CN101466896B - 烷基乙烯酮二聚物水分散体 - Google Patents
烷基乙烯酮二聚物水分散体 Download PDFInfo
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- CN101466896B CN101466896B CN2007800213909A CN200780021390A CN101466896B CN 101466896 B CN101466896 B CN 101466896B CN 2007800213909 A CN2007800213909 A CN 2007800213909A CN 200780021390 A CN200780021390 A CN 200780021390A CN 101466896 B CN101466896 B CN 101466896B
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- aluminum sulfate
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- alkyl ketene
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Abstract
本发明涉及一种烷基乙烯酮二聚物水分散体,其包含至少15重量%的烷基乙烯酮二聚物和至少一种水溶性阳离子型淀粉、硫酸铝以及至少一种由萘磺酸和甲醛形成的缩合产物或木素磺酸或者每种情况下其盐,其中所述分散体包含基于烷基乙烯酮二聚物为2-50重量%的硫酸铝,并且其中硫酸铝含量为2-15重量%的所述分散体还额外包含0.1-5重量%的具有1-10个碳原子的饱和羧酸、苯磺酸、对甲苯磺酸和/或无机酸,以及所述分散体在作为用于纸和纸产品的机内施胶胶料和表面胶料方面的用途。
Description
本发明涉及烷基乙烯酮二聚物水分散体,其包含至少15重量%的烷基乙烯酮二聚物和至少一种水溶性阳离子型淀粉、硫酸铝以及至少一种萘磺酸与甲醛的缩合物或木素磺酸或者每种情况下其盐。
烷基乙烯酮二聚物(AKD)水分散体是可市购的产品。它们用于使纸和卡纸板防水。烷基乙烯酮水分散体通常包含阳离子型淀粉和木素磺酸钠作为稳定剂。术语分散体指的是在作为连续介质的液相中包含固体颗粒的两相体系。术语乳液的意思理解为包含在另一液相中乳化的液滴的两相体系。
用作防水剂的烷基乙烯酮二聚物的熔点约为45-70℃。因此烷基乙烯酮二聚物和水的混合物在低于40℃的温度下为分散体,在高于45℃的温度下为乳液。为使用烷基乙烯酮二聚物分散体作为生产纸和卡纸板的胶料,该分散体必须可稀释且泵送稳定并且在高达32℃的温度下具有几周的贮存期限。
US-A4,240,935公开了包含表氯醇树脂、木素磺酸钠和/或萘磺酸钠盐与甲醛的缩合物作为稳定剂的烷基乙烯酮二聚物水分散体。该水分散体中的固体含量为5-25重量%,烷基乙烯酮二聚物与表氯醇树脂的比为4:1-1:3。
EP-A 369 328公开了固体含量至多为30重量%的烷基乙烯酮二聚物分散体。它们包含0.15-1.5重量%的硫酸铝、0.1-5重量%的具有1-10个碳原子的羧酸、10-30重量%的阳离子型淀粉和1-5重量%的木素磺酸盐或甲醛与萘磺酸盐的缩合物(每种情况均基于烷基乙烯酮二聚物)作为稳定剂,这些分散体在32℃的温度下储存4周后的粘度增加少于100厘沲。
最近几年,趋势是基于用于可消费液体如牛奶或奶油的纸板的容器。这种容器的壁通常在双面,有时只在一面,涂覆有聚乙烯。
为了使这些基于纸板且打算用于可消费液体的容器满足要求,它们必须抗乳酸作用以使乳酸不会在容器的临界点如至少彼此结合的界面透过卡 纸板。另外,这些容器在填充可消费液体前必须用热过氧化氢消毒。这意味着该容器能经受住热过氧化氢的作用。因此乳酸和热过氧化氢溶液的边缘渗透是其中装填可消费液体的容器的关键特性。
WO 2004/022851公开了使用可通过在至少一种助留剂和阳离子聚合物如聚乙烯基胺的存在下用至少一种机内施胶胶料对包含纤维素纤维水浆的纸浆进行机内施胶获得的卡纸板生产液体包装材料。所用机内施胶胶料例如为每种情况下借助阳离子型淀粉乳化的烷基乙烯酮二聚物和/或松香的水分散体。铝化合物基本上只与松香一起使用。
DE-A 10 2004 002 370公开了用于生产包装液体的容器的包装材料,其包含至少一施胶纸或施胶卡纸板与至少一层不透水膜的双层复合材料。该纸或卡纸板包含平均颗粒尺寸为1-1000μm的细碎的水不溶性或水溶性合成聚合物。
本发明的目的是提供贮存期限长且剪切稳定的其它烷基乙烯酮二聚物分散体。另外,当用于生产用于液体包装的卡纸板时,与用已知分散体施胶的产品相比,该分散体应使得容器在边缘渗透,尤其是过氧化氢边缘渗透方面有所改善。
根据本发明,该目的通过包含如下组分的烷基乙烯酮二聚物水分散体实现:至少15重量%的烷基乙烯酮二聚物和至少一种水溶性阳离子型淀粉、硫酸铝以及至少一种萘磺酸与甲醛的缩合物或木素磺酸或者每种情况下其盐(如果该分散体包含2-50重量%的硫酸铝),当硫酸铝含量为2-15重量%时,该分散体还额外包含0.1-5重量%的具有1-10个碳原子的饱和羧酸、苯磺酸、对甲苯磺酸和/或无机酸,每种情况下均基于烷基乙烯酮二聚物。
烷基乙烯酮二聚物水分散体优选基于烷基乙烯酮二聚物包含5-30重量%硫酸铝。特别优选那些基于烷基乙烯酮二聚物包含10-20重量%硫酸铝的烷基乙烯酮二聚物分散体。
例如,烷基乙烯酮二聚物水分散体每种情况下基于烷基乙烯酮二聚物包含:
(a)5-30重量%的硫酸铝,
(b)10-30重量%的至少一种水溶性阳离子型淀粉,
(c)1-5重量%的至少一种萘磺酸与甲醛的缩合物或者萘磺酸盐与甲醛的缩合物和/或木素磺酸或木素磺酸盐,以及
(d)0-5重量%的至少一种具有1-10个碳原子的饱和羧酸、苯磺酸、对甲苯磺酸和/或无机酸。
当含有2-15重量%的硫酸铝时,基于烷基乙烯酮二聚物,该分散体还额外包含0.1-5重量%的具有1-10个碳原子的饱和羧酸、苯磺酸、对甲苯磺酸和/或无机酸。
特别优选的烷基乙烯酮二聚物水分散体是包含15-30重量%的至少一种烷基乙烯酮二聚物以及每种情况下基于烷基乙烯酮二聚物包含如下组分的那些:
(a)10-20重量%的硫酸铝,
(b)15-25重量%的至少一种水溶性阳离子型淀粉,
(c)1.8-4.0重量%的至少一种萘磺酸与甲醛的缩合物或者萘磺酸盐与甲醛的缩合物和/或木素磺酸或木素磺酸盐,以及
(d)0-5重量%的至少一种具有1-10个碳原子的饱和羧酸。
烷基乙烯酮二聚物可以用例如以下通式进行表征:
其中取代基R1和R2为饱和或不饱和、线性或支化的C8-C30烃基。取代基R1和R2包括例如以下基团:辛基、癸基、十二烷基、十四烷基、十六烷基、十八烷基、二十烷基、二十二烷基、二十四烷基、苯基、苄基、β-萘基和环己基。
优选的烷基乙烯酮二聚物包括具有12-20,优选14-18个碳原子的饱和及单或多不饱和以及支化的烃化合物作为R1和R2。
例如通过使羧酰氯与叔胺反应制备通式I的化合物。具有工业重要性的尤其是可通过天然脂肪酸或其混合物的氯化获得的羧酰氯,例如基于由椰子油、妥尔油、蓖麻油、橄榄油、牛油或棕榈仁油获得的脂肪酸的酰基 氯。羧酰氯的典型的实例为肉豆蔻酰氯、棕榈酰氯、硬脂酰氯、油酰氯、山萮酰氯和异硬脂酰氯。特别有利的是利用在EP-A 1 453 821中公开的方法,在没有溶剂的情况下,在65-150℃的温度下剧烈混合而进行羧酰氯与叔胺的反应。
该水分散体包含至少15重量%至30重量%,优选15-25重量%的烷基乙烯酮二聚物。
本发明烷基乙烯酮二聚物水分散体用阳离子型淀粉稳定。合适的阳离子型淀粉包括所有的具有氨基作为阳离子基团的水溶性淀粉。这种淀粉为可市购的产品。它们例如通过使天然淀粉与具有叔或季氮原子的化合物如二烷基氨基烷基环氧化物或二烷基氨基烷基氯化物反应获得。这种化合物的实例为3-氯-2-羟基丙基三甲基氯化铵和缩水甘油基三甲基氯化铵。例如用取代度(D.S.)表示淀粉的阳离子化程度。该值显示了在阳离子型淀粉中每个单糖单元的阳离子基团数量。阳离子型淀粉的取代度D.S.优选为0.01-0.5,且通常为0.02-0.4。阳离子型淀粉还可以通过首先使天然淀粉进行酶降解,然后阳离子化该降解淀粉而获得。具有所述取代度D.S.的淀粉具有足够的阳离子基团数从而使它们在水溶液中带正电荷。
例如,源自马铃薯、木薯、稻、小麦、玉米、高粱和豌豆的淀粉适于作为阳离子型淀粉的基础。这些淀粉的支链淀粉含量可以是例如0.1-100%。水溶性阳离子型淀粉的实例为取代度D.S.为0.17的134EP。优选使用取代度D.S.至少为0.08的阳离子型淀粉。特别优选用叔或季胺改性的且粘度为50-200mPas(用布氏粘度计在20℃的温度下,2号锭子,在固体含量为3.0%时测量)的阳离子型马铃薯淀粉。
烷基乙烯酮二聚物水分散体通常包含10-30重量%,优选15-25重量%的至少一种阳离子型淀粉。它们带正电荷,并且即使在其它分散稳定剂的存在下也总体上带正电荷。
本发明烷基乙烯酮二聚物水分散体基于烷基乙烯酮二聚物包含2-50重量%的硫酸铝。通常,水分散体中的硫酸铝含量为5-30重量%,特别是10-20重量%,每种情况下均基于烷基乙烯酮二聚物。
烷基乙烯酮二聚物水分散体包含至少一种萘磺酸与甲醛的缩合物或萘 磺酸盐与甲醛的缩合物和/或木素磺酸或木素磺酸盐作为其它稳定剂。合适的萘磺酸盐与木素磺酸盐为例如碱金属、铵和碱土金属盐,比如特别是铵、钙、镁、钾和钠盐。特别优选使用木素磺酸的钠盐或萘磺酸钠盐与甲醛的缩合物的钠盐作为分散稳定剂。
例如基于烷基乙烯酮二聚物使用1-5重量%,优选1.8-4重量%的包含磺基或磺酸盐基的分散稳定剂。
当硫酸铝含量基于烷基乙烯酮二聚物为2-15重量%时,本发明烷基乙烯酮二聚物水分散体还基于烷基乙烯酮二聚物额外包含0.1-5重量%的具有1-10个碳原子的饱和羧酸、苯磺酸、对甲苯磺酸和/或无机酸。在更大量硫酸铝的情况下,该烷基乙烯酮二聚物水分散体如果合适还可以额外包含其它酸。合适的其它酸优选为具有1-10个碳原子的羧酸,例如甲酸、乙酸、丙酸、乳酸、水杨酸、马来酸、富马酸、苯甲酸、柠檬酸、己二酸和苯二甲酸。
烷基乙烯酮二聚物水分散体的pH值例如为2.0-4.0。
将上述烷基乙烯酮二聚物水分散体用作纸和纸产品的机内施胶胶料和表面胶料。纸产品的意思应理解为纸板和卡纸板。在纸和纸产品的生产中,所有类型的纤维素纤维(天然和回收纤维,尤其是来自废纸的纤维)均可以用作原料。生产纸浆的合适纤维为所有常规用于此目的的品种,即机械浆、漂白或未漂的化学浆和包括所有一年生植物的纸浆。机械浆包括例如磨木浆、热法机械浆(TMP)、化学热磨机械浆(CTMP)、压力磨木浆、半化学浆、高得率浆和盘磨机械浆(RMP)。例如,作为化学浆合适的是硫酸盐浆、亚硫酸盐浆和碱法浆。优选使用未漂浆,其也被称为未漂牛皮浆。生产纸浆的合适一年生植物例如为稻、小麦、甘蔗和洋麻。对于生产纸浆,还有利的是使用废纸,其可以单独使用或与其它纤维混合使用,或者可以将包含原浆和回收涂布废纸的纤维混合物,例如漂白的硫酸盐松木浆(pine sulfate)与回收涂布废纸的混合物用作原料。
在纸和纸产品的生产中,可以将本发明烷基乙烯酮二聚物水分散体与常规工艺化学品如助留剂、凝聚剂和助滤剂、固定组合物、湿和干强度剂、杀菌剂、染料、烯基琥珀酸酐和松香一起使用。本发明的乳化的烷基乙烯 酮二聚物剪切稳定且具有贮存期限。例如它们可以储存超过三个月。
在纸和纸产品的生产中,优选将本发明烷基乙烯酮二聚物水分散体用作机内施胶胶料。
它们用于例如生产书写纸或印刷纸并且尤其有利的是用于生产包装液体的容器。例如,纸浆可以基于该纸浆的固体含量包含0.01-0.6重量%的烷基乙烯酮二聚物。将纸浆滤水并将该纸和纸产品干燥之后,得到定量例如为40-400g/m2的机内施胶产品。用于生产可消费液体容器的纸板的定量例如为100-300g/m2。对纸或纸产品进行施胶时所用的烷基乙烯酮二聚物的量基于干纸浆例如为0.05-4.0重量%,优选为0.15-0.8重量%。
为了生产包装液体的容器,例如将机内施胶纸产品在其一面或双面层合包含塑料或金属如铝的膜。合适的塑料膜可以由聚乙烯、聚丙烯、聚酰胺或聚酯生产。膜可以例如借助于粘合剂而粘结在施胶纸产品上。通常,将涂覆有粘合剂的膜用于此目的;将它们应用在纸产品的一面或双面,然后压制该复合材料。但是,也可以将粘合剂涂覆在施胶纸产品的表面,然后应用该膜,随后压制该复合材料。但是也可以用机内施胶纸产品通过热作用和压力直接加工热塑性膜以产生复合材料,然后生产出用于生产包装液体的容器的合适半成品。这种包装材料优选用于食品领域,例如用于包装饮料如矿泉水、果汁或牛奶,或者用于生产盛酒容器如酒杯。在该包装材料的情况下,重要的是要具有良好的边缘渗透值,即该施胶纸产品应吸收尽可能少的液体或基本不吸收。这种容器的切割边必须具有高的抗热过氧化氢和乳酸渗透性。
使用本发明烷基乙烯酮二聚物分散体生产的且计划用于液体包装的容器与使用已知烷基乙烯酮二聚物分散体施胶的容器相比,在过氧化氢边缘渗透方面具有改善值,而且在乳酸边缘渗透方面具有非常好的值。
除非明显不同于上下文,实施例中所述的百分数均为重量百分数。
实施例
实施例1
包含以下组分的一共为1000g的配料:
200g C16/C18烷基二烯酮
700g 水
49g 硫酸铝
13.5g 残留水
烷基乙烯酮二聚物水分散体的制备
将30g阳离子型淀粉(可以134EP市购,Lyckeby)和7.5g木素磺酸钠(可以2901市购,BASF AG)加入700g水中。将该混合物加热至95℃并随后加入水(13.5g)。待该混合物冷却至80℃以后,加入200gC16/C18烷基二烯酮混合物(BP 90 Conc)。待烷基二烯酮融化以后,该混合物的温度约为70℃。利用高压均化器(APV-Lab 60型)在170巴的压力下均化该混合物两次。然后向该热乳液中加入49g硫酸铝。通过加入0.1M HCl将该烷基二烯酮分散体的pH值调节为3.6。该分散体的固含量为28%。
在32℃的温度下储存5周后,该烷基二烯酮分散体的粘度为100mPas(在布氏粘度计中,2号锭子,20℃下测量)。
对比例1(重做EP-A0369328的实施例2)
包含以下组分的一共为500g的配料:
100g C16/C18烷基二烯酮
368.4g 0.01M 乙酸
0.33g 硫酸铝(在水中为5%浓度)
加水至 500g。
烷基乙烯酮二聚物水分散体的制备
将22.5g阳离子型淀粉(可以2187市购)和2g木素磺酸钠(可以XD市购)加入368.4g0.01M乙酸中。用0.1M盐酸将pH值调节为5.5。将该混合物加热至95℃并随后加入水(15g)。待该混合物冷却至80℃以后,加入100g C16/C18烷基二烯酮混合物(BP 90 Conc)。 待AKD融化以后,该混合物的温度为65℃。然后利用高压均化器(APV-Lab60型)在170巴的压力下均化该混合物一次。然后向该热乳液中加入0.33g5%浓度的硫酸铝溶液。通过加入0.1M盐酸将该分散体的pH值调节为3.6。固含量为25%。
在32℃下储存5周后,该分散体的粘度为120mPas(在布氏粘度计中,2号锭子,20℃下测量)。
测定可消费饮料液体卡纸板的边缘渗透性
对于每层卡纸板,每种情况下使用表1中所述胶料和0.15%的 215作为助留剂在实验室纸页成形器上生产120g/m2的纸页,然后通过接触烘缸干燥在120℃下干燥5次。表2所示为测定的过氧化氢边缘渗透值。
该卡纸板的面层由包含70%漂白短纤维和30%漂白长纤维的化学浆组成。
该卡纸板的中间层由包含60%CTMP和40%涂布废纸的化学浆组成。
该卡纸板的底层由100%的未漂化学浆组成。
表1
生产卡纸板之后,通过以下方法测定过氧化氢和乳酸的边缘渗透性:
(a)测定纸页重量
(b)将纸页二等分
(c)粘结纸页
(d)将纸页裁成25×75mm的窄条
(e)测定窄条厚度
关于a):测定纸页重量
称重经调整处理的纸页(精确度1mg),然后将重量转化成g/m2。关于b):用平板切纸机将经调整处理的纸页二等分。
关于c):粘结这些纸页
改造带有为固定胶带辊筒而提供的部件的实验室施胶压榨机,以确保胶带确实彼此粘结,即粘合剂表面不与辊筒接触。施胶压榨的速度为2.2m/min,接触压力为4巴。为防止皱折,使二等分的纸页在圆形一侧缩短约1-1.5cm。然后用剪刀裁剪该粘结纸页。
关于d):将粘结纸页裁成测试条
从该粘结纸页裁剪出25×75mm的窄条。此时应确保这些窄条双面均完全被粘合剂膜覆盖,确保在切割区域有折痕,确保边缘清楚而干净。然后记下这些窄条并捆扎起来。另外,为防止粘住纸页边缘,平板切纸机的刀片和刀刃必须时常用丙酮清洁以去除胶带残留。
关于e):测定厚度
测量粘结并裁剪的纸页厚度(精确度0.001mm)。然后减去胶带的厚度以测定净厚度。每张纸页均在粘结后测量厚度,因为此时它们具有更好的均一性。
过氧化物测试
使过氧化物在金属盘中利用70℃的水浴恒温。将样品在干态下称重,置于过氧化物浴中10分钟,加载格栅以确保它们不会漂浮,然后除掉格栅,用滤纸吸收粘附的过氧化物并立即在湿态下重新称重。
乳酸测试
与过氧化物测试不同的只是使用1%浓度的乳酸作为测试液。该测量在室温下进行且作用时间为1小时。
根据以下公式计算:
X=所有窄条的重量差(湿重-干重)之和[g]
W0=每单位面积所要求的重量[g/m2]
W=每单位面积的实际重量[g/m2]
n=测试条的数量
a=窄条的长度[mm]
b=窄条的宽度[mm]
t=窄条的厚度[μm]
表2所列为对于过氧化氢的边缘渗透性结果。
表2
来自以下的卡纸板层 | H2O2边缘渗透[kg/m2] | 层 |
实施例2 | 0.56 | 面层 |
对比例2 | 1.2 | 面层 |
实施例3 | 1.46 | 中间层 |
对比例3 | 2.1 | 中间层 |
实施例4 | 134 | 底层 |
对比例4 | 0.99 | 底层 |
与对比例相比,本发明AKD分散体在过氧化氢渗透值方面表现出显著改善。另一方面,在乳酸边缘渗透方面,显然本发明AKD分散体与对比分散体相比只有轻微改善。
Claims (11)
1.一种烷基乙烯酮二聚物水分散体,其包含至少15重量%的烷基乙烯酮二聚物,和至少一种水溶性阳离子型淀粉、硫酸铝以及至少一种萘磺酸与甲醛的缩合物或萘磺酸盐与甲醛的缩合物和/或木素磺酸或木素磺酸盐,其中所述分散体包含2-50重量%的硫酸铝,在硫酸铝含量为2-15重量%时,所述分散体还额外包含0.1-5重量%的具有1-10个碳原子的饱和羧酸、苯磺酸、对甲苯磺酸和/或无机酸,每种情况下均基于烷基乙烯酮二聚物。
2.如权利要求1所述的烷基乙烯酮二聚物水分散体,其中所述分散体包含基于烷基乙烯酮二聚物为5-30重量%的硫酸铝。
3.如权利要求1所述的烷基乙烯酮二聚物水分散体,其中所述分散体包含基于烷基乙烯酮二聚物为10-20重量%的硫酸铝。
4.如权利要求2所述的烷基乙烯酮二聚物水分散体,其中所述分散体包含基于烷基乙烯酮二聚物为10-20重量%的硫酸铝。
5.如权利要求1或2所述的烷基乙烯酮二聚物水分散体,其包含:
(a)5-30重量%的硫酸铝,
(b)10-30重量%的至少一种水溶性阳离子型淀粉,
(c)1-5重量%的至少一种萘磺酸与甲醛的缩合物或者萘磺酸盐与甲醛的缩合物和/或木素磺酸或木素磺酸盐,以及
(d)0.1-5重量%的至少一种具有1-10个碳原子的饱和羧酸、苯磺酸、对甲苯磺酸和/或无机酸,
每种情况下均基于烷基乙烯酮二聚物。
6.如权利要求1-4中任一项所述的烷基乙烯酮二聚物水分散体,其中所述分散体包含15-30重量%的至少一种烷基乙烯酮二聚物,以及:
(a)10-20重量%的硫酸铝,
(b)15-25重量%的至少一种水溶性阳离子型淀粉,
(c)1.8-4.0重量%的至少一种萘磺酸与甲醛的缩合物或者萘磺酸盐与甲醛的缩合物和/或木素磺酸或木素磺酸盐,和
(d)0.1-5重量%的至少一种具有1-10个碳原子的饱和羧酸,
每种情况下均基于烷基乙烯酮二聚物。
7.如权利要求5所述的烷基乙烯酮二聚物水分散体,其中所述分散体包含15-30重量%的至少一种烷基乙烯酮二聚物,以及:
(a)10-20重量%的硫酸铝,
(b)15-25重量%的至少一种水溶性阳离子型淀粉,
(c)1.8-4.0重量%的至少一种萘磺酸与甲醛的缩合物或者萘磺酸盐与甲醛的缩合物和/或木素磺酸或木素磺酸盐,和
(d)0.1-5重量%的至少一种具有1-10个碳原子的饱和羧酸,
每种情况下均基于烷基乙烯酮二聚物。
8.如权利要求1-7中任一项所述的烷基乙烯酮二聚物水分散体在作为纸和纸产品的机内施胶胶料和表面胶料方面的用途。
9.如权利要求8所述的用途,其中将所述烷基乙烯酮二聚物水分散体用作生产纸和纸产品的机内施胶胶料。
10.如权利要求8或9所述的用途,其中所述纸为书写纸或印刷纸。
11.如权利要求8或9所述的用途,其中所述纸产品为包装液体的容器。
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US8852400B2 (en) | 2010-11-02 | 2014-10-07 | Ecolab Usa Inc. | Emulsification of alkenyl succinic anhydride with an amine-containing homopolymer or copolymer |
US11649382B2 (en) * | 2014-09-26 | 2023-05-16 | Ahlstrom Oyj | Biodegradable cellulose fiber-based substrate, its manufacturing process, and use in an adhesive tape |
FR3026345B1 (fr) * | 2014-09-26 | 2016-09-30 | Ahlstroem Oy | Support a base de fibres cellulosiques, son procede de fabrication et son utilisation en tant que ruban de masquage |
CN107074658B (zh) * | 2014-10-23 | 2019-09-27 | 巴斯夫欧洲公司 | 混凝土疏水化的方法 |
CA2965440C (en) * | 2014-10-23 | 2023-05-23 | Basf Se | Method for producing a prefabricated building material |
CN106917324B (zh) | 2015-12-25 | 2019-11-08 | 艺康美国股份有限公司 | 一种造纸施胶方法及其制备的纸张 |
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US20180030658A1 (en) * | 2016-07-26 | 2018-02-01 | Footprint International, LLC | Methods and Apparatus For Manufacturing Fiber-Based Produce Containers |
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