JPH0356519A - Water-based coating composition and coating method using same - Google Patents
Water-based coating composition and coating method using sameInfo
- Publication number
- JPH0356519A JPH0356519A JP19163389A JP19163389A JPH0356519A JP H0356519 A JPH0356519 A JP H0356519A JP 19163389 A JP19163389 A JP 19163389A JP 19163389 A JP19163389 A JP 19163389A JP H0356519 A JPH0356519 A JP H0356519A
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- parts
- water
- aqueous dispersion
- coating composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 33
- 239000008199 coating composition Substances 0.000 title claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 29
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 44
- 239000006185 dispersion Substances 0.000 claims abstract description 43
- 229920002678 cellulose Polymers 0.000 claims abstract description 35
- 239000001913 cellulose Substances 0.000 claims abstract description 35
- 229920001577 copolymer Polymers 0.000 claims abstract description 35
- 239000000049 pigment Substances 0.000 claims abstract description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 29
- 239000000178 monomer Substances 0.000 claims abstract description 28
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 25
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 238000004132 cross linking Methods 0.000 claims abstract description 11
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000376 reactant Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 abstract description 19
- 239000003973 paint Substances 0.000 abstract description 18
- 238000002156 mixing Methods 0.000 abstract description 10
- 239000007795 chemical reaction product Substances 0.000 abstract description 5
- 239000011247 coating layer Substances 0.000 abstract 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 36
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- 239000002585 base Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000003960 organic solvent Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 11
- 229920000877 Melamine resin Polymers 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 7
- -1 N-alkylimidazoline Chemical compound 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000002932 luster Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 5
- 239000004640 Melamine resin Substances 0.000 description 5
- 239000012736 aqueous medium Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 150000007514 bases Chemical class 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000007974 melamines Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 229960002887 deanol Drugs 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 239000002952 polymeric resin Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 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
- 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
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 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
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
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- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- UPGSWASWQBLSKZ-UHFFFAOYSA-N 2-hexoxyethanol Chemical compound CCCCCCOCCO UPGSWASWQBLSKZ-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- KFVIYKFKUYBKTP-UHFFFAOYSA-N 2-n-(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCNC1=NC(N)=NC(N)=N1 KFVIYKFKUYBKTP-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- CGLVZFOCZLHKOH-UHFFFAOYSA-N 8,18-dichloro-5,15-diethyl-5,15-dihydrodiindolo(3,2-b:3',2'-m)triphenodioxazine Chemical compound CCN1C2=CC=CC=C2C2=C1C=C1OC3=C(Cl)C4=NC(C=C5C6=CC=CC=C6N(C5=C5)CC)=C5OC4=C(Cl)C3=NC1=C2 CGLVZFOCZLHKOH-UHFFFAOYSA-N 0.000 description 1
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- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
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- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 125000002091 cationic group Chemical group 0.000 description 1
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- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- GTBGXKPAKVYEKJ-UHFFFAOYSA-N decyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C(C)=C GTBGXKPAKVYEKJ-UHFFFAOYSA-N 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- RWYFURDDADFSHT-RBBHPAOJSA-N diane Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1.C1=C(Cl)C2=CC(=O)[C@@H]3CC3[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(C)=O)(OC(=O)C)[C@@]1(C)CC2 RWYFURDDADFSHT-RBBHPAOJSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical class OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- BVURNMLGDQYNAF-UHFFFAOYSA-N dimethyl(1-phenylethyl)amine Chemical compound CN(C)C(C)C1=CC=CC=C1 BVURNMLGDQYNAF-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 235000019239 indanthrene blue RS Nutrition 0.000 description 1
- UHOKSCJSTAHBSO-UHFFFAOYSA-N indanthrone blue Chemical compound C1=CC=C2C(=O)C3=CC=C4NC5=C6C(=O)C7=CC=CC=C7C(=O)C6=CC=C5NC4=C3C(=O)C2=C1 UHOKSCJSTAHBSO-UHFFFAOYSA-N 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical compound C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 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
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- JYVLIDXNZAXMDK-UHFFFAOYSA-N methyl propyl carbinol Natural products CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 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
- 239000011707 mineral Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder 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
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は新規にして有用なる水性被覆組$.物、ならび
に該水性被覆組成物を用いる新規にして有用なる塗装方
法に関する。さらに詳細には、本発明は水酸基含有セル
ロース誘導体と無水(メタ)アクリル酸との反応生成物
を用いて得られる特定の共重合物の水性分散物と、その
架橋成分と顔料とを必須の戒分とした水性被覆組成物、
とりわけ、すぐれた塗膜外観および耐候性などを有する
、メタリック顔料を含んだ水性被覆組放物、ならびに該
水性被覆組底物をトップコート用U威物として用いる2
コートlベーク塗装方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention provides a novel and useful aqueous coating set. The present invention relates to a novel and useful coating method using the aqueous coating composition. More specifically, the present invention provides an aqueous dispersion of a specific copolymer obtained using a reaction product of a hydroxyl group-containing cellulose derivative and (meth)acrylic anhydride, its crosslinking component, and a pigment. aqueous coating composition,
In particular, an aqueous coating composition containing a metallic pigment, which has excellent coating film appearance and weather resistance, and the use of the aqueous coating assembly as a U material for a top coat.
This invention relates to a coat l bake painting method.
塗料組成物中に、溶媒に不溶なる微小な架橋重合体樹脂
粒子を配合させることによって、かかる塗料組成物の流
動性を改善せしめるという方法は、すでに、よく知られ
ている。A method of improving the fluidity of a coating composition by incorporating fine crosslinked polymer resin particles that are insoluble in a solvent into the coating composition is already well known.
とくに、特開昭56−157358号公報には、水性塗
料中に特定の微小な架橋重合体樹脂粒子を配合して、メ
タリック顔料の配向を制御せしめることにより、すぐれ
た金属光沢を有する塗膜を提供するという方法が開示さ
れている.
しかしながら、溶媒に不溶なる微小な架橋性重合体樹脂
粒子を配合せしめるというこうした方法に従う限りにお
いては、溶媒の揮発時における樹脂粒子間の融着が必然
的に低下する処から、溶剤型メタリック塗料のような平
滑性にすぐれた、良好な金属光沢塗膜を安定に作製する
ことは、極めて困難であった。In particular, JP-A No. 56-157358 discloses that a coating film with excellent metallic luster can be created by blending specific microscopic crosslinked polymer resin particles into a water-based paint to control the orientation of metallic pigments. A method of providing this information is disclosed. However, as long as this method of blending fine crosslinkable polymer resin particles insoluble in solvents is followed, the fusion between resin particles inevitably decreases when the solvent evaporates, so solvent-based metallic paints cannot be used. It has been extremely difficult to stably produce such a coating film with excellent smoothness and good metallic luster.
一方、溶剤型メタリック塗料についても、特開昭60−
144374号公報に開示されている通り、メタリック
ベース塗料にセルロースアセテートブチレート(以下、
CABと略称する。)を配合させることにより、良好な
外観および性能をもった、すぐれたメタリック塗膜が得
られることが知られている。On the other hand, regarding solvent-based metallic paints,
As disclosed in Japanese Patent No. 144374, cellulose acetate butyrate (hereinafter referred to as
It is abbreviated as CAB. ) is known to provide an excellent metallic coating film with good appearance and performance.
ところが、従来においては、かかるCABを含有する重
合体を安定に水性化せしめるべき有効な方法が見い出さ
れていなかった.
たとえば、特開昭51−28188号公報には、この種
のセルロース誘導体を含有する重合体を、特殊な乳化剤
を多量に用いて水分散化せしめるという方法が開示され
ている。However, until now, no effective method has been found for stably making such CAB-containing polymers aqueous. For example, Japanese Patent Application Laid-open No. 51-28188 discloses a method in which a polymer containing this type of cellulose derivative is water-dispersed using a large amount of a special emulsifier.
しかしながら、このような方法によって得られる水性分
散液は、分散安定性も悪く、配合時や貯蔵時などにおい
て、凝集したり分離したりし易く、しかも、こうした水
性分散液から得られる塗膜も、溶剤型のセルロース誘導
体を含有する重合体溶液からの塗膜に比して、光沢、耐
久性ならびに機械的強度などの面で、著しく劣るなどの
問題点を有している。However, the aqueous dispersion obtained by such a method has poor dispersion stability and tends to aggregate or separate during blending or storage, and furthermore, the coating film obtained from such aqueous dispersion also has poor dispersion stability. Compared to coating films made from polymer solutions containing solvent-based cellulose derivatives, they have problems such as being significantly inferior in terms of gloss, durability, and mechanical strength.
しかるに、本発明者らは上述した従来技術における種々
の欠点ないしは問題点、つまり、未解決課題の存在に鑑
みて、とりわけ、分散安定性が良好で、しかも、メタリ
ック顔料の配向の乱れもなく、したがって、すぐれた金
属光沢を有するfi!膜を与えることのできる、極めて
有用な水性被覆組成物、ならびに該水性被覆組底物を用
いる塗装方法を求めて、鋭意、研究に着手した。However, in view of the various drawbacks or problems in the prior art described above, that is, the existence of unresolved problems, the present inventors have developed a method that has particularly good dispersion stability and does not disrupt the orientation of metallic pigments. Therefore, fi! has excellent metallic luster! In search of an extremely useful aqueous coating composition capable of providing a film and a coating method using the aqueous coating composition, intensive research has been undertaken.
したがって、本発明が解決しようとする課題は、メタリ
ックベース塗料なるベースコート用組成物として用いる
のに適した新しい形の水性塗料を提供することであり、
加えて、かかる新規にして有用なる水性塗料を用いた新
しいメタリック塗装方法をも提供することである。Therefore, the problem to be solved by the present invention is to provide a new type of water-based paint suitable for use as a base coat composition, which is a metallic base paint.
In addition, it is an object of the present invention to provide a new metallic coating method using such a new and useful water-based paint.
そこで、本発明者らは上述した如き解決すべき課題に照
準を合わせて鋭意検討を重ねた結果、水酸基含有セルロ
ース誘導体、とりわけ、CABと無水(メタ)アクリル
酸との反応生威物を用いて得られる特定の共重合物の水
性分散液と、その架橋成分と顔料とを必須の戒分とした
水性被覆組成物を見い出すに及んで、本発明を完成させ
るに到った。Therefore, the present inventors have conducted extensive studies with the aim of solving the above-mentioned problems, and as a result, we have developed a method using a hydroxyl group-containing cellulose derivative, particularly a reaction product of CAB and (meth)acrylic anhydride. The present invention was completed by discovering an aqueous coating composition that essentially contains an aqueous dispersion of the resulting specific copolymer, its crosslinking component, and a pigment.
すなわち、本発明は、一つには、必須の成分として、水
酸基含有セルロース誘導体と無水(メタ)アクリル酸と
を反応させて得られるビニル基含有反応物と、カルボキ
シル基含有ビニルモノマーを必須成分とする重合性ビニ
ルモノマーとの共重合物の水性分散物(A)と、該水性
分散物中の共重合物と反応しうる架橋成分(B)と、顔
l4Cc>とを含んで成る、とりわけ、分散安定性が極
めて良好で、しかも、すぐれた金属光沢を有する塗膜を
与える、極めて有用なる水性被覆組成物を提供しようと
するものであり、二つには、こうした上記の水性被覆組
成物をベースコート用組成物、とりわけ、メタリックベ
ース塗料として用いることから成る、とりわけ、すぐれ
た金属光沢を有する塗膜を与えることのできる、新規に
して有用なるメタリック塗装方法を提供しようとするも
のである。That is, the present invention includes, as essential components, a vinyl group-containing reactant obtained by reacting a hydroxyl group-containing cellulose derivative with (meth)acrylic anhydride, and a carboxyl group-containing vinyl monomer. an aqueous dispersion (A) of a copolymer with a polymerizable vinyl monomer, a crosslinking component (B) capable of reacting with the copolymer in the aqueous dispersion, and a face l4Cc>. The object of the present invention is to provide an extremely useful aqueous coating composition that has extremely good dispersion stability and provides a coating film with excellent metallic luster. It is an object of the present invention to provide a new and useful metallic coating method which consists of a base coat composition, in particular a metallic base paint, which is capable of providing a coating film with an excellent metallic luster.
ここにおいて、まず、本発明の方法において用いられる
水性被覆組成物は、たとえば、次のような方法によって
調製することができる。First, the aqueous coating composition used in the method of the present invention can be prepared, for example, by the following method.
すなわち、9 0. O O〜9 9. 9 5重景%
の水酸基含有セルロース誘導体と0.05〜i o.
o o重量%の無水(メタ)アクリル酸とを、不活性有
機溶剤中で、反応させて得られるビニル基含有反応物の
5〜95重量部と、カルボキシル基含有ビニルモノマー
を少なくとも2重量%含有する重合性ビニルモノマーの
95〜5重量部とを、重合開始剤の存在下で、共重合反
応せしめることにより、カルボキシル基含有変性共重合
物を調製するという第一工程と、次いで、かかる変性共
重合物中に存在するカルボキシル基の少なくとも一部を
、塩基性化合物により中和したのち、該中和物を水中に
分散させるが、そのさいに、上記塩基性化合物を用いて
のpHを、5以上となるように設定せしめるという第二
工程と、さらに、かくして得られるカルボキシル基含有
変性共重合物の水性分散物(A)に対して、該(A)戒
分と反応しうる架橋成分(B)と顔料(C)とを混合せ
しめるという第三工程とを通して、本発明の水性被覆組
成物が得られるが、勿論、これのみに限定されるもので
はない。That is, 90. O O~9 9. 9 5th view%
of hydroxyl group-containing cellulose derivative and 0.05 to io.
Contains 5 to 95 parts by weight of a vinyl group-containing reactant obtained by reacting o o wt % of (meth)acrylic anhydride in an inert organic solvent and at least 2 wt % of a carboxyl group-containing vinyl monomer. A first step of preparing a carboxyl group-containing modified copolymer by copolymerizing 95 to 5 parts by weight of a polymerizable vinyl monomer in the presence of a polymerization initiator; After at least a portion of the carboxyl groups present in the polymer is neutralized with a basic compound, the neutralized product is dispersed in water, and at this time, the pH using the basic compound is adjusted to 5. The second step is to set the above conditions, and further, the crosslinking component (B ) and the pigment (C), the aqueous coating composition of the present invention is obtained, but of course it is not limited thereto.
前記した水酸基含有セルロース誘導体としては、セルロ
ースを原料として得られた水性被覆用樹脂組成物を基質
ないしは基材に塗布し乾燥させて形威される塗膜の表面
が粘着性を示さず、しかも、耐水性や耐油性などにすぐ
れた塗膜を与えることができるようなものが望ましい。The above-mentioned hydroxyl group-containing cellulose derivative is such that an aqueous coating resin composition obtained using cellulose as a raw material is applied to a substrate or a base material, and the surface of the coating film formed by drying does not exhibit tackiness. A material that can provide a coating film with excellent water resistance and oil resistance is desirable.
かかる水酸基含有セルロース誘導体として特に代表的な
もののみを挙げるに止めれば、エステル変性水酸基含有
セルロース誘導体やエーテル変性水酸基含有セルロース
誘導体などである。Typical examples of such hydroxyl group-containing cellulose derivatives include ester-modified hydroxyl group-containing cellulose derivatives and ether-modified hydroxyl group-containing cellulose derivatives.
そして、エステル変性水酸基含有セルロース誘導体の具
体例としては、ニトロセルロース、CAB,セルロース
アセテートブロビオネート、セルロースアセテートフタ
レート、アセチルセルロース、プロビオン酸セルロース
、酪酸セルロース、燐酸セルロースまたは硫酸セルロー
スなどが挙げられるし、エーテル変性水酸基含有セルロ
ース誘導体の具体例としては、メチルセルロース、エチ
ルセルロース、フチルセルロース、ベンジルセルロース
、カルポキシメチルセルロース、カルボキシルエチルセ
ルロース、アミノエチルセルロース、オキシエチルセル
ロース、ヒドロキシエチルセルロース、ヒドロキシプ口
ピルセルロースまたはヒドロキシプ口ピルメチルセルロ
ースなどが挙ケられる。Specific examples of ester-modified hydroxyl group-containing cellulose derivatives include nitrocellulose, CAB, cellulose acetate brobionate, cellulose acetate phthalate, cellulose acetate, cellulose probionate, cellulose butyrate, cellulose phosphate, and cellulose sulfate. Specific examples of ether-modified hydroxyl group-containing cellulose derivatives include methylcellulose, ethylcellulose, phthylcellulose, benzylcellulose, carpoxymethylcellulose, carboxylethylcellulose, aminoethylcellulose, oxyethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose or hydroxypropylmethylcellulose. etc. are mentioned.
当該水酸基含有セルロース誘導体の中でも、セルロース
の部分アセチル化物を、さらにブチルエステル化、つま
り、エステル変性せしめて得られる形のCABの使用が
望ましい。Among the hydroxyl group-containing cellulose derivatives, it is desirable to use CAB obtained by further butyl esterification, that is, ester modification, of a partially acetylated cellulose.
また、当該水酸基含有セルロース誘導体の数平均分子量
としては、3,000〜300, 000なる範囲内が
、好ましくはs,ooo〜150,000なる範囲内が
適切である。Further, the number average molecular weight of the hydroxyl group-containing cellulose derivative is suitably within the range of 3,000 to 300,000, preferably within the range of s,ooo to 150,000.
さらに、当該水酸基含有セルロース誘導体中における水
酸基の含有率としては、0. 4重量%以上が適当であ
る。0.4重量%未満の場合には、当該セルロース誘導
体中に導入できる(メタ)アクリロイル(オキシ)基数
が少なくなるため、グラフF化率が低下し、ひいては、
カルボキシル基含有変性重合体とも言うべきビニル基含
有反応物(共重合物コそれ自体が乳化しにくくなる傾向
にあるので、好ましくない。Furthermore, the content of hydroxyl groups in the hydroxyl group-containing cellulose derivative is 0. A suitable amount is 4% by weight or more. If it is less than 0.4% by weight, the number of (meth)acryloyl (oxy) groups that can be introduced into the cellulose derivative decreases, resulting in a decrease in the graph F conversion rate, and as a result,
A vinyl group-containing reactant (also called a carboxyl group-containing modified polymer) (copolymer) itself tends to become difficult to emulsify, so it is not preferred.
当該水酸基含有セルロース誘導体の市販品として特に代
表的なもののみを例示するに止めれば、アメリカ国イー
ストマン・コダック社製のr CABシリーズ」、rC
APシリーズ」またはr(Aシリーズ」などである。Particularly representative examples of commercially available hydroxyl group-containing cellulose derivatives include "r CAB series" manufactured by Eastman Kodak Company in the United States, rC
"AP series" or r (A series).
前記共重合物たるビニル基含有反応物の調製は、当該水
酸基含有セルロース誘導体と、無水(メタ)アクリル酸
とを、不活性有機溶媒中で、50〜120゜Cなる温度
範囲で、10分間〜8時間のあいだ反応せしめることに
よって行なわれるが、このさいの反応は、無触媒の状態
でも進行はするものの、エステル化触媒を存在させるこ
とにより、一層、促進される。The preparation of the vinyl group-containing reactant as the copolymer is carried out by mixing the hydroxyl group-containing cellulose derivative and (meth)acrylic anhydride in an inert organic solvent at a temperature of 50 to 120°C for 10 minutes to 120°C. The reaction is carried out for 8 hours, and although the reaction proceeds in the absence of a catalyst, it is further accelerated by the presence of an esterification catalyst.
このように、無触媒の下で、水酸基含有セルロース誘導
体に(メタ)アクリロイル(オキシ)基を導入せしめる
ことは、通常の方法では困難であり、反応性のよい無水
(メタ)アクリル酸を用いて、はじめて可能となるもの
である。In this way, it is difficult to introduce (meth)acryloyl (oxy) groups into hydroxyl group-containing cellulose derivatives in the absence of catalysts using normal methods. , is possible for the first time.
かかるエステル化反応の反応率は、酸価あるいはフーリ
エ変換赤外分光光度計(FT−IR)などを利用して測
定することができる。The reaction rate of such esterification reaction can be measured using an acid value or a Fourier transform infrared spectrophotometer (FT-IR).
エステル化触媒としては、アミン、アルカリ金属水酸化
物または鉱酸などが挙げられる。好ましい半エステル化
触媒としては、トリメチルアξン、トリエチルアごン、
トリプロビルアミンなどのトリアルキルアミン;N−ア
ルキルモルホリン;トリエチレンジアξン、N.N’−
ジメチルビペラジン、ヘキサメチレンテトラ逅ン、ピリ
ジン、ピラジン、キノリン、ペンジルジメチルアよン、
α一メチルベンジルジメチルアξン、N−アルキルイミ
ダゾリン、トリフェニルホスフィンまたはトリシクロヘ
キシルホスフィンなどが挙げられる。Esterification catalysts include amines, alkali metal hydroxides, mineral acids, and the like. Preferred half-esterification catalysts include trimethylamine, triethylamine,
Trialkylamines such as triprobylamine; N-alkylmorpholines; triethylene diane, N. N'-
Dimethylbiperazine, hexamethylenetetrazine, pyridine, pyrazine, quinoline, penzyldimethylamine,
Examples include α-methylbenzyldimethylamine, N-alkylimidazoline, triphenylphosphine, and tricyclohexylphosphine.
水酸基含有セルロース誘導体と無水アクリル酸および/
または無水メタクリル酸の使用割合は、重量比で90:
10〜99.95:0.05の範囲が好ましく、95:
5〜9 9. 9 : 0. 1の範囲が特に好ましい
。無水アクリル酸および/または無水メタクリル酸の使
用割合が0.05重量%より少ない場合には、水性媒体
中におけるカルボキシル基含有変性重合体の分散安定性
が劣る傾向にあるので好ましくない。無水アクリル酸ま
たは無水メタクリル酸の使用割合が10重量%より多い
場合には、重合時にカルボキシル基含有変性重合体が高
分子量化しやすく、好ましくない。Hydroxyl group-containing cellulose derivative and acrylic anhydride and/or
Or the ratio of methacrylic anhydride used is 90:
The range of 10 to 99.95:0.05 is preferable, and 95:
5-9 9. 9:0. A range of 1 is particularly preferred. If the proportion of acrylic anhydride and/or methacrylic anhydride used is less than 0.05% by weight, it is not preferred because the dispersion stability of the carboxyl group-containing modified polymer in the aqueous medium tends to be poor. If the proportion of acrylic anhydride or methacrylic anhydride used is more than 10% by weight, the carboxyl group-containing modified polymer tends to have a high molecular weight during polymerization, which is not preferable.
本発明で用いられる前記共重合物の水性分散物(A)中
の共重合物を得るにさいして、まず、ビニル基含有反応
物を調製するにさいして用いる不活性有機溶媒としては
、アセトン、メチルエチルケトン、メチルイソプチルケ
トン、エチルプロビルケトンまたはエチルブチルケトン
などのケトン系溶媒が好ましい。In obtaining the copolymer in the aqueous dispersion (A) of the copolymer used in the present invention, first, as the inert organic solvent used in preparing the vinyl group-containing reactant, acetone, Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, ethyl probyl ketone or ethyl butyl ketone are preferred.
ビニル基含有反応物との共重合反応に用いる重合性ビニ
ルモノマーは、カルボ革シル含有ビニルモノマーを少な
くとも2重量%含有する重合性ビニルモノマーである。The polymerizable vinyl monomer used in the copolymerization reaction with the vinyl group-containing reactant is a polymerizable vinyl monomer containing at least 2% by weight of a carboxylic vinyl monomer.
カルボキシル基含有ビニルモノマーの使用量が2重量%
より少ない場合には、水性媒体中における樹脂の分散安
定性が、どうしても、悪くなる傾向にあるので好ましく
ない。The amount of carboxyl group-containing vinyl monomer used is 2% by weight.
If the amount is less, the dispersion stability of the resin in the aqueous medium inevitably tends to deteriorate, which is not preferable.
カルボキシル基含有ビニルモノマーとしては、アクリル
酸、メタクリル酸、クロトン酸、イタコン酸、マレイン
酸またはフマル酸などが、特に代表的なものである。Particularly typical carboxyl group-containing vinyl monomers include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid.
カルボキシル基含有ビニルモノマー以外の重合性ビニル
モノマーとして特に代表的なもののみを例示するに止め
れば、スチレン、ビニルトルエン、2−メチルスチレン
、t−プチルスチレンもしくはクロルスチレンの如きス
チレン系モノマー;アクリル酸メチル、アクリル酸エチ
ル、アクリル酸イソプロビル、アクリル酸n−ブチル、
アクリル酸イソブチル、アクリル酸n−ア5ル、アクリ
ル酸イソアくル、アクリル酸n−ヘキシル、アクリル酸
2−エチルヘキシル、アクリル酸n−オクチル、アクリ
ル酸デシル、アクリル酸ドデシルの如きアクリル酸エス
テル類;メタクリル酸メチル、メタクリル酸プロビル、
メタクリル酸n−ブチル、メタクリル酸イソブチル、メ
タクリル酸n−アごル、メタクリル酸n−ヘキシル、メ
タクリル酸n一オクチル、メタクリル酸2−エチルヘキ
シル、メタクリル酸デシル、メタクリル酸ドデシルの如
きメタクリル酸エステル類;アクリル酸ヒドロキシエチ
ル、アクリル酸ヒドロキシブロビル、メタクリル酸ヒド
ロキシエチル、メタクリル酸ヒドロキシプ口ビルの如き
ヒドロキシル基含有モノマー;ポリエチレングリコール
、ポリプロピレングリコールの如き(ポリ)アルキレン
グリコールまたはそれらのモノアルキルエーテルのモノ
アクリル酸もしくはモノメタクリル酸エステル系モノマ
ー;グリシジルアクリレート、グリシジルメタクリレー
トの如きグリシジル基含有モノマー;あるいはN−メチ
ロール(メタ)アクリルア果ド、Nーブトキシメチル(
メタ)アクリルアミドの如きN置換(メタ)アクリル系
モノマーなどが挙げられる。Typical examples of polymerizable vinyl monomers other than carboxyl group-containing vinyl monomers include styrene monomers such as styrene, vinyltoluene, 2-methylstyrene, t-butylstyrene, or chlorostyrene; acrylic acid; Methyl, ethyl acrylate, isoprobyl acrylate, n-butyl acrylate,
Acrylic acid esters such as isobutyl acrylate, n-alkyl acrylate, isoalkyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, decyl acrylate, and dodecyl acrylate; Methyl methacrylate, provil methacrylate,
Methacrylic acid esters such as n-butyl methacrylate, isobutyl methacrylate, n-agol methacrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, and dodecyl methacrylate; Hydroxyl group-containing monomers such as hydroxyethyl acrylate, hydroxybrobyl acrylate, hydroxyethyl methacrylate, and hydroxybutyvir methacrylate; monoacrylics of (poly)alkylene glycols such as polyethylene glycol and polypropylene glycol or their monoalkyl ethers; Acid or monomethacrylic acid ester monomers; glycidyl group-containing monomers such as glycidyl acrylate and glycidyl methacrylate; or N-methylol (meth)acrylate, N-butoxymethyl (
Examples include N-substituted (meth)acrylic monomers such as meth)acrylamide.
当該ビニル基含有反応物は、前記ビニル基含有反応物と
前記重合性ビニルモノマーとを溶液重合させることによ
って調製されるのが、特に望ましい。It is particularly desirable that the vinyl group-containing reactant is prepared by solution polymerizing the vinyl group-containing reactant and the polymerizable vinyl monomer.
ビニル基含有反応物と重合性ビニルモノマーの使用割合
は、重量比で5二95〜95:5の範囲が好ましい。ビ
ニル基含有反応物の使用割合が5重量%より少ない場合
には、水酸基含有セルロース誘導体のもつ種々の特性を
生かせない場合があるので好ましくない。ビニル基含有
反応物の使用割合が95重量%より多い場合には、カル
ボキシル基含有変性重合体が自己乳化しにくくなる傾向
にあり好ましくない。The ratio of the vinyl group-containing reactant to the polymerizable vinyl monomer is preferably in the range of 5295 to 95:5 by weight. If the proportion of the vinyl group-containing reactant used is less than 5% by weight, it is not preferable because the various properties of the hydroxyl group-containing cellulose derivative may not be utilized. If the proportion of the vinyl group-containing reactant used is more than 95% by weight, the carboxyl group-containing modified polymer tends to become difficult to self-emulsify, which is not preferable.
特に重合性ビニルモノマーの使用割合が少ないものは、
カルボキシル基含有変性重合体中のセルロース誘導体の
割合が高いため、他の水性のアクリル樹脂、ポリエステ
ル樹脂、ウレタン樹脂に添加することにより、セルロー
ス誘導体が有する特徴を引き出すことができる。この場
合、本発明の被覆組底物を上記水性樹脂に添加する方法
、またはカルボキシル基含有変性重合体の段階で、上記
水性樹脂と混合したのち、水分散化せしめるという方法
を用いることができる。In particular, those with a low proportion of polymerizable vinyl monomer are
Since the proportion of cellulose derivatives in the carboxyl group-containing modified polymer is high, the characteristics of cellulose derivatives can be brought out by adding it to other water-based acrylic resins, polyester resins, and urethane resins. In this case, it is possible to use a method in which the coated bottom of the present invention is added to the aqueous resin, or a method in which it is mixed with the aqueous resin at the stage of the carboxyl group-containing modified polymer and then water-dispersed.
ビニル基含有反応物と重合性ビニルモノマーとの共重合
反応に用いる重合開始剤としては、たとえば、アブビス
イソブチロニトリル、ペンゾイルパーオキサイドまたL
−プチルバーオキシ−2−エチルヘキサネートなどの通
常のラジカル重合開始剤が挙げられる。Examples of the polymerization initiator used in the copolymerization reaction between the vinyl group-containing reactant and the polymerizable vinyl monomer include abbisisobutyronitrile, penzoyl peroxide, and L
Examples include common radical polymerization initiators such as -butylbaroxy-2-ethylhexanate.
共重合反応に用いる有機溶媒としては、たとえば、メタ
ノール、エタノール、プロパノール、ブタノールの如き
アルコール類;メチルセロソルプ、エチルセロソルブ、
プロビルセロソルブ、プチルセロソルブ、メチル力ルビ
トール、エチル力ルビトールの如きエーテルアルコール
類;メチルエチルケトン、ジイソブチルケトンの如きケ
トン類やトルエンの如き芳香族炭化水素などが挙げられ
る。Examples of organic solvents used in the copolymerization reaction include alcohols such as methanol, ethanol, propanol, and butanol; methyl cellosolve, ethyl cellosolve,
Examples include ether alcohols such as provil cellosolve, butyl cellosolve, methyl rubitol, and ethyl rubitol; ketones such as methyl ethyl ketone and diisobutyl ketone; and aromatic hydrocarbons such as toluene.
本発明の水性被覆組成物は、前記重合反応によって得ら
れたカルボキシル基含有変性共重合体に分散液のpHが
5以上となる量の塩基性化合物を加えて、前記変性共重
合体を水性媒体中に分散させることによって得られる。The aqueous coating composition of the present invention is prepared by adding a basic compound in an amount such that the pH of the dispersion becomes 5 or more to the carboxyl group-containing modified copolymer obtained by the polymerization reaction, and dispersing the modified copolymer in an aqueous medium. obtained by dispersing it in
ここで使用される塩基性化合物は、アンモニアや揮発性
のアξンが好ましく、無機塩基は、塗膜中に残留し耐水
性を悪くする傾向があるので好ましくない。The basic compound used here is preferably ammonia or volatile amine, and inorganic bases are not preferred because they tend to remain in the coating film and impair water resistance.
上記アミンとしては、たとえば、トリメチルアミン、ト
リエチルアミン、プチルアくンの如きアルキルアミン類
;ジメチルアミノエタノール、ジエタノールア〔ン、ア
ミノメチルプロバノールの如きアルコールアミン類;ま
たはモルホリンなどが使用できる。また、エチレンジア
ミンやジエチレントリアミンなどの多価アくンも使用で
きる。Examples of the amine that can be used include alkylamines such as trimethylamine, triethylamine, and butylamine; alcohol amines such as dimethylaminoethanol, diethanolamine, and aminomethylprobanol; and morpholine. Moreover, polyhydric amines such as ethylenediamine and diethylenetriamine can also be used.
本発明において水性媒体とは、少なくとも10重量%が
水である水単独もしくは親水性有機溶剤との混合物を意
味する。親水性有機溶剤としては、たとえば、メタノー
ル、エタノール、n−プロパノール、イソプロバノール
、n−ブタノール、sec−ブタノール、tert−ブ
タノール、イソブタノールの如きアルキルアルコール類
:メチルセロソルブ、エチルセロソルブ、プロビルセロ
ソルブ、プチルセロソルブ、ヘキシルセロソルブ、メチ
ル力ルビトール、エチル力ルビトールの如きグリコール
エーテル類;またはメチルセロソルブアセテート、エチ
ルセロソルブアセテートの如きグリコールエーテルエス
テル類などをはじめ、さらには、ジオキサン、ジメチル
ホルムアミド、ダイア七トンアルコール、テトラヒド口
フランなどが使用できる。In the present invention, the aqueous medium means water alone or in a mixture with a hydrophilic organic solvent, in which at least 10% by weight is water. Examples of hydrophilic organic solvents include alkyl alcohols such as methanol, ethanol, n-propanol, isoprobanol, n-butanol, sec-butanol, tert-butanol, and isobutanol; methyl cellosolve, ethyl cellosolve, provil cellosolve; Glycol ethers such as butyl cellosolve, hexyl cellosolve, methyl-rubitol, and ethyl-rubitol; or glycol ether esters such as methyl cellosolve acetate and ethyl cellosolve acetate, as well as dioxane, dimethylformamide, diaheptone alcohol, Tetrahydrofuran, etc. can be used.
本発明において用いられる水性被覆組成物は、分散安定
性が非常に良好であり、さらに含有する有機溶剤を減ら
す必要がある場合には、アセトン、メチルエチルケトン
などの沸点の低い溶剤や、ブタノールやプチルセロソル
ブなどの水と共沸する溶剤を、反応溶剤や分散助剤とし
て用いれば、水性媒体中に、分散後に、常圧もしくは減
圧にて蒸留することにより、安定的にして、かつ容易に
、低有機溶剤含有の被覆組成物を得ることができる。The aqueous coating composition used in the present invention has very good dispersion stability, and if it is necessary to further reduce the amount of organic solvent contained, low boiling point solvents such as acetone, methyl ethyl ketone, butanol and butyl cellosolve can be used. If a solvent that is azeotropic with water, such as Solvent-containing coating compositions can be obtained.
本発明において、前述の(A)成分と反応する架橋戒分
(B)としては、水溶性あるいは水分敵性メラミン樹脂
が挙げられる。が、そのうちでも特に代表的なもののみ
を挙げるに止めれば、「ニカラックMW−30」(日本
カーバイド工業■製品〕、「スミマールM−100J(
住友化学工業■製品〕の如き、ヘキサメトキシメチルメ
ラミンや、「スミマールM−40WJもしくは「ス逅マ
ールM−30WJ (以上、住友化学工業■製品〕の
如き遊離メチロール基を含むメトキシメチルメラミン樹
脂などがある。また、水/メタノール混合溶剤(重量比
35/65)での溶剤希釈率が20以下なる疎水性メラ
ξン樹脂を水溶性樹脂、あるいは、分散剤により水分散
化したメラξン樹脂も使用でき、中でも特に好ましいの
は、ヘキサメトキシメチルメラミン樹脂である。In the present invention, the crosslinking component (B) that reacts with the above-mentioned component (A) includes water-soluble or water-friendly melamine resins. However, to mention only the most representative ones, there are "Nikalak MW-30" (Nippon Carbide Kogyo product), "Sumimar M-100J" (product of Nippon Carbide Industries).
Hexamethoxymethyl melamine, such as Sumitomo Chemical Product), and methoxymethyl melamine resin containing free methylol groups, such as Sumimaru M-40WJ or Sumitomo Chemical Product M-30WJ (hereinafter Sumitomo Chemical Product), etc. There is also a water-soluble resin, or a mela ξ resin made by water dispersing a hydrophobic mela ξ resin with a solvent dilution ratio of 20 or less in a water/methanol mixed solvent (weight ratio 35/65), or a dispersant. Particularly preferred among those that can be used is hexamethoxymethylmelamine resin.
本発明において、前記顔料(C)としては、通常、塗料
の分野で用いられるメタリック顔料および/または着色
顔料などが挙げられる。そのうち、かかるメタリノク顔
料として特に代表的なもののみを挙げるに止めれば、ア
ルミニウムフレークや銅ブロンズフレークなどを挙げる
ことができる。In the present invention, examples of the pigment (C) include metallic pigments and/or colored pigments commonly used in the field of paints. Among them, only representative metal pigments include aluminum flakes and copper bronze flakes.
一方、上記の着色顔料として特に代表的なもののみを挙
げるに止めれば二酸化チタン、酸化鉄、酸化クロム、ク
ロム酸鉛もしくはカーボンブラックの如き無機顔料;ま
たはフタロシアニンプルーフタ口シアニングリーン、カ
ルバゾールバイオレット、アントラピリミジンイエロー
、フラバンスロンイエロー、イソインドリンイエロー、
インダンスロンブルーもしくはキナクリドンバイオレッ
トの如き有機顔料を挙げることができる。本発明におい
ては、上掲された如きメタリック顔料および着色顔料の
少なくとも一種を用いるが、さらにタルクやカオリンな
どの体質顔料をも併用することができる。On the other hand, the above-mentioned color pigments include inorganic pigments such as titanium dioxide, iron oxide, chromium oxide, lead chromate, or carbon black; or phthalocyanine-proof cyanine green, carbazole violet, and anthracite. pyrimidine yellow, flavanthrone yellow, isoindoline yellow,
Organic pigments such as indanthrone blue or quinacridone violet may be mentioned. In the present invention, at least one of the metallic pigments and colored pigments listed above is used, but extender pigments such as talc and kaolin can also be used in combination.
これらの各種顔料のうち、着色顔料または体質顔料は架
橋成分(B)の配合時に加えるのが好ましく、一方、メ
タリック顔料は(A)戒分と(B)戒分との調合時に加
えるのが好ましい。Among these various pigments, coloring pigments or extender pigments are preferably added at the time of blending the crosslinking component (B), while metallic pigments are preferably added at the time of blending (A) Kibun and (B) Kibun. .
次に、本発明の方法を実施するにさいし、水性被覆組威
物における各成分の具体的な配合割合としては、次のよ
うな割合とすることが適当である.すなわち、(A)成
分たる共重合物の水性分散物の樹脂固形分100重量部
に対して、(B)戒分たる架橋剤用樹脂の固形分に換算
して、8〜70重量部程度、好ましくは、10〜60重
量部程度の範囲で配合するのが適切である。かかる(B
)戒分の配合が8重量部未満の場合は、加熱による硬化
反応が不十分となるために、塗膜の耐湿性や耐溶剤性な
どが低下する傾向にあるので好ましくなく、一方、70
重量部より多い場合には、耐チフピング性や耐候性など
が低下すると共に、クリアー上塗り塗料を重ね塗りずる
さい、タレやムラなどの現象が発生するようになるので
好ましくない。また、(C)成分たる顔料はAll或物
に所望の色彩などに応じて、適宜、配合すればよく、(
A)成分と(B)成分とを合計した樹脂固形分100重
量部に対して、通常、l〜230重量部程度の範囲内で
配合するのが適当である。本発明の水性被覆組戒物は、
たとえば、次のようにして調製することができる。すな
わち、前述のようにして調製された共重合物の水性分散
物と架橋剤と、メタリック塗装において用いられる場合
のメタリック顔料とに、通常の方法に従って、脱イオン
水および、必要に応じて、増粘剤や消泡剤などの添加剤
を加えて、固形分10〜40重景%程度で、かつ、粘度
200 〜5000cps /6rpt* (B型粘
度計〉程度に調製して、本発明の目的物たる水性被覆組
底物を得る。本発明の方法において得られる水性被覆組
成物は、2コートlベーク方式で塗装する場合のベース
コートm成物として極めて適している。Next, when carrying out the method of the present invention, it is appropriate to set the specific proportions of each component in the aqueous coating composition as follows. That is, based on 100 parts by weight of the resin solid content of the aqueous dispersion of the copolymer which is the component (A), about 8 to 70 parts by weight in terms of the solid content of the crosslinking agent resin (B), Preferably, it is appropriate to mix in a range of about 10 to 60 parts by weight. It takes (B
) If the amount of the precept is less than 8 parts by weight, the curing reaction by heating will be insufficient, and the moisture resistance and solvent resistance of the coating film will tend to decrease, which is not preferable.
If the amount is more than 1 part by weight, it is not preferable because the chipping resistance and weather resistance will deteriorate, and the clear topcoat will be difficult to overcoat, and phenomena such as sagging and unevenness will occur. In addition, the pigment as component (C) may be blended as appropriate depending on the desired color of the All or object.
Generally, it is appropriate to mix 1 to 230 parts by weight with respect to 100 parts by weight of the total resin solid content of component A) and component (B). The aqueous coated samurai of the present invention is
For example, it can be prepared as follows. That is, the aqueous dispersion of the copolymer prepared as described above, the crosslinking agent, and the metallic pigment when used in metallic coatings are mixed with deionized water and, if necessary, additives, according to conventional methods. By adding additives such as a sticky agent and an antifoaming agent, the solid content is approximately 10 to 40%, and the viscosity is approximately 200 to 5000 cps/6rpt* (B-type viscometer) to achieve the purpose of the present invention. The aqueous coating composition obtained by the method of the present invention is extremely suitable as a base coat composition when applied in a two-coat one-bake system.
たとえば、当該組成物を、lO〜50μ程度の乾燥膜厚
になるように、スプレー塗装などにより被塗物に塗装し
、風乾あるいは温風乾燥などにより、揮発成分が25重
量%以下の程度になるまで乾燥させ、次いで、クリアー
上塗り塗料を、乾燥膜厚15〜70μ程度になるように
、静電スプレー塗装などにより塗り重ねる。しかるのち
、通常のセッティングを行ってから、120〜160℃
程度で15〜30分程度の焼付けを行なって硬化塗膜と
する。ここで用いられるクリアー上塗り塗料としては、
従来において公知のものが使用できる。For example, the composition is applied to an object by spray coating to a dry film thickness of about 10 to 50μ, and then air-dried or warm-air-dried until the volatile components are reduced to about 25% by weight or less. Then, a clear top coat is applied by electrostatic spray coating to a dry film thickness of about 15 to 70 μm. After that, perform the normal setting and then heat the temperature to 120-160℃.
Baking is performed for about 15 to 30 minutes to form a cured coating film. The clear top coat used here is
Conventionally known materials can be used.
そのうちでも特に代表的なもののみを挙げるに止めれば
、アミノアルキッド樹脂、アクリル樹脂、7兆ノアクリ
ル樹脂、アミノオイルフリーアルキソド樹脂、シリコン
ポリエステル樹脂、ふっ素樹脂またはウレタン樹脂系な
どの有機溶剤希釈型塗料が挙げられる。また、クリアー
上塗り塗料としては、環境問題や省資源などの観点から
、有機溶剤の使用量の少ないハイソリッド型のものが望
ましく、さらには、粉体塗料も用いることもできる.〔
発明の効果〕
本発明の水性被覆組底物を用いることにより、次のよう
な効果が得られる。すなわち、(1)本発明において用
いられる共重合物の水性分散物(A)は相溶性の異なる
セルロース誘導体とカルボキシル基含有ビニルモノマー
とを使用して得られるものではあるが、これらが化学的
に一体となって結合している処から、相分離を起こすこ
とがなく、しかも、カルボキシル基を有するものである
処から、水性媒体に対して自己乳化性を有し、したがっ
て、このために分散安定性が非常に良好である.(2)
セルロース誘導体の耐溶剤性が良好なことから、この水
性被覆組戒物がメタリソクベースコート組成物として用
いられた場合、焼付けせず、未硬化の状態で熱硬化樹脂
系クリアー上塗り塗料が塗布されても、上塗り塗料の溶
剤によってベースコートに含まれるメタリック顔料の配
向が乱れる事なく、このために、すぐれた金属光沢を有
する塗膜を容易に得ることができる。(3)有機溶剤の
使用量を大幅に削減できるので、環境問題や省資源など
の観点からも、すぐれている。Among them, organic solvent diluted types such as amino alkyd resin, acrylic resin, 7 trillion acrylic resin, amino oil-free alkydo resin, silicone polyester resin, fluororesin or urethane resin, to name only the most representative ones. One example is paint. Furthermore, from the viewpoint of environmental issues and resource conservation, it is desirable to use a high-solid type clear topcoat that uses a small amount of organic solvent, and powder coatings can also be used. [
Effects of the Invention] By using the aqueous coated bottom of the present invention, the following effects can be obtained. That is, (1) although the aqueous dispersion (A) of the copolymer used in the present invention is obtained using a cellulose derivative and a carboxyl group-containing vinyl monomer that have different compatibility, these are chemically Because they are bonded together, they do not cause phase separation, and because they have carboxyl groups, they have self-emulsifying properties in aqueous media, and therefore have stable dispersion. The properties are very good. (2)
Because cellulose derivatives have good solvent resistance, when this water-based coating composition is used as a metallisoku base coat composition, a thermosetting resin-based clear top coat is applied without baking and in an uncured state. Also, the orientation of the metallic pigments contained in the base coat is not disturbed by the solvent in the top coat, and therefore a coating film with excellent metallic luster can be easily obtained. (3) Since the amount of organic solvent used can be significantly reduced, it is also excellent from the viewpoint of environmental issues and resource conservation.
したがって、本発明の水性被覆組成物は美粧性外観が重
要視される自動車、2輪車または電気製品の如き外板な
どを、2コー}1ベーク方式で塗装ずるさいのベースコ
ート組成物として、極めて好適であり、とくに、メタリ
ック塗装などの装飾塗装を極めて作業性よく、かつ、満
足な仕上げで行うことができる。Therefore, the aqueous coating composition of the present invention can be used as a base coat composition that is extremely difficult to apply on exterior panels of automobiles, two-wheeled vehicles, and electrical appliances where cosmetic appearance is important, using a two-coat one-bake method. It is suitable, and in particular, decorative coatings such as metallic coatings can be performed with extremely good workability and a satisfactory finish.
次に、本発明を参考例、実施例および応用例により、一
層、具体的に説明する。以下において、部および%は特
に断りのない限り、すべて重量基準であるものとする。Next, the present invention will be explained in more detail by reference examples, examples, and application examples. In the following, all parts and percentages are based on weight unless otherwise specified.
参考例1 〔共重合物の水性分散物(A)の調製例〕
まず、窒素ガスで置換された四ツロフラスコに、r C
AB−553 J (アメリカ国イーストマン・コダ
ック社製のセルロース・アセテート・ブチレート;一分
子中の水酸基含有率=4.3%)の125部およびメチ
ルエチルケトンの250部とを仕込んで完全に溶解させ
たのち、さらに、無水メタクリル酸の0. 5部をも仕
込んで、攪拌しながら80℃まで昇温し、同温度に5時
間保持して、ビニル基含有反応物を得た.
次いで、このビニル基含有反応物を含む反応混合物の2
00部に、メチルエチルケトンの100部、n−プタノ
ールの100部、メタクリル酸のlO部、メタクリル酸
メチルの160部、アクリル酸一n−プチルの70部、
および「パーブチル0」 〔日本油脂■製の、ter
t−プチルパーオキシ2−エチルヘキサノエートなるラ
ジカル重合開始剤〕の6部を均一に混合せしめたのち、
その混合液の200部を、窒素ガスで置換された四ツ目
フラスコに仕込んで80℃に加熱し、同温度に保持しな
がら、残りの混合物を4時間を要して滴下し、さらに同
温度に4時間のあいだ、撹拌下に保持して、カルボキシ
ル基含有変性重合体たる変性共重合体を得た。Reference Example 1 [Preparation example of aqueous dispersion (A) of copolymer] First, in a Yotsuro flask purged with nitrogen gas, r C
125 parts of AB-553 J (cellulose acetate butyrate manufactured by Eastman Kodak, USA; hydroxyl group content in one molecule = 4.3%) and 250 parts of methyl ethyl ketone were charged and completely dissolved. Later, 0.0% of methacrylic anhydride was added. 5 parts were also charged, the temperature was raised to 80°C with stirring, and the temperature was maintained for 5 hours to obtain a vinyl group-containing reaction product. 2 of the reaction mixture containing this vinyl group-containing reactant.
00 parts, 100 parts of methyl ethyl ketone, 100 parts of n-butanol, 10 parts of methacrylic acid, 160 parts of methyl methacrylate, 70 parts of n-butyl acrylate,
and “Perbutyl 0” [manufactured by NOF ■, ter
After uniformly mixing 6 parts of t-butylperoxy 2-ethylhexanoate, a radical polymerization initiator,
200 parts of the mixture was charged into a four-eye flask purged with nitrogen gas, heated to 80°C, and while maintained at the same temperature, the remaining mixture was added dropwise over 4 hours, and further heated to the same temperature. The mixture was kept under stirring for 4 hours to obtain a modified copolymer, which is a modified polymer containing carboxyl groups.
しかるのち、前述した如き第一の工程で得られた変性共
重合体を含む反応液に、28%アンモニア水溶液の7部
とプチルセロソルブの60部とを加えて均一に混合して
から、イオン交換水の500部を30分間かけて滴下せ
しめてた処、不揮発分(N V)が24.9%で、かつ
、pllが7.5なる乳青白色の目的共重合体水性分散
物(A)が得られた.以下、これを水性分散物(A−1
)と略記する.このものの粘度は、1週間のあいだ室温
に放置したのちにおいても、何ら、変化が認められなか
った。Thereafter, 7 parts of a 28% ammonia aqueous solution and 60 parts of butyl cellosolve were added to the reaction solution containing the modified copolymer obtained in the first step as described above, mixed uniformly, and then subjected to ion exchange. When 500 parts of water was dropped over 30 minutes, a milky blue-white aqueous dispersion (A) of the objective copolymer with a non-volatile content (N V) of 24.9% and a pll of 7.5 was obtained. was gotten. Hereinafter, this was prepared as an aqueous dispersion (A-1
). No change in the viscosity of this product was observed even after it was left at room temperature for one week.
また、このものから有i溶剤を除去せしめるべく減圧蒸
留にかけてメチルエチルケトンおよびn一プタノールと
一部のプチルセロソルブとを除いた処、NVが40.1
%なる良好な水分散が得られた.
参考例2(同上)
ビニル基含有反応物を含む反応混合物の100部に対し
て、メチルエチルケトンの150部、メタクリル酸のl
O部、メタクリル酸メチルの130部、スチレンの53
部、アクリル酸一n−ブチルの150部および「パーブ
チルO」の6部を均一に混合せしめるように変更した以
外は、参考例lと同様にして、カルボキシル基含有変性
共重合体を得た.
次いで、この変性共重合体を含む反応液に28%アンモ
ニア水の7部を加えて均一に混合したのち、イオン交換
水の550部を2時間かけて滴下した処、NVが31.
8%で、かつ、pHカ7. 8 f&、る乳青白色の目
的共重合体水性分散物を得た。Furthermore, in order to remove the i-containing solvent, methyl ethyl ketone, n-butanol, and some butyl cellosolve were removed by distillation under reduced pressure, and the NV was 40.1.
A good aqueous dispersion of % was obtained. Reference Example 2 (same as above) 150 parts of methyl ethyl ketone and 1 liter of methacrylic acid were added to 100 parts of the reaction mixture containing the vinyl group-containing reactant.
Part O, 130 parts of methyl methacrylate, 53 parts of styrene
A carboxyl group-containing modified copolymer was obtained in the same manner as in Reference Example 1, except that 150 parts of n-butyl acrylate and 6 parts of "Perbutyl O" were uniformly mixed. Next, 7 parts of 28% aqueous ammonia was added to the reaction solution containing this modified copolymer and mixed uniformly, and then 550 parts of ion-exchanged water was added dropwise over 2 hours, resulting in an NV of 31.
8% and a pH of 7. A milky blue-white aqueous dispersion of the desired copolymer was obtained.
この水性分散物は1カ月間のあいだ室温に放置したのち
においても、何ら、変化が認められなかった。No change was observed in this aqueous dispersion even after it was left at room temperature for one month.
また、・この水性分散物中の有機溶剤を減圧留去せしめ
て、メチルエチルケトンを除去した処、NVが41.7
%なる良好な、最終的な形での共重合水性分散物が得ら
れた。以下、これを水性分散物(A−2)と略記する。In addition, when the organic solvent in this aqueous dispersion was distilled off under reduced pressure to remove methyl ethyl ketone, the NV was 41.7.
A copolymerized aqueous dispersion in the final form with a good % was obtained. Hereinafter, this will be abbreviated as aqueous dispersion (A-2).
参考例3(同上〉
ビニル基含有反応物を含む反応混合物に均一に混合せし
めるべき物質の組戒を、メチルエチルケトンの150部
、メタクリル酸の10部、メタクリル酸メチルの30部
、アクリル5g−n−ブチルの20部および「パーブチ
ルO」の20部に変更した以外は、参考例1と同様にし
て、カルボキシル基含有変性共重合体を得た。Reference Example 3 (same as above) The composition of the substances to be uniformly mixed into the reaction mixture containing the vinyl group-containing reactant was 150 parts of methyl ethyl ketone, 10 parts of methacrylic acid, 30 parts of methyl methacrylate, and 5 g-n- of acrylic. A carboxyl group-containing modified copolymer was obtained in the same manner as in Reference Example 1, except that 20 parts of butyl and 20 parts of "perbutyl O" were used.
次いで、この変性共重合体を含む反応液に28%アンモ
ニア水の7部を加えて均一に混合したのち、イオン交換
水の550部を2時間に亘って滴下した処、NVが31
.8%で、かつ、pHが7.8なる乳青白色の目的共重
合体水性分散物が得られた.この水性分散物は室温に1
カ月間のあいだ放置したのちにおいても、粘度の変化な
どは、何ら、認められなかった.
しかるのち、この水性分散物中の有機溶剤を減圧留去せ
しめた処、メチルエチルケトンが除去されて、NVが4
1.7%なる良好な、最終的な形での目的共重合体水性
分散液(A)が得られた.以下、これを水性分散液(A
−3)と略記する.参考例4(対照用の共重合体水性分
散物の調製例)
ビニル基含有反応物を含む反応混合物の使用に替えて、
無水メタクリル酸による処理を、一切、欠如し、つまり
、r CAB−553 Jの125部をメチルエチルケ
トンの250部で完全に溶解せしめた溶液の100部に
、直接、メチルエチルケトンの150部、メタクリル酸
のlO部、メタクリル酸メチルの130部、スチレンの
53部、アクリルfll−n−ブチルの150部および
「パーブチルO」の6部を加えて、参考例2と同様にし
て反応を行なった処、本発明の目的共重合体水性分散物
は全く得られなく、ビニル共重合体のみの水性分散物と
、このr CAB−553 Jとの単なる混合物として
存在するだけのもので、イオン交換水による水性化も果
たさなく、二層に分離してしまった。Next, 7 parts of 28% ammonia water was added to the reaction solution containing this modified copolymer and mixed uniformly, and then 550 parts of ion-exchanged water was added dropwise over 2 hours, resulting in an NV of 31.
.. A milky blue-white aqueous dispersion of the desired copolymer having a concentration of 8% and a pH of 7.8 was obtained. This aqueous dispersion was heated to room temperature for 1
No change in viscosity was observed even after leaving it for several months. Thereafter, the organic solvent in this aqueous dispersion was distilled off under reduced pressure, and methyl ethyl ketone was removed, resulting in an NV of 4.
An aqueous dispersion (A) of the desired copolymer in a good final form of 1.7% was obtained. Hereinafter, this aqueous dispersion (A
-3). Reference Example 4 (Preparation example of copolymer aqueous dispersion for control) Instead of using a reaction mixture containing a vinyl group-containing reactant,
There was no treatment with methacrylic anhydride, i.e., 125 parts of r CAB-553 J were completely dissolved in 250 parts of methyl ethyl ketone, and 150 parts of methyl ethyl ketone and 100 parts of methacrylic acid were directly added to the solution. 130 parts of methyl methacrylate, 53 parts of styrene, 150 parts of acrylic fll-n-butyl, and 6 parts of "perbutyl O" were added, and the reaction was carried out in the same manner as in Reference Example 2. The objective copolymer aqueous dispersion cannot be obtained at all, and exists only as a mere mixture of an aqueous dispersion of only vinyl copolymer and this r CAB-553 J, and it cannot be made aqueous with ion-exchanged water. Without success, it separated into two layers.
参考例5〔架橋成分(B)の調製例〕
温度計、攪拌機、還流冷却器および生戒水分離器を具備
した2lの四ツ目フラスコに、メラミンの126部、8
0%パラホルムの165部、メタノールの480部およ
び脱イオン水の57部を仕込んでから、常法により、7
2部の水を5時間かけて還流脱水せしめた。Reference Example 5 [Example of Preparation of Crosslinking Component (B)] 126 parts of melamine, 8
After charging 165 parts of 0% paraform, 480 parts of methanol and 57 parts of deionized water, 7 parts of
Two parts of water were refluxed for 5 hours.
反応終了後、所定の不揮発分濃度となるまで、メタノー
ル、水およびホルムアルデヒドを減圧留去せしめ、次い
で、冷却が過して、NVがS O. O%なるメトキシ
メチル化メラミン樹脂を得た。以下、これを架橋剤(B
−1)と略記する。After the reaction is completed, methanol, water and formaldehyde are distilled off under reduced pressure until a predetermined nonvolatile content concentration is reached, and then the NV is cooled down to SO. A methoxymethylated melamine resin of 0% was obtained. Hereinafter, this will be used as a crosslinking agent (B
-1).
参考例6 (同上)
参考例5と同様の反応容器に、メラミンの126部、8
0%パラホルムアルデヒドの225部およびn−ブタノ
ールの592部を仕込み、10%水酸化ナトリウム水溶
液にてpHを9.5〜lO.0なる範囲内に調整したの
ち、80℃に1時間のあいだ保持して反応を行なった。Reference Example 6 (Same as above) In a reaction vessel similar to Reference Example 5, 126 parts of melamine and 8 parts of melamine were added.
225 parts of 0% paraformaldehyde and 592 parts of n-butanol were charged, and the pH was adjusted to 9.5 to 10.0 with a 10% aqueous sodium hydroxide solution. After adjusting the temperature to within a range of 0, the temperature was maintained at 80° C. for 1 hour to carry out the reaction.
次いで、ここへn−ブタノールの888部を加え、5%
硫酸水溶液にてpHを7〜7.5まで中和し、60〜7
0℃で、n−ブタノールの減圧濃縮を行なってからが過
して、プトキシメチル化メラミン樹脂を得た。Next, 888 parts of n-butanol was added to this to give a 5%
Neutralize the pH to 7 to 7.5 with an aqueous sulfuric acid solution, and then adjust the pH to 60 to 7.
After concentrating n-butanol under reduced pressure at 0°C, a poxymethylated melamine resin was obtained.
このものは、NVが75%であり、かつ、水/メタノー
ル−35/65(重量比)なる混合溶剤による希釈率が
5なる樹脂の溶液であった。This was a resin solution with an NV of 75% and a dilution ratio of 5 with a mixed solvent of water/methanol-35/65 (weight ratio).
次いで、このブトキシメチル化メラミン樹脂溶液の10
0部を、撹拌機付きの反応容器中に移し、ここへ、予め
、プチルセロソルブ中で、115℃で重合された、メタ
クリル酸メチル/アクリル酸n−ブチル/メタクリル酸
−5 0/4 2/8(重量比〉なる構戒の、酸価が5
2で、25℃におけるガードナー粘度がZ2で、かつ、
NVが40%なるアクリル共重合樹脂の溶液に、ジメチ
ルアミノエタノールを当量、加えて水溶液化した樹脂溶
液の20部を加え、1 , 000 〜I , 500
rpmなるディスパーで、攪拌しながら、脱イオン水の
46部を徐々に加え、しかるのち、さらに1時間のあい
だ、攪拌を続行して水分散化された、NVが50%なる
ブトキシメチル化メラミン樹脂を得た。Then, 10% of this butoxymethylated melamine resin solution
0 parts were transferred into a reaction vessel equipped with a stirrer and thereto were added methyl methacrylate/n-butyl acrylate/methacrylic acid-5 0/4 2/, previously polymerized in butyl cellosolve at 115°C. 8 (weight ratio), the acid value is 5
2, the Gardner viscosity at 25°C is Z2, and
To a solution of an acrylic copolymer resin having an NV of 40%, add an equivalent amount of dimethylaminoethanol to make an aqueous resin solution, and then add 20 parts of the resin solution to a solution of 1,000 to I,500.
46 parts of deionized water was gradually added with stirring using an rpm disperser, and then stirring was continued for an additional hour to obtain a water-dispersed butoxymethylated melamine resin with an NV of 50%. I got it.
以下、これを架橋剤(B−2)と略記する。Hereinafter, this will be abbreviated as crosslinking agent (B-2).
参考例7(アルξニウム顔料濃厚液の調製例)攪拌混合
容器に、金属含有率が60%なるアルξニウムペースト
の25部と、プチルセロソルブの25部とを混合し、1
時間のあいだ撹拌せしめて、目的とするアルミニウム顔
料濃厚液を得た。Reference Example 7 (Example of Preparation of Al ξ Nium Pigment Concentrate) In a stirring mixing container, 25 parts of aluminum ξ nium paste with a metal content of 60% and 25 parts of butyl cellosolve were mixed, and 1
The desired aluminum pigment concentrate was obtained by stirring for a certain period of time.
以下、これを顔料(C−1)と略記する。Hereinafter, this will be abbreviated as pigment (C-1).
参考例8(クリヤー上塗り塗料の調製例)アクリル酸メ
チルの250部、メタクリル酸n−ブチルの250部、
アクリルfll−n−プチルの36部、アクリル酸−2
−ヒドロキシェチルの120部およびメタクリル酸の1
6部と「パーブチルO」のl5部とを用いて、常法によ
り、ヰシレン中で重合を行なって、NVが55%なるア
クリル樹脂の溶液を得た。Reference Example 8 (Preparation example of clear top coat) 250 parts of methyl acrylate, 250 parts of n-butyl methacrylate,
36 parts of acrylic fll-n-butyl, acrylic acid-2
- 120 parts of hydroxyethyl and 1 part of methacrylic acid
Polymerization was carried out in silane by a conventional method using 6 parts and 15 parts of "Perbutyl O" to obtain a solution of an acrylic resin having an NV of 55%.
このものの水酸基価は57で、かつ、酸価は14であっ
た。This product had a hydroxyl value of 57 and an acid value of 14.
次いで、このアクリル樹脂溶液と「スーパーベソカiン
L−127−758 J (大日本インキ化学工業■
製のメラ呉ン樹脂;NV=75%〕とを、75/25(
固形分重量比)となるように混合し、しかるのち、「ス
ワゾーノt/#1500」〔丸善石油■製の芳香族系炭
化水素系溶剤〕により、20℃におけるフォードカップ
ll&l4による粘度が25なる目的塗料を得た。以下
、これを塗料(K−1)と略記する。Next, this acrylic resin solution and "Supervesocain L-127-758 J (Dainippon Ink & Chemicals Co., Ltd.)
Melago resin; NV=75%] and 75/25 (
Then, using "Swazono T/#1500" [aromatic hydrocarbon solvent manufactured by Maruzen Sekiyu ■], the viscosity by Ford cup 11 & 14 at 20°C becomes 25. Got the paint. Hereinafter, this will be abbreviated as paint (K-1).
参考例9(同上)
1スーパーベ,カミンL−127−75B JO代わり
に、「バーノソクON−950J [:大日本インキ
化学工業■製の、ヘキサメチレンジイソシアネートのト
リメチロールプロパン付加物〕を用いて、− 011/
− NGO=1/1 (当量比)となるように混合
し、次いで、「スワゾールlI1500Jで、20℃に
おけるフォードカップI1lIl4による粘度が25秒
となるように調整して、目的塗料を得た。以下、これを
塗料〈K一2)と略記する。Reference Example 9 (same as above) 1 Superbe, Kamin L-127-75B Instead of JO, "Burnosoku ON-950J [: Trimethylolpropane adduct of hexamethylene diisocyanate, manufactured by Dainippon Ink & Chemicals ■]" was used, -011/
- Mixed so that NGO = 1/1 (equivalent ratio), and then adjusted with Swazol lI1500J so that the viscosity by Ford cup IlIl4 at 20 ° C. was 25 seconds to obtain the target paint. , this is abbreviated as paint <K-2).
実施例l
撹拌混合容器に、水性分散物(A−1)の498.7部
、架橋剤(B−1)の125.0部、顔料(C−1)の
50.0部および脱イオン水の376.3部を、攪拌し
ながら順次添加して、さらに1時間のあいだ攪拌下に混
合した.
次いで、この混合物に「アクリゾールASE − 60
J(アメリカ国ローム・アンド・ハース社製の増粘剤
)の3.5部加え、さらにジメチルアミノエタノールの
0.3部をも加えて、NVが30.2%で、かつ、ブル
ソクフィールド粘度(ローターM3、60rpm)が3
50cpsなるメタリノク・ヘースコート用水性被覆組
成物を得た。Example 1 In a stirring mixing vessel, 498.7 parts of aqueous dispersion (A-1), 125.0 parts of crosslinking agent (B-1), 50.0 parts of pigment (C-1), and deionized water. 376.3 parts of the solution were added sequentially with stirring and mixed for an additional hour with stirring. This mixture was then added with ``Acrisol ASE-60''.
J (thickener manufactured by Rohm and Haas, USA) and 0.3 parts of dimethylaminoethanol were added to obtain a solution with an NV of 30.2% and a Brusok field. Viscosity (rotor M3, 60 rpm) is 3
An aqueous coating composition for Metalinok hair coat having a yield of 50 cps was obtained.
実施例2〜6ならびに比較例lおよび2第1表に示され
るような配合組成比に変更した以外は、実施例1と同様
にして、各種のメタリノク・ベースコート用水性被覆組
戒物を得た。Examples 2 to 6 and Comparative Examples 1 and 2 Various water-based coating compositions for metalinoku base coats were obtained in the same manner as in Example 1, except that the composition ratio was changed as shown in Table 1. .
それぞれの水性被覆組底物についての性状値は、同表に
示される通りである。The property values for each aqueous coated bottom are shown in the table.
応用例l〜7
実施例1〜6で得られたそれぞれのメタリ・7ク・ベー
スコート用被覆組成物と、参考例8および9で得られた
それぞれのクリヤー上塗り塗料とを、第2表に示される
ような組み合わせて2コート1ベーク方式による塗装を
行なった。Application Examples 1 to 7 The coating compositions for metallic 7K base coats obtained in Examples 1 to 6 and the clear top coats obtained in Reference Examples 8 and 9 are shown in Table 2. Painting was done using a two-coat, one-bake method using combinations that would allow for better results.
そのさいの被塗物としては、次のような前処理を行なっ
たものを用いた。The object to be coated was one that had undergone the following pretreatment.
すなわち、「ボンデライl− 13030J (日本
パー力ライジング特製の燐酸亜鉛系処理剤〕で処理され
た軟鋼板に、エポキシ樹脂系カチオン電着塗料を電着塗
装せしめ、次いで、その上にアミノポリエステル樹脂系
中塗り塗料を塗装せしめたものを被塗物として用いた。That is, a mild steel plate treated with Bonderai l-13030J (a zinc phosphate treatment agent specially made by Nippon Parriki Rising) is electrocoated with an epoxy resin-based cationic electrodeposition paint, and then an aminopolyester resin-based paint is applied thereon. An object coated with intermediate paint was used as the object to be coated.
まず、メタリック・ベースコート用被覆組成物を、25
℃で、かつ、相対湿度が60%なる塗装雰囲気において
、それぞれ2回ずつ、スプレーガンを用いて吹き付け塗
装せしめて、乾燥膜厚が30ミクロンなるメタリック・
ベース塗膜を形威せしめた。First, the coating composition for metallic base coat was coated with 25% of the coating composition.
℃ and in a painting atmosphere with a relative humidity of 60%, each coat was sprayed twice using a spray gun to form a metallic film with a dry film thickness of 30 microns.
The base coating was made to look impressive.
その2回の塗布の間に、2分間のセッティングを行なっ
た。A 2 minute setting period was provided between the two applications.
そのさいのスプレーガンのエアー圧は5 kg / c
nfとし、塗料の流速は4 0 0 m l /min
,とし、そして、被塗物とこのスプレーガンとの距離は
35cmとした。At that time, the air pressure of the spray gun was 5 kg/c.
nf, and the paint flow rate is 400 ml/min.
, and the distance between the object to be coated and this spray gun was 35 cm.
なお、被塗物上における塗布面が、常時、垂直となるよ
うに、該被塗物が保持されていた。The object to be coated was held so that the surface to be coated on the object was always vertical.
かかる2回の塗装ののち、室温に3分間のあいだ放置し
てから、80℃の温度に10分間保持して風乾させた。After these two coatings, it was left at room temperature for 3 minutes and then kept at a temperature of 80° C. for 10 minutes to air dry.
しかるのち、室温まで冷却してから、クリヤー上塗り塗
料を、スプレーガンにより、乾燥膜厚が40ξクロンと
なるように塗布し、5分間のセソティングののち、12
0〜140℃になる温度で30分間の焼付けを行なった
。Then, after cooling to room temperature, a clear top coat was applied with a spray gun so that the dry film thickness was 40ξcm, and after 5 minutes of sesoting, 12cm
Baking was carried out for 30 minutes at a temperature ranging from 0 to 140°C.
かくして得られたそれぞれの硬化塗膜について諸性能の
評価を行なった。それらの結果は、まとめて、同表に示
す通りである。Various performances of the thus obtained cured coating films were evaluated. The results are summarized in the same table.
なお、評価判定の要領は次の通りである。In addition, the outline of the evaluation judgment is as follows.
○:優れる △:やや劣る ×:劣る○: Excellent △: Slightly inferior ×: Inferior
Claims (1)
び/または無水メタクリル酸とを反応させて得られるビ
ニル基含有反応物と、カルボキシル基含有ビニルモノマ
ーを必須の成分とする重合性ビニルモノマーとの共重合
物の水性分散物(A)と、上記水性分散物中の共重合物
と反応する架橋成分(B)と、顔料(C)とを含んで成
る、水性被覆組成物。 2、ベースコート用組成物として、水酸基含有セルロー
ス誘導体と無水アクリル酸および/または無水メタクリ
ル酸とを反応させて得られるビニル基含有反応物と、カ
ルボキシル基含有ビニルモノマーを必須の成分とする重
合性ビニルモノマーとの共重合物の水性分散物(A)と
、上記水性分散液中の共重合物と反応する架橋成分(B
)と、顔料(C)とを含んで成る水性被覆組成物を用い
ることを特徴とする、2コート1ベーク方式で塗装する
方法。 3、前記水酸基含有セルロース誘導体が、0.4重量%
以上の水酸基を含有し、かつ、3,000〜300,0
00なる数平均分子量を有するものである、請求項1に
記載の水性被覆組成物。 4、前記水酸基含有セルロース誘導体が、0.4重量%
以上の水酸基を含有し、かつ、3,000〜300,0
00なる数平均分子量を有するものである、請求項2に
記載の塗装する方法。[Scope of Claims] 1. A polymerizable vinyl whose essential components are a vinyl group-containing reactant obtained by reacting a hydroxyl group-containing cellulose derivative with acrylic anhydride and/or methacrylic anhydride, and a carboxyl group-containing vinyl monomer. An aqueous coating composition comprising an aqueous dispersion (A) of a copolymer with a monomer, a crosslinking component (B) that reacts with the copolymer in the aqueous dispersion, and a pigment (C). 2. As a base coat composition, a polymerizable vinyl whose essential components are a vinyl group-containing reactant obtained by reacting a hydroxyl group-containing cellulose derivative with acrylic anhydride and/or methacrylic anhydride, and a carboxyl group-containing vinyl monomer. An aqueous dispersion (A) of a copolymer with a monomer, and a crosslinking component (B) that reacts with the copolymer in the aqueous dispersion.
) and a pigment (C). 3. The hydroxyl group-containing cellulose derivative is 0.4% by weight
Contains a hydroxyl group of 3,000 to 300,0
2. The aqueous coating composition of claim 1, having a number average molecular weight of 0.00. 4. The hydroxyl group-containing cellulose derivative is 0.4% by weight
Contains a hydroxyl group of 3,000 to 300,0
The coating method according to claim 2, wherein the coating has a number average molecular weight of 0.00.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP19163389A JP2811773B2 (en) | 1989-07-25 | 1989-07-25 | Aqueous coating composition and coating method using the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP19163389A JP2811773B2 (en) | 1989-07-25 | 1989-07-25 | Aqueous coating composition and coating method using the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0356519A true JPH0356519A (en) | 1991-03-12 |
JP2811773B2 JP2811773B2 (en) | 1998-10-15 |
Family
ID=16277901
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JP19163389A Expired - Lifetime JP2811773B2 (en) | 1989-07-25 | 1989-07-25 | Aqueous coating composition and coating method using the same |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003070835A3 (en) * | 2002-02-23 | 2004-01-22 | Celanese Emulsions Gmbh | Aqueous coating compositions, method for the production thereof and their use for producing, in particular, thixotropic coating compositions |
JP2007224136A (en) * | 2006-02-23 | 2007-09-06 | Fujikura Kasei Co Ltd | Coating composition for base coat |
US8697025B2 (en) | 2007-11-08 | 2014-04-15 | Jx Nippon Oil & Energy Corporation | Raw material charcoal composition for negative electrode material of lithium ion secondary battery and method for producing the same |
US8741125B2 (en) | 2008-12-26 | 2014-06-03 | Jx Nippon Oil & Energy Corporation | Raw oil composition for negative electrode material for lithium ion secondary battery |
US8784644B2 (en) | 2010-06-30 | 2014-07-22 | Jx Nippon Oil & Energy Corporation | Stock oil composition for carbonaceous material for negative electrode of lithium-ion secondary battery |
CN117683186A (en) * | 2023-12-22 | 2024-03-12 | 江阴华理防腐涂料有限公司 | Cellulose modified polyester acrylate aqueous dispersion and preparation method and application thereof |
-
1989
- 1989-07-25 JP JP19163389A patent/JP2811773B2/en not_active Expired - Lifetime
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003070835A3 (en) * | 2002-02-23 | 2004-01-22 | Celanese Emulsions Gmbh | Aqueous coating compositions, method for the production thereof and their use for producing, in particular, thixotropic coating compositions |
JP2007224136A (en) * | 2006-02-23 | 2007-09-06 | Fujikura Kasei Co Ltd | Coating composition for base coat |
US8697025B2 (en) | 2007-11-08 | 2014-04-15 | Jx Nippon Oil & Energy Corporation | Raw material charcoal composition for negative electrode material of lithium ion secondary battery and method for producing the same |
US8741125B2 (en) | 2008-12-26 | 2014-06-03 | Jx Nippon Oil & Energy Corporation | Raw oil composition for negative electrode material for lithium ion secondary battery |
US8784644B2 (en) | 2010-06-30 | 2014-07-22 | Jx Nippon Oil & Energy Corporation | Stock oil composition for carbonaceous material for negative electrode of lithium-ion secondary battery |
CN117683186A (en) * | 2023-12-22 | 2024-03-12 | 江阴华理防腐涂料有限公司 | Cellulose modified polyester acrylate aqueous dispersion and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
JP2811773B2 (en) | 1998-10-15 |
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