JPH0267380A - Acrylic lacquer composition - Google Patents
Acrylic lacquer compositionInfo
- Publication number
- JPH0267380A JPH0267380A JP21626288A JP21626288A JPH0267380A JP H0267380 A JPH0267380 A JP H0267380A JP 21626288 A JP21626288 A JP 21626288A JP 21626288 A JP21626288 A JP 21626288A JP H0267380 A JPH0267380 A JP H0267380A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- carboxylic acid
- acrylic
- amount
- reaction mixture
- 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.)
- Pending
Links
- 239000004923 Acrylic lacquer Substances 0.000 title claims abstract description 21
- 239000000203 mixture Substances 0.000 title claims description 24
- 229920001577 copolymer Polymers 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 239000011541 reaction mixture Substances 0.000 claims abstract description 20
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 claims description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 18
- 239000011248 coating agent Substances 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- -1 acrylic acid) and Chemical class 0.000 abstract description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003973 paint Substances 0.000 description 29
- 239000002904 solvent Substances 0.000 description 20
- 239000000049 pigment Substances 0.000 description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 17
- 239000000243 solution Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000007921 spray Substances 0.000 description 8
- 239000004925 Acrylic resin Substances 0.000 description 7
- 229920000178 Acrylic resin Polymers 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 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 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 239000004922 lacquer Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920001220 nitrocellulos Polymers 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-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
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- BVCOHOSEBKQIQD-UHFFFAOYSA-N 2-tert-butyl-6-methoxyphenol Chemical compound COC1=CC=CC(C(C)(C)C)=C1O BVCOHOSEBKQIQD-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-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
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 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
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000006866 deterioration Effects 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
- 239000012969 di-tertiary-butyl peroxide Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 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
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000002320 enamel (paints) Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000000976 ink 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 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
- UXJXCZLHRLBCLF-UHFFFAOYSA-N n-ethylethanamine;ethyl 2-methylprop-2-enoate Chemical compound CCNCC.CCOC(=O)C(C)=C UXJXCZLHRLBCLF-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 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
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 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
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は改良された新規なアクリル系ラッカー組成物に
関するものである。更に詳しくは、塗料、インキ等各種
用途に有用な、光沢、肉持ち性、鮮映性、耐候性、耐溶
剤性に優れた塗膜を与え、且つ顔料分散性、溶剤希釈性
、スプレー作業性、乾燥性等にも優れたアクリル系ラッ
カー組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention This invention relates to new and improved acrylic lacquer compositions. More specifically, it provides a coating film with excellent gloss, durability, sharpness, weather resistance, and solvent resistance that is useful for various uses such as paints and inks, as well as pigment dispersibility, solvent dilubility, and spray workability. This invention relates to an acrylic lacquer composition that also has excellent drying properties.
(従来の技術)
従来から、アクリル樹脂塗料としてアクリルラッカーが
広く知られ、アルキド樹脂塗料や他の樹脂系塗料よりも
耐候性、耐薬品性、耐水性等に優れているため、高品質
の仕上げが要求される分野に多く使用されている。(Conventional technology) Acrylic lacquer has been widely known as an acrylic resin paint, and it has superior weather resistance, chemical resistance, water resistance, etc. than alkyd resin paints and other resin paints, so it is a high-quality finish. It is widely used in fields that require
アクリルラッカーは、メラミン樹脂のようなアミノ樹脂
やトリレンジイソシアネートのようなインシアネート化
合物やエポキシ樹脂等との三次元化架橋硬化をさせない
で、目′的とする塗膜性能を得ようとするために、一般
にラッカー用のアクリル樹脂は架橋硬化型アクリル樹脂
よシ分子量を大きくし、ガラス転位点(Tg)も高くし
、更に乾燥性等を改良するために、アクリルラッカーに
ニトロセルロースやセルロースアセテートフチレートの
ような繊維素誘導体を多く添加している。Acrylic lacquers are used to achieve the desired coating performance without three-dimensional crosslinking and curing with amino resins such as melamine resins, incyanate compounds such as tolylene diisocyanate, and epoxy resins. In general, acrylic resins for lacquers have higher molecular weights and higher glass transition points (Tg) than cross-linked acrylic resins, and in order to further improve drying properties, nitrocellulose or cellulose acetate edges are added to the acrylic lacquers. A large amount of cellulose derivatives such as lattice are added.
(発明が解決しようとする問題点)
したがって、従来のアクリルラッカーは溶剤希釈性やス
プレー作業時の微粒化が悪く、得られる塗膜は塗装時の
レベリングが悪く々つたシ、光沢、肉持ち性、鮮映性が
劣ったシ、耐候性が悪い等の問題がある。(Problems to be solved by the invention) Therefore, conventional acrylic lacquers have poor solvent dilutability and atomization during spraying, and the resulting coating film has poor leveling during painting, poor gloss, and poor durability. There are problems such as poor image clarity and poor weather resistance.
すなわち、アクリル樹脂の分子量を大きくしたシ、繊維
素誘導体を用いたシすると、溶剤希釈性が悪くなシ、ま
た、スプレー等の塗装粘度に合わすために多くの溶剤を
必要とする結果、塗装時の塗料不揮発分が低くなって、
所定の塗膜厚を得るのに塗布量を多くし、湿潤時の塗膜
厚を厚くしなければならない。したがって、垂直面等は
タレ易くなるし、乾燥した塗膜の肉ヤセも大きくなる。In other words, when the molecular weight of acrylic resin is increased or when a cellulose derivative is used, the solvent dilutability is poor, and as a result, a large amount of solvent is required to match the viscosity of the spray etc. The non-volatile content of the paint becomes low,
To obtain a desired coating thickness, the amount of coating must be increased and the coating thickness when wet must be increased. Therefore, vertical surfaces etc. tend to sag, and the dried paint film becomes more faded.
更に、分子量の大きいものは、スプレー作業時の微粒化
が悪いため、塗膜の肌荒れがはげしく、平滑々塗膜面が
得難く、光沢や見映えが極端に悪くなる。Furthermore, those with a large molecular weight have poor atomization during spraying, resulting in severe roughness of the coating film, difficulty in obtaining a smooth coating surface, and extremely poor gloss and appearance.
このような欠点を改良する方法として、溶剤希釈性やス
プレー作業性を良くするために、強溶剤や強溶剤で高沸
点の溶剤が使用されるが、コストアップになったシ、高
沸点のために乾燥性が悪くなるとか、プラスチック基材
に塗装した場合には基材を犯す“とかの問題があシ十分
に満足されていない。また、光沢や肉持ち性を良くする
ためにラッカー用のアクリル樹脂の組成の一部に、たと
えばスチレンモノマーを導入すると、光沢、肉持ち性は
良くなるが、屋外曝露での黄変が強く、耐候性が悪くな
る。As a way to improve these shortcomings, strong solvents or strong solvents with high boiling points are used to improve solvent dilution and spray workability, but this increases the cost and the high boiling point There are problems such as poor drying properties and damage to the base material when painted on plastic base materials, which are not fully satisfied.Also, in order to improve gloss and durability, paints for lacquer For example, when a styrene monomer is introduced into a part of the composition of the acrylic resin, gloss and durability are improved, but yellowing is strong when exposed outdoors and weather resistance is deteriorated.
また、従来のアクリルラッカー全般の欠点として、顔料
分散性に劣シ、たとえば顔料混線時の増粘や原色塗料の
凝集による顔料沈降、調色塗料での色分かれなどのトラ
ブルを起こしやすいとか、肉持ち性や鮮映性が劣ること
が指摘されておシ、イド#、110.9〜1/1.3
(モル比)を−船人(a)(但し、式中R8は水素原子
またはメチル基をs R2およびR3はそれぞれメチル
基を、nは1または2の整数を表わす。)で示される触
媒(但し、触媒の使用量はα、β−不飽和不飽和カルボ
ン酸1置して得られる反応混合物を重合成分に用いた塗
料用アクリル系樹脂を提案している。該塗料用アクリル
系樹脂は顔料分散性が著しく向上したものであるが、耐
溶剤性、スプレー作業性、耐候性、肉持ち性、溶剤希釈
性、乾燥性等が充分満足しうるものではなかった。In addition, general drawbacks of conventional acrylic lacquers include poor pigment dispersibility, which can easily cause problems such as thickening when pigments are mixed together, pigment sedimentation due to agglomeration of primary color paints, and color separation with toning paints. It has been pointed out that the durability and sharpness of images are poor.
(Molar ratio) - Shipman (a) (However, in the formula, R8 is a hydrogen atom or a methyl group, R2 and R3 are each a methyl group, and n is an integer of 1 or 2.) Catalyst ( However, we have proposed an acrylic resin for paints in which the reaction mixture obtained by reacting α, β-unsaturated carboxylic acid with one catalyst is used as a polymerization component.The acrylic resin for paints is Although the dispersibility was significantly improved, solvent resistance, spray workability, weather resistance, thickening properties, solvent dilutability, drying properties, etc. were not fully satisfactory.
一方、特公昭62−7230号では、特定量のt−ブチ
ルメタアクリレートとその他の共重合可能な単量体を合
計して100!量係となるように重合させて得られる、
数平均分子量が5000〜5ooooで、かつガラス転
移点が60〜95℃なる共重合体と僚維素化合物とを混
合したものが、耐摩耗性および耐アルコール性にすぐれ
ているとの提案がなされているが、このよう人共重合体
では顔料分散性が十分でなく、また得られる塗膜も光沢
、肉持ち性、鮮映性等十分に満足されない等の問題点が
ある。On the other hand, in Japanese Patent Publication No. Sho 62-7230, a specific amount of t-butyl methacrylate and other copolymerizable monomers are combined to yield 100! Obtained by polymerizing in a proportionate manner,
It has been proposed that a mixture of a copolymer with a number average molecular weight of 5000 to 5000 and a glass transition point of 60 to 95°C and a fibrillar compound has excellent abrasion resistance and alcohol resistance. However, such human copolymers have problems such as insufficient pigment dispersibility and resulting coating films that are not fully satisfied with gloss, durability, image clarity, etc.
アクリルラッカーは比較的高価で高品質な高級仕上げ用
塗料として多用されながら、このように問題が多くその
改良要求が強かった。Although acrylic lacquer is often used as a relatively expensive, high-quality, high-grade finishing paint, it has many problems as described above, and there has been a strong demand for improvements.
本発明者らは、上記のような問題点を克服すべく鋭意研
究した結果、光沢、肉持ち性、鮮映性、耐溶剤性、耐候
性に優れた塗膜を与え、且つ顔料分散性、溶剤希釈性、
スプレー作業性、乾燥性にも優れたアクリル系ラッカー
組成物を、その他の諸性能を低下させることなく完成さ
せるに至った。As a result of intensive research to overcome the above-mentioned problems, the inventors of the present invention have created a coating film with excellent gloss, durability, sharpness, solvent resistance, and weather resistance, as well as pigment dispersibility and Solvent dilutability,
An acrylic lacquer composition with excellent spray workability and drying properties was completed without degrading other properties.
(問題点を解決するための手段および作用)即ち本発明
は、
(A) t−ブチルメタアクリレート(1)5〜80
重量係、
CB) メチルメタアクリレ−) (2) 5〜80
重量係、(C) α、β−不飽和カルボン酸1モルに
対しアルキレンオキサイド0.9〜1.3モルを一般式
(a)ORs
(但し、式中R1は水素原子またはメチル基を、&およ
びR8はそれぞれメチル基を、nは1または2の整数を
表わす。)で示される触媒(但し、触媒の使用量はα、
β−不飽和カルボン酸100重′Bk%に対して0゜0
1〜10重ft%)の存在下で反応して得られる反応混
合物(3) 0.1〜10重量係、CD) α、β−
不飽和カルボン酸(4)O〜5重量係および
(E)他の重合性不飽和単全体(5)0〜89.9重量
%
からなる重合性単量体成分(但し、(1)、(2)、(
3)、(4)および(5)成分の合計は100重量重量
%る。)を共重合させて得られる共重合物を必須成分と
して含むアクリル系ラッカー組成物に関するものである
。(Means and effects for solving the problems) That is, the present invention provides: (A) t-butyl methacrylate (1) 5-80
Weight section, CB) Methyl methacrylate) (2) 5-80
Weight ratio, (C) 0.9 to 1.3 mol of alkylene oxide per 1 mol of α, β-unsaturated carboxylic acid to the general formula (a) ORs (However, in the formula, R1 is a hydrogen atom or a methyl group, & and R8 each represent a methyl group, and n represents an integer of 1 or 2.) (However, the amount of catalyst used is α,
0°0 per 100% Bk% of β-unsaturated carboxylic acid
Reaction mixture (3) obtained by reacting in the presence of 0.1-10% by weight (CD) α, β-
Polymerizable monomer component consisting of unsaturated carboxylic acid (4) O to 5% by weight and (E) other polymerizable unsaturated monomers (5) 0 to 89.9% by weight (provided that (1), ( 2), (
The total of components 3), (4) and (5) is 100% by weight. This invention relates to an acrylic lacquer composition containing as an essential component a copolymer obtained by copolymerizing
本発明においてt−ブチルメタアクリレート(1)は重
合性単量体成分中5〜80重量係の範囲内で用いられる
が、t−ブチルメタアクリレート(1)の使用量が5重
量%未満では得られるラッカー組成物を各種塗料用とし
て用いる際、光沢、肉持ち性、鮮映性、溶剤希釈性等が
劣ったものとなシ、逆に80重i%を超えるときはスプ
レー作業性が低下したシ、クラック発生のおそれがあシ
、いずれも好ましくない。In the present invention, t-butyl methacrylate (1) is used within the range of 5 to 80% by weight in the polymerizable monomer components, but if the amount of t-butyl methacrylate (1) used is less than 5% by weight, it is difficult to obtain When using lacquer compositions for various paints, they tend to have poor gloss, durability, sharpness, solvent dilutability, etc. On the other hand, when the lacquer composition exceeds 80% by weight, spray workability deteriorates. Both are undesirable, and there is a risk of cracking.
本発明に用いられるメチルメタアクリレート(2jは、
乾燥性、耐候性、耐溶剤性の向上のために必須の成分で
あシ、5〜80重量係の範囲で使用する。メチルメタア
クリレートの量が5重量%未満では、前記樹脂塗料用と
して用いる際、乾燥性、耐候性、耐溶剤性が不十分であ
シ、逆に80重重量%超えるときは、スプレー作業性、
肉持ち性、溶剤希釈性、光沢が低下するばかシでなく、
クラック発生のおそれがあシいずれも好ましくない。Methyl methacrylate (2j is
It is an essential component for improving dryness, weather resistance, and solvent resistance, and is used in an amount of 5 to 80% by weight. If the amount of methyl methacrylate is less than 5% by weight, the drying properties, weather resistance, and solvent resistance may be insufficient when used as the resin coating, while if it exceeds 80% by weight, the spray workability,
It does not cause deterioration in durability, solvent dilutability, or gloss.
Both are unfavorable as they may cause cracks.
本発明における反応混合物(3)は、α、β−不飽和カ
ルボン酸1モルに対しアルキレンオキサイド0.9〜1
.3モルを一般式(a)
ORs
(但し、式中R1は水素原子またはメチル基を、Rtお
よびR3はそれぞれメチル基を、nは1または2の整数
を表わす。)で示される触媒(但し、触媒の使用量はα
、β−不飽和カルポン酸1oo重fk係に対して0.0
1〜10重量%)の存在下で反応して得られるものであ
る。この際使用されるα、β−不飽和カルボン酸として
は例えば(メタ)アクリル酸が、アルキレンオキサイド
としては例えばエチレンオキサイド、プロピレンオキサ
イドがあげられる。この反応はα、β−不飽和カルボン
酸1モルに対しアルキレンオキサイド0.9〜1.3モ
ルの範囲で行なうが、アルキレンオキサイドの使用量が
0.9モル未満では反応が充分進行せず、逆に1.3モ
ルを超える場合はアルキレンオキサイドが未反応のまま
残存するので好ましくない。The reaction mixture (3) in the present invention contains 0.9 to 1 alkylene oxide per mole of α,β-unsaturated carboxylic acid.
.. 3 moles of a catalyst represented by the general formula (a) ORs (wherein R1 represents a hydrogen atom or a methyl group, Rt and R3 each represent a methyl group, and n represents an integer of 1 or 2) (however, The amount of catalyst used is α
, 0.0 for β-unsaturated carboxylic acid 1oo fk coefficient
1 to 10% by weight). Examples of the α,β-unsaturated carboxylic acid used in this case include (meth)acrylic acid, and examples of the alkylene oxide include ethylene oxide and propylene oxide. This reaction is carried out in the range of 0.9 to 1.3 moles of alkylene oxide per mole of α,β-unsaturated carboxylic acid, but if the amount of alkylene oxide used is less than 0.9 moles, the reaction will not proceed sufficiently. On the other hand, if it exceeds 1.3 moles, the alkylene oxide remains unreacted, which is not preferable.
反応混合物(3)の製造において使用される前記−紋穴
(alで示される触媒としては、例えばジメチルアミノ
エチルアクリレート、ジメチルアミノエチルメタアクリ
レート、ジエチルアミノエチルアクリレート、ジエチル
アミンエチルメタアクリレートなどがあげられる。触媒
の使用量は、α、β−不飽和カルボンr!R100重量
部に対して0.01〜10重量部、好ましくは0.1〜
5重量部の範囲にある量である。α、β−不飽和カルボ
ン酸とアルキレンオキサイドとの反応に用いられる触媒
として、−般に、トリエチルアミン、トリブチルアミン
等の飽和3級アミン類;鉄、クロム、ニッケル等の金属
類またはこれらの塩類等が報告されているが、これらの
触媒の使用によって得られる反応混合物を本発明の反応
混合物(3)の代わシに用いたのでは本発明の目的の一
つである優れた顔料分散性を有する共重合物とはなシ得
ない。Examples of the catalysts represented by al used in the production of the reaction mixture (3) include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, and diethylamine ethyl methacrylate. The amount used is 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of α,β-unsaturated carboxyl r!R.
The amount is in the range of 5 parts by weight. Catalysts used in the reaction between α, β-unsaturated carboxylic acids and alkylene oxides include: - Generally, saturated tertiary amines such as triethylamine and tributylamine; metals such as iron, chromium, and nickel, or salts thereof, etc. However, when the reaction mixture obtained by using these catalysts is used instead of the reaction mixture (3) of the present invention, it has excellent pigment dispersibility, which is one of the objects of the present invention. It cannot be considered a copolymer.
反応混合物(3)は、α、β−不飽和カルボン酸と一般
式(a)で示される触媒との混合物にアルキレンオキサ
イドを導入し、常圧または加圧下に30〜120℃、好
適には50〜100℃の温度に加熱して反応せしめるこ
とによって得られる。反応は、重合を防止するために空
気気流下で行い、重合防止剤を添加することが望ましい
。重合防止剤としては、例えばハイドロキノン、ハイド
ロキノンモノメチルエーテル、t−ブチルヒドロキシア
ニソール、p−ニトロフェノール、フェノチアジン等が
用いられ、その使用量は、α、β−不飽和カルボン酸1
0 ONN郡部対してo、oi〜0.1重量部の範囲に
ある量が好ましい。得られた反応混合物(3)は、蒸留
精製されることなくそのまま共重合成分として使用され
る。蒸留精製して得られる主留分を共重合成分として使
用したのでは本発明の目的である優れた顔料分散性を有
する共重合物を得ることができない。ただし、反応混合
物(3)から過剰の未反応アルキレンオキサイドを空気
吹き込みや減圧蒸留等の方法によって除去することは差
しつかえない。The reaction mixture (3) is prepared by introducing an alkylene oxide into a mixture of an α,β-unsaturated carboxylic acid and a catalyst represented by the general formula (a), and heating the mixture at 30 to 120°C, preferably at 50°C under normal pressure or increased pressure. It is obtained by heating to a temperature of ~100°C to cause a reaction. In order to prevent polymerization, the reaction is preferably carried out under an air stream and a polymerization inhibitor is added. Examples of polymerization inhibitors used include hydroquinone, hydroquinone monomethyl ether, t-butylhydroxyanisole, p-nitrophenol, and phenothiazine.
An amount in the range of o, oi to 0.1 part by weight based on 0 ONN mass is preferred. The obtained reaction mixture (3) is used as it is as a copolymerization component without being purified by distillation. If the main fraction obtained by distillation purification is used as a copolymerization component, a copolymer having excellent pigment dispersibility, which is the object of the present invention, cannot be obtained. However, it is possible to remove excess unreacted alkylene oxide from the reaction mixture (3) by methods such as air blowing or vacuum distillation.
こうして得られる反応混合物(3)は顔料分散性、鮮映
性、光沢が向上した本発明のアクリル系ラッカー組成物
を得るために必須成分で、該反応混合物(3)は重合性
単量体成分中0.1〜lO重量係、好ましくは14〜5
4〜5重量部で使用する。0.1重i%未満の場合は十
分な顔料分散性、鮮映性、光沢を発揮せず、逆に10!
i−%を超える多量では耐水性、耐候性などが低下する
。The reaction mixture (3) thus obtained is an essential component for obtaining the acrylic lacquer composition of the present invention with improved pigment dispersibility, image clarity, and gloss, and the reaction mixture (3) is a polymerizable monomer component. Medium 0.1 to 1O weight ratio, preferably 14 to 5
It is used in an amount of 4 to 5 parts by weight. If it is less than 0.1% by weight, sufficient pigment dispersibility, image clarity, and gloss will not be exhibited, and on the contrary, 10!
If the amount exceeds i-%, water resistance, weather resistance, etc. will decrease.
本発明に用いられるα、β−不飽和カルポン酸(4)と
しては、例えば(メタ)アクリル酸、クロトン酸、イタ
コン酸、マレイン酸、無水マレイン酸等のカルボキシル
基含有不飽和単量体等があげられる。α、β−不飽和カ
ルボン酸(4)の使用量は重合性単量体成分中0〜5重
i%の範囲であるが、前記反応混合物(3)の効果をよ
シ高度に発現させるために必須に用いるのが好ましく、
重合性単量体成分中0.05〜35〜3重量部好ましく
は0.08〜2重盆係とするのが好適である。5重量−
係を超える量を用いた場合は耐水性が低下する。Examples of the α,β-unsaturated carboxylic acid (4) used in the present invention include carboxyl group-containing unsaturated monomers such as (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, and maleic anhydride. can give. The amount of α, β-unsaturated carboxylic acid (4) used is in the range of 0 to 5% by weight based on the polymerizable monomer components, but in order to highly express the effect of the reaction mixture (3). It is preferable to use it indispensably,
It is suitable to use 0.05 to 35 to 3 parts by weight, preferably 0.08 to 2 parts by weight, in the polymerizable monomer component. 5 weight -
If an amount exceeding 100% is used, water resistance will decrease.
本発明に用いられるその他の重合性不飽和単量体(5)
としては、例えばメチルアクリレート、エチル(メタ)
アクリレート、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、ブチル(メタ)アクリレ
ート、イソブチル(メタ)アクリレート、ターシャリ−
ブチルアクリレート、2−エチルヘキシル(メタ)アク
リレート、イソノニル(メタ)アクリレート、オクチル
(メタ)アクリレート、インオクチル(メタ)アクリレ
ート、ラウリル(メタ)アクリレート、ステアリル(メ
タ)アクリレート等のt−ブチルメタアクリレートおよ
びメチルメタアクリレートを除く(メタ)アクリル酸ア
ルキルエステル;シクロヘキシル(メタ)アクリレート
、メチルシクロヘキシル(メタ)アクリレート、ターシ
ャリ−ブチルシクロヘキシル(メタ)アクリレート、シ
クロオクチル(メタ)アクリレート、シクロドデシル(
メタ)アクリレート等の(メタ)アクリル酸シクロアル
キルエステル;(メタ)アクリルアミド、(メタ)アク
リロニトリル、N、N’−ジメチルアミノエチル(メタ
)アクリレート、スチレン、α−メチルスチレン、ビニ
ルトルエン、酢酸ビニル、ビニルピリジン、ビニルイミ
ダゾール等があげられ、これらの1種または2種以上を
用いることができる。Other polymerizable unsaturated monomers (5) used in the present invention
For example, methyl acrylate, ethyl (meth)
Acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tertiary
t-Butyl methacrylate and methyl such as butyl acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, octyl (meth)acrylate, inoctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, etc. (Meth)acrylic acid alkyl esters excluding methacrylate; cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, cyclooctyl (meth)acrylate, cyclododecyl (
(meth)acrylic acid cycloalkyl esters such as meth)acrylate; (meth)acrylamide, (meth)acrylonitrile, N,N'-dimethylaminoethyl (meth)acrylate, styrene, α-methylstyrene, vinyltoluene, vinyl acetate, Examples include vinylpyridine and vinylimidazole, and one or more of these can be used.
その他の重合性単量体(5)は必要によ#)重合性単量
体成分中0〜89.9重f%の範囲で使用する。該単量
体(5)の使用量が89.9重量%を超えると前記成分
(1)〜(3)の使用量が本発明で規定された量忙満た
なくなシ、本発明の特徴が発揮されなくなる。Other polymerizable monomers (5) are used in an amount of 0 to 89.9% by weight based on the polymerizable monomer components (if necessary). If the usage amount of the monomer (5) exceeds 89.9% by weight, the usage amount of the components (1) to (3) will be less than the amount specified in the present invention, and the characteristics of the present invention will not be satisfied. It will no longer be effective.
但し、その他の重合性単量体(5)のうちシクロへキシ
ルメタアクリレートは好ましく使用できる単量体で6D
、重合性単量体成分中シクロヘキシルメタアクリレート
を2〜75重f%用い且つ前記t−ブチルメタアクリレ
ート(5)を5〜78重fZ%用いると、光沢、鮮映性
、溶剤希釈性が特に優れたアクリル系ラッカー組成物を
得る上で顕著な相剰効果を発現する。However, among the other polymerizable monomers (5), cyclohexyl methacrylate is a monomer that can be preferably used, and 6D
When cyclohexyl methacrylate is used in a polymerizable monomer component at 2 to 75 wt. It exhibits a significant synergistic effect in obtaining superior acrylic lacquer compositions.
本発明のアクリル系ラッカー組成物の必須成分たる共重
合物は前記成分(1)〜(5)からなる重合性単量体成
分を重合して得られる。重合は周知の方法に依ることが
でき、例えば溶液重合法、懸濁重合法、塊状重合法、乳
化重合法等が挙げられるが、本発明の特徴を最大限発揮
させるためには溶液重合法によるのが好ましい。The copolymer which is an essential component of the acrylic lacquer composition of the present invention is obtained by polymerizing the polymerizable monomer components consisting of the components (1) to (5). Polymerization can be carried out by well-known methods, such as solution polymerization, suspension polymerization, bulk polymerization, emulsion polymerization, etc., but in order to maximize the features of the present invention, solution polymerization is preferred. is preferable.
溶液重合法を採用する場合、重合開始剤としてはアゾビ
スイソブチロニトリル、ベンゾイルパーオキサイド、ジ
−ターシャリ−ブチルパーオキサイド等のラジカル重合
開始剤を用いることができ、また、重合溶媒としては、
トルエン、キシレンやその他の高沸点の芳香族系溶剤;
酢酸エチル、酢酸ブチルやセロソルブアセテート等のエ
ステル系ル、ブチルアルコール等のアルコール系溶剤を
単独もしくは混合で用いることができる。When employing the solution polymerization method, radical polymerization initiators such as azobisisobutyronitrile, benzoyl peroxide, di-tertiary-butyl peroxide can be used as the polymerization initiator, and as the polymerization solvent,
Toluene, xylene and other high-boiling aromatic solvents;
Ester solvents such as ethyl acetate, butyl acetate and cellosolve acetate, and alcohol solvents such as butyl alcohol can be used alone or in combination.
本発明のアクリル系ラッカー組成物は上記手順によシ得
られる共重合物を必須成分として含んでなるものである
が、通常は適当な有機溶剤の溶液である。また、必要に
応じてニトロセルロースやセルロースアセテートブチレ
ートのような繊維素誘導体などが配合されていても良い
。The acrylic lacquer composition of the present invention, which comprises as an essential component the copolymer obtained by the above procedure, is usually a solution in a suitable organic solvent. Furthermore, cellulose derivatives such as nitrocellulose and cellulose acetate butyrate may be blended as necessary.
共重合物の溶液とするのに用いられる有機溶剤としては
、前記した如き溶液重合時の重合溶剤がそのまま使用で
き、共重合物を比較的高濃度で溶解し得るものであれば
特に制限はない。The organic solvent used to form a solution of the copolymer is not particularly limited as long as the polymerization solvent used in solution polymerization as described above can be used as is, and it can dissolve the copolymer at a relatively high concentration. .
(発明の効果)
本発明のアクリル系ラッカー組成物は、光沢、肉持ち性
、鮮映性、耐候性、耐溶剤性に優れた塗膜を与え、且つ
顔料分散性、溶剤希釈性、スプレー作業性、乾燥性等に
も優れておシ、クリヤー塗料として使用できるほか、公
知の顔料分散法にょシ種々の無機顔料や有機顔料を分散
させ、着色エナメル塗料として使用できる。また、必要
に応じて公知の各種塗料用添加剤を添加することができ
る。(Effects of the Invention) The acrylic lacquer composition of the present invention provides a coating film with excellent gloss, durability, sharpness, weather resistance, and solvent resistance, and also has excellent pigment dispersibility, solvent dilutability, and spray workability. It has excellent properties such as hardness and drying properties, and can be used as a clear paint.It can also be used as a colored enamel paint by dispersing various inorganic and organic pigments using known pigment dispersion methods. Further, various known additives for paints can be added as necessary.
このようにして調製された塗料は、スプレー塗装、ロー
ル塗装、ハケ塗装などの一般的な塗装法によシ、木工製
品、金属、プラスチック類等に塗装することができる。The paint thus prepared can be applied to wood products, metals, plastics, etc. using general coating methods such as spray coating, roll coating, and brush coating.
(実施例)
以下、製造例、実施例および比較例によシ本発明を更に
詳しく説明する。なお、例中の部は重量部を、係は重量
部を示すものとする。(Examples) The present invention will be explained in more detail below using production examples, examples, and comparative examples. In addition, parts in the examples indicate parts by weight, and ``parts'' indicate parts by weight.
製造例1
洗
撹拌機、還吻冷却器、滴下ロート、温度計およびガス吹
込み管を備えた反応器に、アクリル酸144部、ジメチ
ルアミノエチルメタアクリレート4.0部およびハイド
ロキノンモノメチルエーテル0.05部を仕込み、撹拌
下および空気気流下に液温を70℃に昇温した。そこへ
プロピレンオキサイド122部を3時間かけて滴下し、
更に5時間反応させた。この間、液温は70℃に保つよ
うにした。次いで液温を100℃に昇温し、この温度で
2時間反応を継続した後降温した。こうして得られた反
応混合物は、酸価が10 my KOH/、!i+ 。Production Example 1 144 parts of acrylic acid, 4.0 parts of dimethylaminoethyl methacrylate, and 0.05 parts of hydroquinone monomethyl ether were placed in a reactor equipped with a washing stirrer, a reflux condenser, a dropping funnel, a thermometer, and a gas blowing tube. The liquid temperature was raised to 70° C. under stirring and an air stream. 122 parts of propylene oxide was dropped there over 3 hours,
The reaction was further continued for 5 hours. During this time, the liquid temperature was maintained at 70°C. Next, the liquid temperature was raised to 100°C, the reaction was continued at this temperature for 2 hours, and then the temperature was lowered. The reaction mixture thus obtained had an acid value of 10 my KOH/! i+.
水酸基価が345■KOH/ 、!i’の無色透明液状
物質(以下、〔反応混合物A〕という。)であった。The hydroxyl value is 345 KOH/! i' was a colorless and transparent liquid substance (hereinafter referred to as [reaction mixture A]).
製造例2
製造例1で使用したのと同じ反応器にメタアクリル酸1
72部、ジエチルアミノエチルメタアクリレート4.8
部およびハイドロキノンモノメチルエーテル0.06部
を仕込み、撹拌下および空気気流下に液温を70℃に昇
温した。そこへプロピレンオキサイド122部を3時間
かけて滴下し、以下、製造例1と同様の方法で反応させ
た後、降温した。こうして得られた反応混合物は、酸価
が151vKOH/g、水酸基価が310 m9 KO
H/IO無色透明液状物質(以下、〔反応混合物B〕と
いう。)であった。Production Example 2 One part of methacrylic acid was added to the same reactor used in Production Example 1.
72 parts, diethylaminoethyl methacrylate 4.8
1 part and 0.06 part of hydroquinone monomethyl ether were charged, and the liquid temperature was raised to 70° C. while stirring and under a stream of air. 122 parts of propylene oxide was added dropwise thereto over 3 hours, followed by reaction in the same manner as in Production Example 1, and then the temperature was lowered. The reaction mixture thus obtained had an acid value of 151 vKOH/g and a hydroxyl value of 310 m9 KO.
The H/IO colorless transparent liquid substance (hereinafter referred to as [reaction mixture B]) was obtained.
実施例1
撹拌機、温度計、冷却器、窒素ガス導入管のついた4つ
ロフラスコに窒素ガス気流下、トルエン61.1部およ
びブタノール61.1部を仕込み、75℃に昇温した中
に、t−ブチルメタアクリレート15部、メチルメタア
クリレート49.7部、製造例1で得られた反応混合物
図5部、アクリル酸0.3部、ブチルメタアクリレート
30部およびアゾビスイソブチロニトリル0.5部から
なる重合性単量体成分を2時間かけて滴下し、更に75
℃で4時間保持して、共重合物を不揮発分44.9%、
粘度Z、の溶液(共重合物溶液(1)という)として得
た。Example 1 61.1 parts of toluene and 61.1 parts of butanol were charged under a nitrogen gas stream into a four-bottle flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas inlet tube, and the temperature was raised to 75°C. , 15 parts of t-butyl methacrylate, 49.7 parts of methyl methacrylate, 5 parts of the reaction mixture obtained in Production Example 1, 0.3 parts of acrylic acid, 30 parts of butyl methacrylate, and 0 parts of azobisisobutyronitrile. A polymerizable monomer component consisting of .5 parts was added dropwise over 2 hours, and an additional 75 parts
The copolymer was maintained at ℃ for 4 hours to reduce the non-volatile content to 44.9%.
It was obtained as a solution (referred to as copolymer solution (1)) with a viscosity of Z.
実施例2〜6および比較例1〜4
実施例1において使用した重合性単量体混合物の組成を
第1表に示した通シとする以外は実施例1と同様の操作
を繰シ返して共重合物溶液(2)〜(6)および比較共
重合物溶液(1)〜(4)を得た。Examples 2 to 6 and Comparative Examples 1 to 4 The same operations as in Example 1 were repeated except that the composition of the polymerizable monomer mixture used in Example 1 was the same as shown in Table 1. Copolymer solutions (2) to (6) and comparative copolymer solutions (1) to (4) were obtained.
実施例7
実施例1〜6および比較例1〜4で得られた共重合物溶
液(1)〜(6)および比較共重合物溶液(1)〜(4
)を用い、下記の手順で各種の顔料を混練して原色塗料
を調製し、顔料分散性を試験した。結果は第2表に示し
た。また、得られた各色の原色塗料を下記の手順で混合
して調色塗料とし、同じく顔料分散性を試験した。結果
は第3表に示した。Example 7 Copolymer solutions (1) to (6) and comparative copolymer solutions (1) to (4) obtained in Examples 1 to 6 and Comparative Examples 1 to 4
), various pigments were kneaded according to the following procedure to prepare primary color paints, and the pigment dispersibility was tested. The results are shown in Table 2. Further, the obtained primary color paints of each color were mixed according to the following procedure to prepare a toning paint, and the pigment dispersibility was similarly tested. The results are shown in Table 3.
記
〔原色塗料の調製〕
(白色塗料)
共重合物溶液(1)〜(6)および比較共重合物溶液(
1)〜(4)のそれぞれに白色顔料“タイベークR−8
20”(石原産業■製、ルチル型酸化チタン)を樹脂不
揮発分/顔料=1/1(重量比)になるように加え、サ
ンドミル(ガラスピース使用。以下同様。)にて30分
間混練した。これをキシレン/トルエン/酢酸ブチル=
1/1/1(重量比)のシンナー(以下、単に「シンナ
ー」とよぶ。)にて塗料粘度が20秒(フォード・カッ
プ、%4/25℃。[Preparation of primary color paint] (White paint) Copolymer solutions (1) to (6) and comparative copolymer solution (
White pigment "Tie Bake R-8" was applied to each of 1) to (4).
20" (manufactured by Ishihara Sangyo ■, rutile type titanium oxide) was added so that the resin nonvolatile content/pigment ratio was 1/1 (weight ratio), and kneaded for 30 minutes in a sand mill (using a glass piece. The same applies hereinafter). This is xylene/toluene/butyl acetate=
Paint viscosity was 20 seconds (Ford Cup, %4/25°C) with 1/1/1 (weight ratio) thinner (hereinafter simply referred to as "thinner").
以下についても同様。)に々るように希釈したものを試
料とした。The same applies to the following. ) The sample was diluted as much as possible.
(黒色塗料)
共重合物溶液(1)〜(6)および比較共重合物溶液(
1)〜(4)のそれぞれに、黒色顔料“FW−2007
(デグツサ社製、カーボンブラック)を樹脂不揮発分/
顔料=110.04(重量比)になるように加え、サン
ドミルにて30分間混練した。これを、前記の白色塗料
を調製した場合と同様にしてシンナーにて希釈したもの
を試料とした。(Black paint) Copolymer solutions (1) to (6) and comparative copolymer solution (
The black pigment “FW-2007” was added to each of 1) to (4).
(manufactured by Degutsusa, carbon black) as resin non-volatile content/
The pigment was added so that the weight ratio was 110.04, and the mixture was kneaded for 30 minutes using a sand mill. This was diluted with thinner in the same manner as in the case of preparing the white paint described above and used as a sample.
各共重合物溶液を用いて得られた上記白色・黒色の2種
の原色塗料を用いて、下記の配合比率で配合したものを
調色塗料の試料とした。Samples of toning paints were prepared by using the above two primary color paints, white and black, obtained using each copolymer solution and blending them in the following blending ratios.
グレー色:白色塗料/黒色塗料=90/10(重量比)
実施例8
実施例1〜6で得られた共重合物溶液(1)〜(6)お
よび比較例1〜4で得られた比較共重合物溶液(1)〜
(4)をそのitアクリル系シラツカ−組成物1)〜(
6)および比較アクリル系ラッカー組成物(1)〜(4
)とし、これらに酸化チタン(タイベークR−820,
石原産業■製)を顔料重量濃度40%になるように配合
し、サンドミルにて分散し白エナメルを調製した。Gray color: white paint/black paint = 90/10 (weight ratio)
Example 8 Copolymer solutions (1) to (6) obtained in Examples 1 to 6 and comparative copolymer solutions (1) to obtained in Comparative Examples 1 to 4
(4) and its acrylic silica compositions 1) to (
6) and comparative acrylic lacquer compositions (1) to (4)
) and titanium oxide (Tiebake R-820,
(manufactured by Ishihara Sangyo ■) was blended to give a pigment weight concentration of 40% and dispersed in a sand mill to prepare white enamel.
得られた白エナメルのそれぞれをエアースプレーで軟鋼
板に乾燥膜厚20μになるように塗装し、室温で48時
間乾燥した後、塗膜の性能を評価した。塗膜の性能は次
に示す性能試験方法によシ◎〜O〜Δ〜×の4段階で評
価し、その評価結果を第4表に示す。Each of the obtained white enamels was applied to a mild steel plate by air spraying to a dry film thickness of 20 μm, and after drying at room temperature for 48 hours, the performance of the coating film was evaluated. The performance of the coating film was evaluated according to the following performance test method in four grades: ◎~O~Δ~×, and the evaluation results are shown in Table 4.
Claims (1)
重量%、 〔B〕メチルメタアクリレート(2)5〜80重量%、 〔C〕α,β−不飽和カルボン酸1モルに対しアルキレ
ンオキサイド0.9〜1.3モルを、一般式(a) ▲数式、化学式、表等があります▼ (但し、式中R_1は水素原子またはメチル基を、R_
2およびR_3はそれぞれメチル基を、nは1または2
の整数を表わす。)で示される触媒(但し、触媒の使用
量はα,β−不飽和カルボン酸100重量%に対して0
.01〜10重量%)の存在下で反応して得られる反応
混合物(3)0.1〜10重量%、 〔D〕α,β−不飽和カルボン酸(4)0〜5重量%お
よび 〔E〕他の重合性不飽和単量体(5)0〜89.9重量
% からなる重合性単量体成分(但し、(1)、(2)、(
3)、(4)および(5)の成分の合計は100重量%
である。)を共重合させて得られる共重合物を必須成分
として含むアクリル系ラツカー組成物。 2、t−ブチルメタアクリレート(1)の量が重合性単
量体成分中5〜78重量%であり且つ他の重合性不飽和
単量体(5)としてシクロヘキシルメタアクリレートを
重合性単量体成分中2〜75重量%の量で用いるもので
ある請求項1に記載のアクリル系ラツカー組成物。[Claims] 1. [A] t-butyl methacrylate (1) 5-80
% by weight, [B] 5 to 80% by weight of methyl methacrylate (2), [C] 0.9 to 1.3 mol of alkylene oxide per mol of α,β-unsaturated carboxylic acid, general formula (a) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, in the formula, R_1 is a hydrogen atom or a methyl group, and R_
2 and R_3 each represent a methyl group, n is 1 or 2
represents an integer. ) (however, the amount of catalyst used is 0% based on 100% by weight of α,β-unsaturated carboxylic acid)
.. 0.1 to 10% by weight of the reaction mixture (3) obtained by reacting in the presence of 0.01 to 10% by weight), 0 to 5% by weight of [D] α,β-unsaturated carboxylic acid (4) and [E ] Polymerizable monomer component consisting of 0 to 89.9% by weight of other polymerizable unsaturated monomers (5) (However, (1), (2), (
The total of components 3), (4) and (5) is 100% by weight
It is. ) An acrylic lacquer composition containing as an essential component a copolymer obtained by copolymerizing. 2. The amount of t-butyl methacrylate (1) is 5 to 78% by weight in the polymerizable monomer component, and cyclohexyl methacrylate is used as the other polymerizable unsaturated monomer (5). An acrylic lacquer composition according to claim 1, wherein the acrylic lacquer composition is used in an amount of 2 to 75% by weight of the ingredients.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21626288A JPH0267380A (en) | 1988-09-01 | 1988-09-01 | Acrylic lacquer composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21626288A JPH0267380A (en) | 1988-09-01 | 1988-09-01 | Acrylic lacquer composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0267380A true JPH0267380A (en) | 1990-03-07 |
Family
ID=16685797
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP21626288A Pending JPH0267380A (en) | 1988-09-01 | 1988-09-01 | Acrylic lacquer composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0267380A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003003112A (en) * | 2001-06-25 | 2003-01-08 | Mitsubishi Rayon Co Ltd | Composition for acrylic coating material |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5887160A (en) * | 1981-11-18 | 1983-05-24 | Dainippon Ink & Chem Inc | Acrylic lacquer |
JPS5924761A (en) * | 1982-08-02 | 1984-02-08 | Nippon Shokubai Kagaku Kogyo Co Ltd | Acrylic resin for paint |
-
1988
- 1988-09-01 JP JP21626288A patent/JPH0267380A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5887160A (en) * | 1981-11-18 | 1983-05-24 | Dainippon Ink & Chem Inc | Acrylic lacquer |
JPS5924761A (en) * | 1982-08-02 | 1984-02-08 | Nippon Shokubai Kagaku Kogyo Co Ltd | Acrylic resin for paint |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003003112A (en) * | 2001-06-25 | 2003-01-08 | Mitsubishi Rayon Co Ltd | Composition for acrylic coating material |
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