JP2015067740A - Polycarbonate modified acryl resin, coating material and plastic molded article coated by the coating material - Google Patents
Polycarbonate modified acryl resin, coating material and plastic molded article coated by the coating material Download PDFInfo
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- JP2015067740A JP2015067740A JP2013203980A JP2013203980A JP2015067740A JP 2015067740 A JP2015067740 A JP 2015067740A JP 2013203980 A JP2013203980 A JP 2013203980A JP 2013203980 A JP2013203980 A JP 2013203980A JP 2015067740 A JP2015067740 A JP 2015067740A
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- parts
- unsaturated monomer
- weight
- polycarbonate
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 44
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 43
- 239000011347 resin Substances 0.000 title claims abstract description 31
- 229920005989 resin Polymers 0.000 title claims abstract description 31
- 239000004033 plastic Substances 0.000 title claims abstract description 15
- 229920003023 plastic Polymers 0.000 title claims abstract description 15
- 238000000576 coating method Methods 0.000 title abstract description 49
- 239000011248 coating agent Substances 0.000 title abstract description 47
- -1 acryl Chemical class 0.000 title abstract description 35
- 239000000463 material Substances 0.000 title abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 71
- 150000002009 diols Chemical class 0.000 claims abstract description 49
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 28
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 24
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 20
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims abstract description 9
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Polymers C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 58
- 239000004925 Acrylic resin Substances 0.000 claims description 46
- 239000003973 paint Substances 0.000 claims description 26
- 229920000178 Acrylic resin Polymers 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 35
- 239000000758 substrate Substances 0.000 abstract description 7
- 229940035437 1,3-propanediol Drugs 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 48
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 46
- 230000000052 comparative effect Effects 0.000 description 29
- 239000000243 solution Substances 0.000 description 22
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 19
- 238000011156 evaluation Methods 0.000 description 19
- 239000004793 Polystyrene Substances 0.000 description 17
- 229920002223 polystyrene Polymers 0.000 description 17
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 15
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- 238000001816 cooling Methods 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- 238000013461 design Methods 0.000 description 13
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 description 12
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 12
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000005056 polyisocyanate Substances 0.000 description 9
- 229920001228 polyisocyanate Polymers 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 230000035807 sensation Effects 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 208000032544 Cicatrix Diseases 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- AQHHHDLHHXJYJD-UHFFFAOYSA-N propranolol Chemical compound C1=CC=C2C(OCC(O)CNC(C)C)=CC=CC2=C1 AQHHHDLHHXJYJD-UHFFFAOYSA-N 0.000 description 4
- 231100000241 scar Toxicity 0.000 description 4
- 230000037387 scars Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- MYOQALXKVOJACM-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy pentaneperoxoate Chemical compound CCCCC(=O)OOOC(C)(C)C MYOQALXKVOJACM-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- OHTRJOZKRSVAOX-UHFFFAOYSA-N 1,3-diisocyanato-2-methylcyclohexane Chemical compound CC1C(N=C=O)CCCC1N=C=O OHTRJOZKRSVAOX-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- ZVEMLYIXBCTVOF-UHFFFAOYSA-N 1-(2-isocyanatopropan-2-yl)-3-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC(C(C)(C)N=C=O)=C1 ZVEMLYIXBCTVOF-UHFFFAOYSA-N 0.000 description 1
- NQUXRXBRYDZZDL-UHFFFAOYSA-N 1-(2-prop-2-enoyloxyethyl)cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1(CCOC(=O)C=C)C(O)=O NQUXRXBRYDZZDL-UHFFFAOYSA-N 0.000 description 1
- OSNILPMOSNGHLC-UHFFFAOYSA-N 1-[4-methoxy-3-(piperidin-1-ylmethyl)phenyl]ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1CN1CCCCC1 OSNILPMOSNGHLC-UHFFFAOYSA-N 0.000 description 1
- CDDDRVNOHLVEED-UHFFFAOYSA-N 1-cyclohexyl-3-[1-[[1-(cyclohexylcarbamoylamino)cyclohexyl]diazenyl]cyclohexyl]urea Chemical compound C1CCCCC1(N=NC1(CCCCC1)NC(=O)NC1CCCCC1)NC(=O)NC1CCCCC1 CDDDRVNOHLVEED-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- CWJHMZONBMHMEI-UHFFFAOYSA-N 1-tert-butylperoxy-3-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC(OOC(C)(C)C)=C1 CWJHMZONBMHMEI-UHFFFAOYSA-N 0.000 description 1
- VZDIRINETBAVAV-UHFFFAOYSA-N 2,4-diisocyanato-1-methylcyclohexane Chemical compound CC1CCC(N=C=O)CC1N=C=O VZDIRINETBAVAV-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- JGBAASVQPMTVHO-UHFFFAOYSA-N 2,5-dihydroperoxy-2,5-dimethylhexane Chemical compound OOC(C)(C)CCC(C)(C)OO JGBAASVQPMTVHO-UHFFFAOYSA-N 0.000 description 1
- OSXPVFSMSBQPBU-UHFFFAOYSA-N 2-(2-carboxyethoxycarbonyl)benzoic acid Chemical compound OC(=O)CCOC(=O)C1=CC=CC=C1C(O)=O OSXPVFSMSBQPBU-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- PMAAOHONJPSASX-UHFFFAOYSA-N 2-butylperoxypropan-2-ylbenzene Chemical compound CCCCOOC(C)(C)C1=CC=CC=C1 PMAAOHONJPSASX-UHFFFAOYSA-N 0.000 description 1
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 1
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- UZDMJPAQQFSMMV-UHFFFAOYSA-N 4-oxo-4-(2-prop-2-enoyloxyethoxy)butanoic acid Chemical compound OC(=O)CCC(=O)OCCOC(=O)C=C UZDMJPAQQFSMMV-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical class C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 101000642333 Homo sapiens Survival of motor neuron-related-splicing factor 30 Proteins 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N Hydrocyanic acid Natural products N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 101710148027 Ribulose bisphosphate carboxylase/oxygenase activase 1, chloroplastic Proteins 0.000 description 1
- 101710201629 Ribulose bisphosphate carboxylase/oxygenase activase 2, chloroplastic Proteins 0.000 description 1
- 102100036412 Survival of motor neuron-related-splicing factor 30 Human genes 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Laminated Bodies (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、プラスチック基材との高い付着性を有し、耐擦傷性、耐薬品性及び触感に優れる塗膜が得られるポリカーボネート変性アクリル樹脂、塗料及び該塗料で塗装されたプラスチック成形品に関する。 The present invention relates to a polycarbonate-modified acrylic resin, a paint, and a plastic molded article coated with the paint, which have a high adhesion to a plastic substrate and provide a coating film excellent in scratch resistance, chemical resistance and touch.
従来において、ポリオール存在下、アクリル酸エステルを反応させることで得られるアクリル変性ポリオールが提案されており、その硬化塗膜は機械物性、柔軟性、耐久性に優れることが知られている（例えば、特許文献１照。）。 Conventionally, an acrylic modified polyol obtained by reacting an acrylate ester in the presence of a polyol has been proposed, and the cured coating film is known to have excellent mechanical properties, flexibility, and durability (for example, Patent Document 1).
しかしながら、このアクリル変性ポリオールから得られる塗膜は、機械物性等に優れるものの、近年、プラスチック用塗料等で要求される耐薬品性が不十分であるという欠点があった。そこで、プラスチック成形品の表面に優れた機械物性、耐薬品性及び触感を付与することができる材料が求められていた。 However, although the coating film obtained from this acrylic-modified polyol is excellent in mechanical properties and the like, there has been a drawback in recent years that chemical resistance required for plastic coatings and the like is insufficient. Therefore, a material capable of imparting excellent mechanical properties, chemical resistance and tactile sensation to the surface of a plastic molded product has been demanded.
本発明が解決しようとする課題は、プラスチック基材との高い付着性を有し、耐擦傷性、耐薬品性及び触感に優れる塗膜を得ることができるアクリル樹脂、塗料及び該塗料で塗装されたプラスチック成形品を提供することである。 The problem to be solved by the present invention is that an acrylic resin, a paint, and a paint that have a high adhesion to a plastic substrate and can provide a coating film excellent in scratch resistance, chemical resistance, and tactile sensation. Is to provide a plastic molded product.
本発明者等は、上記の課題を解決するため鋭意研究した結果、特定のポリカーボネートジオールの存在下、特定の不飽和単量体を必須成分として含有する不飽和単量体混合物を重合反応させて得られる特定のポリカーボネート変性アクリル樹脂を用いることで、プラスチック基材との高い付着性を有し、耐擦傷性、耐薬品性及び触感に優れる塗膜を得ることができることを見出し、発明を完成させた。 As a result of diligent research to solve the above problems, the present inventors polymerized an unsaturated monomer mixture containing a specific unsaturated monomer as an essential component in the presence of a specific polycarbonate diol. By using the specific polycarbonate-modified acrylic resin obtained, it has been found that a coating film having high adhesion to a plastic substrate and excellent in scratch resistance, chemical resistance and tactile sensation can be obtained, and the invention has been completed. It was.
すなわち、本発明は、１，３−プロパンジオール及び１，４−ブタンジオールを用いて得られるポリカーボネートジオール（Ａ）の存在下、メチルメタクリレート、水酸基を有する不飽和単量体（ｂ１）、カルボキシル基を有する不飽和単量体（ｂ２）及び炭素原子数が２〜８のアルキル基を有する不飽和単量体（ｂ３）を必須成分として含有する不飽和単量体混合物（Ｂ）を反応させて得られるポリカーボネート変性アクリル樹脂であって、前記不飽和単量体混合物（Ｂ）中の前記不飽和単量体（ｂ２）の質量比率が０．１〜１．６質量％の範囲であることを特徴とするポリカーボネート変性アクリル樹脂、塗料及び該塗料で塗装されたプラスチック成形品に関する。 That is, the present invention provides methyl methacrylate, an unsaturated monomer having a hydroxyl group (b1), a carboxyl group in the presence of polycarbonate diol (A) obtained using 1,3-propanediol and 1,4-butanediol. And an unsaturated monomer mixture (B) containing as an essential component an unsaturated monomer (b2) having an alkyl group and an unsaturated monomer (b3) having an alkyl group having 2 to 8 carbon atoms. It is a polycarbonate modified acrylic resin obtained, Comprising: The mass ratio of the said unsaturated monomer (b2) in the said unsaturated monomer mixture (B) is the range of 0.1-1.6 mass%. The present invention relates to a polycarbonate-modified acrylic resin, a paint, and a plastic molded article coated with the paint.
本発明のポリカーボネート変性アクリル樹脂は、プラスチック基材との高い付着性を有し、耐擦傷性、耐薬品性及び触感に優れる塗膜を得られることから、塗料に有用であり、該塗料を各種プラスチック成形品に塗装することができる。したがって、本発明のポリカーボネート変性アクリル樹脂は、携帯電話、スマートフォン、タブレット端末、パソコン、デジタルカメラ、ゲーム機等の電子機器の筐体；テレビ、冷蔵庫、洗濯機、エアコン等の家電製品の筐体；自動車、鉄道車輌等の各種車輌の内装材；浴槽、釣り具などの各種物品を塗装する塗料に好適に用いることができる。 The polycarbonate-modified acrylic resin of the present invention has high adhesion to a plastic substrate, and is useful for paints because it can provide a coating film excellent in scratch resistance, chemical resistance and tactile sensation. Can be painted on plastic moldings. Therefore, the polycarbonate-modified acrylic resin of the present invention is used in a casing of an electronic device such as a mobile phone, a smartphone, a tablet terminal, a personal computer, a digital camera, or a game machine; It can be suitably used for interior materials of various vehicles such as automobiles and railway vehicles; paints for coating various articles such as bathtubs and fishing gears.
本発明のポリカーボネート変性アクリル樹脂は、１，３−プロパンジオール及び１，４−ブタンジオールを用いて得られるポリカーボネートジオール（Ａ）の存在下、メチルメタクリレート、水酸基を有する不飽和単量体（ｂ１）、カルボキシル基を有する不飽和単量体（ｂ２）及び炭素原子数が２〜８のアルキル基を有する不飽和単量体（ｂ３）を必須成分として含有する不飽和単量体混合物（Ｂ）を反応させて得られるポリカーボネート変性アクリル樹脂であって、前記不飽和単量体混合物（Ｂ）中の前記不飽和単量体（ｂ２）の質量比率が０．１〜１．６質量％の範囲であるものである。 The polycarbonate-modified acrylic resin of the present invention is an unsaturated monomer (b1) having a methyl methacrylate and a hydroxyl group in the presence of a polycarbonate diol (A) obtained using 1,3-propanediol and 1,4-butanediol. An unsaturated monomer mixture (B) containing, as essential components, an unsaturated monomer (b2) having a carboxyl group and an unsaturated monomer (b3) having an alkyl group having 2 to 8 carbon atoms A polycarbonate-modified acrylic resin obtained by reaction, wherein the unsaturated monomer (b2) in the unsaturated monomer mixture (B) has a mass ratio of 0.1 to 1.6% by mass. There is something.
まず、ポリカーボネートジオール（Ａ）について説明する。このポリカーボネートジオール（Ａ）は、１，３−プロパンジオール及び１，４−ブタンジオールを用いて得られるポリカーボネートジオールであり、例えば、１，３−プロパンジオール及び１，４−ブタンジオールと、炭酸エステルまたはホスゲンとの反応により得られるものである。 First, the polycarbonate diol (A) will be described. This polycarbonate diol (A) is a polycarbonate diol obtained by using 1,3-propanediol and 1,4-butanediol. For example, 1,3-propanediol and 1,4-butanediol, and carbonate ester Or it is obtained by reaction with phosgene.
次に、前記不飽和単量体混合物（Ｂ）について説明する。この不飽和単量体混合物（Ｂ）は、メチルメタクリレート、水酸基を有する不飽和単量体（ｂ１）、カルボキシル基を有する不飽和単量体（ｂ２）及び炭素原子数が２〜８のアルキル基を有する不飽和単量体（ｂ３）を必須成分として含有するものであり、前記不飽和単量体（ｂ２）の質量比率が０．１〜１．６質量％の範囲のものである。 Next, the unsaturated monomer mixture (B) will be described. This unsaturated monomer mixture (B) includes methyl methacrylate, an unsaturated monomer having a hydroxyl group (b1), an unsaturated monomer having a carboxyl group (b2), and an alkyl group having 2 to 8 carbon atoms. The unsaturated monomer (b3) having an essential component is contained as an essential component, and the mass ratio of the unsaturated monomer (b2) is in the range of 0.1 to 1.6% by mass.
前記水酸基を有する不飽和単量体（ｂ１）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、ポリオキシエチレンモノ（メタ）アクリレート、ポリオキシプロピレンモノ（メタ）アクリレート、ポリオキシブチレンモノ（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、ポリカプロラクトン変性ヒドロキシエチルモノ（メタ）アクリレートなどが挙げられる。これらの中でも、得られる塗膜の外観、耐薬品性、耐擦傷性が優れることから、２−ヒドロキシエチル（メタ）アクリレートが好ましい。なお、これらの不飽和単量体（ｂ１）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 unsaturated monomer (b1) having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxy-n-butyl (meth) acrylate, and 2-hydroxy. Propyl (meth) acrylate, 2-hydroxy-n-butyl (meth) acrylate, 3-hydroxy-n-butyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, glycerin mono (meth) acrylate, Polyoxyethylene mono (meth) acrylate, polyoxypropylene mono (meth) acrylate, polyoxybutylene mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2 -Hide Carboxyethyl phthalate, and polycaprolactone-modified hydroxyethyl mono (meth) acrylate. Among these, 2-hydroxyethyl (meth) acrylate is preferable because the resulting coating film has excellent appearance, chemical resistance and scratch resistance. These unsaturated monomers (b1) 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）アクリロイル基」とは、メタクリロイル基とアクリロイル基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 “(meta) The “) acryloyl group” means one or both of a methacryloyl group and an acryloyl group.
前記カルボキシル基を有する不飽和単量体（ｂ２）としては、例えば、（メタ）アクリル酸、クロトン酸、β−カルボキシエチル（メタ）アクリレート、ω−カルボキシ−ポリカプロラクトンモノ（メタ）アクリレート、２−（メタ）アクリロイルオキシエチルサクシネート、２−（メタ）アクリロイルオキシエチルヘキサヒドロフタル酸等の不飽和モノカルボン酸；マレイン酸、フマル酸、イタコン酸等の不飽和ジカルボン酸又はこれら不飽和ジカルボン酸のハーフエステルなどが挙げられる。これらの中でも、得られる塗膜の耐擦傷性が優れることから、（メタ）アクリル酸が好ましい。また、これらの不飽和単量体（ｂ２）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 unsaturated monomer (b2) having a carboxyl group include (meth) acrylic acid, crotonic acid, β-carboxyethyl (meth) acrylate, ω-carboxy-polycaprolactone mono (meth) acrylate, 2- Unsaturated monocarboxylic acids such as (meth) acryloyloxyethyl succinate and 2- (meth) acryloyloxyethyl hexahydrophthalic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, or unsaturated dicarboxylic acids Examples include half esters. Among these, (meth) acrylic acid is preferable because the resulting coating film has excellent scratch resistance. Moreover, these unsaturated monomers (b2) can be used alone or in combination of two or more.
前記炭素原子数が２〜８のアルキル基を有する不飽和単量体（ｂ３）としては、例えば、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、シクロヘキシル（メタ）アクリレート等が挙げられる。これらの中でも、得られる塗膜の耐薬品性及び耐擦傷性が向上することから、シクロヘキシル（メタ）アクリレートが好ましい。また、これらの不飽和単量体（ｂ３）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 unsaturated monomer (b3) having an alkyl group having 2 to 8 carbon atoms include ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl ( (Meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, Examples include 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate. Among these, cyclohexyl (meth) acrylate is preferable because chemical resistance and scratch resistance of the obtained coating film are improved. Moreover, these unsaturated monomers (b3) can be used alone or in combination of two or more.
さらに、前記不飽和単量体混合物（Ｂ）の成分として、上記の必須原料であるメチルメタクリレート、不飽和単量体（ｂ１）、不飽和単量体（ｂ２）、及び不飽和単量体（ｂ３）以外のその他の単量体（ｂ４）を用いても構わない。その他の単量体（ｂ４）としては、例えば、メチルアクリレート、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、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）アクリロイルオキシ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、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、グリシジル（メタ）アクリレート、酢酸ビニル、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、エチレングリコールジアクリレート等のジアクリレート化合物などが挙げられる。また、これらの不飽和単量体は、単独で用いることも２種以上併用することもできる。 Furthermore, as the component of the unsaturated monomer mixture (B), methyl methacrylate, the unsaturated monomer (b1), the unsaturated monomer (b2), and the unsaturated monomer ( Other monomers (b4) other than b3) may be used. Examples of other monomers (b4) include methyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, and stearyl (meth). Acrylate, behenyl (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) acryloyloxypropyltrimethoxysilane, N, N-dimethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl acid phos Eto, glycidyl (meth) acrylate, vinyl acetate, styrene, alpha-methyl styrene, p- methyl styrene, p- methoxy styrene, such as diacrylate compounds such as ethylene glycol diacrylate. These unsaturated monomers can be used alone or in combination of two or more.
前記不飽和単量体混合物（Ｂ）は、前記不飽和単量体（ｂ２）の質量比率が０．１〜１．６質量％の範囲のものであるが、得られる塗膜の外観、耐薬品性、耐擦傷性が優れることから、０．２〜１．２質量％の範囲が好ましく、０．３〜０．８質量％の範囲がより好ましい。 The unsaturated monomer mixture (B) has a mass ratio of the unsaturated monomer (b2) in the range of 0.1 to 1.6% by mass. The range of 0.2 to 1.2% by mass is preferable and the range of 0.3 to 0.8% by mass is more preferable because of excellent chemical properties and scratch resistance.
前記不飽和単量体混合物（Ｂ）は、上記不飽和単量体（ｂ２）以外に、メチル（メタ）アクリレート、前記不飽和単量体（ｂ１）及び前記不飽和単量体（ｂ３）を必須成分として含有するものであるが、得られる塗膜の耐薬品性が優れることから、メチル（メタ）アクリレートの質量比率が５０〜９５質量％の範囲であり、前記不飽和単量体（ｂ１）の質量比率が１〜３０質量％の範囲であり、前記不飽和単量体（ｂ３）の質量比率が１〜３０質量％の範囲であることが好ましく、メチル（メタ）アクリレートの質量比率が７０〜９０質量％の範囲であり、前記不飽和単量体（ｂ１）の質量比率が３〜２０質量％の範囲であり、前記不飽和単量体（ｂ３）の質量比率が５〜１５質量％の範囲であることがより好ましい。 In addition to the unsaturated monomer (b2), the unsaturated monomer mixture (B) comprises methyl (meth) acrylate, the unsaturated monomer (b1), and the unsaturated monomer (b3). Although contained as an essential component, since the chemical resistance of the resulting coating film is excellent, the mass ratio of methyl (meth) acrylate is in the range of 50 to 95% by mass, and the unsaturated monomer (b1 ) In the range of 1 to 30% by mass, the mass ratio of the unsaturated monomer (b3) is preferably in the range of 1 to 30% by mass, and the mass ratio of methyl (meth) acrylate is It is in the range of 70 to 90% by mass, the mass ratio of the unsaturated monomer (b1) is in the range of 3 to 20% by mass, and the mass ratio of the unsaturated monomer (b3) is 5 to 15% by mass. % Is more preferable.
また、前記不飽和単量体混合物（Ａ）のＦＯＸの式で計算されるガラス転移温度（以下、「設計Ｔｇ」と略称する。）は、得られる塗膜の耐薬品性、耐擦傷性が向上することから、７０〜１１０℃の範囲が好ましい。 Further, the glass transition temperature (hereinafter abbreviated as “design Tg”) calculated by the FOX formula of the unsaturated monomer mixture (A) is the chemical resistance and scratch resistance of the obtained coating film. In order to improve, the range of 70-110 degreeC is preferable.
なお、本発明において、ＦＯＸの式で計算されるガラス転移温度とは、
ＦＯＸの式：１／Ｔｇ＝Ｗ１／Ｔｇ１＋Ｗ２／Ｔｇ２＋・・・
（Ｔｇ：求めるべきガラス転移温度、Ｗ１：成分１の重量分率、Ｔｇ１：成分１のホモポリマーのガラス転移温度）
に従い計算により求めたものである。各成分のホモポリマーのガラス転移温度の値は
、Ｐｏｌｙｍｅｒ Ｈａｎｄｂｏｏｋ（４ｔｈ Ｅｄｉｔｉｏｎ）Ｊ．Ｂｒａｎｄｒｕｐ，Ｅ．Ｈ．Ｉｍｍｅｒｇｕｔ，Ｅ．Ａ．Ｇｒｕｌｋｅ著（Ｗｉｌｅｙ Ｉｎｔｅｒｓｃｉｅｎｃｅ）記載の値を用いた。
In the present invention, the glass transition temperature calculated by the formula of FOX is
Formula of FOX: 1 / Tg = W1 / Tg1 + W2 / Tg2 +
(Tg: glass transition temperature to be obtained, W1: weight fraction of component 1, Tg1: glass transition temperature of homopolymer of component 1)
According to the calculation. The value of the glass transition temperature of the homopolymer of each component is described in Polymer Handbook (4th Edition) J. MoI. Brandrup, E .; H. Immergut, E .; A. Values described by Grulke (Wiley Interscience) were used.
前記ポリカーボネートジオール（Ａ）の存在下、前記不飽和単量体混合物（Ｂ）を反応させて本発明のポリカーボネート変性アクリル樹脂を得る方法としては、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 obtaining the polycarbonate-modified acrylic resin of the present invention by reacting the unsaturated monomer mixture (B) in the presence of the polycarbonate diol (A), a known polymerization method can be used. The polymerization method is preferred because it is the simplest.
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、キシレン等の芳香族系炭化水素化合物；シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン等の脂環式炭化水素化合物；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化合物；酢酸エチル、酢酸ｎ−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等のエステル化合物；ｎ−ブタノール、イソプロピルアルコール、シクロヘキサノール等のアルコール化合物；エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテルなどのグリコール化合物；ヘプタン、ヘキサン、オクタン、ミネラルターペン等の脂肪族炭化水素化合物などが挙げられる。 The 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 in this case include aromatic hydrocarbon compounds such as toluene and xylene; alicyclic hydrocarbon compounds such as cyclohexane, methylcyclohexane, and ethylcyclohexane; acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ketone compounds such as ethyl acetate, ester compounds such as n-butyl acetate and propylene glycol monomethyl ether acetate; alcohol compounds such as n-butanol, isopropyl alcohol and cyclohexanol; glycol compounds such as ethylene glycol monobutyl ether and propylene glycol monomethyl ether And aliphatic hydrocarbon compounds such as heptane, hexane, octane and mineral terpenes.
前記重合開始剤としては、例えば、シクロヘキサノンパーオキサイド、３，３，５−トリメチルシクロヘキサノンパーオキサイド、メチルシクロヘキサノンパーオキサイド等のケトンパーオキサイド化合物；１，１−ビス（ｔｅｒｔ−ブチルパーオキシ）−３，３，５−トリメチルシクロヘキサン、１，１−ビス（ｔｅｒｔ−ブチルパーオキシ）シクロヘキサン、ｎ−ブチル−４，４−ビス（ｔｅｒｔ−ブチルパーオキシ）バレレート、２，２−ビス（４，４−ジｔｅｒｔ−ブチルパーオキシシクロヘキシル）プロパン、２，２−ビス（４，４−ジｔｅｒｔ−アミルパーオキシシクロヘキシル）プロパン、２，２−ビス（４，４−ジｔｅｒｔ−ヘキシルパーオキシシクロヘキシル）プロパン、２，２−ビス（４，４−ジｔｅｒｔ−オクチルパーオキシシクロヘキシル）プロパン、２，２−ビス（４，４−ジクミルパーオキシシクロヘキシル）プロパン等のパーオキシケタール化合物；クメンハイドロパーオキサイド、２，５−ジメチルヘキサン−２，５−ジハイドロパーオキサイド等のハイドロパーオキサイド化合物；１，３−ビス（ｔｅｒｔ−ブチルパーオキシ−ｍ−イソプロピル）ベンゼン、２，５−ジメチル−２，５−ジ（ｔｅｒｔ−ブチルパーオキシ）ヘキサン、ジイソプロピルベンゼンパーオキサイド、ｔｅｒｔ−ブチルクミルパーオキサイド、等のジアルキルパーオキサイド化合物；デカノイルパーオキサイド、ラウロイルパーオキサイド、ベンゾイルパーオキサイド、２，４−ジクロロベンゾイルパーオキサイド等のジアシルパーオキサイド化合物；ビス（ｔｅｒｔ−ブチルシクロヘキシル）パーオキシジカーボネート等のパーオキシカーボネート化合物；ｔｅｒｔ−ブチルパーオキシ−２−エチルヘキサノエート、ｔｅｒｔ−ブチルパーオキシベンゾエート、２，５−ジメチル−２，５−ジ（ベンゾイルパーオキシ）ヘキサン等のパーオキシエステル化合物などの有機過酸化物と、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、１，１’−アゾビス（シクロヘキサン−１−カルボニトリル）等のアゾ化合物とが挙げられる。 Examples of the polymerization initiator include ketone peroxide compounds such as cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, and methylcyclohexanone peroxide; 1,1-bis (tert-butylperoxy) -3, 3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, 2,2-bis (4,4-di tert-butylperoxycyclohexyl) propane, 2,2-bis (4,4-ditert-amylperoxycyclohexyl) propane, 2,2-bis (4,4-ditert-hexylperoxycyclohexyl) propane, 2 , 2-bis (4,4-ditert-octylpa Peroxyketal compounds such as oxycyclohexyl) propane and 2,2-bis (4,4-dicumylperoxycyclohexyl) propane; cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, etc. Hydroperoxide compounds of: 1,3-bis (tert-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, diisopropylbenzene peroxide, tert Dialkyl peroxide compounds such as butyl cumyl peroxide; Diacyl peroxide compounds such as decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, and 2,4-dichlorobenzoyl peroxide; bis (tert Peroxycarbonate compounds such as butylcyclohexyl) peroxydicarbonate; tert-butylperoxy-2-ethylhexanoate, tert-butylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) Organic peroxides such as peroxyester compounds such as hexane, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methyl) butyronitrile, 1,1′-azobis (cyclohexane-1) And azo compounds such as (carbonitrile).
また、前記ポリカーボネートジオール（Ａ）と前記不飽和単量体混合物（Ｂ）との質量比［（Ａ）／（Ｂ）］は、得られる塗膜の耐薬品性、耐擦傷性が優れることから、１０／９０〜９０／１０の範囲が好ましく、１５／８５〜３５／６５又は６０／４０〜８５／１５の範囲がより好ましい。 Further, the mass ratio [(A) / (B)] of the polycarbonate diol (A) and the unsaturated monomer mixture (B) is excellent in chemical resistance and scratch resistance of the resulting coating film. The range of 10/90 to 90/10 is preferable, and the range of 15/85 to 35/65 or 60/40 to 85/15 is more preferable.
本発明のポリカーボネート変性アクリル樹脂の水酸基価は、得られる塗膜の付着性、耐薬品性、耐擦傷性が向上することから、２０〜１５０の範囲が好ましい。 The hydroxyl value of the polycarbonate-modified acrylic resin of the present invention is preferably in the range of 20 to 150 because adhesion, chemical resistance, and scratch resistance of the resulting coating film are improved.
本発明のポリカーボネート変性アクリル樹脂の重量平均分子量（Ｍｗ）は、得られる塗膜の耐擦傷性、耐薬品性が向上することから、３，０００〜３０，０００の範囲が好ましく、４，０００〜１５，０００の範囲がより好ましい。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 polycarbonate-modified acrylic resin of the present invention is preferably in the range of 3,000 to 30,000, since the scratch resistance and chemical resistance of the resulting coating film are improved, and 4,000 to A range of 15,000 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.
本発明の塗料は、本発明のポリカーボネート変性アクリル樹脂を含有するものであるが、得られる塗膜の物性が向上することから、硬化剤（Ｃ）を含有するものであることが好ましい。 Although the coating material of this invention contains the polycarbonate modified acrylic resin of this invention, since the physical property of the coating film obtained improves, it is preferable that it contains a hardening | curing agent (C).
前記硬化剤（Ｃ）としては、例えば、ポリイソシアネート化合物、アミノ樹脂等が挙げられるが、得られる塗膜の耐擦傷性、耐薬品性が優れることから、ポリイソシアネート化合物が好ましい。また、これらの硬化剤（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。 Examples of the curing agent (C) include polyisocyanate compounds, amino resins, and the like, and polyisocyanate compounds are preferred because the resulting coating film has excellent scratch resistance and chemical resistance. These curing agents (C) can be used alone or in combination of two or more.
前記ポリイソシアネート化合物としては、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。 Examples of the polyisocyanate compound include aromatic diisocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, m-xylylene diisocyanate, m-phenylene bis (dimethylmethylene) diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, 1,3-bis. (Isocyanatomethyl) aliphatic or fat such as cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate And cyclic diisocyanate compounds.
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 addition reaction of the diisocyanate compound with a polyhydric alcohol; a compound having an isocyanurate ring obtained by cyclization and trimerization of the diisocyanate compound; Polyisocyanate compound having urea bond or burette bond obtained by reacting the above diisocyanate compound with water; 2-isocyanatoethyl (meth) acrylate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate, (meth) acryloyl A homopolymer of an acrylic monomer having an isocyanate group such as isocyanate; the acrylic monomer having an isocyanate group and other acrylic monomers, vinyl ester compounds, vinyl ether compounds, aromatic vinyl monomers It is also possible to use a copolymer having an isocyanate group obtained by copolymerizing with a monomer, a monomer such as fluoroolefin.
上記のポリイソシアネート化合物は、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 can be used alone or in combination of two or more.
前記硬化剤（Ｃ）がポリイソシアネート化合物である場合の配合量としては、高強度の塗膜が得られることから、ポリイソシアネート化合物中のイソシアネート基と、本発明のポリカーボネート変性アクリル樹脂中の水酸基との当量比（イソシアネート基／水酸基）で、０．５〜２．０となる範囲が好ましく、０．７〜１．３となる範囲がより好ましい。 When the curing agent (C) is a polyisocyanate compound, since a high-strength coating film is obtained, the isocyanate group in the polyisocyanate compound and the hydroxyl group in the polycarbonate-modified acrylic resin of the present invention The equivalent ratio (isocyanate group / hydroxyl group) is preferably in the range of 0.5 to 2.0, more preferably in the range of 0.7 to 1.3.
なお、上記のウレタン化反応は、反応の進行を促進させるため、ウレタン化触媒の存在下で行うこともできる。前記ウレタン化触媒としては、例えば、トリエチルアミン等のアミン化合物、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、オクチル酸亜鉛（２−エチルヘキサン酸亜鉛）等の有機金属化合物などが挙げられる。 In addition, in order to accelerate | stimulate progress of reaction, said urethanation reaction can also be performed in presence of a urethanization catalyst. Examples of the urethanization catalyst include amine compounds such as triethylamine, dibutyltin dioctate, dibutyltin dilaurate, dioctyltin dilaurate, octyltin trilaurate, dioctyltin dineodecanate, dibutyltin diacetate, dioctyltin diacetate, tin dioctylate and the like. And organic metal compounds such as organic tin compounds and zinc octylate (zinc 2-ethylhexanoate).
本発明の塗料は、本発明のポリカーボネート変性アクリル樹脂及び硬化剤（Ｃ）を含有するものであるが、その他の配合物として、溶剤、消泡剤、粘度調整剤、耐光安定剤、耐候安定剤、耐熱安定剤、紫外線吸収剤、酸化防止剤、レベリング剤、顔料分散剤等の添加剤を使用することができる。また、酸化チタン、炭酸カルシウム、アルミニウム粉末、銅粉末、雲母粉末、酸化鉄、カーボンブラック、フタロシアニンブルー、トルイジンレッド、ペリレン、キナクリドン、ベンジジンイエロー等の顔料を使用することもできる。 The paint of the present invention contains the polycarbonate-modified acrylic resin of the present invention and a curing agent (C), but as other blends, a solvent, an antifoaming agent, a viscosity modifier, a light-resistant stabilizer, a weather-resistant stabilizer. Additives such as heat stabilizers, ultraviolet absorbers, antioxidants, leveling agents and pigment dispersants can be used. In addition, pigments such as titanium oxide, calcium carbonate, aluminum powder, copper powder, mica powder, iron oxide, carbon black, phthalocyanine blue, toluidine red, perylene, quinacridone, and benzidine yellow can also be used.
本発明の塗料は、プラスチック基材との高い付着性を有することから、各種プラスチック成形品を塗装する塗料として好適に用いることができるが、本発明の塗料を塗装することのできるプラスチック成形品としては、携帯電話、スマートフォン、タブレット端末、パソコン、デジタルカメラ、ゲーム機等の電子機器の筐体；テレビ、冷蔵庫、洗濯機、エアコン等の家電製品の筐体；自動車、鉄道車輌等の各種車輌の内装材；浴槽、釣り具などが挙げられる。 Since the paint of the present invention has high adhesion to a plastic substrate, it can be suitably used as a paint for coating various plastic molded products, but as a plastic molded product that can be coated with the paint of the present invention. Is a housing for electronic devices such as mobile phones, smartphones, tablet terminals, personal computers, digital cameras, game machines, etc .; housings for household appliances such as TVs, refrigerators, washing machines, air conditioners; various vehicles such as automobiles and railway vehicles Interior materials; bathtubs, fishing gear, etc.
本発明の塗料の塗装方法としては、例えば、スプレー、アプリケーター、バーコーター、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、スクリーン印刷等の方法が挙げられる。また、塗装後、塗膜とする方法としては、常温〜約１２０℃の範囲で乾燥させる方法が挙げられる。 Examples of the coating method of the paint of the present invention include spray, applicator, bar coater, gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, wheeler coater, spin coater, dipping, Examples thereof include screen printing. Moreover, the method of making it a coating film after coating includes the method of drying in the range of normal temperature to about 120 ° C.
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、本発明のポリカーボネート変性アクリル樹脂の水酸基価は、ＪＩＳ試験方法Ｋ ００７０−１９９２に準拠して測定したものである。また、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 with reference to specific examples. The hydroxyl value of the polycarbonate-modified acrylic resin of the present invention is measured according to JIS test method K 0070-1992. 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 connected in series.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 “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 amount: 100 μL (tetrahydrofuran solution with a sample concentration of 4 mg / mL)
Standard sample: A calibration curve was prepared using the following monodisperse 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)
"TSKgel standard polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-550" manufactured by Tosoh Corporation
（実施例１：ポリカーボネート変性アクリル樹脂（１）の合成）
冷却菅、温度計、滴下漏斗、および攪拌機を備えたフラスコに、１，３−プロパンジオールと１，４−ブタンジオールとを共重合したポリカーボネートジオール（旭化成ケミカルズ株式会社製「デュラノールＧ３４５２」、数平均分子量２０００；以下、「ポリカーボネートジオール（Ａ−１）」と略記する。）２００質量部、及びプロピレングリコールモノメチルエーテルアセテート４９０質量部を加え、内温を１３５℃まで上げた。次いで、メチルメタクリレート６８０質量部、２−ヒドロキシエチルアクリレート３５．２質量部、メタクリル酸４．８質量部、シクロへキシルメタクリレート８０質量部、プロピレングリコールモノメチルエーテルアセテート１６０質量部、及びｔｅｒｔ−ブチルパーオキシベンゾエート１６質量部との混合物（設計Ｔｇ９３℃）を５時間にわたって滴下した。滴下終了後も同温度で１７時間反応を継続した後、不揮発分６０質量％になるようにプロピレングリコールモノメチルエーテルアセテートで希釈し、水酸基価が２８、重量平均分子量が１１，０００であるポリカーボネート変性アクリル樹脂（１）の溶液を得た。
(Example 1: Synthesis of polycarbonate-modified acrylic resin (1))
Polycarbonate diol copolymerized with 1,3-propanediol and 1,4-butanediol ("Duranol G3452" manufactured by Asahi Kasei Chemicals Corporation, number average) in a flask equipped with a cooling tank, thermometer, dropping funnel, and stirrer Molecular weight 2000; hereinafter abbreviated as “polycarbonate diol (A-1).) 200 parts by mass and 490 parts by mass of propylene glycol monomethyl ether acetate were added, and the internal temperature was raised to 135 ° C. Next, 680 parts by weight of methyl methacrylate, 35.2 parts by weight of 2-hydroxyethyl acrylate, 4.8 parts by weight of methacrylic acid, 80 parts by weight of cyclohexyl methacrylate, 160 parts by weight of propylene glycol monomethyl ether acetate, and tert-butylperoxy A mixture of 16 parts by weight of benzoate (design Tg 93 ° C.) was added dropwise over 5 hours. After completion of the dropwise addition, the reaction was continued at the same temperature for 17 hours, and then diluted with propylene glycol monomethyl ether acetate so as to have a nonvolatile content of 60% by mass, a polycarbonate-modified acrylic having a hydroxyl value of 28 and a weight average molecular weight of 11,000. A solution of resin (1) was obtained.
（実施例２：ポリカーボネート変性アクリル樹脂（２）の合成）
冷却菅、温度計、滴下漏斗、および攪拌機を備えたフラスコに、ポリカーボネートジオール（Ａ−１）３００質量部、及びプロピレングリコールモノメチルエーテルアセテート５１０質量部を加え、内温を１３５℃まで上げた。次いで、メチルメタクリレート５９５質量部、２−ヒドロキシエチルアクリレート３０．８質量部、メタクリル酸４．２質量部、シクロへキシルメタクリレート７０質量部、プロピレングリコールモノメチルエーテルアセテート１４０質量部、及びｔｅｒｔ−ブチルパーオキシベンゾエート１４質量部との混合物（設計Ｔｇ９３℃）を５時間にわたって滴下した。滴下終了後も同温度で１７時間反応を継続した後、不揮発分６０質量％になるようにプロピレングリコールモノメチルエーテルアセテートで希釈し、水酸基価が３１、重量平均分子量が１１，０００であるポリカーボネート変性アクリル樹脂（２）の溶液を得た。
(Example 2: Synthesis of polycarbonate-modified acrylic resin (2))
300 parts by mass of polycarbonate diol (A-1) and 510 parts by mass of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tank, a thermometer, a dropping funnel, and a stirrer, and the internal temperature was raised to 135 ° C. Next, 595 parts by weight of methyl methacrylate, 30.8 parts by weight of 2-hydroxyethyl acrylate, 4.2 parts by weight of methacrylic acid, 70 parts by weight of cyclohexyl methacrylate, 140 parts by weight of propylene glycol monomethyl ether acetate, and tert-butylperoxy A mixture of 14 parts by weight of benzoate (design Tg 93 ° C.) was added dropwise over 5 hours. After completion of the dropwise addition, the reaction was continued at the same temperature for 17 hours, and then diluted with propylene glycol monomethyl ether acetate so as to have a nonvolatile content of 60% by mass, and a polycarbonate-modified acrylic having a hydroxyl value of 31 and a weight average molecular weight of 11,000. A solution of resin (2) was obtained.
（実施例３：ポリカーボネート変性アクリル樹脂（３）の合成）
冷却菅、温度計、滴下漏斗、および攪拌機を備えたフラスコに、ポリカーボネートジオール（Ａ−１）４００質量部、及びプロピレングリコールモノメチルエーテルアセテート５３０質量部を加え、内温を１３５℃まで上げた。次いで、メチルメタクリレート５１０質量部、２−ヒドロキシエチルアクリレート２６．４質量部、メタクリル酸３．６質量部、シクロへキシルメタクリレート６０質量部、プロピレングリコールモノメチルエーテルアセテート１２０質量部、及びｔｅｒｔ−ブチルパーオキシベンゾエート１２質量部との混合物（設計Ｔｇ９３℃）を５時間にわたって滴下した。滴下終了後も同温度で１７時間反応を継続した後、不揮発分６０質量％になるようにプロピレングリコールモノメチルエーテルアセテートで希釈し、水酸基価が３５、重量平均分子量が９，５００であるポリカーボネート変性アクリル樹脂（３）の溶液を得た。
(Example 3: Synthesis of polycarbonate-modified acrylic resin (3))
400 parts by mass of polycarbonate diol (A-1) and 530 parts by mass of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tank, a thermometer, a dropping funnel, and a stirrer, and the internal temperature was raised to 135 ° C. Next, 510 parts by weight of methyl methacrylate, 26.4 parts by weight of 2-hydroxyethyl acrylate, 3.6 parts by weight of methacrylic acid, 60 parts by weight of cyclohexyl methacrylate, 120 parts by weight of propylene glycol monomethyl ether acetate, and tert-butyl peroxy A mixture of 12 parts by weight of benzoate (design Tg 93 ° C.) was added dropwise over 5 hours. After completion of the dropwise addition, the reaction was continued at the same temperature for 17 hours, and then diluted with propylene glycol monomethyl ether acetate so as to have a nonvolatile content of 60% by mass, a polycarbonate-modified acrylic having a hydroxyl value of 35 and a weight average molecular weight of 9,500. A solution of resin (3) was obtained.
（実施例４：ポリカーボネート変性アクリル樹脂（４）の合成）
冷却菅、温度計、滴下漏斗、および攪拌機を備えたフラスコに、ポリカーボネートジオール（Ａ−１）５００質量部、及びプロピレングリコールモノメチルエーテルアセテート５５０質量部を加え、内温を１３５℃まで上げた。次いで、メチルメタクリレート４２５質量部、２−ヒドロキシエチルアクリレート２２．０質量部、メタクリル酸３．０質量部、シクロへキシルメタクリレート５０質量部、プロピレングリコールモノメチルエーテルアセテート１００質量部、及びｔｅｒｔ−ブチルパーオキシベンゾエート１０質量部との混合物（設計Ｔｇ９３℃）を５時間にわたって滴下した。滴下終了後も同温度で１７時間反応を継続した後、不揮発分６０質量％になるようにプロピレングリコールモノメチルエーテルアセテートで希釈し、水酸基価が３８、重量平均分子量が９，３００であるポリカーボネート変性アクリル樹脂（４）の溶液を得た。
(Example 4: Synthesis of polycarbonate-modified acrylic resin (4))
To a flask equipped with a cooling tank, thermometer, dropping funnel, and stirrer, 500 parts by mass of polycarbonate diol (A-1) and 550 parts by mass of propylene glycol monomethyl ether acetate were added, and the internal temperature was raised to 135 ° C. Next, 425 parts by weight of methyl methacrylate, 22.0 parts by weight of 2-hydroxyethyl acrylate, 3.0 parts by weight of methacrylic acid, 50 parts by weight of cyclohexyl methacrylate, 100 parts by weight of propylene glycol monomethyl ether acetate, and tert-butyl peroxy A mixture of 10 parts by weight of benzoate (design Tg 93 ° C.) was added dropwise over 5 hours. After completion of the dropwise addition, the reaction was continued at the same temperature for 17 hours, and then diluted with propylene glycol monomethyl ether acetate so as to have a nonvolatile content of 60% by mass, and a polycarbonate-modified acrylic having a hydroxyl value of 38 and a weight average molecular weight of 9,300. A solution of resin (4) was obtained.
（実施例５：ポリカーボネート変性アクリル樹脂（５）の合成）
冷却菅、温度計、滴下漏斗、および攪拌機を備えたフラスコに、ポリカーボネートジオール（Ａ−１）７００質量部、及びプロピレングリコールモノメチルエーテルアセテート５９０質量部を加え、内温を１３５℃まで上げた。次いで、メチルメタクリレート２５５質量部、２−ヒドロキシエチルアクリレート１３．２質量部、メタクリル酸１．８質量部、シクロへキシルメタクリレート３０質量部、プロピレングリコールモノメチルエーテルアセテート６０質量部、及びｔｅｒｔ−ブチルパーオキシベンゾエート６質量部との混合物（設計Ｔｇ９３℃）を２時間にわたって滴下した。滴下終了後も同温度で１７時間反応を継続した後、不揮発分６０質量％になるようにプロピレングリコールモノメチルエーテルアセテートで希釈し、水酸基価が４５、重量平均分子量が８，０００であるポリカーボネート変性アクリル樹脂（５）の溶液を得た。
(Example 5: Synthesis of polycarbonate-modified acrylic resin (5))
700 parts by mass of polycarbonate diol (A-1) and 590 parts by mass of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tank, a thermometer, a dropping funnel, and a stirrer, and the internal temperature was raised to 135 ° C. Next, 255 parts by weight of methyl methacrylate, 13.2 parts by weight of 2-hydroxyethyl acrylate, 1.8 parts by weight of methacrylic acid, 30 parts by weight of cyclohexyl methacrylate, 60 parts by weight of propylene glycol monomethyl ether acetate, and tert-butylperoxy A mixture of 6 parts by weight of benzoate (design Tg 93 ° C.) was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued at the same temperature for 17 hours, and then diluted with propylene glycol monomethyl ether acetate so as to have a nonvolatile content of 60% by mass, and the polycarbonate-modified acrylic having a hydroxyl value of 45 and a weight average molecular weight of 8,000. A solution of resin (5) was obtained.
（実施例６：ポリカーボネート変性アクリル樹脂（６）の合成）
冷却菅、温度計、滴下漏斗、および攪拌機を備えたフラスコに、ポリカーボネートジオール（Ａ−１）８００質量部、及びプロピレングリコールモノメチルエーテルアセテート６１０質量部を加え、内温を１３５℃まで上げた。次いで、メチルメタクリレート１７０質量部、２−ヒドロキシエチルアクリレート８．８質量部、メタクリル酸１．２質量部、シクロへキシルメタクリレート２０質量部、プロピレングリコールモノメチルエーテルアセテート４０質量部、及びｔｅｒｔ−ブチルパーオキシベンゾエート４質量部との混合物（設計Ｔｇ９３℃）を２時間にわたって滴下した。滴下終了後も同温度で１７時間反応を継続した後、不揮発分６０質量％になるようにプロピレングリコールモノメチルエーテルアセテートで希釈し、水酸基価が４８、重量平均分子量が６，５００であるポリカーボネート変性アクリル樹脂（６）の溶液を得た。
(Example 6: Synthesis of polycarbonate-modified acrylic resin (6))
800 parts by mass of polycarbonate diol (A-1) and 610 parts by mass of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tank, a thermometer, a dropping funnel, and a stirrer, and the internal temperature was raised to 135 ° C. Next, 170 parts by weight of methyl methacrylate, 8.8 parts by weight of 2-hydroxyethyl acrylate, 1.2 parts by weight of methacrylic acid, 20 parts by weight of cyclohexyl methacrylate, 40 parts by weight of propylene glycol monomethyl ether acetate, and tert-butyl peroxy A mixture with 4 parts by weight of benzoate (design Tg 93 ° C.) was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued at the same temperature for 17 hours, and then diluted with propylene glycol monomethyl ether acetate so as to have a nonvolatile content of 60% by mass, a polycarbonate modified acrylic having a hydroxyl value of 48 and a weight average molecular weight of 6,500. A solution of resin (6) was obtained.
（実施例７：ポリカーボネート変性アクリル樹脂（７）の合成）
冷却菅、温度計、滴下漏斗、および攪拌機を備えたフラスコに、１，３−プロパンジオールと１，４−ブタンジオールとを共重合したポリカーボネートジオール（旭化成ケミカルズ株式会社製「デュラノールＧ３４５０Ｊ」、数平均分子量８００；以下、「ポリカーボネートジオール（Ａ−２）」と略記する。）８００質量部、及びプロピレングリコールモノメチルエーテルアセテート６１０質量部を加え、内温を１３５℃まで上げた。次いで、メチルメタクリレート１７０質量部、２−ヒドロキシエチルアクリレート８．８質量部、メタクリル酸１．２質量部、シクロへキシルメタクリレート２０質量部、プロピレングリコールモノメチルエーテルアセテート４０質量部、及びｔｅｒｔ−ブチルパーオキシベンゾエート４質量部との混合物（設計Ｔｇ９３℃）を２時間にわたって滴下した。滴下終了後も同温度で１７時間反応を継続した後、不揮発分６０質量％になるようにプロピレングリコールモノメチルエーテルアセテートで希釈し、水酸基価が１１５、重量平均分子量が４，２００であるポリカーボネート変性アクリル樹脂（７）の溶液を得た。
(Example 7: Synthesis of polycarbonate-modified acrylic resin (7))
Polycarbonate diol obtained by copolymerization of 1,3-propanediol and 1,4-butanediol (“Duranol G3450J” manufactured by Asahi Kasei Chemicals Corporation, number average) in a flask equipped with a cooling tank, thermometer, dropping funnel, and stirrer Molecular weight 800; hereinafter abbreviated as “polycarbonate diol (A-2)”) 800 parts by mass and 610 parts by mass of propylene glycol monomethyl ether acetate were added, and the internal temperature was raised to 135 ° C. Next, 170 parts by weight of methyl methacrylate, 8.8 parts by weight of 2-hydroxyethyl acrylate, 1.2 parts by weight of methacrylic acid, 20 parts by weight of cyclohexyl methacrylate, 40 parts by weight of propylene glycol monomethyl ether acetate, and tert-butyl peroxy A mixture with 4 parts by weight of benzoate (design Tg 93 ° C.) was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued at the same temperature for 17 hours, and then diluted with propylene glycol monomethyl ether acetate so as to have a nonvolatile content of 60% by mass, and a polycarbonate-modified acrylic having a hydroxyl value of 115 and a weight average molecular weight of 4,200. A solution of resin (7) was obtained.
（実施例８：ポリカーボネート変性アクリル樹脂（８）の合成）
冷却菅、温度計、滴下漏斗、および攪拌機を備えたフラスコに、ポリカーボネートジオール（Ａ−１）８００質量部、及びプロピレングリコールモノメチルエーテルアセテート６１０質量部を加え、内温を１３５℃まで上げた。次いで、メチルメタクリレート１６０．８質量部、２−ヒドロキシエチルアクリレート１８．０質量部、メタクリル酸１．２質量部、シクロへキシルメタクリレート２０質量部、プロピレングリコールモノメチルエーテルアセテート４０質量部、及びｔｅｒｔ−ブチルパーオキシベンゾエート４質量部との混合物（設計Ｔｇ８６℃）を２時間にわたって滴下した。滴下終了後も同温度で１７時間反応を継続した後、不揮発分６０質量％になるようにプロピレングリコールモノメチルエーテルアセテートで希釈し、水酸基価が５２、重量平均分子量が６，４００であるポリカーボネート変性アクリル樹脂（８）の溶液を得た。
(Example 8: Synthesis of polycarbonate-modified acrylic resin (8))
800 parts by mass of polycarbonate diol (A-1) and 610 parts by mass of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tank, a thermometer, a dropping funnel, and a stirrer, and the internal temperature was raised to 135 ° C. Next, 160.8 parts by weight of methyl methacrylate, 18.0 parts by weight of 2-hydroxyethyl acrylate, 1.2 parts by weight of methacrylic acid, 20 parts by weight of cyclohexyl methacrylate, 40 parts by weight of propylene glycol monomethyl ether acetate, and tert-butyl A mixture of 4 parts by weight of peroxybenzoate (designed Tg 86 ° C.) was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued at the same temperature for 17 hours, and then diluted with propylene glycol monomethyl ether acetate so as to have a nonvolatile content of 60% by mass, a polycarbonate-modified acrylic having a hydroxyl value of 52 and a weight average molecular weight of 6,400. A solution of resin (8) was obtained.
（実施例９：ポリカーボネート変性アクリル樹脂（９）の合成）
冷却菅、温度計、滴下漏斗、および攪拌機を備えたフラスコに、ポリカーボネートジオール（Ａ−１）８００質量部、及びプロピレングリコールモノメチルエーテルアセテート６１０質量部を加え、内温を１３５℃まで上げた。次いで、メチルメタクリレート１５３質量部、２−ヒドロキシエチルアクリレート２６．０質量部、メタクリル酸１．２質量部、シクロへキシルメタクリレート２０質量部、プロピレングリコールモノメチルエーテルアセテート４０質量部、及びｔｅｒｔ−ブチルパーオキシベンゾエート４質量部との混合物（設計Ｔｇ８０℃）を２時間にわたって滴下した。滴下終了後も同温度で１７時間反応を継続した後、不揮発分６０質量％になるようにプロピレングリコールモノメチルエーテルアセテートで希釈し、水酸基価が５６、重量平均分子量が６，０００であるポリカーボネート変性アクリル樹脂（９）の溶液を得た。
(Example 9: Synthesis of polycarbonate-modified acrylic resin (9))
800 parts by mass of polycarbonate diol (A-1) and 610 parts by mass of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tank, a thermometer, a dropping funnel, and a stirrer, and the internal temperature was raised to 135 ° C. Next, 153 parts by weight of methyl methacrylate, 26.0 parts by weight of 2-hydroxyethyl acrylate, 1.2 parts by weight of methacrylic acid, 20 parts by weight of cyclohexyl methacrylate, 40 parts by weight of propylene glycol monomethyl ether acetate, and tert-butylperoxy A mixture of 4 parts by weight of benzoate (designed Tg 80 ° C.) was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued at the same temperature for 17 hours, and then diluted with propylene glycol monomethyl ether acetate so as to have a nonvolatile content of 60% by mass, and a polycarbonate-modified acrylic having a hydroxyl value of 56 and a weight average molecular weight of 6,000. A solution of resin (9) was obtained.
（実施例１０：ポリカーボネート変性アクリル樹脂（１０）の合成）
冷却菅、温度計、滴下漏斗、および攪拌機を備えたフラスコに、ポリカーボネートジオール（Ａ−１）８００質量部、及びプロピレングリコールモノメチルエーテルアセテート６１０質量部を加え、内温を１３５℃まで上げた。次いで、メチルメタクリレート１６９．２質量部、２−ヒドロキシエチルアクリレート８．８質量部、メタクリル酸２．０質量部、シクロへキシルメタクリレート２０質量部、プロピレングリコールモノメチルエーテルアセテート４０質量部、及びｔｅｒｔ−ブチルパーオキシベンゾエート４質量部との混合物（設計Ｔｇ９４℃）を２時間にわたって滴下した。滴下終了後も同温度で１７時間反応を継続した後、不揮発分６０質量％になるようにプロピレングリコールモノメチルエーテルアセテートで希釈し、水酸基価が４８、重量平均分子量が６，５００であるポリカーボネート変性アクリル樹脂（１０）の溶液を得た。
(Example 10: Synthesis of polycarbonate-modified acrylic resin (10))
800 parts by mass of polycarbonate diol (A-1) and 610 parts by mass of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tank, a thermometer, a dropping funnel, and a stirrer, and the internal temperature was raised to 135 ° C. Next, 169.2 parts by weight of methyl methacrylate, 8.8 parts by weight of 2-hydroxyethyl acrylate, 2.0 parts by weight of methacrylic acid, 20 parts by weight of cyclohexyl methacrylate, 40 parts by weight of propylene glycol monomethyl ether acetate, and tert-butyl A mixture of 4 parts by weight of peroxybenzoate (design Tg 94 ° C.) was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued at the same temperature for 17 hours, and then diluted with propylene glycol monomethyl ether acetate so as to have a nonvolatile content of 60% by mass, a polycarbonate modified acrylic having a hydroxyl value of 48 and a weight average molecular weight of 6,500. A solution of resin (10) was obtained.
（実施例１１：ポリカーボネート変性アクリル樹脂（１１）の合成）
冷却菅、温度計、滴下漏斗、および攪拌機を備えたフラスコに、ポリカーボネートジオール（Ａ−１）８００質量部、及びプロピレングリコールモノメチルエーテルアセテート６１０質量部を加え、内温を１３５℃まで上げた。次いで、メチルメタクリレート１７０質量部、２−ヒドロキシエチルアクリレート８．８質量部、メタクリル酸１．２質量部、ｎ−ブチルメタクリレート２０質量部、プロピレングリコールモノメチルエーテルアセテート４０質量部、及びｔｅｒｔ−ブチルパーオキシベンゾエート４質量部との混合物（設計Ｔｇ８７℃）を２時間にわたって滴下した。滴下終了後も同温度で１７時間反応を継続した後、不揮発分６０質量％になるようにプロピレングリコールモノメチルエーテルアセテートで希釈し、水酸基価が４８、重量平均分子量が６，８００であるポリカーボネート変性アクリル樹脂（１１）の溶液を得た。
(Example 11: Synthesis of polycarbonate-modified acrylic resin (11))
800 parts by mass of polycarbonate diol (A-1) and 610 parts by mass of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tank, a thermometer, a dropping funnel, and a stirrer, and the internal temperature was raised to 135 ° C. Next, 170 parts by weight of methyl methacrylate, 8.8 parts by weight of 2-hydroxyethyl acrylate, 1.2 parts by weight of methacrylic acid, 20 parts by weight of n-butyl methacrylate, 40 parts by weight of propylene glycol monomethyl ether acetate, and tert-butyl peroxy A mixture of 4 parts by weight of benzoate (designed Tg 87 ° C.) was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued at the same temperature for 17 hours, and then diluted with propylene glycol monomethyl ether acetate so as to have a nonvolatile content of 60% by mass, a polycarbonate-modified acrylic having a hydroxyl value of 48 and a weight average molecular weight of 6,800. A solution of resin (11) was obtained.
（比較例１：比較用樹脂（Ｒ１）の合成）
冷却菅、温度計、滴下漏斗、および攪拌機を備えたフラスコに、ポリカーボネートジオール（Ａ−１）８００質量部、及びプロピレングリコールモノメチルエーテルアセテート６１０質量部を加え、内温を１３５℃まで上げた。次いで、メチルメタクリレート１７１．２質量部、２−ヒドロキシエチルアクリレート８．８質量部、シクロヘキシルメタクリレート２０質量部、プロピレングリコールモノメチルエーテルアセテート４０質量部、及びｔｅｒｔ−ブチルパーオキシベンゾエート４質量部との混合物（設計Ｔｇ９４℃）を２時間にわたって滴下した。滴下終了後も同温度で１７時間反応を継続した後、不揮発分６０質量％になるようにプロピレングリコールモノメチルエーテルアセテートで希釈し、水酸基価が４８、重量平均分子量が６，８００であるポリカーボネート変性アクリル樹脂（Ｒ１）の溶液を得た。
(Comparative Example 1: Synthesis of Comparative Resin (R1))
800 parts by mass of polycarbonate diol (A-1) and 610 parts by mass of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tank, a thermometer, a dropping funnel, and a stirrer, and the internal temperature was raised to 135 ° C. Next, a mixture of 171.2 parts by weight of methyl methacrylate, 8.8 parts by weight of 2-hydroxyethyl acrylate, 20 parts by weight of cyclohexyl methacrylate, 40 parts by weight of propylene glycol monomethyl ether acetate, and 4 parts by weight of tert-butyl peroxybenzoate ( Design Tg 94 ° C.) was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued at the same temperature for 17 hours, and then diluted with propylene glycol monomethyl ether acetate so as to have a nonvolatile content of 60% by mass, a polycarbonate-modified acrylic having a hydroxyl value of 48 and a weight average molecular weight of 6,800. A solution of resin (R1) was obtained.
（比較例２：比較用樹脂（Ｒ２）の合成）
冷却菅、温度計、滴下漏斗、および攪拌機を備えたフラスコに、ポリカーボネートジオール（Ａ−１）８００質量部、及びプロピレングリコールモノメチルエーテルアセテート６１０質量部を加え、内温を１３５℃まで上げた。次いで、メチルメタクリレート１６７．６質量部、２−ヒドロキシエチルアクリレート８．８質量部、メタクリル酸３．６質量部、シクロヘキシルメタクリレート２０質量部、プロピレングリコールモノメチルエーテルアセテート４０質量部、及びｔｅｒｔ−ブチルパーオキシベンゾエート４質量部との混合物（設計Ｔｇ９４℃）を２時間にわたって滴下した。滴下終了後も同温度で１７時間反応を継続した後、不揮発分６０質量％になるようにプロピレングリコールモノメチルエーテルアセテートで希釈し、水酸基価が４８、重量平均分子量が７，０００であるポリカーボネート変性アクリル樹脂（Ｒ２）の溶液を得た。
(Comparative Example 2: Synthesis of Comparative Resin (R2))
800 parts by mass of polycarbonate diol (A-1) and 610 parts by mass of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tank, a thermometer, a dropping funnel, and a stirrer, and the internal temperature was raised to 135 ° C. Next, 167.6 parts by weight of methyl methacrylate, 8.8 parts by weight of 2-hydroxyethyl acrylate, 3.6 parts by weight of methacrylic acid, 20 parts by weight of cyclohexyl methacrylate, 40 parts by weight of propylene glycol monomethyl ether acetate, and tert-butylperoxy A mixture of 4 parts by weight of benzoate (design Tg 94 ° C.) was added dropwise over 2 hours. After completion of the dropping, the reaction was continued at the same temperature for 17 hours, and then diluted with propylene glycol monomethyl ether acetate so as to have a nonvolatile content of 60% by mass, and a polycarbonate-modified acrylic having a hydroxyl value of 48 and a weight average molecular weight of 7,000. A solution of resin (R2) was obtained.
（比較例３：比較用樹脂（Ｒ３）の合成）
冷却菅、温度計、滴下漏斗、および攪拌機を備えたフラスコに、１，６−ヘキサンジオールを重合したポリカーボネートジオール（旭化成ケミカルズ株式会社製「デュラノールＳ６００２」、数平均分子量２０００；以下、「ポリカーボネートジオール（ＲＡ−１）」と略記する。）３００質量部、及びプロピレングリコールモノメチルエーテルアセテート５１０質量部を加え、内温を１３５℃まで上げた。次いで、メチルメタクリレート５９５質量部、２−ヒドロキシエチルアクリレート３０．８質量部、メタクリル酸４．２質量部、シクロへキシルメタクリレート７０質量部、プロピレングリコールモノメチルエーテルアセテート１４０質量部、及びｔｅｒｔ−ブチルパーオキシベンゾエート１４質量部との混合物（設計Ｔｇ９３℃）を５時間にわたって滴下した。滴下終了後も同温度で１７時間反応を継続した後、不揮発分６０質量％になるようにプロピレングリコールモノメチルエーテルアセテートで希釈し、水酸基価が３１、重量平均分子量が１１，１００であるポリカーボネート変性アクリル樹脂（Ｒ３）の溶液を得た。
(Comparative Example 3: Synthesis of Comparative Resin (R3))
Polycarbonate diol obtained by polymerizing 1,6-hexanediol (“Duranol S6002” manufactured by Asahi Kasei Chemicals Corporation, number average molecular weight 2000; hereinafter referred to as “polycarbonate diol ( RA-1) ")) 300 parts by mass and 510 parts by mass of propylene glycol monomethyl ether acetate were added, and the internal temperature was raised to 135 ° C. Next, 595 parts by weight of methyl methacrylate, 30.8 parts by weight of 2-hydroxyethyl acrylate, 4.2 parts by weight of methacrylic acid, 70 parts by weight of cyclohexyl methacrylate, 140 parts by weight of propylene glycol monomethyl ether acetate, and tert-butylperoxy A mixture of 14 parts by weight of benzoate (design Tg 93 ° C.) was added dropwise over 5 hours. After completion of the dropwise addition, the reaction was continued at the same temperature for 17 hours, and then diluted with propylene glycol monomethyl ether acetate so as to have a nonvolatile content of 60% by mass, a polycarbonate-modified acrylic having a hydroxyl value of 31 and a weight average molecular weight of 11,100. A solution of resin (R3) was obtained.
（比較例４：比較用樹脂（Ｒ４）の合成）
冷却菅、温度計、滴下漏斗、および攪拌機を備えたフラスコに、１，４−ブタンジオールと１，６−ヘキサンジオールとを共重合したポリカーボネートジオール（旭化成ケミカルズ株式会社製「デュラノールＴ４６７２」、数平均分子量２０００；以下、「ポリカーボネートジオール（ＲＡ−２）」と略記する。）３００質量部、及びプロピレングリコールモノメチルエーテルアセテート５１０質量部を加え、内温を１３５℃まで上げた。次いで、メチルメタクリレート５９５質量部、２−ヒドロキシエチルアクリレート３０．８質量部、メタクリル酸４．２質量部、シクロへキシルメタクリレート７０質量部、プロピレングリコールモノメチルエーテルアセテート１４０質量部、及びｔｅｒｔ−ブチルパーオキシベンゾエート１４質量部との混合物（設計Ｔｇ９３℃）を５時間にわたって滴下した。滴下終了後も同温度で１７時間反応を継続した後、不揮発分６０質量％になるようにプロピレングリコールモノメチルエーテルアセテートで希釈し、水酸基価が３１、重量平均分子量が１０，６００であるポリカーボネート変性アクリル樹脂（Ｒ４）の溶液を得た。
(Comparative Example 4: Synthesis of Comparative Resin (R4))
Polycarbonate diol obtained by copolymerization of 1,4-butanediol and 1,6-hexanediol (“Duranol T4672” manufactured by Asahi Kasei Chemicals Corporation, number average) in a flask equipped with a cooling tank, thermometer, dropping funnel, and stirrer Molecular weight 2000; hereinafter abbreviated as “polycarbonate diol (RA-2)”) 300 parts by mass and 510 parts by mass of propylene glycol monomethyl ether acetate were added, and the internal temperature was raised to 135 ° C. Next, 595 parts by weight of methyl methacrylate, 30.8 parts by weight of 2-hydroxyethyl acrylate, 4.2 parts by weight of methacrylic acid, 70 parts by weight of cyclohexyl methacrylate, 140 parts by weight of propylene glycol monomethyl ether acetate, and tert-butylperoxy A mixture of 14 parts by weight of benzoate (design Tg 93 ° C.) was added dropwise over 5 hours. After completion of the dropwise addition, the reaction was continued at the same temperature for 17 hours, and then diluted with propylene glycol monomethyl ether acetate so as to have a nonvolatile content of 60% by mass, and a polycarbonate-modified acrylic having a hydroxyl value of 31 and a weight average molecular weight of 10,600. A solution of resin (R4) was obtained.
（比較例５：比較用樹脂（Ｒ５）の調製）
比較用樹脂（Ｒ５）として、「アクリディックＷＸＵ−８８０−ＢＡ」（ＤＩＣ株式会社製のアクリル樹脂溶液、不揮発分５０質量％、固形分水酸基価２１；以下、アクリル樹脂溶液（１）と略記する。）２００質量部（アクリル樹脂（１）として１００質量部）を用いた。
(Comparative Example 5: Preparation of comparative resin (R5))
As a comparative resin (R5), “Acridic WXU-880-BA” (acrylic resin solution manufactured by DIC Corporation, nonvolatile content 50 mass%, solid content hydroxyl value 21; hereinafter abbreviated as acrylic resin solution (1). .) 200 parts by mass (100 parts by mass as the acrylic resin (1)) was used.
（比較例６：比較用樹脂（Ｒ６）の調製）
ポリカーボネートジオール（Ａ−１）８０質量部をダイアセトンアルコール８０質量部で希釈した。次いで、アクリル樹脂溶液（１）４０質量部（アクリル樹脂（１）として２０質量部）を加えた後、均一になるまで撹拌し、水酸基価４６である比較用樹脂（Ｒ６）を得た。
(Comparative Example 6: Preparation of comparative resin (R6))
80 parts by mass of the polycarbonate diol (A-1) was diluted with 80 parts by mass of diacetone alcohol. Subsequently, after adding 40 mass parts (20 mass parts as acrylic resin (1)) of acrylic resin solution (1), it stirred until it became uniform and the resin (R6) for comparison which is the hydroxyl value 46 was obtained.
（比較例７：比較用樹脂（Ｒ７）の調製）
ポリカーボネートジオール（Ａ−１）を比較用樹脂（Ｒ７）として用いた。
(Comparative Example 7: Preparation of comparative resin (R7))
Polycarbonate diol (A-1) was used as a comparative resin (R7).
上記で得られたポリカーボネート変性アクリル樹脂（１）〜（１１）の組成を表１〜２に示す。 The composition of the polycarbonate-modified acrylic resins (1) to (11) obtained above is shown in Tables 1 and 2.
上記で得られた比較用樹脂（Ｒ１）〜（Ｒ７）の組成を表３に示す。 Table 3 shows the compositions of the comparative resins (R1) to (R7) obtained above.
表１〜３中の略号は、それぞれ下記のものである。
ＭＭＡ：メチルメタクリレート
ＨＥＡ：２−ヒドロキシアクリレート
ＭＡＡ：メタクリル酸
ＣＨＭＡ：シクロヘキシルメタクリレート
ＢＭＡ：ｎ−ブチルメタクリレート
The abbreviations in Tables 1 to 3 are as follows.
MMA: methyl methacrylate HEA: 2-hydroxyacrylate MAA: methacrylic acid CHMA: cyclohexyl methacrylate BMA: n-butyl methacrylate
（実施例１２：塗料（１）の調製及び評価） (Example 12: Preparation and evaluation of paint (1))
［塗料の調製］
上記の実施例１で得られたポリカーボネート変性アクリル樹脂（１）の溶液（不揮発分６０質量％）１００質量部及び硬化剤（ＤＩＣ株式会社製「バーノック ＤＮ−９８０」、ポリイソシアネートの不揮発分７５質量％溶液）７．９質量部を均一に混合した。なお、ポリカーボネート変性アクリル樹脂（１）と硬化剤の配合比率は、ポリカーボネート変性アクリル樹脂（１）の水酸基当量と硬化剤のイソシアネート基当量とが１：１となる量とした。次いで、粘度がアネスト岩田株式会社製「粘度カップＮＫ−２」で９〜１０秒（２３℃）になるように混合溶剤（メチルイソブチルケトン／ダイアセトンアルコール／酢酸エチル／酢酸イソブチル＝３０／２０／２０／３０（質量比））で希釈して塗料（１）を調製した。
[Preparation of paint]
100 parts by mass of a solution (60% by mass of nonvolatile content) of the polycarbonate-modified acrylic resin (1) obtained in Example 1 and a curing agent (“Bernock DN-980” manufactured by DIC Corporation, 75% by mass of nonvolatile content of polyisocyanate) % Solution) 7.9 parts by mass were mixed uniformly. The mixing ratio of the polycarbonate-modified acrylic resin (1) and the curing agent was such that the hydroxyl group equivalent of the polycarbonate-modified acrylic resin (1) and the isocyanate group equivalent of the curing agent were 1: 1. Next, a mixed solvent (methyl isobutyl ketone / diacetone alcohol / ethyl acetate / isobutyl acetate = 30/20 /) so that the viscosity is 9 to 10 seconds (23 ° C.) with “Viscosity Cup NK-2” manufactured by Anest Iwata Co., Ltd. 20/30 (mass ratio)) was diluted to prepare paint (1).
［評価用硬化塗膜Ｘの作製］
上記で得られた塗料（１）を、ＡＢＳ（アクリロニトリル−ブタジエン−スチレン共重合体）基材（厚さ１ｍｍ）に乾燥後の膜厚が２０〜３０μｍとなるようにスプレー塗装し、乾燥機にて８０℃、３０分加熱乾燥した後、２５℃で３日乾燥して評価用硬化塗膜を作製した。
[Preparation of cured coating film X for evaluation]
The paint (1) obtained above is spray-coated on an ABS (acrylonitrile-butadiene-styrene copolymer) base material (thickness 1 mm) so that the film thickness after drying is 20 to 30 μm, and is applied to a dryer. After drying at 80 ° C. for 30 minutes, the cured coating film for evaluation was prepared by drying at 25 ° C. for 3 days.
［評価用硬化塗膜Ｙの作製］
上記で得られた塗料（１）を、ＰＣ（ポリカーボネート）基材（厚さ１ｍｍ）に乾燥後の膜厚が２０〜３０μｍとなるようにスプレー塗装し、乾燥機にて８０℃、３０分加熱乾燥した後、２５℃で３日乾燥して評価用硬化塗膜を作製した。
[Preparation of cured coating Y for evaluation]
The paint (1) obtained above is spray-coated on a PC (polycarbonate) substrate (thickness 1 mm) so that the film thickness after drying is 20 to 30 μm, and heated at 80 ° C. for 30 minutes in a dryer. After drying, the cured coating film for evaluation was produced by drying at 25 ° C. for 3 days.
［付着性の評価］
上記で得られた評価用硬化塗膜Ｘ及びＹの上にカッターで２ｍｍ幅の切込みを入れ碁盤目の数を１００個とし、全ての碁盤目を覆うようにセロハンテープを貼り付け、すばやく引き剥がして付着して残っている碁盤目の数から、下記の基準により付着性を評価した。
○：１００個
△：７０〜９９個
×：６９個以下
[Evaluation of adhesion]
A 2 mm wide cut is made on the cured cured coatings X and Y obtained above with a cutter, the number of grids is 100, cellophane tape is applied to cover all grids, and quickly peeled off. From the number of grids remaining attached, the adhesion was evaluated according to the following criteria.
○: 100 pieces Δ: 70 to 99 pieces ×: 69 pieces or less
［耐擦傷性の評価］
上記で得られた評価用硬化塗膜Ｘの表面について、ＪＩＳ Ｓ ６００６：２００７に規定された鉛筆を用いて、ＪＩＳ Ｋ ５６００−５−４：１９９９に準じて、傷跡を生じなかった最も硬い鉛筆の硬度を測定し、下記の基準により耐擦傷性を評価した。
◎：２Ｂ以上
○：３Ｂ〜４Ｂ
△：５Ｂ〜６Ｂ
×：６Ｂで傷跡が生じる
[Evaluation of scratch resistance]
With respect to the surface of the cured coating film for evaluation X obtained above, the hardest pencil that did not cause scars according to JIS K 5600-5-4: 1999, using the pencil specified in JIS S 6006: 2007 The hardness was measured, and scratch resistance was evaluated according to the following criteria.
◎: 2B or more ○: 3B-4B
Δ: 5B-6B
×: Scars occur at 6B
［耐薬品性の評価］
上記で得られた評価用硬化塗膜Ｘの表面に、薬品（エスエスエルヘルスケアジャパン株式会社製「コパトーン・スポーツ ウルトラスウェットプルーフ ＳＰＦ３０」）を、１２ｍｇ／ｃｍ２塗布した後、５５℃の乾燥機で２時間乾燥させた。次いで、中性洗剤で塗膜表面を洗浄した後、室温で２４時間放置し、下記の基準により耐薬品性（耐薬品性試験後の付着性及び耐擦傷性）を評価した。
［耐薬品性試験後の付着性の評価］
耐薬品性試験後の塗膜の上にカッターでＸ字に切込みを入れ、切込み部分を覆うようにセロハンテープを貼り付け、すばやく引き剥がし、下記の基準により付着性を評価した。
○：塗膜の剥離なし
△：部分的に塗膜の剥離あり
×：塗膜全面が剥離
［耐薬品性試験後の耐擦傷性の評価］
耐薬品性試験後の塗膜の表面について、ＪＩＳ Ｓ ６００６：２００７に規定された鉛筆を用いて、ＪＩＳ Ｋ ５６００−５−４：１９９９に準じて、傷跡を生じなかった最も硬い鉛筆の硬度を測定し、下記の基準により耐擦傷性を評価した。
◎：２Ｂ以上
○：３Ｂ〜４Ｂ
△：５Ｂ〜６Ｂ
×：６Ｂで傷跡が生じる
[Evaluation of chemical resistance]
After applying 12 mg / cm 2 of chemical (“Copatone Sports Ultra Sweatproof SPF30” manufactured by SSL Healthcare Japan Co., Ltd.) on the surface of the cured coating film X for evaluation obtained above, it was dried with a dryer at 55 ° C. Dry for 2 hours. Next, the surface of the coating film was washed with a neutral detergent and allowed to stand at room temperature for 24 hours, and chemical resistance (adhesion and scratch resistance after chemical resistance test) was evaluated according to the following criteria.
[Evaluation of adhesion after chemical resistance test]
An incision was made in an X shape with a cutter on the coating film after the chemical resistance test, a cellophane tape was applied so as to cover the incised portion, it was quickly peeled off, and the adhesion was evaluated according to the following criteria.
○: No peeling of coating film △: Partial peeling of coating film ×: Peeling of entire coating film [Evaluation of scratch resistance after chemical resistance test]
Using the pencil specified in JIS S 6006: 2007, the hardness of the hardest pencil that did not cause scars on the surface of the coating film after the chemical resistance test was determined in accordance with JIS K 5600-5-4: 1999. The scratch resistance was evaluated according to the following criteria.
◎: 2B or more ○: 3B-4B
Δ: 5B-6B
×: Scars occur at 6B
［触感の評価］
上記で得られた評価用硬化塗膜Ｘの表面を指で触り、下記の基準により触感を評価した。
○：しっとり感がある
△：ややしっとり感がある
×：しっとり感がない
[Evaluation of tactile sensation]
The surface of the evaluation cured coating film X obtained above was touched with a finger, and the tactile sensation was evaluated according to the following criteria.
○: Moist feeling △: Moist feeling x: Moist feeling
（実施例１３〜２２：塗料（２）〜（１１）の調製及び評価）
実施例１２のポリカーボネート変性アクリル樹脂（１）を、ポリカーボネート変性アクリル樹脂（２）〜（１１）に変更した以外は実施例１２と同様に操作することにより塗料を調製後、評価用硬化塗膜を作製して付着性、耐擦傷性、耐薬品性及び触感を評価した。
(Examples 13 to 22: Preparation and evaluation of paints (2) to (11))
A cured coating film for evaluation was prepared after preparing a paint by operating in the same manner as in Example 12 except that the polycarbonate-modified acrylic resin (1) of Example 12 was changed to polycarbonate-modified acrylic resins (2) to (11). It was prepared and evaluated for adhesion, scratch resistance, chemical resistance and tactile sensation.
（比較例８〜１４：塗料（Ｒ１）〜（Ｒ７）の調製及び評価）
実施例１２のポリカーボネート変性アクリル樹脂（１）を、比較用樹脂（Ｒ１）〜（Ｒ７）に変更した以外は実施例１２と同様に操作することにより塗料を調製後、評価用塗膜を作製して付着性、耐擦傷性、耐薬品性及び触感を評価した。
(Comparative Examples 8 to 14: Preparation and evaluation of paints (R1) to (R7))
A coating film for evaluation was prepared after preparing a paint by operating in the same manner as in Example 12 except that the polycarbonate-modified acrylic resin (1) in Example 12 was changed to comparative resins (R1) to (R7). Adhesion, scratch resistance, chemical resistance and tactile sensation were evaluated.
上記で得られた塗料（１）〜（１１）、及び塗料（Ｒ１）〜（Ｒ７）の評価結果を表４〜６に示す。 The evaluation results of the paints (1) to (11) and the paints (R1) to (R7) obtained above are shown in Tables 4 to 6.
本発明のポリカーボネート変性アクリル樹脂である実施例１〜１１のものから得られる硬化塗膜は、付着性、耐擦傷性、耐薬品性及び触感に優れることが確認された（実施例１２〜２２）。 It was confirmed that the cured coating film obtained from Examples 1 to 11 which are polycarbonate-modified acrylic resins of the present invention is excellent in adhesion, scratch resistance, chemical resistance and touch (Examples 12 to 22). .
一方、比較例１及び２は、不飽和単量体混合物中のカルボキシル基を有する不飽和単量体の質量比率が、本発明の範囲である０．１〜１．６質量部から外れる例であるが、得られる硬化塗膜の耐擦傷性及び耐薬品性が劣ることが確認された（比較例８及び９）。 On the other hand, Comparative Examples 1 and 2 are examples in which the mass ratio of the unsaturated monomer having a carboxyl group in the unsaturated monomer mixture deviates from 0.1 to 1.6 parts by mass within the scope of the present invention. However, it was confirmed that the obtained cured coating film was poor in scratch resistance and chemical resistance (Comparative Examples 8 and 9).
比較例３及び４は、ポリカーボネートジオールとして、１，３−プロパンジオール及び１，４−ブタンジオールを用いて得られたものを用いなかった例であるが、得られる硬化塗膜の耐擦傷性、耐薬品性及び触感が劣ることが確認された（比較例１０及び１１）。 Comparative Examples 3 and 4 are examples in which the polycarbonate diol was not obtained using 1,3-propanediol and 1,4-butanediol, but the scratch resistance of the resulting cured coating film, It was confirmed that the chemical resistance and tactile sensation were inferior (Comparative Examples 10 and 11).
比較例５は、ポリカーボネート変性していないアクリル樹脂の例であるが、得られる塗膜の触感が劣ることが確認された（比較例１２）。 Although the comparative example 5 is an example of the acrylic resin which is not polycarbonate-modified, it was confirmed that the touch feeling of the coating film obtained is inferior (Comparative Example 12).
比較例６は、ポリカーボネートジオールとアクリル樹脂の混合物の例であるが、得られる硬化塗膜の耐擦傷性及び耐薬品性が劣ることが確認された（比較例１３）。 Comparative Example 6 is an example of a mixture of polycarbonate diol and acrylic resin, but it was confirmed that the resulting cured coating film was poor in scratch resistance and chemical resistance (Comparative Example 13).
比較例７は、ポリカーボネートジオールの例であるが、得られる硬化塗膜の耐擦傷性及び耐薬品性が劣ることが確認された（比較例１４）。 Comparative Example 7 is an example of polycarbonate diol, but it was confirmed that the obtained cured coating film was poor in scratch resistance and chemical resistance (Comparative Example 14).
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