JP5996977B2 - Polythiourethane compound, epoxy resin curing agent containing the compound, and one-part curable epoxy resin composition comprising the epoxy resin curing agent - Google Patents
Polythiourethane compound, epoxy resin curing agent containing the compound, and one-part curable epoxy resin composition comprising the epoxy resin curing agent Download PDFInfo
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- JP5996977B2 JP5996977B2 JP2012197075A JP2012197075A JP5996977B2 JP 5996977 B2 JP5996977 B2 JP 5996977B2 JP 2012197075 A JP2012197075 A JP 2012197075A JP 2012197075 A JP2012197075 A JP 2012197075A JP 5996977 B2 JP5996977 B2 JP 5996977B2
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- epoxy resin
- compound
- curing agent
- phenyl
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- 239000003822 epoxy resin Substances 0.000 title claims description 41
- 229920000647 polyepoxide Polymers 0.000 title claims description 41
- 150000001875 compounds Chemical class 0.000 title claims description 37
- 239000000203 mixture Substances 0.000 title claims description 26
- 239000003795 chemical substances by application Substances 0.000 title claims description 25
- 229920002578 polythiourethane polymer Polymers 0.000 title claims description 15
- -1 2 , 6-dimethylphenyl group Chemical group 0.000 claims description 77
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims description 9
- 125000001624 naphthyl group Chemical group 0.000 claims description 9
- 125000005561 phenanthryl group Chemical group 0.000 claims description 9
- 125000003107 substituted aryl group Chemical group 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 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 claims description 4
- 125000004215 2,4-difluorophenyl group Chemical group [H]C1=C([H])C(*)=C(F)C([H])=C1F 0.000 claims description 3
- 125000006276 2-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 claims description 3
- 125000004189 3,4-dichlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(Cl)C([H])=C1* 0.000 claims description 3
- 125000006275 3-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C([H])C(*)=C1[H] 0.000 claims description 3
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 claims description 3
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 claims description 3
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 claims description 3
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 3
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 3
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 3
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 3
- 125000004863 4-trifluoromethoxyphenyl group Chemical group [H]C1=C([H])C(OC(F)(F)F)=C([H])C([H])=C1* 0.000 claims description 3
- 125000004199 4-trifluoromethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C(F)(F)F 0.000 claims description 3
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims description 3
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 3
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 3
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 claims description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 238000003860 storage Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 239000000123 paper Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 229920000768 polyamine Polymers 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 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 4
- 150000002170 ethers Chemical class 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 150000002460 imidazoles Chemical class 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 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 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 3
- 229960001755 resorcinol Drugs 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XMGQYMWWDOXHJM-JTQLQIEISA-N (+)-α-limonene Chemical compound CC(=C)[C@@H]1CCC(C)=CC1 XMGQYMWWDOXHJM-JTQLQIEISA-N 0.000 description 2
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 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
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 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
- 239000000463 material Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Resins (AREA)
Description
本発明はポリチオウレタン化合物に関し、詳しくは、ポリエポキシ化合物と組み合わせることにより、貯蔵安定性及び硬化性に優れた硬化性エポキシ樹脂組成物を提供することができるポリチオウレタン化合物に関する。 The present invention relates to a polythiourethane compound, and more particularly to a polythiourethane compound that can provide a curable epoxy resin composition excellent in storage stability and curability by being combined with a polyepoxy compound.
エポキシ樹脂は、各種基材への接着性に優れている上、その硬化物は、耐熱性、耐薬品性、電気特性、機械特性等に比較的優れているため、塗料、接着剤、各種成型材料等の幅広い用途がある。 Epoxy resins have excellent adhesion to various substrates, and their cured products are relatively excellent in heat resistance, chemical resistance, electrical properties, mechanical properties, etc., so paints, adhesives, and various moldings Wide range of uses such as materials.
従来、エポキシ樹脂組成物は、使用直前に硬化剤や硬化促進剤を添加する二液系が主流であった。二液系は、常温あるいは低温において硬化させることができるという利点を有する反面、使用直前に計量、混合しなければならない上、使用可能な時間が短いために、自動機械への適用が困難である等、使用条件が制限されるという問題がある。 Conventionally, epoxy resin compositions have been mainly two-component systems in which a curing agent or a curing accelerator is added immediately before use. The two-component system has the advantage that it can be cured at room temperature or low temperature, but it must be weighed and mixed immediately before use, and since it can be used for a short time, it is difficult to apply it to an automatic machine. There is a problem that usage conditions are limited.
このような問題を解消するために一液型硬化性エポキシ樹脂組成物が望まれているが、一液型硬化性エポキシ樹脂組成物を得るためには、室温では硬化反応を開始させず、加熱することにより硬化反応を開始させる性質を有する、潜在性硬化剤が必要である。 In order to solve such problems, a one-pack type curable epoxy resin composition is desired, but in order to obtain a one-pack type curable epoxy resin composition, the curing reaction is not started at room temperature. There is a need for a latent curing agent that has the property of initiating a curing reaction.
潜在性硬化剤としては、例えば、ジシアンジアミド、二塩基酸ジヒドラジド、三フッ化ホウ素アミン錯塩、グアナミン類、メラミン、イミダゾール類等が提案されている。
しかしながら、ジシアンジアミド、メラミン、グアナミン類等とエポキシ樹脂を組み合わせた一液型硬化性エポキシ樹脂組成物は、貯蔵安定性には優れているものの、１５０℃以上の高温を長時間加えなければ硬化しないという欠点を有する。また、これらと硬化促進剤を併用して硬化時間を短縮する方法も広く使用されているが、この場合には貯蔵安定性が著しく損なわれるという問題がある。
As the latent curing agent, for example, dicyandiamide, dibasic acid dihydrazide, boron trifluoride amine complex salt, guanamines, melamine, imidazoles and the like have been proposed.
However, a one-part curable epoxy resin composition combining an epoxy resin with dicyandiamide, melamine, guanamines, etc. is excellent in storage stability, but does not cure unless a high temperature of 150 ° C. or higher is applied for a long time. Has drawbacks. In addition, a method of shortening the curing time by using these and a curing accelerator in combination is widely used, but in this case, there is a problem that storage stability is remarkably impaired.
一方、二塩基酸ジヒドラジドやイミダゾール類を潜在性硬化剤として使用した場合には、比較的低温で硬化はするものの、貯蔵安定性に乏しい。また、潜在性硬化剤として三フッ化ホウ素アミン錯塩を含有する一液型硬化性エポキシ樹脂組成物は、貯蔵安定性に優れ、硬化時間が短いという長所がある一方、耐水性に劣る上、金属に対する腐食性を有する等の短所を有する。
更に、硬化物の物性の低下が抑制された熱硬化性樹脂組成物としては、例えば、ポリチオウレタン結合含有化合物を含有する熱硬化性樹脂組成物が提案されているが（特許文献１）、未だ満足できる性能のものは得られていない。
On the other hand, when dibasic acid dihydrazide or imidazole is used as a latent curing agent, it cures at a relatively low temperature but has poor storage stability. In addition, the one-part curable epoxy resin composition containing boron trifluoride amine complex salt as a latent curing agent has the advantages of excellent storage stability and a short curing time, while being inferior in water resistance and metal. It has disadvantages such as being corrosive to
Furthermore, as a thermosetting resin composition in which a decrease in physical properties of the cured product is suppressed, for example, a thermosetting resin composition containing a polythiourethane bond-containing compound has been proposed (Patent Document 1). No satisfactory performance has been obtained yet.
従って本発明の第１の目的は、一液型硬化性エポキシ樹脂用硬化剤として好適な新規化合物を提供することにある。
本発明の第２の目的は、貯蔵安定性及び硬化性に優れた一液型硬化性エポキシ樹脂組成物を提供することができるエポキシ樹脂用硬化剤を提供することにある。
更に、本発明の第３の目的は、貯蔵安定性及び硬化性に優れた一液型硬化性エポキシ樹脂組成物を提供することにある。
Accordingly, a first object of the present invention is to provide a novel compound suitable as a curing agent for a one-component curable epoxy resin.
The second object of the present invention is to provide a curing agent for an epoxy resin that can provide a one-component curable epoxy resin composition excellent in storage stability and curability.
Furthermore, the third object of the present invention is to provide a one-component curable epoxy resin composition excellent in storage stability and curability.
本発明者らは、上記の諸目的を達成するために鋭意検討した結果、特定のポリチオウレタン化合物をエポキシ化合物と組み合わせることにより、貯蔵安定性及び硬化性に優れた一液型硬化性エポキシ樹脂組成物が得られることを見いだし、本発明に到達した。 As a result of intensive investigations to achieve the above-mentioned objects, the present inventors have combined a specific polythiourethane compound with an epoxy compound to produce a one-part curable epoxy resin excellent in storage stability and curability. The inventors have found that a composition can be obtained and have reached the present invention.
即ち本発明は、下記一般式（Ｉ−１）、（Ｉ−２）又は（Ｉ―３）で表されるポリチオウレタン化合物、該ポリチオウレタン化合物からなる群の中から選択された少なくとも１種の化合物を含有するエポキシ樹脂用硬化剤、及び、該エポキシ樹脂用硬化剤を含有してなる、一液型硬化性エポキシ樹脂組成物である。
但し、（Ｉ−１）〜（Ｉ−３）式中のＲ’は、水素原子、非置換のアルキル基、又は、非置換若しくは置換されたフェニル基、ナフチル基、アントリル基若しくはフェナントリル基からなる群の中から選択される非置換又は置換アリール基であり、Ｒ’’は、非置換のアルキル基、又は、フェニル基、4-メチルフェニル基、3-メチルフェニル基、2-メチルフェニル基、2,6-ジメチルフェニル基、3,5-ジメチルフェニル基、4-エチルフェニル基、2,6-ジイソプロピルフェニル基、4-ブチルフェニル基、4-メトキシフェニル基、3-メトキシフェニル基、2-メトキシフェニル基、4-エトキシフェニル基、4-ブロモフェニル基、3-ブロモフェニル基、2-ブロモフェニル基、4-クロロフェニル基、3-クロロフェニル基、2-クロロフェニル基、2,3-ジクロロフェニル基、2,4-ジクロロフェニル基、2,5-ジクロロフェニル基、2,6-ジクロロフェニル基、3,4-ジクロロフェニル基、3,5-ジクロロフェニル基、2,4,6-トリクロロフェニル基、4-クロロ-3-ニトロフェニル基、3-クロロ-4-メチルフェニル基、4-フルオロフェニル基、3-フルオロフェニル基、2-フルオロフェニル基、2,4-ジフルオロフェニル基、2,5-ジフルオロフェニル基、3,4-ジフルオロフェニル基、4-トリフルオロメチルフェニル基、3-トリフルオロメチルフェニル基、2-トリフルオロメチルフェニル基、3,5-ビス(トリフルオロ)フェニル基、4-トリフルオロメトキシフェニル基、4-ニトロフェニル基、3-ニトロフェニル基、2-ニトロフェニル基、3,5-ジニトロフェニル基、ナフチル基、アントリル基及びフェナントリル基からなる群より選択される非置換又は置換アリール基であり、（Ｉ−２）式中のＲ’’’は、水素原子、非置換のアルキル基、又は、非置換若しくは置換されたフェニル基、ナフチル基、アントリル基及びフェナントリル基からなる群より選択される非置換又は置換アリール基である。
That is, the present invention provides at least one selected from the group consisting of a polythiourethane compound represented by the following general formula (I- 1), (I-2) or (I-3 ) and the polythiourethane compound. An epoxy resin curing agent containing a seed compound and a one-component curable epoxy resin composition comprising the epoxy resin curing agent.
However, R ′ in the formulas (I-1) to (I-3 ) consists of a hydrogen atom, an unsubstituted alkyl group , or an unsubstituted or substituted phenyl group, naphthyl group, anthryl group or phenanthryl group. An unsubstituted or substituted aryl group selected from the group , wherein R ″ is an unsubstituted alkyl group , or a phenyl group, a 4-methylphenyl group, a 3-methylphenyl group, a 2-methylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 4-ethylphenyl group, 2,6-diisopropylphenyl group, 4-butylphenyl group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2- Methoxyphenyl group, 4-ethoxyphenyl group, 4-bromophenyl group, 3-bromophenyl group, 2-bromophenyl group, 4-chlorophenyl group, 3-chlorophenyl group, 2-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-di Chlorophenyl group, 2,5-dichlorophenyl group, 2,6-dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2,4,6-trichlorophenyl group, 4-chloro-3-nitrophenyl group 3-chloro-4-methylphenyl group, 4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 3,4-difluoro Phenyl group, 4-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 2-trifluoromethylphenyl group, 3,5-bis (trifluoro) phenyl group, 4-trifluoromethoxyphenyl group, 4-nitro phenyl group, 3-nitrophenyl group, 2-nitrophenyl group, 3,5-dinitrophenyl group, a naphthyl group, unsubstituted or substituted aryl group is selected from the group consisting of anthryl and phenanthryl groups (I-2) R ′ ″ in the formula is a hydrogen atom, an unsubstituted alkyl group, or a non-selected group selected from the group consisting of an unsubstituted or substituted phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. A substituted or substituted aryl group .
本発明により、優れた硬化特性と保存安定性を有する一液型硬化性エポキシ樹脂組成物が得られる。特に、本発明の一液型硬化性エポキシ樹脂組成物は、常温で固体の成分を含まないため、作業性に優れている上、狭所における接着や含浸接着にも適している。 According to the present invention, a one-component curable epoxy resin composition having excellent curing characteristics and storage stability can be obtained. In particular, since the one-component curable epoxy resin composition of the present invention does not contain a solid component at room temperature, it has excellent workability and is also suitable for adhesion in narrow spaces and impregnation adhesion.
本発明のポリチオウレタン化合物は、下記式（Ｉ−１）、（Ｉ−２）又は（Ｉ−３）で表される化合物である。
Polythiourethane compounds of the present invention has the following formula (I-1), a compound represented by (I-2) or (I-3).
前記一般式（Ｉ−１）、（Ｉ−２）及び（Ｉ−３）中のＲ’は、水素原子、非置換のアルキル基、又は、非置換又は置換されたフェニル基、ナフチル基、アントリル基若しくはフェナントリルからなる群の中から選択される非置換又は置換アリール基である。
前記アルキル基としては、例えば、炭素数１〜１２の直鎖型、分岐型又は脂環式のアルキル基等が挙げられ、具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、第三ブチル基等が挙げられる。
R ′ in the general formulas (I-1), (I-2) and (I-3) is a hydrogen atom, an unsubstituted alkyl group, an unsubstituted or substituted phenyl group, a naphthyl group, an anthryl. An unsubstituted or substituted aryl group selected from the group consisting of a group or phenanthryl.
Examples of the alkyl group, for example, linear from 1 to 12 carbon atoms, branched or alicyclic alkyl group and the like, and specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, isobutyl group, Ru and the like tertiary butyl group.
また、前記一般式（Ｉ−１）、（Ｉ−２）及び（Ｉ−３）中のＲ’’は、非置換のアルキル基、又は、フェニル基、4-メチルフェニル基、3-メチルフェニル基、2-メチルフェニル基、2,6-ジメチルフェニル基、3,5-ジメチルフェニル基、4-エチルフェニル基、2,6-ジイソプロピルフェニル基、4-ブチルフェニル基、4-メトキシフェニル基、3-メトキシフェニル基、2-メトキシフェニル基、4-エトキシフェニル基、4-ブロモフェニル基、3-ブロモフェニル基、2-ブロモフェニル基、4-クロロフェニル基、3-クロロフェニル基、2-クロロフェニル基、2,3-ジクロロフェニル基、2,4-ジクロロフェニル基、2,5-ジクロロフェニル基、2,6-ジクロロフェニル基、3,4-ジクロロフェニル基、3,5-ジクロロフェニル基、2,4,6-トリクロロフェニル基、4-クロロ-3-ニトロフェニル基、3-クロロ-4-メチルフェニル基、4-フルオロフェニル基、3-フルオロフェニル基、2-フルオロフェニル基、2,4-ジフルオロフェニル基、2,5-ジフルオロフェニル基、3,4-ジフルオロフェニル基、4-トリフルオロメチルフェニル基、3-トリフルオロメチルフェニル基、2-トリフルオロメチルフェニル基、3,5-ビス(トリフルオロ)フェニル基、4-トリフルオロメトキシフェニル基、4-ニトロフェニル基、3-ニトロフェニル基、2-ニトロフェニル基、3,5-ジニトロフェニル基、ナフチル基、アントリル基及びフェナントリル基からなる群より選択される非置換又は置換アリール基である。
前記アルキル基としては、例えば、炭素数１〜１２の直鎖型、分岐型又は脂環式のアルキル基が挙げられ、具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、第三ブチル基、アミル基、イソアミル基、第三アミル基、ヘキシル基、シクロヘキシル基、ヘプチル基、オクチル基、第三オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基等が挙げられる。
In the general formulas (I-1), (I-2) and (I-3), R ″ represents an unsubstituted alkyl group, a phenyl group, a 4-methylphenyl group, or 3-methylphenyl. Group, 2-methylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 4-ethylphenyl group, 2,6-diisopropylphenyl group, 4-butylphenyl group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 4-ethoxyphenyl group, 4-bromophenyl group, 3-bromophenyl group, 2-bromophenyl group, 4-chlorophenyl group, 3-chlorophenyl group, 2-chlorophenyl group 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,6-dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2,4,6-tri Chlorophenyl, 4-chloro-3-nitrophenyl, 3-chloro Ro-4-methylphenyl group, 4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 3,4-difluorophenyl group, 4-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 2-trifluoromethylphenyl group, 3,5-bis (trifluoro) phenyl group, 4-trifluoromethoxyphenyl group, 4-nitrophenyl group, An unsubstituted or substituted aryl group selected from the group consisting of 3-nitrophenyl group, 2-nitrophenyl group, 3,5-dinitrophenyl group, naphthyl group, anthryl group and phenanthryl group.
Examples of the alkyl group, for example, linear from 1 to 12 carbon atoms, include alkyl groups of the branched or alicyclic, and specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group , Isobutyl group, tertiary butyl group, amyl group, isoamyl group, tertiary amyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, tertiary octyl group, nonyl group, decyl group, undecyl group, dodecyl group, etc. the recited Ru.
また、一般式（Ｉ−２）中のＲ’’’は、水素原子、非置換のアルキル基、又は、非置換若しくは置換されたフェニル基、ナフチル基、アントリル基、フェナントリル基からなる群より選択される非置換又は置換アリール基である。
上記アルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、第三ブチル基、アミル基、イソアミル基、第三アミル基、ヘキシル基、シクロヘキシル基、ヘプチル基、オクチル基、第三オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基等が挙げられる。
R ′ ″ in general formula (I-2) is selected from the group consisting of a hydrogen atom, an unsubstituted alkyl group, or an unsubstituted or substituted phenyl group, naphthyl group, anthryl group, and phenanthryl group. An unsubstituted or substituted aryl group.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, an amyl group, an isoamyl group, a tert-amyl group, a hexyl group, a cyclohexyl group, and a heptyl group. , octyl, tert-octyl group, nonyl group, decyl group, undecyl group, dodecyl group and the Ru mentioned.
本発明のポリチオウレタン化合物は、下記式に示される通り、ポリチオール化合物とイソシアネート化合物とを反応させることにより得られる。
上記の反応におけるチオール化合物とイソシアネート化合物の使用量は、イソシアネート基とメルカプト基の比（[NCO]／［SH］比）として、0.5〜1であることが好ましく、1であることが最も好ましい。
但し、上記反応式中の一般式（Ｉ）は、前記一般式（Ｉ−１）〜（Ｉ−３）を上位概念化した化学式である。
The polythiourethane compound of this invention is obtained by making a polythiol compound and an isocyanate compound react as shown by a following formula.
The amount of the thiol compound and isocyanate compound used in the above reaction is preferably 0.5 to 1, and most preferably 1, as the ratio of isocyanate group to mercapto group ([NCO] / [SH] ratio).
However, the general formula (I) in the above reaction formula is a chemical formula obtained by superposing the general formulas (I-1) to (I-3).
前記反応に使用される触媒としては、例えば、ジブチル錫ラウレート、ジ(2-エチルヘキサン酸))錫等のスズ化合物；テトラアルキルチタネート等のチタン化合物；トリフェニルホスフィン、トリブチルホスフィン、トリシクロヘキシルホスフィン等のホスフィン類；トリエチルアミン、トリブチルアミン、ジアザビシクロウンデセン、ジアザビシクロノネン、1,4-ジアザビシクロ[2.2.2]オクタン等の3級アミン；ピリジン、N,N-ジメチルアミノピリジン等のピリジン類；及び、1-メチルイミダゾール等のイミダゾール類等が挙げられる。 Examples of the catalyst used in the reaction include tin compounds such as dibutyltin laurate and di (2-ethylhexanoic acid) tin; titanium compounds such as tetraalkyl titanate; triphenylphosphine, tributylphosphine, and tricyclohexylphosphine. Phosphines; tertiary amines such as triethylamine, tributylamine, diazabicycloundecene, diazabicyclononene, 1,4-diazabicyclo [2.2.2] octane; pyridines such as pyridine and N, N-dimethylaminopyridine And imidazoles such as 1-methylimidazole.
また、前記反応に使用される溶媒としては、例えば、メチルエチルケトン、メチルアミルケトン、ジエチルケトン、アセトン、メチルイソプロピルケトン、プロピレングリコールモノメチルエーテルアセテート、シクロヘキサノン等のケトン類；テトラヒドロフラン、1,2-ジメトキシエタン、1,2-ジエトキシエタン等のエーテル類；酢酸エチル、酢酸n-ブチル等のエステル類；N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチルピロリドン等のアミド類、イソ-又はn-ブタノール、イソ-又はn-プロパノール、アミルアルコール等のアルコール類；ベンゼン、トルエン、キシレン等の芳香族炭化水素；テレピン油、D-リモネン、ピネン等のテルペン系炭化水素油；ミネラルスピリット、スワゾール#310（コスモ松山石油（株））、ソルベッソ#100（エクソン化学（株））等のパラフィン系溶剤；四塩化炭素、クロロホルム、トリクロロエチレン、塩化メチレン等のハロゲン化脂肪族炭化水素；クロロベンゼン等のハロゲン化芳香族炭化水素；アニリン、トリエチルアミン、ピリジン、ジオキサン、酢酸、アセトニトリル、二硫化炭素、ジメチルスルホキシド、N,N’-ジメチルイミダゾリジノン等が挙げられる。 Examples of the solvent used in the reaction include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, propylene glycol monomethyl ether acetate, and cyclohexanone; tetrahydrofuran, 1,2-dimethoxyethane, Ethers such as 1,2-diethoxyethane; esters such as ethyl acetate and n-butyl acetate; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone, iso- or Alcohols such as n-butanol, iso- or n-propanol and amyl alcohol; aromatic hydrocarbons such as benzene, toluene and xylene; Terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; mineral spirits and swazoles # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solbec Paraffinic solvents such as # 100 (Exxon Chemical Co., Ltd.); Halogenated aliphatic hydrocarbons such as carbon tetrachloride, chloroform, trichloroethylene and methylene chloride; Halogenated aromatic hydrocarbons such as chlorobenzene; Aniline, triethylamine, pyridine, Dioxane, acetic acid, acetonitrile, carbon disulfide, dimethyl sulfoxide, N, N′-dimethylimidazolidinone and the like can be mentioned.
前記反応は、通常、−８０〜２００℃の温度下で、０．５時間〜７２時間かけて行われるが、反応温度は室温〜８０℃であることが好ましく、反応時間は１時間〜８時間であることが好ましい。 The reaction is usually carried out at a temperature of −80 to 200 ° C. for 0.5 to 72 hours. The reaction temperature is preferably room temperature to 80 ° C., and the reaction time is 1 to 8 hours. It is preferable that
本発明のポリチオウレタン化合物は、単独で本発明のエポキシ樹脂用硬化剤として機能するが、必要に応じて、他のエポキシ樹脂硬化剤を併用してもよい。本明細書においては、これらを総称して、以後、本発明のエポキシ樹脂用硬化剤とする。 The polythiourethane compound of the present invention functions alone as the curing agent for epoxy resins of the present invention, but other epoxy resin curing agents may be used in combination as necessary. In the present specification, these are collectively referred to as the epoxy resin curing agent of the present invention.
併用することができるエポキシ樹脂硬化剤としては、例えば、2-エチル-4-メチルイミダゾール、1,2-ジメチルイミダゾール、1-(2-メチルイミダゾール-1-イルメチル)ナフタレン-2-オール等のイミダゾール類；ジエチレントリアミン、トリエチレントリアミン、テトラエチレンペンタミン等のポリアルキルポリアミン類；1,2-ジアミノシクロヘキサン、1,4-ジアミノ-3,6-ジエチルシクロヘキサン、イソホロンジアミン等の脂環式ポリアミン類；m-キシリレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホン等の芳香族ポリアミン類等が挙げられる。 Examples of the epoxy resin curing agent that can be used in combination include imidazoles such as 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, and 1- (2-methylimidazol-1-ylmethyl) naphthalen-2-ol. Polyalkylpolyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine; alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane and isophoronediamine; m -Aromatic polyamines such as xylylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone.
また、前記ポリアミン類と、フェニルグリシジルエーテル、ブチルグリシジルエーテル、ビスフェノールA-ジグリシジルエーテル、ビスフェノールF-ジグリシジルエーテル等のグリシジルエーテル類若しくはカルボン酸のグリシジルエステル類等の各種エポキシ樹脂とを、常法によって反応させることによって製造されるポリエポキシ付加変性物；前記有機ポリアミン類と、フタル酸、イソフタル酸、ダイマー酸等のカルボン酸類とを常法によって反応させることによって製造されるアミド化変性物；又は、前記ポリアミン類とホルムアルデヒド等のアルデヒド類、及び、フェノール、クレゾール、キシレノール、第三ブチルフェノール、レゾルシン等の、核に少なくとも一個のアルデヒド化反応性場所を有するフェノール類とを、常法によって反応させることによって製造されるマンニッヒ化変性物を使用することもできる。
更に、ジシアンジアミド、酸無水物、イミダゾール類等の潜在性硬化剤を併用してもよい。
In addition, the polyamines and phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, glycidyl ethers such as bisphenol F-diglycidyl ether, or various epoxy resins such as glycidyl esters of carboxylic acids, A polyepoxy addition-modified product produced by reacting by the above; an amidation-modified product produced by reacting the organic polyamines with carboxylic acids such as phthalic acid, isophthalic acid, and dimer acid; or The polyamines and aldehydes such as formaldehyde, and phenols having at least one aldehyde-reactive site in the nucleus, such as phenol, cresol, xylenol, tert-butylphenol, resorcin, etc. It is also possible to use a Mannich modified product produced by reacting with the above.
Furthermore, latent curing agents such as dicyandiamide, acid anhydrides, and imidazoles may be used in combination.
本発明の一液型硬化性エポキシ樹脂組成物は、ポリエポキシ化合物及び本発明のエポキシ樹脂用硬化剤を含有する。
本発明の一液型硬化性エポキシ樹脂組成物に使用されるポリエポキシ化合物としては、例えば、ハイドロキノン、レゾルシン、ピロカテコール、フロログルシノール等の単核多価フェノール化合物のポリグリシジルエーテル化合物；ジヒドロキシナフタレン、ビフェノール、メチレンビスフェノール(ビスフェノールF)、メチレンビス(オルトクレゾール)、エチリデンビスフェノール、イソプロピリデンビスフェノール（ビスフェノールA）、イソプロピリデンビス(オルトクレゾール)、テトラブロモビスフェノールA、1,3-ビス(4-ヒドロキシクミルベンゼン）、1,4-ビス(4-ヒドロキシクミルベンゼン)、1,1,3-トリス(4-ヒドロキシフェニル)ブタン、1,1,2,2-テトラ(4-ヒドロキシフェニル)エタン、チオビスフェノール、スルホニルビスフェノール、オキシビスフェノール、フェノールノボラック、オルソクレゾールノボラック、エチルフェノールノボラック、ブチルフェノールノボラック、オクチルフェノールノボラック、レゾルシンノボラック、テルペンフェノール等の多核多価フェノール化合物のポリグリジルエーテル化合物；エチレングリコール、プロピレングリコール、ブチレングリコール、ヘキサンジオール、ポリグリコール、チオジグリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、ソルビトール、ビスフェノールA-エチレンオキシド付加物等の多価アルコール類のポリグリシジルエーテル；マレイン酸、フマル酸、イタコン酸、コハク酸、グルタル酸、スベリン酸、アジピン酸、アゼライン酸、セバシン酸、ダイマー酸、トリマー酸、フタル酸、イソフタル酸、テレフタル酸、トリメリット酸、トリメシン酸、ピロメリット酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、エンドメチレンテトラヒドロフタル酸等の脂肪族、芳香族又は脂環族多塩基酸のグリシジルエステル類；及びグリシジルメタクリレートの単独重合体又は共重合体；N,N-ジグリシジルアニリン、ビス(4-(N-メチル-N-グリシジルアミノ)フェニル)メタン、ジグリシジルオルトトルイジン等のグリシジルアミノ基を有するエポキシ化合物；ビニルシクロヘキセンジエポキシド、ジシクロペンタンジエンジエポキサイド、3,4-エポキシシクロヘキシルメチル-3,4-エポキシシクロヘキサンカルボキシレート、3,4-エポキシ-6-メチルシクロヘキシルメチル-6-メチルシクロヘキサンカルボキシレート、ビス(3,4-エポキシ-6-メチルシクロヘキシルメチル)アジペート等の環状オレフィン化合物のエポキシ化物；エポキシ化ポリブタジエン、エポキシ化スチレン−ブタジエン共重合物等のエポキシ化共役ジエン重合体、トリグリシジルイソシアヌレート等の複素環化合物が挙げられる。
また、これらのポリエポキシ化合物は、末端にイソシアネートを有するプレポリマーによって内部架橋されたもの、又は、多価フェノール、ポリアミン、カルボニル基含有化合物、ポリリン酸エステル等の、多価の活性水素化合物によって高分子量化されたものでもよい。
The one-component curable epoxy resin composition of the present invention contains a polyepoxy compound and the curing agent for epoxy resin of the present invention.
Examples of the polyepoxy compound used in the one-component curable epoxy resin composition of the present invention include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol; dihydroxynaphthalene , Biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxyc Milbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, Thiobisphenol, sulfonylbisphenol, oxybi Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as sphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, terpene phenol; ethylene glycol, propylene glycol, butylene glycol, hexanediol , Polyglycidyl ethers of polyhydric alcohols such as polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid , Suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid Glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as acids, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid; and Glycidyl methacrylate homopolymer or copolymer; N, N-diglycidylaniline, bis (4- (N-methyl-N-glycidylamino) phenyl) methane, epoxy compounds having a glycidylamino group such as diglycidyl orthotoluidine Vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexyl Examples thereof include epoxidized products of cyclic olefin compounds such as methyl) adipate; epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymer, and heterocyclic compounds such as triglycidyl isocyanurate.
In addition, these polyepoxy compounds are highly crosslinked by polyhydric active hydrogen compounds such as those internally cross-linked by a prepolymer having an isocyanate at the terminal, or polyhydric phenols, polyamines, carbonyl group-containing compounds, polyphosphate esters and the like. The molecular weight may be used.
また、ポリエポキシ化合物のエポキシ当量は、７０〜３０００であることが必要であり、特に、９０〜２０００であることが好ましい。
ポリエポキシ化合物のエポキシ当量が７０未満では、硬化物の物性が低下するおそれがあり、３０００よりも大きい場合には、十分な硬化性が得られなくなるおそれがある。
Moreover, the epoxy equivalent of a polyepoxy compound needs to be 70-3000, and it is especially preferable that it is 90-2000.
If the epoxy equivalent of the polyepoxy compound is less than 70, the physical properties of the cured product may be deteriorated. If it is greater than 3000, sufficient curability may not be obtained.
更に、本発明の一液型硬化性エポキシ樹脂組成物は、必要に応じて、硬化触媒；モノグリシジルエーテル類、ジオクチルフタレート、ジブチルフタレート、ベンジルアルコール、コールタール等の反応性又は非反応性の希釈剤又は可塑剤；ガラス繊維、炭素繊維、セルロース、ケイ砂、セメント、カオリン、クレー、水酸化アルミニウム、ベントナイト、タルク、シリカ、微粉末シリカ、二酸化チタン、カーボンブラック、グラファイト、酸化鉄、瀝青物質等の充填剤又は顔料；γ-アミノプロピルトリエトキシシラン、N-β-(アミノエチル)-γ-アミノプロピルトリエトキシシラン、N-β-(アミノエチル)-N’-β-(アミノエチル)-γ-アミノプロピルトリエトキシシラン、γ-アニリノプロピルトリエトキシシラン、γ-グリシドキシプロピルトリエトキシシラン、β-(3,4-エポキシシクロヘキシル)エチルトリエトキシシラン、ビニルトリエトキシシラン、N-β-(N-ビニルベンジルアミノエチル)-γ-アミノプロピルトリエトキシシラン、γ-メタクリロキシプロピルトリメトキシシラン、γ-クロロプロピルトリメトキシシラン、γ-メルカプトプロピルトリメトキシシラン等のシランカップリング剤；キャンデリラワックス、カルナウバワックス、木ろう、イボタロウ、みつろう、ラノリン、鯨ろう、モンタンワックス、石油ワックス、脂肪酸ワックス、脂肪酸エステル、脂肪酸エーテル、芳香族エステル、芳香族エーテル等の潤滑剤；増粘剤；チキソトロピック剤；酸化防止剤；光安定剤；紫外線吸収剤；難燃剤；消泡剤；防錆剤；コロイダルシリカ、コロイダルアルミナ等の常用の添加物を含有してもよく、更に、キシレン樹脂、石油樹脂等の粘着性の樹脂類を併用することもできる。 Furthermore, the one-pack type curable epoxy resin composition of the present invention can be used as necessary by a curing catalyst; reactive or non-reactive dilution of monoglycidyl ethers, dioctyl phthalate, dibutyl phthalate, benzyl alcohol, coal tar, etc. Agent or plasticizer: glass fiber, carbon fiber, cellulose, silica sand, cement, kaolin, clay, aluminum hydroxide, bentonite, talc, silica, finely divided silica, titanium dioxide, carbon black, graphite, iron oxide, bitumen substance, etc. Or γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -N′-β- (aminoethyl)- γ-aminopropyltriethoxysilane, γ-anilinopropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane , Β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, vinyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxy Silane coupling agents such as silane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, etc .; Lubricants such as fatty acid waxes, fatty acid esters, fatty acid ethers, aromatic esters, aromatic ethers; thickeners; thixotropic agents; antioxidants; light stabilizers; ultraviolet absorbers; Agent; may contain conventional additives such as colloidal silica and colloidal alumina Furthermore, xylene resin, may be used in combination tacky resin such as petroleum resin.
本発明の一液型硬化性エポキシ樹脂組成物は、例えば、コンクリート、セメントモルタル、各種金属、皮革、ガラス、ゴム、プラスチック、木、布、紙等に対する塗料あるいは接着剤；包装用粘着テープ、粘着ラベル、冷凍食品ラベル、リムーバルラベル、ＰＯＳラベル、粘着壁紙、粘着床材の粘着剤；アート紙、軽量コート紙、キャストコート紙、塗工板紙、カーボンレス複写機、含浸紙等の加工紙；天然繊維、合成繊維、ガラス繊維、炭素繊維、金属繊維等の収束剤、ほつれ防止剤、加工剤等の繊維処理剤；シーリング材、セメント混和剤、防水材等の建築材料；電子・電気機器用封止剤等の、広範な用途に使用することができる。 The one-component curable epoxy resin composition of the present invention includes, for example, paints or adhesives for concrete, cement mortar, various metals, leather, glass, rubber, plastic, wood, cloth, paper, etc .; adhesive tape for packaging, adhesive Labels, frozen food labels, removable labels, POS labels, adhesive wallpaper, adhesives for adhesive flooring; art paper, lightweight coated paper, cast coated paper, coated paperboard, carbonless copier, impregnated paper and other processed paper; natural Fiber treatment agents such as fibers, synthetic fibers, glass fibers, carbon fibers, metal fibers, etc., fraying preventives, processing agents, etc .; building materials such as sealing materials, cement admixtures, waterproofing materials; sealing for electronic and electrical equipment It can be used for a wide range of applications such as a stopper.
以下、実施例により本発明を更に詳細に説明するが、本発明はこれらの実施例によって何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these Examples.
［NR-1-PhTU（NR-1-フェニルチオウレタン）の合成］
三官能チオールとしてカレンズMT NR-1（昭和電工（株）製の商品名）34.03gを、500mLの二つ口丸底フラスコに仕込み、減圧乾燥及び窒素置換を行った後、無水DMF（関東化学（株）製）42mL及びトリエチルアミン0.83mLを加え、0℃に冷却した。
[Synthesis of NR-1-PhTU (NR-1-phenylthiourethane)]
34.03 g of Karenz MT NR-1 (trade name, manufactured by Showa Denko KK) as a trifunctional thiol was charged into a 500 mL two-necked round bottom flask, dried under reduced pressure and purged with nitrogen, then anhydrous DMF (Kanto Chemical) 42 mL and 0.83 mL triethylamine were added and cooled to 0 ° C.
次いで、フェニルイソシアナート（関東化学（株）製）19.5mLを撹拌しながら添加し、30分間撹拌した後、室温に戻した。更に、3時間撹拌した後、酢酸エチル600mLを加えた。有機相を、蒸留水300mLを用いて洗浄した。上記洗浄を4回行なった後、有機相を硫酸ナトリウムで乾燥し、ろ過して、溶媒を減圧除去した。
このようにして得られた反応生成物を60℃で2時間減圧乾燥して、白色結晶状の目的化合物NR-1-PhTUを56.0g得た。NR-1-PhTUは定量的に得られた。
Subsequently, 19.5 mL of phenyl isocyanate (manufactured by Kanto Chemical Co., Inc.) was added with stirring, and the mixture was stirred for 30 minutes and then returned to room temperature. Further, after stirring for 3 hours, 600 mL of ethyl acetate was added. The organic phase was washed with 300 mL distilled water. After performing the above washing 4 times, the organic phase was dried over sodium sulfate, filtered and the solvent was removed under reduced pressure.
The reaction product thus obtained was dried under reduced pressure at 60 ° C. for 2 hours to obtain 56.0 g of the target compound NR-1-PhTU in the form of white crystals. NR-1-PhTU was obtained quantitatively.
［NR-1-CyTU（NR-1-シクロヘキシルチオウレタン）の合成］
三官能チオール化合物としてカレンズMT NR-1（昭和電工（株）製の商品名）34.03g、及び、ジラウリン酸ジブチルスズ（Bu2SnLau2）（東京化成工業（株）製）0.025gを、300mLの二つ口丸底フラスコに仕込み、減圧乾燥及び窒素置換を行った後、無水DMF（関東化学（株）製）14mLを加えた。
[Synthesis of NR-1-CyTU (NR-1-cyclohexylthiourethane)]
As a trifunctional thiol compound, 34.03 g of Karenz MT NR-1 (trade name manufactured by Showa Denko KK) and 0.025 g of dibutyltin dilaurate (Bu 2 SnLau 2 ) (manufactured by Tokyo Chemical Industry Co., Ltd.) After charging in a two-necked round bottom flask, drying under reduced pressure and nitrogen substitution, 14 mL of anhydrous DMF (manufactured by Kanto Chemical Co., Inc.) was added.
次いで、シクロヘキシルイソシアナート（東京化成工業（株）製）7.6mLを撹拌しながら添加し、室温下で23時間撹拌した後、更にシクロヘキシルイソシアナート（東京化成工業（株）製）7.6mLを添加した。
室温で23時間撹拌した後、トリエチルアミン0.83mLを添加した。3時間後、蒸留水100mLを添加して1時間撹拌した。酢酸エチル100mLを加え、1時間撹拌した後に、更に酢酸エチル100mLを加えた。水相を分離した後、有機相を飽和食塩水100mLを用いて洗浄した。上記洗浄を3回繰り返した後、水相を分離し、有機相を硫酸ナトリウムで乾燥し、ろ過して、溶媒を減圧除去した。
このようにして得られた生成物を60℃で2時間減圧乾燥して、白色結晶状の目的化合物NR-1-CyTUを16.6g得た。
NR-1-CyTUの収率は88%であった。
Next, 7.6 mL of cyclohexyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added with stirring, and after stirring for 23 hours at room temperature, 7.6 mL of cyclohexyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was further added. .
After stirring for 23 hours at room temperature, 0.83 mL of triethylamine was added. After 3 hours, 100 mL of distilled water was added and stirred for 1 hour. After adding 100 mL of ethyl acetate and stirring for 1 hour, 100 mL of ethyl acetate was further added. After separating the aqueous phase, the organic phase was washed with 100 mL of saturated brine. After repeating the above washing three times, the aqueous phase was separated, the organic phase was dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure.
The product thus obtained was dried under reduced pressure at 60 ° C. for 2 hours to obtain 16.6 g of the target compound NR-1-CyTU in the form of white crystals.
The yield of NR-1-CyTU was 88%.
実施例１及び２における反応は下記式（A）により表される。
The reaction in Examples 1 and 2 is represented by the following formula (A).
［TMTP-PhTU（TMTP-フェニルチオウレタン）の合成］
三官能チオールであるTMTP（トリメチロールプロパントリス(3-メルカプトプロピオナート)（淀化学（株）製）15.94gを300mLの二つ口丸底フラスコに仕込み、減圧乾燥した。その後窒素置換し、無水DMF（関東化学（株）製）28mL、トリエチルアミン0.55mLを加え、0℃に冷却した。フェニルイソシアナート（関東化学（株）製）13.0mLを撹拌しながら添加し、30分間撹拌した後、室温に戻した。
[Synthesis of TMTP-PhTU (TMTP-phenylthiourethane)]
A trifunctional thiol, TMTP (trimethylolpropane tris (3-mercaptopropionate) (manufactured by Sakai Chemical Co., Ltd.) (15.94 g) was charged into a 300 mL two-necked round bottom flask and dried under reduced pressure. Anhydrous DMF (manufactured by Kanto Chemical Co., Inc.) 28 mL and triethylamine 0.55 mL were added and cooled to 0 ° C. Phenyl isocyanate (manufactured by Kanto Chemical Co., Ltd.) 13.0 mL was added with stirring, and after stirring for 30 minutes, It returned to room temperature.
3時間撹拌した後、酢酸エチル200mLを加え、有機相を蒸留水200mLを用いて洗浄した。上記洗浄を4回繰り返した後水相を分離し、有機相を、硫酸ナトリウムを用いて乾燥し、ろ過して、溶媒を減圧除去した。
このようにして得られた生成物を60℃で2時間減圧乾燥して、無色粘調物の目的化合物TMTP-PhTU29.8gを得た。TMTP-PhTUの収率は99%であった。
After stirring for 3 hours, 200 mL of ethyl acetate was added and the organic phase was washed with 200 mL of distilled water. After repeating the above washing 4 times, the aqueous phase was separated, the organic phase was dried using sodium sulfate, filtered, and the solvent was removed under reduced pressure.
The product thus obtained was dried under reduced pressure at 60 ° C. for 2 hours to obtain 29.8 g of a colorless viscous target compound TMTP-PhTU. The yield of TMTP-PhTU was 99%.
実施例３における反応は下記式（B）により表される。
The reaction in Example 3 is represented by the following formula (B).
［構造解析］
合成したポリチオウレタンの構造を、1H NMR測定（JNM EX-400、日本電子（株）製）により確認した。
各化合物の重クロロホルム中におけるNMRスペクトルは、図１〜３に示された通りである。尚、図中のxは酢酸エチルのピークを示す。
[Structural analysis]
The structure of the synthesized polythiourethane was confirmed by 1 H NMR measurement (JNM EX-400, manufactured by JEOL Ltd.).
The NMR spectrum of each compound in deuterated chloroform is as shown in FIGS. In the figure, x represents a peak of ethyl acetate.
［硬化物の作製］
アデカレジンEP-4100E（（株）ADEKA製の商品名、ビスフェノールA型エポキシ樹脂、エポキシ当量：190）、実施例１で得られたNR-1-PhTU、Bu2SnLau2（ジブチル錫ジラウレート）、PPh3（トリフェニルホスフフィン）、及びBnOH（ベンジルアルコール）を下記表１の比率で混合し、一液型硬化性エポキシ樹脂組成物を作製した。
[Production of cured product]
Adeka Resin EP-4100E (trade name, manufactured by ADEKA, bisphenol A type epoxy resin, epoxy equivalent: 190), NR-1-PhTU obtained in Example 1, Bu 2 SnLau 2 (dibutyltin dilaurate), PPh 3 (Triphenylphosphine) and BnOH (benzyl alcohol) were mixed at the ratio shown in Table 1 to prepare a one-pack type curable epoxy resin composition.
得られた樹脂組成物を、180℃で1時間加熱することにより、柔軟な硬化物が得られた。
また、前記一液型硬化性エポキシ樹脂組成物の粘度を、粘度計（東京計器（株）製）を用いて測定した結果、初期粘度は26.3Pa・sであり、25℃で1日保管した後の粘度は、67.7Pa・sであった。
The obtained resin composition was heated at 180 ° C. for 1 hour to obtain a flexible cured product.
Moreover, as a result of measuring the viscosity of the one-component curable epoxy resin composition using a viscometer (manufactured by Tokyo Keiki Co., Ltd.), the initial viscosity was 26.3 Pa · s and stored at 25 ° C. for 1 day. The later viscosity was 67.7 Pa · s.
［比較例１］
表１に示された量のEP-4100E、NR-1及びPPh3を混合して、一液型硬化性エポキシ樹脂組成物を得た。
[Comparative Example 1]
EP-4100E, NR-1 and PPh 3 in the amounts shown in Table 1 were mixed to obtain a one-part curable epoxy resin composition.
得られた樹脂組成物について、実施例４の場合と同様に粘度を測定した結果、初期粘度は15.7Pa・sであったが、25℃で保管したところ、1日後には樹脂組成物が硬化し、測定不可能になった。 As a result of measuring the viscosity of the obtained resin composition in the same manner as in Example 4, the initial viscosity was 15.7 Pa · s. When stored at 25 ° C., the resin composition was cured after one day. And it became impossible to measure.
実施例４及び比較例１の一液型硬化性エポキシ樹脂組成物の組成及び保存安定性の評価結果を表１に示す。
この結果から明らかなように、本発明のポリチオウレタン化合物を硬化剤として含有する、一液型熱硬化性エポキシ樹脂組成物は、保存安定性に優れていることが確認された。
As is apparent from this result, it was confirmed that the one-pack thermosetting epoxy resin composition containing the polythiourethane compound of the present invention as a curing agent is excellent in storage stability.
本発明のポリチオウレタン化合物は、保存安定性及び硬化性に優れた一液型硬化性エポキシ樹脂組成物を提供することができるため、塗料、接着剤、粘着剤、加工紙、繊維処理剤、建築材料及び電子・電気機器用封止剤等の広範な用途があり、産業上極めて有用である。 Since the polythiourethane compound of the present invention can provide a one-part curable epoxy resin composition excellent in storage stability and curability, a paint, an adhesive, an adhesive, a processed paper, a fiber treatment agent, It has a wide range of applications such as building materials and sealants for electronic and electrical equipment, and is extremely useful in industry.
Claims (3)
但し、（Ｉ−１）〜（Ｉ−３）式中のＲ’は水素原子、非置換のアルキル基、又は、非置換若しくは置換されたフェニル基、ナフチル基、アントリル基若しくはフェナントリル基からなる群の中から選択される非置換又は置換アリール基であり、Ｒ’’は、非置換のアルキル基、又は、フェニル基、4-メチルフェニル基、3-メチルフェニル基、2-メチルフェニル基、2,6-ジメチルフェニル基、3,5-ジメチルフェニル基、4-エチルフェニル基、2,6-ジイソプロピルフェニル基、4-ブチルフェニル基、4-メトキシフェニル基、3-メトキシフェニル基、2-メトキシフェニル基、4-エトキシフェニル基、4-ブロモフェニル基、3-ブロモフェニル基、2-ブロモフェニル基、4-クロロフェニル基、3-クロロフェニル基、2-クロロフェニル基、2,3-ジクロロフェニル基、2,4-ジクロロフェニル基、2,5-ジクロロフェニル基、2,6-ジクロロフェニル基、3,4-ジクロロフェニル基、3,5-ジクロロフェニル基、2,4,6-トリクロロフェニル基、4-クロロ-3-ニトロフェニル基、3-クロロ-4-メチルフェニル基、4-フルオロフェニル基、3-フルオロフェニル基、2-フルオロフェニル基、2,4-ジフルオロフェニル基、2,5-ジフルオロフェニル基、3,4-ジフルオロフェニル基、4-トリフルオロメチルフェニル基、3-トリフルオロメチルフェニル基、2-トリフルオロメチルフェニル基、3,5-ビス(トリフルオロ)フェニル基、4-トリフルオロメトキシフェニル基、4-ニトロフェニル基、3-ニトロフェニル基、2-ニトロフェニル基、3,5-ジニトロフェニル基、ナフチル基、アントリル基及びフェナントリル基からなる群より選択される非置換又は置換アリール基であり、（Ｉ−２）式中のＲ’’’は、水素原子、非置換のアルキル基、又は、非置換若しくは置換されたフェニル基、ナフチル基、アントリル基及びフェナントリル基からなる群より選択される非置換又は置換アリール基である。 A polythiourethane compound represented by the following general formula (I- 1), (I-2) or (I-3 );
In the formulas (I-1) to (I-3 ) , R ′ is a hydrogen atom , an unsubstituted alkyl group , or a group consisting of an unsubstituted or substituted phenyl group, naphthyl group, anthryl group, or phenanthryl group. An unsubstituted or substituted aryl group selected from : R ″ represents an unsubstituted alkyl group , a phenyl group, a 4-methylphenyl group, a 3-methylphenyl group, a 2-methylphenyl group, 2 , 6-dimethylphenyl group, 3,5-dimethylphenyl group, 4-ethylphenyl group, 2,6-diisopropylphenyl group, 4-butylphenyl group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxy Phenyl group, 4-ethoxyphenyl group, 4-bromophenyl group, 3-bromophenyl group, 2-bromophenyl group, 4-chlorophenyl group, 3-chlorophenyl group, 2-chlorophenyl group, 2,3-dichlorophenyl group, 2 , 4-di Lolophenyl group, 2,5-dichlorophenyl group, 2,6-dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2,4,6-trichlorophenyl group, 4-chloro-3-nitrophenyl group 3-chloro-4-methylphenyl group, 4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 3,4-difluoro Phenyl group, 4-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 2-trifluoromethylphenyl group, 3,5-bis (trifluoro) phenyl group, 4-trifluoromethoxyphenyl group, 4-nitro phenyl group, 3-nitrophenyl group, a 2-nitrophenyl group, 3,5-dinitrophenyl group, a naphthyl group, an unsubstituted or substituted aryl group is selected from the group consisting of anthryl and phenanthryl groups, I-2) R ″ ′ in the formula is a hydrogen atom, an unsubstituted alkyl group, or an unsubstituted or substituted phenyl group selected from the group consisting of a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. Or it is a substituted aryl group .
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