CN1166865A - 含有肟加速剂的磷酸锌涂料组合物 - Google Patents

含有肟加速剂的磷酸锌涂料组合物 Download PDF

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CN1166865A
CN1166865A CN95196423A CN95196423A CN1166865A CN 1166865 A CN1166865 A CN 1166865A CN 95196423 A CN95196423 A CN 95196423A CN 95196423 A CN95196423 A CN 95196423A CN 1166865 A CN1166865 A CN 1166865A
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D·R·冯克
J·A·格里尼
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Abstract

本发明公开了含有一种肟加速剂的磷酸锌涂料组合物。该肟加速剂不会损害环境并且在可以形成单包装系统的磷酸锌涂料组合物的酸性环境中是稳定的。

Description

含有肟加速剂的磷酸锌涂料组合物
发明领域
本发明涉及一种含有稳定的加速剂的含水酸性磷酸盐涂料组合物；涉及用于制备这种组合物的浓缩物；涉及采用这种组合物在金属基体上形成磷酸锌涂层的方法以及涉及所得到的涂层金属基体。
发明背景
长久以来，人们知道在金属基体上形成磷酸锌涂层(也以磷酸锌转化涂层为人们已知)有助于产生耐腐蚀性并且可以增强涂料与已涂覆的金属基体的粘结性。磷酸锌涂层特别适用于在由一种以上的金属组成的基体上，例如车身或零部件，这些金属典型地包括钢、涂锌的钢、铝、锌及其合金。磷酸锌涂层可以通过将金属基体浸没在磷酸锌涂料组合物中、将该组合物喷涂在金属基体上、或者采用浸涂和喷涂的不同组合而施加到金属基体上。重要的是涂层要完全均匀地涂覆到基体的表面上并且涂层的涂覆无需大量时间或劳动力。
磷酸锌涂料组合物是酸性的，含有锌离子和磷酸根离子以及其它一些离子，如锰离子，这取决于特定的用途。为了使磷酸锌涂料快速涂覆到金属上，常常要向磷酸锌涂料组合物中加入加速剂。典型的加速剂是亚硝酸根离子，它是通过将亚硝酸根离子源，如亚硝酸钠、亚硝酸铵等等加入到磷酸锌涂料组合物中产生的。但是亚硝酸根在磷酸锌涂料组合物的酸性环境中不稳定，它会分解成没有加速能力的氮氧化物。因此，不能制成稳定的单包装涂料组合物；而且该亚硝酸根必需在使用前短时间内加入到磷酸锌涂料组合物中。亚硝酸根加速剂的另一个缺点是它们会产生引起废物处理问题的副产物(当对用过的磷酸锌溶液进行处理时)。人们希望有一种在磷酸锌涂料组合物的酸性环境中稳定的并且是环境可以接收的加速剂。
人们还提出了其它一些加速剂用于磷酸锌涂料组合物中，它们包括如芳香族硝基化合物，特别是间-硝基苯磺酸根离子，氯酸根离子、羟胺离子和过氧化氢的加速剂。
本发明的目的在于提供磷酸锌涂料组合物，它包括一种新型的加速剂，该加速剂具有特别好的涂层性能，在磷酸锌溶液的酸性环境中稳定，不会分解并且它是环境可以接受的。本发明的概要
本发明提供了一种用于在金属基体上形成磷酸锌涂层的含水酸性组合物，它包括约0.4-3.0克/升锌离子，约5-20克/升磷酸根离子和约0.5-20克/升肟作为加速剂。
本发明还提供了一种含水酸性浓缩物，它在用含水介质稀释时会形成上述含水酸性组合物，该浓缩物包括约10-100克/升锌离子，约100-400克/升磷酸根离子和约10-400克/升肟作为加速剂。
本发明还提供了用于在金属基体上形成磷酸锌涂层的方法，该方法包括用上述含水酸性磷酸锌涂料组合物与金属接触。
本发明还提供了一种金属基体，它含有通过上述方法而涂覆了1.0-6.0克/平方米磷酸锌涂层。详细描述
该含水酸性组合物中的锌离子含量优选地为约0.5-1.5克/升，更优选地为约0.8-1.2克/升，而磷酸根含量优选地为约8-20克/升，更优选地为约12-14克/升。该锌离子的来源可以是常规的锌离子来源，如硝酸锌、氧化锌、碳酸锌、金属锌等等，而磷酸根离子的来源可以是磷酸、磷酸一钠、磷酸二钠等等。该含水酸性磷酸锌组合物典型地具有约2.5-5.5，更优选地为约3.0-3.5的pH值。
该含水酸性组合物的肟含量是足以使该磷酸锌涂层的形成过程加速的含量，并且通常是以约0.5-20克/升，优选地为约1-10克/升，最优选地为约1-5克/升的量加入。该肟是一种可溶于含水酸性组合物中并且在该溶液中稳定足够长的时间，在pH2.5-5.5下不会过早分解并失去其活性，从而使该磷酸锌涂层在金属基体上的形成过程加速的一种物质。特别适用的肟是乙醛肟(它是优选的)和丙酮肟。
除了锌离子、磷酸根离子和肟以外，该含水酸性磷酸盐组合物还可以含有氟离子、硝酸根离子和各种金属离子，如镍离子、钴离子、钙离子、镁离子、锰离子、铁离子等等。当有这些离子存在时，氟离子的量应该在约0.1-2.5克/升，优选地为约0.25-1.0克/升；硝酸根离子的量应该为约1-10克/升，优选地为约2-5克/升；镍离子的量应为0-约1.8克/升，优选地为0.2-1.2克/升，更优选地为约0.3-0.8克/升；钙离子的含量应为约0-4克/升，优选地为约0.2-2.5克/升；锰离子的含量应为0-约1.5克/升，优选地为约0.2-1.5克/升，更优选地为约0.8-1.0克/升；铁离子的含量应为约0-0.5克/升，优选地为约0.005-0.3克/升。
已经发现在该酸性含水磷酸锌涂料组合物中含有与肟，优选地为乙醛肟结合的氟离子是特别有用的，优选地其含量为约0.25-1.0克/升。氟离子的来源可以是游离氟，例如来自二氟铵、氟化氢、氟化钠、氟化钾、或络合氟离子，如氟硼酸根离子或氟硅酸根离子。还可以采用游离氟与络合氟的混合物。与肟结合使用的氟离子典型地降低了达到用亚硝酸根加速的组合物等同效果所需的肟量。
除了肟加速剂以外，还可以与该肟加速剂一起使用除了亚硝酸根以外的加速剂。典型的加速剂是本领域已知的那些物质，例如芳香族硝基化合物，包括硝基苯磺酸钠，特别是间-硝基苯磺酸钠，氯酸根离子和过氧化氢。这些附加的加速剂如果采用的话，其含量为约0.005-5.0克/升。
根据本发明的特别适用的含水酸性磷酸锌组合物是pH为约3.0-3.5、含有约0.8-1.2克/升锌离子、约12-14克/升磷酸根离子、约0.3-0.8克/升镍离子、约0.8-1.0克/升锰离子、约2.0-5.0克/升硝酸根离子、约0.25-1.0克/升氟离子、约0.5-1.5克/升乙醛肟和约0.1-0.5克/升硝基苯磺酸钠。
本发明的含水酸性组合物可以在所说的浓度中采用上述组分新制得，也可以由含水浓缩物制得，其中各种组分的浓度比较高。浓缩物通常是提前制备并且运送到涂覆地点，在那儿将它们用含水介质，如水稀释或者有时将它们加入到所使用的磷酸锌组合物中。浓缩物是替代活性组分的一种实用方式。此外，本发明的肟加速剂在浓缩液中是稳定的，它们不会过早分解，与在酸性浓缩物中不稳定的亚硝酸盐加速剂相比，这是一个优点。典型的浓缩物通常含有约10-100克/升锌离子，优选地为10-30克/升锌离子，更优选地为约16-20克/升锌子和约100-400克/升磷酸根离子，优选地为160-400克/升磷酸根离子，更优选地为约240-280克/升磷酸根离子以及约10-400克/升，优选地为约10-40克/升肟作为加速剂。任选的组分，如氟离子，通常在该浓缩物中以约2-30克/升，优选地为约5-20克/升的量存在。其它任选的组分包括以约4.0-40克/升，优选地约为15-20克/升的量存在的锰离子；以约4-24克/升，优选地为4.0-12克/升的量存在的镍离子；以约20-200克/升，优选地约为30-100克/升的量存在的硝酸根离子。其它的金属离子，如钴、钙和镁也可以存在。附加的加速剂，如过氧化氢、硝基苯磺酸钠和氯酸根离子也可以存在。
本发明的含水酸性组合物可以用于涂覆有各种金属组合物组成的金属基体，例如黑色金属、钢、镀锌钢、或钢合金、锌或锌合金以及其它的金属组合物，如铝和铝合金。典型地，基体如车身，将含有一种以上的金属或与该金属的合金，本发明的磷酸锌涂料组合物特别适用于涂覆这类基体。
本发明的含水酸性锌组合物可以通过已知的涂覆技术，如浸涂、喷涂、间接喷涂、浸涂而后喷涂或喷涂而后浸涂而施加到金属基体上。典型地，该含水酸性组合物在约90-160华氏度(32-71℃)，优选地在约120-130华氏度(49-54℃)的温度下施加到金属基体上。用于涂覆该磷酸锌涂料组合物的接触时间当将金属基体浸涂该含水酸性组合物中时通常为约0.5-5分钟，而当将该含水酸性组合物喷涂到金属基体上时则为约0.5-3.0分钟。
在该基体上得到的涂层是连续和均匀的，其晶体结构可以是板状的、柱状的或球状的。涂层重量约为1.0-6.0克/平方米。
还可以明白地说，在通过本发明的方法涂覆涂层之前或以后均可以进行一些其它的步骤。举例来说，可以优选地将要涂覆的基体首先清洗以除去油脂、灰尘和其它一些外来物质。这一点可以通过采用常规清洗工艺及材料而做到。它们包括，如中性或强碱清洗剂、酸性清洗剂等等。在用这些清洗剂之后和/或之前通常要用水进行冲洗。
优选地，在清洗步骤之后或作为该步骤的一部分应采用调整步骤，例如在美国专利3310239、2874081和8884351中所说。该调整步骤包括将浓缩的磷酸钛溶液施加到该金属基体上。调整步骤在该金属基体表面上提供了成核位置、导致了可以提高性能的致密填充的结晶涂层的形成。
在形成磷酸锌转化涂层以后，对该涂层进行后处理冲洗，可以使该涂层密封并改善其性能。该冲洗组合物可以含有铬(三价和/或六价)，也可以没有铬。铬后处理例如可以含有约0.005-约0.1％重量铬(Cr+3，Cr+6，或其混合)。没有铬的冲洗可以引入锆化合物，例如参见美国专利3975214、4365000、4457790、4090353、4433015和4157028。
由下列非限制性实施例可以进一步理解本发明，这些实施例是用来说明本发明的，除非另有说明，否则其中所说的所有份均为重量份。
                      实施例1
下列实施例说明了本发明的各种含水酸性组合物的组成、用来将该组合物涂覆到金属基体上的方法、以及对所得到的磷酸锌涂层的评价。其中还提供了采用亚硝酸根加速剂的磷酸锌涂料的对比实施例。对所得到的磷酸锌涂层的晶体尺寸和类型以及所达到的涂层重量进行评价。
表1表2中的实施例1-16表示本发明和对比实施例的含水酸性组合物。表3-8表示在三种金属基体上施加1-16的含水酸性组合物的评价结果。表9和10中的实施例17-22表示本发明的含水酸性浓缩物的例子以及这些浓缩物的制备和稀释。
实施例2-6、实施例9-10和实施例14-16表示本发明的磷酸锌涂料组合物和方法以及通过浸涂法将它们涂覆到金属基体上。实施例1、7和8是用亚硝酸钠加速的对比实施例。
对于实施例1-10采用下列处理方法。
(a)脱脂：首先用碱性脱脂剂(“CHEMKLEEN 166/171ALX”，由PPGIndustries Inc.获得，2％重量)进行清洗，在55℃下，用它喷射金属基体达1分钟；
(b)冲洗：用自来水在室温下冲洗试验板达15-30秒；
(c)调整：在室温下，将冲洗过的试验板浸涂到表面调整剂(“PPGRinse Conditioner”，由PPG Industries Inc.获得，0.1％重量)中达1分钟；随后
(d)磷化：在52-55℃下，将试验板浸涂到表1中的酸性含水组合物中达2分钟；
(e)冲洗：在室温下，用自来水将涂覆过的试验板冲洗15秒钟。
            表1
   含水酸性磷酸锌涂料组合物浓度                  实  施  例  编  号(克/升)     1      2      3      4       5       6       7       8       9       10Zn       0.77   1.87   1.54   1.12    0.93    1.23    0.96    0.90    0.63    0.61Ni       0.43   0.51   0.39   0.43    0.41    0.57     ...     ...     ...     ...Mn       0.96   1.15   0.77   1.00    0.99    1.50     ...     0.83    ...     0.76PO4     11.3   10.1   11.6   13.9    14.0    14.7    16.9    17.2    17.7    18.2NO3     4.1    7.8    7.8    3.6     2.9     7.5     6.8     8.4     6.3     8.3Fe       0.015  0.005  0.021  0.005   0.006   0.004   0.008   0.005   0.011   0.007F        0.60    ...   1.11   ...     0.50    0.25    0.60    0.59    0.58    0.59AAO1     ...   15.0   5.0    2.0     1.0     5.0      ...     ...    1.0     2.0SNBS2    ...    ...   ...    0.26    0.32    ...      ...     ...    0.26    0.23氯酸根     ...    ...    ...    ...     ...    2.2      ...     ...     ...     ...亚硝酸根  0.095   ...    ...    ...     ...     ...    0.095   0.095    ...     ...游离酸3  0.6    0.7    0.7    0.8     0.7     0.6     0.7     0.6     0.7     0.6总酸      15.4   16.2   18.2   17.6    18.6    19.8    20.0    20.4    20.2    20.3
1 AAO是乙醛肟的缩写
2 SNBS是间-硝基苯磺酸钠的缩写
3 以点为单位对游离酸和总酸量进行测定。点等于每克毫当量×100。样品中酸性的毫当量等于用来中和1克样品所需的碱，典型地为氢氧化钾的毫当量(通过电位滴定测定)。
实施例11是采用喷涂技术施加的本发明的一个实施例。采用实施例1-10的处理方法，其不同之处在于“d”磷化步骤，此时在52-55℃下用在表2中给出的含水酸性组合物喷涂测试样品达1分钟。
实施例12和13是采用亚硝酸钠加速的对比实施例。实施例12、14和16的处理方法与实施例1-10的方法相似，有两处不同。在步骤“a”中，金属基体用“CHEMKLEEN 163”(由PPG Industries获得，2％重量)脱脂，在步骤“c”中，冲洗调整剂浓度为0.2％重量。
实施例13和15的处理方法与实施例12、14和16的方法相似，不同之处在于在步骤“c”中，冲洗调整剂浓度为0.1％重量。
           表2
  含水酸性磷酸锌涂料组合物
浓度              实  施  例  编  号
(克/升)      11      12      13     14      15      16     20
Zn          0.88    0.98    0.93   1.01    1.05    1.71
Ni          0.36     ...     ...    ...     ...     ...
Mn          0.92    1.00    0.97   1.01    1.06    0.28
W            ...     ...     ...    ...     ...    0.20
PO4        11.9    8.3     8.0    8.6     8.7     4.70
NO3        2.7     6.7     6.8    6.8     7.2     4.0
Fe          0.006   0.002   0.003  0.008   0.016   0.015
Ca           ...    0.50    0.33   0.53    0.44     ...
F           0.47     ...    0.20    ...    0.21    0.55
AAO         1.0      ...     ...   2.0     2.0     4.75
SNBS        0.27     ...     ...   0.26    0.23     ...
氯酸根       ...     ...     ...    ...     ...     ...
亚硝酸根     ...    0.095   0.095   ...     ...     ...
游离酸      0.6     0.6     0.9    0.8     1.3     0.5
总酸        15.4    12.2    11.7   13.5    14.0    8.4
                      表3在冷轧钢基体上的试验结果
                   实 施 例 编 号
           1      2      3     4     5     6     7     8     9     10外观4         N      P      P     P     C     F     C     C     C     C涂层重量      2.3    5.6    5.1   2.3   2.1   2.9   3.3   3.3   2.1   2.2(克/平方米)晶体尺寸      2-4    10-20  2-7   5-20  1-7   4-12   2-6  2-6   2-8   2-8(微米)
4 用扫描电子显微镜对外观金属测定。在所有实施例中，基体均用连续均匀的、致密的晶体磷酸锌涂层完全覆盖。晶体类型随着磷酸锌涂料组合物和基体而变化。球形基体用“N”表示，板状晶体用“P”表示，柱晶体用“C”表示。
               表4
     在电镀锌钢基体上的试验结果
                 实  施  例  编  号
             1       2       3       4        5       6       7        8       9       10外观             P       P       C       P        P       C       P        P       P       P涂层重量        2.5     2.5     2.8     2.3      2.9     2.7     4.1      3.5     3.1     3.1(克/平方米)晶体尺寸        2-6     2-4     1-2     2-6      2-5     2-4     5-15     2-4     5-10    2-4(微米)
                   表5
         在热浸镀锌钢基体上的试验结果
                    实  施  例  编  号
              1      2      3      4      5       6        7        8       9        10外观4            P      P      P      P      P       C        P        P       P        P涂层重量         2.4    2.5    3.2    3.0    2.8     2.0      4.8      3.9     4.2      3.8(克/平方米)晶体尺寸         4-10   2-6    2-4    2-10   2-6     2-4      5-30     4-8     5-25     5-10(微米)
                 表6
        在冷轧钢基体上的试验结果
                实  施  例  编  号
             11        12       13       14       15       16外观             P         P        C        P        C        P涂层重量        3.2       4.0      3.2      1.6      1.5      3.4(克/平方米)晶体尺寸        10-20     2-8      2-6      5-15     2-6      1-2(微米)
                 表7
        在电镀锌钢基体上的试验结果
              实  施  例  编  号
           11      12      13      14      15      16外观            P       P       P       P       P       P涂层重量       3.6     2.9     3.8     1.8     2.6     2.9(克/平方米)晶体尺寸       10-20   2-4     5-10    5-8     5-12    1-2(微米)
                 表8
        在热浸镀锌钢基体上的试验结果
            实  施  例  编  号
          11     12     13     14     15     16外观           P      P      P      P      P      P涂层重量      1.7    3.5    2.9    2.1    1.9    2.5(克/平方米)晶体尺寸      3-6    5-12   5-12   5-25   2-8    1-2(微米)
                 表9
         含水酸性磷酸锌浓缩组合物浓度                  实  施  例  编  号(克/升)       17     18     19     20     21     22Zn          15.4   37.4   30.8   22.4   18.6   24.6Ni          8.6    10.2   7.8    8.6    8.2    11.4Mn          19.2   23.0   15.4   20.0   19.8   30.0PO4        226    202    236    278    280    294NO3        82     156    156    72     58     150F           12     ...    22.2   ...    10.0   5.0AAO         ...    300    100    40.0   20.0   100SNBS        ...    ...    ...    5.2    6.4    ...氯酸根       ...    ...    ...    ...    ...    44.0表9中的含水酸性磷酸锌浓缩物由下列组分混合物制得。
                     表10重量％                         实    施    例    编
                17       18      19       20      21       22水                 39.84    44.31   43.64    43.90   47.88    22.89H3PO4(75％)      30.75    20.2    23.6     27.8    28.0     29.4HNO3(67％)        9.76     20.5    21.3     8.2     6.2      19.2ZnO                1.93     4.68    3.85     2.80    2.33     3.08MnO                2.48     2.97    2.00     2.58    2.55     3.87Ni(NO3)2(14％Ni) 6.14     7.34    5.61     6.20    5.90     8.20SNBS                ...      ...     ...     0.52    0.64      ...KF(40％)           9.10      ...    (16.8)    ...    2.50     3.79AAO(50％)           ...     (60.0)  (20.0)   8.0     4.0     (20.0)NaClO3(46％)       ...      ...     ...      ...     ...     9.57总份数             100      100      100     100     100      100
将水、磷酸、硝酸和乙醛肟一起混合。向该溶液中加入氧化锌和氧化锰。然后将其余的组分混合到该溶液中。采用过量的酸以确保各种组分完全溶解。
当制备浓缩物时，以不同方式加入组分。举例来说，可以将金属氧化物加入到快速混合的水的罐中以形成金属氧化物料浆。然后将酸加入到该料浆中，随后加入其余的组分。
浓缩物可以在工厂中制备并运送给用户使用。在用户工厂中、用20-100倍水稀释成浴浓缩物(即基于该浓缩物的总量，以1％-5％重量固体采用稀释的浓缩物)。
该含水酸性磷酸锌涂料组合物和浓缩物的上述实施例证实根据覆盖和涂层重量(它们是与耐腐性和与而后涂覆的涂料的粘结性有关的重要因素)，用肟加速的磷酸锌组合物与现有技术相比具有相同或更好的性能。该用肟加速的含水酸性磷酸锌组合物在浓缩物形式下是稳定的，形成便于稀释和在预处理浴中使用的单包装系统。

Claims (30)

1.一种用于在金属基体上形成磷酸锌涂层的含水酸性组合物，它包括约0.4-3.0克/升锌离子，约5-20克/升磷酸根离子，和约0.5-20克/升肟作为加速剂。
2.如权利要求1所定义的含水酸性组合物，其中所说的肟选自乙醛肟和丙酮肟。
3.如权利要求1所定义的含水酸性组合物，其中所说的锌的存在量为约0.8-1.2克/升。
4.如权利要求1所定义的含水酸性组合物，其中所说的磷酸根的存在量为约12-14克/升。
5.如权利要求1所定义的含水酸性组合物，它含有约0.1-2.5克/升氟离子。
6.如权利要求1所定义的含水酸性组合物，它含有约0-1.5克/升锰离子。
7.如权利要求1所定义的含水酸性组合物，它含有约0-1.8克/升镍离子。
8.如权利要求1所定义的含水酸性组合物，它含有约1-10克/升硝酸根离子。
9.如权利要求1所定义的含水酸性组合物，它含有选自钴、钙和镁的一种金属离子。
10.如权利要求1所定义的含水酸性组合物，它含有选自过氧化氢、硝基苯磺酸钠和氯酸根的附加加速剂。
11.一种用于在金属基体上形成磷酸锌涂层的含水酸性组合物，它含有约0.8-1.2克/升锌离子、约12-14克/升磷酸根离子、约0.25-1.0克/升氟离子、约0.8-1.0克/升锰离子、约0.3-0.8克/升镍离子、约2.0-5.0克/升硝酸根离子、约0.3克/升硝基苯磺酸钠和约1-5克/升乙醛肟作为加速剂。
12.一种含水酸性浓缩物，它在用含水介质稀释时会形成在权利要求1中所说的含水酸性组合物，该浓缩物包括约10-100克/升锌离子，约100-400克/升磷酸根离子和约10-400克/升肟作为加速剂。
13.如权利要求12所定义的含水酸性组合物，其中所说的肟选自乙醛肟和丙酮肟。
14.如权利要求12所定义的含水酸性浓缩物，其中所说的锌的存在量为约16-20克/升。
15.如权利要求12所定义的含水酸性浓缩物，其中所说的磷酸根的存在量为约240-280克/升。
16.如权利要求12所定义的含水酸性浓缩物，其中所说的肟的存在量为约10-40克/升。
17.如权利要求12所定义的含水酸性浓缩物，它含有约2-30克/升氟离子。
18.如权利要求12所定义的含水酸性浓缩物，它含有约4-40克/升锰离子。
19.如权利要求12所定义的含水酸性浓缩物，它含有约4-24克/升镍离子。
20.如权利要求12所定义的含水酸性浓缩物，它含有约20-200克/升硝酸根离子。
21.如权利要求12所定义的含水酸性浓缩物，它含有选自钴、钙和镁的一种金属离子。
22.如权利要求12所定义的含水酸性浓缩物，它含有选自过氧化氢、硝基苯磺酸钠和氯酸根的附加加速剂。
23.用于在金属基体上形成磷酸锌涂层的方法，该方法包括用在权利要求1所说的含水酸性磷酸锌组合物与金属接触。
24.如权利要求23所定义的方法，其中所说的肟选自乙醛肟和丙酮肟。
25.如权利要求24所定义的方法，其中所说的肟的存在量为约1-5克/升。
26.如权利要求23所定义的方法，其中所说的含水酸性磷酸锌组合物含有约0.8-1.2克/升锌。
27.如权利要求23所定义的方法，其中所说的含水酸性磷酸锌组合物含有约12-14克/升磷酸根。
28.如权利要求23所定义的方法，其中所说的含水酸性磷酸锌组合物含有约0.1-2.5克/升氟离子。
29.一种金属基体，它含有通过权利要求23的方法涂覆的1.0-6.0克/平方米磷酸锌涂层。
30.权利要求29所说的金属基体，其中该金属选自黑色金属、钢、镀锌钢、钢合金、锌和锌合金、铝和铝合金及其混合物。
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