JP6404965B2 - Powder coating composition and hue maintaining method - Google Patents
Powder coating composition and hue maintaining method Download PDFInfo
- Publication number
- JP6404965B2 JP6404965B2 JP2017025158A JP2017025158A JP6404965B2 JP 6404965 B2 JP6404965 B2 JP 6404965B2 JP 2017025158 A JP2017025158 A JP 2017025158A JP 2017025158 A JP2017025158 A JP 2017025158A JP 6404965 B2 JP6404965 B2 JP 6404965B2
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- JP
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- Prior art keywords
- powder coating
- coating composition
- resin
- hue
- yellow
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000843 powder Substances 0.000 title claims description 135
- 239000008199 coating composition Substances 0.000 title claims description 99
- 238000000034 method Methods 0.000 title claims description 16
- 229920005989 resin Polymers 0.000 claims description 65
- 239000011347 resin Substances 0.000 claims description 65
- 239000012860 organic pigment Substances 0.000 claims description 43
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 35
- 239000003963 antioxidant agent Substances 0.000 claims description 34
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 34
- 230000003078 antioxidant effect Effects 0.000 claims description 28
- 239000003822 epoxy resin Substances 0.000 claims description 22
- 229920000647 polyepoxide Polymers 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 20
- 239000000049 pigment Substances 0.000 claims description 19
- 229920001225 polyester resin Polymers 0.000 claims description 12
- 239000004645 polyester resin Substances 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 229920001187 thermosetting polymer Polymers 0.000 claims description 6
- 239000002530 phenolic antioxidant Substances 0.000 claims description 5
- 238000012423 maintenance Methods 0.000 claims description 3
- 150000008641 benzimidazolones Chemical group 0.000 claims 2
- 238000000576 coating method Methods 0.000 description 78
- 239000011248 coating agent Substances 0.000 description 74
- 235000006708 antioxidants Nutrition 0.000 description 31
- -1 aromatic carboxylic acids Chemical class 0.000 description 31
- 239000003795 chemical substances by application Substances 0.000 description 31
- 238000001723 curing Methods 0.000 description 31
- 239000000203 mixture Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 15
- 239000003973 paint Substances 0.000 description 15
- 239000004593 Epoxy Substances 0.000 description 14
- 239000002245 particle Substances 0.000 description 13
- 238000004383 yellowing Methods 0.000 description 13
- 239000004925 Acrylic resin Substances 0.000 description 12
- 229920000178 Acrylic resin Polymers 0.000 description 12
- 229920000728 polyester Polymers 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- MYONAGGJKCJOBT-UHFFFAOYSA-N benzimidazol-2-one Chemical compound C1=CC=CC2=NC(=O)N=C21 MYONAGGJKCJOBT-UHFFFAOYSA-N 0.000 description 7
- 239000010445 mica Substances 0.000 description 7
- 229910052618 mica group Inorganic materials 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- 239000007983 Tris buffer Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- WZSFTHVIIGGDOI-UHFFFAOYSA-N 4,5,6,7-tetrachloro-3-[2-methyl-3-[(4,5,6,7-tetrachloro-3-oxoisoindol-1-yl)amino]anilino]isoindol-1-one Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C2=C1C(NC1=CC=CC(NC=3C4=C(C(=C(Cl)C(Cl)=C4Cl)Cl)C(=O)N=3)=C1C)=NC2=O WZSFTHVIIGGDOI-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000005562 fading Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000004606 Fillers/Extenders Substances 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 3
- 150000004056 anthraquinones Chemical class 0.000 description 3
- 150000004982 aromatic amines Chemical class 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 2
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 2
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 2
- PFEFOYRSMXVNEL-UHFFFAOYSA-N 2,4,6-tritert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 PFEFOYRSMXVNEL-UHFFFAOYSA-N 0.000 description 2
- HNURKXXMYARGAY-UHFFFAOYSA-N 2,6-Di-tert-butyl-4-hydroxymethylphenol Chemical compound CC(C)(C)C1=CC(CO)=CC(C(C)(C)C)=C1O HNURKXXMYARGAY-UHFFFAOYSA-N 0.000 description 2
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 2
- MRBKEAMVRSLQPH-UHFFFAOYSA-N 3-tert-butyl-4-hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1 MRBKEAMVRSLQPH-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- OBJNZHVOCNPSCS-UHFFFAOYSA-N naphtho[2,3-f]quinazoline Chemical compound C1=NC=C2C3=CC4=CC=CC=C4C=C3C=CC2=N1 OBJNZHVOCNPSCS-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229940117969 neopentyl glycol Drugs 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000004033 plastic Substances 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000005028 tinplate Substances 0.000 description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- RGASRBUYZODJTG-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C RGASRBUYZODJTG-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- FGYJSJUSODGXAR-UHFFFAOYSA-N 1,3,7,9-tetratert-butyl-11-octoxy-5h-benzo[d][1,3,2]benzodioxaphosphocine Chemical compound C1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP(OCCCCCCCC)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C FGYJSJUSODGXAR-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 1
- DXCHWXWXYPEZKM-UHFFFAOYSA-N 2,4-ditert-butyl-6-[1-(3,5-ditert-butyl-2-hydroxyphenyl)ethyl]phenol Chemical compound C=1C(C(C)(C)C)=CC(C(C)(C)C)=C(O)C=1C(C)C1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1O DXCHWXWXYPEZKM-UHFFFAOYSA-N 0.000 description 1
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- GJDRKHHGPHLVNI-UHFFFAOYSA-N 2,6-ditert-butyl-4-(diethoxyphosphorylmethyl)phenol Chemical compound CCOP(=O)(OCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 GJDRKHHGPHLVNI-UHFFFAOYSA-N 0.000 description 1
- UDFARPRXWMDFQU-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(3,5-ditert-butyl-4-hydroxyphenyl)methylsulfanylmethyl]phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CSCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 UDFARPRXWMDFQU-UHFFFAOYSA-N 0.000 description 1
- FLSKKFALEYBSJE-UHFFFAOYSA-N 2,6-ditert-butyl-4-[1-(3,5-ditert-butyl-4-hydroxyphenyl)butyl]phenol Chemical compound C=1C(C(C)(C)C)=C(O)C(C(C)(C)C)=CC=1C(CCC)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 FLSKKFALEYBSJE-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Description
本発明は、粉体塗料組成物および色相維持方法に関する。より詳細には、本発明は、高温に曝される場合であっても白色系の色相を維持することのできる粉体塗料組成物および色相維持方法に関する。 The present invention relates to a powder coating composition and a hue maintaining method. More specifically, the present invention relates to a powder coating composition and a hue maintaining method capable of maintaining a white hue even when exposed to high temperatures.
従来、溶剤を含まず、回収や再利用が容易な塗料組成物として、粉体塗料組成物が知られている。熱により硬化する粉体塗料組成物は、基材に付与された後、たとえば１６０℃以上の焼付け乾燥炉によって硬化される。この場合、硬化された粉体樹脂組成物は、熱やガスによって樹脂成分が黄変し、色相が変化する。そこで、酸化防止剤を配合することにより、樹脂成分の黄変を抑制する技術が提案されている（たとえば特許文献１〜４）。 Conventionally, a powder coating composition is known as a coating composition that does not contain a solvent and can be easily recovered and reused. The powder coating composition that is cured by heat is applied to the substrate, and then cured by, for example, a baking drying oven at 160 ° C. or higher. In this case, in the cured powder resin composition, the resin component is yellowed by heat or gas, and the hue changes. Then, the technique which suppresses yellowing of a resin component by mix | blending antioxidant is proposed (for example, patent documents 1-4).
近年、環境配慮の観点から無溶剤である粉体塗料の利用が進んでいる。しかし、粉体塗料は、１００℃付近で混練するという製造上の理由から、硬化温度が一般の熱硬化型溶剤系塗料と比較して、１４０〜１８０℃と高く設定されている。さらに、実際の塗装時には、生産効率の観点から、より短い時間で硬化させるため、粉体塗料は、より高温である１８０〜２２０℃で加熱される。そのため、熱やガスにより、樹脂の黄変がより生じやすい傾向がある。さらに、白色系では、その黄変が顕著に表れやすい。そのため、一般的には、酸化防止剤などを添加することにより、黄変の抑制が試みられている。しかしながら、特許文献１〜４に記載の技術では、たとえば２００℃以上の高温で熱硬化を行う場合には、樹脂成分の黄変や、ＮＯｘ、ＳＯｘにより生じる黄変を充分に抑制することができない。また、これらの組成物は、２００℃以上の高温では酸化防止剤自体が変色する場合がある。 In recent years, the use of solvent-free powder coatings has been promoted from the viewpoint of environmental considerations. However, the powder coating is set to a high curing temperature of 140 to 180 ° C. compared to a general thermosetting solvent-based coating because of the manufacturing reason of kneading around 100 ° C. Furthermore, at the time of actual coating, in order to cure in a shorter time from the viewpoint of production efficiency, the powder coating is heated at a higher temperature of 180 to 220 ° C. Therefore, the yellowing of the resin tends to occur more easily due to heat and gas. Further, in the white system, the yellowing tends to appear remarkably. Therefore, in general, attempts have been made to suppress yellowing by adding an antioxidant or the like. However, in the techniques described in Patent Documents 1 to 4, for example, when thermosetting is performed at a high temperature of 200 ° C. or higher, yellowing of resin components and yellowing caused by NOx and SOx cannot be sufficiently suppressed. . In these compositions, the antioxidant itself may change color at a high temperature of 200 ° C. or higher.
本発明は、これら従来の課題に鑑みてなされたものであり、高温に曝される場合であっても、白色系の色相を維持することのできる粉体塗料組成物、および、粉体塗料組成物を高温で硬化させる際に、粉体塗料組成物の白色系の色相を維持するための色相維持方法を提供することを目的とする。 The present invention has been made in view of these conventional problems, and a powder coating composition capable of maintaining a white hue even when exposed to high temperatures, and a powder coating composition It is an object of the present invention to provide a hue maintaining method for maintaining a white hue of a powder coating composition when a product is cured at a high temperature.
本発明者は、鋭意研究した結果、樹脂成分に対して特定比率となるように酸化チタンを配合し、かつ、黄色の有機顔料を色相配合用の顔料として配合することにより、粉体塗料組成物が高温に曝される場合であっても、黄色の有機顔料が適宜退色し、これにより、白色系の色相が維持されることを見出し、本発明を完成させた。すなわち、上記課題を解決する本発明の粉体塗料組成物および粉体塗料組成物の色相維持方法には、以下の構成が主に含まれる。 As a result of diligent research, the present inventor has blended titanium oxide so as to have a specific ratio with respect to the resin component, and blended a yellow organic pigment as a pigment for blending a hue. The present invention has been completed by finding that the yellow organic pigment is appropriately discolored even when exposed to a high temperature, thereby maintaining a white hue. That is, the powder coating composition of the present invention and the hue maintaining method of the powder coating composition of the present invention for solving the above-described problems mainly include the following configurations.
（１）樹脂成分と、酸化チタンと、黄色有機顔料とを含み、前記樹脂成分と前記酸化チタンとの配合比率（質量比）は、１００：５０〜１００：１２０である、粉体塗料組成物。 (1) A powder coating composition containing a resin component, titanium oxide, and a yellow organic pigment, wherein a blending ratio (mass ratio) of the resin component and the titanium oxide is 100: 50 to 100: 120 .
このような構成によれば、樹脂成分に対して所定の配合比率となるよう酸化チタンが配合されている。これにより、粉体塗料組成物は、白色系の色相となる。さらに、粉体塗料組成物は、黄色有機顔料が配合されている。黄色有機顔料は、硬化時に高温に曝されることにより、適宜退色する。一方、粉体塗料組成物に含まれる樹脂成分等は、高温に曝されることにより、適宜黄変し得る。その結果、本発明の粉体塗料組成物は、高温に曝される場合において、樹脂成分等の黄変と、黄色有機顔料の退色とが同時に起こり、白色系の色相が維持される。 According to such a structure, the titanium oxide is mix | blended so that it may become a predetermined compounding ratio with respect to the resin component. As a result, the powder coating composition has a white hue. Furthermore, the powder coating composition contains a yellow organic pigment. Yellow organic pigments fade appropriately when exposed to high temperatures during curing. On the other hand, the resin component contained in the powder coating composition can be appropriately yellowed by being exposed to high temperature. As a result, when the powder coating composition of the present invention is exposed to a high temperature, yellowing of the resin component and the fading of the yellow organic pigment occur simultaneously, and a white hue is maintained.
（２）フェノール系酸化防止剤、リン系酸化防止剤およびイオウ系酸化防止剤からなる群から選択される少なくとも１つの酸化防止剤をさらに含む、（１）記載の粉体塗料組成物。 (2) The powder coating composition according to (1), further comprising at least one antioxidant selected from the group consisting of phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.
このような構成によれば、粉体塗料組成物は、高温で熱硬化される場合であっても、白色系の色相がより維持されやすい。 According to such a configuration, even when the powder coating composition is thermally cured at a high temperature, the white hue is more easily maintained.
（３）粉体塗料組成物を熱硬化させる際の色相維持方法であり、樹脂成分と酸化チタンとを配合比率（質量比）が１００：５０〜１００：１２０となるよう含む粉体塗料組成物に、黄色有機顔料をさらに配合する、色相維持方法。 (3) A method of maintaining a hue when thermosetting a powder coating composition, and a powder coating composition containing a resin component and titanium oxide so that the blending ratio (mass ratio) is 100: 50 to 100: 120 A method of maintaining a hue, further comprising adding a yellow organic pigment.
このような構成によれば、粉体塗料組成物は、樹脂成分に対して所定の配合比率となるよう酸化チタンが配合されており、白色系の色相を有している。さらに、粉体塗料組成物は、黄色有機顔料が配合される。黄色有機顔料は、硬化時に高温に曝されることにより、適宜退色する。一方、粉体塗料組成物に含まれる樹脂成分等は、高温に曝されることにより、適宜黄変し得る。その結果、本発明の粉体塗料組成物は、高温に曝される場合において、樹脂成分等の黄変と、黄色有機顔料の退色とが同時に起こり、白色系の色相が維持される。 According to such a configuration, the powder coating composition is blended with titanium oxide so as to have a predetermined blending ratio with respect to the resin component, and has a white hue. Furthermore, a yellow organic pigment is mix | blended with a powder coating composition. Yellow organic pigments fade appropriately when exposed to high temperatures during curing. On the other hand, the resin component contained in the powder coating composition can be appropriately yellowed by being exposed to high temperature. As a result, when the powder coating composition of the present invention is exposed to a high temperature, yellowing of the resin component and the fading of the yellow organic pigment occur simultaneously, and a white hue is maintained.
本発明によれば、高温に曝される場合であっても、白色系の色相を維持することのできる粉体塗料組成物、および、粉体塗料組成物を高温で硬化させる際に、粉体塗料組成物の白色系の色相を維持するための色相維持方法を提供することができる。 According to the present invention, a powder coating composition capable of maintaining a white hue even when exposed to a high temperature, and a powder when the powder coating composition is cured at a high temperature. It is possible to provide a hue maintaining method for maintaining the white hue of the coating composition.
＜粉体塗料組成物＞
本発明の一実施形態の粉体塗料組成物は、樹脂成分と、酸化チタンと、黄色有機顔料とを含む。樹脂成分と酸化チタンとの配合比率（質量比）は、１００：５０〜１００：１２０である。以下、それぞれについて説明する。
<Powder coating composition>
The powder coating composition of one embodiment of the present invention includes a resin component, titanium oxide, and a yellow organic pigment. The compounding ratio (mass ratio) of the resin component and titanium oxide is 100: 50 to 100: 120. Each will be described below.
（樹脂成分）
樹脂成分（結着樹脂）は、従来、粉体塗料組成物に汎用されている熱硬化性樹脂であればよく、特に限定されない。一例を挙げると、樹脂成分は、エポキシ樹脂、ポリエステル樹脂、アクリル樹脂、フッ素樹脂等である。樹脂成分は、併用されてもよい。
(Resin component)
The resin component (binder resin) is not particularly limited as long as it is a thermosetting resin conventionally used for powder coating compositions. For example, the resin component is an epoxy resin, a polyester resin, an acrylic resin, a fluororesin, or the like. The resin component may be used in combination.
エポキシ樹脂は特に限定されない。一例を挙げると、エポキシ樹脂は、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェノールノボラック型またはクレゾールノボラック型エポキシ樹脂、脂環式エポキシ樹脂、水添ビスフェノールＡ型もしくはＡＤ型エポキシ樹脂、プロピレングリコールジグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル等の脂肪族系エポキシ樹脂、脂肪族もしくは芳香族カルボン酸とエピクロルヒドリンとから得られるエポキシ樹脂、脂肪族もしくは芳香族アミンとエピクロルヒドリンとから得られるエポキシ樹脂、複素環エポキシ樹脂、スピロ環含有エポキシ樹脂、エポキシ変性樹脂等である。すなわち、エポキシ系粉体塗料は、当業者間において、エポキシ系粉体塗料として用いられるものであれば特に限定されない。一例を挙げると、エポキシ系粉体塗料は、一分子中に２つ以上のエポキシ基を有する数平均分子量７００〜２８００、エポキシ当量１００〜２５００かつ軟化点が５０〜１５０℃の常温において固体状のエポキシ樹脂が結着樹脂として好適に使用され得る。この際、硬化剤は、特に限定されない。硬化剤は後述のものが用いられ得る。 The epoxy resin is not particularly limited. For example, epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type or cresol novolac type epoxy resin, alicyclic epoxy resin, hydrogenated bisphenol A type or AD type epoxy resin, propylene glycol Aliphatic epoxy resins such as diglycidyl ether and pentaerythritol polyglycidyl ether, epoxy resins obtained from aliphatic or aromatic carboxylic acids and epichlorohydrin, epoxy resins obtained from aliphatic or aromatic amines and epichlorohydrin, heterocyclic rings Examples thereof include epoxy resins, spiro ring-containing epoxy resins, and epoxy-modified resins. That is, the epoxy-based powder coating is not particularly limited as long as it is used as an epoxy-based powder coating by those skilled in the art. For example, the epoxy powder coating is a solid at room temperature having a number average molecular weight of 700 to 2800 having two or more epoxy groups in one molecule, an epoxy equivalent of 100 to 2500, and a softening point of 50 to 150 ° C. Epoxy resins can be suitably used as the binder resin. At this time, the curing agent is not particularly limited. As the curing agent, those described below can be used.
エポキシ樹脂の軟化点は特に限定されない。一例を挙げると、エポキシ樹脂の軟化点は、５０℃以上であることが好ましく、６０℃以上であることがより好ましい。また、エポキシ樹脂の軟化点は、１６０℃以下であることが好ましく、１５０℃以下であることがより好ましい。エポキシ樹脂の軟化点が上記範囲内であることにより、得られる粉体塗料組成物は、良好な被膜外観および被膜性能が得られる。 The softening point of the epoxy resin is not particularly limited. For example, the softening point of the epoxy resin is preferably 50 ° C. or higher, and more preferably 60 ° C. or higher. Moreover, it is preferable that the softening point of an epoxy resin is 160 degrees C or less, and it is more preferable that it is 150 degrees C or less. When the softening point of the epoxy resin is within the above range, the obtained powder coating composition can have good coating appearance and coating performance.
エポキシ樹脂のエポキシ当量は特に限定されない。一例を挙げると、エポキシ当量は、１００ｇ／当量以上であることが好ましく、１５０ｇ／当量以上であることがより好ましく、１８０ｇ／当量以上であることがさらに好ましい。また、エポキシ当量は、２５００ｇ／当量以下であることが好ましく、２２００ｇ／当量以下であることがより好ましく、２０００ｇ／当量以下であることがさらに好ましい。エポキシ当量が上記範囲内であることにより、粉体塗料組成物は、所定の膜厚の塗膜を形成しやすい。なお、本実施形態において、エポキシ当量は、たとえば、１グラム当量のエポキシ基を含む樹脂のグラム数（ｇ／ｅｑ）として算出され得る。 The epoxy equivalent of the epoxy resin is not particularly limited. As an example, the epoxy equivalent is preferably 100 g / equivalent or more, more preferably 150 g / equivalent or more, and further preferably 180 g / equivalent or more. The epoxy equivalent is preferably 2500 g / equivalent or less, more preferably 2200 g / equivalent or less, and still more preferably 2000 g / equivalent or less. When the epoxy equivalent is within the above range, the powder coating composition can easily form a coating film having a predetermined film thickness. In the present embodiment, the epoxy equivalent can be calculated as, for example, the number of grams (g / eq) of a resin containing 1 gram equivalent of an epoxy group.
ポリエステル樹脂は特に限定されない。一例を挙げると、ポリエステル樹脂は、エチレングリコール、プロパンジオール、ヘキサンジオール、ネオペンチルグリコール、トリメチロールプロパン、ペンタエリスリトール等の多価アルコールと、マレイン酸、テレフタル酸、イソフタル酸、フタル酸、コハク酸、グルタル酸、アジピン酸、セバチン酸、β−オキシプロピオン酸等のカルボン酸とを常法に従って重合させて得たものである。すなわち、ポリエステル系粉体塗料は、当業者間において、ポリエステル系粉体塗料として用いられるものであれば、特に限定されない。ポリエステル系粉体塗料は、一分子中に２つ以上の水酸基を有し、軟化点が６０〜１５０℃でかつ、数平均分子量が１０００〜２００００の範囲にあるポリエステル樹脂が結着樹脂として好適に使用され得る。この際、硬化剤は、特に限定されない。硬化剤は後述のものが用いられ得る。また、このポリエステル系粉体塗料には一分子中に少なくとも２つ以上のカルボキシル基を有するポリエステル樹脂を１，３，５−トリグリシジルイソシアヌレート（ＴＧＩＣ）により硬化させる塗料や、グリシジル基含有アクリル樹脂により硬化させる塗料も含まれる。エポキシ−ポリエステルハイブリッド系粉体塗料についても上記ポリエステル系粉体塗料と同様に、当業者間においてポリエステル−エポキシ系粉体塗料と称して用いられている粉体塗料であれば、特に限定されない。一例を挙げると、エポキシ−ポリエステルハイブリッド系粉体塗料は、一分子中に少なくとも２つ以上のカルボキシル基を有するポリエステル樹脂と一分子中に２つ以上のエポキシ基を有するエポキシ樹脂を配合、硬化させるものが好適に使用される。この場合、ポリエステル樹脂が樹脂中に３０重量％以上含まれたものが一般的に用いられる。 The polyester resin is not particularly limited. For example, polyester resins include ethylene glycol, propanediol, hexanediol, neopentylglycol, trimethylolpropane, pentaerythritol and other polyhydric alcohols, maleic acid, terephthalic acid, isophthalic acid, phthalic acid, succinic acid, It is obtained by polymerizing with carboxylic acids such as glutaric acid, adipic acid, sebacic acid and β-oxypropionic acid according to a conventional method. That is, the polyester powder coating is not particularly limited as long as it is used as a polyester powder coating by those skilled in the art. As the polyester-based powder coating material, a polyester resin having two or more hydroxyl groups in one molecule, a softening point of 60 to 150 ° C., and a number average molecular weight of 1,000 to 20,000 is suitably used as a binder resin. Can be used. At this time, the curing agent is not particularly limited. As the curing agent, those described below can be used. In addition, this polyester-based powder coating includes a coating for curing a polyester resin having at least two or more carboxyl groups in one molecule with 1,3,5-triglycidyl isocyanurate (TGIC), or a glycidyl group-containing acrylic resin. Also included are paints that are cured by. The epoxy-polyester hybrid powder coating is not particularly limited as long as it is a powder coating used by those skilled in the art as a polyester-epoxy powder coating in the same manner as the polyester powder coating. As an example, an epoxy-polyester hybrid powder coating material is prepared by blending a polyester resin having at least two or more carboxyl groups in one molecule and an epoxy resin having two or more epoxy groups in one molecule. Those are preferably used. In this case, a polyester resin containing 30% by weight or more in the resin is generally used.
ポリエステル樹脂の数平均分子量（Ｍｎ）は特に限定されない。一例を挙げると、Ｍｎは、５００以上であることが好ましく、２０００以上であることがより好ましい。また、Ｍｎは、１０００００以下であることが好ましく、８００００以下であることがより好ましい。ポリエステル樹脂のＭｎが上記範囲内であることにより、得られる粉体塗料組成物は、貯蔵安定性および被膜性能が優れる。なお、本実施形態において、Ｍｎおよび重量平均分子量（Ｍｗ）は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）によりポリスチレンを標準物質として算出し得る。 The number average molecular weight (Mn) of the polyester resin is not particularly limited. As an example, Mn is preferably 500 or more, and more preferably 2000 or more. Further, Mn is preferably 100,000 or less, and more preferably 80000 or less. When the Mn of the polyester resin is within the above range, the obtained powder coating composition is excellent in storage stability and film performance. In this embodiment, Mn and the weight average molecular weight (Mw) can be calculated using polystyrene as a standard substance by gel permeation chromatography (GPC).
アクリル樹脂は特に限定されない。一例を挙げると、アクリル樹脂は、アクリレートまたはメタクリレートに由来する単位を有する重合体である。アクリル樹脂は、メチルメタクリレート（ＭＭＡ）由来の単位と、ＭＭＡ以外の単量体由来の単位（他の単量体）とからなるメチルメタクリレート共重合体であることが好ましい。アクリル樹脂は、カルボキシ基、水酸基、スルホ基等の硬化剤と反応し得る反応性基を有していてもよい。 The acrylic resin is not particularly limited. As an example, the acrylic resin is a polymer having units derived from acrylate or methacrylate. The acrylic resin is preferably a methyl methacrylate copolymer composed of units derived from methyl methacrylate (MMA) and units derived from monomers other than MMA (other monomers). The acrylic resin may have a reactive group capable of reacting with a curing agent such as a carboxy group, a hydroxyl group, or a sulfo group.
他の単量体は特に限定されない。一例を挙げると、他の単量体は、アルキルアクリレート、アルキルメタクリレート（ただし、メチルメタクリレートを除く）、ヒドロキシアルキルアクリレート、ヒドロキシアルキルメタクリレート、アクリル酸、メタクリル酸、アクリルアミド、メタクリルアミド、メタクリル酸グリシジル、アクリル酸グリシジル、３−トリメトキシシリルプロピルメタクリレート等である。 Other monomers are not particularly limited. For example, other monomers include alkyl acrylate, alkyl methacrylate (except methyl methacrylate), hydroxyalkyl acrylate, hydroxyalkyl methacrylate, acrylic acid, methacrylic acid, acrylamide, methacrylamide, glycidyl methacrylate, acrylic Glycidyl acid, 3-trimethoxysilylpropyl methacrylate and the like.
すなわち、アクリル系粉体塗料は、上記ポリエステル系、エポキシ系粉体塗料と同様に、当業者間においてアクリル系粉体塗料と称して用いられている粉体塗料であれば、特に限定されない。アクリル系粉体塗料は、たとえば、（メタ）アクリル酸エステル系単量体とグリシジル基を分子内に有する（メタ）アクリル酸エステル系単量体の共重合により合成された軟化点６０℃〜１５０℃の（メタ）アクリル系共重合体が結着樹脂として好適に使用される。この際、硬化剤は、特に限定されない。硬化剤は後述のものが用いられ得る。 That is, the acrylic powder paint is not particularly limited as long as it is a powder paint used by those skilled in the art as an acrylic powder paint in the same manner as the polyester and epoxy powder paints. The acrylic powder coating material is, for example, a softening point of 60 ° C. to 150 ° C. synthesized by copolymerization of a (meth) acrylic acid ester monomer and a (meth) acrylic acid ester monomer having a glycidyl group in the molecule. A (meth) acrylic copolymer at 0 ° C. is suitably used as the binder resin. At this time, the curing agent is not particularly limited. As the curing agent, those described below can be used.
アクリル樹脂のガラス転移温度（Ｔｇ）は特に限定されない。一例を挙げると、Ｔｇは、４０℃以上であることが好ましく、４５℃以上であることがより好ましい。また、Ｔｇは、９０℃以下であることが好ましく、８０℃以下であることがより好ましい。アクリル樹脂のＴｇが上記範囲内であることにより、得られる粉体塗料組成物の塗膜は、基材への密着性がより優れる。 The glass transition temperature (Tg) of the acrylic resin is not particularly limited. As an example, Tg is preferably 40 ° C. or higher, and more preferably 45 ° C. or higher. Further, Tg is preferably 90 ° C. or lower, and more preferably 80 ° C. or lower. When the Tg of the acrylic resin is within the above range, the resulting coating film of the powder coating composition is more excellent in adhesion to the substrate.
アクリル樹脂の数平均分子量（Ｍｎ）は特に限定されない。一例を挙げると、Ｍｎは、２００００以上であることが好ましく、３００００以上であることがより好ましい。また、Ｍｎは、１０００００以下であることが好ましく、９００００以下であることがより好ましい。アクリル樹脂のＭｎが上記範囲内であることにより、得られる粉体塗料組成物は、製造時に粉砕されやすく、かつ、ブロッキングが抑えられやすい。また、得られる粉体塗料組成物の塗膜は、基材への密着性がより優れる。 The number average molecular weight (Mn) of the acrylic resin is not particularly limited. For example, Mn is preferably 20000 or more, and more preferably 30000 or more. Further, Mn is preferably 100,000 or less, and more preferably 90000 or less. When the Mn of the acrylic resin is within the above range, the obtained powder coating composition is easily pulverized during production and blocking is easily suppressed. Moreover, the coating film of the obtained powder coating composition is more excellent in the adhesiveness to a base material.
アクリル樹脂の重量平均分子量（Ｍｗ）は特に限定されない。一例を挙げると、Ｍｗは、３００００以上であることが好ましく、４００００以上であることがより好ましい。また、Ｍｗは、２０００００以下であることが好ましく、１５００００以下であることがより好ましい。アクリル樹脂のＭｗが上記範囲内であることにより、得られる粉体塗料組成物は、製造時に粉砕されやすく、かつ、ブロッキングが抑えられやすい。また、得られる粉体塗料組成物の塗膜は、基材への密着性がより優れる。 The weight average molecular weight (Mw) of the acrylic resin is not particularly limited. As an example, Mw is preferably 30000 or more, and more preferably 40000 or more. Moreover, it is preferable that Mw is 200000 or less, and it is more preferable that it is 150,000 or less. When the Mw of the acrylic resin is within the above range, the obtained powder coating composition is easily pulverized during production and blocking is easily suppressed. Moreover, the coating film of the obtained powder coating composition is more excellent in the adhesiveness to a base material.
（酸化チタン）
本実施形態の粉体塗料組成物は、白色系の色相を呈するよう、酸化チタンが配合される。また、酸化チタンが配合されることにより、硬化後の粉体塗料組成物からなる塗膜は、隠蔽性が向上する。
(Titanium oxide)
The powder coating composition of this embodiment is blended with titanium oxide so as to exhibit a white hue. Moreover, the coating property which consists of a powder coating composition after hardening improves a concealment property by mix | blending a titanium oxide.
酸化チタンは特に限定されない。一例を挙げると、酸化チタンは、屈折率および触媒活性の観点から結晶形体はルチル型が好ましく、さらに光触媒反応が進行しにくくなるような表面処理がなされたものが好ましい。より具体的には、酸化チタンは、シリカ、アルミナ、ジルコニア、セレン、有機成分（ポリオール等）等で表面処理された酸化チタンである。これらの表面処理により、酸化チタンの含有量は、８０〜９５質量％程度に調整され得る。また、このような酸化チタンを用いて得られる塗膜は、劣化しにくく、かつ、白色度が優れやすい。 Titanium oxide is not particularly limited. For example, the titanium oxide is preferably a rutile type from the viewpoint of refractive index and catalytic activity, and is preferably subjected to a surface treatment that makes it difficult for the photocatalytic reaction to proceed. More specifically, titanium oxide is titanium oxide surface-treated with silica, alumina, zirconia, selenium, an organic component (polyol, etc.), and the like. By these surface treatments, the content of titanium oxide can be adjusted to about 80 to 95% by mass. Moreover, the coating film obtained using such a titanium oxide is hard to deteriorate and it is easy to be excellent in whiteness.
本実施形態の粉体塗料組成物は、上記した樹脂成分と酸化チタンとが、質量比で、１００：５０〜１００：１２０となるよう配合されている。酸化チタンは、樹脂成分１００質量部に対して、５０質量部以上となるよう配合されればよく、６０質量部以上となるよう配合されることが好ましい。また、酸化チタンは、樹脂成分１００質量部に対して、１２０質量部以下となるよう配合されればよく、８５質量部以下となるよう配合されることが好ましい。樹脂成分１００質量部に対する酸化チタンの配合量が５０質量部未満である場合、得られる粉体塗料組成物は、白色系の色相が呈されにくい。一方、樹脂成分１００質量部に対する酸化チタンの配合量が１２０質量部を超える場合、得られる粉体塗料組成物は、被膜の平滑性が悪くなる傾向がある。 The powder coating composition of this embodiment is blended so that the above-described resin component and titanium oxide are in a mass ratio of 100: 50 to 100: 120. Titanium oxide should just be mix | blended so that it may become 50 mass parts or more with respect to 100 mass parts of resin components, and it is preferable to mix | blend so that it may be 60 mass parts or more. Moreover, titanium oxide should just be mix | blended so that it may become 120 mass parts or less with respect to 100 mass parts of resin components, and it is preferable to mix | blend it so that it may become 85 mass parts or less. When the blending amount of titanium oxide with respect to 100 parts by mass of the resin component is less than 50 parts by mass, the obtained powder coating composition is unlikely to exhibit a white hue. On the other hand, when the compounding quantity of the titanium oxide with respect to 100 mass parts of resin components exceeds 120 mass parts, the powder coating composition obtained tends to deteriorate the smoothness of the film.
（黄色有機顔料）
本実施形態の粉体塗料組成物は、高温での熱硬化後に白色系の色相を維持するために、黄色有機顔料を含む。なお、本実施形態において、「白色系」とは、白色および淡彩色を含む。また、淡彩色は、白色に少量の着色原色を添加することによって得られた色彩である。
(Yellow organic pigment)
The powder coating composition of this embodiment contains a yellow organic pigment in order to maintain a white hue after heat curing at high temperature. In the present embodiment, the “white system” includes white and pale colors. The light color is a color obtained by adding a small amount of a primary color to white.
黄色有機顔料は、粉体塗料組成物が高温に曝されることにより、適宜退色する。本実施形態の粉体塗料組成物は、このように高温に曝されることにより退色し得る黄色有機顔料の性質をあえて利用することにより、高温に曝されることにより適宜黄変する樹脂成分や酸化チタンとのバランスを調整している。すなわち、従来の粉体塗料組成物は、たとえば１８０℃程度で熱硬化される際には黄変をある程度抑制することができていたが、より高温である２１０℃で熱硬化される場合には、樹脂成分が黄変したり、酸化防止剤そのものが黄変することがあった。しかしながら、本実施形態の粉体塗料組成物は、黄色有機顔料が配合されていることにより、元々、若干黄色味を帯びたクリーム系の淡彩色を呈し得る。このような淡彩色（白色系に含まれる）の色相を呈する粉体塗料組成物は、高温に曝されることにより、樹脂成分がいくらか黄変する現象と、黄色有機顔料が退色する現象とが同時に起こり得る。その結果、より高温である２１０℃等で熱硬化される場合であっても、１８０℃程度で熱硬化する場合と同様の色相が維持されることとなる。 The yellow organic pigment is appropriately faded when the powder coating composition is exposed to a high temperature. The powder coating composition of the present embodiment is a resin component that is appropriately yellowed by exposure to high temperature by using the property of the yellow organic pigment that can fade when exposed to high temperature in this way. The balance with titanium oxide is adjusted. That is, the conventional powder coating composition has been able to suppress yellowing to some extent when it is thermally cured at, for example, about 180 ° C., but when it is thermally cured at a higher temperature of 210 ° C. The resin component may turn yellow or the antioxidant itself may turn yellow. However, the powder coating composition of the present embodiment can originally exhibit a slightly yellowish cream-based pale color by incorporating a yellow organic pigment. A powder coating composition exhibiting such a pale hue (included in white) has a phenomenon that the resin component is somewhat yellowed by exposure to a high temperature, and a yellow organic pigment is faded. It can happen at the same time. As a result, even when heat-cured at a higher temperature such as 210 ° C., the same hue as when heat-cured at about 180 ° C. is maintained.
黄色有機顔料は特に限定されない。一例を挙げると、黄色有機顔料は、Ｃ．ｌ．ピグメントイエロー１（ハンザイエローＧ），２，３（ハンザイエロー１０Ｇ），４，５（ハンザイエロー５Ｇ），６，７，１０，１１，１２（ジスアゾイエローＡＡＡ），１３，１４，１６，１７，２４（フラバントロンイエロー），５５（ジスアゾイエローＡＡＰＴ），６１，６１：１，６５，７３，７４（ファストイエロー５ＧＸ），７５，８１，８３（ジスアゾイエローＨＲ），９３（縮合アゾイエロー３Ｇ），９４（縮合アゾイエロー６Ｇ），９５（縮合アゾイエローＧＲ），９７（ファストイエローＦＧＬ），９８，９９（アントラキノン），１００，１０８（アントラピリミジンイエロー），１０９（イソインドリノンイエロー２ＧＬＴ），１１０（イソインドリノンイエロー３ＲＬＴ），１１３，１１７，１２０（ベンズイミダゾロンイエローＨ２Ｇ），１２３（アントラキノンイエロー），１２４，１２８（縮合アゾイエロー８Ｇ），１２９，１３３，１３８（キノフタロンイエロー），１３９（イソインドリノンイエロー），１４７，１５１（ベンズイミダゾロンイエローＨ４Ｇ），１５３（ニッケルニトロソイエロー），１５４（ベンズイミダゾロンイエローＨ３Ｇ），１５５，１５６（ベンズイミダゾロンイエローＨＬＲ），１６７，１６８，１７２，１７３（イソインドリノンイエロー６ＧＬ），１８０（ベンズイミダゾロンイエロー）等である。これらの中でも、有機顔料の劣化退色する温度領域の観点から、黄色有機顔料は、Ｃ．ｌ．ピグメントイエロー１５４（ベンズイミダゾロンイエローＨ３Ｇ）、１０９（イソインドリノンイエロー２ＧＬＴ）であることが好ましい。なお、黄色有機顔料は、併用されてもよい。 The yellow organic pigment is not particularly limited. As an example, yellow organic pigments include C.I. l. Pigment Yellow 1 (Hansa Yellow G), 2, 3 (Hansa Yellow 10G), 4, 5 (Hansa Yellow 5G), 6, 7, 10, 11, 12 (Disazo Yellow AAA), 13, 14, 16, 17, 24 (flavantron yellow), 55 (disazo yellow AAPT), 61, 61: 1, 65, 73, 74 (fast yellow 5GX), 75, 81, 83 (disazo yellow HR), 93 (condensed azo yellow 3G), 94 (condensed azo yellow 6G), 95 (condensed azo yellow GR), 97 (fast yellow FGL), 98, 99 (anthraquinone), 100, 108 (anthrapyrimidine yellow), 109 (isoindolinone yellow 2GLT), 110 ( Isoindolinone Yellow 3RLT), 113, 117, 120 (Benzi Dazolone yellow H2G), 123 (anthraquinone yellow), 124, 128 (condensed azo yellow 8G), 129, 133, 138 (quinophthalone yellow), 139 (isoindolinone yellow), 147, 151 (benzimidazolone yellow H4G) , 153 (nickel nitroso yellow), 154 (benzimidazolone yellow H3G), 155, 156 (benzimidazolone yellow HLR), 167, 168, 172, 173 (isoindolinone yellow 6GL), 180 (benzimidazolone yellow) Etc. Among these, from the viewpoint of the temperature range in which the organic pigment deteriorates and fades, the yellow organic pigment is C.I. l. Pigment Yellow 154 (Benzimidazolone Yellow H3G) and 109 (Isoindolinone Yellow 2GLT) are preferable. The yellow organic pigment may be used in combination.
黄色有機顔料の配合量は特に限定されない。一例を挙げると、黄色有機顔料は、樹脂成分１００質量部に対して、０．０１質量部以上となるよう配合されることが好ましく、０．０３質量部以上となるよう配合されることがより好ましい。また、黄色有機顔料は、樹脂成分１００質量部に対して、１．０質量部以下となるよう配合されることが好ましく、０．５質量部以下となるよう配合されることがより好ましい。樹脂成分１００質量部に対する黄色有機顔料の配合量が０．０１質量未満である場合、得られる粉体塗料組成物は、高温で硬化される際に白色系の色相が維持されにくい。一方、樹脂成分１００質量部に対する黄色有機顔料の配合量が０．５質量部を超える場合、得られる粉体塗料組成物は、黄色の有機顔料の退色が樹脂の黄変よりも強く、色相が維持されないという傾向がある。 The compounding quantity of a yellow organic pigment is not specifically limited. For example, the yellow organic pigment is preferably blended so as to be 0.01 parts by mass or more, more preferably 0.03 parts by mass or more with respect to 100 parts by mass of the resin component. preferable. Moreover, it is preferable to mix | blend a yellow organic pigment so that it may become 1.0 mass part or less with respect to 100 mass parts of resin components, and it is more preferable to mix | blend so that it may be 0.5 mass part or less. When the compounding quantity of the yellow organic pigment with respect to 100 mass parts of resin components is less than 0.01 mass, when the obtained powder coating composition is hardened at high temperature, it is difficult to maintain a white hue. On the other hand, when the blending amount of the yellow organic pigment with respect to 100 parts by mass of the resin component exceeds 0.5 parts by mass, the obtained powder coating composition has a fading of the yellow organic pigment stronger than the yellowing of the resin, and the hue is There is a tendency not to be maintained.
（任意成分）
本実施形態の粉体塗料組成物は、適宜、任意成分が配合されてもよい。任意成分は、酸化防止剤、硬化剤、表面調整剤、紫外線吸収剤、硬化触媒、造核剤、ハイドロタルサイト、難燃剤、防曇剤、防霧剤、防滴剤、金属石鹸、エポキシ化合物、過塩素酸塩、滑剤、改質剤、赤外線吸収剤、充填剤、顔料（着色顔料、体質顔料）、タレ止め剤または沈降防止剤、消泡剤、帯電防止剤、可塑剤、架橋剤、レベリング剤、粘度調整剤、分散剤、ゲル化防止剤、補強剤等が例示される。
(Optional component)
In the powder coating composition of the present embodiment, arbitrary components may be appropriately blended. Optional components include antioxidants, curing agents, surface conditioners, UV absorbers, curing catalysts, nucleating agents, hydrotalcite, flame retardants, anti-fogging agents, anti-fogging agents, drip-proofing agents, metal soaps, epoxy compounds , Perchlorates, lubricants, modifiers, infrared absorbers, fillers, pigments (colored pigments, extender pigments), anti-sagging agents or anti-settling agents, antifoaming agents, antistatic agents, plasticizers, crosslinking agents, Examples include leveling agents, viscosity modifiers, dispersants, anti-gelling agents, reinforcing agents, and the like.
本実施形態の粉体塗料組成物は、特に、任意成分として酸化防止剤を含むことが好ましい。酸化防止剤は特に限定されない。一例を挙げると、酸化防止剤は、フェノール系酸化防止剤、リン系酸化防止剤、イオウ系酸化防止剤、ヒンダードアミン系酸化防止剤、芳香族アミン系酸化防止剤等である。酸化防止剤は、併用されてもよい。これらの中でも、粉体塗料組成物は、高温で熱硬化される際に白色系の色相がより維持されやすい点から、フェノール系酸化防止剤、リン系酸化防止剤およびイオウ系酸化防止剤からなる群から選択される少なくとも１つの酸化防止剤を含むことが好ましい。 In particular, the powder coating composition of this embodiment preferably contains an antioxidant as an optional component. The antioxidant is not particularly limited. For example, the antioxidant is a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, a hindered amine-based antioxidant, an aromatic amine-based antioxidant, or the like. Antioxidants may be used in combination. Among these, the powder coating composition is composed of a phenolic antioxidant, a phosphorus antioxidant, and a sulfur antioxidant because the white hue is more easily maintained when thermally cured at a high temperature. Preferably it comprises at least one antioxidant selected from the group.
フェノール系酸化防止剤は特に限定されない。一例を挙げると、フェノール系酸化防止剤は、２，６−ジ−ｔ−ブチルフェノール、２，４−ジメチル−６−ｔ−ブチルフェノール、２，６−ジ−ｔ−ブチル−４−メチルフェノール、２，６−ジ−ｔ−ブチル−４−エチルフェノール、２，４，６−トリ−ｔ−ブチルフェノール、２，６−ジ−ｔ−ブチル−４−ｓ−ブチルフェノール、２−ｔ−ブチル−４−メトキシフェノール、ビタミンＥ、２，６−ジ−ｔ−ブチル−４−ヒドロキシメチルフェノール、ｎ−オクタデシル−β−（４’−ヒドロキシ−３’、５’−ジ−ブチルフェニル）プロピオネート、２−ｔ−ブチル−６−（３’−ｔ−ブチル−５’−メチル−２’−ヒドロキシベンジル）−４−メチルフェニルアクリレート、プロピルガレート、オクチルガレート、ラウリルガレート、２，２’−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）、２，２’−メチレンビス（４−エチル−６−ｔ−ブチルフェノール）、４，４’−メチレンビス（２，６−ジ−ｔ−ブチルフェノール）、２，２’−メチレンビス（４−メチル−６−シクロヘキシルフェノール）、２，２’−ジヒドロキシ−３，３’−ジ（α−メチルシクロヘキシル）−５，５’−ジメチルジフェニルメタン、２，２’−エチリデン−ビス（４，６−ジ−ｔ−ブチルフェノール）、２，２’−ブチリデンビス（４−メチル−６−ｔ−ブチルフェノール）、４，４’−ブチリデンビス（３−メチル−６−ｔ−ブチルフェノール）、トリエチレングリコール−Ｎ−ビス［３−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオネート］、１，６−ヘキサンジオールビス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、カテコール、ｔ−ブチルカテコール、２−ブチル−４−ヒドロキシアニソール、２，６−ジ−ｔ−ブチル−ｐ−クレゾール、４，４’−チオビス（６−ｔ−ブチル−ｍ−クレゾール）、４，４’−チオビス（３−メチル−６−ｔ−ブチルフェノール）、４，４’−チオビス（４−メチル−６−ｔ−ブチルフェノール）、ビス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）スルフィド、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート）］メタン、３，９−ビス［２−［３−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニロキシ］−１，１−ジメチルエチル］−２，４，８，１０−テトラオキサスピロ［５，５］ウンデカン、ペンタエリスリトールテトラキス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、チオジエチレンビス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、Ｎ，Ｎ’−ヘキサン−１，６−ジイルビス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオンアミド］、ベンゼンプロパン酸，３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシ，Ｃ７−Ｃ９側鎖アルキルエステル、２，４−ジメチル−６−（１−メチルペンタデシル）フェノール、ジエチル［［３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシフェニル］メチル］ホスホネート、３，３’，３’’，５，５’，５’’−ヘキサ−ｔ−ブチル−ａ，ａ’，ａ’’−（メシチレン−２，４，６−トリル）トリ−ｐ−クレゾール、カルシウムジエチルビス［［［３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシフェニル］メチル］ホスホネート、４，６−ビス（オクチルチオメチル）−ｏ−クレゾール、エチレンビス（オキシエチレン）ビス［３−（５−ｔ−ブチル−４−ヒドロキシ−ｍ−トリル）プロピオネート］、ヘキサメチレンビス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、１，３，５−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）−１，３，５−トリアジン−２，４，６（１Ｈ，３Ｈ，５Ｈ）−トリオン、１，３，５−トリス［（４−ｔ−ブチル−３−ヒドロキシ−２，６−キシリル）メチル］−１，３，５−トリアジン−２，４，６（１Ｈ，３Ｈ，５Ｈ）−トリオン、Ｎ−フェニルベンゼンアミンと２，４，６−トリメチルペンテンとの反応生成物、２，６−ジ−ｔ−ブチル−４−（４，６−ビス（オクチルチオ）−１，３，５−トリアジン−２−イルアミノ）フェノール、２，６−ジフェニル−４−オクタデシロキシフェノール、ステアリル（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、ジステアリル（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）ホスホネート、２−オクチルチオ−４，６−ジ（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェノキシ）−ｓ−トリアジン、２，２’−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）、ビス［３，３−ビス（４−ヒドロキシ−３−ｔ−ブチルフェニル）ブチリックアシッド］グリコールエステル、４，４’−ブチリデンビス（２，６−ジ−ｔ−ブチルフェノール）、１，１，３−トリス（２−メチル−４−ヒドロキシ−５−ｔ−ブチルフェニル）ブタン、ビス［２−ｔ−ブチル−４−メチル−６−（２−ヒドロキシ−３−ｔ−ブチル−５−メチルベンジル）フェニル］テレフタレート、１，３，５−トリス（２，６−ジメチル−３−ヒドロキシ−４−ｔ−ブチルベンジル）イソシアヌレート、１，３，５−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）イソシアヌレート、１，３，５−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）−２，４，６−トリメチルベンゼン、１，３，５−トリス［（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオニルオキシエチル］イソシアヌレート、２−ｔ−ブチル−４−メチル−６−（２−アクリロイルオキシ−３−ｔ−ブチル−５−メチルベンジル）フェノール、ピクリン酸等である。 The phenolic antioxidant is not particularly limited. For example, phenolic antioxidants are 2,6-di-t-butylphenol, 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butyl-4-methylphenol, 2 , 6-di-t-butyl-4-ethylphenol, 2,4,6-tri-t-butylphenol, 2,6-di-t-butyl-4-s-butylphenol, 2-t-butyl-4- Methoxyphenol, vitamin E, 2,6-di-t-butyl-4-hydroxymethylphenol, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-butylphenyl) propionate, 2-t -Butyl-6- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, propyl gallate, octyl gallate, lauryl gallate 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-methylenebis (2,6-di-t) -Butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dihydroxy-3,3′-di (α-methylcyclohexyl) -5,5′-dimethyldiphenylmethane, 2, 2,2'-ethylidene-bis (4,6-di-t-butylphenol), 2,2'-butylidenebis (4-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6- t-butylphenol), triethylene glycol-N-bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], 1 6-hexanediol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], catechol, t-butylcatechol, 2-butyl-4-hydroxyanisole, 2,6-di-t -Butyl-p-cresol, 4,4'-thiobis (6-t-butyl-m-cresol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 4,4'-thiobis ( 4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4) -Hydroxyphenyl) propionate)] methane, 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-di Tylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxy) Phenyl) propionamide], benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl ester, 2,4-dimethyl-6- (1-methylpentadecyl) ) Phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-t-butyl-a, a ′, a ″-(mesitylene-2,4,6-tolyl) tri-p-cresol, calcium diethylbis [[[[3,5 -Bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-t- Butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-tris (3,5-di- -T-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris [(4-t-butyl-3 -Hydroxy-2, -Xylyl) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, reaction product of N-phenylbenzenamine and 2,4,6-trimethylpentene, , 6-di-t-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, 2-octylthio-4,6-di (3,5 -Di-t-butyl-4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-t-butylphenol), bis [3,3-bis (4- Droxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (2,6-di-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-) 5-t-butylphenyl) butane, bis [2-t-butyl-4-methyl-6- (2-hydroxy-3-t-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3 , 5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-di-t-butyl-4 -Hydroxyphenyl) propionyloxyethyl] isocyanurate, 2-t-butyl-4-methyl-6- (2-acryloyloxy-3-t-butyl-5-methylbenzyl) phenol, picric acid and the like.
リン系酸化防止剤は特に限定されない。一例を挙げると、リン系酸化防止剤は、トリフェニルホスファイト、トリス（２，４−ジ第三ブチルフェニル）ホスファイト、トリス（ノニルフェニル）ホスファイト、トリス（ジノニルフェニル）ホスファイト、トリス（モノ、ジ混合ノニルフェニル）ホスファイト、ビス（２−ｔ−ブチル−４，６−ジメチルフェニル）・エチルホスファイト、ジフェニルアシッドホスファイト、２，２’−メチレンビス（４，６−ジ−ｔ−ブチルフェニル）オクチルホスファイト、ジフェニルデシルホスファイト、フェニルジイソデシルホスファイト、トリブチルホスファイト、トリス（２−エチルヘキシル）ホスファイト、トリデシルホスファイト、トリラウリルホスファイト、ジブチルアシッドホスファイト、ジラウリルアシッドホスファイト、トリラウリルトリチオホスファイト、ビス（ネオペンチルグリコール）・１，４−シクロヘキサンジメチルジホスファイト、ビス（２，４−ジ−ｔ−ブチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，６−ジ−ｔ−ブチル−４−メチルフェニル）ペンタエリスリトールジホスファイト、ジステアリルペンタエリスリトールジホスファイト、テトラ（Ｃ１２−１５混合アルキル）−４，４’−イソプロピリデンジフェニルホスファイト、ビス［２，２’−メチレンビス（４，６−ジアミルフェニル）］・イソプロピリデンジフェニルホスファイト、水素化−４，４’−イソプロピリデンジフェノールポリホスファイト、テトラトリデシル・４，４’−ブチリデンビス（２−ｔ−ブチル−５−メチルフェノール）ジホスファイト、ヘキサ（トリデシル）・１，１，３−トリス（２−メチル−５−ｔ−ブチル−４−ヒドロキシフェニル）ブタン・トリホスホナイト、９，１０−ジハイドロ−９−オキサ−１０−ホスファフェナンスレン−１０−オキサイド、２−ブチル−２−エチルプロパンジオール・２，４，６−トリ−ｔ−フェノールモノホスファイト等である。 The phosphorus antioxidant is not particularly limited. For example, phosphorus antioxidants include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris. (Mono, dimixed nonylphenyl) phosphite, bis (2-t-butyl-4,6-dimethylphenyl) .ethyl phosphite, diphenyl acid phosphite, 2,2'-methylenebis (4,6-di-t -Butylphenyl) octyl phosphite, diphenyl decyl phosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite Fight, G Lauryl trithiophosphite, bis (neopentyl glycol) 1,4-cyclohexanedimethyl diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t -Butyl-4-methylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetra (C12-15 mixed alkyl) -4,4'-isopropylidene diphenyl phosphite, bis [2,2'-methylenebis (4,6-Diamylphenyl)]-isopropylidene diphenyl phosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, tetratridecyl 4,4'-butylidenebis (2-t-butyl- 5-methylphenol) diphosphite, Oxa (tridecyl) .1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane triphosphonite, 9,10-dihydro-9-oxa-10-phosphafenance Len-10-oxide, 2-butyl-2-ethylpropanediol, 2,4,6-tri-t-phenol monophosphite, and the like.
イオウ系酸化防止剤は特に限定されない。一例を挙げると、イオウ系酸化防止剤は、ジラウリル−３，３’−チオジプロピオネート、ジミリスチル−３，３’−チオジプロピオネート、ジステアリル−３，３’−チオジプロピオネート等である。 The sulfur-based antioxidant is not particularly limited. For example, the sulfur-based antioxidant may be dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, and the like. is there.
酸化防止剤の配合量は特に限定されない。一例を挙げると、酸化防止剤は、樹脂成分１００質量部に対し、０．０１質量部以上となるよう配合されることが好ましく、０．１質量部以上となるよう配合されることがより好ましい。酸化防止剤は、樹脂成分１００質量部に対し、１０質量部以下となるよう配合されることが好ましく、５質量部以下となるよう配合されることがより好ましい。酸化防止剤が上記範囲内となるよう配合されることにより、得られる粉体塗料組成物は、白色系の色相がより維持されやすい。 The blending amount of the antioxidant is not particularly limited. For example, the antioxidant is preferably blended so as to be 0.01 parts by mass or more, more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the resin component. . The antioxidant is preferably blended so as to be 10 parts by mass or less, more preferably 5 parts by mass or less, relative to 100 parts by mass of the resin component. By blending the antioxidant so as to fall within the above range, the resulting powder coating composition is more likely to maintain a white hue.
硬化剤は、樹脂成分の反応性基と反応して樹脂成分を架橋したり高分子量化して、樹脂成分を硬化させるために適宜配合され得る。硬化剤は、樹脂成分が有する反応性基（水酸基、カルボキシ基等）に反応し得る反応性基を２個以上有する。硬化剤の反応性基は、粉体塗料組成物が加熱溶融された際に反応し得る反応性基であることが好ましい。一例を挙げると、反応性基は、常温で高い反応性基を有するイソシアナート基よりもブロック化イソシアナート基が好ましい。ブロック化イソシアナート基は、粉体塗料組成物が加熱溶融された際にブロック剤が脱離してイソシアナート基となり、そのイソシアナート基が反応性基として作用する。 A hardening | curing agent may be mix | blended suitably in order to react with the reactive group of a resin component, to bridge | crosslink a resin component or to make high molecular weight, and to harden a resin component. The curing agent has two or more reactive groups that can react with a reactive group (hydroxyl group, carboxy group, etc.) of the resin component. The reactive group of the curing agent is preferably a reactive group that can react when the powder coating composition is heated and melted. For example, the reactive group is preferably a blocked isocyanate group rather than an isocyanate group having a high reactive group at room temperature. When the powder coating composition is heated and melted, the blocked isocyanate group is released from the blocking agent to become an isocyanate group, and the isocyanate group acts as a reactive group.
硬化剤は特に限定されない。一例を挙げると、硬化剤は、ポリエステル系粉体塗料において、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脂肪族、芳香族または脂環族イソシアネート、あるいはこれらイソシアネートと活性水素基を有する化合物との付加物、さらにはこれらの化合物中のイソシアネート基をメタノール、イソプロパノール、ε−カプロラクタム等のブロック化剤でブロックしたブロックイソシアネート等である。硬化剤は、エポキシ系粉体塗料において、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン等の脂肪族アミン類、ｍ−キシリレンジアミン、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン等の芳香族アミン類、無水フタル酸、テトラヒドロ無水フタル酸、無水トリメリット酸等の無水酸類等である。硬化剤は、アクリル系粉体塗料において、無水フタル酸、テトラヒドロ無水フタル酸、無水トリメリット酸等の無水酸類、ドデカンジカルボン酸等のジカルボン酸類、ジシアンジアミド等である。これら硬化剤は、併用されてもよい。 The curing agent is not particularly limited. For example, the curing agent may be an aliphatic, aromatic or alicyclic isocyanate such as hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, or a compound having an active hydrogen group, in a polyester powder coating. Adducts, and further, blocked isocyanates obtained by blocking isocyanate groups in these compounds with blocking agents such as methanol, isopropanol, and ε-caprolactam. Curing agents are epoxy powder coatings, aliphatic amines such as ethylenediamine, diethylenetriamine, and triethylenetetramine, aromatic amines such as m-xylylenediamine, m-phenylenediamine, and p-phenylenediamine, and phthalic anhydride. Acid anhydrides such as tetrahydrophthalic anhydride and trimellitic anhydride. Curing agents include acrylic anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride and trimellitic anhydride, dicarboxylic acids such as dodecanedicarboxylic acid, dicyandiamide, and the like in acrylic powder coatings. These curing agents may be used in combination.
硬化剤の軟化温度は特に限定されない。一例を挙げると、軟化温度は、１０℃以上であることが好ましく、４０℃以上であることがより好ましい。また、軟化温度は、１２０℃以下であることが好ましく、１００℃以下であることがより好ましい。軟化温度が上記範囲内であることにより、粉体塗料組成物は、室温で硬化しにくく、塊が形成されにくい。また、上記軟化温度の硬化剤は、粉体塗料組成物中に均質に分散されやすく、得られる塗膜の表面平滑性、強度および耐湿性等が向上しやすい。 The softening temperature of the curing agent is not particularly limited. As an example, the softening temperature is preferably 10 ° C. or higher, and more preferably 40 ° C. or higher. The softening temperature is preferably 120 ° C. or lower, and more preferably 100 ° C. or lower. When the softening temperature is within the above range, the powder coating composition is hard to be cured at room temperature and a lump is hardly formed. Moreover, the curing agent having the softening temperature is easily dispersed homogeneously in the powder coating composition, and the surface smoothness, strength, moisture resistance, and the like of the resulting coating film are easily improved.
硬化剤の配合量は特に限定されない。一例を挙げると、硬化剤は、樹脂成分１００質量部に対し、１質量部以上となるよう配合されることが好ましく、２質量部以上となるよう配合されることがより好ましい。硬化剤は、樹脂成分１００質量部に対し、１０質量部以下となるよう配合されることが好ましく、８質量部以下となるよう配合されることがより好ましい。硬化剤が上記範囲内となるよう配合されることにより、得られる粉体塗料組成物は、適切に硬化され、表面平滑性、強度および耐湿性等の優れた塗膜が形成されやすい。 The compounding quantity of a hardening | curing agent is not specifically limited. If an example is given, it will be preferable to mix | blend a hardening | curing agent so that it may become 1 mass part or more with respect to 100 mass parts of resin components, and it is more preferable to mix | blend so that it may become 2 mass parts or more. It is preferable to mix | blend a hardening | curing agent so that it may become 10 mass parts or less with respect to 100 mass parts of resin components, and it is more preferable to mix | blend so that it may be 8 mass parts or less. When the curing agent is blended so as to fall within the above range, the obtained powder coating composition is appropriately cured, and a coating film excellent in surface smoothness, strength, moisture resistance and the like is easily formed.
表面調整剤は特に限定されない。一例を挙げると、表面調整剤は、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート等の（メタ）アクリル酸のアルキルエステル類を原料として得られたアクリル重合体等が例示される。 The surface conditioner is not particularly limited. For example, the surface conditioner is an alkyl of (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, etc. Examples include acrylic polymers obtained using esters as raw materials.
表面調整剤の配合量は特に限定されない。一例を挙げると、表面調整剤は、樹脂成分１００質量部に対し、０．１質量部以上となるよう配合されることが好ましく、０．５質量部以上となるよう配合されることがより好ましい。表面調整剤は、樹脂成分１００質量部に対し、５質量部以下となるよう配合されることが好ましく、３質量部以下となるよう配合されることがより好ましい。表面調整剤が上記範囲内となるよう配合されることにより、得られる粉体塗料組成物を用いて得られる塗膜は、表面平滑性等が優れる。 The blending amount of the surface conditioner is not particularly limited. If an example is given, it is preferable to mix | blend a surface conditioning agent so that it may become 0.1 mass part or more with respect to 100 mass parts of resin components, and it is more preferable to mix | blend so that it may become 0.5 mass part or more. . The surface conditioner is preferably blended so as to be 5 parts by mass or less, more preferably 3 parts by mass or less, relative to 100 parts by mass of the resin component. By blending the surface conditioner to be within the above range, the coating film obtained using the obtained powder coating composition has excellent surface smoothness and the like.
紫外線吸収剤は特に限定されない。一例を挙げると、紫外線吸収剤は、ベンゾトリアゾール系化合物、トリアジン系化合物、ベンゾフェノン系化合物、サリシレート系化合物、シアノアクリルレート系化合物、ニッケル系化合物等である。具体的には、紫外線吸収剤は、２−（２Ｈ−ベンゾトリアゾール−２−イル）−６−（１−メチル−１−フェニルエチル）−４−（１，１，３，３−テトラメチルブチル）フェノール、ベンゼンプロパン酸−３−（２Ｈ−ベンゾトリアゾール−２−イル）−５−（１，１−ジメチルエチル）−４−ヒドロキシ−Ｃ７−９側鎖および直鎖アルキルエステル、オクチル−３−［３−ｔ−ブチル−４−ヒドロキシ−５−（５−クロロ−２Ｈ−ベンゾトリアゾール−２−イル）フェニル］プロピオネート、２−エチルヘキシル−３−［３−ｔ−ブチル−４−ヒドロキシ−５−（５−クロロ−２Ｈ−ベンゾトリアゾール−２−イル）フェニル］プロピオネート、ベンゼンプロパン酸−３−（２Ｈ−ベンゾトリアゾール−２−イル）−５−（１，１−ジメチルエチル）−４−ヒドロキシ−Ｃ７−９側鎖および直鎖アルキルエステル、２−（２−ヒドロキシ−５−ｔ−ブチルフェニル）−２Ｈ−ベンゾトリアゾール、２−（２’−ヒドロキシ−５’−メチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ジ−ｔ−ブチルフェニル）−５−クロロベンゾトリアゾール、２−（２’−ヒドロキシ−３’−ｔ−ブチル−５’−メチルフェニル）−５−クロロベンゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ジ−ｔ−アミルフェニル）クロロベンゾトリアゾール、２−（２’−ヒドロキシ−５’−ｔ−オクチルフェニル）ベンゾトリアゾール、並びに、２，４−ビス「２−ヒドロキシ−４−ブトキシフェニル」−６−（２，４−ジブトキシフェニル）−１，３−５−トリアジン等である。 The ultraviolet absorber is not particularly limited. For example, the ultraviolet absorber is a benzotriazole compound, a triazine compound, a benzophenone compound, a salicylate compound, a cyanoacrylate compound, a nickel compound, or the like. Specifically, the ultraviolet absorber is 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) ) Phenol, benzenepropanoic acid-3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy-C7-9 side chain and linear alkyl ester, octyl-3- [3-t-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate, 2-ethylhexyl-3- [3-t-butyl-4-hydroxy-5 (5-Chloro-2H-benzotriazol-2-yl) phenyl] propionate, benzenepropanoic acid-3- (2H-benzotriazol-2-yl) -5- (1,1-dimethyl) Ruethyl) -4-hydroxy-C7-9 side chain and linear alkyl ester, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5′-methyl) Phenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-t-butyl-5 ′) -Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) chlorobenzotriazole, 2- (2'-hydroxy-5'-t-octyl) Phenyl) benzotriazole, and 2,4-bis “2-hydroxy-4-butoxyphenyl” -6- (2,4-dibutoxyphenyl) -1,3-5 It is a triazine and the like.
着色顔料は特に限定されない。一例を挙げると、着色顔料は、べんがら、カーボンブラック、キナクリドン、ジケトピロロピロール、イソインドリノン、インダンスロン、ペリレン、ペリノン、アントラキノン、ジオキサジン、ベンゾイミダゾロン、トリフェニルメタンキノフタロン、アントラピリミジン、黄鉛、パールマイカ、透明パールマイカ、着色マイカ、干渉マイカ、フタロシアニン、ハロゲン化フタロシアニン、アゾ顔料（アゾメチン金属錯体、縮合アゾ等）、酸化鉄、銅フタロシアニン、縮合多環類顔料等である。着色顔料は併用されてもよい。 The color pigment is not particularly limited. For example, the colored pigments include red bean, carbon black, quinacridone, diketopyrrolopyrrole, isoindolinone, indanthrone, perylene, perinone, anthraquinone, dioxazine, benzimidazolone, triphenylmethanequinophthalone, anthrapyrimidine, yellow Lead, pearl mica, transparent pearl mica, colored mica, interference mica, phthalocyanine, halogenated phthalocyanine, azo pigment (azomethine metal complex, condensed azo, etc.), iron oxide, copper phthalocyanine, condensed polycyclic pigment, and the like. Coloring pigments may be used in combination.
また、塗膜に光輝性を与える光輝性顔料として、パール顔料、アルミニウム粉やステンレス鋼粉などの金属粉や金属フレーク、ガラスビーズやガラスフレーク、雲母、リン片状酸化鉄（ＭＩＯ）等が併用されてもよい。 In addition, pearl pigments, metal powders such as aluminum powder and stainless steel powder, metal flakes, glass beads and glass flakes, mica, and flake iron oxide (MIO) are used in combination as glitter pigments that give the coating film glitter. May be.
着色顔料の配合量は特に限定されない。着色顔料の配合量は、所望される塗膜の色彩、明度、深度等を考慮して適宜調整され得る。 The blending amount of the color pigment is not particularly limited. The blending amount of the color pigment can be appropriately adjusted in consideration of the desired color, brightness, depth, and the like of the coating film.
体質顔料は特に限定されない。一例を挙げると、体質顔料は、炭酸カルシウム、硫酸バリウム、含水珪酸マグネシウム（タルク）、炭酸マグネシウム、硫酸カルシウム（石膏）、珪藻土、マイカ（雲母粉）、ネフェリンサイナイト、シリカ、ノイブルグ珪土等である。体質顔料は併用されてもよい。 The extender is not particularly limited. For example, extender pigments are calcium carbonate, barium sulfate, hydrous magnesium silicate (talc), magnesium carbonate, calcium sulfate (gypsum), diatomaceous earth, mica (mica powder), nepheline sinite, silica, Neuburg silica clay, etc. is there. An extender may be used in combination.
以上、本実施形態の粉体塗料組成物は、樹脂成分に対して所定の配合比率となるよう酸化チタンが配合されている。これにより、粉体塗料組成物は、白色系の色相となる。さらに、粉体塗料組成物は、黄色有機顔料が配合されている。黄色有機顔料は、硬化時に高温に曝されることにより、適宜退色する。一方、粉体塗料組成物に含まれる樹脂成分等は、高温に曝されることにより、適宜黄変し得る。その結果、本実施形態の粉体塗料組成物は、高温に曝される場合において、樹脂成分等の黄変と、黄色有機顔料の退色とが同時に起こり、白色系の色相が維持される。 As described above, the powder coating composition of the present embodiment is blended with titanium oxide so as to have a predetermined blending ratio with respect to the resin component. As a result, the powder coating composition has a white hue. Furthermore, the powder coating composition contains a yellow organic pigment. Yellow organic pigments fade appropriately when exposed to high temperatures during curing. On the other hand, the resin component contained in the powder coating composition can be appropriately yellowed by being exposed to high temperature. As a result, when the powder coating composition of the present embodiment is exposed to a high temperature, yellowing of the resin component and the fading of the yellow organic pigment occur at the same time, and the white hue is maintained.
より具体的には、本実施形態の粉体塗料組成物によって形成される塗膜は、たとえば１８０℃で硬化される場合と、より高温である２１０℃で硬化される場合とを比較すると、２１０℃で硬化させた塗膜の色相（Ｌ、ａ、ｂ値）と１８０℃で硬化させた塗膜の色相（Ｌ、ａ、ｂ値）との変化量（ΔＥ）が１．０以下となり得る。すなわち、本実施形態の粉体塗料組成物によれば、従来は防ぐことが困難であった、より高温での硬化を行った場合の黄変が防がれ、色相が維持され得る。なお、塗膜の色相（Ｌ、ａ、ｂ値）は、たとえば、色彩色差計（コニカミノルタ（株）製、ＣＲ−４００）にて測定し得る。 More specifically, when the coating film formed by the powder coating composition of the present embodiment is cured at, for example, 180 ° C. and when cured at 210 ° C., which is a higher temperature, 210 The amount of change (ΔE) between the hue (L, a, b value) of the coating film cured at ° C and the hue (L, a, b value) of the coating film cured at 180 ° C can be 1.0 or less. . That is, according to the powder coating composition of the present embodiment, yellowing when curing at a higher temperature, which has been difficult to prevent in the past, can be prevented and the hue can be maintained. In addition, the hue (L, a, b value) of the coating film can be measured by, for example, a color difference meter (manufactured by Konica Minolta Co., Ltd., CR-400).
＜粉体塗料組成物の製造方法＞
本実施形態の粉体塗料組成物の製造方法は特に限定されない。一例を挙げると、粉体塗料組成物は、上記した樹脂成分、酸化チタン、黄色有機顔料および任意成分を準備し、これらをスーパーミキサー、ヘンシェルミキサー等を使用して予備混合し、コニーダー、エクストルーダー等の混練機を用いて溶融混練することにより製造され得る。溶融混練時の加熱温度は、焼付硬化温度よりも低く設定される。得られた溶融物は、冷却ロールや冷却コンベヤー等で冷却、固化され、粗粉砕工程および微粉砕工程を経て、所望の粒径に粉砕される。なお、得られた粉体塗料組成物は、流動性付与剤や、帯電調整剤等が外添されてもよい。
<Method for producing powder coating composition>
The manufacturing method of the powder coating composition of this embodiment is not specifically limited. For example, a powder coating composition is prepared by preparing the above resin component, titanium oxide, yellow organic pigment and optional components, and premixing them using a super mixer, a Henschel mixer, etc. It can be produced by melt kneading using a kneader such as the above. The heating temperature at the time of melt kneading is set lower than the bake curing temperature. The obtained melt is cooled and solidified by a cooling roll, a cooling conveyor or the like, and is pulverized to a desired particle size through a coarse pulverization step and a fine pulverization step. The obtained powder coating composition may be externally added with a fluidity imparting agent, a charge adjusting agent and the like.
粉砕後の粉体塗料組成物の体積平均粒径は特に限定されない。一例を挙げると、粉体塗料組成物の体積平均粒径は、２５〜３５μｍである。粉体塗料組成物の体積平均粒子径が上記範囲内であることにより、粉体塗料組成物は、取り扱われやすく、かつ、平滑性の優れた塗膜が形成されやすい。なお、本実施形態において、体積平均粒径は、たとえば、リード・アンド・ノースロップ社製のマイクロトラック−ＩＩ等の電磁波散乱による粒径測定装置によって測定され得る。 The volume average particle size of the powder coating composition after pulverization is not particularly limited. As an example, the volume average particle size of the powder coating composition is 25 to 35 μm. When the volume average particle diameter of the powder coating composition is within the above range, the powder coating composition is easy to handle and a coating film having excellent smoothness is easily formed. In the present embodiment, the volume average particle diameter can be measured by a particle diameter measuring apparatus using electromagnetic wave scattering such as Microtrac-II manufactured by Reed & Northrop.
＜塗膜形成時における色相維持方法＞
粉体塗料組成物は、基材に付与された後、熱硬化されることにより塗膜が形成される。ここで、本実施形態の粉体塗料組成物は、樹脂成分と酸化チタンとを配合比率（質量比）が１００：５０〜１００：１２０となるよう含まれている。また、粉体塗料組成物は、黄色有機顔料がさらに配合されている。このように、所定の配合割合となるように樹脂成分と酸化チタンとが併用されている粉体塗料組成物に対して、さらに黄色有機顔料が配合される。黄色有機顔料は、硬化時に高温に曝されることにより、適宜退色する。一方、粉体塗料組成物に含まれる樹脂成分等は、高温に曝されることにより、適宜黄変し得る。その結果、本実施形態の粉体塗料組成物は、高温に曝される場合において、樹脂成分等の黄変と、黄色有機顔料の退色とが同時に起こり、白色系の色相が維持される。
<Hue maintenance method during coating film formation>
The powder coating composition is applied to a substrate and then thermally cured to form a coating film. Here, the powder coating composition of this embodiment contains a resin component and titanium oxide so that the blending ratio (mass ratio) is 100: 50 to 100: 120. The powder coating composition further contains a yellow organic pigment. In this way, a yellow organic pigment is further blended into the powder coating composition in which the resin component and titanium oxide are used in combination so as to obtain a predetermined blending ratio. Yellow organic pigments fade appropriately when exposed to high temperatures during curing. On the other hand, the resin component contained in the powder coating composition can be appropriately yellowed by being exposed to high temperature. As a result, when the powder coating composition of the present embodiment is exposed to a high temperature, yellowing of the resin component and the fading of the yellow organic pigment occur at the same time, and the white hue is maintained.
粉体塗料組成物の付与される基材は特に限定されない。一例を挙げると、基材は、アルミニウム、ステンレス・スチール、クロム・メッキ、トタン板、ブリキ板等の金属素材または金属製品類；瓦類；ガラス類；各種の無機質建材類；耐熱性のあるプラスチック、木材等である。より具体的には、基材は、自動車車体または自動車部品類；二輪車または二輪車部品類；門扉またはフェンス類等の各種建材類；アルミサッシ類等の各種の建築内外装用資材類；アルミホイールなどのような種々の鉄または非鉄金属類の素材またはプラスチック製品、木工諸製品類等である。基材は、適宜、化成処理、リン酸亜鉛処理、クロメート処理等の表面処理や、電着塗装等が施されてもよい。 The base material to which the powder coating composition is applied is not particularly limited. For example, the base material is a metal material or metal product such as aluminum, stainless steel, chrome plating, tin plate, tin plate; tiles; glass; various inorganic building materials; heat-resistant plastic , Wood, etc. More specifically, the base material is an automobile body or parts; motorcycles or motorcycle parts; various building materials such as gates or fences; various building interior and exterior materials such as aluminum sashes; aluminum wheels, etc. These are various iron or non-ferrous metal materials, plastic products, woodworking products, and the like. The base material may be appropriately subjected to surface treatment such as chemical conversion treatment, zinc phosphate treatment, chromate treatment, and electrodeposition coating.
なお、形成される塗膜は、単層塗膜であってもよく、複層塗膜であってもよい。粉体塗料組成物は、基材表面に直接下塗り塗料として塗布され、低い焼き付け温度（たとえば１４０〜１６０℃）により焼き付けが行われることにより下塗り塗膜が形成されてもよい。また、下塗り塗膜は、その上に、中塗り塗料、上塗り塗料が塗装されてもよい。また、粉体塗料組成物は、中塗り塗料または上塗り塗料として使用されてもよい。この場合、中塗り塗料および上塗り塗料は、溶剤系塗料、水性塗料、粉体塗料等の任意の形態の塗料であってよく、クリヤー塗料、着色ベース塗料、光揮性顔料を含有する塗料等であってよい。 The formed coating film may be a single layer coating film or a multilayer coating film. The powder coating composition may be directly applied to the substrate surface as an undercoat paint, and an undercoat coating film may be formed by baking at a low baking temperature (for example, 140 to 160 ° C.). Further, the undercoat coating film may be coated with an intermediate coating or top coating. The powder coating composition may be used as an intermediate coating or top coating. In this case, the intermediate coating material and the top coating material may be paints of any form such as solvent-based paints, water-based paints, powder paints, clear paints, colored base paints, paints containing volatile pigments, etc. It may be.
塗料を基材に付与する方法は特に限定されない。一例を挙げると、塗料の付与方法は、スプレー塗装法、静電粉体塗装法、流動浸漬法等である。形成される塗膜の厚みは特に限定されない。一例を挙げると、厚みは、３０〜２００μｍである。 The method for applying the paint to the substrate is not particularly limited. For example, the method for applying the paint is a spray coating method, an electrostatic powder coating method, a fluidized dipping method, or the like. The thickness of the coating film to be formed is not particularly limited. As an example, the thickness is 30 to 200 μm.
付与された粉体塗料組成物の加熱条件は特に限定されない。本実施形態の粉体塗料組成物は、高温に曝される場合であっても、白色系の色相が維持される。そのため、焼き付けの加熱温度は、１８０℃以上であってもよく、２００℃以上であってもよい。加熱時間は、加熱温度に応じて適宜設定され得る。 The heating conditions for the applied powder coating composition are not particularly limited. The powder coating composition of this embodiment maintains a white hue even when exposed to high temperatures. Therefore, the heating temperature for baking may be 180 ° C. or higher, or 200 ° C. or higher. The heating time can be appropriately set according to the heating temperature.
以下、実施例により本発明をより具体的に説明する。本発明は、これら実施例に何ら限定されない。 Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to these examples.
使用した原料を以下に示す。
＜樹脂成分＞
ｊＥＲ１００３（三菱化学（株）製、ビスフェノールＡ型エポキシ樹脂、Ｍｗ：１３００、軟化点（環球法）：８９℃、エポキシ当量：６７０〜７７０）
クリルコート１７１６−０（三菱化学（株）製、ポリエステル樹脂、酸価：３０）
＜酸化チタン＞
ＪＲ−７０１（テイカ（株）製、平均粒子径：０．２７μｍ、酸化チタン含有量：９３％以上）
ＴｉＯＮＡ ５９５（交洋貿易（株）製）
＜黄色有機顔料＞
ベンズイミダゾロンイエローＨ３Ｇ（トーヨーカラー（株）製、ＬＩＯＮＯＧＥＮ ＹＥＬＬＯＷ ３Ｇ−Ｆ）
＜その他＞
レジフローＰ６７（エストロンケミカル社製、表面調整剤、アクリル共重合体）
スミライザーＧＡ−８０（住友化学（株）製、フェノール系酸化防止剤）
スミライザーＴＰ−Ｄ（住友化学（株）製、有機イオウ系酸化防止剤）
アデカスタブ ＰＥＰ−３６（ＡＤＥＫＡ社製、リン系酸化防止剤）
カーボンブラック
べんがら
ベスタゴンＢ６８（ヒュルス社製、硬化剤、ピロメリット酸の２−フェニルイミダゾリンとの塩（１：１））
The raw materials used are shown below.
<Resin component>
jER1003 (Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, Mw: 1300, softening point (ring and ball method): 89 ° C., epoxy equivalent: 670 to 770)
Krill coat 1716-0 (Mitsubishi Chemical Corporation, polyester resin, acid value: 30)
<Titanium oxide>
JR-701 (manufactured by Teika Co., Ltd., average particle size: 0.27 μm, titanium oxide content: 93% or more)
TiONA 595 (manufactured by Koyo Trading Co., Ltd.)
<Yellow organic pigment>
Benzimidazolone Yellow H3G (Toyocolor Co., Ltd., LIONOGEN YELLOW 3G-F)
<Others>
Regiflow P67 (Estron Chemical Co., surface conditioner, acrylic copolymer)
Sumilyzer GA-80 (manufactured by Sumitomo Chemical Co., Ltd., phenolic antioxidant)
Sumilyzer TP-D (Sumitomo Chemical Co., Ltd., organic sulfur-based antioxidant)
ADK STAB PEP-36 (manufactured by ADEKA, phosphorus antioxidant)
Carbon Black Bengala Vestagon B68 (manufactured by Huls, hardener, salt of pyromellitic acid with 2-phenylimidazoline (1: 1))
＜実施例１＞
表１に示される処方（単位：質量部）に従って、各原料をミキサー（スーパーミキサーピッコロ、（株）カワタ製）を用いて３０００ｒｐｍで３０秒間の予備混合を行った。次いで、コニーダー（ＰＣＳ３０、ＢＵＳＳ社製）を用いて１１５℃、９０ｒｐｍで混練した。その後、ミキサー（スーパーミキサーピッコロ、（株）カワタ製）を用いて３０００ｒｐｍで９０秒間の粗粉砕を行い、次いで、ピンディスクミル（ＡＬＰＩＮＥ社製）を用いて６０Ｈｚにて微粉砕を行った。得られた粉砕物を、１４０メッシュの篩で篩過し、粉体塗料組成物を得た。
<Example 1>
According to the formulation (unit: parts by mass) shown in Table 1, each raw material was premixed at 3000 rpm for 30 seconds using a mixer (Supermixer Piccolo, manufactured by Kawata Corporation). Subsequently, it knead | mixed at 115 degreeC and 90 rpm using the kneader (PCS30, product made by BUSS). Thereafter, coarse pulverization was performed at 3000 rpm for 90 seconds using a mixer (Super mixer Piccolo, manufactured by Kawata Co., Ltd.), and then fine pulverization was performed at 60 Hz using a pin disk mill (manufactured by ALPINE). The obtained pulverized product was sieved with a 140 mesh sieve to obtain a powder coating composition.
得られた粉体塗料組成物を、日本パーカーライジング（株）製のＰｕｌｓｅ Ｐｏｗｅｒ ＧＸ７０００Ｃを用いてボンデ鋼板に対して静電塗装し、１００℃で５分間の熱硬化を行った。得られた塗膜の膜厚は、６０〜９０μｍであった。 The obtained powder coating composition was electrostatically coated on a bonded steel plate using Pulse Power GX7000C manufactured by Nihon Parker Rising Co., Ltd., and was thermally cured at 100 ° C. for 5 minutes. The film thickness of the obtained coating film was 60 to 90 μm.
＜実施例２〜６、比較例１〜４＞
表１に記載の処方に変更した以外は、実施例１と同様の方法により粉体塗料組成物および塗膜を調製した。
<Examples 2-6, Comparative Examples 1-4>
A powder coating composition and a coating film were prepared in the same manner as in Example 1 except that the formulation shown in Table 1 was changed.
実施例１〜６および比較例１〜４において得られた粉体塗料組成物を付与した塗膜について、色相の変化を、以下の評価方法により評価した。 About the coating film which provided the powder coating composition obtained in Examples 1-6 and Comparative Examples 1-4, the change of the hue was evaluated with the following evaluation methods.
＜色相変化＞
電気炉を用いて、１８０℃または２１０℃にて、塗膜を３０分間硬化させた。それぞれの温度で熱硬化を行った場合の塗膜の色相（Ｌ、ａ、ｂ値）を、色彩色差計（コニカミノルタ（株）製、ＣＲ−４００）にて測定した。得られた色相に基づき、１８０℃で硬化した塗膜の色相（Ｌ、ａ、ｂ値）と２１０℃で硬化した塗膜の色相（Ｌ、ａ、ｂ値）との変化量（ΔＥ）を算出した。
＜被膜外観＞
電気炉を用いて、１８０℃条件下で、３０分間硬化させた塗膜の外観を評価した。ＰＣＩ評価（パウダーコーティングインスティチュート）による粉体塗膜の平滑性の目視判定用基準板を用いて判定した。
◎：粉体塗料の粒子が、溶融し、平滑な面をしていた（ＰＣＩ評価で６以上）。
○：粉体塗料の粒子は、溶融し、塗膜表面に若干の凹凸があった（ＰＣＩ評価で２〜５）。
△：粉体塗料の粒子は、溶融し、粉体塗料の粒子の原形を保持していなかったが、塗膜表面の凹凸が激しかった（ＰＣＩ評価で１以下）。
×：粉体塗料の粒子が、溶融せず、ある程度の粉体塗料の粒子の原形を保持しており、塗膜表面がざらついていた。
<Hue change>
The coating film was cured at 180 ° C. or 210 ° C. for 30 minutes using an electric furnace. The hue (L, a, b value) of the coating film when thermosetting was performed at each temperature was measured with a color difference meter (manufactured by Konica Minolta, Inc., CR-400). Based on the obtained hue, the amount of change (ΔE) between the hue (L, a, b value) of the coating cured at 180 ° C. and the hue (L, a, b value) of the coating cured at 210 ° C. Calculated.
<Appearance of coating>
Using an electric furnace, the appearance of the coating film cured for 30 minutes at 180 ° C. was evaluated. It judged using the reference | standard board for visual judgment of the smoothness of the powder coating film by PCI evaluation (powder coating institute).
(Double-circle): The particle | grains of the powder coating material fuse | melted and had the smooth surface (6 or more by PCI evaluation).
○: The particles of the powder coating melted and had some unevenness on the surface of the coating film (2 to 5 by PCI evaluation).
Δ: Particles of the powder coating melted and did not retain the original shape of the particles of the powder coating, but the unevenness of the coating film surface was severe (1 or less by PCI evaluation).
X: Particles of the powder coating material did not melt, retained some original shape of the particles of the powder coating material, and the coating film surface was rough.
表１に示されるように、実施例１〜６の粉体塗料組成物を用いて得られた塗膜は、２１０℃で熱硬化させた場合と１８０℃で硬化させた場合とを比較した場合の色相の変化量（ΔＥ）が１．０以下であった。そのため、本発明の粉体塗料組成物を用いて得られた塗膜は、より高温（２１０℃）で熱硬化される場合であっても、色相が維持されることが確認された。 As shown in Table 1, the coating films obtained using the powder coating compositions of Examples 1 to 6 were compared with the case where they were cured at 210 ° C and the case where they were cured at 180 ° C. The amount of change in hue (ΔE) was 1.0 or less. Therefore, it was confirmed that the coating film obtained by using the powder coating composition of the present invention maintains the hue even when it is thermally cured at a higher temperature (210 ° C.).
一方、黄色有機顔料を配合しなかった比較例１の粉体塗料組成物は、色相が大きく変化した。また、黄色有機顔料に代えて耐熱性の優れた金属酸化物系の黄色顔料を配合した比較例２や酸化チタン添加量の少ない比較例３の粉体塗料組成物は、色相を充分に維持することができなかった。また、比較例４では、酸化チタン添加量が多いため、色相は維持されるものの、平滑な膜を形成することができず、外観に問題があった。 On the other hand, the hue of the powder coating composition of Comparative Example 1 in which no yellow organic pigment was blended changed greatly. In addition, the powder coating compositions of Comparative Example 2 in which a metal oxide yellow pigment having excellent heat resistance instead of a yellow organic pigment is blended and Comparative Example 3 having a small amount of titanium oxide added sufficiently maintain the hue. I couldn't. In Comparative Example 4, since the amount of titanium oxide added was large, the hue was maintained, but a smooth film could not be formed, and there was a problem in appearance.
Claims (3)
前記樹脂成分と前記酸化チタンとの配合比率（質量比）は、１００：６０〜１００：１２０であり、
前記黄色有機顔料は、ベンズイミダゾロン系顔料であり、
前記樹脂成分は、エポキシ樹脂と、ポリエステル樹脂とを含む、粉体塗料組成物。 Containing a resin component, titanium oxide, and a yellow organic pigment,
The blending ratio (mass ratio) of the resin component and the titanium oxide, 100: 60-100: Ri 120 der,
The yellow organic pigment is a benzimidazolone pigment,
The said resin component is a powder coating composition containing an epoxy resin and a polyester resin .
樹脂成分と酸化チタンとを配合比率（質量比）が１００：６０〜１００：１２０となるよう含む粉体塗料組成物に、黄色有機顔料をさらに配合し、
前記黄色有機顔料は、ベンズイミダゾロン系顔料であり、
前記樹脂成分は、エポキシ樹脂と、ポリエステル樹脂とを含む、色相維持方法。 It is a hue maintenance method when thermosetting a powder coating composition,
A yellow organic pigment is further blended in a powder coating composition containing a resin component and titanium oxide so that the blending ratio (mass ratio) is 100: 60 to 100: 120 ,
The yellow organic pigment is a benzimidazolone pigment,
The said resin component is a hue maintenance method containing an epoxy resin and a polyester resin .
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