CN1228736A - 具有气体屏障性质的多层中空容器 - Google Patents
具有气体屏障性质的多层中空容器 Download PDFInfo
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- CN1228736A CN1228736A CN97197611A CN97197611A CN1228736A CN 1228736 A CN1228736 A CN 1228736A CN 97197611 A CN97197611 A CN 97197611A CN 97197611 A CN97197611 A CN 97197611A CN 1228736 A CN1228736 A CN 1228736A
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- hollow container
- gas shield
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- polyglycolic acid
- multilayer hollow
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Abstract
本发明提供了一种氧气屏障性和碳酸气屏障性都优越的,具有气体屏障特性的多层中空容器及其制造方法。该容器的特征为,它具有在由含有60重量%以上的,用式(1)表示的重复单元的聚乙醇酸制成的层的至少一个单面上,层叠着热可塑性树脂层的多层容器壁的结构。
Description
<技术领域>
本发明涉及具有气体屏障特性的多层中空容器,更具体地说,涉及一种通过将聚烯烃等热可塑性树脂层和聚乙醇酸层组合,显著地改善热可塑性树脂层的氧气屏障特性和/或碳酸气屏障特性的多层中空容器。本发明的具有气体屏障特性的多层中空容器,特别适合于作为饮料用、食品用、日用品用和汽油用等的各种容器。
<背景技术>
以往,作为饮料、食品、日用品和汽油等的各种物品的容器,往往使用各种树脂制的中空容器。具体地说,例如有使用聚烯烃、聚酯、聚苯乙烯、聚氯乙烯等热可塑性树脂的中空容器。但是,由于这些中空容器一般来说,其氧气屏障性、碳酸气屏障性等气体屏障特性不太好,所以用作饮料、食品容器和化妆品容器等不能满足要求。因此,为了改良树脂制的中空容器的气体屏障特性,开发了将由乙烯·乙烯醇共聚体(EVOH),聚酰胺等组成的气体屏障层组合而成的多层中空容器。
但是,由于在高温和高湿度下,EVOH和聚酰胺等气体屏障性树脂层的气体屏障特性大幅度恶化,因此,含有这种层的现有的多层中空容器,作为要求在高温和高湿度下进行蒸馏甑灭菌的处理工序的物品,特别是作为要求长期保存的物品等的中空容器不太好。
近年来,作为对环境污染小的塑料,例如:聚乳酸、聚琥珀酸酯、聚癸内酰胺等生物分解性聚合物引起人们注意,并且正在开发使用这种生物分解性聚合物的中空容器。但是,这些生物分解性聚合物的中空容器的氧气屏障性、碳酸气屏障性等气体屏障特性不太好。另外,当将现有的EVOH和聚酰胺等组成的气体屏障性树脂层,复合在这些生物分解性聚合物层上,以提高气体屏障特性时,存在环境污染增大的问题。
本发明人成功地制造了由聚乙醇酸构成的,气体屏障特性优越的中空容器。但是,只用聚乙醇酸的一个单层,其耐湿性、机械强度和经济性等并不一定很好。
<发明的说明>
本发明的目的是要提供一种具有良好的气体屏障特性,作为要求在高温和高湿度下进行蒸馏甑灭菌处理工序的物品,和要求长期保存的物品等的容器的多层中空容器。
本发明的另一个目的是要提供一种氧气屏障特性,和碳酸气屏障特性都特别优越的、具有气体屏障特性的多层中空容器。
本发明还有一个目的是要提供一种对环境污染小的、具有气体屏障特性的多层中空容器。
本发明人为了克服前述现有技术的缺点,经研究得到了通过将聚乙醇酸制成的层,与热可塑性树脂层组合,使热可塑性树脂层的氧气屏障性和/或碳酸气屏障性显著改善的、具有气体屏障特性的多层中空容器。
例如,在具有聚烯烃/气体屏障性树脂/聚烯烃层这样的构成的容器壁的现有的、具有气体屏障特性的多层中空容器中,当配置聚乙醇酸制成的层代替EVOH和聚酰胺等构成的、具有气体屏障特性的树脂层时,可以得到氧气屏障性和碳酸气屏障性都优越,具有作为要求进行高温和高湿度下的处理工序的物品,或要求长期保存的物品的容器,特性非常好的、具有气体屏障特性的多层中空容器。
当将由EVOH和聚酰胺等构成的具有气体屏障特性的树脂层与聚乙醇酸制成的层组合使用时,可以得到不但氧气屏障性,而且碳酸气屏障性都显著改善的多层中空容器。当将聚乳酸、聚琥珀酸酯和聚癸内酰胺等生物分解性聚合物层,和聚乙醇酸制成的层组合时,可以得到生物分解性(泥土中的崩坏性)不受损害,而气体屏障性和经济性都优越的多层中空容器。
本发明是基于以上的认识而完成的。本发明所提供的具有气体屏障特性的多层中空容器的特征为:在含有60重量%以上的,用(1)
表示的重复单元的聚乙醇酸制成的层的至少一个面上,具有层叠着热可塑性树脂层的多层的容器壁结构。
本发明提供了一种多层中空容器的制造方法,其特征为,将含有60重量%以上的,用式(1)表示的重复单元的聚乙醇酸,至少一种热可塑性树脂,和根据需要而使用的粘接剂,分别用挤出机加热熔融,使它们一起流入多层型坯成形用的模型中,挤出多层的管状型坯,在该型坯还未固化时,用可分开的金属模夹住该型坯的一端,同时吹入空气,将该型坯吹至金属模壁上,再冷却成形。
本发明还提供了一种多层中空容器的制造方法,其特征为,将含有60重量%以上的,用式(1)表示的重复单元的聚乙醇酸,至少一种热可塑性树脂,和根据需要而使用的粘接剂一起喷射出来,形成有底型坯,一旦固化或不固化该型坯,在过冷却状态或熔点Tm以下的温度下,在长度方向延伸或不延伸的状态下,将空气吹入金属模内,将该型坯吹至金属模壁上,再冷却成形。
作为热可塑性树脂层,可以采用例如聚烯烃(包含由芳环烯金属衍生物触媒处理的聚烯烃),聚酯,聚苯乙烯,聚氯乙烯,聚碳酸酯,聚酰胺,聚氨基甲酸乙酯,乙烯·乙烯醇共聚体,聚氯亚乙烯,聚乳酸,聚琥珀酸酯和聚癸内酰胺。
本发明的具有气体屏障特性的多层中空容器在23℃、相对湿度(RH)在80%下测定的容器壁的氧气透过率和碳酸气透过率中至少一个透过率指标,可降低至由这些热可塑性树脂单独构成的中空容器的容器壁的相应透过率值的1/2以下。
聚乙醇酸制成的层的厚度通常为1μm~3mm;而多层容器体侧壁的整个厚度通常为5μm~5mm。另外,为了改善各个间层的粘接性,也可以在各间层之间设置粘接剂层。<优选实施例>具有气体屏障特性的多层中空容器的壁面的构成
本发明的具有气体屏障特性的多层中空容器为至少一层热可塑性树脂层(以下称为基础树脂层)和具有聚乙醇酸制的层的多层中空容器。根据需要,可以在各个司层之间设置粘接剂层。本发明的具有气体屏障特性的多层中空容器体的侧壁的整个厚度,通常为5μm~5mm,较理想是10μm~3mm,最好是20μm~2mm。当这个厚度在5μm以下时,机械强度不够。当这个厚度超过5mm时,在作为中空容器使用的情况下,超过了所要求的品质,价格贵,从生产和经济的观点来看也不好。
本发明的具有气体屏障特性的多层中空容器的基本的层结构如下。这里省略了粘接剂层的表示,而且简略地将聚乙醇酸表示为PGA。
(1)热可塑性树脂/PGA
(2)热可塑性树脂1/PGA/热可塑性树脂1
(3)热可塑性树脂1/PGA/热可塑性树脂2
本发明的具有气体屏障特性的多层中空容器,如果具有前述的基本的层结构,则根据各种要求特性,也可以另外再层叠同种类,或不同种类的各种热可塑性树脂层。另外,热可塑性树脂层和聚乙醇酸制的层做成多层的方法没有特别的限制,例如,可以采用共同挤出法,或共同射出法等各种加工方法。热可塑性树脂层(基础树脂层)
在本发明的具有气体屏障特性的多层中空容器中,作为用于热可塑性树脂层的热可塑性树脂,可以采用例如:超低密度聚乙烯(VLDPE),线状低密度聚乙烯(LLDPE),低密度聚乙烯(LDPE),中密度聚乙烯(MDPE),高密度聚乙烯(HDPE),聚丙烯(PP),乙烯和丙烯橡胶(EPM),乙烯和醋酸乙烯共聚体(EVA),乙烯和丙烯酸酯共聚体(EEA),离子交联聚合物(IO)等聚烯烃;聚对苯二甲酸乙二醇酯(PET),聚萘(PEN)等聚酯;聚苯乙烯(PS),耐冲击性聚苯乙烯(HIPS),苯乙烯·丁二烯·苯乙烯块共聚体(SBS),加氢SBS(即SEBS)等聚苯乙烯类树脂;硬质聚氯乙烯,软质聚氯乙烯等聚氯乙烯(PVC)类树脂;聚碳酸酯(PC),聚酰胺(PA),聚氨基甲酸乙酯(PU),乙烯·乙烯醇共聚体(EVOH),聚氯亚乙烯类树脂(PVDC)等。
作为对环境污染小的热可塑性树脂,最好是聚乳酸,聚琥珀酸酯和聚癸内酰胺等。
在本发明的具有气体屏障特性的多层中空容器中,这些热可塑性树脂层可以单层或多层使用。从加工性和经济性等来看,希望热可塑性树脂层的厚度通常在4μm~5mm,比较理想是10μm~3mm,最好为20μm~2mm范围内。粘接剂层
在本发明中,为了提高热可塑性树脂层(基础树脂层)和聚乙醇酸制的层的粘接性,可以在各个间层中放入粘接剂层。作为粘接剂层所用的粘接剂,可以采用羧基化聚烯烃,环氧化聚烯烃,乙烯和醋酸乙烯共聚体,离子交联聚合物,聚氨基甲酸乙酯,环氧树脂,SBS,SEBS,聚氯丁二烯,苯乙烯和丁二烯共聚橡胶(SBR),天然橡胶(NR)等聚合物。
所谓羧基化聚烯烃是用丙烯酸,甲基丙烯酸,无水马来酸等不饱和酸单体,使聚烯烃变性,再导入羧基而成的聚烯烃。羧基导入可利用共聚法和接枝法中任一种方法。另外,上述不饱和酸单体也可以和甲基丙烯酸酯,丙烯酸酯,醋酸乙烯等乙烯类单体一起使用。
所谓环氧化聚烯烃,是用甲基丙烯酸,含有环氧丙基等环氧基的单体,使聚烯烃变性,再导入环氧基的聚烯烃。环氧基的导入,可以用共聚法和接枝法中任何一种方法。上述含有环氧基的单体,也可以与甲基丙烯酸酯,丙烯酸酯和醋酸乙烯等乙烯类单体一起使用。
在这些粘接剂中,从粘接性和加工性观点来看,羧基化聚烯烃与乙烯和醋酸乙烯共聚体特别好。粘接剂层的厚度,通常为0.5μm~2mm,较理想是2μm~1mm,最好是3μm~0.5mm范围内。这个厚度在0.5μm以下时,粘接性不好。这个厚度超过2mm,则价格贵,从经济方面来说是不利的。聚乙醇酸层
在本发明的具有气体屏障特性的多层中空容器中,为了改善氧气屏障性和/或碳酸气屏障性,作为气体屏障性树脂层,层叠了聚乙醇酸制成的层。在使用一般的热可塑性树脂层的情况下,氧气屏障性和碳酸气屏障性二者都得到改善。
本发明使用的聚乙醇酸为含有用下述式(1)表示的重复单元的聚合物。在该聚合物中,用式(1)表示的重复单元的比例在60重量%以上,比较理想的是在70重量%以上,最好在80重量%以上。当用式(1)表示的重复单元的比例在60重量%以下时,气体屏障特性会受到损害。
作为在用式(1)表示的重复单元以外的重复单元,可以有例如:用式(2)表示的重复单元(式中:n=1~10,m=1~10);用下述式(3)表示的重复单元(式中:j=1~10);用下述式(4)表示的重复单元(式中:R1和R2分别为独立的氢原子或碳的数目为1~10的烷基;k=2~10);用下述式(5)表示的重复单元;和用下述式(6)表示的重复单元。
通过按1重量%以上的比例,将这些重复单元(2)~(6)导入,可以将聚乙醇酸均聚物的熔点Tm降低。如果聚乙醇酸的Tm降低,由于可以降低聚合物的加工温度,因此,可以减少熔融加工时的热分解。通过共聚合作用,可以控制聚乙醇酸的结晶化速度,改良其挤出加工性和延伸加工性。如果这些重复单元(2)~(6)超过40重量%,聚乙醇酸本来固有的气体屏障特性受到损害,因此,会降低其树脂层的强韧性和耐热性等特性。<分子量-熔融粘度>
在本发明的具有气体屏障特性的多层中空容器中所使用的聚乙醇酸为高分子量的聚合物。可以将熔融粘度作为分子量的指标。本发明所使用的聚乙醇酸,在(Tm+20℃)的温度(即,相当于通常的粘融加工温度的温度)和100/秒的剪断速度下所测定的熔融粘度η*,通常为500~100,000Pa·s;比较理想的是1,000~50,000Pa·s;最好为1,500~20,000Pa·s。
当聚乙醇酸的熔融粘度η*在500Pa·s以下时,在中空容器中熔融形成时,熔融体向下拉延,熔融加工困难,或者所得到的树脂层的强韧性不够。当聚乙醇酸的熔融粘度η*超过100,000Pa·s时,熔融加工必须要高的温度,这样,加工时聚乙醇酸的品质会因热而变坏。<热的物性>
本发明所使用的聚乙醇酸的熔点Tm,通常为150℃以上,较理想为180℃以上,最好为200℃以上(许多情况下,在210℃以上)。本发明所使用的聚乙醇酸的熔融焓ΔHm,通常为20焦耳/克(J/g),较理想是30J/g以上,最好为40J/g以上。当聚乙醇酸的Tm或ΔHm降低时,气体屏障性、耐热性和机械强度等不大好。<聚乙醇酸的制造方法>
本发明所使用的聚乙醇酸,例如可用下述的①开环聚合法,或②重缩合法制造。
①在有少量触媒(例如,有机羧酸锡,卤化锡,卤化锑等阳离子触媒)存在的情况下,在大约120℃~250℃的温度下,加热乙醇酸交酯(即,1,4-二氧杂环己烷-2,5-二酮),称为开环聚合法。开环聚合最好利用块状聚合或溶液聚合来进行。
②在有触媒存在,或不存在的情况下,对乙醇酸或乙醇酸烷基酯进行加热、脱水或脱乙醇,称为重缩合法。
为了得到聚乙醇酸共聚体,在上述①或②方法中,作为共聚用单体,可以使用例如乙二醇(-)草酸酯(即1,4-二氧杂环乙烷-2,3-二酮),丙交酯,内酰胺类(例如β-丙内酯,β-丁内酯,叔丁基丁内酯,γ-丁内酯,δ-戊内酯,β-甲基-δ-戊内酯,ε-己内酯等),环丙烷碳酸酯,和1,3-二噁烷等环状单体;乳酸,3-羟基丙烷酸,3-羟基丁烷酸,4-羧基丁烷酸,6-羧基己酸等羟基羧酸,或它的烷基酯;乙二醇,1,4-丁烷二醇等脂肪族二醇,和琥珀酸,己二酸等脂肪族二羧酸或它的烷基酯等实质上的按摩尔比混合的物质;或者是两种以上的上述物质,乙醇酸交酯、乙醇酸或乙醇酸烷基酯适当组合共聚而成也可以。
另外,聚乙醇酸共聚体也可以通过在加热下,使聚乙醇酸,与(例如)具有从上述式(2)~(5)中选出的重复单元的其它聚合体,进行酯交换反应而得到。
前述的制造方法中,①的开环聚合法,由于可得到高分子量的聚乙醇酸,是较好的方法。
在前述①的制造方法中,作为当作单体使用的乙醇酸交酯(乙醇酸的二聚物环状酯),利用本发明人开发的“溶液相解聚合法”(日本专利申请第38404/1997号)得到的,比利用现有的乙醇酸低聚物升华解聚合法得到的单体纯度高;并且可以高收取率,大量得到,因此比较好。通过使用高纯度的乙醇酸交酯作为单体,可以很容易得到高分子量的聚乙醇酸。
利用溶液相解聚合法,(1)在常压或减压下,将乙醇酸低聚物,和含有沸点在230℃~450℃范围内的至少一种高沸点的极性有机溶剂的混合物,加热至引起该低聚物的解聚合的温度;(2)在该溶剂中溶解该低聚物,直至该低聚物的熔融液相的残存率(溶积比)达到0.5以下;(3)在同一温度下,继续加热,进行该低聚物的解聚合;(4)使生成的二量体环状酯(即,乙醇酸交酯),与高沸点极性有机溶剂一起馏出;(5)从馏出物中回收乙醇酸交酯。
作为高沸点极性有机溶剂,可以使用,例如邻苯二甲酸二(2-甲氧基乙基)酯等邻苯二甲酸(烷氧基烷基)酯,二甘醇二苯甲酸酯等亚烷基乙二醇二苯甲酸酯,邻苯二甲酸苄基丁酯,邻苯二甲酸二丁酯等芳香族羧酸酯,磷酸三甲苯酯等芳香族磷酸酯等。对于乙醇酸低聚物,通常按0.3~50倍量(重量比)的比例使用。根据需要,可以与高沸点极性有机溶剂一起,使用聚丙烯乙二醇,聚乙烯乙二醇和四乙烯乙二醇等作为乙醇酸低聚物的可溶化剂。乙醇酸低聚物的解聚合温度,通常为230℃以上,最好为230℃~320℃。解聚合可在常压或减压下进行,但最好在0.1~90.0kPa,即1~900mbar(毫巴)的减压下加热,进行解聚合。
作为本发明所用的聚乙醇酸层,可以单独使用聚乙醇酸的硝化作用。在不妨碍本发明的目的的范围内,也可以使用配合了无机填充剂,其它热可塑性树脂和可塑剂等的树脂组成物。具体地说。对于100重量份的聚乙醇酸,可以使用配合了0~30重量份的无机填充剂,0~30重量份的其它热可塑性树脂,和0~50重量份的可塑剂等的树脂组成物(混合物)。当无机填充剂或其它热可塑性树脂超过30重量份,或者,可塑剂超过50重量份时,所得到的聚乙醇酸层的气体屏障性不足,熔融加工性也降低。
作为无机填充剂,可以采用例如:氧化铝,二氧化硅,硅石氧化铝,氧化锆,氧化钛,氧化铁,氧化卤素,碳酸钙,硅酸钙,磷酸钙,硫酸钙,碳酸镁,硅酸镁,磷酸镁,硫酸镁,高岭土,滑石,云母,铁氧体,碳,硅氮化硅,二硫化钼,玻璃,钛酸钾等粉末;晶须;纤维等。这些无机填充剂可以分别单独,或两种以上组合使用。
作为其它热可塑性树脂可以采用例如:乳酸单聚体和共聚体,草酸乙烯单聚体和共聚体,ε-己内酯单聚体和共聚体,聚琥珀酸酯,聚羟基丁烷酸,羟基丁烷酸和羟基吉草酸共聚体,醋酸纤维素,聚乙烯醇,淀粉,聚谷氨酸酯,天然橡胶,聚乙烯,聚丙烯,苯乙烯和丁二烯共聚橡胶,丙烯腈和丁二烯共聚橡胶,聚异丁烯酸甲酯,聚苯乙烯和苯乙烯,丁二烯-苯乙烯块共聚体,苯乙烯-乙烯·丁烯-苯乙烯块共聚体,ABS树脂,MBS树脂,乙烯-乙烯醇共聚体等。这些热可塑性树脂,可以分别单独或两种以上组合使用。
作为可塑剂可以采用:邻苯二甲酸二(甲氧基乙基)酯,邻苯二甲酸二辛酯,邻苯二甲酸二乙酯,邻苯二甲酸苄基丁酯等邻苯二甲酸酯;二甘醇二苯甲酸酯,乙二醇二苯甲酸酯等安息香酸酯;己二酸二辛酯,癸二酸二辛酯等脂肪族二元酸酯;乙酰基多元酸三丁酯等脂肪族三元酸酯;磷酸二辛酯,磷酸三甲酚酯等磷酸酯;环氧化大豆油等环氧类可塑剂;聚乙二醇二癸酸酯,聚丙二醇二月桂酸酯等聚亚烷基二醇脂肪酸酯等。
这些可塑剂,可以分别单独或两种以上组合使用。本发明还可根据需要,在聚乙醇酸中添加热稳定剂,光稳定剂,防湿剂,防水剂,拒水剂,滑润剂,离型剂,耦连剂,颜料,染料等各种添加剂。这些添加剂的有效量,可分别根据使用目的来使用。具有气体屏障特性的多层中空容器体侧壁的物性
本发明的具有气体屏障特性的多层中空容器体侧壁的氧气透过率和/或碳酸气透过率,与热可塑性树脂的相应值比较,得到改善,通常达到热可塑性树脂相应值的1/2以下,较好的达到1/5以下,最好的达到1/10以下。
即,本发明的具有气体屏障特性的多层中空容器,通过从聚烯烃,聚酯,聚苯乙烯,聚氯乙烯,聚碳酸酯,聚乳酸,聚琥珀酸酯,聚癸内酰胺,聚酰胺,EVOH,聚氨基甲酸乙酯,PVDC等中选择出来的树脂制成的热可塑性树脂层上,组合作为气体屏障性改良材料的聚乙醇酸层,则氧气屏障特性和碳酸气屏障特性中至少有一种特性,与该热可塑性树脂层比较,有惊人的改善。
另外,本发明的具有气体屏障特性的多层中空容器的一大特征是,即使在高温,高湿下接受处理,其气体屏障特性也降低极小。具有气体屏障特性的多层中空容器的制造方法
中空容器做成多层的目的就是,通过做成多层,得到用单一材料得不到的所要求的特性。具体地说,可使中空容器对氧气,碳酸气等具有气体屏障特性,热密封特性;改善其耐湿性,机械强度和大幅度降低成本。
作为本发明的多层中空容器的制造方法,大致可采用下面的方法。
作为具有气体屏障特性的多层中空容器的制造方法,主要采用“多层挤出吹制成形法”和“多层喷射吹制成形法”。在两种吹制成形法中,又分别分为在吹制成形时,沿着一个轴或两个轴方向延伸的“延伸吹制成形法”,和不延伸的“无延伸吹制成形法”。这里,“延伸吹制成形法”是在吹制成形时,利用延伸,使高分子链定向,从而提高透明性,强度,弹性率和气体屏障,生等物理特性的成形法。为了改善这种物理特性,在延伸吹制时,将型坯保持在熔点以下,玻璃化转移点Tg以上的温度是非常重要的。<多层挤出吹制成形法>
本发明的多层挤出吹制成形,首先形成由聚乙醇酸,至少一种热可塑性树脂,和根据需要而使用的粘接剂构成的多层型坯。为此,分别将挤出机加热熔融的各种树脂,流入多层型坯成形用的模型(通常为圆形模型)中;在该模型内部,通过同时或逐次的合流,从该模型挤出管状的型坯。在该熔融挤出的型坯没有固化时,用可分开的金属模夹紧它,紧压型坯的一端。再通过向型坯内部吹入空气,把型坯吹至金属模型壁上,然后冷却。冷却后,打开金属模型,取出成形的产品。当吹制时,使该型坯在过冷却状态或结晶化温度(Tc1)以下,而且在比玻璃转移温度Tg高一些的温度范围内,向一个轴或两个轴方向延伸,则可得到沿着一个轴或两个轴方向定向的成形产品。<多层喷射吹制成形法>
喷射吹制成形是利用射出成形的方法,喷射形成试管状的有底型坯(预塑形坯),然后将该型坯在过冷却状态或玻璃转移点Tg以上,吹制成形。其中,在型坯喷射成形后,在没有固化的状态下,在熔点Tm以下的温度下调节温度,吹制成形的又称热型坯法。另一种情况,在型坯喷射成形后,一旦将型坯冷却固化后,再在Tg以上温度下再进行加热、调节温度,吹制成形的称为冷型坯法。在热型坯法中,又可分为延伸吹制成形和未延伸吹制成形;而冷型坯法通常只有延伸吹制成形。
本发明的多层喷射吹制成形是利用将聚乙醇酸,至少一种热可塑性树脂,和根据需要而使用的粘接剂共同射出(共同喷射)的方法,形成预塑形坯,然后,通过热型坯法或冷型坯法进行吹制成形的。这时,可以进行延伸吹制成形,或无延伸吹制成形。用途
本发明的具有气体屏障特性的多层中空容器,有效地利用其优良的氧气屏障性和/或碳酸气屏障性,可以用于例如,饮料用和食品用的中空容器,化妆品用容器和汽油用容器。特别是用在要求在蒸馏甑灭菌等高温、高湿度下进行处理的物品,尤其是要求长期保存的物品,要求对碳酸气有屏障性的物品,和要求环境污染小的物品等的包装容器更好。
<实施例>
以下举出合成例、实施例和比较例,来具体说明本发明。物性测定法
(1)熔融粘度η*
测定熔融粘度η*作为聚合物分子量的指标。使用厚度约为0.2mm的各种聚合物的非晶片,在150℃下加热5分钟得到的结晶的聚合物,作为试件;采用装有D=0.5mm,L=5mm的喷嘴的毛细试验仪[东洋精机(株)制造],在(Tm+20℃)的温度,和100/秒的剪断速度下进行测定。
(2)聚合物的热的特性
利用厚度约为0.2mm的各种聚合物的非晶片做试件,利用示差走查热量计(DSC;Mettler公司制,TC-10A型),在氮气气流下和在10℃/分的速度下升温,测定其结晶化温度(Tc1),熔点(Tm)和熔融焓(ΔHm)。在5℃/分的升温速度下测定玻璃化转移温度(Tg)。
(3)氧气透过率(O2透过率)
对于从吹制容器体侧壁上切取的各个试件,使用GL科学公司制的两面加湿式气体透过试验机,根据JISK-7126标准,在23℃和80%相对湿度下,测定氧气透过程度;再换算成1mm厚的薄膜,求出氧气透过率。
(4)碳酸气透过率(CO2透过率)
对于从吹制容器体侧壁上切取的各个试件,利用GL科学公司制的两面加湿式气体透过试验机,根据JISK-7126标准,在23℃和80%相对湿度下,测定碳酸气透过程度;再换算成厚度为1mm的薄膜,求出碳酸气透过率。[合成例1]单体合成
将5kg的乙醇酸(和光纯药(株)制)装入10升的高压釜中,一边搅拌,从170℃升温加热至200℃约2小时,同时一边馏出生成水,进行缩合。接着,减压至20kPa(200mbar),保持2小时,馏出低沸点成份,调制成乙醇酸的低聚物。乙醇酸低聚物的熔点Tm为205℃。
将1.2kg乙醇酸低聚物装入10升的烧瓶中,加入联苯酰丁基邻苯二甲酸盐5kg(纯正化学(株)制)作为溶剂,和聚丙烯乙二醇(纯正化学(株)制,#400)1509作为可溶化剂,在氮气氛围中,在5kPa(50mbar)的减压下,加热至大约270℃,进行乙醇酸低聚物的“溶液相的解聚合”;与联苯酰丁基邻苯二甲酸盐一起,馏出生成的乙醇酸交酯。
在得出的共同馏出物中,加入大约两倍容积的环己烷,从联苯酰丁基邻苯二甲酸盐中析出乙醇酸交酯,再滤出分开。再利用醋酸酯对它进行再结晶,进行减压干燥,得到精制的乙醇酸交酯。[聚合物调制例1]
将200g合成例1中得到的乙醇酸交酯装入PFA制的圆筒中,吹入氮气,并在室温下干燥大约30分钟。其次,加入0.04g的SnCl4·6.5H2O作为触媒,吹入氮气,在170℃~175℃下保持聚合2小时。聚合完成后,将该圆筒冷却至室温,粉碎从圆筒中取出的聚合物,在大约150℃和1kPa(=1mbar)以下的条件下,减压干燥一夜,除去残存的单体,即得到聚乙醇酸[聚合物(P-1)]。重复同样的方法,调制必要数量的聚合物(P-1)。[聚合物调制例2]
除了用1969的乙醇酸交酯和49的L-(-)丙交酯的混合物代替2009的乙醇酸交酯以外,进行与聚合物调制例1相同的聚合和后处理,得到乙醇酸-丙交酯共聚体[聚合物(P-2)]。重复同样的方法,调制必要数量的聚合物(P-2)。
表1中表示在聚合物调制例1和2中得到的聚乙醇酸的组成和物理特性。
表1
聚合物调制例 | |||
1 | 2 | ||
单体组成(重量/重量) | GA | GA/LA=98/2 | |
聚合物代码 | P-1 | P-2 | |
η*(Pa·s) | 4000 | 3800 | |
热的性质 | Tg(℃) | 38 | 38 |
Tc1(℃) | 84 | 77 | |
Tm(℃) | 221 | 216 | |
ΔHm(J/g) | 72 | 68 |
(注)GA=乙醇酸交酯,LA=L-(-)-丙交酯[颗粒调制例1]
将聚合物(P-1)在氮气流作用下,供给装着直径为φ3mm的喷嘴的小型两轴混揉挤出机,在大约230℃~235℃的熔融温度下,挤出成股线状,然后在空气中冷却切断,得到颗粒(No.1)。[颗粒调制例2]
除了采用聚合(P-2),将熔融温度变更为大约225℃~230℃以外,与颗粒调制例1同样进行,可调制出颗粒(No.2)。[实施例1]
将颗粒(No.1)中密度聚乙烯(MDPE;M1=109/10分)和羧基化的聚烯烃(注册商标名为MODIC,E-300S,三菱油化(株)制)三种物质,供给5层用的共同喷射成形机,喷射出来,注入预制型坯金属模中,形成预制型坯(外径约2cm,长度约6cm)。其次,在固化前,调温至大约120℃,将预制型坯插入金属模型内。将一根杆插入该预制型坯内,使该预制型坯在长度方向上延伸约2倍;同时,以大约为3的吹气比进行吹制。接着,冷却固化,调制出多层中空容器MB-1(体部外径约6cm,体部长度约10cm,头部外径约2cm,头部长度约1cm,平底的中央凹进去)。[实施例2]
除了用颗粒(No.2)代替颗粒(No.1)以外,与实施例1同样进行,调制出多层中空容器MB-2。[实施例3]
将颗粒(No.1),MDPE(M1=10g/10分)和羧基化聚烯烃(注册商标名为MODIC E-300S)三种物质,供给5层用的多层模头(圆形模型),熔融挤出成管状,做出型坯。将该型坯夹在做瓶子用的可分开的金属模中,夹紧底部,调节温度至大约120℃,以大约为3的吹气比进行吹制。再冷却固化,调制出多层中空容器MB-3(体部外径约6cm,体部长度约10cm,头部外径约2cm,头部长度约1cm,平底的中央凹进去)。[实施例4]
将颗粒(No.1),聚对苯二甲酸乙二醇酯(PET;MI=139/10分),和羧基化聚烯烃(注册商标名为MODIC E-300S)三种物质,供给5层用的共同喷射成形机,将它们喷射出来,注入预制型坯的金属模中,形成预制型坯(外径约为2cm,长度约为6cm),再冷却固化。其次,再加热该预制型坯,调节温度至大约85℃,将该预制型坯插入金属模内。再将一根杆插入该预制型坯内,使该预制型坯在长度方向上延伸约2倍,同时以大约为3的吹气比吹制该预制型坯。接着,冷却固化,即调制成多层中空容器MB-4。[比较例1]
除了将MDPE代替颗粒(No.1)供给共同喷射成形机这点以外,与实施例1同样进行,调制出多层中空容器MB-C1。[比较例2]
除了将PET(M1=13g/10分)代替颗粒(No.1)供给共同喷射成形机这点以外,与实施例4同样进行,调制出多层中空容器MB-C4。<气体屏障性比较>
对于实施例1~4和比较例1~2得到的各种中空容器,切出其体部侧壁,测定各种气体的透过率。另外,对实施例1~4和比较例1~2所采用的MDPE和PET,分别用热压机进行熔融加工,再急剧冷却制成厚度约为0.1mm的基础树脂片BS-1和BS-2。对这些基础树脂片,测定其各种气体的透过率,与上述容器体侧壁的各个气体透过率值比较。结果表示在表2中。
表2
实施例 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 比较例1 | 比较例2 | ||
体部侧壁 | 代码号 | MB-1 | MB-2 | MB-3 | MB-4 | ML-5 | ML-6 | |
构成 | PE/接/PGA/接/PE | PE/接/PGA/接/PE | PE/接/PGA/接/PE | PET/接/PGA/接/PET | PE/接/PE/接/PE | PET/接/PET/接/PET | ||
厚度(μm) | 49/11/10/9/51 | 50/9/10/11/50 | 49/10/10/10/50 | 28/8/10/12/32 | 52/12/9/10/50 | 29/10/10/11/30 | ||
PGA代码号 | P-1 | P-2 | P-1 | P-1 | - | - | ||
O2透过率23℃、80%RH(cm3·mm/m2·天·大气压) | 0.3 | 0.3 | 0.3 | 0.2 | 60 | 3 | ||
CO2透过率23℃、80%RH(cm3·mm/m2·天·大气压) | 1.9 | 2.0 | 2.0 | 1.3 | 260 | 25 | ||
体部侧壁/基础片 | MB-1/BS-1 | MB-2/BS-1 | MB-3/BS-1 | MB-4/BS-2 | MB-C1/BS-1 | MB-C2/BS-2 | ||
体部侧壁/基础片透过率之比 | O2 | 4/1000 | 4/1000 | 4/1000 | 8/100 | - | - | |
CO2 | 6/1000 | 6/1000 | 6/1000 | 7/100 | - | - |
另外,基础树脂片BS-1和BS-2的各种气体透过率的测定结果表示在表3中。
表3
基础片 | 代码号 | BS-1 | BS-2 |
构成 | PE | PET | |
厚度(μm) | 100 | 100 | |
O2透过率23℃、80%RH(cm3·mm/m2·天·大气压) | 70 | 2.5 | |
CO2透过率23℃、80%RH(cm3·mm/m2·天·大气压) | 300 | 20 |
<产业上利用的可能性>
本发明提供了具有优良的气体屏障特性的多层中空容器,它可以作为要求在高温和高湿度下进行蒸馏甑灭菌的处理工序的物品,特别是要求长期保存的物品和尤其是要求对碳酸气有屏障性的物品等的容器。另外,本发明提供了氧气屏障性和碳酸气屏障性都特别优越的多层中空容器。本发明还可提供对环境污染小的、具有气体屏障特性的多层中空容器。
Claims (14)
2.如权利要求1所述的具有气体屏障特性的多层中空容器,其特征为该热可塑性树脂层为从下列物质组成的族中选择出的热可塑性树脂形成的层:聚烯烃,聚酯,聚苯乙烯,聚氯乙烯,聚碳酸酯,聚酰胺,聚氨基甲酸乙酯,乙烯·乙烯醇共聚体,聚氯亚乙烯,聚乳酸,聚琥珀酸酯和聚癸内酰胺。
3.如权利要求1或2所述的具有气体屏障特性的多层中空容器,其特征为,在23℃和相对湿度80%条件下测定的容器壁的氧气透过率和碳酸气透过率中,至少有一个指标只是热可塑性树脂层的容器壁的相应值的1/2以下。
4.如权利要求1至3中任何一项所述的,具有气体屏障特性的多层中空容器,其特征为,在聚乙醇酸层和热可塑性树脂层之间放置着粘接剂层。
5.如权利要求4所述的具有气体屏障特性的多层中空容器,其特征为,该粘接剂层为从下列物质组成的族中选择出的粘接剂形成的层:羧基化聚烯烃,环氧化聚烯烃,乙烯和醋酸乙烯共聚体,离子交联聚合物,聚氨基甲酸乙酯,环氧树脂,苯乙烯·丁二烯·苯乙烯块共聚体的弹性体,加水的苯乙烯·丁二烯·苯乙烯块共聚体的弹性体,聚氯丁二烯,苯乙烯·丁二烯共聚橡胶和天然橡胶。
6.如权利要求1至5中任何一项所述的具有气体屏障特性的多层中空容器,其特征为,该聚乙醇酸层为由在(熔点+20℃)的温度下,和剪断速度为100/秒下测定的熔融粘度η*=500~100,000Pa·s,熔点Tm在150℃以上,并且熔融焓ΔHm为20J/g以上的聚乙醇酸形成的层。
7.如权利要求1至6中任何一项所述的,具有气体屏障特性的多层中空容器,其特征为,聚乙醇酸为乙醇酸交酯的开环聚合体。
8.如权利要求1至6中任何一项所述的具有气体屏障特性的多层中空容器,其特征为,聚乙醇酸为从由下列物质组成的族中选择出的、至少一种共聚单体在0重量%以上,40重量%以下的共聚体:60重量%以上,100重量%以下的乙醇酸交酯,乙二醇(-)草酸脂,内酰胺类,环丙烷碳酸酯和1,3-二氧杂环己烷。
9.如权利要求1至8中任何一项所述的,具有气体屏障特性的多层中空容器,其特征为,它具有热可塑性树脂/粘接剂/聚乙醇酸层这样的构成。
10.如权利要求1至8中任何一项所述的,具有气体屏障特性的多层中空容器,其特征为,它具有热可塑性树脂/粘接剂/聚乙醇酸/粘接剂/热可塑性树脂层这样的构成。
11.如权利要求10所述的,具有气体屏障特性的多层中空容器,其特征为,它具有聚烯烃/粘接剂/聚乙醇酸/粘接剂/聚烯烃层这样的构成。
12.如权利要求10所述的,具有气体屏障特性的多层中空容器,其特征为,它具有聚酯/粘接剂/聚乙醇酸/粘接剂/聚酯层这样的构成。
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JP26554096 | 1996-09-13 | ||
JP265540/1996 | 1996-09-13 |
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CN1070773C CN1070773C (zh) | 2001-09-12 |
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US (1) | US6673403B1 (zh) |
EP (1) | EP0925915B1 (zh) |
KR (1) | KR100451403B1 (zh) |
CN (1) | CN1070773C (zh) |
DE (1) | DE69727304T2 (zh) |
TW (1) | TW357132B (zh) |
WO (1) | WO1998010932A1 (zh) |
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- 1997-08-22 CN CN97197611A patent/CN1070773C/zh not_active Expired - Fee Related
- 1997-08-22 KR KR10-1999-7002019A patent/KR100451403B1/ko not_active IP Right Cessation
- 1997-08-22 WO PCT/JP1997/002923 patent/WO1998010932A1/ja active IP Right Grant
- 1997-08-22 US US09/254,739 patent/US6673403B1/en not_active Expired - Fee Related
- 1997-08-22 EP EP19970935859 patent/EP0925915B1/en not_active Expired - Lifetime
- 1997-09-10 TW TW086113136A patent/TW357132B/zh not_active IP Right Cessation
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CN1972801B (zh) * | 2004-06-25 | 2010-04-14 | 株式会社吴羽 | 聚乙醇酸树脂类多层片材 |
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CN102574322A (zh) * | 2009-08-04 | 2012-07-11 | 三菱瓦斯化学株式会社 | 容器的制造方法 |
Also Published As
Publication number | Publication date |
---|---|
EP0925915A1 (en) | 1999-06-30 |
CN1070773C (zh) | 2001-09-12 |
DE69727304T2 (de) | 2004-10-21 |
EP0925915B1 (en) | 2004-01-21 |
KR20000036033A (ko) | 2000-06-26 |
EP0925915A4 (en) | 2001-05-30 |
DE69727304D1 (de) | 2004-02-26 |
WO1998010932A1 (fr) | 1998-03-19 |
TW357132B (en) | 1999-05-01 |
KR100451403B1 (ko) | 2004-10-06 |
US6673403B1 (en) | 2004-01-06 |
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