JP6163110B2 - Powder mixed paint and painted parts - Google Patents
Powder mixed paint and painted parts Download PDFInfo
- Publication number
- JP6163110B2 JP6163110B2 JP2014007469A JP2014007469A JP6163110B2 JP 6163110 B2 JP6163110 B2 JP 6163110B2 JP 2014007469 A JP2014007469 A JP 2014007469A JP 2014007469 A JP2014007469 A JP 2014007469A JP 6163110 B2 JP6163110 B2 JP 6163110B2
- Authority
- JP
- Japan
- Prior art keywords
- powder
- paint
- pigment
- polyester resin
- fluororesin
- 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.)
- Active
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- 239000000843 powder Substances 0.000 title claims description 119
- 239000003973 paint Substances 0.000 title claims description 79
- 238000000576 coating method Methods 0.000 claims description 75
- 239000011248 coating agent Substances 0.000 claims description 74
- 239000000049 pigment Substances 0.000 claims description 68
- 229920001225 polyester resin Polymers 0.000 claims description 56
- 239000004645 polyester resin Substances 0.000 claims description 56
- 238000002156 mixing Methods 0.000 claims description 11
- 238000009503 electrostatic coating Methods 0.000 claims description 4
- 229920005989 resin Polymers 0.000 description 28
- 239000011347 resin Substances 0.000 description 28
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 10
- 239000003822 epoxy resin Substances 0.000 description 10
- 239000011737 fluorine Substances 0.000 description 10
- 229910052731 fluorine Inorganic materials 0.000 description 10
- 229920000647 polyepoxide Polymers 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- -1 trifluoroethylene, tetrafluoroethylene, bromotrifluoroethylene, chlorotrifluoroethylene, pentafluoropropylene, hexafluoropropylene Chemical group 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 239000012948 isocyanate Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 239000004606 Fillers/Extenders Substances 0.000 description 5
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000004566 building material Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- 239000002253 acid Substances 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
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 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
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 150000002513 isocyanates Chemical class 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
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000004843 novolac epoxy resin Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 230000003449 preventive effect Effects 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
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-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
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- NFGXHKASABOEEW-UHFFFAOYSA-N 1-methylethyl 11-methoxy-3,7,11-trimethyl-2,4-dodecadienoate Chemical compound COC(C)(C)CCCC(C)CC=CC(C)=CC(=O)OC(C)C NFGXHKASABOEEW-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
- GCVQVCAAUXFNGJ-UHFFFAOYSA-N 2-hexadecylbutanedioic acid Chemical compound CCCCCCCCCCCCCCCCC(C(O)=O)CC(O)=O GCVQVCAAUXFNGJ-UHFFFAOYSA-N 0.000 description 1
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-hydroxyoctadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- BGVYDWVAGZBEMJ-UHFFFAOYSA-N 4-[(4-carbamoylphenyl)diazenyl]-N-(2-ethoxyphenyl)-3-hydroxynaphthalene-2-carboxamide Chemical compound CCOc1ccccc1NC(=O)c1cc2ccccc2c(N=Nc2ccc(cc2)C(N)=O)c1O BGVYDWVAGZBEMJ-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 229920013685 Estron Polymers 0.000 description 1
- DNXHEGUUPJUMQT-CBZIJGRNSA-N Estrone Chemical compound OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 DNXHEGUUPJUMQT-CBZIJGRNSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
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- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
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- 125000005907 alkyl ester group Chemical group 0.000 description 1
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- 125000003368 amide group Chemical group 0.000 description 1
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
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- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000001034 iron oxide pigment Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- YPQKTLPPOXNDMC-UHFFFAOYSA-N isocyanic acid;methylcyclohexane Chemical compound N=C=O.CC1CCCCC1 YPQKTLPPOXNDMC-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- OKRNLSUTBJUVKA-UHFFFAOYSA-N n,n,n',n'-Tetrakis(2-hydroxyethyl)adipamide Chemical compound OCCN(CCO)C(=O)CCCCC(=O)N(CCO)CCO OKRNLSUTBJUVKA-UHFFFAOYSA-N 0.000 description 1
- WNWZKKBGFYKSGA-UHFFFAOYSA-N n-(4-chloro-2,5-dimethoxyphenyl)-2-[[2,5-dimethoxy-4-(phenylsulfamoyl)phenyl]diazenyl]-3-oxobutanamide Chemical compound C1=C(Cl)C(OC)=CC(NC(=O)C(N=NC=2C(=CC(=C(OC)C=2)S(=O)(=O)NC=2C=CC=CC=2)OC)C(C)=O)=C1OC WNWZKKBGFYKSGA-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- XWKBMOUUGHARTI-UHFFFAOYSA-N tricalcium;diphosphite Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])[O-].[O-]P([O-])[O-] XWKBMOUUGHARTI-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- AUTOISGCBLBLBA-UHFFFAOYSA-N trizinc;diphosphite Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])[O-].[O-]P([O-])[O-] AUTOISGCBLBLBA-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Description
本発明は、複数の樹脂粉体塗料を混合してなる粉体混合塗料に関し、特に光沢度を幅広く調整することができる粉体混合塗料に関する。また、本発明は、この粉体混合塗料を使用して塗装した塗装建材などの塗装部材に関する。 The present invention relates to a powder mixed paint obtained by mixing a plurality of resin powder paints, and more particularly to a powder mixed paint capable of widely adjusting glossiness. The present invention also relates to a painted member such as a painted building material coated with the powder mixed paint.
長期間にわたる耐久性が求められるアルミニウム合金製建築外装用材料の表面仕上げには、溶剤系フッ素樹脂塗料が数多く採用されている。しかし、ＶＯＣ排出による環境問題から、近年は、溶剤を含まない粉体塗料が注目されている。 Many solvent-based fluororesin paints are used for surface finishing of aluminum alloy building exterior materials that require long-term durability. However, in recent years, a powder coating containing no solvent has attracted attention due to environmental problems caused by VOC emissions.
粉体塗料を使用してアルミサッシ、アルミカーテンウォール、アルミ方立、アルミ門扉等のアルミ建材に塗装する方法としては、ポリエステル塗料とフッ素塗料をブレンドした粉体塗料を使用して静電塗装することによって塗膜を形成することが行われている（特許文献１〜３参照）。 As a method of applying powder coating to aluminum building materials such as aluminum sashes, aluminum curtain walls, aluminum verticals, and aluminum gates, electrostatic coating is performed using a powder coating blended with polyester paint and fluorine paint. Forming a coating film by doing (refer patent documents 1-3).
粉体塗装塗膜の光沢度の調整の方法としては、粗粒子の体質顔料を添加する方法があるが（特許文献１参照）、この方法では、６０°鏡面反射率（６０°グロス）で５０％以下にするのは困難であり、また多量の体質顔料の添加により、塗膜の物性の劣化が著しい。例えば、体質顔料を３０重量％以上添加すると、塗膜が硬く脆くなり、外観不良や耐水性能、耐候性が著しく低下する。 As a method for adjusting the glossiness of the powder coating film, there is a method of adding extender pigments of coarse particles (see Patent Document 1). In this method, 50 ° specular reflectance (60 ° gloss) is 50. % Or less, and the physical properties of the coating film are significantly deteriorated by the addition of a large amount of extender pigments. For example, when an extender is added in an amount of 30% by weight or more, the coating film becomes hard and brittle, and the appearance defect, water resistance, and weather resistance are remarkably lowered.
特許文献２には、ポリエステル塗料を下地側にリッチに分布させ、フッ素塗料を膜表面側にリッチに分布させたポリエステル・フッ素樹脂塗膜が記載されているが、この方法では、光沢度は２５〜４０％と狭い範囲しか調整できない。 Patent Document 2 describes a polyester / fluorine resin coating film in which a polyester paint is distributed richly on the base side and a fluorine paint is distributed richly on the film surface side. Only a narrow range of ~ 40% can be adjusted.
特許文献３には、相互に異なる種類の硬化剤と組み合わせられた２種類の含フッ素樹脂粒子をドライブレンドして６０°鏡面光沢度を３０〜６０％の範囲に任意で調節する粉体塗料が記載されているが、この方法は、含フッ素樹脂と硬化剤との組み合わせによって光沢度を調整しているにすぎない。 Patent Document 3 discloses a powder coating that dry blends two types of fluorine-containing resin particles combined with different types of curing agents to arbitrarily adjust the 60 ° specular gloss to a range of 30 to 60%. Although described, this method merely adjusts the glossiness by a combination of a fluorine-containing resin and a curing agent.
本発明は、新規な方法で硬化塗膜表面の光沢度を広い範囲で調整することができる粉体塗料、及びこの粉体塗料を使用して塗装した塗装部材を提供することを目的とする。 An object of this invention is to provide the powder coating material which can adjust the glossiness of the cured coating-film surface in the wide range by a novel method, and the coating member coated using this powder coating material.
本発明者は、かかる目的を達成するために鋭意検討した結果、２種類以上の樹脂粉体塗料を使用し、それらの塗料間で顔料体積濃度、顔料の種類、使用樹脂のＳＰ値等を特定の範囲で異ならせることにより、塗料の好適な物性を得ながら広い範囲の光沢度を得ることができることを見出し、本発明の完成に至った。 As a result of intensive studies to achieve this object, the present inventor uses two or more types of resin powder paints, and specifies the pigment volume concentration, the type of pigment, the SP value of the resin used, etc. between these paints. Thus, the inventors found that a wide range of glossiness can be obtained while obtaining suitable physical properties of the paint, and the present invention has been completed.
即ち、本発明は以下の（１）〜（４）の構成を有するものである。
（１）顔料を含むフッ素樹脂粉体塗料と、顔料を含むポリエステル樹脂粉体塗料とを含む２種類以上の粉体塗料をドライブレンドしてなる粉体混合塗料であって、フッ素樹脂粉体塗料に含まれる顔料とポリエステル樹脂粉体塗料に含まれる顔料の種類が異なること、フッ素樹脂粉体塗料に含まれる顔料の体積濃度がポリエステル樹脂粉体塗料に含まれる顔料の体積濃度より５ＰＶＣ％以上高いこと、及びフッ素樹脂とポリエステル樹脂の溶解度パラメータ（ＳＰ値）の差が１．０〜１．５であることを特徴とする粉体混合塗料。
（２）フッ素樹脂粉体塗料に含まれる顔料の体積濃度が２５ＰＶＣ％以下であり、ポリエステル樹脂粉体塗料に含まれる顔料の体積濃度が２０ＰＶＣ％以下であることを特徴とする（１）に記載の粉体混合塗料。
（３）粉体混合塗料が、フッ素樹脂粉体塗料を２０〜４０重量％含み、ポリエステル樹脂粉体塗料を８０〜６０重量％含むことを特徴とする（１）又は（２）に記載の粉体混合塗料。
（４）（１）〜（３）のいずれかに記載の粉体混合塗料を使用して静電塗装及び焼き付けを行なうことにより形成された塗膜を有することを特徴とする塗装部材。
That is, the present invention has the following configurations (1) to (4).
(1) A powder mixed paint obtained by dry blending two or more kinds of powder paints including a pigment-containing fluororesin powder paint and a polyester resin powder paint containing a pigment, the fluororesin powder paint The type of pigment contained in the polyester resin powder coating is different from the type of pigment contained in the polyester resin, and the volume concentration of the pigment contained in the fluororesin powder coating is 5 PVC% or more higher than the volume concentration of the pigment contained in the polyester resin powder coating. And a difference in solubility parameter (SP value) between the fluororesin and the polyester resin is 1.0 to 1.5.
(2) The volume concentration of the pigment contained in the fluororesin powder coating is 25 PVC% or less, and the volume concentration of the pigment contained in the polyester resin powder coating is 20 PVC% or less. Powder mixed paint.
(3) The powder according to (1) or (2), wherein the powder mixed paint contains 20 to 40% by weight of fluororesin powder paint and 80 to 60% by weight of polyester resin powder paint. Body mixed paint.
(4) A coated member having a coating film formed by electrostatic coating and baking using the powder mixed paint according to any one of (1) to (3).
本発明の粉体混合塗料によれば、顔料体積濃度が特定ＰＶＣ％以上異なる樹脂粉体塗料を組み合わせているので、光沢度を幅広い範囲で調整することができる。 According to the powder mixed paint of the present invention, since the resin powder paints having different pigment volume concentrations of specific PVC% or more are combined, the glossiness can be adjusted in a wide range.
フッ素樹脂とポリエステル樹脂とでは、化学的な特性、特にＳＰ値や溶融粘度の相違などに起因して、塗膜を形成する熱硬化過程の際の溶融時にフッ素樹脂成分の方が塗膜表面側に存在し易い。このため、フッ素樹脂粉体塗料とポリエステル樹脂粉体塗料との顔料体積濃度を異ならせることにより、加熱溶融時の粘性挙動が大きく変わり、硬化塗膜の表面粗さを調整することができる。表面粗さが大きい場合は、光の拡散反射により光沢度が低下し、表面粗さが小さい場合は、光の拡散反射により光沢度が増大する。従って、フッ素樹脂粉体とポリエステル樹脂粉体との配合割合及び各々の顔料体積濃度を調整することにより、塗膜の光沢度を幅広く調整することが可能となる。また、粉体塗料を構成する樹脂としてフッ素樹脂とポリエステル樹脂とを使用することにより、塗膜が耐久性の良好なものとなる。 Fluororesin and polyester resin have a fluororesin component on the coating surface side when melted during the thermosetting process to form a coating film due to chemical characteristics, especially differences in SP value and melt viscosity. It is easy to exist in. For this reason, by varying the pigment volume concentration of the fluororesin powder coating and the polyester resin powder coating, the viscosity behavior at the time of heating and melting changes greatly, and the surface roughness of the cured coating film can be adjusted. When the surface roughness is large, the glossiness decreases due to diffuse reflection of light, and when the surface roughness is small, the glossiness increases due to diffuse reflection of light. Therefore, the glossiness of the coating film can be widely adjusted by adjusting the blending ratio of the fluororesin powder and the polyester resin powder and the volume concentration of each pigment. Further, by using a fluororesin and a polyester resin as the resin constituting the powder paint, the coating film has good durability.
本発明の粉体混合塗料は、顔料を含むフッ素樹脂粉体塗料と、顔料を含むポリエステル樹脂粉体塗料とを含む２種類以上の粉体塗料をドライブレンドしてなり、フッ素樹脂粉体塗料に含まれる顔料とポリエステル樹脂粉体塗料に含まれる顔料の種類が異なるものである。特に、本発明の粉体混合塗料は、フッ素樹脂粉体塗料に含まれる顔料の体積濃度がポリエステル樹脂粉体塗料に含まれる顔料の体積濃度より５ＰＶＣ％以上高いこと、及びフッ素樹脂とポリエステル樹脂の溶解度パラメータ（ＳＰ値）の差が１．０〜１．５であることを特徴とする。 The powder mixed paint of the present invention is obtained by dry blending two or more kinds of powder paints including a fluororesin powder paint containing a pigment and a polyester resin powder paint containing a pigment. The pigments contained in the polyester resin powder paint are different in type. In particular, the powder mixed paint of the present invention is such that the volume concentration of the pigment contained in the fluororesin powder paint is 5 PVC% or more higher than the volume concentration of the pigment contained in the polyester resin powder paint, and the fluororesin and polyester resin. The difference in solubility parameter (SP value) is 1.0 to 1.5.
本発明で使用されるフッ素樹脂は、含フッ素モノマーを重合（又は共重合）して得られた含フッ素共重合体であり、常温で固体状の樹脂である。特に、軟化点が５０〜１５０℃のものが好ましい。 The fluororesin used in the present invention is a fluorocopolymer obtained by polymerizing (or copolymerizing) a fluoromonomer, and is a solid resin at room temperature. In particular, a softening point of 50 to 150 ° C. is preferable.
含フッ素モノマーとしては、例えば、フッ化ビニル、フッ化ビニリデン、トリフルオロエチレン、テトラフルオロエチレン、ブロモトリフルオロエチレン、クロロトリフルオロエチレン、ペンタフルオロプロピレン、ヘキサフルオロプロピレン、（パー）フルオロアルキルトリフルオロビニルエーテル〔（パー）フルオロアルキル基の炭素数は、１〜１８個である〕等が代表的なものとして挙げられる。 Examples of the fluorine-containing monomer include vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, bromotrifluoroethylene, chlorotrifluoroethylene, pentafluoropropylene, hexafluoropropylene, and (per) fluoroalkyl trifluorovinyl ether. [(Per) fluoroalkyl group has 1 to 18 carbon atoms] and the like.
フッ素樹脂には、上記の含フッ素モノマー以外の重合性モノマーを共重合させることができる。その重合性モノマーとしては、ビニルエーテル類、オレフィン類、アリルエーテル類、ビニルエステル類、アリルエステル類、（メタ）アクリル酸エステル類、クロトン酸エステル類等が挙げられる。 A polymerizable monomer other than the above-mentioned fluorine-containing monomer can be copolymerized with the fluororesin. Examples of the polymerizable monomer include vinyl ethers, olefins, allyl ethers, vinyl esters, allyl esters, (meth) acrylic acid esters, crotonic acid esters, and the like.
フッ素樹脂は、硬化剤等と反応する反応性部位を有していてもよく、上記含フッ素モノマーや重合性モノマーと共に反応性基含有モノマーとの共重合体であってもかまわない。その反応性基としては、水酸基、カルボキシル基、アミド基、アミノ基、ニトリル基、グリシジル基、イソシアネート基等の官能基が挙げられる。これらの中でも、水酸基を反応性基として使用することが、樹脂の安定性や溶融粘度の制御等の点から好ましい。 The fluororesin may have a reactive site that reacts with a curing agent or the like, and may be a copolymer with a reactive group-containing monomer together with the above-mentioned fluorine-containing monomer or polymerizable monomer. Examples of the reactive group include functional groups such as a hydroxyl group, a carboxyl group, an amide group, an amino group, a nitrile group, a glycidyl group, and an isocyanate group. Among these, it is preferable to use a hydroxyl group as a reactive group from the viewpoints of stability of the resin and control of melt viscosity.
本発明で使用されるポリエステル樹脂は、カルボン酸と多価アルコールとを反応させたものであり、常温で固体状の樹脂である。特に、軟化点が１００〜１５０℃のものが好ましい。 The polyester resin used in the present invention is a resin obtained by reacting a carboxylic acid and a polyhydric alcohol, and is a solid resin at room temperature. In particular, the softening point is preferably 100 to 150 ° C.
ポリエステル樹脂の製造に使用することのできるカルボン酸成分としては、例えば、フタル酸、イソフタル酸、テレフタル酸、ナフタレンジカルボン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバチン酸、１，９−ノナンジカルボン酸、１，１０−デカンジカルボン酸、１，１２−ドデカンジカルボン酸、１，２−オクタデカンジカルボン酸、マレイン酸、フマル酸、シクロヘキサンジカルボン酸、ヘキサヒドロフタル酸、テトラヒドロフタル酸、トリメリット酸、ピロメリット酸等の多価カルボン酸、これらの多価カルボン酸の低級アルキルエステル及びその無水物、あるいはリンゴ酸、酒石酸、１，２−ヒドロキシステアリン酸、パラオキシ安息香酸等のヒドロキシカルボン酸等を挙げることができる。 Examples of the carboxylic acid component that can be used in the production of the polyester resin include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebatin. Acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,2-octadecanedicarboxylic acid, maleic acid, fumaric acid, cyclohexanedicarboxylic acid, hexahydrophthalic acid, tetrahydro Polyvalent carboxylic acids such as phthalic acid, trimellitic acid, pyromellitic acid, lower alkyl esters of these polyvalent carboxylic acids and their anhydrides, or malic acid, tartaric acid, 1,2-hydroxystearic acid, p-hydroxybenzoic acid, etc. Of hydroxycarboxylic acid Kill.
また、ポリエステル樹脂の製造に使用することのできる多価アルコール成分としては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、１，２−プロパンジオール、１，３−プロパンジオール、１，３−ブタンジオール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、１，９−ノナンジオール、１，１０−デカンジオール、ネオペンチルグリコール、スピログリコール、１，１０−デカンジオール、１，４−シクロヘキサンジメタノール、トリメチロールエタン、トリメチロールプロパン、グリセリン、ペンタエリスリトール等を挙げることができる。 Examples of the polyhydric alcohol component that can be used for producing the polyester resin include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, and 1,3-butanediol. 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, spiroglycol, 1,10-decanediol, Examples include 1,4-cyclohexanedimethanol, trimethylolethane, trimethylolpropane, glycerin, pentaerythritol and the like.
本発明で使用する顔料としては、粉体塗料で一般的に使用される着色顔料や体質顔料、光輝顔料、防錆顔料等が使用できる。 As the pigment used in the present invention, a color pigment, an extender pigment, a bright pigment, a rust preventive pigment and the like generally used in powder coatings can be used.
着色顔料としては、例えば、酸化チタン、黄色酸化鉄、チタン黄、ベンガラ等の無機系顔料や、シアニンブルー、シアニングリーン、パーマネントエローＦＧＬ、パーマネントレッドＦ５ＲＫ、カルバゾール、キナクリドンレッド、カーボンブラック等の有機顔料等を挙げることができる。 Examples of the color pigment include inorganic pigments such as titanium oxide, yellow iron oxide, titanium yellow, and red rose, and organic pigments such as cyanine blue, cyanine green, permanent yellow FGL, permanent red F5RK, carbazole, quinacridone red, and carbon black. Etc.
体質顔料としては、例えば、硫酸バリウム、炭酸バリウム、炭酸カルシウム、シリカ、酸化亜鉛、タルク、アルミナ等を挙げることができる。 Examples of extender pigments include barium sulfate, barium carbonate, calcium carbonate, silica, zinc oxide, talc, and alumina.
光輝顔料としては、例えば、アルミニウム粉顔料、ニッケル粉顔料、ステンレス粉顔料、銅粉、ブロンズ粉、金粉、銀粉、雲母顔料、グラファイト顔料、ガラスフレーク顔料、鱗片状酸化鉄顔料等を挙げることができる。 Examples of the bright pigment include aluminum powder pigment, nickel powder pigment, stainless powder pigment, copper powder, bronze powder, gold powder, silver powder, mica pigment, graphite pigment, glass flake pigment, and flaky iron oxide pigment. .
防錆顔料としては、例えば、縮合リン酸カルシウム、リン酸アルミニウム、縮合リン酸アルミニウム、リン酸亜鉛、亜リン酸アルミニウム、亜リン酸亜鉛、亜リン酸カルシウム、モリブデン酸亜鉛、モリブデン酸カルシウム、モリブデン酸マンガン等を挙げることができる。 Examples of rust preventive pigments include condensed calcium phosphate, aluminum phosphate, condensed aluminum phosphate, zinc phosphate, aluminum phosphite, zinc phosphite, calcium phosphite, zinc molybdate, calcium molybdate, and manganese molybdate. Can be mentioned.
本発明においては、フッ素樹脂粉体塗料に含まれる顔料とポリエステル樹脂粉体塗料に含まれる顔料の種類が異なる。このように種類の異なる顔料を使用することにより、同一の種類の顔料を使用する場合と比較して、フッ素樹粉体塗料とポリエステル樹脂粉体塗料の粘性挙動の差を大きくすることができる。 In the present invention, the types of pigments contained in the fluororesin powder coating and the pigments contained in the polyester resin powder coating are different. By using different types of pigments in this way, the difference in the viscous behavior between the fluorine resin powder coating and the polyester resin powder coating can be increased as compared with the case of using the same type of pigment.
また、本発明においては、フッ素樹脂粉体塗料に含まれる顔料の体積濃度（ＰＶＣ％値）をポリエステル樹脂粉体塗料に含まれる顔料の体積濃度（ＰＶＣ％値）より５ＰＶＣ％以上、好ましくは１５〜２０ＰＶＣ％高くすることが特徴である。このように両粉体塗料中の顔料体積濃度を異ならせ、さらにフッ素樹脂粉体塗料とポリエステル樹脂粉体塗料との配合割合及び各々の顔料体積濃度を調整することにより、塗膜の光沢度を幅広く調整することができる。また、従来技術では達成不可能であった、光沢度２５以下の低光沢度で外観が良好な塗膜を得ることができる。 In the present invention, the volume concentration (PVC% value) of the pigment contained in the fluororesin powder coating is 5 PVCC or more, preferably 15% from the volume concentration (PVC% value) of the pigment contained in the polyester resin powder coating. It is characterized by an increase of ˜20 PVC%. Thus, by changing the pigment volume concentration in both powder coating materials, and adjusting the blending ratio of the fluororesin powder coating material and the polyester resin powder coating material and the pigment volume concentration of each, the glossiness of the coating film can be increased. Can be adjusted widely. In addition, it is possible to obtain a coating film having a low glossiness of 25 or less and a good appearance, which cannot be achieved by the prior art.
なお、顔料体積濃度（ＰＶＣ％）は、次式によって求めることができる。
顔料体積濃度＝（顔料の重量（ｇ）／顔料の密度（ｇ／ｃｍ３））／（顔料の重量（ｇ）／顔料の密度（ｇ／ｃｍ３）＋樹脂の重量（ｇ）／樹脂の密度（ｇ／ｃｍ３）＋その他の成分の重量（ｇ）／その他成分の密度（ｇ／ｃｍ３））
The pigment volume concentration (PVC%) can be obtained by the following equation.
Pigment volume concentration = (pigment weight (g) / pigment density (g / cm 3 )) / (pigment weight (g) / pigment density (g / cm 3 ) + resin weight (g) / resin weight Density (g / cm 3 ) + weight of other components (g) / density of other components (g / cm 3 ))
本発明においては、フッ素樹脂粉体塗料中の顔料体積濃度は６〜２５ＰＶＣ％程度であることが好ましく、ポリエステル樹脂粉体塗料中の顔料体積濃度は１〜２０ＰＶＣ％程度であることが好ましい。顔料体積濃度が過度に低いと、着色効果及び光沢度調整効果が乏しくなるおそれがあり、顔料体積濃度が過度に高いと、塗膜の特性が低下するおそれがある。 In the present invention, the pigment volume concentration in the fluororesin powder coating is preferably about 6 to 25 PVC%, and the pigment volume concentration in the polyester resin powder coating is preferably about 1 to 20 PVC%. If the pigment volume concentration is excessively low, the coloring effect and glossiness adjusting effect may be poor, and if the pigment volume concentration is excessively high, the properties of the coating film may be deteriorated.
本発明においては、フッ素樹脂とポリエステル樹脂の溶解度パラメーター（ＳＰ値）の差が、１．０〜１．５である。各樹脂のＳＰ値の差が１．０未満の場合、溶融・硬化し塗膜を形成したときにフッ素樹脂とポリエステル樹脂が相溶化する傾向にあり上層・下層のような層分離が起こりにくく、ＳＰ値の差が１．５を超えると、層分離は起こるものの上層と下層の間での層間剥離や外観不良が懸念される。 In the present invention, the difference in solubility parameter (SP value) between the fluororesin and the polyester resin is 1.0 to 1.5. If the difference in SP value of each resin is less than 1.0, the fluororesin and the polyester resin tend to be compatible when melted and cured to form a coating film, and layer separation such as the upper layer and lower layer hardly occurs, When the difference in SP value exceeds 1.5, there is a concern about delamination and poor appearance between the upper layer and the lower layer although layer separation occurs.
本発明においては、樹脂のＳＰ値の算出は、以下のようにして行う。
樹脂をテトラヒドロフラン（ＴＨＦ）に溶解して２．５重量％溶液とし、その溶液の一定量を分取してその体積をＶＴＨＦ（ｍｌ）とし、それにヘキサン（Ｈｅｘａｎｅ）とイオン交換水（Ｗａｔｅｒ）でそれぞれ滴定を行い、白濁した時点の滴下量（ｍｌ）のＶＨｅｘａｎｅ及びＶＷａｔｅｒをそれぞれ下記の式（１）、（２）に代入して、ＳＰｎとＳＰｈをそれぞれ算出する。次に、得られたＳＰｎとＳＰｈを、式（３）に代入してＳＰ値を求める。
ＳＰｎ＝（ＳＰＴＨＦ×ＶＴＨＦ＋ＳＰＨｅｘａｎｅ×ＶＨｅｘａｎｅ）／（ＶＴＨＦ＋ＶＨｅｘａｎｅ）・・・（１）
ＳＰｈ＝（ＳＰＴＨＦ×ＶＴＨＦ＋ＳＰＷａｔｅｒ×ＶＷａｔｅｒ）／（ＶＴＨＦ＋ＶＷａｔｅｒ）・・・（２）
ＳＰ＝１０＾（（ｌｏｇＳＰｎ＋ｌｏｇＳＰｈ）／２）・・・（３）
（ただし、ＳＰＴＨＦ＝９．５、ＳＰＨｅｘａｎｅ＝７．２、ＳＰＷａｔｅｒ＝２３．４）
In the present invention, the SP value of the resin is calculated as follows.
Dissolve the resin in tetrahydrofuran (THF) to make a 2.5 wt% solution, aliquot a portion of the solution to make the volume VTHF (ml), and add hexane (Hexane) and ion-exchanged water (Water). Titration is performed, and the drop amounts (ml) of VHexane and VWater at the time of cloudiness are substituted into the following formulas (1) and (2), respectively, to calculate SPn and SPh, respectively. Next, the obtained SPn and SPh are substituted into Equation (3) to obtain the SP value.
SPn = (SPTHF × VTHF + SPHexane × VHexane) / (VTHF + VHexane) (1)
SPh = (SPTHF × VTHF + SPWater × VWater) / (VTHF + VWater) (2)
SP = 10 ^ ((logSPn + logSPh) / 2) (3)
(However, SPTHF = 9.5, SPHexane = 7.2, SPWater = 23.4)
本発明の粉体混合塗料は、フッ素樹脂粉体塗料を２０〜４０重量％含み、ポリエステル樹脂粉体塗料を８０〜６０重量％含むことが好ましい。 The powder mixed paint of the present invention preferably contains 20 to 40% by weight of fluororesin powder paint and 80 to 60% by weight of polyester resin powder paint.
本発明の粉体混合塗料は、フッ素樹脂、ポリエステル樹脂、及び顔料の成分に加えて、エポキシ樹脂をさらに含有することができる。このエポキシ樹脂は基材との密着性を向上させるためのものであり、その添加量は、１〜５重量部であることが好ましい。 The powder mixed paint of the present invention can further contain an epoxy resin in addition to the components of the fluororesin, the polyester resin, and the pigment. This epoxy resin is for improving the adhesion to the substrate, and the addition amount is preferably 1 to 5 parts by weight.
本発明で使用されるエポキシ樹脂は、常温で固体状の樹脂であり、特に軟化点が、５０〜１５０℃のものが好ましい。このようなエポキシ樹脂としては、従来からエポキシ樹脂粉体塗料の製造に使用されているエポキシ樹脂を使用することができる。 The epoxy resin used in the present invention is a resin that is solid at room temperature, and particularly preferably has a softening point of 50 to 150 ° C. As such an epoxy resin, an epoxy resin that has been conventionally used for producing an epoxy resin powder coating can be used.
具体的には、例えば、ビスフェノールＡ型ジグリシジルエーテル樹脂や、ビスフェノールＦ型ジグリシジルエーテル樹脂、アミノグリシジルエーテル樹脂、ビスフェノールＡＤ型ジグリシジルエーテル樹脂、ビスフェノールＺ型ジグリシジルエーテル樹脂、Ｏ−クレゾールノボラックエポキシ樹脂、フェノールノボラックエポキシ樹脂、ビフェノールグリシジルエーテル樹脂、シクロペンタジエン骨格エポキシ樹脂、ナフタレン骨格エポキシ樹脂、ＧＭＡアクリル樹脂等、もしくはこれらの樹脂の置換基を他のものに置き換えたもの、例えば、ＣＴＢＮやエステル化等の変性を行ったものが挙げられる。 Specifically, for example, bisphenol A type diglycidyl ether resin, bisphenol F type diglycidyl ether resin, aminoglycidyl ether resin, bisphenol AD type diglycidyl ether resin, bisphenol Z type diglycidyl ether resin, O-cresol novolac epoxy Resin, phenol novolac epoxy resin, biphenol glycidyl ether resin, cyclopentadiene skeleton epoxy resin, naphthalene skeleton epoxy resin, GMA acrylic resin, etc., or those in which substituents of these resins are replaced with others, for example, CTBN or esterification And the like modified.
本発明の粉体混合塗料は、上述の成分に加えて硬化剤をさらに含有することができる。 The powder mixed paint of the present invention can further contain a curing agent in addition to the above-described components.
本発明で使用される硬化剤としては、上記のフッ素樹脂、ポリエステル樹脂、エポキシ樹脂と反応し、架橋結合を形成するものであれば特に限定されることなく、従来使用されている各種の硬化剤を使用することができる。硬化剤は、塗膜硬度や耐加水分解性等の塗膜物性の点からイソシアネート化合物が好ましく、特にブロックイソシアネート化合物が好ましい。 The curing agent used in the present invention is not particularly limited as long as it reacts with the above-mentioned fluororesin, polyester resin, and epoxy resin to form a cross-linking bond, and various conventionally used curing agents. Can be used. The curing agent is preferably an isocyanate compound from the viewpoint of coating film properties such as coating film hardness and hydrolysis resistance, and a blocked isocyanate compound is particularly preferable.
ブロックイソシアネート化合物は、室温で固体のものが好ましい。かかるブロックイソシアネート化合物としては、例えば、脂肪族、芳香族、及び芳香脂肪族のジイソシアネート（例えば、トリレンジイソシアネート、４，４’−ジフェニルメタンイソシアネート、キシリ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、４，４’−メチレンビス（シクロヘキシルイソシアネート）、メチルシクロヘキサンジイソシアネート、ビス（イソシアネートメチル）シクロヘキサン、イソホロンジイソシアネート、ダイマー酸ジイソシアネート、リジンジイソシアネート等）と、活性水素を有する低分子化合物とを反応させて得たポリイソシアネートを、ブロック剤と反応させ、マスキングすることにより製造したものが挙げられる。 The blocked isocyanate compound is preferably a solid at room temperature. Examples of such blocked isocyanate compounds include aliphatic, aromatic, and araliphatic diisocyanates (eg, tolylene diisocyanate, 4,4′-diphenylmethane isocyanate, xylylene diisocyanate, hexamethylene diisocyanate, 4,4′-methylene bis). (Cyclohexyl isocyanate), methylcyclohexane diisocyanate, bis (isocyanate methyl) cyclohexane, isophorone diisocyanate, dimer acid diisocyanate, lysine diisocyanate and the like, and a polyisocyanate obtained by reacting a low molecular compound having active hydrogen with a blocking agent What was manufactured by making it react and masking is mentioned.
他の添加剤としては、一般塗料用添加剤である可塑剤、硬化促進剤、架橋促進触媒、表面調整剤、紫外線吸収剤、光安定剤、酸化防止剤、流動性調整剤、垂れ防止剤及び消泡剤等を使用することができる。 Other additives include general paint additives such as plasticizers, curing accelerators, crosslinking accelerators, surface conditioners, UV absorbers, light stabilizers, antioxidants, fluidity modifiers, sag inhibitors, and An antifoaming agent etc. can be used.
本発明の粉体混合塗料は、上記の顔料含有フッ素樹脂粉体とポリエステル樹脂粉体とをドライブレンドすることにより製造される。また、この粉体混合塗料を使用して静電塗装及び焼き付けを行うことにより、部材上に塗膜を形成することができる。塗膜を形成させる部材（塗装部材）としては、アルミ押出成形材、アルミ板材などのアルミ建材が好適であるが、アルミ以外の金属材、各種の無機材、樹脂材、複合材にも適用可能である。 The powder mixed paint of the present invention is produced by dry blending the above-mentioned pigment-containing fluororesin powder and polyester resin powder. Moreover, a coating film can be formed on a member by performing electrostatic coating and baking using this powder mixed paint. Aluminum building materials such as aluminum extrusion molding materials and aluminum plate materials are suitable as members (coating members) that form the coating film, but can also be applied to metal materials other than aluminum, various inorganic materials, resin materials, and composite materials. It is.
本発明の効果を以下の実施例により具体的に示すが、本発明は、規定した構成要件を逸脱しない限り、以下の実施例に限定されるものではない。なお、実施例及び比較例中の「部」及び「％」は、特に明記のない限り、重量基準である。 The effects of the present invention are specifically shown by the following examples. However, the present invention is not limited to the following examples unless it deviates from the defined constituent requirements. In the examples and comparative examples, “parts” and “%” are based on weight unless otherwise specified.
実施例及び比較例においては、以下の原料を使用した。
＜フッ素樹脂＞
旭硝子（株）社製、商品名ルミフロンＬＦ７１０Ｆ（水酸基含有フッ素樹脂）、溶解度パラメーター８．５８
＜ポリエステル樹脂＞
ポリエステル樹脂１：日本ユピカ（株）社製、商品名ユピカコートＧＶ５７０（水酸基含有ポリエステル樹脂）、溶解度パラメーター９．９９
ポリエステル樹脂２：日本ユピカ（株）社製、商品名ユピカコートＧＶ１５０（水酸基含有ポリエステル樹脂）、溶解度パラメーター９．８８
ポリエステル樹脂３：神東塗料（株）自家合成品（水酸基含有ポリエステル樹脂）、溶解度パラメーター９．１１
ポリエステル樹脂４：神東塗料（株）自家合成品（水酸基含有ポリエステル樹脂）、溶解度パラメーター１０．２５
ポリエステル樹脂５：ダイセル・サイテック（株）社製、商品名ＣＲＹＬＣＯＡＴ ４６４２−３（カルボキシル基含有ポリエステル樹脂）、溶解度パラメーター９．７５
In the examples and comparative examples, the following raw materials were used.
<Fluorine resin>
Asahi Glass Co., Ltd., trade name Lumiflon LF710F (hydroxyl group-containing fluororesin), solubility parameter 8.58
<Polyester resin>
Polyester resin 1: Nippon Iupika Co., Ltd., trade name Iupika Coat GV570 (hydroxyl group-containing polyester resin), solubility parameter 9.99
Polyester resin 2: Nippon Iupika Co., Ltd., trade name Iupika Coat GV150 (hydroxyl group-containing polyester resin), solubility parameter 9.88
Polyester resin 3: Shinto Paint Co., Ltd. in-house synthesized product (hydroxyl group-containing polyester resin), solubility parameter 9.11.
Polyester resin 4: Shinto Paint Co., Ltd. in-house synthetic product (hydroxyl group-containing polyester resin), solubility parameter 10.25
Polyester resin 5: manufactured by Daicel Cytec Co., Ltd., trade name CRYLCOAT 4642-3 (carboxyl group-containing polyester resin), solubility parameter 9.75
＜顔料＞
≪着色顔料≫
酸化チタン：デュポン社製、商品名Ｔｉ−Ｐｕｒｅ Ｒ−７０６
カーボンブラック：三菱化学（株）社製、商品名ＭＡ１００
≪体質顔料≫
アルミニウムシリケート：東洋ファインケミカル（株）社製、商品名ミネックスＥＸ
酸化亜鉛：キクチカラー（株）社製、商品名Ｍ−７０Ｌ
＜エポキシ樹脂＞
ダウ・ケミカル（株）社製、Ｄ．Ｅ．Ｒ．６６２−Ｅ
＜硬化剤＞
ブロックイソシアネート：ε−カプロラクタムブロックイソシアネート エボニック・デグサ社製、商品名ＶＥＳＴＡＧＯＮ Ｂ１５３０
ヒドロキシアルキルアミド：ＥＭＳ社製、商品名Ｐｒｉｍｉｄ ＸＬ−５５２
＜表面調整剤＞
ＥＳＴＲＯＮ社製、商品名ＲｅｓｉｆｌｏｗＰ−６７
<Pigment>
≪Coloring pigment≫
Titanium oxide: DuPont, trade name Ti-Pure R-706
Carbon black: product name MA100, manufactured by Mitsubishi Chemical Corporation
<External pigment>
Aluminum silicate: Toyo Fine Chemical Co., Ltd., trade name Minex EX
Zinc oxide: manufactured by Kikuchi Color Co., Ltd., trade name M-70L
<Epoxy resin>
Manufactured by Dow Chemical Co., Ltd. E. R. 662-E
<Curing agent>
Block isocyanate: ε-caprolactam block isocyanate, manufactured by Evonik Degussa, trade name VESTAGON B1530
Hydroxyalkylamide: Product name Primid XL-552 manufactured by EMS
<Surface conditioner>
Product name Resiflow P-67, manufactured by ESTRON
［実施例１〜９、比較例１〜４］
＜粉体混合塗料の作成＞
表１，２に示される原料及び配合割合に従って各原料をよく混合して溶融混練し、微粉砕を経て分級し、フッ素樹脂粉体塗料（Ｆ−１〜Ｆ−２）及びポリエステル樹脂粉体塗料（Ｐ−１〜Ｐ−５）を得た。得られたフッ素樹脂粉体塗料とポリエステル樹脂粉体塗料を表３，４に記載の組み合わせ及び配合割合に従ってドライブレンドし、実施例１〜９及び比較例１〜４の粉体混合塗料を得た。
[Examples 1 to 9, Comparative Examples 1 to 4]
<Making powder mixed paint>
According to the raw materials and blending ratios shown in Tables 1 and 2, the raw materials are thoroughly mixed, melted and kneaded, classified through fine pulverization, fluororesin powder coating (F-1 to F-2) and polyester resin powder coating. (P-1 to P-5) were obtained. The obtained fluororesin powder paint and polyester resin powder paint were dry blended according to the combinations and blending ratios shown in Tables 3 and 4 to obtain powder mixed paints of Examples 1 to 9 and Comparative Examples 1 to 4. .
＜試験板の作成＞
上記実施例１〜９及び比較例１〜４で作成した各粉体混合塗料について、板厚１．５ｍｍの陽極酸化処理アルミ板を垂直方向に吊り下げ、コロナ帯電式静電粉体塗装機（日本パーカライジング社製ＧＸ−３０４型）を使用して−６０ｋＶの電圧で膜圧６０μｍとなるように静電塗装し、電気炉にて１８０℃×２０分の条件で焼き付けて溶融・硬化を行い、そのまま室温になるまで放冷して試験板を作製した。
その後、以下に記載した各種評価試験を行なった。その結果を表３，４に示す。
<Creation of test plate>
For each of the powder mixed paints prepared in Examples 1 to 9 and Comparative Examples 1 to 4, an anodized aluminum plate having a thickness of 1.5 mm was suspended in the vertical direction, and a corona charging electrostatic powder coating machine ( GX-304 type manufactured by Nihon Parkerizing Co., Ltd.) is applied electrostatically to a film pressure of 60 μm at a voltage of −60 kV, and is baked and melted and cured in an electric furnace at 180 ° C. for 20 minutes. The test plate was produced by allowing to cool to room temperature.
Thereafter, various evaluation tests described below were performed. The results are shown in Tables 3 and 4.
・塗膜外観
塗板作製後の塗膜表面の状態を目視にて判定する。
・光沢値
ＪＩＳ Ｋ ５６００−４−７（鏡面光沢度）に準拠し、光沢計（スガ試験機製ＨＧ−６）にて６０°鏡面光沢度を測定する。
・付着性
ＪＩＳ Ｋ ５６００−５−６（クロスカット法）に準拠し、塗膜を１ｍｍ間隔１００マスで碁盤目にカットし、粘着テープ貼付後のテープ剥離によって塗膜の剥離が生じるかどうかを評価する。
・耐おもり落下性
ＪＩＳ Ｋ ５６００−５−３（デュポン式）に準拠し、撃心１／２吋φ、５００ｇのおもりで落下高５０ｃｍに対する塗膜の抵抗性について、塗膜の割れを評価する。
-Appearance of coating film Visually determine the state of the coating film surface after coating plate preparation.
Gloss value According to JIS K 5600-4-7 (specular gloss), the 60 ° specular gloss is measured with a gloss meter (HG-6 manufactured by Suga Test Instruments).
・ Adhesiveness In accordance with JIS K 5600-5-6 (cross-cut method), whether or not the coating film is peeled off by peeling the tape after applying the adhesive tape after cutting the coating film at 100 squares at 1 mm intervals. evaluate.
・ Weight drop resistance Based on JIS K 5600-5-3 (Du Pont type), the crack of the coating film is evaluated for the resistance of the coating film to a drop height of 50 cm with a weight of 1/2 mm φ and a weight of 500 g. .
表３において、実施例１〜３は、フッ素樹脂粉体塗料の種類とポリエステル樹脂粉体塗料の種類の組合わせを固定して、粉体混合塗料中のフッ素樹脂粉体塗料の割合をそれぞれ２０％、３０％、４０％に変化させた例である。実施例４〜６も、フッ素樹脂粉体塗料の種類とポリエステル樹脂粉体塗料の種類の組合わせを固定して、粉体混合塗料中のフッ素樹脂粉体塗料の割合をそれぞれ２０％、３０％、４０％に変化させた例である。実施例７〜９はそれぞれ、粉体混合塗料中のフッ素樹脂粉体塗料の割合を３０％に固定して、フッ素樹脂粉体塗料の種類とポリエステル樹脂粉体塗料の種類の組合わせを変化させた例である。 In Table 3, Examples 1-3 fixed the combination of the kind of fluororesin powder paint and the kind of polyester resin powder paint, and each set the ratio of the fluororesin powder paint in the powder mixed paint to 20 This is an example of changing to%, 30%, and 40%. In Examples 4 to 6, the combination of the type of fluororesin powder coating and the type of polyester resin powder coating was fixed, and the ratio of the fluororesin powder coating in the powder mixed coating was 20% and 30%, respectively. , 40%. In Examples 7 to 9, the ratio of the fluororesin powder paint in the powder mixed paint is fixed to 30%, and the combination of the fluororesin powder paint type and the polyester resin powder paint type is changed. This is an example.
表４において、比較例１〜３は、フッ素樹脂粉体塗料の種類とポリエステル樹脂粉体塗料の種類の組合わせを固定して、粉体混合塗料中のフッ素樹脂粉体塗料の割合をそれぞれ２０％、３０％、４０％に変化させた例である。比較例４は、粉体混合塗料中のフッ素樹脂粉体塗料の割合を３０％に固定して、ＳＰ値差を変化させた例である。 In Table 4, Comparative Examples 1-3 fixed the combination of the kind of fluororesin powder paint and the kind of polyester resin powder paint, and set the ratio of the fluororesin powder paint in the powder mixed paint to 20 respectively. This is an example of changing to%, 30%, and 40%. Comparative Example 4 is an example in which the SP value difference was changed by fixing the ratio of the fluororesin powder paint in the powder mixed paint to 30%.
表３から明らかなように、実施例１〜９は、塗膜外観、光沢値、付着性、及び耐おもり落下性のいずれについても優れている。特に、実施例１〜３の間の光沢値の比較、及び実施例４〜６の間の光沢値の比較から、フッ素樹脂粉体塗料の種類とポリエステル樹脂粉体塗料の種類の組合わせが同一であっても、粉体塗料の配合割合を変化させることにより、光沢度を幅広い範囲（実施例１〜３の間では、光沢度差２１、実施例４〜６の間では、光沢度差２２）で変化させることができることがわかる。 As is clear from Table 3, Examples 1 to 9 are excellent in all of the coating film appearance, gloss value, adhesion, and weight drop resistance. In particular, from the comparison of the gloss values between Examples 1 to 3 and the comparison of the gloss values between Examples 4 to 6, the combination of the type of fluororesin powder coating and the type of polyester resin powder coating is the same. Even so, by changing the blending ratio of the powder paint, the glossiness can be varied within a wide range (glossiness difference 21 between Examples 1-3, glossiness difference 22 between Examples 4-6). ) Can be changed.
これに対して、表４から明らかなように、比較例１〜３は、フッ素樹脂粉体塗料に含まれる顔料の体積濃度とポリエステル樹脂粉体塗料に含まれる顔料の体積濃度の差が０．８ＰＶＣ％と低いため、フッ素樹脂粉体塗料の種類とポリエステル樹脂粉体塗料の種類の組合わせを固定して、粉体塗料の配合割合を変化させても、光沢度差は１１にすぎず、光沢度を実施例のように幅広い範囲で変化させることができない。また、比較例４は、フッ素樹脂とポリエステル樹脂の溶解度パラメータ（ＳＰ値）の差が大きすぎるため、付着性に劣る。 On the other hand, as is clear from Table 4, in Comparative Examples 1 to 3, the difference between the volume concentration of the pigment contained in the fluororesin powder coating material and the volume concentration of the pigment contained in the polyester resin powder coating material was 0.00. Because it is as low as 8 PVC%, even if the combination of the type of fluororesin powder paint and the type of polyester resin powder paint is fixed and the blending ratio of the powder paint is changed, the gloss difference is only 11, The glossiness cannot be changed in a wide range as in the embodiment. Moreover, since the difference of the solubility parameter (SP value) of a fluororesin and a polyester resin is too large, the comparative example 4 is inferior to adhesiveness.
本発明の粉体混合塗料は、硬化塗膜表面の光沢度を広い範囲で調整することができるため、アルミ建材を含む様々な材料の部材を塗装するために、広く利用できる。 The powder mixed paint of the present invention can be widely used for coating members of various materials including aluminum building materials because the glossiness of the surface of the cured coating film can be adjusted in a wide range.
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