CN109562865B - 增强阻隔的涂料 - Google Patents
增强阻隔的涂料 Download PDFInfo
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- CN109562865B CN109562865B CN201780049067.6A CN201780049067A CN109562865B CN 109562865 B CN109562865 B CN 109562865B CN 201780049067 A CN201780049067 A CN 201780049067A CN 109562865 B CN109562865 B CN 109562865B
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- barrier coating
- coating composition
- gas barrier
- substrate
- film
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- 238000000576 coating method Methods 0.000 title claims abstract description 98
- 239000011248 coating agent Substances 0.000 title claims description 71
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- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 104
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 99
- 239000008199 coating composition Substances 0.000 claims abstract description 99
- 239000000758 substrate Substances 0.000 claims abstract description 50
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 102
- 239000007789 gas Substances 0.000 claims description 101
- 239000010408 film Substances 0.000 claims description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- -1 epoxysilanes Chemical class 0.000 claims description 30
- 239000004698 Polyethylene Substances 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000004971 Cross linker Substances 0.000 claims description 14
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- 230000001070 adhesive effect Effects 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000002105 nanoparticle Substances 0.000 claims description 13
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical group CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 claims description 12
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 6
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- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 claims description 5
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- 150000001299 aldehydes Chemical class 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
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- IEJPPSMHUUQABK-UHFFFAOYSA-N 2,4-diphenyl-4h-1,3-oxazol-5-one Chemical group O=C1OC(C=2C=CC=CC=2)=NC1C1=CC=CC=C1 IEJPPSMHUUQABK-UHFFFAOYSA-N 0.000 claims description 3
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- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 claims description 3
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- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 3
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- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 claims description 3
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- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 3
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
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- 150000001298 alcohols Chemical class 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 2
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 2
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- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 229920006233 biaxially oriented polyamide Polymers 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- HHICRQHZPBOQPI-UHFFFAOYSA-L diazanium;zinc;dicarbonate Chemical compound [NH4+].[NH4+].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O HHICRQHZPBOQPI-UHFFFAOYSA-L 0.000 claims description 2
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 claims description 2
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- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 2
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- ZAGMEZATBBNICO-UHFFFAOYSA-N n'-trimethoxysilylethane-1,2-diamine Chemical compound CO[Si](OC)(OC)NCCN ZAGMEZATBBNICO-UHFFFAOYSA-N 0.000 claims description 2
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims description 2
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Abstract
本发明公开了包含胺改性的聚乙烯醇和乙酰乙酸酯改性的聚乙烯醇的气体和湿气阻隔涂料组合物。本发明的阻隔涂料表现出增强的气体和湿气性质。即使在涂覆的基材反复弯曲之后，本发明的阻隔涂料也保持了气体和湿气性质。
Description
相关申请的交叉引用
本申请要求2016年8月12日提交的美国临时申请No.62/374,052和2016年10月12日提交的美国临时申请No.62/407,105的优先权，其全部内容并入本文。
技术领域
本发明涉及阻气涂料组合物和包含阻气涂料组合物的基材。本发明还涉及包含含有阻气涂料组合物的基材的制品。本发明的阻气涂层显示出良好的阻气效果、水蒸气阻挡效果，并且即使在反复弯曲后也能保持阻隔性。
背景技术
许多包装食品、药品、化妆品等对水分、大气氧气和其他气体敏感。蒸气和香气也可能污染包装内容物。合成塑料，例如热塑性塑料，通常用于制造例如食品、化妆品和药品的包装。塑料包装针对氧气和其他气体以及湿气提供一定程度的保护。然而，通常通过用阻隔涂料组合物涂覆塑料基材来增强包装的阻隔性能。
为了改善阻气性，聚合物膜通常涂有无机层，例如金属或金属氧化物。然而，当这些涂膜暴露于高温和/或湿度时，例如用于包装产品的灭菌或巴氏灭菌，气体阻隔性能降低。另外，这些无机涂层一般相当脆，当基材弯曲时产生裂缝，降低了阻气性。
通常将聚合物膜层压，以生产具有多层的包装材料。层压材料中薄膜层之间的阻气涂层通常会损害一种薄膜与另一种薄膜的粘合性。当材料弯曲时，导致层压层分离，从而降低层压材料的阻气性。
US7,288,313公开了一种层压材料，其由涂覆有薄气相沉积层的基材、气体阻隔中间层和另一薄气相沉积层组成。气相沉积层优选是金属或金属氧化物。气体阻隔中间层包含水溶性聚合物。
JP2002-273812、JP2001-145973、JP2005-335110、US2016/0009942描述了一种透明的柔性层压材料，其抗冲击、抗针孔、耐热和防潮，具有优异的阻气性，并且是可循环利用的。层压材料是包含一种或多种无机氧化物沉积薄膜和阻气涂层的柔性薄膜。阻气涂层包含至少一种水溶性聚合物和至少一种金属醇盐或其衍生物。
JP2003-035590公开了一种透明、柔韧、轻质的层压材料。基膜涂有含有铟-铈氧化物、或铟-铈氧化物和钛氧化物和/或锡氧化物的混合物的氧气阻隔层。还使用了低折射率层，其可以是无机层(例如SiOx或AlOx)或有机高聚物(例如丙烯酸树脂)。
WO2015/157593公开了一种阻气膜，其包括具有至少两个涂层的基材。第一涂层包含无机氧化物、金属氧化物或金属。第二涂层包含多羟基聚合物或含氨基甲酸酯的聚合物。
US2004/0115445描述了一种阻气层压板，其包括涂有三层的基材。第一层是无机氧化物。第二(中间)层至少含有水溶性聚合物组分。第三层是另一种无机氧化物的薄沉积。
AlOx涂层的阻气性描述于Galikhanov等(2015),Effect of aluminum oxidecoating on structural,barrier and electret properties of polyethyleneterephthalate films,Transactions on Dielectrics and Electrical Insulation,Vol.22,No.3,1492-1496中。已显示在无机氧化物涂层上的杂化无机-有机聚合物第二涂层进一步改善了气体阻隔性。参见Amberg-Schwab等(2006),Development of passive andactive barrier coatings on the basis of inorganic-organic polymers,Monatshefte für Chemie,137,657-666。
本领域仍然需要即使在高湿度下和弯曲后也能保持气体阻隔性的阻气涂层。
发明内容
本发明提供了包含含有大体积官能团的聚乙烯醇的阻气涂层。本发明的阻气涂层即使在高温和高湿度下也表现出良好的氧气和湿气的阻隔性能，并且即使在反复弯曲之后也能保持气体和湿气的阻隔性能。
在一个具体方面，本发明提供一种阻气涂料组合物，其包含：
a)胺改性的聚乙烯醇；和
b)乙酰乙酸酯改性的聚乙烯醇。
另一方面，本发明提供了一种通过将本发明的阻气涂料组合物涂覆到基材上并在基材上干燥该阻气涂料组合物来增强基材的阻气性的方法。
在一个实施方案中，本发明提供了包含本发明的阻气涂料组合物的基材。
在另一个实施方案中，本发明提供一种制品，例如包装制品，其包含含有本发明的阻气涂层的基材。
具体实施方式
应理解，前面的一般性描述和以下的详细描述仅是示例性和解释性的，并不限制所要求保护的任何主题。
除非另外定义，否则本文使用的所有技术和科学术语具有与本发明所属领域的技术人员通常理解的含义相同的含义。除非另有说明，否则本文整个公开内容中提及的所有专利、专利申请、公开的申请和出版物、网站和其他公开材料出于任何目的通过引用整体并入本文。
本发明提供一种气体和水分阻隔涂料组合物，其包含一种或多种胺改性的聚乙烯醇(polyvinyl alcohol,PVOH)和一种或多种乙酰乙酸酯改性的PVOH。阻隔涂料组合物可任选包含粘合促进剂和交联剂。本发明的阻隔涂层是透明的柔性涂层，其增强了各种基材的气体和蒸汽阻隔性能。有利地，即使在涂覆的基材(例如具有一般来说非常脆并且通过反复弯曲容易损坏的真空或气相沉积金属层(即金属化膜)的柔性基材)反复弯曲之后，阻隔涂料组合物仍保持阻隔性能。
本发明的增强阻隔涂料组合物具有阻挡芳香剂、氧气和其他气体如二氧化碳和氮气进入的能力。此外，阻隔涂料组合物可用作矿物油屏障，也可用作低分子量可迁移物(例如增塑剂、粘合促进剂、消泡剂和填料)的屏障。本发明的阻隔涂料组合物也是水蒸气阻挡层。本发明的阻隔涂料组合物可用于涂覆并赋予各种材料的阻隔性，特别是需要消除或限制暴露于氧气和水分的食品和药品的包装。
定义
在本申请中，除非另外特别说明，否则单数的使用包括复数。如这里所使用的，单数形式“一”、“一个”和“该”也旨在包括复数形式，除非上下文另有明确说明。
在本申请中，除非另有说明，否则“或”的使用意味着“和/或”。
如本文所使用的，术语“包括”和/或“包含”指定所述特征的存在，但不排除一个或多个其他特征、整数、步骤、操作、元件和/或组件的存在或添加。此外，对于在说明书或权利要求中使用术语“包括”、“具有”、“有”、“具备”、“组成”、“包含”或其变体，这些术语旨在以与“包括”一词相似的方式包容。
如本文所用，“基材”是指可以施加油墨或涂料的任何表面或物体。基材包括但不限于纸、织物、塑料、塑料膜或聚合物膜、玻璃、陶瓷、金属、木材、复合材料等。基材可具有一层或多层金属或金属氧化物，或其他无机材料。
如本文所用，“制品”是指基材或生产的产品。制品的实例包括但不限于：基材，例如纸、织物、塑料、塑料膜或聚合物膜、玻璃、陶瓷、金属、木材、复合材料等；和生产的产品，例如出版物(如小册子)、标签和包装材料(如硬纸板或瓦楞纸板)、容器(如瓶子、罐子)、衣服、聚烯烃(如聚乙烯或聚丙烯)、聚酯(如聚对苯二甲酸乙二醇酯)、金属化箔(例如层压铝箔)、金属化聚酯、金属容器等。
如本文所用，“胺改性的聚乙烯醇”、“胺改性的PVOH”等是指在聚合物主链的结构中具有一个或多个反应性胺基的聚乙烯醇(PVOH)聚合物。反应性胺基可以是侧链和/或末端。
如本文所用，“乙酰乙酸酯改性的聚乙烯醇”、“乙酰乙酸酯改性的PVOH”等是指在聚合物主链的结构中具有一个或多个反应性乙酰乙酸酯基团的PVOH聚合物。反应性乙酰乙酸酯基团可以是侧链和/或末端。
如本文所用，“气体和湿气阻隔涂料组合物”、“阻气涂料组合物”、“阻隔涂料组合物”、“气体和湿气阻隔涂料”、“气体阻隔涂层”、和“阻隔涂层”通常是指在即用状态下施用之前以及在施加到基材上并在基材上干燥之后的本发明的涂层组合物。
如本文所用，范围和量可表示为“约”一个特定值或范围。“约”还旨在包括确切的量。因此，“约5％”表示“约5％”，也表示“5％”。“约5％”意味着在应用或目的的典型实验误差范围内。
气体和湿气阻隔涂层及其用途
本发明的阻隔涂料组合物包含通过向PVOH的主链添加大体积的反应性基团而改性的PVOH。具体地，本发明的阻隔涂料组合物包含胺改性的PVOH和乙酰乙酸酯改性的PVOH。
通常认为向PVOH中加入这些大体积的基团对气体和湿气阻隔性能是有害的。大多数具有阻气性的树脂含有极性基团(例如羟基)以增强分子间相互作用，例如氢键。如果聚合物结构含有三维庞大的官能团，则分子间相互作用将受到阻碍，并且自由体积将增加，导致阻气性能的劣化(例如参见US9,079,381)。PVOH中的氢键是阻隔性能的重要因素，并且引入庞大的基团可以增加自由体积，因此允许气体或水更容易地透过阻挡涂层或印刷膜。另外，通过引入乙酰乙酸酯或胺基团的任何方法降低PVOH的羟基含量对阻隔性能具有不利影响，并且改性水平通常较低(例如小于12mol％)。通常认为已众所周知只有完全水解(即大于或等于96％的水解)的PVOH才会显示出阻隔性能。引入骨架修饰或使用部分水解的PVOH(乙酸酯或其他基团复制修饰)将不会提供所需的阻隔性能，因为氢键被破坏，并引入大的体积或自由体积。因此，如果使用部分水解的PVOH或具有较高改性程度的PVOH，涂层将提供一些抗弯曲性，但如果由于任何原因导致下部的AlOx/SiOx涂层或金属化层受损，则这些涂层将不会提供任何阻隔。
此外，通常认为在单一涂料组合物中同时使用胺改性的PVOH和乙酰乙酸酯改性的PVOH会显著降低适用期，并严重限制其使用。胺官能的PVOH和乙酰乙酸酯官能的PVOH之间的反应可在数小时内产生凝胶，因此在大多数转换器类型应用中组合物可使用的时间非常有限，因为在印刷运行期间需要低粘度。
尽管在阻气组合物中同时使用胺改性的PVOH和乙酰乙酸酯改性的PVOH，但本发明的阻隔涂料组合物有利地不会快速凝胶化，并且具有更长的适用期，因此在更长时间的印刷运行中保持在适合的粘度范围内。
本发明的阻隔涂料组合物的其它优点包括减少对用以提高气体和水蒸汽的性质的纳米微粒(填充材料)的需要，从而减少健康问题；环境更有利，因为没有聚偏二氯乙烯(PVDC)型涂料或挤出薄膜；低薄膜重量应用；以及PVOH溶液易于在正确的温度下制造。
适用于本发明的基材包括但不限于涂有金属(例如铝，镍或铬(即金属化薄膜))的非透明聚合物；透明聚合物薄膜具有无机金属氧化物，如AlOx和SiOx层。合适的聚合物膜包括但不限于聚对苯二甲酸乙二醇酯(PET)、流延聚丙烯(CPP)、取向聚丙烯(OPP)、双轴取向聚丙烯(BOPP)、聚乳酸(PLA)、双轴取向聚酰胺(OPA)、聚乙醇酸等。金属化薄膜包括TorayAdvanced Film Co.,Ltd.的VM-CPP和VM-PE。本发明的阻隔涂料组合物可以以单层和层压结构使用，任选与油墨组合。在双层结构中，可以将阻隔涂层施加到前网(front web)上(例如，AlOx/PET或AlOx/OPP)，或密封剂网(例如，VM-PE或VM-CPP)，并且在两种情况下，优选位于层压结构的内侧。层压结构可用于包括干燥、潮湿、冷藏、冷冻和湿食品包装的应用，以及潜在的工业屏障应用。
尽管本发明的组合物优选用作涂料，但它可以以更高的固体含量配制以提供更高的粘性，并且可能用作水基或混合水基/溶剂基粘合剂用于层压。
对于许多应用来说，增强阻隔涂层常见夹在层压板的两个薄膜之间。但膜之间的层压粘合强度随之成为问题。然而，使用本发明的阻隔涂料组合物，可以实现大于1.0N/15mm，优选大于2.0N/15mm的粘合强度。此外，当层压板浸入水中时，粘合强度保持完整，未观察到分层。基于PET-PE的袋，具有聚乙烯代表热封层，即使在浸入水中24小时后也不会在PET-PE界面之间分层。在设定为在80℃至90℃下45分钟的标准条件下，小袋能够在巴氏杀菌试验中继续存在。增强阻隔涂层可以通过各种方法施加。在某些实施方案中，本发明的阻隔涂层可通过柔性版印刷或凹版印刷方法施加。然而，应该理解，本发明不限于这些类型的涂料应用，且可以使用适合于预期目的的任何涂料应用。
本发明的阻隔涂料组合物可以在低薄膜重量施用。阻隔涂层通常以约2至12g/m2的湿膜重量施加(导致膜重量为约0.05至3.0g/m2干燥)，而不需要填料(例如，Cloisite Na+、vermuculites、Somasif ME100等)。即使没有填料，本发明的隔离涂层在0％至90％相对湿度(RH)下载金属化基材上以及在诸如AlOx和SiOx涂覆的PET的基材上提供优异的气体和湿气阻隔性能。已经表明，如果涂覆涂层，则可以获得提供有利的性能平衡的层压材料，使得：
X＝(A/B)×(C/D)>200
其中：
A＝在没有涂层的情况下在23℃和50％相对湿度(RH)下的层压板的氧气透过率(OTR)；
B＝具有涂层的层压板在23℃和50％RH下的OTR；
C＝粘合剂完全固化后的粘合强度，单位为N/15mm；以及
D＝涂层重量，单位为g/m2(干燥)；
设定：
(A/B)>50；
C>2；且
D<0.6。
在某些实施方案中，本发明的隔离涂层优选用于增强具有金属化层(例如铝)或无机氧化物层(例如氧化铝(AlOx)或氧化硅(SiOx))的柔性基材的气体和湿气阻隔性。本发明的隔离涂层还保护这些基材的表面。由于较差的弯曲性能，金属化层和无机化合物层可能包含针孔或者在转换过程中以及在包装过程之前很可能是脆性的或损坏的。小的裂缝、针孔，足以显著降低阻隔性能，否则非常优秀(例如，未受损的AlOx-PET OTR在23℃和90％RH下为1-5cm3/m2/天；以及湿气透过率(MVTR)在38℃和90％RH下为1-5g/m2/天。阻隔性能因供应商和基材类型以及最终应用而异。尽管目前市售的阻隔增强涂层，但它们具有缺点。例如，SunBar LP(Sun Chemical Corp.)含有纳米二氧化硅颗粒，其在层压之前在涂覆的膜上引起光的衍射(彩虹图案)。SunBar LP使用聚乙烯醇，已知其在一系列阻隔应用中非常有效，但由于使用了聚乙烯醇以及聚乙烯醇对水分的敏感性，高RH下的气体阻隔性受到损害。本发明的增强阻隔涂层消除了这些问题，因为其包含胺改性的PVOH和乙酰乙酸酯改性的PVOH，并且含有很少或不含纳米颗粒。
通过首先制备单独的胺改性的PVOH(A部分)和乙酰乙酸酯改性的PVOH(B部分)溶液来制备本发明的阻隔涂料组合物。例如，A部分溶液可包含在70％水和30％乙醇中的胺改性的PVOH，例如Ultiloc 5003或Ultalux AD(均来自Seksui Specialty Chemicals)。A部分溶液还可含有一种或多种交联剂。B部分溶液可包含乙酰乙酸酯官能化的PVOH，例如在70％水和30％乙醇中的Gohsefimer Z200(Nippon Gohsei)。为制备最终的阻隔涂料组合物，将A部分和B部分溶液在室温下混合，得到均匀的溶液。A部分和B部分溶液的优选比例为75-99％(重量)、优选80-97％(重量)的A部分，以及1-25％(重量)、优选3-20％的B部分。A部分和B部分溶液通常以A部分：B部分约75:25至99:1的比例(按重量计)混合。设定A部分溶液的量，并确定B部分溶液的量，使得A部分加B部分的总和等于100wt％。基于阻隔涂料组合物中PVOH的总量，胺改性的PVOH的最终量总是大于乙酰乙酸酯改性的PVOH的最终量。例如，A部分：B部分的比例可以是约80:20；或约90:10；或约94:6；或约95:5；或约97:3。
A部分和B部分溶液易于共混以制备阻隔涂层，或者作为单组分体系，混合适用期为约24小时，优选最多约36小时，最优选最多约48小时。阻隔涂料组合物也可以从稳定的3包装(即A部分、B部分和交联剂的单独包装)开始容易地混合。优选地，阻隔涂料组合物作为稳定的2包装(即A部分与交联剂的单独包装，以及B部分)提供。涂料混合后，优选在48小时内，优选在36小时内，最优选在24小时内使用。
单独使用A部分溶液或B部分溶液不能提供本发明的阻隔涂料组合物的改进的阻隔性能。A部分和B部分之间的交联导致改善的耐水性和抗重复弯曲性(例如，Gelboflexing)。
胺改性的PVOH通常含有少于或等于40mol％的胺基。例如，胺改性的PVOH可含有小于或等于25mol％的胺基；或小于或等于12mol％的胺基。以下方法可用于确定PVOH中总胺值。总胺值是相当于1g样品中的总胺氢含量(碱度)的氢氧化钾(KOH)毫克数。如果样品不是液体，则通过将含有样品的烧瓶放入水浴中使其熔化/溶解。彻底混合样品，称取1至4克，精确至0.0001克(0.1毫克)，放入250毫升烧瓶中。加入50毫升水:酒精(80:20)，煮沸一分钟，以除去可能存在的任何游离氨。冷却至室温。加入5滴溴酚蓝指示剂，用0.2N HCl滴定，同时旋转至黄色终点(即样品溶液变黄)。计算总胺值如下：
总胺值＝(V×N×56.1)/S
其中：
V＝将样品溶液滴定至黄色终点所需HCl的体积(ml)
N＝HCl溶液的当量浓度
S＝使用的样品重量，以g为单位
56.1＝KOH的分子量(即56.1g/mol)
PVOH通常通过水解聚乙酸乙烯酯来合成。为了制备胺改性的PVOH，可以在合成过程中加入酰胺化合物，例如乙烯基甲酰胺。胺改性的PVOH也可以通过使PVOH与胺化合物反应来制备，所述胺化合物例如为氨基缩醛(例如参见US2,739,059)、3-(二甲基氨基)丙胺、3-氨基-1-丙醇、3-甲氧基乙胺、甲氧基丙胺、氨基乙氧基乙醇、3-氨基-1,2-丙二醇、氨基乙基乙醇胺、烯丙胺、3-氨基丙基磺酸盐、3-氨基丙基羧酸盐，及其组合(例如参见US7,714,086)。制备胺改性的PVOH的另一种方法是通过使PVOH与含有伯胺、仲胺、叔胺或季胺官能团的烯键式不饱和单体接枝聚合(例如参见US6,348,256)。
乙酰乙酸酯改性的PVOH可以通过使PVOH与双烯酮化合物反应，或与乙酰乙酸叔丁酯进行酯交换来制备(例如参见US8,679,536)。
基于A部分溶液的总重量，胺改性的PVOH通常以约0.1wt％至约10wt％。例如，胺改性的PVOH可以以约0.1wt％至约9.5wt％的量存在于A部分溶液中；或约0.1wt％至约9wt％；或约0.1wt％至约8.5wt％；或约0.1wt％至约8wt％；或约0.1wt％至约7.5wt％；或约0.1wt％至约7wt％；或约0.1wt％至约6.5wt％；或约0.1wt％至约6wt％；或约0.1wt％至约5.5wt％；或约0.1wt％至约5wt％；或约0.1wt％至约4.5wt％；或约0.1wt％至约4wt％；或约0.1wt％至约3.5wt％；或约0.1wt％至约3wt％；或约0.1wt％至约2.5wt％；或约0.1wt％至约2wt％；或约0.1wt％至约1.5wt％；或约0.1wt％至约1wt％；或约0.1wt％至约0.5wt％；或约0.5wt％至约10wt％；或约0.5wt％至约9.5wt％；或约0.5wt％至约9wt％；或约0.5wt％至约8.5wt％；或约0.5wt％至约8wt％；或约0.5wt％至约7.5wt％；或约0.5wt％至约7wt％；或约0.5wt％至约6.5wt％；或约0.5wt％至约6wt％；或约0.5wt％至约5.5wt％；或约0.5wt％至约5wt％；或约0.5wt％至约4.5wt％；或约0.5wt％至约4wt％；或约0.5wt％至约3.5wt％；或约0.5wt％至约3wt％；或约0.5wt％至约2.5wt％；或约0.5wt％至约2wt％；或约0.5wt％至约1.5wt％；或约0.5wt％至约1wt％；或约1wt％至约10wt％；或约1wt％至约9.5wt％；或约1wt％至约9wt％；或约1wt％至约8.5wt％；或约1wt％至约8wt％；或约1wt％至约7.5wt％；或约1wt％至约7wt％；或约1wt％至约6.5wt％；或约1wt％至约6wt％；或约1wt％至约5.5wt％；或约1wt％至约5wt％；或约1wt％至约4.5wt％；或约1wt％至约4wt％；或约1wt％至约3.5wt％；或约1wt％至约3wt％；或约1wt％至约2.5wt％；或约1wt％至约2wt％；或约1wt％至约1.5wt％的量存在于A部分溶液中。
乙酰乙酸酯改性的PVOH通常含有少于或等于40mol％的乙酰乙酸酯基团。例如，乙酰乙酸酯改性的PVOH可含有少于30mol％的乙酰乙酸酯基团，或少于10mol％的乙酰乙酸酯基团，或少于5mol％的乙酰乙酸酯基团。乙酰乙酸酯基团的存在，通常用于CH3C(O)CH2C(O)O-，可以使用1H质子和13C NMR(100-300MHz)确认。在本发明中，红外(IR)光谱用于证实CH3C(O)CH2C(O)O-中羰基的存在。羰基在1650至1750cm-1的范围内强烈吸收，证实在乙酰乙酸酯改性的PVOH中存在两个羰基带。
基于B部分溶液的总重量，乙酰乙酸酯改性的PVOH通常以约0.1wt％至约10wt％的量存在于B部分溶液中。例如，乙酰乙酸酯改性的PVOH可以以约0.1wt％至约9.5wt％；或约0.1wt％至约9wt％；或约0.1wt％至约8.5wt％；或约0.1wt％至约8wt％；或约0.1wt％至约7.5wt％；或约0.1wt％至约7wt％；或约0.1wt％至约6.5wt％；或约0.1wt％至约6wt％；或约0.1wt％至约5.5wt％；或约0.1wt％至约5wt％；或约0.1wt％至约4.5wt％；或约0.1wt％至约4wt％；或约0.1wt％至约3.5wt％；或约0.1wt％至约3wt％；或约0.1wt％至约2.5wt％；或约0.1wt％至约2wt％；或约0.1wt％至约1.5wt％；或约0.1wt％至约1wt％；或约0.1wt％至约0.5wt％；或约0.5wt％至约10wt％；或约0.5wt％至约9.5wt％；或约0.5wt％至约9wt％；或约0.5wt％至约8.5wt％；或约0.5wt％至约8wt％；或约0.5wt％至约7.5wt％；或约0.5wt％至约7wt％；或约0.5wt％至约6.5wt％；或约0.5wt％至约6wt％；或约0.5wt％至约5.5wt％；或约0.5wt％至约5wt％；或约0.5wt％至约4.5wt％；或约0.5wt％至约4wt％；或约0.5wt％至约3.5wt％；或约0.5wt％至约3wt％；或约0.5wt％至约2.5wt％；或约0.5wt％至约2wt％；或约0.5wt％至约1.5wt％；或约0.5wt％至约1wt％；或约1wt％至约10wt％；或约1wt％至约9.5wt％；或约1wt％至约9wt％；或约1wt％至约8.5wt％；或约1wt％至约8wt％；或约1wt％至约7.5wt％；或约1wt％至约7wt％；或约1wt％至约6.5wt％；或约1wt％至约6wt％；或约1wt％至约5.5wt％；或约1wt％至约5wt％；或约1wt％至约4.5wt％；或约1wt％至约4wt％；或约1wt％至约3.5wt％；或约1wt％至约3wt％；或约1wt％至约2.5wt％；或约1wt％至约2wt％；或约1wt％至约1.5wt％的量存在于B部分溶液中。
基于气体阻隔涂料组合物中PVOH的总重量，胺改性的PVOH通常以约50wt％至约99.9wt％的量存在于气体阻隔涂料组合物中。例如，基于气体阻隔涂料组合物中PVOH的总重量，胺改性的PVOH可以以约50wt％至约99wt％；或约50wt％至约95wt％；或约50wt％至约90wt％；或约50wt％至约85wt％；或约50wt％至约80wt％；或约50wt％至约75wt％；或约50wt％至约70wt％；或约50wt％至约65wt％；或约50wt％至约55wt％；或约55wt％至约99.9wt％；或约55wt％至约99wt％；或约55wt％至约95wt％；或约55wt％至约90wt％；或约55wt％至约85wt％；或约55wt％至约80wt％；或约55wt％至约75wt％；或约55wt％至约70wt％；或约55wt％至约65wt％；或约55wt％至约60wt％；或约60wt％至约99.9wt％；或约60wt％至约99wt％；或约60wt％至约95wt％；或约60wt％至约90wt％；或约60wt％至约85wt％；或约60wt％至约80wt％；或约60wt％至约75wt％；或约60wt％至约70wt％；或约60wt％至约65wt％；或约65wt％至约99.9wt％；或约65wt％至约99wt％；或约65wt％至约95wt％；或约65wt％至约90wt％；或约65wt％至约85wt％；或约65wt％至约80wt％；或约65wt％至约75wt％；或约65wt％至约70wt％；或约70wt％至约99.9wt％；或约70wt％至约99wt％；或约70wt％至约95wt％；或约70wt％至约90wt％；或约70wt％至约85wt％；或约70wt％至约80wt％；或约70wt％至约75wt％；或约75wt％至约99.9wt％；或约75wt％至约99wt％；或约75wt％至约95wt％；或约75wt％至约90wt％；或约75wt％至约85wt％；或约75wt％至约80wt％；或约80wt％至约99.9wt％；或约80wt％至约99wt％；或约80wt％至约95wt％；或约80wt％至约90wt％；或约80wt％至约85wt％；或约85wt％至约99.9wt％；或约85wt％至约99wt％；或约85wt％至约95wt％；或约85wt％至约90wt％的量存在于气体阻隔涂料组合物中。
基于气体阻隔涂料组合物中PVOH的总重量，乙酰乙酸酯改性的PVOH通常以约0.1wt％至约50wt％的量存在于阻气涂料组合物中。例如，乙酰乙酸酯改性的PVOH可以以约0.1wt％至约45wt％；或约0.1wt％至约40wt％；或约0.1wt％至约35wt％；或约0.1wt％至约30wt％；或约0.1wt％至约25wt％；或约0.1wt％至约20wt％；或约0.1wt％至约15wt％；或约0.1wt％至约10wt％；或约0.1wt％至约5wt％；或约0.1wt％至约1wt％；或约0.1wt％至约0.5wt％；或约0.5wt％至约50wt％；或约0.5wt％至约45wt％；或约0.5wt％至约40wt％；或约0.5wt％至约35wt％；或约0.5wt％至约30wt％；或约0.5wt％至约25wt％；或约0.5wt％至约20wt％；或约0.5wt％至约15wt％；或约0.5wt％至约10wt％；或约0.5wt％至约5wt％；或约0.5wt％至约1wt％；或约1wt％至约50wt％；或约1wt％至约45wt％；或约1wt％至约40wt％；或约1wt％至约35wt％；或约1wt％至约30wt％；或约1wt％至约25wt％；或约1wt％至约20wt％；或约1wt％至约15wt％；或约1wt％至约10wt％；或约1wt％至约5wt％；或约5wt％至约50wt％；或约5wt％至约45wt％；或约5wt％至约40wt％；或约5wt％至约35wt％；或约5wt％至约30wt％；或约5wt％至约25wt％；或约5wt％至约20wt％；或约5wt％至约15wt％；或约5wt％至约10wt％的量存在。
本发明的阻气涂料组合物还可包含一种或多种另外的聚合物。合适的另外的聚合物包括但不限于完全或部分水解的聚乙烯醇、完全或部分水解的聚乙烯醇和乙烯-乙烯醇(EVOH)共聚物、水基丙烯酸类、丙烯酸氨基甲酸酯、聚氨酯，及其组合等。当存在时，基于阻隔涂料组合物的总重量，一种或多种另外的聚合物通常以0.1至5wt％的量存在。例如，一种或多种另外的聚合物可以以0.1wt％至约4.5wt％；或约0.1wt％至约4wt％；或约0.1wt％至约3.5wt％；或约0.1wt％至约3wt％；或约0.1wt％至约2.5wt％；或约0.1wt％至约2wt％；或约0.1wt％至约1.5wt％；或约0.1wt％至约1wt％；或约0.1wt％至约0.5wt％；或约0.5wt％至约5wt％；或约0.5wt％至约4.5wt％；或约0.5wt％至约4wt％；或约0.5wt％至约3.5wt％；或约0.5wt％至约3wt％；或约0.5wt％至约2.5wt％；或约0.5wt％至约2wt％；或约0.5wt％至约1.5wt％；或约0.5wt％至约1wt％；或约1wt％至约5wt％；或约1wt％至约4.5wt％；或约1wt％至约4wt％；或约1wt％至约3.5wt％；或约1wt％至约3wt％；或约1wt％至约2.5wt％；或约1wt％至约2wt％；或约1wt％至约1.5wt％的量存在。
本发明的阻隔涂料组合物还可包含一种或多种交联剂。交联剂可以在与B部分溶液混合之前加入到A部分溶液中，或者可以在A部分和B部分混合后加入到涂料组合物中。当存在时，交联剂通常以相对于PVOH组分总重量的约5％至25％的量存在。例如，相对于PVOH组分的总重量，交联剂可以以约5％至约20％；或约5％至约15％；或约5％至约10％；或约5％至约8％的量存在。
合适的交联剂包括但不限于铵锆、碳酸锆铵；碳酸锌，如碳酸锌铵；其他金属碳酸盐；乙酰丙酮酸盐；酮类；醛类和二醛类，如甲醛、乙醛、乙二醛和戊二醛；聚合醛；环氧硅烷类，如3-环氧丙氧基丙基三甲氧基硅烷、3-环氧丙氧基丙基甲基二乙氧基硅烷和2-(3,4-环氧环己基)乙基三甲氧基硅烷；氨基硅烷类，如3-氨基-丙基三甲氧基硅烷、3-氨基丙基三乙氧基硅烷、N-(2-氨基乙基)-3-氨基丙基甲基二甲氧基硅烷、氨基乙基氨基三甲氧基硅烷和氨基乙基氨基丙基硅氧烷；烷氧基硅烷类，如甲基三甲氧基硅烷、甲基三乙氧基硅烷、二甲氧基硅烷、异丁基三甲氧基硅烷、苯基三乙氧基硅烷、正辛基三乙氧基硅烷、乙烯基三甲氧基硅烷和乙烯基三乙酰氧基硅烷。包含乙烯基烷基酮单体单元的含羰基和/或环氧基的聚合物添加剂也可用作交联剂，包括但不限于乙烯基甲基酮、乙烯基乙基酮、双丙酮丙烯酰胺、双丙酮(甲基)丙烯酰胺、双丙酮(甲基)丙烯酸酯。含环氧基的聚合物的实例包括但不限于缩水甘油基甲基(丙烯酸酯)、β-甲基缩水甘油基甲基(丙烯酸酯)、3,4-环氧环己基甲基甲基(丙烯酸酯)、烯丙基缩水甘油醚等。含有二氢唑酮官能团的二氢唑酮衍生物也是合适的交联剂。其他交联剂包括醛-PEG-NHS和缩醛-PEG-NHS，例如乙二醇-双(琥珀酸N-羟基琥珀酰亚胺酯)、癸二酸-双(N-琥珀酰亚胺酯)、二(N-琥珀酰亚胺基)戊二酸酯、N,N'-二琥珀酰亚胺基草酸盐。交联剂可以单独存在，或者两种或多种的组合存在。
有利地，金属基交联剂也可以在本发明的阻隔涂料组合物中起稳定剂的作用，抑制其组合物的过早凝胶化。本领域常见且众所周知,在乙酰乙酸酯官能团存在下发生金属螯合(Zr、Zn、Cu、Ag和Ni)。例如，已知碳酸锆铵交联各种官能团，例如羧基，以提供耐水/耐溶剂性。然而，在乙酰乙酸酯改性的PVOH存在下，锆可以很好地与乙酰乙酸酯基团螯合，减缓胺和乙酰乙酸酯基团的反应，从而为本发明的混合的A部分和B部分溶液提供额外的稳定性和适用期。
本发明的阻隔涂料组合物还可包含一种或多种粘合促进剂。粘合促进剂包括但不限于烷基硅烷，例如甲基三甲氧基硅烷、甲基三乙氧基硅烷、二甲氧基硅烷、异丁基三甲氧基硅烷、苯基三乙氧基硅烷、正辛基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷。钛酸盐和锆酸盐也可用作粘合促进剂，包括但不限于钛酸四烷基酯、乳酸钛铵、二异丙氧基-二乙基乙酰基乙酰钛酸盐、三乙醇胺钛络合物、二羟基钛双(乳酸铵)、乳酸锆、钠盐和乙醇酸锆钠。在某些实施方案中，提供交联的添加剂还可以提供对基材的粘合。粘合促进剂可以单独存在或作为两种或多种的组合存在。当存在时，基于气体阻隔涂料组合物的总重量，粘合促进剂通常以0.1至5wt％的量存在于阻隔组合物中。例如，基于阻隔涂料组合物的总重量，粘合促进剂可以以约0.1wt％至约5wt％的量存在。例如，这些其他添加剂可各自独立地以约0.1wt％至约4.5wt％；或约0.1wt％至约4wt％；或约0.1wt％至约3.5wt％；或约0.1wt％至约3wt％；或约0.1wt％至约2.5wt％；或约0.1wt％至约2wt％；或约0.1wt％至约1.5wt％；或约0.1wt％至约1wt％；或约0.1wt％至约0.5wt％；或约0.5wt％至约5wt％；或约0.5wt％至约4.5wt％；或约0.5wt％至约4wt％；或约0.5wt％至约3.5wt％；或约0.5wt％至约3wt％；或约0.5wt％至约2.5wt％；或约0.5wt％至约2wt％；或约0.5wt％至约1.5wt％；或约0.5wt％至约1wt％；或约1wt％至约5wt％；或约1wt％至约4.5wt％；或约1wt％至约4wt％；或约1wt％至约3.5wt％；或约1wt％至约3wt％；或约1wt％至约2.5wt％；或约1wt％至约2wt％；或约1wt％至约1.5wt％的量存在。
可添加到本发明的阻隔涂料组合物中的其他添加剂包括但不限于消泡剂、脱气剂、表面活化剂(Surface active agents)、表面活性剂(surfactants)、分散剂和本领域已知的其它添加剂，其可在涂料和涂料溶液的制备、涂膜的外观、或改善涂膜性能的任何方面，其组合等提供改进。当存在时，基于阻隔涂料组合物的总重量，这些其它添加剂通常各自独立地存在于阻隔涂层中，其量为约0.1wt％至约5wt％。例如，这些其他添加剂可各自独立地以约0.1wt％至约4.5wt％；或约0.1wt％至约4wt％；或约0.1wt％至约3.5wt％；或约0.1wt％至约3wt％；或约0.1wt％至约2.5wt％；或约0.1wt％至约2wt％；或约0.1wt％至约1.5wt％；或约0.1wt％至约1wt％；或约0.1wt％至约0.5wt％；或约0.5wt％至约5wt％；或约0.5wt％至约4.5wt％；或约0.5wt％至约4wt％；或约0.5wt％至约3.5wt％；或约0.5wt％至约3wt％；或约0.5wt％至约2.5wt％；或约0.5wt％至约2wt％；或约0.5wt％至约1.5wt％；或约0.5wt％至约1wt％；或约1wt％至约5wt％；或约1wt％至约4.5wt％；或约1wt％至约4wt％；或约1wt％至约3.5wt％；或约1wt％至约3wt％；或约1wt％至约2.5wt％；或约1wt％至约2wt％；或约1wt％至约1.5wt％的量存在。
尽管本发明的阻隔涂料组合物通常在没有着色剂的情况下供应，但是可以添加着色剂以提供染色或着色的增强隔离涂层。合适的着色剂的实例包括但不限于有机或无机颜料和染料。染料包括但不限于荧光染料、偶氮染料、蒽醌染料、氧杂蒽染料、吖嗪染料、及其组合等。有机颜料可以是一种颜料或多种颜料的组合，例如颜料黄数12、13、14、17、74、83、114、126、127、174、188；颜料红数2、22、23、48:1、48:2、52、52:1、53、57:1、112、122、166、170、184、202、266、269；颜料橙号5、16、34、36；颜料蓝编号15、15:3、15:4；颜料紫数字3、23、27；和/或颜料绿7号。无机颜料可以是以下非限制性颜料之一：氧化铁、二氧化钛、氧化铬、亚铁氰化铁铵、氧化铁黑、7号颜料黑和/或颜料白6和7。也可以使用其他有机和无机颜料和染料，以及获得所需颜色的组合。当存在时，基于阻隔涂料组合物的总重量，染料和有机颜料通常以约0.1wt％至约10wt％的量存在。当存在时，基于阻隔涂料组合物的总重量，无机颜料通常以约0.1wt％至约40wt％的量存在。
本发明的阻隔涂料组合物优选不含纳米颗粒(填充材料)，该纳米颗粒通常用于增强目前现有隔离涂层的气体和水蒸气性质。然而，阻隔涂料组合物可任选地含有少于30wt％，优选少于15wt％，更优选少于5wt％的纳米颗粒。最优选地，本发明的阻隔涂料组合物不含任何纳米微粒。由于缺乏纳米颗粒，减少了对健康的担心。合适的纳米颗粒包括但不限于高岭石、蒙脱石、凹凸棒石、伊利石、膨润土、埃洛石、高岭土、云母、蛭石、硅藻土和漂白土、煅烧硅酸铝、水合硅酸铝、硅酸铝镁、硅酸钠、硅酸镁，及其组合等。
基于气体阻隔涂料组合物的总重量，本发明的阻隔涂料组合物的总固体含量通常为3wt％至20wt％。例如，阻隔涂料组合物的固体含量可以为3wt％至15wt％；或3wt％至10wt％；或3wt％至5wt％；或5wt％至20wt％；或5wt％至15wt％；或5wt％至10wt％。
本发明的阻隔涂料组合物可任选含有一种或多种溶剂。当存在时，基于阻隔涂料组合物的总重量，溶剂通常以约1wt％至约50wt％的量存在。例如，溶剂可以以约1wt％至约50wt％；或约1wt％至约45wt％；或约1wt％至约40wt％；或约1wt％至约35wt％；或约1wt％至约30wt％；或约1wt％至约25wt％；或约1wt％至约20wt％；或约1wt％至约15wt％；或约1wt％至约10wt％；或约1wt％至约5wt％；或约5wt％至约50wt％；或约5wt％至约45wt％；或约5wt％至约40wt％；或约5wt％至约35wt％；或约5wt％至约30wt％；或约5wt％至约25wt％；或约5wt％至约20wt％；或约5wt％至约15wt％；或约5wt％至约10wt％的量存在。合适的溶剂包括但不限于水、醇、酮、酯及其组合等。
实施例
以下实施例说明了本发明的具体方面，并不意图在任何方面限制其范围，并且不应该如此解释。
测试方法
非挥发物百分含量(％NVC)
将约1g涂料加入培养皿中，并将实际重量记录到小数点后两位。然后将培养皿置于电加热的风扇辅助烘箱中，在150℃下保持30分钟。然后将样品冷却至室温并重新称重。％NVC按如下计算：
％NVC＝(干涂层的最终重量(克)/湿涂层的初始重量(克))×100
粘性
使用Brookfield DV-II+Pro粘度计在25℃下测量粘度。使用LV 2转子，并且在60rpm的剪切速率下测试样品。粘度报告为mPa.s。
储存稳定性
使用(Seta)Zahn cup#2在23℃下测量涂布溶液的初始粘度。初始粘度被认为是应用粘度。将100g涂料溶液组分A和B置于设置在4℃冰箱中的密封玻璃瓶中。定期取出样品(每4-5天)并测量其粘度。粘度或外观和均匀性的变化被认为是负面因素，例如凹版印刷的粘度增加超过25秒，柔版印刷工艺的粘度增加超过30秒。没有可见的相分离是优选的。无大于20FTU(单位雾度)的溶液混浊是优选的。浊度报告为福尔马肼浊度单位(FTU)。
氧气传输率(OTR)
当涂覆到聚酯薄膜上时，涂层的氧气透过率(OTR)利用Mocon Oxtran 2/21透气性测试仪在23℃和90％相对湿度下测定。该条件代表干食品包装的正常测试方案。这意味着将渗透气体(O2)调节至90％RH(23℃)并将运载气体(100％N2)调节至90％RH(23℃)。此外，还评估了在23℃和50/50％相对湿度条件下的Mocon Oxtran 2/21透气性测试仪。
涂层涂有No.0K-Bar(例如，RK Print)，提供约4g/m2的湿膜重量，并在温暖的空气流中干燥(实验室印刷品用吹风机干燥)。
评估了金属化涂层膜和AlOx或SiOx涂层阻隔膜上的增强涂层的OTR。
粘附力
使用DRG 1112聚丙烯带测量粘附力。将25mm宽的条带牢固地压在如上面OTR测试中所述制备的感兴趣的基材上的干燥涂层样品上，并以几种方式除去。首先，将胶带快速以180°拉回。其次，通过将胶带90°拉开并最终以非常慢的速度(例如20mm/min)重复第一次测试。结果报告为“合格”或“不合格”，其中“合格”表示没有涂层被移除。
层压粘合强度
通过将增强涂层施加到金属化涂层膜或AlOx或SiOx涂覆的阻隔膜来制备层压板。将粘合剂施加在干燥的增强涂层的顶部，然后层压到30μm规格的聚(乙烯)膜的处理面上。使用的粘合剂由DIC-Sun Chemical(Sunlam LX-415A和Sunlam SP-75)提供，并根据制造商的说明制备并施加以使最终干膜重量达到3g/m2。然后将层压板在25℃下储存14天以确保异氰酸酯基粘合剂的完全固化。在“T”剥离分离条件下，在JJ Lloyd LRX张力计上使用30mm/min的十字头速度测量粘合强度。层压板样品宽15毫米，结果以克力/15毫米给出。制备用于巴氏灭菌和蒸煮试验的小袋的层压板使用由DIC-Sun Chemical，LX500和KW-75提供的不同粘合剂，并根据制造商的说明制备并应用以使最终干膜重量为4g/m2。
巴氏灭菌试验
基于AlOx或SiOx PET-增强阻隔涂层-粘合剂-PE层压结构制备小袋，并使用热封机密封，使用PE作为热封层。然后将小袋置于85℃的烧杯中45分钟。如果袋在PET-PE层之间没有分层并且在透明层压板中没有出现可见气泡，则给出“合格”等级。
24hr浸水试验
将涂层样品涂覆到所需的基材上(例如，AlOx或SiOx PET)并用粘合剂层压到PE上。然后使用RDM HSE-3实验室热封机将层压板转变成小袋。将热封钳设定在150℃，在50psi下停留1秒。制备含有100％相对湿度的小袋以模拟湿食物。然后将小袋置于一桶自来水中，确保小袋完全浸没24小时以确定是否发生分层。分层通常通过AlOx或SiOx PET基材和PE之间的水进入而发生。如果袋在PET-PE层之间没有分层并且在透明层压板中没有出现可见气泡，则给出“合格”等级。
Gelbo挠曲测试
Gelbo挠曲测试是测量柔性阻隔涂层的挠曲耐久性的测试。Gelbo挠曲测试柔性阻隔涂层是否能抵抗重复应变，这称为柔韧性，或称为Gelbo挠曲。典型的测试样品尺寸为200×280mm，其连接到Gelbo挠曲测试仪设备(Gelbo挠曲测试型号G0002，来自IDMInstruments)。弯曲动作包括扭转运动和水平运动(压缩)，从而反复扭曲和压碎薄膜。测试装置在行程的前90毫米内产生440°的扭转运动，然后是65毫米的水平直线运动。速度高达每分钟50个循环。在Gelbo弯曲之前和之后测量涂层的氧气透过率，以表示阻隔性能的任何变化。
制备A部分和B部分的PVOH溶液
A1部分——含有交联剂溶液的胺改性PVOH
根据表A1中的配方(重量％)制备胺改性的PVOH(来自Sekisui的Ultiloc 5003)的水/乙醇溶液。Al部分的溶液包括稳定的碳酸锆铵交联剂(来自MEL Chemicals的Bacote20)。如上所述测量粘度(使用Brookfield粘度计)和％NVC。
表A1.A1部分的配方
A2部分-不含交联剂溶液的胺改性PVOH
根据表A2中的配方(重量％)制备胺改性的PVOH(来自Sekisui的Ultiloc 5003)的水/乙醇溶液。如上所述测量粘度(使用Brookfield粘度计)和％NVC。
表A2.A2部分的配方
B部分-乙酰乙酸酯改性的PVOH溶液
根据表B中的配方(重量％)制备乙酰乙酸酯改性的PVOH(来自Nippon-Gohsei的Gohsefimer Z200)的水/乙醇溶液。如上所述测量粘度(使用Brookfield粘度计)和％NVC。
表B.B部分的配方
1优选使用去离子水，但也可以使用自来水、蒸馏水、泉水、过滤水等。
实施例1-5包含具有交联剂的胺改性的PVOH和乙酰乙酸酯改性的PVOH的阻隔涂层
通过以各种比例混合A1部分和B部分，制备包含具有交联剂的胺改性的PVOH(A1部分)和乙酰乙酸酯改性的PVOH(B部分)的实施例1至5的阻隔涂料组合物。实施例1至5的制剂，以每种材料的重量％(wt％)示于表1中。
如上所述测试实施例1至5的储存稳定性。所有实施例1至5的储存稳定性测试都合格。
表1实施例1至5的配方
实施例6标准的市售增强涂层系统
SunBar LP双组分阻隔增强涂层系统用作对比屏障涂层。SunBar LP SX001是PVOH溶液，SunBar LP SX004是粘土分散体。两种组分的混合比示于表2中。
表2SunBar LP的配方
实施例7-9包含胺改性的PVOH和乙酰乙酸酯改性的PVOH的阻隔涂层
包含胺改性的PVOH(A2部分)和乙酰乙酸酯改性的PVOH(B部分)的实施例7至9的阻隔涂料组合物通过以各种比例混合部分A2和B部分来制备。实施例7至9的阻隔涂层不含交联剂。实施例7至9的制剂，以每种材料的重量％(wt％)示于表3中。
如上所述测试实施例7至9的储存稳定性。所有实施例7至9的储存稳定性试验都合格。
表3实施例7至9的配方
实施例10在AlOx/PET膜上的实施例1、4、5和6的氧气阻隔性能(OTR)
实施例1、4和5以及对比实施例6使用No.0K棒以4g/m2的湿膜重量印刷为单层实验室印刷品，并使用吹风机在各种无机薄膜层上干燥。如上所述测量氧气透过率，并以cm3/m2/天报告。表4显示了在Toyobo VE100膜(具有陶瓷(二氧化硅/氧化铝)的气相沉积的PET膜)上印刷的每个实施例的OTR。表5显示了在Toray Barrialox Film(A10X/PET)上印刷的每个实施例的OTR。
表4在Toyobo VE100膜上印刷的实施例1、4、5和6的OTR
表5Toray Barrialox膜上的实施例1和6的OTR
表4和5中的结果表明，在相对高湿度下，本发明的阻隔涂层(实施例1、4和5)在Gelbo挠曲之前和之后表现出比市售的阻隔涂层(实施例6)更好的氧气阻隔性能。
实施例11在柔版印刷机上印刷的阻隔涂层的干燥速度和OTR
将实施例1和对比实施例6印刷在来自Ultimate Packaging的AlOx/PET膜上，并测量干燥速度的界限(以m/min计)和OTR。如上所述，通过测量涂层对基材的粘附性来评估干燥速度。结果如表6所示。
表6在柔版印刷机上印刷的隔离涂层的干燥速度和OTR
| 干燥速度界限(m/min) | 50％RH下的OTR | |
| 实施例1 | 130 | 1.70 |
| 实施例6 | 50 | 0.35 |
表6中的结果表明，对比实施例6的干燥速度界限为50m/min。相反，实施例1在90m/min和130m/min的速度下显示出对基材的良好粘附性(报道的干燥速度界限为130m/min)。在柔性版印刷机上印刷的实施例1涂层的阻气性优于在柔性版印刷机上印刷的对比实施例6的阻气性。
实施例12使用阻隔涂层的层压材料的性能
层压粘合强度
将本发明的阻隔涂层印刷在多种AlOx/PET膜上，并将AlOx/PET膜层压到聚乙烯膜上。如上所述测试层压粘合强度。使用本发明的阻隔涂层制备的层压材料的层压粘合强度大于或等于2.0N/15mm。
耐巴氏灭菌性和耐水浸性
将实施例1和对比实施例6印刷在各种AlOx/PET膜上，并将AlOx/PET膜层压到聚乙烯膜上，在150℃/50psi/1秒的时间内热封，并制成小袋。将小袋在80℃的热水中巴氏杀菌45分钟。如上所述在水浸试验中评估小袋。对于这两种测试，评估袋的边缘是否有分层的迹象。“合格”意味着没有分层的迹象。结果如表7A所示。
表7A实施例1和6的巴氏灭菌和浸水表现
表7A中的结果表明，与市售的对比阻隔涂层实施例6和6a相比，本发明实施例1的阻隔涂层显示出优异的耐巴氏灭菌性和耐水浸性。
将实施例2和3以及对比例6印刷在AlOx/PET膜上，并将AlOx/PET膜层压到聚乙烯膜上，在150℃/50psi/1秒的时间内热封，并制成小袋。将小袋在80℃的热水中巴氏杀菌45分钟。评估袋的边缘的分层迹象。“合格”意味着没有分层的迹象。结果如表7B所示。
表7B实施例2、3和6的巴氏灭菌表现和OTR
表7B中的结果表明，与实施例6和6a的市售对比阻隔涂层相比，本发明实施例2和3的阻隔涂层表现出优异的耐巴氏灭菌性和耐水浸性。
实施例13实施例7至9的氧气阻隔性能
将实施例7至9应用于Toyobo VE100膜，并如上所述测量OTR。将涂有实施例7至9的薄膜的OTR与未涂布的Toyobo VE100薄膜的OTR进行比较。结果如表8所示。
表8实施例7至9的OTR
表8中的结果表明，包含无交联剂的胺改性的PVOH和乙酰乙酸酯改性的PVOH的阻隔涂层显著增强了AlOx/PET膜的气体阻隔性能。
已经详细描述了本发明，包括其优选实施方案。然而，应当理解，本领域技术人员在考虑本公开内容后，可以对本发明进行修改和/或改进，这些修改和/或改进落入本发明的范围和精神内。
Claims (42)
1.一种气体阻隔涂料组合物，包含：
a)胺改性的聚乙烯醇；
b)乙酰乙酸酯改性的聚乙烯醇；和
c)一种或多种交联剂，所述一种或多种交联剂选自由以下组成的组：金属碳酸盐、乙酰丙酮酸盐、酮类、醛类、二醛类、聚合醛、环氧硅烷类、氨基硅烷类、烷氧基硅烷类、包括乙烯基烷基酮的单体单元的含羰基和/或含环氧基的聚合物添加剂、二氢唑酮衍生物、醛-PEG-NHS和乙缩醛-PEG-NHS、钛酸盐、锆酸盐及其组合；
其中所述胺改性的聚乙烯醇包含小于或等于10mol％的胺基。
2.根据权利要求1所述的气体阻隔涂料组合物，其中所述乙酰乙酸酯改性的聚乙烯醇包含小于或等于30mol％的乙酰乙酸酯官能团。
3.根据权利要求1所述的气体阻隔涂料组合物，其中所述乙酰乙酸酯改性的聚乙烯醇包含小于或等于5mol％的乙酰乙酸酯官能团。
4.根据权利要求1所述的气体阻隔涂料组合物，其中基于所述气体阻隔涂料组合物中聚乙烯醇的总重量，所述胺改性的聚乙烯醇以50wt％至99.9wt％的量存在。
5.根据权利要求1所述的气体阻隔涂料组合物，其中基于所述气体阻隔涂料组合物中聚乙烯醇的总重量，所述乙酰乙酸酯改性的聚乙烯醇以0.1wt％至50wt％的量存在。
6.根据权利要求1所述的气体阻隔涂料组合物，其中基于所述气体阻隔涂料组合物的总重量，固体含量为3wt％至15wt％。
7.根据权利要求1所述的气体阻隔涂料组合物，其中所述胺改性的聚乙烯在(A)部分溶液中提供，并且所述乙酰乙酸酯改性的聚乙烯在(B)部分溶液中提供，并且胺改性的聚乙烯醇溶液(A)部分与乙酰乙酸酯改性的聚乙烯醇溶液(B)部分的比例为75:25至99:1。
8.根据权利要求1所述的气体阻隔涂料组合物，还包含独立地选自由粘合促进剂、表面活化剂、表面活性剂、分散剂、脱气剂和消泡剂组成的组中的一种或多种添加剂。
9.根据权利要求8所述的气体阻隔涂料组合物，其中基于所述气体阻隔涂料组合物的总重量，所述一种或多种添加剂各自独立地以0.1wt％至5wt％的量存在。
10.根据权利要求1所述的气体阻隔涂料组合物，其中相对于所述气体阻隔涂料组合物的所述聚乙烯醇含量的总重量，所述交联剂以5％至25％的量存在。
11.根据权利要求1所述的气体阻隔涂料组合物，其中所述一种或多种交联剂选自由碳酸锆铵；碳酸锌铵；甲醛；乙醛；乙二醛；戊二醛；3-环氧丙氧基丙基三甲氧基硅烷，3-环氧丙氧基丙基甲基二乙氧基硅烷；2-(3,4-环氧环己基)乙基三甲氧基硅烷；3-氨基-丙基三甲氧基硅烷、3-氨基丙基三乙氧基硅烷、N-(2-氨基乙基)-3-氨基丙基甲基二甲氧基硅烷、氨基乙基氨基三甲氧基硅烷、氨基乙基氨基丙基硅氧烷；甲基三甲氧基硅烷、甲基三乙氧基硅烷、二甲氧基硅烷、异丁基三甲氧基硅烷、苯基三乙氧基硅烷、正辛基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三乙酰氧基硅烷及其组合组成的组。
12.根据权利要求1所述的气体阻隔涂料组合物，其中所述交联剂是碳酸锆铵。
13.根据权利要求1所述的气体阻隔涂料组合物，还包含一种或多种纳米颗粒。
14.根据权利要求13所述的气体阻隔涂料组合物，其中基于所述气体阻隔涂料组合物的总重量，所述一种或多种纳米颗粒以0.1wt％至30wt％的量存在。
15.根据权利要求13所述的气体阻隔涂料组合物，其中基于所述气体阻隔涂料组合物的总重量，所述纳米微粒以小于30wt％的量存在。
16.根据权利要求13所述的气体阻隔涂料组合物，其中基于所述气体阻隔涂料组合物的总重量，所述纳米微粒以小于15wt％的量存在。
17.根据权利要求13所述的气体阻隔涂料组合物，其中基于所述气体阻隔涂料组合物的总重量，所述纳米微粒以小于5wt％的量存在。
18.根据权利要求13所述的气体阻隔涂料组合物，其中所述一种或多种纳米颗粒选自由高岭石、蒙脱石、凹凸棒石、伊利石、膨润土、埃洛石、高岭土、云母、蛭石、硅藻土和漂白土、煅烧硅酸铝、水合硅酸铝、硅酸铝镁、硅酸钠、硅酸镁及其组合组成的组。
19.根据权利要求1所述的气体阻隔涂料组合物，还包含选自由完全和部分水解的聚乙烯醇和乙烯-乙烯醇共聚物、水基丙烯酸类、丙烯酸氨基甲酸酯、聚氨酯分散体及其组合组成的组中的一种或多种。
20.根据权利要求1所述的气体阻隔涂料组合物，还包含一种或多种溶剂。
21.根据权利要求20所述的气体阻隔涂料组合物，其中基于所述气体阻隔涂料组合物的总重量，所述一种或多种溶剂以1wt％至50wt％的量存在。
22.根据权利要求20所述的气体阻隔涂料组合物，其中所述一种或多种溶剂各自独立地选自由水、醇、酮、酯及其组合组成的组。
23.根据权利要求1所述的气体阻隔涂料组合物，其中基于所述气体阻隔涂料组合物的总重量，还包含0.1wt％至40wt％的量的一种或多种着色剂。
24.一种提高基材的气体阻隔性的方法，包括：
a)将根据权利要求1-23中任一项所述的气体阻隔涂料组合物涂布在基材上；以及
b)干燥所述基材上的所述气体阻隔涂料组合物。
25.根据权利要求24所述的方法，其中所述基材选自由聚对苯二甲酸乙二醇酯、流延聚丙烯、取向聚丙烯、聚乳酸和双轴取向聚酰胺组成的组。
26.根据权利要求24或25所述的方法，其中所述基材还包括一个或多个金属层或一个或多个无机层。
27.根据权利要求24所述的方法，其中所述基材是金属化膜，并且包括一层或多层铝、镍或铬。
28.根据权利要求24所述的方法，其中所述基材包括一个或多个金属氧化物层。
29.一种基材，其包含根据权利要求1-23中任一项所述的气体阻隔涂料组合物。
30.根据权利要求29所述的基材，其在23℃和50％相对湿度下的氧气透过率小于1cm3/m2/天。
31.根据权利要求29所述的基材，其在23℃和90％相对湿度下的氧气透过率小于2.75cm3/m2/天。
32.根据权利要求29所述的基材，其在Gelbo挠曲后在23℃和50％相对湿度下具有小于1cm3/m2/天的氧气透过率。
33.一种制品，包含根据权利要求29-32中任一项所述的基材。
34.根据权利要求33所述的制品，其中所述制品是包装制品。
35.根据权利要求33或34所述的制品，其中所述制品耐巴氏灭菌。
36.一种层压膜，包括：
a)作为第一薄膜的根据权利要求29-32中任一项所述的基材；以及
b)粘附到所述第一薄膜的侧面上的作为第二薄膜的第二未涂覆基材，其中在所述第一薄膜的所述侧面上应用所述气体阻隔涂料。
37.根据权利要求36所述的层压膜，其中所述第一薄膜和所述第二薄膜之间的层压粘合强度大于1.0N/15mm。
38.根据权利要求36所述的层压膜，其中所述第一薄膜和所述第二薄膜之间的层压粘合强度大于1.5N/15mm。
39.根据权利要求36所述的层压膜，其中所述第一薄膜和所述第二薄膜之间的层压粘合强度大于2.0N/15mm。
40.一种制品，包括根据权利要求36-39中任一项所述的层压膜。
41.根据权利要求40所述的制品，其中所述制品是包装制品。
42.根据权利要求40或41所述的制品，其中所述制品耐巴氏灭菌。
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| US62/407,105 | 2016-10-12 | ||
| PCT/US2017/046077 WO2018031640A1 (en) | 2016-08-12 | 2017-08-09 | Reinforcement barrier coatings |
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| JP7463961B2 (ja) * | 2019-03-28 | 2024-04-09 | 東洋紡株式会社 | ガスバリア性ポリアミドフィルム |
| NL2023592B1 (en) | 2019-07-30 | 2021-02-23 | Scholle Ipn Ip Bv | Container assembly and method for preparing such a container assembly |
| CN113201160B (zh) * | 2020-02-01 | 2022-08-19 | 中国石油化工股份有限公司 | 一种控湿阻隔复合薄膜及其制备方法和应用 |
| US20230132997A1 (en) * | 2020-03-31 | 2023-05-04 | Dai Nippon Printing Co., Ltd. | Decorative sheet and decorative resin molded article |
| US11932000B2 (en) | 2021-03-23 | 2024-03-19 | Whirlpool Corporation | Refrigerator having a membrane |
| FR3125021B1 (fr) * | 2021-07-08 | 2024-03-22 | Sediver | Procédé de conditionnement d’isolateurs électriques en verre ou porcelaine revêtus de silicone |
| CN113480764B (zh) * | 2021-07-31 | 2021-12-24 | 贵州省材料产业技术研究院 | 一种增强型聚乙烯醇抗菌膜的制备方法及其产品 |
| CN113524843A (zh) * | 2021-08-03 | 2021-10-22 | 海南赛诺实业有限公司 | 一种高阻隔复合膜及其制备方法 |
| CN113755052A (zh) * | 2021-09-18 | 2021-12-07 | 洋紫荆油墨(中山)有限公司 | 一种扣板油墨及其制备方法与应用 |
| CN115612377B (zh) * | 2022-11-23 | 2023-11-21 | 昆明理工大学 | 一种复合涂料在青皮核桃保鲜中的应用 |
Family Cites Families (22)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US5349023A (en) | 1991-12-12 | 1994-09-20 | Kuraray Co., Ltd. | Vinyl alcohol copolymer having terminal amino group |
| US6348256B1 (en) | 1998-09-29 | 2002-02-19 | Celanese International Corporation | Ink jet paper coatings containing amine functional monomer grafted poly(vinyl alcohol) |
| US6656602B1 (en) | 1999-06-04 | 2003-12-02 | Jsr Corporation | Gas barrier coating composition, process for producing the same, and gas barrier coating film |
| JP4032607B2 (ja) | 1999-09-10 | 2008-01-16 | 凸版印刷株式会社 | 可撓性を有するガスバリア性蒸着フィルム |
| JP2002273812A (ja) | 2001-03-16 | 2002-09-25 | Toppan Printing Co Ltd | 積層材料及び漬物包装袋 |
| JP4085814B2 (ja) * | 2001-04-09 | 2008-05-14 | 凸版印刷株式会社 | 積層体 |
| JP4765216B2 (ja) | 2001-07-30 | 2011-09-07 | 凸版印刷株式会社 | 透明ガスバリア積層フイルム |
| US20030187113A1 (en) * | 2002-03-27 | 2003-10-02 | Jsr Corporation | Gas barrier coating composition and method for manufacturing same |
| JP2005335110A (ja) | 2004-05-25 | 2005-12-08 | Toppan Printing Co Ltd | ガスバリア積層体 |
| US20060116471A1 (en) * | 2004-11-26 | 2006-06-01 | Mitsubishi Chemical Corporation | Water soluble resin composition, gas barrier film and packaging material employing it |
| US8679536B2 (en) | 2005-08-24 | 2014-03-25 | Actamax Surgical Materials, Llc | Aldol-crosslinked polymeric hydrogel adhesives |
| EP1932880B8 (en) * | 2005-08-31 | 2012-03-07 | Mitsui Chemicals Tohcello Co., Ltd. | Gas barrier film, gas barrier laminate and method for production of the film or laminate |
| JP5479089B2 (ja) | 2006-05-01 | 2014-04-23 | ナノパック、インク． | フィルム及び構造に対するバリアコーティング |
| EP2326674B9 (en) * | 2008-09-12 | 2014-09-03 | Sekisui Specialty Chemicals America, LLC | Improved barrier layer |
| US20100255326A1 (en) * | 2008-10-07 | 2010-10-07 | Ciba Corporation | Printable gas barriers |
| EP2480710B1 (en) | 2009-09-25 | 2018-01-24 | Toray Plastics (America) , Inc. | Multi-layer high moisture barrier polylactic acid film and its method of forming |
| WO2012115128A1 (ja) * | 2011-02-25 | 2012-08-30 | 日本合成化学工業株式会社 | 水性塗工液及びこれを用いた多層構造体 |
| US20140141262A1 (en) * | 2011-06-29 | 2014-05-22 | Sun Chemical Corporation | Vinyl alcohol polymers with silane side chains and compositions comprising the same |
| KR102197243B1 (ko) | 2013-03-27 | 2021-01-04 | 도판 인사츠 가부시키가이샤 | 적층체 및 가스 배리어 필름 |
| EP2999719B1 (en) * | 2013-05-21 | 2020-07-29 | Sun Chemical Corporation | Acetalized polyvinyl alcohol barrier coatings |
| KR20160143763A (ko) | 2014-04-10 | 2016-12-14 | 나노팩, 인크. | 증기 침착된 코팅 및 중합체 기반 코팅을 합한 증진된 배리어 필름 |
| US20160053133A1 (en) * | 2014-07-28 | 2016-02-25 | Gary W. Beall | Molecularly self-assembling nanocomposite barrier coating for gas barrier applications and flame retardancy |
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| CN109562865A (zh) | 2019-04-02 |
| US11118080B2 (en) | 2021-09-14 |
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