CN101563405A - 多层密封薄膜 - Google Patents

多层密封薄膜 Download PDF

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Publication number
CN101563405A
CN101563405A CNA200780026735XA CN200780026735A CN101563405A CN 101563405 A CN101563405 A CN 101563405A CN A200780026735X A CNA200780026735X A CN A200780026735XA CN 200780026735 A CN200780026735 A CN 200780026735A CN 101563405 A CN101563405 A CN 101563405A
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CN
China
Prior art keywords
pla
polymkeric substance
hot sealing
sealing layer
multilayer film
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Granted
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CNA200780026735XA
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English (en)
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CN101563405B (zh
Inventor
F·邓
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DuPont Teijin Films US LP
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DuPont Teijin Films US LP
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Abstract

描述了一种适合用于密封容器、例如用于食品包装的多层薄膜，和制备这种薄膜的方法。该薄膜特别适合密封由聚乳酸(PLA)制成的容器。该多层薄膜包括a)包含聚合物底层的基体；b)在基体上包含PLA均聚物或共聚物的热封层。热封层还包括分散在其中的粘合促进剂，或可选择地，基体还包括在底层和热封层之间并与之相邻、在聚合物底层表面上的层中的粘合促进剂。在热封层中或在与基体相对的热封层表面上也可以包含防雾剂。

Description

多层密封薄膜
本申请要求2006年7月14日提交的美国临时专利申请第60/831,016号的优先权，该临时专利申请的全部内容通过引用结合在此。
背景技术
聚乳酸(PLA)是高度可生物降解的聚合物，源自天然资源例如玉米。使用PLA制作食品包装盘越来越普遍，至少部分是由于其容易生物降解，以及由PLA制成的盘具有很高的透氧率和透水率、因此非常适合包装新鲜产品的事实。然而，由PLA制成的盘在温度低如104°F(40℃)时就易软化和变形。因为这个缺点，用在PLA盘上的盖膜严格要求热封物必须在低温度(约200°F，或93℃)下用很短的停留时间(少于2秒)形成。传统的密封薄膜或者在足够低的温度下不能热封PLA盘，或者在完成密封后热封强度会随时间降低。共挤出的PLA薄膜具有一个无定型的PLA层和一个结晶的PLA层，其能够在低温度下密封到PLA盘，但是通常这种薄膜非常脆，容易撕裂，在包装线、尤其在高速包装线下不能良好运行。如上所描述的，如能提供这样的盖膜是将会是有益的，该盖膜可满足用于PLA盘密封性能的要求，也能满足实际商业应用所要求的膜加工性能。
发明内容
在一方面，本发明提供了一种多层薄膜，其包括：
a)包括聚合物底层的基体；和
b)在基体上包括PLA聚合物的热封层。该热封层还包括分散在其中的粘合促进剂，或者，基体还包括在聚合物底层和热封层之间并与之相邻、在聚合物底层表面上的层中的粘合促进剂。
在另一方面，本发明提供了一种密封容器，其包括具有开口的器皿，其中所述开口用以上所描述的多层薄膜在该薄膜具有热封层的一侧上将其密封。
在另一方面，本发明提供了一种制备多层薄膜的方法。该方法包括：
a)将涂布液涂敷在包括聚合物底层的基体上，该涂布液包括溶剂和PLA聚合物，其中该涂布液还包括粘合促进剂，或者基体在聚合物底层表面上的层中还包括粘合促进剂，以接收涂布液；和
b)除去溶剂，形成包括PLA聚合物的热封层。
在另一方面，本发明还提供了包含PLA聚合物、共聚聚酯和溶剂的涂布组合物。
具体实施方式
本发明人发现，采用本发明之前的已知方法，将很难实现PLA聚合物与聚对苯二甲酸乙二酯(PET)和许多其他基体的合适的强粘合性。为了解决这个和其他问题，根据本发明的多层薄膜包括包含聚合物底层的基体，和在所述基体上包含PLA聚合物的热封层。热封层和基体的一个或两者都另外包含粘合促进剂，该粘合促进剂增加PLA聚合物和聚合物底层之间的粘合，同时保持良好的低温热封特性。除非另外说明，本文中所用的术语“PLA聚合物”包括乳酸均聚物，或含有至少30摩尔％乳酸重复单元的乳酸共聚物。如果基体包含作为层的粘合促进剂，那么该层可以在聚合物底层制备过程中在线形成，或在聚合物底层制得后离线形成。通常，在热封层(即“热封性”聚合物)中可使用的聚合材料是热塑性聚合物，其软化温度比聚合物底层的软化温度低至少50°F，典型地，低至少100°F，更典型地，低至少150°F。该软化点优选在75°F以上。
如果粘合促进剂分散在热封层中，则分散体可以采取均相溶液的形式，或热封层可以包含聚合物的分散相和具有不同组成的聚合物的连续相。在一些实施方案中，粘合促进剂构成多于50重量％的一种所述相，PLA聚合物构成超过50重量％的另一种所述相。粘合促进剂可以分散在PLA聚合物中，或反之。相信在本发明某些实施方案的热封层中存在的模糊外观表示存在具有不同组成的聚合物的相。在基体上干燥后表现出所述外观和良好的热封性的一种示例性配制物由30％的无定型PLA聚合物(PLA 4060D，一种从Minnetonka，MN的NatureWorks LLC购得的D，L-聚乳酸聚合物)和70％的共聚聚酯(壬二酸/对苯二甲酸/乙二醇，45/55/100摩尔当量)构成。
本发明发现，通过仔细选择粘合促进剂，就能够制得这样的多层薄膜，其可以在PLA不变形的足够低温下被密封到PLA物品例如盘上，同时提供PLA聚合物层和基体之间的良好粘合。此外，至少部分由于存在机械坚固的聚合物底层，这些膜典型地表现出包装线上的优异加工性。
根据本发明，可以使用任何厚度的多层薄膜。典型地，该聚合物底层可具有12至120微米范围内的厚度。热封层典型地具有0.5至20微米范围内的厚度，更典型地，2.0至10微米的厚度。这些相对薄的热封层典型地可通过溶液涂布产生，其比通过其它方法例如挤出涂布或共挤出涂布实现更难。挤出加工PLA聚合物的一个缺点是需要预干燥聚合物，以防止热降解。当PLA聚合物通过溶液涂布、并在典型条件即在低于PLA聚合物热降解温度的加工温度下进行涂敷时，可以取消该额外的预干燥步骤。如果在PLA聚合物和聚合物底层之间存在单独的粘合促进层，那么典型地，该粘合促进层具有0.02至5微米范围内的厚度。
如果热封层包括溶解或者另外分散在其中的粘合促进剂，那么粘合促进剂的量典型地是促进剂和PLA聚合物总重的至少1重量％，更典型地，至少10重量％，最典型地，至少20重量％，或甚至至少30重量％。粘合促进剂的量典型地是促进剂和PLA聚合物总重的至多90重量％，更典型地，至多70重量％，最典型地，至多40重量％。在本发明的要求其中热封层相对清澈(不模糊)的那些实施方案中，粘合促进剂对PLA聚合物的相对含量适宜地稍低一些。例如，典型地，所述粘合促进剂的量是促进剂和PLA聚合物总重的至少20重量％，更典型地，至少30重量％，最典型地，约40重量％。所述量典型地是至多60重量％，更典型地，至多50重量％。在那些要求防止水滴在薄膜表面上形成的情况下，当薄膜被用在促使这种水滴形成的环境(例如冷冻食品的包装)中时，也可以使用如下面另外描述的防雾剂。现在将详细描述构成所述多层薄膜的各组分，接下去再描述如何制备该薄膜及该薄膜的一些典型应用。
热封层
热封层包括至少一种PLA聚合物。本发明所用的合适类型的PLA聚合物可以是本领域已知的任何种类，并可包括乳酸的均聚物和共聚物。合适的共聚单体包括式HOC(R1)(R2)(CH2)nCOOH的那些聚合物，其中R1和R2各自分别是H或取代的或未取代的C1-C5基团，n是0至10的整数。PLA聚合物可以是无定型的(即通过差示扫描量热法测定至少90％为无定型的)，或其可以具有较高的结晶度。典型地，PLA聚合物是至多50％结晶的，更典型地，至多20％结晶的。PLA聚合物可以是乳酸均聚物，该乳酸均聚物可以是一种或多种形态上不同的以下聚合物：D-聚乳酸、L-聚乳酸、D，L-聚乳酸和内消旋聚乳酸。D-聚乳酸和L-聚乳酸是相应的纯的对映体酸的聚合物，并且是光学活性聚合物。D，L-聚乳酸由外消旋乳酸制得，即具有良好限定构象的D-和L-聚乳酸单元的D-聚乳酸和L-聚乳酸的共聚物。内消旋聚乳酸是等摩尔的D-乳酸和L-乳酸的无规共聚物。已知PLA均聚物的形态受聚合物骨架中D异构体和L异构体的比例控制。典型地，D-乳酸含量越高，聚合物的结晶越小。
任何已知的聚合方法例如缩合聚合和开环聚合都能用来聚合乳酸。在缩合聚合中，例如，L-乳酸、D-乳酸或它们的混合物通过本领域已知方式直接进行脱氢缩聚。在开环聚合方法中，丙交酯(即乳酸的环状二聚体)在催化剂的存在下进行聚合以形成聚乳酸。丙交酯可以是L-乳酸的二聚体、D-乳酸的二聚体或L-乳酸和D-乳酸的混合二聚体。这些异构体可以混合并聚合，以获得具有任何要求的组成和结晶度的聚乳酸。
少量的扩链剂例如二异氰酸酯化合物、环氧化合物或酸酐可被用来增加PLA聚合物的分子量。该聚合物可以具有任何的分子量，但是，通常重均分子量在60,000-1,000,000道尔顿的范围内。通常，如果所述分子量小于60,000，就不能获得合适的物理性能。另一方面，如果所述分子量大于1,000,000，则熔融粘度会过高，从而导致较差的成型性能。
PLA聚合物还可以是乳酸与一种或多种共聚单体的共聚物。该共聚单体如果存在，则其合计可构成该PLA聚合物的小于50摩尔％，典型地，小于30摩尔％，或更典型地，小于10摩尔％。该共聚单体的例子包括己内酯；羟基羧酸，例如乙醇酸、3-羟基丁酸、4-羟基丁酸、4-羟基戊酸和6-羟基己酸；多元醇，例如乙二醇、丙二醇、丁二醇、新戊二醇、聚乙二醇、丙三醇和季戊四醇；多元酸，例如丁二酸、己二酸、癸二酸、反丁烯二酸、对苯二甲酸、间苯二甲酸、2，6-萘二甲酸、5-钠代磺基间苯二甲酸、5-四丁基鏻磺基间苯二甲酸盐。在本发明的一些实施方案中，优选共聚单体(如果存在任何一种)是可生物降解的。
在本发明的一些实施方案中，所述薄膜包含防雾剂来减少或消除薄膜内表面由于水滴形成而导致的雾气。防雾剂分散在热封层中和/或位于与基体相对的热封层的表面上。在一些实施方案中，防雾剂用来形成热封层的配制物的一部分，它可以大致停留分散在热封层中，或者可以喷镀(bloom)在表面。或者，它可以通过浸渍、喷射或另外涂布而典型地由合适的溶剂直接涂敷到热封层表面上。合适的防雾剂的实例包括烷氧基化的脂肪醚如
Figure A20078002673500091
502、脱水山梨糖醇酯如
Figure A20078002673500092
103、其他已知的非离子、阴离子和阳离子表面活性剂，例如脂肪酸聚氧烷撑酯、烷氧基化的酚类、混合的甘油一酸酯、甘油二酸酯或甘油三酸酯、多羟基醇的脂肪酸酯、其他聚烷氧基化的化合物等。产品可以从Tarrytown，NY的Ciba Specialty Chemical Corp.获得。如果防雾剂包括在热封层中，那么防雾剂典型地构成所述层的约0.1重量％至约15重量％，更典型地，约0.5重量％至约10重量％。如果直接涂敷至热封层表面，以热封层的重量计，防雾剂的量通常为约0.1重量％至约5重量％，更典型地，约0.1重量％至约1重量％。
热封层可以包括无机颗粒例如硅石，和/或增滑剂例如石蜡和/或聚四氟乙烯分散体。在一些应用中还可以包括抗氧化剂。在一些实施方案中，该热封层中可以不含增塑剂(例如聚二醇或聚醚或这些化合物的酯)、增粘剂和/或无机填料。在一些实施方案中，除了PLA聚合物以外，热封层还可以不含脂族聚酯。
粘合促进剂
本文中所用的术语“粘合促进剂”是指以下的一种材料，当该材料被添加到热封层的PLA聚合物中，或被用作热封层和聚合物底层之间的中间层时，当根据实施例部分的方法(ii)进行测试时，其为热封体提供至少200g/in的强度。典型地，所述强度可以是至少300g/in，更通常是至少400g/in。优选地，该粘合促进剂提供内聚破坏模式，其中当根据方法(ii)分开薄膜时，热封层与其各自的聚合物底层在一起，分离在熔合的热封层内。合适的粘合促进剂包括但不局限于乙烯共聚物，例如EVA(乙烯-醋酸乙烯酯)和EMA(乙烯-丙烯酸甲酯)，以及增粘树脂例如松香酯。
在一些实施方案中，所述粘合促进剂包括共聚聚酯树脂。本文中所用的术语“共聚聚酯”是指一种聚酯，其衍生自至少一种(优选仅一种)芳族二羧酸和至少一种(优选仅一种)脂族二羧酸或其低级烷基(即至多14个碳原子)二酯、以及一种或多种二元醇。在通常温度至多达到约275℃下，共聚聚酯的形成方便地按已知的缩合或酯交换方法进行。示例的芳族二羧酸包括对苯二甲酸、间苯二甲酸、邻苯二甲酸和2，5-、2，6-或2，7-萘二甲酸。示例的脂族二羧酸是通式CnH2n(COOH)2(其中n为2至8)的饱和脂族二羧酸，例如丁二酸、癸二酸、己二酸、壬二酸、辛二酸或庚二酸，优选癸二酸、己二酸和壬二酸，更优选壬二酸。
在一些实施方案中，所述聚酯包含不超过90％的芳族二羧酸(例如对苯二甲酸)和至少10％的脂族二羧酸，其中百分数是所述聚酯的总二酸含量的摩尔百分数。典型地，芳族二羧酸的含量是至少55摩尔％，并可以是60摩尔％或更多。典型地，以共聚聚酯的二羧酸组分计，芳族二羧酸的含量为不多于约80摩尔％，更典型地，不多于70摩尔％，更典型地，不多于65摩尔％。共聚聚酯中的脂族二羧酸的含量以共聚聚酯的二羧酸组分计是典型地至少20摩尔％，更典型地至少35摩尔％，但是，典型地至多45摩尔％。当以重量为基础表示时，芳族和脂族二羧酸的相对量在一定程度上取决于其各自的分子量，但是按重量计，通常是至少55％的芳族二酸和至多45％的脂族二酸。
合适的二元醇包括脂族二元醇，例如烷撑二醇。因此合适的二元醇包括脂族二醇，例如乙二醇、二甘醇、三甘醇、丙二醇、1，3-丁二醇、1，4-丁二醇、1，5-戊二醇、2，2-二甲基-1，3-丙二醇、新戊二醇和1，6-己二醇。通常使用的是乙二醇或1，4-丁二醇。所述共聚聚酯通常是至少50％无定型的，并可以完全是无定型的(即通过差示扫描量热法测定至少90％为无定型)。
如前面所述，共聚聚酯可以与PLA聚合物一起分散在热封层中，和/或形成基体的一部分，即共聚聚酯可以在聚合物底层上形成层。
聚合物底层
假如聚合物底层比仅由PLA均聚物制备的薄膜机械强度更大，那么该聚合物底层可以包含任何本领域已知的成膜聚合物。示例包括但不局限于聚酯薄膜、尼龙薄膜、由聚乙烯或乙烯共聚物制成的薄膜、聚丙烯薄膜和用增韧的PLA材料制成的薄膜。
在本发明的一些实施方案中，所述聚合物底层包含线性聚酯层，典型地是双轴取向的聚酯层。通常线性聚酯具有约0.5至约0.8的特性粘数，最典型的是约0.6。聚酯薄膜的实例包括双轴取向的聚对苯二甲酸乙二酯(PET)薄膜和双轴取向的聚萘二甲酸乙二酯(PEN)薄膜。
尤其有用的是已经双轴取向并热定型的聚对苯二甲酸乙二酯。这种材料在本领域是已知的，例如在Stokes的US 4,375,494中所描述的，其内容通过引用结合在此。
聚对苯二甲酸乙二酯聚合物的制备技术为本领域技术人员所熟知，并在许多文献中公开，例如Wiley，N.Y.的Encyclopedia of Polymer Scienceand Engineering第2版第12卷1-313页。通常该聚合物通过适宜的二羧酸或其低级烷基二酯与乙二醇缩合获得。聚对苯二甲酸乙二酯由对苯二甲酸或其酯形成，聚萘二甲酸乙二酯由2，6-萘二甲酸或其酯形成。
在共挤出的双层聚酯/共聚聚酯膜被用作涂布PLA聚合物的基体的情况下，该双层薄膜复合物便可以由以下方法方便地制得，该方法包括：通过多孔口模头的多重挤出，或复合层的共挤出，例如在US 3,871,947中所广泛描述的，接下来是通过在一个或多个方向上进行拉伸的分子取向，以及热定型。称为单通道共挤出的用于共挤出的方便的方法和设备描述在US 4,165,210和GB 1,115,007中。该方法包括从两个不同的挤出机中同时挤出第一和第二聚酯料流，在通向挤出模头的集合管的筒体中使两股料流整合到一起，并将两种聚酯在流线型流动的条件下一起挤出通过模头，以便两种聚酯占据流体显然不同的区域而不发生相互混合，从而制得薄膜复合材料。
薄膜复合材料的聚对苯二甲酸乙二酯部分的双轴取向通常在约78至125℃的温度范围内在两个互相垂直的方向、通过顺次拉伸复合材料进行。通常，用来拉伸复合材料的条件的作用可以是使第一热结合层部分结晶，在这种情况下，优选在高于第一热结合层的结晶熔融温度、但低于聚对苯二甲酸乙二酯部分的结晶熔融温度的温度条件下，在尺寸约束下热定型薄膜复合材料。然后，听任或促使复合材料冷却，使第一热结合层基本上为无定型，同时在PET部分中保持高结晶度。因此，优选在拉伸操作后典型地在150至250℃的温度范围内进行尺寸约束下的热定型。拉伸和热定型的传统方法在US 3,107,139中被描述。在此描述的各种类的共挤出薄膜复合材料，在底层上引入聚酯底层的共聚聚酯层都可以以名称301H商购自Wilmington，DE的DuPont Teijin Films。如上所指出的，这些膜可以涂布本发明的PLA聚合物，且在PLA涂布配制品中可以含有或不含额外的共聚聚酯。
多层密封薄膜的制备
本发明的多层薄膜可以通过用溶剂中的PLA聚合物溶液(任选还包含粘合促进剂)涂布聚合基体来制得。在本文的上下文中所用的术语“溶剂”是指用于PLA聚合物和粘合促进剂中之一或两者的挥发性载体，所得的混合物可以是乳液、微乳液或其他分散体，在严格意义上还可以是真溶液。合适的溶剂包括但不局限于水、四氢呋喃、甲乙酮、甲苯等。当水被用作溶剂时，可以用乳化剂来制备乳液或微乳液。
如果单独使用PLA聚合物，基体被涂布的一侧必须有粘合促进剂层在其上。例如，可以使用共挤出的多层(典型为两层)聚酯/共聚聚酯膜，虽然还可以使用具有溶剂涂布的共聚聚酯层的聚酯薄膜。在任一种情况下，PLA聚合物此时都可以被涂布到基体上来提供多层薄膜。
涂布可以用本领域的任何方法进行，包括例如反向计量和凹版印刷法(reverse mertering and gravure)。本发明人发现，通过采用溶液涂布方法，就能够制备具有相对薄(例如，0.5-20微米)的热封层的多层薄膜。这种相对薄的层通常很难通过其他方法如挤出或共挤出涂布获得。因此，与通过其他方法例如层压或挤出涂布制备的结构相比，本发明可获得具有高的面积与重量比的多层薄膜。而且，较薄的热封层还可以提供更容易除去(可剥离)的密封体，这在一些应用例如密封包装的食品容器中是有益的。
多层密封膜的应用
如上所述，本发明的薄膜在密封容器例如PLA盘中作为容器的盖膜有特别应用。典型地，这种盘或其他器皿可以由聚乳酸均聚物制成，但是，也可以根据本发明来使用乳酸与共聚单体的共聚物(包括但不局限于上文提到的与在热封层中所用的PLA聚合物有关的那些)。然而，其他种类的容器也可以用这些薄膜密封，根据本发明这样的应用也是可以预期的。基本上任何具有开口的器皿都可以用本发明的多层薄膜在薄膜具有热封层的一侧上密封。
实施例
样品测试
以下测试方法被用在以下的实施例中：
(i)如下测量盘的热封强度。在200°F、35psi的压力下在热封机上热封0.5秒，使薄膜通过热封层被密封到一片PLA盘制得的托盘上。密封薄膜的条(25mm宽)和盘被切割成与密封体成90°，拉开密封体需要的负载用以0.25m·min-1的十字头速度运转的Instron测量。以上过程通常重复4次，计算5个结果的平均值。
(ii)复合膜自身与自身的热封强度通过在35psi的压力下将薄膜的两个样品的热封层置于一起并在230°F加热0.5秒来测量。将密封薄膜冷却到室温，并将密封复合材料切成25mm宽的条。热封强度通过以0.25m·min-1的恒速度测量线性张力下剥离薄膜的层时，每单位宽度的密封体所需要的力来确定。
(iii)结晶度百分数可以通过差示扫描量热法测量。从薄膜取下5mg样品，在Perkin Elmer DSC7B差示扫描量热仪上以80℃/min的速度从0℃加热到300℃。结晶度百分数假设在所有样品中存在结晶。
样品制备
涂布溶液#1的制备：将99克的PLA406D(低结晶度D，L-聚乳酸聚合物，从Minnetonka，MN的NatureWorks LLC购得)、0.5克的KEMAMIDEE防粘剂(从Witco购得)和SYLOID 244增滑剂(从W.R.Grace购得)添加到500克的四氢呋喃(THF)中。混合物搅拌30分钟，制成涂布溶液#1。
涂布溶液#2的制备：将69克PLA 406D、30克壬二酸/对苯二甲酸/乙二醇(45/55/100摩尔当量)的共聚聚酯、0.5克的KEMAMIDE E和0.5克SYLOID 244添加到400克THF中。混合物搅拌30分钟，制成涂布溶液#2。
样品1：通过前辊式辊涂法将涂布溶液#1涂布在92厚度规格(gauge)的MYLAR E膜(双轴取向的聚对苯二甲酸乙二酯膜，由DuPont TeijinFilms制得)上。调节辊子的间隙以使干涂层重量达到8g/m2。将湿涂层在100℃干燥1分钟。
样品2：通过前辊式辊涂法将涂布溶液#1涂布在MYLAR 100OL薄膜(具有共聚聚酯层的双轴取向的聚对苯二甲酸乙二酯薄膜，由DuPontTeijin Films制造)上。调节辊子的间隙以使干涂层重量达到8g/m2。将湿涂层在100℃干燥1分钟。
样品3：通过前辊式辊涂法将涂布溶液#2涂布在92厚度规格的由DuPont Teijin Films制得的MYLAR E薄膜上。调节辊子的间隙以使干涂层重量达到8g/m2。将湿涂层在100℃干燥1分钟。
样品4：通过前辊式辊涂法将涂布溶液#2涂布在由DuPont TeijinFilms制得的MYLAR 100OL膜上。调节辊子的间隙以使干涂层重量达到8g/m2。将湿涂层在100℃干燥1分钟。
分别根据上面的方法(i)和(ii)，将样品1-4中制备的薄膜热封到PLA盘制得的托盘上，以及使自身热封。得到的热封强度见下表中所示，以g/in报告。
  样品1   样品2   样品3   样品4
  方法(i)*   ＜100   450   475   850
  方法(ii)   ＜200   420   320   600
*在样品用Instron剥离之前用手开始密封。
样品1和2的比较显示，仅包含PLA的热封层在具有共聚聚酯的中间层的底膜(样品2)上比在没有中间共聚聚酯层的底膜(样品1)上具有更好的热封性能。此外，比较样品1和3可以看出，在没有中间共聚聚酯层的情况下，将共聚聚酯添加到PLA热封层(样品3)比仅包含PLA的热封层(样品1)具有更好的热封强度。最后，将样品4与样品2或样品3进行比较可以看出，在PLA热封层中包括共聚聚酯并还作为中间层时，它比其自身的任何一个都有更好的性能。
虽然参考具体的实施方案在此解释和描述了本发明，但是本发明不希望局限于所示的细节。相反，在不背离本发明的情况下，可以在权利要求的等效的范畴和范围内在细节上做各种修改。

Claims (33)

1、一种多层薄膜，其包括：
a)包含聚合物底层的基体；和
b)在所述基体上的包含PLA聚合物的热封层；
其中所述热封层还包括分散在热封层中的粘合促进剂，或者，其中所述基体还包括在聚合物底层和热封层之间并与之相邻、在所述聚合物底层表面上的层中的粘合促进剂。
2、权利要求1的多层薄膜，其中所述聚合物底层包含聚对苯二甲酸乙二酯。
3、权利要求1的多层薄膜，其中所述基体包括所述粘合促进剂层，其中所述粘合促进剂层包括共聚聚酯。
4、权利要求1的多层薄膜，其中所述粘合促进剂是共聚聚酯，该共聚聚酯分散在热封层中。
5、权利要求4的多层薄膜，其中共聚聚酯的量是共聚聚酯与PLA聚合物总重的10至90重量％。
6、权利要求4的多层薄膜，其中所述热封层包括聚合物的分散相和具有不同组成的聚合物的连续相，其中所述粘合促进剂构成多于50重量％的一种所述相，PLA聚合物构成多于50重量％的另一种所述相。
7、权利要求1的多层薄膜，其中所述热封层的厚度为0.5至20微米。
8、权利要求1的多层薄膜，其中所述热封层的厚度为2.0至10微米。
9、权利要求1的多层薄膜，其中所述聚酯层包括双轴取向的聚对苯二甲酸乙二酯。
10、权利要求1的多层薄膜，其中PLA聚合物是PLA均聚物或共聚物。
11、权利要求1的多层薄膜，其中PLA聚合物是至多50％结晶的。
12、权利要求1的多层薄膜，其中PLA聚合物是无定型的。
13、权利要求1的多层薄膜，其还包括分散在热封层中或位于与基体相对的热封层表面上的防雾剂。
14、一种密封的容器，其包括具有开口的器皿，其中所述开口用权利要求1的多层薄膜在具有热封层的薄膜一侧上将其密封。
15、权利要求14的密封容器，其中所述器皿由聚乳酸均聚物或共聚物形成。
16、一种制备多层薄膜的方法，其包括以下步骤：
a)将涂布液涂敷到包括聚合物底层的基体上，所述涂布液包括溶剂和PLA聚合物，其中涂布液还包括粘合促进剂，或者基体还包括在所述聚合物底层表面上的层中的粘合促进剂，以接收涂布液；和
b)除去溶剂，形成包括PLA聚合物的热封层。
17、权利要求16的方法，其中所述基体在聚合物底层表面上的层中包括所述粘合促进剂，涂敷涂布液的步骤包括将涂布液涂敷到具有粘合促进剂的表面。
18、权利要求17的方法，其中所述粘合促进剂包括共聚聚酯。
19、权利要求16的方法，其中所述聚合物底层包括聚对苯二甲酸乙二酯层。
20、权利要求19的方法，其中所述聚合物底层包括双轴取向的聚对苯二甲酸乙二酯层。
21、权利要求16的方法，其中所述涂布液包括所述粘合促进剂。
22、权利要求21的方法，其中所述粘合促进剂包括共聚聚酯。
23、权利要求16的方法，其中所述热封层的厚度为0.5至20微米。
24、权利要求16的方法，其中所述热封层的厚度为2.0至10微米。
25、权利要求18的方法，其中所述共聚聚酯是热封性共聚聚酯。
26、权利要求16的方法，其中PLA聚合物是至多50％结晶的。
27、权利要求16的方法，其中PLA聚合物是无定型的。
28、权利要求16的方法，其中PLA聚合物是PLA均聚物或共聚物。
29、权利要求16的方法，其中所述涂布液还包括防雾剂。
30、权利要求16的方法，其还包括步骤b)之后将防雾剂涂敷到热封层上的步骤c)。
31、一种通过权利要求16的方法制备的多层薄膜。
32、一种涂布组合物，其包含PLA聚合物、共聚聚酯和溶剂。
33、权利要求32的涂布组合物，其中所述共聚聚酯的量是共聚聚酯与PLA聚合物总重的10至90重量％。
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CN103153619B (zh) * 2010-09-14 2015-11-25 杜邦泰吉恩胶卷美国有限公司 可热成型的共聚多酯层合物
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CN106459456B (zh) * 2014-03-26 2019-07-23 波士胶股份有限公司 基于溶剂的低温热密封涂层
CN107709181A (zh) * 2015-05-21 2018-02-16 金达胶片美国有限责任公司 层压膜
CN114007863A (zh) * 2019-06-26 2022-02-01 伊士曼化工公司 用于可折叠显示器的多层聚合物缓冲膜
CN114867604A (zh) * 2019-12-18 2022-08-05 凸版印刷株式会社 层叠体

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