JP2021066791A - Coating material for colored coat layer and method for coating the same - Google Patents
Coating material for colored coat layer and method for coating the same Download PDFInfo
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- JP2021066791A JP2021066791A JP2019192423A JP2019192423A JP2021066791A JP 2021066791 A JP2021066791 A JP 2021066791A JP 2019192423 A JP2019192423 A JP 2019192423A JP 2019192423 A JP2019192423 A JP 2019192423A JP 2021066791 A JP2021066791 A JP 2021066791A
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- 238000000576 coating method Methods 0.000 title claims abstract description 102
- 239000011248 coating agent Substances 0.000 title claims abstract description 83
- 239000000463 material Substances 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title description 10
- 229920005989 resin Polymers 0.000 claims abstract description 85
- 239000011347 resin Substances 0.000 claims abstract description 85
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 52
- 239000000049 pigment Substances 0.000 claims abstract description 50
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 49
- 239000003973 paint Substances 0.000 claims description 82
- 239000002270 dispersing agent Substances 0.000 claims description 29
- 230000000873 masking effect Effects 0.000 claims description 15
- 238000003916 acid precipitation Methods 0.000 abstract description 9
- 239000006185 dispersion Substances 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
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- 238000010438 heat treatment Methods 0.000 description 8
- 229920000178 Acrylic resin Polymers 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229920000877 Melamine resin Polymers 0.000 description 6
- 229920002125 Sokalan® Polymers 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 238000010422 painting Methods 0.000 description 6
- 239000004584 polyacrylic acid Substances 0.000 description 6
- 239000002987 primer (paints) Substances 0.000 description 6
- 239000004640 Melamine resin Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
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- 238000001035 drying Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
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- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
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- 239000000203 mixture Substances 0.000 description 3
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- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 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
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
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- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- 125000005907 alkyl ester group Chemical group 0.000 description 2
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- 239000008199 coating composition Substances 0.000 description 2
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- 238000011156 evaluation Methods 0.000 description 2
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- 239000005056 polyisocyanate Substances 0.000 description 2
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- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-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
- JGRXEBOFWPLEAV-UHFFFAOYSA-N 2-ethylbutyl prop-2-enoate Chemical compound CCC(CC)COC(=O)C=C JGRXEBOFWPLEAV-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- GDUZPNKSJOOIDA-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-yl 2-methylprop-2-enoate Chemical compound C1C(OC(=O)C(=C)C)CCC2OC21 GDUZPNKSJOOIDA-UHFFFAOYSA-N 0.000 description 1
- VAYCBEIMJNGBGH-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-yl prop-2-enoate Chemical compound C1C(OC(=O)C=C)CCC2OC21 VAYCBEIMJNGBGH-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- MYONAGGJKCJOBT-UHFFFAOYSA-N benzimidazol-2-one Chemical compound C1=CC=CC2=NC(=O)N=C21 MYONAGGJKCJOBT-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003431 cross linking reagent 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
- 230000003247 decreasing effect Effects 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
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal 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
- 238000002156 mixing Methods 0.000 description 1
- ODNOJYZMLIDHRA-UHFFFAOYSA-N n-(2,2-dihydroxyethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCC(O)O ODNOJYZMLIDHRA-UHFFFAOYSA-N 0.000 description 1
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003960 organic solvent 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
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
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- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000008719 thickening Effects 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
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
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- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、自動車用着色コート層用塗料、及び該塗料を用いた塗装方法、詳しくは、該塗料を用いたツートーン塗装方法に関する。 The present invention relates to a paint for a colored coat layer for automobiles and a coating method using the paint, specifically, a two-tone coating method using the paint.
自動車の塗装膜は、一般に、主に防錆のための電着塗装によるプライマー塗装、プライマー塗装膜と上塗り塗装膜との密着性の向上や平滑性の向上等を目的とする中塗り塗装、及び上塗り塗装を順次行うことによって形成される。また、自動車の塗装は、外観を美しくするだけでなく、別の車両と区別し識別する目的で、車体をツートーンに塗装することがある。例えばパトカーのように、白黒ツートーンに塗装する場合は、中塗り塗装後、車体全体を白色ベース塗料で塗装し、次いでクリア塗料を塗布することによって上塗り塗装膜を形成した後、車体の上側部分をマスキングして、下側部分を黒色ベース塗料及びクリア塗料の順に塗装して上塗り塗装膜を形成する。 In general, coating films for automobiles are primer coating mainly by electrodeposition coating for rust prevention, intermediate coating for the purpose of improving adhesion between the primer coating film and the top coating film, and improving smoothness. It is formed by sequentially performing top coating. In addition, the painting of an automobile may not only make the appearance beautiful, but also paint the vehicle body in two tones for the purpose of distinguishing and distinguishing it from another vehicle. For example, when painting in black and white two-tone like a patrol car, after intermediate coating, the entire vehicle body is painted with white base paint, then clear paint is applied to form a top coat coating film, and then the upper part of the vehicle body is painted. After masking, the lower portion is painted in the order of black base paint and clear paint to form a top coat coating film.
自動車の塗装工程のうち、上塗り塗装は車体に光沢感、平滑感、及び肉持ち感等の美観を与え、その商品価値を向上させるために行われる。そして、この美観を長期に渡って維持するため、上塗り塗装膜は、耐候性、耐水性、耐溶剤性及び耐衝撃性等に優れる必要がある。 Among the painting processes of automobiles, top coating is performed to give the vehicle body an aesthetic appearance such as glossiness, smoothness, and flesh, and to improve its commercial value. In order to maintain this aesthetic appearance for a long period of time, the topcoat coating film needs to be excellent in weather resistance, water resistance, solvent resistance, impact resistance and the like.
このような上塗り塗装に使用する塗料には、一般に、塗装仕上り性が良好であり、耐候性等の塗膜性能にも優れた熱硬化性のアクリル樹脂やポリエステル等の樹脂塗料が使用される。具体的には、メラミン−ホルムアルデヒド樹脂で架橋するメラミン樹脂硬化型樹脂を主剤とする塗料が使用される。 As the paint used for such topcoat coating, a thermosetting acrylic resin, polyester or other resin paint having good coating finish and excellent coating performance such as weather resistance is generally used. Specifically, a paint containing a melamine resin curable resin crosslinked with a melamine-formaldehyde resin as a main component is used.
ところで、近年、酸性雨が森林を衰退させたり、コンクリート中のカルシウム成分を溶かして道路を傷める等の問題が報告されている。風雨に晒される自動車車体の上塗り塗装膜についても、酸性雨による劣化が問題となっている。メラミン樹脂硬化型の塗料による上塗り塗装膜では、メラミン樹脂と水酸基含有アクリル樹脂とが架橋してエーテル結合を形成しているため、長期間酸性雨に触れると、エーテル結合が加水分解してシミや変色等が発生したり、さらには塗膜の破壊へと進行する可能性もある。 By the way, in recent years, problems such as acid rain deteriorating forests and dissolving calcium components in concrete to damage roads have been reported. Deterioration due to acid rain has also become a problem for the topcoat film of automobile bodies that are exposed to wind and rain. In the topcoat film made of melamine resin curable paint, the melamine resin and the hydroxyl group-containing acrylic resin are crosslinked to form an ether bond. Therefore, when exposed to acid rain for a long period of time, the ether bond is hydrolyzed and stains or stains occur. Discoloration or the like may occur, and further, the coating film may be destroyed.
自動車塗装用の塗料として、特許文献１には、（Ａ）特定の脂肪族スルホン酸化合物又は脂肪族スルホン酸化合物のアミン塩、（Ｂ）一分子中にカルボキシ基、カルボン酸無水物基及びアルキルビニルエーテル化合物でブロック化されたカルボキシ基の官能基から選ばれる少なくとも一種を有する化合物、（Ｃ）特定のオルガノシリケートおよび／またはその縮合物、（Ｄ）一分子中にエポキシ基および／またはアルコキシシリル基を有する樹脂、及び（Ｅ）酸化アルミニウムゾル、酸化ケイ素ゾル、酸化ジルコニウムゾル及び酸化アンチモンゾルの中から選ばれる少なくとも一種の無機酸化物ゾルの分散体であって、かつ、不揮発成分が、アクリル系重合体で包含されたコア／シェル構造を有する複合体である分散体を含有してなる耐汚染性塗料組成物が開示されている。この耐汚染性塗料組成物からなる上塗り塗料を被塗装体に塗装して、例えば１４０℃で３０分間、乾燥炉内で加熱すると、塗料組成物に含まれるカルボキシ基とエポキシ基とが反応して、酸エポキシ架橋結合を形成する。この酸エポキシ架橋結合は、酸による加水分解が起こりにくいため、前記耐汚染性塗料組成物を上塗り塗装したクリア塗装膜は、耐酸性雨性等の耐候性が向上する。 As paints for automobile painting, Patent Document 1 states that (A) an amine salt of a specific aliphatic sulfonic acid compound or an aliphatic sulfonic acid compound, and (B) a carboxy group, a carboxylic acid anhydride group and an alkyl in one molecule. A compound having at least one selected from functional groups of carboxy groups blocked with a vinyl ether compound, (C) a specific organosilicate and / or a condensate thereof, (D) an epoxy group and / or an alkoxysilyl group in one molecule. It is a dispersion of at least one inorganic oxide sol selected from the resin having (E) aluminum oxide sol, silicon oxide sol, zirconium oxide sol and antimony oxide sol, and the non-volatile component is acrylic. A stain-resistant coating composition comprising a dispersion which is a composite having a core / shell structure contained in a polymer is disclosed. When a topcoat paint made of this stain-resistant paint composition is applied to an object to be coated and heated in a drying furnace at, for example, 140 ° C. for 30 minutes, the carboxy group and the epoxy group contained in the paint composition react with each other. , Form an acid-epoxy crosslinked bond. Since this acid-epoxy crosslinked bond is less likely to be hydrolyzed by an acid, the clear coating film coated with the stain-resistant coating composition is improved in weather resistance such as acid rain resistance.
しかしながら、前記上塗り塗料の塗布後の架橋反応を高温下に行うと、上塗り塗料中に含まれる着色料と分散体との親和性がなくなり、クリア塗装膜に凝集した顔料が析出してしまうという問題があった。このため、クリア塗装膜中に均一に分散できる顔料の量はせいぜい０．１ｐｗｃと少なく、所望の隠蔽性を有する着色クリア塗膜を形成するには、上塗り塗装の工程を２回以上重ねて行う必要があり、設備や塗装工程の生産性の問題がある。 However, if the cross-linking reaction after the application of the top coat is carried out at a high temperature, the affinity between the colorant contained in the top coat and the dispersion is lost, and the aggregated pigment is precipitated on the clear coating film. was there. Therefore, the amount of the pigment that can be uniformly dispersed in the clear coating film is as small as 0.1 pwc, and in order to form a colored clear coating film having a desired hiding property, the top coating process is repeated twice or more. There is a need, and there is a problem with the productivity of the equipment and painting process.
一方、設備上の理由により、例えば、ルーフを黒色とするツートーン塗装の場合、ルーフを黒色ベース塗料で塗装した後、クリア塗料の塗布工程を省略して、ルーフ部分をマスキングし、マスキングしていない部分に他色のベース塗料を塗布し、クリア塗料を塗布することがある。このような塗装方法では、ルーフにはクリア塗装膜がなく、黒色ベース塗装膜が最外層となるため、車体に充分な耐候性を持たせることができない。このような事情に応えるため、隠蔽性を備えながら、優れた耐候性を有し、さらに、ベース塗料およびクリア塗料の機能を併せ持つ上塗り塗料の開発が要望されていた。 On the other hand, for equipment reasons, for example, in the case of two-tone painting in which the roof is black, after painting the roof with a black base paint, the clear paint application step is omitted, and the roof portion is masked and not masked. A base paint of another color may be applied to the part, and a clear paint may be applied. In such a coating method, the roof does not have a clear coating film, and the black base coating film is the outermost layer, so that the vehicle body cannot have sufficient weather resistance. In order to respond to such a situation, there has been a demand for the development of a topcoat paint which has excellent weather resistance while having a concealing property and also has the functions of a base paint and a clear paint.
本発明は、被塗装物上にベース塗料で塗装した後、さらにクリア塗膜を形成しなくても、酸性雨に対する耐性を向上させることができるベース塗装用塗料および該塗料を用いた塗装方法を提供することを目的とする。 The present invention provides a base coating paint and a coating method using the coating, which can improve resistance to acid rain without further forming a clear coating film after coating the object to be coated with the base coating. The purpose is to provide.
本発明の着色コート層用塗料は、１分子中に１個以上のカルボキシ基を有する樹脂と、１分子中に１個以上のエポキシ基を有する樹脂とからなる多官能性樹脂、または、１分子中にカルボキシ基とエポキシ基とをそれぞれ１個以上を有する多官能性樹脂と、顔料と、１分子中にカルボキシ基とエポキシ基とをそれぞれ１個以上を有する分散剤とを含有することを特徴とする。 The coating material for a colored coat layer of the present invention is a polyfunctional resin composed of a resin having one or more carboxy groups in one molecule and a resin having one or more epoxy groups in one molecule, or one molecule. It is characterized by containing a polyfunctional resin having one or more carboxy groups and one or more epoxy groups, and a pigment and a dispersant having one or more carboxy groups and one or more epoxy groups in one molecule. And.
すなわち、本発明では、多官能性樹脂と同じ官能基を二対有する分散剤を用いることで、分散剤中のカルボキシ基およびエポキシ基と、多官能性樹脂中のカルボキシ基およびエポキシ基が相互作用して、分散剤および多官能性樹脂が良好に混ざり合う。このため、顔料を着色コート層用塗料中に均一に分散させることができる。 That is, in the present invention, by using a dispersant having two pairs of the same functional groups as the polyfunctional resin, the carboxy group and the epoxy group in the dispersant interact with the carboxy group and the epoxy group in the polyfunctional resin. Then, the dispersant and the polyfunctional resin are well mixed. Therefore, the pigment can be uniformly dispersed in the paint for the colored coat layer.
本発明の塗装方法は、被塗装物上に着色トップコート層を形成する方法であり、前記着色トップコート層が、１分子中に１個以上のカルボキシ基を有する樹脂と、１分子中に１個以上のエポキシ基を有する樹脂とからなる多官能性樹脂、または、１分子中にカルボキシ基とエポキシ基とをそれぞれ１個以上を有する多官能性樹脂と、顔料と、１分子中にカルボキシ基とエポキシ基とをそれぞれ１個以上を有する分散剤とを含有する着色コート層用塗料を用いて形成されることを特徴とする。 The coating method of the present invention is a method of forming a colored topcoat layer on an object to be coated, wherein the colored topcoat layer is a resin having one or more carboxy groups in one molecule and one in one molecule. A polyfunctional resin composed of a resin having one or more epoxy groups, a polyfunctional resin having one or more carboxy groups and one epoxy group in one molecule, a pigment, and a carboxy group in one molecule. It is characterized in that it is formed by using a coating material for a colored coat layer containing a dispersant having one or more of an epoxy group and an epoxy group.
前記構成を有する着色コート層用塗料を被塗装物に塗布後、乾燥炉で加熱すると、カルボキシ基およびエポキシ基が架橋して、酸エポキシ結合を形成し、顔料を樹脂中に均一に分散した状態で塗装が完成する。 When the paint for the colored coat layer having the above structure is applied to the object to be coated and then heated in a drying furnace, the carboxy group and the epoxy group are crosslinked to form an acid-epoxy bond, and the pigment is uniformly dispersed in the resin. Painting is completed with.
前記塗装方法は、前記被塗装物上の一部に前記着色コート層用塗料を塗布して着色トップコート層を形成する工程１と、前記被塗装物上の一部に形成した前記着色トップコート層上にマスキング層を形成する工程２と、前記マスキング層上および前記マスキング層を形成していない前記被塗装物上に第２着色塗料を塗布して第２着色層を形成する工程３と、前記第２着色層上にトップクリア層を形成する工程４と、前記マスキング層の設けられた部分を剥離することにより、ツートーン塗装を完成する工程５とを有することが好ましい。 The coating method includes a step 1 of applying the paint for a colored coat layer to a part of the object to be coated to form a colored top coat layer, and the colored top coat formed on a part of the object to be coated. A step 2 of forming a masking layer on the layer, and a step 3 of applying a second colored paint on the masking layer and on the object to be coated on which the masking layer is not formed to form a second colored layer. It is preferable to have a step 4 of forming a top clear layer on the second colored layer and a step 5 of completing the two-tone coating by peeling off the portion provided with the masking layer.
本発明によれば、多官能性樹脂が有する官能基と同じ官能基を二対、すなわち、カルボキシ基およびエポキシ基を持つ分散剤を用いることにより、分散剤および多官能性樹脂が相互作用して良好に混ざり合い、着色コート層用塗料中、顔料を均一に分散させることができる。このような着色コート層用塗料を用いて被塗物を塗装すれば、加熱乾燥時に多官能性樹脂中のカルボキシ基およびエポキシ基と、分散剤中のカルボキシ基およびエポキシ基とが架橋して酸エポキシ結合を形成し、顔料が均一に分散した外塗り塗装膜を形成することができる。このような着色コート層用塗料をベース塗料として用いれば、クリア塗料を塗布しなくても、外観に優れた上塗り塗装を完成できるため、外塗り工程を省略することができる。 According to the present invention, by using two pairs of the same functional groups as the functional groups of the polyfunctional resin, that is, a dispersant having a carboxy group and an epoxy group, the dispersant and the polyfunctional resin interact with each other. It mixes well and the pigment can be uniformly dispersed in the paint for the colored coat layer. When the object to be coated is coated with such a paint for a colored coat layer, the carboxy group and epoxy group in the polyfunctional resin and the carboxy group and epoxy group in the dispersant are crosslinked during heating and drying to form an acid. An epoxy bond can be formed to form an outer coating film in which the pigment is uniformly dispersed. If such a paint for a colored coat layer is used as a base paint, a top coat coating having an excellent appearance can be completed without applying a clear paint, so that the outer coating step can be omitted.
また、カルボキシ基−エポキシ基間の酸エポキシ架橋結合は、酸による加水分解反応が起こり難い。よって、本発明の着色コート層用塗料を用いれば、酸性雨等に対する耐性に優れたベース塗装膜またはクリア塗装膜を形成することができる。 In addition, the acid-epoxy crosslinked bond between the carboxy group and the epoxy group is unlikely to undergo an acid hydrolysis reaction. Therefore, by using the paint for the colored coat layer of the present invention, it is possible to form a base coating film or a clear coating film having excellent resistance to acid rain and the like.
本発明の着色コート層用塗料は、１分子中に１個以上のカルボキシ基を有する樹脂と、１分子中に１個以上のエポキシ基を有する樹脂とからなる多官能性樹脂、または、１分子中にカルボキシ基とエポキシ基とをそれぞれ１個以上を有する多官能性樹脂と、顔料と、１分子中にカルボキシ基とエポキシ基とをそれぞれ１個以上を有する分散剤とを含有する。本発明の着色コート層用塗料は、カルボキシ基およびエポキシ基を持つ多官能性樹脂と、顔料と、カルボキシ基およびエポキシ基を持つ分散剤とからなる。
なお、本発明において、着色コート層用塗料は、ベース塗料およびクリア塗料などの上塗り塗料をいう。
The coating material for a colored coat layer of the present invention is a polyfunctional resin composed of a resin having one or more carboxy groups in one molecule and a resin having one or more epoxy groups in one molecule, or one molecule. It contains a polyfunctional resin having one or more carboxy groups and one or more epoxy groups, a pigment, and a dispersant having one or more carboxy groups and one or more epoxy groups in one molecule. The coating material for a colored coat layer of the present invention comprises a polyfunctional resin having a carboxy group and an epoxy group, a pigment, and a dispersant having a carboxy group and an epoxy group.
In the present invention, the paint for the colored coat layer refers to a top coat paint such as a base paint and a clear paint.
前記多官能性樹脂の一実施形態は、１分子中に１個以上のカルボキシ基を有する樹脂と、１分子中に１個以上のエポキシ基を有する樹脂である。
１分子中に１個以上のカルボキシ基を有する樹脂は、具体的には、分子中にカルボキシ基と水酸基とを有するアクリル系共重合体である。前記アクリル系共重合体は、アクリル系単量体を主成分とし、該アクリル系単量体と、カルボキシ基を有する単量体と、水酸基を有する単量体とを共重合して得られる。
One embodiment of the polyfunctional resin is a resin having one or more carboxy groups in one molecule and a resin having one or more epoxy groups in one molecule.
The resin having one or more carboxy groups in one molecule is specifically an acrylic copolymer having a carboxy group and a hydroxyl group in the molecule. The acrylic copolymer is obtained by copolymerizing an acrylic monomer as a main component, the acrylic monomer, a monomer having a carboxy group, and a monomer having a hydroxyl group.
アクリル系単量体には、メチルアクリレート、ｎ−ブチルアクリレート、イソブチルアクリレート、ラウリルアクリレートおよび２−エチルブチルアクリレート等のアクリル酸の炭素数１〜２４のアルキルエステル類、ならびに、メチルメタクリレート、ｎ−ブチルメタクリレート、イソブチルメタクリレート、２−エチルヘキシルメタクリレート、デシルメタクリレートおよびステアリルメタクリレート等のメタクリル酸の炭素数１〜２４のアルキルエステル類が挙げられる。これらのうち、ｎ−ブチルアクリレートおよびｎ−ブチルメタクリレート等、炭素原子数の比較的小さいものが好ましい。 Acrylate-based monomers include alkyl esters of acrylic acid having 1 to 24 carbon atoms such as methyl acrylate, n-butyl acrylate, isobutyl acrylate, lauryl acrylate and 2-ethylbutyl acrylate, and methyl methacrylate and n-butyl. Examples thereof include alkyl esters having 1 to 24 carbon atoms of methacrylic acid such as methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate and stearyl methacrylate. Of these, those having a relatively small number of carbon atoms, such as n-butyl acrylate and n-butyl methacrylate, are preferable.
カルボキシ基を有する単量体は、例えば、アクリル酸またはメタクリル酸が一般的であるが、マレイン酸、フマル酸、クロトン酸およびイタコン酸等のエチレン性不飽和カルボン酸を用いてもよい。 As the monomer having a carboxy group, for example, acrylic acid or methacrylic acid is generally used, but ethylenically unsaturated carboxylic acids such as maleic acid, fumaric acid, crotonic acid and itaconic acid may be used.
水酸基を有する単量体には、例えば、２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタクリレート、ヒドロキシプロピルアクリレート、ヒドロキシプロピルメタクリレート、Ｎ−メチロールアクリルアミド、Ｎ−メチロールメタクリルアミド、Ｎ−ヒドロキシエチルアクリルアミドおよびＮ−ジヒドロキシエチルメタクリルアミド等が挙げられる。これらの中でも、２−ヒドロキシエチルメタクリレート等が好ましい。 Examples of the monomer having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, N-hydroxyethyl acrylamide and N-. Examples thereof include dihydroxyethyl methacrylamide. Among these, 2-hydroxyethyl methacrylate and the like are preferable.
なお、前記単量体の他に、スチレン、ビニルトルエン、アクリロニトリル、メタクリロニトリル、アクリルアミドおよび酢酸ビニル等も適宜組み合わせて用いてもよい。 In addition to the above-mentioned monomers, styrene, vinyltoluene, acrylonitrile, methacrylonitrile, acrylamide, vinyl acetate and the like may be used in appropriate combinations.
１分子中に１個以上のカルボキシ基を有する樹脂は、前記単量体成分を共重合して得られ、その数平均分子量（Ｍn）は、通常１，０００〜２００，０００、好ましくは２，０００〜１００，０００である。数平均分子量（Ｍn）が１，０００未満であると、充分に硬化した樹脂塗膜を形成できないことがある。一方、数平均分子量（Ｍn）が２００，０００を超えると、樹脂の溶解性が低下して、塗料の粘度が高くなり調製が困難となることがある。 A resin having one or more carboxy groups in one molecule is obtained by copolymerizing the above-mentioned monomer components, and the number average molecular weight (M n ) thereof is usually 1,000 to 200,000, preferably 2. It is 000 to 100,000. If the number average molecular weight (M n ) is less than 1,000, a sufficiently cured resin coating film may not be formed. On the other hand, if the number average molecular weight (M n ) exceeds 200,000, the solubility of the resin may decrease, the viscosity of the coating material may increase, and preparation may become difficult.
次に、１分子中に１個以上のエポキシ基を有する樹脂は、具体的には、分子中にエポキシ基と水酸基とを有するアクリル系共重合体であり、前記１分子中に１個以上のカルボキシ基を有する樹脂と酸−エポキシ硬化型樹脂を形成する。 Next, the resin having one or more epoxy groups in one molecule is specifically an acrylic copolymer having an epoxy group and a hydroxyl group in the molecule, and one or more in the one molecule. It forms an acid-epoxide curable resin with a resin having a carboxy group.
１分子中に１個以上のエポキシ基を有する樹脂は、例えば、エポキシ基を有する単量体と、前記アクリル系単量体とを共重合して得てもよい。 The resin having one or more epoxy groups in one molecule may be obtained, for example, by copolymerizing a monomer having an epoxy group and the acrylic monomer.
前記エポキシ基を有する単量体には、グリシジルメタクリレート、グリシジルアクリレート、３，４−エポキシシクロヘキシルアクリレート、３，４−エポキシシクロヘキシルメタクリレートおよびアリルグリシジルエーテル等が挙げられる。 Examples of the monomer having an epoxy group include glycidyl methacrylate, glycidyl acrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methacrylate, and allyl glycidyl ether.
１分子中に１個以上のエポキシ基を有する樹脂の数平均分子量（Ｍn）は、通常１，０００〜１００，０００、好ましくは１，５００〜１００，０００である。
１分子中に１個以上のカルボキシ基を有する樹脂と、１分子中に１個以上のエポキシ基を有する樹脂とで、一方の平均分子量をやや大きくして、他方の平均分子量をやや小さくしてもよい。これにより、アクリル樹脂の相溶性を高め、両樹脂の相互の架橋反応が良好に進行する。
The number average molecular weight (M n ) of a resin having one or more epoxy groups in one molecule is usually 1,000 to 100,000, preferably 1,500 to 100,000.
With a resin having one or more carboxy groups in one molecule and a resin having one or more epoxy groups in one molecule, the average molecular weight of one is slightly increased and the average molecular weight of the other is slightly decreased. May be good. As a result, the compatibility of the acrylic resin is enhanced, and the mutual cross-linking reaction between the two resins proceeds satisfactorily.
前記多官能性樹脂の他の実施形態は、１分子中にカルボキシ基とエポキシ基とをそれぞれ１個以上を有する多官能性樹脂である。 Another embodiment of the polyfunctional resin is a polyfunctional resin having one or more carboxy groups and one or more epoxy groups in one molecule.
前記いずれの多官能性樹脂においても、そのエポキシ当量は２００〜１０００程度、好ましくは２５０〜５００である。エポキシ当量が２００未満であると、カルボキシ基との反応が局部的に過剰となり、塗膜の硬化時に歪が生じる虞がある。一方、エポキシ当量が１０００を超えると、架橋密度が不足して、実用上充分な塗膜の硬化性を得ることが困難になることがある。なお、このエポキシ当量は、１グラム当量のエポキシ基を含む樹脂のグラム数である。 The epoxy equivalent of any of the above-mentioned polyfunctional resins is about 200 to 1000, preferably 250 to 500. If the epoxy equivalent is less than 200, the reaction with the carboxy group may be locally excessive and distortion may occur when the coating film is cured. On the other hand, if the epoxy equivalent exceeds 1000, the crosslink density may be insufficient, and it may be difficult to obtain practically sufficient curability of the coating film. The epoxy equivalent is the number of grams of the resin containing 1 gram equivalent of the epoxy group.
前記一の実施形態に係る１分子中に１個以上のカルボキシ基を有する樹脂と、１分子中に１個以上のエポキシ基を有する樹脂とからなる多官能性樹脂と、他の実施形態に係る１分子中にカルボキシ基とエポキシ基とをそれぞれ１個以上を有する多官能性樹脂とは、いずれか一方を用いてもよいし、両方を混合して用いてもよい。 The present invention relates to a polyfunctional resin composed of a resin having one or more carboxy groups in one molecule according to the first embodiment, a resin having one or more epoxy groups in one molecule, and another embodiment. As the polyfunctional resin having one or more carboxy groups and one or more epoxy groups in one molecule, either one may be used, or both may be mixed and used.
顔料には、公知の着色顔料が用いられる。塗料中に着色顔料が含まれることで、塗膜表面の微細な凹凸を隠蔽することができる。 As the pigment, a known coloring pigment is used. By including the coloring pigment in the paint, it is possible to hide the fine irregularities on the surface of the coating film.
着色顔料は、アゾレーキ系顔料、ジケトピロロピロール系顔料、ベンズイミダゾロン系顔料、フタロシアニン系顔料、インジゴ系顔料、ペリレン系顔料、キノフタロン系顔料、ジオキサジン系顔料、キナクリドン系顔料、イソインドリノン系顔料および金属錯体等の有機顔料系、並びに黄鉛、黄色酸化鉄、ベンガラ、二酸化チタンおよびカーボンブラック等の無機顔料系のいずれでもよい。
着色コート層用塗料中の着色顔料の濃度（ｐｗｃ）は、通常１〜２０質量％、好ましくは２〜１０質量％である。
なお、「ｐｗｃ」とは、Pigment Weight Concentration（顔料重量濃度）のことであり、塗料固形分に対する顔料の質量濃度をいう。
The coloring pigments are azolake pigments, diketopyrrolopyrrole pigments, benzimidazolone pigments, phthalocyanine pigments, indigo pigments, perylene pigments, quinophthalone pigments, dioxazine pigments, quinacridone pigments, and isoindolinone pigments. And organic pigments such as metal complexes, and inorganic pigments such as yellow lead, yellow iron oxide, red iron oxide, titanium dioxide and carbon black may be used.
The concentration (pwc) of the colored pigment in the paint for the colored coat layer is usually 1 to 20% by mass, preferably 2 to 10% by mass.
In addition, "pwc" means Pigment Weight Concentration, and means the mass concentration of the pigment with respect to the solid content of a paint.
前記多官能性樹脂および分散剤の合計に対して、顔料の添加量は、通常１〜２７質量％、好ましくは２〜１２質量％である。顔料の添加量が２７質量％を超えると、顔料の一部が酸エポキシ結合の隙間に取り込まれず、塗装膜中の分散性を損なうことがある。一方、顔料の添加量が１質量％に満たないと、塗装膜に必要な着色または隠蔽性を付与できないことがある。 The amount of the pigment added is usually 1 to 27% by mass, preferably 2 to 12% by mass, based on the total of the polyfunctional resin and the dispersant. If the amount of the pigment added exceeds 27% by mass, a part of the pigment is not taken into the gaps between the acid-epoxy bonds, which may impair the dispersibility in the coating film. On the other hand, if the amount of the pigment added is less than 1% by mass, it may not be possible to impart the necessary coloring or hiding property to the coating film.
１分子中にカルボキシ基とエポキシ基とをそれぞれ１個以上有する分散剤には、例えば、塩基性ポリアクリル酸樹脂等のスルホン酸塩、カルボン酸塩およびリン酸塩等がある。また、これらの対イオンには、ナトリウム塩、カリウム塩及びトリエタノールアミン塩のほかに、構造中にエステル結合をもつアルキル硫酸エステル塩、アルキルリン酸エステル塩等が挙げられる。これらのうち、塩基性ポリアクリル酸樹脂等のカルボン酸塩およびリン酸塩等が好ましく、塩基性ポリアクリル酸樹脂のリン酸エステル塩がより好ましい。 Dispersants having one or more carboxy groups and one or more epoxy groups in one molecule include, for example, sulfonates such as basic polyacrylic acid resins, carboxylic acid salts, and phosphates. In addition to sodium salt, potassium salt and triethanolamine salt, examples of these counterions include alkyl sulfate ester salts and alkyl phosphate ester salts having an ester bond in the structure. Of these, carboxylic acid salts such as basic polyacrylic acid resin and phosphates are preferable, and phosphoric acid ester salts of basic polyacrylic acid resin are more preferable.
前記分散剤は、多官能性樹脂と同様に、カルボキシ基およびエポキシ基を有する。前記多官能性樹脂と同じ官能基を二対有することで、分散剤中のカルボキシ基およびエポキシ基と、多官能性樹脂中のカルボキシ基およびエポキシ基とが相互作用して、分散剤と多官能性樹脂とが良好に混ざり合う。このため、分散剤が顔料粒子を安定的かつ均一に取り込み、顔料を着色コート層用塗料中で均一に分散させることができる。このような塗料を被塗装物に塗布後、乾燥炉で加熱すると、カルボキシ基およびエポキシ基が架橋して酸エポキシ結合を形成し、顔料が樹脂中に均一に分散された状態で塗装が完成する。図１は、多官能性樹脂および分散剤の間に顔料が入り込み、加熱後、顔料が、酸エポキシ結合の隙間に取り込まれる様子を表している。 The dispersant has a carboxy group and an epoxy group as in the polyfunctional resin. By having two pairs of the same functional groups as the polyfunctional resin, the carboxy group and the epoxy group in the dispersant and the carboxy group and the epoxy group in the polyfunctional resin interact with each other to form the dispersant and the polyfunctional group. Mixes well with the sex resin. Therefore, the dispersant can stably and uniformly take in the pigment particles, and the pigment can be uniformly dispersed in the paint for the colored coat layer. When such a paint is applied to an object to be coated and then heated in a drying furnace, the carboxy group and the epoxy group are crosslinked to form an acid-epoxy bond, and the coating is completed in a state where the pigment is uniformly dispersed in the resin. .. FIG. 1 shows how the pigment enters between the polyfunctional resin and the dispersant, and after heating, the pigment is incorporated into the gaps between the acid-epoxy bonds.
分散剤の添加量は、前記多官能性樹脂に対して、通常３〜６５質量％、好ましくは５〜３５質量％である。分散剤の添加量が６５質量％を超えると、紫外線劣化しやすいことがある。一方、分散剤の添加量が３質量％に満たないと、塗装膜において顔料が均一に分散できないことがある。 The amount of the dispersant added is usually 3 to 65% by mass, preferably 5 to 35% by mass, based on the polyfunctional resin. If the amount of the dispersant added exceeds 65% by mass, it may be easily deteriorated by ultraviolet rays. On the other hand, if the amount of the dispersant added is less than 3% by mass, the pigment may not be uniformly dispersed in the coating film.
本発明の塗装方法は、前記着色コート層用塗料を用いて被塗装物上に着色トップコート層を形成する方法である。
被塗装物は、例えば、鉄板、鋼鉄板、アルミニウムおよびステンレス鋼等である。例えば、被塗装物が自動車の鉄板等である場合、該鉄板上に予めプライマー層を形成してもよい。プライマー層は、電着塗装により車体の表面に形成する塗料や樹脂の膜であり、防食性や中塗り塗装膜との密着性を確保する役割を有する。
The coating method of the present invention is a method of forming a colored top coat layer on an object to be coated by using the coating material for a colored coat layer.
The object to be coated is, for example, an iron plate, a steel plate, aluminum, stainless steel, or the like. For example, when the object to be coated is an iron plate of an automobile or the like, a primer layer may be formed in advance on the iron plate. The primer layer is a paint or resin film formed on the surface of the vehicle body by electrodeposition coating, and has a role of ensuring corrosion resistance and adhesion to the intermediate coating film.
本発明の塗装方法では、被塗装物に着色コート層用塗料を塗布した後、該着色コート層用塗料を室温または加温下に乾燥させる。これにより、水性媒体が蒸発すると共に、カルボキシ基とエポキシ基とが架橋反応して、塗料が硬化する。
なお、被塗装物に着色コート層用塗料を塗布する方法は、限定されるものではなく、刷毛塗り塗装、ロール塗装、またはスプレー塗装等、公知の方法を用いることができる。
In the coating method of the present invention, the paint for the colored coat layer is applied to the object to be coated, and then the paint for the colored coat layer is dried at room temperature or under heating. As a result, the aqueous medium evaporates, and the carboxy group and the epoxy group undergo a cross-linking reaction to cure the paint.
The method of applying the paint for the colored coat layer to the object to be coated is not limited, and known methods such as brush coating, roll coating, and spray coating can be used.
本発明の塗装方法の一実施形態は、自動車の車体にプライマー層を形成し、中塗り塗料を塗布した後、室温または加温下に乾燥させ、中塗り塗装膜上に、本発明に係る着色コート層用塗料を塗布して、室温または加温下に乾燥させてワントーン塗装をする方法である（図２）。 In one embodiment of the coating method of the present invention, a primer layer is formed on the vehicle body of an automobile, an intermediate coating paint is applied, and then the coating method is dried at room temperature or under heating, and the intermediate coating coating film is colored according to the present invention. This is a method in which a coating layer paint is applied and dried at room temperature or under heating for one-tone coating (Fig. 2).
中塗り塗料には、通常、水溶性若しくは水分散性の樹脂成分と、硬化剤と、前記顔料とを含有する公知の塗料、または、有機溶剤に分散させた樹脂成分と硬化剤とを含有する公知の塗料が用いられる。樹脂成分には、アクリル樹脂、ポリエステル樹脂、アルキド樹脂、エポキシ樹脂またはポリウレタン樹脂等の水性樹脂、具体的にはカルボキシ基を有するアクリル樹脂またはポリエステル樹脂等が用いられる。硬化剤は、例えば、メラミン樹脂、ブロックポリイソシアネート等である。
なお、中塗り塗装膜は、衝撃吸収の役割を有する。また、クリア塗装膜を補完する役割を併せ持っていてもよい。
The intermediate coating material usually contains a water-soluble or water-dispersible resin component, a curing agent, a known coating material containing the pigment, or a resin component and a curing agent dispersed in an organic solvent. Known paints are used. As the resin component, an aqueous resin such as an acrylic resin, a polyester resin, an alkyd resin, an epoxy resin or a polyurethane resin, specifically, an acrylic resin or a polyester resin having a carboxy group is used. The curing agent is, for example, a melamine resin, a blocked polyisocyanate, or the like.
The intermediate coating film has a role of shock absorption. It may also have a role of complementing the clear coating film.
本発明の塗装方法の他の実施形態は、前記被塗装物上の一部に前記着色コート層用塗料を塗布して着色トップコート層を形成する工程１と、前記被塗装物上の一部に形成した前記着色トップコート層上にマスキング層を形成する工程２と、前記マスキング層上および前記マスキング層を形成していない前記被塗装物上に第２着色塗料を塗布して第２着色層を形成する工程３と、前記第２着色層上にトップクリア層を形成する工程４と、前記マスキング層の設けられた部分を剥離して、ツートーン塗装を完成する工程５とを有する。具体的な実施形態は、自動車の車体にプライマー層を形成し、中塗り塗料を塗布した後、ルーフ部に本発明に係る着色コート層用塗料を塗布し（工程１）、室温または加温下に乾燥させ、該ルーフ部をマスキングし（工程２）、本発明に係る第２着色塗料を車体全面に塗布し、室温または加温下に乾燥させ（工程３、４）、マスキング層の設けられた部分を剥がすことにより、ツートーン塗装をする方法である（工程５）。上塗り塗料として、着色コート層用塗料を塗布した後、公知のクリア塗料をさらに塗布してもよい（図３）。 Another embodiment of the coating method of the present invention includes a step 1 of applying the paint for a colored coat layer to a part of the object to be coated to form a colored top coat layer, and a part of the object to be coated. The second colored paint is applied on the masking layer and the object to be coated on which the masking layer is not formed in the step 2 of forming the masking layer on the colored top coat layer formed in the second colored layer. It has a step 3 of forming the top clear layer on the second colored layer, a step 4 of forming the top clear layer on the second colored layer, and a step 5 of peeling off the portion provided with the masking layer to complete the two-tone coating. In a specific embodiment, a primer layer is formed on the vehicle body of an automobile, an intermediate coating paint is applied, and then the colored coating layer coating material according to the present invention is applied to the roof portion (step 1) at room temperature or under heating. The roof portion is masked (step 2), the second colored paint according to the present invention is applied to the entire surface of the vehicle body, dried at room temperature or under heating (steps 3 and 4), and a masking layer is provided. This is a method of performing two-tone coating by peeling off the portion (step 5). As the topcoat paint, a paint for a colored coat layer may be applied, and then a known clear paint may be further applied (FIG. 3).
ここで、着色トップコート層は、ベース塗装膜またはクリア塗装膜、すなわち、上塗り塗装膜と同義である。第２着色塗料とは、前記着色コート層用塗料とは異なる顔料を含む着色コート層用塗料であり、該第２着色塗料を塗布した塗装膜を第２着色層という。 Here, the colored topcoat layer is synonymous with a base coating film or a clear coating film, that is, a topcoat coating film. The second colored paint is a paint for a colored coat layer containing a pigment different from the paint for the colored coat layer, and a coating film coated with the second colored paint is called a second colored layer.
なお、クリア塗料には、例えばアクリル樹脂、ポリエステル樹脂、アルキド樹脂、ウレタン樹脂およびエポキシ樹脂等と、ブロックポリイソシアネート、メラミン樹脂および尿素樹脂などの架橋剤と、その他の添加剤とを、有機溶剤または水に溶解または分散させた塗料が用いられる。 The clear paint contains, for example, an acrylic resin, a polyester resin, an alkyd resin, a urethane resin, an epoxy resin, or the like, a cross-linking agent such as a block polyisocyanate, a melamine resin, or a urea resin, and other additives. A paint dissolved or dispersed in water is used.
以下、本発明を実施例に基づきさらに具体的に説明するが、本発明は下記の実施例により制限されるものではない。
〔実施例１〕
多官能性樹脂、分散剤および顔料の合計に対して、溶剤を１０質量％添加して均一に混合した着色コート層用塗料を調製した。
多官能性樹脂、分散剤、顔料および溶剤は下記に示すとおりである。
（ｉ）多官能性樹脂
数平均分子量（Ｍn）が４０００、酸価が１５０ｍｇＫＯＨ／ｇのカルボキシ基含有化合物溶液５０％と、数平均分子量（Ｍn）が３０００、エポキシ基含有量が２．５ｍｍｏｌ／ｇのポリエポキシド樹脂溶液５０％との混合物
なお、前記カルボキシ基含有化合物溶液および前記ポリエポキシド樹脂溶液は、それぞれ、カルボキシ基含有化合物およびポリエポキシド樹脂にソルベント１００（ソルベントナフサ；三協化学（株）製）を添加して、均一に混合した１０％溶液である。
（ii）分散剤
塩基性ポリアクリル酸樹脂、リン酸エステル塩
（iii）顔料
カーボンブラック
Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the following examples.
[Example 1]
A coating material for a colored coat layer was prepared by adding 10% by mass of a solvent to the total of the polyfunctional resin, the dispersant and the pigment and uniformly mixing them.
The polyfunctional resins, dispersants, pigments and solvents are as shown below.
(I) Polyfunctional resin The number average molecular weight (M n ) is 4000, the acid value is 150 mgKOH / g, 50% of the carboxy group-containing compound solution, the number average molecular weight (M n ) is 3000, and the epoxy group content is 2. Mixture with 50% of 5 mmol / g polyepoxide resin solution The carboxy group-containing compound solution and the polyepoxide resin solution are prepared by Solvent 100 (Solvent Nafsa; manufactured by Sankyo Chemical Co., Ltd.) in the carboxy group-containing compound and the polyepoxide resin, respectively. ) Is added and uniformly mixed to obtain a 10% solution.
(Ii) Dispersant Basic polyacrylic acid resin, phosphoric acid ester salt (iii) Pigment Carbon black
〔比較例１〕
実施例１において、分散剤として、酸性ポリアクリル酸樹脂、硫酸エステル塩を使用したこと以外は、実施例１と同様にして、着色コート層用塗料を調製した。
[Comparative Example 1]
A paint for a colored coat layer was prepared in the same manner as in Example 1 except that an acidic polyacrylic acid resin and a sulfate ester salt were used as the dispersant in Example 1.
〔参考例１〕
実施例１において、顔料を使用しなかったこと以外は、実施例１と同様にして、コート層用塗料を調製した。
[Reference Example 1]
A coating material for a coat layer was prepared in the same manner as in Example 1 except that no pigment was used in Example 1.
［着色コート層用塗料の評価］
（１）耐酸性雨性
前記着色コート層用塗料を、電着塗装された基板上に塗布した後、乾燥させて、１５ｃｍ×７ｃｍの大きさの試験片を作製した。前記試験板にｐＨ１．０の硫酸５００μＬを垂らし、ＩＨオーブンにて８０℃で３０分間、加熱して塗膜を形成した後、塗膜のエッチング深さを表面粗さ計サーフテストＳＪ２１０（（株）ミツトヨ製）を用いて評価した。
実施例１では、エッチング深さは０μｍであり、比較例１では、エッチング深さは０．６μｍであった。実施例１の着色コート層用塗料では、分散剤として、塩基性ポリアクリル酸樹脂のリン酸エステル塩が使用されたため、該分散剤と多官能性樹脂との間に形成された酸エポキシ結合中にカーボンブラックが取り込まれて均一性が向上し、耐酸性雨を含む耐候性が向上したものと考えられる。一方、比較例１の着色コート層用塗料は、カーボンブラックの分散性に劣るために、試験片に着色コート層用塗料が疎らに塗布されることとなり、耐酸性雨が不充分であった。
[Evaluation of paint for colored coat layer]
(1) Acid and Rain Resistance The coating material for a colored coat layer was applied onto a electrodeposition-coated substrate and then dried to prepare a test piece having a size of 15 cm × 7 cm. 500 μL of sulfuric acid having a pH of 1.0 was dropped on the test plate and heated in an IH oven at 80 ° C. for 30 minutes to form a coating film, and then the etching depth of the coating film was measured by the surface roughness meter Surftest SJ210 (Co., Ltd.). ) Made by Mitutoyo) was used for evaluation.
In Example 1, the etching depth was 0 μm, and in Comparative Example 1, the etching depth was 0.6 μm. In the paint for the colored coat layer of Example 1, since the phosphoric acid ester salt of the basic polyacrylic acid resin was used as the dispersant, the acid epoxy bond formed between the dispersant and the polyfunctional resin was formed. It is considered that carbon black was incorporated into the paint to improve the uniformity and the weather resistance including acid rain resistance. On the other hand, since the paint for the colored coat layer of Comparative Example 1 was inferior in the dispersibility of carbon black, the paint for the colored coat layer was sparsely applied to the test piece, and the acid rain resistance was insufficient.
（２）分散安定性
参考例１の顔料を含まない塗料（基準）と、実施例１の顔料を混合した塗料を６０℃で１６時間放置した後、それぞれの塗料の粘度変化率を評価した。粘度はＪＩＳ５６００−２−２に規定されたストマー粘度計法を用いてＫＵ値（コンシステンシーを示す数値）を算出した。
基準塗料に対して、増粘の程度が１０％以下のとき、問題なしと判断した。
参考例１および実施例１ともに、経時的に粘度が上昇していたが、実施例１は、参考例１と比較し粘度の増加率が１０％以下であった。
(2) Dispersion Stability A paint (reference) containing no pigment of Reference Example 1 and a paint mixed with the pigment of Example 1 were left at 60 ° C. for 16 hours, and then the viscosity change rate of each paint was evaluated. For the viscosity, the KU value (a numerical value indicating consistency) was calculated using the Stormer viscometer method specified in JIS5600-2-2.
When the degree of thickening was 10% or less with respect to the standard paint, it was judged that there was no problem.
In both Reference Example 1 and Example 1, the viscosity increased with time, but in Example 1, the rate of increase in viscosity was 10% or less as compared with Reference Example 1.
Claims (3)
顔料と、
１分子中にカルボキシ基とエポキシ基とをそれぞれ１個以上を有する分散剤とを含有することを特徴とする着色コート層用塗料。 A polyfunctional resin composed of a resin having one or more carboxy groups in one molecule and a resin having one or more epoxy groups in one molecule, or a carboxy group and an epoxy group in one molecule, respectively. With one or more polyfunctional resins,
With pigments
A coating material for a colored coat layer, which comprises a dispersant having one or more carboxy groups and one or more epoxy groups in one molecule.
前記着色トップコート層が、
１分子中に１個以上のカルボキシ基を有する樹脂と、１分子中に１個以上のエポキシ基を有する樹脂とからなる多官能性樹脂、または、１分子中にカルボキシ基とエポキシ基とをそれぞれ１個以上を有する多官能性樹脂と、
顔料と、
１分子中にカルボキシ基とエポキシ基とをそれぞれ１個以上を有する分散剤とを含有する着色コート層用塗料を用いて形成されることを特徴とする塗装方法。 In the coating method of forming a colored top coat layer on the object to be coated,
The colored top coat layer
A polyfunctional resin composed of a resin having one or more carboxy groups in one molecule and a resin having one or more epoxy groups in one molecule, or a carboxy group and an epoxy group in one molecule, respectively. With one or more polyfunctional resins,
With pigments
A coating method characterized by being formed by using a paint for a colored coat layer containing a dispersant having one or more carboxy groups and one or more epoxy groups in one molecule.
前記被塗装物上の一部に形成した前記着色トップコート層上にマスキング層を形成する工程２と、
前記マスキング層上および前記マスキング層を形成していない前記被塗装物上に第２着色塗料を塗布して第２着色層を形成する工程３と、
前記第２着色層上にトップクリア層を形成する工程４と、
前記マスキング層の設けられた部分を剥離することにより、ツートーン塗装を完成する工程５と、
を有することを特徴とする請求項２に記載の塗装方法。 Step 1 of applying the paint for a colored coat layer to a part of the object to be coated to form a colored top coat layer.
Step 2 of forming a masking layer on the colored top coat layer formed on a part of the object to be coated, and
Step 3 of applying the second colored paint on the masking layer and on the object to be coated on which the masking layer is not formed to form the second colored layer.
Step 4 of forming a top clear layer on the second colored layer,
Step 5 to complete the two-tone coating by peeling off the portion provided with the masking layer.
The coating method according to claim 2, wherein the coating method is characterized by having.
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| JPH08257389A (en) * | 1995-01-27 | 1996-10-08 | Toyo Ink Mfg Co Ltd | Dispersant, epoxy resin aqueous dispersion using the same and aqueous curable resin composition |
| JP2002510740A (en) * | 1998-04-04 | 2002-04-09 | インペリアル・ケミカル・インダストリーズ・ピーエルシー | Aqueous coating composition |
| JP3797468B2 (en) * | 2000-08-24 | 2006-07-19 | Ｂａｓｆコーティングスジャパン株式会社 | Contamination-resistant coating composition, coating finishing method and coated article |
| WO2014132693A1 (en) * | 2013-02-28 | 2014-09-04 | ハリマ化成株式会社 | Fine metal particle dispersant, fine metal particle dispersed liquid, and cured film |
| CN110028876A (en) * | 2019-06-11 | 2019-07-19 | 广讯检测（广东）有限公司 | A kind of circuit board high temperature flame-proof Coating material composition and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08257389A (en) * | 1995-01-27 | 1996-10-08 | Toyo Ink Mfg Co Ltd | Dispersant, epoxy resin aqueous dispersion using the same and aqueous curable resin composition |
| JP2002510740A (en) * | 1998-04-04 | 2002-04-09 | インペリアル・ケミカル・インダストリーズ・ピーエルシー | Aqueous coating composition |
| JP3797468B2 (en) * | 2000-08-24 | 2006-07-19 | Ｂａｓｆコーティングスジャパン株式会社 | Contamination-resistant coating composition, coating finishing method and coated article |
| WO2014132693A1 (en) * | 2013-02-28 | 2014-09-04 | ハリマ化成株式会社 | Fine metal particle dispersant, fine metal particle dispersed liquid, and cured film |
| CN110028876A (en) * | 2019-06-11 | 2019-07-19 | 广讯检测（广东）有限公司 | A kind of circuit board high temperature flame-proof Coating material composition and preparation method thereof |
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