JPS5820987B2 - Thermosetting powder coating composition - Google Patents
Thermosetting powder coating compositionInfo
- Publication number
- JPS5820987B2 JPS5820987B2 JP5294880A JP5294880A JPS5820987B2 JP S5820987 B2 JPS5820987 B2 JP S5820987B2 JP 5294880 A JP5294880 A JP 5294880A JP 5294880 A JP5294880 A JP 5294880A JP S5820987 B2 JPS5820987 B2 JP S5820987B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- resin
- meth
- acrylate
- parts
- 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.)
- Expired
Links
- 239000000843 powder Substances 0.000 title claims description 32
- 239000008199 coating composition Substances 0.000 title claims description 16
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 16
- 229920005989 resin Polymers 0.000 claims description 91
- 239000011347 resin Substances 0.000 claims description 91
- 239000000178 monomer Substances 0.000 claims description 39
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 23
- 229920006026 co-polymeric resin Polymers 0.000 claims description 22
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 13
- 229920000728 polyester Polymers 0.000 claims description 11
- 238000010559 graft polymerization reaction Methods 0.000 claims description 8
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 63
- 238000000576 coating method Methods 0.000 description 50
- 239000011248 coating agent Substances 0.000 description 46
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 45
- -1 isocyanate compounds Chemical class 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 26
- 239000002904 solvent Substances 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 229920001225 polyester resin Polymers 0.000 description 22
- 239000004645 polyester resin Substances 0.000 description 22
- 239000002253 acid Substances 0.000 description 17
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 16
- 239000006185 dispersion Substances 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 15
- 239000000049 pigment Substances 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 14
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 230000007423 decrease Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 8
- 230000000903 blocking effect Effects 0.000 description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000001530 fumaric acid Substances 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 5
- 230000001771 impaired effect Effects 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 238000004383 yellowing Methods 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229930194542 Keto Natural products 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 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 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000010959 steel Substances 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
- 238000005406 washing Methods 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004640 Melamine resin Substances 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 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 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- JBSLOWBPDRZSMB-BQYQJAHWSA-N dibutyl (e)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C\C(=O)OCCCC JBSLOWBPDRZSMB-BQYQJAHWSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007610 electrostatic coating method Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 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
- 230000035484 reaction time Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 description 1
- AKUNSTOMHUXJOZ-UHFFFAOYSA-N 1-hydroperoxybutane Chemical compound CCCCOO AKUNSTOMHUXJOZ-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical class CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- OWHSTLLOZWTNTQ-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS OWHSTLLOZWTNTQ-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- IAVXSALRWMHZKX-UHFFFAOYSA-N C(COCCO)O.C(C)(=O)OCCOCC Chemical class C(COCCO)O.C(C)(=O)OCCOCC IAVXSALRWMHZKX-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical compound [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical class NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- VJECBOKJABCYMF-UHFFFAOYSA-N doxazosin mesylate Chemical compound [H+].CS([O-])(=O)=O.C1OC2=CC=CC=C2OC1C(=O)N(CC1)CCN1C1=NC(N)=C(C=C(C(OC)=C2)OC)C2=N1 VJECBOKJABCYMF-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002954 polymerization reaction product Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Description
【発明の詳細な説明】
本発明は、ポリエステル変性ビニル樹脂と、架橋性共重
合樹脂とからなる熱硬化性粉体塗料組成物に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermosetting powder coating composition comprising a polyester-modified vinyl resin and a crosslinkable copolymer resin.
更に詳しくは、物理性能に優れた、非黄変タイプの熱硬
化性粉体塗料組成物に関する。More specifically, the present invention relates to a non-yellowing type thermosetting powder coating composition with excellent physical performance.
塗料分野において、近年、塗料及び塗装の無公害化ある
いは省資源化が進められ、これに適する塗料として無溶
剤型の粉体塗料が注目を浴び実用化されつつある。In the paint field, in recent years, efforts have been made to make paints and coatings pollution-free and resource-saving, and solvent-free powder paints are attracting attention and being put into practical use as paints suitable for this purpose.
一般に、粉体塗料に使用されている樹脂としては、アク
リル樹脂、ポリエステル樹脂、エポキシ樹脂などが代表
的なものとして知られているが、特に塗膜の平滑性、仕
上り外観、塗膜物性、貯蔵時の安定性（耐ブロッキング
性）などから、アクリル樹脂およびポリエステル樹脂が
好ましいとされている。In general, acrylic resins, polyester resins, epoxy resins, etc. are known as typical resins used in powder coatings. Acrylic resins and polyester resins are preferred from the viewpoint of stability (blocking resistance).
アクリル樹脂が広く使用されている理由としては、前述
した特性もさることながら、アクリル樹脂のもつ耐候性
、硬度付与性、耐汚染性などが挙げられる。The reasons why acrylic resins are widely used include, in addition to the above-mentioned properties, acrylic resins have weather resistance, hardness imparting properties, and stain resistance.
しかし、可撓性、塗膜外観および耐食性の面で難点があ
る。However, it has drawbacks in terms of flexibility, coating appearance, and corrosion resistance.
一方、ポリエステル樹脂は、可撓性、塗膜外観および耐
食性が優れている点が特性として挙げられるが、耐汚染
性などの難点が見られる。On the other hand, polyester resins have excellent flexibility, coating film appearance, and corrosion resistance, but have drawbacks such as stain resistance.
また、これらの樹脂の架橋反応の形式には、自己硬化型
、架橋剤又は硬化剤併用型がある。Further, the types of crosslinking reaction of these resins include a self-curing type and a type using a crosslinking agent or a curing agent.
このような架橋剤又は硬化剤としては二塩基酸、メラミ
ン樹脂、ブロックイソシアネート化合物などが用いられ
ているが、さらに防食性などを補うために、エポキシ樹
脂などが併用されたりする場合もある。Dibasic acids, melamine resins, blocked isocyanate compounds, and the like are used as such crosslinking agents or curing agents, but epoxy resins and the like may also be used in combination to further enhance corrosion resistance.
ところで、架橋剤としてメラミン樹脂を用いた場合、厚
膜に塗装すると焼付は時に発泡（ワキ）が生じるため、
平滑な塗膜が得られないという難点が生じる。By the way, when melamine resin is used as a crosslinking agent, baking may sometimes cause foaming (flanks) when applied to a thick film.
The problem arises that a smooth coating film cannot be obtained.
また、上記の発泡を防ぐためにウレタン（ブロックイン
シアネート化合物）併用系などが用いられているが、こ
れは、高温焼付は時に黄変するという欠点があり、塗膜
外観上、問題があった。Further, in order to prevent the above-mentioned foaming, a combination system of urethane (block in cyanate compound) is used, but this has the drawback of sometimes yellowing when baked at high temperatures, which poses problems in terms of the appearance of the coating film.
又、二塩基酸を用いた場合も同様に、塗膜の耐熱性が劣
るため、オーバーベーク時や高温焼付は時に黄変するこ
とがあった。Similarly, when a dibasic acid is used, the heat resistance of the coating film is also poor, and yellowing may sometimes occur during overbaking or high temperature baking.
本発明はこれらの諸問題点を解決した非黄変タイプで、
しかもワキ及びブロッキングなどの欠点のない光沢、平
滑性及び物理性能などの塗膜性能が優れた熱硬化性粉体
塗料組成物を提供するものである。The present invention is a non-yellowing type that solves these problems.
Moreover, the present invention provides a thermosetting powder coating composition that is free from defects such as wrinkles and blocking and has excellent coating properties such as gloss, smoothness, and physical properties.
即ち、本発明は、
（ＡＸｉ） １〜１０重量％のα・β−不飽和ジカル
ボン酸を構成成分の一つとする、軟化点が４０〜１２０
℃の不飽和ポリエステル樹脂・・・・・・・・・２〜３
０重量％と、
（ｉｉ）（イ）α・β−モノエチレン性不飽和カルボン
酸のヒドロキシアルキルエステル・・・・・・・・・５
〜４０重量％、
（ロ）前記イ）以外のα・β−モノエチレン性不飽和単
量体・・・・・・・・・９５〜６０重量％、から成る単
量体混合物・・・・・・・・・９８〜７０重量％とをグ
ラフト重合して得られる、水酸基価３０〜１８０で、か
つ軟化点が５０〜１３０℃ポリエステル変性ビニル樹脂
・・・・・・・・・５〜９０重量％
（ＢＸａ） α・β−モノエチレン性不飽和カルボン
酸アミドのＮ−アルコキシメチル化単量体・・・・・・
・・・５〜３０重量％、
（ｂ） α・β−モノエチレン性不飽和カルボン酸・
・・・・・・・・０．５〜１０重量％、（ｑ 前記（ａ
）及び（ｂ）以外のα・β−モノエチレン性不飽和単量
体・・・・・・・・・６０〜９０重量％から成る単量体
混合物から得られる軟化点が５０〜１３０℃の架橋性共
重合樹脂・・・・・・・・・９５〜１０重量％
から成る微粉状熱硬化性樹脂粒子よりなる熱硬化性粉体
塗料組成物に関する。That is, the present invention provides (AXi) having a softening point of 40 to 120 and containing 1 to 10% by weight of α/β-unsaturated dicarboxylic acid as one of the constituent components.
Unsaturated polyester resin at °C...2-3
(ii) (a) hydroxyalkyl ester of α/β-monoethylenically unsaturated carboxylic acid 5
~40% by weight, (b) α/β-monoethylenically unsaturated monomer other than the above a) 95 to 60% by weight... ...A polyester-modified vinyl resin with a hydroxyl value of 30 to 180 and a softening point of 50 to 130°C, obtained by graft polymerization of 98 to 70% by weight......5 to 90 Weight% (BXa) N-alkoxymethylated monomer of α/β-monoethylenically unsaturated carboxylic acid amide...
...5-30% by weight, (b) α/β-monoethylenically unsaturated carboxylic acid.
......0.5-10% by weight, (q above (a
) and (b) other than α/β-monoethylenically unsaturated monomers...... monomer mixtures consisting of 60 to 90% by weight with a softening point of 50 to 130°C This invention relates to a thermosetting powder coating composition comprising fine powder thermosetting resin particles comprising 95 to 10% by weight of a crosslinkable copolymer resin.
本発明に使用されるポリエステル変性ビニル樹脂は不飽
和ポリエステル樹脂にα・β−モノエチレン性不飽和単
量体をグラフト重合することによって得られたものであ
り、ポリエステル樹脂のもつ可撓性、塗膜外観の優れて
いる点をビニル樹脂に付与することに特徴がある。The polyester-modified vinyl resin used in the present invention is obtained by graft polymerizing an α/β-monoethylenically unsaturated monomer to an unsaturated polyester resin, and has the flexibility and coating properties of a polyester resin. It is characterized by giving vinyl resin an excellent film appearance.
それ数本発明に使用される不飽和ポリエステル樹脂の原
料として、α・β−不飽和ジカルボン酸を使用すること
が必要である。It is necessary to use α/β-unsaturated dicarboxylic acid as a raw material for the unsaturated polyester resin used in the present invention.
該成分は不飽和ポリエステル樹脂９１〜１０重量％、好
ましくは３〜７重量％の割合で反応せしめることが好ま
しい。It is preferable that the component is reacted with the unsaturated polyester resin in a proportion of 91 to 10% by weight, preferably 3 to 7% by weight.
即ち、該成分が１重量％以下の場合には、ポリエステル
変性ビニル樹脂生成時α・β−モノエチレン性不飽和単
量体に対して十分な量ではなく従ってポリエステル変性
が不十分となり、その結果生成物は不飽和ポリエステル
樹脂とα・β−モノエチレン性不飽和単量体の重合体と
がブレンドされた組成となり、塗膜が白化したりする。That is, if the amount of this component is 1% by weight or less, it will not be a sufficient amount for the α/β-monoethylenically unsaturated monomer when producing the polyester-modified vinyl resin, and therefore the polyester modification will be insufficient. The product has a blended composition of an unsaturated polyester resin and a polymer of α/β-monoethylenically unsaturated monomer, and the coating film may become white.
又架橋性共重合樹脂との反応性の差から、塗膜性能、特
に付着性が低下する傾向を示すので好ましくない。Furthermore, due to the difference in reactivity with the crosslinkable copolymer resin, coating film performance, particularly adhesion, tends to deteriorate, which is not preferable.
一方、該成分が１０重量％以上の場合には、α・β−モ
ノエチレン性不飽和単量体との反応途中でゲル化を伴う
ため好ましくない。On the other hand, if the content of this component is 10% by weight or more, gelation occurs during the reaction with the α/β-monoethylenically unsaturated monomer, which is not preferable.
該α・β−不飽和ジカルボン酸成分の具体例としては、
フマル酸、（無水）マレイン酸、イタコン酸、グルタコ
ン酸、（無水）シトラコン酸等があり、これらは一種も
しくは二種以上の混合物を用いてもよい。Specific examples of the α/β-unsaturated dicarboxylic acid component include:
Examples include fumaric acid, maleic acid (anhydride), itaconic acid, glutaconic acid, and citraconic acid (anhydrous), and these may be used alone or in a mixture of two or more.
本発明に使用される不飽和ポリエステル樹脂の合成にお
いて、前記酸以外のカルボン酸成分を好ましくは２９〜
６９重量％の割合で反応せしめる。In the synthesis of the unsaturated polyester resin used in the present invention, the carboxylic acid component other than the above acid is preferably 29 to
The reaction is carried out at a proportion of 69% by weight.
該成分の具体例としては、（無水）フタル酸、イソフタ
ル酸、テレフタル酸、（無水）トリメリット酸、（無水
）ピロメリット酸、テトラヒドロ（無水）フタル酸、ヘ
キサヒドロ（無水）フタル酸、メチルテトラヒドロ（無
水）フタル酸、メチルへキサヒドロ（無水）フタル酸、
無水ハイミック酸、（無水）コハク酸、アジピン酸、セ
バシン酸、安息香酸、パラ−ターシャリ−ブチル安息香
酸等があり、これらは一種もしくは二種以上の混合物を
用いてもよい。Specific examples of the components include (anhydrous) phthalic acid, isophthalic acid, terephthalic acid, (anhydrous) trimellitic acid, (anhydrous) pyromellitic acid, tetrahydro (anhydrous) phthalic acid, hexahydro (anhydrous) phthalic acid, methyltetrahydro (anhydrous) phthalic acid, methyl hexahydro (anhydrous) phthalic acid,
Examples include hymic anhydride, succinic acid (anhydride), adipic acid, sebacic acid, benzoic acid, para-tertiary-butylbenzoic acid, and these may be used alone or as a mixture of two or more thereof.
本発明に使用される不飽和ポリエステル樹脂の合成に於
ては多価アルコール成分を好ましくは３０〜７０重量％
の割合で反応せしめる。In the synthesis of the unsaturated polyester resin used in the present invention, the polyhydric alcohol component is preferably 30 to 70% by weight.
react at a rate of
該成分の具体例としては、エチレングリコール、ジエチ
レンクリコール、フロピレンゲリコール、ネオペ□ンチ
ルクリコール、シグロピレングリコール、クリセリン、
トリメチロールエタン、トリメチロールプロパン、ペン
タエリスリトール、ジペンタエリスリトール、ブタンジ
オール、ベンタンジオール、ヘキサンジオール、１・４
−シクロヘキサンジメタツール、（水素化）ビスフェノ
ールＡ等があげられる。Specific examples of the ingredients include ethylene glycol, diethylene glycol, phlopyrene gelicol, neopentylic glycol, cyglopylene glycol, chrycerin,
Trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, butanediol, bentanediol, hexanediol, 1.4
-Cyclohexane dimetatool, (hydrogenated) bisphenol A, etc.
これらは一種もしくは二種以上の混合物および必要に応
じて第３級合成飽和脂肪酸のグリシジルエステル（カー
デュラーＥニジエルケミカル社製、商品名）を併用した
ものを用いる。One or a mixture of two or more of these may be used, and if necessary, a glycidyl ester of tertiary synthetic saturated fatty acid (manufactured by Cardular E Nigel Chemical Co., Ltd., trade name) may be used in combination.
その他に、必要に応じて不飽和ポリエステル樹脂の変性
原料としてポリエステル化が可能であって後述する所定
の軟化点、酸価、水酸基価、分子量の各条件を全て満た
すことができる原料であれば使用可能である。In addition, any raw material that can be converted into polyester as a modified raw material for unsaturated polyester resin as needed and that satisfies all of the specified softening point, acid value, hydroxyl value, and molecular weight conditions described below may be used. It is possible.
具体的には石油樹脂、ロジン、フェノール樹脂。Specifically, petroleum resin, rosin, and phenolic resin.
エポキシ樹脂等が例示できる。Examples include epoxy resins.
本発明における不飽和ポリエステル樹脂は、公知の方法
により、１段反応又は多段反応で製造され、その反応方
法に制限はない。The unsaturated polyester resin in the present invention is produced by a single-stage reaction or a multi-stage reaction by a known method, and the reaction method is not limited.
また粉体の製造を湿式法で行う場合には、必要に応じ希
釈剤として後述の重合溶媒を使用することができる。Further, when the powder is produced by a wet method, a polymerization solvent described below can be used as a diluent if necessary.
本発明の不飽和ポリエステル樹脂の軟化点は４０〜１２
０℃、酸価は５０以下（樹脂固形分二以下本発明の酸価
の表示は全て同様とする）、水酸基価は５０〜２５０（
樹脂固形分：以下本発明の水酸基価の表示は全て同様と
する）、分子量は重量平均分子量で８０００〜１２００
００が好ましい。The unsaturated polyester resin of the present invention has a softening point of 40 to 12
0°C, acid value is 50 or less (resin solid content is 2 or less. All acid values in the present invention are indicated in the same manner), hydroxyl value is 50 to 250 (
Resin solid content: (hereinafter, all hydroxyl values in the present invention are expressed in the same way), molecular weight is 8000 to 1200 in weight average molecular weight.
00 is preferred.
尚、重量平均分子量はケルパーミェーションクロマトグ
ラフィー〔東洋曹達■製Ａ３０１型〕により測定した。The weight average molecular weight was measured by Kölpermeation chromatography (Model A301 manufactured by Toyo Soda).
以下、本発明における重量平均分子量は同様に測定した
。Hereinafter, the weight average molecular weight in the present invention was measured in the same manner.
本発明において、前記不飽和ポリエステル樹脂の軟化点
が４０°Ｃより低い場合は、α・β−モノエチレン性不
飽和単量体をグラフト重合した後のポリエステル変性ビ
ニル樹脂の耐ブロッキング性が悪くなり、又、１２０℃
より高い場合には、塗膜とした時の平滑性、鮮映性が損
われる。In the present invention, if the softening point of the unsaturated polyester resin is lower than 40°C, the blocking resistance of the polyester-modified vinyl resin after graft polymerization of the α/β-monoethylenically unsaturated monomer will deteriorate. , also 120℃
If it is higher, the smoothness and sharpness of the film will be impaired.
また、前記不飽和ポリエステル樹脂の酸価が５０以上に
なるとα・β−モノエチレン性不飽和単量体をグラフト
重合した後の、最終塗膜性能に於て耐アルカリ性等が低
下する。Furthermore, if the acid value of the unsaturated polyester resin is 50 or more, the alkali resistance etc. in the final coating film performance after graft polymerization of the α/β-monoethylenically unsaturated monomer will decrease.
また水酸基価が５０より低い場合はα・β−モノエチレ
ン性不飽和単量体をグラフト重合したポリエステル変性
ビニル樹脂と後述する架橋性共重合樹脂との架橋性が不
十分となり易（、また２５０より高い場合には極性基の
増大により得られた塗膜の耐水性が低下する傾向がある
。In addition, if the hydroxyl value is lower than 50, the crosslinkability between the polyester-modified vinyl resin graft-polymerized with an α/β-monoethylenically unsaturated monomer and the crosslinkable copolymer resin described below is likely to be insufficient (and the hydroxyl value is lower than 50). When it is higher, the water resistance of the resulting coating film tends to decrease due to an increase in the number of polar groups.
また重量平均分子量が８０００より低い場合は、ポリエ
ステル樹脂のもつ特性が十分発揮できず、また、１２０
０００以上になるとポリエステル樹脂の分子量が高すぎ
て、α・β−モノエチレン性不飽和単量体をグラフト重
合したポリエステル変性ビニル樹脂が高分子量となりす
ぎて塗膜の平滑性が損われるので好ましくない。In addition, if the weight average molecular weight is lower than 8,000, the properties of the polyester resin cannot be fully exhibited;
If it exceeds 000, the molecular weight of the polyester resin will be too high, and the polyester-modified vinyl resin obtained by graft polymerization of α/β-monoethylenically unsaturated monomer will have too high a molecular weight, which will impair the smoothness of the coating film, which is not preferable. .
本発明におけるポリエステル変性ビニル樹脂は前記不飽
和ポリエステル樹脂に、（イ）α・β−モノエチレン性
不飽和カルボン酸のヒドロキシアルキルエステルと（ロ
）前駆イ）以外のα・β−モノエチレン性不飽和単量体
の１種もしくは２種以上とをグラフト重合させて得られ
たものである。The polyester-modified vinyl resin of the present invention includes (a) a hydroxyalkyl ester of an α/β-monoethylenically unsaturated carboxylic acid and (b) a precursor α/β-monoethylenically unsaturated carboxylic acid other than (a) the unsaturated polyester resin. It is obtained by graft polymerizing one or more saturated monomers.
該ヒト冶キシアルキルエステル単量体は、ポリエステル
変性ビニル樹脂の水酸基価が３０〜１８０になるように
、α・β−モノエチレン性不飽和単量体中５〜４０重量
％、好ましくは８〜３０重量％の範囲で使用する。The human hydroxyalkyl ester monomer is used in an amount of 5 to 40% by weight, preferably 8 to 40% by weight, based on the α/β-monoethylenically unsaturated monomer so that the hydroxyl value of the polyester modified vinyl resin is 30 to 180. It is used in a range of 30% by weight.
該単量体が４０重量％をこえて使用されると、グラフト
重合反応過程におし・てゲル化し易くなる。If the monomer is used in an amount exceeding 40% by weight, gelation tends to occur during the graft polymerization reaction process.
又、得られたポリエステル変性ビニル樹脂は高分子量と
なり、塗膜の平滑性が劣り、しかも架橋性共重合樹脂と
の架橋密度が高くなり過ぎて、塗膜の可撓性、耐水性等
が低下する傾向になり好ましくない。In addition, the resulting polyester-modified vinyl resin has a high molecular weight, resulting in poor coating film smoothness, and the crosslinking density with the crosslinkable copolymer resin becomes too high, resulting in decreased flexibility, water resistance, etc. of the coating film. This is not desirable.
該単量体の具体例としては、２−ヒドロキシエチル（メ
タ）アクリレート、２−ヒドロキシプロピル（メタ）ア
クリレート、３−ヒドロキシプロピル（メタ）アクリレ
ート、２−ヒト狛キシブチル（メタ）アクリレート、３
−ヒドロキシブチル（メタ）アクリレート、４−ヒドロ
キシブチル（メタ）アクリレート、５−ヒドロキシペン
チル（メタ）アクリレート、６−ヒド爾キシヘキシル（
メタ）アクリレート、ネオペンチルグリコールモノ（メ
タ）アクリレート、３−ブトキシ−２−ヒドロキシプロ
ピル（メタ）アクリレート、２−ヒドロキシ−１−フェ
ニルエチル（メタ）アクリレート、ポリプロピレングリ
コールモノ（メタ）アクリレート、グリセリンモノ（メ
タ）アクリレート等があり、これらを一種もしくは二種
以上の混合物として使用してもよい。Specific examples of the monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-human komaxybutyl (meth)acrylate, 3
-Hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (
meth)acrylate, neopentyl glycol mono(meth)acrylate, 3-butoxy-2-hydroxypropyl(meth)acrylate, 2-hydroxy-1-phenylethyl(meth)acrylate, polypropylene glycol mono(meth)acrylate, glycerin mono(meth)acrylate There are meth)acrylates, etc., and these may be used alone or as a mixture of two or more.
また、不飽和ポリエステル樹脂とグラフト重合するため
に使用される前記α・β−モノエチレン性不飽和カルボ
ン酸のヒドロキシアルキルエステル以外の単量体は、単
量体混合物中６０〜９５重量％の範囲で使用する。Furthermore, the monomers other than the hydroxyalkyl ester of the α/β-monoethylenically unsaturated carboxylic acid used for graft polymerization with the unsaturated polyester resin are in the range of 60 to 95% by weight in the monomer mixture. Use with.
該単量体の具体例としては、アクリル酸、メタクリル酸
、イタコン酸、マレイン酸、フマル酸等のα・β−モノ
エチレン性不飽和カルボン酸類：メチル（メタ）アクリ
レート、エチル（メタ）アクリレート、ｎ−プロピル（
メタ）アクリレート、イソプロピル（メタ）アクリレー
ト、ｎ−ブチル（メタ）アクリレート、５ｅｅ−ブチル
（メタ）アクリレート、ｔ−ブチル（メタ）アクリレー
ト、イソブチル（メタ）アクリレート、ｎ−ヘキシル（
メタ）アクリレート、２−エチルヘキシル（メタ）アク
リレート、ｎ−オクチル（メタ）アクリレート、ラウリ
ル（メタ）アクリレート、トリデシル（メタ）アクリレ
ート、ステアリル（メタ）アクリレート等のアクリル酸
又はメタクリル酸のアルキルエステル類：その他Ｎ −
Ｎ’−ジメチルアミンエチル（メタ）アクリレート、グ
リシジル（メタ）アクリレート、シクロヘキシル（メタ
）アクリレート、フェニルメタクリレート、ベンジルメ
タクリレート、フマル酸ジブチルなどのフマル酸のジア
ルキルエステル類、スチレン、ビニルトルエン、α−メ
チルスチレン、（メタ）アクリロニトリル、ビニルアセ
テート等の単量体カ挙げられる。Specific examples of the monomer include α/β-monoethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (
meth)acrylate, isopropyl(meth)acrylate, n-butyl(meth)acrylate, 5ee-butyl(meth)acrylate, t-butyl(meth)acrylate, isobutyl(meth)acrylate, n-hexyl(
Alkyl esters of acrylic acid or methacrylic acid such as meth)acrylate, 2-ethylhexyl(meth)acrylate, n-octyl(meth)acrylate, lauryl(meth)acrylate, tridecyl(meth)acrylate, and stearyl(meth)acrylate: Others N-
Dialkyl esters of fumaric acid such as N'-dimethylamine ethyl (meth)acrylate, glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl methacrylate, benzyl methacrylate, dibutyl fumarate, styrene, vinyltoluene, α-methylstyrene , (meth)acrylonitrile, vinyl acetate, and other monomers.
上記単量体は粉体塗料組成物の使用目的、用途に応じて
１種又は２種以上適宜組合せて使用してもよい。The above monomers may be used alone or in combination of two or more depending on the purpose and use of the powder coating composition.
前記ポリエステル変性ビニル樹脂は、前記不飽和ポリエ
ステル樹脂２〜３０重量％と、前置イ）及び（ロ）のα
・β−モノエチレン性不飽和単量体７０〜９８重量％と
のグラフト重合反応物からなる。The polyester-modified vinyl resin contains 2 to 30% by weight of the unsaturated polyester resin and α in the prefixes a) and (b).
- Consists of a graft polymerization reaction product with 70 to 98% by weight of β-monoethylenically unsaturated monomer.
不飽和ポリエステル樹脂の変性量は、２〜３０重量％で
あり好ましくは、４〜２０重量％が適当である。The amount of modification of the unsaturated polyester resin is 2 to 30% by weight, preferably 4 to 20% by weight.
２重量％より低い場合は、ポリエステル樹脂のもつ可撓
性、塗膜外観に優れている点が十分発揮できず、又３０
重量％以上になると、ビニル樹脂の特性である硬度、耐
汚染性等が損われてくる。If it is less than 2% by weight, the flexibility and excellent coating film appearance of polyester resin cannot be fully demonstrated, and the
If it exceeds % by weight, the properties of vinyl resin such as hardness and stain resistance will be impaired.
本発明のポリエステル変性ビニル樹脂は、通常の溶液重
合、乳化重合、懸濁重合などの方法により製造される。The polyester-modified vinyl resin of the present invention is produced by conventional methods such as solution polymerization, emulsion polymerization, and suspension polymerization.
一般的には、重合温度範囲は約５０〜１５０℃であり、
該温度にもよるが重合反応時間は約４１２時間の範囲で
ある。Generally, the polymerization temperature range is about 50-150°C;
Although it depends on the temperature, the polymerization reaction time is in the range of about 412 hours.
溶液重合法で製造する際に用いられる重合溶媒としては
、例えばメチルアルコール、エチルアルコール、イソプ
ロピルアルコール、ｎ−７”ロピルアルコール等ノアル
コール類、エチレングリコールモノメチルエーテル、エ
チレンクリコールモノエチルエーテル、エチレングリコ
ールモノブチルエーテル、エチレンクリコールモノエチ
ルエーテルアセテート等のエチレングリコール誘導体ニ
ジエチレングリコールモノメチルエーテル、ジエチレン
グリコールモノエチルエーテル、ジエチレングリコール
モノブチルエーテル等のジエチレングリコール誘導体：
酢酸メチル、酢酸エチル、酢酸ブチル等のエステル類：
トルオール、キジロール、芳香族石油ナフサ等の芳香族
炭化水素類：メチルエチルケトン、メチルイソブチルケ
トン等のケトン類等が使用される。Examples of polymerization solvents used in solution polymerization include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and n-7" propyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene. Ethylene glycol derivatives such as glycol monobutyl ether and ethylene glycol monoethyl ether acetate Diethylene glycol derivatives such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether:
Esters such as methyl acetate, ethyl acetate, butyl acetate:
Aromatic hydrocarbons such as toluol, kijirole, aromatic petroleum naphtha, and ketones such as methyl ethyl ketone and methyl isobutyl ketone are used.
これらの重合溶媒は１種又は２種以上を適宜組合せて使
用してもよい。These polymerization solvents may be used alone or in an appropriate combination of two or more.
粉体塗料の製造を湿式法で行う場合には、重合溶媒とし
ては、水可溶性または水混合性溶媒が用いられ、特に水
に対する溶解度が２０℃で１０〜３０重量％程度のもの
が好ましい。When the powder coating is produced by a wet method, a water-soluble or water-miscible solvent is used as the polymerization solvent, and particularly preferably one having a solubility in water of about 10 to 30% by weight at 20°C.
前記重合溶媒の使用量は、ポリエステル変性ビニル樹脂
製造時の不揮発分が１０〜８０重量％、好ましくは２０
〜７０重量％になるような範囲で使用することが好まし
い。The amount of the polymerization solvent used is such that the nonvolatile content during production of the polyester modified vinyl resin is 10 to 80% by weight, preferably 20% by weight.
It is preferable to use it within a range of 70% by weight.
また、使用される重合開始剤としては、例えばベンゾイ
ルパーオキサイド、ｔ−ブチルパーベンゾエート、ｔ−
ブチルヒドロパーオキサイド、クメンヒドロパーオキサ
イド、ジ−ｔ−ブチルパーオキサイド、ｔ−ブチルパー
オクトエート、等の有機過酸化物あるいはアゾビスイソ
ブチロニトリル、アゾジイソ酪酸ニトリルなどのアゾ化
合物が挙げられる。In addition, examples of the polymerization initiator used include benzoyl peroxide, t-butyl perbenzoate, t-
Examples thereof include organic peroxides such as butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, and t-butyl peroctoate, and azo compounds such as azobisisobutyronitrile and azodiisobutyric acid nitrile.
これら重合開始剤の１種もしくは２種以上を適宜混合し
て使用してもよい。These polymerization initiators may be used alone or in an appropriate mixture of two or more.
該重合開始剤は、ポリエステル変性ビニル樹脂製造時の
不揮発分に対して約０．１〜１５重量％の範囲で使用す
る。The polymerization initiator is used in an amount of about 0.1 to 15% by weight based on the nonvolatile content during production of the polyester-modified vinyl resin.
必要ならば、分子量を調整するために連鎖移動剤、例え
ばドデシルメルカプタン、チオグリコール酸−２−エチ
ルヘキシル、四塩化炭素管ヲ使用してもよい。If necessary, chain transfer agents such as dodecyl mercaptan, 2-ethylhexyl thioglycolate, carbon tetrachloride may be used to adjust the molecular weight.
該連鎖移動剤は、ポリエステル変性ビニル樹脂製造時の
不揮発分に対して約０〜５重量％の範囲で使用すること
が好ましい。The chain transfer agent is preferably used in an amount of about 0 to 5% by weight based on the nonvolatile content during production of the polyester-modified vinyl resin.
本発明のポリエステル変性ビニル樹脂の水酸基価は３０
〜１８０、好ましくは５０〜１５０の範囲のものであり
、酸価は５〜３０、好ましくは７〜２７の範囲にあるこ
とが好ましい。The hydroxyl value of the polyester modified vinyl resin of the present invention is 30
-180, preferably 50-150, and the acid value is preferably in the range 5-30, preferably 7-27.
酸価が５より小さくなると熱硬化性が不足するため、塗
膜の硬度、耐水性、耐食性、耐久性等が劣り、他方酸価
が３０より大きくなると塗膜性能特に耐アルカリ性が低
下する。When the acid value is less than 5, the thermosetting property is insufficient, resulting in poor hardness, water resistance, corrosion resistance, durability, etc. of the coating film, while on the other hand, when the acid value is greater than 30, the coating film performance, particularly the alkali resistance, decreases.
また、水酸基価が３０以下の場合、架橋密度が少なくな
り、耐溶剤性が低下する。Moreover, when the hydroxyl value is 30 or less, the crosslinking density decreases and the solvent resistance decreases.
一方１８０より大きい場合、可撓性が低下し、耐水性が
低下するようになる。On the other hand, if it is larger than 180, the flexibility and water resistance will decrease.
本発明のポリエステル変性ビニル樹脂の重量平均分子量
は１００００〜１１０００、好ましくは。The weight average molecular weight of the polyester-modified vinyl resin of the present invention is preferably 10,000 to 11,000.
２００００〜９００００の範囲内にあることが好ましい
。It is preferably within the range of 20,000 to 90,000.
重量平均分子量が１００００以下の場合は塗膜性能及び
粉体塗料の耐ブロッキング性が十分でなくなり、一方重
量平均分子量が１１００００以上の場合は、塗膜の平滑
性が損われ、好ましくない。If the weight average molecular weight is less than 10,000, the coating performance and blocking resistance of the powder coating will be insufficient, while if the weight average molecular weight is more than 110,000, the smoothness of the coating will be impaired, which is not preferable.
本発明のポリエステル変性ビニル樹脂は、軟化点が５０
〜１３０℃、好ましくは６５〜１１０℃のものである。The polyester modified vinyl resin of the present invention has a softening point of 50
-130°C, preferably 65-110°C.
軟化点が５０℃より低くなると、粉体塗料の耐ブロッキ
ング性が低下し、１３０℃より高くなると、塗膜の平滑
性が劣るのでいずれも好ましくない。If the softening point is lower than 50°C, the blocking resistance of the powder coating will decrease, and if it is higher than 130°C, the smoothness of the coating film will be poor, so both are not preferred.
次に、本発明に使用される架橋性共重合樹脂を構成する
α・β−モノエチレン性不飽和単量体混合物としてα・
β〜モノエチレン性不飽和カルボン酸アミドのＮ−アル
コキシメチル化単量体を必須成分として使用するが、該
成分は、ポリエステル変性ビニル樹脂との架橋反応に必
要である。Next, as the α/β-monoethylenically unsaturated monomer mixture constituting the crosslinkable copolymer resin used in the present invention,
An N-alkoxymethylated monomer of β to monoethylenically unsaturated carboxylic acid amide is used as an essential component, and this component is necessary for the crosslinking reaction with the polyester-modified vinyl resin.
醸成分は架橋性共重合樹脂中５〜３０重量％、好ましく
は１０〜２５重量％の割合で反応せし：り。The brewing component is reacted with the crosslinkable copolymer resin in a proportion of 5 to 30% by weight, preferably 10 to 25% by weight.
該成分が５重量％以下の場合には、ポリエ アル変性ビ
ニル樹脂との架橋反応が不十分となり、耐溶剤性が低下
する。If the content of this component is 5% by weight or less, the crosslinking reaction with the polyal-modified vinyl resin will be insufficient, resulting in a decrease in solvent resistance.
また３０重量％以上になると架橋性共重合樹脂の製造時
にゲル化を伴うため好ましくない。Moreover, if it exceeds 30% by weight, gelation occurs during the production of the crosslinkable copolymer resin, which is not preferable.
該成分の具体例としては、Ｎ−メトキシメチル（メタ）
アクリルアミド、Ｎ−エトキシメチル（メタ）アクリル
アミド、Ｎ−ｎ−プロポキシメチル（メタ）アクリルア
ミド、Ｎ−インプロポキシメチル（メタ）アクリルアミ
ド、Ｎ−ｎ−ブトキシメチル（メタ）アクリルアミド、
Ｎ５ｅｅ−ブトキシメチル（メタ）アクリルアミド、Ｎ
−ｔ−ブトキシメチル（メタ）アクリルアミド、Ｎ−イ
ソブトキシメチル（メタ）アクリルアミド、等のα・β
−モノエチレン性不飽和カルボン酸アミドのＮ−アルコ
キシメチル化物：あるいはこれらのＮ−メチロール化物
などが挙げられ、これらは１種もしくは２種以上の混合
物として用いてもよい。Specific examples of this component include N-methoxymethyl (meth)
Acrylamide, N-ethoxymethyl (meth)acrylamide, N-n-propoxymethyl (meth)acrylamide, N-impropoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide,
N5ee-butoxymethyl(meth)acrylamide, N
-α/β of t-butoxymethyl (meth)acrylamide, N-isobutoxymethyl (meth)acrylamide, etc.
- N-alkoxymethylated products of monoethylenically unsaturated carboxylic acid amide: or N-methylolated products thereof, and the like, and these may be used alone or as a mixture of two or more.
本発明においては架橋性共重合樹脂の一成分としてα・
β−モノエチレン性不飽和カルボン酸を０．５〜１０重
量％の範囲で使用する。In the present invention, α-
β-monoethylenically unsaturated carboxylic acid is used in a range of 0.5 to 10% by weight.
該単量体は架橋性共重合樹脂とポリエステル変性ビニル
樹脂との相溶性を向上させるとともに架橋反応を促進す
る効果を有する。The monomer has the effect of improving the compatibility between the crosslinkable copolymer resin and the polyester-modified vinyl resin and promoting the crosslinking reaction.
前記範囲において０．５重量％にみたない場合はその効
果が弱くなり、又１０重量％をこえると硬化塗膜の性能
を低下させるようになるので好ましくない。If the amount is less than 0.5% by weight within the above range, the effect will be weakened, and if it exceeds 10% by weight, the performance of the cured coating film will deteriorate, which is not preferable.
該成分の具体例としては、アクリル酸、メタクリル酸、
クロトン酸、イタコン酸、マレイン酸、フマル酸等が挙
げられ、これらは１種もしくは２種以上の混合物として
用いてもよい。Specific examples of the component include acrylic acid, methacrylic acid,
Examples include crotonic acid, itaconic acid, maleic acid, fumaric acid, etc., and these may be used alone or as a mixture of two or more.
本発明に使用される架橋性共重合樹脂の原料として前記
以外のα・β−モノエチレン性不飽和単量体を６０〜９
０重量％の割合で反応せしめる。As a raw material for the crosslinkable copolymer resin used in the present invention, 60 to 9 α/β-monoethylenically unsaturated monomers other than those mentioned above are used.
The reaction is carried out at a ratio of 0% by weight.
該成分の具体例としては、メチル（メタ）アクリレート
、エチル（メタ）アクリレート、ｎ−プロピル（メタ）
アクリレート、イソプロピル（メタ）アクリレート、ｎ
−ブチル（メタ）アクリレート、５ｅｃ−ブチル（メタ
）アクリレート、ｔ−ブチル（メタ）アクリレート、イ
ンブチル（メタ）アクリレート、ｎ−ヘキシル（メタ）
アクリレート、２−エチルヘキシル（メタ）アクリレー
ト、ｎ−オクチル（メタ）アクリレート、ラウリル（メ
タ）アクリレート、トリデシル（メタ）アクリレート、
ステアリル（メタ）アクリレート等のアクリル酸又はメ
タクリル酸のアルキルエステル類：２−ヒドロキシエチ
ル（メタ）アクリレート、２−ヒドロキシプロピル（メ
タ）アクリレート、３−ヒドロキシプロピル（メタ）ア
クリレート、２−ヒドロキシブチル（メタ）アクリレー
ト、３−ヒドロキシブチル（メタ）アクリレート、４−
ヒドロキシブチル（メタ）アクリレート、５−ヒドロキ
シペンチル（メタ）アクリレート、６−ヒドロキシヘキ
シル（メタ）アクリレート、ネオペンチルグリコールモ
ノ（メタ）アクリレート、３−ブトキシ−２−ヒドロキ
シプロピル（メタ）アクリレート、２−ヒドロキシ−１
−フェニルエチル（メタ）アクリレート、ポリプロピレ
ングリコールモノ（メタ）アクリレート、グリセリンモ
ノ（メタ）アクリレート等のα・β−モノエチレン性不
飽和カルボン酸のヒドロキシアルキルエステル類：その
他Ｎ−Ｎ′−ジメチルアミノエチル（メタ）アクリレー
ト、グリシジル（メタ）アクリレート、シクロヘキシル
（メタ）アクリレート、フェニルメタクリレート、ベン
ジルメタクリレート、フマル酸ジ−ブチルなどのフマル
酸ジ−アルキルエステル類、スチレン、ビニルトルエン
、α−メチルスチレン、（メタ）アクリロニトリル、ビ
ニルアセテート等の単量体が挙げられる。Specific examples of this component include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate,
acrylate, isopropyl (meth)acrylate, n
-Butyl (meth)acrylate, 5ec-butyl (meth)acrylate, t-butyl (meth)acrylate, inbutyl (meth)acrylate, n-hexyl (meth)acrylate
Acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate,
Alkyl esters of acrylic acid or methacrylic acid such as stearyl (meth)acrylate: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, etc. ) acrylate, 3-hydroxybutyl (meth)acrylate, 4-
Hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, neopentyl glycol mono(meth)acrylate, 3-butoxy-2-hydroxypropyl (meth)acrylate, 2-hydroxy -1
-Hydroxyalkyl esters of α/β-monoethylenically unsaturated carboxylic acids such as phenylethyl (meth)acrylate, polypropylene glycol mono(meth)acrylate, glycerin mono(meth)acrylate: Other N-N'-dimethylaminoethyl Fumaric acid dialkyl esters such as (meth)acrylate, glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl methacrylate, benzyl methacrylate, dibutyl fumarate, styrene, vinyltoluene, α-methylstyrene, (meth) ) Examples include monomers such as acrylonitrile and vinyl acetate.
上記単量体は粉体塗料組成物の使用目的、用途に応じて
１種又は２種以上適宜組合せて使用しても差支えない。The above monomers may be used alone or in an appropriate combination of two or more depending on the purpose and use of the powder coating composition.
本発明の架橋性共重合樹脂は通常の溶液重合、乳化重合
、懸濁重合などの方法により製造される。The crosslinkable copolymer resin of the present invention is produced by conventional methods such as solution polymerization, emulsion polymerization, and suspension polymerization.
溶液重合法で製造する際に用いられる重合溶媒としては
、前述した重合溶媒が用いられる。As the polymerization solvent used when manufacturing by the solution polymerization method, the above-mentioned polymerization solvent is used.
粉体塗料の製造を湿式法で行う場合には、重合溶媒とし
ては、前述した水可溶性または水混合性溶媒が用いられ
る。When producing a powder coating by a wet method, the above-mentioned water-soluble or water-miscible solvent is used as the polymerization solvent.
また、使用される重合開始剤も前述した有機過酸化物あ
るいはアゾ化合物が用いられる。Further, the polymerization initiator used is the above-mentioned organic peroxide or azo compound.
分子量を調整するために前述した連鎖移動剤を使用する
こともできる。The chain transfer agents mentioned above can also be used to adjust the molecular weight.
該架橋性共重合樹脂製造時の重合温度は約５０〜１５０
℃、反応時間は約４〜１２時間であり、その際使用され
る重合溶媒は、前記樹脂製造時の不揮発分が１０〜８０
重量％、好ましくは３５〜７５重量％になるような範囲
で１使用する。The polymerization temperature during production of the crosslinkable copolymer resin is about 50 to 150
℃, the reaction time is about 4 to 12 hours, and the polymerization solvent used at that time has a nonvolatile content of 10 to 80
% by weight, preferably 35 to 75% by weight.
又、重合開始剤の使用量は、架橋性共重合樹脂製造時の
不揮発分に対して約０．１〜１５重量％の範囲であり、
連鎖移動剤は同時に約０〜５重量％の範囲で用いること
が好ましい。Further, the amount of the polymerization initiator used is in the range of about 0.1 to 15% by weight based on the nonvolatile content during production of the crosslinkable copolymer resin,
The chain transfer agent is preferably used at the same time in a range of about 0 to 5% by weight.
本発明の架橋性・共重合樹脂の重量平均分子量は１００
００〜１０００００好ましくは２００００〜８００００
の範囲内にあることが好ましい。The weight average molecular weight of the crosslinkable copolymer resin of the present invention is 100
00-100000 preferably 20000-80000
It is preferable that it is within the range of .
重量平均分子量が１００００以下の場合は、塗膜性能が
十分でなく、一方重量平均分子量が１０００００以上の
場合は、塗膜の平滑性が損われるようになる。If the weight average molecular weight is 10,000 or less, the coating film performance will be insufficient, while if the weight average molecular weight is 100,000 or more, the smoothness of the coating film will be impaired.
本発明の架橋性共重合樹脂は、軟化点が５０〜１３０℃
、好ましくは６５〜１００℃のものである。The crosslinkable copolymer resin of the present invention has a softening point of 50 to 130°C.
, preferably 65 to 100°C.
軟化点が５０℃より低くなると粉体塗料の耐ブロッキン
グ性が低下し、１３０℃より高くなると塗膜の平滑性が
劣るので、いずれも好ましくない。If the softening point is lower than 50°C, the blocking resistance of the powder coating will decrease, and if it is higher than 130°C, the smoothness of the coating film will be poor, so both are not preferred.
本発明においてポリエステル変性ビニル樹脂と架橋性共
重合樹脂とは重量比で５／９５〜９０／１０の割合で使
用される。In the present invention, the polyester modified vinyl resin and the crosslinkable copolymer resin are used in a weight ratio of 5/95 to 90/10.
好ましくは１０／９０〜７０／３０である。Preferably it is 10/90 to 70/30.
該範囲において架橋性共重合樹脂が１０重量％より少な
くなれば塗膜の架橋性が不足し、耐溶剤性、耐薬品性等
が低下する傾向になり、一方、該架橋性共重合樹脂が９
５重量％より多くなれば、ポリエステル変性ビニル樹脂
量が少なくなり、本発明の特徴であるポリエステル樹脂
のもつ可撓性、塗膜外観及び耐食性が優れる点などが損
われる。If the crosslinkable copolymer resin is less than 10% by weight within this range, the crosslinkability of the coating film will be insufficient, and solvent resistance, chemical resistance, etc. will tend to decrease;
If it exceeds 5% by weight, the amount of polyester-modified vinyl resin decreases, and the characteristics of the present invention, such as the excellent flexibility, coating appearance, and corrosion resistance of the polyester resin, are impaired.
次に、本発明の熱硬化性粉体塗料組成物を製造するに際
しては、ポリエステル変性ビニル樹脂と架橋性共重合樹
脂との混合物には、必要に応じて公知の硬化促進剤、さ
らにエポキシ樹脂、セルロース系樹脂、アミン樹脂、ポ
リエステル樹脂、ブロックイソシアネート化合物などの
１種もしくは２種以上の塗膜形成樹脂、及び顔料、・・
ジキ防止剤、塗面調整剤などを添加できる。Next, when producing the thermosetting powder coating composition of the present invention, the mixture of the polyester-modified vinyl resin and the crosslinkable copolymer resin is added with a known curing accelerator, if necessary, and an epoxy resin, One or more coating film-forming resins such as cellulose resins, amine resins, polyester resins, blocked isocyanate compounds, and pigments...
Anti-jerk agents, coating surface conditioners, etc. can be added.
該製造方法としては、通常の溶融機械粉砕法及び湿式製
造法が挙げられる。Examples of the manufacturing method include a conventional melt mechanical grinding method and a wet manufacturing method.
溶融機械粉砕法としては、前記各成分〔（Ａ）及び（Ｂ
）成分〕を溶融温度８０〜１１０℃程度で充分に溶融混
練し、これを冷却後粉砕して製造する。As the melt mechanical pulverization method, each of the above components [(A) and (B
) components] are sufficiently melt-kneaded at a melting temperature of about 80 to 110°C, cooled, and then pulverized.
溶融装置としては加熱ロール、加熱ニーダ−、エクスト
ルーダー等が具体例として例示出来る。Specific examples of the melting device include heating rolls, heating kneaders, extruders, and the like.
また、本発明の熱硬化性粉体塗料組成物は、以下に述べ
る如き湿式製造方法によって有利に製造することができ
る。Further, the thermosetting powder coating composition of the present invention can be advantageously produced by a wet production method as described below.
まず、重合溶媒として水可溶性又は水混合性溶剤を用い
て合成した所定量の前記ポリエステル変性ビニル樹脂と
架橋性共重合樹脂との混合樹脂組成物と必要に応じ硬化
触媒、ハジキ防止剤、塗面調整剤及び他の塗膜形成樹脂
等を前記水可溶性溶剤又は水混合性溶剤に溶解して樹脂
溶液とし、さらに必要ならば顔料を加え、練合分散して
顔料分散液とする。First, a mixed resin composition of a predetermined amount of the polyester-modified vinyl resin and a crosslinkable copolymer resin synthesized using a water-soluble or water-miscible solvent as a polymerization solvent, a curing catalyst, an anti-cissing agent, and a coating surface as necessary. A modifier and other coating film-forming resins are dissolved in the water-soluble or water-miscible solvent to obtain a resin solution, and if necessary, a pigment is added and kneaded and dispersed to obtain a pigment dispersion.
この際使用される溶剤は前記溶液重合法に用いられる重
合溶媒と同じものが用いられる。The solvent used in this case is the same as the polymerization solvent used in the solution polymerization method.
また、その使用量は前記樹脂溶液もしくは顔料分散液の
不揮発分が３０〜７０重量％の範囲になるような割合で
使用する。The amount used is such that the nonvolatile content of the resin solution or pigment dispersion is in the range of 30 to 70% by weight.
ついで、この樹脂溶液又は顔料分散液を、その中に含ま
れる水可溶性溶剤又は水混合性溶剤のすべてが溶解する
量の水中に微粒状に乳化する。Next, this resin solution or pigment dispersion is emulsified into fine particles in water in an amount such that all of the water-soluble or water-miscible solvent contained therein is dissolved.
この際使用される水の量は前記樹脂溶液もしくは顔料分
散液の少くとも６倍量（重量）であり、乳化後の口過工
程を考慮すれば、約４０倍量（重量）以下が好ましい。The amount of water used at this time is at least 6 times the amount (by weight) of the resin solution or pigment dispersion, and is preferably about 40 times the amount (by weight) or less in consideration of the mouth-passing step after emulsification.
また、前記樹脂溶液又は顔料分散液の乳化は激しい攪拌
下にある水中に前記溶液又は分散液を滴下、注入、噴霧
等を行う方法、水と前記溶液又は分散液をラインミキサ
ーで混合する方法等が使用できるが、この時攪拌により
混合液の温度が上昇し、樹脂の軟化により樹脂粒子同志
が合体ないしは一体化し、粗大化するのを防ぐためにも
混合液を冷却して液温を３０℃以下に保つことが好まし
い。The resin solution or pigment dispersion can be emulsified by dropping, pouring, or spraying the solution or dispersion into water under vigorous stirring, or by mixing water and the solution or dispersion using a line mixer. However, at this time, the temperature of the mixed liquid increases due to stirring, and in order to prevent the resin particles from coalescing or becoming integrated due to the softening of the resin and becoming coarse, the mixed liquid must be cooled to keep the liquid temperature below 30°C. It is preferable to keep it at
前記攪拌もしくはラインミキサーでの混合は、乳濁微粒
子中の溶剤が水中に移行し、樹脂粒子が形成される迄行
う。The stirring or mixing using a line mixer is carried out until the solvent in the emulsion particles is transferred to water and resin particles are formed.
かくして乳濁微粒子中の溶剤が水中に抽出され、樹脂粒
子が得られる。In this way, the solvent in the emulsion fine particles is extracted into water, and resin particles are obtained.
この樹脂粒子を沢過又は遠心分離等により水−溶剤混合
物と分離し、さらに必要ならば水洗及び分離を必要回数
繰り返し、含水ケーキ状の樹脂粒子を得る。The resin particles are separated from the water-solvent mixture by filtering or centrifugation, and if necessary, water washing and separation are repeated a necessary number of times to obtain water-containing cake-like resin particles.
更に該含水ケーキ状の樹脂粒子を温風（３０〜４０℃）
乾燥して乾燥樹脂粒子を得る。Furthermore, the water-containing cake-like resin particles are heated with hot air (30 to 40°C).
Dry to obtain dry resin particles.
このようにして、好ましくは、平均粒子径１〜１００μ
の間の微粉状熱硬化性樹脂粒子を得る。In this way, preferably an average particle size of 1 to 100μ
Finely powdered thermosetting resin particles are obtained.
更に必要ならば、粉砕機を用いて微粉砕することも可能
である。Furthermore, if necessary, it is also possible to finely pulverize it using a pulverizer.
か（して得られた本発明の樹脂粒子は、一個の粒子中に
ポリエステル変性ビニル樹脂と架橋性共重合樹脂を含有
する。The resin particles of the present invention obtained in this manner contain a polyester-modified vinyl resin and a crosslinkable copolymer resin in one particle.
つまり一個の粒子中に、加熱することにより相互に反応
する基、即ち水酸基とＮ−アルコキシメチル基を必ず含
有する。That is, each particle necessarily contains groups that react with each other when heated, that is, a hydroxyl group and an N-alkoxymethyl group.
従つ４て本発明の組成物は加熱することにより樹脂粒子
中での架橋及び樹脂粒子同志の架橋反応で優れた性能を
有する塗膜が得られるのである。Therefore, when the composition of the present invention is heated, a coating film having excellent performance can be obtained through crosslinking in the resin particles and crosslinking reaction between the resin particles.
本発明の熱硬化性粉体塗料組成物は、粉末静電塗装法、
流動浸漬法などによって被塗物に塗布することが出来る
。The thermosetting powder coating composition of the present invention can be applied by powder electrostatic coating method,
It can be applied to the object by a fluidized dipping method or the like.
該組成物は、従来の粉体塗料に比べて、低温焼付で充分
な塗膜性能及び塗膜外観（平滑性、鮮映性）が得られる
ので、用途として自動車、家電器具、鋼製家具等の塗装
に最適である。Compared to conventional powder coatings, this composition can provide sufficient coating performance and coating appearance (smoothness, sharpness) when baked at low temperatures, so it can be used in automobiles, home appliances, steel furniture, etc. Ideal for painting.
また、屋外で使用されるアンテナ、フェンス、門Ｊ％な
どの鉄製構造物などにも使用できる。It can also be used for antennas, fences, gates, and other iron structures used outdoors.
該組成物の塗装後の加熱硬化条件は、該組成物中の架橋
性官能基の含有量、膜厚などにより異なるが、通常１４
０〜２３０℃の温度範囲の適当な温度で１０〜４０分加
熱処理することにより硬化塗膜とすることが出来る。The heat curing conditions after coating the composition vary depending on the content of crosslinkable functional groups in the composition, film thickness, etc., but usually 14
A cured coating film can be obtained by heat treatment at an appropriate temperature in the temperature range of 0 to 230°C for 10 to 40 minutes.
該組成物は、前述した通り、従来の粉体塗料に比べて低
温で充分硬化させることが出来る。As mentioned above, this composition can be sufficiently cured at a lower temperature than conventional powder coatings.
また、高温で焼付ける場合には短時間で充分な塗膜性能
及び塗膜外観が得られる。In addition, when baking at a high temperature, sufficient coating performance and coating appearance can be obtained in a short time.
例えば、１４０〜１７０℃の場合約２０〜３０分、２０
０〜２３０℃の場合に約５〜１０分である。For example, in the case of 140 to 170°C, approximately 20 to 30 minutes, 20
When the temperature is 0 to 230°C, it is about 5 to 10 minutes.
かくして得られた硬化塗膜は、ポリエステル樹脂のもつ
可撓性、塗膜外観の優れている点と、ビニル共重合樹脂
のもつ硬度、耐汚染性の優れている点を兼ね備えており
、しかも耐ブロッキング性が優れ、高温焼付時に生ずる
発泡（ワキ）、熱黄変などのない優れた塗膜性能を有し
ている。The cured coating film thus obtained combines the flexibility and excellent appearance of polyester resin with the hardness and stain resistance of vinyl copolymer resin. It has excellent blocking properties and has excellent coating performance without foaming (flanks) or thermal yellowing that occurs during high-temperature baking.
以下実施例により本発明を説明する。The present invention will be explained below with reference to Examples.
尚、「部」又は「％」は「重量部」又は「重量％」を表
わす。In addition, "part" or "%" represents "weight part" or "weight %."
〔不飽和ポリエステル樹脂溶液の製造方法〕（１）不飽
和ポリエステル樹脂扁１（以下ＰＥ−１と略記する）
攪拌機、温度計、冷却管及び窒素ガス導入管を備えた反
応容器に、イソフタル酸３７．９部、アジピン酸１６６
部、フマル酸３０部、ネオペンチルグリコール３４．７
部、トリメチロールプロパン７．８部を仕込み、窒素ガ
ス雰囲気下で、２４０℃で約６時間反応させて酸価１０
．０、水酸基価７６、および重量平均分子量２３３００
の樹脂を得た。[Method for producing unsaturated polyester resin solution] (1) Unsaturated polyester resin plate 1 (hereinafter abbreviated as PE-1) Isophthalic acid 37 .9 parts, adipic acid 166
parts, fumaric acid 30 parts, neopentyl glycol 34.7 parts
1 part and 7.8 parts of trimethylolpropane were charged and reacted at 240°C for about 6 hours in a nitrogen gas atmosphere to give an acid value of 10.
．． 0, hydroxyl value 76, and weight average molecular weight 23300
of resin was obtained.
樹脂の軟化温度は約６５〜６８℃であった。The softening temperature of the resin was about 65-68°C.
これをメチルエチルケトンで不揮発分６０％に希釈して
ＰＥ−１とした。This was diluted with methyl ethyl ketone to a non-volatile content of 60% to give PE-1.
（２）不飽和ポリエステル樹脂＆２（以下ＰＥ−２と略
記する）
前記ＰＥ−１を合成したと同様な反応容器に、イソフタ
ル酸４３．０部、アジピン酸１０．０部、フマールｅ
３．０ 部、ネオペンチルグリコール２２．５部、トリ
メチロールプロパン２１．５部を仕込み、窒素ガス雰囲
気下で２２５℃で約３時間反応させて、酸価１８−５、
水酸基価１３１、および重量平均分子量１００５００の
樹脂を得た。(2) Unsaturated polyester resin &2 (hereinafter abbreviated as PE-2) In a reaction vessel similar to that in which PE-1 was synthesized, 43.0 parts of isophthalic acid, 10.0 parts of adipic acid, and fumar e
3.0 parts, 22.5 parts of neopentyl glycol, and 21.5 parts of trimethylolpropane were charged and reacted at 225°C for about 3 hours in a nitrogen gas atmosphere to give an acid value of 18-5,
A resin having a hydroxyl value of 131 and a weight average molecular weight of 100,500 was obtained.
樹脂の軟化温度は約８２〜８５℃であった。これをメチ
ルエチルケトンで不揮発分６０％に希釈してＰＥ−２と
した。The softening temperature of the resin was about 82-85°C. This was diluted with methyl ethyl ketone to a non-volatile content of 60% to give PE-2.
〔ポリエステル変性ビニル樹脂溶液の製造方法〕（１）
攪拌機、温度計、滴下ロード及び冷却管を備えた反
応容器に、メチルエチルケトン３００部を入れ、温度を
８０℃に上げた後、下記の七ツマ−、ポリエステル樹脂
および開始剤混合液を３時間にわたって滴下した。[Method for producing polyester modified vinyl resin solution] (1)
300 parts of methyl ethyl ketone was placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping load, and a cooling tube, and the temperature was raised to 80°C, and then the following mixture of 7-mer, polyester resin, and initiator was added dropwise over 3 hours. did.
メチルメタクリレート２００部、スチレン８０部、エチ
ルアクリレート７５部、２−ヒドロキシエチルメタクリ
レート９０部、アクリル酸５部、前記ポリエステル樹脂
（ＰＥ−１）８３部、アゾビスイソブチロニトリル６部
、滴下終了後アゾビスイソブチロニトリル１部を追加し
、反応温度を８７℃に昇温させた後、４時間反応を行な
い、酸価８．０、水酸基価９１、重量平均分子量５９０
００、および不揮発分５９．９％の樹脂溶液を得た。200 parts of methyl methacrylate, 80 parts of styrene, 75 parts of ethyl acrylate, 90 parts of 2-hydroxyethyl methacrylate, 5 parts of acrylic acid, 83 parts of the above polyester resin (PE-1), 6 parts of azobisisobutyronitrile, after completion of dropping. After adding 1 part of azobisisobutyronitrile and raising the reaction temperature to 87°C, the reaction was carried out for 4 hours. The acid value was 8.0, the hydroxyl value was 91, and the weight average molecular weight was 590.
00, and a resin solution with a nonvolatile content of 59.9% was obtained.
樹脂の軟化温度は約９８〜１００℃であった。The softening temperature of the resin was about 98-100°C.
これをＰＥ−Ｖ−１とした。This was named PE-V-1.
（２）前記ＰＥ−Ｖ−１を合成したと同様な反応容器に
、メチルエチルケトン３００部を入れ、温度を８０℃に
上げた後、下記のモノマー、ポリエステル樹脂および開
始剤混合液を３時間にわたって滴下した。(2) Put 300 parts of methyl ethyl ketone into the same reaction vessel as the one used to synthesize PE-V-1, raise the temperature to 80°C, and then dropwise add the following monomer, polyester resin, and initiator mixture over 3 hours. did.
メチルメタクリレ−）１４０部、スチレン１４０部、エ
チルアクリレート２５部、２−エチルへキシルメタクリ
レート４０部、２−ヒドロキシエチルメタクリレート１
００部、アクリル酸５部、前記ポリエステル樹脂（ＰＥ
−１＞８３部、アゾビスイソブチロニトリル６部。140 parts of methyl methacrylate, 140 parts of styrene, 25 parts of ethyl acrylate, 40 parts of 2-ethylhexyl methacrylate, 1 part of 2-hydroxyethyl methacrylate
00 parts, 5 parts of acrylic acid, the above polyester resin (PE
-1>83 parts, 6 parts of azobisisobutyronitrile.
滴下終了後アゾビスインブチロニトリル１部を追加し、
反応温度を８７℃に昇温させた後、４時間反応を行い、
酸価８．１、水酸基価９９、重量平均分子量６４３００
および不揮発分６０．３％の樹脂溶液を得た。After completing the dropping, add 1 part of azobisin butyronitrile,
After raising the reaction temperature to 87°C, the reaction was carried out for 4 hours,
Acid value 8.1, hydroxyl value 99, weight average molecular weight 64300
A resin solution with a nonvolatile content of 60.3% was obtained.
樹脂の軟化温度は約１０５〜１０７℃であまた。The softening temperature of the resin is about 105-107°C.
これをＰＥ−Ｖ−２とした。This was designated as PE-V-2.
（３）前記ＰＥ−ｖ−ｉを合成したと同様な反応容器に
メチルエチルケト７３１７．５部を入れ、温度を８０℃
に上げた後、下記のモノマー、ポリエステル樹脂および
開始剤混合液を３時間にわたって滴下した。(3) Put 7317.5 parts of methyl ethyl keto into a reaction vessel similar to that in which PE-v-i was synthesized, and adjust the temperature to 80°C.
After raising the temperature to 100 mL, the following monomer, polyester resin, and initiator mixture was added dropwise over 3 hours.
メチルメタクリレート１００部、スチレン１７５部、２
−エチルへキシルメタクリレート８５部、２−ヒドロキ
シエチルメタクリレート１１０部、アクリル酸５部、前
記ポリエステル樹脂（ｐＥ−２）４２部、アゾビスイソ
ブチロニトリル６部。100 parts of methyl methacrylate, 175 parts of styrene, 2
- 85 parts of ethylhexyl methacrylate, 110 parts of 2-hydroxyethyl methacrylate, 5 parts of acrylic acid, 42 parts of the above polyester resin (pE-2), and 6 parts of azobisisobutyronitrile.
滴下終了後アゾビスイソブチロニトリル１部を追加し、
反応温度を８７℃に昇温させた後、４時間反応を行い、
酸価７．９、水酸基価１０８、重量平均分子量８９５０
０および不揮発分６１．５％の樹脂溶液を得た。After finishing dropping, add 1 part of azobisisobutyronitrile,
After raising the reaction temperature to 87°C, the reaction was carried out for 4 hours,
Acid value 7.9, hydroxyl value 108, weight average molecular weight 8950
A resin solution with a non-volatile content of 0 and 61.5% was obtained.
樹脂の軟化温度は約１００〜１０２℃であった。The softening temperature of the resin was about 100-102°C.
これをＰＥ−Ｖ−３とした。This was named PE-V-3.
（１）攪拌機、温度計、滴下ロートおよび冷却管を備え
た反応容器に、メチルエチルケトン３３５部を入れ、温
度を８０℃に上げた後、下記のモノマーおよび開始剤混
合液を３時間にわたって滴下した。(1) 335 parts of methyl ethyl ketone was placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a cooling tube, and after raising the temperature to 80°C, the following monomer and initiator mixture was added dropwise over 3 hours.
メチルメタクリレート１５０部、スチレン１１５部、エ
チルアクリレート７５部、２−エチルへキシルメタクリ
レート２５部、Ｎ−ｎ−ブトキシメチルアクリルアミド
１２５部、アクリル酸１０部、アゾビスイソブチロニト
リル１０部。150 parts of methyl methacrylate, 115 parts of styrene, 75 parts of ethyl acrylate, 25 parts of 2-ethylhexyl methacrylate, 125 parts of N-n-butoxymethylacrylamide, 10 parts of acrylic acid, 10 parts of azobisisobutyronitrile.
滴下終了後アゾビスイソブチロニトリル１，５部を追加
し、反応温度を８７℃に昇温させた後、４時間反応を行
ない、酸価１５．５、重量平均分子量４６３００および
不揮発分５９．１％の樹脂溶液を得た。After the dropwise addition, 1.5 parts of azobisisobutyronitrile was added, the reaction temperature was raised to 87°C, and the reaction was carried out for 4 hours, resulting in an acid value of 15.5, a weight average molecular weight of 46,300, and a non-volatile content of 59. A 1% resin solution was obtained.
樹脂の軟化温度は約８０〜８３℃であった。The softening temperature of the resin was about 80-83°C.
これをＶ−１とした。実施例 １
樹脂溶液（ＰＥ−Ｖ−１） ２１部に、二酸化チタン１
８部、流動助剤（商品名モダフロー：モンサンド社製）
１部、メチルエチルケトン５部を加え、サンドミルで１
０μ以下（グラインドゲージによる測定：以下同じ）に
練合分散後、樹脂溶液（Ｖ−１）４９部、メチルエチル
ケトン６部を加え、攪拌混合して均一な顔料分散液とし
た。This was designated as V-1. Example 1 21 parts of resin solution (PE-V-1) and 1 part of titanium dioxide
8 parts, flow aid (trade name: Modaflow: manufactured by Monsando)
Add 1 part and 5 parts of methyl ethyl ketone, and grind with a sand mill.
After kneading and dispersing to 0μ or less (measured with a grind gauge; the same applies hereinafter), 49 parts of resin solution (V-1) and 6 parts of methyl ethyl ketone were added and mixed with stirring to obtain a uniform pigment dispersion.
該顔料分散液１００部にメチルエチルケトン４０部を更
に加え、攪拌混合した後、これを高速攪拌下にある水温
１５℃の水３５００部中に滴下し、顔料分散液を乳化す
るとともに溶剤を水中へ抽出して樹脂粒子を形成した。After further adding 40 parts of methyl ethyl ketone to 100 parts of the pigment dispersion and stirring and mixing, this was dropped into 3,500 parts of water at a temperature of 15°C under high speed stirring to emulsify the pigment dispersion and extract the solvent into the water. to form resin particles.
その後、１過および水洗を繰り返し、平均粒子径約８５
μの樹脂粒子含水ケーキを得た。After that, filtration and water washing were repeated once, and the average particle size was approximately 85.
A water-containing cake of resin particles of μ was obtained.
この含水ケーキを温風（３５℃）下で乾燥して、本発明
の熱硬化性粉体塗料組成物を得た。This water-containing cake was dried under warm air (35°C) to obtain a thermosetting powder coating composition of the present invention.
実施例 ２
実施例１において樹脂溶液（ＰＥ−Ｖ−１）を樹脂溶液
（ＰＥ−Ｖ−２）におきかえた他はすべて同様にして、
本発明の熱硬化性粉体塗料組成物を得た。Example 2 The same procedure as in Example 1 was carried out except that the resin solution (PE-V-1) was replaced with the resin solution (PE-V-2).
A thermosetting powder coating composition of the present invention was obtained.
実施例 ３
樹脂溶液（ＰＥ−Ｖ−３） １４部、樹脂溶液（Ｖ−１
）１０部に、二酸化チタン１８部、流動助剤（商品名モ
ダフロー：モンサント社製）１部、メチルエチルケトン
５部を加え、ボールミルで１０μ以下に練合分散後、樹
脂溶液（Ｖ−１）。Example 3 14 parts of resin solution (PE-V-3), 14 parts of resin solution (V-1)
), 18 parts of titanium dioxide, 1 part of flow aid (trade name: Modaflow, manufactured by Monsanto), and 5 parts of methyl ethyl ketone were added, and the mixture was kneaded and dispersed in a ball mill to a size of 10 μm or less, resulting in a resin solution (V-1).
４６部、メチルエチルケトン６部を加え、攪拌混合して
、均一な顔料分散液とした。46 parts and 6 parts of methyl ethyl ketone were added and mixed with stirring to obtain a uniform pigment dispersion.
該顔料分散液１００部に、メチルエチルケトン４０部を
更に加え、攪拌混合した後、これを高速攪拌下にある水
温２０℃の水４０００部中に噴霧し、顔料分散液を乳化
するとともに溶剤を水中へ抽出して樹脂粒子を形成した
。40 parts of methyl ethyl ketone was further added to 100 parts of the pigment dispersion, and after stirring and mixing, this was sprayed into 4000 parts of water at a temperature of 20°C under high speed stirring to emulsify the pigment dispersion and remove the solvent into the water. Extraction formed resin particles.
その後、ｒ過および水洗を繰り返し、平均粒子径８０μ
の樹脂粒子含水ケーキを得た。After that, R-filtration and water washing were repeated, and the average particle size was 80 μm.
A cake containing resin particles was obtained.
この含水ケーキを温風（３５℃）下で乾燥して本発明の
熱硬化性粉体塗料組成物を得た。This water-containing cake was dried under warm air (35°C) to obtain a thermosetting powder coating composition of the present invention.
比較例 １
実施例１で使用したポリエステル変性ビニル樹脂溶液（
ＰＥ−Ｖ−１）の組成から変性用ポリエステル樹脂（Ｐ
Ｅ−１）を除いたモノマー組成で、他はすべてポリエス
テル変性ビニル樹脂溶液製造（１）と同様にして反応を
行ない酸価８．５、水酸基価８８（重量平均分子量２１
０００）および不揮発分５９．７％の樹脂溶液を得た。Comparative Example 1 Polyester modified vinyl resin solution used in Example 1 (
From the composition of PE-V-1), the modified polyester resin (P
The reaction was carried out in the same manner as in polyester-modified vinyl resin solution production (1) except for monomer composition E-1).
000) and a resin solution with a nonvolatile content of 59.7% was obtained.
該樹脂溶液２４部に、二酸化チタン１８部、流動助剤（
商品名モダフロー：モンサンド社製）１部、メチルエチ
ルケトン５部を加え、サンドミルで１０μ以下に練合分
散後、更に該樹脂溶液２８．５部および平均縮合度２．
５、エーテル化度２．５および水可溶性成分１％以下の
ブチル化メチロールメラミン樹脂の６０％メチルエチル
ケトン溶液１７．５部、メチルエチルケト７６部を加え
、攪拌混合して均一な顔料分散液とした。To 24 parts of the resin solution, 18 parts of titanium dioxide and a flow aid (
Add 1 part of Modaflow (trade name: manufactured by Monsando) and 5 parts of methyl ethyl ketone, knead and disperse in a sand mill to a size of 10 μm or less, and then add 28.5 parts of the resin solution and an average condensation degree of 2.
5. 17.5 parts of a 60% methyl ethyl ketone solution of a butylated methylol melamine resin with a degree of etherification of 2.5 and a water-soluble component of 1% or less and 76 parts of methyl ethyl keto were added and mixed with stirring to obtain a uniform pigment dispersion.
以下すべて実施例１と同様にして粉体塗料組成物を得た
。A powder coating composition was obtained in the same manner as in Example 1.
比較例 ２
実施例２で使用したポリエステル変性ビニル樹脂溶液（
ＰＥ−Ｖ−２）の組成からポリエステル樹脂（ＰＥ−１
）を除いた、モノマー組成で他はすべてポリエステル変
性ビニル樹脂溶液製造（２）と同様にして反応を行ない
、酸価８．６、水酸基価９６、（重量平均分子量２３６
００）および不揮発分５９．２％の樹脂溶液を得た。Comparative Example 2 Polyester modified vinyl resin solution used in Example 2 (
From the composition of polyester resin (PE-V-2)
), except for the monomer composition, the reaction was carried out in the same manner as in polyester-modified vinyl resin solution production (2).
00) and a resin solution with a nonvolatile content of 59.2% was obtained.
該樹脂溶液２４部に、二酸化チタン１９部、流動助剤（
商品名モダフロー：モンサンド社製）１部、メチルエチ
ルケトン２部を加え、ボールミルで１０μ以下に練合分
散後、更に該樹脂溶液２４５部およびブロックイソシア
ネート化合物（商品名クレランＵ−Ｉ６１０９：バイエ
ル社製）のメチルエチルケト７５０％溶液２９部、ジブ
チルチンジラウレート（解離触媒）０．５部を加え、攪
拌混合して均一な顔料分散液とした。To 24 parts of the resin solution, 19 parts of titanium dioxide and a flow aid (
Add 1 part of Modaflow (trade name: manufactured by Monsando) and 2 parts of methyl ethyl ketone, and after kneading and dispersing in a ball mill to a size of 10μ or less, further add 245 parts of the resin solution and a blocked isocyanate compound (trade name: Clelan U-I6109: manufactured by Bayer). 29 parts of 750% methyl ethyl keto solution and 0.5 part of dibutyltin dilaurate (dissociation catalyst) were added and mixed with stirring to obtain a uniform pigment dispersion.
以下すべて実施例１と同様にして粉体塗料組成物を得た
。A powder coating composition was obtained in the same manner as in Example 1.
以上の各実施例および比較例で作製した粉体塗・料を微
粉砕用ミル〔サンコーミルＳＫ−Ｍ２型：三光理化学工
業■〕で粉砕した後、１００メツシユでふるい分けて調
整した粉末塗料を得た。The powder paints prepared in each of the above examples and comparative examples were pulverized with a fine grinding mill [Sanko Mill SK-M2 type: Sanko Rikagaku Kogyo ■], and then sieved through a 100-mesh screen to obtain the prepared powder paints. Ta.
得られた粉体塗料をリン酸亜鉛系化成処理鋼板（厚さ０
．８ ｍｒｎ ）に静電塗装法により、硬化膜厚約７０
μになるように塗布した後、１８０℃で３０分間焼付け
た。The obtained powder coating was applied to a zinc phosphate chemical conversion treated steel plate (thickness 0
．． 8 mrn) by electrostatic coating method, the cured film thickness is approximately 70 mrn.
After applying the film to a thickness of μ, it was baked at 180° C. for 30 minutes.
この塗装鋼板の塗膜の性能試験結果を第１表に示した。Table 1 shows the performance test results of the coating film of this coated steel plate.
Claims (1)
ボン酸を構成成分の一つとする、軟化点が４０〜１２０
℃の不飽和ポリエステル樹脂・・・・・・・・・２〜３
０重量％と、 （ｉｉ）（イ） α・β−モノエチレン性不飽和カルボ
ン酸ノヒドロキシアルキルエステル・・・・・・・・・
５〜４０重量％、 （ロ）前胆イ）以外のα・β−モノエチレン性不飽和単
量体・・・・・・・・・９５〜６０重量％、から成る単
量体混合物・・・・・・・・・９８〜７０重量％とをグ
ラフト重合して得られる、水酸基価３０〜１８０で、か
つ軟化点が５０〜１３０℃のポリエステル変性ビニル樹
脂・・・・・・・・・５〜９０重量％０ （ＢＸａ） α・β−モノエチレン性不飽和カルボン
酸アミドのＮ−アルコキシメチル化単量体・・・・・・
・・・５〜３０重量％、 （ｂ） α・β−モノエチレン性不飽和カルボン酸・
・・・・・・・・０．５〜１０重量％、（ｃ） Ｍｉ
ＥＹａ）及ヒ（ｂ）以外のα・β−モノエチレン性不飽
和単量体・・・・・・・・・６０〜９０重量％から成る
単量体混合物から得られる、軟化点が５０〜１３０℃の
架橋性共重合樹脂・・・・・・・・・９５〜１０重量％ から成る微粉状熱硬化性樹脂粒子よりなる熱硬化性粉体
塗料組成物。[Scope of Claims] 1(A) (1) Contains 1 to 10% by weight of α/β-unsaturated dicarboxylic acid as one of the constituent components and has a softening point of 40 to 120
Unsaturated polyester resin at °C...2-3
0% by weight, (ii) (a) α/β-monoethylenically unsaturated carboxylic acid nohydroxyalkyl ester...
A monomer mixture consisting of 5 to 40% by weight, (b) α/β-monoethylenically unsaturated monomer other than (a), and 95 to 60% by weight. A polyester modified vinyl resin having a hydroxyl value of 30 to 180 and a softening point of 50 to 130°C, obtained by graft polymerization of 98 to 70% by weight. 5-90% by weight 0 (BXa) N-alkoxymethylated monomer of α/β-monoethylenically unsaturated carboxylic acid amide...
...5 to 30% by weight, (b) α/β-monoethylenically unsaturated carboxylic acid.
...0.5-10% by weight, (c) Mi
α/β-monoethylenically unsaturated monomers other than EYa) and (b)……obtained from a monomer mixture consisting of 60 to 90% by weight, with a softening point of 50 to 90% by weight A thermosetting powder coating composition comprising fine powder thermosetting resin particles comprising 95 to 10% by weight of a crosslinkable copolymer resin at 130°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5294880A JPS5820987B2 (en) | 1980-04-23 | 1980-04-23 | Thermosetting powder coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5294880A JPS5820987B2 (en) | 1980-04-23 | 1980-04-23 | Thermosetting powder coating composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56149471A JPS56149471A (en) | 1981-11-19 |
| JPS5820987B2 true JPS5820987B2 (en) | 1983-04-26 |
Family
ID=12929092
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5294880A Expired JPS5820987B2 (en) | 1980-04-23 | 1980-04-23 | Thermosetting powder coating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5820987B2 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2208613A1 (en) * | 1972-02-24 | 1973-09-06 | Basf Ag | POWDER-FORMED COATING COMPOSITIONS |
| JPS5137086B2 (en) * | 1972-08-25 | 1976-10-13 | ||
| JPS51532A (en) * | 1974-06-24 | 1976-01-06 | Hitachi Chemical Co Ltd | FUNTAITOR YOYOJUSHI SEIBUTSU |
-
1980
- 1980-04-23 JP JP5294880A patent/JPS5820987B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56149471A (en) | 1981-11-19 |
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