WO2022215494A1 - エポキシ樹脂硬化剤、エポキシ樹脂組成物及び塗料 - Google Patents
エポキシ樹脂硬化剤、エポキシ樹脂組成物及び塗料 Download PDFInfo
- Publication number
- WO2022215494A1 WO2022215494A1 PCT/JP2022/012575 JP2022012575W WO2022215494A1 WO 2022215494 A1 WO2022215494 A1 WO 2022215494A1 JP 2022012575 W JP2022012575 W JP 2022012575W WO 2022215494 A1 WO2022215494 A1 WO 2022215494A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- epoxy resin
- curing agent
- polyamine
- epoxy
- diamine
- Prior art date
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 174
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 174
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 104
- 239000000203 mixture Substances 0.000 title claims abstract description 78
- 238000000576 coating method Methods 0.000 title abstract description 58
- 239000011248 coating agent Substances 0.000 title abstract description 56
- 150000004985 diamines Chemical class 0.000 claims abstract description 78
- 229920000768 polyamine Polymers 0.000 claims abstract description 60
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 24
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 7
- 239000004593 Epoxy Substances 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 27
- 239000003973 paint Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 18
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 claims description 16
- 125000003700 epoxy group Chemical group 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 239000004848 polyfunctional curative Substances 0.000 claims description 2
- -1 orthoxylylenediamine Chemical compound 0.000 description 36
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical class NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 25
- 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 16
- 238000011156 evaluation Methods 0.000 description 15
- 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 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000000034 method Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 239000000376 reactant Substances 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
- 238000007259 addition reaction Methods 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 210000003813 thumb Anatomy 0.000 description 4
- 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 4
- 229910000165 zinc phosphate Inorganic materials 0.000 description 4
- KAVGLYSOAJGTPJ-UHFFFAOYSA-N 2-[3-(2-aminoethyl)phenyl]ethanamine Chemical compound NCCC1=CC=CC(CCN)=C1 KAVGLYSOAJGTPJ-UHFFFAOYSA-N 0.000 description 3
- FVHFDNYRMIWPRS-UHFFFAOYSA-N 2-[4-(2-aminoethyl)phenyl]ethanamine Chemical compound NCCC1=CC=C(CCN)C=C1 FVHFDNYRMIWPRS-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- GRPFZJNUYXIVSL-UHFFFAOYSA-N 2-[3-(cyanomethyl)phenyl]acetonitrile Chemical compound N#CCC1=CC=CC(CC#N)=C1 GRPFZJNUYXIVSL-UHFFFAOYSA-N 0.000 description 2
- FNAICUMTBJWHPR-UHFFFAOYSA-N 2-[4-(1-aminopropan-2-yl)phenyl]propan-1-amine Chemical compound NCC(C)C1=CC=C(C(C)CN)C=C1 FNAICUMTBJWHPR-UHFFFAOYSA-N 0.000 description 2
- FUQCKESKNZBNOG-UHFFFAOYSA-N 2-[4-(cyanomethyl)phenyl]acetonitrile Chemical compound N#CCC1=CC=C(CC#N)C=C1 FUQCKESKNZBNOG-UHFFFAOYSA-N 0.000 description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 2
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000009408 flooring Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000004658 ketimines Chemical class 0.000 description 2
- 239000002075 main ingredient Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- UTCOUOISVRSLSH-UHFFFAOYSA-N 1,2-Anthracenediol Chemical compound C1=CC=CC2=CC3=C(O)C(O)=CC=C3C=C21 UTCOUOISVRSLSH-UHFFFAOYSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- HSDVRWZKEDRBAG-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COC(CCCCC)OCC1CO1 HSDVRWZKEDRBAG-UHFFFAOYSA-N 0.000 description 1
- VLKXLWGYPOUERV-UHFFFAOYSA-N 2-[3-(oxiran-2-ylmethoxy)propoxymethyl]oxirane Chemical compound C1OC1COCCCOCC1CO1 VLKXLWGYPOUERV-UHFFFAOYSA-N 0.000 description 1
- AJRJTSCSQBPBJC-UHFFFAOYSA-N 2-[4-(1-aminopropan-2-yl)phenyl]propan-1-amine;dihydrochloride Chemical compound Cl.Cl.NCC(C)C1=CC=C(C(C)CN)C=C1 AJRJTSCSQBPBJC-UHFFFAOYSA-N 0.000 description 1
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- GGIBUEPJJRWWNM-UHFFFAOYSA-N 2-[[2-[2-(oxiran-2-ylmethoxy)phenyl]phenoxy]methyl]oxirane Chemical compound C1OC1COC1=CC=CC=C1C1=CC=CC=C1OCC1CO1 GGIBUEPJJRWWNM-UHFFFAOYSA-N 0.000 description 1
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- BDYVWDMHYNGVGE-UHFFFAOYSA-N [2-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCCC1CN BDYVWDMHYNGVGE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001334 alicyclic compounds Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000001743 benzylic group Chemical group 0.000 description 1
- XMSVKICKONKVNM-UHFFFAOYSA-N bicyclo[2.2.1]heptane-3,4-diamine Chemical compound C1CC2(N)C(N)CC1C2 XMSVKICKONKVNM-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- KEIQPMUPONZJJH-UHFFFAOYSA-N dicyclohexylmethanediamine Chemical compound C1CCCCC1C(N)(N)C1CCCCC1 KEIQPMUPONZJJH-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 210000003811 finger Anatomy 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- GHAIYFTVRRTBNG-UHFFFAOYSA-N piperazin-1-ylmethanamine Chemical compound NCN1CCNCC1 GHAIYFTVRRTBNG-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
- C08G59/184—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents with amines
-
- 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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
-
- 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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
-
- 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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- 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
Definitions
- the present invention relates to epoxy resin curing agents, epoxy resin compositions and paints.
- Epoxy resin compositions using various polyamines such as xylylenediamine as curing agents for epoxy resins are used in the fields of coatings such as anticorrosion coatings for ships, bridges, land and sea iron structures, linings, reinforcements and repair materials for concrete structures, and construction materials. It is widely used in the civil engineering and construction fields, such as flooring materials, linings for water and sewage systems, pavement materials, and adhesives. Among these, it is important that the epoxy resin composition for coating is excellent in appearance, water resistance, chemical resistance, physical properties of the resulting coating film, and the like.
- Polyamines such as xylylenediamine or modified products thereof are known to be useful as epoxy resin curing agents for paints.
- an epoxy resin composition comprising a predetermined modified epoxy resin and an amine-based curing agent as essential components has low viscosity, excellent low-temperature curability, and mechanical strength, moisture resistance, adhesiveness, etc. It is disclosed that it has excellent physical properties and is particularly suitable for civil engineering, paint, and adhesive applications.
- the amine-based curing agent include those containing Mannich reaction-modified meta-xylylenediamine as a main component.
- meta-xylylenediamine When meta-xylylenediamine is used as an epoxy resin curing agent, it has the advantage of being able to achieve rapid curing and high chemical resistance. However, meta-xylylenediamine tends to form a carbonate when reacting with carbon dioxide in the air. Therefore, if meta-xylylenediamine or its modified form is used as a curing agent, the resulting coating film will turn white (brushing). transparency was sometimes reduced. In addition, since meta-xylylenediamine has an aromatic ring, the formed coating film may turn yellow over time, and there is room for improvement in terms of weather resistance as well.
- An object of the present invention is to provide an epoxy resin curing agent, an epoxy resin composition, and a paint containing these that can form a coating film with excellent transparency and weather resistance.
- an epoxy resin curing agent containing a polyamine containing a diamine having a specific structure or an adduct modified form of the polyamine can solve the above problems. That is, the present invention relates to the following. [1] An epoxy resin curing agent containing a polyamine (A) containing a diamine (A1) represented by the following general formula (1) or an adduct-modified polyamine (A).
- R 1 to R 8 each independently represent a hydrogen atom or an aliphatic group having 1 to 5 carbon atoms.
- the diamine (A1) is at least one selected from the group consisting of diamines represented by formulas (1-1) to (1-3) below. Resin hardener.
- an epoxy resin curing agent an epoxy resin composition
- a paint containing these that can form a coating film with excellent transparency and weather resistance.
- the epoxy resin curing agent of the present invention is an epoxy resin curing agent containing a polyamine (A) containing a diamine (A1) represented by the following general formula (1) or an adduct modified form of the polyamine (A). That is, the curing agent contains at least one selected from the group consisting of the polyamine (A) and adduct modified products of the polyamine (A).
- R 1 to R 8 each independently represent a hydrogen atom or an aliphatic group having 1 to 5 carbon atoms.
- xylylenediamine has the problem that it tends to whiten by forming a carbonate by the action of carbon dioxide in the air, and it tends to yellow over time because it has an aromatic ring. Furthermore, since xylylenediamine has a benzyl skeleton, the hydrogen atom at the benzylic position is likely to be abstracted, which is thought to cause deterioration in weather resistance.
- the diamine (A1) represented by the general formula (1) is more stable than xylylenediamine because hydrogen atoms are less likely to be abstracted, and is less likely to whiten even when in contact with carbon dioxide. Therefore, it is considered that the epoxy resin composition containing the epoxy resin curing agent of the present invention using the diamine (A1) has excellent transparency and weather resistance of the coating film formed.
- Diamine (A1) is a diamine represented by the following general formula (1).
- R 1 to R 8 each independently represent a hydrogen atom or an aliphatic group having 1 to 5 carbon atoms.
- Examples of the aliphatic group having 1 to 5 carbon atoms in R 1 to R 8 in the general formula (1) include an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group. .
- the aliphatic group is preferably an alkyl group having 1 to 5 carbon atoms.
- alkyl group examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group and i-pentyl. and the like.
- an alkyl group having 1 to 3 carbon atoms is preferable, a methyl group or an ethyl group is more preferable, and a methyl group is even more preferable.
- R 1 to R 8 in the general formula (1) are each independently a hydrogen atom or a methyl group.
- R 1 to R 8 are more preferably hydrogen atoms, and more preferably 6 or more of R 1 to R 8 are hydrogen atoms.
- all of R 1 to R 8 may be hydrogen atoms.
- R 3 , R 4 , R 7 and R 8 are hydrogen atoms and R 1 , R 2 , R 5 and R 6 are hydrogen atoms or methyl groups.
- R 2 , R 3 , R 4 , R 5 , R 7 and R 8 are hydrogen atoms and R 1 and R 6 are hydrogen atoms or methyl groups.
- the diamine (A1) is preferably a diamine represented by the following general formula (1′), more preferably the following formula ( It is at least one selected from the group consisting of diamines represented by 1-1) to (1-4).
- R 1 , R 2 , R 5 and R 6 each independently represent a hydrogen atom or a methyl group.
- the diamine (A1) is more preferably a diamine represented by the following formulas (1-1) to (1-3). At least one selected from the group.
- the diamine (A1) is preferably a group consisting of the diamine represented by the formula (1-2) and the diamine represented by the formula (1-3). is at least one selected from Further, from the viewpoint of forming a coating film having better weather resistance, the diamine (A1) is preferably selected from the group consisting of the diamine represented by the formula (1-1) and the diamine represented by the formula (1-2). At least one selected.
- the diamine (A1) represented by the general formula (1) can be produced by a known method.
- the diamine represented by the formula (1-1) (p-benzenediethanamine; pBDEA) can be obtained by reducing p-xylylenedicyanide under a hydrogen atmosphere.
- the diamine represented by the formula (1-2) (2-[4-(2-amino-1-methylethyl)phenyl]propylamine; pBDEA-2M) is the It can be manufactured according to the description.
- the diamine (m-benzenediethanamine; mBDEA) represented by the formula (1-3) is obtained by reducing m-xylylenedicyanide under a hydrogen atmosphere.
- the diamine represented by the formula (1-4) can be produced according to the description in Example 3 of Japanese Patent Publication No. 2004-503527.
- the polyamine (A) used in the curing agent of the present invention contains the diamine (A1) represented by the general formula (1).
- the content of the diamine (A1) in the polyamine (A) is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 5% by mass, from the viewpoint of forming a coating film having excellent transparency and weather resistance. % or more, still more preferably 10% by mass or more, still more preferably 15% by mass or more, still more preferably 20% by mass or more, still more preferably 30% by mass or more, still more preferably 40% by mass or more, still more preferably It is preferably 50% by mass or more and 100% by mass or less.
- the polyamine (A) can also contain polyamines other than the diamine (A1).
- Polyamines other than the diamine (A1) are not particularly limited as long as they are compounds having at least two amino groups in the molecule.
- xylylenediamine one or more selected from the group consisting of metaxylylenediamine and paraxylylenediamine is more preferable, and metaxylylenediamine is still more preferable.
- the polyamine (A) preferably contains xylylenediamine in addition to the diamine (A1), and more preferably contains one or more selected from the group consisting of meta-xylylenediamine and para-xylylenediamine. More preferably, it contains meta-xylylenediamine.
- the mass ratio of the diamine (A1) and the polyamine other than the diamine (A1) in the polyamine (A) is a coating film excellent in transparency and weather resistance. From the viewpoint of forming, preferably 1/99 to 99/1, more preferably 5/95 to 99/1, still more preferably 10/90 to 99/1, still more preferably 15/85 to 99/1 be.
- the diamine (A1) is the diamine represented by the formula (1-1) and the polyamine other than the diamine (A1) is xylylenediamine
- the diamine represented by the formula (1-1) and the xylylenediamine The mass ratio is more preferably 20/80 to 99/1, still more preferably 30/70 to 95/5, still more preferably from the viewpoint of forming a coating film excellent in transparency, weather resistance, and water resistance. is 40/60 to 90/10.
- the diamine (A1) is the diamine represented by the formula (1-2) and the polyamine other than the diamine (A1) is xylylenediamine
- the diamine represented by the formula (1-2) and the xylylenediamine The mass ratio is more preferably 20/80 to 99/1, still more preferably 30/70 to 99/1, from the viewpoint of forming a coating film excellent in transparency, weather resistance and water resistance.
- the diamine (A1) is the diamine represented by the formula (1-3) and the polyamine other than the diamine (A1) is xylylenediamine
- the diamine represented by the formula (1-3) and the xylylenediamine The mass ratio is more preferably 20/80 to 99/1 from the viewpoint of forming a coating film excellent in transparency, weather resistance and water resistance.
- a specific example of the adduct modified form of polyamine (A) is a reaction product obtained by reacting polyamine (A) with an epoxy compound having at least one epoxy group, an unsaturated hydrocarbon compound, a carboxylic acid or a derivative thereof, or the like.
- a Mannich reaction product obtained by reacting a polyamine (A) with a phenol compound and an aldehyde compound; a ketimine (ketimine) obtained by reacting a polyamine (A) with a ketone compound; and the like.
- the adduct modified form of polyamine (A) is preferably polyamine (A) and at least one epoxy from the viewpoint of forming a coating film having excellent transparency and weather resistance and from the viewpoint of improving water resistance.
- a reaction composition comprising a reactant with an epoxy compound having a group.
- the reaction composition containing a reaction product of polyamine (A) and an epoxy compound having at least one epoxy group means a product obtained by the reaction of polyamine (A) and the epoxy compound. and means a reaction composition containing a reactant (adduct) of the diamine and the epoxy compound.
- the reaction composition may contain unreacted raw materials and the like.
- the reaction composition is also simply referred to as "the reaction composition”.
- the epoxy compound used in the reaction composition may be a compound having at least one epoxy group, more preferably a compound having two or more epoxy groups.
- Specific examples of the epoxy compound include epichlorohydrin, butyl diglycidyl ether, neopentyl glycol diglycidyl ether, 1,3-propanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6- Polyfunctional epoxy resins having glycidylamino groups derived from hexanediol diglycidyl ether, biphenol diglycidyl ether, dihydroxynaphthalene diglycidyl ether, dihydroxyanthracene diglycidyl ether, triglycidyl isocyanurate, tetraglycidylglycoluril, metaxylylenediamine , 1,3-bis(aminomethyl)cyclohexane-derived polyfunctional epoxy resins having g
- the epoxy compound is more preferably a compound containing an aromatic ring or an alicyclic structure in the molecule.
- a compound containing an aromatic ring therein is more preferred, and a polyfunctional epoxy resin having a glycidyloxy group derived from bisphenol A is even more preferred.
- the reaction composition is obtained by subjecting polyamine (A) and an epoxy compound to a ring-opening addition reaction by a known method.
- a method in which the polyamine (A) is charged into a reactor, and the epoxy compound is added all at once or added dropwise or the like in portions and heated to react.
- the addition reaction is preferably carried out under an inert atmosphere such as nitrogen gas.
- the amount of polyamine (A) and epoxy compound used is not particularly limited as long as the ratio is such that the resulting reactant contains an amino group having an active hydrogen.
- the number of active hydrogens in the polyamine (A) with respect to the number of epoxy groups in the epoxy compound is preferably 50/1 to 4/1. , more preferably 20/1 to 4/1, the polyamine (A) and the epoxy compound are used.
- the temperature and reaction time during the addition reaction can be appropriately selected, but from the viewpoints of reaction rate and productivity, and prevention of decomposition of the raw materials, etc., the temperature during the addition reaction is preferably 50 to 150° C., more preferably 70 to 70° C. 120°C.
- the reaction time is preferably 0.5 to 12 hours, more preferably 1 to 6 hours, after the addition of the epoxy compound is completed.
- the curing agent of the present invention may be a curing agent comprising polyamine (A) or an adduct modified product thereof, and may contain other curing agent components.
- Other curing agent components include curing agent components other than polyamines and their adduct modified products, such as phenolic curing agents.
- the total content of polyamine (A) and its adduct modified product in all curing agent components contained in the curing agent of the present invention is preferably 50 from the viewpoint of forming a coating film excellent in transparency and weather resistance. % by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 95% by mass or more. , and 100% by mass or less.
- the curing agent of the present invention preferably contains an adduct modified form of polyamine (A) from the viewpoint of curability and obtaining good coating film properties, and polyamine (A) and at least one epoxy group It is more preferred to contain a reaction composition comprising a reactant with an epoxy compound having When the curing agent of the present invention contains the above reaction composition as an adduct modified polyamine (A), the content of the reaction composition in the curing agent of the present invention is such that a coating film having excellent transparency and weather resistance can be obtained.
- the curing agent component in the curing agent means a component contained in the curing agent that has two or more active hydrogens capable of reacting with the epoxy groups in the epoxy resin.
- the mass % of the composition refers to the content of the reaction composition relative to the total amount of curable components contained in the curing agent.
- the curing agent of the present invention may further contain a known curing accelerator, a non-reactive diluent such as benzyl alcohol, etc., as long as the effects of the present invention are not impaired.
- the active hydrogen equivalent of the curing agent component in the curing agent of the present invention depends on the component contained in the curing agent, but from the viewpoint of obtaining good coating film properties, it is preferably 40 or more to improve curability. From the viewpoint of, it is preferably 150 or less.
- the active hydrogen equivalent (hereinafter also referred to as "AHEW”) is the mass per mole of active hydrogen in the epoxy resin curing agent.
- Epoxy resin composition contains an epoxy resin and the epoxy resin curing agent.
- a coating film formed from the epoxy resin composition of the present invention has high transparency and weather resistance, and is suitable for use as a paint, for example.
- the epoxy resin which is the main ingredient of the epoxy resin composition, may be any of saturated or unsaturated aliphatic compounds, alicyclic compounds, aromatic compounds, and heterocyclic compounds. From the viewpoint of obtaining a cured product with high water resistance, an epoxy resin containing an aromatic ring or an alicyclic structure in the molecule is preferable.
- Specific examples of the epoxy resin include an epoxy resin having a glycidylamino group derived from metaxylylenediamine, an epoxy resin having a glycidylamino group derived from paraxylylenediamine, and 1,3-bis(aminomethyl).
- the above epoxy resins can be used in combination of two or more.
- epoxy resins having glycidylamino groups derived from metaxylylenediamine epoxy resins having glycidylamino groups derived from paraxylylenediamine, epoxy resins having glycidylamino groups derived from metaxylylenediamine,
- An epoxy resin having a glycidyloxy group derived from bisphenol A and an epoxy resin having a glycidyloxy group derived from bisphenol F is preferable as a main component, and a good coating film is preferable.
- the term "main component" as used herein means that other components may be included within the scope of the present invention, preferably 50 to 100% by mass, more preferably 70 to 100% by mass of the total. , more preferably 90 to 100% by mass.
- the content of the epoxy resin curing agent in the epoxy resin composition of the present invention is the ratio of the number of active hydrogens in the epoxy resin curing agent to the number of epoxy groups in the epoxy resin (number of active hydrogens in the epoxy resin curing agent/epoxy number of epoxy groups in the resin) is preferably 1/0.5 to 1/2, more preferably 1/0.75 to 1/1.5, still more preferably 1/0.8 to 1/1.2. is the amount.
- the epoxy resin composition of the present invention may further contain other components such as fillers, modifying components such as plasticizers, flow control components such as thixotropic agents, pigments, leveling agents, tackifiers, and elastomer fine particles. may be included depending on However, from the viewpoint of effectively obtaining the effects of the present invention, the total amount of the epoxy resin and the epoxy resin curing agent in the epoxy resin composition is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass. % by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and 100% by mass or less.
- the method of preparing the epoxy resin composition of the present invention is not particularly limited, and the epoxy resin, epoxy resin curing agent, and if necessary, other components can be mixed using a known method and apparatus for production.
- the mixing order of each component contained in the epoxy resin composition is not particularly limited, and after the epoxy resin curing agent is prepared, it may be mixed with the epoxy resin. And other components and epoxy resin may be mixed at the same time to prepare.
- a coating film, which is a cured product of the epoxy resin composition of the present invention is obtained by curing the above-described epoxy resin composition of the present invention by a known method. Curing conditions for the epoxy resin composition are appropriately selected according to the application and form, and are not particularly limited.
- the coating film, which is the cured product of the epoxy resin composition of the present invention has excellent transparency and weather resistance, is resistant to whitening, and suppresses yellowing over time after the coating film is formed. can be done.
- the present invention provides a paint containing the epoxy resin composition.
- the paint of the present invention has good transparency and weather resistance of the resulting coating film.
- examples of such paints include marine paints, heavy-duty anticorrosive paints, tank paints, pipe interior paints, exterior paints, and flooring paints.
- the content of the epoxy resin composition in the paint of the present invention is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, from the viewpoint of improving transparency and weather resistance. It is preferably 90% by mass or more, more preferably 95% by mass or more, and may be 100% by mass.
- the present invention will be described in detail below with examples and comparative examples, but the present invention is not limited to the following examples.
- the epoxy resin curing agent, the epoxy resin composition, and the cured products thereof were evaluated according to the following methods.
- ⁇ Dry touch> The epoxy resin composition was applied onto a substrate (zinc phosphate-treated steel plate) in the same manner as described above to form a coating film (thickness immediately after application: 200 ⁇ m). This coating film was heated at 23° C. and 50% R.I. H. After 1, 2 and 7 days, the samples were evaluated by finger touch according to the following criteria. Table 1 shows the results.
- ⁇ Pencil hardness> The epoxy resin composition was applied onto a substrate (zinc phosphate-treated steel plate) in the same manner as described above to form a coating film (thickness immediately after application: 200 ⁇ m). This coating film was heated at 23° C. and 50% R.I. H. After 1, 2 and 7 days, the pencil hardness was measured according to JIS K5600-5-4:1999. Table 1 shows the results.
- ⁇ YI> A weather resistance test was performed according to the ISO4982 Part 3 Method A standard.
- the epoxy resin composition obtained in each example was placed in a mold of 20 mm ⁇ 20 mm ⁇ thickness 2 mm at 23° C. and 50% R.I. H.
- a test piece was prepared by curing in an environment for 7 days.
- the YI value of this test piece was measured in accordance with JIS K7373:2006 using a color difference meter (“COH400” manufactured by Nippon Denshoku Industries Co., Ltd.).
- test piece was placed in a UV tester "Suntest XXL+" (manufactured by Toyo Seiki Seisakusho Co., Ltd.) and irradiated with ultraviolet rays having a wavelength of 300 to 400 nm from a xenon lamp at a temperature of 38 ° C. and an intensity of illuminance of 60 W / m 2 . .
- UV irradiation amount reached 30,000 (kJ/m 2 )
- the test piece was taken out and the YI value was measured in the same manner as described above.
- the difference between the YI values before and after the weather resistance test was defined as the ⁇ YI value.
- Tables 1-4 A smaller ⁇ YI value indicates better weather resistance of the cured product.
- Example 1 (Preparation and Evaluation of Epoxy Resin Curing Agent and Epoxy Resin Composition) [Preparation of epoxy resin curing agent] 41.3 g of pBDEA obtained in Production Example 1 was charged into a 1-liter separable flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, a dropping funnel, and a cooling tube, and stirred for 80 minutes under a nitrogen stream. °C.
- Epoxy Resin Composition As the epoxy resin which is the main ingredient of the epoxy resin composition, a polyfunctional epoxy resin having a glycidyloxy group derived from bisphenol A ("jER828" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 186 g/equivalent) was used.
- the ratio of the number of active hydrogens in the curing agent to the number of epoxy groups in the epoxy resin (number of active hydrogens in the curing agent/number of epoxy groups in the epoxy resin) is 1/1. were blended and mixed to prepare an epoxy resin composition. Using the obtained epoxy resin composition, various evaluations were performed by the methods described above. Table 1 shows the results.
- Example 2 In "Preparation of epoxy resin curing agent" of Example 1, 43.3 g of pBDEA-2M and 16.7 g of jER828 obtained in Production Example 2 were used instead of 41.3 g of pBDEA and 18.7 g of jER828. An epoxy resin curing agent was obtained in the same manner as in Example 1, except for the above. Using the epoxy resin curing agent, an epoxy resin composition was prepared in the same manner as in Example 1, and the above evaluation was performed. Table 1 shows the results.
- Example 3 An epoxy resin curing agent was obtained in the same manner as in Example 1, except that 41.3 g of mBDEA obtained in Production Example 3 was used instead of 41.3 g of pBDEA. Using the epoxy resin curing agent, an epoxy resin composition was prepared in the same manner as in Example 1, and the above evaluation was performed. Table 1 shows the results.
- Epoxy resin curing agent was prepared in the same manner as in Example 1, except that 38.8 g of metaxylylenediamine (MXDA, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used instead of 41.3 g of pBDEA in Example 1. got Using the epoxy resin curing agent, an epoxy resin composition was prepared in the same manner as in Example 1, and the above evaluation was performed. Table 1 shows the results.
- MXDA metaxylylenediamine
- Example 4 In Example 1, the epoxy A resin curing agent was obtained. Using the epoxy resin curing agent, an epoxy resin composition was prepared in the same manner as in Example 1, and the above evaluation was performed. Table 2 shows the results.
- Example 5 An epoxy resin curing agent was obtained in the same manner as in Example 4, except that pBDEA was changed to 3.9 g, MXDA to 35.2 g, and jER828 to 21.0 g. Using the epoxy resin curing agent, an epoxy resin composition was prepared in the same manner as in Example 4, and the above evaluation was performed. Table 2 shows the results.
- Example 6 An epoxy resin curing agent was obtained in the same manner as in Example 4, except that pBDEA was changed to 5.9 g, MXDA to 33.3 g, and jER828 to 20.8 g. Using the epoxy resin curing agent, an epoxy resin composition was prepared in the same manner as in Example 4, and the above evaluation was performed. Table 2 shows the results.
- Example 7 An epoxy resin curing agent was obtained in the same manner as in Example 4, except that pBDEA was changed to 7.86 g, MXDA to 31.44 g, and jER828 to 20.7 g. Using the epoxy resin curing agent, an epoxy resin composition was prepared in the same manner as in Example 4, and the above evaluation was performed. Table 2 shows the results.
- Example 8 An epoxy resin curing agent was obtained in the same manner as in Example 4, except that pBDEA was changed to 20.05 g, MXDA to 20.05 g, and jER828 to 19.9 g. Using the epoxy resin curing agent, an epoxy resin composition was prepared in the same manner as in Example 4, and the above evaluation was performed. Table 2 shows the results.
- Example 9 Same as Example 2, except that 7.94 g of pBDEA-2M, 31.76 g of MXDA, and 20.3 g of jER828 were used instead of 43.3 g of pBDEA-2M and 16.7 g of jER828 in Example 2.
- An epoxy resin curing agent was obtained by the method of Using the epoxy resin curing agent, an epoxy resin composition was prepared in the same manner as in Example 2, and the above evaluation was performed. Table 3 shows the results.
- Example 10 An epoxy resin curing agent was obtained in the same manner as in Example 9, except that pBDEA-2M was changed to 20.5 g, MXDA to 20.5 g, and jER828 to 19.0 g. Using the epoxy resin curing agent, an epoxy resin composition was prepared in the same manner as in Example 9, and the above evaluation was performed. Table 3 shows the results.
- Example 11 Epoxy was prepared in the same manner as in Example 3, except that 7.86 g of mBDEA, 31.44 g of MXDA, and 20.7 g of jER828 were used in place of 41.3 g of mBDEA and 18.7 g of jER828. A resin curing agent was obtained. Using the epoxy resin curing agent, an epoxy resin composition was prepared in the same manner as in Example 3, and the above evaluation was performed. Table 4 shows the results.
- Example 12 An epoxy resin curing agent was obtained in the same manner as in Example 11, except that mBDEA was changed to 20.05 g, MXDA to 20.05 g, and jER828 to 19.9 g. Using the epoxy resin curing agent, an epoxy resin composition was prepared in the same manner as in Example 11, and the above evaluation was performed. Table 4 shows the results.
- an epoxy resin curing agent an epoxy resin composition
- a paint containing these that can form a coating film with excellent transparency and weather resistance.
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Abstract
Description
例えば特許文献1には、所定の変性エポキシ樹脂とアミン系硬化剤とを必須成分とするエポキシ樹脂組成物が、低粘度で低温硬化性に優れ、かつ機械強度、耐湿性及び接着性等の硬化物性にも優れており、特に土木、塗料、接着用途に好適であることが開示されている。該アミン系硬化剤としては、メタキシリレンジアミンのマンニッヒ反応変性物を主成分とするものが例示されている。
すなわち本発明は、下記に関する。
[1]下記一般式(1)で示されるジアミン(A1)を含むポリアミン(A)又は該ポリアミン(A)のアダクト変性体を含有するエポキシ樹脂硬化剤。
(式(1)中、R1~R8はそれぞれ独立に、水素原子又は炭素数1~5の脂肪族基を表す。)
[2]前記アダクト変性体が、前記ポリアミン(A)と、少なくとも1つのエポキシ基を有するエポキシ化合物との反応物を含む反応組成物である、上記[1]に記載のエポキシ樹脂硬化剤。
[3]前記ジアミン(A1)が下記式(1-1)~(1-3)で示されるジアミンからなる群から選ばれる少なくとも1種である、上記[1]又は[2]に記載のエポキシ樹脂硬化剤。
[4]前記ポリアミン(A)中の前記ジアミン(A1)の含有量が5質量%以上である、上記[1]~[3]のいずれか1項に記載のエポキシ樹脂硬化剤。
[5]前記ポリアミン(A)がさらにキシリレンジアミンを含有する、上記[1]~[4]のいずれか1項に記載のエポキシ樹脂硬化剤。
[6]前記エポキシ樹脂硬化剤に含まれる全硬化剤成分中の、前記ポリアミン(A)及びそのアダクト変性体の合計含有量が50質量%以上である、上記[1]~[5]のいずれか1項に記載のエポキシ樹脂硬化剤。
[7]エポキシ樹脂と、上記[1]~[6]のいずれか1項に記載のエポキシ樹脂硬化剤とを含有するエポキシ樹脂組成物。
[8]上記[7]に記載のエポキシ樹脂組成物を含有する塗料。
本発明のエポキシ樹脂硬化剤は、下記一般式(1)で示されるジアミン(A1)を含むポリアミン(A)又は該ポリアミン(A)のアダクト変性体を含有するエポキシ樹脂硬化剤である。すなわち該硬化剤は、前記ポリアミン(A)及び前記ポリアミン(A)のアダクト変性体からなる群から選ばれる少なくとも1種を含有する。
(式(1)中、R1~R8はそれぞれ独立に、水素原子又は炭素数1~5の脂肪族基を表す。)
上記エポキシ樹脂硬化剤を用いることにより、透明性及び耐候性に優れる塗膜を形成できるエポキシ樹脂組成物を提供することができる。以下、本発明のエポキシ樹脂硬化剤を単に「本発明の硬化剤」ともいう。
前記の通り、キシリレンジアミンは空気中の二酸化炭素との作用により炭酸塩を形成して白化しやすく、また芳香環を有することから経時で黄変しやすいという問題があった。さらにキシリレンジアミンに関しては、ベンジル骨格を有するためにベンジル位の水素原子が引き抜かれやすく、これに起因する耐候性低下も生じていると考えられる。
これに対し前記一般式(1)で示されるジアミン(A1)は、キシリレンジアミンと比較して水素原子の引き抜きが起こり難いため安定であり、且つ二酸化炭素と接触しても白化し難い。そのため、ジアミン(A1)を用いた本発明のエポキシ樹脂硬化剤を含有するエポキシ樹脂組成物は、形成される塗膜の透明性及び耐候性が良好になると考えられる。
ジアミン(A1)は、下記一般式(1)で示されるジアミンである。
(式(1)中、R1~R8はそれぞれ独立に、水素原子又は炭素数1~5の脂肪族基を表す。)
前記一般式(1)のR1~R8における、炭素数1~5の脂肪族基としては、炭素数1~5のアルキル基、炭素数2~5のアルケニル基又はアルキニル基が例示される。透明性及び耐候性に優れる塗膜を形成する観点からは、該脂肪族基は炭素数1~5のアルキル基であることが好ましい。該アルキル基としては、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、i-ブチル基、sec-ブチル基、t-ブチル基、n-ペンチル基、i-ペンチル基等が挙げられる。これらの中でも、透明性及び耐候性に優れる塗膜を形成する観点からは、炭素数1~3のアルキル基が好ましく、メチル基又はエチル基がより好ましく、メチル基が更に好ましい。
より好ましい態様は、前記一般式(1)において、R3、R4、R7、及びR8が水素原子で且つR1、R2、R5、及びR6が水素原子又はメチル基であり、更に好ましい態様は、R2、R3、R4、R5、R7、及びR8が水素原子で且つR1及びR6が水素原子又はメチル基である。
(式(1’)中、R1、R2、R5、及びR6はそれぞれ独立に、水素原子又はメチル基を表す。)
例えば前記式(1-1)で示されるジアミン(p-ベンゼンジエタンアミン;pBDEA)は、p-キシリレンジシアニドを水素雰囲気下で還元することにより得られる。前記式(1-2)で示されるジアミン(2-[4-(2-アミノ-1-メチルエチル)フェニル]プロピルアミン;pBDEA-2M)は、特表2004-503527号公報の実施例1の記載に従って製造することができる。
前記式(1-3)で示されるジアミン(m-ベンゼンジエタンアミン;mBDEA)は、m-キシリレンジシアニドを水素雰囲気下で還元することにより得られる。また、前記式(1-4)で示されるジアミンは、特表2004-503527号公報の実施例3の記載に従って製造することができる。
本発明の硬化剤に用いるポリアミン(A)は、前記一般式(1)で示されるジアミン(A1)を含むものである。ポリアミン(A)中のジアミン(A1)の含有量は、透明性及び耐候性に優れる塗膜を形成する観点から、好ましくは1質量%以上、より好ましくは2質量%以上、更に好ましくは5質量%以上、より更に好ましくは10質量%以上、より更に好ましくは15質量%以上、より更に好ましくは20質量%以上、より更に好ましくは30質量%以上、より更に好ましくは40質量%以上、より更に好ましくは50質量%以上であり、また、100質量%以下である。
上記の中でも、ポリアミン(A)又はそのアダクト変性体を含むことにより、得られる塗膜の透明性及び耐候性の改善効果を得るという観点、並びに、硬化性及び良好な塗膜物性を得る観点から、ジアミン(A1)以外のポリアミンとしてはキシリレンジアミンが好ましく、メタキシリレンジアミン及びパラキシリレンジアミンからなる群から選ばれる1種以上がより好ましく、メタキシリレンジアミンが更に好ましい。すなわちポリアミン(A)は、前記ジアミン(A1)以外に、さらにキシリレンジアミンを含有することが好ましく、メタキシリレンジアミン及びパラキシリレンジアミンからなる群から選ばれる1種以上を含有することがより好ましく、メタキシリレンジアミンを含有することが更に好ましい。
ジアミン(A1)が前記式(1-1)で示されるジアミンであり、ジアミン(A1)以外のポリアミンがキシリレンジアミンである場合、式(1-1)で示されるジアミンとキシリレンジアミンとの質量比は、透明性、耐候性、及び耐水性に優れる塗膜を形成する観点から、より更に好ましくは20/80~99/1、より更に好ましくは30/70~95/5、より更に好ましくは40/60~90/10である。
ジアミン(A1)が前記式(1-2)で示されるジアミンであり、ジアミン(A1)以外のポリアミンがキシリレンジアミンである場合、式(1-2)で示されるジアミンとキシリレンジアミンとの質量比は、透明性、耐候性、及び耐水性に優れる塗膜を形成する観点から、より更に好ましくは20/80~99/1、より更に好ましくは30/70~99/1である。
ジアミン(A1)が前記式(1-3)で示されるジアミンであり、ジアミン(A1)以外のポリアミンがキシリレンジアミンである場合、式(1-3)で示されるジアミンとキシリレンジアミンとの質量比は、透明性、耐候性、及び耐水性に優れる塗膜を形成する観点から、より更に好ましくは20/80~99/1である。
ポリアミン(A)のアダクト変性体の具体例としては、ポリアミン(A)と、少なくとも1つのエポキシ基を有するエポキシ化合物、不飽和炭化水素化合物、カルボン酸又はその誘導体等とを反応させた反応生成物;ポリアミン(A)と、フェノール化合物及びアルデヒド化合物とを反応させたマンニッヒ反応物;ポリアミン(A)と、ケトン化合物とを反応させたケトイミン(ケチミン);等が挙げられる。
これらの中でも、ポリアミン(A)のアダクト変性体としては、透明性及び耐候性に優れる塗膜を形成する観点、及び耐水性向上の観点から、好ましくは、ポリアミン(A)と、少なくとも1つのエポキシ基を有するエポキシ化合物との反応物を含む反応組成物である。なお、本明細書において、ポリアミン(A)と、少なくとも1つのエポキシ基を有するエポキシ化合物との反応物を含む反応組成物とは、ポリアミン(A)と該エポキシ化合物との反応により得られる生成物であって、該ジアミンと該エポキシ化合物との反応物(アダクト)を含む反応組成物を意味する。該反応組成物は未反応原料等を含んでいてもよい。以下、該反応組成物を単に「前記反応組成物」ともいう。
該エポキシ化合物の具体例としては、エピクロロヒドリン、ブチルジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、1,3-プロパンジオールジグリシジルエーテル、1,4-ブタンジオールジグリシジルエーテル、1,6-ヘキサンジオールジグリシジルエーテル、ビフェノールジグリシジルエーテル、ジヒドロキシナフタレンジグリシジルエーテル、ジヒドロキシアントラセンジグリシジルエーテル、トリグリシジルイソシアヌレート、テトラグリシジルグリコールウリル、メタキシリレンジアミンから誘導されたグリシジルアミノ基を有する多官能エポキシ樹脂、1,3-ビス(アミノメチル)シクロヘキサンから誘導されたグリシジルアミノ基を有する多官能エポキシ樹脂、ジアミノジフェニルメタンから誘導されたグリシジルアミノ基を有する多官能エポキシ樹脂、パラアミノフェノールから誘導されたグリシジルアミノ基及び/又はグリシジルオキシ基を有する多官能エポキシ樹脂、ビスフェノールAから誘導されたグリシジルオキシ基を有する多官能エポキシ樹脂、ビスフェノールFから誘導されたグリシジルオキシ基を有する多官能エポキシ樹脂、フェノールノボラックから誘導されたグリシジルオキシ基を有する多官能エポキシ樹脂、及びレゾルシノールから誘導されたグリシジルオキシ基を2つ以上有する多官能エポキシ樹脂等が挙げられる。これらは1種を単独で、又は2種以上を組み合わせて用いることができる。
透明性及び耐候性に優れる塗膜を形成する観点、耐水性向上の観点、並びに硬化性の観点からは、エポキシ化合物としては分子中に芳香環又は脂環式構造を含む化合物がより好ましく、分子中に芳香環を含む化合物が更に好ましく、ビスフェノールAから誘導されたグリシジルオキシ基を有する多官能エポキシ樹脂がより更に好ましい。
但し、本発明の硬化剤に含まれる全硬化剤成分中の、ポリアミン(A)及びそのアダクト変性体の合計含有量は、透明性及び耐候性に優れる塗膜を形成する観点から、好ましくは50質量%以上であり、より好ましくは60質量%以上、更に好ましくは70質量%以上、より更に好ましくは80質量%以上、より更に好ましくは90質量%以上、より更に好ましくは95質量%以上であり、また、100質量%以下である。
硬化剤中の硬化剤成分とは、硬化剤中に含まれる、エポキシ樹脂中のエポキシ基と反応し得る活性水素を2つ以上有する成分を意味し、硬化剤中の全硬化剤成分に対する前記反応組成物の質量%とは、硬化剤中に含まれる硬化性成分の総量に対する前記反応組成物の含有割合をいう。
本発明のエポキシ樹脂組成物は、エポキシ樹脂と、前記エポキシ樹脂硬化剤とを含有する。本発明のエポキシ樹脂組成物により形成される塗膜は透明性及び耐候性が高く、例えば塗料として好適に用いられる。
エポキシ樹脂組成物の主剤であるエポキシ樹脂は、飽和又は不飽和の脂肪族化合物や脂環式化合物、芳香族化合物、複素環式化合物のいずれであってもよい。耐水性の高い硬化物を得る観点からは、芳香環又は脂環式構造を分子内に含むエポキシ樹脂が好ましい。
当該エポキシ樹脂の具体例としては、メタキシリレンジアミンから誘導されたグリシジルアミノ基を有するエポキシ樹脂、パラキシリレンジアミンから誘導されたグリシジルアミノ基を有するエポキシ樹脂、1,3-ビス(アミノメチル)シクロヘキサンから誘導されたグリシジルアミノ基を有するエポキシ樹脂、1,4-ビス(アミノメチル)シクロヘキサンから誘導されたグリシジルアミノ基を有するエポキシ樹脂、ジアミノジフェニルメタンから誘導されたグリシジルアミノ基を有するエポキシ樹脂、パラアミノフェノールから誘導されたグリシジルアミノ基及び/又はグリシジルオキシ基を有するエポキシ樹脂、ビスフェノールAから誘導されたグリシジルオキシ基を有するエポキシ樹脂、ビスフェノールFから誘導されたグリシジルオキシ基を有するエポキシ樹脂、フェノールノボラックから誘導されたグリシジルオキシ基を有するエポキシ樹脂及びレゾルシノールから誘導されたグリシジルオキシ基を有するエポキシ樹脂から選ばれる少なくとも1種の樹脂が挙げられる。上記のエポキシ樹脂は、2種以上混合して用いることもできる。
なお、ここでいう「主成分」とは、本発明の趣旨を逸脱しない範囲で他の成分を含みうることを意味し、好ましくは全体の50~100質量%、より好ましくは70~100質量%、さらに好ましくは90~100質量%を意味する。
但し、本発明の効果を有効に得る観点から、エポキシ樹脂組成物中のエポキシ樹脂及びエポキシ樹脂硬化剤の合計量は、好ましくは50質量%以上、より好ましくは70質量%以上、さらに好ましくは80質量%以上、よりさらに好ましくは90質量%以上、よりさらに好ましくは95質量%以上であり、また、100質量%以下である。
本発明のエポキシ樹脂組成物の硬化物である塗膜は、透明性及び耐候性に優れるものとなり、塗膜の白化が生じにくく、且つ塗膜形成後、経時での黄変発生を抑制することができる。
本発明は、前記エポキシ樹脂組成物を含有する塗料を提供する。本発明の塗料は、前記エポキシ樹脂組成物を含有することにより、得られる塗膜の透明性及び耐候性が良好になる。当該塗料としては、例えば、船舶塗料、重防食塗料、タンク用塗料、パイプ内装用塗料、外装用塗料、床材用塗料等が挙げられる。
ガラス板(太佑機材(株)製 25×348×2.0mm)上に、23℃、50%R.H.条件下、各例のエポキシ樹脂組成物を76μmのアプリケーターを用いて塗布し、塗膜を形成した。塗膜を形成したガラス板を塗料乾燥時間測定器(太佑機材(株)製)にセットし、測定器の針が塗膜表面を引っかいた際の条痕を観察して、各乾燥段階(指触乾燥、半乾燥、完全乾燥)への到達時間を以下の基準で測定した。結果を表1~4に示す。時間が短い方が、硬化速度が速いことを示す。
指触乾燥(Set to Touch):ガラス板上に針の跡が残り始める時間
半乾燥(Dust Free):針の跡が塗膜の中から塗膜表面上に浮き出てくる時間
完全乾燥(Dry through):塗膜上に針の跡が残らなくなる時間
基材としてリン酸亜鉛処理鋼板(パルテック(株)製;SPCC-SD PB-N144 0.8×70×150mm)を用いた。23℃、50%R.H.条件下で、基材上に各例のエポキシ樹脂組成物をアプリケーターを用いて塗布し、塗膜を形成した(塗布直後の塗膜厚み:200μm)。この塗膜を23℃、50%R.H.条件下で保存し、1日経過後の外観を目視観察して、透明性を以下の基準で評価した。結果を表1~4に示す。
(透明性)
Ex:濁りがない
G:わずかに濁りがあるが、使用上問題ない
F:白濁している
前記と同様の方法で基材(リン酸亜鉛処理鋼板)上にエポキシ樹脂組成物を塗布して塗膜を形成した(塗布直後の厚み:200μm)。この塗膜を23℃、50%R.H.条件下で保存し、1、2、7日経過後に指触により以下の基準で評価した。結果を表1に示す。
Ex:優秀(約50Nの力で親指を押し付けた際も塗膜のべたつきがなく、指紋の残存もなし)
G:良好(約50Nの力で親指を押し付けた際に塗膜のべたつきはないが、指触後の指紋の残存あり)
F:可(約50Nの力で親指を押し付けた際に塗膜のべたつきあり)
P:不良(約5Nの力で親指を押し付けた際に塗膜のべたつきあり)
前記と同様の方法で基材(リン酸亜鉛処理鋼板)上にエポキシ樹脂組成物を塗布して塗膜を形成した(塗布直後の厚み:200μm)。この塗膜を23℃、50%R.H.条件下で保存し、1、2、7日経過後にJIS K5600-5-4:1999に準拠して鉛筆硬度を測定した。結果を表1に示す。
前記と同様の方法で基材(リン酸亜鉛処理鋼板)上にエポキシ樹脂組成物を塗布して塗膜を形成した(塗布直後の厚み:200μm)。この塗膜を23℃、50%R.H.条件下で保存し、1、2、7日経過後に塗膜表面にスポイトで純水を2~3滴滴下し、その箇所を50mLスクリュー管瓶で蓋をした。24時間経過後に水を拭き取り、外観を目視観察して、以下の基準で評価した。結果を表1~4に示す。
Ex:変化なし
G:わずかに変化はあるが、良好
F:変化あり
ISO4982 Part 3 Method A規格に準拠して耐候性試験を行った。
各例で得られたエポキシ樹脂組成物を、20mm×20mm×厚さ2mmの金型内で、23℃、50%R.H.環境下で7日間硬化させて試験片を作製した。この試験片について色差計(日本電色工業(株)製「COH400」)を用いて、JIS K7373:2006に準拠してYI値を測定した。次いで、試験片をUV試験機「サンテストXXL+」((株)東洋精機製作所製)に入れ、温度38℃で、キセノンランプにより波長300~400nmの紫外線を照度60W/m2の強度で照射した。UV照射量が30,000(kJ/m2)に到達した後に試験片を取り出し、前記と同様にYI値を測定した。また、耐候性試験前後のYI値の差分をΔYI値とした。結果を表1~4に示す。ΔYI値が小さいほど硬化物の耐候性が良好であることを示す。
p-キシリレンジシアニド(東京化成工業(株)製)を水素雰囲気下で還元し、得られた生成物を蒸留精製して、下記式(1-1)で示されるp-ベンゼンジエタンアミン(pBDEA)を得た。ガスクロマトグラフィーを用いて分析した結果、純度は99.7%であった。
特表2004-503527号公報の実施例1の記載に従い、2-[4-(2-アミノ-1-メチルエチル)フェニル]プロピルアミン・二塩酸塩を得た。該塩酸塩を中和した後に溶剤抽出し、得られた抽出物を蒸留精製して、式(1-2)で示される化合物である2-[4-(2-アミノ-1-メチルエチル)フェニル]プロピルアミン(pBDEA-2M)を得た。ガスクロマトグラフィーを用いて分析した結果、純度は94.6%であった。また、希塩酸を用いて中和滴定によって分析した結果、アミノ基の濃度は10.35mmol/gであった。
m-キシリレンジシアニド(東京化成工業(株)製)を水素雰囲気下で還元し、得られた生成物を蒸留精製して、下記式(1-3)で示されるm-ベンゼンジエタンアミン(mBDEA)を得られた。ガスクロマトグラフィーを用いて分析した結果、純度は99.6%であった。
〔エポキシ樹脂硬化剤の調製〕
攪拌装置、温度計、窒素導入管、滴下漏斗及び冷却管を備えた内容積1リットルのセパラブルフラスコに、製造例1で得られたpBDEA 41.3gを仕込み、窒素気流下、攪拌しながら80℃に昇温した。80℃に保ちながら、エポキシ化合物として、ビスフェノールAから誘導されたグリシジルオキシ基を有する多官能エポキシ樹脂(三菱ケミカル(株)製「jER828」、エポキシ当量:186g/当量)18.7g(アミン中の活性水素数/エポキシ化合物中のエポキシ基数=10/1となる量)を2時間かけて滴下した。滴下終了後、100℃に昇温して2時間反応を行い、pBDEAとjER828との反応物を含む反応組成物を得た。ここに非反応性希釈剤であるベンジルアルコールを全体量の40質量%となる量を添加して希釈し、前記反応組成物の濃度が60質量%のエポキシ樹脂硬化剤を得た。エポキシ樹脂硬化剤(ベンジルアルコールを含む全量)の活性水素当量(AHEW)は110.3であった。
〔エポキシ樹脂組成物の調製、評価〕
エポキシ樹脂組成物の主剤であるエポキシ樹脂として、ビスフェノールAから誘導されたグリシジルオキシ基を有する多官能エポキシ樹脂(三菱ケミカル(株)製「jER828」、エポキシ当量186g/当量)を使用した。該エポキシ樹脂と前記エポキシ樹脂硬化剤とを、エポキシ樹脂中のエポキシ基数に対する硬化剤中の活性水素数の比(硬化剤中の活性水素数/エポキシ樹脂中のエポキシ基数)が1/1となるよう配合して混合し、エポキシ樹脂組成物を調製した。
得られたエポキシ樹脂組成物を用いて、前述の方法で各種評価を行った。結果を表1に示す。
実施例1の「エポキシ樹脂硬化剤の調製」において、pBDEA 41.3g、及びjER828 18.7gに替えて、製造例2で得られたpBDEA-2Mを43.3g、jER828を16.7g用いたこと以外は、実施例1と同様の方法でエポキシ樹脂硬化剤を得た。該エポキシ樹脂硬化剤を用いて、実施例1と同様の方法でエポキシ樹脂組成物を調製し、前記評価を行った。結果を表1に示す。
実施例1において、pBDEA 41.3gに替えて、製造例3で得られたmBDEAを41.3g用いたこと以外は、実施例1と同様の方法でエポキシ樹脂硬化剤を得た。該エポキシ樹脂硬化剤を用いて、実施例1と同様の方法でエポキシ樹脂組成物を調製し、前記評価を行った。結果を表1に示す。
実施例1において、pBDEA 41.3gに替えて、メタキシリレンジアミン(MXDA、三菱瓦斯化学(株)製)を38.8g用いたこと以外は、実施例1と同様の方法でエポキシ樹脂硬化剤を得た。該エポキシ樹脂硬化剤を用いて、実施例1と同様の方法でエポキシ樹脂組成物を調製し、前記評価を行った。結果を表1に示す。
実施例1において、pBDEA 41.3g、及びjER828 18.7gに替えて、pBDEA 2.0g、MXDA 37.0g、及びjER828 21.1gを用いたこと以外は、実施例1と同様の方法でエポキシ樹脂硬化剤を得た。該エポキシ樹脂硬化剤を用いて、実施例1と同様の方法でエポキシ樹脂組成物を調製し、前記評価を行った。結果を表2に示す。
実施例4において、pBDEAを3.9g、MXDAを35.2g、jER828を21.0gに変更したこと以外は、実施例4と同様の方法でエポキシ樹脂硬化剤を得た。該エポキシ樹脂硬化剤を用いて、実施例4と同様の方法でエポキシ樹脂組成物を調製し、前記評価を行った。結果を表2に示す。
実施例4において、pBDEAを5.9g、MXDAを33.3g、jER828を20.8gに変更したこと以外は、実施例4と同様の方法でエポキシ樹脂硬化剤を得た。該エポキシ樹脂硬化剤を用いて、実施例4と同様の方法でエポキシ樹脂組成物を調製し、前記評価を行った。結果を表2に示す。
実施例4において、pBDEAを7.86g、MXDAを31.44g、及びjER828を20.7gに変更したこと以外は、実施例4と同様の方法でエポキシ樹脂硬化剤を得た。該エポキシ樹脂硬化剤を用いて、実施例4と同様の方法でエポキシ樹脂組成物を調製し、前記評価を行った。結果を表2に示す。
実施例4において、pBDEAを20.05g、MXDAを20.05g、jER828を19.9gに変更したこと以外は、実施例4と同様の方法でエポキシ樹脂硬化剤を得た。該エポキシ樹脂硬化剤を用いて、実施例4と同様の方法でエポキシ樹脂組成物を調製し、前記評価を行った。結果を表2に示す。
実施例2において、pBDEA-2M 43.3g、及びjER828 16.7gに替えて、pBDEA-2M 7.94g、MXDA 31.76g、及びjER828 20.3gを用いたこと以外は、実施例2と同様の方法でエポキシ樹脂硬化剤を得た。該エポキシ樹脂硬化剤を用いて、実施例2と同様の方法でエポキシ樹脂組成物を調製し、前記評価を行った。結果を表3に示す。
実施例9において、pBDEA-2Mを20.5g、MXDAを20.5g、jER828を19.0gに変更したこと以外は、実施例9と同様の方法でエポキシ樹脂硬化剤を得た。該エポキシ樹脂硬化剤を用いて、実施例9と同様の方法でエポキシ樹脂組成物を調製し、前記評価を行った。結果を表3に示す。
実施例3において、mBDEA 41.3g、及びjER828 18.7gに替えて、mBDEA 7.86g、MXDA 31.44g、及びjER828 20.7gを用いたこと以外は、実施例3と同様の方法でエポキシ樹脂硬化剤を得た。該エポキシ樹脂硬化剤を用いて、実施例3と同様の方法でエポキシ樹脂組成物を調製し、前記評価を行った。結果を表4に示す。
実施例11において、mBDEAを20.05g、MXDAを20.05g、jER828を19.9gに変更したこと以外は、実施例11と同様の方法でエポキシ樹脂硬化剤を得た。該エポキシ樹脂硬化剤を用いて、実施例11と同様の方法でエポキシ樹脂組成物を調製し、前記評価を行った。結果を表4に示す。
さらに表2~4に示すように、実施例2,3,8,11,12のエポキシ樹脂硬化剤を用いたエポキシ樹脂組成物は、比較例1と対比して、得られる塗膜の耐水性も向上することが判った。
Claims (8)
- 前記アダクト変性体が、前記ポリアミン(A)と、少なくとも1つのエポキシ基を有するエポキシ化合物との反応物を含む反応組成物である、請求項1に記載のエポキシ樹脂硬化剤。
- 前記ポリアミン(A)中の前記ジアミン(A1)の含有量が5質量%以上である、請求項1~3のいずれか1項に記載のエポキシ樹脂硬化剤。
- 前記ポリアミン(A)がさらにキシリレンジアミンを含有する、請求項1~4のいずれか1項に記載のエポキシ樹脂硬化剤。
- 前記エポキシ樹脂硬化剤に含まれる全硬化剤成分中の、前記ポリアミン(A)及びそのアダクト変性体の合計含有量が50質量%以上である、請求項1~5のいずれか1項に記載のエポキシ樹脂硬化剤。
- エポキシ樹脂と、請求項1~6のいずれか1項に記載のエポキシ樹脂硬化剤とを含有するエポキシ樹脂組成物。
- 請求項7に記載のエポキシ樹脂組成物を含有する塗料。
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JP2004503527A (ja) | 2000-06-13 | 2004-02-05 | イーライ・リリー・アンド・カンパニー | スルホンアミド誘導体 |
JP2007191527A (ja) * | 2006-01-18 | 2007-08-02 | Japan Epoxy Resin Kk | エポキシ樹脂組成物 |
CN112048151A (zh) * | 2020-07-24 | 2020-12-08 | 福建创立佳科技有限公司 | 一种用于拉挤成型工艺制备芳纶复合芯的树脂组合物 |
WO2021048282A1 (en) * | 2019-09-10 | 2021-03-18 | Gurit (Uk) Ltd | Epoxy resin adhesives |
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JP2007191527A (ja) * | 2006-01-18 | 2007-08-02 | Japan Epoxy Resin Kk | エポキシ樹脂組成物 |
WO2021048282A1 (en) * | 2019-09-10 | 2021-03-18 | Gurit (Uk) Ltd | Epoxy resin adhesives |
CN112048151A (zh) * | 2020-07-24 | 2020-12-08 | 福建创立佳科技有限公司 | 一种用于拉挤成型工艺制备芳纶复合芯的树脂组合物 |
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