JP2022084372A - Designable coating composition - Google Patents
Designable coating composition Download PDFInfo
- Publication number
- JP2022084372A JP2022084372A JP2020196214A JP2020196214A JP2022084372A JP 2022084372 A JP2022084372 A JP 2022084372A JP 2020196214 A JP2020196214 A JP 2020196214A JP 2020196214 A JP2020196214 A JP 2020196214A JP 2022084372 A JP2022084372 A JP 2022084372A
- Authority
- JP
- Japan
- Prior art keywords
- coating film
- resin
- mass
- coating composition
- parts
- 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.)
- Granted
Links
- 239000008199 coating composition Substances 0.000 title claims abstract description 102
- 229920005989 resin Polymers 0.000 claims abstract description 109
- 239000011347 resin Substances 0.000 claims abstract description 109
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 25
- 238000000576 coating method Methods 0.000 claims description 224
- 239000011248 coating agent Substances 0.000 claims description 223
- 229910000831 Steel Inorganic materials 0.000 claims description 57
- 239000010959 steel Substances 0.000 claims description 57
- -1 amine compound Chemical class 0.000 claims description 55
- 229920000178 Acrylic resin Polymers 0.000 claims description 49
- 239000004925 Acrylic resin Substances 0.000 claims description 49
- 239000002245 particle Substances 0.000 claims description 46
- 229920001225 polyester resin Polymers 0.000 claims description 45
- 239000004645 polyester resin Substances 0.000 claims description 45
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 38
- 239000007787 solid Substances 0.000 claims description 33
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 30
- 239000003973 paint Substances 0.000 claims description 25
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 24
- 229920000877 Melamine resin Polymers 0.000 claims description 23
- 239000004640 Melamine resin Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 19
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 16
- 238000006386 neutralization reaction Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 150000003335 secondary amines Chemical class 0.000 claims description 11
- 150000003512 tertiary amines Chemical class 0.000 claims description 10
- 238000009835 boiling Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000011324 bead Substances 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000000049 pigment Substances 0.000 description 51
- 239000000047 product Substances 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000000126 substance Substances 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000000178 monomer Substances 0.000 description 11
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 9
- 150000007974 melamines Chemical class 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 8
- 239000010419 fine particle Substances 0.000 description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 8
- 229920005862 polyol Polymers 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000008096 xylene Substances 0.000 description 8
- 229920003270 Cymel® Polymers 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000005056 polyisocyanate Substances 0.000 description 7
- 229920001228 polyisocyanate Polymers 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000004606 Fillers/Extenders Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 229920003180 amino resin Polymers 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 150000003077 polyols Chemical class 0.000 description 5
- 239000002344 surface layer Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910001335 Galvanized steel Inorganic materials 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005562 fading Methods 0.000 description 3
- 239000008397 galvanized steel Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 150000007519 polyprotic acids Polymers 0.000 description 3
- 239000002987 primer (paints) Substances 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- QBDAFARLDLCWAT-UHFFFAOYSA-N 2,3-dihydropyran-6-one Chemical compound O=C1OCCC=C1 QBDAFARLDLCWAT-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- QDCPNGVVOWVKJG-VAWYXSNFSA-N 2-[(e)-dodec-1-enyl]butanedioic acid Chemical compound CCCCCCCCCC\C=C\C(C(O)=O)CC(O)=O QDCPNGVVOWVKJG-VAWYXSNFSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
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- 239000011651 chromium Substances 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 229940043279 diisopropylamine Drugs 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- CJMZLCRLBNZJQR-UHFFFAOYSA-N ethyl 2-amino-4-(4-fluorophenyl)thiophene-3-carboxylate Chemical compound CCOC(=O)C1=C(N)SC=C1C1=CC=C(F)C=C1 CJMZLCRLBNZJQR-UHFFFAOYSA-N 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、均一な艶消し外観を有する意匠性に優れた塗膜を形成し、かつ耐候性に優れる塗料組成物に関し、鋼板等の基板の塗装に適した塗料組成物を提供するものである。 INDUSTRIAL APPLICABILITY The present invention provides a coating film suitable for coating a substrate such as a steel plate with respect to a coating film having a uniform matte appearance and excellent designability and excellent weather resistance. ..
冷延鋼板やめっき鋼板を基材として塗装を施した塗装鋼板はプレコート鋼板(「PCM」ともいう)とも呼ばれ、シャッター、雨戸、ドア、屋根及びサイディング等の建築部材、クーラー室外機等の電気機器類の外装材、並びに内装材等の各種の部材として用いられている。通常、プレコート鋼板は、鋼板の表面に塗装を施し、塗膜を形成させた後、要求される製品へと加工される。このため、プレコート鋼板に形成される塗膜には、柔軟性と、加工の際、例えば、プレコート鋼板を曲げた際に割れたり剥がれたりしない等、高い加工性とが要求されている。その上、プレコート鋼板は上記部材の外観を構成するため、プレコート鋼板には優れた意匠性が求められている。また、プレコート鋼板には、用途に応じて、耐摩耗性、耐傷付き性、耐食性、耐候性等の各種特性が求められている。 Painted steel sheets coated with cold-rolled steel sheets or plated steel sheets as the base material are also called pre-coated steel sheets (also called "PCM"), and are used for building materials such as shutters, shutters, doors, roofs and siding, and electricity for cooler outdoor units. It is used as an exterior material for equipment and various members such as interior materials. Usually, the pre-coated steel sheet is processed into a required product after the surface of the steel sheet is coated to form a coating film. Therefore, the coating film formed on the pre-coated steel sheet is required to have flexibility and high workability such that it does not crack or peel off during processing, for example, when the pre-coated steel sheet is bent. Moreover, since the pre-coated steel sheet constitutes the appearance of the above-mentioned member, the pre-coated steel sheet is required to have excellent designability. Further, the pre-coated steel sheet is required to have various properties such as wear resistance, scratch resistance, corrosion resistance, and weather resistance, depending on the intended use.
近年、建材用や器物加工用等のプレコート塗装金属板の分野においては、より美粧性に優れた塗装金属板が求められており、粒子径の大きな有機樹脂微粒子を配合した上塗塗料、無機質微粒子を大量に配合した上塗塗料、アミン化合物を配合し塗膜表面と塗膜内部における硬化速度の差を利用して均一な艶消し外観を形成させる上塗塗料等を塗装した艶消塗装金属板等が市場に出ている。 In recent years, in the field of pre-coated metal plates for building materials and equipment processing, there has been a demand for coated metal plates with better cosmetic properties, and topcoat paints and inorganic fine particles containing organic resin fine particles with a large particle size are being used. The market is for topcoat paints that are blended in large quantities, and matte coated metal plates that are coated with topcoat paints that are blended with amine compounds to form a uniform matte appearance by utilizing the difference in curing speed between the surface of the coating and the inside of the coating. It is out in.
また、消費者の高級化志向から、低光沢(艶消し)の塗膜外観への要求が高くなりつつあり、塗料組成物及び塗装方法が種々検討されてきた。例えば、シリカ、炭酸カルシウム、タルク等の体質顔料を塗料組成物中に配合して低光沢としたプレコート鋼板が検討されてきた。しかしながら、これらの塗膜には、加工性や耐候性が劣る等の問題点があった。 In addition, there is an increasing demand for a low-gloss (matte) coating film appearance due to consumers' desire to upgrade, and various coating compositions and coating methods have been studied. For example, precoated steel sheets having low gloss by blending an extender pigment such as silica, calcium carbonate, and talc into a coating composition have been studied. However, these coating films have problems such as inferior processability and weather resistance.
例えば、特許文献1(特開2002-146280号公報)には、均一な艶消し外観を有する塗膜を発生する塗料組成物として、変性ポリエステル樹脂(A)、水酸基を含有するポリエステル樹脂又はアクリル樹脂(B)、低核体メチル化メラミン樹脂(C)及びスルホン酸1当量と沸点30℃以上250℃以下の第2級もしくは第3級アミンとの混合物(D)を含有する塗料組成物の発明が開示されている。 For example, Patent Document 1 (Japanese Unexamined Patent Publication No. 2002-146280) describes a modified polyester resin (A), a polyester resin containing a hydroxyl group, or an acrylic resin as a coating composition for generating a coating film having a uniform matte appearance. (B) Invention of a coating composition containing a low-nuclear methylated melamine resin (C) and a mixture (D) of 1 equivalent of sulfonic acid and a secondary or tertiary amine having a boiling point of 30 ° C. or higher and 250 ° C. or lower. Is disclosed.
特許文献1の塗料組成物では、加工性が改善された艶消し外観を有する塗膜は得られるものの、塗膜の耐候性(退色性)は、特に中彩色から濃彩色にかけての色相領域において、改良の余地がある。なお、本開示において、中彩色、濃彩色とは、塗膜の明度(L*値)によって定義され、明度(L*値)はJIS K 5600-4-4の3.2及びJIS K 5600-4-5に記載に従って算出される。明度(L*値)は、例えば、分光測色計CM-M6(コニカミノルタ社製)等で測定できる。明度(L*値)が40未満である塗色を濃彩色、40以上80未満の塗色を中彩色とする。
本開示の目的は、低光沢、かつ、高耐候性を有する塗膜の形成に寄与できる塗料組成物を提供することにある。
In the coating composition of Patent Document 1, although a coating film having a matte appearance with improved workability can be obtained, the weather resistance (fading property) of the coating film is particularly high in the hue region from medium to deep colors. There is room for improvement. In the present disclosure, the medium color and the deep color are defined by the lightness (L * value) of the coating film, and the lightness (L * value) is 3.2 of JIS K 5600-4-4 and JIS K 5600-. Calculated according to the description in 4-5. The brightness (L * value) can be measured with, for example, a spectrocolorimeter CM-M6 (manufactured by Konica Minolta) or the like. A paint color having a lightness (L * value) of less than 40 is defined as a dark color, and a paint color having a brightness (L * value) of 40 or more and less than 80 is defined as a medium color.
An object of the present disclosure is to provide a coating composition capable of contributing to the formation of a coating film having low gloss and high weather resistance.
上記課題を解決するため、本開示は下記態様を提供する。
[1]
少なくとも塗膜形成樹脂(A)及び架橋剤(B)を含む塗料組成物であり、
該塗料組成物を硬化させた塗膜の表面における、算術平均高さ(Ra)が1.2μm以上であり、かつ展開面積比(Sdr)が800%以上
であることを特徴とする塗料組成物。
[2]
更に、スルホン酸(C)、アミン化合物(D)及び骨材(E)を含む、[1]に記載の塗料組成物。
[3]
前記塗膜形成樹脂(A)は、水酸基を有する樹脂であり、ポリエステル樹脂、アクリル樹脂、ウレタン樹脂及びこれらの変性物からなる群より選ばれる少なくとも1種を含む、[1]又は[2]に記載の塗料組成物。
[4]
前記架橋剤(B)は、メラミン樹脂及び尿素樹脂からなる群より選ばれる少なくとも1種を含む、[1]~[3]のいずれか1つに記載の塗料組成物。
[5]
前記架橋剤(B)の含有量は、前記塗膜形成樹脂(A)の樹脂固形分100質量部に対して、樹脂固形分として5質量部以上100質量部以下である、[1]~[4]のいずれか1つに記載の塗料組成物。
[6]
前記スルホン酸(C)の含有量は、前記塗膜形成樹脂(A)の樹脂固形分100質量部に対して、1.0質量部以上18.0質量部以下である、[2]~[5]のいずれか1つに記載の塗料組成物。
[7]
前記アミン化合物(D)は、沸点50℃以上250℃以下の2級又は3級アミンである、[2]~[6]のいずれか1つに記載の塗料組成物。
[8]
前記アミン化合物(D)による、前記スルホン酸(C)の酸基の中和率は、300%以上3,000%以下である、[2]~[7]のいずれか1つに記載の塗料組成物。
[9]
前記骨材(E)は、アクリル樹脂粒子、ガラスビーズ、アクリロニトリル樹脂粒子、尿素樹脂粒子、セラミック繊維及びシリカ粒子からなる群から選択される少なくとも1種を含む、[2]~[8]のいずれか1つに記載の塗料組成物。
[10]
前記骨材(E)は、アクリル樹脂粒子、尿素樹脂粒子及びシリカ粒子からなる群から選択される少なくとも1種を含み、
シリカ粒子の粒子径は、1μm以上20μm以下である、[2]~[9]のいずれか1つに記載の塗料組成物。
[11]
鋼板及び前記鋼板の少なくとも一方の表面上に塗膜を有する塗装鋼板であって、
前記塗膜は、少なくとも塗膜形成樹脂(A)と、架橋剤(B)とを含む塗料組成物より形成され、
前記塗膜の表面における、算術平均高さ(Ra)が1.2μm以上であり、かつ展開面積比(Sdr)が800%以上、
であることを特徴とする塗装鋼板。
[12]
鋼板及び前記鋼板の少なくとも一方の表面上に塗膜を有する塗装鋼板であって、
前記塗膜は、[1]~[10]のいずれか1つに記載の塗料組成物より形成され、
前記塗膜の表面における、算術平均高さ(Ra)が1.2μm以上であり、かつ展開面積比(Sdr)が800%以上、
であることを特徴とする塗装鋼板。
[13]
[1]~[10]のいずれか1つに記載の塗料組成物を、被塗物に塗装する塗装工程、及び
塗装後の塗料組成物を150℃以上270℃以下の温度で乾燥及び/又は硬化させることを含む、
塗膜の製造方法。
To solve the above problems, the present disclosure provides the following aspects.
[1]
A coating composition containing at least a coating film-forming resin (A) and a cross-linking agent (B).
A coating composition having an arithmetic mean height (Ra) of 1.2 μm or more and a developed area ratio (Sdr) of 800% or more on the surface of a coating film obtained by curing the coating composition. ..
[2]
The coating composition according to [1], further comprising a sulfonic acid (C), an amine compound (D) and an aggregate (E).
[3]
The coating film-forming resin (A) is a resin having a hydroxyl group, and contains at least one selected from the group consisting of polyester resin, acrylic resin, urethane resin and modified products thereof, according to [1] or [2]. The described paint composition.
[4]
The coating composition according to any one of [1] to [3], wherein the cross-linking agent (B) contains at least one selected from the group consisting of a melamine resin and a urea resin.
[5]
The content of the cross-linking agent (B) is 5 parts by mass or more and 100 parts by mass or less as the resin solid content with respect to 100 parts by mass of the resin solid content of the coating film forming resin (A) [1] to [ 4] The coating composition according to any one of.
[6]
The content of the sulfonic acid (C) is 1.0 part by mass or more and 18.0 part by mass or less with respect to 100 parts by mass of the resin solid content of the coating film-forming resin (A), [2] to [ 5] The coating composition according to any one of.
[7]
The coating composition according to any one of [2] to [6], wherein the amine compound (D) is a secondary or tertiary amine having a boiling point of 50 ° C. or higher and 250 ° C. or lower.
[8]
The coating material according to any one of [2] to [7], wherein the neutralization rate of the acid group of the sulfonic acid (C) by the amine compound (D) is 300% or more and 3,000% or less. Composition.
[9]
The aggregate (E) is any of [2] to [8], which comprises at least one selected from the group consisting of acrylic resin particles, glass beads, acrylonitrile resin particles, urea resin particles, ceramic fibers and silica particles. The coating composition according to one.
[10]
The aggregate (E) contains at least one selected from the group consisting of acrylic resin particles, urea resin particles and silica particles.
The coating composition according to any one of [2] to [9], wherein the silica particles have a particle size of 1 μm or more and 20 μm or less.
[11]
A coated steel sheet having a coating film on the surface of a steel sheet and at least one of the steel sheets.
The coating film is formed of a coating composition containing at least a coating film forming resin (A) and a cross-linking agent (B).
The arithmetic mean height (Ra) on the surface of the coating film is 1.2 μm or more, and the developed area ratio (Sdr) is 800% or more.
A painted steel sheet characterized by being.
[12]
A coated steel sheet having a coating film on the surface of a steel sheet and at least one of the steel sheets.
The coating film is formed from the coating composition according to any one of [1] to [10].
The arithmetic mean height (Ra) on the surface of the coating film is 1.2 μm or more, and the developed area ratio (Sdr) is 800% or more.
A painted steel sheet characterized by being.
[13]
A coating step of applying the coating composition according to any one of [1] to [10] to an object to be coated, and drying and / or drying the coating composition after coating at a temperature of 150 ° C. or higher and 270 ° C. or lower. Including curing,
A method for manufacturing a coating film.
本開示の塗料組成物は、低光沢、かつ、高耐候性を有する塗膜の形成に寄与できる。 The coating composition of the present disclosure can contribute to the formation of a coating film having low gloss and high weather resistance.
以下、本開示の塗料組成物について説明する。 Hereinafter, the coating composition of the present disclosure will be described.
本開示の塗料組成物は、少なくとも塗膜形成樹脂(A)及び架橋剤(B)を含み、
該塗料組成物を硬化させた塗膜の表面における、算術平均高さ(Ra)が1.2μm以上であり、かつ展開面積比(Sdr)が800%以上
であることを特徴とする。
本開示の塗料組成物を用いることにより、本開示の塗料組成物を硬化させて得られた塗膜において、光沢が低くなり、かつ、耐候性が良好になる。これは、特定の理論に限定して解釈すべきではないが、以下のように考えられる。本開示の塗料組成物により形成される塗膜は、その表面において特定の算術平均高さ(Ra)及び展開面積比(Sdr)を有する凹凸構造を有する。このような塗膜では、表面積が増加するため、単位面積当たりの紫外線の受光量は減少し、その結果、塗膜の劣化を抑制できると考えられる。更に、本開示の塗料組成物より形成された塗膜が建築部材等に用いられた場合に、紫外線に照射される時間を短くすることができ、その結果、塗膜の劣化を抑制できる。これは、該塗膜が凹凸構造を有するために、ある時刻には太陽に直接照射されていた箇所が、別の時刻には太陽に直接照射されなくなるためと考えられる。更に、塗膜の表面に凹凸構造を有するため、塗膜表面上で光の乱反射が生じ、その結果、塗膜の光沢を低減できるとともに、光が散乱するために塗膜の内部への光の入射を抑制でき、塗膜内部からの劣化も防ぐことができると考えられる。
The coating composition of the present disclosure contains at least a coating film forming resin (A) and a cross-linking agent (B).
The surface of the coating film obtained by curing the coating composition is characterized by having an arithmetic mean height (Ra) of 1.2 μm or more and a developed area ratio (Sdr) of 800% or more.
By using the coating composition of the present disclosure, the coating film obtained by curing the coating composition of the present disclosure has low gloss and good weather resistance. This should not be construed in a specific theory, but it can be thought of as follows. The coating film formed by the coating composition of the present disclosure has an uneven structure having a specific arithmetic mean height (Ra) and a developed area ratio (Sdr) on the surface thereof. Since the surface area of such a coating film increases, it is considered that the amount of ultraviolet rays received per unit area decreases, and as a result, deterioration of the coating film can be suppressed. Further, when the coating film formed from the coating composition of the present disclosure is used for a building member or the like, the time of irradiation with ultraviolet rays can be shortened, and as a result, deterioration of the coating film can be suppressed. It is considered that this is because the coating film has an uneven structure, so that the portion directly irradiated with the sun at one time is not directly irradiated with the sun at another time. Further, since the surface of the coating film has an uneven structure, diffused reflection of light occurs on the surface of the coating film, and as a result, the gloss of the coating film can be reduced, and the light is scattered to cause light to the inside of the coating film. It is considered that the incident can be suppressed and the deterioration from the inside of the coating film can be prevented.
算術平均高さ(「Ra」ともいう)は、塗膜の表面の粗さを示すパラメータであり、塗膜の表面の平均面に対して、各点の高さの差の絶対値の平均を表す。Raが小さい場合には、塗膜表面はより平坦である、すなわち、均一な艶消し外観が十分に形成されていないことを意味する。Raの測定は、JIS B 0601-2001に準拠して測定し、例えば、表面粗さ測定機HANDYSURF E-35B(東京精密社製)等により測定することができる。 The arithmetic mean height (also referred to as "Ra") is a parameter indicating the roughness of the surface of the coating film, and is the average of the absolute values of the height differences of each point with respect to the average surface of the surface of the coating film. show. When Ra is small, it means that the surface of the coating film is flatter, that is, a uniform matte appearance is not sufficiently formed. Ra is measured in accordance with JIS B 0601-2001, and can be measured by, for example, a surface roughness measuring machine HANDYSURF E-35B (manufactured by Tokyo Seimitsu Co., Ltd.).
Raは1.2μm以上、好ましくは2.5μm以上である。Raの上限値は好ましくは6μm、より好ましくは5μmである。得られる塗膜が均一な艶消し外観を有する場合、Raは上記範囲に含まれる値となる。 Ra is 1.2 μm or more, preferably 2.5 μm or more. The upper limit of Ra is preferably 6 μm, more preferably 5 μm. When the obtained coating film has a uniform matte appearance, Ra is a value included in the above range.
展開面積比(「Sdr」ともいう)は、ISO 25178に基づき測定したときの、測定領域における実際の凹凸が反映された表面積(展開面積)が、測定領域における凹凸のない平面の面積に対してどれだけ増大しているかを表すパラメータであり、下記式で表される。このSdrが小さいほど表面が平滑であるといえ、完全に平坦な表面のSdrは0%となる。Sdrは、例えば、レーザー顕微鏡OPTELICS HYBRID C3(レーザーテック社製)等により測定することができる。
展開面積比(Sdr)={(A-B)/B}×100[%]
A:測定領域における実際の凹凸が反映された表面積(展開面積)
B:測定領域における凹凸のない平面の面積
The developed area ratio (also referred to as "Sdr") is the surface area (expanded area) that reflects the actual unevenness in the measurement area when measured based on ISO 25178, with respect to the area of the flat surface without unevenness in the measurement area. It is a parameter indicating how much it has increased, and is expressed by the following equation. It can be said that the smaller the Sdr is, the smoother the surface is, and the Sdr of a completely flat surface is 0%. Sdr can be measured by, for example, a laser microscope OPTELICS HYBRID C3 (manufactured by Lasertec).
Expanded area ratio (Sdr) = {(AB) / B} x 100 [%]
A: Surface area (expanded area) that reflects the actual unevenness in the measurement area
B: Area of a flat surface with no unevenness in the measurement area
Sdrは800%以上、好ましくは1,000%以上である。Sdrの上限値は、好ましくは3,000%、より好ましくは、2,500%である。Sdrが上記範囲内にある場合、得られる塗膜は均一な艶消し外観を有する。 Sdr is 800% or more, preferably 1,000% or more. The upper limit of Sdr is preferably 3,000%, more preferably 2,500%. When Sdr is within the above range, the resulting coating film has a uniform matte appearance.
本開示の塗料組成物を硬化させた塗膜の表面において、Raが1.2μm以上、かつ、Sdrが800%以上であり、この塗膜はより均一な艶消し外観を有し、耐候性に優れる。 On the surface of the coating film obtained by curing the coating composition of the present disclosure, Ra is 1.2 μm or more and Sdr is 800% or more, and this coating film has a more uniform matte appearance and is weather resistant. Excellent.
<塗膜形成樹脂(A)>
塗膜形成樹脂(A)は、架橋剤(B)と反応し得る官能基を有し、かつ、塗膜形成能を有する樹脂である限り特に制限されない。
<Coating film forming resin (A)>
The coating film-forming resin (A) is not particularly limited as long as it has a functional group capable of reacting with the cross-linking agent (B) and has a coating film-forming ability.
塗膜形成樹脂(A)としては、例えば、ポリエステル樹脂及びその変性物(ウレタン変性ポリエステル樹脂、エポキシ変性ポリエステル樹脂、シリコーン変性ポリエステル樹脂等);アクリル樹脂及びその変性物(シリコーン変性アクリル樹脂等);ウレタン樹脂及びその変性物(エステル系ウレタン樹脂、エーテル系ウレタン樹脂、カーボネート系ウレタン樹脂、エポキシ系ウレタン樹脂等);フェノール樹脂及びその変性物(アクリル変性フェノール樹脂、エポキシ変性フェノール樹脂等);フェノキシ樹脂;アルキド樹脂及びその変性物(ウレタン変性アルキド樹脂、アクリル変性アルキド樹脂等);フッ素樹脂等の樹脂を挙げることができる。これらの樹脂は1種のみを単独で用いてもよく、2種以上を併用してもよい。 Examples of the coating film-forming resin (A) include polyester resin and its modified product (urethane-modified polyester resin, epoxy-modified polyester resin, silicone-modified polyester resin, etc.); acrylic resin and its modified product (silicone-modified acrylic resin, etc.); Urethane resin and its modified products (ester-based urethane resin, ether-based urethane resin, carbonate-based urethane resin, epoxy-based urethane resin, etc.); ; Alchid resin and its modified product (urethane modified alkido resin, acrylic modified alkido resin, etc.); Resins such as fluororesin can be mentioned. Only one kind of these resins may be used alone, or two or more kinds thereof may be used in combination.
一実施態様において、塗膜形成樹脂(A)は、ポリエステル樹脂、アクリル樹脂、ウレタン樹脂及びこれらの変性物からなる群から選択される少なくとも1種を含む。艶消し外観の形成のしやすさ、形成される塗膜の高耐候性という観点からは、塗膜形成樹脂(A)は、ポリエステル樹脂、アクリル樹脂、ウレタン樹脂及びこれらの変性物からなる群から選択される少なくとも1種を含むことが好ましい。 In one embodiment, the coating film forming resin (A) contains at least one selected from the group consisting of polyester resin, acrylic resin, urethane resin and modified products thereof. From the viewpoint of ease of forming a matte appearance and high weather resistance of the formed coating film, the coating film forming resin (A) is composed of a group consisting of polyester resin, acrylic resin, urethane resin and modified products thereof. It is preferable to include at least one selected.
一実施態様において、塗膜形成樹脂(A)は、ポリエステル樹脂、アクリル樹脂、及びこれらの変性物からなる群から選択される少なくとも1種を含んでいてもよい。 In one embodiment, the coating film forming resin (A) may contain at least one selected from the group consisting of polyester resin, acrylic resin, and modified products thereof.
好ましくは、塗膜形成樹脂(A)は、水酸基を有する樹脂であり、ポリエステル樹脂、アクリル樹脂、ウレタン樹脂、及びこれらの変性物からなる群より選ばれる少なくとも1種を含む。塗膜の加工性及び耐候性の観点からは、水酸基を有するポリエステル樹脂が好ましい。 Preferably, the coating film-forming resin (A) is a resin having a hydroxyl group, and contains at least one selected from the group consisting of polyester resin, acrylic resin, urethane resin, and modified products thereof. From the viewpoint of processability and weather resistance of the coating film, a polyester resin having a hydroxyl group is preferable.
一実施態様において、上記塗膜形成樹脂(A)の水酸基価(「OHV」ともいう)は、例えば、5mgKOH/g以上200mgKOH/g以下であってもよく、5mgKOH/g以上150mgKOH/g以下であってもよい。このような塗膜形成樹脂(A)を用いることによって、塗膜外観に優れ、耐候性にも優れる塗膜を得ることができる。なお、本開示において、水酸基価は、JIS K 0070に準拠した方法により測定された値である。
本開示の塗料組成物が、複数種の塗膜形成樹脂(A)を含む場合、全塗膜形成樹脂(A)の水酸基価が上記範囲内にあることが好ましい。
別の態様においては、本開示の塗料組成物が、複数種の塗膜形成樹脂(A)を含む場合、塗膜形成樹脂(A)の水酸基価の平均値が上記範囲内に含まれ得る。
In one embodiment, the hydroxyl value (also referred to as “OHV”) of the coating film-forming resin (A) may be, for example, 5 mgKOH / g or more and 200 mgKOH / g or less, and 5 mgKOH / g or more and 150 mgKOH / g or less. There may be. By using such a coating film-forming resin (A), it is possible to obtain a coating film having an excellent coating film appearance and excellent weather resistance. In the present disclosure, the hydroxyl value is a value measured by a method based on JIS K 0070.
When the coating composition of the present disclosure contains a plurality of types of coating film-forming resin (A), it is preferable that the hydroxyl value of all the coating film-forming resin (A) is within the above range.
In another aspect, when the coating composition of the present disclosure contains a plurality of types of the coating film-forming resin (A), the average value of the hydroxyl values of the coating film-forming resin (A) may be included in the above range.
塗膜形成樹脂(A)は、1,000以上40,000以下の数平均分子量を有することができる。
数平均分子量がこのような範囲内であることにより、白ボケ感のない均一な艶消し外観が得られやすくなる。本開示中において、数平均分子量(Mn)は、ゲルパーミエーションクロマトグラフィ(GPC)を用いて測定し、ポリスチレン換算により求めた値である。
The coating film-forming resin (A) can have a number average molecular weight of 1,000 or more and 40,000 or less.
When the number average molecular weight is within such a range, it becomes easy to obtain a uniform matte appearance without a feeling of white blur. In the present disclosure, the number average molecular weight (Mn) is a value measured by gel permeation chromatography (GPC) and determined by polystyrene conversion.
塗膜形成樹脂(A)は、本開示の塗料組成物中に、塗膜形成樹脂(A)及び架橋剤(B)の樹脂固形分の合計100質量部に対して、樹脂固形分として50質量部以上95質量部以下含まれ得る。塗膜形成樹脂(A)の含有量が上記範囲内にあることで塗料組成物からは均一な艶消し外観の塗膜が得られ、その加工性にも優れるという利点がある。 The coating film-forming resin (A) has a resin solid content of 50 parts by mass with respect to a total of 100 parts by mass of the resin solids of the coating film-forming resin (A) and the cross-linking agent (B) in the coating composition of the present disclosure. It may be contained in an amount of 95 parts by mass or less. When the content of the coating film forming resin (A) is within the above range, a coating film having a uniform matte appearance can be obtained from the coating composition, and there is an advantage that the processability is also excellent.
(ポリエステル樹脂)
一実施態様において、ポリエステル樹脂の水酸基価は、例えば5mgKOH/g以上200mgKOH/g以下であってもよく、5mgKOH/g以上150mgKOH/g以下であってもよい。水酸基価が上記範囲内にあることで、得られる塗膜の加工性及び耐候性が優れるという利点がある
(Polyester resin)
In one embodiment, the hydroxyl value of the polyester resin may be, for example, 5 mgKOH / g or more and 200 mgKOH / g or less, or 5 mgKOH / g or more and 150 mgKOH / g or less. When the hydroxyl value is within the above range, there is an advantage that the workability and weather resistance of the obtained coating film are excellent.
ポリエステル樹脂、例えば、その変性物である水酸基含有ポリエステル樹脂の数平均分子量(Mn)は、1,000以上40,000以下であることが好ましく、2,000以上40,000以下であることがより好ましく、2,000以上30,000以下であることが特に好ましい。なお、本開示において、特に言及のない限り、単にポリエステル樹脂と記載する場合、ポリエステル樹脂及びポリエステル樹脂の変性物からなる群から選択される少なくとも1種を含むことを意味する。
ポリエステル樹脂がこのような数平均分子量を有することにより、ポリエステル樹脂と架橋剤(B)との架橋反応が十分に進行し、高い耐湿性を有する塗膜を形成できる。また、上記のような数平均分子量のポリエステル樹脂を有することにより、形成される塗膜の架橋密度が高くなりすぎることを抑制でき、十分な伸び率を有する塗膜を形成でき、例えば、十分な折り曲げ加工性を有する塗膜を形成できる。また更に、上記のような数平均分子量のポリエステル樹脂を有することにより、本開示の塗料組成物は適切な粘度を有し得、取り扱い性が良好となり得る。
The number average molecular weight (Mn) of the polyester resin, for example, the hydroxyl group-containing polyester resin which is a modified product thereof, is preferably 1,000 or more and 40,000 or less, and more preferably 2,000 or more and 40,000 or less. It is preferable, and it is particularly preferable that it is 2,000 or more and 30,000 or less. In the present disclosure, unless otherwise specified, when the term "polyester resin" is simply used, it means that the polyester resin and at least one selected from the group consisting of modified products of the polyester resin are included.
When the polyester resin has such a number average molecular weight, the cross-linking reaction between the polyester resin and the cross-linking agent (B) proceeds sufficiently, and a coating film having high moisture resistance can be formed. Further, by having the polyester resin having a number average molecular weight as described above, it is possible to suppress the crosslink density of the formed coating film from becoming too high, and it is possible to form a coating film having a sufficient elongation rate, for example, sufficient. A coating film having bendability can be formed. Furthermore, by having the polyester resin having a number average molecular weight as described above, the coating composition of the present disclosure can have an appropriate viscosity and can be handled well.
ポリエステル樹脂のガラス転移温度(Tg)は、-35℃以上110℃以下であることが好ましく、例えば、-30℃以上80℃以下であり、-30℃以上60℃以下であることができる。
ポリエステル樹脂のガラス転移温度(Tg)が上記範囲内であることにより、形成される塗膜の透湿性が過度に高くなることなく、塗膜の耐湿性が十分となる。
The glass transition temperature (Tg) of the polyester resin is preferably −35 ° C. or higher and 110 ° C. or lower, for example, −30 ° C. or higher and 80 ° C. or lower, and −30 ° C. or higher and 60 ° C. or lower.
When the glass transition temperature (Tg) of the polyester resin is within the above range, the moisture permeability of the formed coating film does not become excessively high, and the moisture resistance of the coating film becomes sufficient.
ポリエステル樹脂(その変性物を含む)の固形分酸価は、0.1mgKOH/g以上30mgKOH/g以下であり、例えば、0.2mgKOH/g以上30mgKOH/g以下であり、0.3mgKOH/g以上30mgKOH/g以下であってよい。
固形分酸価がこのような範囲であることにより、例えば、耐加水分解性を向上させることができ、耐湿性を有する塗膜を形成できる。
The solid acid value of the polyester resin (including its modified product) is 0.1 mgKOH / g or more and 30 mgKOH / g or less, for example, 0.2 mgKOH / g or more and 30 mgKOH / g or less, and 0.3 mgKOH / g or more. It may be 30 mgKOH / g or less.
When the solid content acid value is in such a range, for example, hydrolysis resistance can be improved and a coating film having moisture resistance can be formed.
ポリエステル樹脂は、多価アルコールと多塩基酸との重縮合により得ることができる。
多価アルコールの具体例としては、例えば、エチレングリコール、ジエチレングリコール、ポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、ポリプロピレングリコール、ネオペンチルグリコール、1,2-ブタンジオール、1,3-ブタンジオール、2,3-ブタンジオール又は1,4-ブタンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオール、水添ビスフェノールA、ヒドロキシアルキル化ビスフェノールA、1,4-シクロヘキサンジメタノール、2,2-ジメチル-3-ヒドロキシプロピル-2,2-ジメチル-3-ヒドロキシプロピオネート(BASHPN)、N,N-ビス-(2-ヒドロキシエチル)ジメチルヒダントイン、ポリカプロラクトンポリオール、グリセリン、ソルビトール、アンニトール、トリメチロールエタン、トリメチロールプロパン、トリメチロールブタン、ヘキサントリオール、ペンタエリスリトール、ジペンタエリスリトール、トリス-(ヒドロキシエチル)イソシアネート等を挙げることができる。多価アルコールは1種のみを単独で用いてもよいし、2種以上を併用してもよい。
多塩基酸の具体例としては、例えば、フタル酸、無水フタル酸、テトラヒドロフタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロフタル酸、ヘキサヒドロ無水フタル酸、メチルテトラフタル酸、メチルテトラヒドロ無水フタル酸、無水ハイミック酸、トリメリット酸、無水トリメリット酸、ピロメリット酸、無水ピロメリット酸、イソフタル酸、テレフタル酸、マレイン酸、無水マレイン酸、フマル酸、イタコン酸、アジピン酸、アゼライン酸、セバシン酸、コハク酸、無水コハク酸、乳酸、ドデセニルコハク酸、ドデセニル無水コハク酸、シクロヘキサン-1,4-ジカルボン酸、無水エンド酸等を挙げることができる。多塩基酸は1種のみを単独で用いてもよいし、2種以上を併用してもよい。
The polyester resin can be obtained by polycondensation of a polyhydric alcohol and a polybasic acid.
Specific examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, 1,2-butanediol, 1,3-butanediol, and 2,3. -Butandiol or 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, hydrogenated bisphenol A, hydroxyalkylated bisphenol A, 1,4-cyclohexanedimethanol, 2,2-dimethyl- 3-Hydroxypropyl-2,2-dimethyl-3-hydroxypropionate (BASHPN), N, N-bis- (2-hydroxyethyl) dimethyl hydantin, polycaprolactone polyol, glycerin, sorbitol, annitol, trimethylolethane, Examples thereof include trimethylolpropane, trimethylolbutane, hexanetriol, pentaerythritol, dipentaerythritol, tris- (hydroxyethyl) isocyanate and the like. Only one type of polyhydric alcohol may be used alone, or two or more types may be used in combination.
Specific examples of the polybasic acid include, for example, phthalic acid, phthalic anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrochloride phthalic acid, methyltetraphthalic acid, methyltetrahydrochloride phthalic acid, and hymic anhydride. Acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, isophthalic acid, terephthalic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, adipic acid, azelaic acid, sebacic acid, succinic acid , Dodecenyl succinic acid, lactic acid, dodecenyl succinic acid, dodecenyl anhydrous succinic acid, cyclohexane-1,4-dicarboxylic acid, endohydrate anhydride and the like. Only one type of polybasic acid may be used alone, or two or more types may be used in combination.
ポリエステル樹脂の変性物としては、例えば、ウレタン変性ポリエステル樹脂、エポキシ変性ポリエステル樹脂、アクリル変性ポリエステル樹脂、シリコーン変性ポリエステル樹脂等の変性ポリエステル樹脂を挙げることができる。例えば、ウレタン変性ポリエステル樹脂は、ポリエステルを主鎖に有し、その末端をイソシアネートで変性させ、ウレタン変性させた樹脂である。例えば、シリコーン変性ポリエステル樹脂を例に挙げれば、これは、ポリエステル樹脂と有機シリコーン(例えば、官能基として-SiOCH3基及び/又は-SiOH基を有する数平均分子量300以上1,000以下程度の有機シリコーン)とを反応させることにより調製することができる。有機シリコーンの使用量は、通常、ポリエステル樹脂100質量部に対して、5質量部以上50質量部以下程度である。また、ウレタン変性ポリエステル樹脂を例に挙げれば、これは、上記ポリエステル樹脂とポリイソシアネート化合物とを反応させて調製することができる。
ポリエステル樹脂及び水酸基含有ポリエステル樹脂変性物として市販品を用いてもよい。市販品としては、例えば、ベッコライト46-118、ベッコライトM-6205-50、ベッコライトM-6401-52、ベッコライトM-6402-50(いずれもDIC社製)、バイロン220、バイロンUR3500、バイロンUR5537、バイロンUR8300、バイロンUR4410、バイロンGK13CS(いずれも東洋紡社製)等を挙げることができる。
Examples of the modified polyester resin include modified polyester resins such as urethane-modified polyester resin, epoxy-modified polyester resin, acrylic-modified polyester resin, and silicone-modified polyester resin. For example, the urethane-modified polyester resin is a resin having polyester in the main chain and having its ends modified with isocyanate to be urethane-modified. For example, a silicone-modified polyester resin may be taken as an example of a polyester resin and an organic silicone (for example, an organic having a number average molecular weight of about 300 or more and 1,000 or less having 3 -SiOCH groups and / or -SiOH groups as functional groups. It can be prepared by reacting with silicone). The amount of the organic silicone used is usually about 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the polyester resin. Further, taking a urethane-modified polyester resin as an example, this can be prepared by reacting the polyester resin with a polyisocyanate compound.
Commercially available products may be used as the polyester resin and the modified product of the hydroxyl group-containing polyester resin. Examples of commercially available products include Beckolite 46-118, Beckolite M-6205-50, Beckolite M-6401-52, Beckolite M-6402-50 (all manufactured by DIC Corporation), Byron 220, and Byron UR3500. Examples thereof include Byron UR5537, Byron UR8300, Byron UR4410, Byron GK13CS (all manufactured by Toyobo Corporation) and the like.
(アクリル樹脂)
一実施態様において、アクリル樹脂の水酸基価は、例えば、5mgKOH/g以上250mgKOH/g以下であってもよく、5mgKOH/g以上100mgKOH/g以下であってもよく、例えば、5mgKOH/g以上70mgKOH/g以下であってもよい。
(acrylic resin)
In one embodiment, the hydroxyl value of the acrylic resin may be, for example, 5 mgKOH / g or more and 250 mgKOH / g or less, 5 mgKOH / g or more and 100 mgKOH / g or less, for example, 5 mgKOH / g or more and 70 mgKOH / g. It may be less than or equal to g.
アクリル樹脂及びその変性物の数平均分子量(Mn)は、1,000以上40,000以下であることが好ましい。なお、本開示において、特に言及のない限り、単にアクリル樹脂と記載する場合、アクリル樹脂及びアクリル樹脂の変性物からなる群から選択される少なくとも1種を含むことを意味する。
アクリル樹脂がこのような数平均分子量を有することにより、アクリル樹脂と架橋剤(B)との架橋反応が十分に進行し、高い耐湿性を有する塗膜を形成できる。また、上記のような数平均分子量のアクリル樹脂を用いることにより、形成される塗膜の架橋密度が高くなりすぎることを抑制でき、十分な伸び率を有する塗膜を形成でき、例えば、十分な折り曲げ加工性を有する塗膜を形成できる。また更に、上記のような数平均分子量のアクリル樹脂を用いることによりを有することにより、本開示の塗料組成物は適切な粘度を有し得、取り扱い性が良好となり得る。
The number average molecular weight (Mn) of the acrylic resin and its modified product is preferably 1,000 or more and 40,000 or less. In the present disclosure, unless otherwise specified, when the term "acrylic resin" is simply used, it means that it contains at least one selected from the group consisting of acrylic resin and modified products of acrylic resin.
When the acrylic resin has such a number average molecular weight, the cross-linking reaction between the acrylic resin and the cross-linking agent (B) proceeds sufficiently, and a coating film having high moisture resistance can be formed. Further, by using the acrylic resin having a number average molecular weight as described above, it is possible to suppress the crosslink density of the formed coating film from becoming too high, and it is possible to form a coating film having a sufficient elongation rate, for example, sufficient. A coating film having bendability can be formed. Furthermore, by using an acrylic resin having a number average molecular weight as described above, the coating composition of the present disclosure can have an appropriate viscosity and can be handled well.
アクリル樹脂のガラス転移温度(Tg)は、-35℃以上110℃以下であることが好ましく、例えば、-30℃以上80℃以下であり、-30℃以上60℃以下であることができる。
アクリル樹脂のガラス転移温度(Tg)が上記範囲内であることにより、塗膜の透湿性が過度に高くなることなく、塗膜の耐湿性が十分となる。
The glass transition temperature (Tg) of the acrylic resin is preferably −35 ° C. or higher and 110 ° C. or lower, for example, −30 ° C. or higher and 80 ° C. or lower, and −30 ° C. or higher and 60 ° C. or lower.
When the glass transition temperature (Tg) of the acrylic resin is within the above range, the moisture permeability of the coating film does not become excessively high, and the moisture resistance of the coating film becomes sufficient.
アクリル樹脂(その変性物を含む)の固形分酸価は、例えば、0.1mgKOH/g以上30mgKOH/g以下であってよい。
固形分酸価がこのような範囲であることにより、例えば、耐加水分解性を向上させることができ、耐湿性を有する塗膜を形成できる。
The solid acid value of the acrylic resin (including its modified product) may be, for example, 0.1 mgKOH / g or more and 30 mgKOH / g or less.
When the solid content acid value is in such a range, for example, hydrolysis resistance can be improved and a coating film having moisture resistance can be formed.
アクリル樹脂としては、例えば、(メタ)アクリル酸ヒドロキシメチル、(メタ)アクリル酸ヒドロキシルエチル、(メタ)アクリル酸ヒドロキシルプロピル、(メタ)アクリル酸ヒドロキシブチル、N-メチロールアクリルアミド等のヒドロキシル基を有する(メタ)アクリル系モノマー及びそのラクトン付加物;(メタ)アクリル酸;(メタ)アクリル酸アルキル等の(メタ)アクリル酸エステル;(メタ)アクリロニトリル等から選択される1種又は2種以上のモノマーからなるアクリル樹脂を挙げることができる。アクリル樹脂は、上記モノマーに由来する構成単位のほか、他のモノマー(例えば、クロトン酸、イタコン酸、フマル酸、マレイン酸等のカルボキシル基含有エチレン性モノマーや、スチレン等のビニル系モノマー等)に由来する構成単位を含んでいてもよい。なお、本開示において、(メタ)アクリル酸は、アクリル酸又はメタクリル酸を表す。
アクリル樹脂の変性物としては、例えば、シリコーン変性アクリル樹脂等の変性アクリル樹脂を挙げることができる。例えば、シリコーン変性アクリル樹脂を例に挙げれば、これは、アクリル樹脂と上記したような有機シリコーンとを反応させることにより調製することができる。有機シリコーンの使用量は、通常、アクリル樹脂100質量部に対して、5質量部以上50質量部以下程度である。
The acrylic resin has a hydroxyl group such as hydroxymethyl (meth) acrylate, hydroxylethyl (meth) acrylate, hydroxylpropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and N-methylolacrylamide (. From one or more monomers selected from (meth) acrylic monomers and lactone adducts thereof; (meth) acrylic acid; (meth) acrylic acid esters such as alkyl (meth) acrylic acid; (meth) acrylonitrile and the like. Acrylic resin can be mentioned. In addition to the structural units derived from the above-mentioned monomers, the acrylic resin can be used for other monomers (for example, carboxyl group-containing ethylenic monomers such as crotonic acid, itaconic acid, fumaric acid, and maleic acid, vinyl-based monomers such as styrene, etc.). It may contain the building blocks from which it is derived. In the present disclosure, (meth) acrylic acid represents acrylic acid or methacrylic acid.
Examples of the modified acrylic resin include modified acrylic resins such as silicone-modified acrylic resins. For example, taking a silicone-modified acrylic resin as an example, this can be prepared by reacting the acrylic resin with the organic silicone as described above. The amount of the organic silicone used is usually about 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the acrylic resin.
アクリル樹脂及びその変性物としては、市販品を用いてもよい。市販品としては、例えば、アクリディックWSG-806(DIC社製)、コータックスSA-105(東レ・ファインケミカル社製)等を挙げることができる。 As the acrylic resin and its modified product, a commercially available product may be used. Examples of commercially available products include Acridic WSG-806 (manufactured by DIC Corporation), Cotax SA-105 (manufactured by Toray Fine Chemical Corporation), and the like.
(ウレタン樹脂)
一実施態様において、ウレタン樹脂は水酸基を有する。本態様においては、ウレタン樹脂の水酸基価は、例えば、5mgKOH/g以上250mgKOH/g以下であってもよく、5mgKOH/g以上100mgKOH/g以下であってもよく、例えば、5mgKOH/g以上70mgKOH/g以下であってもよい。
(Urethane resin)
In one embodiment, the urethane resin has a hydroxyl group. In this embodiment, the hydroxyl value of the urethane resin may be, for example, 5 mgKOH / g or more and 250 mgKOH / g or less, 5 mgKOH / g or more and 100 mgKOH / g or less, for example, 5 mgKOH / g or more and 70 mgKOH / g. It may be less than or equal to g.
ウレタン樹脂及び変性ウレタン樹脂の数平均分子量(Mn)は、1,000以上30,000以下であり、例えば、2,000以上28,000以下であり、2,500以上25,000以下であってよい。一実施態様において、ウレタン樹脂及び変性ウレタン樹脂の数平均分子量(Mn)は、6,000以上15,000以下である。なお、本開示において、特に言及のない限り、単にウレタン樹脂と記載する場合、ウレタン樹脂及びウレタン樹脂の変性物からなる群から選択される少なくとも1種を含むことを意味する。
ウレタン樹脂がこのような数平均分子量をもつことにより、形成される塗膜の架橋密度が高くなりすぎることを抑制でき、十分な伸び率を有する塗膜を形成でき、例えば、十分な折り曲げ加工性を有する塗膜を形成できる。また更に、上記のような数平均分子量のウレタン樹脂を用いることにより、本開示の塗料組成物は適切な粘度を有し得、取り扱い性が良好となり得る。
The number average molecular weight (Mn) of the urethane resin and the modified urethane resin is 1,000 or more and 30,000 or less, for example, 2,000 or more and 28,000 or less, and 2,500 or more and 25,000 or less. good. In one embodiment, the number average molecular weight (Mn) of the urethane resin and the modified urethane resin is 6,000 or more and 15,000 or less. Unless otherwise specified in the present disclosure, the term "urethane resin" simply means that it contains at least one selected from the group consisting of urethane resin and modified products of urethane resin.
When the urethane resin has such a number average molecular weight, it is possible to suppress the crosslink density of the formed coating film from becoming too high, and it is possible to form a coating film having a sufficient elongation rate, for example, sufficient bending workability. Can form a coating film having. Furthermore, by using the urethane resin having a number average molecular weight as described above, the coating composition of the present disclosure can have an appropriate viscosity and can be handled well.
一実施態様において、ウレタン樹脂のガラス転移温度(Tg)は、-30℃以上80℃以下であり、例えば、-30℃以上60℃以下であり、-30℃以上50℃以下であることができる。
ウレタン樹脂のガラス転移温度(Tg)が上記範囲内であることにより、塗膜の透湿性が過度に高くなることなく、塗膜の耐湿性が十分となる。
In one embodiment, the glass transition temperature (Tg) of the urethane resin can be −30 ° C. or higher and 80 ° C. or lower, for example, −30 ° C. or higher and 60 ° C. or lower, and −30 ° C. or higher and 50 ° C. or lower. ..
When the glass transition temperature (Tg) of the urethane resin is within the above range, the moisture permeability of the coating film does not become excessively high, and the moisture resistance of the coating film becomes sufficient.
ウレタン樹脂(その変性物を含む)の固形分酸価は、0.1mgKOH/g以上30mgKOH/g以下であり、例えば、0.2mgKOH/g以上30mgKOH/g以下であり、0.3mgKOH/g以上30mgKOH/g以下であってよい。
固形分酸価がこのような範囲であることにより、例えば、耐加水分解性を向上させることができ、耐湿性を有する塗膜を形成できる。
The solid acid value of the urethane resin (including its modified product) is 0.1 mgKOH / g or more and 30 mgKOH / g or less, for example, 0.2 mgKOH / g or more and 30 mgKOH / g or less, and 0.3 mgKOH / g or more. It may be 30 mgKOH / g or less.
When the solid content acid value is in such a range, for example, hydrolysis resistance can be improved and a coating film having moisture resistance can be formed.
ウレタン樹脂として、例えば、ポリオール化合物とポリイソシアネート化合物とを反応させ、その後に更に鎖伸長剤によって鎖伸長して得られるもの等を挙げることができる。
ポリオール化合物としては、1分子当たり2個以上の水酸基を含有する化合物であれば特に限定されず、例えば、エチレングリコール、プロピレングリコール、ジエチレングリコール、1,6-へキサンジオール、ネオペンチルグリコール、トリエチレングリコール、グリセリン、トリメチロールエタン、トリメチロールプロパン、ポリカーボネートポリオール、ポリエステルポリオール、ビスフェノールヒドロキシプロピルエーテル等のポリエーテルポリオール、ポリエステルアミドポリオール、アクリルポリオール、ポリウレタンポリオール、又はそれらの混合物が挙げられる。
ポリイソシアネート化合物としては、1分子当たり2個以上のイソシアネート基を含有する化合物であれば特に限定されず、例えば、ヘキサメチレンジイソシアネート(HDI)等の脂肪族イソシアネート、イソホロンジイソシアネート(IPDI)等の脂環族ジイソシアネート、トリレンジイソシアネート(TDI)等の芳香族ジイソシアネート、ジフェニルメタンジイソシアネート(MDI)等の芳香脂肪族ジイソシアネート、又はそれらの混合物が挙げられる。
鎖伸長剤としては、分子内に1個以上の活性水素を含有する化合物であれば特に限定されず、水又はアミン化合物を適用できる。アミン化合物としては、エチレンジアミン、プロピレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミン、ジプロピレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン等の脂肪族ポリアミンや、トリレンジアミン、キシリレンジアミン、ジアミノジフェニルメタン等の芳香族ポリアミンや、ジアミノシクロヘキシルメタン、ピペラジン、2,5-ジメチルピペラジン、イソホロンジアミン等の脂環式ポリアミンや、ヒドラジン、コハク酸ジヒドラジド、アジピン酸ジヒドラジド、フタル酸ジヒドラジド等のヒドラジン類や、ヒドロキシエチルジエチレントリアミン、2-[(2-アミノエチル)アミノ]エタノール、3-アミノプロパンジオール等のアルカノールアミン等が挙げられる。
Examples of the urethane resin include those obtained by reacting a polyol compound with a polyisocyanate compound and then further chain-extending with a chain extender.
The polyol compound is not particularly limited as long as it is a compound containing two or more hydroxyl groups per molecule, and for example, ethylene glycol, propylene glycol, diethylene glycol, 1,6-hexanediol, neopentyl glycol, and triethylene glycol. , Polyether polyols such as glycerin, trimethylolethane, trimethylolpropane, polycarbonate polyols, polyester polyols, bisphenol hydroxypropyl ethers, polyesteramide polyols, acrylic polyols, polyurethane polyols, or mixtures thereof.
The polyisocyanate compound is not particularly limited as long as it is a compound containing two or more isocyanate groups per molecule, and for example, an aliphatic isocyanate such as hexamethylene diisocyanate (HDI) and an alicyclic such as isophorone diisocyanate (IPDI). Examples thereof include aromatic diisocyanates such as group diisocyanate and tolylene diisocyanate (TDI), aromatic aliphatic diisocyanates such as diphenylmethane diisocyanate (MDI), and mixtures thereof.
The chain extender is not particularly limited as long as it is a compound containing one or more active hydrogens in the molecule, and water or an amine compound can be applied. Examples of the amine compound include aliphatic polyamines such as ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine and tetraethylenepentamine, and aromatic polyamines such as tolylene diamine, xylylene diamine and diaminodiphenylmethane. , Alicyclic polyamines such as diaminocyclohexylmethane, piperazine, 2,5-dimethylpiperazine and isophoronediamine, hydrazines such as hydrazine, dihydrazide succinate, dihydrazide adipate, dihydrazide phthalate, hydroxyethyldiethylenetriamine, 2- [(2-Aminoethyl) amino] Examples thereof include alkanolamines such as ethanol and 3-aminopropanediol.
一実施態様において、ウレタン樹脂として、エステル系ウレタン樹脂、エーテル系ウレタン樹脂及びカーボネート系ウレタン樹脂を用いてもよい。 In one embodiment, an ester-based urethane resin, an ether-based urethane resin, and a carbonate-based urethane resin may be used as the urethane resin.
<架橋剤(B)>
架橋剤(B)は、塗膜形成樹脂(A)と反応して硬化塗膜を形成する。
<Crosslinking agent (B)>
The cross-linking agent (B) reacts with the coating film-forming resin (A) to form a cured coating film.
架橋剤(B)として、例えば、ポリイソシアネート化合物;ポリイソシアネート化合物のイソシアネート基を活性水素含有化合物でブロックしたブロックポリイソシアネート化合物(「BI」ともいう);アミノ樹脂;フェノール樹脂等を挙げることができる。 Examples of the cross-linking agent (B) include a polyisocyanate compound; a blocked polyisocyanate compound (also referred to as “BI”) in which the isocyanate group of the polyisocyanate compound is blocked with an active hydrogen-containing compound; an amino resin; a phenol resin and the like. ..
架橋剤(B)の含有量(樹脂固形分量)は、塗膜形成樹脂(A)の樹脂固形分100質量部に対し、5質量部以上100質量部以下であってもよく、10質量部以上70質量部以下であってもよく、10質量部以上40質量部以下であってもよく、10質量部以上30質量部以下であってもよい。
架橋剤(B)を上記の量含むことにより、塗膜形成樹脂(A)と架橋剤(B)との架橋反応が良好に進行し、得られる塗膜外観が良好となり、均一な艶消し外観が得られる。また、得られる塗膜の加工性及び耐食性が良好となり得る。
The content (resin solid content) of the cross-linking agent (B) may be 5 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the resin solid content of the coating film forming resin (A). It may be 70 parts by mass or less, 10 parts by mass or more and 40 parts by mass or less, or 10 parts by mass or more and 30 parts by mass or less.
By containing the above-mentioned amount of the cross-linking agent (B), the cross-linking reaction between the coating film-forming resin (A) and the cross-linking agent (B) proceeds satisfactorily, the appearance of the obtained coating film becomes good, and a uniform matte appearance is obtained. Is obtained. In addition, the processability and corrosion resistance of the obtained coating film can be improved.
一実施態様において、架橋剤(B)は、アミノ樹脂である。アミノ樹脂は、無触媒下においても塗膜形成樹脂(A)との架橋反応性に優れており、均一な艶消し外観の形成のしやすさの観点から好ましい。 In one embodiment, the cross-linking agent (B) is an amino resin. The amino resin is excellent in cross-linking reactivity with the coating film-forming resin (A) even under a non-catalyst, and is preferable from the viewpoint of easy formation of a uniform matte appearance.
アミノ樹脂としては、メラミン樹脂、尿素樹脂等を挙げることができ、これらの中ではメラミン樹脂が好ましい。
アミノ樹脂(例えば、メラミン樹脂)は、塗膜形成樹脂(A)との架橋反応性に優れており、得られる塗膜外観が特に良好となり、均一な艶消し外観が得られる。また、得られる塗膜の加工性及び耐食性が良好となり得る。
Examples of the amino resin include melamine resin and urea resin, and among these, melamine resin is preferable.
The amino resin (for example, melamine resin) has excellent cross-linking reactivity with the coating film forming resin (A), the appearance of the obtained coating film is particularly good, and a uniform matte appearance can be obtained. In addition, the processability and corrosion resistance of the obtained coating film can be improved.
「メラミン樹脂」とは、一般的に、メラミンとアルデヒドから合成される熱硬化性の樹脂を意味し、トリアジン核とトリアジン核1つあたり3つの反応性官能基-NX1X2とを有している。メラミン樹脂としては、反応性官能基として-N(CH2OR)2〔Rは炭素数1以上8以下のアルキル基を示す、以下同じ〕を含む完全アルキル化型;反応性官能基として-N(CH2OR)(CH2OH)を含むメチロール基型;反応性官能基として-N(CH2OR)(H)を含むイミノ基型;反応性官能基として、-N(CH2OR)(CH2OH)と-N(CH2OR)(H)とを含む、あるいは-N(CH2OH)(H)を含むメチロール/イミノ基型の4種類を例示することができる。
上記メラミン樹脂のなかでも、完全アルキル化型のメラミン樹脂を用いることが好ましく、このような樹脂としては、メチル化メラミン樹脂、ブチル化メラミン樹脂、メチル、ブチル混合型メラミン樹脂、イソブチル化メラミン樹脂等が挙げられ、これらの中では、メチル化メラミン樹脂、ブチル化メラミン樹脂、メチル、ブチル混合型メラミン樹脂が好ましい。
"Melamine resin" generally means a thermosetting resin synthesized from melamine and aldehyde, and has a triazine nucleus and three reactive functional groups-NX 1 X 2 per triazine nucleus. ing. The melamine resin is a fully alkylated type containing -N (CH 2 OR) 2 [R indicates an alkyl group having 1 or more and 8 or less carbon atoms, the same applies hereinafter] as a reactive functional group; -N as a reactive functional group. Methylol group containing (CH 2 OR) (CH 2 OH); imino group containing -N (CH 2 OR) (H) as reactive functional group; -N (CH 2 OR) as reactive functional group Four types of methylol / imino group types containing (CH 2 OH) and —N (CH 2 OR) (H) or containing —N (CH 2 OH) (H) can be exemplified.
Among the above melamine resins, it is preferable to use a completely alkylated melamine resin, and examples of such a resin include methylated melamine resin, butylated melamine resin, methyl and butyl mixed melamine resin, isobutylated melamine resin and the like. Among these, methylated melamine resin, butylated melamine resin, methyl and butyl mixed type melamine resin are preferable.
メラミン樹脂として市販品を用いてもよい。市販品としては、例えば、サイメル303、サイメル254、サイメル1170、サイメル235、サイメル238、サイメル1123、マイコート715(いずれもダイセル・オルネクス社製)、スミマールM-40S(住友化学社製)、スーパーベッカミンJ-820-60、スーパーベッカミンL-121-60、(いずれもDIC社製)、ユーバン20SE-60(三井化学社製)等を挙げることができる。
上記メラミン樹脂は、1種を単独で用いてもよく、2種以上を併用してもよい。ある態様では、上記メラミン樹脂とポリイソシアネート化合物を併用してもよい。また、必要に応じて、錫化合物、チタン化合物等の金属触媒を用いてもよい。
A commercially available product may be used as the melamine resin. Examples of commercially available products include Cymel 303, Cymel 254, Cymel 1170, Cymel 235, Cymel 238, Cymel 1123, Mycoat 715 (all manufactured by Dicel Ornex), Sumimar M-40S (manufactured by Sumitomo Chemicals), and Supermarket. Examples thereof include Beccamin J-820-60, Super Beccamin L-121-60, (all manufactured by DIC Corporation), Uban 20SE-60 (manufactured by Mitsui Chemicals, Inc.) and the like.
The above-mentioned melamine resin may be used alone or in combination of two or more. In some embodiments, the melamine resin and the polyisocyanate compound may be used in combination. Further, if necessary, a metal catalyst such as a tin compound or a titanium compound may be used.
本開示の塗料組成物は、更に、スルホン酸(C)、アミン化合物(D)及び骨材(E)を含み得る。 The coating composition of the present disclosure may further include a sulfonic acid (C), an amine compound (D) and an aggregate (E).
<スルホン酸(C)>
スルホン酸(C)は、塗膜形成樹脂(A)と架橋剤(B)との反応を促進する触媒であり、加えることによって上記反応時間を短くし得る。また、スルホン酸(C)とアミン化合物(D)とは塩を形成し得る。スルホン酸(C)とアミン化合物(D)との塩は、塗料組成物より形成される塗膜の表面硬化と内部硬化との差を大きくする作用があり、その結果として均一性が高く白ボケの少ない艶消し塗膜を形成することができる。
<Sulfonic acid (C)>
The sulfonic acid (C) is a catalyst that promotes the reaction between the coating film-forming resin (A) and the cross-linking agent (B), and the reaction time can be shortened by adding the sulfonic acid (C). Further, the sulfonic acid (C) and the amine compound (D) can form a salt. The salt of the sulfonic acid (C) and the amine compound (D) has the effect of increasing the difference between the surface curing and the internal curing of the coating film formed from the coating composition, and as a result, the uniformity is high and white blurring occurs. It is possible to form a matte coating film with a small amount of.
スルホン酸(C)の含有量は、塗膜形成樹脂(A)の樹脂固形分100質量部に対して、好ましくは1.0質量部以上18.0質量部以下、より好ましくは2.0質量部以上15.0質量部以下であり、例えば、2.0質量部以上9.0質量部以下であってもよい。
スルホン酸(C)の含有量が上記範囲内にあることで、均一性が高く白ボケの少ない艶消し塗膜が得られ、かつ、得られた塗膜の耐薬品性が優れるという利点がある。
The content of the sulfonic acid (C) is preferably 1.0 part by mass or more and 18.0 parts by mass or less, more preferably 2.0 parts by mass, with respect to 100 parts by mass of the resin solid content of the coating film forming resin (A). It may be 15.0 parts by mass or less, and may be, for example, 2.0 parts by mass or more and 9.0 parts by mass or less.
When the content of the sulfonic acid (C) is within the above range, there is an advantage that a matte coating film having high uniformity and less white blur can be obtained, and the obtained coating film has excellent chemical resistance. ..
スルホン酸としては、例えば、パラトルエンスルホン酸、ドデシルベンゼンスルホン酸、ジノニルナフタレンジスルホン酸、メタンスルホン酸、ジノニルナフタレンスルホン酸等が挙げられ、これらは1種を単独で用いてもよく、2種以上を併用してもよい。 Examples of the sulfonic acid include paratoluene sulfonic acid, dodecylbenzene sulfonic acid, dinonylnaphthalenedisulfonic acid, methanesulfonic acid, dinonylnaphthalenesulfonic acid and the like, and one of these may be used alone or 2 Seeds or more may be used together.
<アミン化合物(D)>
アミン化合物(D)は、スルホン酸(C)の中和に寄与するために存在し、少なくともその一部が本開示の塗料組成物中にスルホン酸(C)との塩として存在し得る。アミン化合物(D)は、均一な艶消し塗膜を形成することに寄与する。
<Amine compound (D)>
The amine compound (D) is present to contribute to the neutralization of the sulfonic acid (C), and at least a part thereof may be present as a salt with the sulfonic acid (C) in the coating composition of the present disclosure. The amine compound (D) contributes to forming a uniform matte coating film.
アミン化合物(D)は、好ましくは、沸点50℃以上250℃以下の2級又は3級アミンである。沸点50℃以上250℃以下の2級又は3級アミンとしては、特に限定されないが、例えば、ジエチルアミン、ジ-n-プロピルアミン、ジイソプロピルアミン、ジイソブチルアミン、ジ-n-ブチルアミン、ジアミルアミン、ジアリルアミン、ジ-sec-ブチルアミン、N-エチル-1,2-ジメチルプロピルアミン、N-メチルヘキシルアミン、ジ-n-オクチルアミン、ピペリジン、2-ピペコリン、3-ピペコリン、4-ピペコリン、2,4-ルペチジン、2,6-ルペチジン、3,5-ルペチジン、3-ピペリジンメタノール、トリエチルアミン、トリブチルアミン、トリアリルアミン、N,N-ジメチルエタノールアミン、N-メチルジアリルアミン、ピリジン、N,N-ジメチルアリルアミン、N-メチルピペリジン、4-エチルピリジン、N-メチルピペラジン、N-メチルモルホリン等が挙げられる。これらは1種を単独で用いてもよく、2種以上を併用して用いてもよい。アミン化合物(D)は、より好ましくは沸点70℃以上220℃以下の2級又は3級アミンである。 The amine compound (D) is preferably a secondary or tertiary amine having a boiling point of 50 ° C. or higher and 250 ° C. or lower. The secondary or tertiary amine having a boiling point of 50 ° C. or higher and 250 ° C. or lower is not particularly limited, and for example, diethylamine, di-n-propylamine, diisopropylamine, diisobutylamine, di-n-butylamine, diamilamine, diallylamine, di. -Sec-butylamine, N-ethyl-1,2-dimethylpropylamine, N-methylhexylamine, di-n-octylamine, piperidine, 2-pipecholine, 3-pipecholine, 4-pipecholine, 2,4-lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-piperidinmethanol, triethylamine, tributylamine, triallylamine, N, N-dimethylethanolamine, N-methyldiallylamine, pyridine, N, N-dimethylallylamine, N-methyl Examples thereof include piperidine, 4-ethylpyridine, N-methylpiperazine, N-methylmorpholin and the like. These may be used alone or in combination of two or more. The amine compound (D) is more preferably a secondary or tertiary amine having a boiling point of 70 ° C. or higher and 220 ° C. or lower.
一実施態様として、アミン化合物(D)は、スルホン酸(C)の酸基の中和率が、好ましくは300%以上、より好ましく320%以上であるように、本開示の塗料組成物に加えることができる。アミン化合物(D)は、スルホン酸(C)の酸基の中和率が3,000%以下となるように加えることができ、例えば2,000%以下、具体的には1,600%以下、より具体的には1,500%以下、更に具体的には550%以下となるように加えることができる。ここで、中和率とは、スルホン酸(C)の酸基の量100モル%に対する、アミン化合物(D)の塩基の量(モル%)をいう。なお、中和率の単位は、単に「%」と記載することもある。
特定の理論に限定して解釈すべきではないが、中和率が上記のような範囲にあることにより、塗料組成物を焼付ける際にアミン化合物(D)が揮発し、この時にアミン化合物(D)の塩基のカウンターとしてのスルホン酸(C)が、形成される膜の表層に移行して濃化すると考えられる。このようにスルホン酸(C)が表層において濃化することにより、表層における硬化反応が促進され、その結果、塗膜表面の凹凸がより良好に形成され、艶消し外観塗膜が形成されやすくなると考えられる。
In one embodiment, the amine compound (D) is added to the coating composition of the present disclosure so that the neutralization rate of the acid group of the sulfonic acid (C) is preferably 300% or more, more preferably 320% or more. be able to. The amine compound (D) can be added so that the neutralization rate of the acid group of the sulfonic acid (C) is 3,000% or less, for example, 2,000% or less, specifically 1,600% or less. , More specifically, it can be added so as to be 1,500% or less, and more specifically, 550% or less. Here, the neutralization rate means the amount of the base of the amine compound (D) (mol%) with respect to the amount of the acid group of the sulfonic acid (C) of 100 mol%. The unit of the neutralization rate may be simply described as "%".
Although not limited to a specific theory, the neutralization rate in the above range causes the amine compound (D) to volatilize when the coating composition is baked, and at this time, the amine compound ( It is considered that the sulfonic acid (C) as a counter for the base of D) migrates to the surface layer of the formed film and is concentrated. By concentrating the sulfonic acid (C) on the surface layer in this way, the curing reaction on the surface layer is promoted, and as a result, the unevenness of the coating film surface is formed better, and the matte appearance coating film is easily formed. Conceivable.
スルホン酸(C)及びアミン化合物(D)は、予め、例えば、20~30℃で10~20分間混合して形成した混合物として、塗料組成物に配合してもよい。このとき、混合物中に、スルホン酸(C)とアミン化合物(D)との塩(例えば、2級又は3級アミンでスルホン酸をブロックしたスルホン酸)が含まれ得る。
別の態様では、スルホン酸(C)とアミン化合物(D)との反応物、例えば、2級又は3級アミンでスルホン酸をブロックしたブロック化スルホン酸化合物の市販品を、塗料組成物に配合してもよい。この場合、アミン化合物(D)を併せて加えることができる。ブロック化スルホン酸化合物の市販品としては、ジノニルナフタレンジスルホン酸、メタンスルホン酸、ジノニルナフタレンスルホン酸と、これらのアミンブロック体を挙げることができる。
また、塗料組成物に、スルホン酸(C)とアミン化合物(D)とを加え、例えば、20~30℃で10~20分間混合してもよい。
The sulfonic acid (C) and the amine compound (D) may be blended in the coating composition as a mixture previously formed by mixing at 20 to 30 ° C. for 10 to 20 minutes. At this time, the mixture may contain a salt of the sulfonic acid (C) and the amine compound (D) (for example, a sulfonic acid obtained by blocking the sulfonic acid with a secondary or tertiary amine).
In another embodiment, a reaction product of the sulfonic acid (C) and the amine compound (D), for example, a commercially available blocked sulfonic acid compound in which the sulfonic acid is blocked with a secondary or tertiary amine is blended in the coating composition. You may. In this case, the amine compound (D) can be added together. Examples of commercially available blocked sulfonic acid compounds include dinonylnaphthalenedisulfonic acid, methanesulfonic acid, dinonylnaphthalenesulfonic acid, and amine-blocked compounds thereof.
Further, the sulfonic acid (C) and the amine compound (D) may be added to the coating composition and mixed at 20 to 30 ° C. for 10 to 20 minutes, for example.
スルホン酸(C)とアミン化合物(D)との塩を加える場合、上記塩の含有量は、塗膜形成樹脂(A)の樹脂固形分100質量部に対して、スルホン酸換算で1.0質量部以上23.0質量部以下が好ましく、2.0質量部以上19.0質量部以下がより好ましい。
なお、本開示において、前記スルホン酸(C)とアミン化合物(D)との塩のような化合物を使用する場合、含有量はスルホン酸換算の量を意味する。
When a salt of the sulfonic acid (C) and the amine compound (D) is added, the content of the salt is 1.0 in terms of sulfonic acid with respect to 100 parts by mass of the resin solid content of the coating film forming resin (A). It is preferably 23.0 parts by mass or more, and more preferably 2.0 parts by mass or more and 19.0 parts by mass or less.
In the present disclosure, when a compound such as a salt of the sulfonic acid (C) and the amine compound (D) is used, the content means an amount in terms of sulfonic acid.
一実施態様において、スルホン酸(C)の含有量が、塗膜形成樹脂(A)の樹脂固形分100質量部に対して、1質量部以上18質量部以下であり、かつ、アミン(D)の中和率が、300%以上3,000%以下の範囲にあることが好ましく、スルホン酸(C)の含有量が2質量部以上15質量部以下であり、かつ、アミン(D)中和率320%以上2,000%以下の範囲にあることがより好ましく、スルホン酸(C)の含有量が2質量部以上15質量部以下であり、かつ、アミン(D)の中和率が320%以上1,500%以下の範囲にあることが更に好ましい。塗料組成物が上記のようなスルホン酸(C)の含有量及び中和率を有することにより、形成される塗膜の表面におけるRa及びSdrの値が特に良好になり得る。また、上記のような塗料組成物を用いることにより、艶消し外観を有し、低光沢、及び高耐候性を有する塗膜が形成され得る。 In one embodiment, the content of the sulfonic acid (C) is 1 part by mass or more and 18 parts by mass or less with respect to 100 parts by mass of the resin solid content of the coating film-forming resin (A), and the amine (D). The neutralization rate of the above is preferably in the range of 300% or more and 3,000% or less, the content of the sulfonic acid (C) is 2 parts by mass or more and 15 parts by mass or less, and the amine (D) is neutralized. The rate is more preferably in the range of 320% or more and 2,000% or less, the content of the sulfonic acid (C) is 2 parts by mass or more and 15 parts by mass or less, and the neutralization rate of the amine (D) is 320. It is more preferably in the range of% or more and 1,500% or less. When the coating composition has the above-mentioned sulfonic acid (C) content and neutralization rate, the Ra and Sdr values on the surface of the formed coating film can be particularly good. Further, by using the coating composition as described above, a coating film having a matte appearance, low gloss and high weather resistance can be formed.
<骨材(E)>
骨材(E)を含むことにより、本開示の塗料組成物より形成される塗膜において、均一性が高く白ボケの少ない艶消し塗膜を安定的に発現させ得る。
<Aggregate (E)>
By containing the aggregate (E), a matte coating film having high uniformity and less white blur can be stably developed in the coating film formed from the coating composition of the present disclosure.
骨材(E)は、塗膜形成樹脂(A)の樹脂固形分100質量部に対して、0.1質量部以上15質量部以下加えてもよく、2質量部以上12質量部以下加えてもよい。
骨材(E)を上記の範囲で加えることにより、均一な艶消し塗膜を特に安定的に発現させることができる。
The aggregate (E) may be added by 0.1 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the resin solid content of the coating film forming resin (A) by adding 2 parts by mass or more and 12 parts by mass or less. May be good.
By adding the aggregate (E) in the above range, a uniform matte coating film can be developed particularly stably.
一実施態様において、骨材(E)は、アクリル樹脂粒子、ガラスビーズ、アクリロニトリル樹脂粒子、尿素樹脂粒子、セラミック繊維及びシリカ粒子からなる群から選択される少なくとも1種を含み、アクリル樹脂粒子、尿素樹脂粒子及びシリカ粒子からなる群から選択される少なくとも1種を含むことが好ましく、シリカ粒子を含むことがより好ましい。
本態様の骨材(E)を含むことにより、本開示の塗料組成物より得られる塗膜において、均一な艶消し塗膜を安定的に発現させ得る。
In one embodiment, the aggregate (E) comprises at least one selected from the group consisting of acrylic resin particles, glass beads, acrylonitrile resin particles, urea resin particles, ceramic fibers and silica particles, and includes acrylic resin particles and urea. It preferably contains at least one selected from the group consisting of resin particles and silica particles, and more preferably contains silica particles.
By including the aggregate (E) of this embodiment, a uniform matte coating film can be stably expressed in the coating film obtained from the coating composition of the present disclosure.
(シリカ粒子)
一実施態様において、骨材(E)はシリカ粒子である。
前記シリカ粒子の平均粒子径は、好ましくは1μm以上20μm以下、より好ましくは2μm以上17μm以下、例えば2μm以上15μm以下、2.5μm以上15μm以下であってもよい。なお、本開示において、骨材(E)の平均粒子径は、レーザー散乱法や回折法等を用いた通常の測定機器により求めた体積平均粒子径(D50)を指すものであり、例えば、レーザー回折式粒度分布測定装置SALD-2300(島津製作所社製)等を使用して測定することができる。
(Silica particles)
In one embodiment, the aggregate (E) is silica particles.
The average particle size of the silica particles may be preferably 1 μm or more and 20 μm or less, more preferably 2 μm or more and 17 μm or less, for example, 2 μm or more and 15 μm or less, and 2.5 μm or more and 15 μm or less. In the present disclosure, the average particle size of the aggregate (E) refers to the volume average particle size (D50) obtained by a normal measuring device using a laser scattering method, a diffraction method, or the like, and is, for example, a laser. The measurement can be performed using a diffraction type particle size distribution measuring device SALD-2300 (manufactured by Shimadzu Corporation) or the like.
シリカ粒子の含有量は、塗膜形成樹脂(A)の樹脂固形分100質量部に対して、0.1質量部以上15質量部以下であってもよく、2質量部以上12質量部以下であってもよい。シリカ粒子の含有量が上記範囲内にあることで、得られる塗膜はより均一な艶消し外観となり得る。 The content of the silica particles may be 0.1 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the resin solid content of the coating film forming resin (A), and may be 2 parts by mass or more and 12 parts by mass or less. There may be. When the content of the silica particles is within the above range, the obtained coating film can have a more uniform matte appearance.
シリカ粒子は、特に限定されないが、湿式法、乾式法のいずれの方法によって製造されたものであってもよい。シリカ粒子としては、例えば、表面が無処理のシリカ粒子、表面が有機物で処理されたシリカ粒子、有機溶剤分散性コロイダルシリカ等を挙げることができる。 The silica particles are not particularly limited, but may be produced by either a wet method or a dry method. Examples of the silica particles include silica particles whose surface is untreated, silica particles whose surface is treated with an organic substance, and organic solvent-dispersible colloidal silica.
シリカ粒子としては、市販品を用いてもよい。市販品としては、サイリシア710、サイリシア740、サイリシア550(以上、いずれも富士シリシア化学社製)、ミズカシルP-73(水澤化学工業社製)、ニップシール E-200A、ニップジェル AZ-6A0(いずれも東ソー・シリカ社製)、GASIL HP270、GASIL HP395(いずれもPQコーポレーション社製)等を挙げることができる。 Commercially available products may be used as the silica particles. Commercially available products include Siricia 710, Siricia 740, Siricia 550 (all manufactured by Fuji Silysia Chemical Ltd.), Mizukasil P-73 (manufactured by Mizusawa Industrial Chemical Ltd.), Nip Seal E-200A, and Nip Gel AZ-6A0 (all manufactured by Tosoh). (Silysia), GASIC HP270, GASIC HP395 (all manufactured by PQ Corporation) and the like can be mentioned.
(アクリル樹脂粒子)
一実施態様において、骨材(E)はアクリル樹脂粒子である。
アクリル樹脂粒子の平均粒子径は、好ましくは1μm以上20μm以下であり、例えば2μm以上15μm以下、2.5μm以上15μm以下であってもよく、5μm以上10μm以下であってもよい。
(Acrylic resin particles)
In one embodiment, the aggregate (E) is acrylic resin particles.
The average particle size of the acrylic resin particles is preferably 1 μm or more and 20 μm or less, and may be, for example, 2 μm or more and 15 μm or less, 2.5 μm or more and 15 μm or less, or 5 μm or more and 10 μm or less.
アクリル樹脂粒子の含有量は、塗膜形成樹脂(A)の樹脂固形分100質量部に対して、0.1質量部以上15質量部以下であってもよく、2質量部以上12質量部以下であってもよい。アクリル樹脂粒子の含有量が上記範囲内にあることで、均一な艶消し外観が形成できる。 The content of the acrylic resin particles may be 0.1 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the resin solid content of the coating film forming resin (A), and is 2 parts by mass or more and 12 parts by mass or less. May be. When the content of the acrylic resin particles is within the above range, a uniform matte appearance can be formed.
アクリル樹脂粒子としては、市販品を用いてもよい。市販品としては、ガンツパール GM-0801(アイカ工業社製)等を挙げることができる。 Commercially available products may be used as the acrylic resin particles. Examples of commercially available products include Ganz Pearl GM-0801 (manufactured by Aica Kogyo Co., Ltd.).
(尿素樹脂粒子)
一実施態様において、骨材(E)は尿素樹脂粒子である。
尿素樹脂粒子の平均粒子径は、好ましくは1μm以上20μm以下であり、例えば2μm以上15μm以下、2.5μm以上15μm以下であってもよい。
(Urea resin particles)
In one embodiment, the aggregate (E) is urea resin particles.
The average particle size of the urea resin particles is preferably 1 μm or more and 20 μm or less, and may be, for example, 2 μm or more and 15 μm or less, and 2.5 μm or more and 15 μm or less.
尿素樹脂粒子の含有量は、塗膜形成樹脂(A)の樹脂固形分100質量部に対して、0.1質量部以上15質量部以下であってもよく、2質量部以上12質量部以下であってもよい。尿素樹脂粒子の含有量が上記範囲内にあることで、より均一な艶消し外観が形成できる。 The content of the urea resin particles may be 0.1 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the resin solid content of the coating film forming resin (A), and is 2 parts by mass or more and 12 parts by mass or less. May be. When the content of the urea resin particles is within the above range, a more uniform matte appearance can be formed.
尿素樹脂粒子としては、市販品を用いてもよい。市販品としては、パーゴパックM4(ロンザ・ジャパン社製)等を挙げることができる。 Commercially available products may be used as the urea resin particles. Examples of commercially available products include Pergopack M4 (manufactured by Lonza Japan) and the like.
一実施態様において、塗膜形成樹脂(A)の樹脂固形分100質量部に対して、スルホン酸(C)は1.0質量部以上18.0質量部以下(具体的には2.0質量部以上9.0質量部以下)、アミン化合物(D)の中和率は300%以上3,000%以下(具体的には300%以上1,500%以下、例えば、550%以下)、骨材(E)は2質量部以上12質量部以下加えてもよい。本態様においては、スルホン酸(C)としては、スルホン酸、アミン化合物(D)としては、2級又は3級アミン、骨材(E)としては、シリカ粒子、アクリル樹脂粒子を用いることが好ましい。 In one embodiment, the sulfonic acid (C) is 1.0 part by mass or more and 18.0 part by mass or less (specifically, 2.0 part by mass) with respect to 100 parts by mass of the resin solid content of the coating film forming resin (A). (Parts or more and 9.0 parts by mass or less), the neutralization rate of the amine compound (D) is 300% or more and 3,000% or less (specifically, 300% or more and 1,500% or less, for example, 550% or less), bone. The material (E) may be added in an amount of 2 parts by mass or more and 12 parts by mass or less. In this embodiment, it is preferable to use sulfonic acid as the sulfonic acid (C), secondary or tertiary amine as the amine compound (D), and silica particles or acrylic resin particles as the aggregate (E). ..
<その他の添加剤>
本開示の塗料組成物は、塗膜形成樹脂(A)に加えて、更に、熱可塑性樹脂を用いることもできる。
熱可塑性樹脂として、例えば、塩素化ポリエチレン、塩素化ポリプロピレン等の塩素化オレフィン系樹脂;塩化ビニル、酢酸ビニル、塩化ビニリデン等をモノマー成分とする単独重合体又は共重合体;セルロース系樹脂;アセタール樹脂;アルキド樹脂;塩化ゴム系樹脂;変性ポリプロピレン樹脂(酸無水物変性ポリプロピレン樹脂等);フッ素樹脂(例えば、フッ化ビニリデン樹脂、フッ化ビニル樹脂、フッ素化オレフィンとビニルエーテルとの共重合体、フッ素化オレフィンとビニルエステルとの共重合体)等を挙げることができる。熱可塑性樹脂は、1種のみを単独で用いてもよく、2種以上を併用してもよい。
熱可塑性樹脂を併用することで、形成される塗膜において、より良好な塗膜物性、例えば、より良好な塗膜強度、伸び等を得ることができる。
<Other additives>
In the coating composition of the present disclosure, a thermoplastic resin can be further used in addition to the coating film forming resin (A).
Examples of the thermoplastic resin include chlorinated olefin resins such as chlorinated polyethylene and chlorinated polypropylene; homopolymers or copolymers containing vinyl chloride, vinyl acetate, vinylidene chloride and the like as monomer components; cellulose resins; acetal resins. Alexandre resin; Rubber chloride resin; Modified polypropylene resin (acid anhydride-modified polypropylene resin, etc.); Fluorine resin (for example, vinylidene fluoride resin, vinyl fluoride resin, copolymer of fluorinated olefin and vinyl ether, fluorination A copolymer of an olefin and a vinyl ester) and the like can be mentioned. As the thermoplastic resin, only one kind may be used alone, or two or more kinds may be used in combination.
By using the thermoplastic resin in combination, it is possible to obtain better coating film physical characteristics, for example, better coating film strength, elongation, etc. in the formed coating film.
本開示の塗料組成物は、更に、その他の添加剤を含有してもよい。その他の添加剤としては、例えば、表面調整剤;体質顔料;着色顔料、染料等の着色剤;ワックス;遮熱顔料;光輝性顔料;溶剤;紫外線吸収剤(ベンゾフェノン系紫外線吸収剤等);酸化防止剤(フェノール系、スルフォイド系、ヒンダードアミン系酸化防止剤等);可塑剤;カップリング剤(シラン系、チタン系、ジルコニウム系カップリング剤等);タレ止め剤;増粘剤;顔料分散剤;顔料湿潤剤;レベリング剤;色分かれ防止剤;沈殿防止剤;消泡剤;凍結防止剤;乳化剤;防腐剤;防かび剤;抗菌剤;安定剤等がある。これらの添加剤は、1種のみを単独で用いてもよいし、2種以上を併用してもよい。 The coating composition of the present disclosure may further contain other additives. Other additives include, for example, surface conditioners; extender pigments; coloring pigments, coloring agents such as dyes; waxes; heat-shielding pigments; brilliant pigments; solvents; ultraviolet absorbers (benzophenone-based ultraviolet absorbers, etc.); oxidation. Inhibitors (phenolic, sulfoid, hindered amine antioxidants, etc.); Plastics; Coupling agents (silane, titanium, zirconium couplings, etc.); Anti-sagging agents; Thickeners; Pigment dispersants; Pigment wetting agents; leveling agents; color separation inhibitors; precipitation inhibitors; antifoaming agents; antifreeze agents; emulsifiers; preservatives; antifungal agents; antibacterial agents; stabilizers and the like. These additives may be used alone or in combination of two or more.
表面調整剤としては、塗料用として当業者に周知のものを使用できる。
好ましい表面調整剤としては、アクリル系、シリコーン系及びフッ素系の界面活性剤等を挙げることができる。これらは1種のみを単独で用いてもよいし、2種以上を併用してもよい。
艶消し外観塗膜は、塗膜の表層部の硬化反応が速いために形成されるが、塗膜の表層部よりも内面側に存在する層(「下層部」ともいう)の流動性が大きすぎると、円形の艶ムラやワレ状肌等の外観不良が生じることがある。表面調整剤を塗料組成物に添加することで、塗膜上下層の反応温度差を保持しながら下層部の流動性を適度な状態に抑制し、上記の塗膜の外観不良を抑制し、均一な縮み肌の形成に寄与し得る。
表面調整剤の含有量は、例えば、塗膜形成樹脂(A)の樹脂固形分100質量部に対して、0.5質量部以上10質量部以下である。
表面調整剤としては、例えば、ディスパロンOX-70(楠本化成社製)を挙げることができる。
As the surface conditioner, those well known to those skilled in the art for paints can be used.
Preferred surface conditioners include acrylic, silicone and fluorine-based surfactants. These may be used alone or in combination of two or more.
The matte appearance coating film is formed because the curing reaction of the surface layer portion of the coating film is fast, but the fluidity of the layer (also referred to as “lower layer portion”) existing on the inner surface side of the surface layer portion of the coating film is large. If it is too much, poor appearance such as circular gloss unevenness and cracked skin may occur. By adding a surface conditioner to the coating composition, the fluidity of the lower layer portion is suppressed to an appropriate state while maintaining the reaction temperature difference between the upper and lower layers of the coating film, and the appearance deterioration of the above coating film is suppressed and uniform. It can contribute to the formation of shrunken skin.
The content of the surface adjusting agent is, for example, 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin solid content of the coating film forming resin (A).
As the surface conditioner, for example, Disparon OX-70 (manufactured by Kusumoto Kasei Co., Ltd.) can be mentioned.
体質顔料としては、炭酸カルシウム、硫酸バリウム、クレー、タルク、マイカ、ガラス繊維等を挙げることができる。これらは1種のみを単独で用いてもよいし、2種以上を併用してもよい。一実施態様において、体質顔料の含有量は、塗膜形成樹脂(A)の樹脂固形分100質量部に対して1質量部以上40質量部以下であり、例えば、10質量部以上30質量部以下である。体質顔料の量がこのような範囲内であることにより、塗膜の耐傷付性を向上させる等の有利な効果がある。 Examples of the extender pigment include calcium carbonate, barium sulfate, clay, talc, mica, glass fiber and the like. These may be used alone or in combination of two or more. In one embodiment, the content of the extender pigment is 1 part by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the resin solid content of the coating film forming resin (A), for example, 10 parts by mass or more and 30 parts by mass or less. Is. When the amount of the extender pigment is within such a range, there is an advantageous effect such as improving the scratch resistance of the coating film.
着色顔料としては、例えば、二酸化チタン、カーボンブラック、グラファイト、酸化鉄、コールダスト等の着色無機顔料;フタロシアニンブルー、フタロシアニングリーン、キナクリドン、ペリレン、アンスラピリミジン、カルバゾールバイオレット、アントラピリジン、アゾオレンジ、フラバンスロンイエロー、イソインドリンイエロー、アゾイエロー、インダスロンブルー、ジブロムアンザスロンレッド、ペリレンレッド、アゾレッド、アントラキノンレッド等の着色有機顔料;アルミニウム粉、アルミナ粉、ブロンズ粉、銅粉、スズ粉、亜鉛粉、リン化鉄、微粒化チタン等を挙げることができる。これらは、1種のみを単独で用いてもよいし、2種以上を併用してもよい。 Colored pigments include, for example, colored inorganic pigments such as titanium dioxide, carbon black, graphite, iron oxide, and cold dust; phthalocyanine blue, phthalocyanine green, quinacridone, perylene, anthrapyrimidine, carbazole violet, anthrapyridine, azoorange, and flavanthrone. Colored organic pigments such as yellow, isoindrin yellow, azo yellow, induthron blue, dibrom anzaslon red, perylene red, azo red, anthraquinone red; aluminum powder, alumina powder, bronze powder, copper powder, tin powder, zinc powder, Examples thereof include iron phosphate and atomized titanium. These may be used alone or in combination of two or more.
遮熱顔料は、無機系遮熱顔料及び/又は有機系遮熱顔料を含む。
無機系遮熱顔料としては、例えば、酸化チタン、酸化マグネシウム、酸化バリウム、酸化カルシウム、酸化亜鉛、酸化ジルコニウム、酸化イットリウム、酸化インジウム、チタン酸ナトリウム、酸化ケイ素、酸化ニッケル、酸化マンガン、酸化クロム、酸化鉄、酸化銅、酸化セリウム、酸化アルミニウム等の金属酸化物系顔料;酸化鉄-酸化マンガン、酸化鉄-酸化クロム(例えば、大日精化社製のダイピロキサイドカラーブラック#9595、アサヒ化成工業社製のBlack6350)、酸化鉄-酸化コバルト-酸化クロム(例えば、大日精化社製のダイピロキサイドカラーブラウン#9290、ダイピロキサイドカラーブラック#9590)、酸化銅-酸化マグネシウム(例えば、大日精化社製のダイピロキサイドカラーブラック#9598)、酸化マンガン-酸化ビスマス(例えば、アサヒ化成工業社製のBlack6301)、酸化マンガン-酸化イットリウム(例えば、アサヒ化成工業社製のBlack6303)等の複合酸化物顔料;アルミニウム、鉄、マグネシウム、マンガン、ニッケル、チタン、クロム、カルシウム等の金属系顔料;更に、鉄-クロム、ビスマス-マンガン、鉄-マンガン、マンガン-イットリウム等の合金系顔料が挙げられる。これらは、単独又は2種以上を組み合せて用いることができる。
有機系遮熱顔料としては、例えば、アゾ系顔料、アゾメチン系顔料、レーキ系顔料、チオインジゴ系顔料、アントラキノン系顔料(アントアンスロン顔料、ジアミノアンスラキノニル顔料、インダンスロン顔料、フラバンスロン顔料、アントラピリミジン顔料等)、ペリレン系顔料、ペリノン系顔料、ジケトピロロピロール系顔料、ジオキサジン系顔料、フタロシアニン系顔料、キニフタロン系顔料、キナクリドン系顔料、イソインドリン系顔料、イソインドリノン系顔料、等が挙げられる。これらは、単独又は2種以上を組み合せて用いることができる。
なお、本開示において、遮熱顔料とは、近赤外波長域(波長:780nm~2,500nm)の光を吸収しないか、又は近赤外波長域(波長:780nm~2,500nm)の光の吸収率が小さい顔料を示す。
The heat-shielding pigment includes an inorganic heat-shielding pigment and / or an organic heat-shielding pigment.
Examples of the inorganic heat-shielding pigment include titanium oxide, magnesium oxide, barium oxide, calcium oxide, zinc oxide, zirconium oxide, yttrium oxide, indium oxide, sodium titanate, silicon oxide, nickel oxide, manganese oxide, and chromium oxide. Metal oxide pigments such as iron oxide, copper oxide, cerium oxide, aluminum oxide; iron oxide-manganese oxide, iron oxide-chromium oxide (for example, Daipiroxide Color Black # 9595 manufactured by Dainichi Seika Co., Ltd., Asahi Kasei Kogyo Co., Ltd. Black 6350), Iron Oxide-Cobalt Oxide-Chrome Oxide (eg, Dipiroxide Color Brown # 9290, Dipiroxide Color Black # 9590), Copper Oxide-Magnetic Oxide (eg, Dainichisei). Composite oxidation of manganese oxide-bismuth oxide (for example, Black6301 manufactured by Asahi Kasei Kogyo Co., Ltd.), manganese oxide-ittrium oxide (for example, Black6303 manufactured by Asahi Kasei Kogyo Co., Ltd.), etc. Material pigments; Metallic pigments such as aluminum, iron, magnesium, manganese, nickel, titanium, chromium and calcium; Further, alloy pigments such as iron-chromium, bismuth-manganese, iron-manganese and manganese-ittrium can be mentioned. These can be used alone or in combination of two or more.
Examples of the organic heat-shielding pigment include azo pigments, azomethine pigments, lake pigments, thioindigo pigments, and anthraquinone pigments (anthanthrone pigments, diaminoanthracinyl pigments, indanslon pigments, flavanthron pigments, and anthra. (Pyrimidine pigments, etc.), perylene pigments, perinone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, phthalocyanine pigments, quiniphthalone pigments, quinacridone pigments, isoindolin pigments, isoindolinone pigments, etc. Be done. These can be used alone or in combination of two or more.
In the present disclosure, the heat-shielding pigment means light in the near-infrared wavelength range (wavelength: 780 nm to 2,500 nm) or light in the near-infrared wavelength range (wavelength: 780 nm to 2,500 nm). Indicates a pigment having a small absorption rate.
光輝性顔料としては、例えば、アルミ箔、ブロンズ箔、スズ箔、金箔、銀箔、チタン金属箔、ステンレススチール箔、ニッケル・銅等の合金箔、箔状フタロシアニンブルー等の箔顔料を挙げることができる。これらは、1種のみを単独で用いてもよいし、2種以上を併用してもよい。 Examples of the brilliant pigment include aluminum foil, bronze foil, tin foil, gold leaf, silver foil, titanium metal foil, stainless steel foil, alloy foil such as nickel and copper, and foil pigment such as foil-like phthalocyanine blue. .. These may be used alone or in combination of two or more.
ワックスとしては、塗料用として当業者に知られているワックスが使用でき、例えば、マイクロクリスタリン、ポリエチレン、ポリプロピレン、パラフィン、カルナウバ及びそれらの変性物等が挙げられる。 As the wax, waxes known to those skilled in the art for paints can be used, and examples thereof include microcrystallin, polyethylene, polypropylene, paraffin, carnauba and modified products thereof.
溶剤としては、例えば、水;エチレングリコールモノブチルエーテル(ブチルセロソルブ)、ジエチレングリコールモノブチルエーテル、トリエチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテルアセテート等のグリコール系有機溶剤;メタノール、エタノール、イソプロピルアルコール、ソルフィット(クラレ社製)等のアルコール系有機溶剤;ジオキサン、テトラヒドロフラン等のエーテル系有機溶剤;3-メトキシブチルアセテート、酢酸エチル、酢酸イソプロピル、酢酸ブチル等のエステル系有機溶媒;メチルエチルケトン、アセトン、メチルイソブチルケトン、シクロヘキサノン、イソホロン等のケトン系有機溶剤;並びに、N-メチル-2-ピロリドン、トルエン、ペンタン、iso-ペンタン、ヘキサン、iso-ヘキサン、シクロヘキサン、ソルベントナフサ、ミネラルスピリット、T-SOL 100、T-SOL 150(いずれも芳香族炭化水素系溶剤、JXTGエネルギー社製)等を挙げることができる。これらは、1種のみを単独で用いてもよいし、2種以上を併用してもよい。 Examples of the solvent include water; ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, and the like. Glycol-based organic solvents such as dipropylene glycol monoethyl ether and propylene glycol monomethyl ether acetate; alcohol-based organic solvents such as methanol, ethanol, isopropyl alcohol and Solfit (manufactured by Claret); ether-based organic solvents such as dioxane and tetrahydrofuran; Ether-based organic solvents such as 3-methoxybutyl acetate, ethyl acetate, isopropyl acetate, butyl acetate; ketone-based organic solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, isophorone; and N-methyl-2-pyrrolidone, toluene. , Pentan, iso-pentane, hexane, iso-hexane, cyclohexane, solvent naphtha, mineral spirit, T-SOL 100, T-SOL 150 (all are aromatic hydrocarbon solvents, manufactured by JXTG Energy Co., Ltd.) and the like. can. These may be used alone or in combination of two or more.
本開示の塗料組成物は、水系塗料であってもよく、有機溶剤系の塗料であってもよい。 The coating composition of the present disclosure may be a water-based coating material or an organic solvent-based coating material.
<塗料組成物の調製方法>
本開示の塗料組成物を調製する方法は、特に限定されない。例えば、サンドグラインドミル、ボールミル、ブレンダー、ペイントシェーカー又はディスパー等の混合機、分散機、混練機等を選択して使用し、各成分を混合することにより、調製することができる。
<Preparation method of paint composition>
The method for preparing the coating composition of the present disclosure is not particularly limited. For example, it can be prepared by selecting and using a mixer such as a sand grind mill, a ball mill, a blender, a paint shaker or a disper, a disperser, a kneader and the like, and mixing each component.
(被塗物)
本開示の塗料組成物の塗装の対象となる被塗物は、例えば、溶融法又は電解法等により製造される亜鉛めっき鋼板、亜鉛-アルミニウム合金めっき鋼板、アルミニウム合金めっき鋼板、溶融亜鉛-アルミニウム-マグネシウム合金めっき鋼板、ステンレス鋼板、冷延鋼板等の金属板が挙げられる。また、これら鋼板又はめっき鋼板以外に、アルミニウム板(アルミニウム合金板を含む)等の金属板も塗装対象とすることができる。
上記金属板は、表面処理されていることが好ましい。具体的には、上記金属板は、アルカリ脱脂処理、湯洗処理、水洗処理等の前処理が施された後に、化成処理が施されていることが好ましい。化成処理は公知の方法で行ってよく、その例にはクロメート処理、リン酸亜鉛処理等の非クロメート処理等が含まれる。上記表面処理としては、使用する鋼板に応じて適宜選択することができるが、重金属を含まない処理が好ましい。
(Applied material)
The object to be coated of the coating composition of the present disclosure is, for example, a galvanized steel sheet, a zinc-aluminum alloy-plated steel sheet, an aluminum alloy-plated steel sheet, or a hot-dip galvanized steel sheet manufactured by a melting method or an electrolytic method. Examples thereof include metal plates such as magnesium alloy plated steel plates, stainless steel plates, and cold-rolled steel plates. In addition to these steel plates or plated steel plates, metal plates such as aluminum plates (including aluminum alloy plates) can also be painted.
The metal plate is preferably surface-treated. Specifically, it is preferable that the metal plate is subjected to a chemical conversion treatment after being subjected to a pretreatment such as an alkaline degreasing treatment, a hot water washing treatment, and a water washing treatment. The chemical conversion treatment may be carried out by a known method, and examples thereof include chromate treatment, non-chromate treatment such as zinc phosphate treatment and the like. The surface treatment can be appropriately selected depending on the steel sheet to be used, but a treatment that does not contain heavy metals is preferable.
<塗装鋼板>
本開示の塗装鋼板は、鋼板、及び、該鋼板の少なくとも一方の表面に本開示の塗料組成物から形成された塗膜を有する。上記塗料組成物は、少なくとも塗膜形成樹脂(A)と、架橋剤(B)とを含む。上記塗膜の表面において、算術平均高さ(Ra)が1.2μm以上であり、かつ展開面積比(Sdr)が800%以上である。
<Painted steel plate>
The coated steel sheet of the present disclosure has a steel sheet and a coating film formed from the coating composition of the present disclosure on at least one surface of the steel sheet. The coating composition contains at least a coating film-forming resin (A) and a cross-linking agent (B). On the surface of the coating film, the arithmetic mean height (Ra) is 1.2 μm or more, and the developed area ratio (Sdr) is 800% or more.
塗料組成物から形成された塗膜の膜厚は、10μm以上25μm以下であり、ある態様においては、膜厚は、15μm以上22μm以下である。 The film thickness of the coating film formed from the coating composition is 10 μm or more and 25 μm or less, and in one embodiment, the film thickness is 15 μm or more and 22 μm or less.
一の態様において、鋼板は、一方の表面に本開示に係る塗料組成物から形成された塗膜を有し、他方の表面に、既知の塗料組成物から形成される塗膜を有する。例えば、他方の表面には、エポキシ樹脂を含む塗料組成物等、公知の塗料組成物から形成された塗膜を有してもよい。 In one embodiment, the steel sheet has a coating film formed from the coating composition according to the present disclosure on one surface and a coating film formed from a known coating composition on the other surface. For example, the other surface may have a coating film formed from a known coating composition such as a coating composition containing an epoxy resin.
塗装鋼板は、鋼板と、本開示の塗料組成物から形成した塗膜との間に、下塗り塗膜を有してもよい。
上記下塗り塗料は従来公知のものであってよく、例えば、従来公知の非クロム系防錆塗料等が挙げられる。
下塗り塗膜を有することで、本開示の塗料組成物から形成された塗膜の密着性、耐食性を高めることができる。
ある態様において、下塗り塗膜の膜厚は、3μm以上15μm以下であり、例えば5μm以上10μm以下である。
The coated steel sheet may have an undercoat coating film between the steel sheet and the coating film formed from the coating composition of the present disclosure.
The undercoat paint may be a conventionally known one, and examples thereof include a conventionally known non-chromium-based rust preventive paint.
By having the undercoat coating film, the adhesion and corrosion resistance of the coating film formed from the coating composition of the present disclosure can be enhanced.
In one embodiment, the film thickness of the undercoat coating film is 3 μm or more and 15 μm or less, for example, 5 μm or more and 10 μm or less.
<塗膜の製造方法>
本開示の塗膜の製造方法は、
被塗物に本開示の塗料組成物を塗装する工程、及び
前記塗料組成物を150℃以上270℃以下の温度で乾燥及び/又は硬化させることを含む。
<Manufacturing method of coating film>
The method for producing a coating film of the present disclosure is as follows.
It comprises a step of applying the coating composition of the present disclosure to an object to be coated, and drying and / or curing the coating composition at a temperature of 150 ° C. or higher and 270 ° C. or lower.
被塗物の表面に塗装下地処理としてリン酸塩処理、クロメート処理等の化成処理を施し、その上に塗料組成物を塗装することが好ましい。このように化成処理を施した金属板面上に、本開示の塗料組成物を塗装することにより、塗膜の金属板面に対する密着性が向上するとともに耐食性も向上する。また、化成処理を施した金属板面に下塗り塗膜(プライマー塗膜)を形成し、その上に塗装することもできる。
本発明の塗料組成物からなる塗膜は、塗料組成物を鋼板等の被塗物に塗布した後、被塗物を加熱する焼付け処理を行なうことによって形成することができる。
塗料組成物の塗装は、被塗物に、バーコーター、ロールコーター、ロールカーテンコーター、カーテンフローコーター、ダイコーター又はスプレーガンを用いて行うことができる。
また、塗装後、被塗物を加熱する焼付け処理方法は特に限定しないが、熱風加熱、赤外線加熱、誘導加熱等の加熱手段により塗膜を焼き付け、樹脂を架橋させて硬化塗膜を得ることができる。焼付け温度(鋼板等の被塗物が達する最高温度)は、通常180℃以上250℃以下であり、焼付け時間は、通常10秒以上200秒以下である。
本発明の塗料組成物を用いて得られる塗膜の膜厚(乾燥膜厚)は、通常1μm以上30μm以下であり、例えば、上塗り塗膜である場合は、好ましくは10μm以上25μm以下である。
It is preferable to apply a chemical conversion treatment such as a phosphate treatment or a chromate treatment to the surface of the object to be coated as a coating base treatment, and then coat the coating composition on the chemical conversion treatment. By coating the coating composition of the present disclosure on the metal plate surface subjected to the chemical conversion treatment in this manner, the adhesion of the coating film to the metal plate surface is improved and the corrosion resistance is also improved. It is also possible to form an undercoat coating film (primer coating film) on the surface of a metal plate that has undergone chemical conversion treatment, and then coat the surface thereof.
The coating film made of the coating composition of the present invention can be formed by applying the coating composition to an object to be coated such as a steel plate and then performing a baking treatment for heating the object to be coated.
The coating composition can be applied to the object to be coated by using a bar coater, a roll coater, a roll curtain coater, a curtain flow coater, a die coater or a spray gun.
The baking method for heating the object to be coated after coating is not particularly limited, but the coating film may be baked by heating means such as hot air heating, infrared heating, induction heating, etc., and the resin may be crosslinked to obtain a cured coating film. can. The baking temperature (the maximum temperature reached by an object to be coated such as a steel sheet) is usually 180 ° C. or higher and 250 ° C. or lower, and the baking time is usually 10 seconds or longer and 200 seconds or lower.
The film thickness (dry film thickness) of the coating film obtained by using the coating composition of the present invention is usually 1 μm or more and 30 μm or less, and for example, in the case of a top coat film, it is preferably 10 μm or more and 25 μm or less.
以下、実施例により、本発明を更に具体的に説明する。本発明は、以下の実施例に限定されない。実施例中「部」及び「%」は、ことわりのない限り質量基準による。 Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited to the following examples. In the examples, "parts" and "%" are based on mass unless otherwise specified.
[塗膜形成樹脂(A)]
塗膜形成樹脂(A-1)~(A-6)として、それぞれ以下のように調製したものを用いた。
[Coating film forming resin (A)]
As the coating film forming resins (A-1) to (A-6), those prepared as follows were used.
<塗膜形成樹脂(A-1)の調製>
温度計、コンデンサー及び撹拌機を備えた反応容器に、ネオペンチルグリコール155質量部、1,6-ヘキサンジオール222質量部、トリメチロールプロパン50質量部、イソフタル酸441質量部、アジピン酸132質量部及びキシレン26質量部を混合し、窒素気流中で230℃にまで徐々に昇温し、生成する水を留去しながら、脱水量が126質量部に達し、反応物が所定の粘度になるまでエステル化反応を行った(工程a1-1)。その後、反応容器の温度を50℃に下げた後、キシレン90質量部、T-SOL150 379質量部及びプロピレングリコールモノメチルエーテルアセテート87質量部を混合し(工程a1-2)、塗膜形成樹脂(A-1)(ポリエステル樹脂1;固形分濃度:60質量%、数平均分子量:3,000、水酸基価:55mgKOH/g)を調製した。
<Preparation of coating film forming resin (A-1)>
In a reaction vessel equipped with a thermometer, condenser and stirrer, 155 parts by mass of neopentyl glycol, 222 parts by mass of 1,6-hexanediol, 50 parts by mass of trimethylolpropane, 441 parts by mass of isophthalic acid, 132 parts by mass of adipic acid and 26 parts by mass of xylene is mixed, the temperature is gradually raised to 230 ° C. in a nitrogen stream, and while distilling off the generated water, the esterification amount reaches 126 parts by mass and the reaction product has a predetermined viscosity. The esterification reaction was carried out (step a1-1). Then, after lowering the temperature of the reaction vessel to 50 ° C., 90 parts by mass of xylene, 379 parts by mass of T-SOL150 and 87 parts by mass of propylene glycol monomethyl ether acetate were mixed (step a1-2) to form a coating resin (A). -1) (Polyester resin 1; solid content concentration: 60% by mass, number average molecular weight: 3,000, hydroxyl value: 55 mgKOH / g) was prepared.
<塗膜形成樹脂(A-2)の調製>
(工程a1-1)のモノマー組成を、ネオペンチルグリコール202質量部、1,6-ヘキサンジオール153質量部、トリメチロールプロパン66質量部及びイソフタル酸579質量部(脱水量:122質量部)に変更した以外は、前記塗膜形成樹脂(A-1)の調製方法と同様にして、塗膜形成樹脂(A-2)(ポリエステル樹脂2;固形分濃度:60質量%、数平均分子量:2,300、水酸基価:70mgKOH/g)を調製した。
<Preparation of coating film forming resin (A-2)>
The monomer composition of (step a1-1) was changed to 202 parts by mass of neopentyl glycol, 153 parts by mass of 1,6-hexanediol, 66 parts by mass of trimethylolpropane and 579 parts by mass of isophthalic acid (dehydrated amount: 122 parts by mass). The coating film forming resin (A-2) (polyester resin 2; solid content concentration: 60% by mass, number average molecular weight: 2, is the same as the preparation method of the coating film forming resin (A-1). 300, hydroxyl value: 70 mgKOH / g) was prepared.
<塗膜形成樹脂(A-3)の調製>
温度計、コンデンサー、滴下ロート及び撹拌機を備えた反応容器に、キシレン87質量部、T-SOL150 219質量部及びプロピレングリコールモノメチルエーテルアセテート292質量部を仕込み、窒素雰囲気下で130℃に昇温した。これに、スチレン300質量部、メタクリル酸メチル61質量部、メタクリル酸n-ブチル510質量部、メタクリル酸ヒドロキシエチル116質量部及びアクリル酸13質量部からなるモノマー溶液と、開始剤としてカヤエステルO(化薬アクゾ社製、t-ブチルパーオキシ2-エチルヘキサネート)85質量部及びキシレン92質量部からなる開始剤溶液を、それぞれ滴下ロートを通じて3時間で等速滴下し、その後、反応物温度を130℃で30分間保持した。次に、カヤエステルO 10質量部及びキシレン40質量部からなる開始剤溶液を30分で等速滴下し、その後、反応物を130℃で2時間保持し、塗膜形成樹脂(A-3)(アクリル樹脂1;固形分濃度:60質量%、数平均分子量:3,500、水酸基価:45mgKOH/g)を調製した。
<Preparation of coating film forming resin (A-3)>
87 parts by mass of xylene, 219 parts by mass of T-SOL150 and 292 parts by mass of propylene glycol monomethyl ether acetate were charged in a reaction vessel equipped with a thermometer, a condenser, a dropping funnel and a stirrer, and the temperature was raised to 130 ° C. under a nitrogen atmosphere. .. To this, a monomer solution consisting of 300 parts by mass of styrene, 61 parts by mass of methyl methacrylate, 510 parts by mass of n-butyl methacrylate, 116 parts by mass of hydroxyethyl methacrylate and 13 parts by mass of acrylic acid, and kayaester O (as an initiator). A starting agent solution consisting of 85 parts by mass of t-butylperoxy2-ethylhexanate (t-butylperoxy2-ethylhexanate) manufactured by Chemical Acid Axo and 92 parts by mass of xylene was added dropwise at a constant rate over 3 hours through a dropping funnel, and then the reaction temperature was adjusted. It was held at 130 ° C. for 30 minutes. Next, an initiator solution consisting of 10 parts by mass of kaya ester O and 40 parts by mass of xylene was added dropwise at a constant velocity in 30 minutes, and then the reaction product was held at 130 ° C. for 2 hours to form a coating resin (A-3). (Acrylic resin 1; solid content concentration: 60% by mass, number average molecular weight: 3,500, hydroxyl value: 45 mgKOH / g) was prepared.
<塗膜形成樹脂(A-4)の調製>
モノマー組成を、スチレン200質量部、メタクリル酸メチル382質量部、アクリル酸n-ブチル282質量部、メタクリル酸ヒドロキシエチル127質量部及びアクリル酸9質量部に変更した以外は、前記塗膜形成樹脂(A-3)の調製方法と同様にして、塗膜形成樹脂(A-4)(アクリル樹脂2;固形分濃度:60質量%、数平均分子量:3,600、水酸基価:50mgKOH/g)を調製した。
<Preparation of coating film forming resin (A-4)>
The coating film-forming resin (except that the monomer composition was changed to 200 parts by mass of styrene, 382 parts by mass of methyl methacrylate, 282 parts by mass of n-butyl acrylate, 127 parts by mass of hydroxyethyl methacrylate and 9 parts by mass of acrylic acid. In the same manner as in the preparation method of A-3), a coating film-forming resin (A-4) (acrylic resin 2; solid content concentration: 60% by mass, number average molecular weight: 3,600, hydroxyl value: 50 mgKOH / g) was used. Prepared.
<塗膜形成樹脂(A-5)の調製>
温度計、コンデンサー及び撹拌機を備えた反応容器に、ネオペンチルグリコール368質量部、1,6-ヘキサンジオール118質量部、イソフタル酸464質量部、アジピン酸51質量部及びキシレン71質量部を混合し、窒素気流中で230℃にまで徐々に昇温し、生成する水を留去しながら、脱水量が113質量部に達し、反応物が所定の粘度になるまでエステル化反応を行った(工程a5-1)。その後、反応容器の温度を50℃に下げた後、ヘキサメチレンジイソシアネート117質量部、ジブチルチンジラウレート0.5質量部、キシレン456質量部及びシクロヘキサノン527質量部を混合し、110℃で反応させた。IR(島津フーリエ変換赤外分光光度計FTIR―8400S:島津製作所社製)でイソシアネート基に由来するピークが消失するまで反応を継続し(工程a5-2)、塗膜形成樹脂(A-5)(ポリウレタン樹脂1;固形分濃度:50質量%、数平均分子量:2,700、水酸基価:42mgKOH/g)を調製した。
<Preparation of coating film forming resin (A-5)>
In a reaction vessel equipped with a thermometer, a condenser and a stirrer, 368 parts by mass of neopentyl glycol, 118 parts by mass of 1,6-hexanediol, 464 parts by mass of isophthalic acid, 51 parts by mass of adipic acid and 71 parts by mass of xylene are mixed. The esterification reaction was carried out until the dehydration amount reached 113 parts by mass and the reaction product had a predetermined viscosity while gradually raising the temperature to 230 ° C. in a nitrogen stream and distilling off the generated water (step). a5-1). Then, after lowering the temperature of the reaction vessel to 50 ° C., 117 parts by mass of hexamethylene diisocyanate, 0.5 part by mass of dibutyltin dilaurate, 456 parts by mass of xylene and 527 parts by mass of cyclohexanone were mixed and reacted at 110 ° C. The reaction was continued until the peak derived from the isocyanate group disappeared in IR (Shimadzu Fourier transform infrared spectrophotometer FTIR-8400S: manufactured by Shimadzu Corporation) (step a5-2), and the coating film forming resin (A-5) was used. (Polyurethane resin 1; solid content concentration: 50% by mass, number average molecular weight: 2,700, hydroxyl value: 42 mgKOH / g) was prepared.
<塗膜形成樹脂(A-6)の調製>
(工程a5-1)のモノマー組成を、ネオペンチルグリコール314質量部、1,6-ヘキサンジオール193質量部及びイソフタル酸493質量部(脱水量:107質量部)に、(工程a5-2)に加えた組成を、ヘキサメチレンジイソシアネート236質量部、ジブチルチンジラウレート0.5質量部、キシレン494質量部及びシクロヘキサノン565質量部に変更した以外は、前記塗膜形成樹脂(A-5)の調製方法と同様にして、塗膜形成樹脂(A-6)(ポリウレタン樹脂2;固形分濃度:50質量%、数平均分子量:4,400、水酸基価:27mgKOH/g)を調製した。
<Preparation of coating film forming resin (A-6)>
The monomer composition of (step a5-1) was added to 314 parts by mass of neopentyl glycol, 193 parts by mass of 1,6-hexanediol and 493 parts by mass of isophthalic acid (dehydrated amount: 107 parts by mass), and to (step a5-2). Except for changing the added composition to 236 parts by mass of hexamethylene diisocyanate, 0.5 parts by mass of dibutyltin dilaurate, 494 parts by mass of xylene and 565 parts by mass of cyclohexanone, the same as the method for preparing the coating film forming resin (A-5). Similarly, a coating film-forming resin (A-6) (polyurethane resin 2; solid content concentration: 50% by mass, number average molecular weight: 4,400, hydroxyl value: 27 mgKOH / g) was prepared.
(実施例1)
[塗料組成物1の調製]
塗膜形成樹脂(A-1)83.4質量部、溶剤としてT-SOL 150/ソルフィット=1/1(質量比)の混合溶液 9.2質量部、着色顔料としていてブラック6350 50.1質量部をディスパーで撹拌、混合し、混合物を得た。
次に、卓上式SGミル1500W型分散機(大平システム社製)に、得られた混合物全量とガラスビーズ100質量部(顔料分散塗料の合計質量と同量(又は1.5倍に相当する量)を入れ、ブラック6350の粒子径が10μm以下となるまで顔料分散を実施し、顔料分散塗料を調製した。
更に、この顔料分散塗料142.7質量部に対して、架橋剤(B-1)15.0質量部、スルホン酸(C-1)2.4質量部、アミン化合物(D-1)4.0質量部、骨材(E-1)5.0質量部及び表面調整剤としてディスパロンOX-70 1.12質量部を、ディスパーで撹拌、混合し、塗料組成物を得た。なお、アミン化合物(D-1)は、スルホン酸(C-1)の中和率が540%となるように加えた。
得られた塗料組成物を、フォードカップNo.4で100秒(25℃)となるようT-SOL 150/シクロヘキサノン=1/1の混合溶液を用いて希釈し、塗料組成物1を得た。
(Example 1)
[Preparation of paint composition 1]
83.4 parts by mass of coating film forming resin (A-1), 9.2 parts by mass of mixed solution of T-SOL 150 / Solfit = 1/1 (mass ratio) as solvent, black 6350 50.1 as coloring pigment The parts by mass were stirred and mixed with a disper to obtain a mixture.
Next, in a desktop SG mill 1500W type disperser (manufactured by Ohira System Co., Ltd.), the total amount of the obtained mixture and 100 parts by mass of glass beads (the same amount as the total mass of the pigment dispersion paint (or the amount corresponding to 1.5 times)). ) Was added, and pigment dispersion was carried out until the particle size of Black 6350 became 10 μm or less to prepare a pigment-dispersed paint.
Further, with respect to 142.7 parts by mass of this pigment dispersion coating material, 15.0 parts by mass of the cross-linking agent (B-1), 2.4 parts by mass of the sulfonic acid (C-1), and the amine compound (D-1) 4. 0 parts by mass, 5.0 parts by mass of aggregate (E-1) and 1.12 parts by mass of Disparon OX-70 as a surface conditioner were stirred and mixed with a disper to obtain a coating composition. The amine compound (D-1) was added so that the neutralization rate of the sulfonic acid (C-1) was 540%.
The obtained paint composition was subjected to Ford Cup No. Diluting with a mixed solution of T-SOL 150 / cyclohexanone = 1/1 so as to be 100 seconds (25 ° C.) at 4 was obtained to obtain a coating composition 1.
[塗装鋼板の製造]
厚さ0.4mmの溶融亜鉛めっき鋼板をアルカリ脱脂した後、リン酸処理剤サーフコートEC2310(日本ペイント・サーフケミカルズ社製)を、鋼板表面及び裏面に塗布することにより化成処理を施し、乾燥した。
次に、得られた鋼板の裏面に、裏面下塗り塗料として、スーパーラックR-90(日本ペイント・インダストリアルコーティングス社製、エポキシ樹脂系塗料)を、乾燥膜厚が5μmとなるようにバーコーターを用いて塗装し、素材到達最高温度230℃となる条件で60秒間焼付けを行い、裏面塗膜を形成した。
下塗り塗料として、フレキコート612WWヨウプライマー(日本ペイント・インダストリアルコーティングス社製、ポリエステル樹脂系プライマー)を、乾燥膜厚が5μmになるようにバーコーターを用いて塗装し、素材到達最高温度215℃となる条件で25秒間焼付けを行い、下塗り塗膜を形成した。
その後、上記で得られた塗料組成物1を、乾燥塗膜が22μmとなるようにバーコーターを用いて塗装し、素材最高到達温度220℃となる条件で25秒間焼付けを行い、表面上塗り塗膜を形成し、塗装鋼板を得た。得られた塗膜の明度(L*値)は23.4であった。
[Manufacturing of painted steel sheets]
After alkaline degreasing a hot-dip galvanized steel sheet with a thickness of 0.4 mm, a phosphoric acid treatment agent Surfcoat EC2310 (manufactured by Nippon Paint Surf Chemicals Co., Ltd.) was applied to the front and back surfaces of the steel sheet for chemical conversion treatment and dried. ..
Next, on the back surface of the obtained steel sheet, Super Rack R-90 (epoxy resin paint manufactured by Nippon Paint Industrial Coatings Co., Ltd.) was applied as a back surface undercoat paint, and a bar coater was applied so that the dry film thickness was 5 μm. It was painted using and baked for 60 seconds under the condition that the maximum temperature reached by the material was 230 ° C. to form a back surface coating film.
As an undercoat paint, a flexible coat 612WW iodine primer (polyester resin primer manufactured by Nippon Paint Industrial Coatings Co., Ltd.) was applied using a bar coater so that the dry film thickness was 5 μm, and the maximum temperature reached by the material was 215 ° C. Baking was performed for 25 seconds under the above conditions to form an undercoat coating film.
Then, the coating composition 1 obtained above is coated with a bar coater so that the dry coating film has a thickness of 22 μm, and baked for 25 seconds under the condition that the maximum temperature of the material reaches 220 ° C., and the surface top coating film is applied. Was formed, and a painted steel plate was obtained. The brightness (L * value) of the obtained coating film was 23.4.
(実施例2~30、比較例1~8)
各成分の種類及び量を、表1A~1Hに記載のように変更した以外は、実施例1と同様にして塗料組成物2~30及び塗料組成物34~41を調製した。得られた塗料組成物を用いて、実施例1の塗装鋼板の製造と同様に、塗装鋼板を形成した。得られた塗膜の明度(L*値)は、いずれも22.5~24.9の範囲(濃彩色)であった。
(Examples 2 to 30, Comparative Examples 1 to 8)
The paint compositions 2 to 30 and the paint compositions 34 to 41 were prepared in the same manner as in Example 1 except that the types and amounts of each component were changed as shown in Tables 1A to 1H. Using the obtained coating composition, a coated steel sheet was formed in the same manner as in the production of the coated steel sheet of Example 1. The brightness (L * value) of the obtained coating films was in the range of 22.5 to 24.9 (dark color).
(実施例31)
顔料種及び量を、ブラック6350 1.2質量部、タイペーク CR-97 1.6質量部、TAROX 合成酸化鉄 HY-100 42.7質量部、TODA COLOR KN-V 1.5質量部に変更した以外は、実施例1と同様にして、塗料組成物31を調整した。得られた塗料組成物31を用いて、実施例1の塗装鋼板の製造と同様に、塗装鋼板を形成した。得られた塗膜の明度(L*値)は51.6(中彩色)であった。
(Example 31)
The pigment type and amount were changed to 1.2 parts by mass of black 6350, 1.6 parts by mass of type CR-97, 42.7 parts by mass of TAROX synthetic iron oxide HY-100, and 1.5 parts by mass of TODA COLOR KN-V. Except for the above, the coating composition 31 was prepared in the same manner as in Example 1. Using the obtained coating composition 31, a coated steel sheet was formed in the same manner as in the production of the coated steel sheet of Example 1. The brightness (L * value) of the obtained coating film was 51.6 (medium coloring).
(実施例32)
顔料種及び量を、COLOR BLACK FW200 BEADS 18.6質量部、タイペーク CR-97 10.4質量部、TODA COLOR KN-V 2.6質量部、LIONOL BLUE SPG-8 6.3質量部に変更した以外は、実施例1と同様にして、塗料組成物32を調整した。得られた塗料組成物32を用いて、実施例1の塗装鋼板の製造と同様に、塗装鋼板を形成した。得られた塗膜の明度(L*値)は18.2(濃彩色)であった。
(Example 32)
The pigment type and amount were changed to 18.6 parts by mass of COLOR BLACK FW200 BEADS, 10.4 parts by mass of Typake CR-97, 2.6 parts by mass of TODA COLOR KN-V, and 6.3 parts by mass of LIONOL BLUE SPG-8. Except for the above, the coating composition 32 was prepared in the same manner as in Example 1. Using the obtained coating composition 32, a coated steel sheet was formed in the same manner as in the production of the coated steel sheet of Example 1. The brightness (L * value) of the obtained coating film was 18.2 (deep color).
(実施例33)
顔料種及び量を、ブラック6350 19.7質量部、タイペーク CR-97 70.3質量部、TAROX 合成酸化鉄 HY-100 4.6質量部、TODA COLOR KN-V 0.1質量部に変更した以外は、実施例1と同様にして、塗料組成物33を調整した。得られた塗料組成物33を用いて、実施例1の塗装鋼板の製造と同様に、塗装鋼板を形成した。得られた塗膜の明度(L*値)は54.7(中彩色)であった。
(Example 33)
The pigment type and amount were changed to 19.7 parts by mass of black 6350, 70.3 parts by mass of typake CR-97, 4.6 parts by mass of TAROX synthetic iron oxide HY-100, and 0.1 parts by mass of TODA COLOR KN-V. Except for the above, the coating composition 33 was prepared in the same manner as in Example 1. Using the obtained coating composition 33, a coated steel sheet was formed in the same manner as in the production of the coated steel sheet of Example 1. The brightness (L * value) of the obtained coating film was 54.7 (medium coloring).
実施例、比較例に用いた下記表中に示される各成分は下記のとおりである。
[架橋剤(B)]
(B-1)サイメル303(オルネクス・ジャパン社製)、メチル化メラミン樹脂;固形分濃度:100質量%
(B-2)スーパーベッカミン L-155-70(DIC社製)、ブチル化メラミン樹脂;固形分濃度:70質量%
(B-3)アミディア G-1850(DIC社製)、尿素樹脂;固形分濃度:60質量%
[スルホン酸(C)]
(C-1)ドデシルベンゼンスルホン酸(花王ケミカル社製)
(C-2)パラトルエンスルホン酸(江南化工社製)
[中和アミン(D)]
(D-1)トリエチルアミン、3級アミン;沸点:90℃
(D-2)ジイソプロピルアミン、2級アミン;沸点:84℃
(D-3)ジエタノールアミン、2級アミン;沸点:268℃
[骨材(E)]
(E-1)ニップシール E-200A(東ソー・シリカ社製)、シリカ微粒子;平均粒子径:3μm
(E―2)ニップジェル AZ-6A0(東ソー・シリカ社製)、シリカ微粒子;平均粒子径:6μm
(E-3)GASIL HP270(PQコーポレーション社製)、シリカ微粒子;平均粒子径:9μm
(E-4)GASIL HP395(PQコーポレーション社製)、シリカ微粒子;平均粒子径:14μm
(E-5)ガンツパール GM-0801(アイカ工業社製)、アクリル樹脂微粒子;平均粒子径:8μm
(E-6)パーゴパックM4(ロンザ・ジャパン社製)、尿素樹脂粒子;粒子径:4μm
(E-7)ガンツパール GM-2801(アイカ工業社製)、アクリル樹脂微粒子;平均粒子径:28μm
[その他]
表面調整剤:
・ディスパロンOX-70(楠本化成社製)、アクリル系表面調整剤;固形分濃度:30質量%
顔料:
・ブラック6350(アサヒ化成工業社製)、クロム鉄酸化物
・COLOR BLACK FW200 BEADS(オリオン・エンジニアドカーボンズ社製)、カーボンブラック
・タイペーク CR-97(石原産業社製)、二酸化チタン
・TAROX 合成酸化鉄 HY-100(チタン工業社製)、黄酸化鉄
・TODA COLOR KN-V(戸田ピグメント社製)、酸化第二鉄
・LIONOL BLUE SPG-8(トーヨーカラー社製)、銅フタロシアニン
溶剤:
・T-SOL 150(JXTGエネルギー社製)、芳香族系溶剤
・ソルフィット(クラレ社製)、アルコール系溶剤
・シクロヘキサノン(昭栄化学工業社製)、ケトン系溶剤
The components shown in the table below used in Examples and Comparative Examples are as follows.
[Crosslinking agent (B)]
(B-1) Cymel 303 (manufactured by Ornex Japan), methylated melamine resin; solid content concentration: 100% by mass
(B-2) Super Beccamin L-155-70 (manufactured by DIC Corporation), butylated melamine resin; solid content concentration: 70% by mass
(B-3) Amidia G-1850 (manufactured by DIC), urea resin; solid content concentration: 60% by mass
[Sulfonic acid (C)]
(C-1) Dodecylbenzene sulfonic acid (manufactured by Kao Chemical Co., Ltd.)
(C-2) P-toluenesulfonic acid (manufactured by Gangnam Kako Co., Ltd.)
[Neutralizing amine (D)]
(D-1) Triethylamine, tertiary amine; boiling point: 90 ° C.
(D-2) Diisopropylamine, secondary amine; boiling point: 84 ° C.
(D-3) Diethanolamine, secondary amine; boiling point: 268 ° C.
[Aggregate (E)]
(E-1) Nip seal E-200A (manufactured by Tosoh Silica), silica fine particles; average particle size: 3 μm
(E-2) Nip gel AZ-6A0 (manufactured by Tosoh Silica), silica fine particles; average particle size: 6 μm
(E-3) GAIR HP270 (manufactured by PQ Corporation), silica fine particles; average particle size: 9 μm
(E-4) GAIR HP395 (manufactured by PQ Corporation), silica fine particles; average particle size: 14 μm
(E-5) Ganzpearl GM-0801 (manufactured by Aica Kogyo Co., Ltd.), acrylic resin fine particles; average particle size: 8 μm
(E-6) Pergopack M4 (manufactured by Lonza Japan), urea resin particles; particle size: 4 μm
(E-7) Ganzpearl GM-2801 (manufactured by Aica Kogyo Co., Ltd.), acrylic resin fine particles; average particle size: 28 μm
[others]
Surface conditioner:
・ Disparon OX-70 (manufactured by Kusumoto Kasei Co., Ltd.), acrylic surface conditioner; solid content concentration: 30% by mass
Pigment:
・ Black 6350 (manufactured by Asahi Kasei Kogyo Co., Ltd.), Chromium iron oxide ・ COLOR BLACK FW200 BEADS (manufactured by Orion Engineered Carbons), Carbon Black Typake CR-97 (manufactured by Ishihara Sangyo Co., Ltd.), Titanium dioxide ・ TAROX synthesis Iron oxide HY-100 (manufactured by Titanium Industry Co., Ltd.), yellow iron oxide / TODA COLOR KN-V (manufactured by Toda Pigment Co., Ltd.), ferric oxide / LIONOL BLUE SPG-8 (manufactured by Toyo Color Co., Ltd.), copper phthalocyanine solvent:
-T-SOL 150 (manufactured by JXTG Energy Co., Ltd.), aromatic solvent-Solfit (manufactured by Kuraray), alcohol-based solvent-cyclohexanone (manufactured by Shoei Chemical Industry Co., Ltd.), ketone solvent
[評価項目]
表の評価結果は、以下のように評価したものである。
[Evaluation item]
The evaluation results in the table are evaluated as follows.
1)算術平均高さ(Ra)
実施例及び比較例で得られた塗膜表面の算術平均高さ(Ra)は、表面粗さ測定機HANDYSURF E-35B(東京精密社製)を用いて、JIS B 0601-2001に準拠して測定した。
1) Arithmetic mean height (Ra)
The arithmetic mean height (Ra) of the coating film surface obtained in Examples and Comparative Examples is based on JIS B 0601-2001 using a surface roughness measuring machine HANDYSURF E-35B (manufactured by Tokyo Seimitsu Co., Ltd.). It was measured.
2)展開面積比(Sdr)
実施例及び比較例で得られた塗膜表面の展開面積比(Sdr)は、レーザー顕微鏡OPTELICS HYBRID C3(レーザーテック社製、拡大倍率:50倍)を用いて、ISO 25178に準拠して測定した。
2) Expanded area ratio (Sdr)
The developed area ratio (Sdr) of the coating film surface obtained in Examples and Comparative Examples was measured using a laser microscope OPTELICS HYBRID C3 (manufactured by Lasertec, magnification: 50 times) in accordance with ISO 25178.
3)塗膜外観
実施例及び比較例で得られた塗膜の外観を目視により観察し、塗膜の艶消し外観の程度を、下記基準に従って評価した。
◎ :塗膜全体が均一でかつ明瞭に艶消し外観が形成されている。
○ :艶消し外観が形成されているが、ごく一部分が不均一及び/又は不明瞭である。
△ :艶消し外観が形成されているが、部分的に不均一及び/又は不明瞭である。
× :艶消し外観が形成されているが、著しく不均一及び/又は不明瞭である。
××:艶消し外観が形成されていない。
3) Appearance of coating film The appearance of the coating film obtained in Examples and Comparative Examples was visually observed, and the degree of matte appearance of the coating film was evaluated according to the following criteria.
⊚: The entire coating film has a uniform and clearly matte appearance.
◯: A matte appearance is formed, but a small part is uneven and / or unclear.
Δ: A matte appearance is formed, but is partially non-uniform and / or unclear.
X: A matte appearance is formed, but is significantly non-uniform and / or unclear.
XX: No matte appearance is formed.
4)光沢度
実施例及び比較例で得られた塗膜の60°光沢度を、光沢計VG 7000(日本電色工業社製)を用い、JIS K 5600-4-7(鏡面光沢度)に準拠して測定した。光沢度は、下記基準に従って評価した。
◎:光沢度が1.0以下
〇:光沢度が1.0を超え1.5以下
△:光沢度が1.5を超え2.5以下
×:光沢度が2.5を超える
4) Glossiness The 60 ° glossiness of the coating film obtained in Examples and Comparative Examples was measured to JIS K 5600-4-7 (mirror glossiness) using a gloss meter VG 7000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.). Measured in compliance. The glossiness was evaluated according to the following criteria.
⊚: Glossiness is 1.0 or less 〇: Glossiness is more than 1.0 and 1.5 or less Δ: Glossiness is more than 1.5 and 2.5 or less ×: Glossiness is more than 2.5
5)促進耐候性
実施例及び比較例で得られた塗装鋼板を、JIS B 7753に規定するサンシャインカーボンアーク灯式促進耐候性試験機であるサンシャインウェザーメーターS80(スガ試験機社製)を使用し、2,000時間及び5,000時間の促進耐候性試験を行った。運転条件は、以下のとおりである。
放射照度:255W/m2
ブラックパネル温度:63℃
水噴射時間:120分中18分
促進耐候性試験後の各塗装鋼板の外観について、色差計SM-T45(スガ試験機社製)を用いて評価を行った。評価基準は次のとおりであり、〇以上を合格とした。
◎ :色差(ΔE)が1.0以下
〇 :ΔEが1.0を超え2.0以下
× :ΔEが2.0を超え5.0以下
××:ΔEが5.0を超える
5) Accelerated weathering resistance For the coated steel sheets obtained in Examples and Comparative Examples, use Sunshine Weather Meter S80 (manufactured by Suga Test Instruments Co., Ltd.), which is a sunshine carbon arc lamp type accelerated weathering resistance tester specified in JIS B 7753. , 2,000 hours and 5,000 hours of accelerated weathering tests were performed. The operating conditions are as follows.
Irradiance: 255 W / m 2
Black panel temperature: 63 ° C
Water injection time: 18 minutes out of 120 minutes The appearance of each coated steel sheet after the accelerated weather resistance test was evaluated using a color difference meter SM-T45 (manufactured by Suga Test Instruments Co., Ltd.). The evaluation criteria are as follows, and 〇 or higher was regarded as acceptable.
⊚: Color difference (ΔE) is 1.0 or less 〇: ΔE is more than 1.0 and 2.0 or less ×: ΔE is more than 2.0 and 5.0 or less × ×: ΔE is more than 5.0
実施例1~33に示すように、形成された塗膜のRa及びSdrの値が特定の範囲内に含まれる場合、形成された塗膜は低光沢で均一な艶消し外観となり、かつ、促進耐候性試験において変退色の小さい良好な耐候性を有することが確認された。
一方で、比較例1~8の塗料組成物に示すように、形成された塗膜のRa及び/又はSdrが特定の範囲から外れる場合には、形成された塗膜が低光沢及び/又は均一な艶消し外観とならない、或いは、促進耐候性試験において変退色が大きく耐候性の劣る結果となった。
As shown in Examples 1 to 33, when the Ra and Sdr values of the formed coating film are included in a specific range, the formed coating film has a low gloss and a uniform matte appearance and is promoted. It was confirmed in the weather resistance test that it had good weather resistance with little discoloration and fading.
On the other hand, as shown in the coating compositions of Comparative Examples 1 to 8, when Ra and / or Sdr of the formed coating film is out of a specific range, the formed coating film has low gloss and / or uniform. The result was that the appearance was not matte, or the discoloration and fading were large in the accelerated weather resistance test, and the weather resistance was inferior.
本開示の塗料組成物によれば、低光沢、かつ、高耐候性を有する塗膜を形成できる。また、低光沢であることから意匠性に優れ、均一性が高く白ボケの少ない艶消し外観を有する塗膜を形成することができる。 According to the coating composition of the present disclosure, it is possible to form a coating film having low gloss and high weather resistance. Further, since it has low gloss, it is possible to form a coating film having excellent designability, high uniformity, and a matte appearance with less white blur.
Claims (13)
該塗料組成物を硬化させた塗膜の表面における、算術平均高さ(Ra)が1.2μm以上であり、かつ展開面積比(Sdr)が800%以上
であることを特徴とする塗料組成物。 A coating composition containing at least a coating film-forming resin (A) and a cross-linking agent (B).
A coating composition having an arithmetic mean height (Ra) of 1.2 μm or more and a developed area ratio (Sdr) of 800% or more on the surface of a coating film obtained by curing the coating composition. ..
シリカ粒子の粒子径は、1μm以上20μm以下である、請求項2~9のいずれか1項に記載の塗料組成物。 The aggregate (E) contains at least one selected from the group consisting of acrylic resin particles, urea resin particles and silica particles.
The coating composition according to any one of claims 2 to 9, wherein the silica particles have a particle size of 1 μm or more and 20 μm or less.
前記塗膜は、少なくとも塗膜形成樹脂(A)と、架橋剤(B)とを含む塗料組成物より形成され、
前記塗膜の表面における、算術平均高さ(Ra)が1.2μm以上であり、かつ展開面積比(Sdr)が800%以上、
であることを特徴とする塗装鋼板。 A coated steel sheet having a coating film on the surface of a steel sheet and at least one of the steel sheets.
The coating film is formed of a coating composition containing at least a coating film forming resin (A) and a cross-linking agent (B).
The arithmetic mean height (Ra) on the surface of the coating film is 1.2 μm or more, and the developed area ratio (Sdr) is 800% or more.
A painted steel sheet characterized by being.
前記塗膜は、請求項1~10のいずれか1項に記載の塗料組成物より形成され、
前記塗膜の表面における、算術平均高さ(Ra)が1.2μm以上であり、かつ展開面積比(Sdr)が800%以上、
であることを特徴とする塗装鋼板。 A coated steel sheet having a coating film on the surface of a steel sheet and at least one of the steel sheets.
The coating film is formed from the coating composition according to any one of claims 1 to 10.
The arithmetic mean height (Ra) on the surface of the coating film is 1.2 μm or more, and the developed area ratio (Sdr) is 800% or more.
A painted steel sheet characterized by being.
塗装後の塗料組成物を150℃以上270℃以下の温度で乾燥及び/又は硬化させることを含む、
塗膜の製造方法。 A coating step of applying the coating composition according to any one of claims 1 to 10 to an object to be coated, and drying and / or curing the coating composition after coating at a temperature of 150 ° C. or higher and 270 ° C. or lower. Including that
A method for manufacturing a coating film.
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