CN101164774B - 层状金属板的制造方法以及通过该方法制造的层状金属板 - Google Patents

层状金属板的制造方法以及通过该方法制造的层状金属板 Download PDF

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Publication number
CN101164774B
CN101164774B CN2006101373226A CN200610137322A CN101164774B CN 101164774 B CN101164774 B CN 101164774B CN 2006101373226 A CN2006101373226 A CN 2006101373226A CN 200610137322 A CN200610137322 A CN 200610137322A CN 101164774 B CN101164774 B CN 101164774B
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laminated metal
plate
metal plate
resin film
fluorine resin
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Expired - Fee Related
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CN2006101373226A
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CN101164774A (zh
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渡边俊夫
松浦勲
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Laminate Industry Co Ltd
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Laminate Industry Co Ltd
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    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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    • B29C65/10—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using hot gases (e.g. combustion gases) or flames coming in contact with at least one of the parts to be joined
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Abstract

在层状金属板的制造方法中，氟树脂薄膜用作塑料膜。在火焰处理之前，金属板的接合面用900℃到1200℃的明火烧1至5秒，使接合面被预热至40℃到70℃。然后，用后继的火焰处理加热金属板的接合面至250℃到450℃。

Description

层状金属板的制造方法以及通过该方法制造的层状金属板
发明的背景 
(1)技术领域
本发明涉及一种其中塑料膜(片)层压于金属板表面上的层状金属板的制造方法，以及使用该方法制造的层状金属板的改进。 
(2)现有技术的描述 
作为用于容纳煤油，动物和植物油，各种溶剂，化学品，粘合剂等物质的金属容器(例如用钢板制成的)，多使用衬锌或衬锡的容器。然而，在许多视所容纳物质而定的情况下，这样的内衬不够用。因此，用烘烤涂覆材料如环氧树脂来形成内衬，或除上述内衬外采用聚乙烯，聚丙烯，聚酯膜等粘合剂来形成内衬。 
除采用上述粘合剂的方法之外，在金属板上粘合内衬材料通常通过热熔合法进行。在热粘合方法中，通过使金属板和合成树脂膜通过一个加热炉，通过由电磁感应线圈在金属板(磁性材料：钢板或类似物)中引起涡电流产生的焦耳热，或者通过本发明的发明人在下文中提及的专利文献1中提出的火焰处理，加热金属板和合成树脂膜。 
按照所述火焰处理方法，在结合前用火焰处理各个表面，随后立刻将金属板和合成树脂膜连续结合在一起。依照这种方法，不需要对金属板或合成树脂膜进行改善粘合性能的预处理，即可获得足够的结合强度，避免了粘合剂之类的有害物质，并且省去大型加热炉或电磁感应装置的使用，因此它具有非常显著的经济优势。 
当用树脂在钢板上形成内衬时，在粘合前必须实施预定的改善粘合性能的预处理(清洁金属板表面或合成树脂层：砂磨，脱脂，洗涤，干燥，打底胶等)。在薄膜内衬如聚乙烯的情况中，钢板侧需预处理并打底胶，薄膜侧需电晕处理，使用其中铺设粘合剂树脂的双层结构 的薄膜，或者在薄膜上打底胶。另一方面，依照该火焰处理方法，这些步骤可省略。 
同时，作为合成树脂薄膜，除通常用作内衬材料的上述聚乙烯薄膜，聚丙烯薄膜和聚酯薄膜之外，惰性的氟树脂薄膜也适于用作内衬材料。氟树脂薄膜在耐蚀性，抗污染性，耐粘附性，耐化学品性，耐热性，不可燃性等方面都有很好的性能。因此，氟树脂薄膜是用于在容纳煤油，动物和植物油，各种溶剂，化学品，粘合剂等物质的金属容器中形成内衬的最好的内衬材料之一。特别地，当用于烹饪设备和食品加工设备，烹饪加热装置如微波炉的内板，饭锅内盘或煤气灶的上面板，厨房材料如抽油烟机用的材料，医疗设备，户外建筑材料如马路外面板，建筑物的房顶或外墙等时，氟树脂薄膜作为内衬材料更加有效。 
氟树脂薄膜存在表面张力小，以及由于其不具有粘着性而难以通过热熔合获得粘合的问题。当一个分子单元含有两个或更多个氟原子时，特别是例如四氟乙烯-全氟烷基乙烯基醚共聚物树脂(PFA)，四氟乙烯-六氟丙烯共聚物(FEP)，或者乙烯-四氟乙烯共聚物树脂(ETFE)，氟树脂薄膜与金属表面的热熔合尤其困难。 
解决氟树脂薄膜热熔合到金属板表面上的问题的一种方法是，如下述专利文献2建议的，将含有聚偏二氟乙烯树脂和丙烯酸系树脂的着色的涂覆薄膜层在热熔合前先铺设于金属表面，然后将其烘烤和干燥。随后，透明的含有聚偏二氟乙烯树脂和丙烯酸系树脂的氟塑料薄膜被热熔合。 
上文提及的现有技术可见于下述文献。 
专利文献1： 
日本专利公开号7-100350。 
专利文献2： 
日本专利未审公开号2000-280402。 
然而，在上述热熔合方法中，需要在热熔合前对金属板进行预处理，并且氟树脂薄膜需要底胶。如较早的专利文献1所建议的，发明人研究了通过采取火焰处理方法来热熔合氟树脂薄膜从而形成内衬是否是可能的，这种简单的方法不需要任何预处理。基于专利文献1描述的方法，使用四氟乙烯-全氟烷基乙烯基醚共聚物树脂(PFA)，四氟乙烯-六氟丙烯共聚物树脂(FEP)，或乙烯-四氟乙烯共聚物树脂(ETFE)进行了各种试验，但是，并没有获得很好的粘着性。
对在聚乙烯，聚丙烯，或聚酯薄膜的情况下没有任何问题地获得优异的粘着性，但在氟树脂薄膜的情况下不能获得优异的粘着性的可能原因进行了研究、分析。结果据推测，常规的对金属板的火焰处理不充分，因为这种材料具有非常小的表面张力，并且不具有粘着性。 
发明概述 
本发明的目的在于提供一种在耐热性，持久性，粘着性等方面均优异，并且具有各种优异的性能如材料的耐蚀性，抗污染性，抗粘附性，耐磨性，可加工性和刚性的层压了氟树脂薄膜的层状金属板的制造方法，另外还提供了使用该方法制造的层状金属板，其中金属板不需要化学转化处理或打底胶，并且可采取热熔合来获得足够的粘合强度而不需要转化氟树脂薄膜的性质。 
为达到上述目的，在本发明层状金属板的制造方法中，将没有经历任何预处理，如脱脂，洗涤，化学转化处理，打底胶处理的厚度为0.1mm到1.00mm的金属板的接合面用1400℃到1600℃的直接火焰处理，并且塑料膜在压力下直接接合。氟树脂薄膜用作塑料膜。在所述火焰处理之前，用900℃到1200℃的直接火焰预热金属板的接合面1至5秒使接合面的表面温度升高至40℃到70℃。 
然后实施火焰处理使金属板接合面的表面温度升高至250℃到450℃。 
本发明的层状金属板通过本文中所描述的制造方法制造，来达到上述目的。 
按照本发明的层状金属板的制造方法，即使表面张力很小并且没有粘着性的氟树脂薄膜，仍能通过在常规的高温热处理之前引入对低温金属板加热至40℃到70℃的预热过程而紧密粘附并有充足接合强度地附着于金属板上。据推测，粘着力的显著提高是因为通过引入低温预热过程，同时金属板在短时间内按常规加热到高温，避免了金属板及其表面的变形。
结果，不需在金属板上进行化学转化处理或打底胶或改变氟树脂薄膜的性质，即可制造出层压了氟树脂薄膜的层状金属板，其中氟树脂薄膜可很好地粘合于金属板上，进行热熔合而具有优异的粘合性，耐热性、持久性和紧密粘着性优异，并有各种优异的性质，如耐蚀性，抗污染性，抗粘附性，耐磨性，可加工性和材料刚性。而且，因为不采用昂贵的粘合剂(粘合剂层)，产品的生产成本较低并且报废时不会带来损害。 
本发明的层状金属板通过上述制造方法制造并且在氟树脂薄膜和金属板之间的粘合强度方面表现出色。因此，在此基础上，层状金属板可用于烹饪设备和食品加工设备，烹饪加热器如微波炉的内板，饭锅内盘或煤气灶的上面板，厨房材料如抽油烟机的材料，医疗设备，户外建筑材料如马路外面板，建筑物的房顶或外墙等，也可用于各种容器。 
更具体地，本发明提供了以下技术方案： 
1.一种层状金属板的制造方法，该方法包括以下步骤： 
用900℃到1200℃的明火对厚度为0.1mm至1.00mm并且没有经过预处理的金属板的接合面进行火焰处理1至5秒，使接合面的温度被预热至40℃到70℃； 
然后用1400℃到1600℃的明火对所述金属板的接合面进行火焰处理以加热金属板的接合面，使接合面的温度升至250℃到450℃；和 
使所述金属板在压力下与氟树脂薄膜直接接合，以形成所述层状金属板。 
2.方案1所述的层状金属板的制造方法，其中所述预处理是脱脂，洗涤，化学转化处理或打底胶处理。 
3.方案1所述的层状金属板的制造方法，其中所述氟树脂薄膜由乙烯-四氟乙烯基共聚物组成。 
4.通过方案1至3中任一项所述的层状金属板的制造方法制造的层状金属板。 
附图简要说明 
附图示出了本发明的实施方案，其中： 
图1是本发明层状金属板的垂直剖面图，和 
图2是显示本发明层状金属板制造方法的简化工艺图。 
优选实施方案的详细描述 
在本发明的实施方案中，氟树脂薄膜优选含有乙烯-四氟乙烯基共聚物。使用氟树脂薄膜的一个优点是它便宜并且一般容易获得。 
或者，与上述材料类似的四氟乙烯-全氟烷基乙烯基醚共聚物树脂(PFA)或四氟乙烯-六氟丙烯共聚物树脂(FEP)也可使用。 
而且，通过改变本发明火焰处理的温度和时间，不用说聚乙烯，聚对苯二甲酸乙二醇酯和聚丙烯，其他不粘附的薄膜也可使用。 
作为构成所述层压了氟树脂薄膜的层状金属板的金属板，可以使用厚度为0.1mm至1.00mm的各种金属板，如冷轧钢板，不锈钢板，铝板，铜板或钛合金板等，和各种电镀金属板如镀锌钢板，镀锌铝合金钢板，镀铝钢板或类似物。这些金属板可以呈切成一定长度的片状或盘卷状。 
上述的氟树脂薄膜可以是单层体或多层体。氟树脂薄膜可以是透明的，有印刷的或着色的。 
实施例1： 
下面参照图1和图2来详细描述本发明层状金属板的制造方法。 
根据图2所示的方法，通过第一火焰喷嘴4对作为金属板3的厚度为0.3mm的TFS钢板(709mm×917mm)施加900℃至1200℃的明火(火焰)4秒作为预加热工艺，来预热金属板3的表面至60℃左右。预热金属板3后立刻(约1秒钟后)使用第二火焰喷嘴5对金属板3施加1400℃到1600℃的明火加热4秒钟，以加热金属板3的表面至300℃。作为氟树脂薄膜2，厚度为50μm的ETFE(由Asahi玻璃有限公司制造：氟隆ETFE：乙烯-四氟乙烯基共聚物)被通过辊6热压粘合，以制备层压了氟树脂薄膜的层状金属板1，如图1所示。在该热压粘合工艺中，金属板3和氟树脂薄膜2的传送速度为15m/min。 
图1是显示氟树脂薄膜2和金属板3层合状态的图，它们的尺寸没有相互关联。 
厚度为50μm的ETFE由第一火焰喷嘴4预热1至5秒的各种时间，结果没有发现问题。金属板的表面温度分别在40℃到70℃的范围内，结果也没有发现问题。而且，用第二火焰喷嘴5的加热进行2至5秒范围的时间，结果没有发现问题。此时表面的加热温度在250℃到450℃的范围内，结果也没有发现问题。 
实施例2： 
尽管附图中没有示出，对作为金属板的厚度为0.3mm的TFS钢板(709mm×917mm)施加900℃到1200℃的明火3秒作为预热工艺，以加热金属板表面至50℃。预热金属板后立刻(约1秒钟后)施加1400℃到1600℃的明火3秒，以加热金属板表面至300℃。作为氟树脂薄膜， 厚度为25μm的ETFE(由Asahi玻璃有限公司制造：氟隆ETFE：乙烯-四氟乙烯基共聚物)经历热压粘合，以制备层压了氟树脂薄膜的层状金属板。在该热压粘合工艺中，金属板3和氟树脂薄膜2的传送速度为15m/min。 
用第一火焰喷嘴4对厚度为25μm的ETFE预热1至5秒范围内的各种时间，结果没有发现问题。金属板的表面温度分别在40℃到70℃的范围内，结果没有发现问题。而且，用第二火焰喷嘴5进行的加热进行2至5秒范围内的时间，结果没有发现问题。此时表面的加热温度在250℃至450℃的范围内，结果没有发现问题。 
对如上所述制造的实施例1和实施例2的层合了氟树脂薄膜的层状金属板进行下述各种性能测试。如实施例1和实施例2所描述的本发明的层合了氟树脂薄膜的层状金属板均有很好的粘附性，并且在耐蚀性，抗污染性，耐热性，非粘附性，可加工性等方面表现出色。 
粘附性： 
根据通常用于测试涂覆材料的JISK5400方法，在测试样品(实施例1和实施例2的层状金属板)的氟树脂薄膜侧切成格子(10×10，间隔1mm)，切痕深度达到金属板，层状金属板经历8mm的Erichsen突出并浸入沸水中3小时。然后，通过胶带剥离试验来评价粘附性。如果完全没有剥离，评价用符号◎来表示，如果有1到5个被剥离的部分，用符号○表示，如果有6到10个被剥离的部分，用符号△表示，如果有11个或更多个被剥离的部分，用符号×表示。 
耐蚀性： 
测试样品(实施例1和实施例2的层状金属板)被弯曲成直角，并且其氟树脂薄膜朝外。基于JIS Z2371，在弯曲状态下，测试样品在5％的盐溶液和35℃的温度的条件下经受盐雾测试1,000小时，并在测试后检查和评价生锈情况。如果完全没有缺陷，评价用符号◎来表示，如果发现弯曲处的一部分生锈，用符号○表示，如果发现弯曲处整个区域生锈，用符号△表示，如果在平板部分发现生锈，用符号×表示。 
可加工性： 
测试样品(实施例1和实施例2的层状金属板)在氟树脂薄膜朝外的情况下重复弯曲成直角，直至测试样品断裂，检查薄膜裂缝和脱落。如果完全没有缺陷，评价用符号◎来表示，如果发现有裂缝或脱落，用符号×表示。 
耐热性： 
测试样品(实施例1和实施例2的层状金属板)在200℃的空气中加热15分钟，并重复该过程20次。然后检查并评价氟树脂薄膜的脱落，收缩，变色等的状态。如果完全没有缺陷，评价用符号◎来表示，如果发现任何缺陷，用符号×表示。 
抗污染性和非粘附性： 
使生发油，头油液，黑墨水，咖啡，红茶，蛋黄酱，番茄酱，酱油，伍斯特郡辣酱油，Wasibi(日本辣根)，和芥末与测试样品(实施例1和实施例2的层状金属板)的氟树脂薄膜面在室温下接触一周。然后，用湿酒精棉擦拭测试样品，并检查和评价粘附情况。如果接触测试样品的各种物质通过一次擦拭可全部擦掉并且测试样品完全没被污染，评价用符号◎来表示，如果测试样品未被污染但需要擦拭两次或更多次，用符号○表示，如果测试样品被污染，用符号×表示。 
上述各种性能测试的结果在下面的表1中列出。表1中并未出现上述的全部指示标记。 
                    表-1
             实施例-1          实施例-2 
粘附性：     ◎                ◎ 
耐蚀性：     ◎                ○ 
可加工性：   ◎                ◎ 
耐热性：     ◎                ◎ 
抗污染性：   ◎                ◎ 
非粘附性：   ◎                ◎ 
工业领域中的通用性： 
由于通过本发明制造方法制造的层状金属板因其优异的粘附性而具有足够的粘合强度，该层状金属板可用于容器内衬，烹饪设备和食品加工设备，烹饪加热器如微波炉的内板，饭锅内盘或煤气灶的上面板，厨房材料如抽油烟机的材料，医疗设备，户外建筑材料如马路的外面板，建筑物的房顶或外墙等。因此，该层状金属板是多用途的。 

Claims (4)

1.一种层状金属板的制造方法，该方法包括以下步骤：
用900℃到1200℃的明火对厚度为0.1mm至1.00mm并且没有经过预处理的金属板的接合面进行火焰处理1至5秒，使接合面的温度被预热至40℃到70℃；
然后用1400℃到1600℃的明火对所述金属板的接合面进行火焰处理以加热金属板的接合面，使接合面的温度升至250℃到450℃；和
使所述金属板在压力下与氟树脂薄膜直接接合，以形成所述层状金属板。
2.权利要求1所述的层状金属板的制造方法，其中所述预处理是脱脂，洗涤，化学转化处理或打底胶处理。
3.权利要求1所述的层状金属板的制造方法，其中所述氟树脂薄膜由乙烯-四氟乙烯基共聚物组成。
4.通过权利要求1至3中任一项所述的层状金属板的制造方法制造的层状金属板。
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