JP7388114B2 - Polymerizable compositions, polymers, lenses, coating agents, methods for producing compounds, and compounds - Google Patents
Polymerizable compositions, polymers, lenses, coating agents, methods for producing compounds, and compounds Download PDFInfo
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- JP7388114B2 JP7388114B2 JP2019187675A JP2019187675A JP7388114B2 JP 7388114 B2 JP7388114 B2 JP 7388114B2 JP 2019187675 A JP2019187675 A JP 2019187675A JP 2019187675 A JP2019187675 A JP 2019187675A JP 7388114 B2 JP7388114 B2 JP 7388114B2
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- 150000001875 compounds Chemical class 0.000 title claims description 117
- 239000000203 mixture Substances 0.000 title claims description 60
- 229920000642 polymer Polymers 0.000 title claims description 23
- 239000011248 coating agent Substances 0.000 title claims description 8
- 238000000034 method Methods 0.000 title description 13
- -1 isocyanate compound Chemical class 0.000 claims description 42
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 25
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 23
- 239000012948 isocyanate Substances 0.000 claims description 23
- 229920005862 polyol Polymers 0.000 claims description 16
- 150000003077 polyols Chemical class 0.000 claims description 16
- 229920006295 polythiol Polymers 0.000 claims description 14
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 description 15
- 239000002585 base Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- 239000005977 Ethylene Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- 239000012043 crude product Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000008096 xylene Substances 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 239000003507 refrigerant Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 150000001342 alkaline earth metals Chemical class 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- 229920002578 polythiourethane polymer Polymers 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 235000010724 Wisteria floribunda Nutrition 0.000 description 4
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 4
- 238000001269 time-of-flight mass spectrometry Methods 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 235000002597 Solanum melongena Nutrition 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000001577 simple distillation Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 3
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 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
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000002649 leather substitute Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- XVKLLVZBGMGICC-UHFFFAOYSA-N o-[3-propanethioyloxy-2,2-bis(propanethioyloxymethyl)propyl] propanethioate Chemical compound CCC(=S)OCC(COC(=S)CC)(COC(=S)CC)COC(=S)CC XVKLLVZBGMGICC-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-UHFFFAOYSA-N 0.000 description 1
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 1
- CVZBYEKCIDMLRV-UHFFFAOYSA-N 1,4-bis(methylsulfanyl)benzene Chemical compound CSC1=CC=C(SC)C=C1 CVZBYEKCIDMLRV-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- PSYGHMBJXWRQFD-UHFFFAOYSA-N 2-(2-sulfanylacetyl)oxyethyl 2-sulfanylacetate Chemical compound SCC(=O)OCCOC(=O)CS PSYGHMBJXWRQFD-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- RFMXKZGZSGFZES-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;2-sulfanylacetic acid Chemical compound OC(=O)CS.OC(=O)CS.OC(=O)CS.CCC(CO)(CO)CO RFMXKZGZSGFZES-UHFFFAOYSA-N 0.000 description 1
- WBEKRAXYEBAHQF-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;3-sulfanylbutanoic acid Chemical compound CC(S)CC(O)=O.CC(S)CC(O)=O.CC(S)CC(O)=O.CCC(CO)(CO)CO WBEKRAXYEBAHQF-UHFFFAOYSA-N 0.000 description 1
- BOZRCGLDOHDZBP-UHFFFAOYSA-N 2-ethylhexanoic acid;tin Chemical compound [Sn].CCCCC(CC)C(O)=O BOZRCGLDOHDZBP-UHFFFAOYSA-N 0.000 description 1
- IPNDIMIIGZSERC-UHFFFAOYSA-N 4-(2-sulfanylacetyl)oxybutyl 2-sulfanylacetate Chemical compound SCC(=O)OCCCCOC(=O)CS IPNDIMIIGZSERC-UHFFFAOYSA-N 0.000 description 1
- HOSGXJWQVBHGLT-UHFFFAOYSA-N 6-hydroxy-3,4-dihydro-1h-quinolin-2-one Chemical group N1C(=O)CCC2=CC(O)=CC=C21 HOSGXJWQVBHGLT-UHFFFAOYSA-N 0.000 description 1
- OAOANFGURTXYPE-UHFFFAOYSA-N C(CC)(=S)OCCCCO Chemical compound C(CC)(=S)OCCCCO OAOANFGURTXYPE-UHFFFAOYSA-N 0.000 description 1
- NOEMSRWQFGPZQS-UHFFFAOYSA-N CCC(O)=S.CCC(O)=S.CCC(O)=S.CCC(CO)(CO)CO Chemical compound CCC(O)=S.CCC(O)=S.CCC(O)=S.CCC(CO)(CO)CO NOEMSRWQFGPZQS-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- RUDUCNPHDIMQCY-UHFFFAOYSA-N [3-(2-sulfanylacetyl)oxy-2,2-bis[(2-sulfanylacetyl)oxymethyl]propyl] 2-sulfanylacetate Chemical compound SCC(=O)OCC(COC(=O)CS)(COC(=O)CS)COC(=O)CS RUDUCNPHDIMQCY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- AOGYCOYQMAVAFD-UHFFFAOYSA-M carbonochloridate Chemical compound [O-]C(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-M 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- WXZKPELXXQHDNS-UHFFFAOYSA-N decane-1,1-dithiol Chemical compound CCCCCCCCCC(S)S WXZKPELXXQHDNS-UHFFFAOYSA-N 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 210000004177 elastic tissue Anatomy 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- ALPIESLRVWNLAX-UHFFFAOYSA-N hexane-1,1-dithiol Chemical compound CCCCCC(S)S ALPIESLRVWNLAX-UHFFFAOYSA-N 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000000752 ionisation method Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- DMEKUKDWAIXWSL-UHFFFAOYSA-N n,n-dimethyl-7-nitro-9h-fluoren-2-amine Chemical compound [O-][N+](=O)C1=CC=C2C3=CC=C(N(C)C)C=C3CC2=C1 DMEKUKDWAIXWSL-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- SKEQOTBKQUCUGK-UHFFFAOYSA-N o-(2-hydroxyethyl) propanethioate Chemical compound CCC(=S)OCCO SKEQOTBKQUCUGK-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、重合性組成物、重合物、レンズ、コーティング剤、化合物の製造方法および化合物に関する。特に、イソシアネート化合物を用いた重合性組成物等に関する。 The present invention relates to polymerizable compositions, polymers, lenses, coating agents, methods for producing compounds, and compounds. In particular, it relates to polymerizable compositions using isocyanate compounds.
イソシアネート化合物は、少なくとも１つのイソシアネート基（－ＮＣＯ）を有する化合物であって、各種用途に広く用いられている。イソシアネート化合物の用途の一例としては、ポリウレタンおよびポリチオウレタンの原料が挙げられる。
一方、イソシアネート化合物に関連する技術としては、特許文献１が挙げられる。
Isocyanate compounds are compounds having at least one isocyanate group (-NCO) and are widely used for various purposes. An example of the use of isocyanate compounds is as a raw material for polyurethane and polythiourethane.
On the other hand, as a technology related to isocyanate compounds, Patent Document 1 can be mentioned.
近年、イソシアネート化合物の需要が拡大している。そのため、新たなイソシアネート化合物が求められるようになっている。そして、新たなイソシアネート化合物は、その特性に応じ、各種工業材料として、色々な用途への展開が期待される。
かかる状況のもと、本発明では、新規なイソシアネート化合物、および、これを用いた重合性組成物、重合物、レンズ、コーティング剤、ならびに、イソシアネート化合物の製造方法を提供することを目的とする。
In recent years, demand for isocyanate compounds has increased. Therefore, new isocyanate compounds are required. The new isocyanate compounds are expected to be used in a variety of applications as various industrial materials, depending on their properties.
Under such circumstances, the present invention aims to provide a novel isocyanate compound, a polymerizable composition, a polymer, a lens, a coating agent using the same, and a method for producing the isocyanate compound.
上記課題のもと、検討を行った結果、下記手段により、上記課題は解決された。
＜１＞式（１）で表される化合物と、ポリオールおよびポリチオールの少なくとも一方を含む、重合性組成物。
＜２＞前記式（１）で表される化合物が、式（１－１）で表される化合物を含む、＜１＞に記載の重合性組成物。
＜３＞前記式（１）で表される化合物として、前記式（１）において、ＲA～ＲDのうち少なくとも１つが、水素原子である化合物を含む、＜１＞または＜２＞に記載の重合性組成物。
＜４＞前記式（１）で表される化合物が、式（２）で表される化合物を含む、＜１＞～＜３＞のいずれか１つに記載の重合性組成物。
＜７＞＜６＞に記載の重合物を含むレンズ。
＜８＞＜６＞に記載の重合物を含むコーティング剤。
＜９＞式（４）で表される化合物に対して、ホスゲンを反応させることを含む、イソシアネート化合物の製造方法。
＜１０＞式（４）で表される化合物が、式（４－１）で表される化合物を含む、＜９＞に記載のイソシアネート化合物の製造方法。
＜１１＞式（１）で表される化合物。
＜１２＞式（１）で表される化合物が、式（１－１）で表される化合物である、＜１１＞に記載の化合物。
＜１３＞前記式（１）で表される化合物は、前記式（１）において、ＲA～ＲDのうち少なくとも１つが、水素原子である化合物である、＜１１＞に記載の化合物。
＜１４＞式（１）で表される化合物が、式（２）で表される化合物である、＜１１＞に記載の化合物。
<1> A polymerizable composition containing a compound represented by formula (1) and at least one of a polyol and a polythiol.
<2> The polymerizable composition according to <1>, wherein the compound represented by formula (1) includes a compound represented by formula (1-1).
<3> The compound represented by the formula (1) described in <1> or <2> includes a compound in which in the formula (1), at least one of R A to R D is a hydrogen atom. polymerizable composition.
<4> The polymerizable composition according to any one of <1> to <3>, wherein the compound represented by formula (1) includes a compound represented by formula (2).
<7> A lens containing the polymer according to <6>.
<8> A coating agent containing the polymer according to <6>.
<9> A method for producing an isocyanate compound, comprising reacting a compound represented by formula (4) with phosgene.
<10> The method for producing an isocyanate compound according to <9>, wherein the compound represented by formula (4) includes a compound represented by formula (4-1).
<11> A compound represented by formula (1).
<12> The compound according to <11>, wherein the compound represented by formula (1) is a compound represented by formula (1-1).
<13> The compound represented by the formula (1) is the compound according to <11>, wherein in the formula (1), at least one of R A to R D is a hydrogen atom.
<14> The compound according to <11>, wherein the compound represented by formula (1) is a compound represented by formula (2).
本発明により、新規なイソシアネート化合物、および、これを用いた重合性組成物、重合物、レンズ、コーティング剤、ならびに、イソシアネート化合物の製造方法を提供可能になった。 The present invention has made it possible to provide a novel isocyanate compound, a polymerizable composition, a polymer, a lens, a coating agent using the same, and a method for producing the isocyanate compound.
以下において、本発明の内容について詳細に説明する。なお、本明細書において「～」とはその前後に記載される数値を下限値および上限値として含む意味で使用される。
本明細書において、各種物性値および特性値は、特に述べない限り、２３℃におけるものとする。
The content of the present invention will be explained in detail below. In addition, in this specification, "~" is used to include the numerical values described before and after it as a lower limit value and an upper limit value.
In this specification, various physical property values and characteristic values are assumed to be at 23° C. unless otherwise stated.
［式（１）で表される化合物］
本発明の化合物は、式（１）で表される化合物である。このような新規なイソシアネート化合物を用いることにより、各種用途への応用が期待できる。特に、ポリウレタンやポリチオウレタンの原料として期待される。
The compound of the present invention is a compound represented by formula (1). The use of such novel isocyanate compounds can be expected to be applied to various uses. In particular, it is expected to be used as a raw material for polyurethane and polythiourethane.
式（１）で表される化合物は、式（１－１）で表される化合物であることが好ましい。
式（１）および式（１－１）の好ましい実施形態の一例は、ＲA～ＲDのうち３つまたは４つは、エチル基であり、それら以外のＲA～ＲDは、水素原子である。エチル基の置換率を高くすることにより、立体障害によりイソシアネート基の反応性を低下させ水との反応をより効果的に抑制できる。
式（１）および式（１－１）の好ましい他の実施形態の一例は、ＲA～ＲDのうち少なくとも２つは、エチル基であり、ＲA～ＲDのうち少なくとも１つは、水素原子である。水素原子を少なくとも１つ含む構成とすることにより、イソシアネート基の反応性が向上し、水中でのハンドリング性とアルコール、チオール類との反応性のバランスが良好になる傾向にある。
A preferred embodiment of formula (1) and formula (1-1) is that three or four of R A to R D are ethyl groups, and the other R A to R D are hydrogen atoms. It is. By increasing the substitution rate of the ethyl group, the reactivity of the isocyanate group can be reduced due to steric hindrance, and the reaction with water can be more effectively suppressed.
In another preferred embodiment of formula (1) and formula (1-1), at least two of R A to R D are ethyl groups, and at least one of R A to R D is It is a hydrogen atom. By having a structure containing at least one hydrogen atom, the reactivity of the isocyanate group tends to be improved, and the balance between handleability in water and reactivity with alcohols and thiols becomes better.
式（１）で表される化合物は、式（２）で表される化合物であることが好ましい。
また、式（１）で表される化合物は、以下の化合物であることも好ましい。
また、式（１）で表される化合物は、２種以上の混合物であってもよい。
式（１）で表される化合物が混合物である場合、式（１）で表される化合物であって、ＲA～ＲDのうち、３つまたは４つがエチル基である化合物の合計割合が、式（１）で表される化合物の合計量の８０質量％以上（好ましくは９０質量％以上）である混合物が例示される。
さらには、式（１）で表される化合物であって、ＲA～ＲDのうち、３つがエチル基である化合物の合計割合が、式（１）で表される化合物の合計量の８０質量％以上（好ましくは９０質量％以上）である混合物が例示される。
また、式（１）で表される化合物であって、ＲA～ＲDのうち、４つがエチル基である化合物の合計割合が、式（１）で表される化合物の合計量の８０質量％以上（好ましくは９０質量％以上）である混合物が例示される。
Further, the compound represented by formula (1) may be a mixture of two or more kinds.
When the compound represented by formula (1) is a mixture, the total proportion of compounds represented by formula (1) in which three or four of R A to R D are ethyl groups is , a mixture in which the total amount of the compound represented by formula (1) is 80% by mass or more (preferably 90% by mass or more).
Furthermore, the total proportion of compounds represented by formula (1) in which three of R A to R D are ethyl groups is 80% of the total amount of compounds represented by formula (1). Examples include mixtures in which the content is 90% by mass or more (preferably 90% by mass or more).
Furthermore, the total proportion of compounds represented by formula (1) in which four of R A to R D are ethyl groups is 80% by mass of the total amount of compounds represented by formula (1). % or more (preferably 90% by mass or more).
[イソシアネート化合物の製造方法]
上記式（１）で表される化合物は、公知の方法で製造できる。イソシアネート化合物の製造方法としては、例えば、式（４）で表される化合物に対して、ホスゲンを反応させることを含む製造方法が挙げられる。
The compound represented by the above formula (1) can be produced by a known method. Examples of the method for producing the isocyanate compound include a method including reacting a compound represented by formula (4) with phosgene.
まず、式（４）で表される化合物について説明する。
式（４）で表される化合物は、原料ジアミンであり、式（４）におけるＲA～ＲDは、式（１）におけるＲA～ＲDと同義であり、好ましい範囲も同様である。
式（４）で表される化合物は、式（４－１）で表される化合物であることが好ましい。
式（４－１）中、ＲA～ＲDは、式（１）におけるＲA～ＲDと同義であり、好ましい範囲も同様である。
First, the compound represented by formula (4) will be explained.
The compound represented by formula (4) is a raw material diamine, and R A to R D in formula (4) have the same meanings as R A to R D in formula (1), and the preferred ranges are also the same.
The compound represented by formula (4) is preferably a compound represented by formula (4-1).
In formula (4-1), R A to R D have the same meanings as R A to R D in formula (1), and the preferred ranges are also the same.
式（４）で表される化合物は、例えば、キシリレンジアミン（好ましくはメタキシリレンジアミン）に、塩基の存在下で、エチレンを充填して、エチレン化することにより得られる。前記エチレン充填時の反応液の温度は０～１０℃が好ましい。また、エチレンの充填圧力が１．５～２．３ＭＰａであることが好ましい。
前記塩基は、炭酸ルビジウム、水酸化ルビジウム、炭酸セシウム、および、水酸化セシウムからなる群より選択される１種以上のアルカリ金属含有化合物と、金属ナトリウムとを含有する塩基組成物であることが好ましい。上記塩基組成物における、アルカリ金属含有化合物と、金属ナトリウムとを含有する塩基組成物は、さらに、アルカリ土類金属含有化合物（周期表第２元素を含有する化合物）を含有することが好ましい。アルカリ土類金属含有化合物（Ｃ）は、Ｍc（ＯＨ）2、ＭcＣＯ3、ＭcＯ（Ｍcはアルカリ土類金属）がより好ましく、酸化マグネシウム、水酸化マグネシウム、および、炭酸マグネシウムからなる群より選択される１種以上のアルカリ土類金属含有化合物を含有することがさらに好ましい。アルカリ土類金属含有化合物を含有することにより、塩基組成物のべたつきを抑え、ハンドリング性を向上することができる。
式（４）で表される化合物を、上記のような製造方法で製造するにより、芳香環に結合しているアルキル基のα位の炭素原子のエチレン化率の高いジアミンが得られ、結果として、エチレン化率の高いイソシアネート化合物が得られる。
式（４）で表される化合物としては、以下の化合物が例示される。
The base is preferably a base composition containing sodium metal and one or more alkali metal-containing compounds selected from the group consisting of rubidium carbonate, rubidium hydroxide, cesium carbonate, and cesium hydroxide. . In the above base composition, the base composition containing an alkali metal-containing compound and metallic sodium preferably further contains an alkaline earth metal-containing compound (a compound containing the second element of the periodic table). The alkaline earth metal-containing compound (C) is more preferably M c (OH) 2 , M c CO 3 , M c O (M c is an alkaline earth metal), and magnesium oxide, magnesium hydroxide, and magnesium carbonate. It is further preferable to contain one or more alkaline earth metal-containing compounds selected from the group consisting of: By containing the alkaline earth metal-containing compound, the stickiness of the base composition can be suppressed and the handling properties can be improved.
By producing the compound represented by formula (4) by the above production method, a diamine with a high ethylenic rate of the α-position carbon atom of the alkyl group bonded to the aromatic ring is obtained, and as a result, , an isocyanate compound with a high ethylenic rate is obtained.
Examples of the compound represented by formula (4) include the following compounds.
また、本発明の製造方法において、式（４）で表される化合物は、１種のみ用いてもよいし、２種以上の混合物を用いてもよい。
式（４）で表される化合物が混合物である場合、式（４）で表される化合物であって、ＲA～ＲDのうち、３つまたは４つがエチル基である化合物の合計割合が、式（４）で表される化合物の合計量の８０質量％以上（好ましくは９０質量％以上）である混合物が例示される。
さらには、式（４）で表される化合物であって、ＲA～ＲDのうち、３つがエチル基である化合物の合計割合が、式（４）で表される化合物の合計量の８０質量％以上（好ましくは９０質量％以上）である混合物が例示される。
また、式（４）で表される化合物であって、ＲA～ＲDのうち、４つがエチル基である化合物の合計割合が、式（４）で表される化合物の合計量の８０質量％以上（好ましくは９０質量％以上）である混合物が例示される。
Moreover, in the manufacturing method of the present invention, only one type of compound represented by formula (4) may be used, or a mixture of two or more types may be used.
When the compound represented by formula (4) is a mixture, the total proportion of compounds represented by formula (4) in which three or four of R A to R D are ethyl groups is , a mixture in which the total amount of the compound represented by formula (4) is 80% by mass or more (preferably 90% by mass or more) is exemplified.
Furthermore, the total proportion of compounds represented by formula (4) in which three of R A to R D are ethyl groups is 80% of the total amount of compounds represented by formula (4). Examples include mixtures in which the content is 90% by mass or more (preferably 90% by mass or more).
Further, the total proportion of compounds represented by formula (4) in which four of R A to R D are ethyl groups is 80% by mass of the total amount of compounds represented by formula (4). % or more (preferably 90% by mass or more).
次に、式（４）で表される化合物とホスゲンの反応について述べる。
本発明では、式（４）で表される化合物に、ホスゲンを反応させて、式（１）で表される化合物を得ることができる。例えば、式（４）で表される化合物と、塩酸を溶剤中で反応させて式（４）で表される化合物と塩酸の塩を得て、その後、これをホスゲンと反応させて式（１）で表される化合物を合成することができる。溶剤としては、芳香族系溶剤やエステル系溶剤が例示され、芳香族系溶剤が好ましく、キシレンがより好ましい。
式（４）で表される化合物とホスゲンの反応は、例えば、１００～１７０℃で行うことができる。
Next, the reaction between the compound represented by formula (4) and phosgene will be described.
In the present invention, the compound represented by formula (1) can be obtained by reacting the compound represented by formula (4) with phosgene. For example, the compound represented by formula (4) is reacted with hydrochloric acid in a solvent to obtain a salt of the compound represented by formula (4) and hydrochloric acid, and then this is reacted with phosgene to obtain the salt of formula (1). ) can be synthesized. Examples of the solvent include aromatic solvents and ester solvents, with aromatic solvents being preferred and xylene being more preferred.
The reaction between the compound represented by formula (4) and phosgene can be carried out, for example, at 100 to 170°C.
また、本発明では、式（１）で表される化合物は、非ホスゲン法で製造してもよい。例えば、式（４）で表される化合物を、ハロゲン化アルキルクロロホルメート、ハロゲン化ジアルキルクロロカーボネートおよびジアルキルカーボネートの少なくとも１種と反応させてビスカルバメートを調製し、その後、これを触媒の存在中、１３０～２５０℃の温度で、溶剤中において熱分解させ、式（１）で表される化合物を合成してもよい。 Further, in the present invention, the compound represented by formula (1) may be produced by a non-phosgene method. For example, a biscarbamate is prepared by reacting a compound represented by formula (4) with at least one of a halogenated alkyl chloroformate, a halogenated dialkyl chlorocarbonate, and a dialkyl carbonate, and then this is reacted in the presence of a catalyst. The compound represented by formula (1) may be synthesized by thermal decomposition in a solvent at a temperature of 130 to 250°C.
［重合性組成物]
式（１）で表される化合物は、ポリオールやポリチオールと共に重合性組成物として用いることができる。すなわち、本発明は、式（１）で表される化合物と、ポリオールおよびポリチオールの少なくとも一方を含む、重合性組成物に関する。
[Polymerizable composition]
The compound represented by formula (1) can be used as a polymerizable composition together with polyol or polythiol. That is, the present invention relates to a polymerizable composition containing a compound represented by formula (1) and at least one of a polyol and a polythiol.
重合性組成物に含まれる式（１）で表される化合物の好ましい範囲は、上記［式（１）で表される化合物］で述べた事項と同様である。
重合性組成物に含まれる式（１）で表される化合物の含有量は、溶剤を除く成分中、下限値が、３０質量％以上であることが好ましく、３５質量％以上であることがより好ましい。また、前記式（１）で表される化合物の含有量の上限値は、溶剤を除く成分中、５５質量％以下であることが好ましく、４０質量％以下であることがより好ましい。
重合性組成物には、式（１）で表される化合物が１種のみ含まれていてもよいし、２種以上含まれていてもよい。２種以上含まれている場合、合計量が上記範囲となることが好ましい。
The preferable range of the compound represented by formula (1) contained in the polymerizable composition is the same as described above for [compound represented by formula (1)].
The lower limit of the content of the compound represented by formula (1) in the polymerizable composition is preferably 30% by mass or more, more preferably 35% by mass or more among the components excluding the solvent. preferable. Further, the upper limit of the content of the compound represented by the formula (1) is preferably 55% by mass or less, more preferably 40% by mass or less in the components excluding the solvent.
The polymerizable composition may contain only one kind of compound represented by formula (1), or may contain two or more kinds. When two or more types are contained, it is preferable that the total amount falls within the above range.
重合性組成物に含まれうるポリオールとしては、１分子中に水酸基を２以上有する化合物であり、一分子中に水酸基を２～６有する化合物が好ましい。ポリオールは、２つ以上の水酸基を有する低分子化合物であってもよいし、２つ以上の水酸基を有するオリゴマーまたはポリマーであってもよい。
ポリオールとしては、具体的には、ポリアルキレングリコール、ポリエステルポリオール、ポリカーボネートポリオール等が例示される。また、ポリオールとしては、国際公開第２０１８／０６１６５８号の段落００２６～００３７、国際公開第２０１８／０２１３９４号の段落０１３４～０２３３の記載を参酌でき、これらの内容は本明細書に組み込まれる。
The polyol that can be included in the polymerizable composition is a compound having two or more hydroxyl groups in one molecule, preferably a compound having 2 to 6 hydroxyl groups in one molecule. The polyol may be a low molecular weight compound having two or more hydroxyl groups, or may be an oligomer or polymer having two or more hydroxyl groups.
Specific examples of the polyol include polyalkylene glycol, polyester polyol, polycarbonate polyol, and the like. Further, as for the polyol, the descriptions in paragraphs 0026 to 0037 of International Publication No. 2018/061658 and paragraphs 0134 to 0233 of International Publication No. 2018/021394 can be referred to, and the contents of these are incorporated herein.
重合性組成物に含まれるうるポリチオールとしては、１分子中にメルカプト基を２以上有する化合物であり、一分子中にメルカプト基を２～６有する化合物が好ましい。
ポリチオールとしては、具体的には、ヘキサンジチオール、デカンジチオール、１，４－ブタンジオールビスチオプロピオネート、１，４－ブタンジオールビスチオグリコレート、エチレングリコールビスチオグリコレート、エチレングリコールビスチオプロピオネート、トリメチロールプロパントリスチオグリコレート、トリメチロールプロパントリスチオプロピオネート、トリメチロールプロパントリス（３－メルカプトブチレート）、ペンタエリスリトールテトラキスチオグリコレート、ペンタエリスリトールテトラキスチオプロピオネート、トリメルカプトプロピオン酸トリス（２－ヒドロキシエチル）イソシアヌレート、１，４－ジメチルメルカプトベンゼン、２、４、６－トリメルカプト－ｓ－トリアジン、２－（Ｎ，Ｎ－ジブチルアミノ）－４，６－ジメルカプト－ｓ－トリアジンなどが挙げられる。また、ポリチオールとしては、特開２０１９－１１９８６０号公報の段落００２０～００４１の記載、特開２０１７－２１１５４７号公報の段落００７８～００８１を参酌でき、これらの内容は本明細書に組み込まれる。
The polythiol contained in the polymerizable composition is a compound having two or more mercapto groups in one molecule, preferably a compound having 2 to 6 mercapto groups in one molecule.
Specific examples of the polythiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropionate. Pionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropion Acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s - Examples include triazines. Further, as for the polythiol, the descriptions in paragraphs 0020 to 0041 of JP 2019-119860A and paragraphs 0078 to 0081 of JP 2017-211547A can be referred to, and the contents thereof are incorporated into the present specification.
重合性組成物に含まれるポリオールおよび／またはポリチオールの含有量は、下限値が、３０質量％以上であることが好ましく、３５質量％以上であることがより好ましい。また、前記ポリオールおよび／またはポリチオールの含有量の上限値は、５５質量％以下であることが好ましく、４０質量％以下であることがより好ましい。
重合性組成物には、ポリオールおよびポリチオールのいずれか１種のみ含まれていてもよいし、２種以上含まれていてもよい。また、ポリオールとポリチオールの混合物であってもよい。本発明の重合性組成物にポリオールおよび／またはポリチオールが２種以上含まれている場合、合計量が上記範囲となることが好ましい。
The lower limit of the content of polyol and/or polythiol contained in the polymerizable composition is preferably 30% by mass or more, more preferably 35% by mass or more. Further, the upper limit of the content of the polyol and/or polythiol is preferably 55% by mass or less, more preferably 40% by mass or less.
The polymerizable composition may contain only one of polyols and polythiols, or may contain two or more of them. It may also be a mixture of polyol and polythiol. When the polymerizable composition of the present invention contains two or more polyols and/or polythiols, the total amount is preferably within the above range.
重合性組成物に含まれる式（１）で表される化合物と、ポリオールおよび／またはポリチオールの総量の質量比は、１：０．１～３．０であることが好ましく、１：０．５～１．５であることがより好ましい。このような範囲とすることにより、より良好な特性を有する重合物が得られる。 The mass ratio of the compound represented by formula (1) and the total amount of polyol and/or polythiol contained in the polymerizable composition is preferably 1:0.1 to 3.0, and 1:0.5. More preferably, it is 1.5 to 1.5. By setting it within such a range, a polymer having better properties can be obtained.
重合性組成物は、上記の他、ウレタン化触媒、チオウレタン化触媒、重合開始剤、重合禁止剤、鎖延長剤等を含んでいてもよい。また、本発明の趣旨を逸脱しない範囲で、式（１）で表される化合物以外のイソシアネート化合物を含んでいてもよい。
ウレタン化触媒およびチオウレタン化触媒としては、アミン系触媒、イミダゾール系触媒、ジアザシクロアミン塩系触媒、金属系触媒等が例示される。ウレタン化触媒およびチオウレタン化触媒の具体例は、特開２０１９－１４３１５０号公報の段落００３４～００３７の記載、特開２０１６－２２２０５０号公報の段落０１３０～０１３２の記載を参酌でき、これらの内容は本明細書に組み込まれる。
式（１）で表される化合物以外のイソシアネート化合物としては、国際公開第２０１７／２０８９５９号の段落００３５～００３７の記載を参酌でき、この内容は本明細書に組み込まれる。
In addition to the above, the polymerizable composition may also contain a urethanization catalyst, a thiourethane catalyst, a polymerization initiator, a polymerization inhibitor, a chain extender, and the like. Moreover, isocyanate compounds other than the compound represented by formula (1) may be included without departing from the spirit of the present invention.
Examples of the urethanization catalyst and thiourethane catalyst include amine catalysts, imidazole catalysts, diazacycloamine salt catalysts, metal catalysts, and the like. For specific examples of urethanization catalysts and thiourethane catalysts, the descriptions in paragraphs 0034 to 0037 of JP2019-143150A and paragraphs 0130 to 0132 of JP2016-222050A can be referred to, and the contents of these Incorporated herein.
As for isocyanate compounds other than the compound represented by formula (1), the description in paragraphs 0035 to 0037 of International Publication No. 2017/208959 can be referred to, the contents of which are incorporated herein.
さらに、重合性組成物の用途に応じて、重合性組成物には、熱安定剤や光安定剤などの安定剤、可塑剤、無機充填剤、滑剤、着色剤、シリコンオイル、発泡剤、難燃剤、表面調整剤、溶剤、バインダー、フィラー、顔料分散剤、導電性付与剤、紫外線吸収剤、酸化防止剤、乾燥防止剤、浸透剤、ｐＨ調整剤、金属封鎖剤、防菌防かび剤、界面活性剤、可塑剤、ワックス、レベリング剤の添加剤を配合してもよい。 Furthermore, depending on the use of the polymerizable composition, the polymerizable composition may include stabilizers such as heat stabilizers and light stabilizers, plasticizers, inorganic fillers, lubricants, colorants, silicone oil, foaming agents, and Fuel, surface conditioner, solvent, binder, filler, pigment dispersant, conductivity imparting agent, ultraviolet absorber, antioxidant, drying inhibitor, penetrant, pH adjuster, metal sequestering agent, antibacterial and fungicidal agent, Additives such as surfactants, plasticizers, waxes, and leveling agents may be added.
［重合物]
本発明は、上記重合性組成物から形成された重合物にも関する。前記重合物の例には、ポリウレタン、ポリチオウレタンが含まれる。
重合性組成物を用いて重合物を製造する方法としては、公知のポリウレタンまたはポリチオウレタンの製造方法が採用できる。本発明では、重合性組成物を所望の型に適用して、成形加工することが好ましい。成形加工法としては、例えば、注型成形法、射出成形法、トランスファー成形法、などがあげられる。また、特開２０１９－１３１７１１号公報の段落００４６～００４７の記載を参酌でき、この内容は本明細書に組み込まれる。
[Polymer]
The present invention also relates to polymers formed from the above polymerizable compositions. Examples of the polymer include polyurethane and polythiourethane.
As a method for producing a polymer using a polymerizable composition, a known method for producing polyurethane or polythiourethane can be employed. In the present invention, it is preferable to apply the polymerizable composition to a desired mold and process it. Examples of the molding method include cast molding, injection molding, and transfer molding. In addition, the descriptions in paragraphs 0046 to 0047 of JP 2019-131711 A can be referred to, and the contents thereof are incorporated into the present specification.
本発明の重合物は、例えば、レンズ、コーティング剤、ポリウレタンエラストマー、接着剤、フォーム、バインダー、弾性繊維、合成皮革、人工皮革、シーリング材、防水材、床材等に用いられ、レンズおよびコーティング剤に好ましく用いられる。
本発明の重合物をレンズに用いる場合、特開２０１７－０９５６９５号公報の記載を参酌でき、これらの内容は本明細書に組み込まれる。
本発明の重合物をコーティング材料に用いる場合、特開２０１５－２０６０１７号公報の記載を参酌でき、これらの内容は本明細書に組み込まれる、
The polymer of the present invention can be used, for example, in lenses, coating agents, polyurethane elastomers, adhesives, foams, binders, elastic fibers, synthetic leather, artificial leather, sealants, waterproof materials, flooring materials, etc. It is preferably used for.
When using the polymer of the present invention for a lens, the description in JP-A-2017-095695 can be referred to, and the contents thereof are incorporated herein.
When using the polymer of the present invention as a coating material, the description in JP-A-2015-206017 can be referred to, the contents of which are incorporated herein.
以下に実施例を挙げて本発明をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。 The present invention will be explained in more detail with reference to Examples below. The materials, usage amounts, proportions, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.
イソシアネート化合物の分析は以下の方法にて行った。
＜イソシアネート化合物の分析＞
（１）ガスクロマトグラフィー（以下、「ＧＣ分析」ということがある）
装置：島津製作所製社製、ＧＣ－２０２５
カラム：アジレント・テクノロジー社製、ＣＰ－Ｓｉｌ８ＣＢｆｏｒＡｍｉｎｅｓ（０．２５μｍ×０．２５ｍｍ×３０ｍ）
カラム温度：８０℃で２分間維持した後、８℃／分の速度で昇温し、１５０℃に達した後、５分間維持し、１５℃／分の速度で昇温し、３００℃に達した後、５分間維持した。
（２）飛行時間形質量分析（以下、「ＴＯＦＭＳ分析」ということがある）
装置：日本電子社製、ＡｃｃｕＴＯＦ ＧＣＸ
イオン化手法：ＦＩ+
（３）核磁気共鳴吸収法（1Ｈ－ＮＭＲ、13Ｃ－ＮＭＲ）
装置：ＢＲＵＫＥＲ製、核磁気共鳴装置ＡＶＡＮＣＥＩＩ６００ＭＨｚ
重水素置換クロロホルム溶剤中で測定を行った。尚、後述のδ（ｐｐｍ）は次式で表される化学シフトを示す。
δ（ｐｐｍ）＝１０6×（νS－νR）／νR
νS：試料の共鳴周波数（Ｈｚ）
νR：標準物質のトリメチルシラン（ＴＭＳ）の共鳴周波数（Ｈｚ）
（４）赤外線（ＩＲ）スペクトル分析
装置：ＦＴ／ＩＲ－４１００ｔｙｐｅＡ
合成反応後溶剤を留去した粗生成物についてＡＴＲ法を用いて、分析を実施した。
The isocyanate compound was analyzed by the following method.
<Analysis of isocyanate compounds>
(1) Gas chromatography (hereinafter sometimes referred to as "GC analysis")
Equipment: Manufactured by Shimadzu Corporation, GC-2025
Column: Agilent Technologies, CP-Sil8CBforAmines (0.25 μm x 0.25 mm x 30 m)
Column temperature: Maintained at 80°C for 2 minutes, then increased the temperature at a rate of 8°C/min. After reaching 150°C, maintained for 5 minutes, then increased the temperature at a rate of 15°C/min, reaching 300°C. After that, it was maintained for 5 minutes.
(2) Time-of-flight mass spectrometry (hereinafter sometimes referred to as "TOFMS analysis")
Equipment: AccuTOF GCX manufactured by JEOL Ltd.
Ionization method: FI +
(3) Nuclear magnetic resonance absorption method ( 1 H-NMR, 13 C-NMR)
Equipment: BRUKER, nuclear magnetic resonance device AVANCE II 600MHz
Measurements were carried out in a deuterated chloroform solvent. Note that δ (ppm), which will be described later, indicates a chemical shift expressed by the following formula.
δ (ppm) = 10 6 × (ν S - ν R )/ν R
ν S : Resonance frequency of sample (Hz)
ν R : Resonance frequency (Hz) of standard material trimethylsilane (TMS)
(4) Infrared (IR) spectrum analyzer: FT/IR-4100typeA
After the synthesis reaction, the solvent was distilled off and the crude product was analyzed using the ATR method.
（塩基組成物の調製）
磁気撹拌子を備えた２００ｍＬのナスフラスコに窒素雰囲気下で、炭酸セシウム（Ｃｓ2ＣＯ3、富士フイルム和光純薬社製）２３．３７５ｇ、金属ナトリウム（Ｎａ、富士フイルム和光純薬社製）１．６５ｇ、酸化マグネシウム（ＭｇＯ、富士フイルム和光純薬社製）１７．６ｇを仕込んだ。このナスフラスコをアルミブロックヒータースターラーに設置して、２５０℃で、１時間加熱撹拌した後に、アルミブロックヒータースターラーから取り外した。上記ナスフラスコを空冷で室温まで冷却して、塩基組成物を得た。
(Preparation of base composition)
In a 200 mL eggplant flask equipped with a magnetic stirrer under a nitrogen atmosphere, 23.375 g of cesium carbonate (Cs 2 CO 3 , manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 1 g of metallic sodium (Na, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) were added. .65 g and 17.6 g of magnesium oxide (MgO, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) were charged. This eggplant flask was placed in an aluminum block heater stirrer, heated and stirred at 250° C. for 1 hour, and then removed from the aluminum block heater stirrer. The above eggplant flask was air-cooled to room temperature to obtain a base composition.
（合成例１：α，α，α’，α’－テトラエチルメタキシリレンジアミンの合成）
冷却水循環ジャケット、撹拌翼を備えた５００ｍＬオートクレーブにアルゴン雰囲気下で、上記で得られた塩基組成物１２．２ｇ、および、テトラヒドロフラン（富士フイルム和光純薬社製、超脱水、安定剤不含グレード）２５ｍＬを入れた後、ジャケットに－５℃の冷媒を循環させ、内溶液温度を１０℃とした。液温が１℃になるように氷冷した１３．２ｇのα，α，α’－トリエチルメタキシリレンジアミンと８０ｍＬのテトラヒドロフランからなる原料溶液を窒素ガスの圧力によりオートクレーブ内に導入しジャケットに冷媒を循環させながら１５分間７００ｒｐｍで撹拌した。撹拌を継続しながらオートクレーブをエチレンガスボンベに接続し、エチレンガス（ジャパンファインプロダクツ社製、エチレン純度：９９．９体積％超）を１．８ＭＰａの圧力で充填した。冷媒の温度を２０℃に変更し、２４時間撹拌を継続し反応を行った。反応液に５３ｍＬのイソプロピルアルコールを加えて反応を停止し、Ｎｏ．５Ｃ桐山ろ紙で塩基組成物残渣を取り除いた。ろ液に３００ｍＬのクロロホルム（富士フイルム和光純薬社製）と２００ｍＬの純水を加えて、分液操作を行った後、有機層側を回収、エバポレーターを用いて溶剤を留去することで１５．６ｇの粗生成物を得た。粗生成物を原料に１２０Ｐａの減圧条件下で単蒸留を行い純度９２％のα，α，α’，α’－テトラエチルメタキシリレンジアミンを得た。
(Synthesis Example 1: Synthesis of α,α,α',α'-tetraethylmethaxylylenediamine)
In an argon atmosphere, 12.2 g of the base composition obtained above and tetrahydrofuran (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., ultra-dehydrated, stabilizer-free grade) were placed in a 500 mL autoclave equipped with a cooling water circulation jacket and a stirring blade. After adding 25 mL, a -5°C refrigerant was circulated through the jacket to bring the internal solution temperature to 10°C. A raw material solution consisting of 13.2 g of α, α, α'-triethyl metaxylylene diamine and 80 mL of tetrahydrofuran, which had been ice-cooled so that the liquid temperature was 1°C, was introduced into the autoclave under nitrogen gas pressure, and the refrigerant was introduced into the jacket. The mixture was stirred at 700 rpm for 15 minutes while circulating. While stirring, the autoclave was connected to an ethylene gas cylinder and filled with ethylene gas (manufactured by Japan Fine Products, ethylene purity: over 99.9% by volume) at a pressure of 1.8 MPa. The temperature of the refrigerant was changed to 20° C., and stirring was continued for 24 hours to carry out the reaction. 53 mL of isopropyl alcohol was added to the reaction solution to stop the reaction, and No. The base composition residue was removed using 5C Kiriyama filter paper. After adding 300 mL of chloroform (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) and 200 mL of pure water to the filtrate and performing a liquid separation operation, the organic layer side was collected and the solvent was distilled off using an evaporator. .6 g of crude product was obtained. Using the crude product as a raw material, simple distillation was performed under reduced pressure conditions of 120 Pa to obtain α,α,α',α'-tetraethyl metaxylylenediamine with a purity of 92%.
（合成例２：α，α，α’－トリエチルメタキシリレンジアミンの合成）
冷却水循環ジャケット、撹拌翼を備えた５００ｍＬオートクレーブにアルゴン雰囲気下で、上記で得られた塩基組成物１９．２ｇ、および、テトラヒドロフラン（富士フイルム和光純薬社製、超脱水、安定剤不含グレード）３０ｍＬを入れた後、ジャケットに－５℃の冷媒を循環させ、内溶液温度を６℃とした。液温が１℃になるように氷冷した１３．２ｇのメタキシリレンジアミン（東京化成工業社製）と７５ｍＬのテトラヒドロフランからなる原料溶液を窒素ガスの圧力によりオートクレーブ内に導入し、ジャケットに冷媒を循環させながら１５分間７００ｒｐｍで撹拌した。撹拌を継続しながらオートクレーブをエチレンガスボンベに接続し、エチレンガス（ジャパンファインプロダクツ社製、エチレン純度：９９．９体積％超）を１．８ＭＰａの圧力で充填した。冷媒の温度を２０℃に変更し、２４時間撹拌を継続し反応を行った。反応液に５３ｍＬのイソプロピルアルコールを加えて反応を停止し、Ｎｏ．５Ｃ桐山ろ紙で塩基組成物残渣を取り除いた。ろ液に３００ｍＬのクロロホルム（富士フイルム和光純薬社製）と２００ｍＬの純水を加えて、分液操作を行った後、有機層側を回収、エバポレーターを用いて溶剤を留去することで２２ｇ（α，α，α’－トリエチルメタキシリレンジアミン含有率５４質量％）の粗生成物を得た。粗生成物を原料に４０～５０Ｐａの減圧条件下で精密蒸留を行い純度９８％のα，α，α’－トリエチルメタキシリレンジアミンを得た。
(Synthesis Example 2: Synthesis of α,α,α'-triethylmethaxylylenediamine)
19.2 g of the base composition obtained above and tetrahydrofuran (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., ultra-dehydrated, stabilizer-free grade) were placed in a 500 mL autoclave equipped with a cooling water circulation jacket and a stirring blade under an argon atmosphere. After adding 30 mL, a -5°C refrigerant was circulated through the jacket to bring the internal solution temperature to 6°C. A raw material solution consisting of 13.2 g of metaxylylene diamine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 75 mL of tetrahydrofuran, which had been ice-cooled so that the liquid temperature was 1°C, was introduced into the autoclave under nitrogen gas pressure, and the refrigerant was introduced into the jacket. The mixture was stirred at 700 rpm for 15 minutes while circulating. While stirring, the autoclave was connected to an ethylene gas cylinder and filled with ethylene gas (manufactured by Japan Fine Products, ethylene purity: over 99.9% by volume) at a pressure of 1.8 MPa. The temperature of the refrigerant was changed to 20° C., and stirring was continued for 24 hours to carry out the reaction. 53 mL of isopropyl alcohol was added to the reaction solution to stop the reaction, and No. The base composition residue was removed using 5C Kiriyama filter paper. After adding 300 mL of chloroform (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) and 200 mL of pure water to the filtrate and performing a liquid separation operation, the organic layer side was collected and the solvent was distilled off using an evaporator to obtain 22 g. A crude product (α,α,α'-triethylmethaxylylenediamine content: 54% by mass) was obtained. Using the crude product as a raw material, precision distillation was performed under reduced pressure conditions of 40 to 50 Pa to obtain α,α,α'-triethylmethaxylylenediamine with a purity of 98%.
（実施例１） α，α，α’，α’－テトラエチルメタキシリレンジイソシアネート化合物（２）の合成
合成例１で得られた純度９２％のα，α，α’，α’－テトラエチルメタキシリレンジアミン５．００ｇにキシレンを加えた後、共沸脱水を行い水分量３２質量ｐｐｍ（カールフィッシャー水分計での分析結果）とした。次いで、キシレン溶剤中に塩化水素を導入して、上記ジアミンを塩酸塩とし、ホスゲンを吹き込み、１２０℃で１時間反応させた。ホスゲンと溶剤のキシレンを留去し、５．８８ｇの粗生成物を得た。粗生成物を原料に２６０Ｐａの減圧条件下で単蒸留を実施した結果、ガスクロマトグラフィー純度９４％の化合物（２）を含有する無色透明の留分４．５１ｇを取得した。
(Example 1) Synthesis of α,α,α',α'-tetraethylmethaxylylene diisocyanate compound (2) α,α,α',α'-tetraethylmethaxylylene with a purity of 92% obtained in Synthesis Example 1 After adding xylene to 5.00 g of diamine, azeotropic dehydration was performed to obtain a water content of 32 mass ppm (analysis result with a Karl Fischer moisture meter). Next, hydrogen chloride was introduced into the xylene solvent to convert the diamine into a hydrochloride salt, phosgene was blown into the xylene solvent, and the mixture was reacted at 120° C. for 1 hour. Phosgene and the solvent xylene were distilled off to obtain 5.88 g of a crude product. As a result of carrying out simple distillation under reduced pressure conditions of 260 Pa using the crude product as a raw material, 4.51 g of a colorless and transparent fraction containing compound (2) with a gas chromatography purity of 94% was obtained.
α，α，α’，α’－テトラエチルメタキシリレンジイソシアネート化合物（２）の各種スペクトルデータは以下のとおりであった。
1Ｈ ＮＭＲ（ＣＤＣｌ3、テトラメチルシラン）δ（ｐｐｍ）：０．７７１、０．７８６、０．８００（１２Ｈ、ｔ、Ａｒ－Ｃ(ＮＣＯ)－ＣＨ2－ＣＨ3におけるＣＨ3の水素）、１．９４８、１．９６２、１．９７７、１．９９２（８Ｈ、ｑ、Ａｒ－Ｃ(ＮＣＯ)－ＣＨ２－ＣＨ3におけるＣＨ2の水素）、７．１９８～７．２３０（３Ｈ、Ａｒ）、７．３１６～７．３４７（１Ｈ、Ａｒ）
13Ｃ ＮＭＲ（ＣＤＣｌ3、テトラメチルシラン）δ（ｐｐｍ）：８．５、３７．０１、６９．４、１２２．０、１２２．９、１２４．２、１２８．４、１４２．２５
ＴＯＦＭＳ分析：ｍ／ｅの理論値（Ｃ18Ｈ24Ｎ2Ｏ2）として３００．１８３２３、実測値３００．１８４８６。
上記においてＡｒはベンゼン環を示している（以下、同じ）。
ＩＲスペクトル分析：２２５２ｃｍ-1（ＮＣＯ伸縮振動）
Various spectral data of α, α, α', α'-tetraethyl metaxylylene diisocyanate compound (2) were as follows.
1 H NMR (CDCl 3 , tetramethylsilane) δ (ppm): 0.771, 0.786, 0.800 (12H, t, hydrogen of CH 3 in Ar-C(NCO)-CH 2 -CH 3 ) , 1.948, 1.962, 1.977, 1.992 (8H, q, hydrogen of CH 2 in Ar-C(NCO)-CH2-CH 3 ), 7.198-7.230 (3H, Ar ), 7.316-7.347 (1H, Ar)
13C NMR ( CDCl3 , tetramethylsilane) δ (ppm): 8.5, 37.01, 69.4, 122.0, 122.9, 124.2, 128.4, 142.25
TOFMS analysis: theoretical m/e value (C 18 H 24 N 2 O 2 ) of 300.18323, actual value of 300.18486.
In the above, Ar represents a benzene ring (the same applies hereinafter).
IR spectrum analysis: 2252 cm -1 (NCO stretching vibration)
（実施例２） α，α，α’－トリエチルメタキシリレンジイソシアネート化合物（３）の合成
合成例２で得られた純度９８％のα，α，α’－トリエチルメタキシリレンジアミン５．００gにキシレンを加えた後、共沸脱水を行い水分量５２質量ｐｐｍ（カールフィッシャー水分計での分析結果）とした。次いでキシレン溶剤中に塩化水素を導入し、原料ジアミンを塩酸塩とし、ホスゲンを吹き込み、１２０℃で１時間反応させた。ホスゲンと溶剤のキシレンを留去し、５.９６ｇの粗生成物を得た。粗生成物を原料に３００Ｐａの減圧条件下で単蒸留を実施した結果、ガスクロマトグラフィー純度９６％の化合物（３）を含有する無色透明の留分４．３３ｇを取得した。
(Example 2) Synthesis of α,α,α'-triethyl metaxylylene diisocyanate compound (3) To 5.00 g of α, α, α'-triethyl metaxylylene diisocyanate with a purity of 98% obtained in Synthesis Example 2 After adding xylene, azeotropic dehydration was performed to obtain a water content of 52 mass ppm (analysis result with a Karl Fischer moisture meter). Next, hydrogen chloride was introduced into the xylene solvent to convert the raw material diamine into a hydrochloride salt, phosgene was blown into the solution, and the mixture was reacted at 120° C. for 1 hour. Phosgene and the solvent xylene were distilled off to obtain 5.96 g of a crude product. As a result of performing simple distillation under reduced pressure conditions of 300 Pa using the crude product as a raw material, 4.33 g of a colorless and transparent fraction containing compound (3) with a gas chromatography purity of 96% was obtained.
α，α，α，α’－トリエチルメタキシリレンジイソシアネート化合物（３）の各種スペクトルデータは以下のとおりであった。
1Ｈ ＮＭＲ（ＣＤＣｌ3、テトラメチルシラン） δ（ｐｐｍ）：０．７８４、０．８０１、０．８１５（６Ｈ、ｔ、Ａｒ－Ｃ(ＮＣＯ)－ＣＨ2－ＣＨ3におけるＣＨ3の水素）、０．９５２、０．９６６、０．９８１（３Ｈ、ｔ、Ａｒ－ＣＨ(ＮＣＯ)－ＣＨ2－ＣＨ3におけるＣＨ3の水素）、１．８２５～１．８８２（２Ｈ、ｍ、Ａｒ－ＣＨ(ＮＣＯ)－ＣＨ2－ＣＨ3におけるＣＨ2の水素）、１．９４２～１．９９２（４Ｈ、ｍ、Ａｒ－Ｃ(ＮＣＯ)－ＣＨ2－ＣＨ3におけるＣＨ2の水素）、４．５４０、４．５５３、４．５６６（１Ｈ、ｔ、Ａｒ－ＣＨ(ＮＣＯ)－ＣＨ2－ＣＨ3におけるＣＨの水素）７．１９３、７．２１１、７．２４３、７．２４６（３Ｈ、Ａｒ）７．３３２、７．３４８、７．３６３（１Ｈ、Ａｒ）。
13Ｃ ＮＭＲ（ＣＤＣｌ3、テトラメチルシラン） δ（ｐｐｍ）：８．５５、１０．５５、３２．９２、３６．９３、３６．９７、６０．８８、６９．２９、１２１．９５、１２３．２０、１２３．２７、１２４．３９、１２５．０３、１２８．７５、１４１．３９、１４２．７６。
ＴＯＦＭＳ分析：ｍ／ｅの理論値（Ｃ16Ｈ20Ｎ2Ｏ2）として２７２．１５１９３、実測値２７２．１５０６３。
ＩＲスペクトル分析：２２５０ｃｍ-1（ＮＣＯ伸縮振動）
Various spectral data of α,α,α,α'-triethylmethaxylylene diisocyanate compound (3) were as follows.
1 H NMR (CDCl 3 , tetramethylsilane) δ (ppm): 0.784, 0.801, 0.815 (6H, t, hydrogen of CH 3 in Ar-C(NCO)-CH 2 -CH 3 ) , 0.952, 0.966, 0.981 (3H, t, hydrogen of CH 3 in Ar-CH(NCO)-CH 2 -CH 3 ), 1.825-1.882 (2H, m, Ar- Hydrogen of CH 2 in CH(NCO)-CH 2 -CH 3 ), 1.942-1.992 (4H, m, hydrogen of CH 2 in Ar-C(NCO)-CH 2 -CH 3 ), 4. 540, 4.553, 4.566 (1H, t, hydrogen of CH in Ar-CH(NCO)-CH 2 -CH 3 ) 7.193, 7.211, 7.243, 7.246 (3H, Ar ) 7.332, 7.348, 7.363 (1H, Ar).
13C NMR ( CDCl3 , tetramethylsilane) δ (ppm): 8.55, 10.55, 32.92, 36.93, 36.97, 60.88, 69.29, 121.95, 123. 20, 123.27, 124.39, 125.03, 128.75, 141.39, 142.76.
TOFMS analysis: theoretical m/e value (C 16 H 20 N 2 O 2 ) of 272.15193, actual value of 272.15063.
IR spectrum analysis: 2250cm -1 (NCO stretching vibration)
（実施例３）
ペンタエリスリトールテトラキスチオプロピオネート（東京化成工業社製）２．２９７ｇとα，α，α’，α’－テトラエチルメタキシリレンジイソシアネート２．７０３ｇ、２－エチルヘキサン酸錫(II)（富士フイルム和光純薬社製）２５ｍｇ、１，４－ジアザビシクロ［２，２，２］オクタン（東京化成工業社製）２５ｍｇを混合し重合性組成物を調製した。
(Example 3)
2.297 g of pentaerythritol tetrakisthiopropionate (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 2.703 g of α, α, α', α'-tetraethylmethaxylylene diisocyanate, tin(II) 2-ethylhexanoate (manufactured by Fujifilm Wa A polymerizable composition was prepared by mixing 25 mg of 1,4-diazabicyclo[2,2,2]octane (manufactured by Tokyo Chemical Industry Co., Ltd.).
（実施例４）
＜重合物の作製＞
重合性組成物を脱気後、２．５ｍｍ厚の平板レンズ用モールドに注入し、オーブン中で昇温速度８℃／時間の条件で４０℃から１２０℃まで昇温後、１２０℃で１２時間保持する条件で加熱し重合硬化を進行させることで、重合物（ポリチオウレタン）（以下、「サンプル」と呼ぶ」）を作製した。得られたサンプルは無色透明であった。
(Example 4)
<Preparation of polymer>
After degassing the polymerizable composition, it was injected into a 2.5 mm thick flat lens mold, heated in an oven from 40°C to 120°C at a heating rate of 8°C/hour, and then heated at 120°C for 12 hours. A polymer (polythiourethane) (hereinafter referred to as "sample") was produced by heating under the same conditions to advance polymerization and curing. The obtained sample was colorless and transparent.
＜重合物の評価＞
重合物の評価は以下の方法により行った。
ガラス転移温度の測定：
サンプルを３ｍｍに切り出し、直径１ｍｍのピンに１０ｇの加重を与え、３０℃から１０℃／分で昇温し、熱機械分析（ＴＭＡ法）測定を行い、ガラス転移温度（℃）を測定した。
屈折率：
上記で得られたサンプルについて、カルニュー精密屈折計（ＫＰＲ－２０００）を用い温度２５℃、湿度５０％の条件で行った。屈折率の波長は、５８９．３ｎｍのＤ線における値である。
黄色度（ＹＩ）：
上記で得られたサンプル（厚み２．５ｍｍ）について、コニカミノルタ社製の分光測色計ＣＭ－５でＹＩを測定した。
ヘイズ値：
上記で得られたサンプル（厚み２．５ｍｍ）について、コニカミノルタ社製の分光測色計ＣＭ－５でＡＳＴＭ Ｄ１００３に準拠して測定した。
各評価結果を表１に示す。
<Evaluation of polymer>
Evaluation of the polymer was performed by the following method.
Measurement of glass transition temperature:
A sample was cut into 3 mm pieces, a 10 g load was applied to a 1 mm diameter pin, the temperature was raised from 30° C. at a rate of 10° C./min, and thermomechanical analysis (TMA method) was performed to measure the glass transition temperature (° C.).
Refractive index:
The samples obtained above were tested using a Kalnew Precision Refractometer (KPR-2000) at a temperature of 25° C. and a humidity of 50%. The wavelength of the refractive index is the value at the D line of 589.3 nm.
Yellowness (YI):
The YI of the sample (thickness 2.5 mm) obtained above was measured using a spectrophotometer CM-5 manufactured by Konica Minolta.
Haze value:
The sample obtained above (thickness: 2.5 mm) was measured in accordance with ASTM D1003 using a spectrophotometer CM-5 manufactured by Konica Minolta.
The results of each evaluation are shown in Table 1.
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