CN101678934A - 耐压性聚酯容器及其生产方法 - Google Patents
耐压性聚酯容器及其生产方法 Download PDFInfo
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- CN101678934A CN101678934A CN200880018773A CN200880018773A CN101678934A CN 101678934 A CN101678934 A CN 101678934A CN 200880018773 A CN200880018773 A CN 200880018773A CN 200880018773 A CN200880018773 A CN 200880018773A CN 101678934 A CN101678934 A CN 101678934A
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- resin
- crystallinity
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- resistant polyester
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Images
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Abstract
一种多层结构的耐压性聚酯容器，所述多层结构包括聚酯树脂内外层和至少一层功能性树脂中间层，其中在容器体部中，所述聚酯树脂内层和外层分别具有结晶度为23％以上和18％以上，其平均值为24％以上。即使当将由加入有粘土的功能性树脂组成的功能性树脂组合物用于中间层时，也能够有效地防止由老化导致的白化。因而，可提供透明性优良的耐压性聚酯容器和生产其的方法。
Description
技术领域
本发明涉及具有功能性树脂中间层的耐压性聚酯容器。更具体地，本发明涉及能够长期维持优良透明性的耐压性聚酯容器及其生产方法。
背景技术
为了改进在塑料包装容器中内容物的保存性，迄今已将多层结构用于容器壁、通过使用聚酯树脂形成的其内外层，和其中间层，所述中间层通过使用乙烯/乙烯醇共聚物或含亚二甲苯基的聚酰胺树脂形成以改进气体阻隔性或通过使用功能性树脂如环烯烃共聚物形成以改进水蒸气(水)阻隔性(专利文献1)。
此外，已进行尝试将功能性树脂与无机填料或其他树脂组合物共混，以进一步改进功能如气体阻隔性或赋予其他功能。例如，以下专利文献2教导了将含亚二甲苯基聚酰胺与有机粘土共混以进一步改进含亚二甲苯基聚酰胺树脂的气体阻隔性。
专利文献1：JP-A-2005-067637
专利文献2：JP-A-2004-142444
发明内容
发明要解决的问题
然而，如果将具有上述功能性树脂中间层的多层结构的耐压性聚酯容器在与单层耐压性聚酯容器的那些相同的条件下双轴拉伸吹塑成型，则中间层经历白化，并且损害透明性，所述白化是因为由长期保存后透过聚酯树脂层的水诱发的结晶导致的。
特别地，包括共混有粘土的功能性树脂中间层的多层结构的耐压性聚酯容器具有拉伸特性，以致在拉伸时产生大的负荷，因此，趋于在该中间层中形成空洞(void)从成型起开始白化。
因此，本发明的目的是提供耐压性聚酯容器及其生产方法，尽管使用通过将功能性树脂与粘土共混获得的功能性树脂组合物作为中间层，但所述耐压性聚酯容器即使经过时间流逝后也有效地防止白化，并以优良的透明性为特色。
用于解决问题的方案
根据本发明，提供耐压性聚酯容器，其具有包括聚酯树脂内外层和至少一层功能性树脂中间层的多层结构，其中，在容器体部中，所述聚酯树脂内层具有结晶度不小于23％，其外层具有结晶度不小于18％，所述内层的结晶度与所述外层的结晶度的平均值不小于24％，并将粘土分散于功能性树脂中。
在本发明的耐压性聚酯容器中，期望功能性树脂包含聚己二酰间苯二甲胺或乙烯/乙烯醇共聚物作为基材树脂。
此外，根据本发明，提供用于生产耐压性聚酯容器的方法，所述耐压性聚酯容器通过双轴拉伸吹塑成型多层预制品来生产，所述多层预制品包括聚酯树脂内外层和至少一层其中分散粘土的功能性树脂中间层，在所述方法中，将所述多层预制品在110至120℃的温度加热下双轴拉伸吹塑成型，以使多层容器成型，在所述多层容器中，在容器体部中，所述聚酯树脂内层具有结晶度不小于23％，其外层具有结晶度不小于18％，所述内层的结晶度与所述外层的结晶度的平均值不小于24％。
发明的效果
根据本发明的耐压性聚酯容器，用作中间层的功能性树脂组合物表现即使经过时间流逝后也有效地防止白化和长期维持优良透明性的优异功能。
此外，根据用于生产本发明的耐压性聚酯容器的方法，不需要用于生产耐热性聚酯容器的方法需要的热固定步骤，在容器体部中聚酯树脂内外层的结晶度位于上述范围内，这使得可以有效地生产耐压性聚酯容器。
附图说明
[图1]为说明本发明耐压性聚酯容器的截面结构的图。
[图2]为说明本发明耐压性聚酯容器的截面结构的图。
[图3]为本发明耐压性聚酯容器的侧面图。
具体实施方式
根据本发明，重要的特征在于，耐压性聚酯容器具有包括聚酯树脂内外层和至少一层功能性树脂中间层的多层结构，其中，在容器体部中，所述聚酯树脂内层具有结晶度不小于23％，其外层具有结晶度不小于18％，所述内层的结晶度与所述外层的结晶度的平均值不小于24％，并将粘土分散于功能性树脂中。
如上所述，通过将功能性树脂与粘土共混获得的功能性树脂组合物在拉伸时产生大的负荷。因此，如果具有该多层结构的耐压性聚酯容器通过与生产常规耐压性聚酯容器相同的方法形成，则该层从成型开始趋于白化，当该容器长期保存时，白化进一步进行。
本发明人已发现：如果在容器体部中，将聚酯树脂内层的结晶度设定为不小于23％，将其外层的结晶度设定为不小于18％，并将所述内层的结晶度与所述外层的结晶度的平均值设定为不小于24％，则具有上述多层结构的耐压性聚酯容器变得没有上述问题。
即，聚酯树脂内外层具有不小于上述值的结晶度的聚酯容器几乎不允许水渗透入中间层。因此，抑制在中间层中的分子运动，抑制结晶，结果，有效地防止由于结晶导致的白化。
根据本发明，形成内外层的聚酯树脂的结晶度χc通过密度法测量，即，根据下式计算，
χc＝[dc(d-da)/d(dc-da)]×100
其中da为完全无定形的聚酯树脂的密度，dc为理论上完全结晶的聚酯树脂的密度，d为样品的密度。
从稍后描述的实施例的结果，本发明的作用和效果将变得显而易见。
即，在聚酯树脂内层具有结晶度不小于23％，其外层具有结晶度不小于18％，其平均值不小于24％的本发明的耐压性聚酯容器中，在50℃、80％RH、72小时下进行的老化测试中，容器的雾度几乎不增加，并维持透明性(实施例1至5)，而当耐压性聚酯容器不满足即使一个上述条件时，雾度增加并损害透明性(比较例1、4和5)。
具有上述特征的本发明的耐压性聚酯容器可通过用于生产耐压性聚酯容器的方法获得，所述耐压性聚酯容器通过以下来生产：双轴拉伸吹塑成型包括聚酯树脂内外层和至少一层功能性树脂中间层的多层预制品，即，在110至120℃温度下加热的同时双轴拉伸吹塑成型该多层预制品来生产。
通常，耐热性聚酯容器通过双轴拉伸吹塑成型法接着热定形或通过具有加热处理步骤的两步骤吹塑成型法来获得。该种耐热性聚酯容器不会变形(distortion)并具有高结晶度。然而，根据本发明，不通过热定形步骤或热处理步骤，能够赋予容器以高结晶度，并且获得的聚酯容器显示耐压性和耐热性。
即，当本发明的耐压性聚酯容器通过双轴拉伸吹塑成型预制品同时在上述温度范围内将其加热来获得时，聚酯树脂内层具有结晶度不小于23％，其外层具有结晶度不小于18％，其平均值不小于24％(实施例1至5)。当耐压性聚酯容器通过根据常规方法的双轴拉伸吹塑成型预制品同时在低于110℃的温度下将其加热来获得时，聚酯树脂内外层具有不位于本发明范围内的结晶度。结果，长期保存后损害透明性(比较例1和4)。
(中间层)
本发明耐压性聚酯容器的中间层使用通过将粘土分散于用作基材树脂的功能性树脂中获得的功能性树脂组合物。
即，通常，功能性树脂在伸长时产生大的应力，并且在伸长时趋于损失透明性；即，趋于容易损害功能性树脂的功能。此外，如果将粘土分散于功能性树脂以改进气体阻隔性，则比单独功能性树脂在伸长时产生更大的应力，由于产生空洞导致损害功能如透明性和气体阻隔性，因此，该问题具体对应于本发明的目的。
此外，通常，功能性树脂为高吸湿性的，由于成型后吸收水分导致显示降低的玻璃化转变温度，此外，使得分子容易移动促进结晶。如果将粘土分散于功能性树脂以改进气体阻隔性，则由于成核剂的效果导致成型时促进结晶。因此，成型后，在那些无定形部分中能够结晶的那些的大部分将已结晶，或推测为几乎不结晶的结构。因此，当保存时抑制中间层结晶，结果，能够有效地防止由于结晶导致的白化。
作为用于本发明的功能性树脂，可示例已知功能性树脂如具有气体阻隔性、水蒸气阻隔性、氧吸收性和氧吸收/气体阻隔性的树脂。具体实例包括气体阻隔性聚酰胺树脂如聚己二酰间苯二甲胺和聚癸二酰间苯二甲胺(polymetaxylylenesebacamide)，以及乙烯/乙烯醇共聚物，和水蒸气阻隔性环烯烃树脂。根据本发明，当使用伸长时产生大的应力和优良气体阻隔性的聚己二酰间苯二甲胺或乙烯/乙烯醇共聚物时，能够显著地显示优良的作用和效果。
作为粘土，可使用云母、蛭石和绿土，优选具有电荷密度为0.25至0.6的2-八面体型或3-八面体型的层状硅酸盐。作为2-八面体型的层状硅酸盐，可示例蒙脱石、贝得石和囊脱石。作为3-八面体型的层状硅酸盐，可示例锂蒙脱石和三八面体蒙脱石(suponite)。
用于本发明的粘土特别期望为用有机性赋予剂(organicproperty-imparting agent)溶胀化处理的粘土。在此情况下，在上述粘土中，蒙脱石具有高溶胀性，由于有机性赋予剂的浸透，溶胀在该层间扩展。
作为有机性赋予剂，可优选使用季铵盐。更优选地，可使用至少一个或多个具有不少于12个碳原子的烷基的季铵盐，如三甲基十二烷基铵盐和三甲基十四烷基铵盐。
期望含粘土功能性树脂以每100重量份功能性树脂为1至10重量份，特别地1至8重量份的比例包含粘土。如果粘土的量小于上述范围，与当以在上述范围内的量添加粘土时相比，通过添加粘土不能充分获得气体阻隔性。另一方面，如果粘土的量大于上述范围，与当以上述范围内的量添加粘土时相比，成型性变差。
此外，可将上述含粘土功能性树脂与氧化性有机组分和过渡金属催化剂的组合共混，以赋予其氧吸收性。
作为氧化性有机组分，可示例在侧链上或在末端具有官能团并且能够被氧化的那些。具体地，可示例用酸或酸酐改性的多烯低聚物或聚合物，如丁二烯和用无水马来酸改性的丁二烯。作为过渡金属催化剂，可使用元素周期表第VIII族的金属组分，如铁、钴和镍，然而，本发明绝不仅限于这些。
期望氧化性有机组分以每100重量份功能性树脂为2至10重量份的量共混，过渡金属催化剂以作为金属计算的至少300ppm的量共混。
用于本发明的功能性树脂可根据已知配方与以下物质在它们不损害本发明目的范围内共混：粘土或氧化性组分与过渡金属催化剂的组合，以及已知树脂共混剂(blending agents)如脱氧剂(disoxidant)、填料、着色剂、热稳定剂、老化稳定剂、抗氧化剂、防老剂、光稳定剂、紫外线吸收剂、抗静电剂、润滑剂如金属皂或蜡，以及改质(reforming)树脂或橡胶。
(内外层)
作为用于本发明的内外层的聚酯树脂，可使用包括二羧酸组分和二醇组分的已知聚酯树脂。
作为二羧酸组分，从机械性质和热性质的观点，期望不低于50％，特别地，不低于80％的二羧酸组分为对苯二甲酸。然而，自然，可包含除了对苯二甲酸之外的羧酸组分。作为除了对苯二甲酸之外的羧酸组分，可示例间苯二酸、萘二羧酸、对-β-氧乙氧基苯甲酸、联苯基-4，4’二羧酸、二苯氧基乙烷-4，4’-二羧酸、间苯二酸5-磺酸钠(5-sodiumsulfoisophthalic acid)、六氢对苯二甲酸、己二酸和癸二酸。
作为二醇组分，从机械性质和热性质的观点，期望不低于50％，特别地，不低于80％的二醇组分为乙二醇。作为除乙二醇之外的二醇组分，可示例1，4-丁二醇、丙二醇、新戊二醇、1，6-己二醇、二甘醇、三甘醇、环己烷二甲醇、双酚A的环氧乙烷加合物、甘油和三羟甲基丙烷。
此外，上述二羧酸组分和二醇组分可包含三官能以上的高官能多元酸和多元醇；即，多元酸如偏苯三酸、均苯四酸、苯三甲酸、1，1，2，2-乙烷四羧酸、1，1，2-乙烷三羧酸、1，3，5-戊烷三羧酸、1，2，3，4-环戊烷四羧酸和联苯基-3，4，3’，4’-四羧酸，多元醇如季戊四醇、甘油、三羟甲基丙烷、1，2，6-己三醇、山梨醇和1，1，4，4-四(羟基甲基)环己烷。
期望用于本发明的内外层的聚酯树脂具有通过使用重量比1∶1的苯酚/四氯乙烷混合溶剂在30℃下测量的0.60至1.40dL/g的固有粘度。此外，期望聚酯树脂具有200至275℃的熔点(Tm)，以改进多层容器的耐热性和加工性。此外，期望聚酯树脂具有不低于30℃，特别地，50至120℃的玻璃化转变点。
用于本发明的内外层的聚酯树脂可根据已知配方与例如以下已知树脂用共混剂在它们不损害最终成型制品的品质范围内共混：着色剂、抗氧化剂、稳定剂、各种抗静电剂、脱模剂、润滑剂和成核剂。
(多层结构)
本发明的耐压性聚酯容器可采用各种层构造，只要其包括聚酯树脂内外层和至少一层共混有粘土的功能性树脂组合物中间层即可。该层构造可具有如图1所示在聚酯树脂内层1与外层2之间共混有粘土的功能性树脂组合物中间层3。或者，如图2所示，该层构造可包括聚酯树脂内层1和外层2，以及插入聚酯树脂内层1与聚酯树脂中间层4之间，和聚酯树脂外层2与聚酯树脂中间层4之间的两层功能性树脂中间层3a、3b。
在生产多层容器中，虽然通常不需要，但可将粘合剂树脂插入树脂层之间。作为粘合剂树脂，可示例热塑性树脂，所述热塑性树脂以1至700毫当量(meq)/100g树脂，特别地，10至500meq/100g树脂的浓度在主链或侧链上包含基于羧酸、羧酸酐、羧酸盐、羧酸酰胺或羧酸酯的羰基(-C0-)。粘合剂树脂的优选实例包括乙烯/丙烯酸共聚物、离子化交联烯烃共聚物、马来酸酐接枝聚乙烯、马来酸酐接枝聚丙烯、丙烯酸接枝聚烯烃、乙烯/乙酸乙烯酯共聚物和共聚合的聚酯。
在本发明的耐压性聚酯容器中，期望体部具有200至600μm，特别地，240至500μm的总厚度，尽管其可依赖于容器的体积(重量)和容器的用途而改变。
重要的是，从容器的透明性的观点，为中间层的包括含粘土功能性树脂组合物的层的厚度小于20μm，特别地为5至15μm，并且该中间层的厚度为体部总厚度的3至10％。
如果使多个包括含粘土的功能性树脂组合物中间层存在，期望各中间层具有厚度为小于20μm，特别地为8至15μm，中间层作为整体具有体部总厚度的3至20％的厚度。
(生产方法)
通过使具有上述多层结构的预制品成型，在110至120℃，特别地112至118℃的高温下加热该预制品，沿轴向拉伸牵引该预制品，同时，沿周向吹塑拉伸该预制品，可生产具有已知耐压性底部形状例如如图3所示的所谓花瓣形状或在底部中心具有凹部的原野形(champaign shape)的本发明的耐压性聚酯容器。如上所述根据本发明，可将内外层的结晶度设定为位于上述范围内，而不进行热定形。
多层预制品可通过例如以下的已知成型方法来生产：共挤出成型法，其将含粘土功能性树脂组合物和聚酯树脂一起共挤出；同步注塑成型法，其将含粘土功能性树脂组合物和聚酯树脂同时注射入金属模具中；顺序注塑法，其将聚酯树脂、含粘土功能性树脂组合物和聚酯树脂顺序注射入金属模具中；压缩成型法，其通过使用芯金属模具和腔金属模具将含粘土功能性树脂组合物和聚酯树脂共挤出产物压缩成型。
当采用这些体系的任何一种时，成型的预制品应在过冷状态下，即，在无定形状态下，期望将包括含粘土的功能性树脂组合物中间层封入热塑性聚酯的内外层中。
期望通过如上所述的冷型坯体系进行成型多层预制品和拉伸吹塑成型预制品。然而，也允许通过热型坯体系进行拉伸吹塑成型而不完全冷却成型的多层预制品。
在进行拉伸吹塑成型之前，通过如热风、红外线加热器或高频诱导加热等的手段将预制品预热至拉伸温度。此处，根据本发明，预制品通过将其在比常规拉伸吹塑成型的温度更高的温度下，即，在110至120℃下，特别地在112至118℃下加热来拉伸吹塑是特别重要的。如果预制品的温度低于上述温度，含粘土功能性树脂组合物在伸长时产生大的应力，因此，不能预期由于拉伸取向导致结晶促进，长期保存后透明性降低，容易发生空洞，并且获得的聚酯容器的透明性劣化。另一方面，如果预制品的温度高于上述范围，则预制品软化，在拉伸吹塑成型时偏离预制品的中心，劣化成型性。因此，获得的聚酯容器的厚度变得不均匀，预制品在拉伸吹塑成型前结晶，不能再成型。
将加热的预制品进给至已知拉伸吹塑成型机中，并设置在金属模具中，通过推入拉伸棒中沿轴向牵引和拉伸，并通过吹动流体沿周向拉伸。此处，期望通过使用在300至600℃下加热的加热体和/或通过使用150至220℃的热风加热多层预制品内部。
即，在双轴拉伸吹塑成型在上述范围内的温度下加热的预制品时，预制品的内部通过插入在高温下加热的加热体和/或通过吹送高温的热风来加热，由此预制品内部的温度变得更高，在拉伸吹塑成型时维持高的预制品中的温度，促进其应变的松弛以及松弛在伸长时产生大应力的包括含粘土的功能性树脂组合物中间层的张力，有效地抑制功能如透明性和气体阻隔性的劣化。
期望用于内部加热的时间依赖于预热预制品的温度和用于内部加热的加热体的设定温度而改变，并优选8至20秒，特别地10至15秒。此外，期望将用于拉伸吹塑成型的热风吹入设置在金属模具中的预制品2至3秒。
为最终产品的耐压性聚酯容器的拉伸比优选作为面积比为1.5至25倍，作为沿轴向的拉伸比为1.2至6倍，作为沿周向的拉伸比为1.2至4.5倍。
通过本发明的方法获得的耐压性聚酯容器，在其容器体部中，具有不小于23％的聚酯树脂内层的结晶度，不小于18％的其外层的结晶度，和不小于24％的内层结晶度与外层结晶度的平均值，并且即使当长期保存时也能够长期维持不大于6％的优良雾度。
由于用作中间层的含粘土功能性树脂组合物，本发明的耐压性聚酯容器具有各种功能如气体阻隔性、氧吸收性和水蒸气阻隔性，并能够有效地用作防止内容物味道通过氧而降低的容器。可填充的内容物特别优选本身产生压力的饮料如啤酒、碳酸化软饮料、含果汁碳酸化饮料等，然而，本发明绝不仅限于这些。
实施例
将通过以下实施例进一步描述本发明，然而，其不限制本发明。
[测量结晶度]
将宽度5mm和长度5mm的试验片从获得的多层瓶的体部中央切出。将内聚酯层和外聚酯层从试验片剥离。将样品浸渍于在20℃下的水/硝酸钙型密度梯度管中2小时，其后，读取样品的位置以求得试验片的密度d(g/cm3)。结晶度χc(％)根据下式从获得的密度求得，
χc＝[1.455×(d-1.335)/(d×(1.455-1.335))]×100
其中1.335为完全无定形的聚对苯二甲酸乙二酯树脂的密度，1.455为理论上完全结晶的聚对苯二甲酸乙二酯树脂的密度。
[测量雾度]
将宽度30mm和长度40mm的试验片从刚成型后的多层瓶和在50℃80％RH的环境中保存72小时后的多层瓶的体部中央切出。通过使用color计算机[S&M COLOUR COMPUTER MODELSM-4：由Suga Shikenki Co.制造]测量在它们的多层形式中试验片的雾度。
[实施例1]
通过使用装配有以下三个注塑机，即，用于PET内外层的注塑机(a)，用于PET中间层的注塑机(b)和用于功能性树脂的注塑机(c)的共注塑成型机，通过将在150℃下干燥4小时的聚对苯二甲酸乙二酯(PET)树脂[BK6180，由Nihon Unipet Co.制造]进给至注塑机(a)和(b)中，并通过使用双轴挤出机将通过熔融捏合聚己二酰间苯二甲胺树脂(MXD6)[T620，由Nihon Unipet Co.制造]和3重量％的溶胀化处理的天然蒙脱石获得的树脂组合物作为功能性树脂进给至注塑机(c)，由顺序注塑成型法获得具有PET的内外层和中间层和在它们中的功能性树脂的层的两种五层(a/c/b/c/a)多层预制品，重量为33g。
通过使用石英加热器，将预制品从其外部预热至111℃的表面温度，并在纵向为3.0倍和横向为3.0倍的拉伸比下双轴拉伸吹塑成型，从而获得多层瓶，其具有体积为516ml，在体部中的层厚度，即内PET层(100μm)/内功能性树脂层(10μm)/中间PET层(110μm)/外功能性树脂层(11μm)/外PET层(130μm)。
测量获得的多层瓶的内PET层和外PET层的结晶度和雾度。
[实施例2]
除了预热多层预制品至表面温度为118℃之外，以与实施例1相同的方式成型多层瓶，并测量其结晶度和雾度。
[实施例3]
除了使用通过使用双轴挤出机熔融捏合乙烯/乙烯醇共聚物(EVOH)(Eval F101：由Kuraray Eval Co.制造)和3重量％的溶胀化处理的天然蒙脱石获得的树脂组合物作为功能性树脂，预热多层预制品至表面温度为114℃之外，以与实施例1相同的方式成型多层瓶，并测量其结晶度和雾度。
[实施例4]
除了预热多层预制品至表面温度为116℃之外，以与实施例3相同的方式成型多层瓶，并测量其结晶度和雾度。
[实施例5]
除了预热多层预制品至表面温度为113℃之外，以与实施例1相同的方式成型多层瓶，并测量其结晶度和雾度。
[比较例1]
除了预热多层预制品至表面温度为109℃之外，以与实施例1相同的方式成型多层瓶，并测量其结晶度和雾度。
[比较例2]
除了预热多层预制品至表面温度为121℃之外，以与实施例1相同的方式成型多层瓶。瓶的厚度分布不均匀。
[比较例3]
除了预热多层预制品至表面温度为127℃之外，以与实施例1相同的方式尝试成型多层瓶。然而，预制品结晶，不能成型。
[比较例4]
除了预热多层预制品至表面温度为107℃之外，以与实施例3相同的方式成型多层瓶，并测量其结晶度和雾度。
[比较例5]
除了使用聚己二酰间苯二甲胺树脂(MXD 6)[T620，由NihonUnipet Co.制造]作为功能性树脂之外，以与实施例5相同的方式成型多层瓶，并测量其结晶度和雾度。
表1
*1：瓶厚度分布不均匀
*2：由于预制品结晶导致不能成型
Claims (3)
1.一种耐压性聚酯容器，其具有包括聚酯树脂内外层和至少一层功能性树脂中间层的多层结构，其中，在所述容器体部中，所述聚酯树脂内层具有结晶度不小于23％，其外层具有结晶度不小于18％，所述内层的结晶度与所述外层的结晶度的平均值不小于24％，将粘土分散于所述功能性树脂中。
2.根据权利要求1所述的耐压性聚酯容器，其中所述功能性树脂包含聚己二酰间苯二甲胺或乙烯/乙烯醇共聚物作为基材树脂。
3.一种用于生产耐压性聚酯容器的方法，所述耐压性聚酯容器通过双轴拉伸吹塑成型多层预制品来生产，所述多层预制品包括聚酯树脂内外层和至少一层分散粘土的功能性树脂中间层，其中，将所述多层预制品在110至120℃的温度加热下双轴拉伸吹塑成型，以使多层容器成型，其中所述容器体部中，所述聚酯树脂内层具有结晶度不小于23％，其外层具有结晶度不小于18％，所述内层的结晶度与所述外层的结晶度的平均值不小于24％。
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| US20080257883A1 (en) | 2007-04-19 | 2008-10-23 | Inbev S.A. | Integrally blow-moulded bag-in-container having an inner layer and the outer layer made of the same material and preform for making it |
| US20150266621A1 (en) | 2007-04-19 | 2015-09-24 | Anheuser-Busch Inbev S.A. | Integrally Blow-Moulded Bag-in-Container Having Interface Vents Opening to the Atmosphere at Location Adjacent to Bag's Mouth, Preform for Making It; and Processes for Producing the Preform and Bag-in-Container |
| WO2009119549A1 (ja) | 2008-03-27 | 2009-10-01 | 東洋製罐株式会社 | 延伸発泡プラスチック容器及びその製造方法 |
| JP5652204B2 (ja) * | 2008-09-29 | 2015-01-14 | 東洋製罐株式会社 | 軽量多層ポリエステル容器 |
| JP5387054B2 (ja) * | 2009-03-03 | 2014-01-15 | 東洋製罐株式会社 | 耐落下衝撃性に優れた多層プラスチック容器 |
| KR101103992B1 (ko) | 2009-07-09 | 2012-01-06 | 어드밴스드 테크놀러지 머티리얼즈, 인코포레이티드 | 라이너 베이스의 저장 시스템, 라이너 및 반도체 공정에 고순도 재료를 공급하는 방법 |
| JP6087833B2 (ja) | 2010-11-23 | 2017-03-01 | アドバンスド テクノロジー マテリアルズ，インコーポレイテッド | ライナーベースの分注器 |
| JP5932847B2 (ja) | 2011-03-01 | 2016-06-08 | アドバンスド テクノロジー マテリアルズ，インコーポレイテッド | 入れ子式吹込み成形ライナーおよびオーバーパックならびにその作製方法 |
| CN107454873B (zh) * | 2014-12-12 | 2020-05-22 | 陶氏环球技术有限责任公司 | 多层结构，包括多层结构的层合物和包括层合物的制品 |
| KR101998159B1 (ko) * | 2017-04-20 | 2019-07-09 | 주식회사 엘지생활건강 | 음료 용기 및 그 제조 방법 |
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| JP2002103428A (ja) * | 2000-09-29 | 2002-04-09 | Toyo Seikan Kaisha Ltd | 多層プリフォームおよびこれを用いて製造した多層ボトル |
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| JP2003012023A (ja) * | 2001-04-27 | 2003-01-15 | Toyo Seikan Kaisha Ltd | 保存性に優れた多層プラスチック容器 |
| EP1405874B1 (en) * | 2002-10-03 | 2014-03-26 | Mitsubishi Gas Chemical Company, Inc. | Process for production of polyamide composite material |
| JP4321197B2 (ja) * | 2002-10-03 | 2009-08-26 | 三菱瓦斯化学株式会社 | ポリアミド複合材料の製造方法 |
| JP2005067637A (ja) | 2003-08-21 | 2005-03-17 | Mitsubishi Gas Chem Co Inc | 中空容器 |
| JP2005255736A (ja) * | 2004-03-09 | 2005-09-22 | Toyo Seikan Kaisha Ltd | バリアー性及び透明性を有する生分解性容器 |
| AU2005249842B2 (en) * | 2004-06-04 | 2010-04-22 | Mitsubishi Gas Chemical Company, Inc. | Gas-barrier multilayer structure and process for producing the same |
| JP2006027701A (ja) * | 2004-07-20 | 2006-02-02 | Toyo Seikan Kaisha Ltd | 果実飲料充填プラスチック多層容器 |
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| US20100116707A1 (en) | 2010-05-13 |
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| JP5305610B2 (ja) | 2013-10-02 |
| WO2008126744A1 (ja) | 2008-10-23 |
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| EP2130782A1 (en) | 2009-12-09 |
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