CN1145663C - 从全芳香的无定形的可拉伸的液晶体聚合物和非液晶体聚酯形成的层压品及其形成方法 - Google Patents
从全芳香的无定形的可拉伸的液晶体聚合物和非液晶体聚酯形成的层压品及其形成方法 Download PDFInfo
- Publication number
- CN1145663C CN1145663C CNB981245978A CN98124597A CN1145663C CN 1145663 C CN1145663 C CN 1145663C CN B981245978 A CNB981245978 A CN B981245978A CN 98124597 A CN98124597 A CN 98124597A CN 1145663 C CN1145663 C CN 1145663C
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- layer product
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- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- 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
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- B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
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Abstract
本发明提供了包括膜,片材,预型件,容器和其它制品的多层层压品,它们有至少一层全芳香的无定形的可拉伸的液晶聚合物层与至少一种非液晶热塑性聚酯层以及制造和拉伸这种多层制品的方法。该层压品适于热成型和拉伸吹塑应用并且可在低于液晶聚合物熔融态的温度下以高的总拉伸比将其拉伸而没有破裂或撕裂。可以从该层压品生产适于食品或饮料产品的容器。
Description
本发明涉及多层层压品,包括膜,片材,预型件,容器和其它制品,包括至少一层具有至少一种非液晶聚酯层的全芳香的无定形的可拉伸的液晶聚合物以及制造和拉伸这种液晶聚合物和这种多层制品的方法。在此申请中所公开的内容与同日申请的共同未决专利申请系列号08/954 377,08/954378,08/954 997和08/955 000相关。
多层层压品、容器和其它制品在工业,特别是在包装方面具有大量用途。Kirk-Othmer Encyclopedia of Chemical Technology,Third edition,Volume 10,第216页(1980),Wiley-Interscience Publication,JohnWiley&Sons,New York详述了用于制造这种制品的一般材料和方法以及它们的用途。另一重要制品例如是W.Schrenk and E.Veazey,Encyclopedia of Polymer Science and Engineering,Vol.7,106(1980)中的“膜,多层”。通常是通过注射或挤压操作共处理(coprocessing)单个聚合物或通过层压单个成型的层到一起或通过这些方法的结合制造这些制品。在此所讨论的共处理是指成型和/或接着加工至少两层聚合物材料,每层包括不同的聚合物材料。在这些应用中所用的通常的聚合物包括聚乙烯,聚丙烯,乙烯-醋酸乙烯酯共聚物,乙烯-乙烯醇共聚物,乙烯-丙烯酸甲酯共聚物,聚氯乙烯,聚1,1-二氯乙烯,聚酰胺,聚酯,聚碳酸酯,聚苯乙烯,丙烯腈共聚物及其类似物。在层压品,膜,薄片及其类似物中所希望的性能取决于目的用途,但是通常包括良好的机械性能例如可拉伸强度和抗冲强度,可加工性,耐撕裂性,气障性,隔湿性,光学性能,热稳定性和尺寸稳定性等等。
Lustig等的US专利号5,256,351和Wilhoit的US专利号5,283,128公开了从聚乙烯得到的双向拉伸热塑性膜及其制备方法。Vicik等的US专利号5,460,861还教导从聚烯烃得到的改性多层膜。Lustig等的US专利号4,911,963公开了一种从尼龙得到的定向多层膜。Shah的US专利号5,004,647描述了一种包括乙烯-乙烯醇共聚物的共挤出(coextruded)多层薄膜。
许多从各聚合物的混合物形成有用制品的方法需要对混合物的所有成分在一个或多个方向上进行拉伸,膨胀或延展,或设法变形如折叠,使起皱痕等等。可以使这种拉伸,延展或其它的变形与从熔体形成层压品或单层同时进行,或可以是接着成形操作的一部分。使用制品可能还需要变形。这些成型方法包括但不限于挤压薄膜的单轴和双轴拉伸,多层层压品的热成型,挤压或注压管状物的吹制,预型件或型坯的拉伸吹制成型,使层压品起皱痕或折叠以形成盒子,扭合膜以形成包装物等等。
通常将结合各种不同聚合物层是用于形成具有不同优良性能的多层层压品的方法,它们可以适用于不同的聚合物层,另一方面还可减少所使用的较昂贵聚合物的用量。
容器成型的许多方法需要管状物的折叠或多层结构的交叠。在这种情况下,人们希望避皱
折(wrinkle)以确保各种层保持彼此键合和避免任一层破裂或撕裂。容器成型的其它的方法需要在足以拉伸在层压品中存在的任何聚合材料的温度下均匀拉伸或膨胀多层层压品。其优点是能共处理层压品例如将其折叠,拉伸,膨胀或压缩而不破裂或撕裂或破坏任何层的整体性。
热致液晶聚合物是在熔融相为液体结晶性的(即各向异性的)聚合物。人们已经使用其它术语如“液晶”,“液晶体”和“各向异性”描述这些聚合物。认为这些聚合物的分子链平行排列。通常如此顺序排列分子的相态是指液晶态或液体结晶性材料的向列相。一般可以从沿着分子的长轴具有长(链)的,平直和十分刚性的单体制备这些聚合物。
通常,液晶聚合物(“LCPs”)具有非常令人希望的性能,如良好的耐化学性,高机械强度和对气体、潮湿和香气的良好阻挡性。但是,难于制造LCPs本身或与其它材料的热粘合制品。还难于在LCPs制成的制品上书写和印刷。LCPs比常规的聚酯更昂贵。另外的几种常用LCPs甚至在薄膜形式都不具有高的光学透明度。一般只有将其加热到加工温度范围约200℃-约320℃,优选从约220℃-约300℃,才能拉伸或变形LCPs。通常膜和瓶子的成型加工需要超过100%的伸长率。对于没有可测量熔点的无定形的LCPs,该加工温度范围是指“熔融态”。另外,在可将常规LCPs变形的温度范围内,它们具有非常低的熔融强度并且易破。从常规LCPs制得的管状不能进行没有皱折的折叠。含有一种或多种常规LCP层的膜或层压品难于进行不脱层和不爆裂的折叠。只有在拉伸前将其加热或在熔融态(此温度对于共同加工的层压品中的其它层太高),含有常规LCP层的预型件或型坯才不会在LCP层破裂或撕裂。
Ide等的US专利号4,384,016披露当具有各向异性的性能的聚合物在熔融相通过缝型模头挤出和在熔融相(即热致液晶聚合物)拉伸时,可以得到具有高轴向性的膜和片材。但是,Ide等认为这种膜或片材的横向性差可能限制它们在某些结构应用中的使用,并建议将一块单轴取向的片材以一定的角度与另外一块片材层压以得到多轴取向的片材。文献没有披露由Ide等所推荐的层状多轴取向的片材的拉伸或拉制。
另一种生产多轴取向的液晶聚合物膜的方法是由Harvey等在U.S.专利号5,288,529中所建议的,其中使轴流性液晶聚合物材料受到横的方向力使轴向流动变形,然后巩固所得到的微型结构取向以获得具有接近各向同性机械性能的液晶聚合物膜。Harvey等建议一种在挤压过程中剪切取向的方法以克服液晶聚合物膜在机械性方面的不足,所公开的膜不适于某些应用,因为作为盘管聚合物(如聚对苯二甲酸乙二醇酯)容器挤压后不能吹制或拉伸。更具体的是,所公开的包括相对直链的或微丝分子的液晶聚合物膜在挤出方向的模头中分子变成高取向的,和趋于无规的普通盘管聚合物相比流动液晶聚合物变成各向异性。因为在各向异性模头中液晶聚合物变成高度取向的,因此已揭示基本上不能在其微丝取向的横向上拉伸聚合物。
M0riya的US专利号5,534,209公开了许多液晶聚合物的物理性能对聚合物中液晶区域取向方向非常敏感。这对于线性产品如长丝和纤维是非常理想的,但是在具有平面状如带,膜,片材等等的产品中常常不希望有各向异性。Moriya还披露如Harvey等已经公开了的那些剪切取向方法,该方法的缺点是不能制造不形成小孔,裂缝和其它疵点的薄多轴取向膜。Moriya指出在熔融加工具有非常高加工粘度的热致液晶聚合物的情况下,通过剪切取向方法难于得到具有均匀光滑表面和均匀厚度的膜。这进一步提高了膜的撕裂敏感性及其对卷缩和划痕的灵敏度。
Moriya通过往在两个载体膜的相对嵌衬里表面之间的空隙中所形成的熔融区内加入热致液晶聚合物得到一种具有无规取向的液晶聚合物膜。通过在液晶聚合物的熔点或以上拉伸由液晶膜和两个载体膜形成的夹层结构可以多轴取向用Moriya的方法形成的无规取向的液晶聚合物膜。
Sumida等的US专利号5,364,669和5,405,565都公开了各种包括一层具有气障性的液晶聚合物层,一层粘合剂层和从热塑塑料如聚对苯二甲酸亚烷基(polyalkylene)酯,烯烃聚合物,酰胺纤维,聚碳酸酯和类似物形成的热塑层的复合膜。该复合膜适于作食品包装材料。Sumida等指出可以从熔融态对熔化的液晶聚合物双轴拉伸,但是应该从模头向下挤出以防止当从模头向上挤出熔化的液晶聚合物膜时出现与低熔融粘度和熔融的膜脆弱不易得到的相关问题。所提供的Sumida等的方法的实施例中,在290℃以吹胀比5.5和拉伸比6.0挤出Vectra A900(HoechstCelanese Corporation of Somerville,New Jersey的商标)全芳香液晶聚酯树脂以得到多轴取向的液晶聚合物膜。没有披露用吹塑法和拉伸吹塑法得到瓶子或罐。
人们常常希望通过热成型和/或吹塑方法从多层层压品得到成型的制品因为它们是批量生产成型制品的成本有效方法。但是,这种方法经常既不能实施也没有用于上述方法的必须被熔融拉伸的材料如全芳香的Vectra 液晶体树脂和其它可熔融加工的液晶体聚合物。因此,人们希望有一种可拉伸的液晶体聚合物,它不仅在熔融态,而且在温度高于液晶体聚合物的Tg但低于熔融态温度可被拉伸,或在低于约200℃可被拉伸。此外,人们还希望从这种包括一层这样的可拉伸的液晶体聚合物层的层压品成型层压品和制品。
共聚物或不同成分的聚合材料的混合物经常用于对所得到的共聚物或混合物提供单个成分聚合物材料本身所不具有的混合性能。例如可以建议将具有良好机械性和气障性的可熔融加工的液晶体材料与热塑性聚合材料混合以得到在较低温度下具有气障性,良好机械性和可拉伸性的共聚物或混合物。
但是,人们已经认识到所制备的这种共聚物或混合物可以具有“反协同效应”。即使使聚合物与混合物相容并形成共聚物或混合物,聚合物的混合物也比预先所希望的性能要差。这种效应的准确机理还不完全清楚,但是共聚物或混合物的性能常常接近每种单个成分聚合物至少所希望性能的结合而不是每种的最好性能。甚至当获得良好的性能时,所得到的聚合材料可能有某种缺点。
Kashimura等的U.S.专利号5,326,848公开了通过混合的共聚合反应方法生产热致液晶聚酯,其中将聚酯如聚对苯二甲酸乙二醇酯(PET),聚萘酸乙二醇酯(PEN),或PET和PEN的共聚物与基于羟基萘甲酸和羟基苯甲酸单元的或单独基于羟基萘甲酸单元的常规液晶聚酯结构单元混合。Kashimura等打算得到具有良好可成型性又有气障性的层压品并公开了具有液晶聚酯组合物层与其它聚合物层如聚酯,聚烯烃和聚酰胺的层压品以生产层压的容器如杯子和瓶子。披露了通过深拉未拉伸的片材,聚酯组合物能制备成形,它包括PET与基于羟基萘甲酸和羟基苯甲酸的单元混合。但是所披露的这种深拉组合物的气障性有时可能比通过所公开的其它组合物(没披露适于深拉)得到的气障性差。在Kashimura等所公开的所有液晶聚酯组合物中,在液晶体聚酯中必须存在至少15%摩尔的脂肪二羟基(dihydroxy)成分。尽管公开了瓶子的成型和吹塑,但是既没有说明也没有公开成型瓶子或吹塑的拉伸比。已经公开了以3×3的比率双轴拉伸加热到100℃-240℃的组合物的膜。
由Kashimura等所公开的生产液晶体聚酯组合物的方法包括一种聚合物如PET,PEN或这些聚酯的共聚物与基于羟基萘甲酸和羟基苯甲酸或单独基于羟基萘甲酸的单体反应。这种混合聚合物/单体共聚反应需要至少15%摩尔液晶体聚酯组合物是脂肪二羟基成分。在与液晶聚酯单体部分混合前,这种脂肪成分必须与对苯二甲酸和/或萘二羧酸成分混合,因为它阻止形成所希望的混合聚合物。Kashimura等所公开的生产这种LCPs的方法是非常不稳定的,因此,难于开发成可获得实际数量的液晶聚合物组合物的大规模商业化的方法。
人们已经推荐了包括LCP层的可拉伸多层层压品和制品。例如JP5,177,797披露可以从包括热塑性树脂和LCP层的层压品制备多层容器。其它类似性质和有益的披露包括在例如JP 5,177,796A;JP1,199,841A;JP 5,169,605A;和WO 9,627,492A中。
1996年12月5日申请的待审查的系列号08/761,042的申请公开了包括在中间的LCP层和在外面的可剥离的热塑层的层压品。1996年12月5日申请的待审查的系列号08/761,109的申请公开了包括在中间的染色的LCP层和在外面的不可剥离热塑层的极化的(polarizer)层压品。同一日期申请的待审查系列号08/954 377,08/954 378,08/954 997的申请公开了用于制造多层的粘合剂,多层中至少一层来自LCP。
人们希望生产可拉伸的LCPs,还希望生产包括与一层或多层非-LCP层结合的一层或多层LCP层的多层层压品或制品以得到具有所有各层的最好性能的多层结构,如具有良好气障性,机械性,光性能和相对低成本的多层结构。人们希望这种液晶聚合物和多层结构不仅在LCP组合物处于熔融态的温度可拉伸,而且在较低的温度即在温度高于LCP组合物的Tg但低于LCP组合物处于熔融态的温度范围下可拉伸。人们希望能够对这种LCP或LCP层压品拉伸一次以上得到高拉伸比。人们希望通过可预知的,稳定的能用于大规模的商业生产的方法来生产一种用于这种层压品的LCP。
本发明提供包括全芳香的,无定形的,低温可拉伸的液晶体聚合物和非液晶体热塑聚酯的单层以及多层层压品。下面所描述的用于本发明的液晶体聚合物可以从适当的单体部分经济地以大规模的商业方法重复地生产并具有良好的阻挡性。用于本发明的液晶聚合物或聚合物不仅在其熔融态可被拉伸,而且在温度高于液晶体聚合物组合物的Tg但低于约200℃也可被拉伸。可以对它们进行一次以上的拉伸,和对其进行整面积的拉伸,拉伸比大于10,或更优选大于15而没有破裂和/或撕裂。
本发明的层压品用于成型具有适用于许多领域应用特点的多层膜,片材,预型件和型坯以及其它制品,这些领域包括例如食品,化妆品,化学和工业包装。甚至当以拉伸比大于15进行整面积拉伸时,本发明的多层层压品在层压片的任何一层上都没有破裂和/或撕裂。
本发明还提供制备这种包括膜,片材,预型件或型坯或其它制品的层压品的方法。
本发明还提供从液晶体聚合物组合物与非液晶体热塑聚酯的层压片得到的有用制品。
现在人们已经可以从至少一层可拉伸的,全芳香的无定形或“玻璃态”LCPs和至少一层非液晶体聚酯制备包括膜,片材,预型件和型坯的多层层压品容器以及其它类似制品(在下文中通称“制品”)。还可以制备用于本发明的可拉伸LCP的单层。
本发明的多层层压品包括至少一种全芳香的无定形可拉伸的液晶体聚合物层和至少一种热塑的非液晶体聚酯层。可在低于液晶体聚合物(“LCP”)熔融态的温度对液晶体聚合物层和从本发明的液晶体聚合物层制备的层压品进行拉伸。可从下面所描述的液晶体聚合物得到液晶体聚合物层。本发明的LCP层在低于其熔融态的温度是可拉伸的,不需要加入大量(substantial amounts)的非LCP热塑聚合物,填料或添加剂。但是,可以加入一定量的非LCP热塑聚合物,填料或添加剂而对LCP层或本发明层压品的阻挡性或可拉伸性没有不利的影响。加入典型量的高达总量的10%摩尔的非LCP热塑聚合物,填料或添加剂,和包括至少约LCP层的90%摩尔的适于本发明的LCP。在本发明的另一实验方案中,液晶体聚合物层基本包括液晶体聚合物。该液晶体聚合物是每个单体单元为全芳香的,即液晶体聚合物是自如下面进一步所描述的没有脂肪成分的单体衍生的。
在差热扫描量热法(DSC)分析中液晶体聚合物是无定形的,即具有玻璃化转变温度(Tg)但没有熔点转变(Tm)。相反,在DSC分析中半结晶性液晶聚合物既具有Tg又具有Tm。
用于本发明的液晶体聚合物组合物具有加工温度范围,在此温度中组合物描述为熔融态,其范围为约200℃-约320℃,或更优选从约220℃-约300℃。液晶体聚合物组合物不仅在熔融态可被拉伸,而且在低于熔融温度和高于液晶体聚合物组合物的Tg温度可被拉伸。在本发明中以整面积的拉伸比至少为约10,更优选至少为约15对液晶体聚合物组合物进行拉伸,在层压品的任何层都没有任何破裂或撕裂的出现。
在此所描述的用于多层制品的液晶体聚合物是具有相对线性结构的全芳香的聚合物,它在熔融相具有液晶体行为。它们包括但是不限于全芳香的无定形的聚酯或全芳香的无定形的聚酯酰胺。在本发明的实验方案中,液晶体聚合物优选包括如U.S.专利5,672,296所描述的重复单元,(在此将其全部引作参考),相应的通式如下:
-[P1]m-[P2]n-[P3]q-其中P1是芳香的羟基羧酸或芳香的氨基羧酸;P2是芳香的二羧酸;P3是酚的化合物;m,n和q代表各个单体的摩尔百分含量,范围一般每个从5-70%。m优选的范围约5-40%,n是约5-40%和q是约5-40%。除了P1,P2和p3外,另外的单体部分如第二种芳香羟基羧酸部分或一种芳香氨基羧酸部分-[P4]r-和二酚的部分-[P5]S可以是聚合物重复单元部分,其中r是约5-20%摩尔,s是约5-20%摩尔。P4不同于P1,P5不同于P3。还可以有另外的单体,如苯基氢醌,甲基氢醌和类似物。在上述的通式中,单体P1和P4选自由4-羟基苯甲酸,2-羟基-6-萘甲酸,4-氨基苯甲酸,和4-羧基-4’-羟基-1,1’-联苯基组成的组。优选4-羟基苯甲酸。P2可以是对苯二甲酸,间苯二甲酸,邻苯二甲酸,2-苯基对苯二甲酸,1,2-萘二羧酸1,4-萘二羧酸,2,6-萘二羧酸和4,4’-联苯基二羧酸;优选对苯二甲酸。P3选自由间苯二酚,氢醌,甲基氢醌,苯基氢醌,儿茶酚和4,4’-二羟基联苯基组成的组;优选4,4’-二羟基联苯基。P5是选自间苯二酚,氢醌,儿茶酚,4,4’-二羟基联苯基和双酚A的二酚。
在本发明的优选试验方案中,液晶体聚合物更优选包括全芳香的包括下面的五个单体单元的热致液晶聚酯:4-羟基苯甲酸,6-羟基-2-萘甲酸,对苯二甲酸,4,4’-二羟基联苯基和间苯二酚,摩尔比分别为30∶30∶20∶10∶10(下文称为COTBPR)。在Shen等的U.S.专利号5,656,714中公开了COTBPR,在此引入其全部作为参考。尽管特别地优选,但是COTBPR只是许多在此揭示的可以在本发明实施中适用的各种全芳香的无定形可拉伸的液晶体聚酯组合物中的一种。Shen等还公开了在本发明实施中不适用的半结晶性全芳香液晶体组合物。在前述的U.S.专利号5,672,296的表I中列出了既无定形又半结晶性组合物的例子。
本发明的多层结构包括至少一层上面所描述的全芳香的无定形可拉伸的LCP。另外的一层或几层可以包括非液晶体聚酯。如上述所讨论的,热致液晶体聚酯是在熔融相是液晶体的(即各向异性)聚合物。非液晶体聚酯被定义为在熔融相不是液晶体的聚合物。换句话说,它们在熔融相是各向同性的。用于制备本发明的多层结构的非液晶体聚酯的例子包括但不限于聚对苯二甲酸乙二醇酯,聚间苯二甲酸乙二醇酯,聚2,6-萘乙二醇酯(polyethylene-2,6-naphthalate),聚对苯二甲酸丁二醇酯,聚对苯二甲酸丙二醇酯,共聚酯其中二酸成分可以是对苯二甲酸和其衍生物,间苯二甲酸和其衍生物,萘二羧酸的1,2-,1,3-,1,4-,1,5-1,6-,1,7-,1,8-,2,3-2,4-,2,5-,2,6-,2,7-,2,8-异构体和其衍生物,4,4’-联苯基二羧酸和其衍生物,4,4’-联苯基醚二羧酸和其衍生物,1,2-二苯乙烯二羧酸和其衍生物,5-12个碳原子的线性与单和双环脂肪二羧酸和其衍生物,共聚酯其中二醇成分可以是2-1 2个碳原子的线性脂肪二醇和其衍生物,2-甲基丙二醇,2,2’-二甲基丙二醇,环己二醇,环己基二甲醇,1,3-二(2-羟基乙氧基)苯和其衍生物,1,4-二(2-羟基乙氧基)苯和其衍生物,二(4-β-羟基乙氧基苯基)砜和其衍生物,二乙二醇,聚乙二醇,聚丙二醇,聚亚丁基二醇(polytetramethylene glycol),以及自多羟基醇如甘油三羟甲基丙烷(trimethylolpropane)三乙基丙烷或季戊四醇(在一定量的范围内,聚酯的熔融加工不受影响)衍生的结构单元,上述聚酯和共聚酯组合物的混合物,可再生的(post consumer recycle)PET以及它们的混合物。由于PET非常有效,因此优选PET。在本发明的多层层压品中,非液晶体聚酯可以包括选自由对苯二甲酸,间苯二甲酸和萘二羧部分组成的组的单体残基和它们的混合物。非液晶体聚酯还可以包括选自由乙二醇,丙二醇和丁二醇部分组成的组的单体残基和它们的混合物。
包括LCPs和非聚酯热塑性物质如聚烯烃的层压品和其它制品也是人们所希望的,并且是在同一日期申请的待审查专利申请系列号08/955 000中的主题。
本发明的液晶体聚合物层和多层层压品在各种温度下,在轴向(“MD”)和横向(“TD”)都具有良好的拉伸性。可在任一单MD或TD方向,或双轴顺序地或同时对其进行拉伸或将其拉伸或在模中膨胀成型。本发明的层压品具有良好的机械性,光学和阻挡性。通常不需要粘合剂粘合层压品的各层。但是,如果有人希望,也可以将上述同一日期申请的待审查专利申请所描述的粘合剂用于这种应用。还可以以相同方法将这种粘合剂作为另外的层共挤压。
在本发明的实施方案中还可以使用几种不同的方法来制备本发明的LCP层或可以包括二,三,四,五或更多层的本发明的多层层压品。可以按照所希望的应用和所用的装置选择在层压品中各层的顺序以及在层压品中内层和外层的性质。这些变化是本领域技术人员公知的。层压品可以另外含有其它的可选择的层如热密封层,卫生当局许可的食品接触层,粘合剂层,着色层,防紫外线层,除氧层和含有回收物料或循环材料的层。还可以以上面所描述的相同方法共挤压这些层或接着分开加入这些层。另外,可以将包括含有LCP的共挤压层的一层或多层挤压敷到如包括铝箔,纸板或钢的其它层上。
通常,成型全芳香的,无定形的,低温可拉伸的液晶聚合物的层的方法可以是适用的任何加工热致LCP的方法。这些成型LCP层的方法包括但不限于,注塑,挤压,压缩成型或覆盖到基质上。在本发明的优选实施方案中,在两个外部保护层(稍后去掉)之间共挤压LCP中心层以形成薄的、光滑的LCP单层。用这种方法可以形成0.5密耳薄的LCP层。
成型包括至少一层用于本发明的LCP层和至少一层非液晶体聚酯层的层压品的方法可以是适用的任何结合两层或多层热塑性聚合物以形成层压品的方法。常规的三种成型层压品的方法是典型的方法不是形成层压品的可能方法的穷举。第一种是在固化前即其都在熔融态时使两个聚合物层结合。挤压方法如给料(feedblock)共挤压或多种(multi-manifold)共挤压是这种方法的典型方法,都是形成按照本发明的层压品可接受的方法。另外的一种是使未固化的即熔融聚合物层与固化的聚合物层结合。如挤压覆盖和挤压层压的方法属于这一类,并且适于形成本发明的层压品。使固化的层结合是形成层压品的第三种方法,层压和某些覆盖方法适于以这种方式形成本发明的层压品。
在一个典型的方法中,使用常规的给料共挤压方法共挤压适于发明的LCP和适合的非液晶聚酯以使聚合物物流正对模头出口结合。聚合物物流接合在一起,而它们仍高于熔点,在模头的出口得到多层膜。还可以以平面状,管状或其它构型挤出本发明的多层层压品。另外,可以在狭缝或其它开口共挤压管状层压品以形成平面共挤压物。可以在挤压过程中,挤压后,或既在挤压过程中又在挤压后拉伸本发明的多层层压品。还可以通过螺旋绕组从本发明的多层层压品成型管状多层层压品。其它适用的方法如压缩或注塑也可以用于生产本发明的包括膜,片材,预型件,型坯和其它制品的层压品。
用适当的方法可以将多层结构成型为制品。LCP层和含有LCP的本发明多层层压品具有适于热成型,吹塑和其它用加热和拉伸能大量生产成型制品方法的理想性能。这种方法是本领域技术人员公知的。在James L.Throne的著作“Thermoforming”(Hanser Publishers,NewYork,1987)中描述了可以将膜或片材成型为有用的制品的各种技术,在此引入作为参考。类似的是,如果以管或型坯的形式共挤压含有LCP的本发明层压品,那么这些非常适于吹塑。在Donald V.Rosato和Dominick V.Rosato编辑的“Blow Mol ding Handbook”(HanserPublishers,1988)上描述了各种的吹塑技术如挤压吹塑,注射吹塑,拉伸吹塑等等。用本领域技术人员公知的注塑或共注塑还可以生产适于各种吹塑方法的型坯。另外,用这些方法的结合可以成型容器,例如挤压含有LCP层的多层型坯,挤压吹塑该型坯以形成成型嵌衬,注塑聚酯如聚对苯二甲酸乙二醇酯或类似物,围绕嵌衬的外面形成预型件,和最后拉伸吹塑预型件以形成瓶子,罐或其它容器。另外,通过热成型平面板可以生产多层嵌衬。在Slat等的U.S.专利号5,443,766和5,464,106中描述了这些嵌衬成型方法,在此引入其全部公开作参考。这些拉伸吹制容器用于各种包装应用如食品,饮料,化妆品,化学和工业产品。
在拉伸LCP层或包括至少一层按照本发明的LCP的多层层压品的方法中,形成LCP层或包括至少一层全芳香的无定形的可拉伸的液晶体聚合物层和至少一层热塑的,非液晶体的聚酯层的多层层压品。在温度低于液晶体聚合物的熔融温度以及温度在液晶体聚合物的熔融态范围内的温度可拉伸多层层压品。在按照本发明的方法中,在温度高于Tg和低于液晶体聚合物的熔融态温度可以对多层层压品在拉伸之前加热。在本发明的方法中可用各种热成型方法拉伸多层层压品,热成型方法包括但不限于真空成型,模塞热成型(plug assist thermoforming),压塑和类似方法。通过共挤压各个层或分别形成各层和将它们交叠在一起,或通过任何其它可接受的形成层压品的方法可形成本发明的多层层压品。
通过热成型将多层层压品拉伸为具有最内表面和最外表面的形状。另外,然后将热成型的层压品放在模中,将热塑性材料注入到模中以形成与热成型的层压品的最外表面接触的外层。
在本发明的另一实施方案中,通过单个的或一起涂敷(coating)到基质上可形成液晶体聚合物层和非液晶体聚酯层。该涂敷方法可以是挤压涂敷,分散涂敷,溶剂涂敷或任何其它的可接受的涂敷方法。可以将多层层压品以涂层形式施于基质如纸板,铝或钢板上。接着将基质拉伸或变形以形成包装,容器或其它的涂敷的制品。
在本发明的另外一实施方案中,本发明的多层层压品可以是用于吹塑的可拉伸的多层预型件形式。按照本发明生产这种用于吹塑的可拉伸的多层预型件的方法包括形成具有一内表面,一外表面,一开端和一反端(opposite),和包括热塑性非液晶体聚酯的第一层的步骤。也形成具有一内表面,一外表面,一开端和一反端(opposite),的第二层。第二层包括全芳香的无定形的可拉伸的液晶体聚合物。在温度低于液晶体聚合物熔融态温度预型件是可拉伸的,一层的内表面与另一层的外表面接触,两层的开端和封端是一致的。通过挤压或注塑,或通过任何其它的适于生产本发明的多层可拉伸预型件的方法形成预型件层。用例如吹塑法,拉伸吹塑法,双轴拉伸吹塑法和类似的方法可将本发明的可拉伸的多层预型件在模内膨胀以形成容器。
另外,可在一端或两端折叠和密封以管或型坯的形式共挤压的单层或多层层压品以形成管,袋子或小包。可选择地***一或多个分散装置或孔。另外,为了形成所谓的直立(stand-up)囊以这种方法进行折叠和交叠。这种成型的制品非常适于各种包装应用,包括用于食品,饮料,化妆品,化学,农药和汽车的容器或需要用这种包装保护的各种固体制品。还可以用公知的缝合和密封或螺旋缠绕技术和类似技术从这种平面多层膜形成管状,袋子和囊。
用上述方法以及其它本领域技术人员公知的方法成型的膜,片材,层压品,杯子,浴盆,盘子,桶,瓶子,罐,袋子,囊,管状和盒子和类似物,在某些情况,当与其它已知的LCPs相比时具有一定的透明度。可选择的是用已知的技术如涂敷,印刷或一层或多层的着色等等可将制品制成半透明的或不透明的。
通过挤压涂敷一层或多层包括至少一层LCP的聚合物层到另外已经形成的基质上,也可从得到的多层结构形成有用的容器。可以从一种或多种聚合物,或从一种或多种金属层或从纤维素层如纸板或前述的各种结合形成此基质。然后通过交叠或其它变形结构和形成适当密封以封闭该结构,将这种多层结构变成容器。用这种方法成型的典型容器包括盒子或各种形状和各种尺寸的管等等,可以选择性地配置一些类型的开口设备(opening device)或分散口。这些容器广泛用于各种包装的应用,特别是用于食品和饮料的无菌包装。
此所描述的并用于形成本发明的层压品的聚合物和方法并不以任何方式限制层压品中的各种层厚。并且各层之间具有相同或不同的厚度;相应地选择设备。这种技术是本领域技术人员公知的。
多层层压品以及在此所描述的制品除了对氧气和潮湿有高的阻挡性外,还具有机械性,光学性和热性能的良好结合,以及化学稳定性和能被印刷和被装饰以使其理想地适于各种应用如食品和饮料容器,化妆品包装,药物包装,溶剂储存器,化学药品容器,煤气罐等等或用于包装各种生活消费品和工业产品。即使无定形的,全芳香的可拉伸的LCPs本身的初始费用多少有些高,但是以本发明所给的制品范围内的厚度使用能使成本有效。
为了进一步说明本发明而提供下面的实施例。但是,本发明的范围不只限于这些。
实施例1
共挤压包括三层的多层膜:将从Hoechst Trevira,a Hoechst groupcompany,Charlotte,North Carolina买到的商标牌号“T80”瓶树脂的PET树脂加到3.5英寸直径的单螺杆挤压机中,挤压机出口最后熔融温度270℃。同时将全芳香的,无定形的包括下面的五个单体单元的热致液晶聚酯:4-羟基苯甲酸,6-羟基-2-萘甲酸,对苯二甲酸,4,4’-二羟基联苯基和间苯二酚,摩尔比分别为30∶30∶20∶10∶10(COTBPR)加入到具有2英寸直径螺杆,挤压机出口最后熔融温度285℃的单螺杆挤压机中。将两个熔融物料加料到由Cloeren of Orange,Texas提供的Cloeren five-layerAABAA并流块(combining block)上。将Cloeren并流块装在EDI单缝模头(自Extrusion Die Incorporated,Chippewa Falls,Wisconsin)上。将熔融的聚合物物料递送到进料机在机中聚合物流被分开,PET分流到进料机的A道,LCP流加入进料机的B道。物料被混合,从模唇排出多层层压品。所得到的多层层压结构紧密接触到冷却辊上并在缠绕辊上收卷。在挤压加工过程中,用装在冷却辊后的β测量计连续监测挤压膜的全部厚度。生产出具有下面三层结构(从上面到下面)的多层膜:PET,6.5密耳/COTBPR,3密耳/PET,6.5密耳。
实施例2
单轴和双轴拉伸实验:在具有夹紧设备,红外加热设备和双数字传动装置的Bruckner Stretching Frame Model Karo II(自BrucknerMaschinenbau,Tittmoning,Germany)上双轴或单轴拉伸实施例1中所描述的PET/COTBPR/PET共挤压膜的七个样品。拉伸架接收横向(TD)6”×纵向(MD)6”的样品。用红外加热***加热膜样品。用红外高温计测量膜表面温度,当膜达到表I所示的设定拉伸温度时开始拉伸。表I总结了这些拉伸试验的结果。在表I中拉伸比是拉伸后膜的长度与起始长度的比。当双轴拉伸膜时,总拉伸比是TD和MD线性拉伸比的乘积。上述的PET/COTBPR/PET共挤压膜在各种温度,显示良好的单轴和双轴(在纵向(MD)和在横向(TD))的可拉伸性。例如通过在145℃单轴拉伸,在纵向可得到5×1的拉伸比,和在135℃和145℃得到3×3双轴拉伸总拉伸比为9。层间厚度均匀使各层呈极透明和美观。该膜显示良好的层与层之间的粘合。对单轴拉伸膜通过进行广角X-射线衍射测量确定分子的取向水平。按照ASTM3985和DIN53380 Part 3,使用自Mordern ControlsIncorporated,North Minneapolis,Minnesota的OxTran 100仪器,在23℃进行氧气透过的测量。
表1
批号 | 拉伸温度[℃] | 拉伸比TD MD | 总拉伸比 | 氧透过率* | |
1 | 125 | 3 | 2 | 6 | 0.195 |
2 | 135 | 3 | 2 | 6 | 0.218 |
3 | 135 | 3 | 3 | 9 | 0.211 |
4 | 145 | 3 | 3 | 9 | 0.287 |
5 | 145 | 1 | 3 | 3 | |
6 | 145 | 1 | 4 | 4 | |
7 | 145 | 1 | 5 | 5 |
*单位:cc/100平方英寸天大气压
实施例3:
单轴拉伸多层膜:将自实施例2的相同Bruckner拉伸装置用于从实施例1所用的相同可拉伸COTBPR制备的单轴拉伸样品。在多层层压品结构中COTBPR层是中心层,在COTBPR层任一面上有10密耳聚对苯二甲酸乙二醇酯-间苯二甲酸乙二醇酯共聚物层,其包括17.5%重量的间苯二甲酸单元和余量的二羧酸单元。用与实施例1所述相同的设备,以相同的方式将17.5%重量的间苯二甲酸共聚物(下文指“PETIP”)与COTBPR一起挤压。用两个不同厚度的1密耳和5密耳COTBPR作中心层,得到两种不同多层层压品。第一种多层层压品包括:10密耳PETIP/1密耳COTBPR/10密耳PETIP。第二种多层层压品包括:10密耳PETIP/5密耳COTBPR/10密耳PETIP。在三种不同的拉伸温度下以在挤压纵向(MD)拉伸比2.5拉伸两种不同的层压品。保持横向恒定宽度。用红外加热器加热样品并用红外高温计测量膜表面温度,当达到表II所示的希望拉伸温度时,接着以每秒1.25英寸的拉伸速度开始拉伸。层间厚度均匀并在COTBPR层上观察不到裂缝。全均匀拉伸即跨过被拉伸层压品的整个宽阔的区域(expanse)在所有样品中都实现均匀降低LCP的原始厚度。
表II
批号 | COTBPR层厚度[密耳] | 拉伸温度[℃] | 拉伸比TD MD | 备注 | |
1 | 1 | 125 | 1 | 2.5 | 全均匀拉伸 |
2 | 5 | 125 | 1 | 2.5 | 全均匀拉伸 |
3 | 1 | 135 | 1 | 2.5 | 全均匀拉伸 |
4 | 5 | 135 | 1 | 2.5 | 全均匀拉伸 |
5 | 1 | 145 | 1 | 2.5 | 全均匀拉伸 |
6 | 5 | 145 | 1 | 2.5 | 全均匀拉伸 |
对比例:
单轴拉伸多层膜:将自实施例2的相同Bruckner拉伸装置用于单轴拉伸在多层结构范围内的2密耳VectranFA膜样品,该多层结构具有如实施例3的在VectranFA膜两面上的10密耳PETIP层。VectranFA是从VectraA950全芳香LCP树脂(从Hoechst Ticona,a Hoechstgroup company,Summit,New Jersey购得的)生产的膜。用与实施例1相同的设备以相同的方式生产多层层压品。在挤压纵向(MD)拉伸比2.5使用四种不同的拉伸温度。横向保持恒定宽度。用红外加热器加热样品并用红外高温计测量膜表面温度,当达到表III所示的希望拉伸温度时,接着以1.25”/秒的拉伸速度开始拉伸。只要开始拉伸,当所有的拉伸温度高达175℃Vectran层就破裂。因为PETIP开始熔融,不能达到较高的拉伸温度。
表III
批号 | COTBPR层厚度[密耳] | 拉伸温度[℃] | 拉伸比TD MD | 备注 | |
1 | 2 | 125 | 1 | 2.5 | Vectran层脆性断裂不能拉伸 |
2 | 2 | 135 | 1 | 2.5 | Vectran层脆性断裂不能拉伸 |
3 | 2 | 145 | 1 | 2.5 | Vectran层脆性断裂不能拉伸 |
4 | 2 | 175 | 1 | 2.5 | Vectran层脆性断裂不能拉伸 |
实施例4:
拉伸吹塑多层瓶:用三步形成12盎司多层容器。第一步通过共挤压吹塑方法生产三层预制件嵌衬,使用的装置包括11/2”螺杆直径Arburg压机(press)和15mm螺杆直径BOY 15压机(press)(购自Boy MachinesCorporation,Exton,Pennsylvania)其与带环状喷嘴的多层流动混合头相连,后者将1/2英寸直径管型坯送入单模腔。在型坯上闭合模具以夹断型坯的两头。然后使型坯膨胀以形成嵌衬。在预定瓶壁面将多层嵌衬剪成长33/8英寸和直径0.68英寸。通常三层是相等厚度的,所以COTBPR中心层是约0.008并位于0.025英寸壁厚的基本上中心的位置。三层嵌衬的内层和外层包括用10%间苯二甲酸改性的T98 PET瓶树脂(购自Hoechst Trevira)。在270℃,COTBPR树脂具有熔融粘度5680泊。将三层嵌衬放到Arburg压模机上并用86H PET瓶树脂(购自HoechstTrevira)注射的0.14英寸层过模压(over mol ded)以形成预型件。然后在Sidel多工位(multi-station)吹塑拉伸机上吹塑拉伸预型件以形成12盎司具有遍及聚酯壁的均匀COTBPR层和良好透明性的容器。与形成该层的原始嵌衬0.008英寸厚度相比测得在器壁面积上的COTBPR层厚为0.0013英寸。这些厚度测量值表明对于在容器中的可拉伸COTBPR的总面积拉伸比为6.67。
实施例5:
拉伸吹塑后热成型:将在5密耳厚中心COTBPR层两面上的自实施例3的具有10密耳PETIP聚酯多层片材切成7×7英寸的块。然后在145℃热成型这些多层片材以形成嵌衬。热成型后平均嵌衬厚20.16密耳,表示平均拉伸比1.24。将嵌衬放到注模机的中心上,并用聚酯瓶树脂Polyclear N 10(购自Hoechst Trevira)过模塑,用10%重量的萘二酸改性。在过模塑步骤中,将熔融的N 10树脂注入到三层热成型嵌衬的外表面上以形成具有N 10/PETIP/COTBPR/PETIP结构的四层预型件。然后将预型件再加热到145℃并拉伸吹塑成具有遍及器壁的均匀COTBPR层而没有破碎和裂缝并具有良好透明性的500ml宽口容器。测得在器壁面积上的COTBPR层厚0.45密耳。该厚度测量值表明对于容器中的COTBPR的总面积拉伸比为11.1。
Claims (38)
1.一种多层层压品包括:(a)至少一层全芳香的无定形的在低于200℃的温度下可拉伸的液晶体聚合物层,和(b)至少一层非液晶体聚酯层,其中该多层层压品在低于200℃和低于全芳香的液晶体聚合物层(a)的熔融态的温度下,被拉伸至少2.5的总拉伸比,以达到层(b)中的分子定向。
2.按照权利要求1的多层层压品,其中所述的拉伸的全芳香的液晶体聚合物层(a)是聚酯和具有相应下式的重复单元:
-[P1]m-[P2]n-[P3]q-其中P1,P2和P3代表单体部分的残基,P1是芳香的羟基羧酸,P2是芳香的二羧酸,P3是酚的化合物;m,n和q代表具有m=n=q=5-40%的各个单体的摩尔百分含量。
3.权利要求2的多层层压品,其中所述拉伸的全芳香液晶体聚合物层(a)另外含有单体部分-[P4]r和[P5]S的重复单元,其中-[P4]r是不同于P1的仲芳香羟基羧酸部分,-[P5]S是不同于P3的酚部分,r和s代表各单体的摩尔百分含量,r是5-30%摩尔,s是5-20%摩尔。
4.权利要求3的多层层压品,其中P1是4-羟基苯甲酸,P2是对苯二甲酸,P3是4,4’-二羟基联苯基,P4是6-羟基-2-萘酸,P5是间苯二酚;m是5-40%,n是5-40%,q是5-40%,r是5-30%和s是5-10%。
5.权利要求3的多层层压品,其中P1是4-羟基苯甲酸,P2是对苯二甲酸,P3是4,4’-二羟基联苯基,P4是6-羟基-2-萘酸,P5是间苯二酚;m是30%,n是20%,q是10%,r是30%和s是10%。
6.权利要求1的多层层压品,其中所说的非液晶体聚酯层(b)包括选自由对苯二甲酸,间苯二甲酸,萘二羧酸,乙二醇,丙二醇和丁二醇部分及其混合物组成的组的单体残基。
7.权利要求1的多层层压品,其中所说的非液晶体聚酯层(b)选自由聚对苯二甲酸乙二醇酯;聚间苯二甲酸乙二醇酯;聚2,6-萘二酸乙二醇酯;聚对苯二甲酸丁二醇酯;聚对苯二甲酸丙二醇酯;可再生回收的聚对苯二甲酸乙二醇酯;共聚酯其中二酸成分是对苯二甲酸及其衍生物,间苯二甲酸及其衍生物,萘二羧酸的1,2-,1,3-,1,4-,1,5-1,6-,1,7-,1,8-,2,3-2,4-,2,5-,2,6-,2,7-,2,8-异构体及其衍生物,4,4’-联苯基二羧酸和其衍生物,4,4’-联苯基醚二羧酸和其衍生物,1,2-二苯乙烯二羧酸和其衍生物,5-12个碳原子的线性与单和双环脂肪二羧酸和其衍生物,共聚酯其中二醇成分是2-12个碳原子的线性脂肪二醇和其衍生物,2-甲基丙二醇,2,2’-二甲基丙二醇,环己二醇,环己基二甲醇,1,3-二(2-羟基乙氧基)苯和其衍生物,1,4-二(2-羟基乙氧基)苯和其衍生物,二(4-β-羟基乙氧基苯基)砜和其衍生物,二乙二醇,聚乙二醇,聚丙二醇,聚亚丁基二醇,甘油和其衍生物,三羟甲基丙烷和其衍生物,三羟乙基丙烷和其衍生物,季戊四醇及其衍生物;它们的化合物和混合物组成的组。
8.权利要求1的多层层压品,其中将所述全芳香液晶体聚合物层(a)和所述的非液晶体聚酯层(b)共挤压以形成多层层压品,和随后在低于200℃和低于层(a)的熔融态的温度下拉伸至少2.5的总拉伸比。
9.权利要求8的多层层压品,其中所述的共挤压层压品接着在模内膨胀进行拉伸。
10.权利要求8的多层层压品,其中接着将所述的共挤压层压品进行吹塑产生所述拉伸。
11.权利要求1的多层层压品,其中是通过用选自单轴拉伸,多轴拉伸,和在模内吹塑的方法在低于200℃和低于层(a)的熔融态的温度下将该层压品拉伸至少2.5的总拉伸比。
12.权利要求1的多层层压品,其中所述的层压品选自平面状,管状,缠绕状的形式和通过开口管状层压品形成平面状。
13.权利要求1的多层层压品,其中将所述的层压品按其成形接着热成型为一形状。
14.一种从权利要求1的多层层压品形成的容器,其中所述的容器选自由热成型的容器,注射吹制成的容器,挤出吹制成的容器和拉伸吹制成的容器组成的组。
15.权利要求1的多层层压品形成的容器,其中所述的容器选自由包,袋和管组成的组。
16.权利要求15的容器,其中所述容器为管式并且管子的一端或两端已封闭。
17.权利要求15的容器,其中通过折叠和密封平面层压品以形成管子和封闭管子的一端或多端从管子形成容器。
18.一种从权利要求1的多层层压品形成的容器,其中所述的容器选自由盒子和罐组成的组。
19.权利要求1的多层层压品制成的容器,其中所述拉伸的全芳香的液晶体聚合物层(a)是聚酯并具有相应的以下通式的重复单元:
-[P1]m-[P2]n-[P3]q-其中P1,P2和P3代表单体部分的残基,P1是芳香的羟基羧酸,P2是芳香的二羧酸,P3是酚的化合物;m,n和q代表具有m=n=q=各5-40%的各个单体的摩尔百分含量。
20.权利要求19的多层层压品制成的容器,其中所述拉伸的全芳香液晶体聚合物层(a)另外含有单体部分-[P4]r和[P5]s的重复单元,其中-[P4]r是不同于P1的仲芳香羟基羧酸部分,-[P5]s是不同于P3的酚部分,r和s代表各单体的摩尔百分含量,r是5-20%摩尔,s是5-30%摩尔。
21.权利要求20的多层容器,其中P1是4-羟基苯甲酸,P2是对苯二甲酸,P3是4,4’-二羟基联苯基,P4是6-羟基-2-萘酸,P5是间苯二酚;m是5-40%,n是5-40%,q是5-40%,r是5-30%和s是5-10%。
22.权利要求20的多层容器,其中P1是4-羟基苯甲酸,P2是对苯二甲酸,P3是4,4’-二羟基联苯基,P4是6-羟基-2-萘酸,P5是间苯二酚;m是30%,n是20%,q是10%,r是30%和s是10%。
23.权利要求1的多层层压品制成的容器,其中所说的非液晶体聚酯层(b)包括选自由对苯二甲酸,间苯二甲酸,萘二羧酸,乙二醇,丙二醇和丁二醇部分及其混合物组成的组的单体残基。
24.权利要求1的多层层压品制成的容器,其中所说的非液晶体聚酯层(b)选自由聚对苯二甲酸乙二醇酯;聚间苯二甲酸乙二醇酯;聚2,6-萘二酸乙二醇酯;聚对苯二甲酸丁二醇酯;聚对苯二甲酸丙二醇酯;可再生回收的聚对苯二甲酸乙二醇酯;共聚酯其中二酸成分是对苯二甲酸及其衍生物,间苯二甲酸及其衍生物,萘二羧酸的1,2-,1,3-,1,4-,1,5-,1,6-,1,7-,1,8-,2,3-2,4-,2,5-,2,6-,2,7-,2,8-异构体及其衍生物,4,4’-联苯基二羧酸和其衍生物,4,4’-联苯基醚二羧酸和其衍生物,1,2-二苯乙烯二羧酸和其衍生物,5-12个碳原子的线性与单和双环脂肪二羧酸和其衍生物,共聚酯其中二醇成分是2-12个碳原子的线性脂肪二醇和其衍生物,2-甲基丙二醇,2,2’-二甲基丙二醇,环己二醇,环己基二甲醇,1,3-二(2-羟基乙氧基)苯和其衍生物,1,4-二(2-羟基乙氧基)苯和其衍生物,二(4-β-羟基乙氧基苯基)砜和其衍生物,二乙二醇,聚乙二醇,聚丙二醇,聚亚丁基二醇,甘油和其衍生物,三羟甲基丙烷和其衍生物,三羟乙基丙烷和其衍生物,季戊四醇及其衍生物;它们的化合物和混合物组成的组。
25.制造多层层压品的方法,包括将(a)至少一层全芳香的在低于200℃下可拉伸的液晶体聚合物层和(b)至少一层非液晶体聚酯层结合形成多层层压品,和随后在低于200℃和低于层(a)的熔融态的温度下将该多层层压品拉伸至少2.5的总拉伸比,以达到层(b)中的分子定向。
26.权利要求25制成多层层压品的方法,其中在高于玻璃化转变温度和低于所说的全芳香液晶体聚合物熔融态的温度的温度下进行上述拉伸。
27.权利要求26的制成多层层压品的方法,其中通过模内膨胀进行所述拉伸。
28.权利要求25的制成多层层压品的方法,其中通过共挤出制成层(a)和层(b),并结合在一起。
29.权利要求25的制成多层层压品的方法,其中通过注模制成层(a)和层(b),并结合在一起。
30.权利要求25的制成多层层压品的方法,其中通过热成型将所述的多层层压品拉伸为具有最内表面和最外表面的形状,进一步包括下列步骤:将热成型的多层层压品放在模中,将热塑性材料注入到所说的模中以形成所说的注射热塑材料的外层,其与所述的热成型的层压品的最外表面接触。
31.权利要求25的制成多层层压品的方法,其中最初提供所述层压品作为预型件,其后在模内膨胀产生所述拉伸。
32.权利要求31的制成多层层压品的方法,其中双轴拉伸所述的预型件。
33.权利要求25的制成多层层压品的方法,其中所述全芳香液晶体聚合物是具有下面相应的通式的重复单元的聚酯:
-[P1]m-[P2]n-[P3]q-其中P1,P2和P3代表单体部分的残基,P1是芳香的羟基羧酸;P2是芳香的二羧酸;P3是酚化合物;m,n和q代表具有m=n=q=5-40%的各个单体的摩尔百分含量。
34.权利要求33的制成多层层压品的方法,其中所述全芳香液晶体聚酯另外含有单体部分-[P4]r和[P5]s的重复单元,其中-[P4]r是不同于P1的仲芳香羟基羧酸部分,-[P5]s是不同于P3的酚部分,r和s代表各单体的摩尔百分含量,r是5-30%摩尔,s是5-20%摩尔。
35.权利要求34的制成多层层压品的方法,其中P1是4-羟基苯甲酸,P2是对苯二甲酸,P3是4,4’-二羟基联苯基,P4是6-羟基-2-萘酸,P5是间苯二酚;m是5-40%,n是5-40%,q是5-40%,r是5-30%和s是5-10%。
36.权利要求34的制成多层层压品的方法,其中P1是4-羟基苯甲酸,P2是对苯二甲酸,P3是4,4’-二羟基联苯基,P4是6-羟基-2-萘酸,P5是间苯二酚;m是30%,n是20%,q是10%,r是30%和s是10%。
37.权利要求25的制成多层层压品的方法,其中所说的非液晶体聚酯(b)包括选自由对苯二甲酸,间苯二甲酸,萘二羧酸,乙二醇,丙二醇和丁二醇部分及其混合物组成的组的单体残基。
38.权利要求25的制成多层层压品的方法,其中所说的非液晶体聚酯(b)选自由聚对苯二甲酸乙二醇酯;聚间苯二甲酸乙二醇酯;聚2,6-萘二酸乙二醇酯;聚对苯二甲酸丁二醇酯;聚对苯二甲酸丙二醇酯;可再生回收的聚对苯二甲酸乙二醇酯;共聚酯其中二酸成分是对苯二甲酸及其衍生物,间苯二甲酸及其衍生物,萘二羧酸的1,2-,1,3-,1,4-,1,5-1,6-,1,7-,1,8-,2,3-2,4-,2,5-,2,6-,2,7-,2,8-异构体及其衍生物,4,4’-联苯基二羧酸和其衍生物,4,4’-联苯基醚二羧酸和其衍生物,1,2-二苯乙烯二羧酸和其衍生物,5-12个碳原子的线性与单和双环脂肪二羧酸和其衍生物,共聚酯其中二醇成分是2-12个碳原子的线性脂肪二醇和其衍生物,2-甲基丙二醇,2,2’-二甲基丙二醇,环己二醇,环己基二甲醇,1,3-二(2-羟基乙氧基)苯和其衍生物,1,4-二(2-羟基乙氧基)苯和其衍生物,二(4-β-羟基乙氧基苯基)砜和其衍生物,二乙二醇,聚乙二醇,聚丙二醇,聚亚丁基二醇,甘油和其衍生物,三羟甲基丙烷和其衍生物,三羟乙基丙烷和其衍生物,季戊四醇及其衍生物;它们的化合物和混合物组成的组。
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-
1997
- 1997-10-20 US US08/954,379 patent/US6268026B1/en not_active Expired - Fee Related
-
1998
- 1998-10-08 TW TW087116729A patent/TW376362B/zh not_active IP Right Cessation
- 1998-10-14 EP EP19980308364 patent/EP0909781A3/en not_active Withdrawn
- 1998-10-16 AU AU89375/98A patent/AU8937598A/en not_active Abandoned
- 1998-10-19 KR KR1019980043634A patent/KR100616174B1/ko not_active IP Right Cessation
- 1998-10-19 BR BR9804009A patent/BR9804009A/pt not_active Application Discontinuation
- 1998-10-20 JP JP29798598A patent/JPH11268191A/ja active Pending
- 1998-10-20 CN CNB981245978A patent/CN1145663C/zh not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
EP0909781A3 (en) | 1999-05-19 |
KR100616174B1 (ko) | 2007-04-25 |
JPH11268191A (ja) | 1999-10-05 |
TW376362B (en) | 1999-12-11 |
BR9804009A (pt) | 1999-12-14 |
CN1235173A (zh) | 1999-11-17 |
KR19990037189A (ko) | 1999-05-25 |
US6268026B1 (en) | 2001-07-31 |
EP0909781A2 (en) | 1999-04-21 |
AU8937598A (en) | 1999-05-06 |
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