CN103958625A - 涂覆组合物、涂覆基底的方法、经涂覆的基底、包装材料和液体包装 - Google Patents

涂覆组合物、涂覆基底的方法、经涂覆的基底、包装材料和液体包装 Download PDF

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CN103958625A
CN103958625A CN201280051907.XA CN201280051907A CN103958625A CN 103958625 A CN103958625 A CN 103958625A CN 201280051907 A CN201280051907 A CN 201280051907A CN 103958625 A CN103958625 A CN 103958625A
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application composition
substrate
heavy curtain
coating
carried out
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CN103958625B (zh
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J·拉尔森
A·卡尔森
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BILLERUDKORSNAES GAEVLE FROEVI AB
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BILLERUDKORSNAES GAEVLE FROEVI AB
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/30—Processes for applying liquids or other fluent materials performed by gravity only, i.e. flow coating
    • B05D1/305—Curtain coating
    • 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
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
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    • B65D25/00—Details of other kinds or types of rigid or semi-rigid containers
    • B65D25/14—Linings or internal coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D3/00—Rigid or semi-rigid containers having bodies or peripheral walls of curved or partially-curved cross-section made by winding or bending paper without folding along defined lines
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    • B65D85/72—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for for edible or potable liquids, semiliquids, or plastic or pasty materials
    • 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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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
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  • Chemical Kinetics & Catalysis (AREA)
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  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Health & Medical Sciences (AREA)
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Abstract

本发明涉及一种能够帘幕涂覆的气体阻隔性涂覆组合物，所述涂覆组合物包含聚合物和表面活性剂，其中，所述聚合物选自由聚乙烯醇和多糖或其混合物组成的组，其中，所述多糖能够溶解或分散或悬浮在水中，所述表面活性剂是水溶性非离子型乙氧基化醇。本发明还涉及一种利用所述涂覆组合物提供具有气体阻隔层的基底的方法和一种通过用所述涂覆组合物涂覆所述基底而获得的具有至少一个气体阻隔层(2)的经涂覆的基底(1)。此外，本发明还涉及一种包含涂覆有所述涂覆组合物的经涂覆的纸板的包装材料，和包含这种包装材料的液体包装。

Description

涂覆组合物、涂覆基底的方法、经涂覆的基底、包装材料和液体包装
技术领域
本发明涉及一种包含聚合物和表面活性剂的涂覆组合物，其中，所述聚合物选自由聚乙烯醇和多糖或其混合物组成的组。特别而言，本发明涉及一种适用于帘幕涂覆的气体阻隔性涂覆组合物。本发明还涉及利用所述涂覆组合物提供具有气体阻隔层的基底的方法、经涂覆的基底、包含经涂覆的纸板的包装材料和包含这种包装材料的液体包装。
背景技术
帘幕涂覆是将液体涂覆组合物的线流沉积在移动基底(例如纸网(paper web))的表面上的涂覆方法。所述涂覆组合物形成自由下落的液体片层，直到其碰撞在待涂覆的移动基底的表面上。
帘幕涂覆是非常适合于用液体阻隔层来涂覆纸网的技术，因为阻隔性物质必须形成覆盖整个表面(或尽可能接近整个表面)的膜。然而，帘幕涂覆法易受到某些缺陷的影响，例如不规则踵状物的形成、空气挟带和帘幕不稳定性，这些缺陷可能使经涂覆的表面展现出或大或小的无涂层区域。为了在涂层覆盖物中发现这些缺陷(这些缺陷因例如液体涂层中的气泡而可以非常小)，可以通过在经涂覆的表面上施加有色测试液来进行测试。任何缺陷都将呈现为有色区域或所谓的“针孔”。对于一些应用，特别重要的是，涂层不能包含任何缺陷或只能包含极少的缺陷，例如，在食品工业中或对于液体包装(即，包含液体的包装)而言。
之前已知，多糖和聚乙烯醇是阻隔气体的良好屏障。已知，在例如基于纸板基底的包装材料中，沉积在基底上的包含多糖和/或聚乙烯醇的涂层适合作为阻隔氧气、气味、香气等的屏障。
在帘幕涂覆中，要求适合的动态表面张力(由下落的帘幕中的Mach角测量获得)来使自由下落的涂覆液帘幕形成稳定的帘幕且不具有孔形式的缺陷。通常，对于牛顿流体，涂覆液的动态表面张力应当小于40mNm，以满足不形成孔的下落帘幕的标准。然而，作为非牛顿流体的多糖和聚乙烯醇却具有明显更高的表面张力，在流速低时会形成不稳定的帘幕。
为了降低聚乙烯醇的表面张力，已提出向聚乙烯醇中添加表面活性物质(即，表面活性剂)，例如，如EP2182113所述，使用Air Products的EnviroGem AE03类型的表面活性剂。然而，已发现即使在使用表面活性剂时改进了帘幕的稳定性，涂层的阻隔效果也会变差，差到使其不能用于制造液体包装的程度。作为其他实例，已提出了向聚乙烯醇中添加相对大量的乙醇或类似的醇，但是这对于造纸工业中的涂覆问题并不是令人满意的解决方案，因为这要求对所产生的挥发性有机化合物(VOC)进行操作和回收。
总之，为了使用帘幕涂覆获得基底上的阻隔层，例如纤维基底(例如纸板)上的聚乙烯醇或多糖阻隔层，有必要使用降低动态表面张力的添加物以获得稳定的过程，但这些添加物同时会对膜的形成产生负面效果，因此阻隔层会具有缺陷。
发明内容
本发明的一个目的是提供一种适用于帘幕涂覆的、特别是用于上文提到的应用领域的改进的涂覆组合物。
另一目的是获得一种会产生适用于食品工业的最终产品的涂层，所述涂层不含任何毒性或不健康物质，且能够安全使用。此外，当用于包装材料中时，所述涂层在用于食品或液体包装中时必须不能含有任何能够迁移至食品中的物质或发散出任何气味或香气的物质。
本发明实现了这些目的。
根据本发明的第一方面，定义了一种能够帘幕涂覆的气体阻隔性涂覆组合物，所述涂覆组合物包含聚合物和表面活性剂，其中，所述聚合物选自由聚乙烯醇和多糖或其混合物组成的组，其中，所述多糖能够溶解或分散或悬浮在水中，所述表面活性剂是水溶性非离子型乙氧基化醇。所述涂覆组合物使得可以获得稳定的帘幕，且在所涂覆的基底(例如纤维基底，例如纸板)的涂层中针孔数量少。所述涂层提供了对气体(例如氧气、香气和气味)的良好的阻隔品质。
优选的是，所述多糖可以包括淀粉、淀粉衍生物、MFC(微原纤纤维素(microfibrillar cellulose))和半纤维素。
根据本发明的一个实施方式，所述聚合物仅包含聚乙烯醇，或包含与淀粉和/或淀粉衍生物和/或MFC和/或半纤维素成混合物的聚乙烯醇。
根据另一个实施方式，所述聚合物仅包含淀粉或仅包含淀粉衍生物，或包含其混合物，或包含与MFC和/或半纤维素成混合物的淀粉或淀粉衍生物中任一种。
根据又一个实施方式，所述聚合物仅包含MFC或仅包含半纤维素，或包含其混合物。
根据本发明的另一个实施方式，表面活性剂可以是饱和的异C13醇。根据该实施方式的另一特征，表面活性剂具有式RO(CH2CH2O)xH，其中R=异C13H27，且x为8以上。
根据本发明的另一实施方式，表面活性剂可以是基于C10-吉布特醇(Guerbetalcohol)的聚乙二醇烷基醚，且乙氧基化度为7以上。
根据本发明的又一实施方式，表面活性剂可以是饱和的短链脂肪醇。根据该实施方式的另一特征，表面活性剂具有式RO(CH2CH2O)xH，其中R=饱和的短链醇，且x为5以上。
所述涂覆组合物可以包含非离子型乙氧基化醇表面活性剂，相对于完全干燥的涂覆组合物的总重量，所述表面活性剂的浓度可以是0.05重量%～2.0重量%、优选0.1重量%～1.0重量%、更优选0.2重量%～0.5重量%。
所述组合物的固相含量可以是4%～20%、优选7%～15%或6%～12%、或甚至8%～10%。余量为水。
此外，所述涂覆组合物可以包含扁平颗粒，例如，其可以包含纳米颗粒形式的蒙脱石粘土。这具有改进气体阻隔功能的优点。添加到聚乙烯醇中的粘土或其他适合的扁平或纳米形式的添加剂的量可以是组合物总干重的1干重%～20干重%、优选3%～15%、更优选5%～10%。
所述涂覆组合物可以优选包含聚合物作为选定的主成分，其占组合物干物质的重量百分比为约80%～99.5%，而该主成分之外的添加剂(例如其他聚合物或扁颗粒以及表面活性剂)的量在组合物干物质中的重量百分比为约0.05%～20%。
优选的是，选作主成分的聚合物的重量百分比是85%～98%，而添加剂的重量百分比是2%～15%。然而，应强调的是，上述物质的以任意重量比的任意组合都可考虑在本发明的范围内。
根据本发明的第二方面，定义了一种以至少一个涂覆步骤提供具有气体阻隔层的基底的方法，所述方法包括：在至少一个涂覆步骤中，通过用定义涂覆组合物的任一个权利要求中所限定的涂覆组合物对基底进行帘幕涂覆，而施涂所述涂覆组合物。
因此，所述方法可以仅包括一个施涂所述组合物的涂层的涂覆步骤，所述组合物仅含聚乙烯醇，或仅含任何上述多糖(淀粉、淀粉衍生物、MFC、半纤维素)，或含有其混合物，在该混合物中，主成分是聚乙烯醇，或者主成分是淀粉或淀粉衍生物或MFC或半纤维素。可以预见任意组合。
所述方法还可以包括用选自所有上述可能性中的组合物施涂第二涂层的第二步骤。通常，每个涂覆步骤之后将是干燥步骤。选作第一层和第二层的涂覆组合物可以是相同的涂覆组合物或不同的涂覆组合物。
因此，所述方法可以包括：在第一步骤中用包含聚乙烯醇的涂覆组合物对基底进行帘幕涂覆，并在第二步骤中用包含聚乙烯醇的涂覆组合物对基底进行帘幕涂覆。
作为另一选择，所述方法可以包括：在第一步骤中用包含多糖的涂覆组合物对基底进行帘幕涂覆，并在第二步骤中用包含多糖的涂覆组合物对基底进行帘幕涂覆。
作为再一选择，所述方法可以包括：在第一步骤中用包含多糖的涂覆组合物对基底进行帘幕涂覆，并在第二步骤中用包含聚乙烯醇的涂覆组合物对基底进行帘幕涂覆。
作为又一选择，所述方法可以包括：在第一步骤中用包含聚乙烯醇的涂覆组合物对基底进行帘幕涂覆，并在第二步骤中用包含多糖的涂覆组合物对基底进行帘幕涂覆。
作为再一种选择，所述方法可以包括：在第一步骤中用包含聚乙烯醇、MFC、纳米颗粒形式的粘土和水溶性非离子型乙氧基化醇的涂覆组合物对基底进行帘幕涂覆，并在第二步骤中用包含淀粉或淀粉衍生物以及水溶性非离子型乙氧基化醇的涂覆组合物对基底进行帘幕涂覆。这些涂覆的相反顺序也是可行的。
作为又一种选择，所述方法可以包括：在第一步骤中用包含聚乙烯醇、半纤维素、纳米颗粒形式的粘土和水溶性非离子型乙氧基化醇的涂覆组合物对基底进行帘幕涂覆，并在第二步骤中用包含淀粉或淀粉衍生物以及水溶性非离子型乙氧基化醇的涂覆组合物对基底进行帘幕涂覆；或反过来进行。
额外的涂覆步骤当然也是可预见的，而且，在可能的涂覆组合物的整体范围内，相同或不同的涂覆组合物的层的任意组合是可行的。额外的涂覆步骤的实例是颜料涂覆步骤，该步骤非常适合在用所述涂覆气体阻隔性涂覆组合物进行涂覆之前进行。
此外，至少一个涂层的涂覆重量可以是0.4g/m2以上且小于7.0g/m2。阻隔层的涂覆重量可以是0.8g/m2以上且小于7.0g/m2，优选为1.2g/m2～4.0g/m2，更优选为1.6g/m2～3.2g/m2。
根据一个特征，基底可以是纤维基底或纸或纸板。然而，可以想到在其他基底上实施本发明而不脱离本发明的范围。
根据本发明的第三方面，定义了一种具有至少一个气体阻隔层的经涂覆的基底，其通过用定义涂覆组合物的任一个权利要求所限定的涂覆组合物涂覆基底而获得。
所述气体阻隔层可以是特别针对氧气的阻隔层，也可以是针对包括气味和/或香气在内的气体的阻隔层。
此外，所述经涂覆的基底的气体阻隔层的涂覆重量可以是0.8g/m2以上且小于7.0g/m2，优选为1.2g/m2～4.0g/m2，更优选为1.6g/m2～3.2g/m2。
在一个实施方式中，所述经涂覆的基底可以是纸板，所述纸板包含至少一个涂覆有所述涂覆组合物的纤维类层。作为另一选择，所述基底可以是需要所关注类型的阻隔层的纸或任何其他基底。
根据本发明的第四方面，定义了一种包含上文定义的经涂覆的纸板的包装材料，所述包装材料在所述经涂覆的纸板的每一面上还包含低密度聚乙烯层，且OTR值小于40ml/m2·24h·1atm，或优选甚至小于10ml/m2·24h·1atm。OTR表示氧气透过率，其测量仪器是Mocon Ox Tran2/21。
根据本发明的第五方面，定义了一种由上文定义的包装材料制成的液体包装。
如上文提到的，通常，对于牛顿流体，涂覆液的动态表面张力应当小于40mNm，以满足不形成孔的下落幕帘的标准。然而，根据本发明，已有利地发现，作为非牛顿流体的多糖和聚乙烯醇因其弹性而不必需要和牛顿流体一样低的表面张力。由此需要获得流速和表面张力以及非牛顿流体特性之间的良好关系。帘幕稳定性的一些常见概念是在液体帘幕不断裂的情况下所能达到的最低流速和使帘幕自己愈合成完全无缺陷的液体帘幕的最低流速。根据本发明，已令人惊奇的发现，即使在极低的流速下，例如低于4.0升/分钟*米，多糖和聚乙烯醇的表面张力的动态表面张力值也可以达到最多50mNm且仍无缺陷地运行。
其他特征和优点将从以下对本发明的详细说明和测试例中变得显而易见。
附图说明
现将参照说明本发明的不同方面和实施方式的仅以实例给出的测试例和所附示意图来更详细地描述本发明，在附图中：
图1a～1d示意性地示出了本发明的经涂覆的基底的实例，和
图2a～2d示意性地示出了本发明的包装材料的实例。
具体实施方式
在寻找适合的表面活性剂和适合的方法的过程中，测试了据声称适合于帘幕涂覆的许多不同的市售表面活性剂。但是，发现它们都不适合，因为他们要么不能提供稳定的帘幕要么不能提供足够好的阻隔层。
在进行了许多测试之后，令人惊奇地发现了一组表面活性剂，它们能够提供所需的稳定帘幕效果和具有可接受量的针孔的高品质阻隔层。该组表面活性剂是非离子型乙氧基化醇，例如由BASF销售的商品Lutensol ON和Lutensol TO。具体而言，发现Lutensol ON50、Lutensol ON70和Lutensol TO8能提供所要求的结果。
根据BASF提供的产品信息，Lutensol ON类型是非离子型表面活性剂。它们是从饱和的合成短链脂肪醇制成的聚乙二醇烷基醚。它们符合下式：
RO(CH2CH2O)xH，其中
R=饱和的合成短链脂肪醇
x=3、5、6、7、8或11
该产品名中的数字代码通常表示乙氧基化度。Lutensol ON类型是通过使脂肪醇与环氧乙烷以化学计量比反应而制得的。将乙氧基化温度保持得尽可能低。这与原料的高纯度组合时确保获得了高性能低毒性产品。根据获自BASF的其他信息，R可以是异C10。
根据BASF提供的产品信息，Lutensol TO类型是非离子型表面活性剂。它们从饱和的异C13醇制得。它们符合以下结构式：RO(CH2CH2O)xH，其中
R=异C13H27
x=3、5、6、6.5、7、8、10、12、15或20
该产品名中的数字代码表示乙氧基化度。Lutensol TO类型是通过使异C13羰基合成醇(oxo alcohol)与环氧乙烷以化学计量比反应而制得的。将乙氧基化温度保持得尽可能低。这与原料的高纯度组合时确保获得了高性能低毒性产品。
对于Lutensol ON50，x(乙氧基化度)为5；对于Lutensol ON70，x为7。还测试了分子量较低的Lutensol ON——Lutensol ON30(x=3)，但未产生所需的效果。
对于Lutensol TO8，x为8。Lutensol TO8的分子量约为600g/mol。对于该组，还测试了分子量较低的Lutensol TO——Lutensol TO6(x=6)，但未产生所需的效果。
具有所需效果的非离子型乙氧基化醇是水溶性的且提供了相对慢的润湿。另一方面，Lutensol ON30和TO6不是水溶性的。Lutensol ON在乙氧基化度为5以上时为水溶性的，而Lutensol TO在乙氧基化度为8以上时为水溶性的。
另一种这样的水溶性非离子型乙氧基化醇是Lutensol XP。根据BASF提供的产品信息，Lutensol XP类型是支化的非离子型表面活性剂。它们是基于C10-Guerbet醇和环氧乙烷的聚乙二醇烷基醚。XP类型是通过使C10醇与环氧乙烷以化学计量比反应而制得的。产品名中的数字部分表示乙氧基化的一般程度。该产品在乙氧基化度为7以上时是水溶性的。
在使用以下包含聚乙烯醇的液体涂覆组合物进行测试时获得了令人满意的良好结果：所述液体涂覆组合物的溶液根据具体产品的说明书配制，并按照以下浓度向该溶液中添加所关注的表面活性剂：
表面活性剂浓度(按原样添加的表面活性剂占完全干燥的组合物的总重量的重量百分比)：0.05%～2%、优选0.1%～1.0%或甚至0.2%～5.0%；组合物的固相含量：4%～20%、优选7%～15%或甚至8%～10%。
通过以帘幕涂覆法将液体涂覆组合物沉积在移动的纤维类网上来进行测试。所述网是纸板。
测试结果列于表1中。该表中的结果是对以帘幕涂覆法涂覆的纸板进行测量而得到的，该纸板具有两层本发明的涂覆组合物，每层的涂覆重量与另一层相同或不同，总涂覆重量为2.0g/m2～5.0g/m2。在该表中，还示出了用仅包含聚乙烯醇(PvOH)的涂覆组合物和包含聚乙烯醇及市售表面活性剂Aerosol OT75(Cytec,USA，其包含“磺基琥珀酸二辛酯钠”)的比较用测试，但未产生令人满意的气体阻隔层。
表1：测试例
KIT=TAPPI T559KIT测试(纸和板对油脂、油和蜡的排斥性)
AO2IR是环境氧气进入速率的简写，其是用Perm-Mate仪器(由PBI Dansensor或Systech Illinois提供)测量氧气透过的方法。
OTR是氧气透过率的简写，其用仪器Mocon Ox Tran2/21在23℃和50%RH下测得。低KIT数表示仅针对脂肪有抗性；高KIT数表示针对脂肪和溶剂有高抗性。
低AO2IR值表示针对气体透过有高抗性。
OTR是对包含本发明的设置有30g/m2聚乙烯层的经涂覆的纸板的包装材料进行测量而得到的。低OTR值表示良好的阻隔功能。
所述涂覆组合物还可以包含扁平形式或纳米颗粒形式的上文提到的蒙脱石粘土或滑石、高岭土或其他类似的固体添加剂，并同时保持良好的阻隔效果，这也在测试中得到了证实。用蒙脱石(Cloisite)进行的测试也示于表1中。添加到聚乙烯醇中的粘土或其他适合的扁平或纳米形式的添加剂的量可以是组合物总干重的1干重%～20干重%、优选3%～15%、更优选5%～10%。
特别好的阻隔效果是显示出小于40ml/m2*24h*1atm或甚至小于10ml/m2*24h*1atm的氧气透过率(OTR)值的结果。
还将聚乙烯醇替换为淀粉进行了相同的测试。如表中可以看出，包含淀粉和表面活性剂的液体涂覆组合物也显示出了良好的测试结果：OTR小于40ml/m2*24h*1atm。
此外，按如下方式获得涂层并进行了相同的测试：用包含聚乙烯醇、蒙脱石粘土和MFC以及表面活性剂的液体组合物形成第一层，用包含淀粉和表面活性剂的液体组合物形成第二层。该涂层也产生了令人满意的良好测试结果，如表1所示。
可以预见的是，基于用淀粉和MFC获得的良好测试结果，还可以以与淀粉和MFC相同的方式单独使用或混合使用已知是良好屏障的半纤维素，主要是木糖胶(xylanes)和木糖葡聚糖(xyloglucanes)。
在网基底的速度为420m/分钟～850m/分钟时进行了测试，并获得了良好的结果。在至少6升/分钟*m的帘幕流速和稳定帘幕条件下，能够显示出，理论上可以具有250m/分钟～1500m/分钟或更高的速度，且施加在两个层中的涂覆重量为0.4g/m2～4.0g/m2、总共0.8g/m2～8.0g/m2，并取得了令人满意的阻隔效果。
应通常理解的是，本发明不限于具有以上商品名的表面活性剂产品，而由其他供应商或制造商以其他商品名销售的类似的/相应的产品也会因此有效。还应提及的是，在不脱离本发明的范围的情况下，预见了混合两种以上表面活性剂的可能性，还能够预见可以向涂覆组合物中添加其他组分。
用于上述测试的聚乙烯醇由Kuraray Nordic Oy以产品范围Mowiol6/98、15/99和28/99的形式提供，并且按照供应商的说明书将其溶于热水中来制备。所使用的淀粉是由Solam AB提供的羟丙基化的氧化淀粉产品Solcoat P150。按照供应商的说明书，将该淀粉溶于热水中来制备。微原纤纤维素(MFC)由Innventia AB提供，并且作为即用型纤维悬浮液提供。蒙脱石粘土由Southern Clay Products,USA以产品CloisiteNa+的形式提供。还用高岭土和滑石进行了测试，其具有与蒙脱石类似的良好结果。所用的高岭土由Imerys以产品Barrisurf LX的形式提供。所用的滑石由FinnTalc Oy以产品Finntalc C10B的形式提供。应明白的是，还可以使用其他类似类型的聚乙烯醇和其他品牌的上述物质，而不脱离本发明的范围。总之，本发明可以获得适用于液体包装的涂覆有阻隔层的纸板，其中，聚乙烯醇/多糖层提供了氧气阻隔性，而其他额外的层(例如聚乙烯)提供了液体阻隔性和密封性。
所关注的液体涂覆组合物通常能够通过向冷水中添加所用的聚合物(聚乙烯醇和/或多糖)并在适用时添加粉末形式的蒙脱石(或滑石或高岭土)来制备。如果使用MFC或半纤维素，其通常为预悬浮形式。由此获得了使所填加的物质溶解或悬浮或分散在水中的液体。随后加热该液体。制备后，应当使液体冷却，而后添加表面活性剂，随后，所得的组合物即可用于帘幕涂覆法。作为另一选择，可以各自制备每种物质，例如将其溶解(或悬浮或分散在冷水中)，而后将这些物质彼此混合、加热，随后添加表面活性剂，从而获得最终的组合物。
图1a～1d示意性地示出了本发明的经涂覆的基底的实例。图1a中示出了经涂覆的基底，其中，基底1是包含至少一个纤维类层的纸板，该纸板涂覆有气体阻隔涂层2，气体阻隔涂层2包含本发明的涂覆组合物。在图1b中，经涂覆的基底在纸板层1的反面上进一步设置有颜料涂层3，即，在纸板层1的未涂覆阻隔涂层2的面上涂覆有颜料涂层3。在图1c中，图1a中的经涂覆的基底也涂覆有颜料涂层3，但在该实施例中，颜料涂层3设置于纸板层1和气体阻隔涂层2之间。因此，阻隔涂层2施涂在已施涂的颜料涂层3的上面。最后，在图1d中，向图1c的经涂覆的纸板提供了额外的颜料涂层3，从而使纸板层1在两面上都具有颜料涂层3，并具有施涂在一个颜料涂层3上的阻隔涂层2。
图2a～2d示意性地示出了本发明的包装材料的实例。图2a～2d图示了与图1a～1d分别对应的经涂覆的基底，每个基底在两面上都提供了聚乙烯层4。
本发明不限于所公开的实施例，而是可以以对本领域技术人员显而易见的多种方式在所附权利要求的范围内进行修改。

Claims (30)

1.一种能够帘幕涂覆的气体阻隔性涂覆组合物，所述涂覆组合物包含聚合物和表面活性剂，其中，所述聚合物选自由聚乙烯醇和多糖或其混合物组成的组，其中，所述多糖能够溶解或分散或悬浮在水中，所述表面活性剂是水溶性非离子型乙氧基化醇。
2.如权利要求1所述的涂覆组合物，其特征在于，所述多糖包括淀粉、淀粉衍生物、MFC(微原纤纤维素)和半纤维素。
3.如权利要求2所述的涂覆组合物，其特征在于，所述聚合物仅包含聚乙烯醇，或包含与淀粉和/或淀粉衍生物和/或MFC和/或半纤维素成混合物的聚乙烯醇。
4.如权利要求2所述的涂覆组合物，其特征在于，所述聚合物仅包含淀粉或仅包含淀粉衍生物，或包含其混合物，或者包含与MFC和/或半纤维素成混合物的淀粉或淀粉衍生物中任一种。
5.如权利要求2所述的涂覆组合物，其特征在于，所述聚合物仅包含MFC或仅包含半纤维素，或包含其混合物。
6.如权利要求1～5中任一项所述的涂覆组合物，其特征在于，所述表面活性剂是饱和的异C13醇。
7.如权利要求6所述的涂覆组合物，其特征在于，所述表面活性剂具有式RO(CH2CH2O)xH，其中R=异C13H27，且x为8以上。
8.如权利要求1～5中任一项所述的涂覆组合物，其特征在于，所述表面活性剂是基于C10-吉布特醇的聚乙二醇烷基醚，且乙氧基化度为7以上。
9.如权利要求1～5中任一项所述的涂覆组合物，其特征在于，所述表面活性剂是饱和的短链脂肪醇。
10.如权利要求9所述的涂覆组合物，其特征在于，所述表面活性剂具有式RO(CH2CH2O)xH，其中R=饱和的短链醇，且x为5以上。
11.如前述权利要求中任一项所述的涂覆组合物，其特征在于，所述涂覆组合物包含非离子型乙氧基化醇表面活性剂；相对于完全干燥的涂覆组合物的总重量，所述表面活性剂的浓度是0.05重量%～2.0重量%、优选0.1重量%～1.0重量%、更优选0.2重量%～0.5重量%。
12.如前述权利要求中任一项所述的涂覆组合物，其特征在于，所述涂覆组合物包含的组分的固相含量为4%～20%、优选为6%～12%、更优选为8%～10%。
13.如前述权利要求中任一项所述的涂覆组合物，其特征在于，所述涂覆组合物包含扁平颗粒。
14.如权利要求13所述的涂覆组合物，其特征在于，所述涂覆组合物包含纳米颗粒形式的蒙脱石粘土。
15.如前述权利要求中任一项所述的涂覆组合物，其特征在于，所述涂覆组合物包含聚合物作为选定的主成分，所述聚合物占所述组合物的干物质的重量百分比为约80%～99.5%，向所述主成分添加的添加剂的量占所述组合物的干物质的重量百分比为约0.05%～20%，所述添加剂为例如其他聚合物或扁平颗粒以及表面活性剂。
16.一种以至少一个涂覆步骤提供施涂有气体阻隔层的基底的方法，所述方法包括：在至少一个涂覆步骤中，通过用权利要求1～15中任一项所述的涂覆组合物对所述基底进行帘幕涂覆，而施涂所述涂覆组合物。
17.如权利要求16所述的方法，所述方法包括：在第一步骤中用包含聚乙烯醇的涂覆组合物对所述基底进行帘幕涂覆，并在第二步骤中用包含聚乙烯醇的涂覆组合物对所述基底进行帘幕涂覆。
18.如权利要求16所述的方法，所述方法包括：在第一步骤中用包含多糖的涂覆组合物对所述基底进行帘幕涂覆，并在第二步骤中用包含多糖的涂覆组合物对所述基底进行帘幕涂覆。
19.如权利要求16所述的方法，所述方法包括：在第一步骤中用包含多糖的涂覆组合物对所述基底进行帘幕涂覆，并在第二步骤中用包含聚乙烯醇的涂覆组合物对所述基底进行帘幕涂覆。
20.如权利要求16所述的方法，所述方法包括：在第一步骤中用包含聚乙烯醇的涂覆组合物对所述基底进行帘幕涂覆，并在第二步骤中用包含多糖的涂覆组合物对所述基底进行帘幕涂覆。
21.如权利要求16所述的方法，所述方法可以包括：在第一步骤中用包含聚乙烯醇、MFC、纳米颗粒形式的粘土和水溶性非离子型乙氧基化醇的涂覆组合物对所述基底进行帘幕涂覆，并在第二步骤中用包含淀粉或淀粉衍生物以及水溶性非离子型乙氧基化醇的涂覆组合物对所述基底进行帘幕涂覆；或反过来进行。
22.如权利要求16所述的方法，所述方法可以包括：在第一步骤中用包含聚乙烯醇、半纤维素、纳米颗粒形式的粘土和水溶性非离子型乙氧基化醇的涂覆组合物对所述基底进行帘幕涂覆，并在第二步骤中用包含淀粉或淀粉衍生物以及水溶性非离子型乙氧基化醇的涂覆组合物对所述基底进行帘幕涂覆；或反过来进行。
23.如权利要求16～22中任一项所述的方法，其中，至少一个涂层的涂覆重量是0.4g/m2以上且小于7.0g/m2。
24.如权利要求16～23中任一项所述的方法，其中，所述气体阻隔层的涂覆重量是0.8g/m2以上且小于7.0g/m2。
25.如权利要求16～24中任一项所述的方法，其中，所述基底是纤维基底或纸或纸板。
26.一种经涂覆的基底，所述经涂覆的基底具有至少一个气体阻隔层(2)，所述经涂覆的基底通过用权利要求1～15中任一项所述的涂覆组合物涂覆基底(1)而获得。
27.如权利要求26所述的经涂覆的基底，其中，所述气体阻隔层(2)的涂覆重量是0.8g/m2以上且小于7.0g/m2。
28.如权利要求26～27中任一项所述的经涂覆的基底，其中，所述基底(1)是纸板，所述纸板包含至少一个涂覆有所述涂覆组合物的纤维类层。
29.一种包装材料，所述包装材料包含权利要求28所述的经涂覆的纸板，所述包装材料在所述经涂覆的纸板的每一面上还包含低密度聚乙烯层(4)，且所述包装材料的OTR值小于40ml/m2·24h·1atm、且优选小于10ml/m2·24h·1atm。
30.一种由权利要求29所述的包装材料制成的液体包装。
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