CN114867772A - 制造包含微原纤化纤维素的纤维素膜的方法 - Google Patents
制造包含微原纤化纤维素的纤维素膜的方法 Download PDFInfo
- Publication number
- CN114867772A CN114867772A CN202080090154.8A CN202080090154A CN114867772A CN 114867772 A CN114867772 A CN 114867772A CN 202080090154 A CN202080090154 A CN 202080090154A CN 114867772 A CN114867772 A CN 114867772A
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- oil
- film
- cellulose
- mfc
- film forming
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
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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
- C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
- C09D101/02—Cellulose; Modified cellulose
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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
- C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
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- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
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- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/36—Polyalkenyalcohols; Polyalkenylethers; Polyalkenylesters
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
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Abstract
提供制造包含微原纤化纤维素(MFC)的纤维素膜的方法,所述方法包括以下步骤:将一种或多种植物油的含水乳液施加至流延基材的表面。因此可实现MFC膜的改进的脱离。
Description
技术领域
本发明涉及制造包含微原纤化纤维素(MFC)的纤维素膜的方法。还提供MFC膜。
背景技术
有利的是使用亲水性的膜成形聚合物例如聚乙烯醇来强化纤维素膜的阻隔性质和增强。特别地,这样的添加剂可用于微原纤化纤维素(MFC)的膜,其中由于MFC的精细度,纤维间结合是弱的。
在纤维素膜制造中当在基材上流延时发生的一个问题是这样的组分可赋予的膜和基材之间的非常高的粘附程度。即便在非常低的剂量下,膜成形聚合物可产生如此高的粘附性使得干燥时纤维素膜无法从流延基材分离。该问题的解决方案包括从流延基材洗刷或冲洗纤维素膜。然而,这样的解决方案在连续生产工艺中是有效性较低的,其中机器速度高并且纤维素膜需要从流延基材以精确且受控的方式分离。
已知在光学膜和塑料膜行业中使用基于含氟聚合物、硅烷、硅烷醇或硅氧烷的脱离剂将塑料膜从流延基材分离。这样的脱离剂通常是有毒的并且因此不适合生产旨在用于例如食物接触的膜。
仍需要包含MFC的纤维素膜从流延基材的脱离中的改进。
发明内容
因此,在第一方面中提供制造包含微原纤化纤维素(MFC)的纤维素膜的方法,所述方法包括以下步骤:
a.提供具有至少一个表面的流延基材;
b.将一种或多种植物油的含水乳液施加至所述流延基材的所述表面;
c.将膜成形组合物在所述流延基材的经处理的表面上流延,所述膜成形组合物包含MFC和亲水性的膜成形聚合物;
d.将膜成形组合物在流延基材上干燥以形成包含微原纤化纤维素(MFC)的纤维素膜;和
e.将形成的纤维素膜从流延基材分离。
还提供了脱离剂促进包含MFC和亲水性的膜成形聚合物的纤维素膜从流延基材的表面的脱离的用途,所述脱离剂为一种或多种植物油的含水乳液。
进一步地,提供纤维素膜,其包含微原纤化纤维素(MFC)和亲水性的膜成形聚合物,所述纤维素膜界定了表面,其中至少一种植物油存在于所述表面上。
本发明的进一步细节从以下描述和从属权利要求是显而易见的。
具体实施方式
已经发现含有MFC和亲水性的膜成形聚合物的纤维素膜从流延基材的脱离的显著的改进可通过将脱离剂(其为至少一种植物油)的薄层在MFC膜在流延基材的表面上成形之前施加在所述流延基材的表面上而实现。这样的脱离剂能够从流延基材的表面分离整洁、未损坏的含有膜成形聚合物的MFC膜。特别地,此类脱离剂可为基本上无毒的,并且可在连续生产期间添加以及提供脱离性质中的快速响应,能够精确控制膜粘附性和脱离,而不影响MFC膜自身的性质(例如氧阻隔性质)。
特别地,甚至低剂量的植物油脱离剂也可提供脱离的显著改进。这是重要的,因为某些化学品可充当“剥离剂”,并且以低剂量施加因此是可用的。
本发明中使用的植物油可被允许用于直接食物接触,根据来自FDA的“GRAS”规定或可符合BfR推荐XXXVI。植物油可为可食用的。
使用本发明的脱离剂能够以可控方式调节MFC膜对流延基材的粘附性。
提供制造包含微原纤化纤维素(MFC)的纤维素膜的方法;即MFC膜。该方法包括以下大体步骤:
a.提供具有至少一个表面的流延基材;
b.将一种或多种植物油的含水乳液施加至所述流延基材的所述表面;
c.将膜成形组合物在所述流延基材的经处理的表面上流延,所述膜成形组合物包含MFC和亲水性的膜成形聚合物;
d.将膜成形组合物在流延基材上干燥以形成包含微原纤化纤维素(MFC)的纤维素膜;和
e.将形成的纤维素膜从流延基材分离。
MFC膜的一个优点是它们对可见光可为透明的。因此优选地,当对定量为约30gsm的膜使用标准DIN 53147测量时,MFC膜的透明度大于50%、优选大于65%、且更优选大于75%。注意到MFC膜可对可见光具有高透明度但对UV光具有差的透明度。
本文所述的MFC膜可提供至少针对脂/油、水分、氧或气味之一的提高的阻隔性。MFC膜适宜地具有根据ASTM D-3985在10-50gsm之间的定量下小于5000cc/m2/24h(23℃,50%RH),更优选范围为100-1000cc/m2/24h的氧气透过率(OTR)值。在这些条件下,OTR也可低于100cc/m2/24h,例如0.1-100cc/m2/24h。
进一步地,根据本发明制造的MFC膜的拉伸强度(指数)的至少60%、更优选至少70%、或最优选至少80%可被保持,与不使用本发明的脱离剂制造的相同组成的参比MFC膜相比。当脱离剂以低量施加并且由此不影响膜的拉伸强度时,这是特别相关的。
流延基材
该方法需要具有至少一个表面的流延基材。流延基材可为常用于流延纤维质悬浮体的任意这样的基材。基材可由塑料或金属,或其组合形成。在一个实施方式中,其中方法是连续的,流延基材为带,例如金属带。
其上流延MFC膜(膜成形组合物)的表面可为基本上平面的,或可具有纹理,或可具有有纹理的区域并且其它区域为基本上平面的。表面可具有用于排走来自膜成形组合物的液体的开口。
其上流延膜成形组合物的表面(例如带)可具有1-300m的长度和0.2-10m的宽度。表面还可涂覆有例如陶瓷或塑料涂层例如以调节表面能。
如果表面有纹理,其可以无规方式或预定图案含有凹部或凸出区域。例如,可通过蚀刻非导通或导通通道在有纹理的表面中形成凹部的图案。还可沉积材料以形成凸出区域。一个实例是使用激光技术用于雕刻有纹理的表面。
在一个实施方式中,其中流延基材为金属带,表面可具有经研磨或抛光的最后一道涂饰(finish)以提供光滑的膜表面。对于非常光滑的膜表面,可使用镜品质抛光的金属带。金属带也可具有聚合物涂层,例如PTFE涂层。
脱离剂
将一种或多种植物油的含水乳液施加至所述流延基材的表面。如上文所述,使用这样的植物油能够从流延基材的表面分离整洁、未损坏的含有膜成形聚合物的MFC膜。
基于植物油的脱离剂用于薄纸行业,来改变杨克缸(Yankee cylinder)表面性质用于基于薄纸的纸的良好起褶(起皱),见例如Pratima Bajpai的“Pulp and paperindustry chemicals”(2015,ISBN 978-0-12-803408-8)和WO2011156313A1。然而,起褶与流延是不同的工艺,并且薄纸通常不含MFC纤维。这样的脱离剂一般不用于流延工艺或包含MFC的纤维素膜。
适宜地,将乳液施加至所述流延基材的表面使得一种或多种植物油以以下水平涂覆:0.1–500mg/m2、优选0.5–150mg/m2。含水乳液可包含低量的植物油,例如0.01-20wt%、优选0.01-10wt%、更优选0.1-5wt%的所述一种或多种植物油,同时仍提供从流延基材的良好脱离。
所述一种或多种植物油可选自:辣木油、棕榈油、棕榈仁油、卡诺拉油、椰子油、豆油、向日葵油、菜籽油、花生油、棉籽油、橄榄油、亚麻籽油、玉米油、红花油、核桃油、芝麻油、杏仁油、蓖麻油、菜油、假亚麻油、汉麻油、芥子油、萝卜油、兰提油(ramtil oil)、米糠油、桐油、海蓬子油、麻风树油或基于藻类的油。
一种或多种植物油的含水乳液应具有足够低的粘度使得其可喷洒或铺散在表面上。当根据DIN 53015在20℃下测量时,植物油的含水乳液的粘度适宜地小于1000mPas、优选小于500mPas。
含水乳液可含有稳定剂或乳化剂。乳化剂可选自:非离子型、阳离子型或阴离子型乳化剂。乳液中的平均粒度为10-1000nm或优选20-400nm。
膜成形组合物
本发明的膜成形组合物包含MFC和亲水性的膜成形聚合物。该组合物典型地为MFC的含水分散体,其中溶解有亲水性的膜成形聚合物。优选地,膜成形组合物为含水组合物,其包含10–99wt%MFC、优选50-99wt%MFC、更优选70-95wt%MFC,基于膜成形组合物的总固含量计。
当用Brookfield粘度计在100rpm在20℃下测量时,膜成形组合物的粘度应大于500cP、优选大于1000cP。
微原纤化纤维素(MFC)
本发明提供包含微原纤化纤维素(MFC)的纤维素膜。MFC在本技术的上下文中应意指纳米尺度的纤维素纤维或纤丝,其中至少一个维度,优选直径,小于1000nm。MFC悬浮体也可包含部分或完全未原纤化的纤维素或木质纤维素纤维。纤维素纤维优选原纤化至这样的程度,形成的MFC的最终比表面积为约1至约500m2/g,例如10至300m2/g或更优选50-200m2/g(当用BET方法测量经溶剂交换且冷冻干燥的材料时)。MFC的均值平均纤丝直径为1-1000nm,优选10-1000nm。MFC可通过分析高分辨率SEM或ESEM图像表征。
优选地,MFC膜中的MFC含量为至少10wt%、优选50wt%、更优选至少60wt%、且最优选至少70wt%,基于总固含量计。在一个实施方式中,MFC膜包含至多50wt%、例如至多30wt%、适宜地至多20wt%的部分或完全未原纤化的纤维素或木质素纤维,其具有大于1000nm的均值平均纤丝直径,基于总固含量计。
存在多种制造MFC的方法,比如单或多道次精磨,预水解后接精磨,或高剪切解离或纤丝释放。通常需要一种或数种预处理步骤以使得MFC制造既能量高效又可持续。待供应的浆的纤维素纤维可因此以酶或化学方式预处理,例如以降低半纤维素或木质素的量。纤维素纤维可在原纤化之前被化学改性,其中纤维素分子含有不同于(或多于)原始纤维素中发现的官能团。这样的基团尤其包括羧甲基、醛和/或羧基(通过N-氧基介导氧化获得的纤维素,例如"TEMPO"),或季铵(阳离子型纤维素)。在上述方法之一中改性或氧化之后,更易于将纤维解离成MFC。
MFC可含有一些半纤维素;该量取决于植物源。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)的机械解离用适宜的设备进行,所述设备例如精磨机、研磨机、均质器、胶化器、摩擦研磨机、超声仪、单螺杆或双螺杆挤出机、流化器,例如微流化器或宏流化器或流化器型均质器。取决于MFC制造方法,产物还可含有细粒(fines)、或纳米结晶纤维素或例如存在于木纤维或造纸工艺中的其它化学品。该产物还可含有各种量的没有被有效原纤化的微米尺寸的纤维颗粒。
MFC可从木纤维素纤维(来自硬木或软木纤维两者)来生产。其还可从微生物来源、农业纤维例如麦草浆、竹、甘蔗渣、或其它非木纤维源制造。其优选从浆制造,其包括来自原生纤维的浆,例如机械、化学和/或热机械浆。其还可从废纸或再循环的纸,即消费前和消费后的废料制造。
MFC可为天然的(即化学上未改性),或其可被化学改性。磷酸化的MFC典型地通过如下获得:使浸泡在NH4H2PO4的溶液中的纤维素纤维、水和脲反应,并且随后使纤维原纤化。一个特别的方法涉及提供纤维素浆纤维在水中的悬浮体,和用磷酸化试剂将在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、三氯氧磷、磷酸氢二铵和磷酸二氢钠。
该膜还可包括其它纤维素组分。
亲水性的膜成形聚合物
膜成形组合物包含亲水性的膜成形聚合物。该聚合物有助于将膜的MFC纤维结合在一起。膜成形组合物典型地包含0.1–50wt%、优选0.1-25wt%、更优选0.1-15wt%的所述膜成形聚合物,基于膜成形组合物的总固含量计。术语“亲水性”意指–当呈固体形式时–聚合物具有小于90度、优选小于70度的与水的接触角。
适宜地,所述膜成形聚合物选自:聚乙烯醇(PVA)、纤维素衍生物、聚丙烯酰胺、聚乙烯亚胺、丙烯酸类聚合物和聚乙二醇(PEG)。优选的膜成形聚合物为聚乙二醇(PEG)和聚乙烯醇(PVA)。
潜在地,还使用这些膜成形聚合物的部分或完全水解的衍生物。水解程度可为85-99%。
膜成形聚合物–特别是PVA–也可用各种官能团(例如硅烷醇或羧酸)衍生化。
用作膜成形聚合物的纤维素衍生物包括甲基纤维素、羟丙基纤维素、羟乙基纤维素、乙基羟乙基纤维素、羧甲基纤维素钠(NaCMC)或羧甲基纤维素(CMC)。纤维素衍生物还可包括淀粉或半纤维素、或其衍生物。
膜成形组合物可包含一种亲水性的膜成形聚合物或两种或更多种亲水性的膜成形聚合物。在一个实施方式中,各亲水性的膜成形聚合物可选自:聚乙烯醇(PVA)、纤维素衍生物、聚丙烯酰胺、聚乙烯亚胺、丙烯酸类聚合物和聚乙二醇(PEG)、以及其部分或完全水解的衍生物。
膜成形
以上描述的膜成形组合物流延在所述流延基材的经处理的表面上。流延可以以下速度进行:10至500m/min、优选20至300m/min。膜成形组合物可具有10至90℃、优选20至70℃、更优选20至60℃的温度。
膜成形组合物在流延基材上干燥以形成包含微原纤化纤维素(MFC)的纤维素膜。在干燥步骤中,进行干燥和任选的脱水。干燥可通过蒸发的方式进行,其中干燥方法可为穿透干燥、接触干燥、红外干燥、蒸气干燥、这些的组合或本领域技术人员已知的任意其它方法。干燥期间,膜成形组合物的温度可小于90℃、优选小于80℃。还可包括分开的脱水步骤,或刚好在流延之后或在将膜流延和干燥至一定干燥度之后。脱水可通过挤压脱水、毛细脱水、过滤或重力脱水的方式进行。例如,脱水步骤可后接蒸发干燥。干燥步骤和任选的脱水步骤的目的是达到75-99%、更优选80-97%的纤维素膜的最终干燥度。
然后,将形成的纤维素膜从流延基材分离。
本发明的方法可包括对纤维素膜进行的额外转化步骤,例如印刷、涂覆、层压等。一个额外步骤可为清洗纤维素膜以从纤维素膜去除过量的含水乳液。保留在MFC膜上的植物油的任意量可为非常低的,但可通过UV或UV-Vis光谱法检测到。因为其特性UV光谱,植物油可用作示踪化学品和/或化学指纹图谱。
其它组分
本方法中使用的膜成形组合物和所得纤维素膜可包含一种或多种额外组分。
在一方面,膜成形组合物包含0.1–30wt%、优选0.1-25wt%、更优选0.1-15wt%的填料,优选矿物填料例如粘土,基于膜成形组合物的总固含量计。典型的填料可为纳米粘土、膨润土、二氧化硅或硅酸盐、碳酸钙、滑石等。优选地,填料的至少一部分为片状填料。优选地,填料的一个维度应具有1nm至10μm的平均厚度或长度。如果例如用光散射技术测定填料的粒度分布,则优选的粒度应为大于90%低于2μm。其它填料可选自层状硅酸盐、金属氧化物、碳纳米管和金属纳米颗粒。
进一步地,膜成形组合物可进一步包含一种或多种稳定剂或增塑剂。在一个特别的方面,增塑剂为C1-C24多元醇、优选C1-C12多元醇、更优选C1-C6多元醇例如山梨醇。膜成形组合物可包含1-40wt%、优选3-20%的此类增塑剂,基于膜成形组合物的总固含量计。在一个方面,膜成形组合物不包含植物油。
膜成形组合物还可含有增强剂,例如纤维素衍生物或天然淀粉或改性淀粉,例如,阳离子型淀粉、非离子型淀粉、阴离子型淀粉或两性淀粉。在进一步的实施方式中,膜成形组合物还可含有截留和排液化学品。在仍进一步的实施方式中,膜成形组合物还可含有其它典型的加工或性能化学品,例如染料或荧光增白剂、消泡剂、湿强度树脂、杀生物剂、疏水剂、阻隔化学品、增塑剂、保湿剂等。
在一个实施方式中,一种或多种植物油的含水乳液可提供在纤维素膜和流延基材之间的0.5和5N/m之间的粘附性。
一般地,本发明还提供了一种或多种植物油的含水乳液促进包含MFC和亲水性的膜成形聚合物的纤维素膜从流延基材的表面的脱离的用途。
还提供了包含微原纤化纤维素(MFC)和亲水性的膜成形聚合物的纤维素膜,所述纤维素膜界定了表面,其中至少一种植物油存在于所述表面上。本文提供的纤维素膜在干燥时典型地具有10-60gsm的定量。以上对于本发明的方法提供的所有细节也尽可能地适用于纤维素膜自身。
优选地,在将本文定义的纤维素膜从流延基材分离的点处,本文定义的纤维素膜具有75-99%的固含量,最优选80-97%。
例如,纤维素膜可用作食物、电子产品或化妆品的包装材料。
该膜还可包含聚合物,例如水溶性聚合物和天然胶。水溶性聚合物可例如为聚乙烯醇,而天然胶可为例如瓜尔胶、纤维素衍生物、半纤维素和其它多糖。
实施例
实施例1(对比)
将包含微原纤化纤维素、聚乙烯醇和膨润土的膜流延成形在移动的钢带上以获得740μm的湿膜厚度,然后脱水和干燥。钢带具有PTFE涂层,Ra粗糙度0.9μm并且表面能40-42mN/m。
用于制造膜的悬浮体的固含量为4.24wt-%,含有95.76wt-%的水,3.69wt-%的微原纤化纤维素,0.37wt-%的聚乙烯醇和0.18wt-%的膨润土。
将膜干燥至高于95wt-%的最终固含量,并且尝试将膜从钢带分离并且将其带到卷取机作为自立型膜以制造连续的膜卷。
膜和钢带之间的粘附性如此之高以致于无法将膜从钢带分离并且必须将机器停止。
实施例2
将如实施例1中提供的MFC膜配方流延成形,但现在不同之处是用乳液处理带以控制对带的粘附性。
通过使用卵磷脂作为乳化剂制备菜籽油的含水乳液。首先在厨房共混器中将6g的大豆卵磷脂分散在100g的菜籽油中,随后添加1000g的水并且混合乳液直到其看起来是均匀的。然后将乳液用水稀释以达到2wt-%的菜籽油最终浓度。
使用与实施例1中相同的流延成形条件和钢带,但在此用雾化喷嘴将乳液以82g/min的速率在将MFC悬浮体进料至钢带之前喷洒在移动钢带的顶部表面上。该带以4.8m2/min的速度移动。用连续刮抹带表面的橡胶刮刀从带表面收取35g/min的乳液,以移除过量的水和乳液。从流延和喷洒区域周围的表面收取17g/min。因此,30g/min为保留在钢带表面上的乳液的量,对应于6.25g/m2。考虑到2wt-%的植物油浓度,钢带上的菜籽油量因此为125mg/m2。
在此情况中,干燥的膜可容易地从钢带基材分离并且自立型的膜被卷绕以制造连续的膜卷。分别地,125mg/m2有效剂量的乳液形式的菜籽油是有效的,而一些残留乳液留在钢带和干燥的膜的表面上。
实施例3
如实施例2中那样制备MFC组合物,但将乳液中的菜籽油浓度降低至0.2wt-%。
还有,12.5g/m2剂量提供了基本上干燥的膜从钢带表面的成功脱离,并且可卷绕连续的自立型的膜。用较低剂量的菜籽油乳液,膜和钢带表面表现出较少的来自乳液的残留。
实施例4(对比)
还用包含微原纤化纤维素,聚乙烯醇,膨润土和聚乙二醇的膜重复实验。将湿膜流延在移动的钢带上以获得690μm的湿膜厚度,随后脱水和干燥。使用如实施例1中那样的钢带。悬浮体含有95.66wt-%的水、3.62wt-%的MFC、0.36wt-%的聚乙烯醇、0.18wt-%的膨润土和0.18wt-%的聚乙二醇,共有4.34wt-%的总固含量。
在未在将膜流延之前喷洒施加菜籽油乳液的情况下,粘附性还是过高以致于无法在干燥后从钢带移除膜。
实施例5
使用与实施例4中相同的膜组成、相同的流延成形条件和相同的钢带,但现在用菜籽油乳液处理带。将菜籽油乳液以对应于125mg/m2的有效菜籽油量的剂量喷洒。带的处理的正面效果是明显的,可在没有问题的情况下将MFC膜剥离。
实施例6
使用与实施例4中相同的膜组成、相同的流延成形条件和相同的钢带,但现在用菜籽油乳液处理带。将菜籽油乳液以对应于12.5mg/m2的有效菜籽油量的剂量喷洒。带的处理的正面效果是明显的,可在没有问题的情况下将MFC膜剥离。带的处理的正面效果是明显的,可在没有问题的情况下将MFC膜剥离。
表1
通过以下从试验评估粘附性,追踪在干燥段之后在转移至卷绕之前从钢带脱离的膜或幅材。幅材粘附性还可通过对幅材脱离行为在线成像或通过例如光谱学方式来监控,以分析金属带上的残留。卷绕通过追踪卷材的品质来评估,例如张力、卷材尺寸等。不均匀或过高的幅材粘附性可导致幅材张力和后续卷材品质的问题。过高的幅材粘附性还会导致幅材破裂或类似的缺陷。
尽管已经参照多个实施方式描述了本发明,但是这些不应被认为是对本发明的限制。本领域技术人员可根据需要通过组合各个方面和实施方式来提供落入权利要求范围内的其它实施方式。
Claims (18)
1.制造包含微原纤化纤维素(MFC)的纤维素膜的方法,所述方法包括以下步骤:
a.提供具有至少一个表面的流延基材;
b.将一种或多种植物油的含水乳液施加至所述流延基材的所述表面;
c.将膜成形组合物在所述流延基材的经处理的表面上流延,所述膜成形组合物包含MFC和亲水性的膜成形聚合物;
d.将膜成形组合物在流延基材上干燥以形成包含微原纤化纤维素(MFC)的纤维素膜;和
e.将形成的纤维素膜从流延基材分离。
2.根据权利要求1的方法,其中所述膜成形组合物为含水组合物,其包含10–99wt%MFC、优选50-99wt%MFC、更优选70-95wt%MFC,基于膜成形组合物的总固含量计。
3.根据前述权利要求任一项的方法,其中所述膜成形组合物包含0.1–50wt%、优选0.1-25wt%、更优选0.1-15wt%的所述膜成形聚合物,基于膜成形组合物的总固含量计。
4.根据前述权利要求任一项的方法,其中所述膜成形聚合物选自:聚乙烯醇(PVA)、纤维素衍生物、聚丙烯酰胺、聚乙烯亚胺、丙烯酸类聚合物和聚乙二醇(PEG)、以及其部分或完全水解的衍生物;优选地选自:聚乙二醇(PEG)和聚乙烯醇(PVA)以及其部分或完全水解的衍生物。
5.根据前述权利要求任一项的方法,其中所述膜成形组合物包含0.1–30wt%、优选0.1-25wt%、更优选0.1-15wt%的填料,优选矿物填料例如粘土,基于膜成形组合物的总固含量计。
6.根据前述权利要求任一项的方法,其中所述纤维素膜的干定量为10-60gsm。
7.根据前述权利要求任一项的方法,其中一种或多种植物油以以下水平施加至所述流延基材的表面:0.1–500mg/m2、优选0.5–150mg/m2。
8.根据前述权利要求任一项的方法,其中所述含水乳液包含0.01-20wt%、优选0.01-10wt%、更优选0.1-5wt%的所述一种或多种植物油。
9.根据前述权利要求任一项的方法,其中所述一种或多种植物油选自:辣木油、棕榈油、棕榈仁油、卡诺拉油、椰子油、豆油、向日葵油、菜籽油、花生油、棉籽油、橄榄油、亚麻籽油、玉米油、红花油、核桃油、芝麻油、杏仁油、蓖麻油、菜油、假亚麻油、汉麻油、芥子油、萝卜油、兰提油、米糠油、桐油、海蓬子油、麻风树油或基于藻类的油。
10.根据前述权利要求任一项的方法,其中膜成形组合物还包含一种或多种稳定剂和/或增塑剂。
11.根据权利要求10的方法,其中增塑剂为C1-C24多元醇、优选C1-C12多元醇、更优选C1-C6多元醇例如山梨醇。
12.根据权利要求5的方法,其中填料选自:层状硅酸盐、金属氧化物、碳纳米管和金属纳米颗粒。
13.根据前述权利要求任一项的方法,其中含水乳液包含一种或多种乳化剂。
14.根据权利要求13的方法,其中乳化剂选自:非离子型、阳离子型或阴离子型乳化剂。
15.根据前述权利要求任一项的方法,其中在将纤维素膜从流延基材分离的点处,纤维素膜具有75-99%的固含量,优选80-97%。
16.一种或多种植物油的含水乳液促进包含MFC和亲水性的膜成形聚合物的纤维素膜从流延基材的表面的脱离的用途。
17.包含微原纤化纤维素(MFC)和亲水性的膜成形聚合物的纤维素膜,所述纤维素膜界定了表面,其中至少一种植物油存在于所述表面上。
18.如权利要求17中所定义的纤维素膜,其具有75-99%的固含量,优选80-97%。
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BR112022012378A2 (pt) | 2022-08-30 |
CA3165725A1 (en) | 2021-07-01 |
WO2021130668A1 (en) | 2021-07-01 |
CN114867772B (zh) | 2024-02-13 |
EP4081578A1 (en) | 2022-11-02 |
SE1951556A1 (en) | 2021-06-24 |
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US20230002572A1 (en) | 2023-01-05 |
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