CN101563429A - 灰白色和灰色的自沉积涂层 - Google Patents
灰白色和灰色的自沉积涂层 Download PDFInfo
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- CN101563429A CN101563429A CNA200780039468XA CN200780039468A CN101563429A CN 101563429 A CN101563429 A CN 101563429A CN A200780039468X A CNA200780039468X A CN A200780039468XA CN 200780039468 A CN200780039468 A CN 200780039468A CN 101563429 A CN101563429 A CN 101563429A
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- reactive metal
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
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- C—CHEMISTRY; METALLURGY
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- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
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Abstract
一种用灰白色或灰色着色的自沉积涂层涂覆金属基底的组合物，其包含水、聚合物树脂、HF和颜料颗粒，所述颜料颗粒包含二氧化钛核、中间氧化锆和/或氧化铝层、和外部有机层，任选地颗粒用阴离子表面活性剂处理。
Description
技术领域
[0001]本发明涉及用于通过金属和自沉积涂覆浴之间的化学反应在金属基底上生产着色的聚合物涂层的组合物及方法，取代传统的炭黑颗粒或除传统的炭黑颗粒之外所述自沉积涂覆浴使用颜料颗粒，颜料颗粒已经对于自沉积浴是稳定化。更特别地，本发明涉及通过自沉积涂覆浴生产的白色至灰白色和灰色涂层，以及沉积涂层叠的方法，自沉积涂覆浴本身，形成该浴的浓缩物。
背景技术
[0002]在钢铁上工业应用自沉积已经有大约三十年了，并且目前对于用途是公知的。详细来说，参见例如美国专利No.3592699(Steinbrecher等人)；美国专利No.4108817和4178400(均属于Lochel)；美国专利No.4180603(Howell.Jr.)；美国专利No.4242379和4243704(均属于Hall等人)；美国专利No.4289826(Howell.Jr.)；和美国专利No.5342694(Ahmed)以及美国专利No.5500460(Ahmed等人)和美国专利No.6645633(Weller等人)。所有这些专利公开的内容作为参考在此一并引用。
[0003]自沉积组合物通常是液体，通常是水溶液、水性乳液或含水分散体的形式，其中插入物体的活性金属表面涂覆有粘附树脂或聚合物膜，其中金属物体在浴中保持时间越长，该膜增加厚度，尽管在不与活性金属接触的情况下，但是对于任何树脂或聚合物的自发沉淀或絮凝作用来说液体是长时间稳定的。“活性金属”定义为在电动序中那些比氢更具活性的金属，即当引入到液体溶液、乳液或分散体中时，它以相当大的比率开始自发地溶解(伴有氢气的放出)。这种组合物，以及用这些组合物在金属表面上形成涂层的方法，在本文中并且在本说明书中，普遍地表示为“自沉积”或“自沉积的”组合物、分散体、乳液、悬浮液、浴、溶液、过程、方法或类似术语。自沉积通常与电沉积形成对照，电沉积可以制造很类似的粘附膜但是要求要涂覆的金属或其他物体与直流电源连接以实现涂覆。在自沉积中没有这样的外部电流，作为替代使用加速剂。
[0004]自沉积加速剂组分是一种例如酸、氧化剂和/或复合试剂的物质，其能够使得活性金属从与自沉积组合物接触的活性金属表面溶解，从而驱动涂料的沉积。自沉积加速剂组分可以选自氢氟酸及其盐、氟硅酸及其盐、氟钛酸及其盐、铁离子、醋酸、磷酸、硫酸、硝酸、过氧化氢、过氧酸、柠檬酸及其盐、和酒石酸及其盐。自沉积加速剂组分可以选自自沉积现有技术中已知的用于该目的或类似的提供满意结果的任何材料或材料的组合。
[0005]自沉积组合物通常还可以含有一种或多种附加成分。这些附加成分可以包括表面活性剂(乳化剂或分散剂)、填料、杀虫剂、泡沫控制剂、流动控制(流平)剂、和/或炭黑颜料。
[0006]在没有颜料的存在下，自沉积涂层倾向于是无色的或微黄至绿色，并且对于许多商业用途不能提供足够的遮盖力。加入颜料是增加涂层遮盖力的传统方法。已经证明由于该浴的强酸本性(其具有的pH范围从1.0至4.0)向自沉积浴中引入颜料是有问题的。以前，自沉积涂层已经限于黑色，使用所谓的“炭黑”颜料，其在酸中稳定并且可分散在工作浴中。
[0007]传统的颜料是适用于油漆，其通常具有的pH值从5.5到10。由于缺少那些在酸性自沉积浴中可以预见稳定的颜料，涂料和自沉积浴之间在pH值上的明显区别限制了那些可以用于自沉积浴的颜料。由于不同颜料不可预料的性能(包括溶解在浴中，不能与聚合物一起沉积在活性金属基底上，使得清洗掉活性金属基底的涂层显现，并且在浴中与其他组分反应以导致浴的“破裂”，以及开始分散以在罐的底部形成软泥浆)，到目前为止向自沉积中引入非炭黑颜料以制造非黑色涂料的尝试都不成功。
[0008]形成白色或灰白色自沉积涂层的特殊问题是自沉积浴中颜料有限的稳定性，其通常受定期加入的氧化剂的支配并且包含强酸。特别地，由于氟化氢(HF)的存在，因此二氧化钛(TiO2)(经济且常用的白色颜料)在自沉积浴化学作用中是不稳定的。在HF的存在中，TiO2水解为氟钛酸并且浴变得不稳定。这些向二氧化钛的转变使其不能用于作为白色颜料在金属基底上沉积以生成白色、灰白色或灰色涂料。先前尝试单独使用二氧化钛颗粒的另一个缺点是颗粒不能保持分散并且会形成需要处理的软泥浆。
发明内容
[0009]本发明涉及水性液体组合物(溶液或分散体)的用途，仅与液体组合物接触，活性金属表面可以被组合物涂敷，得到粘附的白色至灰白色或灰色聚合物膜，其随着接触时间延长增加厚度，尽管在缺少与活性金属接触的情况下，在长时间内液体组合物对于任何固体聚合物的自发沉淀或絮凝是稳定的。(为了本申请的目的，术语“活性金属”理解为包括铁和所有在电动序中比铁活泼的金属和合金。)在本说明书中并且常用于现有技术中，上述的液体组合物表述为“自沉积”或“自沉积的”组合物、分散体、乳液、悬浮液、浴、溶液、或类似术语。
[0010]本发明的一个目的在于提供用于涂覆活性金属表面的自沉积浴组合物，其包含：包括酸和至少一种氧化剂的自沉积加速剂的水溶液，所述酸的用量使组合物具有大约1.6至大约3.8的pH值；均匀分散在整个组合物中的形成涂层的聚合物材料的颗粒；均匀分散在整个组合物中的对所述酸稳定的非黑色固体颜料颗粒的组分；包括阴离子表面活性剂的乳化组分；任选地，不同于乳化组分的第二种稳定表面活性剂；以及，任选地，在所述组合物形成的涂层中适合作为填料的细分固体和/或黑色颜料；在缺乏外部电位的情况下所述组合物有效地化学侵蚀浸入其中的活性金属表面以从该活性金属表面溶解金属来释放所述金属的离子并且足以使得所述聚合物材料和所述非黑色固体颜料颗粒以初始粘附涂层的形式沉积在活性金属表面上，其中所述表面沉浸在所述组合物中时间越长，所述初始粘附涂层的重量或厚度增加。
[0011]本发明进一步的目的在于提供一种组合物，其中酸是氢氟酸并且非黑色固体颜料包含二氧化钛核、无机材料(所需地不同于二氧化钛的氧化物)的第一涂层、以及有机材料的第二涂层。氧化物的第一涂层可以包括本质上不溶于酸的氧化物。在本发明的一个实施方式中，氧化物选自氧化铝、氧化锆及其混合物。本发明的还有一个目的在于提供一种组合物，其中有机材料的第二涂层包括阴离子分散添加剂，阳离子分散添加剂或非离子分散添加剂。
[0012]在本发明的一个实施方式中，有机材料的第二涂层包含聚丙烯酸酯、多磷酸酯、阳离子化聚丙烯酸酯、表氯醇树脂、双氰胺树脂、聚甲基丙烯酸酯、聚醚多元醇和聚酯中的至少一种。在另一个实施方式中，聚甲基丙烯酸酯选自甲基丙烯酸季二甲基氨基乙酯、三聚氰胺-甲醛树脂及其混合物。
[0013]本发明进一步的目的在于提供一种组合物，其中非黑色固体颜料颗粒与聚合物材料的重量比，按照优选的递增顺序，从大约1、2.5、5、7.5、10、15、20、25、26、27、或28，并且按照优选的递增顺序小于50、49、48、47、46、45、44、43、42、41、40、39、38、37、36、35、34、33、32、或31。
[0014]本发明进一步的目的在于提供一种组合物，其中阴离子表面活性剂选自具有至少一个硫酸根、磺酸根、磷酸根、或磷酸根官能团的表面活性剂。
[0015]本发明进一步的目的在于提供一种组合物，其中所述阴离子表面活性剂保持形成涂层的聚合物材料的颗粒和非黑色固体颜料颗粒的组分的分散，使得所述聚合物材料和所述颜料颗粒以初始粘附涂层的形式沉积在活性金属表面上。
[0016]本发明另一个目的在于提供一种组合物，其中所述组合物包括足量的黑色颜料以提供由该组合物形成的灰色涂层。
[0017]本发明进一步的目的在于提供一种组合物，其中所述聚合物材料选自苯乙烯-丁二烯聚合物、丙烯腈-丁二烯聚合物、聚乙烯、丙烯酸类聚合物、四氟乙烯聚合物、聚氯乙烯、聚氨酯树脂、苯乙烯-丙烯酸类聚合物、环氧类聚合物、和环氧-丙烯酸类聚合物材料。
[0018]本发明进一步的目的在于提供一种组合物，其中所述氧化剂选自过氧化氢、重铬酸盐、过硼酸盐、溴酸盐、高锰酸盐、亚硝酸盐、硝酸盐和氯酸盐。
[0019]本发明进一步的目的在于提供一种组合物，其中所述酸选自氢氟酸、硫酸、盐酸、硝酸、磷酸、氢溴酸、氢碘酸、乙酸、氯乙酸、三氯乙酰、乳酸、酒石酸和聚丙烯酸。
[0020]本发明另一个目的在于提供一种在活性金属基底表面上沉积白色至灰白色或灰白色自沉积涂层的方法，该方法包括：
-用权利要求1至15任意一项所述的组合物与活性金属基底表面接触0.5至10分钟，以在表面上形成白色至灰白色或灰白色初始粘附涂层；
-用含水的清洗剂清洗初始粘附涂层；
-任选地，干燥初始粘附涂层；并且
-将初始粘附涂层固化以形成固化的白色至灰白色或灰色涂层。
[0021]本发明另一个目的在于提供一种用于形成自沉积浴的水性自沉积浓缩组合物，其包含：
-均匀分散在整个组合物中形成涂层的聚合物材料的颗粒；
-均匀分散在整个组合物中的非黑色固体颜料颗粒，所述非黑色固体颜料颗粒包含二氧化钛核、不同于二氧化钛的氧化物的第一涂层以及有机材料的第二涂层；
-包括阴离子表面活性剂的乳化组分；
-任选地不同于乳化组分的第二种稳定表面活性剂；以及
-任选地在所述组合物形成的涂层中适合作为填料的细分固体和/或黑色颜料；
其中非黑色固体颜料颗粒与聚合物材料的重量比为1-49wt％。
[0022]除了操作实施例以外，或另外明确指出之处，在本说明书中指示材料用量或反应条件的所有数量应该理解为用“约”一词来修饰。
附图说明
[0023]图1描述了一种用于本发明的二氧化钛颜料的横截面视图。
[0024]申请人已经开发了一种适用于作为单独涂层或作为通用工业领域底漆的白色至灰白色或灰色着色的自沉积涂层，其包含单独的二氧化钛颜料颗粒或与黑色颜料，例如炭黑结合的二氧化钛颜料颗粒。通过开发一种具有对浴稳定的二氧化钛颗粒的新型自沉积浴组合物，已经克服了使用了常规二氧化钛颜料颗粒的自沉积浓缩物和浴的不稳定性。
[0025]在制造稳定的二氧化钛自沉积涂覆浴中遇到的第一个困难是二氧化钛颗粒在自沉积浴的酸性环境中的不稳定性。在缺少任何额外的外部涂料层例如有机层沉积在二氧化钛颗粒上的情况下，自沉积浴的酸性将溶解或水解二氧化钛。特别地氢氟酸将与二氧化钛反应以生成氟钛酸。
[0026]自沉积浴包含一种加速剂组分，其希望地包括铁阳离子、氢氟酸、和过氧化氢。在根据本发明的工作组合物中，对于每种成分独立地：铁阳离子的浓度优选是至少，按照给定的顺序增加优选性，0.5、0.8、或1.0g/l，并且独立地优选不超过，按照给定的顺序增加优选性，2.95、2.90、2.85、2.80或2.75g/l；在阴离子中氟的浓度优选是至少，按照给定的顺序增加优选性，0.5、0.8、1.0、1.2、1.4、1.50、1.55、1.60、1.80、2.0g/l并且独立的优选不超过，按照给定的顺序增加优选性，20、17、15、13、12、11、10、7.0、5.0或4.0g/l；并且加入到新鲜制备的操作的组合物中的过氧化氢的用量优选为至少，按照给定的顺序增加优选性，0.050、0.10、0.20、0.30或0.40g/l，并且独立地优选不超过，按照给定的顺序增加优选性，2.1、1.8、1.5、1.2、1.00、0.90或0.80g/l。
[0027]优选地，加速剂组分选自其足够强和足够用量以给予自沉积组合物氧化-还原电位的那些，通过和自沉积液体组合物接触的铂或其他惰性金属电极的电位测量，其按照给定的顺序增加优选性，比标准氢电极氧化力高出至少150、175、200、225或250mV，并且独立地优选是，照给定的顺序增加优选性，比标准氢电极氧化力高出不超过550、525、500、475或450mV。令人希望地加速剂组分还包括氢阳离子源，即酸，其量足以使自沉积浴的pH值至少为，按照给定的顺序增加优选性，1.0、1.4、1.6、1.8或2.0并且独立地优选不超过，按照给定的顺序增加优选性，3.8、3.6、3.2、3.0、2.8或2.6。
[0028]典型地二氧化钛颗粒用氧化铝和二氧化硅稳定。二氧化硅在HF中是不稳定的，如同在某种程度上在HF中的氧化铝。到目前为止，二氧化硅涂敷的颗粒没有证明对HF稳定；令人希望地，在二氧化钛颗粒上的涂料包括，按照给定的顺序增加优选性，小于30、20、10、5、4、3、2、1wt％二氧化硅。在涂有氧化铝的二氧化钛颗粒的测试中，铝从二氧化钛颗粒滤出进入到自沉积浴中以形成氟化铝。铝的滤出现象发现可以通过在浴中增加HF用量来修正。在额外的测试中，发现了单独使用或与氧化铝结合使用的氧化锆可以保护二氧化钛自沉积浴酸性条件的影响。
[0029]制备稳定的、白色至灰白色或灰色自沉积浴的第二个障碍是保持二氧化钛悬浮在水性自沉积浓缩物和浴中，并且保证聚合物和颜料颗粒两者的所需沉积量。令人希望地，在一个实施方式中在聚合物颗粒和颜料颗粒之间的沉淀比较均等。
[0030]已经发现相对于彼此的二氧化钛颗粒的疏水性/亲水性和聚合物颗粒的疏水性/亲水性是控制二氧化钛颗粒是否分散在浴中并且粘附地在活性金属基底上沉积以获得所需颜色中的变量。
[0031]使用的表面活性剂的类型和用于聚合物颗粒的表面活性剂组成会影响在聚合物和颜料颗粒之间的相对相容性，从而影响相对沉积速率。由于没有单一理论的约束，可以假定与亲水性二氧化钛颗粒结合使用的疏水性聚合物颗粒引起了在自沉积浴中的表面活性剂向乳液微粒的迁移，从而留下表面活性剂被剥夺的二氧化钛颜料，并且最终导致二氧化钛颗粒从分散体沉淀出来。更亲水表面活性剂的选择导致更多表面活性剂可以用来帮助分散颜料颗粒。令人希望地，在两种颗粒之间表面活性剂有比较均等的分配，并且保持平衡条件如以使聚合物颗粒和颜料颗粒的分散体在没有活性金属的情况下是稳定的。
[0032]在一些实施方式中，阴离子表面活性剂的乳化组分足以向阴离子稳定的聚合物颗粒和非白色固体颜料颗粒提供合适的稳定性。一般地，使自沉积浴中的聚合物颗粒是阴离子稳定的。正如在现有技术中所知的，可以通过将阴离子表面活性剂混入聚合物或通过向聚合物乳液中加入阴离子表面活性剂来完成这种聚合物稳定作用。在一些情形中，两种方法都被使用。这种包括阴离子表面活性剂的乳化组分可以达到除聚合物颗粒之外固体颜料颗粒的稳定分散和合适沉积。
[0033]在其他实施方式中，可以包括第二种稳定表面活性剂以便进一步促进固体颜料颗粒的稳定分散和合适沉积。
[0034]应该选择表面活性剂组配(也就是乳化组分和不同于乳化组分的任何第二种稳定表面活性剂)并且表面活性剂组配应该以足够的浓度存在以使聚合物颗粒乳化或分散，并且使在自沉积组合物中的颜料颗粒分散，以便在没有自沉积组合物与任何活性金属接触的情况下，在25℃下在自沉积组合物制备后至少24小时的储存期之内没有整体相的分离或离析，其可用常规的未受协助的肉眼察觉。
[0035]通常优选阴离子表面活性剂，不过也可以使用两性的以及非离子型表面活性剂。用于本发明中的阴离子表面活性剂包括具有硫酸根、磺酸根、磷酸根、或膦酸根端基的阴离子表面活性剂。在一个实施方式中，用于涂覆二氧化钛颜料颗粒和稳定聚合物颗粒的阴离子表面活性剂选自烷氧基化的醚硫酸盐，例如通过非限定的例子，Polystep B-40；RhodapexTM CO-128、-433，和-436以及TexaponTM E-12和K-12。
[0036]已经成功地在自沉积浴中测试改性的TiO2的分解和在金属基底上沉积的能力。令人希望地，改性的二氧化钛颗粒在自沉积浴中通常存在的酸性条件下足够稳定；并且在一个特别的实施方式中，在HF的存在下足够稳定，使得固体颜料颗粒仍然可在被放入自沉积浴中的金属上沉积。可以相信颗粒不水解，然而可接受不妨碍沉淀和浴稳定性的颜料颗粒的水解程度。
[0037]主要地通过颜料颗粒的至少下列特征来决定表现性能(化学的、光化学的和物理性质)：颜料的颗粒尺寸和颜料颗粒表面的化学组成。TiO2颗粒表面的化学组成可以通过用不同于二氧化钛的第二种材料的无机层涂覆它们来进行改进。
[0038]许多商品等级的TiO2具有无机表面处理以及有时具有有机表面处理，其中并非所有的都适合于在自沉积浴中使用。最常用于二氧化钛的无机表面改性剂是氧化铝和硅石的沉淀涂层。申请人的研究已经表明，为用于自沉积浴中，需要第一层包含在用于自沉积浴的酸(通常为HF)中具有低溶解度的无机材料。优选地，无机材料在用于自沉积浴的酸中是实质上不溶的。作为此处使用的，“实质上不溶的”是指该材料在环境温度下具有的溶解性小于，按照递增优选的次序，0.5，0.25，0.1，0.075，0.05，0.025，0.01，0.0075，0.005，0.0025，或0.001g/100毫升酸。优选地，无机层是金属氧化物，例如通过非限定例子氧化锆和/或氧化铝。
[0039]一旦用第一层即无机层涂覆，颜料颗粒被第二层即有机层涂覆。替代地，颜料颗粒可以同时与无机材料和有机材料接触，从而形成第一无机层和第二外部有机层，或者可以形成复合涂层。
[0040]通常地，有机层的组分选自颜料领域的技术人员熟知的物质，其用于在水性溶液介质中分散固体颜料，例如通过非限定的例子，在自沉积过程期间帮助分散颗粒而不会妨碍颗粒在金属基底上沉积的阴离子添加剂、阳离子添加剂和非离子添加剂。
[0041]合适的阴离子添加剂包括例如聚丙烯酸酯或多磷酸酯及类似物；阳离子添加剂包括例如阳离子化聚丙烯酸酯或聚甲基丙烯酸酯，如甲基丙烯酸季二甲基氨基乙酯或三聚氰胺-甲醛树脂、表氯醇树脂、双氰胺树脂及类似物。非离子添加剂包括多元醇和/或聚酯及类似物。许多其他合适用于颜料的涂料在美国专利No.3825438中叙述，在此一并引用。
附图说明
[0042]图1是用于本发明的颜料颗粒的横断面图。在这个实施方式中，颜料颗粒包含由混合氧化锆/氧化铝层(2)涂覆随后由外部有机层(3)涂覆的TiO2核(1)，参见图1。任选地，涂覆的TiO2颜料可以随后用阴离子表面活性剂处理，其形成第三外层(4)。令人希望地阴离子表面活性剂基于硫酸盐化合物，也就是说具有硫酸根官能团，以促进颜料颗粒向聚合物乳液颗粒的均匀沉积和消耗速率。
[0043]TiO2核的内部第一无机层和第二有机层表面处理连同用阴离子表面活性剂的后处理，在酸性含有HF的自沉积浴中提供了稳定且可沉积的TiO2颜料浆液。随着改性TiO2颗粒向自沉积浴的成功引入，自沉积涂覆工艺提供了以传统的黑色、白色至灰白色和以灰色底纹提供涂层。涂层的颜色是与二氧化钛颜料结合使用的黑色颜料的用量的函数。
[0044]已经测试了包括改性TiO2颗粒的自沉积涂层，其中该颗粒从含有这些颗粒的自沉积浴中沉淀出来，并且该自沉积涂层显示出与相应的黑色商业产品相似的耐腐蚀性和物理性能。在具有不同数量的改性TiO2颗粒的浴中涂覆的薄板用聚合物涂料以均匀的白色至灰色色度涂覆金属基底。得到的涂覆的薄板在组合物的颜色性能、覆盖力和着色力上显示出一致性。
[0045]本发明的一个实施方式提供了一种用于沉积水性灰白色自沉积涂层的组合物，其包含：改性TiO2颗粒和至少一种乳液聚合物。令人希望地该改性TiO2颗粒作为水性淤浆提供，以帮助组分向组合物中的引入。任选地，TiO2淤浆进一步用阴离子表面活性剂改性，其优选基于硫酸根、磺酸根、磷酸奶或膦酸根端基。替代地，阴离子表面活性剂和包含改性TiO2颗粒的淤浆可以分别加入到浴中。乳液聚合物可以是丙烯酸类、苯乙烯-丙烯酸类、环氧类、环氧-丙烯酸类、聚氨酯分散体，或本领域技术人员已知的任何其他适用于自沉积过程的可水分散的离子稳定的聚合物。
[0046]本发明的另一个实施方式提供了一种适用于在金属基底上沉积灰色自沉积涂层的水性组合物，其包含：改性TiO2颜料颗粒、黑色颜料颗粒、优选炭黑、和至少一种乳液聚合物。令人希望地，两种颜料作为水性淤浆提供，以有助于引入组合物和使炭黑淤浆是阴离子稳定的。任选地，TiO2淤浆进一步用阴离子表面活性剂改性，其优选基于硫酸根、磺酸根、磷酸根、或膦酸根端基。替代地，阴离子表面活性剂和包含改性TiO2颗粒的淤浆可以分别加入到浴中。乳液聚合物可以是丙烯酸类、苯乙烯-丙烯酸类、环氧类，环氧-丙烯酸类、聚氨酯分散体，或本领域技术人员已知的任何其他适用于自沉积过程的可水分散的离子稳定的聚合物。
[0047]本发明的另一方面，自沉积涂覆浴通过下述方法制备：按足以形成自沉积浴的用量将上述一种自沉积组合物与水、HF、铁和过氧化氢混合，其中不挥发物的百分比在1-20wt％的范围内。
[0048]本发明的实践可以进一步从下列工作实施例中评价。
具体实施方式
实施例1
35％不挥发物的灰白色自沉积涂料组合物浓缩物按照下列方式配制而成：
向1.5升容器中加入211.65g的去离子水，5.63g具有20％不挥发性(活性)的阴离子表面活性剂，786.4g具有42+/-1％不挥发物的阴离子改性的聚合物乳液，以及132.6g具有50+/-1％不挥发物的TiO2颜料淤浆。活性颜料与聚合物粘结剂的比是20％。在淤浆中TiO2颜料被制造商描述为具有氧化锆和氧化铝的第一内层和聚醚多元醇的第二外层。TiO2颜料和聚合物颗粒保持均匀地分散在浓缩物中。
实施例2
6％不挥发物的20毫升铁滴定、灰白色自沉积涂覆浴使用实施例1组合物按照下列方式配制而成：
在1.5升的容器中，混合下列物质：
5.20g HF
1.70g铁粉
3.62g过氧化氢35％
蒸馏水加至1.0升。
将材料混合数分钟。在缓慢搅拌下，257.1g实施例1的组合物加入到该1.5升的容器中。最后加入足量的蒸馏水以达到1.5升。混合该浴1小时。并且在连续搅动下将浴的参数调节至下列参数：
氧化还原值 275-400mV
Lineguard 101仪表读数 100-700微安
总不挥发物百分比 1-10％
湿涂料固体 20-50％
启动滴定 10-40毫升
浴温度 20-25°F
导电率 1200-10000微西门子
在灰白色浴准备好以及参数最佳化之后，按照下列方法处理金属薄板：
A.用碱性清洗剂清洁-2分钟
B.温水清洗-1分钟
C.去离子水清洗-1分钟
D.与实施例2的自沉积加工浴接触-2分钟
F.水清洗-1分钟
G.用
Reaction Rinse E2(从Henkel公司商购获得)处理-1分钟
H.在53℃下烘箱固化7分钟，并且在185℃下固化40分钟。
得到的涂覆的薄板在颜色上呈轻微地灰白色，在颜色是均匀的并且显示出良好的覆盖力。
实施例3
35％不挥发物的灰色自沉积涂层组合物浓缩物按照下列方式配制而成：
向一升的烧瓶中加入211.14g去离子水、5.63g具有20％不挥发物的(活性)的阴离子表面活性剂、3.38g具有30％不挥发物的黑色颜料淤浆、786.4g具有42+/-1％不挥发物的阴离子改性的聚合物乳液、以及132.6g具有50+/-1％不挥发物的实施例1的TiO2颜料淤浆。活性颜料与聚合物粘结剂的比为20％。
6％不挥发物、20毫升铁滴定、灰色自沉积涂覆浴，使用实施例3组合物按照实施例2的过程配制而成。该浴混合一小时并且在连续搅动下将浴的参数调节至实施例2的参数。
在灰色浴准备好并且参数最佳化之后，按照实施例2的方法处理金属薄板。得到的涂覆的薄板在颜色上呈轻微地灰白色，在颜色是均匀的并且显示出良好的覆盖力。
实施例4
以不同的颜料浴粘结剂比例按照实施例3配制灰色自沉积浴。比例从5∶95颜料∶粘结剂到50∶50颜料∶粘结剂。在不同比例下的物理和耐腐蚀性能如下列表1所示：
表1
| 颜料∶粘结剂比例 | 交叉粘结性ASTMD3359-02 | 反向碰撞(in.1b.) | 耐溶剂性M.E.K.双面摩擦 | 铅笔硬度ASTMD3363-00 | 中性盐水喷雾试验(504小时下的划线蠕变总mm)ASTM B117 | 稳定性 |
| 5∶95 | 5B | ＞80 | ＞200 | ＞3H | 1.6 | 稳定 |
| 10∶90 | 5B | ＞80 | ＞200 | ＞3H | 1.5 | 稳定 |
| 17∶87 | 5B | ＞80 | ＞200 | ＞3H | 2.9 | 稳定 |
| 30∶70 | 5B | ＞80 | ＞200 | ＞3H | 1.2 | 稳定 |
| 40∶60 | 5B | ＞80 | ＞200 | ＞3H | 1.4 | 稳定 |
| 50∶50 | 5B | ＞80 | ＞200 | ＞3H | 未测试 | *不稳定 |
*不稳定的意思是TiO2不能沉积和从自沉积浴中沉淀出来。
实施例5对比实验
35％不挥发物、灰色自沉积涂层组合物按照以下方法配制而成：
向1.5升烧瓶中加入92.7g的去离子水，5.63g具有20％不挥发物(活性)的阴离子表面活性剂，3.38g具有30％不挥发物的黑色颜料淤浆，904.89g具有42+/-1％不挥发物的阴离子改性聚合物乳液，以及132.6g具有50+/-1％不挥发物的实施例1的TiO2颜料淤浆。活性颜料与聚合物粘结剂的比为20％。
在这个实施例中，相对于上述的实施例改变了用于制造乳化液的表面活性剂。使用的表面活性剂具有与实施例1-4的表面活性剂类似的离子端基，但是减少烷氧基化作用的摩尔数使实施例5的表面活性剂具有较少的亲水性。
一种6％不挥发物、20毫升铁滴定灰色自沉积涂覆浴使用实施例5组合物按照实施例2的过程配制而成。
该浴混合一小时并且在连续搅动下将浴的参数调节至实施例2的参数。在灰色浴准备好并且参数最佳化之后，按照实施例2的方法处理金属薄板。得到的涂覆的薄板在颜色上呈褐色，指示没有沉积出颜料。在自沉积浴老化几天后，颜料从浴中分离或被变得不稳定。在乳剂和颜料颗粒之间改变浴的疏水/亲水平衡导致在颗粒之间的表面活性剂不等的分配，从表面活性剂中夺取了颜料颗粒，并且因此发生颜料颗粒的去稳定作用。
Claims (17)
1.一种用于涂覆活性金属表面的自沉积浴组合物，包含：
a.包括酸和至少一种氧化剂的自沉积加速剂的水溶液，所述酸的用量使组合物具有大约1.6至大约3.8的pH值；
b.均匀分散在整个组合物中的形成涂层的聚合物材料的颗粒；
c.均匀分散在整个组合物中的对所述酸稳定的非黑色固体颜料颗粒的组分；
d.包括阴离子表面活性剂的乳化组分；以及，任选地，
e.黑色颜料和/或适合在所述组合物形成的涂层中作为填料的细分固体；
在缺乏外部电位的情况下所述组合物有效地化学侵蚀浸入其中的活性金属表面以从该活性金属表面溶解金属来释放所述金属的离子并且足以使得所述聚合物材料和所述非黑色固体颜料颗粒以初始粘附涂层的形式沉积在活性金属表面上，其中所述表面沉浸在所述组合物中时间越长，所述初始粘附涂层的重量或厚度增加。
2.根据权利要求1的组合物，其中所述酸是氢氟酸并且所述非黑色固体颜料颗粒包含二氧化钛核、不同于二氧化钛的氧化物的第一涂层和有机材料的第二涂层。
3.根据权利要求2的组合物，其中所述氧化物的第一涂层包含实质上不溶于所述酸的氧化物。
4.根据权利要求2的组合物，其中所述氧化物的第一涂层包含选自氧化铝、氧化锆及其混合物的氧化物。
5.根据权利要求2的组合物，其中所述有机材料的第二涂层包含阴离子分散添加剂、阳离子分散添加剂或非离子分散添加剂。
6.根据权利要求2的组合物，其中所述有机材料的第二涂层包含聚丙烯酸酯、多磷酸酯、阳离子化聚丙烯酸酯、表氯醇树脂、双氰胺树脂、聚甲基丙烯酸酯、多元醇和聚酯中的至少一种。
7.根据权利要求6的组合物，其中所述聚甲基丙烯酸酯选自甲基丙烯酸季二甲基氨基乙酯、三聚氰胺-甲醛树脂及其混合物。
8.根据权利要求1的组合物，其中非黑色固体颜料颗粒与聚合物材料的重量比的范围为1-49wt％。
9.根据权利要求1的组合物，其中所述阴离子表面活性剂选自具有至少一个硫酸根、磺酸根、磷酸根、或膦酸根官能团的表面活性剂。
10.根据权利要求1的组合物，其中所述阴离子表面活性剂保持形成涂层的聚合物材料的颗粒和非黑色固体颜料颗粒的组分的分散，使得所述聚合物材料和所述颜料颗粒以初始粘附涂层的形式沉积在活性金属表面上。
11.根据权利要求1的组合物，其中所述组合物包括足量的黑色颜料以提供由该组合物形成的灰色涂层。
12.根据权利要求1的组合物，其中所述聚合物材料选自苯乙烯-丁二烯聚合物、丙烯腈-丁二烯聚合物、聚乙烯、丙烯酸类聚合物、四氟乙烯聚合物、聚氯乙烯、聚氨酯树脂、苯乙烯-丙烯酸类聚合物、环氧类聚合物、和环氧-丙烯酸类聚合物材料。
13.根据权利要求1的组合物，其中所述氧化剂选自过氧化氢、重铬酸盐、过硼酸盐、溴酸盐、高锰酸盐、亚硝酸盐、硝酸盐和氯酸盐。
14.根据权利要求1的组合物，其中所述酸选自氢氟酸、硫酸、盐酸、硝酸、磷酸、氢溴酸、氢碘酸、乙酸、氯乙酸、三氯乙酰、乳酸、酒石酸和聚丙烯酸。
15.根据权利要求1的组合物，其中所述氧化剂是过氧化氢。
16.一种在活性金属基底表面上沉积白色至灰白色或灰色自沉积涂层的方法，包括：
-用根据权利要求1至15任何一项的组合物与活性金属基底表面接触0.5至10分钟，以在所述表面上形成白色至灰白色或灰色初始粘附涂层；
-用包括水的清洗剂清洗所述初始粘附涂层；
-任选地，干燥所述初始粘附涂层；以及
-固化所述初始粘附涂层以形成固化的白色或灰色涂层。
17.用于形成自沉积浴的自沉积浓缩物组合物，包含：
-分散在整个组合物中的形成涂层的聚合物材料的颗粒；
-分散在整个组合物中的非黑色固体颜料颗粒，所述非黑色固体颜料颗粒包含二氧化钛核、不同于二氧化钛的氧化物的第一涂层和有机材料的第二涂层；以及
-包括阴离子表面活性剂的乳化组分；
其中非黑色固体颜料颗粒与聚合物材料的重量比的范围为1-49wt％。
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-
2007
- 2007-09-18 BR BRPI0718471A patent/BRPI0718471B1/pt not_active IP Right Cessation
- 2007-09-18 CA CA2663920A patent/CA2663920C/en active Active
- 2007-09-18 CA CA2881591A patent/CA2881591C/en active Active
- 2007-09-18 KR KR1020097007901A patent/KR20090079202A/ko not_active Application Discontinuation
- 2007-09-18 WO PCT/US2007/020186 patent/WO2008036259A1/en active Application Filing
- 2007-09-18 JP JP2009529209A patent/JP5587604B2/ja not_active Expired - Fee Related
- 2007-09-18 US US11/857,182 patent/US8313570B2/en active Active
- 2007-09-18 CN CN200780039468XA patent/CN101563429B/zh not_active Expired - Fee Related
- 2007-09-18 EP EP07838403A patent/EP2081999B1/en active Active
- 2007-09-19 TW TW96134904A patent/TW200831624A/zh unknown
-
2012
- 2012-05-07 US US13/465,409 patent/US8871309B2/en active Active
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2014
- 2014-09-08 US US14/479,867 patent/US9718092B2/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103608393A (zh) * | 2011-06-17 | 2014-02-26 | 汉高股份有限及两合公司 | 用于组合的金属基材的单浴自沉积涂层及其制备和使用方法 |
| CN103608393B (zh) * | 2011-06-17 | 2016-08-17 | 汉高股份有限及两合公司 | 用于组合的金属基材的单浴自沉积涂层及其制备和使用方法 |
| US10323314B2 (en) | 2011-06-17 | 2019-06-18 | Henkel Ag & Co. Kgaa | Single bath autodeposition coating for combination metal substrates and methods therefor |
| CN106543827A (zh) * | 2016-11-27 | 2017-03-29 | 湖南金裕化工有限公司 | 水溶性化学自吸附涂料 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20130004782A1 (en) | 2013-01-03 |
| US8871309B2 (en) | 2014-10-28 |
| EP2081999B1 (en) | 2013-01-16 |
| EP2081999A1 (en) | 2009-07-29 |
| BRPI0718471B1 (pt) | 2017-04-11 |
| KR20090079202A (ko) | 2009-07-21 |
| EP2081999A4 (en) | 2009-12-02 |
| JP5587604B2 (ja) | 2014-09-10 |
| CA2881591A1 (en) | 2008-03-27 |
| TW200831624A (en) | 2008-08-01 |
| BRPI0718471A2 (pt) | 2014-03-18 |
| US8313570B2 (en) | 2012-11-20 |
| US20080069960A1 (en) | 2008-03-20 |
| US9718092B2 (en) | 2017-08-01 |
| WO2008036259A1 (en) | 2008-03-27 |
| CA2663920C (en) | 2015-11-24 |
| CN101563429B (zh) | 2012-10-03 |
| US20140377541A1 (en) | 2014-12-25 |
| CA2663920A1 (en) | 2008-03-27 |
| CA2881591C (en) | 2018-01-23 |
| JP2010503773A (ja) | 2010-02-04 |
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