CN107592891A - 含有表面处理水性聚合物涂层的涂布基底及其制备和使用方法 - Google Patents
含有表面处理水性聚合物涂层的涂布基底及其制备和使用方法 Download PDFInfo
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- CN107592891A CN107592891A CN201680027162.1A CN201680027162A CN107592891A CN 107592891 A CN107592891 A CN 107592891A CN 201680027162 A CN201680027162 A CN 201680027162A CN 107592891 A CN107592891 A CN 107592891A
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- waterborne polymeric
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Classifications
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- B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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Abstract
本发明公开了例如被涂布的基底,其包含被经表面处理的水性聚合物涂层涂布的纤维素基基底。在一些实施方案中,水性聚合物涂层是使用电晕处理进行表面处理的。也公开了制备和使用所述被涂布的基底的方法。
Description
相关申请的交叉引用
本申请要求2015年5月12日递交的美国临时申请No.62/160,252的优先权,将其内容全部引入本文以供参考。
发明领域
本发明涉及改进的用于纤维素基基底的水性聚合物涂层,及其制备和使用方法。
背景
在纤维素基底上的聚乙烯膜提供优良的阻隔性能(即,防水、油脂、油和湿气)。因为聚乙烯膜在低温下是热塑性的,其可以自身热密封,在不使用额外粘合剂的情况下提供粘合。由于关注可持久性,在工业上已经致力于减少对于在纤维素基底上的涂层使用聚乙烯,例如通过使用水性聚合物涂料代替聚乙烯。但是,理想的是在纤维素基基底(cellulose-based substrate)上具有改进性能的水性聚合物涂层。例如,当装满时,液体压力可以在杯子底部变得明显,导致在杯子底部与侧壁粘合的地方有时出现泄漏。泄漏也可以在粘合困难形状的地方出现。因此,需要具有改进粘合性的水性聚合物涂层。也需要具有在重叠边缘之间的改进粘合性的纤维素基底。本文公开的组合物和方法解决这些问题和其它需要。
发明概述
本文公开了例如被涂布的基底,其包含具有经表面处理的水性聚合物涂层的纤维素基基底。被涂布的基底可以包含纤维素基基底和在纤维素基基底表面上的水性聚合物涂层,其中水性聚合物涂层已经进行表面处理。在一些实施方案中,表面处理可以是高能放电。在一些实例中,水性聚合物涂层可以使用电晕处理进行表面处理。在一些实施方案中,纤维素基基底是纸板。在一些实施方案中,水性聚合物涂层含有纯的丙烯酸型共聚物,苯乙烯-丙烯酸型共聚物,苯乙烯-丁二烯共聚物,乙烯基丙烯酸型共聚物,或其组合。在一些实施方案中,水性聚合物涂层含有低聚物稳定化的苯乙烯-丙烯酸型共聚物胶乳,表面活性剂稳定化的苯乙烯丙烯酸型共聚物胶乳,或其组合。水性聚合物涂层可以具有2-30g/m2的涂布重量(例如10-25g/m2)。在一些实施方案中,水性聚合物涂层还含有选自以下材料的经过表面处理的颜料:表面活性剂;疏水改性的聚合物;苯乙烯-丙烯酸型树脂乳液;苯乙烯-丁二烯胶乳乳液;硅烷、硅氧烷、硅氧烷/有机硅树脂共混物,和它们的碳基类似物,以及它们的组合,从而形成经处理的颜料。
这里也公开了例如纸杯,其包含侧部和底部,和在纸杯的第一表面上的第一水性聚合物涂层,其中第一表面包括一个或多个侧部内表面或底部内表面,其中第一水性聚合物涂层已经进行表面处理,和其中侧部的底边经由含有第一水性聚合物涂层的密封粘合到底部的侧边。第一表面可以包括纸杯底部的内表面,纸杯侧部的内表面,或这两者。在一些实施方案中,纸杯包含在纸杯第二表面上的含有半结晶聚合物的第二涂层。当第一表面是侧部内表面时,第二表面可以包括纸杯底部的内表面。当第一表面是底部内表面时,第二表面可以包括纸杯侧部的内表面。纸杯侧部的底边可以经由含有第一水性聚合物涂层和第二涂层的密封粘合到底部的侧边。纸杯的侧部可以沿着侧边与其自身粘合。在一些实施方案中,第一水性聚合物涂层已经用高能放电进行表面处理。在一些实例中,第一水性聚合物涂层已经进行电晕处理。
在一些实施方案中,半结晶聚合物含有低密度聚乙烯、脂族芳族聚酯、尼龙或其组合。在一些实例中,半结晶聚合物可以是低密度聚乙烯均聚物或低密度聚乙烯共聚物。半结晶聚合物可以任选地具有极性官能度。在一些实施方案中,低密度聚乙烯共聚物可以是乙烯和含有丙烯酸甲酯、甲基丙烯酸或其组合的单体形成的共聚物。第二涂层可以具有0.4-2密耳的厚度。第二涂层可以具有95-105℃的熔点温度。第二涂层可以具有0.65-1.1g/cm3的密度。
在一些实施方案中,用热咖啡在90℃的起始温度下基本上填充纸杯之后达到30分钟,纸杯没有显示沿着纸杯密封处的泄漏。
也公开了制备本文所述的被涂布的基底和纸杯的方法。这些方法可以包括对水性聚合物涂层进行电晕处理。在一些实施方案中,电晕处理是在1-4(例如2-4)瓦特/每平方英尺每分钟下进行的。
在下文中描述一个或多个实施方案的细节。其它特征、目标和优点将从以下描述和权利要求体现出来。
附图简述
图1是显示电晕处理、颜料(粘土)和树脂对于在150℃下热密封的影响的帕累托图(Pareto chart),在p=0.5的标准化效果估算下进行(95%置信水平)。
图2是显示电晕处理、颜料(粘土)和树脂对于在200℃下热密封的影响的帕累托图,在p=0.5的标准化效果估算下进行(95%置信水平)。
图3是显示电晕处理、颜料(粘土)和树脂对于在250℃下热密封的影响的帕累托图,在p=0.5的标准化效果估算下进行(95%置信水平)。
图4是显示电晕处理和颜料(粘土)对于在150℃下热密封的影响的预期平均值的图,在p=0.5的标准化效果估算下进行(95%置信水平)。
图5是显示电晕处理和颜料(粘土)对于在200℃下热密封的影响的预期平均值的图,在p=0.5的标准化效果估算下进行(95%置信水平)。
图6是显示电晕处理和颜料(粘土)对于在250℃下热密封的影响的预期平均值的图,在p=0.5的标准化效果估算下进行(95%置信水平)。
图7是显示电晕处理、颜料(粘土)和树脂对于抗粘连性的影响的帕累托图,在p=0.5的标准化效果估算下进行(95%置信水平)。
图8是显示颜料和树脂对于抗粘连性的影响的预期平均值的图,在p=0.5的标准化效果估算下进行(95%置信水平)。
图9是是显示电晕处理、颜料(粘土)和树脂对于泄漏的影响的帕累托图,在p=0.5的标准化效果估算下进行(95%置信水平)。
图10是显示颜料和树脂对于泄漏的影响的预期平均值的图,在p=0.5的标准化效果估算下进行(95%置信水平)。
图11是被水性聚合物涂层涂布的纸板表面的图像。
图12是被水性聚合物涂层涂布的电晕处理纸板表面的图像。
发明详述
具体而言,本发明涉及被涂布的基底,其包含具有经表面处理的水性聚合物涂层的纤维素基基底。被涂布的基底包含纤维素基基底和在纤维素基基底表面上的水性聚合物涂层,其中水性聚合物涂层已经进行表面处理。在一些实施方案中,水性聚合物涂层可以使用高能放电进行表面处理。例如,第一水性聚合物涂层可以使用电晕处理进行表面处理。本发明也涉及纸杯,其包含被涂布的基底。本发明也公开了生产纸杯和被涂布的基底的方法。在一些实施方案中,本发明也涉及纸杯,其包含上述被水性聚合物涂层涂布的纤维素基基底。在一些实施方案中,纸杯也可以包含被半结晶聚合物涂层涂布的纤维素基基底。
纤维素基基底可以包括任何能被半结晶聚合物和/或水性聚合物涂层涂布的纸。纤维素基基底可以包括纤维素纤维和/或其它纤维,例如聚合物纤维。在一些实施方案中,纤维素基基底包括纸、纸板或卡纸板。纤维素基基底可以包括再循环纸。纤维素基基底可以例如适合用作离型纸、纸盘或纸杯。
在一些实施方案中,纤维素基基底的基重可以是80g/m2或更大(例如90g/m2或更大,100g/m2或更大,110g/m2或更大,120g/m2或更大,130g/m2或更大,140g/m2或更大,150g/m2或更大,160g/m2或更大,170g/m2或更大,180g/m2或更大,190g/m2或更大,200g/m2或更大,210g/m2或更大,220g/m2或更大,230g/m2或更大,240g/m2或更大,250g/m2或更大,260g/m2或更大,270g/m2或更大,280g/m2或更大,290g/m2或更大,300g/m2或更大,310g/m2或更大,320g/m2或更大,330g/m2或更大,340g/m2或更大,350g/m2或更大,360g/m2或更大,370g/m2或更大,380g/m2或更大,390g/m2或更大,400g/m2或更大,450g/m2或更大或500g/m2或更大)。在一些实施方案中,纤维素基基底的基重可以是600g/m2或更小(例如550g/m2或更小,500g/m2或更小,450g/m2或更小,420g/m2或更小,390g/m2或更小,380g/m2或更小,370g/m2或更小,360g/m2或更小,350g/m2或更小,340g/m2或更小,330g/m2或更小,320g/m2或更小,310g/m2或更小,300g/m2或更小,290g/m2或更小,280g/m2或更小,270g/m2或更小,260g/m2或更小,250g/m2或更小,240g/m2或更小,230g/m2或更小,220g/m2或更小,210g/m2或更小,200g/m2或更小,190g/m2或更小,180g/m2或更小,170g/m2或更小,160g/m2或更小,150g/m2或更小,140g/m2或更小,130g/m2或更小,120g/m2或更小,110g/m2或更小,100g/m2或更小,90g/m2或更小,80g/m2或更小,或70g/m2或更小)。在一些实施方案中,纤维素基基底的基重是80-600g/m2(例如90-550g/m2,100-500g/m2,110-450g/m2,或120-400g/m2)。在一些实施方案中,纤维素基基底具有适用于纸杯中的基重(例如285-400g/m2)。
水性聚合物涂层可以在纤维素基基底的表面上,其中水性聚合物涂层已经进行表面处理。水性聚合物涂层可以含有水性聚合物,其是可溶于水和/或可水分散的。在一些实施方案中,水性聚合物涂层可以含有纯的丙烯酸型共聚物,苯乙烯-丙烯酸型共聚物,苯乙烯-丁二烯共聚物,乙烯基丙烯酸型共聚物,或其组合。在一些实施方案中,水性聚合物涂层含有聚乙酸乙烯酯聚合物或乙烯-乙烯基丙烯酸型共聚物。
在一些实施方案中,水性聚合物涂层是如美国专利申请公开No.2011/0046284中所述的涂层,将其全部内容引入本文以供参考。例如,水性聚合物涂层可以包含具有至少一个以下所需特性的颜料:
·适合于给定应用的可接受的流变行为;
·受控的表面积,工程化流变粒子;
·超细尺寸的粒子;
·高度多孔粒子,其具有为了目标阻隔涂布应用所设计的孔径分布和表面积;和
·高表面积粒子。
颜料也可以进行热处理工艺,然后在进行或不进行热处理的情况下可以用能促进拒水和/或显著延缓目标物质扩散速率的材料处理(高的表面张力或接触角)。颜料可以用可包括但不限于以下的材料处理:
·表面活性剂,例如硬脂酸酯;
·疏水改性聚合物,例如聚乙烯亚胺(PEI);
·苯乙烯-丙烯酸型树脂乳液化合物;
·苯乙烯-丁二烯胶乳化合物;
·硅烷、硅氧烷、硅氧烷/有机硅树脂共混物,和它们的碳基类似物;和
·它们的组合。
在一些实施方案中,颜料可以用共聚物处理,共聚物例如是从包括以下的单体衍生的苯乙烯丙烯酸型共聚物:苯乙烯,(甲基)丙烯酸,(甲基)丙烯酸酯,(甲基)丙烯酸型胺,(甲基)丙烯腈,和它们的混合物。例如,苯乙烯丙烯酸型共聚物可以包含苯乙烯和至少一种以下物质:(甲基)丙烯酸,衣康酸,(甲基)丙烯酸甲基酯,(甲基)丙烯酸乙基酯,(甲基)丙烯酸正丁基酯,(甲基)丙烯酸异丁基酯,(甲基)丙烯酸叔丁基酯,(甲基)丙烯酸2-乙基己基酯,(甲基)丙烯酸型胺,(甲基)丙烯腈,和(甲基)丙烯酸羟基乙基酯。
在一些实施方案中,颜料可以用从包括以下的单体衍生的苯乙烯-丁二烯共聚物处理:苯乙烯,丁二烯,(甲基)丙烯酸型胺,(甲基)丙烯腈,衣康酸,和(甲基)丙烯酸。苯乙烯-丁二烯共聚物也可以包含0-3phm(份/每百份单体)的一种或多种交联单体,例如二乙烯基苯。
颜料体系可以是稳定的浆液,其可以含有任何上述颜料以及分散剂、任选的消泡剂和增稠剂的组合。分散剂可以是胶乳、淀粉或聚乙烯醇(PVOH)。天然增稠助剂包括例如淀粉或蛋白质,或合成聚合物例如STEROCOLL FS(可从BASF Corporation获得),可以用于增稠/稳定颜料体系。阻隔涂料配制剂包含颜料体系,任选的消泡剂/脱气剂/抑泡剂,交联剂(例如乙二醛或AZC),以及粘合剂。粘合剂可以是苯乙烯-丙烯酸树脂乳液(SA)、苯乙烯-丁二烯胶乳(SB胶乳)、PVOH、淀粉、蛋白质和其组合,其也可以对阻隔性能做出贡献。
在一些实施方案中,水性聚合物涂层可以具有2g/m2或更大的涂布重量(例如3g/m2或更大,4g/m2或更大,5g/m2或更大,6g/m2或更大,7g/m2或更大,8g/m2或更大,9g/m2或更大,10g/m2或更大,11g/m2或更大,12g/m2或更大,13g/m2或更大,14g/m2或更大,15g/m2或更大,16g/m2或更大,17g/m2或更大,18g/m2或更大,19g/m2或更大,20g/m2或更大,21g/m2或更大,22g/m2或更大,23g/m2或更大,24g/m2或更大,25g/m2或更大,26g/m2或更大,27g/m2或更大,28g/m2或更大,或29g/m2或更大)。在一些实施方案中,水性聚合物涂层可以具有30g/m2或更小的涂布重量(例如29g/m2或更小,28g/m2或更小,27g/m2或更小,26g/m2或更小,25g/m2或更小,24g/m2或更小,23g/m2或更小,22g/m2或更小,21g/m2或更小,20g/m2或更小,19g/m2或更小,18g/m2或更小,17g/m2或更小,16g/m2或更小,15g/m2或更小,14g/m2或更小,13g/m2或更小,12g/m2或更小,11g/m2或更小,10g/m2或更小,9g/m2或更小,8g/m2或更小,7g/m2或更小,6g/m2或更小,5g/m2或更小,4g/m2或更小,或3g/m2或更小)。在一些实施方案中,水性聚合物涂层可以具有2-30g/m2的涂布重量(例如5-28g/m2,或10-25g/m2)。涂布重量可以用克涂料/每平方米纤维素基基底的单位表示,并且可以直接通过所施加的涂料量和被涂料涂布的纤维素基基底的表面积计算。在一些实施方案中,水性聚合物涂料可以按照基于被涂布的纤维素基基底计小于15重量%的量涂布。
在一些实施方案中,本文公开的纤维素基基底和/或纸杯还包含含有半结晶聚合物的第二涂层。在这里,含有半结晶聚合物的第二涂层也称为半结晶聚合物涂层。在一些实施方案中,半结晶聚合物可以含有低密度聚乙烯(LDPE),“官能化”低密度聚乙烯共聚物,脂族芳族聚酯,脂族芳族聚酯/聚乳酸(PLA)共混聚合物,脂族聚酰胺(尼龙),有机硅(包括铂催化的有机硅),或其组合。半结晶聚合物的合适例子可以包括乙烯与包含丙烯酸甲酯、甲基丙烯酸或其组合的单体形成的共聚物。在一些实施方案中,在乙烯共聚物中的丙烯酸型单体的量可以是40%或更小。例如,在乙烯共聚物中的丙烯酸型单体的量可以是4-25%,4-20%,6-15%,6-13%。在一些实施方案中,半结晶聚合物含有可组合的、可生物降解的聚合物。
在一些实施方案中,第二涂层可以含有低密度聚乙烯均聚物或低密度聚乙烯共聚物。在一些实施方案中,聚乙烯共聚物可以任选地含有极性官能度(即,可以改性以包含官能单体,从而低密度聚乙烯共聚物的极性大于低密度聚乙烯均聚物的极性)。第二涂层可以含有通过乙烯单体和丙烯酸型单体聚合制备的低密度聚乙烯共聚物。丙烯酸型单体可以选自甲基丙烯酸,丙烯酸甲酯,或其组合。制备这些共聚物的方法是本领域已知的,它们可以例如使用配位或自由基聚合制备。在一些实施方案中,丙烯酸型单体的存在量是基于低密度聚乙烯共聚物重量计的3%或更大(例如4%或更大,5%或更大,6%或更大,7%或更大,8%或更大,9%或更大,10%或更大,11%或更大,12%或更大,13%或更大,14%或更大,15%或更大,16%或更大,17%或更大,18%或更大,或19%或更大)。在一些实施方案中,丙烯酸型单体的存在量是基于低密度聚乙烯共聚物重量计的20%或更小(例如19%或更小,18%或更小,17%或更小,16%或更小,15%或更小,14%或更小,13%或更小,12%或更小,11%或更小,10%或更小,9%或更小,8%或更小,7%或更小,6%或更小,5%或更小,或4%或更小)。在一些实施方案中,丙烯酸型单体的存在量是基于低密度聚乙烯共聚物重量计的3-20%(例如4-15%或5-10%)。
在一些实施方案中,通过ASTM D792(2008)检测,半结晶聚合物具有0.65g/cm3或更大的密度(例如0.7g/cm3或更大,0.75g/cm3或更大,0.8g/cm3或更大,0.85g/cm3或更大,0.9g/cm3或更大,0.95g/cm3或更大,1g/cm3或更大,1.05g/cm3或更大,1.1g/cm3或更大,1.15g/cm3或更大,1.2g/cm3或更大,1.25g/cm3或更大,1.3g/cm3或更大,1.35g/cm3或更大,1.4g/cm3或更大,或145g/cm3或更大)。在一些实施方案中,通过ASTM D792(2008)检测,半结晶聚合物具有1.5g/cm3或更小的密度(例如1.45g/cm3或更小,1.4g/cm3或更小,1.35g/cm3或更小,1.3g/cm3或更小,1.25g/cm3或更小,1.2g/cm3或更小,1.15g/cm3或更小,1.1g/cm3或更小,1g/cm3或更小,0.95g/cm3或更小,0.9g/cm3或更小,0.85g/cm3或更小,0.8g/cm3或更小,0.75g/cm3或更小,或0.7g/cm3或更小)。在一些实施方案中,通过ASTM D792(2008)检测,半结晶聚合物具有0.65-1.5g/cm3的密度(例如0.7-1.4g/cm3或0.75-1.25g/cm3)。
在一些实施方案中,通过ASTM D1238(2010)检测,半结晶聚合物具有2g/10min或更大的熔体流速(例如3g/10min或更大,4g/10min或更大,5g/10min或更大,6g/10min或更大,7g/10min或更大,8g/10min或更大,9g/10min或更大,10g/10min或更大,11g/10min或更大,12g/10min或更大,或13g/10min或更大)。在一些实施方案中,通过ASTM D1238(2010)检测,半结晶聚合物具有14g/10min或更小的熔体流速(例如13g/10min或更小,12g/10min或更小,11g/10min或更小,10g/10min或更小,9g/10min或更小,8g/10min或更小,7g/10min或更小,6g/10min或更小,5g/10min或更小,4g/10min或更大,或3g/10min或更大)。
在一些实施方案中,通过ASTM D3418(2012-e1)检测,半结晶聚合物具有70℃或更高的熔点温度(DSC)(例如80℃或更高,90℃或更高,110℃或更高,120℃或更高,130℃或更高,140℃或更高,150℃或更高,160℃或更高,170℃或更高,180℃或更高,190℃或更高,或200℃或更高)。在一些实施方案中,通过ASTM D3418(2012-e1)检测,半结晶聚合物具有210℃或更低的熔点温度(DSC)(例如200℃或更低,190℃或更低,180℃或更低,170℃或更低,160℃或更低,150℃或更低,140℃或更低,130℃或更低,120℃或更低,110℃或更低,100℃或更低,90℃或更低,或80℃或更低)。在一些实施方案中,通过ASTM D3418(2012-e1)检测,半结晶聚合物具有70-210℃的熔点温度(DSC)(例如80-200℃,90-180℃,或100-150℃)。在一些实施方案中,通过ASTM D3418(2012-e1)检测,半结晶聚合物具有多于一个(例如2个)熔点温度峰。
在一些实施方案中,通过ASTM D1525(2009)检测,半结晶聚合物具有40℃或更高的维卡软化点(例如45℃或更高,50℃或更高,55℃或更高,60℃或更高,65℃或更高,70℃或更高,75℃或更高,80℃或更高,85℃或更高,或90℃或更高)。在一些实施方案中,通过ASTM D1525(2009)检测,半结晶聚合物具有40-95℃的维卡软化点(例如50-90℃,或60-85℃)。
在一些实施方案中,半结晶聚合物涂层可以具有0.4密耳或更大的厚度(例如0.5密耳或更大,0.6密耳或更大,0.7密耳或更大,0.8密耳或更大,0.9密耳或更大,1密耳或更大,1.1密耳或更大,1.2密耳或更大,1.3密耳或更大,1.4密耳或更大,1.5密耳或更大,1.6密耳或更大,1.7密耳或更大,1.8密耳或更大,或1.9或更大)。在一些实施方案中,半结晶聚合物涂层可以具有2密耳或更小的厚度(例如1.9密耳或更小,1.8密耳或更小,1.7密耳或更小,1.6密耳或更小,1.5密耳或更小,1.4密耳或更小,1.3密耳或更小,1.2密耳或更小,1密耳或更小,0.9密耳或更小,0.8密耳或更小,0.7密耳或更小,0.6密耳或更小,或0.5密耳或更小)。在一些实施方案中,半结晶聚合物涂层可以具有0.4-2密耳的厚度(例如0.5-1.8密耳,0.6-1.6密耳,或0.75-1.5密耳)。涂层厚度可以基于涂料密度和被涂布的纤维素基基底的重量计算。
在一些实施方案中,半结晶聚合物涂料可以按照基于被涂布的纤维素基基底计的小于15重量%的量施用。
在一些实施方案中,水性聚合物涂层和/或半结晶聚合物涂层可以还包含一种或多种添加剂。在一些实施方案中,一种或多种添加剂可以包括无机填料和/或涂料颜料。无机填料通常具有显著比例的粒径大于2微米的粒子,而涂料颜料具有显著比例的粒径小于2微米的粒子。在一些实施方案中,可以加入无机填料和/或涂料颜料以向纸赋予特定的性能,例如平滑性,白度,增加的密度或重量,降低的孔隙率,增加的不透明性,平坦度,光泽度等。无机填料和/或涂料颜料可以包括碳酸钙(沉淀或研磨),高岭土,粘土,滑石,硅藻土,云母,硫酸钡,碳酸镁,蛭石,石墨,炭黑,氧化铝,氧化硅(热解法或沉淀在粉末或分散体中),胶态二氧化硅,硅胶,氧化钛,氢氧化铝,三水合铝,轧光白,和氧化镁。在一些实施方案中,水性聚合物涂层和/或半结晶聚合物涂层可以仅仅包含无机填料或涂料颜料,或可以包含无机填料和涂层颜料的共混物(例如重量比率为90:10,80:20,70:30,60:40,50:50,40:60,30:70,20:80或10:90)。
在一些实施方案中,水性聚合物涂层和/或半结晶聚合物涂层可以包含无毒的抗腐蚀颜料。这种抗腐蚀颜料的例子包括但不限于:磷酸盐型抗腐蚀颜料,例如磷酸锌、磷酸钙、磷酸铝、磷酸钛、磷酸硅,以及它们的正磷酸盐和熔融磷酸盐。
在一些实施方案中,水性聚合物涂层和/或半结晶聚合物涂层可以包含一种或多种染料和/或着色颜料,从而制备着色或带图案的纸或改变纸的色调。染料的例子可以包括基础染料,酸染料,阴离子直接染料,和阳离子直接染料。着色颜料的例子包括有机颜料和无机颜料,其是阴离子颜料分散体和阳离子颜料分散体的形式。
在一些实施方案中,水性聚合物涂层和/或半结晶聚合物涂层可以包含添加剂,例如增稠剂,分散剂,引发剂,稳定剂,链转移剂,缓冲剂,盐,防腐剂,阻燃剂,润湿剂,保护胶体,杀微生物剂,腐蚀抑制剂,交联剂,交联促进剂,以及润滑剂。在一些实施方案中,水性聚合物涂层和/或半结晶聚合物涂层可以含有用于防止解聚的添加剂(例如用于防止光引发的添加剂)。
本文所述的纤维素基基底可以包含一种或多种类型的涂层(例如两种类型的涂层)。在一些实施方案中,本文所述的纤维素基基底(例如在本文所述的纸杯上)可以在基底上具有多于一层的涂层,其中这些涂层可以含有相同或不同的涂料。在一些实施方案中,纤维素基基底含有水性聚合物涂料层。在一些实施方案中,纤维素基基底含有被施涂到半结晶聚合物涂料层上的水性聚合物涂料层。在一些实施方案中,纤维素基基底含有被施涂到水性聚合物涂料层上的半结晶聚合物涂料层。在一些实施方案中,纤维素基基底含有水性聚合物涂层和/或半结晶聚合物涂层和额外涂层。
本发明也涉及纸杯,其具有被水性聚合物涂层、半结晶聚合物涂层或其组合涂布的纤维素基基底。纸杯可以具有内表面、外表面、底部和侧部。水性聚合物涂层可以在纸杯的第一表面和/或第二表面上。半结晶聚合物涂层可以在纸杯的第二表面上。在一些实施方案中,第一表面包括一个或多个侧部内表面或底部内表面。在一些实施方案中,第二表面包括一个或多个侧部内表面或底部内表面。第二表面可以包括纸杯底部的内表面,其中第一表面是侧部的内表面。第一表面可以包括纸杯底部的内表面,其中第二表面是侧部的内表面。在一些实施方案中,底部的整个内表面被涂布。在一些实施方案中,仅仅一部分(例如10%或更大,20%或更大,30%或更大,40%或更大,50%或更大,60%或更大,70%或更大,80%或更大,或90%或更大)的底部内表面被涂布。在一些实施方案中,侧部的整个内表面被涂布。在一些实施方案中,仅仅一部分(例如10%或更大,20%或更大,30%或更大,40%或更大,50%或更大,60%或更大,70%或更大,80%或更大,或90%或更大)的侧部内表面被涂布。
可以使用造纸机在磨机中或通过印刷方法将水性涂料施涂到纤维素基基底上。半结晶聚合物涂料可以通过熔体挤出方法施涂到纤维素基基底上。在一些实施方案中,半结晶聚合物涂料可以在185℃或更高的熔体挤出温度下施涂到纤维素基基底上(例如190℃或更高,200℃或更大,210℃或更高,220℃或更高,230℃或更大,240℃或更高,250℃或更高,260℃或更高,270℃或更高,280℃或更高,290℃或更高,300℃或更高,或310℃或更高)。熔体挤出温度可以是320℃或更低(例如315℃或更低,310℃或更低,300℃或更低,290℃或更低,280℃或更低,270℃或更低,260℃或更低,250℃或更低,240℃或更低,230℃或更低,220℃或更低,210℃或更低,200℃或更低,或190℃或更低)。半结晶聚合物涂料的熔体挤出温度可以是185-325℃(例如215-320℃或235-315℃)。
在纤维素基底上的水性聚合物涂层可以使用任何适用于改进基底表面的方法进行表面处理,从而改进粘合性。在一些实施方案中,水性聚合物涂层可以被氧化、平滑化(例如燃烧在基底表面上的纤维)或其组合,从而改进粘合性。在一些实施方案中,表面处理可以包括高能放电,例如电离放电和/或热放电。这里使用的“高能放电”表示能改变在材料表面上的分子键和/或能量的能源。在一些实施方案中,能源可以打断在材料表面上的分子键。断裂的键现在自由地附着于自由基和在高能放电环境中存在的其它粒子。在一些实例中,水性聚合物涂层可以使用选自以下的方法进行表面处理(例如可以进行物理表面处理或热处理):电晕处理,等离子放电处理,火焰处理,或其组合。水性聚合物涂层的表面处理可以改进热密封性和/或表面粘合性,例如在纤维素基基底层之间(例如杯原料(cupstock)层)。
在一些实施方案中,水性聚合物涂层在合适的功率下进行电晕处理。水性聚合物涂层可以在1瓦特或更大的功率水平下进行电晕处理。在一些实施方案中,水性聚合物涂层在1-4瓦特/每平方英尺每分钟的功率水平下进行电晕处理(例如2瓦特或更大,2.5瓦特或更大,3瓦特或更大,或3.5瓦特或更大)。在一些实施方案中,水性聚合物涂层在4瓦特或更小的功率下进行电晕处理(例如3.5瓦特或更小,3瓦特或更小,2.5瓦特或更小,或2瓦特或更小)。在一些实施方案中,水性聚合物涂层在2–4瓦特/每平方英尺每分钟下进行电晕处理。在纤维素基底上的水性聚合物涂层暴露于电晕处理的时间可以很短。例如,暴露时间可以小于1秒。在一些实施方案中,电晕处理可以在涂布生产线上正在移动的纸或纸板基底网上进行。在一些实施方案中,水性聚合物涂层可以在使用100ft/min或更大的线速度的涂布生产线上进行电晕处理。例如,水性聚合物涂层可以使用500-5000ft/min的线速度进行电晕处理,例如500-1000ft/min。在一些实施方案中,可以使用以下公式确定瓦特密度,即被施加到基底上的能量:
通常,较高的瓦特密度可以产生较高的达因水平(检测表面能)。在一些实施方案中,表面能的增加可以提高表面的可润湿性和粘合特性。一旦知道瓦特密度以获得达到特定达因水平的水性聚合物涂层,就可以由此密度预期参数变化的结果(如果有的话),例如线速度。
在一些实施方案中,本文所述的半结晶聚合物涂层进行表面处理。可以采用任何能增加低密度聚乙烯均聚物或低密度聚乙烯共聚物的表面活性的表面处理,例如通过氧化聚合物。表面处理的实例可以包括本文所述的那些,例如电晕放电、等离子放电和火焰处理。在一些实施方案中,半结晶聚合物涂层经由电晕处理在2-4瓦特/每平方英尺每分钟下进行表面处理(例如2、2.5、3、3.5或4)。在一些实施方案中,半结晶聚合物涂层经由电晕处理在2–3瓦特/每平方英尺每分钟下进行表面处理。在一些实施方案中,半结晶聚合物涂层的电晕处理时间小于1秒。在一些实施方案中,半结晶聚合物涂层可以在使用100ft/min或更大的线速度的涂布生产线上进行电晕处理。例如,半结晶聚合物涂层可以使用500-5000ft/min的线速度进行电晕处理,例如500-1000ft/min。
在一些实施方案中,与未表面处理的涂层的情况相比,水性聚合物涂层和/或半结晶聚合物涂层的表面热处理、例如电晕处理对纸的防泄漏性、防污性和/或防粘连性没有不利影响。例如,在一些实施方案中,水性聚合物涂层和/或半结晶聚合物涂层可以在电晕处理之前和之后具有相似水平的防泄漏性、防污性和/或防粘连性。
一个或多个涂层可以涂布到纤维素基基底上以形成被涂布的基底,其中被涂布的基底然后成型为纸杯。纸杯可以按照本领域公知用于形成纸杯的任何方式形成。在一些实施方案中,纸杯可以如下生产:(a)将含有第一水性聚合物涂料的第一涂层施用到第一纸基底的至少一部分表面上;(b)将第二水性聚合物涂层施用到第二基底的至少一部分表面上;(c)从第一纸基底和第二纸基底之一形成侧壁,并使侧壁沿着侧边与其自身粘合;(d)从第一纸基底和第二纸基底之一形成底部;和(e)使沿着底边的侧壁粘合到沿着侧边的底部,从而形成纸杯。在一些实施方案中,纸杯是如下生产的:(a)将含有第一水性聚合物涂料的第一涂层施用到第一纸基底的至少一部分表面上以形成第一个被涂布的纸基底;(b)将含有低密度聚乙烯均聚物或共聚物的第二涂层在比低密度聚乙烯均聚物或共聚物的熔点温度更高的温度下施用到第二纸基底的至少一部分表面上,从而形成第二个被涂布的纸基底,其中低密度聚乙烯均聚物或共聚物任选地含有极性官能度;(c)从第一纸基底和第二纸基底之一形成侧壁,并使侧壁沿着侧边与其自身粘合;(d)从第一纸基底和第二纸基底中的另一个形成底部;和(e)使沿着底边的侧壁粘合到沿着侧边的底部,从而形成纸杯。在一些实施方案中,可以使用第一水性聚合物涂层使得侧壁沿着侧边与其自身粘合。被例如低密度聚乙烯均聚物或共聚物涂层涂布的底部可以与被例如水性聚合物涂层涂布的侧部(即侧壁)接触,并且纸杯的侧部可以使用诱导密封、脉冲密封、加压密封或其组合来结合。在其它实施方案中,被例如水性聚合物涂层涂布的底部可以与被例如水性聚合物涂层涂布的侧部(即侧壁)接触,并且纸杯的侧部可以使用诱导密封、脉冲密封、加压密封或其组合来结合。在一些实施方案中,纸杯的侧部可以使用加热与其自身粘合或与纸杯底部粘合。例如在底部上和在侧部上的涂层可以被加热到高于第二涂层的维卡软化点,从而产生密封和形成杯。在一些实施方案中,纸杯的侧部可以在不加热的情况下与其自身或与纸杯底部粘合。纸杯可以是防泄漏和/或防污的。
第一涂层可以用于粘合纸基底,其中第一基底包含含有水性聚合物涂料分散体的第一涂层(例如通过乙烯基芳族单体和丙烯酸型单体聚合制备),第二纸基底含有第二水性聚合物涂料分散体,它们是通过粘合第一涂层和第二水性聚合物涂层而粘附的,从而将第一基底与第二基底粘合。在一些实施方案中,第一基底包含含有水性聚合物涂料分散体的第一涂层,并且第二纸基底含有低密度聚乙烯均聚物或共聚物,其中这些纸基底是通过粘合第一涂层和第二涂层而粘附的,从而将第一基底与第二基底粘合。水性第一涂层可以与其自身粘合或与被第二涂层涂布的表面粘合。例如,第一涂层可以粘合到第二低密度聚乙烯均聚物或共聚物涂层,或粘合到被第二涂层涂布的表面。第一涂层可以粘合到未涂布的表面。
本文所述的水性聚合物涂层可以用于任何纤维素基基底上,和用于其中使用半结晶聚合物涂层的任何应用中。例如,水性聚合物涂层和被涂布的基底可以用于纸杯中,包括例如一次性纸杯。作为杯子的替代性方案,本文所述的涂层可以用于涂布用于生产以下物品的纸:用于干食品的纸袋,例如咖啡、茶、糖粉;用于液体的纸袋,例如化妆品、清洁剂、饮料;管状层压物;纸承载袋;用于冰淇淋、糖果的纸层压产品和共挤出物(例如巧克力棒和慕斯棒);纸胶粘带;卡纸板杯(例如纸杯),酸奶罐,舒芙蕾(soufflé)杯;金属盘,或肉盘;缠绕纸板容器(例如罐、鼓),用于外部包装的湿强度纸箱(例如红酒瓶、食品);涂布卡纸板的水果箱;快速食品盘;夹板壳;饮料纸箱和用于液体的纸箱,例如洗涤剂和清洁剂,冷冻食品纸箱,冰包装(例如冰杯、用于锥形冰淇淋薄饼的包装材料);纸标签;或花盆和植物盆。
与不包含第一涂层的应用相比,水性聚合物涂层和/或半结晶聚合物涂层可以向纸提供防泄漏性和/或防污性。与不包含水性聚合物涂层和/或半结晶聚合物涂层的应用相比,水性聚合物涂层和/或半结晶聚合物涂层可以向纸提供防泄漏性和/或防污性。在一些实施方案中,水性聚合物涂层和/或半结晶聚合物涂层可以提供对纸涂料配制剂的流变性能的改进。
本文所述的纸杯可以用于盛放例如热液体,例如咖啡或茶,并保持防泄漏和/或防污性。能提供对水、湿分、油脂、氧气等的阻隔性能的涂料也必须具有在生产工艺期间形成密封和不粘连的能力。例如,在用于容纳冷或热液体的杯中所用的纸板的纸必须能当纸或纸板的前面和背面连接时密封并经受温度和压力,而且密封本身也必须能抵抗液体或潮湿蒸气,并且保持存在时的完整性。例如,当暴露于热咖啡达到30分钟时,本文所述的纸杯能显示减少或清除从纸杯底部界面的泄漏。例如,当暴露于热咖啡达到30分钟时,本文所述的纸杯能显示减少或清除在纸杯底部界面处的污染。另外,在被切割/成型为纸杯的底部或侧部之前,本文所述的纸杯当缠绕到纸卷上时,能显示挤出涂布纸的最小粘连倾向(即涂布表面之间的粘合,或者涂布表面与未涂布表面之间的粘合)。理想的是对纸卷的涂布侧面和/或未涂布侧面的粘合损失程度小。在一些实施方案中,当解开纸卷时,纸卷显示层分离,且没有对纸卷中的涂布侧面或未涂布侧面造成表面损伤。另外,本文所述的涂层、被涂布的基底和/或纸杯可以显示低的密封起始温度,最小的毛细管泄漏,改进的在高温和短停留时间下的二次热密封,抗挠曲断裂性,以及耐高温性(达到水的沸点)。另外,理想的是对于所有组分的完全FDA许可,并且不会引起感官行为。
涂层的耐水性可以用Cobb方法检测,参见TAPPI T 441(2001),将其全部内容引入本文以供参考。此方法测定在规定时间内在标准条件下被纸、纸板和波纹纤维板吸收的水的量,并在一些实施方案中,本文所述的被涂布的基底能通过在此实验方法中规定的耐水性实验。吸水性可以是纸或纸板的各种特征的函数,包括但不限于施胶和孔隙率。
热密封性能可以使用Sencorp型号12ASL/1密封机评价。可以设定顶部和底部夹头的温度,例如是315℃。被涂布的片材可以面对面放置,并在各种时间和压力下密封。压力可以例如在从20psi至30psi至40psi的范围内变化。在密封和冷却到室温之后,两块板可以分开,并评价其粘合水平。这些样品可以基于以下标准按照1-5评级:
1-无粘合
2-粘合,但是没有剩余物或纤维撕裂
3-粘合,具有涂料转移或轻微的纤维撕裂(<5%的表面积)
4-一些纤维撕裂(5–50%)
5-纤维撕裂(>50%)
因为在尽可能少的时间和压力下的最大粘合是理想的,所以评级5能确保足够的热密封。
热密封也可以使用Qualitest HST-H3热密封检测仪进行定量。可以设定顶部和底部夹头的温度,例如250℃或更低,200℃或更低,或150℃或更低,从而模拟形成杯的操作。保压时间可以在给定压力、例如40psi和例如在380n/m或更大的力下调节,从而实现在基底之间的“可接受的”纤维撕裂。
半结晶聚合物涂层可以具有低的密封起始温度。密封起始温度可以通过将涂料施用到50lb牛皮纸上检测,检测达到1lb/in(4.4N/25.4mm)的热密封强度时的温度,并注意在Topwave密封机上的条件。另外,密封性能可以通过ASTM F2029(2008)检测,热粘合密封可以通过ASTM F1921(2012)检测。抗挠曲断裂性可以通过用于塑料膜的ASTM F392(2011)检测。另外,检测在涂层中的针孔对于确保足够的纸涂布覆盖率而言是重要的。其它实验方法和工序也可以用于检测本文所述的涂层和杯的改进性能。
纸杯也可以使用咖啡保持实验检测,其中可以用咖啡在约90℃的起始温度下基本上填充纸杯(例如12oz.标准纸杯),并保持至少30分钟。然后,可以目测纸杯以寻找从侧缝或底缝的泄漏。如果在30分钟后可以看到任何泄漏或污渍,则认为纸杯没有通过此咖啡保持实验;如果纸杯能通过此咖啡保持实验,则认为其是防泄漏的(和防污的)。
实施例
实施例1:被水性聚合物和半结晶聚合物涂层涂布的电晕处理纸板的热密封实验
水性聚合物涂层:作为水性聚合物涂料的树脂G含有高岭土基颜料(25份),被低聚物稳定化的苯乙烯-丙烯酸型共聚物胶乳(56.25份),和被表面活性剂稳定化的苯乙烯-丙烯酸型共聚物胶乳(18.75份)。作为水性聚合物涂料的C2S3含有高岭土基颜料(23.5份),被低聚物稳定化的苯乙烯-丙烯酸型共聚物胶乳(46.3份),和被表面活性剂稳定化的苯乙烯-丙烯酸型共聚物胶乳(30.2份)。作为水性聚合物涂料的Coat 30含有高岭土基颜料(11.75份),云母颜料(11.75份),被低聚物稳定化的苯乙烯-丙烯酸型共聚物胶乳(46.3份),和被表面活性剂稳定化的苯乙烯-丙烯酸型共聚物胶乳(30.2份)。作为水性聚合物涂料的树脂35含有高岭土基颜料(23.5份),被低聚物稳定化的苯乙烯-丙烯酸型共聚物胶乳(46.3份),被表面活性剂稳定化的苯乙烯-丙烯酸型共聚物胶乳(30.2份),和稳定化的蜡乳液(10份)。作为水性聚合物涂料的树脂57含有高岭土基颜料(35份),被低聚物稳定化的苯乙烯-丙烯酸型共聚物胶乳(39.3份),和被表面活性剂稳定化的苯乙烯-丙烯酸型共聚物胶乳(25.7份)。
半结晶聚合物涂层:聚乙烯(PE)是可商购的低密度聚乙烯(LDPE)均聚物或共聚物。用于挤出涂料的低密度聚乙烯均聚物可以具有4-12g/10min的熔体指数,密度为0.915-0.925g/cm3。用于挤出涂料的低密度聚乙烯共聚物可以包括乙烯与丙烯酸甲酯的共聚物(6-13%丙烯酸甲酯),或乙烯与甲基丙烯酸的共聚物(4-10%甲基丙烯酸)。聚乙烯共聚物可以具有4-12g/10min的熔体指数,密度为0.920-0.940g/cm3。
方法:下面提供高速轨道方法以模拟在工业纸杯成型操作中在两个被涂布的纸板基底之间的粘合。将两个3"正方形纸板样品切成要检测的样品。一个纸板样品用水性聚合物涂料涂布,例如参见表1第3列。水性涂布的样品然后进行电晕处理,例如参见表1第4列。第二个纸板样品用1密耳(25微米)厚度的低密度PE(LDPE)均聚物或官能化LDPE共聚物挤出涂布,例如参见表1第5列。经涂布的样品然后安装到水平“轨道”上,其中被涂布的侧面彼此之间物理接触(在一些最小力作用下以使它们保持在一起)。然后,将样品在高速下输送经过热风机,使它们暴露于高温。温度可以是约500-1050°F,速度可以是约100-2390cm/min。对于较快的速度,需要较高的温度以允许向纸基底传热,从而当试图分开样品时提供100%纤维撕裂。然后对冷却(室温)的样品进行手动分离纤维撕裂分析,其中将两个正方形样品按照90度的角度互相拉开。基于0-9的级别,确定被拉开的样品的相对粘合值(表1,最后一列),其中0是无粘合,4是显示“最小可接受的”纤维撕裂的阈值(即优良的粘合),9是最佳(100%纤维撕裂)。
在下表中,在对比例中使用的聚乙烯均聚物和共聚物是与本发明实施例中相似的。
表1:被树脂G水性聚合物涂布的纸板的高速轨道粘合性评级。
EMA表示含有乙烯和丙烯酸甲酯的低密度聚乙烯共聚物。EMMA表示含有乙烯和甲基丙烯酸的低密度聚乙烯共聚物。
表2:被C2S3水性聚合物涂布的纸板的高速轨道粘合性评级。
表3:被Coat30水性聚合物涂布的纸板的高速轨道粘合性评级。
表4:被树脂35水性聚合物涂布的纸板的高速轨道粘合性评级。
表5:被树脂57水性聚合物涂布的纸板的高速轨道粘合性评级。
实施例2:被水性聚合物涂层涂布的纸板的Qualitest热密封实验
研究电晕处理的水性涂层在纸板样品上的热密封。对于每个检测的样品,切割两个1"正方形纸板样品。用水性聚合物涂布这两个纸板样品,每个水性涂层的成分和用量显示在表6中。
经过热密封的涂布纸板的剥离强度和纤维撕裂(基底损伤)汇总于表7-9中。图1-3显示分别在150℃、200℃和250℃下密封时的电晕处理和颜料的帕累托图,其中标准化效果估算值p=0.5。图4-6显示对于热密封变量的预期平均值。
表6:水性聚合物涂层的组成。
·每个样品中的总固体含量如上配制。pH是8.5。
表7:被水性聚合物涂布的纸板样品在250℃下热密封时的Qualitest剥离强度
·密封温度:250℃;保压时间:1秒(在纸表面上100℃)
·1英寸宽的样品在2in/min下进行剥离实验。
表8:被水性聚合物涂布的纸板样品在200℃热密封时的Qualitest剥离强度
·密封温度:200℃;保压时间:1秒(在纸表面上80℃)
·1英寸宽的样品在2in/min下进行剥离实验。
表9:被水性聚合物涂布的纸板样品在150℃热密封时的Qualitest剥离强度。
·密封温度:150℃;保压时间:1秒(在纸表面上65℃)
·1英寸宽的样品在2in/min下进行剥离实验。
抗粘连性:抗粘连性是在样品上在60psi、50℃下24小时评价的。样品样品进行1-5评级(表10),基于以下级别:5=不发粘(无粘连);4=低度发粘;3=严重发粘;2=在分离时基底损伤,小于25%损伤;1=在分离时基底损伤,大于25%损伤(最严重的粘连)。图7和8显示了帕累托图和预期平均值,与电晕处理和在热密封时的颜料有关,标准化效果估算值p=0.5。
表10:被水性聚合物涂布的纸板的抗粘连性
样品 | 对比 | 电晕处理 |
CO2014-0133-1 | 4 | 4 |
CO2014-0133-2 | 5 | 5 |
CO2014-0133-3 | 4 | 3 |
CO2014-0133-4 | 4 | 4 |
泄漏实验:将被涂布的纸板样品沿着垂直线和水平线折叠。红色颜料分散体在水中的溶液施用于折叠处。使此溶液在折痕部分上停留10分钟,然后擦除。然后通过计数沿着折痕的按每英寸计的圆点数目来评价样品(表11),并基于以下级别评级:5=0个圆点/英寸;4=1-5个圆点/英寸;3=6-10个圆点/英寸;2=11-30个圆点/英寸;1=>30个圆点/英寸。图9和10显示了帕累托图和预期平均值,与电晕处理和在密封时的颜料有关,标准化效果估算值p=0.5。
表11:被水性聚合物涂布的纸板的泄漏实验
如表9-11所示,电晕处理的样品具有显著提高的剥离强度,且同时提供对粘连和泄漏的不明显影响。抗粘连性的变化是出乎预料的,因为剥离强度的提高通常导致相应的粘连增加。
分析研究:用FT-IR、原子力显微镜(AFM)和配备能量分散X-射线光谱(EDS)的扫描电子显微镜(SEM)分析经处理的表面和未处理的表面。经处理的纸板表面是经电晕处理的含水聚合物。图11和12是AFM图像,分别显示未处理和经电晕处理的纸板表面的表面粗糙度。在未处理纸板的表面上看到两相体系,其中与电晕处理的表面相比,软的树脂相看来更多地聚集在表面上。在经电晕处理的纸板的表面上看到峰和谷,这对粗糙表面做出贡献,能提供较大的表面积以增加在电晕处理的涂布样品之间的粘合强度。
研究经涂布的纸板样品在各种电晕处理水平时的剥离强度和抗粘连性:如上所述,在各种电晕处理水平时检测被CO2014-0133-1涂布的纸板样品(14点SBS板)的剥离强度和抗粘连性。将所有纸板样品在150℃下热密封。粘连实验是在50℃、60psi下进行24小时,结果显示在图12中。
表12:经电晕处理的涂布纸板的剥离强度和抗粘连性
F-F表示基底的前面到前面;F-B表示基底的前面到背面。基底的前面进行电晕处理。
所附权利要求书的组合物和方法在范围上不受本文中描述的特定组合物和方法限制,它们意在举例说明权利要求的几个方面,并且在功能上相当的任何组合物和方法意在落在权利要求书的范围内。除本文中显示和描述的那些外,该组合物和方法的各种修改意在落在所附权利要求书的范围内。此外,尽管仅明确描述了本文中公开的某些代表性组合物和方法步骤,但组合物和方法步骤的其它组合也意在落在所附权利要求书的范围内,即使没有明确列举。因此,在本文中可能明确提到步骤、要素、组分或成分的组合;但是,即使没有明确指定,也包括步骤、要素、组分和成分的其它组合。本文所用的术语“包含”及其变体与术语“包括”及其变体同义使用,并且是开放的非限制性术语。尽管术语“包含”和“包括”在本文中已用于描述各种实施方案,但可以使用术语“基本由...构成”和“由...构成”代替“包含”和“包括”以提供更具体的本发明实施方案并且也作出公开。除了实施例或其它注明之处,在说明书和权利要求中用于表示成分数量、反应条件等的所有数字都应理解为不意欲限制采用与权利要求等同的方案的情况,至少应当理解为明确数字和常规舍入方式。
Claims (45)
1.一种被涂布的基底,其包含:
纤维素基基底,和
在纤维素基基底表面上的水性聚合物涂层,
其中水性聚合物涂层已经用高能放电进行表面处理。
2.根据权利要求1的被涂布的基底,其中纤维素基基底是纸板。
3.根据权利要求1或2的被涂布的基底,其中水性聚合物涂层含有纯的丙烯酸型共聚物,苯乙烯-丙烯酸型共聚物,苯乙烯-丁二烯共聚物,乙烯基丙烯酸型共聚物,或其组合。
4.根据权利要求1–3中任一项的被涂布的基底,其中水性聚合物涂层含有低聚物稳定化的苯乙烯丙烯酸型共聚物胶乳,表面活性剂稳定化的苯乙烯丙烯酸型共聚物胶乳,或其组合。
5.根据权利要求1–4中任一项的被涂布的基底,其中水性聚合物涂层具有2-30g/m2的涂布重量。
6.根据权利要求1–5中任一项的被涂布的基底,其中水性聚合物涂层具有10-25g/m2的涂布重量。
7.根据权利要求1–6中任一项的被涂布的基底,其中水性聚合物涂层还含有已经用选自以下的材料处理的颜料:表面活性剂;疏水改性的聚合物;苯乙烯-丙烯酸型树脂乳液;苯乙烯-丁二烯胶乳乳液;硅烷、硅氧烷、硅氧烷/有机硅树脂共混物,和它们的碳基类似物;以及它们的组合,从而形成经处理的颜料。
8.根据权利要求1–7中任一项的被涂布的基底,其中水性聚合物涂层是使用电晕处理进行表面处理的。
9.纸杯,其包含:
侧部和底部,和
在纸杯的第一表面上的第一水性聚合物涂层,其中第一表面包括一个或多个侧部内表面或底部内表面,
其中第一水性聚合物涂层已经用高能放电进行表面处理,和
其中侧部的底边经由含有第一水性聚合物涂层的密封粘合到底部的侧边。
10.根据权利要求9的纸杯,其中第一水性聚合物涂层含有纯的丙烯酸型共聚物,苯乙烯-丙烯酸型共聚物,苯乙烯-丁二烯共聚物,乙烯基丙烯酸型共聚物,或其组合。
11.根据权利要求9或10的纸杯,其中第一表面包括纸杯底部的内表面。
12.根据权利要求9-11中任一项的纸杯,其中第一表面包括纸杯侧部的内表面。
13.根据权利要求9或10的纸杯,其中第一表面同时包括侧部内表面和底部内表面。
14.根据权利要求9-13中任一项的纸杯,其中第一水性聚合物涂层是使用电晕处理进行表面处理的。
15.根据权利要求9-12或14中任一项的纸杯,其中还在纸杯的第二表面上包含含有半结晶聚合物的第二涂层,其中当第一表面是侧部内表面时,第二表面包括纸杯底部的内表面;或者当第一表面是底部内表面时,第二表面包括纸杯侧部的内表面;和其中侧部的底边经由含有第一水性聚合物涂层和第二涂层的密封粘合到底部的侧边。
16.根据权利要求15的纸杯,其中半结晶聚合物含有低密度聚乙烯、脂族芳族聚酯、尼龙或其组合。
17.根据权利要求15或16的纸杯,其中半结晶聚合物含有低密度聚乙烯均聚物或低密度聚乙烯共聚物。
18.根据权利要求15-17中任一项的纸杯,其中半结晶聚合物具有极性官能度。
19.根据权利要求15-18中任一项的纸杯,其中半结晶聚合物包括低密度聚乙烯共聚物,其是乙烯和包含丙烯酸甲酯、甲基丙烯酸或其组合的单体形成的共聚物。
20.根据权利要求15-19中任一项的纸杯,其中第二涂层具有0.5-2密耳的厚度。
21.根据权利要求15-20中任一项的纸杯,其中半结晶聚合物具有95-105℃的熔点温度。
22.根据权利要求15-21中任一项的纸杯,其中第二涂层具有0.65-1.1g/cm3的密度。
23.根据权利要求9-22中任一项的纸杯,其中第一水性聚合物涂层还含有已经用选自以下的材料处理的颜料:表面活性剂;疏水改性的聚合物;苯乙烯-丙烯酸型树脂乳液;苯乙烯-丁二烯胶乳乳液;硅烷、硅氧烷、硅氧烷/有机硅树脂共混物,和它们的碳基类似物;以及它们的组合,从而形成经处理的颜料。
24.根据权利要求9-23中任一项的纸杯,其中纸杯的侧部沿着侧边与其自身粘合。
25.根据权利要求9-24中任一项的纸杯,其中用热咖啡在90℃的起始温度下基本上填充纸杯之后达到30分钟,纸杯没有显示沿着纸杯密封处的泄漏。
26.一种制备经处理和涂布的基底的方法,此方法包括:
用水性聚合物涂层涂布纤维素基基底以形成被涂布的基底,和
对被涂布的基底进行电晕处理,从而形成经处理和涂布的基底。
27.根据权利要求26的方法,其中水性聚合物涂层含有纯的丙烯酸型共聚物,苯乙烯-丙烯酸型共聚物,苯乙烯-丁二烯共聚物,乙烯基丙烯酸型共聚物,或其组合。
28.根据权利要求26或27的方法,其中电晕处理是在1-4瓦特/每平方英尺每分钟下进行的。
29.一种生产纸杯的方法,包括:
从第一纤维素基基底形成侧壁和/或底部,其中第一纤维素基基底的至少一部分表面被第一水性聚合物涂层涂布,然后用高能放电进行表面处理,
使侧壁沿着侧边与其自身粘合;和
使沿着底边的侧壁粘合到沿着侧边的底部,从而形成含有第一水性聚合物涂层的密封。
30.根据权利要求29的方法,其中第一水性聚合物涂层含有纯的丙烯酸型共聚物,苯乙烯-丙烯酸型共聚物,苯乙烯-丁二烯共聚物,乙烯基丙烯酸型共聚物,或其组合。
31.根据权利要求29或30的方法,其中第一水性聚合物涂层还含有已经用选自以下的材料处理的颜料:表面活性剂;疏水改性的聚合物;苯乙烯-丙烯酸型树脂乳液;苯乙烯-丁二烯胶乳乳液;硅烷、硅氧烷、硅氧烷/有机硅树脂共混物,和它们的碳基类似物;以及它们的组合。
32.根据权利要求29-31中任一项的方法,其中包括从第一纤维素基基底形成侧壁。
33.根据权利要求29-32中任一项的方法,其中包括从第一纤维素基基底形成底部。
34.根据权利要求29-33中任一项的方法,其中第一水性聚合物涂层是使用电晕处理进行表面处理的。
35.根据权利要求26-33中任一项的方法,其中还包括提供第二纤维素基基底,其中至少一部分的第二纤维素基基底被半结晶聚合物涂布,并且如果第一纤维素基基底形成底部,则第二纤维素基基底形成侧壁;和如果第一纤维素基基底形成侧壁,则第二纤维素基基底形成底部。
36.根据权利要求35的方法,其中半结晶聚合物含有低密度聚乙烯、脂族芳族聚酯、尼龙或其组合。
37.根据权利要求35或36的方法,其中半结晶聚合物含有低密度聚乙烯均聚物或低密度聚乙烯共聚物。
38.根据权利要求35-37中任一项的方法,其中半结晶聚合物具有极性官能度。
39.根据权利要求35-38中任一项的方法,其中通过在比半结晶聚合物的熔点温度更高的温度下挤出涂料,将第二涂层涂布到第二纤维素基基底上,从而形成被涂布的纤维素基基底。
40.根据权利要求35-39中任一项的方法,其中半结晶聚合物具有高于95℃的熔点温度。
41.根据权利要求34-40中任一项的方法,其中将第二涂层按照0.5-2密耳的厚度涂布到第二纤维素基基底上。
42.根据权利要求35-41中任一项的方法,其中第二涂层具有0.65-1.1g/cm3的密度。
43.根据权利要求35-42中任一项的方法,其中第一纤维素基基底是底部,并且第二纤维素基基底是侧壁。
44.根据权利要求34-42中任一项的方法,其中第一纤维素基基底是侧壁,并且第二纤维素基基底是底部。
45.根据权利要求34-44中任一项的方法,其中电晕处理是在1-4瓦特/每平方英尺每分钟下进行的。
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- 2016-05-12 WO PCT/US2016/032087 patent/WO2016183314A1/en active Application Filing
- 2016-05-12 CN CN201680027162.1A patent/CN107592891A/zh active Pending
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CN111073011A (zh) * | 2019-12-26 | 2020-04-28 | 中国乐凯集团有限公司 | 一种双涂层三醋酸纤维素酯薄膜 |
CN113201963A (zh) * | 2021-05-06 | 2021-08-03 | 海南必凯水性新材料有限公司 | 一种牛皮纸专用的热封乳液及其制备方法 |
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US10889938B2 (en) | 2021-01-12 |
EP3294949A1 (en) | 2018-03-21 |
WO2016183314A1 (en) | 2016-11-17 |
JP2018524199A (ja) | 2018-08-30 |
KR20180005216A (ko) | 2018-01-15 |
JP6789980B2 (ja) | 2020-11-25 |
US20210172120A1 (en) | 2021-06-10 |
EP3294949B1 (en) | 2020-07-08 |
US20180135251A1 (en) | 2018-05-17 |
JP6789980B6 (ja) | 2020-12-16 |
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