CN1020689C - 层压的金属板及其制造工艺 - Google Patents
层压的金属板及其制造工艺 Download PDFInfo
- Publication number
- CN1020689C CN1020689C CN88107081A CN88107081A CN1020689C CN 1020689 C CN1020689 C CN 1020689C CN 88107081 A CN88107081 A CN 88107081A CN 88107081 A CN88107081 A CN 88107081A CN 1020689 C CN1020689 C CN 1020689C
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- China
- Prior art keywords
- temperature
- polyester
- metallic plate
- internal layer
- described technology
- 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.)
- Expired - Fee Related
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- Laminated Bodies (AREA)
Abstract
一种用同时层压法生产包括聚合物/金属/聚合物层压金属板的工艺,以及此种工艺生产的层压金属板。它包括:(i)在金属板表面上同时层压分内外两层的复合聚酯膜,内层为软化温度低于200℃而熔点介于150至200℃之间的非晶线性聚酯,外层为结晶度大于30%而熔点高于250℃的二轴取向线性聚酯,金属板预加热到使内层软化(最好是熔化)而粘合在板上,但外层不熔化;(ii)将层压制品重新加热,使聚合物膜粘接在板上而外层不熔化。此种层压制品用于制造容器或其各种部件。
Description
本发明涉及一种生产层压金属板的工艺,同时涉及用此种工艺生产的层压金属板。
将聚合物材料层压在金属带之类的金属板上,是一种人所共知而文献众多的技术。制成的层压制品有许多用途,如制造食品和饮料容器以及喷雾器用的罐子筒体和罐子顶盖。
为了使金属板具有良好的抗腐蚀性能,金属板的涂层常采用聚酯涂层。通常试图用结晶状的具有取向结构的聚酯树脂作为金属板的涂层,因为此种聚酯膜对氧气、水份和蒸汽的渗透性小。但是,人们发现,将此种结晶状的二轴取向聚酯膜粘合在金属板上是不容易的。
这一问题的一种解决办法是,利用需要将金属板加热到高温从而至少熔化部分二轴取向聚酯的工艺条件,将二轴取向聚酯层压到金属板上。此种方案被包括在例如GB759876和GB2123746中。但是,虽然这种解决办法具有一定的优点,但它取决于层压期间金属带温度的精细控制和用耐极高温材料制作的层压轧辊,这种极高温是为了将二轴取向的聚对苯二甲酸乙二醇酯膜层压到金属带上所必需的。
另一种解决办法是在结晶状聚酯层和粘合该聚酯层的金属板之间提供一层中间粘合剂。这种解决问题的办法公开在例如GB2164899中,它要求为了涂敷聚酯树脂膜而在金属板上涂敷环氧树脂粘合剂。这种办法允许层压工艺在较低的层压温度下完成,但产生一层在深冲操作中可成形性相当差的涂层,并且对于解决上述问题来说是一种相当费钱的方法。
同样,GB1501353说明了一种聚酯、α烯烃共聚物和环氧化合物的混合物,用以配制一种适合于将热塑性树脂层压到金属衬底上的粘合剂。GB2055687说明了一种利用一层粘合剂将二轴取向的聚酯膜热粘接到金属板上而形成的层压制品,这层粘合剂是由包括一种高熔点聚酯和一种低熔点聚酯的聚合物混合体做成的。聚酯的混合物可以包括聚烯烃树脂。
上述专利没有一个涉及到聚酯-金属层压制品制成的深冲成形的罐头筒中产生的问题。
常规的粘合剂可以用来粘接金属板和聚酯膜。例如,以异氰酸盐为基的粘合剂可以在聚酯膜和金属板被引入层压辊隙中接触之前涂在聚酯膜或金属板上。
实际上,如果人们企图用按照GB2123746和GB2164899做成的层压制品来制造罐头筒,通常采用的方法是将直径189mm的圆盘深冲成形为高100mm而直径为65mm的罐头筒(在罐头工业中广泛采用的规格),则此时观察到聚酯涂层的严重破裂,导致金属涂层的显著损坏。结果是成品容器装了食品后的储存寿命大为缩短,以致此种容器从商业观点看是不能接受的。深冲过程中涂层的破裂是成形工艺中层压取向膜的延展超过其拉伸极限而导致取向聚酯断裂的结果。这种现象影响GB2123746和GB2164899中说明的取向聚酯涂层,也影响那些用其它不注意涂层抗拉性能的技术所生产和层压的取向聚酯涂层。
GB1566422中也说明了聚酯在金属衬底上的层压方法。
这一专利说明书指出,其中说明的层压制品适用于采用深冲工艺。但是,在GB1566422中说明的形成层压制品所用的聚酯是一些类别非常特殊的聚酯,它们的固有粘度为1.2至1.8,在层压膜中的结晶度为30%或更小。这种特殊类别的聚酯的固有粘度范围排除了常规的商售聚对苯二甲酸乙二醇酯均质聚合物材料,如二轴取向的聚对苯二甲酸乙二醇酯,而通常当需要使金属板具有良好的抗腐蚀性能时,由于这种二轴取向的聚酯对氧气、水份和蒸汽的渗透性很低,因而常将它选作金属板的层压材料。
本发明的目的是提供一种从常规的商售二轴取向聚酯材料生产聚合物/金属层压制品的工艺,它不需要利用高温来使聚酯材料加热层压到金属板上,而能得到更好的合成层压制品,其性能适于用深冲工艺成形为罐头筒或容器。
按照本发明的第一个方面,本发明提供一种通过同时层压的方法生产聚合物/金属/聚合物层压制品的工艺,该工艺包括:
(ⅰ)在金属板的每个主要表面上同时层压一层复合的聚酯膜(A),它包括一个内层(A1)和一个外层(A2),内层(A1)为软化温度(Ts-A1)低于200℃而熔点(Tm-A1)高于150℃但低于250℃的基本上为非结晶状的线性聚
酯,外层(A2)为结晶度大于30%而其熔点(Tm-A2)高于250℃的二轴取向的线性聚酯,金属板已被加热到高于内层(A1)聚酯的软化温度(Ts-A1)的温度T1,T1最好高于内层(A1)聚酯的熔点(Tm-A1),从而使内层(A1)软化,最好是熔化,并由此粘合在金属板上,但T1低于当外层(A2)的外表面与温度为T1的金属带相接触时会熔化的温度(Tm-A2)。
(ⅱ)将合成的层压制品重新加热到温度T2,该温度要能足以使聚合物膜(A1)与金属板的相应表面相互作用并粘接在其上面,而外层(A2)的外表面仍然低于温度(Tm-A2)。
按照本发明的第二个方面,本发明提供一种在其每一个主要表面上粘合了聚合物膜的层压金属板,聚合物膜是通过同时热层压法粘合到金属板上的,粘合到金属板的每个主要表面上的聚合物膜是一种复合的聚酯膜(A),它包括一个内层(A1)和一个外层(A2),内层(A1)为软化温度低于200℃而熔点高于150℃但低于250℃的基本上为非结晶状的线性聚酯,外层(A2)为熔点高于250℃的二轴取向的线性聚酯。
最好每一层复合聚酯膜(A)是一种用互挤法制备的膜。
本发明的层压工艺分几个阶段完成,在第一阶段,金属被预加热到高于内层(A1)聚酯的软化温度(Ts-A1)的温度T1,T1最好高于内层(A1)聚酯的熔点(Tm-A1),但T1低于当外层(A2)的外表面与温度为T1的金属带相接触时会熔化的温度(Tm-A2)。温度T1通常为120至260℃最好为200至250℃。
在第二阶段,聚酯膜和金属被一起带入层压辊隙,从而形成紧密均匀而没有皱纹的接触。在这一阶段,接触层为非晶态聚酯的内层(A1)、金属,而在相对的金属面上为另一层聚酯膜(A)的内层(A1)。
在第三阶段,重新加热合成的层压制品,最好采用对金属芯进行感应加热的方法,从250℃加热到这样选定的温度,使得二轴取向聚酯的外层(A2)的外表面保持低于二轴取向聚酯的熔点(Tm-A2),从而控制聚酯膜(A)的二轴取向层(A2)的熔化程度。
虽然聚酯膜(A)的外表面保持低于它的熔点,但是随着金属芯温度高于该聚酯的熔点,在金属与每一个内聚酯层(A1)之间产生快速的相互作用。为了实现这种相互作用,层压制品在约250℃以上保持1至30秒,然后便层压制品冷却到约200℃的温度,再用水迅速而均匀地骤冷。由于在骤冷前使聚酯层冷却到200℃或以下,聚酯膜起泡的危险被减到了最小。此外,在聚酯可以显著地重结晶以前,层压制品必须骤冷。聚对苯二甲酸乙二醇酯的结晶率在约160至180℃达到最大值;因此,在约200℃的温度对用聚对苯二甲酸乙二醇酯涂层制成的层压制品骤冷是适当的。
我们已经发现,如果二轴取向的聚酯膜(A)的外表面保持低于它们的熔点,就可以保存二轴取向的聚酯膜如聚对苯二甲酸乙二醇酯的优异性能的足够部分。我们也已发现,外层(A2)中残余部分的非晶态的(熔化的)和二轴取向的(非熔化的)聚酯控制涂层的拉伸性能和深冲操作中的可成形性。保存的二轴取向的量与深冲性能成相反关系,必须加以控制,以配合所希望的成形要求。
后层压区中的温度可以变化。以控制性能,特别是聚酯涂层中所希望的可成形性。如果使用感应加热来重新加热层压辊隙下游的层压制品,那末可以十分容易地实现这种控制。最好可以使用一个合适的高温计来鉴别聚酯的温度,例如用一个在7.8微米处工作的单频率器件,聚酯在7.8微米处具有最佳的发射能力。或者是,可以使用能辨别从二轴取向到结晶状非取向或非晶态的聚酯的变化的器件,以指示聚酯膜的状态(例如,用X射线衍射仪)。
在层压过程之前金属板应当加热到的准确温度T1取决于待层压的聚酯膜的厚度,也取决于该聚酯膜的化学性质,对于双金属挤压的二轴取向聚对苯二甲酸乙二醇酯来说,140℃至160℃的温度是合适的。
用于重新加热层压辊隙下游的层压制品的温度T2通常处于250至270℃的范围,所采用的准确温度将取决于层压制品骤冷之前的停顿时间和聚酯膜涂层与金属之间的相对质量。高于270℃的温度导致完全熔化聚对苯二甲酸乙二醇酯膜,导致二轴取向及其有关性能的破坏。上述范围的下端温度取决于这样一种要求,即在将层压制品加热到所需温度的极短时间内在金属板和粘合于其上的聚合物膜
之间获得满意的粘接强度。商品生产通常要求的停顿时间仅约2秒钟。
涂敷聚合物膜的金属衬底通常为金属带形式,它们一般是钢或铝或其合金,通常为包装工业中使用的钢或铝基产品。
厚度范围通常对钢为0.05mm至0.4mm,对铝为0.02mm至0.4mm。
钢可以镀锡,最好经过常规的铬处理纯化,或者换一种形式,可以是镀镍或镀锌的钢,黑钢板或磷酸盐处理的黑钢板,后者最好在磷酸盐处理后用铬酸盐漂洗。
最佳的钢成品为有一层金属铬和一层氧化铬的电解镀铬钢(ECCS)。使用这种钢,金属铬和氧化铬的含量可以广泛变化。通常,金属铬的含量范围为0.01至0.20g/m2,而氧化铬的范围为0.005至0.05g/m2。ECCS通常是从含有含硫催化剂或含氟催化剂的沉积体系中得到的。
金属板或金属带的每一面都涂敷一层复合的聚酯膜(A),聚酯膜最好在涂敷到金属板或金属带之前是通过互挤法和取向处理而制备成的。复合的聚酯膜(A)包括一个较薄的内层(A1)和一个较厚的外层(A2),内层(A1)为软化温度低于200℃而熔点高于150℃但低于250℃的基本上为非结晶状的聚酯,外层(A2)为结晶度大于30%而熔点高于250℃的二轴取向的线性聚酯。
高结晶度的外层(A2)最好是聚对苯二甲酸乙二醇酯。内层(A1)最好是线性共聚酯,例如约80摩尔%的对苯二甲酸乙二醇酯和20摩尔%的异苯二甲酸亚乙酯的非晶共聚物。对苯二甲酸和两种醇如乙二醇和环己烷-二甲醇的共聚酯也适合于用作内层(A1)。
外层(A2)中的二轴取向聚酯通常具有大于30%的结晶度,最好为40至50%。
聚酯树脂的结晶度可以用如GB1566422中说明的X射线衍射技术测量,或者应用下列关系式从密度的测量求得:
Vc=(P-Pa)·(Pc-Pa)1
式中Vc=体积百分率结晶度
P=试样密度
Pa=非晶物质的密度
Pc=结晶物质的密度
P可以利用氯化锌/水或正庚烷/四氯化碳混合物在密度柱中测量。
用作外层的二轴取向聚酯膜可以具有一个取向程度的范围,并可通过在高于聚合物的玻璃态转变温度的温度下沿向前方向以2.2至3.8倍压延非晶态挤压聚合物的方法来形成,同样可以以2.2至4.2倍沿横向压延,通常取2.2×2.2至3.0×3.0倍。在深冲的金属容器中使用层压涂层的场合,取向最好限制在沿前方和横向以约2.5倍压延。
热凝固温度通常为200至220℃,最好为210至220℃。较低的热凝固温度一般会增大在重新加热时已取向膜的收缩趋势。
通常内层(A1)应当是连续的,并具有约2至3微米的典型厚度。外聚酯层(A2)对内聚酯层(A1)的厚度之比最好为12至3,组合层的总厚度最好为12至25微米。
如果需要,一或多层聚酯可以包含一种无机防粘剂,如粒径为0.5至5微米的合成氧化硅。
外聚酯层(A2)可以任意地包含一定比例的内层(A1)所用的聚酯,通常为重量的0.5至10%。这些材料可以通过在制膜期间将双金属挤压的聚酯膜边角料加入到PET(聚对苯二甲酸二乙醇酯)挤压机中去而得到。这种外加聚酯的存在改善了聚酯膜的可成形性。
同样,如果需要,外聚酯层(A2)可以加入二氧化钛之类常规颜料。
内聚酯层(A1)的主要功用是在低于结晶状外聚酯层(A2)的熔点以下的温度下加热密封到金属表面上的。
重要的是,如果内层在其熔点以上粘接,则这一层必须在聚酯膜取向和热凝固之后保持其非晶态性质。
本发明特别可取的方面是在涂敷聚酯膜之前金属温度采用200℃至250℃的范围,采用二轴取向的聚对苯二甲酸乙二醇酯膜而其取向是通过沿两个方向以一个约2.2×2.2至3.0×3.0倍压延而形成的,以及在涂敷聚酯膜之后采用感应加热对层压制品进行再加热并在涂层(A2)的二轴取向部分内控制熔化程度。
在本说明书的全部范围内,固有粘度是在浓度为5g/L的O-氧苯酚溶液内在25℃测量的。
现在给出下面的例子,用以进一步说明本发明。
例子1和2(作比较用)
在ECCS金属带的每一面上层压了二轴取向的聚对苯二甲酸乙二醇酯膜的层压制品是按照GB2123746的说明制备的,制备层压制品所用的材料的详细名称列于表1。当用于制备罐头筒或罐顶时这些层压制品的性能示于表3(例6和7)。
例子3至5
聚合物/金属/聚合物层压制品是在如附图9或10中示意说明的设备中用层压工艺制备的。金属板M用加热器1预加热到适当的温度T1。温度T1通常位于120至260℃范围内。聚酯膜A从进料辊2和4送入,被层压到层压辊6、8之间的预加热金属板的相对两面上,层压辊6、8的直径通常为100-400mm。层压过程通常在层压辊之间用每米200-400牛顿的辊隙力完成。
在层压辊隙中,在金属板和聚合物膜之间建立起了紧密均匀而没有皱纹的接触。在层压辊的下游,合成的层压制品被重新加热(最好利用感应加热器10)到温度T2,在这一温度下聚合物膜(A)将与金属板相互作用并粘接于其上。温度T2通常在250至270℃范围内,金属聚合物层压制品在温度T2或低于T2的温度(通常高于200℃)保持一个短时间,通常不多于2秒,而后用水快速而均匀地骤冷到低于聚酯膜(A)的玻璃态转变温度。骤冷可以用任何常规的方式完成,但通常可以如图9中所示使层压制品通过水桶12来完成,或者如图10中所示使层压制品通过冷淬水帘14来完成。
通常,图9中举例说明的以垂直方式完成层压过程的工艺是最好的。金属带垂直运动通过层压阶段,可以提高骤冷速率,并使骤冷更好更均匀。
图9也表示用图9的设备举例说明的工艺中得到的典型的温度分布示意图。
表1举出了被层压到金属带中的聚合物类型及每层的厚度。例子1和2是作为比较而给出的。这些层压制品是采用如GB2123746中说明的工艺而制得的。例子3至5中所说明的类型的层压制品是采用本发明的工艺在表2列举的条件下制得的。(见表)
表1的说明
金属:罐顶用的厚0.21mm的ECCS和冲压成形的罐头筒用的厚0.18mm的ECCS。
聚酯A:在例子3至5中,内层(A1)的聚酯为非结晶状(即非晶态)聚酯,它是对苯二甲酸乙二醇酯(约80摩尔%)和异苯二甲酸亚乙酯(约20摩尔%)的共聚物。聚酯的软化温度为约140℃,聚酯的熔点为210℃。聚酯的固有粘度为0.6至0.7。
二轴PET(Ⅰ):代表具有约3.2×3.2取向程度和约45%结晶度及约260℃熔点的二轴取向聚对苯二甲酸乙二醇酯。
二轴PET(Ⅱ):代表具有约2.5×2.5取向程度和约50%结晶度及约260℃熔点的二轴取向聚对苯二甲酸乙二醇酯。
二轴PET(Ⅲ):代表由5%的80∶20摩尔%的对苯二甲酸乙二醇酯和异苯二甲酸亚乙酯的共聚物组成的二轴取向聚对苯二甲酸乙二醇酯。该聚合物的取向程度约为3.2×3.2,结晶度约为50%,熔点约为260℃。(见表)
例子6至15的金属/聚合物层压制品被制成容器和罐子的不同部件,如易拉罐和气溶胶罐顶盖或饮料罐顶盖。附图中图2至图8例示了用本发明的金属/聚合物层压制品可以制成的典型产品的形状,这些图举例说明了易开食品罐顶盖或非易开食品罐顶盖,易拉罐和部分压平罐壁的罐头筒,易开饮料罐顶盖,喷雾器杯,喷雾器锥形筒和喷雾器圆盖。
例子6至15的层压制品在成形为易拉罐或喷雾器/饮料罐顶盖之后的性能为产品的各种试验所证实。结果示于表3。
成形时的性能
当层压制品成形为食品罐(直径65mm高100mm的易拉罐)、喷雾器顶盖部件和饮料罐顶盖之后,对聚对苯二甲酸乙二醇酯涂层的有效范围进行了监控。用目测法和在铜的酸溶液中浸泡两分钟而后检查沉积在暴露的金属面积上的铜的方法评价了有效范围。结果示于表3中冠有“成形”的两行。
蒸馏时的性能
用本层压制品制成的罐头筒装满了PH为4.3%的柠檬酸(0.65%)、氯化钠(1.0%)和苹果酸(0.42%)溶液,在罐头筒上密封了顶盖,在121℃蒸馏1小时,冷却罐头筒,打开并检查聚合物膜的状况。结果示于表3中冠有“蒸馏”的一行。
XRD相对峰值高度(见表2)
在X射线衍射仪中放置二轴取向的膜或层压制品。当平面试样暴露于基本上单色的X射线束时,用合适的探测器测量计数率。试样和探测器相对于X射线束联机转动,保持这样的几何形状,使得试样和X射线束之间的角度(θ)与探测器和X射线束之间的角度保持1∶2的比例,如标准的粉末衍射扫描中那样。这些装置在平行于试样表面的平面上产生信息。
在二轴取向的PET中,(1,0,0)平面在θ=13°给出高的计数率,但是在非晶态的PET中不存在这一峰值。层压制品和原始聚酯膜的θ=13°峰值高度之比与残留取向量有关。表2中的相对XRD(X射线衍射)峰值高度为层压制品PET涂层和相应的游离膜在θ=13°的计数率之比。
表3中给出的结果表示,按照本发明所述的层压制品可以满意地用于浅冲部件和深冲部件(见例子8至15)。
由例子10、12、14例示的在本发明工艺的最佳工艺条件下制备的层压制品很容易制成性能合格的浅冲部件和深冲部件,它们不产生防腐蚀层的损坏。相反,由例子6和7例示的先有技术GB2123746的层压聚酯当层压制品深度冲压时受到损坏。GB2123746的聚酯在有限的伸长后就断裂了,而当制造深冲罐头筒时很容易超越这一限度,结果聚酯涂层断裂,金属板抗腐蚀的防护作用受到损坏。
表2和表3中的例子10、12、14说明了按照本发明所述的最佳工艺条件。这些例子中所获得的层压制品的性能与例子9、13中获得的性能的比较表明,在层压过程之前使用低至150℃的金属温度可能造成在成形和蒸馏后聚酯膜在金属板上粘合不良。在膜加到金属之前的最佳金属温度为200-250℃,低于外层(A2)中PET的熔点。
例子15说明,如果重新加热的条件(如温度)高到导致聚酯涂层完全熔化,涂层在蒸馏时变成不透明,并被认为不合格。(见表)
表1 金属聚合物层压制品的成分
例子 A2层 A1层 A1层 A2层
1 二轴PET(Ⅰ) - 金 - 二轴PET(Ⅰ)
(12μ) - 属 (12μ)
2 二轴PET(Ⅰ) I E - 二轴PET(I)
(16μ) C (16μ)
3 二轴PET(I) 聚酯A C 聚酯A 二轴PET(I)
(12μ) (3μ) S (3μ) (12μ)
4 二轴PET(I) 聚酯A 金 聚酯A 二轴PET(Ⅱ)
(12μ) (3μ) 属 (3μ) (12μ)
5 二轴PET(Ⅲ) 聚酯A 带 聚酯A 二轴PET(Ⅲ)
(12μ) (3μ) (3μ) (12μ)
表2
例子 膜的类型 金属温度 层压制品重新加热 层压制品XRD
T1(℃) 技术 近似温度T2(℃) 相对峰值高度 实际高度
6 如例1 280 - - 0.3 2000
7 如例2 280 - - 0.4 2400
8 如例3 150 感应 240 0.7 5000
9 如例3 150 感应 255 0.2 1400
10 如例3 220 感应 255 0.2 1400
11 如例4 220 感应 240 0.6 4200
12 如例4 220 感应 255 0.2 1400
13 如例4 150 感应 255 0.2 1400
14 如例5 220 感应 255 - -
15 如例3 220 红外 270 0.1 700
表3 层压制品性能
例子 易拉罐 喷雾器/饮料罐顶盖
成形 蒸馏 成形
6 罐壁顶部涂层开裂 涂层开裂区发生腐蚀 满意
7 同上 同上 满意
8 同上 同上,而且涂层从罐底脱落 满意
9 满意 涂层从罐底脱落 满意
10 满意 满意 满意
11 罐壁顶部涂层发生少许开裂 涂层开裂区发生少许腐蚀 满意
12 满意 满意 满意
13 满意 涂层从罐底脱落 满意
14 满意 满意 -
15 满意 变红色 满意
Claims (19)
1、一种通过同时层压的方法生产包括聚合物/金属/聚合物层压的金属板的工艺,该工艺包括:
(i)在金属板的每个主要表面上同时层压一层复合的聚酯膜(A),它包括一个内层(A1)和一个外层(A2),内层(A1)为软化温度(Ts-A1)低于200℃而熔点(Tm-Al)高于150℃但低于250℃的基本上为非结晶状的线性聚酯,外层(A2)为结晶度大于30%而其熔点(Tm-A2)高于250℃的二轴取向的线性聚酯,金属板已被加热到高于内层(A1)聚酯的软化温度(Ts-A1)的温度T1,T1最好高于内层(A1)聚酯的熔点(Tm-Al),从而使内层(A1)软化,最好是熔化,并由此粘合在金属板上,但T1低于当外层(A2)的外表面与温度为T1的金属带相接触时会熔化的温度(Tm-A2);
(ii)将合成的层压制品重新加热到温度T2,该温度要能足以使聚合物膜(A1)与金属板的相应表面相互作用并粘接在其上面,而外层(A2)的外表面仍然低于温度(Tm-A2)。
2、一种按照权利要求1所述的工艺,其特征在于,温度T1为120至260℃。
3、一种按照权利要求2所述的工艺,其特征在于,温度T1为200至250℃。
4、一种按照权利要求1所述的工艺,其中层压制品用感应加热方法重新加热。
5、一种按照上述权利要求1中所述的工艺,其特征在于,温度T2为250至270℃。
6、一种按照权利要求5所述的工艺,其特征在于,层压制品被加热到250至270℃范围的温度,而后在骤冷前在200℃以上至少保持1秒钟。
7、一种按照权利要求6所述的工艺,其特征在于,层压制品被加热到250℃的温度,而后在骤冷前在240℃以上保持2秒钟。
8、一种按照权利要求6所述的工艺,其特征在于,层压制品被迅速而均匀地骤冷,最好是通过浸在水桶中或水沿制品带骤冷。
9、一种按照上述权利要求中任何一项所述的工艺,其特征在于内层(A1)的聚酯为对苯二甲酸乙二醇酯和异苯二甲酸亚乙酯的共聚物,或者是由对苯二甲酸和两种醇(通常为乙二醇和环己烷-二甲醇)组成的共聚物。
10、一种按照权利要求1至8中任一项所述的工艺,其特征在于,内层(A1)的聚脂为对苯二甲酸乙二醇酯和异苯二甲酸亚乙酯的共聚物,对苯二甲酸乙二醇酯与异苯二甲酸亚乙酯的摩尔比为80∶20。
11、一种按照上述权利要求1至8中任何一项所述的工艺,其特征在于,外层(A2)为二轴取向的聚对苯二甲酸乙二醇酯。
12、一种按照权利要求1至8中任一项所述的工艺,其特征在于,外层(A2)为二轴取向的聚对苯二甲酸乙二醇酯,并具有40至50%的结晶度。
13、一种按照上述权利要求1至8中任何一项所述的工艺,其特征在于,金属板为镀有一层金属铬和一层氧化铬的电解镀铬钢。
14、一种在其每一个主要表面上粘合了聚合物膜的层压金属板,聚合物膜是通过同时热层压法粘合到金属板上的,其特征在于,粘合到金属板的每个主要表面上的聚合物膜是一种复合聚酯膜(A),它包括一个内层(A1)和一个外层(A2),内层(A1)为软化温度低于200℃而熔点高于150℃但低于250℃的基本上为非结晶状的线性聚酯,外层(A2)为熔点高于250℃的二轴取向的线性聚酯。
15、一种按照权利要求14所述的层压金属板,其特征在于,内层(A1)的聚酯为对苯二甲酸乙二醇酯和异苯二甲酸亚乙酯的共聚物,或者是由对苯二甲酸和两种醇(通常为乙二醇和环己烷-二甲醇)组成的共聚物。
16、一种按照权利要求15所述的层压金属板,其特征在于,对苯二甲酸乙二醇酯与异苯二甲酸亚乙酯的摩尔比为80∶20。
17、一种按照权利要求14、15或16所述的层压金属板,其特征在于,外层(A2)为二轴取向的聚对苯二甲酸乙二醇酯。
18、一种按照权利要求14至16中任何一项所述的层压金属板,其特征在于,金属板为镀有一层金属铬和一层氧化铬的电解镀铬钢。
19、将权利要求14至16中任何一项所述的层压的金属板用于制造容器或容器的部件。
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WO2013157379A1 (ja) * | 2012-04-19 | 2013-10-24 | Jfeスチール株式会社 | ラミネート金属板および食品用缶詰容器 |
US10674738B2 (en) * | 2014-12-31 | 2020-06-09 | Toray Plastics (America), Inc. | Starch coated polyester film for release of canned meat products |
CN107538881B (zh) * | 2016-06-28 | 2019-12-27 | 宝山钢铁股份有限公司 | 一种覆膜金属板的生产方法及设备 |
WO2018184911A1 (en) | 2017-04-03 | 2018-10-11 | Tata Steel Ijmuiden B.V. | Process for producing a polymer coated metal substrate and a metal strip substrate provided with a polymer coating |
EP3479919A1 (de) * | 2017-11-01 | 2019-05-08 | Suisse Technology Partners Ag | Kaltumformverfahren für bleche oder metallfolien |
US20190193339A1 (en) * | 2017-12-21 | 2019-06-27 | GM Global Technology Operations LLC | Laser-induced micro-anchor structural and passivation layer for metal-polymeric composite joining and methods for manufacturing thereof |
US20210206529A1 (en) * | 2018-05-31 | 2021-07-08 | Toyo Seikan Co., Ltd. | Resin-coated steel can and method for producing the same |
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GB759876A (en) * | 1954-05-21 | 1956-10-24 | Ici Ltd | Coating or laminating process |
US2861022A (en) * | 1956-01-19 | 1958-11-18 | Du Pont | Thermoplastic film-metal-laminated structure and process |
JPS543498B2 (zh) * | 1973-02-02 | 1979-02-23 | ||
US3914502A (en) * | 1973-02-02 | 1975-10-21 | Toyo Boseki | Heat-adhesive laminated film |
JPS558022B2 (zh) * | 1975-02-10 | 1980-03-01 | ||
JPS5265588A (en) * | 1975-11-26 | 1977-05-31 | Toray Ind Inc | Covered metal structures and manufacturing thereof |
JPS5610451A (en) * | 1979-07-05 | 1981-02-02 | Toray Industries | Resin coated metallic plate for vessel |
AU530007B2 (en) * | 1981-04-02 | 1983-06-30 | Dow Chemical Company, The | Laminated container body and manufacture thereof |
JPS57187247A (en) * | 1981-05-15 | 1982-11-17 | Mitsui Petrochemical Ind | Thermoplastic polyester multilayer coated metal laminate |
JPS6047103B2 (ja) * | 1981-11-13 | 1985-10-19 | 東洋鋼鈑株式会社 | ポリエステル樹脂フイルム被覆金属板の製造方法 |
SE446703B (sv) * | 1982-01-20 | 1986-10-06 | Tetra Pak Finance & Trading | Sett att framstella ett for djupdragning eller streckning lempat laminatmaterial, genom settet framstellt laminat samt av laminatet tillverkad artikel |
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AU595007B2 (en) * | 1986-02-25 | 1990-03-22 | Grain Security Foundation Ltd | Laminates and laminated articles |
-
1987
- 1987-10-15 GB GB878724238A patent/GB8724238D0/en active Pending
-
1988
- 1988-10-12 JP JP63508367A patent/JPH02501640A/ja active Pending
- 1988-10-12 EP EP88309502A patent/EP0312303B1/en not_active Expired - Lifetime
- 1988-10-12 CA CA000579939A patent/CA1309939C/en not_active Expired - Lifetime
- 1988-10-12 ES ES198888309502T patent/ES2032976T3/es not_active Expired - Lifetime
- 1988-10-12 BR BR888807249A patent/BR8807249A/pt not_active IP Right Cessation
- 1988-10-12 DE DE8888309502T patent/DE3871708T2/de not_active Expired - Lifetime
- 1988-10-12 ZA ZA887614A patent/ZA887614B/xx unknown
- 1988-10-12 HU HU886245A patent/HU209756B/hu not_active IP Right Cessation
- 1988-10-12 WO PCT/GB1988/000853 patent/WO1989003304A1/en active IP Right Grant
- 1988-10-12 RU SU884614289A patent/RU2046720C1/ru active
- 1988-10-12 AT AT88309502T patent/ATE76810T1/de not_active IP Right Cessation
- 1988-10-12 AU AU25546/88A patent/AU599520B2/en not_active Ceased
- 1988-10-12 PT PT88731A patent/PT88731B/pt not_active IP Right Cessation
- 1988-10-12 AR AR88312161A patent/AR246460A1/es active
- 1988-10-12 PL PL88275222A patent/PL162279B1/pl unknown
- 1988-10-12 GB GB8823925A patent/GB2211135B/en not_active Expired - Lifetime
- 1988-10-12 MY MYPI88001144A patent/MY104338A/en unknown
- 1988-10-12 DD DD88320673A patent/DD283106A5/de not_active IP Right Cessation
- 1988-10-12 US US07/378,201 patent/US5059460A/en not_active Expired - Fee Related
- 1988-10-13 YU YU01903/88A patent/YU190388A/xx unknown
- 1988-10-14 CN CN88107081A patent/CN1020689C/zh not_active Expired - Fee Related
- 1988-10-14 CS CS886805A patent/CS680588A3/cs unknown
- 1988-12-12 NZ NZ226531A patent/NZ226531A/en unknown
-
1989
- 1989-06-13 BG BG88822A patent/BG50929A3/bg unknown
- 1989-06-14 DK DK292889A patent/DK292889A/da unknown
- 1989-06-14 FI FI892903A patent/FI96399C/fi not_active IP Right Cessation
- 1989-10-17 YU YU02021/89A patent/YU202189A/xx unknown
-
1992
- 1992-06-04 GR GR920401070T patent/GR3004798T3/el unknown
- 1992-08-06 SG SG783/92A patent/SG78392G/en unknown
- 1992-10-01 HK HK742/92A patent/HK74292A/xx not_active IP Right Cessation
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