CN100513137C - 多层双轴拉伸吹塑瓶及其制造方法 - Google Patents

多层双轴拉伸吹塑瓶及其制造方法 Download PDF

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Publication number
CN100513137C
CN100513137C CNB2005800011289A CN200580001128A CN100513137C CN 100513137 C CN100513137 C CN 100513137C CN B2005800011289 A CNB2005800011289 A CN B2005800011289A CN 200580001128 A CN200580001128 A CN 200580001128A CN 100513137 C CN100513137 C CN 100513137C
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China
Prior art keywords
pet
nylon mxd
stretch blow
biaxial stretch
blow molded
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Expired - Fee Related
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CNB2005800011289A
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CN1860014A (zh
Inventor
佐藤卓
飞田寿德
伊藤大辅
尾泽纪生
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Kureha Corp
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Kureha Corp
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    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/22—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor using multilayered preforms or parisons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
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    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/16—Making multilayered or multicoloured articles
    • B29C45/1642—Making multilayered or multicoloured articles having a "sandwich" structure
    • B29C45/1646—Injecting parison-like articles
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    • B32B27/08—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 of synthetic resin
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Abstract

本发明提供一种多层双轴拉伸吹塑瓶，其具有PET/尼龙MXD6/PET的3层结构或PET/尼龙MXD6/PET/尼龙MXD6/PET的5层结构、且在温度23℃和相对湿度80%的条件下测定出的尼龙MXD6层的氧气透过系数为6.0×10-14·cm3·cm/cm2·sec·cmHg或其以下；还提供利用低拉伸温度和高拉伸倍率下进行双轴拉伸吹塑成型的该瓶的制造方法。

Description

多层双轴拉伸吹塑瓶及其制造方法
技术领域
本发明涉及一种具有聚对苯二甲酸乙二酯/尼龙MXD6/聚对苯二甲酸乙二酯的3层结构或聚对苯二甲酸乙二酯/尼龙MXD6/聚对苯二甲酸乙二酯/尼龙MXD6/聚对苯二甲酸乙二酯的5层结构、且尼龙MXD6层的氧气阻挡性得到显著改善的多层双轴拉伸吹塑瓶，及其制造方法。
背景技术
聚对苯二甲酸乙二酯(以下简称为“PET”)成型得到的PET瓶，不仅强度、透明性、光泽等物理性能优异，而且卫生性和安全性也优异。
作为PET瓶的成型方法，一般采用直接吹塑成型法和拉伸吹塑成型法。直接吹塑成型法是一种使用挤出机或注模机来制造熔融状态的型坯，并将该型坯吹入到吹塑模具中来进行成型的方法。很多PET瓶是通过拉伸吹塑成型法制造的。在拉伸吹塑成型法中，通过注射成型或挤出成型来制造预成型坯，并将该预成型坯控制在一定的温度，然后在吹塑模具内，通过拉伸杆沿纵向拉伸，并通过高压空气沿横向拉伸，制造双轴拉伸吹塑瓶。
PET的熔融粘度低，因此当通过挤出成型制造预成型坯时，存在断面尺寸稳定性降低(drawdown)的问题。因此，通常采用下述方法，即，利用PET的注射成型来制造预成型坯，在小于等于PET的熔点的温度下、对该预成型坯进行拉伸吹塑成型的注射拉伸吹塑成型法。该注射拉伸吹塑成型法包括，不将注射成型的预成型坯完全冷却而在热状态下进行拉伸吹塑的热型坯法，和在将注射成型的预成型坯冷却至室温后、再加热至拉伸温度来进行拉伸吹塑的冷型坯法。
通过PET的拉伸吹塑成型法得到的双轴拉伸吹塑瓶的耐热性、透明性、光泽、香味保留性等优异，且二氧化碳气体阻挡性和氧气阻挡性也比较良好。但是，PET的双轴拉伸吹塑瓶，作为清酒或啤酒等酒类、汽水或可乐等碳酸饮料、果实饮料(除了果汁之外，还包括茶、咖啡、运动饮料等)、药品等的容器，其氧气阻挡性或二氧化碳气体阻挡性尚不充分，从贮存期限(内容物的味道的变化)的观点出发，要求改善气体阻挡性。
以前，作为改善PET的双轴拉伸吹塑瓶的气体阻挡性的方法，提出了在中间层中设置气体阻挡性树脂的具有PET/气体阻挡性树脂/PET的3层结构或者PET/气体阻挡性树脂/PET/气体阻挡性树脂/PET的5层结构的多层双轴拉伸吹塑瓶，并且已经在市场上销售。作为气体阻挡性树脂，包括乙烯-乙烯醇共聚物(以下简称为“EVOH”)、尼龙MXD6等代表性的实例。具有这样的层结构的多层双轴拉伸吹塑瓶一般是通过下述注射拉伸吹塑成型法制造的，所述注射拉伸吹塑成型法，是将PET和气体阻挡性树脂进行共注射成型来制造多层预成型坯，将该多层预成型坯再加热至拉伸温度，然后在吹塑模具内进行双轴拉伸吹塑成型的方法。
在这些气体阻挡性树脂中，虽然EVOH在低湿度下的气体阻挡性优异，但是在高湿度下发生吸湿而导致气体阻挡性降低。因此，含有EVOH层的多层双轴拉伸吹塑瓶不适合用作含水食品、干馏食品(retort food)类的包装材料。
与此相对，尼龙MXD6在分子中不包含氯原子，即使在高湿度下、气体阻挡性也没有太大变化。此外，尼龙MXD6的注射成型温度和拉伸吹塑成型温度，与PET的成型温度基本一致，与PET的共注射成型性优异，并且还能够顺利地实施双轴拉伸吹塑成型。
但是，与其他气体阻挡性树脂相比，尼龙MXD6存在气体阻挡性相当低的缺点。在要充分延长酒类、二氧化碳气体饮料、药品等那样的含有二氧化碳气体的或者容易由于氧化而导致变质的内容物的贮存期限方面，尼龙MXD6受到限制。
目前，对于具有PET/尼龙MXD6/PET的3层结构或者PET/尼龙MXD6/PET/尼龙MXD6/PET的5层结构的多层双轴拉伸吹塑瓶，为了提高氧气阻挡性而在尼龙MXD6层中含有钴盐等氧吸收剂的多层双轴拉伸吹塑瓶被制成啤酒瓶并在市场上销售。但是，如果在尼龙MXD6中含有大量的像钴盐那样的无机填料，则存在很难顺利地实施双轴拉伸吹塑成型、或者拉伸吹塑成型条件受到限制、或者瓶的透明性受损等问题。
还提出了一种气体阻挡性双轴拉伸吹塑瓶，其是在由PET/气体阻挡性树脂/PET的3层组成的双轴拉伸吹塑瓶中，作为中间层的阻挡性树脂，使用了下述气体阻挡性树脂的瓶，所述气体阻挡性树脂以0.1～10重量％的比例含有通过正电荷有机化合物进行离子交换反应而获得的硅酸盐复合体(特开2001-1476号公报，以下称为“文献1”)。在该文献1中，作为气体阻挡性树脂，公开了EVOH和尼龙MXD6。
如果在中间层的尼龙MXD6中含有硅酸盐复合体，则可以得到氧透过率小的多层双轴拉伸吹塑瓶。但是，添加硅酸盐复合体的方法，除了成本高之外，也有可能对瓶的拉伸吹塑成型性、透明性产生不良影响。实际上，在上述文献1中记载了，为了制造上述硅酸盐复合体，必须将对层状结晶的硅酸盐的正电荷有机化合物离子的导入量严格控制在一定的范围内，如果导入量超出规定范围，则不能得到均一的硅酸盐复合体，或者硅酸盐复合体向气体阻挡性树脂的分散性降低。
另外，当制造PET/尼龙MXD6/PET的3层结构或PET/尼龙MXD6/PET/尼龙MXD6/PET的5层结构的多层双轴拉伸吹塑成型容器时，拉伸倍率和拉伸温度等拉伸条件通常被设定为与PET瓶的拉伸条件一致。当使用PET的预成型坯来制造双轴拉伸吹塑瓶时，一般通常将纵向(轴方向)的拉伸倍率(拉伸比)控制在约1.5倍～约2.0倍的范围内，将横向(圆周方向)的拉伸倍率控制在约4.0倍～约4.6倍的范围内，并且，当在面积倍率为约9倍或其以下而在上述各范围内增加横向拉伸倍率时，则纵向的拉伸倍率减小(飽和ポリエステル樹脂ハンドブツク、日刊工业新闻社发行，1989年12月22日第1版第1次印刷，第627页，表12.14)。
关于拉伸温度，一般广泛采用PET的玻璃化转变温度～熔点的温度，但实际上，为了提高PET的定向结晶性并且防止瓶子的白化，经常将预成型坯的拉伸温度提高到95℃～100℃左右。
因此，具有PET/尼龙MXD6/PET的3层结构或PET/尼龙MXD6/PET/尼龙MXD6/PET的5层结构的多层双轴拉伸吹塑瓶通常也是在上述拉伸条件下制造的。
例如，在上述文献1的实施例1～4中，公开了使用在尼龙MXD6中以2～4重量％的比例含有硅酸盐复合体的气体阻挡性树脂，制造PET/气体阻挡性树脂/PET的3层结构的双轴拉伸吹塑瓶的实验例。从这些实施例可知，将通过注射成型制造的多层预成型坯(重量29g、高110mm、直径25mm)再加热至100℃的拉伸温度，然后在纵向拉伸倍率为1.8～1.9倍程度(瓶高200mm)、横向的拉伸倍率为略小于4倍程度(瓶容量500ml)的成型条件下进行双轴拉伸吹塑成型。在该文献1的比较例1中示出了，使用不含硅酸复合盐的尼龙MXD6，在与上述相同拉伸的条件下制造具有PET/尼龙MXD6/PET的3层结构的多层双轴拉伸吹塑瓶。
但是，根据本发明者的研究结果，再次发现：当采用这样的目前的拉伸条件时，在不添加硅酸盐复合体或钴盐等的用于提高氧气阻挡性的无机填料的情况下，不能制造氧气阻挡性得到充分提高的多层双轴拉伸吹塑瓶。
发明内容
本发明的课题在于提供一种多层双轴拉伸吹塑瓶，其具有PET/尼龙MXD6/PET的3层结构或PET/尼龙MXD6/PET/尼龙MXD6/PET的5层结构，并且即使在尼龙MXD6层中不含有用于提高氧气阻挡性的无机填料等添加剂，也能够显著提高尼龙MXD6层的氧气阻挡性。
本发明者们为了解决上述问题而进行了深入的研究，结果发现，通过在较低拉伸温度与较高拉伸倍率的组合的拉伸吹塑成型条件下，对通过共注射成型制造的具有PET/尼龙MXD6/PET的3层结构或PET/尼龙MXD6/PET/尼龙MXD6/PET的5层结构的多层预成型坯进行双轴拉伸吹塑成型，可以显著提高尼龙MXD6层的氧气阻挡性。
具体来说，通过在86～94℃、优选87～93℃的极限低的拉伸温度、且在纵向拉伸倍率为2.10倍或其以上、横向拉伸倍率为4.65倍或其以上的高拉伸倍率下，对通过共注射成型制造的具有PET/尼龙MXD6/PET的3层结构或PET/尼龙MXD6/PET/尼龙MXD6/PET的5层结构的多层预成型坯进行双轴拉伸吹塑成型，可以得到在温度23℃和相对湿度为80％的条件下测定出的尼龙MXD6层的氧气透过系数为6.0×10-14·cm3·cm/cm2·sec·cmHg或其以下、优选为5.5×10-14·cm3·cm/cm2·sec·cmHg或其以下的多层双轴拉伸吹塑瓶。
如果在文献1等中公开的目前的典型的拉伸吹塑条件下，例如在拉伸温度100℃、纵向拉伸倍率1.9倍、横向拉伸倍率4.5倍的拉伸吹塑成型条件下，将上述多层预成型坯成型为多层双轴拉伸吹塑瓶，则在温度23℃和相对湿度80％的条件下测定出的尼龙MXD6层的氧气透过系数仅为9.0×10-14·cm3·cm/cm2·sec·cmHg左右。由此可见，本发明的尼龙MXD6层的氧气阻挡性的改善效果是令人惊讶的。
还发现，在双轴拉伸尼龙MXD6单层薄膜的情况下，即使对拉伸温度和拉伸倍率进行各种改变，也不能得到氧气透过系数为6.0×10-14·cm3·cm/cm2·sec·cmHg或其以下的双轴拉伸薄膜。因此，特定条件下的多层双轴拉伸吹塑成型产生的如上所述的尼龙MXD6层的氧气阻挡性的改善效果是非常独特的。本发明是基于上述发现而完成的。
因此，根据本发明，可以提供一种多层双轴拉伸吹塑瓶，其是具有聚对苯二甲酸乙二酯/尼龙MXD6/聚对苯二甲酸乙二酯的3层结构或聚对苯二甲酸乙二酯/尼龙MXD6/聚对苯二甲酸乙二酯/尼龙MXD6/聚对苯二甲酸乙二酯的5层结构的多层双轴拉伸吹塑瓶，其特征在于，在温度23℃和相对湿度80％的条件下测定出的尼龙MXD6层的氧气透过系数为6.0×10-14·cm3·cm/cm2·sec·cmHg或其以下。
此外，根据本发明，可以提供一种多层双轴拉伸吹塑瓶的制造方法，其特征在于，将聚对苯二甲酸乙二酯与尼龙MXD6进行共注射成型，成型为具有聚对苯二甲酸乙二酯/尼龙MXD6/聚对苯二甲酸乙二酯的3层结构或聚对苯二甲酸乙二酯/尼龙MXD6/聚对苯二甲酸乙二酯/尼龙MXD6/聚对苯二甲酸乙二酯的5层结构的多层预成型坯，接着，在86～94℃的拉伸温度下、在2.10倍或其以上的纵向拉伸倍率、4.65倍或其以上的横向拉伸倍率的条件下，对该多层预成型坯进行双轴拉伸吹塑成型，得到在温度23℃和相对湿度80％的条件下测定出的尼龙MXD6层的氧气透过系数为6.0×10-14·cm3·cm/cm2·sec·cmHg或其以下的多层双轴拉伸吹塑瓶。
具体实施方式
聚对苯二甲酸乙二酯(PET)是利用对苯二甲酸与乙二醇的缩聚反应，伴随着水的生成而合成的(直接聚合法)。PET也可以通过对苯二甲酸二甲酯与乙二醇的酯交换反应来合成(酯交换法)。从容易得到高分子量且着色少的PET的观点出发，优选通过固相聚合得到的PET。
在本发明中，作为PET，可以使用一般的瓶子用的PET。也适合使用与环己烷二甲醇(CHMD)等进行共聚而成的PET。PET的熔点通常为250℃～255℃。可以通过调整二甘醇等的共聚单体含量，来使PET的熔点为所希望的值。瓶子用PET的IV值通常为0.7～1.0。
尼龙MXD6是通过间苯二甲基二胺与己二酸的缩聚得到的结晶性聚酰胺，也被称为聚酰胺MXD6。尼龙MXD6在主链中具有含芳香环的化学结构，与其他尼龙相比，其氧气阻挡性和二氧化碳气体阻挡性等的气体阻挡性优异。
在市售的尼龙MXD6中，还有玻璃纤维强化型和玻璃·矿物质并用强化型等，在本发明中，使用非强化型级别的尼龙MXD6。非强化型级别的尼龙MXD6的代表性的特性包括：比重(ASTM D792)为1.21、在65％的相对湿度下的吸水率(ASTM D570)为3.00％、在1.82Mpa的负荷下的热变形温度(ASTM D648)为93℃等，但是并不限于此。尼龙MXD6的熔点为243℃，通过DSC分析通常在75℃可以观察到玻璃转化温度。本发明所使用的尼龙MXD6实质上不含有硅酸盐复合体、钴盐等的用于提高氧气阻挡性的无机填料。从拉伸吹塑成型性和透明性等的方面出发，优选尼龙MXD6实质上不含有添加剂。
为了制造具有PET/尼龙MXD6/PET的3层结构或PET/尼龙MXD6/PET/尼龙MXD6/PET的5层结构的多层双轴拉伸吹塑瓶，首先，通过注射成型来制造具有这些层结构的容器状的多层预成型坯。为了制造多层预成型坯，使用多层注射成型机，在例如255～285℃的机筒温度、35～45℃的模具温度下，将PET与尼龙MXD6共注射成型。
作为多层预成型坯中的PET与尼龙MXD6的使用比例，PET通常为85～98重量％，优选为88～95重量％，尼龙MXD6通常为2～15重量％，优选为5～12重量％。在本发明中，为了以高拉伸倍率进行双轴拉伸吹塑成型，多层预成型坯优选形成短、厚壁的形状。多层预成型坯的形状可以基于目标多层双轴拉伸吹塑瓶的形状和厚度等来设计。在多层预成型坯中，可以根据常规方法，设置形成瓶子的口部(螺纹部分或帽嵌合部分等)的部分。通常，将多层预成型坯冷却至室温。
为了通过冷型坯法进行拉伸吹塑成型，要将多层预成型坯再加热至拉伸温度。作为预成型坯的加热方式，包括(近)红外加热、覆盖有金属管的加热、石英加热、感应加热等方式，但优选采用能够在厚度方向和长度方向对多层预成型坯进行均匀加热的方式。也可以使多层预成型坯通过拉伸吹塑成型机的加热区来进行再加热。
在本发明中，可以将拉伸温度精密地调节到86～94℃，优选87～93℃的范围内。可以通过在刚进行多层预成型坯的再加热之后，使用红外传感器等来测定多层预成型坯的温度，而实施拉伸温度的测定。如果拉伸温度过低，则双轴拉伸吹塑成型变得困难，瓶的主体部分容易白化。如果拉伸温度过高，即使提高拉伸倍率也不能改善尼龙MXD6层的氧气阻挡性。
使用拉伸吹塑成型机，对达到拉伸温度的多层预成型坯进行拉伸吹塑成型。将多层预成型坯导入拉伸吹塑成型机的吹塑模具内，在该吹塑模具内利用拉伸杆、沿纵向(轴方向)拉伸，并吹入高压空气、沿横向(圆周方向)拉伸。一般来说是插放入拉伸杆开始纵向的拉伸，并在适当的时期吹入高压空气。
在本发明中，使纵向拉伸倍率为2.10倍或其以上、且使横向拉伸倍率为4.65倍或其以上。纵向的拉伸倍率优选为2.15～3.30倍，更优选为2.20～3.00倍。横向的拉伸倍率优选为4.70～5.50倍，更优选为4.80～5.20倍。如果这些拉伸倍率过低，则不能提高尼龙MXD6层的氧气阻挡性。如果这些拉伸倍率过高，则难以制造短而且壁厚的多层预成型坯，其结果是，拉伸吹塑成型本身变得很困难。
目前，如果将纵向的拉伸倍率过度提高，则进行纵向的取向，横向的拉伸变得困难，因此，在双轴拉伸吹塑瓶的成型中，存在抑制其拉伸倍率的倾向。在本发明中，通过调整到极限的拉伸温度，可以在同时提高横向和纵向的拉伸倍率。
所谓纵向的拉伸倍率，是指口部下方的瓶长度(BL)相对于口部下方的多层预成型坯的长度(PL)的比(BL/PL)。横向的拉伸倍率表示瓶的主体部分的内径(BD)相对于多层预成型坯的内径(PD)的比(BD/PD)。
在本发明中，通过在较低的拉伸温度下、且在较高的纵向和横向的拉伸倍率下进行拉伸吹塑成型，可以得到在温度23℃和相对湿度80％的条件下测定出的尼龙MXD6层的氧气透过系数为6.0×10-14·cm3·cm/cm2·sec·cmHg或其以下、优选为5.5×10-14·cm3·cm/cm2·sec·cmHg或其以下、更优选为5.3×10-14·cm3·cm/cm2·sec·cmHg或其以下的多层双轴拉伸吹塑瓶。尼龙MXD6层的氧气透过系数的下限值通常为4.5×10-14·cm3·cm/cm2·sec·cmHg，多数情况为4.8×10-14·cm3·cm/cm2·sec·cmHg左右。
为了测定多层拉伸吹塑瓶的尼龙MXD6层的氧气透过系数，从该瓶的主体部分切取样品片，从该样品片中除去PET层，取出尼龙MXD6单层。在温度23℃和相对湿度80％的条件下测定该尼龙MXD6层的氧透过率。也测定尼龙MXD6层的厚度。根据这些测定值，计算出氧气透过系数。
对本发明的多层双轴拉伸吹塑瓶的形状和大小，没有特别限制，可以制成例如与市场上流通的PET瓶等相同的形状和大小的瓶。本发明的多层双轴拉伸吹塑瓶的层结构为PET/尼龙MXD6/PET的3层结构或PET/尼龙MXD6/PET/尼龙MXD6/PET的5层结构，然而，在很多用途中，PET/尼龙MXD6/PET的3层结构就可以发挥充分的性能。PET层，也包括混合有10重量％左右的PET瓶(PET单层瓶)的粉碎物的循环层的PET层。进而，被配置成5层结构的芯层的PET层，可以是由5层结构的瓶的粉碎物构成的循环层。
本发明的多层双轴拉伸吹塑瓶的主体部分的厚度(总层厚)通常为200～400μm，优选为230～350μm。主体部分的PET层的合计厚度通常为190～350μm，优选为200～300μm。主体部分的尼龙MXD6层的厚度(在2层的情况下，为其合计厚度)通常为10～80μm，优选为30～60μm。
本发明的多层双轴拉伸吹塑瓶的尼龙MXD6层的氧气阻挡性得到显著改善，因此适合用作要求高度的氧气阻挡性或二氧化碳阻挡性的啤酒等酒类、碳酸饮料、果汁饮料、药品、化妆品等的容器。此外，本发明的多层双轴拉伸吹塑瓶使用尼龙MXD6作为气体阻挡性树脂，因此即使在高湿度环境下、气体阻挡性的降低也很小，也适合用作含水食品或干馏食品类的容器。
本发明的多层双轴拉伸吹塑瓶具有优异的气体阻挡性，因而适合用作单位容量的表面积大的内容量为710ml或其以下、特别是280～550ml的小容量瓶。一般来说，如果瓶子的容量变小，则多层预成型坯也变小，拉伸吹塑成型也变得困难，而根据本发明，令人惊讶的是，能够充分应对这种小容量瓶的成型。
实施例
下面通过列举实施例和比较例，来对本发明进行具体的说明。氧气透过系数和拉伸温度的测定方法如下所述。
(1)氧气透过系数：
使用モダンコントロ—ル社制的OX-TRAN 2/20，在温度23℃和相对湿度80％的条件下，测定尼龙MXD6层(薄膜)的氧气透过率，根据该测定值和薄膜厚度来求出氧气透过系数。
(2)拉伸温度：
在预成型坯刚通过拉伸吹塑成型机的再加热区之后，通过红外传感方式的温度测定机来测定该预成型坯的温度。
实施例1
通过使用三菱エンジニアリングプラスチツクス社制的尼龙MXD6(商品名“レニ—6007”)作为中间层(8重量％)、在内外层中使用イ—ストマンケミカル社制的聚对苯二甲酸乙二酯(商品名“EASTAPAK9921W”)，利用多层注射成型机(Kretec公司制造的IN90)，使内外层的注射温度(机筒前端温度)为280℃、使中间层的注射温度为270℃、使模具温度为5℃，制造重28g、全长110mm、口部下方的长度89.1mm(口部长度20.9mm)、外径22mm、内径14.7mm的多层预成型坯。
使用シデル(Sidel)社制的拉伸吹塑成型机SBO-2，在成型循环为950BPH(Bottle Per Hour：每1小时所成型的瓶子的个数，再加热时间约为70秒)、多层预成型坯的再加热温度(拉伸温度)为92℃的条件下，使用拉伸杆沿纵向以2.30倍的拉伸倍率(口部下方的瓶子长度/口部下方的预成型坯的长度)进行拉伸，使用压缩空气沿横向以4.90倍的拉伸倍率(瓶主体部分的内径/预成型坯内径)将该多层预成型坯进行拉伸，从而成型为多层双轴拉伸吹塑瓶。
通过这种方式得到的多层双轴拉伸吹塑瓶的容积为710ml、口部下的长度为207mm、主体部分的外径为72.9mm、主体部分的厚度为250μm。此外，主体部分的各层的厚度为PET层100μm/尼龙MXD6层50μm/PET层100μm。从该瓶的主体部分切取样品片(约100mm×约100mm)，然后，从该样品片中除去内外的PET层，仅取出尼龙MXD6层。测定尼龙MXD6层的氧气透过率和厚度，计算出氧气透过系数(其他实施例和比较例也同样)。结果如表1所示。
实施例2
与实施例1同样操作，制造重28g、全长110mm、口部下方的长度89.1mm(口部长度20.9mm)、外径22mm、内径14.7mm的多层预成型坯。使用该多层预成型坯，并且使用与实施例1不同的吹塑模具、将纵向拉伸倍率从2.30倍改为2.80倍，除此之外，与实施例1同样操作，进行拉伸吹塑成型，制造多层双轴拉伸吹塑瓶。这样得到的多层双轴拉伸吹塑瓶的口部下方长度为249mm、主体部分的外径为72.9mm。结果如表1所示。
实施例3
与实施例1同样操作，制造多层预成型坯。使用该多层预成型坯，并且将再加热温度(拉伸温度)从88℃改为92℃，除此之外，与实施例1同样操作，进行拉伸吹塑成型，制造多层双轴拉伸吹塑瓶。结果如表1所示。
实施例4
与实施例2同样操作，制造多层预成型坯。使用该多层预成型坯，并且将再加热温度(拉伸温度)从88℃改为92℃，除此之外，与实施例2同样地进行拉伸吹塑成型，制造多层双轴拉伸吹塑瓶。结果如表1所示。
比较例1
与实施例1同样操作，制造多层预成型坯。使用该多层预成型坯，并且使用与实施例1不同的吹塑模具，分别将再加热温度(拉伸温度)从88℃改为100℃、将纵向拉伸倍率从2.30倍改为1.90倍、将横向拉伸倍率从4.90倍改为4.50倍，除此之外，与实施例1同样操作，进行拉伸吹塑成型，制造多层双轴拉伸吹塑瓶。这样得到的多层双轴拉伸吹塑瓶的口部下方长度为169mm、主体部分的外径为66.2mm。结果如表1所示。
比较例2
与实施例1同样操作，制造多层预成型坯。使用该多层预成型坯，并且将再加热温度(拉伸温度)从88℃改为100℃，除此之外，与实施例1同样操作，进行拉伸吹塑成型，制造多层双轴拉伸吹塑瓶。结果如表1所示。
比较例3
与实施例2同样操作，制造多层预成型坯。使用该多层预成型坯，并且将再加热温度(拉伸温度)从92℃改为100℃，除此之外，与实施例2同样操作，进行拉伸吹塑成型，制造多层双轴拉伸吹塑瓶。结果如表1所示。
比较例4
与实施例1同样操作，制造多层预成型坯。使用该多层预成型坯，并且使用与实施例1不同的吹塑模具，分别将再加热温度(拉伸温度)从88℃改为97℃、将纵向拉伸倍率从2.30倍改为1.90倍、将横向拉伸倍率从4.90倍改为4.50倍，除此之外，与实施例1同样操作，进行拉伸吹塑成型，制造多层双轴拉伸吹塑瓶。这样得到的多层双轴拉伸吹塑瓶的口部下方长度为169mm、主体部分的外径为66.2mm。结果如表1所示。
比较例5
与实施例1同样操作，制造多层预成型坯。使用该多层预成型坯，并且将再加热温度(拉伸温度)从88℃改为97℃，除此之外，与实施例1同样操作，进行拉伸吹塑成型，制造多层双轴拉伸吹塑瓶。这样得到的多层双轴拉伸吹塑瓶的容积为710ml、口部下方长度为207mm、主体部分的外径为72.9mm。结果如表1所示。
比较例6
在实施例3中，使用与实施例1不同的吹塑模具，并分别将纵向拉伸倍率从2.30倍改为1.90倍、将横向拉伸倍率从4.90倍改为4.50倍，除此之外，通过与实施例3相同的方式进行拉伸吹塑成型，制造多层双轴拉伸吹塑瓶。这样得到的多层双轴拉伸吹塑瓶的容积为710ml、口部下方长度为169mm、主体部分的外径为66.2mm。结果如表1所示。
比较例7
在实施例3中，使用不同的吹塑模具，并且将横向拉伸倍率从4.90倍改为4.50倍，除此之外，与实施例3同样操作，进行拉伸吹塑成型，制造多层双轴拉伸吹塑瓶。这样得到的多层双轴拉伸吹塑瓶的口部下方长度为207mm、主体部分的外径为66.2mm。结果如表1所示。
比较例8
在实施例1中，将再加热温度(拉伸温度)从88℃改为84℃，除此之外，与实施例1同样操作，进行拉伸吹塑成型，制造多层双轴拉伸吹塑瓶。这样得到的多层双轴拉伸吹塑瓶的口部下方长度为207mm、主体部分的外径为72.9mm。结果如表1所示。
表1(多层双轴拉伸吹塑成型)
Figure C200580001128D00161
由表1所示的结果可以清楚地看出，在采用与通常的双轴拉伸吹塑成型条件相同的条件的情况下(比较例1)，尼龙MXD6层的氧气透过系数为9.3×10-14·cm3·cm/cm2·sec·cmHg。即使对纵向和横向的拉伸倍率进行各种改变，在拉伸温度在通常的较高的范围内(比较例2～5)的情况下，也不能大幅改善尼龙MXD6层的氧气透过系数。
此外，即使降低拉伸温度，在纵向和/或横向的拉伸倍率低于本发明所规定的范围(比较例6～7)的情况下，也不能大幅改善尼龙MXD6层的氧气透过系数。如果过度降低拉伸温度(比较例8)，则瓶的主体部分的PET层发生白化。
与此相对，在通过将拉伸温度控制在所限定的低温范围内、并且提高纵向和横向的拉伸倍率来制造多层双轴拉伸吹塑瓶(实施例1～4)的情况下，可以将尼龙MXD6层的氧气透过系数控制在5.5×10-14·cm3·cm/cm2·sec·cmHg或其以下。
比较例9
使用挤出机(プラ技研社制的PEX40-24H型)、在280℃的机筒温度下将三菱エンジニアリングプラスチツクス社制的尼龙MXD6(商品名“レニ—6007”)从T模头中挤出，制造厚度为280μm的未拉伸薄片。测定该未拉伸薄片的氧透过系数。结果如表2所示。
比较例10
与比较例9一样，制造厚度为280μm的尼龙MXD6的未拉伸薄片。使用东洋精机制作所制造的双轴拉伸装置，以7m/分钟的拉伸速度、92℃的拉伸温度、2.50倍的纵向(MD)拉伸倍率、4.50倍的横向(TD)拉伸倍率，对该未拉伸薄膜进行双轴拉伸，制造尼龙MXD6单层的双轴拉伸薄膜。氧气透过系数的测定结果如表2所示。
比较例11～18
除了如表2所示那样改变拉伸温度和纵横拉伸倍率之外，采用与实施例10同样的方式来制造尼龙MXD6单层的双轴拉伸薄膜。关于这些双轴拉伸薄膜的氧气透过系数，测定结果如表2所示。
表2(MXD6的双轴拉伸薄膜)
Figure C200580001128D00171
由表2所示的结果可以清楚地看出，尼龙MXD6的未拉伸薄片(比较例9)的氧气透过率很大、气体阻挡性不充分。如果单独对尼龙MXD6的未拉伸薄膜进行双轴拉伸(比较例10～18)，则虽然能够减小氧气透过系数，但是不能降低至6.0×10-14·cm3·cm/cm2·sec·cmHg或其以下。
在单独对尼龙MXD6的未拉伸薄片进行双轴拉伸(比较例10～18)的情况下，与多层双轴拉伸吹塑成型的情况相比(实施例1～4)不能充分提高氧气阻挡性的理由虽然在现阶段不一定清楚，但是，可以认为这是由于，在使用通过分子链进行应力的传递的双轴拉伸装置的拉伸法中，容易引起分子链被切断、微观结构破坏，与此相对，在多层双轴拉伸吹塑成型法中，由于应力直接作用于尼龙MXD6分子，因此容易形成均一的结构，其结果是，气体阻挡性得到显著提高。
工业可利用性
根据本发明，可以提供了一种具有PET/尼龙MXD6/PET的3层结构或PET/尼龙MXD6/PET/尼龙MXD6/PET的5层结构的多层双轴拉伸吹塑瓶，其即使在尼龙MXD6层中不含有用于提高氧气阻挡性的无机填料等添加剂，也可以显著提高尼龙MXD6层的氧气阻挡性。
根据本发明，由于可以使用实质上不含例如无机填料等添加剂的尼龙MXD6，因而可以在不损害双轴拉伸吹塑成型的顺利实施的条件下，提供透明性、光泽、耐热性、强度等优异、且氧气阻挡性得到显著改善的多层双轴拉伸吹塑瓶。
本发明的多层双轴拉伸吹塑瓶通过充分利用其优异的气体阻挡性、透明性、耐热性、光泽性等特性，可以用作清酒、啤酒等酒类、汽水或可乐等碳酸饮料、果实饮料(除了果汁之外，还包括茶、咖啡、运动饮料等)、药品等的容器。此外，本发明的双轴拉伸吹塑瓶即使在高湿度下、其气体阻挡性的降低也很少，因而也适合用作含水食品或干馏食品类的包装容器。

Claims (14)

1.一种多层双轴拉伸吹塑瓶，是具有聚对苯二甲酸乙二酯/尼龙MXD6/聚对苯二甲酸乙二酯的3层结构或聚对苯二甲酸乙二酯/尼龙MXD6/聚对苯二甲酸乙二酯/尼龙MXD6/聚对苯二甲酸乙二酯的5层结构的多层双轴拉伸吹塑瓶，其特征在于，该多层双轴拉伸吹塑瓶是将多层预成型坯在86～94℃的拉伸温度下、在2.15～3.30倍的纵向拉伸倍率、且在4.70～5.50倍的横向拉伸倍率下进行双轴拉伸吹塑成型获得的，在温度23℃和相对湿度80％的条件下测定出的尼龙MXD6层的氧气透过系数为6.0×10-14·cm3·cm/cm2·sec·cmHg或其以下。
2.如权利要求1所述的多层双轴拉伸吹塑瓶，在温度23℃和相对湿度80％的条件下测定出的尼龙MXD6层的氧气透过系数为5.5×10-14·cm3·cm/cm2·sec·cmHg或其以下。
3.如权利要求1所述的多层双轴拉伸吹塑瓶，在温度23℃和相对湿度80％的条件下测定出的尼龙MXD6层的氧气透过系数为5.3×10-14·cm3·cm/cm2·sec·cmHg或其以下。
4.如权利要求1所述的多层双轴拉伸吹塑瓶，纵向拉伸倍率为2.20～3.00倍，且横向拉伸倍率为4.80～5.20倍。
5.如权利要求1所述的多层双轴拉伸吹塑瓶，尼龙MXD6层是由不含无机填料的尼龙MXD6构成的层。
6.如权利要求1所述的多层双轴拉伸吹塑瓶，瓶的主体部分的总层厚为200～400μm，PET层的合计厚度为190～350μm，且尼龙MXD6层的合计厚度为10～80μm。
7.一种多层双轴拉伸吹塑瓶的制造方法，其特征在于，通过将聚对苯二甲酸乙二酯与尼龙MXD6进行共注射成型，成型为具有聚对苯二甲酸乙二酯/尼龙MXD6/聚对苯二甲酸乙二酯的3层结构或聚对苯二甲酸乙二酯/尼龙MXD6/聚对苯二甲酸乙二酯/尼龙MXD6/聚对苯二甲酸乙二酯的5层结构的多层预成型坯，接着，在86～94℃的拉伸温度下、在2.15～3.30倍的纵向拉伸倍率、且在4.70～5.50倍的横向拉伸倍率下，对该多层预成型坯进行双轴拉伸吹塑成型，得到在温度23℃和相对湿度80％的条件下测定出的尼龙MXD6层的氧气透过系数为6.0×10-14·cm3·cm/cm2·sec·cmHg或其以下的多层双轴拉伸吹塑瓶。
8.如权利要求7所述的制造方法，在聚对苯二甲酸乙二酯为85～98重量％、尼龙MXD6为2～15重量％的比例下，将聚对苯二甲酸乙二酯与尼龙MXD6进行共注射成型，形成预成型坯。
9.如权利要求7所述的制造方法，在87～93℃的拉伸温度下对该多层预成型坯进行双轴拉伸吹塑成型。
10.如权利要求7所述的制造方法，在纵向拉伸倍率为2.20～3.00倍、且横向拉伸倍率4.80～5.20倍的条件下，对该多层预成型坯进行双轴拉伸吹塑成型。
11.如权利要求7所述的制造方法，获得在温度23℃和相对湿度80％的条件下测定出的尼龙MXD6层的氧气透过系数为5.5×10-14·cm3·cm/cm2·sec·cmHg或其以下的多层双轴拉伸吹塑瓶。
12.如权利要求7所述的制造方法，获得在温度23℃和相对湿度80％的条件下测定出的尼龙MXD6层的氧气透过系数为5.3×10-14·cm3·cm/cm2·sec·cmHg或其以下的多层双轴拉伸吹塑瓶。
13.如权利要求7所述的制造方法，尼龙MXD6是不含无机填料的尼龙MXD6。
14.如权利要求7所述的制造方法，获得瓶的主体部分的总层厚为200～400μm，PET层的合计厚度为190～350μm，且尼龙MXD6层的合计厚度为10～80μm的多层双轴拉伸吹塑瓶。
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