CN102026880B - 阻隔性优异的合成树脂制容器 - Google Patents
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Abstract
本发明提供一种即便长期保存也不会在未延伸部产生白浊、且阻隔性优异的合成树脂制容器。本发明的PET瓶包括由PET构成的基材层(11)、及透气性低于所述基材层(11)的阻隔层(12),且使所述阻隔层(12)在由含间二甲苯基的聚酰胺构成的阻隔材中,含有具有间二甲苯间苯二甲酰胺结构和六亚甲基间苯二甲酰胺结构的非晶性聚酰胺。在所述非晶性聚酰胺中,使用间苯二甲胺和间苯二甲酸的共聚物(MXDI)、与六亚甲基二胺和间苯二甲酸的共聚物(6I)的共聚酰胺,使阻隔层(12)中的非晶性聚酰胺的含有率为大于等于15wt%、且小于等于25wt%的范围内。
Description
技术领域
本发明涉及一种具有由合成树脂构成的基材层、及透气性低于所述基材层的阻隔层的合成树脂制容器,其阻隔性优异。
背景技术
众所周知,以聚对苯二甲酸乙二酯(PET,polyethylene terephthalate)瓶为代表的合成树脂制容器会使极微量的氧气或二氧化碳气体等透过,为了阻止这些气体透过,而建议在由PET树脂构成的基材层上,积层着气体阻隔层的构造(例如,参照日本专利特开2007-8582号公报)。
发明内容
然而,当将这种容器吹塑成形(blow molding)时,若长期保存此产品,那么有时未延伸部(例如,当吹塑成形品为瓶子时,此瓶的瓶颈部)会产生白浊。这种白浊虽然对容器自身的性能并无任何问题,但存在影响容器外观的问题。
对此,本申请案发明人发现白浊的原因在于气体阻隔层。例如,若以采用由间苯二甲胺和己二酸的缩聚反应所得的聚酰胺MXD6(三菱瓦斯化学株式会社制)作为气体阻隔层的材料为例,那么白浊的原因在于MXD6结晶。而且,在因MXD6的回潮率(moisture percentage)上升而使玻璃转移温度和结晶温度(crystallization temperature)下降的情况下将促进MXD6结晶。
因此,本申请案发明人认为如果将至少气体阻隔层的结晶温度提高,那么可抑制未伸延部中产生白浊的情况。
木发明应解决的问题在于,如果将具有基材层和阻隔层且阻隔性优异的合成树脂制容器吹塑成形,进行长期保存,便会在未延伸部产生白浊,而本发明的目的在于提供一种即便长期保存,也不会在未延伸部中产生白浊、且阻隔性优异的合成树脂制容器。
作为本发明的阻隔性优异的合成树脂制容器是具有由合成树脂构成的基材层、及透气性低于所述基材层的阻隔层,且阻隔性优异的合成树脂制容器,其特征在于:所述阻隔层是由结晶化峰值温度大于等于150℃的合成树脂所构成。
另外,所谓“结晶化峰值温度”是指使用差示扫描量热仪(DSC,differentialscanning calorimeter),测量由结晶所引起的发热量,并基于所述发热量特性所计算出的温度,本发明中是指从20℃起以10℃/min的升温速度而加热到270℃为止,将此状态维持5分钟后,暂时水冷到20℃为止,进而,从20℃起以10℃/min的升温速度而加热到270℃为止后的结晶化峰值温度。
而且,作为结晶化峰值温度的更佳范围,为大于等于150℃、且小于等于170℃的范围。
作为本发明的阻隔层,可列举含有具有间二甲苯间苯二甲酰胺结构和六亚甲基间苯二甲酰胺结构的非晶性聚酰胺,且所述非晶性聚酰胺在阻隔层中的含有比率为大于等于15wt%、且小于等于25wt%的范围。
作为阻隔层的具体例,可列举由所述非晶性聚酰胺、及透气性低于构成基材层的材质的阻隔材所构成,且所述阻隔材为含间二甲苯基的聚酰胺。而且,作为含间二甲苯基的聚酰胺,可列举使间苯二甲胺和己二酸缩聚反应所得的聚酰胺。
相对于此,作为所述非晶性聚酰胺,可列举间苯二甲胺和间苯二甲酸的共聚物(MXDI:间二甲苯间苯二甲酰胺)、与己二胺和间苯二甲酸的共聚物(6I:聚六亚甲基间苯二甲酰胺)的共聚酰胺(MXDI/6I)。此外,作为所述基材层,可列举由聚对苯二甲酸乙二酯构成者。
根据本发明,如果使用从20℃起以10℃/min的升温速度加热到270℃为止,并将此状态维持5分钟后,暂时水冷到20℃为止,进而,从20℃起以10℃/min的升温速度加热到270℃为止时的结晶峰值温度大于等于150℃的合成树脂作为阻隔层,那么,作为吹塑成形品即便长期保存,它的未伸延部也将难以产生白浊。
即,根据本发明,一方面能够长期发挥气体阻隔性能一方面又无损美观。因此,根据本发明,可提供一种即便长期保存也难以产生白浊、且阻隔性优异的合成树脂制容器。
而且,如果使用含有具有间二甲苯间苯二甲酰胺结构和六亚甲基间苯二甲酰胺结构的非晶性聚酰胺,且所述非晶性聚酰胺在阻隔层中的含有比率为大于等于15wt%、且小于等于25wt%的范围的合成树脂作为所述阻隔层,那么,可以利用容易的方法来实现所述白浊的防止效果。
此外,当所述阻隔层是由所述非晶性聚酰胺、和透气性低于构成基材层的材质的阻隔材所构成时,如果采用含间二甲苯基的聚酰胺作为所述阻隔材,那么,将起到优异的防止白浊的效果。
而且,如果采用间苯二甲胺和间苯二甲酸的共聚物(MXDI)、与己二胺和间苯二甲酸的共聚物(6I)的共聚酰胺作为本发明的非晶性聚酰胺,那么,将起到优异的防止白浊的效果。
附图说明
图1是以局部截面来表示本发明的PET瓶1的侧视图。
符号的说明
1PET瓶
2瓶嘴部
3瓶颈部
4瓶肩部
5瓶体部
6瓶底部
11基材层
12气体阻隔层
具体实施方式
以下,参照图式,对本发明的一实施例进行详细说明。
图1是以局部截面来表示本发明的PET瓶1的侧视图。
符号1是由瓶嘴部2、瓶颈3、瓶肩部4、瓶体部5以及瓶底部6构成的吹塑成形瓶(以下,简称为“瓶”)。如图中的区域X所示,此瓶1是将造形瓶本体的形成基本形状的基材层11作为内层及外层,且气体阻隔层12插入在这些基材层11之间的积层体。
基材层11是由聚对苯二甲酸乙二酯树脂(以下,称为“PET树脂”)或以PET树脂为主成分的合成树脂所构成。
气体阻隔层12中,使用如下的合成树脂:在经过从20℃状态起以升温速度10℃/min加热到270℃为止,并将此状态维持5分钟的第一步骤(以下,称为“1st_Run”)之后,暂时水冷到20℃为止,进而从20℃起以升温速度10℃/min加热到270℃为止的第二步骤(以下,称为“2nd_Run”)后的结晶化峰值温度Tpc为大于等于150℃、且小于等于170℃之范围。
作为具体例而言,气体阻隔层12是使用以透气性低于基材层11的阻隔材为主成分,且含有具有间二甲苯间苯二甲酰胺结构和六亚甲基间苯二甲酰胺结构的非晶性聚酰胺(以下,称为“非晶性聚酰胺”)的合成树脂。
而且,阻隔材中可列举含间二甲苯基的聚酰胺,例如,由间苯二甲胺和己二酸的共聚物构成。
相对于此,非晶性聚酰胺中,可列举例如间苯二甲胺和间苯二甲酸的共聚物(MXDI)、与己二胺和间苯二甲酸的共聚物(6I)的共聚酰胺。
气体阻隔层12中的非晶性聚酰胺的含有率设为大于等于15wt%、且小于等于25wt%的范围。即,使阻隔材和非晶性聚酰胺的混合率(重量比)为阻隔材∶非晶性聚酰胺=85∶15~75∶25。
根据本发明,如果使用经过2nd_Run之后的结晶化峰值温度Tpc为大于等于150℃、且小于等于170℃的范围的合成树脂作为气体阻隔层12,那么,作为吹塑成形品即便长期保存,它的未伸延部即瓶颈部3也将难以产生白浊。
即,根据瓶1,一方面长期发挥气体阻隔性能一方面无损美观。因此,根据瓶1,可以提供即便长期保存也难以产生白浊、且阻隔性优异的吹塑成形瓶。
尤其,如同本实施例一样,如果使用含有具有间二甲苯间苯二甲酰胺结构和六亚甲基间苯二甲酰胺结构的非晶性聚酰胺,且所述非晶性聚酰胺在阻隔层12中的含有比率为大于等于15wt%、且小于等于25wt%的范围的合成树脂作为阻隔层12,那么,可以利用容易的方法来实现所述白浊的防止效果。
此外,如同本实施例一样,当阻隔层12由非晶性聚酰胺、及透气性低于构成基材层11的材质(本实施例中为PET树脂)的阻隔材所构成时,如果使用含间二甲苯基的聚酰胺作为所述阻隔材,那么,可以起到优异的白浊防止的效果。
而且,如同本实施例的一样,如果使用间苯二甲胺和间苯二甲酸的共聚物(MXDI)、与己二胺和间苯二甲酸的共聚物(6I)的共聚酰胺作为非晶性聚酰胺,那么,可以起到优异的白浊防止的效果。
另外,基于本发明的容器的层结构,并不限定于本实施例的层结构,可以是至少基材层11和气体阻隔层12的两层结构。而且,依据本发明,也可以仅由气体阻隔层12形成该瓶1。
实施例
以下,表示利用基于JIS K 7121的方法来测量本发明的实施例和所述比较例时的评估。
用于评估的样品是从总重量32g且500ml内容量的图1所示的瓶中,将基材层11去除,将位于其瓶颈部3的气体阻隔层12的一部分的约10mg作为试验片,测量装置使用差示扫描量热仪DSC6220(SIINT公司制造)。
而且,以下的表1~3所示的测量值分别为外推结晶化开始温度Tic、结晶化峰值温度Tpc以及外推结晶化结束温度Tec,添加量的单位系统为wt%(重量百分比)。
而且,表1~3的测量值均为经过从20℃状态起以升温速度10℃/min加热到270℃为止,并将此状态维持5分钟的“1st_Run”之后,暂时水冷到20℃为止,进而从20℃起以升温速度10℃/min加热到270℃为止的“2nd_Run”后所测量的数值。
另外,表1是将瓶嘴部2未延伸部的阻隔层作为样品。而且,表2是将作为延伸部的瓶体部4的阻隔层作为样品。
[表1]
[表2]
比较例1是仅由MXD6(三菱瓦斯化学株式会社制造s6011)阻隔材构成的样品。而且,比较例2是以90∶10的比例将作为阻隔材的MXD6、和非晶性聚酰胺(Grivory HB FE7103EMS公司制造)混合而成的样品。
相对于此,实施例1~3是分别使和比较例2相同的阻隔材以及非晶性聚酰胺为85∶15、80∶20、75∶25。
使所述比较例1、2以及实施例1~3分别装填水,并在23℃-55%RH的保存环境下进行保存后,比较例1在第46天于瓶颈部3中产生白浊,比较例2在第70天于瓶颈部3中产生白浊,实施例1~3则在经过第3个月的时间点也未产生白浊。
相对于此,使所述比较例1、2以及实施例1~3分别装填水,并在40℃-75%RH的保存环境下进行保存后,比较例1、2分别在第8天和第11天于瓶颈部3中产生白浊,而实施例1~3分别在第12天、第14天、第14天于瓶颈部3中产生白浊。
[表3]
23℃-55%RH | 40℃-75%RH | |
比较例1 | 46天白浊 | 8天白浊 |
比较例2 | 70天白浊 | 11天白浊 |
实施例1 | 3个月以上 | 12天白浊 |
实施例2 | 3个月以上 | 14天白浊 |
实施例3 | 3个月以上 | 14天白浊 |
而且,如果参照表1~3则可知,外推结晶化结束温度Tec和外推结晶化开始温度Tic的温度范围越大、即,结晶速度越慢,那么越难以产生白浊。
而且,以下的表4是分别在1st_Run和2nd_Run中对所述比较例1、实施例1~3,测量中间点玻璃转移温度Tmg、结晶化峰值温度Tpc以及溶解峰值温度Tpm所得的结果。
[表4]
进而,表5是分别将瓶颈部3的气体阻隔层12剥离后的试验片的一部分在吸水率2%附近的中间点玻璃转移温度Tmg、结晶化峰值温度Tpc以及溶解峰值温度Tpm的DSC测量所得的结果。另外,吸水率是利用京都电子工业制造卡尔费休水分测定仪MKC-610在测量温度180℃下所测量的。
[表5]
根据表5的结果可以看出:如果吸水率变大,那么玻璃转移温度和结晶温度都将下降。由此可知,不仅提高以结晶化峰值温度Tpc为代表的结晶温度来抑制未延伸部的白浊产生,而且关于玻璃转移温度也是相同的情况。
[产业上的可利用性]
本发明容器不仅限于瓶,只要是以内容物的品质保持为目的的容器,那么可以用于各种形态的容器。
Claims (5)
1.一种阻隔性优异的合成树脂制容器,具有由合成树脂构成的基材层、及透气性低于所述基材层的阻隔层,且阻隔性优异,其特征在于:
所述阻隔层是由从20℃起以10℃/min的升温速度而加热到270℃为止,将此状态维持5分钟后,暂时水冷到20℃为止,进而,从20℃起以10℃/min的升温速度而加热到270℃为止后的结晶化峰值温度大于等于150℃且小于等于170℃的合成树脂所构成。
2.根据权利要求1所述的阻隔性优异的合成树脂制容器,其特征在于:所述阻隔层含有具有间二甲苯间苯二甲酰胺结构和六亚甲基间苯二甲酰胺结构的非晶性聚酰胺,
且所述非晶性聚酰胺在阻隔层中的含有比率为大于等于15wt%、且小于等于25wt%的范围的合成树脂。
3.根据权利要求2所述的阻隔性优异的合成树脂制容器,其特征在于:所述阻隔层由所述非晶性聚酰胺、和透气性低于构成基材层的材质的阻隔材所构成,
且所述阻隔材为含间二甲苯基的聚酰胺。
4.根据权利要求2所述的阻隔性优异的合成树脂制容器,其特征在于:所述非晶性聚酰胺是间苯二甲胺和间苯二甲酸的共聚物(MXDI)、与己二胺和间苯二甲酸的共聚物(6I)的共聚酰胺(MXDI/6I)。
5.根据权利要求1或2所述的阻隔性优异的合成树脂制容器,其特征在于:基材层是由聚对苯二甲酸乙二酯所构成。
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3154392B2 (ja) * | 1995-09-29 | 2001-04-09 | 宇部興産株式会社 | ガスバリヤー性に優れたポリアミド樹脂およびその製造方法 |
CN1934004A (zh) * | 2004-03-26 | 2007-03-21 | 株式会社吉野工业所 | 具有高气体阻绝性的合成树脂容器 |
CN1950235A (zh) * | 2004-05-07 | 2007-04-18 | 西门子公司 | 用于机动车的燃油供给装置 |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58183243A (ja) * | 1982-04-22 | 1983-10-26 | 株式会社吉野工業所 | 合成樹脂製2軸延伸ブロ−成形壜体 |
JPH075831B2 (ja) * | 1986-10-24 | 1995-01-25 | 旭電化工業株式会社 | ポリアミド組成物 |
JPH075831Y2 (ja) | 1988-08-17 | 1995-02-15 | 松下電器産業株式会社 | 遠心脱水機用内蓋 |
US5175238A (en) | 1989-07-21 | 1992-12-29 | Amoco Corporation | Polyamide having improved gas barrier properties from adipic acid, isophthalic acid and m-xylylene diamine |
JPH075831A (ja) | 1993-06-16 | 1995-01-10 | Sekisui Chem Co Ltd | 埋設物表示シート |
JPH1149941A (ja) * | 1997-08-06 | 1999-02-23 | Toyobo Co Ltd | ポリエステル樹脂製容器 |
TW431967B (en) * | 1998-04-09 | 2001-05-01 | Kuraray Co | Coinjection stretch blow molded container |
JP2001010675A (ja) * | 1999-06-29 | 2001-01-16 | Tsutsumi Yotaro | 酸素吸収性包装体 |
AU780900B2 (en) * | 2000-12-08 | 2005-04-21 | Toyo Seikan Kaisha Ltd. | Packaging material and multi-layer container |
US6410156B1 (en) | 2001-03-06 | 2002-06-25 | Honeywell International Inc. | Oxygen scavenging polyamide compositions suitable for pet bottle applications |
TWI281891B (en) | 2002-03-01 | 2007-06-01 | Teijin Ltd | Biaxially oriented multi-layered laminated film and method for manufacture thereof |
KR100743165B1 (ko) | 2002-06-05 | 2007-07-27 | 가부시키가이샤 요시노 고교쇼 | 기능적 특성이 우수한 합성수지제 용기 및 그 제조 방법 |
CN1550326B (zh) | 2003-05-06 | 2010-08-25 | 三菱瓦斯化学株式会社 | 多层容器 |
US20050009976A1 (en) * | 2003-07-10 | 2005-01-13 | Honeywell International, Inc. | Delamination-resistant, barrier polyamide compositions for 3-layer pet beverage bottles |
US20060230553A1 (en) * | 2005-04-14 | 2006-10-19 | Helmut Thullen | Process for tinting, dyeing or doping of moulded components made of transparent (co)polyamides in aqueous dye bath |
JP4946010B2 (ja) | 2005-05-31 | 2012-06-06 | 日本ゼオン株式会社 | 多層プラスチック容器 |
US8778470B2 (en) * | 2006-01-18 | 2014-07-15 | Mitsubishi Gas Chemical Company, Inc. | Multi-layer bottle |
DE502006003349D1 (de) * | 2006-12-28 | 2009-05-14 | Ems Chemie Ag | Mit flachen Glasfasern verstärkte Polyamidformmassen sowie daraus hergestellte Spritzgussteile |
JP5148199B2 (ja) * | 2007-07-31 | 2013-02-20 | 株式会社吉野工業所 | バリア性に優れた合成樹脂製容器 |
US20090061212A1 (en) * | 2007-08-29 | 2009-03-05 | Wurtzel Kenneth C | Reduced Crystallizing Aromatic Nylon |
JP4986912B2 (ja) * | 2008-03-31 | 2012-07-25 | 株式会社吉野工業所 | バリア性に優れた合成樹脂製容器 |
JP3154392U (ja) | 2009-07-30 | 2009-10-15 | 呉 志賢 | 振動式洗浄装置 |
-
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- 2008-03-31 JP JP2008093490A patent/JP4986912B2/ja active Active
-
2009
- 2009-02-23 WO PCT/JP2009/053192 patent/WO2009122820A1/ja active Application Filing
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3154392B2 (ja) * | 1995-09-29 | 2001-04-09 | 宇部興産株式会社 | ガスバリヤー性に優れたポリアミド樹脂およびその製造方法 |
CN1934004A (zh) * | 2004-03-26 | 2007-03-21 | 株式会社吉野工业所 | 具有高气体阻绝性的合成树脂容器 |
CN1950235A (zh) * | 2004-05-07 | 2007-04-18 | 西门子公司 | 用于机动车的燃油供给装置 |
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