CN101511578A - 各向异性泡沫-薄膜复合结构 - Google Patents

各向异性泡沫-薄膜复合结构 Download PDF

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CN101511578A
CN101511578A CNA200780032984XA CN200780032984A CN101511578A CN 101511578 A CN101511578 A CN 101511578A CN A200780032984X A CNA200780032984X A CN A200780032984XA CN 200780032984 A CN200780032984 A CN 200780032984A CN 101511578 A CN101511578 A CN 101511578A
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structure according
froth bed
layer
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M·A·巴里耶
D·布兰德
M·H·马佐尔
E·贝尔
J·杜利
J·A·加西亚
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Dow Global Technologies LLC
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Abstract

与除了至少一个泡沫层的泡孔具有各向异性取向外，在所有方面均相同的泡沫－薄膜复合结构相比较，其中至少一个泡沫层的泡孔具有各向异性取向的多层泡沫－薄膜复合结构显示了至少一种提高的韧性、抗撕裂性和抗刺穿性。

Description

各向异性泡沫-薄膜复合结构
技术领域
本发明涉及多层结构。一方面，本发明涉及泡沫-薄膜多层结构，另一方面，本发明涉及其中泡沫层包含各向异性泡孔(anisotropic cell)的泡沫-薄膜多层结构。再一方面，本发明涉及制备该结构的方法，以及还在另一方面，本发明涉及该结构的用途。
背景技术
多层泡沫-薄膜复合结构是公知的，例如美国专利3,557,265和5,215,691中所述的结构。可以通过各种方法制备这些结构，包括层压和共挤出，在各种应用中的使用，包括信封、装货袋、立式袋、标签、热成型包装和显窃启包装(tamper-evident packaging)。然而，这些结构的各种性能还有改进的空间，尤其是韧性、抗撕裂性和抗刺穿性。
发明内容
在本发明的一个具体实施方案中，与除了至少一个泡沫层的泡孔具有各向异性取向外，在所有方面均相同的泡沫-薄膜复合结构相比较，其中至少一个泡沫层的泡孔具有各向异性取向的多层泡沫-薄膜复合结构显示了至少一种提高的韧性、抗撕裂性和抗刺穿性。在本发明的另一个具体实施方案中，以单、双或多向方式使至少一个泡沫层具有各向异性泡孔取向，例如分别通过拉伸、拉幅机或吹泡、或热成型。还在本发明的另一个具体实施方案中，在包装应用中使用多层泡沫-薄膜复合结构。
优选具体实施方案的描述
“各向异性”、“各向异性取向”、“各向异性泡孔取向”及类似术语是指多层泡沫-薄膜复合结构的泡沫层中的典型泡孔具有不对称的形状，典型地是指在一个维上比在其它维上较大的形状。在泡孔取向之后，泡孔各向异性比(宽/厚或x/y)典型地为约2：1至约10：1，优选为约3：1至约5：1。
本发明的多层泡沫-薄膜复合结构典型地包含至少两层的A/B结构，优选为5至约300层，更优选为约15至约75层。结构的外层包含泡沫或者薄膜，或者一层是薄膜，另一层是泡沫。每层相互邻接，并与最接近的层结合在一起，优选薄膜层和泡沫层交替。薄膜层包含固态的、非膨胀的热塑性树脂材料，所述树脂材料典型地具有约0.10微米(μm)至约100微米，优选为约0.5微米至约50微米，更优选为约1微米至约30微米的厚度。泡沫层包含膨胀的蜂窝状热塑性树脂泡沫材料，所述树脂泡沫材料典型地具有约10微米至约1,000微米，优选为约50微米至约500微米，更优选为约75微米至约300微米的厚度。层彼此之间通常平行相互交叉，即相互交织。本发明的多层泡沫-薄膜复合结构的横截面厚度取决于层数和挤出设备的厚度容量，但是典型地厚度范围为约10微米至约25毫米(mm)，优选为约10微米至约5毫米，更优选为约100微米至约2毫米。泡沫的泡孔可以是开放或封闭的。
可以通过多种方法制备本发明的多层泡沫-薄膜复合结构，例如美国专利3,557,265和5,202,074披露的分配(feedblock)和层倍增(layermultiplication)技术，如Dooley，J.和Tung，H.，Co-extrusion，Encyclopediaof Polymer Science and Technology，John Wiley & Sons，Inc.，New York(2002)披露的顺序层加法(sequential layering)，或如美国专利3,884,606披露的直接分配法。在一个优选的具体实施方案中，共挤出至少两个相同或不类似的热塑性材料的料流来制备所述结构。本领域熟知两种或两种以上合成树脂材料的共挤出或同时挤出，且它们已经被用于制备包含许多层(例如50、100或几百层)的板或薄膜。在美国专利3,565,985、3,557,265和3,884,606中阐述了该方法。
共挤出被广泛地描述为制备相互交叉的不同合成树脂材料的复合流(composite stream)的方法，在该方法中，至少一种材料包含热塑性树脂组合物，该热塑性树脂组合物含有至少一种发泡剂或膨胀剂，该方法包括至少提供热塑化的(heat-plastified)合成树脂材料的第一料流(first stream)和热塑化的热塑性材料的第二料流(second stream)，两者都不包含发泡剂或膨胀剂，在足以基本上抑制发泡剂活性的压力下，将至少一种发泡剂添加到至少热塑化的料流中，分别将每个料流分成多个第一分料流(first substream)和多个第二分料流(second substream)，合并分料流以形成具有相互交叉的第一分料流和第二分料流的复合流，并使该料流形成所需的具有至少一个主表面的结构，其中复合流的层通常平行于所需结构的主表面。在层倍增-结合方法中，例如美国专利3,557,265中的图2-4，6和7所示的分配器(feedblock)和模具组件，热塑化的热塑性材料的各个料流分成多个分料流和分料流合并成相互交叉层的复合流受到影响。
拉伸多层泡沫-薄膜复合结构(单、双或多轴)，同时在熔融态中获得宏观的泡孔取向。拉伸的例子包括，但不限于，(i)在槽模(slot die)与薄膜或铸板辊之间的单轴拉伸，(ii)或用于自由表面吹泡(双轴)的型坯吹胀(parison inflation)，或吹胀进入模具(吹膜，多轴)，(iii)拉幅机拉伸，同时或顺序双轴，和(iv)管内真空成型(多轴)。典型的拉伸比(基于单轴拉伸方法)在约2：1至约10：1的范围内，优选在约3：1至约5：1的范围内。
对于多维(dimensioned)制品，可以重新加热多层泡沫-薄膜复合结构来影响拉伸操作。一旦拉伸或伸长，在辅助下(例如冷辊，淬灭等)或不在辅助下，通过冷却来稳定多层薄膜-泡沫复合结构，即平衡至环境温度。
在本发明的实践中，可以使用任何可形成薄膜或可被吹塑(即发泡)的大多数热塑性聚合物材料，包括但不限于，热塑性聚烯烃、脂肪族和芳族聚酯、聚氨酯和这些材料的各种掺合物。这些聚合物和其它聚合物可用作可膨胀的聚合物组合物，或薄膜成型组合物，或者同样的聚合物材料可以用作各个目的，例如，在相同的多层泡沫-薄膜复合结构中，聚苯乙烯既可以用作可膨胀的聚合物，又可以用作薄膜成型聚合物。
许多热塑性聚烯烃非常适合用于本发明的实践中，这些热塑性聚烯烃包括例如聚乙烯、聚丙烯和聚丁烯、聚氯乙烯(硬和柔韧)、聚苯乙烯、乙基纤维素、聚(氯乙烯)-偏氯乙烯、聚甲基丙烯酸甲酯等的聚烯烃。用于本发明的烯烃聚合物的具体例子包括超低密度聚乙烯(ULDPE，例如由The Dow Chemical Company(“Dow”)制备的ATTANETM乙烯/1-辛烯聚乙烯，其密度通常在约0.900至0.925之间，熔体指数(I2)通常在约0.5至10之间)，线型低密度聚乙烯(LLDPE，例如由Dow制备的DOWLEXTM乙烯/1-辛烯聚乙烯，其密度通常在约0.92至0.94之间，I2通常在约0.5至30之间)，均匀支化的、线型乙烯/α-烯烃共聚物(例如，Mitsui Chemicals America，Inc.的
Figure A200780032984D0008103746QIETU
聚合物和ExxonMobil Chemical(ExxonMobil)的EXACTTM聚合物)，均匀支化的、基本上线型乙烯/α-烯烃聚合物(例如由Dow制备的AFFINITYTM和ENGAGETM聚合物，描述于美国专利5,272,236、5,278,272和5,380,810中)，催化的线型统计烯烃共聚物(catalytic linearstatistical olefin copolymer)(例如，Dow制备的INFUSETM聚乙烯/烯烃嵌段聚合物，尤其是聚乙烯/α-烯烃嵌段聚合物，特别是聚乙烯/1-辛烯嵌段聚合物，描述于WO 2005/090425、2005/090426和2005/090427中)，高压、自由基聚合的乙烯共聚物，例如乙烯/乙酸乙烯酯(EVA)和乙烯/丙烯酸酯和乙烯/甲基丙烯酸酯聚合物(例如E.I.Du Pont duNemours & Co.(Du Pont)分别的
Figure A200780032984D00081
和聚合物)和乙烯/丙烯酸和乙烯/甲基丙烯酸(例如，Dow的PRIMACORTM EAA聚合物和Du Pont的NUCREL EMAA聚合物)，和各种聚丙烯树脂(例如，Dow制备的和
Figure A200780032984D00084
聚丙烯树脂和ExxonMobil制备的
Figure A200780032984D00085
聚丙烯树脂)。
可以使用大多数任意的已知发泡剂，包括气体材料、挥发性液体和能分解成气体和其它副产物的化学试剂。代表性的发泡剂包括，但不限于，氮气、二氧化碳、空气、氯甲烷、氯乙烷、戊烷、异戊烷、全氟甲烷、一氯三氟甲烷、二氯二氟甲烷、三氯一氟甲烷、全氟乙烷、1-氯-1，1-二氟乙烷、一氯五氟乙烷、二氯四氟乙烷、三氯三氟乙烷、全氟丙烷、一氯七氟丙烷、二氯六氟丙烷、全氟丁烷、氯化无氟丁烷、全氟环丁烷、偶氮二甲酰胺、偶氮二异丁腈、苯磺酰肼、4，4-苯酚磺酰-半卡巴肼(sulfonyl-semicarbazide)、对苯磺酰-半卡巴肼、偶氮二羧酸钡、N，N’二甲基-N，N’-二亚硝基对苯二酸酰胺和三肼基三嗪。目前，部分卤化的烃是优选的发泡剂。一般地，以每100份聚合物1至100重量份的量的发泡剂或膨胀剂，将发泡剂掺入要发泡的树脂组合物。已经发现，在薄膜成型组合物中加入少量膨胀剂，例如每100份聚合物0.1至1份膨胀剂，能够改进泡沫层和薄膜层之间的相容性和粘合性。实施该变体也能够改进膜质量。必须在足以抑制其活性的压力下，将发泡剂掺入其熔体流中，也就是说，在膨胀剂的掺入过程中和接下来的组合物加工过程中的抑制熔体流发泡，直至料流从共挤出模具挤出。一般地，该压力应为至少500psig，优选为至少1000psig。
每个泡沫层的密度典型地为约0.03克/立方厘米至约0.8克/立方厘米，优选为约0.10克/立方厘米至约0.5克/立方厘米，由ASTM D3575-93W-B测定。多层泡沫-薄膜复合结构的密度典型地为约0.05克/立方厘米至约0.9克/立方厘米，优选为约0.15克/立方厘米至约0.6克/立方厘米。
多层泡沫-薄膜复合结构可以由一个或多个皮或盖层(cap layer)组成以改进结构通过模具的流动稳定性。如果存在，每个皮层以结构总重量计可以包括大于0重量％到至多约40重量％，优选为约5重量％至约30重量％。皮层可以是非粘着的，这样制造之后可将其从结构的其它部分移除。而且，多层薄膜-泡沫复合结构可以加入一个或多个功能，例如阻气层(例如，乙烯乙烯基醇共聚物或聚偏氯乙烯的薄膜)或脱氧剂。
可以在本发明的复合材料中掺入在可膨胀聚合物组合物中常规添加的添加剂，例如催化剂或促进剂、表面活性剂、阻燃添加剂、孔隙度控制剂、抗氧化剂、着色剂、颜料、填料等。一般以常规量使用所述添加剂。在特别优选的具体实施方案中，已经发现在可挤出的聚合物组合物中，尤其是在那些不含膨胀剂或只含少量的改进性能的膨胀剂的聚合物组合物中，掺入0.1重量％至25重量％，优选1重量％至20重量％，最优选5重量％至15重量％的炭黑，得到具有增加的隔热值(insulation value)的产品。
本发明的多层泡沫-薄膜复合结构具有多种潜在用途，其比在这些应用中更常规使用的结构具有某些优势。下面是这些用途的非限定代表：
柔韧和刚性的、中密度的、可热成型板用于汽车、耐用品、器具和包装应用。与许多常规选择相比，本发明的结构经常显示较轻的质量和物理性能、拉伸性能和/或柔韧性的较好保留，这些性能对这些应用是重要的。
用于汽车、建筑物和结构、和器具应用的声质控制板和地毯衬。本发明的结构经常比软木更耐用，且可以带有装饰表面。
抗刺穿制品，例如信封、装货袋和包(例如，水泥袋)、袋、低密度膜(例如，单层屋面)和肉制品包装膜。
拉伸和挤出吹膜制得的制品。由本发明技术制得的制品比其它技术制得的类似制品经常具有较轻的质量和较好的隔热性能。
膜例如向下计量(down-gauged)(质量)的膜；可生物降解的地膜；抗撕裂的低密度收缩包装膜和防水布；抗滥用的水泡眼包装；和增加透明度的膜。
阻隔氧、水和/或化学物质的泡沫-薄膜复合材料(例如，用于食品、医药、电子包装)。
隔热和/或防弹房屋覆盖。
低介电材料，例如用于电子学上用的电线和电缆覆板和半导体板。
用于工业、汽车(泡棉胶带)和伤口护理(绷带)的高强度弹性带。
具有高撕裂强度和隔热性能的装饰标签和标签或签条。
具有抗撕裂性和触觉学(haptics)的人造皮革(例如，用于衣服和工作鞋)。
用于保护衣服的可透气的织物。
用于内壁和办公室的合成软木。
用于粘合和组装的压敏胶带。
汽车内部应用(例如，仪表盘的皮，汽车地毯，汽车内饰件(headliner)，门板、座椅织物下面的垫，按钮垫、地板垫和遮阳板)。
用于热膨胀控制系数的填充体系。
尺寸稳定的、吸湿体系。
用于工业、安全或商品运输应用的保护复合结构。
用于控制渗透的叶状结构(例如，垂直层)。
其中干扰发泡的添加剂(例如，阻燃剂、无机填料、活性包装添加剂等)位于薄膜组份中的结构。
将功能添加剂置于泡孔组份中用于功能化；例如，抗干扰指示器(tamper resistant indicator)、离子交换添加剂、脱氧剂和渗透控制剂。
塑料纸或纸板。
用于建筑物和结构应用的低密度塑料复合材料(例如，甲板、护墙板、围栏、墙面板、隔热覆板)。
具有非织造性能的弹性结构。
具有隔热性能的重量轻的、可微波的塑料容器。
瓦楞板。
隔热的低密度管或筒(加压或不加压)。
具有隔热和/或消音性能的管套。
用于门和窗密封的挤出型材和衬垫(汽车，建筑物和结构及器具应用)。
用于汽车、工业和包装(包括饮料)应用的衬垫和盖衬。
用于工业捆绑的抗撕裂带。
用于汽车、建筑物和结构应用的具有隔热和声学和减震性的加热、通风和空调管道。
在薄板和薄膜中用于改进加工性的孔径控制(cell-size control)(例如，减少管网破裂)。
薄膜层压的削割泡沫的替代。
具有改进撕裂强度的人造草皮(休闲市场)。
用于软钢技术的约束层(用于减噪和减震的金属-塑料层压材料)。
舰船内部件(例如，重量轻、防水、质软、不打滑应用)。
下面的例子用于解释本发明的某些具体实施方案。除非另有说明，所有的份和百分比均以重量计。对照例具有1x的拉伸速度；本发明实施例具有大于1x的拉伸速度。
具体实施方式
使用由两个直径0.75英寸的单螺杆挤出机组成的共挤出生产线(投料两种组分)制备具有不同程度大泡孔(macro-cellular)取向的泡沫-薄膜样品。一种组分包含化学发泡剂，其通过齿轮泵进入两层的A/B分配器和与美国专利5,202,074描述的设计相似的一系列两通道层倍增器。然后，多层的进料流直接进入横截面尺寸为7.6x0.2厘米(cm)(宽x厚)的模具。膨胀的泡沫材料挤出在配有气刀的冷铸轧辊上。改变该铸轧辊的速度以在纵向上拉伸样品和取向泡孔结构。将整个挤出速度维持恒定在大约2.3千克/小时(kg/hr)。
接下来制备挤出物，并使用体视光学显微镜表征泡孔尺寸。通过人工泡孔计数来确定纵向(长)、宽和厚方向(分别为x，y和z)上的平均泡孔尺寸，各向异性比表示为分别在x和z方向上的泡孔尺寸的比。通过平均三个正交方向上的尺寸来获得未拉伸样品的平均泡孔尺寸。根据ASTM D3575-93 W-B计算密度，通过在Instron Universal试验机上以100％/分钟的拉伸速度测试模切样品(尺寸22mm x 4.8mm x板厚)来确定拉伸性能。所有的测试在环境条件(约23C和大气压)下进行。
条件和结果报告于表1和2中。实施例1、3、5、7、10、12、15和17是对照例(每个的拉伸速度是1x)。这些其中薄膜由三层组成的实施例具有比其余实施例更高的密度。对于泡孔尺寸，Z是垂直测量，Y是横向或宽的测量，X是纵向或长的测量。如这些结果所证明，与它们的三层类似物相比，较低密度的拉伸样品在纵向上伸长显示出显著的增加，而在横向上韧性变化不明显。
Figure A200780032984D00131
Figure A200780032984D00141
Figure A200780032984D00151
尽管前述实施例相当详细地描述了本发明，但是该细节是用于说明的目的，并不用于限制如下述权利要求书所述的发明。在本申请中引用的所有美国专利和公开的专利申请并入本文作为参考。

Claims (25)

1、一种多层泡沫-薄膜复合结构，其包含至少一个薄膜层，该薄膜层与包含各向异性泡孔的至少一个泡沫层邻接。
2、根据权利要求1所述的结构，其中泡沫层的各向异性泡孔具有大于1的各向异性的长(X)/厚(Z)比。
3、根据权利要求1所述的结构，其中泡沫层的各向异性泡孔具有大于约2的各向异性的X/Z比。
4、根据权利要求1所述的结构，其包含至少三层，其中两层是外层。
5、根据权利要求4所述的结构，其中薄膜层和泡沫层交替。
6、根据权利要求5所述的结构，其中至少两层是薄膜层。
7、根据权利要求5所述的结构，其中至少两层是泡沫层。
8、根据权利要求1所述的结构，其包含至少15层，其中两层是外层。
9、根据权利要求8所述的结构，其中外层是薄膜层。
10、根据权利要求8所述的结构，其中外层是泡沫层。
11、根据权利要求1所述的结构，其中薄膜层和泡沫层的至少一层包含聚烯烃。
12、根据权利要求1所述的结构，其中薄膜层和泡沫层包含聚烯烃。
13、根据权利要求12所述的结构，其中聚烯烃是聚乙烯或聚内烯。
14、根据权利要求1所述的结构，其包含阻氧层、防水层和化学阻隔层中的至少一层。
15、一种制备多层泡沫-薄膜复合结构的方法，所述结构包含至少一个薄膜层和至少一个泡沫层，所述泡沫层包含各向异性泡孔，该方法包括共挤出泡沫-薄膜层压材料，并使该共挤出层压材料在至少一个方向上进行变形加工。
16、根据权利要求15所述的方法，其中所述变形加工包括在槽模和薄膜或铸板辊之间以预设的拉伸比拉伸该结构。
17、根据权利要求15所述的方法，其中所述变形加工包括型坯吹胀。
18、根据权利要求15所述的方法，其中所述变形加工包括拉幅机拉伸。
19、根据权利要求15所述的方法，其中所述变形加工包括管内真空成型。
20、根据权利要求16所述的方法，其中所述拉伸比为至少约2：1。
21、根据权利要求15所述的方法，其中在至少两个方向上使共挤出层压材料变形。
22、根据权利要求15所述的方法，其中在三个方向上使共挤出层压材料变形。
23、根据权利要求1所述的结构，其中泡沫层的泡孔是开放的。
24、根据权利要求1所述的结构，其中薄膜层的泡孔是封闭的。
25、与至少一个泡沫层邻接的至少一个薄膜层，其中所述泡沫层包含各向异性泡孔。
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