JP2011131134A - Method for forming multilayer coating film - Google Patents
Method for forming multilayer coating film Download PDFInfo
- Publication number
- JP2011131134A JP2011131134A JP2009291052A JP2009291052A JP2011131134A JP 2011131134 A JP2011131134 A JP 2011131134A JP 2009291052 A JP2009291052 A JP 2009291052A JP 2009291052 A JP2009291052 A JP 2009291052A JP 2011131134 A JP2011131134 A JP 2011131134A
- Authority
- JP
- Japan
- Prior art keywords
- coating film
- mass
- solid content
- acrylic resin
- water
- 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 181
- 239000011248 coating agent Substances 0.000 title claims abstract description 174
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 46
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 46
- 239000007787 solid Substances 0.000 claims abstract description 41
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 30
- 239000000839 emulsion Substances 0.000 claims abstract description 28
- 229920005862 polyol Polymers 0.000 claims abstract description 22
- 150000003077 polyols Chemical class 0.000 claims abstract description 22
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 20
- 229920000570 polyether Polymers 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 19
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 14
- 239000004640 Melamine resin Substances 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 6
- 239000010959 steel Substances 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims description 68
- 239000003973 paint Substances 0.000 claims description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 239000000049 pigment Substances 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 44
- 239000002253 acid Substances 0.000 claims description 31
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 23
- 229920001225 polyester resin Polymers 0.000 claims description 17
- 239000004645 polyester resin Substances 0.000 claims description 17
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 10
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 239000008199 coating composition Substances 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 239000002932 luster Substances 0.000 claims description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- 125000005399 allylmethacrylate group Chemical group 0.000 claims description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 27
- -1 poly (oxy (1-oxo-1,6-hexanediyl)) Polymers 0.000 description 23
- 238000004519 manufacturing process Methods 0.000 description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 5
- 229960002887 deanol Drugs 0.000 description 5
- 238000004070 electrodeposition Methods 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000009503 electrostatic coating Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- JLBXCKSMESLGTJ-UHFFFAOYSA-N 1-ethoxypropan-1-ol Chemical compound CCOC(O)CC JLBXCKSMESLGTJ-UHFFFAOYSA-N 0.000 description 2
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Chemical class 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 102100040160 Rabankyrin-5 Human genes 0.000 description 2
- 101710086049 Rabankyrin-5 Proteins 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
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- 235000014113 dietary fatty acids Nutrition 0.000 description 2
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- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
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- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
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- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- KCAMXZBMXVIIQN-UHFFFAOYSA-N octan-3-yl 2-methylprop-2-enoate Chemical compound CCCCCC(CC)OC(=O)C(C)=C KCAMXZBMXVIIQN-UHFFFAOYSA-N 0.000 description 1
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- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 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
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- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 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
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- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
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- 239000004431 polycarbonate resin Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、自動車車体等に形成される複層塗膜の形成方法およびその方法により得られた複合塗膜に関するものである。 The present invention relates to a method for forming a multilayer coating film formed on an automobile body and the like, and a composite coating film obtained by the method.
近年、環境に対する影響を考慮して、塗料中に含まれる有機溶剤の量を低減するために、塗料の水性化が検討されている。自動車用塗装においては、ベース塗膜を形成し、その上にクリヤー塗膜を形成することが一般的であるが、この系においてベース塗料を水性化することがこれまで行われてきた。 In recent years, considering the influence on the environment, in order to reduce the amount of the organic solvent contained in the paint, water-based paints have been studied. In automotive coatings, it is common to form a base coating and then form a clear coating thereon, but it has been practiced to make the base coating water-based in this system.
このような系に適応する水性ベース塗料として、例えば、特開昭６３−１９３９６８号公報（特許文献１）には、アクリルエマルションである水分散性フィルム形成性アクリル重合体、疎水性メラミン樹脂および顔料からなる水性被覆組成物が開示されている。また、特開昭６３−２６５９７４号公報（特許文献２）には、炭素数４〜１２のアルキル基を有するモノマーをコア部、アクリルアミドまたはメタクリル酸を含むシェル部を有するエマルション樹脂を含む水性塗料がそれぞれ開示されている。 As an aqueous base paint adapted to such a system, for example, JP-A-63-193968 (Patent Document 1) discloses a water-dispersible film-forming acrylic polymer that is an acrylic emulsion, a hydrophobic melamine resin, and a pigment. An aqueous coating composition is disclosed. Japanese Patent Application Laid-Open No. 63-265974 (Patent Document 2) discloses an aqueous coating material containing an emulsion resin having a core portion of a monomer having an alkyl group having 4 to 12 carbon atoms and a shell portion containing acrylamide or methacrylic acid. Each is disclosed.
本発明者等は既に特開２００１−２４０７９１号公報（特許文献３）において、水性ベース塗料を用いた塗装方法において、塗膜外観と作業性の改善を提案した。この技術では、水性ベースコート塗料において、特定のモノマーをアクリルエマルション樹脂の合成に用いることにより水とのなじみが改善され塗膜外観が向上し、酸価を調節して塗装作業性を改善した。この特許文献３の技術は、優れた性能を発揮するものであり、自動車塗装に十分利用できるものである。最近、自動車塗装の塗膜外観において、特に光輝性顔料を配合したメタリック塗装の場合、高いフリップフロップ性（いわゆる、ＦＦ性）が要求されている。フリップフロップ性を高くするには、光輝性顔料が一定の配向を持って塗料中に存在する必要があるが、その場合塗膜表面にムラがめだつことがある。高いフリップフロップ性を有すると共に、ムラの無い塗膜外観が要求されている。 The present inventors have already proposed improvement of coating film appearance and workability in a coating method using an aqueous base paint in Japanese Patent Application Laid-Open No. 2001-240791 (Patent Document 3). In this technique, in a water-based base coat paint, the use of a specific monomer for the synthesis of an acrylic emulsion resin improves the familiarity with water, improves the appearance of the coating film, and adjusts the acid value to improve the paint workability. The technique of Patent Document 3 exhibits excellent performance and can be sufficiently used for automobile painting. Recently, a high flip-flop property (so-called FF property) has been demanded in the appearance of automobile paint coatings, particularly in the case of metallic paints blended with a luster pigment. In order to increase the flip-flop property, the glitter pigment needs to be present in the paint with a certain orientation, and in this case, unevenness on the coating film surface may be noticeable. There is a demand for a coating film appearance that has high flip-flop properties and no unevenness.
特開２００３−２９２８７７号公報（特許文献４）には、水性ベース塗膜とクリヤー塗膜を同時に硬化させることよりなる塗膜形成方法において、水性ベース塗料中に１分子中に一級水酸基を平均０．０２個以上有し、数平均分子量３００〜３，０００であり、水トレランスが２．０以上であるポリエーテルポリオールを配合することが開示されている。この特許文献４で利用されているポリエーテルポリオールは、広範囲な多価アルコールのアルキレンオキサイド付加物が含まれているが、グリセリンの三つの水酸基がプロピレンオキサイドでエーテル化されたものは具体的に例示されていない。また、特許文献４にはフリップフロップ性を高くすることは記載しているが、フリップフロップ性が高くかつムラの無い塗膜については認識されていない。 Japanese Patent Application Laid-Open No. 2003-292877 (Patent Document 4) discloses a coating film forming method comprising simultaneously curing an aqueous base coating film and a clear coating film, and the average number of primary hydroxyl groups per molecule in the aqueous base coating is 0. It is disclosed that a polyether polyol having 0.02 or more, a number average molecular weight of 300 to 3,000, and a water tolerance of 2.0 or more is blended. The polyether polyol used in Patent Document 4 contains a wide range of alkylene oxide adducts of polyhydric alcohols, but specific examples include those in which three hydroxyl groups of glycerin are etherified with propylene oxide. It has not been. Further, Patent Document 4 describes that the flip-flop property is increased, but a coating film having a high flip-flop property and no unevenness is not recognized.
本発明は、上記特許文献３の技術を改善して、フリップフロップ性（ＦＦ性）が高くてムラのない複層塗膜形成方法を提供する。 This invention improves the technique of the said patent document 3, and provides the multilayer coating-film formation method with high flip-flop property (FF property), and without a nonuniformity.
即ち、本発明は、自動車用鋼板上に形成された中塗り塗膜上に、水性ベース塗料を塗装してベース塗膜を形成した後、有機溶剤型クリヤー塗料を塗布してクリヤー塗膜を形成し、上記ベース塗膜とクリヤー塗膜とを加熱し硬化させる複層塗膜の形成方法であって、
前記水性ベース塗料が、樹脂固形分１００質量％中、
（ａ）アクリル樹脂エマルションが固形分で１０〜６０質量％、
（ｂ）水溶性アクリル樹脂が固形分で５〜４０質量％、および
（ｃ）メラミン樹脂が固形分で２０〜４０質量％、
（ｄ）下記化学式で表される数平均分子量４００〜２，０００のポリエーテルポリオール２〜２５質量％
含有することを特徴とする複層塗膜の形成方法を提供する。
That is, in the present invention, a water-based base coating is formed on an intermediate coating film formed on an automotive steel plate to form a base coating, and then an organic solvent-type clear coating is applied to form a clear coating. And a method of forming a multilayer coating film in which the base coating film and the clear coating film are heated and cured,
The water-based paint is in a resin solid content of 100% by mass,
(A) Acrylic resin emulsion is 10-60 mass% in solid content,
(B) Water-soluble acrylic resin is 5 to 40% by mass in solid content, and (c) Melamine resin is 20 to 40% by mass in solid content,
(D) 2 to 25% by mass of a polyether polyol having a number average molecular weight of 400 to 2,000 represented by the following chemical formula
Provided is a method for forming a multilayer coating film characterized by containing.
上記アクリル樹脂エマルション（ａ）は、好ましくは、架橋性モノマーを０．２〜２０質量％含んだモノマー混合物をエマルション重合して得られる。 The acrylic resin emulsion (a) is preferably obtained by emulsion polymerization of a monomer mixture containing 0.2 to 20% by mass of a crosslinkable monomer.
架橋性モノマーは、アリルメタクリレート、エチレングリコールジメタクリレートまたはジビニルベンゼンであるのが好ましい。 The crosslinkable monomer is preferably allyl methacrylate, ethylene glycol dimethacrylate or divinylbenzene.
架橋性モノマーは、アクリル樹脂エマルション合成用のモノマー混合物中に０．５〜２０質量％の量で含有するのが好ましい。 The crosslinkable monomer is preferably contained in the monomer mixture for synthesizing the acrylic resin emulsion in an amount of 0.5 to 20% by mass.
上記のアクリル樹脂エマルション（ａ）を合成するモノマー混合物は、好ましくは、架橋性モノマー、酸基を有するα，β−エチレン性不飽和モノマー、水酸基を有するα，β−エチレン性不飽和モノマーおよびその他のα，β−エチレン性不飽和モノマーを含有する。 The monomer mixture for synthesizing the acrylic resin emulsion (a) is preferably a crosslinkable monomer, an α, β-ethylenically unsaturated monomer having an acid group, an α, β-ethylenically unsaturated monomer having a hydroxyl group, and others. Of α, β-ethylenically unsaturated monomers.
上記のアクリル樹脂エマルション（ａ）は、より好ましくは、酸価３〜５０ｍｇＫＯＨ／ｇ、水酸基価１０〜１５０ｍｇＫＯＨ／ｇを有する。 The acrylic resin emulsion (a) preferably has an acid value of 3 to 50 mgKOH / g and a hydroxyl value of 10 to 150 mgKOH / g.
本発明の水性ベース塗料は、更に、光輝性顔料を含むものである。 The aqueous base paint of the present invention further contains a luster pigment.
本発明の水性ベース塗料は、更に、ポリエステル樹脂を含有するものである。 The aqueous base paint of the present invention further contains a polyester resin.
本発明では、水性ベース塗料と有機溶剤型クリヤー塗料とをウェット・オン・ウェットで塗り重ねて、両塗膜と同時に焼付硬化するツーコート・ワンベーク方法で複層塗膜を形成する場合に、水性ベース塗料中に特定の化学式で表される数平均分子量４００〜２，０００を有するグリセリンにプロピレンオキシドを付加したポリエーテルポリオールを配合すると、フリップフロップ性（ＦＦ性）が高い時でもムラが生じないことが解った。 In the present invention, when forming a multilayer coating film by a two-coat one-bake method in which a water-based base paint and an organic solvent-type clear paint are applied by wet-on-wet and baked and cured simultaneously with both paint films, When blending a polyether polyol in which propylene oxide is added to glycerin having a number average molecular weight of 400 to 2,000 represented by a specific chemical formula in the paint, there will be no unevenness even when the flip-flop property (FF property) is high. I understand.
フリップフロップ性は塗料中に含まれている光輝性顔料の配向に基づくが、光輝性顔料の配向が揃ってＦＦ性が高くなった場合に、塗膜のムラがより目立つようになる。水性ベース塗料をスプレーガンでスプレー塗装した後に通常プレヒートを行うのであるが、本発明者等の研究によれば、光輝性顔料の配向とムラはその水性ベース塗料の塗着時からプレヒートまでの塗着塗膜の粘度上昇に関連することが解った。従来の水性ベース塗料では、塗着したベース塗膜はプレヒートまでの間に、かなりに急激に粘度が上昇することが解った。本発明では、特定のポリエーテルポリオールを添加すると、水性ベース塗料が塗着した時点からプレヒートまでの間で、粘度上昇が最初は低く抑えられるが、ある時点から急激に粘度が上昇するようにコントロールされて、光輝性顔料の配向がよくなると共に、塗膜のムラが生じないようにできることが確認された。 The flip-flop property is based on the orientation of the glitter pigment contained in the paint, but when the orientation of the glitter pigment is aligned and the FF property is increased, the unevenness of the coating film becomes more conspicuous. Normally, pre-heating is performed after spraying a water-based base paint with a spray gun, but according to studies by the present inventors, the orientation and unevenness of the glittering pigment are determined from the time of application of the water-based base paint to the pre-heating. It was found that this was related to an increase in the viscosity of the coating film. It has been found that with a conventional aqueous base paint, the viscosity of the applied base coating film increases considerably abruptly before preheating. In the present invention, when a specific polyether polyol is added, the increase in viscosity is initially suppressed to a low level between the time when the water-based base coating is applied and the time when it is preheated. As a result, it was confirmed that the orientation of the glittering pigment was improved and the coating film was not uneven.
本発明の複合塗膜形成方法は、自動車用鋼板上に形成された中塗り塗膜上に、水性ベース塗料を塗装してベース塗膜を形成した後、有機溶剤型クリヤー塗料を塗布してクリヤー塗膜を形成し、上記ベース塗膜とクリヤー塗膜とを加熱し硬化させる複層塗膜の形成方法において、上記水性ベース塗料が、樹脂固形分１００質量％中、
（ａ）アクリル樹脂エマルションが固形分で１０〜６０質量％、
（ｂ）水溶性アクリル樹脂が固形分で５〜４０質量％、および
（ｃ）メラミン樹脂が固形分で２０〜４０質量％、
（ｄ）下記化学式で表される数平均分子量４００〜２，０００のポリエーテルポリオール２〜２５質量％
含有することを特徴とするものである。
In the method for forming a composite coating film of the present invention, a water-based base coating is formed on an intermediate coating film formed on a steel plate for automobiles to form a base coating, and then an organic solvent type clear coating is applied to the clear coating. In the method for forming a multilayer coating film in which a coating film is formed and the base coating film and the clear coating film are heated and cured, the water-based base coating is in a resin solid content of 100% by mass,
(A) Acrylic resin emulsion is 10-60 mass% in solid content,
(B) Water-soluble acrylic resin is 5 to 40% by mass in solid content, and (c) Melamine resin is 20 to 40% by mass in solid content,
(D) 2 to 25% by mass of a polyether polyol having a number average molecular weight of 400 to 2,000 represented by the following chemical formula
It is characterized by containing.
水性ベース塗料
本発明の複層塗膜形成方法に用いられる水性ベース塗料は、（ａ）アクリル樹脂エマルションが固形分で１０〜６０質量％、（ｂ）水溶性アクリル樹脂が固形分で５〜４０質量％、（ｃ）メラミン樹脂が固形分で２０〜４０質量％および（ｄ）特定のポリエーテルポリオールを含有する。
Aqueous base paint The aqueous base paint used in the method for forming a multilayer coating film of the present invention has (a) an acrylic resin emulsion in a solid content of 10 to 60% by mass, and (b) a water-soluble acrylic resin in a solid content of 5 to 40. % By mass, (c) 20 to 40% by mass of the melamine resin in solid content and (d) a specific polyether polyol.
成分（ａ）
成分（ａ）のアクリル樹脂エマルションは、α，βーエチレン性不飽和モノマーの混合物をエマルション重合することによって得られる。上記モノマー混合物は、酸基または水酸基を有するα，β−エチレン性不飽和モノマーをその中に含むことにより、酸価および水酸基価を有することができる。酸価や水酸基価は、水溶性や架橋性に寄与する。
Ingredient (a)
The acrylic resin emulsion of component (a) is obtained by emulsion polymerization of a mixture of α, β-ethylenically unsaturated monomers. The monomer mixture can have an acid value and a hydroxyl value by including an α, β-ethylenically unsaturated monomer having an acid group or a hydroxyl group therein. The acid value and the hydroxyl value contribute to water solubility and crosslinkability.
上記酸基を有するα，β−エチレン性不飽和モノマーとしては、アクリル酸、メタクリル酸、アクリル酸二量体、クロトン酸、２−アクリロイルオキシエチルフタル酸、２−アクリロイルオキシエチルコハク酸、ω−カルボキシ−ポリカプロラクトンモノ（メタ）アクリレート、イソクロトン酸、α−ハイドロ−ω−（（１−オキソ−２−プロペニル）オキシ）ポリ（オキシ（１−オキソ−１，６−ヘキサンジイル））、マレイン酸、フマル酸、イタコン酸、３−ビニルサリチル酸、３−ビニルアセチルサリチル酸、２−アクリロイルオキシエチルアシッドフォスフェート、２−アクリルアミド−２−メチルプロパンスルホン酸等を挙げることができる。これらの中で好ましいものは、アクリル酸、メタクリル酸、アクリル酸二量体である。 Examples of the α, β-ethylenically unsaturated monomer having an acid group include acrylic acid, methacrylic acid, acrylic acid dimer, crotonic acid, 2-acryloyloxyethylphthalic acid, 2-acryloyloxyethyl succinic acid, ω- Carboxy-polycaprolactone mono (meth) acrylate, isocrotonic acid, α-hydro-ω-((1-oxo-2-propenyl) oxy) poly (oxy (1-oxo-1,6-hexanediyl)), maleic acid , Fumaric acid, itaconic acid, 3-vinylsalicylic acid, 3-vinylacetylsalicylic acid, 2-acryloyloxyethyl acid phosphate, 2-acrylamido-2-methylpropanesulfonic acid, and the like. Among these, acrylic acid, methacrylic acid, and acrylic acid dimer are preferable.
一方、水酸基を有するα，β−エチレン性不飽和モノマーとしては、（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル、（メタ）アクリル酸ヒドロキシブチル、アリルアルコール、メタクリルアルコール、（メタ）アクリル酸ヒドロキシエチルとε−カプロラクトンとの付加物を挙げることができる。これらの中で好ましいものは、（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシブチル、（メタ）アクリル酸ヒドロキシエチルとε−カプロラクトンとの付加物である。 On the other hand, as the α, β-ethylenically unsaturated monomer having a hydroxyl group, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, allyl alcohol, methacryl alcohol, (meth) Mention may be made of adducts of hydroxyethyl acrylate and ε-caprolactone. Among these, preferred are hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, and an adduct of hydroxyethyl (meth) acrylate and ε-caprolactone.
さらに、上記モノマー混合物はさらにその他のα，β−エチレン性不飽和モノマーを含んでいてもよい。上記その他のα，β−エチレン性不飽和モノマーとしては、（メタ）アクリル酸エステル（例えば（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ−プロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔ−ブチル、（メタ）アクリル酸２−エチルヘキシル、メタクリル酸ラウリル、アクリル酸フェニル、（メタ）アクリル酸イソボルニル、メタクリル酸シクロヘキシル、（メタ）アクリル酸ｔ−ブチルシクロヘキシル、（メタ）アクリル酸ジシクロペンタジエニル、（メタ）アクリル酸ジヒドロジシクロペンタジエニル等）、重合性アミド化合物（例えば、（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−ブトキシメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジブチル（メタ）アクリルアミド、Ｎ，Ｎ−ジオクチル（メタ）アクリルアミド、Ｎ−モノブチル（メタ）アクリルアミド、Ｎ−モノオクチル（メタ）アクリルアミド２，４−ジヒドロキシ−４’−ビニルベンゾフェノン、Ｎ−（２−ヒドロキシエチル）アクリルアミド、Ｎ−（２−ヒドロキシエチル）メタクリルアミド等）、重合性芳香族化合物（例えば、スチレン、α−メチルスチレン、ビニルケトン、ｔ−ブチルスチレン、パラクロロスチレン及びビニルナフタレン等）、重合性ニトリル（例えば、アクリロニトリル、メタクリロニトリル等）、α−オレフィン（例えば、エチレン、プロピレン等）、ビニルエステル（例えば、酢酸ビニル、プロピオン酸ビニル等）、ジエン（例えば、ブタジエン、イソプレン等）、重合性芳香族化合物、重合性ニトリル、α−オレフィン、ビニルエステル、及びジエンを挙げることができる。これらは目的により選択することができるが、親水性を容易に付与する場合には（メタ）アクリルアミドを用いることが好ましい。 Furthermore, the monomer mixture may further contain other α, β-ethylenically unsaturated monomers. Examples of the other α, β-ethylenically unsaturated monomers include (meth) acrylate esters (for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) acrylic). N-butyl acid, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl methacrylate, phenyl acrylate, isobornyl (meth) acrylate, cyclohexyl methacrylate, ( (Meth) acrylic acid t-butylcyclohexyl, (meth) acrylic acid dicyclopentadienyl, (meth) acrylic acid dihydrodicyclopentadienyl, etc.), polymerizable amide compounds (for example, (meth) acrylamide, N-methylol ( (Meth) acrylamide, N-butoxymethyl (meth) acrylic N, N-dimethyl (meth) acrylamide, N, N-dibutyl (meth) acrylamide, N, N-dioctyl (meth) acrylamide, N-monobutyl (meth) acrylamide, N-monooctyl (meth) acrylamide 2, 4-dihydroxy-4′-vinylbenzophenone, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, etc.), polymerizable aromatic compounds (for example, styrene, α-methylstyrene, vinyl ketone, t-butylstyrene, parachlorostyrene, vinylnaphthalene, etc.), polymerizable nitriles (eg, acrylonitrile, methacrylonitrile, etc.), α-olefins (eg, ethylene, propylene, etc.), vinyl esters (eg, vinyl acetate, propionic acid) Vinyl), dienes ( Examples thereof include butadiene and isoprene), polymerizable aromatic compounds, polymerizable nitriles, α-olefins, vinyl esters, and dienes. These can be selected depending on the purpose, but (meth) acrylamide is preferably used when hydrophilicity is easily imparted.
成分（ａ）のアクリル樹脂エマルションを形成するモノマー混合物は、必要に応じて、架橋性モノマーをモノマーの総量に基づいて０．２〜２０質量％、好ましくは０．５〜２０質量％含有する。架橋性モノマーが０．２質量％未満の場合は、塗装時の固形分が低下して、タレが発生する傾向がある。また、光輝性顔料の配向が乱れてＦＦ性が低下する。架橋性モノマーが２０質量％を超えると、樹脂がゲル化して、エマルションの合成が困難になる傾向がある。 The monomer mixture forming the acrylic resin emulsion of component (a) contains 0.2 to 20% by mass, preferably 0.5 to 20% by mass of a crosslinkable monomer based on the total amount of monomers, as necessary. When the crosslinkable monomer is less than 0.2% by mass, the solid content during coating tends to decrease and sagging tends to occur. Further, the orientation of the glitter pigment is disturbed and the FF property is lowered. When the crosslinkable monomer exceeds 20% by mass, the resin tends to gel and the synthesis of the emulsion tends to be difficult.
架橋性モノマーは、分子内に２つ以上のラジカル重合可能なエチレン性不飽和基を有する化合物であり、例えば、ジビニルベンゼン、エチレングリコールジ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、アリル（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート等のジビニル化合物が挙げられ、トリアリルシアヌレート、ペンタエリスリトールトリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等も挙げられる。架橋性モノマーは、上記のモノマーの組合せであってもよい。好ましい架橋性モノマーは、アリル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレートおよびジビニルベンゼンである。これらの架橋性モノマーは、比較的取扱が容易であるからである。なお、本明細書において「（メタ）アクリル」とはアクリルとメタクリルとの両方を意味するものとする。 The crosslinkable monomer is a compound having two or more radically polymerizable ethylenically unsaturated groups in the molecule. For example, divinylbenzene, ethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, polyethylene glycol Di (meth) acrylate, allyl (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexane di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate And diaryl compounds such as triallyl cyanurate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. The crosslinkable monomer may be a combination of the above monomers. Preferred crosslinkable monomers are allyl (meth) acrylate, ethylene glycol di (meth) acrylate and divinylbenzene. This is because these crosslinkable monomers are relatively easy to handle. In this specification, “(meth) acryl” means both acrylic and methacrylic.
アクリル樹脂エマルション（ａ）は、必要に応じて、酸価または水酸基価を有するのが好ましい。アクリル樹脂の酸価または水酸基価はそれが合成されるモノマー混合物の酸価または水酸基価と実質上同じである。本発明で用いるモノマー混合物は酸価が好ましくは３〜５０ｍｇＫＯＨ／ｇであり、より好ましくは７〜４０ｍｇＫＯＨ／ｇである。酸価が３ｍｇＫＯＨ／ｇ未満では、作業性を向上させることができず、５０ｍｇＫＯＨ／ｇを上回ると、塗膜の耐水性が低下する。一方、上記水性ベース塗料が硬化性を有する必要がある場合には、モノマー混合物は水酸基価が１０〜１５０ｍｇＫＯＨ／ｇであり、好ましくは２０〜１００ｍｇＫＯＨ／ｇである必要がある。水酸基価が１０ｍｇＫＯＨ／ｇ未満では、充分な硬化性が得られず、１５０ｍｇＫＯＨ／ｇを上回ると、塗膜の耐水性が低下する。また、上記モノマー混合物を共重合して得られるポリマーのガラス転移温度は、−２０〜８０℃の間であることが、得られる塗膜の機械的物性の点から好ましい。 The acrylic resin emulsion (a) preferably has an acid value or a hydroxyl value as required. The acid value or hydroxyl value of the acrylic resin is substantially the same as the acid value or hydroxyl value of the monomer mixture in which it is synthesized. The monomer mixture used in the present invention has an acid value of preferably 3 to 50 mgKOH / g, more preferably 7 to 40 mgKOH / g. If the acid value is less than 3 mgKOH / g, the workability cannot be improved, and if it exceeds 50 mgKOH / g, the water resistance of the coating film decreases. On the other hand, when the aqueous base coating material needs to have curability, the monomer mixture needs to have a hydroxyl value of 10 to 150 mgKOH / g, preferably 20 to 100 mgKOH / g. When the hydroxyl value is less than 10 mgKOH / g, sufficient curability cannot be obtained, and when it exceeds 150 mgKOH / g, the water resistance of the coating film is lowered. Moreover, it is preferable from the point of the mechanical physical property of the coating film obtained that the glass transition temperature of the polymer obtained by copolymerizing the said monomer mixture is between -20-80 degreeC.
本発明の水性ベース塗料に含まれるアクリル樹脂エマルションは、上記モノマー混合物を乳化重合して得られるものである。ここで行われる乳化重合は、通常よく知られている方法を用いて行うことができる。具体的には、水、または必要に応じてアルコールなどのような有機溶剤を含む水性媒体中に乳化剤を溶解させ、加熱撹拌下、上記モノマー混合物および重合開始剤を滴下することにより行うことができる。乳化剤と水とを用いて予め乳化したモノマー混合物を同様に滴下してもよい。 The acrylic resin emulsion contained in the aqueous base paint of the present invention is obtained by emulsion polymerization of the monomer mixture. The emulsion polymerization carried out here can be carried out using a generally well-known method. Specifically, it can be carried out by dissolving the emulsifier in water or an aqueous medium containing an organic solvent such as alcohol as required, and dropping the monomer mixture and the polymerization initiator under heating and stirring. . A monomer mixture emulsified in advance using an emulsifier and water may be similarly dropped.
好適に用いうる重合開始剤としては、アゾ系の油性化合物（例えば、アゾビスイソブチロニトリル、２，２’−アゾビス（２−メチルブチロニトリル）および２，２’−アゾビス（２，４−ジメチルバレロニトリル）など）、および水性化合物（例えば、アニオン系の４，４’−アゾビス（４−シアノ吉草酸）、２，２−アゾビス（Ｎ−（２−カルボキシエチル）−２−メチルプロピオンアミジンおよびカチオン系の２，２’−アゾビス（２−メチルプロピオンアミジン））；並びにレドックス系の油性過酸化物（例えば、ベンゾイルパーオキサイド、パラクロロベンゾイルパーオキサイド、ラウロイルパーオキサイドおよびｔ−ブチルパーベンゾエートなど）、および水性過酸化物（例えば、過硫酸カリおよび過硫酸アンモニウムなど）が挙げられる。 Suitable polymerization initiators include azo oily compounds (for example, azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile) and 2,2′-azobis (2,4 -Dimethylvaleronitrile) and the like, and aqueous compounds (for example, anionic 4,4'-azobis (4-cyanovaleric acid), 2,2-azobis (N- (2-carboxyethyl) -2-methylpropion) Amidine and cationic 2,2′-azobis (2-methylpropionamidine)); and redox oily peroxides (eg, benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide and t-butyl perbenzoate) Etc.), and aqueous peroxides such as potassium persulfate and ammonium persulfate It is below.
乳化剤には、当業者に通常使用されているものを用いうるが、反応性乳化剤、例えば、アントックス（Ａｎｔｏｘ）ＭＳ−６０（日本乳化剤社製）、エレミノールＪＳ−２（三洋化成工業社製）、アデカリアソープＮＥ−２０（旭電化社製）およびアクアロンＨＳ−１０（第一工業製薬社製）などが特に好ましい。 As the emulsifier, those commonly used by those skilled in the art can be used. However, reactive emulsifiers such as Antox MS-60 (manufactured by Nippon Emulsifier Co., Ltd.), Eleminol JS-2 (manufactured by Sanyo Chemical Industries Ltd.) Adekaria soap NE-20 (Asahi Denka Co., Ltd.) and Aqualon HS-10 (Daiichi Kogyo Seiyaku Co., Ltd.) are particularly preferred.
また、分子量を調節するために、ラウリルメルカプタンのようなメルカプタンおよびα−メチルスチレンダイマーなどのような連鎖移動剤を必要に応じて用いうる。 In order to adjust the molecular weight, a mercaptan such as lauryl mercaptan and a chain transfer agent such as α-methylstyrene dimer may be used as necessary.
反応温度は開始剤により決定され、例えば、アゾ系開始剤では６０〜９０℃であり、レドックス系では３０〜７０℃で行うことが好ましい。一般に、反応時間は１〜８時間である。モノマー混合物の総量に対する開始剤の量は、一般に０．１〜５質量％であり、好ましくは０．２〜２質量％である。 The reaction temperature is determined by the initiator, and for example, it is preferably 60 to 90 ° C. for an azo initiator and 30 to 70 ° C. for a redox system. In general, the reaction time is 1 to 8 hours. The amount of the initiator relative to the total amount of the monomer mixture is generally 0.1 to 5% by mass, preferably 0.2 to 2% by mass.
上記乳化重合は多段階で行うことができ、例えば、二段階で行うことができる。すなわち、まず上記α，β−エチレン性不飽和モノマー混合物のうちの一部（モノマー混合物１）を乳化重合し、ここに上記α，β−エチレン性不飽和モノマー混合物の残り（モノマー混合物２）をさらに加えて乳化重合を行うものである。 The emulsion polymerization can be performed in multiple stages, for example, in two stages. That is, first, a part (monomer mixture 1) of the α, β-ethylenically unsaturated monomer mixture is subjected to emulsion polymerization, and the remainder of the α, β-ethylenically unsaturated monomer mixture (monomer mixture 2) is added thereto. In addition, emulsion polymerization is performed.
ここでクリヤー塗膜とのなじみ防止の点から、モノマー混合物１はアミド基を有するα，β−エチレン性不飽和モノマーを含有していることが好ましい。またこの時、モノマー混合物２は、アミド基を有するα，β−エチレン性不飽和モノマーを含有していないことがさらに好ましい。なお、モノマー混合物１および２を一緒にしたものが、上記モノマー混合物であるため、先に示した上記α，β−エチレン性不飽和モノマー混合物の要件は、モノマー混合物１および２を一緒にしたものが満たすことになる。 The monomer mixture 1 preferably contains an α, β-ethylenically unsaturated monomer having an amide group from the viewpoint of preventing the compatibility with the clear coating film. At this time, it is more preferable that the monomer mixture 2 does not contain an α, β-ethylenically unsaturated monomer having an amide group. Since the mixture of monomer mixtures 1 and 2 is the monomer mixture, the requirement for the α, β-ethylenically unsaturated monomer mixture described above is the combination of monomer mixtures 1 and 2. Will meet.
上記アクリル樹脂エマルションの体積平均粒子径は０．０１〜１．０μｍの範囲であることが好ましい。体積平均粒子径が０．０１μｍ未満であると作業性の改善の効果が小さく、１．０μｍを上回ると得られる塗膜の外観が悪化する恐れがある。この粒子径の調節は、例えば、モノマー組成や乳化重合条件を調整することにより可能である。 The volume average particle size of the acrylic resin emulsion is preferably in the range of 0.01 to 1.0 μm. When the volume average particle diameter is less than 0.01 μm, the effect of improving workability is small, and when it exceeds 1.0 μm, the appearance of the obtained coating film may be deteriorated. The particle size can be adjusted, for example, by adjusting the monomer composition and emulsion polymerization conditions.
上記アクリル樹脂エマルションは、必要に応じて塩基で中和することにより、ｐＨ５〜１０で用いることができる。これは、このｐＨ領域における安定性が高いからである。この中和は、乳化重合の前または後に、ジメチルエタノールアミンやトリエチルアミンのような３級アミンを系に添加することにより行うことが好ましい。 The said acrylic resin emulsion can be used by pH 5-10 by neutralizing with a base as needed. This is because the stability in this pH region is high. This neutralization is preferably carried out by adding a tertiary amine such as dimethylethanolamine or triethylamine to the system before or after emulsion polymerization.
成分（ａ）のアクリル樹脂エマルションは、水性ベース塗料中に１０〜６０質量％、好ましくは１５〜５０質量％の量で配合する。１０質量％未満では、高固形分化と良好なＦＦ性が得られない。６０質量％を超えると、塗着時の粘度上昇が速すぎ、得られる塗膜の色ムラが発生する。 The acrylic resin emulsion of component (a) is blended in the aqueous base paint in an amount of 10 to 60% by mass, preferably 15 to 50% by mass. If it is less than 10% by mass, high solid differentiation and good FF properties cannot be obtained. When it exceeds 60 mass%, the viscosity increase at the time of application will be too fast, and color unevenness of the resulting coating film will occur.
成分（ｂ）
本発明の水性ベース塗料は、水溶性アクリル樹脂（ｂ）を含有する。水溶性アクリル樹脂は、水性ベース塗料中に５〜４０質量％、好ましくは１０〜３０質量％の量で含有する。５質量％より少ないと、塗着時の粘度上昇が速すぎ、得られる塗膜の色ムラが発生する。４０質量％を超えると、良好なＦＦ性が出なくなる。
Ingredient (b)
The aqueous base paint of the present invention contains a water-soluble acrylic resin (b). The water-soluble acrylic resin is contained in the aqueous base paint in an amount of 5 to 40% by mass, preferably 10 to 30% by mass. When it is less than 5% by mass, the viscosity increase during coating is too fast, and color unevenness of the resulting coating film occurs. When it exceeds 40 mass%, favorable FF property will not come out.
水溶性アクリル樹脂は、数平均分子量３０００〜５００００、好ましくは６０００〜３００００であることが好ましい。３０００より小さいと作業性および硬化性が十分でなく、５００００を越えると塗装時の不揮発分が低くなりすぎ、かえって作業性が悪くなる。 The water-soluble acrylic resin has a number average molecular weight of 3,000 to 50,000, preferably 6,000 to 30,000. If it is less than 3000, workability and curability are not sufficient, and if it exceeds 50000, the non-volatile content at the time of coating becomes too low, and workability is rather deteriorated.
また、水溶性アクリル樹脂は１０〜１００ｍｇＫＯＨ／ｇ、更に２０〜８０ｍｇＫＯＨ／ｇの酸価を有することが好ましく、上限を越えると塗膜の耐水性が低下し、下限を下回ると樹脂の水分散性が低下する。また、２０〜１８０ｍｇＫＯＨ／ｇ、更に３０〜１６０ｍｇＫＯＨ／ｇの水酸基価を有することが好ましく、上限を越えると塗膜の耐水性が低下し、下限を下回ると塗膜の硬化性が低下する。 The water-soluble acrylic resin preferably has an acid value of 10 to 100 mg KOH / g, more preferably 20 to 80 mg KOH / g. When the upper limit is exceeded, the water resistance of the coating film is lowered, and when the lower limit is exceeded, the water dispersibility of the resin is reduced. Decreases. Further, it preferably has a hydroxyl value of 20 to 180 mgKOH / g, more preferably 30 to 160 mgKOH / g. When the upper limit is exceeded, the water resistance of the coating film decreases, and when the lower limit is exceeded, the curability of the coating film decreases.
この水溶性アクリル樹脂は、先のモノマー混合物のところで述べた酸基を有するα，β−エチレン性不飽和モノマーを必須成分とし、それ以外のα，β−エチレン性不飽和モノマーとともに溶液重合を行うことにより得ることができる。 This water-soluble acrylic resin has an α, β-ethylenically unsaturated monomer having an acid group described in the previous monomer mixture as an essential component, and performs solution polymerization together with other α, β-ethylenically unsaturated monomers. Can be obtained.
なお、上記水溶性アクリル樹脂は、通常、塩基性化合物、例えばモノメチルアミン、ジメチルアミン、トリメチルアミン、トリエチルアミン、ジイソプロピルアミン、モノエタノールアミン、ジエタノールアミン及びジメチルエタノールアミンのような有機アミンで中和し、水に溶解させて用いるが、この中和は、水溶性アクリル樹脂そのものに対して行っても、後述する水性ベース塗料の製造時に行ってもよい。 The water-soluble acrylic resin is usually neutralized with a basic compound, for example, an organic amine such as monomethylamine, dimethylamine, trimethylamine, triethylamine, diisopropylamine, monoethanolamine, diethanolamine, and dimethylethanolamine, and added to water. Although it dissolves and uses, this neutralization may be performed with respect to water-soluble acrylic resin itself, or may be performed at the time of manufacture of the water-based base coating material mentioned later.
成分（ｃ）
本発明の水性ベース塗料は、メラミン樹脂（ｃ）を硬化剤として含有する。メラミン樹脂は、水溶性であっても、非水溶性であってもよい。メラミン樹脂のなかでも水トレランスが３．０以上のものを用いることが、安定性上好ましい。ここで用いる水トレランスとは、親水性の度合を評価するためのものであり、その値が高いほど親水性が高いことを意味する。水トレランス値の測定方法は、２５℃において、１００ｍｌビーカー内で、サンプル０．５ｇをアセトン１０ｍｌに混合して分散させ、ビュウレットを用いてイオン交換水を徐々に加え、混合物が白濁を生じるまでに要するイオン交換水の量（ｍｌ）を測定し、このイオン交換水の量（ｍｌ）を水トレランス値としたものである。
Ingredient (c)
The aqueous base paint of the present invention contains melamine resin (c) as a curing agent. The melamine resin may be water-soluble or water-insoluble. Among the melamine resins, it is preferable in terms of stability to use a water tolerance of 3.0 or more. The water tolerance used here is for evaluating the degree of hydrophilicity, and the higher the value, the higher the hydrophilicity. The water tolerance value was measured by mixing 0.5 g of a sample in 10 ml of acetone and dispersing in a 100 ml beaker at 25 ° C., and gradually adding ion-exchanged water using a burette until the mixture became cloudy. The amount (ml) of ion exchange water required is measured, and this amount (ml) of ion exchange water is used as a water tolerance value.
メラミン樹脂の含有量は水性ベースコート組成物中の樹脂固形分に対し、２０〜４０質量％であることが好ましい。２０質量％未満では硬化性が低下し、４０質量％を超えると塗料の安定性が低下するおそれがある。 The content of the melamine resin is preferably 20 to 40% by mass with respect to the resin solid content in the aqueous base coat composition. If it is less than 20% by mass, the curability is lowered, and if it exceeds 40% by mass, the stability of the paint may be lowered.
成分（ｄ）
本発明では、水性ベース塗料中に化学式：
で表される数平均分子量４００〜２，０００のポリエーテルポリオールが２〜２５質量％、好ましくは５〜２０質量％の量で添加される。添加量が２質量％より少ないと、得られる塗膜の色ムラが発生する。２５質量％を超えると、ＦＦ性が悪くなる。
Ingredient (d)
In the present invention, the water-based base paint has the chemical formula:
A polyether polyol having a number average molecular weight of 400 to 2,000 represented by is added in an amount of 2 to 25% by mass, preferably 5 to 20% by mass. If the amount added is less than 2% by mass, color unevenness of the resulting coating film occurs. When it exceeds 25 mass%, FF property will worsen.
上記ポリエーテルポリオールは、グリセリンの３個のヒドロキシル基の全てがアルキレンオキシドでエーテル付加されている。アルキレンオキシドの付加数は、上記化学式（１）中でｌ、ｍおよびｎで表され、ｌ、ｍおよびｎは１〜１２の自然数である。また、上記ポリエーテルポリオールは、数平均分子量４００〜２，０００，好ましくは４００〜１，０００である。数平均分子量が４００より小さいと、ムラが悪くなり、２，０００より大きいとＦＦ性が悪くなる。 In the polyether polyol, all three hydroxyl groups of glycerin are ether-added with alkylene oxide. The addition number of alkylene oxide is represented by l, m and n in the chemical formula (1), and l, m and n are natural numbers of 1 to 12. The polyether polyol has a number average molecular weight of 400 to 2,000, preferably 400 to 1,000. When the number average molecular weight is smaller than 400, unevenness is worsened, and when it is larger than 2,000, FF properties are worsened.
上記ポリエーテルポリオールは、市販品が存在する。具体的には、三洋化成工業株式会社から市販のＧＰ−４００（ｌ／ｍ／ｎ＝１〜２／１〜２／１〜２；数平均分子量４００）あるいはＧＰ−１０００（ｌ／ｍ／ｎ＝４〜６／４〜６／４〜６；数平均分子量１０００）である。 Commercially available products exist for the polyether polyol. Specifically, GP-400 (l / m / n = 1 to 2/1 to 2/1 to 2; number average molecular weight 400) or GP-1000 (l / m / n) commercially available from Sanyo Chemical Industries, Ltd. = 4-6 / 4-6 / 4-6; number average molecular weight 1000).
その他の成分
本発明の水性ベース塗料は、顔料を含む。顔料としては、光輝性顔料および着色顔料が挙げられる。光輝性顔料としては、形状は特に限定されず、また着色されていてもよいが、例えば、平均粒径（Ｄ50）が２〜５０μｍであり、かつ厚さが０．１〜５μｍであるものが好ましい。また、平均粒径が１０〜３５μｍの範囲のものが光輝感に優れ、さらに好適に用いられる。具体的には、アルミニウム、銅、亜鉛、鉄、ニッケル、スズ、酸化アルミニウム等の金属または合金等の無着色あるいは着色された金属製光輝剤およびその混合物が挙げられる。この他に干渉マイカ顔料、ホワイトマイカ顔料、グラファイト顔料などもこの中に含めるものとする。
Other Components The aqueous base paint of the present invention contains a pigment. Examples of pigments include glitter pigments and colored pigments. The shape of the glitter pigment is not particularly limited and may be colored. For example, the pigment having an average particle diameter (D 50 ) of 2 to 50 μm and a thickness of 0.1 to 5 μm Is preferred. Those having an average particle diameter in the range of 10 to 35 μm are excellent in glitter and are more preferably used. Specific examples include non-colored or colored metallic brightening agents such as aluminum, copper, zinc, iron, nickel, tin, and aluminum oxide, and alloys, and mixtures thereof. In addition, interference mica pigments, white mica pigments, graphite pigments, and the like are included in this.
一方、着色顔料としては、例えば有機系のアゾキレート系顔料、不溶性アゾ系顔料、縮合アゾ系顔料、フタロシアニン系顔料、インジゴ顔料、ペリノン系顔料、ペリレン系顔料、ジオキサン系顔料、キナクリドン系顔料、イソインドリノン系顔料、金属錯体顔料等が挙げられ、無機系では黄鉛、黄色酸化鉄、ベンガラ、カーボンブラック、二酸化チタン等が挙げられる。 On the other hand, as the colored pigment, for example, organic azo chelate pigment, insoluble azo pigment, condensed azo pigment, phthalocyanine pigment, indigo pigment, perinone pigment, perylene pigment, dioxane pigment, quinacridone pigment, isoindo Examples thereof include linone pigments and metal complex pigments. Examples of inorganic pigments include chrome lead, yellow iron oxide, bengara, carbon black, and titanium dioxide.
本発明の水性ベース塗料中の全顔料濃度（ＰＷＣ）としては、０．１〜５０質量％であることが好ましい。さらに好ましくは、０．５〜４０質量％であり、特に好ましくは、１．０〜３０質量％である。上限を越えると塗膜外観が低下する。また、光輝性顔料が含まれる場合、その顔料濃度（ＰＷＣ）としては、一般的に１８．０質量％以下であることが好ましい。上限を越えると塗膜外観が低下する。さらに好ましくは、０．０１〜１５．０質量％であり、特に好ましくは、０．０１〜１３．０質量％である。 The total pigment concentration (PWC) in the aqueous base paint of the present invention is preferably 0.1 to 50% by mass. More preferably, it is 0.5-40 mass%, Most preferably, it is 1.0-30 mass%. When the upper limit is exceeded, the appearance of the coating film deteriorates. When a bright pigment is included, the pigment concentration (PWC) is generally preferably 18.0% by mass or less. When the upper limit is exceeded, the appearance of the coating film deteriorates. More preferably, it is 0.01-15.0 mass%, Most preferably, it is 0.01-13.0 mass%.
またさらに、本発明の水性ベース塗料には、上塗り塗膜とのなじみ防止、塗装作業性を確保するために、その他の粘性制御剤を添加することができる。粘性制御剤としては、一般にチクソトロピー性を示すものを使用でき、例えば、架橋あるいは非架橋の樹脂粒子、脂肪酸アマイドの膨潤分散体、アマイド系脂肪酸、長鎖ポリアミノアマイドの燐酸塩等のポリアマイド系のもの、酸化ポリエチレンのコロイド状膨潤分散体等のポリエチレン系等のもの、有機酸スメクタイト粘土、モンモリロナイト等の有機ベントナイト系のもの、ケイ酸アルミ、硫酸バリウム等の無機顔料、顔料の形状により粘性が発現する偏平顔料等を挙げることができる。 Furthermore, other viscosity control agents can be added to the water-based base paint of the present invention in order to prevent familiarity with the top coat film and to ensure coating workability. As the viscosity control agent, those generally showing thixotropy can be used, for example, polyamide-based ones such as crosslinked or non-crosslinked resin particles, swelling dispersions of fatty acid amides, amide fatty acids, and long-chain polyaminoamide phosphates. Viscosity develops depending on the shape of polyethylene, such as colloidal swelling dispersion of polyethylene oxide, organic bentonite such as organic acid smectite clay, montmorillonite, inorganic pigments such as aluminum silicate and barium sulfate, etc. A flat pigment etc. can be mentioned.
本発明に用いられる水性メタリックベース塗料中には、上記成分の他に塗料に通常添加される添加剤、例えば、表面調整剤、増粘剤、酸化防止剤、紫外線防止剤、消泡剤等を配合してもよい。これらの配合量は当業者の公知の範囲である。 In the aqueous metallic base paint used in the present invention, in addition to the above-mentioned components, additives usually added to the paint, such as surface conditioners, thickeners, antioxidants, UV inhibitors, antifoaming agents, etc. You may mix | blend. These compounding amounts are within the range known to those skilled in the art.
上記水性ベース塗料は、成分（ｃ）のメラミン樹脂硬化剤の他に、他の硬化剤を含んでもよい。そのような硬化剤としては、塗料一般に用いられているものを使用することができる。このようなものとして、ブロックイソシアネート、エポキシ化合物、アジリジン化合物、カルボジイミド化合物、オキサゾリン化合物、金属イオン等が挙げられる。得られた塗膜の諸性能、コストの点からブロックイソシアネート樹脂が一般的に用いられる。 In addition to the melamine resin curing agent of component (c), the aqueous base paint may contain other curing agents. As such a hardening | curing agent, what is generally used for the coating material can be used. Examples of such compounds include blocked isocyanates, epoxy compounds, aziridine compounds, carbodiimide compounds, oxazoline compounds, and metal ions. A blocked isocyanate resin is generally used from the viewpoint of various performances and costs of the obtained coating film.
上記ブロックイソシアネートとしては、トリメチレンジイソシアネート、ヘキサメチレンジイソシアネート、キシリレンジイソシアネート、イソホロンジイソシアネート等のポリイソシアネートに活性水素を有するブロック剤を付加させることによって得ることができるものであって、加熱によりブロック剤が解離してイソシアネート基が発生するものが挙げられる。 The above-mentioned blocked isocyanate can be obtained by adding a blocking agent having active hydrogen to a polyisocyanate such as trimethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, etc. Examples include those that dissociate and generate isocyanate groups.
本発明の水性ベース塗料には、更に必要に応じて、ポリエステル樹脂を配合してもよい。ポリエステル樹脂は酸成分およびアルコール成分を縮重合して得られる。上記酸成分としては特に限定されず、アジピン酸、セバシン酸、イソフタル酸、無水フタル酸等の多価カルボン酸化合物およびそれらの無水物を挙げることができる。さらに、酸成分として、ジメチロールプロピオン酸等の１分子中にカルボン酸基と水酸基とを有する化合物を用いることができる。また、上記アルコール成分としては特に限定されず、エチレングリコール、トリメチロールプロパン、ネオペンチルグリコール等の多価アルコール化合物を挙げることができる。上記ポリエステル樹脂は、好ましくは、樹脂固形分酸価１０〜８０ｍｇＫＯＨ／ｇ、および数平均分子量１０００〜１５０００を有する。ポリエステル樹脂は、得られる塗膜の色ムラを抑制するために添加される。ポリエステル樹脂の塗料中の配合量は、５〜３０質量％、好ましくは１０〜２０質量％である。５質量％より少ないと、色ムラ抑制の効果が小さく、３０質量％より多いと、フリップフロップ性が低下するおそれがある。 If necessary, the water-based base coating material of the present invention may further contain a polyester resin. The polyester resin is obtained by condensation polymerization of an acid component and an alcohol component. The acid component is not particularly limited, and examples thereof include polyvalent carboxylic acid compounds such as adipic acid, sebacic acid, isophthalic acid, and phthalic anhydride, and anhydrides thereof. Furthermore, as an acid component, a compound having a carboxylic acid group and a hydroxyl group in one molecule such as dimethylolpropionic acid can be used. Moreover, it does not specifically limit as said alcohol component, Polyhydric alcohol compounds, such as ethylene glycol, a trimethylol propane, neopentyl glycol, can be mentioned. The polyester resin preferably has a resin solid content acid value of 10 to 80 mgKOH / g and a number average molecular weight of 1000 to 15000. The polyester resin is added to suppress color unevenness of the obtained coating film. The compounding quantity in the coating material of a polyester resin is 5-30 mass%, Preferably it is 10-20 mass%. If it is less than 5% by mass, the effect of suppressing color unevenness is small, and if it is more than 30% by mass, the flip-flop property may be lowered.
本発明に用いられる塗料の製造方法は、後述するものを含めて、特に限定されず、顔料等の配合物をニーダーまたはロール等を用いて混練、分散する等の当業者に周知の全ての方法を用い得る。 The method for producing the paint used in the present invention is not particularly limited, including those described later, and all methods well known to those skilled in the art such as kneading and dispersing a compound such as a pigment using a kneader or a roll. Can be used.
有機溶剤型クリヤー塗料
上記有機溶剤型クリヤー塗料は、特に限定されず、塗膜形成性樹脂および硬化剤等を含有するクリヤー塗料を利用できる。更に下地の意匠性を妨げない程度であれば着色顔料を含有することもできる。
Organic solvent type clear paint The organic solvent type clear paint is not particularly limited, and a clear paint containing a film-forming resin and a curing agent can be used. Furthermore, a color pigment can also be contained as long as it does not interfere with the design of the base.
上記有機溶剤型クリヤー塗料の好ましい例としては、透明性あるいは耐酸エッチング性等の点から、アクリル樹脂および／またはポリエステル樹脂とアミノ樹脂及び／またはイソシアネートとの組合わせ、あるいはカルボン酸・エポキシ硬化系を有するアクリル樹脂および／またはポリエステル樹脂系等が挙げられる。 Preferred examples of the organic solvent-type clear coating include a combination of an acrylic resin and / or a polyester resin with an amino resin and / or an isocyanate, or a carboxylic acid / epoxy curing system in terms of transparency or acid etching resistance. And acrylic resin and / or polyester resin system.
更に、上記有機溶剤型クリヤー塗料には、塗装作業性を確保するために、粘性制御剤が添加されていることが好ましい。粘性制御剤は、一般にチクソトロピー性を示すものを使用できる。このようなものとして、例えば、上述の水性ベースコート組成物のところで述べたものを使用することができる。また必要により、硬化触媒、表面調整剤等を含むことができる。 Furthermore, it is preferable that a viscosity control agent is added to the organic solvent-type clear coating material in order to ensure coating workability. As the viscosity control agent, those generally showing thixotropy can be used. As such a thing, what was described in the above-mentioned aqueous | water-based basecoat composition can be used, for example. Moreover, a curing catalyst, a surface conditioner, etc. can be included if necessary.
被塗物
本発明の塗膜形成方法は、種々の基材、例えば金属、プラスチック、発泡体等、特に金属表面、および鋳造物に有利に用い得るが、カチオン電着塗装可能な金属製品に対し、特に好適に使用できる。
The coating film forming method of the present invention can be advantageously used for various substrates such as metals, plastics, foams, etc., particularly metal surfaces, and castings. Can be used particularly preferably.
上記金属製品としては、例えば、鉄、銅、アルミニウム、スズ、亜鉛等およびこれらの金属を含む合金が挙げられる。具体的には、乗用車、トラック、オートバイ、バス等の自動車車体および部品が挙げられる。これらの金属は予めリン酸塩、クロム酸塩等で化成処理されたものが特に好ましい。 Examples of the metal products include iron, copper, aluminum, tin, zinc and the like and alloys containing these metals. Specific examples include automobile bodies and parts such as passenger cars, trucks, motorcycles, and buses. These metals are particularly preferably those subjected to chemical conversion treatment with phosphate, chromate or the like in advance.
上記化成処理された鋼板上に電着塗膜が形成されていても良く、この電着塗料としては、カチオン型及びアニオン型を使用できるが、カチオン型電着塗料組成物が防食性において優れた複層塗膜を与えるため好ましい。 An electrodeposition coating film may be formed on the chemical conversion treated steel sheet. As this electrodeposition coating, a cation type and an anion type can be used, but the cationic type electrodeposition coating composition is excellent in corrosion resistance. This is preferable because it gives a multilayer coating film.
上記プラスチック製品としては、ポリプロピレン樹脂、ポリカーボネート樹脂、ウレタン樹脂、ポリエステル樹脂、ポリスチレン樹脂、ＡＢＳ樹脂、塩化ビニル樹脂、ポリアミド樹脂等のものが挙げられる。具体的には、スポイラー、バンパー、ミラーカバー、グリル、ドアノブ等の自動車部品等が挙げられる。これらのプラスチック製品は、トリクロロエタンで蒸気洗浄または中性洗剤で洗浄されたものが好ましく、また、さらに静電塗装を可能にするためのプライマー塗装が施されていてもよい。 Examples of the plastic product include polypropylene resin, polycarbonate resin, urethane resin, polyester resin, polystyrene resin, ABS resin, vinyl chloride resin, polyamide resin and the like. Specific examples include automobile parts such as spoilers, bumpers, mirror covers, grills, and door knobs. These plastic products are preferably those washed with steam or neutral detergent with trichloroethane, and may further be provided with a primer coating to enable electrostatic coating.
上記基材上にはさらに必要に応じて、中塗り塗膜が形成されていてもよい。中塗り塗膜の形成には中塗り塗料が用いられる。この中塗り塗料には、塗膜形成性樹脂、硬化剤、有機系や無機系の各種着色顔料及び体質顔料等が含有される。 If necessary, an intermediate coating film may be formed on the substrate. An intermediate coating is used to form the intermediate coating film. The intermediate coating contains a film-forming resin, a curing agent, various organic and inorganic color pigments, extender pigments, and the like.
上記中塗り塗料に含まれる塗膜形成性樹脂は、特に限定されるものではなく、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、ウレタン樹脂等の塗膜形成性樹脂が利用でき、これらは、先の水性ベースコート組成物のところで挙げた硬化剤と組み合わせて用いられる。得られた塗膜の諸性能、コストの点からアミノ樹脂および／またはイソシアネート樹脂が一般的に用いられる。 The film-forming resin contained in the intermediate coating is not particularly limited, and film-forming resins such as acrylic resin, polyester resin, alkyd resin, epoxy resin, and urethane resin can be used. It is used in combination with the curing agent mentioned in the previous aqueous base coat composition. An amino resin and / or an isocyanate resin is generally used in view of various performances and costs of the obtained coating film.
上記中塗り塗料に含まれる着色顔料としては、先の水性ベースコート組成物の記載で挙げたものを同様に用いることができる。標準的には、カーボンブラックと二酸化チタンとを主要顔料としたグレー系中塗り塗料や上塗りとの色相を合わせたセットグレーや各種の着色顔料を組み合わせた、いわゆるカラー中塗り塗料を用いることが好ましい。更に、アルミニウム粉、マイカ粉等の扁平顔料が添加されていても良い。これらの中塗り塗料中には、上記成分の他に塗料に通常添加される添加剤、例えば、表面調整剤、酸化防止剤、消泡剤等が配合されていてもよい。 As the color pigment contained in the intermediate coating composition, those described in the description of the aqueous base coat composition can be used in the same manner. As a standard, it is preferable to use a so-called color intermediate coating that combines carbon black and titanium dioxide as main pigments with a gray intermediate coating or a set gray that combines the hue of the top coating and various colored pigments. . Furthermore, flat pigments such as aluminum powder and mica powder may be added. In these intermediate coating materials, in addition to the above components, additives usually added to the coating material, for example, surface conditioners, antioxidants, antifoaming agents and the like may be blended.
複層塗膜形成方法
本発明の複層塗膜形成方法では、必要により電着塗膜および中塗り塗膜を形成した被塗物上に、水性ベース塗料によるベース塗膜及び有機溶剤型クリヤー塗料によるクリヤー塗膜を、順次形成することができる。
Multilayer coating film forming method In the multilayer coating film forming method of the present invention, a base coating film and an organic solvent-type clear coating composition using an aqueous base coating material are coated on an object on which an electrodeposition coating film and an intermediate coating film are formed if necessary. The clear coating film can be formed sequentially.
本発明で、水性ベース塗料を、自動車車体に塗装する場合は、外観を高めるために、エアー静電スプレー塗装による多ステージ塗装、好ましくは２ステージで塗装するか、或いは、エアー静電スプレー塗装と、通称「μμ（マイクロマイクロ）ベル」、「μ（マイクロ）ベル」あるいは「メタベル」等と言われる回転霧化式の静電塗装機とを組み合わせた塗装方法等により塗膜を形成する方法を用いることができる。 In the present invention, when an aqueous base paint is applied to an automobile body, in order to enhance the appearance, it is applied in multiple stages by air electrostatic spray painting, preferably in two stages, or air electrostatic spray painting. , A method of forming a coating film by a coating method combined with a rotary atomizing electrostatic coating machine called “μμ (micro micro) bell”, “μ (micro) bell” or “metabell” Can be used.
本発明における、水性ベース塗料による塗装時の塗膜の膜厚は所望の用途により変化するが、多くの場合１０〜３０μｍが有用である。上限を越えると、鮮映性が低下したり、塗装時にムラあるいは流れ等の不具合が起こることがあり、下限を下回ると、下地が隠蔽できず膜切れが発生する。 In the present invention, the film thickness of the coating film when applied with a water-based base paint varies depending on the desired application, but in many cases, 10 to 30 μm is useful. If the upper limit is exceeded, sharpness may deteriorate, or defects such as unevenness or flow may occur during coating. If the lower limit is exceeded, the substrate cannot be concealed and film breakage occurs.
本発明の複層塗膜形成方法では、未硬化のベース塗膜の上にさらにクリヤー塗料を塗布し、クリヤー塗膜を形成すること（ウェット・オン・ウェット塗装）が焼き付け乾燥炉を省略することができ、経済性及び環境面からも好ましい。なお、良好な仕上がり塗膜を得るために、クリヤー塗料を塗布する前に、未硬化のベース塗膜を４０〜１００℃で２〜１０分間加熱しておくことが望ましい。 In the multilayer coating film forming method of the present invention, a clear coating is further applied on the uncured base coating to form a clear coating (wet-on-wet coating), omitting the baking and drying oven. It is preferable from the viewpoint of economy and environment. In order to obtain a good finished coating film, it is desirable to heat the uncured base coating film at 40 to 100 ° C. for 2 to 10 minutes before applying the clear coating.
本発明の塗膜形成方法において、上記ベース塗膜を形成した後に塗装されるクリヤー塗膜は、上記ベース塗膜に起因する凹凸、チカチカ等を平滑にし、保護するために形成される。塗装方法として具体的には、先に述べたμμベル、μベル等の回転霧化式の静電塗装機により塗膜を形成することが好ましい。 In the coating film forming method of the present invention, the clear coating film that is applied after forming the base coating film is formed to smooth and protect the unevenness, flickering, and the like caused by the base coating film. Specifically, as a coating method, it is preferable to form the coating film by a rotary atomizing electrostatic coating machine such as the μμ bell or μbell described above.
上記クリヤー塗料により形成されるクリヤー塗膜の乾燥膜厚は、一般に１０〜８０μｍ程度が好ましく、より好ましくは２０〜６０μｍ程度である。上限を越えると、塗装時にワキあるいはタレ等の作業性の不具合が起こることもあり、下限を下回ると、下地の凹凸が隠蔽できない。 The dry film thickness of the clear coating film formed from the clear coating is generally preferably about 10 to 80 μm, more preferably about 20 to 60 μm. If the upper limit is exceeded, workability problems such as peeling or sagging may occur during painting, and if the lower limit is not reached, the underlying irregularities cannot be concealed.
上述のようにして得られたクリヤー塗膜は、先に述べたように未硬化のベース塗膜とともに焼き付ける、いわゆる２コート１ベークによって塗膜形成を行うことが好ましい。焼き付け温度を８０〜１８０℃、好ましくは１２０〜１６０℃に設定することで高い架橋度の硬化塗膜が得られる。上限を越えると、塗膜が固く脆くなり、下限未満では硬化が充分でない。硬化時間は硬化温度により変化するが、１２０〜１６０℃で１０〜３０分が適当である。 The clear coating film obtained as described above is preferably formed by so-called two-coat one-bake, which is baked together with an uncured base coating film as described above. By setting the baking temperature to 80 to 180 ° C, preferably 120 to 160 ° C, a cured coating film having a high degree of crosslinking can be obtained. If the upper limit is exceeded, the coating film becomes hard and brittle, and if it is less than the lower limit, curing is not sufficient. The curing time varies depending on the curing temperature, but 10 to 30 minutes at 120 to 160 ° C. is appropriate.
本発明で形成される複層塗膜の膜厚は、多くの場合３０〜３００μｍであり、好ましくは５０〜２５０μｍである。上限を越えると、冷熱サイクル等の膜物性が低下し、下限を下回ると膜自体の強度が低下する。 In many cases, the film thickness of the multilayer coating film formed in the present invention is 30 to 300 μm, preferably 50 to 250 μm. When the upper limit is exceeded, film physical properties such as a cooling cycle decrease, and when the lower limit is exceeded, the strength of the film itself decreases.
以下、具体的な実施例を挙げて本発明を詳細に説明するが、本発明は以下の実施例により限定されるものではない。なお、以下「部」とあるのは「質量部」を意味する。 EXAMPLES Hereinafter, although a specific Example is given and this invention is demonstrated in detail, this invention is not limited by a following example. Hereinafter, “part” means “part by mass”.
製造例１ アクリル樹脂エマルション１の製造
反応容器に脱イオン水１２６．５部を加え、窒素気流中で混合撹拌しながら８０℃に昇温した。次いで、アクリル酸メチル２７．６１部、アクリル酸エチル５３．０４部、スチレン４．００部、メタクリル酸２−ヒドロキシエチル９．２８部、メタクリル酸３．０７部およびメタクリル酸アリル３．００部のモノマー混合物１００部、アクアロンＨＳ−１０（ポリオキシエチレンアルキルプロペニルフェニルエーテル硫酸エステル、第一工業製薬社製）０．７部、アデカリアソープＮＥ−２０（α−［１−［（アリルオキシ）メチル］−２−（ノニルフェノキシ）エチル］−ω−ヒドロキシオキシエチレン、旭電化社製）０．５部、および脱イオン水８０部からなるモノマー乳化物と、過硫酸アンモニウム０．３部、および脱イオン水１０部からなる開始剤溶液とを２時間にわたり並行して反応容器に滴下した。滴下終了後、２時間同温度で熟成を行った。次いで、４０℃まで冷却し、４００メッシュフィルターで濾過した後、脱イオン水７０部およびジメチルアミノエタノール０．３２部を加えｐＨ６．５に調整し、平均粒子径１５０ｎｍ、不揮発分２５％、固形分酸価２０ｍｇＫＯＨ／ｇ、水酸基価４０ｍｇＫＯＨ／ｇの単層のアクリル樹脂エマルションを得た。
Production Example 1 Production of acrylic resin emulsion 1 126.5 parts of deionized water was added to a reaction vessel, and the mixture was heated to 80 ° C. while being mixed and stirred in a nitrogen stream. Next, 27.61 parts of methyl acrylate, 53.04 parts of ethyl acrylate, 4.00 parts of styrene, 9.28 parts of 2-hydroxyethyl methacrylate, 3.07 parts of methacrylic acid and 3.00 parts of allyl methacrylate Monomer mixture 100 parts, Aqualon HS-10 (polyoxyethylene alkyl propenyl phenyl ether sulfate ester, Daiichi Kogyo Seiyaku Co., Ltd.) 0.7 parts, Adeka Soap NE-20 (α- [1-[(allyloxy) methyl]) 2- (nonylphenoxy) ethyl] -ω-hydroxyoxyethylene (manufactured by Asahi Denka Co., Ltd.), 0.5 part, and a monomer emulsion comprising 80 parts of deionized water, 0.3 part of ammonium persulfate, and deionized water An initiator solution consisting of 10 parts was dropped into the reaction vessel in parallel over 2 hours. After completion of the dropping, aging was performed at the same temperature for 2 hours. Next, after cooling to 40 ° C. and filtration through a 400 mesh filter, 70 parts of deionized water and 0.32 part of dimethylaminoethanol were added to adjust the pH to 6.5, the average particle size was 150 nm, the non-volatile content was 25%, the solid content was A single-layer acrylic resin emulsion having an acid value of 20 mgKOH / g and a hydroxyl value of 40 mgKOH / g was obtained.
製造例２ 水溶性アクリル樹脂の製造
反応容器にトリプロピレングリコールメチルエーテル２３．８９部およびプロピレングリコールメチルエーテル１６．１１部を加え、窒素気流中で混合撹拌しながら１０５℃に昇温した。次いで、メタクリル酸メチル１３．１部、アクリル酸エチル６８．４部、メタクリル酸２−ヒドロキシエチル１１．６部およびメタクリル酸６．９部を含むモノマー混合物を作成し、そのモノマー混合物１００部、トリプロピレングリコールメチルエーテル１０．０部およびターシャルブチルパーオキシ２−エチルヘキサノエート１部からなる開始剤溶液を３時間にわたり並行して反応容器に滴下した。滴下終了後、０．５時間同温度で熟成を行った。
Production Example 2 Production of water-soluble acrylic resin 23.89 parts of tripropylene glycol methyl ether and 16.11 parts of propylene glycol methyl ether were added to a reaction vessel, and the mixture was heated to 105 ° C. with mixing and stirring in a nitrogen stream. Next, a monomer mixture containing 13.1 parts of methyl methacrylate, 68.4 parts of ethyl acrylate, 11.6 parts of 2-hydroxyethyl methacrylate and 6.9 parts of methacrylic acid was prepared. An initiator solution consisting of 10.0 parts of propylene glycol methyl ether and 1 part of tertiary butyl peroxy 2-ethylhexanoate was dropped into the reaction vessel in parallel over 3 hours. After completion of the dropping, aging was performed at the same temperature for 0.5 hours.
さらに、トリプロピレングリコールメチルエーテル５．０部およびターシャルブチルパーオキシ２−エチルヘキサノエート０．３部からなる開始剤溶液を０．５時間にわたり反応容器に滴下した。滴下終了後、２時間同温度で熟成を行った。 Further, an initiator solution consisting of 5.0 parts of tripropylene glycol methyl ether and 0.3 part of tertiary butyl peroxy 2-ethylhexanoate was dropped into the reaction vessel over 0.5 hours. After completion of the dropping, aging was performed at the same temperature for 2 hours.
脱溶剤装置により、減圧下（７０ｔｏｒｒ）１１０℃で溶剤を１６．１部留去した後、脱イオン水２０４部およびジメチルアミノエタノール７．１部を加えて水溶性アクリル樹脂溶液を得た。得られた水溶性アクリル樹脂溶液の不揮発分は３０％であり、固形分酸価４０ｍｇＫＯＨ／ｇ、水酸基価５０ｍｇＫＯＨ／ｇ、粘度は１４０ポイズ（Ｅ型粘度計１ｒｐｍ／２５℃）であった。 After removing 16.1 parts of the solvent at 110 ° C. under reduced pressure (70 torr) using a solvent removal apparatus, 204 parts of deionized water and 7.1 parts of dimethylaminoethanol were added to obtain a water-soluble acrylic resin solution. The obtained water-soluble acrylic resin solution had a nonvolatile content of 30%, a solid content acid value of 40 mg KOH / g, a hydroxyl value of 50 mg KOH / g, and a viscosity of 140 poise (E-type viscometer 1 rpm / 25 ° C.).
製造例３ ポリエステル樹脂の製造
攪拌機、コンデンサー、温度計を具備した反応容器にジメチルテレフタル酸３７２部、ジメチルイソフタル酸３８０部、２−メチル−１，３−プロパンジオール５７６部、１，５−ペンタンジオール２２２部、テトラブチルチタネート０．４１部を仕込み、１６０℃から２３０℃まで昇温しつつ４時間かけてエステル交換反応を行った。次いで系内を徐々に減圧していき、２０分かけて５ｍｍＨｇまで減圧し、さらに０．３ｍｍＨｇ以下の真空下まで減圧して、２６０℃にて４０分間重縮合反応を行った。窒素雰囲気下、２２０℃まで冷却し、無水トリメリット酸を２３部投入し、２２０℃で３０分間反応を行ってポリエステル樹脂を得た。得られたポリエステル樹脂は、ＮＭＲの組成分析の結果、カルボン酸成分がモル比でテレフタル酸／イソフタル酸／トリメリット酸：４８／４９／３であり、ポリオール成分がモル比で２−メチル−１，３−プロパンジオール／１，５−ペンタンジオール：６５／３５であった。つまりポリカルボン酸成分、ポリオール成分のそれぞれの合計量を１００モル％としたとき、芳香族ジカルボン酸が９７モル％、イソフタル酸が４９モル％、所定のジオールの合計量が６５モル％、エチレングリコールは０モル％であった。
Production Example 3 Production of Polyester Resin In a reaction vessel equipped with a stirrer, condenser and thermometer, 372 parts of dimethyl terephthalic acid, 380 parts of dimethyl isophthalic acid, 576 parts of 2-methyl-1,3-propanediol, 1,5-pentanediol 222 parts and 0.41 part of tetrabutyl titanate were charged, and a transesterification reaction was carried out over 4 hours while heating from 160 ° C to 230 ° C. Next, the pressure inside the system was gradually reduced, the pressure was reduced to 5 mmHg over 20 minutes, and the pressure was further reduced to a vacuum of 0.3 mmHg or less, and a polycondensation reaction was performed at 260 ° C. for 40 minutes. The mixture was cooled to 220 ° C. in a nitrogen atmosphere, 23 parts of trimellitic anhydride was added, and a reaction was performed at 220 ° C. for 30 minutes to obtain a polyester resin. As a result of NMR compositional analysis, the obtained polyester resin had a carboxylic acid component in a molar ratio of terephthalic acid / isophthalic acid / trimellitic acid: 48/49/3, and a polyol component in a molar ratio of 2-methyl-1 , 3-propanediol / 1,5-pentanediol: 65/35. That is, when the total amount of each of the polycarboxylic acid component and the polyol component is 100 mol%, the aromatic dicarboxylic acid is 97 mol%, the isophthalic acid is 49 mol%, the total amount of the predetermined diol is 65 mol%, ethylene glycol Was 0 mol%.
得られた樹脂について、以下の通り、特性値を測定した。
（１）数平均分子量：ポリスチレン標準サンプル基準を用いたゲルパーミエーションクロマトグラフィ（ＧＰＣ）で測定したところ、１２０００であった。
（２）酸価：試料０．２ｇを精秤し２０ｍｌのクロロホルムに溶解した後、０．０１Ｎの水酸化カリウム（エタノール溶液）で滴定したところ、１６．１ｍｇＫＯＨ／ｇであった。
About the obtained resin, the characteristic value was measured as follows.
(1) Number average molecular weight: It was 12000 when measured by gel permeation chromatography (GPC) using polystyrene standard sample standards.
(2) Acid value: 0.2 g of a sample was precisely weighed and dissolved in 20 ml of chloroform, and then titrated with 0.01 N potassium hydroxide (ethanol solution) to find 16.1 mg KOH / g.
このポリエステル樹脂１００部に、ブチルセロソルブ４０部、トリエチルアミン２．７部を投入した後、８０℃で１時間攪拌を行って溶解させた。次いで、イオン交換水１９３部をゆるやかに添加し、不揮発分３０％のポリエステル樹脂を含んだポリエステルの水分散体１を得た。平均粒子径を測定するために、専用セルにイオン交換水だけを入れ、この分散体を１滴添加しかき混ぜ、樹脂固形分濃度０．１質量％に調整して動的光散乱式粒径測定装置ＬＢ−５００（堀場製作所社製）によって、２０℃で測定したところ、３５ｎｍであった。 To 100 parts of this polyester resin, 40 parts of butyl cellosolve and 2.7 parts of triethylamine were added, followed by stirring at 80 ° C. for 1 hour for dissolution. Next, 193 parts of ion-exchanged water was gently added to obtain a polyester aqueous dispersion 1 containing a polyester resin having a nonvolatile content of 30%. In order to measure the average particle size, only ion-exchanged water is put into a dedicated cell, and only 1 drop of this dispersion is mixed, and the resin solid content concentration is adjusted to 0.1% by mass to measure the dynamic light scattering particle size. It was 35 nm when measured at 20 degreeC with apparatus LB-500 (made by Horiba, Ltd.).
製造例４ リン酸基含有アクリル樹脂の合成
攪拌機、温度調整器、冷却管を備えた１リットルの反応容器にエトキシプロパノール４０部を仕込み、これにスチレン４部、ｎ−ブチルアクリレート３５．９６部、エチルヘキシルメタアクリレート１８．４５部、２−ヒドロキシエチルメタクリレート１３．９２部、メタクリル酸７．６７部、エトキシプロパノール２０部に、ホスマーＰＰ（ユニケミカル社製アシッドホスホオキシヘキサ（オキシプロピレン）モノメタクリレート）２０部を溶解した溶液４０部、及びアゾビスイソブチロニトリル１．７部からなるモノマー溶液１２１．７部を１２０℃で３時間滴下した後、１時間さらに攪拌を継続した。得られた樹脂は、酸価１０５ｍｇＫＯＨ／ｇ、うちリン酸基による酸価５５ｍｇＫＯＨ／ｇ、水酸基価６０ｍｇＫＯＨ／ｇ、数平均分子量６０００のアクリルワニスで、不揮発分が６３％であった。
Production Example 4 Synthesis of phosphoric acid group-containing acrylic resin 40 parts of ethoxypropanol was charged into a 1 liter reaction vessel equipped with a stirrer, a temperature controller, and a condenser, and 4 parts of styrene, 35.96 parts of n-butyl acrylate, Ethylhexyl methacrylate 18.45 parts, 2-hydroxyethyl methacrylate 13.92 parts, methacrylic acid 7.67 parts, ethoxypropanol 20 parts, Phosmer PP (Acid phosphooxyhexa (oxypropylene) monomethacrylate) 20 manufactured by Unichemical Co., Ltd. 40 parts of the dissolved solution and 121.7 parts of a monomer solution consisting of 1.7 parts of azobisisobutyronitrile were added dropwise at 120 ° C. for 3 hours, and stirring was further continued for 1 hour. The obtained resin was an acrylic acid varnish having an acid value of 105 mgKOH / g, of which an acid value of 55 mgKOH / g based on a phosphoric acid group, a hydroxyl value of 60 mgKOH / g and a number average molecular weight of 6000, and a nonvolatile content of 63%.
実施例１
＜水性メタリックベース塗料の製造＞
先の製造例１で得られたエマルション樹脂を１６０部（固形分２５％）、１０質量％ジメチルアミノエタノール１０部、製造例２の水溶性アクリル樹脂３３部（樹脂固形分３０％）、製造例３のポリエステル樹脂３３部（樹脂固形分３０％）、メラミン樹脂としてサイメル２０４（三井サイテック社製混合アルキル化型メラミン樹脂、固形分８０％、水トレランス３．６ｍｌ）を３８部、ＧＰ−１０００（三洋化成工業社から市販のグリセリンのプロピレンオキシド付加物で、化学式：
のｌ／ｍ／ｎ＝４〜６／４〜６／４〜６のもの；数平均分子量１０００；固形分１００％）１０部（塗料樹脂固形分中１０質量％）、光輝性顔料としてアルペーストＭＨ８８０１（旭化成社製アルミニウム顔料）２１部（固形分６５％、ＰＷＣ１２％）、リン酸基含有アクリル樹脂５部、ラウリルアシッドフォスフェート０．３部を添加し、さらに、２−エチルヘキサノール３０部、アデカノールＵＨ−８１４Ｎ３．３部（ＡＤＥＫＡ社製増粘剤、固形分３０％）を均一分散することにより水性メタリックベース塗料を得た。
Example 1
<Manufacture of water-based metallic base paint>
160 parts of emulsion resin obtained in previous Production Example 1 (solid content 25%), 10 parts by weight of dimethylaminoethanol 10 parts, 33 parts of water-soluble acrylic resin of Production Example 2 (resin solid content 30%), Production Example 3 parts of polyester resin 3 (resin solid content 30%), 38 parts of Cymel 204 (mixed alkylated melamine resin manufactured by Mitsui Cytec Co., Ltd., solid content 80%, water tolerance 3.6 ml) as a melamine resin, GP-1000 ( A propylene oxide adduct of glycerin commercially available from Sanyo Chemical Industries, chemical formula:
1 / m / n = 4 to 6/4 to 6/4 to 6; number average molecular weight 1000; solid content 100%) 10 parts (10% by mass in coating resin solid content), Alpaste as glitter pigment MH8801 (Asahi Kasei Corporation aluminum pigment) 21 parts (solid content 65%, PWC 12%), phosphoric acid group-containing acrylic resin 5 parts, lauryl acid phosphate 0.3 parts, and further, 2-ethylhexanol 30 parts, An aqueous metallic base coating was obtained by uniformly dispersing 3.3 parts of Adecanol UH-814N (a thickener manufactured by ADEKA, solid content 30%).
＜複合塗膜形成方法（ツーコート・ワンベーク）＞
リン酸亜鉛処理した厚み０．８ｍｍ、縦３０ｃｍ、横４０ｃｍのダル鋼板に、カチオン電着塗料「パワートップＵ−５０」（日本ペイント社製）を、乾燥膜厚が２０μｍとなるように電着塗装し、１６０℃で３０分間焼き付けた塗板に、２５秒（Ｎｏ．４フォードカップを使用し、２０℃で測定）に、予め希釈されたグレー中塗り塗料「オルガＯＰ−３０」（日本ペイント社製ポリエステル・メラミン系塗料）を、乾燥膜厚３５μｍとなるようにエアスプレーで２ステージ塗装し、１４０℃で３０分間、焼き付けた。
<Composite coating film formation method (two-coat / one-bake)>
Cathodic electrodeposition paint "Power Top U-50" (manufactured by Nippon Paint Co., Ltd.) is electrodeposited onto a dull steel sheet with a thickness of 0.8mm, length 30cm, width 40cm treated with zinc phosphate so that the dry film thickness is 20 µm. Painted and baked at 160 ° C. for 30 minutes, pre-diluted gray intermediate coating “Olga OP-30” (Nippon Paint Co., Ltd.) in 25 seconds (measured at 20 ° C. using a No. 4 Ford cup) Polyester / melamine-based paint) was applied in two stages by air spraying to a dry film thickness of 35 μm, and baked at 140 ° C. for 30 minutes.
冷却後、先の製造例の水性メタリックベース塗料を、脱イオン交換水を用いて６０００ｍＰａ・ｓ（Ｂ型粘度計を使用し、６ｒｐｍの条件にて、２０℃で測定）に希釈した。室温２３℃、湿度６８％の条件下で乾燥膜厚１５μｍになるように「カートリッジベル」で２ステージ塗装した。２回の塗布の間に、１分３０秒間のインターバルセッティングを行った。２回目の塗布後、１分３０秒間のインターバルをとって、セッティングを行った。その後、８０℃で５分間のプレヒートを行った。 After cooling, the aqueous metallic base paint of the previous production example was diluted to 6000 mPa · s (measured at 20 ° C. under the condition of 6 rpm using a B-type viscometer) using deionized water. Two-stage coating was performed with a “cartridge bell” so that the dry film thickness was 15 μm under conditions of room temperature of 23 ° C. and humidity of 68%. An interval setting of 1 minute 30 seconds was performed between the two coatings. After the second application, setting was performed with an interval of 1 minute and 30 seconds. Thereafter, preheating was performed at 80 ° C. for 5 minutes.
プレヒート後、塗装板を室温まで放冷し、クリヤー塗料としてマックフロー−Ｏ−１８１０（日本ペイント社製溶剤型クリヤー塗料）、乾燥膜厚３５μｍとなるように１ステージ塗装し、７分間セッティングした。ついで、塗装板を乾燥機で１４０℃で３０分間焼き付けを行うことにより、複合塗膜を得た。 After preheating, the coated plate was allowed to cool to room temperature, applied as a clear coating material, Macflow-O-1810 (solvent type clear coating material manufactured by Nippon Paint Co., Ltd.), coated in one stage to a dry film thickness of 35 μm, and set for 7 minutes. Next, the coated film was baked at 140 ° C. for 30 minutes with a dryer to obtain a composite coating film.
得られた塗膜について、ＦＦ性とムラを評価した。評価方法は以下の通りであった。結果を表１に示す。 About the obtained coating film, FF property and nonuniformity were evaluated. The evaluation method was as follows. The results are shown in Table 1.
＜ＦＦ性評価＞
ミノルタ株式会社から市販のミノルタＣＭ−５１２ｍ３を用いて、塗膜に垂直にある受光部を０°とした場合に、２５°、４５°、７５°となる角度から光源を照射して測定されるＬ＊値を測定し、その測定値からフリップフロップ値を算出した。
ＦＦ値（フリップフロップ値）＝２５°Ｌ＊値／７５°Ｌ＊値の比で表す。ＦＦ性は２．１５以上（２５度のＬ＊値が９８以上）が合格である。
<FF property evaluation>
Using a Minolta CM-512m3 commercially available from Minolta Co., Ltd., measurement is performed by irradiating a light source from angles of 25 °, 45 °, and 75 ° when the light receiving portion perpendicular to the coating film is 0 °. The L * value was measured, and the flip-flop value was calculated from the measured value.
FF value (flip-flop value) = expressed as a ratio of 25 ° L * value / 75 ° L * value. The FF property is 2.15 or more (L * value of 25 degrees is 98 or more).
＜ムラランク＞
Ａ３サイズのパネルに塗装したメタリック塗膜の色ムラを目視評価し、その発生程度をランク付けした。
ランク５：メタリックムラが見えない。
ランク４：ランク３とランク５の中間程度のムラが見える。
ランク３：メタリックムラが若干見える。
ランク２：ランク１とランク３の中間程度のムラが見える。
ランク１：メタリックムラが目立つ。
<Murarank>
The color unevenness of the metallic coating film applied to the A3 size panel was visually evaluated, and the degree of occurrence was ranked.
Rank 5: Metallic unevenness is not visible.
Rank 4: Unevenness between rank 3 and rank 5 is visible.
Rank 3: Some metallic unevenness is visible.
Rank 2: Unevenness in the middle between Rank 1 and Rank 3 is visible.
Rank 1: Metallic unevenness is conspicuous.
実施例２
実施例１の水性メタリックベース塗料の製造時に、ＧＰ１０００ １０部の代わりに、ＧＰ４００（三洋化成工業社から市販のグリセリンのプロピレンオキシド付加物で、化学式：
のｌ／ｍ／ｎ＝１〜２／１〜２／１〜２のもの；数平均分子量４００；固形分１００％）を１０部（塗料樹脂固形分中１０質量％）配合した水性メタリックベース塗料を製造した。それらの塗料を用いて、ツーコート・ワンベーク塗装を実施例１と同様に行って、積層塗膜を得た。得られた積層塗膜について、FF性とムラを実施例１と同様に測定し、結果を表１に示す。
Example 2
When producing the aqueous metallic base paint of Example 1, instead of 10 parts of GP1000, GP400 (a propylene oxide adduct of glycerin commercially available from Sanyo Chemical Industries, chemical formula:
1 / m / n = 1 to 2/1 to 2/1 to 2; number-average molecular weight 400; solid content 100%) in 10 parts (10% by mass in the solid content of the coating resin). Manufactured. Using these paints, two-coat / one-bake coating was performed in the same manner as in Example 1 to obtain a laminated coating film. About the obtained laminated coating film, FF property and nonuniformity were measured like Example 1, and a result is shown in Table 1.
比較例１
実施例１の水性メタリックベース塗料の製造時に、ＧＰ１０００ １０部の代わりに、ＧＰ３０００（三洋化成工業社から市販のグリセリンのプロピレンオキシド付加物で、化学式：
のｌ／ｍ／ｎ＝１２〜２０／１２〜２０／１２〜２０のもの；数平均分子量３０００；固形分１００％）を１０部（塗料樹脂固形分中１０質量％）配合した水性メタリックベース塗料を製造した。それらの塗料を用いて、ツーコート・ワンベーク塗装を実施例１と同様に行って、積層塗膜を得た。得られた積層塗膜について、FF性とムラを実施例１と同様に測定し、結果を表１に示す。
Comparative Example 1
In the production of the water-based metallic base paint of Example 1, instead of 10 parts of GP1000, GP3000 (a propylene oxide adduct of glycerin commercially available from Sanyo Chemical Industries, chemical formula:
1 / m / n = 12-20 / 12-20 / 12-20; number-average molecular weight 3000; solid content 100%) in an amount of 10 parts (10% by mass in the coating resin solid content) Manufactured. Using these paints, two-coat / one-bake coating was performed in the same manner as in Example 1 to obtain a laminated coating film. About the obtained laminated coating film, FF property and nonuniformity were measured like Example 1, and a result is shown in Table 1.
比較例２
実施例１の水性メタリックベース塗料の製造時に、ＧＰ１０００を１０部ではなく３０部（塗料樹脂固形分中３０質量％）配合した水性メタリックベース塗料を製造した。それらの塗料を用いて、ツーコート・ワンベーク塗装を実施例１と同様に行って、積層塗膜を得た。得られた積層塗膜について、FF性とムラを実施例１と同様に測定し、結果を表１に示す。
Comparative Example 2
During the production of the aqueous metallic base paint of Example 1, an aqueous metallic base paint containing 30 parts of GP1000 (30% by mass in the solid content of the paint resin) instead of 10 parts was produced. Using these paints, two-coat / one-bake coating was performed in the same manner as in Example 1 to obtain a laminated coating film. About the obtained laminated coating film, FF property and nonuniformity were measured like Example 1, and a result is shown in Table 1.
比較例３
実施例１の水性メタリックベース塗料の製造時に、ＧＰ１０００ １０部の代わりに、ＰＸ１０００（三洋化成工業株式会社から市販の２官能ポリエーテルポリオール、数平均分子量４００，水酸基価２７８ｍｇＫＯＨ／ｇ、一級／二級水酸基価比＝１００／０；固形分１００％）を１０部（塗料樹脂固形分中１０質量％）配合した水性メタリックベース塗料を製造した。それらの塗料を用いて、ツーコート・ワンベーク塗装を実施例１と同様に行って、積層塗膜を得た。得られた積層塗膜について、FF性とムラを実施例１と同様に測定し、結果を表１に示す。
Comparative Example 3
PX1000 (bifunctional polyether polyol commercially available from Sanyo Chemical Industries Ltd., number average molecular weight 400, hydroxyl value 278 mgKOH / g, primary / secondary) instead of 10 parts of GP1000 during the production of the aqueous metallic base paint of Example 1 A water-based metallic base paint containing 10 parts (10% by mass in the solid content of the coating resin) of hydroxyl value ratio = 100/0; solid content of 100% was produced. Using these paints, two-coat / one-bake coating was performed in the same manner as in Example 1 to obtain a laminated coating film. About the obtained laminated coating film, FF property and nonuniformity were measured like Example 1, and a result is shown in Table 1.
比較例４
実施例１の水性メタリックベース塗料の製造時に、製造例２で得られた水溶性アクリル樹脂（本発明の成分（ｂ））を用いない以外は実施例１と同様に水性メタリックベース塗料を製造した。それらの塗料を用いて、ツーコート・ワンベーク塗装を実施例１と同様に行って、積層塗膜を得た。得られた積層塗膜について、FF性とムラを実施例１と同様に測定し、結果を表１に示す。
Comparative Example 4
A water-based metallic base paint was produced in the same manner as in Example 1 except that the water-soluble acrylic resin obtained in Production Example 2 (component (b) of the present invention) was not used during the production of the water-based metallic base paint of Example 1. . Using these paints, two-coat / one-bake coating was performed in the same manner as in Example 1 to obtain a laminated coating film. About the obtained laminated coating film, FF property and nonuniformity were measured like Example 1, and a result is shown in Table 1.
上記結果から明らかなように、本発明の範囲内のポリエーテルポリオールを使用すると、ＦＦ性も高く、ムラも極めてよいランクを示す。比較例１は、ポリエーテルポリオールのｌ、ｍおよびｎ値が本願発明の範囲外のものを用いた例であり、ＦＦ性は優れているが、ムラのランクが悪くなることが解る。比較例２は、本発明の範囲内のポリエーテルポリオールを用いているのだが、その使用量が多い場合であり、その場合ムラは優れたランクを示すものの、ＦＦ性が悪くなる。比較例３では、本発明のポリエーテルポリオールとは化学構造的に違うポリエーテルポリオール（特許文献４（特開２００３−２９２８７７号公報）で使用のポリエーテルポリオール）を用いた例であり、ＦＦ性は高いがムラが非常に悪い値を示している。比較例５は、本発明の要件である水溶性アクリル樹脂を含まない例であり、ＦＦ性は良好であるが、ムラが極めて悪い。 As is apparent from the above results, when a polyether polyol within the scope of the present invention is used, the FF property is high and the unevenness is extremely good. Comparative Example 1 is an example using a polyether polyol having l, m and n values outside the range of the present invention, and it is understood that the FF property is excellent but the unevenness rank is deteriorated. In Comparative Example 2, the polyether polyol within the scope of the present invention is used, and this is a case where the amount used is large. In this case, the unevenness shows an excellent rank, but the FF property deteriorates. Comparative Example 3 is an example using polyether polyol (polyether polyol used in Patent Document 4 (Japanese Patent Laid-Open No. 2003-292877)) having a chemical structure different from that of the polyether polyol of the present invention. Is very high but unevenness is very bad. Comparative Example 5 is an example that does not include the water-soluble acrylic resin that is a requirement of the present invention. The FF property is good, but the unevenness is extremely bad.
本発明の複層塗膜形成方法は、自動車車体等の高外観塗膜を形成する際に利用することができる。 The multilayer coating film forming method of the present invention can be used when forming a high-appearance coating film such as an automobile body.
Claims (8)
前記水性ベース塗料が、樹脂固形分１００質量％中、
（ａ）アクリル樹脂エマルションが固形分で１０〜６０質量％、
（ｂ）水溶性アクリル樹脂が固形分で５〜４０質量％、および
（ｃ）メラミン樹脂が固形分で２０〜４０質量％、
（ｄ）下記化学式で表される数平均分子量４００〜２，０００のポリエーテルポリオール２〜２５質量％
含有することを特徴とする複層塗膜の形成方法。 The base coating film is formed by coating a water-based base paint on the intermediate coating film formed on the steel sheet for automobiles to form a base coating film, and then applying an organic solvent type clear coating composition to form the clear coating film. And a clear coating film is heated and cured to form a multilayer coating film,
The water-based paint is in a resin solid content of 100% by mass,
(A) Acrylic resin emulsion is 10-60 mass% in solid content,
(B) Water-soluble acrylic resin is 5 to 40% by mass in solid content, and (c) Melamine resin is 20 to 40% by mass in solid content,
(D) 2 to 25% by mass of a polyether polyol having a number average molecular weight of 400 to 2,000 represented by the following chemical formula
A method for forming a multilayer coating film, comprising:
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