JP7425076B2 - Two-component paint composition - Google Patents
Two-component paint composition Download PDFInfo
- Publication number
- JP7425076B2 JP7425076B2 JP2021546522A JP2021546522A JP7425076B2 JP 7425076 B2 JP7425076 B2 JP 7425076B2 JP 2021546522 A JP2021546522 A JP 2021546522A JP 2021546522 A JP2021546522 A JP 2021546522A JP 7425076 B2 JP7425076 B2 JP 7425076B2
- Authority
- JP
- Japan
- Prior art keywords
- coating
- coating composition
- film
- note
- epoxy resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003973 paint Substances 0.000 title claims description 45
- 239000000203 mixture Substances 0.000 title claims description 38
- 238000000576 coating method Methods 0.000 claims description 84
- 239000011248 coating agent Substances 0.000 claims description 79
- 239000008199 coating composition Substances 0.000 claims description 62
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 61
- 150000001875 compounds Chemical class 0.000 claims description 50
- 239000005056 polyisocyanate Substances 0.000 claims description 48
- 229920001228 polyisocyanate Polymers 0.000 claims description 48
- 239000003822 epoxy resin Substances 0.000 claims description 41
- 229920000647 polyepoxide Polymers 0.000 claims description 41
- 239000010457 zeolite Substances 0.000 claims description 29
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 28
- 229910021536 Zeolite Inorganic materials 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 23
- -1 fatty acid amine-modified epoxy resins Chemical class 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 20
- 239000011148 porous material Substances 0.000 claims description 19
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 8
- 239000000194 fatty acid Substances 0.000 claims description 8
- 229930195729 fatty acid Natural products 0.000 claims description 8
- 238000010276 construction Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 30
- 239000002987 primer (paints) Substances 0.000 description 23
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 19
- 239000002808 molecular sieve Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- 239000000049 pigment Substances 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 15
- 230000007797 corrosion Effects 0.000 description 15
- 238000005260 corrosion Methods 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000000377 silicon dioxide Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 238000005342 ion exchange Methods 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 9
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 8
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 8
- 238000000518 rheometry Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000004925 Acrylic resin Substances 0.000 description 7
- 229920000178 Acrylic resin Polymers 0.000 description 7
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 7
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 6
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 101100433727 Caenorhabditis elegans got-1.2 gene Proteins 0.000 description 5
- 239000004606 Fillers/Extenders Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000003618 dip coating Methods 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- 239000010960 cold rolled steel Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 235000019832 sodium triphosphate Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- OHLKMGYGBHFODF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=C(CN=C=O)C=C1 OHLKMGYGBHFODF-UHFFFAOYSA-N 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
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 235000005956 Cosmos caudatus Nutrition 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical group [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical class N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 2
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 150000001622 bismuth compounds Chemical class 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
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- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 2
- 238000007607 die coating method Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
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- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 239000002075 main ingredient Substances 0.000 description 2
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- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 2
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- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
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- 230000002265 prevention Effects 0.000 description 2
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- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- GFNDFCFPJQPVQL-UHFFFAOYSA-N 1,12-diisocyanatododecane Chemical compound O=C=NCCCCCCCCCCCCN=C=O GFNDFCFPJQPVQL-UHFFFAOYSA-N 0.000 description 1
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 description 1
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- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
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- CGLVZFOCZLHKOH-UHFFFAOYSA-N 8,18-dichloro-5,15-diethyl-5,15-dihydrodiindolo(3,2-b:3',2'-m)triphenodioxazine Chemical compound CCN1C2=CC=CC=C2C2=C1C=C1OC3=C(Cl)C4=NC(C=C5C6=CC=CC=C6N(C5=C5)CC)=C5OC4=C(Cl)C3=NC1=C2 CGLVZFOCZLHKOH-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
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- IFIDXBCRSWOUSB-UHFFFAOYSA-M potassium;1,5-dichloro-4,6-dioxo-1,3,5-triazin-2-olate Chemical compound [K+].ClN1C(=O)[N-]C(=O)N(Cl)C1=O IFIDXBCRSWOUSB-UHFFFAOYSA-M 0.000 description 1
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- XWKBMOUUGHARTI-UHFFFAOYSA-N tricalcium;diphosphite Chemical class [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])[O-].[O-]P([O-])[O-] XWKBMOUUGHARTI-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
-
- 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
-
- 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
- C09D7/63—Additives non-macromolecular organic
-
- 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
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
-
- 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
- C09D7/66—Additives characterised by particle size
- C09D7/68—Particle size between 100-1000 nm
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- 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
- C09D7/66—Additives characterised by particle size
- C09D7/69—Particle size larger than 1000 nm
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- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
Description
本発明は、２液型塗料組成物に関する。また、本発明は、当該２液型塗料組成物を用いた、複層塗膜形成方法、建設機械又は産業機械に関する。 The present invention relates to a two-component coating composition. The present invention also relates to a method for forming a multilayer coating film, a construction machine, or an industrial machine using the two-component coating composition.
ブルドーザー、油圧ショベル、ホイールローダ等の建設機械又は産業機械の塗装において、所望の要求性能に応じて、様々な塗料組成物が使用されている。 BACKGROUND ART In coating construction machines or industrial machines such as bulldozers, hydraulic excavators, and wheel loaders, various coating compositions are used depending on desired performance requirements.
近年の建機、産機メーカーからの塗料に対する要望として、下塗及び上塗塗装仕様におけるウエットオンウエット塗装の仕上り外観及び防食性の向上がある。 In recent years, construction machinery and industrial equipment manufacturers have requested paints to improve the finished appearance and corrosion resistance of wet-on-wet coatings for base coat and top coat specifications.
特許文献１には、特に鉄部の防錆作用に優れた一液型下塗り塗料組成物として、エポキシ樹脂及び／又は変性エポキシ樹脂を樹脂成分とする塗料組成物が開示されている。 Patent Document 1 discloses a paint composition containing an epoxy resin and/or a modified epoxy resin as a resin component, as a one-component undercoat paint composition that is particularly excellent in rust prevention effect on iron parts.
特許文献２には、ビスフェノールＡ型エポキシ樹脂ワニスを樹脂成分とする主剤とポリアミドアミン系硬化剤とから構成されるエポキシ樹脂系下塗り塗料と、変性アクリルポリオール樹脂ワニスを樹脂成分とする主剤とイソシアネート樹脂ワニス硬化剤とから構成されるウレタン樹脂系上塗り塗料と、を備えたことを特徴とする超重防食塗料が開示されている。 Patent Document 2 discloses an epoxy resin-based undercoat paint composed of a base resin having a bisphenol A type epoxy resin varnish as a resin component and a polyamide amine curing agent, and a base coat having a modified acrylic polyol resin varnish as a resin component and an isocyanate resin. A super-heavy-duty anticorrosive paint is disclosed, which is characterized by comprising a urethane resin top coat comprising a varnish hardening agent.
特許文献３には、防食性及び耐候性の両方が優れた複層塗膜形成方法として、ウエットオンウエット仕様の下塗り塗膜及び上塗り塗膜からなる複層塗膜において、下塗り塗膜と上塗り塗膜の表面張力の差を限定した方法が開示され、本方法において、樹脂成分として、アクリル樹脂、エポキシ樹脂及びイソシアネート化合物を含有する下塗り塗料組成物が開示されている。 Patent Document 3 describes a method for forming a multilayer coating film with excellent corrosion resistance and weather resistance in a multilayer coating film consisting of a wet-on-wet undercoat film and a topcoat film. A method is disclosed in which the difference in surface tension of the membrane is limited, and in this method, an undercoat composition containing an acrylic resin, an epoxy resin, and an isocyanate compound as resin components is disclosed.
しかしながら、特許文献１又は２に記載された下塗り塗料組成物は、上塗塗料とのウエットオンウエット適性が不十分であるため、下塗及び上塗塗装仕様の仕上り外観が不十分であった。 However, the undercoat paint composition described in Patent Document 1 or 2 has insufficient wet-on-wet compatibility with the topcoat paint, so the finished appearance of the undercoat and topcoat paint specifications is unsatisfactory.
さらに、特許文献３に記載された塗膜形成方法で得られた複層塗膜は、防食性が不十分であり、また、ウエットオンウエット性が不十分となって、仕上り外観が低下する場合があった。 Furthermore, the multilayer coating film obtained by the coating film forming method described in Patent Document 3 has insufficient corrosion resistance, and also has insufficient wet-on-wet properties, resulting in poor finished appearance. was there.
本発明は、上記従来の実情に鑑みてなされたものであって、本発明の課題は、仕上り外観及び防食性に優れる複層塗膜が得られる２液型塗料組成物を提供することである。また、本発明の課題は、該塗料組成物により得られる塗膜を有する複層塗膜の形成方法、該塗料組成物を用いた、建設機械又は産業機械を提供することである。 The present invention has been made in view of the above-mentioned conventional circumstances, and an object of the present invention is to provide a two-component coating composition that can provide a multilayer coating film with excellent finished appearance and corrosion resistance. . Further, an object of the present invention is to provide a method for forming a multilayer coating film having a coating film obtained using the coating composition, and to provide a construction machine or an industrial machine using the coating composition.
本発明者等は、鋭意検討した結果、特定分子量範囲のエポキシ樹脂、ポリイソシアネート化合物、特定平均粒子径範囲の硫酸バリウム及び特定細孔径範囲のゼオライトを含有する組成物によれば、上記課題の解決が達成できることを見出し、本発明の２液型塗料組成物（以下、単に「本発明の塗料組成物」と称することがある。）を完成するに至った。 As a result of intensive studies, the present inventors have found that the above problems can be solved by a composition containing an epoxy resin with a specific molecular weight range, a polyisocyanate compound, barium sulfate with a specific average particle size range, and zeolite with a specific pore size range. The inventors have discovered that the following can be achieved, and have completed the two-component coating composition of the present invention (hereinafter sometimes simply referred to as "the coating composition of the present invention").
すなわち、本発明は下記＜１＞～＜５＞に関するものである。
＜１＞重量平均分子量５０００～２５０００のエポキシ樹脂（Ａ）、ポリイソシアネート化合物（Ｂ）、平均粒子径０．０１～５．０μｍの硫酸バリウム（Ｃ）及び細孔径０．５０ｎｍ以下のゼオライト（Ｄ）を含有し、
前記エポキシ樹脂（Ａ）及び前記ポリイソシアネート化合物（Ｂ）の固形分総量を基準にして、前記エポキシ樹脂（Ａ）の含有量が６０～９０質量％、前記ポリイソシアネート化合物（Ｂ）の含有量が１０～４０質量％、前記硫酸バリウム（Ｃ）の含有量が１～１００質量％、前記ゼオライト（Ｄ）の含有量が１０～４０質量％である、２液型塗料組成物。
＜２＞前記エポキシ樹脂（Ａ）が、脂肪酸変性エポキシ樹脂、アミン変性エポキシ樹脂及び脂肪酸アミン変性エポキシ樹脂からなる群から選ばれる少なくとも１種である、＜１＞に記載の２液型塗料組成物。
＜３＞前記ポリイソシアネート化合物（Ｂ）が、芳香族ポリイソシアネート化合物である、＜１＞又は＜２＞に記載の２液型塗料組成物。
＜４＞被塗物に、下塗塗料組成物を塗装して下塗塗膜を形成する工程、及び
前記下塗塗膜に上塗塗料組成物を塗装して上塗塗膜を形成する工程を有し、
前記下塗塗料組成物が＜１＞～＜３＞のいずれか１つに記載の２液型塗料組成物である、複層塗膜形成方法。
＜５＞＜１＞～＜３＞のいずれか１つに記載の２液型塗料組成物を用いて塗装された、建設機械又は産業機械。
That is, the present invention relates to the following <1> to <5>.
<1> Epoxy resin (A) with a weight average molecular weight of 5,000 to 25,000, a polyisocyanate compound (B), barium sulfate (C) with an average particle size of 0.01 to 5.0 μm, and zeolite (D) with a pore size of 0.50 nm or less ),
Based on the total solid content of the epoxy resin (A) and the polyisocyanate compound (B), the content of the epoxy resin (A) is 60 to 90% by mass, and the content of the polyisocyanate compound (B) is A two-component coating composition, wherein the content of the barium sulfate (C) is 1 to 100% by mass, and the content of the zeolite (D) is 10 to 40% by mass.
<2> The two-component coating composition according to <1>, wherein the epoxy resin (A) is at least one selected from the group consisting of fatty acid-modified epoxy resins, amine-modified epoxy resins, and fatty acid amine-modified epoxy resins. .
<3> The two-component coating composition according to <1> or <2>, wherein the polyisocyanate compound (B) is an aromatic polyisocyanate compound.
<4> A step of coating an object to be coated with an undercoat paint composition to form an undercoat film, and a step of applying a topcoat paint composition to the undercoat film to form a topcoat film,
A method for forming a multilayer coating film, wherein the undercoat coating composition is the two-component coating composition according to any one of <1> to <3>.
<5> A construction machine or an industrial machine coated with the two-component coating composition according to any one of <1> to <3>.
本発明の塗料組成物は、基体樹脂として、エポキシ樹脂を用いているので、速乾性に優れる。本発明の塗料組成物は、硬化剤として、ポリイソシアネート化合物を用いているので、反応性にも優れている。そのため、本発明の塗料組成物は、ウエットオンウエット適性も優れている。 Since the coating composition of the present invention uses an epoxy resin as the base resin, it has excellent quick drying properties. Since the coating composition of the present invention uses a polyisocyanate compound as a curing agent, it also has excellent reactivity. Therefore, the coating composition of the present invention also has excellent wet-on-wet suitability.
さらに、本発明の塗料組成物は、体質顔料として、特定の小さい平均粒子径範囲の硫酸バリウムを用いているため、得られる複層塗膜の平滑性も向上する。そのため、本発明の塗料組成物によって仕上り外観に優れた複層塗膜を得ることができる。 Furthermore, since the coating composition of the present invention uses barium sulfate having a specific small average particle size range as an extender, the smoothness of the resulting multilayer coating film is also improved. Therefore, a multilayer coating film with excellent finished appearance can be obtained using the coating composition of the present invention.
また、本発明の塗料組成物は、吸水材として特定細孔径範囲のゼオライトを用いているため、耐水性や耐食性に優れた複層塗膜を得ることができる。さらにまた、本発明の塗料組成物は、２液型のエポキシ樹脂／ポリイソシアネート化合物硬化系であるため防食性にも優れている。 Moreover, since the coating composition of the present invention uses zeolite having a specific pore diameter range as a water absorbing material, a multilayer coating film with excellent water resistance and corrosion resistance can be obtained. Furthermore, since the coating composition of the present invention is a two-component epoxy resin/polyisocyanate compound curing system, it also has excellent corrosion resistance.
したがって、本発明の塗料組成物によれば、仕上り外観及び防食性に優れる複層塗膜を得ることができる。 Therefore, according to the coating composition of the present invention, a multilayer coating film with excellent finished appearance and corrosion resistance can be obtained.
［２液型塗料組成物］
本発明の塗料組成物は、重量平均分子量５０００～２５０００のエポキシ樹脂（Ａ）、ポリイソシアネート化合物（Ｂ）、平均粒子径０．０１～５．０μｍの硫酸バリウム（Ｃ）及び細孔径０．５０ｎｍ以下のゼオライト（Ｄ）を含有する組成物である。以下、詳細に述べる。
[Two-component coating composition]
The coating composition of the present invention comprises an epoxy resin (A) having a weight average molecular weight of 5,000 to 25,000, a polyisocyanate compound (B), barium sulfate (C) having an average particle size of 0.01 to 5.0 μm, and a pore size of 0.50 nm. This is a composition containing the following zeolite (D). This will be described in detail below.
＜エポキシ樹脂（Ａ）＞
エポキシ樹脂（Ａ）は、ポリフェノール化合物とエピハロヒドリンとの反応によって得られる芳香族系のエポキシ樹脂が好ましい。
<Epoxy resin (A)>
The epoxy resin (A) is preferably an aromatic epoxy resin obtained by a reaction between a polyphenol compound and epihalohydrin.
芳香族系のエポキシ樹脂の形成のために用いられるポリフェノール化合物としては、例えば、ビス（４－ヒドロキシフェニル）－２，２－プロパン［ビスフェノールＡ］、ビス（４－ヒドロキシフェニル）メタン［ビスフェノールＦ］、ビス（４－ヒドロキシシクロヘキシル）メタン［水添ビスフェノールＦ］、２，２－ビス（４－ヒドロキシシクロヘキシル）プロパン［水添ビスフェノールＡ］、４，４’－ジヒドロキシベンゾフェノン、ビス（４－ヒドロキシフェニル）－１，１－エタン、ビス（４－ヒドロキシフェニル）－１，１－イソブタン、ビス（４－ヒドロキシ－３－ｔｅｒｔ－ブチル－フェニル）－２，２－プロパン、ビス（２－ヒドロキシナフチル）メタン、テトラ（４－ヒドロキシフェニル）－１，１，２，２－エタン、４，４’－ジヒドロキシジフェニルスルホン、フェノールノボラック、クレゾールノボラック等を挙げることができる。 Examples of polyphenol compounds used for forming aromatic epoxy resins include bis(4-hydroxyphenyl)-2,2-propane [bisphenol A] and bis(4-hydroxyphenyl)methane [bisphenol F]. , bis(4-hydroxycyclohexyl)methane [hydrogenated bisphenol F], 2,2-bis(4-hydroxycyclohexyl)propane [hydrogenated bisphenol A], 4,4'-dihydroxybenzophenone, bis(4-hydroxyphenyl) -1,1-ethane, bis(4-hydroxyphenyl)-1,1-isobutane, bis(4-hydroxy-3-tert-butyl-phenyl)-2,2-propane, bis(2-hydroxynaphthyl)methane , tetra(4-hydroxyphenyl)-1,1,2,2-ethane, 4,4'-dihydroxydiphenylsulfone, phenol novolak, cresol novolak, and the like.
また、芳香族系のエポキシ樹脂の中でも、ビスフェノールＡから誘導されるエポキシ樹脂を好適に使用することができる。 Furthermore, among aromatic epoxy resins, epoxy resins derived from bisphenol A can be suitably used.
また、エポキシ樹脂（Ａ）としては、変性エポキシ樹脂を好適に使用することができる。変性エポキシ樹脂としては、例えば、脂肪酸変性エポキシ樹脂、アミン変性エポキシ樹脂、脂肪酸アミン変性エポキシ樹脂、ウレタン変性エポキシ樹脂、アクリル変性エポキシ樹脂、ポリエステル変性エポキシ樹脂等を挙げることができる。 Moreover, as the epoxy resin (A), a modified epoxy resin can be suitably used. Examples of modified epoxy resins include fatty acid-modified epoxy resins, amine-modified epoxy resins, fatty acid amine-modified epoxy resins, urethane-modified epoxy resins, acrylic-modified epoxy resins, and polyester-modified epoxy resins.
上記変性エポキシ樹脂のうち、特に、脂肪酸変性エポキシ樹脂、アミン変性エポキシ樹脂、脂肪酸アミン変性エポキシ樹脂を好適に使用することができる。 Among the above-mentioned modified epoxy resins, fatty acid-modified epoxy resins, amine-modified epoxy resins, and fatty acid amine-modified epoxy resins can be particularly preferably used.
これらのエポキシ樹脂の市販品としては、例えば、アラキード９２０１Ｎ、アラキード９２０３Ｎ、アラキード９２０５、アラキード９２０８、モデピクス４０１（以上、荒川化学工業株式会社製、商品名）、ＥＰＩＣＬＯＮ Ｈ－４０５－４０、ＥＰＩＣＬＯＮ Ｈ－３０４－４０、ＥＰＩＣＬＯＮ Ｈ－４０３－４５、ＥＰＩＣＬＯＮ Ｈ－４０８－４０（以上、ＤＩＣ株式会社製、商品名）、ＥＰＯＭＩＫ Ｒ１４０、ＥＰＯＭＩＫ Ｒ３０１、ＥＰＯＭＩＫ Ｒ３０４、ＥＰＯＭＩＫ Ｒ３０７、ＥＰＯＭＩＫ Ｕ４６６ＢＴ６０、ＥＰＯＭＩＫ Ｕ４５５ＣＴ６０、ＥＰＯＭＩＫ Ｕ４５２ＣＴ６０、エポキー８１１、エポキー８７２、エポキー８９１、（以上、三井化学株式会社、商品名）等を挙げることができる。 Commercially available products of these epoxy resins include, for example, Arachide 9201N, Arakido 9203N, Arakido 9205, Arakido 9208, Modepix 401 (trade name, manufactured by Arakawa Chemical Co., Ltd.), EPICLON H-405-40, and EPICLON H-. 304-40, EPICLON H-403-45, EPICLON H-408-40 (manufactured by DIC Corporation, product name), EPOMIK R140, EPOMIK R301, EPOMIK R304, EPOMIK R307, EPOMIK U466BT60, EPOMIK U455CT60, EPOMIK U452CT60, Examples include Epokey 811, Epokey 872, and Epokey 891 (all trade names manufactured by Mitsui Chemicals, Inc.).
エポキシ樹脂（Ａ）は、仕上り外観、硬度及び塗装固形分濃度の観点から、重量平均分子量が５０００～２５０００の範囲内であり、７０００～２２０００の範囲内が好ましく、１００００～２００００の範囲内がより好ましい。 The epoxy resin (A) has a weight average molecular weight within the range of 5,000 to 25,000, preferably within the range of 7,000 to 22,000, and more preferably within the range of 10,000 to 20,000, from the viewpoint of finished appearance, hardness, and coating solid content concentration. preferable.
本発明の明細書における重量平均分子量又は数平均分子量は、ゲルパーミエーションクロマトグラフ（ＧＰＣ）を用いて測定した重量平均分子量又は数平均分子量を、標準ポリスチレンの分子量を基準にして換算した値である。具体的には、ゲルパーミュエーションクロマトグラフとして、「ＨＬＣ８１２０ＧＰＣ」（商品名、東ソー社製）を使用し、カラムとして、「ＴＳＫｇｅｌ Ｇ－４０００ＨＸＬ」、「ＴＳＫｇｅｌ Ｇ－３０００ＨＸＬ」、「ＴＳＫｇｅｌ Ｇ－２５００ＨＸＬ」及び「ＴＳＫｇｅｌ Ｇ－２０００ＨＸＬ」（商品名、いずれも東ソー社製）の４本を使用し、移動相：テトラヒドロフラン、測定温度：４０℃、流速：１ｍＬ／ｍｉｎ及び検出器：ＲＩの条件下で重量平均分子量又は数平均分子量を測定することができる。 The weight average molecular weight or number average molecular weight in the specification of the present invention is a value obtained by converting the weight average molecular weight or number average molecular weight measured using gel permeation chromatography (GPC) based on the molecular weight of standard polystyrene. . Specifically, "HLC8120GPC" (trade name, manufactured by Tosoh Corporation) was used as a gel permeation chromatograph, and "TSKgel G-4000HXL", "TSKgel G-3000HXL", and "TSKgel G-2500HXL" were used as columns. ” and “TSKgel G-2000HXL” (trade names, both manufactured by Tosoh Corporation) under the conditions of mobile phase: tetrahydrofuran, measurement temperature: 40°C, flow rate: 1 mL/min, and detector: RI. Weight average molecular weight or number average molecular weight can be measured.
エポキシ樹脂（Ａ）は、付着性の観点から、水酸基価が好ましくは５０～３００ｍｇＫＯＨ／ｇの範囲内であり、より好ましくは５０～２５０ｍｇＫＯＨ／ｇの範囲内であり、さらに好ましくは５０～２００ｍｇＫＯＨ／ｇの範囲内である。 From the viewpoint of adhesion, the epoxy resin (A) preferably has a hydroxyl value within the range of 50 to 300 mgKOH/g, more preferably within the range of 50 to 250 mgKOH/g, and even more preferably 50 to 200 mgKOH/g. It is within the range of g.
また、仕上り外観及び防食性の観点から本発明の塗料組成物において、エポキシ樹脂（Ａ）及び後述のポリイソシアネート化合物（Ｂ)の固形分総量を基準にして、エポキシ樹脂（Ａ）の含有量は６０～９０質量％であり、好ましくは７０～９０質量％である。 In addition, from the viewpoint of finished appearance and corrosion resistance, in the coating composition of the present invention, the content of epoxy resin (A) is determined based on the total solid content of epoxy resin (A) and polyisocyanate compound (B) described below. The content is 60 to 90% by weight, preferably 70 to 90% by weight.
＜ポリイソシアネート化合物（Ｂ）＞
ポリイソシアネート化合物（Ｂ）は、１分子中に遊離のイソシアネート基を２個以上有する化合物である。
<Polyisocyanate compound (B)>
The polyisocyanate compound (B) is a compound having two or more free isocyanate groups in one molecule.
ポリイソシアネート化合物（Ｂ）としては、従来からポリウレタン製造に使用されているものを使用することができる。具体的には例えば、脂肪族ポリイソシアネート化合物、脂環式ポリイソシアネート化合物、芳香脂肪族ポリイソシアネート化合物、芳香族ポリイソシアネート化合物及びその粗製物、これらのポリイソシアネート化合物の変性物等を挙げることができる。ポリイソシアネート化合物（Ｂ）は単独で、或いは２種以上を併用して使用することができる。 As the polyisocyanate compound (B), those conventionally used in polyurethane production can be used. Specific examples include aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, araliphatic polyisocyanate compounds, aromatic polyisocyanate compounds and their crude products, and modified products of these polyisocyanate compounds. . The polyisocyanate compound (B) can be used alone or in combination of two or more.
上記脂肪族ポリイソシアネート化合物の具体例としては、エチレンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート（ＨＤＩ）、ドデカメチレンジイソシアネート、１，６，１１－ウンデカントリイソシアネート、２，２，４－トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート、２，６－ジイソシアナトメチルカプロエート、ビス（２－イソシアナトエチル）フマレート、ビス（２－イソシアナトエチル）カーボネート、２－イソシアナトエチル－２，６－ジイソシアナトヘキサノエート等を挙げることができる。 Specific examples of the aliphatic polyisocyanate compounds include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate. , lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis(2-isocyanatoethyl) fumarate, bis(2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexano Eth, etc. can be mentioned.
上記脂環式ポリイソシアネート化合物の具体例としては、イソホロンジイソシアネート（ＩＰＤＩ）、ジシクロヘキシルメタン－４，４’－ジイソシアネート（水添ＭＤＩ）、シクロヘキシレンジイソシアネート、メチルシクロヘキシレンジイソシアネート（水添ＴＤＩ）、ビス（２－イソシアナトエチル）－４－シクロヘキセン－１，２－ジカルボキシレート、２，５－及び／又は２，６－ノルボルナンジイソシアネート等を挙げることができる。 Specific examples of the alicyclic polyisocyanate compounds include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis( Examples include 2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate, 2,5- and/or 2,6-norbornane diisocyanate, and the like.
上記芳香脂肪族ポリイソシアネート化合物の具体例としては、ｍ－及び／又はｐ－キシリレンジイソシアネート（ＸＤＩ）、α，α，α’，α’－テトラメチルキシリレンジイソシアネート（ＴＭＸＤＩ）等を挙げることができる。 Specific examples of the above-mentioned araliphatic polyisocyanate compounds include m- and/or p-xylylene diisocyanate (XDI), α, α, α', α'-tetramethylxylylene diisocyanate (TMXDI), etc. can.
上記芳香族ポリイソシアネート化合物の具体例としては、１，３－及び／又は１，４－フェニレンジイソシアネート、２，４－及び／又は２，６－トリレンジイソシアネート（ＴＤＩ）、粗製ＴＤＩ、２，４’－及び／又は４，４’－ビフェニルメタンジイソシアネート（ＭＤＩ）、４，４’－ジイソシアナトビフェニル、３，３’－ジメチル－４，４’－ジイソシアナトビフェニル、３，３’－ジメチル－４，４’－ジイソシアナトジフェニルメタン、粗製ＭＤＩ、１，５－ナフチレンジイソシアネート、４，４’，４”－トリフェニルメタントリイソシアネート、ｍ－及びｐ－イソシアナトフェニルスルホニルイソシアネート等を挙げることができる。 Specific examples of the aromatic polyisocyanate compound include 1,3- and/or 1,4-phenylene diisocyanate, 2,4- and/or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4-phenylene diisocyanate, '- and/or 4,4'-biphenylmethane diisocyanate (MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl -4,4'-diisocyanatodiphenylmethane, crude MDI, 1,5-naphthylene diisocyanate, 4,4',4''-triphenylmethane triisocyanate, m- and p-isocyanatophenylsulfonyl isocyanate, etc. Can be done.
また、上記ポリイソシアネート化合物の変性物としては、具体的には、変性ＭＤＩ（ウレタン変性ＭＤＩ、カルボジイミド変性ＭＤＩ、トリヒドロカルビルホスフェート変性ＭＤＩ）、ウレタン変性ＴＤＩ、ビウレット変性ＨＤＩ、イソシアヌレート変性ＨＤＩ、イソシアヌレート変性ＩＰＤＩ等のポリイソシアネート化合物の変性物；及びこれらの２種以上の混合物（例えば、変性ＭＤＩとウレタン変性ＴＤＩの混合物）等を挙げることができる。 In addition, specific examples of the modified polyisocyanate compound include modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbylphosphate-modified MDI), urethane-modified TDI, biuret-modified HDI, isocyanurate-modified HDI, and isocyanurate-modified HDI. Examples include modified products of polyisocyanate compounds such as modified IPDI; and mixtures of two or more thereof (for example, a mixture of modified MDI and urethane modified TDI).
本発明の塗料組成物の乾燥性や防食性の観点から、上記ポリイソシアネート化合物（Ｂ）のうち、芳香族ポリイソシアネート化合物及びその粗製物、芳香族ポリイソシアネート化合物の変性物を好適に使用することができる。 From the viewpoint of drying properties and anticorrosion properties of the coating composition of the present invention, among the polyisocyanate compounds (B), aromatic polyisocyanate compounds, crude products thereof, and modified products of aromatic polyisocyanate compounds are preferably used. Can be done.
上記の芳香族ポリイソシアネート化合物のなかでも特に、ＭＤＩ、ＴＤＩ、ウレタン変性ＭＤＩ、ウレタン変性ＴＤＩを好適に使用することができる。 Among the above-mentioned aromatic polyisocyanate compounds, MDI, TDI, urethane-modified MDI, and urethane-modified TDI can be particularly preferably used.
このようなポリイソシアネート化合物の市販品としては、例えば、タケネートＤ－１６５Ｎ、タケネートＤ－１０２、タケネートＤ－１０４（三井化学社製）等を挙げることができる。 Examples of commercially available polyisocyanate compounds include Takenate D-165N, Takenate D-102, and Takenate D-104 (manufactured by Mitsui Chemicals).
また、仕上り外観及び防食性の観点から本発明の塗料組成物において、エポキシ樹脂（Ａ）及びポリイソシアネート化合物（Ｂ)の固形分総量を基準にして、ポリイソシアネート化合物（Ｂ）の含有量は１０～４０質量％であり、好ましくは１０～３０質量％である。 In addition, from the viewpoint of finished appearance and corrosion resistance, in the coating composition of the present invention, the content of the polyisocyanate compound (B) is 10% based on the total solid content of the epoxy resin (A) and the polyisocyanate compound (B). ~40% by weight, preferably 10~30% by weight.
＜硫酸バリウム（Ｃ）＞
本発明の塗料組成物は、平均粒子径が０．０１～５μｍ、好ましくは０．０５～４μｍ、さらに好ましくは０．０５～３μｍの硫酸バリウム（Ｃ）を含有する。（以下、平均粒子径０．０１～５μｍの硫酸バリウム（Ｃ）を単に硫酸バリウム（Ｃ）と略称する）。
<Barium sulfate (C)>
The coating composition of the present invention contains barium sulfate (C) having an average particle diameter of 0.01 to 5 μm, preferably 0.05 to 4 μm, and more preferably 0.05 to 3 μm. (Hereinafter, barium sulfate (C) with an average particle diameter of 0.01 to 5 μm will be simply referred to as barium sulfate (C)).
なお、本明細書において、平均粒子径は、動的光散乱法による粒度分布測定により得られる値である。具体的には、例えばＵＰＡ－ＥＸ２５０（商品名、日機装株式会社製、動的光散乱法による粒度分布測定装置）を用いて硫酸バリウム（Ｃ）の平均粒子径を測定することができる。 Note that in this specification, the average particle diameter is a value obtained by particle size distribution measurement using a dynamic light scattering method. Specifically, the average particle diameter of barium sulfate (C) can be measured using, for example, UPA-EX250 (trade name, manufactured by Nikkiso Co., Ltd., particle size distribution measuring device using dynamic light scattering method).
このような硫酸バリウム（Ｃ）の市販品としては、バリファインＢＦ－２０（堺化学工業社製、商品名、平均粒子径０．０３μｍの硫酸バリウム）、ＢＡＲＩＡＣＥ Ｂ－３０（堺化学工業社製、商品名、平均粒子径０．３μｍの硫酸バリウム）、ＳＰＡＲＷＩＴＥ（スパーワイト）Ｗ－５ＨＢ（Ｓｉｎｏ－Ｃａｎ社製、商品名、硫酸バリウム粉末、平均粒子径：１．６μｍ）等を挙げることができる。 Commercially available products of barium sulfate (C) include BARIACE B-20 (manufactured by Sakai Chemical Industry Co., Ltd., trade name, barium sulfate with an average particle size of 0.03 μm) and BARIACE B-30 (manufactured by Sakai Chemical Industry Co., Ltd.). , trade name, barium sulfate with an average particle diameter of 0.3 μm), SPARWITE W-5HB (manufactured by Sino-Can, trade name, barium sulfate powder, average particle diameter: 1.6 μm), etc. .
本発明の塗料組成物における硫酸バリウム（Ｃ）の含有量は、仕上り外観の観点から、エポキシ樹脂（Ａ）及びポリイソシアネート化合物（Ｂ)の固形分総量を基準にして、１～１００質量％であり、好ましくは５～８０質量％であり、さらに好ましくは１０～７５質量％である。 From the viewpoint of finished appearance, the content of barium sulfate (C) in the coating composition of the present invention is 1 to 100% by mass based on the total solid content of the epoxy resin (A) and the polyisocyanate compound (B). The content is preferably 5 to 80% by mass, more preferably 10 to 75% by mass.
＜ゼオライト（Ｄ）＞
ゼオライトは結晶性アルミノ珪酸塩の総称であり、構成元素は、Ａｌ、Ｓｉ、Ｏ、カチオン(陽イオン)で、ＳｉＯ４とＡｌＯ４から形成される四面体構造（Ｓｉ４＋又はＡｌ３＋を中心として形成される四面体）を基本構造とする化合物である。それらが複雑に且つ規則正しく繋がることで、直径が数Å～十数Åの小さな分子とほぼ同じ大きさの細孔が１次元、２次元又は３次元に規則的に形成されている。これがゼオライトの特徴である。
<Zeolite (D)>
Zeolite is a general term for crystalline aluminosilicates, and its constituent elements are Al, Si, O, and cations, and it has a tetrahedral structure formed from SiO 4 and AlO 4 (centered on Si 4+ or Al 3+ ). It is a compound whose basic structure is a tetrahedron formed. By connecting them in a complex and regular manner, pores with diameters of several angstroms to several tens of angstroms, approximately the same size as small molecules, are regularly formed in one, two, or three dimensions. This is a characteristic of zeolite.
ゼオライトの細孔内にはカチオンが存在しており、カチオンに基づいてゼオライトの諸機能が発現する。ゼオライトの細孔には、その直径より小さな分子のみが進入でき、大きな分子と篩い分けができることから、ゼオライトの中にはモレキュラーシーブ（分子篩）と呼ばれるものがある。 Cations exist within the pores of zeolite, and the various functions of zeolite are expressed based on the cations. Some zeolites are called molecular sieves because only molecules smaller than their diameter can enter the pores of zeolites and can be screened out from larger molecules.
ゼオライトには、含水アルミノケイ酸塩を主成分とした天然ゼオライトと、Ｎａ２Ｏ・Ａｌ２Ｏ３・ｘＳｉＯ２・ｙＨ２Ｏを主成分とした合成ゼオライトがある。合成ゼオライトはパ－ムチットとも呼ばれ、炭酸ナトリウム、シリカ、アルミナ又はカオリンを共融する乾式法、又はケイ酸ナトリウムとアルミン酸ナトリウムを合わせてゲルを沈澱させる湿式法によって製造される。 Zeolites include natural zeolites whose main components are hydrated aluminosilicate and synthetic zeolites whose main components are Na2O.Al2O3.xSiO2.yH2O . Synthetic zeolites, also called palmchit, are produced by a dry method by eutecticizing sodium carbonate, silica, alumina or kaolin, or by a wet method by combining sodium silicate and sodium aluminate to precipitate a gel.
天然ゼオライト、合成ゼオライトのいずれもイオン交換能を有し、脱水しても結晶構造が変化せず、脱水した後に分子サイズの細孔が得られ、大きい吸着能を有する。また、水熱合成によりアルミノケイ酸ナトリウムゲルを結晶化し脱水した後に一定サイズの細孔が得られるものは、一般にモレキュラーシーブと呼ばれている。 Both natural zeolite and synthetic zeolite have ion exchange ability, their crystal structure does not change even after dehydration, molecular-sized pores are obtained after dehydration, and they have large adsorption capacity. Moreover, a product in which pores of a certain size are obtained after crystallizing and dehydrating sodium aluminosilicate gel by hydrothermal synthesis is generally called a molecular sieve.
顔料として、硫酸バリウム（Ｃ）とゼオライト（Ｄ）を併用することにより、本発明の塗料組成物の耐水性を向上させることができる。 By using barium sulfate (C) and zeolite (D) together as pigments, the water resistance of the coating composition of the present invention can be improved.
ゼオライト（Ｄ）としては、仕上がり性、防食性の観点から、一般にモレキュラーシーブと呼ばれているものを好適に使用することができる。ゼオライトを粉末状やペレット状に成型したものが市販されており、原料のゼオライトの種類によってモレキュラーシーブ３Ａ、モレキュラーシーブ４Ａ、モレキュラーシーブ５Ａ、モレキュラーシーブ１３Ｘ等が市販されている。数字は上記細孔のおおよその直径(オングストローム)を、大文字のアルファベットはゼオライトの種類を表しており、ＡはＬＴＡ型ゼオライト、ＸはＦＡＵ型ゼオライトを表している。 As the zeolite (D), what is generally called a molecular sieve can be suitably used from the viewpoint of finishability and corrosion resistance. Zeolite molded into powder or pellet form is commercially available, and depending on the type of zeolite used as the raw material, Molecular Sieve 3A, Molecular Sieve 4A, Molecular Sieve 5A, Molecular Sieve 13X, etc. are commercially available. The numbers represent the approximate diameters (angstroms) of the pores, and the capital letters represent the type of zeolite, with A representing LTA type zeolite and X representing FAU type zeolite.
上記モレキュラーシーブのうち、モレキュラーシーブ３Ａ、モレキュラーシーブ５Ａが好ましく、特にモレキュラーシーブ５Ａを好適に使用することができる。 Among the above molecular sieves, molecular sieve 3A and molecular sieve 5A are preferred, and molecular sieve 5A can be particularly preferably used.
モレキュラーシーブ結晶の細孔付近にある金属カチオンの位置と大きさにより、この細孔の有効直径は変化し、例えばモレキュラーシーブ５Ａはモレキュラーシーブ４Ａのナトリウムイオンをカルシウムイオンで置換したものである。 The effective diameter of the pores changes depending on the position and size of the metal cations near the pores of the molecular sieve crystal. For example, molecular sieve 5A is obtained by replacing the sodium ions of molecular sieve 4A with calcium ions.
ゼオライト（Ｄ）の細孔径（細孔の有効直径）の範囲は仕上り外観の観点から、０．５０ｎｍ以下の範囲内であり、好ましくは０．１０～０．５０ｎｍの範囲内であり、さらに好ましくは０．２０～０．５０ｎｍの範囲内である。 From the viewpoint of finished appearance, the range of the pore diameter (effective diameter of the pores) of the zeolite (D) is within the range of 0.50 nm or less, preferably within the range of 0.10 to 0.50 nm, and more preferably within the range of 0.10 to 0.50 nm. is within the range of 0.20 to 0.50 nm.
なお、ゼオライト（Ｄ）の細孔径は、窒素ガス吸着法によって測定できる。 Note that the pore diameter of zeolite (D) can be measured by a nitrogen gas adsorption method.
本発明の塗料組成物におけるゼオライト（Ｄ）の含有量は、仕上り外観の観点から、エポキシ樹脂（Ａ）及びポリイソシアネート化合物（Ｂ)の固形分総量を基準にして、１０～４０質量％であり、好ましくは１５～３０質量％であり、さらに好ましくは１５～２５質量％である。 From the viewpoint of finished appearance, the content of zeolite (D) in the coating composition of the present invention is 10 to 40% by mass based on the total solid content of the epoxy resin (A) and the polyisocyanate compound (B). , preferably 15 to 30% by weight, more preferably 15 to 25% by weight.
＜防錆顔料＞
本発明の塗料組成物には、防食性の向上を目的として防錆顔料を含有させることができる。防錆顔料としては、具体的には例えば、酸化亜鉛、亜リン酸塩化合物、リン酸塩化合物、モリブテン酸塩系化合物、ビスマス化合物、金属イオン交換シリカ等を挙げることができる。
<Rust prevention pigment>
The coating composition of the present invention can contain an anticorrosion pigment for the purpose of improving anticorrosion properties. Specific examples of the antirust pigment include zinc oxide, phosphite compounds, phosphate compounds, molybdate compounds, bismuth compounds, metal ion exchange silica, and the like.
上記亜リン酸塩化合物としては、ＥＸＰＥＲＴ ＮＰ－１０００、ＥＸＰＥＲＴ ＮＰ－１０２０Ｃ等の亜リン酸カルシウム化合物、ＥＸＰＥＲＴ ＮＰ－１１００、ＥＸＰＥＲＴ ＮＰ－１１０２等の亜リン酸アルミニウム化合物を挙げることができる（ＥＸＰＥＲＴシリーズはいずれも東邦顔料社製、商品名）。 Examples of the above-mentioned phosphite compounds include calcium phosphite compounds such as EXPERT NP-1000 and EXPERT NP-1020C, and aluminum phosphite compounds such as EXPERT NP-1100 and EXPERT NP-1102. Also manufactured by Toho Pigment Co., Ltd. (product name).
上記リン酸塩化合物としては、金属化合物で処理されたトリポリリン酸２水素アルミニウム等を挙げることができる。上記金属化合物としては、亜鉛、カルシウム、マグネシウム、マンガン、ビスマス、コバルト、スズ、ジルコニウム、チタニウム、ストロンチウム、銅、鉄、リチウム、アルミニウム、ニッケル、及びナトリウムの塩化物、水酸化物、炭酸化物、硫酸物等を挙げることができる。 Examples of the phosphate compound include aluminum dihydrogen tripolyphosphate treated with a metal compound. The above metal compounds include chlorides, hydroxides, carbonates, and sulfuric acids of zinc, calcium, magnesium, manganese, bismuth, cobalt, tin, zirconium, titanium, strontium, copper, iron, lithium, aluminum, nickel, and sodium. I can list things.
上記金属化合物で処理されたトリポリリン酸２水素アルミニウムの市販品としては、Ｋ－ＷＨＩＴＥ １４０、Ｋ－ＷＨＩＴＥ Ｃａ６５０、Ｋ－ＷＨＩＴＥ ４５０Ｈ、Ｋ－ＷＨＩＴＥ Ｇ－１０５、Ｋ－ＷＨＩＴＥ １０５、Ｋ－ＷＨＩＴＥ Ｋ－８２（いずれもテイカ社製、商品名）等を挙げることができる。 Commercial products of aluminum dihydrogen tripolyphosphate treated with the above metal compound include K-WHITE 140, K-WHITE Ca650, K-WHITE 450H, K-WHITE G-105, K-WHITE 105, K-WHITE K- 82 (all manufactured by Teika, trade name), and the like.
上記モリブテン酸塩系化合物の市販品としては、例えば、ＬＦボウセイ Ｍ－ＰＳＮ、ＬＦボウセイ ＭＣ－４００ＷＲ、ＬＦボウセイ ＰＭ－３００、ＬＦボウセイ ＰＭ－３０８（いずれもキクチカラー社製、商品名）等を挙げることができる。 Examples of commercially available molybutate-based compounds include LF Bousei M-PSN, LF Bousei MC-400WR, LF Bousei PM-300, and LF Bousei PM-308 (all manufactured by Kikuchi Color Co., Ltd., trade names). can be mentioned.
上記ビスマス化合物としては、例えば、酸化ビスマス、水酸化ビスマス、塩基性炭酸ビスマス、硝酸ビスマス、ケイ酸ビスマス及び有機酸ビスマス等を挙げることができる。 Examples of the bismuth compound include bismuth oxide, bismuth hydroxide, basic bismuth carbonate, bismuth nitrate, bismuth silicate, and bismuth organic acids.
上記金属イオン交換シリカとしては、例えば、カルシウムイオン交換シリカ、マグネシウムイオン交換シリカ等を挙げることができる。これらの金属イオン交換シリカとしてはリン酸変性金属イオン交換シリカを使用することもできる。 Examples of the metal ion exchange silica include calcium ion exchange silica, magnesium ion exchange silica, and the like. As these metal ion exchange silicas, phosphoric acid modified metal ion exchange silicas can also be used.
上記カルシウムイオン交換シリカは、微細な多孔質のシリカ担体にイオン交換によって、カルシウムイオンが導入されたシリカ微粒子である。カルシウムイオン交換シリカの市販品としては、ＳＨＩＥＬＤＥＸ（シールデックス、登録商標）Ｃ３０３、ＳＨＩＥＬＤＥＸＡＣ‐３、ＳＨＩＥＬＤＥＸＣ‐５（以上いずれもＷ．Ｒ．Ｇｒａｃｅ＆Ｃｏ．社製）、サイロマスク５２（富士シリシア社製）等を挙げることができる。 The calcium ion-exchanged silica is fine silica particles in which calcium ions are introduced into a fine porous silica carrier by ion exchange. Commercially available calcium ion exchange silica products include SHIELDEX (registered trademark) C303, SHIELDEXAC-3, SHIELDEXC-5 (all manufactured by WR Grace & Co.), and Silomask 52 (manufactured by Fuji Silicia). etc. can be mentioned.
上記マグネシウムイオン交換シリカは、微細な多孔質のシリカ担体にイオン交換によって、マグネシウムイオンが導入されたシリカ微粒子である。マグネシウムイオン交換シリカの市販品としては、サイロマスク５２Ｍ（富士シリシア社製）、ノビノックスＡＣＥ－１１０（ＳＮＣＺ社製・フランス）等を挙げることができる。 The magnesium ion-exchanged silica is fine silica particles in which magnesium ions are introduced into a fine porous silica carrier by ion exchange. Examples of commercially available magnesium ion-exchanged silica include Silomask 52M (manufactured by Fuji Silicia) and Novinox ACE-110 (manufactured by SNCZ, France).
本発明の塗料組成物において防錆顔料を使用する場合、使用量は、エポキシ樹脂（Ａ）及びポリイソシアネート化合物（Ｂ)の固形分総量を基準にして、１～５０質量％、特に１０～４０質量％であることが、仕上り外観及び防食性の観点からから好ましい。 When using the anticorrosive pigment in the coating composition of the present invention, the amount used is 1 to 50% by mass, particularly 10 to 40% by mass, based on the total solid content of the epoxy resin (A) and the polyisocyanate compound (B). % by mass is preferable from the viewpoint of finished appearance and corrosion resistance.
＜着色顔料＞
本発明の塗料組成物には、所望の色とすることを目的として、着色顔料を使用することができる。着色顔料としては、具体的には、チタン白、モリブデン酸亜鉛、モリブデン酸カルシウム、カーボンブラック、黒鉛（グラファイト）、鉄黒（アイアンブラック）、紺青、群青、コバルトブルー、銅フタロシアニンブルー、インダンスロンブルー、黄鉛、合成黄色酸化鉄、べんがら、透明べんがら、ビスマスバナデート、チタンイエロー、亜鉛黄（ジンクエロー）、モノアゾイエロー、オーカー、ジスアゾ、イソインドリノンイエロー、金属錯塩アゾイエロー、キノフタロンイエロー、ベンズイミダゾロンイエロー、モノアゾレッド、無置換キナクリドンレッド、アゾレーキ（Ｍｎ塩）、キナクリドンマゼンダ、アンサンスロンオレンジ、ジアンスラキノニルレッド、ペリレンマルーン、ペリレンレッド、ジケトピロロピロールクロムバーミリオン、塩素化フタロシアニングリーン、臭素化フタロシアニングリーン、ピラゾロンオレンジ、ベンズイミダゾロンオレンジ、ジオキサジンバイオレット、ペリレンバイオレット等を挙げることができる。
<Colored pigment>
Coloring pigments can be used in the coating composition of the present invention for the purpose of providing a desired color. Specific examples of coloring pigments include titanium white, zinc molybdate, calcium molybdate, carbon black, graphite, iron black, navy blue, ultramarine blue, cobalt blue, copper phthalocyanine blue, and indanthrone. Blue, yellow lead, synthetic yellow iron oxide, red iron oxide, clear red iron oxide, bismuth vanadate, titanium yellow, zinc yellow, monoazo yellow, ocher, disazo, isoindolinone yellow, metal complex azo yellow, quinophthalone yellow, benzimidazo Ron yellow, monoazo red, unsubstituted quinacridone red, azo lake (Mn salt), quinacridone magenta, anthanthrone orange, dianthraquinonyl red, perylene maroon, perylene red, diketopyrrolopyrrole chrome vermilion, chlorinated phthalocyanine green, bromine Examples include phthalocyanine green, pyrazolone orange, benzimidazolone orange, dioxazine violet, and perylene violet.
本発明の塗料組成物において着色顔料を使用する場合、使用量は、エポキシ樹脂（Ａ）及びポリイソシアネート化合物（Ｂ)の固形分総量を基準にして、２０～１５０質量％、特に４０～１３０質量％であることが、仕上り外観の観点から好ましい。 When a colored pigment is used in the coating composition of the present invention, the amount used is 20 to 150% by mass, particularly 40 to 130% by mass, based on the total solid content of the epoxy resin (A) and the polyisocyanate compound (B). % is preferable from the viewpoint of finished appearance.
＜体質顔料＞
本発明の塗料組成物には必要に応じて体質顔料（硫酸バリウム（Ｃ）を除く）を含有させることができる。
<Extender pigment>
The coating composition of the present invention may contain extender pigments (excluding barium sulfate (C)) if necessary.
上記体質顔料としては、例えば、クレー、シリカ、硫酸バリウム（硫酸バリウム（Ｃ）を除く）、タルク、炭酸カルシウム、ホワイトカーボン、珪藻土、炭酸マグネシウムアルミニウムフレーク、雲母フレーク等を挙げることができる。 Examples of the extender pigment include clay, silica, barium sulfate (excluding barium sulfate (C)), talc, calcium carbonate, white carbon, diatomaceous earth, magnesium aluminum carbonate flakes, mica flakes, and the like.
本発明の塗料組成物において体質顔料を使用する場合、使用量は、エポキシ樹脂（Ａ）及びポリイソシアネート化合物（Ｂ)の固形分総量を基準にして、２０～１５０質量％、特に４０～１４０質量％、さらに特に４０～１３０質量％であることが、耐水性及び防食性の観点から好ましい。 When an extender pigment is used in the coating composition of the present invention, the amount used is 20 to 150% by mass, particularly 40 to 140% by mass, based on the total solid content of the epoxy resin (A) and the polyisocyanate compound (B). %, more particularly 40 to 130% by mass, from the viewpoint of water resistance and corrosion resistance.
＜レオロジーコントロール剤＞
本発明の塗料組成物には、塗料組成物の流動性を制御して仕上り外観及び塗装作業性の向上させることを目的として、レオロジーコントロール剤を使用することができる。
<Rheology control agent>
A rheology control agent can be used in the coating composition of the present invention for the purpose of controlling the fluidity of the coating composition and improving the finished appearance and coating workability.
レオロジーコントロール剤としては、具体的には例えば、粘土鉱物（例えば、金属ケイ酸塩、モンモロリロナイト）、アクリル樹脂（例えば、分子中にアクリル酸エステル又はメタクリル酸エステルのポリマー、オリゴマーからなる構造を含むもの）、ポリオレフィン（例えば、ポリエチレン、ポリプロピレン等）、アマイド（例えば、高級脂肪酸アマイド、ポリアマイド、オリゴマー等）、ポリカルボン酸（分子中に少なくとも２つ以上のカルボキシル基を有する誘導体を含む）、セルロース（ニトロセルロース、アセチルセルロース、セルロースエーテル等種々の誘導体を含む）、及びウレタン（分子中にウレタン構造を含むポリマー、オリゴマー等）、ウレア（分子中にウレア構造を含むポリマー、オリゴマー等）、ウレタンウレア（分子中にウレタン構造とウレア構造を含むポリマー、オリゴマー等）等を挙げることができる。 Specific examples of rheology control agents include clay minerals (e.g., metal silicates, montmorillonite), acrylic resins (e.g., polymers and oligomers with acrylic esters or methacrylic esters in the molecule). ), polyolefins (e.g., polyethylene, polypropylene, etc.), amides (e.g., higher fatty acid amides, polyamides, oligomers, etc.), polycarboxylic acids (including derivatives having at least two or more carboxyl groups in the molecule), Cellulose (including various derivatives such as nitrocellulose, acetyl cellulose, cellulose ether, etc.), urethane (polymer, oligomer, etc. containing a urethane structure in the molecule), urea (polymer, oligomer, etc. containing a urea structure in the molecule), urethane Examples include urea (polymer, oligomer, etc. containing a urethane structure and a urea structure in the molecule), and the like.
レオロジーコントロール剤の市販品としては、例えば、ディスパロン６９００（楠本化成（株）製）、ディスパロンＡ６０３（楠本化成（株）製）、チクゾールＷ３００（共栄社化学（株））等のアマイドワックス；ディスパロン４２００（楠本化成（株）製）等のポリエチレンワックス；ＣＡＢ（セルロース・アセテート・ブチレート、イーストマン・ケミカル・プロダクツ社製）、ＨＥＣ（ヒドロキシエチルセルロース、住友精化（株）製）、疎水化ＨＥＣ（大同化成工業（株）製）、ＣＭＣ（カルボキシメチルセルロース、第一工業製薬（株）製）等のセルロース系のレオロジーコントロール剤；ＢＹＫ－４１０、ＢＹＫ－４１１、ＢＹＫ－４２０、ＢＹＫ－４２５（以上、ビックケミー（株）製）等のウレタンウレア系のレオロジーコントロール剤；フローノンＳＤＲ－８０（共栄社化学（株））等の硫酸エステル系アニオン系界面活性剤；フローノンＳＡ－３４５ＨＦ（共栄社化学（株））等のポリオレフィン系のレオロジーコントロール剤；フローノンＨＲ－４ＡＦ（共栄社化学（株））等の高級脂肪酸アマイド系のレオロジーコントロール剤；等を挙げることができる。 Commercially available rheology control agents include amide waxes such as Disparon 6900 (manufactured by Kusumoto Kasei Co., Ltd.), Disparon A603 (manufactured by Kusumoto Kasei Co., Ltd.), Thikusol W300 (manufactured by Kyoeisha Chemical Co., Ltd.); Polyethylene wax such as CAB (cellulose acetate butyrate, manufactured by Eastman Chemical Products), HEC (hydroxyethylcellulose, manufactured by Sumitomo Seika Co., Ltd.), hydrophobized HEC (Daido Chemical Co., Ltd.), etc. Cellulose-based rheology control agents such as CMC (carboxymethyl cellulose, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.); BYK-410, BYK-411, BYK-420, BYK-425 (bykchemy ( Urethane urea-based rheology control agents such as Flowon SDR-80 (Kyoeisha Chemical Co., Ltd.); sulfate ester-based anionic surfactants such as Flowon SA-345HF (Kyoeisha Chemical Co., Ltd.) rheology control agents based on higher fatty acids such as Fluonon HR-4AF (Kyoeisha Kagaku Co., Ltd.); and the like.
本発明の塗料組成物においてレオロジーコントロール剤を使用する場合、使用量は、エポキシ樹脂（Ａ）及びポリイソシアネート化合物（Ｂ)の固形分総量を基準にして、０．１～２０質量％、特に０．５～１５質量％、さらに特に０．８～１０質量％の範囲内であることが、仕上り外観及び塗装作業性の観点から好ましい。 When a rheology control agent is used in the coating composition of the present invention, the amount used is 0.1 to 20% by mass, especially 0.1 to 20% by mass, based on the total solid content of the epoxy resin (A) and the polyisocyanate compound (B). The content is preferably in the range of .5 to 15% by mass, more particularly 0.8 to 10% by mass, from the viewpoint of finished appearance and painting workability.
＜その他の成分＞
本発明の塗料組成物にはさらに必要に応じて、顔料分散剤、表面調整剤、界面活性剤、消泡剤、硬化剤（ポリイソシアネート化合物（Ｂ）を除く）、硬化触媒、防腐剤、凍結防止剤等を含有させることができる。
<Other ingredients>
The coating composition of the present invention further includes pigment dispersants, surface conditioners, surfactants, antifoaming agents, curing agents (excluding polyisocyanate compound (B)), curing catalysts, preservatives, freezing agents, etc., as necessary. It may contain an inhibitor and the like.
＜塗料組成物の塗装＞
本発明の塗料組成物は、フリー（遊離）のイソシアネート基を有するポリイソシアネート化合物（Ｂ）を構成成分とするため、常温で基体樹脂であるエポキシ樹脂（Ａ）との架橋反応が進行する。本発明の塗料組成物は、エポキシ樹脂（Ａ）を含有する主剤と、ポリイソシアネート化合物（Ｂ）を含有する硬化剤との２液型塗料であり、通常、塗装直前に主剤と硬化剤とを混合し、有機溶剤等の溶媒を必要に応じて添加して粘度調整することにより好適に使用される。
<Coating of paint composition>
Since the coating composition of the present invention contains a polyisocyanate compound (B) having a free isocyanate group as a constituent component, the crosslinking reaction with the epoxy resin (A) which is the base resin proceeds at room temperature. The coating composition of the present invention is a two-component coating consisting of a base agent containing an epoxy resin (A) and a curing agent containing a polyisocyanate compound (B). It is suitably used by mixing and adjusting the viscosity by adding a solvent such as an organic solvent as necessary.
その際、硫酸バリウム（Ｃ）、ゼオライト（Ｄ）及び必要に応じて使用される成分は、一般に、主剤側に配合しておくことが好ましい。主剤側への配合は、例えばディスパー、ホモジナイザー等の混合装置を用いて行うことができる。 At that time, barium sulfate (C), zeolite (D), and components used as necessary are generally preferably blended into the main ingredient. Blending to the main ingredient side can be carried out using a mixing device such as a disper or a homogenizer.
本発明の塗料組成物の塗装は、例えば、浸漬塗り、刷毛塗り、ロール刷毛塗り、スプレーコート、ロールコート、スピンコート、ディップコート、バーコート、フローコート、静電塗装、エアレス塗装、電着塗装、ダイコート等の塗装方法によって行うことができる。得られる塗膜の乾燥膜厚は、通常１０μｍ～１５０μｍ、好ましくは３０μｍ～８０μｍの範囲内が適している。 The coating composition of the present invention can be applied, for example, by dip coating, brush coating, roll brush coating, spray coating, roll coating, spin coating, dip coating, bar coating, flow coating, electrostatic coating, airless coating, and electrodeposition coating. This can be done by a coating method such as , die coating or the like. The dry thickness of the resulting coating film is usually in the range of 10 μm to 150 μm, preferably 30 μm to 80 μm.
被塗物としては、冷延鋼板、黒皮鋼板、合金化亜鉛メッキ鋼板、電気亜鉛メッキ鋼板等、及びこれらを素材とするブルドーザー、油圧ショベル、ホイールローダ等の建設機械又は産業機械等を挙げることができる。これらは必要に応じて、ショットブラスト、表面調整、表面処理等を施したものであってもよい。 Examples of objects to be coated include cold-rolled steel sheets, black-skinned steel sheets, alloyed galvanized steel sheets, electrogalvanized steel sheets, etc., as well as construction machines or industrial machines such as bulldozers, hydraulic excavators, and wheel loaders made of these materials. Can be done. These may be subjected to shot blasting, surface conditioning, surface treatment, etc., as necessary.
本発明の塗料組成物は、仕上り外観及び防食性に優れるので、上記被塗物に塗装するための下塗塗料（プライマー塗料）、特にウエットオンウエット仕様の下塗塗膜及び上塗塗膜からなる複層塗膜における下塗塗膜形成の下塗塗料組成物として、好適に使用することができる。 Since the coating composition of the present invention has excellent finished appearance and corrosion resistance, it can be used as an undercoat (primer paint) to be applied to the above-mentioned objects, especially a multi-layer coating consisting of a wet-on-wet undercoat and a topcoat. It can be suitably used as an undercoat paint composition for forming an undercoat film in a paint film.
ウエットオンウエット仕様とは、未硬化の下塗塗膜上に上塗塗膜を形成する複層塗装工程の仕様である。 The wet-on-wet specification is a specification for a multilayer coating process in which a topcoat film is formed on an uncured basecoat film.
［複層塗膜形成方法］
本発明の複層塗膜形成方法は、被塗物に、下塗塗料組成物を塗装して下塗塗膜を形成する工程、及び下塗塗膜に上塗塗料組成物を塗装して上塗塗膜を形成する工程を有する。また、本発明の複層塗膜形成方法においては、下塗塗膜形成の下塗塗料組成物として、本発明の塗料組成物を使用する。
[Multilayer coating formation method]
The multi-layer coating film forming method of the present invention includes a step of coating an object with an undercoat paint composition to form an undercoat film, and a step of coating an undercoat paint film with a topcoat paint composition to form a top coat film. It has a process of Furthermore, in the method for forming a multilayer coating film of the present invention, the coating composition of the present invention is used as an undercoat paint composition for forming an undercoat film.
本発明の塗料組成物は、ウエットオンウエット適性に優れているので、特に、被塗物上に、本発明の塗料組成物による下塗塗膜（未硬化塗膜）を形成し、該下塗塗膜（未硬化塗膜）上に、上塗塗料組成物による上塗塗膜を形成し、両塗膜を同時に乾燥して塗膜を形成する方法、において好適に使用することができる。 Since the coating composition of the present invention has excellent wet-on-wet suitability, in particular, it is possible to form an undercoat film (uncured paint film) of the paint composition of the present invention on an object to be coated. It can be suitably used in a method in which a top coat is formed using a top coat composition on an uncured paint film, and both coats are simultaneously dried to form a paint film.
本発明の複層塗膜形成方法における被塗物は、上述のものを用いることができる。 As the object to be coated in the method for forming a multilayer coating film of the present invention, those described above can be used.
本発明の複層塗膜形成方法における上塗塗料組成物としては、従来公知の塗料組成物を制限なく使用することができる。具体的には例えば、ウレタン樹脂系塗料、アクリル樹脂系塗料、シリコン樹脂系塗料、弗素樹脂系塗料、油性系塗料、フタル酸樹脂系塗料等を使用することができる。 As the top coating composition in the method for forming a multilayer coating film of the present invention, conventionally known coating compositions can be used without limitation. Specifically, for example, urethane resin paints, acrylic resin paints, silicone resin paints, fluororesin paints, oil-based paints, phthalate resin paints, etc. can be used.
上記ウエットオンウエットの塗膜形成方法において、本発明の塗料組成物の塗装は、前記の塗装方法によって行うことができる。下塗塗膜の乾燥膜厚は、通常１０μｍ～１５０μｍ、好ましくは２０μｍ～６０μｍの範囲内が適している。 In the wet-on-wet coating film forming method described above, the coating composition of the present invention can be applied by the coating method described above. The dry thickness of the undercoat film is normally in the range of 10 μm to 150 μm, preferably in the range of 20 μm to 60 μm.
下塗塗膜（未硬化塗膜）上への、上塗塗料組成物の塗装は、例えば、浸漬塗り、刷毛塗り、ロール刷毛塗り、スプレーコート、ロールコート、スピンコート、ディップコート、バーコート、フローコート、静電塗装、エアレス塗装、電着塗装、ダイコート等の塗装方法によって行うことができる。上塗塗膜の乾燥膜厚は、通常、１０μｍ～１５０μｍ、好ましくは２０μｍ～６０μｍの範囲内が適している。 The top coat composition can be applied onto the undercoat film (uncured film) by, for example, dip coating, brush coating, roll brush coating, spray coating, roll coating, spin coating, dip coating, bar coating, flow coating. , electrostatic coating, airless coating, electrodeposition coating, die coating, and other coating methods. The dry film thickness of the top coat is usually in the range of 10 μm to 150 μm, preferably 20 μm to 60 μm.
次いで、常温～１６０℃で１０～１２０分間、好ましくは６０～１２０℃で２０～９０分間乾燥させることにより、複層塗膜を得ることができる。 Next, a multilayer coating film can be obtained by drying at room temperature to 160°C for 10 to 120 minutes, preferably at 60 to 120°C for 20 to 90 minutes.
本発明の塗料組成物を塗装して該未硬化塗膜を形成した後、必要に応じて、常温でのセッティング又は予備加熱を行うこともできる。 After coating the coating composition of the present invention to form the uncured coating film, setting at room temperature or preheating can be performed as necessary.
以下、製造例、実施例及び比較例により、本発明をさらに詳細に説明するが、本発明はこれらに限定されるものではない。各例中の「部」は質量部、「％」は質量％を示す。 Hereinafter, the present invention will be explained in more detail with reference to Production Examples, Examples, and Comparative Examples, but the present invention is not limited thereto. In each example, "part" indicates part by mass, and "%" indicates mass %.
［下塗塗料組成物（プライマー塗料組成物）の製造］
＜実施例１＞プライマー塗料組成物Ｎｏ．１の製造
以下の工程１～工程２によって、プライマー塗料組成物Ｎｏ．１を得た。
[Manufacture of undercoat paint composition (primer paint composition)]
<Example 1> Primer coating composition No. Production of Primer Coating Composition No. 1 by the following steps 1 and 2. I got 1.
工程１：
ＥＰＯＭＩＫ Ｕ４６６ＢＴ６０（注１）４０部（固形分）、ＢＬＡＮＣ ＦＩＸＥ ＭＩＣＲＯ（注５）６０部、ＴＩ－ＳＥＬＥＣＴ ＴＳ－６２００（注１１）６０部、Ｋ－ＷＨＩＴＥ １０５（注１２）３０部、サンライト ＳＬ－１５００（注１３）８０部、及びモレキュラーシーブ５Ａ（注１９）２０部に、酢酸ブチルを適量加え、サンドミルにて分散し、顔料分散ペーストを得た。
Process 1:
EPOMIK U466BT60 (Note 1) 40 parts (solid content), BLANC FIXE MICRO (Note 5) 60 parts, TI-SELECT TS-6200 (Note 11) 60 parts, K-WHITE 105 (Note 12) 30 parts, Sunlight SL An appropriate amount of butyl acetate was added to 80 parts of -1500 (Note 13) and 20 parts of Molecular Sieve 5A (Note 19) and dispersed in a sand mill to obtain a pigment dispersion paste.
工程２：
上記にて得た顔料分散ペーストに、ＥＰＯＭＩＫ Ｕ４６６ＢＴ６０（注１）４０部（固形分）、及びディスパロン Ａ６０３－２０Ｘ（注１４）１．５部（固形分）を配合し、表面調整剤、消泡剤を加えて撹拌し、酢酸ブチルを加えて、固形分を調整した。さらに後述の冷間圧延鋼板への塗装直前にタケネートＤ－１０２（注１５）２０部（固形分）及び酢酸ブチルを加え固形分６０質量％、塗装粘度２０秒／２５℃（イワタカップで測定）のプライマー塗料組成物Ｎｏ．１を得た。
Process 2:
40 parts (solid content) of EPOMIK U466BT60 (Note 1) and 1.5 parts (solid content) of Disparon A603-20X (Note 14) were added to the pigment dispersion paste obtained above, and a surface conditioner and antifoaming agent were added. The solid content was adjusted by adding butyl acetate. Immediately before painting the cold-rolled steel plate described below, 20 parts (solid content) of Takenate D-102 (Note 15) and butyl acetate are added to give a solid content of 60% by mass and a coating viscosity of 20 seconds/25°C (measured with an Iwata cup). Primer paint composition No. I got 1.
＜実施例２～１４＞プライマー塗料組成物Ｎｏ．２～１４の製造
配合内容を表１に示すものとした以外は、実施例１と同様にして、プライマー塗料組成物Ｎｏ．２～１４を得た。
<Examples 2 to 14> Primer coating composition No. Production of Primer Coating Compositions No. 2 to 14 Primer paint composition No. 2 to 14 were obtained.
＜比較例１～９＞プライマー塗料組成物Ｎｏ．１５～２３の製造
配合内容を表２に示すものとした以外は、実施例１と同様にして、各プライマー塗料組成物Ｎｏ．１５～Ｎｏ．２３を得た。
<Comparative Examples 1 to 9> Primer paint composition No. Production of Primer Coating Compositions No. 15 to 23 Each primer coating composition No. 15~No. I got 23.
なお、塗料組成物Ｎｏ．１５及び２２の工程１においてはＥＰＯＭＩＫ Ｕ４６６ＢＴ６０（注１）をＥＰＩＣＬＯＮ １０５０（注３）とした。 In addition, coating composition No. In Step 1 of 15 and 22, EPOMIK U466BT60 (Note 1) was replaced with EPICLON 1050 (Note 3).
なお、表１～２において、（注１）～（注２０）の詳細は下記のとおりである。 In Tables 1 and 2, details of (Note 1) to (Note 20) are as follows.
（注１）ＥＰＯＭＩＫ Ｕ４６６ＢＴ６０：三井化学株式会社、商品名、脂肪酸アミン変性ビスフェノールＡ型エポキシ樹脂、水酸基価１０８ｍｇＫＯＨ／ｇ、重量平均分子量１３０００
（注２）ＥＰＯＭＩＫ Ｕ４５２ＣＴ６０：三井化学株式会社、商品名、変性ビスフェノールＡ型エポキシ樹脂、水酸基価１５６ｍｇＫＯＨ／ｇ、重量平均分子量１００００
（注３）ＥＰＩＣＬＯＮ １０５０：ＤＩＣ株式会社、商品名、ビスフェノールＡ型エポキシ樹脂、重量平均分子量２０００、水酸基価１０６ｍｇＫＯＨ／ｇ
（注４）アラキード９２０５：荒川化学工業株式会社、商品名、重量平均分子量３００００、水酸基価２１５ｍｇＫＯＨ／ｇ
(Note 1) EPOMIK U466BT60: Mitsui Chemicals, Inc., trade name, fatty acid amine modified bisphenol A epoxy resin, hydroxyl value 108mgKOH/g, weight average molecular weight 13000
(Note 2) EPOMIK U452CT60: Mitsui Chemicals, Inc., trade name, modified bisphenol A type epoxy resin, hydroxyl value 156mgKOH/g, weight average molecular weight 10000
(Note 3) EPICLON 1050: DIC Corporation, trade name, bisphenol A type epoxy resin, weight average molecular weight 2000, hydroxyl value 106mgKOH/g
(Note 4) Arachide 9205: Arakawa Chemical Industry Co., Ltd., trade name, weight average molecular weight 30,000, hydroxyl value 215mgKOH/g
（注５）ＢＬＡＮＣ ＦＩＸＥ ＭＩＣＲＯ：ザハトラーベン株式会社、商品名、硫酸バリウム、平均粒子径０．７μｍ、吸油量１３ｍｌ／１００ｇ
（注６）硫酸バリウム ＨＦ：深州嘉信化工有限責任公司、商品名、硫酸バリウム、平均粒子径０．９μｍ、吸油量１４ｍｌ／１００ｇ
（注７）ＳＰＡＲＷＩＴＥ Ｗ－５ＨＢ：Ｓｉｎｏ－Ｃａｎ Ｍｉｃｒｏｎｉｚｅｄ Ｐｒｏｄｕｃｔ ｃｏ．，Ｌｔｄ、商品名、硫酸バリウム、平均粒子径１．６μｍ、吸油量１３ｍｌ／１００ｇ
（注８）ＢＡＲＩＦＩＮＥ ＢＦ－２０：堺化学工業株式会社、商品名、硫酸バリウム、平均粒子径０．０３μｍ、吸油量２４ｍｌ／１００ｇ
（注９）硫酸バリウム ＢＡ：堺化学工業株式会社、商品名、硫酸バリウム、平均粒子径８μｍ、吸油量８ｍｌ／１００ｇ
（注１０）ＬＡＫＡＢＡＲ ＳＦ：ＬＡＫＡＶＩＳＵＴＨ ＬＴＤ、商品名、硫酸バリウム、平均粒子径１０．４μｍ、吸油量１０ｍｌ／１００ｇ
(Note 5) BLANC FIXE MICRO: Sachtraben Co., Ltd., product name, barium sulfate, average particle size 0.7 μm, oil absorption 13 ml/100 g
(Note 6) Barium sulfate HF: Shenzhou Jiaxin Chemical Co., Ltd., trade name, barium sulfate, average particle size 0.9μm, oil absorption 14ml/100g
(Note 7) SPARWITE W-5HB: Sino-Can Micronized Product co. , Ltd., trade name, barium sulfate, average particle size 1.6μm, oil absorption 13ml/100g
(Note 8) BARIFINE BF-20: Sakai Chemical Industry Co., Ltd., trade name, barium sulfate, average particle size 0.03 μm, oil absorption 24 ml/100 g
(Note 9) Barium sulfate BA: Sakai Chemical Industry Co., Ltd., trade name, barium sulfate, average particle size 8 μm, oil absorption 8 ml/100 g
(Note 10) LAKABAR SF: LAKAVISUTH LTD, trade name, barium sulfate, average particle size 10.4μm, oil absorption 10ml/100g
（注１１）ＴＩ－ＳＥＬＥＣＴ ＴＳ－６２００：ケマーズ株式会社、商品名、二酸化チタン
（注１２）Ｋ－ＷＨＩＴＥ １０５：テイカ株式会社製、商品名、トリポリリン酸二水素アルミニウム
（注１３）サンライト ＳＬ－１５００：竹原化学工業株式会社、商品名、炭酸カルシウム
(Note 11) TI-SELECT TS-6200: Chemours Co., Ltd., product name, titanium dioxide (Note 12) K-WHITE 105: Made by Teika Co., Ltd., product name, aluminum dihydrogen tripolyphosphate (Note 13) Sunlight SL- 1500: Takehara Chemical Industry Co., Ltd., product name, calcium carbonate
（注１４）ディスパロン Ａ６０３－２０Ｘ：楠本化成株式会社、商品名、脂肪酸アマイドワックス
（注１５）タケネートＤ－１０２：三井化学株式会社、商品名、ポリイソシアネート化合物、ＴＤＩ系ウレタンポリマー（ウレタン変性ＴＤＩ）
（注１６）スミジュール Ｎ３３００：住化コベストロウレタン株式会社、商品名、イソシアヌレート変性ＨＤＩ（ＨＤＩの３量体）
（注１７）ミリオネートＣＡ－１Ａ：保土谷化学株式会社、商品名、ＭＤＩ系ポリイソシアネート
(Note 14) Disparon A603-20X: Kusumoto Kasei Co., Ltd., trade name, fatty acid amide wax (Note 15) Takenate D-102: Mitsui Chemicals Co., Ltd., trade name, polyisocyanate compound, TDI-based urethane polymer (urethane-modified TDI)
(Note 16) Sumidur N3300: Sumika Covestrourethane Co., Ltd., trade name, isocyanurate-modified HDI (trimer of HDI)
(Note 17) Millionate CA-1A: Hodogaya Chemical Co., Ltd., trade name, MDI polyisocyanate
（注１８）モレキュラーシーブ ３Ａ：ユニオン昭和株式会社、商品名、ナトリウムカルシウムアミノシリケート、細孔径０．２５ｎｍ
（注１９）モレキュラーシーブ ５Ａ：ユニオン昭和株式会社、商品名、ナトリウムカルシウムアミノシリケート、細孔径０．４２ｎｍ
（注２０）モレキュラーシーブ １３Ｘ：ユニオン昭和株式会社、商品名、ナトリウムカルシウムアミノシリケート、細孔径１．０ｎｍ
(Note 18) Molecular sieve 3A: Union Showa Co., Ltd., trade name, sodium calcium aminosilicate, pore size 0.25 nm
(Note 19) Molecular sieve 5A: Union Showa Co., Ltd., trade name, sodium calcium aminosilicate, pore size 0.42 nm
(Note 20) Molecular sieve 13X: Union Showa Co., Ltd., trade name, sodium calcium aminosilicate, pore size 1.0 nm
［上塗塗料組成物の製造］
＜製造例Ｎｏ．１＞アクリル樹脂溶液の製造
スワゾール１０００（コスモ石油株式会社製、芳香族炭化水素系溶媒）２８部、トルエン８５部、スチレン４１．６部、ｎ－ブチルアクリレート６．９部、イソブチルメタクリレート１９部、プラクセルＦＭ－３（注２１）１５部、２－ヒドロキシエチルメタクリレート１７部、アクリル酸０．５部、ジ－ｔｅｒｔ－ブチルハイドロパーオキサイド８部を窒素ガス下で１１０℃において反応させて、固形分質量濃度４５％のアクリル樹脂溶液を得た。得られたアクリル樹脂は、酸価３．９ｍｇＫＯＨ／ｇ、水酸基価９４．９ｍｇＫＯＨ／ｇ、重量平均分子量１１，０００であった。
[Manufacture of top coating composition]
<Manufacturing example No. 1> Production of acrylic resin solution Swazol 1000 (manufactured by Cosmo Oil Co., Ltd., aromatic hydrocarbon solvent) 28 parts, toluene 85 parts, styrene 41.6 parts, n-butyl acrylate 6.9 parts, isobutyl methacrylate 19 parts, 15 parts of Plaxel FM-3 (Note 21), 17 parts of 2-hydroxyethyl methacrylate, 0.5 parts of acrylic acid, and 8 parts of di-tert-butyl hydroperoxide were reacted at 110°C under nitrogen gas to reduce the solid content. An acrylic resin solution having a mass concentration of 45% was obtained. The obtained acrylic resin had an acid value of 3.9 mgKOH/g, a hydroxyl value of 94.9 mgKOH/g, and a weight average molecular weight of 11,000.
（注２１）プラクセルＦＭ－３：ダイセル化学工業株式会社製、商品名、２－ヒドロキシエチルアクリレートのε－カプロラクトン変性ビニルモノマー (Note 21) Plaxel FM-3: manufactured by Daicel Chemical Industries, Ltd., trade name, ε-caprolactone modified vinyl monomer of 2-hydroxyethyl acrylate
＜製造例Ｎｏ．２＞上塗塗料組成物Ｎｏ．１の製造
製造例Ｎｏ．１で得たアクリル樹脂溶液８０部（固形分）、ＴＩ－ＳＥＬＥＣＴ ＴＳ－６２００（注１１）１２部、ホスターパームエローＨ－３Ｇ（注２２）１２部、ＢＡＲＩＦＩＮＥ ＢＦ－２０（注８）１５部、Ｂａｙｆｅｒｒｏｘ４９０５（注２３）１２部及びＴＩＮＵＶＩＮ２９２（注２４）１部を配合し、スワゾール１０００（コスモ石油株式会社製、芳香族炭化水素系溶媒）で固形分を調整した混合物を、サンドミルにて分散することによって主剤塗料を得た。さらに後述のプライマー塗膜への塗装直前に、スミジュール Ｎ３３００（注１６）２０部（固形分）及びＫＢＭ－４０３（注２５）０．５部を混合撹拌し、固形分６０％の上塗塗料組成物Ｎｏ．１を得た。
<Manufacturing example No. 2> Top coating composition No. Production of 1 Production example No. 80 parts (solid content) of the acrylic resin solution obtained in step 1, 12 parts of TI-SELECT TS-6200 (Note 11), 12 parts of Hoster Palm Yellow H-3G (Note 22), 15 parts of BARIFINE BF-20 (Note 8) , 12 parts of Bayferrox 4905 (Note 23) and 1 part of TINUVIN 292 (Note 24), and the solid content was adjusted with Swazol 1000 (manufactured by Cosmo Oil Co., Ltd., aromatic hydrocarbon solvent), and the mixture was dispersed using a sand mill. By this, a base paint was obtained. Furthermore, immediately before coating on the primer coating described below, 20 parts (solid content) of Sumidur N3300 (Note 16) and 0.5 part of KBM-403 (Note 25) were mixed and stirred to form a top coat with a solid content of 60%. Item No. I got 1.
（注２２）ホスターパームエローＨ－３Ｇ：クラリアント社製、商品名、ハンザエロー系黄色顔料
（注２３）Ｂａｙｆｅｒｒｏｘ ４９０５：Ｌａｎｘｅｓｓ株式会社、商品名、赤色顔料
（注２４）ＴＩＮＵＶＩＮ２９２：ＢＡＳＦ株式会社、商品名、光安定化剤
（注２５）ＫＢＭ－４０３：信越化学株式会社、商品名、エポキシ基含有シランカップリング剤
(Note 22) Hoster Palm Yellow H-3G: Manufactured by Clariant, trade name, Hansa yellow yellow pigment (Note 23) Bayferrox 4905: Lanxess Corporation, trade name, red pigment (Note 24) TINUVIN292: BASF Corporation, trade name , Light stabilizer (Note 25) KBM-403: Shin-Etsu Chemical Co., Ltd., trade name, epoxy group-containing silane coupling agent
［複層塗膜形成塗板の作製］
＜複層塗膜形成塗板Ｎｏ．１の作製＞
下記の工程１～工程３によって、複層塗膜形成塗板Ｎｏ．１を得た。
[Preparation of multilayer coating film forming coated plate]
<Multi-layer coating film forming coating plate No. Preparation of 1>
By the following steps 1 to 3, multilayer coating film forming coated plate No. I got 1.
工程１：
冷間圧延鋼板（大きさ０．８×７０×１５０ｍｍ、パルボンド＃３０２０）に実施例１で得られたプライマー塗料組成物Ｎｏ．１を用い、乾燥膜厚が４０μｍになるようにスプレー塗装し、２５℃で３分間セッティング（静置）し、プライマー塗膜（下塗塗膜）を得た。
Process 1:
Primer paint composition No. 1 obtained in Example 1 was applied to a cold rolled steel plate (size 0.8 x 70 x 150 mm, Palbond #3020). 1 to a dry film thickness of 40 μm, and was set (left standing) at 25° C. for 3 minutes to obtain a primer film (undercoat film).
工程２：
次いで、１０部のカンペ工業用ウレタンシンナー２０５（関西ペイント社製、２液ウレタン塗料用シンナー）を、１００部の上塗塗料組成物Ｎｏ．１に対して配合し配合塗料を得た。得られた配合塗料を、上記プライマー塗膜上に、乾燥膜厚が４０μｍになるようにスプレー塗装にてウエットオンウエットで塗装して、上塗塗膜を形成し、複層塗膜を得た。
Process 2:
Next, 10 parts of Kanpe Industrial Urethane Thinner 205 (manufactured by Kansai Paint Co., Ltd., two-component urethane paint thinner) was added to 100 parts of top coating composition No. 1 to obtain a blended paint. The obtained blended paint was applied wet-on-wet by spray coating onto the primer coating film to a dry film thickness of 40 μm to form a topcoat film to obtain a multilayer coating film.
工程３：
工程２によって得られた複層塗膜を、２５℃で１０分間セッティングした後、８０℃で３０分間加熱乾燥させ、さらに室温（２０℃）で７２時間乾燥させて複層塗膜形成塗板Ｎｏ．１を得た。
Step 3:
The multilayer coating film obtained in step 2 was set at 25°C for 10 minutes, then heated and dried at 80°C for 30 minutes, and further dried at room temperature (20°C) for 72 hours to obtain multilayer coating film forming coated plate No. I got 1.
＜複層塗膜形成塗板Ｎｏ．２～Ｎｏ．１４の作製＞（実施例用）
プライマー塗料組成物Ｎｏ．１をプライマー塗料組成物Ｎｏ．２～Ｎｏ．１４とした以外は、複層塗膜形成塗板Ｎｏ．１と同様にして、複層塗膜形成塗板Ｎｏ．２～Ｎｏ．１４を得た。
<Multi-layer coating film forming coating plate No. 2~No. Preparation of 14> (for Example)
Primer paint composition No. 1 as primer coating composition No. 1. 2~No. Except for No. 14, multi-layer coating film forming coating plate No. In the same manner as in 1, a multilayer coating film was formed on coated plate No. 1. 2~No. I got 14.
＜複層塗膜形成塗板Ｎｏ．１５～Ｎｏ．２３の作製＞（比較例用）
プライマー塗料組成物Ｎｏ．１をプライマー塗料組成物Ｎｏ．１５～Ｎｏ．２３とした以外は、複層塗膜形成塗板Ｎｏ．１と同様にして、複層塗膜形成塗板Ｎｏ．１５～Ｎｏ．２３を得た。
<Multi-layer coating film forming coating plate No. 15~No. Preparation of 23> (for comparative example)
Primer paint composition No. 1 as primer coating composition No. 1. 15~No. Except for No. 23, multi-layer coating film forming coating plate No. 23 was used. In the same manner as in 1, a multilayer coating film was formed on coated plate No. 1. 15~No. I got 23.
［塗膜性能試験］
各複層塗膜形成塗板について、後記の試験項目につき塗膜性能試験を行った。試験結果を表１及び表２に示す。
[Coating film performance test]
A coating film performance test was conducted on each multilayer coating plate with respect to the test items described below. The test results are shown in Tables 1 and 2.
＜仕上り外観（注２６）＞
各複層塗膜形成塗板の塗面外観を下記基準に基づき目視で評価した。
<Finished appearance (Note 26)>
The appearance of the coated surface of each multilayer coated plate was visually evaluated based on the following criteria.
◎：上塗塗膜とプライマー塗膜の混層がなく平滑性が良好で、かつ６０度光沢値が９０以上であった。
○：上塗塗膜とプライマー塗膜の混層がなく平滑性が良好で、かつ６０度光沢値が７５以上９０未満であった。
△：上塗塗膜とプライマー塗膜が混層しており、うねり、ツヤビケ及びチリ肌から選ばれる少なくとも１種の仕上り外観の低下がやや見られ、６０度光沢値が６０以上７５未満であった。
×：上塗塗膜とプライマー塗膜の混層が著しく、うねり、ツヤビケ、チリ肌から選ばれる少なくとも１種の仕上り外観の低下が著しく、６０度光沢値が６０未満であった。
◎: There was no mixed layer of top coat and primer coat, the smoothness was good, and the 60 degree gloss value was 90 or more.
Good: There was no mixed layer of top coat and primer coat, the smoothness was good, and the 60 degree gloss value was 75 or more and less than 90.
Δ: The topcoat film and the primer film were mixed, and at least one kind of deterioration in the finished appearance selected from waviness, glossiness, and dusty skin was observed, and the 60 degree gloss value was 60 or more and less than 75.
×: The mixed layer of the top coat film and the primer film was significant, and at least one type of finish appearance selected from waviness, glossiness, and dusty skin was significantly deteriorated, and the 60 degree gloss value was less than 60.
＜鉛筆硬度（注２７）＞
ＪＩＳ Ｋ ５６００－５－４に準じて、各複層塗膜形成塗板面に対し約４５°の角度に鉛筆の芯を当て、芯が折れない程度に強く塗板面に押し付けながら前方に均一な速さで約１０ｍｍ動かした。塗膜が破れなかった最も硬い鉛筆の硬度記号を鉛筆硬度とし、下記基準に基づき評価した。
<Pencil hardness (Note 27)>
In accordance with JIS K 5600-5-4, place the lead of a pencil at an angle of about 45° to the surface of each multi-layer paint film, and move it forward at a uniform speed while pressing firmly against the surface of the surface of the paint so that the lead does not break. I moved it about 10mm. The hardness code of the hardest pencil that did not break the coating film was defined as pencil hardness, and evaluation was made based on the following criteria.
◎：鉛筆硬度がＨ以上であった。
○：鉛筆硬度がＦ以上Ｈ未満であった。
△：鉛筆硬度がＨＢ以上Ｆ未満であった。
×：鉛筆硬度がＨＢ未満であった。
◎: Pencil hardness was H or higher.
○: Pencil hardness was F or more and less than H.
Δ: Pencil hardness was HB or more and less than F.
×: Pencil hardness was less than HB.
＜付着性（注２８）＞
ＪＩＳ Ｋ ５６００－５－６に準じて、各複層塗膜形成塗板の２ｍｍ碁盤目試験を行い、碁盤目の残数を下記基準に基づき評価した。
<Adhesion (Note 28)>
In accordance with JIS K 5600-5-6, a 2 mm grid test was conducted for each multilayer coating plate, and the number of grid marks remaining was evaluated based on the following criteria.
◎：碁盤目の残数が分類１以上であった。
○：碁盤目の残数が分類２以上分類１未満であった。
△：碁盤目の残数が分類３以上分類２未満であった。
×：碁盤目の残数が分類３未満であった。
◎: The number remaining on the grid was classified as 1 or higher.
○: The number remaining on the grid was greater than or equal to classification 2 and less than classification 1.
△: The number remaining in the grid was 3 or more and less than 2.
×: The remaining number of grid points was less than classification 3.
＜耐水性（注２９）＞
各複層塗膜形成塗板について、２３℃の温水に１０日間浸漬した後の外観を下記基準に基づき評価した。
<Water resistance (Note 29)>
The appearance of each multilayer coated plate after being immersed in warm water at 23° C. for 10 days was evaluated based on the following criteria.
◎：試験前の塗膜に対して、全く外観の変化が認められなかった。
○：試験前の塗膜に対して、わずかにツヤびけ、フクレ又は変色が見られたが、製品とした時に問題の無いレベルであった。
△：試験前の塗膜に対して、若干、ツヤびけ、ワレ、フクレ又は変色が見られ、製品として劣るレベルであった。
×：試験前の塗膜に対して、著しく、ツヤびけ、ワレ、フクレ又は変色が見られた。
◎: No change in appearance was observed with respect to the coating film before the test.
○: Slight gloss, blistering, or discoloration was observed in the coating film before the test, but it was at a level that caused no problems when used as a product.
Δ: Some glossiness, cracking, blistering, or discoloration was observed in the coating film before the test, and the level was poor as a product.
×: Significant loss of gloss, cracking, blistering, or discoloration was observed in the coating film before the test.
＜防食性（注３０）＞
各複層塗膜形成塗板に、ナイフでクロスカット傷を入れ、これをＪＩＳ Ｚ－２３７１に準じて１２０時間耐塩水噴霧試験を行い、ナイフ傷からの錆、フクレ幅によって下記基準に基づき評価した。
<Corrosion resistance (Note 30)>
Cross-cut scratches were made with a knife on each multilayer coating coating plate, and a 120-hour salt spray resistance test was conducted according to JIS Z-2371, and the rust and blistering width from the knife scratches were evaluated based on the following criteria. .
◎：錆、フクレの最大幅が、カット部から２ｍｍ未満(片側)であった。
○：錆、フクレの最大幅が、カット部から２ｍｍ以上でかつ３ｍｍ未満(片側)であった。
△：錆、フクレの最大幅が、カット部から３ｍｍ以上でかつ４ｍｍ未満(片側)であった。
×：錆、フクレの最大幅が、カット部から４ｍｍ以上(片側)であった。
◎: The maximum width of rust and blisters was less than 2 mm from the cut portion (on one side).
Good: The maximum width of rust and blisters was 2 mm or more from the cut portion and less than 3 mm (on one side).
Δ: The maximum width of rust and blisters was 3 mm or more from the cut portion and less than 4 mm (on one side).
×: The maximum width of rust and blisters was 4 mm or more from the cut portion (on one side).
本発明を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。本出願は２０１９年９月１７日出願の日本特許出願（特願２０１９－１６８４９７）に基づくものであり、その内容はここに参照として取り込まれる。 Although the invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application (Japanese Patent Application No. 2019-168497) filed on September 17, 2019, the contents of which are incorporated herein by reference.
本発明の２液型塗料組成物によって、仕上り外観及び防食性に優れる複層塗膜を有する塗装物品を提供することができる。 By using the two-component coating composition of the present invention, it is possible to provide a coated article having a multilayer coating film with excellent finished appearance and corrosion resistance.
Claims (5)
前記エポキシ樹脂（Ａ）及び前記ポリイソシアネート化合物（Ｂ）の固形分総量を基準にして、前記エポキシ樹脂（Ａ）の含有量が６０～９０質量％、前記ポリイソシアネート化合物（Ｂ）の含有量が１０～４０質量％、前記硫酸バリウム（Ｃ）の含有量が１～１００質量％、前記ゼオライト（Ｄ）の含有量が１０～４０質量％である、２液型塗料組成物。 Contains an epoxy resin (A) with a weight average molecular weight of 5,000 to 25,000, a polyisocyanate compound (B), barium sulfate (C) with an average particle size of 0.01 to 5.0 μm, and zeolite (D) with a pore size of 0.50 nm or less. death,
Based on the total solid content of the epoxy resin (A) and the polyisocyanate compound (B), the content of the epoxy resin (A) is 60 to 90% by mass, and the content of the polyisocyanate compound (B) is A two-component coating composition, wherein the content of the barium sulfate (C) is 1 to 100% by mass, and the content of the zeolite (D) is 10 to 40% by mass.
前記下塗塗膜に上塗塗料組成物を塗装して上塗塗膜を形成する工程を有し、
前記下塗塗料組成物が請求項１～３のいずれか１項に記載の２液型塗料組成物である、複層塗膜形成方法。 a step of coating an object to be coated with an undercoat paint composition to form an undercoat film, and a step of applying a topcoat paint composition to the undercoat film to form a topcoat film,
A method for forming a multilayer coating film, wherein the undercoat coating composition is the two-component coating composition according to any one of claims 1 to 3.
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| JP2019168497 | 2019-09-17 | ||
| PCT/JP2020/027161 WO2021053942A1 (en) | 2019-09-17 | 2020-07-10 | Two-part coating composition |
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