JP4477483B2 - Curable resin composition, clear coating composition and method for forming multilayer coating film using the same - Google Patents
Curable resin composition, clear coating composition and method for forming multilayer coating film using the same Download PDFInfo
- Publication number
- JP4477483B2 JP4477483B2 JP2004370982A JP2004370982A JP4477483B2 JP 4477483 B2 JP4477483 B2 JP 4477483B2 JP 2004370982 A JP2004370982 A JP 2004370982A JP 2004370982 A JP2004370982 A JP 2004370982A JP 4477483 B2 JP4477483 B2 JP 4477483B2
- Authority
- JP
- Japan
- Prior art keywords
- coating film
- isocyanate compound
- hydroxyl group
- containing acrylic
- acrylic resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000576 coating method Methods 0.000 title claims description 90
- 239000011248 coating agent Substances 0.000 title claims description 88
- 239000008199 coating composition Substances 0.000 title claims description 39
- 239000011342 resin composition Substances 0.000 title claims description 35
- 238000000034 method Methods 0.000 title claims description 32
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 64
- -1 isocyanate compound Chemical class 0.000 claims description 61
- 239000012948 isocyanate Substances 0.000 claims description 49
- 229920000178 Acrylic resin Polymers 0.000 claims description 46
- 239000004925 Acrylic resin Substances 0.000 claims description 46
- 239000007787 solid Substances 0.000 claims description 20
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 6
- 239000000178 monomer Substances 0.000 description 39
- 239000002253 acid Substances 0.000 description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- 238000001723 curing Methods 0.000 description 20
- 150000002596 lactones Chemical class 0.000 description 14
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 229920000877 Melamine resin Polymers 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 8
- 239000003973 paint Substances 0.000 description 8
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 238000004070 electrodeposition Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- 229920006243 acrylic copolymer Polymers 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000013007 heat curing Methods 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 2
- IZSHZLKNFQAAKX-UHFFFAOYSA-N 5-cyclopenta-2,4-dien-1-ylcyclopenta-1,3-diene Chemical group C1=CC=CC1C1C=CC=C1 IZSHZLKNFQAAKX-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 2
- 150000007970 thio esters Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- KQALJCGUCSYRMJ-UHFFFAOYSA-N 1,3,5-triethyl-2,4-bis(isocyanatomethyl)benzene Chemical compound CCC1=CC(CC)=C(CN=C=O)C(CC)=C1CN=C=O KQALJCGUCSYRMJ-UHFFFAOYSA-N 0.000 description 1
- IKYNWXNXXHWHLL-UHFFFAOYSA-N 1,3-diisocyanatopropane Chemical compound O=C=NCCCN=C=O IKYNWXNXXHWHLL-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- PEZADNNPJUXPTA-UHFFFAOYSA-N 1,5-bis(isocyanatomethyl)-2,4-dimethylbenzene Chemical compound CC1=CC(C)=C(CN=C=O)C=C1CN=C=O PEZADNNPJUXPTA-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- ZFULLBHCELUWST-UHFFFAOYSA-N 1-isocyanato-4-(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=C(N=C=O)C=C1 ZFULLBHCELUWST-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- JOWZLGXQYYCMSK-UHFFFAOYSA-N 2,4-bis(isocyanatomethyl)-1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=C(CN=C=O)C(C)=C1CN=C=O JOWZLGXQYYCMSK-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- ULKFLOVGORAZDI-UHFFFAOYSA-N 3,3-dimethyloxetan-2-one Chemical compound CC1(C)COC1=O ULKFLOVGORAZDI-UHFFFAOYSA-N 0.000 description 1
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical group OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- OQSSNGKVNWXYOE-UHFFFAOYSA-N N=C=O.N=C=O.CCC(C)CC(C)(C)C Chemical compound N=C=O.N=C=O.CCC(C)CC(C)(C)C OQSSNGKVNWXYOE-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
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- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
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- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
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- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
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- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
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- 230000000379 polymerizing effect Effects 0.000 description 1
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- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、硬化性樹脂組成物、それをバインダーとするクリヤー塗料組成物、並びにそのクリヤー塗料組成物を用いた複層塗膜の形成方法に関する。 The present invention relates to a curable resin composition, a clear coating composition using the same as a binder, and a method for forming a multilayer coating film using the clear coating composition.
自動車用の上塗り塗料に用いられるバインダーとしては、水酸基含有重合体とメラミン重合体硬化剤とを組み合わせて用いることが一般的であった。しかしながら、このようなメラミン重合体を硬化剤として用いることにより得られる硬化塗膜は、一般に耐酸性に劣り、近年問題となっている酸性雨により特に劣化され易く、外観上の不具合を生じるという問題を有していた。このようにメラミン重合体を硬化剤として用いることにより得られる塗膜が耐酸性に劣るのはメラミン重合体中のトリアジン環に起因するので、メラミン重合体を硬化剤として用いる限り耐酸性に劣る欠点は解消されなかった。 As a binder used in a top coating for automobiles, it is common to use a combination of a hydroxyl group-containing polymer and a melamine polymer curing agent. However, the cured coating film obtained by using such a melamine polymer as a curing agent is generally inferior in acid resistance, and is particularly easily deteriorated by acid rain which has become a problem in recent years, resulting in problems in appearance. Had. Since the coating film obtained by using melamine polymer as a curing agent in this way is inferior in acid resistance due to the triazine ring in the melamine polymer, the disadvantage is inferior in acid resistance as long as melamine polymer is used as a curing agent. Was not resolved.
このような欠点を解決するために、特開平２−４５５７７号公報（特許公報１）及び特開平３−２８７６５０号公報（特許公報２）には、メラミン重合体を使用しない塗料組成物が記載されている。このような塗料組成物は、カルボン酸基とエポキシ基とを反応させることにより生じるエステル結合を架橋点とするので、耐酸性は良好であり、自動車用上塗り塗膜として十分な耐候性も有している。 In order to solve such drawbacks, JP-A-2-45577 (Patent Publication 1) and JP-A-3-287650 (Patent Publication 2) describe coating compositions that do not use a melamine polymer. ing. Such a coating composition has an ester bond generated by reacting a carboxylic acid group and an epoxy group as a cross-linking point, and therefore has good acid resistance and sufficient weather resistance as a top coat film for automobiles. ing.
さらに、特開２００３−２５３１９１号公報（特許公報３）には、ハーフエステル酸基含有アクリル共重合体と、エポキシ基含有アクリル共重合体と、カルボキシル基含有ポリエステル重合体及びカルボキシル基含有アクリル重合体からなる群より選択される少なくとも１つのカルボキシル基含有重合体とからなり、式：−（ＣＨ２）ｎ−（式中、ｎは４以上の整数を表す）で表されるソフトセグメント部を所定量有しているクリヤー塗料組成物が記載されている。このようなクリヤー塗料組成物は、耐傷性、耐酸性及び耐溶剤性の全ての性質においてバランスの良い物性を有する塗膜を形成することができるものである。
本発明は、上記従来技術をベースとし、耐傷性（特に耐擦り傷性）と耐酸性（特に耐硫酸性）を更に向上せしめた硬化膜（例えば塗膜）を形成することが可能な硬化性樹脂組成物及びクリヤー塗料組成物、並びに耐傷性と耐酸性が非常に優れている複層塗膜を形成することが可能な方法を提供することを目的とする。 The present invention is based on the above prior art, and is a curable resin capable of forming a cured film (for example, a coating film) with further improved scratch resistance (particularly scratch resistance) and acid resistance (particularly sulfuric acid resistance). It is an object of the present invention to provide a composition and a clear coating composition, and a method capable of forming a multilayer coating film having very excellent scratch resistance and acid resistance.
本発明者らは、上記目的を達成すべく鋭意研究を重ねた結果、水酸基含有アクリル樹脂と多官能イソシアネート化合物とを含有する硬化性樹脂組成物において、後者としてイソシアヌレート型イソシアネート化合物を用い、更にソフトセグメント部の全量を所定量とすることにより上記目的が達成されることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventors have used an isocyanurate type isocyanate compound as the latter in a curable resin composition containing a hydroxyl group-containing acrylic resin and a polyfunctional isocyanate compound. The inventors have found that the above object can be achieved by setting the total amount of the soft segment portion to a predetermined amount, and have completed the present invention.
すなわち、本発明の硬化性樹脂組成物は、水酸基含有アクリル樹脂と多官能イソシアネート化合物とを含有する硬化性樹脂組成物であって、
前記多官能イソシアネート化合物の全量中における６０質量％以上がイソシアヌレート型イソシアネート化合物であり、
前記硬化性樹脂組成物は、下記一般式（１）：
−（ＣＨ２）ｎ− （１）
（式中、ｎは４〜９の整数を表す。）
で表され且つ前記硬化性樹脂組成物の主鎖中又は架橋結合鎖中に存在するソフトセグメント部を、前記水酸基含有アクリル樹脂及び多官能イソシアネート化合物の固形分全量に対して２５〜５０質量％有しており、
前記水酸基含有アクリル樹脂における前記ソフトセグメント部の含有割合は、前記水酸基含有アクリル樹脂の固形分全量に対して７〜３０質量％であり、
前記多官能イソシアネート化合物における前記ソフトセグメント部の含有割合は、前記多官能イソシアネート化合物の固形分全量に対して６０質量％以下であり、
前記水酸基含有アクリル樹脂と前記多官能イソシアネート化合物との配合割合は、前記水酸基含有アクリル樹脂中の水酸基の数１に対して前記多官能イソシアネート化合物中のイソシアネート基が０．５〜１．５の範囲内となる配合割合である、
ことを特徴とするものである。
That is, the curable resin composition of the present invention is a curable resin composition containing a hydroxyl group-containing acrylic resin and a polyfunctional isocyanate compound,
60% by mass or more in the total amount of the polyfunctional isocyanate compound is an isocyanurate type isocyanate compound,
The curable resin composition has the following general formula (1):
- (CH 2) n - ( 1)
(In the formula, n represents an integer of 4 to 9. )
And the soft segment portion present in the main chain or the cross-linked chain of the curable resin composition in an amount of 25 to 50% by mass based on the total solid content of the hydroxyl group-containing acrylic resin and polyfunctional isocyanate compound. and it is,
The content ratio of the soft segment portion in the hydroxyl group-containing acrylic resin is 7 to 30% by mass with respect to the total solid content of the hydroxyl group-containing acrylic resin,
The content ratio of the soft segment portion in the polyfunctional isocyanate compound is 60% by mass or less based on the total solid content of the polyfunctional isocyanate compound,
The mixing ratio of the hydroxyl group-containing acrylic resin and the polyfunctional isocyanate compound is such that the isocyanate group in the polyfunctional isocyanate compound is 0.5 to 1.5 with respect to the number of hydroxyl groups in the hydroxyl group-containing acrylic resin. It is the blending ratio that is inside,
It is characterized by this.
また、本発明のクリヤー塗料組成物は、前記本発明の硬化性樹脂組成物をバインダーとして含有することを特徴とするものである。 The clear coating composition of the present invention is characterized by containing the curable resin composition of the present invention as a binder.
また、本発明の複層塗膜の形成方法は、被塗装物に対してトップコートを有する複層塗膜を形成する方法であって、前記本発明のクリヤー塗料組成物を前記トップコートとして塗装することを特徴とする方法である。 The method for forming a multilayer coating film of the present invention is a method for forming a multilayer coating film having a top coat on an object to be coated, and the clear coating composition of the present invention is applied as the top coat. It is the method characterized by doing.
本発明の複層塗膜の形成方法においては、前記被塗装物にベース塗料組成物を塗布してベース未硬化塗膜を得た後、前記ベース未硬化塗膜に前記クリヤー塗料組成物を塗布してクリヤー未硬化塗膜を得、前記ベース未硬化塗膜及びクリヤー未硬化塗膜を同時に加熱して硬化させることが好ましい。 In the method for forming a multilayer coating film of the present invention, after applying a base coating composition to the object to be coated to obtain a base uncured coating film, the clear coating composition is applied to the base uncured coating film. Thus, it is preferable that a clear uncured coating film is obtained, and the base uncured coating film and the clear uncured coating film are simultaneously heated and cured.
本発明によれば、耐傷性（特に耐擦り傷性）と耐酸性（特に耐硫酸性）を更に向上せしめた硬化膜（例えば塗膜）を形成することが可能な硬化性樹脂組成物及びクリヤー塗料組成物、並びに耐傷性と耐酸性が非常に優れている複層塗膜を形成することが可能な方法を提供することが可能となる。 ADVANTAGE OF THE INVENTION According to this invention, the curable resin composition and clear coating material which can form the cured film (for example, coating film) which improved scratch resistance (especially abrasion resistance) and acid resistance (especially sulfuric acid resistance) further. It is possible to provide a composition and a method capable of forming a multilayer coating film having very excellent scratch resistance and acid resistance.
以下、本発明をその好適な実施形態に即して詳細に説明する。 Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.
先ず、本発明の硬化性樹脂組成物について説明する。すなわち、本発明の硬化性樹脂組成物は、硬化膜形成性樹脂としての水酸基含有アクリル樹脂と、硬化剤としての多官能イソシアネート化合物とを含有する硬化性樹脂組成物であって、(i)前記多官能イソシアネート化合物のうちの少なくとも一部がイソシアヌレート型イソシアネート化合物であり、(ii)前記硬化性樹脂組成物は、下記一般式（１）：
−（ＣＨ２）ｎ− （１）
（式中、ｎは４以上の整数を表す。）
で表されるソフトセグメント部を、前記水酸基含有アクリル樹脂及び多官能イソシアネート化合物の固形分全量に対して２５〜５０質量％有していることを特徴とするものである。
First, the curable resin composition of the present invention will be described. That is, the curable resin composition of the present invention is a curable resin composition containing a hydroxyl group-containing acrylic resin as a cured film-forming resin and a polyfunctional isocyanate compound as a curing agent. At least a part of the polyfunctional isocyanate compound is an isocyanurate type isocyanate compound, and (ii) the curable resin composition has the following general formula (1):
- (CH 2) n - ( 1)
(In the formula, n represents an integer of 4 or more.)
It is characterized by having 25-50 mass% with respect to the solid content whole quantity of the said hydroxyl-containing acrylic resin and a polyfunctional isocyanate compound.
上記水酸基含有アクリル樹脂と多官能イソシアネート化合物とを含有する本発明の硬化性樹脂組成物における硬化システムは、以下のようなものである。すなわち、加熱により多官能イソシアネート化合物のイソシアネート基と水酸基含有アクリル樹脂中の水酸基とが反応することにより架橋点が形成され、水酸基含有アクリル樹脂が多官能イソシアネート化合物を介して架橋されることにより硬化が進行して高い架橋密度が達成されるものである。そして、本発明の硬化性樹脂組成物を用いて膜形成後に加熱硬化して成形した硬化膜において、上記ソフトセグメント部は主鎖中又は架橋結合鎖中に存在することとなる。このように主鎖中又は架橋鎖中にソフトセグメント部が存在していることによって、硬化膜に優れた耐傷性が有効に付与されることとなる。 The curing system in the curable resin composition of the present invention containing the hydroxyl group-containing acrylic resin and the polyfunctional isocyanate compound is as follows. That is, when the isocyanate group of the polyfunctional isocyanate compound reacts with the hydroxyl group in the hydroxyl group-containing acrylic resin by heating, a crosslinking point is formed, and the hydroxyl group-containing acrylic resin is crosslinked through the polyfunctional isocyanate compound to cure. Proceeding to achieve high crosslink density. And in the cured film shape | molded by heat-curing after film | membrane formation using the curable resin composition of this invention, the said soft segment part will exist in a principal chain or a crosslinked bond chain. Thus, the presence of the soft segment portion in the main chain or the crosslinked chain effectively imparts excellent scratch resistance to the cured film.
上記一般式（１）で表されるソフトセグメント部の量は、後述する水酸基含有アクリル樹脂及び多官能イソシアネート化合物の固形分全量中に含まれるソフトセグメント部の質量の割合を表す数値である。上記一般式（１）で表されるソフトセグメント部は、一般式（１）中のｎが４以上であることが必要である。上記ｎが３以下の場合は、ソフトセグメントとしての性質を十分に有さないためである。このように上記ｎは４以上の整数を表し、４〜９であることが好ましく、４又は５であることがより好ましい。上記ｎが４〜９であるものは、前記一般式（１）で表されるソフトセグメント部を有する単量体及び重合体の製造が容易であり、取扱性にも優れる傾向にある。また、上記ｎの値が相違する２種類以上のソフトセグメント部を併用しても良い。 The amount of the soft segment portion represented by the general formula (1) is a numerical value representing the mass ratio of the soft segment portion included in the total solid content of the hydroxyl group-containing acrylic resin and polyfunctional isocyanate compound described later. The soft segment represented by the general formula (1) needs to have n in the general formula (1) of 4 or more. This is because when n is 3 or less, it does not have sufficient properties as a soft segment. As described above, n represents an integer of 4 or more, preferably 4 to 9, and more preferably 4 or 5. When n is 4 to 9, the monomer and polymer having the soft segment represented by the general formula (1) can be easily produced, and the handleability tends to be excellent. Further, two or more types of soft segment portions having different values of n may be used in combination.
本発明の硬化性樹脂組成物においては、上記割合で前記ソフトセグメント部を有することによって、硬化膜の耐傷性を高水準に維持しつつその耐酸性を更に向上せしめるという効果が奏される。硬化性樹脂組成物の固形分全量中の上記ソフトセグメント部の割合が２５質量％未満の場合は、ソフトセグメント部によって耐傷性が向上するという効果が十分に得られない。他方、上記ソフトセグメント部の割合が５０質量％を超える場合は、十分な耐酸性及び耐溶剤性が得られないという問題がある。また、上記ソフトセグメント部の割合の下限は３０質量％であることが好ましく、他方、上記ソフトセグメント部の割合の上限は４５質量％であることが好ましい。 In the curable resin composition of this invention, by having the said soft segment part in the said ratio, the effect that the acid resistance is further improved is maintained, maintaining the scratch resistance of a cured film at a high level. When the ratio of the soft segment portion in the total solid content of the curable resin composition is less than 25% by mass, the effect that the scratch resistance is improved by the soft segment portion is not sufficiently obtained. On the other hand, when the proportion of the soft segment exceeds 50% by mass, there is a problem that sufficient acid resistance and solvent resistance cannot be obtained. Moreover, it is preferable that the minimum of the ratio of the said soft segment part is 30 mass%, and on the other hand, it is preferable that the upper limit of the ratio of the said soft segment part is 45 mass%.
なお、上記ソフトセグメント部を有する水酸基含有アクリル樹脂は、その重合反応時に上記一般式（１）で表されるソフトセグメント部を有する単量体を配合することによって得ることができる。したがって、上記ソフトセグメント部の水酸基含有アクリル樹脂中の含有量は、重合するために使用した単量体組成物の配合量及び単量体中に含まれるソフトセグメント部の量に基づいて理論的に計算することによって算出することができる。また、本発明の硬化性樹脂組成物中のラクトン含有モノマー由来のソフトセグメント部の含有量は、重合するために使用したラクトン含有モノマーの配合量及びそれに含まれるソフトセグメント部の量に基づいて理論的に計算することによって算出することができる。さらに、本発明の硬化性樹脂組成物中の水酸基含有アクリル樹脂由来のソフトセグメント部の含有量並びに多官能イソシアネート化合物由来のソフトセグメント部の含有量は、それらの配合量及びそれらに含まれるソフトセグメント部の量に基づいて理論的に計算することによって算出することができる。 In addition, the hydroxyl-containing acrylic resin which has the said soft segment part can be obtained by mix | blending the monomer which has a soft segment part represented by the said General formula (1) at the time of the polymerization reaction. Therefore, the content of the soft segment portion in the hydroxyl group-containing acrylic resin is theoretically based on the blending amount of the monomer composition used for polymerization and the amount of the soft segment portion contained in the monomer. It can be calculated by calculating. Further, the content of the soft segment portion derived from the lactone-containing monomer in the curable resin composition of the present invention is theoretically based on the blending amount of the lactone-containing monomer used for polymerization and the amount of the soft segment portion contained therein. It can be calculated by calculating automatically. Furthermore, the content of the soft segment portion derived from the hydroxyl group-containing acrylic resin and the content of the soft segment portion derived from the polyfunctional isocyanate compound in the curable resin composition of the present invention are the blended amount and the soft segment contained in them. It can be calculated by calculating theoretically based on the amount of parts.
本発明の硬化性樹脂組成物において硬化膜形成性樹脂として使用する水酸基含有アクリル樹脂（水酸基含有アクリル共重合体）としては、水酸基含有エチレン性不飽和モノマーとその他のエチレン性不飽和モノマーとを共重合させて得られるものが挙げられる。本発明にかかる水酸基含有アクリル樹脂は、数平均分子量（Ｍｎ）が１０００〜１００００であることが好ましく、１１００〜８０００であることが更に好ましい。数平均分子量が前記下限未満では塗装作業性及び硬化膜との混層性が低下する傾向にあり、他方、前記上限を超えると塗装時の不揮発分が低くなり、作業性が悪くなる傾向にある。また、水酸基含有アクリル樹脂の数平均分子量が１２００〜７０００の範囲であることが、硬化膜外観の観点から特に好ましい。また、本発明にかかる水酸基含有アクリル樹脂の水酸基価は、５０〜３００ｍｇＫＯＨ／ｇであることが好ましく、７０〜２６０ｍｇＫＯＨ／ｇであることが更に好ましい。水酸基価が前記上限を超えると硬化膜にした場合に耐水性が低下する傾向にあり、他方、前記下限未満では硬化膜の硬化性が低下する傾向にある。 The hydroxyl group-containing acrylic resin (hydroxyl group-containing acrylic copolymer) used as the cured film-forming resin in the curable resin composition of the present invention includes a hydroxyl group-containing ethylenically unsaturated monomer and another ethylenically unsaturated monomer. What is obtained by polymerizing is mentioned. The hydroxyl group-containing acrylic resin according to the present invention preferably has a number average molecular weight (Mn) of 1000 to 10,000, and more preferably 1100 to 8000. When the number average molecular weight is less than the lower limit, the coating workability and the layering property with the cured film tend to be lowered. On the other hand, when the upper limit is exceeded, the non-volatile content at the time of coating is lowered and the workability tends to be deteriorated. Moreover, it is especially preferable from the viewpoint of a cured film appearance that the number average molecular weights of a hydroxyl-containing acrylic resin are the range of 1200-7000. Moreover, it is preferable that the hydroxyl value of the hydroxyl-containing acrylic resin concerning this invention is 50-300 mgKOH / g, and it is still more preferable that it is 70-260 mgKOH / g. If the hydroxyl value exceeds the above upper limit, the water resistance tends to decrease when the cured film is formed. On the other hand, if the hydroxyl value is less than the lower limit, the curability of the cured film tends to decrease.
さらに、本発明に係る水酸基含有アクリル樹脂における全ソフトセグメント部の含有割合は、その固形分全量に対して７〜３０質量％であることが好ましい。全ソフトセグメント部の含有割合が前記下限未満の場合は耐傷性が十分に向上した硬化膜を得られにくくなる傾向にあり、他方、前記上限を超える場合は十分な耐酸性を有する硬化膜を得られにくくなる傾向にある。また、本発明に係る水酸基含有アクリル樹脂においては、ラクトン部（ラクトン含有モノマーを用いた場合におけるそのラクトン部分）の含有割合が水酸基含有アクリル樹脂の固形分全量に対して２５質量％以下であることが好ましく、ラクトン含有モノマー由来のソフトセグメント部の含有割合が水酸基含有アクリル樹脂の固形分全量に対して１５質量％以下であることが好ましい。ラクトン含有モノマー由来のソフトセグメント部の含有割合が前記上限を超える場合は、十分な耐酸性を有する硬化膜が得られにくくなる傾向にある。 Furthermore, it is preferable that the content rate of all the soft segment parts in the hydroxyl-containing acrylic resin which concerns on this invention is 7-30 mass% with respect to the solid content whole quantity. When the content ratio of all the soft segment parts is less than the lower limit, it tends to be difficult to obtain a cured film having sufficiently improved scratch resistance. On the other hand, when it exceeds the upper limit, a cured film having sufficient acid resistance is obtained. There is a tendency to become difficult. In the hydroxyl group-containing acrylic resin according to the present invention, the content ratio of the lactone portion (the lactone portion when a lactone-containing monomer is used) is 25% by mass or less based on the total solid content of the hydroxyl group-containing acrylic resin. It is preferable that the content of the soft segment portion derived from the lactone-containing monomer is 15% by mass or less based on the total solid content of the hydroxyl group-containing acrylic resin. When the content ratio of the soft segment portion derived from the lactone-containing monomer exceeds the upper limit, a cured film having sufficient acid resistance tends to be hardly obtained.
本発明にかかる水酸基含有アクリル樹脂は、水酸基含有エチレン性不飽和モノマーとその他のエチレン性不飽和モノマーとを共重合させることにより得ることができるが、この共重合における配合割合は、上記アクリル樹脂を製造するのに用いるエチレン性不飽和モノマーの総量を基準にして、水酸基含有エチレン性不飽和モノマーが５〜６０質量％（より好ましくは８〜５０質量％）、その他のエチレン性不飽和モノマーが９５〜４０質量％（より好ましくは９２〜５０質量％）であることが好ましい。上記水酸基含有エチレン性不飽和モノマーの含有量が前記下限を下回ると製造安定性が低下する傾向にあり、他方、前記上限を超えると硬化膜にした場合の耐水性が低下する傾向にある。 The hydroxyl group-containing acrylic resin according to the present invention can be obtained by copolymerizing a hydroxyl group-containing ethylenically unsaturated monomer and another ethylenically unsaturated monomer. The blending ratio in this copolymerization is the above-mentioned acrylic resin. Based on the total amount of the ethylenically unsaturated monomer used for the production, the hydroxyl group-containing ethylenically unsaturated monomer is 5 to 60% by mass (more preferably 8 to 50% by mass), and the other ethylenically unsaturated monomer is 95%. It is preferable that it is -40 mass% (more preferably 92-50 mass%). If the content of the hydroxyl group-containing ethylenically unsaturated monomer is less than the lower limit, the production stability tends to be lowered. On the other hand, if the content exceeds the upper limit, the water resistance of the cured film tends to be lowered.
上記水酸基含有エチレン性不飽和モノマーとしては、具体的には、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、５−ヒドロキシペンチル（メタ）アクリレート、６−ヒドロキシヘキシル（メタ）アクリレート、７−ヒドロキシヘプチル（メタ）アクリレート、８−ヒドロキシオクチル（メタ）アクリレート、９−ヒドロキシノニル（メタ）アクリレート、アリルアルコール、メタクリルアルコール、並びにこれらとラクトン類（β−プロピオラクロン、ジメチルプロピオラクトン、ブチルラクトン、γ−バレロラクトン、ε−カプロラクトン、γ−カプロラクトン、γ−カプリロラクトン、クロトラクトン、δ−バレロラクトン、δ−カプロラクトン等）との付加物等が挙げられる。なお、このような水酸基含有エチレン性不飽和モノマーは単独でも、２種以上を混合して用いることもできる。 Specific examples of the hydroxyl group-containing ethylenically unsaturated monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 5-hydroxypentyl (meth). Acrylate, 6-hydroxyhexyl (meth) acrylate, 7-hydroxyheptyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 9-hydroxynonyl (meth) acrylate, allyl alcohol, methacryl alcohol, and lactones ( β-propiolaclone, dimethylpropiolactone, butyllactone, γ-valerolactone, ε-caprolactone, γ-caprolactone, γ-caprolactone, crotolactone, δ-valerolactone, δ-caprolacto Adducts and the like of an equal). Such hydroxyl group-containing ethylenically unsaturated monomers can be used alone or in admixture of two or more.
また、得られる硬化膜の耐傷性をより向上させるという観点から、上記水酸基含有エチレン性不飽和モノマーの少なくとも一部として前記ソフトセグメント部を有するものを用いることが好ましく、中でも耐酸性をもより向上させるという観点から、炭素数４〜９のヒドロキシアルキル基を有するヒドロキシアルキル（メタ）アクリレートを用いることが特に好ましい。すなわち、本発明にかかる水酸基含有アクリル樹脂は、少なくとも一部のモノマーとして炭素数４〜９のヒドロキシアルキル基を有するヒドロキシアルキル（メタ）アクリレートを用いて得たものであることが好ましく、入手が容易で取扱性にも優れるという観点から、４−ヒドロキシブチル（メタ）アクリレート又は６−ヒドロキシヘキシル（メタ）アクリレートを用いて得たものであることが特に好ましい。また、上記炭素数４〜９のヒドロキシアルキル基を有するヒドロキシアルキル（メタ）アクリレートの配合割合は、水酸基含有アクリル樹脂を製造するのに用いるモノマーの総量を基準にして、３０〜６０質量％であることが好ましい。上記ヒドロキシアルキル（メタ）アクリレートの配合割合が上記下限未満の場合は、得られる硬化膜の耐傷性が低下する傾向にあり、他方、上記上限を超える場合は、得られる硬化膜の耐酸性及び耐水性が低下する傾向にある。 Further, from the viewpoint of further improving the scratch resistance of the resulting cured film, it is preferable to use one having the soft segment portion as at least a part of the hydroxyl group-containing ethylenically unsaturated monomer, and in particular, the acid resistance is further improved. It is particularly preferable to use a hydroxyalkyl (meth) acrylate having a hydroxyalkyl group having 4 to 9 carbon atoms from the viewpoint of making it. That is, the hydroxyl group-containing acrylic resin according to the present invention is preferably obtained using a hydroxyalkyl (meth) acrylate having a hydroxyalkyl group having 4 to 9 carbon atoms as at least a part of the monomer, and is easily available. From the viewpoint of excellent handling properties, it is particularly preferable to use 4-hydroxybutyl (meth) acrylate or 6-hydroxyhexyl (meth) acrylate. Moreover, the mixture ratio of the said hydroxyalkyl (meth) acrylate which has a C4-C9 hydroxyalkyl group is 30-60 mass% on the basis of the total amount of the monomer used for manufacturing a hydroxyl-containing acrylic resin. It is preferable. When the blending ratio of the hydroxyalkyl (meth) acrylate is less than the above lower limit, the scratch resistance of the resulting cured film tends to be reduced. On the other hand, when it exceeds the upper limit, the acid resistance and water resistance of the cured film obtained are Tend to decrease.
また、このような水酸基含有エチレン性不飽和モノマーであって前記ソフトセグメント部を有するものとして、２−ヒドロキシエチル（メタ）アクリレートとε−カプロラクトンとの付加物を用いることも好ましい。 Moreover, it is also preferable to use an adduct of 2-hydroxyethyl (meth) acrylate and ε-caprolactone as such a hydroxyl group-containing ethylenically unsaturated monomer having the soft segment portion.
上記その他のエチレン性不飽和モノマーとしては、特に限定されるものではないが、先ず、カルボキシル基を有するエチレン性不飽和モノマーを挙げることができる。その例として、（メタ）アクリル酸誘導体｛例えば、アクリル酸、メタクリル酸、クロトン酸、イソクロトン酸、アクリル酸二量体、アクリル酸にε−カプロラクトンを付加させたα−ハイドロ−ω−（（１−オキソ−２−プロペニル）オキシ）ポリ（オキシ（１−オキソ−１，６−ヘキサンジイル））等｝；並びに不飽和二塩基酸、そのハーフエステル、ハーフアミド及びハーフチオエステル｛例えば、マレイン酸、フマル酸、イタコン酸、そのハーフエステル、ハーフアミド及びハーフチオエステル等｝が挙げられる。更に、カルボキシル基を有するもの以外のエチレン性不飽和モノマーの例としては、（メタ）アクリレートエステルモノマー｛例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、イソブチルアクリレート、ｔ−ブチルアクリレート、２−エチルヘキシル（メタ）アクリレート、ラウリルメタアクリレート、フェニルアクリレート、イソボルニル（メタ）アクリレート、シクロヘキシルメタクリレート、ｔ−ブチルシクロヘキシル（メタ）アクリレート、ジシクロペンタジエニル（メタ）アクリレート、ジヒドロジシクロペンタジエニル（メタ）アクリレート等｝、重合性芳香族化合物（例えば、スチレン、α−メチルスチレン、ビニルケトン、ｔ−ブチルスチレン、パラクロロスチレン、ビニルナフタレン等）、重合性ニトリル（例えば、アクリロニトリル、メタクリロニトリル等）、α−オレフィン（例えば、エチレン、プロピレン等）、ビニルエステル（例えば、酢酸ビニル、プロピオン酸ビニル等）、ジエン（例えば、ブタジエン、イソプレン等）、必要によりイソシアネート基含有モノマー等を挙げることができる。なお、このようなその他のエチレン性不飽和モノマーは単独でも、２種以上を混合して用いることもできる。 Although it does not specifically limit as said other ethylenically unsaturated monomer, First, the ethylenically unsaturated monomer which has a carboxyl group can be mentioned. Examples thereof include (meth) acrylic acid derivatives {e.g., acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, acrylic acid dimer, α-hydro-ω-((1 -Oxo-2-propenyl) oxy) poly (oxy (1-oxo-1,6-hexanediyl)) etc.}; and unsaturated dibasic acids, their half esters, half amides and half thioesters {eg maleic acid, Fumaric acid, itaconic acid, its half ester, half amide, half thioester, etc.}. Furthermore, examples of ethylenically unsaturated monomers other than those having a carboxyl group include (meth) acrylate ester monomers {eg, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl acrylate , T-butyl acrylate, 2-ethylhexyl (meth) acrylate, lauryl methacrylate, phenyl acrylate, isobornyl (meth) acrylate, cyclohexyl methacrylate, t-butylcyclohexyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, dihydro Dicyclopentadienyl (meth) acrylate, etc.}, polymerizable aromatic compounds (eg, styrene, α-methylstyrene, vinyl ketone, t-butylstyrene, parachlorostyrene) Vinyl naphthalene, etc.), polymerizable nitriles (eg, acrylonitrile, methacrylonitrile, etc.), α-olefins (eg, ethylene, propylene, etc.), vinyl esters (eg, vinyl acetate, vinyl propionate, etc.), dienes (eg, butadiene) , Isoprene, and the like) and, if necessary, an isocyanate group-containing monomer. Such other ethylenically unsaturated monomers can be used alone or in admixture of two or more.
上記の水酸基含有エチレン性不飽和モノマーとその他のエチレン性不飽和モノマーとを共重合させることにより本発明に好適な水酸基含有アクリル樹脂を得ることができるが、重合方法は特に制限されず、溶液ラジカル重合のような公知文献等に記載されている通常の方法を用いることができる。例えば、重合温度６０〜１６０℃で２〜１０時間かけて適当なラジカル重合開始剤とモノマー混合溶液とを適当な溶媒中へ滴下しながら撹拌する方法が挙げられる。ここで用いうるラジカル重合開始剤は、通常重合に際して使用するものであれば特に限定されず、アゾ系化合物（例えば、ジメチル−２，２´−アゾビスイソブチレート）、過酸化物（例えば、ｔ−ブチルパーオキシ−２−エチルヘキサノエート）等が挙げられる。このような開始剤の量は、不飽和モノマーの総量に対して一般に０．１〜１５質量％であり、好ましくは０．５〜１２質量％である。また、ここで用いうる溶媒は、反応に悪影響を与えないものであれば特に限定されず、例えば、ケトン、炭化水素系溶媒（例えば、プロピレングリコールモノメチルエーテルアセテート、キシレン）等が挙げられる。更に、分子量を調節するために、ラウリルメルカプタンのようなメルカプタンや、α−メチルスチレンダイマーのような連鎖移動剤を必要に応じて用いることができる。 本発明の硬化性樹脂組成物において硬化剤として使用する多官能イソシアネート化合物は、そのうちの少なくとも一部がイソシアヌレート型イソシアネート化合物（いわゆるイソシアヌレート）であることが必要である。このようなイソシアヌレート型イソシアネート化合物を用いないと、耐傷性を高水準に維持しつつ耐酸性を更に向上するという本発明の効果が達成されない。 A hydroxyl group-containing acrylic resin suitable for the present invention can be obtained by copolymerizing the above hydroxyl group-containing ethylenically unsaturated monomer with another ethylenically unsaturated monomer, but the polymerization method is not particularly limited, and the solution radical Ordinary methods described in known documents such as polymerization can be used. For example, a method of stirring while dropping a suitable radical polymerization initiator and a monomer mixed solution into a suitable solvent at a polymerization temperature of 60 to 160 ° C. over 2 to 10 hours can be mentioned. The radical polymerization initiator that can be used here is not particularly limited as long as it is usually used in polymerization, and an azo compound (for example, dimethyl-2,2′-azobisisobutyrate), a peroxide (for example, t-butylperoxy-2-ethylhexanoate) and the like. The amount of such initiator is generally 0.1 to 15% by mass, preferably 0.5 to 12% by mass, based on the total amount of unsaturated monomers. Moreover, the solvent which can be used here will not be specifically limited if it does not have a bad influence on reaction, For example, a ketone, hydrocarbon solvent (for example, propylene glycol monomethyl ether acetate, xylene) etc. are mentioned. Furthermore, in order to adjust the molecular weight, a mercaptan such as lauryl mercaptan or a chain transfer agent such as α-methylstyrene dimer can be used as necessary. The polyfunctional isocyanate compound used as a curing agent in the curable resin composition of the present invention is required to be at least partly an isocyanurate type isocyanate compound (so-called isocyanurate). If such an isocyanurate type isocyanate compound is not used, the effect of the present invention of further improving the acid resistance while maintaining the scratch resistance at a high level cannot be achieved.
このようなイソシアヌレート型イソシアネート化合物としては、一般に５〜２４、好ましくは６〜１８個の炭素原子を含んでいるジイソシアネートの三量体を挙げることができ、かかるイソシアネート化合物はいわゆるアシンメトリー型のものであってもよい。このようなイソシアヌレート型イソシアネート化合物を構成するジイソシアネートとしては、例えば、トリメチレンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート（ＨＤＩ）、２，２，４−トリメチルへキサンジイソシアネート、ウンデカンジイソシアネート−（１，１１）、リジンエステルジイソシアネート、シクロヘキサン−１，３−及び１，４−ジイソシアネート、１−イソシアナト−３−イソシアナトメチル−３，５，５−トリメチルシクロヘキサン（イソホロンジイソシアネート：ＩＰＤＩ）、４，４’−ジイソシアナトジシクロメタン、ω，ω’−ジプロピルエーテルジイソシアネート、チオジプロピルジイソシアネート、シクロヘキシル−１，４−ジイソシアネート、ジシクロヘキシルメタン−４，４’−ジイソシアネート、１，５−ジメチル−２，４−ビス（イソシアナトメチル）ベンゼン、１，５−トリメチル−２，４−ビス（ω−イソシアナトエチル）−ベンゼン、１，３，５−トリメチル−２，４−ビス（イソシアナトメチル）ベンゼン、１，３，５−トリエチル‐２，４−ビス（イソシアナトメチル）ベンゼン、ジシクロヘキシルジメチルメタン−４，４’−ジイソシアネート等が挙げられる。また、２，４−ジイソシアナトトルエン及び／又は２，６−ジイソシアナトトルエン、４，４’−ジイソシアナトジフェニルメタン、１，４−ジイソシアナトイソプロピルベンゼンのような芳香族ジイソシアネートも用いることができる。 As such an isocyanurate type isocyanate compound, a trimer of diisocyanate generally containing 5 to 24, preferably 6 to 18 carbon atoms can be mentioned. Such an isocyanate compound is a so-called asymmetric type. There may be. Examples of the diisocyanate constituting such an isocyanurate type isocyanate compound include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexane diisocyanate, undecane diisocyanate- (1,11 ), Lysine ester diisocyanate, cyclohexane-1,3- and 1,4-diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (isophorone diisocyanate: IPDI), 4,4′-di Isocyanatodicyclomethane, ω, ω'-dipropyl ether diisocyanate, thiodipropyl diisocyanate, cyclohexyl-1,4-diisocyanate, dicyclohexyl Methane-4,4′-diisocyanate, 1,5-dimethyl-2,4-bis (isocyanatomethyl) benzene, 1,5-trimethyl-2,4-bis (ω-isocyanatoethyl) -benzene, 1, 3,5-trimethyl-2,4-bis (isocyanatomethyl) benzene, 1,3,5-triethyl-2,4-bis (isocyanatomethyl) benzene, dicyclohexyldimethylmethane-4,4′-diisocyanate, etc. Can be mentioned. Also, use aromatic diisocyanates such as 2,4-diisocyanatotoluene and / or 2,6-diisocyanatotoluene, 4,4'-diisocyanatodiphenylmethane, 1,4-diisocyanatoisopropylbenzene. Can do.
本発明にかかるイソシアヌレート型イソシアネート化合物は、単独でも、２種以上を混合して用いることもできる。また、本発明においては、上記イソシアヌレート型イソシアネート化合物を、それ以外の脂肪族、脂環式、芳香族基含有脂肪族又は芳香族の多官能イソシアネート化合物（好適には前記ジイソシアネート又はその二量体）と組み合わせて混合物として使用することもできる。この場合、多官能イソシアネート化合物の全量中における上記イソシアヌレート型イソシアネート化合物の含有割合が６０質量％以上であることが好ましい。上記イソシアヌレート型イソシアネート化合物の含有割合が前記下限未満の場合は、十分な耐酸性を有する硬化膜が得られにくくなる傾向にある。 The isocyanurate type isocyanate compounds according to the present invention can be used alone or in combination of two or more. In the present invention, the isocyanurate-type isocyanate compound is converted into an aliphatic, alicyclic, aromatic group-containing aliphatic or aromatic polyfunctional isocyanate compound (preferably the diisocyanate or a dimer thereof). ) And can also be used as a mixture. In this case, the content ratio of the isocyanurate type isocyanate compound in the total amount of the polyfunctional isocyanate compound is preferably 60% by mass or more. When the content ratio of the isocyanurate type isocyanate compound is less than the lower limit, a cured film having sufficient acid resistance tends to be hardly obtained.
なお、前記ソフトセグメント部は上述の多官能イソシアネート化合物中に存在していてもよく、本発明に係る多官能イソシアネート化合物における前記ソフトセグメント部の含有割合は、その固形分全量に対して６０質量％以下であることが好ましい。 In addition, the said soft segment part may exist in the above-mentioned polyfunctional isocyanate compound, The content rate of the said soft segment part in the polyfunctional isocyanate compound which concerns on this invention is 60 mass% with respect to the solid content whole quantity. The following is preferable.
本発明の硬化性樹脂組成物は、硬化膜形成性樹脂としての水酸基含有アクリル樹脂と、硬化剤としての多官能イソシアネート化合物とを含有するものであり、水酸基含有アクリル樹脂と多官能イソシアネート化合物との配合割合は水酸基含有アクリル樹脂中の水酸基の数１に対して多官能イソシアネート化合物中のイソシアネート基が０．５〜１．５の範囲内であることが好ましい。上記多官能イソシアネート化合物の配合割合が前記下限未満では十分な硬化が得られなくなる傾向にあり、他方、前記上限を超えると未反応のイソシアネート基が空気中の水分と反応して硬化膜のTmが上昇し耐傷性が悪くなる傾向にある。 The curable resin composition of the present invention contains a hydroxyl group-containing acrylic resin as a cured film-forming resin and a polyfunctional isocyanate compound as a curing agent, and includes a hydroxyl group-containing acrylic resin and a polyfunctional isocyanate compound. The blending ratio is preferably such that the isocyanate group in the polyfunctional isocyanate compound is within the range of 0.5 to 1.5 with respect to the number of hydroxyl groups in the hydroxyl group-containing acrylic resin. When the blending ratio of the polyfunctional isocyanate compound is less than the lower limit, sufficient curing tends not to be obtained.On the other hand, when the upper limit is exceeded, the unreacted isocyanate group reacts with moisture in the air and the Tm of the cured film is reduced. It tends to rise and scratch resistance becomes worse.
上記硬化性樹脂組成物は、有機スズ化合物硬化触媒を有するものであっても良い。上記有機スズ化合物触媒としては特に限定されず、ジブチルスズジラウレート、ジブチルスズジアセテート、ジブチルスズジオクテート等が挙げられる。硬化触媒の配合量は、硬化性樹脂組成物中の重合体固形分全量１００質量部に対し、下限０．００５質量部、上限０．０５質量部であることが好ましい。 The curable resin composition may have an organotin compound curing catalyst. The organotin compound catalyst is not particularly limited, and examples thereof include dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin dioctate. The blending amount of the curing catalyst is preferably a lower limit of 0.005 parts by mass and an upper limit of 0.05 parts by mass with respect to 100 parts by mass of the total amount of polymer solids in the curable resin composition.
以上説明した本発明の硬化性樹脂組成物を硬化させることによって、耐傷性（特に耐擦り傷性）と耐酸性（特に耐硫酸性）が非常に優れている塗膜、被覆材、樹脂フィルム等の各種の硬化膜を得ることができる。なお、本発明の硬化性樹脂組成物を硬化させる方法及びその条件は特に制限されず、常法が適宜採用され、例えば１００〜１８０℃程度の温度で加熱硬化させる方法が好適に採用される。 By curing the curable resin composition of the present invention described above, coating films, coating materials, resin films, etc. that have very excellent scratch resistance (particularly scratch resistance) and acid resistance (particularly sulfuric acid resistance) Various cured films can be obtained. The method for curing the curable resin composition of the present invention and the conditions thereof are not particularly limited, and a conventional method is appropriately employed. For example, a method of thermally curing at a temperature of about 100 to 180 ° C. is suitably employed.
また、本発明の硬化性樹脂組成物は、得られる硬化膜の架橋密度が０．８×１０−３ｍｏｌ／ｃｃ以上（特に好ましくは１．０×１０−３〜２．５×１０−３ｍｏｌ／ｃｃ）となるように調製されていることが好ましい。得られる硬化膜の架橋密度が上記下限未満の場合は、水シミ等に対する耐汚染性が十分に向上せず、耐傷性の維持性も低下してしまう傾向にある。 In the curable resin composition of the present invention, the resulting cured film has a crosslink density of 0.8 × 10 −3 mol / cc or more (particularly preferably 1.0 × 10 −3 to 2.5 × 10 −3). mol / cc) is preferably prepared. When the crosslink density of the obtained cured film is less than the above lower limit, the stain resistance against water spots or the like is not sufficiently improved, and the scratch resistance maintenance property tends to be lowered.
なお、このような架橋密度は以下の方法により求めたものである。すなわち、強制伸縮振動型粘弾性測定装置(オリエンテック株式会社製、バイブロン)を用いて昇温時の動的弾性率（Ｅ'）を求め、このＥ'が極小となる温度とその極小値から次式により算出する。なお、測定周波数は１１Hzとする。
Ｅ'＝３ｎＲＴ （ｎ：架橋密度、Ｒ：気体定数、Ｔ：絶対温度）。
Such crosslink density is obtained by the following method. That is, a dynamic elastic modulus (E ′) at the time of temperature rise is obtained using a forced stretching vibration type viscoelasticity measuring device (Vibron, manufactured by Orientec Co., Ltd.), and the temperature at which E ′ is minimized and the minimum value thereof are obtained. Calculated by the following formula. The measurement frequency is 11 Hz.
E ′ = 3 nRT (n: crosslink density, R: gas constant, T: absolute temperature).
次に、本発明のクリヤー塗料組成物について説明する。すなわち、本発明のクリヤー塗料組成物は、前記本発明の硬化性樹脂組成物をバインダー成分として含有することを特徴とするものである。上記本発明のクリヤー塗料組成物中には、上記バインダー成分の他、紫外線吸収剤、ヒンダードアミン光安定剤、酸化防止剤、架橋樹脂粒子、表面調整剤等を配合しても良い。上記架橋樹脂粒子を用いる場合は、本発明のクリヤー塗料組成物の樹脂固形分に対して、下限０．０１質量％、上限１０質量％の割合で配合することが好ましい。上記下限は、０．１質量％であることがより好ましく、上記上限は、５質量％であることがより好ましい。上記架橋樹脂粒子の添加量が１０質量％を超えると得られる塗膜の外観が悪化する傾向にあり、他方、０．０１質量％未満であるとレオロジーコントロール効果が得られない傾向にある。 Next, the clear coating composition of the present invention will be described. That is, the clear coating composition of the present invention is characterized by containing the curable resin composition of the present invention as a binder component. In addition to the binder component, the clear coating composition of the present invention may contain an ultraviolet absorber, a hindered amine light stabilizer, an antioxidant, crosslinked resin particles, a surface conditioner, and the like. When the crosslinked resin particles are used, it is preferable that the lower limit is 0.01% by mass and the upper limit is 10% by mass with respect to the resin solid content of the clear coating composition of the present invention. The lower limit is more preferably 0.1% by mass, and the upper limit is more preferably 5% by mass. When the added amount of the crosslinked resin particles exceeds 10% by mass, the appearance of the obtained coating film tends to deteriorate, and when it is less than 0.01% by mass, the rheology control effect tends to be not obtained.
本発明のクリヤー塗料組成物は、スプレー塗装、刷毛塗り塗装、浸漬塗装、ロール塗装、流し塗装等により塗装することができる。また、本発明のクリヤー塗料組成物は、いかなる基板、例えば、木、金属、ガラス、布、プラスチック、発泡体等、特に、プラスチック及び金属表面（例えば、スチール、アルミニウム及びこれらの合金）に有利に用いることができ、特に自動車用のクリヤー塗料として好適に使用することができる。 The clear coating composition of the present invention can be applied by spray coating, brush coating, dip coating, roll coating, flow coating, or the like. The clear coating composition of the present invention is also advantageous for any substrate, such as wood, metal, glass, cloth, plastic, foam, etc., especially plastic and metal surfaces (eg, steel, aluminum and alloys thereof). In particular, it can be suitably used as a clear paint for automobiles.
次に、本発明の複層塗膜の形成方法について説明する。すなわち、本発明の複層塗膜の形成方法は、被塗装物に対してトップコートを有する複層塗膜を形成する方法であって、前記本発明のクリヤー塗料組成物を前記トップコートとして塗装することを特徴とする方法である。 Next, the formation method of the multilayer coating film of this invention is demonstrated. That is, the method for forming a multilayer coating film of the present invention is a method for forming a multilayer coating film having a top coat on an object to be coated, and the clear coating composition of the present invention is applied as the top coat. It is the method characterized by doing.
上記被塗装物としては、種々の基材、例えば金属成型品、プラスチック成型品、発泡体等に用いることができるが、自動車用の複層塗膜を形成させる被塗装物としては、鉄、アルミニウム及びこれらの合金等の金属成型品やプラスチック成型品等を挙げることができる。カチオン電着塗装可能な金属成型品に対して適用することが好ましい。上記被塗装物は、表面が化成処理されていることが好ましい。更に、被塗装物は、電着塗膜が形成されていてもよい。上記電着塗料としては、カチオン型及びアニオン型を使用できるが、防食性の観点から、カチオン型電着塗料であることが好ましい。 As the object to be coated, it can be used for various substrates such as metal molded products, plastic molded products, foams, etc., but as the objects to be coated to form a multilayer coating film for automobiles, iron, aluminum And metal molded products such as these alloys, plastic molded products, and the like. It is preferable to apply to metal molded products that can be subjected to cationic electrodeposition coating. The surface of the object to be coated is preferably subjected to chemical conversion treatment. Furthermore, an electrodeposition coating film may be formed on the object to be coated. As the electrodeposition paint, a cation type and an anion type can be used. From the viewpoint of anticorrosion, a cation type electrodeposition paint is preferable.
また、更に必要に応じて、中塗り塗膜が形成されていてもよい。中塗り塗膜の形成には中塗り塗料が用いられる。上記中塗り塗料としては特に限定されず、当業者によってよく知られている水性又は有機溶剤型のもの等を挙げることができる。 Furthermore, an intermediate coating film may be formed as necessary. An intermediate coating is used to form the intermediate coating film. The intermediate coating is not particularly limited, and examples thereof include water-based or organic solvent-type ones well known by those skilled in the art.
本発明の複層塗膜の形成方法においては、前記被塗装物にベース塗料組成物を塗布してベース未硬化塗膜を得た後、前記ベース未硬化塗膜に本発明のクリヤー塗料組成物を塗布してクリヤー未硬化塗膜を得、前記ベース未硬化塗膜及びクリヤー未硬化塗膜を同時に加熱して硬化させることが好ましい。また、ベース、クリヤー硬化塗膜上に第２クリヤーとして本発明のクリヤー塗料組成物を塗布し、加熱して硬化させることも可能である。 In the method for forming a multilayer coating film of the present invention, a base coating composition is applied to the object to be coated to obtain a base uncured coating film, and then the clear coating composition of the present invention is applied to the base uncured coating film. It is preferable that a clear uncured coating film is obtained by coating the base uncured coating film and the clear uncured coating film is heated and cured simultaneously. It is also possible to apply the clear coating composition of the present invention as the second clear on the base and clear cured coating film, and to cure by heating.
上記ベース塗料としては特に限定されず、例えば、塗膜形成性樹脂、硬化剤、有機系、無機系又は光輝材等の着色顔料及び体質顔料等を含んでいてもよい。上記ベース塗料の形態としては特に限定されず、水性又は有機溶剤型のもの等を挙げることができる。 It does not specifically limit as said base coating material, For example, coloring pigments, extender pigments, etc., such as a film-forming resin, a hardening | curing agent, an organic type, an inorganic type, or a luster material, may be included. The form of the base paint is not particularly limited, and examples thereof include an aqueous or organic solvent type.
上記被塗装物に対して、上記ベース塗料を塗装する方法としては特に限定されず、スプレー塗装、回転霧化式塗装等を挙げることができ、外観向上の観点から、これらの方法を用いた多ステージ塗装、又は、これらを組み合わせた塗装方法であることが好ましい。 The method of applying the base paint to the object to be coated is not particularly limited, and examples thereof include spray coating and rotary atomizing coating. From the viewpoint of improving the appearance, many of these methods are used. It is preferable that the coating method is stage coating or a combination thereof.
本発明の複層塗膜の形成方法における上記ベース塗料による塗装膜厚は、乾燥膜厚で下限が１０μｍ、上限が２０μｍの範囲内であることが好ましい。また、本発明の複層塗膜の形成方法において、上記ベース塗料が水性のものである場合、良好な仕上がり塗膜を得るために、上記クリヤー塗料組成物を塗装する前に、ベース未硬化塗膜を４０〜１００℃で２〜１０分間加熱しておくことが望ましい。 It is preferable that the coating film thickness by the said base coating material in the formation method of the multilayer coating film of this invention is a dry film thickness in the range whose lower limit is 10 micrometers and whose upper limit is 20 micrometers. In the method for forming a multilayer coating film of the present invention, when the base coating material is water-based, the base uncured coating is applied before the clear coating composition is applied in order to obtain a good finished coating film. It is desirable to heat the membrane at 40-100 ° C. for 2-10 minutes.
本発明の複層塗膜の形成方法において本発明のクリヤー塗料組成物を塗装する方法としては、具体的には、マイクロマイクロベル、マイクロベルと呼ばれる回転霧化式の静電塗装機による塗装方法を挙げることができる。 As a method for applying the clear coating composition of the present invention in the method for forming a multilayer coating film of the present invention, specifically, a micro-microbell, a coating method using a rotary atomizing electrostatic coater called a microbell Can be mentioned.
本発明の複層塗膜の形成方法における上記クリヤー塗料の塗装膜厚は、乾燥膜厚で下限が３０μｍ、上限が４５μｍの範囲内であることが好ましい。また、上記の方法によって形成されたベースの未硬化塗膜及びクリヤーの未硬化塗膜は、同時に加熱されて硬化されることが好ましく、それによって複層塗膜が形成される。上記加熱温度は、下限が１００℃、上限が１８０℃の範囲内で行うことが好ましい。また、下限が１２０℃、上限が１６０℃であることがより好ましい。加熱硬化時間は、硬化温度等によって変化するが、上記加熱硬化温度で行う場合は、１０〜３０分であることが適当である。 In the method for forming a multilayer coating film of the present invention, the coating thickness of the clear coating is preferably a dry film thickness with a lower limit of 30 μm and an upper limit of 45 μm. Moreover, it is preferable that the base uncured coating film and the clear uncured coating film formed by the above method are simultaneously heated and cured, thereby forming a multilayer coating film. It is preferable to perform the said heating temperature within the range whose lower limit is 100 degreeC and whose upper limit is 180 degreeC. More preferably, the lower limit is 120 ° C and the upper limit is 160 ° C. The heat-curing time varies depending on the curing temperature or the like, but when it is performed at the above-mentioned heat-curing temperature, it is appropriate to be 10 to 30 minutes.
このようにして得られた複層塗膜の膜厚は、下限が４０μｍ、上限が６５μｍの範囲内であることが好ましい。上記本発明の複層塗膜の形成方法によって得られた複層塗膜は、耐傷性（特に耐擦り傷性）と耐酸性（特に耐硫酸性）が非常に優れている。 Thus, it is preferable that the film thickness of the obtained multilayer coating film exists in the range whose lower limit is 40 micrometers and whose upper limit is 65 micrometers. The multilayer coating film obtained by the method for forming a multilayer coating film of the present invention has very good scratch resistance (particularly scratch resistance) and acid resistance (particularly sulfuric acid resistance).
以下、実施例及び比較例に基づいて本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。なお、本実施例中でおいて単に「％」と記載した場合は、「質量％」を指すものとする。 EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example. In this example, when “%” is simply described, it means “mass%”.
（合成例１）水酸基含有アクリル樹脂ａの合成
撹拌羽根、窒素導入管、冷却コンデンサー及び滴下ロートを備えた２Ｌのガラス容器に、プロピレングリコールモノメチルエーテルアセテート３５８．０ｇ及びキシレン９０．０ｇを加え、窒素雰囲気下１３０℃に加温した。その容器に、滴下ロートを用いてプロピレングリコールモノメチルエーテルアセテート１００．０ｇ、ｔｅｒｔ−ブチルパーオキシ−２−エチルヘキサノエート１００．０ｇ、スチレン１４０．０ｇ、アクリル酸−ｎ−ブチル８５．４ｇ、メタクリル酸−ｎ−ブチル１３３．７ｇ、メタクリル酸−２−エチルヘキシル３５．０ｇ、アクリル酸−４−ヒドロキシブチル３０５．９ｇ、プラクセルＦＭ−２（２−ヒドロキシエチルメタクリレートとε−カプロラクトンの１：２付加物、ダイセル工業社製）３００．０ｇを３時間かけて等速滴下した。その後１３０℃で０．５時間保持し、５０．０ｇのプロピレングリコールモノメチルエーテルアセテートに溶解したｔｅｒｔ−ブチルパーオキシ−２−エチルヘキサノエート１０．０ｇを３０分で等速滴下した。更に、１３０℃で１．０時間加温を続けることによって、目的の水酸基含有アクリル樹脂ａを得た。
(Synthesis Example 1) Synthesis of hydroxyl group-containing acrylic resin a To a 2 L glass container equipped with a stirring blade, a nitrogen introduction tube, a cooling condenser and a dropping funnel, 358.0 g of propylene glycol monomethyl ether acetate and 90.0 g of xylene were added, and nitrogen was added. Warm to 130 ° C. under atmosphere. In the container, using a dropping funnel, 100.0 g of propylene glycol monomethyl ether acetate, 100.0 g of tert-butylperoxy-2-ethylhexanoate, 140.0 g of styrene, 85.4 g of acrylic acid-n-butyl, methacryl Acid-n-butyl 133.7 g, methacrylate-2-ethylhexyl 35.0 g, acrylic acid-4-hydroxybutyl 305.9 g, plaxel FM-2 (1: 2 adduct of 2-hydroxyethyl methacrylate and ε-caprolactone) (Manufactured by Daicel Kogyo Co., Ltd.) was dropped at a constant rate over 30 hours. Thereafter, the mixture was kept at 130 ° C. for 0.5 hour, and 10.0 g of tert-butylperoxy-2-ethylhexanoate dissolved in 50.0 g of propylene glycol monomethyl ether acetate was added dropwise at a constant rate in 30 minutes. Furthermore, the objective hydroxyl-containing acrylic resin a was obtained by continuing a heating at 130 degreeC for 1.0 hour.
合成した水酸基含有アクリル樹脂ａについて、ＧＰＣを用いて得られた標準ポリスチレン換算の分子量の値はＭｎ＝４５００、Ｍｗ＝１０８００であった。また、水酸基価は１６６ｍｇＫＯＨ／ｇ、計算Ｔｇは−１７℃、樹脂固形分は６３．２％、ラクトン部含有率は１９．１１％であった。更に、水酸基含有アクリル樹脂ａにおける前記ソフトセグメント部の含有率は、その固形分全量に対して２３．６３％であり、ラクトン含有モノマー由来ソフトセグメント部の含有率は１１．７３％であった。上記の水酸基含有アクリル樹脂ａの組成及び諸物性を表１に示す。 About the synthesized hydroxyl group-containing acrylic resin a, the molecular weight values in terms of standard polystyrene obtained using GPC were Mn = 4500 and Mw = 10800. The hydroxyl value was 166 mgKOH / g, the calculated Tg was −17 ° C., the resin solid content was 63.2%, and the lactone moiety content was 19.11%. Furthermore, the content rate of the said soft segment part in the hydroxyl-containing acrylic resin a was 23.63% with respect to the solid content whole quantity, and the content rate of the lactone-containing monomer origin soft segment part was 11.73%. Table 1 shows the composition and various physical properties of the hydroxyl group-containing acrylic resin a.
（合成例２〜４）水酸基含有アクリル樹脂ｂ〜ｄの合成
表１に示すモノマー成分、溶媒及び重合開始剤を用い、それらの配合量を表１に示すようにした以外は合成例１と同様にして、水酸基含有アクリル樹脂ｂ〜ｄをそれぞれ合成した。なお、プラクセルＦＭ−１としては２−ヒドロキシエチルメタクリレートとε−カプロラクトンの１：１付加物（ダイセル工業社製）、プラクセルＦＭ−５としては２−ヒドロキシエチルメタクリレートとε−カプロラクトンの１：５付加物（ダイセル工業社製）を用いた。
(Synthesis Examples 2 to 4) Synthesis of Hydroxyl-Containing Acrylic Resins b to d The same as Synthesis Example 1 except that the monomer components, the solvent, and the polymerization initiator shown in Table 1 were used, and the blending amounts thereof were shown in Table 1. Thus, hydroxyl group-containing acrylic resins b to d were respectively synthesized. Plaxel FM-1 is a 1: 1 addition product of 2-hydroxyethyl methacrylate and ε-caprolactone (manufactured by Daicel Industries), and Plaxel FM-5 is a 1: 5 addition of 2-hydroxyethyl methacrylate and ε-caprolactone. The thing (made by Daicel Industrial Co., Ltd.) was used.
合成した水酸基含有アクリル樹脂ｂ〜ｄの分子量（Ｍｎ）、分子量（Ｍｗ）、水酸基価、計算Ｔｇ、樹脂固形分、ラクトン部含有率、樹脂固形分中の全ソフトセグメント部含有率、ラクトン含有モノマー由来ソフトセグメント部含有率及びラクトンフリーモノマー由来ソフトセグメント部含有率はそれぞれ表１に示す通りであった。 Molecular weight (Mn), molecular weight (Mw), hydroxyl value, calculated Tg, resin solid content, lactone part content, total soft segment content in resin solids, lactone-containing monomer The origin soft segment part content and the lactone free monomer origin soft segment part content were as shown in Table 1, respectively.
（実施例１〜４及び比較例１〜４）
表２に示した配合に従い、各成分を混合し、ディスパーで攪拌することによって実施例１〜４及び比較例１〜４のクリヤー塗料組成物を得た。上記クリヤー塗料組成物を、プロピレングリコールモノメチルエーテルアセテート／３−エトキシプロピオン酸エチル＝１／２（質量比）からなるシンナーによってＮｏ．４フォードカップで２５秒／２０℃となるようにそれぞれ希釈した。なお、ビュレット型イソシアネート硬化剤としては、住化バイエルウレタン（株）社製スミジュールＮ−７５を用い、イソシアヌレート型イソシアネート硬化剤としては、住化バイエルウレタン（株）社製スミジュールＮ３３００を用い、アシンメトリー型イソシアネート硬化剤としては、住化バイエルウレタン（株）社製デスモジュールＸ２４１０を用いた。
(Examples 1-4 and Comparative Examples 1-4)
According to the composition shown in Table 2, the components were mixed and stirred with a disper to obtain the clear coating compositions of Examples 1 to 4 and Comparative Examples 1 to 4. The clear coating composition was subjected to No. 1 using a thinner composed of propylene glycol monomethyl ether acetate / 3-ethyl ethyl ethoxypropionate = 1/2 (mass ratio). Each was diluted with a 4 Ford cup to 25 ° C / 20 ° C. In addition, Sumika Bayer Urethane Co., Ltd. Sumidur N-75 is used as a burette type isocyanate curing agent, and Sumika Bayer Urethane Co., Ltd. Sumidur N3300 is used as an isocyanurate type isocyanate curing agent. As an asymmetric isocyanate curing agent, Desmodur X2410 manufactured by Sumika Bayer Urethane Co., Ltd. was used.
次に、リン酸亜鉛処理した１５０×３００×０．８ｍｍのダル鋼板に、パワートップＵ−５０（日本ペイント社製カチオン電着塗料）を、乾燥膜厚が２０μｍとなるように電着塗装し、１６０℃で３０分間焼付けた塗板に、Ｎｏ．４フォードカップで２５秒／２０℃となるように、予め希釈されたオルガＰ−２（日本ペイント社製メラミン硬化型ポリエステル樹脂系グレー中塗り塗料）を、乾燥膜厚が３５μｍとなるようにエアスプレーで２ステージ塗装し、１４０℃で３０分間焼き付けた後冷却して、中塗り基板を得た。上記中塗り基板上に、スーパーラックＭ−２６０ブラック（日本ペイント社製水性ベース塗料）を、室温２５℃、湿度８５％の条件下で、乾燥膜厚１５μｍとなるようにスプレー塗装した後、８０℃で３分間のプレヒートを行った。プレヒート後、塗装板を室温まで放冷し、第１クリヤーとしてスーパーラックＯ−１７０（日本ペイント社製アクリル系メラミン硬化型クリヤ塗料）を乾燥膜厚３０μｍになるように塗装し、１４０℃で２５分間加熱硬化した。上記第１クリヤー基板を＃２０００水研ペーパーで研磨した後、希釈した上記各クリヤー塗料組成物を、乾燥膜厚３５μｍとなるようにスプレー塗装した後、乾燥炉にて１４０℃で２５分間加熱して、基板上に複層塗膜を形成した。 Next, power top U-50 (cationic electrodeposition paint manufactured by Nippon Paint Co., Ltd.) is electrodeposited onto a 150 × 300 × 0.8 mm dull steel plate treated with zinc phosphate so that the dry film thickness is 20 μm. No. 1 was applied to the coated plate baked at 160 ° C. for 30 minutes. Olga P-2 (melamine curable polyester resin-based gray intermediate coating material manufactured by Nippon Paint Co., Ltd.) diluted in advance so as to be 25 seconds / 20 ° C. in a 4 Ford cup is air-dried so that the dry film thickness becomes 35 μm. Two-stage coating was performed by spraying, baking was performed at 140 ° C. for 30 minutes, and then cooling to obtain an intermediate coated substrate. After spray coating Superlac M-260 Black (Nippon Paint Co., Ltd. water-based base paint) on the above-mentioned intermediate coating substrate under conditions of room temperature of 25 ° C. and humidity of 85% to a dry film thickness of 15 μm, 80 Preheating was performed at 3 ° C. for 3 minutes. After preheating, the coated plate is allowed to cool to room temperature, and Superlac O-170 (acrylic melamine curable clear paint manufactured by Nippon Paint Co., Ltd.) is applied as the first clear so as to have a dry film thickness of 30 μm. Heat cured for minutes. After polishing the first clear substrate with # 2000 water research paper, each of the diluted clear coating compositions was spray-coated to a dry film thickness of 35 μm, and then heated at 140 ° C. for 25 minutes in a drying furnace. A multilayer coating film was formed on the substrate.
実施例１〜４及び比較例１〜４で得られたクリヤー塗料組成物の固形分全量中における各種ソフトセグメント部の含有率（ラクトン含有モノマー由来ソフトセグメント部含有率、ラクトンフリーモノマー由来ソフトセグメント部含有率、水酸基含有アクリル樹脂由来の全ソフトセグメント部含有率、イソシアネート硬化剤由来のソフトセグメント部含有率、全ソフトセグメント部の含有率（質量％））は、表２に示す通りである。 Content of various soft segment parts in the total solid content of the clear coating compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 4 (lactone-containing monomer-derived soft segment part content, lactone-free monomer-derived soft segment part Table 2 shows the content, the total soft segment part content derived from the hydroxyl group-containing acrylic resin, the soft segment part content derived from the isocyanate curing agent, and the total soft segment part content (mass%).
＜耐酸性試験＞
実施例１〜４及び比較例１〜４のクリヤー塗料組成物を用いて得られた複層塗膜について、以下の評価方法によって４０％硫酸水溶液による耐酸性の評価を行った。
<Acid resistance test>
About the multilayer coating film obtained using the clear coating composition of Examples 1-4 and Comparative Examples 1-4, the acid-proof evaluation by 40% sulfuric acid aqueous solution was performed with the following evaluation methods.
すなわち、先ず、イオン交換水と試薬特級の硫酸により４０％硫酸水溶液を作製した。次に、上記硫酸水溶液を、実施例１〜４及び比較例１〜４のクリヤー塗料組成物を用いて得られた複層塗膜上に０．６ｍｌずつ滴下し、加熱オーブン中に８０℃で３０分保持した後、水洗した。その後、複層塗膜上のスポット跡を目視観察し、以下の基準に基づいて評価した。得られた結果を表２に示す。
○：スポット部に塗膜のハガレは認められないもの。
△：スポット部の塗膜の一部にハガレが認められたもの。
×：スポット部の塗膜が完全にハガレているもの。
That is, first, a 40% sulfuric acid aqueous solution was prepared from ion-exchanged water and reagent-grade sulfuric acid. Next, 0.6 ml of the above sulfuric acid aqueous solution was dropped on the multilayer coating film obtained by using the clear coating compositions of Examples 1 to 4 and Comparative Examples 1 to 4 at 80 ° C. in a heating oven. After holding for 30 minutes, it was washed with water. Thereafter, the spot marks on the multilayer coating film were visually observed and evaluated based on the following criteria. The obtained results are shown in Table 2.
○: No peeling of the coating film is observed in the spot portion.
(Triangle | delta): The peeling was recognized in a part of coating film of a spot part.
X: The film of the spot part is completely peeled off.
＜耐擦り傷性試験＞
実施例１〜４及び比較例１〜４のクリヤー塗料組成物を用いて得られた複層塗膜について、以下の評価方法によって耐擦り傷性の評価を行った。
<Abrasion resistance test>
The multilayer coating films obtained using the clear coating compositions of Examples 1 to 4 and Comparative Examples 1 to 4 were evaluated for scratch resistance by the following evaluation methods.
すなわち、先ず、ミニ洗車機の台上に、試験用ダスト（７種類混合、粒度２７〜３１μｍ）１５ｇ及び水１００ｇからなる試験用ダスト組成物を広げた後、水を流さずにミニ洗車機を回転（４５ｒｐｍ）、一往復させて、洗車機ブラシにダストを付着させた。その後、台上に塗板（７０ｍｍ×１５０ｍｍ）を固定し、塗板上に鋳物砂約５ｇをふりかけた後、水を流さずにミニ洗車機を回転（９６ｒｐｍ）させて３往復させた。試験後、水洗及び乾燥を行った。塗板の２０°光沢を測定し、この２０°光沢の試験前の２０°光沢に対する割合である光沢保持率（初期２０°ＧＲ（％））を算出した。得られた結果を表２に示す。 That is, first, after spreading a test dust composition consisting of 15 g of test dust (7 types mixed, particle size 27 to 31 μm) and 100 g of water on a mini car wash table, the mini car wash machine is run without flowing water. It was rotated (45 rpm) and reciprocated once to allow dust to adhere to the car wash brush. Thereafter, a coated plate (70 mm × 150 mm) was fixed on the table, and about 5 g of foundry sand was sprinkled on the coated plate, and then the mini car washer was rotated (96 rpm) and reciprocated three times without flowing water. After the test, washing and drying were performed. The 20 ° gloss of the coated plate was measured, and the gloss retention (initial 20 ° GR (%)), which is the ratio of the 20 ° gloss to the 20 ° gloss before the test, was calculated. The obtained results are shown in Table 2.
表２に示した結果から明らかなように、本発明のクリヤー塗料組成物を用いて得られた複層塗膜は、耐傷性（耐擦り傷性）と耐酸性（耐硫酸性）が非常に優れていたのに対し、比較例のクリヤー塗料組成物を用いて得られた複層塗膜は特に耐酸性が劣るものであった。 As is apparent from the results shown in Table 2, the multilayer coating film obtained using the clear coating composition of the present invention has very excellent scratch resistance (scratch resistance) and acid resistance (sulfuric acid resistance). On the other hand, the multilayer coating film obtained by using the clear coating composition of the comparative example was particularly inferior in acid resistance.
以上説明したように、本発明によれば、耐傷性（特に耐擦り傷性）と耐酸性（特に耐硫酸性）を更に向上せしめた硬化膜（例えば塗膜）を形成することが可能な硬化性樹脂組成物を得ることが可能となる。したがって、本発明の硬化性樹脂組成物をバインダーとして含有する本発明のクリヤー塗料組成物によって、耐傷性と耐酸性が非常に優れているクリヤー塗膜を形成することが可能となる。そして、本発明のクリヤー塗料組成物を用いた本発明の複層塗膜の形成方法によれば、耐傷性と耐酸性が非常に優れている自動車用複層塗膜を効率良くかつ確実に形成することが可能となる。 As described above, according to the present invention, the curability capable of forming a cured film (for example, a coating film) with further improved scratch resistance (particularly scratch resistance) and acid resistance (particularly sulfuric acid resistance). A resin composition can be obtained. Therefore, the clear coating composition of the present invention containing the curable resin composition of the present invention as a binder can form a clear coating film having very excellent scratch resistance and acid resistance. Then, according to the method for forming a multilayer coating film of the present invention using the clear coating composition of the present invention, a multilayer coating film for automobiles having excellent scratch resistance and acid resistance is efficiently and reliably formed. It becomes possible to do.
Claims (4)
前記多官能イソシアネート化合物の全量中における６０質量％以上がイソシアヌレート型イソシアネート化合物であり、
前記硬化性樹脂組成物は、下記一般式（１）：
−（ＣＨ２）ｎ− （１）
（式中、ｎは４〜９の整数を表す。）
で表され且つ前記硬化性樹脂組成物の主鎖中又は架橋結合鎖中に存在するソフトセグメント部を、前記水酸基含有アクリル樹脂及び多官能イソシアネート化合物の固形分全量に対して２５〜５０質量％有しており、
前記水酸基含有アクリル樹脂における前記ソフトセグメント部の含有割合は、前記水酸基含有アクリル樹脂の固形分全量に対して７〜３０質量％であり、
前記多官能イソシアネート化合物における前記ソフトセグメント部の含有割合は、前記多官能イソシアネート化合物の固形分全量に対して６０質量％以下であり、
前記水酸基含有アクリル樹脂と前記多官能イソシアネート化合物との配合割合は、前記水酸基含有アクリル樹脂中の水酸基の数１に対して前記多官能イソシアネート化合物中のイソシアネート基が０．５〜１．５の範囲内となる配合割合である、
ことを特徴とする硬化性樹脂組成物。 A curable resin composition containing a hydroxyl group-containing acrylic resin and a polyfunctional isocyanate compound,
60% by mass or more in the total amount of the polyfunctional isocyanate compound is an isocyanurate type isocyanate compound,
The curable resin composition has the following general formula (1):
- (CH 2) n - ( 1)
(In the formula, n represents an integer of 4 to 9. )
And the soft segment portion present in the main chain or the cross-linked chain of the curable resin composition in an amount of 25 to 50% by mass based on the total solid content of the hydroxyl group-containing acrylic resin and polyfunctional isocyanate compound. and it is,
The content ratio of the soft segment portion in the hydroxyl group-containing acrylic resin is 7 to 30% by mass with respect to the total solid content of the hydroxyl group-containing acrylic resin,
The content ratio of the soft segment portion in the polyfunctional isocyanate compound is 60% by mass or less based on the total solid content of the polyfunctional isocyanate compound,
The mixing ratio of the hydroxyl group-containing acrylic resin and the polyfunctional isocyanate compound is such that the isocyanate group in the polyfunctional isocyanate compound is 0.5 to 1.5 with respect to the number of hydroxyl groups in the hydroxyl group-containing acrylic resin. It is the blending ratio that is inside,
A curable resin composition characterized by that.
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