CN117165938A - 金属表面处理剂、以及具有皮膜的金属材料及其制造方法 - Google Patents

金属表面处理剂、以及具有皮膜的金属材料及其制造方法 Download PDF

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Publication number
CN117165938A
CN117165938A CN202311250549.1A CN202311250549A CN117165938A CN 117165938 A CN117165938 A CN 117165938A CN 202311250549 A CN202311250549 A CN 202311250549A CN 117165938 A CN117165938 A CN 117165938A
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Prior art keywords
resin
treatment agent
compound
surface treatment
mass
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Inventor
德江大
铃木亮介
望月太郎
作本舞
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Nihon Parkerizing Co Ltd
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Nihon Parkerizing Co Ltd
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Publication of CN117165938A publication Critical patent/CN117165938A/zh
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    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
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Abstract

本发明提供一种能够在金属材料的表面或表面上形成能够保持抗菌性能的皮膜的新型金属表面处理剂，还提供具有皮膜的金属材料及其制造方法。一种金属表面处理剂，其包含通过将下式(1)所表示的化合物(a)与下式(2)或下式(3)所表示的化合物(b)进行聚合得到的共聚物(A)和水溶性或水分散性的树脂(B)，进行聚合的所述化合物(a)的摩尔量(aM)与所述化合物(b)的摩尔量(bM)的比[aM∶bM]在90∶10～20∶80的范围内，所述共聚物(A)的重均分子量为50000以上，所述树脂(B)为选自聚氨酯系树脂、聚乙烯醇系树脂、聚酰胺系树脂、环氧系树脂、酚系树脂及聚乙烯吡咯烷酮系树脂中的一种或两种以上，所述共聚物(A)的质量(AW)与所述树脂(B)的质量(BW)的比[AW/BW]在0.05～1.0的范围内。

Description

金属表面处理剂、以及具有皮膜的金属材料及其制造方法
本申请是中国申请号为202080010008.X的发明专利申请的分案申请，原申请的发明名称为“金属表面处理剂、以及具有皮膜的金属材料及其制造方法”，申请日为2020年1月23日。
技术领域
本发明涉及金属表面处理剂、以及使用它的具有皮膜的金属材料的制造方法和通过该制造方法得到的具有皮膜的金属材料。
背景技术
一直以来都在开发着关于具有抗菌性能的皮膜的技术。例如，专利文献1中公开了使用含有水分散性二氧化硅、水性聚氨酯树脂和水性嵌段化氨基甲酸酯预聚物的热交换器用亲水化处理剂形成的亲水性皮膜。专利文献2中公开了通过含有壳聚糖衍生物的亲水化处理剂形成的皮膜，上述壳聚糖衍生物是壳聚糖所具有的一部分或全部的伯氨基与在吸电子基的α位上具有碳-碳原子间不饱和基的化合物进行加成而成的。
现有技术文献
专利文献
专利文献1：日本特开平8-60031号公报；
专利文献2：日本特开2010-185024号公报。
发明内容
发明要解决的问题
本发明的目的在于提供一种能够在金属材料的表面或表面上形成能够保持抗菌性能的皮膜的新型金属表面处理剂、以及使用它的具有皮膜的金属材料的制造方法和通过该制造方法得到的具有皮膜的金属材料。
用于解决问题的方案
本发明人为了解决上述问题而进行了深入研究，结果发现，通过组合特定的树脂，能够在金属材料的表面或表面上形成能够保持抗菌性能的皮膜，从而完成了本发明。
即，本发明为下述内容等。
[1]一种金属表面处理剂，其包含：
通过使下式(1)所表示的化合物(a)与下式(2)或下式(3)所表示的化合物(b)聚合得到的共聚物(A)；和
水溶性或水分散性的树脂(B)，
进行聚合的上述化合物(a)的摩尔量(aM)与上述化合物(b)的摩尔量(bM)的比[aM∶bM]在90∶10～20∶80的范围内，
上述共聚物(A)的重均分子量为50000以上。
[化学式1]
[式(1)中，R1和R2各自独立地表示氢原子或碳原子数为1～4的烷基，R3和R4各自独立地表示碳原子数为1～5的烷基，X-表示卤素原子的离子或酸根阴离子，
式(2)中，R5表示氢原子或甲基，R6和R7各自独立地表示氢原子、碳原子数为1～4的烷基、苄基或者碳原子数为2或3的羟基烷基，
式(3)中，R8表示氢原子或甲基。]；
[2]根据上述[1]所述的金属表面处理剂，上述树脂(B)为选自聚氨酯系树脂、聚乙烯醇系树脂、聚酰胺系树脂、环氧系树脂、酚系树脂和聚乙烯吡咯烷酮系树脂中的一种或两种以上；
[3]根据上述[1]或[2]所述的金属表面处理剂，其中，上述共聚物(A)的质量(AW)与上述树脂(B)的质量(BW)的比[AW/BW]在0.05～1.0的范围内；
[4]根据上述[1]～[3]中任一项所述的金属表面处理剂，其还包含交联成分(C)；
[5]根据上述[4]所述的金属表面处理剂，其中，上述交联成分(C)为含羧基化合物(其中，共聚物(A)除外)和/或水溶性金属化合物；
[6]根据上述[4]或[5]所述的金属表面处理剂，其中，上述交联成分(C)的质量(CW)与上述质量(AW)和上述质量(BW)的合计质量的比[CW/(AW+BW)]在0.03～0.43的范围内；
[7]一种具有皮膜的金属材料的制造方法，其包括：使上述[1]～[6]中任一项所述的金属表面处理剂接触金属材料的表面或表面上的工序；使接触的上述金属表面处理剂干燥的工序；
[8]一种具有皮膜的金属材料，其通过上述[7]所述的制造方法得到。
发明效果
根据本发明，能够提供一种能够在金属材料的表面或表面上形成能够保持抗菌性能的皮膜的新型金属表面处理剂、以及使用它的具有皮膜的金属材料的制造方法和通过该制造方法得到的具有皮膜的金属材料。
具体实施方式
以下，对本实施方式的金属表面处理剂、以及使用它的具有皮膜的金属材料的制造方法和通过该制造方法得到的具有皮膜的金属材料进行说明。
(金属表面处理剂)
本实施方式的金属表面处理剂包含特定的共聚物(A)和水溶性或水分散性的树脂(B)。通过该金属表面处理剂，能够在金属材料的表面或表面上形成能够保持抗菌性能的皮膜。
<共聚物(A)>
共聚物(A)只要是通过将上述的式(1)所表示的化合物(a)(以下简单称作“化合物(a)”)与上述的式(2)或式(3)所表示的化合物(b)(以下简单称作“化合物(b)”)聚合得到的共聚物，则没有特别限制，可以为交替共聚物、无规共聚物、嵌段共聚物和接枝共聚物中的任一种。这些共聚物能够通过公知的聚合法制造。在制造共聚物(A)时，化合物(a)的摩尔量(aM)与化合物(b)的摩尔量(bM)的比在90∶10～20∶80的范围内即可，优选在80∶20～40∶60的范围内，更优选在70∶30～60∶40的范围内。
作为共聚物(A)的重均分子量，只要为50000以上则没有特别限制，优选为100000以上，更优选为500000以上。上限值优选为2000000以下。另外，重均分子量能够通过凝胶渗透色谱(GPC)分析求出。凝胶渗透色谱中使用的标准聚合物为聚乙二醇。
式(1)中的R1～R4和X-、式(2)中的R5～R7、以及式(3)中的R8如下所述。R1～R2各自独立地表示氢原子或碳原子数为1～4的烷基。R3～R4各自独立地表示碳原子数为1～5的烷基。X-表示卤素原子的离子或酸根阴离子。R5表示氢原子或甲基。R6和R7各自独立地表示氢原子、碳原子数为1～4的烷基、苄基或者碳原子数为2或3的羟基烷基。R8表示氢原子或甲基。另外，烷基可以是直链状，也可以是支链状。卤素原子为例如氟原子、氯原子、溴原子、碘原子等。酸根阴离子为例如CH3COO-等羧酸根阴离子等。作为羟基烷基，能够举出例如1-羟基乙基、2-羟基乙基、1-羟基丙基、2-羟基丙基、3-羟基丙基、2-羟基-1-甲基乙基等。
<水溶性或水分散性的树脂(B)>
作为水溶性或水分散性的树脂(B)(以下简单称作“树脂(B)”)，没有特别限制，从本发明的效果优异的方面出发，优选使用例如聚氨酯系树脂、聚乙烯醇系树脂、聚酰胺系树脂、环氧系树脂、酚系树脂、聚乙烯吡咯烷酮系树脂等。另外，树脂(B)可以是聚氨酯树脂、聚乙烯醇树脂、聚酰胺树脂、环氧树脂、酚树脂、聚乙烯吡咯烷酮树脂等均聚物；也可以是用其它化合物使该均聚物的侧链改性的改性物等，也可以是组合两种以上这些树脂、改性物的共聚物。这些树脂可以单独使用一种，也可以组合并用两种以上。
本实施方式的金属表面处理剂中的共聚物(A)与树脂(B)的添加比例没有特别限制，共聚物(A)的质量(AW)与树脂(B)的质量(BW)的比[AW/BW]优选在0.05～1.00的范围内，更优选在0.10～0.90的范围内，特别优选在0.20～0.80的范围内。
<其它成分>
本实施方式的金属表面处理剂除水性介质以外可以仅由共聚物(A)和树脂(B)形成，也可以还包含其它成分。作为其它成分，能够举出例如交联成分(C)、表面活性剂等。
作为交联成分(C)，只要是除了共聚物(A)、树脂(B)以外的连结树脂(B)的成分，则没有特别限定，能够举出例如含羧基化合物、水溶性金属化合物等。作为含羧基化合物，能够举出例如柠檬酸、1,2,3,4-丁烷四羧酸、酒石酸、苹果酸等。水溶性金属化合物的水溶性是指在1L的25℃的水中能够溶解1g该化合物。作为水溶性金属化合物，只要为水溶性，则没有特别限制，能够举出例如二异丙氧基钛双(三乙醇胺)钛等有机钛化合物；硫酸铬(III)、硝酸铬(III)等含铬化合物；六氟锆酸等无机系含锆化合物；六氟钛酸等无机系含钛化合物等。另外，有机钛化合物的意思是具有有机基团的含钛化合物。
在本实施方式的金属表面处理剂还包含交联成分(C)的情况下，共聚物(A)与树脂(B)与交联成分(C)的添加比例没有特别限制，交联成分(C)的质量(CW)与共聚物(A)的质量(AW)和树脂(B)的质量(BW)的合计质量的比[CW/(AW+BW)]优选在0.03～0.43的范围内，更优选在0.1～0.3的范围内。
作为表面活性剂，能够使用阳离子性、阴离子性、两性、非离子性等表面活性剂，能够举出例如烷基胺盐、烷基三甲基卤化铵等阳离子性表面活性剂；烷基磺酸酯、聚氧乙烯烷基苯基醚硫酸盐、十二烷基二苯基醚二磺酸钠、十二烷基硫酸钠等阴离子性表面活性剂；烷基氨基丙酸盐、烷基二甲基甜菜碱等两性表面活性剂；聚氧乙烯烷基苯基醚、聚氧亚烷基脂肪酸酯、脂肪酸甘油酯、山梨醇酐脂肪酸酯、聚氧乙烯甘油脂肪酸、聚氧乙烯丙二醇脂肪酸酯等非离子性表面活性剂等，它们可以单独使用一种，也可以组合使用两种以上。
<水系介质>
作为水系介质，只要包含50质量％以上的水，则没有特别限制，可以仅由水形成，也可以是包含水和水混溶性有机溶剂的混合液。作为水混溶性有机溶剂，只要可与水混合，则没有特别限定，可举出例如：丙酮、甲乙酮等酮系溶剂；N,N’-二甲基甲酰胺、二甲基乙酰胺等酰胺系溶剂；甲醇、乙醇、异丙醇等醇系溶剂；乙二醇单丁基醚、乙二醇单己基醚等醚系溶剂；1-甲基-2-吡咯烷酮、1-乙基-2-吡咯烷酮等吡咯烷酮系溶剂等。
这些水混溶性有机溶剂可以与水混合一种，也可以与水混合两种以上。
(金属表面处理剂的制造方法)
本实施方式的金属表面处理剂能够通过例如在水性介质中混合规定量的共聚物(A)和树脂(B)、根据需要而添加的其它成分来制造。
(具有皮膜的金属材料及其制造方法)
本实施方式的具有皮膜的金属材料的制造方法(以下简单称作“本实施方式的制造方法”)包括：接触工序，使上述的金属表面处理剂接触金属材料的表面或表面上；干燥工序，将接触了的金属表面处理剂干燥。通过该制造方法，可得到在表面或表面上具有能够保持抗菌性能的皮膜的金属材料。另外，本实施方式的制造方法可以在接触工序之前进行脱脂工序和/或化学转化处理工序。
<金属材料>
形成皮膜的金属材料的形状、结构等没有特别限定，能够举出例如板状、箔状等。关于金属材料的种类，也没有特别限定，可举出例如：钢铁材料(例如冷压钢板、热压钢板、黑皮材料、酸洗钢板、高强度钢板、工具钢、合金工具钢、球状化石墨铸铁、灰铸铁等)；镀层材料，例如镀锌材料(例如电镀锌、热镀锌、含铝镀锌、电镀锌、镀锌镍、镀锌钴、蒸镀锌等)、锌合金镀层材料(例如合金化热镀锌、Zn-Al合金镀层、Zn-Al-Mg合金镀层、电镀锌合金等)、镀铝材料、镀镍材料、镀锡材料、镀铬材料、铬合金镀层材料(例如Cr-Ni合金镀层等)等；铝材料或铝合金材料(例如1000系、2000系、3000系、4000系、5000系、6000系、铝铸件、铝合金铸件、压铸材料等)；铜材料或铜合金材料；钛材料或钛合金材料；镁材料或镁合金材料等。
<接触工序>
作为接触方法，能够举出例如喷涂法、浸渍法、辊涂法、棒涂法、帘式涂敷法、旋涂法、或这些的组合等方法，但并不限定于这些。接触温度、接触时间可根据金属表面处理剂的组成、浓度适当设定，通常，接触温度在0℃以上且50℃以下的范围内，接触时间在1秒以上且300秒以下的范围内。
<干燥工序>
干燥方法没有特别限制，能够举出使用公知的干燥设备、例如分批式的干燥炉、连续式的热风循环式干燥炉、传送带式的热风干燥炉、使用感应加热式加热器的电磁感应加热炉等的干燥方法等。干燥温度、干燥时间可根据金属材料的种类、接触的金属表面处理剂的组成或量来适当设定，通常，干燥温度在120℃以上且200℃以下的范围内，干燥时间在2秒以上且1800秒以下的范围内。
<脱脂工序>
作为脱脂方法，只要能够除去油脂类、污垢，则可以为任何方法，能够举出例如溶剂脱脂、使用碱系或酸系脱脂剂等的公知的方法。另外，在进行脱脂工序后进行接触工序或化学转化处理工序的情况下，可以在脱脂工序后且接触工序或化学转化处理工序前进行对金属材料的表面或表面上进行水洗的工序，也可以不进行该工序。在进行水洗的情况下，接下来可以干燥金属材料的表面或表面上，也可以不干燥。
<化学转化处理工序>
化学转化处理工序只要是形成化学转化皮膜的处理，则没有特别限定，可举出例如锆化学转化处理工序、钛化学转化处理工序、铪化学转化处理工序、磷酸盐化学转化处理工序、铬酸盐化学转化处理工序等。在化学转化处理工序后且接触工序前可以进行对金属材料的表面或表面上进行水洗的工序，也可以不进行该工序。在进行水洗的情况下，接下来可以干燥金属材料的表面或表面上，也可以不干燥。另外，作为化学转化处理工序，在进行使用磷酸锌的磷酸盐化学转化处理工序的情况下，可以在脱脂工序与磷酸盐化学转化处理工序之间，对金属材料进行用于提高磷酸盐化学转化处理的反应性的表面调节处理工序。作为该表面调节处理方法，能够使用公知的方法。
<化学转化处理剂>
化学转化处理工序通过使化学转化处理剂接触金属材料的表面或表面上来进行。作为化学转化处理剂，能够举出例如锆化学转化处理剂、钛化学转化处理剂、铪化学转化处理剂、磷酸盐化学转化处理剂、铬酸盐化学转化处理剂等，但不限定于这些。化学转化处理剂的接触可举出公知的方法，例如浸渍处理法、喷涂处理法、冲洗处理法或这些的组合等处理法，但不限定于这些。各种化学转化处理工序中的化学转化处理剂的温度或接触时间能够根据化学转化处理工序的种类、化学转化处理剂的浓度等适当设定。
<皮膜>
通过金属表面处理剂在金属材料的表面或表面上形成的皮膜的厚度只要能够发挥本发明的性能，则没有特别限制，例如优选在0.1μm以上且2.0μm以下的范围内，更优选在0.3μm以上且1.5μm以下的范围内。
实施例
使用实施例和比较例对本发明进行进一步详细地说明。另外，本发明并不限定于以下的实施例。
(金属表面处理剂的制备)
实施例01至07的金属表面处理剂和比较例01至05的金属表面处理剂的组成如表1所示。在表1中，聚合物、水溶性或水分散性树脂(B)以及交联成分(C)的栏内示出的各记号在表2～4内详细示出。各金属表面处理剂能够通过在水中混合各成分来制备。各金属表面处理剂中的固体成分含量调节为4％。另外，各聚合物的制造方法之后叙述。
[表1]
表1实施例和比较例的金属表面处理剂的组成
[表2]
表2聚合物的种类
[表3]
表3水溶性或水分散性的树脂(B)的种类
No. 种类 制造商 产品名
B1 聚氨酯树脂 第一工业制造株式会社 Superflex E-2000
B2 聚乙烯醇 株式会社Kuraray Kuraray Poval PVA-103
B3 改性聚酰胺树脂 Toray株式会社 AQ Nylon T-70
[表4]
表4交联成分(C)的种类
No. 种类 制造商 产品名
C1 有机钛 Matsumoto Fine Chemical株式会社 ORGATIx TC-400
C2 1，2，3，4-丁烷四羧酸 新日本理化株式会社 RIKACID BT-W
C3 硫酸铬(III) 日本化学工业株式会社 35％硫酸铬
有机钛：二异丙氧基钛双(三乙醇胺)钛
(各种聚合物的制造)
聚合物A1的制造
混合201g的化合物(a)的水溶液(60％)、53g的化合物(b)和580g的水，在氮气中升温至70℃。接着，加入15g的过硫酸铵的水溶液(20％)，在70℃使其反应15小时后，进行冷却，终止反应，制造聚合物A1。
聚合物A2的制造
混合81g的化合物(a)的水溶液(60％)、30g的水，搅拌该混合物，使其均匀地溶解后，升温至70℃，一边搅拌，一边添加6g的过硫酸铵的水溶液(20％)。开始发热后，一边保持70～80℃，一边滴加混合了108g的化合物(b)的水溶液(80％)和108g的水的水溶液。滴加结束后，进行2小时反应。其后，加入70g的水，搅拌后，进行冷却，终止反应。其后，加入氢氧化钠水溶液(20％)，调节至pH4.8，制造聚合物A2。
聚合物A3的制造
混合221g的化合物(a)的水溶液(60％)、51g的化合物(b)和322g的水，在氮气中升温至70℃。接着，加入15g的过硫酸铵的水溶液(20％)，在70℃使其反应7小时后，进行冷却，终止反应，制造聚合物A3。
聚合物A4的制造
混合362g的化合物(a)的水溶液(60％)、15g的化合物(b)和774g的水，在氮气中升温至70℃。接着，加入15g的过硫酸铵的水溶液(20％)，在70℃使其反应10小时后，进行冷却，终止反应，制造聚合物A4。
聚合物A5的制造
混合306g的化合物(a)的水溶液(60％)、300g的水，搅拌该混合物，使其均匀地溶解后，升温至70℃，一边搅拌，一边添加6g的过硫酸铵的水溶液(20％)。开始发热后，一边保持70～80℃，一边滴加混合了48g的化合物(b)的水溶液(80％)和150g的水的水溶液。滴加结束后，进行2小时反应。其后，加入150g的水，搅拌后，进行冷却，终止反应。其后，加入氢氧化钠水溶液(20％)，调节至pH4.8，制造聚合物A5。
聚合物A6的制造
混合308g的化合物(a)的水溶液(60％)、51g的化合物(b)和786g的水，在氮气中升温至70℃。接着，加入15g的过硫酸铵的水溶液(20％)，在70℃使其反应10小时后，进行冷却，终止反应，制造聚合物A6。
聚合物D2的制造
混合161g的化合物(a)的水溶液(60％)、383g的化合物(b)和960g的水，在氮气中升温至70℃。接着，加入15g的过硫酸铵的水溶液(20％)，在70℃使其反应6小时后，进行冷却，终止反应，制造聚合物D2。
聚合物D3的制造
混合56g的化合物(a)的水溶液(60％)、4g的化合物(b)和124g的水，在氮气中升温至70℃。接着，加入15g的过硫酸铵的水溶液(20％)，在70℃使其反应5小时后，进行冷却，终止反应，制造聚合物D3。
聚合物的重均分子量的测定
通过凝胶渗透色谱(GPC)分析求出聚合物A1～A6、D2和D3的重均分子量。其结果示于表2。
(评价样品的制作)
作为试验材料，使用铝板(株式会社PALTEK制A1050P，尺寸：40mm×40mm，板厚：0.8mm)(M1)和热镀锌钢板[镀层单位面积质量每面50g/m2(两面镀层)，尺寸：40mm×40mm，板厚：0.6mm](M2)。
通过将各试验材料在60℃浸渍于碱系脱脂剂[使FINE CLEANER 315E(日本帕卡濑精株式会社制)以质量浓度成为2％的方式溶解于水的溶液]2分钟来进行脱脂处理。其后，对试验材料的表面进行水洗。
通过将进行了脱脂处理和水洗的试验材料在60℃浸渍于锆系化学转化剂[使PALCOAT 3790M(日本帕卡濑精株式会社制)以质量浓度成为20％的方式溶解于水、调节为pH3.7的溶液]2分钟来进行化学转化处理。化学转化处理后，对试验材料的表面进行水洗。
将通过化学转化处理形成化学转化皮膜的试验材料在20℃浸渍于各金属表面处理剂15秒后，用鼓风干燥机在150℃加热干燥6分钟，由此制作具有皮膜的试验材料(评价样品No.1～12)。
(抗菌性能评价方法)
按照ISO 22196：2011(膜密合法)记载的评价方法，对评价样品No.1～12的抗菌性能(初始)进行评价。另外，作为细菌，分别使用金黄色葡萄球菌(Staphylococcus aureus)和大肠杆菌(Escherichia coli)。使用式[对象菌的减少率(％)＝100-Y/Z×100]算出对象菌的减少率，基于以下的抗菌性能判断基准评价抗菌性能。式中，Y表示加入评价样品进行培养时形成的菌落数，Z表示不加入评价样品进行培养时形成的菌落数。
此外，在去离子水中浸渍96小时后，对自然干燥的评价样品No.1～12的抗菌性能(保持性)也同样地进行评价。这些结果示于表5。
<抗菌性能判断基准>
◎(有抗菌性能)：对象菌的减少率为99.9％以上
〇(有抗菌性能)：对象菌的减少率为99.0％以上且小于99.9％
×(抗菌性能不充分)：对象菌的减少率小于99.0％
(防霉性能评价方法)
按照ISO 846：1997A法记载的评价方法，对评价样品No.1～12的防霉性能(初始)进行评价。另外，作为霉，使用混合孢子悬浮液(混合菌：黑曲霉(Aspergillus niger)、嗜松青霉(Penicillium pinophilum)、球毛壳菌(Chaetomium globosum)、木霉(Trichoderma)、宛氏拟青霉(Paecilomyces variotii)这5种)。防霉性能以菌丝的发育状态为指标，基于防霉性能判断基准来评价。
此外，在去离子水中浸渍96小时后，对自然干燥的评价样品No.1～12的防霉(保持性)也同样地进行评价。这些结果示于表5。
<防霉性能判断基准>
◎(有防霉性)：肉眼或显微镜下未确认到霉的发育。
〇(有防霉性)：肉眼未确认到霉的发育，但在显微镜下能够明显地确认到。×(防霉性不充分)：肉眼可确认到霉的发育。
[表5]
表5评价结果

Claims (7)

1.一种金属表面处理剂，其包含：
通过将下式(1)所表示的化合物(a)与下式(2)或下式(3)所表示的化合物(b)进行聚合得到的共聚物(A)；和
水溶性或水分散性的树脂(B)，
进行聚合的所述化合物(a)的摩尔量(aM)与所述化合物(b)的摩尔量(bM)的比[aM∶bM]在90∶10～20∶80的范围内，
所述共聚物(A)的重均分子量为50000以上，
所述树脂(B)为选自聚氨酯系树脂、聚乙烯醇系树脂、聚酰胺系树脂、环氧系树脂、酚系树脂及聚乙烯吡咯烷酮系树脂中的一种或两种以上，
所述共聚物(A)的质量(AW)与所述树脂(B)的质量(BW)的比[AW/BW]在0.05～1.0的范围内，
式(1)中，R1和R2各自独立地表示氢原子或碳原子数为1～4的烷基，R3和R4各自独立地表示碳原子数为1～5的烷基，X-表示卤素原子的离子或酸根阴离子，
式(2)中，R5表示氢原子或甲基，R6和R7各自独立地表示氢原子、碳原子数为1～4的烷基、苄基或者碳原子数为2或3的羟基烷基，
式(3)中，R8表示氢原子或甲基。
2.根据权利要求1所述的金属表面处理剂，其还包含交联成分(C)。
3.根据权利要求2所述的金属表面处理剂，其中，所述交联成分(C)为含羧基化合物(其中，共聚物(A)除外)和/或水溶性金属化合物。
4.根据权利要求2所述的金属表面处理剂，其中，所述交联成分(C)的质量(CW)与所述质量(AW)和所述质量(BW)的合计质量的比[CW/(AW+BW)]在0.03～0.43的范围内。
5.根据权利要求3所述的金属表面处理剂，其中，所述交联成分(C)的质量(CW)与所述质量(AW)和所述质量(BW)的合计质量的比[CW/(AW+BW)]在0.03～0.43的范围内。
6.一种具有皮膜的金属材料的制造方法，其包括：使权利要求1～5中任一项所述的金属表面处理剂接触金属材料的表面或表面上的工序；和使接触的所述金属表面处理剂干燥的工序。
7.一种具有皮膜的金属材料，其是通过权利要求6所述的制造方法得到的。
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