CN85109244A - 共挤出的多层塑料片材和瓶子的套筒标签 - Google Patents
共挤出的多层塑料片材和瓶子的套筒标签 Download PDFInfo
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Abstract
用于各种容器上坚韧的热收缩无皱纹共挤出多层片材套筒标签,它能用超声波,热空气和热合方法封合,但尤其适用于溶剂封合。片材为一种坚韧的表皮层/脆性聚苯乙烯发泡层结构,表皮层由一种聚烯烃,一种作相容性试剂的丁二烯/苯乙烯嵌段共聚物和一种聚苯乙烯组成。相容性试剂提供了适当的粘结性以保持整个标签结构具有表皮层的韧性,而聚烯烃使得表皮层在标签加热收缩时具有所希望的收缩速率和适当收缩性。
Description
本发明涉及一种共挤出的多层塑料片材,它适用于加工成为容器的套筒标签,这种标签坚韧又能很容易用溶剂或超声波、热空气和热合方法快速地封合。本发明尤其涉及一种由聚苯乙烯发泡层和固态表皮层构成的共挤出多层塑料片材。发泡层和表皮层一起挤出。发泡层为套筒内层(紧挨容器一面),表皮层是用由聚烯烃、聚苯乙烯和丁二烯/苯乙烯嵌段共聚物组成的一种可挤出掺合物加工而成的。嵌段共聚物组份使得表皮层和发泡层界面间具有理想的相溶性和粘结性。掺合物中的聚烯烃使表皮层的收缩速率更容易控制,以便能与发泡层的收缩速率相一致。聚烯烃也使得表面层具有较小的收缩力,所以在发泡层底面不会出现皱纹。
因此,本发明涉及的是一种用于玻璃瓶等容器的套筒标签,这种标签由坚韧表皮层和脆性发泡层结构的能热收缩共挤出多层塑料片材制成。这种套筒标签可在容器上成型,例如:用包卷(Wrapping)或者把予先成型好的管状套筒标签从容器下部向上推套的方法成型。这种共挤出多层标签最显著特征是它特别适于用包卷的方法或用溶剂封合(Senling)的方法将标签封合在诸如装饮料或啤酒的玻璃瓶等容器上。
在本发明前,人们已提出过用层压片材作为容器的套筒标签,例如:詹姆斯·格雷彼丁(James Karabedine)在美国专利第3,979,000号和4,069,934号,恩伯(Amberg)等在美国专利第3,760,968号,他们全归属于奥威斯-因力努斯(Owens-Illinois)有限公司。左鲍(Tsubone)等在美国专利第4,463,861号也提出了一种层压片(共挤出的双层片)和一种包卷容器用的能热收缩的套筒标签。这种层压片套筒标签由固态膜和发泡膜构成,固态膜的材质是含苯乙烯残留份大于50%(重量)的聚苯乙烯,发泡膜是由含苯乙烯量大于50%(重量)的聚苯乙烯和/或含量不大于30%(重量)的橡胶组成的。
但这些含有聚苯乙烯层的共挤出多层套筒标签并没有满意的韧性。此外要在容器上热收缩这种含有聚苯乙烯发泡底面的共挤出(表皮层/发泡层)多层标签是很困难的,特别是在不经预热的冷玻璃瓶上要达到无冷皱纹(即在紧靠瓶子的发泡层上不起皱纹)和无表皮皱纹(即在表皮面上不起皱)更难,尤其是在瓶颈、瓶下部这些通常直径变得很小的部位,多层标签的收缩一定要比瓶身部位更多。
本发明的一个目的是提供一种容器用的共挤出塑料多层片套筒标签,这种套筒标签可以用超声波、热空气和热合方法封合,但它特别适宜用溶剂封合。这种片材是由坚韧的表皮层/脆性的聚苯乙烯发泡层构成的,表皮层由一种聚烯烃、一种作为相溶性试剂的丁二烯/苯乙烯嵌段共聚物和一种聚苯乙烯组成。相溶性试剂提供了适当的粘结性以保持整个标签有着表皮层的韧性,而聚烯烃的作用是当标签在容器上热收缩时使得表皮层具有理想的收缩速率和一定的收缩力。
本发明的一个目的是提供一种坚韧无皱纹热收缩的共挤出多层塑料套筒标签,这样标签推荐采用溶剂封合。此种标签由脆性的聚苯乙烯发泡层(紧挨于容器的一层)和表面坚韧的表皮层构成,表皮层由聚烯烃、作相容性试剂的苯乙烯/丁二烯嵌段共聚物和聚苯乙烯组成的一种掺合物加工而成。聚烯烃使得表皮层有着理想的收缩速率和收缩力,以使得热收缩标签不出现皱纹。
从下述的说明书,权利要求和附图将把本发明的这些目的以及其它目的了解的很清楚。
图1,是一个玻璃容器和按本发明制造的热收缩共挤出多层塑料套筒标签的正视图。
图2,是共挤出多层标签围绕图1容器还没有完全包卷好时的透视图。
图3,是一热收缩共挤出多层片套筒标签放大的断面图。
图4,是一个玻璃容器和热收缩共挤出多层塑料标签的透视图,说明热收缩标签。在瓶颈无皱纹。
图5是一段共挤出多层塑料标签断面放大透视图,说明脆性发泡层上有一个小裂缝,尽管接连裂缝处的表皮层被拉伸了,但仍能保持整个标签的韧性未受损失。
本发明提供了一种容器上用的共挤出塑料多层片材套筒标签,它可以用超声波,热空气和热合方法封合,但它尤其适宜于用溶剂封合。这种片材为坚韧的表皮层/脆性的聚苯乙烯发泡层结构。表皮层由一种聚烯烃、一种作相容性试剂的丁二烯/苯乙烯嵌段共聚物和一种聚苯乙烯所组成。相容性试剂提供了一定的粘结性,使得整个标签结构有着表皮层的韧性。聚烯烃使得表皮层在标签加热收缩时具有理想的收缩速率和适当的收缩力。
更详细讲,本发明提供了一种适宜于制成诸容器的容剂封合套筒标签的共挤出多层塑料片材,它也能用超声波,热空气和热合方法封合。这种片材标签由一种发泡聚苯乙烯为套筒内层(紧挨容器的一层)和一层表皮所构成。表皮层通过挤出由聚烯烃、聚苯乙烯和一种作用相容剂组成的掺合物成型的。相溶剂为苯乙烯/丁二烯嵌段共聚物,共聚物中结合的苯乙烯含量约为35到55%(重量),共聚物的数均分子量约为50,000到100,000。加入一定量的聚烯烃使表皮层有更易控制的收缩速率,以便当标签的表皮层受到外热时,表皮层与发泡层的收缩速率更相一致,以免在表皮层外表面出现不希望有的皱纹。当在表皮层外表面受热时聚烯烃也使表皮层只有适当收缩力而不会使发泡层的底面形成皱纹。
再看附图图1表示出一个玻璃容器,容器主体(9),直径较小的容器下部(9a),在容器上既平整又无皱纹的共挤出多层热收缩套筒标签(10)。图上还画出接缝封口(12),它可以用溶剂封合,或用超声波、热空气或热合方法封合。
图2中表示出标签(10)围绕容器(8)未完全包卷好的情况。它以溶剂封合,发泡聚苯乙烯底面涂以如二氯甲烷等活泼溶剂。共挤出标签(10)由一层外表坚韧的表皮聚合物层(15)和一脆性的聚苯乙烯发泡层(20)构成,发泡层的底面(22)为紧挨容器一面,标签的前缘部位(25)和后缘部位(27)。在前缘附近画出的(65)地方,表示瞬间即可固化的聚合物(聚苯乙烯)二氯甲烷粘性溶液在发泡层上的部位,在后缘上的(66)也有这种粘剂溶液存在,当封合后它们的粘结强度将随时间延续变得越来越大。
在待审查的美国专利申请顺序号第555,786号/1983年11月28日由丰米(Fumi)提出的申请中,已提出过溶剂封合方法,它与本申请归属于同一代理人,因此本申请将其引用。
图4中表示了一个有保护层(68)和细颈(68a)的玻璃容器(67)。画出了在容器上有接缝封口(69a)的无皱纹坚韧的热收缩共挤出多层套筒标签(69)。即使在直径较小的容器下部或者瓶颈部位(68a)发生热收缩,标签也无皱纹。
应注意坚韧的表皮层(15)和脆性发泡层(20)之间一定不能粘结太牢,否则将发挥不出表皮层韧性的长处。如在放大的断面图5中所见,为了提高整个标签结构的韧性,表皮层和发泡层的剪切粘合强度应比坚韧表皮层的屈服强度低才行。当如图5上所示箭头方向给制品加力时,发泡层(20)在(70)处出现转微的撕裂,并与表皮层接面拉开,但表皮层耐住撕裂,只发生拉伸,出现轻微的细颈(80),一直拉伸到表皮层的弹性极限时才会断裂。
图3表示一段坚韧表皮层/脆性发泡层共挤出多层片材标签的放大断面。虽然不想用理论加以解释,但假定的标签结构中可用三角形(85)表示在表皮层和发泡层介面附近以及介面上分布的许多苯乙烯的位置。这些很小苯乙烯基因偶然分布于表皮层,而主要广泛分布于发泡层,从而沿着介面形成了能相容粘合的区域和地方,特别是在采用溶剂封合办法进行边缝接口封合更是如此。
要保持标签具有韧性,就需要在表皮层中有一定量的苯乙烯/丁二烯嵌段共聚物作相容性试剂,以使表皮层/发泡层介面有适当的相容性和粘结性,所以要达到一定韧性是个难题。此外要达到如图1和图2那样,标签平整而无皱纹地披复于直径较小的底部和颈部,还有个进行热收缩共挤出多层片套筒标签的工艺问题。
对于未加热(冷)的瓶子,用聚苯乙烯发泡层/聚苯乙烯表皮层构成的那种片材标签是很难而且几乎不可能排除出现冷皱纹的。虽在表皮层中使用聚乙烯可以防止冷皱纹出现,但是往往会引起表皮层皱纹。然而按本发明所指出的办法用聚烯烃/嵌段共聚物/聚苯乙烯掺合物加工成表皮层,则能消除表皮层皱纹现象,所以这种掺合物使得几乎不可能的情况得到解决。
下面对标签收缩的一般要求和用本发明解决的特殊问题加以说明。
实际上,人们要求纵向收缩性稍高(约60%)而希望横向收缩性较低或无收缩性(一般均少于10%左右)。所说的这些值指总的收缩性,即如把样品加热到挤出熔融温度所能达到的收缩量,但实际上人们进行标签收缩过程中极小可能达到如此高的温度。
用无定形聚苯乙烯时,人们可以把发泡样品加热同时测定随温度升高的样品收缩量,通常,样品收缩从tg(发泡材料的软化点)开始,逐渐随温度升高而增加;例如,200°F……3.8%,205°F……6%,210°F……16%,220°F……42%,230°F……50%,250°F……65%。
通常对标签材料尺寸变化的要求比取向(收缩性)要求小。事实上,人们不会或也不可能把样品加热到上述那样高的温度,否则标签将变得很脆弱而出现维护问题,而且当收缩性达到很大时,其收缩力将大为减小,结果重力和离心力都能克服这种收缩力。
至此,已讨论了纵向和横向取向问题。在制造过程中,人们还提出所谓“Z”方向的取向作用(其它方向称“X”和“Y”)。这是由于对挤出的发泡层两边冷却速度差异所造成的。如果表皮层是一种非发泡、导热性很好的材料,当它与相对的发泡材料在相同条件下冷却时,那么片材表皮层一面将比发泡层一面有更大取向作用,当这种样品受热后,样品不仅在纵向和横向有收缩,而且由于表皮层表面收缩的比相对的发泡面要大,所以将会产生向表皮层一面卷曲现象。
事实上,有上述性质的样品,当把它围绕瓶子收缩时,则在容器上边和下边的标签将出现不希望有的脱离容器向外收缩现象,而且由于从外表面一侧施加收缩热,却在标签背面得到热最慢,因此标签将起皱卷拢。注意当外表面受热时,因片材背面与容器接触存在热损失问题,所以容器材料导热性愈好,则得到一种美观受欢迎的标签将愈成问题,也就是讲容器的材质金属比玻璃差,玻璃比塑料差,塑料比纸差。而发泡塑料容器要比不发泡的好。
标签的皱纹或冷皱纹是由于表皮层面比相对的发泡层面取向程度大,而且标签背面得到足够热量开始收缩之前表皮层面已发生收缩的原因所造成的。在加热其间,表皮层和挨着表皮层的基化收缩力将变得很大,足以克服标签中尚未加热部位(即背面)的刚性。一旦让受此种收缩力作用的基片与容器壁密切的接触时,基片很快达到容器壁温度,而在大多数情况下容器壁温度都要比产生收缩所需要的温度低,所以如上述,其结果则出现起皱纹的收缩标签,人们通常把这种缺陷称之为“冷”皱纹。
与之相反的情况是表面层一面在收缩后起皱纹。当标签是一种如用本发明一样的共挤出多层结构片材时,出现这种缺陷的可能性更大。这种缺陷是由于表皮层和发泡层基片向的取向失调造成的。尤其是当标签材料受热发生收缩时,如果表皮层和基片的收缩程度不一致,那么将发生起皱。在这种情况下发泡层将比表面层收缩的更历害,从而导致起皱,出现有皱纹的表面。
由此可见,出现这种称之为“表皮”皱纹的条件与前面造成“冷”皱纹的条件是截然不同的,后者是由于表皮层收缩太大造成了“冷”皱纹,而前者是因表皮层没有充分地收缩而导致“表皮”出现皱纹。实际上造成这些缺陷的原因更复杂,因为这些收缩实际上都与片材中的温度梯度相关的。无论人们采用红外线或热空气加热使标签收缩,标签的外表面往往总比靠容器的底面更热,而且如上所述,容器对热收缩的影响也是由于造成温度梯度和影响温度梯度大小之故。
因为玻璃或取向的塑料容器等形状不尽相同,所以就要求标签有不同的收缩性,同时对刚生产出的热容器可以用联机直接包卷标签而入库过的容器用脱机包卷标签,它们之间温度相差可达100°F以上,因此对标签的性能要求就更高。有种玻璃套筒标签机器装有预热瓶子的装置,标签可在热瓶子上收缩。目前采用一种滚轧标签(rollon lahal)的设想,以降低投资和操作成本,它对标签性能的要求就更高了。
从技术上讲,用共挤出方法制造发泡层时,纵向、横向和“Z”(或通过片材方向)的取向程度是受线速度,片的内外面冷却速度等等许多可变因素所控制的。
“Z”方向的取向程度,主要通过调节在某一特定线速度下的内外面冷却速度加以控制。当采用聚苯乙烯为表皮层聚合物时(无论用通用级或橡胶改性的耐冲击级聚苯乙烯),为了控制“Z”向的取向程度,操作条件都要求很严。如表皮层外面冷却很快将会导致非发泡的表度层有着比发泡层更大的取向。另外,聚苯乙烯表皮层将产生很大的收缩力,因此当再加热时,会倾向于出现冷皱纹。即使优选制造工艺使得表皮层和发泡层收缩性相等,但温度较高的加热源是位于表皮层一侧,它造成的温度梯度将使得聚苯乙烯表皮层具有足够大的收缩力而导致“冷”皱纹出现,尤其是在未经预热的瓶子或容器上收缩时。
为了确保这种含聚苯乙烯表皮层的共挤出片材收缩时发泡层不出现向表皮一面收缩,在制造过程中应对共挤出片材不断进行检验。否则,即在经予热的瓶子上,也会得到有冷皱纹的标签。
本发明通过在表皮层中加入含相容性试剂的聚烯烃,使操作范围大为加宽。
1.随着在表皮层中加入中等或高含量(5到50%重量)的聚烯烃,则表皮层的取向收缩力大为减小,从而减小了标签结构向表皮层一侧卷曲的倾向,消除了产生“冷”皱纹的可能。
2.高含量的聚乙烯(比如30到50%重量)增加了标签耐化学腐蚀性。因为工业上无毒机械润滑油中采用的植物油类化合物对苯乙烯聚合物有着有害的作用,特别是当聚合物在拉伸情况下更历害。
3.当在同样条件处理时,聚烯烃的结晶性会降低聚苯苯烯的取向程度。在用共挤出制造的条件下,人们可同时冷却聚苯乙烯发泡层和聚烯烃/嵌段共聚物的表皮层,而不会使表皮材料发生太大的取向,这除减少收缩力之外,也有助于减少出现“冷”皱纹现象。
4.由于较小的收缩力和表皮取向程度,所以在生产速度较快时,可以采用比单用聚苯乙烯为表皮层情况更高的温度进行加热,以加速标签收缩。
5.辊挤标签(roll stock loblels)发生收缩其横向取向程度较小。有时(特别是用在诸如取向的塑料充(碳酸)气酒瓶时)通用级聚苯乙烯制成的表皮层会出现平行于纵向的裂缝线。所以在任何时候都必须适当平衡横向的取向作用使它既防止出现裂缝但又要不造成横向卷曲。在表皮层掺合物中加入聚烯烃解决了这一问题。
6.应指出,为有助阻挡碎玻璃飞溅可以增加较坚韧的聚烯烃表皮层厚度,因为它比通用级或冲击级的聚苯乙烯表皮层更坚韧。
7.如人们采用溶剂封合方法,那么高含量聚烯烃的使用足以解决由于标签使用技术不正确或发泡材料多变性引起的有关接缝口开裂问题。特别是用在诸如取向的聚对苯二甲酸乙二醇酯充(碳酸)气酒瓶时(这种瓶灌酒后要发生膨胀)。
在表皮层中加入聚乙烯的优点之一是挤出这种片状的标签材料时冷却速度的调节与向表皮层一面卷曲现象之间关系很小。这优点对于防止一般性的“冷”皱纹和非预热瓶子不可避免出现的“冷”皱纹起着重要的作用。
虽然表皮皱纹并不如单用聚苯乙烯为表皮层时那样严重。而且它能够通过含有聚烯烃的掺合物所提供的充分表皮取向程度和减小发泡基材的纵向取向作用加以消除。
若要求收缩速率为20%(或25~40%),那么为使表皮层也能以20%左右速率与基材一同收缩,让表皮层得到充分冷却就很重要。这可以在实验室里对发生20%收缩后的样品检查起皱现象和卷曲量加以验证,如发现严重的表皮起皱(或卷曲)则说明表皮没有得到充分取向。
本技术中所用的嵌段共聚物是一种用阴离子聚合反应制备的苯乙烯/丁二烯嵌段共聚物。它是种热塑橡胶,在室温下呈现硫化弹性体的行为。共聚体中的苯乙烯刚性链段好象起着交链作用以防止聚丁二烯骨架的蠕变。在高温下,这种嵌段共聚物呈现正常的塑性流动。
嵌段共聚物中的丁二烯组份可以用异戌间二烯、或乙烯、丁烯替代。正如从美国壳牌化学公司(Shell Chemical Co.)可买到的Kraton 1102和1107橡胶材料。
从弗尔斯通(Firestone)、阿克隆(Akron)和奥希阿(Ohio)等公司可买到的stereon 840 A和其它Stereon弹性体是更好的丁二烯/苯乙烯嵌段共聚弹性体,这些嵌段共聚物含有35到55%(重量)的结合苯乙烯,并有着约50,000到100,000的数均分子量,Stereon 840A手册中列举了含53%和43%(重量)结合苯乙烯以及60,000到80,000数均分子量的两种嵌段共聚物。
相容性试剂使得表皮和发泡层之间具有适当的粘结量。由于在表皮层中用了相容性试剂使粘结性受到了限制,从而增强了整体标签结构的韧性。相容性试剂就是含35到55%(重量)结合苯乙烯和具有50,000到100,000数均分子量的丁二烯苯乙烯嵌段共聚物。
人们已知道多层片材的挤出技术,例如詹姆斯依·海得(James E·Heider)的美国专利第4,244,900号作过一般性论述,众所周知作热收缩套筒标签的多层片材可以用共挤出方法生产,即同时挤出一层发泡膜(例如聚苯乙烯发泡膜)和一层非发泡固态表皮膜(例如聚苯乙烯膜)。这种制品的发泡膜一面通常要比表皮膜面冷却得更快,所以当把这种制品作各种容器热收缩套筒标签使用时,发泡面要比表皮层面有更大的收缩性。当把制品加热到发泡材料的软化点(tg)左右时(如180°F或200°F直到230°F或250°F),则表皮和发泡层要进行取向并将收缩在容器上。在高速生产操作中,收缩套筒标签常常采用红外线加热源。人们在技术上已知道在容器上加热收缩塑料套筒标签(包括由一种固态聚合物表面层和发泡层共挤出结构的多层套筒标签)的方法和装置。多层标签的固态表皮层厚度可为1/4或1/2到5密耳,发泡层厚为了到20密耳,最好为4到12密耳。
用下述标签整体结构人们已取得很好效果:由40%(重量)高压聚乙烯、40%(重量)的丁二烯/苯乙烯嵌段共聚物(含43%的结合苯乙烯并有80,000的数均分子量)和20%(重量)的聚苯乙烯组成表面层,厚度为2密耳,表皮层粘结在约5密耳厚共挤出的聚苯乙烯发泡层上。在上述标签结构中换成用40%(重量)高密度聚乙烯,20%重量嵌段共聚物和40%聚苯乙烯组成表皮层或者表面层厚度改为1/2密耳。用10%(重量)聚乙烯,10%(重量)嵌段共聚物和80%(重量)聚苯乙烯组成表皮层并用10-1/2密耳的发泡层制成的标签也都取得很好效果。这种坚韧表皮/脆性发泡结构的制品通过加入抗氧剂或稳定剂(包括紫外线吸收剂,受阻胺类光稳定剂,抗氧剂和镍型淬灭剂)防止受热,光和氧引起的降解作用。合适的稳定剂包括以羟酚基本并噻唑为基础的紫外吸收剂,如汽巴-嘉基Ciba-Geigy)公司的Tinuvn 328;受阻胺类光稳定剂包括汽巴-嘉基公司的Tinuvin292;抗氧剂包括阻碍酚类化合物(如Iganox 1010,1076和汽巴-嘉基公司的B225,后者是一种有机磷酸酯和一种阻碍酚混合物)和磷酸镍(如汽巴-嘉基公司的Ir gastab 2002)。
此外,在某些应用中,可以用乙烯/醋酸乙烯酯、乙烯/乙基丙烯酸酯共聚物作为相容性试剂来制造坚韧的共挤出多层标签,其中醋酸乙烯酯或乙基丙酸酯,甲基丙烯酸酯或残留含量与相容性相关,所以一般它们至少含量为10%或12%或15%(重量)。乙烯/醋酸乙烯酯共聚物中的聚乙烯部份起着聚烯烃组份的全部或部份作用。当醋酸乙烯酯、乙基丙烯酸酯或甲基丙烯酸酯含量低于10%或11%时,则乙烯/醋酸乙烯酯,乙烯/乙基丙烯酸酯或乙烯/甲基丙烯酸酯共聚物可以全作为聚烯烃组份。同此在某些情况下利用乙烯/醋酸乙烯酯或乙烯/乙基丙烯酯酯共聚物起聚烯烃和相容性试剂组份的部份或者全部作用能得到一种坚韧的标签,这种标签能既无冷皱纹又无表皮皱纹地热收缩于诸容器上。
典型的乙烯/醋酸乙烯酯或乙基丙烯酯酯的共聚物是那些含有醋酸乙烯酯或乙基丙烯酯酯最低于40%(重量)、而乙烯含量超过约60%(重量)的共聚物,这些典型的共聚物如美国U·S·I化学品公司大量供应的含有醋酸乙烯组份约为18到33%(重量),乙烯组份含量约为67到82%(重量),熔融指数范围为0.4到约125的乙烯/醋酸乙烯酯共聚物。最佳的是为醋酸乙烯酯含量在28到31%(重量)范围,并有约1-3左右熔融指数的共聚物。乙烯和α·β单烯不饱和羧酸烷基酯的典型共聚物是由那些含3~5个碳的丙烯酸和含1~3碳原子的烷基构成的羧酸酯(例如由丙烯酸,甲基丙烯酸或乙基丙烯酸与甲基、乙基或丙基组成的羧酸酯)与乙烯的共聚物。这种共聚中乙烯含量超过75%(重量),单烯不饱和羧酸烷基酯部分含量将小于25%(重量),为最佳。希望这种共聚物有小于约21的熔融指数,最佳熔融指数在1到3范围。最为喜欢使用的共聚物是联合碳化物公司(Union Carbide Co.)大量供应的一种乙烯和乙基丙烯酸酯共聚物。这种共聚物中乙基丙烯酸酯组份约在1.7到22.5%(重量),而乙烯组份约为98.3%到约77.5%(重量),熔融指数约为0.1到21范围。特别合适的共聚物是那些含有乙基丙烯酸酯组成约为11%到22%(重量),乙烯含量约为89%到78%(重量)的共聚物。那些含有乙基丙烯酸酯组成约为15到18%(重量),乙烯含量约为82到85%(重量)的共聚物尤其适合,它们都有约1到3范围的熔融指数。典型的乙烯和α-β单烯不饱和羧酸其聚物也是大量可买到的共聚物,其中羧酸含有3到5个碳,例如:丙烯酸、甲基丙烯酸或乙基丙烯酸,较典型的这种共聚物是那些含有乙烯组份超过约65%(最好是超过80%)而其中α-β单烯不饱和羧酸含量小于约35%(重量)(最好是小于20%重量)的共聚物,这些共聚物最好有约1到5左右的熔融指数。
在表皮和发泡层中所用的材料都可以大量买到,技术熟练的人将容易选取适用材料。聚苯乙烯,一般推荐使用通用级或耐冲击级聚苯乙烯。这种典型聚苯乙烯可以从道化学公司(Dow Chemical Co.)买到(牌号为484),或从科斯登化学公司(Cosden Chemical Co.)买到(牌为550)。适合此目的应用可大量买到的典型聚苯乙烯还包括那些重均分子量超过100,000(例如为240,000到320,000)和熔体流动指数约为1到5左右的产品(ASTM试验标准D12378-70,以ASTM条件G测定)。特别适合的聚苯乙烯约为280,000的重均分子量和约2.0的熔体流动指数。
在新的表皮层聚合体掺混物中、聚烯烃的成份可以采用聚取烯,包括高密度聚乙烯(推荐用)和低密度聚乙烯(密度约为0.910到0.925),也包括线性低密度聚乙烯或者至少含有50%(重量)乙烯的共聚物(例如乙烯/乙基丙烯酸酯、乙烯/醋酸乙烯酯,乙烯/甲基丙酸酯等共聚物)聚烯烃也可以是聚丙烯、聚丁烯或它们的共聚物。
Claims (25)
1、一种适宜于制成诸容器的溶剂封合套筒标签的共挤出多层片材,它也可用超声波、热空气和热合方法封合,本发明特征在于套筒标签的里层(紧挨容器的一层)为发泡聚苯乙烯,而外表皮层是通过挤出一种由聚烯烃、聚苯乙烯和起相溶性试剂作用的苯乙烯/丁二烯嵌段共聚物(共聚物中苯乙烯含量约为35%到55%重量,共聚物的数均分子量约为50,000到100,000)组成的掺合物成型的。使用一定量的相溶性试剂以使得表皮层和发泡层界面间有适当的相溶性和粘结性,从而增强了标签的韧性,加入一定量的聚烯烃使得表皮层在热收缩时能有着与发泡相一致的收缩速率,避免在表皮层外表面出现不希望有的皱纹,使用了聚烯烃也使得在表皮层外表面受热时表皮层能有一个不足以使发泡层底面形成皱纹的收缩力。
2、一种按权利要求1规定的片材,其中掺合物是由约为5~50%(重量)聚烯烃、约为15到25%(重量)的聚苯乙烯和大约5到50%(重量)的相溶性试剂组成的。
3、一种按权利要求2规定的片材,其中聚烯烃为高密度聚乙烯,嵌段共聚物的相溶性试剂约含38到53%(重量)的结合苯乙烯。
4、一种按权利要求1规定的片材,其中掺合物由约40%(重量)的高密度聚乙烯、约20%(重量)的聚苯乙烯和约40%(重量)的苯乙烯/丁二烯嵌段共聚物(约含43%重量的结合苯乙烯)所组成。
5、一种按权利要求3规定的片材,其中掺合物中包括有一种抗氧剂,以防止暴露于热和氧后,嵌段共聚物发生降解。
6、一种按权利要求1规定的片材,其中表皮层中的聚烯烃使得表皮层有一定的收缩速率,从而使整个标签收缩后在表皮层外表面和发泡层底面均无皱纹和缺陷,甚至使得标签的端部收缩也能比整齐包卷在容器主体部位的标签收缩至少大20%。
7、一种按权利要求1规定的片材,其中表皮层中聚烯烃含量约为20到40%(重量)。
8、一种按权利要求7规定的片材,其中聚烯烃是高密度聚乙烯,用量约为30到40%(重量)。
9、一种按权利要求8规定的片材,其中聚乙烯用量约为40%(重量)。
10、一种适合于成型为诸容器套筒标签的共挤多层片材,聚苯乙烯发泡材料适用于作紧靠容器的套筒里层,通过挤出一种掺合物成型得固态表皮层,其外表皮适合于印刷和修饰,这种掺合物是由约5到50%(重量)的聚烯烃、约15到25%(重量)的聚苯乙烯和一定量的相溶性试剂所组成的,相溶性试剂使表皮层和发泡层界面间具有相溶性和所希望的粘结量,以便使标签具有韧性、可封合性和良好封合强度,相溶性试剂为苯乙烯/丁二烯嵌段共聚物,聚烯烃使表面层有着一定收缩速率和收缩性,从而使标签能在容器上热收缩而无皱纹。
11、一种按权利要求10规定的片材,其中嵌段共聚物含量约为5到50%(重量)。
12、一种按权利要求10规定的片材,其中标签是用于玻璃容器上的。
13、一种按权利要求10规定的片材,其中标签是用于玻璃容器上的,同时用二氯甲烷作溶剂封合标签的接口。
14、一种容器和一种共挤出多层片套筒标签,但其中片材按权利要求1规定。
15、一种玻璃容器和在它周围包卷后的共挤出多层片材套筒标签以及封合后的边缝接口,该片材按权利要求1规定。
16、按权利要求10规定的片材,其中标签的边缝接口是用溶剂封合法封合的。
17、一种适合于制成诸容器的溶剂封合套筒标签的共挤出多层片材,它也可用超声波,热空气和热合办法封合,这种片状标签以发泡聚苯乙烯为套筒里层(紧靠容器的一面),而通过挤出一种掺合物成型得外表皮层,掺合物由含2到4个碳原子的烯烃聚合物、聚苯乙烯和能增强烯烃组份相溶性试剂所组成的,相溶性试剂为苯乙烯/丁二烯嵌段共聚物,其中结合苯乙烯含量约为35到55%(重量),它的数均分子量约为50,000到100,000,采用一定量的相容性试剂以使得表皮层和发泡层界面间具有适当的相容性和粘结性从而增强了标签的韧性,使用一定量的烯烃聚合物组份,使得表皮层能在标签受外热时具有与发泡层相一致的收缩速率,从而防止表皮层外表面出现不希望有的皱纹,烯烃聚合物组份也使得表皮层在它外表面受热时有适当收缩力,而不致使发泡层底面出现皱纹。
18、一种按权利要求17规定的片材,其中掺合物中聚烯烃、聚苯乙烯和约为5到50%(重量)相容性试剂所组成,相容性试剂为乙烯/乙基丙烯酸酯共聚物。
19、一种按权利要求17规定的片材,其中掺合物由聚烯烃、聚苯乙烯和一种相容性试剂组成,相容性试剂为乙烯/醋酸乙烯酯共聚物。
20、一种按权利要求17规定的片材,其中掺合物由聚苯乙烯和一种相容性试剂组成,相容性试剂为乙烯/乙基丙烯酸酯或乙烯/醋酸乙烯酯共聚物,相容性试剂同时起着烯烃聚合物作用。
21、一种适合于制成诸容器的热收缩套筒标签的共挤出多层片材,它由发泡聚苯乙烯层作套筒里层(紧靠容器的一面),而通过挤出一种掺合物成型得外表皮层,掺合物由含2到4个碳原子的烯烃聚合物、聚苯乙烯和一种能对烯烃聚合物组份起到增强相容性作用的相容性试剂所组成,相容性试剂为苯乙烯/丁二烯的嵌段共聚物,其中结合苯乙烯含量约为35到55%(重量),数均分子量约为50,000到100,000,使用一定量相容性试剂使得表皮层和发泡层界面间有着适当的相容性和粘结性,因此增强了标签的韧性,一定用量的烯烃聚合物使得表皮层在标签受到外热时能产生与发泡层相一致的收缩速率,以免在表皮层的外表面出现不希望有的皱纹,它的用量也对表皮层外表面受热时使表皮层产生适当收缩力而不足以使发泡层底面出现皱纹。
22、一种按权利要求21规定的片材,其中掺合物由聚烯烃、聚乙烯和约5到50%(重量)的相容性试剂组成,相容性试剂是乙烯/乙基丙烯酸酯共聚物。
23、一种按权利要求21规定的片材,其中掺混物由聚烯烃、聚苯乙烯和一种相容性试剂组成,相容性试剂为乙烯/醋酸乙烯酯共聚物。
24、一种按权利要求21规定的片材,其中掺合物由聚苯乙烯和一种相容性试剂组成,相容性试剂为乙烯/乙基丙烯酸酯或乙烯/醋酸乙烯酯或乙烯/甲基丙烯酸酯共聚物,相容性试剂也起着聚烯烃组份的作用。
25、一种按权利要求21规定的片材,其中相容性试剂为乙烯/甲基丙烯酸酯共聚物。
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-
1985
- 1985-01-14 US US06/691,250 patent/US4626455A/en not_active Expired - Lifetime
- 1985-11-06 IE IE2770/85A patent/IE56644B1/xx unknown
- 1985-11-11 NZ NZ214144A patent/NZ214144A/xx unknown
- 1985-11-15 CA CA000495410A patent/CA1237862A/en not_active Expired
- 1985-11-18 IN IN920/MAS/85A patent/IN166648B/en unknown
- 1985-11-19 ZA ZA858859A patent/ZA858859B/xx unknown
- 1985-12-12 AU AU51134/85A patent/AU574249B2/en not_active Expired
- 1985-12-18 KR KR1019850009553A patent/KR900003350B1/ko not_active IP Right Cessation
- 1985-12-19 CN CN85109244.6A patent/CN1005769B/zh not_active Expired
- 1985-12-20 NO NO855237A patent/NO855237L/no unknown
- 1985-12-27 MX MX1114A patent/MX162579A/es unknown
-
1986
- 1986-01-10 PT PT81821A patent/PT81821B/pt not_active IP Right Cessation
- 1986-01-10 GR GR860064A patent/GR860064B/el unknown
- 1986-01-13 EP EP86300232A patent/EP0191550B1/en not_active Expired
- 1986-01-13 AT AT86300232T patent/ATE37838T1/de not_active IP Right Cessation
- 1986-01-13 FI FI860151A patent/FI860151A/fi not_active Application Discontinuation
- 1986-01-13 ES ES550813A patent/ES8701609A1/es not_active Expired
- 1986-01-13 DE DE8686300232T patent/DE3660895D1/de not_active Expired
- 1986-01-13 DK DK14586A patent/DK14586A/da not_active Application Discontinuation
- 1986-01-14 JP JP61004461A patent/JPS61164825A/ja active Granted
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105189112A (zh) * | 2013-03-15 | 2015-12-23 | 艾利丹尼森公司 | 层压泡沫绝热标签 |
CN109080228A (zh) * | 2018-08-10 | 2018-12-25 | 深圳市通产丽星股份有限公司 | 挤出管及其制备方法 |
CN109080228B (zh) * | 2018-08-10 | 2020-11-13 | 深圳市通产丽星股份有限公司 | 挤出管及其制备方法 |
CN109470769A (zh) * | 2018-09-30 | 2019-03-15 | 中国建筑科学研究院有限公司 | 一种超声反射法检测套筒灌浆饱满度的方法及系统 |
Also Published As
Publication number | Publication date |
---|---|
KR900003350B1 (ko) | 1990-05-16 |
AU574249B2 (en) | 1988-06-30 |
ES550813A0 (es) | 1986-12-01 |
GR860064B (en) | 1986-04-29 |
NO855237L (no) | 1986-07-15 |
CA1237862A (en) | 1988-06-14 |
NZ214144A (en) | 1988-09-29 |
FI860151A (fi) | 1986-07-15 |
ATE37838T1 (de) | 1988-10-15 |
MX162579A (es) | 1991-05-27 |
JPS61164825A (ja) | 1986-07-25 |
US4626455A (en) | 1986-12-02 |
KR860005697A (ko) | 1986-08-11 |
ES8701609A1 (es) | 1986-12-01 |
FI860151A0 (fi) | 1986-01-13 |
ZA858859B (en) | 1986-08-27 |
AU5113485A (en) | 1986-07-17 |
CN1005769B (zh) | 1989-11-15 |
IE852770L (en) | 1986-07-14 |
DK14586D0 (da) | 1986-01-13 |
IE56644B1 (en) | 1991-10-23 |
EP0191550B1 (en) | 1988-10-12 |
IN166648B (zh) | 1990-06-30 |
PT81821B (pt) | 1987-11-30 |
EP0191550A1 (en) | 1986-08-20 |
JPH021664B2 (zh) | 1990-01-12 |
DK14586A (da) | 1986-07-15 |
PT81821A (en) | 1986-02-01 |
DE3660895D1 (en) | 1988-11-17 |
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