CN115190922A - 用于制造层叠镀锡钢的方法、由此生产的层叠镀锡钢及其用途 - Google Patents

用于制造层叠镀锡钢的方法、由此生产的层叠镀锡钢及其用途 Download PDF

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CN115190922A
CN115190922A CN202080093936.7A CN202080093936A CN115190922A CN 115190922 A CN115190922 A CN 115190922A CN 202080093936 A CN202080093936 A CN 202080093936A CN 115190922 A CN115190922 A CN 115190922A
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Prior art keywords
tin
plated steel
laminated
layer
thermoplastic
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Inventor
J·P·彭宁
D·康德拉蒂尤克
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Tata Steel Ijmuiden BV
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Tata Steel Ijmuiden BV
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Publication of CN115190922A publication Critical patent/CN115190922A/zh
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    • C25D5/48After-treatment of electroplated surfaces
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48After-treatment of electroplated surfaces
    • C25D5/50After-treatment of electroplated surfaces by heat-treatment
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Abstract

本发明涉及制造用于包装应用的层叠镀锡钢的方法,所述层叠镀锡钢包含镀锡钢片材和覆盖所述镀锡钢钢片材的至少一侧的热塑性层叠层,涉及由此生产的层叠镀锡钢及其在生产包装目的用容器的方法中的用途。

Description

用于制造层叠镀锡钢的方法、由此生产的层叠镀锡钢及其 用途
发明领域
本发明涉及制造用于包装应用的层叠镀锡钢(tinplate)的方法,所述层叠镀锡钢包含镀锡钢片材和覆盖所述镀锡钢钢片材的至少一侧的热塑性层叠层,涉及由此生产的层叠镀锡钢及其在生产包装目的用容器的方法中的用途。
发明背景
锡轧制产品传统上包括电解镀锡钢、电解镀铬钢(还称作无锡钢或TFS)和黑钢板。虽然不受它限制,但是锡轧制产品的大多数应用由容器工业使用在食品和饮料工业的罐、端盖和罩的制造中。
在包装工业中使用涂覆聚合物的基材在罐和罐部件的生产中变得越来越常见。可通过将熔融的聚合物膜直接挤出至金属性基材上或通过生产在集成或分开的层叠方法步骤中随后作为固体膜层叠至金属性基材上的热塑性聚合物膜来产生涂覆聚合物的基材。最适合于这个方法的热塑性聚合物是聚酯例如PET和聚烯烃例如PE或PP。
涂覆聚合物的包装钢中使用的金属性基材材料大多数是电解铬涂覆钢(ECCS),有时还称作无锡钢(TFS),其为电化学涂覆有非常薄的铬和氧化铬层的冷轧钢。在这个电解方法中在钢表面上形成的铬/氧化铬层提供附着有机涂层如热塑性聚合物涂层的优异表面层。因此,基于ECCS基材的涂覆聚合物的包装钢表现出优异的附着性和成罐性质。类似地,在描述为三价铬涂覆钢
Figure BDA0003754715420000011
的最近发展中,将非常薄的铬和氧化铬层电化学施加在冷轧钢顶部上,提供具有优异性质的涂覆聚合物的钢。
然而,在包装应用中使用涂覆铬的钢具有一些缺点例如缺少可焊接性和在一些介质、尤其是酸性(食物)介质中差的耐腐蚀性。镀锡钢(其为在任一侧上提供有锡层的钢基材)是既耐腐蚀的又可焊接的,并因此代表这些性质重要时的合适的替代基材材料。虽然在聚合物涂层和镀锡钢表面之间的附着不如聚合物涂层和铬/氧化铬表面之间的附着好,但是仍可实现高水平的附着水平并可获得具有好的成罐性质的产品。
镀锡钢是在两个表面上涂覆有锡的轻型钢带。锡通常通过电沉积施加。镀锡钢可在两侧上设置有相同厚度的锡或具有不同厚度(不同涂层)。镀锡钢可以生产状态使用,或它可以经历例如通过感应或电阻加热的大于锡的熔融温度的热处理,所谓的软熔,通过在钢基材和锡层之间的界面处形成不活泼FeSn2-合金层以增强产品的耐腐蚀性。如在WO2012045791-A1中公开,特定类型的热处理的镀锡钢设置有FeSn(50原子%铁和50原子%锡)合金层。这通过在513℃和625℃之间的温度下在还原气氛中扩散退火含有至多1000mg/m2和优选在至少100和/或至多600mg/m2之间的沉积锡的镀锡钢产生,在所述温度下锡层转化成由以1:1比率Fe:Sn的FeSn组成的铁-锡合金。FeSn层可涂覆有另外的锡层。这使锡的总量降低,尽管存在沉积两个锡层。
镀锡钢表面的重要方面在于对氧化锡生长非常不稳定,并因此需要钝化。如果没有钝化镀锡钢表面,氧化物层可在它的表面上形成,并且在储存过程中取决于储存条件这个层将继续在厚度上生长。氧化锡层赋予产品微黄色的外观并一旦向表面施加有机涂层例如漆或聚合物涂层时将导致粘附性损失。许多年来,镀锡钢最常见的钝化处理基于使用铬酸盐溶液,即含有六价铬的溶液,使用浸渍或电解辅助方法(分别为“300”和“311”钝化处理)将新镀锡的钢带暴露于该溶液。然而,六价铬目前被认为是对环境可能有害并构成工人安全风险的有毒物质。
发明目的
本发明的目的是提供制造层叠镀锡钢的方法。
另一目的是提供不涉及六价铬技术的制造层叠镀锡钢的方法。
另一目的依然是提供制造层叠镀锡钢的方法,其不使用六价铬,可焊接并具有在层叠层和镀锡钢之间的优异粘附性。
目的还是提供不使用六价铬技术生产的层叠镀锡钢,其可焊接并具有在层叠层和镀锡钢之间的优异粘附性,并且这适合于制备金属罐和金属罐部件。
发明描述
一个或多个目的使用制造用于包装应用的层叠镀锡钢的方法实现,所述层叠镀锡钢包含镀锡钢片材和覆盖所述镀锡钢片材的至少一侧的热塑性层叠层,所述层叠层由单个层或多个层组成,其中每个层含有热塑性芳族(共)聚酯或其共混物或包含至少90摩尔%的亚丙基单元的聚烯烃,该方法包括随后的步骤:
·通过电镀的方式向冷轧钢片材的一侧或两侧上提供锡层来产生镀锡钢片材;
·任选地通过大于锡的熔融温度退火来热处理所述镀锡钢片材;
·任选地通过电镀的方式向经热处理的镀锡钢片材的一侧或两侧上提供另外的锡层;
·通过将所述镀锡钢片材浸入具有的pH为8-12的包含磷酸根离子、硼酸根离子、硫酸根离子或碳酸根离子或它们的组合的水溶液中来使所述镀锡钢片材经历表面处理;
·漂洗并干燥所述镀锡钢片材;
·任选地向所述镀锡钢片材施加无铬、不漂洗、原位干燥的钝化处理溶液;
·干燥经钝化的镀锡钢片材;
·任选地卷绕所述镀锡钢片材用于储存或运输和展开用于进一步加工;
·提供所述热塑性层叠层用于涂覆在所述镀锡钢片材的至少一侧上;
·预加热所述镀锡钢片材并将所述热塑性层叠层层叠至经预加热的镀锡钢片材以产生层叠镀锡钢;
·后加热所述层叠镀锡钢至高得足以熔融所述层叠层的温度;
·冷却经后加热的层叠镀锡钢。
在本发明的上下文中镀锡钢定义为包括锡层的钢基材,层叠层是待层叠至镀锡钢上的聚合物涂层,并且具有层叠至镀锡钢上的层叠层的镀锡钢被称作层叠镀锡钢(参见图9a-c)。
根据本发明的方法提供这样的方法,该方法提供可以以镀锡钢带的形式提供的镀锡钢片材,并向镀锡钢片材提供层叠层。镀锡钢的表面条件在层叠层的粘附中是关键的并且根据本发明的方法确保镀锡钢的表面适合于与层叠层热结合。使镀锡钢的表面适合的方式是通过将镀锡钢浸入可为缓冲溶液的水溶液中,或浸渍时通过将阴极电流施加至镀锡钢上,并任选通过向镀锡钢片材额外施加无铬、不漂洗、原位干燥的钝化处理溶液。这导致清洁和易受影响的表面,从该表面已一定程度去除任何污染物和锡氧化物,使得在热结合之后的粘附性与用六价铬处理钝化的现有技术镀锡钢的粘附性具有相同品质。如果镀锡钢的储存条件是这样使得基本上没有发生氧化锡生长,通过将镀锡钢片材浸入具有的pH为8-12的包含磷酸根离子、硼酸根离子、硫酸根离子或碳酸根离子或它们的组合的水溶液的表面中处理,其中任选同时将阴极电流施加至镀锡钢可为足够的,并且可以不需要额外施加无铬、不漂洗、原位干燥的钝化处理溶液。
优选地,水溶液的pH不低于8.5和/或不高于11.5。合适的最大pH值为11或甚至10.5。水溶液优选含有来自周期表的第1族(例如Na+、K+)或第2族(例如Mg2+、Ca2+)的阳离子或多原子阳离子(例如NH4 +)和多原子阴离子(磷酸根、硼酸根、硫酸根、碳酸根等)。另外,阴离子可为有机酸的共轭碱(例如乙酸盐、柠檬酸盐)。此外,电解质可含有其它化学添加剂例如表面活性剂、润湿剂、消泡剂等以支持电化学处理。
优选地水溶液含有仅碳酸根作为阴离子,优选作为碳酸钠添加至水溶液,并优选没有硼酸根、磷酸根、硫酸根等。通过非限制性实例的方式,建议在去离子水中含有不大于1g/l Na2CO3.10H2O的pH在9.5和10之间的十水合碳酸钠溶液。
然而,如果预期镀锡钢的这些储存条件由于湿度、储存温度、储存持续时间等较不有利,可通过向镀锡钢片材额外施加无铬、不漂洗、原位干燥的钝化处理溶液而不通过电解沉积来钝化镀锡钢片材的表面。
钝化处理溶液可基于锆、钛、锆与钛的组合、磷酸盐,例如US10011915中公开的含有元素Zr、Ti、Hf的水溶性无机化合物的酸性水溶液。实例是
Figure BDA0003754715420000051
M-NT1455、Bonderite M-NT1456和Bonderite M-NT10456(Henkel)或
Figure BDA0003754715420000052
Z801(ADChemicals)。在本发明上下文中,钝化处理溶液不是基于硅烷或硅氧烷的溶液,因为这些没有改进镀锡钢和热塑性层叠层之间的粘附性。所以根据本发明,钝化处理溶液不含硅烷、不含硅氧烷且不是基于Si的。
不漂洗、原位干燥体系相对于电解体系的优点在于溶液易于施加,在紧凑的施加单元中使用简单的设备,允许容易装配在现有的生产线上,并且更通用的化学品是可用的。可通过对于这样的钝化体系而言通常的施加技术将钝化处理溶液施加至表面处理的镀锡钢表面。合适的施加技术包括:浸渍、用挤压辊浸渍、转子喷射施加、通过使用光整辊支撑的转子喷射施加、喷射施加、喷射-挤压施加、通过辊涂机系统施加、通过狭缝涂覆施加、狭缝幕涂等。
可卷绕经表面处理和任选钝化的镀锡钢用于储存和运输并之后展开,或者可将其立即转移至其中将层叠层在线层叠至预加热的镀锡钢上的层叠装置。
本发明还体现在一种方法,其中通过以下提供热塑性层叠层:
·提供预产生的单轴或双轴取向的热塑性层叠层,或
·在一个或多个挤出机中熔融热塑性聚合物粒料以形成一个或多个层并通过使熔融的一种或多种聚合物通过扁平的(共)挤出模头和/或两个或更多个压延辊来形成由所述一个或多个层组成的热塑性层叠层;之后:
A.
·冷却热塑性层叠层以形成固体热塑性层叠层;
·任选修整热塑性层叠层的边缘;
·通过仅在纵向方向上施加拉伸力通过在拉伸装置中拉伸固体热塑性层叠层来减小固体热塑性层叠层的厚度;
·任选修整经拉伸的热塑性层叠层的边缘;
·将层叠层层叠至经预加热的镀锡钢片材上;
或之后
B.
·在扁平的(共)挤出模头和浇注辊之间牵拉挤出的热塑性层叠层,并在浇注辊上浇注成其最终期望厚度以快速冷却经牵拉的热塑性层,其中浇注和冷却的热塑性层叠层基本上无取向;
·任选修整浇注和冷却的热塑性层叠层的边缘;
·将浇注和冷却的热塑性层叠层在线层叠至经预加热的镀锡钢片材上。
优选通过挤出涂覆和层叠的方式进行层叠层至镀锡钢的施加方法,其中将聚合物熔融并在扁平的(共)挤出模头中成型为薄的热膜,其中挤出的聚合物膜随后引导至浇注或冷却辊上并然后层叠至经预加热的镀锡钢基材以形成层叠镀锡钢。然后层叠镀锡钢通常通过压送辊(roll-nip)组件,其将层叠层牢牢压在基材上以确保完全接触和粘附。镀锡钢的预加热温度必须足够高以促进层叠层与镀锡钢的粘附,但不太高至引起层叠层粘到装置上或引起层叠层劣化。优化的预加热温度因此取决于层叠层和层叠设备的组合。
对挤出涂覆和层叠的替代是膜层叠,其中将固体层叠层供应并涂覆至经加热的镀锡钢上并通过压送辊组件压在镀锡钢上以确保层叠层与经预加热的镀锡钢的完全接触和粘附。这个固体层叠层可预生产并甚至从外部供应商拿来,或它可在现场生产并随后层叠至镀锡钢片材上。
在两种情况下,在压送辊组件中将层叠层层叠至镀锡钢上之后,将层叠镀锡钢在后加热装置中后加热至大于一个或多个层叠层的熔点的温度,或者如果层叠层由不同的聚合物组成,后加热至大于多层体系中具有最高熔融温度的层叠层的熔点的温度。后加热的目的是减小或消除层叠层中的任何残余取向。
在这个后加热之后,将层叠镀锡钢立即以足够高的冷却速率冷却至足低够以尽可能多地抑制结晶,优选完全抑制结晶的温度。水淬火是适当且常使用的。对于大多数聚酯而言小于50℃的淬火温度是好的准则。小于玻璃化温度(Tg),聚合物链不再可移动。50℃的值小于大多数芳族(共)聚酯的玻璃化温度。聚烯烃具有低得多的Tg,甚至小于0℃,所以这里问题是尽可能多地抑制结晶并特别是避免大(球状)晶体的生长。在这样的淬火中实现的冷却速率不是特别关键,只要它足够快,并且合适的值位于约50至300℃/s之间,例如约100℃/s。需要的预加热和后加热温度以及冷却速率和冷却温度取决于使用的聚合物类型并可在以上基础上容易确定。后加热温度优选为至少235℃。
作为层叠层,发明可使用如权利要求2中要求保护的预生产的双轴或单轴取向的聚合物膜,在线浇注和拉伸的单轴取向的聚合物膜,或在线浇注和牵拉的未拉伸的聚合物膜。
层叠层中的聚酯是热塑性芳族(共)聚酯或它们的共混物。特别地,关于此参考聚对苯二甲酸乙二醇酯(PET)、IPA改性的聚对苯二甲酸乙二醇酯(IPA-PET)、CHDM改性的聚对苯二甲酸乙二醇酯(PETg)、聚对苯二甲酸丁二醇酯(PBT)、聚萘二甲酸乙二醇酯(PEN)或它们的共聚物或共混物。
层叠层中的聚丙烯选自以下:聚丙烯、聚丙烯共聚物、化学改性的聚烯烃例如马来酸酐接枝的聚丙烯。后者主要用作粘附层。聚丙烯主要用作本体层。
在本发明的上下文中“在线”应理解为构成连续操作序列的集成部分。因此,在层叠层和层叠镀锡钢的在线生产中,在连续且不间断的操作序列中进行产生层叠层和涂覆层叠层至经预加热的镀锡钢上。
本发明还体现在层叠镀锡钢,其中层叠层至少在变为包装例如容器或罐内侧的一侧上形成,并且层叠层中一个或多个层中的聚酯含有至少80mol%且优选85mol%的对苯二甲酸乙二醇单元或其中聚酯是包含至多35mol%的CHDM或20mol%的IPA的共聚酯。
本发明还体现在层叠镀锡钢,其中层叠层至少在变为包装例如容器或罐内侧的一侧上形成,并且层叠层中一个或多个层中的聚酯含有至少80mol%且优选85mol%的对苯二甲酸丁二醇单元。
本发明还体现在层叠镀锡钢,其中层叠层至少在变为包装例如容器或罐内侧的至少一侧上形成,并且层叠层中一个或多个中的聚酯含有含85摩尔%的对苯二甲酸乙二醇单元的聚酯和含至少85摩尔%的对苯二甲酸丁二醇单元的聚酯的共混物。
本发明还体现在层叠镀锡钢,其中包装例如容器或罐的至少一侧上的一个或多个层叠层包含一个或多个基本上由聚丙烯组成的聚丙烯层。
本发明还体现在层叠镀锡钢,其中一个或多个层叠层包含由马来酸酐接枝聚丙烯组成的粘附层。
在本发明的另一实施方案中,层叠镀锡钢经历拉伸操作,其中拉伸操作通过以下实现:
·使材料通过平整机并施加0-3%之间、优选至少0.2%的厚度压下量;或
·使材料通过拉伸矫直机。
为了实现在层叠层和镀锡钢之间的紧密结合,有必要使用升高的温度和/或热处理例如基材的预加热和层叠镀锡钢的后加热。这些热处理由于时效作用可负面影响钢基材的整体机械性质。通过平整小程度(即在0-3%之间,优选至少0.2%,更优选至少0.5%)拉伸涂覆聚合物的钢基材或使材料通过拉伸矫直机。这样的处理改进整体机械,可改进带形状并且这样的材料调节方法可能还可用于改变表面组织。发明人发现了应力开裂在用于包装应用的涂覆聚合物的钢基材中发展直接与基材的机械行为有关。在出现应力开裂和由于不连续的屈服现象基材显示不均匀的局部变形(吕德斯线)的区域之间存在强的相关性。通过平整或拉伸矫直涂覆聚合物的基材,抑制了这些不连续的屈服现象。
本发明还体现在一种方法,其中经钝化的镀锡钢片材的一侧或两侧上的层叠层是多层涂层体系,所述涂层体系至少包含用于粘附至经钝化的镀锡钢片材的粘附层、表面层和在粘附层和表面层之间的本体层。
根据本发明涉及产生在线浇注和牵拉未拉伸的聚合物膜的方法特别适合于生产如在WO2019110616-A1中描述的3件式罐体用层叠镀锡钢。
本发明还体现在优选实施方案,其中浇注和冷却的热塑性层叠层使用切割装置(11)在纵向方向上切割成至少N个宽层叠层(9a-9d)和(N-1)个窄带(10a-10c)(其中N为至少2),之后通过排出装置(12)引导窄带远离宽层叠层,并随后通过压送辊组件(4a,4b)将宽层叠层涂覆至经预加热的镀锡钢上以获得具有在纵向方向上由没有所述宽层叠层的窄带(10a-10c)空间隔开的多个宽层叠层(9a-9d)的层叠镀锡钢,并且其中镀锡钢的边缘保持没有所述宽层叠层,之后后加热层叠镀锡钢和冷却经后加热的层叠镀锡钢。
这个实施方案导致涂覆有由通过在线挤出产生的单个较宽的热塑性层叠层生产的热塑性层叠层的窄带的层叠镀锡钢。在窄带之间存在未层叠镀锡钢的非常窄的带,并且如此生产的层叠镀锡钢特别适合于生产3件式罐体用坯料。
在实施方案中,层叠层具有在5和35μm之间的厚度。
在根据本发明的方法中层叠层按照它的主要聚合物成分定义。然而,除了聚合物成分,在聚合物中可存在添加剂例如抗氧化剂、热稳定剂、UV吸收剂、增塑剂、颜料、成核剂、抗静电剂、脱模剂、抗粘连剂等。
当在聚合过程中使用多于一种二酸或二醇时产生共聚酯。当一起使用乙二醇(EG)和至多35%环己二甲醇(CHDM)时,产生被称作甘醇改性的聚对苯二甲酸乙二醇酯(PETg)的共聚酯。当至多20mol%的对苯二甲酸被间苯二甲酸(IPA)代替时,结果是IPA-PET共聚酯。
优选地,镀锡钢钢基材使用的钢是碳钢,优选低碳钢、极低碳钢、超低碳钢或HSLA钢。钢基材的厚度通常在0.10和0.49mm之间。这些未合金化(ULC、LC和ELC)或微合金化(HSLA)的钢材是相对便宜的基材并提供好的强度和可成形性。通过公知的方法例如铸造、热轧和冷轧的方式生产钢。低碳钢通常包含0.05至0.15重量%C和超低碳钢典型地包含0.02至0.05重量%C。极低碳钢包含典型地小于0.01重量%C。按照规定了某种元素可存在多少仍被认为是非合金钢的EN10020-2000,除了碳以外可存在其它元素。
本发明还体现在通过根据本发明的方法获得的层叠镀锡钢,用于生产3件式罐用坯料的层叠镀锡钢,和根据本发明的层叠镀锡钢在生产包装目的用罐或罐零件的方法中的用途。
实施例
现在将通过以下非限制性实施例的方式解释本发明。
将厚度0.17mm和TH550平整度的冷轧低碳钢在商业镀锡生产线上电镀锡以生产在产品的测试侧上具有1.0、2.0、2.8或5.6g/m2的锡涂覆重量的镀锡钢。在大多数情况下使锡层软熔但在两个情况下(实施例7和8)关闭软熔装置以生产非软熔的镀锡钢。生产状态的镀锡钢随后使用根据以上概述的不同方法的镀锡工艺在线钝化。
在实施例1-6(其反映现有技术)中,通过在阴极电流下将带材通过重铬酸钠溶液即传统的“CDC”(阴极重铬酸盐)或“311”钝化处理来钝化镀锡钢。
在实施例7-10中,通过在没有施加电流的情况下将带材首先通过碳酸钠溶液(以9.5-10的pH为特征)来施加无铬钝化。在漂洗和干燥之后,通过喷射盘连同光整辊的方式施加Bonderite M-NT1456的溶液。Bonderite溶液的浓度对应于0.25g/l Ti并以约4ml/m2的湿膜厚度施加,旨在产生0.8-1.2mg/m2 Ti的干燥钝化膜厚度。原位(in place)干燥湿膜并且随后卷绕带材。
在实施例11和12中,在没有施加电流的情况下将带材通过实施例7-10的碳酸钠溶液。在漂洗和干燥之后,在没有施加Bonderite溶液的情况下卷绕带材。如果使镀锡钢通过碳酸钠溶液和将镀锡钢与热塑性层叠层层叠之间的时间短暂,则这些实施例显示在没有向镀锡钢施加无铬钝化处理溶液的情况下可获得好的粘附。
在实施例13和14中,将带材通过实施例7-12的碳酸钠溶液同时施加对应于40C/m2的电荷密度的阳极电流。在漂洗和干燥之后,通过喷射盘连同光整辊的方式施加BonderiteM-NT1456的溶液。Bonderite溶液的浓度对应于0.25g/l Ti并以约4ml/m2的湿膜厚度施加,旨在产生0.8-1.2mg/m2 Ti的干燥钝化膜厚度。原位干燥湿膜并且随后卷绕带材。
通过挤出涂覆和层叠工艺的方式向以上描述的各种镀锡钢材料施加聚酯涂层。施加两种类型的聚合物涂层:
·涂层类型A由15μm厚度的单层组成,所述单层由可从Indorama(PET)商购得到的聚(对苯二甲酸乙二醇酯)型号N180组成。
·涂层类型B由接触金属基材的具有3μm厚度的粘附层和12μm厚度的顶层组成。粘附层是由70重量%的甘醇改性的聚(对苯二甲酸乙二醇酯)(PETg)(可从Eastman ChemicalCompany商购得到的Eastar Copolyester 6763)和30重量%的聚(对苯二甲酸乙二醇酯)型号N180组成的混合物。顶层由聚(对苯二甲酸乙二醇酯)型号N180(PET)组成。
在聚合物涂覆方法中,将镀锡钢预加热至温度使得当使层叠层与镀锡钢接触时镀锡钢温度为至少170℃。在施加层叠层之后,将层叠镀锡钢短暂再加热至275℃的温度,随后在冷水槽中淬火,干燥并卷绕。
在以下表1中给出本实施例中不同层叠镀锡钢的概述。实施例1-6反映现有技术,其中镀锡钢基材是用六价铬钝化溶液(311)钝化的镀锡钢。实施例7-12是发明实施例,其中镀锡钢基材是无铬镀锡钢。实施例13-14是对照实施例,其中镀锡钢基材是无铬镀锡钢。
材料的评价
通过180°T-剥离测试的干粘附性
通过在平坦的片材料上进行的180°T-剥离测试来完成涂层粘附性的定量评价。对于这个测试,从涂覆聚合物的材料切割出15mm宽的带材。将带材的窄端放入小体积的18%盐酸中以蚀刻钢基底并获得短长度(几毫米)的自由聚合物涂层。将胶带贴在自由涂层上,并随后使用以25mm/min运行的拉伸测试仪以180°角将涂层从基材剥离。T-剥离力测量为开始剥离过程所需的最大负载值(以N/15mm表示)。
通过横切测试的干粘附性
根据ISO 2409,使用横切测试评价在平坦材料上的涂层粘附性。使用由4个间隔5mm的切割刀片组成的特殊切割工具,并使用实验室规模的电机驱动切割设备将横切施加至15×7.5cm的平板。在施加横切之后,通过使用一片25mm宽的Scotch 610号胶带剥离涂层,并通过公知的范围为0(无脱层)-5(全部脱层)的Gitterschnitt(GT)等级表示结果,来评价涂层粘附性。所有测试都一式三份进行。
在各种介质中灭菌后的粘附性
将尺寸为15×7.5mm的平板置于CertoClav“压力锅”灭菌设备内的测试介质中,并且然后施加灭菌的合适时间和温度条件。表2中描述各种介质和测试条件。在灭菌工序之后,使板冷却并干燥,并通过如以上描述的横切测试来评价粘附性(在小于4小时内)。
脱层界面的XPS(X-射线光电子能谱法)分析
新脱层样品的表面化学分析和近表面化学分析通过Kratos Axis Ultra仪器进行,使用Al单色源(1486.7eV),在15kV加速电压和15mA发射电流下。通过XPS深度分布使用Ar+溅射研究新暴露表面的表面下组成。在每次XPS测量之后,在提供1nm/min的溅射速度的2kV的加速电压和3×3mm溅射区域的60μA引出电流下进行溅射循环。在新脱层的表面的基材和涂层侧上进行分析。通过将环氧树脂(Betamate 1496)施加到涂覆聚合物的金属的样品,之后在约175℃下固化20分钟,和随后将样品浸入液氮从而实现脱层,其中相对厚的环氧层由于在低温下环氧收缩而将聚合物涂层从基材剥离。XPS分析在室温下在超高真空(1×10-9mbar)中进行以减轻大气的影响。然后使用CasaXPS处理每个检测元素所获得的XPS谱图,以在距表面不同深度处产生不同物质的浓度(原子%)。
通过横切测试对涂覆聚合物的镀锡钢上的粘附性的评价总是使用至少三个板进行,并且由于测试的属性和结果的解释,在不同的板之间GT粘附性值可存在小的变化。基于我们的经验,我们已经确定聚合物涂层在镀锡钢基材上的粘附性对于最终的终端用途应用将是足够的,只要在三个测试的板中最高GT粘附性值(即最差的粘附性结果)不高于2。此外,为了进行成型步骤而不使涂层脱层,干燥T-剥离粘附性值应至少为5N/15mm。
表4中给出来由本实施例产生的粘附结果。基于以上标准,可看出根据现有技术使用铬钝化的材料都显示好的性能。对于涂层类型A,干燥T-剥离粘附性值在8-11N/15mm范围内,而对于涂层类型B,该值在6.5-8.5N/15mm范围内。此外,横切粘附性值都在需要的范围内。镀锡钢基材的锡涂覆重量在所研究的范围内似乎对测试结果没有任何显著影响。
本发明实施例7-12还证明了优异的粘附性质,其中干燥T-剥离粘附性值(仅涂层类型B)在7-9N/15mm范围内,并且在所有情况下横切粘附性值等级为2或更低。有趣的是,当在清洗步骤之后不施加Bonderite钝化溶液(实施例11和12)时,也实现了优异的粘附。应注意在这种情况下,其基本上对应于“未钝化的”镀锡钢,在镀锡钢材料的生产和用聚合物层涂覆之间经过的时间内,氧化锡层可在镀锡钢的最外表面上形成,并且该氧化锡层可损害聚合物涂层的粘附性。因此,当使用这种方法时,应良好地控制在镀锡钢材料的生产和用聚合物层涂覆之间经过的时间,和镀锡钢材料的储存条件(例如温度、相对湿度)。
在使用阳极电流进行清洁步骤的对照实施例13-14中,观察到非常差的涂层粘附性。干燥T-剥离粘附性值非常低(实施例13中2.0N/15mm)或难以测量(实施例14中<0.5N/15mm,其中涂层几乎自发地从基材脱层),并且这在横切粘附性值中类似地引人注目:在许多情况下等级为3,并且在最有侵蚀性的介质(即含有乙酸的介质)中甚至高达4或5。
通过XPS分析脱层界面表明对照实施例14中的差的粘附性可归因于在聚合物和锡层之间的界面处存在锡氧化物物质,主要是SnO2。图4和5分别显示对于代表现有技术的铬钝化的镀锡钢的来自实施例4的材料而言镀锡钢基材和剥离的聚合物涂层的XPS深度分布。在基材侧和脱层的聚合物侧上,深度分布都主要显示有机碳。这意味着在远离锡表面一定距离(几十纳米)处,通过聚合物本身内的内聚失效而发生聚合物涂层的脱层。这意味着聚合物和锡表面之间的粘附非常强。图6和7分别显示对于代表无铬钝化的镀锡钢的来自本发明实施例8的材料而言镀锡钢基材和剥离的聚合物涂层的XPS深度分布,包括在没有施加电流的情况下在碳酸钠溶液中清洁和随后施加Bonderite M-NT1456溶液的步骤。在基材侧,深度分布主要显示具有非常薄的氧化锡(主要是SnO)层(约1nm)的锡。该薄SnO层可在分离聚合物涂层之后的样品制备过程中形成。在剥离的涂层侧,主要观察到有机碳。这个结果表明在有机涂层(即Bonderite层和/或聚合物涂层的有机部分)和锡之间的明确界面上发生脱层,从而在涂层和基材之间提供强的结合,如在横切测试中的高的T剥离粘附力和好的粘附性能反映。最后,图8和9分别显示对于代表无铬钝化的镀锡钢的来自对照实施例14的材料而言镀锡钢基材和剥离的聚合物涂层的XPS深度分布,包括在碳酸钠溶液中清洁同时施加电流和随后施加Bonderite M-NT1456溶液的步骤。在基材侧和聚合物侧上的深度分布都显示大量的氧化锡,主要是SnO2,厚度为几纳米。氧化锡明显存在于脱层界面的两侧的事实意味着在氧化物层内发生脱层。从T-剥离粘附性值可明显看出这个氧化物层弱并导致聚合物涂层从镀锡钢表面容易脱层。因此,必须避免存在这样的氧化物层以便在聚合物涂层和镀锡钢基材之间实现好的粘附。
表1本发明的实施例中镀锡钢基材的性质、钝化类型和聚合物涂层(苏打=碳酸钠)
Figure BDA0003754715420000151
表2产物评价测试
测试 描述 介质 条件
测试1 干粘附性 不适用 不适用
测试2 Bouillon Plasmal 12g/l Maggi+2g/l Plasmal 121℃/90min
测试3 乙酸 1%乙酸 121℃/60min
测试4 含盐测试 3.6%NaCl 121℃/90min
测试5 维生素C 1g/l维生素C+3.6%NaCl 121℃/90min
测试6 软化水 121℃/60min
测试7 盐-酸 18.7g/l NaCl+30g/l乙酸 121℃/60min
作为发明人对镀锡钢的表面处理关于氧化锡形成和稳定性以及关于有机和聚合物涂层的粘附性的广泛研究的一部分,本发明人研究了两种广泛类型的无铬钝化处理溶液的性能:基于硅氧烷的那些和基于锆和钛化合物的那些。基于硅氧烷的处理体系的公知实例是来自Chemetall的
Figure BDA0003754715420000152
MM0705。基于锆/钛的处理体系的公知实例是来自Henkel的BonderiteTM M-NT1456。使用安装在商业生产线上的喷射施加,将两种体系施加到在两侧上具有2.8g/m2 Sn的锡涂覆重量的镀锡钢上。选择涂覆条件和无铬钝化处理溶液组成,以得到0.6-0.8mg/m2 Si或Ti的处理层厚度,此后通过表面表征(XPS)证实。然后测定氧化锡和氧化锡生长速率并与铬钝化(“311”)镀锡钢和未钝化镀锡钢比较。
材料表面上存在的氧化锡的量可使用库仑法来确定。氧化锡层通过在0.01M氢溴酸(HBr)溶液中的受控的小阴极电流被还原,所述氢溴酸通过用氮洗涤而不含氧。通过测量还原电势来监测氧化物的还原过程,并将对于完全还原而言所通过的电荷(A*t)作为氧化锡层厚度的量度。对于测试,使用具有在一端大约4cm直径的圆形孔和Ag/AgCl参比电极的圆柱电池。电池的另一端含有铂对电极。测试样品覆盖该孔,其使用O形环密封以形成明确限定区域的水密连接,并使用气压缸将测试样品紧固就位。电池通过柔性管与电解质溶液连接,使得它可在氮气氛下填充和排空。使用恒电势仪-恒电流仪向样品施加-0.50A/m2的阴极电流密度,并测量电势直至还原完成。测试结果表示为还原氧化物层所需的总电荷密度(以C/m2计)。通过将测试板置于40℃下和80%相对湿度的气候室内两周,并然后测量存在于表面上的氧化锡的量并与接收状态的镀锡钢材料中存在于表面上的氧化锡的量进行比较,来检查氧化物层的稳定性。
在表3中总结这个研究的结果。与基于Si的Oxsilan体系相比,基于Zr/Ti的Bonderite体系在镀锡钢表面上提供了更薄且更稳定的氧化锡层。基于这个结果,显然基于Zr/Ti的体系理想地适用于本发明,而基于Si的体系则不适用。
表3在钝化之后氧化锡层稳定性对比
Figure BDA0003754715420000161
**在气候室中40℃和80%RH下暴露两周
Figure BDA0003754715420000171
Figure BDA0003754715420000181
附图简要描述
现在将通过以下非限制性附图的方式解释本发明。
图1显示一些术语的定义。
图2显示固体膜层叠过程的示意说明。
图3显示浇注膜层叠过程的示意说明。
图4至9显示在层叠层从镀锡钢分离之后层叠镀锡钢的XPS分布以研究层叠层和镀锡钢之间结合的属性。
图10至12显示3件式罐用层叠镀锡钢的生产阶段。
在图2中,镀锡钢片材或带材(1)通过第一加热装置(2),其中镀锡钢的温度升高至适合于层叠的预热温度T1。两卷层叠层(3a,3b)同时展开,并与经预加热的镀锡钢一起通过包含一对层叠辊(4a,4b)的压送辊组件。层叠镀锡钢(5)通过第二加热装置(6),其中层叠镀锡钢的温度升高至后加热设定点T2。在第二加热装置之后,层叠镀锡钢由通过淬火装置(7)立即冷却以达到室温。在第一加热装置中预加热镀锡钢的方法没有特别限制,并且可包括使带材在加热的辊上方通过、传导加热、感应加热、辐射加热等。在第二加热装置中后加热层叠镀锡钢的方法优选是非接触方法,例如在热气体环境中加热或感应加热。淬火装置的直接冷却方法没有特别限制,并且可包括施加冷空气或通过冷水浴等。在图2中,在卷上提供层叠层。然而,在已经拉伸和冷却至固体和拉伸的热塑性层叠层之后,也可直接从挤出模头提供层叠层。
在图3中,从平模(14)挤出层叠层,在挤出模头和浇注辊之间形成的狭窄间隙中向下牵拉,并在快速冷却的流延辊(13)上流延成其最终所需厚度。因为在液体条件下进行牵拉降至最终厚度,所以浇铸层叠层基本上是非取向的。然后可以以与图2中描述的方法类似的方式将层叠层层叠至镀锡钢1上。
为了产生3件式罐用材料,将挤出的层叠层切开(11),并且将宽层叠层(9a-9d)之间的窄聚合物带(lOa-lOd)引开并除去。由挤出的聚合物膜产生的宽层叠层(9a-9d)的数目可为2或更多。在说明性附图中,通过实例的方式使用四个宽层叠层(9a-9d)的数目,但是本发明也正好适用于两个、三个或更多个宽聚合物膜。从待排出的宽层叠层(9a-9d)之间切出的窄聚合物带(10)的数目原则上总是比待层叠至镀锡钢上的宽层叠层的数目少1。挤出层叠层(3)的宽度应小于镀锡钢的宽度以允许镀锡钢的边缘保持未涂覆。如果聚合物膜变得太宽而不能使镀锡钢的边缘保持未涂覆(即裸露),则可需要在线修整聚合物膜的边缘。将这些切断的边缘从层叠层引开,并且在层叠过程中将层叠层涂覆到镀锡钢上,使镀锡钢的最外边缘从聚合物裸露。这优于在层叠过程之后涂覆聚合物涂层的边缘并磨掉或以其它方式去除边缘的替代方案。聚合物膜的切断边缘的引开可通过切割废料提取装置例如通过抽吸装置(12)来进行。
图10以顶视图(未按比例)显示镀锡钢1以及挤出和冷却的层叠层3。在图10的底部图中描绘了切口情况,其中待去除的小带为阴影线(10a-10c),并且待层叠至镀锡钢的宽层叠层使用9a-9d。图11显示层叠镀锡钢的顶视图,其中显示裸露的带和裸露的边缘。这些裸露的边缘和裸露的带是形成焊接在一起的三件式罐体所需要的。图11还示意性地显示(顶部图左手侧,虚线)可如何将层叠镀锡钢纵向地切开成四个窄的层叠镀锡钢带,以及可如何生产用于3件式罐的单独坯料。这些坯料中每个都具有不含聚合物的边缘,因此可焊接以生产3件式罐体(参见图13)。
图11中的底部图显示沿A-A的横截面。图12显示在镀锡钢的两侧上提供层叠层的相同情况。图13显示焊接的3件式罐体的横截面,并且该图的左手侧显示焊接部分的放大部分。清楚地显示裸露的镀锡钢边缘以及宽聚合物膜带3a的边缘和两个裸露边缘通过焊接结合在一起的部分。随后用漆17覆盖焊接的和裸露的金属以保护金属免受腐蚀。漆优选无BPA。

Claims (14)

1.制造用于包装应用的层叠镀锡钢的方法,所述层叠镀锡钢包含镀锡钢片材和覆盖所述镀锡钢片材的至少一侧的热塑性层叠层,所述层叠层由多个层组成,其中每个层含有热塑性芳族(共)聚酯或其共混物或包含至少90摩尔%的亚丙基单元的聚烯烃,所述方法包括随后的步骤:
·通过电镀的方式向冷轧钢片材的一侧或两侧上提供锡层来产生镀锡钢片材;
·通过将所述镀锡钢片材浸入具有的pH为8-12的包含磷酸根离子、硼酸根离子、硫酸根离子或碳酸根离子或它们的组合的水溶液中来使所述镀锡钢片材经历表面处理;
·漂洗并干燥所述镀锡钢片材;
·任选地向所述镀锡钢片材施加无铬、无漂洗、原位干燥的钝化处理溶液;
·干燥经钝化的镀锡钢片材;
·提供所述热塑性层叠层用于涂覆在所述镀锡钢片材的至少一侧上;
·预加所述热镀锡钢片材并将所述热塑性层叠层层叠至经预加热的镀锡钢片材以产生层叠镀锡钢;
·后加热所述层叠镀锡钢至高得足以熔融所述层叠层的温度;
·冷却经后加热的层叠镀锡钢。
2.根据权利要求1所述的方法,其中用于层叠至经预加热的镀锡钢片材上的所述热塑性层叠层通过以下提供:
·提供预产生的单轴或双轴取向的热塑性层叠层,或
·在一个或多个挤出机中熔融热塑性聚合物粒料以形成一个或多个层并通过使熔融的一种或多种聚合物通过扁平的(共)挤出模头和/或两个或更多个压延辊来形成由所述一个或多个层组成的所述热塑性层叠层;之后:
A.
·冷却所述热塑性层叠层以形成固体热塑性层叠层;
·任选修整所述热塑性层叠层的边缘;
·通过仅在纵向方向上施加拉伸力通过在拉伸装置中拉伸所述固体热塑性层叠层来减小所述固体热塑性层叠层的厚度;
·任选修整经拉伸的热塑性层叠层的边缘;
·将所述层叠层层叠至经预加热的镀锡钢片材上;
·后加热所述层叠镀锡钢至高得足以熔融所述层叠层的温度;
·冷却经后加热的层叠镀锡钢,
或之后
B.
·在扁平的(共)挤出模头和浇注辊之间牵拉挤出的热塑性层叠层,并在所述浇注辊上浇注成其最终期望厚度以快速冷却经牵拉的热塑性层,其中浇注和冷却的热塑性层叠层基本上无取向;
·任选修整所述浇注和冷却的热塑性层叠层的边缘;
·将所述浇注和冷却的热塑性层叠层在线层叠至经预加热的镀锡钢板片上。
·后加热所述层叠镀锡钢至高得足以熔融所述层叠层的温度;
·冷却经后加热的层叠镀锡钢。
3.根据权利要求1至2中任一项所述的层叠镀锡钢,其中所述层叠层至少在变为包装例如容器或罐内侧的一侧上形成,并且所述层叠层中一个或多个层中的聚酯含有至少80mol%且优选85mol%的对苯二甲酸乙二醇单元或其中所述聚酯是包含至多35mol%的CHDM或20mol%的IPA的共聚酯。
4.根据权利要求1至2中任一项所述的层叠镀锡钢,其中所述层叠层至少在变为包装例如容器或罐内侧的一侧上形成,并且所述层叠层中一个或多个层中的聚酯含有至少80mol%且优选85mol%的对苯二甲酸丁二醇单元。
5.根据权利要求1至2中任一项所述的层叠镀锡钢,其中所述层叠层至少在变为包装例如容器或罐内侧的至少一侧上形成,并且所述层叠层中一个或多个中的聚酯含有含85摩尔%的对苯二甲酸乙二醇单元的聚酯和含至少85摩尔%的对苯二甲酸丁二醇单元的聚酯的共混物。
6.根据权利要求1至2中任一项所述的层叠镀锡钢,其中包装例如容器或罐的至少一侧上的一个或多个层叠层包含一个或多个基本上由聚丙烯组成的聚丙烯层。
7.根据权利要求1、2或6所述的层叠镀锡钢,其中所述一个或多个层叠层包含由马来酸酐接枝聚丙烯组成的粘附层。
8.根据前述权利要求中任一项所述的方法,其中所述层叠镀锡钢经历拉伸操作,其中所述拉伸操作通过以下实现:
·使材料通过平整机并施加0-3%之间、优选至少0.2%的厚度压下量;或
·使材料通过拉伸矫直机。
9.根据前述权利要求中任一项所述的方法,其中经钝化的镀锡钢片材的一侧或两侧上的所述层叠层是多层涂层体系,所述涂层体系至少包含用于粘附至经钝化的镀锡钢片材的粘附层、表面层和在所述粘附层和所述表面层之间的本体层。
10.根据权利要求1或2所述的方法,其中将所述浇注和冷却的热塑性层叠层使用切割装置(11)在纵向方向上切割成至少N个宽层叠层(9a-9d)和(N-1)个窄条(10a-10c),其中N为至少2,之后通过排出装置(12)引导所述窄条远离所述宽层叠层,并随后通过压送辊组件(4a,4b)将所述宽层叠层涂覆至经预加热的镀锡钢上以获得具有在纵向方向上由没有所述宽层叠层的窄条(10a-10c)空间隔开的多个宽层叠层(9a-9d)的层叠镀锡钢,并且其中所述镀锡钢的边缘保持没有所述宽层叠层,之后后加热所述层叠镀锡钢和冷却经后加热的层叠镀锡钢。
11.根据权利要求1至10中任一项所述的方法,其中所述层叠层具有在5和35μm之间的厚度。
12.通过根据权利要求1至11中任一项的方法获得的层叠镀锡钢。
13.用于生产3件式罐用坯料的层叠镀锡钢。
14.权利要求12或13的层叠镀锡钢在生产包装目的用罐和罐零件的方法中的用途。
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