CN1396863A - 金属表面的复合防护层 - Google Patents
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Abstract
制备一种金属管或导管的金属基片如钢板用的复合防护层。所述防护层,当它涂布到一种平板金属表面时,它仍通过如那些用于制造肋条钢管的冷成型方法保持其与所述金属的粘结。所述涂层在两个粘膜之间组成一个夹心材料层。
Description
本发明涉及金属表面的防护层,更具体地说,涉及在冷成型时能保持粘结在这类金属表面上的防护层。本发明还涉及可冷成型的防护金属表面。本发明更具体地是涉及可冷成型的金属基片,它具有一种防护层涂布在其至少一个主平面之上,并涉及由这类基片制造得到的产品。举例来说,所述产品包括用于多种不同最终用途应用的管线以及电线和电缆产品。
金属表面易于受到多种不同来源如湿气、空气和范围广泛的化合物的腐蚀。这种易受攻击性倾向于限制金属在许多应用领域包括生活污水管系统或雨水管系统和含有酸性化合物的工业生产过程的使用。
一种提高金属表面如金属管道内表面的耐腐蚀的方法,是采用一种混凝土内衬。这种方法只具有有限的成功,因为混凝土难以在这类金属表面上形成一种稳定的粘结。混凝土还会断裂、碎裂并从所述金属表面上脱离,能明显地使所述金属暴露出来。另一种方法集中于由塑料层压钢板形成金属管道。WCI Steel Company ofWarren(Ohio)采用这种方法用来制备一种称作Poly-Coat的产品。一般地,先层压一种塑料或聚合物材料如炭黑填充的乙烯/丙烯酸(EAA)共聚物化合物,到一种合适的金属如钢板的表面上。接着将所述层压制品改建为管道,聚合物涂布表面变成内管壁。所述聚合物涂层的厚度通常不超过0.10英寸(0.25cm)。
美国专利USP4975138公开了一种用来形成一种涂层金属物体的方法。该方法包括三个连续步骤。首先制备一种层压制品,它包括一个未成型的金属基片通过一个热塑粘结层粘结到一个非涂层织物上。第二步,将所述层压制品成型为一种希望的形状,同时保留所述基片、织物和热塑粘结层之间的粘结。最后,在所述织物上涂布一种涂层。这类涂层倾向于缺乏均匀的厚度,至少在涂布到所述形状的内表面如内管表面时是这样的。为了保证具有最小的涂层厚度,人们通常是采用过量的涂料,从而提高了成本费用,而且,很可能会干扰管道内部的流体动力学。
USP5316606公开了一种用来成型聚合物层压金属管道的方法。该方法从钢板开始,它具有一种涂布到其至少一个表面上的EAA共聚物和一种聚乙烯/丙烯酸的混合物的共挤出的聚合物层。所述涂层钢板,在经过异形拉模(profile former)形成通道和接缝部件之后,使之与一个加热的聚乙烯内衬接触。施加的压力在所述加热的聚乙烯内衬与所述涂层钢板之间实现粘结。该方法通过成型所述钢板为一段管道而结束。
本发明的第一个方面提供一种用于金属表面的复合防护层,它包括:
a.一种用来粘结所述涂层到所述金属表面上的内粘膜,所述内粘膜包括:
1)一个由乙烯和丙烯酸共聚物形成的第一层,和
2)一个由EAA共聚物形成的第二层,所述第一层粘结在所述金属表面上,而所述第二层粘结在所述第一层上;
b.一个与所述内粘膜的第二层相邻并粘结在其上的加强层;和
c.一个与所述加强层相邻的外粘膜,所述外层包括:
1)一个由EAA共聚物形成的第一层,和
2)一个由EAA共聚物形成的第二层,所述第一层粘结在所述加强层上,而所述第二层粘结在所述第一层上。
本发明的第二个方面提供一种用于金属表面的复合防护层,它包括:
a.一种用来粘结所述涂层到所述金属表面上的内粘膜,所述内粘膜包括:
1)一个由羟基-苯氧基醚聚合物形成的第一层,和
2)一个由羟基-苯氧基醚聚合物形成的第二层,所述第一层粘结在所述金属表面上,而所述第二层粘结在所述第一层上;
b.一个与所述内粘膜的第二层相邻并粘结在其上的加强层;和
c.一个与所述加强层相邻的外粘膜,所述外层包括:
1)一个由羟基-苯氧基醚聚合物形成的第一层,和
2)一个由羟基-苯氧基醚聚合物形成的第二层,所述第一层粘结在所述加强层上,而所述第二层粘结在所述第一层上。
无论是第一个方面还是第二方面的复合涂层的外粘膜的第一层,优选地其具有的表面能超过所述外粘第二层的表面能。所述第一层经受电晕放电、火焰处理或其它常规表面改性,可提高所述第一层的表面能。
在第三个方面,本发明包括一种可冷成型的涂层金属物体,它包括:
a.金属基片;
b.第一个方面或第二个方面的复合防护层。
此处所用术语“互聚物”是表示一种其中具有聚合的两种或多种可聚合单体的聚合物。同样地,它包括共聚物(通常认为包括两种可聚合单体)、三聚物(三种可聚合单体)和四聚物(四种可聚合单体)。术语“共聚物”和“互聚物”在整个申请中可以互换使用。
本发明的复合防护层包括至少三层。简单地说,所述涂层是位于两个粘膜即内粘和外粘膜之间的夹心加强层。
所述内粘膜优选包括至少两层,一个第一层或金属粘结层,和一个第二层或内基层(inner base layer)。当所述涂层涂布到所述基片上时,所述金属粘结层在复合涂层和金属基片之间形成粘结。所述金属粘结层理想地占总膜层厚度的10-50%,优选为10-30%,更优选为15-25%。对于仅有两层的情形,所述第二层补足总膜厚度与所述金属粘结层厚度之间的所有差值。如果需要,所述内基层其自身可包括两层或多层。另外,尽管所述第一层名义上是一种金属粘结层,但是,所述第一层也可粘结到其它基片上。
所述内粘膜的金属粘结层和基极层,优选地都含有一种乙烯和一种烯属不饱和羧酸的共聚物,更优选含有一种EAA共聚物。所述EAA共聚物优选具有的丙烯酸,以总共聚物重量计,其含量范围为3-9wt%。含量在此范围之外的羧酸特别是丙烯酸也可使用,只要人们能够接受这类含量伴随而来的性能改变即可。另外,可采用两种或多种具有不违反本发明的范围和精神的不同羧酸含量共聚物的混合物。
用于所述内粘膜中第一层和第二层中的优选聚合物,包括乙烯和至少一种含有羧基官能团和其衍生物的可共聚的共聚单体的互聚物和酸酐改性的聚烯烃。合适的聚合物包括乙烯与1.0-50.0wt%烯属不饱和羧酸如丙烯酸或甲基丙烯酸或一种其C1-4烷基酯的互聚物。其它合适的聚合物包括乙烯的均聚物和互聚物,包括上述的互聚物,通过与一种活性的羧酸酸酐进行反应而改性。其它合适的聚合物包括乙烯和一氧化碳的共聚物。均聚物的例子包括低密度聚乙烯(LDPE)和高密度聚乙烯(HDPE)。其它合适聚合物包括羟基-苯氧基醚聚合物,也称作热塑性环氧(苯氧基)树脂。特别优选的共聚物包括EAA共聚物,更加优选的为一种具有丙烯酸含量多达共聚物重量10wt%的EAA共聚物。
当用来实施本发明以制备所述聚合物层时,优选的羟基-苯氧基醚聚合物包括:(1)具有下式表示的重复单元的羟基-官能化的聚醚:(2)具有下式表示的重复单元的酰胺-和羟甲基-官能化的聚醚:(3)具有下式表示的重复单元的羟基-官能化的聚(醚磺酰胺):或(4)具有由下述任一结构式表示的重复单元的聚(羟基酰胺醚): 或(5)具有下式表示的重复单元的聚(羟基酯醚):(6)具有由下述任一结构式表示的重复单元的聚(羟基酰胺醚):或(7)具有下式表示的重复单元的聚(羟氨基醚):和(8)具有下式表示的重复单元的羟基-苯氧基醚聚合物:其中,每个Ar单独地表示二价芳基、取代的二价芳基或杂环芳基,或不同的二价芳基、取代的芳基或杂环芳基的组合;R单独地为氢或一价烃基;每个Ar1为二价芳基或带有酰胺或羟甲基的二价芳基的组合;每个Ar2与Ar可以相同也可以不同,单独地为二价芳基、取代的二价芳基或杂环芳基,或不同的二价芳基、取代的芳基或杂环芳基的组合;R1单独地主要为亚烃基,如二价芳基、取代的二价芳基、二价杂环芳基、二价亚烃基、二价取代的亚烃基或二价杂亚烃基或这些基团的组合;R2单独地为一价烃基;A为胺基或不同胺基的组合;X为胺基、亚芳基二氧、亚芳基二磺基酰氨基或亚芳基二羧基或这些基团的组合;和Ar3为一种由下述任一结构式表示的“阳基环”部分:或其中,Y为无、共价键或连接基团,其中合适的连接基团包括例如氧原子、硫原子、羰基、磺酰基或亚甲基或类似的键;n为10-1000的整数;x为0.01-1.0;和y为0-0.5。
术语“主要为亚烃基”表示一种主要为烃的二价基团,但是,它任选地可含有少量的杂原子部分如氧、硫、亚氨基、磺酰基和磺酰氧基(sulfoxyl)。
由结构式I表示的羟基-官能化的聚醚,例如,可通过采用如US5164472所述方法,使一种缩水甘油醚或缩水甘油醚的混合物与一种二羟酚或二羟酚的混合物进行反应而制备得到。或者,羟基-官能化的聚醚是由一种二羟酚或二羟酚混合物与一种表卤代醇之间的反应而产生的,如Reinking,Barnabeo和Hale在Journal of AppliedPolymer Science,Volume 7,Page 2135(1963)中所述。
由结构式II表示的酰胺-和羟甲基-官能化聚醚的制备,举例来说,包括一种缩水甘油醚如双酚A的缩水甘油醚与一种具有侧链酰胺基、N-取代的酰胺基和/或羟烷基的二羟酚如2,2-二(4-羟苯基)乙酰胺和3,5-二羟苯酰胺之间的反应。USP5115075和USP5218075两个都公开了这类反应。
尽管一般地乙烯/羧酸共聚物特别是EAA共聚物是优选的,但是,当所述内粘膜的一层或两层含有或包括不同的聚合物时也可获得合适的结果。这类不同的聚合物包括乙烯/甲基丙烯酸(EMAA)共聚物、环氧聚合物或接枝烯烃聚合物,特别是马来酸酐(MAH)接枝的聚烯烃如聚乙烯。
所述外粘膜优选具有与所述内粘膜相同的层结构和组成。更优选地,所述外粘膜的第一层通过一种表面处理进行改性,以增强与所述加强层的粘结。采用常规装置和操作参数的电晕放电处理,能够获得令人满意的结果。可提高所述外粘膜表面能的火焰处理或其它技术可用来替代电晕放电处理。熟练的技术人员很容易理解这类处理或技术的常规装置和操作参数。
本发明所述防护层的内粘层和外粘层可包括不同的添加剂。这类添加剂包括抗粘连剂、抗氧化剂、颜料如炭黑或UV稳定剂。这些添加剂都是本领域公知的,它们可由众多的供应商购得。当该添加剂为颜料时,可采用任意的常规方法将所述颜料引入到粘结层中,优选是引入到粘结层的基极层中。例如,可在聚合载体中使用所述颜料的浓缩物。
所述内粘层和外粘层可通过任意本领域已知的技术形成。这类技术包括浇铸共挤出方法和吹膜共挤出方法。
所述加强材料合适地包括任意的纺织品、针织品或无纺布。实例包括天然纤维如棉花、羊毛、人造纤维和纤维素的织物,合成的聚合纤维如芳香尼龙纤维、聚酯、聚丙烯、萨纶、聚苯乙烯、聚酰胺、聚丙烯酸或聚甲基丙烯,和无机纤维如玻璃纤维、碳、钢、铝、不锈钢、陶瓷或氧化铝,它们可由任意合适的编织法、缝合法、簇绒法、粘合法、网状结合法或针法制备得到。优选的织物是非编织的聚酯,其中所述绒毛是由针刺所产生的。
本发明所述防护层还具有良好的耐磨性。防护层的耐磨性对于决定它是否符合全部性能指标是非常重要的。具有低耐磨性的防护层,较具有高耐磨性的涂层,倾向于更容易和快速地从金属表面上磨损掉。换句话说,低耐磨性涂层较高耐磨性涂层倾向于快地失去作用。这将反过来会使金属表面暴露,从而导致金属表面发生腐蚀。本发明的防护层相对于如镀锌或镀铝的金属处理和有机涂层如沥青和聚合物改性的沥青来说,其耐磨性得到提高。实验室规模试验可以证实这种提高,如American Society for Testing and Materials(ASTM)G-9 Cathodic Disbondment,ASTM 926 Bedload Abrasion,Impact resistance,Freeze Thaw Testing and Rotating Disk Exposure。
本发明的防护层能理想地适合于金属表面如不锈钢的防护。尽管不想局限于任何一种特定的金属表面或产品,但是,所述防护层非常适合用于金属管道(它是与聚合物内衬整体地成型的)的防护层。所述防护层可用来替代USP5316606中所教导的HDPE内衬和共挤出的EAA共聚物和聚乙烯/EAA混合物的薄膜的组合。
当涂布可改建为管道的钢基片时,对涂层管道目测就能发现,管道或其它物体在按ASTM 762规定经过90°角冷成型后,在复合防护层和基片之间基本没有发生层离(delamination)。当存在有层离时,更优选地不超过所述涂层管道表面积的10%。表面积层离更加优选是不超过5%,进一步优选是不超过2%。
USP5316606公开了在金属片(钢)中成形轧制波纹或肋条之前,涂布一种共挤出薄膜到金属管道表面上。将一种与所述薄膜相比相对厚的HDPE内衬,在所述肋条或波纹成型之后和在螺旋形缠绕使所述钢板形成管道部件之前或之后,涂布到所述内衬之上。
本发明的防护层具有足够的厚度,可保护金属基片如钢板在较由聚合物改性的沥青涂层提供的更长时间内不受磨损。当用作基极以涂布另外的涂层如HEPE内衬时,可提高耐磨性。本发明防护层的厚度合适地为至少0.010英寸(0.025cm)。所述涂层可厚达0.030英寸(0.076cm)。当采用更厚的涂层时,它们的性能不会有明显的提高,仅能增加涂层的费用成本。所述厚度希望地其范围为0.011-0.025英寸(0.028-0.064cm),优选范围为0.012-0.020英寸(0.030-0.051cm)。代表性的性能可由涂层厚度为0.013-0.015英寸(0.033-0.038cm)而获得,尤其是在厚度为0.014英寸(0.036cm)时。
所述防护层可涂布到金属基片的任意或所有侧面上,涂层侧面的数目取决于想要的最终用途。在所述防护层涂布之后,将所述涂层金属基片或物体成型为想要的形状。最优选地,所述金属是呈薄片形式,且所述防护层不会影响随后的压制波纹、弯曲、拔丝或成型操作。而且,这些成型操作优选不会影响所述防护层的整体性。
USP4791800的相关教导,公开了一种成形轧制方法和用来在条带材料中形成肋条以制备螺旋状肋条管道的装置。所得到的管道具有相对平坦的主要被直角肋条隔离开的区域。人们可以容易地使用这种方法和装置,将薄片金属条带材料(它涂布在具有本发明防护层的一个或两个主平面上)改建为螺旋状肋条管道。
所述金属基片合适的厚度为0.064-0.109英寸(1.6-2.8mm)。本发明防护层对于厚度低于0.064英寸的基片能起很好的作用。涂布这种防护层到厚度超过0.109英寸的金属基片上,根据基片厚度和涂层基片冷成型或变形的程度,会得到不同的结果。
尽管所述防护层可满足许多需要,但是,如果需要的话,人们可涂布一种或多种常规涂层材料如高密度聚乙烯,通过采用常规技术和装置如离心浇铸(它公开在USP4838317的第11栏62行-第12栏39行之中),或者是在预处理的波纹状薄片金属上挤压加工熔融聚合物(它公开在USP5316606的第4栏13行-第5栏41行之中)。USP4838317和USP5316606的全部内容引入本文作为参考。其它的涂层材料包括:树脂类材料,例如,包括那些含有其它材料如石料、橡胶共聚物如嵌段共聚物、增塑剂或油类和纤维填料的沥青组合物;天然或合成的涂漆、涂料或油漆、塑料溶胶;活性的树脂形成材料,如环氧树脂、聚酯、聚氨脂等。如果需要的话,如填料或固体粒子之类的其它材料也可加入到这些涂料之中,使所述表面具有想要的性能如耐磨性、抗滑性或质地。其它合适的涂料包括那些含有普通水泥和其它粘结涂料的物质,例如,混凝土和石膏。优选地,所述涂料包含沥青材料,其是以热熔体通过浸渍完全成型的金属物体到熔化的涂料之中进行涂布的,或者是通过喷雾所述涂料到其上而进行涂布的。
下述实施例将对本发明作详细的说明,但决不是限制本发明。除非有特别的规定,所有份数和百分比都是以重量为基准的。阿拉伯数字标记本发明的实施例,字母表的字母表示对比例。实施例1
在两个分离的双层EAA膜网(DAF 625,the Dow ChemicalCompany)之间夹入0.40盎司/平方码(0.011 kg/0.84m2)重量的纺粘聚酯网(直线4.4支/丝极纤维,Reemay“SV”grade 2004,XamaxIndustries,Inc.),以形成一种三网复合结构。每个双层膜网的厚度为6毫英寸(0.15mm),其中基极层占膜网厚度的85%,而表层占膜网厚度的15%。
所述基极层含有96wt%的EAA共聚物(5.5wt%丙烯酸,以共聚物重量为基准)、2wt%抗阻塞浓缩物(二氧化硅(SiO2)存在于低密度聚乙烯(LDPE)载体中,CN 734,Southwest Chemical)、2wt%抗氧化剂浓缩物(85wt%LDPE,15wt%SiO2和150ppm的二叔丁基(对甲酚),以LDPE和SiO2的总重量计,CN 734,Southwest Chemical),和11重量份的黑色浓缩物(Southwest 1000,Southwest Chemical),以100重量份的EAA共聚物、抗阻塞浓缩物和抗氧化浓缩物的总重量计。所述的颜色浓缩物含有62.7wt%LDPE、35.0wt%炉黑、1.8wt%四(亚甲基3,5-二-叔丁基-4-羟基苯丙醛)和0.5wt%二硬脂基硫代二丙酸酯,所有百分比都是以浓缩物重量为基准。
所述表层不含有颜色浓缩物,但在别的方面具有与所述基极层相同的组成。
为了获得一个处理的表面层,对一个膜网即所述外粘膜进行电晕放电处理。另一个膜网即所述内粘膜不接受这种处理。
通过组合所述网制备夹层结构,使所述聚酯网位于所述外粘膜的电晕处理表层和所述内粘膜的基极层之间。使所述夹层结构或三网复合结构经过加热的(160℃)轧辊,形成一个单一滚卷的复合防护层。所述轧辊对所述夹心层施加压力以促进所述复合涂层的形成。
层压所述复合防护层到一个清洁且预处理镀锌的钢板上(12规格或0.109英寸(2.77mm),它是经预热到400°F(204℃)的温度)),是通过采用由氯丁橡胶轧辊施加压力而进行的(100磅/平方英寸(689Kpa))。层压是采用125英尺/分钟(38.5m/min.)的线速和410°F(210℃)的温度进行的。在55°F(12.8℃)水浴中淬火所述层压制品。
冷成型所述层压制品为一种直径为48英寸(122cm)螺旋形有肋条的波纹状钢管。USP4791800的全部内容引入本文作为参考,USP4838317和USP5316606两者前面已经引入作为参考,它们都描述了制备螺旋形有肋条的波纹状钢管的制备方法。
对得到的冷成型钢管的目测检查表明,99%的涂层是牢固地粘结在所述钢板基片上的。通常的机械除去装置对所述涂层影响很小。与之形成对比的是,有些常规涂层则具有多达90%从所述钢板基片的层离,机械装置很容易地除去大部分的涂层。实施例2
重复实施例1,但是采用两种不同的EAA膜网厚度,颜色浓缩物的含量减至6重量份,改变所述颜色为灰色,改变成型所述防护层的方法和改变层压条件。一个EAA膜网的厚度为8.0毫英寸(0.20mm),它是用作内粘层。另一个EAA膜网的厚度为48.0毫英寸(0.10mm),它是用作外粘层。所述灰色浓缩物(Ampacet 19252,AmpacetCorporation)含有49.0wt%的LDPE、49.0wt%二氧化钛、1.0wt%槽法炭黑、0.6wt%群青颜料和0.4wt%十八烷酸,所有百分比都是以浓缩物重量为基准。
替代实施例1中采用加热的轧辊,组合所述夹层结构,将它放入到一个印压机中,施加压力(25吨(22727kg)并加热(400°F(204℃))一分钟,以促进复合防护层的形成。如实施例1所述,层压所述涂层到一个清洁且预处理镀锌的钢板上,但是降低线速为25英尺/分钟(7.6m/min.)和温度为400°F(204℃)。在55°F(12.8℃)水浴中淬火所述层压制品。
采用一种单辊成型机冷成型所述矩形单肋条为所述层压制品。采用一种与标准形成方法(它是采用多个形成模缓慢且逐渐地形成肋条)相对的单通道经过一个单成型模,所述单辊成型机快速地形成所述矩形的肋条。
对得到的冷成型钢管的目测检查表明,98%的涂层是牢固地粘结在所述钢板基片上的。通常的机械除去装置如刮刀仅能除去10%的涂层。实施例3
重复实施例2,但是改变纺粘聚酯网为0.50盎司/平方码(0.014kg/0.84m2)重量(直线2.2支/丝极纤维,Remay2250,XamaxIndustries,Inc.),并采用如实施例1所述的两个6毫英寸(0.15mm)的膜网。对得到的冷成型层压制品的目测检查表明,具有与实施例1相同的结果。实施例4
重复实施例3,但是用一种尼龙网材料(Thermanet,源自Conwed Plastics)替代所述纺粘聚酯网。对得到的冷成型层压制品的目测检查表明,具有与实施例1相同的结果。所述层压制品的表面具有一种模拟尼龙网材料的网格图形的大致结构。
采用改变的金属基片、膜网、加强材料、层压条件和冷成型条件,也可得到相似的结果,它们都公开在本文中。而且,所述冷成型层压制品可用作涂布进一步涂层如聚乙烯层的有效的基片,它可采用本文所述技术进行。
Claims (13)
1.一种用于金属表面的复合防护层,它包括:
a.一个用来粘结所述涂层到所述金属表面上的内粘膜,所述内粘膜包括:
1)一个由乙烯和丙烯酸共聚物形成的第一层,和
2)一个由乙烯和丙烯酸共聚物形成的第二层,所述第一层粘结在所述金属表面上,而所述第二层粘结在所述第一层上;
b.一个与所述内粘膜的第二层相邻并粘结在其上的加强层;和
c.一个与所述加强层相邻的外粘膜,所述外层包括:
1)一个由乙烯和丙烯酸共聚物形成的第一层,和
2)一个由乙烯和丙烯酸共聚物形成的第二层,所述第一层粘结在所述加强层上,而所述第二层粘结在所述第一层上。
2.如权利要求1所述防护层,其中所述外粘膜的第一层为电晕处理层。
3.如权利要求1所述防护层,其中所述每个内粘膜和外粘膜中的第二层还包括一种颜色浓缩物。
4.如权利要求3所述防护层,其中所述颜色浓缩物含有乙烯和丙烯酸的共聚物、聚乙烯和炭黑。
5.如权利要求1所述防护层,其中所述加强层含有一种非编织材料。
6.如权利要求5所述防护层,其中所述非编织材料为纺粘聚酯。
7.一种用于金属表面的复合防护层,它包括:
a.一种用来粘结所述涂层到所述金属表面上的内粘膜,所述内粘膜包括:
1)一个由羟基-苯氧基醚聚合物形成的第一层,和
2)一个由羟基-苯氧基醚聚合物形成的第二层,所述第一层粘结在所述金属表面上,而所述第二层粘结在所述第一层上;
b.一个与所述内粘膜的第二层相邻并粘结在其上的加强层;和
c.一个与所述加强层相邻的外粘膜,所述外层包括:
1)一个由羟基-苯氧基醚聚合物形成的第一层,和
2)一个由羟基-苯氧基醚聚合物形成的第二层,所述第一层粘结在所述加强层上,而所述第二层粘结在所述第一层上。
8.一种可冷成型的涂层金属物体,它包括:
a.金属基片;
b.权利要求1的复合防护层。
9.如权利要求8所述物体,其中所述金属基片为镀锌钢板。
10.如权利要求8所述物体,其中所述金属基片的厚度为0.064-0.109英寸(1.6-2.8mm)。
11.如权利要求8所述物体,其中在经过如ASTM 762所规定的对所述物体进行90°角的冷成型之后,所述物体在所述复合防护层和所述基片之间基本上没有发生层离。
12.如权利要求11所述物体,其中从所述基片上层离的复合防护层不超过10%。
13.一种可冷成型的涂层金属物体,它包括:
a.金属基片;
b.权利要求7的复合防护层。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US18080100P | 2000-02-07 | 2000-02-07 | |
US60/180,801 | 2000-02-07 |
Publications (1)
Publication Number | Publication Date |
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CN1396863A true CN1396863A (zh) | 2003-02-12 |
Family
ID=22661808
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CN01804447A Pending CN1396863A (zh) | 2000-02-07 | 2001-01-29 | 金属表面的复合防护层 |
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Country | Link |
---|---|
US (1) | US6617019B2 (zh) |
EP (1) | EP1265750A1 (zh) |
JP (1) | JP2003521398A (zh) |
KR (1) | KR20020072578A (zh) |
CN (1) | CN1396863A (zh) |
AU (1) | AU773071B2 (zh) |
CA (1) | CA2397395A1 (zh) |
CZ (1) | CZ20022668A3 (zh) |
MX (1) | MXPA02007628A (zh) |
TW (1) | TW527281B (zh) |
WO (1) | WO2001056786A1 (zh) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
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DK200000237A (da) * | 2000-02-15 | 2001-08-16 | Tresu Anlaeg As | Bjælke for kammerrakel samt kammerrakel |
US20050070660A1 (en) * | 2003-08-11 | 2005-03-31 | Daniel Bode | Curable polymeric water based coating compositions and resulting coatings with barrier properties for gases and coated substrates and containers |
US8247051B2 (en) * | 2003-08-11 | 2012-08-21 | The Glidden Company | Curable polymeric water based coating compositions and resulting coatings with barrier properties for gases and laminate structures |
GB2431374A (en) * | 2005-10-20 | 2007-04-25 | 3M Innovative Properties Co | Adhesive pad comprising fibrous layer of metal and polymeric fibers |
US20080136169A1 (en) * | 2006-09-29 | 2008-06-12 | Offshore Joint Services, Inc. | Pipeline field joint coating for wet insulation with improved adhesion |
ES2644494T3 (es) | 2007-09-11 | 2017-11-29 | Dow Global Technologies Llc | Composiciones y artículos preparados a partir de las mismas |
US8361611B2 (en) * | 2009-03-20 | 2013-01-29 | Whiteoptics Llc | Diffusively light reflective paint composition, method for making paint composition, and diffusively light reflective articles |
WO2010108160A2 (en) * | 2009-03-20 | 2010-09-23 | Eric William Hearn Teather | Diffusive light reflectors with polymeric coating |
EP2408867A4 (en) * | 2009-03-20 | 2013-03-06 | Eric William Hearn Teather | COLOR COMPOSITION USING DIFFUSER LIGHT REFLECTION, PROCESS FOR PREPARING THE COLOR COMPOSITION, AND ARTICLES WITH DIFFUSER LIGHT REFLECTION |
KR102292011B1 (ko) * | 2014-01-10 | 2021-08-20 | 고마쓰 마테레 가부시키가이샤 | 섬유 강화 수지 재료 및 그것을 이용한 섬유 강화 수지 성형체 |
DE102018115846A1 (de) | 2018-06-29 | 2020-01-02 | Tdc International Ag | Ummanteltes Rohr und Rohrverbindung, Rohrverbund |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
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US3908066A (en) * | 1973-05-11 | 1975-09-23 | United States Steel Corp | Protecting metal and metal products |
US4838317A (en) | 1980-10-14 | 1989-06-13 | Andre James R | Hydraulically efficient ribbed pipe |
US4975138A (en) * | 1986-07-07 | 1990-12-04 | The Dow Chemical Company | Method for coating formed metal objects and products formed thereby |
CA1286586C (en) * | 1987-03-26 | 1991-07-23 | Shigeki Yokoyama | Finish laminates for high frequency circuits |
GB8724241D0 (en) * | 1987-10-15 | 1987-11-18 | Metal Box Plc | Laminated metal sheet |
US4791800A (en) | 1987-10-26 | 1988-12-20 | Pacific Roller Die Co., Inc. | Roll forming process and apparatus for making ribs in strip material |
JPH01258482A (ja) | 1988-04-08 | 1989-10-16 | Fanuc Ltd | ガスレーザ装置用放電管 |
US5164472A (en) | 1990-01-18 | 1992-11-17 | The Dow Chemical Company | Hydroxy-functional polyethers as thermoplastic barrier resins |
US5115075A (en) | 1990-05-08 | 1992-05-19 | The Dow Chemical Company | Amide and hydroxymethyl functionalized polyethers as thermoplastic barrier resins |
US5218075A (en) | 1990-05-08 | 1993-06-08 | The Dow Chemical Company | Amide and hydroxymethyl functionalized polyethers as thermoplastic barrier resins |
CH689799A5 (de) * | 1995-11-28 | 1999-11-30 | Alusuisse Lonza Services Ag | Verpackungsbehälter aus einem mehrschichtigen Verbund |
US5846619A (en) | 1997-02-06 | 1998-12-08 | Sonoco Products Company | Polymeric liner ply for tubular containers and methods and apparatus for manufacturing same |
US6270869B1 (en) * | 1998-12-02 | 2001-08-07 | Alusuisse Technology & Management Ltd. | Cold formable laminate films |
-
2001
- 2001-01-29 CZ CZ20022668A patent/CZ20022668A3/cs unknown
- 2001-01-29 JP JP2001556659A patent/JP2003521398A/ja active Pending
- 2001-01-29 KR KR1020027010128A patent/KR20020072578A/ko not_active Application Discontinuation
- 2001-01-29 AU AU33082/01A patent/AU773071B2/en not_active Ceased
- 2001-01-29 WO PCT/US2001/002858 patent/WO2001056786A1/en active IP Right Grant
- 2001-01-29 EP EP01905174A patent/EP1265750A1/en not_active Withdrawn
- 2001-01-29 CA CA002397395A patent/CA2397395A1/en not_active Abandoned
- 2001-01-29 MX MXPA02007628A patent/MXPA02007628A/es not_active Application Discontinuation
- 2001-01-29 US US09/772,063 patent/US6617019B2/en not_active Expired - Lifetime
- 2001-01-29 CN CN01804447A patent/CN1396863A/zh active Pending
- 2001-02-06 TW TW090102511A patent/TW527281B/zh not_active IP Right Cessation
Also Published As
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MXPA02007628A (es) | 2003-01-28 |
TW527281B (en) | 2003-04-11 |
CA2397395A1 (en) | 2001-08-09 |
JP2003521398A (ja) | 2003-07-15 |
WO2001056786A1 (en) | 2001-08-09 |
US20010044022A1 (en) | 2001-11-22 |
CZ20022668A3 (cs) | 2003-05-14 |
US6617019B2 (en) | 2003-09-09 |
AU3308201A (en) | 2001-08-14 |
KR20020072578A (ko) | 2002-09-16 |
EP1265750A1 (en) | 2002-12-18 |
AU773071B2 (en) | 2004-05-13 |
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