CN113165013A - 金属表面处理 - Google Patents

金属表面处理 Download PDF

Info

Publication number
CN113165013A
CN113165013A CN201980075377.4A CN201980075377A CN113165013A CN 113165013 A CN113165013 A CN 113165013A CN 201980075377 A CN201980075377 A CN 201980075377A CN 113165013 A CN113165013 A CN 113165013A
Authority
CN
China
Prior art keywords
polymer
coating
conversion
varnish
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.)
Pending
Application number
CN201980075377.4A
Other languages
English (en)
Inventor
M-P·拉布
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.)
Rhodia Operations SAS
Original Assignee
Rhodia Operations SAS
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 Rhodia Operations SAS filed Critical Rhodia Operations SAS
Publication of CN113165013A publication Critical patent/CN113165013A/zh
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • 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
    • C09D143/00—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 containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/02—Homopolymers or copolymers of monomers containing phosphorus
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/002—Priming paints
    • 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
    • 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
    • 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
    • C23C22/78—Pretreatment of the material to be coated
    • 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
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/20—Metallic substrate based on light metals
    • B05D2202/25—Metallic substrate based on light metals based on Al
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/51—One specific pretreatment, e.g. phosphatation, chromatation, in combination with one specific coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Paints Or Removers (AREA)

Abstract

本发明涉及至少一种聚合物P用于处理旨在被涂料、清漆或粘合剂涂覆的金属表面的用途，所述聚合物通过以下项的混合物的自由基共聚获得：(i)丙烯酸；(ii)甲基丙烯酸；和(iii)至少一种甲基丙烯酸2‑羟乙酯磷酸酯。本发明还涉及利用此聚合物P进行涂覆的方法、包含所述聚合物P并且可用于这些方法的组合物、以及所获得的经涂覆的材料。

Description

金属表面处理
本发明涉及金属基表面的处理的领域，并且尤其是旨在用成膜有机组合物(如涂料、清漆或粘合剂组合物)涂覆的金属表面。本发明更具体地涉及所述金属表面的处理，其旨在提供尤其是抗腐蚀保护和/或增强成膜有机物的附着。
为了在金属表面(尤其是在铝或钢)上提供此类效果，已经提出了若干种方法，包括尤其是在金属表面上沉积无机涂层，尤其是所谓的“转化涂层”。
术语“转化涂层”在本领域中是众所周知的，并且是指在金属表面上形成的层，该层是在所述表面(尤其是在铝)上的天然氧化物的有利替代物，并且它是通过与金属表面的化学元素反应在金属表面上受控化学形成膜而获得的，使得从金属材料中溶解的至少一些阳离子沉积在所述转化涂层中。
典型地，涂层(如转化涂层)是通过使金属表面与含有金属阳离子和氟离子的溶液反应而获得的。过去，已经提出了含铬涂层(典型地通过表面与包含H2CrF6的溶液的反应获得的)，并且最近，提出了基于例如锆、钛或其他金属的较低毒性的涂层(例如通过表面与包含H2TiF6、H2ZrF6、H2HfF6、H2AlF6、H2SiF6、H2GeF6、H2SNF4、或HBF4的溶液的反应获得的)。转化涂层可以包括其他化合物，例如像硅烷前体。
为了提高在涂层(如转化涂层)上的耐腐蚀性和涂料粘附性，已知添加了一些添加剂，尤其是有机聚合物。在这一点上，例如已经描述了使用聚丙烯酸。一种典型的添加剂是从陶氏化学公司(DOW)(先前从罗门哈斯公司(Rohm&Haas))可获得的ACUMERTM 1510，已经针对这种应用对其进行了广泛描述。关于这一点的更多细节，可尤其参考WO 97/13588、US 4,191,596或US 4921552。
本发明的一个目的是提供一种用于处理金属表面的新方法，所述方法给予良好的该金属表面的抗腐蚀保护和成膜有机组合物(如施加到该金属表面的涂料、清漆或粘合剂组合物)的良好附着。
为此目的，本发明提出利用一种特定的聚合物，优选地与转化涂层的形成一起(即，之前、期间或之后)，这有利地导致经处理的金属表面，其显示出以下是非常令人感兴趣的：当被成膜组合物(如涂料、清漆或粘合剂组合物)涂覆时，在表面与经涂覆的组合物之间获得了良好的附着。此外，表面获得了良好的保护，尤其是抗腐蚀保护。
更确切地，本发明利用至少一种聚合物P，所述聚合物是通过丙烯酸、甲基丙烯酸和至少一种具有下式(a)的甲基丙烯酸2-羟乙酯磷酸酯的混合物的自由基共聚获得的聚合物：
Figure BDA0003066580050000021
其中n是0、1或2。
典型地，所述聚合物P是通过丙烯酸、甲基丙烯酸和若干种具有式(a)的甲基丙烯酸2-羟乙酯磷酸酯的混合物的混合物的自由基共聚获得的，其中n的值不同。
优选地，所述聚合物P是通过混合物的自由基共聚获得的，基于丙烯酸、甲基丙烯酸和具有式(a)的甲基丙烯酸2-羟乙酯磷酸酯的总量，所述混合物具有以下摩尔比：
-丙烯酸(AA)：从80％至90％(例如，约83％-85％)，
-甲基丙烯酸(MAA)：5％至15％(例如，约11％-13％)
-甲基丙烯酸2-羟乙酯磷酸酯：2％至6％(例如，约4％)。
此外，根据本发明使用的聚合物P优选地具有至少7,500Da，例如10kDa至1500kDa、例如10kDa至150kDa、值得注意地在10与100kDa之间的分子量。典型地，根据本发明使用的聚合物P具有从10至40kDa，例如20至30kDa的分子量。
尤其适用于本发明的聚合物P是重均分子量为约20至30kDa的无规共聚物，该无规共聚物是丙烯酸、甲基丙烯酸和具有式(a)的甲基丙烯酸2-羟乙酯磷酸酯的混合物的共聚产物，优选地以约85:11:4或83:13:4的摩尔比。
适用于本发明的商业产品是例如从索尔维公司(SOLVAY)可获得的聚合物
Figure BDA0003066580050000031
8801。
在本发明的范围内，诸位发明人现在已经观察到，使用聚合物P导致保护和促进金属表面与涂覆在所述表面上的涂料之间的附着，其优选地好于用常用添加剂如ACUMERTM1510观察到的那些。
根据具体的方面，本发明的一个具体目的是至少一种如上定义的聚合物P用于处理旨在被涂料、清漆或粘合剂涂覆的金属表面的用途。有待处理的金属表面是优选地包含选自铝、钢、锌、镁及其合金的金属的表面。本发明对铝或铝合金的金属表面尤其感兴趣。
根据令人感兴趣的实施例，通过所述表面与转化组合物的反应，将转化涂层施加在有待处理的金属表面上(换句话说，将转化组合物施加在金属表面上，以在其上形成转化涂层)。在那种情况下，典型地：
-所述转化组合物包含聚合物P的全部或部分作为添加剂；和/或
-将所述转化涂层施加在金属表面上并且然后将所述聚合物P的全部或部分施加在所述转化涂层上。
根据与前一个相容的另一个可能的实施例，所述聚合物P的全部或部分存在于施加在所述表面上的涂料、清漆或涂层中，优选地在将转化涂层施加在所述金属表面上之后。
根据另一个方面，本发明的另一个具体目的是一种用涂料、清漆或粘合剂，优选用涂料涂覆金属表面的方法，所述方法包括用至少一种组合物处理所述表面的步骤，所述组合物包含至少一种如上定义的聚合物P。在那个范围内，所述包含所述聚合物P的组合物典型地可以是：
-包含聚合物P的转化组合物；和/或
-所述聚合物P的溶液或分散体，其优选地在将转化涂层施加在有待处理的表面上之后施加在所述表面上；和/或
-所述涂料、清漆或粘合剂，其可以包含所述聚合物P的全部或部分。
包含聚合物P的转化组合物和包含所述聚合物的涂料、清漆或粘合剂组合物还构成了本发明的具体目的。
典型地，聚合物P存在于转化组合物中和/或施加在转化涂层上的溶液或分散体中。在那种情况下，涂料、清漆或粘合剂被施加在先前通过聚合物处理的表面上。根据一些具体的实施例，施加了可以在经处理的表面与涂料、清漆或粘合剂之间施加的附加层(例如，这是在第一位点上处理金属箔，然后必须在第二位点上对其进行涂覆，例如涂上涂料的情况：在那种情况下，可以在经处理的箔上施加润滑剂，以便允许将箔轧制并且便于其运输)。
根据又另一个方面，本发明的具体目的是包含金属表面的材料，所述金属表面包括全部或部分地(i)用如上定义的聚合物P处理和(ii)被涂料、清漆或粘合剂覆盖的金属表面。
这些材料包括尤其具有金属表面的材料，所述金属表面全部或部分地被以下项覆盖：
-至少一个涂层(典型地转化涂层和/或涂料、清漆或粘合剂层)，其包含至少一种聚合物P；
和/或
-层(典型地转化涂层)，其包含如上所定义的聚合物P与经处理的表面的金属或在所述层中存在的另一种化合物的反应产物。
现在将更详细地描述具体特征和可能的实施例。
经处理的金属表面
任何金属表面都可以用本发明的聚合物P处理，但是本发明尤其适用于处理以下项的金属表面：
-铝或铝基合金；或
-钢，例如镀锌钢(热浸镀锌HDG或电解镀锌EG)；或冷轧钢(CRS)；或
-镁或镁基合金；或
-锌或锌基合金
本发明对铝和铝合金的金属表面尤其感兴趣，如在所附实例中测试的铝合金AA5005，或其他合金，如1xxx、2xxx、3xxx、4xxx、5xxxx、6xxx系列的那些，如AA1050、2024、3003、5182、5754、6111、6016、6060、6063、6182。
转化涂层
当根据本发明将转化涂层施加在有待处理的金属表面上时，所述转化涂层可以通过使所述表面与从现有技术中已知的任何转化组合物接触来获得。
使金属表面与转化组合物的接触可以通过本身已知的任何方式进行，如在转化浴中的浸涂、或喷涂，作为说明性的实例。
根据本发明使用的转化组合物典型地可以包含氟阴离子和阳离子金属，例如化合物，如H2CrF6，或更优选地无铬化合物，如H2TiF6、H2ZrF6、H2HfF6、H2AlF6、H2SiF6、H2GeF6、H2SNF4或HBF4。
转化组合物还可以包含其他化合物，例如像硅烷前体，和/或铈盐，和/或钼酸铽。
此外，根据具体的实施例，转化组合物可以包含根据本发明使用的用于处理表面的聚合物P的全部或部分。在那种情况下，转化层的施加本身导致根据本发明的表面处理。
在其他方面，所述处理典型地是在形成转化层之后通过使带有转化层的金属表面与聚合物P(它们典型地可以以聚合物P的溶液或悬浮液的形式施加在转化层上，或者在施加在转化层上的涂料、清漆或粘合剂组合物内)接触而获得的。
根据具体的实施例，可以考虑在转化组合物中和在施加在转化层上的涂料、清漆或粘合剂组合物内使用聚合物P。
以下实例说明了本发明。
实例
已经在此实例中对
Figure BDA0003066580050000061
8801进行了测试，并将其与ACUMER 1510进行了比较。
已经在铝合金面板(AA5005，来自Q-Panel公司)上，用通常的实验室设备(烧杯、烘箱、……)、粉末涂覆装置(来自工业系统公司(Industrie Systemes)的GEMA 2C)和腐蚀室(Q-FOG CRH 600L，来自QFOG公司)进行了测试。
在每个测试中，应用了以下方案：
■清洁和蚀刻
它是通过将有待测试的每个面板浸入组合的清洁-蚀刻浴(其是1L浴)中进行的，典型地是通过稀释可商购的配制品DBT ALU 200(可从Chemtec Aertec公司获得)(将5g的DBT ALU 200溶于995g水中)进行的。将面板在50℃在轻微搅拌(200rpm)下浸入清洁-蚀刻浴中持续3min。然后用1L的去离子水冲洗面板。
■处理
它是通过将在前一步骤的清洁/蚀刻之后获得的面板浸入处理浴中进行的，所述处理浴是通过在水中稀释以下项制成的1L浴：
-浓度为200ppm活性物(0.02wt％)的六氟化锆H2ZrF6；和
-有待测试的添加剂(根据本发明的
Figure BDA0003066580050000062
8801；或对比实例中的ACUMERTM1510)，浓度为下表给出的从50ppm活性物(0.005wt％)最高达1,000ppm(0.1wt％)：
将面板浸入25℃的处理浴中持续2min。没有将其冲洗。用压缩空气将过量的浴液从表面冲洗掉。然后将面板在60℃的烘箱中干燥30min。
■涂覆：
然后将每个面板用来自里波尔公司(RIPOL)(BIANCO RAL 9010)的聚酯白色粉末涂料涂上涂料。
测试
然后根据类似于在以下列出的在以下标准中描述的那些方案对每个板进行测试：
-乙酸盐喷雾：T＝35(+/-2)℃，[NaCl]＝50(+/-5)g/L，pH＝3.1-3.3(ISO 9227)
-划线方案：如ISO 17872中所述的
-如ISO 4628-3中所述引用的生锈程度
-如ISO 4628-2中所述引用的起泡程度
生锈结果
(根据ISO 4628-3评估)
Figure BDA0003066580050000071
Figure BDA0003066580050000081
无论浓度如何，对比实例的生锈看起来更快。
起泡结果
(根据ISO 4628-2评估)
Figure BDA0003066580050000082
再一次地，根据本发明的聚合物的结果更好。

Claims (13)

1.至少一种聚合物P用于处理旨在被涂料、清漆或粘合剂涂覆的金属表面的用途，所述聚合物通过以下项的混合物的自由基共聚获得：(i)丙烯酸；(ii)甲基丙烯酸；和(iii)至少一种具有下式(a)的甲基丙烯酸2-羟乙酯磷酸酯：
Figure FDA0003066580040000011
其中n是0、1、或2。
2.如权利要求1所述的用途，其中，所述聚合物P是通过混合物的自由基共聚获得的，基于丙烯酸、甲基丙烯酸和具有式(a)的甲基丙烯酸2-羟乙酯磷酸酯的总量，所述混合物具有以下摩尔比：
-丙烯酸：从80％至90％
-甲基丙烯酸：5％至15％
-甲基丙烯酸2-羟乙酯磷酸酯：2％至6％。
3.如权利要求1或2所述的用途，其中，所述聚合物P具有至少7,500Da，例如10kDa至1500kDa的分子量。
4.如权利要求1至3中任一项所述的用途，其中，所述金属表面是包含选自铝、钢、锌、镁及其合金的金属的表面。
5.如权利要求4所述的用途，其中，所述金属表面是铝或铝合金的表面。
6.如权利要求1至5中任一项所述的用途，其中，将转化组合物施加在所述金属表面上以在其上形成转化涂层，并且其中：
-所述转化组合物包含所述聚合物P的全部或部分作为添加剂；和/或
-将所述转化涂层施加在所述金属表面上，并且然后将所述聚合物P的全部或部分施加在所述转化涂层上。
7.如权利要求1至6中任一项所述的用途，其中，所述聚合物P的全部或部分存在于施加在所述表面上的涂料、清漆或涂层中，优选地在将转化涂层施加在所述金属表面上之后。
8.一种用于用涂料、清漆或粘合剂涂覆金属表面的方法，所述方法包括用至少一种组合物处理所述表面的步骤，所述组合物包含至少一种如权利要求1至3中任一项所定义的聚合物P。
9.如权利要求所述的方法，所述方法用于用涂料涂覆金属表面。
10.如权利要求8或9所述的方法，其中，所述包含所述聚合物P的组合物是：
-包含聚合物P的转化组合物；和/或
-所述聚合物P的溶液或分散体，其优选地在将转化涂层施加在有待处理的表面上之后施加在所述表面上；和/或
-所述涂料、清漆或粘合剂，其包含聚合物P。
11.一种转化组合物，其包含至少一种如权利要求1至3中任一项所定义的聚合物P。
12.一种涂料、清漆或粘合剂组合物，其包含至少一种如权利要求1至3中任一项所定义的聚合物P。
13.一种包括金属表面的材料，所述金属表面全部或部分地(i)用至少一种如权利要求1至3中任一项所定义的聚合物P处理和(ii)被涂料、清漆或粘合剂覆盖，所述材料是典型地具有金属表面的材料，所述金属表面全部或部分地被以下项覆盖：
-至少一个涂层(典型地转化涂层和/或涂料、清漆或粘合剂层)，其包含至少一种如权利要求1至3中任一项所定义的聚合物P；
和/或
-层(典型地转化涂层)，其包含至少一种如权利要求1至3中任一项所定义的聚合物P与经处理的表面的金属或所述层中存在的另一种化合物的反应产物。
CN201980075377.4A 2018-11-27 2019-11-27 金属表面处理 Pending CN113165013A (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP18208616.5A EP3659715A1 (en) 2018-11-27 2018-11-27 Metal surface treatment
EPEP18208616 2018-11-27
PCT/EP2019/082790 WO2020109411A1 (en) 2018-11-27 2019-11-27 Metal surface treatment

Publications (1)

Publication Number Publication Date
CN113165013A true CN113165013A (zh) 2021-07-23

Family

ID=64500277

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201980075377.4A Pending CN113165013A (zh) 2018-11-27 2019-11-27 金属表面处理

Country Status (5)

Country Link
US (1) US20220002562A1 (zh)
EP (2) EP3659715A1 (zh)
CN (1) CN113165013A (zh)
BR (1) BR112021008656A2 (zh)
WO (1) WO2020109411A1 (zh)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AR106776A1 (es) 2015-12-01 2018-02-14 Colgate Palmolive Co Composiciones de cuidado oral
CN115667438A (zh) * 2020-05-19 2023-01-31 罗地亚经营管理公司 金属表面处理
EP4006116A1 (en) 2020-11-26 2022-06-01 Rhodia Operations Metal surface treatment
US20230374666A1 (en) 2020-10-09 2023-11-23 Rhodia Operations Metal surface treatment
EP4225864A1 (en) 2020-10-09 2023-08-16 Rhodia Operations Metal surface treatment

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1950543A (zh) * 2004-05-07 2007-04-18 汉高两合股份公司 金属基材上的有色转化层
CN107236440A (zh) * 2017-07-11 2017-10-10 邢台福缘新材料有限公司 一种多重改性高耐盐雾丙烯酸分散体的制备方法
US20180125771A1 (en) * 2016-11-08 2018-05-10 Colgate-Palmolive Company Oral Care Compositions

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4191596A (en) 1978-09-06 1980-03-04 Union Carbide Corporation Method and compositions for coating aluminum
JPS61192707A (ja) * 1985-02-22 1986-08-27 Nippon Kayaku Co Ltd 硬化性組成物及び接着剤
US4921552A (en) 1988-05-03 1990-05-01 Betz Laboratories, Inc. Composition and method for non-chromate coating of aluminum
US5641542A (en) 1995-10-11 1997-06-24 Betzdearborn Inc. Chromium-free aluminum treatment
US7060327B2 (en) * 2003-11-13 2006-06-13 Henkel Corporation Corrosion protective methacrylate adhesives for galvanized steel and other metals
CN106589213B (zh) * 2016-12-15 2019-05-03 广东海特高新材料有限公司 一种水性金属漆用自交联丙烯酸乳液及其制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1950543A (zh) * 2004-05-07 2007-04-18 汉高两合股份公司 金属基材上的有色转化层
US20180125771A1 (en) * 2016-11-08 2018-05-10 Colgate-Palmolive Company Oral Care Compositions
CN107236440A (zh) * 2017-07-11 2017-10-10 邢台福缘新材料有限公司 一种多重改性高耐盐雾丙烯酸分散体的制备方法

Also Published As

Publication number Publication date
WO2020109411A1 (en) 2020-06-04
US20220002562A1 (en) 2022-01-06
EP3659715A1 (en) 2020-06-03
BR112021008656A2 (pt) 2021-08-10
EP3887067A1 (en) 2021-10-06

Similar Documents

Publication Publication Date Title
CN113165013A (zh) 金属表面处理
EP1404894B1 (en) Corrosion resistant coatings for aluminum and aluminum alloys
CN113015582B (zh) 用于金属表面处理的聚合物
US9234283B2 (en) Process for treating metal surfaces
CN100460559C (zh) 化学转化涂层剂及经表面处理的金属
ES2462291T3 (es) Proceso de tratamiento de artículos polimetálicos
JP2004218070A (ja) 塗装前処理方法
CA2312807A1 (en) Chromium-free corrosion protection agent and method for providing corrosion protection
JP2003522833A (ja) 防錆剤及び金属表面の防錆方法
RU2363769C2 (ru) Состав для нанесения покрытий
CN1527889A (zh) 防腐剂和金属表面的腐蚀防护方法
JP7052137B1 (ja) 化成処理剤、表面処理金属、及び表面処理方法
US11958989B2 (en) Method for treating surfaces of aluminum containing substrates
KR102654575B1 (ko) 카테콜 화합물 및 관능화된 공-반응 화합물의 예비 형성된 반응 생성물로 변환-코팅된 금속 기재의 처리
JP7117292B2 (ja) 鋼、亜鉛めっき鋼、アルミニウム、アルミニウム合金、マグネシウムおよび／または亜鉛－マグネシウム合金を含む金属表面を腐食保護前処理するための改善された方法
AU2011311640A1 (en) Method for passivating a metallic surface using a basic composition
CN107532305B (zh) 在转化处理之前的包含聚合物的预漂洗
CN115667438A (zh) 金属表面处理
WO2008069977A1 (en) Acidic zincating solution
CN116783326A (zh) 用于镀锌钢的改善的Cr(III)基就地干燥的涂料组合物
WO2014025484A1 (en) Steel-pre-paint treatment composition
JPS61502063A (ja) 金属処理
JP2021501263A (ja) 三価クロム化合物を使用して金属表面を処理するためのプロセスおよび組成物
JPH02263986A (ja) 金属表面のリン酸亜鉛処理方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination