术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者设备所固有的要素。
最后应说明的是：以上所述仅为本发明的优选实施例而已，并不用于限制本发明，尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (10)
1.一种双向拉伸聚丙烯热封薄膜，包括外表层、芯层和内表层，其特征在于：所述热封薄膜自上而下由外表层、芯层、内表层三层结构共挤制得，所述芯层包括以下重量组分：87～92份均聚聚丙烯、5～10份氢化石油树脂、0.8～1.2份纳米玻璃粉、0.4～0.8份碳酸钙、0.25～2.5份成核剂、0.2～0.5份稳定剂、0.01～0.2份抗氧剂。
2.根据权利要求1所述的一种双向拉伸聚丙烯热封薄膜，其特征在于：所述外表层包括以下重量组分：93～95份无规共聚聚丙烯、5～9份乙烯-1-辛烯共聚物、0.3～0.6份水滑石、1～2份石英、0.8～1.2份纳米玻璃粉、0.1～0.3份聚醚改性硅油、0.5～1.2份水杨酸乙基己酯、0.25～2.5份成核剂、2～3.5份抗静电剂、0.05～0.3份爽滑剂。
3.根据权利要求1所述的一种双向拉伸聚丙烯热封薄膜，其特征在于：所述内表层包括以下重量组分：93～95份无规共聚聚丙烯、5～9份乙烯-1-辛烯共聚物、0.1～0.3份聚醚改性硅油、0.5～1.5份柠檬酸三乙酯、0.2～0.5份月桂酸单甘油酯、0.1～1.0份纳米玻璃粉、0.2～1份乳酸钠、0.2～0.5份吡咯烷酮羧酸钠/脯氨酸、0.01～0.2份抗氧剂。
4.根据权利要求1所述的一种双向拉伸聚丙烯热封薄膜，其特征在于：所述纳米玻璃粉所需原料包括以下重量组分：2.9～6.0份硝酸锌、7.5～15.0份硝酸铝、12.5～37.6份碳酸锌、0.8～2.4份二氧化钛、7.8～15份氢氧化铝、25～27份长石、18～30份正硅酸乙酯。
5.一种双向拉伸聚丙烯热封薄膜的制备工艺，其特征在于，包括以下步骤：
1)原料配制：取外表层、芯层和内表层所需物料分别制得外表层原料、芯层原料和内表层原料；
2)三层共挤：取外表层原料、芯层原料和内表层原料利用三层共挤技术制得薄膜A；
3)纵向拉伸：取薄膜A进行纵向拉伸，制得薄膜B；
4)横向拉伸：取薄膜B进行横向拉伸，制得薄膜C；
5)加工处理：取薄膜C进行热处理并时效处理，分切制得成品热封薄膜。
6.根据权利要求5所述的一种双向拉伸聚丙烯热封薄膜的制备工艺，其特征在于：所述步骤1)原料配制包括以下步骤：
a)芯层原料制备：
取碳酸钠溶于去离子水，加入十二烷基硫酸钠、聚乙烯醇于40～60℃温度下，加热搅拌25～35min，制得混合溶液，取纳米玻璃粉置于氯化钙水溶液中进行搅拌，加入混合溶液持续搅拌45～75s，降低搅拌速度并超声处理21～27h，取产物洗涤除水后加入偶联剂溶液，搅拌并超声处理20～30min，然后置于100～120℃温度下进行烘干，烘干时间为1～4h，制得负载有碳酸钙的纳米玻璃粉；
取均聚聚丙烯、氢化石油树脂加热熔融，并搅拌混合，再分别加入负载有碳酸钙的纳米玻璃粉、成核剂、稳定剂、抗氧剂混合均匀，制得芯层原料；
b)外表层原料制备：
取纳米玻璃粉置于偶联剂溶液中浸渍20～30min，烘干后加入抗静电剂于45～65℃温度下搅拌15～25min，制得改性抗静电剂；
取石英缓慢加热至870～1050℃，保温10～20min，冷却至室温，加入水滑石充分研磨，过筛后加入偶联剂溶液，搅拌并超声处理20～30min，烘干后加入水杨酸乙基己酯，搅拌1～4h，制得改性水杨酸乙基己酯；
取无规共聚聚丙烯、乙烯-1-辛烯共聚物、聚醚改性硅油加热熔融，并搅拌混合，再分别加入改性水杨酸乙基己酯、改性抗静电剂、成核剂、爽滑剂混合均匀，制得外表层原料；
c)内表层原料制备：
取乳酸钠、吡咯烷酮羧酸钠溶于去离子水，加入月桂酸单甘油酯于30～40℃温度下剪切乳化3～5min，制得改性月桂酸单甘油酯；
取纳米玻璃粉置于偶联剂溶液搅拌并超声处理20～30min，然后置于100～120℃温度下进行烘干，烘干时间为1～4h，制得改性纳米玻璃粉；
取无规共聚聚丙烯、乙烯-1-辛烯共聚物、聚醚改性硅油加热熔融，分别加入柠檬酸三乙酯、改性月桂酸单甘油酯、改性纳米玻璃粉和抗氧剂混合均匀，制得内表层原料。
7.根据权利要求6所述的一种双向拉伸聚丙烯热封薄膜的制备工艺，其特征在于：所述纳米玻璃粉的制备包括以下步骤：
取氢氧化钠溶液加入聚山梨酯-80和植物油，剪切乳化并超声处理10～15min，制得乳化溶液；取硝酸锌、硝酸铝溶于乙醇水溶液，加入乳化溶液混合均匀，静置12～18h，水洗烘干后，制得铝酸锌胶体；取正硅酸乙酯和无水乙醇搅拌混合，并加入盐酸水溶液持续搅拌1～3h，静置18～24h，制得二氧化硅胶体；
取碳酸锌、氢氧化铝、长石、二氧化钛混合研磨，过筛后与二氧化硅胶体混合，置于1000～1200℃温度下进行烧结，烧结时间为1～2h，取出速冷，再次进行研磨，加入铝酸锌胶体置于245～270℃温度下保温1～2h，研磨过筛，制得纳米玻璃粉。
8.根据权利要求5所述的一种双向拉伸聚丙烯热封薄膜的制备工艺，其特征在于：所述步骤2)三层共挤的工艺参数为：共挤温度为175～195℃，冷却时降温速度为2～5℃/min。
9.根据权利要求5所述的一种双向拉伸聚丙烯热封薄膜的制备工艺，其特征在于：所述步骤3)纵向拉伸和步骤4)横向拉伸的工艺参数为：
纵向拉伸温度为90～120℃，纵向拉伸倍数为5.8～6.3倍，横向拉伸温度为120～135℃，横向拉伸倍数为6.5～8倍。
10.根据权利要求5所述的一种双向拉伸聚丙烯热封薄膜的制备工艺，其特征在于：所述步骤5)加工处理包括以下步骤：取薄膜C置于120～135℃温度下保温3～5min，松弛30～75s，并以10～30℃/min快速降温至36～56℃，避光静置3～11d，此时环境温度为20～28℃，相对湿度为55～65％，最后分切制得成品。
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