CN1167461A - 用聚萘二甲酸乙二醇酯(pen)制造的多层预制型坯和容器及其制造方法 - Google Patents

用聚萘二甲酸乙二醇酯(pen)制造的多层预制型坯和容器及其制造方法 Download PDF

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Publication number
CN1167461A
CN1167461A CN94194528A CN94194528A CN1167461A CN 1167461 A CN1167461 A CN 1167461A CN 94194528 A CN94194528 A CN 94194528A CN 94194528 A CN94194528 A CN 94194528A CN 1167461 A CN1167461 A CN 1167461A
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pen
layer
mer
poly
pet
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CN1064585C (zh
Inventor
韦恩·N·科莱特
史蒂文·L·施密特
瑟普耶·M·克瑞思奈可玛
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Graham Packaging Pet Technologies Inc
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Continental PET Technologies Inc
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Abstract

本发明涉及一种具有至少一层包括聚萘二甲醇乙二醇酯(PEN)以加强其氧防护性能和热性能的多层预制型坯和容器及其制备方法。PEN层可以是PEN的均聚物，共聚物或混合物。为增加上述性能，芯层可进一步包括PEN的共聚物或混合物。或者，PEN可仅包含在里层中。

Description

用聚萘二甲酸乙二醇酯(PEN)制造的 多层预制型坯和容器及其制造方法
                    发明领域
本发明涉及吹塑容器的改进，更具体的是具有多层透明侧壁的预制型坯和容器，侧壁包括一种用来增强热和防护性能的聚萘二甲酸乙二醇酯(PEN)的均聚物混合物或其共聚物，一层或多层能承受PEN的高定向温度和平面拉伸比，同时保持容器透明的添加层。此容器特别适用于可再装和/或热装的饮料容器。
                   发明背景
自从1987年用大陆PET技术发明聚对苯二甲酸乙二醇酯(PET)以来，PET可再装碳酸软饮料(CSD)瓶的市场在全球范围内有了显著增长。此瓶在欧洲，中美洲和南美洲的大部都有商业化生产，并且现在正在进入远东市场。
可再装的瓶减少了垃圾填埋和可处理的塑料饮料瓶的回收问题。另外，可再装瓶为现在还被玻璃瓶占有的，但又禁止使用不可回收包装的市场提供了一种更安全，重量更轻的塑料瓶。其目的是生产一种经济的，具有能经受多次重装循环的物理性能的可再装瓶。
通常，可再装塑料瓶在最少10次，优选20次循环后必须能保持其功能和美学上的性能才是经济可行的。一个循环(如图3所示)通常包括(1)空容器热碱洗涤，(2)污染物检测(在洗涤之前或之后)，(3)仓库存储，(4)分发给批发和销售网点和(5)用户购买，使用和倒空，最后回到饮料生产企业。
为了实现商业可行性，可再装容器必须满足一些重要的性能标准，它们包括：
1.高清晰度(透明)以便在线目检；
2.在容器的使用期中不变形；和
3.耐碱洗诱导的应力破裂和渗漏。
一种商业上成功的PET可再装CSD容器现在由可口可乐公司在欧洲进行销售(此后称“现有技术的CSD容器”)。这种容器用单层具有3-5％1，4-环己烷二甲醇(CHDM)或间苯二甲酸(IPA)等共聚用单体的聚对苯二甲酸乙二醇酯(PET)均聚物制造。预制型坯的侧壁厚度约为5-7mm，是可处理一次性瓶的预制型坯的侧壁厚度的2-2.5倍，本瓶由预制型坯拉伸吹塑得到。这使瓶的侧壁平均厚度(即0.5-0.7mm)比耐机械损伤和不变形所需较大的厚度，基于平面拉伸比为10∶1。直筒部(标记以下的圆柱形侧壁部分)的平均结晶度为15-20％。高共聚物含量避免在注塑过程中在预制型坯中形成可视的结晶，即混浊。因为预制型坯的混浊导致瓶的不透明，不利于商用可再装容器所需的在线目检，所以它是不希望有的。与已有技术容器有关的各个部分在大陆PET技术中的美国专利Nos.4,725,464，4,755,404，5,066,528和5,198,248中有所描述。
已有技术CSD容器在重装过程中，经受超过20次温度高达60℃的碱洗，证实了其领域可行性。虽然它是成功的，但是依然存在改进容器的商业需要，以便允许洗涤温度超过60℃，并减少产品味道的转移。当味料成分从第一种产品(如一种无醇饮料)迁移到瓶壁中，然后在下次装填时再渗入第二种产品中(如苏打水)便产生了味道的转移，从而影响了第二种产品的味道。提高温度可以提高效率和/或减少碱洗时间，果汁或牛奶等特定的食品也可能要求提高温度。
聚萘二甲酸乙二醇酯(PEN)是另一种用于制造吹塑容器的潜在聚酯。PEN具有所需的抗氧渗能力--5倍于PET，并具有较高的热稳定温度--约为250F°(120℃)，而PET只有175F°(80℃)。这些性质在氧敏感产品(如食品和化妆品)的容器和/或经受高温的容器(如可再装或热装容器)中是有用的。然而PEN比PET昂贵的多，而且具有不同的工艺要求，因此PEN还没有被成功地用于商业吹塑饮料容器中。
                  发明概述
本发明提出了一种预制型坯和容器及其制造方法，其中预制型坯和容器包括至少一个具有聚萘二甲酸乙二醇酯(PEN)用于提高防护性能和/或耐热性能的第一种聚合物层。第一种聚合物是PEN的均聚物，共聚物，或混合物。PEN提供于多层结构中，其中其它聚合物层在通过应变定向和结晶以提高PEN物理性能的温度和拉伸比下，进行加工，特别是吹塑(法)。
第一种聚合物的至少一层为表层或里层。PEN在表层提高了耐热性能和减少了味道转移。然而PEN在里层也能提高耐热性能和避免产品与PEN接触，如果需要避免上述接触。
在第一种高PEN实施方案中，容器的侧壁包括具有约80-100％PEN和0-20％PET(以层总重量计)的应变硬化的高PEN共聚物或混合物的内层和外层(表层)，和PETG等不可应变硬化的聚酯的芯层(里层)。PETG是一种含有约30％环己烷二甲醇(CHDM)的聚对苯二甲酸乙二醇酯(PET)的共聚物。另外芯层也可以是PEN/PETG的混合物。PEN在表面(表层)用于提高性能，包括提高抗氧渗能力和良好的物理性能，即耐冲击，耐压，耐应力破裂，降低产品味道转移和热稳定等。PETG层基本是不可结晶化的，可以在适于表层高PEN层的定向温度和最优平面拉伸比下被拉伸。另外，PETG粘合到高PEN层，在膨胀的容器中也不会脱层。而且PETG芯层以比PEN低的成本增加了容器的壁厚，使整个容器坚固。根据具体的例子，可再装碳酸饮料容器具有一个基本透明的多层侧壁，侧壁包括90％PEN/10％PET(以层总重量计)的内和外层，和一个PETG芯层，内∶芯层∶外层的相对厚度比为25∶50∶25。
在高PEN浓度时，PET均聚物不能作为芯层，因为其定向温度大大低于PEN的定向温度--即PEN最低定向温度为260°F(127℃)，基于255°F(123℃)的玻璃化温度。在此温度下，PET均聚物会结晶，不再经受应变硬化(定向)，使最终容器不透明，并缺乏足够的强度。相反，PETG基本是不结晶的，可以在适于PEN的定向温度和最优平面拉伸比下被拉伸，即为15-20∶1。
在第二个低PEN实施方案中，容器侧壁包括具有1-20％PEN和80-99％PET(以层总重量计)的应变硬化的低PEN共聚物或混合物的内层和外层，和PET等应变硬化的聚酯的芯层(里层)。在低PEN浓度时，对应力硬化的低PEN内和外层以及应力硬化的PET芯层可以达到定向温度和拉伸比可行的匹配。在具体的例子中，具有一个透明侧壁的热装容器包括10％PEN/90％PET(以层总重量计)的内和外层，和一个低PET共聚物的芯层，内层∶芯层∶外层的相对厚度为30∶40∶30。低PET共聚物可含有10％，最好是0-2％共聚物(以共聚物总重量计)。此实施方案实现了PEN增强的物理性能(在表面)与PEN增加的成本和处理要求之间较好平衡。
在第三个中PEN实施方案中，容器侧壁包括具有20-80％PEN和20-80％如PET等另一种聚酯的基本无定形PEN共聚物或混合物的内层和外层，和如PET等应变硬化的聚酯的芯层。在具体的例子中，可再装碳酸饮料容器具有一个基本透明的多层侧壁，侧壁包括具有50％PEN/50％PET(以层总重量计)的内和外层，和一个低共聚物PET芯层，内层∶芯层∶外层的相对厚度比为30∶40∶30。在另一个例子中，相同材料的热装容器侧壁的内层∶芯层∶外层的相对厚度比为15∶70∶15。PET芯层应力硬化以控制吹塑过程中的物料分布。
本发明的这些和其它特点将结合以下的详细描述和选择实施方案的图示予以更具体的说明。
             附图的简要说明
图1是根据本发明的实施方案的1.5升可再装充碳酸饮料瓶的侧视和部分剖面简图；
图2是图1中剖线2-2处局部放大图，更加详细地显示了PEN的表层(内层和外层)和第二种聚合物里层(芯层)；
图3是说明可再装容器所必经循环的示意图；
图4是用于制造根据本发明的多层预制型坯的注塑腔的剖面简图；
图5是图4中注塑腔底部的局部放大图，显示了一定量的PEN被注入并在与模面接触时被冷却，以形成预制型坯的表层(内层和外层)；
图6是与图5相似的局部放大图，显示了一定量的第二种聚合物被注入以形成预制型坯的里层(芯层)，PEN和第二种聚合物的孔道流形成了多层预制型坯；
图7是本发明最终多层预制型坯的放大的剖面图；
图8是由图7的预制型坯制造的容器的底部局部放大剖视图；
图9是另外一种预制型坯实施方案的局部剖视图，第三种PEN被注入，并在底形成部的中心部分取代了第二种聚合物；和
图10是由图9的预制型坯制造的容器的底部局部放大剖视图。
                 详细描述
参照附图，图1显示了1.5升可再装碳酸饮料瓶，其为本发明的一个实施方案。瓶10是整体塑料预制型坯吹胀的，具有基本透明多层侧壁的容器，它由图7中的多层预制型坯制造而成。容器主体包括一个开口的顶部和一个封闭的底部18，顶部具有一个直径较小的颈部12，颈部上有螺纹用于和带螺纹的瓶盖(未画出)相匹配。在瓶颈12和底18之间是基本垂直的侧壁15(由瓶的垂直轴或中心线CL确定)，包括上部的一个斜面肩形凸出部14和一个大致成圆柱形的直筒部16。底18是加厚的香槟形底，具有一个加厚的中心浇铸口部分20，向外逐渐到侧壁，沿半径方向依次为一个外凹的顶22，一个内凹的突边24，一个半径逐渐增加的拱形外底部分26用于平滑过渡到侧壁直筒部16。突边24大致成环形，瓶靠此部支撑，突边相对较厚以防止应力破裂。顶和突边构成了底的加厚部分，大约为直筒部16厚度的3-4倍。在突边上面是较薄的外底部分26，大约为加厚底部的50-70％，其逐步上升与侧壁相连。较薄的外底部26提高了抗冲击性能。
因为图的比例尺较小，图1不能够详细显示瓶10的多层侧壁。然而，图2显示了具有PEN表层32和34(内层和外层)和第二种聚合物里层30(芯层)的直筒部16的剖面图。在这个实施方案中，第二种聚合物是基本不结晶的高共聚物PET，称为PETG，或PETG和PEN的混合物。直筒部的芯层30的厚度大约为0.0093英寸(0.24mm)，直筒部的内层和外层32和34的厚度大约都为0.0047英寸(0.12mm)。肩形凸出部14和底18拉伸较小，因此比直筒部16厚而且定向程度小。容器的高度大约为13.2英寸(335mm)，直径(最宽处)大约为3.6英寸(92mm)。
用于制造图1中的容器的预制型坯如图7所示。预制型坯110具有厚度大约为0.280英寸(7mm)的直筒形成部116，其包括厚度大约为0.140英寸(3.5mm)的预制芯层130和厚度大约都为0.070英寸(1.8mm)的内层和外层132和134。容器直筒部16以大约为15∶1的平均平面拉伸比进行拉伸。平面拉伸比是预制型坯直筒成形部116与容器直筒部16的平均厚度之比，“平均”是分别沿预制型坯和容器部的长度方向确定的。对于容积大约为0.5-2.0升，直筒部壁厚大约为0.5-0.8mm的可再装的碳酸饮料瓶，较好的平面拉伸比大约为12-20∶1，最好为15-20∶1。环向拉伸大约为6-7倍，轴向拉伸大约为3-4倍。由此生产的容器直筒部具有所需的耐机械损伤性能，预制型坯的侧壁也是透明的。具体的直筒部厚度和所选择的拉伸比取决于瓶的尺寸，内部压力(例如啤酒为2atm，软饮料为4atm)和所使用材料的加工特性(例如被确定的特征粘度)。
可构成特定层全部或部分的聚萘二甲酸乙二醇酯(PEN)是一种由2，6-萘二甲酸二甲酯和乙二醇反应生成的聚酯。PEN聚合物包含重复的2，6-萘二甲酸乙二醇酯单元，其分子式如下：
     聚(2，6-萘二甲酸乙二醇酯)(PEN)
PEN树脂可以从Amoco Chemical Company(Chicago，Illi-nois)购买，其特征粘度为0.67dL/g，分子量为20,000。PEN的玻璃化温度Tg约为123℃，熔点Tm约为267℃。
可构成所有层全部或部分的聚对苯二甲酸乙二醇酯(PET)是一种由对苯二甲酸或其成酯衍生物和乙烯反应生成的聚酯。PET聚合物包含重复的对苯二甲酸乙二醇酯单元，其分子式如下：
       聚(对苯二甲酸乙二醇酯)(PET)
PET的玻璃化温度Tg约为73℃，Tm约为253℃。
在一个实施方案中，本发明使用了在PEN的定向温度下基本是不结晶的高PET共聚物，如PETG。此高共聚物PETG是含有30％(以总重量计)共聚单体环己烷二甲醇(CHDM)的PET。PETG可以从Eastman Chemical in Kingsport(Tennessee)购买，型号为KODAR PETG共聚酯6763。共聚单体(如CHDM取代乙二醇部分)破坏了PET聚合物的骨架(即交替的酸和乙二醇单元)，降低了分子结晶度。当共聚单体成为骨架的一部分时最有效，但是它也形成带支链的共聚物。另外一种适宜的高共聚物PET含有大量的间苯二酸(IPA)，使聚合物基本不结晶和无定形。
另外一种实施方案使用了PEN和PET的混合物。例如，一种重量比为25∶75的PEN/PETG混合物可以通过熔融混和这两种聚合物制备。与PETG芯层相比，多层中PEN/PETG混合物芯层可具有更好的热和防护性能，和更高的层相容性。PEN，PET以及其它聚酯的相似的化学结构(和/或其间的氢键)提供了必需的熔融相容性和层粘合。作为另一个实施方案，PEN可以与PET均聚物或低共聚物相混和或共聚。低含量PEN共聚物或混合物可以含有约10％PEN(以重量计)和另外一种聚酯，如PET均聚物或共聚物。“PET共聚物”意味着可购买到的瓶级PET，其可具有高达10％(以重量计)，通常为5％的其它共聚物单体，即间苯二酸(IPA)，环己烷二甲醇(CHDM)或二甘醇。
特征粘度(I.V.)影响聚酯树脂的可处理性。特征粘度大约为0.8的聚对苯二甲酸乙二醇酯在CSD工业中得到广泛应用。对各种应用，其范围大约为0.55到1.04，更好为0.65到0.85。特征粘度的测定根据ASTM D-2857进行。使用30℃下0.0050±0.0002g/ml聚合物溶液，溶剂含有o-氯酚(熔点为0℃)，特征粘度(I.V.)由下式给出：
I.V.＝(ln(Vsohn./Vsol.))/C
其中
Vsoln.是以任一单位表示的溶液粘度；
Vsol.是以相同单位表示的溶剂粘度；和
C是以g聚合物/100ml溶液表示的浓度。
吹制的容器应该基本透明，一种透明度的测定是穿过侧壁的透射光混浊百分比(HT)，其由下式给出：
HT＝[Yd÷(Yd+Ys)]×100
其中Yd穿过样品的漫射光，Ys是穿过样品的反射光。漫射光和反射光的大小根据ASTM方法D 1003采用任一标准色差仪，如Hunterlab，Inc制造的D25D3P进行测定。本发明的重复使用容器应该具有约小于10％，更优选小于5％的混浊百分比(通过直筒部侧壁)。
预制型坯应该基本也是透明的，应该具有不大于约10％，最好不大于约5％的通过侧壁的混浊百分比。
根据沿瓶不同的拉伸比，在图1的容器中从瓶颈到瓶底的高度方向上的PEN表层不同位置上具有不同程度的应力诱导结晶。结晶百分比根据ASTM 1505如下测定：
结晶百分比＝[(dS-da)/(dc-da)]×100
其中ds是以g/cm3表示的样品密度，da是0结晶百分比的非定形膜的密度，dc是由单位晶胞参数计算出的晶体密度。容器的直筒部16拉伸最大，应具有至少约为15％，最好约为20％的平均结晶百分比。15-25％的结晶百分比对于再装和热装应用是适宜的。
通过热设定产生应力诱导和热诱导的结晶组合可进一步提供结晶百分比。热诱导结晶可以在低温下进行以保证透明性，即保持容器与吹塑模接触。在某些应用中，侧壁表面的高度结晶就足够了。
图3显示了商用可再装容器的典型再装循环。用于模拟上述循环的测试过程将在下面给出。在此说明书和权利要求中所采用的，经受指定次数的再装而无破裂的能力和/或最大容积变化根据以下测试过程确定。
每个容器进行典型的商用碱洗溶液用3.5％重量的氢氧化钠和饮用水配制。洗涤液保持在指定的洗涤温度，如60℃。去盖的瓶子在溶液中浸渍15分钟以模拟商用瓶洗系统的时间/温度条件。去除洗涤液后，瓶子用饮用水冲洗，并填装4.0±0.2atm的碳酸水溶液(以模拟碳酸软饮料的容器)，加盖后，在38℃对流恒温器中，50％的相对湿度下放置24小时。提高炉温是用来模拟较低环境温度下，较长时间的商用储存。从炉中取出之后，倒空容器，并开始相同的再装循环直到损坏。
损坏是指任一导致渗漏和压降的瓶壁上的破裂。通过比较再装之前和之后室温下容器盛装液体的容积以测定容积变化。
本发明的可再装容器10能够在60℃的洗涤温度下经受至少20次再装循环而无损坏而且容积变化不超过1.5％。根据气相色谱质谱联用计测定，此容器也显示了味道转移至少减少20％(与现有技术CSD瓶相比)。
图4-6说明了一种用于制造本发明的多层预制型坯的定量的，顺序的共注塑设备。这种设备在1987年12月1日授予Krishnakumar等人的美国专利No.4,710,118中有详细描述，在此结合全面参考。
如图4所示，一个注塑模单元40包括一个外模腔42，一个生成瓶颈的瓶颈模44和一个芯46。瓶颈模44和芯模46封闭了模腔42的上端，而下端具有开口48，开口48封闭承接挤出机的旋转阀部件52的类喷嘴形端50。阀部件52密封安装在阀块54中，阀块54在此形成具有接收注塑头的常规喷嘴60的第一个通道56。通道56沿径向通向旋转阀部件52，后者具有一个在其一端与大致径向的，可与通道56对齐的通道64相连的通道62。阀块54也与第二个物料加注器66相连，加注器66包括一个加注活塞68和一个通向阀块54的通道70。阀块54具有可与通道70轴向对齐相连的径向通道72。阀部件52还具有从通道62大致径向伸出的通道74，因此通道74与通道64周向隔开，使通道64与通道56相连时，通道74与通道72分离。旋转阀部件52，通道64与通道56分离，通道74却与通道72相连。因此，物料可以选择性地来自第一个供应设备60(注塑头)或第二个供应设备66。
根据本实施方案，第一供应设备60传递用于内层和外层的PEN。第二个供应设备66传递用于芯层的PETG(或一种PEN/PETG的混合物)。
参照图5，确定量的第一种树脂76被注入模腔42的底部，当其流经模腔时，由于包括芯46的模单元40的相对温度低，树脂76发生固化以形成第一种物料表层的内层和外层78，80。
如图6简示，第二种树脂86接下来被注入模腔。第二种树脂86将在层78，80之间进行管道流，同时它将超过以前注入的原料76。因为它不与较冷的模壁接触，所以里层芯物料冷却得较慢；然而，因为芯层基本是不结晶的，所以它防止了混浊。
图7显示了前述制造的预制型坯110，其包括一个PETG芯层130和PEN内层和外层132，134，除了在注入口120处伸入外层的芯物料130的一部分外，内层和外层基本是连续的。预制型坯110包括一个上部瓶颈112，一个从上到下厚度不断增加的斜形肩成形部114，一个具有均一厚度的直筒成形部116和一个底成形部118。底部118包括一个厚度远大于直筒部116的，将形成容器底部加厚突边的上部圆柱形加厚部121，和一个厚度减小的，用于形成容器凹入顶的斜形下部119。具有适于重复使用应用的较好剖面的预制型坯在1991年11月19日授予Krishnakumar等人的美国专利No.5,066,528中有所描述，在此结合参考。在制造前述的优选的1.5升瓶时，直筒部116的芯层130的厚度大约是每个内层和外层132和134的两倍。
如图8所示的吹制容器具有一个香槟形底部150，其包括一个中心注塑口部152，中心凹入顶154，突边156，和外底部158。根据具体部位所达到相对拉伸程度，芯层160和内层和外层162和164的厚度沿底部是变化的，但是在整体上壁厚在径向远离注塑口152时逐渐减小。
图9显示了一个预制型坯底成形部218的另外一个实施方案，其中第三种树脂至少被注入底成形部的中心部236，优选注入壁厚减小的较下的底部219，其会更迅速地冷却，不易混浊。236部分取代了芯物料230，并优选是与内层和外层232，234相同的物料，以便在前述共注入过程中在下一个预制型坯开始制造前清除喷嘴的芯树脂，从而避免将芯树脂注入下一个预制型坯的内层和外层。如图10所示，由图9中预制型坯吹制的香槟形容器底250包括一个注塑口部252，顶254，突边256和外底258。在壁中，底包括内层和外层262和264以及芯层260。芯层260在注塑口和凹入区域之间至少266被部分取代。
另外一些在制造可再装聚酯饮料瓶中重要的因素在1982年6月15日授予Krishnakumar等人的美国专利No.4,334,627,1988年2月16日授予Collette的美国专利No.4,725,464和1991年11月19日授予Krishnakumar等人的美国专利No.5,066,528中有所描述，结合于此以便全面参考。
预制型坯的扩展应在所使用的PEN聚酯物料的分子定向温度范围内进行。通常，一种可定向热塑物料的分子定向在正好高于玻璃化温度(低于此温度或很窄的温度范围时聚合物呈玻璃态)到正好低于熔融温度的范围内发生。实际操作中，容器的定向要在窄得多的温度范围内进行，被称为分子定向温度范围。原因是当温度非常接近玻璃化温度时，物料过于坚硬以致无法用通常的设备拉伸。当温度增加时，可处理性提高的很快，但是在或接近开始形成所谓球状微结晶的大量结晶集合的温度就达到了实际的上限，因为球状微结晶增长不利于定向过程。对基本无定形的聚酯物料，分子定向温度通常比玻璃化温度高约20到65°F(11到36℃)，最好是30到40°F(17到22℃)。典型的玻璃化温度为255°F(123℃)的无定形PEN聚合物最小定向温度约为260°F(127℃)，最好的范围是270-295°F(132-146℃)。
在优选的再加热拉伸吹制过程中，热注塑预制型坯在使用前冷却到室温，然后在扩展步骤前再加热到定向温度范围内。再加热的预制型坯在拉伸吹制装置中定位，其中一个拉伸喷杆伸入预制型坯开口端，将预制型坯端拉向内腔吹塑模的一个底，从而轴向拉伸预制型坯的侧壁，同时或接着使吹制介质通过喷杆里或其周围的开口进入预制型坯的里层，以易于将预制型坯向外拉伸，使之与模的内表面吻合。拉伸的程度可根据吹制容器所需形状和壁厚变化，可通过固定起始预制型坯和最终容器的尺寸来控制。
在另外一个集成过程中，热注塑预制型坯被部分冷却，并在用适宜的，与前述相似的吹制或拉伸/吹制结合的设备扩展前使其在定向温度范围内平衡。
可以在多层结构中为各种目的加入附加层或添加剂，例如抗渗材料附加层(如水汽，氧，二氧化碳或光)，高热稳定性材料，循环PET，使用过的PET等等。这些附加层需要在层间使用粘合剂粘合以防止脱层。循环的PET特制可以用于芯层，其不会与产品接触。可以采用不同的底结构，例如一种足形底具有大致半球形底壁，它有一组向外伸出的，终止于最低支撑足的腿，在腿之间是辐射状的脊(其为底壁的一部分)。虽然物料，壁厚，预制型坯和瓶的轮廓，以及处理技术对于一种特定的最终产品都可以是不同的，但同样包含在本发明范围之内。此容器可以用于其它加压或不加压如啤酒，果汁或牛奶等饮料中，或其它非饮料类产品。
本发明的优点，如抑制浑浊和在高温下增强的耐应力破裂性能，特别适合作为热装容器，例如在1989年9月5日授予Collette的美国专利No.4,863,046所描述的，在此结合全面参考。热装容器通常必需经受180-185°F的高温(产品装填温度)，2-5psi的正内压(装填线压力)而无明显的变形(即容积变化不大于1％)。本发明的优点特别适于作为可再装和热装的组合容器。
作为另一个例子，表层中低含量PEN共聚物或混合物(即至多10％，根据PEN重量)可以使使用温度增加5℃(碱洗温度从60°增加到65℃或热装温度从83°增加到88℃)，从提高的性能与成本比看，“增加了其价值”。
虽然本发明的几个实施方案被予以详细地说明和描述，但是只要不背离在附加权利要求中所确定的本发明的精神和范围，物料，预制型坯结构，容器结构和制造本预制型坯和容器的方法的变化都是可以理解的。

Claims (39)

1.一种多层容器包括：
一个整体扩展塑料预制型坯的，基本透明多层侧壁的容器，侧壁包括至少一个具有聚萘二甲酸乙二醇酯(PEN)均聚物，共聚物，或混合物的第一种聚合物层，和第二种聚合物的另外一层，其中的第二种聚合物在高于第一种聚合物定向温度的温度下拉伸后仍然基本透明。
2.权利要求1的多层容器，其中至少第一种聚合物的一层作为表层，第二种聚合物层作为里层。
3.权利要求2的多层容器，包括应变硬化的高PEN第一种聚合物的内层和外层(表层)，其中第一种聚合物由80-100％PEN和0-20％PET(以层总重量计)构成，和不可应变硬化的聚对苯二甲酸乙二醇酯(PET)芯层(里层)。
4.权利要求3的多层容器，其中的第二种聚合物是a)PETG；或b)PEN和PETG的共聚物或混合物。
5.权利要求3的多层容器，其中的第二种聚合物是PEN和PET共聚物的共聚物或混合物，PET共聚物包含0～10％的共聚物。
6.权利要求3的多层容器，其中的内层和外层各由90％PEN和10％PET构成，第二种聚合物由PETG构成，内层∶芯层∶外层的厚度比为25∶50∶25。
7.权利要求2的多层容器，包括应变硬化的低PEN含量第一种聚合物的内层和外层(表层)，其中第一种聚合物含有1-20％PEN和80-99％PET(以层总重量计)，以及含有基本应变硬化的PET低共聚物芯层(里层)的第二聚合物。
8.权利要求7的多层容器，其中内层和外层各含有10％PEN和90％PET构成，芯层(里层)由具有0-2％共聚物的PET共聚物，其中内层∶芯层∶外层的厚度比为30∶40∶30。
9.权利要求2的多层容器，包括基本无定形的中PEN含量第一种聚合物的内层和外层(表层)，其中第一种聚合物由20-80％PEN和20-80％PET(以层总重量计)构成，以及芯层(里层)的第二聚合物是基本应变硬化的PET低共聚物。
10.权利要求9的多层容器，其中的内层和外层各由50％PEN和50％PET构成，芯层(里层)由具有0-2％共聚物的PET低共聚物构成。
11.权利要求9的多层容器，其中内层∶芯层∶外层的厚度比为30∶40∶30和15∶70∶15。
12.权利要求1的多层容器，其中侧壁以12-20∶1的平面拉伸比进行扩展。
13.权利要求2的多层容器，其中表层平均结晶至少为15％。
14.权利要求1的多层容器，其中容器在60℃的碱洗温度下可以经受至少20次再装循环而无损伤，且最大容积变化约为±1.5％。
15.权利要求1的多层容器，其中的容器是独立加压的饮料容器。
16.权利要求1的多层容器，其中容器是一种热装容器。
17.权利要求1的多层容器，其中第二种聚合物包括循环或使用过的PET。
18.权利要求2的多层容器，其中第一种聚合物是一种低PEN共聚物或由1-20％PEN和80-99％PETG构成的混合物，芯层是由80-100％PEN和0-20％PET构成的高PEN第二种聚合物(以层总重量计)。
19.权利要求2的多层容器，其中第一种聚合物是一种低PEN共聚物或由1-20％PEN和80-99％PETG构成的混合物，芯层是由20-80％PEN和20-80％PET构成的中PEN第二种聚合物(以层总重量计)。
20.权利要求2的多层容器，其中第一种聚合物是一种高PEN共聚物或由80-100％PEN和0-20％PET构成的混合物，芯层是由80-100％PEN和0-20％PET构成的高PEN第二种聚合物(以层总重量计)。
21.权利要求1的多层容器，其中至少第一种聚合物的一层作为里层。
22.权利要求21的多层容器，包括PET低共聚物的内层和外层(表层)，和一个由1-20％PEN和80-99％PET构成的低PEN第一种聚合物的芯层(里层)。
23.权利要求21的多层容器，包括PET低共聚物的内层和外层(表层)，和一个由20-80％PEN和20-80％PET构成的中PEN第一种聚合物的芯层(里层)。
24.权利要求21的多层容器，包括PET高共聚物的内层和外层(表层)，和一个由1-20％PEN和80-99％PET(按总层重量计)构成的低PEN第一种聚合物的芯层(里层)。
25.权利要求21的多层容器，包括PET高共聚物的内层和外层(表层)，和一个由20-80％PEN和20-80％PET(按总层重量计)构成的中PEN第一种聚合物的芯层(里层)。
26.权利要求21的多层容器，包括PET高共聚物的内层和外层(表层)，和一个由80-100％PEN和0-20％PET(按总层重量计)构成的高PEN第一种聚合物的芯层(里层)。
27.一个用于吹塑一个容器的预制型坯，预制型坯包括至少一个具有聚萘二甲酸乙二醇酯(PEN)均聚物，共聚物，或混合物的第一种聚合物层，和第二种聚合物的另外一层的多层侧壁形成部分，其中第二种聚合物在高于第一种聚合物定向温度的温度下拉伸后仍然基本透明。
28.权利要求27的多层预制型坯，其中至少第一种聚合物的一层作为表层，第二种聚合物层作为里层。
29.权利要求27的多层预制型坯，其中至少第一种聚合物的一层作为里层。
30.权利要求28的多层预制型坯，包括由80-100％PEN(按总层重量计)和20-0％PET构成的高PEN第一种聚合物的内层和外层(表层)，第二种聚合物是聚酯。
31.权利要求28的多层预制型坯，包括由1-20％PEN(按总层重量计)和80-99％PET构成的低PEN第一种聚合物的内层和外层(表层)，第二种聚合物是低共聚物PET。
32.权利要求28的多层预制型坯，包括由20-80％PEN和80-20％PET(按总层重量计)构成的中PEN第一种聚合物的内层和外层(表层)，第二种聚合物是低共聚物PET。
33.一种用于制造具有基本透明的多层侧壁制品的方法，包括：
提供具有聚萘二甲酸乙二醇酯(PEN)均聚物，共聚物，或混合物的第一种聚合物，以及在高于第一种聚合物定向温度的温度下拉伸后仍然基本透明的第二种聚合物；和
形成在升高的温度下制造基本无定形和透明的，具有至少第一种聚合物的一层和第二种聚合物的另一层的多层侧壁成形部的预制型坯。
34.权利要求33的方法，其中至少第一种聚合物的一层作为表层，第二种聚合物层作为里层。
35.权利要求33的方法，其中至少第一种聚合物的一层作为里层。
36.权利要求34的方法，进一步包括：
在第一种聚合物的定向温度下膨胀预制型坯，形成具有双轴定向表层的，基本透明的多层侧壁的容器。
37.权利要求36的方法，其中扩展步骤包括形成平均应力诱导结晶至少为15％的容器侧壁。
38.权利要求34的方法，其中的预制型坯侧壁成形部具有厚度为壁厚50％的第二种聚合物芯层(里层)，以及第一种聚合物内层和外层(表层)。
39.权利要求36的方法，其中的侧壁成形部以12-20∶1区域拉伸比进行扩展。
CN94194528A 1993-12-15 1994-12-13 具有透明的多层侧壁的容器及其制造方法 Expired - Fee Related CN1064585C (zh)

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SG47925A1 (en) 1998-04-17
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CA2179174C (en) 2000-05-23
DE69420861D1 (de) 1999-10-28
WO1995016554A1 (en) 1995-06-22
EP0734316B1 (en) 1999-09-22
US5628957A (en) 1997-05-13
EP0734316B2 (en) 2006-09-27
NZ278214A (en) 1998-01-26
AU690193B2 (en) 1998-04-23
DE69420861T2 (de) 2000-02-10
AU1435395A (en) 1995-07-03
EP0734316A1 (en) 1996-10-02
CN1064585C (zh) 2001-04-18

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