CA2877139C - Coated sheet materials having high solar reflective index and corrosion resistance, and methods of making same - Google Patents
Coated sheet materials having high solar reflective index and corrosion resistance, and methods of making same Download PDFInfo
- Publication number
- CA2877139C CA2877139C CA2877139A CA2877139A CA2877139C CA 2877139 C CA2877139 C CA 2877139C CA 2877139 A CA2877139 A CA 2877139A CA 2877139 A CA2877139 A CA 2877139A CA 2877139 C CA2877139 C CA 2877139C
- Authority
- CA
- Canada
- Prior art keywords
- metal sheet
- coated metal
- carbon particles
- cured coating
- graphenic carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000005260 corrosion Methods 0.000 title claims abstract description 22
- 230000007797 corrosion Effects 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 title abstract description 37
- 238000000034 method Methods 0.000 title abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 54
- 239000002184 metal Substances 0.000 claims abstract description 54
- 238000000576 coating method Methods 0.000 claims abstract description 34
- 239000011248 coating agent Substances 0.000 claims abstract description 25
- 239000011347 resin Substances 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000004816 latex Substances 0.000 claims abstract description 21
- 229920000126 latex Polymers 0.000 claims abstract description 21
- 229910001335 Galvanized steel Inorganic materials 0.000 claims abstract description 11
- 239000008397 galvanized steel Substances 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims description 87
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 72
- 229910052799 carbon Inorganic materials 0.000 claims description 69
- 239000000049 pigment Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 14
- 238000012360 testing method Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- 239000002562 thickening agent Substances 0.000 claims description 5
- 238000004132 cross linking Methods 0.000 claims description 2
- 229910001463 metal phosphate Inorganic materials 0.000 claims description 2
- 230000002708 enhancing effect Effects 0.000 claims 1
- 239000008199 coating composition Substances 0.000 description 50
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 17
- 239000010408 film Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000002243 precursor Substances 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000000280 densification Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- -1 vinyl aromatic compound Chemical class 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000013530 defoamer Substances 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002987 primer (paints) Substances 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005325 percolation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229920005692 JONCRYL® Polymers 0.000 description 2
- FLIACVVOZYBSBS-UHFFFAOYSA-N Methyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC FLIACVVOZYBSBS-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- 229960002887 deanol Drugs 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000012972 dimethylethanolamine Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- ZAZKJZBWRNNLDS-UHFFFAOYSA-N methyl tetradecanoate Chemical compound CCCCCCCCCCCCCC(=O)OC ZAZKJZBWRNNLDS-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- APAUNQLFVGBQQW-UHFFFAOYSA-N (1,2,2-trimethylcyclohexyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1(C)CCCCC1(C)C APAUNQLFVGBQQW-UHFFFAOYSA-N 0.000 description 1
- CLHPBURJMZXHFZ-UHFFFAOYSA-N (1,2,2-trimethylcyclohexyl) prop-2-enoate Chemical compound CC1(C)CCCCC1(C)OC(=O)C=C CLHPBURJMZXHFZ-UHFFFAOYSA-N 0.000 description 1
- XPEMPJFPRCHICU-UHFFFAOYSA-N (1-tert-butylcyclohexyl) prop-2-enoate Chemical compound C=CC(=O)OC1(C(C)(C)C)CCCCC1 XPEMPJFPRCHICU-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- LVJZCPNIJXVIAT-UHFFFAOYSA-N 1-ethenyl-2,3,4,5,6-pentafluorobenzene Chemical compound FC1=C(F)C(F)=C(C=C)C(F)=C1F LVJZCPNIJXVIAT-UHFFFAOYSA-N 0.000 description 1
- HLOUDBQOEJSUPI-UHFFFAOYSA-N 1-ethenyl-2,3-dimethylbenzene Chemical class CC1=CC=CC(C=C)=C1C HLOUDBQOEJSUPI-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- LXOFYPKXCSULTL-UHFFFAOYSA-N 2,4,7,9-tetramethyldec-5-yne-4,7-diol Chemical compound CC(C)CC(C)(O)C#CC(C)(O)CC(C)C LXOFYPKXCSULTL-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- DABQKEQFLJIRHU-UHFFFAOYSA-N 2-Propenoic acid, 2-methyl-, 3,3,5-trimethylcyclohexyl ester Chemical compound CC1CC(OC(=O)C(C)=C)CC(C)(C)C1 DABQKEQFLJIRHU-UHFFFAOYSA-N 0.000 description 1
- KWIPUXXIFQQMKN-UHFFFAOYSA-N 2-azaniumyl-3-(4-cyanophenyl)propanoate Chemical compound OC(=O)C(N)CC1=CC=C(C#N)C=C1 KWIPUXXIFQQMKN-UHFFFAOYSA-N 0.000 description 1
- WOYWLLHHWAMFCB-UHFFFAOYSA-N 2-ethylhexyl acetate Chemical compound CCCCC(CC)COC(C)=O WOYWLLHHWAMFCB-UHFFFAOYSA-N 0.000 description 1
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 1
- XTVRLCUJHGUXCP-UHFFFAOYSA-N 3-methyleneheptane Chemical compound CCCCC(=C)CC XTVRLCUJHGUXCP-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YRYZGVBKMWFWGT-UHFFFAOYSA-N Methyl 4-phenylbutanoate Chemical compound COC(=O)CCCC1=CC=CC=C1 YRYZGVBKMWFWGT-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 108091006629 SLC13A2 Proteins 0.000 description 1
- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940090948 ammonium benzoate Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 235000001465 calcium Nutrition 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000001815 facial effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229940094522 laponite Drugs 0.000 description 1
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000013615 primer Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/48—Stabilisers against degradation by oxygen, light or heat
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/004—Reflecting paints; Signal paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
- C09D5/028—Pigments; Filters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
- E04D5/00—Roof covering by making use of flexible material, e.g. supplied in roll form
- E04D5/10—Roof covering by making use of flexible material, e.g. supplied in roll form by making use of compounded or laminated materials, e.g. metal foils or plastic films coated with bitumen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B80/00—Architectural or constructional elements improving the thermal performance of buildings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/254—Polymeric or resinous material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31692—Next to addition polymer from unsaturated monomers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Structural Engineering (AREA)
- Civil Engineering (AREA)
- Architecture (AREA)
- Paints Or Removers (AREA)
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Roof Covering Using Slabs Or Stiff Sheets (AREA)
Abstract
Coated sheet materials having high solar reflective index and corrosion resistance, and methods of making such coated sheet materials, are disclosed. In certain embodiments, the sheet materials comprise metal such as galvanized steel roofing sheets, and the coating is deposited from a latex resin.
Description
, , COATED SHEET MATERIALS HAVING HIGH SOLAR
REFLECTIVE INDEX AND CORROSION RESISTANCE, AND METHODS OF MAKING SAME
FIELD OF THE INVENTION
[0001] The present invention relates to coated sheet materials having high solar reflective index and corrosion resistance, and methods of making such coated sheet materials.
BACKGROUND OF THE INVENTION
REFLECTIVE INDEX AND CORROSION RESISTANCE, AND METHODS OF MAKING SAME
FIELD OF THE INVENTION
[0001] The present invention relates to coated sheet materials having high solar reflective index and corrosion resistance, and methods of making such coated sheet materials.
BACKGROUND OF THE INVENTION
[0002] Sheet materials used in architectural and other applications often require corrosion resistant properties. For example, steel and other types of metal roofing sheet materials must withstand exposure to environmental conditions for extended periods of time. Galvanized steel roofing sheets have conventionally been pre-treated with chromium-containing compositions to increase corrosion resistance. Such pretreatments may be conducted on long strips of the steel, which are then coiled into rolls for subsequent use.
[0003] Galvanized steel and other types of metal roofing materials may have high solar reflectance properties, but they tend to heat up when exposed to sunlight due to their low thermal emittance properties. As a result of such solar heating, the underlying structures can require significant amounts of energy to cool, e.g., by air conditioning.
[0004] Several recent US and state government regulations require metal roofing to meet certain solar reflective index values to avoid overheating. Solar reflective index (SRI) is calculated based upon the combination of solar reflectance and thermal emittance, with an SRI value of 65, 70 or higher being required to meet certain government regulations. Solar reflectance is measured as a percentage of solar radiation in the visible, infrared and ultraviolet regions of the electromagnetic spectrum that is reflected from a surface, with a value of 0 or 0% corresponding to zero reflectance and a value of 1 or 100% corresponding to total reflectance. Thermal emittance is measured as the ability of a surface to shed heat, with a value of 0 or 0% corresponding to zero thermal emittance and a value of 1 or 100% corresponding to total thermal emittance. In - I -, order to reduce overheating, metal roofing with both relatively high solar reflectance and thermal emittance is desired.
[0005] Conventional metal roofing fails to meet certain government energy regulations, and the use of conventional pretreatments decreases the solar reflective index below that of the untreated metal.
SUMMARY OF THE INVENTION
SUMMARY OF THE INVENTION
[0006] An aspect of the invention provides a coated metal sheet comprising a metal substrate, and a cured coating covering at least a portion of the metal substrate, wherein: (a) the cured coating: (i) is deposited from a composition comprising a latex resin, (ii) is substantially clear, (iii) is substantially free of reflective pigments, and (iv) has a dry film thickness of at least 1 micron; and (b) the coated metal sheet has a solar reflective index of at least 65 and a corrosion resistance of at least 500h with no corrosion spots when subjected to an ASTM B117 salt spray test.
[0007] Another aspect of the invention provides a coated roof sheeting material comprising a sheet metal substrate, and a coating covering at least a portion of the sheet metal substrate, wherein the coating consists essentially of a cured latex resin, and wherein the coated roof sheeting material has a solar reflectance of at least 65 percent, a thermal emittance of at least 40 percent, and a corrosion resistance of at least 500h with no corrosion spots when subjected to an ASTM B117 salt spray test.
[0008] A further aspect of the invention provides a method of coating a sheet metal substrate comprising applying a coating composition comprising a latex resin that is substantially free of reflective pigments to the sheet metal substrate at a wet film thickness of at least 1 micron, and curing the coating composition to produce a coated metal sheet having a solar reflective index of at least 65 and a corrosion resistance of at least 500h with no corrosion spots when subjected to an ASTM B117 salt spray test.
, BRIEF DESCRIPTION OF THE DRAWINGS
, BRIEF DESCRIPTION OF THE DRAWINGS
[0009] Fig. 1 is a partially schematic side view of a coated roof sheeting material in accordance with an embodiment of the present invention, illustrating solar reflectance and thermal emittance properties.
[0010] Fig. 2 is a partially schematic side view illustrating a method of coating and coiling metal sheets in rolling mill, including the use of a roll coater for applying a coating composition to the sheets in accordance with an embodiment of the present invention.
[0011] Fig. 3 is a graph of total solar reflectance (TSR) vs. dry film thickness (DFT) for coated metal sheets in accordance with embodiments of the present invention.
[0012] Fig. 4 is a graph of thermal emittance (TE) vs. DFT for coated metal sheets in accordance with embodiments of the present invention.
[0013] Fig. 5 is a graph of solar reflective index (SRI) vs. DFT for coated metal sheets in accordance with embodiments of the present invention.
[0014] Fig. 6 is a graph of TSR vs. DFT for coated metal sheets in accordance with embodiments of the present invention.
[0015] Fig. 7 is a graph of TE vs. DFT for coated metal sheets in accordance with embodiments of the present invention.
[0016] Fig. 8 is a graph of SRI vs. DFT for coated metal sheets in accordance with embodiments of the present invention.
DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION
DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION
[0017] Fig. 1 schematically illustrates a coated sheet material 10 in accordance with an embodiment of the present invention including a substrate sheet 12 and a coating layer 14. In certain embodiments, the coated sheet 10 may be used in architectural applications, such as roof sheeting material for a building 16 or other structure. The coating 14 has a dry film thickness T typically greater than 1 micron, for example, greater than 2 or 3 microns. In certain embodiments, the dry film thickness T of the coating 14 may be from 3 to 10 or 20 microns. The substrate sheet 12 may be of any desired , thickness, such as from 0.5 to 3 mm. For example, the thickness of galvanized steel roof sheeting materials may range from 0.5 to 2 mm in certain embodiments. Although the sheet 12 shown in Fig. 1 is flat, any other shape may be provided, such as corrugated, ribbed, and the like.
1001811 As illustrated in Fig. 1, a portion of solar radiation incident on the coated sheet 10 is reflected from its surface with a total solar reflectance TSR
value. As used herein, the term "total solar reflectance" means a measure of the ability of a surface material to reflect sunlight ¨ including the visible, infrared, and ultraviolet wavelengths ¨
on a scale of 0% to 100%. In certain embodiments, the total solar reflectance TSR of the coated sheet 10 is at least 60%, for example, at least 62% or 65%.
100191 As further illustrated in Fig. 1, the coated sheet 10 has thermal emittance TE properties. As used herein, the term "thermal emittance" refers to the ability of a material to release absorbed heat. A number between 0 and 1, or 0% and 100%, is used to express emittance. In certain embodiments, the thermal emittance TE of the coated sheet 10 is at least 0.3 (30%), for example, at least 0.4 (40%) or 0.5 (50%).
[0020] The total solar reflectance TSR and emittance TE properties, as schematically illustrated in Fig. 1, may be combined to yield a solar reflective index ("SRI"). As used herein, the term "solar reflective index" is a value that incorporates both solar reflectance and emittance in a single value to represent a material's temperature in the sun. SRI quantifies how hot a surface would get relative to standard black and standard white surfaces. It is calculated using equations based on previously measured values of solar reflectance and emittance as laid out in the American Society for Testing and Materials Standard E 1980. In accordance with ASTM Standard E 1980, values of TSR
and TE are input into a standard equation to calculate the SRI value. In certain embodiments, the solar reflective index SRI is at least 65, for example, at least 70 or 75.
[0021] In accordance with embodiments of the invention, the coating composition comprises a latex resin. The latex resin may, or may not, be self-crosslinking. The latex resin typically comprises from 20 to 60 weight percent of the coating composition, for example, from about 30 to about 50 weight percent. In certain embodiments, suitable monomers used for preparing the latex resins may include vinyl aromatic monomers such as styrene, cycloaliphatic monomers such as cyclohexyl methacrylate, and long-chain aliphatic monomers such as 2-ethylhexyl acrylate, MMA and/or 2-ethylhexyl methacrylate. Other types of monomers include cyclohexene, 2-ethyl-1-hexene, cyclohexanol, alpha-methylstyrene, 2-ethylhexanol, 2-ethylhexyl acetate, methyl-4-phenyl butyrate, methyl myristate and/or methyl palmitate.
[0022] In certain embodiments, the monomers used in the latex resin comprise a vinyl aromatic compound, such as a vinyl aromatic monomer, which, in certain embodiments, comprises a compound that has a calculated Tg of least 100 C.
Specific examples of vinyl aromatic compounds are styrene (which has a calculated Tg of 100 C), a-methylstyrene (which has a calculated Tg of 168 C), vinyltoluene, p-methylstyrene, ethylvinylbenzene, vinylnaphthalene, vinylxylenes, a-methylstyrene dimer (meth)acrylate, penta fluoro styrene, and the like. In certain embodiments, styrene or another vinyl aromatic monomer may comprise the most predominant monomer of the resin on a weight percent basis.
[0023] In certain embodiments, the monomers of the latex resin include cycloaliphatic (meth)acrylate monomers, such as trimethylcyclohexyl acrylate, t-butyl cyclohexyl acrylate, dicyclopentadiene (meth)acrylate, trimethylcyclohexyl methacrylate (calculated Tg of 98 C), cyclohexyl methacrylate (calculated Tg of 83 C), isobornyl methacrylate (calculated Tg of 110 C), 2-ethylhexyl methacrylate, tetrahydrofurfuryl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate (calculated Tg of 125 C), and/or 4-t-butylcyclohexyl methacylate, and the like.
[0024] In certain embodiments, the monomers of the latex resin include an alkyl(meth)acrylate, which, in certain embodiments, comprises a compound that has a calculated Tg of least 100 C. Specific examples of alkyl(meth)acrylates are C1-alkyl(meth)acrylates, such as methyl(meth)acrylate (which has a calculated Tg of 105 C), propyl(meth)acrylate, butyl(meth)acrylate, isobutyl(meth)acrylate, hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, octyl(meth)acrylate, decyl(meth)acrylate, dodecyl(meth)acrylate, pentadecyl(meth)acrylate, hexadecyl(meth)acrylate, octadecyl(meth)acrylate, and nonadecyl(meth)acrylate, and mixtures thereof.
Other monomers include, for example, nitriles, such as acrylonitrile and/or methacrylonitrile.
[0025] Some non-limiting examples of latex resins that may be used in the coating compositions of the present invention are commercially available from Nuplex, Lubrizol, Rohm and Haas, Alberdingk Boley Company, Omnova and DSM Neoresins, such as Joncryl 1982, Caroboset CR-781, Alberdingk AC 2403, Alberdingk 2360, Neocryl XK-98 and the like.
[0026] The latex resin may have an average particle size of from 50 nm to 300 nm, for example from 60 nm to 100 or 150 nm; a glass transition temperature (TG) of from -20 to 100 C, typically from zero to 20 or 50 C; and an acid number of from 0 to 20, typically from 2 to 10.
[0027] The coating compositions of the present invention may be waterborne. In certain embodiments, water may comprise from 20 to 80 weight percent of the coating compositions, for example, from 50 to 65 weight percent. In certain embodiments, the coating compositions comprise less than 10 weight percent organic solvents, for example, less than 7 or 4 weight percent, based on the total weight of the composition.
The resin solids content of the coating compositions may be relatively high, for example, greater than 35 or 40 weight percent, based on the total weight of the composition.
[0028] The coating compositions may have little or no volatile organic content (VOC). For example, the coating compositions may comprise less than 1.5 weight percent VOCs, for example, less than 1 or 0.5 weight percent VOCs, based on the total weight of the composition. In certain embodiments, the coating compositions are substantially free of VOCs.
[0029] The coating compositions may further comprise at least one coalescing agent in an amount of up to 10 weight percent, for example, in an amount of from 2 to 3 weight percent, based on the total weight of the coating composition. Examples of suitable coalescing agents include butyl carbitol commercially available from Dow Chemical Company, DowanolTM DPM, DowanolTM DPnB, DowanolTM PPh, butyl cellosolve or DowanolTM DPnP. In accordance with embodiments of the present invention, the coalescing agents form a thin film around the latex resin particles, which helps them coalesce. Improved coalescence of the latex resin particles results in very fine particle sizes and a uniform microstructure, which provides improved corrosion , protection in comparison with other types of coatings having larger resin particle sizes.
For example, in accordance with certain embodiments of the present invention, the average resin particle size may be less than 150 nanometers, for example, less than 100 or 80 nanometers.
[0030] In certain embodiments, wax may be added to the coating compositions in amounts up to 10 weight percent, for example, from 0.5 to 3 weight percent, based on the total weight of the coating composition. Suitable types of wax include Ceraflour 913, Worleeadd 352, AquamatTM 272, AquamatTM 270, Aquacer 539, and combinations thereof. For example, wax sold under the designation AquamatTM 272 by BYK
Chemie may be used. The type and amount of wax may be controlled in order to improve scratch resistance of the coated sheet materials. For example, when the coated sheets are formed into coils, the use of wax additives may reduce or prevent scratching during the coiling an uncoiling processes, as well as during subsequent installation and use of the coated sheet materials. In certain embodiments, the amount of wax added to the coating composition is limited in order to avoid unwanted slippage when the coated sheets are coiled, e.g., to prevent unwanted "telescoping" of the coils due to low friction between the adjacent coil layers.
[0031] Various other additives may optionally be added to the coating compositions in accordance with certain embodiments of the invention. For example, suitable additives include thickeners, defoamers, surfactants, rust inhibitors, pH control agents, silica, and tints.
[0032] Suitable thickeners include AcrysolTM ASE-60, Aquatix 8421, DSX-1550, and Laponite RD. When used, such thickening agents may be present in amounts up to 7 weight percent, for example, from 0.5 to 4 weight percent, based on the total weight of the coating composition.
100331 Suitable defoamers include BYKTm-011, BYKTm-20, BYKTm-32, BYKTM
34 and DrewplusTM L-419 available from Ashland in amounts up to 2 weight percent, for example, from 0.1 to 0.5 weight percent, based on the total weight of the coating composition.
[0034] Suitable surfactants include ZOnY1TM FSP available from DuPont, Surfynol 104E available from Air Products, BYKTM 346, and BYKTM 348 in amounts up to 2 weight percent, for example, from 0.1 to 0.5 weight percent, based on the total weight of the coating composition.
[0035] Suitable rust inhibitors include HaloxTM 550, HaloxTM Flash X-150, 330, HaloxTM SZP-391, ammonium benzoate, and sodium nitrite in typical amounts up to 1 weight percent, for example, from 0.4 to 0.6 weight percent, based on the total weight of the coating composition.
[0036] In certain embodiments, the coating compositions are substantially free of certain metal salts such as metal phosphates, phosphocarbonates and phosphosilicates.
For example, the compositions may be substantially free of zinc phosphate, calcium phosphate, calcium phosphosilicate and/or calcium-enriched silica.
[0037] Suitable pH control agents include any water soluble amine such as dimethylethanol amine (DMEA) available from Avecia in typical amounts up to 1 weight percent, for example, from 0.01 to 0.2 weight percent, based on the total weight of the coating composition.
[0038] In accordance with certain embodiments of the invention, the coatings are substantially free of chrome. In such embodiments, chrome is not purposely added to the coating compositions and is only present in trace levels or as an impurity.
[0039] In certain embodiments, chromate-containing materials may be added to the coating compositions. Such chromate-containing coating compositions may be particularly useful as primer coatings. For example, strontium chromate may be added in amounts up to 12 weight percent, for example, from 0.2 to 1 weight percent, based on the total weight of the coating composition. Such strontium chromate-containing additives may provide improved corrosion resistance properties. When used as primer coatings, the coating compositions may further include colorants and tints typically used in primers, such as titanium dioxide and the like.
[0040] In certain embodiments, silica may be added to the coating compositions, for example, in amounts from 0.1 to 2 or 3 weight percent or more. Some examples of silica include LoVe1TM 275 silica from PPG Industries and AerosiITM 200 silica from Air Products.
[0041] In certain embodiments, the coating compositions and cured coatings are substantially free of reflective pigments. As used herein, the term "reflective pigment"
means plate-like or sheet-like interference pigments such as mica, silicates, silicon dioxide and aluminum oxide. Solarflair 9870 from Eckart is an example of a reflective pigment. As used herein, the term "substantially free of reflective pigments"
means that the coatings have zero or minimal amounts of reflective pigments while achieving the desired level of solar reflectance and/or solar reflective index. For example, the cured coatings may have less than 2 or 1 weight percent reflective pigment. Although the coatings may be substantially free of reflective pigments, they still maintain sufficient solar reflectance properties and solar reflective index values, e.g., SRIs of 65 or greater.
The cost of reflective pigment additives may thus be avoided, while still providing a desired level of solar reflectance.
[0042] In certain embodiments, at least one colored pigment or tint may be added to the coating compositions. Colored pigments and tints are different from reflective interference pigments and include standard inorganic and organic pigments, such as those found in conventional paints and primers. For example, various colored pigments are listed in the Dry Color Manufacturers Association (DCMA) classifications. Such colored pigments and tints typically comprise particles having substantially equiaxed morphologies, e.g., aspect ratios of about 1:1, in comparison with plate-like and sheet-like reflective interference pigments having relatively high aspect ratios.
One suitable type of colored pigment includes TiO2 in an amount up to 35 weight percent, for example, from 1 to 25 weight percent, based on the total weight of the coating composition. Aquext white tint commercially available from PPG Industries and Corrosperse 176E chrome tint commercially available from Wayne Pigments are examples of suitable tints.
[0043] In certain embodiments, the coating is substantially free of colored pigments and tints. For example, the coatings may be substantially clear and colorless.
[0044] In certain embodiments, conductive particles such as graphenic carbon particles may be added to the coating compositions in amounts of to 5 weight percent, for example, from 1 to 2 weight percent, based on the total weight of the coating composition. Such graphenic carbon particles may provide improved thermal emissivity properties. The graphenic carbon particles may be obtained from commercial sources, or may be made in accordance with the methods and apparatus described in U.S.
Patent Nos. 8,486,363 and 8,486,364. Exemplary commercially available graphenic carbon particles are available from Angstron and XG Sciences.
[0045] As used herein, the term "graphenic carbon particles" means carbon particles having structures comprising one or more layers of one-atom-thick planar sheets of sp2-bonded carbon atoms that are densely packed in a honeycomb crystal lattice. The average number of stacked layers may be less than 100, for example, less than 50. In certain embodiments, the average number of stacked layers is 30 or less, such as 20 or less, 10 or less, or, in some cases, 5 or less. The graphenic carbon particles may be substantially flat, however, at least a portion of the planar sheets may be substantially curved, curled, creased or buckled. The particles typically do not have a spheroidal or equiaxed morphology.
[0046] In certain embodiments, the graphenic carbon particles present in the compositions of the present invention have a thickness, measured in a direction perpendicular to the carbon atom layers, of no more than 10 nanometers, no more than 5 nanometers, or, in certain embodiments, no more than 4 or 3 or 2 or 1 nanometers, such as no more than 3.6 nanometers. In certain embodiments, the graphenic carbon particles may be from 1 atom layer up to 3, 6, 9, 12, 20 or 30 atom layers thick, or more. In certain embodiments, the graphenic carbon particles present in the compositions of the present invention have a width and length, measured in a direction parallel to the carbon atoms layers, of at least 50 nanometers, such as more than 100 nanometers, in some cases more than 100 nanometers up to 500 nanometers, or more than 100 nanometers up to 200 nanometers. The graphenic carbon particles may be provided in the form of ultrathin flakes, platelets or sheets having relatively high aspect ratios (aspect ratio being defined as the ratio of the longest dimension of a particle to the shortest dimension of the particle) of greater than 3:1, such as greater than 10:1.
[0047] In certain embodiments, the graphenic carbon particles used in the compositions of the present invention have relatively low oxygen content. For example, the graphenic carbon particles used in certain embodiments of the compositions of the present invention may, even when having a thickness of no more than 5 or no more than 2 nanometers, have an oxygen content of no more than 2 atomic weight percent, such as no more than 1.5 or 1 atomic weight percent, or no more than 0.6 atomic weight, such as about 0.5 atomic weight percent. The oxygen content of the graphenic carbon particles can be determined using X-ray Photoelectron Spectroscopy, such as is described in D. R.
Dreyer et al., Chem. Soc. Rev. 39, 228-240 (2010).
[0048] In certain embodiments, the graphenic carbon particles used in the compositions of the present invention have a B.E.T. specific surface area of at least 50 square meters per gram, such as 70 to 1000 square meters per gram, or, in some cases, 200 to 1000 square meters per grams or 200 to 400 square meters per gram. As used herein, the term "B.E.T. specific surface area" refers to a specific surface area determined by nitrogen adsorption according to the ASTMD 3663-78 standard based on the Brunauer-Emmett-Teller method described in the periodical "The Journal of the American Chemical Society", 60, 309 (1938).
[0049] In certain embodiments, the graphenic carbon particles used in the compositions of the present invention have a Raman spectroscopy 2D/G peak ratio of at least 1.1, for example, at least 1.2 or 1.3. As used herein, the term "2D/G
peak ratio"
refers to the ratio of the intensity of the 2D peak at 2692 cm-1 to the intensity of the G
peak at 1,580 cm-I.
[0050] In certain embodiments, the graphenic carbon particles used in the compositions of the present invention have a relatively low bulk density. For example, the graphenic carbon particles used in certain embodiments of the present invention are characterized by having a bulk density (tap density) of less than 0.2 g/cm3, such as no more than 0.1 g/cm3. For the purposes of the present invention, the bulk density of the graphenic carbon particles is determined by placing 0.4 grams of the graphenic carbon particles in a glass measuring cylinder having a readable scale. The cylinder is raised approximately one-inch and tapped 100 times, by striking the base of the cylinder onto a hard surface, to allow the graphenic carbon particles to settle within the cylinder. The volume of the particles is then measured, and the bulk density is calculated by dividing 0.4 grams by the measured volume, wherein the bulk density is expressed in terms of g/cm3.
[0051] In certain embodiments, the graphenic carbon particles used in the compositions of the present invention have a compressed density and a percent densification that is less than the compressed density and percent densification of graphite powder and certain types of substantially flat graphenic carbon particles. Lower compressed density and lower percent densification are each currently believed to contribute to better dispersion and/or rheological properties than graphenic carbon particles exhibiting higher compressed density and higher percent densification. In certain embodiments, the compressed density of the graphenic carbon particles is 0.9 or less, such as less than 0.8, less than 0.7, such as from 0.6 to 0.7. In certain embodiments, the percent densification of the graphenic carbon particles is less than 40%, such as less than 30%, such as from 25 to 30%.
[0052] For purposes of the present invention, the compressed density of graphenic carbon particles is calculated from a measured thickness of a given mass of the particles after compression. Specifically, the measured thickness is determined by subjecting 0.1 grams of the graphenic carbon particles to cold press under 15,000 pound of force in a 1.3 centimeter die for 45 minutes, wherein the contact pressure is 500 MPa.
The compressed density of the graphenic carbon particles is then calculated from this measured thickness according to the following equation:
Compressed Density (g/cm3) = 0.1 grams I1*(1.3cm/2)2*(measured thickness in cm) [0053] The percent densification of the graphenic carbon particles is then determined as the ratio of the calculated compressed density of the graphenic carbon particles, as determined above, to 2.2 g/cm3, which is the density of graphite.
[0054] In certain embodiments, the graphenic carbon particles have a measured bulk liquid conductivity of at least 100 microSiemens, such as at least 120 microSiemens, such as at least 140 microSiemens immediately after mixing and at later points in time, such as at 10 minutes, or 20 minutes, or 30 minutes, or 40 minutes. For the purposes of the present invention, the bulk liquid conductivity of the graphenic carbon particles is determined as follows. First, a sample comprising a 0.5% solution of graphenic carbon particles in butyl cellosolve is sonicated for 30 minutes with a bath sonicator.
Immediately following sonication, the sample is placed in a standard calibrated electrolytic conductivity cell (K=1). A Fisher Scientific AB 30 conductivity meter is introduced to the sample to measure the conductivity of the sample. The conductivity is plotted over the course of about 40 minutes.
[0055] In accordance with certain embodiments, percolation, defined as long range interconnectivity, occurs between the conductive graphenic carbon particles. Such percolation may reduce the resistivity of the coating compositions. The conductive graphenic particles may occupy a minimum volume within the coating such that the particles form a continuous, or nearly continuous, network. In such a case, the aspect ratios of the graphenic carbon particles may affect the minimum volume required for percolation. Furthermore, the surface energy of the graphenic carbon particles may be the same or similar to the surface energy of the elastomeric rubber.
Otherwise, the particles may tend to flocculate or demix as they are processed.
[0056] The graphenic carbon particles utilized in the compositions of the present invention can be made, for example, by thermal processes. In accordance with embodiments of the invention, the graphenic carbon particles are produced from carbon-containing precursor materials that are heated to high temperatures in a thermal zone.
For example, the graphenic carbon particles may be produced by the systems and methods disclosed in United States Patent Nos. 8,486,363 and 8,486,364.
[0057] In certain embodiments, the graphenic carbon particles may be made by using the apparatus and method described in United States Patent No. 8,486,363 at [0022]
to [0048] in which (i) one or more hydrocarbon precursor materials capable of forming a two-carbon fragment species (such as n-propanol, ethane, ethylene, acetylene, vinyl chloride, 1,2-dichloroethane, allyl alcohol, propionaldehyde, and/or vinyl bromide) is introduced into a thermal zone (such as a plasma); and (ii) the hydrocarbon is heated in the thermal zone to a temperature of at least 1,000 C to form the graphenic carbon particles. In other embodiments, the graphenic carbon particles may be made by using the apparatus and method described in United States Patent No. 8,486,364 at [0015] to [0042] in which (i) a methane precursor material (such as a material comprising at least 50 percent methane, or, in some cases, gaseous or liquid methane of at least 95 or 99 percent purity or higher) is introduced into a thermal zone (such as a plasma); and (ii) the methane precursor is heated in the thermal zone to form the graphenic carbon particles.
Such methods can produce graphenic carbon particles having at least some, in some cases all, of the characteristics described above.
[0058] During production of the graphenic carbon particles by the methods described above, a carbon-containing precursor is provided as a feed material that may be contacted with an inert carrier gas. The carbon-containing precursor material may be heated in a thermal zone, for example, by a plasma system. In certain embodiments, the precursor material is heated to a temperature ranging from 1,000 C to 20,000 C, such as 1,200 C to 10,000 C. For example, the temperature of the thermal zone may range from 1,500 to 8,000 C, such as from 2,000 to 5,000 C. Although the thermal zone may be generated by a plasma system, it is to be understood that any other suitable heating system may be used to create the thermal zone, such as various types of furnaces including electrically heated tube furnaces and the like.
[0059] The gaseous stream may be contacted with one or more quench streams that are injected into the plasma chamber through at least one quench stream injection port. The quench stream may cool the gaseous stream to facilitate the formation or control the particle size or morphology of the graphenic carbon particles. In certain embodiments of the invention, after contacting the gaseous product stream with the quench streams, the ultrafine particles may be passed through a converging member.
After the graphenic carbon particles exit the plasma system, they may be collected. Any suitable means may be used to separate the graphenic carbon particles from the gas flow, such as, for example, a bag filter, cyclone separator or deposition on a substrate.
[0060] Without being bound by any theory, it is currently believed that the foregoing methods of manufacturing graphenic carbon particles are particularly suitable for producing graphenic carbon particles having relatively low thickness and relatively high aspect ratio in combination with relatively low oxygen content, as described above.
Moreover, such methods are currently believed to produce a substantial amount of graphenic carbon particles having a substantially curved, curled, creased or buckled morphology (referred to herein as a "3D" morphology), as opposed to producing predominantly particles having a substantially two-dimensional (or flat) morphology.
This characteristic is believed to be reflected in the previously described compressed density characteristics and is believed to be beneficial in the present invention because, it is currently believed, when a significant portion of the graphenic carbon particles have a 3D morphology, "edge to edge" and "edge-to-face" contact between graphenic carbon particles within the composition may be promoted. This is thought to be because particles having a 3D morphology are less likely to be aggregated in the composition (due to lower Van der Waals forces) than particles having a two-dimensional morphology.
Moreover, it is currently believed that even in the case of "face to face"
contact between the particles having a 3D morphology, since the particles may have more than one facial plane, the entire particle surface is not engaged in a single "face to face"
interaction with another single particle, but instead can participate in interactions with other particles, including other "face to face" interactions, in other planes. As a result, graphenic carbon particles having a 3D morphology are currently thought to provide the best conductive pathway in the present compositions and are currently thought to be useful for obtaining electrical conductivity characteristics sought by the present invention, particularly when the graphenic carbon particles are present in the composition in relatively low amounts.
[0061] Fig. 2 schematically illustrates a roll coating method for applying coating compositions onto sheet materials in accordance with an embodiment of the present invention. In the embodiment shown, the coating operation may be conducted in a conventional rolling mill. Metal sheet material, such as galvanized steel or the like, is provided in a long strip 5 that passes under oppositely-rotating coating rollers 20 and 22, which are fed with a supply of a coating composition 24. The uncoated strip 5 passes =
under the coating rollers 20 and 22, where a layer of the coating composition 24 is deposited on the upper surface of the sheet material. The coated sheet material 10 may be formed into a coil 26 for storage and transportation for use in various applications, such as galvanized steel roof sheeting.
[0062] During the roll coating process, the coating composition is typically applied to the sheet material 5 with a wet film thickness of at least 1 micron, typically at least 1 or 5 microns. In certain embodiments, the wet film thickness of the coating material is from 5 to 15 or 20 microns. In certain embodiments, the deposition rate of the coating composition may be at least 200 ft/min, typically at least 300 ft/min or 350 ft/min.
[0063] After application, the coating compositions typically dry and cure quickly with minimal VOC emissions. Curing times are typically in less than 1 minute, for example, less than 10 or 5 seconds. Typical curing temperatures are below 300 F, for example, below 275 or 250 F. In certain embodiments, curing times may be less than 3 or 2 seconds at temperatures of 225 F or 200 F, or less.
[0064] The dry film thickness of the cured coating is typically at least 1 micron up to 15 or 20 microns. For example, the dry film thickness may be from 5 to microns. In accordance with the present invention, such relatively thin coating layers have been found to significantly increase the solar reflective index of metal roof sheeting materials.
[0065] The following examples illustrate various aspects of the present invention, but are not intended to limit the scope of the invention.
EXAMPLES
[0066] Coating compositions were prepared and tested as described in Tables 1-below.
Table 1 Coating Composition Nos. 1-3 Components Sample No. Sample No. 2 Sample No.
Acrylic Latex Resin 198.10 199.18 165.41 Deionized Water 15.23 17.84 85.30 Defoamer 0.48 0.48 0.51 Surfynol Surfactant 1.04 1.04 1.06 Surfactant 1.04 1.04 1.06 Coalescing Agent 10.01 10.01 10.15 Chrome Tint 5.98 5.98 White Tint 154.63 Rust Inhibitor 2.41 2.43 2.46 Thickener 3.55 3.55 5.36 Deionized Water 3.55 3.55 0.54 pH Control Agent 0.53 0.53 0.54 Deionized Water 0.53 0.53 0.54 Wax 3.64 3.64 10.52 Total Weight in Grams 246.09 243.82 444.06 Table 2 Coating Composition No. 4 Components Sample No. 4 Latex Resin 201.14 UC Intermediate' 22.27 Deionized Water 3.70 Defoamer 0.13 Rust Inhibitor Pigment 8.05 Surfactant 0.24 Silica 1.08 Deionized Water 0.10 Total Weight in Grams 236.62 I Acrylic Emulsion Joncryl 538 (98.88); Defoamer (0.74); Deionized Water (5.0); Silica (25.11); Corrosion Pigment (49.78); Reflective Pigment (25.11); and Defoamer (0.26).
100671 The components listed in Tables 1 and 2 above were added together in the order described in each table under gentle stirring. The coating compositions were allowed to equilibrate overnight before panel preparation. Viscosity and pH
were checked the next day. The coating compositions were applied to galvanized steel substrates using a wire drawdown bar. The coated panels were placed in a conveyor oven set at a temperature to obtain a peak metal temperature of 190 F in two seconds dwell time (line speed). The coated panels were tested, with the results shown in Table 3 below.
Table 3 Test Results Sample No. 1 Sample No. 2 Sample No. 3 Sample No. 4 % Weight Solids 41.82 41.62 45.0 44.03 Viscosity (Seconds) 10-15 10-15 12-20 9-25 (measured using #4 Zahn Cup at room temperature) Dry Film Thickness 0.15-0.20 0.15-0.20 0.4-0.5 (mils) 0.15-0.25 (mils) (mils) (mils) 10.2-12.7 3.8-6.4 (microns) 3.8-5.1 3.8-5.1 (microns) (microns) (microns) Pencil Hardness HB-F HB-F HB-F
T-Bendl 1/3 np/nc 1/3 np/nc 1/3 np/nc 1/3 np/nc Reverse Impact2 Pass Pass Pass Pass X-Hatch Adhesion3 Pass Pass Pass Pass Butler Immersion No Corrosion No Corrosion No Corrosion Corrosion ¨ fail Salt Spray No Black Spots No Black Spots No Black Spots Corrosion ¨ fail Wet Stack No Pressure No Pressure No Pressure Pressure Mottling Mottling Mottling mottling, black spots TSR (%) 66.8 65 70.7 66.8 TE (%) 54 58 78 54 100681 In accordance with the pencil hardness test, ASTM D3363, a pencil is held firmly against the coating at a 45 degree angle and pushed away from the operator in a 0.25 inch stroke. Sufficient pressure is exerted downward and forward either to cut or scratch the film. The process is repeated down the hardness scale until a pencil is found that will not cut through the film to the substrate. The scale of hardness is:
6B (very soft) up to a 6H (very hard).
1001811 As illustrated in Fig. 1, a portion of solar radiation incident on the coated sheet 10 is reflected from its surface with a total solar reflectance TSR
value. As used herein, the term "total solar reflectance" means a measure of the ability of a surface material to reflect sunlight ¨ including the visible, infrared, and ultraviolet wavelengths ¨
on a scale of 0% to 100%. In certain embodiments, the total solar reflectance TSR of the coated sheet 10 is at least 60%, for example, at least 62% or 65%.
100191 As further illustrated in Fig. 1, the coated sheet 10 has thermal emittance TE properties. As used herein, the term "thermal emittance" refers to the ability of a material to release absorbed heat. A number between 0 and 1, or 0% and 100%, is used to express emittance. In certain embodiments, the thermal emittance TE of the coated sheet 10 is at least 0.3 (30%), for example, at least 0.4 (40%) or 0.5 (50%).
[0020] The total solar reflectance TSR and emittance TE properties, as schematically illustrated in Fig. 1, may be combined to yield a solar reflective index ("SRI"). As used herein, the term "solar reflective index" is a value that incorporates both solar reflectance and emittance in a single value to represent a material's temperature in the sun. SRI quantifies how hot a surface would get relative to standard black and standard white surfaces. It is calculated using equations based on previously measured values of solar reflectance and emittance as laid out in the American Society for Testing and Materials Standard E 1980. In accordance with ASTM Standard E 1980, values of TSR
and TE are input into a standard equation to calculate the SRI value. In certain embodiments, the solar reflective index SRI is at least 65, for example, at least 70 or 75.
[0021] In accordance with embodiments of the invention, the coating composition comprises a latex resin. The latex resin may, or may not, be self-crosslinking. The latex resin typically comprises from 20 to 60 weight percent of the coating composition, for example, from about 30 to about 50 weight percent. In certain embodiments, suitable monomers used for preparing the latex resins may include vinyl aromatic monomers such as styrene, cycloaliphatic monomers such as cyclohexyl methacrylate, and long-chain aliphatic monomers such as 2-ethylhexyl acrylate, MMA and/or 2-ethylhexyl methacrylate. Other types of monomers include cyclohexene, 2-ethyl-1-hexene, cyclohexanol, alpha-methylstyrene, 2-ethylhexanol, 2-ethylhexyl acetate, methyl-4-phenyl butyrate, methyl myristate and/or methyl palmitate.
[0022] In certain embodiments, the monomers used in the latex resin comprise a vinyl aromatic compound, such as a vinyl aromatic monomer, which, in certain embodiments, comprises a compound that has a calculated Tg of least 100 C.
Specific examples of vinyl aromatic compounds are styrene (which has a calculated Tg of 100 C), a-methylstyrene (which has a calculated Tg of 168 C), vinyltoluene, p-methylstyrene, ethylvinylbenzene, vinylnaphthalene, vinylxylenes, a-methylstyrene dimer (meth)acrylate, penta fluoro styrene, and the like. In certain embodiments, styrene or another vinyl aromatic monomer may comprise the most predominant monomer of the resin on a weight percent basis.
[0023] In certain embodiments, the monomers of the latex resin include cycloaliphatic (meth)acrylate monomers, such as trimethylcyclohexyl acrylate, t-butyl cyclohexyl acrylate, dicyclopentadiene (meth)acrylate, trimethylcyclohexyl methacrylate (calculated Tg of 98 C), cyclohexyl methacrylate (calculated Tg of 83 C), isobornyl methacrylate (calculated Tg of 110 C), 2-ethylhexyl methacrylate, tetrahydrofurfuryl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate (calculated Tg of 125 C), and/or 4-t-butylcyclohexyl methacylate, and the like.
[0024] In certain embodiments, the monomers of the latex resin include an alkyl(meth)acrylate, which, in certain embodiments, comprises a compound that has a calculated Tg of least 100 C. Specific examples of alkyl(meth)acrylates are C1-alkyl(meth)acrylates, such as methyl(meth)acrylate (which has a calculated Tg of 105 C), propyl(meth)acrylate, butyl(meth)acrylate, isobutyl(meth)acrylate, hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, octyl(meth)acrylate, decyl(meth)acrylate, dodecyl(meth)acrylate, pentadecyl(meth)acrylate, hexadecyl(meth)acrylate, octadecyl(meth)acrylate, and nonadecyl(meth)acrylate, and mixtures thereof.
Other monomers include, for example, nitriles, such as acrylonitrile and/or methacrylonitrile.
[0025] Some non-limiting examples of latex resins that may be used in the coating compositions of the present invention are commercially available from Nuplex, Lubrizol, Rohm and Haas, Alberdingk Boley Company, Omnova and DSM Neoresins, such as Joncryl 1982, Caroboset CR-781, Alberdingk AC 2403, Alberdingk 2360, Neocryl XK-98 and the like.
[0026] The latex resin may have an average particle size of from 50 nm to 300 nm, for example from 60 nm to 100 or 150 nm; a glass transition temperature (TG) of from -20 to 100 C, typically from zero to 20 or 50 C; and an acid number of from 0 to 20, typically from 2 to 10.
[0027] The coating compositions of the present invention may be waterborne. In certain embodiments, water may comprise from 20 to 80 weight percent of the coating compositions, for example, from 50 to 65 weight percent. In certain embodiments, the coating compositions comprise less than 10 weight percent organic solvents, for example, less than 7 or 4 weight percent, based on the total weight of the composition.
The resin solids content of the coating compositions may be relatively high, for example, greater than 35 or 40 weight percent, based on the total weight of the composition.
[0028] The coating compositions may have little or no volatile organic content (VOC). For example, the coating compositions may comprise less than 1.5 weight percent VOCs, for example, less than 1 or 0.5 weight percent VOCs, based on the total weight of the composition. In certain embodiments, the coating compositions are substantially free of VOCs.
[0029] The coating compositions may further comprise at least one coalescing agent in an amount of up to 10 weight percent, for example, in an amount of from 2 to 3 weight percent, based on the total weight of the coating composition. Examples of suitable coalescing agents include butyl carbitol commercially available from Dow Chemical Company, DowanolTM DPM, DowanolTM DPnB, DowanolTM PPh, butyl cellosolve or DowanolTM DPnP. In accordance with embodiments of the present invention, the coalescing agents form a thin film around the latex resin particles, which helps them coalesce. Improved coalescence of the latex resin particles results in very fine particle sizes and a uniform microstructure, which provides improved corrosion , protection in comparison with other types of coatings having larger resin particle sizes.
For example, in accordance with certain embodiments of the present invention, the average resin particle size may be less than 150 nanometers, for example, less than 100 or 80 nanometers.
[0030] In certain embodiments, wax may be added to the coating compositions in amounts up to 10 weight percent, for example, from 0.5 to 3 weight percent, based on the total weight of the coating composition. Suitable types of wax include Ceraflour 913, Worleeadd 352, AquamatTM 272, AquamatTM 270, Aquacer 539, and combinations thereof. For example, wax sold under the designation AquamatTM 272 by BYK
Chemie may be used. The type and amount of wax may be controlled in order to improve scratch resistance of the coated sheet materials. For example, when the coated sheets are formed into coils, the use of wax additives may reduce or prevent scratching during the coiling an uncoiling processes, as well as during subsequent installation and use of the coated sheet materials. In certain embodiments, the amount of wax added to the coating composition is limited in order to avoid unwanted slippage when the coated sheets are coiled, e.g., to prevent unwanted "telescoping" of the coils due to low friction between the adjacent coil layers.
[0031] Various other additives may optionally be added to the coating compositions in accordance with certain embodiments of the invention. For example, suitable additives include thickeners, defoamers, surfactants, rust inhibitors, pH control agents, silica, and tints.
[0032] Suitable thickeners include AcrysolTM ASE-60, Aquatix 8421, DSX-1550, and Laponite RD. When used, such thickening agents may be present in amounts up to 7 weight percent, for example, from 0.5 to 4 weight percent, based on the total weight of the coating composition.
100331 Suitable defoamers include BYKTm-011, BYKTm-20, BYKTm-32, BYKTM
34 and DrewplusTM L-419 available from Ashland in amounts up to 2 weight percent, for example, from 0.1 to 0.5 weight percent, based on the total weight of the coating composition.
[0034] Suitable surfactants include ZOnY1TM FSP available from DuPont, Surfynol 104E available from Air Products, BYKTM 346, and BYKTM 348 in amounts up to 2 weight percent, for example, from 0.1 to 0.5 weight percent, based on the total weight of the coating composition.
[0035] Suitable rust inhibitors include HaloxTM 550, HaloxTM Flash X-150, 330, HaloxTM SZP-391, ammonium benzoate, and sodium nitrite in typical amounts up to 1 weight percent, for example, from 0.4 to 0.6 weight percent, based on the total weight of the coating composition.
[0036] In certain embodiments, the coating compositions are substantially free of certain metal salts such as metal phosphates, phosphocarbonates and phosphosilicates.
For example, the compositions may be substantially free of zinc phosphate, calcium phosphate, calcium phosphosilicate and/or calcium-enriched silica.
[0037] Suitable pH control agents include any water soluble amine such as dimethylethanol amine (DMEA) available from Avecia in typical amounts up to 1 weight percent, for example, from 0.01 to 0.2 weight percent, based on the total weight of the coating composition.
[0038] In accordance with certain embodiments of the invention, the coatings are substantially free of chrome. In such embodiments, chrome is not purposely added to the coating compositions and is only present in trace levels or as an impurity.
[0039] In certain embodiments, chromate-containing materials may be added to the coating compositions. Such chromate-containing coating compositions may be particularly useful as primer coatings. For example, strontium chromate may be added in amounts up to 12 weight percent, for example, from 0.2 to 1 weight percent, based on the total weight of the coating composition. Such strontium chromate-containing additives may provide improved corrosion resistance properties. When used as primer coatings, the coating compositions may further include colorants and tints typically used in primers, such as titanium dioxide and the like.
[0040] In certain embodiments, silica may be added to the coating compositions, for example, in amounts from 0.1 to 2 or 3 weight percent or more. Some examples of silica include LoVe1TM 275 silica from PPG Industries and AerosiITM 200 silica from Air Products.
[0041] In certain embodiments, the coating compositions and cured coatings are substantially free of reflective pigments. As used herein, the term "reflective pigment"
means plate-like or sheet-like interference pigments such as mica, silicates, silicon dioxide and aluminum oxide. Solarflair 9870 from Eckart is an example of a reflective pigment. As used herein, the term "substantially free of reflective pigments"
means that the coatings have zero or minimal amounts of reflective pigments while achieving the desired level of solar reflectance and/or solar reflective index. For example, the cured coatings may have less than 2 or 1 weight percent reflective pigment. Although the coatings may be substantially free of reflective pigments, they still maintain sufficient solar reflectance properties and solar reflective index values, e.g., SRIs of 65 or greater.
The cost of reflective pigment additives may thus be avoided, while still providing a desired level of solar reflectance.
[0042] In certain embodiments, at least one colored pigment or tint may be added to the coating compositions. Colored pigments and tints are different from reflective interference pigments and include standard inorganic and organic pigments, such as those found in conventional paints and primers. For example, various colored pigments are listed in the Dry Color Manufacturers Association (DCMA) classifications. Such colored pigments and tints typically comprise particles having substantially equiaxed morphologies, e.g., aspect ratios of about 1:1, in comparison with plate-like and sheet-like reflective interference pigments having relatively high aspect ratios.
One suitable type of colored pigment includes TiO2 in an amount up to 35 weight percent, for example, from 1 to 25 weight percent, based on the total weight of the coating composition. Aquext white tint commercially available from PPG Industries and Corrosperse 176E chrome tint commercially available from Wayne Pigments are examples of suitable tints.
[0043] In certain embodiments, the coating is substantially free of colored pigments and tints. For example, the coatings may be substantially clear and colorless.
[0044] In certain embodiments, conductive particles such as graphenic carbon particles may be added to the coating compositions in amounts of to 5 weight percent, for example, from 1 to 2 weight percent, based on the total weight of the coating composition. Such graphenic carbon particles may provide improved thermal emissivity properties. The graphenic carbon particles may be obtained from commercial sources, or may be made in accordance with the methods and apparatus described in U.S.
Patent Nos. 8,486,363 and 8,486,364. Exemplary commercially available graphenic carbon particles are available from Angstron and XG Sciences.
[0045] As used herein, the term "graphenic carbon particles" means carbon particles having structures comprising one or more layers of one-atom-thick planar sheets of sp2-bonded carbon atoms that are densely packed in a honeycomb crystal lattice. The average number of stacked layers may be less than 100, for example, less than 50. In certain embodiments, the average number of stacked layers is 30 or less, such as 20 or less, 10 or less, or, in some cases, 5 or less. The graphenic carbon particles may be substantially flat, however, at least a portion of the planar sheets may be substantially curved, curled, creased or buckled. The particles typically do not have a spheroidal or equiaxed morphology.
[0046] In certain embodiments, the graphenic carbon particles present in the compositions of the present invention have a thickness, measured in a direction perpendicular to the carbon atom layers, of no more than 10 nanometers, no more than 5 nanometers, or, in certain embodiments, no more than 4 or 3 or 2 or 1 nanometers, such as no more than 3.6 nanometers. In certain embodiments, the graphenic carbon particles may be from 1 atom layer up to 3, 6, 9, 12, 20 or 30 atom layers thick, or more. In certain embodiments, the graphenic carbon particles present in the compositions of the present invention have a width and length, measured in a direction parallel to the carbon atoms layers, of at least 50 nanometers, such as more than 100 nanometers, in some cases more than 100 nanometers up to 500 nanometers, or more than 100 nanometers up to 200 nanometers. The graphenic carbon particles may be provided in the form of ultrathin flakes, platelets or sheets having relatively high aspect ratios (aspect ratio being defined as the ratio of the longest dimension of a particle to the shortest dimension of the particle) of greater than 3:1, such as greater than 10:1.
[0047] In certain embodiments, the graphenic carbon particles used in the compositions of the present invention have relatively low oxygen content. For example, the graphenic carbon particles used in certain embodiments of the compositions of the present invention may, even when having a thickness of no more than 5 or no more than 2 nanometers, have an oxygen content of no more than 2 atomic weight percent, such as no more than 1.5 or 1 atomic weight percent, or no more than 0.6 atomic weight, such as about 0.5 atomic weight percent. The oxygen content of the graphenic carbon particles can be determined using X-ray Photoelectron Spectroscopy, such as is described in D. R.
Dreyer et al., Chem. Soc. Rev. 39, 228-240 (2010).
[0048] In certain embodiments, the graphenic carbon particles used in the compositions of the present invention have a B.E.T. specific surface area of at least 50 square meters per gram, such as 70 to 1000 square meters per gram, or, in some cases, 200 to 1000 square meters per grams or 200 to 400 square meters per gram. As used herein, the term "B.E.T. specific surface area" refers to a specific surface area determined by nitrogen adsorption according to the ASTMD 3663-78 standard based on the Brunauer-Emmett-Teller method described in the periodical "The Journal of the American Chemical Society", 60, 309 (1938).
[0049] In certain embodiments, the graphenic carbon particles used in the compositions of the present invention have a Raman spectroscopy 2D/G peak ratio of at least 1.1, for example, at least 1.2 or 1.3. As used herein, the term "2D/G
peak ratio"
refers to the ratio of the intensity of the 2D peak at 2692 cm-1 to the intensity of the G
peak at 1,580 cm-I.
[0050] In certain embodiments, the graphenic carbon particles used in the compositions of the present invention have a relatively low bulk density. For example, the graphenic carbon particles used in certain embodiments of the present invention are characterized by having a bulk density (tap density) of less than 0.2 g/cm3, such as no more than 0.1 g/cm3. For the purposes of the present invention, the bulk density of the graphenic carbon particles is determined by placing 0.4 grams of the graphenic carbon particles in a glass measuring cylinder having a readable scale. The cylinder is raised approximately one-inch and tapped 100 times, by striking the base of the cylinder onto a hard surface, to allow the graphenic carbon particles to settle within the cylinder. The volume of the particles is then measured, and the bulk density is calculated by dividing 0.4 grams by the measured volume, wherein the bulk density is expressed in terms of g/cm3.
[0051] In certain embodiments, the graphenic carbon particles used in the compositions of the present invention have a compressed density and a percent densification that is less than the compressed density and percent densification of graphite powder and certain types of substantially flat graphenic carbon particles. Lower compressed density and lower percent densification are each currently believed to contribute to better dispersion and/or rheological properties than graphenic carbon particles exhibiting higher compressed density and higher percent densification. In certain embodiments, the compressed density of the graphenic carbon particles is 0.9 or less, such as less than 0.8, less than 0.7, such as from 0.6 to 0.7. In certain embodiments, the percent densification of the graphenic carbon particles is less than 40%, such as less than 30%, such as from 25 to 30%.
[0052] For purposes of the present invention, the compressed density of graphenic carbon particles is calculated from a measured thickness of a given mass of the particles after compression. Specifically, the measured thickness is determined by subjecting 0.1 grams of the graphenic carbon particles to cold press under 15,000 pound of force in a 1.3 centimeter die for 45 minutes, wherein the contact pressure is 500 MPa.
The compressed density of the graphenic carbon particles is then calculated from this measured thickness according to the following equation:
Compressed Density (g/cm3) = 0.1 grams I1*(1.3cm/2)2*(measured thickness in cm) [0053] The percent densification of the graphenic carbon particles is then determined as the ratio of the calculated compressed density of the graphenic carbon particles, as determined above, to 2.2 g/cm3, which is the density of graphite.
[0054] In certain embodiments, the graphenic carbon particles have a measured bulk liquid conductivity of at least 100 microSiemens, such as at least 120 microSiemens, such as at least 140 microSiemens immediately after mixing and at later points in time, such as at 10 minutes, or 20 minutes, or 30 minutes, or 40 minutes. For the purposes of the present invention, the bulk liquid conductivity of the graphenic carbon particles is determined as follows. First, a sample comprising a 0.5% solution of graphenic carbon particles in butyl cellosolve is sonicated for 30 minutes with a bath sonicator.
Immediately following sonication, the sample is placed in a standard calibrated electrolytic conductivity cell (K=1). A Fisher Scientific AB 30 conductivity meter is introduced to the sample to measure the conductivity of the sample. The conductivity is plotted over the course of about 40 minutes.
[0055] In accordance with certain embodiments, percolation, defined as long range interconnectivity, occurs between the conductive graphenic carbon particles. Such percolation may reduce the resistivity of the coating compositions. The conductive graphenic particles may occupy a minimum volume within the coating such that the particles form a continuous, or nearly continuous, network. In such a case, the aspect ratios of the graphenic carbon particles may affect the minimum volume required for percolation. Furthermore, the surface energy of the graphenic carbon particles may be the same or similar to the surface energy of the elastomeric rubber.
Otherwise, the particles may tend to flocculate or demix as they are processed.
[0056] The graphenic carbon particles utilized in the compositions of the present invention can be made, for example, by thermal processes. In accordance with embodiments of the invention, the graphenic carbon particles are produced from carbon-containing precursor materials that are heated to high temperatures in a thermal zone.
For example, the graphenic carbon particles may be produced by the systems and methods disclosed in United States Patent Nos. 8,486,363 and 8,486,364.
[0057] In certain embodiments, the graphenic carbon particles may be made by using the apparatus and method described in United States Patent No. 8,486,363 at [0022]
to [0048] in which (i) one or more hydrocarbon precursor materials capable of forming a two-carbon fragment species (such as n-propanol, ethane, ethylene, acetylene, vinyl chloride, 1,2-dichloroethane, allyl alcohol, propionaldehyde, and/or vinyl bromide) is introduced into a thermal zone (such as a plasma); and (ii) the hydrocarbon is heated in the thermal zone to a temperature of at least 1,000 C to form the graphenic carbon particles. In other embodiments, the graphenic carbon particles may be made by using the apparatus and method described in United States Patent No. 8,486,364 at [0015] to [0042] in which (i) a methane precursor material (such as a material comprising at least 50 percent methane, or, in some cases, gaseous or liquid methane of at least 95 or 99 percent purity or higher) is introduced into a thermal zone (such as a plasma); and (ii) the methane precursor is heated in the thermal zone to form the graphenic carbon particles.
Such methods can produce graphenic carbon particles having at least some, in some cases all, of the characteristics described above.
[0058] During production of the graphenic carbon particles by the methods described above, a carbon-containing precursor is provided as a feed material that may be contacted with an inert carrier gas. The carbon-containing precursor material may be heated in a thermal zone, for example, by a plasma system. In certain embodiments, the precursor material is heated to a temperature ranging from 1,000 C to 20,000 C, such as 1,200 C to 10,000 C. For example, the temperature of the thermal zone may range from 1,500 to 8,000 C, such as from 2,000 to 5,000 C. Although the thermal zone may be generated by a plasma system, it is to be understood that any other suitable heating system may be used to create the thermal zone, such as various types of furnaces including electrically heated tube furnaces and the like.
[0059] The gaseous stream may be contacted with one or more quench streams that are injected into the plasma chamber through at least one quench stream injection port. The quench stream may cool the gaseous stream to facilitate the formation or control the particle size or morphology of the graphenic carbon particles. In certain embodiments of the invention, after contacting the gaseous product stream with the quench streams, the ultrafine particles may be passed through a converging member.
After the graphenic carbon particles exit the plasma system, they may be collected. Any suitable means may be used to separate the graphenic carbon particles from the gas flow, such as, for example, a bag filter, cyclone separator or deposition on a substrate.
[0060] Without being bound by any theory, it is currently believed that the foregoing methods of manufacturing graphenic carbon particles are particularly suitable for producing graphenic carbon particles having relatively low thickness and relatively high aspect ratio in combination with relatively low oxygen content, as described above.
Moreover, such methods are currently believed to produce a substantial amount of graphenic carbon particles having a substantially curved, curled, creased or buckled morphology (referred to herein as a "3D" morphology), as opposed to producing predominantly particles having a substantially two-dimensional (or flat) morphology.
This characteristic is believed to be reflected in the previously described compressed density characteristics and is believed to be beneficial in the present invention because, it is currently believed, when a significant portion of the graphenic carbon particles have a 3D morphology, "edge to edge" and "edge-to-face" contact between graphenic carbon particles within the composition may be promoted. This is thought to be because particles having a 3D morphology are less likely to be aggregated in the composition (due to lower Van der Waals forces) than particles having a two-dimensional morphology.
Moreover, it is currently believed that even in the case of "face to face"
contact between the particles having a 3D morphology, since the particles may have more than one facial plane, the entire particle surface is not engaged in a single "face to face"
interaction with another single particle, but instead can participate in interactions with other particles, including other "face to face" interactions, in other planes. As a result, graphenic carbon particles having a 3D morphology are currently thought to provide the best conductive pathway in the present compositions and are currently thought to be useful for obtaining electrical conductivity characteristics sought by the present invention, particularly when the graphenic carbon particles are present in the composition in relatively low amounts.
[0061] Fig. 2 schematically illustrates a roll coating method for applying coating compositions onto sheet materials in accordance with an embodiment of the present invention. In the embodiment shown, the coating operation may be conducted in a conventional rolling mill. Metal sheet material, such as galvanized steel or the like, is provided in a long strip 5 that passes under oppositely-rotating coating rollers 20 and 22, which are fed with a supply of a coating composition 24. The uncoated strip 5 passes =
under the coating rollers 20 and 22, where a layer of the coating composition 24 is deposited on the upper surface of the sheet material. The coated sheet material 10 may be formed into a coil 26 for storage and transportation for use in various applications, such as galvanized steel roof sheeting.
[0062] During the roll coating process, the coating composition is typically applied to the sheet material 5 with a wet film thickness of at least 1 micron, typically at least 1 or 5 microns. In certain embodiments, the wet film thickness of the coating material is from 5 to 15 or 20 microns. In certain embodiments, the deposition rate of the coating composition may be at least 200 ft/min, typically at least 300 ft/min or 350 ft/min.
[0063] After application, the coating compositions typically dry and cure quickly with minimal VOC emissions. Curing times are typically in less than 1 minute, for example, less than 10 or 5 seconds. Typical curing temperatures are below 300 F, for example, below 275 or 250 F. In certain embodiments, curing times may be less than 3 or 2 seconds at temperatures of 225 F or 200 F, or less.
[0064] The dry film thickness of the cured coating is typically at least 1 micron up to 15 or 20 microns. For example, the dry film thickness may be from 5 to microns. In accordance with the present invention, such relatively thin coating layers have been found to significantly increase the solar reflective index of metal roof sheeting materials.
[0065] The following examples illustrate various aspects of the present invention, but are not intended to limit the scope of the invention.
EXAMPLES
[0066] Coating compositions were prepared and tested as described in Tables 1-below.
Table 1 Coating Composition Nos. 1-3 Components Sample No. Sample No. 2 Sample No.
Acrylic Latex Resin 198.10 199.18 165.41 Deionized Water 15.23 17.84 85.30 Defoamer 0.48 0.48 0.51 Surfynol Surfactant 1.04 1.04 1.06 Surfactant 1.04 1.04 1.06 Coalescing Agent 10.01 10.01 10.15 Chrome Tint 5.98 5.98 White Tint 154.63 Rust Inhibitor 2.41 2.43 2.46 Thickener 3.55 3.55 5.36 Deionized Water 3.55 3.55 0.54 pH Control Agent 0.53 0.53 0.54 Deionized Water 0.53 0.53 0.54 Wax 3.64 3.64 10.52 Total Weight in Grams 246.09 243.82 444.06 Table 2 Coating Composition No. 4 Components Sample No. 4 Latex Resin 201.14 UC Intermediate' 22.27 Deionized Water 3.70 Defoamer 0.13 Rust Inhibitor Pigment 8.05 Surfactant 0.24 Silica 1.08 Deionized Water 0.10 Total Weight in Grams 236.62 I Acrylic Emulsion Joncryl 538 (98.88); Defoamer (0.74); Deionized Water (5.0); Silica (25.11); Corrosion Pigment (49.78); Reflective Pigment (25.11); and Defoamer (0.26).
100671 The components listed in Tables 1 and 2 above were added together in the order described in each table under gentle stirring. The coating compositions were allowed to equilibrate overnight before panel preparation. Viscosity and pH
were checked the next day. The coating compositions were applied to galvanized steel substrates using a wire drawdown bar. The coated panels were placed in a conveyor oven set at a temperature to obtain a peak metal temperature of 190 F in two seconds dwell time (line speed). The coated panels were tested, with the results shown in Table 3 below.
Table 3 Test Results Sample No. 1 Sample No. 2 Sample No. 3 Sample No. 4 % Weight Solids 41.82 41.62 45.0 44.03 Viscosity (Seconds) 10-15 10-15 12-20 9-25 (measured using #4 Zahn Cup at room temperature) Dry Film Thickness 0.15-0.20 0.15-0.20 0.4-0.5 (mils) 0.15-0.25 (mils) (mils) (mils) 10.2-12.7 3.8-6.4 (microns) 3.8-5.1 3.8-5.1 (microns) (microns) (microns) Pencil Hardness HB-F HB-F HB-F
T-Bendl 1/3 np/nc 1/3 np/nc 1/3 np/nc 1/3 np/nc Reverse Impact2 Pass Pass Pass Pass X-Hatch Adhesion3 Pass Pass Pass Pass Butler Immersion No Corrosion No Corrosion No Corrosion Corrosion ¨ fail Salt Spray No Black Spots No Black Spots No Black Spots Corrosion ¨ fail Wet Stack No Pressure No Pressure No Pressure Pressure Mottling Mottling Mottling mottling, black spots TSR (%) 66.8 65 70.7 66.8 TE (%) 54 58 78 54 100681 In accordance with the pencil hardness test, ASTM D3363, a pencil is held firmly against the coating at a 45 degree angle and pushed away from the operator in a 0.25 inch stroke. Sufficient pressure is exerted downward and forward either to cut or scratch the film. The process is repeated down the hardness scale until a pencil is found that will not cut through the film to the substrate. The scale of hardness is:
6B (very soft) up to a 6H (very hard).
- 18 -[0069] In accordance with the Butler immersion test, ASTM D870, panels with cut edges are placed in a cup of covered tap water, and placed in a humidity cabinet 100F/100% humidity, for 1000 hours. The panels are then removed from the water, and visually evaluated for any red or white rust, black spots and or blisters on the faces and edges of the panels.
[0070] In accordance with the salt spray test, ASTM B117, panels are placed with taped cut edges in a 95F/5% NaC1 solution cabinet for 1000 hours. The panels are then removed from the cabinet and visually evaluated for any red or white rust, black spots and blister defects on the faces of the panels.
[0071] In accordance with the wet stack test, ASTM D7376-10A, panels are sprayed with DI-water, stacked face to face, and clipped together in a bundle to simulate a wound coil. The bundles are placed in a 100F/100% humidity cabinet for 1000 hours.
The bundles are then removed and visually evaluated for dark stains or white stains (pressure mottling).
[0072] Galvanized steel panels coated with compositions similar to Sample Nos.
1 and 2 described above were tested for TSR, TE and SRI properties at various dry film thicknesses (DFT). The results are shown in the plots of Figs. 3, 4 and 5.
[0073] Galvanized steel panels coated with compositions similar to Sample Nos.
1 and 2 described above, but with additions of interference pigment available from Eckart under the designation SolarFlair in an amount of 5 weight percent based on the total weight of the coating composition, were tested for TSR, TE and SRI properties at various dry film thicknesses (DFT). The results are shown in the plots of Figs. 6, 7 and 8.
[0074] Different types of graphenic carbon were added in an amount of 1 weight percent to coating compositions similar to Sample No. 1 above. Sample No. 5 included graphenic carbon particles produced in accordance with U.S. Patent No.
8,486,364.
Sample No. 6 included commercially available graphenic carbon particles from Angstron sold under the designation N-006-010-P. Sample No. 7 included commercially available graphenic carbon particles from XG Sciences sold under the designation X-GNP-M-25.
Panels were prepared by drawdown on a galvanized steel substrate at a film thickness of
[0070] In accordance with the salt spray test, ASTM B117, panels are placed with taped cut edges in a 95F/5% NaC1 solution cabinet for 1000 hours. The panels are then removed from the cabinet and visually evaluated for any red or white rust, black spots and blister defects on the faces of the panels.
[0071] In accordance with the wet stack test, ASTM D7376-10A, panels are sprayed with DI-water, stacked face to face, and clipped together in a bundle to simulate a wound coil. The bundles are placed in a 100F/100% humidity cabinet for 1000 hours.
The bundles are then removed and visually evaluated for dark stains or white stains (pressure mottling).
[0072] Galvanized steel panels coated with compositions similar to Sample Nos.
1 and 2 described above were tested for TSR, TE and SRI properties at various dry film thicknesses (DFT). The results are shown in the plots of Figs. 3, 4 and 5.
[0073] Galvanized steel panels coated with compositions similar to Sample Nos.
1 and 2 described above, but with additions of interference pigment available from Eckart under the designation SolarFlair in an amount of 5 weight percent based on the total weight of the coating composition, were tested for TSR, TE and SRI properties at various dry film thicknesses (DFT). The results are shown in the plots of Figs. 6, 7 and 8.
[0074] Different types of graphenic carbon were added in an amount of 1 weight percent to coating compositions similar to Sample No. 1 above. Sample No. 5 included graphenic carbon particles produced in accordance with U.S. Patent No.
8,486,364.
Sample No. 6 included commercially available graphenic carbon particles from Angstron sold under the designation N-006-010-P. Sample No. 7 included commercially available graphenic carbon particles from XG Sciences sold under the designation X-GNP-M-25.
Panels were prepared by drawdown on a galvanized steel substrate at a film thickness of
- 19 -microns. The panels were then cured at peak metal temperature of 190 F for 2 seconds using a conveyer oven. The panels were tested, with the results shown below in Table 4.
Table 4 Test Results Salt Sample Graphene Diameter Thickness TSR TE SRI
Spray ¨
No. Graphene Type (microns) (nm) 1000h 1 0% NA NA NA 66.3 0.55 70 Excellent 5 1% Graphenic 59.7 0.54 59 very few Carbon blisters Particles 6 1% Commercially <14 10-20 42.2 0.72 41 Excellent available graphenic carbon 7 1% Commercially 25 6 59.5 0.56 60 dense available blisters graphenic carbon [0075] For purposes of this detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
[0076] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the
Table 4 Test Results Salt Sample Graphene Diameter Thickness TSR TE SRI
Spray ¨
No. Graphene Type (microns) (nm) 1000h 1 0% NA NA NA 66.3 0.55 70 Excellent 5 1% Graphenic 59.7 0.54 59 very few Carbon blisters Particles 6 1% Commercially <14 10-20 42.2 0.72 41 Excellent available graphenic carbon 7 1% Commercially 25 6 59.5 0.56 60 dense available blisters graphenic carbon [0075] For purposes of this detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
[0076] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the
- 20 -specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard variation found in their respective testing measurements.
[0077] Also, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of "1 to 10" is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.
[0078] In this application, the use of the singular includes the plural and plural encompasses singular, unless specifically stated otherwise. In addition, in this application, the use of "or" means "and/or" unless specifically stated otherwise, even though "and/or" may be explicitly used in certain instances.
[0079] It will be readily appreciated by those skilled in the art that modifications may be made to the invention without departing from the concepts disclosed in the foregoing description. Such modifications are to be considered as included within the following claims unless the claims, by their language, expressly state otherwise.
Accordingly, the particular embodiments described in detail herein are illustrative only and are not limiting to the scope of the invention which is to be given the full breadth of the appended claims and any and all equivalents thereof.
[0077] Also, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of "1 to 10" is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.
[0078] In this application, the use of the singular includes the plural and plural encompasses singular, unless specifically stated otherwise. In addition, in this application, the use of "or" means "and/or" unless specifically stated otherwise, even though "and/or" may be explicitly used in certain instances.
[0079] It will be readily appreciated by those skilled in the art that modifications may be made to the invention without departing from the concepts disclosed in the foregoing description. Such modifications are to be considered as included within the following claims unless the claims, by their language, expressly state otherwise.
Accordingly, the particular embodiments described in detail herein are illustrative only and are not limiting to the scope of the invention which is to be given the full breadth of the appended claims and any and all equivalents thereof.
-21 -
Claims (17)
1. A coated metal sheet comprising:
a metal substrate; and a cured coating covering at least a portion of the metal substrate, wherein:
(a) the cured coating:
(i) is deposited from a composition comprising a latex resin, (ii) is clear, (iii) comprises 0 to less than 1 wt. % of reflective pigments, and (iv) has a dry film thickness of at least 1 micron; and (b) the coated metal sheet has a solar reflective index of at least 65 measured according to ASTM Standard E 1980 and a corrosion resistance of at least 500h with no corrosion spots when subjected to an ASTM B117 salt spray test.
a metal substrate; and a cured coating covering at least a portion of the metal substrate, wherein:
(a) the cured coating:
(i) is deposited from a composition comprising a latex resin, (ii) is clear, (iii) comprises 0 to less than 1 wt. % of reflective pigments, and (iv) has a dry film thickness of at least 1 micron; and (b) the coated metal sheet has a solar reflective index of at least 65 measured according to ASTM Standard E 1980 and a corrosion resistance of at least 500h with no corrosion spots when subjected to an ASTM B117 salt spray test.
2. The coated metal sheet of Claim 1, wherein the latex resin is self-crosslinking.
3. The coated metal sheet of Claim 1, wherein the latex resin is prepared from at least one vinyl aromatic monomer.
4. The coated metal sheet of Claim 1, wherein the latex resin has an average particle size of from 50 to 300 nm.
5. The coated metal sheet of Claim 1, wherein the dry film thickness is at least 2 microns.
6. The coated metal sheet of Claim 1, wherein the dry film thickness is from 3 to 20 microns.
7. The coated metal sheet of Claim 1, wherein the cured coating further comprises a coalescing agent, wax, viscosity enhancing agent and/or a thickening agent.
8. The coated metal sheet of Claim 1, wherein the cured coating further comprises from 0.5 to 3 weight percent wax.
9. The coated metal sheet of Claim 1, wherein the cured coating is free of chrome.
10. The coated metal sheet of Claim 1, wherein the cured coating is free of metal phosphate.
11. The coated metal sheet of Claim 1, wherein the cured coating further comprises graphenic carbon particles.
12. The coated metal sheet of Claim 11, wherein the cured coating comprises up to 5 weight percent of the graphenic carbon particles.
13. The coated metal sheet of Claim 1, wherein the metal is in the form of a coil.
14. The coated metal sheet of Claim 1, wherein the metal substrate comprises a metal roofing sheet.
15. The coated metal sheet of Claim 1, wherein the metal substrate comprises galvanized steel.
16. The coated metal sheet of Claim 1, wherein the coated metal sheet has a solar reflective index of at least 65 measured according to ASTM Standard E 1980.
17. The coated metal sheet of Claim 1, wherein the coated metal sheet has a thermal emittance of at least 40 percent measured according to ASTM Standard E 1980.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201261661532P | 2012-06-19 | 2012-06-19 | |
| US61/661,532 | 2012-06-19 | ||
| US13/786,516 US20130337258A1 (en) | 2012-06-19 | 2013-03-06 | Coated sheet materials having high solar reflective index and corrosion resistance, and methods of making same |
| US13/786,516 | 2013-03-06 | ||
| PCT/US2013/046324 WO2013192180A2 (en) | 2012-06-19 | 2013-06-18 | Coated sheet materials having high solar reflective index and corrosion resistance, and methods of making same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2877139A1 CA2877139A1 (en) | 2013-12-27 |
| CA2877139C true CA2877139C (en) | 2017-11-07 |
Family
ID=49756179
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2877139A Expired - Fee Related CA2877139C (en) | 2012-06-19 | 2013-06-18 | Coated sheet materials having high solar reflective index and corrosion resistance, and methods of making same |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US20130337258A1 (en) |
| EP (1) | EP2861680A2 (en) |
| CN (2) | CN108559328A (en) |
| AU (1) | AU2013277333B2 (en) |
| CA (1) | CA2877139C (en) |
| HK (1) | HK1204644A1 (en) |
| IN (1) | IN2014DN10769A (en) |
| MY (1) | MY167799A (en) |
| NZ (1) | NZ703067A (en) |
| SG (2) | SG10201609098QA (en) |
| WO (1) | WO2013192180A2 (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8486363B2 (en) | 2011-09-30 | 2013-07-16 | Ppg Industries Ohio, Inc. | Production of graphenic carbon particles utilizing hydrocarbon precursor materials |
| US9832818B2 (en) | 2011-09-30 | 2017-11-28 | Ppg Industries Ohio, Inc. | Resistive heating coatings containing graphenic carbon particles |
| US9938416B2 (en) | 2011-09-30 | 2018-04-10 | Ppg Industries Ohio, Inc. | Absorptive pigments comprising graphenic carbon particles |
| US10240052B2 (en) | 2011-09-30 | 2019-03-26 | Ppg Industries Ohio, Inc. | Supercapacitor electrodes including graphenic carbon particles |
| US10294375B2 (en) | 2011-09-30 | 2019-05-21 | Ppg Industries Ohio, Inc. | Electrically conductive coatings containing graphenic carbon particles |
| US9988551B2 (en) | 2011-09-30 | 2018-06-05 | Ppg Industries Ohio, Inc. | Black pigments comprising graphenic carbon particles |
| US9761903B2 (en) | 2011-09-30 | 2017-09-12 | Ppg Industries Ohio, Inc. | Lithium ion battery electrodes including graphenic carbon particles |
| US9475946B2 (en) | 2011-09-30 | 2016-10-25 | Ppg Industries Ohio, Inc. | Graphenic carbon particle co-dispersions and methods of making same |
| US10763490B2 (en) | 2011-09-30 | 2020-09-01 | Ppg Industries Ohio, Inc. | Methods of coating an electrically conductive substrate and related electrodepositable compositions including graphenic carbon particles |
| US20160297973A9 (en) * | 2012-06-19 | 2016-10-13 | Ppg Industries Ohio, Inc. | Primer compositions for application to sheet materials and methods of applying same |
| SG11201502325SA (en) * | 2012-09-28 | 2015-04-29 | Ppg Ind Ohio Inc | Electrically conductive coatings containing graphenic carbon particles |
| DE102013004611B4 (en) | 2013-03-14 | 2014-12-24 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Coating, process for its preparation and its use |
| EP3114415B1 (en) | 2014-03-07 | 2023-06-28 | Zinniatek Limited | Solar thermal roofing system |
| WO2015152343A1 (en) * | 2014-04-03 | 2015-10-08 | 電気化学工業株式会社 | Cross-copolymer, and resin composition |
| US20150326176A1 (en) * | 2014-05-08 | 2015-11-12 | Sunplicity LLC | System and method of rooftop solar energy production |
| CN106062095A (en) * | 2014-10-23 | 2016-10-26 | 亮源产业（以色列）有限公司 | High-temperature solar-absorptive coatings with high thermal conductivity and low emissivity, and methods for use thereof |
| WO2016099466A1 (en) * | 2014-12-16 | 2016-06-23 | Boral Ip Holdings (Australia) Pty Limited | Reflective coating films and methods of making and using the same |
| CN105514188B (en) * | 2015-12-25 | 2017-10-03 | 中国科学院上海高等研究院 | A kind of antireflective self-cleaning film and preparation method thereof |
| EP3585955B1 (en) * | 2017-02-21 | 2024-10-09 | Zinniatek Limited | Substrate having decorated surface and method of production |
| WO2022272115A1 (en) * | 2021-06-24 | 2022-12-29 | Bmic Llc | Building materials comprising graphene and related methods |
| MX2022008284A (en) | 2021-07-01 | 2023-01-02 | Bmic Llc | Graphene-containing roofing materials and related methods. |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT352843B (en) * | 1978-04-27 | 1979-10-10 | Vianova Kunstharz Ag | PROCESS FOR THE PREPARATION OF AQUATIC COATING EMULSIONS |
| US4313861A (en) * | 1980-02-28 | 1982-02-02 | Union Carbide Corporation | Latex autodeposition coatings |
| JPS60102978A (en) * | 1983-11-11 | 1985-06-07 | Nippon Light Metal Co Ltd | Blank member having hydrophilic film |
| US20050004272A1 (en) * | 2003-06-23 | 2005-01-06 | Thauming Kuo | Small-particle latex compositions based on waterborne alkyd seeds |
| JP4791490B2 (en) * | 2006-02-02 | 2011-10-12 | 三菱樹脂株式会社 | Solar cell backsheet |
| DE102007011553A1 (en) * | 2007-03-09 | 2008-09-11 | Chemetall Gmbh | A method of coating metallic surfaces with an aqueous polymer-containing composition, the aqueous composition, and the use of the coated substrates |
| CN101815761A (en) * | 2007-10-02 | 2010-08-25 | 巴斯夫公司 | A coating composition and a reflective coating system including same |
| EP2240405A4 (en) * | 2008-02-05 | 2011-06-15 | John M Crain | Coatings containing functionalized graphene sheets and articles coated therewith |
| WO2009134907A1 (en) * | 2008-04-30 | 2009-11-05 | James Stephens | Shingle and method of using the shingle |
| US8361611B2 (en) * | 2009-03-20 | 2013-01-29 | Whiteoptics Llc | Diffusively light reflective paint composition, method for making paint composition, and diffusively light reflective articles |
| US11142654B2 (en) * | 2010-11-03 | 2021-10-12 | Chemetall Gmbh | Composition and process for the generation of a clear or translucent emissive coating |
-
2013
- 2013-03-06 US US13/786,516 patent/US20130337258A1/en not_active Abandoned
- 2013-06-18 CN CN201810425644.3A patent/CN108559328A/en not_active Withdrawn
- 2013-06-18 NZ NZ703067A patent/NZ703067A/en not_active IP Right Cessation
- 2013-06-18 WO PCT/US2013/046324 patent/WO2013192180A2/en active Application Filing
- 2013-06-18 IN IN10769DEN2014 patent/IN2014DN10769A/en unknown
- 2013-06-18 CA CA2877139A patent/CA2877139C/en not_active Expired - Fee Related
- 2013-06-18 SG SG10201609098QA patent/SG10201609098QA/en unknown
- 2013-06-18 CN CN201380038265.4A patent/CN104470996A/en active Pending
- 2013-06-18 EP EP13736684.5A patent/EP2861680A2/en not_active Withdrawn
- 2013-06-18 HK HK15105250.7A patent/HK1204644A1/en unknown
- 2013-06-18 SG SG11201408424VA patent/SG11201408424VA/en unknown
- 2013-06-18 MY MYPI2014003480A patent/MY167799A/en unknown
- 2013-06-18 AU AU2013277333A patent/AU2013277333B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| CN104470996A (en) | 2015-03-25 |
| AU2013277333B2 (en) | 2015-07-16 |
| HK1204644A1 (en) | 2015-11-27 |
| CA2877139A1 (en) | 2013-12-27 |
| CN108559328A (en) | 2018-09-21 |
| EP2861680A2 (en) | 2015-04-22 |
| IN2014DN10769A (en) | 2015-09-04 |
| WO2013192180A3 (en) | 2014-04-03 |
| NZ703067A (en) | 2016-01-29 |
| AU2013277333A1 (en) | 2015-01-22 |
| SG11201408424VA (en) | 2015-01-29 |
| WO2013192180A2 (en) | 2013-12-27 |
| MY167799A (en) | 2018-09-26 |
| US20130337258A1 (en) | 2013-12-19 |
| SG10201609098QA (en) | 2016-12-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2877139C (en) | Coated sheet materials having high solar reflective index and corrosion resistance, and methods of making same | |
| EP1328589B1 (en) | Method for coating metal surfaces with an aqueous, polymer-containing composition, said aqueous composition and the use of the coated substrates | |
| AU2011325325B2 (en) | Coating composition comprising a sheet silicate pigment and process for the generation of a clear or translucent emissive coating | |
| Huang et al. | Preparation and characterization of silica/fluorinated acrylate copolymers hybrid films and the investigation of their icephobicity | |
| US9732237B2 (en) | Coating composition, and method for forming coating film | |
| MX2008002629A (en) | Coating compositions exhibiting corrosion resistance properties, related coated substrates, and methods. | |
| KR20120074841A (en) | Plate type zirconium phosphate and preparation method thereof | |
| US20180002532A1 (en) | Aqueous corrosion resistant coatings with surface-hydrophobic inorganic particles | |
| US8038786B2 (en) | Composition for cutting off heat-ray, film formed therefrom, and method for forming the composition and the film | |
| Amin et al. | Covalent polymer functionalization of graphene/graphene oxide and its application as anticorrosion materials | |
| KR101949000B1 (en) | Primer compositions for application to sheet materials and methods of applying same | |
| Al-Dulaimi et al. | Corrosion protection of carbon steel using polyaniline composite with inorganic pigments | |
| US20170137638A1 (en) | Films and coatings containing borosilicate flake glass | |
| Zhu et al. | Flaky polyacrylic acid/aluminium composite particles prepared using in-situ polymerization | |
| KR101858336B1 (en) | Lustrous coating material composition, lustrous resin film, and multilayer coating film | |
| JP7062596B2 (en) | Water-based corrosion resistant coating composition | |
| CN103436061A (en) | Environment-friendly nano power cable anticorrosive paint | |
| JP5719232B2 (en) | Glittering paint composition, glittering resin film and laminated coating film | |
| Ren et al. | Deposition of colored inorganic coating layers on lamellar sericite surface and the pigmentary performances | |
| WO2018130176A1 (en) | Composition for thermal insulation coating | |
| CN104250461B (en) | A kind of automobile external-use coating and preparation method thereof | |
| KR101645063B1 (en) | Plate type zirconium phosphate and preparation method thereof | |
| Rodrigues et al. | Development of PMMA-CeO2 anticorrosive hybrid coatings with self-healing property | |
| KR102722765B1 (en) | Paint composition for steel sheet of automobile having improved property | |
| Caselis et al. | Preparation and characterization of UV-cured epoxy/clay nanocomposite coatings on carbon steel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request |
Effective date: 20141217 |
|
| MKLA | Lapsed |
Effective date: 20210618 |