CN103917353A - 多部件带、膜、线及其制造方法 - Google Patents

多部件带、膜、线及其制造方法 Download PDF

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Publication number
CN103917353A
CN103917353A CN201280049832.1A CN201280049832A CN103917353A CN 103917353 A CN103917353 A CN 103917353A CN 201280049832 A CN201280049832 A CN 201280049832A CN 103917353 A CN103917353 A CN 103917353A
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CN
China
Prior art keywords
layer
pla
film
band
ground floor
Prior art date
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Pending
Application number
CN201280049832.1A
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English (en)
Inventor
费姆克·德·洛斯
费尔南多·埃布拉贡
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.)
Lankhorst Indutech BV
Lankhorst Pure Composites BV
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Lankhorst Indutech BV
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Publication date
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Publication of CN103917353A publication Critical patent/CN103917353A/zh
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    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
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    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/05—Filamentary, e.g. strands
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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)
  • Woven Fabrics (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Multicomponent Fibers (AREA)
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Abstract

本发明涉及聚乳酸（PLA）的共挤出带、膜和线等及其制备方法，本发明涉及挤出带、膜或线，其包含：基于PLA的第一相，尤其是第一层，及同样基于PLA但是具有不同的密封性质的第二相，尤其是第二层，其中，所述第二层的熔融峰部温度或密封起始温度低于所述第一层的熔融峰部温度和/或熔融密封起始温度；或其中所述第二层的维卡软化点低于所述第一层的维卡软化点。

Description

多部件带、膜、线及其制造方法
技术领域
本发明涉及聚乳酸（PLA）的共挤出带、膜、线等及其制造方法。
背景技术
聚乳酸具有结构式–[–C(CH3)–C(O)–O–]n–，其中n>>1。PLA的主要性能之一为它的可堆肥性（compostable)，即可在酶作用的影响下在堆肥条件堆肥一段时间后降解，使其特别适于应用于一次性物品。其另一主要性能为固有的紫外光稳定性及阻燃性。这使得此材料适于例如作为用于室外及室内用途的毯子的应用。
WO-A-2010/074576描述了基本上由PLA组成的带。发现这类生物可降解性带尤其在农业中的用途，特别是园艺中用于捆绑植物，也可用于绳索及包装用途。
发明内容
本发明的目为提供可用在除了像这样的带的以外的其它用途中的材料。PLA是一种欠缺强度及韧性的材料，这限制了它的应用。WO-A-2010/074576描述的带设法保持所述材料的可堆肥性，且同时给予强度及韧性有大幅增加。然而，这些带限于在一维方向的应用，即，它们仅在拉伸及单方向中有用。
本发明的一个目的为扩展这些已知的带的应用扩到2维及3维的制品，没有注塑或加热成形的PLA部件的缺点，例如差的强度及断裂韧度。尤其地，目的为提供PLA带、膜、线等，其可通过例如由此形成织物，然后所述织物可随后压制模塑成期望的形状，而进一步加工成各种形状的产品。由此获得的这些成型品可堆肥。
US-A-2009/0148715描述了包含无定形及结晶PLA的层合体。这些已知的材料还包含乙烯-丙烯酸酯共聚物。这些材料不是生物可降解的。
US-A-6153276描述了乳酸类聚合物，其在化学方面与PLA不同。
JP-A-2003/170560描述了层合体，其中基层（A）由聚乳酸酯组成，并且通过混合防粘结剂及特定的生物可降解性树脂而获得层（B）。已知的PLA材料的另一个限制为其最高工作温度，一般限于50℃。这限制了这些已知的PLA材料在否则会受益于PLA的可堆肥性的，例如餐饮及食品服务的一次性物品的应用中的使用。因此本发明另一目的为提供一种材料，其可在较高温度使用而不会有变形或其他功能性丧失。
本发明人发现为了满足上述目的及其它目的至少一部分，所述PLA产品应由至少2个相组成的织造或缠绕的带、膜或线构成，各相包含不同类型的PLA，尤其是在软化性能方面不同的PLA组合物，尤其是在根据ISO306如维卡（Vicat）检验定义的软化温度、它们的密封起始温度和/或其（最低）熔融峰部温度方面。这些相可通过共挤压处理而分离为两层，或可在单一层中混合。因此在第一方面中，本发明涉及挤出带、膜或线，包含基于PLA的第一相，尤其第一层，以及同样基于PLA的但具有不同的密封性质的第二相，尤其是第二层。
密封性质的这些差异可表达如下：根据本发明，第二层应具有如通过ASTM F88测得的低于第一层的熔融峰部温度的密封起始温度。通过差示扫描热量计（DSC）确定熔融峰部温度，例如当以10℃/min的加热速度加热，并且为材料开始熔融的第一个峰部（即最低温度）。由于DSC曲线显现出宽的肩部或平坦区（plateau），所以对于一些材料，不可能确定熔融峰部温度。在这些情况下，也可使用第一层的密封起始温度，以使第二层的密封起始温度低于第一层。
或者，第一层与第二层在密封性能的差异可表示为通过ISO306定义的维卡软化点的差异，以根据本发明另一个实施方式，第二层应具有比第一层的维卡软化点低的维卡软化点。维卡软化点是用10N负荷通过具有1平方毫米的圆形或方形截面的平头针刺入样品1mm的深度的温度。该第二相能以分开的层共挤出在该第一相的上面。或者，可将两相都挤出成包括两相的单一层。根据本发明，第一相中的PLA的熔融温度或功能与第二相中的PLA的熔融温度或功能不同。
本发明中使用的用于两相的PLA材料，优选由多于95wt%，更优选多于98wt%的PLA组成。可通过添加其它树脂及作添加剂，例如功能性添加剂，像熔融强度增强剂、紫外光吸收剂、阻隔增强剂、结晶促进剂或阻碍剂、链延长剂、阻燃剂、填剂、塑化剂、发泡剂、增容剂、热稳定剂、润滑剂、抗微生物剂、抗氧化剂、抗静电剂、增韧剂（toughener）、色素、脱模助剂或澄清剂，而改变各相的组成。
本发明的材料以及由其制造的物品生物可降解，意味着他们能在天然存在的微生物，例如细菌、真菌等作用下在一段时间后分解。此外，本发明的材料及物品同样优选可堆肥，意思是它们能以与纸相同或更快的足够高的速度生物降解。
在相以单独的层存在的实施方式中，优选该带、膜或线具有内层及外层，其中主要由该外层接触坏境，以使当编织或缠绕时，主要由一个带、膜或线的外层（没有或只有一小范围的内层）接触其它带、膜或线的外层。然后，可选择该外层具有优异的密封性，而可优化内层的机械强度。然后，最外层作为黏胶发挥作用。
除了或替代地被选择以增强黏着性以外，还可选择外层以改善合成材料的其它性能，例如，通过选择由具有高耐擦性或低磨擦系数的PLA组合物组成的外层，而改善合成产品的磨擦性质。
第二层（例如外层）可包含无定形的PLA或具有比起第一层低的结晶性的PLA。典型地，无定形PLA具有比起结晶性PLA低的软化温度（或密封起始温度或熔融峰部温度）。
第一层（尤其核层）可包含半结晶性或结晶性PLA。这可使用例如优选地具有小于6wt%的D-乳酸含量的高光学纯度PLLA制造，或使用立体复合物（stereocomplex）PLA（sc-PLA）或立体嵌段（stereoblock）PLA（sb-PLA）制造。典型地，从带的测定密度以及结晶相的已知的密度（α多形体为1.285g/cm3，β多形体为1.301，并且无定形相为1.245g/cm3）计算得到的结晶度为约25%或更大，优选大于45%。每当存在β多形体时，可通过广角x射线衍射（WAXD）或红外分光光谱（IR）测定结晶相的α多形体与β多形体间的比例。本实施方式虽然大部分由受荷（load-bearing）结晶相构成，但直到达到熔融的开始（onset）才会熔融，可为非常高，例如高于100℃，例如约140℃，因此允许该材料可用于热的食品及饮料。
加热时，当该材料一达到其玻璃化转变温度（Tg)，无定形PLA就开始软化。这可通过储能模量从就在Tg（约55℃）之前的3000MPa突然下降到密封起始温度（80℃）的约5MPa而观察到。在这个温度，无定形PLA能有效地形成密封。该密封的故障模式（failure mode）将决定该织造的共挤出带在热压或热成形时形成固体的能力，且取决于该密封温度，决定该受荷层的机械性质及热性能，以及密封时施加的压力及时间。密封的可能的破坏模式为剥离、分层、撕裂，或分层与撕裂的组合。由于半结晶相的高强度，本实施方式中密封的最可能发生的故障模式为剥离及分层。在密封温度，PLA半结晶层将随着储能模量（G’）从约3000MPa降低至约500MPa或低密度聚乙烯在室温的硬度的约2倍减小而软化。该无定形相的密封温度也符合起始PLA结晶快速生长的温度，这将会适当地改善受荷层的结晶性及热与机械性质。为了应用于热食品及饮料，第一层的期望熔融温度（Tm）的范围优选高于96℃，此可通过组合热及压力诱发性结晶和/或选择成核剂而实现。因此，半结晶相的Tm远远地超越针对食品服务的2005FDA规章指南，该指南要求针对热食品的温度为60℃，并超过水类热饮的最高温度。半结晶PLA在100℃时储能模量有降低，这在文献据报告为根据结晶程度，比在室温测量的值低了约1至2个数量级。这导致30MPa至300MPa的弹性系数。本发明的材料当加热至100℃时，显示储能模量比在室温测得的数量级的减小，例如0.68GPa。
可设计本发明的带、膜或线产生关于密封的优异的性能。当这样的带、膜或线加工成织物，然后在压模中加工时，获得具有优异的机械性能的产品，但仍保持其生物可降解性，尤其是如E模数表示的优异的硬度和在断裂时伸长率的增加表示的改善的断裂韧性，即注塑或否则模塑或挤出的片或膜。此外，获得符合食品接触法规的产品。
可拉伸包含此PLA的带、膜或线等。优选地，以大于1:4的总拉伸（draw）比进行拉伸。并非总能在一个拉伸步骤中拉伸至大于1:4的拉伸比，而且可能造成机械性质不足或不稳定的加工。因此，优选在多于一次的拉伸步骤中进行拉伸至总拉伸比，其中于第一个拉伸步骤中，拉长比小于1:4，并进行第二个或更多的拉伸步骤，使获得大于1:4，优选大于1:5的总拉伸比。通常，优选保持总拉伸长比小于1:14，优选小于1:8。通过实施拉伸步骤，观察到PLA材料变白。这表示强度增加。通过在多级拉伸步骤中进行拉伸，可获得材料性质的优异的控制。基于机械性质，优选进行拉伸直到观察到变白。典型地，在这个情况下，拉伸比为1:5或更大。
如上述，本发明的带、膜或线等可以提供改善的密封性质。为了由带、膜或线制出二维或三维的产品，需将其彼此黏合。这可经由结晶相的熔融或使用黏胶而通过结晶相局部预熔，无定形相受控制的熔融而实现。该黏胶可经由浇铸处理而应用为带或织物间的薄膜，或应用为共挤出层。本发明的方案描述了共挤出层，其中使制造部件及相关废料所需的操作数有净减少。发现其它满足混合产品的要求的方案为使用部分结晶化的PLA材料。这可通过改变加工条件、添加阻碍结晶化的添加剂或树脂或增加使用的PLA的D-乳酸含量而实现，这可产生具有结晶相及无定形相的带或线无定形。
本发明中描述的产品的密封性质可通过密封起始温度的方式定量，可根据ASTMF1921确定密封起始温度。在这个检测方法中，将带沿长度折叠并密封自己。然后通过空气冷却。冷却后，通过以恒定的速度拉而再次分开将密封的两端，并且通过测量以N表示的密封强度和确定分离整个密封的表面的功的量（以mJ表示）而确定密封强度。步骤如下。将膜样本固定于连接到负荷传感器的上部样品夹扣及连接到剥离致动器的下部样品夹扣。将膜样本通过样品插入构件而插入于密封棒之间。制造密封。当密封时间结束时，以及在预设的延迟时间后，将该剥离致动器以预设的速度向下移并且将该热封完全剥离分开。
本发明涉及PLA“带、膜或线（或类似物）”，即特征为长度比厚度长相当多的任意形状。典型地，该带、膜或线产品为条状物品，具有大于厚度的100倍的长度。例如，典型的卷轴可包含约5000米的具有0.1mm或更小的厚度的带膜或线。该带膜或线也可扭转，在这个情况下，典型的直径为约2.5mm。其截面可为任意形状。典型地为圆形、方形或矩形。在共挤出带或线的情况下，该第一层（典型地核层）直接接触该第二层（典型地外层）。该第二层可部分或完全包围该第一层。除此第二层，也可存在第三层或甚至更多的PLA层，其具有与其它两个层不同的组成，尤其是关于功能、软化温度或结晶性不同。该第二层及第三（或甚至更多）层可共同部分地或完全地包围该第一层。
未拉伸的PLA有非常低的扯断伸长率及抗拉强度（tenacity），这反映在由这样的材料制成的注塑或否则模制部分的膜或带的差的能量吸收。在拉伸期间，PLA由于应力引发的分子排列而经历玻璃状至半结晶的转变。这由带或膜从透明变色为白色反映。此效果显示为依赖于温度的不同的拉伸比，并且较高温度的拉伸移动此效果移到较高的拉伸比。较高拉伸会使抗拉强度保持增长，但所生产的膜或带的断裂韧性再次下降。以小于4的总拉伸比（SR）单轴或双轴拉伸，会产生相当脆弱且难以操作的膜及带。
如本技术领域技术人员熟知，将带、膜或线拉伸会使其结构改变，尤其是由于分子（聚合链）重排。增加的抗张强度和增加的弹性系数（E-模数）反映这个改变。因此抗张强度和/或E-模数实际上为产品的特性，并且可用于表征将本发明的带、膜或线。根据本发明，可提供具有150MPa或更高，优选240MPa或更高的抗张强度的产品。断裂时的伸长率优选高于7%，但典型地7～25%。E-模数优选为4.5GPa或更高，更优选6.5GPa或更高。
作为对照，未拉伸的PLA带、膜或线典型地具有约60MPa的抗张强度、4%的断裂时的伸长率和约3GPa的E-模数。
以实验室规模将多纤丝进行旋转拉伸的技术的状况，据Gupta等人（Progress inPolymer Science，32(2007)455-482）的报道强度和模数目前分别超过1000MPa和10GPa。这与此材料的理论极限很好地对照，该材料为具有15GPa的弹性系数的最坚硬的PLA的α多形体。PLA的β多形体模数较低（7GPa），且可在较高温度制造。认为该α多形体结晶结构形成斜方晶系（orthorhombic）的晶格，而已知β多形体形成三方晶系（trigonal）结构。
可编织本发明的带、膜或线，例如作为平织织物。在机械性质方面，这是改善最终产物的均匀性的优异的构形。其它构形也是可能的，例如斜纹织（twill）织物或缎纹（satin）织物、单方向排列及压制的带或纤丝缠绕的部件。
该织造物由于其独特的构形，在其强度及弹性系数上有限制，该限制为在机械方向为带的50%以下。这是由于该织物将由在机械方向以及横向都拉伸并且在起皱褶的过渡区偏离平面的带组成的事实。由于大分子的正交各向异性（orthotropic）排列，在横向的性能可最多比机械方向会低至1或2个数量级。因而能获得的最小硬度及强度各为3GPa及75MPa，因此，使用编织的PLA带或线织物将提供与耐久的产品中发现的那些类似的硬度和强度的产品，如下表1中描述：
表1
一些上述材料的破坏伸强率低，使其固有地易碎，而这里所述的材料具有在7～25%的范围内的破坏伸长率，使其为有韧性的材料。
可使用该技术领域中已知的方法确定这里使用的E-模数。除非另外说明，这里使用的所有的值均使用标准测试EN10002的方法而获得。
优选通过浇铸膜挤出或吹塑膜挤出而制造本发明的带、膜、线等的各层。当该产品使用了2层或更多层时，这些层通过共挤出接合，即通过使来自于2或更多个挤出机的、含有2种或更多种不同的具有如上述的变化的热性能的不同原材料的增塑树脂通过，并且同时挤出它们通过层状结构的模具。
这里使用的总拉伸比，主要是指单向拉伸，尤其在机械（纵向）方向拉伸。然而，有些横向拉伸通常是不能避免的，尤其当实施吹塑膜挤出时。根据本发明，在机械方向（X）的总拉伸比大于4，而对膜的横向方向（Y）的总拉伸比优选小于1.5，以使这些拉伸比的比值（X/Y，双轴拉伸纵横比）为2.7或更大，但优选4或更大。
具体实施方式
在优选的实施方式中，本发明的带、膜或线包含一个具有Tm的中心层和具有所述中心层的Tm的密封温度的外层。根据该实施方式，所述带、膜或线优选为ABA型，即三明治结构，其中“A”并且外层，并且“B”表示核层。
在另一个优选的实施方式中，根据本发明的带、膜或线具有包含半结晶PLA的内层和包含无定形PLA的外层无定形。该内层虽大部分结晶，但仍能承受足以熔融在外面无定形层中的黏胶的高温无定形而不熔融。
在另一个优选的实施方式中，根据本发明的带、膜或线具有包含结晶PLA相及无定形PLA相的单层无定形。通过使用仔细地控制的加热处理，在带或线内的无定形相将会熔融或软化而作用为黏胶，同时结晶相保持不变。
图2a及2b示意地描述了本发明的带、膜或线。图2a显示了实施方式，其中层A的密封起始温度低于层B的熔融温度。同样适用于图2b，图2b显示了另外的层A’，该层A’可以与层A组成相同（ABA型）或为另一种组成。
图3a、3b及3c示意地显示了本发明的带、膜或线的其它可能的变化。图3a的实施方式为包含中心核B的带、膜或线，纤维状的部件A缠绕该中心核B，其中层A同样具有低于层B的熔融温度的密封起始温度。在图3b描述的实施方式中，具有较低密封起始温度的材料并非应用为连续的层，而是应用为分离的岛或相，然而仍能获得本发明的益处。在图3c的实施方式中，例如通过并入相A到层B中而应用相A及B，使得只有最终的带、膜或线的表面显示分离相A与相B。
优选在一层或多层，优选在所有层中使用PLA，该PLA富含对映体，优选为主要对映异构体的L型对映异构体，更优选组成PLA的单体单元的多于85wt%，更优选多于90wt%，最优选96～98wt%之间的L-乳酸。发现这改进了加工性及机械性能。或者一个或更多相可被50%L-乳酸及50%D-乳酸的混合物取代。此混合物可形成具有增强的耐温性及机械性能的立体复合体化合物。
通过引用合并于此的WO-A-2004/103673（Ward等）描述了用于生产聚合物物品的方法。可根据本发明，即通过使用PLA有利地使用此文献中描述的技术。因此，根据这个实施方式，本发明的方法步骤：（a）形成具有连续层的层片（ply），即（i）由PLA材料，尤其至少包括至少结晶相的PLA的股线组成的第一层；（ii）无定形PLA材料或具有低于第一层的结晶性的PLA半结晶材料的第二层无定形：（iii）由PLA材料，尤其包括至少结晶相的PLA的股线组成的第三层，其中，该第一层及第三层的熔融峰部温度高于第二层根据ASTM F1921确定的密封温度；（b）对该层片施以足以熔融第一层及第三层的一部分的时间、温度及压力条件；将该层片压紧；（c）冷却将该已压紧的层。产生的物品具有良好的机械性能，还能在比未采用第二层的物品低的压紧温度制造，导致更可控制的制造工艺。
本发明的PLA带、膜或线可进一步包含添加剂以改进加工性或改变光学性质。优选地，所述带、膜或线不含或基本实质上不含（即，通常包含低于0.5wt%）塑化剂，并且可由多于95%PLA构成。
在优选的实施方式中，使用图1中示意描述的设备制造所述带、膜或线。
参照图1，在本发明的方法的一个实施方式中，将通常为颗粒形态的PLA原材料给料到2台不同的挤出机（挤出机A及B，11)，在此被推进通过单一模具2而获得共挤出产品。然后，通过将该材料给料在放置于具有典型15～45℃的温度的水浴中的第三辊17上，而在冷却步骤12中冷却该材料。然后，该材料给料到切割机4，在此将该带切成两条或更多的条。通过先将材料给料到第一辊13，然后给料到第一烘箱14，在此加热到典型地75～95℃，优选80～90℃的温度，然后给料到第二辊15，而实施第一拉伸步骤。通过选择第二辊15的辊速快于第一辊13的辊速，而拉伸该PLA材料。然后，通过由先将该材料给料到第二烘箱16，在此加热到典型95～170℃，优选100～110℃的温度，然后给料到第三辊17，其中，选择第三辊17的辊速快于第二辊15的辊速，而实施第二拉伸步骤。然后，通过先将该材料给料到第三烘箱18，在此加热至典型地90～150℃的温度，然后给料到第四辊19，在此选择第四辊19的辊速慢于第三辊17，而实施松弛步骤。此步骤减少或完全避免带、膜或线在接下来的操作中收缩。然后，可以通过原纤化器（fibrillator）110原纤化获得的产品，以机械性能的减少为代价而给予它纺织品用途的较柔软的质感。最后，产品在缠绕步骤111中缠绕在卷轴上。
在所述方法的变化中，可使用75℃与170℃之间的温度在单一的操作中拉伸该长条状的膜。温度的选择取决于想要的劲度及抗拉强度。较低温度可带来较高弹性系数，弹性系数随温度升高而减少。温度的升高将会改善抗拉强度，直到达到平坦区，然后再度降低。在单一拉伸操作可获得的最大拉伸比可低于两次拉伸操作获得的最大拉伸比。该方法的稳定性也可受影响。该方法还可包括松弛步骤及原纤化操作。
根据本发明，该PLA原材料可以AB或ABA构形共挤出，其中A为例如无定形、功能层或黏着层，并且B为例半结晶层或受荷层。然后，通过将该材料给料在放置于具有典型15～45℃的温度的水浴中的第三辊17的上面，而冷却该材料。然后，该材料给料到切割机4，在此将该带切成两条或更多的条。通过先将材料给料到第一辊13，然后给料到第一烘箱，在此加热到典型地75～95℃，优选80～90℃，然后给料到第二辊15，而实施第一拉伸步骤。通过选择第二辊15的辊速快于第一辊13的辊速，而拉伸该PLA共挤出的材料。然后，通过由先将该材料给料到第二烘箱，在此加热到典型95～170℃，优选100～110℃的温度，然后给料到第三辊17，其中，选择第三辊17的辊速快于第二辊15的辊速，而实施第二拉伸步骤。然后，通过先将该材料给料到第三烘箱，在此加热至典型90～150℃的温度，然后给料到第四辊19，在此选择第四辊19的辊速慢于第三辊17，而实施松弛步骤。此步骤是为了减少或完全避免带或线在接下来的操作中收缩。然后，可以原纤化获得的产品，以机械性能的减少为代价而给予它纺织品用途的较柔软的质感。最后在管上缠绕产品以制成用于后续加工卷丝管（bobbin）。
导辊优选用于第一辊、第二辊及第三辊。在由挤出机染料（dye）形成膜后，优选将其给料到冷却浴，典型地在15～45℃的相当低的温度，优选约20～35℃的装有水的水浴。这“冻结（freeze)”了膜，并防止膜中的所谓缩颈（neck-in）。
优选地，该出制器在拉伸前用具有至少为2，优选至少5，例如约8的熔融流动指数的聚乙烯（PE）清洗，或者用具有至少为2，优选至少5，例如约8的熔融流动指数的聚丙烯(PP)清洗。
可通过吹塑膜挤出法（也称为管状膜挤出）或吹塑膜共挤出法制造本发明的带、膜或线。吹塑膜挤出为本身已知的方法。该方法包括通过圆环形模具挤出塑料，然后以“气泡状”膨胀。这样，可在单一操作中产生管状化（平面及角板两者）。可通过例如气泡中的空气体积（空气流速）、挤出器的输出，以及牵引（hauloff）的速度的因素控制膜宽度及厚度。可通过输送速度及空气流速控制该膜的双轴取向。可依照与上述相同的步骤拉伸由此途径制造的材料。
本发明的带、膜或线具有优异的断裂伸长率，典型地7～20%，优选约10%。
参照例
以图1中示意性描述的方案加工PLA带。
来自NatureWork的等级4032D的具有4%的D-丙交酯含量的PLA颗粒给料到挤出机B。该挤出机具有超过30:1的直径的比的长度和通用的螺杆。
设定料斗部的温度为40℃，并且设定标准温度曲线为从挤出机第一部分的180℃逐步提高至最后部分及转接器的200℃。设定挤压头为190℃。
设定图1的冷却辊（3）为6.8m/min。设定纵向切分机组后开始第一次牵引为7.3m/min。设定烘箱1为80℃。设定牵引2中的第二导辊为39m/min。总拉伸比为5.2。
实施例1
以图1示意性描述的设定处理2种不同类型的PLA。
将来自NatureWork的等级4060D与4032D、D-丙交酯含量分别为12%与4%的PLA的颗粒分别给料到2台挤出机A及B。该挤出机具有30:1的L/D比，并且具有通用的螺杆。以每分钟20转（rpm）的速度操作挤出机A，产生10kg/min的产量。以30rpm的速度操作挤出机B，产生78kg/min的产量。来自挤出机A的PLA与来自挤出机B的PLA的比为87/13。
设定料斗部的温度为40℃，并且设定标准温度曲线为从挤出机第一部分的180℃逐步提高至最后部分及转接器的200℃。设定挤压头为190℃。
设定图1的冷却辊（3）为6.8m/min。设定纵向切分机组后开始第一次牵引为7.3m/min。设定烘箱1为80℃。设定牵引2中的第二导辊为39m/min。总拉伸比为5.2。
获得布局为ABA的共挤出带，具有1190丹尼（denier）的细度（runnage）、2.5gf/den的抗拉强度、17%的破坏应变。表2也给出了这些结果。
实施例2～6
如表2中表示，改变挤出机的速度设定及第二导辊的设定，重复实施例1，产生对于各层分别的不同量的PLA及不同的拉伸比。表2还给出了产生的性能。
表2
对于所有测试的样本，弹性系数为6.5GPa。较高的拉伸比并未产生较高的抗拉强度和弹性系数，表明最适加工条件为不同的烘箱温度或拉伸比。当提高SR时应力-应变曲线的唯一改变的部分在增强前一点的降伏点（yield point）之后。由于较高的SR产生较低的伸长率以及因此较低的韧性，所以由于探针较早的脆性破坏而使抗拉强度未增加。
测试来自实施例1、5及6的样本的密封。
实施例1直到130℃未显示任何可见的密封。即便在此高温，虽然收缩极高，B层仍无明显的熔融或软化。
实施例5与6显示从90℃以上的良好的密封性能。
如下表3描述，测试实施例6系关于弹性系数随温度降低。
表3
温度 弦线模量（2-3%变形）
23℃ 6.50GPa
40℃ 3.86GPa
50℃ 2.23GPa
70℃ 1.57GPa
实施例7～8
如表4中表示，挤出机的速度设定及第二导辊的设定保持不变，并分别用与第二拉伸操作以不同的拉伸比重复实施例1。表4还给出了产生的性能。
表4
对于弹性系数，实施例7及8为6.7GPa及6.8GPA，略高于单一拉伸操作实施例的平均值6.5GPA。双拉伸操作与单一拉伸操作相比，同样带来中间产物的抗拉强度方面小的提高，是生产流程稳定性的主要改善。

Claims (12)

1.一种带、膜或线，包含第一层及第二层，所述第一层及第二层均以PLA为基础，其中，所述第二层在所述第一层上共挤出，其中，所述第二层的密封起始温度和/或熔融峰部温度低于所述第一层的密封起始温度和/或熔融峰部温度。
2.一种带、膜或线，包含第一层及第二层，所述第一层及第二层均以PLA为基础，其中，所述第二层在所述第一层上共挤出，其中，所述第二层的维卡软化点低于所述第一层的维卡软化点。
3.如前述任一项权利要求所述的带、膜或线，包含另一层，所述另一层在所述第一层上共挤出，优选形成ABA型的带、膜或线。
4.如权利要求3所述的带、膜或线，其中，所述第一层，优选所述内层包含半结晶PLA，并且所述第二层，优选所述外层，包含无定形PLA或结晶性低于所述第一层的PLA。
5.如前述任一项权利要求所述的带、膜或线，被拉伸至总拉伸比至少为4。
6.如前述任一项权利要求所述的带、膜或线，以一个或更多个拉伸阶段拉伸。
7.一种物品，通过将包含前述任一项权利要求所述的带、膜或线的织造膜或非织造膜进行热处理而制备。
8.如权利要求7所述的物品，其抗拉强度为75MPa或更高，优选为120MPa或更高。
9.如权利要求7或8所述的物品，其断裂伸长率为7～25%，优选为10～15%。
10.如权利要求7至9的任一项所述的物品，其中，所述物品的E-模数为2.5GPa或更高，优选为3.5GPa或更高。
11.如权利要求7至10的任一项所述的物品，所述物品是生物可降解的。
12.如前述权利要求所述的物品，所述物品是可堆肥的。
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