CN1842412A - 制备具有高阻透性和改善的透明度的单层pet瓶的方法 - Google Patents
制备具有高阻透性和改善的透明度的单层pet瓶的方法 Download PDFInfo
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Abstract
本发明包含聚酯和部分芳族聚酰胺与离子增容剂和钴盐的共混料。可以将该共混料加工成为容器,所述的容器比本领域中已知的容器具有改善的颜色和透明度下同时具有主动或被动的氧阻透性和二氧化碳阻透性。部分芳族聚酰胺优选为间-亚二甲苯基己二酰二胺。离子增容剂优选为5-钠磺基间苯二甲酸或5-锌磺基间苯二甲酸,或它们的二烷基酯如二甲基酯(SIM)和乙二醇酯(SIPEG)。钴盐选自乙酸钴、碳酸钴、氯化钴、氢氧化钴、环烷酸钴、油酸钴、亚油酸钴、辛酸钴、硬脂酸钴、硝酸钴、磷酸钴、硫酸钴、钴(乙二醇盐),或它们两种或多种的混合物。存在的部分芳族聚酰胺为所述组合物的约1至约10重量%。存在的离子增容剂为所述组合物的约0.1至约2.0摩尔-%。存在的钴盐为所述组合物的约20至约500ppm。
Description
发明背景
1)发明领域
本发明涉及聚酰胺在聚酯中的增容共混料,形成这样的组合物的方法,以及由这样的组合物制成的容器。具体而言,所述组合物比以前的共混料具有更低的黄色。可以将该共混料在加入过渡金属催化剂的条件下用作被动的阻气剂或主动的氧清除剂。
2)现有技术
已经将塑料用来代替玻璃和金属包装材料,原因在于它们更轻的重量、与玻璃相比降低的破裂,以及潜在的低成本。聚酯的一个主要缺点在于它相对高的透气性。这限制了充气软饮料和氧气敏感物质如啤酒和果汁的贮藏寿命。
含有低透气性聚合物作为内层,采用聚酯作为其它层的多层瓶已经商业化。这些低透气性聚合物共混到聚酯中的共混料还没有取得成功,原因在于由两相体系中的域形成的雾度。优选的聚酰胺是含有间-亚二甲苯基的部分芳族聚酰胺,特别是聚(间-亚二甲苯基己二酰二胺),MXD6。
Mitsubishi Gas Chemical Company,Inc.,Tokyo Japan的MXD6公报(TRNo.0009-E)清楚地表明,含有5重量-%MXD6层的多层瓶的雾度为~1%,与此相比较的是,对于相同的5重量-%的共混物,为15%。
但是,部分芳族聚酰胺作为低透气性聚合物的使用导致得到的容器黄色的提高。
Kushida等的美国专利4,501,781公开了一种中空吹塑双轴取向瓶成型容器,其包含对聚对苯二甲酸乙二醇酯(PET)树脂和含亚二甲苯基的聚酰胺树脂的混合物。同时公开了单层和多层容器,但是没有关于瓶子颜色的信息。
Long等的美国专利5,650,469公开了共混有低含量(0.05至2.0重量-%)聚酰胺的对苯二甲酸基聚酯对于降低容器的乙醛含量的应用。这些共混料比由对苯二甲酸二甲酯基聚酯制成的相应共混料产生更低的黄色,但是对于显著降低(减小)气透性所需要的更高级别而言,仍然是不满意的。
Mills等的美国专利5,258,233、5,266,413和5,340,884公开了一种聚酯组合物,其包含0.05至2.0重量-%的低分子量聚酰胺。在0.5重量-%的MXD6的共混料下,瓶子的雾度从0.7%增加至1.2%。未给出透气性或颜色数据。
Igarashi等的美国专利4,837115公开了一种氨基封端的聚酰胺与PET的共混料,以降低乙醛含量。在加入0.5重量-%MXD6的条件下,雾度没有提高,但在2重量-%下,雾度从1.7%增加至2.4%。未给出透气性或颜色数据。
Bell等的美国专利6,239,233公开一种酸封端的聚酰胺与PET的共混料,与氨基封端的聚酰胺相比,其黄色降低。未给出透气性数据。
Al Ghatta等的美国专利6,346,307公开了四羧酸二酐对于降低MXD6在PET中的共混料的分散域尺寸的应用。实施例没有给出颜色数据,但是,在10重量-%MXD6共混料的水平下,氧透气性从0.53降低至0.12ml/瓶/天/atm,并且二氧化碳透气性从18.2降低至7.02ml/瓶/天/atm。
Turner等的美国专利6,444,283公开了在与PET共混时,低分子量的MXD6聚酰胺比更高分子量的MXD6聚酰胺的雾度低。实施例没有给出颜色数据,但是,在2重量-%MXD6(Mitsubishi Chemical Company,等级6007)下,定向膜的氧透气性从8.1降低至5.7cc-mil/100 in2-atm-天,与此相比较的是,对于低分子量的MXD6,为6.1。
Koyayashi等的美国专利4,957,980公开了马来酸酐接枝共聚多酯对于增容聚酯-MXD6共混料的应用。
Fagerburg等的美国专利4,499,262公开了磺基改性的聚酯,其具有改善的乙醛生成速率,并且具有更低的临界平面拉伸比。未讨论与聚酰胺的共混料。
Katsumasa等的日本专利2663578 B2公开了0.5至10摩尔%的5-磺基间苯二甲酸酯共聚物作为聚酯-MXD6共混料的增容剂的应用。未给出颜色数据。
例如,在下面的专利中公开了过渡金属催化剂在聚酰胺多层容器和含有PET的共混料中促进氧清除的应用。
Cochran等的美国专利5,021,515、5,639,815和5,955,527公开了钴盐作为优选的过渡金属催化剂和MXD6作为优选的聚酰胺的应用。没有聚酰胺共混料的颜色或雾度的数据。
Hong的美国专利5,281,360和5,866,649和Kim的美国专利6,288,161公开了MXD6与PET以及钴盐催化剂的共混料。没有聚酰胺共混料的颜色或雾度的数据。
You等的美国专利5,623,047公开了含有碱金属乙酸盐(优选30ppm乙酸钴)的催化剂组合物对于掩蔽由对苯二甲酸聚合的聚酯中的黄色的应用。
Kim等的美国专利申请2003/0134966A1公开了辛酸钴和含二甲苯基的聚酰胺的应用,用于多层挤出吹塑,以改善透明度。与注射拉伸吹塑容器相比,挤出吹塑使聚酰胺域尺寸最小化。未给出颜色数据。
需要一种改善阻气性的聚酯组合物,其可以被注射拉伸吹塑成为单层容器,所述的容器具有降低的黄色和足够的雾度。对于要求长的贮藏寿命如啤酒和其它氧气敏感物质的容器特别需要。这些专利都没有公开怎样达到这些性能的平衡。
发明概述
本发明是对本领域中已知的聚酯/聚酰胺共混料的改进,即,这些组合物具有降低的黄色。
最广泛而言,本发明包含聚酯和部分芳族聚酰胺与离子增容剂和钴盐的增容共混料。
本发明最宽的范围还包含一种容器,其在比本领域中已知的容器具有改善的颜色和透明度的条件下同时具有主动和被动的氧阻透性和二氧化碳阻透性。
最广泛而言,本发明还包含一种容器,其中,可以独立地平衡阻气性和颜色之间的平衡。
最广泛而言,本发明是一种将聚酯和聚酰胺与离子增容器和钴盐共混的方法。
附图简述
附图是用于帮助本领域的技术人员理解本发明,而不是想要以任何超出本发明范围的方式限制本发明的范围。
图1所示为实施例3选择批次的氧渗透速度的曲线图。
图2所示为实施例4的批次的氧渗透速度的曲线图。
发明详述
本发明的组合物包含:聚酯、部分芳族聚酰胺、离子增容剂和钴盐。
通常,聚酯可以通过下面的两种方法之一来制备,即:(1)酯方法和(2)酸方法。酯方法是这样一种方法,其中二羧酸酯(如,对苯二甲酸二甲酯)在酯交换反应中与1,2-亚乙基二醇或其它二元醇反应。因为该反应是可逆的,通常需要除去醇(当采用对苯二甲酸二甲酯时,甲醇),以将原料完全转化成单体。用于酯交换反应的一些催化剂是周知的。过去,通过在酯交换反应结束时引入磷化合物,例如多磷酸,于是使催化活性消除。首先,使酯交换催化剂失活,以防止在聚合物中产生黄色。
然后,单体进行缩聚,并且在此反应中采用的催化剂通常为锑、锗或钛化合物,或它们的混合物。
在制备聚酯的第二种方法中,通过直接酯化反应,酸(例如,对苯二甲酸)与二元醇(例如,1,2-亚乙基二醇)反应,生成单体和水。与酯方法一样,该反应也是可逆的,因此为使反应完成,必须除去水。直接酯化步骤不需要催化剂。然后,单体进行缩聚,以正如酯方法中的那样,生成聚酯,并且所采用的催化剂和条件通常与酯方法中的催化剂和条件相同。
对于多数容器应用而言,将此熔体相聚酯通过固态聚合而进一步聚合为更高的分子量。
概括而言,在酯方法中,有两个步骤,即(1)酯交换和(2)缩聚。在酸方法中,也有两个步骤,即(1)直接酯化和(2)缩聚。
适宜的聚酯由二元酸或二元酯组分与二元醇组分的反应来制备,所述的二元酸或二元酯组分包含:至少65摩尔-%、优选至少70摩尔-%、更优选至少75摩尔-%、再更优选至少95摩尔-%的对苯二甲酸或对苯二甲酸C1-C4二烷基酯,并且所述的二元醇组分包含:至少65摩尔-%、优选至少70摩尔-%、更优选至少75摩尔-%、再更优选至少95摩尔-%的1,2-亚乙基二醇。还优选二元酸组分是对苯二甲酸并且二元醇组分是1,2-亚乙基二醇,从而生成聚对苯二甲醇乙二醇酯(PET)。所有二元酸组分的摩尔百分比之和为100摩尔-%,并且所有二元醇组分的摩尔百分比之和为100摩尔-%。
在由一种或多种不同于1,2-亚乙基二醇的二元醇组分改性聚酯组分的情况下,所述聚酯的适宜二元醇组分可以选自:1,4-环己烷二甲醇、1,2-丙二醇、1,4-丁二醇、2,2-二甲基-1,3-丙二醇、2-甲基-1,3-丙二醇(2MPDO)、1,6-己二醇、1,2-环己二醇、1,4-环己二醇、1,2-环己烷二甲醇、1,3-环己烷二甲醇,以及在链中含有一个或多个氧原子的二元醇,如二甘醇、三甘醇、双丙甘醇、三丙甘醇或它们的混合物,等。一般而言,这些二元醇含有2至18个、优选2至8个碳原子。环脂族二元醇可以采用它们的顺式或反式构型,或这两种型式的混合物。优选的改性二元醇组分是1,4-环己烷二甲醇或二甘醇或它们的混合物。
在由一种或多种不同于对苯二甲酸的酸组分改性聚酯组分的情况下,所述线性聚酯的适宜酸组分(脂族、脂环族或芳族二羧酸)可以选自:例如,间苯二甲酸、1,4-环己二羧酸、1,3-环己二羧酸、琥珀酸、戊二酸、己二酸、癸二酸、1,12-十二烷二酸、2,6-萘二甲酸、联苯甲酸,或它们的混合物,等。在聚合物的制备中,通常优选使用其官能酸衍生物,如二羧酸的二甲酯、二乙酸或二丙酯。在实际的情况下,可以采用这些酸的酸酐或酰卤。与对苯二甲酸相比,这些酸改性剂通常延迟结晶速率。
本发明还特别关注的是通过使至少85摩尔-%来自对苯二甲酸或对苯二甲酸二甲酯的对苯二甲酸酯与上面所述的任何一种共聚单体反应制备的改性聚酯。
除了由对苯二甲酸(或对苯二甲酸二甲酯)和1,2-亚乙基二醇制备的聚酯,或如上所述的改性聚酯外,本发明还包括使用100%的芳族二元酸,如2,6-萘二甲酸或联苯酸,或它们的二元酯,以及通过使至少85摩尔-%来自这些芳族二元酸/二元酯的二羧酸酯与上面所述的任何一种共聚单体反应制备的改性聚酯。
优选用作共混料的阻气性组分的聚酰胺选自:部分芳族聚酰胺,其酰胺键含有至少一种芳环和非芳族物质。优选的部分芳族聚酰胺包括:聚(间-亚二甲苯基己二酰二胺)、聚(间苯二甲酰己二胺)、聚(六亚甲基己二酰二胺-共-间苯二甲酰胺)、聚(六亚甲基己二酰二胺-共-对苯二甲酰胺)、聚(六亚甲基间苯二甲酰胺-共-对苯二甲酰胺),或它们两种或多种的混合物。最优选的是:聚(间-亚二甲苯基己二酰二胺)。
根据容器所需要的阻气性,聚酰胺的优选范围为组合物的1至10重量%。
离子增容剂优选为含有金属磺酸盐基团的共聚多酯。磺酸盐的金属离子可以是Na+、Li+、K+、Zn++、Mn++、Ca++等。磺酸盐基团被连接至芳族酸核如苯、萘、二苯基、氧二苯基、磺酰基二苯基或亚甲基二苯基核上。
优选地,芳族酸核是磺基邻苯二甲酸、磺基对苯二甲酸、磺基间苯二甲酸、4-磺基萘-2,7-二甲酸和它们的酯。最优选地,磺基单体是5-钠磺基间苯二甲酸或5-锌磺基间苯二甲酸,且最优选地,它们的二烷基酯如二甲基酯(SIM)和乙二醇酯(SIPEG)。5-钠磺基间苯二甲酸或5-锌磺基间苯二甲酸用于降低容器雾度的最优选范围为0.1至2.0摩尔-%。
用于本发明的适宜钴化合物包括:除了别的以外,乙酸钴、碳酸钴、氯化钴、氢氧化钴、环烷酸钴、油酸钴、亚油酸钴、辛酸钴、硬脂酸钴、硝酸钴、磷酸钴、硫酸钴、钴(乙二醇盐),或它们两种或多种的混合物。至于用于主动氧清除的过渡金属催化剂,优选长链脂肪酸的盐,最优选辛酸钴或硬脂酸钴。为了对被动阻气性共混料进行颜色控制,可以使用任何钴化合物,其中优选乙酸钴。
令人惊奇的发现,离子增容剂,除了改善阻气性和改善雾度外,还与钴盐一起显著降低树脂、坯料和容器的黄色。对于含有1至10重量-%部分芳族聚酰胺和0.1至2.0摩尔-%离子增容剂的共混料而言,Co的优选范围为20至500ppm。
尽管不要求,但是在聚酯/聚酰胺共混料中可以使用添加剂。常规已知的添加剂包括但不限于下列添加剂:染料、颜料、填料、支化剂、再热剂、防粘剂、抗氧化剂、抗静电剂、杀生物剂、发泡剂、偶联剂、阻燃剂、热稳定剂、抗冲改性剂、UV和可见光稳定剂、结晶助剂、润滑剂、增塑剂、加工助剂、乙醛和其它清除剂以及滑爽剂,或它们的混合物。
聚酯、离子增容剂、钴盐和部分芳族聚酰胺的共混料可以通过下面的方法常规地制备:将所述的组分加入至制备坯料的注塑机的进料口中,所述的坯料可以被拉伸吹塑成为容器的形状。如果使用的是为聚酯容器而设计的常规聚酯基础树脂,那么使用这样一种方法来制备含有离子增容剂,和任选的用于主动清除的过渡金属催化剂以及部分芳族聚酰胺的的聚酯母料:使用用于这三种组分的计重喂料器。备选地,聚酯树脂可以与离子增容剂以及任选的用于主动清除的过渡金属催化剂聚合,以生成共聚物。该共聚物可以与部分芳族尼龙在注塑机中混合。备选地,可以将所有的共混料共混在一起,或者作为母料的共混物,并且作为单一材料进料至挤出机。应当设计挤出机的混合部分以制备均匀的共混料。这可以通过以下方法来确定:测量坯料的热性能以及观察单一的玻璃化转变温度,与此相对比的部分芳族聚酰胺和聚酰的两个单独玻璃化转变温度。
这些工艺步骤适于例如形成充气软饮料、水或啤酒瓶,以及用于热装罐应用的容器。本发明可用于任何用于制备聚酯容器的常规已知的方法中。
测试程序
1.膜的氧和二氧化碳渗透性,被动的
用Mocon Ox-Tran 2/20型号(MOCON Minneapolis,MN)测量在0%相对湿度、1个大气压和25℃下的膜样品的氧流量。将98%氮与2%氢的混合物用作载气,并且将100%氧用作测试气体。在测试之前,将样品在单元内的氮气中调节最小24小时,以除去溶解于PET基质中的痕量大气氧。继续调节,直到得到稳定的基线,其中氧流量对于一个30分钟的循环的改变小于1%。接着,将氧引入测试室内。当流量达到其中氧流量在30分钟的测试循环期间的改变小于1%的稳定状态时,测试结束。根据PET共聚物的渗透系数的文献方法,由费克扩散第二定律,采用适宜的边界条件,进行氧渗透性的计算。文献文件是:Sekelik等,Journal of Polymer SciencePart B:Polymer Physics,1999,Volume 37,Pages 847-857。第二篇文献文件是Qureshi等,Journal of Polymer Science Part B:Polymer Physics,2000,Volume 38,Pages 1679-1686。第三篇文献文件是Polyakova等,Journal ofPolymer Science Part B:Polymer Physics,2001,Volume 39,Pages1889-1899。
以相同的方式,用二氧化碳代替氧气,并且使用Mocon Permatran-C4/40仪器测量膜的二氧化碳渗透性。
所有的膜渗透性值的单位为(cc(STP).cm)/(m2.atm.天))。
2.膜的氧渗透性,主动清除剂
使用与上面所述的用于被动氧渗透性相同的方法,不同之处在于,不需要使氧流量平衡至稳定状态。在将氧引入至室中之后,从0到至少350小时测量氧量的减少。处理数据得到表观渗透系数(APC),该系数为与氧接触量的时间的函数(cc(STP).cm)/(m2.atm.天)。得到的APC数据不是以标准渗透系数表示的稳定状态值。所产生的APC是描述在固定的时间点氧渗透的数据,尽管该系数慢慢地随着时间而改变。这些改变在用于在任何固定的时间点测量它们的值所需要的时间期间太小,以致于不能检测。根据用于PET共聚物的渗透系数的文献方法,由费克扩散第二定律,采用适宜的边界条件,以与被动阻气渗透性所描述的相同方式,进行APC的计算。
3.瓶子的二氧化碳渗透性
使用MOCON Permatran C-200 CO2 Permeation System测量瓶子的二氧化碳渗透性。测试在22℃进行。用氮气吹扫瓶子,然后在60psi(4.01MPa)的压力下用CO2加压。将瓶子放置于环境条件下3天,并且测量压力。舍弃其中压力降低至低于56psi(3.75Mpa)的瓶子,将其余的瓶子重新加压至60psi(4.01MPa)并且放置于测试室中,所述的测试室已经用氮气吹扫了至少5小时。一天后,在8小时的时间期限内,花费30分钟的时间,进行在测试室中的CO2测量。氮对于传感器的流速为100cm3/min,并且对于载气流的流速为460cm3/min。结果报告为cm3/瓶/天。
4.特性粘度(IV)
通过溶解0.2克的无定形聚合物组合物于20毫升25℃二氯乙酸中,并且使用乌氏粘度计以确定相对粘度(RV),来确定特性粘度(IV)。使用等式:IV=[(RV-1)×0.691]+0.063来将RV转换为IV。
5.颜色
用Hunter Lab ColorQuest II仪器测量坯料和瓶壁的雾度。将D65光源与CIE 1964 10℃标准观察器一起使用。将雾度限定为CIE Y漫透射率相对于CIE Y总透射率的百分比。用相同的仪器测量坯料和瓶壁的颜色,并且使用CIELAB色标报告,L*是亮度的尺度,a*是红色(+)或绿色(-)的尺度,且b*黄色(+)或蓝色(-)的尺度。
6.二甘醇(DEG)
通过在220±5℃的密封反应器中,用氢氧化铵的水溶液水解聚合物约2小时来测定聚合物DEG(二甘醇)的含量。然后,由气相色谱分析水解产物的液体部分。气相色谱仪是Hewlett Packard的FID检测器(HP5890,HP7673A)。氢氧化铵是28至30重量%的Fisher Scientific的氢氧化铵并且是试剂级的。
7.间苯二甲酸和萘二甲酸
使用带有紫外检测器的Hewlett Packard Liquid Chromatograph(HPLC),在285纳米处测量无定形聚合物中存在的间苯二甲酸和萘二甲酸的百分比。在230℃的不锈钢反应釜中,将无定形聚合物样品在稀硫酸(10ml酸于1升的去离子水中)中水解3小时。冷却后,将来自反应釜中的水溶液与三份体积的甲醇(HPLC级)和内标溶液混合。将混合溶液引入HPLC中,进行分析。
8.金属含量
用Atom Scan 16 ICP Emission Spectrograph测量磨碎聚合物样品的金属含量。通过在乙醇胺中加热而使样品溶液,并且冷却后,将蒸馏水加入,以使对苯二甲酸结晶出来。将溶液离心,并且分析上清液。通过分析样品的原子发射,与已知金属离子浓度的溶液的数据进行比较,确定聚合物样品中保留的金属的实验值。
9.坯料与瓶子的加工
在固态聚合之后,将本发明的树脂典型地在170-180℃干燥4-6小时,熔化并且挤出成为坯料。对于0.59升软饮料瓶,例如,每一坯料采用约24克的树脂。然后将坯料加热至约100-120℃,并且在约12.5的拉伸比下吹塑成为0.59升的异形瓶。拉伸比是径向上的拉伸乘以长度(轴向)方向上的拉伸。因此,如果将坯料吹成瓶子,则可以将其拉伸其长度的约2倍并且拉伸其直径的约6倍,得到12(2×6)的拉伸比。由于瓶子尺寸是固定的,可以使用不同的坯料尺寸,以得到不同的拉伸比。
10.扫描电子显微照片
通过下面的方法由压缩模塑来制备膜:在压制机中在没有压力的情况下于275℃加热3分钟,然后压力在0至300psi之间循环数次,然后在300psi下保持4分钟。将膜用冰水急冷。用刀片在膜表面上对这些膜切口,以促进脆性断裂,浸入液氮中30分钟,移出并且用手在垂直于厚度方向上断裂。用100埃金涂敷断裂表面,并且使用JEOL 840A扫描电子显微镜观察。
给出下面的实施例以举例说明本发明,但是应当理解的是,这些实施例是用于举例说明的目的,并不意欲限制本发明的范围。
实施例
制备反映典型商业配方的各种聚酯(PET)树脂。共聚单体包括作为结晶延迟剂的间苯二甲酸(或其二甲基酯)(IPA)和二甘醇(DEG),以及萘二甲酸(或其二甲基酯)(NDC),以提高可以灌装容器的温度。
首先制备IV为约0.6的无定形聚酯,然后将其固相聚合至最终的树脂IV。使用的添加剂是乙酸锰、乙酸锌、乙酸钴、三氧化锑和多磷酸。这些树脂的分析结果列于表1中。
表1
树脂号 | A | B | C | D |
方法 | TA | DMT | DMT | DMT |
IV | 0.83 | 0.82 | 0.84 | 0.81 |
IPA,重量-% | 2.5 | 3.1 | 0 | 0 |
NDC,重量-% | 0 | 0 | 5 | 5 |
DEG重量-% | 1.5 | 0.7 | 0.6 | 0.6 |
钴,ppm | 30 | 40 | 100 | 0 |
制备一系列的共聚多酯,从而含有各种量的5-磺基间苯二甲酸(SIPA),使用SIPA的酯或乙醇酸酯(gylcolate)。以标准的方式进行熔融相聚合,但是对于树脂S3,无定形树脂不进行固态聚合。在树脂S1的情况下,使用乙酸锌代替乙酸锰作为酯交换催化剂。这些树脂的分析结果列于表2中。
表2
树脂号 | S1 | S2 | S3 |
方法 | DMT | DMT | DMT |
IV | 0.84 | 0.82 | 0.56 |
SIPA,摩尔-% | 0.11 | 1.3 | 1.7 |
钴,ppm | 0 | 0 | 40 |
通过向使用75ppmZn(乙酸锌形式)、250ppmSb(三氧化锑形式)、60ppmP(多磷酸形式)和2.5重量-%IPA而制备的聚酯中迟加入2重量-%的辛酸钴,制备将用作主动氧清除用过渡金属催化剂的钴盐的母料。该材料的IV为0.35-0.40。
除非另外指明,在共混料中使用的部分芳族尼龙是Mitsubishi GasChemical,Tokyo Japan的Type6007。Type6007的数均分子量为25,900并且其在271℃和1000sec-1下的熔体粘度为280Pa.s。
除非另外指明,坯料是在Arburg注塑机上,使用24g的材料制备的,并且在Sidel SBO2拉伸吹塑机上吹塑成为0.59升的异形瓶。瓶子的侧壁厚度为约0.25mm。
实施例1
通过将聚酯树脂D或S1与钴母料和MXD6共混来研究SIPA与Co的相互作用对坯料和瓶子黄色的影响。坯料和瓶子侧壁的黄色值(b*)列于表3中(b*值越低是为负值,对应于黄色越小)。
表3
批号 树脂 Co, MXD6, SIPA, 坯料 δ1 瓶子 δ2ppm 重量 摩尔 b*-% -% |
1 D 0 0 0 11 对照 3.6 对照2 D 0 5 0 19.3 8.3 7.1 3.53 D 100 0 0 0.7 -10.3 1 -2.64 D 200 5 0 4.2 -6.8 3.5 -0.15 S1 0 0 0.11 16.3 对照 4.6 对照6 S1 0 5 0.11 17.5 1.2 5.5 0.97 S1 100 0 0.11 -0.8 -17.1 1.1 -3.58 S1 200 5 0.11 -6.6 -22.9 2 -2.6 |
1坯料相对于对照的b*差值。
2瓶子相对于对照的b*差值。
该表表明200ppm含量下,钴盐将更多地偏移由含有5重量-%MXD6的共混料造成的黄色,但是更重要的是,在0.11摩尔-%SIPA的存在下,有协同效应,并且明显的是,Co盐对于偏移黄色更加有效。
实施例2
使用树脂C作为对照,进行类似的试验,结果示于表4中。
表4
批号 | 树脂 | Co,ppm | MXD6,重量-% | SIPA,摩尔-% | 坯料b* | 瓶子b* |
9 | C | 100 | 0 | 0 | -0.1 | 1.2 |
10 | C | 200 | 5 | 0 | 3.6 | 5.7 |
11 | S1 | 200 | 5 | 0.11 | -3.5 | 3.6 |
这些坯料和瓶子侧壁的雾度列于表5中。
表5
批号 | 树脂 | Co,ppm | MXD6,重量-% | SIPA,摩尔-% | 坯料雾度,% | 瓶子雾度,% |
9 | C | 100 | 0 | 0 | 9.5 | 1.3 |
10 | C | 200 | 5 | 0 | 16.4 | 13.9 |
11 | S1 | 200 | 5 | 0.11 | 14.3 | 8.2 |
这些结果再次表明:除了离子增容剂降低含有5重量-%MXD6的瓶子侧壁的雾度外,作为降低黄色的手段,离子增容剂对钴盐的协同效应。
实施例3
进行另一试验,其中在0.11摩尔-%的恒定SIPA含量下,改变MXD6的量,并且结果列于表6中。
表6
批号 | 树脂 | Co,ppm | MXD6,重量-% | SIPA,摩尔-% | 坯料b* | 瓶子b* |
12 | C | 100 | 0 | 0 | 0.4 | 0.8 |
13 | S1 | 100 | 0 | 0.11 | -1.8 | 1.1 |
14 | C | 200 | 3 | 0 | 1.4 | 2.4 |
15 | S1 | 200 | 3 | 0.11 | -7.4 | 1.9 |
16 | C | 200 | 4 | 0 | 1.0 | 2.8 |
17 | S1 | 200 | 4 | 0.11 | -7.8 | 2.0 |
18 | C | 200 | 5 | 0 | 3.2 | 3.2 |
19 | S1 | 200 | 5 | 0.11 | -6.1 | 2.6 |
在MXD6的所有含量下,离子增容剂的结合降低了黄色。
测量瓶子侧壁的氧渗透性,并且将结果绘制于图1中。这表明:在每一种MXD6浓度下,离子增容剂降低该渗透性。令人惊奇的是,氧渗透性与MXD6浓度存在非线性关系,其中在5重量-%MXD6下具有非常低的值。
实施例4
为了更好地定义作为MXD6浓度函数的氧渗透性,使用聚酯A作为基础树脂制备一系列共混料。使用的MXD6的浓度为1、2、3、4、4.5和5重量-%,各自含有100ppm的辛酸钴。测量瓶子侧壁的氧渗透性,并且结果示于图2中。
这说明氧渗透性在4.5和5重量-%MXD6之间具有令人惊奇的降低。
实施例5
进行另一试验,其中将MXD6含量保持在5重量-%恒定,并且改变SIPA的浓度,结果列于表7中。在这些批次中,基础聚酯树脂是A,且使用SIPA聚合物S2的母料。
表7
批号 | 树脂 | Co,ppm | MXD6,重量-% | SIPA,摩尔-% | 坯料b* | 瓶子b* |
20 | A | 30 | 0 | 0 | 3.8 | 1.0 |
21 | A | 130 | 5 | 0 | 0.5 | 4.1 |
22 | A/S2 | 130 | 5 | 0.13 | -2.5 | 3.6 |
23 | A/S2 | 130 | 5 | 0.26 | -2.9 | 3.7 |
24 | A/S2 | 130 | 5 | 0.65 | -3.6 | 3.3 |
25 | S2 | 100 | 5 | 1.3 | -9.1 | 2.8 |
这些结果表明,可以将离子增容剂用作母料,以与钴以及在上面的实施例1-3中使用的共聚物一起获得黄色的协同降低。
实施例6
代替使用钠作为SIPA盐,通过使用用于共聚物S1的方法,制备使用二价锌酯的共聚多酯。由于该Zn共聚多酯比S1更黄,不能给出Na-SIPA和Zn-SIPA之间相对差值的比较。但是,作为对照,使用0.11摩尔-%SIPA(含MXD6的批次含有100ppmCo),由PET树脂A制备的瓶子侧壁的雾度比较于下表8中。
表8
批号 | MXD6,重量-% | SIPA类型 | 雾度,% |
26 | 0 | 无 | 5.5 |
27 | 5 | 无 | 14.2 |
28 | 5 | Na | 12.0 |
29 | 5 | Zn | 9.6 |
明显的是,二价离子增容剂对于降低瓶子侧壁雾度比一价离子增容剂更有效。
实施例7
制备低分子量MXD6。在氮气气氛下,将438g己二酸、428.4g间-亚二甲苯基二胺和500g去离子水的混合物装入至2-升高压釜中。将混合物搅拌15分钟,然后加热至回流30分钟。将水蒸馏掉,并且在60-90分钟的期限内,将温度升高至275℃。在挤出之前,将混合物在275℃搅拌30分钟。该聚合物在1000sec-1和271℃下的粘度为9.5Pa.s(相比较的是,对于商品6007,为280Pa.s)。
按照实施例3的程序,使用该低分子量MXD6(LMW)与商品6007相比较。结果列于表9中。
表9
批号 | 树脂 | Co,ppm | MXD6类型 | MXD6,重量-% | SIPA,摩尔-% | 坯料b* | 瓶子b* |
32 | C | 200 | 6007 | 3 | 0 | 2.0 | 2.5 |
33 | C | 200 | LMW | 3 | 0 | 3.4 | 2.1 |
34 | C | 200 | 6007 | 5 | 0 | 4.2 | 3.5 |
35 | C | 200 | LMW | 5 | 0 | 1.1 | 3.6 |
36 | S1 | 200 | 6007 | 5 | 0.11 | -6.1 | 2.6 |
37 | S1 | 200 | LMW | 5 | 0.11 | -6.6 | 2.0 |
这说明具有低分子量的MXD6比6007的颜色更好(黄色更少)。
同样测量这些批次的雾度,并且结果列于下表10中。
表10
批号 | 树脂 | Co,ppm | MXD6类型 | MXD6,重量-% | SIPA,摩尔-% | 坯料雾度,% | 瓶子雾度,% |
32 | C | 200 | 6007 | 3 | 0 | 50.3 | 10.9 |
33 | C | 200 | LMW | 3 | 0 | 48.3 | 7.7 |
34 | C | 200 | 6007 | 5 | 0 | 50.1 | 14.0 |
35 | C | 200 | LMW | 5 | 0 | 49.9 | 11.8 |
36 | S1 | 200 | 6007 | 5 | 0.11 | 49.3 | 11.1 |
37 | S1 | 200 | LMW | 5 | 0.11 | 45.4 | 7.4 |
低分子量MXD6与SIPA的结合使用显著地降低了瓶子侧壁的雾度。
实施例7
为了确定离子增容剂对MXD6域尺寸的影响,制备一系列膜并且将其断裂。将PET树脂B与含有S3SIPA共聚多酯和6007MXD6的共混物一起使用。测量域尺寸并且结果列于表11中。
表11
MXD6,重量-% | SIPA,摩尔-% | 域尺寸,μm |
10 | 0 | 0.8-1.5 |
20 | 0 | 2.2-4.5 |
20 | 1.35 | 0.2-0.5 |
10 | 0.03 | 0.5-1.5 |
10 | 0.08 | 0.5-1.5 |
10 | 0.16 | 0.2-0.5 |
这表明在低于0.2摩尔-%的低含量SIPA的情况下,将含有10重量-%MXD6的共混料的域尺寸减小至小于0.5μm。
实施例8
使用C作为基础PET树脂,S3 SIPA共聚多酯和6007 MXD6,制备一系列瓶子。测量瓶子在0%相对湿度下的被动氧渗透性,并且结果列于表12中。
表12
批号 | MXD6,重量-% | SIPA,摩尔-% | O2渗透性(cc(STP).cm)/(m2.atm.天)) |
38 | 0 | 0 | 0.180 |
39 | 2.5 | 0 | 0.181 |
40 | 2.5 | 0.3 | 0.164 |
41 | 5 | 0 | 0.138 |
42 | 5 | 0.3 | 0.131 |
43 | 5 | 0.6 | 0.145 |
44 | 10 | 0 | 0.079 |
45 | 10 | 0.3 | 0.054 |
46 | 10 | 0.6 | 0.051 |
这表明离子增容剂在给定MXD6含量改善了氧阻气性,可能是由于域尺寸的降低,如实施例7所示,域尺寸的降低增加了域的数量。
实施例9
按照实施例7的程序,制备聚酰胺,其中用间苯二甲酸代替12%的己二酸。该聚酰胺在171℃和1000sec-1下的熔体粘度为237Pa.s。将该聚酰胺在5重量-%含量下与PET树脂C和离子增容剂S3共混,得到共混料中的SIPA浓度为0.6摩尔-%。由该共混料制备瓶子,并且氧渗透速率测量为0.155(cc(STP).cm)/(m2.atm.天)。这可以与用5重量-%MXD6达到的批次43所测量的0.145的氧渗透速率相比。
实施例10
测量的由PET树脂A制备的0.5升瓶子的二氧化碳传输速率为8.6cc/瓶/天。加入5重量-%MXD6将此速率降低至4.5cc/瓶/天。
实施例11
使用上面对于辛酸钴所述的相同方法,通过使用硬脂酸钴和环烷酸钴代替辛酸钴而制备母料。使用PET基础树脂D,使用不同量的MXD6和不同浓度的辛酸钴、硬脂酸钴和环烷酸钴制备瓶子。测量瓶子壁的氧渗透性,并且将在100小时后的值(此时,该速率处于平衡状态,参见附图1)列于表13中。
表13
批号 | MXD6,重量-% | 钴盐 | Co,ppm | 氧渗透性@100小时,(cc(STP).cm)/(m2.atm.天)) |
47 | 0 | - | - | 0.150 |
48 | 1.75 | 辛酸盐 | 200 | 0.098 |
49 | 1.75 | 辛酸盐 | 400 | 0.120 |
50 | 1.75 | 硬脂酸盐 | 100 | 0.098 |
51 | 1.75 | 硬脂酸盐 | 200 | 0.122 |
52 | 3.0 | 辛酸盐 | 400 | 0.120 |
53 | 3.0 | 辛酸盐 | 60 | 0.048 |
54 | 5.0 | 辛酸盐 | 100 | 0.005 |
55 | 5.0 | 硬脂酸盐 | 30 | 0.005 |
56 | 5.0 | 硬脂酸盐 | 50 | <0.005 |
57 | 5.0 | 环烷酸盐 | 50 | <0.005 |
事实上,过量的过渡金属催化剂可以作为抗氧化剂并且提高氧渗透性,比较批次48和49,批号52和53。
尽管已经详细描述了本发明的特殊实施方案,但是应当理解本发明的范围不会相应地受到限制,并且本发明包括在后附权利要求的精神和条件之内的所有改变和改进。
Claims (30)
1.一种容器用组合物,其包含:聚酯、部分芳族聚酰胺、离子增容剂和钴盐。
2.权利要求1的组合物,其中存在的所述部分芳族聚酰胺为所述组合物的约1至约10重量%。
3.权利要求1的组合物,其中存在的所述离子增容剂为所述组合物的约0.1至约2.0摩尔-%。
4.权利要求1的组合物,其中存在的所述钴盐为所述组合物的约20至约500ppm。
5.权利要求1的组合物,其中所述部分芳族聚酰胺含有间-亚二甲苯基。
6.权利要求5的组合物,其中所述间-亚二甲苯基聚酰胺是间-亚二甲苯基己二酰二胺。
7.权利要求1的组合物,其中所述部分芳族聚酰胺选自:聚(间苯二甲酰己二胺)、聚(六亚甲基己二酰二胺-共-间苯二甲酰胺)、聚(六亚甲基己二酰二胺-共-对苯二甲酰胺)、聚(六亚甲基间苯二甲酰胺-共-对苯二甲酰胺),或它们两种或多种的混合物。
8.权利要求1的组合物,其中所述钴盐选自:乙酸钴、碳酸钴、氯化钴、氢氧化钴、环烷酸钴、油酸钴、亚油酸钴、辛酸钴、硬脂酸钴、硝酸钴、磷酸钴、硫酸钴、钴(乙二醇盐),或它们两种或多种的混合物。
9.权利要求1的组合物,其中所述离子增容剂优选为含有金属磺酸盐的共聚多酯。
10.权利要求9的组合物,其中所述磺酸盐的金属离子可以是Na+、Li+、K+、Zn++、Mn++、Ca++等。
11.权利要求10的组合物,其中所述磺酸盐基团被连接至芳族酸核或酯等价物上,所述的芳族酸核或酯等价物选自:苯、萘、二苯基、氧二苯基、磺酰基二苯基或亚甲基二苯基核。
12.权利要求11的组合物,其中所述的芳族酸核或酯等价物是磺基邻苯二甲酸、磺基对苯二甲酸、磺基间苯二甲酸、4-磺基萘-2,7-二甲酸和它们的酯。
13.权利要求12的组合物,其中所述的离子增容剂是5-钠磺基间苯二甲酸或5-锌磺基间苯二甲酸,或它们的二烷基酯如二甲基酯(SIM)和乙二醇酯(SIPEG)。
14.一种坯料或容器,其包含:聚酯、部分芳族聚酰胺、离子增容剂和钴盐的组合物。
15.权利要求14的坯料或容器,其中存在的所述部分芳族聚酰胺为所述组合物的约1至约10重量%。
16.权利要求14的坯料或容器,其中存在的所述离子增容剂为所述组合物的约0.1至约2.0摩尔-%。
17.权利要求14的坯料或容器,其中存在的所述钴盐为所述组合物的约20至约500ppm。
18.权利要求14的坯料或容器,其中所述部分芳族聚酰胺含有间-亚二甲苯基。
19.权利要求18的坯料或容器,其中所述间-亚二甲苯基聚酰胺是间-亚二甲苯基己二酰二胺。
20.权利要求14的坯料或容器,其中所述部分芳族聚酰胺选自:聚(间苯二甲酰己二胺)、聚(六亚甲基己二酰二胺-共-间苯二甲酰胺)、聚(六亚甲基己二酰二胺-共-对苯二甲酰胺)、聚(六亚甲基间苯二甲酰胺-共-对苯二甲酰胺),或它们两种或多种的混合物。
21.权利要求14的坯料或容器,其中所述钴盐选自:乙酸钴、碳酸钴、氯化钴、氢氧化钴、环烷酸钴、油酸钴、亚油酸钴、辛酸钴、硬脂酸钴、硝酸钴、磷酸钴、硫酸钴、钴(乙二醇盐),或它们两种或多种的混合物。
22.权利要求14的坯料或容器,其中所述离子增容剂优选为含有金属磺酸盐的共聚多酯。
23.权利要求22的坯料或容器,其中所述磺酸盐的金属离子可以是Na+、Li+、K+、Zn++、Mn++、Ca++等。
24.权利要求23的坯料或容器,其中所述磺酸盐基团被连接至芳族酸核或酯等价物上,所述的芳族酸核或酯等价物选自:苯、萘、二苯基、氧二苯基、磺酰基二苯基或亚甲基二苯基核。
25.权利要求24的坯料或容器,其中所述的芳族酸核或酯等价物是磺基邻苯二甲酸、磺基对苯二甲酸、磺基间苯二甲酸、4-磺基萘-2,7-二甲酸和它们的酯。
26.权利要求25的坯料或容器,其中所述的离子增容剂是5-钠磺基间苯二甲酸或5-锌磺基间苯二甲酸,或它们的二烷基酯如二甲基酯(SIM)和乙二醇酯(SIPEG)。
27.一种聚酯容器,其在氧气中100小时后的氧气渗透速率<0.01cc(STP)-cm/m2-atm-天。
28.权利要求27的容器,其包含:聚酯、部分芳族聚酰胺、离子增容剂和钴盐的组合物。
29.权利要求27的容器,其壁b*小于2.5。
30.一种聚酯容器,其二氧化碳传输速率基于0.59升瓶小于7cc/瓶/天。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US49831103P | 2003-08-26 | 2003-08-26 | |
US60/498,311 | 2003-08-26 | ||
PCT/US2004/025257 WO2005023530A1 (en) | 2003-08-26 | 2004-08-05 | Method to make single-layer pet bottles with high barrier and improved clarity |
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CN1842412A true CN1842412A (zh) | 2006-10-04 |
CN1842412B CN1842412B (zh) | 2011-09-14 |
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US (2) | US7919159B2 (zh) |
EP (1) | EP1663630B1 (zh) |
KR (1) | KR100847273B1 (zh) |
CN (1) | CN1842412B (zh) |
AT (1) | ATE450367T1 (zh) |
AU (1) | AU2004270649B2 (zh) |
BR (1) | BRPI0413600B1 (zh) |
DE (1) | DE602004024419D1 (zh) |
DK (1) | DK1663630T3 (zh) |
ES (1) | ES2335772T3 (zh) |
HR (1) | HRP20060117B1 (zh) |
LT (1) | LT5415B (zh) |
MX (1) | MXPA06002222A (zh) |
PL (1) | PL1663630T3 (zh) |
PT (1) | PT1663630E (zh) |
RU (1) | RU2324712C2 (zh) |
SI (1) | SI1663630T1 (zh) |
UA (1) | UA81055C2 (zh) |
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Cited By (3)
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CN102906191A (zh) * | 2010-06-30 | 2013-01-30 | 科莱恩色母粒(意大利)股份公司 | 氧清除塑料材料 |
TWI486394B (zh) * | 2009-06-11 | 2015-06-01 | M & G Usa Corp | 具有改良的氧反應性之聚醯胺-聚二烯摻合物 |
CN110382621A (zh) * | 2017-02-24 | 2019-10-25 | 特雷维拉控股股份有限公司 | 具有改善性能的聚对苯二甲酸乙二醇酯容器 |
Families Citing this family (46)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101048275A (zh) * | 2004-08-31 | 2007-10-03 | 因维斯塔技术有限公司 | 具有低雾度的聚酯-聚酰胺共混物 |
US7375154B2 (en) | 2004-12-06 | 2008-05-20 | Eastman Chemical Company | Polyester/polyamide blend having improved flavor retaining property and clarity |
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US9725293B2 (en) | 2005-11-29 | 2017-08-08 | Petainer Lidkoping Ab | System and method for distribution and dispensing of beverages |
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US20090234053A1 (en) | 2008-03-14 | 2009-09-17 | Zeynep Ergungor | Copper containing polyester-polyamide compositions |
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US9381709B2 (en) | 2009-05-07 | 2016-07-05 | Reliance Industries Limited | Oxygen scavenging polyester composition |
JP5832993B2 (ja) | 2009-05-07 | 2015-12-16 | リライアンス、インダストリーズ、リミテッドReliance Industries Limited | 脱酸素ポリエステル組成物 |
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EP2681225A4 (en) | 2011-03-02 | 2014-08-06 | Futurefuel Chemical Co | METALLIC SALTS OF SULFO-5-ISOPHTHALIC ACID DIALKYL ESTER AND PROCESS FOR PRODUCTION THEREOF |
ITMI20110452A1 (it) | 2011-03-22 | 2012-09-23 | Plastic Relife Srl | Film multistrato in materiale termoplastico riciclabile, contenitore comprendente tale film e relativa confezione |
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ES2434825B1 (es) | 2012-06-11 | 2014-11-07 | Nanobiomatters Research & Development, S.L. | Materiales activos basados en cerio con capacidad catalítica y procedimiento para su obtención |
EP2708574A1 (en) | 2012-09-18 | 2014-03-19 | Clariant International Ltd. | Oxygen scavenging plastic material |
US9370916B2 (en) | 2013-03-07 | 2016-06-21 | Mullinix Packages, Inc. | Poly(ethylene terephthalate)(CPET) multilayer oxygen-scavenging containers and methods of making |
US9340316B2 (en) | 2013-03-07 | 2016-05-17 | Mullinix Packages, Inc. | Poly(ethylene terephthalate)(APET) multilayer oxygen-scavenging containers and methods of making |
EP3101054B1 (en) | 2014-01-31 | 2020-04-22 | Mitsubishi Gas Chemical Company, Inc. | Method for granulating polyamide or polyamide composition |
EP2915842A1 (en) | 2014-03-08 | 2015-09-09 | Clariant International Ltd. | Oxygen scavenging composition for plastic material |
WO2016020938A1 (en) | 2014-08-05 | 2016-02-11 | Ester Industries Limited | A process for preparation of modified polyethylene terphthalate with improved barrier, mechanical and thermal properties and products thereof |
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CA2968230C (en) | 2014-11-18 | 2023-10-03 | Plastipak Packaging, Inc. | Polyaminomethylbenzyloxalamides and compositions and methods related thereto |
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US20200061957A1 (en) * | 2018-08-24 | 2020-02-27 | The Procter & Gamble Company | Microtextured substrates and laminates comprising printing and packages made from the same |
WO2020100001A1 (en) | 2018-11-12 | 2020-05-22 | Invista North America S.A R.L. | Polymer blends with improved oxygen absorption capacity |
TW202043366A (zh) * | 2019-05-29 | 2020-12-01 | 遠東新世紀股份有限公司 | 高分子組成物、其製品及製備樹脂組成物的方法 |
Family Cites Families (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5493043A (en) | 1977-12-29 | 1979-07-23 | Unitika Ltd | Resin composition and its production |
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 |
US4499262A (en) | 1984-03-09 | 1985-02-12 | Eastman Kodak Company | Process for the preparation of sulfo-modified polyesters |
US4837115A (en) | 1986-07-30 | 1989-06-06 | Toyo Seikan Kaisha, Ltd. | Thermoplastic polyester composition having improved flavor-retaining property and vessel formed therefrom |
JPS63288993A (ja) | 1987-05-20 | 1988-11-25 | Sumitomo Electric Ind Ltd | ダイヤモンドの気相合成法 |
AU611181B2 (en) * | 1987-07-27 | 1991-06-06 | Constar International Inc. | Improvements in and relating to packaging |
GB2207439B (en) | 1987-07-27 | 1992-02-12 | Metal Box Plc | Improvements in and relating to packaging |
US4957980A (en) | 1988-08-08 | 1990-09-18 | Toyo Boseki Kabushiki Kaisha | Polyester resin composition and hollow molded article thereof |
JP2663578B2 (ja) | 1988-11-17 | 1997-10-15 | 東洋紡績株式会社 | ポリエステル中空成形体 |
US20030134966A1 (en) * | 1990-01-31 | 2003-07-17 | Kim Yong Joo | Barrier compositions and articles made therefrom |
US5281360A (en) | 1990-01-31 | 1994-01-25 | American National Can Company | Barrier composition and articles made therefrom |
US6288161B1 (en) | 1990-01-31 | 2001-09-11 | Pechiney Emballage Flexible Europe | Barrier compositions and articles made therefrom |
US5300572A (en) * | 1991-06-14 | 1994-04-05 | Polyplastics Co., Ltd. | Moldable polyester resin compositions and molded articles formed of the same |
US5258233A (en) | 1992-04-02 | 1993-11-02 | Eastman Kodak Company | Polyester/polyamide blend having improved flavor retaining property and clarity |
US5266413A (en) | 1992-05-18 | 1993-11-30 | Eastman Kodak Company | Copolyester/polyamide blend having improved flavor retaining property and clarity |
US5623047A (en) | 1995-03-28 | 1997-04-22 | Industrial Technology Research Institute | Catalytic compositions for the preparation of poly(ethylene terephthalate) with improved color |
US5650469A (en) | 1995-10-25 | 1997-07-22 | Eastman Chemical Company | Polyester/polyamide blend having improved flavor retaining property and clarity |
US6083585A (en) * | 1996-09-23 | 2000-07-04 | Bp Amoco Corporation | Oxygen scavenging condensation copolymers for bottles and packaging articles |
IT1301690B1 (it) | 1998-06-11 | 2000-07-07 | Sinco Ricerche Spa | Miscele di resine poliestere aventi elevate proprieta' di barriera aigas. |
US6239233B1 (en) | 1998-10-09 | 2001-05-29 | Eastman Chemical Company | Polyester/polyamide blends with improved color |
AU6505000A (en) | 1999-07-30 | 2001-02-19 | Eastman Chemical Company | Polyester-polyamide blends with reduced gas permeability and low haze |
US6525123B1 (en) * | 2000-05-19 | 2003-02-25 | Chevron Phillips Chemical Company Lp | Compatible blend systems from ethylene vinyl alcohol and oxygen scavenging polymers |
US6508463B1 (en) * | 2000-10-26 | 2003-01-21 | Pitney Bowes Inc. | Method and apparatus for staging envelopes |
US6933055B2 (en) * | 2000-11-08 | 2005-08-23 | Valspar Sourcing, Inc. | Multilayered package with barrier properties |
US20040013833A1 (en) * | 2002-03-21 | 2004-01-22 | Lee Robert A. | Compatibilized polyester/polyamide blends |
-
2004
- 2004-05-08 UA UAA200602010A patent/UA81055C2/uk unknown
- 2004-08-05 DK DK04780147.7T patent/DK1663630T3/da active
- 2004-08-05 KR KR1020067003993A patent/KR100847273B1/ko not_active IP Right Cessation
- 2004-08-05 AT AT04780147T patent/ATE450367T1/de active
- 2004-08-05 PT PT04780147T patent/PT1663630E/pt unknown
- 2004-08-05 SI SI200431299T patent/SI1663630T1/sl unknown
- 2004-08-05 MX MXPA06002222A patent/MXPA06002222A/es active IP Right Grant
- 2004-08-05 AU AU2004270649A patent/AU2004270649B2/en not_active Ceased
- 2004-08-05 BR BRPI0413600A patent/BRPI0413600B1/pt not_active IP Right Cessation
- 2004-08-05 PL PL04780147T patent/PL1663630T3/pl unknown
- 2004-08-05 ES ES04780147T patent/ES2335772T3/es active Active
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- 2004-08-05 RU RU2006105756/04A patent/RU2324712C2/ru not_active IP Right Cessation
- 2004-08-05 WO PCT/US2004/025257 patent/WO2005023530A1/en active IP Right Grant
- 2004-08-05 US US10/569,614 patent/US7919159B2/en not_active Expired - Fee Related
- 2004-08-05 CN CN2004800244759A patent/CN1842412B/zh not_active Expired - Fee Related
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI486394B (zh) * | 2009-06-11 | 2015-06-01 | M & G Usa Corp | 具有改良的氧反應性之聚醯胺-聚二烯摻合物 |
CN102906191A (zh) * | 2010-06-30 | 2013-01-30 | 科莱恩色母粒(意大利)股份公司 | 氧清除塑料材料 |
CN102906191B (zh) * | 2010-06-30 | 2014-06-18 | 科莱恩色母粒(意大利)股份公司 | 氧清除塑料材料 |
CN103951948A (zh) * | 2010-06-30 | 2014-07-30 | 科莱恩色母粒(意大利)股份公司 | 氧清除塑料材料 |
CN103951948B (zh) * | 2010-06-30 | 2016-08-31 | 科莱恩色母粒(意大利)股份公司 | 氧清除塑料材料 |
CN110382621A (zh) * | 2017-02-24 | 2019-10-25 | 特雷维拉控股股份有限公司 | 具有改善性能的聚对苯二甲酸乙二醇酯容器 |
TWI770126B (zh) * | 2017-02-24 | 2022-07-11 | 德商翠維拉控股有限公司 | 具改良性能的聚對苯二甲酸乙二酯容器及增大容器之爆裂壓力之方法 |
Also Published As
Publication number | Publication date |
---|---|
ATE450367T1 (de) | 2009-12-15 |
KR100847273B1 (ko) | 2008-07-21 |
BRPI0413600B1 (pt) | 2016-02-16 |
SI1663630T1 (sl) | 2010-04-30 |
ZA200601383B (en) | 2007-04-25 |
EP1663630A4 (en) | 2007-07-11 |
RU2324712C2 (ru) | 2008-05-20 |
EP1663630B1 (en) | 2009-12-02 |
EP1663630A1 (en) | 2006-06-07 |
AU2004270649B2 (en) | 2007-04-26 |
DE602004024419D1 (de) | 2010-01-14 |
AU2004270649A1 (en) | 2005-03-17 |
US7943216B2 (en) | 2011-05-17 |
RU2006105756A (ru) | 2006-08-27 |
US20100209641A1 (en) | 2010-08-19 |
BRPI0413600A (pt) | 2006-10-17 |
HRP20060117A2 (en) | 2006-05-31 |
HRP20060117B1 (hr) | 2015-02-13 |
UA81055C2 (uk) | 2007-11-26 |
US20060246245A1 (en) | 2006-11-02 |
LT2006015A (en) | 2007-01-25 |
US7919159B2 (en) | 2011-04-05 |
PT1663630E (pt) | 2010-02-03 |
CN1842412B (zh) | 2011-09-14 |
DK1663630T3 (da) | 2010-04-12 |
LT5415B (lt) | 2007-04-25 |
MXPA06002222A (es) | 2006-05-22 |
KR20070029619A (ko) | 2007-03-14 |
ES2335772T3 (es) | 2010-04-05 |
WO2005023530A1 (en) | 2005-03-17 |
PL1663630T3 (pl) | 2010-04-30 |
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