JPH02235969A - Resin composition for thermosetting powder coating material - Google Patents
Resin composition for thermosetting powder coating materialInfo
- Publication number
- JPH02235969A JPH02235969A JP5513889A JP5513889A JPH02235969A JP H02235969 A JPH02235969 A JP H02235969A JP 5513889 A JP5513889 A JP 5513889A JP 5513889 A JP5513889 A JP 5513889A JP H02235969 A JPH02235969 A JP H02235969A
- Authority
- JP
- Japan
- Prior art keywords
- glycidyl group
- curing agent
- powder coating
- fluoroolefin
- resin composition
- 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.)
- Pending
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 35
- 239000011248 coating agent Substances 0.000 title claims abstract description 26
- 239000000843 powder Substances 0.000 title claims description 29
- 239000011342 resin composition Substances 0.000 title claims description 12
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 11
- 239000000463 material Substances 0.000 title description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract description 36
- 229920001577 copolymer Polymers 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 2
- 230000001737 promoting effect Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 8
- 239000011347 resin Substances 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 7
- 150000007519 polyprotic acids Polymers 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 150000008064 anhydrides Chemical class 0.000 abstract 1
- -1 vinyl butylene, vinylidene butylene, trifluoroethylene, tetrafluoroethylene Chemical group 0.000 description 17
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 4
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 3
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 229920001567 vinyl ester resin Polymers 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 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
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-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
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-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
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical group C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 1
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- WUMVZXWBOFOYAW-UHFFFAOYSA-N 1,2,3,3,4,4,4-heptafluoro-1-(1,2,3,3,4,4,4-heptafluorobut-1-enoxy)but-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)F WUMVZXWBOFOYAW-UHFFFAOYSA-N 0.000 description 1
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 1
- MLRVZFYXUZQSRU-UHFFFAOYSA-N 1-chlorohexane Chemical compound CCCCCCCl MLRVZFYXUZQSRU-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- YAOJJEJGPZRYJF-UHFFFAOYSA-N 1-ethenoxyhexane Chemical compound CCCCCCOC=C YAOJJEJGPZRYJF-UHFFFAOYSA-N 0.000 description 1
- XXCVIFJHBFNFBO-UHFFFAOYSA-N 1-ethenoxyoctane Chemical compound CCCCCCCCOC=C XXCVIFJHBFNFBO-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 description 1
- OUELSYYMNDBLHV-UHFFFAOYSA-N 2-ethenoxyethylbenzene Chemical compound C=COCCC1=CC=CC=C1 OUELSYYMNDBLHV-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- XYFRHHAYSXIKGH-UHFFFAOYSA-N 3-(5-methoxy-2-methoxycarbonyl-1h-indol-3-yl)prop-2-enoic acid Chemical compound C1=C(OC)C=C2C(C=CC(O)=O)=C(C(=O)OC)NC2=C1 XYFRHHAYSXIKGH-UHFFFAOYSA-N 0.000 description 1
- PLZIKMVNRWVJKM-UHFFFAOYSA-N 9-ethenoxy-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-hexadecafluorononane Chemical compound FC(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)COC=C PLZIKMVNRWVJKM-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004135 Bone phosphate Substances 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- GACVWNWIFGIOKS-UHFFFAOYSA-N C=COC(C(C(C(C1(F)F)(F)F)(F)F)(F)F)(C1(F)F)F Chemical compound C=COC(C(C(C(C1(F)F)(F)F)(F)F)(F)F)(C1(F)F)F GACVWNWIFGIOKS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229940090012 bentyl Drugs 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- LSRPARCOXAUYNP-UHFFFAOYSA-N cyclohexylidene(oxido)oxidanium Chemical compound [O-][O+]=C1CCCCC1 LSRPARCOXAUYNP-UHFFFAOYSA-N 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
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 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 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- CMXXMZYAYIHTBU-UHFFFAOYSA-N ethenyl 2-hydroxybenzoate Chemical class OC1=CC=CC=C1C(=O)OC=C CMXXMZYAYIHTBU-UHFFFAOYSA-N 0.000 description 1
- WNMORWGTPVWAIB-UHFFFAOYSA-N ethenyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC=C WNMORWGTPVWAIB-UHFFFAOYSA-N 0.000 description 1
- ZLHVSEPPILCZHH-UHFFFAOYSA-N ethenyl 4-tert-butylbenzoate Chemical compound CC(C)(C)C1=CC=C(C(=O)OC=C)C=C1 ZLHVSEPPILCZHH-UHFFFAOYSA-N 0.000 description 1
- JZRGFKQYQJKGAK-UHFFFAOYSA-N ethenyl cyclohexanecarboxylate Chemical compound C=COC(=O)C1CCCCC1 JZRGFKQYQJKGAK-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- OTCVAHKKMMUFAY-UHFFFAOYSA-N oxosilver Chemical class [Ag]=O OTCVAHKKMMUFAY-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は新規にして有用なる熱硬化性粉体塗料用樹脂組
成物に関する。さらに詳細には、本発明はペース樹脂成
分としてのグリ/ノル基含有フルオロオレフィン共重合
体と、硬化剤成分としてのグリシジル基反応性化合物と
を必須の成分として含んで成るか、あるいはグリシジル
基含有フルオロオレフィン共重合体と、グリシジル基反
応性の硬化剤と、硬化触媒とを含んで成る、いわゆる、
ふっ素樹脂系粉体塗料用の樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a new and useful resin composition for thermosetting powder coatings. More specifically, the present invention comprises a glycidyl group-containing fluoroolefin copolymer as a paste resin component and a glycidyl group-reactive compound as a curing agent component, or a glycidyl group-containing A so-called fluoroolefin copolymer, a glycidyl group-reactive curing agent, and a curing catalyst.
The present invention relates to a resin composition for fluororesin-based powder coatings.
この種のふっ素樹脂系の粉体塗料用の樹脂として、ぶつ
化ビニリデンを主成分とする熱可塑性タイプのものがあ
る。As this type of fluororesin-based resin for powder coatings, there is a thermoplastic type resin whose main component is vinylidene fluoride.
ふっ素樹脂(フルオロオレフィン共重合体うは、耐薬品
性をはじめとして、耐熱性、耐摩耗性、非粘着性および
耐候性が良好であるために、広範に利用されてはいるも
のの、その反面で、融点が高い処から、粉砕に特殊な装
置が必要となるし、昼温での溶融焼伺けもまた必敬であ
るなどの不都合があって、粉体塗料としての利用が殆ん
ど為されてはいない、というのが現状である。Fluororesins (fluoroolefin copolymers) are widely used due to their good chemical resistance, heat resistance, abrasion resistance, non-stick properties, and weather resistance. However, because of its high melting point, special equipment is required for crushing it, and it is also indispensable to melt and bake it at daytime temperature, so it is rarely used as a powder coating. The current situation is that this has not been done.
また、特開昭59−120661号公報には、側鎖に(
・{−)フルオロアルキル基をもった単量体を共重合さ
せて得られる樹脂を添加剤として用いることによりビニ
ル共重合樹脂を改質せしめる技術が開示されてはいるが
、かかる添加用樹脂それ自体、相溶性の上で、ならひに
粉体塗料に使用する場合の耐プロソキング性の上で、添
加量に制限があった。Furthermore, in Japanese Patent Application Laid-Open No. 59-120661, (
・Although a technique has been disclosed for modifying a vinyl copolymer resin by using a resin obtained by copolymerizing a monomer having a {-)fluoroalkyl group as an additive, such additive resins and As such, there are limits to the amount added due to compatibility and, in particular, resistance to prosodication when used in powder coatings.
さらに、熱硬化性の粉体塗料としてのアクリル粉体塗料
は、耐候性、耐汚染性または外観などがすぐれるもので
あるだめに広く用いられてはいるか、長期の耐候性が要
求される用途には不十分なものであり、したがって、従
来の製造方式による扱い易い形の、熱硬化性の高耐候性
粉体塗料の実用化が望まれている。Furthermore, acrylic powder coatings, which are thermosetting powder coatings, are widely used for their excellent weather resistance, stain resistance, and appearance, or for applications that require long-term weather resistance. Therefore, it is desired to put into practical use a thermosetting, highly weather resistant powder coating that is easy to handle using conventional manufacturing methods.
そこで、本発明者らは上述した従来技術における種々の
欠点の存在に鑑みて、常用されている硬化条件で、つま
り、汎用の粉体塗料におけると同様な硬化条件で硬化可
能な、ふっ素樹脂系粉体塗料を得ることを目的として鋭
意研討を重ねた結果、特定の分子量と軟化点とを有し、
しかも反応性基(官能基)としてのグリシジル基を含有
するフルオロオレフィン共重合体と、とのグリシ・ソル
基と反応しうる硬化剤との組み合わせになる組成物が、
硬化性にすぐれるものであるから、耐溶剤性にすぐれる
ほか、極めて耐候性にすぐれる硬化塗膜を与えることを
見い出して、本発明を完成されるに到った。Therefore, in view of the various shortcomings in the prior art described above, the present inventors developed a fluororesin system that can be cured under commonly used curing conditions, that is, under the same curing conditions as general-purpose powder coatings. As a result of intensive research aimed at obtaining a powder coating, we found that it has a specific molecular weight and softening point,
Moreover, the composition is a combination of a fluoroolefin copolymer containing a glycidyl group as a reactive group (functional group) and a curing agent that can react with the glycysol group.
Since it has excellent curability, it has been found that it can provide a cured coating film that not only has excellent solvent resistance but also has extremely excellent weather resistance, and has completed the present invention.
すなわち、本発明は必須の成分として、環球法により測
定された軟化点が60〜150℃で、数平均分子量がi
,ooo〜100,000で、かつ、グリシジル基を含
有するフルオロオレフィン共重合体(A)と、グリシジ
ル基反応性の硬化剤(B)とを含んで成る、あるいは、
こうしたフルオロオレフィン共重合体(A)とグリシジ
ル基反応性硬化剤(B)と、これの共重合体(A)と硬
化剤(B)との架橋反応を促進させるための硬化触媒(
C)とを含んで成る粉体塗料用樹脂組成物を提供するも
のである。That is, in the present invention, as essential components, the softening point measured by the ring and ball method is 60 to 150°C, and the number average molecular weight is i.
, ooo to 100,000 and comprising a glycidyl group-containing fluoroolefin copolymer (A) and a glycidyl group-reactive curing agent (B), or
Such a fluoroolefin copolymer (A), a glycidyl group-reactive curing agent (B), and a curing catalyst for promoting the crosslinking reaction between the copolymer (A) and the curing agent (B).
C) A resin composition for powder coating is provided.
ここにおいて、上記したフルオロオレフィン共重合体(
A)としては、たとえば、ぶつ化ビニル、ぶつ化ビニリ
デン、トリフルオロエチレン、テトラフルオロエチレン
、プロモトリフルオロエチレン、クロロトリフルオ口エ
チレン、ペンタフルオロプロピレン へキザフルオロプ
ロピレン、または(パー)フルオロアルキル基の炭素数
が1〜18なる(・ソ−)フルオロアルキルトリフルオ
口ビニルエーテルの如き、フルオロオレフイン単位を必
須の構成単位として含有し、なおかつ、側鎖に水酸基や
グリシジル基などの反応性基(官能基)をも持ったもの
などが挙けられるが、そうした意味においても、当該フ
ルオロオレフィン共重合体(ト)としては、■上掲され
た如きフルオロオレフィン〔以下、これを(a−1)な
る一反応成分とする。〕と、後掲する如き、それぞれ、
グリシジノレ基を含有する単量体〔以下、これを(a−
2)なる一反応成分とする。〕と、これらのフルオロオ
レフィン(a−1)およびグリシジル基含有単量体(&
−2)と共重合可能な他の単量体〔以下、これを(a3
)なる一反応成分とする。〕とを共重合させることによ
り得られるものが望ましい。Here, the above-mentioned fluoroolefin copolymer (
Examples of A) include vinyl butylene, vinylidene butylene, trifluoroethylene, tetrafluoroethylene, promotrifluoroethylene, chlorotrifluoroethylene, pentafluoropropylene, hexafluoropropylene, or the carbon of a (per)fluoroalkyl group. Contains a fluoroolefin unit as an essential constituent unit, such as (.so-)fluoroalkyl trifluorovinyl ether having a number of 1 to 18, and also has a reactive group (functional group) such as a hydroxyl group or a glycidyl group in the side chain. In this sense, the fluoroolefin copolymer (g) is a fluoroolefin as listed above [hereinafter referred to as one reaction component (a-1)]. shall be. ] and as listed below, respectively.
A monomer containing a glycidinole group [hereinafter referred to as (a-
2) One reaction component. ] and these fluoroolefins (a-1) and glycidyl group-containing monomers (&
-2) and other monomers copolymerizable [hereinafter referred to as (a3
) as one reaction component. ] is preferable.
かかる上記グリシジル基含有単量体(a−2)として代
表的なものには、グリシジルビニノレエーテル、(β−
メチル)グリシジルアクリレート、(βメチル)グリシ
ジルメタクリレートまたはアリルグリシジルエーテルな
どがあるが、共重合性という観点からは、ビニルエーテ
ル系のものの使用が望ましい。これに対し、アクリル系
のものは、前掲された如き各種のフルオロオレフイン(
a一1)との共重合性が不十分である処から、その使用
量としても、当該目的共重合体(A)の重合率を低下さ
せないような範囲内に止めるべきである。Typical examples of the glycidyl group-containing monomer (a-2) include glycidyl vinyl ether, (β-
Examples include methyl)glycidyl acrylate, (β-methyl)glycidyl methacrylate, and allylglycidyl ether, but from the viewpoint of copolymerizability, it is desirable to use vinyl ethers. On the other hand, acrylic materials include various fluoroolefins (
Since copolymerizability with a-1) is insufficient, the amount used should be kept within a range that does not reduce the polymerization rate of the target copolymer (A).
さらに、前掲された如きフルオロオレフイ/(a−1)
およびグリシジル基含有単量体(a−2)と共重合可能
な他の単量体(a−3)の代表例としては、メチルビニ
ルエーテル、エチルビニルエーテル、n−グロビルビニ
ルエーテル、イソフロヒルビニルエーテル、n−プチル
ビニルエーテル、イソブチルビニルエーテル、tert
−プチルビニルエーテル、n−ベンチルビニル、n−ヘ
キシルビニルエーテル、n−オクチルビニルエーテルモ
シ<ld2−エチルヘキシルビニルエーテルの如キアル
キルビニルエーテル類;シクロベンチルビニルエーテル
、シクロヘキシルビニルエーテルもL<はメチルシクロ
ヘキシルビニルエーテルの如キシクロアルキルビニルエ
ーテル類;ベン・ゾルビニルエーテルもしくはフェネチ
ルビニルエーテルの如キアラルキルビニルエーテル類:
2,2,3.3−テトラフルオ口プロビルビニルエー
テル、2.2,3,3,4.4,5.5−オクタフルオ
ロベンチルビニルエーテル、2,2.3,3,4,4,
5,5,6,6,7,7,8,8.9,9−へキサデカ
フルオロノニルビニルエーテル、パーフルオロメチルビ
ニルエーテル、パーフルオロエチルビニルエーテル i
+ − 7ルオログロビルビニルエーテル、ノヤーフル
オロオクチルビニルエーテル4L<はパフルオロシクロ
ヘキシルビニルエーテルの如キ(ハー)フルオロアルキ
ルビニルエーテル類;マたは酢酸ビニル、プロピオン酸
ビニル、n一酪酸ビニル、イソ酪酸ビニル、ピバリン酸
ビニル、カプロン酸ビニル、バーサティック酸ヒニル、
ラウリン酸ビニル、ステアリン酸ビニル、安息香酸ビニ
ル、p − t ert−ブチル安息香酸ビニル、サリ
チ/l’ rll ヒ=ルモシくハシクロヘキサンカル
ポン酸ビニルの如キカルポン酸ビニルエステル’lAf
xト7b:挙げられるし、さらには、エチレン、グロビ
レン、塩化ビニル、塩化ビニリデン、(メタ)アクリロ
ニトリルまたは各種(メタ)アクリル酸エステル類など
も使用することができる。Furthermore, fluoroolefin/(a-1) as listed above
Typical examples of other monomers (a-3) copolymerizable with the glycidyl group-containing monomer (a-2) include methyl vinyl ether, ethyl vinyl ether, n-globin vinyl ether, isofurohir vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert
- Alkyl vinyl ethers such as butyl vinyl ether, n-bentyl vinyl, n-hexyl vinyl ether, n-octyl vinyl ether, <ld2-ethylhexyl vinyl ether; Classes: Chiralkyl vinyl ethers such as ben-zorvinyl ether or phenethyl vinyl ether:
2,2,3.3-tetrafluoropropylene vinyl ether, 2.2,3,3,4.4,5.5-octafluorobentyl vinyl ether, 2,2.3,3,4,4,
5,5,6,6,7,7,8,8.9,9-hexadecafluorononyl vinyl ether, perfluoromethyl vinyl ether, perfluoroethyl vinyl ether i
+ - 7 Fluoroglobin vinyl ether, Noyafluorooctyl vinyl ether 4L< is fluoroalkyl vinyl ethers such as perfluorocyclohexyl vinyl ether; Other is vinyl acetate, vinyl propionate, vinyl n-monobutyrate, vinyl isobutyrate , vinyl pivalate, vinyl caproate, hinyl versatate,
Vinyl laurate, vinyl stearate, vinyl benzoate, p-tert-butyl vinyl benzoate, salicylic acid vinyl esters such as vinyl hacyclohexanecarboxylate.
x-7b: In addition, ethylene, globylene, vinyl chloride, vinylidene chloride, (meth)acrylonitrile or various (meth)acrylic acid esters can also be used.
当該共重合可能な他の単量体(a−3)のうち、目的共
重合体へ)の調製時における重合率の向上および塗膜の
耐候性の向上化などの面から、アルキルビニルエーテル
類;シクロアルキルビニルエテル類およびカルデン酸ビ
ニルエステル類よシナる群から選ばれる少なくとも1種
を用いるのが望ましいし、就中、得られる塗料の貯蔵安
定性(耐プロソギング性)や塗膜の硬度などの面から、
シクロアルキルビニルエーテル類、あるいはシクロヘキ
サンカルボン酸ビニル、酢酸ビニル、安息香酸ビニルも
しくはp − tert−ブチル安息香酸ビニル、また
は第三級炭素原子に結合したカルー?キシル基を有する
05〜C18なる脂肪族カルポン酸のビニルエステル類
よυなる群から選ばれる少なくとも1種を用いるのが望
ましい。Among the other copolymerizable monomers (a-3), alkyl vinyl ethers; It is desirable to use at least one member selected from the group consisting of cycloalkyl vinyl ethers and caldic acid vinyl esters. From the side,
cycloalkyl vinyl ethers, or vinyl cyclohexanecarboxylate, vinyl acetate, vinyl benzoate or vinyl p-tert-butylbenzoate, or caru-bonded to a tertiary carbon atom? It is desirable to use at least one member selected from the group consisting of vinyl esters of aliphatic carboxylic acids of 05 to C18 having a xyl group.
以上に掲げられた各種の探応成分から目的とするフルオ
ロオレフィン共重合体囚を得るには、フルオロオレフィ
ン(a−1)の15〜70重i%と、グリシジル基含有
単量体(a−2)の5〜40重景%と、共重合可能な他
の単量体( a−3 )の5〜80重量%とを、好まし
くは、(a−1)の20〜60重量%、(a−2)の1
0〜40M量%および(a一3)の10〜70重量%を
、これら全反応成分の合計量が100重量%となるよう
に共重合させればよい。In order to obtain the desired fluoroolefin copolymer from the various search components listed above, 15 to 70% by weight of the fluoroolefin (a-1) and the glycidyl group-containing monomer (a- 2) and 5 to 80% by weight of the other copolymerizable monomer (a-3), preferably 20 to 60% by weight of (a-1), ( a-2) 1
0 to 40% by weight of M and 10 to 70% by weight of (a-3) may be copolymerized such that the total amount of all these reaction components is 100% by weight.
フルオロオレフィン(a−1)の使用量が15重量%未
満の場合には、耐候性が不十分であるし、一方、70重
量%を超える場合には、塗膜の光沢が低くなくなるので
、いずれも好捷しくけなく、また、グリシジル基含有単
量体(a−2)の使用量が5重量%未満では、どうして
も硬化性が低く、したがって得られる塗膜の耐溶剤性が
不十分となるし、一方、40重量%を超えると、硬化剤
(B)の使用量が多くなり、その結果として、どうして
も耐候性の低下を招くことになるので、いずれも好まし
くなく、さらに共重合可能な他の単量体(a3)の使用
量が5重量%未満の場合には、塗膜の光沢が不十分とな
り易く、一方、80重量%を超えると、どうしても耐候
性が低下するようになるので、いずれも好ましくない。If the amount of fluoroolefin (a-1) used is less than 15% by weight, the weather resistance will be insufficient, while if it exceeds 70% by weight, the gloss of the coating will not be low, so Moreover, if the amount of the glycidyl group-containing monomer (a-2) used is less than 5% by weight, the curability will inevitably be low, and the resulting coating film will therefore have insufficient solvent resistance. On the other hand, if it exceeds 40% by weight, the amount of curing agent (B) used will increase, which will inevitably lead to a decrease in weather resistance, which is undesirable. If the amount of monomer (a3) used is less than 5% by weight, the gloss of the coating film tends to be insufficient, while if it exceeds 80% by weight, the weather resistance inevitably decreases. Neither is preferable.
そして、当該フルオロオレフイン共重合体(A)を調製
するには、また、ラジカル重合開始剤の存在下で、塊状
重合、溶液(加圧〕重合、懸濁重合1たは乳化重合など
の公知の方法により、回分式、半連続式または連続式の
いずれかの操作で行なえばよい。In order to prepare the fluoroolefin copolymer (A), known methods such as bulk polymerization, solution (pressure) polymerization, suspension polymerization 1 or emulsion polymerization may be carried out in the presence of a radical polymerization initiator. Depending on the method, it may be carried out in a batch, semi-continuous or continuous manner.
上記したラジカル重合開始剤としては、アセチルt4−
オキサイドもしくはペンゾイルノe−オキザイドの如き
ノアシルバーオキサイド類;メチルエチルケトンパーオ
キサイドもしくはシクロヘキサノン・やーオキサイドの
如きケトン系パーオキサイド類;過酸化水素もしくはt
ert−ブチルノ・イドロパーオキサイドの如きハイド
ロパーオキサイド類;ヅーtert−ブチルパーオキサ
イドもしくはジクミルノ々−オキサイドの如きジアルキ
ル!+−オキサイド類: tert−プチルパーオキシ
アセテートもしくはtert−プチルパーオキシビパレ
ートの如きアルキルA’−オキシエステル類;または過
硫酸カリウムもしくは過硫酸アンモニウムの如き過硫酸
塩;アルいはアゾビスインブチロニトリル、アゾビスイ
ソバレロニトリルの如きアゾ系化合物などが代表的万も
のであるが、これらは必要に応じて、亜硫酸水素ナトリ
ウムもしくはビロ亜硫酸ナトリウムの如き無機系還元剤
、またはナフテン酸コバルトもしくはジメチルアニリン
の如き有機系還元剤と組み合わせた形で用いてもよい。As the above-mentioned radical polymerization initiator, acetyl t4-
Noah silver oxides such as oxide or penzoylno-e-oxide; ketone peroxides such as methyl ethyl ketone peroxide or cyclohexanone oxide; hydrogen peroxide or t
Hydroperoxides such as ert-butyl hydroperoxide; dialkyls such as tert-butyl peroxide or dicumyl oxide! +-Oxides: Alkyl A'-oxyesters such as tert-butylperoxyacetate or tert-butylperoxybiparate; or persulfates such as potassium persulfate or ammonium persulfate; al or azobisinbutyro Typical examples include azo compounds such as nitrile and azobisisovaleronitrile, but if necessary, these may be combined with an inorganic reducing agent such as sodium bisulfite or sodium birosulfite, or cobalt naphthenate or dimethylaniline. It may also be used in combination with an organic reducing agent such as.
共重合反応方法としては、前掲した如き各種の方法のう
ち,溶液重合法が最も簡便である。そのさいに用いられ
る溶剤として代表的なものにはトルエン、キシレン、/
クロヘキサン、n−へキサンもしくはオクタンの如き炭
化水素系;酢酸メチル、酢酸エチルもしくは酢酸プチル
の如きエステル系;アセトン、メチルエチルケトン、メ
チルイソブチルケトンもしくはシクロヘキサノンの如き
ケトン系;ジメチルホルムアミドもしくはジメチルアセ
トアミドの如きアミド系;またはメタノール、エタノー
ル、イソプロパノール、n−ブタノール、インプタノー
ル、sec−プタノールもしくはエチレングリコールモ
ノアルキルエーテルの如きアルコール系溶剤、あるいは
これらの混合物などがある。As a copolymerization reaction method, among the various methods listed above, the solution polymerization method is the simplest. Typical solvents used in this process include toluene, xylene,
Hydrocarbons such as chlorhexane, n-hexane or octane; esters such as methyl acetate, ethyl acetate or butyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; amides such as dimethylformamide or dimethylacetamide. or alcoholic solvents such as methanol, ethanol, isopropanol, n-butanol, imptanol, sec-butanol or ethylene glycol monoalkyl ether, or mixtures thereof.
壕だ、こうした共重合反応を行なうにさいしては、分子
量調節剤としてラウリルメル力ブタン、オクチルメル力
ブタン、2−メルカプトエタノ−ル捷たはα−メチルス
チレン・ダイマーの如き各種の連鎖移動剤をも使用する
ことができる。However, when carrying out such a copolymerization reaction, various chain transfer agents such as lauryl mer-butane, octyl mer-butane, 2-mercaptoethanol, or α-methylstyrene dimer are used as molecular weight regulators. can also be used.
共重合反応を行なうにさいしては、また、−20℃より
150℃なる範囲内の温度が適当であるし、概ね1 0
0 K9/ cm2以下の反応圧力が適当である。When carrying out the copolymerization reaction, a temperature within the range of -20°C to 150°C is appropriate, and the temperature is approximately 10°C.
A reaction pressure of 0 K9/cm2 or less is suitable.
このようにして得られるフルオロオレフィン共重合体(
A)の分散液壕たけ溶液から、媒質である水または溶剤
を除去する方法としては、公知の方法のいずれもが利用
できるのが、とりわけ、減圧下に加熱留出せしめるとい
う方法が推奨できる。The fluoroolefin copolymer obtained in this way (
As a method for removing water or a solvent as a medium from the dispersion solution in A), any of the known methods can be used, and in particular, a method of heating and distilling under reduced pressure is recommended.
そして、得られる当該共重合体仏)の数平均分子量とし
ては、通常、i,ooo〜100,000 、好ましく
は3,000〜20,000なる範囲が、甘た当該共重
合体(A)の工?キシ当量としては、通常、270〜2
,000,好ましくは、350〜1,500なる範囲内
が、それぞれに適切である。The number average molecular weight of the obtained copolymer (A) is usually in the range of i,ooo to 100,000, preferably 3,000 to 20,000. Engineering? The xy equivalent is usually 270-2
,000, preferably in the range from 350 to 1,500.
さらに、当該フルオロオレフイン共重合体(A)の軟化
点としては、通常、60〜150℃、好ましくは80〜
130℃なる範囲内が適切である。Furthermore, the softening point of the fluoroolefin copolymer (A) is usually 60 to 150°C, preferably 80 to 150°C.
A temperature within the range of 130°C is suitable.
この軟化点が60℃未満である場合には、粉体塗料の耐
ブロッキング性に難点が現われ易くなるし、一方、15
0℃を超えて余りに高くなると、どうしても、塗膜の平
滑性などが劣るようになるので、いずれも好ましくない
。If this softening point is less than 60°C, problems tend to appear in the blocking resistance of the powder coating;
If the temperature is too high, exceeding 0°C, the smoothness of the coating film will inevitably deteriorate, which is not preferable.
次いで、前記したグリシジル基反応性硬化剤(B)、つ
マシ、フルオロオレフィン共重合体(A)中のグリシジ
ル基と反応性を有する硬化剤の代表例としては、少なく
とも2個のカルポキシル基を有する化合物が挙げられる
が、そのうちでも、特に多塩基酸系化合物またはそれら
の酸無水物系化合物の使用が望ましい。Next, representative examples of the glycidyl group-reactive curing agent (B), the curing agent having reactivity with the glycidyl group in the fluoroolefin copolymer (A), and those having at least two carpoxyl groups. Examples include compounds, among which it is particularly desirable to use polybasic acid compounds or their acid anhydride compounds.
まず、かかる多塩基酸系化合物の代表例としては、一分
子中に2個以上のカルポキシル基を有するアクリル樹脂
、もしくは一分子中に2個以上のカルボキシル基を有す
るポリエステル樹脂、またハ、アジピン酸、セバシン酸
、アゼライン酸、デカンニ酸、ヘキサデカ/二酸、アイ
コサンニ酸もしくはテトラアイコサンニ酸の如き脂肪族
二塩基酸類が挙けられるし、あるいは、イソフタル酸の
如き芳香族二塩基酸類;または、ヘキサヒドロフタル酸
もしくはテトラヒドロフタル酸の如き脂環式二塩基酸類
;さらにはトリメリット酸の如き三塩基酸なども挙げら
れるし、勿論ながら、一般式HOOC −{CF 2}
−− COOH [ I ]で示される
ノや−フルオロニ塩基酸もまた使用できる。First, typical examples of such polybasic acid compounds include acrylic resins having two or more carboxyl groups in one molecule, polyester resins having two or more carboxyl groups in one molecule, and c) adipic acid. , aliphatic dibasic acids such as sebacic acid, azelaic acid, decanoic acid, hexadeca/diacid, icosaniic acid or tetraicosaniic acid; or aromatic dibasic acids such as isophthalic acid; Examples include alicyclic dibasic acids such as hydrophthalic acid or tetrahydrophthalic acid; further tribasic acids such as trimellitic acid; and, of course, those having the general formula HOOC -{CF 2}
-Ya-fluoronibasic acid represented by --COOH [I] can also be used.
次いで、前記した多塩基酸無水物系化合物の代表例とし
ては、一分子中に2個以上の酸無水基を有するアクリル
樹脂またはポリエステル樹脂などが挙げられるし、ある
いは、無水トリメリット酸または無水ピロメリット酸な
どが挙げられる。Typical examples of the polybasic acid anhydride compounds mentioned above include acrylic resins or polyester resins having two or more acid anhydride groups in one molecule, or trimellitic anhydride or pyroanhydride. Examples include mellitic acid.
前掲された種々の化合物は単独使用でも、2種以上の併
用でもよいことは勿論であるが、これらの各種の化合物
のうち、耐プロッキング性や諸物性などの面からは、脂
肪族二塩基酸類、就中、直鎖の二塩基酸の使用が望まし
いし、耐候性などの面からは、パー7ルオロニ塩基酸の
使用が望ましい。Of course, the various compounds listed above can be used alone or in combination of two or more, but among these various compounds, from the viewpoint of blocking resistance and various physical properties, aliphatic dibasic It is desirable to use acids, especially linear dibasic acids, and from the viewpoint of weather resistance, it is desirable to use per-7 fluoronibasic acids.
r1ら)
そして、当該グリシジル基反応性硬化剤(B)の使用量
としては、前記グリシジル基含有フルオロオレフィン共
重合体囚中に存在するこの(β−メチル)グリシジル基
に対して0.5〜15倍当量の割合となるような範囲内
が適切であシ、かかる範囲内の量を配合することが望ま
しい。r1 et al.) The amount of the glycidyl group-reactive curing agent (B) used is 0.5 to 0.5 to the (β-methyl)glycidyl group present in the glycidyl group-containing fluoroolefin copolymer. It is appropriate to have a ratio of 15 times equivalent, and it is desirable to blend the amount within this range.
さらにまた、前記した硬化触媒(C)の代表例としてハ
、トリフェニルホスフィンの如! 各種ホ/l. 7イ
ン類や、2−メチルイミダゾールの如き各種イミダゾー
ル類などが挙げられる。Furthermore, as a representative example of the above-mentioned curing catalyst (C), triphenylphosphine may be used. Various ho/l. Examples include 7ynes and various imidazoles such as 2-methylimidazole.
かくして得られ゛る本発明の粉体塗料用樹脂組成物には
、さらに必要に応じて、顔料、各種樹脂類、流動調整剤
、酸化防止剤、紫外線吸収剤またはシランカップリング
剤などの、公知慣用の各種添加剤を加えることができる
のは勿論である。The thus obtained resin composition for powder coating of the present invention may further contain known pigments, various resins, fluidity regulators, antioxidants, ultraviolet absorbers, silane coupling agents, etc., as necessary. Of course, various conventional additives can be added.
そして、本発明の組成物は、前掲された如きそれぞれの
成分を、熱ロールやコニーダーなどの混線機により、8
0〜150℃程度の温度で溶融混練し、次いで粉砕する
ことによって得られる。The composition of the present invention can be prepared by mixing each of the above-mentioned components with a mixer such as a hot roll or a co-kneader.
It is obtained by melt-kneading at a temperature of about 0 to 150°C and then pulverizing.
次に、本発明を参考例、実施例および比較例によシー層
具体的に説明するが、以下において、部および%は特に
断シのない限シ、すべて重量基準であるものとする。Next, the present invention will be explained in detail with reference to Reference Examples, Examples, and Comparative Examples. In the following, all parts and percentages are based on weight unless otherwise noted.
参考例1〜7〔フルオロオレフイン共重合体(A)の調
製例〕
内容積が1lなるステンレス製の耐圧容器内に、メチル
イソブチルケトンの4001と、第1表に示されている
通りの、[パーブチル PV J [日本油脂〔株〕製
の過酸化物系ラジカル重合開始剤〕と、ビス(1,2,
2.6.6−ペンタメチルー4−ビベリジニル)セバケ
ートト、エチルビニルエーテル( EVE )、シクロ
ヘキシビニルエーテル( CHVE ) 、グリシジル
ビニルエーテル(GVE) 、グリシジルメタクリレー
} (GMA)、グリシジルアクリレート(GA)Jペ
オバ 9」(オランダ国シェル社製の、第三級炭素原子
に結合したカルデキシル基を有するC,の脂肪族カルデ
ン酸のビニルエステル;以下,YV−9と略記する。〕
、安息香酸ビニル(VBZ)またはp(l8)
tert−ブチル安息香酸ビニル( VPTBZ )を
仕込んで、ドライアイス/メタノール浴で−70℃に冷
却し、窒素ガスを吹き込んで耐圧容器内の空気を置換し
た。Reference Examples 1 to 7 [Preparation example of fluoroolefin copolymer (A)] In a stainless steel pressure-resistant container with an internal volume of 1 liter, 4001 of methyl isobutyl ketone and [ as shown in Table 1] were added. Perbutyl PV J [peroxide-based radical polymerization initiator manufactured by NOF Corporation] and bis(1,2,
2.6.6-pentamethyl-4-biveridinyl) sebacate, ethyl vinyl ether (EVE), cyclohexyvinyl ether (CHVE), glycidyl vinyl ether (GVE), glycidyl methacrylate (GMA), glycidyl acrylate (GA) Vinyl ester of C, aliphatic caldenic acid having a caldexyl group bonded to a tertiary carbon atom, manufactured by Shell, Netherlands; hereinafter abbreviated as YV-9.]
, vinyl benzoate (VBZ) or p(l8) tert-butyl vinyl benzoate (VPTBZ), cooled to -70°C in a dry ice/methanol bath, and replaced the air in the pressure vessel by blowing in nitrogen gas. did.
次いで、液化採取したクロルトリフルオ口エチレン(
CTFE )または、ヘキサフルオ口プロピレン(RF
P)を同表に示される通りの重量比で仕込んで封管した
し、一方、テトラフルオロエチレン(TFE)を用いる
場合には、バルブ付きの耐圧容器を使用し、上述したと
同様に各原料の仕込みを行なったのち、TFEポンペか
ら、とのTFEを加圧封入し、その後、バルブを閉めて
から秤量した。Next, the liquefied and collected chlortrifluoroethylene (
CTFE) or hexafluoropropylene (RF
P) at the weight ratio shown in the same table and sealed in a tube. On the other hand, when using tetrafluoroethylene (TFE), a pressure-resistant container with a valve was used, and each raw material was charged in the same manner as described above. After the preparation, TFE of and was sealed under pressure from a TFE pump, and then the valve was closed and weighed.
しかるのち、これらのそれぞれの耐圧容器を、60℃に
加温された回転式恒温水槽に入れて、16時間反応を行
なってから、内容物を取シ出し、さらに減圧、加熱条件
下に、溶剤および揮発分を留去して、各糧の目的共重合
体を得た。Thereafter, each of these pressure-resistant containers was placed in a rotary thermostatic water bath heated to 60°C, and after a 16-hour reaction, the contents were taken out, and the solvent was added under reduced pressure and heating conditions. Then, the volatile components were distilled off to obtain the desired copolymers for each food.
それぞれのフルオロオレフィン共重合体(A)について
、各特性値を測定した処、同表に示されるような結果が
得られた。When each characteristic value was measured for each fluoroolefin copolymer (A), the results shown in the table were obtained.
実施例1〜9および比較例1
各参考例で得られたそれぞれのフルオロオレフィン共重
合体(A)を、第2表に示されている通りの重量比の硬
化剤(B)および充填剤を混合し、あるいは硬化剤(B
)、硬化触媒(C)および充填剤を混合し、冷却し、粉
砕してから、150メッシュの金網にて分級して粉体塗
料を得た。Examples 1 to 9 and Comparative Example 1 Each fluoroolefin copolymer (A) obtained in each reference example was mixed with a curing agent (B) and a filler in the weight ratios shown in Table 2. Mixing or hardening agent (B
), a curing catalyst (C), and a filler were mixed, cooled, pulverized, and then classified using a 150-mesh wire mesh to obtain a powder coating.
次いで、それぞれの粉体塗料を08闘厚のデンデライト
処理鋼板に、焼付後の膜厚が60〜70ミクロンとなる
ように各別に静電塗装し、180℃で20分間焼付を行
なって、各種の硬化塗膜を得た。Next, each powder coating was applied electrostatically to a Denderite-treated steel plate with a thickness of 08 to give a film thickness of 60 to 70 microns after baking, and baked at 180°C for 20 minutes. A cured coating film was obtained.
なお、比較例1としては、市販のアクリル系粉体塗料、
つ1,?、ふっ素不含で、かつ、グリシソル基含有の従
来型粉体塗料を用いた。In addition, as Comparative Example 1, commercially available acrylic powder paint,
1,? , a conventional powder coating that is fluorine-free and contains glycisol groups was used.
それぞれの塗膜について諸物性の評価を行なった処、同
表に示されるような結果が得られた。When various physical properties of each coating film were evaluated, the results shown in the table were obtained.
なお、各物性の評価の要領ならびに基準は、次に示す通
りである。Note that the procedures and criteria for evaluating each physical property are as shown below.
平 滑 性・・・目視により判定
光 沢・・−JIS K5400の6・7項に準拠
エリクセン・・・JIS Z − 2247に準拠この
エリクセン値が大きいほど、
可撓性にすぐれることを意味する。Smoothness: determined by visual inspection Gloss: - Compliant with JIS K5400 Sections 6 and 7 Erichsen: Compliant with JIS Z-2247 The larger the Erichsen value, the better the flexibility. .
耐ブロンキンク牲・・粉体塗料の157を4 Q ur
nφの試MIfK[Jf2L、20y−/CTn2 の
荷重をかけて35℃に240時間放置
してから試料を取り出し、ぞのさ
い、元の粉末状に戻る場合には
「良好」とし、ブロッキングが認
められる場合には「不艮」とした。Broken kink resistance... 4 Qur about powder coating 157
nφ test MIfK [Jf2L, 20y-/CTn2 was applied and the sample was left at 35℃ for 240 hours. If the sample returned to its original powder state after that, it was considered "good" and blocking was observed. If it was, it was marked as ``not disgraced.''
耐 候 性・・・サンシャイン・ウェザオメーターにか
けて1,000時間後の、光沢の
保持率を以て表示し、数値の高い
ものほど、耐候性にすぐれている
ことを意味する。Weather resistance: It is expressed as the gloss retention rate after 1,000 hours on a Sunshine Weatherometer, and the higher the value, the better the weather resistance.
,−9
/′
〔発明の効果〕
第2表の結果からも明らかなように、本発明の粉体塗料
用樹脂組成物は、従来型粉体塗料を遥かに凌駕する耐候
性を有すると共に、種々の物性のバランスKも優れるも
のであることが知れる。, -9/' [Effects of the Invention] As is clear from the results in Table 2, the resin composition for powder coatings of the present invention has weather resistance that far exceeds that of conventional powder coatings, and It can be seen that the balance K of various physical properties is also excellent.
Claims (1)
で、かつ、環球法による軟化点が60〜150℃なる、
グリシジル基を有するフルオロオレフィン共重合体と、
(B)このグリシジル基と反応性を有する硬化剤とを、
必須の成分として含んで成る、熱硬化性粉体塗料用樹脂
組成物。 2、(A)数平均分子量が1,000〜100,000
で、かつ、環球法による軟化点が60〜150℃なる、
グリシジル基を有するフルオロオレフィン共重合体と、
(B)このグリシジル基と反応性を有する硬化剤と、(
C)上記したグリシジル基含有フルオロオレフィン共重
合体(A)と上記したグリシジル基反応性硬化剤(B)
との架橋反応を促進させるための硬化触媒とを、必須の
成分として含んで成る、熱硬化性粉体塗料用樹脂組成物
。 3、前記グリシジル基含有フルオロオレフィン共重合体
(A)が、フルオロオレフィン(a−1)の15〜70
重量%と、グリシジル基を有する単量体(a−2)の5
〜40重量%と、上記したフルオロオレフィン(a−1
)およびグリシジル基含有単量体(a−2)と共重合可
能な他の単量体(a−3)の5〜80重量%とを、これ
らの(a−1)、(a−2)および(a−3)なる全単
量体の合計量が100重量%となるように共重合させて
得られるものである、請求項1または2に記載の熱硬化
性粉体塗料用樹脂組成物。 4、前記グリシジル基反応性硬化剤(B)が少なくとも
2個のカルボキシル基を有する化合物である、請求項1
または2に記載の熱硬化性粉体塗料用樹脂組成物。 5、前記グリシジル基反応性硬化剤(B)が、長鎖の脂
肪族直鎖二塩基酸である、請求項1、2または4に記載
の熱硬化性粉体塗料用樹脂組成物。 6、前記グリシジル基反応性硬化剤(B)が、一般式 ▲数式、化学式、表等があります▼〔 I 〕 〔但し、式中のnは1〜24なる 整数であるものとする。〕 で示され化合物である、請求項1、2または4に記載の
熱硬化性粉体塗料用樹脂組成物。[Claims] 1. (A) Number average molecular weight is 1,000 to 100,000
and the softening point according to the ring and ball method is 60 to 150°C.
A fluoroolefin copolymer having a glycidyl group,
(B) a curing agent that is reactive with this glycidyl group,
A resin composition for a thermosetting powder coating, comprising the following as an essential component. 2. (A) Number average molecular weight is 1,000 to 100,000
and the softening point according to the ring and ball method is 60 to 150°C.
A fluoroolefin copolymer having a glycidyl group,
(B) a curing agent that is reactive with this glycidyl group;
C) The above glycidyl group-containing fluoroolefin copolymer (A) and the above glycidyl group-reactive curing agent (B)
A resin composition for a thermosetting powder coating, comprising as an essential component a curing catalyst for promoting a crosslinking reaction with a thermosetting powder coating. 3. The glycidyl group-containing fluoroolefin copolymer (A) has 15 to 70 of the fluoroolefin (a-1).
5% by weight of the monomer (a-2) having a glycidyl group
~40% by weight, and the above-mentioned fluoroolefin (a-1
) and 5 to 80% by weight of the other monomer (a-3) copolymerizable with the glycidyl group-containing monomer (a-2), these (a-1), (a-2) The resin composition for a thermosetting powder coating according to claim 1 or 2, which is obtained by copolymerizing the monomers (a-3) and (a-3) such that the total amount is 100% by weight. . 4. Claim 1, wherein the glycidyl group-reactive curing agent (B) is a compound having at least two carboxyl groups.
or the resin composition for thermosetting powder coating according to 2. 5. The resin composition for a thermosetting powder coating according to claim 1, 2 or 4, wherein the glycidyl group-reactive curing agent (B) is a long-chain aliphatic linear dibasic acid. 6. The glycidyl group-reactive curing agent (B) has the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [I] [However, n in the formula shall be an integer from 1 to 24. ] The resin composition for thermosetting powder coating according to claim 1, 2 or 4, which is a compound represented by the following.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5513889A JPH02235969A (en) | 1989-03-09 | 1989-03-09 | Resin composition for thermosetting powder coating material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5513889A JPH02235969A (en) | 1989-03-09 | 1989-03-09 | Resin composition for thermosetting powder coating material |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH02235969A true JPH02235969A (en) | 1990-09-18 |
Family
ID=12990418
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP5513889A Pending JPH02235969A (en) | 1989-03-09 | 1989-03-09 | Resin composition for thermosetting powder coating material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH02235969A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999057208A1 (en) * | 1998-05-01 | 1999-11-11 | Daikin Industries, Ltd. | Thermosetting powder coating composition |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01103670A (en) * | 1987-07-31 | 1989-04-20 | Nippon Oil & Fats Co Ltd | Thermosetting powder coating composition |
-
1989
- 1989-03-09 JP JP5513889A patent/JPH02235969A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01103670A (en) * | 1987-07-31 | 1989-04-20 | Nippon Oil & Fats Co Ltd | Thermosetting powder coating composition |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999057208A1 (en) * | 1998-05-01 | 1999-11-11 | Daikin Industries, Ltd. | Thermosetting powder coating composition |
US6673454B1 (en) | 1998-05-01 | 2004-01-06 | Daikin Industries, Ltd. | Thermosetting powder coating composition |
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