CN1159835A - 用于处理金属的组合物及方法 - Google Patents
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Abstract
通过对包含以下成分的含水酸性液体进行干燥,可以在金属(特别是冷轧钢)上形成无铬的转换涂层,该涂层与普通铬酸盐转换涂层相比,至少在抗腐蚀质量上等效:(A)一种阴离子成分,所述各个阴离子包括(i)至少4个氟原子,(ii)至少选自钛、锆、铪、硅与硼元素中的1个原子。任选地(iii)可离解的氢原子,任选地(iv)1个或多个氧原子;(B)一种选自钴、镁、锰、锌、镍、锡、锆、铁与铜元素的阳离子成分,上述成分的阳离子总数与成分(A)内的阴离子总数之比至少为1∶5;(C)足够的游离酸以使该组合物的pH值在0.5~5.0的范围内;(D)一种选自含磷的无机含氧阴离子与膦酸盐阴离子的成分;(E)一种选自水溶性与水可分散性有机聚合物与聚合物形成的树脂的成分,优选还包括一种选自钨酸盐、钼酸盐、钨硅酸盐与钼硅酸盐阴离子的成分。
Description
本申请是共同未决申请系列No.08/100,533(1993.7.30)的部分续篇。本发明的背景
发明所属领域
在本发明涉及使用酸性含水组合物处理金属表面以便在金属上形成转换涂层的组合物及方法;该转换涂层可为后续涂覆提供极好的基础。本发明很适合于处理铁与钢、镀锌铁与镀锌钢、锌及其包含至少50原子%锌的合金、铝及其包含至少50原子%铝的合金。优选所处理的表面主要是铁类金属表面;更优选所处理的表面是冷轧钢的表面。
对有关技术的说明
在先有技术中已经认识到各种各样的材料都适宜于本发明的一般目的,但是大多数的材料都包含有碍于环境保护的6价铬。本发明的一个目的是避免任何实际使用6价铬和诸如铁氰化物等已被规定属于对环境有害的其他材料。
本发明的说明
除非在权利要求与操作实例中,或另外特意指出的地方之外,在本说明中所指在反应和/或使用中涉及的物质或条件的数值都应理解为,在说明本发明的广泛范围内被字“约”所限定。通常优选所述数值极限内的实践。此外,除非特意指出有相反意思:百分数、“份”及比值都是相对重量而言的;术语“聚合物”包括低聚物;适于或优选用于本发明所给目的的物质类族或分类的说明是指:任何二种或多种类族或分类物质的混合物同样适于或优选用于本发明的目的;按化学术语说明的成分意指在向本说明中所规定的任何组合物中添加时的成分,并且不必考虑在混合之后混合物各成分的相互化学反应;呈离子态各物质的特性意思是存在足够的平衡离子以使该组合物作为一个整体是电中性的(从而所规定的任何平衡离子最好尽可能地选自明显按离子态规定的其它成分之中,另外,除了要避免不利于本发明所述目的的平衡离子以外,也可以自由地选择这种平衡离子);术语“摩尔”及其变异可以应用于元素、离子与任何被原子序数与类型所定义的其它化学核素,以及具有明确限定的分子的化合物。对本发明的概述
业已发现,通过使金属表面同以下详述的组合物在足够的温度下接触足够的时间,可以赋予活泼金属表面、特别是铁与钢以及其它铁类金属表面以极好的抗腐蚀性,特别是接着使用含有有机粘结剂的涂料如油漆或清漆进行常规涂覆后,尤其如此。优选用该组合物在整个要处理的金属表面涂覆一层基本上均匀的涂层,然后使该涂层在该金属表面上干燥,而无需进行中间冲洗。
本发明的组合物包含基本上、优选地或更优选地由水与以下成分组成:
(A)一种氟金属酸盐阴离子,所述各种阴离子包含(i)至少4个氟原子,(ii)至少选自钛、锆、铪、硅、铝与硼元素的1个原子,以及任选地1个或2个(iii)可离解的氢原子,(iv)1个或多个氧原子,该阴离子优选氟钛酸盐(即TiF6 -2)或氟锆酸盐(即ZrF6 -2)阴离子,更优选氟钛酸盐阴离子;
(B)一种选自钴、镁、锰、锌、镍、锡、铜、锆、铁与锶元素的2价或4价阳离子成分;成分(B)总重的60%优选包含钴、镍、锰或镁,更优选包含锰、钴或镍;优选是其优选性按给定的次序逐渐增加,使得该成分的阳离子总数与成分(A)内的阴离数之比至少为1∶5、1∶3、2∶5、3∶5、7∶10或4∶5;独立地,优选性按给定的次序逐渐增加,使得该成分的阳离子总数与成分(A)内的阴离子数之比不大于3∶1、5∶2、5∶3、10∶7、5∶4或1.1∶1;
(C)一种含磷的无机含氧阴离子和/或磷酸盐阴离子成分,以及
(D)一种水溶性和/或水可分散性的有机聚合物和/或聚合物形成的树脂,优选它们的数量应使该组合物内的有机聚合物与聚合物形成的树脂的固体含量与成分(A)的固体含量之比,优选性按次序逐渐增加地在下面给出的范围内:1∶5~3∶1、1∶2~3∶1、0.75∶1.0~1.9∶1.0、0.9∶1.0~1.60∶1.0、1.07∶1.0~1.47∶1.0或1.17∶1.0~1.37∶1.0;
(E)游离酸,其数量应足够使工作组合物的pH值在0.5~5.0、优选1.7~4.0、更优选2.0~4.0、更进一步优选2.0~3.5的范围内;任选地1种或多种:
(F)溶解的氧化剂,优选过氧化合物,更优选过氧化氢;
(G)一种选自钨酸盐、钼酸盐、钨硅酸盐与钼硅酸盐阴离子的成分;优选成分(G)的数量应使成分(G)内的钨与钼的总摩尔数与成分(A)内的钛、锆、铪、硅、铝与硼的总摩尔数之比,优选性按照给定次序逐渐增加地不小于0.001、0.005、0.01、0.03、0.05、0.06、0.07、0.08、0.09、0.10、0.11、0.12、0.13、0.14、0.15、0.160、0.163、0.166、0.169、0.172或0.175,按照给定次序逐渐增加优选性,独立地,优选性按照给定次序逐渐增加地不大于2、1、0.7、0.5、0.4、0.35、0.31、0.29、0.28、0.27或0.26;
(H)一种选自溶解的或分散的对沉降稳定的配合物的成分,所述配合物是由于各物质之间的反应而生成的,在反应前该物质可以是成分(A)的一部分和1种或多种选自金属与准金属元素及其氧化物、氢氧化物与碳酸盐,以使其生成一种不是上述成分(A)到(G)中任何一部分的反应产物;优选这种成分是由于与二氧化硅或五氧化二钒反应而生成的反应产物。
不用说所列出的各种成分不必全部都由单独的化学制品提供,例如,优选氟金属酸盐阴离子与含3价磷的阴离子二者以相应的酸形态添加,从而还提供某些(通常是全部)所需的游离酸以用于成分(E),此外,如果该组合物的酸度足够高而且同其接触的基底主要是铁类金属的话,当该液态组合物首先同基底接触时,可以由从基底溶解的铁提供成分(B)而无需预先存在于该液态组合物中。
本发明的各种实施方案包括在处理金属中直接使用的工作组合物、可以是一种浓缩物,将其用水稀释即可制得上述工作组合物、用本发明的组合物处理金属的各种方法以及包括各种附加步骤的补充方法,该附加步骤本身是一种常规方法,例如预清洁、冲洗以及特别有利的是涂漆或某些类似的涂保护膜的方法,该方法将含有有机粘结剂的保护膜涂料涂覆在按照本发明比较狭义的实施方案而形成的整个转换涂层上。包括按照本发明方法的表面处理而生产的制品也在本发明的范围内。最佳实施方案说明
由于各种各样的原因,如上定义的本发明的各种组合物最好应基本上不含有先有技术中用于类似目的的组合物中的许多种成分。特别是优选性按照下面给定的次序逐渐增加,优选是各自独立地为下列的最小成分,以使得在本发明的方法中直接同金属接触时,这些组合物包含不大于1.0、0.35、0.10、0.08、0.04、0.02、0.01、0.001或0.0002%的以下各个成分:6价铬;铁氰酸盐;亚铁氰酸盐;硫酸盐及硫酸;碱金属及铵阳离子;吡唑化合物;糖类;葡糖酸及其盐类;甘油;α-甘庚酸(α-glucheptanoic acial)及其盐类;肌醇磷酸酯及其盐类。
此外,在金属表面上适当干燥上述组合物涂层外还包括其它步骤的本发明方法中,优选性按下列给定次序逐渐增加,优选在这些其它步骤中没有任何步骤使金属表面同任何包含大于1.0、0.35、0.10、0.08、0.04、0.02、0.01、0.003、0.001或0.0002%6价铬的组合物接触,只有当最终保护涂层体系包含有机粘结剂时,尤其是该体系包括底涂层时,该组合物才允许包含6价铬作为一种成分。在该保护涂层内任何这种6价铬通常被有机粘结剂完全所封闭,以避免有害的环境影响。
在本发明的一个实施方案中,优选将上述酸性含水组合物涂覆到金属表面并在短时间间隔进行干燥。根据按给定次序而增加的优选性,在该时间间隔期间,液态涂料被涂覆到待处理的金属上并现场进行干燥,当利用加热来加速这一过程时,该时间间隔不大于25、15、9、7、4、3、1.8、1.0或0.7秒(本文以后缩写为“sec”)。为了促进本发明方法的快速完成,经常优选将本发明中所用的酸性含水组合物涂覆到热金属表面,例如在进行最初的清洁之后先用热水冲洗,然后在非常短的时间内用本发明的含水组合物处理,和/或使用红外或微波辐射加热和/或对流加热以便极快地实现对已涂敷的涂层进行干燥。在这种一种操作中,通常优选30~200℃、更优选40~90℃的峰值温度。
在另一种实施方案中,当在可接受的经济成本允许使用足够的时间时,该方案在技术上是等效的并且也令人满意,本发明的组合物可以被涂覆到金属基底并随后在不超过40℃温度时进行干燥。但在这种情况下,没有快速干燥的特别优点。
本发明处理的效率似乎主要取决于在被处理表面的单位面积上被干燥的活性成分的总量、性质以及活性成分彼此之间的比例,而不取决于所用酸性含水组合物的浓度。从而,如果要涂敷的表面是一种连续的平坦板材或卷材并使用精确控制的涂敷技术如滚筒涂料器,就可以有效地将单位面积少量的浓缩组合物直接进行使用。另一方面,使用某些涂敷设备,使用较稀的酸性含水组合物与使用含有同量活性成分的较浓液态涂料具有同等效果。通常,按照随给定次序而增加的优选性,一般优选工作组合物具有至少0.010、0.020、0.026或0.032克摩尔/千克(全部组合物)(此后简写为M/kg)浓度的成分(A),至少0.015、0.030、0.038或0.045克摩尔(磷)/千克(此后简写为“Mp/kg”)浓度的成分(C)以及至少0.10、0.20、0.26或0.35%(固体)的成分(D)。特别当涂敷控制精确到足以计量本发明要处理的金属表面上相对较薄的工作组合物的均匀薄膜时,包含5到10倍上述数量的活性成分的工作组合物一般实际上也加以使用。
最好选择本发明方法中使用的组合物数量以便在已处理的表面上增加的总质量(在干燥后)为5~500毫克/米2(以后简写为“mg/m2”),优选为10~400mg/m2或更优选为50~300mg/m2。由本发明方法形成的保护膜增加的质量一般可通过测量在上述成分(A)的阴离子内增加的金属原子的重量或质量进行监测和控制。这些金属原子的数量可以通过在本专业中众所周知的几种常规分析技术进行测量。通常最可靠的测量包括从已知涂敷基底的区域上溶解涂料并测定所得溶液内感兴趣金属的含量。然后可以从成分(A)内的金属量与干燥后剩下的部分中全部组合物的总质量之间的已知相互关系计算出增加的总质量。为此计算目的,假定,该工作组合物的全部水,包括在其操作期间添加到该成分的任何固体成分内水合的任何水都被干燥而排出,但涂敷到所测量表面上的工作组合物液膜的全部其它成分仍留在已干燥的涂层内。
在本发明要使用的浓缩酸性含水组合物中,或者直接作为工作组合物或者作为活性成分源用于制造较稀的工作组合物,上述成分(A)的浓度优选为0.15~1.0M/kg,或更优选为0.30~0.75M/kg。
以上定义的成分(C)将理解为包括可能存在于该组合物内的全部以下无机酸及其盐类:次磷酸(H3PO2)、亚磷酸(H3PO3)、焦磷酸(H4P2O7)、正磷酸(H3PO4)、三聚磷酸(H5P3O10)以及具有Hx+2PxO3x+1化学式的缩合磷酸,式中x是大于3的正整数。成分(C)也包括全部膦酸及其盐类。在浓缩组合物中,全部组合物的成分(C)浓度优选为0.15~1.0Mp/kg,或更优选为0.30~0.75Mp/kg。
通常,无机磷酸盐、尤其是正磷酸盐、亚磷酸盐、次磷酸盐、和/或焦磷酸盐,主要是正磷酸盐优选用于成分(C),因为它们都比较经济。膦酸盐还适宜于并有利于使用非常硬的水,因为膦酸盐是钙离子更有效的配合剂。原子价小于5的3价磷的酸及其盐类对于氧化剂可能不如其它磷酸及其盐类稳定;最好在包含氧化剂的本发明组合物内少用。
成分(D)最好选自环氧树脂、氨基塑料(即密胺-甲醛与尿素-甲醛)树脂、鞣酸类、酚醛树脂和具有足够数量的烷基与在酚醛环上的烷基-氨甲基取代基以使该聚合物具有水溶性或水可分散性的乙烯苯酚聚合物。更优选,成分(D)选自环氧树脂,和/或最优选仅仅选自1个或多个y-(N-R1-N-R2-氨甲基)-4-羟基-苯乙烯的聚合物和/或共聚物,式中y=2、3、5或6,R1代表含有1~4个碳原子的烷基类,R2表示符合化学式H(CHOH)nCH2-取代基类,式中,n是从1到7的整数,优选从3到5。这些聚合物的平均分子量最好在700~70,000的范围内,优选在3,000~20,000范围内。在浓缩组合物内成分(D)的浓度最好为1.0~10%,或优选为4.5~7.5%。
如果使用的话,成分(F)最好以一定的数量存在于本发明的工作组合物内,该数量应提供氧化当量/升(组合物)的浓度等于包含0.5~15、优选1.0~9.0%过氧化氢的浓度。(本文使用的术语“氧化当量”应理解为等于氧化剂的克重量被氧化剂的克当量所除的得数。氧化剂的当量重量是该氧化剂的克分子量除以该分子作为氧化剂而发生的价态变化数时所获的数值;通常这仅是一种元素,例如过氧化氢中的氧。)
通常优选存在上述成分(G),因为用这种组合物进行后续涂敷所处理的表面的粘附力通常得到提高,超过了用其它缺少成分(G)的类似组合物在所处理的表面上达到的粘附力。
在上述成分(H)中的术语“对沉降稳定的”意思是,当在25℃贮存100小时、或优选1000小时时,包含该组合物的材料不会出现任何肉眼可看得见的沉降现象或分离出清晰的液相。可以通过向包含全部或部分成分(A)的含水组合物中添加1种或多种金属和/或准金属元素,或者它们的氧化物、氢氧化物和/或磷酸盐来制取成分(H)材料。通常自发的化学反应可将添加的元素、氧化物、氢氧化物或碳酸盐转化为可溶性物质。通过加热或搅拌该组合物可以加速形成这种可溶性物质的反应。由于存在具有适宜配位基的组合物,如过氧化物和氟化物,从而也有助于可溶性物质的形成。当以浓缩组合物使用时,成分(H)的数量最好不大于通过向该浓缩组合物添加(优选性随着给定的次序逐渐增加)最大达50、20、12、8、5或4‰(以该浓缩组合物的最终总质量为基础)的金属或准金属元素或其化学计量当量的氧化物、氢氧化物或碳酸盐所形成的数量。独自无关地,当以浓缩组合物使用时,成分(H)的数量最好至少与通过向该浓缩组合物添加(优选性随着给定的次序逐渐增加)至少0.1、0.20、0.50或1.0‰(以该浓缩组合物的最终总质量为基础)的金属或准金属元素或其化学计量当量的氧化物、氢氧化物或碳酸盐所形成的同样大的数量。
本发明的工作组合物可以按本领域普通技术人员所熟知的任何常规方法涂敷在金属工件上和将其干燥。例如,可以通过将该表面浸渍在该液态组合物的容器内、将该组合物喷涂在该表面上、使该工件在上辊和下辊之间通过用浸渍在该液态组合物容器内的下辊涂敷该工件的表面,等等,或这些方法的组合法实现将液膜涂敷在金属上。在干燥前应通过任何常规方法如在重力作用下滴流、涂刷器、使其在两辊之间通过等方法去除可能残留在金属表面上的过量液态组合物。也可以通过任何常规方法如热空气干燥箱加热、暴露在红外辐射下、微波加热等来完成干燥。
对于平坦的与特别是连续的平坦工件如片材和卷材,通常优选使用按任何若干排列的滚筒、随后在不同阶段进行干燥。在使用液态组合物时的温度可以是该组合物处于液态范围内的任何温度,尽管在使用滚筒涂敷中考虑到方便和经济、但通常优选正常室温,即20~30℃。在大多数连续处理卷材的情况下,优选快速操作,在该情况下,通常优选产生上述范围峰值金属温度的红外辐射加热进行干燥。
另一方面,特别是如果基底形状不适于滚筒涂敷,可以将组合物喷涂在基底的表面上,从而能适当进行干燥。可以按需要经常重复这种循环,直到达到所要求的涂层厚度为止(通常以mg/m2为单位计量)。关于这种类型的操作,在使用工作组合物期间金属基底表面的温度最好在20~300℃范围内,优选30~100℃,更优选30~90℃。
本发明要处理的金属表面最好首先清除任何污渍、特别是有机污渍以及外部金属粉粒和/或夹杂物。可以通过本专业人员熟知的并适宜于要处理的特定基底形状的方法来完成上述清洁步骤。例如,对于镀锌钢表面,最好用普通热碱性清洁剂清洗基底,然后用热水冲洗、刮擦和干燥。对于铝,最好首先使待处理的表面同普通热碱性清洁剂接触。然后在热水内漂洗,然后任选地在同上述酸性含水组合物接触以前,先与一种用于中和的酸接触。
本发明特别适宜于处理将要进行以下后续进一步保护处理的表面,该后续保护处理是将普通的有机涂料如油漆、清漆等涂敷已按照本发明处理过的整个表面。
通过参考以下非限定性的工作实例可以进一步认识本发明的实践,参照对比例也可以进一步认识本发明的优点。浓缩组合物的制取
在表1和表2中示出了浓缩组合物。按照美国专利4,963,596第11栏39-52行的指示制取在大多数实施例中用于成分(D)的取代乙烯基苯酚聚合物。该溶液包含30%的固态聚合物,其余为水。该溶液被定义为“氨甲基取代的聚乙烯酚”(Aminomethy 1 Substituted polyviyl phenol)。在这些实施例中另一种被用于成分(D)的RIX95928环氧树脂(来自Rhone-Poulenc)被其供应商说明为主要是双酚-A二环氧甘油醚(diglycidyl ethers of bisphenol-A)聚合物悬浮液,其中某些环氧基团已经转变成羟基,聚合物分子被磷酸盐包覆。
表1
成分 | 组合物号内各部分成分的浓度 | ||||||||||||
1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | |
无离子水 | 649 | 646 | 641 | 636 | 646 | 647 | 640 | 638 | 634 | 649 | 646 | 641 | 336 |
含60%H2TiF6的水 | 81 | 80 | 81 | 80 | 80 | 80 | 80 | 82 | 82 | 81 | 80 | 81 | 84 |
含75%H3PO4的水 | 46 | 46 | 47 | 46 | 46 | 46 | 46 | 47 | 46 | 46 | 46 | 47 | 46 |
氨甲基取代的聚乙烯酚 | 204 | 204 | 206 | 204 | 204 | 204 | 204 | 208 | 204 | 204 | 204 | 206 | 205 |
碳酸镍(NiCO3) | 36 | ||||||||||||
碳酸镁(MgCO3) | 20 | 20 | 21 | ||||||||||
氧化锰(MnO) | 24 | 21 | 20 | 20 | 20 | 24.4 | 24 | 24 | 4 | ||||
碳酸锌(ZnCO3) | 4 | ||||||||||||
碳酸钴(CoCO3) | 34 | 4 | |||||||||||
化学计量当量为40%ZrO2的锆基碳酸盐 | 10 | ||||||||||||
金属锡粉 | 3 | ||||||||||||
金属铁粉 | 0.6 | ||||||||||||
五氧化二钒(V2O5) | 2 | ||||||||||||
30%H2O2的水 | 8 | 293 |
表2
一般通过向大部分所需要的水中添加酸性成分、然后如果使用的话在上述这些成分之中最后添加氧化锰(II)来溶解金属和/或金属盐或氧化物成分、然后添加有机成膜剂,然后如果使用的话添加二氧化硅、最终如果使用的话添加过氧化氢来制取该浓缩物。
成分 | 组合物号内各部分的浓度 | |||||||||
14 | 15 | 16 | 17 | 18 | 19 | 20 | 21 | 22 | 23 | |
无离子水 | 636 | 646 | 647 | 692 | 701 | 697 | 666 | 457 | 622 | 623 |
含60%H2TiF6的水 | 80 | 80 | 80 | 84 | 50 | 80 | 84 | 82 | 82 | |
含75%H3PO4的水 | 46 | 46 | 46 | 45 | 46 | 45 | 47 | 47 | ||
氨甲基取代的聚乙烯酚 | 204 | 204 | 204 | 204 | 204 | 204 | 208 | 208 | ||
Rhne-Poulenc RIX 95928环氧树脂悬浮液(40%固体) | 153 | 230 | ||||||||
钨硅酸(H8SiW12O42) | 13 | |||||||||
钼硅酸(H8SiMo12O42) | 12 | |||||||||
氧化锰(MnO) | 20 | 20 | 24 | 28 | 28 | |||||
碳酸锌(ZnCO3) | ||||||||||
碳酸钴(CoCO3) | 34 | 4 | ||||||||
金属锡粉 | 3 | |||||||||
化学计量当量为40%ZrO2的锆基碳酸盐 | 15 | 15 | ||||||||
Silica(SiO2)-Cab-O-SilTM M-5 | 5 | 5 | ||||||||
30%H2O2的水 | 294 |
作为表1和2中部分组合物示出的金属锡和铁同酸成分反应产生作为成分(B)一部分的阳离子,同时完全相信,在该表中示出的五氧化二钒和二氧化硅同部分氟钛酸和/或过氧化氢反应,以组成上述定义的成分(H)。例如,当五氧化二钒和过氧化氢被添加到表1示出的浓缩组合物(Concentrate Composition)9中时,此刻当该部分组合物已经包含氟钛酸和磷酸但不含氧化锰(II)时,该混合物溶解并形成一种棕淡红色色彩的溶液。该棕淡红色是某些包含过氧配位基的钒配合物的已知颜色。在添加氧化锰(II)以后,大量地逸出气体,相信它就是氧气,此时该溶液变成绿色。即使向这种溶液中添加少量的过氧化氧也会再产生棕红色。使用浓缩物制取工作组合物
一般通过用去离子水稀释该浓缩物,在某些情况下还添加附加成分来制取工作组合物。在表3中给出了详情。在进行制备时,组合物18不是按照本发明进行的,因为组合物18缺少成分(B)。然而,当该成分用于冷轧钢时,钢的反应性溶解作用十分强烈,以致足够的铁被溶解进工作组合物中,使该组合物具有本发明的功能。一般工艺条件和试验方法
使用含有22g/L PARCOCLEANER 338(可在市场上从the ParherAmchem Division of HenKel Corp.,Madison Heights Michigon,USA得到)的含水清洁剂喷射清洁冷轧钢试件。在清洗后,用热水冲洗、用刮板刮擦该板材,在用以下各实施例和对比例所述的酸性含水组合物滚涂以前进行干燥。上述涂敷液体在产生约50℃峰值金属温度的红外线干燥处内进行闪蒸干燥。
表3
实施例和对比例号的工作组合物 | 工作组合物中的各部分 | |||||
无离子水 | 浓缩物 | 含30%H2O2的水 | 含75%H3PO4的水 | 1-羟基-乙烯-1,1-二磷酸 | 含48%HF的水 | |
1 | 166 | 34 | ||||
2 | 166 | 34 | ||||
3 | 166 | 34 | ||||
4 | 172 | 28 | ||||
5 | 172 | 28 | ||||
6 | 172 | 28 | ||||
7 | 172 | 28 | ||||
8 | 172 | 28 | ||||
9 | 172 | 28 | ||||
10 | 166 | 34 | 10 | |||
11 | 166 | 34 | 10 | |||
12 | 166 | 34 | 10 | |||
13 | 166 | 34 | ||||
14 | 166 | 34 | 10 | |||
15 | 166 | 34 | 10 | |||
16 | 166 | 34 | 10 | |||
17a | 171 | 29 | 8.5 | 0.77 | ||
17b | 171 | 29 | 8.5 | 0.85 |
续表3
实施例和对比例号的工作组合物 | 工作组合物中的各部分 | |||||
无离子水 | 浓缩物 | 含30%H2O2的水 | 含75%H3PO4的水 | 1-羟基-乙烯-1,1-二磷酸 | 含48%HF的水 | |
18 | 171 | 30 | 8.8 | |||
19 | 172 | 28 | 10 | |||
20 | 170 | 30 | 10 | 1.0 | ||
21a | 166 | 34 | ||||
21b | 166 | 34 | 0.5 | |||
21c22 | 166 | 34100 | 1.0 | |||
23 | 100 |
表3备注用于各工作组合物的浓缩物具有与该编号工作组合物同样的数字编号。空白格表示在上述工作组合物中没有注明成分,在该工作组合物同将要处理的基底接触时也没有向其中添加其它的成分。组合物21a~21c是对比例。 |
此时,通过使涂料溶解在含水盐酸中并使用感应耦合等离子谱测定法(它可测量特定元素的数量)测定所得溶液中的钛含量的方法,在某些样品上测定该涂层单位面积的质量。
在干燥以后,一般按照制造商的指示用普通油漆或油漆体系涂敷上述板材。使用下表中的油漆体系及其标志符号:Specialty Coating Company,Inc.的408-1-W-249高反射率白色聚酯漆-标明“A”。Specialty Coating Company,Inc.的408-1-K-247 60G Metalux黑色聚酯漆-标明“B”。Specialty Coating Company,Inc.的408-1-W-976 80G Newell白色漆-标明“C”。
按照American soeiety for Testing Materials(以后称“ASTM”)Method D4145-83进行T-弯曲试验;按照ASTM Method D 2794-84E1使用140英寸-磅的冲击力进行冲击试验;按照ASTM Method B-117-90Standard进行168小时的盐喷雾试验,报告划线渗水值(ScribeCreepage)。控制(A型对比例)
用含铬现场干燥处理的BONDERITETM1402W制取此处所用的组合物,该原料在市场上可从Parkev Amchem Div.of Henkel Corp.MadisonHeigkts.Mickigan,USA得到。按照制造厂指示的那样在其它对比例的相同条件下制取和使用上述材料。
“对比”结果、工作实例和对比例示于表4中。本发明的大多数实施例得到的试验结果在各个方面都优于或更好于使用6价铬的“对比例”。
表4
工作组合物号 | 涂层量mg/M2 | 试验结果 | ||||||||
A系涂料 | B系涂料 | C系涂料 | ||||||||
0T-弯曲 | 冲击 | 盐雾 | 1T-弯曲 | 冲击 | 盐雾 | 0T-弯曲 | 冲击 | 盐雾 | ||
1 | 140 | 9.8 | 10 | 1-2 | 10 | 10 | 2-4 | 10 | 10 | 1-2 |
2 | 140 | 9.9 | 10 | 1-2 | ||||||
3 | 140 | 9.9 | 10 | 1-3 | ||||||
4 | 200 | 9.8 | 10 | 1-2 | 10 | 10 | 2-4 | 9.9 | 10 | 0-12s |
5 | 180 | 9.9 | 10 | 0-1 | 9.9 | 10 | 2-2 | 9.9 | 10 | 0-1 |
6 | 140 | 9.0 | 10 | 0-1 | 9.9 | 10 | 1-2 | 10 | 10 | 0-1 |
7 | 140 | 9.9 | 10 | 0-12s | 8.5 | 10 | 2-2 | 10 | 10 | 0-1 |
8 | 90 | 9.8 | 10 | 0-1 | 10 | 10 | 2-2 | 10 | 10 | 0-1 |
9 | 110 | 9.8 | 10 | 0-1s | 10 | 10 | 1-12s | 10 | 10 | 0-1 |
10 | 140 | 9.4 | 10 | 0-1 | 10 | 10 | 2-4 | 10 | 10 | 0-1 |
11 | 140 | 9.9 | 10 | 0-1 | 10 | 10 | 0-1 | |||
12 | 140 | 9.9 | 10 | 0-1 | ||||||
13 | 150 | 9.0 | 10 | 0-1S | 10 | 10 | 3-3 | 10 | 10 | 0-1s |
14 | 200 | 10 | 10 | 0-1s | 10 | 10 | 4-5 | 10 | 10 | 0-1s |
续表4
工作组合物号 | 涂层量mg/M2 | 试验结果 | ||||||||
A系涂料 | B系涂料 | C系涂料 | ||||||||
0T-弯曲 | 冲击 | 盐雾 | 1T-弯曲 | 冲击 | 盐雾 | 0T-弯曲 | 冲击 | 盐雾 | ||
15 | 180 | 9.9 | 10 | 0-1 | 9.9 | 10 | 3-4 | 9.9 | 10 | 1-1 |
16 | 140 | 9.9 | 10 | 1-1 | 9.9 | 10 | 4-4 | 10 | 10 | 0-12s |
17a | 150 | 9.8 | 10 | 1-1 | 10 | 10 | 4-5 | 10 | 10 | 1-1 |
17b | 150 | 9.8 | 10 | 1-1 | 10 | 10 | 8-8 | 10 | 10 | 1-1 |
18 | 150 | 9.6 | 10 | 1-1 | 10 | 10 | 4-4 | 10 | 10 | 0-2 |
19 | 180 | 9.7 | 10 | 3-3 | 10 | 10 | 5-5 | 10 | 10 | 3-3 |
20 | 300 | 9.7 | 10 | 0-1 | ||||||
21a | 140 | 10 | 10 | 6-12 | 10 | 10 | 12-16 | 10 | 10 | 9-12 |
21b | 140 | 10 | 10 | 14-14 | 10 | 10 | 失败 | 10 | 10 | 失败 |
21c | 140 | 9.5 | 10 | 16-16 | 10 | 10 | 失败 | 10 | 10 | 失败 |
22 | 130 | 9.9 | 10 | 0-1 | 9.5 | 10 | 2-2 | 9.8 | 10 | 0-1 |
23 | 200 | 9.0 | 10 | 0-1 | 9.0 | 10 | 2-2 | 9.9 | 10 | 1-1 |
对比 | 200 | 9.9 | 10 | 1-12s | 10 | 10 | 2-3 | 10 | 10 | 0-12s |
对比 | 300 | 10 | 10 | 1-2 | 10 | 10 | 2-4 | 10 | 10 | 1-2 |
表4备注空白格意指无试验 |
Claims (20)
1.一种用于处理金属表面的含水液态组合物,或者直接或者用另外的水稀释后使用,所述组合物主要由水和以下成分组成:
(A)至少约0.15M/kg的氟金属酸盐阴离子成分,各个所述阴离子包括(i)至少4个氟原子,(ii)至少选自钛、锆、铪、硅、铝和硼元素的1个原子,以及任选地1个或多个的(iii)可离解氢原子和(iv)氧原子;
(B)一种选自钴、镁、锰、锌、镍、锡、铜、锆、铁和锶各元素的2价或4价阳离子的成分,它们的数量应使该成分的阳离子总数与成分(A)内的阴离子总数之比至少约为1∶5,但不大于3∶1;
(C)至少约0.15Mp/kg选自含磷的无机含氧阳离子和膦酸盐阴离子的成分;
(D)至少约1.0%选自水溶性和水可分散性的有机聚合物与聚合物形成的树脂的成分,该成分的数量也应使该组合物内的有机聚合物与聚合物形成的树脂的固体含量与成分(A)内的固体含量之比在约1∶2到3∶1的范围内,以及
(E)足够的游离酸以使得该组合物的pH值从约0.5到约5.0。
2.根据权利要求1的组合物,它还包括选自钨酸盐、钼酸盐、钨硅酸盐和钼硅酸盐阴离子的成分(G),它们的数量应使该组合物内的钨与钼的总摩尔数与成分(A)内的钛、锆、铪、硅、铝和硼的总摩尔数之比不小于约0.03,还优选地包括1种或2种已溶解氧化剂的成分(E)和已溶解或已分散的对沉降稳定的配合物的成分(H),所述配合物是由于各物质之间的反应而生成的,在反应前该物质可以是成分(A)的一部分和1种或多种选自金属与准金属元素及其氧化物、氢氧化物及碳酸盐,以使其生成一种不是成分(A)到(G)中一部分的反应产物。
3.根据权利要求2的组合物,其中,成分(A)选自氟钛酸盐和氟锆酸盐阴离子;至少60%的成分(B)选自钴、镍、锰和镁,该成分的阳离子总数与成分(A)内的阴离子数之比至少约有1∶5,但不大于5∶2;成分(C)选自正磷酸盐、亚磷酸盐、次磷酸盐、膦酸盐和焦磷酸盐阴离子;成分(D)选自环氧树脂、氨基塑料树脂、鞣酸类、酚醛树脂和具有足够数量的烷基与在酚醛环上的烷基-氨甲基取代基以使该聚合物具有至少1%水溶性或水可分散性的乙烯苯酚聚合物;成分(D)的数量应使该组分内的有机聚合物与聚合物形成的树脂的固体含量与成分(A)内的固物含量之比在约0.75∶1.0~1.9∶1的范围内。
4.根据权利要求3的组合物,其中,成分(A)是用氟钛酸盐阴离子配制的;至少60%的成分(B)选自钴、镍与锰,该成分的阳离子总数与成分(A)内的阴离子数之比至少约为1∶3,但不大于10∶7;成分(C)的数量从约0.30~0.75Mp/kg;成分(D)选自环氧树脂和1个或多个y-(N-R1-N-R2-氨甲基)-4-羟基-苯乙烯的聚合物与共聚物,其中y=2、3、5或6,R1表示含有1~4个碳原子的烷基,R2表示符合化学式H(CHOH)nCH2-的取代基,式中n是从1~7的整数,取代苯乙烯聚合物具有从约700~约70,000的平均分子量;成分(D)的浓度从约4.5~约7.5%;成分(D)的数量应使该组合物内的有机聚合物与聚合物形成的树脂的固体含量与成分(A)的固体含量之比在约0.90∶1.0~1.6∶1的范围内。
5.一种用于处理金属表面的方法,所述方法包括以下步骤:
(I)用基本上均匀的含水酸性液态组合物涂料涂覆金属表面,该组合物主要由水和以下成分组成:
(A)一种氟金属酸盐阴离子成分,各种所述阴离子包括(i)至少4个氟原子,(ii)至少选自钛、锆、铪、硅、铝和硼元素的1个原子,任选地(iii)可离解的氢原子,任选地(iv)1个或多个氧原子;
(B)一种选自钴、镁、锰、锌、镍、锡、铜、锆、铁与锶的2价或4价阳离子成分,它们的数量应使该成分的阳离子总数与成分(A)内的阴离子数之比至少约为1∶5,但不大于约3∶1;
(C)一种选自含磷的无机含氧阴离子和膦酸盐阴离子的成分;
(D)一种选自水溶性与水可分散性有机聚合物与聚合物形成的树脂的成分;
(E)游离酸,以使该组分的pH值在约0.5~约5.0的范围内;
(II)对在步骤(I)涂覆了涂料的金属表面适当位置进行干燥,而无需中间冲洗。
6.根据权利要求5的方法,其中,在步骤(I)所涂含水酸性液态组合物还包括选自钨酸盐、钼酸盐、钨硅酸盐与钼硅酸盐阴离子的成分(G),它们的数量应使该组合物内的钨与钼的总摩尔数与成分(A)内的钛、锆、铪、硅、锆和硼的总摩尔数之比不小于约0.03,上述组合物任选地还包含1种或2种溶解氧化剂的成分(F)和已溶解或已分散的对沉降稳定的配合物的成分(H),所述配合物是由于各物质之间的反应而生成的,在反应前该物质可以是成分(A)的一部分和1种或多种选自金属与准金属元素及其氧化物、氢氧化物与碳酸盐,以使其生成一种不是成分(A)~(G)的一部分的反应产物。
7.根据权利要求6的方法,其中,在步骤(I)所涂液态组合物内,成分(A)的浓度至少约为0.01M/kg;成分(B)的阳离子总数与成分(A)内的阴离子数之比至少约为1∶5,但不大于3∶1;成分(C)的浓度至少约为0.015Mp/kg;成分(D)的浓度至少约为0.10%,成分(G)的数量应使该组合物内的镍与钼的总摩尔数与成分(A)内的钛、锆、铪、硅、铬与硼的总摩尔数之比从约0.06到约0.7。
8.根据权利要求7的方法,其中,在步骤(I)所涂液态组合物内,成分(A)选自氟钛酸盐与氟锆酸盐阴离子,成分(A)的浓度至少约为0.020M/kg;至少60%的成分(B)选自钴、镍、锰与镁,上述成分的阳离子总数与成分(A)内的阴离子数之比至少约为1∶3,但不大于约5∶2;成分(C)选自正磷酸盐、亚磷酸盐、次磷酸盐、膦酸盐与焦磷酸盐阴离子,成分(C)的浓度至少约为0.030Mp/kg;成分(D)选自环氧树脂、氨基塑料树脂、鞣酸类、酚醛树脂和具有足够数量的烷基与在酚醛环上的烷基-氨甲基取代基,以使该聚合物具有至少1%水溶性或水可分散性的乙烯苯酚聚合物;成分(D)的数量应使该组合物内的有机聚合物与聚合物形成的树脂的固体含量与成分(A)的固体含量之比在约1∶2到3.0∶1.0的范围内;成分(D)的浓度至少约为0.20%;成分(G)的数量应使该组合物内的钨与钼的总摩尔数与成分(A)内的钛、锆、铪、硅、铝与硼的总摩尔数之比从约0.09至约0.5。
9.根据权利要求8的方法,其中,在步骤(I)所涂液态组合物内,成分(A)的浓度至少约为0.026M/kg;成分(B)选自钴、镍与锰,上述成分的阳离子总数与成分(A)内的阴离子数之比至少约为1∶3,但不大于约10∶7;成分(C)的浓度至少约为0.0380Mp/kg;成分(D)选自环氧树脂、和1种或多种y-(N-R1-N-R2-氨甲基)-4-羟基-苯乙烯的聚合物与共聚物,式中y=2、3、5或6,R1表示一种含有1~4个碳原子的烷基类,R2表示符合化学式H(CHON)nCH2-的取代基,式中n是1~7的整数,取代苯乙烯聚合物具有从约700到约70,000的平均分子量,成分(D)的数量应使该组合物内的有机聚合物与聚合物形成的树脂的固体含量与成分(A)的固体含量之比在约0.75∶1.0~约1.9∶1.0的范围内;成分(D)的浓度至少约为0.26%,成分(G)的数量应使该组合物内的钨与钼的总摩尔数与成分(A)内的钛、锆、铪、硅、铝与硼的总摩尔数之比从约0.12~约0.35。
10.根据权利要求9的方法,在步骤(I)所涂液态组合物内,成分(A)的浓度至少约为0.032M/kg;成分(B)的阳离子总数与成分(A)内的阴离子数之比至少约为2∶5,但不大于约5∶4;成分(C)的浓度至少约为0.045Mp/kg;成分(D)选自1种或多种y-(N-R1-N-R2-氨甲基)-4-羟基-苯乙烯的聚合物与共聚物,式中y=2、3、5或6,R1表示甲基,R2表示符合化学式H(CHOH)nCH2-的取代基,式中n是4~6的整数,取代苯乙烯聚合物具有从约3,000到约20,000的平均分子量,成分(D)的数量应使该组合物内的有机聚合物与聚合物形成的树脂的固体含量与成分(A)的固体含量之比在约0.90∶1.0~约1.6∶1.0的范围内;成分(D)的浓度至少约为0.35%,成分(G)的数量应使该组合物内的钨与钼的总摩尔数与成分(A)内的钛、锆、铪、硅、铝与硼的总摩尔数之比从约0.15~约0.31。
11.根据权利要求10的方法,其中,在步骤(I)所涂液态组合物内,成分(B)的阳离子总数与成分(A)内的阴离子数之比至少约为2∶5,但不大于约1.1∶1.0;成分(D)的数量应使该组合物内的有机聚合物与聚合物形成的树脂的固体含量与成分(A)的固体含量之比在约1.07∶1.0~约1.47∶1.0的范围内;成分(G)的数量应使该组合物内的钨与钼的总摩尔数与成分(A)内的钛、锆、铪、硅、铝与硼的总摩尔数之比从约0.160~约0.27。
12.根据权利要求11的方法,其中,所涂覆的金属是冷轧钢,在该方法步骤(II)终了时涂覆的涂料数量在50~300mg/m2的范围内。
13.根据权利要求10的方法,其中,所涂覆的金属是冷轧钢,在该方法步骤(II)终了时涂覆的涂料数量在50~300mg/m2的范围内。
14.根据权利要求9的方法,其中,所涂覆的金属是冷轧钢,在该方法步骤(II)终了时涂覆的涂料数量在50~300mg/m2的范围内。
15.根据权利要求8的方法,其中,所涂覆的金属是冷轧钢,在该方法步骤(II)终了时涂覆的涂料数量在10~400mg/m2的范围内。
16.根据权利要求7的方法,其中,所涂覆的金属是冷轧钢,在该方法步骤(II)终了时涂覆的涂料数量在10~400mg/m2的范围内。
17.根据权利要求6的方法,其中,所涂覆的金属是冷轧钢,在该方法步骤(II)终了时涂覆的涂料数量在5~500mg/m2的范围内。
18.根据权利要求5的方法,其中,所涂覆的金属是冷轧钢,在该方法步骤(II)终了时涂覆的涂料数量在5~500mg/m2的范围内。
19.根据权利要求4的方法,其中,所涂覆的金属是冷轧钢,在该方法步骤(II)终了时涂覆的涂料数量在5~500mg/m2的范围内。
20.根据权利要求5的方法,该方法还包括以下辅助步骤,在步骤(I)以前按常规清洁要处理的金属;在步骤(II)以后用含有有机粘结剂的常规保护涂料涂覆已处理的金属表面。
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CN100391625C (zh) * | 2005-06-27 | 2008-06-04 | 宝山钢铁股份有限公司 | 具有耐碱性和耐溶剂性的镀锌钢板 |
CN100391623C (zh) * | 2005-06-27 | 2008-06-04 | 宝山钢铁股份有限公司 | 具有耐碱性和耐溶剂性的用于镀锌钢板的表面处理剂 |
CN100465339C (zh) * | 2006-08-02 | 2009-03-04 | 西南铝业(集团)有限责任公司 | 无铬化学转化剂 |
CN102027157B (zh) * | 2008-03-11 | 2013-07-31 | 凯密特尔有限责任公司 | 用钝化剂涂覆金属表面的方法,该钝化剂及其用途 |
US10422042B2 (en) | 2008-03-17 | 2019-09-24 | Henkel Ag & Co. Kgaa | Metal treatment coating compositions, methods of treating metals therewith and coated metals prepared using the same |
CN101603174B (zh) * | 2009-07-28 | 2010-12-08 | 武汉钢铁(集团)公司 | 彩色涂层钢板用无铬预处理剂 |
CN104894544A (zh) * | 2009-10-08 | 2015-09-09 | Ppg工业俄亥俄公司 | 补充剂组合物和补充预处理组合物的方法 |
CN104894544B (zh) * | 2009-10-08 | 2017-11-21 | Ppg工业俄亥俄公司 | 补充剂组合物和补充预处理组合物的方法 |
CN107012455A (zh) * | 2009-12-28 | 2017-08-04 | 汉高股份有限及两合公司 | 含有锆、铜、锌和硝酸盐的金属预处理组合物和在金属基材上相关的涂层 |
CN107012455B (zh) * | 2009-12-28 | 2019-06-04 | 汉高股份有限及两合公司 | 含有锆、铜、锌和硝酸盐的金属预处理组合物和在金属基材上相关的涂层 |
US11131027B2 (en) | 2009-12-28 | 2021-09-28 | Henkel Ag & Co. Kgaa | Metal pretreatment composition containing zirconium, copper, zinc and nitrate and related coatings on metal substrates |
Also Published As
Publication number | Publication date |
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FI970859A (fi) | 1997-04-28 |
ZA957333B (en) | 1996-04-18 |
US5449415A (en) | 1995-09-12 |
EP0777763A4 (en) | 1997-11-26 |
EP0777763A1 (en) | 1997-06-11 |
AU3409995A (en) | 1996-03-27 |
EP0777763B1 (en) | 2001-10-31 |
DE69523608D1 (de) | 2001-12-06 |
KR970705656A (ko) | 1997-10-09 |
DE69523608T2 (de) | 2002-08-08 |
WO1996007772A1 (en) | 1996-03-14 |
AU690326B2 (en) | 1998-04-23 |
JPH10505636A (ja) | 1998-06-02 |
MX9701474A (es) | 1997-05-31 |
FI970859A0 (fi) | 1997-02-28 |
ATE207979T1 (de) | 2001-11-15 |
CA2198381A1 (en) | 1996-03-14 |
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