CN109971265B - Aqueous latex suitable for use in formulating coil coating compositions - Google Patents
Aqueous latex suitable for use in formulating coil coating compositions Download PDFInfo
- Publication number
- CN109971265B CN109971265B CN201910328438.5A CN201910328438A CN109971265B CN 109971265 B CN109971265 B CN 109971265B CN 201910328438 A CN201910328438 A CN 201910328438A CN 109971265 B CN109971265 B CN 109971265B
- Authority
- CN
- China
- Prior art keywords
- aqueous latex
- acid
- weight
- acrylate
- coil coating
- 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.)
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- 239000008199 coating composition Substances 0.000 title claims abstract description 82
- 229920000126 latex Polymers 0.000 title claims abstract description 76
- 239000004816 latex Substances 0.000 title claims abstract description 70
- 239000000178 monomer Substances 0.000 claims abstract description 67
- 239000000203 mixture Substances 0.000 claims abstract description 46
- 238000000576 coating method Methods 0.000 claims abstract description 44
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 39
- 239000011248 coating agent Substances 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 17
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims description 42
- -1 alkyl mercaptan Chemical compound 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000003431 cross linking reagent Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 13
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- 239000003995 emulsifying agent Substances 0.000 claims description 12
- 239000000839 emulsion Substances 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000012986 chain transfer agent Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000012855 volatile organic compound Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 239000012966 redox initiator Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 150000002978 peroxides Chemical class 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- DETXZQGDWUJKMO-UHFFFAOYSA-N 2-hydroxymethanesulfonic acid Chemical compound OCS(O)(=O)=O DETXZQGDWUJKMO-UHFFFAOYSA-N 0.000 claims description 4
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-araboascorbic acid Natural products OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 claims description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 claims description 4
- 235000010350 erythorbic acid Nutrition 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229940026239 isoascorbic acid Drugs 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- XRXANEMIFVRKLN-UHFFFAOYSA-N 2-hydroperoxy-2-methylbutane Chemical compound CCC(C)(C)OO XRXANEMIFVRKLN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004318 erythorbic acid Substances 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 229940001607 sodium bisulfite Drugs 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 claims description 2
- NYYSPVRERVXMLJ-UHFFFAOYSA-N 4,4-difluorocyclohexan-1-one Chemical compound FC1(F)CCC(=O)CC1 NYYSPVRERVXMLJ-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 229960000448 lactic acid Drugs 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 229940099690 malic acid Drugs 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- VSVCAMGKPRPGQR-UHFFFAOYSA-N propan-2-one;sulfurous acid Chemical compound CC(C)=O.OS(O)=O VSVCAMGKPRPGQR-UHFFFAOYSA-N 0.000 claims description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims 2
- INRFMNKGJCROAZ-UHFFFAOYSA-N 2-hydroxy-2-sulfinylacetic acid Chemical compound OC(=O)C(O)=S=O INRFMNKGJCROAZ-UHFFFAOYSA-N 0.000 claims 1
- 150000001356 alkyl thiols Chemical class 0.000 claims 1
- 125000005342 perphosphate group Chemical group 0.000 claims 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 239000000654 additive Substances 0.000 description 11
- 239000000049 pigment Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 238000009826 distribution Methods 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 6
- 229920003180 amino resin Polymers 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 239000004971 Cross linker Substances 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 2
- DTXCLQMVQDIXOO-UHFFFAOYSA-N 2-methyldodecyl prop-2-enoate Chemical compound CCCCCCCCCCC(C)COC(=O)C=C DTXCLQMVQDIXOO-UHFFFAOYSA-N 0.000 description 2
- VISWPKGUIWDFQG-UHFFFAOYSA-N 2-methyloctyl prop-2-enoate Chemical compound CCCCCCC(C)COC(=O)C=C VISWPKGUIWDFQG-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
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- 239000004925 Acrylic resin Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229920003270 Cymel® Polymers 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
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- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
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- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 2
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 2
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- MSYLJRIXVZCQHW-UHFFFAOYSA-N formaldehyde;6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound O=C.NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 MSYLJRIXVZCQHW-UHFFFAOYSA-N 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- SCFQUKBBGYTJNC-UHFFFAOYSA-N heptyl prop-2-enoate Chemical compound CCCCCCCOC(=O)C=C SCFQUKBBGYTJNC-UHFFFAOYSA-N 0.000 description 2
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N methylguanidine Chemical compound CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- MDYPDLBFDATSCF-UHFFFAOYSA-N nonyl prop-2-enoate Chemical compound CCCCCCCCCOC(=O)C=C MDYPDLBFDATSCF-UHFFFAOYSA-N 0.000 description 2
- 229940065472 octyl acrylate Drugs 0.000 description 2
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- YGPZXPHFJSYIKP-UHFFFAOYSA-N nonadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCCOC(=O)C(C)=C YGPZXPHFJSYIKP-UHFFFAOYSA-N 0.000 description 1
- VABATIYWCXGQQP-UHFFFAOYSA-N nonadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCCOC(=O)C=C VABATIYWCXGQQP-UHFFFAOYSA-N 0.000 description 1
- LKEDKQWWISEKSW-UHFFFAOYSA-N nonyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCOC(=O)C(C)=C LKEDKQWWISEKSW-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- MOOYVEVEDVVKGD-UHFFFAOYSA-N oxaldehydic acid;hydrate Chemical compound O.OC(=O)C=O MOOYVEVEDVVKGD-UHFFFAOYSA-N 0.000 description 1
- YOTGRUGZMVCBLS-UHFFFAOYSA-N pentadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCOC(=O)C(C)=C YOTGRUGZMVCBLS-UHFFFAOYSA-N 0.000 description 1
- GOZDOXXUTWHSKU-UHFFFAOYSA-N pentadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCOC(=O)C=C GOZDOXXUTWHSKU-UHFFFAOYSA-N 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- CSNFMBGHUOSBFU-UHFFFAOYSA-N pyrimidine-2,4,5-triamine Chemical compound NC1=NC=C(N)C(N)=N1 CSNFMBGHUOSBFU-UHFFFAOYSA-N 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000002426 superphosphate Substances 0.000 description 1
- KQYLUTYUZIVHND-UHFFFAOYSA-N tert-butyl 2,2-dimethyloctaneperoxoate Chemical compound CCCCCCC(C)(C)C(=O)OOC(C)(C)C KQYLUTYUZIVHND-UHFFFAOYSA-N 0.000 description 1
- VSJBBIJIXZVVLQ-UHFFFAOYSA-N tert-butyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(C)(C)C VSJBBIJIXZVVLQ-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- BWSZXUOMATYHHI-UHFFFAOYSA-N tert-butyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(C)(C)C BWSZXUOMATYHHI-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- ATZHWSYYKQKSSY-UHFFFAOYSA-N tetradecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C(C)=C ATZHWSYYKQKSSY-UHFFFAOYSA-N 0.000 description 1
- XZHNPVKXBNDGJD-UHFFFAOYSA-N tetradecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C=C XZHNPVKXBNDGJD-UHFFFAOYSA-N 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- HUUBMTMJIQHAEN-UHFFFAOYSA-N triazole-1,4-diamine Chemical compound NC1=CN(N)N=N1 HUUBMTMJIQHAEN-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 description 1
- KRLHYNPADOCLAJ-UHFFFAOYSA-N undecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCOC(=O)C(C)=C KRLHYNPADOCLAJ-UHFFFAOYSA-N 0.000 description 1
- RRLMGCBZYFFRED-UHFFFAOYSA-N undecyl prop-2-enoate Chemical compound CCCCCCCCCCCOC(=O)C=C RRLMGCBZYFFRED-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- B05D7/16—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 using synthetic lacquers or varnishes
-
- 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
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- 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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
-
- 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
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明涉及一种适用于配制卷材涂料组合物的水性胶乳，所述水性胶乳包含由单体混合物经乳液聚合形成的丙烯酸类聚合物，所述单体混合物包含，相对于所述单体混合物的总重，a)1‑35重量％的(甲基)丙烯酸羟基C1‑C20烷基酯；b)0.1‑20重量％的具有酸官能团的烯属不饱和单体；和c)45‑98.9重量％的不同于a)和b)中的烯属不饱和单体；其中，所述丙烯酸类聚合物的数均分子量在4000‑30000g/mol的范围内，且重均分子量在10000‑70000g/mol的范围内。本发明还涉及一种包含该水性胶乳的卷材涂料组合物以及包含由该卷材涂料组合物形成的涂层的卷材制品。The present invention relates to an aqueous latex suitable for formulating a coil coating composition, the aqueous latex comprising an acrylic polymer formed by emulsion polymerization of a monomer mixture comprising, relative to the monomer mixture the total weight of a) 1-35% by weight of hydroxy C1-C20 alkyl (meth)acrylates; b) 0.1-20% by weight of ethylenically unsaturated monomers with acid functionality; and c) 45-98.9% by weight % by weight of ethylenically unsaturated monomers different from a) and b); wherein the number-average molecular weight of the acrylic polymer is in the range of 4,000-30,000 g/mol, and the weight-average molecular weight is in the range of 10,000-70,000 g/mol mol range. The present invention also relates to a coil coating composition comprising the aqueous latex and a coil article comprising a coating formed from the coil coating composition.
Description
Technical Field
The present invention relates to an aqueous latex suitable for use in formulating coil coating compositions. The invention also relates to a method for preparing a water-based latex suitable for formulating coil coating compositions and to coil coating compositions comprising the water-based latex.
Background
The coil coating is a special coating used for coating the surfaces of steel plates and aluminum plates to prepare precoated coils. At present, the coil coating technology is mainly developed towards the direction of ultra-long service life, product functionalization and environmental friendliness, and the new application field is not disconnected. With the progress of technology, the application of coil coatings is becoming wider and wider, and coil coatings are adopted in the fields of ship interior decoration, household appliances, furniture, interior and exterior buildings and the like.
In recent years, there has been an increasing demand for high gloss coil coatings in order to improve the texture of the appearance of products. The resin components of the common high-gloss paint are generally of polyacrylate, polyester, nitrocellulose, polyurethane and the like. However, most of these resin products are suitable for formulating solvent-based coil coatings, especially for formulating solvent-based coil coatings having high gloss. The use of such solvent-based coil coatings inevitably produces pollution, which adversely affects the health of the construction personnel and users.
Currently, there is a desire in the market for more resin products suitable for formulating aqueous coil coatings, in particular for formulating aqueous coil coatings with high gloss, to reduce the emission of organic volatile components (VOC).
Disclosure of Invention
The present invention satisfies the above compelling needs of the coatings industry and provides an acrylic resin product suitable for formulating waterborne coil coatings having high gloss and balanced properties.
Specifically, the present invention provides, in one aspect, an aqueous latex suitable for use in formulating coil coating compositions, the aqueous latex comprising an acrylic polymer formed by emulsion polymerization of a monomer mixture comprising, relative to the total weight of the monomer mixture,
a) 1-35% by weight of a hydroxy C1-C20 alkyl (meth) acrylate;
b)0.1 to 20% by weight of an ethylenically unsaturated monomer having an acid function; and
c)45 to 98.9 wt.% of ethylenically unsaturated monomers other than a) and b);
wherein the number average molecular weight of the acrylic polymer is in the range of 4000-30000g/mol, and the weight average molecular weight is in the range of 10000-70000 g/mol.
In another aspect, the present invention provides a method for preparing an aqueous latex suitable for use in formulating coil coating compositions, comprising the steps of:
(1) mixing a monomer mixture, a chain transfer agent, a partial emulsifier and deionized water to obtain a pre-emulsion, and mixing a partial thermal initiator and the deionized water to obtain a thermal initiator solution;
(2) dripping the pre-emulsion and a thermal initiator solution into a mixture formed by the rest of emulsifier, the rest of thermal initiator and deionized water at the same time within the temperature range of 70-90 ℃ to react to obtain a first reaction solution;
(3) adding a second initiator, a reducing agent and optionally a metal catalyst into the first reaction liquid at the temperature of 50-60 ℃ to form a redox initiation system, and further polymerizing the residual monomer mixture to obtain a second reaction liquid; and
(4) neutralizing the second reaction solution, and filtering to obtain the water-based latex;
wherein the aqueous latex comprises an acrylic polymer formed from emulsion polymerization of a monomer mixture,
wherein the monomer mixture comprises, relative to the total weight of the monomer mixture,
a) 1-35% by weight of a hydroxy C1-C20 alkyl (meth) acrylate;
b)0.1 to 20% by weight of an ethylenically unsaturated monomer having an acid function; and
c)45 to 98.9 wt.% of ethylenically unsaturated monomers other than a) and b); and is
Wherein the number average molecular weight of the acrylic polymer is in the range of 4000-30000g/mol, and the weight average molecular weight is in the range of 10000-70000 g/mol.
In yet another aspect, the present invention provides a coil coating composition comprising,
(i) an aqueous latex suitable for use in formulating coil coating compositions according to the present invention; and
(ii) optionally a cross-linking agent, and optionally a cross-linking agent,
wherein a cured coating formed from the coating composition has a 60 ° gloss of 70 or more at a PVC of 30% or more.
In yet another aspect, the present invention provides a web product comprising:
a web substrate having at least one major surface;
a coating applied directly or indirectly to a major surface of the web substrate, the coating being formed from a web coating composition of the present invention.
The inventors of the present invention have pioneered an aqueous latex suitable for use in formulating coil coating compositions, said aqueous latex comprising an acrylic polymer formed from a monomer mixture by emulsion polymerization, wherein the acrylic polymer has a number average molecular weight in the range of 4000-30000g/mol and a weight average molecular weight in the range of 10000-70000 g/mol. Preferably, the hydroxyl number of the acrylic polymer is 30mg KOH/g or more, preferably in the range of 30 to 50mg KOH/g. From such aqueous latexes suitable for use in formulating coil coating compositions, substantially VOC free aqueous coil coating compositions can be formulated.
The inventors of the present invention have surprisingly found that a cured coating formed from a coil coating composition comprising the aqueous latex according to the present invention has a 60 ° gloss of 70 or more at a PVC of 30% or more, which meets the market demand for high gloss aqueous coil coatings.
The present inventors have also surprisingly found that such aqueous latexes suitable for formulating coil coating compositions can be formulated to form aqueous coil coating compositions having lower VOC emissions than other aqueous resins commonly used in the coil coating market (e.g., water-soluble acrylic resins, aqueous polyester resins, etc.).
The details of one or more embodiments of the invention are set forth in the description below. Other features, objects, and advantages of the invention will be apparent from the description and from the claims.
Definition of
As used herein, unless otherwise indicated, "a", "an", "the", "at least one", and "one or more" are used interchangeably herein, as well as where no numerical word is used. Thus, for example, a coating composition comprising "an" additive can be interpreted to mean that "one or more" additives are included in the coating composition. The use of a singular form herein is intended to include the plural form as well, unless the context clearly indicates otherwise.
Where a composition is described as including or comprising a particular component, optional components not contemplated by the present invention are not contemplated as being excluded from the composition and it is contemplated that the composition may consist of or consist of the recited component or where a method is described as including or comprising a particular process step, optional process steps not contemplated by the present invention are not contemplated as being excluded from the method and it is contemplated that the method may consist of or consist of the recited process step.
For the sake of brevity, only some numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form ranges not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and similarly any upper limit may be combined with any other upper limit to form a range not explicitly recited. Also, although not explicitly recited, each point or individual value between endpoints of a range is encompassed within the range. Thus, each point or individual value can form a range not explicitly recited as its own lower or upper limit in combination with any other point or individual value or in combination with other lower or upper limits.
In the present invention, a "high gloss coating" or a "high gloss coating" refers to a coating having a gloss of at least 70, preferably at least 75, measured with the aid of a Sheen small pore gloss meter at a reflection angle of 60 °. By "high gloss (or high gloss, high gloss) coil coating composition" is meant that the coating formed from the coil coating composition is a high gloss coating as defined above.
The term "Pigment Volume Concentration (PVC)" as used herein means the volume of the color and extender pigments (i.e., non-binder solids) in the coating composition as a percentage of the total volume of all non-volatile components (polymer, color and extender pigments) present in the coating composition. PVC reflects the volume relationship between the pigment filler and the polymer particles in the coating film. In the case where the binder solid (polymer) and the non-binder solid comprise multiple components, ideal mixing is assumed and all volumes are additive. Briefly, according to the present invention, the Pigment Volume Concentration (PVC) can be represented by the following formula:
it is well known that the volume of a substance can be determined by the ratio of its mass to its density. In the present invention, the volume of each pigment/filler is determined by the ratio of the mass of the particulate solids to the density thereof, and the volume of the pigment/filler is the sum of the volumes of the particulate solids of the respective pigment/filler. Similarly, the volume of the polymer particles is determined by the ratio of the mass of the solid portion in the aqueous latex to the density of the polymer particles, assuming that the density of the polymer particles is 1g/cm3。
When used in the context of "coil coating composition", the term "substantially free" of Volatile Organic Compounds (VOC) means that the VOC content of the coil coating composition is below the detection limit of standard GB18582-2008, i.e. below 2g/l of coating composition.
In the present invention, the term "(meth) acrylate" means acrylate, methacrylate or a mixture of both.
In the present invention, the numerical ranges defined by endpoints include all any number within the range, for example, a range of 1 to 5 encompasses the numbers 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, and the like. Moreover, the disclosed numerical ranges include all subranges within the broad range, for example, a range of 1 to 5 includes subranges 1 to 4, 1.5 to 4.5, 1 to 2, etc.
The terms "preferred" and "preferably" refer to embodiments of the invention that may provide certain benefits under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. In addition, recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention.
Detailed Description
According to a first aspect of the present invention, there is provided an aqueous latex suitable for use in formulating coil coating compositions, said aqueous latex comprising an acrylic polymer formed by emulsion polymerization of a monomer mixture comprising, relative to the total weight of the monomer mixture,
a) 1-35% by weight of a hydroxy C1-C20 alkyl (meth) acrylate;
b)0.1 to 20% by weight of an ethylenically unsaturated monomer having an acid function; and
c)45 to 98.9 wt.% of ethylenically unsaturated monomers other than a) and b);
wherein the number average molecular weight of the acrylic polymer is in the range of 4000-30000g/mol, and the weight average molecular weight is in the range of 10000-70000 g/mol.
In the aqueous latex suitable for formulating a coil coating composition according to the present invention, the molecular weight and the molecular weight distribution of the acrylic polymer are important parameters affecting the gloss of the coil coating composition. In one embodiment of the present invention, the number average molecular weight (Mn) of the acrylic polymer is in the range of 4000-30000g/mol, preferably 4000-20000g/mol, the weight average molecular weight (Mw) is in the range of 10000-70000g/mol, preferably 10000-40000g/mol, and the molecular weight distribution coefficient (D ═ Mw/Mn) is in the range of 1.5-4.7. The molecular weight and the molecular weight distribution coefficient may be determined using Gel Permeation Chromatography (GPC), such as Agilent 1260.
In the aqueous latexes suitable for formulating coil coating compositions according to the invention, the hydroxyl value of the acrylic polymer also affects the gloss of the coil coating composition to some extent. Thus, according to embodiments of the present invention, the acrylic polymer has a hydroxyl number of 30mg KOH/g or more. In one embodiment of the invention, the acrylic polymer has a hydroxyl number of 30 to 50mg KOH/g, preferably between 35 and 45mg KOH/g. The hydroxyl number is determined by titration.
The inventors of the present invention have surprisingly found that aqueous latexes of acrylic polymers having a molecular weight and a molecular weight distribution within the above ranges, preferably also having a hydroxyl number within the above ranges, can be formulated to form coil coating compositions having high gloss, even at high PVC, e.g. 30%, 35%, 40% or higher, coil coating compositions having high gloss can still be obtained.
In the aqueous latex suitable for formulating a coil coating composition according to the present invention, the acrylic polymer may have a glass transition temperature (Tg) of 5 ℃ to 35 ℃, preferably 8 ℃ to 28 ℃.
The term "Tg" herein denotes the glass transition temperature, which is the temperature at which a polymer transitions from a glassy, brittle state to a rubbery state. The Tg value can be determined experimentally using techniques such as Differential Scanning Calorimetry (DSC) or calculated using the Fox equation. Unless otherwise stated, the Tg values and ranges given herein are based on the Tg calculated using the Fox equation.
The Tg (in open form) of a copolymer with n copolymerized comonomers is given by the weight fraction W of each comonomer type and the Tg (in open form) of the homopolymer from each comonomer according to the Fox equation:
the calculated Tg in degrees Kelvin can be easily converted to degrees Celsius (. degree. C.).
While not wishing to be bound by theory, the inventors believe that the Tg of the acrylic polymer greatly affects the ability of the acrylic polymer as a film-forming resin to coagulate into a film. According to the present invention, the Tg of the acrylic polymer is designed to be 5 ℃ to 35 ℃, preferably 8 ℃ to 28 ℃ in order to obtain the desired film-forming property and coating processability resistance of the polymer.
In the aqueous latex suitable for formulating coil coating compositions according to the present invention, the acrylic polymer aggregates to constitute the dispersed phase. In certain embodiments, the dispersed phase has a particle size in the range of 100nm to 400 nm. The size of the dispersed phase can be measured by the Z-average particle size, which is well known in the art, and refers to the size of the dispersed phase as determined by dynamic light scattering, such as by a Marvlen Zetasizer 3000HS microscopic particle size analyzer. In the embodiment of the present invention, the dispersed phase has a particle size of 100-300nm, preferably 120-280nm, and more preferably 120-250 nm.
The aqueous latex suitable for formulating coil coating compositions according to the present invention is formed by emulsion polymerization of a monomer mixture comprising, relative to the total weight of the monomer mixture, a)1 to 35% by weight of a hydroxy C1-C20 alkyl (meth) acrylate; b)0.1 to 20% by weight of an ethylenically unsaturated monomer having an acid function; and c) from 45 to 98.9% by weight of ethylenically unsaturated monomers other than those in a) and b).
Examples of suitable hydroxy C1-C20 alkyl (meth) acrylates include, but are not limited to, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or any combination thereof. Preferably, the hydroxy C1-C20 alkyl (meth) acrylate is selected from at least one of hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, more preferably, from hydroxyethyl methacrylate.
Examples of suitable ethylenically unsaturated monomers having acid functionality include, but are not limited to, phosphate functional monomers, phosphonate functional monomers, sulfonate functional monomers, carboxylic acid functional monomers, or any combination thereof. Preferably, the ethylenically unsaturated monomer with acid functionality is selected from at least one of phosphate functionalized or carboxylic acid functionalized monomers, more preferably from at least one of carboxylic acid functionalized monomers, such as at least one of acrylic acid, methacrylic acid, beta-carboxyethyl acrylate, crotonic acid, fumaric acid, maleic anhydride, itaconic acid, or monoalkyl esters or anhydrides of dibasic acids (e.g., monoalkyl esters of maleic acid). Particularly preferred is acrylic acid or methacrylic acid, with methacrylic acid being most particularly preferred.
As examples of free-radically polymerizable phosphoric acid-functional monomers, phosphonic acid-functional monomers and sulfonic acid-functional monomers, there have been described, for example, WO 00/39181 (page 8, line 13 to page 9, line 19).
In the aqueous latexes suitable for formulating coil coating compositions according to the invention, the monomer mixture also comprises other ethylenically unsaturated monomers different from the above-mentioned hydroxy C1-C20 alkyl (meth) acrylates and ethylenically unsaturated monomers having an acid function. Examples of suitable ethylenically unsaturated monomers other than those in a) and b) include, but are not limited to, C1-C20 alkyl (meth) acrylates and vinyl aromatic compounds having up to 20 carbon atoms.
According to one embodiment of the present invention, the monomer mixture comprises, relative to the total weight of the monomer mixture,
a) 1-35% by weight of a hydroxy C1-C20 alkyl (meth) acrylate;
b)0.1 to 20% by weight of an ethylenically unsaturated monomer having an acid function;
c1) 10-70% by weight of a C1-C20 alkyl (meth) acrylate; and
c2)1 to 40% by weight of a vinylaromatic compound having up to 20 carbon atoms.
Examples of suitable C1-C20 alkyl methacrylates suitable for use in the present invention include, but are not limited to, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, 2-methyloctyl methacrylate, 2-tert-butyl heptyl methacrylate, 3-isopropyl heptyl methacrylate, decyl methacrylate, undecyl methacrylate, 5-methylundecyl methacrylate, dodecyl methacrylate, and, 2-methyldodecyl methacrylate, tridecyl methacrylate, 5-methyltrodecyl methacrylate, tetradecyl methacrylate, pentadecyl methacrylate, hexadecyl methacrylate, 2-methylhexadecyl methacrylate, heptadecyl methacrylate, 5-isopropylheptadecyl methacrylate, 5-ethyloctadecyl methacrylate, octadecyl methacrylate, nonadecyl methacrylate, eicosyl methacrylate, cycloalkyl methacrylates (e.g., cyclopentyl methacrylate, cyclohexyl methacrylate, 3-vinyl-2-butylcyclohexyl methacrylate, cycloheptyl methacrylate, cyclooctyl methacrylate, etc.), Bornyl methacrylate and isobornyl methacrylate. Preference is given to methyl methacrylate, ethyl methacrylate, butyl methacrylate or tert-butyl methacrylate, particular preference to methyl methacrylate, tert-butyl methacrylate or butyl methacrylate.
Examples of suitable C1-C20 alkyl acrylates suitable for use in the present invention include, but are not limited to, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, 2-methyl-octyl acrylate, 2-tert-butyl heptyl acrylate, 3-isopropyl heptyl acrylate, decyl acrylate, undecyl acrylate, 5-methyl undecyl acrylate, dodecyl acrylate, 2-methyl dodecyl acrylate, tridecyl acrylate, 5-methyl tridecyl acrylate, methyl dodecyl acrylate, propyl acrylate, isopropyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, 2-methyl-octyl acrylate, 2-methyl dodecyl acrylate, tridecyl acrylate, 5-, Tetradecyl acrylate, pentadecyl acrylate, hexadecyl acrylate, 2-methylhexadecyl acrylate, heptadecyl acrylate, 5-isopropylheptadecyl acrylate, 5-ethyloctadecyl acrylate, octadecyl acrylate, nonadecyl acrylate, eicosyl acrylate, cycloalkyl acrylates, such as cyclopentyl acrylate, cyclohexyl acrylate, 3-vinyl-2-butylcyclohexyl acrylate, cycloheptyl acrylate, cyclooctyl acrylate, bornyl acrylate, and isobornyl acrylate. Preference is given to ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate or cyclohexyl acrylate, particular preference to ethyl acrylate, n-butyl acrylate or 2-ethylhexyl acrylate.
Examples of vinyl aromatic compounds having up to 20 carbon atoms include, but are not limited to, styrene, vinyl toluene, o-methyl styrene, p-methyl styrene, α -butyl styrene, 4-n-decyl styrene, halogenated styrenes (e.g., monochlorostyrene, dichlorostyrene, tribromostyrene, or tetrabromostyrene), with styrene being preferred.
Emulsion polymerization techniques for preparing aqueous latexes from the above-described monomer mixtures containing ethylenically unsaturated monomers are diverse, such as single-stage polymerization processes, multistage polymerization processes, continuous processes, and the like. It is well known that an aqueous latex can be prepared using a seed polymerization process in order to control the structure and composition of polymer micelles contained in the aqueous latex.
The aqueous latices suitable for formulating coil coating compositions according to the invention are prepared by the following process: (1) mixing a monomer mixture, a chain transfer agent, a partial emulsifier and deionized water to obtain a pre-emulsion, and mixing a partial thermal initiator and the deionized water to obtain a thermal initiator solution; (2) dripping the pre-emulsion and a thermal initiator solution into a mixture formed by the rest of emulsifier, the rest of thermal initiator and deionized water at the same time within the temperature range of 70-90 ℃ to react to obtain a first reaction solution; (3) adding a second initiator, a reducing agent and optionally a metal catalyst into the first reaction liquid at the temperature of 50-60 ℃ to form a redox initiation system, and further polymerizing the residual monomer mixture to obtain a second reaction liquid; (4) neutralizing the second reaction solution, and filtering to obtain the water-based latex.
Typically, the aqueous latex thus obtained has a solids content of from 40 to 60%.
Examples of useful emulsifiers include anionic surfactants, nonionic surfactants, or combinations thereof as are well known in the art. The nonionic surfactant comprises alkylphenol ethoxylates and fatty alcohol polyoxyethylene ether. Preferably, alkylphenol ethoxylates are used. Anionic surfactants include aliphatic carboxylates, aliphatic sulfonates, aliphatic sulfates, and aliphatic phosphates. Preferably, alkali metal salts, such as Na, K or Li, or alkaline earth metal salts, such as Ca or Ba, are used. In one embodiment according to the invention, an aliphatic sulfonate is used, preferably an alkali metal salt of dodecylsulfonic acid, more preferably Sodium Dodecylsulfonate (SDS). Preferably, the emulsifier is present in an amount of 0.5-5 wt.%, relative to the total charge.
Any known thermal initiator may be used to initiate the polymerization reaction. Examples of suitable thermal initiators include persulfates, such as ammonium persulfate or alkali metal persulfates (including potassium, sodium or lithium); peroxides, such as cumyl hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, dioctyl peroxide, tert-butyl pervalerate, tert-butyl perisononanoate, tert-butyl peroctoate, tert-butyl perneodecanoate, di (2-ethylhexyl) peroxydicarbonate, di (isotridecyl) peroxydicarbonate; azo compounds, such as azobis (isobutyronitrile) and azobis (4-cyanovaleric acid). Preferably, water-soluble thermal initiators persulfates, such as ammonium persulfate, potassium persulfate, and sodium persulfate, are used. More specifically, ammonium persulfate was used as the thermal initiator. Preferably, the thermal initiator is present in an amount of 0.1 to 2% by weight relative to the total charge.
According to the invention, during the preparation of the aqueous latex, a chain transfer agent is added, chosen from isopropanol, halogenated compounds, linear or branched C4-C22One or more of alkyl mercaptans, mercaptoalkanoic acids and alkyl mercaptoalkanoates, preferably straight or branched C4-C22The alkyl mercaptans, more preferably one or more of n-dodecyl mercaptan and t-dodecyl mercaptan, are preferably present in an amount of 0.1 to 5 wt.%, relative to the total charge. The chain transfer agent may be added in one or more portions or continuously, linearly or non-linearly over most or all of the reaction period.
According to the invention, in order to further polymerize the remaining monomer mixture during the preparation of the aqueous latex, a redox initiation system is also used, comprising a second initiator, a reducing agent and optionally a metal catalyst.
Examples of the second initiator include, but are not limited to, peroxides such as hydrogen peroxide, sodium peroxide, potassium peroxide, t-butyl hydroperoxide, t-amyl hydroperoxide, and cumyl hydroperoxide; persulfates such as ammonium persulfate, potassium persulfate, sodium persulfate; perborate; and one or more of a superphosphate; peroxides are preferred, and one or more of hydrogen peroxide, t-butyl hydroperoxide, t-amyl hydroperoxide and cumyl hydroperoxide are more preferred. Typically, the second initiator is present in an amount of 0.01 to 5 wt% relative to the total charge.
Examples of such reducing agents include, but are not limited to, one or more of sodium formaldehyde sulfoxylate, sodium sulfite, sodium bisulfite, sodium thiosulfate, sodium sulfide, sodium hydrosulfide, sodium hydrosulfite, formamidinesulfinic acid, hydroxymethanesulfonic acid, acetone bisulfite, ethanolamine, glycolic acid, glyoxylic acid hydrate, ascorbic acid, isoascorbic acid, lactic acid, malic acid, 2-hydroxy-2-sulfinatoacetic acid, tartaric acid, and salts of such acids; one or more of sodium bisulfite, ascorbic acid and erythorbic acid are preferred. Typically, the reducing agent is present in an amount of 0.01 to 5 wt% relative to the total charge.
The metal catalyst is selected from one or more of iron, copper, manganese, silver, platinum, vanadium, nickel, chromium, palladium and cobalt catalysts, preferably an iron catalyst. Preferably, the metal catalyst is present in an amount of 0.001 to 1 wt% relative to the total charge.
In the above emulsion polymerization process, the reaction conditions of the reaction temperature, the stirring speed and the like can be determined empirically by those skilled in the art. Preferably, the reaction temperature is maintained below 100 ℃ throughout the reaction, more preferably the reaction temperature is in the range of from 30 to 95 ℃, most preferably from 50 to 90 ℃. In addition, the polymerization is preferably carried out at a pH of 4 to 8.
According to another aspect of the present invention, there is provided a process for preparing an aqueous latex suitable for use in formulating coil coating compositions, comprising the steps of: (1) mixing a monomer mixture, a chain transfer agent, a partial emulsifier and deionized water to obtain a pre-emulsion, and mixing a partial thermal initiator and the deionized water to obtain a thermal initiator solution; (2) dripping the pre-emulsion and a thermal initiator solution into a mixture formed by the rest of emulsifier, the rest of thermal initiator and deionized water at the same time within the temperature range of 70-90 ℃ to react to obtain a first reaction solution; (3) adding a second initiator, a reducing agent and optionally a metal catalyst into the first reaction liquid at the temperature of 50-60 ℃ to form a redox initiation system, and further polymerizing the residual monomer mixture to obtain a second reaction liquid; (4) neutralizing the second reaction solution, and filtering to obtain the water-based latex;
the aqueous latex comprises an acrylic polymer formed by emulsion polymerization of a monomer mixture comprising, relative to the total weight of the monomer mixture,
a) 1-35% by weight of a hydroxy C1-C20 alkyl (meth) acrylate;
b)0.1 to 20% by weight of an ethylenically unsaturated monomer having an acid function; and
c)45 to 98.9 wt.% of ethylenically unsaturated monomers other than a) and b);
wherein the number average molecular weight of the acrylic polymer is in the range of 4000-30000g/mol, and the weight average molecular weight is in the range of 10000-70000 g/mol.
In the aqueous latexes suitable for formulating coil coating compositions prepared by the process according to the invention, the hydroxyl number of the acrylic polymer also affects the gloss of the coil coating composition to some extent. According to certain embodiments of the present invention, the acrylic polymer preferably has a hydroxyl number of 30mg KOH/g or more. In one embodiment of the invention, the acrylic polymer has a hydroxyl number of 30 to 50mg KOH/g, preferably between 35 and 45mg KOH/g.
The inventors have surprisingly found that the aqueous latices according to the invention can be used alone or in combination with crosslinkers capable of crosslinking therewith to give high gloss coil coating compositions curable under high temperature baking conditions. Without wishing to be bound by any theory, applicants believe that the gloss of the cured coating is primarily affected by the molecular weight size and distribution of the acrylic polymer in the aqueous latex, and that the hydroxyl value of the acrylic polymer in the aqueous latex also affects the gloss of the resulting cured coating to some extent. The present invention provides an aqueous latex containing an acrylic polymer having a specific molecular weight and molecular weight distribution and hydroxyl value by selecting a specific amount of polymerizable monomer and specific process conditions. Coating compositions formulated from such aqueous latexes exhibit high gloss after curing to a paint film, particularly 60 ° gloss of 70 or greater at PVC levels of 30% or greater.
Thus, according to another aspect of the present invention, there is provided a coil coating composition comprising,
(i) an aqueous latex suitable for use in formulating coil coating compositions according to the present invention; and
(ii) optionally a cross-linking agent, and optionally a cross-linking agent,
wherein a cured coating formed from the coating composition has a 60 ° gloss of 70 or more at a PVC of 30% or more.
The aqueous latices according to the invention may be used alone or in combination with other conventional aqueous latices suitable for formulating coil coating compositions. The dosage can be adjusted according to the requirements of practical application. In one embodiment according to the present invention, the amount of the aqueous latex suitable for formulating a coil coating composition according to the present invention is in the range of 30 to 85 wt. -%, preferably in the range of 30 to 70 wt. -%, more preferably in the range of 35 to 65 wt. -%, relative to the total weight of the coil coating composition.
In the coil coating composition according to the invention, the crosslinking agent is optional. The desired cross-linking agent may be selected according to the requirements of the actual application. In some embodiments of the invention, non-limiting examples of crosslinking agents include amino resin crosslinking agents. The amino resin means a condensation product of aldehydes such as formaldehyde, acetaldehyde, crotonaldehyde, and benzaldehyde and amino or amide group-containing substances such as urea, melamine, and benzoguanamine. Examples of suitable aminoplast resins include, but are not limited to, melamine-formaldehyde resins, benzoguanamine-formaldehyde resins, urea-formaldehyde resins. Condensation products of other amines and amides, such as aldehyde condensates of triazines, diazines, triazoles, guanidines, guanamines, and alkyl-and aryl-substituted melamines, may also be used. Some examples of such compounds are N, N' -dimethylurea, benzourea, dicyandiamide, methylguanidine, ethylguanidine, glycoluril, ammeline, 2-chloro-4, 6-diamino-1, 3, 5-triazine, 6-methyl-2, 4-diamino-1, 3, 5-triazine, 3, 5-diaminotriazole, triaminopyrimidine, 2-mercapto-4, 6-diaminopyrimidine, 3,4, 6-tris (ethylamino) -1,3, 5-triazine, and the like. Although the aldehyde used is typically formaldehyde, other aldehydes such as acetaldehyde, crotonaldehyde, acrolein, benzaldehyde, furfural, glyoxal, and the like, and mixtures thereof, may also be used. According to the present invention, a melamine-formaldehyde crosslinking agent, a benzoguanamine-formaldehyde crosslinking agent, a glycoluril-formaldehyde crosslinking agent, or a combination thereof may be used as the amino resin crosslinking agent. Amino resin crosslinkers are commercially available, non-limiting examples of suitable commercially available amino resin crosslinkers include Cymel303LF, Cymel 1123, Cymel 1170, and the like from Cytec.
The amount of cross-linking agent may depend on various factors including, for example, the type of cross-linking agent, the time and temperature of baking, the molecular weight of the polymer, and the desired properties of the coating. The crosslinking agent is generally present in an amount of up to 50 wt%, preferably up to 30 wt%, more preferably up to 15 wt%, still more preferably up to 5 wt%. If used, the crosslinking agent is generally present in an amount of at least 0.1 wt.%, more preferably at least 1 wt.%, even more preferably at least 1.5 wt.%. These weight percentages are based on the total weight of the coil coating composition.
The coil coating composition of the present invention may also contain conventional additives that do not adversely affect the coil coating composition or the cured coating derived therefrom. Suitable additives include, for example, those agents that improve the processability or manufacturability of the composition, enhance the aesthetics of the composition, improve certain functional properties or characteristics of the coating composition or cured composition resulting therefrom (such as adhesion to a substrate), or reduce cost. Additives that may be included are, for example, fillers, lubricants, coalescents, wetting agents, plasticizers, defoamers, colorants, antioxidants, flow control agents, thixotropic agents, dispersants, adhesion promoters, thickeners, pH adjusters, solvents, or combinations thereof. The individual optional ingredients are present in amounts sufficient for their intended purpose, but preferably such amounts do not adversely affect the coil coating composition or the cured coating resulting therefrom. In a preferred embodiment, the coil coating composition of the present invention may comprise thickeners, dispersants, defoamers, wetting agents, fillers, film forming aids, mold inhibitors, preservatives or any combination thereof as conventional additives. According to the invention, the total amount of conventional additives is from 0.1% to about 40% by weight relative to the total weight of the coil composition.
In one embodiment of the present invention, the coil coating composition according to the present invention comprises, relative to the weight of the coil coating composition, from 30 to 85% by weight of an aqueous latex suitable for formulating coil coating compositions; 5-15% by weight of water; 0-15 wt% of a cross-linking agent; and 0-40 wt% of other additional additives selected from one or more of pigments, fillers, film-forming aids, defoamers, dispersants, wetting agents and thickeners.
As examples of the film-forming assistant, alcohols such as ethylene glycol, propylene glycol, hexylene glycol, benzyl alcohol and the like; alcohol esters such as lauryl alcohol ester; alcohol ethers such as ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol n-propyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether, dipropylene glycol propyl ether, dipropylene glycol butyl ether, tripropylene glycol n-butyl ether and the like; alcohol ether esters such as hexylene glycol butyl ether acetate and the like. As an example of a pigment, R706 available from dupont, usa can be used. As an example of the defoaming agent, SN 154 available from S-NOPCO of Japan can be used. As an example of a dispersant, P30 available from Arkema, France may be used. As an example of a thickener, PLUS 330 available from ASHLAND, usa, can be used.
The water-based latex prepared by the invention is suitable for preparing the coil coating composition, has good film-forming property, can form a film only by a small amount of film-forming additives or without the film-forming additives, greatly reduces the VOC content in the coating, and enables the coating to better meet the environmental protection requirement. Thus, in a preferred embodiment, the coil coating composition according to the invention is substantially free of volatile organic compounds.
The coil coating compositions of the present invention have utility in a variety of applications. Embodiments of the present invention also include a web article comprising a web substrate having at least one major surface; and a coating layer applied directly or indirectly on a major surface of the web substrate, the coating layer being formed from a web coating composition of an embodiment of the present invention.
In certain embodiments of the present invention, the coil coating composition of the present invention may be used in conjunction with a primer, in which case the coil article of the present invention comprises a coil substrate, a primer layer, and a coating layer formed from the coil coating composition of the present invention. In certain embodiments, the primer is an epoxy acrylic primer.
In other embodiments of the present invention, the coil coating composition of the present invention may be applied without a primer, directly on a major surface of a coil substrate.
The coil substrates that may benefit from being coated on their surface with the coil coating composition of the present invention are typically metal substrates, non-limiting examples of which include hot rolled steel, cold rolled steel, hot dip galvanized sheet, electro galvanized sheet, aluminum sheet, tin sheet, various grades of stainless steel, and aluminum-zinc alloy coated steel sheet (e.g., GALVALUE steel sheet or GAL panel).
The coatings formed from the coil coating compositions of the present invention are typically cured or hardened in a temperature environment of about 200-400 deg.C, more preferably about 220-300 deg.C. For coil coating operations, the coating is typically baked for 20-100 seconds to a Peak Metal Temperature (PMT) of about 220 ℃ and 250 ℃.
Hereinafter, the present disclosure will be described more specifically by examples. These examples are for illustrative purposes only and are not to be construed as limiting the scope of the invention, as various modifications and variations within the scope of the present disclosure will be apparent to those skilled in the art. All parts, percentages, and ratios reported in the following examples are on a weight basis unless otherwise stated, and all reagents used in the examples are commercially available and can be used directly without further treatment.
Examples
Preparation of aqueous latices
In a pre-emulsification kettle, weighing deionized water, an emulsifier, ammonia water, each monomer and a chain transfer agent to obtain a monomer pre-emulsion. In the initiator dropping kettle, part of the initiator is put into water to obtain an initiator solution. Then, putting part of the emulsifier, the initiator and the deionized water into a reaction kettle, heating to 70-90 ℃, putting the monomer pre-emulsion and the initiator solution into the reaction kettle at a constant speed within a certain time and at a certain temperature, and carrying out emulsion polymerization to obtain the emulsion containing the acrylic polymer. After cooling to 50-60 ℃, adding tert-butyl hydroperoxide and a reducing agent, further polymerizing residual monomers by using the redox initiation system, adjusting the pH by adding ammonia water according to needs, and filtering to obtain the aqueous latex.
Six kinds of aqueous latices of examples 1 to 3 and comparative examples 1 to 3 were prepared according to the procedures shown above using the formulations shown in Table 1, respectively.
Preparation of coil coating compositions
The six aqueous latexes prepared above were each formulated into a white topcoat having a PVC content of about 43%.
Preparation of coated coil products
The white topcoats of examples 1 and 2 and comparative examples 1 and 2, respectively, were applied to GAL panels coated with an epoxy acrylic primer, with a Dry Film Thickness (DFT) of 15-18 microns and a PMT of 224 and 232 ℃.
The white topcoats of example 3 and comparative example 3 were each applied directly to GAL panels at a dry film thickness DFT of 8-12 microns and a PMT of 224-.
The 60 ℃ gloss of the white coatings formed above was determined according to GB/T13448-.
TABLE 1
The above results show that coil coating compositions exhibiting high gloss can be formulated using the aqueous latexes of the invention, and that the mechanical properties of the resulting coating compositions are comparable to those of coil coating compositions formulated using conventional commercial acrylic emulsions.
The results of the above table show that molecular weight and molecular weight distribution are important factors in determining whether aqueous latexes of acrylic polymers can be formulated to form coil coating compositions having high gloss, and that hydroxyl number also affects the gloss of the coil coating to some extent. The aqueous latexes according to the invention can be formulated to form coil coating compositions having high gloss, even at high PVC.
The entire disclosures of all patents, patent applications, and publications, as well as electronically available materials, cited herein are hereby incorporated by reference. The foregoing detailed description and examples have been given for clarity of understanding only. No unnecessary limitations are to be understood therefrom. The invention is not limited to the exact details shown and described, and variations apparent to those skilled in the art are intended to be included within the invention defined by the claims.
In some embodiments, the invention illustratively disclosed herein may be practiced in the absence of any element which is not specifically disclosed herein. While the invention has been described with reference to a number of embodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope and spirit of the invention as disclosed herein.
Claims (28)
1. An aqueous latex suitable for use in formulating coil coating compositions, said aqueous latex comprising an acrylic polymer formed by emulsion polymerization of a monomer mixture comprising, relative to the total weight of the monomer mixture,
a) 1-35% by weight of a hydroxy C1-C20 alkyl (meth) acrylate;
b)0.1 to 20% by weight of an ethylenically unsaturated monomer having an acid function; and
c)45 to 98.9 wt.% of ethylenically unsaturated monomers other than a) and b);
wherein the number average molecular weight of the acrylic polymer is in the range of 4000-30000g/mol, and the weight average molecular weight is in the range of 10000-70000 g/mol.
2. The aqueous latex of claim 1, wherein the acrylic polymer has a hydroxyl number of 30mg KOH/g or greater.
3. The aqueous latex of claim 1, wherein the hydroxyl number of the acrylic polymer is in the range of 30-50mg KOH/g.
4. The aqueous latex of claim 1, wherein the acrylic polymer has a glass transition temperature of 5 ℃ to 35 ℃.
5. The aqueous latex of claim 1, wherein the acrylic polymer has a glass transition temperature of 8 ℃ to 28 ℃.
6. The aqueous latex of claim 1, comprising a dispersed phase having a particle size in the range of 100nm to 400 nm.
7. The aqueous latex of claim 1, wherein the monomer mixture comprises, relative to the total weight of the monomer mixture,
a) 1-35% by weight of a hydroxy C1-C20 alkyl (meth) acrylate;
b)0.1 to 20% by weight of an ethylenically unsaturated monomer having an acid function;
c1) 10-70% by weight of a C1-C20 alkyl (meth) acrylate; and
c2)1 to 40% by weight of a vinylaromatic compound having up to 20 carbon atoms.
8. The aqueous latex according to any one of claims 1 to 7, wherein the aqueous latex is prepared by:
(1) mixing a monomer mixture, a chain transfer agent, a partial emulsifier and deionized water to obtain a pre-emulsion, and mixing a partial thermal initiator and the deionized water to obtain a thermal initiator solution;
(2) dripping the pre-emulsion and the thermal initiator solution into a mixture formed by the rest of emulsifier, the rest of thermal initiator and deionized water at the same time within the temperature range of 70-90 ℃ to react to obtain a first reaction solution;
(3) adding a second initiator, a reducing agent and optionally a metal catalyst into the first reaction liquid at the temperature of 50-60 ℃ to form a redox initiation system, and further polymerizing the residual monomer mixture to obtain a second reaction liquid; and
(4) neutralizing the second reaction solution, and filtering to obtain the water-based latex.
9. The aqueous latex of claim 8, wherein the thermal initiator is a water soluble thermal initiator.
10. The aqueous latex of claim 8, wherein the thermal initiator is one or more of ammonium persulfate, potassium persulfate, and sodium persulfate.
11. The aqueous latex of claim 8, wherein the thermal initiator is ammonium persulfate.
12. The aqueous latex of claim 8, wherein the thermal initiator is present in an amount of 0.1-2 wt% relative to the total charge.
13. The aqueous latex of claim 8, wherein the chain transfer agent is selected from isopropanol, halogenated compounds, linear or branched C4-C22One or more of an alkyl thiol, a mercaptoalkanoic acid, and an alkyl mercaptoalkanoate.
14. The aqueous latex of claim 8, wherein the chain transfer agent is selected from linear or branched C4-C22An alkyl mercaptan.
15. The aqueous latex of claim 8, wherein the chain transfer agent is selected from one or more of n-dodecyl mercaptan and t-dodecyl mercaptan.
16. The aqueous latex of claim 8, wherein the second initiator is selected from one or more of peroxides, persulfates, perborates, and perphosphates.
17. The aqueous latex of claim 8, wherein the second initiator is selected from peroxides.
18. The aqueous latex of claim 8, wherein the second initiator is selected from one or more of hydrogen peroxide, t-butyl hydroperoxide, t-amyl hydroperoxide, and cumyl hydroperoxide.
19. The aqueous latex of claim 8, wherein the second initiator is present in an amount of 0.1 to 5 wt% relative to the total charge.
20. The aqueous latex of claim 8, wherein the reducing agent is selected from one or more of sodium formaldehyde sulfoxylate, sodium sulfite, sodium bisulfite, sodium thiosulfate, sodium sulfide, sodium hydrosulfide, sodium dithionite, formamidinesulfinic acid, hydroxymethanesulfonic acid, acetone bisulfite, ethanolamine, glycolic acid, glyoxylic acid, ascorbic acid, erythorbic acid, lactic acid, malic acid, 2-hydroxy-2-sulfinylacetic acid, tartaric acid, and salts of the acids.
21. The aqueous latex of claim 8, wherein the reducing agent is selected from one or more of sodium bisulfite, ascorbic acid, and erythorbic acid.
22. The aqueous latex according to claim 8, wherein the reducing agent is present in an amount of 0.01 to 5 wt.%, relative to the total charge.
23. The aqueous latex of claim 8, wherein the metal catalyst is selected from one or more of iron, copper, manganese, silver, platinum, vanadium, nickel, chromium, palladium, and cobalt catalysts.
24. The aqueous latex of claim 8, wherein the metal catalyst is selected from iron catalysts.
25. The aqueous latex of claim 8, wherein the metal catalyst is present in an amount of 0.001 to 1 wt% relative to the total charge.
26. A coil coating composition comprising, in combination,
(i) the aqueous latex of any one of claims 1-25; and
(ii) optionally a cross-linking agent, and optionally a cross-linking agent,
wherein a cured coating formed from the coating composition has a 60 ° gloss of 70 or greater at 30% PVC.
27. The coil coating composition as set forth in claim 26 being substantially free of volatile organic compounds.
28. A roll good article comprising:
a web substrate having at least one major surface; and
a coating applied directly or indirectly to a major surface of the web substrate, the coating formed from the web coating composition of claim 27.
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| KR102433112B1 (en) * | 2022-04-22 | 2022-08-18 | 주식회사 동일폴리머 | Method for preparing aqueous acrylic emulsion |
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| WO2017191167A1 (en) * | 2016-05-04 | 2017-11-09 | Basf Se | Process for preparing an aqueous polymer latex |
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| DE69811293T2 (en) * | 1997-06-20 | 2003-10-23 | Rohm And Haas Co., Philadelphia | polymer compositions |
| CN101798373B (en) * | 2010-03-31 | 2011-09-28 | 鞍山润德精细化工有限公司 | Production process and production line for water-borne acrylic acid modified polyester resin |
| CN102796442B (en) * | 2011-05-24 | 2017-04-19 | 广东华润涂料有限公司 | Unsaturated polyester paint composition |
| CN109384876B (en) * | 2018-10-24 | 2021-07-16 | 黄河三角洲京博化工研究院有限公司 | Water-based emulsion for coil coating and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1501089A (en) * | 1974-01-17 | 1978-02-15 | Rohm & Haas | Coating compositions |
| WO2017191167A1 (en) * | 2016-05-04 | 2017-11-09 | Basf Se | Process for preparing an aqueous polymer latex |
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