CN113015582B - 用于金属表面处理的聚合物 - Google Patents
用于金属表面处理的聚合物 Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 69
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 51
- 239000002184 metal Substances 0.000 title claims abstract description 51
- 238000004381 surface treatment Methods 0.000 title description 3
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 239000002966 varnish Substances 0.000 claims abstract description 23
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000853 adhesive Substances 0.000 claims abstract description 18
- 230000001070 adhesive effect Effects 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 18
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 15
- FHEHIXJLCWUPCZ-UHFFFAOYSA-N 4-prop-2-enylbenzene-1,2-diol Chemical compound OC1=CC=C(CC=C)C=C1O FHEHIXJLCWUPCZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004922 lacquer Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- PARWTEYYJSDGQM-UHFFFAOYSA-N 3-prop-2-enylbenzene-1,2-diol Chemical compound OC1=CC=CC(CC=C)=C1O PARWTEYYJSDGQM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000007739 conversion coating Methods 0.000 claims description 26
- 239000003973 paint Substances 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 13
- 239000010410 layer Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 229910000838 Al alloy Inorganic materials 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000012790 adhesive layer Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 7
- 229920002125 Sokalan® Polymers 0.000 description 5
- -1 fluoride ions Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000001542 size-exclusion chromatography Methods 0.000 description 4
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000000569 multi-angle light scattering Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- KUQRLZZWFINMDP-BGNLRFAXSA-N 2-[(3r,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O KUQRLZZWFINMDP-BGNLRFAXSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- DXIGZHYPWYIZLM-UHFFFAOYSA-J tetrafluorozirconium;dihydrofluoride Chemical compound F.F.F[Zr](F)(F)F DXIGZHYPWYIZLM-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- 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
-
- 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
- C08F212/00—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
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/22—Oxygen
- C08F212/24—Phenols or alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- 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
- 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
- C23C22/73—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 characterised by the process
-
- 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
-
- 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
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- 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
Abstract
本发明涉及通过以下项的混合物的自由基共聚获得的聚合物：(1)丙烯酸；(2)甲基丙烯酸；以及(3)至少一种烯丙基儿茶酚，其选自4‑烯丙基苯‑1,2‑二醇、3‑烯丙基苯‑1,2‑二醇、及其混合物。这些聚合物尤其是可用于处理旨在被涂漆、清漆或粘合剂涂覆的金属表面。本发明还涉及使用此聚合物P的涂覆方法、包含该聚合物P并且可用于这些方法的组合物、以及获得的经涂覆的材料。
Description
本发明涉及基于金属的表面、并且尤其是旨在涂覆有成膜有机组合物(诸如涂漆、清漆或粘合剂组合物)的金属表面的处理的领域。本发明更尤其涉及所述金属表面的处理，目的在于提供尤其是抗腐蚀的保护和/或成膜有机物的粘附性的增强。
为了在金属表面上、尤其是在铝或钢上提供此类效果，已经提出了若干种方法，尤其包括在金属表面沉积无机涂层，尤其是所谓的“转化涂层”。
术语“转化涂层”是本领域众所周知的并且是指在金属表面上形成的层，其是所述表面上(尤其是铝上)的自然氧化物的有利替代物，并且其是通过与金属表面的化学元素反应在金属表面上膜的受控的化学形成而获得，这样使得溶解自金属材料的阳离子中的至少一些沉积在转化涂层中。
典型地，涂层(诸如转化涂层)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。在过去，已经提出了含铬的涂层(典型地通过使表面与包含H2CrF6的溶液反应而获得)，并且最近提出了，基于例如锆、钛或其他金属的毒性较小的涂层(例如通过使表面与包含H2TiF6、H2ZrF6、H2HfF6、H2AlF6、H2SiF6、H2GeF6、H2SNF4或HBF4的溶液反应而获得)。转化涂层可以包含其他化合物诸如像硅烷前体。
为了增强涂层(诸如转化涂层)上的耐腐蚀性和涂漆粘附力，已知的是添加一些添加剂，尤其是有机聚合物。在这一点上，例如已经描述了聚丙烯酸的使用。典型的添加剂是从陶氏公司(DOW)(和从先前的罗门哈斯公司(Rohm&Haas))可获得的ACUMERTM 1510，已针对此种应用进行了广泛描述。关于这一点上的更多细节，尤其可以参考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，其赋予金属表面良好的抗腐蚀保护并且赋予施加在金属表面的成膜有机组合物(诸如涂漆、清漆或粘合剂组合物)良好的粘附性。
为此目的，本发明提出使用特定的聚合物，优选地与转化涂层的形成一起(即之前、期间或之后)，这有利地致使形成经处理的金属表面，其显示出是非常有兴趣的：当被成膜组合物诸如涂漆、清漆或粘合剂组合物涂覆时，在表面与涂覆组合物之间获得了良好的粘附性。另外，获得了表面的良好保护，尤其是抗腐蚀。
更确切地，本发明使用了至少一种聚合物P，其是
通过以下项的混合物的自由基共聚获得的聚合物：
-丙烯酸(AA)；
-甲基丙烯酸(MAA)；以及
-至少一种烯丙基儿茶酚，其选自4-烯丙基苯-1,2-二醇；3-烯丙基苯-1,2-二醇、及其混合物。
化合物4-烯丙基苯-1,2-二醇和3-烯丙基苯-1,2-二醇分别具有下式：
聚合物P典型地含有作为该烯丙基儿茶酚的这两种异构体的混合物，典型地具有在30/70与70/30之间，例如在50/50与70/30之间的4-烯丙基苯-1,2-二醇与3-烯丙基苯-1,2-二醇的摩尔比率。
该聚合物P优选地含有含量为以mol计10％至90％的丙烯酸(AA)；含量为以mol计1％至70％的甲基丙烯酸(MAA)，以及含量为以mol计1％至20％的烯丙基儿茶酚，每个摩尔比率是基于AA、MAA和烯丙基儿茶酚的总量计算的。
聚合物P的分子量典型地在10与150kDa之间，例如在15与100kDa之间。
根据一个具体实施例，聚合物P含有含量为1至5％mol的烯丙基儿茶酚。在此情况下，聚合物P总体上含有含量为至多70％mol的MAA并且具有80kDa或更小的分子量Mw。
根据另一个具体实施例，聚合物P含有含量为5至10％mol的烯丙基儿茶酚。在此情况下，聚合物P总体上含有含量为至多40％mol的MAA并且具有40kDa或更小的分子量Mw。
根据另一个具体实施例，聚合物P含有含量为10至15％mol的烯丙基儿茶酚。在此情况下，聚合物P总体上含有含量为至多20％mol的MAA并且具有30kDa或更小的分子量Mw。
根据另一个具体实施例，聚合物P含有含量为15至20％mol的烯丙基儿茶酚。在此情况下，聚合物P总体上含有含量为至多10％mol的MAA并且具有20kDa或更小的分子量Mw。
根据第一方面，以诸位发明人的了解，本领域中并没有描述如上所述的聚合物P，其构成了本发明的主题。
在本发明的范围内，诸位发明人现已观察到，使用聚合物P产生了保护以及金属表面与涂覆在表面上的涂漆之间的粘附性的提升，这些比使用常用添加剂诸如ACUMERTM 1510观察到的那些更好。
根据具体方面，本发明的一个具体目的是至少一种如上定义的聚合物P用于处理旨在被涂漆、清漆或粘合剂涂覆的金属表面的用途。待处理的金属表面优选地是包含选自铝、钢、锌、镁及它们的合金的金属的表面。本发明尤其感兴趣的是铝或铝合金的金属表面。
根据感兴趣的实施例，通过使所述表面与转化组合物反应，将转化涂层施加在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)。在此情况下，典型地：
-转化组合物包含作为添加剂的聚合物P的全部或部分；和/或
-将该转化涂层施加在该金属表面上并且然后将该聚合物P的全部或部分施加在该转化涂层上。
根据另一个可能的实施例(与前一个相容)，聚合物P的全部或部分存在于涂漆、清漆或涂层中，该涂漆、清漆或涂层施加在该表面上、优选地在该金属表面上施加了转化涂层之后施加在该表面上。
根据另一个方面，本发明的另一个具体目的是一种用于用涂漆、清漆或粘合剂(优选地用涂漆)涂覆金属表面的方法，该方法包括用至少一种包含至少一种如上定义的聚合物P的组合物处理所述表面的步骤。在所述范围内，包含聚合物P的组合物可以典型地是：
-包含聚合物P的转化组合物；和/或
-该聚合物P的溶液或分散体，优选地在待处理的该表面上施加了转化涂层之后施加在该表面上；和/或
-可以包含聚合物P的全部或部分的涂漆、清漆或粘合剂。
包含聚合物P的转化组合物以及含有聚合物P的涂漆、清漆或粘合剂也构成本发明的具体目的。
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。在此情况下，将涂漆、清漆或粘合剂施加在先前经聚合物处理的表面上。根据一些具体实施例，可以将附加层施加在经处理的表面与涂漆、清漆或粘合剂之间(这是例如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漆的情况：在此情况下，可以在经处理的箔上施加润滑剂，以便允许将箔轧制并且易于其运输)。
根据也另一个方面，本发明的具体目的是包含金属表面的材料，该金属表面全部或部分地(i)用如上定义的聚合物P处理并且(ii)被涂漆、清漆或粘合剂覆盖。
这些材料包括尤其具有全部或部分地被以下项覆盖的金属表面的材料：
-至少一个包含至少一种聚合物P的涂层(典型地转化涂层和/或涂漆、清漆或粘合剂层)；
和/或
-层(典型地转化涂层)，其包含如上定义的聚合物P与经处理表面的金属或存在于所述层中的另一种化合物的反应产物。
现在将更详细地描述本发明的具体特征和可能的实施例。
经处理的金属表面
可以用本发明的聚合物P处理任何金属表面，但是本发明尤其适用于处理以下项的金属表面：
-铝或基于铝的合金；或
-钢，例如镀锌钢(热浸镀锌HDG或电镀锌EG)；或冷轧钢(CRS)；或
-镁或基于镁的合金；或
-锌或基于锌的合金。
本发明尤其感兴趣的是铝和铝合金(诸如在所附实例中测试的铝合金AA5005或其他合金诸如系列1xxx、2xxx、3xxx、4xxx、5xxxx、6xxx(诸如AA1050、2024、3003、5182、5754、6111、6016、6060、6063、6182)的那些的金属表面。
转化涂层
当根据本发明，将转化涂层施加在待处理金属表面上时，其可以通过使表面与现有技术已知的任何转化组合物接触而获得。
如说明性实施例，可以通过任何本身已知的手段使金属表面与转化组合物接触，诸如在转化浴中浸涂或喷涂。
根据本发明所使用的转化组合物可以典型地含有氟阴离子和阳离子金属，例如化合物，诸如H2CrF6或更优选地不含铬的化合物，诸如H2TiF6、H2ZrF6、H2HfF6、H2AlF6、H2SiF6、H2GeF6、H2SNF4或HBF4。
转化组合物还可以包含其他化合物，诸如像硅烷前体、和/或铈盐、和/或钼酸铽。
此外，根据具体实施例，转化组合物可以含有根据本发明用于处理表面所使用的聚合物P的全部或部分。在此情况下，转化层的施加本身致使根据本发明的表面处理。
另外，典型地，在转化层形成之后，通过使携带转化层的金属表面与聚合物P(其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，或在施加在转化层上的涂漆、清漆或粘合剂组合物内)接触而得到处理。
根据具体实施例，可以设想在转化组合物中和施加在转化涂层上的涂漆、清漆或粘合剂中都使用聚合物P。
以下实例说明了本发明。
实例
实例1
根据本发明的聚合物P1的合成
聚(AA-stat-MAA-stat-烯丙基儿茶酚)26/70/4mol％
如下制备聚合物P1：
在500mL三颈圆底烧瓶中添加具有60/40的4-烯丙基苯-1,2-二醇与3-烯丙基苯-1,2-二醇的摩尔比率的4-烯丙基儿茶酚(5.50g，36.6mmol)、58.4％在水中的丙烯酸(AA)(1.47g，11.9mmol)和5％在水中的2,2'-偶氮双(2-甲基丙脒)二盐酸盐(V-50)(74.49g，13.7mmol)。在氮气下搅拌20分钟后，将圆底烧瓶放入66℃的油浴中。10分钟后，在2小时内滴加两种具有58.4％的AA(13.96g，113.1mmol)和58.4％的甲基丙烯酸(MAA)(37.79g，256.4mmol)的水溶液。完成后，分别在4小时和6小时内再次滴加两种具有58.4％的AA(13.96g，113.1mmol)和58.4％的MAA(56.68g，384.5mmol)的水溶液。在最后2小时的蒸煮后，将圆底烧瓶从油浴中移出，并且通过1H NMR光谱法(AA转化率＝99％；MAA转化率＝97％；4-烯丙基儿茶酚转化率＝91％)以及通过尺寸排阻色谱法(Mw＝57kg/mol；Mn＝21kg/mol；)分析反应混合物。
使用布鲁克公司(Brucker)的300MHz光谱仪记录质子核磁共振(1H NMR)光谱。为了测量AA、MAA和4-烯丙基儿茶酚的转化率，将四滴反应混合物在约1g的氘化水(D2O)中稀释。
通过配备有多角度激光散射(MALLS)Mini Dawn TREOS检测器和安捷伦公司(Agilent)的浓度检测器(RI检测器)的尺寸排阻色谱仪(SEC)测量摩尔质量。SEC系统在三柱Agilent Aquagel OH混合H，8μm，3*30cm上以1mL/min的流速运行，并具有以下流动相：H2O 100％vol.、0.1M NaCl、25mM NaH2PO4、25mM Na2HPO4缓冲溶液(pH 7)。聚合物样品已经以0.5wt％溶解于流动相中持续至少4小时，然后在微孔过滤器(0.45μm)中过滤。获得绝对摩尔质量，其中聚(丙烯酸)的dn/dC等于0.1875mL/g。
实例2
实例1的聚合物的用途
已经用常用实验室设备(烧杯、烘箱、…)、粉末涂覆装置(来自IndustrieSysteses公司的GEMA 2C)、以及腐蚀室(来自QFOG公司的Q-FOG CRH 600L)在铝合金面板(来自Q-Panel公司的AA5005)上进行了测试。
在每个测试中，应用了以下方案：
■清洗和蚀刻
其通过将每个待测试的面板浸入组合的清洗-蚀刻浴中进行，该浴为典型地通过稀释可商购的配制品，DBT ALU 200(从Chemtec Aertec公司可获得)(5g DBT ALU 200进入995g水中)制得的1L浴。在50℃下、在轻轻搅拌(200rpm)下将面板浸入清洗-蚀刻浴中持续3min。然后用1L去离子水冲洗该面板。
■处理
其通过将前述步骤清洗/蚀刻之后获得的面板浸入处理浴中进行，该浴为通过在水中稀释以下项制得的1L浴：
-浓度为200ppm活性物质(0.02wt％)的六氟化锆H2ZrF6；以及
-在下表中给出的浓度为从50ppm活性物质(0.005wt％)至1,000ppm(0.1wt％)的待测试的添加剂(根据本发明实例1的聚合物P1对比在对比实例中的ACUMERTM 1510)：
在25℃下将面板在处理浴中浸没2min。对其不进行冲洗。用压缩空气将过量的浴溶液从表面冲洗掉。然后在60℃下将面板在烘箱中干燥30min。
■涂漆：
然后将每个面板涂有来自RIPOL公司的聚酯白色粉末涂漆(BIANCORAL 9010)。
测试
然后根据与以下列出的下列标准中描述的那些类似的方案对每个面板进行测试：
-乙酸盐喷雾：T＝35(+/-2)℃，[NaCl]＝50(+/-5)g/L，pH＝3.1-3.3(ISO 9227)
-刻划方案：如在ISO 17872中所述
-生锈程度，引用如在ISO 4628-3中描述的
-起泡程度，引用如在ISO 4628-2中描述的
生锈结果
根据ISO 4628-3评估
不管聚合物浓度是多少，用对比实例比用本发明的聚合物更快出现生锈。
起泡结果
根据ISO 4628-2评估
在此再次地，本发明的聚合物甚至在1000h之后比对比物质明显更好。
Claims (18)
1.一种聚合物P，其通过以下项的混合物的自由基共聚而获得：
-丙烯酸；
-甲基丙烯酸；以及
-至少一种烯丙基儿茶酚，其含有在30/70与70/30之间的具有下式的4-烯丙基苯-1,2-二醇与3-烯丙基苯-1,2-二醇摩尔比率的烯丙基儿茶酚混合物
。
2. 如权利要求1所述的聚合物P，其具在10与150 kDa之间的分子量。
3.如权利要求1所述的聚合物P，其含有含量为以mol计10%至90%的丙烯酸（AA）；含量为以mol计1%至70%的甲基丙烯酸（MAA），以及含量为以mol计1%至20%的烯丙基儿茶酚，每个摩尔比率是基于AA、MAA和烯丙基儿茶酚的总量计算的。
4.至少一种如权利要求1至3中任一项所述的聚合物P用于处理旨在被涂漆、清漆或粘合剂涂覆的金属表面的用途。
5.如权利要求4所述的用途，其中，该金属表面是包含选自铝、钢、锌、镁以及它们的合金的金属的表面。
6.如权利要求5所述的用途，其中，该金属表面是铝或铝合金的表面。
7. 如权利要求4至6中任一项所述的用途，其中，将转化组合物施加在该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作为添加剂的聚合物P的全部或部分；和/或
-将该转化涂层施加在该金属表面上，并且将该聚合物P的全部或部分施加在该转化涂层上。
8.如权利要求4至6中任一项所述的用途，其中，该聚合物P的全部或部分存在于涂漆、清漆或涂层中，该涂漆、清漆或涂层施加在该表面上。
9.如权利要求8所述的用途，其中，该涂漆、清漆或涂层在该金属表面上施加了转化涂层之后施加在该表面上。
10.一种用于用涂漆、清漆或粘合剂涂覆金属表面的方法，该方法包括用至少一种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的组合物处理所述表面的步骤。
11.如权利要求10所述的方法，该方法用于用涂漆涂覆金属表面。
12. 如权利要求10或11所述的方法，其中，包含该聚合物P的该组合物是：
-包含聚合物P的转化组合物；和/或
-该聚合物P的溶液或分散体；和/或
-包含聚合物P的该涂漆、清漆或粘合剂。
13.如权利要求12所述的方法，其中，该聚合物P的溶液或分散体，在待处理的该表面上施加了转化涂层之后施加在该表面上。
14.一种转化组合物，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。
15.一种涂漆、清漆或粘合剂组合物，其含有至少一种如权利要求1至3中任一项所定义的聚合物P。
16.一种材料，其包含全部或部分地(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处理的并且(ii)被涂漆、清漆或粘合剂覆盖的金属表面，所述材料是具有以下金属表面的材料，该金属表面全部或部分地被以下项覆盖：
-至少一个涂层，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；
和/或
-层，其包含该至少一种如权利要求1至3中任一项所定义的聚合物P与该经处理的表面的金属或存在于该层中的另一种化合物的反应产物。
17.如权利要求16所述的材料，其中该至少一个涂层为转化涂层和/或涂漆、清漆或粘合剂层。
18.如权利要求16所述的材料，其中该层为转化涂层。
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| US4761189A (en) * | 1982-12-23 | 1988-08-02 | Gerhard Collardin Gmbh | Process and aqueous compositions for treating metal surfaces |
| US5534082A (en) * | 1992-04-01 | 1996-07-09 | Henkel Corporation | Composition and process for treating metal |
| CN106574372A (zh) * | 2014-01-23 | 2017-04-19 | 凯密特尔有限责任公司 | 涂覆金属表面的方法、由此涂覆的基底及其用途 |
| WO2018119376A1 (en) * | 2016-12-22 | 2018-06-28 | Henkel Ag & Co. Kgaa | Treatment of conversion-coated metal substrates with preformed reaction products of catechol compounds and functionalized co-reactant compounds |
| WO2018119368A1 (en) * | 2016-12-22 | 2018-06-28 | Henkel Ag & Co. Kgaa | Reaction products of catechol compounds and functionalized co-reactant compounds for metal pretreatment applications |
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| US4191596A (en) | 1978-09-06 | 1980-03-04 | Union Carbide Corporation | Method and compositions for coating aluminum |
| 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 |
| KR101942325B1 (ko) * | 2012-02-10 | 2019-04-11 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | 부식 방지 코팅 |
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- 2019-11-27 CN CN201980074620.0A patent/CN113015582B/zh active Active
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| US4761189A (en) * | 1982-12-23 | 1988-08-02 | Gerhard Collardin Gmbh | Process and aqueous compositions for treating metal surfaces |
| US5534082A (en) * | 1992-04-01 | 1996-07-09 | Henkel Corporation | Composition and process for treating metal |
| CN106574372A (zh) * | 2014-01-23 | 2017-04-19 | 凯密特尔有限责任公司 | 涂覆金属表面的方法、由此涂覆的基底及其用途 |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP3659716A1 (en) | 2020-06-03 |
| US20220002456A1 (en) | 2022-01-06 |
| CN113015582A (zh) | 2021-06-22 |
| EP3887068A1 (en) | 2021-10-06 |
| BR112021006893A2 (pt) | 2021-07-20 |
| WO2020109413A1 (en) | 2020-06-04 |
| EP3887068B1 (en) | 2022-09-14 |
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