CN1474743A - 多层预成型体及其制造方法 - Google Patents
多层预成型体及其制造方法 Download PDFInfo
- Publication number
- CN1474743A CN1474743A CNA01819057XA CN01819057A CN1474743A CN 1474743 A CN1474743 A CN 1474743A CN A01819057X A CNA01819057X A CN A01819057XA CN 01819057 A CN01819057 A CN 01819057A CN 1474743 A CN1474743 A CN 1474743A
- Authority
- CN
- China
- Prior art keywords
- intermediate layer
- preform
- injection
- blow molding
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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Images
Classifications
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- B29C45/16—Making multilayered or multicoloured articles
- B29C45/1642—Making multilayered or multicoloured articles having a "sandwich" structure
- B29C45/1646—Injecting parison-like articles
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Abstract
本发明提供了一种多层中空容器用预成型体及其制造方法，该多层中空容器用预成型体具有优异的成型性、生产率，并且即使大量填充回收材料，容器的特性也不降低。该多层吹塑成型中空容器的有底预成型体的筒体和底部由3层结构组成，该3层结构的最内层和最外层由第1材料构成，中间层由第2材料构成，并且底部中间层的壁厚(tc)比筒体中间层的壁厚(to)薄(tc＜to)。该成型体的制造方法如下：在同一成型工序中，依次连续实施(i)注射第1材料的工序、(ii)同时注射第1材料和第2材料的工序及(iii)注射第1材料的工序，从而将第1材料和第2材料填充到注射成型金属模具的模槽中。
Description
技术领域
本发明涉及一种多层吹塑成型中空容器用有底预成型体及其制造方法。更具体说，本发明涉及一种以聚对苯二甲酸乙二醇酯或聚萘二甲酸乙二醇酯为主要材料、使用回收树脂材料进行多层化、回收性及物性优异的多层中空容器用有底预成型体及其制造方法。
现有技术
双色成型、夹层成型等在同一注射成型工序中制得由不同种树脂材料构成的多层成型品的方法已众所周知。对于吹塑成型中空容器，用气体阻隔性树脂材料作为中间材料的多层预成型体也已商品化。
上述多层预成型体一般是用被称为夹层成型法的注射成型法制造的，在该夹层成型法中，通过注射第1材料后注射第2材料、使其成为表层是第1材料、中间层是第2材料的2种3层结构。但是，在以往的夹层成型法中，由于中空容器的预成型体一般通过在底部配置浇口来填充树脂，因此底部由第2材料构成的中间层厚度增加，而由第1材料构成的表层厚度减少。因此，当第2材料的机械强度低时，会产生中空容器的底部强度降低和当第2材料价格高时成本上升等问题。
另一方面，近年来用聚对苯二甲酸乙二醇酯生产瓶子，其回收系统不断发展，对于回收PET瓶的再利用成为人们思考的问题。因此，使用回收材料制造多层瓶的研究在不断进行，但由于回收材料的强度差，因此目前将其作为瓶子再利用是困难的。特开平2-258310号公报及特开平7-178801号公报公开了通过调整填充第1材料及第2材料的定时，在底部进而形成由第1材料构成的芯体层，得到5层结构。由于该方法以减少价格高的第2树脂材料的填充量，从而降低制造成本为目的，因此为了提高机械强度，必须抑制第2材料的填充量。
如果使用上述方法，即使使用回收材料，为了不使瓶子的强度，特别是落下时的冲击强度降低，必须大幅度减少回收材料的填充量。因此，该方法不能说是适宜于提供回收性优异的预成型体。
发明内容
本发明的一个目的在于提供一种多层中空容器用预成型体。
本发明的另一目的在于提供一种即使大量填充回收材料、容器的特性也不降低并且具有优异的成型性、生产率的多层中空容器用预成型体。
本发明的再一目的还在于提供一种用于在使多层预成型体的多层结构、即机械强度差的第2材料的壁厚分布最适化的同时，实现其壁厚分布的制造方法。
本发明的其他目的及优点如下所述。
根据本发明，第1，本发明的上述目的及优点通过一种吹塑成型中空容器的有底预成型体而实现，该吹塑成型中空容器有底预成型体为具有多层结构的吹塑成型中空容器有底预成型体，筒体和底部由3层结构组成，该3层结构的最内层和最外层由第1材料构成，中间层由第2材料构成，并且底部中间层的壁厚(tc)比筒体中间层的壁厚(to)薄(tc＜to)。
此外，第2，本发明的上述目的及优点通过一种用于制造吹塑成型中空容器有底预成型体的方法而实现，该方法为制造具有筒体和底部的吹塑成型中空容器有底预成型体的方法，其中，在同一成型工序中将第1材料和第2材料填充到注射成型金属模具的模槽中，筒体和底部的最外层和最内层由第1材料构成，中间层由第2材料构成，在同一成型工序中，按所述顺序连续实施(i)注射第1材料的工序、(ii)同时注射第1材料和第2材料的工序及(iii)注射第1材料的工序。
附图的简要说明
图1为在本发明的方法中使用的多层夹层用热流道系统及预成型体金属模具模槽一部分的模式断面图。
图2为注射第1材料后、注射第2材料所得到的以往具有3层结构预成型体的模式断面图。
图3为注射第1材料后，注射第2材料，最后再次注射第1材料所得到的以往具有3层结构预成型体的模式断面图。
图4为注射第1材料后，注射第2材料，再次填充规定量的第1材料，从预成型体底部到筒体下成为5层结构的以往具有5层结构预成型体的模式断面图。
图5为用本发明的方法制得的具有3层结构的预成型体实施形态的模式断面图。
发明优选的实施方式
以下对本发明进行详细的说明。
[第1材料及第2材料]
在本发明中，第1材料及第2材料使用热塑性树脂，优选芳香族聚酯。
作为芳香族聚酯，优选使用主要二羧酸成分由对苯二甲酸或萘二甲酸构成且主要二元醇成分为乙二醇的均聚酯或共聚酯。
优选地，作为以萘二甲酸为主要二羧酸成分并且以乙二醇为主要二元醇成分的芳香族聚酯，其萘二甲酸优选占全部二羧酸单元的50～100摩尔％，更优选占81～100摩尔％，进一步优选占91～100摩尔％，并且其乙二醇优选占全部二元醇单元的50～100摩尔％，更优选占81～100摩尔％，进一步优选占91～100摩尔％。
优选地，作为以对苯二甲酸为主要二羧酸成分并且以乙二醇为主要二元醇成分的芳香族聚酯，其对苯二甲酸优选占全部二羧酸成分的50～100摩尔％，更优选占81～100摩尔％，进一步优选占91～100摩尔％，并且其乙二醇优选占全部二元醇单元的50～100摩尔％，更优选占81～100摩尔％，进一步优选占91～100摩尔％。
作为乙二醇以外能够共聚的二元醇成分，可以例举的实例包括丙二醇、1，4-丁二醇、1，5-戊二醇、1，6-己二醇、新戊二醇、二乙二醇等脂肪族二元醇；1，4-环己烷二醇等脂环族二元醇；双酚A、双酚A的环氧烷加成物等芳香族二元醇；聚乙二醇、聚1，4-丁二醇等多元醇；间苯二酚、对苯二酚、二羟基联苯、二羟乙氧基苯基芴等芴等。
此外，作为萘二甲酸及对苯二甲酸以外能够共聚的二羧酸成分，可以例举的实例包括间苯二甲酸、叔丁基邻苯二甲酸、二苯氧基乙烷二羧酸等芳香族二羧酸；丁二酸、己二酸、癸二酸等脂肪族二羧酸；联苯二羧酸、二苯醚二羧酸、二苯氧基乙烷二羧酸、甲苯二羧酸、二苯基甲酮二羧酸、二苯硫醚二羧酸、二苯砜二羧酸等。
在以萘二甲酸为主要二羧酸成分的聚酯中，作为能够共聚的二羧酸成分，除上述例示化合物以外，可以共聚对苯二甲酸，此外，在以对苯二甲酸为主要二羧酸成分的聚酯中，作为能够共聚的二羧酸成分，除上述例示化合物外，可以共聚萘二甲酸。
在上述芳香族聚酯中，也可以进一步共聚羟基羧酸或三官能以上的多官能性化合物。
作为能够共聚的羟基羧酸成分，可以例举的实例包括羟基苯甲酸、羟基联苯羧酸等。作为三官能基以上的多官能性化合物，可以例举的实例包括例如甘油、三羟甲基丙烷、季戊四醇、偏苯三酸等。
在不损害所得到的芳香族聚酯理想特性的范围内，可以使用这些部分。
上述芳香族聚酯可以使用以往已知的芳香族聚酯的一般聚合方法制得。作为其一例，可以例举的方法是：一边将甲醇馏去，一边使乙二醇、萘二甲酸二甲酯及根据需要使用的共聚成分进行酯交换反应，其后在减压下进行缩聚反应。进而为了提高所制得的聚萘二甲酸乙二醇酯的极限粘度数，可以进行固相聚合。
此外，在不损害特性的范围内，可以在用于本发明的聚对苯二甲酸乙二醇酯及聚萘二甲酸乙二醇酯中混合使用其他种类的热塑性树脂。此外，根据目的的不同，也可以混合使用各种稳定剂、着色剂、润滑剂、填充剂等。
[有底预成型体]
具有本发明多层结构的吹塑成型中空容器的有底预成型体，其筒体和底部由3层结构组成。3层结构的最外层和最内层由作为同一材料的第1材料构成，并且中间层由与第1材料不同的第2材料构成。
第1材料的原料优选以对苯二甲酸乙二醇酯为主要重复单元的聚酯或以萘二甲酸乙二醇酯为主要重复单元的聚酯，其中特别优选聚对苯二甲酸乙二醇酯及聚萘二甲酸乙二醇酯。
此外，作为第2材料，优选使用由与第1材料相同的原料构成的回收材料。成为第2材料的回收材料是本应废弃的材料。该回收材料的产生过程、处理过程并无限制。作为实例，其包括将生产过程中产生的剩余材料或废弃材料、回收得到的制品等根据需要实施洗涤、粉碎、分选、造粒等各种处理而得到的片状或粒状的回收树脂材料、将上述剩余材料或废弃材料进行降解得到的原料再次经过聚合工序而制造的再生树脂材料、或使分选的剩余材料或废弃材料再次进行聚合反应而得到的再生树脂材料等。
本发明的有机预成型体在结构上的最大特征在于：底部中间层的壁厚(tc)比筒体中间层的壁厚(to)薄(tc＜to)。
由于具有上述结构，即使将机械强度差的回收材料用于中间层，也可以使中空容器自身的机械强度、特别是耐落下冲击性十分理想。
本发明的有底预成型体，优选地，在通过吹塑成型将该有底预成型体制成吹塑成型中空容器时，在从底部到筒体的方向上，其中间层的顶端位于基本上没有被拉伸的部位。
此外，在本发明的有底预成型体中，其中间层优选占10重量％以上，更优选占20～50重量％。
以下对本发明的预成型体的制造方法进行说明。
本发明的制造方法，是在同一成型工序中将第1材料和第2材料填充到注射成型金属模具的模槽中而制造本发明预成型体的方法，在这种情况下，在同一成型工序中，按所述顺序连续实施(i)注射第1材料的工序、(ii)同时注射第1材料和第2材料的工序及(iii)注射第1材料的工序。
用附图的实施状态对本发明的方法进行说明。
图1表示注射成型用金属模具的热流道喷嘴部分及预成型体模槽的一部分。第1材料及第2材料分别通过各自的集流腔，即通过第1材料的集流腔1及第2材料的集流腔2被供给到多重管喷嘴部20。在多重管喷嘴部的顶端有用阀销3可以闭锁流路的阀门，与注射顺序配合可以进行流路的闭锁，能够防止第1材料逆流到第2材料的流路中。多重管喷嘴的结构包括：位于中心部的阀销3，其后的第2材料的流路5，位于最外层的第1材料的流路4。此外，40为浇口部分，50为流道部分，60为喷嘴合流部。该结构是已知的多层夹层成型用热流道系统。在本发明中对该结构并无特别限定。
从该热流道喷嘴部出发，首先配置的是分成3部分的部件组成的模槽。其由模槽本体6、用于形成中空成型体的型芯模槽7、成为中空容器的带有螺纹口部的颈环部8构成，具有与通常注射成型用金属模具相同的结构。第1材料及第2材料从各自的料筒中通过热流道集流腔被注射，在热流道喷嘴部合流后，被填充到模槽中。第1材料、第2材料的填充定时通过料筒中的注射定时进行控制。
如上所述，在本发明的方法中，在同一成型工序中按所述顺序连续实施上述工序(i)、(ii)及(iii)的注射定时是重要的。
为了说明这一点，用图2、图3及图4首先就以往技术的具体例进行说明。
所谓2种材料的夹层成型，一般是在将第1材料填充到模槽中的1次注射后接着进行注射第2材料的2次注射，完成一连串的注射工序。如果以该顺序成型，则如图2所示，在成型体中形成中间层，成为一般称为夹层结构的2种3层结构。A为1次注射形成的表皮层，B为2次注射形成的由第2材料构成的中间层。通过改变1次注射量和2次注射量的比，可以改变第2材料的填充量和由第2材料构成的中间层的顶端位置。但是，由于在这种情况下填充量和中间层的顶端位置有关，因此独立地进行控制是困难的。此外，当使用上述成型方法时，不可避免的现象是：中间层的壁厚分布是顶端薄，在浇口附近达到最大厚度。如本发明所述，当使用机械强度差的回收材料作为第2材料时，在吹塑成型形成的中空容器中，在实际使用方面机械强度的最大问题是底部的落下强度。由于底部的拉伸倍率低，即使使用通常新制造的材料，与被拉伸的筒体比较，也存在着耐冲击强度差的倾向。为此，有必要使用某种方法减少底部附近由第2材料构成的中间层的厚度。如果按上述方法，使用回收材料成型1升的瓶子，作为回收材料的第2材料的填充量可以超过40重量％使用。但是，如果在填充内容物的状态下，进行从1.5m的高度使其落到混凝土面上的落下冲击性评价，则不使用回收材料的瓶子耐落下冲击，而使用回收材料按上述方法成型的瓶子由于落下冲击，其底部产生龟裂，甚至破坏。
此外，当用由第2材料构成的2次注射结束注射过程时，在由上述多重管构成的热流道喷嘴的合流部残留有若干第2材料，与接下来的注射过程中作为1次注射的第1材料混合。在这种情况下，由于回收材料混入到第1材料中，有可能与中空成型体的填充内容物接触，因此中空容器的卫生性成为问题。此外，喷嘴部及溢料面为第2材料，因此有可能产生浇口切割性、拉丝性等生产工序上的问题。
因此，改善注射顺序，进行由第1材料构成的1次注射、接着进行由第2材料构成的2次注射、进而进行由第1材料构成的3次注射。此时注射的图案及所制得成型品的层结构如图3所示。为了降低底部的中间层厚度，使中间层顶端成为筒体上部左右，进而在注射过程终段再次注射第1材料，则达到在喷嘴部及溢料面无第2材料残留。C为3次注射形成的贯入层。在这种情况下，通过用第1材料实施3次注射从而将喷嘴部的第2材料置换，避免了在随后的注射工序中第2材料混入到第1材料中。在一种情况下，为了改善底部机械强度而使第2材料的填充量减少，但底部中间层的壁厚却无法那样变薄。在一种情况下，使中间层的顶端位于筒体上部。如果该中间层的顶端在吹塑成型时位于被拉伸的部位，由于作为回收材料的第2材料与作为新制造的第1材料的拉伸特性不同，因此在所制得的吹塑成型中空容器中，中间层顶端残留有作为拉伸不均的痕迹，因此实用上成为问题。此外，由于减少了第2材料的填充量，因此不适于制备最大量填充回收材料的具有优异特性的中空容器。
鉴于上述课题，如果在上述注射图案中增加3次注射量，则可以在中间层中进而贯入由第1材料构成的层，制得具有5层结构的预成型体。通过调整该3次注射量，可以减少底部的中间层壁厚。此时的注射图案及制得的成型体结构如图4所示。可以发现，使用该方法时，底部由第2材料构成的中间层壁厚有效地减少。但是，如果考虑实际吹塑成型的中空容器和预成型体的位置关系，作为中空容器在落下时最受冲击的部位，底部的边缘部位于预成型体的筒体下方。因此，为了使该筒体下方的中间层的壁厚充分地变薄，有必要填充直到通过3次注射形成的贯入层顶端位置达到预成型体筒体中央附近。因此，由于3次注射量即第1材料填充量增加，因此不适宜最大限度填充由回收材料构成的第2材料。
以下用图5对本发明进行说明。根据本发明的方法，为了兼顾上述回收性即回收材料填充量增加以及中空容器强度，如上所述，在1次注射中注射第1材料后，在2次注射中将第1材料和第2材料同时注射，进而在3次注射中只注射第1材料。这种情况下的注射图案和制得的成型品的构成如图5所示。在这种情况下，优选调整1次注射的注射量，使在从底部到筒体的方向上，由第2材料构成的中间层的顶端位置到达吹塑成型时中空容器上基本上没有被拉伸的部位即颈环部或其附近。当该1次注射量少时，中间层顶端位置成为容器筒体，其位置容易产生由拉伸不均引起的条纹。此外，当1次注射量过多时，由于中间层顶端位置有时甚至达到有底预成型体的开口端部，因此第2材料在最内层露出，有可能与中空成型体中填充的内装物接触。在2次注射中，有必要同时注射第1材料与第2材料。此时，第1材料和第2材料在热流道喷嘴的合流部合流成层状，填充到模槽中。因此，通过使各材料的注射率改变，可以能动地调整由第2材料构成的中间层的壁厚。在本发明中，考虑到希望尽可能增加回收材料的填充量，在2次注射中极力降低第1材料的注射率而提高第2材料的注射率是有效的。但是，在这种情况下，如果急剧减少第1材料的注射，则在成型品表面会产生折皱状的流痕。从防止流痕的观点出发，优选地，2次注射中第1材料的注射率(V21)和第2材料的注射率(V22)的合计注射率(V2)与1次注射的注射率(V1)的关系为V1＝V2。优选地，2次注射中第1材料的注射率(V21)与第2材料的注射率(V22)的关系为0.1＜V21/V22＜1。当1＜V21/V22时，第2材料的填充量依预成型体形状的不同而不同，但10重量％以下的情况是不太理想的。在本发明中，优选第2材料即中间层占10重量％以上。另一方面，当0.1＞V21/V22时，在第1材料的注射基本上急剧减少的同时，第2材料的注射急剧增加。在实际成型机中，要迟于第1材料的注射和第2材料的注射若干时间，或者存在热流道内熔融树脂的压力传播滞后等，因此，即使进行这样急剧的注射率变动，由于仍会产生流痕，因此不适宜实用。优选地，V21/V22满足0.2＜V21/V22＜0.5。
此外，根据本发明，即使使用机械强度差的回收材料，为了获得中空容器自身的机械强度特别是耐落下冲击性，以预成型体筒体(to)与预成型体底部(tc)比较，由第2材料构成的中间层的壁厚必须使tc＜to。如上所述，在通常的夹层成型中tc＞to，因此无法制得作为本发明目的的具有优异机械强度的中空容器。为了实现本发明的效果，需要进行3次注射。由于该3次注射的填充量因预成型体的形状及预成型体吹塑成型所得到的中空容器的形状的不同而相差很大，因此对该填充量并无特别限定。作为其一例，可以调整3次注射的顶端位置，直到达到相当于落下时最受冲击的底部边缘部的位置。如果使用本发明的方法，由于在3次注射顶端，中间层壁厚急剧减少，因此没有必要填充超出必要范围的第1材料，其结果便是可以最大限度填充由回收材料构成的第2材料。如果按照本发明的方法用回收材料成型1升的瓶子，则作为回收材料的第2材料的填充量为28重量％。但是，如果在填充内装物的状态下，使其从1.5m的高度落到混凝土面上进行落下冲击性评价，与没有使用回收材料的瓶子一样，使用回收材料、按本发明的方法成型的瓶子不仅耐落下冲击，而且不产生龟裂破坏。
如以上说明的那样，由本发明所提供的预成型体构成的中空容器，即使与新制造的材料一起使用机械性能差的回收材料，回收材料也不会与作为中空成型体中填充的内容物的食品等接触。此外，根据本发明，在维持中空容器机械强度的情况下，可以增加回收材料的使用量。
Claims (8)
1.一种吹塑成型中空容器的有底预成型体，具有多层结构，筒体和底部由3层结构组成，该3层结构的最内层和最外层由第1材料构成，中间层由第2材料构成，并且底部中间层的壁厚(tc)比筒体中间层的壁厚(to)薄(tc＜to)。
2.根据权利要求1记载的有底预成型体，其中，第1材料和第2材料均为热塑性树脂，并且第2材料主要由回收的第1材料构成。
3.根据权利要求1记载的有底预成型体，其中，第1材料主要由聚对苯二甲酸乙二醇酯或聚2，6-萘二甲酸乙二醇酯构成。
4.根据权利要求1记载的有底预成型体，其中，在通过吹塑成型将该有底预成型体制成吹塑成型中空容器时，在从底部到筒体的方向上，中间层的顶端位于基本上没有被拉伸的部位。
5.根据权利要求1记载的有底预成型体，其中，中间层占10重量％以上。
6.一种制造吹塑成型中空容器的有底预成型体的方法，其为制造具有筒体和底部的吹塑成型中空容器的有底预成型体的方法，其中，在同一成型工序中将第1材料和第2材料填充到注射成型金属模具的模槽中，筒体和底部的最外层和最内层由第1材料构成，中间层由第2材料构成，在同一成型工序中，依次连续实施(i)注射第1材料的工序、(ii)同时注射第1材料和第2材料的工序及(iii)注射第1材料的工序。
7.根据权利要求6的方法，其中，应使注射第1材料的工序(i)及同时注射第1材料和第2材料的工序(ii)满足下式(1)及(2)：
0.5＜V1/V2＜2 (1)
其中，V1为工序(i)的注射率，V2为工序(ii)的注射率；
0.1＜V21/V22＜1 (2)
其中，V21为工序(ii)中第1材料的注射率，V22为工序(ii)中第2材料的注射率。
8.一种吹塑成型中空成型体，其通过对权利要求1的有底预成型体进行吹塑成型而制得。
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| AU2012200320B2 (en) * | 2005-04-28 | 2012-11-15 | Yoshino Kogyosho Co., Ltd. | Synthetic resin bottle having a gradation pattern, and process for injection molding the preform for use in such a bottle |
| JP4771315B2 (ja) * | 2006-08-31 | 2011-09-14 | 株式会社吉野工業所 | 多層ブロー容器 |
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| CH699063B1 (de) * | 2006-10-24 | 2010-01-15 | Alpla Werke | Preform für die Herstellung von biaxial gereckten Kunststoffflaschen und aus dem Preform hergestellte Kunststoffflasche. |
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| RU2570053C2 (ru) * | 2010-04-23 | 2015-12-10 | Мицубиси Гэс Кемикал Компани, Инк. | Многослойный контейнер, пресс-форма для многослойного контейнера и способ изготовления многослойного контейнера |
| JP2012232463A (ja) * | 2011-04-28 | 2012-11-29 | Yoshino Kogyosho Co Ltd | プリフォームの射出成形装置、射出成形方法及び合成樹脂製壜体 |
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| WO2002032650A1 (fr) | 2002-04-25 |
| CA2426276A1 (en) | 2003-04-17 |
| EP1332861A1 (en) | 2003-08-06 |
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