CN1659008A - 耐热聚酯容器及其制造方法 - Google Patents
耐热聚酯容器及其制造方法 Download PDFInfo
- Publication number
- CN1659008A CN1659008A CN038131226A CN03813122A CN1659008A CN 1659008 A CN1659008 A CN 1659008A CN 038131226 A CN038131226 A CN 038131226A CN 03813122 A CN03813122 A CN 03813122A CN 1659008 A CN1659008 A CN 1659008A
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- Prior art keywords
- polyester container
- heat
- formed products
- temperature
- container
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Links
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Images
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Abstract
本发明提供一种,具有优异的耐热性,在进行食品、饮料等的填充和密封后能够进行蒸馏杀菌处理,即使经过所述蒸馏杀菌处理,容器的器身也不会发生变形的具有很高的耐热性的聚酯容器及其制造方法。根据本发明,可提供一种耐热聚酯容器,其特征是,作为聚酯容器,该聚酯容器的器身处的以公式收缩率(%)=(收缩量/标距)×100(1)表达的收缩率达到0.66%时的温度为120℃以上,式中,收缩量,是对从聚酯容器的器身上切下的、具有20mm的标距的试片,在不施加预载荷、从30℃起的升温速率为3℃/min的条件下,采用TMA法测得的。
Description
技术领域
本发明涉及对聚对苯二甲酸乙二醇酯等聚酯树脂制成的预塑形坯进行双向拉伸吹塑成形而得到的耐热聚酯容器及其制造方法,特别是涉及进行内容物的填充和密封后要进行蒸馏杀菌的聚酯容器。
背景技术
在将聚对苯二甲酸乙二醇酯等聚酯树脂制成的预塑形坯加热至玻化温度(Tg)以上、热结晶化温度以下的温度后,对其进行双向拉伸吹塑成形而制成的广口瓶或酒瓶形状的容器,具有很好的透明性、抗冲击性、气体阻隔性,作为各种食品、调味品、饮料的容器得到广泛应用。
一般来说,为了使聚酯容器具有耐热性,要对聚酯树脂制成的预塑形坯的口部适当进行加热使之结晶化,通过双向拉伸吹塑成形使之结晶化,进而,为了消除因进行上述双向拉伸吹塑成形而产生的应变,要在结晶化温度以上的温度下进行热定形,但是,若所得到的聚酯容器放置在70℃以上的温度下,则会由于热收缩而发生很大的变形。
此外,为了使聚酯容器具有更高的耐热性,有人提出这样一种方法,即,对聚酯树脂制成的预塑形坯的口部进行适当加热使之结晶化,以一次吹塑模具对所述预塑形坯进行双向拉伸吹塑成形而制成一次中间成形品,在热缩烘箱内充分加热使之高度结晶化而制成二次中间成形品,再以二次吹塑模具对该二次中间成形品进行双向拉伸吹塑成形加工(例如特公平7-67732号)。
这种方法,是对通过一次吹塑成形进行了双向拉伸吹塑成形的一次中间成形品进行加热使之强制性收缩而成形为二次中间成形品,再进行吹塑成形而使该二次中间成形品几乎不发生拉伸变形地变成瓶状的。
但是,对于耐热聚酯容器的器身,为了防止因杀菌时受热而膨胀、或者因杀菌后减压而变形,需要制成具有减压吸收面(镜面部)等的减压吸收结构、具有增强环、增强筋等的增强结构,而按照前述特公平7-67732号所记载的、将二次中间成形品使之几乎不发生拉伸变形地吹塑成形为酒瓶形状的方法,不可能在聚酯容器的器身上形成所述减压吸收面和增强环等。
特别是,对于以婴儿食品等食品、放牛奶咖啡等饮料为内容物,填充后必须在100℃以上、特别是在120℃下进行20至50分钟高温蒸馏杀菌的聚酯容器来说,也无法形成减压吸收面、增强环等。
此外,在上述方法中,二次中间成形品与最终成品容器大小相同或大体相同,因此,存在着在以二次模具对二次中间成形品进行双向拉伸吹塑成形时,容易发生二次吹塑模具钳夹二次中间成形品的表面的所谓模具钳夹等问题。
另一方面,本申请人曾提出这样一种聚酯容器及其制造方法,即,着眼于聚酯容器在进行前述高温蒸馏杀菌时底部发生变形、白化等现象,使得至少容器的底部在DSC曲线上的150℃以上、熔融起始点以下处具有峰值(特开2001-150522号);但是这种方法也同样存在着蒸馏杀菌时器身发生变形的问题有待解决。
发明的公开
本发明的目的是,提供一种,具有优异的耐热性,在进行食品、饮料等的填充和密封后能够进行蒸馏杀菌处理,即使经过所述蒸馏杀菌处理,容器的器身也不会发生变形的具有很高的耐热性的聚酯容器及其制造方法。
根据本发明,可提供一种耐热聚酯容器,其特征是,作为聚酯容器,该聚酯容器的器身处的以下面的公式(1)表达的收缩率达到0.66%时的温度为120℃以上,
收缩率(%)=(收缩量/标距)×100……(1)
式中,收缩量,是对从聚酯容器的器身上切下的、具有20mm的标距的试片,在不施加预载荷、从30℃起的升温速率为3℃/min的条件下,采用TMA法测得的。
作为本发明的聚酯容器,最好是,器身上具有减压吸收面,所述收缩量和温度T,是该减压吸收面之间的柱部处的值。
根据本发明,还能够提供一种耐热聚酯容器的制造方法,其特征是,对聚酯树脂制成的预塑形坯以一次模具进行双向拉伸吹塑成形制成一次中间成形品,在对所述一次中间成形品进行加热使之收缩成为二次中间成形品后,在对所述二次中间成形品以加热至150至210℃的二次模具,进行可使以下面的公式(2)表达的器身的厚度减少率达到5%以上的双向拉伸吹塑成形的同时进行热定形,
厚度减少率(%)={(t1-t2)/t2}×100……(2)
式中,t1是二次中间成形品的器身的壁厚,t2是作为最终成形品的聚酯容器的器身的壁厚。
作为本发明的聚酯容器的制造方法,最好是,所得到的聚酯容器在其器身上具有减压吸收面,所述厚度减少率,是器身上所形成的减压吸收面之间的柱部处的值。
在本发明的耐热聚酯容器中,所述收缩率和温度T是这样定义的,即,对经过热收缩的二次中间成形品以二次模具进行双向拉伸吹塑成形的同时进行热定形而得到聚酯容器,从该聚酯容器的器身上切下如图4所示标距为20mm的试片,在不施加预载荷、从30℃起的升温速率为3℃/min的条件下,对该试片进行热机械检测(thermomechanical analysis,简称为TMA),在检测结果(图5)中,符合上述公式(1)的收缩率和收缩0.66%时的温度便是所述收缩率和温度T。
特别是,所述收缩率及收缩0.66%时的温度T,最好是器身上所形成的减压吸收面之间的柱部处的值。由于该减压吸收面之间的柱部,是与减压吸收面相比耐热性较差的部位,因此,对该部位进行检测,可使得本发明的耐热聚酯容器的优越性明显地显现出来。
若所述收缩率为0.66%时的温度T为120℃以上,则可使聚酯容器的容积收缩率较小,比如说可抑制在2%以下。即,当所述收缩率为0.66%时的温度T为120℃以上时,热收缩后的二次中间成形品的器身,在二次吹塑成形时可被二次模具充分双向拉伸,并且得到热定形,与现有的聚酯容器相比,耐热性大幅度提高。因此,在向容器内填充婴儿食品等食品、加牛奶咖啡等饮料后,能够在100℃以上、特别是120℃这一高温下进行20至50分钟的蒸馏杀菌处理。
相对于此,若所述收缩率为0.66%时的温度T不足120℃,则耐热性差,难以完全经受如上所述的高温下的蒸馏杀菌处理。
另外,之所以将收缩率以0.66%作为基准,是由于对于耐热聚酯容器来说,作为可供实用的容器其发生最大收缩时的收缩率为0.66%左右,显然,即使在高于高温蒸馏杀菌温度120℃的温度下,只要收缩率低于该收缩率便具有优异的耐热性。
此外,在本发明的耐热聚酯容器的制造方法中,若所述器身的厚度减少率不足5%,则所得到的聚酯容器在上述收缩率为0.66%时的温度T将不足120℃,耐热性变差,而且,在进行如上所述的吹塑成形时,会发生褶皱等成形不良现象;若超过30%,则会出现二次吹塑成形时发生破裂或取出后变形等问题。
此外,就上述厚度减少率而言,最好是,聚酯容器的器身的壁厚t2,是器身上所形成的减压吸收面之间的柱部处的值。使得该减压吸收面之间的柱部的壁厚比减压吸收面厚,并对该部位进行检测,便能够使本发明的耐热聚酯容器的制造方法的优越性更为明显地显现出来。
附图的简要说明
图1是本发明耐热聚酯容器的一个例子的侧视图。
图2是本发明耐热聚酯容器的另一个例子的侧视图。
图3是对本发明的耐热聚酯容器制造方法进行说明的附图。
图4是以TMA法测定收缩率时所使用的试片的附图。
图5是展示TMA法检测结果的TMA曲线图。
发明的最佳实施形式
[聚酯容器]
本发明的耐热聚酯容器,其特征是,器身处的以上述公式(1)表达的收缩率为0.66%时的温度T为120℃以上。
本发明的耐热聚酯容器,并不限于此,也可以做成图1所示的广口型瓶状容器,或图2所示的酒瓶状容器。
图1所示的广口的聚酯容器1,由广口口部2、肩部3、器身4以及底部5构成,所述器身上形成有减压吸收面6。是一种口部2经过热处理已结晶化,肩部3、器身4和底部5经过后述的二次模具热定形而成的聚酯容器,所述器身4的减压吸收面6之间的柱部7的收缩率为0.66%时的温度T为120℃以上。
而图2所示的本发明聚酯容器21呈酒瓶状,由口部22、肩部23、上器身24a、下器身24b以及底部25构成,在所述下器身24b上,形成有减压吸收面26和柱部27,而在所述上器身24a和下器身24b的衔接部位,形成有下凹增强环28。图2所示的容器也同样,减压吸收面26之间的柱部27处的、收缩率为0.66%时的温度T为120℃以上。
作为构成本发明聚酯容器的材料,只要是能够进行双向拉伸吹塑成形以及能够结晶化的聚酯树脂可任意选用,可以使用对苯二甲酸乙二醇类热塑性聚酯、聚对苯二甲酸丁二醇酯(ポリブチレンテレフタレ-ト)、ボリエチレンナフタレ一ト等聚酯,也可以使用这些聚酯与聚烯烃、聚碳酸酯或ァリレ一ト树脂等的混合物。本发明的聚酯容器所使用的对苯二甲酸乙二醇类热塑性聚酯,最好是,其酯重复单位的大部分即70摩尔%以上、特别是80摩尔%以上为对苯二甲酸乙二醇酯单位,玻化温度(Tg)为50至90℃、特别是55至80℃,融点(Tm)为200至275℃、特别是220至270℃的热塑性聚酯树脂。
作为这样的热塑性聚酯树脂,就耐热性而言,以均聚对苯二甲酸乙二醇酯为宜,但也可以使用还含有少量对苯二甲酸乙二醇酯单位之外的酯单位的共聚物聚酯。
作为对苯二甲酸之外的二元酸,可列举出间苯二甲酸、邻苯二甲酸、萘二甲酸等芳香族三羧酸;环巳酮三羧酸等脂环族三羧酸;丁二酸、巳二酸、癸二酸、ドデカンゾオン酸等脂族三羧酸的一种或两种以上的组合。
此外,作为乙二醇之外的二醇成分,可列举出丙二醇、1,4-丁二醇、二甘醇、1,6-巳二醇、环巳烷二甲醇、双酚A的环氧乙烷加合物等的一种或两种以上。
此外,也可以使用,在对苯二甲酸乙二醇类热塑性聚酯中,混合5至25%左右玻化温度较高的、例如ボリエチレンナフタレ—ト、聚碳酸酯、或聚芳酯而成的复合材料,这样做还能够提高高温下的材料强度。另外,还可以将聚对苯二甲酸乙二醇酯与上述玻化温度较高的材料层叠起来使用。此外,还可以根据需要,在上述聚酯树脂中混合光滑剂、改性剂、颜料、紫外线吸收剂等。
本发明中所使用的对苯二甲酸乙二醇类热塑性聚酯,应至少具有足以形成薄膜的分子量,根据用途可使用注塑类或挤出类材料。其固有粘度(IV),一般应为0.6至1.4dl/g,尤以0.63至1.3dl/g的范围为佳。
本发明的聚酯容器,既可以由单层的前述聚酯树脂构成,也可以制作成,在构成内外层的聚酯树脂层的中间形成有气体阻隔层的多层结构。
作为构成气体阻隔层的热塑性树脂,例如可列举出,乙烯-乙烯醇共聚物、聚酰胺、聚偏二氯乙烯类树脂、聚乙烯醇、含氟树脂等。
作为更理想的气体阻隔树脂,可列举出,乙烯含有量为20至60摩尔%、特别是25至50摩尔%的乙烯-醋酸乙烯共聚物,经过皂化其皂化度达到96摩尔%以上、特别是99摩尔%以上而得到的乙烯-醋酸乙烯共聚物之皂化物。
作为其它理想的气体阻隔树脂,可列举出,相对于每100个数量的碳,酰胺基的数量在5至50个、特别是6至20个的范围内的聚酰胺类;例如尼龙6、尼龙6,6、尼龙6/6,6共聚物、间二甲苯己二酰二胺(メタキシリレンァゾパミド)(MXD6)、尼龙6,10、尼龙11、尼龙12、尼龙13等。
在以聚酯树脂形成的单层构成本发明的聚酯容器的场合,也可以向聚酯树脂中混合可氧化有机成分以及钴等过渡性金属催化剂,利用过渡性金属催化剂对可氧化有机成分进行氧化的作用而使之具有捕获氧的功能。作为可氧化有机成分,可列举出聚酰胺、特别是含有苯二甲基的聚酰胺。
此外,对于如前所述聚酯树脂分为内外层、中间具有气体阻隔层的多层结构来说,构成气体阻隔层的树脂本身也可以采用具有可吸收氧的性能的材料,赋予气体阻隔层以可吸收氧的性能。作为这种树脂,可列举出例如利用树脂的氧化反应的树脂,可以采用在聚丁二烯、聚异戊二烯、聚丙烯、乙烯·氧化碳共聚物等酸性有机材料,以及,在6-尼龙、12-尼龙、メタキシリレンジァミン(MX)尼龙那样的聚酰胺类中,添加作为氧化催化剂含有钴、铑、铜等过渡性金属的有机酸盐类,或ベンゾフエン、ァセトヮエン、クロロケトン类那样的光增感剂而成的材料。在使用上述氧化吸氧材料的场合,通过照射紫外线、电子射线等高能射线,还能够获得更好的效果。
此外,还可以使构成气体阻隔层的前述气体阻隔性树脂中含有可氧化的有机成分,从而能够使气体阻隔层在不会因氧化老化而降低气体阻隔性的情况下获得可吸收氧的性能。作为这种氧化有机成分,最好是从多烯烃中衍生的多烯烃聚合物,最好是向其中引入羧酸、羧酸酐基、氢氧基。作为上述官能团,可列举出丙烯酸、甲基丙烯酸、马来酸、不饱和羧酸、无水马来酸、不饱和羧酸的酐等,而作为过渡性金属催化剂以钴为宜。
此外,还可列举出以,在构成气体阻隔层的前述气体阻隔性树脂中混合具有还原性的金属粉例如还原性铁粉、还原性锌、还原性锡粉、金属低位氧化物、还原性金属化合物的一种或两种以上而成的材料,为主成分的材料等,根据需要,还可以将它们与碱金属、碱土金属的氢氧化物、碳酸盐、亚硫酸盐、有机酸盐、卤化物、还有活性炭、活性铝那样的添加剂组合起来使用。还可以列举出结构内具有多价苯酚的高分子化合物,例如含有多价苯酚的酚醛树脂等。为了保证透明或半透明,这些氧吸收剂的平均颗粒直径一般应在10μm以下,尤以5μm以下为宜。
在前述气体阻隔层树脂、氧吸收性树脂、氧吸收材料中,可以混合填充剂、着色剂、热稳定剂、气候稳定剂、防氧化剂、防老化剂、光稳定剂、紫外线吸收剂、防静电剂、金属皂或蜡等光滑剂、改性剂。
再有,在制作所述多层结构时,还可以根据需要使各树脂层之间具有粘接剂或粘接剂层。
[聚酯容器的制造方法]
如前所述,本发明的耐热聚酯容器的制造方法,其特征是,对聚酯树脂制成的预塑形坯以一次模具进行双向拉伸吹塑成形制成一次中间成形品,在对所述一次中间成形品进行加热使之收缩成为二次中间成形品后,在对所述二次中间成形品以加热至150至210℃的二次模具,进行可使以前述式(2)表达的器身的厚度减少率达到5%以上的双向拉伸吹塑成形的同时进行热定形。
图3是对图1所示本发明的耐热聚酯容器的制造方法进行说明的附图,也就是说,如图3所示,本发明的耐热聚酯容器1可这样得到,即,通过适当的加热手段使聚酯树脂制成的预塑形坯10的口部结晶化而使所述口部获得耐热性,将所述预塑形坯加热至玻化温度(Tg)以上的温度、例如95至115℃,以一次模具进行双向拉伸吹塑成形制成一次中间成形品11(一次吹塑工序),对所述一次中间成形品11进行加热使之热收缩,从而得到进行所述双向拉伸吹塑成形时所产生的应变得以消除的二次中间成形品12(加热收缩工序),之后,对所述二次中间成形品12,以加热至150至210℃的二次模具,进行使以前述公式(2)表达的器身的厚度较少率达到5%以上、最好是5至30%的双向拉伸吹塑成形的同时进行热定形(二次吹塑·热定形工序)。在图3所示的具体例子中,最好是,器身上形成有减压吸收面6以及柱部7,以前述公式(2)表达的厚度较少率是柱部7处的值。
作为上述一次吹塑工序中一次模具的温度,在与通过成形而得到的一次中间成形品的器身和底部相对应部分的温度相同的场合,最好是室温至250℃之间的温度,若模具温度超过250℃,会导致材料熔融,分模不良。
而为了使从颈部到器身的收缩稳定,最好是,一次模具部分的与通过成形而得到的一次中间成形品的器身和底部相对应部分的温度不同。在这种场合,与器身相对应的部分的温度最好是在70℃至250℃的范围内,若不足70℃,则由于加热不充分而无法获得足够的收缩稳定性,若超过250℃,则会导致材料熔融,分模不良。另一方面,与底部相对应的部分的温度最好是在室温至250℃的范围内,若超过250℃,则会导致材料熔融,分模不良。
此外,一次吹塑工序中的拉伸倍率,一般来说最好是,纵向在1.5至5倍、横向在1至4倍、面积倍率在3至20倍的范围内,特别是对于图1所示的广口聚酯容器,最好是纵向在2至4倍、横向在至3.5倍、面积倍率在4至20倍的范围内,对于图3所示的酒瓶状聚酯容器,最好是纵向在2.5至4倍、横向在1至4倍、面积倍率在4至13倍的范围内。
此外,作为上述加热收缩工序中的加热条件,最好是,将表面的平均温度控制在100℃至250℃,若平均温度不足100℃,则以二次模具进行拉伸吹塑时无法充分成形,若超过250℃,则会导致材料熔融,二次吹塑时发生破裂,因热结晶化而白化。
而作为上述二次吹塑·热定形工序中二次模具的温度,最好是,与所成形的二次中间成形品的器身和底部相对应部分的温度分别为150℃至210℃,若不足150℃,则无法充分减小成形应力,因而无法获得所希望的耐热性,若超过210℃,则会导致分模不良,取出时发生变形或造成外观不良。
此外,在必要时,为了防止从二次模具中取出聚酯容器时发生变形,要以20至25℃的空气进行0.5秒至3秒的冷却性吹塑。
此外,作为二次吹塑工序中的拉伸倍率,一般来说最好是,纵向在1至1.2倍、横向在1.05至1.3倍、面积倍率在1.05至1.3倍的范围内,特别是对于图1所示的广口聚酯容器,最好是,纵向在1至1.1倍、横向在1.05至1.2倍、面积倍率在1.05至1.15倍的范围内,对于图3所示的酒瓶状聚酯容器,最好是,纵向在1至1.1倍、横向在1.05至1.25倍、面积倍率在1.05至1.2倍的范围内。
此外,二次吹塑模具中的热定形,一般来说最好是在1至5秒的范围内。
关于在对聚酯树脂制成的预塑形坯以一次模具进行双向拉伸吹塑成形、通过热处理使之热收缩、以二次模具进行双向拉伸吹塑成形时对所述一次模具、加热处理时的热收缩、二次模具进行的温度控制,已经有多种方案,而在本发明中,为了制造出,即使在填充婴儿食品等食品、放牛奶咖啡等饮料后以100℃以上、特别是120℃这一高温进行20至50分钟的蒸馏杀菌处理,器身也不会变形的高耐热聚酯容器,尤其需要对上述一次吹塑工序以及二次吹塑工序中的拉伸倍率、以及热缩内的加热收缩时间进行调整,以使得对经过了热收缩的二次中间成形品以二次模具进行双向拉伸吹塑成形的同时进行热定形时,能够使以前述公式(2)表达的厚度较少率达到5%以上、最好是达到5%至30%。
在本发明的聚酯容器的制造方法中,是使用现有的公知注塑成形机制作出与注塑用预塑形坯模具的形状相对应的预塑形坯的。
此外,在制成多层结构的场合,也可以使用共注注塑成形机,内外层以聚酯树脂制造,在内外层之间插入至少一层或者更多层的中间层,制作出与注塑用预塑形坯模具的形状相对应的预塑形坯。此外,也可以使用多级注塑机,首先以一次模具注塑出由聚酯树脂构成的一次预塑形坯,然后将所述一次预塑形坯移放到二次模具中,在其表面注塑用来构成中间层的树脂制作出二次预塑形坯,再将所述二次预塑形坯移放到三次模具中在其表面注塑聚酯树脂而形成外层,从而制作出多层预塑形坯。
此外,也可以采用压缩成形方法制造预塑形坯,在这种场合,可将熔融树脂块在实质上温度不降低的情况下向阴模供给并以阳模进行压缩成形。而为多层结构时,可在构成内外层的熔融树脂块中设置中间层树脂,将该熔融树脂块在实质上温度不降低的情况下向阴模供给并以阳模进行压缩成形。
为了使如上获得的预塑形坯的口颈部具有耐热性,可在预塑形坯阶段对所述口颈部进行热处理使之结晶化而白化。
也可以在双向拉伸吹塑成形之后使双向拉伸部分的口颈部结晶化而白化。
实施例
[实施例1]
在以适当的手段使聚对苯二甲酸乙二醇酯树脂制成的预塑形坯的口部结晶化(白化)之后,将预塑形坯加热至玻化温度以上的115℃,以与器身以及底部相对应的部分均被加热至160℃的一次模具,进行拉伸倍率为纵向2.8倍、横向2.8倍、面积7.8倍的双向拉伸吹塑成形,制作出比最终成品的聚酯容器大的、器身直径100mm、高度100mm的横截面形状为圆形的一次中间成形品。
其次,对上述一次中间成形品进行烘箱加热,加热到其表面温度平均为180℃而使之热收缩,制作出器身壁厚(t1)0.5mm(颈部之下45mm处)、器身直径65mm、高度90mm的横截面形状为圆形的二次中间成形品。
继而,对该二次中间成形品,以至少与器身4相对应的部分的温度为150℃的二次模具,进行纵向1.01倍、横向1.04倍、面积1.05倍的双向拉伸吹塑成形,对除了口部2之外的肩部3、器身以及底部进行3秒的热定形,制作出具有减压吸收面6、所述减压吸收面6之间的柱部7的壁厚(t2)0.45mm(颈部之下45mm处)(厚度减少率=(t1-t2)/t2×100=5%)、器身直径70mm、高度95mm的如图1所示的广口耐热聚酯容器。
并且,在从二次模具中将聚酯容器取出时,对容器内部以25℃的空气进行1秒吹塑的冷却性吹塑。
[实施例2]
制作出与实施例1相比,除了二次模具的温度为160℃以及进行双向拉伸吹塑成形时的拉伸倍率为纵向1.1倍、横向1.18倍、面积1.3倍不同之外,其它与实施例1相同的聚酯容器。
[实施例3]
在以适当的手段使聚对苯二甲酸乙二醇酯树脂制成的预塑形坯的口部结晶化(白化)之后,将预塑形坯加热至玻化温度以上的105℃,以与器身相对应的部分被加热至130℃、与底部相对应的部分均被加热至90℃的一次模具,进行拉伸倍率为纵向2.8倍、横向3.5倍、面积9.8倍的双向拉伸吹塑成形,制作出比最终成品聚酯容器大的、器身直径85mm、高度210mm的横截面形状为圆形的一次中间成形品。
其次,对上述一次中间成形品进行烘箱加热,加热到其表面温度平均为180℃而使之热收缩,制作出器身壁厚(t1)0.48mm(颈部之下80mm处)、器身直径56mm、高度158mm的横截面形状为圆形的二次中间成形品。
继而,对该二次中间成形品,以至少与器身24a、24b相对应的部分的温度为180℃的二次模具,进行纵向1.03倍、横向1.17倍、面积1.2倍的双向拉伸吹塑成形,对除了口部22之外的肩部23、器身24以及底部25进行2秒的热定形,制作出具有减压吸收面26、所述减压吸收面26之间的柱部27的壁厚(t2)0.38mm(颈部之下80mm处)(厚度减少率=(t1-t2)/t2×100=20%)、器身直径70mm、高度165mm的如图3所示的酒瓶状耐热聚酯容器。
并且,在从二次模具中将聚酯容器取出时,进行对容器内部以25℃的空气进行0.8秒吹塑的冷却性吹塑。
[实施例4]
制作出与实施例3相比,除了二次模具的温度为210℃以及进行双向拉伸吹塑成形时的拉伸倍率为纵向1.1倍、横向1.09倍、面积1.1倍不同之外,其它与实施例3相同的聚酯容器。
[对比例1]
制作出与实施例1相比,除了二次模具的温度为130℃以及进行双向拉伸吹塑成形时的拉伸倍率为纵向1倍、横向1.02倍、面积1.02倍不同之外,其它与实施例1相同的聚酯容器。
[对比例2]
制作出与实施例3相比,除了二次模具的温度为140℃以及进行双向拉伸吹塑成形时的拉伸倍率为纵向1.01倍、横向1.02倍、面积1.03倍不同之外,其它与实施例1相同的聚酯容器。
(评价)
[收缩率]
从聚酯容器的器身上的减压吸收面之间的柱部切出标距20mm、宽度3mm的图4所示的试片,进行了TMA检测。
作为检测设备使用的是动态粘弹性检测装置(Seiko Instruments Inc,DMS-6100),对试片的预加载荷为0(N),在3℃/min的升温条件下进行TMA检测。
如图5所示,以X轴为试片温度(℃),以Y轴为试片收缩率,30℃时的收缩率为0%,从收缩量/标距求取收缩率,确认所述收缩率为0.66%时的温度T。
其结果示于表1中。
[耐热性]
在25℃下向聚酯容器填充加牛奶咖啡,以聚丙烯制成的塑料螺纹盖密封后,在120℃下进行30分钟蒸馏杀菌时容器的收缩率示于表1中。
产业上利用的可能性
本发明的耐热聚酯容器,具有非常好的耐热性,可以在食品、饮料等的填充和密封后在高温下进行蒸馏杀菌处理,尤其适用于,以婴儿食品等食品、放牛奶咖啡等饮料为内容物,填充后需要在100℃以上特别是120℃这一高温下进行20至50分钟蒸馏杀菌的内容物。
此外,根据本发明的耐热聚酯容器的制造方法,能够很容易地制作出与现有的聚酯容器相比,耐热性大幅度提高的聚酯容器。
表1
二次模具的温度(℃) | 二次模具的拉伸倍率(纵×横×=面积) | 壁厚减少率(%) | 评 价 | |||
收缩率为0.66%时的温度T(℃) | 耐热性(容积收缩率%) | 成形性(减压吸收面、柱部等) | ||||
实施例1 | 150℃ | 1.01×1.04=1.05 | 5% | 128.1 | 1.8 | 良好 |
实施例2 | 160℃ | 1.1×1.18=1.3 | 30% | 123.7 | 2 | 良好 |
实施例3 | 180℃ | 1.03×1.17=1.2 | 20% | 150.3 | 1.5 | 良好 |
实施例4 | 210℃ | 1.01×1.09=1.1 | 10% | 201.8 | 0.8 | 良好 |
比较例1 | 130℃ | 1×1.02=1.02 | 2% | 102.3 | 9.6 | 发生减压吸收面成形不良以及模具钳夹等现象 |
比较例2 | 140℃ | 1.01×1.02=1.03 | 3% | 116.8 | 3.9 | 发生减压吸收面成形不良以及模具钳夹等现象 |
Claims (4)
1.一种耐热聚酯容器,其特征是,
作为聚酯容器,该聚酯容器的器身处的以下面的公式(1)表达的收缩率达到0.66%时的温度T为120℃以上,
收缩率(%)=(收缩量/标距)×100……(1)
式中,收缩量,是对从聚酯容器的器身上切下的、具有20mm的标距的试片,在不施加预载荷、从30℃起的升温速率为3℃/min的条件下,采用TMA法测得的。
2.如权利要求1所述耐热聚酯容器,其特征是,所述聚酯容器在其器身上具有减压吸收面,所述收缩率和温度T,是该减压吸收面之间的柱部处的值。
3.一种耐热聚酯容器的制造方法,其特征是,
对聚酯树脂制成的预塑形坯以一次模具进行双向拉伸吹塑成形制成一次中间成形品,在对所述一次中间成形品进行加热使之收缩成为二次中间成形品后,在对所述二次中间成形品以加热至150至210℃的二次模具,进行可使以下面的公式(2)表达的器身的厚度减少率达到5%以上的双向拉伸吹塑成形的同时进行热定形,
厚度减少率(%)={(t1-t2)/t2}×100……(2)
式中,t1是二次中间成形品的器身的壁厚,t2是作为最终成形品的聚酯容器的器身的壁厚。
4.如权利要求3所述的耐热聚酯容器的制造方法,其特征是,所述聚酯容器在其器身上具有减压吸收面,所述厚度减少率,是器身上所形成的减压吸收面之间的柱部处的值。
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