CN114630936A - 具有提升的水蒸气阻隔的mfc基材 - Google Patents
具有提升的水蒸气阻隔的mfc基材 Download PDFInfo
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- CN114630936A CN114630936A CN202080074508.XA CN202080074508A CN114630936A CN 114630936 A CN114630936 A CN 114630936A CN 202080074508 A CN202080074508 A CN 202080074508A CN 114630936 A CN114630936 A CN 114630936A
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- CN
- China
- Prior art keywords
- surface treatment
- treatment composition
- mfc
- acid
- cellulosic substrate
- Prior art date
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Abstract
提供包括(a)至少一个包含MFC的纤维素基材的层和(b)布置在所述纤维素基材的至少一个表面上的第一阻隔层的阻隔材料,以及用于降低纤维素基材的水蒸气透过率(WVTR)的方法。
Description
技术领域
提供包括(a)至少一个包括微纤化纤维素的纤维素基材的层和(b)布置在所述纤维素基材的至少一个表面上的第一阻隔层的阻隔材料,以及用于降低纤维素基材的水蒸气透过率(WVTR)和任选地改善纤维素基材的氧气阻隔(OTR)和/或对油和/或油脂的阻隔的方法。
背景技术
基于纤维素的基材的一个问题在于,它们对水分非常敏感并且在高相对湿度(RH)下基本上不提供氧气阻隔且在低或高RH下几乎不提供或不提供水分阻隔。另外问题在于,纤维素膜非常难以通过使用例如在造纸机上的丝网的湿法成网制造,因为快速脱水是困难的且影响幅材品质和特别地随后的阻隔性质。
纳米纤维素材料例如微纤化纤维素材料的水分敏感度问题记载于很多科技文章中,它们包括水蒸气–引发的溶胀和例如良好的氧气阻隔的许多理论及效果,请见综述例如Wang,J.等人(Moisture and Oxygen Barrier Properties of Cellulose Nanomaterial-Based Films,ACS Sustainable Chem.Eng.,2018,6(1),pp 49–70)。除纤维素结晶度和聚合物添加剂的作用外(Kontturi,K.,Kontturi,E.,Laine,J.,Specific water uptake ofthin films from nanofibrillar cellulose,Journal of Materials Chemistry A,2013,1,13655),已经提议许多各种各样的疏水涂覆溶液。
这些问题不仅适用于净(未加工的,neat)基材而且适用于转换基材(即其中基材例如与其它基材例如纸或纸板层叠的那些,所述其它基材也因水分扩散会导致阻隔性质随时间降低而缺乏(不具)水分阻隔)。
一个挑战在于,形成具有很多阻隔性质的薄基材而不使用塑料层例如PE,或能够减少塑料层或施加的塑料层的厚度。本技术容许形成具有提升的阻隔性质(对于氧气、水蒸气和其它气体)的可持续基材或膜而不使用塑料层叠体或涂层。该基材可与聚合物或塑料层层叠以实现超级阻隔性质或提供其它特征例如热密封性或液体阻隔。
发明内容
提供用于降低包括微纤化纤维素(MFC)的纤维素基材的水蒸气透过率(WVTR)的方法,所述方法包括如下步骤:
a.提供包括MFC的纤维素基材;
b.将第一表面处理组合物施加到所述纤维素基材的至少一个表面,所述第一表面处理组合物包括水溶性聚合物和交联剂;和
c.容许所述第一表面处理组合物固化以在所述纤维素基材的所述至少一个表面上形成第一阻隔层。
还提供阻隔材料,包括:
-至少一个包括MFC的纤维素基材的层,
-布置在所述纤维素基材的至少一个表面上的第一阻隔层,所述第一阻隔层通过将包括水溶性聚合物和交联剂的第一表面处理组合物施加到所述纤维素基材和容许所述第一表面处理组合物固化,由此形成第一阻隔层而形成。
本发明的另外方面在下面的详细描述、实施例和所附的权利要求中阐述。
具体实施方式
已经发现,MFC基材的水蒸气阻隔性质的显著改善可通过如下实现
a.提供包括MFC的纤维素基材;
b.将第一表面处理组合物施加到所述纤维素基材的至少一个表面,所述第一表面处理组合物包括水溶性聚合物和交联剂;和
c.容许所述第一表面处理组合物固化以在所述纤维素基材的所述至少一个表面上形成第一阻隔层。
因此,本文中公开了用于降低包括MFC的纤维素基材的水蒸气透过率(WVTR)的方法,所述方法包括如下步骤:
a.提供包括MFC的纤维素基材;
b.将第一表面处理组合物施加到所述纤维素基材的至少一个表面,所述第一表面处理组合物包括水溶性聚合物和交联剂;和
c.容许所述第一表面处理组合物固化以在所述纤维素基材的所述至少一个表面上形成第一阻隔层。
阻隔材料–其可根据本文中描述的方法制造–包括:
-至少一个包括MFC的纤维素基材的层,
-布置在所述纤维素基材的至少一个表面上的第一阻隔层,所述第一阻隔层通过将包括水溶性聚合物和交联剂的第一表面处理组合物施加到所述纤维素基材和容许所述第一表面处理组合物固化,由此形成第一阻隔层而形成。
在不局限于理论的情况下据信,本文中公开的阻隔材料的改善性质在于,一个层提供良好的氧气阻隔(在该情形中MFC的基材)且一个阻隔层提供良好的WVTR(交联层),和其中具有交联剂的施加的涂层能够向基础基材提供补充的物理和机械性质。
在一种实施方式中,阻隔层可呈一个、两个或更多个阻隔层的形式且布置在基材的一个或两个面上。在一种实施方式中,第一阻隔层布置在基材的仅一个表面上或在基材的两面上。在一种实施方式中,第一和第二阻隔层布置在基材的仅一个表面上或在基材的两面上。
优选地,本文中公开的阻隔材料同时改善至少两种阻隔性质,例如改善的WVTR、改善的OTR、对油和/或油脂的阻抗性。在一种实施方式中,涂层将主要产生良好的水蒸气阻隔,但其还将有助于改善基材的OTR。在一种实施方式中,阻隔材料将提供良好的对于源于食物的油和/或油脂的抗性。
在另外实施方式中,阻隔材料用于包装或包裹应用例如工业、食物、化妆品和个人护理或电子器件应用。阻隔材料也可用于包装纸,包括防油脂纸或作为例如用于吸管的基础片材。
下面描述本发明的方法和阻隔材料的细节。本发明方法的细节可应用于本发明的阻隔材料,且经过必要的修正,反之亦然。
包括MFC的纤维素基材
本技术需要包括微纤化纤维素(MFC)的纤维素基材。
MFC存在不同的同义词,例如纤维素微原纤、原纤化纤维素、纳米纤维素、纳米原纤化纤维素、原纤聚集体、纳米级纤维素原纤、纤维素纳米纤维、纤维素纳米原纤、纤维素微纤维、纤维素原纤、微纤丝状纤维素、微原纤聚集体和纤维素微原纤聚集体。纤维素纤维优选地原纤化至这样的程度:当对于溶剂交换和冷冻干燥的材料用BET方法测定时,形成的纳米纤维素的最终比表面积为约1至约400m2/g、例如10至300m2/g或更优选地50-200m2/g。MFC的平均原纤直径为1-1000nm、优选地10-1000nm。在一种实施方式中,MFC包括至少50wt%、例如至少60wt%、适宜地至少70wt%的具有小于100nm的平均原纤直径的原纤。MFC可通过分析高分辨率SEM或ESEM图像来表征。
存在用于生产微纤化纤维素的各种方法,例如单或多遍(pass,道次)精制、预水解后接原纤的精制或高剪切崩解或释放。为了使微纤化纤维素制造既节能又可持续,经常需要一个或若干个预处理步骤。因此,可将待供应的浆的纤维素纤维酶促地或化学地预处理,以例如减少半纤维素或木质素的量。纤维素纤维可在原纤化前化学改性,其中纤维素分子包括除原始纤维素中发现的以外的(或更多的)官能团。这样的基团尤其地包括羧甲基、醛和/或羧基基团(通过N-氧基介导氧化例如"TEMPO"获得的纤维素)或季铵(阳离子纤维素)。在上述方法之一中改性或氧化之后,更容易将纤维崩解为微纤化纤维素。
微纤化纤维素可包括一些半纤维素;量取决于植物来源。预处理的纤维例如水解的、预溶胀的或氧化的纤维素原材料的机械崩解通过适合设备例如精制器、研磨机、均化器、胶化器(colloider)、摩擦研磨机、超声发生器、单-或双-螺杆挤出机、流化器例如微流化器、大型流化器或其它流化器类型的均化器实施。取决于MFC制造方法,产物还可包括细料或纳米结晶纤维素或例如木纤维中或造纸工艺中存在的其它化学化合物。产物还可包括各种量的尚未有效原纤化的微米级纤维颗粒。
MFC可由来自阔叶木或针叶木纤维两者的木纤维素纤维制造。其也可由微生物来源、农业纤维例如麦秸浆、竹子、甘蔗渣或其它非木纤维来源制造。其优选地由包括来自原生纤维的浆的浆例如机械、化学和/或热机械浆制成。其也可由损纸或再生纸(即预-和后-消费者废弃物)制成。
MFC可为原始的(即未化学改性的)或其可为化学改性的。
磷酸化纳米纤维素(亦称磷酸化微纤化纤维素;P-MFC)典型地通过将浸泡在NH4H2PO4、水和尿素的溶液中的纤维素纤维反应和随后将纤维原纤化为P-MFC而获得。一种具体方法包括:提供纤维素浆纤维在水中的悬浮体和用磷酸化试剂将所述水悬浮体中的纤维素浆纤维磷酸化,随后用本领域常见的方法原纤化。适宜的磷酸化试剂包括磷酸、五氧化二磷、氯氧化磷、磷酸氢二铵和磷酸二氢钠。
微纤化纤维素的悬浮体用于形成纤维素基材。典型地,纤维素基材以基于总固体含量在0.01-100wt%之间例如在30和100wt%之间、适宜地在40和100wt%之间、例如在50和100wt%之间或在70和100wt%之间的量包括微纤化纤维素。
用于形成纤维素基材的悬浮体典型地为含水悬浮体。悬浮体可包括从造纸工艺知晓的另外的化学组分。它们的示例可为纳米填料或填料例如纳米粘土、膨润土、滑石、碳酸钙、高岭土、SiO2、Al2O3、TiO2、石膏等。纤维质基材还可包括增强试剂,例如纤维素衍生物或天然淀粉或改性淀粉例如比如阳离子淀粉、非离子淀粉、阴离子淀粉或两性淀粉。增强试剂还可为合成聚合物。在进一步的实施方式中,纤维质基材还可包括助留和助滤化学品例如阳离子聚丙烯酰胺、阴离子聚丙烯酰胺、二氧化硅、纳米粘土、矾、P-DADMAC、PEI、PVAm等。在又一进一步实施方式中,纤维素基材还可包括其它典型的工艺或性能化学品,例如染料或荧光增白试剂、消泡剂、湿强度树脂、杀生物剂、疏水试剂、阻隔化学品等。
微纤化纤维素悬浮体可另外包括阳离子或阴离子微纤化纤维素;例如羧甲基化微纤化纤维素。在一种实施方式中,阳离子或阴离子微纤化纤维素以微纤化纤维素总量的小于50wt%的量、优选地以小于40wt%的量或更优选地以小于30wt%的量存在。
纤维素基材的由悬浮体的形成工艺可为流延或湿法成网,以形成在基材上的不将纤维素基材从其除去的自立式膜或涂层。本方法中形成的纤维素基材应理解为具有两个相反的主平面。因此,纤维素基材可为膜或涂层,和最优选为膜。纤维素基材可具有在1-80之间、优选地在10-50gsm之间、例如比如10-40gsm、最优选地在20-35gsm之间的克重。特别是对于涂层,克重可为低的,例如0.1-20gsm或更优选地甚至0.1-10gsm。
在本文描述的方法的一个方面中,纤维素基材在其已经干燥后,例如在其具有40-99.5%重量、例如比如60-99%重量、80-99%重量或90-99%重量的固体含量时进行表面处理。
在本文描述的方法的一个方面中,待表面处理的纤维素基材已经通过优选地在纸或纸板机器上的多孔丝网上湿法成网形成和具有50-99%重量的固体含量。
在本文描述的方法的另一方面中,待表面处理的纤维素基材已经通过流延形成和具有50-99%重量的固体含量。
在本文描述的方法的另一方面中,纤维素基材在其已经干燥后,例如在其具有50-99%重量、例如比如60-99%重量、80-99%重量或90-99%重量的固体含量时进行表面处理。
在本文描述的方法的另一方面中,纤维素基材在其已经干燥之前,例如在其具有0.1-50%重量、例如比如1-40%重量或10-30%重量的固体含量时进行表面处理。
在本文描述的方法的另一方面中,待表面处理的纤维素基材为具有范围为1-100g/m2在处理后的克重、更优选地范围为10-50g/m2在处理后的克重的自立式膜。可将该自立式膜直接附接到载体基材上或经由一个或多个连结层附接。
在一种实施方式中,载体基材为纸或纸板、或者塑料或矿物涂覆的纸或纸板。基材的实例为例如防油脂纸、玻璃纸、羊皮纸、标签纸、袋和纸袋纸、浸渍纸、固体漂白的板、固体未漂白的板、折叠盒板、白色衬里芯片板、瓦楞纸板。
因此,本文中公开的阻隔材料可在离线或在线工艺中施加在所述基材上。优选地,可将本文中公开的阻隔材料进一步层叠和制造成期望的最终产品。
浆纤维和粗细料的量可在0-60wt%的范围内。浆纤维和细料的量可事后例如通过将干或湿样品崩解、随后分级和分析级分粒度而估计。优选地,分级和分析从未干燥的配浆以分别测定细料和纤维的量。
纤维素基材还可包括范围为1-50%重量的一种或多种填料,例如纳米填料。典型的纳米填料可为纳米粘土、膨润土、二氧化硅或硅酸盐、碳酸钙、滑石粉等。优选地,填料的至少一部分为板状填料。优选地,填料的一个维度应具有1nm至10μm的平均厚度或长度。若例如用光散射技术测定填料的粒度分布,则优选的粒度应为这样的:大于90%在2μm以下。
表面处理的纤维素基材优选地具有3-12的表面-pH或更优选地5.5-11的表面-pH。更特别地,表面处理的纤维素基材可具有高于3、优选地高于5.5的表面-pH。特别是,表面处理的纤维素基材可具有小于12、优选地小于11的表面-pH。
纤维素基材的表面pH对最终产品(即干产品)测量。“表面pH”通过使用置于表面上的新鲜纯水而测量。进行五次平行测量且计算平均pH值。将感测器用纯或超纯水冲洗且然后将纸样品置于潮湿/湿感测器表面上且在30s后记录pH。将标准pH计用于所述测量。
在表面处理之前,纤维素基材适宜地具有范围为100-5000cc/m2/24h(38℃,85%RH)、更优选地范围为100-1000cc/m2/24h的根据ASTM D-3985的在10-50gsm之间的克重下的氧透过率(OTR)值。
纤维素基材的克重优选为10-50gsm。典型地,这样的基材基本上不具有或具有非常低的水蒸气阻隔。因此,基材可具有大于100g/m2/d、优选地大于200g/m2/d和更优选地大于500g/m2/d的在施加所述第一表面处理组合物之前的WVTR(在23℃和50%RH下)。
基材可为半透明或透明的。在一种实施方式中,纤维素基材具有至少75%、优选地至少80%的根据DIN 53147测量的半透明度。MFC基材也可为在例如纸板上的MFC涂层或膜。基材轮廓(概况,profile)通过例如甚至水分轮廓或通过超压延或通过再湿化和再-干燥而控制。因此,本文中公开的方法可进一步包括在施加所述第一表面处理组合物之前压延纤维素基材的步骤。
第一表面处理组合物
将第一表面处理组合物施加到纤维素基材的至少一个表面。第一表面处理组合物包括水溶性聚合物和交联剂。
因此,第一阻隔层通过将第一表面处理组合物施加到所述纤维素基材和容许所述第一表面处理组合物固化而形成。第一表面处理组合物典型地以1-10gsm、优选地1-4gsm的涂覆重量施加。
固化程度可通过不同手段测定但固化效果经常看作改善的阻隔性质。固化程度也可例如作为新类型键的形成通过使用光谱方法检测。
在一种实施方式中,选择能够将第一表面处理组合物交联,由此与在没有交联剂情况下完成的相应表面处理相比改变其物理-化学性质的交联剂。交联剂和聚合物的比率优选地在5:95和95:5之间和更优选地在10:90和90:10之间和更优选地在20:80和80:20之间和最优选地在30:70和70:30(w/w)之间。
优选的是,交联剂也能够将MFC交联,且在水溶性聚合物和MFC之间交联,于是增大基材的完整性。因此,交联剂不仅特别地将阻隔层交联,而且将阻隔层与基材交联和甚至在一定程度上在基材本身内交联。
交联剂适宜地选自有机酸、优选地有机多元酸;和有机酸或有机多元酸的金属盐;或有机酸和有机酸金属盐的混合物。“有机酸”为包括羧酸部分(-CO2H)的有机分子,而“有机多元酸”为包括多于一个这样的羧酸部分的有机分子。适宜的有机酸选自柠檬酸、乳酸、乙酸、甲酸、草酸、尿酸、苹果酸、1,2,3,4-丁烷四羧酸、丙二酸或酒石酸。柠檬酸为最优选的。柠檬酸的量可在5:95至95:5(w/w)之间变化,但比率可取决于聚合物、涂覆方法和施加的层而变化。
适宜的有机酸或多元酸的金属盐为钠、钾、镁或钙盐,钠盐为最优选的,例如柠檬酸钠。通过包括有机酸或多元酸的金属盐,可提供其中交联剂包括有机酸(优选地有机多元酸)和所述有机酸的金属盐的缓冲的水溶液。在一种实施方式中,制作具体的缓冲溶液,使得现成混合物具有较高pH值。缓冲的溶液的优选pH范围为例如4-6或5-7或6-8或7-9或8-10或9-11。
第一表面处理组合物的总固体含量大于10%w/w、和优选地大于15%w/w。
典型地,第一表面处理组合物包括至少2%、例如至少5%、例如至少10%w/w的水溶性聚合物。水溶性聚合物选自聚乙烯醇、聚丙烯酸酯(盐)、多糖例如比如淀粉、纤维素或瓜尔胶;或其混合物或共聚物,和优选地选自聚乙烯醇。实例可为聚乙烯醇和多糖的混合物。
术语“聚乙烯醇”包括部分或完全水解的、乙基化的、阳离子化的或羧基化的聚乙烯醇。术语“淀粉”包括改性淀粉,例如阴离子、阳离子、非离子或疏水改性的淀粉。术语“纤维素”包括纤维素衍生物(包括半纤维素)、适宜地羧甲基纤维素钠(NaCMC)、羟乙基纤维素(HEC)和乙基羟乙基纤维素(EHEC)。
值得注意的是,水溶性聚合物(例如聚乙烯醇)的溶液一般不用于水分阻隔,因其本身易于在水或水分中溶解。
在一种实施方式中,可提供具有小于60gsm或更优选地小于50gsm和最优选地小于40gsm的克重的纤维素基材和一个第一阻隔层。
可重复方法的步骤b.和c.,使得施加多于一个、例如比如2、3、4、5或10个第一阻隔层。因此,阻隔材料可包括多于一个、例如比如2、3、4、5或10个第一阻隔层。
令人意外的是,当施加第一表面处理组合物时未发生起泡,因为特别是成膜聚合物可导致表皮形成和因此的起泡趋势是相当常见的。
进一步的表面处理组合物
在一个方面中–在第一表面处理组合物的固化之后–可将第二表面处理组合物施加至第一阻隔层。第二表面处理组合物包括第二水溶性聚合物和任选的交联剂。容许所述第二表面处理组合物干燥和/或固化形成第二阻隔层。
第二表面处理组合物和/或底漆(打底)表面处理组合物典型地另外包括金属盐。
在一个替代方案中,第二表面处理组合物不含交联剂。在这样的情形中,水溶性聚合物不交联/固化,而是仅仅干燥和形成膜或涂层。
典型地,第一和第二表面处理组合物为水溶性聚合物和–在适用情况下–所述交联剂的水溶液。
在一个优选方面中,第一表面处理组合物和第二表面处理组合物包括相同的水溶性聚合物。这提供提升的在由此形成的阻隔层之间的相容性。术语“相同”在应用于水溶性聚合物时意指,两种这样的聚合物由相同单体形成,虽然它们在其它性质例如分子重量方面可不同。
以类似方式,第一表面处理组合物、第二表面处理组合物可包括相同交联剂。这可容许在阻隔层之间交联以及在同一阻隔层中内部地交联。
表面处理组合物、特别是第一表面处理组合物典型地具有在3和7之间的pH。这可通过在组合物中包括缓冲剂而实现,如上所述。
用于施加表面处理组合物的适宜方法包括借助印刷机例如柔版印刷、轮转凹印、旋转或平台丝网印刷、反向轮转凹印、喷墨或平版印刷机、网纹辊型施加器或其改造形式;或膜压、表面施胶、刮板或棒涂覆、喷涂或帘涂。涂覆可离线或在线完成。
优选地,涂层以至少一个具有1-10gsm、优选地1-4gsm的干涂层重量的层施加。
涂层优选地在至少一面上且在至少一个步骤中施加。若使用例如用于施加表面处理溶液的印刷机,则每次印刷停驻(站,station)的施加量为在湿态时的2-80gsm或更优选地在湿态时的3-40gsm(基于网纹辊孔体积和100%转移效率)。液体的干含量优选地高于1wt%或更优选地>5%和最优选地>10wt%。
为易于施加,表面处理组合物可具有在100-10 000mPas之间或更优选地300-8000mPas和最优选地500-3000mPas的在100rpm和23℃下测量的Brookfield粘度。
基材的压延可使用例如一个或多个具有高的辊隙负荷和温度的压延辊隙(例如超压延机中)在线或离线地完成。还有,可采用通过例如杨克(Yankee)式滚筒的平滑化。还有,压延可在较高温度下完成以确保固化和改善的交联。可使用温度例如T>120℃或更优选地>140℃或最优选地>160℃但小于240℃(滚筒温度),就此,压延是指通过施加额外的热量和压力来改善交联的后处理。实施例呈现来自使用未压延的基材和超压延的基材两者的结果,即在表面处理之前。
材料性质
用于生产纤维素基材的MFC悬浮体–在涂覆前–具有大于50、优选地大于60和更优选地大于70的根据ISO 5267-1的Schopper-Riegler(SR)值。SR值为纤维素纤维的精制度的度量,且为悬浮体的滤阻性的度量。必须理解,只有对于较粗的MFC等级和某些细的微纤化纤维素-纤维混合物,可准确测定SR值,因为较高含量的非常细的原纤可通过丝网且因此残留悬浮体中的提供抗脱水性的实际固体含量减少。
在施加表面处理组合物之前,在一种实施方式中纤维素基材具有小于25000s/100ml、优选地小于20 000s/100ml和更优选地小于15 000s/100ml的根据ISO 5636-5的空气阻力值。本技术允许该空气阻力值的增大。因此,在第一表面处理组合物的固化后,在一个实施方式中纤维素基材具有大于25000s/100ml、优选地大于30 000s/100ml和更优选地大于40000s/100ml的在所述第一表面处理组合物的固化后的根据ISO 5636-5的空气阻力值。在另外实施方式中,空气阻力是不可测量的,即太高以至于不能使用ISO方法5636-5测量。
本技术还允许改善的作为WVTR测量的水蒸气阻隔性质。因此,在施加第一表面处理组合物之前,纤维素基材典型地具有大于100g/m2/d、优选地大于200g/m2/d和更优选地大于500g/m2/d的在之前的WVTR(在23℃和50%RH下)。
在第一表面处理组合物的固化之后,纤维素基材典型地具有小于100g/m2/d、优选地小于75g/m2/d和更优选地小于50g/m2/d的WVTR(在23℃和50%RH下)。
在第一表面处理组合物的固化后,纤维素基材典型地具有大于5h、优选地大于15h、和更优选地大于20h的在所述第一表面处理组合物的固化之后根据改造的ASTM F119-82方法的抗油脂性(在23℃和50%RH下)。
实施例
包括100%微纤化片材的幅材是使用湿法成网方法使用长网造纸机设想(concept)随后经历挤压(压榨)部和干燥部制备的。将基材制备成32gsm的定量且干燥至小于10wt%的水分含量。微纤化纤维素具有92的Schopper-Riegler值。所述基材以未压延形式和在使用超压延机压延后两者使用。
聚乙烯醇(Poval 15-99,Kuraray)通过在高温下以1小时在搅拌下溶解而制备。容许该溶液冷却至室温,之后与交联试剂(柠檬酸)混合。PVOH和柠檬酸的混合物以50/50比率制成且将pH调至4.4。混合物的干含量为17wt-%。
将聚合物溶液通过分别使用一次和两次印刷停驻的柔版印刷单元施加。网纹辊孔体积为15cm3/m2。中期(Interim,临时)的后干燥通过IR干燥器完成。速度为13m/min。预计的涂覆重量为约0.3-1g/m2。处理基材的仅一面且分析处理的面。
使用的测试方法为:
Schopper-Riegler(SR)(ISO 5267-1)
氧透过率(OTR)(ASTM F-1927),
水蒸气透过率(WVTR)(ASTM F-1249)
抗油脂性,鸡脂肪,60℃(改造的ASTM F119-82)
实施例1–对比例
制备32gsm具有2003(s/100ml)空气阻力(格利-希尔(Gurley–Hill))值的基材。该样品不具有气体阻隔性质,这也由低的G-H值指示。
实施例2–对比例
样品与实施例1相同但将基材超压延。特别地在光泽方面小幅改善但在阻隔性质方面并未改善。
实施例3–对比例
将样品2与聚乙烯膜(挤出涂层)层叠。该膜具有良好的水蒸气阻隔性质且也具有良好的氧气阻隔。
实施例4
使用一次印刷停驻,用不含交联剂的PVOH溶液将实施例1中使用的幅材进行表面处理。格利-希尔值为644s/100ml(3次测量的平均值),指示差的阻隔性质。
实施例5
根据以上描述,用一个印刷辊隙(nip)将实施例2中使用的幅材进行表面处理。将PVOH与柠檬酸混合且将pH调至4。G-H为42300s/100ml且进行阻隔测试,如下表中所示。所有的阻隔结果均是良好的。
实施例6
实施例2中使用的幅材运行通过2个印刷辊隙,其中PVOH和柠檬酸混合物在第一辊隙中且PVOH在第二辊隙中。该组合产生非常好的阻隔性质,如下表中所示。
空格和N.D.意指测试未完成,因为样品具有缺陷或通不过格利希尔测试,即G-H值是低的。
尽管已经通过多种实施方式和实施例的描述说明本发明,同时已经相当详细地描述这些实施方式和实施例,但申请人不希望将所附权利要求的范围限缩或以任何方式限制至这样的细节。对于本领域技术人员而言,另外的优势和变型将容易地出现。因此,本发明就其较宽方面来说不限于显示和描述的具体细节、代表性方法、和说明性实施例。因此,可作出与这些细节的偏离但未偏离申请人总体发明构思的精神或范围。
Claims (21)
1.用于降低包含微纤化纤维素(MFC)的纤维素基材的水蒸气透过率(WVTR)的方法,所述方法包括如下步骤:
i.提供包括MFC的纤维素基材;
ii.将第一表面处理组合物施加到所述纤维素基材的至少一个表面,所述第一表面处理组合物包括水溶性聚合物和交联剂;和
iii.容许所述第一表面处理组合物固化以在所述纤维素基材的所述至少一个表面上形成第一阻隔层。
2.根据权利要求1所述的方法,其中包含MFC的所述纤维素基材包括至少40%w/w MFC、优选地至少60%w/w MFC、更优选地至少80%w/w MFC。
3.根据前述权利要求的任一项所述的方法,其中所述交联剂选自:有机酸、优选地有机多元酸;和有机酸或有机多元酸的金属盐;或有机酸和有机酸的金属盐的混合物。
4.根据权利要求3所述的方法,其中有机酸选自柠檬酸、乳酸、乙酸、甲酸、草酸、尿酸、苹果酸、1,2,3,4-丁基四羧酸、马来酸或酒石酸,优选地柠檬酸。
5.根据权利要求3-4的任一项所述的方法,其中第一表面处理组合物为缓冲的水溶液,其中交联剂包括有机酸、优选地有机多元酸和所述有机酸的金属盐例如柠檬酸钠。
6.根据前述权利要求的任一项所述的方法,其中所述水溶性聚合物选自聚乙烯醇、聚丙烯酸酯、多糖例如比如淀粉、纤维素、瓜尔胶;或其混合物或共聚物,优选地选自聚乙烯醇。
7.根据前述权利要求的任一项所述的方法,其中所述基材具有小于25 000s/100ml、优选地小于20 000s/100ml和更优选地小于15 000s/100ml的在施加所述第一表面处理组合物之前的根据ISO 5636-5的空气阻力值以及大于25 000s/100ml、优选地大于30 000s/100ml和更优选地大于40000s/100ml的在所述第一表面处理组合物的固化之后的根据ISO5636-5的空气阻力值。
8.根据前述权利要求的任一项所述的方法,其中所述基材具有大于100g/m2/d、优选地大于200g/m2/d和更优选地大于500g/m2/d的在施加所述第一表面处理组合物之前的根据ASTM F-1249测量的WVTR(在23℃和50%RH下)以及小于100g/m2/d、优选地小于75g/m2/d和更优选地小于50g/m2/d的在所述第一表面处理组合物的固化之后的根据ASTM F-1249测量的WVTR(在23℃和50%RH下)。
9.根据前述权利要求的任一项所述的方法,其中第一表面处理组合物以1-10gsm、优选地1-4gsm的涂覆重量施加。
10.根据前述权利要求的任一项所述的方法,进一步包括如下步骤–在所述第一表面处理组合物的固化之后–将第二表面处理组合物施加到所述第一阻隔层,所述第二表面处理组合物包括第二水溶性聚合物和任选的交联剂;和容许所述第二表面处理组合物干燥和/或固化以形成第二阻隔层。
11.根据前述权利要求的任一项所述的方法,其中第一表面处理组合物包括至少10%w/w水溶性聚合物。
12.根据前述权利要求的任一项所述的方法,其中重复步骤ii和iii使得施加多于一个、例如比如2、3、4、5或10个第一阻隔层。
13.根据前述权利要求的任一项所述的方法,其中第一表面处理组合物具有在3和7之间的pH。
14.阻隔材料,其包括
-至少一个包括MFC的纤维素基材的层,
-布置在所述纤维素基材的至少一个表面上的第一阻隔层,所述第一阻隔层通过将包括水溶性聚合物和交联剂的第一表面处理组合物施加到所述纤维素基材和容许所述第一表面处理组合物固化,因此形成第一阻隔层而形成,其中所述阻隔材料具有小于100g/m2/d、优选地小于75g/m2/d和更优选地小于50g/m2/d的根据ASTM F-1249测量的WVTR(在23℃和50%RH下)。
15.根据权利要求14所述的阻隔材料,其中包括MFC的所述纤维素基材包括至少40%w/w MFC、优选地至少60%w/w MFC、更优选地至少80%w/w MFC。
16.根据权利要求14-15的任一项所述的阻隔材料,其中所述交联剂选自:有机酸、优选地有机多元酸;和有机酸或有机多元酸的金属盐;或有机酸和有机酸的金属盐的混合物。
17.根据权利要求14-16的任一项所述的阻隔材料,其中第一表面处理组合物为缓冲的水溶液,其中交联剂包括有机酸、优选地有机多元酸和所述有机酸的金属盐。
18.根据权利要求14-17的任一项所述的阻隔材料,其中所述水溶性聚合物选自聚乙烯醇、聚丙烯酸酯、多糖例如比如淀粉、纤维素或瓜尔胶;或其混合物或共聚物,优选地聚乙烯醇。
19.根据权利要求14-18的任一项所述的阻隔材料,进一步包括在所述第一阻隔层上的第二阻隔层,所述第二阻隔层通过将包括第二水溶性聚合物和任选的交联剂的第二表面处理组合物施加到所述第一阻隔层,和容许所述第二表面处理组合物干燥和/或固化而形成。
20.根据权利要求14-19的任一项所述的阻隔材料,其中第二表面处理组合物不含交联剂。
21.根据权利要求14-20的任一项所述的阻隔材料,其包括多于一个、例如比如2、3、4、5或10个第一阻隔层。
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US (1) | US20220389658A1 (zh) |
EP (1) | EP4055223A4 (zh) |
JP (1) | JP2023500241A (zh) |
CN (1) | CN114630936A (zh) |
BR (1) | BR112022008476A2 (zh) |
CA (1) | CA3157414A1 (zh) |
SE (1) | SE544673C2 (zh) |
WO (1) | WO2021090192A1 (zh) |
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SE2150737A1 (en) * | 2021-06-10 | 2022-12-11 | Stora Enso Oyj | Biobased barrier film for packaging material |
SE2250127A1 (en) * | 2022-02-10 | 2023-08-11 | Stora Enso Oyj | Surface-treated gas barrier film |
EP4273318A1 (en) | 2022-05-04 | 2023-11-08 | B&T Entwicklungs- und Vermarktungsgesellschaft mbH | Layered structure |
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US20180245289A1 (en) * | 2015-09-17 | 2018-08-30 | Stora Enso Oyj | Surface sizing of dense films |
CN109415875A (zh) * | 2016-06-22 | 2019-03-01 | 斯道拉恩索公司 | 微原纤化的膜 |
WO2019123405A1 (en) * | 2017-12-22 | 2019-06-27 | Stora Enso Oyj | Multilayer film comprising microfibrillated cellulose |
WO2019171279A1 (en) * | 2018-03-08 | 2019-09-12 | Stora Enso Oyj | A method for producing a film having good barrier properties and improved strain at break |
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ES2895479T3 (es) * | 2011-06-10 | 2022-02-21 | Mayr Melnhof Karton Ag | Método para producir un material de embalaje recubierto y un material de embalaje con al menos una capa de bloqueo para compuestos hidrófobos |
US20130175218A1 (en) * | 2011-12-16 | 2013-07-11 | The Research Foundation Of State University Of New York | Polymeric nanofibrous composite membranes for energy efficient ethanol dehydration |
LT2740685T (lt) * | 2012-12-06 | 2017-04-10 | Mayr-Melnhof Karton Ag | Dengtos pakavimo medžiagos gamybos būdas ir hidrofobinių mišinių pakavimo medžiaga su bent vienu apsauginiu sluoksniu |
JP6313755B2 (ja) * | 2013-05-08 | 2018-04-18 | 日本製紙株式会社 | 紙製バリア包装材料 |
KR20160020524A (ko) * | 2013-07-19 | 2016-02-23 | 아사히 가세이 셍이 가부시키가이샤 | 미세 셀룰로오스 섬유 시트 |
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JP6637259B2 (ja) * | 2015-06-04 | 2020-01-29 | 大王製紙株式会社 | 農業用シート |
BR112018073594B1 (pt) * | 2016-05-16 | 2023-05-16 | Melodea Ltd | Método para modificar a taxa de transmissão de oxigênio (otr) de um filme ou revestimento sólido |
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2019
- 2019-11-04 SE SE1951259A patent/SE544673C2/en unknown
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2020
- 2020-11-04 EP EP20885115.4A patent/EP4055223A4/en active Pending
- 2020-11-04 BR BR112022008476A patent/BR112022008476A2/pt not_active Application Discontinuation
- 2020-11-04 CA CA3157414A patent/CA3157414A1/en active Pending
- 2020-11-04 US US17/755,338 patent/US20220389658A1/en active Pending
- 2020-11-04 JP JP2022525089A patent/JP2023500241A/ja not_active Abandoned
- 2020-11-04 CN CN202080074508.XA patent/CN114630936A/zh active Pending
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US20180245289A1 (en) * | 2015-09-17 | 2018-08-30 | Stora Enso Oyj | Surface sizing of dense films |
CN109415875A (zh) * | 2016-06-22 | 2019-03-01 | 斯道拉恩索公司 | 微原纤化的膜 |
CN107574723A (zh) * | 2017-09-14 | 2018-01-12 | 安徽蓝韵包装有限公司 | 一种防油食品包装纸及其制备方法 |
WO2019123405A1 (en) * | 2017-12-22 | 2019-06-27 | Stora Enso Oyj | Multilayer film comprising microfibrillated cellulose |
WO2019171279A1 (en) * | 2018-03-08 | 2019-09-12 | Stora Enso Oyj | A method for producing a film having good barrier properties and improved strain at break |
Also Published As
Publication number | Publication date |
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SE544673C2 (en) | 2022-10-11 |
US20220389658A1 (en) | 2022-12-08 |
JP2023500241A (ja) | 2023-01-05 |
EP4055223A4 (en) | 2023-11-22 |
EP4055223A1 (en) | 2022-09-14 |
CA3157414A1 (en) | 2021-05-14 |
WO2021090192A1 (en) | 2021-05-14 |
BR112022008476A2 (pt) | 2022-07-12 |
SE1951259A1 (en) | 2021-05-05 |
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