JPH0439325A - Polyester resin composition and powder-coating composition - Google Patents
Polyester resin composition and powder-coating compositionInfo
- Publication number
- JPH0439325A JPH0439325A JP14661690A JP14661690A JPH0439325A JP H0439325 A JPH0439325 A JP H0439325A JP 14661690 A JP14661690 A JP 14661690A JP 14661690 A JP14661690 A JP 14661690A JP H0439325 A JPH0439325 A JP H0439325A
- Authority
- JP
- Japan
- Prior art keywords
- polyester resin
- acid
- composition
- curing agent
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 31
- 239000008199 coating composition Substances 0.000 title claims abstract description 10
- 229920001225 polyester resin Polymers 0.000 title claims description 39
- 239000004645 polyester resin Substances 0.000 title claims description 39
- 239000002253 acid Substances 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 26
- 229920005862 polyol Polymers 0.000 claims abstract description 16
- 150000003077 polyols Chemical class 0.000 claims abstract description 16
- 150000002009 diols Chemical class 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 4
- -1 isocyanate compound Chemical class 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 230000009477 glass transition Effects 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 42
- 239000011248 coating agent Substances 0.000 abstract description 40
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000758 substrate Substances 0.000 abstract description 4
- 230000000379 polymerizing effect Effects 0.000 abstract description 3
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000005336 cracking Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 15
- 239000003973 paint Substances 0.000 description 13
- 229910000831 Steel Inorganic materials 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 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
- 229920001195 polyisoprene Polymers 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 5
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 238000005809 transesterification reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical class CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008094 contradictory effect Effects 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002483 hydrogen compounds Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-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
- 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 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- MLRVZFYXUZQSRU-UHFFFAOYSA-N 1-chlorohexane Chemical compound CCCCCCCl MLRVZFYXUZQSRU-UHFFFAOYSA-N 0.000 description 1
- 125000004830 1-ethyl-1-methylethylene group Chemical group [H]C([H])([H])C([H])([H])C([*:1])(C([H])([H])[H])C([H])([H])[*:2] 0.000 description 1
- 125000004812 1-ethylethylene group Chemical group [H]C([H])([H])C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- WKJICCKTDQDONB-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxycarbonyl)cyclohexane-1-carboxylic acid Chemical compound OC(=O)C1CCCCC1C(=O)OCC1OC1 WKJICCKTDQDONB-UHFFFAOYSA-N 0.000 description 1
- LXUNZSDDXMPKLP-UHFFFAOYSA-N 2-Methylbenzenethiol Chemical compound CC1=CC=CC=C1S LXUNZSDDXMPKLP-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N 2-propanol Substances CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical group CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- REIDAMBAPLIATC-UHFFFAOYSA-N 4-methoxycarbonylbenzoic acid Chemical compound COC(=O)C1=CC=C(C(O)=O)C=C1 REIDAMBAPLIATC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 240000001980 Cucurbita pepo Species 0.000 description 1
- 235000009852 Cucurbita pepo Nutrition 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Natural products NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 108010008488 Glycylglycine Proteins 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229930003836 cresol Natural products 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
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007610 electrostatic coating method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- SOOARYARZPXNAL-UHFFFAOYSA-N methyl-thiophenol Natural products CSC1=CC=CC=C1O SOOARYARZPXNAL-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical compound OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 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
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】
「産業上の利用分野］
本発明は、ポリエステル樹脂組成物、及びそれを含有し
、硬度と加工性のハラノスに優れ且つ耐候性に優れた硬
化膜を与える粉体塗料組成物に関する。Detailed Description of the Invention "Field of Industrial Application" The present invention relates to a polyester resin composition and a powder coating containing the same that provides a cured film with excellent hardness and processability, and excellent weather resistance. Regarding the composition.
［従来の技術］
近年、無公害、省資源、省力化といった観点から、家電
製品、自動車部品用途を中心として、予め鋼板に塗装を
施した後、加工を行うプレコー・ト鋼板の用途が拡大し
ている。[Conventional technology] In recent years, the use of pre-coated steel sheets, which are processed after painting the steel sheet in advance, has expanded, mainly for home appliances and automobile parts, from the viewpoint of pollution-free, resource-saving, and labor-saving. ing.
従ってプレコート鋼板に用いられる塗料は、他の一般の
塗料に要求される硬化膜の密着性、光沢、耐候性等の性
質の他に、加工性（例えば、折り曲げ性）と硬度という
相反する特性を要求される。Therefore, in addition to properties such as cured film adhesion, gloss, and weather resistance that are required of other general coatings, the coatings used for pre-coated steel sheets also have contradictory properties such as processability (for example, bendability) and hardness. required.
このような２つの相反する特性を満足させる方法として
、特公昭６２−２１８３０号公報、特開昭５１８７７０
号公報には、１，５−ベンタンジオール、１．６−ヘキ
サンジオール、セパチン酸等の柔らかいセグメントを持
つ単量体を共重合したポリエステル樹脂を使用すること
により、硬化膜の硬度と加工性を向上させることが提案
されている。As a method to satisfy these two contradictory characteristics, Japanese Patent Publication No. 62-21830 and Japanese Patent Application Laid-Open No. 518770
The publication discloses that the hardness and processability of the cured film can be improved by using a polyester resin copolymerized with monomers having soft segments such as 1,5-bentanediol, 1,6-hexanediol, and cepatic acid. It is proposed to improve.
［発明か解決しようとする課題］
しかし上記公報による硬化膜は、加工性は向上するが、
ポリエステル樹脂のガラス転移温度および塗膜の硬度は
どうしても低下してしまい、さらに塗膜の耐水性および
耐候性が低下するという問題を有する。そこでネオペン
チルグリコール、／クロヘキサンジメタツール等をセグ
２メントとして導入しポリマー鎖の剛直性を増大させて
Ｔｇを高くしたり、架橋剤の含有量を増やして硬度、耐
候性を向上する試みかなされているが、今度は塗膜か硬
くなり過ぎ、折り曲げ時に塗膜の破損かおこり、加工性
が十分でない。また、ソフトセグメントや可塑剤を入れ
たり、架橋剤を減少させれば塗膜は柔軟になり加工性は
向上するが、逆に硬度、耐候性が低下する。[Problem to be solved by the invention] However, although the cured film according to the above publication improves workability,
There is a problem in that the glass transition temperature of the polyester resin and the hardness of the coating film inevitably decrease, and the water resistance and weather resistance of the coating film also decrease. Therefore, attempts were made to introduce neopentyl glycol, /chlorohexane dimetatool, etc. as a segment to increase the rigidity of the polymer chain and increase Tg, and to increase the content of crosslinking agent to improve hardness and weather resistance. However, this time the paint film became too hard, the paint film was damaged when bent, and the workability was not sufficient. Furthermore, if a soft segment or plasticizer is added or the amount of crosslinking agent is reduced, the coating film becomes flexible and processability improves, but hardness and weather resistance decrease.
このように、十分な硬度と、且つ折り曲げ時に破損等の
起きない良好な加工性を兼備した硬化膜を与えるような
プレコート鋼板用塗料は、未た見出されていない。As described above, a paint for pre-coated steel sheets that provides a cured film that has both sufficient hardness and good workability that does not cause breakage during bending has not yet been found.
本発明の目的は、硬化膜に優れた耐候性、耐水性、密着
性、光沢等を付与するという’ｆｆｆ４としての基本的
な性能を維持しながら、これらの加工性と硬度のバラン
スを改善し、両者を満足するプレコート鋼板用粉体塗料
のポリエステル樹脂組成物を提供することにある。The purpose of the present invention is to improve the balance between processability and hardness while maintaining the basic performance of 'fff4, which is to impart excellent weather resistance, water resistance, adhesion, gloss, etc. to the cured film. The object of the present invention is to provide a polyester resin composition for a powder coating for pre-coated steel sheets that satisfies both of the above.
「課題を解決するための手段］
上記目的を達成するため、分子構造の堅固な芳香環の濃
度を減少させることなく、ポリエステル鎖の自由回転を
成る程度立体的に制御するアルキル置換脂肪族ジオール
及び／又は柔軟構造の脂肪族ジオールを、ポリエステル
鎖中にセグメントとして適度に配合すれば、優れた功を
奏する事を見出し本発明を成すに至った。"Means for Solving the Problems" In order to achieve the above object, an alkyl-substituted aliphatic diol and The present inventors have discovered that excellent results can be achieved by appropriately blending an aliphatic diol with/or a flexible structure as a segment into a polyester chain, and have thus completed the present invention.
即ち本発明は、（１）芳香族ジカルボン酸を少なくとも
８０モル％含有する酸成分、及び（１１）ポリオール成
分として一般式、Ｈ○＋Ｒ−）−ＯＨ
［式中、Ｒは炭素数４又は５の分枝鎖
を有してもよいアルキレン基、ｎは５
〜５０の整数を示す。］
で表わされるジオール
かう調製され、該ジオールがポリエステル樹脂中の１−
Ｌ３０重量％含有するポリエステル樹脂組成物を提供す
る。That is, the present invention provides (1) an acid component containing at least 80 mol% of an aromatic dicarboxylic acid, and (11) a polyol component of the general formula H○+R-)-OH [wherein R is a carbon number of 4 or 5]. an alkylene group which may have a branched chain; n is an integer of 5 to 50; ] The diol represented by
A polyester resin composition containing 30% by weight of L is provided.
本発明のポリエステル樹脂は、上記芳香族ンカルホン酸
含有酸成分（１）と、ポリオール成分（１１）とを重合
して得られる。The polyester resin of the present invention is obtained by polymerizing the aromatic carbonic acid-containing acid component (1) and the polyol component (11).
酸成分（ｉ）中に含有される芳香族／カルホン酸として
は、例えばテレフタル酸、イソフタル酸、オルソフタル
酸、ナフタレンジカルボン酸、または４，４′−ジフェ
ニルカルボン酸等があげられるが、耐候性の面よりテレ
フタル酸またはイソフタル酸か好ましい。Examples of the aromatic/carphonic acid contained in the acid component (i) include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalene dicarboxylic acid, or 4,4'-diphenylcarboxylic acid. Terephthalic acid or isophthalic acid is preferable.
酸成分（Ｉ）は、−Ｆ記芳香族ジカルホノ酸を少なくと
も８０モル％以上含有する。これらの含有量か多い程、
硬化膜の耐候性、耐水性、及び硬度は大きくなる。８０
モル％未満だと硬化膜の硬度が十分てなく好ましくない
。尚、その他の酸として、アジピン酸、セパチン酸、フ
ハク酸等の脂肪族ジカルボン酸、及びトリメリ、）・酸
等の芳香族トリーｈルホノ酸等も配合可能であるか、こ
れらの配合量は２０モル％未満である必要かある。Acid component (I) contains at least 80 mol % of -F aromatic dicarphonic acid. The higher the content of these,
The weather resistance, water resistance, and hardness of the cured film are increased. 80
If it is less than mol%, the hardness of the cured film will not be sufficient, which is not preferable. In addition, as other acids, aliphatic dicarboxylic acids such as adipic acid, sepathic acid, and succinic acid, and aromatic tri-sulfonoic acids such as trimeri acid, etc. can also be blended. Does it need to be less than mol%?
ポリオール成分（１１）は、−峡式
％式％
［式中、Ｒは炭素数４又は５の分枝鎖を有してもよいア
ルキレン基、ｎは５〜５０の整数を示す。］
で表わされ、１種以上の脂肪族ジオールを含有すること
ができる。The polyol component (11) is represented by the formula % [wherein R is an optionally branched alkylene group having 4 or 5 carbon atoms, and n is an integer of 5 to 50]. ] and can contain one or more aliphatic diols.
置換基Ｒは炭素原子を４又は５個有し、直鎖状でも分枝
状でもよいアルキレン基である。具体的には、例えばテ
トラメチレン基（−ＣＨ、−ＣＨ。The substituent R is an alkylene group having 4 or 5 carbon atoms and which may be linear or branched. Specifically, for example, a tetramethylene group (-CH, -CH.
ＣＨ，−ＣＨ，−）、２−メチルテトラメチレン基（−
ＣＨ，−ＣＨ−ＣＨ，−ＣＨ，−ＣＨ，−）、１−エチ
ルエチレン基（−ＣＨ−Ｃ，Ｈ，−ＣＨ，−）、及び１
−ｉｓｏプロピルエチレン基（−ＣＨ−ＣＨ（ＣＨ３）
、−ＣＨ，−）、１−エチル−１−メチルエチレン基（
’−Ｃ−ＣＨ３・Ｃ、Ｈｓ−ＣＨｔ−）等が挙げられる
。CH, -CH, -), 2-methyltetramethylene group (-
CH, -CH-CH, -CH, -CH, -), 1-ethylethylene group (-CH-C,H, -CH, -), and 1
-isopropylethylene group (-CH-CH(CH3)
, -CH,-), 1-ethyl-1-methylethylene group (
'-C-CH3.C, Hs-CHt-) and the like.
そのような脂肪族ジオールとしては、例えば−般式 ％式％［］ （式中、Ｃは５〜５０の整数。） て表わされるジオール、 一般式、 ＣＨ。Such aliphatic diols include, for example - general formula %formula%[] (In the formula, C is an integer from 5 to 50.) Diol represented by general formula, CH.
ＨＯ＋ＣＨ２−ＣＨ−ＣＨｔ−ＣＨｔ→ ○Ｈ−［Ｂ１
（式中、ｍは５〜５０の整数。）
で表わされるジオール、皮ひ
一般式
％式％
（式中、Ｒ１は水素原子若しくはメチル基、Ｒ１はエチ
ル基若しくはイソプロピル基、ｎは５〜５０の整数。）
で表わされるジオール等が挙げられる。」二記ポリオー
ル成分（１１）には、これらジオールのうちの１種以上
が含有される。HO+CH2-CH-CHt-CHt→ ○H-[B1
(In the formula, m is an integer of 5 to 50.) A diol represented by the general formula % formula % (In the formula, R1 is a hydrogen atom or a methyl group, R1 is an ethyl group or an isopropyl group, and n is 5 to 50 An integer of ). The polyol component (11) contains one or more of these diols.
上記一般式［Ａ］及び［Ｂ］で表わされる／オールとし
ては、分子量３００〜４０００．好ましくは６００〜２
５００、重合ｆ’ｉ ５〜５０、好ましくは１０〜３５
の水素化１，４−ポリブタ／エン／オール及び水素化１
．４−ポリイソプレンジオールのそれぞれを使用出来る
。The /ol represented by the above general formulas [A] and [B] has a molecular weight of 300 to 4000. Preferably 600-2
500, polymerization f'i 5-50, preferably 10-35
Hydrogenation of 1,4-polybuta/ene/ol and hydrogenation of 1
．． Each of the 4-polyisoprene diols can be used.
又、上記一般式ＩＣ−１で表わされる／オールとしては
、分子ｆｆ１３００〜４０００、好ましくは６００〜２
５００、重合度５〜５０、好ましくは１０〜３５の、水
素化１，２−若しくは３，４−ポリイソプレンジオール
、又は水素化１，２−ポリブタジェンジオールが使用出
来ル。Further, /ol represented by the above general formula IC-1 has a molecule ff of 1300 to 4000, preferably 600 to 2
Hydrogenated 1,2- or 3,4-polyisoprene diol or hydrogenated 1,2-polybutadiene diol having a polymerization degree of 500 and a degree of polymerization of 5 to 50, preferably 10 to 35 can be used.
上記［Ａ、］〜［Ｃ］で表わされるジオールは、例えば
それぞれ相当するポリブタンエン若しくはポリイソプレ
ンの過酸化水素を開始剤とするラジカル重合あるいはア
ニオン重合により水酸基末端液状ポリブタジェン若しく
は水酸基末端液状ポリイソプレンを得、さらにこれらを
水素還元する事により合成出来る。又、一部は市販され
ている。The diols represented by [A,] to [C] above can be obtained by, for example, radical polymerization or anionic polymerization of the corresponding polybutene or polyisoprene using hydrogen peroxide as an initiator, to obtain a hydroxyl-terminated liquid polybutadiene or a hydroxyl-terminated liquid polyisoprene. , which can be further synthesized by hydrogen reduction. Some of them are also commercially available.
ポリオール成分（１１）中の上記１種以上の脂肪族ジオ
ールの含有量は、調製されたポリエステル樹脂中に１〜
３０重量％含まれるような量である。The content of the one or more aliphatic diols in the polyol component (11) is 1 to 1 in the prepared polyester resin.
The amount is such that it is contained in an amount of 30% by weight.
１重量％未満ては、塗膜の加工性が４−分でなく、又２
０重量％を超えると塗膜硬度か低下するので好ましくな
い。If it is less than 1% by weight, the processability of the coating film will not be 4 minutes or 2 minutes.
If it exceeds 0% by weight, the hardness of the coating film decreases, which is not preferable.
ポリオール成分（■１）には、その他のポリオールを添
加してもよい。その他のポリオールとしては、例工ｆｆ
エチレングリコール、プロピレングリコール、１，４−
ブタ７ノオール、１，３−ブタン／オール、ネオペンチ
ルグリコール、ヒトロキノピいリンク酸不才ペノチルグ
リコールエステル、１４−シクロヘキサンジメタツール
、２．２．４−トノメチルベンタンジオール、２−エチ
ル−２−フチルー１．３−プロパン／オールなどが使用
できる。特にネオペンチルグリコール、ヒドロ牛／ビバ
リノク酸ネオペンチルグリコールエステル、１４−７ク
ロヘ牛サン／メタノールか好ましい。また、３価以トの
ポリオール、例えば、）・リッチロールエタン、トリメ
チロールフロパン、ベノタエブスリトールなともＩＡ
Ｉ’ｌｌ Ｌ −，７、Ｌい。Other polyols may be added to the polyol component (1). Other polyols include example ff
Ethylene glycol, propylene glycol, 1,4-
Buta-7ol, 1,3-butane/ol, neopentyl glycol, human quinolinic acid penotyl glycol ester, 14-cyclohexane dimetatool, 2.2.4-tonomethylbentanediol, 2-ethyl-2 -phthyl-1,3-propane/ol, etc. can be used. Particularly preferred are neopentyl glycol, hydrooxal/bivalinochic acid neopentyl glycol ester, and 14-7 clohesyl san/methanol. In addition, trivalent or higher polyols, such as ), rich olethane, trimethylolfuropane, and benotaebusritol, are also used.
I'll L -, 7, L.
本発明のポリエステル杓町Ａ１１１戊物は、１−記酸成
分（１）とポリオール成分へ、１）Ｎを鈴’ＦＪ ｌｊ
、）市１′ケ法、例えばエステル交換、または的接エス
テル化とそれに続く溶融重縮合反応にて、１１．ｊ〕ｊ
Ｊ“ニーることか出東る。、使用する触媒等も公知のも
の、例えはノブ千ルスズオキサイト、二酸化アン壬モノ
、酢酸亜鉛、酢酸マンガン、酢酸コハル）・、酢酸カル
／ラム、酢［ｆ３ 、テトラフ壬ルチや不−１・、子ト
ライソブロビルチタネート等を使用してよい。又上記重
合法に於いて上記酸成分（ｉ）とポリオール成分（１１
）の添加は、それぞれ全量を同時に加えて重合を行なっ
ても良いし、それぞれ複数回に分けて添加して重合して
もよい。The polyester Dakimachi A111 of the present invention is produced by adding 1) N to the 1-diacid component (1) and the polyol component.
,) by a method such as transesterification or direct esterification followed by melt polycondensation reaction, 11. j〕j
The catalysts used are also known ones, such as tin oxide, aluminum dioxide, zinc acetate, manganese acetate, cohal acetate), calcium acetate/rum, Vinegar [f3], tetrafluoroyl titanate, triisobrobyl titanate, etc. may be used.In the above polymerization method, the above acid component (i) and the polyol component (11) may be used.
) may be added in their entirety at the same time for polymerization, or may be added in multiple portions for polymerization.
上記重合反応組成に於いて、酸成分（１）とポリオール
成分（１１）は本質的には化学量論量でよいが、例えば
酸成分１モルに対し、ポリオール成分は１８０〜１．３
モル、触媒はポリエステル全重量に対して０．０１−０
．５重量％が好ましい。In the above polymerization reaction composition, the acid component (1) and the polyol component (11) may be used in essentially stoichiometric amounts;
Mol, catalyst is 0.01-0 based on the total weight of polyester
．． 5% by weight is preferred.
重合条件は、適宜選択されるが例えば２００〜２５０℃
で４〜ｌＯ時間で行なうことが出来る。Polymerization conditions are appropriately selected, for example, 200 to 250°C.
This can be done in 4 to 10 hours.
このようにして得られる本発明のポリエステル樹脂は、
一般に酸価１０〜１００、あるいは水酸基価１０〜１０
０、ガラス転移温度４０〜７０℃、及び数平均分子量２
０００〜１００００を有する。The polyester resin of the present invention obtained in this way is
Generally acid value 10-100 or hydroxyl value 10-10
0, glass transition temperature 40-70°C, and number average molecular weight 2
000 to 10000.
硬化剤かエボ牛７化合物との組み合わせにおいては酸価
か１０未満では硬化不足になり、１００を越える場合に
は逆に架橋密度か高くなり過き、加工性か著しく低下す
る。同様に、硬化剤かイソ／アネート化合物のブロック
体との組み合わゼにおいても水酸基価が１０未満では硬
化不足になり、１００を越える場合には逆に架橋密度か
高くなり過ぎ、加工性が著しく低下する。又ガラス転移
温度が４０°Ｃ以下では、粉体塗料の貯蔵安定性（ブロ
ッキング性）が悪くなり、７０°Ｃを越えると塗膜外観
（平滑性）か低下する。数平均分子量か２０００未満で
は塗膜の加工性が低下し、１００００を越えると塗膜外
観（平滑性）が低下する。When used in combination with a curing agent or the Evogyu 7 compound, if the acid value is less than 10, curing will be insufficient, and if it exceeds 100, the crosslinking density will become too high and the processability will be significantly reduced. Similarly, in the case of combinations of curing agents and blocks of iso/anate compounds, if the hydroxyl value is less than 10, curing will be insufficient, and if it exceeds 100, the crosslinking density will become too high, resulting in a marked decrease in workability. do. If the glass transition temperature is below 40°C, the storage stability (blocking property) of the powder coating will deteriorate, and if it exceeds 70°C, the appearance (smoothness) of the coating film will deteriorate. If the number average molecular weight is less than 2,000, the processability of the coating film will deteriorate, and if it exceeds 10,000, the appearance (smoothness) of the coating film will deteriorate.
本発明の粉体塗料組成物は、上記ポリエステル樹脂組成
物、硬化剤、及び硬化触媒を含有する。The powder coating composition of the present invention contains the above polyester resin composition, a curing agent, and a curing catalyst.
硬化剤としては、分子中にエポキシ基を２個以上有する
エポキシ化合物、又は分子中にイソンア不−ト基を２個
以北有するイソ／アネート化合物のブロック体等か挙げ
られる。上記エポキシ化合物としては、例えばビスフェ
ノールＡのジグリシジルエーテル、水素化ビスフェノー
ルＡのングリ／ンルエーテル、オルソフタル酸／グリ／
ジルエステル、イソフタル酸ノグリ／ノルエステル、テ
レフタル酸ングリシ／ルエステル、ｐ−オキン安息香酸
グリシジルエステルエーテル、テトラハイドロフタル酸
ジグリ／ジルエステル、ヘキサハイドロフタル酸ングリ
シジルエステル、コハク酸／グリシジルエステル、アジ
ピン酸ジグリンンルエステル、セバンン酸ジグリシンル
エステル、エチレングリコールジグリシジルエーテル、
プロピレングリコールジグリシジルエーテル、１．４−
ブタンジオールジグリシジルエーテル、１．６−ヘキサ
ン／オールジグリシジルエーテル、トリメリット酸トリ
グリ／ジルエステル、トリグリ７ジルイソンアヌレート
、ハイドロキノン／クリ／ノルエーテル等およびそのオ
リゴマー又はそのポリエステル樹脂による変性エボ牛７
化合物等を挙げることか出来る。Examples of the curing agent include epoxy compounds having two or more epoxy groups in the molecule, or blocks of iso/anate compounds having two or more iso-atom groups in the molecule. Examples of the above-mentioned epoxy compounds include diglycidyl ether of bisphenol A, glycidyl ether of hydrogenated bisphenol A, orthophthalic acid/glycidyl ether,
dily ester, isophthalic acid noglycidyl/nor ester, terephthalic acid glycidyl/lyle ester, p-okynebenzoic acid glycidyl ester ether, tetrahydrophthalic acid digly/dyl ester, hexahydrophthalic acid glycidyl ester, succinic acid/glycidyl ester, adipic acid dilycidyl ester Glycine ester, sebanic acid diglycine ester, ethylene glycol diglycidyl ether,
Propylene glycol diglycidyl ether, 1.4-
Butanediol diglycidyl ether, 1,6-hexane/ol diglycidyl ether, trimellitic acid trigly/dyle ester, trigly7dylisone annurate, hydroquinone/cri/nor ether, etc., and their oligomers or their polyester resins 7
Can list compounds etc.
上記インシアネート化合物のブロック体としては、分子
中にイソンア不−ト基を２個以上有するイソシアネート
化合物と、ブロック化剤とを自体公知の方法により付加
反応させたもの等か挙げられる。上記分子中にイソンア
不−ト基を２個以上有するイソ／アネート化合物として
は、例えば芳香族、脂肪族、芳香脂肪族のジイソ／アネ
ート、３価以上のポリイソシアネートかあり、低分子化
合物、高分子化合物のいずれでもよい。たとえばテトラ
メチレンジイソシアネート、ヘキサメチレンジイソシア
ネート、トルエンジイソシアネート、ジフェニルメタン
／イソシアネート、水素化ジフェニルメタンジイソシア
ネート、キシリレンジイソシアネート、水素化キシリレ
ンジイソシアネート、インホロンジイソシアネート、イ
ンホロンジイソシアネートの３量体などのイソ／アネー
ト化合物、あるいはこれらのイソシアネート化合物の過
剰量と、たとえばエチレングリコール、プロピレングリ
コール、トリメチロールプロパン、クリセリン、ソルビ
トール、エチレンンアミン、モノエタ／−ルアミン、／
エタノールアミン、］・リエタノールアミン等の低分子
活性水素化合物又は各種ポリエステルポリオール類、ポ
リエステルポリオール類、ポリアミド類等の高分子活性
水素化合物などとを反応させて得られる末端イソシアネ
ート基含有化合物等が挙げられる。Examples of the above-mentioned blocks of incyanate compounds include those obtained by addition-reacting an isocyanate compound having two or more isonica atom groups in the molecule with a blocking agent by a method known per se. Examples of the above-mentioned iso/anate compounds having two or more iso-anot groups in the molecule include aromatic, aliphatic, and araliphatic diiso/anates, trivalent or higher-valent polyisocyanates, low-molecular compounds, and polymers. Any molecular compound may be used. Iso/anate compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane/isocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, inphorone diisocyanate, trimer of inphorone diisocyanate, or Excess amounts of these isocyanate compounds, such as ethylene glycol, propylene glycol, trimethylolpropane, chrycerin, sorbitol, ethyleneamine, monoethylamine, /
Examples include terminal isocyanate group-containing compounds obtained by reacting low-molecular active hydrogen compounds such as ethanolamine, ]-reethanolamine, or high-molecular active hydrogen compounds such as various polyester polyols, polyester polyols, and polyamides. It will be done.
上記ブロック化剤としては、たとえばフェノール、チオ
フェノール、メチルチオフェノール、エチルフェノール
、クレゾール、キシレノール、レゾルシ／−ル、ニトロ
フェノール、クロロフェノール等のフェノール類、アセ
トキシム、メチルエチルケトオキシム、シクロへキサノ
ンオキシム等のオキシム類、メタノール、エタノール、
フロパノール１、フタノール等のアルコール類、エチレ
ンクロルヒドリン、１３−ジクロロ−２−プロパツール
等のハロゲン置換アルコール類、ｔ−ブタノール、ｔ−
ペンタノール、ｔ−ブタンチオール等の第３級アルコー
ル類、ε−カプロラクタム、δハレロラクタム、γ−ブ
チロラクタム、β−プロピルラクタム等のラクタム類か
挙げられ、その他にも芳香族アミン類、イミド類、活性
メチレン化合物、メルカプタン類、イミン類、尿素類、
７アリ一ル化合物類なとも挙げられる。Examples of the blocking agent include phenols such as phenol, thiophenol, methylthiophenol, ethylphenol, cresol, xylenol, resorcinol, nitrophenol, and chlorophenol; acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime; Oximes, methanol, ethanol,
Alcohols such as furopanol 1 and phthanol, halogen-substituted alcohols such as ethylene chlorohydrin and 13-dichloro-2-propanol, t-butanol, t-
Examples include tertiary alcohols such as pentanol and t-butanethiol, lactams such as ε-caprolactam, δ-halerolactam, γ-butyrolactam, and β-propyllactam, as well as aromatic amines, imides, and active substances. methylene compounds, mercaptans, imines, ureas,
Also included are 7-aryl compounds.
硬化触媒としては通常用いられるものでよく、例えばン
ブチルスズジラウレートのようなスズ化合物およびヘン
／ホンメチルアミンのような三級アミン化合物か挙げら
れる。The curing catalyst may be any one commonly used, including tin compounds such as nbutyltin dilaurate and tertiary amine compounds such as hene/hon methylamine.
本発明の粉体塗料組成物の組成に於いて、上記ポリエス
テル樹脂組成物と硬化剤との組成比は９５１５〜７０／
３０である。組成比が９５１５より大きいと硬化膜の硬
度、耐候性、耐汚染性等が十分でなく、又７０／３０未
満だと硬化膜の加工性が低下し好ましくない。又硬化触
媒の配Ｑｉは、ポリエステル樹脂組成物１００部につき
０１〜５部か好ましい。In the composition of the powder coating composition of the present invention, the composition ratio of the above polyester resin composition and curing agent is 9515 to 70/
It is 30. If the composition ratio is greater than 9515, the hardness, weather resistance, stain resistance, etc. of the cured film will not be sufficient, and if it is less than 70/30, the processability of the cured film will deteriorate, which is undesirable. Further, the ratio Qi of the curing catalyst is preferably 01 to 5 parts per 100 parts of the polyester resin composition.
本発明の粉体塗料組成物には、その他添加剤として例え
ば紫外線吸収剤、酸化防止剤、表面調整剤等を加えても
よい。Other additives such as ultraviolet absorbers, antioxidants, surface conditioners, etc. may be added to the powder coating composition of the present invention.
上記粉体塗料組成物はクリアー被覆組成物として調合し
てもよく、またそれらを顔料とともに配合し、ペイント
を形成してもよい。顔料は常套のいかなるタイプのもの
を用いてもよいか、例えばＭ（ＩＪＳ、酸化鉛、ストロ
ンチウムクロ（１−、、カーホンブラ５．り、コール９
スト、二酸化チクン、フタロンアニノブルー、タルク、
硫酸〕−リウムまたは色顔料、例えばカドミウムイエロ
ー、カドミウムレッド、クロミウムイエローおよび金属
顔料、例えばアルミニウムフレーク等であってもよい。The powder coating compositions described above may be formulated as clear coating compositions, or they may be formulated with pigments to form paints. Any conventional type of pigment may be used; for example, M (IJS, lead oxide, strontium black (1-, carbon black), coal 9.
st, chikun dioxide, phthalone anino blue, talc,
]-lium sulfate or color pigments such as cadmium yellow, cadmium red, chromium yellow and metal pigments such as aluminum flakes.
ペイント中の顔料含有量は適宜選択されるか、例えばポ
リエステル樹脂組成物１００部につき１０〜１００部が
好ましい。The pigment content in the paint is appropriately selected, and is preferably 10 to 100 parts per 100 parts of the polyester resin composition.
本発明の粉体塗料組成物の調製は、通常の方法で行なう
事か出来る。即ち、例えば上記各配合剤を適当な溶剤に
均一に溶解若しくは分散させた後、これを噴霧乾燥等の
方法で乾燥粉体化して調製される。成るいは、上記各配
合剤を溶融し、ミキサー等で混練した後、冷却固化し、
これを粉砕機等で粉砕して調製される。得られた粉体塗
ｔ）の平均粒径は特に限定されないか、例えば５〜３０
μか好ましい。そのために、必要に応し得られた粉体を
ふるい分ｉｔ してもよい。The powder coating composition of the present invention can be prepared by conventional methods. That is, for example, it is prepared by uniformly dissolving or dispersing each of the above-mentioned ingredients in a suitable solvent, and then drying and powdering the resultant by a method such as spray drying. Alternatively, each of the above ingredients is melted, kneaded with a mixer, etc., and then cooled and solidified.
It is prepared by pulverizing this using a pulverizer or the like. The average particle size of the powder coating t) obtained is not particularly limited, for example 5 to 30
μ is preferable. For this purpose, the obtained powder may be sieved if necessary.
粉体塗料の塗装方法としては、公知の如何なる方法でも
よい。例えばあらかしめ加熱した基材になんらかの方法
で粉体塗料を付着させ、被塗物の熱によって粉体塗料を
溶融させ均一な連続被膜を形成させる方法（スプレー法
、流動浸漬法）、粉体塗料を塗装時に加熱し溶融状態で
被塗物に空行させる方法（ｔ′８射法、プラズマ溶ｑ、
１法）、粉体粒子に荷電し静電気力で被塗物に粉体塗料
を空行させた後焼付は乾燥させる方法（静電塗装法）等
がある。Any known method may be used to apply the powder coating. For example, a method in which a powder coating is applied by some method to a base material that has been warmed and heated, and the powder coating is melted by the heat of the object to form a uniform continuous film (spray method, fluidized dipping method), powder coating A method of heating it during coating and passing it onto the object in a molten state (t'8 spray method, plasma melting method,
Method 1), a method in which powder particles are charged and the powder coating is applied to the object to be coated using electrostatic force, and then the coating is dried (electrostatic coating method).
上記粉体塗料か塗装される基材としては、本質的にいか
なる基材、例えば、金属、カラス等、または種々のブラ
イマー面であ−っでもよい。特に塗料は金属表面、例え
ばスチールおよびアルミニウムに有利である。一般に、
膜［１／は所望の用途により変化する。本くの場合、２
０〜１０（’ｔμかイＩ゛用である。The substrate to which the powder coating is applied can be essentially any substrate, such as metal, glass, etc., or various brimer surfaces. The paint is particularly advantageous for metal surfaces, such as steel and aluminum. in general,
The membrane [1/ will vary depending on the desired application. In case of book, 2
0 to 10 ('tμ or iI゛).
基材に塗装した塗膜の硬化は、１６０〜２５０°Ｃで高
い架橋度の硬化塗膜をイＩＬる。硬化時間は硬化温度等
により変化するか、２００〜２５０ ”Ｃ−Ｃ１〜５分
、あるいは１６０〜２００’Ｃて１．）〜３０分か適当
である。The coating film applied to the substrate is cured at 160 to 250°C to form a cured coating film with a high degree of crosslinking. The curing time varies depending on the curing temperature, etc., and is suitably 1 to 5 minutes at 200 to 250''C, or 1.) to 30 minutes at 160 to 200'C.
［発明の効製
本発明の塗料組Ｆ戊物は粉体−Ｃあ１瓢ｆＩ−機ｌ？Ｉ
剤下を含まないため低公害で４３つる。[Effects of the Invention The paint assembly of the present invention is powder-C A1 Gourd fI- Machine L? I
43 vines with low pollution because it does not contain chemicals.
さらに、本発明のポリエステル樹脂のｒ〒成に（１５用
するジオールは、従来使用される１、５−ベンタンジオ
ール、１．６−へ牛サンジオール等に比べ、メチレン鎖
か長いことや、ヒドロキソル基のβ位にアルキル基か存
在していたりしてポリマーの疎水性か高くなり、さらに
β位のアルキル基がエステル結合を立体障害的に保護す
るので耐加水分解性が良くなり、その結果として塗膜の
耐水性および耐候性が改善されている。Furthermore, the diol used in the composition of the polyester resin of the present invention (15) has a longer methylene chain and hydroxyl than the conventionally used 1,5-bentanediol, 1,6-bentanediol, etc. The presence of an alkyl group at the β-position of the group increases the hydrophobicity of the polymer, and the alkyl group at the β-position protects the ester bond with steric hindrance, resulting in improved hydrolysis resistance. The water and weather resistance of the paint film is improved.
更に又本発明のポリエステル樹脂は、堅固な分子構造を
有する芳香環部と比較的柔軟な分子構造を有するジオー
ル部から構成されているので、硬化膜は十分な硬度を有
しつつ、且つ塗装基材を折り曲げたりした時に硬化膜に
ヒビや割れか発生しない優れた加工性を兼備する。Furthermore, since the polyester resin of the present invention is composed of an aromatic ring part with a rigid molecular structure and a diol part with a relatively flexible molecular structure, the cured film has sufficient hardness and is compatible with coating bases. It also has excellent workability, with no cracks or cracks in the cured film when the material is bent.
更に硬化膜は、密着性、光沢等に優れており、従って本
発明の粉体塗料組成物は、例えばプレコート鋼板用塗料
に適する。Furthermore, the cured film has excellent adhesion, gloss, etc., and therefore the powder coating composition of the present invention is suitable, for example, as a coating for pre-coated steel plates.
［実施例： 以下、本発明を実施例で更に詳しく説明する。[Example: Hereinafter, the present invention will be explained in more detail with reference to Examples.
尚、断らない限り「部」は重量部である。In addition, unless otherwise specified, "parts" are parts by weight.
ポリエステル樹脂組成物の調製
（実施例１）
加熱装置、撹拌機、窒素導入管、および分留塔を有する
反応容器にジメチルテレフタレート（ＤＭＴ Ｐ）３２
．０８部（５０モル％）、ネオペンチルグリコール（Ｎ
ＰＣ）３４．４７部、ＥＰＯＬ（水素化ポリイソプレン
ジオール、１．４−／１．２＝構造の混合物、分子ｆｆ
１−１．８６０、平均繰返し数ｎ２６、出光石油化学（
株）製）８．６７部、トリメチロールプロパン（ＴＭＰ
）１．９１Ｌ ジブチルスズオキサイド０．０５部を仕
込み、乾燥窒素下加熱を開始し、原料を融解させた。次
いで１３０℃〜２１０°Ｃの温度でエステル交換反応さ
せメタノールを留出させた。２１０’Ｃでエステル交換
反応を継続し、メタノール１０．６部を捕集した後冷却
した。さらにテレフタル酸２７．４４部（５０モル％）
を加えて２４０’Ｃで脱水エステル化反応を行った。反
応は、樹脂酸価２０の時点て終了した。Preparation of polyester resin composition (Example 1) Dimethyl terephthalate (DMT P) 32
．． 08 parts (50 mol%), neopentyl glycol (N
PC) 34.47 parts, EPOL (hydrogenated polyisoprene diol, mixture of 1.4-/1.2 = structure, molecule ff
1-1.860, average number of repetitions n26, Idemitsu Petrochemical (
Co., Ltd.) 8.67 parts, trimethylolpropane (TMP)
) 1.91L 0.05 part of dibutyltin oxide was charged, and heating under dry nitrogen was started to melt the raw materials. Then, a transesterification reaction was carried out at a temperature of 130°C to 210°C to distill methanol. The transesterification reaction was continued at 210'C, and 10.6 parts of methanol was collected, followed by cooling. In addition, 27.44 parts (50 mol%) of terephthalic acid
was added to carry out a dehydration esterification reaction at 240'C. The reaction was completed when the resin acid value reached 20.
得られたポリエステル樹脂Ａは水酸基価３５、酸価２、
数平均分子量（ポリスチレン換算）５２００てあった。The obtained polyester resin A had a hydroxyl value of 35, an acid value of 2,
The number average molecular weight (polystyrene equivalent) was 5,200.
また、示差走査熱量計（ＤＳＣ）で測定したポリエステ
ル樹脂のガラス転移温度（Ｔｇ）は５２℃であった。Further, the glass transition temperature (Tg) of the polyester resin measured by a differential scanning calorimeter (DSC) was 52°C.
（実施例２〜７及び比較例１〜４）
表−１の組成に基づき、実施例１と同様の反応方法で各
ポリエステル樹脂Ｂ−Ｇ及びＯ−Ｒを合成した。得られ
た各ポリエステル樹脂の水酸基価、酸価、数平均分子量
（ポリスチレン換算）、ＴｇＯ表の値を表−１に示した
。(Examples 2 to 7 and Comparative Examples 1 to 4) Based on the compositions in Table 1, polyester resins BG and OR were synthesized using the same reaction method as in Example 1. The hydroxyl value, acid value, number average molecular weight (in terms of polystyrene), and TgO table values of each of the obtained polyester resins are shown in Table 1.
（実施例８）
加熱装置、撹拌機、窒素導入管、および分留塔を有する
反応容器に７メチルテレフタレート（ＤＭＴ Ｐ）３２
．１９部（４６モル％）、ネオペンチルグリコール（Ｎ
ＰＣ）３４ ８０部、ＥＰＯＬ（水素化ポリイソプレン
／オール、１，４．−／１．２−構造の混合物、分子量
−１８６０、平均繰返し数ｎ２６、出光石油化学（株）
製）１０．０４部、ジブチルスズオキサイド０．０５部
を仕込み、乾燥窒素下加熱を開始し、原料を融解させた
。次いて１３０°Ｃ〜２１０’Ｃの温度でエステル交換
反応させメタノールを留出させた。２１０’Ｃでエステ
ル交換反応を継続し、メタノール１０．８部を捕集した
後冷却した。さらにテレフタル酸２７．５８部を加えて
２４０°Ｃで脱水エステル化反応を行った。(Example 8) 7 Methyl terephthalate (DMT P) 32 was placed in a reaction vessel having a heating device, a stirrer, a nitrogen introduction tube, and a fractionating column.
．． 19 parts (46 mol%), neopentyl glycol (N
PC) 34 80 parts, EPOL (hydrogenated polyisoprene/ol, mixture of 1,4.-/1.2-structure, molecular weight -1860, average repeating number n26, Idemitsu Petrochemical Co., Ltd.)
Co., Ltd.) and 0.05 part of dibutyltin oxide were charged, and heating under dry nitrogen was started to melt the raw materials. Then, a transesterification reaction was carried out at a temperature of 130°C to 210'C to distill methanol. The transesterification reaction was continued at 210'C, and 10.8 parts of methanol was collected, followed by cooling. Furthermore, 27.58 parts of terephthalic acid was added to carry out a dehydration esterification reaction at 240°C.
反応は、樹脂酸価１０．０の時点で終了した。さらにま
た、無水トリメリット酸２．３１部（３モル％）、無水
フタル酸２．７９部（５モル％）を加え２１０℃でエス
テル化反応を続け、酸価３５．０で反応を終了した。The reaction was completed when the resin acid value reached 10.0. Furthermore, 2.31 parts (3 mol%) of trimellitic anhydride and 2.79 parts (5 mol%) of phthalic anhydride were added to continue the esterification reaction at 210°C, and the reaction was completed at an acid value of 35.0. .
得られたポリエステル樹脂Ｈは水酸基価１、酸価３５、
数平均分子量（ポリスチレン換算）５６００てあった。The obtained polyester resin H had a hydroxyl value of 1, an acid value of 35,
The number average molecular weight (polystyrene equivalent) was 5,600.
また、示差走査熱量計（ＤＳＣ）でＵｌ＋定したポリエ
ステル樹脂のカラス転移温度（Ｔ ｇ）は５５°Ｃであ
った。Further, the glass transition temperature (Tg) of the polyester resin was determined by differential scanning calorimeter (DSC) to be 55°C.
（実施例９〜１４及び比較例５〜８）
表−１の組成に基つき、実施例８と同様の反応方法で各
ポリエステル樹脂＋−Ｘ及びＳ〜■を合成した各ポリエ
ステル樹脂の水酸基価、酸価、数平均分子量（ポリスチ
レン換算）、Ｔｇの表の値を表
１に示した。(Examples 9 to 14 and Comparative Examples 5 to 8) Hydroxyl value of each polyester resin +-X and S to , acid value, number average molecular weight (polystyrene equivalent), and Tg values are shown in Table 1.
粉体塗ｔ１組成物の調製伎ひその塗膜性能（実施例１５
）
実施例１て得られたポリエステル樹脂Ａを用い、塗土Ｉ
配合−１に基−）き配合し、ドライプレンター（三）４
゛化丁１機（株）製、商品名ヘン／エルミキ廿−）によ
り約３０ｆ′ν合した後、１００°Ｃの温度条件て押出
混練機（ブス社製、商品名ブスコニーター）を使用して
溶融混練した。冷却後、粉砕機で微粉砕したちのを１５
０メ、／ユの金網て濾過し、）分（本ｖｒ事）を得た。Preparation of powder coating T1 composition and coating film performance (Example 15)
) Coating soil I using polyester resin A obtained in Example 1.
Blend based on formulation-1 and dry planer (3) 4
After mixing for about 30 f'ν with a ``Hen/Ermiki 廿-'' manufactured by Kato Iki Co., Ltd., the mixture was mixed using an extrusion kneader (manufactured by Bus Co., Ltd., trade name Busconiter) at a temperature of 100°C. It was melted and kneaded. After cooling, finely grind 15 pieces using a crusher.
It was filtered through a wire mesh of 0m, /y to obtain ).
空事４配合−１
ポリエステル樹脂Ａ ８０□パ：１；クレラ７
Ｌ Ｉ ” ′）０１酸化チタン
１０部
７７千ル錫、ラウレート１部
モタフロ−１］部
１） イソ十ロンノイノ／マネー）（ＩＰＤＩ）のカプ
ロラフタム フロック Ｉ３ａンｃ ｒ ｌ ５’Ｊ、
ＮＣ○当１ｔ＝３６５゜
２）：モン号ント社製表面謁１整剤。Air 4 combination-1 Polyester resin A 80□Pa: 1; Kurera 7
L I '')01 titanium oxide
10 parts 77,000 L tin, laurate 1 part Motaflow - 1] Part 1) Caprolatum floc of Isotenronnoino/Money) (IPDI) I3a an cr l 5'J,
NC○1t=365°2): Surface audience 1 adjustment manufactured by Mongoto Co., Ltd.
得られた粉体塗料を厚さ０６凹のリン酸亜鉛処理を施し
た鋼板上に静電塗装し、２３０°Ｃで５分間焼付けて硬
化塗膜を得た。得られた試験板の塗膜性能を表−２に示
した。The obtained powder coating was electrostatically coated onto a zinc phosphate-treated steel plate having a thickness of 06 concave and baked at 230° C. for 5 minutes to obtain a cured coating. The coating performance of the obtained test plate is shown in Table 2.
（実施例１６〜２１及び比較例９〜１２）ポリエステル
樹脂Ａの替わりに、各ポリエステル樹脂）３− Ｇ 支
ひＯ−Ｒを用いた以外は実施例１５と同様にして、それ
ぞれ粉体塗料又ひ硬化塗膜を得た。得られた試験板の塗
膜性能を表−２に示した。たたし、実施例２０と実施例
２１に−）いては塗装」配合時、ポリエステル樹脂とク
レランビＩとの比室をそれぞれ７０ｆｆｌ；’３０部、
８５韻／・１５部とした。(Examples 16 to 21 and Comparative Examples 9 to 12) Powder coating or A hardened coating film was obtained. The coating performance of the obtained test plate is shown in Table 2. However, in Example 20 and Example 21, the ratio of polyester resin and Klerambi I was 70ffl; 30 parts, respectively, when blending the coating.
85 rhymes/15 parts.
（実施例２２）
実施例８て得られたポリエステル樹脂■」を用い、塗料
配合−２に基つき配合し、ｌ・ライフレジクー（三井化
下機（株）製、商品名ヘン／エルミキ→十−）により約
３０ｆ′ν間混合した後、１００°Ｃの温度条件て押出
混練機（ブス社製、商品名ブスコニーダー）を使用して
溶融混練した。冷却後、粉砕機で微粉砕したものを１５
０メノンユの金網で濾過−粉体塗料を得た。(Example 22) Using the polyester resin "■" obtained in Example 8, it was blended based on paint formulation-2, and L. Life Resiku (manufactured by Mitsui Kashimiki Co., Ltd., trade name: Hen/Elmiki) was applied. The mixture was mixed for about 30 f'v using an extrusion kneader (manufactured by Bus Co., Ltd., trade name: Busco Kneader) at a temperature of 100°C. After cooling, finely pulverize with a pulverizer to 15
A powder coating was obtained by filtration with a wire mesh of 0 menonyu.
塗料配合−２
ポリエステル樹脂Ｈ８７部
ＴＧＩＣ” １３部
酸化チタン ４０部
モダフロー １部
２と同様にして、それぞれ粉体塗料及び硬化塗膜を得た
。得られた試験板の塗膜性能を表−２に示した。たたし
、実施例２７と実施例２８については塗料配合時、ポリ
エステル樹脂とＴＧＩＣとの比率をそれぞれ８０部／２
０部、９０部／１０部とした。Paint formulation-2 Polyester resin H 87 parts TGIC" 13 parts Titanium oxide 40 parts Modaflow A powder paint and a cured paint film were obtained in the same manner as in Part 1 and 2. The film performance of the obtained test plates is shown in Table 2. However, for Examples 27 and 28, the ratio of polyester resin to TGIC was 80 parts/2 when compounding the paint.
0 parts, 90 parts/10 parts.
１）コトリグリシンルイソ／アヌレート、日産化学（株
）製。1) Cotriglycine luiso/annulate, manufactured by Nissan Chemical Co., Ltd.
得られた粉体塗料を厚さ０．５ｉπのリン酸亜鉛処理を
施した鋼板上に静電塗装し、２３０°Ｃて５分間焼付け
て硬化塗膜を得た。得られた試験板の塗膜性能を表−２
に示した。The obtained powder coating was electrostatically coated onto a steel plate treated with zinc phosphate to a thickness of 0.5iπ, and baked at 230° C. for 5 minutes to obtain a cured coating. Table 2 shows the coating film performance of the obtained test plate.
It was shown to.
（実施例２３〜２８及び比較例１３〜１６）ポリエステ
ル樹脂Ｈの替わりに、各ポリエステル樹脂Ｉ−Ｘ及びＳ
−Ｖを用いた以外は実施例２表−２より明らかなように
、本発明の水酸基を有するボッエステル樹脂と硬化剤と
してプロ２クイソンア不一ト化合物とを組み合わせた場
合（実施例１５〜２１）、あるいは本発明のカルポキ／
ル基を有するポリエステル樹脂と硬化剤としてポリエポ
キシ化合物とを組み合わせた場合（実施例２２〜２８）
、硬度と加工性（ｉ衝撃性、エリクセン、屈曲性）のバ
ランスが優れており、さらに耐沸水性、耐食性、耐候性
に優れた塗膜を得ることかできる。(Examples 23 to 28 and Comparative Examples 13 to 16) Instead of polyester resin H, each polyester resin I-X and S
As is clear from Table 2 of Example 2, except that -V was used, when the Bossester resin having a hydroxyl group of the present invention was combined with a pro2quison achromat compound as a curing agent (Examples 15 to 21) , or Karpoki of the present invention/
When a polyester resin having a group is combined with a polyepoxy compound as a curing agent (Examples 22 to 28)
It has an excellent balance between hardness and workability (i.e. impact strength, Erichsen, and flexibility), and it is possible to obtain coating films with excellent boiling water resistance, corrosion resistance, and weather resistance.
特許出願人 日本ペイント株式会社Patent applicant: Nippon Paint Co., Ltd.
Claims (4)
％含有する酸成分、及び （ｉｉ）ポリオール成分として一般式、 ▲数式、化学式、表等があります▼ ［式中、Ｒは炭素数４又は５の分枝鎖を有してもよいア
ルキレン基、ｎは５〜５０の整数を示す。］ で表わされるジオール から調製され、該ジオールがポリエステル樹脂中の１〜
３０重量％含有するポリエステル樹脂組成物。(1) (i) An acid component containing at least 80 mol% of an aromatic dicarboxylic acid, and (ii) a polyol component that has a general formula, ▲mathematical formula, chemical formula, table, etc.▼ [In the formula, R has 4 carbon atoms or an alkylene group which may have 5 branched chains; n represents an integer of 5 to 50; ] The diol is prepared from a diol represented by
A polyester resin composition containing 30% by weight.
硬化剤を含有し、ポリエステル樹脂組成物と硬化剤との
組成比（ポリエステル樹脂組成物／硬化剤）が９５／５
〜７０／３０である粉体塗料組成物。(2) Contains the polyester resin composition and curing agent according to claim (1), and the composition ratio of the polyester resin composition and curing agent (polyester resin composition/curing agent) is 95/5.
A powder coating composition that is ~70/30.
転移温度４０〜７０℃、及び数平均分子量２０００〜１
００００を有し、硬化剤が、分子中にエポキシ基を２個
以上有するエポキシ化合物である請求項（２）記載の粉
体塗料組成物。(3) The polyester resin has an acid value of 10 to 100, a glass transition temperature of 40 to 70°C, and a number average molecular weight of 2000 to 1.
0000, and the curing agent is an epoxy compound having two or more epoxy groups in the molecule.
ス転移温度４０〜７０℃、及び数平均分子量２０００〜
１００００を有し、硬化剤が分子中にイソシアネート基
を２個以上有するイソシアネート化合物のブロック体で
ある請求項（２）記載の粉体塗料組成物。(4) The polyester resin has a hydroxyl value of 10 to 100, a glass transition temperature of 40 to 70°C, and a number average molecular weight of 2000 to 2000.
10,000, and the curing agent is a block body of an isocyanate compound having two or more isocyanate groups in the molecule.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14661690A JPH0439325A (en) | 1990-06-05 | 1990-06-05 | Polyester resin composition and powder-coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14661690A JPH0439325A (en) | 1990-06-05 | 1990-06-05 | Polyester resin composition and powder-coating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0439325A true JPH0439325A (en) | 1992-02-10 |
Family
ID=15411768
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14661690A Pending JPH0439325A (en) | 1990-06-05 | 1990-06-05 | Polyester resin composition and powder-coating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0439325A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006095901A1 (en) * | 2005-03-11 | 2006-09-14 | Toyo Boseki Kabushiki Kaisha | Copolymerized polyester resin, method for producing same, and resin composition containing copolymerized polyester resin |
| JP2006282938A (en) * | 2005-04-04 | 2006-10-19 | Toyobo Co Ltd | Process for producing copolyester resin, copolyester resin and resin composition for coating material and coated metal plate produced by applying the same |
| JP2009143226A (en) * | 2007-11-22 | 2009-07-02 | Toyobo Co Ltd | Readily bondable polyester film for optical use and laminated polyester film for optical use |
| JP4547644B1 (en) * | 2009-05-22 | 2010-09-22 | 東洋紡績株式会社 | Easy-adhesive polyester film for optics |
| JP2021195383A (en) * | 2020-06-09 | 2021-12-27 | 川上塗料株式会社 | Powder coating composition |
-
1990
- 1990-06-05 JP JP14661690A patent/JPH0439325A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006095901A1 (en) * | 2005-03-11 | 2006-09-14 | Toyo Boseki Kabushiki Kaisha | Copolymerized polyester resin, method for producing same, and resin composition containing copolymerized polyester resin |
| JP2006282938A (en) * | 2005-04-04 | 2006-10-19 | Toyobo Co Ltd | Process for producing copolyester resin, copolyester resin and resin composition for coating material and coated metal plate produced by applying the same |
| JP2009143226A (en) * | 2007-11-22 | 2009-07-02 | Toyobo Co Ltd | Readily bondable polyester film for optical use and laminated polyester film for optical use |
| JP4547644B1 (en) * | 2009-05-22 | 2010-09-22 | 東洋紡績株式会社 | Easy-adhesive polyester film for optics |
| WO2010134416A1 (en) * | 2009-05-22 | 2010-11-25 | 東洋紡績株式会社 | Highly adhesive polyester film for optical use |
| JP2011005854A (en) * | 2009-05-22 | 2011-01-13 | Toyobo Co Ltd | Easily adhesive polyester film for optical use |
| JP2011005858A (en) * | 2009-05-22 | 2011-01-13 | Toyobo Co Ltd | Easily adhesive polyester film for optical use |
| JP2021195383A (en) * | 2020-06-09 | 2021-12-27 | 川上塗料株式会社 | Powder coating composition |
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