CN101198748A - 显示疏油性及疏水性的薄片状产品 - Google Patents
显示疏油性及疏水性的薄片状产品 Download PDFInfo
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Abstract
一种制备具有疏水性和疏油性中的至少一种性能的纤维素薄片的方法，其包括以下步骤：在冲击区域的至少一个成形织物上沉积纤维素纤维的原料，由此在成形过程中形成一种网；在加热步骤之前，使含有一种增粘剂、一种有机纳米颗粒聚合物和一种碳氟化合物的一种水基组合物在一预选的结合步骤中与该网结合，在加热步骤中将该网置于60℃以上的温度下；并且在干燥过程中与该网一起加热固化该组合物。一种在制备过程中赋予纤维素薄片以疏水性和疏油性中的至少一种性能的水基组合物，包括一种增粘剂、一种有机纳米颗粒和一种碳氟化合物。一种纤维素薄片或其层，具有疏水性和疏油性中的至少一种性能。获得了纤维素薄片的改进的抗油性或抗水性。
Description
技术领域
本发明提供一种溶胶-凝胶纳米颗粒材料及其使用方法，以改进薄片状产品例如纸张的特性，以便提高其疏水性和疏油性，从而使所述产品对水和油均相对不可渗透。可将该溶胶-凝胶纳米颗粒材料加入至形成薄片状产品的原料中，或者可将其以涂层的形式施用于一个或两个表面。
背景技术
拟施加于无纺的薄片状产品——例如纸张及相关的纤维素基产品——以提供一种物理防护层从而使其具有疏水性或疏油性，或同时具有疏水性和疏油性的涂布处理是已知的。例如参见授予Honnorat等的US 5,330,622。其它处理方法也是已知的并已被使用。
同样，用于多种目的的对造纸机网毯的涂布处理也是已知的，尤其是为了提供防护层以改善织物的抗污性、抗污染物附着的能力，以及改善相分离及提高疏水性。
近来，对于该类处理，已经使用溶胶-凝胶涂布法，溶胶-凝胶涂布法是指通过制造玻璃的溶胶-凝胶法形成涂层，其中玻璃由合适的化合物在低温下通过液相中的化学聚合形成；所形成的凝胶可通过后续的烧结消除间隙液体并使形成的固体残余物崩塌而得到玻璃。
所述溶胶-凝胶涂布法已用于在尤其是纺织的和无纺的纺织品上形成防护层，以改善其抗污性和抗污染物附着的能力。此外，已知可用溶胶-凝胶涂布法处理造纸织物，例如通透式干燥(TAD)织物，以提高其疏水性。涂层使织物带入TAD部分的水量较少，从而降低了蒸发薄片中的水所需的能量，因为这部分能量只用来干燥薄片，而非薄片和支撑织物二者。
对于相分离设备，例如滤布，已知可有利地使用有机改性的称为“ormocer”的陶瓷。例如，Sayers等的US 5,980,986要求保护一种使用至少一种ormocer作为涂层的方法；Sayers等的US 5,932,291要求保护一种将ormocer用于造纸机网毯中的方法；及Sayers等的US 5,989,651要求保护一种使用至少一种ormocer作为涂层以促进相分离的方法，该法通过在挤出前向聚合物熔体中加入ormocer，并用挤出的聚合物熔体涂覆相分离设备而实现。
上述三篇相关专利涉及一种含全氟化物质的ormocer的用途。本领域技术人员可意识到，这些ormocer为含有氟化物质的有机/无机杂化聚合物，其由下述物质构成：
1.一种可交联的有机硅(如，带有环氧基或异丁烯酰基；见US5,932,291，第50-60行，第1列)——一种与基底(此处为一种织物)产生良好附着的物质，和
2.一种带有全氟化侧链的有机硅。
因此该ormocer由一种极性的和一种疏水的成分构成，并含有陶瓷微粒。
该组中的这三篇相关专利没有一篇指出在含ormocer的涂层中所用的化学试剂是否为水基的或至少部分为溶剂基的。但是，由于在这些专利的优先权日之时(1993年11月16日和1994年2月1日)，只有含溶剂的涂层是已知的，因此上述专利的公开内容只能被认为是涉及至少部分溶剂基涂层的用途。
为了赋予纤维素产品以用于其特定的预期用途时所需的物理特性，还已知可向原料中加入任选的添加剂，然后再将原料通过流浆箱输送到成形织物上的冲击点。该类添加剂包括用于改善固体保留或不透明性的填充物及其它物质。例如，Gill的US 5,147,507教导使用阴离子和阳离子聚合物以减少所需的施胶剂的量并改善填充物保留、排出及不透明性；及Sinclair等的US 4,925,530教导使用添加剂以获得改善的保留性。此外，Westman等的US 6,551,457教导使用添加剂以减少使用冲压装置的工艺过程中的脱层问题；在所述添加剂中，阴离子聚合物可为有机物或无机物，且有机聚合物可含有疏水基团。
此外，使用施胶剂例如松香、淀粉、蜡等的施胶处理也是已知的；例如参见，Pickard等的US 3,993,640，其公开了将环状酰胺用于处理纤维素材料的用途；Pelletier等的US 2003/0127210，其教导使用水分散性的聚酯；Williams等的US 2004/0221976，其教导使用疏水的聚合物；及Ikeda等的EP 0277633，其教导使用淀粉醚。其它处理方法也是已知的并已被使用。
还建议使用添加剂来改善适印性。例如，Matsuda等的US 5,849,447教导了一种含亲水纤维和疏水纤维混合物的用于喷墨印刷或电子照相印刷的非涂布纸；及Malmstrom等的US 2004/0226675教导添加多糖和一种聚合物分散体而达到此目的。
本发明人现已发现，可通过添加含有最高约30重量％固体的水-基溶胶-凝胶分散体而使纸张具有疏水性和疏油性中的至少一种性质，所述分散体可在造纸工艺的几点中的任意点处加入，直到可通过加热或其它适宜方式进行固化的位置。由此，分散体可直接加入制造纸张产品的原料浆液中，或可将其以雾状或其它已知的涂布方式在初始纸页形成后施用于其上。在向原料浆液中加入水基溶胶-凝胶分散体之后，或在下一步骤中将分散体施用于纸页并接着固化所形成的纸张产品之上或之中的涂层后，油墨在处理过的纸张中的渗透被减少，从而提供更清晰的影像，降低或消除了向纸张背面的渗透(bleedthrough)，并潜在地降低了所消耗的油墨。
优选地，所述水基溶胶-凝胶分散体为由以下组分构成的三组分体系：
1.一种增粘剂，
2.含有一种有机预聚物的纳米颗粒材料，和
3.一种碳氟聚合物。
更优选地，所述增粘剂为具有一种以下官能团的有机官能增粘剂，所述官能团为乙烯基、甲基丙烯酸酯基、环氧基、氨基或巯基基团之一。
优选地，所述纳米颗粒材料包括有机纳米颗粒例如包括聚乙烯或聚丙烯在内的纳米蜡，或缩合硅烷类的预聚物，例如甲基三乙氧基硅烷、丙基三乙氧基硅烷、辛基三甲氧基硅烷、辛基三乙氧基硅烷或苯基三甲氧基硅烷等。使用硅烷预聚物的一个优点为，可与增粘剂反应而形成有机预聚物的网状结构。
优选地，所述碳氟聚合物为氟代丙烯酸酯或氟代烷基-聚氨酯共聚物。其它类似的碳氟聚合物也可能是合适的。
上述材料以下述比例混合：约10-25重量％的增粘剂，10-25重量％的纳米颗粒材料，以及约30-70重量％的碳氟聚合物。
根据本发明的教导，适用于生产纤维素基的薄片状产品——例如纸张等——的一种溶胶-凝胶涂布物质可商购获得，其为一种存在于水中的30重量％固体的稀释液，商标名为“Sogetec”，产自Comp-Tex GmbH，Zur Lohe 48，D-52353 Düren，德国。该产品作为一种水基的织物浸渍处理剂出售，其可赋予被处理的基质以永久的疏水性和疏油性。我们已发现，Sogetec及类似物质的有效施用率为每升水约1-10重量％固体。
已发现特别适合于本方法的一种“Sogetec”商品为Sogetec041/30。如上所述，其它类似的包括三组分水基溶胶-凝胶分散体系的处理剂也可能适合于赋予薄片状纤维素基产品——例如纸张、板材等——所述的疏水和/或疏油性，并可包含X-CleanTextile ProtectVP-V1/1/KNK-10，其可由德国Saarbruecken的Theodore HeussStrasse 11a的Nano-X GmbH获得。
经过处理的材料而后在约60℃至约210℃的温度固化，以使纳米颗粒处理有效。已发现当固化温度在约100℃至200℃范围内时处理的持久性增强。
本发明的添加剂分散体与现有技术中的添加剂具有几个不同之处。首先，所述分散体含有两种分离的体系，该两种体系彼此间不发生反应，即，它们之间既不形成共价键也不会结合为共混物(alloy)的形式。为此目的特别选择的碳氟树脂的薄膜、优选沉积在碳氟树脂上的氟代丙烯酸酯，较只由碳氟树脂构成涂层时要薄得多。此外，本发明的添加剂分散体中的疏水组分与现有技术中ormocer的任何组分无关，并且不合无机(即陶瓷)微粒。
此外，本发明的添加剂分散体中的碳氟树脂特别设计用来与有机硅产品一起使用，并完全不同于美国专利No.5,932,291教导的氟硅烷的全氟侧链。
实验工作
在实验室中使用重力纸页成形器重复纸页成形过程。在该仪器中，使原料溶液在重力作用下通过已知的成形织物，从而在织物表面形成纸网。而后将由此形成的纸页干燥，从成形织物上移开，并检验。在确定纳米颗粒材料对造纸工艺的影响的实验工作中，使用再制浆的静电感光复印纸作为纤维源以形成定量约20至25gsm(每平方米的克数)的手抄纸。
实验中，将0.1重量％的Sogetec 041/30材料的固体(即，0.3％的该液体)加入含再制浆的造纸纤维和适量水的纸浆中。用不含任何Sogetec 041/30材料的原料作为对照。手抄纸(即织物上形成的小纸页)使用如上所述的重力纸页成形器由该稀释液形成。然后将实验手抄纸及对照手抄纸在约105℃的温度在同样条件下干燥。该提高温度下的干燥过程也起到使实验手抄纸中Sogetec 041/30材料固化的作用。然后将油滴和水滴分别施用于实验手抄纸和对照手抄纸各自的表面。
发现由含有约0.1重量％的Sogetec 041/30材料固体的纸浆原料制得的手抄纸，与不阻止并立即将油和水吸收的对照纸页相比，能够阻止施用的油和水。对实验手抄纸和对照手抄纸的检验表明，施用于含0.1重量％的Sogetec 041/30材料固体的实验手抄纸表面的油滴和水滴，在纸页的表面维持珠状数小时，而不会渗透到纸页的表面以下。该效果在颗粒材料的浓度低至1.0ppm(每百万中的份数)都可观察到。相比之下，不含任何Sogetec 041/30材料的手抄纸将各种液滴立即吸收。
在实验过程中Sogetec 041/30溶胶-凝胶材料也以如下方式施用：首先干燥纸页，然后在约0.1重量％的Sogetec 041/30固体浓度下浸涂该纸页，接着再将其干燥；发现这种施用方法产生了与上述基本相同的结果。在实验测试中使用的另一种施用方法为，用水中含约0.1重量％的Sogetec 041/30的固体的气溶胶液体对手抄纸进行喷雾，喷雾过程借助喷雾器施用到湿纸页的非织物接触侧。而后将该纸页干燥并固化。在相同实验的第二种情况下，将含0.1重量％的Sogetec041/30固体的水喷雾到干纸页上，接着将其再干燥。该第二种喷雾方法，即喷雾到干纸页上并接着将其再干燥及固化，似乎使防护特性产生“一侧性”(换句话说，似乎只有纸页的一侧具有防护特性)。
在制备及对固化的处理纸页进行初步测试后，通过将油滴和水滴施用于纸页上数周的时间而进行进一步的测试。在各种情况下，都保持了防护效果。当印刷油墨以常规方式施用到固化的处理纸页后，该纸页显示出不渗透性，而且书写图像较未处理的对照纸页更为清晰。
因而，无纺的薄片状产品，尤其是纸张及类似的纤维素基产品，加入下述一种纳米颗粒材料后使其既具有疏水性又具有疏油性，所述纳米颗粒材料由一种溶胶-凝胶型方法形成，其包括纳米蜡或在固化过程中与一种氟代胺反应的缩合的硅烷预聚物。该材料可小量地加入形成纤维素薄片产品的原料中，或者可将纤维素薄片在干燥步骤之前，通过常规的喷雾法施用含该纳米颗粒材料的水基溶液、或通过在上述含有纳米颗粒材料的水基溶液中浸涂该薄片而进行处理。不管是采用将纳米颗粒材料加入产品中还是施用于产品上的方法，都必须将薄片状产品加热以使纳米颗粒材料固化，从而得到增强的防护特性。固化后，纳米颗粒材料使该薄片具有了疏水和疏油特性，其有助于阻止水和油的渗透。
发明内容
因此，在第一种宽泛的实施方案中，本发明旨在提供一种制备具有疏水性和疏油性中的至少一种性能的纤维素薄片的方法，所述方法包括
(i)在冲击区域的至少一个成形织物上沉积纤维素纤维的原料，由此在成形过程中形成一种网；
(ii)在加热步骤之前，使含有一种增粘剂、一种有机纳米颗粒聚合物和一种碳氟化合物的一种水基组合物在一预选的结合步骤中与该网结合，在加热步骤中将该网置于60℃以上的温度下；并且
(iii)在干燥过程中与该网一起加热固化该组合物。
在该实施方案中，该水基组合物材料优选以添加剂的形式在冲击点上游的某处加入原料中，加入的量为原料重量的0.001％至1％。之后，纤维素产品可由已知的方法形成。但是，也可将含有水基组合物添加剂材料的原料作为一个单独的层加入一种多层纸张结构中；经过处理的原料可用作，例如，多层纸张产品的一个内部防护层，或其一个或两个外层。不管含添加剂材料的原料位于何处，形成的薄片都必须加热以使添加剂材料固化。
在该实施方案的一种变形方式中，将该水基组合物材料在成形过程中(即当该薄片非常湿时)以雾状施用于该薄片的一侧或两侧，形成薄片的涂层。然后将该薄片通过常规的薄片干燥过程干燥，作为一个单独的过程或在常规的薄片干燥过程之中使涂层加热固化。
在第二种宽泛的实施方案中，本发明还试图提供一种在制备过程中赋予纤维素薄片以疏水性和疏油性中的至少一种性能的组合物，该组合物包括一种增粘剂、一种有机纳米颗粒聚合物和一种碳氟化合物。
在第三种宽泛的实施方案中，本发明还试图提供一种具有疏水性和疏油性中的至少一种性能的纤维素薄片，其由纤维素纤维的原料以一种网的形式制备，其中所述网与一种含一种增粘剂、一种有机纳米颗粒聚合物及一种碳氟化合物的水基组合物相结合。
在本发明的各种实施方案中，存在于水基组合物中的增粘剂优选为一种有机官能化的硅烷，其官能团优选选自乙烯基、环氧基、氨基、巯基和甲基丙烯酸酯基。该有机纳米颗粒聚合物优选选自聚乙烯或聚丙烯纳米蜡，或一种缩合硅烷的预聚物，所述缩合硅烷优选选自甲基三乙氧基硅烷、丙基三乙氧基硅烷、辛基三甲氧基硅烷、辛基三乙氧基硅烷或苯基三甲氧基硅烷。碳氟化合物优选选自氟代丙烯酸酯和氟代烷基-聚氨酯共聚物。
在水基组合物材料中，上述三种主要组分优选以10-25％增粘剂、10-25％有机纳米颗粒和30-70％的一种碳氟化合物的含量存在。
在本发明的各种实施方案中，水基组合物材料的加热固化优选在约60℃至约210℃、更优选在约100℃至200℃的温度进行。
如上所述，本发明的经过处理的纤维素薄片在多层薄片结构中可包括一层或多层，并且在第四种宽泛的实施方案中，本发明旨在提供一种具有疏水性和疏油性中的至少一种性能的多层纤维素薄片，其中至少一层由纤维素纤维的原料以一种网的形式制备，其中所述网与一种含一种增粘剂、一种有机纳米颗粒聚合物及一种碳氟化合物的水基组合物相结合。
Claims (24)
1.一种制备具有疏水性和疏油性中的至少一种性能的纤维素薄片的方法，所述方法包括
(i)在冲击区域的至少一个成形织物上沉积一种纤维素纤维的原料，由此在成形过程中形成一种网；
(ii)在加热步骤之前，使含有一种增粘剂、一种有机纳米颗粒聚合物和一种碳氟化合物的一种水基组合物在一预选的结合步骤中与该网结合，在加热步骤中将该网置于60℃以上的温度下；并且
(iii)在干燥过程中与该网一起加热固化该组合物。
2.如权利要求1所述的方法，其中所述水基组合物通过在成形过程中涂布所述网的至少一侧而与该网结合。
3.如权利要求1所述的方法，其中所述水基组合物通过在冲击区域沉积之前添加到原料中而与该网结合。
4.如权利要求3所述的方法，其中所述水基组合物中的固体在加入原料中之后，在原料中以0.001％至1％的范围的含量存在。
5.如权利要求4所述的方法，还包括在多层纤维素薄片中加入至少一层所述薄片的步骤。
6.如权利要求1-5中任一项所述的方法，其中所述水基组合物中的增粘剂为一种有机官能化的硅烷，有机纳米颗粒聚合物选自聚乙烯或聚丙烯的纳米蜡和一种缩合硅烷的预聚物，并且碳氟化合物选自氟代丙烯酸酯和氟代烷基-聚氨酯共聚物。
7.如权利要求6所述的方法，其中所述的有机官能化的硅烷中的官能团选自乙烯基、环氧基、氨基、巯基和甲基丙烯酸酯基。
8.如权利要求1-7中任一项所述的方法，其中所述水基组合物中的增粘剂以10-25重量％的范围存在，有机纳米颗粒聚合物以10-25重量％的范围存在并且碳氟化合物以30-70重量％的范围存在。
9.如权利要求6所述的方法，其中所述缩合硅烷选自甲基三乙氧基硅烷、丙基三乙氧基硅烷、辛基三甲氧基硅烷、辛基三乙氧基硅烷和苯基三甲氧基硅烷。
10.如权利要求1-9中任一项所述的方法，其中所述的加热固化步骤在60℃至210℃之间的温度进行。
11.如权利要求1-9中任一项所述的方法，其中所述的加热固化步骤在100℃至200℃之间的温度进行。
12.一种在制备过程中赋予纤维素薄片以疏水性和疏油性中的至少一种性能的组合物，包括一种增粘剂、一种有机纳米颗粒聚合物和一种碳氟化合物。
13.如权利要求12所述的组合物，其中所述的增粘剂为一种有机官能化的硅烷，所述有机纳米颗粒聚合物选自聚乙烯或聚丙烯的纳米蜡和一种缩合硅烷的预聚物，并且所述碳氟化合物选自氟代丙烯酸酯和氟代烷基-聚氨酯共聚物。
14.如权利要求13所述的组合物，其中所述的有机官能化的硅烷中的官能团选自乙烯基、环氧基、氨基、巯基和甲基丙烯酸酯基。
15.如权利要求12所述的组合物，其中所述缩合硅烷选自甲基三乙氧基硅烷、丙基三乙氧基硅烷、辛基三甲氧基硅烷、辛基三乙氧基硅烷和苯基三甲氧基硅烷。
16.如权利要求12-15中任一项所述的组合物，其中所述增粘剂以10-25重量％的范围存在，有机纳米颗粒聚合物以10-25重量％的范围存在并且碳氟化合物以30-70重量％的范围存在。
17.一种具有疏水性和疏油性中的至少一种性能、并由纤维素纤维的原料以一种网的形式制备的纤维素薄片，其中所述网与一种含一种增粘剂、一种有机纳米颗粒聚合物及一种碳氟化合物的水基组合物相结合。
18.如权利要求17所述的纤维素薄片，其中所述的水基组合物被结合到所述原料中。
19.一种具有疏水性和疏油性中的至少一种性能的多层纤维素薄片，其中至少一层由纤维素纤维的原料以一种网的形式制备，其中所述网与一种含一种增粘剂、一种有机纳米颗粒聚合物及一种碳氟化合物的水基组合物相结合。
20.如权利要求17所述的纤维素薄片，其中所述的水基组合物被涂布于所述的网上。
21.如权利要求17-20中的任一项所述的纤维素薄片，其中所述的增粘剂为一种有机官能化的硅烷，所述有机纳米颗粒聚合物选自聚乙烯或聚丙烯的纳米蜡和一种缩合硅烷的预聚物，并且所述碳氟化合物选自氟代丙烯酸酯和氟代烷基-聚氨酯共聚物。
22.如权利要求21所述的纤维素薄片，其中所述的有机官能化的硅烷中的官能团选自乙烯基、环氧基、氨基、巯基和甲基丙烯酸酯基。
23.如权利要求21所述的纤维素薄片，其中所述缩合硅烷选自甲基三乙氧基硅烷、丙基三乙氧基硅烷、辛基三甲氧基硅烷、辛基三乙氧基硅烷或苯基三甲氧基硅烷。
24.如权利要求17-23中任一项所述的纤维素薄片，其中在所述的水基组合物中，增粘剂以10-25重量％的范围存在，有机纳米颗粒聚合物以10-25重量％的范围存在并且碳氟化合物以30-70重量％的范围存在。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0513699A GB2427868A (en) | 2005-07-04 | 2005-07-04 | Cellulosic products having oleophobic and hydrophobic properties |
| GB0513699.9 | 2005-07-04 | ||
| PCT/CA2006/001097 WO2007003051A1 (en) | 2005-07-04 | 2006-07-04 | Sheet-like products exhibiting oleophobic and hydrophobic properties |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101198748A true CN101198748A (zh) | 2008-06-11 |
| CN101198748B CN101198748B (zh) | 2011-06-08 |
Family
ID=34856643
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006800216372A Expired - Fee Related CN101198748B (zh) | 2005-07-04 | 2006-07-04 | 显示疏油性及疏水性的薄片状产品 |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US8007638B2 (zh) |
| EP (1) | EP1899532A1 (zh) |
| CN (1) | CN101198748B (zh) |
| CA (1) | CA2611758A1 (zh) |
| GB (1) | GB2427868A (zh) |
| WO (1) | WO2007003051A1 (zh) |
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| CN104831591A (zh) * | 2015-04-21 | 2015-08-12 | 青岛大学 | 利用浒苔制备纸浆模塑缓冲防震包装制品的生产工艺 |
| CN107614392A (zh) * | 2015-05-21 | 2018-01-19 | 东洋制罐株式会社 | 表面上具有凝胶状覆膜的结构体 |
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| FR2953990B1 (fr) | 2009-12-14 | 2013-01-11 | Commissariat Energie Atomique | Dispositif d'encapsulation a etancheite amelioree |
| CN102277777B (zh) * | 2011-07-18 | 2012-11-07 | 陕西科技大学 | 一种天然纤维/纳米SiO2复合材料纸的制备方法及其所使用的水乳液 |
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| EP3362599A4 (en) * | 2015-10-14 | 2019-05-29 | HeiQ Pty Ltd | METHOD FOR CONFERRING A HYDROPHOBIC CHARACTER |
| US10568240B2 (en) | 2016-06-30 | 2020-02-18 | Ford Global Technologies, Llc | Coolant flow distribution using coating materials |
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| US10560002B2 (en) | 2017-03-29 | 2020-02-11 | Ford Global Technologies, Llc | Coolant flow distribution using coating materials |
| US10622868B2 (en) | 2017-03-29 | 2020-04-14 | Ford Global Technologies, Llc | Coolant flow distribution using coating materials |
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- 2006-07-04 WO PCT/CA2006/001097 patent/WO2007003051A1/en not_active Application Discontinuation
- 2006-07-04 CN CN2006800216372A patent/CN101198748B/zh not_active Expired - Fee Related
- 2006-07-04 CA CA002611758A patent/CA2611758A1/en not_active Abandoned
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104831591A (zh) * | 2015-04-21 | 2015-08-12 | 青岛大学 | 利用浒苔制备纸浆模塑缓冲防震包装制品的生产工艺 |
| CN104831591B (zh) * | 2015-04-21 | 2018-09-21 | 青岛大学 | 利用浒苔制备纸浆模塑缓冲防震包装制品的生产工艺 |
| CN107614392A (zh) * | 2015-05-21 | 2018-01-19 | 东洋制罐株式会社 | 表面上具有凝胶状覆膜的结构体 |
| CN107614392B (zh) * | 2015-05-21 | 2019-05-03 | 东洋制罐株式会社 | 表面上具有凝胶状覆膜的结构体 |
| US10710764B2 (en) | 2015-05-21 | 2020-07-14 | Toyo Seikan Co., Ltd. | Structure having a gel-like coating on the surface thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101198748B (zh) | 2011-06-08 |
| GB2427868A (en) | 2007-01-10 |
| GB0513699D0 (en) | 2005-08-10 |
| EP1899532A1 (en) | 2008-03-19 |
| CA2611758A1 (en) | 2007-01-11 |
| US8007638B2 (en) | 2011-08-30 |
| WO2007003051A1 (en) | 2007-01-11 |
| US20080190574A1 (en) | 2008-08-14 |
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