JP2021004229A - Novel isocyanurate compound having thiol groups and use thereof - Google Patents
Novel isocyanurate compound having thiol groups and use thereof Download PDFInfo
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- JP2021004229A JP2021004229A JP2019128803A JP2019128803A JP2021004229A JP 2021004229 A JP2021004229 A JP 2021004229A JP 2019128803 A JP2019128803 A JP 2019128803A JP 2019128803 A JP2019128803 A JP 2019128803A JP 2021004229 A JP2021004229 A JP 2021004229A
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- compound
- isocyanurate
- epoxy resin
- present
- thiol group
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- -1 isocyanurate compound Chemical class 0.000 title claims abstract description 75
- 125000003396 thiol group Chemical group [H]S* 0.000 title claims abstract description 29
- 239000003822 epoxy resin Substances 0.000 claims abstract description 26
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 abstract description 22
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 11
- 239000007983 Tris buffer Substances 0.000 abstract description 10
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- 239000004848 polyfunctional curative Substances 0.000 abstract 2
- 239000000243 solution Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000002904 solvent Substances 0.000 description 11
- 239000004593 Epoxy Substances 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 150000003566 thiocarboxylic acids Chemical class 0.000 description 9
- 239000000126 substance Substances 0.000 description 7
- 239000012989 trithiocarbonate Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 150000003573 thiols Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 238000006606 decarbonylation reaction Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical group CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 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
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- SSUJUUNLZQVZMO-UHFFFAOYSA-N 1,2,3,4,8,9,10,10a-octahydropyrimido[1,2-a]azepine Chemical compound C1CCC=CN2CCCNC21 SSUJUUNLZQVZMO-UHFFFAOYSA-N 0.000 description 1
- XGINAUQXFXVBND-UHFFFAOYSA-N 1,2,6,7,8,8a-hexahydropyrrolo[1,2-a]pyrimidine Chemical compound N1CC=CN2CCCC21 XGINAUQXFXVBND-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-M 3-mercaptopropionate Chemical compound [O-]C(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-M 0.000 description 1
- DGUJJOYLOCXENZ-UHFFFAOYSA-N 4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenol Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 DGUJJOYLOCXENZ-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- AFYPFACVUDMOHA-UHFFFAOYSA-N chlorotrifluoromethane Chemical compound FC(F)(F)Cl AFYPFACVUDMOHA-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 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
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
Abstract
Description
本発明は、新規なチオール基を有するイソシアヌレート化合物、そのチオール基を有するイソシアヌレート化合物の製造方法、およびそのチオール基を有するイソシアヌレート化合物を含む樹脂組成物に関する。特には耐水性に優れた樹脂組成物に用いられるチオール基を有するイソシアヌレート化合物、そのチオール基を有するイソシアヌレート化合物の製造方法、およびそのチオール基を有するイソシアヌレート化合物を含む樹脂組成物に関する。 The present invention relates to a novel isocyanurate compound having a thiol group, a method for producing an isocyanurate compound having the thiol group, and a resin composition containing the isocyanurate compound having the thiol group. In particular, the present invention relates to an isocyanurate compound having a thiol group used in a resin composition having excellent water resistance, a method for producing an isocyanurate compound having a thiol group, and a resin composition containing an isocyanurate compound having the thiol group.
従来、チオール化合物は、コーティング材料、ＵＶ及び熱硬化塗料、接着剤、インキ、レジスト材料、光学材料、樹脂原料などの広範囲で用いられる。特に多官能チオールでは高い密着強度が得られることからエポキシ樹脂や不飽和基を有するモノマーの硬化剤として使用できるとされている（特許文献１）。 Conventionally, thiol compounds are widely used in coating materials, UV and thermosetting paints, adhesives, inks, resist materials, optical materials, resin raw materials and the like. In particular, polyfunctional thiols are said to be usable as curing agents for epoxy resins and monomers having unsaturated groups because high adhesion strength can be obtained (Patent Document 1).
特に、イソシアヌル酸と加水分解性基を持たないチオールで構成された化合物を用いた硬化物は、剛直なイソシアヌル酸と、強い疎水基を有していることから、水が浸入しにくく、耐水性が要求される用途にも使用することが可能とされている（特許文献２）。 In particular, a cured product using a compound composed of isocyanuric acid and a thiol having no hydrolyzable group has rigid isocyanuric acid and a strong hydrophobic group, so that it is difficult for water to penetrate and water resistance. It is possible to use it for applications requiring the above (Patent Document 2).
このような背景から産業界では、耐加水分解性に優れるエポキシ樹脂硬化物を与えるエポキシ樹脂用硬化剤が要望されている。 Against this background, the industry is demanding a curing agent for epoxy resin that provides a cured product of an epoxy resin having excellent hydrolysis resistance.
一方、市場で供給されているイソシアヌル酸とチオール基が配置する側鎖で構成された化合物としては１，３，５−トリス［（３−メルカプトプロピオニルオキシ）エチル］イソシアヌレートおよび１，３，５‐トリス［（３‐メルカプトブチリルオキシ）エチル］イソシアヌレートが存在するが、いずれも側鎖に加水分解性基を含んでおり、イソシアヌル酸と加水分解をしないエーテル基を含む側鎖で構成された化合物は存在しない。 On the other hand, commercially available compounds composed of isocyanuric acid and a side chain in which a thiol group is arranged include 1,3,5-tris [(3-mercaptopropionyloxy) ethyl] isocyanurate and 1,3,5. -Tris [(3-mercaptobutyryloxy) ethyl] isocyanurate is present, but all contain hydrolyzable groups in the side chains and are composed of side chains containing isocyanuric acid and non-hydrolyzable ether groups. There is no compound.
新規なチオール基を有するイソシアヌレート化合物を硬化剤として含み、耐加水分解性に優れるエポキシ樹脂組成物を提供することを課題とする。 An object of the present invention is to provide an epoxy resin composition containing an isocyanurate compound having a novel thiol group as a curing agent and having excellent hydrolysis resistance.
本発明者らは上記課題を解決すべく検討した結果、下記式（Ｉ）で表されるチオール基を有するイソシアヌレート化合物が上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of studies to solve the above problems, the present inventors have found that an isocyanurate compound having a thiol group represented by the following formula (I) can achieve the above object, and have completed the present invention.
即ち本発明は下記式（Ｉ）で表されるチオール基を有するイソシアヌレート化合物をエポキシ樹脂硬化剤として使用することで、上記課題を解決し、本発明を完成するに至ったものである。 That is, the present invention has solved the above problems and completed the present invention by using an isocyanurate compound having a thiol group represented by the following formula (I) as an epoxy resin curing agent.
本発明によれば、下記式（Ｉ）
また、本発明によれば、上記式（Ｉ）で表されるチオール基を有するイソシアヌレート化合物を含むエポキシ樹脂用硬化剤が提供される。 Further, according to the present invention, there is provided a curing agent for an epoxy resin containing an isocyanurate compound having a thiol group represented by the above formula (I).
更に、本発明によれば、上記エポキシ樹脂用硬化剤を含むエポキシ樹脂組成物が提供される。 Further, according to the present invention, an epoxy resin composition containing the above-mentioned curing agent for epoxy resin is provided.
本発明による上記式（Ｉ）で表されるチオール基を有するイソシアヌレート化合物は、イソシアヌレート環の有する３個の窒素原子上の水素原子が、チオール基を有する置換基にて置換された新規な化合物である。 The isocyanurate compound having a thiol group represented by the above formula (I) according to the present invention is a novel compound in which a hydrogen atom on three nitrogen atoms of the isocyanurate ring is substituted with a substituent having a thiol group. It is a compound.
また、本発明による上記式（Ｉ）で表されるチオール基を有するイソシアヌレート化合物は、エポキシ樹脂用硬化剤として有用である。更に分子中に加水分解性のエステル基を持たないので、従来のポリチオール類よりも、耐加水分解性にすぐれるエポキシ樹脂硬化物を与える。 Further, the isocyanurate compound having a thiol group represented by the above formula (I) according to the present invention is useful as a curing agent for epoxy resins. Furthermore, since it does not have a hydrolyzable ester group in the molecule, it provides a cured epoxy resin having better hydrolysis resistance than conventional polythiols.
本発明に係る式（Ｉ）に示されるチオール基を有するイソシアヌレート化合物は下記化学式スキームのようにイソシアヌル酸の窒素上に不飽和アルキル基が置換したトリエン化合物（ＩＩ）にチオカルボン酸類を付加させた後に、生成したチオカルボニル基を分解させることにより合成される。
式中（ＩＩ）で表される１，３，５−トリス［２−（２−プロペン−１−イロキシ）エチル］イソシアヌレートの調製は、ＷＯ２０１５１０６４３８に記載されている１，３，５−トリス（ヒドロキシエチル）イソシアヌレートとハロゲン化アリルとの反応など、様々な方法によって得られる。The isocyanurate compound having a thiol group represented by the formula (I) according to the present invention is obtained by adding thiocarboxylic acids to the triene compound (II) in which an unsaturated alkyl group is substituted on the nitrogen of isocyanuric acid as in the following chemical formula scheme. Later, it is synthesized by decomposing the generated thiocarbonyl group.
The preparation of 1,3,5-tris [2- (2-propen-1-yloxy) ethyl] isocyanurate represented by (II) in the formula is described in WO2015106438. It can be obtained by various methods such as the reaction of (hydroxyethyl) isocyanurate with allyl halide.
本発明に用いられる式（ＩＩＩ）で表されるトリチオカルボネート化合物は、トリエン化合物（ＩＩ）とチオカルボン酸との反応により得られる。 The trithiocarbonate compound represented by the formula (III) used in the present invention is obtained by reacting the triene compound (II) with a thiocarboxylic acid.
Ｒのアルキル基としては、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｉ−‐ブチル基、ｓ−ブチル基、ｔ−ブチル基、ｎ−ペンチル基、１−メチル−ｎ−ブチル基、２−メチル−ｎ−ブチル基、３−メチル−ｎ−ブチル基、１，１−ジメチル−ｎ−プロピル基、１，２−ジメチル−ｎ−プロピル基、２，２−ジメチル−ｎ−プロピル基、１−エチル−ｎ−プロピル基等が挙げられるが、好ましくはメチル基である。 As the alkyl group of R, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, 1 -Methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2, Examples thereof include 2-dimethyl-n-propyl group and 1-ethyl-n-propyl group, but a methyl group is preferable.
また、上記式（Ｉ）で表されるチオール基を有するイソシアヌレート化合物は、式（ＩＩＩ）のトリチオカルボネート化合物の分解反応により得られる。 The isocyanurate compound having a thiol group represented by the above formula (I) is obtained by a decomposition reaction of the trithiocarbonate compound of the formula (III).
上記、トリエン化合物（ＩＩ）と上記チオカルボン酸との反応において、上記チオカルボン酸類はトリエン化合物（ＩＩ）１モルに対して、通常、２．５〜１０モルの割合にて用いられ、好ましくは３．０〜５．０モルの割合にて用いられる。 In the reaction between the triene compound (II) and the thiocarboxylic acid, the thiocarboxylic acids are usually used at a ratio of 2.5 to 10 mol, preferably 2.5 to 10 mol, per 1 mol of the triene compound (II). It is used at a ratio of 0 to 5.0 mol.
上記トリエン化合物（ＩＩ）と上記チオカルボン酸類との反応において触媒を用いることができる。上記触媒としては、例えば、アゾビスイソブチロニトリルや過酸化ベンゾイルが好ましい。触媒の使用量はトリエン化合物（ＩＩ）１モルに対して、通常、０．００１〜１．２モルの割合にて用いられ、好ましくは０．００５〜０．４モルの割合にて用いられる。 A catalyst can be used in the reaction between the triene compound (II) and the thiocarboxylic acids. As the catalyst, for example, azobisisobutyronitrile or benzoyl peroxide is preferable. The amount of the catalyst used is usually 0.001 to 1.2 mol, preferably 0.005 to 0.4 mol, based on 1 mol of the triene compound (II).
上記トリエン化合物（ＩＩ）と上記チオカルボン酸との反応において、必要に応じて、溶媒を用いてもよい。溶媒は反応を阻害しない限りは、特に、制限されることは無いが、例えば、水、メタノール、エタノール、イソプロピルアルコールのようなアルコール類、ヘキサン、ヘプタンのような脂肪族炭化水素類、アセトン、２−ブタノンのようなケトン類、酢酸エチル、酢酸ブチルのようなエステル類、ベンゼン、トルエン、キシレンのような芳香族炭化水素類、塩化メチレン、クロロホルム、四塩化炭素、クロロトリフルオロメタン、ジクロロエタン、クロロベンゼン、ジクロロベンゼンのようなハロゲン化炭化水素類、ジエチルエーテル、ジイソプロピルエーテル、テトラヒドロフラン、ジオキサン、ジメトキシエタン、ジエチレングリコールジメチルエーテルのようなエーテル類、ホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン、ヘキサメチルホスホロトアミドのようなアミド類、ジメチルスルホキシドのようなスルホキシド類等を挙げることができる。このような溶媒は、単独で、又は２種以上を組み合わせて用いられる。 If necessary, a solvent may be used in the reaction between the triene compound (II) and the thiocarboxylic acid. The solvent is not particularly limited as long as it does not inhibit the reaction, but for example, water, alcohols such as methanol, ethanol and isopropyl alcohol, aliphatic hydrocarbons such as hexane and heptane, acetone, 2 -Ketones such as butanone, esters such as ethyl acetate, butyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, chlorotrifluoromethane, dichloroethane, chlorobenzene, Halogenated hydrocarbons such as dichlorobenzene, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, ethers such as diethylene glycol dimethyl ether, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, N- Examples thereof include amides such as methyl-2-pyrrolidone and hexamethylphosphorotamide, and sulfoxides such as dimethyl sulfoxide. Such a solvent may be used alone or in combination of two or more.
上記トリエン化合物（ＩＩ）と上記チオカルボン酸との反応は、通常、−１０〜２００℃の範囲の温度で行われ、好ましくは、２５〜１５０℃の範囲の温度で行われる。また、反応時間は反応温度にもよるが、通常、１〜４８時間の範囲であり、好ましくは１〜１５時間の範囲である。 The reaction between the triene compound (II) and the thiocarboxylic acid is usually carried out at a temperature in the range of −10 to 200 ° C., preferably in the temperature range of 25 to 150 ° C. The reaction time depends on the reaction temperature, but is usually in the range of 1 to 48 hours, preferably in the range of 1 to 15 hours.
上記トリエン化合物（ＩＩ）と上記チオカルボン酸との反応終了後、得られた反応混合物から過剰のチオカルボン酸と溶媒を留去した後、残留物として式（ＩＩＩ）で表されるトリチオカルボネート化合物を得ることができる。 After completion of the reaction between the triene compound (II) and the thiocarboxylic acid, excess thiocarboxylic acid and the solvent were distilled off from the obtained reaction mixture, and then the trithiocarbonate compound represented by the formula (III) as a residue. Can be obtained.
得られたトリチオカルボネート化合物（ＩＩＩ）を種々の反応剤にて反応させることにより、本発明のチオール基を有するイソシアヌレート化合物（Ｉ）を得ることができる。 By reacting the obtained trithiocarbonate compound (III) with various reactants, the isocyanate compound (I) having a thiol group of the present invention can be obtained.
トリチオカルボネート化合物（ＩＩＩ）からチオール基を有するイソシアヌレート化合物（Ｉ）を得る時に用いられる反応としては酸によるエステル交換反応、もしくは還元剤による脱カルボニル化反応が挙げられる。 Examples of the reaction used for obtaining the isocyanate compound (I) having a thiol group from the trithiocarbonate compound (III) include a transesterification reaction with an acid and a decarbonylation reaction with a reducing agent.
酸によるエステル交換反応に用いられる酸は塩酸、硫酸、メタンスルホン酸、ｐ−トルエンスルホン酸等の酸性物質が挙げられるが、好ましくは、硫酸、塩酸である。 Examples of the acid used in the ester exchange reaction with an acid include acidic substances such as hydrochloric acid, sulfuric acid, methanesulfonic acid, and p-toluenesulfonic acid, but sulfuric acid and hydrochloric acid are preferable.
酸によるエステル交換反応に用いられる溶媒としてはアルコール系の溶媒が用いられ、例えばメタノール、エタノール、ｎ−プロパノール、イソプロピルアルコール、ｎ−ブタノール、２−メチル−１−プロパノール、２−ブタノール、２−メチル−２‐プロパノール等が挙げられるが、好ましくはメタノール、エタノールである。 Alcohol-based solvents are used as the solvent used for the ester exchange reaction with an acid, for example, methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl. -2-Propanol and the like can be mentioned, but methanol and ethanol are preferable.
上記トリチオカルボネート化合物（ＩＩＩ）の酸によるエステル交換反応は、通常、０〜１２０℃の範囲の温度で行われ、好ましくは、５０〜１００℃の範囲の温度で行われる。また、反応時間は反応温度にもよるが、通常、１〜２４時間の範囲であり、好ましく５〜１０時間の範囲である。 The transesterification reaction of the trithiocarbonate compound (III) with an acid is usually carried out at a temperature in the range of 0 to 120 ° C, preferably in the temperature range of 50 to 100 ° C. The reaction time depends on the reaction temperature, but is usually in the range of 1 to 24 hours, preferably in the range of 5 to 10 hours.
還元剤による脱カルボニル化反応に用いられる還元剤は、水素化ホウ素ナトリウム等のヒドリド還元剤や、ナトリウムメトキシド、ナトリウムエトキシド等のアルコキシド化合物が挙げられる。 Examples of the reducing agent used in the decarbonylation reaction with the reducing agent include hydride reducing agents such as sodium borohydride and alkoxide compounds such as sodium methoxide and sodium ethoxide.
還元剤による脱カルボニル化反応に用いられる溶媒としては、アルコール系の溶媒が用いられ、例えばメタノール、エタノール、ｎ−プロパノール、イソプロピルアルコール、ｎ−ブタノール、２−メチル−１−プロパノール、２−ブタノール、２−メチル−２‐プロパノール等が挙げられるが、好ましくはメタノール、エタノールである。場合により上記の溶媒にヘキサン、ヘプタンのような脂肪族炭化水素類、ベンゼン、トルエン、キシレンのような芳香族炭化水素類、ジエチルエーテル、ジイソプロピルエーテル、テトラヒドロフラン、ジオキサン、ジメトキシエタン、ジエチレングリコールジメチルエーテルのようなエーテル類等を混合して用いてもよい。 As the solvent used for the decarbonylation reaction with the reducing agent, an alcohol solvent is used, for example, methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, 2-methyl-1-propanol, 2-butanol, and the like. Examples thereof include 2-methyl-2-propanol, but methanol and ethanol are preferable. In some cases, the above solvents include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, diethylene glycol dimethyl ether and the like. Ethers and the like may be mixed and used.
上記トリチオカルボネート化合物（ＩＩＩ）の還元剤による脱カルボニル化反応は、通常、０〜１２０℃の範囲の温度で行われ、好ましくは、４０〜８０℃の範囲の温度で行われる。また、反応時間は反応温度にもよるが、通常、１〜２４時間の範囲であり、好ましく８〜１８時間の範囲である。 The decarbonylation reaction of the trithiocarbonate compound (III) with a reducing agent is usually carried out at a temperature in the range of 0 to 120 ° C., preferably in the temperature range of 40 to 80 ° C. The reaction time depends on the reaction temperature, but is usually in the range of 1 to 24 hours, preferably in the range of 8 to 18 hours.
また、例えば、抽出操作やカラムクロマトグラフィー等の方法によって、得られた反応混合物から目的とする式（Ｉ）で表される本発明のチオール基を有するイソシアヌレート化合物を分離、精製してもよい。 Further, for example, an isocyanurate compound having a thiol group of the present invention represented by the target formula (I) may be separated and purified from the obtained reaction mixture by a method such as an extraction operation or column chromatography. ..
本発明によるエポキシ樹脂用硬化剤に、式（Ｉ．）で表される本発明のチオール基を有するイソシアヌレート化合物を用い、多官能エポキシ化合物および、硬化促進剤を用いて硬化させることでエポキシ樹脂を与える。 As the curing agent for epoxy resin according to the present invention, an isocyanurate compound having a thiol group of the present invention represented by the formula (I.) is used, and the epoxy resin is cured by using a polyfunctional epoxy compound and a curing accelerator. give.
本発明において、使用されるエポキシ化合物としては、平均して１分子当たり２個以上のエポキシ基を有するエポキシ化合物であり、そのような多価エポキシ化合物としては、特に限定されないが、例えば、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＡＤ、カテコール、レゾルシノール等の多価フェノール、グリセリンやポリエチレングリコール等の多価アルコールとエピクロルヒドリンを反応させて得られるポリグリシジルエーテル類、グリシジルエーテルエステル類、ポリグリシジルエステル類等が挙げられる。これらの多価エポキシ化合物は１種を単独で用いてもよいし、２種以上を任意の割合で組み合わせてもよい。 In the present invention, the epoxy compound used is an epoxy compound having two or more epoxy groups per molecule on average, and such a polyvalent epoxy compound is not particularly limited, but for example, bisphenol A. , Bisphenol F, bisphenol AD, catechol, resorcinol and other polyvalent phenols, polyglycidyl ethers obtained by reacting polyhydric alcohols such as glycerin and polyethylene glycol with epichlorohydrin, glycidyl ether esters, polyglycidyl esters and the like. Be done. One of these polyvalent epoxy compounds may be used alone, or two or more thereof may be combined at an arbitrary ratio.
本発明におけるアミン類からなる硬化促進剤は、特に限定されないが、トリエチルアミン、トリブチルアミン等のトリアルキルアミン、４−ジメチルアミノピリジン、ベンジルジメチルアミン、２，４，６−トリス（ジメチルアミノメチル）フェノール、１，８−ジアザビシクロ（５，４，０）−ウンデセン、１，５−ジアザビシクロ（４，３，０）−ノネン等のアミン化合物が挙げられる。これらは、１種を単独で用いてもよく、２種以上組み合わせてもよい。 The curing accelerator composed of amines in the present invention is not particularly limited, but is limited to trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, and 2,4,6-tris (dimethylaminomethyl) phenol. , 1,8-Diazabicyclo (5,4,0) -undecene, 1,5-diazabicyclo (4,3,0) -nonen and the like. These may be used alone or in combination of two or more.
本発明によるエポキシ樹脂組成物において、式（Ｉ）で表される本発明のチオール基を有するイソシアヌレート化合物は、エポキシ化合物のエポキシ当量数に対する式（Ｉ）で表される本発明のチオール基を有するイソシアヌレート化合物のＳＨ当量数の比、即ち、上記本発明の化合物のＳＨ当量数／エポキシ化合物のエポキシ当量数なる当量数比が０．５〜１．２となるように用いられる。また、上記硬化促進剤は、エポキシ化合物１００重量部に対して、通常、０．１〜１５重量部の範囲で用いられる。 In the epoxy resin composition according to the present invention, the isocyanurate compound having the thiol group of the present invention represented by the formula (I) is the thiol group of the present invention represented by the formula (I) with respect to the epoxy equivalent of the epoxy compound. It is used so that the ratio of the SH equivalents of the isocyanurate compound to have, that is, the equivalent ratio of the SH equivalents of the compound of the present invention to the epoxy equivalents of the epoxy compound is 0.5 to 1.2. Further, the curing accelerator is usually used in the range of 0.1 to 15 parts by weight with respect to 100 parts by weight of the epoxy compound.
以下、実施例を挙げて更に具体的に説明するが、本発明が実施例によって何ら限定されないことは勿論である。 Hereinafter, the present invention will be described in more detail with reference to Examples, but it goes without saying that the present invention is not limited to the Examples.
実施例１
１，３，５−トリス［２−（３−メルカプトプロピルオキシ）エチル］イソシアヌレートの合成
１，３，５−トリス［２−（２−プロペン−１−イロキシ）エチル］イソシアヌレート４．７１ｇ（１２．３ｍｍｏｌ）とチオ酢酸６．２９ｇ（８２．５ｍｍｏｌ）をＴＨＦ６０ｍｌに混合し、アゾビスイソブチロニトリル０．４１ｇ（２．５０ｍｍｏｌ）を添加した。これを６５℃にて１７時間反応させ、反応混合物を濃縮することでトリスチオアセテート体を得た（６．８０ｇ）。この化合物に硫酸０．９０ｇ（９．１８ｍｍｏｌ）とメタノール２６ｍｌを加えて５時間加熱還流した。その後、室温まで冷却し、トルエン３０ｍｌと水２０ｍｌを加え、抽出を行った。有機層を水３０ｍｌで３回洗浄し、無水硫酸マグネシウムで乾燥、ろ過した。ろ液から溶媒を留去し、黄色油状残渣をシリカゲルカラムクロマトグラフィー（ヘキサン／クロロホルム）で精製することにより１，３，５−トリス［２−（３−メルカプトプロピルオキシ）エチル］イソシアヌレートを得た。収量５．５９ｇ、収率９４．０％であった。
この化合物の構造特定のための分析結果を示す。
１Ｈ−ＮＭＲ（溶媒：ＣＤＣｌ３、内部標準物質：ＴＭＳ）
４．１１（ｔ，Ｊ＝５．７Ｈｚ，６Ｈ），３．６６（ｔ，Ｊ＝５．７Ｈｚ，６Ｈ），２．５８（ｑ，Ｊ＝７．３Ｈｚ，６Ｈ），１．８４（ｑｕｉｎ，Ｊ＝６．５Ｈｚ，６Ｈ）），１．３８（ｔ，Ｊ＝８．０Ｈｚ，３Ｈ）
１３Ｃ−ＮＭＲ（溶媒：ＣＤＣｌ３、内部標準物質：ＴＭＳ）
１４８．９５，６８．６０，６７．１５，４１．８２，３３．６３，２１．２９Example 1
Synthesis of 1,3,5-tris [2- (3-mercaptopropyloxy) ethyl] isocyanurate 1,3,5-tris [2- (2-propen-1-yloxy) ethyl] isocyanurate 4.71 g ( 12.3 mmol) and 6.29 g (82.5 mmol) of thioacetic acid were mixed with 60 ml of THF, and 0.41 g (2.50 mmol) of azobisisobutyronitrile was added. This was reacted at 65 ° C. for 17 hours, and the reaction mixture was concentrated to obtain a tristhioacetate compound (6.80 g). 0.90 g (9.18 mmol) of sulfuric acid and 26 ml of methanol were added to this compound, and the mixture was heated under reflux for 5 hours. Then, the mixture was cooled to room temperature, 30 ml of toluene and 20 ml of water were added, and extraction was performed. The organic layer was washed 3 times with 30 ml of water, dried over anhydrous magnesium sulfate, and filtered. The solvent was distilled off from the filtrate, and the yellow oily residue was purified by silica gel column chromatography (hexane / chloroform) to obtain 1,3,5-tris [2- (3-mercaptopropyloxy) ethyl] isocyanurate. It was. The yield was 5.59 g and the yield was 94.0%.
The analysis result for specifying the structure of this compound is shown.
1 1 H-NMR (solvent: CDCl 3 , internal standard substance: TMS)
4.11 (t, J = 5.7Hz, 6H), 3.66 (t, J = 5.7Hz, 6H), 2.58 (q, J = 7.3Hz, 6H), 1.84 (quin) , J = 6.5Hz, 6H)), 1.38 (t, J = 8.0Hz, 3H)
13 C-NMR (solvent: CDCl 3 , internal standard substance: TMS)
148.95, 68.60, 67.15, 41.82, 33.63, 21.29
エポキシ樹脂組成物の調製
実施例２及び比較例のエポキシ樹脂組成物を調製するために以下の原料を用いた。
成分（Ａ）ビスフェノールＡグリシジルエーテル 東京化成品
成分（Ｂ）１）１，３，５−トリス［２−（３−メルカプトプロピルオキシ）エチル］イソシアヌレート（実施例１の化合物）
２）１，３，５−トリス［（３−メルカプトプロピオニルオキシ）エチル］イソシアヌレート（チオール化合物１）東京化成品
３）トリメチロールプロパントリス（３−メルカプトプロピオネート）（チオール化合物２）東京化成品
成分（Ｃ）トリス（ジメチルアミノメチル）フェノール（ＤＭＰ−３０）東京化成品Preparation of Epoxy Resin Composition The following raw materials were used to prepare the epoxy resin compositions of Example 2 and Comparative Example.
Ingredient (A) Bisphenol A Glycidyl Ether Tokyo Chemicals Ingredient (B) 1) 1,3,5-Tris [2- (3-mercaptopropyloxy) ethyl] isocyanurate (compound of Example 1)
2) 1,3,5-Tris [(3-mercaptopropionyloxy) ethyl] isocyanurate (thiol compound 1) Tokyo Chemicals 3) Trimethylol propanthris (3-mercaptopropionate) (thiol compound 2) Tokyo Product Ingredients (C) Tris (Dimethylaminomethyl) Phenol (DMP-30) Tokyo Chemicals
表１に示す種類の成分（Ａ）、成分（Ｂ）及び成分（Ｃ）を、表１に示す重量比で混合してエポキシ樹脂を調製した。混合した物をサンドペーパー（＃２４０）で研磨したアルミニウム板（Ａ５０５２、１００×２５×１．５ｍｍ）に塗布し、８０℃で２時間、硬化させて試験片を作製した。 An epoxy resin was prepared by mixing the components (A), components (B) and components (C) of the types shown in Table 1 at the weight ratios shown in Table 1. The mixture was applied to an aluminum plate (A5052, 100 × 25 × 1.5 mm) polished with sandpaper (# 240) and cured at 80 ° C. for 2 hours to prepare a test piece.
作製した試験片について、作製直後の物と、８５℃、８５％ＲＨ恒温恒湿機で１０００時間曝露させたものの引張せん断接着強さをそれぞれＪＩＳ Ｋ６８５０に準拠して測定した。結果を表１に示す。 With respect to the prepared test pieces, the tensile shear adhesive strength of the one immediately after preparation and the one exposed at 85 ° C. and 85% RH constant temperature and humidity for 1000 hours were measured in accordance with JIS K6850, respectively. The results are shown in Table 1.
本発明の１，３，５−トリス［２−（３−メルカプトプロピルオキシ）エチル］イソシアヌレートを硬化剤として配合したエポキシ樹脂組成物の硬化物は、恒温恒湿機の引張せん断接着強さが作製直後と比較して強度劣化が見られず、市販のチオール化合物１及びチオール化合物２をそれぞれ硬化剤として配合したエポキシ樹脂組成物の硬化物に比べて、耐湿性に優れていることが示される。 The cured product of the epoxy resin composition containing 1,3,5-tris [2- (3-mercaptopropyloxy) ethyl] isocyanurate of the present invention as a curing agent has a tensile shear adhesive strength of a constant temperature and humidity chamber. No deterioration in strength was observed as compared with immediately after production, and it is shown that the moisture resistance is excellent as compared with the cured product of the epoxy resin composition containing each of the commercially available thiol compound 1 and thiol compound 2 as a curing agent. ..
本発明のチオール基を有するイソシアヌレート化合物は新規な含硫黄化合物の合成中間体として有用であるほか、特にエポキシ樹脂用硬化剤として有用である。 The isocyanurate compound having a thiol group of the present invention is useful as a synthetic intermediate for a novel sulfur-containing compound, and is particularly useful as a curing agent for epoxy resins.
また、このように、本発明のチオール基を有するイソシアヌレート化合物を硬化剤として含むエポキシ樹脂組成物は、接着、シーリング、封止、注型、成形、塗装、コーティング等の用途に好適に用いることができる。 Further, as described above, the epoxy resin composition containing the isocyanurate compound having a thiol group of the present invention as a curing agent is suitably used for applications such as adhesion, sealing, sealing, casting, molding, painting and coating. Can be done.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113045860A (en) * | 2021-03-29 | 2021-06-29 | 湖南创瑾技术研究院有限公司 | Packaging molding compound and preparation method and application thereof |
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