CN102555369B - 阻气热封复合膜及包含此复合膜的真空绝热板 - Google Patents

阻气热封复合膜及包含此复合膜的真空绝热板 Download PDF

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CN102555369B
CN102555369B CN201010610021.7A CN201010610021A CN102555369B CN 102555369 B CN102555369 B CN 102555369B CN 201010610021 A CN201010610021 A CN 201010610021A CN 102555369 B CN102555369 B CN 102555369B
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徐瑞鸿
龚丹诚
翁彰明
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Abstract

本发明提供一种阻气热封复合膜，包括：一热封层，是由超低密度聚乙烯、低密度聚乙烯、线型低密度聚乙烯、高密度聚乙烯、茂金属聚乙烯、茂金属线型低密度聚乙烯、乙烯-醋酸乙烯共聚物、乙烯-丙烯共聚物或乙烯-丙烯-丁烯三聚物所构成；以及一阻气层，包括多个复合层，形成于该热封层上，每一复合层包括单层或多层的金属或其氧化物层形成于一高分子基材的单面或双面上，其中该高分子基材是由单轴或双轴延伸的聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚酰亚胺、乙烯-乙烯醇共聚物、或其组合所构成。本发明亦提供一种包含此复合膜的真空绝热板。

Description

阻气热封复合膜及包含此复合膜的真空绝热板
技术领域
本发明是涉及一种阻气热封材料，特别是涉及一种阻气热封复合膜及包含此复合膜的真空绝热板。
背景技术
高阻气性膜材具有极高的气体阻隔性及可挠性，用于真空密封或阻气包装，杜绝显著气体穿透的效果，可长达数年之久。在传统常用阻气膜材中，塑料膜材的阻气性远无法达到上述要求。玻璃材料虽具有良好气体阻隔性，但其制作耗能、几无可挠性及厚重等缺点使其应用不易。金属膜材如铝箔则有制作耗能及不可回收的缺点，且其高导热性使其不适合应用于特定产品(如真空绝热板)。有鉴于单一材料无法达到理想性质，复合膜材如蒸镀金属、SiOx的塑料膜材遂被发明出来，以同时达到可挠及高阻气特性。惟其阻气性质仍需作显著提升。
发明内容
本发明的目的在于提供一种兼具可挠性和高阻气性的阻气热封复合膜。
本发明的一实施方式，提供一种阻气热封复合膜，包括：一热封层，是由超低密度聚乙烯(verylowdensitypolyethylene，VLDPE)、低密度聚乙烯(lowdensitypolyethylene，LDPE)、线型低密度聚乙烯(linearlowdensitypolyethylene，LLDPE)、高密度聚乙烯(highdensitypolyethylene，HDPE)、茂金属聚乙烯(metallocenepolyethylene，mPE)、茂金属线型低密度聚乙烯(metallocenelinearlowdensitypolyethylene，mLLDPE)、乙烯-醋酸乙烯共聚物(ethylenevinylacetate，EVA)、乙烯-丙烯(ethylene-propylene，EP)共聚物、或乙烯-丙烯-丁烯(ethylene-propylene-butene，EPB)三聚物所构成；以及一阻气层，包括多个复合层，形成于该热封层上，每一所述复合层包括一高分子基材与单层或多层的金属或其氧化物层，形成于该高分子基材的单面或双面上，其中该高分子基材是由单轴或双轴延伸的聚对苯二甲酸乙二醇酯(polyethyleneterephthalate，PET)、聚对苯二甲酸丁二醇酯(polybutyleneterephthalate，PBT)、聚酰亚胺(polyimide，PI)、乙烯-乙烯醇(ethylene/vinylalcohol，EVOH)共聚物、或其组合所构成。
本发明的阻气热封复合膜还包括至少一前导物(primer)层，形成于所述该高分子基材与所述金属或其氧化物层之间或所述金属或其氧化物层之间。该前导物层是由聚氨酯丙烯酸酯(urethaneacrylate)、环氧丙烯酸酯(epoxyacrylate)、有机硅丙烯酸酯(siliconeacrylate)、或其混合物所构成。本发明的阻气热封复合膜还包括一保护层，形成于该阻气层上。该保护层是由单轴或双轴延伸的聚对苯二甲酸乙二醇酯(PET)、聚酰胺(polyamide，PA)、聚萘二甲酸乙酯(poly(ethylene-2，6-naphthalate)，PEN)、或聚酰亚胺(PI)所构成。
本发明的阻气热封复合膜结构包含三部分，依序为：保护层、高阻气复合层及气密热封层。结构中，保护层提供可印刷特性及保护其内的高阻气复合层免于物理性损害；高阻气复合层可提供高阻气特性；气密热封层则提供可热封性质。而于高阻气复合层中导入的前导物层，可促进金属接着及阻气效果。
本发明提供一种可挠性、高阻气性、质轻、节能、可回收的阻气热封复合膜，取代传统可挠式铝箔高阻气膜，适合应用于高阻气食品、药物包装材及冷冻柜、冰箱、冰库、建筑物的真空绝热板，作为节能减碳材。其氧气穿透率可小于0.01cc/m2day·atm；水蒸气穿透率可小于0.01g/m2day；热封强度大于1,500g/25mm。此外，本发明的阻气热封复合膜制备工艺节能简单，适合卷对卷(rolltoroll)生产，且由于复合膜中的热封层Tg小于零度，因此，在低温应用下耐候性佳。
本发明的一实施方式，提供一种真空绝热板(vacuuminsulationpanel，VIP)，包括：一发泡材，该发泡材的密度小于0.1g/cm3，开孔率大于90％，气泡大小为小于250μm，可承受压力大于1kg/cm2；以及一上述的阻气热封复合膜，包覆该发泡材，该阻气复合膜的氧气穿透率小于0.01cc/m2day·atm，水蒸气穿透率小于0.01cc/m2day。
附图说明
图1是根据本发明的一实施方式的一种阻气热封复合膜结构的示意图；
图2是根据本发明的一实施方式的一种阻气热封复合膜结构的示意图；
图3是根据本发明的一实施方式的一种阻气热封复合膜结构的示意图；以及
图4是根据本发明的一实施方式的一种开孔PS发泡体内部结构图；
其中，主要组件符号说明：
10、58～PET保护膜；
12、22、32、44、54、60、70、78～接合胶层；
14、24、62～双面镀铝的PET膜；
16、26、38、48、64～PET；
18、28、40、50、66、76～铝膜；
20、30、42、52、68～前导物层；
34、80～PE气密热封层；
36、46～单面蒸镀二层铝膜的PET膜；
56～EP共聚物气密热封层；
72～单层镀铝的EVOH膜；
74～EVOH。
为让本发明的上述目的、特征及优点能更明显易懂，下文特举一较佳实施例，作详细说明如下：
具体实施方式
本发明的一实施例，提供一种阻气热封复合膜，包括一热封层，由超低密度聚乙烯(VLDPE)、低密度聚乙烯(LDPE)、线型低密度聚乙烯(LLDPE)、高密度聚乙烯(HDPE)、茂金属聚乙烯(mPE)、茂金属线型低密度聚乙烯(mLLDPE)、乙烯-醋酸乙烯共聚物(EVA)、乙烯-丙烯(EP)共聚物、或乙烯-丙烯-丁烯(EPB)三聚物所构成，以及一阻气层，包括多个(至少二个)复合层，形成于热封层上，每一复合层包括一高分子基材与单层或多层的金属或其氧化物层，其中单层或多层的金属或其氧化物层形成于高分子基材的单面或双面上，高分子基材由单轴或双轴延伸的聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚酰亚胺(PI)、乙烯-乙烯醇(EVOH)共聚物、或其组合(例如表面形成有乙烯-乙烯醇(EVOH)共聚物的聚对苯二甲酸乙二醇酯(PET))所构成。
上述金属或其氧化物层可包括周期表第三周期或第四周期的金属元素及其氧化物(例如Al、Cr、Cu、Ti、Zn、Al2O3、CaO、TiO2或ZnO等)。在一实施例中，藉由例如真空蒸镀法(vacuumevaporation)形成单层或多层的金属或其氧化物层于高分子基材的单面或双面上。
本发明的阻气热封复合膜中还包括至少一前导物层，形成于高分子基材与金属或其氧化物层之间或两金属或其氧化物层之间，以促进金属接着及阻气效果。前导物层可由聚氨酯丙烯酸酯、环氧丙烯酸酯、有机硅丙烯酸酯、或其混合物所构成。
本发明的阻气热封复合膜中还包括一保护层，形成于阻气层上。保护层可由单轴或双轴延伸的聚对苯二甲酸乙二醇酯(PET)、聚酰胺(PA)、聚萘二甲酸乙酯(PEN)、或聚酰亚胺(PI)所构成。
本发明的阻气热封复合膜中还包括一接合胶层，形成于热封层、阻气层与保护层之间以及阻气层中的两复合层之间，以贴合热封层、阻气层与保护层以及阻气层中的两复合层。接合胶可包括环氧树脂系、聚氨酯系、压克力系、纤维素系、或低密度聚乙烯。
上述热封层的厚度介于12～100微米，较佳介于20～60微米。上述高分子基材的厚度介于10～50微米，例如介于12～50微米，较佳介于12～25微米。上述金属或其氧化物层的厚度介于30～100纳米，较佳为40～80纳米。上述保护层的厚度介于12～50微米，较佳介于12～25微米。
本发明的阻气热封复合膜结构包含三部分，依序为：保护层、高阻气复合层及气密热封层。结构中，保护层提供可印刷特性及保护其内的高阻气复合层免于物理性损害；高阻气复合层可提供高阻气特性；气密热封层则提供可热封性质。而于高阻气复合层中导入的前导物层，可促进金属接着及阻气效果。
本发明提供一种可挠性、高阻气性、质轻、节能、可回收的阻气热封复合膜，取代传统可挠式铝箔高阻气膜，适合应用于高阻气食品、药物包装材及冷冻柜、冰箱、冰库、建筑物的真空绝热板，作为节能减碳材。其氧气穿透率可小于0.01cc/m2day·atm；水蒸气穿透率可小于0.01g/m2day；热封强度大于1,500g/25mm。此外，本发明阻气热封复合膜制备工艺节能简单，适合卷对卷生产，且由于复合膜中的热封层Tg小于零度，因此，在低温应用下耐候性佳。
本发明的一实施例，提供一种真空绝热板(VIP)，包括一发泡材，发泡材的密度小于0.1g/cm3，开孔率大于90％，气泡尺寸小于250μm，较佳小于100μm，可承受压力大于1kg/cm2，以及一上述的阻气热封复合膜，包覆发泡材，阻气复合膜的氧气穿透率小于0.01cc/m2day·atm，水蒸气穿透率小于0.01cc/m2day。
上述发泡材可由开孔性的聚苯乙烯(polystyrene，PS)或聚丙烯(polypropylene，PP)所构成。
本发明真空绝热板的热传导系数小于0.01W/m·k。
【实施例1】本发明阻气热封复合膜的制作(1)
以蒸镀、贴合方式制作多层复合膜，请参阅图1，由上而下分别为：PET保护膜10(厚度为13μm)，环氧树脂接合胶层12(厚度为7μm)，双面镀铝的PET膜14(PET16厚度为17μm，铝膜18厚度为30nm，前导物层20厚度为7μm)，环氧树脂接合胶层22(厚度为7μm)，双面镀铝的PET膜24(PET26厚度为17μm，铝膜28厚度为30nm，前导物层30厚度为7μm)，环氧树脂接合胶层32(厚度为7μm)，PE气密热封层34(厚度为60μm)。此实施例制作的阻气热封复合膜其氧气穿透率小于0.01cc/m2day.atm；热封强度大于1,500g/25mm。
【实施例2】本发明阻气热封复合膜的制作(2)
以蒸镀、贴合方式制作多层复合膜，请参阅图2，由上而下分别为：单面蒸镀二层铝膜的PET膜36(PET38厚度为17μm，铝膜40厚度为30nm，前导物层42厚度为7μm，蒸镀面朝向环氧树脂接合胶层44)，环氧树脂接合胶层44(厚度为7μm)，单面蒸镀二层铝膜的PET膜46(PET48厚度为17μm，铝膜50厚度为30nm，前导物层52厚度为7μm，蒸镀面朝向环氧树脂接合胶层44)，环氧树脂接合胶层54(厚度为7μm)，EP共聚物气密热封层56(厚度为60μm)。此实施例制作的阻气热封复合膜其氧气穿透率小于0.01cc/m2day.atm；水蒸气穿透率小于0.01g/m2day；热封强度大于1,500g/25mm。
【实施例3】本发明阻气热封复合膜的制作(3)
以蒸镀、贴合方式制作多层复合膜，请参阅图3，由上而下分别为：PET保护膜58(厚度为13μm)，环氧树脂接合胶层60(厚度为7μm)，双面镀铝的PET膜62(PET64厚度为17μm，铝膜66厚度为30nm，前导物层68厚度为7μm)，环氧树脂接合胶层70(厚度为7μm)，单面镀铝的EVOH膜72(EVOH74厚度为20μm，乙烯含量为44％，铝膜76厚度为30nm，蒸镀面朝向与铝膜76相接着的环氧树脂接合胶层70)，环氧树脂接合胶层78(厚度为7μm)，PE气密热封层80(厚度为60μm)。此实施例制作的阻气热封复合膜其氧气穿透率小于0.01cc/m2day.atm；热封强度大于1,500g/25mm。
【实施例4】本发明真空绝热板中发泡材的制作
本实施例所使用的材料为分子量介于20万到30万之间的聚苯乙烯(PS)。首先是PS与其它树脂(例如低密度聚乙烯(LDPE))和填充剂(例如碳酸钙、碳黑)和成核剂(例如硬脂酸钙、硬脂酸锌)在150℃～200℃之下利用挤出机将PS树脂与其它添加剂混炼均匀，并制造成为PS树脂粒状物，再利用连续方式制造发泡材。连续方式的制备工艺以Tandem方式排列两挤出机，两挤出机互相连接，第二支挤出机连接模头。PS树脂粒状物放入第一支挤出机，其作用为熔融PS树脂、灌入气体例如二氧化碳(CO2)和混合气体与PS树脂，温度设定为180℃～220℃之间；第二支挤出机用于冷却及输送熔融混合气体的PS树脂到达模头，温度设定为120℃～140℃之间，熔融混合气体的PS树脂经过模头产生发泡材，模头压力设定值可为800psi～2000psi。此实施例制作的发泡材其密度为0.05～0.09g/cm3，气泡尺寸为80～250μm，开孔率大于95％，可承受压力大于1kg/cm2。
【实施例5】本发明真空绝热板的制作
PS树脂经过连续方式制程，以CO2为发泡气体，得到开孔PS发泡板材(制作方法如实施例4所揭示)，再放入阻气热封复合膜袋(制作方法如实施例1～3所揭示)，抽真空及热封成为真空绝热板，真空压力必须低于0.75torr(1mbar)。此实施例制作的真空绝热板其热传导系数为0.006～0.01w/m.k。
虽然本发明已以较佳实施例揭露如上，然其并非用以限定本发明，任何熟习此项技艺者，在不脱离本发明的精神和范围内，当可作更动与润饰，因此本发明的保护范围当视后附的权利要求书所界定的范围为准。

Claims (14)

1.一种阻气热封复合膜，包括：
一热封层，是由超低密度聚乙烯、低密度聚乙烯、线型低密度聚乙烯、高密度聚乙烯、茂金属聚乙烯、茂金属线型低密度聚乙烯、乙烯-醋酸乙烯共聚物、乙烯-丙烯共聚物或乙烯-丙烯-丁烯三聚物所构成；以及
一阻气层，由多个复合层所组成，形成于该热封层上，每一所述复合层包括单层或多层的金属层形成于一高分子基材的单面或双面上，其中该高分子基材是由单轴或双轴延伸的聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚酰亚胺、乙烯-乙烯醇共聚物、或其组合所构成，其中至少一所述复合层包括双层的铝层形成于所述聚对苯二甲酸乙二醇酯的高分子基材上；
以及
一前导物层，形成于所述高分子基材与所述金属层之间，或所述金属层之间，其中所述前导物层是由聚氨酯丙烯酸酯、环氧丙烯酸酯、有机硅丙烯酸酯、或其混合物所构成。
2.如权利要求1所述的阻气热封复合膜，其中所述金属层是由周期表第三周期或第四周期的金属元素所构成。
3.如权利要求2所述的阻气热封复合膜，其中所述金属层为Al、Cr、Cu、Ti或Zn。
4.如权利要求1所述的阻气热封复合膜，还包括一保护层，形成于所述阻气层上。
5.如权利要求4所述的阻气热封复合膜，其中所述保护层是由单轴或双轴延伸的聚对苯二甲酸乙二醇酯、聚酰胺、聚萘二甲酸乙酯或聚酰亚胺所构成。
6.如权利要求4所述的阻气热封复合膜，还包括一接合胶，形成于所述热封层、阻气层与保护层之间以及所述阻气层中的这些复合层之间。
7.如权利要求1所述的阻气热封复合膜，其中所述热封层的厚度介于12～100微米。
8.如权利要求1所述的阻气热封复合膜，其中所述高分子基材的厚度介于12～50微米。
9.如权利要求1所述的阻气热封复合膜，其中所述金属层的厚度介于30～100纳米。
10.如权利要求4所述的阻气热封复合膜，其中所述保护层的厚度介于12～50微米。
11.一种真空绝热板，包括：
一发泡材，该发泡材的密度小于0.1g/cm3，开孔率大于90％，气泡尺寸为小于250μm，可承受压力大于1kg/cm2；以及
一如权利要求1所述的阻气热封复合膜，包覆该发泡材，该阻气复合膜的氧气穿透率小于0.01cc/m2day·atm，水蒸气穿透率小于0.01cc/m2day。
12.如权利要求11所述的真空绝热板，其中所述发泡材是由开孔性的聚苯乙烯或聚丙烯所构成。
13.如权利要求11所述的真空绝热板，其中所述发泡材的气泡尺寸小于100μm。
14.如权利要求11所述的真空绝热板，其中所述真空绝热板的热传导系数小于0.01W/m·k。
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