CN107709663B - 包括两亲性聚合物的膜产品或膜的制造方法 - Google Patents
包括两亲性聚合物的膜产品或膜的制造方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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Abstract
膜的制造方法,其中所述膜在纸或纸板机中制造,其中所述方法包括提供纳米原纤化多糖溶液的步骤,其中所述溶液包括0.01至50重量%的纳米原纤化多糖,以及其中纳米原纤化多糖为微原纤化纤维素、纳米原纤化纤维素、纳米晶体纤维素,微晶纤维素、纤维素晶须和纤维素衍生物或者它们的组合或混合物中的任一种,其中所述方法进一步包括以下步骤:提供两亲性聚合物;和提供所述两亲性聚合物和包括纳米原纤化多糖的所述溶液的混合物,由此获得中间溶液;将所述中间溶液引入泡沫体中;在纸或纸板机中提供所述泡沫体。
Description
技术领域
本发明涉及在纸或纸板(board)制造过程中的纸或纸板(paper board)的制造方法及其产品,其中所述方法包括提供纳米原纤化多糖和两亲性聚合物的混合物。
背景技术
在造纸工业中传统的泡沫体成形中,例如纸或泡沫体涂料(涂层,coating)的成网(幅)(湿法成幅(湿铺)技术)中,泡沫体稳定性可能难以实现。表面活性化学物质例如十二烷基硫酸钠(SDS)可用于实现泡沫的所需的泡沫体稳定性,但是这些类型的添加剂通常对最终产品具有负面影响,即降低的强度,和/或损害强度或阻隔性能的迁移的风险。此外,一些这样的表面活性化学物质是不期望的,因为它们可能在食品或液体包装材料中不被允许。
传统的泡沫体成形描述于GB 1 395 757中,其中发泡的纤维分散体用于造纸中。将表面活性剂加入到纤维浆中,以向待被放置在造纸机的抄网(wire,网部)上的分散体提供至少65%的空气含量。在Wiggins Teaoe Radofoam工艺中也已经描述了湿法成幅的成形,其中将纤维以含水形式的悬浮体输送到传统的长网造纸机(Fourdrinier machine)的抄网上。
近年来,在纸和纸板制造过程中使用微原纤化多糖如微原纤化纤维素(MFC)、纳米纤维素或纳米晶体纤维素(NCC)已变得越来越令人感兴趣。然而,MFC的使用具有一些缺点,即形成的阻隔层或膜具有高的干燥收缩率,以及比例如由传统纸浆制成的纸容易吸收更多的水。由MFC制成或包括MFC的膜或阻隔涂层的脱水通常是相当困难的,因此需要更高的用于脱水的能量,并且降低了制造过程的效率和速度。
在WO2013/160564A1中公开了一种方法,其中通过制造水、疏水性胶浆(size)例如烷基烯酮二聚体(AKD)、表面活性剂例如氧基化的C11-醇和微原纤化纤维素的泡沫体形成纤维幅(纤维网)的经疏水化施胶的(hydrophobically sized)层。
需要一种通过使用泡沫体或者传统的、或重新设计的湿法成幅技术形成湿幅材(wet web)的方法,该湿幅材可进一步被脱水和干燥成自支撑膜或用作在较高的相对湿度下具有改善的气体和气味(aroma)阻隔性能的阻隔涂层。在包括微原纤化纤维的分散体中使用两亲性淀粉进一步提供基本上不含添加剂(例如SDS)的阻隔配制剂。
发明内容
本发明的目的在于提供一种改进的用于以下的方法:形成幅材(webs,纸幅),随后形成自支撑膜或待涂覆在纸或纸板上的涂层(涂料),直接地或者作为自支撑膜,其消除或减轻现有技术的泡沫体的至少一些缺点。
该目的通过根据所附的独立权利要求的方法来实现。在所附的从属权利要求中以及在以下的描述和附图中对实施方式进行阐述。
根据第一方面,提供一种制造膜的方法,其中所述膜在纸或纸板机中制造,其中所述方法包括提供纳米原纤化多糖的溶液的步骤,其中所述溶液包括0.01至50重量%的纳米原纤化多糖以及其中纳米原纤化多糖为微原纤化纤维素、纳米原纤化纤维素、纤维素晶须和纤维素衍生物或者它们的组合或混合物中的任一种。所述方法进一步包括以下步骤:提供两亲性聚合物;和提供所述两亲性聚合物和包括纳米原纤化多糖的所述溶液的混合物,由此获得中间溶液(中间体溶液);将所述中间溶液引入泡沫体中;在纸或纸板机中提供所述泡沫体。
“两亲性聚合物”是指所谓的具有亲水性和疏水性(或亲脂性)基团两者的表面活性聚合物。
通过该方法可形成具有优异的水分阻隔性能(防潮性能)、或为疏水性的,即低透氧率的幅材或膜或涂层,而不需要使用传统的表面活性化学物质,或更具体地诸如表面活性剂的化学物质,所述化学物质在许多应用中并且由于各种原因是不期望的。这些膜还可具有改善的水分透过率(WVTR)值。甚至进一步地,与包括表面活性剂的膜或涂层相比,这些膜或涂层可具有提高的拉伸强度。该组合物或混合物还可具有对气味和油脂或其它脂肪类物质的优异的阻隔性。
通过用纳米原纤化多糖和两亲性聚合物形成泡沫体可在无需使用例如SDS的表面活性剂的情况下生产用于造纸的泡沫体,其已被证明具有优异的稳定性和良好的复合成形能力。因此,所述泡沫体可用于纸或纸板是可生物降解的的应用中,或者用于对化学物质的产品安全性是最为重要的应用中,例如在食品包装中。泡沫体可用于形成幅材或作为方法中的涂层(涂料)材料。
所述方法因此可进一步包括以下步骤:将泡沫体供给至成形网(forming fabric)以形成泡沫体幅材,在成形网上使泡沫体幅材脱水,使泡沫体幅材干燥以形成纸或纸板产品;或者在所述纸或纸板制造机器中将所述泡沫体作为涂层(涂料)施加的步骤。
因此,纸或纸板产品可为例如在纸或纸板上的阻隔膜(自支撑的或层压的)、或阻隔涂层,其具有良好的阻隔性能,即具有较好的氧气透过率性质,特别是在较高的相对湿度(RH)值(即高于50%RH值)下。此外,两亲性聚合物和纳米原纤化多糖的混合物已被证实具有比包括纳米原纤化多糖的传统湿法成幅幅材(wet laid webs,湿铺幅材)更好的脱水能力。由纳米原纤化多糖和两亲性聚合物的混合物获得的这种阻隔膜还可提供其它有利的阻隔性质,例如对气味、油脂或其它脂肪类物质。
根据一种实施方式,两亲性聚合物选自:辛烯基琥珀酸酐(OSA)淀粉、十二烷基琥珀酸酐(DDSA)淀粉、疏水改性的乙基羟乙基纤维素(HM-EHEC)、疏水改性的羟乙基纤维素(HM-HEC)、疏水改性的羧甲基纤维素(HM-CMC)、疏水改性的淀粉(HM-淀粉)、疏水改性的纳米晶体纤维素或其组合或混合物中的任一种。还可使用诸如烷基琥珀酸酐(ASA)的物质。
据另一种实施方式,两亲性聚合物是包含>2%乙酸酯基团,或者更优选地大于10%乙酸酯基团,甚至更优选地>15%乙酸酯基团的聚乙烯醇。
两亲性聚合物可为辛烯基琥珀酸酐(OSA)淀粉或n-OSA淀粉。淀粉的表面活性主要由OSA基团或n-OSA基团提供。此外,OSA淀粉通常被认为是在食品和包装工业中安全使用并且是对环境友好的产品。与其它类型的表面活性化学物质相比,其使用相对便宜,并且可被引入传统的造纸工艺而不必对该工艺进行任何其它的改变。
根据一种实施方式,OSA淀粉可以1至10%(重量/重量)的量提供,基于(即,按计算)纳米原纤化多糖溶液中纤维的量。这意味着添加了相对大量的两亲性聚合物或疏水改性的淀粉。相对大的量还意味着在这样的应用中通常不被认为是有用的量。
根据第一方面的一种实施方式,所述方法可进一步包括在所述微原纤化多糖的存在下蒸煮或热处理两亲性聚合物的步骤。
通过这种方法,可共同原纤化例如OSA淀粉和纳米原纤化多糖,如MFC。
该方法可进一步包括在所述两亲性聚合物的存在下形成所述纳米原纤化多糖的步骤。
根据第一方面的一种实施方式,当混合物被引入泡沫体时,所述方法可包括向所述纸或纸板制造机器的湿部提供作为添加剂的所述泡沫体。
因此泡沫体添加剂可在所述湿部中用作增强剂或膨胀剂(填充剂),或用作涂布剂(涂层剂)。
根据第二方面,提供通过根据第一方面的方法获得的纸或纸板产品。
根据第二方面,所述产品可为具有在50%的相对湿度下测量的小于20cm3/m2/天、或在50%的相对湿度下测量的小于15cm3/m2/天、或在50%的相对湿度下测得的小于10cm3/m2/天或在50%的相对湿度下测得的小于5cm3/m2/天的氧气透过率(OTR)的阻隔膜或阻隔涂层。OTR值是在23℃下测量的。所述纸或纸板因此具有非常低的OTR值。阻隔物可以是水分(湿气)阻隔物,但也可以是气味或油脂阻隔物(即脂肪类物质)。
具体实施方式
本发明涉及一种可在本领域技术人员已知的传统造纸或纸板制造机器或工艺中适用的制造方法。
根据一种实施方式,提供了纳米原纤化多糖的溶液。
该溶液包括0.01至50重量%、或0.1至15重量%、或0.1至2.5重量%的纳米原纤化多糖。
所述纳米原纤化多糖可为微原纤化纤维素(MFC)、纳米原纤化纤维素、纤维素晶须和纤维素衍生物或者它们的组合或混合物中的任一种。
纳米原纤化多糖的定义包括使用静电纺丝或使用传统纺丝技术纺丝的细菌纤维素或纳米纤维素。在这些情况下,材料优选为多糖,但不仅限于多糖。多糖可为例如淀粉、蛋白质、纤维素衍生物等。在该定义中还包括下文更详细定义的微原纤化纤维素。
微原纤化纤维素(MFC)也被称作纳米纤维素。它是一种通常由来自阔叶木或针叶木纤维两者的木质纤维素纤维制成的材料。它还可由微生物来源,农业纤维如麦草浆、竹子或其它非木质纤维来源制成。在微原纤化纤维素中,单独的微纤丝(microfibrils)已经部分或完全地彼此分离。微原纤化纤维素纤丝(fibril)通常是非常薄的(约20nm)并且长度通常为100nm至10μm。然而,微纤丝也可以是更长的,例如10-200μm,但由于长度分布宽,因而甚至可发现2000μm的长度。MFC的定义包括已经被原纤化的并且在表面上具有微纤丝的纤维和已分开的(separated)并且位于浆料水相中的微纤丝。此外,MFC的定义还包括纤维素晶须。纤丝也可以是聚合物涂覆的纤丝,即化学或物理改性的纤丝。
根据本发明的方法还包括提供两亲性聚合物,并且随后将所述两亲性聚合物与包括纳米原纤化多糖的溶液混合。这意味着形成包括如上所述的量的纳米原纤化多糖、两亲性聚合物和剩余部分的水的第二溶液。选择两亲性聚合物的量使得溶液包括纳米原纤化多糖、两亲性聚合物、其它可能的添加剂和水直至100%。根据一种实施方式,两亲性聚合物的溶液包括1-100%、更优选地1-50%、且最优选地1-10%的两亲性聚合物(重量/重量)。
根据一种实施方式,在原液(储备液)中,两亲性聚合物的量可为1-10%,基于纳米原纤化多糖的量,或基于纤维的量。“两亲性聚合物”是指具有亲水性和疏水性(或亲脂性)基团两者的聚合物。术语两亲性聚合物和表面活性聚合物两者均在本说明书中使用。
两亲性聚合物或表面活性聚合物可以是所谓的疏水表面活性聚合物。在那些表面活性聚合物中,对本发明有用的是例如乙基羟乙基纤维素(EHEC)、疏水改性的(HM)乙基羟乙基纤维素(HM-EHEC)、羟乙基纤维素(HEC)、疏水改性的羟乙基纤维素、HM-HEC、羟丙基化的纤维素(HPC)、疏水改性的羧甲基纤维素(HM-CMC)、HM-淀粉、羟丙基化的淀粉等。两亲性聚合物还可以是辛烯基琥珀酸酐(OSA)淀粉、十二烷基琥珀酸酐(DDSA)淀粉、具有疏水性质的羧甲基纤维素(CMC)中的任一种。根据一种实施方式,两亲性聚合物是疏水改性的聚乙烯醇(PVOH),例如乙烯改性的PVOH。根据另一种实施方式,表面活性聚合物可为含有>2%的乙酸酯基团、或更优选地大于10%的乙酸酯基团、甚至更优选地>15%的乙酸酯基团的聚乙烯醇。
两亲性聚合物也可以是带电荷的两亲性聚合物。电荷可有助于保留(滞留)。
两亲性聚合物或表面活性聚合物还可以是不同的两亲性聚合物或表面活性聚合物的混合物或上述两亲性聚合物或表面活性聚合物的衍生物。
根据一种实施方式,在原液中,OSA淀粉的量可为1%-10%的范围内,基于纳米原纤化多糖的量,或基于纤维的量。
两亲性聚合物可具有特定的浊点(浑浊温度,cloud temperature)。包括干燥在内的工艺温度可在该特定的浊点下进行,从而“活化”聚合物。可通过特定的pH、温度或添加剂活化两亲性聚合物。通过相应地调节温度,可因此控制,即引发例如由混合物形成的泡沫体或使其塌陷。
根据一种优选的实施方式,两亲性聚合物为OSA淀粉或n-OSA淀粉。
中间产物或溶液通过这种混合物获得,随后其可进一步被用于纸或纸板制造工艺中。
根据一种实施方式,可将中间溶液引入泡沫体。这可通过任何传统手段来实现,例如以机械方式,即搅动;或以化学方式,通过添加发泡化学物质。还可通过向中间溶液中加入例如宏观的、微米或纳米气泡实现。
随后可在造纸或纸板制造工艺中以不同的方式使用所述泡沫体。根据一种实施方式,泡沫体可用于泡沫体成形工艺,即幅材的泡沫体成形,其中随后对该幅材进行压制并干燥以形成片材或膜产品。片材或膜可用作单层纸,或者用作(例如板或其它纸产品的)阻隔物(barrier,组隔层)、阻隔层压体或涂层。
根据另一种实施方式,泡沫体可在该方法(工艺)中用作涂层(涂料)或者用作湿部添加剂。
根据一种实施方式,该方法包括在两亲性聚合物的存在下原纤化纤维素纤维。这可促进两亲性聚合物的溶解,因为这些物质可具有有限的或至少低的溶解度。在两亲性聚合物的存在下进行纤维的原纤维化还可使得通过原纤化过程形成的纤丝稳定化。
根据另一种实施方式,在形成泡沫体或在流浆箱(head-box)中供给混合物之前,两亲性聚合物例如OSA淀粉与纳米原纤化多糖微原纤化纤维素一起被蒸煮或加热。
通过上述方法,因此可形成纸或纸板产品,其中该产品包括或构成片材或膜,所述片材或膜相应地通过使用中间溶液(即如泡沫体一样的(作为泡沫体的,as foam)纳米原纤化多糖和表面活性聚合物的混合物)形成。
通过该方法形成的片材或膜可以是或者可作为用于水分、以及用于气味、油脂或其它脂肪类物质的阻隔物。
根据一种实施方式,片材或膜,所述产品为具有在50%的相对湿度下测量的小于20cm3/m2/天、或在50%的相对湿度下测量的小于15cm3/m2/天、或在50%的相对湿度下测得的小于10cm3/m2/天或在50%的相对湿度下测得的小于5cm3/m2/天的氧气透过率(OTR)的阻隔膜或阻隔涂层。根据一种实施方式,OTR为在50%的相对湿度下测量的1-5cm3/m2/天,或在50%的相对湿度下测量的2-4cm3/m2/天。OTR值是在23℃下测量的。
根据一种实施方式,对于原纸,通过该方法形成的纸或膜的定量(basis weight,基重)或克重可为原纸的10-100g/m2、或10-40g/m2、或10-30g/m2、或10-25g/m2。
鉴于本发明的以上详细描述,其它修改和变化对于本领域技术人员将变为显而易见的。然而,显而易见的是,可在不脱离本发明的精神和范围的情况下进行这样的其它修改和变化。
Claims (12)
1.一种制造膜的方法,其中所述膜在纸或纸板机中制造,其中所述方法包括提供纳米原纤化多糖的溶液的步骤,其中所述溶液包括0.01至50重量%的纳米原纤化多糖,以及其中所述纳米原纤化多糖为微原纤化纤维素、纳米原纤化纤维素、或者它们的组合或混合物中的任一种,其特征在于,所述方法进一步包括以下步骤:
提供两亲性聚合物;和
提供所述两亲性聚合物和包括纳米原纤化多糖的所述溶液的混合物,由此获得中间溶液;
使所述中间溶液成为泡沫体;
在纸或纸板机中提供所述泡沫体,
其中所述两亲性聚合物选自辛烯基琥珀酸酐(OSA)淀粉、十二烷基琥珀酸酐(DDSA)淀粉、疏水改性的乙基羟乙基纤维素(HM-EHEC)、疏水改性的羟乙基纤维素(HM-HEC)、疏水改性的羧甲基纤维素(HM-CMC)、疏水改性的淀粉(HM-淀粉)、疏水改性的纳米晶体纤维素、疏水改性的聚乙烯醇或者它们的组合或混合物中的任一种。
2.如权利要求1所述的方法,其中所述微原纤化纤维素为纤维素晶须。
3.如权利要求1所述的方法,其中所述方法进一步包括以下步骤:
将所述泡沫体供给至成形网以形成泡沫体幅材;
在成形网上使所述泡沫体幅材脱水;
使所述泡沫体幅材干燥以形成膜。
4.如权利要求1所述的方法,其中所述方法进一步包括在所述纸或纸板制造机器中将所述泡沫体作为涂层施加的步骤。
5.如权利要求1所述的方法,其中两亲性聚合物为辛烯基琥珀酸酐(OSA)淀粉。
6.如权利要求5所述的方法,其中基于纳米原纤化多糖溶液中的纤维的量,以1至10重量%的量提供OSA淀粉。
7.如权利要求1-4中任一项所述的方法,其中所述方法进一步包括在所述纳米原纤化多糖的存在下蒸煮两亲性聚合物的步骤。
8.如权利要求1-4中任一项所述的方法,其中所述方法进一步包括在所述两亲性聚合物的存在下形成所述纳米原纤化多糖的步骤。
9.如权利要求1所述的方法,其中所述方法包括向所述纸或纸板制造机器的湿部提供作为添加剂的所述泡沫体。
10.纸或纸板产品,其包括通过如权利要求1至9中任一项所述的方法获得的膜。
11.如权利要求10所述的纸或纸板产品,其中所述产品包括具有在50%的相对湿度下测量的小于20cm3/m2/天、或在50%的相对湿度下测量的小于15cm3/m2/天、或在50%的相对湿度下测得的小于10cm3/m2/天或在50%的相对湿度下测得的小于5cm3/m2/天的氧气透过率(OTR)的阻隔膜或阻隔涂层。
12.如权利要求10所述的纸或纸板产品,其中所述产品为原纸,并且其中该原纸具有10-100g/m2、或10-40g/m2、或10-30g/m2、或10-25g/m2的定量。
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CA2988517A1 (en) | 2016-12-29 |
AU2016284940A1 (en) | 2017-12-21 |
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AU2016284940B2 (en) | 2020-02-27 |
JP2018520273A (ja) | 2018-07-26 |
EP3314056A4 (en) | 2019-01-16 |
CN107709663A (zh) | 2018-02-16 |
EP3314056A1 (en) | 2018-05-02 |
US20180355557A1 (en) | 2018-12-13 |
BR112017028127B1 (pt) | 2022-04-19 |
SE540731C2 (en) | 2018-10-23 |
JP6816040B2 (ja) | 2021-01-20 |
SE1550896A1 (en) | 2016-12-27 |
WO2016207783A1 (en) | 2016-12-29 |
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