CN104769047A - Mixtures for the coating of metallic surfaces - Google Patents
Mixtures for the coating of metallic surfaces Download PDFInfo
- Publication number
- CN104769047A CN104769047A CN201380057711.6A CN201380057711A CN104769047A CN 104769047 A CN104769047 A CN 104769047A CN 201380057711 A CN201380057711 A CN 201380057711A CN 104769047 A CN104769047 A CN 104769047A
- Authority
- CN
- China
- Prior art keywords
- multipolymer
- weight
- coating
- dispersion
- copolymer dispersion
- 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
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 35
- 239000011248 coating agent Substances 0.000 title claims abstract description 33
- 239000000203 mixture Substances 0.000 title description 12
- 239000006185 dispersion Substances 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 46
- 229920001577 copolymer Polymers 0.000 claims abstract description 40
- 239000010452 phosphate Substances 0.000 claims abstract description 15
- -1 phosphonate ions Chemical class 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 7
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
- 239000000080 wetting agent Substances 0.000 claims description 15
- 238000005260 corrosion Methods 0.000 claims description 14
- 230000007797 corrosion Effects 0.000 claims description 14
- 150000002500 ions Chemical class 0.000 claims description 13
- 229910019142 PO4 Inorganic materials 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 11
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 229910000831 Steel Inorganic materials 0.000 claims description 7
- 238000007739 conversion coating Methods 0.000 claims description 7
- 239000010959 steel Substances 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000010422 painting Methods 0.000 claims description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 2
- 125000005499 phosphonyl group Chemical group 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910000157 magnesium phosphate Inorganic materials 0.000 abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 2
- 150000008064 anhydrides Chemical class 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 239000000654 additive Substances 0.000 description 14
- 239000011701 zinc Substances 0.000 description 14
- 230000000996 additive effect Effects 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 235000021317 phosphate Nutrition 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 10
- 239000011877 solvent mixture Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 239000003513 alkali Substances 0.000 description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 8
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 8
- 229920002125 Sokalan® Polymers 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 229920001038 ethylene copolymer Polymers 0.000 description 6
- 229910000400 magnesium phosphate tribasic Inorganic materials 0.000 description 6
- 239000004584 polyacrylic acid Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
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- 238000002161 passivation Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 150000002191 fatty alcohols Chemical class 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000001996 bearing alloy Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000007046 ethoxylation reaction Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 150000003009 phosphonic acids Chemical class 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- 239000004435 Oxo alcohol Substances 0.000 description 2
- 229920002257 Plurafac® Polymers 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229960002887 deanol Drugs 0.000 description 2
- 229960002380 dibutyl phthalate Drugs 0.000 description 2
- 239000012972 dimethylethanolamine Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000008393 encapsulating agent Substances 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000004137 magnesium phosphate Substances 0.000 description 2
- 235000010994 magnesium phosphates Nutrition 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 125000005702 oxyalkylene group Chemical group 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 159000000000 sodium salts Chemical group 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OAAZUWWNSYWWHG-UHFFFAOYSA-N 1-phenoxypropan-1-ol Chemical compound CCC(O)OC1=CC=CC=C1 OAAZUWWNSYWWHG-UHFFFAOYSA-N 0.000 description 1
- UPLPHRJJTCUQAY-WIRWPRASSA-N 2,3-thioepoxy madol Chemical compound C([C@@H]1CC2)[C@@H]3S[C@@H]3C[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@](C)(O)[C@@]2(C)CC1 UPLPHRJJTCUQAY-WIRWPRASSA-N 0.000 description 1
- WMDZKDKPYCNCDZ-UHFFFAOYSA-N 2-(2-butoxypropoxy)propan-1-ol Chemical compound CCCCOC(C)COC(C)CO WMDZKDKPYCNCDZ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- GVNHOISKXMSMPX-UHFFFAOYSA-N 2-[butyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCN(CCO)CCO GVNHOISKXMSMPX-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- YEBLAXBYYVCOLT-UHFFFAOYSA-N 2-hydroxy-n,n-dimethylpropanamide Chemical compound CC(O)C(=O)N(C)C YEBLAXBYYVCOLT-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N Lactic Acid Natural products CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
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- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
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- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 125000005600 alkyl phosphonate group Chemical group 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
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- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
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- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
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- 238000006471 dimerization reaction Methods 0.000 description 1
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
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- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
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- 239000011654 magnesium acetate Substances 0.000 description 1
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- PSEXPFNBJCCKPF-UHFFFAOYSA-N magnesium;methanesulfonic acid Chemical compound [Mg].CS(O)(=O)=O PSEXPFNBJCCKPF-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
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- HZAXFHJVJLSVMW-UHFFFAOYSA-N monoethanolamine hydrochloride Natural products NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- YPEWWOUWRRQBAX-UHFFFAOYSA-N n,n-dimethyl-3-oxobutanamide Chemical compound CN(C)C(=O)CC(C)=O YPEWWOUWRRQBAX-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
-
- 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
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D123/04—Homopolymers or copolymers of ethene
- C09D123/08—Copolymers of ethene
- C09D123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
A method for coating metallic surfaces, in which the metallic surface is contacted with an aqueous copolymer dispersion, wherein the aqueous copolymer dispersion contains an effective amount of magnesium ions and phosphate or phosphonate ions, and wherein the copolymers present in the dispersion are formed from the following components: (A) from 20 to 95% by weight of monoethylenically unsaturated hydrocarbons and/or hydrocarbons having two conjugated double bonds, (B) from 5 to 80% by weight of monoethylenically unsaturated monomers having acid groups and/or the anhydrides or salts thereof. The invention further provides metallic surfaces coated with such copolymers and for the use of such aqueous copolymer dispersions for coating of metallic surfaces.
Description
Invention describes
The present invention relates to by making metallic surface contact and the method for coating metal surfaces with moisture copolymer dispersion.The invention further relates to the metallic surface through multipolymer coating and the purposes of moisture copolymer dispersion in coating metal surfaces.
Other embodiments of the present invention can find in claims, specification sheets and embodiment.Should understand the present subject matter determined above feature and will described below those, not only can be used in the various combinations specifically shown, and can be used for, in other combinations, and not departing from scope of the present invention.The present invention is more specifically preferably those embodiments that the feature of wherein all present subject matter has preferred and particularly preferred definition respectively respectively with particularly preferred embodiment.
Knownly utilize moisture copolymer dispersion coated surface.
WO 2004/108601 A1 describe comprise the ethylene copolymer wax that at least one neutralizes at least partly water dispersion as auxiliary agent purposes in the treatment of waste water, the ethylene copolymer wax of described at least part of neutralization is selected from and comprises at least one ethylenic unsaturated carboxylic acid of (A) 26.1-39 % by weight and the ethene of (B) 61-73.9 % by weight those ethylene copolymer waxes as comonomer using copolymerized form, and at least one ethylenic unsaturated carboxylic acid of (A ') 20.5-38.9 % by weight is comprised with copolymerized form, those ethylene copolymer waxes of at least one ethylenically-unsaturated carboxylic acid ester of the ethene of (B ') 60-79.4 % by weight and (C ') 0.1-15 % by weight.The ethylene copolymer wax of part neutralization is through alkaline matter, and preferred amines neutralizes at least partly.Alkaline matter also can be alkali-metal carbonate and/or supercarbonate.
WO 2008/092853A1 describes a kind of by utilizing the preparaton treat surface of paraffinic hydrocarbons and the method for coated surface of being substantially free of, and this preparaton comprises and utilizes basic metal to neutralize at least partly and the multipolymer prepared by the ethylenic unsaturated carboxylic acid of ethene and 25.5-35 % by weight.This preparaton comprises at least one non-ionic type or anionic material, at least one defoamer and optional other components further.Basic component can also be alkali-metal carbonate and/or supercarbonate.
WO 2007/137963 A1 describes to utilize has comprising the ethylenic unsaturated carboxylic acid of 15.5-19.9 % by weight with copolymerized form and comprising the water dispersion coating plastic of the ethylene copolymer of at least one alkali or the method for metallic surface of the molar mass of 2000-20000g/mol, is wherein provided with at least one other coatings through the surface of coating.The example of selected alkali is an alkali metal salt, and more preferably amine.
WO 2006/066824 A1 describes the method utilizing alkene and/or diene, acid monomer and the optional multipolymer coating metal surfaces of other monomers, and wherein metallic surface does not remove this pollution before coating through oil and/or grease contamination.Polymkeric substance used utilizes alkali to neutralize; The preferable alloy positively charged ion of specifying comprises Mg
2+ion.But, not mentioned phosphoric acid salt, the especially use of trimagnesium phosphate.
WO 98/10023 describes the aqueous polymer dispersion comprised by alkene and the polymkeric substance be made up of acidic comonomer, at least one tinting material and/or corrosion inhibitor and is protecting metallic surface with the purposes in protection against corrosion.Corrosion inhibitor used is preferably pigment, its insoluble and the restriction transparency of film and surface property in aqueous phase.
Above-mentioned dispersion, about the corrosion control of metallic surface, especially must be improved in the passivation on surface comprising steel and/or zinc or zinc-bearing alloy.
The object of this invention is to provide improving one's methods of a kind of process metal surfaces, it can be particularly advantageous in the passivation on the surface comprising steel and/or zinc or zinc-bearing alloy.
As from disclosure of the present invention, these and other objects realize by the various embodiments of invention formulation.
Therefore a theme of the present invention is a kind of for by making metallic surface contact and the method for coating metal surfaces with moisture copolymer dispersion, wherein moisture copolymer dispersion includes the magnesium ion of effective amount and the mixture of phosphate radical or phosphonium acid ion or phosphate radical and phosphonium acid ion, and the multipolymer be wherein present in dispersion is formed (aufgebaut) by following component:
(A) 20-95 % by weight Mono-olefinic unsaturated hydrocarbons and/or there is the hydrocarbon of two conjugated double bonds,
(B) the Mono-olefinic unsaturated monomer comprising acidic group and/or its acid anhydrides or salt of 5-80 % by weight.
At this, the amount of component (A) and (B) is based on the total amount of component (A) and (B).100 % by weight in the total amount of this component (A) and (B).Component (A) preferably exists with 20-95 % by weight and (B) exists with 5-50 % by weight.
Surprisingly, the metallic surface of the inventive method process has been found to utilize obviously than more anticorrosive according to those of prior art.
For the purpose of the present invention, moisture copolymer dispersion is the mixture comprising water and multipolymer.Be present in water-containing solvent mixture at this water, wherein water-containing solvent mixture substantially, is more preferably completely made up of water.Multipolymer can dispersion, emulsion or be present in water-containing solvent mixture as molecular solution.
Water-containing solvent mixture preferably comprises the water of 75 % by weight to 100 % by weight.In addition to water, water-containing solvent mixture also optionally can comprise organic solvent.This organic solvent preferably comprises the compound being selected from alcohol, ether, ester, ketone and acid amides.This organic solvent uses usually used as paint ingredients, and known by prior art for technical personnel.The example of these solvents is that alcohol is as methyl alcohol, ethanol, propyl alcohol, butanols, phenoxypropanol or ethylene glycol, ketone is as acetone, methyl ethyl ketone, pimelinketone, oligomeric and the alkylene glycol ether of optional part etherificate is as glycol ether, triglycol, Tetraglycol 99, butyl glycol, butyl diglycol, 2, 2, 4-trimethylammonium-1, 3-pentanediol mono isobutyrate, dimerization butyl glycol, dipropylene glycol n-butyl ether, dimethyl ether, ester is as hexanodioic acid, dimethyl ester of succsinic acid and pentanedioic acid and composition thereof, lactic acid 2-ethylhexyl, butyl phthalate, dibutyl phthalate, acid amides is as dimethyl acetoacetamide, N-Methyl pyrrolidone or N, N-dimethyl lactic amide.Also can use water unmixability solvent on a small quantity, wherein example is hydro carbons.Select in this case to make do not have visible additionally to be formed mutually on a small quantity; Usually on a small quantity, be less than 5 % by weight based on entire mixture.
Multipolymer in water-containing solvent mixture is preferably main with molecular dispersion form or to be existed by the very thin dispersion with the mean particle size of below 100nm of Dynamic Light Scattering Determination according to DINISO 13321.This means the considerable change that they can not cause water-containing solvent transparency, more can not cause forming throw out.
Multipolymer preferably has more than 20000g/mol, very preferably the molecular weight M of more than 50000g/mol
w(weight average).More especially the molecular weight of multipolymer is 20000-200000g/mol, very preferably 50000-200000g/mol.
In a preferred embodiment of the inventive method, the multipolymer be present in dispersion comprises following component as other components:
(C) ethylenically unsaturated monomers being different from (A) and (B) of 0-30 % by weight.
In another preferred embodiment of the inventive method, the total amount of magnesium ion, phosphate anion and phosphonium acid ion is 0.1-5 % by weight based on the amount of multipolymer, preferred 0.2-3.5 % by weight, more preferably 0.4-2 % by weight, very preferably 0.6-1.6 % by weight.
For the inventive method, preferably magnesium ion and phosphate radical or phosphonium acid ion are added moisture copolymer dispersion with the form of the salt comprising trimagnesium phosphate or phosphonic acids magnesium.Preferred salt is the hydrate of trimagnesium phosphate, phosphonic acids magnesium, eight hydrated magnesium phosphates or other these salt thus.This compound also can be Partial protons form, such as, as hydrophosphate or dihydrogen phosphate and corresponding phosphonate.Also trimagnesium phosphate or phosphonic acids magnesium and other salt can be used, such as, with the mixing salt of ammonium compound, alkali metal compound or alkaline earth metal compound.The example of this compound is ammonium magnesium phosphate or trimagnesium phosphate sodium.
In a preferred embodiment of the inventive method, component (A) is the alkene that at least one is selected from ethene, propylene, 1-butylene, 2-butylene, 1-amylene, 1-hexene, 1-heptene and 1-octene.
In another preferred embodiment of the inventive method, the acidic group in (B) is the group that at least one is selected from carboxyl, sulfonic acid group and phosphonyl group.
More preferably component (A) is for ethene and component (B) is (methyl) vinylformic acid.
In a preferred embodiment of the inventive method, the acidic group be present in multipolymer of 0.5-50 % by mole exists with the form of the group of neutralization.This neutralization disperses in a solvent preferably by making polymkeric substance at elevated temperatures and adds alkali and carry out.
Normally one or more have the material of alkalescence effect to alkali used, and example is alkali-metal oxyhydroxide and/or carbonate and/or supercarbonate, or preference is if amine is as ammonia, and such as organic amine is as alkylamine, N-alkyl ethanol amine, alkanolamine and polyamines.
The example of alkylamine comprises following compound: triethylamine, diethylamide, ethylamine, Trimethylamine, dimethyl amine, methylamine.Preferred amine in hydroxyalkyl, has 2-18 C atom in each case and optionally in alkyl, has 1-6 C atom in each case, preferably there is 2-6 C atom in alkanol groups and optionally there are the monoalkanolamine of 1 or 2 C atom, N, N-dialkylalkanolamines, N-alkylalkanolamines, dioxane hydramine, N-alkylalkanolamines and three alkanolamines in alkyl.Particularly preferably thanomin, diethanolamine, trolamine, methyldiethanolamine, n-butyldiethanolamine, N, N-dimethylethanolamine and 2-amino-2-methyl third-1-alcohol.Particularly preferably ammonia and N, N-dimethylethanolamine.The example of the polyamines that can mention comprises following compound: quadrol, Tetramethyl Ethylene Diamine (TMEDA), diethylenetriamine and Triethylenetetramine (TETA).
Multipolymer is prepared by method known to the skilled.Such as prepare multipolymer according to the method described in WO 2004/108601 A1.
The mixture of multipolymer and water-containing solvent mixture is prepared by method known to the skilled.Multipolymer is such as made to be scattered in by being pre-mixed in the solvent mixture of generation.
With regard to the inventive method, preferably with there is water or have the water comprising at least 75 % by weight water-containing solvent mixture preparaton form use multipolymer.Particularly preferably multipolymer is only being prepared in the water of solvent in this case, and the relative concentration of multipolymer is 0.5-50 % by weight in the summation of all components of preparaton.
Moisture copolymer dispersion in the methods of the invention is preferably used by injection, spraying, dipping, blade coating or electrophoretic painting.
Also the inventive method can be used for apply various metals surface.Metallic surface preferably comprises and is selected from Mg, Al, steel, Zn, and is coated with the metal of steel of Zn, Al, Ni, Sn, Cr or its alloy; More preferably metallic surface comprises Metal Zn.
In another embodiment of the inventive method, moisture copolymer dispersion is contacted with inter coat, and wherein inter coat contacts with metallic surface.The conversion coating of inter coat preferably for making metal surface passivation.The example of this coating is Cr conversion coating, phosphate coat, polymer-based carbon aftertreatment, the passivating coating comprising Ti compound or Zr compound, coating of metal oxides, laminated coating, crosslinked with silicane coating or oil, especially rust preventive oil.This inter coat is preferably Cr conversion coating.Know as understood by the skilled person, these conversion coatings are by comprising oxidising agent (as NO
3 -) acidity (pH0.5-5) produce containing the solution of Cr (III) or Cr (VI).This make the Zn minimum dissolving in surface and final pH increase from the teeth outwards with formed according to apply parameter (temperature, pH value of solution, application time) have the coat-thickness of 20nm to 2 μm containing the oxidation/hydroxide reticulation of Cr and Zn.By prior art (US 19810265487, DE 19638176A) known so-called chromating, chromite facture (chromiting) or passivating coating.Also can remove some or all of inter coat before utilizing moisture copolymer dispersion process, this removing is such as carried out in alkali cleaning bath.The oil base material of non-degreasing or only partially skimmed directly utilizes copolymer dispersion process by the inventive method.
In another embodiment of the inventive method, other corrosion inhibitors that copolymer dispersion comprises film forming agent, linked, wetting agent or is different from multipolymer are as other components.
In addition, as mentioned above, copolymer dispersion and film can be made to form auxiliary agent mix.The latter can be solvent or solvent mixture, and particularly have the evaporation number according to DIN 53170 of 50-20000 those, example is butyl glycol or butyl diglycol.But also can add non-evaporated compounds, particularly with oxyalkylene, more especially ethylene oxide and/or propylene oxide reaction alcohol.These alcohol can be monohydroxies or polyhydric.These compounds can cause solution better to be sprawled on the metal surface.Also oligomeric or polymeric alcohol can such as be used, as the alcoxylates of polyorganosiloxane ramification.
Can add as mentioned above other component-example be linked as various silicon compound, nano particle, there is the component of epoxy group(ing) and/or isocyanate groups and be different from the corrosion inhibitor of multipolymer.The example of suitable silicon compound is formula Y, X-Si-(OR)
3-xsilyl ether and silanol, wherein X and Y is the organic group of any hope, and R is H or alkyl, and x is 0 or 1.These compounds also can be nanoparticle dispersion or the oligomeric compound carrying out preliminary condensation.
As mentioned above, also wetting agent can be added copolymer dispersion.The example of suitable wetting agent is non-ionic type, anionic or cationic surfactant, more especially the ethoxylate of the ethoxylation of fatty alcohol and/or propoxylation products or oxypropylene-oxyethylene segmented copolymer, ethoxylation or propoxylated fatty alcohol or oxo alcohol and oleic acid or alkylphenol, alkyl phend ether sulfate, alkyl polyglycoside, alkyl phosphonates, phosphonic acids alkyl phenyl ester, alkyl phosphate or alkyl phenyl phosphate ester.The C of other examples particularly polyethoxylated
10-C
30the C of fatty alcohol or polyethoxylated
11-C
31oxo alcohol.
Preferred use low-foam wetting agents, example is ethoxylation and/or the propoxylation products of the fatty alcohol of end-group termination, and wherein alcohol end group reacts and obtains ether as methyl ether or ethyl ether.
Particularly preferred wetting agent is the alkoxy fatty alcohols of formula (I)
R
1-(OCH
2CHR
2)
x(OCH
2CHR
3)
y-OR
4(I)
Wherein
R
1linear or the C of branching
6-C
24alkyl,
R
2and R
3h or C that is linear or branching
1-C
16alkyl,
R
4h or C that is linear or branching
1-C
8alkyl,
X is the integer of 1-200, and
Y is the integer of 0-80.
Oxyalkylene units in formula (I) can be arranged or arrange at random by one or more block.
The present invention further provides the metallic surface through multipolymer coating that can obtain according to any embodiment of the inventive method.
Generally speaking, the thickness on the metal surface containing the layer of multipolymer is 0.1-30 μm, preferred 0.2-30 μm, more preferably 0.5-10 μm, very preferably 1-6 μm.
In the present invention in an embodiment of the metallic surface of coating, containing one or more enamelled coatings copolymer layer also existing lamination applying.
Can be the form of any hope usually through the metallic surface of coating.Metallic surface is preferably the surface of formed body or plates, more preferably the surface of coiled material, line, pipe, plate, workpiece, forming part, union piece and/or union piece.
Copolymer dispersion can be applied to sheet or shaping metallic surface, such as, be applied to coiled material, line and pipe, or be applied to other formed bodys or plates.
When using formed body, apply copolymer dispersion preferably by dipping or spray method.In this case after drying, the film through applying preferably has 0.2-30 μm, more especially 0.5-10 μm, the very preferably average coating thicknesses of 1-6 μm.
Drying is carried out by multiple method.Under many circumstances, the common drying at the temperature slightly improved is enough.Workpiece (formed body or plates) preferably stores 5-20 minute in an oven at 80 DEG C.But, as required and when needed, higher temperature and longer or shorter time can be set.
Another theme of the present invention is the purposes of moisture copolymer dispersion in coating metal surfaces including the magnesium ion of effective amount and the mixture of phosphate radical or phosphonium acid ion or phosphate radical and phosphonium acid ion, and the multipolymer be wherein present in dispersion is formed by following component:
(A) 20-95 % by weight Mono-olefinic unsaturated hydrocarbons and/or there is the hydrocarbon of two conjugated double bonds,
(B) the Mono-olefinic unsaturated monomer comprising acidic group and/or its acid anhydrides or salt of 5-80 % by weight.
At this, the amount of component (A) and (B) is based on the total amount of component (A) and (B).At this, the total amount of component (A) and (B) is 100 % by weight.Component (A) preferably exists with 20-95 % by weight and component (B) exists with 5-50 % by weight.
In a preferred embodiment of purposes of the present invention, the multipolymer be present in dispersion comprises following component as other components:
(C) ethylenically unsaturated monomers being different from (A) and (B) of 0-30 % by weight.
At this, the total amount of magnesium ion, phosphate anion and phosphonium acid ion is 0.1-5 % by weight based on the amount of multipolymer, preferred 0.2-3.5 % by weight, more preferably 0.4-2 % by weight, very preferably 0.6-1.6 % by weight.
With regard to purposes of the present invention, preferably make moisture copolymer dispersion contact with inter coat, wherein make this inter coat contact with metallic surface.
In another embodiment of the inventive method, moisture copolymer dispersion comprises other additives as additional component.Other additives of preferred use are dispersion agent, dispersing auxiliary and/or wetting agent.
The example of dispersion agent is polyacrylic acid or acrylic copolymer.These polyacrylic acid or acrylic copolymer are preferably in their sodium-salt form.Further preferred dispersants has 1000-30000g/mol, more especially the molecular weight Mw (weight average) of 2000-10000g/mol.The total amount of dispersion agent is 0.01-1 % by weight based on the amount of the multipolymer in moisture copolymer dispersion.Preferred use 0.01-0.2 % by weight.
In moisture copolymer dispersion, use dispersion agent to cause surprising improvement in stability in storage.
The example of dispersing auxiliary is tensio-active agent.The total amount of dispersing auxiliary is 0.01-0.1 % by weight based on the amount of the multipolymer in moisture copolymer dispersion.
The example of wetting agent is nonionic surface active agent.The total amount of wetting agent is 0.01-0.1 % by weight based on the amount of the multipolymer in moisture copolymer dispersion.
With regard to purposes of the present invention, particularly preferably be and coating is used as so-called encapsulant, wherein Cr conversion coating is used as inter coat.In this case, encapsulant causes the obvious improvement of the corrosion control aspect of performance at Cr conversion coating.
The invention provides improving one's methods for metal finishing, the method can be particularly advantageous for the passivation on the surface comprising steel and/or zinc or zinc-bearing alloy.
The present invention is illustrated by embodiment, and embodiment does not limit present subject matter.
Embodiment
Polymer A:
21 % by weight (amounts based on water) have the molecular weight of about 30000 D with the ethene of the weight ratio of 70:30 and acrylic acid multipolymer and 3.5 % by weight alkali, the aqueous solution of dimethylethanolamine (amount based on water).
Polymer B:
21 % by weight (amounts based on water) have the molecular weight of about 90000 D with the ethene of the weight ratio of 73:27 and the multipolymer of methacrylic acid and the alkali of 3.5 % by weight, the aqueous solution of dimethylethanolamine (amount based on water).
Embodiment 1-11:
Additive A:
Additive 1: eight hydrated magnesium phosphate
Additive 2: methylsulfonic acid magnesium
Additive 3: magnesium acetate
Additive 4: Sodium phosphate dibasic
Respective additive 1-4 is added polymers soln, and makes solution stirring at least 3 hours subsequently.
Selected additive in % by weight amount based on the amount of multipolymer used.
By the copolymer concentration that the water that the adds respective amount total amount be adjusted to by aqueous compositions based on preparation is 20 % by weight.
By the zinc plated sheet metal of oil, (size is about 220mm*10mm*0.5mm, Zn additional content 100g/m
2) be dipped in ethyl acetate about 1 minute and utilize paper handkerchief to wipe subsequently.
Subsequently they are bathed (from Surtec at soda-wash solution
germany Ci Wengenbeige's
133,4% concentration) at 60 DEG C place 30 seconds.
After this their are immersed containing in the bath of tap water 2-3 time at 60 DEG C, and immerse subsequently in the bath containing the water softened completely, make its drip-dry subsequently, and utilize pressurized air to blow away.
Apply polymers soln by scraper and apply dry metal sheet.Select scraper with the wet-film thickness obtaining 12 μm in this case.Dry metal sheet (about 12 seconds, PMT (Peak metal temperature) 50 DEG C) in pressure air drying cabinet subsequently, and at 80 DEG C, in loft drier, store 10 minutes subsequently.
At laboratory storage after 48 hours, make the neutral salt spray test that metal sheet stands according to DIN EN ISO 9227.According to EN ISO 10289:2001, after 24 hours, determine corrosion control degree RI24.Result is summed up in Table 1.
Table 1:
Embodiment shows and produces favourable corrosion control by adding trimagnesium phosphate.The amount of additive A is the amount based on multipolymer.
The corrosion control provided by preparation under many circumstances also improves by magnesium ion or phosphate radical, and it is obtained by other compounds of these ions.But, when the raising normally result in corrosion-resistant is slightly lower than use (eight hydrations) trimagnesium phosphate.
Embodiment 12-16
Above-mentioned multipolymer also can apply by dipping method.In that case, base materials employed is the metallic test plate of galvanizing and electrogalvanizing.As mentioned above zinc plated sheet metal pre-treatment is flooded subsequently in the copolymer emulsion with different concns, wherein study different dipping time and repeatedly flood.
Water is utilized polymer B to be diluted to the copolymer concentration of 12 % by weight also by polymer impregnated twice.The drip-dry time is between impregnation steps 1 minute.
Result (base material):
A) electrogalvanizing base material is applied to:
B) electrogalvanizing is applied to and the base material of Cr (III) passivation/chromite process:
According to the result (table 2) after the neutral salt spray test of DIN EN ISO 9227.
Table 2:
CA (24): in the corroded area of the % of the metal sheet area exposed after 24 hours
CA (28d): in the erosional surface area of the % of the metal sheet area exposed after 28 days
The amount of additive A is based on the amount of multipolymer.
Very large advantage is the following fact: nonionic surface active agent (such as Plurafac LF 300-alkoxy fatty alcohols) can be utilized to prepare multipolymer, and can not havoc corrosion control.In addition, result be when flood apply, significantly improve the visual appearance (very evenly and without burr) of sealing and mechanical property (with do not contain wetting agent and be about 6g/m
2polymeric coating compare about 3g/m containing wetting agent
2more thin polymer coating).
Polymer B optionally to be mixed with the additive 1 of 1.6 % by weight (amounts based on multipolymer) with wetting agent Plurafac LF 300 (alkoxy fatty alcohols).Result is summed up in table 3.
Table 3:
| Embodiment | Base material | Additive 1 | Wetting agent (% by weight) | CA(24) | CA(28d) | Additional content (g/m 2) |
| Comparative example 5 | a) | 1.0 | 10 | 4.0 | ||
| 14 | a) | 1.6 | 1.0 | 7 | 2.9 | |
| Comparative example 6 | b) | - | 1.0 | 25 | 4.1 | |
| 15 | b) | 1 | 1.0 | 13 | 3.1 | |
| 16 | b) | 1 | 0.1 | 10 | 3.1 |
CA (24): in the corroded area of the % of the metal sheet area exposed after 24 hours
CA (28d): in the erosional surface area of the % of the metal sheet area exposed after 28 days
The amount of additive 1 is based on the amount of multipolymer.
The amount of wetting agent is based on the amount of polymer B.
Under the existence of wetting agent, the film utilizing composition of the present invention to obtain is thinner relative to contrast system, and it is showing higher corrosion control according in the neutral salt spray test of DIN EN ISO 9227.
Embodiment 17
Use the solution from embodiment 7, the stability in storage of aqueous copolymers solution is tested.Carry out within the time of 3 months at the temperature that this test is each comfortable 10,20 or 60 DEG C.The stability of solution is assessed by visual inspection.Due to the gel formation in solution surface, solution is obviously unstable.
Table 4: the result of stability test
| Dispersion agent | Temperature [DEG C] | Gel formation time |
| 10 | - | |
| 20 | After one month | |
| 60 | After one week | |
| Polyacrylic acid | 10 | - |
| Polyacrylic acid | 20 | - |
| Polyacrylic acid | 60 | - |
Polyacrylic acid used be there is 4000g/mol the polyacrylic sodium salt of weight average low molecule quality (from BASF SE's
cP 10).Polyacrylic concentration is 0.05 % by weight based on the multipolymer of embodiment 7.
Dispersion agent is used reliably to prevent from forming gel even at elevated temperatures.
Claims (15)
1., by making metallic surface contact and a method for coating metal surfaces with moisture copolymer dispersion, wherein moisture copolymer dispersion includes the magnesium ion of effective amount and phosphate radical or phosphonium acid ion, the wherein multipolymer be present in dispersion and is formed by following component:
(A) 20-95 % by weight Mono-olefinic unsaturated hydrocarbons and/or there is the hydrocarbon of two conjugated double bonds,
(B) the Mono-olefinic unsaturated monomer comprising acidic group and/or its acid anhydrides or salt of 5-80 % by weight.
2. method according to claim 1, the multipolymer be wherein present in dispersion comprises following component as other components:
(C) ethylenically unsaturated monomers being different from (A) and (B) of 0-30 % by weight.
3., according to the method for claim 1 or 2, wherein the total amount of magnesium ion, phosphate anion and phosphonium acid ion is 0.1-5 % by weight based on the amount of multipolymer.
4. method as claimed in one of claims 1-3, wherein component (A) is selected from the alkene of ethene, propylene, 1-butylene, 2-butylene, 1-amylene, 1-hexene, 1-heptene and 1-octene at least one.
5. method as claimed in one of claims 1-4, the acidic group wherein in component (B) is the group that at least one is selected from carboxyl, sulfonic acid group and phosphonyl group.
6. method as claimed in one of claims 1-5, wherein makes the acidic group neutralization be present in multipolymer of 0.5-50 % by mole.
7. method as claimed in one of claims 1-6, wherein applies multipolymer by spraying, injection, dipping, blade coating or electrophoretic painting.
8. method as claimed in one of claims 1-7, is wherein present in the metal of metallic surface for being selected from Mg, Al, steel, Zn, and is coated with the one in the steel of Zn, Al, Ni, Sn, Cr or its alloy.
9. method as claimed in one of claims 1-8, wherein make moisture copolymer dispersion contact with inter coat, wherein this inter coat contacts with metallic surface.
10. method according to claim 9, wherein inter coat is Cr conversion coating.
11. methods as claimed in one of claims 1-10, wherein copolymer dispersion other corrosion inhibitors of comprising film forming agent, linked, wetting agent or being different from described multipolymer are as other components.
12. 1 kinds of metallic surfaces through multipolymer coating that can be obtained by the method any one of claim 1-11.
, wherein there are the one or more lacquerings being positioned at the coating superimposed layer containing multipolymer and applying in 13. metallic surfaces through coating according to claim 12.
14. include the magnesium ion of effective amount and the purposes of moisture copolymer dispersion in coating metal surfaces of phosphate radical or phosphonium acid ion, and the multipolymer be wherein present in dispersion is formed by following component:
(A) 20-95 % by weight Mono-olefinic unsaturated hydrocarbons and/or there is the hydrocarbon of two conjugated double bonds,
(B) the Mono-olefinic unsaturated monomer comprising acidic group and/or its acid anhydrides or salt of 5-80 % by weight.
15. purposes according to claim 14, wherein make moisture copolymer dispersion contact with inter coat, and inter coat contact with metallic surface.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP12191614.2 | 2012-11-07 | ||
| EP12191614 | 2012-11-07 | ||
| PCT/EP2013/072923 WO2014072249A1 (en) | 2012-11-07 | 2013-11-04 | Mixtures for the coating of metallic surfaces |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104769047A true CN104769047A (en) | 2015-07-08 |
Family
ID=47172478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380057711.6A Pending CN104769047A (en) | 2012-11-07 | 2013-11-04 | Mixtures for the coating of metallic surfaces |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP2917287A1 (en) |
| JP (1) | JP2016505350A (en) |
| KR (1) | KR20150083111A (en) |
| CN (1) | CN104769047A (en) |
| AU (1) | AU2013343699B2 (en) |
| BR (1) | BR112015009915A2 (en) |
| RU (1) | RU2015121544A (en) |
| WO (1) | WO2014072249A1 (en) |
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|---|---|---|---|---|
| EA201890831A1 (en) * | 2018-04-26 | 2019-10-31 | COMPOSITIONS BASED ON AQUEOUS DISPERSIONS OF POLYMERS CONTAINING N-ALKYLPYRROLIDONES, AND ALSO USE |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2121419B (en) * | 1982-06-01 | 1985-07-31 | Int Paint Plc | Anti-corrosive paint |
| JP2001240978A (en) * | 2000-03-02 | 2001-09-04 | Kansai Paint Co Ltd | Surface treatment method for zinc system plated steel products and aqueous surface treating composition |
| US20050276983A1 (en) * | 2001-10-17 | 2005-12-15 | Seiji Kashiwada | Metal object-coating method and primer composition used in the same |
| JP4263099B2 (en) * | 2001-10-17 | 2009-05-13 | 関西ペイント株式会社 | Metal object coating method and primer composition used in the method |
| JP4061054B2 (en) * | 2001-11-21 | 2008-03-12 | 関西ペイント株式会社 | Aqueous surface treatment composition and surface treatment method for galvanized steel |
| JP4694164B2 (en) * | 2004-07-29 | 2011-06-08 | ユニチカ株式会社 | Rust-proof coating agent and laminated metal material |
| US20070116880A1 (en) * | 2005-11-22 | 2007-05-24 | Anderson Albert G | Method for coating vehicle bodies and parts thereof with rust-preventive ionomeric coatings |
| US20070114131A1 (en) * | 2005-11-22 | 2007-05-24 | Anderson Albert G | Method for coating vehicle bodies and parts thereof with rust-preventive ionomeric coatings |
| EP2049708B1 (en) * | 2006-07-25 | 2017-06-21 | Basf Se | Method of passivating metallic surfaces by means of copolymers having phosphoric acid and/or phosphonic acid groups |
| WO2008092853A1 (en) * | 2007-02-01 | 2008-08-07 | Basf Se | Method for coating surfaces and aqueous formulations suited therefor |
| US7789953B2 (en) * | 2008-03-28 | 2010-09-07 | Praxair S.T. Technology, Inc. | High temperature resistant coating compositions |
| WO2011075712A2 (en) * | 2009-12-18 | 2011-06-23 | Latitude 18, Inc. | Inorganic phosphate corrosion resistant coatings |
-
2013
- 2013-11-04 CN CN201380057711.6A patent/CN104769047A/en active Pending
- 2013-11-04 JP JP2015541096A patent/JP2016505350A/en active Pending
- 2013-11-04 AU AU2013343699A patent/AU2013343699B2/en not_active Expired - Fee Related
- 2013-11-04 RU RU2015121544A patent/RU2015121544A/en not_active Application Discontinuation
- 2013-11-04 WO PCT/EP2013/072923 patent/WO2014072249A1/en active Application Filing
- 2013-11-04 EP EP13791765.4A patent/EP2917287A1/en not_active Withdrawn
- 2013-11-04 BR BR112015009915A patent/BR112015009915A2/en not_active IP Right Cessation
- 2013-11-04 KR KR1020157014865A patent/KR20150083111A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| JP2016505350A (en) | 2016-02-25 |
| BR112015009915A2 (en) | 2017-07-11 |
| EP2917287A1 (en) | 2015-09-16 |
| AU2013343699B2 (en) | 2016-11-10 |
| RU2015121544A (en) | 2016-12-27 |
| KR20150083111A (en) | 2015-07-16 |
| WO2014072249A1 (en) | 2014-05-15 |
| AU2013343699A1 (en) | 2015-05-14 |
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Application publication date: 20150708 |