JP4962122B2 - Thermal latent curing catalyst for thermosetting resin - Google Patents
Thermal latent curing catalyst for thermosetting resin Download PDFInfo
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- JP4962122B2 JP4962122B2 JP2007119589A JP2007119589A JP4962122B2 JP 4962122 B2 JP4962122 B2 JP 4962122B2 JP 2007119589 A JP2007119589 A JP 2007119589A JP 2007119589 A JP2007119589 A JP 2007119589A JP 4962122 B2 JP4962122 B2 JP 4962122B2
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- thermosetting resin
- catalyst
- resin composition
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims description 56
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 49
- 229920005989 resin Polymers 0.000 title claims description 13
- 239000011347 resin Substances 0.000 title claims description 13
- -1 diamine compound Chemical class 0.000 claims description 70
- 150000001875 compounds Chemical class 0.000 claims description 37
- 239000011342 resin composition Substances 0.000 claims description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 125000003700 epoxy group Chemical group 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 5
- 229910052719 titanium Chemical group 0.000 claims description 5
- 239000010936 titanium Chemical group 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 125000004423 acyloxy group Chemical group 0.000 claims description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 34
- 239000003822 epoxy resin Substances 0.000 description 26
- 229920000647 polyepoxide Polymers 0.000 description 26
- 230000015572 biosynthetic process Effects 0.000 description 23
- 238000003786 synthesis reaction Methods 0.000 description 23
- 239000000243 solution Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 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 9
- 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 9
- 239000000203 mixture Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000011968 lewis acid catalyst Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 7
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical class OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- KLDZYURQCUYZBL-UHFFFAOYSA-N 2-[3-[(2-hydroxyphenyl)methylideneamino]propyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCN=CC1=CC=CC=C1O KLDZYURQCUYZBL-UHFFFAOYSA-N 0.000 description 4
- 239000002841 Lewis acid Substances 0.000 description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 229910000071 diazene Inorganic materials 0.000 description 4
- IPKKHRVROFYTEK-UHFFFAOYSA-N dipentyl phthalate Chemical compound CCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCC IPKKHRVROFYTEK-UHFFFAOYSA-N 0.000 description 4
- 150000007517 lewis acids Chemical class 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 4
- 239000004246 zinc acetate Substances 0.000 description 4
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 3
- RURPJGZXBHYNEM-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]propyliminomethyl]phenol Chemical compound C=1C=CC=C(O)C=1C=NC(C)CN=CC1=CC=CC=C1O RURPJGZXBHYNEM-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
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical group OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IFNXAMCERSVZCV-UHFFFAOYSA-L zinc;2-ethylhexanoate Chemical compound [Zn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O IFNXAMCERSVZCV-UHFFFAOYSA-L 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- 125000005654 1,2-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([*:2])C([H])([*:1])C1([H])[H] 0.000 description 2
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- 125000005655 1,3-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([*:2])C1([H])[H] 0.000 description 2
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 2
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 2
- WZUODJNEIXSNEU-UHFFFAOYSA-N 2-Hydroxy-4-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C(O)=C1 WZUODJNEIXSNEU-UHFFFAOYSA-N 0.000 description 2
- JODRRPJMQDFCBJ-UHFFFAOYSA-N 2-Hydroxy-4-methylbenzaldehyde Chemical compound CC1=CC=C(C=O)C(O)=C1 JODRRPJMQDFCBJ-UHFFFAOYSA-N 0.000 description 2
- NJLQUTOLTXWLBV-UHFFFAOYSA-N 2-ethylhexanoic acid titanium Chemical compound [Ti].CCCCC(CC)C(O)=O.CCCCC(CC)C(O)=O.CCCCC(CC)C(O)=O.CCCCC(CC)C(O)=O NJLQUTOLTXWLBV-UHFFFAOYSA-N 0.000 description 2
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- YAUYVAMZCWQECM-UHFFFAOYSA-M C(C)C(C(=O)[O-])CCCC.[O-2].[Zr+3] Chemical compound C(C)C(C(=O)[O-])CCCC.[O-2].[Zr+3] YAUYVAMZCWQECM-UHFFFAOYSA-M 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 description 2
- QHXLIQMGIGEHJP-UHFFFAOYSA-N boron;2-methylpyridine Chemical compound [B].CC1=CC=CC=N1 QHXLIQMGIGEHJP-UHFFFAOYSA-N 0.000 description 2
- ULEAQRIQMIQDPJ-UHFFFAOYSA-N butane-1,2-diamine Chemical compound CCC(N)CN ULEAQRIQMIQDPJ-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 208000018459 dissociative disease Diseases 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 239000004849 latent hardener Substances 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- JJVNINGBHGBWJH-UHFFFAOYSA-N ortho-vanillin Chemical compound COC1=CC=CC(C=O)=C1O JJVNINGBHGBWJH-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- IFFPHDYFQRRKPZ-UHFFFAOYSA-N phenol;titanium Chemical compound [Ti].OC1=CC=CC=C1.OC1=CC=CC=C1.OC1=CC=CC=C1.OC1=CC=CC=C1 IFFPHDYFQRRKPZ-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920002189 poly(glycerol 1-O-monomethacrylate) polymer Polymers 0.000 description 2
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 2
- 125000006239 protecting group Chemical group 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000006268 reductive amination reaction Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000013008 thixotropic agent Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 2
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
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- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
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- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- DUILGEYLVHGSEE-UHFFFAOYSA-N 2-(oxiran-2-ylmethyl)isoindole-1,3-dione Chemical compound O=C1C2=CC=CC=C2C(=O)N1CC1CO1 DUILGEYLVHGSEE-UHFFFAOYSA-N 0.000 description 1
- UQJMVMCSDLZSJA-UHFFFAOYSA-N 2-[[2-[(2-hydroxy-3,5-dimethylphenyl)methylideneamino]cyclohexyl]iminomethyl]-4,6-dimethylphenol Chemical compound CC1=CC(=C(C(=C1)C=NC2CCCCC2N=CC3=CC(=CC(=C3O)C)C)O)C UQJMVMCSDLZSJA-UHFFFAOYSA-N 0.000 description 1
- ZRZMJLZLTSUJRL-UHFFFAOYSA-N 2-[[2-[(2-hydroxy-4-methylphenyl)methylideneamino]phenyl]iminomethyl]-5-methylphenol Chemical compound CC=1C=C(C(C=NC2=C(C=CC=C2)N=CC=2C(O)=CC(=CC=2)C)=CC=1)O ZRZMJLZLTSUJRL-UHFFFAOYSA-N 0.000 description 1
- PGYJSURPYAAOMM-UHFFFAOYSA-N 2-ethenoxy-2-methylpropane Chemical compound CC(C)(C)OC=C PGYJSURPYAAOMM-UHFFFAOYSA-N 0.000 description 1
- GNUGVECARVKIPH-UHFFFAOYSA-N 2-ethenoxypropane Chemical compound CC(C)OC=C GNUGVECARVKIPH-UHFFFAOYSA-N 0.000 description 1
- OFYFURKXMHQOGG-UHFFFAOYSA-J 2-ethylhexanoate;zirconium(4+) Chemical compound [Zr+4].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O OFYFURKXMHQOGG-UHFFFAOYSA-J 0.000 description 1
- IQKFCYQDLYNVNU-UHFFFAOYSA-N 2-ethylhexanoic acid oxygen(2-) titanium(4+) Chemical compound [O-2].[Ti+4].C(C)C(C(=O)O)CCCC.[O-2] IQKFCYQDLYNVNU-UHFFFAOYSA-N 0.000 description 1
- ZRXHQNQYIKVKNQ-UHFFFAOYSA-N 2-ethylhexanoic acid;zinc Chemical compound [Zn].CCCCC(CC)C(O)=O ZRXHQNQYIKVKNQ-UHFFFAOYSA-N 0.000 description 1
- DSXKMMAQDSAZAC-UHFFFAOYSA-N 2-hydroxy-3,5-dimethylbenzaldehyde Chemical compound CC1=CC(C)=C(O)C(C=O)=C1 DSXKMMAQDSAZAC-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- DSSAWHFZNWVJEC-UHFFFAOYSA-N 3-(ethenoxymethyl)heptane Chemical compound CCCCC(CC)COC=C DSSAWHFZNWVJEC-UHFFFAOYSA-N 0.000 description 1
- OFQBYHLLIJGMNP-UHFFFAOYSA-N 3-ethoxy-2-hydroxybenzaldehyde Chemical compound CCOC1=CC=CC(C=O)=C1O OFQBYHLLIJGMNP-UHFFFAOYSA-N 0.000 description 1
- IPPQNXSAJZOTJZ-UHFFFAOYSA-N 3-methylsalicylaldehyde Chemical compound CC1=CC=CC(C=O)=C1O IPPQNXSAJZOTJZ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- AHIPJALLQVEEQF-UHFFFAOYSA-N 4-(oxiran-2-ylmethoxy)-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1COC(C=C1)=CC=C1N(CC1OC1)CC1CO1 AHIPJALLQVEEQF-UHFFFAOYSA-N 0.000 description 1
- YQHAGJMEOJLAJT-UHFFFAOYSA-N 4-ethoxy-2-hydroxybenzaldehyde Chemical compound CCOC1=CC=C(C=O)C(O)=C1 YQHAGJMEOJLAJT-UHFFFAOYSA-N 0.000 description 1
- WRQOPPZJPSGEDO-UHFFFAOYSA-N 5-oxabicyclo[4.1.0]heptane Chemical compound C1CCOC2CC21 WRQOPPZJPSGEDO-UHFFFAOYSA-N 0.000 description 1
- RBHIUNHSNSQJNG-UHFFFAOYSA-N 6-methyl-3-(2-methyloxiran-2-yl)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2(C)OC2CC1C1(C)CO1 RBHIUNHSNSQJNG-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 238000011914 asymmetric synthesis Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 1
- ZXOATMQSUNJNNG-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,3-dicarboxylate Chemical compound C=1C=CC(C(=O)OCC2OC2)=CC=1C(=O)OCC1CO1 ZXOATMQSUNJNNG-UHFFFAOYSA-N 0.000 description 1
- JQDCYGOHLMJDNA-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) butanedioate Chemical compound C1OC1COC(=O)CCC(=O)OCC1CO1 JQDCYGOHLMJDNA-UHFFFAOYSA-N 0.000 description 1
- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-UHFFFAOYSA-N 0.000 description 1
- NFVGWOSADNLNHZ-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) decanedioate Chemical compound C1OC1COC(=O)CCCCCCCCC(=O)OCC1CO1 NFVGWOSADNLNHZ-UHFFFAOYSA-N 0.000 description 1
- NNTOJPXOCKCMKR-UHFFFAOYSA-N boron;pyridine Chemical compound [B].C1=CC=NC=C1 NNTOJPXOCKCMKR-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- RZIPTXDCNDIINL-UHFFFAOYSA-N cyclohexane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCCC1(C(O)=O)C(O)=O RZIPTXDCNDIINL-UHFFFAOYSA-N 0.000 description 1
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- WTNDADANUZETTI-UHFFFAOYSA-N cyclohexane-1,2,4-tricarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)C(C(O)=O)C1 WTNDADANUZETTI-UHFFFAOYSA-N 0.000 description 1
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 description 1
- BQQUFAMSJAKLNB-UHFFFAOYSA-N dicyclopentadiene diepoxide Chemical compound C12C(C3OC33)CC3C2CC2C1O2 BQQUFAMSJAKLNB-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000005040 ion trap Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical class NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- BEOOHQFXGBMRKU-UHFFFAOYSA-N sodium cyanoborohydride Chemical compound [Na+].[B-]C#N BEOOHQFXGBMRKU-UHFFFAOYSA-N 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- YJVLWFXZVBOFRZ-UHFFFAOYSA-N titanium zinc Chemical compound [Ti].[Zn] YJVLWFXZVBOFRZ-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- YNPXMOHUBANPJB-UHFFFAOYSA-N zinc;butan-1-olate Chemical compound [Zn+2].CCCC[O-].CCCC[O-] YNPXMOHUBANPJB-UHFFFAOYSA-N 0.000 description 1
- YMTQMTSQMKJKPX-UHFFFAOYSA-L zinc;diphenoxide Chemical compound [Zn+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 YMTQMTSQMKJKPX-UHFFFAOYSA-L 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- TYSXNZUFDKPFED-UHFFFAOYSA-N zinc;propan-1-olate Chemical compound [Zn+2].CCC[O-].CCC[O-] TYSXNZUFDKPFED-UHFFFAOYSA-N 0.000 description 1
- DJIFSIBYHXVGSS-UHFFFAOYSA-J zirconium(4+);tetraphenoxide Chemical compound [Zr+4].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 DJIFSIBYHXVGSS-UHFFFAOYSA-J 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Epoxy Resins (AREA)
Description
本発明は、熱硬化性樹脂用熱潜在性硬化触媒、および該触媒を添加した熱硬化性樹脂組成物、より詳しくは、エポキシ化合物を含む熱硬化性樹脂組成物に関する。 The present invention is a thermosetting resin heat latent curing catalyst, and a thermosetting resin composition was added the catalyst, more particularly, to a thermosetting resin composition comprising an epoxy compound.
従来、ルイス酸触媒が様々な分野において用いられている。特にエポキシ樹脂組成物をはじめとする熱硬化性樹脂組成物においては、より低温短時間で硬化物を得るために金属塩をはじめとするルイス酸触媒が用いられている。しかしながら、ルイス酸触媒を添加した時点より反応が進行するため、ルイス酸触媒を添加することで熱硬化性樹脂組成物のポットライフが短縮してしまうことが問題となっていた。
以上のような問題を解決すべく、常温では活性を示さず、加熱した際に始めて活性を示す熱潜在性触媒の開発が行われている（例えば、非特許文献１、特許文献１）。しかしながら、これまで開発された熱潜在性触媒においては、熱潜在性が必ずしも高いとはいえず、特に室温では全く活性を示さず、１００〜１５０℃といった比較的低温で顕著な活性を示す熱潜在性触媒は無かった。さらには、熱潜在性触媒の多くは工業的に生産することが難しく、製造コストが高いものが多かった。
また、特許文献１や２に記載のヘミアセタールエステル基含有化合物は熱潜在性を有する硬化剤としてエポキシ樹脂組成物などに用いられる。しかしながら、保護基の解離反応に時間を要するため、低温短時間で硬化する熱硬化性樹脂組成物を得ることが難しかった。保護基の解離反応はルイス酸触媒によって活性化される。したがって、ヘミアセタールエステル基含有化合物を硬化剤とした熱硬化性樹脂組成物を幅広い用途に適応するためには、熱潜在性の高いルイス酸触媒が求められていた。
Conventionally, Lewis acid catalysts have been used in various fields. In particular, in a thermosetting resin composition including an epoxy resin composition, a Lewis acid catalyst such as a metal salt is used to obtain a cured product at a lower temperature and in a shorter time. However, since the reaction proceeds from the time when the Lewis acid catalyst is added, there is a problem that the pot life of the thermosetting resin composition is shortened by adding the Lewis acid catalyst.
In order to solve the above problems, thermal latent catalysts that do not show activity at normal temperature and show activity only when heated have been developed (for example, Non-Patent Document 1 and Patent Document 1). However, the thermal latent catalysts developed so far do not necessarily have high thermal potential, and especially show no activity at room temperature and show remarkable activity at a relatively low temperature such as 100 to 150 ° C. There was no sex catalyst. Furthermore, many of the heat latent catalysts are difficult to industrially produce and many have high production costs.
In addition, the hemiacetal ester group-containing compounds described in Patent Documents 1 and 2 are used in epoxy resin compositions and the like as curing agents having thermal potential. However, since it takes time for the dissociation reaction of the protective group, it has been difficult to obtain a thermosetting resin composition that cures at a low temperature in a short time. The protecting group dissociation reaction is activated by a Lewis acid catalyst. Therefore, in order to adapt a thermosetting resin composition using a hemiacetal ester group-containing compound as a curing agent to a wide range of uses, a Lewis acid catalyst having high thermal potential has been demanded.
一方、不斉合成反応に用いられる触媒として、Ｎ，Ｎ’−ジサリチリデン−１，２−ジアミノプロパンなどのサレン錯体が知られている（非特許文献２）。サレン錯体は、２個の窒素原子と２個の酸素原子からなる配座が剛直なサレン骨格に固定された構造をとることによって、反応場を立体規制して触媒反応を進める働きを有している。
非特許文献３には、サレン錯体の熱潜在性触媒としての用途が開示されている。しかしながら、一般的にＮ，Ｎ’−ジサリチリデン−１，２−ジアミノプロパンなどのサレン化合物は、剛直骨格構造を保つようにＣ＝Ｎ結合と芳香環とが配置されているが、一方でこの間の結合の共役構造によって可視光を吸収するため、黄色〜橙色に着色している。そのため熱硬化性組成物を硬化させた際に、透明性が要求される用途には使用することができない。
熱硬化性組成物の分野では、硬化用の触媒として用いて、優れた潜在性を有しながら、無色透明である熱潜在性触媒が求められているのである。
On the other hand, salen complexes such as N, N′-disalicylidene-1,2-diaminopropane are known as catalysts used in asymmetric synthesis reactions (Non-patent Document 2). The salen complex has a structure in which a conformation composed of two nitrogen atoms and two oxygen atoms is fixed to a rigid salen skeleton, and has a function of advancing a catalytic reaction by sterically regulating the reaction field. Yes.
Non-Patent Document 3 discloses the use of a salen complex as a thermal latent catalyst. However, in general, in a salen compound such as N, N′-disalicylidene-1,2-diaminopropane, a C═N bond and an aromatic ring are arranged so as to maintain a rigid skeleton structure. In order to absorb visible light by the conjugated structure of the bond, it is colored yellow to orange. Therefore, when the thermosetting composition is cured, it cannot be used for applications requiring transparency.
In the field of thermosetting compositions, there is a need for thermolatent catalysts that are colorless and transparent while having excellent potential as a catalyst for curing.
本発明の第一の目的は、優れた潜在性を有しながら、無色透明である熱硬化性樹脂用熱潜在性硬化触媒を提供することにある。
本発明の第二の目的は、保存安定性と硬化特性、さらに硬化物の透明性に優れた熱硬化性樹脂組成物を提供することにある。
The first object of the present invention is to provide a thermolatent curing catalyst for thermosetting resins that is colorless and transparent while having excellent latency.
The second object of the present invention is to provide a thermosetting resin composition excellent in storage stability and curing characteristics, and further in the transparency of a cured product.
本発明者らは前記の課題を解決するために鋭意検討を重ねた結果、特定の金属錯体が優れた潜在性を有する熱潜在性触媒になりうることの知見を得て、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have obtained the knowledge that a specific metal complex can be a thermal latent catalyst having excellent potential, and complete the present invention. It came to.
すなわち、本発明は以下の〔１〕〜〔２〕である。
〔１〕下記式（１）で表されるジアミン化合物（Ａ）と、下記式（２）で表される金属塩（Ｂ）とを反応させて得られる熱硬化性樹脂用熱潜在性硬化触媒（以下、「熱潜在性触媒」と略すことがある）。
That is, this invention is the following [1]-[2].
[1] Thermal latent curing catalyst for thermosetting resin obtained by reacting diamine compound (A) represented by the following formula (1) and metal salt (B) represented by the following formula (2) (Hereafter, it may be abbreviated as “thermal latent catalyst”) .
（式中のＲ1は炭素数１〜８の脂肪族または芳香族炭化水素基であり、Ｒ2は水素原子、炭素数１〜６のアルコキシ基または炭素数１〜６の炭化水素基である。ｎ１は０〜４の整数である。）
ＭＸn2 ・・・ （２）
（式中のＭは亜鉛、ジルコニウムまたはチタンであり、Ｘは酸素原子、アルコキシ基、フェノキシ基またはアシルオキシ基であり、ｎ２が２以上の場合はＸで示される複数の基は互いに同一でも異なっていてもよく、またＸで示される基は互いに結合して環を形成していてもよい。ｎ２はＭの価数を満たす整数である。）
〔２〕前記の〔１〕に記載の熱硬化性樹脂用熱潜在性硬化触媒０．０１〜１０重量％、ヘミアセタールエステル基含有化合物２９．９９〜７０重量％、エポキシ基含有化合物２９．９９〜７０重量％からなる熱硬化性樹脂組成物。
(In the formula, R 1 is an aliphatic or aromatic hydrocarbon group having 1 to 8 carbon atoms, and R 2 is a hydrogen atom, an alkoxy group having 1 to 6 carbon atoms or a hydrocarbon group having 1 to 6 carbon atoms. N1 is an integer of 0 to 4.)
MX n2 (2)
(In the formula, M is zinc, zirconium or titanium, X is an oxygen atom, an alkoxy group, a phenoxy group or an acyloxy group, and when n2 is 2 or more, a plurality of groups represented by X are the same or different from each other) And the groups represented by X may be bonded to each other to form a ring, and n2 is an integer satisfying the valence of M.)
[2] Thermal latent curing catalyst for thermosetting resin according to [1] above, 0.01 to 10% by weight, hemiacetal ester group-containing compound 29.99 to 70% by weight, epoxy group-containing compound 29.99 A thermosetting resin composition comprising -70% by weight.
本発明によって、室温（４０℃）以下ではルイス酸触媒活性を示さず、高温雰囲気下において優れたルイス酸触媒活性を有する熱硬化性樹脂用熱潜在性硬化触媒が提供される。
また、本発明によれば、保存安定性と硬化特性、さらに硬化物の透明性に優れた熱硬化性樹脂組成物が提供される。
According to the present invention, there is provided a thermolatent curing catalyst for a thermosetting resin which does not exhibit Lewis acid catalytic activity at room temperature (40 ° C.) or less and has excellent Lewis acid catalytic activity in a high temperature atmosphere.
Moreover, according to this invention, the thermosetting resin composition excellent in storage stability and a hardening characteristic, and also transparency of hardened | cured material is provided.
以下において本発明を詳しく説明する
１．熱潜在性触媒
本発明の熱潜在性触媒は、ジアミン化合物（Ａ）と金属塩（Ｂ）とを反応させて得られる。前記の反応は、ジアミン化合物（Ａ）と金属塩（Ｂ）の両者の等モル比での反応である。本発明の熱潜在性触媒は、ジアミン化合物（Ａ）の２つのアミンのＮ原子が、金属塩（Ｂ）の金属に対して配位した構造を有する。
本発明の熱潜在性触媒に用いるジアミン化合物（Ａ）は下記式（１）で表される構造を有する。
The present invention will be described in detail below. Thermal latent catalyst The thermal latent catalyst of the present invention is obtained by reacting the diamine compound (A) with the metal salt (B). Said reaction is reaction by equimolar ratio of both a diamine compound (A) and a metal salt (B). The thermal latent catalyst of the present invention has a structure in which N atoms of two amines of the diamine compound (A) are coordinated to the metal of the metal salt (B).
The diamine compound (A) used for the thermal latent catalyst of the present invention has a structure represented by the following formula (1).
式（１）において、Ｒ1は炭素数１〜８の脂肪族または芳香族炭化水素基である。Ｒ1の炭素数が８を超えるとジアミン化合物（Ａ）と金属塩（Ｂ）の金属原子からなる環が不安定となり、熱潜在性が低下する。 In formula (1), R 1 is an aliphatic or aromatic hydrocarbon radical having 1 to 8 carbon atoms. When the carbon number of R 1 exceeds 8, the ring composed of the metal atom of the diamine compound (A) and the metal salt (B) becomes unstable, and the thermal potential is lowered.
式（１）において、Ｒ1の炭素数１〜８の脂肪族または芳香族炭化水素基としては具体的には、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基、ヘキシレン基、ヘプチレン基、オクチレン基等のアルキレン基；１，２−シクロヘキシレン基、１，３−シクロヘキシレン基、１，４−シクロヘキシレン基等のシクロアルキレン基；ｏ−フェニレン基、ｍ−フェニレン基、ｐ−フェニレン基等のアリーレン基などが挙げられる。これらの中で調製の容易性からメチレン基、エチレン基、プロピレン基、１，２−シクロヘキシレン基、１，３−シクロヘキシレン基、ｏ−フェニレン基、ｍ−フェニレン基が好ましく挙げられる。 In the formula (1), specific examples of the aliphatic or aromatic hydrocarbon group having 1 to 8 carbon atoms of R 1 include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and a heptylene group. Alkylene groups such as octylene group; cycloalkylene groups such as 1,2-cyclohexylene group, 1,3-cyclohexylene group and 1,4-cyclohexylene group; o-phenylene group, m-phenylene group, p-phenylene And arylene groups such as a group. Among these, methylene group, ethylene group, propylene group, 1,2-cyclohexylene group, 1,3-cyclohexylene group, o-phenylene group, and m-phenylene group are preferable because of easy preparation.
式（１）においてＲ２は水素原子、炭素数１〜６のアルコキシ基または炭素数１〜６の炭化水素基である。式（１）におけるＲ２のアルコキシ基および炭化水素基の炭素数が６を超えるとジアミン化合物（Ａ）の分子量が大きくなり、熱硬化性樹脂組成物としたときの熱潜在性触媒の配合量が大きくなるため、熱硬化性樹脂組成物を硬化させた際に可塑成分として働き、硬化物の物性を低下させるおそれがある。
式（１）における炭素数１〜６のアルコキシ基の具体例としてはメトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基、シクロヘキシルオキシ基などが挙げられる。炭素数１〜６の炭化水素基の具体例としてはメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、シクロヘキシル基などが挙げられる。これらの中で好ましくは水素原子、メトキシ基、エトキシ基、プロポキシ基、メチル基、エチル基、プロピル基などが挙げられる。
In Formula (1), R 2 is a hydrogen atom, an alkoxy group having 1 to 6 carbon atoms, or a hydrocarbon group having 1 to 6 carbon atoms. When the number of carbon atoms of the alkoxy group and hydrocarbon group of R 2 in formula (1) exceeds 6, the molecular weight of the diamine compound (A) increases, and the amount of the thermal latent catalyst when it is used as a thermosetting resin composition Therefore, when the thermosetting resin composition is cured, it acts as a plastic component, and there is a possibility that the physical properties of the cured product are lowered.
Specific examples of the alkoxy group having 1 to 6 carbon atoms in the formula (1) include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, and a cyclohexyloxy group. Specific examples of the hydrocarbon group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a cyclohexyl group. Of these, hydrogen atom, methoxy group, ethoxy group, propoxy group, methyl group, ethyl group, propyl group and the like are preferable.
本発明において、ジアミン化合物（Ａ）と金属塩（Ｂ）との反応は０〜８０℃という比較的低温で進行し、反応時間１〜８時間で比較的高収率で熱潜在性触媒を得ることができる。
前記の反応を行う際に、反応系を均一にし、粘度を下げる目的で溶剤を用いても良い。前記の反応の際に用いられる溶剤としては特に限定されないが、ジアミン化合物（Ａ）と金属塩（Ｂ）とが溶解し、得られる熱潜在性触媒は溶解しない溶剤であることが製造工程上好ましい。このような溶剤としてはエタノールをはじめとしたアルコール類が挙げられる。
ジアミン化合物（Ａ）は下記式（３）で表されるジイミン化合物の還元的アミノ化により合成することができる。
In the present invention, the reaction between the diamine compound (A) and the metal salt (B) proceeds at a relatively low temperature of 0 to 80 ° C., and a thermal latent catalyst is obtained with a relatively high yield in a reaction time of 1 to 8 hours. be able to.
In carrying out the above reaction, a solvent may be used for the purpose of making the reaction system uniform and lowering the viscosity. Although it does not specifically limit as a solvent used in the case of the said reaction, It is preferable on a manufacturing process that a diamine compound (A) and a metal salt (B) melt | dissolve, and the thermal latent catalyst obtained does not melt | dissolve. . Examples of such a solvent include alcohols such as ethanol.
The diamine compound (A) can be synthesized by reductive amination of a diimine compound represented by the following formula (3).
（式中のＲ１は炭素数１〜８の脂肪族または芳香族炭化水素基であり、Ｒ２は水素原子、炭素数１〜６のアルコキシ基または炭素数１〜６の炭化水素基である。ｎ１は０〜４の整数である。）
還元的アミノ化には水素化アルミニウムリチウム（ＬＡＨ）、水素化アミノホウ素リチウム（ＬＡＢ）、水素化ホウ素ナトリウム、水素化トリアセトキシホウ素ナトリウム、水素化シアノホウ素ナトリウム、ピリジンボラン、ピコリンボランなどの還元剤を使用することができる。
さらに上記式（３）で表されるジイミン化合物は下記式（４）のように、比較的安価で入手性の良いジアミン化合物（ａ１）とアルデヒド化合物（ａ２）とを反応させることにより得ることができる。ジアミン化合物（ａ１）とアルデヒド化合物（ａ２）との反応は０〜８０℃という比較的低温で進行し、反応時間１〜８時間において比較的高収率でジイミン化合物を得ることができる。
(In the formula, R 1 is an aliphatic or aromatic hydrocarbon group having 1 to 8 carbon atoms, and R 2 is a hydrogen atom, an alkoxy group having 1 to 6 carbon atoms, or a hydrocarbon group having 1 to 6 carbon atoms. N1 is an integer of 0 to 4.)
Reductive agents such as lithium aluminum hydride (LAH), lithium aminoborohydride (LAB), sodium borohydride, sodium triacetoxyborohydride, sodium cyanoborohydride, pyridine borane, picoline borane for reductive amination Can be used.
Furthermore, the diimine compound represented by the above formula (3) can be obtained by reacting a relatively inexpensive and readily available diamine compound (a1) with an aldehyde compound (a2) as shown in the following formula (4). it can. The reaction of the diamine compound (a1) and the aldehyde compound (a2) proceeds at a relatively low temperature of 0 to 80 ° C., and a diimine compound can be obtained with a relatively high yield in a reaction time of 1 to 8 hours.
（式中のＲ１は炭素数１〜８の脂肪族または芳香族炭化水素基であり、Ｒ２は水素原子、炭素数１〜６のアルコキシ基または炭素数１〜６の炭化水素基である。ｎ１は０〜４の整数である。）
上記式（４）の反応に用いられるジアミン化合物（ａ１）としてはエチレンジアミン、１，２−プロパンジアミン、１，３−プロパンジアミン、１，２−ブタンジアミン、１，４−ブタンジアミン、１，２−シクロヘキサンジアミンなどの脂肪族ジアミン化合物；ｏ−フェニレンジアミン、ｍ−フェニレンジアミン、ｐ−フェニレンジアミンなどの芳香族ジアミン化合物などが挙げられる。金属塩（Ｂ）と反応させ、錯体としたときに金属原子Ｍと配位子とが形成する環の安定性の観点から、エチレンジアミン、１，２−プロパンジアミン、１，３−プロパンジアミン、１，２−ブタンジアミン、１，２−シクロヘキサンジアミン、ｏ−フェニレンジアミンが好ましく挙げられる。
上記式（４）の反応に用いられるアルデヒド化合物（ａ２）としてはサリチルアルデヒド構造を有しているものであればよい。好ましくはサリチルアルデヒド、３−メチルサリチルアルデヒド、４−メチルサリチルアルデヒド、３，５−ジメチルサリチルアルデヒド、３−メトキシサリチルアルデヒド、４−メトキシサリチルアルデヒド、３−エトキシサリチルアルデヒド、４−エトキシサリチルアルデヒドなどが挙げられる。
上記式（４）の反応を行う際に、反応系を均一にし、粘度を下げる目的で溶剤を用いても良い。この際に用いられる溶剤としては特に限定されないが、ジアミン化合物（ａ１）とアルデヒド化合物（ａ２）とが溶解する溶剤であることが製造工程上好ましい。得られるジイミン化合物（Ａ）と金属塩（Ｂ）との反応において好ましく用いられることから、ジアミン化合物（ａ１）とアルデヒド化合物（ａ２）との反応においても、メタノールをはじめとするアルコール類、ジクロロメタンなどのハロゲン化炭化水素類が挙げられる。
(In the formula, R 1 is an aliphatic or aromatic hydrocarbon group having 1 to 8 carbon atoms, and R 2 is a hydrogen atom, an alkoxy group having 1 to 6 carbon atoms, or a hydrocarbon group having 1 to 6 carbon atoms. N1 is an integer of 0 to 4.)
Examples of the diamine compound (a1) used in the reaction of the above formula (4) include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,2-butanediamine, 1,4-butanediamine, 1,2 -Aliphatic diamine compounds such as cyclohexanediamine; aromatic diamine compounds such as o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine. From the viewpoint of the stability of the ring formed by the metal atom M and the ligand when reacted with the metal salt (B) to form a complex, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1 , 2-butanediamine, 1,2-cyclohexanediamine, and o-phenylenediamine are preferable.
The aldehyde compound (a2) used in the reaction of the above formula (4) may be any one having a salicylaldehyde structure. Preferably, salicylaldehyde, 3-methylsalicylaldehyde, 4-methylsalicylaldehyde, 3,5-dimethylsalicylaldehyde, 3-methoxysalicylaldehyde, 4-methoxysalicylaldehyde, 3-ethoxysalicylaldehyde, 4-ethoxysalicylaldehyde and the like are preferable. Can be mentioned.
In carrying out the reaction of the above formula (4), a solvent may be used for the purpose of making the reaction system uniform and lowering the viscosity. Although it does not specifically limit as a solvent used in this case, It is preferable on a manufacturing process that it is a solvent in which a diamine compound (a1) and an aldehyde compound (a2) melt | dissolve. Since it is preferably used in the reaction between the resulting diimine compound (A) and the metal salt (B), alcohols including methanol, dichloromethane, etc. also in the reaction between the diamine compound (a1) and the aldehyde compound (a2) And halogenated hydrocarbons.
本発明において用いられる金属塩（Ｂ）は、下記式（２）で表される構造を有する。
ＭＸn2 ・・・ （２）
上記式（２）においてＭは亜鉛、ジルコニウムまたはチタンであり、Ｘは酸素原子、アルコキシ基、フェノキシ基またはアシルオキシ基であり、ｎ２が２以上の場合はＸで示される複数の基は互いに同一でも異なっていてもよく、またＸで示される基は互いに結合して環を形成していてもよい。ｎ２はＭの価数を満たす整数である。
ＭＸn2としては酸化亜鉛、酸化ジルコニウム、酸化チタンなどの亜鉛、ジルコニウムまたはチタンの酸化物、亜鉛プロポキシド、亜鉛ブトキシド、ジルコニウムプロポキシド、ジルコニウムブトキシド、チタンプロポキシド、チタンブトキシドなどの亜鉛、ジルコニウムまたはチタンのアルコキシド；亜鉛フェノキシド、ジルコニウムフェノキシド、チタンフェノキシドなどの亜鉛、ジルコニウムまたはチタンのフェノキシド；シュウ酸亜鉛、酢酸亜鉛、２−エチルヘキサン酸亜鉛、酢酸ジルコニウム、２−エチルヘキサン酸ジルコニウム、２−エチルヘキサン酸酸化ジルコニウム、酢酸チタン、２−エチルヘキサン酸チタン、２−エチルヘキサン酸酸化チタンなどの亜鉛、ジルコニウムまたはチタンのカルボン酸塩が挙げられる。これらの中で調製の容易性と入手性から、好ましくはシュウ酸亜鉛、酢酸亜鉛、２−エチルヘキサン酸亜鉛、酢酸ジルコニウム、２−エチルヘキサン酸酸化ジルコニウム、酢酸チタン、２−エチルヘキサン酸酸化チタンなどの亜鉛、ジルコニウムまたはチタンのカルボン酸塩が挙げられる。
The metal salt (B) used in the present invention has a structure represented by the following formula (2).
MX n2 (2)
In the above formula (2), M is zinc, zirconium or titanium, X is an oxygen atom, an alkoxy group, a phenoxy group or an acyloxy group, and when n2 is 2 or more, a plurality of groups represented by X may be the same as each other They may be different, and the groups represented by X may be bonded to each other to form a ring. n2 is an integer that satisfies the valence of M.
MX n2 includes zinc such as zinc oxide, zirconium oxide and titanium oxide, zirconium or titanium oxide, zinc propoxide, zinc butoxide, zirconium propoxide, zirconium butoxide, titanium propoxide, titanium butoxide and the like, zirconium or titanium Zinc, zirconium or titanium phenoxide such as zinc phenoxide, zirconium phenoxide, titanium phenoxide; zinc oxalate, zinc acetate, zinc 2-ethylhexanoate, zirconium acetate, zirconium 2-ethylhexanoate, 2-ethylhexanoic acid Zinc, zirconium or titanium carboxylates such as zirconium oxide, titanium acetate, titanium 2-ethylhexanoate, titanium 2-ethylhexanoate and the like can be mentioned. Of these, zinc oxalate, zinc acetate, zinc 2-ethylhexanoate, zirconium acetate, zirconium oxide 2-ethylhexanoate, titanium acetate, titanium oxide 2-ethylhexanoate are preferred because of their ease of preparation and availability. And zinc, zirconium or titanium carboxylates.
本発明の熱潜在性触媒は、配座を形成する窒素原子が芳香環からメチレン基で結ばれた構造を有することによって、高いアミン塩基性を維持して、中心金属をしっかりと保持することができる。このため、嵩高い２つの芳香環が反応性の被触媒分子に対して、低温での潜在化温度領域では立体的な排除効果を示しながら、高温での非潜在化温度領域では非常に高い触媒活性を示すものと考えられる。また、上記のようにサレン錯体のように弱い共役塩基を補う平面配座構造で潜在性を保持する必要が無く、二重結合の共役からの着色の問題も起こりえない。 The thermal latent catalyst of the present invention has a structure in which a nitrogen atom forming a conformation is connected to a methylene group from an aromatic ring, thereby maintaining high amine basicity and firmly holding a central metal. it can. For this reason, it is a catalyst that exhibits a steric exclusion effect in the latent temperature region at low temperatures and a very high catalyst in the non-latent temperature region at high temperatures, while the two bulky aromatic rings are reactive catalyst molecules. It is considered to show activity. In addition, as described above, it is not necessary to maintain the potential with a planar conformation structure that supplements a weak conjugated base like a salen complex, and the problem of coloring from conjugation of a double bond cannot occur.
本発明の熱潜在性触媒は常温ではルイス酸触媒活性を有しないため、ルイス酸により触媒される熱硬化性樹脂と組み合わせると、ポットライフに優れる熱硬化性樹脂組成物が得られる。熱硬化性樹脂としては、代表的にエポキシ樹脂やビスマレイミド樹脂、シアナート樹脂（ウレタン樹脂など）、ポリイミド樹脂が挙げられる。これらの熱硬化性樹脂の中では、触媒活性化効果の点からエポキシ樹脂が好ましく挙げられる。 Since the thermolatent catalyst of the present invention does not have Lewis acid catalytic activity at room temperature, a thermosetting resin composition excellent in pot life can be obtained when combined with a thermosetting resin catalyzed by Lewis acid. Typical examples of the thermosetting resin include epoxy resin, bismaleimide resin, cyanate resin (urethane resin, etc.) and polyimide resin. Among these thermosetting resins, an epoxy resin is preferable from the viewpoint of catalyst activation effect.
２．熱硬化性樹脂組成物
本発明の熱硬化性樹脂組成物は、前記本発明の熱潜在性触媒、ヘミアセタールエステル基含有化合物、およびエポキシ基含有化合物からなる。
＜ヘミアセタールエステル基含有化合物＞
本発明において、ヘミアセタールエステル基含有化合物とは、１分子中に２個以上のヘミアセタールエステル基を有する化合物をいう。ヘミアセタールエステル基含有化合物は、カルボン酸のカルボキシル基がビニルエーテル化合物によって潜在化された化合物であり、特開平０８−０４１２０８号公報などに記載の公知の方法により合成することが出来る。
ヘミアセタールエステル基含有化合物は低温短時間の加熱ではカルボン酸を再生することが難しい。したがって、エポキシ基含有化合物の硬化剤として使用する際には、カルボン酸を再生する反応の触媒であるルイス酸触媒を添加することが望まれる。しかしながら、熱潜在性の無いルイス酸触媒を添加した際には、室温においてもカルボン酸を再生する反応が進行し、十分なポットライフを得ることが難しい。本発明の熱潜在性触媒は潜在性が高いため、ヘミアセタールエステル化合物と組み合わせることによって、ポットライフが長く保存安定性に優れる熱硬化性樹脂組成物となる。さらには、ジアミン化合物（Ａ）の塩基性が低いため、ヘミアセタールエステル化合物のカルボキシル基再生反応を阻害することなく、良好な硬化物を得ることができる。
2. Thermosetting resin composition The thermosetting resin composition of the present invention comprises the thermal latent catalyst of the present invention, a hemiacetal ester group-containing compound, and an epoxy group-containing compound.
<Hemiacetal ester group-containing compound>
In the present invention, the hemiacetal ester group-containing compound refers to a compound having two or more hemiacetal ester groups in one molecule. The hemiacetal ester group-containing compound is a compound in which the carboxyl group of a carboxylic acid is made latent by a vinyl ether compound, and can be synthesized by a known method described in JP-A-08-041208.
It is difficult for a hemiacetal ester group-containing compound to regenerate carboxylic acid by heating at a low temperature for a short time. Therefore, when used as a curing agent for an epoxy group-containing compound, it is desirable to add a Lewis acid catalyst that is a catalyst for the reaction of regenerating carboxylic acid. However, when a Lewis acid catalyst having no thermal potential is added, a reaction for regenerating the carboxylic acid proceeds even at room temperature, and it is difficult to obtain a sufficient pot life. Since the thermolatent catalyst of the present invention has high potential, combining with a hemiacetal ester compound provides a thermosetting resin composition having a long pot life and excellent storage stability. Furthermore, since the basicity of the diamine compound (A) is low, a good cured product can be obtained without inhibiting the carboxyl group regeneration reaction of the hemiacetal ester compound.
前記のカルボン酸のうち本発明において好適に用いられるものは、アジピン酸などの脂肪族多価カルボン酸；フタル酸などの芳香族ジカルボン酸；シクロヘキサンジカルボン酸などの脂環式ジカルボン酸；１，２，４−ベンゼントリカルボン酸（以下、トリメリット酸）などの芳香族トリカルボン酸；１，２，４−シクロヘキサントリカルボン酸（以下、ＣＨＴＡ）などの脂環式トリカルボン酸；１，２，４，５−ベンゼンテトラカルボン酸（ピロメリット酸）などの芳香族テトラカルボン酸；シクロヘキサンテトラカルボン酸などの脂環式テトラカルボン酸が挙げられる。さらには、グリセリンやポリビニルアルコールなどの多価アルコールと無水フタル酸、１，３，４−ベンゼントリカルボン酸−３，４−無水物（無水トリメリット酸）などの酸無水物との反応により得られるハーフエステル体も好ましく挙げられる。なお、以上のカルボン酸の中では、硬化性に優れる硬化物が得られることから、ピロメリット酸、トリメリット酸またはＣＨＴＡが、より好適に挙げられる。
前記のビニルエーテル化合物としては、例えばイソプロピルビニルエーテル、ｎ−プロピルビニルエーテル、ｎ−ブチルビニルエーテル、イソブチルビニルエーテル、ｔ−ブチルビニルエーテル、２−エチルへキシルビニルエーテル、シクロへキシルビニルエーテルなどの炭素数３〜８のアルキルビニルエーテル類が挙げられる。本発明のエポキシ樹脂組成物用いることができるビニルエーテル化合物として、好ましくは前記カルボン酸との反応性、ヘミアセタールエステルとしたときの安定性などの観点からｎ−プロピルビニルエーテルおよびイソブチルビニルエーテルが挙げられる。
Among the above carboxylic acids, those suitably used in the present invention include aliphatic polycarboxylic acids such as adipic acid; aromatic dicarboxylic acids such as phthalic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; Aromatic tricarboxylic acids such as 1,4-benzenetricarboxylic acid (hereinafter trimellitic acid); alicyclic tricarboxylic acids such as 1,2,4-cyclohexanetricarboxylic acid (hereinafter CHTA); 1,2,4,5- Examples thereof include aromatic tetracarboxylic acids such as benzenetetracarboxylic acid (pyromellitic acid); and alicyclic tetracarboxylic acids such as cyclohexanetetracarboxylic acid. Furthermore, it can be obtained by reacting polyhydric alcohols such as glycerin and polyvinyl alcohol with acid anhydrides such as phthalic anhydride and 1,3,4-benzenetricarboxylic acid-3,4-anhydride (trimellitic anhydride). A half ester body is also preferred. In addition, in the above carboxylic acid, since the hardened | cured material excellent in sclerosis | hardenability is obtained, pyromellitic acid, trimellitic acid, or CHTA is mentioned more suitably.
Examples of the vinyl ether compound include alkyl vinyl ethers having 3 to 8 carbon atoms such as isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, and cyclohexyl vinyl ether. Kind. Preferred vinyl ether compounds that can be used in the epoxy resin composition of the present invention include n-propyl vinyl ether and isobutyl vinyl ether from the viewpoints of reactivity with the carboxylic acid and stability when a hemiacetal ester is used.
＜エポキシ基含有化合物＞
本発明において、エポキシ基含有化合物とは、エポキシ基を１分子中に２個以上有する化合物をいう。前記のエポキシ基含有化合物としては、具体的には、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビフェノール型またはビキシレノール型のエポキシ樹脂またはそれらの混合物、ナフタレン基含有エポキシ樹脂、スチルベン型エポキシ樹脂、脂環式エポキシ樹脂およびその誘導体、ハイドロキノン型エポキシ樹脂、フルオレン骨格を有するエポキシ樹脂、テトラフェニロールエタン型エポキシ樹脂、ＤＰＰ（ジ−ｎ−ペンチルフタレート）型エポキシ樹脂、トリスヒドロキシフェニルメタン型エポキシ樹脂、ジシクロペンタジエンフェノール型エポキシ樹脂などの芳香族ポリグリシジルエーテル；
<Epoxy group-containing compound>
In the present invention, the epoxy group-containing compound refers to a compound having two or more epoxy groups in one molecule. Specific examples of the epoxy group-containing compound include bisphenol A type epoxy resins, bisphenol A novolac type epoxy resins, bisphenol F type epoxy resins, bisphenol A type epoxy resins, bisphenol S type epoxy resins, and phenol novolac type epoxy resins. , Cresol novolac type epoxy resin, biphenol type or bixylenol type epoxy resin or a mixture thereof, naphthalene group-containing epoxy resin, stilbene type epoxy resin, alicyclic epoxy resin and its derivatives, hydroquinone type epoxy resin, fluorene skeleton Epoxy resin, tetraphenylolethane type epoxy resin, DPP (di-n-pentylphthalate) type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclo Aromatic polyglycidyl ethers, such as printer diene phenol epoxy resin;
水添ビスフェノールＡ型エポキシ樹脂、水添ビスフェノールＦ型エポキシ樹脂、各種芳香族グリシジルエーテル類の水添または半水添エポキシ樹脂、その他脂肪族ポリオールのグリシジルエーテルなどの脂肪族グリジジルエーテル類；アジピン酸ジグリシジルエステル、コハク酸ジグリシジルエステル、セバシン酸ジグリシジルエステル、ヘキサヒドロフタル酸ジグリシジルエステルなどの炭素数２〜５０の脂肪族ポリジグリシジルエステル；１，２−シクロヘキサンジカルボン酸ビス（２，３−エポキシプロピル）エステル、ダイマー酸ジグリシジルエステル、３級カルボン酸グリシジルエステルなどの脂肪族グリジジルエステル類；フタル酸ジグリシジルエステル、イソフタル酸ジグリシジルエステルなどの炭素数７〜５０の芳香族ジグリシジルエステル；１，２：８，９ジエポキシリモネン、３，４−エポキシシクロヘキセニルメチル−３’，４’−エポキシシクロヘキセンカルボキシレート、ε−カプロラクトン変成３，４−エポキシシクロヘキセニルメチル−３’，４’−エポキシシクロヘキセンカルボキシレート、３，１−ビス（３，４−エポキシシクロヘキシルメチル）アジペート、２−（７−オキサビシクロ［４．１．０］ヘプチル３−）−スピロ［１，３−ジオン−５，３’−［７］オキサビシクロ［４．１．０］ヘプタン、ジシクロペンタジエンジオキサイドなどの脂環式エポキシ化合物；Ｎ，Ｎ−ジグリシジル−４−グリシジルオキシアニリン、テトラグリシジルジアミノフェニルメタン、アニリンジグリシジルエーテル、Ｎ−（２−メチルフェニル）−Ｎ−（オキシラニルメチル）オキシランメタンアミン、Ｎ−グリシジルフタルイミドなどのグリジジルアミン類；トリス（２，３−エポキシプロピル）イソシアヌレートなどの複素環式エポキシ化合物；その他に、ブタジエンの単独重合体または共重合体のエポキシ基含有化合物；グリシジル（メタ）アクリレートなどのエポキシ基含有モノマーの重合体などが挙げられる。
以上のエポキシ基含有化合物の中では、硬化性と透明性に優れる硬化物が得られることから、ビスフェノールＡ型エポキシ樹脂、グリシジル（メタ）アクリレートなどのエポキシ基含有モノマーの重合体などがより好適に挙げられる。
Hydrogenated bisphenol A type epoxy resins, hydrogenated bisphenol F type epoxy resins, hydrogenated or semi-hydrogenated epoxy resins of various aromatic glycidyl ethers, and other aliphatic glycidyl ethers such as glycidyl ethers of aliphatic polyols; adipic acid C2-C50 aliphatic polydiglycidyl ester such as diglycidyl ester, succinic acid diglycidyl ester, sebacic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester; 1,2-cyclohexanedicarboxylic acid bis (2,3- (Epoxypropyl) ester, dimer acid diglycidyl ester, aliphatic glycidyl ester such as tertiary carboxylic acid glycidyl ester; aromatic diglycidyl ester such as phthalic acid diglycidyl ester and isophthalic acid diglycidyl ester 1,2: 8,9 diepoxy limonene, 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, ε-caprolactone modified 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, 3,1-bis (3,4-epoxycyclohexylmethyl) adipate, 2- (7-oxabicyclo [4.1.0] heptyl 3-)-spiro [1,3-dione Alicyclic epoxy compounds such as -5,3 '-[7] oxabicyclo [4.1.0] heptane, dicyclopentadiene dioxide; N, N-diglycidyl-4-glycidyloxyaniline, tetraglycidyldiaminophenylmethane Aniline diglycidyl ether, N- (2-methylphenyl) -N- (oxy Ranylmethyl) oxiranemethanamine, glycidylamines such as N-glycidylphthalimide; heterocyclic epoxy compounds such as tris (2,3-epoxypropyl) isocyanurate; other butadiene homopolymer or copolymer epoxy Group-containing compounds; polymers of epoxy group-containing monomers such as glycidyl (meth) acrylate.
Among the above epoxy group-containing compounds, a cured product having excellent curability and transparency can be obtained. Therefore, a polymer of an epoxy group-containing monomer such as bisphenol A type epoxy resin or glycidyl (meth) acrylate is more preferable. Can be mentioned.
＜熱硬化性樹脂組成物の配合＞
本発明の熱硬化性樹脂組成物における本発明の熱潜在性触媒の配合量は０．０１〜１０重量％であり、好ましくは０．１〜５重量％、さらに好ましくは、０．５〜２重量％である。０．０１重量％未満であると触媒としての効果が発現せず、１０重量％を上回ると触媒配位子の可塑化効果が硬化性に悪影響を及ぼす。
本発明の熱硬化性樹脂組成物におけるヘミアセタールエステル基含有化合物の配合量は２９．９９〜７０重量％であり、好ましくは３４．４９〜６０重量％、さらに好ましくは、４９．９９〜５５重量％である。また、本発明の熱硬化性樹脂組成物におけるエポキシ基含有化合物の配合量は２９．９９〜７０重量％であり、好ましくは３９．９９〜６５重量％、さらに好ましくは、４４．９９〜５０重量％である。ヘミアセタールエステル基含有化合物が２９．９９重量％未満であったり、エポキシ基含有化合物が７０重量％を上回ったりすると、成分の相溶性の違いから熱硬化性樹脂組成物の硬化物の透明性に悪影響を及ぼす可能性があり、ヘミアセタールエステル基含有化合物が７０重量％を上回ったり、エポキシ基含有化合物が２９．９９重量％未満であったりすると、熱硬化性樹脂組成物の効果反応の進行に必要なモル比が不均衡になり硬化性に悪影響を及ぼす可能性がある。
<Formulation of thermosetting resin composition>
The blending amount of the thermal latent catalyst of the present invention in the thermosetting resin composition of the present invention is 0.01 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.5 to 2%. % By weight. If it is less than 0.01% by weight, the effect as a catalyst is not exhibited, and if it exceeds 10% by weight, the plasticizing effect of the catalyst ligand adversely affects the curability.
The compounding quantity of the hemiacetal ester group containing compound in the thermosetting resin composition of this invention is 29.99-70 weight%, Preferably it is 34.49-60 weight%, More preferably, 49.99-55 weight %. Moreover, the compounding quantity of the epoxy-group containing compound in the thermosetting resin composition of this invention is 29.99-70 weight%, Preferably it is 39.99-65 weight%, More preferably, 44.99-50 weight% %. When the hemiacetal ester group-containing compound is less than 29.99% by weight or the epoxy group-containing compound exceeds 70% by weight, the transparency of the cured product of the thermosetting resin composition is improved due to the compatibility of the components. If the hemiacetal ester group-containing compound exceeds 70% by weight or the epoxy group-containing compound is less than 29.99% by weight, the effect reaction of the thermosetting resin composition progresses. The required molar ratio can become unbalanced and adversely affect curability.
本発明の熱硬化性樹脂組成物には、溶剤、増粘剤、チキソ剤、紫外線吸収剤、充填材、炭酸ガス発生防止剤、可撓性付与剤、酸化防止剤、可塑剤、滑剤、表面処理剤、難燃剤、帯電防止剤、着色剤、レベリング剤、イオントラップ剤、摺動性改良剤、耐衝撃性付与剤、揺変性付与剤、表面張力低下剤、消泡剤、光拡散剤、抗酸化剤、蛍光剤等の添加剤を添加して使用することができる。
本発明の熱硬化性樹脂組成物の調整に際しては、上記の必須成分を一括配合しても良いし、熱硬化性樹脂組成物の溶剤希釈物を得るべく各成分を溶剤に溶解した後に逐次配合しても良い。各成分配合後、羽根形撹拌機、デソルバー、ニーダー、ボールミル混和機、ロール分散機等の既知の混和装置を用いて成分の混和を行うことができる。
The thermosetting resin composition of the present invention includes a solvent, a thickener, a thixotropic agent, an ultraviolet absorber, a filler, a carbon dioxide generation inhibitor, a flexibility imparting agent, an antioxidant, a plasticizer, a lubricant, and a surface. Treatment agent, flame retardant, antistatic agent, colorant, leveling agent, ion trap agent, sliding property improver, impact resistance imparting agent, thixotropic agent, surface tension reducing agent, antifoaming agent, light diffusing agent, Additives such as antioxidants and fluorescent agents can be added and used.
In preparing the thermosetting resin composition of the present invention, the above-described essential components may be blended together, or after each component is dissolved in a solvent to obtain a solvent dilution of the thermosetting resin composition, blended sequentially. You may do it. After blending each component, the components can be mixed using a known mixing device such as a blade-type stirrer, a desolver, a kneader, a ball mill mixer, a roll disperser or the like.
次に実施例および比較例を挙げて本発明をさらに具体的に説明する。
以下に本実施例および比較例で用いた測定方法、評価方法を示す。
＜重量平均分子量＞
重量平均分子量（Ｍｗ）は、東ソー（株）製ゲルパミエーションクロマトグラフィー装置ＨＬＣ−８２２０ＧＰＣを用い、カラムとして東ソー（株）製ＳＵＰＥＲ ＨＺ−Ｍを用い、測定温度４０℃、ＴＨＦを溶離液とし、ＲＩ検出器により測定してポリスチレン換算により求めた。
＜粘度＞
粘度は、循環式恒温水浴を装備したＢ型粘度計（東機産業（株）製）を用いて温度２０℃で測定した。
酸価および全酸当量は、ＪＩＳ Ｋ ００７０：１９９２「化学製品の酸価、けん化価、エステル価、よう素価、水酸基価及び不けん化物の試験方法」の加水分解酸価測定によって測定した。
＜エポキシ当量＞
エポキシ当量は、ＪＩＳ Ｋ ７２３６：２００１「エポキシ樹脂のエポキシ当量の求め方」によって規定される方法によって測定した。
＜核磁気共鳴スペクトル（ＮＭＲ）＞
核磁気共鳴スペクトル（ＮＭＲ）は、ＢＲＵＫＥＲ製ＡＶＡＮＣＥ４００（溶媒は、クロロホルム−ｄ（ＣＤＣｌ３）あるいはＤＭＳＯ−ｄ６を用い、化学シフトは、内部標準としてテトラメチルシランのピークを０．００ｐｐｍとした。）にて測定を行い、δおよびＪ値はｐｐｍで表し、４００ＭＨｚとした。
Next, the present invention will be described more specifically with reference to examples and comparative examples.
The measurement methods and evaluation methods used in the examples and comparative examples are shown below.
<Weight average molecular weight>
The weight average molecular weight (Mw) was measured using a gel permeation chromatography apparatus HLC-8220GPC manufactured by Tosoh Corporation, SUPER HZ-M manufactured by Tosoh Corporation as a column, measurement temperature 40 ° C., and THF as an eluent. It measured with RI detector and calculated | required by polystyrene conversion.
<Viscosity>
The viscosity was measured at a temperature of 20 ° C. using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd.) equipped with a circulating constant temperature water bath.
The acid value and total acid equivalent were measured by hydrolysis acid value measurement according to JIS K 0070: 1992 “Testing method for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponified product of chemical products”.
<Epoxy equivalent>
The epoxy equivalent was measured by a method defined by JIS K 7236: 2001 “How to Determine Epoxy Equivalent of Epoxy Resin”.
<Nuclear magnetic resonance spectrum (NMR)>
Nuclear magnetic resonance spectrum (NMR) was AVANCE400 manufactured by BRUKER (the solvent used was chloroform-d (CDCl 3 ) or DMSO-d6, and the chemical shift was tetrappmsilane peak of 0.00 ppm as an internal standard). The δ and J values are expressed in ppm and set to 400 MHz.
＜合成例１：ジアミン化合物Ａ−１の合成＞
撹拌子、滴下ロート、三方コックを備え、窒素置換した２口フラスコに、和光純薬工業（株）製Ｎ，Ｎ’−ビス（サリチリデン）−１，３−プロパンジアミン５．６４重量部とメタノール１０重量部を入れて撹拌し、そこにピコリンボラン２．１０重量部を投入し室温で３時間撹拌し続けた。反応液に１０％塩酸を５０重量部加えて室温で３０分撹拌し、その後、氷温に冷却したところに２０％炭酸ナトリウム水溶液を５０重量部加えて３０分撹拌した。反応液を酢酸エチル１００重量部で２回抽出し、飽和食塩水１００重量部で洗浄後、硫酸マグネシウムで脱水し溶媒を減圧留去してジアミン化合物Ａ−１を得た（乾燥後重量４．９０重量部）。得られた生成物の構造は、１ＨＮＭＲにて同定を行った。
<Synthesis Example 1: Synthesis of Diamine Compound A-1>
A two-necked flask equipped with a stirrer, a dropping funnel and a three-way cock and purged with nitrogen, 5.64 parts by weight of N, N′-bis (salicylidene) -1,3-propanediamine manufactured by Wako Pure Chemical Industries, Ltd. and methanol 10 parts by weight was added and stirred, and 2.10 parts by weight of picoline borane was added thereto and stirring was continued for 3 hours at room temperature. To the reaction solution, 50 parts by weight of 10% hydrochloric acid was added and stirred at room temperature for 30 minutes. After cooling to ice temperature, 50 parts by weight of 20% aqueous sodium carbonate solution was added and stirred for 30 minutes. The reaction solution was extracted twice with 100 parts by weight of ethyl acetate, washed with 100 parts by weight of saturated brine, dehydrated with magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain diamine compound A-1 (weight after drying: 4. 90 parts by weight). The structure of the obtained product was identified by 1 HNMR.
1ＨＮＭＲ（ＣＤＣｌ3、４００ＭＨｚ）：１３．４（ｓ，２Ｈ，−ＯＨ），７．１６（ｍ，２Ｈ，−Ｃ6Ｈ4−），６．９９（ｍ，２Ｈ，−Ｃ6Ｈ4−），６．８１（ｍ，４Ｈ，−Ｃ6Ｈ4−），３．９９（ｓ，４Ｈ，−ＣＨ2−），２．７５（ｔ，４Ｈ，Ｊ＝２．３５，−ＣＨ2−），１．７９（ｑ，２Ｈ，Ｊ＝２．２２，−ＣＨ2−）
＜合成例２：ジアミン化合物Ａ−２の合成＞
Ｎ，Ｎ'−ビス（サリチリデン）−１，３−プロパンジアミンの代わりにＮ，Ｎ'−ビス（３−エトキシサリチリデン）−１，３−エチレンジアミンを５．３６重量部使用した以外は合成例１と同様な手法でＡ−２を合成し、生成物の同定を行った。
＜合成例３：ジアミン化合物Ａ−３の合成＞
Ｎ，Ｎ'−ビス（サリチリデン）−１，３−プロパンジアミンの代わりにＮ，Ｎ'−ビス（４−メチルサリチリデン）−ｏ−フェニレンジアミンを６．３２重量部使用した以外は合成例１と同様な手法でＡ−３を合成し、生成物の同定を行った。
＜合成例４：ジアミン化合物Ａ−４の合成＞
Ｎ，Ｎ'−ビス（サリチリデン）−１，３−プロパンジアミンの代わりにＮ，Ｎ'−ビス（３，５−ジメチルサリチリデン）−１，２−シクロヘキサンジアミンを７．５７重量部使用した以外は合成例１と同様な手法でＡ−４を合成し、生成物の同定を行った。
合成例１〜４の結果を表１に示す。
1 HNMR (CDCl 3 , 400 MHz): 13.4 (s, 2H, —OH), 7.16 (m, 2H, —C 6 H 4 —), 6.99 (m, 2H, —C 6 H 4) -), 6.81 (m, 4H , -C 6 H 4 -), 3.99 (s, 4H, -CH 2 -), 2.75 (t, 4H, J = 2.35, -CH 2 −), 1.79 (q, 2H, J = 2.22, —CH 2 —)
<Synthesis Example 2: Synthesis of Diamine Compound A-2>
Synthesis except that 5.36 parts by weight of N, N′-bis (3-ethoxysalicylidene) -1,3-ethylenediamine was used instead of N, N′-bis (salicylidene) -1,3-propanediamine. A-2 was synthesized in the same manner as in Example 1, and the product was identified.
<Synthesis Example 3: Synthesis of Diamine Compound A-3>
Synthesis example except that 6.32 parts by weight of N, N′-bis (4-methylsalicylidene) -o-phenylenediamine was used instead of N, N′-bis (salicylidene) -1,3-propanediamine A-3 was synthesized by the same method as in Example 1, and the product was identified.
<Synthesis Example 4: Synthesis of Diamine Compound A-4>
In place of N, N′-bis (salicylidene) -1,3-propanediamine, 7.57 parts by weight of N, N′-bis (3,5-dimethylsalicylidene) -1,2-cyclohexanediamine was used. A-4 was synthesized in the same manner as in Synthesis Example 1 except that the product was identified.
The results of Synthesis Examples 1 to 4 are shown in Table 1.
表中のＲ1、Ｒ2は、それぞれ式（１）におけるＲ1、Ｒ2に相当する。
＜合成例５：多価ヘミアセタールエステル化合物（ＢＴＭＡ）の合成＞
温度計、還流冷却器、撹拌機、滴下ロートを備えた４つ口フラスコに、ＰＭＡ２７重量部、三菱ガス化学（株）製トリメリット酸（以下、ＴＭＡ）を２７重量部、ｎ−プロピルビニルエーテルを４６重量部加え、撹拌しながら加熱し７０℃に昇温した。次いで、温度を保ちながら６時間撹拌し続けたところ、溶液の酸価０．７３ｍｇＫＯＨ／ｇの潜在化された硬化剤溶液（ＢＴＭＡ）が得られた。
＜合成例６：多価ヘミアセタールエステル化合物（ＢＣＨＴＡ）の合成＞
ＴＭＡの代わりにＣＨＴＡを使用した以外は合成例５と同様の方法で、溶液の酸価０．８２ｍｇＫＯＨ／ｇの潜在化された硬化剤溶液（ＢＣＨＴＡ）を得た。
R 1 and R 2 in the table correspond to R 1 and R 2 in the formula (1), respectively.
<Synthesis Example 5 : Synthesis of polyvalent hemiacetal ester compound (BTMA)>
In a four-necked flask equipped with a thermometer, reflux condenser, stirrer, and dropping funnel, 27 parts by weight of PMA, 27 parts by weight of trimellitic acid (hereinafter, TMA) manufactured by Mitsubishi Gas Chemical Co., Ltd., and n-propyl vinyl ether 46 parts by weight was added and heated with stirring to 70 ° C. Subsequently, stirring was continued for 6 hours while maintaining the temperature, and a latent hardener solution (BTMA) having an acid value of 0.73 mgKOH / g of the solution was obtained.
<Synthesis Example 6 : Synthesis of polyvalent hemiacetal ester compound (BCHTA)>
A latent hardener solution (BCHTA) having a solution acid value of 0.82 mg KOH / g was obtained in the same manner as in Synthesis Example 5 except that CHTA was used instead of TMA.
＜重合例１：エポキシ基含有重合体（ＰＧＭＡ）の合成＞
温度計、還流冷却器、撹拌機、滴下ロートを備えた容量５００ｍＬの４つ口フラスコに、プロピレングリコールモノメチルエーテルアセテートを１６０ｇ仕込み、撹拌しながら加熱して８０℃に昇温した。次いで、８０℃の温度でグリシジルメタクリレート１１４重量部、シクロヘキシルメタクリレート８６重量部、日本油脂（株）製の過酸化物系重合開始剤「パーヘキシルＯ（；商品名、純度９３％）」９重量部、およびプロピレングリコールモノメチルエーテルアセテート３３ｇを予め均一混合したもの（滴下成分）を、２時間かけて滴下ロートより等速滴下した。滴下終了後、９８℃の温度を７時間維持した後、反応を終了した。重量平均分子量（Ｍｗ）３２，０００、固形分５２％、粘度２１Ｐａ・ｓ（２０℃）および溶液のエポキシ当量５２０ｇ／ｍｏｌのエポキシ基を有する重合体溶液（ＰＧＭＡ）を得た。
<Polymerization Example 1: Synthesis of Epoxy Group-Containing Polymer (PGMA)>
160 g of propylene glycol monomethyl ether acetate was charged into a 500 mL four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, and heated to 80 ° C. with stirring. Subsequently, 114 parts by weight of glycidyl methacrylate, 86 parts by weight of cyclohexyl methacrylate at a temperature of 80 ° C., 9 parts by weight of a peroxide-based polymerization initiator “Perhexyl O (; trade name, purity 93%)” manufactured by NOF Corporation, Then, 33 g of propylene glycol monomethyl ether acetate previously mixed uniformly (dropping component) was dropped at a constant rate from a dropping funnel over 2 hours. After completion of the dropping, the temperature was maintained at 98 ° C. for 7 hours, and then the reaction was terminated. A polymer solution (PGMA) having an epoxy group having a weight average molecular weight (Mw) of 32,000, a solid content of 52%, a viscosity of 21 Pa · s (20 ° C.) and an epoxy equivalent of 520 g / mol of the solution was obtained.
＜実施例１−１：熱潜在性触媒Ｌ−１の合成＞
撹拌子を備え、窒素置換した２口フラスコに、ジアミン化合物Ａ−１を２．８６重量部、酢酸亜鉛１．８３重量部、メタノール１０重量部を投入し、室温で８時間撹拌した。反応終了後の反応液から白色沈殿を濾別し、メタノールで洗浄後、減圧乾燥して熱潜在性触媒Ｌ−１を得た（乾燥後重量２．９８重量部）。
＜実施例１−２：熱潜在性触媒Ｌ−２の合成＞
撹拌子を備え、窒素置換した２口フラスコに、ジアミン化合物Ａ−２を２．７２重量部、２−エチルヘキサン酸酸化ジルコニウム３．９４重量部、メタノール１０重量部を投入し、室温で８時間撹拌した。反応終了後の反応液から白色沈殿を濾別し、メタノールで洗浄後、減圧乾燥して熱潜在性触媒Ｌ−２を得た（乾燥後重量５．６８重量部）。
＜実施例１−３：熱潜在性触媒Ｌ−３の合成＞
撹拌子を備え、窒素置換した２口フラスコに、ジアミン化合物Ａ−３を３．２０重量部、２−エチルヘキサン酸酸化チタン３．５０重量部、メタノール１０重量部を投入し、室温で８時間撹拌した。反応終了後の反応液から白色沈殿を濾別し、メタノールで洗浄後、減圧乾燥して熱潜在性触媒Ｌ−３を得た（乾燥後重量６．１２重量部）。
<Example 1-1 : Synthesis of thermal latent catalyst L-1>
2.86 parts by weight of diamine compound A-1, 1.83 parts by weight of zinc acetate and 10 parts by weight of methanol were added to a two-necked flask equipped with a stir bar and purged with nitrogen, and stirred at room temperature for 8 hours. A white precipitate was filtered from the reaction solution after completion of the reaction, washed with methanol, and dried under reduced pressure to obtain a thermal latent catalyst L-1 (weight after drying: 2.98 parts by weight).
<Example 1-2 : Synthesis of thermal latent catalyst L-2>
A 2-neck flask equipped with a stirrer and purged with nitrogen was charged with 2.72 parts by weight of diamine compound A-2, 3.94 parts by weight of zirconium oxide 2-ethylhexanoate, and 10 parts by weight of methanol, and at room temperature for 8 hours. Stir. A white precipitate was filtered from the reaction solution after completion of the reaction, washed with methanol, and dried under reduced pressure to obtain a thermal latent catalyst L-2 (weight after drying: 5.68 parts by weight).
<Example 1-3 : Synthesis of thermal latent catalyst L-3>
A 2-neck flask equipped with a stirrer and purged with nitrogen was charged with 3.20 parts by weight of diamine compound A-3, 3.50 parts by weight of 2-ethylhexanoic acid titanium oxide, and 10 parts by weight of methanol, and at room temperature for 8 hours. Stir. A white precipitate was filtered from the reaction solution after completion of the reaction, washed with methanol, and dried under reduced pressure to obtain a thermal latent catalyst L-3 (weight after drying: 6.12 parts by weight).
＜実施例１−４：熱潜在性触媒Ｌ−４の合成＞
撹拌子を備え、窒素置換した２口フラスコに、ジアミン化合物Ａ−４を３．７９重量部、チタンプロポキシド２．８４重量部、メタノール１０重量部を投入し、室温で８時間撹拌した。反応終了後の反応液から白色沈殿を濾別し、メタノールで洗浄後、減圧乾燥して熱潜在性触媒Ｌ−４を得た（乾燥後重量６．２８重量部）。
＜参考例１：熱潜在性触媒Ｌ−５の合成＞
撹拌子を備え、窒素置換した２口フラスコに、Ｎ，Ｎ'−ビス（サリチリデン）−１，２−プロパンジアミンを２．８２重量部、酢酸亜鉛１．８３重量部、メタノール１０重量部を投入し、室温で８時間撹拌した。反応終了後の反応液から黄色沈殿を濾別し、メタノールで洗浄後、減圧乾燥して熱潜在性触媒Ｌ−５を得た（乾燥後重量２．８５重量部）。
＜熱硬化性樹脂組成物の配合＞
十分に乾燥させた試験管に撹拌子、エポキシ基含有化合物、ヘミアセタールエステル基含有化合物、および熱潜在性触媒を所定量加えて均一になるまで撹拌して熱硬化性樹脂組成物を得た。
調製した熱硬化性樹脂組成物に対して、保存安定性、硬化性および硬化膜の透明性についての試験評価を行い、熱潜在性触媒としての性能を判断した。
<Example 1-4 : Synthesis of thermal latent catalyst L-4>
To a two-necked flask equipped with a stirrer and purged with nitrogen, 3.79 parts by weight of diamine compound A-4, 2.84 parts by weight of titanium propoxide, and 10 parts by weight of methanol were added, and stirred at room temperature for 8 hours. A white precipitate was filtered off from the reaction solution after completion of the reaction, washed with methanol, and dried under reduced pressure to obtain a thermal latent catalyst L-4 (weight 6.28 parts by weight after drying).
<Reference Example 1: Synthesis of thermal latent catalyst L-5>
A 2-neck flask equipped with a stir bar and purged with nitrogen was charged with 2.82 parts by weight of N, N′-bis (salicylidene) -1,2-propanediamine, 1.83 parts by weight of zinc acetate, and 10 parts by weight of methanol. And stirred at room temperature for 8 hours. A yellow precipitate was filtered off from the reaction solution after completion of the reaction, washed with methanol, and dried under reduced pressure to obtain thermal latent catalyst L-5 (weight: 2.85 parts by weight after drying).
<Formulation of thermosetting resin composition>
A predetermined amount of a stirrer, an epoxy group-containing compound, a hemiacetal ester group-containing compound, and a thermal latent catalyst were added to a sufficiently dried test tube and stirred until uniform to obtain a thermosetting resin composition.
The prepared thermosetting resin composition was evaluated for storage stability, curability and transparency of the cured film, and the performance as a heat latent catalyst was judged.
＜保存安定性＞
上記熱硬化性樹脂組成物について、調製直後の粘度と４０℃にて１０日間静置した後の粘度の比から保存安定性を評価した。粘度上昇率（％）は次式に基づく。
粘度上昇率（％）＝（４０℃にて１０日放置後の粘度）／（調製直後の粘度）×１００
粘度上昇率が１１０％以下であると、実用に供することができると判断できる。
＜硬化性＞
また、前記の熱硬化性樹脂組成物を、ブリキ板にバーコーターで塗布し、１５０℃、１時間の条件で硬化させて熱硬化性樹脂組成物の硬化物としての硬化膜を得た。この硬化膜に対し、アセトンをしみこませたティシュー紙で擦ることによって、熱硬化性樹脂組成物の硬化性を確認した。１００往復擦っても傷が目視で確認できなければ○、傷が目視で確認できれば×と判定した。
＜硬化膜の透明性＞
さらに、前記の熱硬化性樹脂組成物を、１ｍｍ厚のガラス板にバーコーターで塗布し、１５０℃、１時間の条件で硬化させて熱硬化性樹脂組成物の硬化物としての硬化膜を得た。この硬化膜の透明性を（株）島津製作所製分光光度計ＵＶ−２４５０を用いて波長４００ｎｍでの透過率を測定することにより評価した。透過率（％）は、未塗工のガラス板の透過率を１００％としたときの波長４００ｎｍでの透過率（％）で表した。
透過率が９０％以上であると、実用に供することのできる透明性であると判断できる。
＜実施例１〜４、および比較例１〜５＞
実施例１〜４、および比較例１〜５について、配合組成と性能評価結果を表２に示す。
<Storage stability>
About the said thermosetting resin composition, storage stability was evaluated from ratio of the viscosity immediately after preparation, and the viscosity after leaving still at 40 degreeC for 10 days. The viscosity increase rate (%) is based on the following formula.
Viscosity increase rate (%) = (viscosity after standing at 40 ° C. for 10 days) / (viscosity immediately after preparation) × 100
It can be judged that it can use for practical use as a viscosity increase rate is 110% or less.
<Curing property>
Moreover, the said thermosetting resin composition was apply | coated to the tin plate with the bar coater, and it hardened | cured on 150 degreeC and the conditions for 1 hour, and obtained the cured film as a hardened | cured material of a thermosetting resin composition. The cured film was rubbed with tissue paper soaked with acetone to confirm the curability of the thermosetting resin composition. If the scratch was not visually confirmed even after 100 reciprocations, it was judged as ◯, and if the scratch was visually confirmed, it was judged as x.
<Transparency of cured film>
Furthermore, the thermosetting resin composition is applied to a 1 mm thick glass plate with a bar coater and cured at 150 ° C. for 1 hour to obtain a cured film as a cured product of the thermosetting resin composition. It was. The transparency of the cured film was evaluated by measuring the transmittance at a wavelength of 400 nm using a spectrophotometer UV-2450 manufactured by Shimadzu Corporation. The transmittance (%) was expressed as the transmittance (%) at a wavelength of 400 nm when the transmittance of an uncoated glass plate was 100%.
If the transmittance is 90% or more, it can be determined that the transparency is practical.
<Examples 1-4 and Comparative Examples 1-5>
Table 2 shows the composition and performance evaluation results for Examples 1 to 4 and Comparative Examples 1 to 5.
表中の略号は、下記の通りである。
Ｌ−６：２−エチルヘキサン酸亜鉛
Ｌ−７： オクチル酸亜鉛とＮ−メチルモルホリンの反応物（特開２００１−３５００１０号公報記載：ＬＣＡＴ−１）
Ｌ−８：塩化亜鉛とＯ，Ｏ−ジ−ｐ−メチルベンジルフェニルフォスフォネートの反応物（Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ、３３巻，２３５９頁（２０００年）記載）
Abbreviations in the table are as follows.
L- 6 : zinc 2-ethylhexanoate L- 7 : reaction product of zinc octylate and N-methylmorpholine (Japanese Patent Laid-Open No. 2001-350010: LCAT-1)
L- 8 : Reaction product of zinc chloride and O, O-di-p-methylbenzylphenyl phosphonate (Macromolecules, 33, 2359 (2000))
実施例１〜４において、本発明の熱潜在性触媒Ｌ−１〜Ｌ−４は熱硬化性樹脂組成物として配合したときに４０℃、１０日の保存期間においても活性を示さず、１５０℃、１時間の硬化温度においては触媒活性を示すことから、優れた熱潜在性触媒であることが明らかとなった。また、本発明の熱硬化性樹脂組成物を硬化して得られる硬化膜が非常に優れた透明性を有することも判った。
一方、比較例１において触媒を配合しない場合では硬化性が不足しており、本発明の熱潜在性触媒とは構造の異なる熱潜在性触媒を用いた場合、硬化膜の透明性が不足したり（比較例２、５）、保存安定性が不足したり（比較例３、４）して、本発明の課題を解決し得ないことが明らかとなった。
In Examples 1-4, thermal latent catalysts L-1 to L-4 of the present invention is 40 ° C. when formulated as a thermosetting resin composition, exhibited no activity in storage period of 10 days, 0.99 ° C. Since it showed catalytic activity at a curing temperature of 1 hour, it was revealed that it was an excellent thermal latent catalyst. Moreover, it turned out that the cured film obtained by hardening | curing the thermosetting resin composition of this invention has the very outstanding transparency.
On the other hand, in the case where no catalyst is blended in Comparative Example 1, the curability is insufficient, and when a thermal latent catalyst having a structure different from that of the thermal latent catalyst of the present invention is used, the transparency of the cured film is insufficient. (Comparative Examples 2 and 5) It became clear that the storage stability was insufficient (Comparative Examples 3 and 4), and the problems of the present invention could not be solved.
Claims (2)
ＭＸn2 ・・・ （２）
（式中のＭは亜鉛、ジルコニウムまたはチタンであり、Ｘは酸素原子、アルコキシ基、フェノキシ基またはアシルオキシ基であり、ｎ２が２以上の場合はＸで示される複数の基は互いに同一でも異なっていてもよく、またＸで示される基は互いに結合して環を形成していてもよい。ｎ２はＭの価数を満たす整数である。） A heat latent curing catalyst for a thermosetting resin obtained by reacting a diamine compound (A) represented by the following formula (1) with a metal salt (B) represented by the following formula (2).
MX n2 (2)
(In the formula, M is zinc, zirconium or titanium, X is an oxygen atom, an alkoxy group, a phenoxy group or an acyloxy group, and when n2 is 2 or more, a plurality of groups represented by X are the same or different from each other) And the groups represented by X may be bonded to each other to form a ring, and n2 is an integer satisfying the valence of M.)
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