WO2020036023A1 - ポリイソシアヌレート原料組成物、及びポリイソシアヌレートの製造方法 - Google Patents
ポリイソシアヌレート原料組成物、及びポリイソシアヌレートの製造方法 Download PDFInfo
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- WO2020036023A1 WO2020036023A1 PCT/JP2019/027532 JP2019027532W WO2020036023A1 WO 2020036023 A1 WO2020036023 A1 WO 2020036023A1 JP 2019027532 W JP2019027532 W JP 2019027532W WO 2020036023 A1 WO2020036023 A1 WO 2020036023A1
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- WIPO (PCT)
- Prior art keywords
- group
- carbon atoms
- polyisocyanurate
- compound
- alkyl group
- Prior art date
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- 229920000582 polyisocyanurate Polymers 0.000 title claims abstract description 248
- 239000000203 mixture Substances 0.000 title claims abstract description 166
- 239000002994 raw material Substances 0.000 title claims abstract description 132
- 239000011495 polyisocyanurate Substances 0.000 title claims description 246
- 238000004519 manufacturing process Methods 0.000 title claims description 69
- 150000001875 compounds Chemical class 0.000 claims abstract description 324
- 239000012948 isocyanate Substances 0.000 claims abstract description 162
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 151
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 137
- 239000004593 Epoxy Substances 0.000 claims abstract description 128
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 107
- 125000004663 dialkyl amino group Chemical group 0.000 claims abstract description 68
- 125000003118 aryl group Chemical group 0.000 claims abstract description 61
- 125000005843 halogen group Chemical group 0.000 claims abstract description 57
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 52
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 52
- 125000003277 amino group Chemical group 0.000 claims abstract description 34
- 125000004432 carbon atom Chemical group C* 0.000 claims description 374
- 125000003545 alkoxy group Chemical group 0.000 claims description 78
- 239000003054 catalyst Substances 0.000 claims description 77
- 238000010438 heat treatment Methods 0.000 claims description 47
- 238000002156 mixing Methods 0.000 claims description 39
- 239000000853 adhesive Substances 0.000 claims description 31
- 230000001070 adhesive effect Effects 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 22
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 10
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 8
- 239000005056 polyisocyanate Substances 0.000 claims description 8
- 229920001228 polyisocyanate Polymers 0.000 claims description 8
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 7
- QXRRAZIZHCWBQY-UHFFFAOYSA-N 1,1-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1(CN=C=O)CCCCC1 QXRRAZIZHCWBQY-UHFFFAOYSA-N 0.000 claims description 6
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 abstract 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 abstract 1
- 125000003709 fluoroalkyl group Chemical group 0.000 abstract 1
- 229910052698 phosphorus Inorganic materials 0.000 description 44
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 37
- 239000011574 phosphorus Substances 0.000 description 37
- -1 aliphatic isocyanate Chemical class 0.000 description 23
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 19
- 238000005187 foaming Methods 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- 238000005829 trimerization reaction Methods 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 239000007795 chemical reaction product Substances 0.000 description 15
- 125000001424 substituent group Chemical group 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 14
- 125000001931 aliphatic group Chemical group 0.000 description 12
- 238000004770 highest occupied molecular orbital Methods 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 11
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 8
- 125000004437 phosphorous atom Chemical group 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 150000001721 carbon Chemical group 0.000 description 7
- 238000005755 formation reaction Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 125000000962 organic group Chemical group 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910000975 Carbon steel Inorganic materials 0.000 description 5
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 239000010962 carbon steel Substances 0.000 description 5
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 5
- 125000006239 protecting group Chemical group 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- HQALMCRHKZQISO-UHFFFAOYSA-N 2-ethyloxirane Chemical compound CCC1CO1.CCC1CO1 HQALMCRHKZQISO-UHFFFAOYSA-N 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Chemical class 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 2
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 2
- 238000003775 Density Functional Theory Methods 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000010511 deprotection reaction Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003077 quantum chemistry computational method Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- XFZJGFIKQCCLGK-UHFFFAOYSA-M 1,1-dimethyl-4-phenylpiperazinium iodide Chemical compound [I-].C1C[N+](C)(C)CCN1C1=CC=CC=C1 XFZJGFIKQCCLGK-UHFFFAOYSA-M 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical group O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 description 1
- ZQHOBMCUHOGGTD-UHFFFAOYSA-N 1,3-diisocyanato-1,2,3,3a,4,5-hexahydropentalene Chemical compound C1CC2C(CC(C2=C1)N=C=O)N=C=O ZQHOBMCUHOGGTD-UHFFFAOYSA-N 0.000 description 1
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 1
- ICLCCFKUSALICQ-UHFFFAOYSA-N 1-isocyanato-4-(4-isocyanato-3-methylphenyl)-2-methylbenzene Chemical compound C1=C(N=C=O)C(C)=CC(C=2C=C(C)C(N=C=O)=CC=2)=C1 ICLCCFKUSALICQ-UHFFFAOYSA-N 0.000 description 1
- LYDHLGJJJAWBDY-UHFFFAOYSA-N 1-isocyanato-4-[2-(4-isocyanatocyclohexyl)propan-2-yl]cyclohexane Chemical compound C1CC(N=C=O)CCC1C(C)(C)C1CCC(N=C=O)CC1 LYDHLGJJJAWBDY-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
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- OWEBGWBRTKTKHR-UHFFFAOYSA-N 2-[4-[4-(oxiran-2-yl)phenyl]phenyl]oxirane Chemical group C1OC1C1=CC=C(C=2C=CC(=CC=2)C2OC2)C=C1 OWEBGWBRTKTKHR-UHFFFAOYSA-N 0.000 description 1
- WDGCBNTXZHJTHJ-UHFFFAOYSA-N 2h-1,3-oxazol-2-id-4-one Chemical group O=C1CO[C-]=N1 WDGCBNTXZHJTHJ-UHFFFAOYSA-N 0.000 description 1
- HVMHLMJYHBAOPL-UHFFFAOYSA-N 4-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)propan-2-yl]-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2OC2CC1C(C)(C)C1CC2OC2CC1 HVMHLMJYHBAOPL-UHFFFAOYSA-N 0.000 description 1
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 1
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 description 1
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- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- 101000653548 Homo sapiens Trichoplein keratin filament-binding protein Proteins 0.000 description 1
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- 101100189356 Mus musculus Papolb gene Proteins 0.000 description 1
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- 102100030645 Trichoplein keratin filament-binding protein Human genes 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
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- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
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- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
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- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
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- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
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- 238000009499 grossing Methods 0.000 description 1
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
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- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ABCGFHPGHXSVKI-UHFFFAOYSA-O meso-tetrakis(n-methyl-4-pyridyl)porphine(4+) Chemical compound C1=C[N+](C)=CC=C1C(C1=CC=C(N1)C(C=1C=C[N+](C)=CC=1)=C1C=CC(=N1)C(C=1C=C[N+](C)=CC=1)=C1C=CC(N1)=C1C=2C=C[N+](C)=CC=2)=C2N=C1C=C2 ABCGFHPGHXSVKI-UHFFFAOYSA-O 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000006606 n-butoxy group Chemical group 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
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 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
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000035484 reaction time Effects 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
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 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
- YCCHNFGPIFYNTF-UHFFFAOYSA-N tertiary cymene hydroperoxide Natural products CC1=CC=C(C(C)(C)OO)C=C1 YCCHNFGPIFYNTF-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- KGLSETWPYVUTQX-UHFFFAOYSA-N tris(4-isocyanatophenoxy)-sulfanylidene-$l^{5}-phosphane Chemical compound C1=CC(N=C=O)=CC=C1OP(=S)(OC=1C=CC(=CC=1)N=C=O)OC1=CC=C(N=C=O)C=C1 KGLSETWPYVUTQX-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/003—Polymeric products of isocyanates or isothiocyanates with epoxy compounds having no active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
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- 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
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
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- C08G18/166—Catalysts not provided for in the groups C08G18/18 - C08G18/26
- C08G18/168—Organic compounds
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1883—Catalysts containing secondary or tertiary amines or salts thereof having heteroatoms other than oxygen and nitrogen
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/725—Combination of polyisocyanates of C08G18/78 with other polyisocyanates
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/757—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the cycloaliphatic ring by means of an aliphatic group
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
-
- 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
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4028—Isocyanates; Thioisocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/50—Phosphorus bound to carbon only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5397—Phosphine oxides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on 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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/02—Polyureas
Definitions
- the present invention relates to a polyisocyanurate raw material composition and a method for producing polyisocyanurate.
- the present invention also relates to a polyisocyanurate production kit, a cured polyisocyanurate raw material, a catalyst for a polyisocyanurate production reaction, and an adhesive using the polyisocyanurate raw material composition.
- Polyisocyanurate is a resin in which isocyanurate rings are arbitrarily linked. It is said that heat resistance and flame retardancy are improved by introducing an isocyanurate ring structure into a polyurethane foam, but polyisocyanurate itself has not been used industrially.
- Polyisocyanurate is synthesized by a trimerization reaction of a polyfunctional isocyanate.
- tertiary amines, quaternary ammonium salts, metal salts, and the like have been used as a catalyst for the isocyanate trimerization reaction (for example, Patent Document 1).
- catalysts such as tertiary amines, quaternary ammonium salts, and metal salts have high hygroscopicity and cause foaming during thermosetting.
- examples of the catalyst having low hygroscopicity include a phosphorus catalyst.
- a phosphorus catalyst the reaction efficiency of the polyfunctional isocyanate trimerization reaction is low, and a sufficient amount of isocyanurate rings for thermosetting cannot be generated.
- the present invention has been made in view of the above circumstances, less foaming during heat curing, a method for producing a polyisocyanurate having good curability, and a polyisocyanurate raw material composition usable for the production method, It is an object to provide a polyisocyanurate production kit and a catalyst for a polyisocyanurate production reaction. It is another object of the present invention to provide a polyisocyanurate with less foaming, that is, a cured material of a polyisocyanurate raw material, which is produced by the production method. Another object of the present invention is to provide an adhesive using the polyisocyanurate raw material composition.
- a polyisocyanurate raw material composition comprising a polyfunctional isocyanate, a compound (I) represented by the following general formula (I), and an epoxy compound.
- R 1 and R 2 each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, amino A monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
- both R 1 and R 2 do not become hydrogen atoms.
- R 3 to R 5 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, Represents a monoalkylamino group, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
- Each of the three R 1 to R 5 may be the same or different.
- a polyisocyanurate raw material composition comprising a polyfunctional isocyanate and a compound (I) represented by the following general formula (I).
- R 1 and R 2 each independently represent a hydrogen atom, an alkoxy group having 1 to 12 carbon atoms, an alkyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, amino A monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
- both R 1 and R 2 do not become hydrogen atoms.
- R 3 to R 5 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, Represents a monoalkylamino group, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
- Each of the three R 1 to R 5 may be the same or different.
- the polyfunctional isocyanate is at least one selected from the group consisting of diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, bis (isocyanatomethyl) cyclohexane, and modified polyisocyanates thereof.
- the polyisocyanurate raw material composition according to any one of 1) to [3].
- R 1 and R 2 in the general formula (I) each independently represent a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, a monoalkylamino group having 1 to 4 carbon atoms, or a group having 2 to 2 carbon atoms.
- a kit for producing a polyisocyanurate comprising: (a) a polyfunctional isocyanate, (b) a compound represented by the following general formula (I), and (c) an epoxy compound; (C) Kits housed in different containers.
- R 1 and R 2 each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, amino A monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
- both R 1 and R 2 do not become hydrogen atoms.
- R 3 to R 5 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, Represents a monoalkylamino group, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
- Each of the three R 1 to R 5 may be the same or different.
- a kit for producing a polyisocyanurate comprising (d) a composition containing a polyfunctional isocyanate and a compound (I) represented by the following general formula (I), and (c) an epoxy compound, (D) and (c) are each housed in different containers.
- R 1 and R 2 each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, amino A monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
- both R 1 and R 2 do not become hydrogen atoms.
- R 3 to R 5 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, Represents a monoalkylamino group, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
- Each of the three R 1 to R 5 may be the same or different.
- a polystyrene comprising: (d) a composition containing a polyfunctional isocyanate and a compound (I) represented by the following general formula (I); and (e) a composition containing a polyfunctional isocyanate and an epoxy compound.
- R 1 and R 2 each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, amino A monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
- both R 1 and R 2 do not become hydrogen atoms.
- R 3 to R 5 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, Represents a monoalkylamino group, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
- Each of the three R 1 to R 5 may be the same or different.
- a polyisocyanurate production kit comprising: (e) a composition containing a polyfunctional isocyanate and an epoxy compound; and (b) a compound (I) represented by the following general formula (I),
- the kits (e) and (b) are housed in different containers.
- R 1 and R 2 each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, amino A monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
- both R 1 and R 2 do not become hydrogen atoms.
- R 3 to R 5 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, Represents a monoalkylamino group, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
- Each of the three R 1 to R 5 may be the same or different.
- the polyfunctional isocyanate is at least one selected from the group consisting of diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, bis (isocyanatomethyl) cyclohexane, and modified polyisocyanates thereof.
- R 1 and R 2 in the general formula (I) each independently represent a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, a monoalkylamino group having 1 to 4 carbon atoms, or a group having 2 to 2 carbon atoms. 8.
- R 1 and R 2 each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 2 to 10 carbon atoms, and a carbon atom having 6 to 12 carbon atoms.
- both R 1 and R 2 do not become hydrogen atoms.
- R 3 to R 5 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, Represents a monoalkylamino group, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
- Each of the three R 1 to R 5 may be the same or different.
- an epoxy compound (i) a reaction product of an epoxy compound and a polyfunctional isocyanate, (iii) a reaction product of the epoxy compound and the compound (I), and (iv) an epoxy compound and an epoxy compound
- the polyisocyanurate raw material cured product according to [14] comprising at least one compound selected from the group consisting of: [16] R 1 and R 2 in the general formulas (I) and (I ′) each independently represent a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, a monoalkylamino group having 1 to 4 carbon atoms, Or the polyisocyanurate raw material cured product according to [14] or [15], which is a dialkylamino group having 2 to 8 carbon atoms (however, both R 1 and R 2 are not hydrogen atoms).
- a mixing step of mixing a polyfunctional isocyanate, a compound (I) represented by the following general formula (I), and an epoxy compound, and a heating step of heating the mixture obtained in the mixing step A method for producing a polyisocyanurate.
- R 1 and R 2 each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, amino A monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
- both R 1 and R 2 do not become hydrogen atoms.
- R 3 to R 5 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, Represents a monoalkylamino group, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
- Each of the three R 1 to R 5 may be the same or different.
- the polyfunctional isocyanate is at least one selected from the group consisting of diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, bis (isocyanatomethyl) cyclohexane, and modified polyisocyanates thereof. 17] The method for producing a polyisocyanurate according to any one of [21].
- R 1 and R 2 in the general formula (I) each independently represent a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, a monoalkylamino group having 1 to 4 carbon atoms, or a group having 2 to 2 carbon atoms.
- a catalyst for a polyisocyanurate production reaction comprising a combination of a compound (I) represented by the following general formula (I) and an epoxy compound.
- R 1 and R 2 each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, amino A monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
- both R 1 and R 2 do not become hydrogen atoms.
- R 3 to R 5 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, Represents a monoalkylamino group, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
- Each of the three R 1 to R 5 may be the same or different.
- a kit for producing a polyisocyanurate comprising a combination of a compound (I) represented by the following general formula (I) and an epoxy compound as a catalyst for a polyisocyanurate production reaction.
- R 1 and R 2 each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, amino A monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
- R 1 and R 2 do not become hydrogen atoms.
- R 3 to R 5 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, Represents a monoalkylamino group, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
- Each of the three R 1 to R 5 may be the same or different.
- An adhesive comprising the polyisocyanurate raw material composition according to any one of [1] to [5].
- a method for producing a polyisocyanurate with less foaming during thermosetting and good curability, and a polyisocyanurate raw material composition, a polyisocyanurate production kit and a polyisocyanurate production kit that can be used in the production method A catalyst for an isocyanurate production reaction is provided. Further, there is provided a polyisocyanurate having a low foaming, that is, a cured material of a polyisocyanurate raw material, which is produced by the production method. Further, an adhesive using the polyisocyanurate raw material composition is provided.
- FIG. 15 is a scatter diagram illustrating the relationship between the HOMO level and the average charge at the ortho position of the compounds described in Table 14.
- polyisocyanurate refers to a compound having a structure in which a plurality of isocyanurate rings are arbitrarily linked via a divalent organic group.
- polyisocyanurate raw material composition refers to a composition containing either or both of a polyisocyanurate raw material (a reaction product of a polyisocyanurate production reaction) and a polyisocyanurate production reaction catalyst.
- polyisocyanurate or “polyisocyanurate” refers to those used for production of a cured material of a raw material.
- the "kit for producing polyisocyanurate” is a kit containing a raw material for polyisocyanurate and a catalyst for a polyisocyanurate production reaction, and is used for producing a cured product of polyisocyanurate or polyisocyanurate raw material. It is something that can be done.
- the “cured material of polyisocyanurate raw material” refers to a cured product containing polyisocyanurate obtained by heating a polyisocyanurate raw material composition.
- the carbon number does not include the carbon number of the substituent.
- the present invention provides a polyisocyanurate comprising a polyfunctional isocyanate, a compound represented by the following general formula (I) (hereinafter, also referred to as “compound (I)”), and an epoxy compound.
- a raw material composition is provided.
- R 1 and R 2 each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, amino A monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
- both R 1 and R 2 do not become hydrogen atoms.
- R 3 to R 5 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, Represents a monoalkylamino group, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
- Each of the three R 1 to R 5 may be the same or different.
- the polyfunctional isocyanate those generally used for the production of polyisocyanurate can be used without particular limitation.
- the number of isocyanato groups contained in the polyfunctional isocyanate is not particularly limited as long as it is two or more, but is preferably 2 to 5, more preferably 2 or 3, and still more preferably 2.
- the polyfunctional isocyanate include an aliphatic isocyanate and an aromatic isocyanate.
- the aliphatic isocyanate is a polyfunctional isocyanate containing an aliphatic hydrocarbon group and two or more isocyanato groups.
- the aliphatic hydrocarbon group may be a linear or branched aliphatic hydrocarbon group, or may be an aliphatic hydrocarbon group containing a ring in the structure.
- Examples of the aliphatic hydrocarbon group having a ring in the structure include an alicyclic group, a group in which an alicyclic group is bonded to a terminal of a linear or branched aliphatic hydrocarbon group, and an alicyclic group.
- a group interposed in the middle of a chain or branched aliphatic hydrocarbon group may, for example, be mentioned.
- the aliphatic hydrocarbon group preferably has 1 to 15 carbon atoms, more preferably has 3 to 10 carbon atoms, and still more preferably has 5 to 10 carbon atoms.
- Aromatic isocyanate is a polyfunctional isocyanate containing at least one aromatic ring and two or more isocyanato groups.
- the aromatic ring is not particularly limited as long as it is a cyclic conjugated system having (4n + 2) ⁇ electrons, and may be monocyclic or polycyclic.
- the aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring.
- the number of carbon atoms in the aromatic ring is preferably from 6 to 15, more preferably from 6 to 12.
- the number of aromatic rings contained in the aromatic isocyanate is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1 or 2.
- the aromatic isocyanate may contain an aliphatic hydrocarbon group in addition to the aromatic ring and the isocyanato group. Examples of the aliphatic hydrocarbon group include the same groups as those described above as the aliphatic hydrocarbon group in the aliphatic isocyanate.
- aliphatic isocyanate examples include tetramethylene-1,4-diisocyanate, pentamethylene-1,5-diisocyanate, hexamethylene-1,6-diisocyanate, octamethylene-1,8-diisocyanate, dodecamethylene-1, 12-diisocyanate, 2,2,4-trimethylhexamethylene-1,6-diisocyanate, 2,4,4-trimethylhexamethylene-1,6-diisocyanate, 1-isocyanate-3,3,5-trimethyl-5 -Isocyanatomethylcyclohexanecis-cyclohexane-1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexanetrans-cyclohexane-1,4-diisocyanate, dicyclohexylmethane- , 4'-diisocyanate, ⁇ ,
- aromatic isocyanate examples include tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, diphenylmethane-2,4′-diisocyanate, diphenylmethane-4,4′-diisocyanate, and naphthylene-1,5-diisocyanate.
- Tolylene diisocyanate, vitrylene diisocyanate, anisidine diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, diphenylether-4,4'-diisocyanate, triphenylmethane-4,4 ', 4 "- Examples include, but are not limited to, triisocyanate, tris (4-isocyanatophenyl) thiophosphate, xylylene-1,3-diisocyanate, xylylene-1,4-diisocyanate, and the like.
- the polyfunctional isocyanate is a polyphenylpolymethylene polyisocyanate of the type obtained by condensing aniline with formalin and then phosgenating, at room temperature containing a carbodiimide group or a uretonimine group as described in German Patent No. 1092007.
- Liquid diphenylmethane diisocyanates, or modified polyisocyanates containing a urethane bond, an allophanate bond, an isocyanurate ring structure, a urea bond, a biuret bond, a uretdione ring structure, or the like may be used.
- the polyfunctional isocyanate may be an isocyanate-based prepolymer obtained by excessively reacting the above-described isocyanate with a polyol used in the urethane industry.
- polyfunctional isocyanate diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, bis (isocyanatomethyl) cyclohexane, and modified polyisocyanates thereof are preferable.
- a commercially available polyfunctional isocyanate may be used.
- Commercially available polyfunctional isocyanates include, for example, Millionate (registered trademark) MT (Tosoh), Coronate (registered trademark) T-65 (Tosoh), Coronate (registered trademark) T-80 (Tosoh), Coronate (registered trademark) T-100 (Tosoh), HDI (Tosoh), Duranate (registered trademark) 50M (Asahi Kasei Chemicals), Takenate (registered trademark) 600 (Mitsui Chemicals), Coronate (registered trademark) HX (Tosoh), Duranate (registered trademark) TPA -100 (Asahi Kasei Chemicals), Duranate (registered trademark) 24A-100 (Asahi Kasei Chemicals), Duranate (registered trademark) D201 (Asahi Kasei Chemicals) and the like.
- the polyfunctional isocyanate may be one in which an isocyanate group is blocked.
- "Isocyanato group blocked” means that the isocyanato group is protected by a protecting group.
- the protecting group those generally used as a protecting group for an isocyanato group can be used without particular limitation.
- the polyfunctional isocyanate one type may be used alone, or two or more types may be used in combination.
- the ratio of the polyfunctional isocyanate in the polyisocyanurate raw material composition of the present embodiment is, for example, 80 mol% or more and less than 100 mol%.
- the proportion of the polyfunctional isocyanate in the polyisocyanurate raw material composition is preferably from 85 mol% to 99.99 mol%, more preferably from 90 mol% to 98 mol%, and still more preferably from 93 mol% to 97 mol%. .
- the proportion of the polyfunctional isocyanate is at least the lower limit of the above range, good heat resistance can be realized.
- the proportion of the polyfunctional isocyanate is not more than the upper limit of the above range, it is easy to balance with other components.
- Compound (I) is a compound represented by the following general formula (I).
- R 1 and R 2 each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, amino A monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
- both R 1 and R 2 do not become hydrogen atoms.
- R 3 to R 5 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, Represents a monoalkylamino group, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
- Each of the three R 1 to R 5 may be the same or different.
- R 1 and R 2 each independently represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, amino A monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
- both R 1 and R 2 do not become hydrogen atoms.
- the alkoxy group having 1 to 10 carbon atoms in R 1 and R 2 preferably has 1 to 4 carbon atoms, more preferably has 1 to 3 carbon atoms, and still more preferably has 1 or 2 carbon atoms.
- An alkoxy group is a group represented by -OR (R is an alkyl group).
- R is an alkyl group.
- the alkyl group for R may be linear or branched, and may have a ring in the structure. preferable. Examples of the alkyl group include those similar to the methyl group and the alkyl group having 2 to 10 carbon atoms described below.
- alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group and a tert-butoxy group. Among them, a methoxy group or an ethoxy group is preferable, and a methoxy group is more preferable.
- the alkyl group having 2 to 10 carbon atoms in R 1 and R 2 may be linear or branched, and may have a ring in the structure.
- the alkyl group having 2 to 10 carbon atoms in R 1 and R 2 preferably has 2 to 5 carbon atoms, and more preferably 2 or 3 carbon atoms.
- linear or branched alkyl group examples include an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, Examples include an isopentyl group and a sec-pentyl group.
- the linear or branched alkyl group for R 1 and R 2 may have a substituent.
- “may have a substituent” means that a hydrogen atom (—H) of a hydrocarbon group may be substituted with a monovalent group.
- substituents examples include an amino group, a carboxy group, a cyano group, and a halogen atom.
- halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- linear or branched alkyl group for R 1 and R 2 those having no substituent are more preferable.
- Examples of the alkyl group having a ring in the structure include a cycloalkyl group, a group in which a cycloalkane ring is bonded to a terminal of a linear or branched alkyl group, and a cycloalkyl group in the middle of a linear or branched alkyl group. And a group having an alkane ring interposed.
- the cycloalkane ring may be monocyclic or polycyclic, but is preferably monocyclic.
- alkyl group having a ring in the structure examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a group in which a linear or branched alkyl group is bonded to the cycloalkyl group.
- the alkyl group containing a ring in the structure of R 1 and R 2 may have a substituent. Examples of the substituent include an amino group, a carboxy group, a cyano group, and a halogen atom.
- the aryl group having 6 to 12 carbon atoms in R 1 and R 2 preferably has 6 to 10 carbon atoms.
- Specific examples of the aryl group include a phenyl group, a tolyl group, an o-xylyl group, a naphthyl group, a biphenyl group and the like.
- the aryl group having 6 to 12 carbon atoms in R 1 and R 2 may have a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an amino group, a carboxy group, a cyano group, and a halogen atom.
- the fluorinated alkyl group having 1 to 10 carbon atoms in R 1 and R 2 preferably has 1 to 5 carbon atoms, more preferably has 1 to 3 carbon atoms, and still more preferably has 1 or 2 carbon atoms.
- Specific examples of the fluorinated alkyl group having 1 to 10 carbon atoms for R 1 and R 2 include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group and the alkyl groups exemplified as the alkyl groups having 2 to 10 carbon atoms. And a group in which part or all of the hydrogen atoms of the above are substituted with fluorine atoms.
- halogen atom in R 1 and R 2 examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, a fluorine atom is preferable as the halogen atom in R 1 and R 2 .
- Each alkyl group in the monoalkylamino group having 1 to 10 carbon atoms or the dialkylamino group having 2 to 20 carbon atoms in R 1 and R 2 preferably has 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, The numbers 1 to 3 are more preferable, and the numbers 1 or 2 are more preferable.
- the alkyl group may be linear or branched, and may have a ring in the structure.
- Specific examples of the monoalkylamino group having 1 to 10 carbon atoms or the dialkylamino group having 2 to 20 carbon atoms in R 1 and R 2 include a methylamino group, a dimethylamino group, and a hydrogen atom of the amino group. Examples thereof include groups in which one or two are substituted with the alkyl groups exemplified as the alkyl groups having 2 to 10 carbon atoms.
- R 1 and R 2 are preferably an electron donating group from the viewpoint of reactivity. At least one of R 1 and R 2 is preferably an electron donating group, and more preferably both R 1 and R 2 are electron donating groups. Specific examples of the electron donating group include, for example, an alkoxy group and an amino group. More specifically, R 1 and R 2 each independently represent an alkoxy group having 1 to 10 carbon atoms, an amino group, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
- a hydrogen atom preferably an alkoxy group having 1 to 10 carbon atoms, a monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, or a hydrogen atom, more preferably an alkoxy group having 1 to 4 carbon atoms.
- a monoalkylamino group having 1 to 4 carbon atoms, a dialkylamino group having 2 to 8 carbon atoms or a hydrogen atom is more preferable.
- R 1 and R 2 are preferably an ethoxy group, a methoxy group, a methylamino group, a dimethylamino group or a hydrogen atom, and particularly preferably a hydrogen atom, a methylamino group, a dimethylamino group or a methoxy group.
- R 1 and R 2 do not become hydrogen atoms.
- Preferred combinations of R 1 and R 2 include a combination of electron donating groups and a combination of an electron donating group and a hydrogen atom.
- each of three R 1 and R 2 may be the same or different.
- Three R 1 may be different from each other, two of three may be the same and one may be different, all three may be the same, but all three R 1 are the same
- Three R 2 may be different from each other, two of three may be the same and one may be different, or all three may be the same, but all three R 2 are the same It is preferred that
- R 3 to R 5 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, amino A monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
- the alkyl group having 1 to 10 carbon atoms in R 3 to R 5 preferably has 1 to 5 carbon atoms, more preferably has 1 to 3 carbon atoms, and still more preferably has 1 or 2 carbon atoms.
- Examples of the alkyl group having 1 to 10 carbon atoms for R 3 to R 5 include a methyl group and those similar to the alkyl groups having 2 to 10 carbon atoms for R 1 and R 2 .
- the alkoxy group having 1 to 10 carbon atoms in R 3 to R 5 preferably has 1 to 4 carbon atoms, more preferably has 1 to 3 carbon atoms, and still more preferably has 1 or 2 carbon atoms.
- Specific examples of the alkoxy group having 1 to 10 carbon atoms include those similar to the alkoxy groups having 1 to 10 carbon atoms for R 1 and R 2 .
- the alkoxy group having 1 to 10 carbon atoms in R 3 to R 5 is preferably a methoxy group or an ethoxy group, and more preferably a methoxy group.
- R 1 and R 2 an aryl group having 6 to 12 carbon atoms, a fluorinated alkyl group having 1 to 10 carbon atoms, a monoalkylamino group having 1 to 10 carbon atoms, and a dialkylamino having 2 to 20 carbon atoms And the same groups as those described above as the halogen group.
- R 3 to R 5 are preferably a hydrogen atom or an electron donating group from the viewpoint of reactivity. More specifically, R 3 to R 5 are preferably a hydrogen atom, an alkoxy group, an amino group, a monoalkylamino group, or a dialkylamino group, and are preferably a hydrogen atom, an alkoxy group, a monoalkylamino group, or a dialkylamino group. More preferred.
- each of three R 3 to R 5 may be the same or different.
- Three R 3 may be different from each other, two of three may be the same and one may be different, or all three may be the same, but all three R 3 are the same
- Three R 4 may be different from each other, two of three may be the same and one may be different, or all three may be the same, but all three R 4 are the same
- Three R 5 may be different from each other, two of three may be the same and one may be different, or all three may be the same, but all three R 5 are the same It is preferred that
- Preferable examples of the compound (I) represented by the general formula (I) include a compound represented by the following general formula (I-1).
- R 1, R 2 and R 4 are the same as R 1, R 2 and R 4 in the general formula (I). Each of the three R 1 , R 2 and R 4 may be the same or different. ]
- R 1 and R 2 include the same as those described as R 1 and R 2 in the general formula (I).
- R 1 and R 2 are preferably an alkoxy group having 1 to 10 carbon atoms, a monoalkylamino group having 1 to 10 carbon atoms, or a dialkylamino group having 2 to 20 carbon atoms.
- the alkoxy group having 1 to 10 carbon atoms is preferably 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, further preferably an ethoxy group or a methoxy group, and particularly preferably a methoxy group.
- the alkyl group of the monoalkylamino group having 1 to 10 carbon atoms or the dialkylamino group having 2 to 20 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. , A methylamino group or a dimethylamino group is more preferred.
- R 4 examples include the same ones as those described as R 4 in the general formula (I).
- R 4 is preferably a hydrogen atom or an alkoxy group having 1 to 10 carbon atoms.
- the alkoxy group having 1 to 10 carbon atoms is preferably 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, further preferably an ethoxy group or a methoxy group, and particularly preferably a methoxy group.
- compound (I) examples include phosphorus catalyst Nos. Listed in Tables 15 to 20 described below. Also included are compounds from 12 to 170.
- the ratio of the compound (I) in the polyisocyanurate raw material composition of the present embodiment is, for example, more than 0 mol% and 10 mol% or less.
- the proportion of compound (I) in the polyisocyanurate raw material composition is preferably from 0.001 mol% to 5 mol%, more preferably from 0.01 mol% to 2 mol%, and more preferably from 0.05 mol% to 2 mol%. % Is more preferable.
- the proportion of the compound (I) is at least the lower limit of the above range, good reaction efficiency can be realized.
- the proportion of the compound (I) is at most the upper limit of the above range, it will be easier to balance with other components.
- the epoxy compound in the present embodiment is a compound containing one or more epoxy groups.
- the epoxy compound those generally used for the trimerization reaction of isocyanate can be used without particular limitation.
- the epoxy equivalent of the epoxy compound is not particularly limited, but is preferably from 50 g / mol to 1000 g / mol, more preferably from 100 g / mol to 500 g / mol, and still more preferably from 100 g / mol to 300 g / mol.
- the epoxy compound include, for example, monoepoxides such as allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, butylene oxide, propylene oxide, octylene oxide, styrene oxide, glycidol, and glycidyl ester of versatic acid;
- monoepoxides such as allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, butylene oxide, propylene oxide, octylene oxide, styrene oxide, glycidol, and glycidyl ester of versatic acid
- Diglycidyl 1,2-cyclohexanedicarboxylate diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, butadiene epoxide, 3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexanecarboxylate, bicyclohexene dioxide, 4,4'-di (1,2-epoxyethyl) diphenyl ether, 4,4'-di (1,2-epoxyethyl) biphenyl, 2,2-bis (3,4-epoxycyclohexyl) propane, di-resorcinol Glycidyl ether, diglycidyl ether of methylphloroglysin, bis (2,3-epoxycyclopentyl) ether, 2- (3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxy-6-methylcyclohexyl
- Triglycidyl isocyanurate triglycidyl ether of para-aminophenol, polyallyl glycidyl ether, 1,3,5- (1,2-epoxyethyl) benzene-2,2′-4,4′-tetraglycidoxybenzophenone, Examples thereof include tri- or higher-functional epoxides such as tetraglycidoxytetraphenylethane, polyglycidyl ether of phenol novolak, polyglycidyl ether of cresol novolak, triglycidyl ether of glycerin, and triglycidyl ether of trimethylolpropane.
- tri- or higher-functional epoxides such as tetraglycidoxytetraphenylethane, polyglycidyl ether of phenol novolak, polyglycidyl ether of cresol novolak, triglycidyl ether of glycerin
- epoxy compounds include phenyl glycidyl ether, styrene oxide, diglycidyl 1,2-cyclohexanedicarboxylate, diglycidyl ether of bisphenol A, triglycidyl isocyanurate, polyglycidyl ether of phenol novolak, and polyglycidyl ether of cresol novolak And the like are preferable because they can be easily obtained industrially.
- the proportion of the epoxy compound in the polyisocyanurate raw material composition of the present embodiment is, for example, more than 0 mol% and 20 mol% or less.
- the proportion of compound (I) in the polyisocyanurate raw material composition is preferably from 0.001 mol% to 15 mol%, more preferably from 0.005 mol% to 10 mol%, and more preferably from 0.1 mol% to 7 mol%. % Is more preferable.
- the proportion of the compound (I) is at least the lower limit of the above range, good reaction efficiency can be realized.
- the proportion of the compound (I) is at most the upper limit of the above range, it will be easier to balance with other components.
- the ratio (molar ratio) of the epoxy compound to the polyfunctional isocyanate is preferably 100 / 0.001 to 100/15, more preferably 100 / 0.005 to 100/10, and more preferably 100 / 0.005 to 100/10. 1 to 100/7 is more preferred.
- the polyisocyanurate raw material composition of the present embodiment may contain other components in addition to the polyfunctional isocyanate, the compound (I) and the epoxy compound.
- Other components include, for example, solvents, curing accelerators, silane coupling agents, antioxidants, release agents, defoamers, emulsifiers, thixotropic agents, smoothing agents, flame retardants, pigments, fillers, shrinkage
- An example is a relaxation agent.
- the trimerization reaction of the polyfunctional isocyanate proceeds, and polyisocyanurate is generated.
- the compound (I) and the epoxy compound mainly function as a catalyst for a trimerization reaction of the polyfunctional isocyanate.
- Phosphorus catalysts generally have low hygroscopicity and suppress foaming during heating.
- the reactivity is low and sufficient curability (yield) cannot be obtained. There was a problem.
- the compound (I) exhibits a high reactivity when used as a catalyst for the polyisocyanurate formation reaction by having the specific structure represented by the general formula (I), as shown in Examples described later. And sufficient curability (yield) can be realized. That is, since the compound (I) has low hygroscopicity and high reactivity as a catalyst, foaming can be suppressed and sufficient curability can be obtained when thermally cured.
- the present invention provides a polyisocyanurate raw material composition comprising a polyfunctional isocyanate and a compound (I).
- polyfunctional isocyanate The polyfunctional isocyanate is the same as that described in the description of the first embodiment. Preferred examples of the polyfunctional isocyanate include those similar to those described in the first embodiment. Among them, as the polyfunctional isocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, bis (isocyanatomethyl) cyclohexane, and modified polyisocyanates thereof are preferable.
- the proportion of the polyfunctional isocyanate in the polyisocyanurate raw material composition of the present embodiment is, for example, 90 mol% or more and less than 100 mol%.
- the proportion of the polyfunctional isocyanate in the polyisocyanurate raw material composition is preferably from 95 mol% to 99.99 mol%, more preferably from 98 mol% to 99.99 mol%, and more preferably from 98 mol% to 99.95 mol%. The following are more preferred.
- the proportion of the polyfunctional isocyanate is at least the lower limit of the above range, good heat resistance can be realized.
- the proportion of the polyfunctional isocyanate is not more than the upper limit of the above range, it is easy to balance with other components.
- Compound (I) is the same as that described in the description of the first embodiment. Preferred examples of the compound (I) are also the same as those described in the first embodiment.
- R 1 and R 2 in the general formula (I) each independently represent a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, or a monoalkylamino group having 1 to 4 carbon atoms. Or a dialkylamino group having 2 to 8 carbon atoms (however, both R 1 and R 2 are not hydrogen atoms).
- R 1 and R 2 in the aforementioned general formula (I-1) each independently represent a hydrogen atom, a carbon atom or a carbon atom.
- the alkoxy group having 1 to 4 carbon atoms is preferably an alkoxy group having 1 to 3 carbon atoms, more preferably an ethoxy group or a methoxy group, and further preferably a methoxy group.
- the alkyl group of the monoalkylamino group having 1 to 4 carbon atoms or the dialkylamino group having 2 to 8 carbon atoms an alkyl group having 1 to 4 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms is more preferable.
- a methylamino group or a dimethylamino group is more preferred.
- Specific examples of the compound (I) include compounds represented by any of the above formulas (I-1-1) to (I-1-10), and phosphorus catalyst Nos. 12 to 170 compounds.
- the ratio of the compound (I) in the polyisocyanurate raw material composition of the present embodiment is, for example, more than 0 mol% and 10 mol% or less.
- the proportion of compound (I) in the polyisocyanurate raw material composition is preferably from 0.001 mol% to 5 mol%, more preferably from 0.01 mol% to 2 mol%, and more preferably from 0.05 mol% to 2 mol%. % Is more preferable.
- the proportion of the compound (I) is at least the lower limit of the above range, good reaction efficiency can be realized.
- the proportion of the compound (I) is at most the upper limit of the above range, it will be easier to balance with other components.
- the polyisocyanurate raw material composition of the present embodiment may contain other components in addition to the polyfunctional isocyanate and the compound (I).
- the same components as those described in the first embodiment can be used.
- the trimerization reaction of the polyfunctional isocyanate proceeds, and polyisocyanurate is generated.
- the epoxy compound the same compounds as those described in the description of the first embodiment can be used.
- the compound (I) and the epoxy compound mainly function as a catalyst for the trimerization reaction of the polyfunctional isocyanate, similarly to the polyisocyanurate raw material composition of the first embodiment. Since compound (I) has low hygroscopicity and high reactivity as a catalyst, foaming can be suppressed and sufficient curability (yield) can be obtained when heated.
- the kit for producing a polyisocyanurate of the present embodiment includes a polyfunctional isocyanate, a compound (I), and an epoxy compound.
- the kit of the present embodiment includes (a) a polyfunctional isocyanate, (b) a compound (I), (c) an epoxy compound, (d) a composition containing the polyfunctional isocyanate and the compound (I), and (e)
- An example is provided in which a composition containing a polyfunctional isocyanate and an epoxy compound is appropriately combined with a composition containing the composition in different containers.
- the amounts of the polyfunctional isocyanate, the compound (I), and the epoxy compound contained in each container are not particularly limited, but a mixing ratio in which the respective components are mixed during production of the polyisocyanurate. It is preferable to set the amount according to.
- the container is not particularly limited, and may be any container.
- the material of the container may be any material as long as it does not corrode due to the contents, and examples thereof include glass, resin, and metal.
- the present invention is a kit for producing a polyisocyanurate, comprising: (a) a polyfunctional isocyanate, (b) a compound (I), and (c) an epoxy compound, wherein the kit comprises the above (a) to ( c) provides a kit, each contained in a different container.
- polyfunctional isocyanate The polyfunctional isocyanate is the same as that described in the description of the first embodiment in the section “[Polyisocyanurate raw material composition]”. Preferred examples of the polyfunctional isocyanate also include the same ones as those described in the first embodiment of the above-mentioned “[Polyisocyanurate raw material composition]”.
- the compound (I) is the same as that described in the description of the first embodiment in the section “[Polyisocyanurate raw material composition]”. Preferred examples of the compound (I) also include the same compounds as those described in the first embodiment of the above-mentioned “[Polyisocyanurate raw material composition]”.
- the compound (I) is preferably contained in a container in a state of being dissolved in a solvent.
- the solvent is not particularly limited as long as it can dissolve the compound (I), and a known organic solvent or the like can be used.
- epoxy compound The epoxy compound is the same as that described in the description of the first embodiment in the section of “[Polyisocyanurate raw material composition]”. Preferred examples of the epoxy compound also include the same compounds as those described in the first embodiment in the section of “[Polyisocyanurate raw material composition]”.
- polyisocyanurate (a) a polyfunctional isocyanate, (b) compound (I), and (c) an epoxy compound included in the kit of the present embodiment may be mixed. By heating the mixture, the trimerization reaction of the polyfunctional isocyanate proceeds, and polyisocyanurate can be obtained.
- the present invention is a kit for producing a polyisocyanurate, comprising: (d) a composition containing a polyfunctional isocyanate and a compound (I); and (c) an epoxy compound, wherein the (d) And (c) provide kits, each contained in a different container.
- composition (d) The kit of the present embodiment includes a composition containing a polyfunctional isocyanate and the compound (I) (hereinafter, referred to as “composition (d)”).
- composition (d) is the same as the polyisocyanurate raw material composition according to the second embodiment described in the section “[Polyisocyanurate raw material composition]”.
- epoxy compound The epoxy compound is the same as in the kit according to the first embodiment.
- the composition (d) and the epoxy compound (c) included in the kit of the present embodiment may be mixed. By heating the mixture, the trimerization reaction of the polyfunctional isocyanate proceeds, and polyisocyanurate can be obtained.
- the present invention relates to a method for producing a polyisocyanurate, comprising: (d) a composition containing a polyfunctional isocyanate and a compound (I); and (e) a composition containing a polyfunctional isocyanate and an epoxy compound.
- a kit wherein the kits (d) and (e) are provided in different containers.
- composition (d) The composition (d) is the same as the kit according to the second embodiment.
- composition (e) The kit of the present embodiment includes a composition containing a polyfunctional isocyanate and an epoxy compound (hereinafter, referred to as “composition (e)”).
- the polyfunctional isocyanate contained in the composition (e) is the same as that described in the description of the first embodiment in the section “[Polyisocyanurate raw material composition]”.
- Preferred examples of the polyfunctional isocyanate also include the same ones as those described in the first embodiment of the above-mentioned “[Polyisocyanurate raw material composition]”.
- the polyfunctional isocyanate may be the same as or different from the polyfunctional isocyanate contained in the composition (d).
- the epoxy compound contained in the composition (e) is the same as that described in the description of the first embodiment in the section “[Polyisocyanurate raw material composition]”.
- Preferred examples of the epoxy compound also include the same compounds as those described in the first embodiment in the section of “[Polyisocyanurate raw material composition]”.
- composition (d) and the composition (e) included in the kit of the present embodiment may be mixed. By heating the mixture, the trimerization reaction of the polyfunctional isocyanate proceeds, and polyisocyanurate can be obtained.
- the present invention provides a polyisocyanurate production kit comprising (e) a composition containing a polyfunctional isocyanate and an epoxy compound, and (b) a compound (I), wherein the (e) And (b) provide kits, each contained in a different container.
- composition (e) The composition (e) is the same as the kit according to the third embodiment.
- Compound (I) Compound (I) is the same as in the kit according to the first embodiment.
- composition (e) and the compound (b) contained in the kit of the present embodiment may be mixed. By heating the mixture, the trimerization reaction of the polyfunctional isocyanate proceeds, and polyisocyanurate can be obtained.
- kits of the first to fourth embodiments can include arbitrary components in addition to the components listed above.
- examples of the optional configuration include, for example, instructions for producing polyisocyanurate, and a mold for casting the polyisocyanurate raw material composition.
- the polyfunctional isocyanate contained in the kit of the first embodiment or the polyfunctional isocyanate contained in the composition (d) or the composition (e) contained in the kit of the second to fourth embodiments may be used.
- the kits of the first to fourth embodiments may optionally include a reagent for deprotecting the block polyfunctional isocyanate.
- the present invention provides a cured polyisocyanurate raw material obtained by heating a polyisocyanurate raw material composition containing a polyfunctional isocyanate, compound (I), and an epoxy compound.
- the cured polyisocyanurate raw material contains, in addition to polyisocyanurate generated from polyfunctional isocyanate, unreacted polyfunctional isocyanate, dimer, catalyst, modified catalyst, and other impurities.
- the polyisocyanurate is not particularly limited as long as it has a structure in which a plurality of isocyanurate rings are arbitrarily linked via a divalent organic group.
- the structure of polyisocyanurate can be represented, for example, by the following general formula (II).
- R represents a divalent organic group
- n represents an integer of 2 or more.
- a plurality of Rs may be the same or different.
- R is a divalent organic group derived from a polyfunctional isocyanate.
- R is an aliphatic hydrocarbon group (for example, an alkylene group).
- R is an aromatic hydrocarbon group (for example, an arylene group).
- Polyisocyanurate has a structure in which isocyanurate rings are randomly bonded via a divalent organic group, and it is difficult to specify the entire structure.
- the cured polyisocyanurate raw material of the present embodiment may contain a plurality of types of polyisocyanurates having different structures and molecular weights.
- the cured polyisocyanurate raw material of the present embodiment may contain a compound (I) and an epoxy compound as described below, and a reaction product (modified product) thereof.
- the polyfunctional isocyanate is the same as that described in the description of the first embodiment in the section “[Polyisocyanurate raw material composition]”. Preferred examples of the polyfunctional isocyanate also include the same ones as those described in the first embodiment of the above-mentioned “[Polyisocyanurate raw material composition]”.
- the compound (I) is the same as that described in the description of the first embodiment in the above section “[Polyisocyanurate raw material composition]”. Preferred examples of the compound (I) also include the same compounds as those described in the first embodiment of the above-mentioned “[Polyisocyanurate raw material composition]”.
- the epoxy compound is the same as that described in the description of the first embodiment in the above section “[Polyisocyanurate raw material composition]”. Preferred examples of the epoxy compound also include the same compounds as those described in the first embodiment in the section of “[Polyisocyanurate raw material composition]”.
- the cured polyisocyanurate raw material of the present embodiment can be obtained by mixing a polyfunctional isocyanate, the compound (I), and the epoxy compound and heating the mixture. "Heating” can be performed in the same manner as in the heating step described in the section of "[Method for Producing Polyisocyanurate]" below.
- the cured polyisocyanurate raw material of the present embodiment comprises polyisocyanurate and the compound (I) and a compound represented by the following general formula (I ′) (hereinafter, also referred to as “compound (I ′)”). And at least one compound selected from the group consisting of:
- R 1 and R 2 represent a hydrogen atom, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, Represents an amino group, a monoalkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
- both R 1 and R 2 do not become hydrogen atoms.
- R 3 to R 5 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, Represents a monoalkylamino group, a dialkylamino group having 2 to 20 carbon atoms, a carboxy group, a cyano group, a fluorinated alkyl group having 1 to 10 carbon atoms, or a halogen atom.
- Each of the three R 1 to R 5 may be the same or different.
- the proportion of polyisocyanurate in the cured polyisocyanurate raw material of the present embodiment is, for example, preferably from 70% by mass to less than 100% by mass, and more preferably from 80 to 99% by mass.
- the compound (I) is the same as that described in the description of the first embodiment in the section “[Polyisocyanurate raw material composition]”. Preferred examples of the compound (I) also include the same compounds as those described in the first embodiment of the above-mentioned “[Polyisocyanurate raw material composition]”.
- Compound (I ′) is an oxide of compound (I).
- R 1 ⁇ R 5 in the general formula (I ') is the same as R 1 ⁇ R 5 in the general formula (I).
- Preferred examples of R 1 ⁇ R 5 in the general formula (I ') include the same as those of the preferred examples of R 1 ⁇ R 5 in the general formula (I).
- Preferred examples of the compound (I ′) include a compound represented by the following general formula (I′-1).
- R 1, R 2 and R 4 are the same as R 1, R 2 and R 4 in the above general formula (I '). Each of the three R 1 , R 2 and R 4 may be the same or different. ]
- R 1, R 2 and R 4 in the general formula (I'-1) is the same as R 1, R 2 and R 4 in the general formula (I ').
- R 1 and R 2 in the general formula (I′-1) each independently represent a hydrogen atom, an alkoxy group having 1 to 4 carbon atoms, a monoalkylamino group having 1 to 4 carbon atoms, or a carbon atom having 1 to 4 carbon atoms. It is preferably 2 to 8 dimethylamino groups (however, both R 1 and R 2 are not hydrogen atoms).
- the alkoxy group having 1 to 4 carbon atoms is preferably an alkoxy group having 1 to 3 carbon atoms, more preferably an ethoxy group or a methoxy group, and further preferably a methoxy group.
- Each alkyl group of the monoalkylamino group having 1 to 4 carbon atoms or the dialkylamino group having 2 to 8 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.
- a methylamino group or a dimethylamino group is more preferred.
- the compound (I ′) contained in the cured polyisocyanurate raw material of the present embodiment may be one type or two or more types.
- the polyisocyanurate raw material cured product of the present embodiment may contain only the compound (I), may contain only the compound (I ′), and may contain both the compound (I) and the compound (I ′). May be included.
- the compound (I ′) is an oxide of the compound (I).
- the total ratio of the compound (I) and the compound (I ′) in the cured polyisocyanurate raw material of the present embodiment is, for example, preferably 0.001 to 5% by mass, and more preferably 0.001 to 1% by mass. More preferably, there is.
- the cured polyisocyanurate raw material of the present embodiment contains other components in addition to the polyisocyanurate and at least one compound selected from the group consisting of compound (I) and compound (I ′). Is also good. Examples of other components include (i) an epoxy compound, (ii) a reaction product of an epoxy compound and a polyfunctional isocyanate, (iii) a reaction product of the epoxy compound and the above compound (I), and (iv) an epoxy compound. (Hereinafter, (i) to (iv) may be collectively referred to as “epoxy compound or the like”).
- epoxy compound The epoxy compound is the same as that described in the description of the first embodiment in the above section “[Polyisocyanurate raw material composition]”. Preferred examples of the epoxy compound also include the same compounds as those described in the first embodiment in the section of “[Polyisocyanurate raw material composition]”.
- the reaction product of the epoxy compound and the polyfunctional isocyanate is a compound generated by the reaction between the polyfunctional isocyanate and the epoxy compound during the heating reaction.
- the reaction product of the epoxy compound and the polyfunctional isocyanate is not particularly limited as long as it is a compound generated by reacting the epoxy compound with the polyfunctional isocyanate. Examples of the reactant include a compound containing an oxazolidone ring.
- the reaction product of the epoxy compound and the compound (I) is a compound formed by reacting the epoxy compound with the compound (I) during a heating reaction.
- the reaction product of the epoxy compound and the compound (I) is not particularly limited as long as it is a compound generated by reacting the epoxy compound with the compound (I).
- the epoxy compound is a compound represented by the following general formula (E)
- a compound represented by the following general formula (E-1) is exemplified. You.
- R 1 ⁇ R 5 are the same as R 1 ⁇ R 5 in the general formula (I). Each of the three R 1 to R 5 may be the same or different.
- Re 1 is an organic group.
- Re 1 in the general formulas (E) and (E-1) is a phenoxymethyl group.
- a reaction product of an epoxy compound and an epoxy compound is a compound generated by the reaction of two or more epoxy compounds during a heating reaction.
- the reaction product of the epoxy compounds is not particularly limited as long as it is a compound generated by the reaction of two or more epoxy compounds.
- the reaction product of the epoxy compound and the epoxy compound may be a polymer having a repeating unit represented by the following general formula (E-2) Is exemplified.
- Re 1 is an organic group.
- Re 1 in the general formula (E-2) is a phenoxymethyl group.
- the total ratio of the epoxy compound and the like in the cured polyisocyanurate raw material of the present embodiment is, for example, preferably 0.001 to 30% by mass, and more preferably 0.01 to 20% by mass.
- Examples of the cured polyisocyanurate raw material of the present embodiment include polyisocyanurate in an amount of 70% by mass or more and less than 100% by mass (preferably 79% by mass to 99.98% by mass); compound (I) and compound (I ′). ) In a total amount of more than 0% by mass and 5% by mass or less (preferably 0.001 to 1% by mass); and an epoxy compound or the like in a total amount of more than 0% by mass and less than 30% by mass (preferably 0.01 to 20% by mass) and those contained.
- the polyisocyanurate raw material cured product of the present embodiment is produced using compound (I) as a catalyst, it has little foaming and sufficient hardness. Therefore, the cured polyisocyanurate raw material of this embodiment can be used for various applications such as paints, adhesives, sealing materials, and optical components.
- the present invention provides a mixing step of mixing a polyfunctional isocyanate, the compound (I) represented by the general formula (I), and an epoxy compound, and a mixture obtained in the mixing step. And a heating step of heating the polyisocyanurate.
- the mixing step is a step of mixing the polyfunctional isocyanate, the compound (I), and the epoxy compound.
- polyfunctional isocyanate The polyfunctional isocyanate is the same as that described in the description of the first embodiment in the section “[Polyisocyanurate raw material composition]”. Preferred examples of the polyfunctional isocyanate also include the same ones as those described in the first embodiment of the above-mentioned “[Polyisocyanurate raw material composition]”.
- the compound (I) is the same as that described in the description of the first embodiment in the section “[Polyisocyanurate raw material composition]”. Preferred examples of the compound (I) also include the same compounds as those described in the first embodiment of the above-mentioned “[Polyisocyanurate raw material composition]”.
- epoxy compound The epoxy compound is the same as that described in the description of the first embodiment in the section of “[Polyisocyanurate raw material composition]”. Preferred examples of the epoxy compound also include the same compounds as those described in the first embodiment in the section of “[Polyisocyanurate raw material composition]”.
- the mixing ratio (molar ratio) of the epoxy compound to the polyfunctional isocyanate is preferably 100 / 0.001 to 100/15, more preferably 100 / 0.005 to 100/10, and more preferably 100 / 0.005 to 100/10. More preferably, it is 0.1 to 100/7.
- the order in which the polyfunctional isocyanate, the compound (I), and the epoxy compound are mixed is not particularly limited, but from the viewpoint of suppressing unintended progress of the reaction, the compound (I) and the epoxy compound are first mixed. It is preferable not to mix them.
- the mixing step may be, for example, a step of mixing an epoxy compound with a mixture (d) of the polyfunctional isocyanate and the compound (I).
- the mixture (d) the polyisocyanurate raw material composition according to the second embodiment described in the section “[Polyisocyanurate raw material composition]” can be used.
- the mixing step may be, for example, a step of mixing the compound (I) with a mixture (e) of a polyfunctional isocyanate and an epoxy compound.
- a mixture (e) of a polyfunctional isocyanate and an epoxy compound As the mixture (e), the same mixture (e) as the composition (e) included in the polyisocyanurate production kit according to the fourth embodiment described in the above section “[Polyisocyanurate production kit]” is used. Can be.
- the mixing step may be, for example, a step of mixing a mixture (d) of a polyfunctional isocyanate and a compound (I) with a mixture (e) of a polyfunctional isocyanate and an epoxy compound.
- the mixture (d) the same mixture (d) as the composition (d) included in the polyisocyanurate production kit according to the third embodiment described in the section of “[Polyisocyanurate production kit]” is used.
- the mixture (e) may be the same as the composition (e) contained in the polyisocyanurate production kit according to the third embodiment described in the section of “[Polyisocyanurate production kit]”. Can be used.
- the blocked isocyanate group may be subjected to a deprotection reaction before, after, or during the mixing step.
- the deprotection reaction can be appropriately selected depending on the type of the protecting group that blocks the isocyanate group.
- the heating step is a step of heating the mixture obtained in the mixing step.
- a mixture of the polyfunctional isocyanate, the compound (I), and the epoxy compound is appropriately stirred, poured into a mold, and then subjected to a heating reaction.
- the heating temperature may be any temperature that is sufficient for the polyisocyanurate formation reaction to proceed, for example, 40 to 240 ° C., and preferably 60 to 200 ° C.
- the heating time may be a time sufficient for the production of the polyisocyanurate, for example, 1 to 360 minutes, and preferably 30 to 180 minutes.
- Heating may be performed in two stages. For example, in the first stage, heating may be performed at a relatively low temperature, and in the second stage, heating may be performed at a higher temperature than the first stage.
- the heating temperature in the first stage is, for example, 60 to 120 ° C., and preferably 70 to 110 ° C.
- the heating time in the first stage is from 1 to 180 minutes, preferably from 30 to 150 minutes.
- the heating temperature in the second stage is, for example, 120 to 240 ° C., preferably 150 to 210 ° C.
- the heating time in the second stage is from 1 to 180 minutes, preferably from 30 to 150 minutes.
- Polyisocyanurate or a cured product of polyisocyanurate raw material can be produced as described above.
- the polyfunctional isocyanate trimerization reaction proceeds efficiently using the compound (I) and the epoxy compound as catalysts.
- the compound (I) has low hygroscopicity, it is possible to obtain a polyisocyanurate or a polyisocyanurate raw material cured product with less foaming.
- the present invention provides a catalyst for a polyisocyanurate production reaction, comprising a combination of the compound (I) represented by the general formula (I) and an epoxy compound.
- the present invention provides a method for producing a polyisocyanurate, comprising a combination of the compound (I) represented by the general formula (I) and an epoxy compound as a catalyst for a polyisocyanurate generation reaction. Provide kit for use.
- the compound (I) is the same as that described in the description of the first embodiment in the section “[Polyisocyanurate raw material composition]”. Preferred examples of the compound (I) also include the same compounds as those described in the first embodiment of the above-mentioned “[Polyisocyanurate raw material composition]”.
- the epoxy compound is the same as that described in the description of the first embodiment in the section of “[Polyisocyanurate raw material composition]”. Preferred examples of the epoxy compound also include the same compounds as those described in the first embodiment in the section of “[Polyisocyanurate raw material composition]”.
- the present invention provides an adhesive comprising the polyisocyanurate raw material composition. Since the polyisocyanurate raw material composition has good curability and excellent adhesiveness, it can be suitably used for adhesive applications.
- the material of the adherend is not particularly limited, and examples thereof include metal materials such as aluminum, chromium, copper, magnesium, nickel, tin, titanium, zinc, and alloys using two or more metals; polyamide, polycarbonate, and polyether. Examples include plastic materials such as ether ketone, polyimide, and epoxy resin.
- the adherend may have been previously subjected to a surface treatment such as a degreasing treatment, an etching treatment, or a chemical treatment in order to improve the adhesive strength.
- the polyisocyanurate raw material composition may be prepared in the state of the polyisocyanurate production kit. That is, the kit for producing polyisocyanurate may be used as an adhesive kit.
- a general method can be applied as a method of bonding an adherend.
- the adhesive of the present embodiment is a thermosetting adhesive because it is cured by heat.
- Examples 1 to 40 showed good results for both gel time and foaming.
- Comparative Examples 1 to 69 the gel time was long and did not cure within 360 minutes, so that a cured polyisocyanurate raw material could not be obtained, or even when a cured polyisocyanurate raw material could be obtained, foaming was often observed.
- Comparative Examples 61 to 69 the compound (I) was used as a catalyst, and no epoxy compound was used. However, the gel time was long, and a cured polyisocyanurate raw material could not be obtained. From these results, in Examples 1 to 40, it was confirmed that foaming during thermosetting was suppressed and curability was good. Also, from the results in Table 12 (Comparative Examples 61 to 69), it was confirmed that an epoxy compound was necessary for the progress of the polyisocyanurate formation reaction.
- Phosphorus catalyst No. 5 and phosphorus catalyst No. 5 Reference numeral 11 denotes a phosphorus catalyst in which a methoxy group as a substituent is bonded to the para-position and the ortho-position of a benzene ring, respectively. Although both had the same HOMO level, a large difference was observed in the reaction time. In order to investigate the cause, a transition state calculation is performed based on the density functional theory B3LYP / 6-31 + G * method, and the phosphorus catalyst performs nucleophilic attack on 1,2-ethyloxirane (epoxy compound) as a cocatalyst. The activation barrier at the time was calculated.
- Phosphorous catalyst no. 5 and phosphorus catalyst No. 5 As a result of observing the structure in the above transition state calculation with No. 11, the hydrogen atom of 1,2-ethyloxirane and the oxygen atom at the ortho position of the phosphorus catalyst are hydrogen-bonded, and the 1,2-oxirane is attracted to the phosphorus catalyst molecule, As a result, it was found that the distance between the phosphorus atom, which is the reaction point, and the carbon of 1,2-ethyloxirane was shortened.
- the substituent atom directly bonded to the ortho-position carbon of the phosphorus atom is electrically negative. It turned out to be necessary.
- the phosphorus catalyst No. 5 has an average charge of 0.1435
- phosphorus catalyst No. 5 has an average charge of 0.1435.
- the average charge at the ortho position of No. 11 was -0.1805, and 11 was found to be more electrically negative. From the above, the fact that the atom of the substituent directly bonded to the ortho-position carbon of the phosphorus atom is electrically negative is the second index for screening the catalyst for the polyisocyanurate generation reaction having a high reaction rate. I understand.
- the “average charge at the ortho position” is the average value of the Mulliken charge of the atom directly bonded to the carbon atom among the substituents bonded to the ortho position of the three cyclic molecules directly bonded to the phosphorus atom.
- the above phosphorus catalyst No. In 1 TPP
- a hydrogen atom bonded to a carbon atom on both sides of a carbon atom bonded to a phosphorus atom corresponds thereto. Since the benzene ring is bonded to three phosphorus atoms, there are six such atoms.
- the average of the Mulliken charges of these six atoms is defined as "the average charge in the ortho position”.
- the HOMO level was plotted on the horizontal axis (x-axis), and the average charge in the ortho position was plotted on the vertical axis (y-axis).
- the result is shown in FIG. In FIG. 1, the numbers attached to the plots correspond to the phosphorus catalyst Nos.
- the phosphorus catalyst (phosphorous catalyst used in Examples 1 to 40; phosphorus catalysts Nos. 9 to 11: black circles) showing good curability in the evaluation test of the polyisocyanurate raw material composition was , Y ⁇ 28.5x + 5.644 (x: HOMO level / au; y: average charge in ortho position).
- a phosphorus catalyst satisfying the condition of the following formula (1) favorably promotes the polyisocyanurate formation reaction and can be suitably used as a catalyst for the polyisocyanurate formation reaction.
- R 1 ⁇ R 5, R 11 ⁇ R 15, and R 21 ⁇ R 25 is a R 1 ⁇ R 5, R 11 ⁇ R 15, and R 21 ⁇ R 25 in the following general formula
- “H” is a hydrogen atom
- "OMe” is a methoxy group
- “NHMe” is a monomethylamino group
- “NMe2” is a dimethylamino group.
- the phosphorus catalyst No. used in Examples 1 to 40 was used. 9 to 11, the phosphorus catalyst Nos. It is thought that a phosphorus catalyst of 12 to 170 can also be suitably used as a catalyst for the polyisocyanurate production reaction.
- Adhesives 1 to 4 were respectively applied to carbon steel sheets, and two carbon steel sheets were overlapped so that the overlap length was 12.5 mm, and excess adhesive that had protruded was removed.
- the two superposed carbon steel sheets were heated at 100 ° C. for 180 minutes using a circulating thermostat (VTR-111, Isuzu Seisakusho), and further heated at 200 ° C. for 60 minutes to obtain a test piece. Produced.
- adhesives 1 to 4 all exhibited an adhesive strength of 10 MPa or more. From these results, it was confirmed that the adhesive using the polyisocyanurate raw material composition had excellent adhesiveness.
- the foaming at the time of heat hardening is few, and the manufacturing method of the polyisocyanurate with favorable curability, the polyisocyanurate raw material composition which can be used for the said manufacturing method, and the kit for polyisocyanurate manufacture are provided. Is done. Further, there is provided a polyisocyanurate or a polyisocyanurate composition which is produced by the above-mentioned production method and has little foaming.
- the polyisocyanurate or the cured product of the polyisocyanurate raw material can be used for various applications such as paints, adhesives, sealing materials, and various molded products.
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Abstract
Description
本願は、2018年8月13日に、日本に出願された特願2018-152261号、及び2019年2月4日に、日本に出願された特願2019-018223号に基づき優先権を主張し、その内容をここに援用する。
一方、吸湿性の低い触媒としてはリン触媒が挙げられる。しかし、リン触媒では、多官能イソシアネート三量化反応の反応効率が低く、熱硬化に十分な量のイソシアヌレート環を生成することができない。
[1]多官能イソシアネートと、下記一般式(I)で表される化合物(I)と、エポキシ化合物と、を含む、ポリイソシアヌレート原料組成物。
[4]前記多官能イソシアネートが、ジフェニルメタンジイソシアネート、トリレンジイソシアネート、ヘキサメチレンジイソシアネート、ビス(イソシアナトメチル)シクロヘキサン、及びこれらの改質ポリイソシアネート類からなる群より選択される少なくとも1種である、[1]~[3]のいずれか一つに記載のポリイソシアヌレート原料組成物。
[5]前記一般式(I)中のR1及びR2が、それぞれ独立に、水素原子、炭素数1~4のアルコキシ基、炭素数1~4のモノアルキルアミノ基、又は炭素数2~8のジアルキルアミノ基(ただし、R1及びR2の両方が水素原子になることはない)である、[1]~[4]のいずれか一つに記載のポリイソシアヌレート原料組成物。
[9](d)多官能イソシアネートと下記一般式(I)で表される化合物(I)とを含む組成物、及び(e)多官能イソシアネートとエポキシ化合物とを含む組成物、を含む、ポリイソシアヌレート製造用キットであって、前記(d)及び(e)は、それぞれ異なる容器に収容されている、キット。
[12]前記一般式(I)中のR1及びR2が、それぞれ独立に、水素原子、炭素数1~4のアルコキシ基、炭素数1~4のモノアルキルアミノ基、又は炭素数2~8のジアルキルアミノ基(ただし、R1及びR2の両方が水素原子になることはない)である、[6]~[11]のいずれか一つに記載のポリイソシアヌレート製造用キット。
[13][1]~[5]のいずれか一つに記載のポリイソシアヌレート原料組成物を加熱してなるポリイソシアヌレート原料硬化物。
[14]ポリイソシアヌレートと、
下記一般式(I)で表される化合物(I)及び下記一般式(I’)で表される化合物(I’)からなる群より選択される少なくとも1種の化合物と、
を含む、ポリイソシアヌレート原料硬化物。
[16]前記一般式(I)及び(I’)中のR1及びR2が、それぞれ独立に、水素原子、炭素数1~4のアルコキシ基、炭素数1~4のモノアルキルアミノ基、又は炭素数2~8のジアルキルアミノ基(ただし、R1及びR2の両方が水素原子になることはない)である、[14]又は[15]に記載のポリイソシアヌレート原料硬化物。
[17]多官能イソシアネートと、下記一般式(I)で表される化合物(I)と、エポキシ化合物と、を混合する混合工程と、前記混合工程で得られた混合物を加熱する加熱工程とを含む、ポリイソシアヌレートの製造方法。
[19]前記混合工程が、前記多官能イソシアネートと前記エポキシ化合物との混合物(e)に、前記化合物(I)を混合する工程である、[17]に記載のポリイソシアヌレートの製造方法。
[20]前記混合工程が、前記多官能イソシアネートと前記化合物(I)との混合物(d)に、前記多官能イソシアネートと前記エポキシ化合物との混合物(e)を混合する工程である、[17]に記載のポリイソシアヌレートの製造方法。
[21]前記多官能イソシアネートに対する前記化合物(I)の混合割合(モル比)が、多官能イソシアネート/化合物(I)=100/0.001~100/5である、[17]~[20]のいずれか一つに記載のポリイソシアヌレートの製造方法。
[22]前記多官能イソシアネートが、ジフェニルメタンジイソシアネート、トリレンジイソシアネート、ヘキサメチレンジイソシアネート、ビス(イソシアナトメチル)シクロヘキサン、及びこれらの改質ポリイソシアネート類からなる群より選択される少なくとも1種である、[17]~[21]のいずれか一つに記載のポリイソシアヌレートの製造方法。
[23]前記一般式(I)中のR1及びR2が、それぞれ独立に、水素原子、炭素数1~4のアルコキシ基、炭素数1~4のモノアルキルアミノ基、又は炭素数2~8のジアルキルアミノ基(ただし、R1及びR2の両方が水素原子になることはない)である、[17]~[22]のいずれか一つに記載のポリイソシアヌレートの製造方法。
[24]前記加熱工程を40~240℃の温度で行う、[17]~[23]のいずれか一つに記載のポリイソシアヌレートの製造方法。
[25]前記加熱工程が、60~120℃で1~180分間加熱した後、さらに120~240℃で1~180分間加熱する工程である、[24]に記載のポリイソシアヌレートの製造方法。
[26]下記一般式(I)で表される化合物(I)と、エポキシ化合物と、の組み合わせを含む、ポリイソシアヌレート生成反応用の触媒。
[27]下記一般式(I)で表される化合物(I)と、エポキシ化合物と、の組み合わせを、ポリイソシアヌレート生成反応用の触媒として含む、ポリイソシアヌレート製造用キット。
[28][1]~[5]のいずれか一つに記載のポリイソシアヌレート原料組成物からなる接着剤。
本明細書において、「ポリイソシアヌレート原料組成物」とは、ポリイソシアヌレートの原料(ポリイソシアヌレート生成反応の反応物)及びポリイソシアヌレート生成反応の触媒のいずれか又は両方を含有する組成物であって、ポリイソシアヌレート又はポリイソシアヌレート原料硬化物の製造に用いられるものをいう。
本明細書において、「ポリイソシアヌレート製造用キット」とは、ポリイソシアヌレートの原料及びポリイソシアヌレート生成反応の触媒を含むキットであって、ポリイソシアヌレート又はポリイソシアヌレート原料硬化物の製造に用いられるものである。
本明細書において、「ポリイソシアヌレート原料硬化物」とは、ポリイソシアヌレート原料組成物を加熱して得られた、ポリイソシアヌレートを含有する硬化物をいう。
本明細書において、アルキル基、アルコキシ基、フッ化アルキル基、及びアリール基の炭素数について言及する場合、該炭素数には置換基における炭素数は含まないものとする。
≪第1実施形態≫
一実施形態において、本発明は、多官能イソシアネートと、下記一般式(I)で表される化合物(以下、「化合物(I)」ともいう。)と、エポキシ化合物と、を含む、ポリイソシアヌレート原料組成物を提供する。
「多官能イソシアネート」とは、イソシアナト基(-N=C=O)を2個以上含む化合物を意味する。多官能イソシアネートは、ポリイソシアヌレートの製造に一般的に用いられるものを特に制限なく用いることができる。多官能イソシアネートが含むイソシアナト基の数は、2個以上であれば特に限定されないが、2~5個が好ましく、2又は3個がより好ましく、2個がさらに好ましい。多官能イソシアネートとしては、例えば、脂肪族イソシアネート、及び芳香族イソシアネート等が挙げられる。
また、多官能イソシアネートは、ウレタン工業で使用されるポリオールに、上記のようなイソシアネートを過剰に反応して得られるイソシアネート基体予備重合体であってもよい。
本実施形態のポリイソシアヌレート原料組成物における多官能イソシアネートの割合としては、例えば、80モル%以上100モル%未満が例示される。ポリイソシアヌレート原料組成物における多官能イソシアネートの割合は、85モル%以上99.99モル%以下が好ましく、90モル%以上98モル%以下がより好ましく、93モル%以上97モル%以下がさらに好ましい。多官能イソシアネートの割合が前記範囲の下限値以上であると、良好な耐熱性が実現できる。また、多官能イソシアネートの割合が前記範囲の上限値以下であると、他の成分とのバランスがとりやすくなる。
化合物(I)は、下記一般式(I)で表される化合物である。
アルコキシ基は、-OR(Rはアルキル基)で表される基である。前記Rにおけるアルキル基は、直鎖状であってもよく、分岐鎖状であってもよく、構造中に環を含むものであってもよいが、直鎖状又は分岐鎖状のアルキル基が好ましい。前記アルキル基としては、メチル基及び後述する炭素数2~10のアルキル基で挙げるものと同様のものが挙げられる。
炭素数1~10のアルコキシ基の具体例としては、メトキシ基、エトキシ基、n-プロポキシ基、iso-プロポキシ基、n-ブトキシ基、tert-ブトキシ基等が挙げられる。中でも、メトキシ基又はエトキシ基が好ましく、メトキシ基がより好ましい。
直鎖状又は分岐鎖状のアルキル基としては、例えば、エチル基、プロピル基、イソプロピル基、n-ブチル基、sec-ブチル基、イソブチル基、tert-ブチル基、n-ペンチル基、ネオペンチル基、イソペンチル基、sec-ペンチル基等が挙げられる。
R1及びR2における直鎖状又は分岐鎖状のアルキル基は、置換基を有していてもよい。本明細書において、「置換基を有していてもよい」とは、炭化水素基の水素原子(-H)が1価の基で置換されていてもよいことを意味する。置換基としては、例えば、アミノ基、カルボキシ基、シアノ基、ハロゲン原子等が例示される。前記置換基としてのハロゲン原子としては、フッ素原子、塩素原子、臭素原子、及びヨウ素原子が挙げられる。
R1及びR2における直鎖状又は分岐鎖状のアルキル基としては、置換基を有さないものがより好ましい。
R1及びR2における構造中に環を含むアルキル基は、置換基を有していてもよい。置換基としては、例えば、アミノ基、カルボキシ基、シアノ基、ハロゲン原子等が例示される。
R1及びR2における炭素数6~12のアリール基は、置換基を有していてもよい。置換基としては、例えば、炭素数1~5のアルキル基、アミノ基、カルボキシ基、シアノ基、ハロゲン原子等が例示される。
炭素数1~10のアルコキシ基の具体例としては、前記R1及びR2における炭素数1~10のアルコキシ基として挙げたものと同様のものが挙げられる。中でも、R3~R5における炭素数1~10のアルコキシ基は、メトキシ基又はエトキシ基が好ましく、メトキシ基がより好ましい。
中でも、R1及びR2としては、炭素数1~10のアルコキシ基、炭素数1~10のモノアルキルアミノ基、又は炭素数2~20のジアルキルアミノ基が好ましい。炭素数1~10のアルコキシ基としては、炭素数1~4が好ましく、炭素数1~3がより好ましく、エトキシ基又はメトキシ基がさらに好ましく、メトキシ基が特に好ましい。炭素数1~10のモノアルキルアミノ基又は炭素数2~20のジアルキルアミノ基が有する各アルキル基としては、炭素数1~4のアルキル基が好ましく、炭素数1~3のアルキル基がより好ましく、メチルアミノ基又はジメチルアミノ基がさらに好ましい。
中でも、R4としては、水素原子又は炭素数1~10のアルコキシ基が好ましい。炭素数1~10のアルコキシ基としては、炭素数1~4が好ましく、炭素数1~3がより好ましく、エトキシ基又はメトキシ基がさらに好ましく、メトキシ基が特に好ましい。
本実施形態のポリイソシアヌレート原料組成物における化合物(I)の割合としては、例えば、0モル%超10モル%以下が例示される。ポリイソシアヌレート原料組成物における化合物(I)の割合は、0.001モル%以上5モル%以下が好ましく、0.01モル%以上2モル%以下がより好ましく、0.05モル%以上2モル%以下がさらに好ましい。化合物(I)の割合が前記範囲の下限値以上であると、良好な反応効率を実現できる。また、化合物(I)の割合が前記範囲の上限値以下であると、他の成分とのバランスがとりやすくなる。
本実施形態におけるエポキシ化合物は、1個以上のエポキシ基を含む化合物である。エポキシ化合物は、イソシアネートの三量化反応に一般的に用いられるものを特に制限なく使用することができる。エポキシ化合物のエポキシ当量は、特に限定されないが、50g/mol~1000g/molが好ましく、100g/mol~500g/molがより好ましく、100g/mol~300g/molがさらに好ましい。
本実施形態のポリイソシアヌレート原料組成物におけるエポキシ化合物の割合としては、例えば、0モル%超20モル%以下が例示される。ポリイソシアヌレート原料組成物における化合物(I)の割合は、0.001モル%以上15モル%以下が好ましく、0.005モル%以上10モル%以下がより好ましく、0.1モル%以上7モル%以下がさらに好ましい。化合物(I)の割合が前記範囲の下限値以上であると、良好な反応効率を実現できる。また、化合物(I)の割合が前記範囲の上限値以下であると、他の成分とのバランスがとりやすくなる。
本実施形態のポリイソシアヌレート原料組成物は、上記多官能イソシアネート、化合物(I)及びエポキシ化合物に加えて、他の成分を含有していてもよい。他の成分としては、例えば、溶剤、硬化促進剤、シランカップリング剤、酸化防止剤、離型剤、消泡剤、乳化剤、揺変性付与剤、平滑剤、難燃剤、顔料、充填剤、収縮緩和剤等が例示される。
一実施形態において、本発明は、多官能イソシアネートと、化合物(I)と、を含む、ポリイソシアヌレート原料組成物を提供する。
多官能イソシアネートは、前記第1実施形態の説明で記載したものと同様である。多官能イソシアネートの好ましい例も、前記第1実施形態で挙げたものと同様のものが挙げられる。
中でも、多官能イソシアネートとしては、ジフェニルメタンジイソシアネート、トリレンジイソシアネート、ヘキサメチレンジイソシアネート、ビス(イソシアナトメチル)シクロヘキサン、及びこれらの改質ポリイソシアネート類等が好ましい。
本実施形態のポリイソシアヌレート原料組成物における多官能イソシアネートの割合としては、例えば、90モル%以上100モル%未満が例示される。ポリイソシアヌレート原料組成物における多官能イソシアネートの割合は、95モル%以上99.99モル%以下が好ましく、98モル%以上99.99モル%以下がより好ましく、98モル%以上99.95モル%以下がさらに好ましい。多官能イソシアネートの割合が前記範囲の下限値以上であると、良好な耐熱性が実現できる。また、多官能イソシアネートの割合が前記範囲の上限値以下であると、他の成分とのバランスがとりやすくなる。
化合物(I)は、前記第1実施形態の説明で記載したものと同様である。化合物(I)の好ましい例も、前記第1実施形態で挙げたものと同様のものが挙げられる。
中でも、化合物(I)としては、前記一般式(I)中のR1及びR2が、それぞれ独立に、水素原子、炭素数1~4のアルコキシ基、炭素数1~4のモノアルキルアミノ基、又は炭素数2~8のジアルキルアミノ基(ただし、R1及びR2の両方が水素原子になることはない)である化合物が好ましい。
また、化合物(I)としては、前記一般式(I-1)で表される化合物が好ましく、前記一般式(I-1)中のR1及びR2が、それぞれ独立に、水素原子、炭素数1~4のアルコキシ基、炭素数1~4のモノアルキルアミノ基、又は炭素数2~8のジアルキルアミノ基(ただし、R1及びR2の両方が水素原子になることはない)である化合物がより好ましい。
前記において、炭素数1~4のアルコキシ基としては、炭素数1~3のアルコキシ基が好ましく、エトキシ基又はメトキシ基がより好ましく、メトキシ基がさらに好ましい。炭素数1~4のモノアルキルアミノ基又は炭素数2~8のジアルキルアミノ基が有するアルキル基としては、炭素数1~4のアルキル基が好ましく、炭素数1~3のアルキル基がより好ましく、メチルアミノ基又はジメチルアミノ基がさらに好ましい。
化合物(I)の具体例としては、前記式(I-1-1)~(I-1-10)のいずれかで表される化合物、並びに後述の表15~20に記載のリン触媒No.12~170の化合物が挙げられる。
本実施形態のポリイソシアヌレート原料組成物における化合物(I)の割合としては、例えば、0モル%超10モル%以下が例示される。ポリイソシアヌレート原料組成物における化合物(I)の割合は、0.001モル%以上5モル%以下が好ましく、0.01モル%以上2モル%以下がより好ましく、0.05モル%以上2モル%以下がさらに好ましい。化合物(I)の割合が前記範囲の下限値以上であると、良好な反応効率を実現できる。また、化合物(I)の割合が前記範囲の上限値以下であると、他の成分とのバランスがとりやすくなる。
本実施形態のポリイソシアヌレート原料組成物は、上記多官能イソシアネート及び化合物(I)に加えて、他の成分を含有していてもよい。他の成分としては、前記第1実施形態で挙げたものと同様のものが挙げられる。
本実施形態のポリイソシアヌレート製造用キットは、多官能イソシアネート、化合物(I)、及びエポキシ化合物、を含む。
本実施形態のキットとしては、(a)多官能イソシアネート、(b)化合物(I)、(c)エポキシ化合物、(d)多官能イソシアネートと化合物(I)とを含む組成物、及び(e)多官能イソシアネートとエポキシ化合物とを含む組成物、をそれぞれ異なる容器に収容したものを適宜組み合わせて備えるものが例示される。
本実施形態のキットにおいて、各容器に収容される多官能イソシアネート、化合物(I)、及びエポキシ化合物の各量は、特に限定されないが、ポリイソシアヌレートの製造の際に各成分を混合する混合比に応じた量とすることが好ましい。
例えば、本実施形態のキットに含まれる多官能イソシアネートの合計のモル量と、化合物(I)の合計のモル量とのモル比は、多官能イソシアネート/化合物(I)=100/0.001~100/5が好ましく、100/0.01~100/2がより好ましく、100/0.05~100/2がさらに好ましい。
また、例えば、本実施形態のキットに含まれる多官能イソシアネートの合計のモル量と、エポキシ化合物の合計のモル量とのモル比は、多官能イソシアネート/エポキシ化合物=100/0.001~100/15が好ましく、100/0.005~100/10がより好ましく、100/0.1~100/7がさらに好ましい。
前記容器は、特に限定されず、任意の容器であってよい。容器の材質は、内容物により腐食しないものであればよく、例えば、ガラス、樹脂、金属等が挙げられる。
一実施形態において、本発明は、(a)多官能イソシアネート、(b)化合物(I)、及び(c)エポキシ化合物、を含む、ポリイソシアヌレート製造用キットであって、前記(a)~(c)は、それぞれ異なる容器に収容されている、キットを提供する。
多官能イソシアネートは、前記「[ポリイソシアヌレート原料組成物]」の項の第1実施形態の説明で記載したものと同様である。多官能イソシアネートの好ましい例も、前記「[ポリイソシアヌレート原料組成物]」の項の第1実施形態で挙げたものと同様のものが挙げられる。
化合物(I)は、前記「[ポリイソシアヌレート原料組成物]」の項の第1実施形態の説明で記載したものと同様である。化合物(I)の好ましい例も、前記「[ポリイソシアヌレート原料組成物]」の項の第1実施形態で挙げたものと同様のものが挙げられる。
なお、化合物(I)は、溶剤に溶解された状態で容器に収容されていることが好ましい。溶剤は、化合物(I)を溶解できるものであれば特に限定されず、公知の有機溶剤等を用いることができる。
エポキシ化合物は、前記「[ポリイソシアヌレート原料組成物]」の項の第1実施形態の説明で記載したものと同様である。エポキシ化合物の好ましい例も、前記「[ポリイソシアヌレート原料組成物]」の項の第1実施形態で挙げたものと同様のものが挙げられる。
一実施形態において、本発明は、(d)多官能イソシアネートと化合物(I)とを含む組成物、及び(c)エポキシ化合物、を含む、ポリイソシアヌレート製造用キットであって、前記(d)及び(c)は、それぞれ異なる容器に収容されている、キットを提供する。
本実施形態のキットは、多官能イソシアネートと化合物(I)とを含む組成物(以下、「組成物(d)」という)を含む。
組成物(d)は、前記「[ポリイソシアヌレート原料組成物]」の項で説明した第2実施形態にかかるポリイソシアヌレート原料組成物と同様のものである。
エポキシ化合物は、前記第1実施形態にかかるキットと同様である。
一実施形態において、本発明は、(d)多官能イソシアネートと化合物(I)とを含む組成物、及び(e)多官能イソシアネートとエポキシ化合物とを含む組成物、を含む、ポリイソシアヌレート製造用キットであって、前記(d)及び(e)は、それぞれ異なる容器に収容されている、キットを提供する。
組成物(d)は、前記第2実施形態にかかるキットと同様である。
本実施形態のキットは、多官能イソシアネートとエポキシ化合物とを含む組成物(以下、「組成物(e)」という)を含む。
組成物(e)に含まれる多官能イソシアネートは、前記「[ポリイソシアヌレート原料組成物]」の項の第1実施形態の説明で記載したものと同様である。多官能イソシアネートの好ましい例も、前記「[ポリイソシアヌレート原料組成物]」の項の第1実施形態で挙げたものと同様のものが挙げられる。
多官能イソシアネートは、前記組成物(d)に含まれる多官能イソシアネートと同じものであってもよく、異なるものであってもよい。
一実施形態において、本発明は、(e)多官能イソシアネートとエポキシ化合物とを含む組成物、及び(b)化合物(I)、を含む、ポリイソシアヌレート製造用キットであって、前記(e)及び(b)は、それぞれ異なる容器に収容されている、キットを提供する。
組成物(e)は、前記第3実施形態にかかるキットと同様である。
化合物(I)は、前記第1実施形態にかかるキットと同様である。
一実施形態において、本発明は、多官能イソシアネートと、化合物(I)と、エポキシ化合物と、を含むポリイソシアヌレート原料組成物を、加熱させてなる、ポリイソシアヌレート原料硬化物を提供する。ポリイソシアヌレート原料硬化物中には、多官能イソシアネートから生成したポリイソシアヌレートの他、未反応の多官能イソシアネートや二量体、触媒、触媒の変性物、その他不純物が含まれている。
三量化反応に用いた多官能イソシアネートが脂肪族イソシアネートである場合、Rは脂肪族炭化水素基(例えばアルキレン基)となる。三量化反応に用いた多官能イソシアネートが芳香族イソシアネートである場合、Rは芳香族炭化水素基(例えばアリーレン基)となる。
化合物(I)は、上記「[ポリイソシアヌレート原料組成物]」の項の第1実施形態の説明で記載したものと同様である。化合物(I)の好ましい例も、前記「[ポリイソシアヌレート原料組成物]」の項の第1実施形態で挙げたものと同様のものが挙げられる。
エポキシ化合物は、上記「[ポリイソシアヌレート原料組成物]」の項の第1実施形態の説明で記載したものと同様である。エポキシ化合物の好ましい例も、前記「[ポリイソシアヌレート原料組成物]」の項の第1実施形態で挙げたものと同様のものが挙げられる。
化合物(I)は、前記「[ポリイソシアヌレート原料組成物]」の項の第1実施形態の説明で記載したものと同様である。化合物(I)の好ましい例も、前記「[ポリイソシアヌレート原料組成物]」の項の第1実施形態で挙げたものと同様のものが挙げられる。
化合物(I’)は、前記化合物(I)の酸化物である。
前記一般式(I’)中のR1~R5は、前記一般式(I)中のR1~R5と同様である。前記一般式(I’)中のR1~R5の好ましい例としては、前記一般式(I)中のR1~R5の好ましい例として挙げたものと同様のものが挙げられる。化合物(I’)としては、前記化合物(I)の好ましい例として挙げたものの酸化物が好ましい。
化合物(I’)の好ましい例としては、下記一般式(I’-1)で表される化合物が挙げられる。
中でも、前記一般式(I’-1)中のR1及びR2は、それぞれ独立に、水素原子、炭素数1~4のアルコキシ基、炭素数1~4のモノアルキルアミノ基、又は炭素数2~8のジメチルアミノ基(ただし、R1及びR2の両方が水素原子になることはない)であることが好ましい。前記において、炭素数1~4のアルコキシ基としては、炭素数1~3のアルコキシ基が好ましく、エトキシ基又はメトキシ基がより好ましく、メトキシ基がさらに好ましい。炭素数1~4のモノアルキルアミノ基又は炭素数2~8のジアルキルアミノ基が有する各アルキル基としては、炭素数1~4のアルキル基が好ましく、炭素数1~3のアルキル基がより好ましく、メチルアミノ基又はジメチルアミノ基がさらに好ましい。
本実施形態のポリイソシアヌレート原料硬化物に含まれる化合物(I’)は、1種であってもよく、2種以上であってもよい。
本実施形態のポリイソシアヌレート原料硬化物は、ポリイソシアヌレート並びに化合物(I)及び化合物(I’)からなる群より選択される少なくとも1種の化合物に加えて、他の成分を含有していてもよい。他の成分としては、例えば、(i)エポキシ化合物、(ii)エポキシ化合物と多官能イソシアネートとの反応物、(iii)エポキシ化合物と上記化合物(I)との反応物、及び(iv)エポキシ化合物とエポキシ化合物との反応物等(以下、(i)~(iv)をまとめて「エポキシ化合物等」という場合がある)が挙げられる。
エポキシ化合物は、上記「[ポリイソシアヌレート原料組成物]」の項の第1実施形態の説明で記載したものと同様である。エポキシ化合物の好ましい例も、前記「[ポリイソシアヌレート原料組成物]」の項の第1実施形態で挙げたものと同様のものが挙げられる。
エポキシ化合物と多官能イソシアネートとの反応物は、加熱反応の際に、多官能イソシアネートとエポキシ化合物とが反応して生じる化合物である。エポキシ化合物と多官能イソシアネートとの反応物は、エポキシ化合物と多官能イソシアネートとが反応して生じる化合物であれば、特に限定されない。該反応物としては、例えば、オキサゾリドン環を含む化合物が例示される。
エポキシ化合物と化合物(I)との反応物は、加熱反応の際に、エポキシ化合物と化合物(I)とが反応して生じる化合物である。エポキシ化合物と化合物(I)との反応物は、エポキシ化合物と化合物(I)とが反応して生じる化合物であれば、特に限定されない。例えば、エポキシ化合物が下記一般式(E)で表される化合物である場合、エポキシ化合物と化合物(I)との反応物としては、下記一般式(E-1)で表される化合物が例示される。
エポキシ化合物とエポキシ化合物との反応物(エポキシ化合物どうしの反応物)は、加熱反応の際に、2個以上のエポキシ化合物が反応して生じる化合物である。エポキシ化合物どうしの反応物は、2個以上のエポキシ化合物が反応して生じる化合物であれば、特に限定されない。例えば、エポキシ化合物が前記一般式(E)で表される化合物である場合、エポキシ化合物とエポキシ化合物との反応物としては、下記一般式(E-2)で表される繰り返し単位を有する重合体が例示される。
一実施形態において、本発明は、多官能イソシアネートと、前記一般式(I)で表される化合物(I)と、エポキシ化合物と、を混合する混合工程と、前記混合工程で得られた混合物を加熱する加熱工程とを含む、ポリイソシアヌレートの製造方法を提供する。
混合工程は、多官能イソシアネートと、化合物(I)と、エポキシ化合物と、を混合する工程である。
多官能イソシアネートは、前記「[ポリイソシアヌレート原料組成物]」の項の第1実施形態の説明で記載したものと同様である。多官能イソシアネートの好ましい例も、前記「[ポリイソシアヌレート原料組成物]」の項の第1実施形態で挙げたものと同様のものが挙げられる。
化合物(I)は、前記「[ポリイソシアヌレート原料組成物]」の項の第1実施形態の説明で記載したものと同様である。化合物(I)の好ましい例も、前記「[ポリイソシアヌレート原料組成物]」の項の第1実施形態で挙げたものと同様のものが挙げられる。
エポキシ化合物は、前記「[ポリイソシアヌレート原料組成物]」の項の第1実施形態の説明で記載したものと同様である。エポキシ化合物の好ましい例も、前記「[ポリイソシアヌレート原料組成物]」の項の第1実施形態で挙げたものと同様のものが挙げられる。
多官能イソシアネートに対するエポキシ化合物の混合割合(モル比)としては、多官能イソシアネート/エポキシ化合物=100/0.001~100/15が好ましく、100/0.005~100/10がより好ましく、100/0.1~100/7がさらに好ましい。
加熱工程は、前記混合工程で得られた混合物を加熱する工程である。
加熱時間は、ポリイソシアヌレートの生成に十分な時間であればよく、例えば、1~360分を例示することができ、30~180分が好ましい。
一実施形態において、本発明は、前記一般式(I)で表される化合物(I)と、エポキシ化合物と、の組み合わせを含む、ポリイソシアヌレート生成反応用の触媒を提供する。
また、一実施形態において、本発明は、前記一般式(I)で表される化合物(I)と、エポキシ化合物と、の組み合わせを、ポリイソシアヌレート生成反応用の触媒として含む、ポリイソシアヌレート製造用キットを提供する。
エポキシ化合物は、前記「[ポリイソシアヌレート原料組成物]」の項の第1実施形態の説明で記載したものと同様である。エポキシ化合物の好ましい例も、前記「[ポリイソシアヌレート原料組成物]」の項の第1実施形態で挙げたものと同様のものが挙げられる。
一実施形態において、本発明は、前記ポリイソシアヌレート原料組成物からなる接着剤を提供する。
前記ポリイソシアヌレート原料組成物は、硬化性がよく、優れた接着性を有するため、接着剤用途に好適に用いることができる。被着体の材料は特に限定されず、例えば、アルミニウム、クロム、銅、マグネシウム、ニッケル、錫、チタン、亜鉛、および2種類以上の金属を用いた合金等の金属材料;ポリアミド、ポリカーボネート、ポリエーテルエーテルケトン、ポリイミド、およびエポキシ樹脂等のプラスチック材料等が挙げられる。
前記ポリイソシアヌレート原料組成物を接着剤として用いる場合、被着体の接着方法としては、一般的な方法を適用することができる。例えば、本実施形態の接着剤(前記ポリイソシアヌレート原料組成物)の適量を一方の被着体に塗布した後、もう一方の被着体を前記接着剤の塗布面に接着し、前記「[ポリイソシアヌレートの製造方法]」の「≪加熱工程≫」に記載の条件と同様の加熱条件で硬化させることができる。本実施形態の接着剤は、熱により硬化するため、熱硬化型接着剤である。
(実施例1~40、比較例1~69)
多官能イソシアネート及び触媒(化合物(I)または他の触媒)の混合物(d)と、多官能イソシアネート及びエポキシ化合物の混合物(e)とを調製した。前記混合物(d)及び混合物(e)を混合し、ポリイソシアヌレート原料組成物を作製した。多官能イソシアネート、触媒、及びエポキシ化合物の配合比(モル比)は、表1~11の各例に従い、実施例1~40及び比較例1~69のポリイソシアヌレート原料組成物を得た。
実施例1~40、比較例1~69のポリイソシアヌレート原料組成物をガラス容器に入れ、オイルバス(EOS-200RD、アズワン株式会社)で80℃まで加熱した。80℃で保持しながら、30分毎にゲル化しているかを確認し、ゲル化するまでの時間を測定した。なお、ゲル化は、流動性の有無を目視により評価し、流動性がなくなった時点でゲル化したと判断した。
結果を表1~12に示した。表中の評価基準は、以下のとおりである。
評価基準
A:360分未満でゲル化が確認された。
B:360分以上経過してもゲル化が確認されなかった。
実施例1~40、比較例1~69のポリイソシアヌレート原料組成物をアルミ容器に入れ、循環式恒温器(VTR-111、株式会社いすゞ製作所)で80℃、180分間熱して、ポリイソシアヌレート原料硬化物を作製した。作製した硬化物をマイクロスコープ(RH-2000、株式会社ハイロックス)で観察し、任意の1cm×1cm四方にある泡の数を測定した。
結果を表1~12に示した。表中の評価基準は、以下のとおりである。
評価基準
A:泡の数が10個未満
B:泡の数が10個以上
-:評価対象外(ポリイソシアヌレート原料硬化物を作製できない(硬化しない))
一方、比較例1~69では、ゲルタイムが長くて360分以内に硬化せず、ポリイソシアヌレート原料硬化物を得られないか、ポリイソシアヌレート原料硬化物を得られた場合でも発泡が多く観察された。比較例61~69は、触媒として化合物(I)を用い、エポキシ化合物を用いなかったものであるが、ゲルタイムが長く、ポリイソシアヌレート原料硬化物を得られなかった。
これらの結果により、実施例1~40では、熱硬化の際の発泡が抑制され、かつ硬化性が良好であることが確認された。また、表12(比較例61~69)の結果から、ポリイソシアヌレート生成反応の進行には、エポキシ化合物が必要なことが確認された。
リン触媒TMPP、DMPP、TOAP、TPP、TOTP、TPTP、TPAP、DPCP、TCHP、TOCP、DPPP、DPPSTに関して、密度汎関数法、及びB3LYP/6-31G*法に基づく量子化学計算を実施した。リン原子上の非共有電子対を反映するHOMOの準位を計算した。前記各リン触媒の構造式を以下に示す。量子化学計算の実施結果を表14に示す。
以上のことから、リン原子のオルト位の炭素に直接結合する置換基の原子が電気的に陰性であることが、反応速度が速いポリイソシアヌレート生成反応用触媒をスクリーニングする第二の指標となることがわかった。
y<28.5x+5.644 ・・・(1)
x:HOMOの準位/a.u.
y:オルト位の平均電荷
(接着剤1~4)
実施例17、18、39、及び40のポリイソシアヌレート原料組成物を、それぞれ接着剤1~4として使用し、以下の方法で引張せん断接着強さの評価を行った。結果を表22に示す。
JIS K6850(接着剤-剛性被着材の引張せん断接着強さ試験方法)に従い、試験片の作製、及び引張せん断接着強さの測定を行った。
被着材として、1.6×25×100mmの炭素鋼板(S45C-P、日本テストパネル株式会社)を使用した。使用する炭素鋼板はJIS K6848-2に従い、アセトン脱脂処理を行った。
接着剤1~4をそれぞれ炭素鋼板に塗布し、2枚の炭素鋼板を重ね長さが12.5mmとなるように重ね合わせ、はみ出した余分な接着剤を取り除いた。重ね合わせた2枚の炭素鋼板を、循環式恒温器(VTR-111、株式会社いすゞ製作所)を用いて、100℃で、180分加熱後、更に200℃で、60分加熱して試験片を作製した。
万能材料試験機(INSTRON 5900R、インストロンジャパンカンパニイリミテッド)を用いて、3mm/分の試験速度で前期試験片の接着強さを測定した。なお、本測定はn=5で実施し、その平均値を引張せん断接着強さとした。結果を表22に示した。
Claims (19)
- 多官能イソシアネートと、下記一般式(I)で表される化合物(I)と、エポキシ化合物と、を含む、ポリイソシアヌレート原料組成物。
- 多官能イソシアネートと、下記一般式(I)で表される化合物(I)と、を含む、ポリイソシアヌレート原料組成物。
- 前記多官能イソシアネートに対する前記化合物(I)の割合(モル比)が、多官能イソシアネート/化合物(I)=100/0.001~100/5である、請求項1又は2に記載のポリイソシアヌレート原料組成物。
- 前記多官能イソシアネートが、ジフェニルメタンジイソシアネート、トリレンジイソシアネート、ヘキサメチレンジイソシアネート、ビス(イソシアナトメチル)シクロヘキサン、及びこれらの改質ポリイソシアネート類からなる群より選択される少なくとも1種である、請求項1~3のいずれか一項に記載のポリイソシアヌレート原料組成物。
- 前記一般式(I)中のR1及びR2が、それぞれ独立に、水素原子又は炭素数1~4のアルコキシ基(ただし、R1及びR2の両方が水素原子になることはない)である、請求項1~4のいずれか一項に記載のポリイソシアヌレート原料組成物。
- (a)多官能イソシアネート、(b)下記一般式(I)で表される化合物、及び(c)エポキシ化合物、を含む、ポリイソシアヌレート製造用キットであって、前記(a)~(c)は、それぞれ異なる容器に収容されている、キット。
- (d)多官能イソシアネートと下記一般式(I)で表される化合物(I)とを含む組成物、及び(c)エポキシ化合物、を含む、ポリイソシアヌレート製造用キットであって、前記(d)及び(c)は、それぞれ異なる容器に収容されている、キット。
- (d)多官能イソシアネートと下記一般式(I)で表される化合物(I)とを含む組成物、及び(e)多官能イソシアネートとエポキシ化合物とを含む組成物、を含む、ポリイソシアヌレート製造用キットであって、前記(d)及び(e)は、それぞれ異なる容器に収容されている、キット。
- (e)多官能イソシアネートとエポキシ化合物とを含む組成物、及び(b)下記一般式(I)で表される化合物(I)、を含む、ポリイソシアヌレート製造用キットであって、前記(e)及び(b)は、それぞれ異なる容器に収容されている、キット。
- 請求項1~5のいずれか一項に記載のポリイソシアヌレート原料組成物を加熱してなるポリイソシアヌレート原料硬化物。
- ポリイソシアヌレートと、
下記一般式(I)で表される化合物(I)及び下記一般式(I’)で表される化合物(I’)からなる群より選択される少なくとも1種の化合物と、
を含む、ポリイソシアヌレート原料硬化物。
- 多官能イソシアネートと、下記一般式(I)で表される化合物(I)と、エポキシ化合物と、を混合する混合工程と、前記混合工程で得られた混合物を加熱する加熱工程とを含む、ポリイソシアヌレートの製造方法。
- 前記混合工程が、前記多官能イソシアネートと前記化合物(I)との混合物(d)に、前記エポキシ化合物を混合する工程である、請求項12に記載のポリイソシアヌレートの製造方法。
- 前記混合工程が、前記多官能イソシアネートと前記エポキシ化合物との混合物(e)に、前記化合物(I)を混合する工程である、請求項12に記載のポリイソシアヌレートの製造方法。
- 前記加熱工程を40~240℃の温度で行う、請求項12~14のいずれか一項に記載のポリイソシアヌレートの製造方法。
- 前記加熱工程が、60~120℃で1~180分間加熱した後、さらに120~240℃で1~180分間加熱する工程である、請求項15に記載のポリイソシアヌレートの製造方法。
- 下記一般式(I)で表される化合物(I)と、エポキシ化合物と、の組み合わせを含む、ポリイソシアヌレート生成反応用の触媒。
- 下記一般式(I)で表される化合物(I)と、エポキシ化合物と、の組み合わせを、ポリイソシアヌレート生成反応用の触媒として含む、ポリイソシアヌレート製造用キット。
- 請求項1~5のいずれか一項に記載のポリイソシアヌレート原料組成物からなる接着剤。
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