CN115516168A - 适合于金属化的涂覆的纸基材 - Google Patents
适合于金属化的涂覆的纸基材 Download PDFInfo
- Publication number
- CN115516168A CN115516168A CN202180032675.2A CN202180032675A CN115516168A CN 115516168 A CN115516168 A CN 115516168A CN 202180032675 A CN202180032675 A CN 202180032675A CN 115516168 A CN115516168 A CN 115516168A
- Authority
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- China
- Prior art keywords
- paper substrate
- cellulose
- coated paper
- coating
- cellulose ether
- Prior art date
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- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical group CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims 2
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Classifications
-
- 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
- C09D101/08—Cellulose derivatives
- C09D101/26—Cellulose ethers
- C09D101/28—Alkyl ethers
-
- D—TEXTILES; PAPER
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- 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
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/18—Highly hydrated, swollen or fibrillatable fibres
-
- 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
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/34—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising cellulose or derivatives thereof
-
- 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
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/52—Cellulose; Derivatives thereof
-
- 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
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
- D21H23/52—Addition to the formed paper by contacting paper with a device carrying the material
- D21H23/54—Rubbing devices, e.g. brush, pad, felt
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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
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/10—Packing paper
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
-
- 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
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
-
- 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
- D21H19/00—Coated paper; Coating material
- D21H19/02—Metal coatings
- D21H19/06—Metal coatings applied as liquid or powder
-
- 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
- D21H19/00—Coated paper; Coating material
- D21H19/02—Metal coatings
- D21H19/08—Metal coatings applied as vapour, e.g. in vacuum
-
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Abstract
本发明涉及尤其适合于金属化和提供阻隔性质且使用真空沉积技术施加的其它纳米涂层的涂覆的纸基材。本发明还涉及涂覆的纸基材的制备方法。本发明还涉及包括涂覆的纸基材的包装材料。
Description
技术领域
本发明涉及尤其适合于金属化和提供阻隔性质且使用真空沉积技术施加的其它纳米涂层的涂覆的纸基材。本发明还涉及涂覆的纸基材的制备方法。本发明还涉及包括涂覆的纸基材的包装材料。
背景技术
用于敏感物体的包装需要具有足够的阻隔性质。尤其是一些干的或液体食物产品需要高的阻隔以保护被包装物并且例如延长货架寿命。典型地,铝或成膜聚合物例如胶乳或热塑性聚合物用于这些意图并且通常提供足够的在油或油脂和/或香味或气体例如氧气的渗透或扩散方面的性质。铝或成膜聚合物也提供提升的水蒸气阻隔,这对于在高相对湿度条件下的阻隔和包装功能性或减少被包装的液体产品的蒸发是重要的。成膜聚合物还保护纸板免受液体包装产品的润湿。
然而,使用铝和特别是包含铝箔的层压体的一个问题是,其造成环境挑战,在再循环过程方面可成问题,并且取决于用量可导致不可堆肥的包装材料。因此,期望使用尽可能少量的铝。然而,同时必须维持包装材料的阻隔性质。
本领域知晓的是,提供可为有机或无机的例如陶瓷或金属纳米涂层的纳米涂层。纳米涂层非常薄,例如厚度为约0.1nm至约100nm。例如,金属化表面使用非常少量的金属或金属氧化物例如铝或Al2O3、AlOx、MgO或ZnO。例如,原子层沉积(ALD)、动态复合沉积(DCD)、化学气相沉积(CVD)、例如等离子体CVD、物理气相沉积(PVD)和金属等离子体-沉积为适合在表面上提供少量金属的技术。然而,如下仍是必要的:包装材料当提供有纳米涂层(例如金属化的)时能够维持阻隔性质并且是足够抗裂化的。
成膜聚合物例如胶乳和热塑性基于化石的聚合物的一个问题是,获得的包装材料典型地不被认为是单材料并且再循环问题可出现。很多成膜聚合物的另外问题在于,成膜聚合物通常以含水溶液或分散体的形式提供。溶液或分散体的水含量可破坏纸基材。亲水纤维素材料典型地提供对氧气的阻隔性质但对水和水蒸气敏感。
因此,调整基材使得可施加非常少量的纳米涂层。
发明内容
已经意外地发现,前述问题的一些或全部可通过提供涂覆的纸基材解决,所述纸基材具有在15g/m2至100g/m2的范围内的克重,所述涂层包括纤维素醚,其中涂覆的表面具有在0.1-8.0μm的范围内的以1.0MPa测量的PPS光滑度。
更具体地,已经意外地发现,纤维素醚涂层提供光滑表面、特别是纳米级水平上的光滑表面,其便于使用非常少量的金属例如铝提供纳米涂层例如金属化表面。例如,原子层沉积(ALD)、动态复合沉积(DCD)、化学气相沉积(CVD)、物理气相沉积(PVD)和金属等离子体-沉积为可用于仅使用非常少量的金属提供阻隔性质的技术。
纸基材的纳米级粗糙度可使用本领域中知晓的方法测定。例如,粗糙度可通过原子力显微术或通过使用扫描电子显微术测定。
根据本发明的纸基材的纳米级表面粗糙度是低的,即表面在纳米尺度上非常光滑。粗糙度通常被描述为密集间隔的不规则性。纳米级粗糙度可通过原子力显微术测量。例如,可使用原子力显微术观察纤维素醚涂覆的基材(即在已经施加任何纳米涂层之前)的区域(area,面积)、优选地5um x 5um和100um x 100um之间的区域。可测定表面结构,即峰和谷,并且可计算均方根(RMS)粗糙度或峰-对-谷高度参数,量化纳米级表面粗糙度(Peltonen J.等人Langmuir,2004,20,9428-9431)。对于根据本发明的纤维素醚涂覆的基材,因此测定的RMS通常在100nm以下、优选地在80nm以下。
PPS(Parker Print Surf)光滑度可根据ISO 8791-4测定。
根据本发明的纸基材可包括多个层。例如,纸基材可包括具有少量微纤化纤维素的一个层和具有大量微纤化纤维素的一个层。有利地,纸基材的一个层为包括大量微纤化纤维素的膜。
具体实施方式
根据本发明使用的微纤化纤维素(MFC)可使用本领域中知晓的方法而制备。
具有在15g/m2至100g/m2的范围内的克重的纸基材可使用本领域中知晓的方法制备。优选地,纸基材的克重在15g/m2至50g/m2的范围内、更优选地在20g/m2至45g/m2的范围内。纸基材可为例如玻璃纸、防油脂纸或纳米纸,只要其具有在限定范围内的克重。纸基材可例如由浆(pulp,纸浆),例如由软木和/或硬木制备的牛皮纸浆来制备。可精制用于制造纸基材的浆,并且纸基材可由精制至不同程度的浆混合物制备。例如,纸基材可由混合有40-60wt-%高度精制的浆(例如具有70°的SR)和10-40wt-%微纤化纤维素(MFC)的10-20wt-%低精制的浆(例如具有在15-25°的范围内的肖伯尔瑞格勒(Schopper Riegler)度SR)制备。
优选地,根据本发明的纸基材包括总量小于5wt-%的塑料材料或其它基于化石的材料。
优选地,纸基材包括至少60重量%的微纤化纤维素、更优选地至少70重量%的微纤化纤维素。
在根据本发明的纸基材中使用的MFC可为原生的或改性的(例如比如PCC涂覆的MFC)并且可为原生的和改性的MFC的混合物以及原生MFC和不同类型的改性MFC的混合物。MFC可由浆例如溶解浆制成。
纸基材在涂覆之前优选具有阻隔性质,使得膜的格利希尔(Gurley Hill)孔隙率值高于4000s/100ml、优选地高于6000s/100ml和最优选地高于10 000s/100ml。格利希尔值可使用本领域中知晓的方法(ISO 5636-5)测定。
纸基材可任选地在用纤维素醚的涂覆之前例如使用软辊隙带式压延机或超级压延机压延。
使用纤维素醚的涂覆通过本领域中知晓的涂覆方法实施。
纤维素醚的实例包括二乙基氨基乙基纤维素、乙基纤维素、乙基甲基纤维素、羟基乙基纤维素、羟基乙基甲基纤维素、羟丙基纤维素和甲基纤维素。用于涂覆的纤维素醚为优选地甲基纤维素或乙基纤维素。优选地,纤维素醚具有在0.5-2.5、优选地低于2.1的范围内的取代度(DS)。纤维素醚可例如使用高压流化器或均化机在一个或多个高剪切步骤中预处理。
纤维素醚可为原纤化形式,例如甲基化纳米纤维素。这样的纤维素醚可例如如在US20180319957A1中所公开的来制备。
在涂覆步骤中施加到纸基材的纤维素醚的量优选地在0.1g/m2至8g/m2、优选地1g/m2至6g/m2的范围内。纤维素醚涂层可在纸基材的一面或两面上以一层或多层提供。
纤维素醚优选地以溶液、分散体、乳液或泡沫的形式施加。纤维素醚可以颗粒形式施加,即纤维素醚可以包括以颗粒形式分散的纤维素醚的分散体形式提供。这样的分散体还可包括溶解的纤维素醚。
优选地,纤维素醚以在非水溶剂、优选地有机溶剂中的溶液、分散体、乳液或泡沫的形式提供。优选地,所述悬浮体、溶液、乳液或泡沫中使用的溶剂的至少80wt-%、更优选地至少90wt-%、甚至更优选地至少95wt-%为非水的。优选地,使用的溶剂具有小于50的介电常数。适合的溶剂包括乙醇、异丙醇、甲乙酮及其混合物。
优选地,用于涂覆的纤维素醚溶液、分散体、乳液或泡沫的使用布氏(Brookfield)粘度计以100rpm转速和使用RV Series Viscometer和主轴数3测定的粘度小于2000mPas、更优选地小于1000mPas、最优选地小于800mPas。
包含纤维素醚的溶液、分散体、乳液或泡沫可包括一种或多于一种醚。纤维素醚可为原纤化或非原纤化的。溶液、分散体或乳液还可包括添加剂例如填料和/或交联剂例如柠檬酸。溶液、分散体、乳液或泡沫中纤维素醚的浓度优选地在1wt-%至99wt-%的范围内、更优选地在5wt-%至95wt-%的范围内、例如5wt-%至50wt-%或10wt-%至50wt-%或20wt-%至50wt-%,基于纤维素醚的重量和溶液、分散体、乳液或泡沫的总重量。
当施加纤维素醚涂层时,纤维素醚涂层施加到其上的纸的水分含量优选地小于50wt-%、更优选地小于20wt-%、最优选地小于10wt-%、甚至更优选地小于5wt-%。
在干燥纤维素醚涂层后,涂覆的纸基材的水分含量小于5wt-%、优选地小于3wt-%、更优选地小于2wt-%。在干燥纤维素醚涂层后,在纤维素醚的悬浮体、分散体、乳液或泡沫中使用的溶剂的残余含量小于5wt-%(基于涂覆基材的总重量)、优选地小于3wt-%、更优选地小于2wt-%、最优选地小于1wt-%。
在基材和涂覆介质之间的接触角优选地在65度以下、更优选地在45度以下和甚至更优选地在30度以下,以在涂覆步骤中确保足够的润湿和成膜。
在施加纤维素醚涂层后,将涂层使用本领域中知晓的方法干燥。优选地,涂层用棒、凹版印刷、反向凹版印刷、光滑辊或刮板涂覆施加。涂层还可通过幕涂、泡沫涂覆、喷涂、刮板涂覆或例如通过印刷施加。
涂覆的纸基材可任选地在用纤维素醚涂覆后压延,例如使用软辊隙带式压延机或超级压延机。
任选地,可重复纤维素醚涂覆步骤以提供若干涂层。用于任选的后续涂覆步骤的涂覆溶液、分散体或乳液可与第一步骤的相同或不同。例如,用于第二或后续涂层的溶液、分散体或乳液的粘度可低于用于第一涂层的溶液、分散体或乳液的粘度。
涂覆的纸基材具有在0.1-8.0μm的范围内的以1.0MPa测量的PPS光滑度。优选地,PPS光滑度在0.2至5.0μm的范围内、例如在0.4-2.0μm的范围内。更优选地,PPS光滑度在0.5-5.0μm的范围内、例如在1.0-4.0μm或1.0-3.0μm的范围内。
根据本发明的纸基材优选具有小于100μm例如小于70μm、小于45μm、小于40μm或小于35μm的在涂覆前的厚度。厚度根据ISO 3034测定。
根据本发明的涂覆的纸基材优选具有小于100μm、例如小于70μm、小于45μm、小于40μm或小于35μm的厚度。厚度根据ISO 3034测定。
纸基材在用纤维素醚涂覆后优选具有这样的阻隔性质:使得克重为10-50gsm的纸基材在50% RH、23℃下测量的OTR(氧气透过率)值(在标准条件下测量)优选地<200cc/(m2*天)、优选地<150、更优选地<120和最优选地<100。涂覆的纸基材典型地具有非常高的油和油脂阻隔性质。典型地,根据本发明的涂覆的纸基材的在60℃进行的使用ASTM F119-8的修改方案(使用平坦试样,2个平行样品)测定的耐鸡脂肪性超过48小时。
涂覆的纸基材可以其本身(独立地)提供或为包装材料的一部分。涂覆的纸基材可例如为以多层或多片层(ply)结构的形式的包装材料的部分,其中一个层或片层可为纸板。例如,根据本发明的涂覆的纸基材可提供在纸板层上。
根据本发明的涂覆的纸基材可例如在涂覆有纤维素醚的一面或两面上提供有纳米涂层。纳米涂覆优选为原子层沉积(ALD)、动态复合沉积(DCD)、化学气相沉积(CVD)、物理气相沉积(PVD)和金属等离子体-沉积。优选地,纳米涂层直接提供在涂覆有纤维素醚的一面或两面上。可替代地,可在提供纳米涂层之前在涂覆有纤维素醚的一面或两面上提供预涂层。优选地,提供金属作为纳米涂层。更优选地,提供铝作为纳米涂层。在提供纳米涂层后,包装材料的根据标准ISO 15106-2/ASTM F1249以50%相对湿度和23℃测定的水蒸气透过率小于5、更优选地小于3。
包装材料的其它组分可包括材料例如热塑性聚合物例如聚丙烯或聚乙烯,优选地生物衍生的或衍生自可再生资源例如PLA、PHA、PHB、PBS、醋酸纤维素和改性淀粉。另外的实例为蜡和热熔胶。额外的实例包括乙烯类聚合物(基于PVC和PVDC的)、基于丙烯酸酯和苯乙烯丙烯酸酯的聚合物、丙烯酸酯/聚烯烃共聚物、苯乙烯共聚物、聚酯、聚丙烯分散体、乙烯共聚物(EAA和EMAA)、乙烯三聚体(EVA)或苯乙烯丙烯酸类胶乳或苯乙烯丁二烯胶乳。这样的材料可例如通过分散涂覆、挤出涂覆或乳液涂覆或通过印刷作为涂层施加。
根据本发明的涂覆的纸基材和/或包装材料可为生物可降解的和/或可堆肥的。在本上下文中,可堆肥性依据ISO 18606定义,即整个材料中以小于1%浓度存在的成分不需要展现生物可降解性。然而,这样的成分的总和不应超过5%。生物可降解性定义如下:最终的需氧生物可降解性应当对于整个材料或对于在该材料中以多于1%(干质量)的浓度存在的各有机成分而测定。以在1-10%之间的水平存在的成分应当单独测试。
根据本发明的涂覆的纸和/或包装材料可例如用作盖子、液体包装产品或袋。
微纤化纤维素(MFC)在专利申请的上下文中应意指至少一个维度小于100nm的纳米级纤维素颗粒纤维或原纤维。MFC包括部分或全部原纤化的纤维素或木质纤维素纤维。释放的原纤维具有小于100nm的直径,而实际的原纤维直径或粒度分布和/或长宽比(长度/宽度)取决于来源和制造方法。
最小的原纤维称为基本原纤维并且具有大约2-4nm的直径(参见例如Chinga-Carrasco,G.,Cellulose fibres,nanofibrils and microfibrils,:The morphologicalsequence of MFC components from a plant physiology and fibre technology pointof view,Nanoscale research letters 2011,6:417),而如下是常见:基本原纤维的聚集形式,也定义为微原纤维(Fengel,D.,Ultrastructural behavior of cell wallpolysaccharides,Tappi J.,March 1970,Vol 53,No.3.),为例如通过使用扩展精制工艺或压降崩解工艺生产MFC时获得的主要产物。取决于来源和制造方法,原纤维的长度可从大约1微米至多于10微米变化。粗MFC等级可包含相当大分数的原纤化纤维,也就是从管胞(纤维素纤维)突出的原纤维,以及一定量的从管胞(纤维素纤维)释放的原纤维。
MFC存在不同的首字母缩略词例如纤维素微原纤维、原纤化的纤维素、纳米原纤化的纤维素、原纤维聚集体、纳米级纤维素原纤维、纤维素纳米纤维、纤维素纳米原纤维、纤维素微纤维、纤维素原纤维、微原纤状纤维素、微原纤维聚集体和纤维素微原纤维聚集体。MFC还可以各种物理或物理-化学性质例如大的表面积或其当分散于水中时以低固体(1-5wt%)形成凝胶状材料的能力为特征。纤维素纤维优选地被原纤化至这样的程度:形成的MFC当对冷冻干燥的材料用BET方法测定时的最终比表面积为约1-约300m2/g,例如1-200m2/g或更优选地50-200m2/g。
存在用于生产MFC的各种方法,例如单遍或多遍精制、在预水解后精制或者原纤维的高剪切崩解或释放。为了使MFC制造既节能又可持续,通常需要一个或若干个预处理步骤。因此,可酶促地或化学地预处理所供应的浆的纤维素纤维,以例如减少半纤维素或木质素的量。可在原纤化之前将纤维素纤维进行化学改性,其中纤维素分子包含除原始纤维素中发现的官能团之外的(或更多的)官能团。这样的基团尤其包括羧甲基(CM)、醛和/或羧基基团(通过N-氧基介导的氧化例如"TEMPO"获得的纤维素)或季铵(阳离子纤维素)。在上述方法之一中改性或氧化之后,更容易将纤维崩解为MFC或纳米原纤状尺寸原纤维。
纳米原纤状纤维素可包含一些半纤维素;量取决于植物来源。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崩解通过适合的设备例如精制机、研磨机、均化机、胶化器(colloider)、摩擦研磨机、超声发生器、流化器例如微流化器、大型流化器或流化器型均化机实施。取决于MFC制造方法,产物还可包含细料或纳米晶体纤维素或例如在木纤维中或在造纸过程中存在的其它化学品。产物还可包含不同量的尚未有效原纤化的微米尺寸纤维颗粒。
MFC由来自硬木或软木纤维两者的木纤维素纤维制成。其也可由微生物来源、农业纤维例如麦秆浆、竹子、甘蔗渣或其它非木纤维来源制成。其优选地由包括来自原生纤维的浆(例如机械、化学和/或热机械浆)的浆制成。其也可由损纸(broke,废纸)或再生纸制成。
根据另外实施方式,悬浮体可包括不同类型的纤维混合物,例如微纤化纤维素和一定量的其它类型的纤维例如牛皮纸(kraft)纤维、细料、增强纤维、合成纤维、溶解浆、TMP或CTMP、PGW等。
纸基材还可包括其它工艺或功能添加剂,例如填料、颜料、湿强度化学品、干强度化学品、助留化学品、交联剂、软化剂或增塑剂、粘着底漆、润湿剂、杀生物剂、光学染料、荧光增白剂、消泡化学品、疏水化化学品例如AKD、ASA、蜡、树脂等。添加剂也可使用施胶压机添加。
实施例
对比例1
包含精制纤维和大量MFC的薄基材被制备成使得配料(不含化学品)具有90的SR值。由其使用湿法铺设(在织物丝网例如长网造纸机(fourdrinier)上脱水)方法制备基材,以37g/m2的克重为目的。格利希尔值为大约11 400(s/100ml)。
对比例2
用以200m/min运行的11辊隙Multical超级压延机将34g/m2基于对比例1的基础基材超级压延。压力为400kN/m并且将幅材幅材用蒸汽加湿。压延样品的Gurley-Hill值为16900s/100ml。
实施例1
使用棒涂机(台式涂覆机)将以上基础基材(对比例1)用浓度为大约9.5wt%的甲基化纳米纤维素(纤维素醚)涂覆。涂层重量为4.0g(1-面涂覆)并且获得的格利希尔值为42300,其为对于所用设备而言的最大值,由此确认非常致密的基材。
实施例2
将来自对比例2的基材用甲基化纳米纤维素以2.9g/m2涂覆重量处理。处理后的格利希尔值为42 300(最大值),确认在低涂覆重量后的致密基材。使用的纤维素醚为根据US20180319957A1获得的甲基化纤维素。
实施例3(溶解在溶剂中的乙基化纳米纤维素)
将乙基化纳米纤维素溶解或分散于含有92.1wt-%乙醇、2.0wt-%甲乙酮和5.9wt-%水的乙醇中。
然后,用刷子在具有5500s/100ml的格利希尔值的如上所述的MFC基材表面上施加乙基化纳米纤维素(MEC 1000;Innotech)溶液。在施加涂层后,容许膜在环境空气中干燥。测试一个或两个层的添加。观察到在膜的顶部上施加仅一层1或5wt-%乙基化纳米纤维素溶液将结构密封,使得格利希尔值从5500s/100ml增至42300s/100ml(用L&W透气计可测量的最大值)。
实施例4
当进行除使用基本上不含水(<0.5%)的溶剂外与实施例3相同的实验时,不仅看到在格利希尔上相同的效果,而且WVTR(水蒸气透过率,根据标准ISO 15106-2/ASTM F1249以50%相对湿度和23℃测定)进一步降至约190g/m2/天。还有,看到显著更少的收缩和起皱。
实施例5(对比)
制备包括高度精制的纤维素(70%)和漂白的牛皮纸浆的幅材。表面并不致密(格利希尔14 800s/100ml)并且PPS(1.0MPa)相对高,在7.9μm。
实施例6(对比)
使用实验室压延机将来自实施例5的样品在150℃温度和150kN/m线负荷下压延。粗糙度降低至2.8μm(PPS,1.0MPa)并且透气性增加(28 400s/100ml)。
实施例7(对比)
在此情况中,将实施例5的基础幅材用水涂覆并且然后干燥和如实施例6中所述的那样进行压延。
实施例8
在该实施例中,将甲基纳米纤维素(流化的)在实施例5中所述的基础幅材上施加。涂层重量为大约6g/m2。然后将样品干燥并且如实施例6中所述地压延。在该情况中,透气性值为42 300s/100ml,这是使用装置的最大值并且因此确认了致密的基材。PPS粗糙度为2.4μm(PPS 1.0MPa)。OTR值显著提高,确认了致密的基材。
*使用ASTM F119-8的修改方案测定的耐鸡脂肪性在60℃进行。
这确认,甲基纤维素或甲基纳米纤维素以及乙基纤维素或乙基纳米纤维素可充当提供用于例如真空沉积的良好且致密的基材的成膜剂。
鉴于以上本发明的详细描述,其它修改和改变对于本领域技术人员将变得明晰。然而,应当明确的是,可实施这样的其它修改和改变而不偏离本发明的精神和范围。
Claims (14)
1.涂覆的纸基材,所述纸基材具有在15g/m2至100g/m2的范围内的克重,具有包括纤维素醚的涂层,其中涂覆的表面具有在0.1-8.0μm的范围内的PPS光滑度。
2.根据权利要求1所述的涂覆的纸基材,其中涂覆的表面具有在0.4-8.0μm的范围内的PPS光滑度。
3.根据权利要求2所述的涂覆的纸基材,其中涂覆的表面具有在1.0-3.0μm的范围内的PPS光滑度。
4.根据权利要求1-3任一项所述的涂覆的纸基材,其中施加的涂层的量在1g/m2至8g/m2的范围内。
5.根据权利要求1-4任一项所述的涂覆的纸基材,其中涂层已经以悬浮体、溶液、乳液或泡沫的形式施加。
6.根据权利要求5所述的涂覆的纸基材,其中在所述悬浮体、溶液、乳液或泡沫中使用的溶剂的至少80wt-%为非水的。
7.根据权利要求1-6任一项所述的涂覆的纸基材,其中纤维素醚为甲基纤维素、乙基纤维素、甲基纳米纤维素或乙基纳米纤维素。
8.根据权利要求1-7任一项所述的涂覆的纸基材,其中涂覆的纸基材的厚度小于70μm。
9.包装材料,包括根据权利要求1-8任一项所述的涂覆的纸基材。
10.根据权利要求1-8任一项所述的涂覆的纸基材的制造方法,包括如下步骤
a)提供具有在15g/m2至100g/m2的范围内的克重的纸基材;
b)将步骤a)的纸基材在纸的至少一侧上用纤维素醚涂覆以获得使至少一个表面具有在0.1-8.0μm的范围内的PPS光滑度的涂覆的纸基材。
11.根据权利要求10所述的方法,其中施加的涂层的量在1g/m2至8g/m2的范围内。
12.根据权利要求10或11所述的方法,其中涂层以悬浮体、溶液、乳液或泡沫的形式施加。
13.根据权利要求12所述的方法,其中在所述悬浮体、溶液、乳液或泡沫中使用的溶剂的至少80wt-%为非水的。
14.根据权利要求10-13任一项所述的方法,其中纤维素醚为甲基纤维素、乙基纤维素、甲基纳米纤维素或乙基纳米纤维素。
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