JPH0465475A - Epoxy resin composition - Google Patents
Epoxy resin compositionInfo
- Publication number
- JPH0465475A JPH0465475A JP2175386A JP17538690A JPH0465475A JP H0465475 A JPH0465475 A JP H0465475A JP 2175386 A JP2175386 A JP 2175386A JP 17538690 A JP17538690 A JP 17538690A JP H0465475 A JPH0465475 A JP H0465475A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- prepolymer
- parts
- blocked
- diisocyanate
- 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
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 28
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 28
- 239000000203 mixture Substances 0.000 title claims abstract description 14
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 26
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 26
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 18
- 239000004593 Epoxy Substances 0.000 claims abstract description 9
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 abstract description 14
- 239000011248 coating agent Substances 0.000 abstract description 13
- 229920001610 polycaprolactone Polymers 0.000 abstract description 5
- 239000004632 polycaprolactone Substances 0.000 abstract description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 125000002723 alicyclic group Chemical group 0.000 abstract 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000002981 blocking agent Substances 0.000 description 13
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 12
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 11
- 125000005442 diisocyanate group Chemical group 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 239000010408 film Substances 0.000 description 8
- -1 hydroxyl compound Chemical class 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 229920005862 polyol Polymers 0.000 description 5
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000002923 oximes Chemical class 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 150000003951 lactams Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 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 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 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
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L tin(ii) bromide Chemical compound Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 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
- 230000002087 whitening effect Effects 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-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
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- NPUQCECELINJML-UHFFFAOYSA-N 2-ethylimidazole Chemical compound CCC1=NC=C[N]1 NPUQCECELINJML-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
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 240000000972 Agathis dammara Species 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004859 Copal Substances 0.000 description 1
- 229920002871 Dammar gum Polymers 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 241000782205 Guibourtia conjugata Species 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- MNFORVFSTILPAW-UHFFFAOYSA-N azetidin-2-one Chemical compound O=C1CCN1 MNFORVFSTILPAW-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- FSEUPUDHEBLWJY-HWKANZROSA-N diacetylmonoxime Chemical compound CC(=O)C(\C)=N\O FSEUPUDHEBLWJY-HWKANZROSA-N 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 210000004392 genitalia Anatomy 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000010985 glycerol esters of wood rosin Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- AEXITZJSLGALNH-UHFFFAOYSA-N n'-hydroxyethanimidamide Chemical compound CC(N)=NO AEXITZJSLGALNH-UHFFFAOYSA-N 0.000 description 1
- IONSZLINWCGRRI-UHFFFAOYSA-N n'-hydroxymethanimidamide Chemical compound NC=NO IONSZLINWCGRRI-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium(IV) ethoxide Substances [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、エポキシ樹脂と、ポリエステルポリオールと
脂肪族および／または脂環族ジイソシアナートからなる
プレポリマーの末端イソシアナート基をブロック化剤で
ブロックしたブロックポリイソシアナートとからなる、
可撓性と耐擦過性に優れたプレコートメタル用エポキシ
樹脂組成物に関する。Detailed Description of the Invention (Industrial Field of Application) The present invention is directed to the use of a blocking agent to block the terminal isocyanate groups of a prepolymer consisting of an epoxy resin, a polyester polyol, and an aliphatic and/or alicyclic diisocyanate. Consisting of blocked polyisocyanate,
This invention relates to an epoxy resin composition for precoated metal that has excellent flexibility and scratch resistance.
（従来の技術）
エポキシ樹脂系塗料は、優れた密着性と耐食性を有する
ため、金属表面の保護コーテイング材として巾広く使用
されている。特に、下塗りコーテイング材として性能が
卓越しているために、その需要は益々増加する傾向にあ
る。(Prior Art) Epoxy resin paints have excellent adhesion and corrosion resistance, and are therefore widely used as protective coating materials for metal surfaces. In particular, because of its outstanding performance as an undercoat coating material, the demand for it is on the rise.
一方、プレコートメタルは、金属被塗物を成形加工する
前に、あらかしめ工場で平らな切板、あるいは連続した
コイル状態で塗装して得られるもので、次のような特徴
がある。On the other hand, pre-coated metal is obtained by coating a metal object on a flat cut plate or a continuous coil in a preconditioning factory before it is molded, and has the following characteristics.
■ 塗着効率が良いので、塗料の使用量が減り、省資源
、コストダウンが図れる、
■ 品質が安定する、
■ 排気はオーブン中心となり、集中的に処理し易い等
、基本的に省資源、省コスト、公害対策といった面で優
れた特長を有している。■ Good coating efficiency reduces the amount of paint used, saving resources and reducing costs; ■ Stable quality; ■ Exhaust gas is centrally located in the oven, making it easier to treat centrally, which basically saves resources. It has excellent features in terms of cost savings and pollution control.
このために、プレコートメタルの需要は、従来の屋根材
から、外壁材、内壁材、シャッター材、雨戸材、物置材
等の建材分野へと伸長しつつある。For this reason, demand for precoated metal is expanding from conventional roofing materials to building materials such as exterior wall materials, interior wall materials, shutter materials, shutter materials, and storage materials.
さらに、近年、冷蔵庫、洗濯機、電子レンジ、オーディ
オボックス等の家電製品、あるいは自動車用防錆鋼板へ
の適用も検討され始めている。Furthermore, in recent years, applications have begun to be considered for home appliances such as refrigerators, washing machines, microwave ovens, and audio boxes, as well as rust-proof steel sheets for automobiles.
このような用途の拡大に伴って、より高度な加工性とよ
り苛酷な条件での耐久性が求められるようになり、プレ
コートの要求性能は、益々高度なものとなっている。With the expansion of such uses, higher workability and durability under harsher conditions are required, and the required performance of precoat is becoming increasingly sophisticated.
エポキシ樹脂は、耐食性、密着性に優れているという利
点がある反面、可撓性が劣り、加工性がよくないという
欠点を有するために、プレコートメタル用コーティング
素材として期待は大きいにもかかわらず、用途が限定さ
れているのが実情である。Although epoxy resin has the advantages of excellent corrosion resistance and adhesion, it has the disadvantages of poor flexibility and poor processability, so despite its high expectations as a coating material for pre-coated metal, The reality is that its uses are limited.
そのため、エポキシ樹脂の各種変性、可撓性、硬化剤と
の組合せ等が提案されている。特公昭５８−２５３４８
号公報、特公昭５Ｂ−４６１３４号公報、特公平１−３
７４２６号公報には、アルカノールアミン変性エポキシ
樹脂とポリイソシアナートを含む塗料組成物の提案がな
されている。Therefore, various modifications of epoxy resins, flexibility, combinations with hardening agents, etc. have been proposed. Special Public Service No. 58-25348
Publication No. 5B-46134, Special Publication No. 1-3
No. 7426 proposes a coating composition containing an alkanolamine-modified epoxy resin and a polyisocyanate.
これらは防錆性に優れた塗料を与えるものではあるが、
ＰＣＭのように苛酷な加工条件に耐えうる設計になって
いない。Although these provide paints with excellent rust prevention properties,
It is not designed to withstand harsh processing conditions like PCM.
一方、エポキシ樹脂と、ブロックイソシアネートとの組
合せについて、特公昭５３−１５９６０号公報、特公昭
６２−２５６８４号公報に、その技術の擾示がなされて
いる。これらの特許の主旨は、エポキシ樹脂の潜在型硬
化剤として、特殊なブロックイソシアナートを用いると
ころにあり、加工性、防錆性等の向上を目指す本発明と
は目的を異にする。On the other hand, regarding the combination of an epoxy resin and a blocked isocyanate, Japanese Patent Publication No. 53-15960 and Japanese Patent Publication No. 62-25684 disclose the technology. The gist of these patents is to use a special blocked isocyanate as a latent curing agent for epoxy resins, and their purpose is different from the present invention, which aims to improve processability, rust prevention, etc.
また、弊社は優れた可撓性を与える樹脂組成物として、
特願平１−１７１０８２号においてポリエステルとジイ
ソシアナートからなる末端イソシアナートプレポリマー
をブロックしたブロックポリイソシアナートと多価ヒド
ロキシル化合物よりなる組成物を提案している。しかし
ながら、多価ヒドロキシル化合物としてのエポキシ樹脂
についての検討はなされていない。In addition, our company has developed resin compositions that provide excellent flexibility.
Japanese Patent Application No. 1-171082 proposes a composition consisting of a blocked polyisocyanate obtained by blocking a terminal isocyanate prepolymer consisting of a polyester and a diisocyanate, and a polyhydric hydroxyl compound. However, no study has been made on epoxy resins as polyvalent hydroxyl compounds.
（発明が解決しようとする課題）
本発明の目的は、従来技術の課題点であった、可撓性が
ありかつ表面硬度の高い、極めて加工性に優れたプレコ
ートメタル用エポキシ樹脂組成物を提供することにある
。(Problems to be Solved by the Invention) The purpose of the present invention is to provide an epoxy resin composition for precoated metal that is flexible, has high surface hardness, and has extremely excellent workability, which has been a problem with the prior art. It's about doing.
本発明のもう一つの目的は、−液性で貯蔵安定性に優れ
、かつ硬化した塗膜は密着性と防錆性が良好であるプレ
コートメタル用エポキシ樹脂組成物を与えることにある
。Another object of the present invention is to provide an epoxy resin composition for precoated metal that is liquid-based and has excellent storage stability, and the cured coating film has good adhesion and rust prevention properties.
（課題を解決するための手段）
本発明者は、前記の課題を解決すべく、鋭意研究の結果
、本発明を完成するに至った。(Means for Solving the Problems) In order to solve the above-mentioned problems, the present inventor has completed the present invention as a result of intensive research.
すなわち、本発明は；
（ａ） エポキシ当量が３００以上であるエポキシ樹
脂１００重量部と、
（ｂ）数平均分子量５００〜２．０００．１分子中の平
均水酸基数２〜３のポリエステルポリオールと、脂肪族
および／または脂環族ジイソシアナートとを反応させて
得られる末端にイソシアナート基を持つプレポリマーで
あって、その末端がブロックされているフ゛ロツクポリ
イソシアナート５〜９０重量部、
とが配合されてなるプレコートメタル用エポキシ樹脂組
成物である。That is, the present invention includes: (a) 100 parts by weight of an epoxy resin having an epoxy equivalent of 300 or more; (b) a polyester polyol having an average number of hydroxyl groups in the molecule of 500 to 2.000.1; 5 to 90 parts by weight of a prepolymer having isocyanate groups at the terminals obtained by reacting with an aliphatic and/or alicyclic diisocyanate, the terminals of which are blocked; This is an epoxy resin composition for pre-coated metal.
本発明で使用するエポキシ樹脂（ａ）は、特に限定する
ものではないが、例えば多価フェノールとエピハロヒド
リンとの縮合物が挙げられ、最も代表的なものはビスフ
ェノールＡとエピクロルヒドリンとの縮合物である。The epoxy resin (a) used in the present invention is not particularly limited, but includes, for example, a condensate of polyhydric phenol and epihalohydrin, and the most typical one is a condensate of bisphenol A and epichlorohydrin. .
エポキシ樹脂のエポキシ当量は３００以上のものが用い
られる。３００より小さい場合は可撓性の良好な塗膜を
得ることができず、かつ、貯蔵安定性も満足なレベルの
ものとはならない、好ましくは、６００〜５０００の範
囲が良好な結果を得ることができる。エポキシ当量が５
０００を越える場合は、密着性が低下する傾向がある。The epoxy resin used has an epoxy equivalent of 300 or more. If it is less than 300, it will not be possible to obtain a coating film with good flexibility, and the storage stability will not be at a satisfactory level. Preferably, a value in the range of 600 to 5000 will give good results. I can do it. Epoxy equivalent is 5
If it exceeds 000, the adhesion tends to decrease.
本発明に用いる数平均分子量５００〜２０００．１分子
中の平均水酸基数２〜３のポリエステルポリオールを構
成するジオールまたはトリオールとしては、炭素数２〜
２０の直鎖または分岐状のアルキル基を有するものが使
用できる。その代表的な例としては、エチレングリコー
ル、プロピレングリコール、１，４−ブタンジオール、
１３ブタンジオール、ｌ、５−ベンタンジオール、ネオ
ペンチルグリコール、１．６−ヘキサンジオル、１．８
−オクタンジオール、２，２．４−トリメチル−１，３
−ベンタンジオール、グリセリン、トリメチロールプロ
パンなどがある。所望の平均水酸基数に応じて、ジオー
ルおよびトリオールの使用量を調節する。また、分岐状
のアルキル基を有するジオール、トリオールを使用する
と、得られるポリエステルポリオールの溶剤溶解性、エ
ポキシ樹脂との相溶性に好ましい影響を与える。The diol or triol constituting the polyester polyol having a number average molecular weight of 500 to 2,000.1 and having an average number of hydroxyl groups in one molecule of 2 to 3 carbon atoms has 2 to 3 carbon atoms.
Those having 20 straight chain or branched alkyl groups can be used. Typical examples include ethylene glycol, propylene glycol, 1,4-butanediol,
13-butanediol, l,5-bentanediol, neopentyl glycol, 1.6-hexanediol, 1.8
-octanediol, 2,2,4-trimethyl-1,3
- Bentanediol, glycerin, trimethylolpropane, etc. The amounts of diols and triols used are adjusted depending on the desired average number of hydroxyl groups. Further, when a diol or triol having a branched alkyl group is used, the solvent solubility of the resulting polyester polyol and the compatibility with the epoxy resin are favorably influenced.
また、本発明に用いる数平均分子量５００〜２゜０００
．１分子中の平均水酸基数２〜３のポリエステルポリオ
ールを構成するカルボン酸としては、炭素数２〜２０の
ジカルボン酸が用いられる。例えば、アジピン酸、アゼ
ライン酸、セバシン酸などが挙げられる。イソフタル酸
、テレフタル酸等の芳香族２塩基酸も使用しうるが、本
発明の組成物の可撓性を損なわないような範囲で使用し
なければならない。In addition, the number average molecular weight used in the present invention is 500 to 2゜000.
．． As the carboxylic acid constituting the polyester polyol having an average number of hydroxyl groups in one molecule of 2 to 3, a dicarboxylic acid having 2 to 20 carbon atoms is used. Examples include adipic acid, azelaic acid, and sebacic acid. Aromatic dibasic acids such as isophthalic acid and terephthalic acid may also be used, but they must be used within a range that does not impair the flexibility of the composition of the present invention.
本発明のポリエステルポリオールは、前記のジオール／
トリオールとジカルボン酸等の原料成分から常法により
、通常ｌＯＯ〜２５０℃の温度範囲でエステル化反応に
よって合成されるものである。また、好ましいポリエス
テルポリオールとしてポリカプロラクトンポリオールが
ある。ポリカプロラクトンポリオールは、ε−カプロラ
クトンを２価あるいは３価のアルコールを開始網として
、触媒の存在下に開環重合して得ることができる。The polyester polyol of the present invention comprises the above diol/
It is synthesized from raw materials such as triol and dicarboxylic acid by an esterification reaction in a conventional manner at a temperature range of 100 to 250°C. Moreover, polycaprolactone polyol is a preferable polyester polyol. Polycaprolactone polyol can be obtained by ring-opening polymerization of ε-caprolactone using a divalent or trivalent alcohol as an initiation network in the presence of a catalyst.
開始剤としては、エチレングリコール、プロピレングリ
コール、１，３−ブチレングリコール、ネオペンチルグ
リコール等の２価アルコールと、トリメチロールプロパ
ン、グリセリン等の３価アルコールが用いられる。低粘
度のプレポリマーを得るという面からは、分岐を有する
多価アルコールが好ましい。As the initiator, dihydric alcohols such as ethylene glycol, propylene glycol, 1,3-butylene glycol, and neopentyl glycol, and trihydric alcohols such as trimethylolpropane and glycerin are used. From the viewpoint of obtaining a low-viscosity prepolymer, branched polyhydric alcohols are preferred.
触媒としては、テトラブチルチタネート、テトラプロピ
ルチタネート、テトラエチルチタネート等の有機チタン
系化合物；オクチル酸スズ、ジブチルスズオキシド、ジ
ブチルスズジラウレート、塩化第１スズ、臭化第１スズ
等のスズ系化合物が用いられる。As the catalyst, organic titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, and tetraethyl titanate; tin compounds such as tin octylate, dibutyltin oxide, dibutyltin dilaurate, stannous chloride, and stannous bromide are used.
ε−カプロラクトンの開環重合は、Ｎ２ガス雰囲気で、
ε−カプロラクトン、上記の開始剤を所望の分子量にな
るようにモル比を設定し、更にεカプロラクトンに対し
て触媒を０．１〜１１００ｐｐ添加し、１５０〜２００
°Ｃの温度で４〜１０時間反応させることによって得ら
れる。カプロラクトンポリオールとして重版されている
ものには、プラクセル３０５、プラクセル３０８、プラ
クセル３１２ＡＬ、プラクセル２０５、プラクセル２１
２ＡＬ（いずれもダイセル化学工業■製、商品名）等が
ある。The ring-opening polymerization of ε-caprolactone is carried out in an N2 gas atmosphere.
Set the molar ratio of ε-caprolactone and the above-mentioned initiator to the desired molecular weight, and further add 0.1 to 1100 pp of catalyst to ε-caprolactone.
Obtained by reaction for 4-10 hours at a temperature of °C. Reprinted caprolactone polyols include Plaxel 305, Plaxel 308, Plaxel 312AL, Plaxel 205, Plaxel 21
2AL (both manufactured by Daicel Chemical Industries, trade name), etc.
本発明のポリエステルポリオールの数平均分子量は、５
００〜２，０００の範囲にあることが必要である。数平
均分子量が５００未満のポリエステルポリオールとジイ
ソシアナートからなるプレポリマーのブロック体を用い
た塗膜は、可撓性に劣る。また、数平均分子量が２，０
００を越えるポリエステルポリオールとジイソシアナー
トを用いた場合、ブロック体にした後の潜在ＮＣＯ基の
含有量が低くなり過ぎ、実用性に乏しい。さらに、エポ
キシ樹脂との相溶性を低下する傾向にある。The number average molecular weight of the polyester polyol of the present invention is 5
It must be in the range of 00 to 2,000. A coating film using a prepolymer block consisting of a polyester polyol and diisocyanate having a number average molecular weight of less than 500 has poor flexibility. In addition, the number average molecular weight is 2.0
When a polyester polyol exceeding 0.00 and a diisocyanate are used, the content of latent NCO groups after forming into a block becomes too low, resulting in poor practicality. Furthermore, it tends to reduce the compatibility with epoxy resins.
本発明において、ポリエステルポリオールの数平均分子
量は、水酸基価を測定し、次式により求めたものである
；
水酸基価：ＪＩＳ−Ｋｉ５７７の６．４に準じで測定し
た値。In the present invention, the number average molecular weight of the polyester polyol is determined by measuring the hydroxyl value and using the following formula; Hydroxyl value: Value measured according to 6.4 of JIS-Ki577.
Ｎ：ポリエステルポリオール１分子中の平均水＃水測の
数。N: Average water in one molecule of polyester polyol #Number of water measurements.
本発明におけるジイソシアナートとしては、脂肪族およ
び／または脂環族ジイソシアナートが用いられる。As the diisocyanate in the present invention, aliphatic and/or alicyclic diisocyanate is used.
また、脂肪族ジイソシアナートとしては、炭素数４〜３
０のものが、脂環族ジイソシアナートとしては、炭素数
８〜３０のものが好ましく用いられる。In addition, as the aliphatic diisocyanate, carbon number 4 to 3
As the alicyclic diisocyanate, those having 8 to 30 carbon atoms are preferably used.
脂肪族または脂環族ジイソシアナートの例としテハ、１
．４−テトラメチレンジイソシアナート、１．５−ペン
タメチレンジイソシアナート、１６−へキサメチレンジ
イソシアナート、２．２４−トリメチル−１，６−へキ
サメチレンジイソシアナート、リジンジイソシアナート
、３−イソシアナートメチル−３，５，５−トリメチル
シクロヘキシルイソシアナート（イソホロンジイソシア
ナート）、１．３−ビス（イソシアナートメチル）−シ
クロヘキサン、４．４’ −ジシクロヘキシルメタンジ
イソシアナート等を挙げることができる。Examples of aliphatic or cycloaliphatic diisocyanates include Teha, 1
．． 4-tetramethylene diisocyanate, 1.5-pentamethylene diisocyanate, 16-hexamethylene diisocyanate, 2.24-trimethyl-1,6-hexamethylene diisocyanate, lysine diisocyanate, 3 -isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 1,3-bis(isocyanatomethyl)-cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, etc. can.
ポリエステルポリオールと脂肪族および／または脂環族
ジイソシアナートとの反応は、下記のように行われる。The reaction between the polyester polyol and the aliphatic and/or alicyclic diisocyanate is carried out as follows.
反応温度は、常温〜２００℃の範囲、好ましくは８０〜
１４０°Ｃの範囲で行われる。反応温度が低い場合は反
応の完結に時間がかかりすぎ、逆に２００ ’Ｃを越え
る反応条件では、望ましくない副反応が起こってプレポ
リマーの粘度が上昇したり、生成するプレポリマーに著
しい着色が生したりして実用的でない。The reaction temperature ranges from normal temperature to 200°C, preferably from 80°C to
The temperature range is 140°C. If the reaction temperature is low, the reaction takes too long to complete; conversely, if the reaction temperature exceeds 200'C, undesirable side reactions may occur, increasing the viscosity of the prepolymer or causing significant coloration of the prepolymer produced. It's not practical because it's too late.
反応の際には、無溶剤でも良いし、イソシアナート基に
不活性な任意の溶剤を用いても良い、また、必要であれ
ば、イソシアナート基と水酸基との反応促進のための触
媒を用いても良い。During the reaction, no solvent may be used, or any solvent inert to isocyanate groups may be used, and if necessary, a catalyst may be used to promote the reaction between isocyanate groups and hydroxyl groups. It's okay.
反応に際して、ジイソシアナートとポリエステルポリオ
ールの仕込み当量比は、Ｎ ＣＯｌｏ Ｈ比５〜４０が
好ましい。この当量比が５より小さい場合は、ジイソシ
アナートとポリエステルポリオール間に逐次付加反応が
起こり、高分子量体が生成するため、プレポリマーの粘
度が上界する。この粘度上昇は、未反応ジイソシアナー
トの診去を困難にする。また、高粘度のプレポリマーの
ブロック体は、多価ヒドロキシル化合物との相溶性が低
下するし、可撓性が悪くなる。また、ＮＣ０１０Ｈ当量
比が４０を越えると、生産性が悪くなるため好ましくな
い。In the reaction, the equivalent ratio of diisocyanate and polyester polyol to be charged is preferably N COlo H ratio of 5 to 40. If this equivalent ratio is less than 5, a sequential addition reaction occurs between the diisocyanate and the polyester polyol, producing a high molecular weight substance, and thus the viscosity of the prepolymer becomes upper bound. This increase in viscosity makes it difficult to remove unreacted diisocyanate. In addition, a block of a highly viscous prepolymer has reduced compatibility with a polyhydric hydroxyl compound and poor flexibility. Moreover, if the NC010H equivalent ratio exceeds 40, productivity will deteriorate, which is not preferable.
反応が終了したならば、反応混合物中の未反応のジイソ
シアナートを、例えば薄膜蒸発装置、溶剤抽出等公知の
方法により回収する。未反応のジイソシアナートの残留
量が多いと、熱硬化時にジイソシアナートモノマーに起
因する臭気、毒性、刺激性等が問題になる。When the reaction is completed, unreacted diisocyanate in the reaction mixture is recovered by a known method such as a thin film evaporator or solvent extraction. If the residual amount of unreacted diisocyanate is large, problems such as odor, toxicity, irritation, etc. due to the diisocyanate monomer will arise during heat curing.
次に、本発明のブロンクボリイソシアナートは、前述の
ＮＧＯ基末端プレポリマーを公知の方法により各種のブ
ロック化剤と反応することにより得られる。Next, the bronc polyisocyanate of the present invention can be obtained by reacting the aforementioned NGO group-terminated prepolymer with various blocking agents by a known method.
この反応に用いられるブロック化剤としては、４Ｍｔば
フェノール系、ラクタム系、オキシム系、活性メチレン
系、アルコール系、メルカプタン系、酸アミド系、イミ
ド系、アミン系、イミダゾール系、′尿素系等のブロッ
ク化剤が使用されうるが、フェノール系、ラクタム系、
オキシム系、イミダゾール系等のブロック化剤が有利に
使用される。Blocking agents used in this reaction include 4Mt, phenol type, lactam type, oxime type, active methylene type, alcohol type, mercaptan type, acid amide type, imide type, amine type, imidazole type, 'urea type, etc. Blocking agents may be used, including phenolics, lactams,
Oxime-based, imidazole-based, and other blocking agents are advantageously used.
ブロック化剤の具体例としては、次のものが挙げられる
；
フェノール系ブロック化剤：
フェノール、クレゾール、キシレノール、エチルフェノ
ール等、
ラクタム系プロ、ツク化剤：
ε−カプロラクタム、δ−バレロラクタム、βブチロラ
クタム、β〜プロピオラクタム等、オキシム系ブロック
化剤：
ホルムアミドオキシム、アセトアミドオキシム、アセト
オキシム、メチルエチルケトオキシム、ジアセチルモノ
オキシム、ヘンシフエノンオキシム、シクロへキサノン
オキシム等、
活性メチレン系ブロック化剤：
マロン酸ジエチル、マロン酸ジメチル、アセト酢酸エチ
ル、アセト酢酸メチル、アセチルアセトン等、
アルコール系プロンク化荊：
メタノール、エタノール、プロパツール、イソプロパツ
ール、ブタノール、２−エチルヘキサノール、エチレン
グリコールモノメチルエーテル、エチレングリコールモ
ノエチルエーテル、エチレングリコールモノブチルエー
テル等、
イミダゾール系ブロック化剤：
イミダゾール、２−メチルイミダゾール、２エチルイミ
ダゾール、２−エチル−４−メチルイミダゾール、２−
ウンデシルイミダゾール、２フエニルイミタソール、２
−フェニル−４−メチルイミダゾニル等。Specific examples of blocking agents include the following; Phenolic blocking agents: phenol, cresol, xylenol, ethylphenol, etc. Lactam-based blocking agents: ε-caprolactam, δ-valerolactam, β Oxime-based blocking agents such as butyrolactam, β-propiolactam, etc. Active methylene-based blocking agents such as formamide oxime, acetamidoxime, acetoxime, methyl ethyl ketoxime, diacetylmonoxime, hensifenone oxime, cyclohexanone oxime, etc.: Diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate, acetylacetone, etc. Alcohol-based protons: methanol, ethanol, propatool, isoproptool, butanol, 2-ethylhexanol, ethylene glycol monomethyl ether, ethylene glycol Monoethyl ether, ethylene glycol monobutyl ether, etc., imidazole-based blocking agents: imidazole, 2-methylimidazole, 2ethylimidazole, 2-ethyl-4-methylimidazole, 2-
undecyl imidazole, 2 phenyl imitasol, 2
-phenyl-4-methylimidazonyl and the like.
本発明のブロックポリイソシアナートを製造するための
具体的方法としては、ＮＧＯ基末端プレポリマーとブロ
ック化剤とをＮＣＯ基／プロンクツク中の活性水素の当
量比０．９〜１．１、好ましくは、０．９５〜１．０５
で公知の方法により反応される。As a specific method for producing the blocked polyisocyanate of the present invention, the NGO group-terminated prepolymer and the blocking agent are mixed in an equivalent ratio of NCO group/active hydrogen in the block of 0.9 to 1.1, preferably , 0.95-1.05
The reaction is carried out by a method known in the art.
このブロック化の反応は無溶剤でも行えるが、活性水素
を持たない、エステル系、エーテル系、ケトン系、芳香
族系等の適当な溶剤中で行うのが好ましい。また、反応
に際しては、錫、亜鉛、鉛等の有機金属及び３級アミン
等を触媒として用いても良い。Although this blocking reaction can be carried out without a solvent, it is preferably carried out in a suitable solvent, such as an ester, ether, ketone, or aromatic solvent, which does not contain active hydrogen. Furthermore, in the reaction, organic metals such as tin, zinc, and lead, tertiary amines, and the like may be used as catalysts.
本発明のエポキシ樹脂とブロックポリイソシアナートの
配合比率は、エポキシ樹脂１００重量部に対して、ブロ
ックポリイソシアナートを５〜９０重量部、配合するこ
とが好ましい。ブロックポリイソシアナートの量が５重
量部より少ない場合には、充分な可撓性を有する塗膜は
得られない。The blending ratio of the epoxy resin and block polyisocyanate of the present invention is preferably 5 to 90 parts by weight of the block polyisocyanate per 100 parts by weight of the epoxy resin. If the amount of blocked polyisocyanate is less than 5 parts by weight, a coating film with sufficient flexibility cannot be obtained.
また、ブロックポリイソシアナートの量が９０重量部を
越えると、塗膜が柔軟になりすぎ、表面硬度が低くなる
。On the other hand, if the amount of blocked polyisocyanate exceeds 90 parts by weight, the coating film will become too flexible and the surface hardness will decrease.
本発明の組成物においては、前記の必須成分の他に、ト
ルエン、キシレン等の芳香族炭化水素類；アセトン、メ
チルエチルケトン、メチルイソブチルケトン、ジイソブ
チルケトン等のケトン類；酢酸エチル、酢酸ｎ−ブチル
、酢酸イソブチル、酢酸セロソルブ等のエステル類など
通常の塗料用溶剤を含有することができる。In the composition of the present invention, in addition to the above-mentioned essential components, aromatic hydrocarbons such as toluene and xylene; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone; ethyl acetate, n-butyl acetate, It can contain common paint solvents such as esters such as isobutyl acetate and cellosolve acetate.
本発明の組成物においては、顔料、添加剤及びその他の
塗料用副資材などを適当添加することができる。In the composition of the present invention, pigments, additives, and other auxiliary materials for coating materials can be appropriately added.
顔料、添加物の例としては、ガラス繊維、アスベスト繊
維、ホウ素繊維、炭素繊維、セルロース、ポリエチレン
粉末；鉱物性ケイ酸塩、例えばアスベスト、及び雲母粉
、カオリン、酸化アルミニウム、水酸化アルミニウム、
セラコラ、三酸化アンチモン、シリカ、パライト、ゼオ
ライト、二酸化チタン、タルク、カーボンブラック、グ
ラファイト；酸化物系着色顔料、例えば酸化鉄、又は金
属粉、例えば鉄粉、亜鉛末、鉛粉、アルミニウム粉末、
防錆顔料、例えば鉛丹、クロム酸鉛、リン酸亜鉛、塩基
性硫酸鉛、モリブデン酸亜鉛、更には有機系着色顔料、
例えばフタロシアニンブルーフタロシアニングリーンな
どがあり、また各種の分散剤、揺変性付与削なども含め
てこれらは用途に応じて適宜用いられる。Examples of pigments and additives include glass fibers, asbestos fibers, boron fibers, carbon fibers, cellulose, polyethylene powder; mineral silicates such as asbestos, and mica powder, kaolin, aluminum oxide, aluminum hydroxide,
Ceracola, antimony trioxide, silica, pallite, zeolite, titanium dioxide, talc, carbon black, graphite; oxide coloring pigments such as iron oxide, or metal powders such as iron powder, zinc powder, lead powder, aluminum powder,
Antirust pigments such as red lead, lead chromate, zinc phosphate, basic lead sulfate, zinc molybdate, and organic coloring pigments,
Examples include phthalocyanine blue and phthalocyanine green, and these, including various dispersants and thixotropic additives, can be used as appropriate depending on the purpose.
また、塗料用副資材としては、例えば、フタル酸、アジ
ピン酸、アゼライト酸、セバシン酸、マレイン酸、トリ
メリント酸、クエン酸、オレイン酸、リシノール酸、ス
テアリン酸並びにその他の脂肪酸；リン酸、スルホン酸
、グリコール、グリセロール、パラフィンおよびジフェ
ニルなどから誘導される可塑剤；ポリエステル、ポリエ
ーテル、アルキンド樹脂、ブタジェンを含む共重合体な
どの重合形可塑剤；石油樹脂、塩化ゴム、塩素化ポリプ
ロピレン、クマロン樹脂、キシレン樹脂、ブチラール樹
脂、ケトン樹脂、スチレン−ブタジェン樹脂などの合成
樹脂；コーパル樹脂、ダンマル、エステルガム、ギルツ
ナイト、アスファルト、ピッチ液体又は固形ビチューメ
ンなどの天然または加工樹脂など、防食塗料の原料とし
て通常に用いられているものが使用できる。In addition, auxiliary materials for paints include, for example, phthalic acid, adipic acid, azelite acid, sebacic acid, maleic acid, trimellitic acid, citric acid, oleic acid, ricinoleic acid, stearic acid, and other fatty acids; phosphoric acid, sulfonic acid. , glycols, glycerol, paraffin and diphenyl, etc.; polymeric plasticizers such as polyesters, polyethers, alkynd resins, copolymers containing butadiene; petroleum resins, chlorinated rubber, chlorinated polypropylene, coumaron resins, Synthetic resins such as xylene resins, butyral resins, ketone resins, styrene-butadiene resins; natural or processed resins such as copal resin, dammar, ester gum, giltonite, asphalt, pitch liquid or solid bitumen, commonly used as raw materials for anticorrosion coatings. You can use what is currently available.
塗装方法としては、ハケ、エアレススプレーローラー等
の方法で塗装され、焼き付は温度として５０〜２５０°
Ｃの温度が用いられる。The painting method is brush, airless spray roller, etc., and the baking temperature is 50 to 250 degrees.
A temperature of C is used.
以下、実施例によりさらに詳しく本発明の説明を行うが
、これらによって本発明を限定するものではない。Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited by these.
〈ブロックポリイソシアナートの製造〉合成例１
温度針、冷却器、攪拌器付の２１フラスコに、ヘキサメ
チレンジイソシアナート（ＨＭＤＩ）７９２．４ｇ （
９，４３当量）とポリカプロラクトンポリオール「プラ
クセル３０５Ｊ （ダイセル化学工業■製、商品名、
数平均分子量５５０、水酸基価３０．５■ＫＯＨ／ｇ）
１１５．３ｇ （０゜６３当量）とを仕込み、攪拌下１
００℃で１時間反応させた。<Manufacture of block polyisocyanate> Synthesis Example 1 792.4 g of hexamethylene diisocyanate (HMDI) was placed in a 21 flask equipped with a temperature needle, a condenser, and a stirrer.
9,43 equivalents) and polycaprolactone polyol “Plaxel 305J (manufactured by Daicel Chemical Industries, Ltd., trade name,
Number average molecular weight 550, hydroxyl value 30.5 KOH/g)
115.3g (0゜63 equivalent) and stirred
The reaction was carried out at 00°C for 1 hour.
かくして得られた反応液を１６０°Ｃ１０，２■Ｈｇで
Ｅ！ｗｉ！！留し、未反応のＨＭＤ Ｉを除去した。The reaction solution thus obtained was heated to E! at 160°C and 10.2■Hg. Wi! ! to remove unreacted HMDI.
缶底液として、ＮＧＯ濃度１１．７重量％（理論値１２
．０重量％）、２５°Ｃにおける粘度が４゜８００ｃｐ
、ガスクロマトグラフィーにより分析した遊離ＨＭＤ
Ｉモノマーが０．２重量％の淡黄色透明なポリイソシア
ナートプレポリマー２０９゜９ｇを得た（プレポリマー
Ｉ）。As the bottom liquid of the can, the NGO concentration was 11.7% by weight (theoretical value 12%).
．． 0% by weight), viscosity at 25°C is 4°800cp
, free HMD analyzed by gas chromatography
209.9 g of a pale yellow transparent polyisocyanate prepolymer containing 0.2% by weight of monomer I was obtained (prepolymer I).
次に、温度計、冷却器、攪拌器、窒素導入管付のフラス
コに、プレポリマー１ １００部、セルソルブアセテー
ト３１．０部、メチルエチルケトオキシム２４．２部を
仕込み、５０°Ｃで２時間反応させ、ブロックポリイソ
シアナートＡ溶液を得た。得られたブロックポリイソシ
アナートＡ溶液の潜在ＮＧＯ含有量が７．５％、固形分
は８０％であった。Next, 100 parts of Prepolymer 1, 31.0 parts of Cellsolve Acetate, and 24.2 parts of methyl ethyl ketoxime were placed in a flask equipped with a thermometer, condenser, stirrer, and nitrogen inlet tube, and the mixture was reacted at 50°C for 2 hours. A blocked polyisocyanate A solution was obtained. The resulting blocked polyisocyanate A solution had a latent NGO content of 7.5% and a solid content of 80%.
合成例２
プレポリマー■ １００部、セルソルブアセテート３２
部、フェノール２６．２部を仕込み、合成例１と同様の
方法でブロックポリイソシアナートＢ溶液を得た。得ら
れたブロックポリイワシアナ−１−Ｂ溶液の潜在ＮＣＯ
含を量が７．４％、固形分は８０％であった。Synthesis Example 2 Prepolymer ■ 100 parts, Cellsolve Acetate 32
1 part, and 26.2 parts of phenol were charged, and a blocked polyisocyanate B solution was obtained in the same manner as in Synthesis Example 1. Latent NCO of the obtained blocked polysardineana-1-B solution
The content was 7.4% and the solid content was 80%.
合成例３
プレポリマー１１００部、セルソルブアセテート３１部
、２−メチルイミダゾール２２，８部を仕込み、合成例
１と同様の方法でブロックポリイソシアナートＣ溶液を
得た。得られたブロックポリイソシアナートＣ溶液の潜
在ＮＧＯ含存量が７．６％、固形分は８０％であった。Synthesis Example 3 A block polyisocyanate C solution was obtained in the same manner as in Synthesis Example 1 by charging 1,100 parts of prepolymer, 31 parts of cellosolve acetate, and 22.8 parts of 2-methylimidazole. The obtained blocked polyisocyanate C solution had a latent NGO content of 7.6% and a solid content of 80%.
合成例４
温度計、冷却器、ａ性器、窒素導入管付のフラスコに、
１．４−ブタンジオール４５０部、アジピン酸５８４部
を仕込み、常法により２２０°Ｃで１０時間反応させ、
酸価４．５■ＫＯＨ／ｇ、水酸基価１１０■ＫＯＨ／ｇ
で、１分子量中の平均水酸基数が２のポリエステルポリ
オール８２０部を得た。水酸基価から計算で求められる
ポリエステルポリオールの数平均分子量は１，０２０で
あった。Synthesis Example 4 In a flask equipped with a thermometer, a cooler, a genitalia, and a nitrogen introduction tube,
450 parts of 1.4-butanediol and 584 parts of adipic acid were charged and reacted at 220°C for 10 hours using a conventional method.
Acid value 4.5 ■KOH/g, hydroxyl value 110 ■KOH/g
Thus, 820 parts of polyester polyol having an average number of hydroxyl groups per molecular weight of 2 was obtained. The number average molecular weight of the polyester polyol calculated from the hydroxyl value was 1,020.
上記の方法で得られたポリエステルポリオール３００部
、１．６−へキサメチレンジイソシアナート（ＨＭＤＩ
）７４１部を仕込み、攪拌下、１００℃で１０時間反応
させた。300 parts of polyester polyol obtained by the above method, 1,6-hexamethylene diisocyanate (HMDI
) and reacted at 100° C. for 10 hours with stirring.
かくして得られた反応液を、ＴＲ膜蒸発装置を用いて、
１回目０． ８＋＋ｍＨｇ／ １６０ ”Ｃ１２回目０
゜２ｍＨｇ／１６０℃、の条件下で未反応ＨＭＤ １を
除去した。ＮＣＯ含有量６．２％、未反応ＨＭＤＩが０
．２％のプレポリマー３７４部が得られた（プレポリマ
ー■）。The reaction solution thus obtained was evaporated using a TR film evaporator.
1st time 0. 8++mHg/ 160”C12th 0
Unreacted HMD 1 was removed under conditions of 2 mHg/160°C. NCO content 6.2%, unreacted HMDI 0
．． 374 parts of a 2% prepolymer were obtained (prepolymer ■).
次に、上記の方法で得られたプレポリマー３７４部、酢
酸エチル１１３部、ブロンク他剤としてメチルエチルケ
トオキシム３９．３部を仕込み、５０°Ｃで２時間反応
させ、ブロックポリイソシアナートＤ溶液を得た。得ら
れたブロックポリイソシアナートＢ溶液の潜在ＮＧＯ含
存置が４．１％、固形分は７５％であった。Next, 374 parts of the prepolymer obtained by the above method, 113 parts of ethyl acetate, and 39.3 parts of methyl ethyl ketoxime as a bronch agent were charged and reacted at 50°C for 2 hours to obtain a block polyisocyanate D solution. Ta. The resulting blocked polyisocyanate B solution had a latent NGO content of 4.1% and a solid content of 75%.
合成例５
温度計、冷却器、撹拌器付の２１フラスコに、ヘキサメ
チレンジイソシアナート（ＨＭＤＩ）１５１２．０ｇ
（１８当量）とポリカプロラクトンポリオール「プラク
セル３０３．（ダイセル化学工業■製、商品名、数平均
分子量３００、水酸基価５４０ｕＫＯＨ／ｇ）１２０ｇ
（１，１５当量）とを仕込み、攪拌下１００°Ｃで１
時間反応させた。Synthesis Example 5 1512.0 g of hexamethylene diisocyanate (HMDI) was placed in a 21 flask equipped with a thermometer, condenser, and stirrer.
(18 equivalents) and polycaprolactone polyol "Plaxel 303. (manufactured by Daicel Chemical Industries, Ltd., trade name, number average molecular weight 300, hydroxyl value 540uKOH/g) 120g
(1.15 equivalents) and heated at 100°C with stirring
Allowed time to react.
かくして得られた反応液を１６０″Ｃ，０，２ｍＨｇで
薄膜蒸留し、未反応のＨＭＤ Ｉを除去した。The reaction solution thus obtained was subjected to thin film distillation at 160''C and 0.2 mHg to remove unreacted HMDI.
缶底液として、ＮＧＯ濃度１４．７重量％の淡黄色透明
なポリイソシアナートプレポリマーを得た（プレポリマ
ー■）。A pale yellow transparent polyisocyanate prepolymer with an NGO concentration of 14.7% by weight was obtained as a bottom liquid (prepolymer ■).
上記の方法で得られたプレポリマーＩ［［１００部、セ
ルソルブアセテート３３．０部、メチルエチルケトオキ
シム３０．５部を仕込み、５０°Ｃで２時間反応させ、
ブロックポリイソシアナートＥ溶液を得た。得られたブ
ロックポリイソシアナートＥ溶液の潜在ＮＧＯ含有量は
９．０％、固形分は８０％であった。100 parts of prepolymer I obtained by the above method, 33.0 parts of cellosolve acetate, and 30.5 parts of methyl ethyl ketoxime were charged and reacted at 50°C for 2 hours.
A blocked polyisocyanate E solution was obtained. The resulting blocked polyisocyanate E solution had a latent NGO content of 9.0% and a solid content of 80%.
合成例６
温度計、冷却器、攪拌器、窒素導入前付のフラスコに、
１．４−ブタンジオール１，０８０部、アジピッ６１．
６０６部を仕込み、常法により２２０℃で１０時間反応
させ、酸価１．ＯｍｇＫＯｆ（７ｇ、水酸基価４８■Ｋ
ＯＨ／ｇで、１分子中の平均水酸基数が２のポリエステ
ルポリオール２２００部を得た。水酸基価から計算で求
められるポリエステルポリオールの数平均分子量は２，
３３３であった。Synthesis Example 6 In a flask equipped with a thermometer, condenser, stirrer, and nitrogen introduction,
1,080 parts of 4-butanediol, 61 parts of Adipid.
606 parts were charged and reacted at 220°C for 10 hours in a conventional manner to give an acid value of 1. OmgKOf (7g, hydroxyl value 48 K
2,200 parts of polyester polyol having an average number of hydroxyl groups per molecule of 2 in terms of OH/g was obtained. The number average molecular weight of polyester polyol calculated from the hydroxyl value is 2,
It was 333.
かくして得られたポリエステルポリオール３゜０部、１
６−へキサメチレンジイソシアナート（ＨＭＤＩ）４５
０部を仕込み、攪拌下１００℃で１０時間反応させた。3.0 parts of the polyester polyol thus obtained, 1
6-hexamethylene diisocyanate (HMDI) 45
0 part was charged and reacted at 100° C. for 10 hours with stirring.
得られた反応液を、薄膜蒸発装置を用いて、１回目０．
８ｍｎＨｇ／ｌ ６０°Ｃ１２回目０．２ｍ＋Ｈｇ／１
６０℃の条件下で未反応のＨＭＤ Ｉを除去し、ＮＧＯ
含有量が３．１％のプレポリマー■が得られた。The obtained reaction solution was heated to 0.0% for the first time using a thin film evaporator.
8mnHg/l 60°C 12th 0.2m+Hg/1
Unreacted HMD I was removed at 60°C, and NGO
A prepolymer (■) with a content of 3.1% was obtained.
次に、プレポリマー■１００部、酢酸エチル１０６．４
部、ブロック化剤として、メチルエチルケトオキシム６
．４部を仕込み、５０°Ｃで２時間反応さセ、ブロック
ポリイソシアナートＦ溶液を得た。得られたブロックポ
リイソシアナートＦ溶液の潜在ＮＧＯ含有量は１．５％
、固形分は５０％であった。Next, 100 parts of prepolymer ■, 106.4 parts of ethyl acetate
part, methyl ethyl ketoxime 6 as a blocking agent
．． 4 parts were charged and reacted at 50°C for 2 hours to obtain a blocked polyisocyanate F solution. The latent NGO content of the obtained blocked polyisocyanate F solution was 1.5%.
, solids content was 50%.
実施例１〜６及び比較例１〜５
合成例１〜６で合成したブロックポリイソシアナート溶
液、希釈剤セロソルブアセテート、及びＡＥＲ３３１Ｒ
（旭化成工業■製、エポキシレジン、エポキシ当量１９
０）、ＡＥＲ６６１Ｒ（旭化成工業■製、エポキシレジ
ン、エポキシ当量４７５）、ＡＥＲ６６４Ｒ（旭化成工
業■製、エポキシレジン、エポキシ当量９５０）、ＡＥ
Ｒ６６９Ｒ（旭化成工業■製、エポキシレジン、エポキ
シ当量２．５００）を第１〜２表に示す割合で配合し、
本発明の塗料組成物を得た。Examples 1 to 6 and Comparative Examples 1 to 5 Block polyisocyanate solutions synthesized in Synthesis Examples 1 to 6, diluent cellosolve acetate, and AER331R
(Manufactured by Asahi Kasei Corporation, epoxy resin, epoxy equivalent: 19
0), AER661R (manufactured by Asahi Kasei Kogyo ■, epoxy resin, epoxy equivalent weight 475), AER664R (manufactured by Asahi Kasei Kogyo ■, epoxy resin, epoxy equivalent weight 950), AE
R669R (manufactured by Asahi Kasei Kogyo ■, epoxy resin, epoxy equivalent weight 2.500) was blended in the proportions shown in Tables 1 and 2,
A coating composition of the present invention was obtained.
この組成物を用い、ブリキ板に３０μｍの厚みに塗布し
、２５０℃、３０秒間の焼き付は硬化を実施した。被塗
物の比較試験を行った結果を第１〜２表にまとめた。This composition was applied to a tin plate to a thickness of 30 μm, and baked at 250° C. for 30 seconds to harden it. The results of comparative tests on coated objects are summarized in Tables 1 and 2.
表において、各種試験は以下の通りである。In the table, the various tests are as follows.
■ 鉛筆硬度： ＪＩＳ Ｋ−５４００６，１４に準する。■ Pencil hardness: Conforms to JIS K-54006, 14.
■ ゴバン目密着試験： ＪＩＳ Ｇ−３３１２に準する。■ Goban adhesion test: Conforms to JIS G-3312.
■ 耐屈曲性： ＯＴ折り曲げ加工後のクランクの状況を見る。■ Flexibility: Check the condition of the crank after OT bending.
クランクなし Ｏ、クラック発生 ×、■ 耐沸水性： 煮沸１時間後、塗膜の外観の観察する。No crank O, cracking ×, ■ Boiling water resistance: After 1 hour of boiling, the appearance of the coating film was observed.
白化なし Ｏ１白化 ×、
■ 貯蔵安定性：
１力月の放置後に、
変化なし Ｏ、ゲル化 ×、
（発明の効果）
本発明の塗料組成物は、上記の通り、表面硬度（鉛筆硬
度）と耐屈曲性に優れ、また、密着性、耐沸水性、貯蔵
安定性に優れた塗膜が得られた。No whitening O1 Whitening ×, ■ Storage stability: No change after standing for one month O, Gelling ×, (Effects of the invention) As described above, the coating composition of the present invention has a high surface hardness (pencil hardness). A coating film with excellent bending resistance, adhesion, boiling water resistance, and storage stability was obtained.
（ほか１名）(1 other person)
Claims (1)
００重量部と、 （ｂ）数平均分子量５００〜２，０００、１分子中の平
均水酸基数２〜３のポリエステルポリオールと、脂肪族
および／または脂環族ジイソシアナートとを反応させて
得られる末端にイソシアナート基を持つプレポリマーで
あって、その末端がブロックされているブロックポリイ
ソシアナート５〜９０重量部、 とが配合されてなるプレコートメタル用エポキシ樹脂組
成物。[Scope of Claims] (a) Epoxy resin 1 having an epoxy equivalent of 300 or more
(b) obtained by reacting a polyester polyol with a number average molecular weight of 500 to 2,000 and an average number of hydroxyl groups in one molecule of 2 to 3, and an aliphatic and/or alicyclic diisocyanate. An epoxy resin composition for precoat metal, which is a prepolymer having isocyanate groups at the ends, and contains 5 to 90 parts by weight of blocked polyisocyanate whose ends are blocked.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2175386A JPH0465475A (en) | 1990-07-04 | 1990-07-04 | Epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2175386A JPH0465475A (en) | 1990-07-04 | 1990-07-04 | Epoxy resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0465475A true JPH0465475A (en) | 1992-03-02 |
Family
ID=15995204
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2175386A Pending JPH0465475A (en) | 1990-07-04 | 1990-07-04 | Epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0465475A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0953043A (en) * | 1995-06-05 | 1997-02-25 | Asahi Chem Ind Co Ltd | One-component cold-curing urethane coating composition |
| WO2003095195A1 (en) * | 2002-05-14 | 2003-11-20 | Nippon Steel Corporation | Coated metal material capable of being welded which is excellent in corrosion resistance of worked zone |
| JP2012107172A (en) * | 2010-11-18 | 2012-06-07 | Ppg Industries Ltd | Method for producing imidazole blocked polyurethane resin having improved flexibility, imidazole blocked polyurethane resin produced using the method, and coating for precoated automobile steel plate containing the resin |
-
1990
- 1990-07-04 JP JP2175386A patent/JPH0465475A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0953043A (en) * | 1995-06-05 | 1997-02-25 | Asahi Chem Ind Co Ltd | One-component cold-curing urethane coating composition |
| WO2003095195A1 (en) * | 2002-05-14 | 2003-11-20 | Nippon Steel Corporation | Coated metal material capable of being welded which is excellent in corrosion resistance of worked zone |
| US7390564B2 (en) | 2002-05-14 | 2008-06-24 | Nippon Steel Corporation | Coated metal material capable of being welded which is excellent in corrosion resistance of worked zone |
| JP2012107172A (en) * | 2010-11-18 | 2012-06-07 | Ppg Industries Ltd | Method for producing imidazole blocked polyurethane resin having improved flexibility, imidazole blocked polyurethane resin produced using the method, and coating for precoated automobile steel plate containing the resin |
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