CN114407462A - 一种具有高表面能的双向拉伸聚丙烯基膜 - Google Patents
一种具有高表面能的双向拉伸聚丙烯基膜 Download PDFInfo
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Abstract
一种具有高表面能的双向拉伸聚丙烯基膜，由以下至少五层结构通过共挤出和双向拉伸工艺制成，五层结构在基膜厚度方向上依次为：外层、钩链层、主拉伸层、过渡层和内层，外层是高表面能层，该层能够通过化学键形式来提高基膜与其他膜或层之间的高表面附着力，钩链层是主拉伸层与外层材料之间的极性以及相容性的过渡；主拉伸层是在双向拉伸加工过程中承担主要拉伸任务的功能层；过渡层是主拉伸层与内层材料之间熔融温度的过渡；内层为热封层。本发明通过在表层赋予极性，获得高表面能的基膜，从而实现PE基材表面的高附着力。通过聚烯烃的重量大于或等于基膜总重量的90%的设计，满足了产品易回收、易高值利用的环保要求。
Description
技术领域
本发明涉及聚丙烯薄膜领域，特别涉及一种具有高表面能的双向拉伸聚丙烯基膜。这种聚丙烯基膜其表面能可以达到38达因/cm及其以上。
背景技术
废弃塑料尤其是功能性软包装难以回收再利用是全球高度关注的迫切解决的难题。高阻隔功能性单材化的设计理念是全球软包装新材料发展的首选方向。
市售的高阻隔功能化薄膜，通常以聚酯薄膜为基膜，利用聚酯材料良好的极性，满足基膜与阻隔涂层和阻隔蒸镀层的足够的附着力和持久性，以获得稳定的、可控的、持久的阻隔性能。
聚丙烯是一种表面能较低、表面呈疏水性和惰性的非极性材料，其粘结性、抗静电性、亲水性差，与极性聚合物或无机填料的相容性也不好，这样的客观因素都限制了聚丙烯基膜通过赋能获得高阻隔性。因此，当需要赋予聚乙烯单材化基膜高阻隔而进行复合、阻隔涂层或阻隔蒸镀时，膜的高表面能是被考虑的第一个因素，通常，薄膜的表面能的大小可以通过表面张力来表征，要求基膜表面的张力达到38达因/cm甚至更高。而聚乙烯的表面张力只有31达因/cm甚至更低。
现有技术主要通过对基膜的表面处理技术来增加其表面张力。较为常见的方式是电晕放电处理和极性底涂法。电晕放电采用高频高压或中频高压放电，对塑料表面进行处理，使其表面呈多孔性从而活化，以提高塑料薄膜表面对涂层或镀层的黏附力，改善薄膜的表面能；然而电晕处理虽然能增加表面能，但是处理效果非常不稳定，甚至放置几天后处理效果就消失了，这对于日常生产而言非常不便。而极性底涂是通过对塑料表面进行涂覆，类似于涂胶水的过程，从而提高阻隔镀层在PE基材表面的附着力。然而底涂除了增加了生产工序以及涂料的溶剂问题，同样都存在着环保的问题，不符合我们国家倡导的低碳和VOCs排放要求。因此如何有效提高聚丙烯薄膜的表面能是软包装可回收、再利用功能性单材化材料发展迫切需要解决的关键技术。
鉴于此，如何设计一种高表面能的双向拉伸聚丙烯基膜是本发明研究的课题。
发明内容
本发明提供一种具有高表面能的双向拉伸聚丙烯基膜，其目的是要从结构设计来解决聚丙烯基膜其表面能低的问题。
为达到上述目的，本发明采用的技术方案是：
一种具有高表面能的双向拉伸聚丙烯基膜，所述聚丙烯基膜由以下至少五层结构通过共挤出和双向拉伸工艺制成，所述五层结构在聚丙烯基膜厚度方向上依次为：外层、钩链层、主拉伸层、过渡层和内层，其特征在于：
所述外层是高表面能层，该层能够通过化学键形式来提高基膜与其他膜或层之间的高表面附着力，所述外层的表面张力大于或等于38达因/厘米，所述外层的材料包括含有以下至少一种官能团的聚合物：
羧基；
羟基；
酰胺基；
酯基；
所述聚合物中的官能团按极性的大小排列顺序如下：羧基＞羟基＞酰胺基＞酯基；
所述外层的重量小于或等于聚丙烯基膜总重量的10%；
所述钩链层是指主拉伸层与外层材料之间的极性以及相容性的过渡，以满足界面粘合要求；
所述钩链层的材料包括含有以下至少一种官能团的改性聚烯烃：
羧基；
酯基；
所述改性聚烯烃为改性聚乙烯和/或改性聚丙烯；
所述改性聚烯烃中的官能团按极性的大小排列顺序如下：羧基＞酯基；
所述改性聚烯烃中所使用的官能团的极性大于或等于外层所使用的聚合物中的官能团的极性；
所述钩链层至少为一层；
所述主拉伸层是在双向拉伸加工过程中承担主要拉伸任务的功能层，主拉伸层的重量大于或等于所述聚丙烯基膜总重量的40%，该主拉伸层的材料为聚丙烯，所述主拉伸层至少为一层；
所述过渡层是指主拉伸层与内层材料之间熔融温度的过渡，以满足加工要求，所述过渡层的材料为聚丙烯，所述过渡层至少为一层；
所述内层为热封层，所述内层的材料为聚丙烯，所述内层的重量小于或等于所述聚丙烯基膜总重量的20%；
所述聚丙烯基膜中的聚烯烃的重量大于或等于所述聚丙烯基膜总重量的90%。
其中，所述聚丙烯基膜的外层经过电晕处理以辅助提升表面能。
其中，所述其他膜或层是指通过蒸镀、涂布、复合、印刷工艺手段附着于基膜外层表面的膜或层。其中，所述主拉伸层中聚丙烯的密度大于或等于过渡层中聚丙烯的平均密度，小于或等于过渡层中聚烯烃的平均密度。其中，所述过渡层中聚丙烯或聚烯烃的平均密度大于或等于内层中聚丙烯或聚烯烃的平均密度。
其中，所述基膜可利用物理回收的方法直接回收并进行再利用。
其中，所述基膜3021的热封强度大于或等于6牛/15毫米（即，6N/15mm，N表示牛顿，15mm表示毫米宽度）。
其中，含有改性聚乙烯和改性聚丙烯的统称为改性聚烯烃。
以下为本发明技术方案的相关解释：
1. 表面能是创造物质表面时对分子间化学键破坏的度量。在固体物理理论中，表面原子比物质内部的原子具有更多的能量，因此，根据能量最低原理，原子会自发的趋于物质内部而不是表面。表面能的另一种定义是，材料表面相对于材料内部所多出的能量。表面自由能是物体表面分子间作用力的体现，与固体表面的润湿性能密切相关，在表面化学中具有重要的地位。
2. 镀层/涂层与基膜之间可以通过机械结合、物理吸附等形成氢键和化学键，互相扩散等作用结合在一起，这些作用所产生的附着力，决定了镀膜与基膜之间的层间附着力。
3. 表面能通常跟分子的极性有一定的相关性，分子极性大的，一般表面能相对会高一些，分子极性小的，一般表面能低一些。
4. 有机化学反应主要发生在官能团上，官能团对有机物的性质起决定作用，常见官能团碳碳双键、羟基、羧基、酰胺基、酯基等。
以下为常见官能团的极性大小排列顺序：
烷烃（—CH3，—CH2—）＜烯烃（—CH=CH—）＜酯类（—COOR）＜酰胺（—NHCO—CH3）＜醇类（—OH）＜羧酸类（—COOH）。
5. 下表为常用塑料薄膜的润湿张力值(温度：20摄氏度)：
6. 本发明技术方案中所述的水性阻隔涂层选择聚乙烯醇、聚酯、聚氨酯、丙烯酸中的一种，包括以聚乙烯醇、聚酯、聚氨酯、丙烯酸为主的改性材料，其目的在于快速干燥，提高工艺速度。
7. 固体表面的润湿性由其化学组成和微观结构决定。固体表面自由能越大,越容易被液体润湿,反之亦然。因而,寻求和制备高表面自由能的固体表面成为制备亲水的前提条件。
研究表明,影响材料表面润湿性的主要因素有:材料表面能、表面粗糙度以及表面微/纳结构,本发明中采用的技术方案是通过提高材料表面能的途径来达到本发明的目的，具体是通过化学键形式来提高基膜的表面能，从而提高与其他膜或涂层或镀层之间的附着力。
本发明的设计原理和效果：
1. 本发明技术方案通过在聚丙烯基膜的外层赋予极性，获得具有高表面能，从而实现阻隔镀层或涂层在PP基材表面的高附着力。
2. 本发明PP基膜结构中，内层材料的表面张力（34达因/cm）低于外层材料的表面张力（大于38达因/cm），PE基膜外层的表面润湿良好，从而使镀层或涂层可以牢固地黏附在PE基膜的表面，并不易反粘到内层。
3. 本发明PP基膜结构中，通过在主拉伸层与外层之间设置钩链层，实现了主拉伸层材料与外层材料之间的极性和相容性的过渡，保证了界面之间有可靠的结合力。
4. 本发明PP基膜结构中，聚烯烃的重量大于或等于所述聚丙烯基膜总重量的90%，满足了产品易回收、易再利用的环保要求。
5.本发明采用一步成型的共挤出双向拉伸生产工艺，实现了减量、低碳，无VOCs排放的绿色包装要求，顺应了低碳、清洁生产、易回收、易循环再利用的环保要求。
具体实施方式
下面结合实施例对本发明作进一步描述：
本实施例中所涉及的英文代号的中文含义分别为：
1. 极性聚合物：酯基（EVA为乙烯-醋酸乙烯共聚物、EAA为乙烯丙烯酸甲酯共聚物、EMAA为乙烯-甲基丙烯酸甲酯共聚物）、羟基（EVOH为乙烯-乙烯醇共聚物）、酰胺基（PA6为尼龙6），羧基（马来酸酐接枝烯烃共聚物）；
2. 非极性聚合物：PO为热塑性聚烯烃；PP为聚丙烯、COPP为共聚聚丙烯、LDPE为低密度聚乙烯、MDPE为中密度聚乙烯、HDPE为高密度聚乙烯、MPP为茂金属聚丙烯、MPE为茂金属聚乙烯、TPU为热塑性聚氨酯弹性体橡胶、EPP为聚丙烯发泡（本实施例中EPP为PP线上发泡，即挤出加工过程中发泡）。
下表为实施例中所用材料的典型密度：
实施例1：
钩链层所含官能团（羧基）的极性大于外层所含官能团（羟基）的极性；
高表面层的表面张力为50达因/厘米，大于38达因/厘米。
实施例2：
钩链层所含官能团（羧基）的极性大于外层所含官能团（羟基）的极性；
高表面层的表面张力为46达因/厘米，大于38达因/厘米。
实施例3：
钩链层所含官能团（酯基）的极性等于外层所含官能团（酯基）的极性；
高表面层的表面张力为40达因/厘米，大于38达因/厘米。
实施例4：
钩链层所含官能团（酯基）的极性等于外层所含官能团（酯基）的极性；
高表面层的表面张力为40达因/厘米，大于38达因/厘米。
本实施例可热封。
实施例5：
钩链层所含官能团（酯基）的极性等于外层所含官能团（酯基）的极性；
高表面层的表面张力为40达因/厘米，大于38达因/厘米。
本实施例可热封。
实施例6：
钩链层所含官能团（羧基）的极性大于外层所含官能团（羟基）的极性；
高表面层的表面张力为40达因/厘米，大于38达因/厘米。
实施例7：
钩链层所含官能团（酯基）的极性等于外层所含官能团（酯基）的极性；
高表面层的表面张力为40达因/厘米，大于38达因/厘米。
实施例8：
钩链层所含官能团（酯基）的极性等于外层所含官能团（酯基）的极性；
高表面层的表面张力为42达因/厘米，大于38达因/厘米。
实施例9：
钩链层所含官能团（酯基）的极性等于外层所含官能团（酯基）的极性；
高表面层的表面张力为42达因/厘米，大于38达因/厘米。
本领域技术人员知晓的是，EPP（聚丙烯发泡）的密度要低于典型密度。
以上实施例皆可电晕提高表面能。
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。
Claims (7)
1.一种具有高表面能的双向拉伸聚丙烯基膜，所述聚丙烯基膜由以下至少五层结构通过共挤出和双向拉伸工艺制成，所述五层结构在聚丙烯基膜厚度方向上依次为：外层、钩链层、主拉伸层、过渡层和内层，其特征在于：
所述外层是高表面能层，该层能够通过化学键形式来提高基膜与其他膜或层之间的高表面附着力，所述外层的表面张力大于或等于38达因/厘米，所述外层的材料包括含有以下至少一种官能团的聚合物：
羧基；
羟基；
酰胺基；
酯基；
所述聚合物中的官能团按极性的大小排列顺序如下：羧基＞羟基＞酰胺基＞酯基；
所述外层的重量小于或等于聚丙烯基膜总重量的10%；
所述钩链层是指主拉伸层与外层材料之间的极性以及相容性的过渡，以满足界面粘合要求；
所述钩链层的材料包括含有以下至少一种官能团的改性聚烯烃：
羧基；
酯基；
所述改性聚烯烃为改性聚乙烯和/或改性聚丙烯；
所述改性聚烯烃中的官能团按极性的大小排列顺序如下：羧基＞酯基；
所述改性聚烯烃中所使用的官能团的极性大于或等于外层所使用的聚合物中的官能团的极性；
所述钩链层至少为一层；
所述主拉伸层是在双向拉伸加工过程中承担主要拉伸任务的功能层，主拉伸层的重量大于或等于所述聚丙烯基膜总重量的40%，该主拉伸层的材料为聚丙烯，所述主拉伸层至少为一层；
所述过渡层是指主拉伸层与内层材料之间熔融温度的过渡，以满足加工要求，所述过渡层的材料为聚丙烯，所述过渡层至少为一层；
所述内层为热封层，所述内层的材料为聚丙烯，所述内层的重量小于或等于所述聚丙烯基膜总重量的20%；
所述聚丙烯基膜中的聚烯烃的重量大于或等于所述聚丙烯基膜总重量的90%。
2.根据权利要求1中所述的聚丙烯基膜，其特征在于：所述聚丙烯基膜的外层经过电晕处理以辅助提升表面能。
3.根据权利要求1中所述的聚丙烯基膜，其特征在于：所述其他膜或层是指通过蒸镀、涂布、复合、印刷工艺手段附着于基膜外层表面的膜或层。
4.根据权利要求1中所述的聚丙烯基膜，其特征在于：所述主拉伸层中聚丙烯的密度大于或等于过渡层中聚丙烯的平均密度，小于或等于过渡层中聚烯烃的平均密度。
5.根据权利要求1中所述的聚丙烯基膜，其特征在于：所述过渡层中聚丙烯或聚烯烃的平均密度大于或等于内层中聚丙烯或聚烯烃的平均密度。
6.根据权利要求1-5之一中所述的聚丙烯基膜，其特征在于：所述基膜可利用物理回收的方法直接回收并进行再利用。
7.根据权利要求1-5之一中所述的聚丙烯基膜，其特征在于：所述基膜的热封强度大于或等于6牛/15毫米。
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