TWI405666B - 阻氣熱封複合膜及包含此複合膜之真空絕熱板 - Google Patents

阻氣熱封複合膜及包含此複合膜之真空絕熱板 Download PDF

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TWI405666B
TWI405666B TW099142987A TW99142987A TWI405666B TW I405666 B TWI405666 B TW I405666B TW 099142987 A TW099142987 A TW 099142987A TW 99142987 A TW99142987 A TW 99142987A TW I405666 B TWI405666 B TW I405666B
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gas barrier
layer
heat seal
composite film
film according
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TW099142987A
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TW201223765A (en
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Ray Hsu
Dan Cheng Kong
Chang Ming Wong
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Ind Tech Res Inst
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Priority to CN201010610021.7A priority patent/CN102555369B/zh
Priority to US13/050,817 priority patent/US8747986B2/en
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Description

阻氣熱封複合膜及包含此複合膜之真空絕熱板
本發明係有關於一種阻氣熱封材料，特別是有關於一種阻氣熱封複合膜及包含此複合膜之真空絕熱板。
高阻氣性膜材具有極高的氣體阻隔性及可撓性，用於真空密封或阻氣包裝，杜絕顯著氣體穿透之效果，可長達數年之久。在傳統常用阻氣膜材中，塑膠膜材的阻氣性遠無法達到上述要求。玻璃材料雖具有良好氣體阻隔性，但其製作耗能、幾無可撓性及厚重等缺點使其應用不易。金屬膜材如鋁箔則有製作耗能及不可回收的缺點，且其高導熱性使其不適合應用於特定產品(如真空絕熱板)。有鑒於單一材料無法達到理想性質，複合膜材如蒸鍍金屬、SiOx 之塑膠膜材遂被發明出來，以同時達到可撓及高阻氣特性。惟其阻氣性質仍需作顯著提升。
本發明之一實施例，提供一種阻氣熱封複合膜，包括：一熱封層，係由超低密度聚乙烯(very low density polyethylene,VLDPE)、低密度聚乙烯(low density polyethylene,LDPE)、線型低密度聚乙烯(linear low density polyethylene,LLDPE)、高密度聚乙烯(high density polyethylene,HDPE)、茂金屬聚乙烯(metallocene polyethylene,mPE)、茂金屬線型低密度聚乙烯(metallocene linear low density polyethylene,mLLDPE)、乙烯-醋酸乙烯共聚物(ethylene vinyl acetate,EVA)、乙烯-丙烯(ethylene-propylene,EP)共聚物或乙烯-丙烯-丁烯(ethylene-propylene-butene,EPB)三聚物所構成；以及一阻氣層，包括複數個複合層，形成於該熱封層上，每一該複合層包括一高分子基材與單層或複數層之金屬或其氧化物層，形成於該高分子基材之單面或雙面上，其中該高分子基材係由單軸或雙軸延伸之聚對苯二甲酸乙二醇酯(polyethylene terephthalate,PET)、聚對苯二甲酸丁二醇酯(polybutylene terephthalate,PBT)、聚亞醯胺(polyimide,PI)、乙烯-乙烯醇(ethylene/vinyl alcohol,EVOH)共聚物或其組合所構成。
本發明阻氣熱封複合膜更包括至少一前導物(primer)層，形成於該高分子基材與該金屬或其氧化物層之間或該等金屬或其氧化物層之間。該前導物(primer)層係由聚氨酯丙烯酸酯(urethane acrylate)、環氧丙烯酸酯(epoxy acrylate)、有機矽丙烯酸酯(silicone acrylate)或其混合物所構成。本發明阻氣熱封複合膜更包括一保護層，形成於該阻氣層上。該保護層係由單軸或雙軸延伸之聚對苯二甲酸乙二醇酯(polyethylene terephthalate,PET)、聚醯胺(polyamide,PA)、聚對萘二甲酸乙酯(poly(ethylene-2,6-naphthalate),PEN)或聚亞醯胺(polyimide,PI)所構成。
本發明阻氣熱封複合膜結構包含三部分，依序為：保護層、高阻氣複合層及氣密熱封層。結構中，保護層提供可印刷特性及保護其內之高阻氣複合層免於物理性損害；高阻氣複合層可提供高阻氣特性；氣密熱封層則提供可熱封性質。而於高阻氣複合層中導入的前導物(primer)層，可促進金屬接著及阻氣效果。
本發明提供一種可繞性、高阻氣性、質輕、節能、可回收之阻氣熱封複合膜，取代傳統可繞式鋁箔高阻氣膜，適合應用於高阻氣食品、藥物包裝材及冷凍櫃、冰箱、冰庫、建築物之真空絕熱板，作為節能減碳材。其氧氣穿透率可小於0.01 cc/m2 day‧atm；水蒸氣穿透率可小於0.01g/m2 day；熱封強度大於1,500g/25mm。此外，本發明阻氣熱封複合膜製程節能簡單，適合捲對捲(roll to roll)生產，且由於複合膜中的熱封層Tg小於零度，因此，在低溫應用下耐候性佳。
本發明之一實施例，提供一種真空絕熱板(vacuum insulation panel,VIP)，包括：一發泡材，該發泡材之密度小於0.1g/cm3 ，開孔率大於90%，氣泡大小為小於250μm，可承受壓力大於1kg/cm2 ；以及一上述之阻氣熱封複合膜，包覆該發泡材，該阻氣複合膜之氧氣穿透率小於0.01cc/m2 day‧atm，水蒸氣穿透率小於0.01cc/m2 day。
為讓本發明之上述目的、特徵及優點能更明顯易懂，下文特舉一較佳實施例，作詳細說明如下：
本發明之一實施例，提供一種阻氣熱封複合膜，包括一熱封層，由超低密度聚乙烯(very low density polyethylene,VLDPE)、低密度聚乙烯(low density polyethylene,LDPE)、線型低密度聚乙烯(linear low density polyethylene,LLDPE)、高密度聚乙烯(high density polyethylene,HDPE)、茂金屬聚乙烯(metallocene polyethylene,mPE)、茂金屬線型低密度聚乙烯(metallocene linear low density polyethylene,mLLDPE)、乙烯-醋酸乙烯共聚物(ethylene vinyl acetate,EVA)、乙烯-丙烯(ethylene-propylene,EP)共聚物或乙烯-丙烯-丁烯(ethylene-propylene-butene,EPB)三聚物所構成，以及一阻氣層，包括複數個(至少二個)複合層，形成於熱封層上，每一複合層包括一高分子基材與單層或複數層之金屬或其氧化物層，其中單層或複數層之金屬或其氧化物層形成於高分子基材之單面或雙面上，高分子基材由單軸或雙軸延伸之聚對苯二甲酸乙二醇酯(polyethylene terephthalate,PET)、聚對苯二甲酸丁二醇酯(polybutylene terephthalate,PBT)、聚亞醯胺(polyimide,PI)、乙烯-乙烯醇(ethylene/vinyl alcohol,EVOH)共聚物或其組合(例如表面形成有乙烯-乙烯醇(EVOH)共聚物之聚對苯二甲酸乙二醇酯(PET))所構成。
上述金屬或其氧化物層可包括週期表第三周期或第四周期之金屬元素及其氧化物(例如Al、Cr、Cu、Ti、Zn、Al2 O3 、CaO、TiO2 或ZnO等)。在一實施例中，藉由例如真空蒸鍍法(vacuum evaporation)形成單層或複數層之金屬或其氧化物層於高分子基材之單面或雙面上。
本發明阻氣熱封複合膜中更包括至少一前導物(primer)層，形成於高分子基材與金屬或其氧化物層之間或兩金屬或其氧化物層之間，以促進金屬接著及阻氣效果。前導物(primer)層可由聚氨酯丙烯酸酯(urethane acrylate)、環氧丙烯酸酯(epoxy acrylate)、有機矽丙烯酸酯(silicone acrylate)或其混合物所構成。
本發明阻氣熱封複合膜中更包括一保護層，形成於阻氣層上。保護層可由單軸或雙軸延伸之聚對苯二甲酸乙二醇酯(polyethylene terephthalate,PET)、聚醯胺(polyamide,PA)、聚對萘二甲酸乙酯(poly(ethylene-2,6-naphthalate),PEN)或聚亞醯胺(polyimide,PI)所構成。
本發明阻氣熱封複合膜中更包括一接合膠層，形成於熱封層、阻氣層與保護層之間以及阻氣層中之兩複合層之間，以貼合熱封層、阻氣層與保護層以及阻氣層中之兩複合層。接合膠可包括環氧樹脂系、聚氨酯系、壓克力系、纖維素系或低密度聚乙烯。
上述熱封層之厚度介於12~100微米，較佳介於20~60微米。上述高分子基材之厚度介於10~50微米，較佳介於12~25微米。上述金屬或其氧化物層之厚度介於30~100奈米，較佳為40~80奈米。上述保護層之厚度介於12~50微米，較佳介於12~25微米。
本發明阻氣熱封複合膜結構包含三部分，依序為：保護層、高阻氣複合層及氣密熱封層。結構中，保護層提供可印刷特性及保護其內之高阻氣複合層免於物理性損害；高阻氣複合層可提供高阻氣特性；氣密熱封層則提供可熱封性質。而於高阻氣複合層中導入的前導物(primer)層，可促進金屬接著及阻氣效果。
本發明提供一種可繞性、高阻氣性、質輕、節能、可回收之阻氣熱封複合膜，取代傳統可繞式鋁箔高阻氣膜，適合應用於高阻氣食品、藥物包裝材及冷凍櫃、冰箱、冰庫、建築物之真空絕熱板，作為節能減碳材。其氧氣穿透率可小於0.01 cc/m2 day‧atm；水蒸氣穿透率可小於0.01g/m2 day；熱封強度大於1,500g/25mm。此外，本發明阻氣熱封複合膜製程節能簡單，適合捲對捲(roll to roll)生產，且由於複合膜中的熱封層Tg小於零度，因此，在低溫應用下耐候性佳。
本發明之一實施例，提供一種真空絕熱板(vacuum insulation panel,VIP)，包括一發泡材，發泡材之密度小於0.1g/cm3 ，開孔率大於90%，氣泡尺寸小於250μm，較佳小於100μm，可承受壓力大於1kg/cm2 ，以及一上述之阻氣熱封複合膜，包覆發泡材，阻氣複合膜之氧氣穿透率小於0.01cc/m2 day‧atm，水蒸氣穿透率小於0.01cc/m2 day。
上述發泡材可由開孔性之聚苯乙烯(polystyrene,PS)或聚丙烯(polypropylene,PP)所構成。
本發明真空絕熱板之熱傳導係數小於0.01W/m‧k。
【實施例1】 本發明阻氣熱封複合膜之製作(1)
以蒸鍍、貼合方式製作多層複合膜，請參閱第1圖，由上而下分別為：PET保護膜10(厚度為13μm)，環氧樹脂接合膠層12(厚度為7μm)，雙面鍍鋁之PET膜14(PET 16厚度為17μm，鋁膜18厚度為30nm，前導物(primer)層20厚度為7μm)，環氧樹脂接合膠層22(厚度為7μm)，雙面鍍鋁之PET膜24(PET26厚度為17μm，鋁膜28厚度為30nm，前導物(primer)層30厚度為7μm)，環氧樹脂接合膠層32(厚度為7μm)，PE氣密熱封層34(厚度為60μm)。此實施例製作之阻氣熱封複合膜其氧氣穿透率小於0.01cc/m2 day‧atm；熱封強度大於1,500g/25mm。
【實施例2】 本發明阻氣熱封複合膜之製作(2)
以蒸鍍、貼合方式製作多層複合膜，請參閱第2圖，由上而下分別為：單面蒸鍍二層鋁膜之PET膜36(PET 38厚度為17μm，鋁膜40厚度為30nm，前導物(primer)層42厚度為7μm，蒸鍍面朝向環氧樹脂接合膠層44)，環氧樹脂接合膠層44(厚度為7μm)，單面蒸鍍二層鋁膜之PET膜46(PET 48厚度為17μm，鋁膜50厚度為30nm，前導物(primer)層52厚度為7μm，蒸鍍面朝向環氧樹脂接合膠層44)，環氧樹脂接合膠層54(厚度為7μm)，EP共聚物氣密熱封層56(厚度為60μm)。此實施例製作之阻氣熱封複合膜其氧氣穿透率小於0.01cc/m2 day‧atm；水蒸氣穿透率小於0.01g/m2 day；熱封強度大於1,500g/25mm。
【實施例3】 本發明阻氣熱封複合膜之製作(3)
以蒸鍍、貼合方式製作多層複合膜，請參閱第3圖，由上而下分別為：PET保護膜58(厚度為13μm)，環氧樹脂接合膠層60(厚度為7μm)，雙面鍍鋁之PET膜62(PET 64厚度為17μm，鋁膜66厚度為30nm，前導物(primer)層68厚度為7μm)，環氧樹脂接合膠層70(厚度為7μm)，單面鍍鋁之EVOH膜72(EVOH 74厚度為20μm，乙烯含量為44%，鋁膜76厚度為30nm，蒸鍍面朝向與鋁膜76相接著之環氧樹脂接合膠層70)，環氧樹脂接合膠層78(厚度為7μm)，PE氣密熱封層80(厚度為60μm)。此實施例製作之阻氣熱封複合膜其氧氣穿透率小於0.01cc/m2 day‧atm；熱封強度大於1,500g/25mm。
【實施例4】 本發明真空絕熱板中發泡材之製作
本實施例所使用之材料為分子量介於20萬到30萬之間的聚苯乙烯(PS)。首先是PS與其他樹脂(例如低密度聚乙烯(low density polyethylene,LDPE))和填充劑(例如碳酸鈣、碳黑)和成核劑(例如硬脂酸鈣、硬脂酸鋅)在150℃~200℃之下利用押出機將PS樹脂與其他添加劑混鍊均勻，並製造成為PS樹脂粒狀物，再利用連續方式製造發泡材。連續方式的製程以Tandem方式排列兩押出機，兩押出機互相連接，第二支押出機連接模頭。PS樹脂粒狀物放入第一支押出機，其作用為熔融PS樹脂、灌入氣體例如二氧化碳(CO2 )和混合氣體與PS樹脂，溫度設定為180℃~220℃之間；第二支押出機用於冷卻及輸送熔融混合氣體的PS樹脂到達模頭，溫度設定為120℃~140℃之間，熔融混合氣體的PS樹脂經過模頭產生發泡材，模頭壓力設定值可為800psi~2000psi。此實施例製作之發泡材其密度為0.05~0.09g/cm3 ，氣泡尺寸為80~250μm，開孔率大於95%，可承受壓力大於1 kg/cm2 。
【實施例5】 本發明真空絕熱板之製作
PS樹脂經過連續方式製程，以CO2 為發泡氣體，得到開孔PS發泡板材(製作方法如實施例4所揭示)，再放入阻氣熱封複合膜袋(製作方法如實施例1~3所揭示)，抽真空及熱封成為真空絕熱板，真空壓力必須低於0.75torr(1mbar)。此實施例製作之真空絕熱板其熱傳導係數為0.006~0.01w/m‧k。
雖然本發明已以較佳實施例揭露如上，然其並非用以限定本發明，任何熟習此項技藝者，在不脫離本發明之精神和範圍內，當可作更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。
10、58．．．PET保護膜
12、22、32、44、54、60、70、78．．．接合膠層
14、24、62．．．雙面鍍鋁之PET膜
16、26、38、48、64．．．PET
18、28、40、50、66、76．．．鋁膜
20、30、42、52、68．．．前導物層
34、80．．．PE氣密熱封層
36、46．．．單面蒸鍍二層鋁膜之PET膜
56．．．EP共聚物氣密熱封層
72．．．單層鍍鋁之EVOH膜
74．．．EVOH
第1圖係根據本發明之一實施例，一種阻氣熱封複合膜結構；
第2圖係根據本發明之一實施例，一種阻氣熱封複合膜結構；
第3圖係根據本發明之一實施例，一種阻氣熱封複合膜結構；以及
第4圖係根據本發明之一實施例，一種開孔PS發泡體內部結構圖。
10．．．PET保護膜
12、22、32．．．接合膠層
14、24．．．雙面鍍鋁之PET膜
16、26．．．PET
18、28．．．鋁金屬膜
20、30．．．前導物層
34．．．PE氣密熱封層

Claims (16)

  1. 一種阻氣熱封複合膜，包括：一熱封層，係由超低密度聚乙烯(very low density polyethylene,VLDPE)、低密度聚乙烯(low density polyethylene,LDPE)、線型低密度聚乙烯(linear low density polyethylene,LLDPE)、高密度聚乙烯(high density polyethylene,HDPE)、茂金屬聚乙烯(metallocene polyethylene,mPE)、茂金屬線型低密度聚乙烯(metallocene linear low density polyethylene,mLLDPE)、乙烯-醋酸乙烯共聚物(ethylene vinyl acetate,EVA)、乙烯-丙烯(ethylene-propylene,EP)共聚物或乙烯-丙烯-丁烯(ethylene-propylene-butene,EPB)三聚物所構成；以及一阻氣層，包括複數個複合層，形成於該熱封層上，每一該複合層包括複數層之金屬或其氧化物層形成於一高分子基材之單面或雙面上，其中該高分子基材係由單軸或雙軸延伸之聚對苯二甲酸乙二醇酯(polyethylene terephthalate,PET)、聚對苯二甲酸丁二醇酯(polybutylene terephthalate,PBT)、聚亞醯胺(polyimide,PI)、乙烯-乙烯醇(ethylene/vinyl alcohol，EVOH)共聚物或其組合所構成。
  2. 如申請專利範圍第1項所述之阻氣熱封複合膜，其中該金屬或其氧化物層係由週期表第三周期或第四周期之金屬元素或其氧化物所構成。
  3. 如申請專利範圍第2項所述之阻氣熱封複合膜，其中該金屬或其氧化物層包括Al、Cr、Cu、Ti、Zn、Al2 O3 、CaO、TiO2 或ZnO。
  4. 如申請專利範圍第1項所述之阻氣熱封複合膜，更包括至少一前導物(primer)層，形成於該高分子基材與該金屬或其氧化物層之間或該等金屬或其氧化物層之間。
  5. 如申請專利範圍第4項所述之阻氣熱封複合膜，其中該前導物(primer)層係由聚氨酯丙烯酸酯(urethane acrylate)、環氧丙烯酸酯(epoxy acrylate)、有機矽丙烯酸酯(silicone acrylate)或其混合物所構成。
  6. 如申請專利範圍第1項所述之阻氣熱封複合膜，更包括一保護層，形成於該阻氣層上。
  7. 如申請專利範圍第6項所述之阻氣熱封複合膜，其中該保護層係由單軸或雙軸延伸之聚對苯二甲酸乙二醇酯(polyethylene terephthalate,PET)、聚醯胺(polyamide,PA)、聚對萘二甲酸乙酯(poly(ethylene-2,6-naphthalate),PEN)或聚亞醯胺(polyimide,PI)所構成。
  8. 如申請專利範圍第6項所述之阻氣熱封複合膜，更包括一接合膠，形成於該熱封層、該阻氣層與該保護層之間以及該阻氣層中之該等複合層之間。
  9. 如申請專利範圍第1項所述之阻氣熱封複合膜，其中該熱封層之厚度介於12~100微米。
  10. 如申請專利範圍第1項所述之阻氣熱封複合膜，其中該高分子基材之厚度介於12~50微米。
  11. 如申請專利範圍第1項所述之阻氣熱封複合膜，其中該金屬或其氧化物層之厚度介於30~100奈米。
  12. 如申請專利範圍第1項所述之阻氣熱封複合膜，其中該保護層之厚度介於12~50微米。
  13. 一種真空絕熱板，包括：一發泡材，該發泡材之密度小於0.1g/cm3 ，開孔率大於90%，氣泡尺寸為小於250μm，可承受壓力大於1kg/cm2 ；以及一如申請專利範圍第1項所述之阻氣熱封複合膜，包覆該發泡材，該阻氣複合膜之氧氣穿透率小於0.01cc/m2 day‧atm，水蒸氣穿透率小於0.01cc/m2 day。
  14. 如申請專利範圍第13項所述之真空絕熱板，其中該發泡材係由開孔性之聚苯乙烯或聚丙烯所構成。
  15. 如申請專利範圍第13項所述之真空絕熱板，其中該發泡材之氣泡尺寸小於100μm。
  16. 如申請專利範圍第13項所述之真空絕熱板，其中該真空絕熱板之熱傳導係數小於0.01W/m‧k。
TW099142987A 2010-12-09 2010-12-09 阻氣熱封複合膜及包含此複合膜之真空絕熱板 TWI405666B (zh)

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