JPWO2016047458A1 - Modified epoxy resin for paints and one-pack / lacquer type paints - Google Patents
Modified epoxy resin for paints and one-pack / lacquer type paints Download PDFInfo
- Publication number
- JPWO2016047458A1 JPWO2016047458A1 JP2016550101A JP2016550101A JPWO2016047458A1 JP WO2016047458 A1 JPWO2016047458 A1 JP WO2016047458A1 JP 2016550101 A JP2016550101 A JP 2016550101A JP 2016550101 A JP2016550101 A JP 2016550101A JP WO2016047458 A1 JPWO2016047458 A1 JP WO2016047458A1
- Authority
- JP
- Japan
- Prior art keywords
- component
- epoxy resin
- modified epoxy
- weight
- paint
- 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.)
- Granted
Links
- 239000003973 paint Substances 0.000 title claims abstract description 52
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 49
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 49
- 239000004922 lacquer Substances 0.000 title claims description 6
- 239000004593 Epoxy Substances 0.000 claims abstract description 47
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 150000001412 amines Chemical class 0.000 claims abstract description 14
- 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 claims abstract description 11
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 8
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 8
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 8
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920001515 polyalkylene glycol Polymers 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 33
- 238000000576 coating method Methods 0.000 claims description 30
- 239000011248 coating agent Substances 0.000 claims description 27
- 125000003700 epoxy group Chemical group 0.000 claims description 18
- 125000003277 amino group Chemical group 0.000 claims description 14
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 9
- 229920001451 polypropylene glycol Polymers 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 9
- 238000007711 solidification Methods 0.000 abstract description 4
- 230000008023 solidification Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 20
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 13
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- -1 polyoxyethylene Polymers 0.000 description 11
- 239000007787 solid Substances 0.000 description 9
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 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 4
- 239000000049 pigment Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 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 2
- SYWDPPFYAMFYQQ-KTKRTIGZSA-N (z)-docos-13-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCCN SYWDPPFYAMFYQQ-KTKRTIGZSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- ATOUXIOKEJWULN-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane Chemical compound O=C=NCCC(C)CC(C)(C)CN=C=O ATOUXIOKEJWULN-UHFFFAOYSA-N 0.000 description 1
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- CDULGHZNHURECF-UHFFFAOYSA-N 2,3-dimethylaniline 2,4-dimethylaniline 2,5-dimethylaniline 2,6-dimethylaniline 3,4-dimethylaniline 3,5-dimethylaniline Chemical class CC1=CC=C(N)C(C)=C1.CC1=CC=C(C)C(N)=C1.CC1=CC(C)=CC(N)=C1.CC1=CC=C(N)C=C1C.CC1=CC=CC(N)=C1C.CC1=CC=CC(C)=C1N CDULGHZNHURECF-UHFFFAOYSA-N 0.000 description 1
- XNIOWJUQPMKCIJ-UHFFFAOYSA-N 2-(benzylamino)ethanol Chemical compound OCCNCC1=CC=CC=C1 XNIOWJUQPMKCIJ-UHFFFAOYSA-N 0.000 description 1
- VVHFXJOCUKBZFS-UHFFFAOYSA-N 2-(chloromethyl)-2-methyloxirane Chemical compound ClCC1(C)CO1 VVHFXJOCUKBZFS-UHFFFAOYSA-N 0.000 description 1
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- WWHHPOAJVOMEAI-UHFFFAOYSA-N 3-(2,3-dihydroxyphenyl)sulfanylbenzene-1,2-diol Chemical compound OC1=CC=CC(SC=2C(=C(O)C=CC=2)O)=C1O WWHHPOAJVOMEAI-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- HDONYZHVZVCMLR-UHFFFAOYSA-N N=C=O.N=C=O.CC1CCCCC1 Chemical compound N=C=O.N=C=O.CC1CCCCC1 HDONYZHVZVCMLR-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 150000003946 cyclohexylamines Chemical class 0.000 description 1
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical compound C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 description 1
- NISGSNTVMOOSJQ-UHFFFAOYSA-N cyclopentanamine Chemical class NC1CCCC1 NISGSNTVMOOSJQ-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- LQKYCMRSWKQVBQ-UHFFFAOYSA-N n-dodecylaniline Chemical class CCCCCCCCCCCCNC1=CC=CC=C1 LQKYCMRSWKQVBQ-UHFFFAOYSA-N 0.000 description 1
- OXHJCNSXYDSOFN-UHFFFAOYSA-N n-hexylaniline Chemical class CCCCCCNC1=CC=CC=C1 OXHJCNSXYDSOFN-UHFFFAOYSA-N 0.000 description 1
- KBNHOFDIDSVFMZ-UHFFFAOYSA-N n-nonylaniline Chemical class CCCCCCCCCNC1=CC=CC=C1 KBNHOFDIDSVFMZ-UHFFFAOYSA-N 0.000 description 1
- FRCFWPVMFJMNDP-UHFFFAOYSA-N n-propan-2-ylaniline Chemical compound CC(C)NC1=CC=CC=C1 FRCFWPVMFJMNDP-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- LRTFPLFDLJYEKT-UHFFFAOYSA-N para-isopropylaniline Chemical compound CC(C)C1=CC=C(N)C=C1 LRTFPLFDLJYEKT-UHFFFAOYSA-N 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 229940117803 phenethylamine Drugs 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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Abstract
本発明は、ビスフェノール型エポキシ樹脂(a1)および特定のポリアルキレングリコールジグリシジルエーテル類(a2)を含むエポキシ化合物と、1級および2級からなる群より選ばれる1種以上のアミン類(a3)とを特定比率で反応させて得られるアミン変性エポキシ樹脂(A)と、ポリイソシアネート(B)とを特定割合で反応させてなる塗料用変性エポキシ樹脂である。当該塗料用変性エポキシ樹脂は、防食性などの塗膜性能を維持しながら、更に塗膜の柔軟性の向上および塗料のハイソリッド化を実現しうる。The present invention relates to an epoxy compound containing a bisphenol type epoxy resin (a1) and a specific polyalkylene glycol diglycidyl ether (a2), and one or more amines (a3) selected from the group consisting of primary and secondary Is a modified epoxy resin for paints obtained by reacting an amine-modified epoxy resin (A) obtained by reacting at a specific ratio with polyisocyanate (B) at a specific ratio. The modified epoxy resin for paints can realize further improvement of the flexibility of the paint film and high solidification of the paint while maintaining the paint film performance such as corrosion resistance.
Description
本発明は、塗料用変性エポキシ樹脂および一液・ラッカー型塗料に関する。 The present invention relates to a modified epoxy resin for paint and a one-component lacquer-type paint.
ビスフェノールAとエピクロルヒドリン等とを反応させて製造されるビスフェノールA型エポキシ樹脂は、該樹脂中のエポキシ基および水酸基の反応性に起因して、優れた防食性、密着性、耐薬品性等を有するため、塗料用樹脂として広く使用されている。 The bisphenol A type epoxy resin produced by reacting bisphenol A with epichlorohydrin has excellent corrosion resistance, adhesion, chemical resistance, etc. due to the reactivity of the epoxy group and hydroxyl group in the resin. Therefore, it is widely used as a paint resin.
ところで、エポキシ樹脂は一般に自己硬化性を有しないため、エポキシ樹脂塗料を常温で硬化させる場合には、硬化剤としてポリアミン、ポリアミド等を配合した二液反応型塗料として使用される。 By the way, since an epoxy resin generally does not have a self-curing property, when the epoxy resin coating is cured at room temperature, it is used as a two-component reactive coating in which polyamine, polyamide or the like is blended as a curing agent.
しかしながら、二液反応型塗料は基材に塗布する直前に硬化剤を配合しなければならず、取り扱いが不便であり、しかもポットライフ(可使時間)の点からも実用上種々の制限を受けやすい。そのため、エポキシ樹脂としての密着性、防食性等の特性を維持し、しかも常温乾燥でき、かつ硬化剤を配合する必要のない一液・ラッカー型塗料用樹脂が切望されていた。 However, two-component reactive paints must be mixed with a curing agent just before being applied to the substrate, which is inconvenient to handle and is subject to various practical limitations from the standpoint of pot life. Cheap. Therefore, there has been a strong demand for a one-pack, lacquer-type coating resin that maintains properties such as adhesion and corrosion resistance as an epoxy resin, can be dried at room temperature, and does not need to contain a curing agent.
この課題を解決するために、従来、エポキシ樹脂をアミン類等で開環させ、さらにポリイソシアネート化合物を反応させて得られる変性エポキシ樹脂が開発され、提供されていた(特許文献1、2を参照)。これらの変性エポキシ樹脂は、エポキシ樹脂の特性である防食性、密着性、耐薬品性等の性能を有し、しかも常温乾燥でき、かつ硬化剤を配合する必要のない一液・ラッカー型塗料を提供できるとの利点がある。 In order to solve this problem, conventionally, a modified epoxy resin obtained by ring-opening an epoxy resin with an amine or the like and further reacting with a polyisocyanate compound has been developed and provided (see Patent Documents 1 and 2). ). These modified epoxy resins have the properties of epoxy resin such as anticorrosion, adhesion, chemical resistance, etc., and can be dried at room temperature and do not need to contain curing agents. There is an advantage that it can be provided.
しかしながら、近年、前記塗料において、塗膜の防食性などの諸特性を維持しつつ、更に塗膜の柔軟性の向上および塗料のハイソリッド化(高固形分化)を実現できる塗料用変性エポキシ樹脂の開発が望まれていた。 However, in recent years, a modified epoxy resin for paints that can improve the flexibility of the paint film and achieve high solidification (high solidification) of the paint while maintaining various properties such as the anticorrosive property of the paint film in the paint. Development was desired.
本発明は、上記課題を解決するものであり、前記の変性エポキシ樹脂が有する防食性などの塗膜性能を維持しながら、更に塗膜の柔軟性の向上および塗料のハイソリッド化を実現できる、塗料用変性エポキシ樹脂を提供することを目的とする。 The present invention solves the above-mentioned problems, and while maintaining the coating film performance such as anticorrosion property of the modified epoxy resin, it is possible to further improve the flexibility of the coating film and make the coating highly solid. It aims at providing the modified epoxy resin for coating materials.
本発明者は前記課題を解決すべく鋭意検討を重ねた結果、特定の塗料用変性エポキシ樹脂を用いることにより前記課題を解決できることを見出し、本発明を完成させるに至った。 As a result of intensive studies to solve the above problems, the present inventor has found that the above problems can be solved by using a specific modified epoxy resin for paint, and has completed the present invention.
すなわち、本発明は、アミン変性エポキシ樹脂(A)とポリイソシアネート(B)との反応生成物である変性エポキシ樹脂であって、前記(A)がビスフェノール型エポキシ樹脂(a1)95〜50重量%およびエポキシ当量100〜600であるポリアルキレングリコールジグリシジルエーテル類(a2)5〜50重量%(但し、前記(a1)および(a2)の合計が90重量%以上である。)を含むエポキシ化合物と、1級および2級からなる群より選ばれる1種以上のアミン類(a3)との反応生成物であり、{前記(a1)および(a2)を含むエポキシ化合物のエポキシ基数}/{前記(a3)のアミノ基の活性水素数}の割合が、100/90〜100/110であることを特徴とする塗料用変性エポキシ樹脂に関する。また本発明は、前記の変性エポキシ樹脂を含有する一液・ラッカー型塗料に関する。 That is, the present invention is a modified epoxy resin that is a reaction product of an amine-modified epoxy resin (A) and a polyisocyanate (B), wherein the (A) is a bisphenol-type epoxy resin (a1) 95 to 50% by weight. And an epoxy compound containing 5 to 50% by weight of polyalkylene glycol diglycidyl ethers (a2) having an epoxy equivalent of 100 to 600 (provided that the sum of (a1) and (a2) is 90% by weight or more) It is a reaction product with one or more amines (a3) selected from the group consisting of primary and secondary, and {the number of epoxy groups of the epoxy compound containing (a1) and (a2)} / {the above ( The ratio of active hydrogen number of amino group in a3) is 100/90 to 100/110. The present invention also relates to a one-component lacquer type paint containing the modified epoxy resin.
本発明によれば、防食性などの塗膜性能を維持しながら、更に塗膜の柔軟性の向上および塗料のハイソリッド化を実現しうる、塗料用変性エポキシ樹脂を提供することができる。また、該変性エポキシ樹脂を用いて得られる本発明の一液・ラッカー型塗料は、溶剤含有率を低減できるため、環境適性の観点でも好適である。 ADVANTAGE OF THE INVENTION According to this invention, the modified epoxy resin for coating materials which can implement | achieve the improvement of the softness | flexibility of a coating film and high solidification of a coating material can be further provided, maintaining coating film performance, such as corrosion resistance. In addition, the one-component lacquer-type paint of the present invention obtained by using the modified epoxy resin can reduce the solvent content, and thus is suitable from the viewpoint of environmental suitability.
本発明の塗料用変性エポキシ樹脂は、アミン変性エポキシ樹脂(A)(以下、(A)成分という)とポリイソシアネート(B)(以下、(B)成分という)との反応生成物である変性エポキシ樹脂であって、前記(A)がビスフェノール型エポキシ樹脂(a1)(以下、(a1)成分という)95〜50重量%およびエポキシ当量100〜600であるポリアルキレングリコールジグリシジルエーテル類(a2)(以下、(a2)成分という)5〜50重量%(但し、前記(a1)および(a2)の合計が90重量%以上である。)を含むエポキシ化合物と、1級および2級からなる群より選ばれる1種以上のアミン類(a3)(以下、(a3)成分という)との反応生成物であり、{前記(a1)および(a2)を含むエポキシ化合物のエポキシ基数}/{前記(a3)のアミノ基の活性水素数}の割合が、100/90〜100/110であることを特徴とする。 The modified epoxy resin for coating of the present invention is a modified epoxy which is a reaction product of an amine-modified epoxy resin (A) (hereinafter referred to as “component (A)”) and polyisocyanate (B) (hereinafter referred to as “component (B)”). Polyalkylene glycol diglycidyl ethers (a2) (a) in which (A) is a bisphenol type epoxy resin (a1) (hereinafter referred to as component (a1)) of 95 to 50% by weight and an epoxy equivalent of 100 to 600 Hereinafter, from the group consisting of an epoxy compound containing 5 to 50% by weight (referred to as component (a2)) (provided that the sum of (a1) and (a2) is 90% by weight or more) and a primary and secondary group It is a reaction product with one or more selected amines (a3) (hereinafter referred to as component (a3)), and {the epoxy compound containing (a1) and (a2) Ratio of alkoxy groups} / {the number active hydrogens of the amino groups of the (a3)} is characterized in that it is a 100 / 90-100 / 110.
(a1)成分としては、ビスフェノール類とエピクロルヒドリンまたはβ−メチルエピクロルヒドリン等のハロエポキシドとの反応により得られるものが挙げられる。ビスフェノール類としては、フェノールまたは2,6−ジハロフェノールとホルムアルデヒド、アセトアルデヒド、アセトン、アセトフェノン、シクロヘキサノン、ベンゾフェノン等のアルデヒド類もしくはケトン類との反応の他、ジヒドロキシフェニルスルフィドの過酸による酸化、ハイドロキノン同士のエーテル化反応等により得られるものが挙げられる。ビスフェノール類の具体例としては、例えば2,2−ビス(4−ヒドロキシフェニル)プロパン(ビスフェノールΑ)、ビス(4−ヒドロキシフェニル)メタン(ビスフェノールF)等が挙げられる。(a1)成分は、それぞれ単独で、または2種以上を適宜に組み合わせて使用される。 Examples of the component (a1) include those obtained by reaction of bisphenols with haloepoxides such as epichlorohydrin or β-methylepichlorohydrin. Bisphenols include reactions of phenol or 2,6-dihalophenol with aldehydes or ketones such as formaldehyde, acetaldehyde, acetone, acetophenone, cyclohexanone, benzophenone, oxidation of dihydroxyphenyl sulfide with peracid, hydroquinone Those obtained by the etherification reaction of Specific examples of bisphenols include 2,2-bis (4-hydroxyphenyl) propane (bisphenolΑ), bis (4-hydroxyphenyl) methane (bisphenol F), and the like. (A1) A component is used individually or in combination of 2 or more types, respectively.
(a1)成分のエポキシ当量は、必ずしも限定はされないが、低粘度化の観点からは100〜5,000であることが好ましく、150〜2,000であることがより好ましい。エポキシ当量が当該範囲であると、得られる塗料用変性エポキシ樹脂の分子量が過度に増大せず、該樹脂は比較的低粘度となるため、該樹脂を用いて得られる塗料のハイソリッド化が容易になるという利点がある。 The epoxy equivalent of the component (a1) is not necessarily limited, but is preferably 100 to 5,000, more preferably 150 to 2,000 from the viewpoint of reducing the viscosity. When the epoxy equivalent is within this range, the molecular weight of the resulting modified epoxy resin for coating does not increase excessively, and the resin has a relatively low viscosity, so that it is easy to make the coating obtained using the resin highly solid. There is an advantage of becoming.
(a2)成分は、得られる変性エポキシ樹脂に柔軟性を付与し、かつ該樹脂の低粘度化を実現するための必須構成成分である。(a2)成分としては、各種ポリアルキレングリコールのジグリシジルエーテル類であって、そのエポキシ当量が100〜600であり、好ましくは200〜500のものである。該範囲のエポキシ当量を有する(a2)成分を用いることにより、得られる塗料用変性エポキシ樹脂の粘度を効果的に低減することができる。そのため、該変性エポキシ樹脂を用いて、目的とする塗料のハイソリッド化を実現できる。 The component (a2) is an essential component for imparting flexibility to the resulting modified epoxy resin and realizing a low viscosity of the resin. As the component (a2), diglycidyl ethers of various polyalkylene glycols having an epoxy equivalent of 100 to 600, preferably 200 to 500. By using the component (a2) having an epoxy equivalent in this range, the viscosity of the resulting modified epoxy resin for coating can be effectively reduced. Therefore, using the modified epoxy resin, it is possible to achieve a high solidity of the target paint.
(a2)成分は、炭素数1〜4のアルキレンを有する、ポリアルキレングリコールジグリシジルエーテル類が好ましく用いられ、具体例としては、ポリエチレングリコールジグリシジルエーテル類、ポリプロピレングリコールジグリシジルエーテル類、ポリオキシエチレンポリオキシプロピレングリコールジグリシジルエーテル類、ポリブチレングリコールジグリシジルエーテル類などが挙げられる。これらはそれぞれ単独で、または二種以上を適宜に組み合わせて使用される。これらの中でも、塗膜の防食性の点から、ポリプロピレングリコールジグリシジルエーテル類がより好ましい。また、(a2)成分は、応力緩和効果を有するため、得られる塗膜の柔軟性を向上しうる利点がある。 As the component (a2), polyalkylene glycol diglycidyl ethers having an alkylene having 1 to 4 carbon atoms are preferably used. Specific examples include polyethylene glycol diglycidyl ethers, polypropylene glycol diglycidyl ethers, polyoxyethylene. Examples include polyoxypropylene glycol diglycidyl ethers and polybutylene glycol diglycidyl ethers. These may be used alone or in appropriate combination of two or more. Among these, polypropylene glycol diglycidyl ethers are more preferable from the viewpoint of corrosion resistance of the coating film. Moreover, since the component (a2) has a stress relaxation effect, there is an advantage that the flexibility of the obtained coating film can be improved.
(a1)成分および(a2)成分以外のエポキシ化合物としては、エポキシ化油、ダイマー酸ジグリシジル、1,6−ヘキサンジオールジグリシジルエーテルなどが挙げられる。(a1)成分および(a2)成分以外のエポキシ化合物は、それぞれ単独で、または2種以上を適宜に組み合わせて使用される。 Examples of the epoxy compound other than the component (a1) and the component (a2) include epoxidized oil, diglycidyl dimer acid, 1,6-hexanediol diglycidyl ether, and the like. The epoxy compounds other than the component (a1) and the component (a2) are used alone or in appropriate combination of two or more.
前記エポキシ化合物における(a1)成分および(a2)成分の合計は90重量%以上である。エポキシ化合物における(a1)成分および(a2)成分の合計は、塗膜の防食性の観点から、95重量%以上が好ましく、97重量%以上がより好ましく、100重量%が最も好ましい。 The total of the (a1) component and the (a2) component in the epoxy compound is 90% by weight or more. The total of the (a1) component and the (a2) component in the epoxy compound is preferably 95% by weight or more, more preferably 97% by weight or more, and most preferably 100% by weight, from the viewpoint of the corrosion resistance of the coating film.
前記エポキシ化合物における(a1)成分の使用割合は、エポキシ化合物100重量%あたり、95〜50重量%であり、好ましくは95〜75重量%である。(a1)成分の使用割合が50重量%以上であると、得られる塗膜の硬度や耐薬品性を向上でき、また95重量%以下であると高い防食性と密着性を実現することができる。 The use ratio of the component (a1) in the epoxy compound is 95 to 50% by weight, preferably 95 to 75% by weight, per 100% by weight of the epoxy compound. When the proportion of component (a1) used is 50% by weight or more, the hardness and chemical resistance of the resulting coating film can be improved, and when it is 95% by weight or less, high corrosion resistance and adhesion can be realized. .
前記エポキシ化合物における(a2)成分の使用割合は、エポキシ化合物100重量%あたり、5〜50重量%であり、好ましくは5〜25重量%である。 The use ratio of the component (a2) in the epoxy compound is 5 to 50% by weight, preferably 5 to 25% by weight, per 100% by weight of the epoxy compound.
(a3)成分としては、アルカノールアミン類、脂肪族アミン類、芳香族アミン類、脂環族アミン類、芳香核置換脂肪族アミン類等であって、炭素数が2〜20のものがあげられ、これらをそれぞれ単独で、または二種以上を適宜に組み合わせて使用しうる。 Examples of the component (a3) include alkanolamines, aliphatic amines, aromatic amines, alicyclic amines, aromatic nucleus-substituted aliphatic amines having 2 to 20 carbon atoms. These may be used alone or in appropriate combination of two or more.
該アルカノールアミン類としては、例えば、モノエタノールアミン、ジエタノールアミン、モノイソプロパノールアミン、ジイソプロパノールアミン、ジ−2−ヒドロキシブチルアミン、N−メチルエタノールアミン、N−エチルエタノールアミン、N−ベンジルエタノールアミン等が挙げられ、これらはそれぞれ単独で、または2種以上を適宜に組み合わせて使用される。本発明の塗料用変性エポキシ樹脂の製造に際して、(A)成分と(B)成分との反応性や、得られる変性エポキシ樹脂の分子量調整などを考慮すれば、(a3)成分のうち、アルカノールアミン類の使用量は5〜50重量%程度であり、好ましくは10〜40重量%である。 Examples of the alkanolamines include monoethanolamine, diethanolamine, monoisopropanolamine, diisopropanolamine, di-2-hydroxybutylamine, N-methylethanolamine, N-ethylethanolamine, N-benzylethanolamine and the like. These may be used alone or in appropriate combination of two or more. In the production of the modified epoxy resin for paints of the present invention, considering the reactivity of the components (A) and (B) and the adjustment of the molecular weight of the resulting modified epoxy resin, among the components (a3), alkanolamine The amount used is about 5 to 50% by weight, preferably 10 to 40% by weight.
前記の脂肪族アミン類としては、エチルアミン、プロピルアミン、ブチルアミン、ヘキシルアミン、ラウリルアミン、ステアリルアミン、パルミチルアミン、オレイルアミン、エルシルアミン等の一級アミン類やジエチルアミン、ジプロピルアミン、ジブチルアミン等の二級アミン類があげられる。芳香族アミン類としては、トルイジン類、キシリジン類、クミジン(イソプロピルアニリン)類、ヘキシルアニリン類、ノニルアニリン類、ドデシルアニリン類等があげられる。脂環族アミン類としては、シクロペンチルアミン類、シクロヘキシルアミン類、ノルボニルアミン類があげられる。また、芳香核置換脂肪族アミン類としては、ベンジルアミン、フェネチルアミン等が挙げられる。これらのアミン類は、それぞれ単独で、または2種以上を適宜に組み合わせて使用されるが、塗料のハイソリッド化を実現できるよう、アルカノールアミン類と併用することが好ましい。 Examples of the aliphatic amines include primary amines such as ethylamine, propylamine, butylamine, hexylamine, laurylamine, stearylamine, palmitylamine, oleylamine, and erucylamine, and secondary amines such as diethylamine, dipropylamine, and dibutylamine. Secondary amines. Examples of aromatic amines include toluidines, xylidines, cumidine (isopropylaniline), hexylanilines, nonylanilines, dodecylanilines and the like. Examples of the alicyclic amines include cyclopentylamines, cyclohexylamines, and norbornylamines. Examples of the aromatic nucleus-substituted aliphatic amines include benzylamine and phenethylamine. These amines are used singly or in appropriate combination of two or more, but are preferably used in combination with alkanolamines so that a high solid state of the paint can be realized.
(A)成分は、(a1)成分および(a2)成分を含むエポキシ化合物と、(a3)成分とを下記の条件下で反応させることにより製造することができる。すなわち、{(a1)成分および(a2)成分を含むエポキシ化合物のエポキシ基数}/{(a3)成分のアミノ基の活性水素数}が100/90〜100/110となるように、各成分の使用量を決定する。該使用割合とすることにより、各成分の未反応物を容易に低減しうる意義がある。 The component (A) can be produced by reacting an epoxy compound containing the components (a1) and (a2) with the component (a3) under the following conditions. That is, {the number of epoxy groups of the epoxy compound containing the components (a1) and (a2)} / {the number of active hydrogens of the amino group of the component (a3)} is 100/90 to 100/110. Determine usage. By setting the ratio to be used, there is a significance that unreacted substances of each component can be easily reduced.
前記(a1)成分および(a2)成分を含むエポキシ化合物のエポキシ基数は、エポキシ化合物に含まれる各成分のエポキシ基数の合計である。(a1)成分のエポキシ基数は、(a1)成分の仕込み重量を、(a1)成分のエポキシ当量で除して算出できる。(a2)成分並びに、(a1)成分および(a2)成分以外のエポキシ化合物のエポキシ基数も上記のように算出できる。 The number of epoxy groups in the epoxy compound containing the component (a1) and the component (a2) is the total number of epoxy groups in each component contained in the epoxy compound. The number of epoxy groups in the component (a1) can be calculated by dividing the charged weight of the component (a1) by the epoxy equivalent of the component (a1). The number of epoxy groups of the epoxy compound other than the component (a2) and the components (a1) and (a2) can also be calculated as described above.
前記(a3)成分のアミノ基の活性水素数は、(a3)成分の仕込みモル量に、(a3)成分の一分子あたりのアミノ基の活性水素数を乗じて算出できる。また、(a3)成分のアミノ基の活性水素数は、(a3)成分の仕込み重量を、(a3)成分のアミン当量で除しても算出できる。尚、(a3)成分が複数の成分を含む場合、(a3)成分のアミノ基の活性水素数は、各成分のアミノ基の活性水素数の合計である。 The number of active hydrogens of the amino group of the component (a3) can be calculated by multiplying the charged molar amount of the component (a3) by the number of active hydrogens of amino groups per molecule of the component (a3). The number of active hydrogens of the amino group of the component (a3) can also be calculated by dividing the charged weight of the component (a3) by the amine equivalent of the component (a3). When the component (a3) includes a plurality of components, the number of active hydrogens in the amino group of the component (a3) is the total number of active hydrogens in the amino group of each component.
(A)成分の製造における反応温度は、通常、50〜250℃程度であり、好ましくは80〜150℃程度である。反応温度が50℃未満であると反応速度が小さくなりすぎ、250℃を超えると、(a1)成分および(a2)成分を含むエポキシ化合物中のエポキシ基と水酸基との反応、または該エポキシ基同士の反応等が起こり、反応生成物がゲル化しやすくなる場合がある。また、反応時間は反応温度に依存するため特に限定されないが、製造効率の面から通常は3〜10時間程度であり、好ましくは3〜6時間である。 (A) The reaction temperature in manufacture of a component is about 50-250 degreeC normally, Preferably it is about 80-150 degreeC. When the reaction temperature is less than 50 ° C., the reaction rate becomes too low, and when it exceeds 250 ° C., the reaction between the epoxy group and the hydroxyl group in the epoxy compound containing the component (a1) and the component (a2), or between the epoxy groups In some cases, the reaction product is easily gelled. The reaction time is not particularly limited because it depends on the reaction temperature, but is usually about 3 to 10 hours, preferably 3 to 6 hours from the viewpoint of production efficiency.
(B)成分としては、芳香族、脂肪族または脂環族の各種公知のポリイソシアネートが挙げられ、これらはそれぞれ単独で、または二種以上を適宜に組み合わせて使用される。(B)成分の具体例としては、1,5−ナフチレンジイソシアネート、4,4’−ジフェニルメタンジイソシアネート、4,4’−ジフェニルジメチルメタンジイソシアネート、4,4’−ジベンジルイソシアネート、ジアルキルジフェニルメタンジイソシアネート、テトラアルキルジフェニルメタンジイソシアネート、1,3−フェニレンジイソシアネート、1,4−フェニレンジイソシアネート、トリレンジイソシアネート、ブタン−1,4−ジイソシアネート、ヘキサメチレンジイソシアネート、2,2,4−トリメチルヘキサメチレンジイソシアネート、2,4,4−トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート、シクロヘキサン−1,4−ジイソシアネート、キシリレンジイソシアネート、ジシクロヘキシルメタン−4,4’−ジイソシアネート、1,3−ビス(イソシアネートメチル)シクロヘキサン、メチルシクロヘキサンジイソシアネート、オルトトルイジンジイソシアネート、ポリフェニルポリイソシアネート、イソホロンジイソシアネート等があげられる。これらポリイソシアネートのうち好ましくは、トリレンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネートなどが挙げられる。 As the component (B), various known polyisocyanates such as aromatic, aliphatic or alicyclic can be used, and these can be used alone or in appropriate combination of two or more. Specific examples of the component (B) include 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetra Alkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4 -Trimethylhexamethylene diisocyanate, lysine diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, dicyclohexane Rumetan-4,4'-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, ortho-toluidine diisocyanate, polyphenyl polyisocyanates, isophorone diisocyanate and the like. Of these polyisocyanates, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like are preferable.
本発明の塗料用変性エポキシ樹脂の製造においては、{(B)成分のイソシアネート基数}/{(A)成分の水酸基数}が、通常は0.001〜0.15、好ましくは0.005〜0.08となるように、両成分を反応させればよい。当該比率が0.001以上であると、得られる塗料用変性エポキシ樹脂の分子量が適度に高くなり、常温乾燥しうる一液型のラッカー型塗料用樹脂として好適である。一方、0.15以下であると過度の高分子量化を抑制することができ、ハイソリッド型塗料の調製に好適である。 In the production of the modified epoxy resin for paints of the present invention, {number of isocyanate groups of component (B)} / {number of hydroxyl groups of component (A)} is usually 0.001 to 0.15, preferably 0.005. What is necessary is just to make both components react so that it may be set to 0.08. When the ratio is 0.001 or more, the molecular weight of the resulting modified epoxy resin for coatings is appropriately high, which is suitable as a one-pack type lacquer coating resin that can be dried at room temperature. On the other hand, when it is 0.15 or less, excessive increase in the molecular weight can be suppressed, which is suitable for preparing a high solid paint.
前記(B)成分のイソシアネート基数は、(B)成分の仕込みモル量に、(B)成分の一分子あたりのイソシアネート基数を乗じて算出できる。また、(B)成分のイソシアネート基数は、(B)成分の仕込み重量を、(B)成分のイソシアネート当量で除しても算出できる。尚、(B)成分が複数の成分を含む場合、(B)成分のイソシアネート基数は、各成分のイソシアネート基数の合計である。 The number of isocyanate groups in the component (B) can be calculated by multiplying the charged molar amount of the component (B) by the number of isocyanate groups per molecule of the component (B). Further, the number of isocyanate groups in the component (B) can be calculated by dividing the charged weight of the component (B) by the isocyanate equivalent of the component (B). In addition, when (B) component contains several components, the number of isocyanate groups of (B) component is the sum total of the number of isocyanate groups of each component.
前記(A)成分の水酸基数は、(a1)成分および(a2)成分を含むエポキシ化合物と(a3)成分との反応生成物の水酸基数である。反応生成物の水酸基数は、(i):(a1)成分および(a2)成分を含むエポキシ化合物の水酸基数と、(ii):(a3)成分の水酸基数と、(iii):(a1)成分および(a2)成分を含むエポキシ化合物と(a3)成分との反応(エポキシ基の開環反応)により理論的に算出される水酸基数との合計である。 The number of hydroxyl groups in the component (A) is the number of hydroxyl groups in the reaction product of the epoxy compound containing the components (a1) and (a2) and the component (a3). The number of hydroxyl groups in the reaction product is as follows: (i): the number of hydroxyl groups of the epoxy compound containing the components (a1) and (a2), the number of hydroxyl groups of the component (ii): (a3), and (iii): (a1) It is the total of the number of hydroxyl groups calculated theoretically by the reaction (epoxy group ring-opening reaction) between the component and the epoxy compound containing the component (a2) and the component (a3).
前記(i):(a1)成分および(a2)成分を含むエポキシ化合物の水酸基数は、エポキシ化合物に含まれる各成分の水酸基数の合計である。(a1)成分の水酸基数は、(a1)成分の仕込みモル量に、(a1)成分の一分子あたりの水酸基数を乗じて算出できる。(a2)成分並びに、(a1)成分および(a2)成分以外のエポキシ化合物の水酸基数も上記のように算出できる。 The number of hydroxyl groups in the epoxy compound containing the component (i): (a1) and the component (a2) is the total number of hydroxyl groups in each component contained in the epoxy compound. The number of hydroxyl groups in the component (a1) can be calculated by multiplying the charged molar amount of the component (a1) by the number of hydroxyl groups per molecule of the component (a1). The number of hydroxyl groups of the epoxy compound other than the component (a2) and the components (a1) and (a2) can also be calculated as described above.
前記(ii):(a3)成分の水酸基数は、(a3)成分の仕込みモル量に、(a3)成分の一分子あたりの水酸基数を乗じて算出できる。尚、(a3)成分が複数の成分を含む場合、(a3)成分の水酸基数は、各成分の水酸基数の合計である。 The number of hydroxyl groups of the component (ii): (a3) can be calculated by multiplying the charged molar amount of the component (a3) by the number of hydroxyl groups per molecule of the component (a3). When the component (a3) includes a plurality of components, the number of hydroxyl groups in the component (a3) is the total number of hydroxyl groups in each component.
前記(iii):(a1)成分および(a2)成分を含むエポキシ化合物と(a3)成分との反応(エポキシ基の開環反応)により理論的に算出される水酸基数は、当該反応によりエポキシ基1つあたり水酸基が1つ生じることから、(a1)成分および(a2)成分を含むエポキシ化合物のエポキシ基数のうち、(a3)成分との反応により理論的に消費されるエポキシ基数と同値である。尚、上記の理論的に算出される水酸基数は、(a1)成分および(a2)成分を含むエポキシ化合物中のエポキシ基と水酸基との反応、または該エポキシ基同士の反応等の副反応を考慮しないで求められる。 The number of hydroxyl groups theoretically calculated by the reaction (epoxy group ring-opening reaction) between the (iii): epoxy compound containing the components (a1) and (a2) and the component (a3) is determined by the reaction. Since one hydroxyl group is generated per one, the number of epoxy groups of the epoxy compound containing the components (a1) and (a2) is the same as the number of epoxy groups theoretically consumed by the reaction with the component (a3). . The theoretically calculated number of hydroxyl groups takes into account side reactions such as the reaction between the epoxy group and the hydroxyl group in the epoxy compound containing the components (a1) and (a2), or the reaction between the epoxy groups. Not required.
上記(B)成分と(A)成分の反応条件は特に限定されないが、反応温度は、通常20〜200℃程度であり、好ましくは50〜150℃である。また、反応時間は製造効率の面から通常は3〜10時間程度であり、好ましくは3〜6時間である。 Although the reaction conditions of the said (B) component and (A) component are not specifically limited, Reaction temperature is about 20-200 degreeC normally, Preferably it is 50-150 degreeC. The reaction time is usually about 3 to 10 hours, preferably 3 to 6 hours from the viewpoint of production efficiency.
該反応においては、溶剤を使用できるが、前記各成分に対して不活性なものでなければならない。該不活性溶剤としては、例えば、トルエン、キシレン等の炭化水素類、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類、酢酸エチル、酢酸ブチル等のエステル類、メチルセロソルブアセテート、セロソルブアセテート等のセロソルブアセテート類等の活性水素を有しないものが挙げられ、これらをそれぞれ単独で、または2種以上を適宜に組み合わせて使用できる。なお、本発明の塗料用変性エポキシ樹脂の製造後であれば、稀釈溶剤として、メチルセロソルブ、エチルセロソルブ等のセロソルブ類;イソプロピルアルコール、n−ブチルアルコール等のアルコール類;などの活性水素を有する溶剤も差し支えなく使用しうる。 In the reaction, a solvent can be used, but it must be inert to the respective components. Examples of the inert solvent include hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, esters such as ethyl acetate and butyl acetate, and cellosolve acetate such as methyl cellosolve acetate and cellosolve acetate. And the like that do not have active hydrogen, such as those, can be used alone, or two or more can be used in appropriate combination. In addition, if it is after manufacture of the modified epoxy resin for coatings of this invention, as solvents for dilution, active solvents such as cellosolves such as methyl cellosolve and ethyl cellosolve; alcohols such as isopropyl alcohol and n-butyl alcohol; Can be used without any problem.
本発明の塗料用変性エポキシ樹脂の重量平均分子量(ゲルパーメーションクロマトグラフィーによるポリスチレン換算値)は、格別限定されないが、通常は5,000〜100,000であり、好ましくは15,000〜40,000である。重量平均分子量が5,000以上とすることで長期の高い防食性、耐水性等を有する一液・ラッカー型塗料用樹脂が得られ、また100,000以下とすることで、高粘度化を抑制したハイソリッド型塗料用に適する樹脂が得られる。 Although the weight average molecular weight (polystyrene conversion value by gel permeation chromatography) of the modified epoxy resin for paint of the present invention is not particularly limited, it is usually 5,000 to 100,000, preferably 15,000 to 40, 000. When the weight average molecular weight is 5,000 or more, a one-part lacquer-type coating resin having a long-term high anticorrosion property and water resistance can be obtained, and when it is 100,000 or less, high viscosity is suppressed. The resin suitable for the high solid type paint is obtained.
本発明の塗料用変性エポキシ樹脂の固形分濃度については、格別限定されず、塗料化した場合の粘度等を考慮して適宜に決定すればよいが、通常は、30〜80重量%程度とされる。また、得られる塗料の取り扱い性の点から、該樹脂溶液の粘度はR〜Z7(ガードナー法,25℃)程度に調整して用いられる。The solid content concentration of the modified epoxy resin for paint according to the present invention is not particularly limited and may be appropriately determined in consideration of the viscosity and the like when formed into a paint, but is usually about 30 to 80% by weight. The Moreover, from the point of the handleability of the coating material obtained, the viscosity of the resin solution is adjusted to about R to Z 7 (Gardner method, 25 ° C.).
前記の塗料用変性エポキシ樹脂を含む一液・ラッカー型塗料(以下、本塗料という)について、以下に説明する。本塗料は、常温乾燥用塗料として使用できるほか、強制乾燥塗料、焼付け塗料などとしても好適である。また、本塗料は、被塗物、用途など格別限定されず広範に適用できるが、防食性、密着性等の性能を考慮すれば、下塗り用に好適である。 The one-component lacquer type paint (hereinafter referred to as the present paint) containing the above-described modified epoxy resin for paint is described below. The paint can be used as a room temperature drying paint, and is also suitable as a forced drying paint or a baking paint. In addition, the present paint can be applied in a wide range without being particularly limited such as an object to be coated and a use, but is suitable for undercoating in consideration of performance such as corrosion resistance and adhesion.
本塗料の調製では、カーボン、酸化チタン等の着色顔料、タルク、炭酸カルシウム、硫酸バリウム等の体質顔料、リンモリブデン酸アルミニウム、リン酸亜鉛等の防錆顔料を適宜に配合することができる。また、本塗料には、必要に応じて、メラミン樹脂、尿素樹脂、イソシアネート、ブロックイソシアネート等の硬化剤や、公知各種の溶剤、その他の添加剤を適宜に配合してもよい。本塗料をハイソリッド型として調製する場合は、不揮発分が通常50〜80重量%程度、好ましくは70〜80重量%とされ、また溶剤含有率は通常20〜50重量%程度、好ましくは20〜30重量%とされる。 In the preparation of this paint, coloring pigments such as carbon and titanium oxide, extender pigments such as talc, calcium carbonate, and barium sulfate, and rust preventive pigments such as aluminum phosphomolybdate and zinc phosphate can be appropriately blended. Moreover, you may mix | blend suitably hardeners, such as a melamine resin, a urea resin, isocyanate, blocked isocyanate, various known solvents, and other additives with this coating material as needed. When preparing this paint as a high solid type, the non-volatile content is usually about 50 to 80% by weight, preferably 70 to 80% by weight, and the solvent content is usually about 20 to 50% by weight, preferably 20 to 20% by weight. 30% by weight.
以下に本発明を実施例により更に具体的に説明する。ただし、本発明はこれら実施例に限定されるものではない。また実施例中、「部」は特に断りのない限り「重量部」を意味する。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the examples, “parts” means “parts by weight” unless otherwise specified.
実施例1
撹拌機、冷却器、温度計および窒素ガス導入管を備えた反応容器に、ビスフェノール型エポキシ樹脂(東都化成(株)製、商品名「エポトートYD−014」、エポキシ当量950g/eq)900部、ポリプロピレングリコールジグリシジルエーテル(ナガセケムテックス(株)製、商品名「デナコールEX−931」、エポキシ当量472g/eq)100部、ジエタノールアミン19.5部、モノエタノールアミン1.4部、オレイルアミン(商品名「ファーミンO」、花王ケミカル(株)製)120.9部およびキシレン689部を仕込み、これらを窒素気流下、100℃で5時間反応させて、アミン変性エポキシ樹脂(A1)を得た。次いで、同反応容器にイソホロンジイソシアネート(B)3.3部、シクロヘキサノン459部を仕込み、これらを窒素気流下で100℃において4時間反応させることにより、塗料用変性エポキシ樹脂を得た。この樹脂の物性値を表1に示す。なお、重量平均分子量の測定は以下の方法で行った。Example 1
In a reaction vessel equipped with a stirrer, a cooler, a thermometer and a nitrogen gas introduction tube, 900 parts of a bisphenol type epoxy resin (manufactured by Toto Kasei Co., Ltd., trade name “Epototo YD-014”, epoxy equivalent 950 g / eq), Polypropylene glycol diglycidyl ether (manufactured by Nagase ChemteX Corp., trade name “Denacol EX-931”, epoxy equivalent 472 g / eq) 100 parts, diethanolamine 19.5 parts, monoethanolamine 1.4 parts, oleylamine (trade name) “Farmin O” (manufactured by Kao Chemical Co., Ltd.) 120.9 parts and 689 parts of xylene were charged and reacted at 100 ° C. for 5 hours under a nitrogen stream to obtain an amine-modified epoxy resin (A1). Next, 3.3 parts of isophorone diisocyanate (B) and 459 parts of cyclohexanone were charged in the same reaction vessel, and these were reacted at 100 ° C. for 4 hours under a nitrogen stream to obtain a modified epoxy resin for paint. The physical properties of this resin are shown in Table 1. The weight average molecular weight was measured by the following method.
(重量平均分子量の測定)
装置: HLC−8220(東ソー(株)製)
カラム: TSKgel α−2500×1、α−3000×1
分離溶媒: DMF(LiBr 5mmol/kg含有)
流量: 1ml/min
温度: 40℃
標準: ポリスチレン(Measurement of weight average molecular weight)
Apparatus: HLC-8220 (manufactured by Tosoh Corporation)
Column: TSKgel α-2500 × 1, α-3000 × 1
Separation solvent: DMF (containing 5 mmol / kg of LiBr)
Flow rate: 1ml / min
Temperature: 40 ° C
Standard: Polystyrene
実施例2〜11および比較例1〜2
実施例1おいて、(a1)成分の種類、(a2)成分の種類、および(a3)成分の種類、(a1)成分と(a2)成分の使用割合、{(a1)成分および(a2)成分のエポキシ基数}と{(a3)成分のアミノ基の活性水素数}との使用割合、ならびに(A)成分と(B)成分の使用割合のいずれか少なくとも1つの項目を、表1に示すように変えた他は実施例1と同様に反応させて、各種の塗料用変性エポキシ樹脂を得た。これらの物性値を表1に示す。
Examples 2-11 and Comparative Examples 1-2
In Example 1, (a1) component type, (a2) component type, and (a3) component type, (a1) component and (a2) component use ratio, {(a1) component and (a2) Table 1 shows at least one of the usage ratio of the number of epoxy groups of the component} and the number of active hydrogen groups of the amino group of (a3) and the usage ratio of the components (A) and (B). The reaction was carried out in the same manner as in Example 1 except that the various modified epoxy resins for paints were obtained. These physical property values are shown in Table 1.
表1中、(a1)成分、(a2)成分、(a3)成分および(B)成分に係る数値は、いずれも仕込み重量部を示す。また各記号は、以下を意味する。
YD014:ビスフェノール型エポキシ樹脂(新日鉄住金(株)製、商品名「エポトートYD−014」、Mw.1400、エポキシ当量:950g/eq、一分子あたりの水酸基数:3.7)
PPGGE1:ポリプロピレングリコールジグリシジルエーテル(ナガセケムテックス(株)製、商品名「EX−931」、Mw.940、エポキシ当量:472g/eq、一分子あたりの水酸基数:0)
PPGGE2:ポリプロピレングリコールジグリシジルエーテル(三洋化成工業(株)製、商品名「グリシエールPP−300P」、Mw.590、エポキシ当量:295g/eq、一分子あたりの水酸基数:0)
PEGGE1:ポリエチレングリコールジグリシジルエーテル(ナガセケムテックス(株)製、商品名「デナコールEX−841」、Mw.728、エポキシ当量:364g/eq、一分子あたりの水酸基数:0)
PBGGE1:ポリブチレングリコールジグリシジルエーテル(阪本薬品工業(株)製、商品名「SR−PTMG」、Mw.862、エポキシ当量:431g/eq、一分子あたりの水酸基数:0)
DEA:ジエタノールアミン(三井化学(株)製、Mw.105、一分子あたりのアミノ基の活性水素数:1、アミン当量:105g/eq、一分子あたりの水酸基数:2)
MEA:モノエタノールアミン(三井化学(株)製、Mw.61、一分子あたりのアミノ基の活性水素数:2、アミン当量:30.5g/eq、一分子あたりの水酸基数:1)
OA :オレイルアミン(花王ケミカル(株)製、商品名「ファーミンO」、Mw.260、一分子あたりのアミノ基の活性水素数:2、アミン当量:130g/eq、一分子あたりの水酸基数:0)
官能基比率:{(a1)成分および(a2)成分を含むエポキシ化合物のエポキシ基数}/{(a3)成分のアミノ基の活性水素数}
IPDI:イソホロンジイソシアネート(住友バイエルウレタン(株)製、Mw.222、一分子あたりのイソシアネート基数:2、イソシアネート当量:111g/eq)
NCO基/OH基:{(B)成分のイソシアネート基数}/{(A)成分の水酸基数}
NV(%):固形分濃度
Mw:重量平均分子量
Vis:ガードナー粘度(25℃)In Table 1, the numerical values relating to the component (a1), the component (a2), the component (a3) and the component (B) all indicate the parts by weight charged. Moreover, each symbol means the following.
YD014: bisphenol type epoxy resin (manufactured by Nippon Steel & Sumikin Co., Ltd., trade name “Epototo YD-014”, Mw.1400, epoxy equivalent: 950 g / eq, number of hydroxyl groups per molecule: 3.7)
PPGGE1: Polypropylene glycol diglycidyl ether (manufactured by Nagase ChemteX Corporation, trade name “EX-931”, Mw.940, epoxy equivalent: 472 g / eq, number of hydroxyl groups per molecule: 0)
PPGGE2: Polypropylene glycol diglycidyl ether (manufactured by Sanyo Kasei Kogyo Co., Ltd., trade name “Glicier PP-300P”, Mw. 590, epoxy equivalent: 295 g / eq, number of hydroxyl groups per molecule: 0)
PEGGE1: Polyethylene glycol diglycidyl ether (manufactured by Nagase ChemteX Corporation, trade name “Denacol EX-841”, Mw.728, epoxy equivalent: 364 g / eq, number of hydroxyl groups per molecule: 0)
PBGGE1: Polybutylene glycol diglycidyl ether (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., trade name “SR-PTMG”, Mw.862, epoxy equivalent: 431 g / eq, number of hydroxyl groups per molecule: 0)
DEA: Diethanolamine (Mitsui Chemicals, Mw. 105, number of active hydrogens of amino group per molecule: 1, amine equivalent: 105 g / eq, number of hydroxyl groups per molecule: 2)
MEA: monoethanolamine (Mitsui Chemicals, Mw. 61, number of active hydrogens of amino group per molecule: 2, amine equivalent: 30.5 g / eq, number of hydroxyl groups per molecule: 1)
OA: oleylamine (manufactured by Kao Chemical Co., Ltd., trade name “Farmin O”, Mw. 260, number of active hydrogens of amino group per molecule: 2, amine equivalent: 130 g / eq, number of hydroxyl groups per molecule: 0 )
Functional group ratio: {number of epoxy groups in the epoxy compound containing the components (a1) and (a2)} / {the number of active hydrogens in the amino group of the component (a3)}
IPDI: isophorone diisocyanate (manufactured by Sumitomo Bayer Urethane Co., Ltd., Mw. 222, number of isocyanate groups per molecule: 2, isocyanate equivalent: 111 g / eq)
NCO group / OH group: {number of isocyanate groups in component (B)} / {number of hydroxyl groups in component (A)}
NV (%): solid content concentration Mw: weight average molecular weight Vis: Gardner viscosity (25 ° C.)
(各種塗料の調製および試験用塗膜の調製)
以下に示す組成の混合物をそれぞれペイントシェイカーで練合してラッカー型塗料を調製した(濃度70%)。得られた塗料を、脱脂ダル鋼板(SPCC−SD、0.8×70×150mm)上に、乾燥後の膜厚が30μmとなるように、バーコーターにより塗布し、強制乾燥(80℃×20分)後、常温(20℃、60%R.H.)で6日放置し、試験用塗膜を調製し、以下の試験に供した。
(組成)
・各実施例、比較例で得られた各ラッカー型塗料用樹脂 200部(固形分100部)
・酸化チタン 80部
・カーボンブラック 4部
・沈降性硫酸バリウム 80部
・リン酸アルミニウム系防錆顔料 16部
・キシレン 10部
・シクロヘキサノン 10部(Preparation of various paints and test coatings)
Mixtures having the compositions shown below were kneaded with a paint shaker to prepare lacquer-type paints (concentration: 70%). The obtained paint was applied on a degreased dull steel plate (SPCC-SD, 0.8 × 70 × 150 mm) with a bar coater so that the film thickness after drying was 30 μm, and forced drying (80 ° C. × 20 Minutes) and then allowed to stand at room temperature (20 ° C., 60% RH) for 6 days to prepare a test coating film, which was subjected to the following tests.
(composition)
-200 parts of resin for each lacquer type paint obtained in each example and comparative example (solid content 100 parts)
・ Titanium oxide 80 parts ・ Carbon black 4 parts ・ Precipitable barium sulfate 80 parts ・ Aluminum phosphate-based rust preventive pigment 16 parts ・ Xylene 10 parts ・ Cyclohexanone 10 parts
(塗膜の評価試験)
(1)鉛筆硬度
JIS K5400に準拠する。
(2)柔軟性(折り曲げ試験)
チンフリースチール板(0.3×120×200mm)上に、乾燥後の膜厚が30μmとなるように、バーコーターにより前記の各塗料を塗布し、強制乾燥(80℃×20分)後、常温(20℃、60%R.H.)で6日放置し、試験片を得た。各試験片を万力によって折り曲げ、折り曲げ部のワレの有無を確認した。間に挟む板(前記チンフリースチール板)の枚数で柔軟性を評価した(2Tとは挟み込む板が2枚で折り曲げ、ワレがないことを示す)。
(3)防食性
JIS K5400に準じて行い、塩水噴霧テスト10日間及び20日間後のセロハンテープ剥離幅(mm)で示した。
これらの評価結果を表2に示す。
(1) Pencil hardness Conforms to JIS K5400.
(2) Flexibility (bending test)
On the chin-free steel plate (0.3 × 120 × 200 mm), each paint was applied with a bar coater so that the film thickness after drying was 30 μm, and after forced drying (80 ° C. × 20 minutes), The test piece was obtained by leaving it at room temperature (20 ° C., 60% RH) for 6 days. Each test piece was bent with a vise and the presence or absence of cracks in the bent portion was confirmed. Flexibility was evaluated by the number of plates (the chin-free steel plate) sandwiched between them (2T indicates that there are two plates to be sandwiched and there is no cracking).
(3) Corrosion resistance It was performed according to JIS K5400, and the cellophane tape peel width (mm) after 10 days and 20 days of the salt spray test was shown.
These evaluation results are shown in Table 2.
表3の結果より、本発明の塗膜性能(各実施例)は、比較例に比べて鉛筆硬度、柔軟性、防食性のバランスに優れ、かつ各該性能が良好と認められる。 From the results of Table 3, it is recognized that the coating film performance (each example) of the present invention is excellent in the balance of pencil hardness, flexibility, and anticorrosion properties as compared with the comparative example, and each performance is good.
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