CN86102410A - 多层容器及其成型方法 - Google Patents

多层容器及其成型方法 Download PDF

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CN86102410A
CN86102410A CN86102410.9A CN86102410A CN86102410A CN 86102410 A CN86102410 A CN 86102410A CN 86102410 A CN86102410 A CN 86102410A CN 86102410 A CN86102410 A CN 86102410A
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中村喜则
折元宏行
佐藤晃一
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Nissei ASB Machine Co Ltd
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Abstract

本发明提供一种多层容器，其断面结构包括至少三层，多层容器由注塑成型的多层型坯用吹塑或定向吹塑成型方法制得，多层型坯包括形成型坯本体的第一种树脂和具有比第一种树脂的隔气性能或耐热性能好的第二种树脂，第二种树脂在第一种树脂之中作为中间层，中间层的厚度小于外层的厚度并且向外层一侧偏移，第一种树脂由中间层分隔成内层和外层，内层和外层的厚度比为1.5∶1，或更大一些，最好是在3.50∶1范围内。

Description

本发明是关于一种多层的容器，这种合成树脂的容器的断面结构至少有三层，用来盛装充碳酸气的饮料或果汁。
用吹塑或取向吹塑方法制成的塑料包装容器具有重量轻和不怕摔的优点，但其耐热性能和隔气性能不如玻璃容器。当这种容器用来装饮料的时候，为了抑制在高温条件下灌装的果汁、氧气、碳酸或其他东西的渗漏，必须对这种容器做进一步的改进。
从上述原因出发，已经发展出一种至少有三层的多层容器，形成这种容器本体所用的树脂（比如聚对苯二甲酸乙酯）中，采用了另外一种树脂作为中间层，这可以弥补前面所讲的那种树脂的缺点。作为另外几种中间层的材料，可以采用乙烯-乙烯醇共聚物和聚碳酸酯酰胺等，前者具有很好的隔气性能，后者具有耐热性能。
这种多层结构的容器可以用一个挤压成型或注塑成型的多层型坯用吹塑或取向吹塑方法来生产，就和在单层容器的情况相同，并且要在形成容器本体的树脂中间或者里面加上一层中间层。当中间层加在容器本体的树脂中间时，被中间层分开的内层和外层在厚度上没有什么差别，但是当中间层的位置靠里侧的时候，容器的内层和外层的厚度就不同了，此时，内层的厚度要比外层薄得多。
在多层容器中，各层的厚度大小取决于用挤压方法或注塑方法生产的多层的带底的型坯的厚度分配，并且型坯各层的厚度比例将成为容器各层厚度分配比例，加工过程中没有什么变化。
在吹塑多层带底的型坯时使用一个双层喷咀，喷咀的外通道与喷咀的出口相通，喷咀的内通道则与外通道的最末端相连通，如美国专利No.4，174，413中所提出的那样，同时，分别通过这个外通道和内通道将第一种树脂和第二种树脂注射到空腔之中，第一种树脂形成容器本体，而第二种树脂形成中间层。中间层的厚度可以随两种树脂的量而变化，但是这个中间层总是向里侧偏移，因此，内层的厚度总是较薄。
象乙烯-乙烯醇共聚物（EVOH），聚酰胺（PA）等这类树脂，水份吸收得越多则氧气、碳酸等的渗漏越利害。另一方面，用作充碳酸气饮料瓶的双轴取向的聚脂树脂，对水蒸汽的渗透性要比上面所讲的树脂小些，但是水蒸汽的渗透性又受一般树脂的厚度的影响。
所以，在一个内层壁厚较小的多层容器中，既使形成容器所用的树脂是双轴取向的聚对苯二甲酸乙酯，由于吸收水份的影响，中间层的隔气性能也会大大降低，并且氧气和碳酸的渗漏会有所增加。因此，这种容器不适用于啤酒，充碳酸气饮料和类似产品，因为这些东西都需要储存一个较长的时间，另外，要想用这种容器来装那些怕有氧气渗漏的食品和饮料，既使是多层容器也得进一步改进其隔气性能。
同样，为了增加容器的耐热性能，既使作为中间层的第二种树脂是一种耐热的树脂，也不希望内层的厚度太薄，而应使内层的厚度尽可能地厚一些。不过，到目前为止，还没有能够制做内层厚度大于外层厚度的耐热的三层容器。
本发明正是要解决上面所讲的有关多层容器所存在的问题。本发明的一个目的是要提供一种新型的多层容器，或者是一种具有良好耐热性能的内层厚度比以往结构的内层厚度大的多层容器，这种容器可以减小氧气和碳酸的渗漏，可以在较长时间内保持隔气性，既使在较高的温度下也能保持隔气性，同时，所采用的材料是一般多层容器所用的相同的树脂。
本发明的另一个目的是提供一种新的成型方法，这种方法包括注塑成型一个多层的型坯，通过使用一种双层喷咀注射进去一个中间层的办法使所成型的多层容器的内层厚度大于外层，并且可以从上述这个多层的型坯得到具有良好的隔气性能的多层容器。
因此，本发明可以提供一种多层容器以及其成型方法，这种容器由第一种树脂和第二种树脂所组成，第一种树脂形成容器本体，而第二种树脂具有比第一种树脂大的隔气性能或耐热性能，第二种树脂作为中间层夹在第一种树脂之中，上述容器本体至少有三层，即上述的中间层，以及由上述的中间层分隔开的内层和外层，由于中间层向外层方向偏移，所以形成的内层的厚度要比外层厚度大得多，另外，在第二种树脂具有隔气性的情况下，容器内部的温度对于中间层的影响会被内层的壁厚所减弱，而在第二种树脂具有耐热性的情况下，则将由于较厚的内层和中间层的作用而使容器能以承受得住装瓶时的高温。
下面说明一下附图。
图1所示是用按照本发明的方法成型的多层型坯得到的多层容器的部分剖开和放大的断面图。
图2所示是按照本发明成型的多层型坯的断面图。
图3至图5分别表示喷咀部分和模子，以说明本发明的成型方法的工作顺序：
图3所示是形成多层型坯本体的第一种树脂已注入一部分的断面图;
图4A所示是喷咀上端部分和出口部分的断面图，表示形成中间层的第二种树脂已注入形成容器本体的树脂中间的状况;
图4B所示是喷咀上端部分和出口部分的断面图，表示第二种树脂正在注入的情况;
图4C所示是喷咀上端部分和出口部分的断面图，表示第一种和第二种树脂同时被注入的情况;
图5所示是多层型坯已经成型完毕的情况。
图1表示一个呈瓶状的多层容器，它具有三层的结构，其中内层11和外层12由相同的热树脂形成，而中间层13则由具有良好隔气性能的热塑树脂形成。
中间层13向外层12一侧偏移，因此内层11的壁厚要比外层12的厚度大得多。
内层11和外层12的厚度之比最好在1.5∶1以上，并且内层的厚度越大则隔气性能越好。
上面所讲的多层容器1可以用三层结构的多层型坯2用吹塑或取向吹塑方法成型，在这个多层型坯中，形成型坯本体的树脂被中间层23分隔成内层21和外层22，内层和外层具有不同的厚度，中间层则由另外一种树脂注入前面讲的那种树脂中而形成。
这种多层型坯2是用图3及其它图所示的双层喷咀进行注射成型的，这种双层喷咀3有两个同轴的通道，外通道32与喷口31相通，而内通道33则与外通道32的末端相连通。
在用一般的双层喷咀进行多层型坯的成型过程中，形成型坯的第一种树脂是通过喷咀的外通道32注入模子4中去的，但在本发明的方法中，第一种树脂5是从内通道33注入的，而从外通道32注入形成中间层的树脂6。树脂6的注入压力最好是在这样的范围内，它能使第一种树脂5象芯子一样保留在喷咀的喷口31中间。
往模子4中注射树脂时，首先经内通道33注入适当数量的第一种树脂5：在这种情况下，对于聚对苯二甲酸乙酯（以下称作“PET”）来说，注射的压力大约为65公斤/厘米2，注射时间大约为3.5秒，在这之后，注射暂停，并从外通道32注入第二种树脂6，注射时的压力为90公斤/厘米2，注射时间为0.1到1.0秒。
在第一种树脂5停止注射时所注入的第二种树脂6向注有第一种树脂5的空腔的外侧偏移，如图4A所示。
这样的结果如图4B所示的那样，先注射进去的第一种树脂5的一部分由于模子4的冷却作用而形成表面层5a和5b，而其余部分则在从内通道33到喷咀的喷口31的这一段里面以芯子5c的形式保留在那里，这个芯子5c使树脂6不会从喷咀喷口31的中心进入第一种树脂5的中心部分，而是经过喷咀喷口31沿着芯子5c的圆周表面分布开来。
在注射了一段时间以后，再次注入第一种树脂5，同时也注入第二种树脂6。第二种树脂6的注射时间约为1.6秒，而第一种树脂5在再次注射开始后的注射时间约为3.4秒，并且两次注入的树脂都在第一种树脂5由于冷却而形成的表面层之间流动，如图4c所示。由此，外表面层5b由第二种树脂6从流动的第一种树脂5那里移走了并且形成为外表面层22，其厚度并没有增加。内表面层5a与随第二种树脂6一起注入的第一种树脂5熔合在一起，从而增加了厚度，形成一个厚的内表面层21。最终的结果如图5所示，形成了一个具有三层结构的多层型坯2，其中间层23偏向外表面层22一侧。
在上面所讲的注射成型的过程中使用了乙烯-乙烯醇共聚物作为第二种树脂6。当中间层23是用包含甲氧基物（methoxylene    group）的聚酰胺成型的时候，第二种树脂6可以在形成型坯的树脂5注入以后单独注入，在这以后可以再单独地注入第一种树脂5，也可以在注入第一种树脂5的同时将第二种树脂6注射进去。
不过，不论第二种树脂6注入的时间如何安排，第一种树脂5总是从内通道33中首先注入，接着从外通道32将第二种树脂6注射进去，这样就有可能使多层型坯2中被第二种树脂6所形成的中间层23隔开的内层21具有比外层22大得多的厚度。
当第二种树脂6的量减少时，中间层23的厚度也自然会减小，但是这时外层22的厚度没有多大的变化，而且内层21的厚度则会增加。
这样，内层21和中间层22的厚度可以相互调节以提高容器的隔气性能和耐热性能。在有些情况下，第二种树脂6的量可以减少以降低成本费用，因为一般来说第二种树脂6要比第一种树脂5贵一些。
用上面所讲的多层带底的型坯2用常规的方法进行取向吹塑成型得到的双轴取向的三层容器的隔气效果列在下面：
实施例和比较的实例
容器种类：用于充碳酸气饮料的圆底瓶
0.7升，26克
第一种树脂：PET：TEIJIN    TR-8550
第二种树脂：PA：MXD-6    尼龙
第三种树脂：EVOH：KURARE    EVERL
E-105
使用的机器：ASB-50HT    197（由NISSEI    ASB制造）
注射能力：第一种树脂：3，50盎司（φ38螺旋）
第二种树脂：1，0盎司（φ19螺旋）
氧气和碳酸气的渗漏系数（每瓶）：CC/2公斤，24小时，
1大气压。
氧气渗漏的测量设备：MOCON    两通道气体渗漏测量仪
碳酸气渗漏的测量设备：MOCON    五通道气体渗漏测量仪
（测量一个充满4-容积石灰水的容器）
测量条件：相对湿度：内部-100%RH，
外部-65%RH，
室温：24℃
保留一星期。
实施例1，2和比较的实例1
容器的结构：外层/中间层/内层
PET/PA/PET
Figure 86102410_IMG2
实施例3，4和比较的实例2
容器的结构：外层/中间层/内层
PET/EVOH/PET
从上面所讲的实施例和比较实例可以看得很清楚，按照本发明的方法制做的内层厚度大于外层厚度的容器，其隔气效果已经比一般结构的外层厚度较大的容器提高了。
此外，也可以注意到，如果一个耐热的多层容器使用耐热树脂来作中间层的材料，比如聚碳酸酯，多芳基化聚对苯二甲酸乙酯（U-POLYMER）或类似的材料，那么这种内层比较厚的容器将具有很好的耐热性能，这样的容器既使是在高达85℃的温度下也不会产生热变形。

Claims (5)

1、一种由至少三层组成的多层容器，由注塑成型的多层型坯用吹塑或者定向吹塑的成型方法制得，该型坯包括形成其本体的第一种树脂以及隔气性能或耐热性能高于第一种树脂的第二种树脂，上述的第二种树脂处于第一种树脂之中作为中间层，上述中间层的厚度小于外层的厚度并且偏向上述外层，由上述的中间层将上述的第一种树脂分隔成内层和外层，内层厚度与外层厚度之比为1.5∶1或更大一些，并且最好是在3.5∶1的范围内。
2、权利要求1所讲的多层容器，其中第一种树脂为聚对苯二甲酸乙酯，而第二种树脂为乙烯一乙烯醇共聚物。
3、权利要求1所讲的多层容器，其中第一种树脂为聚对苯二甲酸乙酯，而第二种树脂为多芳基化树脂或者聚碳酸酯。
4、一种多层容器的成形方法包括：使用一个具有外通道和内通道的双层喷咀，其外通道与喷咀的喷口相连而内通道与上述外通道的末端相连通，从上述的内通道把形成型坯本体的第一种树脂注射到空腔中，把形成中间层的第二种树脂注射到上述第一种树脂中，中间层成型过程中向外层偏移，因此形成一个至少具有三层的多层型坯，由中间层将由第一种树脂形成的内外层分隔开，内层的厚度大于由同样树脂形成的外层的厚度，将上述的多层型坯用吹塑或定向吹塑的方法成型为一个多层容器，其内层的厚度要比外层的厚度大得多。
5、权利要求4所讲的多层容器成型方法，其中将一定量的第一种树脂通过双层喷咀的内通道注射到空腔中，此后就暂时停止注射这种树脂，而通过喷咀的外通道将第二种树脂注射到空腔内的第一种树脂中去，以后再开始通过内通道注射第一种树脂，同时注射第二种树脂，此后，停止注射第二种树脂，再过一些时间停止注射第一种树脂以形成一个多层的型坯。
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