CN1041774A - 临时保护涂料组合物 - Google Patents

临时保护涂料组合物 Download PDF

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CN1041774A
CN1041774A CN89107776A CN89107776A CN1041774A CN 1041774 A CN1041774 A CN 1041774A CN 89107776 A CN89107776 A CN 89107776A CN 89107776 A CN89107776 A CN 89107776A CN 1041774 A CN1041774 A CN 1041774A
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wax
protective cover
acid
coating
composition
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CN1032481C (zh
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埃罗·詹姆斯·范巴斯克瑞克
鲁道夫·马斯卡
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PPG Industries Inc
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Abstract

一种用在金属表面的可成型、可焊接的临时保护涂料，该涂料包括含蜡的用碱中和的具有酸或碱功能的共聚物。

Description

本发明涉及用于使未经处理的金属衬底印化的临时保护涂料组合物。更准确地说，本发明涉及含有加聚物和蜡的含水临时保护涂料组合物，它可用作轧钢厂（mill）的纯化组合物。
在轧钢厂中，主要是用轧钢油（mill        oil）或化学处理方法使金属钝化，以防止或减少腐蚀，特别是白锈。轧钢油的缺点是难以有效地清除，且其防腐蚀的效果也不够好。化学处理，特别是使用成膜材料的处理方法的缺点是其与接着涂到衬底上的材料和所用的工艺是不相容的。
与本技术有关的含有可溶于碱的含羧基的聚合物（或）蜡的保护涂料组合物在技术上是众所周知的。大多数这类组合物显然都用于涂漆或抛光的表面，而用于未经处理的金属衬底时效果较差。
可是，这里感兴趣的保护涂料组合物应适合涂在无屏蔽的金属衬底上。而且，这些保护涂料组合物应能与接着涂敷的预处理组合物相容，应该是可成形、可焊接的，而且可用含水的碱溶液清除，它们还应能防止或减少腐蚀，特别是呈白锈状态的腐蚀。本发明提供的就是这类临时保护涂料组合物。
按照上面所述，本发明包括一种用以涂在金属衬底上的可成形、可焊接的含水临时涂料组合物，该组合物含有一种中和的具有酸或碱的功能的聚合物与一种润滑组合物的组合物，润滑组合物主要是由较大量的蜡组合的，蜡的含量要足以使其所涂敷的金属衬底具有可压延性和可成形性。
在本发明的实施方案中使用了一种用碱中和的具有酸功能的聚合物。该具有酸功能的聚合物与蜡的组合物的制备方法是使多种烯属不饱和单体（其中至少有一种是具有酸功能的）在蜡（如烃类蜡）的存在下在溶剂中进行共聚。使所得的组合物在碱（如氢氧化铵）的存在下在水中分散。
当本发明的较好的实施方案中的保护涂料组合物用作钝化剂时，能产生耐腐蚀、可压延、可成形、可焊接的涂层，且该涂层易于用碱或酸的水溶液清除。
“可成形的”或“可成形性”这一术语是指涂了涂料的金属薄板在弯曲时不会在涂膜内产生明显的裂纹或空隙的能力。“可压延的”或“可压延性”这一术语是指涂了涂料的金属薄板在冲压成形成弯曲的三维形状时不会产生明显的破裂和损坏的能力。“可焊接的”或“可焊接性”这一术语是指可用常用的点焊焊嘴和压力在涂了涂料的金属薄板上进行点焊的能力。不难理解，上述性能会受所选用的金属薄板的特性影响。但无论如何，本发明的保护涂料组合物使上述性能得到显著的改善。
本发明的较好的实施方案中的含水临时保护涂料组合物的特点在于其是可压延、可成形、可焊接的，而且易于用碱的水溶液清除。下面将更为详细地描述本发明的保护涂料组合物的这些方面和其他方面的特点。
本发明所使用的用酸或碱中和的官能聚合物的玻璃化温度（Tg）约为-30～100℃，最好约为-15～30℃，重均分子量约为3，000～90，000，最好约为5，000～30，000。一般，该聚合物为溶液聚合的自由基加聚物。这些聚合物可以具有酸或碱的功能。按照本发明，具有酸功能的聚合物可由多种烯属不饱和单体（其中至少有一种是具有酸功能的）在溶剂介质中进行聚合而制得。这类具有酸功能的单体的例子有丙烯酸、甲基丙烯酸、巴豆酸、衣康酸、马来酸等。具有酸功能的单体的用量可以是单体总重量的约5～100%，一般，用量约为10～40%（重量），最好为10～30%（重量）。可以使用的可共聚的烯属不饱和单体有乙烯基单体（如苯乙烯、乙烯基甲苯等）、丙烯酸酯类或甲基丙烯酸酯类（如甲基丙烯酸甲酯、丙烯酸丁酯和丙烯酸（2-乙基已基）酯）。
具有碱功能的聚合物可由多种烯属不饱和单体（其中至少有一种是具有碱功能的在溶剂介质中进行聚合而制得。具有碱功能的单体的例子有（甲基）丙烯酸氨烷基酯、（甲基）丙烯酸叔丁基氨乙基酯、（甲基）丙烯酸二异丁基氨乙基酯的（甲基）丙烯酸二甲基氨乙基酯。具有碱功能的单体的用量约为1～50%，最好约为5～20%。
可用于本发明的润滑剂组合物主要是由蜡组成的。正是蜡使保护涂料组合物具有可压延性蜡的熔点一般约为140°F。适用的蜡包括具有不同熔点的和不同等级的烃类蜡，如蜂蜡、巴西棕榈蜡及其混合物。蜡的用量约占蜡与聚合物的总重的5～70%，最好为10～30%。润滑剂组合物中还可含硅油、二硫化钼、石墨、烃油、植物油、脂肪酸和树脂之类的添加剂。在较为适合的实施方案中、加聚物是在加蜡的情况下制备的，估计蜡与聚合物之间产生了接枝反应，虽然并不是必须这样。但应认识到，聚合物可以在不加蜡的情况下制备，然后与蜡一起使用，所用的蜡最好是粉未或液体状态。
在本发明的最佳实施方案中，用石墨或与其相当的物质作添加剂，从而使所涂的保护涂料组合物在焊接时的导电性能改善。这类添加剂一般都呈颗粒状使用。其用量要足以使较厚的涂膜能进行焊接。在本发明中，这类添加剂宜用于厚度为1.5毫米/英寸2或更厚的涂膜中。
保护涂料组合物的制备方法是用水将含蜡的、用酸或碱中和的溶液聚合物稀释，使其具有便于涂敷的粘度。在这过程中可至少使官能高聚物部分地中和。中和可在稀释前或在稀释时进行。宜采用挥发性中和剂。所谓“挥发性”是指该中和剂在涂层进行干燥或烘烤时会从涂层中逸出。具有酸功能的聚合物用碱中和。碱的例子有氨（包括氢氧化铵）、伯胺或仲胺（例如乙醇胺、二乙醇胺、N-甲基乙醇胺、二甲基乙醇胺、甲胺、乙胺、三乙胺和吗啉）。具有碱功能的聚合物可用诸如醋酸、乳酸、磷酸之类的有机酸或无机酸中和。
本发明可使用消泡剂、湿润剂或附加的共溶剂之类的添加剂。本发明的一个明显的特点是该保护涂料组合物不含或基本上不含会产生对水敏感和降低耐腐蚀性等不良后果的外来的表面活性剂。
实施本发明时，可用喷涂、刷涂、浸涂、辊涂、幕涂等常用方法将保护涂料组合物涂在金属衬属衬底上。涂料的用量约为0.3～4毫克/平方英寸，较好的约为0.5～3毫克/平方英寸，最好约为1.0～2.0毫克/平方英寸。当然，不难理解，表面粗糙度和孔隙度不同的衬底所需保护涂料组合物涂膜的厚度也不同。使所涂的涂料晾干或在很短的时间内强制干燥或烘干。这样生成的涂层具有抗粘着性，即涂了涂料的衬底叠放时不会粘着在一起。
使碱或酸的水溶液与涂了涂料的衬底接触便能很容易地清除所涂的涂料。所谓“接触”是指喷射、浸渍、浸泡等方法。值得注意的是，在生产实践中喷射的清洁剂不能直接喷到制品内的封闭部分，因而不能很好地清除那里的常用润滑剂。本发明的涂料组合物能显著地改善制品的耐腐蚀性。本质上是由于用浸泡的方法能把涂料完全从封闭区域清除，从而使制品的所有表面都得到适当的预处理。因而使接着涂上去的油漆层的粘合力得到显著的改善。溶液的浓度取决于特定的碱或酸溶液的性质、清除的温度和溶液达到的中和程度。清除保护涂料后，衬底可直接使用，或涂上其他涂层，如转化涂层。
本发明的一个明显的特点是本发明的保护涂料可在室温下通过浸泡的方法使之有效地清除。
由于本发明的保护涂料组合物较易清除，我们认为该组合物可单独使用，也可再加少量轧钢油后使用。保护涂料组合物是可清除、可压延、可成形、可焊接的，且耐腐蚀。清除保护涂料组合物后，衬底可不经进一步处理而直接使用，也可接着再加涂层。
下面的实施例对本发明作进一步的说明，但本发明不限于这些。
实施例1A
本实施例说明含蜡的水基丙烯酸树脂的制备方法。
在室温下将一种由135克丁基溶纤剂、22.5克丁醇和101.3克SHELLMAX（软化点约为60℃的一种石油蜡，系SheLL        oil        Co产品）的混合物组成的组合物加入将有温度计、搅拌器、滴液漏斗、回流冷凝器和用于保持氮气层的装置的反应容器中。用大约30分钟的时间将该组合物加热至回流，达到回流温度后，在搅拌下开始同时将进料A和进料X渐渐加入容器中，加料时间持续3小时。进料A是由317.2克丙烯酸丁酯、202.5克苯乙烯、135.0克丙烯酸和20.3克甲基丙烯酸二乙基氨乙基酯的混合物组成的，而进料X则是由6.8克丁基溶纤剂和20.3克过苯甲酸叔丁酯的混合物组成的。在150℃下将进料A和进料X加完后，再将由2.3克丁基溶纤剂和2.3克过苯甲酸叔丁酯组成进料B加入，并使该反应混合物反应2小时。然后在141℃下将由2.3克过苯甲酸叔丁酯和2.3克丁基溶纤剂组成的进料C加入，并使反应混合物反应1小时。然后将反应混合物冷却至79℃（50/50树脂/M-pryol混合物在固体含量为41.1%时具有Z-5 Gardnez-Hold+粘度）。接着用15分钟时间将含有112.5克去离子水和107.1克氢氧化铵的进料D加入，并保持15分钟。最后在72℃下用1.5小时的时间将含1968.0克去离子水的进料E加入反应混合物中。分析结果：酸的毫当量为0.429，碱的毫当量为0.453，重均分子量（Mn）为10.924，在20转/分（PPM）下粘度为4320厘泊（Brookfield 4号心轴），PH为9.30，固体含量为22.9%（在110℃下测定2小时）。
实施例1B
本实施例进一步说明含蜡的水基丙烯酸聚合物的制备方法。制备过程中使用了下列成分：
成份        重量份
反应器进料
丁基溶纤剂        140.0
丁醇        23.3
SHELLMAX        483.0
进料X
丁基溶纤剂        7.00
过苯甲酸叔丁酯        9.7
进料A
丙烯酸        322.0
1-十二烷硫醇        4.8
进料B
丁基溶纤剂        2.4
过苯甲酸叔丁酯        2.4
进料C
丁基溶纤剂        2.4
过苯甲酸叔丁酯        2.4
进料D
去离子水        117.0
氢氧化铵        271.1
进料E
去离子水        2040
在室温下将由反应器进料组成的组合物加入-装有温度计、搅拌器、滴液漏斗、回流冷凝器和用于保持氮气层的装置的反应容器中。用约30分钟的时间将该组合物加热至回流。达到回流温度后，在搅拌下开始同时将进料A和进料X渐渐加入容器中，加料时间持续3小时。在135℃下将进料A和进料X加完后，将进料B加入，并保持2小时。在125℃下将进料C加入，并保护1小时。然后将反应混合物冷却到80℃（树脂固体含量为82.2%）。用15分钟时间将进料D加入反应混合物中并保持15分钟。在72℃下用1.5小时的时间将进料E加入反应混合物中。分析结果：酸的毫当量为0.921，碱的毫当量为0.805，重均分子量为1410，20RPM下的粘度为465厘泊（Brookfield4号心轴），PH为7.10，固体含量为26.8%（在110℃下测定2小时）。
实施例Ⅱ
用水将实施例Ⅰ的水基丙烯酸醇聚合物稀释至固体含量达12%，并用流涂法将其涂在刚清洗干净的镀锌板上。晾干15分钟至不粘手为止，然后在105℃下强制干燥5分钟。结果在板上形成一层涂膜，其重量为0.8～0.9毫克/英寸2。
实施例Ⅲ
将实施例IB中的水基丙烯酸聚合物稀释，使其固体含量达20%，然后用-6号金属丝缠绕的牵引杆（drawbar）将其涂在刚清洗干净的镀锌板上，并在550°F下烘烤50秒，使金属的最高温度达420°F，接着使之骤冷。面上生成的涂膜的重量为1.1毫克/平方英寸。将该涂了涂料的薄板于140°F下在工业用碱清洗剂中，浸1分钟，并在热的自来水中漂洗30秒。这样就得到无水膜残迹表明其具有很高清洁度的板。
比较实施例Ⅰ
作为实施例Ⅱ的板的对照试验，将市场上能买到的用以防止镀锌钢或其他钢腐蚀的轧钢油涂在刚清洗干净的镀锌的板上。滴两滴Quakev 61A-US油（Quakov Chemical Co产品）在4×12英寸的板上，并用一已经该油浸湿的情况的白棉线手套的指套抹开。所成涂膜的重量为0.6～0.8毫克/英寸2，这多于市场上能买到的镀锌钢发运来时所涂的油，后者的重量约为0.4毫克/英寸2。
评定试验：
湿气腐蚀试验
将实施例Ⅱ的板与比较实施例Ⅰ的板叠在一起，夹紧，并放入湿润箱中，在115±5°F和100%相对湿度的条件下放置一周。
实施例Ⅱ的试验板从湿润箱中段出后，浸入150°F的1%碱清洗剂溶液中清洗30秒。所用清洗剂CHEMKLEEN49是Chemfil公司的产品。板漂洗后无水膜残迹，这说明它是很干净的。用目视法将经过湿气试验的板与未经湿气试验但用同样的方法清洗过的板进行比较，本发明经过湿气试验的板的颜色有明显的变化，即使有变化也是很小的。颜色不变就说明锌层没有发生多少氧化作用。
比较实施例1的板（涂轧钢油的）从湿润箱中取出后，浸入同样的1%碱清洗剂溶液中清洗3分钟。漂洗后，板上有很多水珠，这说明该板并没有清洗干净。用溶剂擦拭并再浸洗30秒后，板上才无水膜残迹，说明已干净。用目视法将经过湿气试验的板与未经湿气试验但用同样的方法清洗过的板进行比较，发现经过湿气试验的板的颜色比未经试验的板深得多。面上的灰色涡流状花纹说明锌已明显地氧化。
实施例Ⅳ
为了试验实施例Ⅱ的保护涂料组合物的可压延性和润滑性，用实施例Ⅱ的方法再涂一些镀锌板。涂层的重量约为1.0～1.1毫克/英寸2。
比较实施例Ⅱ
作为实施例Ⅳ的对照试验，将一种能在市场上买到的水基压延润滑剂Pillsbury FB-27MC涂在刚清洗干净的镀锌板上。在板上滴18滴FB-27MC润滑剂，并用一已经该润滑剂浸湿的清洁的白棉线手套的指套将其抹开，使其分布在5×13英寸的板面上，然后使其干燥。润滑剂的用量约为0.6毫克/英寸2。
制造试验
为了试验可压延性、可成形（制造）性和可洁净性，将实施例Ⅳ和比较实施例Ⅱ的板压延成高度为1英寸、边长为1-7/16英寸的方杯。使方杯侧面上的一个区域变形以产生+20%最大应变（major        shan）和-12%最小应变（minor        Shan）。使方杯侧面上的另一区域变形以产生+60%最大应变和-35%最小应变。使方杯的四角变形以产生+160%最大应变和-40%最小应变。实施例Ⅳ的板上的涂层是临时涂料组合物，制成干燥的，没有另加的润滑剂。比较实施例Ⅱ的板除了已涂的压延润滑剂外，在成形方杯之前再涂抹过量的FB-27MC润滑油。
实施例Ⅳ的涂了临时涂料组合物的板压延成方杯后在整个方杯的表面有一层均匀的涂膜。仅在杯角发现有锌衬底的极轻微的磨损。在杯的侧面有少量擦伤。在150°F下在1%        CHEMKLEEN        49溶液中浸洗1分钟并经漂洗后，所得成形制件完全没有水膜残迹。
比较实施例Ⅱ的板是涂了水基压延润滑剂的，压延成方杯后，在方杯的四个侧面上都可看到有严重的磨损和磨光的痕迹。这些区域的磨损和磨光说明该润滑剂不能在压模和衬底之间提供有效的液体隔离层。
在150°F下将一方杯在1%        CHEMKLEEN        49溶液中浸洗1分钟，随后用水漂洗，在方杯上留有水珠，这表明润滑剂没有有效地清除。
可见，实施例Ⅱ和Ⅳ的临时涂料组合物防止锌表面腐蚀和制造过程中损坏的效果比常用的压延润滑剂好得多。此外，保护涂料组合物比常用的润滑剂易于清除，因此能使制件清洗适当。
可焊接性试验
为了研究本发明的保护涂料组合物的可点焊性，制备了不同玻璃化温度的保护涂料组合物和由其涂敷而成的不同厚度的涂薄。用两种方法试验其可焊接性。第一种方法是将涂了保护涂料的薄板进行连续点焊，至少有500个点焊焊接点，同时观察焊接电极上是否有不导电的炭沉积，或是否仍保持清洁，足以传导点焊所需的约10，000安培的电流。第二种方法是在焊接点较少的情况下试验涂层可被点焊焊接电极穿透的能力。使用的是经过连续焊接已有一定程度衰变的电极。
如果约10，000安培的电流能通过电极和涂了涂料的薄板，那么该焊接被认为是成功的。如果在焊接过程中听到很响的开裂声，同时在周围的涂层中产生黑色焦化物，但约10，000安培的电流仍能通过薄板，那么该点焊被认为是勉强合格的如果焊接电极虽象通常的情况那样把板挤压在一起，但由于电阻过大而没有电流通过，那么这种点焊被认为是不合格的。如果在某些焊接点有约10，000安培的电流通过，而在另一些焊接点则由于电阻过大而没有电流通过，那么可焊接性被认为是几乎不合格的。
进行焊接试验时采用在6伏下最大电流输出为22，000安培的台座式点焊机。该机是新泽西州Lors        Corporahon的产品，型号为150AP。电极用525磅的力将两块要焊接的薄板挤压在一起，该力与通常用于0.030英寸镀锌钢板的点焊的挤压力是一样的。
实施例Ⅴ
用水将实施例Ⅰ的水基聚合物稀释到固体含量达12%，并用流涂的方法将其涂到刚清洗干净的镀锌薄板的两面，晾干到不粘手，然后再在105℃下强制干燥5分钟。所成涂膜的重量为0.96～1.37毫克/英寸2。在薄板上点焊750个焊点后，焊接电极仍能使约10，000安培的电流通过涂了涂料的薄板。进行750个焊点的焊接试验时，在板的涂层较厚（重量为1.3毫克/英寸2）的一面，有时能看到涂层烧焦的现象，但在板的涂层重量约为1.0毫米/英寸2的表面上未看到有烧焦的现象。约10，000安培的电流能通过750个焊点的焊接试验中的每个点焊点。这种涂料的涂层重量约为1.0毫克/英寸2时，其可点焊性被认为是合格的，涂层重量约为1.3毫克/英寸2时，其可点焊性被认为是勉强合格。
令人惊奇和意想不到的是，本发明的涂料-润滑剂会在压力和热的连续作用下从点焊电极处流掉，这样就不会累积起不导电的焦炭。
实施例Ⅵ
将实施例Ⅴ的第一种焊接试验中用过的旧的衰变的焊接电极用于第二种焊接试验，后者是试验涂料-润滑剂在常用的挤压力作用下被点焊电极穿透的能力。
下表所示为用于试验被焊接电极穿透的能力的具有不同玻璃化温度（Tg）的保护涂料组合物。
表Ⅰ
丙烯酸        丙烯酸        甲基丙烯
聚合物        Tg        苯乙烯        酸二甲基        蜡%
丁酯%        %        氨乙基酯
%
A        5℃        47        30        20        3        15
B        -11℃        60        20        20        -        15
C        -27℃        73        7        20        -        15
用表Ⅱ所示重量的涂膜进行电极穿透试验所得的可焊接性结果如下：
表Ⅱ
聚合物 Tg 毫克/英寸2电极穿透试验
A        +5℃        1.0        合格
A        +5℃        1.3        勉强合格
B        -11℃        1.4        合格
B        -11℃        1.84        勉强合格
B        -11℃        2.58        几乎不能焊接
C        -27℃        2.12        合格
C        -27℃        2.97        勉强合格
C        -27℃        5.5        几乎不能焊接
保护涂料组合物的其他性能
要求临时保护涂料组合物具有的其他性能是柔韧性和涂了涂料的衬底叠在一起时的抗粘着性。
柔韧性：
为了试验柔韧性，将涂了本发明的保护涂料组合物的镀锌薄板弯曲，绕0.075英寸半径的圆弧弯曲即所谓“5T”弯曲，也就是使涂了涂料的薄板围绕半径为薄板厚度的5倍的圆弧弯曲。然后将弯曲的试片在5%硝酸铜（Cu（NO3）2）溶液中浸10秒钟，接着进行漂洗。在露出锌金属的任何表面上都会形成含铜的沉积物。试验后在弯曲区域出现的棕色或黑色表示该处的保护涂料组合物产生了裂纹或多孔性。
柔韧性试验是用下列组分的涂料-润滑剂进行的。
表Ⅲ
甲基丙烯
聚合        苯乙        丙烯酸        丙烯        蜡        5T弯曲+
Tg℃        酸二甲基
物 烯% 丁酯 酸% 氨乙基酯 % Cu（NO3）2试验
%        %
D        35        50        30        20        -        2        点色沉积物
E        5        30        47        20        3        15        浅灰色沉积物
F        -12        17        60        20        3        15        无影响
抗粘着性：
为了试验抗粘着性，将涂了本发明的保护涂料组合物的衬底在120°F和150磅/英寸2力的作用下压叠在一起，保持16小时，然后冷却。将叠在一起的板分开，试验各块薄板是否有涂膜被热和压力损坏，及分开称作“解脱”时是否使涂膜损坏。为了试验涂膜是否损坏，将进行了抗粘着试验的试片浸在5%硝酸铜溶液中，接着进行漂洗，观察涂膜厚度非常小的区域或由于进行抗粘着性试验时与另一涂了涂料的薄板粘附在一起而使涂膜受到“解脱”的区域是否有棕色或黑色沉积物。
用下列保护涂料组合物进行了试验，该组合物在镀锌钢表面上形成的干膜的重量为1.4～1.5毫克/英寸2：
表Ⅳ
保护涂料        丙烯酸        苯乙烯        丙烯酸        蜡
Tg
组合物        丁酯%        %        %        %
G        -11℃        60        20        20        15
H        -27℃        73        7        20        15
抗粘着性试验后，发现在涂了涂料组合物H的大多数试片上都有深色的致密的铜沉积物，这说明受热、压力的作用和进行薄板的分离后，涂膜的完整性很差。涂了涂料-润滑剂G的试片在抗粘着性试验后，在试验区域仅有极轻微的铜沉积物，这表明该涂膜仍能保护其下面的金属表面，使其免受机械损伤和腐蚀。
除了可清除、可压延和可焊接这些性能外，某些实施方案中的保护涂料组合物还具有柔韧性和抗粘着性。虽然这里已对本发明作了详细的描述和说明，但不用说，还可进行各种变化而不偏离本发明的范围和精神，这对于擅长本技术的人来说是显而易见的。因此，要把针对本发明的权利要求书看作是包括了本发明的各个方面，擅长与本发明有关的技术的人要把权利要求书与本发明一样对待。

Claims (14)

1、一种用于金属衬底的含水临时保护涂料，该涂料包含：
一种中和的具有酸或碱的功能的聚合物和一种润滑组合物，该润滑组合物主要是由蜡组成的(蜡的含量足以使金属具有可成形性)，还可含导电填料。
2、权利要求1所述的保护涂料组合物，其中中和的具有酸或碱的功能的聚合物为溶液加聚物。
3、权利要求1所述的保护涂料组合物，其中聚合物是由多种烯属不饱和单体（其中至少有一种是具有酸功能的）进行自由基加成聚合而制得的。
4、权利要求3所述的保护涂料组合物，其中具有酸功能的单体的含量占单体总重的5～100%。
5、权利要求1所述的保护涂料组合物，其中具有酸功能的聚合物是用挥发性胺进行碱中和的。
6、权利要求1所述的保护涂料组合物，其中蜡的含量占涂料固体总重的5～70%。
7、权利要求6所述的保护涂料组合物，其中蜡的含量约为10～30%（重量）。
8、权利要求6所述的保护涂料组合物，其中蜡为烃类蜡、巴西棕榈蜡或蜂蜡。
9、权利要求1所述的保护涂料组合物，其中共聚物与蜡是结合在一起制得的，是通过多种烯属不饱和单体在有蜡存在的情况下在溶剂中进行自由基加成聚合而制得的。
10、一种为金属衬底提供装饰涂层或保护涂层的方法，该方法包括将权利要求1的组合物涂到衬底上。
11、权利要求10所述的一种方法，该方法还包括用碱或酸的水溶液清除临时保护涂料组合物。
12、权利要求11所述的方法，其中临时保护涂料组合物是通过将衬底浸在碱或酸的水溶液中而清除的。
13、一种用权利要求10所述的方法制得的物品。
14、一种用权利要求11所述的方法制得的物品。
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