CN1079844C - 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

Info

Publication number
CN1079844C
CN1079844C CN95196423A CN95196423A CN1079844C CN 1079844 C CN1079844 C CN 1079844C CN 95196423 A CN95196423 A CN 95196423A CN 95196423 A CN95196423 A CN 95196423A CN 1079844 C CN1079844 C CN 1079844C
Authority
CN
China
Prior art keywords
grams per
per liter
aqueous acidic
enriched material
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN95196423A
Other languages
English (en)
Other versions
CN1166865A (zh
Inventor
D·R·冯克
J·A·格里尼
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PPG Industries Inc
Original Assignee
PPG Industries Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by PPG Industries Inc filed Critical PPG Industries Inc
Publication of CN1166865A publication Critical patent/CN1166865A/zh
Application granted granted Critical
Publication of CN1079844C publication Critical patent/CN1079844C/zh
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations
    • C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite anions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
    • C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/22—Orthophosphates containing alkaline earth metal cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/362—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also zinc cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
    • C23C22/42—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also phosphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
    • C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides

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。
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。
羟胺离子加速剂的一个实例叙述在Parker Chemical Company的公开的欧洲专利申请315059中。该专利文献叙述了羟胺已经以足够的量用于磷酸盐涂料中，以形成主要是球形和/或柱形的晶体结构。另外法国专利1294077公开了一种在非水溶剂中磷化处理金属的方法，所述溶剂含有具有基团
Figure C9519642300061
的有机化合物，例如二甲基乙肟。
此外，日本专利文件公开号JP57054279公开了一种用于钢制品的防腐蚀方法，包括向钢表面施加含氮和硫的杂环化合物和一种金属盐。该杂环化合物具有以下结构：
式中X可为羟基、胺、肼、酰基、肟、硫醇、硫酰基化合物或氢、烷基或烯丙基，而Y是一个饱和化合物。
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。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。
本发明一种优选含水酸性组合物含有0.8-1.2克/升锌离子、12-14克/升磷酸根离子、和肟加速剂是以1-5克/升的量存在的乙醛肟，还含有0.3克/升硝基苯磺酸钠作为加速剂，并且另外含有0.25-1.0克/升氟离子、0.8-1.0克/升锰离子、0.3-0.8克/升镍离子、2.0-5.0克/升硝酸根离子。
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 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，尤其是约0.3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，也可以含水浓缩物的形式制得，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、4457790和4433015。
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(“CHEMKLEEN166/171ALX”，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(“PPCRinse 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   8.3
Fe          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
1AAO是乙醛肟的缩写
2SNBS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“CHEMKLEEN163”(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    20Zn        0.88    0.98   0.93  1.01  1.05  1.71Ni        0.36     …          …         …        …        …
Mn        0.92   1.00   0.97   1.01   1.06   0.28W          …         …         …           …           …         0.20PO4      11.9   8.3    8.0    8.6    8.7    4.70NO3      2.7    6.7    6.8    6.8    7.2    4.0Fe        0.006  0.002  0.003  0.008  0.016  0.015Ca         …        0.50   0.33   0.53   0.44   …F         0.47    …        0.20    …        0.21    0.55AAO       1.0     …         …          2.0    2.0    4.75SNBS      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   号
                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)NaCl03(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 (33)

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0.4-3.0克/升锌离子，5-20克/升磷酸根离子，和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，其中所说的锌离子的存在量为0.8-1.2克/升。
4.如权利要求1所定义的含水酸性组合物，其中所说的磷酸根离子的存在量为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.如权利要求1所定义的含水酸性组合物，它含有0.8-1.2克/升锌离子、12-14克/升磷酸根离子、和肟加速剂是以1-5克/升的量存在的乙醛肟，还含有0.3克/升硝基苯磺酸钠作为加速剂，并且另外含有0.25-1.0克/升氟离子、0.8-1.0克/升锰离子、0.3-0.8克/升镍离子、2.0-5.0克/升硝酸根离子。
12.如权利要求1所定义的含水酸性组合物，其中所述的肟选自在含水酸性组合物中可溶并且稳定的、在pH值为2.5和5.5之间保持足够时间而不会预先分解并失去活性的、并且加速磷酸锌涂层在金属基体上的形成的肟。
13.如权利要求10所定义的含水酸性组合物，其中所述的硝基苯磺酸钠的量为0.1-0.5克/升。
14.一种含水酸性浓缩物，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10-100克/升锌离子，100-400克/升磷酸根离子和10-400克/升肟作为加速剂。
15.如权利要求14所定义的含水酸性浓缩物，其中所说的肟选自乙醛肟和丙酮肟。
16.如权利要求14所定义的含水酸性浓缩物，其中所说的锌的存在量为16-20克/升。
17.如权利要求14所定义的含水酸性浓缩物，其中所说的磷酸根的存在量为240-280克/升。
18.如权利要求14所定义的含水酸性浓缩物，其中所说的肟的存在量为10-40克/升。
19.如权利要求14所定义的含水酸性浓缩物，它含有2-30克/升氟离子。
20.如权利要求14所定义的含水酸性浓缩物，它含有4-40克/升锰离子。
21.如权利要求14所定义的含水酸性浓缩物，它含有4-24克/升镍离子。
22.如权利要求14所定义的含水酸性浓缩物，它含有20-200克/升硝酸根离子。
23.如权利要求14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。
24.如权利要求14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。
25.如权利要求14所定义的含水酸性浓缩物，其中用来稀释浓缩物成含水酸性组合物的含水介质可将浓缩物稀释20-100倍。
26.如权利要求24所定义的含水酸性浓缩物，其中附加加速剂的量使得当浓缩物稀释20-100倍后，附加加速剂的量为0.005-5.0克/升。
27.用于在金属基体上形成磷酸锌涂层的方法，该方法包括用一种含水酸性磷酸锌组合物与金属接触，所述组合物包括0.4-3.0克/升锌离子，5-20克/升磷酸根离子，以及0.5-20克/升的肟作为加速剂。
28.如权利要求27所定义的方法，其中所说的肟选自乙醛肟和丙酮肟。
29.如权利要求28所定义的方法，其中所说的肟的存在量为1-5克/升。
30.如权利要求27所定义的方法，其中所说的含水酸性磷酸锌组合物含有0.8-1.2克/升锌。
31.如权利要求27所定义的方法，其中所说的含水酸性磷酸锌组合物含有12-14克/升磷酸根离子。
32.如权利要求27所定义的方法，其中所说的含水酸性磷酸锌组合物含有0.1-2.5克/升氟离子。
33.如权利要求27所定义的方法，其中所述的金属基体选自镀锌钢和钢合金。
CN95196423A 1994-11-23 1995-11-01 含有肟加速剂的磷酸锌涂料组合物 Expired - Fee Related CN1079844C (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/344,441 1994-11-23
US08/344,441 US5588989A (en) 1994-11-23 1994-11-23 Zinc phosphate coating compositions containing oxime accelerators

Publications (2)

Publication Number Publication Date
CN1166865A CN1166865A (zh) 1997-12-03
CN1079844C true CN1079844C (zh) 2002-02-27

Family

ID=23350561

Family Applications (1)

Application Number Title Priority Date Filing Date
CN95196423A Expired - Fee Related CN1079844C (zh) 1994-11-23 1995-11-01 含有肟加速剂的磷酸锌涂料组合物

Country Status (15)

Country Link
US (1) US5588989A (zh)
EP (1) EP0792389B1 (zh)
JP (1) JP3267979B2 (zh)
KR (1) KR100250366B1 (zh)
CN (1) CN1079844C (zh)
AR (1) AR000189A1 (zh)
AT (1) ATE167529T1 (zh)
AU (1) AU684399B2 (zh)
CA (1) CA2206805C (zh)
DE (1) DE69503069T2 (zh)
ES (1) ES2120241T3 (zh)
MX (1) MX9703675A (zh)
TR (1) TR199501481A1 (zh)
WO (1) WO1996016204A1 (zh)
ZA (1) ZA959678B (zh)

Families Citing this family (98)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5653790A (en) * 1994-11-23 1997-08-05 Ppg Industries, Inc. Zinc phosphate tungsten-containing coating compositions using accelerators
US5797987A (en) * 1995-12-14 1998-08-25 Ppg Industries, Inc. Zinc phosphate conversion coating compositions and process
DE19716075A1 (de) * 1997-04-17 1998-10-22 Henkel Kgaa Mit Hydroxylamin und Chlorat beschleunigtes Phosphatierverfahren
US5954892A (en) * 1998-03-02 1999-09-21 Bulk Chemicals, Inc. Method and composition for producing zinc phosphate coatings on metal surfaces
US6248225B1 (en) 1998-05-26 2001-06-19 Ppg Industries Ohio, Inc. Process for forming a two-coat electrodeposited composite coating the composite coating and chip resistant electrodeposited coating composition
US6423425B1 (en) 1998-05-26 2002-07-23 Ppg Industries Ohio, Inc. Article having a chip-resistant electrodeposited coating and a process for forming an electrodeposited coating
US6676820B2 (en) 2001-03-02 2004-01-13 Ppg Industries Ohio, Inc. Process for electrocoating metal blanks and coiled metal substrates
GB2374088A (en) * 2001-03-29 2002-10-09 Macdermid Plc Conversion treatment of zinc and zinc alloy surfaces
DE10155666A1 (de) * 2001-11-13 2003-05-22 Henkel Kgaa Mit Hydroxylamin und organischen Stickstoffverbindungen beschleunigtes Phosphatierverfahren
ES2213500B1 (es) * 2004-05-04 2005-05-01 Delphi Diesel Systems S.L. Prodecimiento de obtencion de un recubrimiento mediante fosfatado en una pieza de hierro o acero, y pieza de hierro o acero correspondiente.
US8147713B2 (en) * 2006-06-30 2012-04-03 Ppg Industries Ohio, Inc. Composition and method for scale removal and leak detection
US20080314479A1 (en) * 2007-06-07 2008-12-25 Henkel Ag & Co. Kgaa High manganese cobalt-modified zinc phosphate conversion coating
US20100190923A1 (en) 2009-01-27 2010-07-29 Shanti Swarup Method for producing a dispersion comprising a one stage reaction product and an associated coating
US8486538B2 (en) 2009-01-27 2013-07-16 Ppg Industries Ohio, Inc Electrodepositable coating composition comprising silane and yttrium
US8361301B2 (en) 2009-03-31 2013-01-29 Ppg Industries Ohio, Inc. Electrocoating composition comprising a crater control additive
US8563648B2 (en) 2009-10-28 2013-10-22 Ppg Industries Ohio, Inc. Coating composition comprising an alkoxysilane, a polysiloxane, and a plurality of particles
US8497359B2 (en) 2010-02-26 2013-07-30 Ppg Industries Ohio, Inc. Cationic electrodepositable coating composition comprising lignin
US8288504B2 (en) 2010-03-10 2012-10-16 Ppg Industries Ohio, Inc. Method of making a cyclic guanidine from dicyandiamide and coating compositions containing same
US8148490B2 (en) 2010-03-10 2012-04-03 Ppg Industries Ohio, Inc. Method of making a cyclic guanidine from a guanidinium salt and a weak acid and coating compositions containing the same
US8840962B2 (en) 2010-05-14 2014-09-23 Ppg Industries Ohio, Inc. Substantially defect-free sound and vibration damping coating
US8277626B2 (en) 2010-06-11 2012-10-02 Ppg Industries Ohio, Inc. Method for depositing an electrodepositable coating composition onto a substrate using a plurality of liquid streams
US8557099B2 (en) 2010-10-25 2013-10-15 Ppg Industries Ohio, Inc. Electrocurtain coating process for coating solar mirrors
US8535501B2 (en) 2011-01-28 2013-09-17 Ppg Industries Ohio, Inc. Electrical contact arrangement for a coating process
US9534074B2 (en) 2012-06-25 2017-01-03 Ppg Industries Ohio, Inc. Aqueous resinous dispersions that include a zinc (II) amidine complex and methods for the manufacture thereof
US8945365B2 (en) 2012-07-13 2015-02-03 Ppg Industries Ohio, Inc. Electrodepositable coating compositions exhibiting resistance to cratering
US9017815B2 (en) 2012-09-13 2015-04-28 Ppg Industries Ohio, Inc. Near-infrared radiation curable multilayer coating systems and methods for applying same
US20170306497A1 (en) * 2016-04-25 2017-10-26 Ppg Industries Ohio, Inc. System for nickel-free zinc phosphate pretreatment
CN109642098B (zh) 2016-07-26 2022-02-11 Ppg工业俄亥俄公司 包含1,1-二活化的乙烯基化合物的可电沉积的涂料组合物
CA3052051C (en) 2017-02-07 2021-10-26 Ppg Industries Ohio, Inc. Low-temperature curing adhesive compositions
EP3589703B1 (en) 2017-03-01 2021-05-12 PPG Industries Ohio, Inc. Electrodepositable coating compositions
US10370545B2 (en) 2017-09-19 2019-08-06 Ppg Industries Ohio, Inc. Low VOC anionic electrodepositable coating composition
TW201922765A (zh) 2017-10-10 2019-06-16 美商片片堅俄亥俄州工業公司 離子液體
US10273253B1 (en) 2017-10-10 2019-04-30 Ppg Industries Ohio, Inc. Method for producing an ionic liquid
EP3728484A1 (en) 2017-12-20 2020-10-28 PPG Industries Ohio, Inc. Coating compositions having improved corrosion resistance
EP3728486A1 (en) 2017-12-20 2020-10-28 PPG Industries Ohio, Inc. Electrodepositable coating compositions and electrically conductive coatings resulting therefrom
US11732125B2 (en) 2018-02-09 2023-08-22 Ppg Industries Ohio, Inc. Coating compositions
US10947408B2 (en) 2018-06-27 2021-03-16 Prc-Desoto International, Inc. Electrodepositable coating composition
WO2020023786A1 (en) 2018-07-25 2020-01-30 Ppg Industries Ohio, Inc. A product coated with an aqueous or powder coating composition comprising an acrylic polyester resin
EP3827058A1 (en) 2018-07-25 2021-06-02 PPG Industries Ohio Inc. A product coated with an aqueous or powder coating composition comprising an acrylic polyester resin
US20220127448A1 (en) 2018-09-20 2022-04-28 Ppg Industries Ohio, Inc. Thiol-containing composition
WO2020077333A1 (en) 2018-10-12 2020-04-16 Ppg Industries Ohio, Inc. Compositions containing thermally conductive fillers
KR20210072056A (ko) 2018-10-15 2021-06-16 피피지 인더스트리즈 오하이오 인코포레이티드 전도성 기판 전기코팅 시스템
KR20210077721A (ko) 2018-10-23 2021-06-25 피피지 인더스트리즈 오하이오 인코포레이티드 기능성 폴리에스터 및 이의 생산 방법
EP3894485A1 (en) 2018-12-13 2021-10-20 PPG Industries Ohio Inc. Polyhydroxyalkylamide materials for use as crosslinkers
KR20210114043A (ko) 2019-01-23 2021-09-17 피피지 인더스트리즈 오하이오 인코포레이티드 전도성 기재를 전기 코팅하기 위한 시스템
CA3133856A1 (en) 2019-03-20 2020-09-24 Ppg Industries Ohio, Inc. Two component coating compositions
CA3138013A1 (en) 2019-04-27 2020-11-05 Ppg Industries Ohio, Inc. Curable coating compositions
US11485874B2 (en) 2019-06-27 2022-11-01 Prc-Desoto International, Inc. Addition polymer for electrodepositable coating compositions
US11274167B2 (en) 2019-06-27 2022-03-15 Prc-Desoto International, Inc. Carbamate functional monomers and polymers and use thereof
US11313048B2 (en) 2019-06-27 2022-04-26 Prc-Desoto International, Inc. Addition polymer for electrodepositable coating compositions
FR3098817A1 (fr) 2019-07-16 2021-01-22 Ppg Industries Ohio, Inc. Compositions contenant des charges thermiquement conductrices
EP4010398A1 (en) 2019-08-06 2022-06-15 PPG Industries Ohio Inc. Adhesive compositions
KR20220047609A (ko) 2019-08-23 2022-04-18 피피지 인더스트리즈 오하이오 인코포레이티드 코팅 조성물
US20220325129A1 (en) 2019-08-23 2022-10-13 Prc-Desoto International, Inc. Coating compositions
US20220363917A1 (en) 2019-09-06 2022-11-17 Ppg Industries Ohio, Inc. Electrodepositable coating compositions
US20220372207A1 (en) 2019-09-23 2022-11-24 Ppg Industries Ohio, Inc. Curable compositions
CN114829476B (zh) 2019-12-11 2024-04-12 Ppg工业俄亥俄公司 含有导热填料的组合物
CN115087709A (zh) 2019-12-20 2022-09-20 Ppg工业俄亥俄公司 包含层状硅酸盐颜料和分散剂的可电沉积的涂层组合物
US11466175B2 (en) 2019-12-30 2022-10-11 Ppg Industries Ohio, Inc. Silicone-based electrodepositable coating composition
CN114846044A (zh) 2019-12-31 2022-08-02 Ppg工业俄亥俄公司 可电沉积的涂层组合物
CA3168168A1 (en) 2020-02-26 2021-09-02 Sijmen J. VISSER Two-layer dielectric coating
US11485864B2 (en) 2020-02-26 2022-11-01 Ppg Industries Ohio, Inc. Electrodepositable coating composition having improved crater control
US11597791B2 (en) 2020-03-27 2023-03-07 Ppg Industries Ohio, Inc. Crosslinking material and uses thereof
WO2021211185A1 (en) 2020-04-15 2021-10-21 Ppg Industries Ohio, Inc. Compositions containing thermally conductive fillers
AU2021256983B2 (en) 2020-04-15 2024-03-14 Ppg Industries Ohio, Inc. Compositions containing thermally conductive fillers
WO2021211182A1 (en) 2020-04-15 2021-10-21 Ppg Industries Ohio, Inc. Compositions containing thermally conductive fillers
MX2022012970A (es) 2020-04-15 2023-01-05 Ppg Ind Ohio Inc Composiciones que contienen agentes de relleno térmicamente conductores.
EP4136162A1 (en) 2020-04-15 2023-02-22 PPG Industries Ohio Inc. Compositions containing thermally conductive fillers
EP4136140A1 (en) 2020-04-15 2023-02-22 PPG Industries Ohio Inc. Compositions containing thermally conductive fillers
WO2021222358A1 (en) 2020-04-30 2021-11-04 Ppg Industries Ohio, Inc. Phenolic resin and coating compositions using the same
US20230272209A1 (en) 2020-07-07 2023-08-31 Ppg Industries Ohio, Inc. Curable coating compositions
KR20230120662A (ko) 2020-12-18 2023-08-17 피피지 인더스트리즈 오하이오 인코포레이티드 열 전도성 및 전기 절연성 및/또는 난연성 전착성 코팅조성물
KR20230125044A (ko) 2020-12-31 2023-08-28 피피지 인더스트리즈 오하이오 인코포레이티드 인산염 저항성 전착성 코팅 조성물
KR20230136748A (ko) 2021-01-29 2023-09-26 피피지 인더스트리즈 오하이오 인코포레이티드 코팅된 기재
WO2022165274A1 (en) 2021-01-29 2022-08-04 Ppg Industries Ohio, Inc. Coating composition
EP4301818A1 (en) 2021-03-02 2024-01-10 PRC-Desoto International, Inc. Corrosion inhibiting coatings comprising aluminum particles, magnesium oxide and an aluminum and/or iron compound
WO2022187855A1 (en) 2021-03-05 2022-09-09 Ppg Industries Ohio, Inc. Electrodepositable coating compositions
CN117377727A (zh) 2021-03-05 2024-01-09 Prc-迪索托国际公司 包括聚硫化物腐蚀抑制剂的涂层组合物
CN117321150A (zh) 2021-03-05 2023-12-29 Prc-迪索托国际公司 腐蚀抑制涂料组合物
EP4314187A1 (en) 2021-03-26 2024-02-07 PPG Industries Ohio Inc. Coating compositions
WO2022272015A1 (en) 2021-06-24 2022-12-29 Prc-Desoto International, Inc. Systems and methods for coating multi-layered coated metal substrates
CA3218801A1 (en) 2021-06-24 2022-12-29 Corey James DEDOMENIC Electrodepositable coating compositions
KR20240023159A (ko) 2021-07-01 2024-02-20 피피지 인더스트리즈 오하이오 인코포레이티드 전착성 코팅 조성물
KR20240026234A (ko) 2021-07-01 2024-02-27 피피지 인더스트리즈 오하이오 인코포레이티드 전착성 코팅 조성물
KR20240027803A (ko) 2021-07-01 2024-03-04 피피지 인더스트리즈 오하이오 인코포레이티드 전착성 코팅 조성물
CA3228687A1 (en) 2021-09-09 2023-03-16 Masayuki Nakajima Adhesive composition with lightweight filler
CA3230010A1 (en) 2021-09-16 2023-03-23 Ppg Industries Ohio, Inc. Curing of coating compositions by application of pulsed infrared radiation
WO2023097177A1 (en) 2021-11-24 2023-06-01 Ppg Industries Ohio, Inc. (co)polymer-acrylic block copolymers and coating compositions containing the same
WO2023102525A1 (en) 2021-12-02 2023-06-08 Ppg Industries Ohio, Inc. Coating compositions
WO2023219658A2 (en) 2022-03-02 2023-11-16 Prc-Desoto International, Inc. Multi-layered coated metal substrates
WO2023183770A1 (en) 2022-03-21 2023-09-28 Ppg Industries Ohio, Inc. Electrodepositable coating compositions
WO2023240057A1 (en) 2022-06-06 2023-12-14 Ppg Industries Ohio, Inc. Coating compositions
WO2024039927A1 (en) 2022-08-16 2024-02-22 Ppg Industries Ohio, Inc. Coating compositions
WO2024040217A1 (en) 2022-08-19 2024-02-22 Ppg Industries Ohio, Inc. Electrodepositable coating compositions
WO2024040260A1 (en) 2022-08-19 2024-02-22 Ppg Industries Ohio, Inc. Coating compositions
WO2024044576A1 (en) 2022-08-22 2024-02-29 Ppg Industries Ohio, Inc. Coating compositions
WO2024059451A1 (en) 2022-09-16 2024-03-21 Ppg Industries Ohio, Inc. Solvent-borne coating compositions comprising a water-dispersible polyisocyanate
WO2024073305A1 (en) 2022-09-27 2024-04-04 Ppg Industries Ohio, Inc. Electrodepositable coating compositions

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1294077A (fr) * 1960-07-15 1962-05-18 Parker Ste Continentale Procédé de phosphatation des métaux dans des solvants non aqueux
US4186035A (en) * 1978-10-16 1980-01-29 Diamond Shamrock Corporation Chromium containing coating
EP0315059A1 (en) * 1987-10-30 1989-05-10 HENKEL CORPORATION (a Delaware corp.) Process and composition for zinc phosphate coating

Family Cites Families (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2298280A (en) * 1939-02-02 1942-10-13 Parker Rust Proof Co Treatment of metal
DE1072055B (zh) * 1952-08-28
US2884351A (en) * 1956-01-25 1959-04-28 Parker Rust Proof Co Method of cold rolling ferrous strip stock
US2874081A (en) * 1956-08-02 1959-02-17 Parker Rust Proof Co Pretreatment solution for phosphate coating, method of preparing the same and process of treating metal surfaces
US3637533A (en) * 1967-02-14 1972-01-25 Givaudan Corp Perfume-containing compositions containing certain oximes as olfactory agents
US3975214A (en) * 1972-04-24 1976-08-17 Oxy Metal Industries Corporation Tannin containing compositions
US3907966A (en) * 1972-06-28 1975-09-23 Kennecott Copper Corp Nickel extraction and stripping using oximes and ammoniacal carbonate solutions
US4029704A (en) * 1972-08-25 1977-06-14 Imperial Chemical Industries Limited Oximes
US3867506A (en) * 1973-07-19 1975-02-18 Kennecott Copper Corp Cobalt stripping from oximes
US3923554A (en) * 1974-02-07 1975-12-02 Detrex Chem Ind Phosphate coating composition and method
SE406940B (sv) * 1974-04-13 1979-03-05 Collardin Gmbh Gerhard Forfarande for framstellning av fosfatbeleggningar med sprutningsmetoden pa jern och stal
US4108817A (en) * 1976-12-30 1978-08-22 Amchem Products, Inc. Autodeposited coatings
US4149909A (en) * 1977-12-30 1979-04-17 Amchem Products, Inc. Iron phosphate accelerator
US4335243A (en) * 1978-02-13 1982-06-15 Sterling Drug Inc. Oximes of 11-(3-oxooctyl)-hexahydro-2,6-methano-3-benzazocines
JPS5811513B2 (ja) * 1979-02-13 1983-03-03 日本ペイント株式会社 金属表面の保護方法
JPS5811514B2 (ja) * 1979-05-02 1983-03-03 日本ペイント株式会社 金属表面の保護方法
JPS5754279A (ja) * 1980-09-19 1982-03-31 Nippon Steel Corp Tetsukoseihinnoboshokuho
DE3101866A1 (de) * 1981-01-22 1982-08-26 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur phosphatierung von metallen
US4673444A (en) * 1981-03-16 1987-06-16 Koichi Saito Process for phosphating metal surfaces
US4433015A (en) * 1982-04-07 1984-02-21 Parker Chemical Company Treatment of metal with derivative of poly-4-vinylphenol
JPS5935681A (ja) * 1982-08-24 1984-02-27 Nippon Paint Co Ltd カチオン型電着塗装用金属表面のリン酸塩処理方法
DE3475321D1 (en) * 1983-05-04 1988-12-29 Ici Plc Corrosion inhibition
US4457790A (en) * 1983-05-09 1984-07-03 Parker Chemical Company Treatment of metal with group IV B metal ion and derivative of polyalkenylphenol
US5176843A (en) * 1985-05-16 1993-01-05 Imperial Chemical Industries Plc Composition and use of the composition for the extraction of metals from aqueous solution
GB8515561D0 (en) * 1985-06-19 1985-07-24 Ici Plc Anti-corrosion meal complex compositions
US4793867A (en) * 1986-09-26 1988-12-27 Chemfil Corporation Phosphate coating composition and method of applying a zinc-nickel phosphate coating
GB9108221D0 (en) * 1991-04-18 1991-06-05 Ici Plc Compound preparation and use
US5312491A (en) * 1992-06-08 1994-05-17 Binter Randolph K Rust inhibiting compositions and methods for protecting metal surfaces with same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1294077A (fr) * 1960-07-15 1962-05-18 Parker Ste Continentale Procédé de phosphatation des métaux dans des solvants non aqueux
US4186035A (en) * 1978-10-16 1980-01-29 Diamond Shamrock Corporation Chromium containing coating
EP0315059A1 (en) * 1987-10-30 1989-05-10 HENKEL CORPORATION (a Delaware corp.) Process and composition for zinc phosphate coating

Also Published As

Publication number Publication date
AR000189A1 (es) 1997-05-21
JP2002509579A (ja) 2002-03-26
TR199501481A1 (tr) 1996-10-21
JP3267979B2 (ja) 2002-03-25
CA2206805C (en) 2001-03-27
DE69503069D1 (de) 1998-07-23
MX9703675A (es) 1997-08-30
WO1996016204A1 (en) 1996-05-30
CA2206805A1 (en) 1996-05-30
CN1166865A (zh) 1997-12-03
ES2120241T3 (es) 1998-10-16
ATE167529T1 (de) 1998-07-15
KR100250366B1 (ko) 2000-04-01
US5588989A (en) 1996-12-31
AU684399B2 (en) 1997-12-11
EP0792389B1 (en) 1998-06-17
AU4018495A (en) 1996-06-17
ZA959678B (en) 1997-05-14
EP0792389A1 (en) 1997-09-03
DE69503069T2 (de) 1999-01-07

Similar Documents

Publication Publication Date Title
CN1079844C (zh) 含有肟加速剂的磷酸锌涂料组合物
RU2439197C2 (ru) Способ антикоррозионной обработки чистых непокрытых металлических поверхностей (варианты) и кислый, не содержащий хром водный раствор для обработки упомянутых поверхностей
CN1038949C (zh) 处理金属基质的磷酸盐水涂液及其浓缩液组合物及处理方法
CN1079845C (zh) 用含金属的后冲洗液进行磷酸盐化的方法
US20040163735A1 (en) Chemical conversion coating agent and surface-treated metal
EP1433875A1 (en) Chemical conversion coating agent and surface-treated metal
EP1433877A1 (en) Pretreatment method for coating
JP2004500479A (ja) りん酸塩処理、ポストリンス及び陰極電着塗装の一連の方法
JP4187162B2 (ja) 化成処理剤及び表面処理金属
CA2018100A1 (en) Compositions and method for applying coatings to metallic surfaces
CN1129961A (zh) 无镍的磷酸盐化处理方法
US20040020564A1 (en) Adhesion promoter in conversion solutions
US6231688B1 (en) Composition and process for zinc phosphate conversion coating
CN1064415C (zh) 低含量铜和锰的锌磷酸盐处理方法
KR19990087077A (ko) 저농도의 니켈 및/또는 코발트를 이용한 아연-포스파타이징 방법
CN1032146C (zh) 金属表面综合处理液及其处理工艺
CA2591141A1 (en) Iron phosphating process that reduces laser scale resulting in improved paint adhesion
WO1996017976A1 (en) Zinc phosphate conversion coating composition and process
CZ279329B6 (cs) Prostředek pro fosfátování kovů, zejména před kataforézou
KR920016563A (ko) 포스페이트 피복 조성물 및 아연-니켈-망간 포스페이트 피복물의 도포 방법

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C53 Correction of patent of invention or patent application
COR Change of bibliographic data

Free format text: CORRECT: APPLICANT; FROM: PPG INDUSTRIES INC. TO: PPG IND OHIO INC.

CP03 Change of name, title or address

Address after: American Ohio

Applicant after: PPG Industries, Inc.

Address before: American Pennsylvania

Applicant before: PPG Industries Inc.

C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20020227

Termination date: 20101101