CN107667060A - 膜 - Google Patents

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Publication number
CN107667060A
CN107667060A CN201680027093.4A CN201680027093A CN107667060A CN 107667060 A CN107667060 A CN 107667060A CN 201680027093 A CN201680027093 A CN 201680027093A CN 107667060 A CN107667060 A CN 107667060A
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CN
China
Prior art keywords
film
coating
component
film according
packaging structure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201680027093.4A
Other languages
English (en)
Inventor
卡罗琳·泽伊费尔特
乔纳森·休伊特
杰米·莫法特
伊丽莎白·塔特洛克
亚当·埃德金斯
劳伦斯·詹姆斯·戴维森·马修斯
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Food Fresh Technology Holding Co Ltd
Innovia Films Ltd
Original Assignee
Food Fresh Technology Holding Co Ltd
Innovia Films Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Food Fresh Technology Holding Co Ltd, Innovia Films Ltd filed Critical Food Fresh Technology Holding Co Ltd
Publication of CN107667060A publication Critical patent/CN107667060A/zh
Pending legal-status Critical Current

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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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00—Preservation or chemical ripening of fruit or vegetables
    • A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
    • A23B7/144—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of gases, e.g. fumigation; Compositions or apparatus therefor
    • A23B7/152—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10 in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere comprising other gases in addition to CO2, N2, O2 or H2O ; Elimination of such other gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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Abstract

用在包装结构中的膜，其包括在膜表面上的涂层，所述涂层包含粘合剂和能够从与包装结构中的膜接触的环境中除去挥发性有机化合物的粒状突起组分。还提供了包括这种膜的包装结构和包括该包装结构的包装件。

Description

膜
技术领域
本发明涉及用于包装结构的膜，特别是包括能够除去挥发性有机化合物的组分的膜。
改进包装内的环境可能非常重要，且可以通过多种方法实现。当包装含有有机物如食品时，这种改进尤其重要。有机物会发出挥发性有机化合物(VOCs)如乙烯或三甲胺，这会对有机物本身的质量产生影响。
从包装环境中去除VOCs有助于延长保质期，并提高有机物如新鲜产品和园艺产品的市场品质，以及这些物质随时间延续的质量。它还有助于减少或消除不需要的气味并保持有机物的颜色和/或坚固度。
乙烯作为熟成激素，会导致包装中有机物过度熟成，从而降低其质量，并引起黄变和剥离损坏。乙烯还会由于应力由有机物产生，因此它的去除有助于减轻应力对有机物的影响。目前有许多方法可以从包装环境中除去乙烯，如通风、化学技术、吸附、光催化法、化学催化法和清除。
一种方法是抑制乙烯在有机物自身中的作用，这又可以减少由产品释放到包装中的乙烯的量。这种乙烯阻断技术包括1-甲基环丙烯(1-MCP)以及硫代硫酸银(STS)，前者阻断乙烯结合点并作为气体外源性施用，后者主要限于用于鲜切花并通过将鲜切花茎放置在含有STS的溶液中施用。
氨基乙氧基乙烯甘氨酸(AVG)是另一种乙烯阻断剂，其通过阻断植物组织中乙烯的产生而用作植物生长调节剂。通常在收获前1至3周，将其喷洒到有机物上。然而，这种方法会导致在防止成熟中较长久的效用。
可替代地，一旦释放出了乙烯或其他VOCs，可以把它们从环境中除去。通常基于铂和/或氧化铝的催化体系是本领域众所周知的，以将乙烯氧化成二氧化碳和水。然而，这些通常在升高的温度(通常高于200℃)下起作用，因此对于在这样的温度下会被损坏的物质不是特别有用。还有报道采用二氧化钛进行乙烯的光催化氧化的用途，其可以在室温下发生。
本领域中还已知的是化学计量氧化剂(stoichiometric oxidising agents)，其大多是基于高锰酸钾(KMnO4)，其再次氧化乙烯并自身被还原。然而，该方法还可导致产生部分氧化的物质如羧酸、乙醛和甲醛。这样的体系在高湿度下也不能很好地起作用，因此通常以某种方式不与水接触。
吸着剂在本领域中也是已知的，以从环境中除去VOCs，特别是乙烯。这些化合物通过吸着VOCs而起作用，并且通常是基于高表面积材料。通常用于除去乙烯的吸着剂包括活性炭、粘土和沸石。
沸石是特别公知的用于从环境中除去乙烯的吸着剂，并且在GB2252968、WO2007/052074和WO2011/001186中公开了合适的沸石组合物。然而，它们也会被水毒化，因此当商业化使用这些化合物时，需要防止或至少阻碍沸石与水接触的措施。
沸石在现有技术的包装中通常以在制造过程中插入到包装内的单独结构的形式使用。所述结构包括基材如膜(通常使用双轴取向的聚丙烯)，其形成通常面积约1.75平方英寸(约20cm2)的过滤器。然后施加隔膜(membrane)(如多孔隔膜，比如TyvekTM)，使得水不能与沸石直接接触。将沸石涂覆在隔膜上，随后施加基材。然后将完成的过滤器放置在包装内的有机物旁边或附近。另外，类似结构的片材可用作运输衬里或袋子，或者可以将所述结构引入到气泡包裹层(bubble wrap layer)或吸湿垫内，或层压到其它结构。
如在EP1525802、WO2008/110020、JPH02119938和JPH02222725中所公开的，将以上讨论的组分直接引入膜内或涂层内也是本领域已知的。然而，所述组分使用量少并且被包埋到可渗透相关VOC的粘合剂材料层内。这样确保了所述组分免受湿气和其他可能降低其效率的因素，同时仍然能够从环境中除去VOC。
US5807630公开了受控的渗透性膜，其包括成膜聚合物和任选的分散聚合物和惰性多孔填料，其可以具有涂覆在其上的表面改性剂。惰性多孔填料以有效降低膜的二氧化碳渗透性与氧气渗透性之比的量存在，并且填料的粒径大于成膜聚合物的本征膜厚度。
US2005/0147772公开了包括两层的包装材料，在两层之间限定了空腔。在空腔中容纳了能够将气体保留在其中的物质，并且其中一层可渗透气态乙烯而不能渗透水蒸气。
US2002/0090425公开了包括气体可渗透隔膜的容器，所述隔膜包括(1)微孔膜和(2)微孔膜上的聚合物涂层。所述容器能够在受控条件下储存和/或熟化香蕉。
US4847145公开了用于保持蔬菜和水果新鲜的膜，其具有乙烯吸附活性。所述膜优选含有细孔材料。
EP2060392公开了至少两层的聚酯膜，其包括至少一种包含负载银的沸石的抗微生物改性的外层，其中层厚度不大于沸石的中值粒度的1.3倍。
JPS63309137公开了含有1至30重量％结晶沸石的合成聚合物膜层，其具有>＝3.2埃的孔径和<＝20mum的粒径，并且可以用作片材、袋子或瓦楞纸箱的衬里。
发明内容
本发明是考虑了前述内容而设计的。
根据本发明的第一方面，提供用于包装结构中或用作包装结构的膜，其包括在膜表面上的涂层，所述涂层包含粘合剂和能够从与包装结构中的膜接触的环境中除去挥发性有机化合物的粒状突起(protuberant)组分。
通常，与膜接触的环境是大气环境，从包含在包装结构内的有机物发出至少一种挥发性有机化合物进入所述大气环境中。具体考虑了改性的和未改性的大气包装结构。
突起组分可能能够通过任何有效的方法，如吸附、吸收或化学改性从与包装结构中的膜接触的环境中除去挥发性有机化合物。为了方便起见，本文我们将使用术语“清除”来描述从与包装结构接触的环境中可能除去挥发性有机化合物的所有机理，并相应地理解术语“清除剂”和“清除组分”。
将清除剂引入到膜涂层中，其突起可以提高挥发性有机化合物的去除效率。该突起增加了清除剂或清除剂活性组分相对于环境的表面积，从而增加了其对挥发性有机化合物的可用性。此外，它改善了反应的动力学，因为挥发性有机化合物不必穿过大量的膜材料。然而，可能重要的是在清除剂周围有足够的涂层材料将其锚固在涂层内。
因此，借助于清除剂的突起提高了其关于从周围大气中去除挥发性组分的功效，增加了清除组分与周围环境之间的接触表面积，所述接触表面积超过了如果组分不是突起的而是完全包埋在涂层中所可以实现的。这种突起的布置可以以多种方式实现，如使用薄涂层和/或在涂层中高浓度的组分和/或通过参考涂层厚度(或涂层重量)选择突起组分的尺寸在至少一个尺度上大于涂层重量。从其中除去挥发性有机化合物的环境可以至少部分地被膜包围或包封。
清除组分是粒状材料。颗粒可能会突起出涂层，因此可能会暴露(即，可能没有任何涂层覆盖它们的至少一部分)。或者，薄层涂层可能覆盖颗粒。在这个意义上说，“突起”并不一定意味着“暴露”，因为涂层的材料可以延伸越过突起组分。因此，突起组分从涂层突起，意味着所述组分从膜的表面延伸超过涂层的基本厚度(即，在不存在突起组分的情况下涂层的厚度)。越过突起组分存在的少量涂层材料不会消除突起组分的活性，因为周围大气中的挥发性组分能够穿过涂层材料接触突起组分。但是，通过所述组分的突起提高了这些挥发性组分能够通过涂层与组分接触的程度，所述程度超过了如果相同组分不是突起的而是完全包埋在涂层中所能获得的。因此，清除组分的突起代表了相对于现有技术组合物的显著优点。
所述涂层可以比所述组分的颗粒的平均直径更薄。这可以确保一些所述组分将从涂层中突出。它还可以提供改善的光学性质，如改进的透明性。此外，由于需要更少的涂层材料，所述膜可以制造成本更低。
涂层中的平均粘合剂厚度(即，不存在任何颗粒的情况下，单独的粘合剂的厚度)可以参考清除剂的粒度来选择，以确保清除剂的突起。涂层中的平均粘合剂厚度优选小于突起组分的粒度。例如，涂层中的平均粘合剂厚度可以为突起组分的粒度的约10％至约90％、约20％至约80％或约25％至约75％。如果涂层中的清除剂颗粒的量低，使得在膜和涂层表面之间的涂层中只有一个颗粒，这是特别优选的。作为整体的涂层的厚度(即粘合剂和颗粒的组合厚度)也可以小于突起组分的粒度。
施加到膜上的涂层中的平均粘合剂厚度可以为0.1μm至10μm，例如0.25μm至8.5μm、0.5μm至7.5μm或0.7μm至6.0μm。
另外或可替代地，可以选择清除剂颗粒和粘合剂的相对量以确保清除剂的突起。具体地，可以使用比粘合剂的量高的量的颗粒，使得颗粒在膜和涂层的表面之间的方向上搁置彼此之上。换句话说，由于颗粒的堆积，垂直于膜的轴穿过在膜和涂层表面之间的涂层材料中的一个以上颗粒。
在此实施方案中，取决于所用的颗粒的量，作为整体的涂层厚度可以大于单个突起组分的粒度，但是小于二个、三个、四个或更多突起组分组合的粒度，使得所述组分是突起的。此外，涂层中的平均粘合剂厚度可以小于、大于或等于单个突起组分的粒度。
段落中的“粒度”可以表示多个d1-99中的任何一个，例如d10、d50或d90，或者指在颗粒的正态或非正态分布中的任何其它选择的粒度。例如，可以使用算术平均粒度。
上面提及的清除剂的粒度可以通过例如激光散射使用例如Beckmann Coulter粒度仪以数量或体积来测定，并由体积百分比确定平均粒度(参见下面的图6)。
所述涂层可以包括流涂涂层(flood coating)，例如通过凹版印刷、反向凹版印刷或任何其它涂覆技术施加到膜上的水性流涂涂层。其它涂覆技术如狭缝式模(slot die)或挤出涂覆也在本发明的范围内。流涂涂层的使用提供了涂层材料跨越膜的均匀分布，这又提供了能够除去挥发性有机化合物的组分的均匀分布。然而，也可以使用图案化涂层。
能够从环境中除去挥发性有机化合物的组分在涂层中的浓度可以为0.001至50gm-2，优选为0.005至30gm-2，更优选为0.01至14gm-2，例如为0.1至10gm-2和最优选0.1至5gm-2。以此水平，可以从与包装结构接触的环境中除去足够的挥发性有机化合物，特别是乙烯。然而，该水平足够低以降低成本并保持膜所需要的特征，如透明度。
使用涂层，特别是薄涂层可以产生不是完全不透明的膜，使得仍然可以通过膜看到包装结构的内容物。此外，涂层保持了分散体内能够除去挥发性有机化合物的组分的稳定性。当它是水性形式而不使用需要惰性气氛的溶剂时，更容易处理所述组分。因此，这确保了能够除去挥发性有机化合物的组分保持比否则可能预期的更长时间的功能。
涂层可以包括烯烃、酯、醚、尿烷或丙烯酸聚合物、蜡、包括被认为是消泡剂或分散剂的那些的另外的防水化合物，或这些物质的组合。能够除去挥发性有机化合物的组分可能被水毒化，因此减少与组分接触的水的量的涂层可能是有益的。
所述膜可以是聚合物膜。根据本发明的聚合物膜可以通过本领域已知的任何方法制备，术语包括但不限于流延片(cast sheet)、流延膜(cast film)或吹塑膜(blownfilm)。膜可以包括聚烯烃膜，例如聚乙烯、聚丙烯、聚丁烯、其混合物、其共混物和其共聚物(嵌段和无规)和/或其它已知的聚烯烃。
或者，所述膜可以包括聚酯膜、聚酰胺膜、聚氨酯膜、聚卤乙烯膜、乙酸酯膜或生物聚合物膜如纤维素膜、PLA膜、淀粉基膜或PHA膜。
所述膜还可以包括作为面涂层(topcoat)的功能性阻隔层。该层可用于限制组分的功能部分的迁移。所述层还可以保护能够除去挥发性有机化合物的组分免受组分尘污或免于水，这对于暴露(即不被涂层覆盖)的组分的那些部分可能是特别重要的。当所述组分是沸石时，这可能尤为重要，因为这些组分会通过与水接触被毒化或以其它方式而受到损害(compromised)。
由于监管的原因也可以使用面涂层，例如，如果所述膜要用于与食品接触。也可以使用面涂层改善膜的美观性，这可能由于表面拓扑而使膜更有光泽和/或更透明。还可以使用面涂层以提高膜的热封性、可印刷性或剥离性。
所述面涂层阻隔层可以包括在涂覆步骤中施加的单独的层。这是在膜表面上形成面涂层阻隔层的简单且便宜的方法。
另外或可替代地，面涂层阻隔层可以包括从初始涂层迁移到表面以形成阻隔的组分，其可以是疏水阻隔。在此实施方案中，面涂层阻隔层可以由初始涂层中存在的组分形成，所述组分然后迁移到表面形成这种阻隔。
挥发性有机化合物可以是乙烯或乙醛。乙烯会导致各种有机材料熟化。因此，从包装结构中去除乙烯可以增加有机材料的保质期。在本发明范围内的有机挥发性化合物中可能提及的其它材料包括其它植物生长调节剂，如：赤霉素(GA)，例如GA4GA7和GA3；细胞分裂素，如CPPU和激动素；生长素，如1-萘乙酸(NAA)、2,4-D,3-吲哚乙醛酸(IAld)、3-吲哚乙酸(IAA)、3-吲哚丙酮酸(IPA)和吲哚丁酸(IBA)；和抑制剂/阻滞剂，如脱落酸(ABA)、嘧啶醇(ancymidolm)、西维因、矮壮素、氯代IPC(chloro IPC)、丁酰肼、调嘧醇、单氰胺(H2CN2)、氟磺酰草胺、甲哌鎓、多效唑、调环酸钙和琥珀酸(SADH)。
能够从包装结构中与膜接触的环境中除去乙烯的组分可以包括吸着剂。所述吸着剂可以是微孔材料如沸石、海泡石或可以是ZSM5的硅藻土、或粘土。沸石或其它微孔材料可以例如用金属如钯掺杂。特别考虑钯掺杂的沸石，如WO2011/001186中所述。
吸着剂，特别是沸石吸着剂，是本领域中众所周知的，用于从环境中除去乙烯。它们易于得到并且其化学性质众所周知。
清除剂可以在包装链中的任何合适的温度下起作用，例如-30℃至50℃。
所述涂层包括粘合剂。合适的粘合剂可以通过非限制性实例选自下列物质和其两种或多种相容的混合物：水分散性的或其它可溶性的(在合适的溶剂体系中)丙烯酸和丙烯酸聚合物及共聚物、丙烯酸酯、尿烷、尿烷丙烯酸酯、异氰酸酯、环氧化物、苯乙烯丁二烯橡胶、环化橡胶、氯化橡胶、苯乙烯丁二烯/马来酸酐共聚物、苯乙烯丙烯酸酯、油墨粘合剂、纤维素材料、醋酸纤维素、醋酸纤维素烷酸酯(alkyrate)(例如丁酸酯和丙酸酯)、聚乙烯醇缩丁醛、聚乙烯醇缩甲醛、聚乙酸乙烯酯、聚乙烯醇、硝化纤维素、乙基纤维素、羧甲基纤维素、乙基羟乙基纤维素、羟丙基纤维素、PvOH、聚乙烯亚胺、三聚氰胺甲醛、脲甲醛、萜烯树脂、醇酸树脂、酚醛树脂、松香、酯松香、亚麻子油、硅树脂、不饱和聚酯树脂、饱和聚酯树脂、EVA、淀粉、聚羟基链烷酸酯、聚酰胺、聚酰亚胺、聚酰胺酰亚胺、PvdC、PvB。
在一些情况下，可以优选使用基本上不含氨的粘合剂材料。特别是当清除组分包含关于VOC去除的功能性可能被氨的存在所损害的组分时，情况更是如此。
所述膜或所述膜涂层可以包括一种或多种功能材料，用于关于膜的功能或美学特征的其它目的。合适的功能材料可以选自下列物质的一种或多种、其混合物和/或其组合：UV吸收剂、染料；颜料、着色剂、金属化和/或拟金属化涂层；润滑剂、抗静电剂(阳离子的、阴离子的和/或非离子的，例如聚(氧乙烯)脱水山梨醇单油酸酯)、抗氧化剂(例如亚磷酸、三(2,4-二叔丁基苯基)酯)、表面活性剂、硬化助剂(stiffening aids)、滑动助剂(slipaids)(例如热滑动助剂或冷滑动助剂，其提高膜在约室温下令人满意地通过表面滑动的能力，例如微晶蜡)；光泽改进剂、降解助剂(prodegradants)、用于改变膜的气体和/或水分可渗透性的阻隔涂层(如聚偏二卤乙烯，例如PVdC)；防粘连助剂(例如微晶蜡，例如平均粒度为约0.1至约0.6μm)；降粘添加剂例如热解法二氧化硅、二氧化硅、硅酮胶)；粒状材料(例如滑石)；增塑剂；增加COF的添加剂(例如碳化硅)；从周围环境中除去恶臭材料的添加剂；改善油墨粘合力和/或可印刷性的添加剂、增加硬度(stiffness)的添加剂(例如烃树脂)；增加收缩的添加剂(例如硬树脂)。
能够将挥发性有机化合物从环境中除去的组分与涂层的粘合剂组分的干重比可以在200:1至1:200之间，优选在100:1至1:100之间，或者在50:1至1:50之间，或在30:1至1:30之间。发现这些比例提供了能够除去挥发性有机化合物的组分在膜上的均匀分布，以及减少尘污和增加对基材的粘合。然而，能够从环境中除去挥发性有机化合物的组分与涂层组分或粘合剂的较高比例增加了组分对大气的暴露，从而提高挥发性有机组分的去除速率。同样，优选的比例取决于所选择的粘合剂的性质，并且对于某些粘合剂材料，可以优选增加(或减少)相对于粒状清除剂的量使用的粘合剂的量。
根据本发明的第二方面，提供了包括上述膜的包装结构。
所述膜可以形成包装结构的覆盖层(cover layer)或基层(base layer)。所述膜也能够至少部分地包围或包封待包装在包装结构中的物品。另外或替代地，所述膜可以至少部分地层压到气泡包裹层或吸湿垫。这可以保护包装结构的内容物免受损坏。所述膜也可以形成运输衬里或袋子的一部分，或者可以层压到另一个基材，如可热成形的膜、片材或底盘(tray)。
根据本发明的第三方面，提供了包装件(package)，其包括能够发出由上述包装结构至少部分包封或包围的挥发性有机化合物的物品。所述物品可以是可食用的或园艺物品。
根据本发明的第三方面，提供了包装件，其包括能够发出由上述包装结构至少部分包封或包围的挥发性有机化合物的物品。所述物品可以是可食用的或园艺物品。
附图说明
现在将仅参考以下实施例和附图，借助于实施例更具体地描述根据本发明的一个或多个实施方案，其中：
图1示出了实施例3的样品002的切开的边缘的扫描电子显微镜图像；
图2a示出了实施例3的样品001的光学显微镜图像；
图2b示出了实施例3的样品002的光学显微镜图像；
图3示出了实施例3的乙烯颗粒的粒度分布图；
图4示出了实施例3的样品001的表面的扫描电子显微镜图像；
图5示出了沸石颗粒内得到的EDX谱图；
图6示出了参考下面的实施例4，在声处理之前(141222_01_02)和声处理3分钟之后(150217_02_01)的粒度分析，表明如实施例4所述的根据本发明使用的特定清除剂的典型粒度分布；
图7示出了实施例5(没有外涂层)的涂覆材料的横剖面的SEM图像；和
图8示出了实施例6(带有外涂层)的涂覆材料的横剖面的SEM图像。
具体实施方式
现在将仅参考以下实施例，借助于实施例更具体地描述根据本发明的一个或多个实施方案：
实施例1
将BOPP膜涂底漆，然后干燥。为了避免IPA(异丙醇)与钯掺杂的沸石(清除剂)接触，独立地制成了水和清除剂的水基浆料。维持搅拌使浆料不沉降。使用丙烯酸共聚物(WB1240)作为粘合剂，比例为1:9的清除剂:粘合剂，将其用k棒拉下来，并在90℃或更高的烘箱中干燥设定的时间。样品的总(干)涂层重量为0.18-0.2g/m2的清除剂粉末，其通过计算涂层的总重量除以比例来评估。
通过保持表面上的清除剂的干重(为0.8g/m2)但改变粘合剂的量(以及因此粘合剂的涂层重量)形成不同的比例，来评估清除剂:粘合剂的比例的影响。发现：清除剂与粘合剂的比率小于1:1是必要的，以此特定的粘合剂来获得具有可接受的外观的膜以及必需的VOC清除能力。
实施例2
将BOPP膜涂底漆，然后干燥。为了避免IPA(异丙醇)与钯掺杂的沸石(清除剂)接触，独立地制成了水和清除剂的水基浆料。维持搅拌使浆料不沉降。使用AQ2093(乙烯丙烯酸共聚物)作为粘合剂，比例为9:1的粘合剂:清除剂，将其用k棒拉下来，并在90℃或更高的烘箱中干燥设定的时间。样品的总(干)涂层重量为0.18-0.2g/m2的清除剂粉末，其通过计算涂层的总重量除以比例来评估。
通过保持表面上的清除剂的干重(为0.8g/m2)但改变粘合剂的量(以及因此粘合剂的涂层重量)形成不同的比例，来评估清除剂:粘合剂的比例的影响。发现：1:1的比例得到伴随不完全扩展的条纹涂层，并且当用硬币刮擦时，清除剂“被弄成粉末(dusted)”。较低的清除剂:粘合剂比率全都得到无条纹的均匀涂层。
用于乙烯吸收的方法
取10×10cm的样品，折叠并密封到20ml玻璃顶空小瓶中，并用丁基橡胶隔片卷曲密封。一式三份，分析样品。将3000μl乙烯(100％)注入含有样品的密封小瓶中。类似地制备相应的空白样品，用作校准标准。在GC-FID分析之前，将制备好的样品在环境实验室条件下静置7天。
以27％的固体配制1:2比例的清除剂:粘合剂，得到表面上的总清除剂含量为0.8gsm。使用聚乙烯亚胺底漆对50μm BOPP涂底漆，然后将涂层施加到其上，得到12μm的总的湿厚度。提交这些样品用于乙烯吸附测试，具有如下所示的重复结果。
重复 乙烯吸收(μl/100cm2)
1 174
2 280
使用铵模板形成沸石清除剂的孔，因此清除剂可能对NH3敏感。在此实施例中使用的粘合剂是NH3稳定化的，因此可能阻碍乙烯吸收。
实施例3
生成两个根据实施例2的膜，其中一个的涂层引入0.1g/m2清除剂(清除剂:粘合剂的比为1:18)(样品001)和另一个的涂层引入0.2g/m2清除剂(清除剂:粘合剂的比为1:9)(样品002)。从两个样品切取一定区域，并放置在玻璃载片上的碳标签上，使用微分干涉相衬(DIC)使用zeiss axio M2m成像仪复合光学显微镜进行成像。
为了使清除剂颗粒对比度最大，还摄取了反射光图像并数字化增强。使用NIS元件软件计数表面颗粒。然后将原始数据导出到Excel进行进一步处理和调整，以便产生每mm2的代表性的粒子计数和表面粒度分布的图形表示。
还从放置在碳标签上的样品001中取区域并镀金，用于扫描电子显微镜(SEM)成像。还在粒子上进行能量色散X射线分析(EDX)。
这次从样品002取另一个区域并切片。首先使用标准的一次性刀片，然后使用金刚石刀来改善剖面。然后将所述剖面放置在SEM样品保持器中，并将切开的边缘镀碳。将清除剂颗粒切片处的区域成像，并再次进行EDX分析，以确定是否可以检测到钯。
图2a和2b清楚地表明引入到膜表面上的样品001和002的涂层中的颗粒。粒度分布如图3所示。粒子分布宽，并且必须记住，在图1中清晰地示意出的涂层覆盖(coverage)会增加测量的粒度。
在此实施例中，钯乙烯清除剂是在沸石载体上。沸石是通常用作商业吸附剂的微孔的铝硅酸盐矿物。沸石颗粒在图1中清晰可见。EDX分析确定了铝、硅和氧的存在，如图5所示。钯仅以低水平存在而未被检测到。图1和2b表明，尽管很好地包埋在涂层中，但至少一些颗粒已经穿透到表面上。通过此，对电子束透明的非常薄的层仍然可以给出非常薄的覆盖是可能的。
可以在膜表面上清楚地看到乙烯清除剂颗粒。它们被牢固地包埋到涂层内并且看起来穿透了涂层。然而，由于粒度分布宽，较小的颗粒很可能被非常薄的涂层覆盖。EDX分析清楚地确定了硅、铝和氧的存在，并且还通过XRF测定了钯的存在。
实施例4
使用声处理制备含有钯掺杂的沸石(清除剂)的水基分散体，以促进去除附聚体。如图6所示，粒度为20-40μm的附聚体被去除。得到的平均粒度(声处理后)是4.6μm。
使用聚氨酯分散体作为粘合剂体系，其中加入清除剂，形成具有27％固体含量的涂层溶液。将其拉下来至电晕处理的(38mN/m dyne)50μm BOPP(Innovia Films有限公司)上，得到湿厚度为12μm。膜表面上的总的干涂层重量为2.0gsm，其中总清除剂含量为0.8gsm。干燥后通过带拉脱(tape pull-off)测定涂层对膜基材的100％粘附(即0％的涂层去除)。测定了重复配方的乙烯吸收，结果如下所示。
重复 乙烯吸收(μl/100cm2)
1 996
2 876
实施例5
使用声处理制备含有钯掺杂的沸石(清除剂)的水基分散体，以促进去除附聚体。除去粒度为20-40μm的附聚体，得到的平均粒度为4.6μm。使用聚氨酯分散体作为粘合剂体系，以形成固体含量为36.6％的涂层。将其以100m/min的速度涂覆到电晕处理(38mN/mdyne)过的50μm BOPP(Innovia Films有限公司)上，得到20gsm的湿涂层重量。
通过涂层洗去(wash-off)测定干涂层重量为8.5gsm，其中总的清除剂含量为5.8gsm。通过带测试(tape test)此材料显示出对基材的95％的涂层粘附。使用SDL AtlasCrock Meter以50mmx50mm的布在3.5x13.5cm的样品尺寸上进行磨损测试，其中在测试区域中100％的涂层去除。使用Gelbo挠曲测试仪进行的第二次磨损测试，显示比Crock仪更少的涂层去除。将A4样品安装到机器上并挠曲200次，导致涂层轻微但可见的裂纹。
图7示出了此材料的剖面的SEM图像。一式两份地测量膜的乙烯吸收，结果如下所示：
重复 乙烯吸收(μl/12.5cm2)
1 1261
2 1128
实施例6
用20％固体的聚氨酯分散体外涂覆(overcoated)实施例5中描述的膜，得到涂层重量为1.8gsm，样品的(底漆的、涂覆的和外涂覆的)总涂层重量为10.4gsm。通过干燥后的带拉脱显示出涂层对基材的100％粘附。此外，在使用SDL Atlas Crock Meter(20个循环)进行的磨损测试之后，观察到零涂层去除，并且使用Gelbo挠曲测试仪(200个循环)观察到有限的涂层去除。与没有外涂覆的材料相比，在挠曲条件下有较少的涂层去除。
图8示出了此材料的横剖面的SEM图像。一式两份地测量膜的乙烯吸收，结果如下所示，并证明了外涂层不影响活性涂层的功效。
重复 乙烯吸收(μl/12.5cm2)
1 1505
2 1170

Claims (22)

1.一种用在包装结构中或用作包装结构的膜，其包括在膜表面上的涂层，所述涂层包含粘合剂和能够从与包装结构中的膜接触的环境中除去挥发性有机化合物的粒状突起组分。
2.根据前述权利要求中任一项所述的膜，其中施加到所述膜的涂层中的平均粘合剂厚度为0.1μm至10μm。
3.根据前述权利要求中任一项所述的膜，其中所述涂层中的平均粘合剂厚度参照清除剂的粒度选择，以确保所述突起组分的突起。
4.根据前述权利要求中任一项所述的膜，其中所述涂层中的平均粘合剂厚度小于所述突起组分的粒度。
5.根据前述权利要求中任一项所述的膜，其中所述涂层中的平均粘合剂厚度为所述突起组分的粒度的约10％至约90％、约20％至约80％或约25％至约75％。
6.根据前述权利要求中任一项所述的膜，其中所述涂层包括施加到所述膜的流涂涂层。
7.根据前述权利要求中任一项所述的膜，其中所述涂层包括丙烯酸聚合物和/或蜡。
8.根据前述权利要求中任一项所述的膜，其中所述膜还包括作为面涂层的功能性阻隔层。
9.根据权利要求8所述的膜，其中所述阻隔层包括在涂覆步骤中施加的单独的层。
10.根据权利要求8所述的膜，其中所述阻隔层包括从涂层迁移到表面的组分。
11.根据前述权利要求中任一项所述的膜，其中所述挥发性有机化合物是乙烯、乙醛或植物生长调节剂。
12.根据权利要求11所述的膜，其中能够从与包装结构中的膜接触的环境中除去乙烯的组分包括吸着剂。
13.根据权利要求12所述的膜，其中所述吸着剂包括微孔材料。
14.根据权利要求13所述的膜，其中所述微孔材料包括沸石或粘土。
15.根据权利要求13或权利要求14所述的膜，其中所述微孔材料包括：
a.掺杂的微孔材料；
b.金属掺杂的微孔材料；和/或
c.钯掺杂的微孔材料。
16.根据前述权利要求中任一项所述的膜，其中能够从环境中除去挥发性有机化合物的组分的浓度为0.001至50gm-2。
17.根据前述权利要求中任一项所述的膜，其中能够从环境中除去挥发性有机化合物的组分与所述涂层的粘合剂组分的干重比为200:1至1:200。
18.一种包括任一前述权利要求的膜的包装结构。
19.根据权利要求18所述的包装结构，其中所述膜形成所述包装结构的覆盖层和/或基层。
20.根据权利要求18或19所述的包装结构，其中所述膜至少部分地层压到气泡包裹层或吸湿垫或另外的基材。
21.一种包装件，其包括能够发出挥发性有机化合物的物品，所述挥发性有机化合物至少部分地被权利要求18至20中任一项所述的包装结构包封或包围。
22.根据权利要求21所述的包装件，其中所述物品是可食用的或园艺物品。
CN201680027093.4A 2015-05-12 2016-05-11 膜 Pending CN107667060A (zh)

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CA2982417A1 (en) 2016-11-17
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