WO2019065571A1 - Curable resin composition, paint, and article - Google Patents
Curable resin composition, paint, and article Download PDFInfo
- Publication number
- WO2019065571A1 WO2019065571A1 PCT/JP2018/035304 JP2018035304W WO2019065571A1 WO 2019065571 A1 WO2019065571 A1 WO 2019065571A1 JP 2018035304 W JP2018035304 W JP 2018035304W WO 2019065571 A1 WO2019065571 A1 WO 2019065571A1
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- Prior art keywords
- copolymer
- mass
- paint
- meth
- parts
- Prior art date
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- 239000003973 paint Substances 0.000 title claims abstract description 32
- 239000011342 resin composition Substances 0.000 title claims abstract description 22
- 229920001577 copolymer Polymers 0.000 claims abstract description 52
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 22
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 16
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 6
- 239000011976 maleic acid Substances 0.000 claims description 6
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 12
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 41
- -1 industrial machines Substances 0.000 description 21
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 18
- 239000004793 Polystyrene Substances 0.000 description 17
- 239000000178 monomer Substances 0.000 description 17
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- 239000002253 acid Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 8
- IAXXETNIOYFMLW-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) 2-methylprop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C(=C)C)CC1C2(C)C IAXXETNIOYFMLW-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
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- 238000006243 chemical reaction Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
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- 238000003756 stirring Methods 0.000 description 7
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
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- 239000002904 solvent Substances 0.000 description 6
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- 239000000049 pigment Substances 0.000 description 4
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- 239000004033 plastic Substances 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 101710148027 Ribulose bisphosphate carboxylase/oxygenase activase 1, chloroplastic Proteins 0.000 description 3
- 101710201629 Ribulose bisphosphate carboxylase/oxygenase activase 2, chloroplastic Proteins 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
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- 238000002360 preparation method Methods 0.000 description 3
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- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- 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
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
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- 239000004566 building material Substances 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
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- CQQXCSFSYHAZOO-UHFFFAOYSA-L [acetyloxy(dioctyl)stannyl] acetate Chemical compound CCCCCCCC[Sn](OC(C)=O)(OC(C)=O)CCCCCCCC CQQXCSFSYHAZOO-UHFFFAOYSA-L 0.000 description 1
- NBJODVYWAQLZOC-UHFFFAOYSA-L [dibutyl(octanoyloxy)stannyl] octanoate Chemical compound CCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCC NBJODVYWAQLZOC-UHFFFAOYSA-L 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- XFSBVAOIAHNAPC-WSORPINJSA-N acetylbenzoylaconine Chemical compound O([C@H]1[C@]2(O)C[C@H]3C45[C@@H]6[C@@H]([C@@]([C@H]31)(OC(C)=O)[C@@H](O)[C@@H]2OC)[C@H](OC)C4[C@]([C@@H](C[C@H]5OC)O)(COC)CN6CC)C(=O)C1=CC=CC=C1 XFSBVAOIAHNAPC-WSORPINJSA-N 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005233 alkylalcohol 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
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 229940072049 amyl acetate Drugs 0.000 description 1
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- ZCGHEBMEQXMRQL-UHFFFAOYSA-N benzyl 2-carbamoylpyrrolidine-1-carboxylate Chemical compound NC(=O)C1CCCN1C(=O)OCC1=CC=CC=C1 ZCGHEBMEQXMRQL-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- NUMHJBONQMZPBW-UHFFFAOYSA-K bis(2-ethylhexanoyloxy)bismuthanyl 2-ethylhexanoate Chemical compound [Bi+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O NUMHJBONQMZPBW-UHFFFAOYSA-K 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- NCEXYHBECQHGNR-UHFFFAOYSA-N chembl421 Chemical compound C1=C(O)C(C(=O)O)=CC(N=NC=2C=CC(=CC=2)S(=O)(=O)NC=2N=CC=CC=2)=C1 NCEXYHBECQHGNR-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- QAEKNCDIHIGLFI-UHFFFAOYSA-L cobalt(2+);2-ethylhexanoate Chemical compound [Co+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O QAEKNCDIHIGLFI-UHFFFAOYSA-L 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000006006 cyclotrimerization reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ZPJMVXJOGCCDPH-UHFFFAOYSA-M methyl(trioctyl)azanium;acetate Chemical compound CC([O-])=O.CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC ZPJMVXJOGCCDPH-UHFFFAOYSA-M 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
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 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
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- MADOXCFISYCULS-UHFFFAOYSA-N octyl 2-sulfanylacetate Chemical compound CCCCCCCCOC(=O)CS MADOXCFISYCULS-UHFFFAOYSA-N 0.000 description 1
- ZMHZSHHZIKJFIR-UHFFFAOYSA-N octyltin Chemical compound CCCCCCCC[Sn] ZMHZSHHZIKJFIR-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000012462 polypropylene substrate Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- 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
- 229940090181 propyl acetate Drugs 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- MCZDHTKJGDCTAE-UHFFFAOYSA-M tetrabutylazanium;acetate Chemical compound CC([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC MCZDHTKJGDCTAE-UHFFFAOYSA-M 0.000 description 1
- MRYQZMHVZZSQRT-UHFFFAOYSA-M tetramethylazanium;acetate Chemical compound CC([O-])=O.C[N+](C)(C)C MRYQZMHVZZSQRT-UHFFFAOYSA-M 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
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- IFNXAMCERSVZCV-UHFFFAOYSA-L zinc;2-ethylhexanoate Chemical compound [Zn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O IFNXAMCERSVZCV-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
Definitions
- the present invention relates to a curable resin composition excellent in pot life and curability, a paint, and an article having a cured coating film of the paint.
- a two-component urethane paint in which a resin having a hydroxyl group and a polyisocyanate compound are combined is used in various applications such as automobile exteriors, automobile repair, plastics, industrial machines, building materials and the like.
- coexistence of pot life and curability is an issue, and for example, a paint composition containing a hydroxyl group-containing resin, a polyisocyanate compound, and an organic tin compound, which contains phosphoric acid in the paint Coating compositions and the like in which groups are present have been proposed (see, for example, Patent Document 1).
- the problem to be solved by the present invention is to provide a curable resin composition having a long pot life and excellent curability, a paint, and an article having a cured coating film of the paint.
- the present inventors are usable by using the curable resin composition containing the copolymer which has a specific structure, a polyisocyanate compound, and a curing catalyst.
- the inventors have found that a cured coating film excellent in curability can be obtained even under a long time and under room temperature curing conditions, and the present invention has been completed.
- the present invention is a curable resin composition containing a copolymer (A) having a hydroxyl group, a polyisocyanate compound (B), and an organic metal catalyst (C), wherein the copolymer (A) is
- the present invention relates to a curable resin composition characterized by having a structure derived from unsaturated dicarboxylic acid monoester (a1).
- the curable resin composition of the present invention has a long working life and is excellent in curability, it is suitable for various coatings for automobile exteriors, automobile repair, plastics, industrial machines, building materials, wood floors, etc. It can be used for
- the curable resin composition of the present invention is a curable resin composition comprising a copolymer (A) having a hydroxyl group, a polyisocyanate compound (B), and an organic metal catalyst (C), wherein the copolymer is (A) has a structure derived from unsaturated dicarboxylic acid monoester (a1).
- the copolymer (A) is obtained, for example, by copolymerizing an unsaturated dicarboxylic acid monoester (a1), a monomer having a hydroxyl group (a2), and another monomer (a3).
- Examples of the unsaturated dicarboxylic acid monoester (a1) include monoesters of dicarboxylic acids such as maleic acid, itaconic acid, citraconic acid and fumaric acid and alcohols, and the balance of pot life and curability is Maleic acid monoester is preferred because it improves more.
- maleic acid monoester a monoester of maleic acid such as monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate and the like with an improved balance of pot life and curability can be obtained.
- monoesters of maleic acid such as monomethyl maleate, monoethyl maleate, monobutyl maleate and the like and an alkyl alcohol having 1 to 4 carbon atoms are more preferable.
- Examples of the hydroxyl group-containing monomer (a2) include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxy-n-butyl (meth) acrylate, 2-hydroxypropyl (for example) Meta) acrylate, 2-hydroxy-n-butyl (meth) acrylate, 3-hydroxy-n-butyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, glycerin mono (meth) acrylate, polyethylene glycol Mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, hydroxyl group at terminal Lactone-modified (meth) acrylate that.
- Examples of the other monomer (a3) include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (for example, Meta) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (me
- (meth) acrylic acid refers to one or both of methacrylic acid and acrylic acid
- (meth) acrylate refers to one or both of methacrylate and acrylate
- (meth) acrylic acid The term “acryloyl” refers to one or both of methacryloyl and acryloyl.
- the amount of the unsaturated dicarboxylic acid monoester (a1) used is the mass ratio in the monomer component which is the raw material of the copolymer (A) because the balance of pot life and curability is further improved.
- the range of 0.1 to 10% by mass is preferable, the range of 0.1 to 5% by mass is more preferable, and the range of 0.5 to 3% by mass is more preferable.
- the use amount of the monomer (a2) having a hydroxyl group is 1 to 70 as a mass ratio in the monomer component which is a raw material of the copolymer (A) since the physical properties of the cured product are further improved.
- the range of mass% is preferable, the range of 5 to 60 mass% is more preferable, and the range of 10 to 50 mass% is more preferable.
- the unsaturated dicarboxylic acid monoester (a1), the monomer having the hydroxyl group (a2), and the other monomer (a3) are known as raw materials.
- solution radical polymerization is preferable because it is the most simple.
- the above-mentioned solution radical polymerization method is a method in which each monomer as a raw material is dissolved in a solvent and a polymerization reaction is performed in the presence of a polymerization initiator.
- the solvent that can be used at this time include hydrocarbon solvents such as toluene, xylene, cyclohexane, n-hexane and octane; methanol, ethanol, iso-propanol, n-butanol, iso-butanol and sec-butanol Alcohol solvents such as ethylene glycol monomethyl ether; ester solvents such as methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate and amyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone Be These solvents may be used alone or
- polymerization initiator used in the production of the acrylic resin (A) for example, 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylbutyronitrile), azobiscyanovaleric acid, etc. Azo compounds of: tert-butyl peroxypivalate, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, di-tert-butyl peroxide, cumene hydroperoxide, benzoyl peroxide, tert Organic peroxides such as butyl hydroperoxide; and inorganic peroxides such as hydrogen peroxide, ammonium persulfate, potassium persulfate and sodium persulfate. These polymer initiators can be used alone or in combination of two or more.
- the polymerization initiator is preferably used in a range of 0.1 to 10% by mass with respect to the total of the monomers as the raw material of the copoly
- a chain transfer agent such as lauryl mercaptan, octyl mercaptan, 2-mercaptoethanol, octyl thioglycolate, 3-mercaptopropionic acid, ⁇ -methylstyrene dimer, etc. may be used. it can.
- the acid value of the copolymer (A) is preferably in the range of 0.4 to 45 mg KOH / g, more preferably in the range of 0.4 to 25 mg KOH / g, because the balance of pot life and curability is further improved.
- the range of 2 to 15 mg KOH / g is more preferred.
- the hydroxyl value of the copolymer (A) is preferably in the range of 4 to 300 mg KOH / g, more preferably in the range of 20 to 260 mg KOH / g, since the balance of pot life and curability is further improved. A range of 220 mg KOH / g is more preferred.
- the acid value and the hydroxyl value of the copolymer in the present invention are measured in accordance with JIS test method K 0070-1992.
- the weight average molecular weight (Mw) of the copolymer (A) is preferably in the range of 2,000 to 100,000, more preferably in the range of 2,000 to 50,000, and in the range of 2,000 to 30,000. Is more preferred.
- the weight average molecular weight (Mw) is a value converted to polystyrene based on gel permeation chromatography (hereinafter abbreviated as "GPC") measurement.
- the said polyisocyanate compound (B) is demonstrated.
- the polyisocyanate compound (B) include aromatic diisocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, m-xylylene diisocyanate, m-phenylene bis (dimethyl methylene) diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, 1, Fats such as 3-bis (isocyanatomethyl) cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate And cycloaliphatic diisocyanate compounds and the like.
- polyisocyanate compound a prepolymer having an isocyanate group obtained by subjecting the above diisocyanate compound to an addition reaction with a polyhydric alcohol; a compound having an isocyanurate ring obtained by cyclotrimerization of the above diisocyanate compound; Polyisocyanate compounds having a urea bond or a biuret bond obtained by reacting the above diisocyanate compound with water; 2-isocyanatoethyl (meth) acrylate, 3-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate, (meth) acryloyl group Homopolymer of an acrylic monomer having an isocyanate group such as isocyanate; an acrylic monomer having the above-mentioned isocyanate group and other acrylic monomers, vinyl ester compounds, vinyl ether compounds, aromatic vinyl A copolymer having an isocyanate group obtained by copolymerizing with a monomer or a monomer such
- the above polyisocyanate compounds (B) can be used alone or in combination of two or more.
- the curing catalyst (C) will be described.
- the curing catalyst (C) include organotin compounds such as dibutyltin dioctoate, dibutyltin dilaurate, dioctyltin dilaurate, octyltin trilaurate, dioctyltin dineodecanate, dibutyltin diacetate, dioctyltin diacetate, tin dioctylate and the like; Organometallic compounds other than tin such as dibutyl titanium dichloride, tetrabutyl titanate, cobalt 2-ethylhexanoate, zinc 2-ethylhexanoate, bismuth 2-ethylhexanoate, zirconium naphthenate, lead naphthenate, etc .; triethylamine, triethylenediamine, Tertiary amine compounds such as diazabicycloundecene,
- organic tin compounds are preferable because the balance of pot life and curability is further improved.
- the polyisocyanate compound (B) in the curable resin composition of the present invention, since the balance of pot life and curability is further improved, the polyisocyanate compound
- the equivalent ratio (NCO / OH) of the isocyanate group (NCO) of (B) to the hydroxyl group (OH) of the copolymer (A) is preferably in the range of 0.2 to 2, preferably 0.5 to The range of 1.5 is more preferable.
- the content of the curing catalyst (C) in the curable resin composition of the present invention is 0. 0 to the copolymer (A) because the balance of pot life and curability is further improved.
- the range of 01 to 2% by mass is preferable, and the range of 0.02 to 1% by mass is more preferable.
- the curable resin composition of the present invention has a long pot life and can be suitably used as a coating because a cured coating film having excellent curability can be obtained even under ordinary temperature curing conditions.
- the paint of the present invention contains the curable resin composition of the present invention, but as other compounds, inorganic pigments, organic pigments, extender pigments, coloring pigments, high-brightness pigments, cellulose derivatives, waxes, surface active Agents, stabilizers, flow control agents, dyes, leveling agents, rheology control agents, ultraviolet absorbers, antioxidants, plasticizers, antistatic agents, antifoam agents, viscosity control agents, light stabilizers, weather stabilizers, heat resistance Stabilizers, pigment dispersants and the like can be used.
- the coating method of the paint of the present invention varies depending on the article to be coated, but, for example, a gravure coater, a roll coater, a comma coater, a knife coater, an air knife coater, a curtain coater, a kiss coater, a shower coater, a wheel coater, a spin coater, dipping, Methods such as screen printing, spray, applicator, bar coater, brush etc. may be mentioned.
- the paint of the present invention is preferably diluted with an organic solvent in order to adjust the viscosity to the above-mentioned coating method.
- organic solvent include aromatic hydrocarbon solvents such as toluene and xylene; methanol, ethanol, isopropanol, t-butanol, propylene glycol monomethyl ether, propylene glycol normal propyl ether, ethylene glycol monobutyl ether, diacetone alcohol and the like Alcohol solvents; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, normal propyl acetate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate and the like; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone etc. Be These solvents may be used alone or in combination of
- the paint of the present invention can impart a cured coating film excellent in appearance and various coating film properties to the surface of various articles.
- the paint of the present invention may be applied directly to an article to be coated, or a primer coating material compatible with the article to be coated may be applied and then the paint composition of the present invention may be applied.
- Materials of articles to be coated include various metals such as iron, copper, zinc, aluminum, magnesium and alloys thereof; polycarbonate, acrylonitrile-butadiene-styrene copolymer, polymer alloy of PC-ABS, polymethyl methacrylate And various plastics such as polyethylene terephthalate, polyamide and polypropylene, and fiber-reinforced plastics obtained by adding fillers such as glass fibers to these plastics; wood and the like.
- Articles having a cured coating film formed using the paint of the present invention include, for example, interior and exterior materials of various vehicles such as automobiles and railway cars; industrial machines, outer walls, roofs, glass, decorative panels, wooden floors, etc. Interior and exterior materials of buildings; Civil engineering members such as soundproof walls and drainage channels; Housings for home appliances such as TVs, refrigerators, washing machines, air conditioners; Electronic devices such as personal computers, smart phones, mobile phones, digital cameras, game machines
- the case includes a case of an OA device such as a printer and a facsimile.
- the acid value and the hydroxyl value of the copolymer are measured in accordance with JIS test method K 0070-1992, and the weight average molecular weight (Mw) is measured under the following GPC measurement conditions.
- Measuring device High-speed GPC device ("HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were used in series connection. "TSKgel G5000" (7.8 mm ID ⁇ 30 cm) ⁇ 1 "TSK gel G 4000” (7.8 mm ID ⁇ 30 cm) ⁇ 1 "TSK gel G 3000" (7.8 mm ID ⁇ 30 cm) ⁇ 1 This "TSKgel G2000" (7.8 mm ID ⁇ 30 cm) ⁇ 1 detector: RI (differential refractometer) Column temperature: 40 ° C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection volume: 100 ⁇ L (tetrahydrofuran solution with a sample concentration of 4 mg / mL) Standard sample: A calibration curve was prepared using the following monodispersed polystyrene.
- Synthesis Example 1 Synthesis of Copolymer (A-1) In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe, and a nitrogen gas inlet, 67 parts by mass of butyl acetate was charged, and the temperature was raised to 125 ° C. while stirring under a nitrogen atmosphere. Then, 30 parts by mass of styrene (hereinafter abbreviated as "St”), 10 parts by mass of methyl methacrylate (hereinafter abbreviated as "MMA”), and isobutyl methacrylate (hereinafter abbreviated as "IBMA”) 38.
- St styrene
- MMA methyl methacrylate
- IBMA isobutyl methacrylate
- Synthesis Example 2 Synthesis of Copolymer (A-2) In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe, and a nitrogen gas inlet, 67 parts by mass of butyl acetate was charged, and the temperature was raised to 125 ° C. while stirring under a nitrogen atmosphere. Then, 30 parts by mass of St, 10 parts by mass of MMA, 38.1 parts by mass of IBMA, 20 parts by mass of 2-HEMA, 1.5 parts by mass of monomethyl maleate (hereinafter abbreviated as "MMM”), and PO After 4 parts by mass of the mixture is added dropwise over 4 hours and allowed to react at 125 ° C.
- MMMM monomethyl maleate
- Synthesis Example 3 Synthesis of Copolymer (RA-1) In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe, and a nitrogen gas inlet, 67 parts by mass of butyl acetate was charged, and the temperature was raised to 125 ° C. while stirring under a nitrogen atmosphere. Subsequently, a mixture of 30 parts by mass of St, 10 parts by mass of MMA, 40 parts by mass of IBMA, 20 parts by mass of 2-HEMA, and 4 parts by mass of PO was dropped over 4 hours and reacted at 125 ° C.
- Synthesis Example 4 Synthesis of Copolymer (RA-2)
- a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe, and a nitrogen gas inlet 67 parts by mass of butyl acetate was charged, and the temperature was raised to 125 ° C. while stirring under a nitrogen atmosphere.
- 30 parts by weight of St 10 parts by weight of MMA, 39 parts by weight of IBMA, 20 parts by weight of 2-HEMA, 0.5 parts by weight of methacrylic acid (hereinafter abbreviated as "MAA"), and 4 parts by weight of PO
- MAA methacrylic acid
- Synthesis Example 5 Synthesis of Copolymer (RA-3)
- a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe, and a nitrogen gas inlet 67 parts by mass of butyl acetate was charged, and the temperature was raised to 125 ° C. while stirring under a nitrogen atmosphere.
- 30 parts by weight of St 10 parts by weight of MMA, 39 parts by weight of IBMA, 20 parts by weight of 2-HEMA, 2.8 parts by weight of methacrylic acid (hereinafter abbreviated as "MAA"), and 4 parts by weight of PO
- MAA methacrylic acid
- Synthesis Example 6 Synthesis of Copolymer (RA-4) In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe, and a nitrogen gas inlet, 67 parts by mass of butyl acetate was charged, and the temperature was raised to 125 ° C. while stirring under a nitrogen atmosphere. Then, a mixture of 30 parts by mass of St, 10 parts by mass of MMA, 39 parts by mass of IBMA, 20 parts by mass of 2-HEMA, 1 parts by mass of MAA and 4 parts by mass of PO is added dropwise over 4 hours. After reacting for time, butyl acetate was added to adjust the non-volatile content, and a 60% by mass solution of copolymer (RA-4) was obtained. The hydroxyl value of the copolymer (RA-4) was 80, the acid value was 6.8, and the weight average molecular weight was 11,000.
- Synthesis Example 7 Synthesis of Copolymer (RA-5) In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe, and a nitrogen gas inlet, 67 parts by mass of butyl acetate was charged, and the temperature was raised to 125 ° C. while stirring under a nitrogen atmosphere. Next, 30 parts by mass of St, 10 parts by mass of MMA, 39.2 parts by mass of IBMA, 20 parts by mass of 2-HEMA, 0.8 parts by mass of acrylic acid (hereinafter abbreviated as "AA”) and 4 parts by mass of PO Part 4 mixture is added dropwise over 4 hours, and allowed to react at 125 ° C.
- AA acrylic acid
- copolymer (RA-5) The hydroxyl value of the copolymer (RA-5) was 81, the acid value was 6.7, and the weight average molecular weight was 11,000.
- Example 1 Preparation and Evaluation of Paint (1) A polyisocyanate compound ("N3300" manufactured by Covestro Co., Ltd.) was added to 100 parts by mass (60 parts by mass as a copolymer (A-1)) of a 60% by mass solution of the copolymer (A-1) obtained in Synthesis Example 1.
- a polyisocyanate compound (“N3300” manufactured by Covestro Co., Ltd.) was added to 100 parts by mass (60 parts by mass as a copolymer (A-1)) of a 60% by mass solution of the copolymer (A-1) obtained in Synthesis Example 1.
- Example 2 Preparation and Evaluation of Paint (2) A paint (2) is prepared in the same manner as in Example 1 except that the copolymer (A-2) is used instead of the copolymer (A-1) used in Example 1, The time and the curability were evaluated.
- Table 1 shows the compositions and the evaluation results of the paints (1) to (2) and (R1) to (R5) obtained above.
- Comparative Examples 1 to 5 are examples of those having no structure derived from unsaturated dicarboxylic acid monoester (a1) in the copolymer, but it was confirmed that the usable time or the curability was insufficient. It was done.
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Abstract
Provided are a curable resin composition, a paint, and an article having a cured coating film of the paint, the curable resin composition being characterized by containing a copolymer (A) having a hydroxyl group, a polyisocyanate compound (B), and a curing catalyst (C), wherein the copolymer (A) has a structure derived from an unsaturated dicarboxylic acid monoester (a1). This curable resin composition may be suitably used for a paint and an article having a cured coating film of the paint because the composition has a long available time and excellent curability.
Description
本発明は、可使時間及び硬化性に優れる硬化性樹脂組成物、塗料、及び該塗料の硬化塗膜を有する物品に関する。
The present invention relates to a curable resin composition excellent in pot life and curability, a paint, and an article having a cured coating film of the paint.
従来、水酸基を有する樹脂とポリイソシアネ－ト化合物とを組み合わせた２液型ウレタン塗料は、自動車外装用、自動車補修用、プラスチック用、産業機械用、建材用等の各種用途に利用されている。これらの塗料では、可使時間と硬化性の両立が課題となっており、例えば、水酸基含有樹脂、ポリイソシアネ－ト化合物、有機錫化合物を含有する塗料組成物であって、該塗料中にリン酸基が存在する塗料組成物等が提案されている（例えば、特許文献１参照。）。
Heretofore, a two-component urethane paint in which a resin having a hydroxyl group and a polyisocyanate compound are combined is used in various applications such as automobile exteriors, automobile repair, plastics, industrial machines, building materials and the like. In these paints, coexistence of pot life and curability is an issue, and for example, a paint composition containing a hydroxyl group-containing resin, a polyisocyanate compound, and an organic tin compound, which contains phosphoric acid in the paint Coating compositions and the like in which groups are present have been proposed (see, for example, Patent Document 1).
しかしながら、この塗料組成物は、強制乾燥条件においては良好な硬化性を有するものの、常温硬化性が不十分であるという問題があった。そこで、可使時間が長く、常温硬化性にも優れる材料が求められていた。
However, although this paint composition has good curability under forced drying conditions, there is a problem that the room temperature curability is insufficient. Therefore, a material having a long pot life and excellent room temperature curability has been desired.
本発明が解決しようとする課題は、可使時間が長く、硬化性に優れる硬化性樹脂組成物、塗料、該塗料の硬化塗膜を有する物品を提供することである。
The problem to be solved by the present invention is to provide a curable resin composition having a long pot life and excellent curability, a paint, and an article having a cured coating film of the paint.
本発明者等は、上記課題を解決すべく鋭意研究を重ねた結果、特定の構造を有する共重合体、ポリイソシアネート化合物、及び硬化触媒を含有する硬化性樹脂組成物を用いることで、可使時間が長く、常温硬化条件下においても、硬化性に優れる硬化塗膜が得られることを見出し、本発明を完成した。
MEANS TO SOLVE THE PROBLEM As a result of repeating earnest research in order to solve the said subject, the present inventors are usable by using the curable resin composition containing the copolymer which has a specific structure, a polyisocyanate compound, and a curing catalyst. The inventors have found that a cured coating film excellent in curability can be obtained even under a long time and under room temperature curing conditions, and the present invention has been completed.
すなわち、本発明は、水酸基を有する共重合体（Ａ）、ポリイソシアネート化合物（Ｂ）、及び有機金属触媒（Ｃ）を含有する硬化性樹脂組成物であって、前記共重合体（Ａ）が、不飽和ジカルボン酸モノエステル（ａ１）由来の構造を有することを特徴とする硬化性樹脂組成物に関する。
That is, the present invention is a curable resin composition containing a copolymer (A) having a hydroxyl group, a polyisocyanate compound (B), and an organic metal catalyst (C), wherein the copolymer (A) is The present invention relates to a curable resin composition characterized by having a structure derived from unsaturated dicarboxylic acid monoester (a1).
本発明の硬化性樹脂組成物は、可使時間が長く、硬化性に優れることから、自動車外装用、自動車補修用、プラスチック用、産業機械用、建材用、木床用等の各種塗料に好適に用いることができる。
Since the curable resin composition of the present invention has a long working life and is excellent in curability, it is suitable for various coatings for automobile exteriors, automobile repair, plastics, industrial machines, building materials, wood floors, etc. It can be used for
本発明の硬化性樹脂組成物は、水酸基を有する共重合体（Ａ）、ポリイソシアネート化合物（Ｂ）、及び有機金属触媒（Ｃ）を含有する硬化性樹脂組成物であって、前記共重合体（Ａ）が、不飽和ジカルボン酸モノエステル（ａ１）由来の構造を有するものである。
The curable resin composition of the present invention is a curable resin composition comprising a copolymer (A) having a hydroxyl group, a polyisocyanate compound (B), and an organic metal catalyst (C), wherein the copolymer is (A) has a structure derived from unsaturated dicarboxylic acid monoester (a1).
まず、前記共重合体（Ａ）について説明する。この共重合体（Ａ）は、例えば、不飽和ジカルボン酸モノエステル（ａ１）、水酸基を有する単量体（ａ２）及びその他の単量体（ａ３）を共重合することにより得られる。
First, the copolymer (A) will be described. The copolymer (A) is obtained, for example, by copolymerizing an unsaturated dicarboxylic acid monoester (a1), a monomer having a hydroxyl group (a2), and another monomer (a3).
前記不飽和ジカルボン酸モノエステル（ａ１）としては、例えば、マレイン酸、イタコン酸、シトラコン酸、フマル酸等のジカルボン酸とアルコールとのモノエステルが挙げられるが、可使時間及び硬化性のバランスがより向上することから、マレイン酸モノエステルが好ましい。
Examples of the unsaturated dicarboxylic acid monoester (a1) include monoesters of dicarboxylic acids such as maleic acid, itaconic acid, citraconic acid and fumaric acid and alcohols, and the balance of pot life and curability is Maleic acid monoester is preferred because it improves more.
前記マレイン酸モノエステルとしては、可使時間及び硬化性のバランスがより向上することから、マレイン酸モノメチル、マレイン酸モノエチル、マレイン酸モノブチル、マレイン酸モノオクチル等のマレイン酸とアルキルアルコールとのモノエステルが好ましく、マレイン酸モノメチル、マレイン酸モノエチル、マレイン酸モノブチル等のマレイン酸と炭素原子数が１～４のアルキルアルコールとのモノエステルがより好ましい。
As the maleic acid monoester, a monoester of maleic acid such as monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate and the like with an improved balance of pot life and curability can be obtained. Are preferred, and monoesters of maleic acid such as monomethyl maleate, monoethyl maleate, monobutyl maleate and the like and an alkyl alcohol having 1 to 4 carbon atoms are more preferable.
前記水酸基を有する単量体（ａ２）としては、例えば、２－ヒドロキシエチル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシ－ｎ－ブチル（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、２－ヒドロキシ－ｎ－ブチル（メタ）アクリレート、３－ヒドロキシ－ｎ－ブチル（メタ）アクリレート、１，４－シクロヘキサンジメタノールモノ（メタ）アクリレート、グリセリンモノ（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、２－（メタ）アクリロイルオキシエチル－２－ヒドロキシエチルフタレート、末端に水酸基を有するラクトン変性（メタ）アクリレート等が挙げられる。
Examples of the hydroxyl group-containing monomer (a2) include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxy-n-butyl (meth) acrylate, 2-hydroxypropyl (for example) Meta) acrylate, 2-hydroxy-n-butyl (meth) acrylate, 3-hydroxy-n-butyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, glycerin mono (meth) acrylate, polyethylene glycol Mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, hydroxyl group at terminal Lactone-modified (meth) acrylate that.
前記その他の単量体（ａ３）としては、例えば、（メタ）アクリル酸、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（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（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、ｎ－ペンチル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート、ｎ－ヘプチル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、ドデシル（メタ）アクリレート、トリデシル（メタ）アクリレート、セチル（メタ）アクリレート、ステアリル（メタ）アクリレート、ベヘニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、４－ｔｅｒｔ－ブチルシクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ベンジル（メタ）アクリレート、アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、（メタ）アクリロニトリル、３－（メタ）アクリロイルプロピルトリメトキシシラン、Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、グリシジル（メタ）アクリレート、２－（メタ）アクリロイルオキシエチルアシッドホスフェート、スチレン、α－メチルスチレン、ｐ－メチルスチレン、ｐ－メトキシスチレン等が挙げられる。また、これらの単量体は、単独で用いることも２種以上併用することもできる。
Examples of the other monomer (a3) include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (for example, Meta) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate , Cyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, acrylamide, N, N-dimethyl (meth) acrylamide (Meth) acrylonitrile, 3- (meth) acryloylpropyltrimethoxysilane, N, N-dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, styrene, α- Methylstyrene, p-methylstyrene, p-methoxystyrene and the like can be mentioned. In addition, these monomers can be used alone or in combination of two or more.
なお、本発明において、「（メタ）アクリル酸」とは、メタクリル酸とアクリル酸の一方又は両方をいい、「（メタ）アクリレート」とは、メタクリレートとアクリレートの一方又は両方をいい、「（メタ）アクリロイル」とは、メタクリロイルとアクリロイルの一方又は両方をいう。
In the present invention, “(meth) acrylic acid” refers to one or both of methacrylic acid and acrylic acid, “(meth) acrylate” refers to one or both of methacrylate and acrylate, and “(meth) acrylic acid” The term "acryloyl" refers to one or both of methacryloyl and acryloyl.
前記不飽和ジカルボン酸モノエステル（ａ１）の使用量は、可使時間及び硬化性のバランスがより向上することから、前記共重合体（Ａ）の原料である単量体成分中の質量比率で、０．１～１０質量％の範囲が好ましく、０．１～５質量％の範囲がより好ましく、０．５～３質量％の範囲がさらに好ましい。
The amount of the unsaturated dicarboxylic acid monoester (a1) used is the mass ratio in the monomer component which is the raw material of the copolymer (A) because the balance of pot life and curability is further improved. The range of 0.1 to 10% by mass is preferable, the range of 0.1 to 5% by mass is more preferable, and the range of 0.5 to 3% by mass is more preferable.
前記水酸基を有する単量体（ａ２）の使用量は、硬化物の物性がより向上することから、前記共重合体（Ａ）の原料である単量体成分中の質量比率で、１～７０質量％の範囲が好ましく、５～６０質量％の範囲がより好ましく、１０～５０質量％の範囲がさらに好ましい。
The use amount of the monomer (a2) having a hydroxyl group is 1 to 70 as a mass ratio in the monomer component which is a raw material of the copolymer (A) since the physical properties of the cured product are further improved. The range of mass% is preferable, the range of 5 to 60 mass% is more preferable, and the range of 10 to 50 mass% is more preferable.
前記共重合体（Ａ）の製造方法としては、前記不飽和ジカルボン酸モノエステル（ａ１）、前記水酸基を有する単量体（ａ２）、前記その他の単量体（ａ３）を原料として、公知の重合方法で行うことができるが、溶液ラジカル重合法が最も簡便であることから好ましい。
As a method for producing the copolymer (A), the unsaturated dicarboxylic acid monoester (a1), the monomer having the hydroxyl group (a2), and the other monomer (a3) are known as raw materials. Although polymerization can be carried out, solution radical polymerization is preferable because it is the most simple.
上記の溶液ラジカル重合法は、原料である各単量体を溶剤に溶解し、重合開始剤存在下で重合反応を行う方法である。この際に用いることができる溶剤としては、例えば、トルエン、キシレン、シクロヘキサン、ｎ－ヘキサン、オクタン等の炭化水素系溶剤；メタノール、エタノール、ｉｓｏ－プロパノール、ｎ－ブタノール、ｉｓｏ－ブタノール、ｓｅｃ－ブタノール、エチレングリコールモノメチルエーテル等のアルコール系溶剤；酢酸メチル、酢酸エチル、酢酸ｎ－ブチル、酢酸イソブチル、酢酸アミル等のエステル系溶剤；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤などが挙げられる。これらの溶剤は、単独で用いることも２種以上併用することもできる。
The above-mentioned solution radical polymerization method is a method in which each monomer as a raw material is dissolved in a solvent and a polymerization reaction is performed in the presence of a polymerization initiator. Examples of the solvent that can be used at this time include hydrocarbon solvents such as toluene, xylene, cyclohexane, n-hexane and octane; methanol, ethanol, iso-propanol, n-butanol, iso-butanol and sec-butanol Alcohol solvents such as ethylene glycol monomethyl ether; ester solvents such as methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate and amyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone Be These solvents may be used alone or in combination of two or more.
前記アクリル樹脂（Ａ）の製造で用いる重合開始剤としては、例えば、２，２’－アゾビス（イソブチロニトリル）、２，２’－アゾビス（２－メチルブチロニトリル）、アゾビスシアノ吉草酸等のアゾ化合物；ｔｅｒｔ－ブチルパーオキシピバレート、ｔｅｒｔ－ブチルパーオキシベンゾエート、ｔｅｒｔ－ブチルパーオキシ－２－エチルヘキサノエート、ジ－ｔｅｒｔ－ブチルパーオキサイド、クメンハイドロパーオキサイド、ベンゾイルパーオキサイド、ｔｅｒｔ－ブチルハイドロパーオキサイド等の有機過酸化物；過酸化水素、過硫酸アンモニウム、過硫酸カリウム、過硫酸ナトリウム等の無機過酸化物などが挙げられる。これらの重合体開始剤は、単独で用いることも２種以上併用することもできる。また、前記重合開始剤は、前記共重合体（Ａ）の原料となる単量体の合計に対して、０．１～１０質量％の範囲内で使用することが好ましい。
As a polymerization initiator used in the production of the acrylic resin (A), for example, 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylbutyronitrile), azobiscyanovaleric acid, etc. Azo compounds of: tert-butyl peroxypivalate, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, di-tert-butyl peroxide, cumene hydroperoxide, benzoyl peroxide, tert Organic peroxides such as butyl hydroperoxide; and inorganic peroxides such as hydrogen peroxide, ammonium persulfate, potassium persulfate and sodium persulfate. These polymer initiators can be used alone or in combination of two or more. The polymerization initiator is preferably used in a range of 0.1 to 10% by mass with respect to the total of the monomers as the raw material of the copolymer (A).
また、前記重合開始剤とともに、必要に応じて、ラウリルメルカプタン、オクチルメルカプタン、２－メルカプトエタノール、チオグリコール酸オクチル、３－メルカプトプロピオン酸、α－メチルスチレン・ダイマー等の連鎖移動剤も用いることができる。
In addition to the polymerization initiator, if necessary, a chain transfer agent such as lauryl mercaptan, octyl mercaptan, 2-mercaptoethanol, octyl thioglycolate, 3-mercaptopropionic acid, α-methylstyrene dimer, etc. may be used. it can.
前記共重合体（Ａ）の酸価は、可使時間及び硬化性のバランスがより向上することから、０．４～４５ｍｇＫＯＨ／ｇの範囲が好ましく、０．４～２５ｍｇＫＯＨ／ｇの範囲がより好ましく、２～１５ｍｇＫＯＨ／ｇの範囲がさらに好ましい。
The acid value of the copolymer (A) is preferably in the range of 0.4 to 45 mg KOH / g, more preferably in the range of 0.4 to 25 mg KOH / g, because the balance of pot life and curability is further improved. Preferably, the range of 2 to 15 mg KOH / g is more preferred.
前記共重合体（Ａ）の水酸基価は、可使時間及び硬化性のバランスがより向上することから、４～３００ｍｇＫＯＨ／ｇの範囲が好ましく、２０～２６０ｍｇＫＯＨ／ｇの範囲がより好ましく、４０～２２０ｍｇＫＯＨ／ｇの範囲がさらに好ましい。
The hydroxyl value of the copolymer (A) is preferably in the range of 4 to 300 mg KOH / g, more preferably in the range of 20 to 260 mg KOH / g, since the balance of pot life and curability is further improved. A range of 220 mg KOH / g is more preferred.
なお、本発明における共重合体の酸価及び水酸基価は、ＪＩＳ試験方法Ｋ ００７０－１９９２に準拠して測定したものである。
The acid value and the hydroxyl value of the copolymer in the present invention are measured in accordance with JIS test method K 0070-1992.
前記共重合体（Ａ）の重量平均分子量（Ｍｗ）は、２，０００～１００，０００の範囲が好ましく、２，０００～５０，０００の範囲がより好ましく、２，０００～３０，０００の範囲がさらに好ましい。ここで、重量平均分子量（Ｍｗ）はゲル浸透クロマトグラフィー（以下、「ＧＰＣ」と略記する。）測定に基づきポリスチレン換算した値である
The weight average molecular weight (Mw) of the copolymer (A) is preferably in the range of 2,000 to 100,000, more preferably in the range of 2,000 to 50,000, and in the range of 2,000 to 30,000. Is more preferred. Here, the weight average molecular weight (Mw) is a value converted to polystyrene based on gel permeation chromatography (hereinafter abbreviated as "GPC") measurement.
前記ポリイソシアネート化合物（Ｂ）について説明する。前記ポリイソシアネート化合物（Ｂ）としては、例えば、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、ｍ－キシリレンジイソシアネート、ｍ－フェニレンビス（ジメチルメチレン）ジイソシアネート等の芳香族ジイソシアネート化合物；ヘキサメチレンジイソシアネート、リジンジイソシアネート、１，３－ビス（イソシアナトメチル）シクロヘキサン、２－メチル－１，３－ジイソシアナトシクロヘキサン、２－メチル－１，５－ジイソシアナトシクロヘキサン、４，４’－ジシクロヘキシルメタンジイソシアネート、イソホロンジイソシアネート等の脂肪族又は脂環式ジイソシアネート化合物などが挙げられる。
The said polyisocyanate compound (B) is demonstrated. Examples of the polyisocyanate compound (B) include aromatic diisocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, m-xylylene diisocyanate, m-phenylene bis (dimethyl methylene) diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, 1, Fats such as 3-bis (isocyanatomethyl) cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate And cycloaliphatic diisocyanate compounds and the like.
また、前記ポリイソシアネート化合物として、上記のジイソシアネート化合物を多価アルコールと付加反応させて得られるイソシアネート基を有するプレポリマー；上記のジイソシアネート化合物を環化三量化させて得られるイソシアヌレート環を有する化合物；上記のジイソシアネート化合物を水と反応させて得られる尿素結合やビュレット結合を有するポリイソシアネート化合物；２－イソシアナトエチル（メタ）アクリレート、３－イソプロペニル－α，α－ジメチルベンジルイソシアネート、（メタ）アクリロイルイソシアネート等のイソシアネート基を有するアクリル単量体の単独重合体；前記イソシアネート基を有するアクリル単量体と、その他のアクリル単量体、ビニルエステル化合物、ビニルエーテル化合物、芳香族ビニル単量体、フルオロオレフィン等の単量体と共重合することによって得られるイソシアネート基を有する共重合体なども用いることができる。
Further, as the polyisocyanate compound, a prepolymer having an isocyanate group obtained by subjecting the above diisocyanate compound to an addition reaction with a polyhydric alcohol; a compound having an isocyanurate ring obtained by cyclotrimerization of the above diisocyanate compound; Polyisocyanate compounds having a urea bond or a biuret bond obtained by reacting the above diisocyanate compound with water; 2-isocyanatoethyl (meth) acrylate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate, (meth) acryloyl group Homopolymer of an acrylic monomer having an isocyanate group such as isocyanate; an acrylic monomer having the above-mentioned isocyanate group and other acrylic monomers, vinyl ester compounds, vinyl ether compounds, aromatic vinyl A copolymer having an isocyanate group obtained by copolymerizing with a monomer or a monomer such as fluoroolefin can also be used.
上記のポリイソシアネート化合物（Ｂ）は、単独で用いることも２種以上併用することもできる。
The above polyisocyanate compounds (B) can be used alone or in combination of two or more.
前記硬化触媒（Ｃ）について説明する。前記硬化触媒（Ｃ）としては、例えば、ジブチル錫ジオクテート、ジブチル錫ジラウレート、ジオクチル錫ジラウレート、オクチル錫トリラウレート、ジオクチル錫ジネオデカネート、ジブチル錫ジアセテート、ジオクチル錫ジアセテート、ジオクチル酸錫等の有機錫化合物；ジブチルチタニウムジクロライド、テトラブチルチタネート、２－エチルヘキサン酸コバルト、２－エチルヘキサン酸亜鉛、２－エチルヘキサン酸ビスマス、ナフテン酸ジルコニウム、ナフテン酸鉛等の錫以外の有機金属化合物；トリエチルアミン、トリエチレンジアミン、ジアザビシクロウンデセン、Ｎ，Ｎ－ジメチルベンジルアミン、Ｎ－メチルモルホリン等の三級アミン化合物；トリオクチルメチルアンモニウム酢酸塩、テトラブチルアンモニウム酢酸塩、トリオクチルメチルアンモニウム炭酸塩、テトラメチルアンモニウム酢酸塩、トリエチルメチルアンモニウム－２－エチルヘキサン酸塩等の四級アンモニウム塩などが挙げられる。なお、これらの硬化触媒（Ｃ）は、単独で用いることも２種以上併用することもできる。
The curing catalyst (C) will be described. Examples of the curing catalyst (C) include organotin compounds such as dibutyltin dioctoate, dibutyltin dilaurate, dioctyltin dilaurate, octyltin trilaurate, dioctyltin dineodecanate, dibutyltin diacetate, dioctyltin diacetate, tin dioctylate and the like; Organometallic compounds other than tin such as dibutyl titanium dichloride, tetrabutyl titanate, cobalt 2-ethylhexanoate, zinc 2-ethylhexanoate, bismuth 2-ethylhexanoate, zirconium naphthenate, lead naphthenate, etc .; triethylamine, triethylenediamine, Tertiary amine compounds such as diazabicycloundecene, N, N-dimethylbenzylamine, N-methylmorpholine; trioctyl methyl ammonium acetate, tetrabutyl ammonium acetate, Octyl methyl ammonium carbonate, tetramethyl ammonium acetate, as quaternary ammonium salts such as triethylmethylammonium 2-ethylhexanoic acid salts. These curing catalysts (C) can be used alone or in combination of two or more.
前記硬化触媒（Ｃ）の中でも、可使時間及び硬化性のバランスがより向上することから有機錫化合物が好ましい。
Among the curing catalysts (C), organic tin compounds are preferable because the balance of pot life and curability is further improved.
本発明の硬化性樹脂組成物中の前記共重合体（Ａ）及び前記ポリイソシアネート化合物（Ｂ）の含有量としては、可使時間及び硬化性のバランスがより向上することから、前記ポリイソシアネート化合物（Ｂ）の有するイソシアネート基（ＮＣＯ）と前記共重合体（Ａ）の有する水酸基（ＯＨ）との当量比（ＮＣＯ／ＯＨ）が、０．２～２である範囲が好ましく、０．５～１．５である範囲がより好ましい。
With regard to the content of the copolymer (A) and the polyisocyanate compound (B) in the curable resin composition of the present invention, since the balance of pot life and curability is further improved, the polyisocyanate compound The equivalent ratio (NCO / OH) of the isocyanate group (NCO) of (B) to the hydroxyl group (OH) of the copolymer (A) is preferably in the range of 0.2 to 2, preferably 0.5 to The range of 1.5 is more preferable.
本発明の硬化性樹脂組成物中の前記硬化触媒（Ｃ）の含有量としては、可使時間及び硬化性のバランスがより向上することから、前記共重合体（Ａ）に対して、０．０１～２質量％の範囲が好ましく、０．０２～１質量％の範囲がより好ましい。
The content of the curing catalyst (C) in the curable resin composition of the present invention is 0. 0 to the copolymer (A) because the balance of pot life and curability is further improved. The range of 01 to 2% by mass is preferable, and the range of 0.02 to 1% by mass is more preferable.
本発明の硬化性樹脂組成物は、可使時間が長く、常温硬化条件下においても、硬化性に優れる硬化塗膜が得られることから、塗料に好適に用いることができる。
The curable resin composition of the present invention has a long pot life and can be suitably used as a coating because a cured coating film having excellent curability can be obtained even under ordinary temperature curing conditions.
本発明の塗料は、本発明の硬化性樹脂組成物を含有するものであるが、その他の配合物として、無機顔料、有機顔料、体質顔料、着色顔料、高輝顔料、セルロース誘導体、ワックス、界面活性剤、安定剤、流動調整剤、染料、レベリング剤、レオロジーコントロール剤、紫外線吸収剤、酸化防止剤、可塑剤、帯電防止剤、消泡剤、粘度調整剤、耐光安定剤、耐候安定剤、耐熱安定剤、顔料分散剤等を使用することができる。
The paint of the present invention contains the curable resin composition of the present invention, but as other compounds, inorganic pigments, organic pigments, extender pigments, coloring pigments, high-brightness pigments, cellulose derivatives, waxes, surface active Agents, stabilizers, flow control agents, dyes, leveling agents, rheology control agents, ultraviolet absorbers, antioxidants, plasticizers, antistatic agents, antifoam agents, viscosity control agents, light stabilizers, weather stabilizers, heat resistance Stabilizers, pigment dispersants and the like can be used.
本発明の塗料の塗装方法としては、塗装する物品により異なるが、例えば、グラビアコーター、ロールコーター、コンマコーター、ナイフコーター、エアナイフコーター、カーテンコーター、キスコーター、シャワーコーター、ホイーラーコーター、スピンコーター、ディッピング、スクリーン印刷、スプレー、アプリケーター、バーコーター、刷毛等の方法が挙げられる。
The coating method of the paint of the present invention varies depending on the article to be coated, but, for example, a gravure coater, a roll coater, a comma coater, a knife coater, an air knife coater, a curtain coater, a kiss coater, a shower coater, a wheel coater, a spin coater, dipping, Methods such as screen printing, spray, applicator, bar coater, brush etc. may be mentioned.
さらに、本発明の塗料は、上記の塗装方法に適した粘度に調整するため、有機溶剤で希釈することが好ましい。この有機溶剤としては、例えば、トルエン、キシレン等の芳香族炭化水素溶剤；メタノール、エタノール、イソプロパノール、ｔ－ブタノール、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ノルマルプロピルエーテル、エチレングリコールモノブチルエーテル、ダイアセトンアルコール等のアルコール溶剤；酢酸エチル、酢酸ブチル、酢酸イソブチル、酢酸ノルマルプロピル、プロピレングリコールモノメチルエーテルアセテート、３－エトキシプロピオン酸エチル等のエステル溶剤；メチルエチルケトン、メチルイソブチルケトン、ジイソブチルケトン、シクロヘキサノン等のケトン溶剤などが挙げられる。これらの溶剤は、単独で用いることも、２種以上を併用することもできる。
Furthermore, the paint of the present invention is preferably diluted with an organic solvent in order to adjust the viscosity to the above-mentioned coating method. Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene; methanol, ethanol, isopropanol, t-butanol, propylene glycol monomethyl ether, propylene glycol normal propyl ether, ethylene glycol monobutyl ether, diacetone alcohol and the like Alcohol solvents; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, normal propyl acetate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate and the like; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone etc. Be These solvents may be used alone or in combination of two or more.
本発明の塗料は、各種物品の表面に、外観及び各種塗膜物性に優れる硬化塗膜を付与することができる。
The paint of the present invention can impart a cured coating film excellent in appearance and various coating film properties to the surface of various articles.
本発明の塗料は、被塗装物となる物品に、直接塗装してもよいし、被塗装物に適合したプライマー塗材を塗装してから、本発明の塗料組成物を塗装してもよい。
The paint of the present invention may be applied directly to an article to be coated, or a primer coating material compatible with the article to be coated may be applied and then the paint composition of the present invention may be applied.
被塗装物となる物品の材質としては、鉄、銅、亜鉛、アルミニウム、マグネシウム等の各種金属及びこれらの合金；ポリカーボネート、アクリロニトリル－ブタジエン－スチレン共重合体、ＰＣ－ＡＢＳのポリマーアロイ、ポリメチルメタクリレート、ポリエチレンテレフタレート、ポリアミド、ポリプロピレン等の各種プラスチック及びこれらのプラスチックにガラス繊維等のフィラーを入れた繊維強化プラスチック；木材などが挙げられる。
Materials of articles to be coated include various metals such as iron, copper, zinc, aluminum, magnesium and alloys thereof; polycarbonate, acrylonitrile-butadiene-styrene copolymer, polymer alloy of PC-ABS, polymethyl methacrylate And various plastics such as polyethylene terephthalate, polyamide and polypropylene, and fiber-reinforced plastics obtained by adding fillers such as glass fibers to these plastics; wood and the like.
本発明の塗料を用いて形成された硬化塗膜を有する物品としては、例えば、自動車、鉄道車輌等の各種車輌の内外装材；産業機械、外壁、屋根、ガラス、化粧板、木床等の建築物の内外装材；防音壁、排水溝等の土木部材；テレビ、冷蔵庫、洗濯機、エアコン等の家電製品の筐体；パソコン、スマートフォン、携帯電話、デジタルカメラ、ゲーム機等の電子機器の筐体；プリンター、ファクシミリ等のＯＡ機器の筐体などが挙げられる。
Articles having a cured coating film formed using the paint of the present invention include, for example, interior and exterior materials of various vehicles such as automobiles and railway cars; industrial machines, outer walls, roofs, glass, decorative panels, wooden floors, etc. Interior and exterior materials of buildings; Civil engineering members such as soundproof walls and drainage channels; Housings for home appliances such as TVs, refrigerators, washing machines, air conditioners; Electronic devices such as personal computers, smart phones, mobile phones, digital cameras, game machines The case includes a case of an OA device such as a printer and a facsimile.
以下に本発明を具体的な実施例を挙げてより詳細に説明する。なお、共重合体の酸価及び水酸基価は、ＪＩＳ試験方法Ｋ ００７０－１９９２に準拠して測定したものであり、重量平均分子量（Ｍｗ）は、下記のＧＰＣ測定条件で測定したものである。
Hereinafter, the present invention will be described in more detail by way of specific examples. The acid value and the hydroxyl value of the copolymer are measured in accordance with JIS test method K 0070-1992, and the weight average molecular weight (Mw) is measured under the following GPC measurement conditions.
［ＧＰＣ測定条件］
測定装置：高速ＧＰＣ装置（東ソー株式会社製「ＨＬＣ－８２２０ＧＰＣ」）
カラム：東ソー株式会社製の下記のカラムを直列に接続して使用した。
「ＴＳＫｇｅｌ Ｇ５０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ４０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ３０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ２０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
検出器：ＲＩ（示差屈折計）
カラム温度：４０℃
溶離液：テトラヒドロフラン（ＴＨＦ）
流速：１．０ｍＬ／分
注入量：１００μＬ（試料濃度４ｍｇ／ｍＬのテトラヒドロフラン溶液）
標準試料：下記の単分散ポリスチレンを用いて検量線を作成した。 [GPC measurement conditions]
Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were used in series connection.
"TSKgel G5000" (7.8 mm ID × 30 cm) × 1 "TSK gel G 4000" (7.8 mm ID × 30 cm) × 1 "TSK gel G 3000" (7.8 mm ID × 30 cm) × 1 This "TSKgel G2000" (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 4 mg / mL)
Standard sample: A calibration curve was prepared using the following monodispersed polystyrene.
測定装置：高速ＧＰＣ装置（東ソー株式会社製「ＨＬＣ－８２２０ＧＰＣ」）
カラム：東ソー株式会社製の下記のカラムを直列に接続して使用した。
「ＴＳＫｇｅｌ Ｇ５０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ４０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ３０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ２０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
検出器：ＲＩ（示差屈折計）
カラム温度：４０℃
溶離液：テトラヒドロフラン（ＴＨＦ）
流速：１．０ｍＬ／分
注入量：１００μＬ（試料濃度４ｍｇ／ｍＬのテトラヒドロフラン溶液）
標準試料：下記の単分散ポリスチレンを用いて検量線を作成した。 [GPC measurement conditions]
Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were used in series connection.
"TSKgel G5000" (7.8 mm ID × 30 cm) × 1 "TSK gel G 4000" (7.8 mm ID × 30 cm) × 1 "TSK gel G 3000" (7.8 mm ID × 30 cm) × 1 This "TSKgel G2000" (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 4 mg / mL)
Standard sample: A calibration curve was prepared using the following monodispersed polystyrene.
（単分散ポリスチレン）
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－５００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－１０００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－２５００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－５０００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－１」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－２」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－４」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－１０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－２０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－４０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－８０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－１２８」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－２８８」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－５５０」 (Monodispersed polystyrene)
Tosoh Corporation "TSKgel standard polystyrene A-500"
Tosoh Corporation "TSKgel standard polystyrene A-1000"
Tosoh Corporation "TSKgel standard polystyrene A-2500"
Tosoh Corporation "TSKgel standard polystyrene A-5000"
Tosoh Corporation "TSKgel standard polystyrene F-1"
Tosoh Corporation "TSKgel standard polystyrene F-2"
Tosoh Corporation "TSKgel standard polystyrene F-4"
Tosoh Corporation "TSKgel standard polystyrene F-10"
Tosoh Corporation "TSKgel standard polystyrene F-20"
Tosoh Corporation "TSKgel standard polystyrene F-40"
Tosoh Corporation "TSKgel standard polystyrene F-80"
Tosoh Corporation "TSKgel standard polystyrene F-128"
Tosoh Corporation "TSKgel standard polystyrene F-288"
Tosoh Corporation "TSKgel standard polystyrene F-550"
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－５００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－１０００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－２５００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－５０００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－１」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－２」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－４」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－１０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－２０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－４０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－８０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－１２８」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－２８８」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－５５０」 (Monodispersed polystyrene)
Tosoh Corporation "TSKgel standard polystyrene A-500"
Tosoh Corporation "TSKgel standard polystyrene A-1000"
Tosoh Corporation "TSKgel standard polystyrene A-2500"
Tosoh Corporation "TSKgel standard polystyrene A-5000"
Tosoh Corporation "TSKgel standard polystyrene F-1"
Tosoh Corporation "TSKgel standard polystyrene F-2"
Tosoh Corporation "TSKgel standard polystyrene F-4"
Tosoh Corporation "TSKgel standard polystyrene F-10"
Tosoh Corporation "TSKgel standard polystyrene F-20"
Tosoh Corporation "TSKgel standard polystyrene F-40"
Tosoh Corporation "TSKgel standard polystyrene F-80"
Tosoh Corporation "TSKgel standard polystyrene F-128"
Tosoh Corporation "TSKgel standard polystyrene F-288"
Tosoh Corporation "TSKgel standard polystyrene F-550"
（合成例１：共重合体（Ａ－１）の合成）
攪拌機、温度計、滴下ロート、冷却管及び窒素ガス導入口を備えた反応容器に、酢酸ブチル６７質量部を仕込んで、窒素雰囲気下で、攪拌しながら、１２５℃まで昇温した。次いで、スチレン（以下、「Ｓｔ」と略記する。）３０質量部、メチルメタクリレート（以下、「ＭＭＡ」と略記する。）１０質量部、イソブチルメタクリレート（以下、「ＩＢＭＡ」と略記する。）３８．１質量部、２－ヒドロキシエチルメタクリレート（以下、「２－ＨＥＭＡ」と略記する。）２０質量部、マレイン酸モノブチル（以下、「ＭＢＭ」と略記する。）１．９質量部、及びｔｅｒｔ－ブチルパーオキシ－２－エチルヘキサノエート（以下、「Ｐ－Ｏ」と略記する。）４質量部の混合物を４時間かけて滴下し、１２５℃でさらに７時間反応させた後、不揮発分を調整するために酢酸ブチルを添加し、共重合体（Ａ－１）の６０質量％溶液を得た。この共重合体（Ａ－１）の水酸基価は８３、酸価は６．８、重量平均分子量は１１，０００であった。 Synthesis Example 1: Synthesis of Copolymer (A-1)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe, and a nitrogen gas inlet, 67 parts by mass of butyl acetate was charged, and the temperature was raised to 125 ° C. while stirring under a nitrogen atmosphere. Then, 30 parts by mass of styrene (hereinafter abbreviated as "St"), 10 parts by mass of methyl methacrylate (hereinafter abbreviated as "MMA"), and isobutyl methacrylate (hereinafter abbreviated as "IBMA") 38. 1 part by mass, 20 parts by mass of 2-hydroxyethyl methacrylate (hereinafter abbreviated as "2-HEMA"), 1.9 parts by mass of monobutyl maleate (hereinafter abbreviated as "MBM"), and tert-butyl A mixture of 4 parts by mass of peroxy-2-ethylhexanoate (hereinafter abbreviated as "PO") is added dropwise over 4 hours, allowed to react at 125 ° C for another 7 hours, and then the non-volatile matter is adjusted. Then, butyl acetate was added to obtain a 60% by mass solution of the copolymer (A-1). The hydroxyl value of the copolymer (A-1) was 83, the acid value was 6.8, and the weight average molecular weight was 11,000.
攪拌機、温度計、滴下ロート、冷却管及び窒素ガス導入口を備えた反応容器に、酢酸ブチル６７質量部を仕込んで、窒素雰囲気下で、攪拌しながら、１２５℃まで昇温した。次いで、スチレン（以下、「Ｓｔ」と略記する。）３０質量部、メチルメタクリレート（以下、「ＭＭＡ」と略記する。）１０質量部、イソブチルメタクリレート（以下、「ＩＢＭＡ」と略記する。）３８．１質量部、２－ヒドロキシエチルメタクリレート（以下、「２－ＨＥＭＡ」と略記する。）２０質量部、マレイン酸モノブチル（以下、「ＭＢＭ」と略記する。）１．９質量部、及びｔｅｒｔ－ブチルパーオキシ－２－エチルヘキサノエート（以下、「Ｐ－Ｏ」と略記する。）４質量部の混合物を４時間かけて滴下し、１２５℃でさらに７時間反応させた後、不揮発分を調整するために酢酸ブチルを添加し、共重合体（Ａ－１）の６０質量％溶液を得た。この共重合体（Ａ－１）の水酸基価は８３、酸価は６．８、重量平均分子量は１１，０００であった。 Synthesis Example 1: Synthesis of Copolymer (A-1)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe, and a nitrogen gas inlet, 67 parts by mass of butyl acetate was charged, and the temperature was raised to 125 ° C. while stirring under a nitrogen atmosphere. Then, 30 parts by mass of styrene (hereinafter abbreviated as "St"), 10 parts by mass of methyl methacrylate (hereinafter abbreviated as "MMA"), and isobutyl methacrylate (hereinafter abbreviated as "IBMA") 38. 1 part by mass, 20 parts by mass of 2-hydroxyethyl methacrylate (hereinafter abbreviated as "2-HEMA"), 1.9 parts by mass of monobutyl maleate (hereinafter abbreviated as "MBM"), and tert-butyl A mixture of 4 parts by mass of peroxy-2-ethylhexanoate (hereinafter abbreviated as "PO") is added dropwise over 4 hours, allowed to react at 125 ° C for another 7 hours, and then the non-volatile matter is adjusted. Then, butyl acetate was added to obtain a 60% by mass solution of the copolymer (A-1). The hydroxyl value of the copolymer (A-1) was 83, the acid value was 6.8, and the weight average molecular weight was 11,000.
（合成例２：共重合体（Ａ－２）の合成）
攪拌機、温度計、滴下ロート、冷却管及び窒素ガス導入口を備えた反応容器に、酢酸ブチル６７質量部を仕込んで、窒素雰囲気下で、攪拌しながら、１２５℃まで昇温した。次いで、Ｓｔ ３０質量部、ＭＭＡ １０質量部、ＩＢＭＡ ３８．１質量部、２－ＨＥＭＡ ２０質量部、マレイン酸モノメチル（以下、「ＭＭＭ」と略記する。）１．５質量部、及びＰ－Ｏ ４質量部の混合物を４時間かけて滴下し、１２５℃でさらに７時間反応させた後、不揮発分を調整するために酢酸ブチルを添加し、共重合体（Ａ－２）の６０質量％溶液を得た。この共重合体（Ａ－２）の水酸基価は８７、酸価は６．８、重量平均分子量は１１，０００であった。 Synthesis Example 2 Synthesis of Copolymer (A-2)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe, and a nitrogen gas inlet, 67 parts by mass of butyl acetate was charged, and the temperature was raised to 125 ° C. while stirring under a nitrogen atmosphere. Then, 30 parts by mass of St, 10 parts by mass of MMA, 38.1 parts by mass of IBMA, 20 parts by mass of 2-HEMA, 1.5 parts by mass of monomethyl maleate (hereinafter abbreviated as "MMM"), and PO After 4 parts by mass of the mixture is added dropwise over 4 hours and allowed to react at 125 ° C. for additional 7 hours, butyl acetate is added to adjust the nonvolatile content, and a 60% by mass solution of the copolymer (A-2) I got The hydroxyl value of the copolymer (A-2) was 87, the acid value was 6.8, and the weight average molecular weight was 11,000.
攪拌機、温度計、滴下ロート、冷却管及び窒素ガス導入口を備えた反応容器に、酢酸ブチル６７質量部を仕込んで、窒素雰囲気下で、攪拌しながら、１２５℃まで昇温した。次いで、Ｓｔ ３０質量部、ＭＭＡ １０質量部、ＩＢＭＡ ３８．１質量部、２－ＨＥＭＡ ２０質量部、マレイン酸モノメチル（以下、「ＭＭＭ」と略記する。）１．５質量部、及びＰ－Ｏ ４質量部の混合物を４時間かけて滴下し、１２５℃でさらに７時間反応させた後、不揮発分を調整するために酢酸ブチルを添加し、共重合体（Ａ－２）の６０質量％溶液を得た。この共重合体（Ａ－２）の水酸基価は８７、酸価は６．８、重量平均分子量は１１，０００であった。 Synthesis Example 2 Synthesis of Copolymer (A-2)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe, and a nitrogen gas inlet, 67 parts by mass of butyl acetate was charged, and the temperature was raised to 125 ° C. while stirring under a nitrogen atmosphere. Then, 30 parts by mass of St, 10 parts by mass of MMA, 38.1 parts by mass of IBMA, 20 parts by mass of 2-HEMA, 1.5 parts by mass of monomethyl maleate (hereinafter abbreviated as "MMM"), and PO After 4 parts by mass of the mixture is added dropwise over 4 hours and allowed to react at 125 ° C. for additional 7 hours, butyl acetate is added to adjust the nonvolatile content, and a 60% by mass solution of the copolymer (A-2) I got The hydroxyl value of the copolymer (A-2) was 87, the acid value was 6.8, and the weight average molecular weight was 11,000.
（合成例３：共重合体（ＲＡ－１）の合成）
攪拌機、温度計、滴下ロート、冷却管及び窒素ガス導入口を備えた反応容器に、酢酸ブチル６７質量部を仕込んで、窒素雰囲気下で、攪拌しながら、１２５℃まで昇温した。次いで、Ｓｔ ３０質量部、ＭＭＡ １０質量部、ＩＢＭＡ ４０質量部、２－ＨＥＭＡ ２０質量部、及びＰ－Ｏ ４質量部の混合物を４時間かけて滴下し、１２５℃でさらに７時間反応させた後、不揮発分を調整するために酢酸ブチルを添加し、共重合体（Ａ－２）の６０質量％溶液を得た。この共重合体（ＲＡ－１）の水酸基価は８５）、酸価は０．５、重量平均分子量は１１，００）であった。 Synthesis Example 3 Synthesis of Copolymer (RA-1)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe, and a nitrogen gas inlet, 67 parts by mass of butyl acetate was charged, and the temperature was raised to 125 ° C. while stirring under a nitrogen atmosphere. Subsequently, a mixture of 30 parts by mass of St, 10 parts by mass of MMA, 40 parts by mass of IBMA, 20 parts by mass of 2-HEMA, and 4 parts by mass of PO was dropped over 4 hours and reacted at 125 ° C. for another 7 hours Thereafter, butyl acetate was added to adjust the non-volatile content to obtain a 60% by mass solution of the copolymer (A-2). The hydroxyl value of this copolymer (RA-1) was 85), the acid value was 0.5, and the weight average molecular weight was 11,00).
攪拌機、温度計、滴下ロート、冷却管及び窒素ガス導入口を備えた反応容器に、酢酸ブチル６７質量部を仕込んで、窒素雰囲気下で、攪拌しながら、１２５℃まで昇温した。次いで、Ｓｔ ３０質量部、ＭＭＡ １０質量部、ＩＢＭＡ ４０質量部、２－ＨＥＭＡ ２０質量部、及びＰ－Ｏ ４質量部の混合物を４時間かけて滴下し、１２５℃でさらに７時間反応させた後、不揮発分を調整するために酢酸ブチルを添加し、共重合体（Ａ－２）の６０質量％溶液を得た。この共重合体（ＲＡ－１）の水酸基価は８５）、酸価は０．５、重量平均分子量は１１，００）であった。 Synthesis Example 3 Synthesis of Copolymer (RA-1)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe, and a nitrogen gas inlet, 67 parts by mass of butyl acetate was charged, and the temperature was raised to 125 ° C. while stirring under a nitrogen atmosphere. Subsequently, a mixture of 30 parts by mass of St, 10 parts by mass of MMA, 40 parts by mass of IBMA, 20 parts by mass of 2-HEMA, and 4 parts by mass of PO was dropped over 4 hours and reacted at 125 ° C. for another 7 hours Thereafter, butyl acetate was added to adjust the non-volatile content to obtain a 60% by mass solution of the copolymer (A-2). The hydroxyl value of this copolymer (RA-1) was 85), the acid value was 0.5, and the weight average molecular weight was 11,00).
（合成例４：共重合体（ＲＡ－２）の合成）
攪拌機、温度計、滴下ロート、冷却管及び窒素ガス導入口を備えた反応容器に、酢酸ブチル６７質量部を仕込んで、窒素雰囲気下で、攪拌しながら、１２５℃まで昇温した。次いで、Ｓｔ ３０質量部、ＭＭＡ １０質量部、ＩＢＭＡ ３９質量部、２－ＨＥＭＡ ２０質量部、メタクリル酸（以下、「ＭＡＡ」と略記する。）０．５質量部及びＰ－Ｏ ４質量部の混合物を４時間かけて滴下し、１２５℃でさらに７時間反応させた後、不揮発分を調整するために酢酸ブチルを添加し、共重合体（ＲＡ－２）の６０質量％溶液を得た。この共重合体（ＲＡ－２）の水酸基価は８７、酸価は３．８、重量平均分子量は１１，０００であった。 Synthesis Example 4 Synthesis of Copolymer (RA-2)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe, and a nitrogen gas inlet, 67 parts by mass of butyl acetate was charged, and the temperature was raised to 125 ° C. while stirring under a nitrogen atmosphere. Then, 30 parts by weight of St, 10 parts by weight of MMA, 39 parts by weight of IBMA, 20 parts by weight of 2-HEMA, 0.5 parts by weight of methacrylic acid (hereinafter abbreviated as "MAA"), and 4 parts by weight of PO The mixture was added dropwise over 4 hours, and allowed to react at 125 ° C. for additional 7 hours, and then butyl acetate was added to adjust the nonvolatile content to obtain a 60% by mass solution of the copolymer (RA-2). The hydroxy value of this copolymer (RA-2) was 87, the acid value was 3.8, and the weight average molecular weight was 11,000.
攪拌機、温度計、滴下ロート、冷却管及び窒素ガス導入口を備えた反応容器に、酢酸ブチル６７質量部を仕込んで、窒素雰囲気下で、攪拌しながら、１２５℃まで昇温した。次いで、Ｓｔ ３０質量部、ＭＭＡ １０質量部、ＩＢＭＡ ３９質量部、２－ＨＥＭＡ ２０質量部、メタクリル酸（以下、「ＭＡＡ」と略記する。）０．５質量部及びＰ－Ｏ ４質量部の混合物を４時間かけて滴下し、１２５℃でさらに７時間反応させた後、不揮発分を調整するために酢酸ブチルを添加し、共重合体（ＲＡ－２）の６０質量％溶液を得た。この共重合体（ＲＡ－２）の水酸基価は８７、酸価は３．８、重量平均分子量は１１，０００であった。 Synthesis Example 4 Synthesis of Copolymer (RA-2)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe, and a nitrogen gas inlet, 67 parts by mass of butyl acetate was charged, and the temperature was raised to 125 ° C. while stirring under a nitrogen atmosphere. Then, 30 parts by weight of St, 10 parts by weight of MMA, 39 parts by weight of IBMA, 20 parts by weight of 2-HEMA, 0.5 parts by weight of methacrylic acid (hereinafter abbreviated as "MAA"), and 4 parts by weight of PO The mixture was added dropwise over 4 hours, and allowed to react at 125 ° C. for additional 7 hours, and then butyl acetate was added to adjust the nonvolatile content to obtain a 60% by mass solution of the copolymer (RA-2). The hydroxy value of this copolymer (RA-2) was 87, the acid value was 3.8, and the weight average molecular weight was 11,000.
（合成例５：共重合体（ＲＡ－３）の合成）
攪拌機、温度計、滴下ロート、冷却管及び窒素ガス導入口を備えた反応容器に、酢酸ブチル６７質量部を仕込んで、窒素雰囲気下で、攪拌しながら、１２５℃まで昇温した。次いで、Ｓｔ ３０質量部、ＭＭＡ １０質量部、ＩＢＭＡ ３９質量部、２－ＨＥＭＡ ２０質量部、メタクリル酸（以下、「ＭＡＡ」と略記する。）２．８質量部及びＰ－Ｏ ４質量部の混合物を４時間かけて滴下し、１２５℃でさらに７時間反応させた後、不揮発分を調整するために酢酸ブチルを添加し、共重合体（ＲＡ－３）の６０質量％溶液を得た。この共重合体（ＲＡ－３）の水酸基価は８０、酸価は１８．１、重量平均分子量は１１，０００であった。 Synthesis Example 5 Synthesis of Copolymer (RA-3)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe, and a nitrogen gas inlet, 67 parts by mass of butyl acetate was charged, and the temperature was raised to 125 ° C. while stirring under a nitrogen atmosphere. Next, 30 parts by weight of St, 10 parts by weight of MMA, 39 parts by weight of IBMA, 20 parts by weight of 2-HEMA, 2.8 parts by weight of methacrylic acid (hereinafter abbreviated as "MAA"), and 4 parts by weight of PO The mixture was added dropwise over 4 hours, and allowed to react at 125 ° C. for additional 7 hours, and then butyl acetate was added to adjust the nonvolatile content to obtain a 60% by mass solution of copolymer (RA-3). The hydroxyl value of the copolymer (RA-3) was 80, the acid value was 18.1, and the weight average molecular weight was 11,000.
攪拌機、温度計、滴下ロート、冷却管及び窒素ガス導入口を備えた反応容器に、酢酸ブチル６７質量部を仕込んで、窒素雰囲気下で、攪拌しながら、１２５℃まで昇温した。次いで、Ｓｔ ３０質量部、ＭＭＡ １０質量部、ＩＢＭＡ ３９質量部、２－ＨＥＭＡ ２０質量部、メタクリル酸（以下、「ＭＡＡ」と略記する。）２．８質量部及びＰ－Ｏ ４質量部の混合物を４時間かけて滴下し、１２５℃でさらに７時間反応させた後、不揮発分を調整するために酢酸ブチルを添加し、共重合体（ＲＡ－３）の６０質量％溶液を得た。この共重合体（ＲＡ－３）の水酸基価は８０、酸価は１８．１、重量平均分子量は１１，０００であった。 Synthesis Example 5 Synthesis of Copolymer (RA-3)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe, and a nitrogen gas inlet, 67 parts by mass of butyl acetate was charged, and the temperature was raised to 125 ° C. while stirring under a nitrogen atmosphere. Next, 30 parts by weight of St, 10 parts by weight of MMA, 39 parts by weight of IBMA, 20 parts by weight of 2-HEMA, 2.8 parts by weight of methacrylic acid (hereinafter abbreviated as "MAA"), and 4 parts by weight of PO The mixture was added dropwise over 4 hours, and allowed to react at 125 ° C. for additional 7 hours, and then butyl acetate was added to adjust the nonvolatile content to obtain a 60% by mass solution of copolymer (RA-3). The hydroxyl value of the copolymer (RA-3) was 80, the acid value was 18.1, and the weight average molecular weight was 11,000.
（合成例６：共重合体（ＲＡ－４）の合成）
攪拌機、温度計、滴下ロート、冷却管及び窒素ガス導入口を備えた反応容器に、酢酸ブチル６７質量部を仕込んで、窒素雰囲気下で、攪拌しながら、１２５℃まで昇温した。次いで、Ｓｔ ３０質量部、ＭＭＡ １０質量部、ＩＢＭＡ ３９質量部、２－ＨＥＭＡ ２０質量部、ＭＡＡ １質量部及びＰ－Ｏ ４質量部の混合物を４時間かけて滴下し、１２５℃でさらに７時間反応させた後、不揮発分を調整するために酢酸ブチルを添加し、共重合体（ＲＡ－４）の６０質量％溶液を得た。この共重合体（ＲＡ－４）の水酸基価は８０、酸価は６．８、重量平均分子量は１１，０００であった。 Synthesis Example 6: Synthesis of Copolymer (RA-4)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe, and a nitrogen gas inlet, 67 parts by mass of butyl acetate was charged, and the temperature was raised to 125 ° C. while stirring under a nitrogen atmosphere. Then, a mixture of 30 parts by mass of St, 10 parts by mass of MMA, 39 parts by mass of IBMA, 20 parts by mass of 2-HEMA, 1 parts by mass of MAA and 4 parts by mass of PO is added dropwise over 4 hours. After reacting for time, butyl acetate was added to adjust the non-volatile content, and a 60% by mass solution of copolymer (RA-4) was obtained. The hydroxyl value of the copolymer (RA-4) was 80, the acid value was 6.8, and the weight average molecular weight was 11,000.
攪拌機、温度計、滴下ロート、冷却管及び窒素ガス導入口を備えた反応容器に、酢酸ブチル６７質量部を仕込んで、窒素雰囲気下で、攪拌しながら、１２５℃まで昇温した。次いで、Ｓｔ ３０質量部、ＭＭＡ １０質量部、ＩＢＭＡ ３９質量部、２－ＨＥＭＡ ２０質量部、ＭＡＡ １質量部及びＰ－Ｏ ４質量部の混合物を４時間かけて滴下し、１２５℃でさらに７時間反応させた後、不揮発分を調整するために酢酸ブチルを添加し、共重合体（ＲＡ－４）の６０質量％溶液を得た。この共重合体（ＲＡ－４）の水酸基価は８０、酸価は６．８、重量平均分子量は１１，０００であった。 Synthesis Example 6: Synthesis of Copolymer (RA-4)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe, and a nitrogen gas inlet, 67 parts by mass of butyl acetate was charged, and the temperature was raised to 125 ° C. while stirring under a nitrogen atmosphere. Then, a mixture of 30 parts by mass of St, 10 parts by mass of MMA, 39 parts by mass of IBMA, 20 parts by mass of 2-HEMA, 1 parts by mass of MAA and 4 parts by mass of PO is added dropwise over 4 hours. After reacting for time, butyl acetate was added to adjust the non-volatile content, and a 60% by mass solution of copolymer (RA-4) was obtained. The hydroxyl value of the copolymer (RA-4) was 80, the acid value was 6.8, and the weight average molecular weight was 11,000.
（合成例７：共重合体（ＲＡ－５）の合成）
攪拌機、温度計、滴下ロート、冷却管及び窒素ガス導入口を備えた反応容器に、酢酸ブチル６７質量部を仕込んで、窒素雰囲気下で、攪拌しながら、１２５℃まで昇温した。次いで、Ｓｔ ３０質量部、ＭＭＡ １０質量部、ＩＢＭＡ ３９．２質量部、２－ＨＥＭＡ ２０質量部、アクリル酸（以下、「ＡＡ」と略記する。）０．８質量部及びＰ－Ｏ ４質量部の混合物を４時間かけて滴下し、１２５℃でさらに７時間反応させた後、不揮発分を調整するために酢酸ブチルを添加し、共重合体（ＲＡ－５）の６０質量％溶液を得た。この共重合体（ＲＡ－５）の水酸基価は８１、酸価は６．７、重量平均分子量は１１，０００であった。 Synthesis Example 7: Synthesis of Copolymer (RA-5)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe, and a nitrogen gas inlet, 67 parts by mass of butyl acetate was charged, and the temperature was raised to 125 ° C. while stirring under a nitrogen atmosphere. Next, 30 parts by mass of St, 10 parts by mass of MMA, 39.2 parts by mass of IBMA, 20 parts by mass of 2-HEMA, 0.8 parts by mass of acrylic acid (hereinafter abbreviated as "AA") and 4 parts by mass of PO Part 4 mixture is added dropwise over 4 hours, and allowed to react at 125 ° C. for additional 7 hours, and then butyl acetate is added to adjust the nonvolatile content to obtain a 60% by mass solution of copolymer (RA-5) The The hydroxyl value of the copolymer (RA-5) was 81, the acid value was 6.7, and the weight average molecular weight was 11,000.
攪拌機、温度計、滴下ロート、冷却管及び窒素ガス導入口を備えた反応容器に、酢酸ブチル６７質量部を仕込んで、窒素雰囲気下で、攪拌しながら、１２５℃まで昇温した。次いで、Ｓｔ ３０質量部、ＭＭＡ １０質量部、ＩＢＭＡ ３９．２質量部、２－ＨＥＭＡ ２０質量部、アクリル酸（以下、「ＡＡ」と略記する。）０．８質量部及びＰ－Ｏ ４質量部の混合物を４時間かけて滴下し、１２５℃でさらに７時間反応させた後、不揮発分を調整するために酢酸ブチルを添加し、共重合体（ＲＡ－５）の６０質量％溶液を得た。この共重合体（ＲＡ－５）の水酸基価は８１、酸価は６．７、重量平均分子量は１１，０００であった。 Synthesis Example 7: Synthesis of Copolymer (RA-5)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe, and a nitrogen gas inlet, 67 parts by mass of butyl acetate was charged, and the temperature was raised to 125 ° C. while stirring under a nitrogen atmosphere. Next, 30 parts by mass of St, 10 parts by mass of MMA, 39.2 parts by mass of IBMA, 20 parts by mass of 2-HEMA, 0.8 parts by mass of acrylic acid (hereinafter abbreviated as "AA") and 4 parts by mass of PO Part 4 mixture is added dropwise over 4 hours, and allowed to react at 125 ° C. for additional 7 hours, and then butyl acetate is added to adjust the nonvolatile content to obtain a 60% by mass solution of copolymer (RA-5) The The hydroxyl value of the copolymer (RA-5) was 81, the acid value was 6.7, and the weight average molecular weight was 11,000.
（実施例１：塗料（１）の調製及び評価）
合成例１で得られた共重合体（Ａ－１）の６０質量％溶液１００質量部（共重合体（Ａ－１）として６０質量部）に、ポリイソシアネート化合物（コベストロ社製「Ｎ３３００」、ヘキサメチレンジイソシアヌレート型ポリイソシアネート）２２質量部、希釈シンナー（キシレン／酢酸ブチル／プロピレングリコールモノメチルエーテルアセテート／３－エトキシプロピオン酸エチル＝５／３／１／１（質量比））１０質量部、ジブチル錫ジラウレート０．２質量部を加えて、ディスパーで均一に混合し、塗料（１）を得た。 Example 1 Preparation and Evaluation of Paint (1)
A polyisocyanate compound ("N3300" manufactured by Covestro Co., Ltd.) was added to 100 parts by mass (60 parts by mass as a copolymer (A-1)) of a 60% by mass solution of the copolymer (A-1) obtained in Synthesis Example 1. 22 parts by mass of hexamethylenediisocyanurate type polyisocyanate, 10 parts by mass of diluted thinner (xylene / butyl acetate / propylene glycol monomethyl ether acetate / 3-ethyl ethyl ethoxyacetate = 5/3/1 (mass ratio)), 0.2 parts by mass of dibutyltin dilaurate was added and uniformly mixed with a disper to obtain a paint (1).
合成例１で得られた共重合体（Ａ－１）の６０質量％溶液１００質量部（共重合体（Ａ－１）として６０質量部）に、ポリイソシアネート化合物（コベストロ社製「Ｎ３３００」、ヘキサメチレンジイソシアヌレート型ポリイソシアネート）２２質量部、希釈シンナー（キシレン／酢酸ブチル／プロピレングリコールモノメチルエーテルアセテート／３－エトキシプロピオン酸エチル＝５／３／１／１（質量比））１０質量部、ジブチル錫ジラウレート０．２質量部を加えて、ディスパーで均一に混合し、塗料（１）を得た。 Example 1 Preparation and Evaluation of Paint (1)
A polyisocyanate compound ("N3300" manufactured by Covestro Co., Ltd.) was added to 100 parts by mass (60 parts by mass as a copolymer (A-1)) of a 60% by mass solution of the copolymer (A-1) obtained in Synthesis Example 1. 22 parts by mass of hexamethylenediisocyanurate type polyisocyanate, 10 parts by mass of diluted thinner (xylene / butyl acetate / propylene glycol monomethyl ether acetate / 3-ethyl ethyl ethoxyacetate = 5/3/1 (mass ratio)), 0.2 parts by mass of dibutyltin dilaurate was added and uniformly mixed with a disper to obtain a paint (1).
［可使時間の評価］
上記で得られた塗料（１）の２５℃での粘度をイワタカップ（ＮＫ－２）で測定した後、サンプル瓶に入れ、密封状態で２５℃の恒温槽に放置した。１時間後に恒温槽から取り出し、再び塗料の粘度を測定し、下記基準により可使時間を評価した。
○：粘度の変化率が３０％未満
△：粘度の変化率が３０％以上４０％未満
×：粘度の変化率が４０％以上 [Evaluation of pot life]
The viscosity at 25 ° C. of the paint (1) obtained above was measured with an Iwata cup (NK-2), placed in a sample bottle, and left in a thermostat at 25 ° C. in a sealed state. After 1 hour, it was removed from the thermostat, the viscosity of the paint was measured again, and the usable time was evaluated according to the following criteria.
○: change rate of viscosity is less than 30% Δ: change rate of viscosity is 30% or more and less than 40% ×: change rate of viscosity is 40% or more
上記で得られた塗料（１）の２５℃での粘度をイワタカップ（ＮＫ－２）で測定した後、サンプル瓶に入れ、密封状態で２５℃の恒温槽に放置した。１時間後に恒温槽から取り出し、再び塗料の粘度を測定し、下記基準により可使時間を評価した。
○：粘度の変化率が３０％未満
△：粘度の変化率が３０％以上４０％未満
×：粘度の変化率が４０％以上 [Evaluation of pot life]
The viscosity at 25 ° C. of the paint (1) obtained above was measured with an Iwata cup (NK-2), placed in a sample bottle, and left in a thermostat at 25 ° C. in a sealed state. After 1 hour, it was removed from the thermostat, the viscosity of the paint was measured again, and the usable time was evaluated according to the following criteria.
○: change rate of viscosity is less than 30% Δ: change rate of viscosity is 30% or more and less than 40% ×: change rate of viscosity is 40% or more
［硬化性の評価］
上記で得られた塗料（１）をポリプロピレン基材に乾燥後の膜厚が４０μｍとなるようにスプレー塗装した。その後、２５℃で１時間放置し、硬化塗膜を作製した。得られた硬化塗膜を基材から剥がして、５０ｍｍ×５０ｍｍの大きさに切断して秤量した後、アセトンに浸漬し、２４時間後に取り出した。取り出した硬化塗膜を１０８℃で１時間乾燥し、再び秤量した。硬化塗膜のアセトン浸漬前後の質量から、下式に従ってゲル分率を計算し、以下の基準により硬化性を評価した。
ゲル分率（％）＝（浸漬後の硬化塗膜質量）／（浸漬前の硬化塗膜質量）×１００
○：ゲル分率が８０％以上
△：ゲル分率が７５％以上８０％未満
×：ゲル分率が７５％未満 [Evaluation of curability]
The paint (1) obtained above was spray-coated on a polypropylene substrate such that the film thickness after drying was 40 μm. Thereafter, it was left at 25 ° C. for 1 hour to prepare a cured coating. The obtained cured coating was peeled from the substrate, cut into a size of 50 mm × 50 mm, weighed, immersed in acetone, and taken out after 24 hours. The cured film taken out was dried at 108 ° C. for 1 hour and weighed again. The gel fraction was calculated according to the following equation from the mass before and after immersion in acetone of the cured coating film, and the curability was evaluated according to the following criteria.
Gel fraction (%) = (weight of cured coating after immersion) / (weight of cured coating before immersion) × 100
○: gel fraction of 80% or more Δ: gel fraction of 75% to less than 80% ×: gel fraction of less than 75%
上記で得られた塗料（１）をポリプロピレン基材に乾燥後の膜厚が４０μｍとなるようにスプレー塗装した。その後、２５℃で１時間放置し、硬化塗膜を作製した。得られた硬化塗膜を基材から剥がして、５０ｍｍ×５０ｍｍの大きさに切断して秤量した後、アセトンに浸漬し、２４時間後に取り出した。取り出した硬化塗膜を１０８℃で１時間乾燥し、再び秤量した。硬化塗膜のアセトン浸漬前後の質量から、下式に従ってゲル分率を計算し、以下の基準により硬化性を評価した。
ゲル分率（％）＝（浸漬後の硬化塗膜質量）／（浸漬前の硬化塗膜質量）×１００
○：ゲル分率が８０％以上
△：ゲル分率が７５％以上８０％未満
×：ゲル分率が７５％未満 [Evaluation of curability]
The paint (1) obtained above was spray-coated on a polypropylene substrate such that the film thickness after drying was 40 μm. Thereafter, it was left at 25 ° C. for 1 hour to prepare a cured coating. The obtained cured coating was peeled from the substrate, cut into a size of 50 mm × 50 mm, weighed, immersed in acetone, and taken out after 24 hours. The cured film taken out was dried at 108 ° C. for 1 hour and weighed again. The gel fraction was calculated according to the following equation from the mass before and after immersion in acetone of the cured coating film, and the curability was evaluated according to the following criteria.
Gel fraction (%) = (weight of cured coating after immersion) / (weight of cured coating before immersion) × 100
○: gel fraction of 80% or more Δ: gel fraction of 75% to less than 80% ×: gel fraction of less than 75%
（実施例２：塗料（２）の調製及び評価）
実施例１で使用した共重合体（Ａ－１）の代わりに、共重合体（Ａ－２）を使用した以外は、実施例１と同様にして、塗料（２）を調製し、可使時間及び硬化性を評価した。 Example 2 Preparation and Evaluation of Paint (2)
A paint (2) is prepared in the same manner as in Example 1 except that the copolymer (A-2) is used instead of the copolymer (A-1) used in Example 1, The time and the curability were evaluated.
実施例１で使用した共重合体（Ａ－１）の代わりに、共重合体（Ａ－２）を使用した以外は、実施例１と同様にして、塗料（２）を調製し、可使時間及び硬化性を評価した。 Example 2 Preparation and Evaluation of Paint (2)
A paint (2) is prepared in the same manner as in Example 1 except that the copolymer (A-2) is used instead of the copolymer (A-1) used in Example 1, The time and the curability were evaluated.
（比較例１～５：塗料（Ｒ１）～（Ｒ５）の調製及び評価）
実施例１で使用した共重合体（Ａ－１）の代わりに、共重合体（ＲＡ－１）～（ＲＡ－５）を使用した以外は、実施例１と同様にして、塗料（ＲＡ－１）～（ＲＡ－５）を調製し、可使時間及び硬化性を評価した。 Comparative Examples 1 to 5 Preparation and Evaluation of Coatings (R1) to (R5)
A paint (RA-A) was prepared in the same manner as in Example 1, except that copolymers (RA-1) to (RA-5) were used instead of the copolymer (A-1) used in Example 1. 1) to (RA-5) were prepared, and their pot life and curability were evaluated.
実施例１で使用した共重合体（Ａ－１）の代わりに、共重合体（ＲＡ－１）～（ＲＡ－５）を使用した以外は、実施例１と同様にして、塗料（ＲＡ－１）～（ＲＡ－５）を調製し、可使時間及び硬化性を評価した。 Comparative Examples 1 to 5 Preparation and Evaluation of Coatings (R1) to (R5)
A paint (RA-A) was prepared in the same manner as in Example 1, except that copolymers (RA-1) to (RA-5) were used instead of the copolymer (A-1) used in Example 1. 1) to (RA-5) were prepared, and their pot life and curability were evaluated.
上記で得られた塗料（１）～（２）及び（Ｒ１）～（Ｒ５）の組成及び評価結果を表１に示す。
Table 1 shows the compositions and the evaluation results of the paints (1) to (2) and (R1) to (R5) obtained above.
実施例１及び２の評価結果から、本発明の硬化性樹脂組成物は、可使時間及び硬化性に優れることが確認された。
From the evaluation results of Examples 1 and 2, it was confirmed that the curable resin composition of the present invention is excellent in pot life and curability.
一方、比較例１～５は、共重合体中に、不飽和ジカルボン酸モノエステル（ａ１）由来の構造を有しないものの例であるが、可使時間又は硬化性が不十分であることが確認された。
On the other hand, Comparative Examples 1 to 5 are examples of those having no structure derived from unsaturated dicarboxylic acid monoester (a1) in the copolymer, but it was confirmed that the usable time or the curability was insufficient. It was done.
Claims (5)
- 水酸基を有する共重合体（Ａ）、ポリイソシアネート化合物（Ｂ）、及び硬化触媒（Ｃ）を含有する硬化性樹脂組成物であって、前記共重合体（Ａ）が、不飽和ジカルボン酸モノエステル（ａ１）由来の構造を有することを特徴とする硬化性樹脂組成物。 It is a curable resin composition containing the copolymer (A) which has a hydroxyl group, a polyisocyanate compound (B), and a curing catalyst (C), Comprising: The said copolymer (A) is unsaturated dicarboxylic acid monoester. (A1) A curable resin composition having a structure derived from (a1).
- 前記不飽和ジカルボン酸モノエステル（ａ１）が、マレイン酸モノエステルである請求項１記載の硬化性樹脂組成物。 The curable resin composition according to claim 1, wherein the unsaturated dicarboxylic acid monoester (a1) is a maleic acid monoester.
- 前記硬化触媒（Ｃ）が有機錫化合物である請求項１又は２記載の硬化性樹脂組成物。 The curable resin composition according to claim 1, wherein the curing catalyst (C) is an organotin compound.
- 請求項１～３いずれか１項記載の硬化性樹脂組成物を含有することを特徴とする塗料。 A paint comprising the curable resin composition according to any one of claims 1 to 3.
- 請求項４記載の塗料の硬化塗膜を有することを特徴とする物品。 An article having a cured coating of the paint according to claim 4.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017188184 | 2017-09-28 | ||
| JP2017-188184 | 2017-09-28 |
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| WO2019065571A1 true WO2019065571A1 (en) | 2019-04-04 |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/JP2018/035304 WO2019065571A1 (en) | 2017-09-28 | 2018-09-25 | Curable resin composition, paint, and article |
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| JPH10158311A (en) * | 1996-12-03 | 1998-06-16 | Dainippon Ink & Chem Inc | Non-aqueous dispersion type resin and resin composition for paint using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5187591A (en) * | 1974-12-20 | 1976-07-31 | Bayer Ag | Akurirujushino seizohoho |
| JPS58112073A (en) * | 1981-12-25 | 1983-07-04 | Dainippon Toryo Co Ltd | Automotive repair painting method |
| JPH04149287A (en) * | 1990-10-12 | 1992-05-22 | Dainippon Ink & Chem Inc | Top-coating method |
| JPH04317776A (en) * | 1991-04-16 | 1992-11-09 | Dainippon Ink & Chem Inc | Clear finish coating method for metal substrates |
| JPH0525420A (en) * | 1991-06-21 | 1993-02-02 | Asahi Chem Ind Co Ltd | Hydroxylated fluorocopolymer and coating composition containing the same as main component |
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| JP2008150521A (en) * | 2006-12-19 | 2008-07-03 | Toei Kasei Kk | Resins for paints, curable paints and painted products |
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