JP2017132798A - Peroxide and thermosetting resin composition - Google Patents
Peroxide and thermosetting resin composition Download PDFInfo
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- JP2017132798A JP2017132798A JP2017077454A JP2017077454A JP2017132798A JP 2017132798 A JP2017132798 A JP 2017132798A JP 2017077454 A JP2017077454 A JP 2017077454A JP 2017077454 A JP2017077454 A JP 2017077454A JP 2017132798 A JP2017132798 A JP 2017132798A
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- Prior art keywords
- group
- peroxide
- carbon atoms
- represented
- ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 150000002978 peroxides Chemical class 0.000 title claims abstract description 92
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 51
- 239000011342 resin composition Substances 0.000 title claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 49
- 125000000962 organic group Chemical group 0.000 claims abstract description 25
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 14
- 125000001867 hydroperoxy group Chemical group [*]OO[H] 0.000 claims abstract description 6
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 5
- 230000000977 initiatory effect Effects 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 54
- 239000003822 epoxy resin Substances 0.000 claims description 40
- 229920000647 polyepoxide Polymers 0.000 claims description 40
- -1 hydroperoxyhydroxyethyl group Chemical group 0.000 claims description 37
- 239000004973 liquid crystal related substance Substances 0.000 claims description 34
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- 125000003700 epoxy group Chemical group 0.000 claims description 17
- 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 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 14
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical class C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000000565 sealant Substances 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 9
- 239000007870 radical polymerization initiator Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000000732 arylene group Chemical group 0.000 claims description 5
- 125000005336 allyloxy group Chemical group 0.000 claims description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 claims description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 2
- PLDLPVSQYMQDBL-UHFFFAOYSA-N 2-[[3-(oxiran-2-ylmethoxy)-2,2-bis(oxiran-2-ylmethoxymethyl)propoxy]methyl]oxirane Chemical compound C1OC1COCC(COCC1OC1)(COCC1OC1)COCC1CO1 PLDLPVSQYMQDBL-UHFFFAOYSA-N 0.000 claims description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 2
- 229930185605 Bisphenol Natural products 0.000 claims description 2
- 208000007976 Ketosis Diseases 0.000 claims description 2
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 150000002584 ketoses Chemical class 0.000 claims description 2
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 2
- 229960001553 phloroglucinol Drugs 0.000 claims description 2
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 2
- 229940079877 pyrogallol Drugs 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 150000005846 sugar alcohols Chemical class 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 150000001323 aldoses Chemical class 0.000 claims 1
- 150000001721 carbon Chemical group 0.000 claims 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 abstract description 6
- 239000002245 particle Substances 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 25
- 230000008569 process Effects 0.000 description 15
- 239000002904 solvent Substances 0.000 description 13
- 125000004429 atom Chemical group 0.000 description 10
- 238000001723 curing Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 125000005843 halogen group Chemical group 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000007789 sealing Methods 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 125000004434 sulfur atom Chemical group 0.000 description 8
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- 239000010954 inorganic particle Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000011109 contamination Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 125000001188 haloalkyl group Chemical group 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 239000011258 core-shell material Substances 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 150000002825 nitriles Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- KZSBTZUWHMJUHH-UHFFFAOYSA-N NOCC(COO)O Chemical compound NOCC(COO)O KZSBTZUWHMJUHH-UHFFFAOYSA-N 0.000 description 3
- KCGDYDRLXAAOOI-UHFFFAOYSA-N NOCC1OOC1 Chemical compound NOCC1OOC1 KCGDYDRLXAAOOI-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000010828 elution Methods 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
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000005395 methacrylic acid group Chemical group 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 125000004437 phosphorous atom Chemical group 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000001174 sulfone group Chemical group 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 235000012222 talc Nutrition 0.000 description 3
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- GCYHRYNSUGLLMA-UHFFFAOYSA-N 2-prop-2-enoxyethanol Chemical group OCCOCC=C GCYHRYNSUGLLMA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 125000005641 methacryl group Chemical group 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- NPENBPVOAXERED-UHFFFAOYSA-N (4-benzoylphenyl)-phenylmethanone Chemical class C=1C=C(C(=O)C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 NPENBPVOAXERED-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- MLKIVXXYTZKNMI-UHFFFAOYSA-N 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one Chemical compound CCCCCCCCCCCCC1=CC=C(C(=O)C(C)(C)O)C=C1 MLKIVXXYTZKNMI-UHFFFAOYSA-N 0.000 description 1
- PWMWNFMRSKOCEY-UHFFFAOYSA-N 1-Phenyl-1,2-ethanediol Chemical compound OCC(O)C1=CC=CC=C1 PWMWNFMRSKOCEY-UHFFFAOYSA-N 0.000 description 1
- XZKLXPPYISZJCV-UHFFFAOYSA-N 1-benzyl-2-phenylimidazole Chemical compound C1=CN=C(C=2C=CC=CC=2)N1CC1=CC=CC=C1 XZKLXPPYISZJCV-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- BRKORVYTKKLNKX-UHFFFAOYSA-N 2,4-di(propan-2-yl)thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC(C(C)C)=C3SC2=C1 BRKORVYTKKLNKX-UHFFFAOYSA-N 0.000 description 1
- UXCIJKOCUAQMKD-UHFFFAOYSA-N 2,4-dichlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC(Cl)=C3SC2=C1 UXCIJKOCUAQMKD-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
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- 238000004448 titration Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001834 xanthenyl group Chemical group C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 125000004933 β-carbolinyl group Chemical group C1(=NC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
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Abstract
Description
本発明は、過酸化物及び熱硬化性樹脂組成物に関する。 The present invention relates to a peroxide and a thermosetting resin composition.
液晶表示パネルの製造方法として液晶滴下工法が知られている。液晶滴下工法とは、光及び熱併用硬化型液晶シール剤を、電極パターン及び配向膜が形成された基板上へ塗布し、さらにその液晶シール剤が塗布された基板、又はこれと対となる基板に液晶を滴下した後、対向基板を貼り合わせて、第一段階として紫外線照射等により光硬化を行うことで基板の速やかな固定つまりセルギャップ形成を行い、第二段階として圧締治具フリーによる熱硬化によりシール剤を完全硬化させることで、液晶表示パネルを製造する手法である。このような液晶滴下工法では、未硬化の液晶シール剤と液晶とが接触した状態で光硬化ならびに熱硬化反応が進行するため、液晶シール剤には、硬化の工程中、すなわち、光硬化前後、熱硬化前後における液晶シール剤由来の液晶への汚染の低減が求められる。同様に、電子部品の気密シール剤等の封止剤にも、硬化の工程中における封止剤由来の電子部品への汚染の低減が求められる。 A liquid crystal dropping method is known as a method for manufacturing a liquid crystal display panel. The liquid crystal dropping method is a method in which a light and heat combined curable liquid crystal sealant is applied onto a substrate on which an electrode pattern and an alignment film are formed, and the substrate on which the liquid crystal sealant is further applied, or a pair of substrates. After the liquid crystal is dropped on the substrate, the opposite substrate is bonded, and the substrate is quickly fixed by photo-curing by ultraviolet irradiation or the like, so that the substrate is quickly fixed, that is, the cell gap is formed. This is a technique for manufacturing a liquid crystal display panel by completely curing a sealant by thermal curing. In such a liquid crystal dropping method, photocuring and thermosetting reaction proceed in a state where the uncured liquid crystal sealing agent and the liquid crystal are in contact with each other, so the liquid crystal sealing agent has a curing process, that is, before and after photocuring, Reduction of the contamination to the liquid crystal derived from the liquid crystal sealant before and after thermosetting is required. Similarly, a sealing agent such as an airtight sealant for electronic components is also required to reduce contamination of the electronic component derived from the sealing agent during the curing process.
上記に関連して、硬化性樹脂と熱硬化剤に、熱ラジカル重合開始剤と光ラジカル重合開始剤を併用する液晶シール剤が開示されている（例えば、特許文献１及び２参照）。 In relation to the above, a liquid crystal sealing agent is disclosed in which a thermal radical polymerization initiator and a photo radical polymerization initiator are used in combination with a curable resin and a thermosetting agent (see, for example, Patent Documents 1 and 2).
特許文献１又は２に記載された熱ラジカル重合開始剤を含む液晶シール剤では、熱重合性が充分とは言い難い場合があった。
本発明は、熱ラジカル重合開始能を有する過酸化物及びそれらを含む熱硬化性樹脂組成物を提供することを課題とする。
In the liquid crystal sealing agent containing the thermal radical polymerization initiator described in Patent Document 1 or 2, it may be difficult to say that the thermal polymerization property is sufficient.
This invention makes it a subject to provide the peroxide which has thermal radical polymerization initiating ability, and the thermosetting resin composition containing them.
＜１＞ 下記一般式（Ｉ）で表される過酸化物である。 <1> A peroxide represented by the following general formula (I).
（式中、Ｒ１は有機基を表す。Ｒ２及びＲ３は、一方がヒドロキシ基であり他方がヒドロパーオキシ基であるか、Ｒ２とＲ３が一緒になってパーオキシ基を表す） (In the formula, R 1 represents an organic group. One of R 2 and R 3 is a hydroxy group and the other is a hydroperoxy group, or R 2 and R 3 together represent a peroxy group)
＜２＞ 下記一般式（ＩＩ）で表されるアリルエーテル誘導体を過酸化物と接触させて得られる＜１＞に記載の過酸化物である。
（式中、Ｒ１は一般式（Ｉ）におけるＲ１と同義である）
<2> The peroxide according to <1>, which is obtained by bringing an allyl ether derivative represented by the following general formula (II) into contact with a peroxide.
(Wherein, R 1 has the same meaning as R 1 in the general formula (I))
＜３＞ 一般式（Ｉ）におけるＲ１が、水素原子、ハロゲン原子、炭素原子、酸素原子、窒素原子、ホウ素原子、リン原子、ケイ素原子及び硫黄原子からなる群より選択される２以上の原子から構成される有機基である＜１＞又は＜２＞に記載の過酸化物である。
＜４＞ 一般式（Ｉ）におけるＲ１が、エポキシ基を有する有機基である＜１＞〜＜３＞いずれか１つに記載の過酸化物である。
<3> Two or more atoms selected from the group consisting of R 1 in the general formula (I) are a hydrogen atom, a halogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a boron atom, a phosphorus atom, a silicon atom, and a sulfur atom The peroxide according to <1> or <2>, which is an organic group composed of
<4> The peroxide according to any one of <1> to <3>, wherein R 1 in the general formula (I) is an organic group having an epoxy group.
＜５＞ 下記一般式（ＩＩ）で表されるアリルエーテル誘導体と過酸化物とを接触させることを含む＜１＞〜＜４＞のいずれか１つに記載の過酸化物の製造方法である。 <5> The method for producing a peroxide according to any one of <1> to <4>, comprising bringing an allyl ether derivative represented by the following general formula (II) into contact with a peroxide. .
＜６＞ ＜１＞〜＜４＞のいずれか１項に記載の過酸化物と、重合性化合物とを含む熱硬化性樹脂組成物である。
＜７＞ 光重合開始剤を更に含む＜６＞に記載の熱硬化性樹脂組成物である。
＜８＞ 液晶滴下シール剤用である＜６＞又は＜７＞に記載の熱硬化性樹脂組成物である。
<6> A thermosetting resin composition comprising the peroxide according to any one of <1> to <4> and a polymerizable compound.
<7> The thermosetting resin composition according to <6>, further including a photopolymerization initiator.
<8> The thermosetting resin composition according to <6> or <7>, which is for a liquid crystal dropping sealant.
本発明によれば、熱ラジカル重合開始能を有する過酸化物及びそれらを含む熱硬化性樹脂組成物を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the peroxide which has thermal radical polymerization initiating ability, and the thermosetting resin composition containing them can be provided.
本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の目的が達成されれば、本用語に含まれる。また本明細書において「〜」を用いて示された数値範囲は、「〜」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。さらに本明細書において組成物中の各成分の含有量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。
「（メタ）アクリル」とは「アクリル」及び「メタクリル」の少なくとも一方を意味する。
In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. . In the present specification, a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. Further, in the present specification, the content of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. Means.
“(Meth) acryl” means at least one of “acryl” and “methacryl”.
［過酸化物］
本発明の過酸化物は、下記一般式（Ｉ）で表される。式中、Ｒ１は有機基を表す。Ｒ２及びＲ３は、一方がヒドロキシ基であり他方がヒドロパーオキシ基であるか、Ｒ２とＲ３が一緒になってパーオキシ基を表す。すなわち本発明の化合物は、下記一般式（Ｉａ）、（Ｉｂ）及び（Ｉｃ）のいずれかで表される。本発明の過酸化物は、特定の構造を有することで、優れた熱ラジカル重合活性を示す。
[Peroxide]
The peroxide of the present invention is represented by the following general formula (I). In the formula, R 1 represents an organic group. One of R 2 and R 3 is a hydroxy group and the other is a hydroperoxy group, or R 2 and R 3 together represent a peroxy group. That is, the compound of the present invention is represented by any one of the following general formulas (Ia), (Ib) and (Ic). The peroxide of this invention shows the outstanding thermal radical polymerization activity by having a specific structure.
また本発明の過酸化物は、下記一般式（ＩＩ）で表されるアリルエーテル誘導体を過酸化物と接触させて得られる過酸化物であることが好ましい。一般式（ＩＩ）におけるＲ１は、一般式（Ｉ）におけるＲ１と同義である。 The peroxide of the present invention is preferably a peroxide obtained by bringing an allyl ether derivative represented by the following general formula (II) into contact with a peroxide. R 1 in the general formula (II) has the same meaning as R 1 in the general formula (I).
Ｒ１で表される有機基は、少なくとも１つの炭素原子を含む基であれば特に制限されない。Ｒ１で表される有機基を構成する原子としては、水素原子、ハロゲン原子、炭素原子、酸素原子、窒素原子、ホウ素原子、リン原子、ケイ素原子、硫黄原子等を挙げることができる。
Ｒ１は、水素原子、ハロゲン原子、炭素原子、酸素原子、窒素原子、ホウ素原子、リン原子、ケイ素原子及び硫黄原子からなる群より選択される２以上の原子から構成される有機基であることが好ましく、水素原子、ハロゲン原子、炭素原子、酸素原子及び硫黄原子からなる群より選択される２以上の原子から構成される有機基であることがより好ましく、水素原子、ハロゲン原子、炭素原子、酸素原子及び硫黄原子からなる群より選択される２以上の原子から構成され、炭素数が１〜５００の有機基であることが更に好ましく、水素原子、ハロゲン原子、炭素原子、酸素原子及び硫黄原子からなる群より選択される２以上の原子から構成され、炭素数が１〜１６０であり、分子量が１５〜４０００の有機基であることが更に好ましく、水素原子、炭素原子、酸素原子及び硫黄原子からなる群より選択される２以上の原子から構成され、炭素数が３〜４０であり、分子量が１００〜６５０の有機基であることが特に好ましい。
なお、ハロゲン原子としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子が挙げられる。
The organic group represented by R 1 is not particularly limited as long as it is a group containing at least one carbon atom. Examples of the atoms constituting the organic group represented by R 1 include a hydrogen atom, a halogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a boron atom, a phosphorus atom, a silicon atom, and a sulfur atom.
R 1 is an organic group composed of two or more atoms selected from the group consisting of hydrogen atom, halogen atom, carbon atom, oxygen atom, nitrogen atom, boron atom, phosphorus atom, silicon atom and sulfur atom. Is more preferable, and is more preferably an organic group composed of two or more atoms selected from the group consisting of a hydrogen atom, a halogen atom, a carbon atom, an oxygen atom and a sulfur atom, and a hydrogen atom, a halogen atom, a carbon atom, It is more preferably an organic group composed of two or more atoms selected from the group consisting of an oxygen atom and a sulfur atom, and having 1 to 500 carbon atoms, a hydrogen atom, a halogen atom, a carbon atom, an oxygen atom, and a sulfur atom. More preferably, the organic group is composed of two or more atoms selected from the group consisting of carbon atoms having 1 to 160 carbon atoms and a molecular weight of 15 to 4000. It is particularly preferably an organic group composed of two or more atoms selected from the group consisting of an atom, a carbon atom, an oxygen atom and a sulfur atom, having 3 to 40 carbon atoms and having a molecular weight of 100 to 650.
In addition, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.
また、Ｒ１で表される有機基は、少なくとも１つのエポキシ基を有する有機基であることもまた好ましい。Ｒ１で表される有機基がエポキシ基を有する場合、分子内のエポキシ基の総数は１〜３０であることが好ましく、１〜１０であることがより好ましい。
更に、Ｒ１で表される有機基は、一般式（Ｉ）におけるＲ１以外の部分構造、すなわちヒドロパーオキシヒドロキシプロピルオキシ構造及び１，２−ジオキセタニル−３−メチルオキシ構造の少なくとも一方をＲ１の部分構造として更に有していてもよい。
The organic group represented by R 1 is also preferably an organic group having at least one epoxy group. When the organic group represented by R 1 has an epoxy group, the total number of epoxy groups in the molecule is preferably 1 to 30, and more preferably 1 to 10.
Furthermore, the organic group represented by R 1 represents at least one of a partial structure other than R 1 in the general formula (I), that is, a hydroperoxyhydroxypropyloxy structure and a 1,2-dioxetanyl-3-methyloxy structure. it may further have as a partial structure of R 1.
Ｒ１で表される有機基を構成する部分構造としては、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、炭素数１〜１０のハロアルキル基、炭素数２〜１０のアルケニル基、炭素数６〜２０のアリール基、炭素数７〜２１のアラルキル基、総原子数５〜３０のヘテロアリール基、ヒドロキシ基、エポキシ基、酸素原子、カルボニル基、スルホン基、パーオキシ基、ヒドロパーオキシ基、ヒドロパーオキシヒドロキシプロピルオキシ基、１，２−ジオキセタニルメチルオキシ基、これらの組合せ等を挙げることができる。
有機基を構成するアルキル基、アルケニル基、アルキレン基及びアルケニレン基は、直鎖状、分岐鎖状及び環状のいずれであってもよい。また有機基を構成する部分構造は置換基を有していてもよく、置換基としては上記部分構造を挙げることができる。
ハロアルキル基におけるハロゲン原子としては、フッ素原子、塩素原子、臭素原子等が挙げられ、置換数は１〜３である。
ヘテロアリール基は、炭素原子の他に、少なくとも酸素原子、硫黄原子及び窒素原子からなる群から選択される１以上のヘテロ原子を含む、総原子数５〜３０の単環又は多環の複素環基であり、イミダゾリル基、キサンテニル基、チオキサンテニル基、チエニル基、ジベンゾフリル基、クロメニル基、イソチオクロメニル基、フェノキサチイニル基、ピロリル基、ピラゾリル基、ピラジニル基、ピリミジニル基、ピリダジニル基、インドリジニル基、イソインドリル基、インドリル基、インダゾリル基、プリニル基、キノリジニル基、イソキノリル基、キノリル基、フタラジニル基、ナフチリジニル基、キノキサリニル基、キナゾリニル基、シンノリニル基、プテリジニル基、カルバゾリル基、β−カルボリニル基、フェナントリジニル基、アクリジニル基、ペリミジニル基、フェナントロリニル基、フェナジニル基、イソチアゾリル基、フェノチアジニル基、イソオキサゾリル基及びフラザニル基等が挙げられる
Examples of the partial structure constituting the organic group represented by R 1 include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, and an alkenyl having 2 to 10 carbon atoms. Group, aryl group having 6 to 20 carbon atoms, aralkyl group having 7 to 21 carbon atoms, heteroaryl group having 5 to 30 total atoms, hydroxy group, epoxy group, oxygen atom, carbonyl group, sulfone group, peroxy group, hydro A peroxy group, a hydroperoxyhydroxypropyloxy group, a 1,2-dioxetanylmethyloxy group, a combination thereof, and the like can be given.
The alkyl group, alkenyl group, alkylene group and alkenylene group constituting the organic group may be linear, branched or cyclic. Moreover, the partial structure which comprises an organic group may have a substituent, and the said partial structure can be mentioned as a substituent.
Examples of the halogen atom in the haloalkyl group include a fluorine atom, a chlorine atom, and a bromine atom, and the number of substitutions is 1 to 3.
The heteroaryl group is a monocyclic or polycyclic heterocycle having 5 to 30 total atoms, including at least one heteroatom selected from the group consisting of an oxygen atom, a sulfur atom and a nitrogen atom in addition to a carbon atom Imidazolyl group, xanthenyl group, thioxanthenyl group, thienyl group, dibenzofuryl group, chromenyl group, isothiochromenyl group, phenoxathiinyl group, pyrrolyl group, pyrazolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl Group, isoindolyl group, indolyl group, indazolyl group, purinyl group, quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxalinyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, carbazolyl group, β-carbolinyl group, Nantridinyl group, Kurijiniru group, perimidinyl group, phenanthrolinyl group, phenazinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, and a furazanyl group
Ｒ１で表される有機基は、炭素数１〜１０のアルキル基、炭素数１〜１０のハロアルキル基、炭素数６〜２０のアリール基、炭素数７〜１１のアラルキル基からなる群より選択され、ヒドロキシ基、炭素数１〜１０のアルキル基、フェニル基、ベンジル基、炭素数１〜１０のアルコキシ基、グリシジルオキシ基、アリルオキシ基、ヒドロパーオキシヒドロキシプロピルオキシ基及び１，２−ジオキセタニルメチルオキシ基からなる群より選択される少なくとも１つの置換基を有していてもよい有機基；又は炭素数１〜１０のアルキル基、炭素数１〜１０のハロアルキル基、炭素数６〜２０のアリール基、炭素数７〜１１のアラルキル基、ヒドロキシ基、エポキシ基、ヒドロパーオキシ基及びジオキセタニルメチルオキシ基からなる群より選択される少なくとも１種の基と、炭素数１〜６のアルキレン基、炭素数６〜１０のアリーレン基、酸素原子、パーオキシ基、カルボニル基及びスルホン基からなる群より選択される少なくとも１種の基から構成される有機基であることが好ましく；少なくとも１つのエポキシ基と、炭素数１〜６のアルキレン基、炭素数６〜１０のアリーレン基、酸素原子、カルボニル基及びスルホン基からなる群より選択される少なくとも１種の基を含み、必要に応じて、炭素数１〜６のアルキル基、炭素数１〜１０のハロアルキル基、炭素数６〜２０のアリール基、炭素数７〜１１のアラルキル基及びヒドロキシ基からなる群より選択される少なくとも１種の置換基を含んで構成される有機基であることがより好ましい。 The organic group represented by R 1 is selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 11 carbon atoms. Hydroxy group, alkyl group having 1 to 10 carbon atoms, phenyl group, benzyl group, alkoxy group having 1 to 10 carbon atoms, glycidyloxy group, allyloxy group, hydroperoxyhydroxypropyloxy group, and 1,2-dioxetanyl An organic group optionally having at least one substituent selected from the group consisting of a methyloxy group; or an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, and an alkyl group having 6 to 20 carbon atoms. Selected from the group consisting of an aryl group, an aralkyl group having 7 to 11 carbon atoms, a hydroxy group, an epoxy group, a hydroperoxy group, and a dioxetanylmethyloxy group And at least one group selected from the group consisting of an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 10 carbon atoms, an oxygen atom, a peroxy group, a carbonyl group and a sulfone group. Preferably selected from the group consisting of at least one epoxy group, an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 10 carbon atoms, an oxygen atom, a carbonyl group, and a sulfone group. An alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 11 carbon atoms, as necessary. And an organic group comprising at least one substituent selected from the group consisting of hydroxy groups.
また一般式（Ｉ）で表される過酸化物は、２以上のエポキシ基を有するエポキシ樹脂が有する１つのエポキシ基を、ヒドロパーオキシヒドロキシエチル基又はジオキセタニル基に置換した化合物であることもまた好ましい。２以上のエポキシ基を有するエポキシ樹脂としては、炭素数２〜１０のアルキレングリコールジグリシジルエーテル、ポリアルキレングリコールジグリシジルエーテル、グリセリントリグリシジルエーテル、ペンタエリスリトールテトラグリシジルエーテル、ジペンタエリスリトールヘキサグリシジルエーテル等の脂肪族エポキシ樹脂；ビスフェノール（例えば、Ａ、Ｆ、ＡＦ、Ｂ、Ｃ、ＡＰ、ＢＰ、Ｅ、Ｇ、Ｓ、Ｍ、ＰＨ、Ｚ、Ｐ等）型エポキシ樹脂、ビフェニルジグリシジルエーテル、ナフタレンジグリシジルエーテル、ＶＧ３１０１Ｌ（株式会社プリンテック製）、ＤＭ−ＢＩＰＤ−Ｆ（旭有機材工業社製）のテトラグリシジルエーテル、ＤＭ−ＢＩＯＣ−Ｆ（旭有機材工業社製）のテトラグリシジルエーテル等の芳香族エポキシ樹脂；フロログルシノール、ピロガロール、アルドース、ケトース、糖アルコール等のポリグリシジルエーテルなどを挙げることができる。 The peroxide represented by the general formula (I) may be a compound in which one epoxy group of an epoxy resin having two or more epoxy groups is substituted with a hydroperoxyhydroxyethyl group or a dioxetanyl group. Also preferred. Examples of the epoxy resin having two or more epoxy groups include alkylene glycol diglycidyl ether having 2 to 10 carbon atoms, polyalkylene glycol diglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, dipentaerythritol hexaglycidyl ether and the like. Aliphatic epoxy resin; bisphenol (for example, A, F, AF, B, C, AP, BP, E, G, S, M, PH, Z, P, etc.) type epoxy resin, biphenyl diglycidyl ether, naphthalene diglycidyl Aromatic compounds such as ether, VG3101L (manufactured by Printec Co., Ltd.), DM-BIPD-F (manufactured by Asahi Organic Materials Co., Ltd.), tetraglycidyl ether of DM-BIOC-F (manufactured by Asahi Organic Materials Industries Co., Ltd.) Epoxy resin Phloroglucinol, pyrogallol, mention may be made of an aldose, ketose, and polyglycidyl ethers such as sugar alcohol.
また一般式（Ｉ）で表される過酸化物は、芳香族エポキシ樹脂のアルコール開環体をアリル化して得られるアリルエーテル誘導体を過酸化物と接触させて得られる過酸化物であることもまた好ましい。 The peroxide represented by the general formula (I) may be a peroxide obtained by bringing an allyl ether derivative obtained by allylation of an alcohol ring-opened aromatic epoxy resin with a peroxide. Also preferred.
以下に、一般式（Ｉ）で表される過酸化物の具体例を示すが、本発明はこれらに限定されない。下記化学式中、Ａは下記化学式で示されるヒドロパーオキシヒドロキシプロピルオキシ基又は１，２−ジオキセタニルメチルオキシ基を表す。「＊」は結合位置を示す。Ｘは水素原子、ヒドロキシ基、炭素数１〜１０のアルキル基、フェニル基、ベンジル基、炭素数１〜１０のアルコキシ基、グリシジルオキシ基、アリルオキシ基、ヒドロパーオキシヒドロキシプロピルオキシ基、１，２−ジオキセタニルメチルオキシ基等を表す。Ｙはヒドロキシ基、フェニルオキシ基又は炭素数１〜１０のアルコキシ基を表す。 Specific examples of the peroxide represented by the general formula (I) are shown below, but the present invention is not limited thereto. In the following chemical formula, A represents a hydroperoxyhydroxypropyloxy group or a 1,2-dioxetanylmethyloxy group represented by the following chemical formula. “*” Indicates a binding position. X is a hydrogen atom, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, a phenyl group, a benzyl group, an alkoxy group having 1 to 10 carbon atoms, a glycidyloxy group, an allyloxy group, a hydroperoxyhydroxypropyloxy group, 1, 2 -Represents a dioxetanylmethyloxy group or the like. Y represents a hydroxy group, a phenyloxy group, or an alkoxy group having 1 to 10 carbon atoms.
［過酸化物の製造方法］
一般式（Ｉ）で表される過酸化物（以下、「第一の過酸化物」ともいう）は、例えば、下記反応式に示すように、対応するアリルエーテル誘導体（好ましくは、一般式（ＩＩ）で表されるアリルエーテル誘導体）と、一般式（Ｉ）で表される過酸化物以外の過酸化物（好ましくは、一般式（III）で表される過酸化物、以下、「第二の過酸化物」ともいう）とを接触させること（以下、「接触工程」ともいう）を含む製造方法で得ることができる。すなわち、一般式（Ｉ）で表される過酸化物は、アリルエーテル誘導体と、一般式（Ｉ）で表される過酸化物以外の過酸化物との反応生成物であることが好ましい。
[Production method of peroxide]
The peroxide represented by the general formula (I) (hereinafter also referred to as “first peroxide”) is, for example, a corresponding allyl ether derivative (preferably represented by the general formula ( II) and a peroxide other than the peroxide represented by the general formula (I) (preferably a peroxide represented by the general formula (III), And a “second peroxide”) (hereinafter also referred to as “contact process”). That is, the peroxide represented by the general formula (I) is preferably a reaction product of an allyl ether derivative and a peroxide other than the peroxide represented by the general formula (I).
式中、Ｒ１、Ｒ２及びＲ３は上記と同義である。Ｒ４はそれぞれ独立に、水素原子、アルキル基、アシル基、アルキルオキシカルボニル基、アリールオキシカルボニル基、スルホ基等を表す。一般式（III）で表される過酸化物は、アルカリ金属等と塩を構成していてもよい。Ｒ４におけるアルキル基及びアリール基は置換基を有していてもよい。置換基としては、アルキル基、アリール基、ハロゲン原子、ヒドロパーオキシ基等を挙げることができる。
なお、一般式（ＩＩ）で表されるアリルエーテル誘導体に一般式（III）で表される過酸化物を接触させると、一般式（Ｉａ）〜（Ｉｃ）で表される過酸化物に加えて、以下に示すような一般式（Ｉｄ）で表される化合物が得られることがある。
In the formula, R 1 , R 2 and R 3 are as defined above. R 4 each independently represents a hydrogen atom, an alkyl group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a sulfo group, or the like. The peroxide represented by the general formula (III) may constitute a salt with an alkali metal or the like. The alkyl group and aryl group in R 4 may have a substituent. Examples of the substituent include an alkyl group, an aryl group, a halogen atom, and a hydroperoxy group.
In addition, when the peroxide represented by the general formula (III) is brought into contact with the allyl ether derivative represented by the general formula (II), in addition to the peroxides represented by the general formulas (Ia) to (Ic) Thus, a compound represented by the general formula (Id) as shown below may be obtained.
第二の過酸化物としては、過酸化水素、ｔ−ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、ｐ−メンタンハイドロパーオキサイド、ジイソプロピルベンゼンパーオキサイド、ジクミルパーオキサイド、ｔ−ブチルクミルパーオキサイド、ジ−ｔ−ブチルパーオキサイド、メチルエチルケトンパーオキサイド、過酢酸、ｍ−クロロ過安息香酸、ｔ−ブチルパーオキシアセテート、過硫酸カリウム等を挙げることができる。中でも水又はアルコールに溶解可能な過酸化物であることが好ましく、水溶性の過酸化物であることがより好ましく、過酸化水素、ｔ−ブチルハイドロパーオキサイド、過酢酸及び過硫酸カリウムからなる群より選択される少なくとも１種であることが更に好ましい。
ここで水又はアルコールに溶解可能とは、２５℃において純水又はアルコール１００ｇに１ｇ以上溶解することを意味し、５ｇ以上溶解することが好ましく、１０ｇ以上溶解することが更に好ましい。
The second peroxide includes hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene peroxide, dicumyl peroxide, t-butyl cumyl peroxide, di- Examples thereof include -t-butyl peroxide, methyl ethyl ketone peroxide, peracetic acid, m-chloroperbenzoic acid, t-butyl peroxyacetate, potassium persulfate, and the like. Among them, a peroxide that is soluble in water or alcohol is preferable, a water-soluble peroxide is more preferable, and a group consisting of hydrogen peroxide, t-butyl hydroperoxide, peracetic acid, and potassium persulfate. More preferably, it is at least one selected from more.
Here, “soluble in water or alcohol” means that 1 g or more is dissolved in 100 g of pure water or alcohol at 25 ° C., preferably 5 g or more, more preferably 10 g or more.
アリルエーテル誘導体と、第二の過酸化物とを接触させる接触工程は、第一の過酸化物が生成可能であれば特に制限されない。
接触工程においては、例えば、アリルエーテル誘導体に含まれるアリル基１モルに対して、第二の過酸化物を１モル〜１００モル用いることが好ましく、１モル〜２０モル用いることがより好ましく、４モル〜１０モル用いることが更に好ましい。
接触工程における温度は、０〜６０℃であることが好ましく、１５〜５０℃であることがより好ましく、２０〜４０℃であることが更に好ましい。
接触工程における接触時間は、３時間〜２４時間であることが好ましく、３時間〜１０時間であることがより好ましく、３時間〜６時間であることが更に好ましい。
The contact step of bringing the allyl ether derivative into contact with the second peroxide is not particularly limited as long as the first peroxide can be generated.
In the contacting step, for example, 1 mol to 100 mol of the second peroxide is preferably used with respect to 1 mol of the allyl group contained in the allyl ether derivative, more preferably 1 mol to 20 mol. It is more preferable to use mol to 10 mol.
The temperature in the contacting step is preferably 0 to 60 ° C, more preferably 15 to 50 ° C, still more preferably 20 to 40 ° C.
The contact time in the contact step is preferably 3 hours to 24 hours, more preferably 3 hours to 10 hours, and still more preferably 3 hours to 6 hours.
接触工程には、溶媒を用いてもよい。溶媒としては、メタノール、エタノール、プロパノール、イソプロパノール、ｎ−ブタノール等のアルコール溶剤、アセトニトリル、プロピオニトリル、ベンゾニトリル等のニトリル溶剤、水などを挙げることができる。これらの溶媒は１種単独でも２種以上を組み合わせて用いてもよい。 A solvent may be used in the contacting step. Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, isopropanol and n-butanol, nitrile solvents such as acetonitrile, propionitrile and benzonitrile, and water. These solvents may be used alone or in combination of two or more.
接触工程に２種以上の溶媒を組み合わせて用いる場合、例えば、アルコール溶剤とニトリル溶剤を組み合わせて用いることが好ましい。この場合アルコール溶剤とニトリル溶剤の混合比（アルコール溶剤／ニトリル溶剤）は、１／９９〜９９／１であることが好ましく、１０／９０〜９０／１０であることがより好ましく、３０／７０〜７０／３０であることが更に好ましい。 When two or more solvents are used in combination in the contacting step, for example, it is preferable to use a combination of an alcohol solvent and a nitrile solvent. In this case, the mixing ratio of the alcohol solvent and the nitrile solvent (alcohol solvent / nitrile solvent) is preferably 1/99 to 99/1, more preferably 10/90 to 90/10, and 30/70 to More preferably, it is 70/30.
接触工程に溶媒を用いる場合、溶媒の使用量は例えば、アリルエーテル誘導体に含まれるアリル基１モルに対して、１モル〜１００モル用いることが好ましく、１モル〜５０モル用いることがより好ましく、４モル〜１５モル用いることが更に好ましい。 When using a solvent for a contact process, it is preferable to use 1 mol-100 mol, and it is more preferable to use 1 mol-50 mol with respect to 1 mol of allyl groups contained in an allyl ether derivative, More preferably, 4 mol to 15 mol is used.
接触工程には、塩基を用いてもよい。塩基としては、炭酸ナトリウム、炭酸カリウム、水酸化ナトリウム、水酸化カリウム等の無機塩基を挙げることができる。これらの塩基は１種単独でも２種以上を組み合わせて用いてもよい。
接触工程に塩基を用いる場合、塩基の使用量は例えば、アリルエーテル誘導体に含まれるアリル基１モルに対して、０．０１モル〜１０モル用いることが好ましく、０．０５モル〜５モル用いることがより好ましく、０．１モル〜１モル用いることが更に好ましい。
A base may be used in the contacting step. Examples of the base include inorganic bases such as sodium carbonate, potassium carbonate, sodium hydroxide, and potassium hydroxide. These bases may be used alone or in combination of two or more.
When a base is used in the contacting step, the amount of base used is preferably 0.01 mol to 10 mol, preferably 0.05 mol to 5 mol, per 1 mol of allyl group contained in the allyl ether derivative. Is more preferable, and 0.1 mol to 1 mol is more preferable.
過酸化物の製造方法は、接触工程に加えて、必要に応じてその他の工程を含んでいてもよい。その他の工程としては、精製工程、溶媒留去工程等を挙げることができる。過酸化物の製造方法は、接触工程と、接触工程後に行われる精製工程とを含むことが好ましい。 In addition to the contact step, the method for producing a peroxide may include other steps as necessary. Examples of other steps include a purification step and a solvent distillation step. It is preferable that the manufacturing method of a peroxide includes a contact process and the refinement | purification process performed after a contact process.
精製工程は、接触工程で得られる反応混合物から、第一の過酸化物以外の化合物の少なくとも一部を除去する工程であれば、特に制限されない。精製工程は、接触工程で得られる反応混合物から、第二の過酸化物の少なくとも一部を除去する工程であることが好ましく、水を用いて反応混合物から第二の過酸化物の少なくとも一部を除去する水洗工程であることがより好ましい。 A refinement | purification process will not be restrict | limited especially if it is a process of removing at least one part of compounds other than a 1st peroxide from the reaction mixture obtained at a contact process. The purification step is preferably a step of removing at least a part of the second peroxide from the reaction mixture obtained in the contacting step, and at least a part of the second peroxide from the reaction mixture using water. It is more preferable that it is a water washing process which removes.
また、過酸化物の製造方法は、接触工程後に、クエンチ剤との接触工程を含まないことが好ましい。クエンチ剤は、過酸化物を分解可能な化合物であれば特に制限されない。例えば、亜硫酸ナトリウム等の亜硫酸塩、チオ硫酸ナトリウム等のチオ硫酸塩などを挙げることができる。 Moreover, it is preferable that the manufacturing method of a peroxide does not include the contact process with a quenching agent after a contact process. The quenching agent is not particularly limited as long as it is a compound capable of decomposing peroxide. For example, sulfites such as sodium sulfite and thiosulfates such as sodium thiosulfate can be used.
一般式（Ｉ）で表される過酸化物は、特徴的な構造を有することから、例えば、熱ラジカル重合開始剤として好適に用いることができる。 Since the peroxide represented by the general formula (I) has a characteristic structure, it can be suitably used as, for example, a thermal radical polymerization initiator.
一般式（Ｉ）で表される過酸化物を、熱ラジカル重合開始剤として用いる場合、その使用温度は４５℃以上であることが好ましく、６０℃以上であることがより好ましく、８０℃〜２００℃であることが更に好ましい。 When the peroxide represented by the general formula (I) is used as a thermal radical polymerization initiator, the use temperature is preferably 45 ° C or higher, more preferably 60 ° C or higher, and 80 ° C to 200 ° C. It is still more preferable that it is ° C.
［熱硬化性樹脂組成物］
本発明の熱硬化性樹脂組成物は、一般式（Ｉ）で表される過酸化物と、重合性化合物とを含み、必要に応じてその他の成分を含んでいてもよい。一般式（Ｉ）で表される過酸化物を含むことで優れた熱硬化性を達成することができる。
[Thermosetting resin composition]
The thermosetting resin composition of the present invention contains a peroxide represented by the general formula (I) and a polymerizable compound, and may contain other components as necessary. By including the peroxide represented by the general formula (I), excellent thermosetting can be achieved.
（過酸化物）
熱硬化性樹脂組成物は、一般式（Ｉ）で表される過酸化物の少なくとも１種を含む。一般式（Ｉ）で表される過酸化物の詳細は既述の通りである。熱硬化性樹脂組成物は、一般式（Ｉ）で表される過酸化物を１種単独でも２種以上を組み合わせて含んでいてもよい。
(Peroxide)
The thermosetting resin composition contains at least one peroxide represented by the general formula (I). The details of the peroxide represented by the general formula (I) are as described above. The thermosetting resin composition may contain one or a combination of two or more peroxides represented by the general formula (I).
熱硬化性樹脂組成物における一般式（Ｉ）で表される過酸化物の含有量は特に制限されず、熱硬化性樹脂組成物の目的、構成等に応じて適宜選択することができる。例えば、過酸化物の含有量は、熱硬化性の観点から、重合性化合物（好ましくは、ラジカル重合性化合物）の総量１００質量部に対して、０．０１〜１００質量部であることが好ましく、０．０１〜５０質量部であることがより好ましく、０．０１〜３０質量部であることが更に好ましい。 The content of the peroxide represented by the general formula (I) in the thermosetting resin composition is not particularly limited, and can be appropriately selected according to the purpose, configuration, and the like of the thermosetting resin composition. For example, the content of the peroxide is preferably 0.01 to 100 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable compound (preferably radically polymerizable compound) from the viewpoint of thermosetting. It is more preferable that it is 0.01-50 mass parts, and it is still more preferable that it is 0.01-30 mass parts.
（重合性化合物）
熱硬化性樹脂組成物は、少なくとも１種の重合性化合物を含む。重合性化合物は、公知の材料が使用できる。重合性化合物は、ラジカル重合性化合物であることが好ましく、液晶への溶解による汚染性の観点から、（メタ）アクリル酸エステルモノマー及び／又はこれらのオリゴマー並びにビスフェノールＡ型エポキシ樹脂と（メタ）アクリル酸とを反応させて得られる部分（メタ）アクリル化エポキシ樹脂からなる群より選択される少なくとも１種であることがより好ましく、ビスフェノールＡ型エポキシ樹脂と（メタ）アクリル酸とを反応させて得られる部分（メタ）アクリル化エポキシ樹脂から選択される少なくとも１種が更に好ましい。
重合性化合物は１種単独でも２種以上を組み合わせて用いてもよい。
(Polymerizable compound)
The thermosetting resin composition contains at least one polymerizable compound. As the polymerizable compound, known materials can be used. The polymerizable compound is preferably a radical polymerizable compound, and from the viewpoint of contamination due to dissolution in liquid crystal, (meth) acrylic acid ester monomers and / or oligomers thereof, bisphenol A type epoxy resin and (meth) acrylic. More preferably, it is at least one selected from the group consisting of partially (meth) acrylated epoxy resins obtained by reacting with acids, and obtained by reacting bisphenol A type epoxy resins with (meth) acrylic acid. More preferred is at least one selected from partially (meth) acrylated epoxy resins.
A polymeric compound may be used individually by 1 type or in combination of 2 or more types.
（メタ）アクリル酸エステルモノマー及び／又はこれらのオリゴマーとしては、好ましくは、２−ヒドロキシエチル（メタ）アクリレート、ジ、トリ及びテトラエチレングリコールジ（メタ）アクリレート、エポキシ変性ジ（メタ）アクリレート並びにウレタン変性ジ（メタ）アクリレートからなる群より選択される少なくとも１種であり、より好ましくは、エポキシ変性ジ（メタ）アクリレート及びウレタン変性ジ（メタ）アクリレートからなる群より選択される少なくとも１種であり、更に好ましくは、エポキシ変性ジ（メタ）アクリレートである。 (Meth) acrylic acid ester monomers and / or oligomers thereof are preferably 2-hydroxyethyl (meth) acrylate, di, tri and tetraethylene glycol di (meth) acrylate, epoxy-modified di (meth) acrylate and urethane. It is at least one selected from the group consisting of modified di (meth) acrylate, more preferably at least one selected from the group consisting of epoxy-modified di (meth) acrylate and urethane-modified di (meth) acrylate More preferably, it is epoxy-modified di (meth) acrylate.
ビスフェノールＡ型エポキシ樹脂と（メタ）アクリル酸とを反応して得られる部分（メタ）アクリル化エポキシ樹脂は次のようにして得られる。まずビスフェノールＡ型エポキシ樹脂と（メタ）アクリル酸とを塩基性触媒、好ましくは３価の有機リン化合物及び／又はアミン化合物の存在下で、エポキシ基１当量に対して（メタ）アクリル酸を１０〜９０当量％を反応させる。次いで、この反応生成物を濾過、遠心分離及び／又は水洗等の処理により塩基性触媒を除去して精製する。塩基性触媒としては、エポキシ樹脂と（メタ）アクリル酸との反応に用いられる公知の塩基性触媒を使用することができる。また塩基性触媒をポリスチレン等のポリマーに担持させた、ポリマー担持塩基性触媒を使用することもできる。ここで、３価の有機リン化合物及びアミン化合物としては、例えば、国際公開第２０１２／０７７７２０号の段落番号００３１〜００３２の記載を参照することができる。 A partial (meth) acrylated epoxy resin obtained by reacting a bisphenol A type epoxy resin with (meth) acrylic acid is obtained as follows. First, bisphenol A type epoxy resin and (meth) acrylic acid are added in the presence of a basic catalyst, preferably a trivalent organic phosphorus compound and / or an amine compound. ˜90 equivalent% is reacted. Next, the reaction product is purified by removing the basic catalyst by filtration, centrifugation, and / or washing with water. As a basic catalyst, the well-known basic catalyst used for reaction of an epoxy resin and (meth) acrylic acid can be used. Further, a polymer-supported basic catalyst in which a basic catalyst is supported on a polymer such as polystyrene can also be used. Here, as a trivalent organic phosphorus compound and an amine compound, the description of the paragraph numbers 0031-0032 of international publication 2012/0777720 can be referred, for example.
熱重合性樹脂組成物における重合性化合物の含有量は特に制限されない。熱重合性樹脂組成物の取扱い性、すなわち、脱泡性、塗布性、印刷性等の観点から、熱重合性樹脂組成物中における重合性化合物の含有量は、１〜９９質量％であることが好ましく、１０〜９０質量％であることがより好ましく、５０〜９０質量％であることが更に好ましい。 The content of the polymerizable compound in the thermopolymerizable resin composition is not particularly limited. From the viewpoint of handleability of the thermopolymerizable resin composition, that is, defoaming property, coating property, printability, etc., the content of the polymerizable compound in the thermopolymerizable resin composition is 1 to 99% by mass. Is preferable, it is more preferable that it is 10-90 mass%, and it is still more preferable that it is 50-90 mass%.
熱重合性樹脂組成物は、一般式（Ｉ）で表される過酸化物の調製時に生成することがある、一般式（Ｉｄ）で表される化合物の少なくとも１種を更に含んでいてもよい。なお、一般式（Ｉｄ）で表される化合物におけるＲ１の好ましい態様は、一般式（Ｉ）におけるＲ１と同様である。
熱重合性樹脂組成物が、一般式（Ｉｄ）で表される化合物を含む場合、熱重合性樹脂組成物中の一般式（Ｉｄ）で表される化合物の含有量は、一般式（Ｉ）で表される過酸化物に対して１〜１００００質量％であることが好ましく、１０〜５０００質量％であることがより好ましく、１００〜３０００質量％であることが更に好ましい。また、熱重合性樹脂組成物は、一般式（Ｉｄ）で表される化合物を１種単独でも２種以上を組み合わせて含むことができる。
The thermopolymerizable resin composition may further contain at least one compound represented by the general formula (Id), which may be generated during the preparation of the peroxide represented by the general formula (I). . A preferable embodiment of R 1 in the compound represented by formula (Id) are the same as R 1 in the general formula (I).
When the thermopolymerizable resin composition contains the compound represented by the general formula (Id), the content of the compound represented by the general formula (Id) in the thermopolymerizable resin composition is the general formula (I). It is preferable that it is 1-10000 mass% with respect to the peroxide represented by this, It is more preferable that it is 10-5000 mass%, It is still more preferable that it is 100-3000 mass%. Moreover, a thermopolymerizable resin composition can contain the compound represented by general formula (Id) individually by 1 type or in combination of 2 or more types.
熱重合性樹脂組成物は、必要に応じて光重合開始剤の少なくとも１種を含んでいてもよい。熱重合性化合物が光重合開始剤を含むことで、光熱重合硬化性樹脂組成物を構成することができ、例えば、液晶シール剤として好適に用いることができる。
光重合開始剤は、特に限定されず、通常用いられる光重合開始剤から適宜選択して用いることができる。光重合開始剤の具体例としては、４−フェノキシジクロロアセトフェノン、４−ｔ−ブチル−ジクロロアセトフェノン、４−ｔ−ブチル−トリクロロアセトフェノン、ジエトキシアセトフェノン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、１−（４−イソプロピルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン、１−（４−ドデシルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン、４−（２−ヒドロキシエトキシフェニル）−２−ヒドロキシ−２−プロピルケトン、１−ヒドロキシシクロヘキシルフェニルケトン、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノプロパン−１−オン等のアセトフェノン系化合物；ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、ベンジルジメチルケタール等のベンゾイン系化合物；ベンゾフェノン、ベンゾイル安息香酸、ベンゾイル安息香酸メチル、４−フェニルベンゾフェノン、ヒドロキシベンゾフェノン、アクリル化ベンゾフェノン、４−ベンゾイル−４’−メチルジフェニルサルファイド、３，３’−ジメチル−４−メトキシベンゾフェノン等のベンゾフェノン系化合物；チオキサントン、２−クロルチオキサントン、２−メチルチオキサントン、２，４−ジメチルチオキサントン、イソプロピルチオキサントン、２，４−ジクロロチオキサントン、２，４−ジエチルチオキサントン、２，４−ジイソプロピルチオキサントン等のチオキサントン系化合物；１−フェニル−１，２−プロパンジオン−２（Ｏ−エトキシカルボニル）オキシム、２，４，６−トリメチルベンゾイルジフェニルホスフィンオキサイド、メチルフェニルグリオキシレート、９，１０−フェナントレンキノン、カンファーキノン、ジベンゾスベロン、２−エチルアントラキノン、４’，４”−ジエチルイソフタロフェノン、３，３’，４，４’−テトラ（ｔ−ブチルパーオキシカルボニル）ベンゾフェノン、１−［４−（３−メルカプトプロピルチオ）フェニル］−２−メチル−２−モルホリン−４−イル−プロパン−１−オン、１−［４−（１０−メルカプトデカニルチオ）フェニル］−２−メチル−２−モルホリン−４−イル−プロパン−１−オン、１−（４−｛２−［２−（２−メルカプトエトキシ）エトキシ］エチルチオ｝フェニル）−２−メチル−２−モルホリン−４−イル−プロパン−１−オン、１−［３−（メルカプトプロピルチオ）フェニル］−２−ジメチルアミノ−２−ベンジル−プロパン−１−オン、１−［４−（３−メルカプトプロピルアミノ）フェニル］−２−ジメチルアミノ−２−ベンジル−プロパン−１−オン、１−［４−（３−メルカプト−プロポキシ）フェニル］−２−メチル−２−モルホリン−４−イル−プロパン−１−オン、ビス（η５−２，４−シクロペンタジエン−１−イル）ビス［２，６−ジフルオロ−３−（１Ｈ−ピロール−１−イル）フェニル］チタニウム、α−アリルベンゾイン、α−アリルベンゾインアリールエーテル、１−［４−（フェニルチオ）フェニル］オクタン−１，２−ジオン２−（Ｏ−ベンゾイルオキシム）、１‐［６‐（２‐メチルベンゾイル）‐９‐エチル‐９Ｈ‐カルバゾール‐３‐イル］エタノンＯ‐アセチルオキシム、ビス（２，４，６−トリメチルベンゾイル）−フェニルホスフィンオキサイド、１，３−ビス（ｐ−ジメチルアミノベンジリデン）アセトンなどを例示することができる。光重合開始剤は１種単独でも２種以上を組み合わせて用いることができる。
The thermopolymerizable resin composition may contain at least one photopolymerization initiator as required. When the thermopolymerizable compound contains a photopolymerization initiator, a photothermal polymerization curable resin composition can be formed, and for example, it can be suitably used as a liquid crystal sealant.
The photopolymerization initiator is not particularly limited, and can be appropriately selected from commonly used photopolymerization initiators. Specific examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane -1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4 -(2-hydroxyethoxyphenyl) -2-hydroxy-2-propyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, etc. Acetophenone compounds; benzoin, benzoin methyl ether, benzoy Benzoin compounds such as ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'- Benzophenone compounds such as methyldiphenyl sulfide and 3,3′-dimethyl-4-methoxybenzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, Thioxanthone compounds such as 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone; 1-phenyl-1, 2-propanedione-2 (O-ethoxycarbonyl) oxime, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, 9,10-phenanthrenequinone, camphorquinone, dibenzosuberone, 2-ethylanthraquinone 4 ', 4 "-diethylisophthalophenone, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 1- [4- (3-mercaptopropylthio) phenyl] -2- Methyl-2-morpholin-4-yl-propan-1-one, 1- [4- (10-mercaptodecanylthio) phenyl] -2-methyl-2-morpholin-4-yl-propan-1-one, 1- (4- {2- [2- (2-mercaptoethoxy) ethoxy] ethylthio} phenyl) -2 Methyl-2-morpholin-4-yl-propan-1-one, 1- [3- (mercaptopropylthio) phenyl] -2-dimethylamino-2-benzyl-propan-1-one, 1- [4- ( 3-mercaptopropylamino) phenyl] -2-dimethylamino-2-benzyl-propan-1-one, 1- [4- (3-mercapto-propoxy) phenyl] -2-methyl-2-morpholin-4-yl -Propan-1-one, bis (η 5 -2,4-cyclopentadien-1-yl) bis [2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl] titanium, α-allylbenzoin , Α-allylbenzoin aryl ether, 1- [4- (phenylthio) phenyl] octane-1,2-dione 2- (O-benzoyloxime), 1- [6- (2-Methylbenzoyl) -9-ethyl-9H-carbazol-3-yl] ethanone O-acetyloxime, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 1,3-bis (p-dimethyl) Aminobenzylidene) acetone and the like can be exemplified. A photoinitiator can be used individually by 1 type or in combination of 2 or more types.
熱重合性化合物が光重合開始剤を含む場合、光重合開始剤の含有量は、重合性化合物の総量を１００質量部とした場合に、０．０１〜１０質量部であることが好ましく、０．０１〜５質量部であることがより好ましい。 When the thermally polymerizable compound contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.01 to 10 parts by mass when the total amount of the polymerizable compound is 100 parts by mass. More preferably, the content is 0.01 to 5 parts by mass.
熱硬化性樹脂組成物は、必要に応じて熱硬化剤の少なくとも１種を含んでいてもよい。熱重合性化合物が熱硬化剤を含むことで、例えば、液晶シール剤としてより好適に用いることができる。
熱硬化剤としては特に限定されず、通常用いられる熱硬化剤から適宜選択して用いることができる。熱硬化剤の具体例としては、ヒドラジド化合物、アミンアダクト化合物、イミダゾール化合物等が挙げられる。これらの化合物は、例えば、１種のヒドラジド化合物、１種のヒドラジド化合物と１種のイミダゾール化合物との組合せ、１種のヒドラジド化合物と２種以上のアミンアダクト化合物との組合せ、１種のヒドラジド化合物と２種以上のアミンアダクト化合物と２種以上のイミダゾール化合物との組合せ、及び２種以上のヒドラジド化合物と２種以上のアミンアダクト化合物との組合せのように、それぞれを単独で使用しても、複数の化合物を組み合わせて使用してもよい。熱硬化剤は、市販されている製品を用いることができる。
The thermosetting resin composition may include at least one thermosetting agent as necessary. When a thermopolymerizable compound contains a thermosetting agent, it can be used more suitably as a liquid crystal sealing agent, for example.
It does not specifically limit as a thermosetting agent, It can select from the thermosetting agent used normally, and can use it suitably. Specific examples of the thermosetting agent include hydrazide compounds, amine adduct compounds, and imidazole compounds. These compounds include, for example, one hydrazide compound, a combination of one hydrazide compound and one imidazole compound, a combination of one hydrazide compound and two or more amine adduct compounds, and one hydrazide compound. Or a combination of two or more amine adduct compounds and two or more imidazole compounds, and a combination of two or more hydrazide compounds and two or more amine adduct compounds, A plurality of compounds may be used in combination. As the thermosetting agent, a commercially available product can be used.
ヒドラジド化合物としては、アジピン酸ジヒドラジド、１，３−ビス（ヒドラジノカルボノエチル）−５−イソプロピルヒダントイン、７，１１−オクタデカジエン−１，１８−ジカルボヒドラジド、１，３−ビス［ヒドラジノカルボノエチル−５−イソプロピルヒダントイン］等が挙げられる。 Examples of the hydrazide compound include adipic acid dihydrazide, 1,3-bis (hydrazinocarbonoethyl) -5-isopropylhydantoin, 7,11-octadecadien-1,18-dicarbohydrazide, 1,3-bis [hydra And dinocarbonoethyl-5-isopropylhydantoin].
アミンアダクト化合物としては、市販品として、味の素ファインテクノ社製、アミキュアＰＮ−２３、アミキュアＰＮ−３０、アミキュアＭＹ−２４、アミキュアＭＹ−Ｈ等が挙げられる。 As an amine adduct compound, Ajinomoto Fine Techno Co., Amicure PN-23, Amicure PN-30, Amicure MY-24, Amicure MY-H, etc. are mentioned as a commercial item.
イミダゾール化合物としては、２−メチルイミダゾール、２−フェニルイミダゾール、２−ウンデシルイミダゾール、２−ヘプタデシルイミダゾール、２−フェニル−４−メチルイミダゾール、１−ベンジル−２−フェニルイミダゾール、１−ベンジル−２−メチルイミダゾール、１−シアノエチル−２−メチルイミダゾール、１−シアノエチル−２−フェニルイミダゾール等が挙げられる。 Examples of imidazole compounds include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2. -Methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole and the like.
熱硬化性樹脂組成物が熱硬化剤を含む場合、熱硬化剤の含有量は、十分な熱反応性を有し、且つ、保存安定性を維持する観点から、重合性化合物１００質量部に対して、５〜５０質量部であることが好ましく、５〜３０質量部であることがより好ましい。 When the thermosetting resin composition contains a thermosetting agent, the content of the thermosetting agent has sufficient thermal reactivity and maintains the storage stability with respect to 100 parts by mass of the polymerizable compound. It is preferably 5 to 50 parts by mass, and more preferably 5 to 30 parts by mass.
熱硬化性樹脂組成物は、フィラー粒子の少なくとも１種を含むことができる。フィラー粒子を含むことで、熱硬化性樹脂組成物の粘度制御、熱硬化性樹脂組成物を硬化させた硬化物の強度向上、または線膨張性が抑制されることによる熱硬化性樹脂組成物の接着信頼性の向上等の効果が得られる。フィラー粒子としては、無機粒子および／又は有機樹脂粒子が好ましく使用できる。線膨張係数が小さく、接着強度の発現のため硬化収縮率を低減させる観点から、無機粒子が好ましい。
フィラー粒子は１種単独でも２種以上を組み合わせて用いてもよい。
The thermosetting resin composition can contain at least one filler particle. By including filler particles, the viscosity of the thermosetting resin composition, the strength improvement of the cured product obtained by curing the thermosetting resin composition, or the thermosetting resin composition by suppressing the linear expansion property Effects such as improved adhesion reliability can be obtained. As the filler particles, inorganic particles and / or organic resin particles can be preferably used. Inorganic particles are preferred from the viewpoint of a low linear expansion coefficient and a reduction in curing shrinkage due to the development of adhesive strength.
The filler particles may be used alone or in combination of two or more.
無機粒子としては、シール剤に好適に用いられる粒子径が得られやすい観点から炭酸カルシウム、炭酸マグネシウム、硫酸バリウム、硫酸マグネシウム、珪酸アルミニウム、酸化チタン、アルミナ、酸化亜鉛、二酸化ケイ素、カオリン、タルク、ガラスビーズ、セリサイト、活性白土、ベントナイト、窒化アルミニウム及び窒化ケイ素からなる群から選ばれる少なくとも１種以上の無機粒子が好ましく、二酸化ケイ素、タルク、アルミナ及びベントナイトからなる群から選ばれる少なくとも１種以上の無機粒子がより好ましく、二酸化ケイ素及び／又はタルクが更に好ましく、二酸化ケイ素が更に好ましい。 As the inorganic particles, calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, titanium oxide, alumina, zinc oxide, silicon dioxide, kaolin, talc, from the viewpoint of easily obtaining a particle size suitably used for a sealant, At least one or more inorganic particles selected from the group consisting of glass beads, sericite, activated clay, bentonite, aluminum nitride and silicon nitride are preferable, and at least one or more selected from the group consisting of silicon dioxide, talc, alumina and bentonite. Inorganic particles are more preferable, silicon dioxide and / or talc are more preferable, and silicon dioxide is still more preferable.
有機樹脂粒子としては、硬化時の応力緩和による接着強度としての添加効果を発現させる観点から、ポリメタクリル酸メチル粒子、ポリスチレン粒子、これらを構成するモノマーと他のモノマーとを共重合させて得られる共重合体粒子、ポリエステル粒子、ポリウレタン粒子、ゴム粒子、及び高いガラス転移温度を有する共重合体を含むシェルと低いガラス転移温度を有する共重合体のコアとから構成されるコアシェルタイプ粒子からなる群から選ばれる少なくとも１種の有機樹脂粒子が好ましく、ポリエステル粒子、ポリウレタン粒子、ゴム粒子、及び高いガラス転移温度を有する共重合体を含むシェルと低いガラス転移温度を有する共重合体のコアとから構成されるコアシェルタイプ粒子からなる群から選ばれる少なくとも１種の有機樹脂粒子がより好ましく、高いガラス転移温度を有する共重合体を含むシェルと低いガラス転移温度を有する共重合体のコアとから構成されるコアシェルタイプ粒子が更に好ましい。また、コアシェルタイプ粒子では、高いガラス転移温度を有する共重合体がポリメタクリル酸で、低いガラス転移温度を有する共重合体がブチルアクリレートであることが好ましい。 The organic resin particles are obtained by copolymerizing polymethyl methacrylate particles, polystyrene particles, and monomers constituting them with other monomers from the viewpoint of developing an effect of addition as adhesive strength by stress relaxation during curing. Group consisting of core-shell type particles composed of copolymer particles, polyester particles, polyurethane particles, rubber particles, and a shell containing a copolymer having a high glass transition temperature and a core of the copolymer having a low glass transition temperature At least one organic resin particle selected from the group consisting of polyester particles, polyurethane particles, rubber particles, and a shell containing a copolymer having a high glass transition temperature and a core of the copolymer having a low glass transition temperature. At least one organic tree selected from the group consisting of core-shell type particles More preferably the particles, core-shell type particles composed of a core of a copolymer having a shell and a low glass transition temperature comprising a copolymer having a high glass transition temperature is more preferable. In the core-shell type particles, it is preferable that the copolymer having a high glass transition temperature is polymethacrylic acid and the copolymer having a low glass transition temperature is butyl acrylate.
フィラー粒子の粒子径は特に限定されず、目的等に応じて適宜選択することができる。例えば、体積平均粒子径として、０．１μｍ〜１．５μｍであることが好ましく、０．５μｍ〜１．５μｍであることがより好ましい。フィラー粒子の体積平均粒子径は、レーザー回折散乱法で測定することができる。 The particle diameter of the filler particles is not particularly limited and can be appropriately selected according to the purpose and the like. For example, the volume average particle diameter is preferably 0.1 μm to 1.5 μm, and more preferably 0.5 μm to 1.5 μm. The volume average particle diameter of the filler particles can be measured by a laser diffraction scattering method.
熱硬化性樹脂組成物がフィラー粒子として無機粒子又は有機樹脂粒子を含む場合、無機粒子の含有量は、応力分散効果による接着性の改善、線膨張率の改善の観点から、重合性化合物１００質量部に対して、２〜４０質量部であることが好ましく、５〜３０質量部であることが更に好ましい。また、有機樹脂粒子の含有量は、硬化時の応力緩和による接着強度としての添加効果を発現させる観点から、重合性化合物１００質量部に対して、２〜４０質量部であることが好ましく、５〜３０質量部であることが更に好ましい。 When the thermosetting resin composition contains inorganic particles or organic resin particles as filler particles, the content of the inorganic particles is 100 masses of the polymerizable compound from the viewpoint of improvement of adhesiveness due to stress dispersion effect and improvement of linear expansion coefficient. The amount is preferably 2 to 40 parts by mass, more preferably 5 to 30 parts by mass with respect to parts. In addition, the content of the organic resin particles is preferably 2 to 40 parts by mass with respect to 100 parts by mass of the polymerizable compound, from the viewpoint of developing an addition effect as an adhesive strength by stress relaxation during curing. More preferably, it is -30 mass parts.
熱硬化性樹脂組成物は、カップリング剤の少なくとも１種を含むことができる。カップリング剤としてはシランカップリング剤等を挙げることができる。
シランカップリング剤として具体的には、γ−アミノプロピルトリメトキシシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、及びγ−イソシアネートプロピルトリメトキシシランからなる群から選ばれる１種以上の化合物が好ましく、γ−グリシドキシプロピルトリメトキシシランがより好ましい。
The thermosetting resin composition can contain at least one coupling agent. Examples of coupling agents include silane coupling agents.
Specifically, the silane coupling agent is selected from the group consisting of γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-isocyanatopropyltrimethoxysilane. One or more compounds are preferable, and γ-glycidoxypropyltrimethoxysilane is more preferable.
熱硬化性樹脂組成物がカップリング剤を含む場合、カップリング剤の含有量は、接着強度、特に耐湿強度の保持の観点から、重合性化合物１００質量部に対して、０．１〜１０質量部であることが好ましく、０．５〜２質量部であることがより好ましい。 When the thermosetting resin composition contains a coupling agent, the content of the coupling agent is 0.1 to 10 masses with respect to 100 parts by mass of the polymerizable compound from the viewpoint of maintaining adhesive strength, particularly moisture resistance strength. Part is preferable, and 0.5 to 2 parts by mass is more preferable.
熱硬化性樹脂組成物は、必要に応じてエラストマー、連鎖移動剤、イオントラップ剤、イオン交換剤、レベリング剤、顔料、染料、可塑剤、消泡剤等の添加剤を更に含むことができる。 The thermosetting resin composition may further contain additives such as an elastomer, a chain transfer agent, an ion trapping agent, an ion exchange agent, a leveling agent, a pigment, a dye, a plasticizer, and an antifoaming agent as necessary.
本発明の熱硬化性樹脂組成物は、未硬化状態における成分の溶出が抑制される。したがって、熱硬化性樹脂組成物を液晶シール剤に適用した場合には、液晶の汚染を低減することができる。また電子部品の気密シール剤等の封止剤に適用した場合には、硬化の工程中における封止剤由来の電子部品の汚染を低減することができる。 In the thermosetting resin composition of the present invention, elution of components in an uncured state is suppressed. Therefore, when the thermosetting resin composition is applied to the liquid crystal sealant, the contamination of the liquid crystal can be reduced. In addition, when applied to a sealing agent such as an airtight sealant for electronic components, contamination of the electronic component derived from the sealing agent during the curing process can be reduced.
以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
［製造例１］
（ＢｉｓＡ−ジグリシジルエーテルのエチレングリコールモノアリルエーテル開環体の製造）
攪拌機、温度計、還流冷却管を備えた２０００ｍＬガラス製三ツ口フラスコに、ビスフェノールＡ型エポキシ樹脂；エピクロンＥＸＡ８５０ＣＲＰ〔ＤＩＣ社製〕２８０ｇ、エチレングリコールモノアリルエーテル〔ＴＣＩ社製〕８００ｇ（４．７５当量／エポキシ基）、クロロホルム〔関東化学社製〕５６０ｇ、ホウフッ化錫水溶液〔森田化学社製〕１．６ｇ（１．５ミリ当量／エポキシ基）を入れ、攪拌しながら６０℃に昇温した。反応開始後、４時間攪拌を継続し、高速液体クロマトグラフィーによる確認により、反応がほぼ進行しなくなった時点で反応終了とした。上記反応液を３０００ｍＬガラス製ビーカーに移し、クロロホルム〔関東化学社製〕５００ｇ、水５００ｇを入れ、しばらく攪拌後、静置させた。水層を分離、除去した後、同様の操作を繰り返した。水層のｐＨが７．０以上であることを確認し、有機層を減圧条件下（６０ｍｍＨｇ以下、６０℃）濃縮した。無色透明粘稠液体を３６５ｇ得た。
[Production Example 1]
(Production of ethylene glycol monoallyl ether ring-opened product of BisA-diglycidyl ether)
In a 2000 mL glass three-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, 280 g of bisphenol A type epoxy resin; Epicron EXA850CRP (manufactured by DIC), 800 g of ethylene glycol monoallyl ether (manufactured by TCI) (4.75 equivalent / Epoxy group), chloroform [manufactured by Kanto Chemical Co., Ltd.] 560 g, tin borofluoride aqueous solution [manufactured by Morita Chemical Co., Ltd.] 1.6 g (1.5 meq / epoxy group) were added, and the temperature was raised to 60 ° C. with stirring. Stirring was continued for 4 hours after the start of the reaction, and the reaction was terminated when the reaction almost did not proceed as confirmed by high performance liquid chromatography. The reaction solution was transferred to a 3000 mL glass beaker, 500 g of chloroform (manufactured by Kanto Chemical Co., Inc.) and 500 g of water were added, and the mixture was stirred for a while and allowed to stand. After separating and removing the aqueous layer, the same operation was repeated. After confirming that the pH of the aqueous layer was 7.0 or higher, the organic layer was concentrated under reduced pressure (60 mmHg or lower, 60 ° C.). 365 g of a colorless transparent viscous liquid was obtained.
［製造例２］
（テトラアリルエーテル化合物の製造）
攪拌機、温度計、還流冷却管を備えた１０００ｍＬガラス製三ツ口フラスコに、製造例１で得られた化合物２００ｇ、塩化アリル〔ＴＣＩ社製〕１１２ｇ（２．０当量／水酸基）、塩化テトラブチルアンモニウム〔ＴＣＩ社製〕２．３６ｇ（０．０１当量／水酸基）、ジメチルスルホキシド〔関東化学社製〕１００ｇを混合させた。室温条件下、４８％水酸化ナトリウム水溶液〔関東化学社製〕１２２ｇ（２．０当量／水酸基）を２時間かけて滴下した。滴下終了後、室温で１２時間攪拌を継続し、高速液体クロマトグラフィーによる確認により、反応がほぼ進行しなくなった時点で反応終了とした。上記反応液を３０００ｍＬガラス製ビーカーに移し、クロロホルム〔関東化学社製〕５００ｇ、水５００ｇを入れ、しばらく攪拌後、静置させた。水層を分離、除去した後、同様の操作を繰り返した。水層のｐＨが７．０以下であることを確認し、有機層を減圧条件下（６０ｍｍＨｇ以下、６０℃）濃縮した。無色透明液体として下記化学式で表わされるテトラアリルエーテル化合物を２１０ｇ得た。
[Production Example 2]
(Production of tetraallyl ether compound)
In a 1000 mL glass three-necked flask equipped with a stirrer, thermometer and reflux condenser, 200 g of the compound obtained in Production Example 1, 112 g of allyl chloride [manufactured by TCI] (2.0 equivalents / hydroxyl group), tetrabutylammonium chloride [ 2.36 g (0.01 equivalent / hydroxyl group) of TCI] and 100 g of dimethyl sulfoxide [manufactured by Kanto Chemical Co., Ltd.] were mixed. Under room temperature conditions, 122 g (2.0 equivalents / hydroxyl group) of 48% aqueous sodium hydroxide (manufactured by Kanto Chemical Co., Inc.) was added dropwise over 2 hours. After completion of the dropwise addition, stirring was continued at room temperature for 12 hours, and the reaction was terminated when the reaction almost did not proceed as confirmed by high performance liquid chromatography. The reaction solution was transferred to a 3000 mL glass beaker, 500 g of chloroform (manufactured by Kanto Chemical Co., Inc.) and 500 g of water were added, and the mixture was stirred for a while and allowed to stand. After separating and removing the aqueous layer, the same operation was repeated. After confirming that the pH of the aqueous layer was 7.0 or less, the organic layer was concentrated under reduced pressure conditions (60 mmHg or less, 60 ° C.). As a colorless transparent liquid, 210 g of a tetraallyl ether compound represented by the following chemical formula was obtained.
［製造例３］
以下のようにして、部分エステル化エポキシ樹脂（部分メタアクリル化エポキシ樹脂）を製造した。
（ビスフェノールＡ型エポキシ樹脂の部分メタクリレート化エポキシ樹脂の合成）
ビスフェノールＡ型エポキシ樹脂（ＥＸＡ８５０ＣＲＰ、ＤＩＣ株式会社製）３２０．２ｇ、メタクリル酸（東京化成社製）９０．４ｇ、ＰＳ−ＰＰｈ３（ポリスチレン（ＰＳ）にトリフェニルホスフィン（ＰＰｈ３）を担持した塩基性触媒、バイオタージ社製）１．５ｇ、及びＢＨＴ（ジブチルヒドロキシトルエン）１００ｍｇを混合し１００℃で６時間撹拌した。反応終了後、濾過により触媒を除去し部分メタクリレート化エポキシ樹脂を得た。
[Production Example 3]
A partially esterified epoxy resin (partially methacrylated epoxy resin) was produced as follows.
(Synthesis of partially methacrylated epoxy resin of bisphenol A type epoxy resin)
320.2 g of bisphenol A type epoxy resin (EXA850CRP, manufactured by DIC Corporation), 90.4 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), PS-PPh 3 (polystyrene (PS) carrying triphenylphosphine (PPh 3 ) 1.5 g of a catalytic catalyst (manufactured by Biotage) and 100 mg of BHT (dibutylhydroxytoluene) were mixed and stirred at 100 ° C. for 6 hours. After completion of the reaction, the catalyst was removed by filtration to obtain a partially methacrylated epoxy resin.
［実施例１］
（過酸化物を含有するエポキシ樹脂の製造）
攪拌機、温度計、還流冷却管を備えた１０００ｍＬガラス製三ツ口フラスコに、製造例２で得られた化合物５０ｇ、メタノール〔関東化学社製〕１２８ｇ（１２．５当量／アリル基）、アセトニトリル〔関東化学社製〕１０５ｇ（８．０当量／アリル基）、炭酸カリウム〔関東化学社製〕１７ｇ（０．４当量／アリル基）を混合させた。反応系内が２０〜４０℃の温度範囲になるように調節しながら３０〜３５％の過酸化水素水〔関東化学社製〕２１７ｇ（６．０当量／アリル基）を３時間かけて滴下した。滴下終了後、室温で３時間攪拌を継続し、高速液体クロマトグラフィーによる確認により、反応がほぼ進行しなくなった時点で反応終了とした。上記反応液を１０００ｍＬガラス製ビーカーに移し、クロロホルム〔関東化学社製〕２５０ｇ、水２５０ｇを入れ、しばらく攪拌後、静置させた。水層を分離した後、同様の操作を繰り返した。水層のｐＨが７．０以下、および過酸化水素濃度が測定限界以下であることを確認し、有機層を減圧条件下（６０ｍｍＨｇ以下、６０℃）濃縮した。無色透明粘稠液体として、下記化学式群に示すような一般式（Ｉ）で表わされる過酸化物とエポキシ樹脂の混合物を４４ｇ得た。
[Example 1]
(Manufacture of epoxy resin containing peroxide)
In a 1000 mL glass three-necked flask equipped with a stirrer, a thermometer, and a reflux condenser, 50 g of the compound obtained in Production Example 2, 128 g (12.5 equivalents / allyl group) of methanol (manufactured by Kanto Chemical Co.), acetonitrile [Kanto Chemical Co., Ltd.] 105 g (8.0 equivalent / allyl group) and 17 g (0.4 equivalent / allyl group) of potassium carbonate [manufactured by Kanto Chemical Co., Ltd.] were mixed. 217 g (6.0 equivalents / allyl group) of 30 to 35% hydrogen peroxide water (manufactured by Kanto Chemical Co., Inc.) was added dropwise over 3 hours while adjusting the temperature in the reaction system to be in the temperature range of 20 to 40 ° C. . After completion of the dropping, stirring was continued for 3 hours at room temperature, and the reaction was terminated when the reaction almost did not proceed as confirmed by high performance liquid chromatography. The reaction solution was transferred to a 1000 mL glass beaker, 250 g of chloroform (manufactured by Kanto Chemical Co., Inc.) and 250 g of water were added, and the mixture was stirred for a while and allowed to stand. After the aqueous layer was separated, the same operation was repeated. After confirming that the pH of the aqueous layer was 7.0 or less and the hydrogen peroxide concentration was below the measurement limit, the organic layer was concentrated under reduced pressure conditions (60 mmHg or less, 60 ° C.). As a colorless transparent viscous liquid, 44 g of a mixture of a peroxide represented by the general formula (I) as shown in the following chemical formula group and an epoxy resin was obtained.
得られた混合物について、エポキシ当量、粘度、塩素濃度及び過酸化物濃度を以下のようにして測定した。
エポキシ当量を、過塩素酸法で測定したところ、エポキシ当量１９６ｇ／ｅｑであった。
粘度を、ＥＨＤ型粘度計を用いて２５℃で測定したところ、粘度９．７７５Ｐａ・ｓであった。
塩素濃度を、蛍光Ｘ線法を用いて測定したところ、塩素濃度２３１ｐｐｍであった。
過酸化物濃度を、ヨウ素滴定法を用いて測定したところ、過酸化物濃度１０．５質量％であった。
About the obtained mixture, the epoxy equivalent, the viscosity, the chlorine concentration, and the peroxide concentration were measured as follows.
When the epoxy equivalent was measured by the perchloric acid method, the epoxy equivalent was 196 g / eq.
When the viscosity was measured at 25 ° C. using an EHD type viscometer, the viscosity was 9.775 Pa · s.
When the chlorine concentration was measured using a fluorescent X-ray method, the chlorine concentration was 231 ppm.
When the peroxide concentration was measured using an iodometric titration method, the peroxide concentration was 10.5% by mass.
［実施例２］
上記で得られた過酸化物を含有するエポキシ樹脂の１０質量部と、重合性化合物として上記で得られた部分メタクリル化エポキシ樹脂の１００質量部とを、スリーワンモータを用いて混合して、熱硬化性樹脂組成物を得た。なお、過酸化物を含有するエポキシ樹脂中の過酸化物濃度は１０．５質量％である。
[Example 2]
10 parts by mass of the epoxy resin containing peroxide obtained above and 100 parts by mass of the partially methacrylated epoxy resin obtained above as a polymerizable compound were mixed using a three-one motor, A curable resin composition was obtained. In addition, the peroxide density | concentration in the epoxy resin containing a peroxide is 10.5 mass%.
（評価）
得られた熱硬化性樹脂組成物の硬化性を以下のようにして評価した。
熱硬化性樹脂組成物を２５ｍｍ×２５ｍｍ厚さ０．７ｍｍのＬＣＤ用ガラスと、２５ｍｍ×２５ｍｍ厚さ０．１ｍｍのＰＥＴフィルムにより、熱硬化性樹脂組成物の厚みが０．５ｍｍになるようにはさみ、表１に示す条件で加熱処理又は紫外線照射処理して、硬化性評価用のサンプルとした。
サンプルのＩＲスペクトルをＦＴ−ＩＲ（Ｓｐｅｃｔｒｕｍ Ｏｎｅ、パーキンエルマー社製）を用いて測定し、得られたＩＲスペクトルのメタクリル基のピーク面積よりメタクリル基の反応率（転化率、メタクリル反応率）を算出した。反応率の算出はメタクリル基の吸収１６３０ｃｍ−１（又は９４５ｃｍ−１）の面積の減少をベンゼン環の二重結合の吸収１５００ｃｍ−１の面積を基準として計算した。
加熱処理は恒温層を用いて行った。また、紫外線照射処理は、紫外線照射装置（ＵＶＸ−０１２２４Ｓ１、ウシオ電機製）により、１００ｍＷ／ｃｍ２の紫外線照射照度で３０００ｍＪ／ｃｍ２の光エネルギーで照射を行った。なお、加熱処理と紫外線照射処理の両方を行った場合は、紫外線照射処理後に加熱処理を行った。
(Evaluation)
The curability of the obtained thermosetting resin composition was evaluated as follows.
The thermosetting resin composition is made of 25 mm × 25 mm 0.7 mm thick LCD glass and 25 mm × 25 mm 0.1 mm thick PET film so that the thermosetting resin composition has a thickness of 0.5 mm. Scissors were subjected to heat treatment or ultraviolet irradiation treatment under the conditions shown in Table 1 to obtain samples for evaluation of curability.
The IR spectrum of the sample was measured using FT-IR (Spectrum One, manufactured by PerkinElmer), and the reaction rate (conversion rate, methacrylic reaction rate) of the methacrylic group was calculated from the peak area of the methacrylic group of the obtained IR spectrum. did. The calculation of the reaction rate was calculated based on the decrease in the area of 1630 cm −1 (or 945 cm −1 ) absorption of the methacryl group, based on the area of 1500 cm −1 absorption of the double bond of the benzene ring.
The heat treatment was performed using a constant temperature layer. The ultraviolet irradiation treatment, an ultraviolet irradiation device (UVX-01224S1, manufactured by Ushio) by, was irradiated with light energy of 3000 mJ / cm 2 ultraviolet radiation illuminance of 100 mW / cm 2. Note that when both the heat treatment and the ultraviolet irradiation treatment were performed, the heat treatment was performed after the ultraviolet irradiation treatment.
表１から、熱処理温度が８０℃及び１００℃では、ほとんど硬化が進行しなかった。熱処理温度が１２０℃において、熱処理時間が１０分（ｍｉｎ）ではほぼ反応していないが、２０分では急激に反応が進み、３０分で硬化物が得られた（反応率は９３％）。
紫外線照射処理のみでの過酸化物の分解による樹脂組成物の硬化は確認されなかった。
紫外線照射処理後にも過酸化物は十分に残存しており、紫外線照射処理後の加熱処理で問題なく硬化物が得られた（反応率は９５％）。
From Table 1, when the heat treatment temperature was 80 ° C. and 100 ° C., the curing hardly proceeded. At a heat treatment temperature of 120 ° C., there was almost no reaction when the heat treatment time was 10 minutes (min), but the reaction proceeded rapidly in 20 minutes, and a cured product was obtained in 30 minutes (reaction rate was 93%).
Curing of the resin composition due to decomposition of the peroxide only by the ultraviolet irradiation treatment was not confirmed.
The peroxide remained sufficiently even after the ultraviolet irradiation treatment, and a cured product was obtained without any problem by the heat treatment after the ultraviolet irradiation treatment (reaction rate was 95%).
［実施例３］
実施例２において、過酸化物を含有するエポキシ樹脂の配合量（質量部）を表２に示すように変更したこと以外は、実施例２と同様にして熱硬化性樹脂組成物を調製し、同様にして硬化性（反応率％）を評価した。
[Example 3]
In Example 2, a thermosetting resin composition was prepared in the same manner as in Example 2 except that the compounding amount (parts by mass) of the epoxy resin containing peroxide was changed as shown in Table 2. Similarly, curability (reaction rate%) was evaluated.
［比較例１］
実施例３において、過酸化物を含有するエポキシ樹脂を配合しなかった場合は、いずれの加熱処理条件でも反応率は０％であった。
[Comparative Example 1]
In Example 3, when an epoxy resin containing a peroxide was not blended, the reaction rate was 0% under any heat treatment conditions.
［実施例４〜７、比較例２〜５］
部分メタクリル化エポキシ樹脂、実施例１で得られた過酸化物を含有するエポキシ樹脂、過酸化物非含有エポキシ樹脂、光重合開始剤（ＢＡＳＦ社製ＩＲＧＡＣＵＲＥ ３６９（２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタノン−１））、及び熱硬化剤（味の素ファインテクノ社製アミキュアＶＤＨ（１，３−ビス（ヒドラジノカルボノエチル）−５−イソプロピルヒダントイン））を下記表３に示す配合量（質量部）で混合して、熱硬化性樹脂組成物を調製し、実施例２と同様にして評価した。
過酸化物非含有エポキシ樹脂は、特開２０１２−０７７２０２号公報の記載に準じて調製した下記エポキシ樹脂である。
[Examples 4-7, Comparative Examples 2-5]
Partially methacrylated epoxy resin, epoxy resin containing peroxide obtained in Example 1, peroxide-free epoxy resin, photoinitiator (IRGACURE 369 (2-benzyl-2-dimethylamino-, manufactured by BASF) 1- (4-morpholinophenyl) -butanone-1)) and a thermosetting agent (Amicor VDH (1,3-bis (hydrazinocarbonoethyl) -5-isopropylhydantoin) manufactured by Ajinomoto Fine Techno Co.) A thermosetting resin composition was prepared by mixing in the blending amount (parts by mass) shown in FIG. 3, and evaluated in the same manner as in Example 2.
The peroxide-free epoxy resin is the following epoxy resin prepared according to the description of JP2012-0777202.
なお、エポキシ反応率は、ＩＲスペクトルにおけるエポキシ基の吸収９１０ｃｍ−１の面積の減少をベンゼン環の二重結合の吸収１５００ｃｍ−１の面積を基準として計算した。 Incidentally, the epoxy reaction rate was calculated to decrease the area of the absorbing 910 cm -1 for epoxy groups in the IR spectrum based on the area of absorption 1500 cm -1 of the double bonds of the benzene ring.
表３から、アリルエーテル化合物を酸化することによって得られるグリシジルエーテル化合物に含まれる過酸化物が、熱重合開始剤として良好に機能することが分かる。 From Table 3, it can be seen that the peroxide contained in the glycidyl ether compound obtained by oxidizing the allyl ether compound functions well as a thermal polymerization initiator.
［溶出性試験］
液晶への溶出性の評価は液晶の相転移温度であるＮＩ点（Nematic-Isotropic point）の変化により行った。液晶のＮＩ点は液晶の各成分の混合組成により決定され、各配合で固有の値となる。一般的に、これら液晶に何らかの不純物（他成分）が混入することによりＮＩ点は低下することが知られており、不純物混入具合をＮＩ点より評価することが出来る。
[Elution test]
The elution property to the liquid crystal was evaluated by changing the NI point (Nematic-Isotropic point) which is the phase transition temperature of the liquid crystal. The NI point of the liquid crystal is determined by the mixed composition of each component of the liquid crystal and is a unique value for each formulation. In general, it is known that the NI point is lowered by mixing some impurities (other components) into these liquid crystals, and the degree of impurity mixing can be evaluated from the NI point.
（測定用試料の作製）
アンプル瓶に、上記で得られた過酸化物を含有するエポキシ樹脂又は過酸化物非含有エポキシ樹脂を０．１ｇ入れ、それぞれに液晶（ＭＬＣ−１１９００−０８０、メルク社製）１ｇを加えた。このアンプル瓶を１２０℃オーブンに１時間投入し、その後室温で静置して室温（２５℃）に戻ってから液晶部分を取り出し０．２μｍフィルターによりろ過し、評価用の液晶サンプルとした。
(Preparation of measurement sample)
0.1g of the peroxide-containing epoxy resin or peroxide-free epoxy resin obtained above was put in an ampoule bottle, and 1g of liquid crystal (MLC-11900-080, manufactured by Merck & Co., Inc.) was added to each. This ampoule bottle was placed in a 120 ° C. oven for 1 hour, and then allowed to stand at room temperature. After returning to room temperature (25 ° C.), the liquid crystal portion was taken out and filtered through a 0.2 μm filter to obtain a liquid crystal sample for evaluation.
（ＮＩ点の測定）
ＮＩ点の測定には示差走査型熱量計（ＤＳＣ、パーキンエルマー社製、Ｐｙｒｉｓ６）を使用した。評価用の液晶サンプル１０ｍｇをアルミサンプルパンに封入し、昇温速度５℃／分の条件で測定を行った。
(NI point measurement)
A differential scanning calorimeter (DSC, manufactured by PerkinElmer, Inc., Pyris 6) was used for measurement of the NI point. A 10 mg liquid crystal sample for evaluation was sealed in an aluminum sample pan, and the measurement was performed under the condition of a temperature rising rate of 5 ° C./min.
過酸化物を含有するエポキシ樹脂から得られた評価用の液晶サンプルのＮＩ点は９１．６４℃であり、ブランクからの変化量（ΔＮＩ点）は−０．４１℃であった。一方、過酸化物非含有エポキシ樹脂から得られた評価用の液晶サンプルのＮＩ点は９１．６０℃であり、ブランクからの変化量（ΔＮＩ点）は−０．４３℃であった。
以上から、エポキシ樹脂における過酸化物構造の有無は、液晶汚染性に影響しないことが分かる。
The NI point of the liquid crystal sample for evaluation obtained from the epoxy resin containing a peroxide was 91.64 ° C., and the amount of change from the blank (ΔNI point) was −0.41 ° C. On the other hand, the NI point of the liquid crystal sample for evaluation obtained from the peroxide-free epoxy resin was 91.60 ° C., and the amount of change from the blank (ΔNI point) was −0.43 ° C.
From the above, it can be seen that the presence or absence of the peroxide structure in the epoxy resin does not affect the liquid crystal contamination.
Claims (11)
（式中、Ｒ１は、少なくとも１つのエポキシ基と、炭素数１〜６のアルキレン基、炭素数６〜１０のアリーレン基、及び酸素原子を含み、必要に応じて、炭素数１〜６のアルキル基である置換基を含んで構成され、炭素数が４０までであり、分子量が６５０までの有機基を表す。Ｒ２及びＲ３は、一方がヒドロキシ基であり他方がヒドロパーオキシ基であるか、Ｒ２とＲ３が、これらが結合する炭素原子と一緒になってパーオキシ結合を有する四員環構造を形成する。） The thermal radical polymerization initiator using the peroxide represented by the following general formula (I).
(In the formula, R 1 includes at least one epoxy group, an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 10 carbon atoms, and an oxygen atom, and optionally has 1 to 6 carbon atoms. An organic group having a substituent having an alkyl group and having a carbon number of up to 40 and a molecular weight of up to 650. One of R 2 and R 3 is a hydroxy group and the other is a hydroperoxy group. Or R 2 and R 3 together with the carbon atom to which they are attached form a four-membered ring structure having a peroxy bond.)
（式中、Ｒ１は、アリルオキシ基、炭素数１〜６のアルキレン基、炭素数６〜１０のアリーレン基、及び酸素原子を含み、必要に応じて、炭素数１〜６のアルキル基である置換基を含んで構成され、炭素数が４０までであり、分子量が６５０までの有機基を表す。） The thermal radical polymerization initiation according to claim 1, wherein the peroxide represented by the general formula (I) is a reaction product of an allyl ether derivative represented by the following general formula (II) and a peroxide. Agent.
(In the formula, R 1 includes an allyloxy group, an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 10 carbon atoms, and an oxygen atom, and if necessary, is an alkyl group having 1 to 6 carbon atoms. (It represents an organic group that includes a substituent, has up to 40 carbon atoms, and has a molecular weight of up to 650.)
前記２以上のエポキシ基を有するエポキシ樹脂は、炭素数２〜１０のアルキレングリコールジグリシジルエーテル、ポリアルキレングリコールジグリシジルエーテル、グリセリントリグリシジルエーテル、ペンタエリスリトールテトラグリシジルエーテル、ジペンタエリスリトールヘキサグリシジルエーテル、ビスフェノール型エポキシ樹脂、ビフェニルジグリシジルエーテル、ナフタレンジグリシジルエーテル、芳香族テトラグリシジルエーテル、フロログルシノールのポリグリシジルエーテル、ピロガロールのポリグリシジルエーテル、アルドースのポリグリシジルエーテル、ケトースのポリグリシジルエーテル、糖アルコールのポリグリシジルエーテル、又は、下記式：
である、過酸化物。 A peroxide obtained by substituting one epoxy group of an epoxy resin having two or more epoxy groups with a hydroperoxyhydroxyethyl group or a dioxetanyl group,
The epoxy resin having two or more epoxy groups is alkylene glycol diglycidyl ether having 2 to 10 carbon atoms, polyalkylene glycol diglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, dipentaerythritol hexaglycidyl ether, bisphenol. Type epoxy resin, biphenyl diglycidyl ether, naphthalene diglycidyl ether, aromatic tetraglycidyl ether, phloroglucinol polyglycidyl ether, pyrogallol polyglycidyl ether, aldose polyglycidyl ether, ketose polyglycidyl ether, sugar alcohol poly Glycidyl ether or the following formula:
Is a peroxide.
〔式中、Ａは下記化学式：
で示されるヒドロパーオキシヒドロキシプロピルオキシ基又は１，２−ジオキセタニルメチルオキシ基を表す。「＊」は結合位置を示す。Ｘはグリシジルオキシ基を表す。Ｙはヒドロキシ基、フェニルオキシ基又は炭素数１〜１０のアルコキシ基を表す。〕 Any one peroxide represented by the following formula.
[In the formula, A represents the following chemical formula:
Represents a hydroperoxyhydroxypropyloxy group or a 1,2-dioxetanylmethyloxy group represented by “*” Indicates a binding position. X represents a glycidyloxy group. Y represents a hydroxy group, a phenyloxy group, or an alkoxy group having 1 to 10 carbon atoms. ]
〔式中、Ａは下記化学式：
で示されるヒドロパーオキシヒドロキシプロピルオキシ基又は１，２−ジオキセタニルメチルオキシ基を表す。「＊」は結合位置を示す。〕 The peroxide of Claim 4 which is any one represented by a following formula.
[In the formula, A represents the following chemical formula:
Represents a hydroperoxyhydroxypropyloxy group or a 1,2-dioxetanylmethyloxy group represented by “*” Indicates a binding position. ]
（式中、Ｒ１は、アリルオキシ基、炭素数１〜６のアルキレン基、炭素数６〜１０のアリーレン基及び酸素原子を含み、必要に応じて、炭素数１〜６のアルキル基である置換基を含んで構成され、炭素数が４０までであり、分子量が６５０までの有機基を表す。） The method includes contacting an allyl ether derivative represented by the following general formula (II) with a peroxide to obtain a peroxide represented by the general formula (I). A method for producing a thermal radical polymerization initiator.
(In the formula, R 1 includes an allyloxy group, an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 10 carbon atoms, and an oxygen atom, and optionally, a substitution that is an alkyl group having 1 to 6 carbon atoms. An organic group having up to 40 carbon atoms and a molecular weight of up to 650.
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