CN101203367A - 具有增强机械性能和循环时间的低iv的pet基共聚物预型件、用其制成的容器及方法 - Google Patents

具有增强机械性能和循环时间的低iv的pet基共聚物预型件、用其制成的容器及方法 Download PDF

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Publication number
CN101203367A
CN101203367A CNA2006800220433A CN200680022043A CN101203367A CN 101203367 A CN101203367 A CN 101203367A CN A2006800220433 A CNA2006800220433 A CN A2006800220433A CN 200680022043 A CN200680022043 A CN 200680022043A CN 101203367 A CN101203367 A CN 101203367A
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China
Prior art keywords
preform
container
pet copolymer
intrinsic viscosity
repetitive
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CNA2006800220433A
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English (en)
Inventor
石昱
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Coca Cola Co
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Coca Cola Co
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Publication of CN101203367A publication Critical patent/CN101203367A/zh
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Abstract

一种预型件具有低IV并且包括PET共聚物，该共聚物包括具有来自乙二醇和二甘醇的重复单元的二醇成分和具有来自对苯二甲酸和萘二甲酸的重复单元的二酸成分。二甘醇和萘二甲酸的总量在聚(对苯二甲酸乙酯)共聚物中按从约0.1摩尔百分数至小于2.8摩尔百分数的量存在。预型件在制造容器时是有用的，并且公开了对应方法。

Description

具有增强机械性能和循环时间的低IV的PET基共聚物预型件、用其制成的容器及方法
技术领域
本发明涉及由拥有低水平的二醇和二酸改性的低固有粘度和低拉伸比的聚对苯二甲酸乙二酯(PET)基树脂组分制成的预型件以及它们的容器。
背景技术
聚(对苯二甲酸乙二酯)和其共聚物，通常在工业中简称为“PET”，由于其重量轻且机械和隔气性能的组合优良，已经广泛地用来制造用于碳酸软饮料、果汁、水等的容器。然而，当用于碳酸软饮料(CSD)用途时，由于被叫做环境应力龟裂的现象，必须使用高分子量PET。
高分子量PET具有高固有粘度(IV)。在传统上，在制造CSD容器时希望最小IV是0.80dL/g，优选的IV据说是0.82dL/g或更高。高IV或高分子量PET具有0.80dL/g以上的IV和较少链端，并认为与化学侵蚀剂有较小的相互作用，并因此应力龟裂较少。另外，高IV的PET认为具有较多链缠绕，这可比低IV的PET耗散更多的应力。
然而，高IV的PET要求较长的固态聚合(SSP)时间和由于较高熔化粘度的较高注射模制温度。较高注射模制温度意味着在注射模制期间PET的较大退化和较多能量消耗。高IV的PET也比低IV的PET制造昂贵。尽管如此，最近几年的一般趋势是使用具有约0.84dL/g或更高IV的PET，以避免环境应力龟裂问题的困扰，即使高IV的PET生产成本较高并且从树脂到容器的转化成本较高。较低IV的PET，尽管生产和转化成本较低，但不具有足够的机械强度。这不仅由低IV的PET的较低应力龟裂阻力表明，而且也在PET的自然拉伸比中表明。
对于本领域的技术人员熟知的是，自然拉伸比是PET的固有性质。PET的自然拉伸比取决于PET组分、PET的IV、拉伸温度及拉伸率。在相同拉伸温度和拉伸率下，PET的自然拉伸比随IV或分子量的增大而减小。认为减小由来自高分子量PET的链缠绕引起的。在容器用途中，容器由注射吹制模制过程制成。预型件首先被注射模制，然后在一步或两步过程中吹制模制成容器。
自然拉伸比确定预型件设计。当设计预型件时，重要的是，对于对应瓶子的预型件的拉伸比比聚合物的自然拉伸比大，从而聚合物可达到和通过应变硬化点。只有在PET拉伸过应变硬化点之后，它才开始形成稳定取向和应变诱导结晶度。如果预型件设计成聚合物在吹制模制期间未达到应变硬化点，或者刚达到应变硬化点，则瓶子的生成取向和结晶度将实质较低，并且瓶子的材料分布将更不均匀。这些性能又不仅影响瓶子的机械性能，如侧壁刚度和在压力下的热膨胀，它们也影响穿过容器侧壁的气体透过性和在容器中存储的产品的存放寿命。因此，非常重要的是，根据聚合物的自然拉伸比设计预型件。
这里所使用的拉伸比是在现有技术中熟知的术语，并且按如下定义：
拉伸比＝(最大容器直径/预型件内径)×[(容器完成后的高度)/(预型件完成后的高度)]
由于较高IV的PET具有较低自然拉伸比，所以较低拉伸比预型件可用于较高IV的PET。对于本领域的技术人员也熟知的是，较低拉伸比预型件意味着在相同预型件重量下具有较薄侧壁的较长或较大直径预型件。较薄侧壁意味着，在注射模制期间冷却较快(冷却时间与侧壁厚度的平方成比例)并且周期时间较短。对于用IPA或CHDM改性的普通瓶子级低IV的PET，预型件必须具有较高拉伸比以模制成诸如瓶子之类的容器。较高拉伸比预型件意味着较厚侧壁和较长冷却时间，这样转换成生产率的降低。如果预型件为了高IV的PET而设计，并且低IV用来模制这样的预型件，则当吹制成瓶子时材料将不适当地拉伸，并且侧壁将会结晶和定向。这将引起对于CSD容器的蠕变增大和瓶子侧壁刚度的减小。
因而，在现有技术中存在对于较低IV的PET预型件的需要，该较低IV的PET预型件具有通常用于高IV的PET的常规构造，但对于制造具有适当机械性能和应力龟裂阻力的容器也是有用的。
发明内容
本发明通过提供具有低拉伸比的低IV的PET共聚物预型件而满足以上需要，从而传统的高IV的PET预型件构造可用来用预型件制造容器而不管低IV。通常，低IV的PET预型件意味着预型件具有较高拉伸比，以形成具有希望机械性能的容器。然而，本发明的预型件挑战传统，并且生产一种具有希望机械性能的容器，即使它具有较低IV和较低拉伸比。因为特征的这种独特组合，本发明的预型件可用来在比较高IV的PET预型件短的周期时间下制造容器。
更具体地说，本发明的预型件包括聚(对苯二甲酸乙二酯)共聚物，该共聚物包括具有来自乙二醇和二甘醇的重复单元的二醇成分和具有来自对苯二甲酸和萘二甲酸的重复单元的二酸成分，其中，分别基于二醇成分的100摩尔百分数和二酸成分的100摩尔百分数，在PET共聚物中存在的二甘醇和萘二甲酸的总量是从约0.1摩尔百分数至小于约2.8摩尔百分数的量。另外，预型件具有小于0.77dL/g的固有粘度。这意味着，二甘醇的摩尔百分比是基于100摩尔百分数的二醇成分并且萘二甲酸的摩尔百分比是基于100摩尔百分数的二酸成分。这种定义适用于贯穿本说明书的摩尔百分比。
本发明也包括用上述预型件制成的容器和用来制造预型件和容器的方法。
另外，本发明包括用来减少用于制造容器的周期时间的方法，该方法包括步骤：
(1)提供包括具有来自乙二醇和二甘醇的重复单元的二醇成分和具有来自对苯二甲酸和萘二甲酸的重复单元的二酸成分的PET共聚物熔体，其中，分别基于二醇成分的100摩尔百分数和二酸成分的100摩尔百分数，在PET共聚物中存在的二甘醇和萘二甲酸的总量是从约0.1摩尔百分数至小于约2.8摩尔百分数的量，
(2)然后把PET共聚物注射到模具中，
(3)然后冷却模具和包含的聚合物，
(4)然后把具有小于0.77dL/g固有粘度的预型件与模具脱开，
(5)然后重新加热预型件，及
(6)然后把预型件吹制模制成容器；
其中，与用包括PET共聚物和具有至少0.77dL/g的固有粘度的预型件制造第二容器的第二周期时间相比，减少用来制造容器的周期时间。
本发明的其它目的、特征及优点由如下详细描述、附图及权利要求书将变得明显。
附图说明
图1是具有常规构造的、用按照本发明优选实施例的PET共聚物制成的注射模制预型件的剖视图。
图2是按照本发明优选实施例由图1的预型件制成的吹制模制容器的剖视图。
具体实施方式
本发明包括具有低拉伸比的低IV的PET共聚物预型件以及用上述预型件制成的容器和用来制造预型件和容器的方法。另外，本发明包括用来减少用于制造容器的周期时间的方法。
根据一个实施例，把PET共聚物制成注射模制预型件，该注射模制预型件然后吹制模制成容器。预型件包括敞开端口形成部分、中间本体形成部分及封闭底形成部分。预型件包括PET共聚物，该PET共聚物包括具有来自乙二醇和二甘醇的重复单元的二醇成分和具有来自对苯二甲酸和萘二甲酸的重复单元的二酸成分，其中二甘醇和萘二甲酸的总量按从约0.1摩尔百分数至约2.8摩尔百分数的量存在于PET共聚物中。二醇成分和二酸成分的摩尔百分数包括在PET共聚物组分中的所有残余共聚用单体，如在PET共聚物的制造过程期间或经过其形成的那些。在整个说明书的所有实例中，PET共聚物基于包括二醇成分的100摩尔百分数和二酸成分的100摩尔百分数的总共200摩尔百分数。这意味着，二甘醇的摩尔百分比是基于100摩尔百分数的二醇成分并且萘二甲酸的摩尔百分比是基于100摩尔百分数的二酸成分。这种定义适用于整个说明书的摩尔百分比。
在PET共聚物中的二甘醇和萘二甲酸每一种的量在两者的总量内可变化到某种程度。在优选实施例中，二甘醇和萘二甲酸的总量按从约1.1摩尔百分数至约2.8摩尔百分数的量，并且更优选地，按从约1.2摩尔百分数至约2.3摩尔百分数的量，存在于聚(对苯二甲酸乙二酯)共聚物中。在PET共聚物中存在的二甘醇优选地处于从1.3至2.5摩尔百分数并且更优选地从1.5至2.2摩尔百分数的量。在PET共聚物中存在的萘二甲酸优选地处于从0.2至1摩尔百分数并且优选地从0.2至0.75摩尔百分数，并且更优选地从0.25至0.75摩尔百分数的量。
PET共聚物预型件优选地具有根据ASTM D4603-96测量的小于0.77dL/g、优选地从约0.6至小于约0.77dL/g、更优选地从约0.70至小于约0.76dL/g、并且甚至更优选地从约0.70至约0.74dL/g的固有粘度(IV)。
希望地，本发明的预型件包括反应级PET共聚物树脂，意味着PET树脂是在共聚用单体与非聚合物混合物之间的化学反应的直接产物。
优选的非对苯二甲酸二酸成分是2，6-萘二甲酸(NDC)。
在本发明的PET共聚物中的DEG水平在从约0.1至约2.0摩尔百分数的范围内，该水平在常规PET(下文“常规PET”)的制造中存在的DEG的典型残余水平之下。常规PET典型地包含从约2.4至约2.9摩尔百分数的DEG，这等效于约1.3至约1.6的更普遍提到的重量百分数值。在PET制造领域的技术人员一般把DEG当作聚合物制造的无害副产品；因此，几乎没有进行旨在减小在打算用于容器的PET中的DEG水平的努力。因而，为了实现用来制造本发明的预型件的PET共聚物中的较低DEG水平，必定出现对用于容器的PET制造过程的修改。可采用适于用来减小聚酯的DEG含量的任何方法。适当的方法包括减小在酯化或酯转移反应中二酸或二酯相对于乙二醇的摩尔比值；降低酯化或酯转移反应的温度，包括四烃基铵盐等的DEG抑制添加剂的添加；及再循环回酯化或酯转移反应的乙二醇的DEG含量的减小。
在本发明的实施例中，不管低IV和常规构造，当用来制造容器时预型件具有在从约8至约13范围中的拉伸比，并且更希望的是从约8至约12。这里所使用的拉伸比参考在本领域中熟知的术语，并且按如下定义：
拉伸比＝(最大容器直径/预型件内径)×[(容器完成后的高度)/(预型件完成后的高度)]
自然拉伸比是聚合物的固有性质。相对于预型件的聚合物的自由吹制体积的测量-用在这里的例子中，其提供一种测量聚合物的自然拉伸比的方法。聚合物的自然拉伸比通过确定在用来制造容器的吹制模制过程中使用的预型件的拉伸比极限影响预型件设计。具有较低自然拉伸比的聚合物允许以较低拉伸比设计预型件。借助于聚合物的自然拉伸比的理解，可选择诸如高度、内径及壁厚之类的预型件尺寸，从而预型件可被吹制模制成具有诸如重量、高度、最大直径、热稳定性及侧壁刚度之类的一定选择物理性能的容器。
在本发明的另一个实施例中，一种用来减少用于制造容器的周期时间的方法包括步骤：
(1)提供包括具有来自乙二醇和二甘醇的重复单元的二醇成分和具有来自对苯二甲酸和萘二甲酸的重复单元的二酸成分的PET共聚物熔体，其中，分别基于二醇成分的100摩尔百分数和二酸成分的100摩尔百分数，在PET共聚物中存在的二甘醇和萘二甲酸的总量是从约0.1摩尔百分数至约2.8摩尔百分数的量，
(2)然后把PET共聚物注射到模具中，
(3)然后冷却模具和包含的聚合物，
(4)然后把具有小于0.77dL/g固有粘度的预型件与模具脱开，
(5)然后重新加热预型件，及
(6)然后把预型件吹制模制成容器；
其中，与用包括PET共聚物和具有至少0.77dL/g的固有粘度的预型件用来制造第二容器的第二周期时间相比，减少用来制造容器的周期时间。
在又一个方法实施例中，一种用来制造在制造容器时使用的预型件的方法包括注射模制PET共聚物，该PET共聚物包括具有来自乙二醇和二甘醇的重复单元的二醇成分和具有来自对苯二甲酸和萘二甲酸的重复单元的二酸成分。在PET共聚物中存在的二甘醇和萘二甲酸的总量是从约0.1摩尔百分数至约2.8摩尔百分数的量，并且预型件具有小于0.77dL/g的固有粘度。
在另一个实施例中，一种用来制造容器的方法包括吹制模制注射模制预型件，该注射模制预型件具有敞开端口形成部分、中间本体形成部分及封闭底形成部分，并且包括PET共聚物。PET共聚物包括具有来自乙二醇和二甘醇的重复单元的二醇成分和具有来自对苯二甲酸和萘二甲酸的重复单元的二酸成分。在PET共聚物中存在的二甘醇和萘二甲酸的总量是从约0.1摩尔百分数至约2.8摩尔百分数的量，并且预型件具有小于0.77dL/g的固有粘度。
标题为“用于低自然拉伸比PET共聚物的预型件、用其制造的容器及方法”并且提交于2005年5月11日的共同待审专利申请的公开通过参考特意包括在这里，其公开了一种预型件，该预型件关于一定环向比值和轴向比值极限具有减小的拉伸比，相对于由在现有技术中可得到的PET树脂制成的预型件，由具有较低自然拉伸比的LNSR聚合物制成。这个参考文件也公开了一种具有优良机械性能的拉伸吹制模制容器，特别是饮料容器，由这种预型件设计制成。而且，这个参考文件公开了一种透明容器，或大体透明、不模糊或大体不模糊的拉伸吹制模制容器。此外，低自然拉伸比聚合物独立地公开在于2004年10月18日提交在美国专利和商标局的共同待审美国专利申请No.10/967,803中，并且在其中要求保护，该专利申请是于2003年10月30日提交在美国专利和商标局的美国专利申请No.10/696,858的继续申请，后者按照35U.S.C.§119要求于2002年11月1日提交的美国临时专利申请序列号为60/423,221的优先权，该申请的公开也通过参考特意全部包括在这里。
具体地说，本发明的实施例适于用来制造用于在碳酸和非碳酸软饮料工业和食品工业中的包装用途的容器。PET共聚物预型件通过用诸如熔化成形之类的常规方法将上述聚酯组分形成预型件而制成。适当的熔化成形过程包括但不限于，注射模制、挤压、热成形及压缩模制。容器在单级、双级及双重吹制模制制造系统中由预型件制成。这样的方法对于本领域的技术人员是熟知的，并且适当预型件和容器结构的例子公开在美国专利5,888,598中，该专利的公开也通过参考特意全部包括在这里。希望的最终结果是具有足够机械和阻隔性能的透明容器，以提供对于包含饮料或食品生产的适当保护。
理想地，通过把聚酯注射模制成具有可吹制几何形式的预型件而形成容器预型件。然后把预型件或可吹制型材包含在具有希望容器的体积轮廓的模具空腔内，并且通过在模具空腔的约束内用压缩空气吹制预型件而使它膨胀。
在薄壁一次使用PET饮料容器的制造中所使用的可买到的设备，可以用来制造按照本发明实施例的容器。另外，也可以使用在制造常规厚壁可重新填充PET容器时使用的工业设备。
按照本发明的实施例，适当容器可以由具有敞开顶端和瓶颈成品部分的圆柱形注射模制预型件吹制模制。预型件可以具有锥形肩形成部分、沿圆柱侧面的大体均匀厚度及优选地在香槟设计中的底形成部分，但包括具有诸如花瓣之类的瓶底杯或带脚设计的半球形瓶底。在优选实施例中，预型件是无定形的和大体透明的，并且被注射模制。
按照本发明的优选实施例，容器预型件以后放置在吹制模制设备中，该吹制模制设备具有：上部模具段，它啮合瓶颈成品部分；中部模具段，具有形成容器侧壁形状的内部空腔；及下部模具段，具有形成容器底的外凹拱形部分的上部表面。按照标准再加热拉伸吹制模具过程，注射模制预型件首先被重新加热到约70℃至130℃的适于拉伸和取向的温度，被放置在吹制模具中，及然后把轴向拉伸杆插入在敞开上端部中并且向下运动以轴向拉伸预型件。以后或同时地，把膨胀气体引入到预型件的内部，以使肩部、侧壁及底形成部分径向向外膨胀成与模具段的内部表面相接触。生成吹制容器具有与预型件相同的瓶颈成品部分，该瓶颈成品部分具有外螺纹和象预型件的最下部瓶颈凸缘。瓶子的剩余部分经受膨胀，一直到变化的程度。可除去瓶盖附加到容器的敞开上端部上。瓶盖包括基础部分，该基础部分具有与在瓶颈成品部分上的外螺纹相啮合的内螺纹。
在生产透亮或透明容器时重要的考虑是，首先生产透亮或透明预型件。在注射模制步骤期间，热诱导结晶可出现在聚合物到预型件的转换中。热诱导结晶往往在聚合物中形成巨大晶粒，伴随有模糊的形成。为了使晶粒的形成最小化并因而具有透亮预型件，热结晶的速率需要足够慢，从而可生产具有很小或没有结晶度的预型件。然而，如果热结晶的速率太慢，则可能不利地影响PET树脂的生产速率，因为PET必须在固态聚合之前热晶化，一种用来增大PET的分子量并且同时除去有害乙醛的过程。固态聚合增大聚合物的分子量，从而由聚合物制成的容器将具有必需的强度。用来减小热结晶速率的现有技术工艺包括使用包含一定量的共聚用单体的PET。最普通使用的共聚用单体调节剂是间苯二酸或1，4-环己烷二甲醇，它们在从1.5至3.0摩尔百分数的范围内的水平下被添加。
抵消减小在注射模制期间的热结晶速率的需要是，增大在吹制模制期间发生的应变诱导结晶度的速率的需要。应变诱导结晶度由PET的快速机械变形生成，并且产生极小的透明的晶粒。在容器侧壁中存在的结晶度的量与容器的强度和阻隔性能相关。以前，已经证明，把PET的DEG量从2.9增大到4.0摩尔百分数，与包含在2.4至2.9摩尔百分数DEG的常规PET相比，引起PET的结晶速率的增大。用于这种现象的原理是，由较高DEG含量生成的增大聚合物链灵活性允许聚合物链更迅速地排序和填充成聚合物晶体。
在本发明的PET共聚物中，热结晶的减小速率和应变诱导结晶的增大速率都意外地发现借助于在很低量下的NDC和DEG的共聚用单体改性而发生。认为NDC由于NDC部分的刚性阻碍聚合物链灵活性而减小热结晶速率，并因而使晶粒的形成更困难。NDC的添加也已经发现增强PET链的刚性，并且导致由PET共聚物制成的容器的侧壁刚度的意外增大。此外并且与期望相反，相对于常规PET，减小在PET共聚物中的DEG含量导致应变诱导结晶速率的增大。
低量DEG和NDC的这种独特组合的后果，至少在优选实施例中是，即使当降低PET共聚物的IV时与常规PET的自然拉伸比相比PET共聚物的自然拉伸比也减小。通常，低IV的PET预型件意味着，预型件具有较高拉伸比以形成具有希望机械性能的容器。然而，本发明的预型件挑战传统，并且生产一种具有希望机械性能的容器，即使它具有较低IV和较低拉伸比。因为特征的这种独特组合，本发明的预型件可用来在比较高IV的PET预型件要短的周期时间下制造容器。
参见图1，表明了具有常规构造的聚酯预型件10，但没有按比例画出。预型件10通过注射模制本发明的PET共聚物而制成，并且包括螺纹瓶颈成品部分12，该螺纹瓶颈成品部分12在其下端部处在盖顶凸缘14中终止。在盖顶凸缘14下面，有在逐渐减小外径的段18中终止的一般圆柱形段16，以便提供增大的壁厚。在段18下面，有细长瓶体段20。从盖顶凸缘14到细长瓶体段20的封闭端部21测量预型件的高度。
在图1中表明的预型件10可吹制模制以形成在图2中表明的容器22。容器22包括外壳24，该外壳24包括限定瓶口28的螺纹瓶颈成品部分26、在螺纹瓶颈成品部分下面的盖顶凸缘30、从盖顶凸缘延伸的锥形段32、在锥形段下面延伸的瓶体段34及在容器的底部处的瓶底36。从盖顶凸缘30到在瓶底36处的封闭端测量容器的高度。容器22适于用来制成包装饮料38，如在图2中表明的那样。包装饮料38包括在容器22中的碳酸苏打饮料和密封容器的瓶口28的瓶盖40。
根据本发明的优选实施例，预型件的中间本体形成部分具有从1.5至8mm的壁厚。此外，根据优选实施例，预型件的中间本体形成部分具有从10至30mm的内径，并且预型件的高度-它从与成品部分相对的预型件的封闭端到成品部分延伸，是从50至150mm。优选地，按照本发明优选实施例制成的容器具有在0.25至3升的范围内的体积和0.25至0.65mm的壁厚。
在本说明书中，参考预型件10和生成容器22的尺寸。预型件的高度H是从与成品部分12相对的预型件的封闭端21到成品部分的盖顶凸缘14的距离。预型件10的内径ID是在预型件的细长瓶体段20的内壁之间的距离。预型件10的壁厚T也在预型件的细长瓶体段20处测量。容器22的高度H′是从与成品部分26相对的容器的瓶底36的封闭端到成品部分的盖顶凸缘30的距离。最大容器直径MD是沿容器22的高度在其最宽点处的容器直径。预型件的环向拉伸比等于最大容器直径除以预型件内径，并且轴向拉伸比等于在成品部分下面的容器高度除以在成品部分下面的预型件高度。预型件的拉伸比等于环向拉伸比和轴向拉伸比的乘积。
预型件10、容器22及包装饮料38只不过是本发明的典型实施例。应该理解，按照本发明的实施例可制成具有各种构造的各种预型件和容器。
以上描述了本发明，并且下面通过例子进一步表明，例子绝不应解释成对本发明的范围加以限制。相反，要清楚地理解，可以采用各种其它实施例、修改及其等效物，这些在阅读这里的描述之后将呈现在本领域的技术人员眼前，而不脱离本发明的精神和/或附属权利要求书的范围。
例1
预型件用三种不同的PET共聚物树脂制成。C1，一种比较树脂，是常规PET共聚物树脂，并且R1和R2是根据本发明实施例制成的树脂。PET树脂在真空炉中在135℃下过夜干燥，以在注射模制之前实现低于50ppm的湿度水平。用试验室规模的Arburg(阿博格)单元空腔注射机进入常规预型件模具中以拉伸比为约14进行注射模制。预型件然后自由地吹制到汽泡以确定每种聚合物的拉伸比。对于每种预型件变量进行自由吹制，并且气泡在psi(每平方英寸)下在100℃和105℃的温度下吹制。测量和记录每个气泡的拉伸比。
试样材料的详细描述列在表1中。
                      表1树脂描述
  树脂组分  IPA(摩尔％)  NDC(摩尔％)  DEG(摩尔％)   预型件IV
  C1  2.8  0  2.9   0.78
  R1  0  0.5  1.5   0.79
  R2  0  0.5  1.5   0.76
     表2由自由吹制气泡计算的面积拉伸比
  树脂   面积拉伸比   拉伸比％减小
  C1   14.81   0
  R1   11.81   20％
  R2   11.23   24％
表1表明，R1和R2具有相同的树脂组分，但R2具有比R1低的IV。表2表明，R2和R1具有类似的自然拉伸比。R2具有比R1低的拉伸比。在0.76的IV下，R2具有比C1低的拉伸比。因此，用R2树脂制成的并且具有对于C1设计的构造的预型件应该没有问题地吹制模制成CSD容器。
例2
为了进一步表明具有较低IV的本发明实施例的拉伸比，如在表3中表示的那样制成更多的树脂。预型件如例1中那样模制，并且自由吹制。树脂C1和C2是常规PET共聚物树脂，并且树脂R3是具有较低IV的较低IV的PET共聚物树脂。来自C2和R3的预型件也用Sidel SBO 1机器吹制模制成500ml Coca-Cola轮廓瓶。
                       表3树脂描述
  树脂组分  IPA(摩尔％)  NDC(摩尔％)  DEG(摩尔％)   预型件IV
  C1  2.8  0  2.9   0.78
  C2  2.8  0  2.9   0.74
  R3  0  0.3  2.0   0.73
     表4由自由吹制气泡计算的面积拉伸比
  树脂   面积拉伸比   拉伸比％减小
  C1   14.81   0
  C2   15.12   -2％
  R3   12.55   15％
表4表明，当使用通常CSD级PET时，低IV(0.74)的确具有比较高IV(0.78)树脂稍高的拉伸比。但当使用根据本发明实施例组分制成的树脂时，低IV(0.73)仍然具有比高IV常规PET(0.78)低的拉伸比。为了进一步证明IV的效果，C2和R3预型件如以上描述的那样吹制成瓶子。这与对于常规PET共聚物树脂在IV与拉伸比之间的关系相反。
为了进一步证明IV的效果，C1和R3预型件如以上描述的那样使用对于常规PET共聚物树脂C1设计的预型件构造吹制成瓶子。使用根据ASTM D 1505-85的密度柱方法对于两组瓶子测量侧壁的结晶度。该结果在表5中示出。
  表5瓶子的结晶度
  树脂   结晶度
  C2   20.6％
  R3   25.9％
如表明的那样，用C2树脂制成的瓶子具有比用R3树脂制成的瓶子低的结晶度，指示比较树脂C2预型件没有充分拉伸，并且使用为高IV常规C2树脂设计的预型件构造没有实现高水平的取向和结晶度。为了进一步证明这点，如下面表示的那样对这些瓶子进行进一步试验。
根据下文所描述的Coca-Cola公司的标准过程进行热稳定性试验。热稳定性试验用来测量由温度和压力应力引起的瓶子尺寸的物理变化。按如下进行热稳定性测量：
测量“所接收的”试验瓶子尺寸和厚度。然后瓶子用水碳酸填充到4.1+/-0.1的体积，并且盖上瓶盖。填充瓶子暴露于环境温度过夜，并且测量尺寸以确定百分数变化。瓶子暴露于38℃，并且测量尺寸以确定百分数变化。
12个试验试样使用永久墨水标记在瓶子的底部半部上标有试验要求和试样号。在环境温度下进行尺寸测量之后，把试样存储在38℃的环境腔室中24小时。对于在38℃环境腔室之后调节的填充瓶子完成填充点下降、隆起及尺寸的测量。对于测试的每一天，计算所有尺寸的最小、最大、平均及标准偏差值。关键尺寸变化列在表7中。
                    表6瓶子的热稳定性
  树脂   标签直径变化％   填充点下降(英寸)   高度变化％
  R3   0.86％   0.839   2％
  C2   2.17％   0.975   2％
如在表6中表明的那样，用比较C2树脂制成的瓶子具有比用R3树脂制成的那些差的热膨胀，指示为比较树脂C1设计的预型件不适于低IV C2树脂。然而，R3树脂可使用为比较性较高IV的C1树脂设计的预型件。在这种情况下，由R3树脂制成的瓶子满足来自Coca-Cola公司的热稳定性技术规格，而由C2树脂制成的瓶子不满足热稳定性技术规格。
根据下文描述的修改ASTM方法对于用树脂C2和R3制成的瓶子进行侧壁挠曲试验。侧壁挠曲与侧壁刚度相关。实现特定侧壁挠曲需要的力越大，瓶子侧壁的刚度越大。
    表7瓶子的侧壁挠曲
  树脂   平均侧壁挠曲(lbf)
  C2   6.46
  R3   7.88
表7表明，用低IV的R3制成的瓶子具有比用常规低IV的C2树脂制成的那些高的侧壁刚度，指示R3树脂制成具有比用低IV的C2树脂制成的瓶子高的机械强度的瓶子，可能归因于C2树脂在较高IV的C1树脂预型件设计中不足以拉伸到达到高取向和结晶度的事实。
用C2和R3树脂制成的瓶子经受下面所描述的加速应力龟裂试验。为了加速应力龟裂阻力测试，随机选择每个变量的二十五(25)个试样，并且充碳酸气到4.1-4.5体积的CO2。把试样在72_和50％RH的环境下存储24小时。然后把这些瓶子每一个的瓶底区域浸入在稀释氢氧化钠(0.1％)溶液中。然后在3小时的过程中认真检查每个瓶子，以便探测穿过瓶底裂纹的二氧化碳泄漏或摧毁性瓶底失效。如果探测到任何碳酸泄漏或瓶底破坏，则记录到这个失效点的时间。
                    表8加速应力龟裂
  树脂   到失效的平均时间(小时)   通过3小时试验的瓶子数#
  C2   0.56   1
  R3   2.43   11
如在表8中看到的那样，用C2树脂制成的瓶子具有非常差的应力龟裂阻力，而用R3树脂制成的瓶子具有可接受的应力龟裂阻力。数据表明，C2树脂，如对于低IV期望的那样，由于缺乏应力龟裂阻力不能用于CSD包装。然而，R3树脂意外地表现出较高应力龟裂阻力。
例3
为了进一步证明按照本发明实施例使用的树脂的好处，制成具有在表9中所示的不同组分的一系列低IV树脂(R4、R5及R6)。树脂注射模制成500ml预型件，并且如例1中描述的那样自由吹制。自由吹制气泡的体积被记录作为拉伸比的指示。与面积拉伸比相比，体积更容易测量并且不需要计算。
                     表9树脂描述
树脂   IPA摩尔％   NDC摩尔％   DEG摩尔％ 预型件IV
  C1   3.0   0   2.9   0.78
  R4   0   0.4   1.5   0.74
  R5   0   0.4   1.8   0.72
  R6   0   0.4   2.3   0.72
          表10自由吹制结果
  树脂   气泡体积(ml)   ％减少
  C1   789   0
  R4   636   19％
  R5   687   13％
  R6   695   12％
表10表明按照本发明实施例制成的低IV(小于0.75)树脂R4、R5及R6仍然具有比较高IV(0.78)下控制树脂低的拉伸比。为了进一步证明树脂R4、R5及R6的值，它们如在以上例1中描述的那样再次模制成预型件，并且吹制成500ml轮廓瓶。
来自例3的树脂注射模制成预型件，然后如在例1中那样吹制成瓶子。然后这些瓶子如在例2中那样经受热稳定性测量。结果表示在表11中。
                  表11热稳定性结果
  树脂   标签直径变化％   高度变化％   填充点下降(英寸)
  C1   1.1   1.5   0.64
  R4   l.0   1.4   0.59
  R5   1.1   1.4   0.61
  R6   1.1   1.4   0.59
如可在表11中看到的那样，尽管用于树脂R4至R6的预型件IV的范围从0.72至0.74，但它们在热稳定性方面表现得与具有0.78的预型件IV的比较树脂C1相同。
应该理解，以上涉及了本发明的具体实施例，并且其中可以进行多种变更，而不脱离由如下权利要求书定义的本发明的范围。

Claims (42)

1.一种预型件，具有敞开端口形成部分、中间本体形成部分及封闭底形成部分，并且包括PET共聚物，该PET共聚物包括具有来自乙二醇和二甘醇的重复单元的二醇成分和具有来自对苯二甲酸和萘二甲酸的重复单元的二酸成分，其中，分别基于二醇成分的100摩尔百分数和二酸成分的100摩尔百分数，在PET共聚物中存在的二甘醇和萘二甲酸的总量处于从约0.1摩尔百分数至约2.8摩尔百分数的量，并且预型件具有小于0.77dL/g的固有粘度。
2.根据权利要求1所述的预型件，其中，在PET共聚物中存在的二甘醇和萘二甲酸的总量处于从约1.2摩尔百分数至约2.3摩尔百分数的量。
3.根据权利要求1所述的预型件，其中，来自萘二甲酸的重复单元按从约0.2至约1.0摩尔百分数的量存在于PET共聚物中。
4.根据权利要求1所述的预型件，其中，来自萘二甲酸的重复单元按从约0.2至约0.75摩尔百分数的量存在于PET共聚物中。
5.根据权利要求1所述的预型件，其中，来自萘二甲酸的重复单元按从约0.25至约0.75摩尔百分数的量存在于PET共聚物中。
6.根据权利要求1所述的预型件，其中，来自二甘醇的重复单元按从约1.3至约2.5摩尔百分数的量存在于PET共聚物中。
7.根据权利要求1所述的预型件，其中，来自二甘醇的重复单元按从约1.5至约2.2摩尔百分数的量存在于PET共聚物中。
8.根据权利要求1所述的预型件，其中，来自萘二甲酸的重复单元按从约0.2至约1.0摩尔百分数的量存在于PET共聚物中，并且来自二甘醇的重复单元按从1.3至约2.5摩尔百分数的量存在于PET共聚物中。
9.根据权利要求1所述的预型件，其中，萘二甲酸是2，6-萘二甲酸。
10.根据权利要求1所述的预型件，其中，来自萘二甲酸的重复单元是2，6-萘二甲酸，并且按从约0.2至约1.0摩尔百分数的量存在于PET共聚物中，并且来自二甘醇的重复单元按从约1.3至约2.5摩尔百分数的量存在于PET共聚物中。
11.根据权利要求1所述的预型件，其中，预型件具有在从约0.60dL/g至小于0.77dL/g的范围内的固有粘度。
12.根据权利要求1所述的预型件，其中，预型件具有小于0.76的固有粘度。
13.根据权利要求1所述的预型件，其中，预型件具有在从约0.70dL/g至小于0.76dL/g的范围内的固有粘度。
14.根据权利要求1所述的预型件，其中，预型件具有在从约0.70dL/g至约0.74dL/g的范围内的固有粘度。
15.根据权利要求1所述的预型件，其中，预型件具有在从约8至约13范围中的拉伸比。
16.根据权利要求1所述的预型件，其中，预型件具有在从约8至约12范围中的拉伸比。
17.一种通过吹制模制权利要求1的预型件而制成的容器。
18.根据权利要求17所述的容器，其中，预型件的中间本体形成部分具有从约1.5至约8mm的壁厚度和从约10至约30mm的内径，并且预型件具有成品部分、与成品部分相对的封闭端部及从约50至约150mm的从封闭端部到成品部分的高度。
19.根据权利要求17所述的容器，其中，容器具有在从约0.25至约3升的范围内的体积。
20.根据权利要求7所述的容器，其中，容器是瓶子、鼓形物、玻璃水瓶或冷却器。
21.一种包装饮料，包括通过吹制模制权利要求1的预型件而制成的容器和在容器中的饮料。
22.一种用来制造在制造容器时使用的预型件的方法，包括注射模制PET共聚物，该PET共聚物包括具有来自乙二醇和二甘醇的重复单元的二醇成分和具有来自对苯二甲酸和萘二甲酸的重复单元的二酸成分，其中，分别基于二醇成分的100摩尔百分数和二酸成分的100摩尔百分数，在PET共聚物中存在的二甘醇和萘二甲酸的总量处于从约0.1摩尔百分数至约2.8摩尔百分数的量，并且预型件具有小于0.77dL/g的固有粘度。
23.根据权利要求22所述的方法，其中，预型件具有在从约0.60dL/g至小于0.77dL/g的范围内的固有粘度。
24.根据权利要求22所述的方法，其中，预型件具有小于0.76的固有粘度。
25.根据权利要求22所述的方法，其中，预型件具有在从约0.70dL/g至小于0.76dL/g的范围内的固有粘度。
26.根据权利要求22所述的方法，其中，预型件具有在从约0.70dL/g至约0.74dL/g的范围内的固有粘度。
27.根据权利要求22所述的方法，其中，预型件具有在从约8至约13范围中的拉伸比。
28.根据权利要求22所述的方法，其中，预型件具有在从约8至约12范围中的拉伸比。
29.一种用来制造容器的方法，包括吹制模制注射模制的预型件，该预型件
(a)具有敞开端口形成部分、中间本体形成部分及封闭底形成部分，并且
(b)包括PET共聚物，该PET共聚物包括具有来自乙二醇和二甘醇的重复单元的二醇成分和具有来自对苯二甲酸和萘二甲酸的重复单元的二酸成分，其中，分别基于二醇成分的100摩尔百分数和二酸成分的100摩尔百分数，在PET共聚物中存在的二甘醇和萘二甲酸的总量处于从约0.1摩尔百分数至约2.8摩尔百分数的量，并且预型件具有小于0.77dL/g的固有粘度。
30.根据权利要求29所述的方法，其中，预型件具有在从约0.60dL/g至小于0.77dL/g的范围内的固有粘度。
31.根据权利要求29所述的方法，其中，预型件具有小于0.76的固有粘度。
32.根据权利要求29所述的方法，其中，预型件具有在从约0.70dL/g至小于0.76dL/g的范围内的固有粘度。
33.根据权利要求29所述的方法，其中，预型件具有在从约0.70dL/g至约0.74dL/g的范围内的固有粘度。
34.根据权利要求29所述的方法，其中，预型件具有在从约8至约13范围中的拉伸比。
35.根据权利要求29所述的方法，其中，预型件具有在从约8至约12范围中的拉伸比。
36.一种用来减少用于制造容器的循环时间的方法，包括步骤：
(1)提供包括具有来自乙二醇和二甘醇的重复单元的二醇成分和具有来自对苯二甲酸和萘二甲酸的重复单元的二酸成分的PET共聚物熔体，其中，分别基于二醇成分的100摩尔百分数和二酸成分的100摩尔百分数，在PET共聚物中存在的二甘醇和萘二甲酸的总量是从约0.1摩尔百分数至约2.8摩尔百分数的量，
(2)然后把PET共聚物注射到模具中，
(3)然后冷却模具和包含的聚合物，
(4)然后把具有小于0.77dL/g固有粘度的预型件与模具脱开，
(5)然后重新加热预型件，及
(6)然后把预型件吹制模制成容器；
其中，与用包括PET共聚物和具有至少0.77dL/g的固有粘度的预型件用来制造第二容器的第二循环时间相比，减少用来制造容器的周期时间。
37.根据权利要求36所述的方法，其中，预型件具有小于0.76的固有粘度。
38.根据权利要求36所述的方法，其中，预型件具有在从约0.60dL/g至小于0.77dL/g的范围内的固有粘度。
39.根据权利要求36所述的方法，其中，预型件具有在从约0.70dL/g至小于0.76dL/g的范围内的固有粘度。
40.根据权利要求36所述的方法，其中，预型件具有在从约0.70dL/g至约0.74dL/g的范围内的固有粘度。
41.根据权利要求36所述的方法，其中，预型件具有在从约8至约13范围中的拉伸比。
42.根据权利要求36所述的方法，其中，预型件具有在从约8至约12范围中的拉伸比。
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